US 2011 003 4667A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2011/0034667 A1 Fujdala et al. (43) Pub. Date: Feb. 10, 2011
(54) PROCESSES FOR POLYMERC on Feb. 6, 2010, provisional application No. 61/302. PRECURSORS FORAGS 095, filed on Feb. 6, 2010, provisional application No. SILVER-CONTAINING PHOTOVOLTACS 61/326,540, filed on Apr. 21, 2010.
(75) Inventors: Kyle L. Fujdala, San Jose, CA Publication Classification (US); Wayne A. Chomitz, Oakland, CA (US); Zhongliang Zhu, San (51) Int. Cl. Jose, CA (US); Matthew C. C08G 7S/00 (2006.01) Kuchta, San Francisco, CA (US); C07F I/10 (2006.01) Qinglan Huang, Niskayuna, NY C08G 79/00 (2006.01) (US) (52) U.S. Cl...... 528/373; 556/28: 528/395 Correspondence Address: Eckman Basu LLP (57) ABSTRACT 2225 E. Bayshore Road, Suite 200 This invention relates to processes for compounds, polymeric Palo Alto, CA 94.303-3220 (US) compounds, and compositions used to prepare semiconduc (73) Assignee: PRECURSOR ENERGETICS, tor and optoelectronic materials and devices including thin INC., Santa Clara, CA (US) film and band gap materials. This invention provides a range of compounds, polymeric compounds, compositions, mate (21) Appl. No.: 12/859,039 rials and methods directed ultimately toward photovoltaic applications, transparent conductive materials, as well as (22) Filed: Aug. 18, 2010 devices and systems for energy conversion, including Solar cells. In particular, this invention relates to polymeric precur Related U.S. Application Data Sor compounds and precursor materials for preparing photo voltaic layers. A compound may contain repeating units {M’ (63) Continuation of application No. 12/848,890, filed on (ER)(ER) and M(ER)(ER), wherein M is Ag, each M’ Aug. 2, 2010. is In or Ga, each E is S. Se, or Te, and each R is independently (60) Provisional application No. 61/231,158, filed on Aug. selected, for each occurrence, from alkyl, aryl, heteroaryl, 4, 2009, provisional application No. 61/302,094, filed alkenyl, amido, silyl, and inorganic and organic ligands.
(RE). BABABB Patent Application Publication Feb. 10, 2011 Sheet 1 of 20 US 2011/0034667 A1
(REBABABB Patent Application Publication Feb. 10, 2011 Sheet 2 of 20 US 2011/0034667 A1
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Patent Application Publication Feb. 10, 2011 Sheet 6 of 20 US 2011/0034667 A1
Fig. 6
SYNTHESIS OF POLYMERIC PRECURSORS AND INKS
SUBSTRATES
| MATERIALS
SEMCONDUCTOR AND OPTOELECTRONIC DEVICES
ENERGY CONVERSION SYSTEMS Patent Application Publication Feb. 10, 2011 Sheet 7 of 20 US 2011/0034667 A1
Fig. 7
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(Cuos Agg2(Se'Bu)} 8. N
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8
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Fig. 15
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t O 3: Temperature (°C) Patent Application Publication Feb. 10, 2011 Sheet 17 of 20 US 2011/0034667 A1
Fig. 17
Ctigos AgginSe2
Patent Application Publication Feb. 10, 2011 Sheet 18 of 20 US 2011/0034667 A1
Cup. Agginsey
xx-xx-xx-xx-xx-xx-xx-xxxx 8 “...... 8: ------2-theta (deg) Patent Application Publication Feb. 10, 2011 Sheet 19 of 20 US 2011/0034667 A1
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2-theta (deg) US 2011/0034667 A1 Feb. 10, 2011
PROCESSES FOR POLYMERC optoelectronic materials are often less efficient and less Suc PRECURSORS FORAGS cessful in achieving desired compositions and properties. For SILVER-CONTAINING PHOTOVOLTACS example, no molecule is currently known that can be used alone, without other compounds, to readily prepare a layer CROSS REFERENCE TO RELATED from which CIGS materials of any arbitrary stoichiometry APPLICATIONS can be made. Compounds or compositions that can fulfill this goal have long been needed. 0001. This application is a continuation of prior U.S. 0008. A further difficulty is the need to heat the substrate application Ser. No. 12/848,890, filed Aug. 2, 2010, which to high temperatures to finish the film. This can cause claims the benefit of U.S. Provisional Application No. unwanted defects due to rapid chemical or physical transfor 61/231,158, filed Aug. 4, 2009, U.S. Provisional Application mation of the layers. High temperatures may also limit the No. 61/302,094, filed Feb. 6, 2010, U.S. Provisional Appli nature of the substrate that can be used. For example, it is cation No. 61/302,095, filed Feb. 6, 2010, and U.S. Provi desirable to make thin film photovoltaic layers on a flexible sional Application No. 61/326,540, filed Apr. 21, 2010, each Substrate Such as a polymer or plastic that can be formed into of which is hereby incorporated by reference in its entirety. a roll for processing and installation on a building or outdoor structure. Polymer substrates may not be compatible with the BACKGROUND high temperatures needed to process the semiconductor lay 0002 The development of photovoltaic devices such as ers. Preparing thin film photovoltaic layers on a flexible sub Solar cells is important for providing a renewable source of strate is an important goal for providing renewable solar energy and many other uses. The demand for power is ever energy and developing new generations of electro-optical rising as the human population increases. In many geographic products. areas, Solar cells may be the only way to meet the demand for 0009 Moreover, methods for large scale manufacturing of power. The total energy from Solar light impinging on the CIGS and related thin film solar cells can be difficult because earth for one hour is about 4x10' joules. It has been esti of the chemical processes involved. In general, large scale mated that one hour of total Solar energy is as much energy as processes for solar cells are unpredictable because of the is used worldwide for an entire year. Thus, billions of square difficulty in controlling numerous chemical and physical meters of efficient solar cell devices will be needed. parameters involved in forming an absorber layer of suitable 0003 Photovoltaic devices are made by a variety of pro quality on a substrate, as well as forming the other layers cesses in which layers of semiconducting material are created required to make an efficient solar cell and provide electrical on a Substrate. Layers of additional materials are used to conductivity. protect the photovoltaic semiconductor layers and to conduct 0010 What is needed are compounds, compositions and electrical energy out of the device. Thus, the usefulness of an processes to produce materials for photovoltaic layers, espe optoelectronic or Solar cell product is in general limited by the cially thin film layers for solar cell devices and other products. nature and quality of the photovoltaic layers. 0004 For example, one way to produce a solar cell product BRIEF SUMMARY involves depositing a thin, light-absorbing, Solid layer of the 0011. This invention relates to compounds and composi material copper indium gallium diselenide, known as tions used to prepare semiconductor and optoelectronic mate “CIGS, on a substrate. A solar cell having a thin film CIGS rials and devices including thin film and band gap materials. layer can provide low to moderate efficiency for conversion of This invention provides a range of compounds, compositions, sunlight to electricity. The CIGS layer can be made by pro materials and methods directed ultimately toward photovol cessing at relatively high temperatures several elemental taic applications and other semiconductor materials, as well Sources containing the atoms needed for CIGS. In general, as devices and systems for energy conversion, including Solar CIGS materials are complex, having many possible Solid cells. In particular, this invention relates to novel processes, phases. compounds and materials for preparing semiconductor mate 0005. The CIGS elemental sources must be formed or rials including CAIGS Cu/Ag/In/Ga? S/Se materials. deposited, either individually or as a mixture, in a thin, uni 0012. This invention provides a range of compounds, form layer on the substrate. For example, deposition of the compositions, materials and methods for preparing semicon CIGSSources can be done as a co-deposition, or as a multistep ductors and materials, as well as optoelectronic devices and deposition. The difficulties with these approaches include photovoltaic layers. Among other things, this disclosure pro lack of uniformity of the CIGS layers, such as the appearance vides precursor molecules and compositions for making and of different Solid phases, imperfections in crystalline par using semiconductors such as for photovoltaic layers, Solar ticles, Voids, cracks, and other defects in the layers. cells and other uses. In particular, this invention encompasses 0006 For example, some methods for solar cells are dis compounds and compositions containing a combination of closed in U.S. Pat. Nos. 5,441,897, 5,976,614, 6,518,086, the elements copper, silver, indium, gallium, selenium, and 5,436,204, 5,981,868, 7,179,677, 7,259,322, U.S. Patent sulfur, including CuAgInGaS/Se or CAIGS, which are useful Publication No. 2009/0280598, and PCT International Appli for thin film solar cells and other uses. cation Publication NOS. WO2008.057119 and 0013. In some embodiments, this invention includes poly WO2O08063190. meric precursor compounds and compositions for preparing 0007. A significant problem is the inability in general to semiconductors, optoelectronic devices and photovoltaic lay precisely control the Stoichiometric ratios of the metal atoms CS. in the layers. Many semiconductor and optoelectronic appli 0014. The compounds and compositions of this disclosure cations are highly dependent on the ratios of certain metal are stable and advantageously allow control of the Stoichiom atoms in the material. Without direct control over those sto etry of the atoms in the semiconductors, particularly the metal ichiometric ratios, processes to make semiconductor and atOmS. US 2011/0034667 A1 Feb. 10, 2011
0.015. In various embodiments of this invention, chemi (RE)-BB(AB),(AB), (RE)-BB(AB'),(AB),(AB'), cally and physically uniform semiconductor layers can be (RE)-BB(AB'),(AB),(AB'), (RE)-BB(AB),(AB), prepared with the polymeric precursor compounds described (RE)-BB(AB),(AB),(AB), and a mixture of any of the herein. foregoing, wherein A is the repeat unit {M (ER)(ER), B is 0016. The compounds and compositions of this disclosure the repeat unit {M'(ER)(ER)}, p is one or more, n is one or are useful to prepare semiconductor layers having enhanced more, or n is two or more, or n is three or more, and m is one uniformity and Superior properties. O. O. 0017. In further embodiments, solar cells and other prod ucts can be made in processes operating at relatively low 0021 Embodiments of this invention may further provide temperatures with the compounds and compositions of this an ink comprising one or more precursor compounds above disclosure. and one or more carriers. An ink may be a solution of the 0018. The polymeric precursor compounds and composi compounds in an organic carrier, and may contain a dopant or tions of this disclosure can provide enhanced processability alkali dopant. An ink may further contain one or more com for solar cell production, and the ability to be processed on a ponents selected from the group of a Surfactant, a dispersant, variety of substrates including polymers at relatively low an emulsifier, an anti-foaming agent, a dryer, a filler, a resin temperatures. The advantages provided by the compounds, binder, a thickener, a viscosity modifier, an anti-oxidant, a compositions, and materials of this invention in making pho flow agent, a plasticizer, a conductivity agent, a crystalliza tovoltaic layers and other semiconductors and devices are tion promoter, an extender, a film conditioner, an adhesion generally obtained regardless of the morphology or architec promoter, and a dye. ture of the semiconductors or devices. 0022. This disclosure further provides methods for mak 0019. In some embodiments, this invention provides a range of compounds comprising repeating units {M(ER) ing a precursor compound comprising: a) providing mono (ER) and M (ER)(ER), wherein each M is Cu or Ag, mer compounds M'(ER), M’(ER), M'(ER) and M' each M is In or Ga, each E is S, Se, or Te, and each R is (ER); and b) contacting the monomer compounds; wherein independently selected, for each occurrence, from alkyl, aryl, M' is In, M' is Ga, M' is Cu, and M' is Ag, each E is S, heteroaryl, alkenyl, amido, silyl, and inorganic and organic Se, or Te, and each R is independently selected, for each ligands. A compound may be a CAIGS, AIGS, CAIS, CAGS, occurrence, from alkyl, aryl, heteroaryl, alkenyl, amido, silyl, AIS, or AGS precursor compound. A compound can have the and inorganic and organic ligands. In certain embodiments, empirical formula (C-Ag), M. 'M',), (S,Se)R), the methods provide a CAIGS, AIGS, CAIS, CAGS, AIS, or wherein M' and M' are different atoms of Group 13, AGS precursor compound. wherein X is from 0 to 1, y is from 0 to 1, Z is from 0 to 1, u is 0023. In further aspects, this invention includes articles from 0.5 to 1.5, v is from 0.5 to 1.5, w is from 2 to 6, and R comprising one or more compounds or inks above deposited represents R groups, of which there are w in number, which onto a Substrate. The depositing can be done by spraying, are each independently selected from alkyl, aryl, heteroaryl, spray coating, spray deposition, spray pyrolysis, printing, alkenyl, amido, silyl, and inorganic and organic ligands. A screen printing, inkjet printing, aerosoljet printing, ink print compound may be deficient or enriched in the quantity of a ing, jet printing, stamp/pad printing, transfer printing, pad Group 11 atom. A compound can be an inorganic polymer or printing, flexographic printing, gravure printing, contact coordination polymer, and may be linear, branched, cyclic, or printing, reverse printing, thermal printing, lithography, elec a mixture of any of the foregoing. A compound can be an trophotographic printing, electrodepositing, electroplating, alternating copolymer, a block copolymer, or a random electroless plating, bath deposition, coating, dip coating, wet copolymer. coating, spin coating, knife coating, roller coating, rod coat 0020. In some aspects, a compound may have any one of ing, slot die coating, meyerbar coating, lip direct coating, the formulas: (RE)-BB(AB) (RE)-B(AB),B, (RE)-B capillary coating, liquid deposition, Solution deposition, (AB), B(AB), (RE)-(BA), BB, (RE)-B(BA),B, (RE)- layer-by-layer deposition, spin casting, Solution casting, and (BA), B(BA), B, *(AB), *(BA), (RE)-(BB) combinations of any of the forgoing. The Substrate may be (AABB), (RE)-(BB)(AABB),(AB), (RE)-(B)(AABB), selected from a semiconductor, a doped semiconductor, sili (B)(AB) (RE)-B(AB), (RE)-(BA),B, con, gallium arsenide, insulators, glass, molybdenum glass, silicon dioxide, titanium dioxide, Zinc oxide, silicon nitride, a metal, a metal foil, molybdenum, aluminum, beryllium, cad mium, cerium, chromium, cobalt, copper, gallium, gold, lead, manganese, molybdenum, nickel, palladium, platinum, rhe E ER - a nium, rhodium, silver, stainless steel, Steel, iron, strontium, MSME ER tin, titanium, tungsten, Zinc, Zirconium, a metal alloy, a metal silicide, a metal carbide, a polymer, a plastic, a conductive R polymer, a copolymer, a polymer blend, a polyethylene S. R. R. R. terephthalate, a polycarbonate, a polyester, a polyester film, a M1TYMBINMA 1 YMB2 mylar, a polyvinyl fluoride, polyvinylidene fluoride, a poly n1n/n/E E in E ethylene, a polyetherimide, a polyetherSulfone, a polyether R R R R p ketone, a polyimide, a polyvinylchloride, an acrylonitrile R. R. R. butadiene styrene polymer, a silicone, an epoxy, paper, coated paper, and combinations of any of the forgoing. The Substrate M1TYMBITYM42n1n 1-1N SMB2 E E E may be a shaped substrate including a tube, a cylinder, a R R R R p roller, a rod, a pin, a shaft, a plane, a plate, a blade, a vane, a 0 00 000 ABAB2AB3 oooooo curved Surface or a spheroid. 0024. In some embodiments, this invention provides methods for making an article by (a) providing one or more US 2011/0034667 A1 Feb. 10, 2011 compounds or inks above; (b) providing a Substrate; and (c) 0035 FIG. 4 shows an embodiment of a polymeric pre depositing the compounds or inks onto the Substrate. cursor compound (MPP-CAIGS). As shown in FIG. 4, the 0025. This invention includes materials having the empiri structure of the compound can be represented by the formula cal formula (Cu, Ag,), (In Ga),(S1-Se...), where X is (RE),BA(BA), B(BA), B, wherein A is the repeat unit {M from 0.001 to 1, y is from 0 to 1, Z is from 0 to 1, u is from 0.5 (ER)}, B is the repeat unit {M (ER).}, E is a chalcogen, and to 1.5, V is from 0.5 to 1.5, and w is from 1 to 3. R is a functional group. 0026. In certain embodiments, this invention provides 0036 FIG. 5 shows an embodiment of a polymeric pre methods for making a material comprising, (a) providing one cursor compound (MPP-CAIGS). As shown in FIG. 5, the or more compounds or above; (b) providing a Substrate; (c) structure of the compound can be represented by the formula depositing the compounds or inks onto the Substrate; and (d) “(BA), wherein A is the repeat unit {M'(ER)}, B is the heating the substrate at a temperature of from about 20°C. to repeat unit {M (ER)}. Eis a chalcogen, and R is a functional about 650° C. in an inert atmosphere, thereby producing a group. material. 0037 FIG. 6: Schematic representation of embodiments 0027. In some embodiments, this disclosure provides a of this invention in which polymeric precursors and ink com thin film material made by a process comprising, (a) provid positions are deposited onto particular Substrates by methods ing one or more compounds or inks above; (b) providing a including spraying, coating, and printing, and are used to Substrate; (c) depositing the compounds or inks onto the make semiconductor and optoelectronic materials and Substrate; and (d) heating the Substrate at a temperature of devices, as well as energy conversion systems. from about 20° C. to about 650° C. in an inert atmosphere, 0038 FIG. 7: Schematic representation of a solar cell thereby producing a thin film material having a thickness of embodiment of this invention. from 0.05 to 10 micrometers. 0039 FIG. 8 shows the transition of a polymeric precursor 0028. In further embodiments, this invention discloses a embodiment (MPP) of this invention represented by the photovoltaic absorber having the empirical formula (Cu, repeat unit formula (CuosAgo2(Se'Bu). In} into a Cuos Ago. Ag),(In-Ga,), (S1-Se...), where X is from 0.001 to 1, y is 2InSea material as determined by thermogravimetric analysis. from 0 to 1, Z is from 0 to 1, u is from 0.5 to 1.5, V is from 0.5 to 1.5, and w is from 1 to 3. 0040 FIG.9 shows the transition of a polymeric precursor 0029 Embodiments of this invention include methods for embodiment (MPP) of this invention represented by the making a photovoltaic absorber layer on a Substrate compris repeat unit formula (Cuo Agos(Se'Bu). In} into a Cuo Ago. ing, (a) providing one or more compounds or inks above; (b) sInSea material as determined by thermogravimetric analysis. providing a Substrate; (c) depositing the compounds or inks 0041 FIG. 10 shows the transition of a polymeric precur onto the Substrate; and (d) heating the Substrate at a tempera sor embodiment (MPP) of this invention represented by the ture of from about 100° C. to about 650° C. in an inert repeat unit formula (Cuoss Ago (Se'Bu)sos Ino, Gaos into atmosphere, thereby producing a photovoltaic absorber layer a Cuoss Ago. Ino, Gao Sea material as determined by ther having a thickness of from 0.001 to 100 micrometers. mogravimetric analysis. 0030. In some embodiments, this invention includes a 0042 FIG. 11 shows the transition of a polymeric precur photovoltaic device made with polymeric precursors. In cer sor embodiment (MPP) of this invention represented by the tain aspects, this invention contemplates a photovoltaic sys repeat unit formula (Cuos Agos (Se'Bu), Ino, Gaos into a tem and methods for providing electrical power using a pho Cuos Agos Ino, Gao. Sea material as determined by thermo tovoltaic device or system to convert light into electrical gravimetric analysis. energy. 0043 FIG. 12 shows the transition of a polymeric precur 0031. This brief summary, taken along with the detailed sor embodiment (MPP) of this invention represented by the description of the invention, as well as the figures, the repeat unit formula Agos(Se'Bu) oIn} into a Agos InSe2 appended examples and claims, as a whole, encompass the material as determined by thermogravimetric analysis. disclosure of the invention. 0044 FIG. 13 shows the transition of a polymeric precur sor embodiment (MPP) of this invention represented by the BRIEF DESCRIPTION OF THE DRAWINGS repeat unit formula Ags(Se'Bu) as In} into a Ags InSe2 0032 FIG. 1 shows an embodiment of a polymeric pre material as determined by thermogravimetric analysis. PFIG. cursor compound (MPP-CAIGS). As shown in FIG. 1, the 14 shows the transition of a polymeric precursor embodiment structure of the compound can be represented by the formula (MPP) of this invention represented by the repeat unit for (RE). BABABB, wherein A is the repeat unit {M'(ER), Bis mula Ag(Se'Bu)Ga} into a AgGaSe material as deter the repeat unit {M(ER), E is a chalcogen, and R is a mined by thermogravimetric analysis. functional group. 0045 FIG. 15 shows the transition of a polymeric precur 0033 FIG. 2 shows an embodiment of a polymeric pre sor embodiment (MPP) of this invention represented by the cursor compound (MPP-CAIGS). As shown in FIG. 2, the repeat unit formula (Agos(Se'Bu)ssino.20Gaoso into a Ago. structure of the compound can be represented by the formula 8InooGaoso Sea material as determined by thermogravimet (RE). BABABBABAB, wherein A is the repeat unit {M (ER) ric analysis. }, B is the repeat unit {M'(ER)}, E is a chalcogen, and R is 0046 FIG. 16 shows the transition of a polymeric precur a functional group. sor embodiment (MPP) of this invention represented by the 0034 FIG. 3 shows an embodiment of a polymeric pre repeat unit formula Ag(Se'Bu), Inoso Gaozo into a AgIno. cursor compound (MPP-CAIGS). As shown in FIG. 3, the soGaozo Sea material as determined by thermogravimetric structure of the compound can be represented by the formula analysis. (RE).BA(BA),BB, wherein A is the repeat unit {M'(ER)}, 0047 FIG. 17 shows the X-ray diffraction pattern of a B is the repeat unit {M (ER), E is a chalcogen, and R is a CAIS material made with the polymeric precursor Cuo. functional group. 05Agogs(Se'Bu). In}. US 2011/0034667 A1 Feb. 10, 2011
0048 FIG. 18 shows the X-ray diffraction pattern of a 0060. In further embodiments, this invention provides a CAIS material made with the polymeric precursor Cuo. range of polymeric precursor compounds for which the solu 1 Agos(Se'Bu). In}. bility can advantageously be controlled and selectively var 0049 FIG. 19 shows the X-ray diffraction pattern of a AIS ied. In these embodiments, the solubility of a polymeric pre material made with the polymeric precursor Ag(Se'Bu). In}. cursor can be enhanced by variation of the nature and 0050 FIG. 20 shows the X-ray diffraction pattern of a AIS molecular size and weight of one or more organic ligands material made with the polymeric precursor Agos(Se'Bu). attached to the compound. The control of polymeric precur 9In}. sor Solubility can allow the preparation of inks having con trolled Viscosity, for example, among other properties. DETAILED DESCRIPTION 0061. In general, the structure and properties of the poly 0051. This disclosure provides a range of novel polymeric meric compounds, compositions, and materials of this inven compounds, compositions, materials and methods for semi tion provide advantages in making photovoltaic layers, semi conductor and optoelectronic materials and devices including conductors, and devices regardless of the morphology, thin film photovoltaics and various semiconductor band gap architecture, or manner of fabrication of the semiconductors materials. or devices. 0052 Among other advantages, the polymeric com 0062. The polymeric precursor compounds of this inven pounds, compositions, materials and methods of this inven tion are desirable for preparing semiconductor materials and tion can provide a precursor compound for making semicon compositions. A polymeric precursor may have a chain struc ductor and optoelectronic materials, including CAIGS ture containing two or more different metal atoms which may absorber layers for solar cells and other devices. In some be bound to each other through interactions or bridges with embodiments, the optoelectronic Source precursor com one or more chalcogen atoms of chalcogen-containing moi pounds of this invention can be used alone, without other eties. compounds, to prepare a layer from which CAIGS, AIGS, 0063. With this structure, when a polymeric precursor is CAIS, CAGS, AIS, AGS and other materials can be made. used in a process such as deposition, coating or printing on a CAIGS refers to Cu/Ag/In/Ga/S/Se, and further definitions Substrate or Surface, as well as processes involving annealing, are given below. sintering, thermal pyrolysis, and other semiconductor manu 0053 Polymeric precursor compounds may also be used facturing processes, use of the polymeric precursors can in a mixture with additional compounds to control Stoichiom enhance the formation of a semiconductor and its properties. etry of a layer or material. 0064. The polymeric precursor compounds and composi 0054. In general, the ability to select a predetermined sto tions of this invention may advantageously be used in pro ichiometry in advance means that the Stoichiometry is con cesses for solar cells that avoid additional sulfurization or trollable. Selenization steps. 0055. This invention provides polymeric compounds and 0065 For example, the use of a polymeric precursor in compositions for photovoltaic applications, as well as devices semiconductor manufacturing processes can enhance the for and systems for energy conversion, including Solar cells. mation of M-E-M'bonding, Such as is required for chalcogen 0056. The polymeric compounds and compositions of this containing semiconductor compounds and materials, disclosure include polymeric precursor compounds and poly wherein M is an atom of one of Groups 3 to 12, M' is an atom meric precursors for materials for preparing novel semicon of Group 13, and E is a chalcogen. ductor and photovoltaic materials, films, and products. Among other advantages, this disclosure provides stable 0066. In some embodiments, a polymeric precursor com polymeric precursor compounds for making and using lay pound contains a chalcogenide bridge having the formula ered materials and photovoltaics, such as for Solar cells and M“(E)M', M (E)M or M-(E)M. other uses. 0067. A polymeric precursor compound may advanta 0057. A photovoltaic absorber material of this disclosure geously contain linkages between atoms, where the linkages can retain the precise Stoichiometry of the precursor used to are desirably found in a material of interest, such as a CAIGS, make the absorber material. AIGS, CAIS, CAGS, AIS, or AGS material, which material 0058 Polymeric precursors can advantageously form a can be made from the polymeric precursor, or a combination thin, uniform film. In some embodiments, a polymeric pre of polymeric precursors. cursor is an oil that can be processed and deposited in a 0068. The polymeric precursor compounds of this disclo uniform layer on a Substrate. This invention provides poly Sure are stable and advantageously allow control of the sto meric precursors that can be used neat to make a thin film, or ichiometry, structure, and ratios of the atoms in a semicon can be processed in an ink composition for deposition on a ductor material or layer, in particular, the metal atoms. Substrate. The polymeric precursors of this invention can have 0069. Using polymeric precursor compounds in any par Superior processability to form a thin film for making photo ticular semiconductor manufacturing process, the stoichiom voltaic absorber layers and solar cells. etry of the metal atoms can be determined and controlled. The 0059. In certain aspects, this invention provides polymeric structure of a polymeric precursor may contain a number of precursor compounds having enhanced solubility in organic different metal atoms. Polymeric precursors having different solvents. The solubility of a polymeric precursor makes it metal atoms, and different numbers of metal atoms can be advantageous for preparing photovoltaic materials using any contacted in precise amounts to control the metal atom sto one of various processes that require deposition of the pre ichiometry in a semiconductor manufacturing process. For cursor on a Substrate, such as for making thin film Solar cells. processes operating at relatively low temperatures, such as A polymeric precursor may have enhanced solubility in one certain printing, spraying, and deposition methods, the poly or more carriers for preparing an ink to be deposited on a meric precursor compounds can maintain the desired Stoichi substrate. ometry. As compared to processes involving multiple sources US 2011/0034667 A1 Feb. 10, 2011 for semiconductor preparation, the polymeric precursors of dently selected, for each occurrence, from alkyl, aryl, het this invention can provide enhanced control of uniformity. eroaryl, alkenyl, amido, silyl, and inorganic and organic 0070 These advantageous features allow enhanced con ligands. trol over the structure of a semiconductor material made with 0084. A polymeric compound comprising repeating units the polymeric precursor compounds of this invention. The {M (ER)(ER) and M(ER)(ER), wherein each M is Cu polymeric precursors of this disclosure are Superior building or Ag, each M is In or Ga, each E is S. Se, or Te, and each R blocks for semiconductor materials because they may pro is independently selected, for each occurrence, from alkyl, vide atomic-level control of semiconductor composition. aryl, heteroaryl, alkenyl, amido, silyl, and inorganic and 0071. The polymeric precursor compounds, compositions organic ligands. and methods of this disclosure may allow direct and precise control of the stoichiometric ratios of metal atoms. For I0085. The compound above wherein each E is sulfur or example, in some embodiments, a polymeric precursor can be Selenium. used alone, without other compounds, to readily prepare a I0086. The compound above wherein E is selenium. layer from which CAIGS, AIGS, CAIS, CAGS, AIS, or AGS I0087. The compound above wherein the compound is a materials of any arbitrary Stoichiometry can be made. CAIGS, AIGS, CAIS, CAGS, AIS, or AGS precursor com 0072. In certain aspects, polymeric precursor compounds pound. can be used to form nanoparticles that can be used in various I0088. The compound above wherein the compound has methods to prepare semiconductor materials. the empirical formula (Cu, Ag,),(M'.M.),(S,Se) 0073 Embodiments of this invention may further provide R), wherein M' and M’ are different atoms of Group 13, processes using nanoparticles of polymeric precursors to wherein X is from 0 to 1, y is from 0 to 1, Z is from 0 to 1, u is enhance the formation and properties of a semiconductor from 0.5 to 1.5, v is from 0.5 to 1.5, w is from 2 to 6, and R material. represents R groups, of which there are w in number, which 0074. In aspects of this invention, chemically and physi are each independently selected from alkyl, aryl, heteroaryl, cally uniform semiconductor layers can be prepared with alkenyl, amido, silyl, and inorganic and organic ligands. In polymeric precursor compounds. some embodiments, x is from 0.001 to 0.5, y is from 0 to 1, Z 0075. The compounds and compositions of this disclosure is from 0.5 to 1, u is from 0.5 to 1.5, v is from 0.5 to 1.5, w is are useful to prepare semiconductor layers having enhanced from 2 to 6. In some embodiments, x is from 0.001 to 0.3, y is uniformity and Superior properties. from 0 to 1, Z is from 0.7 to 1, u is from 0.5 to 1.5, V is 1, w is 0076. In further embodiments, solar cells and other prod from 3 to 5. In some embodiments, x is from 0.001 to 0.1, y is ucts can be made in processes operating at relatively low from 0 to 1, Z is from 0.8 to 1, u is from 0.5 to 1.5, V is 1, w is temperatures using the polymeric precursor compounds and from 3.5 to 4.5. compositions of this disclosure. I0089. The compound above wherein the compound is 0077. The polymeric precursors of this disclosure are use deficient or enriched in the quantity of a Group 11 atom. ful to prepare inks that can be used in various methods to 0090 The compound above wherein the compound is an prepare semiconductor materials. inorganic polymer or coordination polymer. 0078. The polymeric precursor compounds and composi 0091. The compound above wherein the compound is lin tions of this disclosure can provide enhanced processability ear, branched, cyclic, or a mixture of any of the foregoing. for solar cell production. 0092. The compound above wherein each R is indepen 0079 Certain polymeric precursor compounds and com dently selected, for each occurrence, from (C1-8)alkyl, or positions of this disclosure provide the ability to be processed from (C1-6)alkyl, or from (C1-4)alkyl, or from (C1-3)alkyl, at relatively low temperatures, as well as the ability to use a or from (C1-2)alkyl. variety of substrates including flexible polymers in solar 0093. The compound above wherein the compound is an cells. oil at a temperature below about 100° C. 0094. The compound above further comprising three or Embodiments of Polymeric Precursors for CAIGS and AIGS more repeating units {M (ER)(ER)}. Silver-Containing Photovoltaics 0.095 The compound above further comprising three or 0080 Embodiments of this invention include: more repeating units {M'(ER)(ER)}. I0081. A compound comprising repeating units {M (ER) 0096. The compound above further comprising the for (ER) and M(ER)(ER), wherein each M is Cu or Ag, mula (AB), wherein A is the repeat unit {M'(ER)(ER)}, Bis each M is In or Ga, each E is S. Se, or Te, and each R is the repeat unit {M (ER)(ER)}, n is two or more, and R is independently selected, for each occurrence, from alkyl, aryl, independently selected, for each occurrence, from alkyl, aryl, heteroaryl, alkenyl, amido, silyl, and inorganic and organic heteroaryl, alkenyl, amido, silyl, and inorganic and organic ligands. ligands. 0082. A compound comprising two or more repeating 0097. The compound above wherein the compound is an units M(ER)(ER)} and two or more repeating units {M alternating copolymer, a block copolymer, or a random (ER)(ER)}, wherein each M' is Cuor Ag, each M is In or Ga, copolymer. each E is S, Se, or Te, and each R is independently selected, 0098. The compound above wherein the compound has for each occurrence, from alkyl, aryl, heteroaryl, alkenyl, any one of the formulas: (RE)-BB(AB) (RE)-B(AB),B, amido, silyl, and inorganic and organic ligands. (RE)-B(AB), B(AB), (RE)-(BA), BB, (RE)-B(BA),B, I0083. A compound comprising repeating units {M'(ER) (RE)-(BA), B(BA), B, *(AB) '(BA), (RE)-(BB) (ER) or M(ER)(ER), wherein each M' is Cuor Ag, each (AABB), (RE)-(BB)(AABB),(AB), (RE)-(B)(AABB), M” is In or Ga, each E is S, Se, or Te, and each R is indepen (B)(AB) (RE)-B(AB), (RE)-(BA),B, US 2011/0034667 A1 Feb. 10, 2011
0109 The method above wherein M' and M’ are both In, or M' and Mare both Ga. R 0110. The method above wherein M' and Mare both | ER Ag. M3 1 in ME NE1 V 0111. The method above wherein M' and M' are both ER Ag, and M' and M’ are both In or M' and M' are both Ga. R 0112 The method above wherein the compound is a CAIGS, AIGS, CAIS, CAGS, AIS, or AGS precursor com Mi NMB1 isYMd is YMB2 is pound. N1 E1 E1 NE 0113. A compound made by a process comprising reacting R R R R /, monomers M (ER), M (ER), M (ER) and M'(ER), is is wherein M' is In, M' is Ga, M' is Cu, and M' is Ag, each M NMB1 YMg YMB2 E is S, Se, or Te, and each R is independently selected, for N1 N1 NE1 NE each occurrence, from alkyl, aryl, heteroaryl, alkenyl, amido, R R R R p silyl, and inorganic and organic ligands. 0 00 000ABABABoooooo 0114. An article comprising one or more compounds or inks above deposited onto a Substrate. (RE)-BB(AB),(AB), (RE)-BB(AB'),(AB),(AB), 0115 The article above wherein the depositing is done by (RE)-BB(AB'),(AB),(AB), (RE)-BB(AB),(AB), spraying, spray coating, spray deposition, spray pyrolysis, (RE)-BB(AB),(AB),(AB), and a mixture of any of the printing. Screen printing, inkjet printing, aerosoljet printing, foregoing, wherein A is the repeat unit {M'(ER)(ER)}, Bis ink printing, jet printing, stamp/pad printing, transfer print the repeat unit {M (ER)(ER)}, p is one or more, n is one or ing, pad printing, flexographic printing, gravure printing, more, and m is one or more. contact printing, reverse printing, thermal printing, lithogra 0099. An ink comprising one or more compounds above phy, electrophotographic printing, electrodepositing, electro and one or more carriers. plating, electroless plating, bath deposition, coating, dip coat 0100. The ink above wherein the ink is a solution of the ing, wet coating, spin coating, knife coating, roller coating, compounds in an organic carrier. rod coating, slot die coating, meyerbar coating, lip direct 0101 The ink above wherein the ink is a slurry or suspen coating, capillary coating, liquid deposition, Solution deposi sion of the compounds in an organic carrier. tion, layer-by-layer deposition, spin casting, Solution casting, 0102 The ink above further comprising a dopant or alkali and combinations of any of the forgoing. dopant. 0116. The article above wherein the substrate is selected 0103) The ink above further comprising an additional from the group of a semiconductor, a doped semiconductor, indium-containing compound, an additional gallium-con silicon, gallium arsenide, insulators, glass, molybdenum taining compound, or a molybdenum-containing compound. glass, silicon dioxide, titanium dioxide, Zinc oxide, silicon 0104. The ink above further comprising one or more com nitride, a metal, a metal foil, molybdenum, aluminum, beryl ponents selected from the group of a Surfactant, a dispersant, lium, cadmium, cerium, chromium, cobalt, copper, gallium, an emulsifier, an anti-foaming agent, a dryer, a filler, a resin gold, lead, manganese, molybdenum, nickel, palladium, binder, a thickener, a viscosity modifier, an anti-oxidant, a platinum, rhenium, rhodium, silver, stainless steel, Steel, iron, flow agent, a plasticizer, a conductivity agent, a crystalliza strontium, tin, titanium, tungsten, Zinc, Zirconium, a metal tion promoter, an extender, a film conditioner, an adhesion alloy, a metal silicide, a metal carbide, a polymer, a plastic, a promoter, and a dye. conductive polymer, a copolymer, a polymer blend, a poly 0105. The ink above further comprising one or more com ethylene terephthalate, a polycarbonate, a polyester, a poly ponents selected from the group of a conducting polymer, ester film, a mylar, a polyvinyl fluoride, polyvinylidene fluo silver metal, silver selenide, silver sulfide, copper metal, ride, a polyethylene, a polyetherimide, a polyetherSulfone, a indium metal, gallium metal, Zinc metal, an alkali metal, an polyetherketone, a polyimide, a polyvinylchloride, an acry alkali metal salt, an alkaline earth metal salt, a Sodium chal lonitrile butadiene styrene polymer, a silicone, an epoxy, cogenate, a calcium chalcogenate, cadmium Sulfide, cad paper, coated paper, and combinations of any of the forgoing. mium selenide, cadmium telluride, indium sulfide, indium 0117 The article above wherein the substrate is a shaped Selenide, indium telluride, gallium sulfide, gallium selenide, Substrate including a tube, a cylinder, a roller, a rod, a pin, a gallium telluride, Zinc sulfide, Zinc selenide, Zinc telluride, shaft, a plane, a plate, a blade, a vane, a curved surface or a copper Sulfide, copper selenide, copper telluride, molybde spheroid. num sulfide, molybdenum selenide, molybdenum telluride, 0118. A method for making an article, the method com and mixtures of any of the foregoing. pr1S1ng: 0106 A method for making a precursor compound com prising: 0119 (a) providing one or more compounds or inks above: 0107 a) providing monomer compounds M'(ER), M’ I0120 (b) providing a substrate; and (ER). M'(ER) and M'(ER); and 0121 (c) depositing the compounds or inks onto the Sub 0108 b) contacting the monomer compounds; Strate. wherein M' is In, M' is Ga, M' is Cu, and M' is Ag, each 0.122 The method above wherein step (c) is repeated. E is S, Se, or Te, and each R is independently selected, for I0123. The method above further comprising heating the each occurrence, from alkyl, aryl, heteroaryl, alkenyl, amido, substrate at a temperature of from about 100° C. to about 400° silyl, and inorganic and organic ligands. C. to convert the compounds or inks to a material. US 2011/0034667 A1 Feb. 10, 2011
0.124. The method above further comprising heating the 0151 (d) heating the substrate at a temperature of from substrate at a temperature of from about 100° C. to about 400° about 20°C. to about 650° C. in an inert atmosphere, thereby C. to convert the compounds or inks to a material, followed by producing a material. repeating step (c). 0152. A thin film material made by a process comprising, 0.125. The method above further comprising annealing the 0153 (a) providing one or more compounds or inks above: material by heating the Substrate at a temperature of from 0154 (b) providing a substrate; about 300° C. to about 650° C. 0155 (c) depositing the compounds or inks onto the sub 0126 The method above further comprising heating the strate; and substrate at a temperature of from about 100° C. to about 400° 0156 (d) heating the substrate at a temperature of from C. to convert the compounds or inks to a material, and anneal about 20°C. to about 650° C. in an inert atmosphere, thereby ing the material by heating the Substrate at a temperature of producing a thin film material having a thickness of from 0.05 from about 300° C. to about 650° C. to 10 micrometers. 0127. The method above further comprising heating the 0157. A photovoltaic absorber having the empirical for substrate at a temperature of from about 100° C. to about 400° mula (Cul-Ag),(In-Ga,), (S1-Se...), where X is from C. to convert the compounds or inks to a material, depositing 0.001 to 1, y is from 0 to 1, Z is from 0 to 1, u is from 0.5 to 1.5, the compounds or inks onto the Substrate, and annealing the V is from 0.5 to 1.5, and w is from 1 to 3. material by heating the Substrate at a temperature of from 0158. The photovoltaic absorber above wherein X is from about 300° C. to about 650° C. 0.001 to 0.7, y is from 0 to 1, Z is from 0.5 to 1, u is from 0.7 0128. The method above further comprising: to 1.1, V is from 0.9 to 1.1, and w is from 1.5 to 2.5. 0129 (d) heating the substrate at a temperature of from 0159. The photovoltaic absorber above wherein X is from about 100° C. to about 400° C. to convert the compounds or 0.001 to 0.5, y is from 0 to 1, Z is from 0.5 to 1, u is from 0.7 inks to a material; to 1.1, V is from 0.9 to 1.1, and w is from 1.5 to 2.5. 0130 (e) depositing the compounds or inks onto the sub 0160 The photovoltaic absorber above wherein X is from Strate; 0.001 to 0.3, y is from 0 to 1, Z is from 0.5 to 1, u is from 0.7 0131 (f) repeating steps (d) and (e); and to 1.1, V is from 0.9 to 1.1, and w is from 1.5 to 2.5. 0132 (g) annealing the material by heating the substrate at 0.161 A photovoltaic device comprising the photovoltaic a temperature of from about 300° C. to about 650° C. absorber above. 0133. The method above further comprising: 0162. A system for providing electrical power comprising 0134 (d) heating the substrate at a temperature of from a photovoltaic device above. about 100° C. to about 400° C. to convert the compounds or 0163 A method for providing electrical power comprising inks to a material; using a photovoltaic system above to convert light into elec 0135 (e) annealing the material by heating the substrate at trical energy. a temperature of from about 300° C. to about 650° C.; and 0164. A method for making a photovoltaic absorber layer 0.136 (f) repeating steps (c), (d) and (e). on a Substrate comprising, 0.137 The method above further comprising an optional 0.165 (a) providing one or more compounds or inks above: step of selenization or sulfurization, either before, during or 0166 (b) providing a substrate; after any step of heating or annealing. 0.167 (c) depositing the compounds or inks onto the sub 0138 An article made by the method above. strate; and 0.139. A photovoltaic device made by the method above. 0168 (d) heating the substrate at a temperature of from 0140. A material having the empirical formula (Cu, Ag) about 100° C. to about 650° C. in an inert atmosphere, thereby (In Ga),(S1-Se...), where X is from 0.001 to 1, y is from 0 producing a photovoltaic absorberlayer having a thickness of to 1, Z is from 0 to 1, u is from 0.5 to 1.5, V is from 0.5 to 1.5, from 0.001 to 100 micrometers. and w is from 1 to 3. 0141. The material above whereinx is from 0.001 to 0.3, y Empirical Formulas of Precursor Compounds is from 0 to 1, Z is from 0.5 to 1, u is from 0.7 to 1.1, V is from 0169. This disclosure provides a range of polymeric pre 0.9 to 1.1, and w is from 1.8 to 2.4. cursor compounds having two or more different metal atoms 0142. The material above wherein X is from 0.3 to 0.6, y is and chalcogen atoms. from 0 to 1, Z is from 0.5 to 1, u is from 0.7 to 1.1, V is from 0170 In certain aspects, a polymeric precursor compound 0.9 to 1.1, and w is from 1.8 to 2.4. contains metal atoms, and atoms of Group 13, as well as 0143. The material above wherein X is from 0.6 to 1, y is combinations thereof. Any of these atoms may be bonded to from 0 to 1, Z is from 0.5 to 1, u is from 0.7 to 1.1, V is from one or more atoms selected from atoms of Group 15, S, Se, 0.9 to 1.1, and w is from 1.8 to 2.4. and Te, as well as one or more ligands. 0144. The material above wherein the material is a semi 0171 A polymeric precursor compound may be a neutral conductor. compound, or an ionic form, or have a charged complex or 0145 The material above wherein the material is in the counterion. In some embodiments, an ionic form of a poly form of a thin film. meric precursor compound may contain a divalent metal 014.6 An optoelectronic device comprising the material atom, or a divalent metal atom as a counterion. above. 0172 A polymeric precursor compound may contain 0147 A method for making a material comprising, atoms selected from the transition metals of Group 3 through 0148 (a) providing one or more compounds orinks above; Group 12, B, Al. Ga, In, T1, Si, Ge, Sn, Pb. As, Sb, and Bi. 0149 (b) providing a substrate; 0173 Any of these atoms may be bonded to one or more 0150 (c) depositing the compounds or inks onto the sub atoms selected from atoms of Group 15, S, Se, and Te, as well strate; and as one or more ligands. US 2011/0034667 A1 Feb. 10, 2011
0174. A polymeric precursor compound may contain rubber-like solid, oily substance, or liquid. In certain embodi atoms selected from Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, B, Al, ments, a polymeric precursor is melt processable as a flow Ga, In, T1, Si, Ge. Sn, Pb, and Bi. Any of these atoms may be able melt at a temperature below about 200° C., or below bonded to one or more atoms selected from atoms of Group about 180°C., or below about 160° C., or below about 140° 15, S, Se, and Te, as well as one or more ligands. C., or below about 120° C., or below about 100° C., or below 0.175. In some embodiments, a polymeric precursor com about 80°C., or below about 60° C., or below about 40°C. pound may contain atoms selected from Cu, Zn, Ga, In, Tl, Si. 0185. A polymeric precursor compound of this invention Ge. Sn, and Pb. Any of these atoms may be bonded to one or can be crystalline or amorphous, and can be soluble in various more atoms selected from atoms of Group 15, S, Se, and Te. non-aqueous solvents. as well as one or more ligands. 0186 A polymeric precursor compound may contain 0176). In some embodiments, a polymeric precursor com ligands, or ligand fragments, orportions of ligands that can be pound may contain atoms selected from Cu, Zn, Ga, In, Tl, Si. removed under mild conditions, at relatively low tempera Ge. Sn, and Pb. Any of these atoms may be bonded to one or tures, and therefore provide a facile route to convert the poly more chalcogen atoms, as well as one or more ligands. meric precursor to a material or semiconductor. The ligands, 0177. In some variations, a polymeric precursor com or some atoms of the ligands, may be removable in various pound may contain atoms selected from Ag, Cu, Ga., and In. processes, including certain methods for depositing, spray Any of these atoms may be bonded to one or more atoms ing, and printing, as well as by application of energy. selected from S. Se, and Te, as well as one or more ligands. 0187. These advantageous features allow enhanced con trol over the compositional structure of a semiconductor Polymeric Precursor Structure and Properties (MPP) material made with the polymeric precursor compounds of 0.178 A polymeric precursor compound of this disclosure this invention. is stable at ambient temperatures. Polymeric precursors can be used for making layered materials, optoelectronic materi Polymeric Precursors for Semiconductors and Optoelectron als, and devices. Using polymeric precursors advantageously ics (MPP-CAIGS) allows control of the stoichiometry, structure, and ratios of 0188 This invention provides a range of polymeric pre various atoms in a material, layer, or semiconductor. cursor structures, compositions, and molecules having two or 0179 Polymeric precursor compounds of this invention more different metal atoms. may be solids, Solids with low melting temperatures, semi 0189 In some embodiments, a polymeric precursor com solids, flowable solids, gums, or rubber-like solids, oily sub pound contains atoms M” of Group 13 selected from Ga, In, stances, or liquids at ambient temperatures, or temperatures and a combination thereof. moderately elevated from ambient. Embodiments of this dis 0190. These polymeric precursor compounds further con closure that are fluids at temperatures moderately elevated tain monovalent metal atoms M" selected from Cu, Ag, and a from ambient can provide Superior processability for produc mixture thereof. The atoms M' may be any combination of tion of Solar cells and other products, as well as the enhanced atoms of Cu and Ag. ability to be processed on a variety of Substrates including 0191 The polymeric precursors of this disclosure can be flexible substrates. considered inorganic polymers or coordination polymers. 0180. In general, a polymeric precursor compound can be 0.192 The polymeric precursors of this disclosure may be processed through the application of heat, light, kinetic, represented in different ways, using different formulas to mechanical or other energy to be converted to a material, describe the same structure. including a semiconductor material. In these processes, a 0193 In some aspects, a polymeric precursor of this dis polymeric precursor compound undergoes a transition to closure may be a distribution of polymer molecules or chains. become a material. The conversion of a polymeric precursor The distribution may encompass molecules or chains having compound to a material can be done in processes known in the a range of chain lengths or molecular sizes. A polymeric art, as well as the novel processes of this disclosure. precursor can be a mixture of polymers, polymer molecules 0181 Embodiments of this invention may further provide or chains. The distribution of a polymeric precursor can be processes for making optoelectronic materials. Following the centered or weighted about a particular molecular weight or synthesis of a polymeric precursor compound, the compound chain mass. can be deposited, sprayed, or printed onto a substrate by 0194 Embodiments of this invention further provide poly various means. meric precursors that can be described as AB alternating 0182 Conversion of the polymeric precursor compound addition copolymers. to a material can be done during or after the process of 0.195 The AB alternating addition copolymer is in general depositing, spraying, or printing the compound onto the Sub composed of repeat units A and B. The repeat units A and B Strate. are each derived from a monomer. The repeat units A and B 0183) A polymeric precursor compound of this disclosure may also be referred to as being monomers, although the may have a transition temperature below about 400° C., or empirical formula of monomer A is different from the empiri below about 300° C., or below about 280°C., or below about cal formula of repeat unit A. 260° C., or below about 240° C., or below about 220° C., or (0196) The monomer for M can be M'(ER), where M is below about 200° C. Cu or Ag. In certain embodiments, M' is Ag. 0184. In some aspects, polymeric precursors of this dis (0197) The monomer for M? can be M’(ER), where M' is closure include molecules that are melt processable at tem Ga, In, or a mixture of Ga and In. peratures below about 100°C. In certain aspects, a polymeric 0.198. In a polymeric precursor, monomers of A link to precursor can be fluid, flowable, flowable melt, or semisolid monomers of B to provide a polymer chain, whether linear, at relatively low temperatures and can be processed as a neat cyclic, or branched, or of any other shape, that has repeat units solid, semisolid, neat flowable melt, flowable solid, gum, A, each having the formula M'(ER)}, and repeat units B, US 2011/0034667 A1 Feb. 10, 2011 each having the formula {M'(ER)}. The repeat units A and repeat unit {M'(ER), B is the repeat unit {M (ER), E is B may appear in alternating order in the chain, for example, a chalcogen, and R is a functional group defined below. 800 ABABABABAB000. 0207. In another example, an embodiment of a polymeric 0199. In some embodiments, a polymeric precursor may precursor compound of Formula 8 is shown in FIG. 4. As have atoms M” in the structure, where M is Ga or In in shown in FIG. 4, the structure of the compound can be rep resented by the formula (RE). BA(BA), B(BA), B, wherein A random order. is the repeat unit {M'(ER)}, B is the repeat unit {M (ER)}, 0200. The polymeric precursor compounds of this inven E is a chalcogen, and R is a functional group defined below. tion may be made with any desired stoichiometry with respect 0208. In a further example, an embodiment of a polymeric to the number of different metal atoms and Group 13 elements precursor compound of Formula 10 is shown in FIG. 5. As and their respective ratios. The stoichiometry of a polymeric shown in FIG. 5, the structure of the compound can be rep precursor compound may be controlled through the concen resented by the formula" (BA), wherein A is the repeat trations of monomers, or repeating units in the polymer unit {M'(ER), B is the repeat unit M’(ER), E is a chains of the precursors. chalcogen, and R is a functional group defined below. 0201 In some aspects, this disclosure provides polymeric 0209. A polymeric precursor having one of Formulas 1-8 precursors which are inorganic AB alternating addition and 11-13 may be of any length or molecular size. The values copolymers having one of the following Formulas 1 through of nand m can be one (1) or more. In certain embodiments, the 13: values of n and mare 2 or more, or 3 or more, or 4 or more, or 5 or more, or 6 or more, or 7 or more, or 8 or more, or 9 or (RE)-B(AB), Formula 1: more, or 10 or more. In some embodiments, n and m are independently from 2 to about one million, or from 2 to about (RE)-(BA),BIT Formula 2: 100,000, or from 2 to about 10,000, or from 2 to about 5000, or from 2 to about 1000, or from 2 to about 500, or from 2 to (RE)-BB(AB), Formula 3: about 100, or from 2 to about 50. 0210. A cyclic polymeric precursor having one of Formu (RE)-B(AB), B Formula 4: las 9 or 10 may be of any molecular size. The value of n may (RE)-B(AB), B(AB), Formula 5: be two (2) or more. In certain variations, the values of n and m are 2 or more, or 3 or more, or 4 or more, or 5 or more, or 6 or (RE)-(BA),BB Formula 6: more, or 7 or more, or 8 or more, or 9 or more, or 10 or more. In some embodiments, forcyclic Formulas 9 and 10, n is from (RE)-B(BA), B Formula 7: 2 to about 50, or from 2 to about 20, or from 2 to about 16, or from 2 to about 14, or from 2 to about 12, or from 2 to about (RE)-(BA), B(BA), B Formula 8: 10, or from 2 to about 8. (0211. In another aspect, the repeat units {M (ER)} and cyclic (AB), Formula 9: {M'(ER) may be considered “handed” because the metal atom M' and the Group 13 atom Mappear on the left, while cyclic (BA), Formula 10: the chalcogenatom E appears to the right side. Thus, a linear terminated chain will in general require an additional chalco (RE)-(BB)(AABB), Formula 11: gen group or groups on the left terminus, as in Formulas 1-8 and 11-13, to complete the structure. A cyclic chain, as (RE)-(BB)(AABB), (AB), Formula 12: described by Formulas 9 and 10, does not require an addi tional chalcogen group or groups for termination. (RE)-(B)(AABB), (B)(AB), Formula 13: 0212. In certain aspects, structures of Formulas 1-8 and where A and B are as defined above, E is S, Se, or Te, and R 11-13, where n and m are one (1), may be described as is defined below. adducts. For example, adducts include (RE)-BBAB, (RE)- 0202 Formulas 1 and 2 describe ionic forms that have a BABB, and (RE)-BABBAB. counterion or counterions not shown. Examples of counteri 0213. In some embodiments, a polymeric precursor may include a structure that is an AABB alternating block copoly ons include alkali metal ions, Na, Li, and K. mer. For example, a polymeric precursor or portions of a 0203 The formulas RE-B(AB), and RE-(BA) B may precursor structure may contain one or more consecutive describe stable molecules under certain conditions. repeat units {AABB. A polymeric precursor having an 0204 For example, an embodiment of a polymeric precur AABB alternating block copolymer may be represented by sor compound of Formula 4 is shown in FIG.1. As shown in Formula 1 1 above. FIG. 1, the structure of the compound can be represented by 0214. In some aspects, this disclosure provides polymeric the formula (RE), BABABB, wherein A is the repeat unit precursors which are inorganic AB alternating addition {M'(ER)}, B is the repeat unit {M (ER)}, E is a chalcogen, copolymers having the repeat units of Formula 14 and R is a functional group defined below. 0205. In another example, an embodiment of a polymeric precursor compound of Formula 5 is shown in FIG. 2. As Formula 14 shown in FIG. 2, the structure of the compound can be rep resented by the formula (RE), BABABBABAB, wherein A is the repeat unit {M (ER), B is the repeat unit M’(ER), E E ER is a chalcogen, and R is a functional group defined below. MSCM&C ER 0206. In a further example, an embodiment of a polymeric precursor compound of Formula 6 is shown in FIG. 3. As R shown in FIG. 3, the structure of the compound can be rep resented by the formula (RE). BA(BA), BB, wherein A is the where atoms Mare Ga or In, and each E is S, Se, or Te. US 2011/0034667 A1 Feb. 10, 2011 10
0215. In certain aspects, this invention provides polymeric 0218 Infurther aspects, this invention provides polymeric precursors having a number n of the repeat units of Formula precursors which may be represented by Formula 16 14, where n may be 1 or more, or 2 or more, or 3 or more, or 4 or more, or 5 or more, or 6 or more, or 7 or more, or 8 or more, or 9 or more, or 10 or more, or 11 or more, or 12 or Formula 16 O. 0216. The AB copolymer of Formula 14 may also be rep resented as (AB), or (BA), which represents a polymer of any chain length. Another way to represent certain AB copolymers is the formula e ABAB". 0217. In further variations, this invention provides poly where atoms M' and Mare the same or different atoms of meric precursors that may be represented by Formula 15 Group 13 selected from Gaand In, atoms M' and Mare the same or different and are atoms selected from Cu and Ag, each E is S, Se, or Te, and p is one (1) or more. Formula 15 0219. In another aspect, this disclosure provides inorganic R R R R AB alternating copolymers which may be represented by Manver'Yvernme." Formula 17 NE1 NE1 NE1 E sessee ABAB2ABessess Formula 17 R R R R p where B', B, and B are repeat units containing atoms M', M”, and M”, respectively, which are atoms of Ga and In. where atoms M' and Mare the same or different atoms of 0220 Some examples of empirical formulas for mono Group 13 selected from Ga, and In, each E is S, Se, or Te, and mers and polymeric precursors of this invention are Summa p is one (1) or more. rized in Table 1.
TABLE 1. Empirical formulas for monomers, repeat units and polymeric precursors Formula Representative Constitutional Chain Unit Description A. From monomer M (ER), where M is Cuor Ag {M(ER)} From monomer M(ER), where M is Ga, In AB Polymer chain repear unit ABA An adduct, trimer, or oligomer BAB2 {M (ER).M (ER),M’(ER)} Polymer chain repeat unit, M and M? may be the same or different, a trimer or oligomer ABAB2 {M-(ER)M(ER),M (ER), M2(ER), Alternating copolymer (AB), a etramer or oligomer ABABAB Polymer, or an AB trimer, or an oligomer
(AB), or --A-B- O --B-A-- Polymer of any (BA), chain length oo oABABoo o Polymer of any ength, whether inear, branched, or cyclic AABB alternating block copolymer cyclic (AB) O Cyclic polymer cyclic (BA) chain, oligomer or Octaner US 2011/0034667 A1 Feb. 10, 2011
0221. In Table 1, the “representative constitutional chain mer in a dimeric or higher form, when used as a reagent can unit refers to the repeating unit of the polymer chain. In provide the monomer form. For example, compounds of the general, the number and appearance of electrons, ligands, or empirical formula Cu(ER) may occur in aggregated forms R groups in a representative constitutional chain repeating that are insoluble, and when used as a reagent can provide the unit does not necessarily reflect the oxidation state of the monomer form for reaction with M'(ER). metal atom. For example, the chain repeating unit A, which is 0226. The polymeric precursors of this invention obtained {M'(ER), arises from the monomer M'(ER), where M is by reacting monomers M (ER) and M(ER) can be advan a metal atom of monovalent oxidation state 1 (I or one) tageously highly soluble in organic solvent, whereas one or selected from Cu and Ag. It is to be understood that the more of the monomers may have been insoluble. repeating unit exists in the polymer chain bonded to two other 0227. As used herein, the terms “polymer and “poly repeating units, or to a repeating unit and a chain terminating meric' refer to a polymerized moiety, a polymerized mono unit. Likewise, the chain repeating unit B, which is {M'(ER) mer, a repeating chain made of repeating units, or a polymer }, arises from the monomer M'(ER), where M is a Group chain or polymer molecule. A polymer or polymer chain may 13 atom of trivalent oxidation state 3 (III or three) selected be defined by recitation of its repeating unit or units, and may from Ga, In, and a mixture thereof. In one aspect, monomer have various shapes or connectivities such as linear, M(ER), and monomer M(ER), combine to form an AB branched, cyclic, and dendrimeric. Unless otherwise speci repeating unit, which is {M'(ER). M*(ER)}. fied, the terms polymer and polymeric include homopoly 0222. In some aspects, this disclosure provides AB alter mers, copolymers, block copolymers, alternating polymers, nating copolymers which may also be alternating with respect terpolymers, polymers containing any number of different to M' or M. A polymeric precursor that is alternating with monomers, oligomers, networks, two-dimensional networks, respect to M' may contain chain regions having alternating three-dimensional networks, crosslinked polymers, short and atoms M' and M'. A polymeric precursor that is alternating long chains, high and low molecular weight polymer chains, with respect to M” may contain chain regions having alter macromolecules, and otherforms of repeating structures Such nating atoms M' and M'. as dendrimers. Polymers include those having linear, 0223) Infurther aspects, this disclosure provides AB alter branched and cyclic polymer chains, and polymers having nating block copolymers which may contain one or more long or short branches. blocks of n repeat units, represented as (AB), or (BA), 0228. As used herein, the term “polymeric component' where the block of repeat units contains only one kind of atom refers to a component of a composition, where the component M' selected from Group 13. A block may also be a repeat is a polymer, or may form a polymer by polymerization. The unit represented as (A'B), or (BA'), where the block of term polymeric component includes a polymerizable mono repeat units contains only one kind of atom M'. A polymeric mer or polymerizable molecule. A polymeric component may precursor of this disclosure may contain one or more blocks have any combination of the monomers or polymers which of repeat units having different Group 13 atoms in each block, make up any of the example polymers described herein, or or different atoms M' in each block. For example, a poly may be a blend of polymers. meric precursor may have one of the following formulas: 0229 Embodiments of this invention may further provide polymeric precursors having polymer chain structures with (RE)-BB(AB), (AB’), Formula 18: repeating units. The Stoichiometry of these polymeric precur (RE)--BB(AB'),(AB’),(AB'), Formula 19: sors may be precisely controlled to provide accurate levels of any desired arbitrary ratio of particular atoms. Precursor com (RE)--BB(AB'),(AB’),(AB'), Formula 20: pounds having controlled Stoichiometry can be used to make bulk materials, layers, and semiconductor materials having (RE)-BB(AB), (AB), Formula 21: controlled Stoichiometry. In some aspects, precisely control ling the Stoichiometry of a polymeric precursor may be (RE)-BB(A'B),(A’B),(A'B). Formula 22: achieved by controlling the Stoichiometry of the reagents, where B', B represent repeat units M' (ER), and M’ reactants, monomers or compounds used to prepare the poly (ER), respectively, where M', M’ are In, Ga., respec meric precursor. tively, and where A'. A represent repeat units {M'(ER).} 0230. For the polymeric precursors of this invention, the and M'(ER)}, respectively, where M', M'are Cu and group R in the formulas above, or a portion thereof, may be a Ag, respectively. In Formulas 18 through 22, the values of n, good leaving group in relation to a transition of the polymeric m, and p may be 2 or more, or 3 or more, or 4 or more, or 5 or precursor compound at elevated temperatures or upon appli more, or 6 or more, or 7 or more, or 8 or more, or 9 or more, cation of energy. or 10 or more, or 11 or more, or 12 or more. 0231. The functional groups R in the formulas above and 0224. In certain embodiments, an M monomer can con in Table 1 may each be the same or different from the other tain a chelating group -ERE-, for example, having the formula and are groups attached through a carbon or non-carbonatom, M(ERE). including alkyl, aryl, heteroaryl, alkenyl, amido, silyl, and 0225. In some embodiments, a monomer may exist in a inorganic and organic ligands. In some embodiments, the dimeric form under ambient conditions, or a trimeric or groups Rare each the same or different from the other and are higher form, and can be used as a reagent in Such forms. It is alkyl groups attached through a carbon atom. understood that the term monomer would refer to all such 0232. In some aspects, the monomer for M can be repre forms, whether found under ambient conditions, or found sented as M(ER), and the monomer for M can be repre during the process for synthesizing a polymeric precursor sented as M'(ER), where R' and Rare the same or different from the monomer. The formulas M'(ER) and M(ER), for and are groups attached through a carbon or non-carbonatom, example, should be taken to encompass the monomer in Such including alkyl, aryl, heteroaryl, alkenyl, amido, silyl, and naturally-occurring dimeric or higher forms, if any. A mono inorganic and organic ligands. In some embodiments, the US 2011/0034667 A1 Feb. 10, 2011 groups RandR are each the same or different from the other BB, (RE)-B(BA),B, (RE)-(BA), B(BA), B, *(AB), and are alkyl groups attached through a carbon atom. *(BA), (RE)-(BB)(AABB), (RE)-(BB)(AABB), 0233. In certain variations, the monomer for M” may be (AB) (RE)-(B)(AABB)(B)(AB) (RE)-B(AB), and M(ER')(ER), where R' and Rare different and are groups (RE)-(BA),BI, wherein A is the repeat unit {M'(ER)(ER) attached through a carbon or non-carbon atom, including }, B is the repeat unit {M (ER)(ER)}, n is one or more, or n alkyl, aryl, heteroaryl, alkenyl, amido, silyl, and inorganic is two or more, or n is three or more, and m is one or more. In and organic ligands. In some embodiments, the groups R' and further aspects, a polymeric precursor may be a block copoly R., of M*(ER')(ER), are different and are alkyl groups mer containing one or more blocks of repeat units, wherein attached through a carbon atom. each block contains only one kind of atom M'. 0234. In some embodiments, polymeric precursor com 0243 A precursor compound of this disclosure may be a pounds advantageously do not contain a phosphine ligand, or combination ofu (1-x) equivalents of M'(ER), ux equiva a ligand or attached compound containing phosphorus, lents of M'(ER), v(1-y) equivalents of M'(ER), vy arsenic, or antimony, or a halogen ligand. equivalents of M'(ER), wherein M' is Cu and M' is Ag, 0235 Infurther embodiments, the groups R may indepen M' and Mare different atoms of Group 13, wherein the dently be (C1-22)alkyl groups. compound has the empirical formula (M'M',), (M'. 0236. In these embodiments, the alkyl group may be a M”,), (S,Se)R), whereinx is from 0 to 1, y is from 0 to (C1)alkyl (methyl), or a (C2)alkyl (ethyl), or a (C3)alkyl, or a 1, Z is from 0 to 1, u is from 0.5 to 1.5, V is from 0.5 to 1.5, w (C4)alkyl, or a (C5)alkyl, or a (C6)alkyl, or a (C7)alkyl, or a is from 2 to 6, and R represents R groups, of which there are (C8)alkyl, or a (C9)alkyl, or a (C10)alkyl, or a (C11)alkyl, or w in number, which are independently selected from alkyl, a (C12)alkyl, or a (C13)alkyl, or a (C14)alkyl, or a (C15) aryl, heteroaryl, alkenyl, amido, silyl, and inorganic and alkyl, or a (C16)alkyl, or a (C17)alkyl, or a (C18)alkyl, or a organic ligands. In these embodiments, a precursor com (C19)alkyl, ora (C20)alkyl, or a (C21)alkyl, or a (C22)alkyl. pound can have the stoichiometry useful to prepare CAIGS, 0237. In certain embodiments, the groups R may indepen AIGS, CAIS, CAGS, AIS and AGS materials, including dently be (C1-12)alkyl groups. In these embodiments, the materials deficient or enriched in the quantity of a Group 11 alkyl group may be a (C1)alkyl (methyl), or a (C2)alkyl atom. In certain embodiments, M' is Inandy is from 0.65 to (ethyl), or a (C3)alkyl, or a (C4)alkyl, or a (C5)alkyl, or a O.85. (C6)alkyl, or a (C7)alkyl, or a (C8)alkyl, or a (C9)alkyl, or a 0244. A precursor compound of this disclosure may con (C10)alkyl, or a (C11)alkyl, or a (C12)alkyl. tain a quantity of atoms of Group 11 from 0.33 to 3, or from 0238. In certain embodiments, the groups R may indepen 0.33 to 0.9, or from 0.33 to 1, or from 1 to 2, or from 1.2 to 2.5, dently be (C1-6)alkyl groups. In these embodiments, the alkyl or from 2 to 3, as a ratio of moles of atoms of Group 11 to the group may be a (C1)alkyl (methyl), or a (C2)alkyl (ethyl), or total moles of atoms of Group 13, for example as the ratio (Cu a (C3)alkyl, or a (C4)alkyl, or a (C5)alkyl, or a (C6)alkyl. plus Ag) to (In plus Ga), or (Cu+Ag):(In--Ga). 0239. A polymeric precursor compound may be crystal 0245. In further embodiments, a precursor compound can line, or non-crystalline. contain S, Se and Te. 0240. In some embodiments, a polymeric precursor may 0246 A precursor compound of this disclosure may be a be a compound comprising repeating units {M (ER)(ER)} combination of u(1-x) equivalents of Cu(ER), ux equiva and {M'(ER)(ER)}, wherein M' is a monovalent metal atom lents of Ag(ER), v(1-y) equivalents of In(ER), vy equiva selected from Cu and Ag, M' is an atom of Group 13, E is S, lents of Ga(ER), wherein the compound has the empirical Se, or Te, and R is independently selected, for each occur formula (Cu, Ag,),(In-Ga,), ((S1-Se...)R), wherein X is rence, from alkyl, aryl, heteroaryl, alkenyl, amido, silyl, and from 0 to 1, y is from 0 to 1, Z is from 0 to 1, u is from 0.5 to inorganic and organic ligands. In certain embodiments, the 1.5, V is from 0.5 to 1.5, w is from 2 to 6, and R represents R atoms M” in the repeating units {M'(ER)(ER)} are randomly groups, of which there are w in number, which are indepen selected from atoms of Group 13. In certain variations, M' is dently selected from alkyl, aryl, heteroaryl, alkenyl, amido, Ag and the atoms Mare selected from indium and gallium. silyl, and inorganic and organic ligands. E may be only selenium in a polymeric precursor, and the 0247. In some embodiments, a precursor compound can groups R may be independently selected, for each occur be a combination of w(1-z) equivalents of M'' (ER), w Z rence, from (C1-6)alkyl. equivalents of M'(ER), x equivalents of M'(ER), y 0241 Embodiments of this invention may further provide equivalents of M’(ER), wherein M' is Cu and M' is Ag, polymeric precursors that are linear, branched, cyclic, or a M' and Mare different atoms of Group 13, wherein the mixture of any of the foregoing. Some polymeric precursors compound has the empirical formula (Cu, Ag), In,Ga, may be a flowable melt at a temperature below about 100° C. (ER)-(ER)-(ER)-(ER), w is from 0.5 to 1.5, zis 0242. In some aspects, a polymeric precursor may contain from 0 to 1, X is from 0 to 1, y is from 0 to 1, X plus y is one, in repeating units {M'(ER)(ER) and n repeating units {M and wherein R. R. R. Rare the same or each different, and (ER)(ER)}, wherein n is one or more, or n is two or more, or are independently selected, for each occurrence, from alkyl, n is three or more, or n is four or more, or n is eight or more. aryl, heteroaryl, alkenyl, amido, silyl, and inorganic and The repeating units M(ER)(ER)} and M(ER)(ER) may organic ligands. In these embodiments, a precursor com be alternating. A polymeric precursor may be described by pound can have the stoichiometry useful to prepare CAIGS, the formula (AB), wherein A is the repeat unit {M (ER)(ER) AIGS, CAIS, CAGS, AIS and AGS materials, including }, B is the repeat unit {M (ER)(ER)}, n is one or more, or n materials deficient in the quantity of a Group 11 atom. is two or more, and R is independently selected, for each 0248. In some embodiments, a precursor compound can occurrence, from alkyl, aryl, heteroaryl, alkenyl, amido, silyl, be a combination of w equivalents of Ag(ER), X equivalents and inorganic and organic ligands. In some variations, a poly of InCER), y equivalents of Ga(ER), wherein the com meric precursor may have any one of the formulas (RE)-BB pound has the empirical formula Ag, In,Ga (ER), (ER)s. (AB), (RE)-B(AB),B, (RE)-B(AB), B(AB) (RE)-(BA) (ER). w is from 0.5 to 1.5. X is from 0 to 1, y is from 0 to 1,
US 2011/0034667 A1 Feb. 10, 2011 14
0264. Examples of polymeric precursor compounds of this disclosure include compounds having any one of the repeat unit formulas: {Culao Ago.o. (Se'Bu) is (Se'Bu)(Ino. REACTION SCHEME 1: 7Gaos)(Se'Bu)}, {Cuso Agono (SBu),(SBu)(Inoss Gao. initiation 15)(STBu)}: {Cu120Ago20CSBu)4(Bu)(InosoCiao.20) MP (ER) + M (ER) - T M (ER2)(ER)M(ER) (SBu)}: {Cullo Ago20(Se'Bu), (S"Bu)(Ino.75Gao as) 1 (Se'Bu)}, {CuoAgoo (SBu)2(Se'Bu)(Se'Bu)(Ino, Gao. 3)(Se'Bu)2); and {Culos-Agoos (Se'Bu), (SBu)(InocGaol) (SBu)}. (0275. In Reaction Scheme 1, M (ER) and M(ER) are 0265 Examples of polymeric precursor compounds of monomers that form the first adduct 1, M“(ER)M(ER). this disclosure include compounds having any one of the Reaction Scheme 1 represents the initiation of a polymeriza repeat unit formulas: {Cuoco Ago.o. (Se'Bu)(Se'Bu)(Ino. tion of monomers. In one aspect, Reaction Scheme 1 repre 7Gaos)(Se'Bu)}, {Cuoss Agono (SBu)cos(SBu)(InossGao. sents the formation of the intermediate adduct AB. In general, 15)(STBu)}: {Cuoso Ago20CSBu)(S"Bu)(InosoGao.20) among other steps, the polymerization reaction may form (S"Bu)}, {CuozsAgo20(Se'Bu)oos(Se'Bu)(InozsGao.2s) polymer chains by adding monomers to the first adduct 1, so (Se'Bu)}, {Cuoio Agoso (SBu)(Se'Bu)(Ino, Gao)(Se'Bu) that the first adduct 1 may be a transient molecule that is not 2}: {Cuoss Agoso (Se'Bu)oos (SBu)(InocGaol)(SBu)2}: observed when a longer chain is ultimately produced. When {Cuoco Agoao(Se'Bu)2(Inos Ciaos)(Se'Bu)2}: Cuoso Agoso additional monomers are bound to either end of the first (Se'Bu)(Se'Bu)(Inos Gaos)(Se'Bu)}, {Cuoso Agoes (SBu) adduct 1, then the first adduct 1 becomes a repeating unit AB oos (SBu)(Inos Gaos)(SBu)}, {Cuoso Agozo (SBu)(SBu) in the polymer chain. (Ino-Gao)(S"Bu)}, {Cuo.20Ago.7s.(Se'Bu)ogs(Se'Bu)(Ino. 0276. In general, to prepare a polymeric precursor, the 4Gaos)(Se'Bu)2}: {Cuo.20Agoso (SBu)(Se'Bu)(Inos Gaoz) compounds M (ER) and M'(ER) can be generated by vari (Se'Bu)}: {Cuoio Agoss(Se'Bu)oos(SBu)(Inos Gao.7) ous reactions. (0277 For example, a compound M'(ER) can be prepared (SBu)2); and {Cuoio Agogo (Se'Bu)2(Inos Gaoz)(SeBu)2}. by reacting MX with M*(ER). M*(ER) can be prepared by Preparation of Polymeric Precursors (MPP) reacting E with LiR to provide Li(ER). Li(ER) can be acidi 0266 Embodiments of this invention provide a family of fied to provide HER, which can be reacted with Na(OR) or polymeric precursor molecules and compositions which can K(OR) to provide Na(ER) and K(ER), respectively. In these be synthesized from monomers. Monomers of this disclosure reactions, E., R and Mare as defined above. include a compound containing an atom M of Group 13 (0278. In another example, a compound M'(ER) can be selected from Ga and In, and a compound containing a prepared by reacting MX with (RE)Si(CH4). The com monovalent atom M' selected from Cu and Ag. pound (RE)Si(CH) can be made by reacting M*(ER) with 0267 Advantageously facile routes for the synthesis and XSi(CH), where M is Na, Li, or K, and X is halogen. isolation of polymeric precursor compounds of this invention (0279. In another example, a compound M'(ER) can be have been discovered, as described below. prepared by reacting MO with HER. In particular, Cu(ER) 0268. This disclosure provides a range of polymeric pre can be prepared by reacting CuO with HER. cursor compositions which can be transformed into semicon 0280 For example, a compound M'(ER) can be prepared ductor materials and semiconductors. In some aspects, the by reacting M'X with M*(ER). M*(ER) can be prepared as polymeric precursor compositions are precursors for the for described above. mation of semiconductor materials and semiconductors. (0281. In another example, a compound M(ER) can be 0269. In general, the polymeric precursor compositions of prepared by reacting MX with (RE)Si(CH4). The com this invention are non-oxide chalcogen compositions. pound (RE)Si(CH) can be made as described above. 0270. In some embodiments, the polymeric precursor (0282. In another example, a compound M(ER) can be compositions are sources or precursors for the formation of prepared by reacting MR with HER. absorber layers for solar cells, including CAIGS, AIGS, 0283 Moreover, in the preparation of a polymeric precur CAIS, CAGS, AIS, and AGS absorber layers. sor, a compound MM (ER) can optionally be used in place 0271 A polymeric precursor compound may be made of a portion of the compound M'(ER). For example, a com with any desired stoichiometry with respect to the number of pound MM (ER) can be prepared by reacting MX with 4 different metal atoms and Group 13 elements and their equivalents of M" (ER), where M is Na, Li, or K, and X is respective ratios. halogen. The compound M(ER) can be prepared as 0272. As discussed below, a polymeric precursor com described above. pound may be made by reacting monomers to produce a 0284. The propagation of the polymeric precursor can be polymer chain. The polymeric precursor formation reactions represented in part by the formulas in Reaction Scheme 2. The can include initiation, propagation, and termination. formulas in Reaction Scheme 2 represent only some of the 0273 Methods for making a polymeric precursor may reactions and additions which may occur in propagation of include the step of contacting a compound M(ER), with a the polymeric precursor. compound M'(ER), where M', M', E, and Rare as defined above. 0274 As shown in Reaction Scheme 1, a method for mak REACTION SCHEME 2: ing a polymeric precursor may include the step of contacting propogation a compound M(ER"), with a compound M'(ER), where 1 + MPOER) - - M", M', and E areas defined above and the groups RandR (RE)M(ER)M (ER2)(ER)M(ERI) of the compounds may be the same or different and are as 2 defined above. US 2011/0034667 A1 Feb. 10, 2011 15
(ER) and M'(ER), as well as M'(ER) and M'(ER) dur -continued ing polymerization or propagation. propogation 1 + M (ER2) - M4 (ER2)(ER)M(ER)M (ER2) 0293 Certain reactions or additions of the polymeric pre cursor propagation may include the formation of chain 3 branches. As shown in Reaction Scheme 5, the addition of a monomer M'(ER) to the adduct molecule 2 may produce a 0285. In Reaction Scheme 2, the addition of a monomer branched chain 8. M(ER), or M(ER) to the first adduct 1, may produce additional adducts 2 and 3, respectively. In one aspect, Reac tion Scheme 2 represents the formation of the adduct (RE)- REACTION SCHEME 5: BAB, as well as the adduct intermediate AB-M'(ER). In branching general, the adducts 2 and 3 may be transient moieties that are 7 + MA(ER2) --> not observed when a longer chain is ultimately produced. (RE)M(ER)M (ER2)(ER)M(ER)M (ER2)(ER)M(ER) 0286 The products of the initial propagation steps may continue to add monomers in propagation. As shown in Reac tion Scheme 3, adduct 2 may add a monomer M(ER") or M (ER).
REACTION SCHEME3: propogation 2 + M.ER) - T (RE)MP (ER)M (ER2)(ER)M(ER)M (ER2) (4) M (ER2)(ER)M(ER)M (ER2)(ER)M(ER) (5) 0294 The propagation of the polymeric precursor can be ropogation represented in part by the formulas in Reaction Schemes 2, 3, 2 + MPER); PEE"> 4 and 5. The formulas in Reaction Schemes 2, 3, 4 and 5 represent only some representative reactions and additions (RE)M(ER)M(ER)M (ER2)(ER)M(ER). which may occur in propagation of the polymeric precursor. (6) 0295 Termination of the propagating polymer chain may occur by several mechanisms. 0287. In one aspect, Reaction Scheme 3 represents the (0296) In general, because of the valencies of the atoms M' formation of the intermediate adduct (RE)-BAB-M (ER) 4, and M', a completed polymer chain may terminate in a M’ as well as the adduct (RE)-BBAB 6. In general, the mol unit, but not an M' unit. In some aspects, a chain terminating ecules 4, 5 and 6 may be transient molecules that are not unit is a to B unit, or a (ER).Be unit. observed when a longer chain is ultimately produced. 0297. In some aspects, the propagation of the polymeric 0288 Other reactions and additions which may occur precursor chain may terminate when either of the monomers include the addition of certain propagating chains to certain M’(ER) or M'(ER) becomes depleted. other propagating chains. For example, as shown in Reaction 0298. In certain aspects, as shown in Reaction Scheme 6, Scheme 4, adduct 1 may add to adduct 2 to form a longer the propagation of the polymeric precursor chain may termi chain. nate when a growing chain represented by the formula (RE)- BB reacts with another chain having the same terminal (RE)-B unit to form a chain having the formula REACTION SCHEME 4: BooooooBB000000B. propogation 1 + 2 --> (RE)M(ER)M (ER2)(ER)M(ER)M (ER2)(ER)M(ER) REACTION SCHEME 6: 7 termination 2 (RE-BooooooooooooooooooB) -> 0289. In one aspect, Reaction Scheme 4 represents the (RE) BooooooooooooooooooBBooooooooooooooooooB formation of the adduct (RE)-BABAB 7. 0290 Any of the moieties 4, 5, 6, and 7 may be transient, 0299. In Reaction Scheme 6, two chains have combined, and may not be observed when a longer chain is ultimately where the propagation of the polymer chain is essentially produced. terminated and the product chain (RE), Bette‘BBette‘B has 0291. In some variations, a propagation step may provide chain terminating units that are B units. a stable molecule. For example, moiety 6 may be a stable 0300. In further aspects, the propagation of the polymeric molecule. precursor chain may terminate when the growing chain forms 0292. In general, AB alternating block copolymers as a ring. As shown in Reaction Scheme 7, a propagating chain described in Formulas 18 through 22 may be prepared by Such as 5 may terminate by cyclization in which the polymer sequential addition of the corresponding monomers M' chain forms a ring. US 2011/0034667 A1 Feb. 10, 2011 16
are the same or different and are groups attached through a carbon or non-carbon atom, including alkyl, aryl, heteroaryl, REACTION SCHEME 7: alkenyl, amido, silyl, and inorganic and organic ligands. In ER some embodiments, the groups R. R' are the same ordifferent MF M-ER2 cyclization ER21 in Y V and are alkyl groups attached through a carbon atom. 5 - - -- I ER ER termination W A. - ER NMB 0310. In further aspects, the monomers M'(ER)(ER). MS E. YER and M’(ER)(ER), can be used for polymerization, where ERI ERI N M the groups R. R. R. Rare each the same or different from Y. sir ERI -M/ the others and are groups attached through a carbon or non 2 \ ER I 2 carbon atom, including alkyl, aryl, heteroaryl, alkenyl, ER3-M1" NMB-ER amido, silyl, and inorganic and organic ligands. In some ER embodiments, the groups R. R. R. Rare each the same or different from the others and are alkyl groups attached 0301 A polymeric precursor compound may be a single through a carbon atom. chain, or a distribution of chains having different lengths, structures or shapes, such as branched, networked, dendrim 0311 Embodiments of this invention may further provide eric, and cyclic shapes, as well as combinations of the forgo that the Stoichiometry of a polymeric precursor compound ing. A polymeric precursor compound may be any combina may be controlled to any desired level through the adjustment tion of the molecules, adducts and chains described above in of the amounts of each of the monomers provided in the Reaction Schemes 1 through 7. formation reactions. 0302) A polymeric precursor of this disclosure may be made by the process of providing a first monomer compound 0312. As shown in Reaction Scheme 8, a polymerization having the formula M'(ER'), providing a second monomer to form a polymeric precursor may be initiated with a mixture compound having the formula M'(ER), and contacting the of monomers M (ER), M'(ER), and M'(ER) having first monomer compound with the second monomer com any arbitrary ratios of Stoichiometry. pound. 0303. In some embodiments, the first monomer compound may be a combination of compounds having the formulas REACTION SCHEME 8: M'(ER), and M(ER), wherein M' and Mare differ initiation ent atoms of Group 13, and R', Rare the same or different m MP (ER) + n MP(ER2) + M (ER) -> and are independently selected from alkyl, aryl, heteroaryl, M4 (ER)(ER12), MPlmMP2)(ER12) alkenyl, amido, silyl, and inorganic and organic ligands. 1' 0304. In some variations, the second monomer compound may be a combination of compounds having the formulas M'' (ER) and M'(ER), wherein M' is Cu and M' is Ag, 0313. In Reaction Scheme 8, a polymerization can be per and R. Rare defined the same as R' and R. formed with a mixture of monomers in any desired amounts. 0305. In further aspects, a method for making a polymeric In certain variations, a polymerization to form a polymeric precursor may include the synthesis of a compound contain precursor may be initiated with a mixture of any combination ing two or more atoms of M and contacting the compound of the monomers described above, where the number of with a compound M'(ER), where M', M', E and R are as equivalents of each monomer is adjusted to any arbitrary defined above. For example, (ER). M'(ER),M’(ER), can level. be reacted with M'(ER), where M' and M’ are the same or 0314. In some variations, a polymerization to form a poly different atoms of Group 13. 0306 Methods for making a polymeric precursor include meric precursor can be done using the monomers M'(ER') embodiments in which the first monomer compound and the and M'(ER), for example, which can be contacted in any second monomer compound may be contacted in a process of desired quantity to produce any arbitrary ratio of M' to M'. depositing, spraying, coating, or printing. In certain embodi In some aspects, for alternating copolymers of monomers ments, the first monomer compound and the second monomer M(ER) and M'(ER), the ratio of M to M' in the polymeric compound may be contacted at a temperature of from about precursor can be controlled from a ratio as low as 1:2 in the -60° C. to about 100° C., or from about 0°C. to about 200° C. unit BAB, for example, to a ratio of 1:1 in an alternating (AB), polymeric precursor, to a ratio of 1.5:1 or higher. The Controlled Stoichiometry of Polymeric Precursors (MPP) ratio of M to M' in the polymeric precursor may be 0.5 to 0307. A polymeric precursor compound may be made 1.5, or 0.5 to 1, or 1 to 1, or 1 to 0.5, or 1.5 to 0.5. As discussed with any desired stoichiometry with respect to the number of above, in further embodiments, a polymeric precursor com different metal atoms and Group 13 elements and their pound may be made with any desired stoichiometry with respective ratios. respect to the number of different metal atoms and Group 13 0308. In some embodiments, the stoichiometry of a poly elements and their respective ratios. meric precursor compound may be controlled through the 0315. In certain aspects, a polymerization to form a poly numbers of equivalents of the monomers in the formation meric precursor can be done to form a polymeric precursor reactions. having any ratio of M' to M'. As shown in Reaction Scheme 0309. In some aspects, the monomers M'(ER) and M’ 9, a polymeric precursor having the composition {p (ER") can be used for polymerization. Examples of these M(ER)/m M'(ER)/n M’(ER) may be formed using the monomers are InCER), and Ga(ER'), where the groups R. R' mixture of monomers mM'(ER)+n M'(ER)+p M'(ER). US 2011/0034667 A1 Feb. 10, 2011 17
10322. As used herein, the expression M' is enriched, or M is enriched relative to M' refers to a composition or REACTION SCHEME9: formula in which there are more atoms of M" than M. 0323. As shown in Reaction Scheme 11, a polymeric pre m MP (ER) + n MP(ER) + p M (ER) -> cursor having the empirical formula M' (M'. M,,), ((S1 {p M(ER)/m M(ER) in M(ER)} zSe)R) may be formed using the mixture of monomers polymeric precursor M'' (ER), M’(ER), and M(ER).
0316. In certain variations, any number of monomers of REACTION SCHEME 11: M'(ER) and any number of monomers of M*(ER) can be used in the formation reactions. For example, a polymeric (1-) MP (ER) + () MP(ER) + M (ER) -> precursor may be made with the monomers M'(ER), M' {M, (MPM),(ER).) (ER), M'(ER), and M'(ER"), where the number of polymeric precursor equivalents of each monomer is an independent and arbitrary amount. 0317 For example, the ratios of the atoms M':M in a 0324. A precursor compound of this disclosure may be a polymeric precursor may be about 0.5:1 or greater, or about combination of u(1-x) equivalents of Cu(ER), ux equiva 0.6:1 or greater, or about 0.7:1 or greater, or about 0.8:1 or lents of Ag(ER), v(1-y) equivalents of In(ER), vy equiva greater, or about 0.9:1 or greater, or about 0.95:1 or greater. In lents of Ga(ER), wherein the compound has the empirical certain variations, the ratios of the atoms M':M” in a poly formula (Cu, Ag,),(In Ga),((S1-Se...)R), wherein X is meric precursor may be about 1:1 or greater, or about 1.1:1 or from 0 to 1, y is from 0 to 1, Z is from 0 to 1, u is from 0.5 to greater. 1.5, V is from 0.5 to 1.5, w is from 2 to 6, and R represents R 0318. In further examples, the ratios of the atoms M':M groups, of which there are w in number, which are indepen in a polymeric precursor may be from about 0.5 to about 1.2, dently selected from alkyl, aryl, heteroaryl, alkenyl, amido, or from about 0.6 to about 1.2, or from about 0.7 to about 1.1, silyl, and inorganic and organic ligands. or from about 0.8 to about 1.1, or from about 0.8 to about 1, or 0325 A precursor compound of this disclosure may be a from about 0.9 to about 1. In some examples, the ratios of the combination of u(1-x) equivalents of Cu(ER), ux equiva atoms M':M in a polymeric precursor may be about 0.80, or lents of Ag(ER), v(1-y) equivalents of In(ER), vy equiva about 0.82, or about 0.84, or about 0.86, or about 0.88, or lents of Ga(ER), wherein the compound has the empirical about 0.90, or about 0.92, or about 0.94, or about 0.96, or formula (Cu, Ag,),(In-Ga,), ((S1-Se...)R), wherein X is about 0.98, or about 1.00, or about 1.02, or about 1.1, or about from 0 to 1, y is from 0 to 1, Z is from 0 to 1, u is from 0.7 to 1.2, or about 1.3, or about 1.5. In the foregoing ratios M“M”, 1.0, V is from 0.9 to 1.1, w is from 3.6 to 4.4, and R represents the ratio refers to the sum of all atoms of M" or M, respec R groups, of which there are w in number, which are inde tively, when there are more than one kind of M" or M, such pendently selected from alkyl, aryl, heteroaryl, alkenyl, as M'' and M' and M and M'. amido, silyl, and inorganic and organic ligands. 0319. As shown in Reaction Scheme 10, a polymeric pre 0326 In some embodiments, a precursor compound can cursor compound having the repeating unit composition {M' be a combination of w(1-z) equivalents of Cu(ER"), wz. (ER).(m M'n M)(ER)} may be formed using the mix equivalents of Ag(ER), X equivalents of In(ER), y equiva ture of monomers m M'(ER)+n M’(ER)+M (ER). lents of Ga(ER), wherein the compound has the empirical formula (Cu 1-Ag), In,Ga,(ER' )wa (ER)-(ER )s. (ER), w is from 0.5 to 1.5., Z is from 0 to 1, X is from 0 to 1, REACTION SCHEME 10: y is from 0 to 1.x plusy is one, and wherein R', R. R. Rare the same or each different, and are independently selected, for m MP (ER) + n M2(ER) + M (ER) -- each occurrence, from alkyl, aryl, heteroaryl, alkenyl, amido, {M (ER)(m MP, nM)(ER).) silyl, and inorganic and organic ligands. polymeric precursor 0327. In some embodiments, a precursor compound can repeating unit be a combination of w(1-z) equivalents of Cu(ER"), wz. equivalents of Ag(ER), X equivalents of InCER), y equiva lents of Ga(ER), wherein the compound has the empirical formula (Cu 1-Ag), In,Ga,(ER' )wa (ER)-(ER )s. In Reaction Scheme 10, the sum of m and n is one. (ER). w is from 0.7 to 1.0, Z is from 0 to 1, X is from 0 to 1, 0320 Embodiments of this invention may further provide y is from 0 to 1.x plusy is one, and wherein R', R. R. Rare a polymeric precursor made from monomers of M'(ER) and the same or each different, and are independently selected, for M(ER), where the total number of equivalents of mono each occurrence, from alkyl, aryl, heteroaryl, alkenyl, amido, mers of M'(ER) is less than the total number of equivalents of silyl, and inorganic and organic ligands. monomers of M(ER). In certain embodiments, a polymeric 0328. The empirical formula of a polymeric precursor can precursor may be made that is substoichiometric or deficient be, for example, the following: M' (M' M,,), (S1-Se...) in atoms of M relative to atoms of M. R), where M', M' and M’ are as defined above, R is as 0321) As used herein, the expression M' is deficient, or defined above, u is from 0.5 to 1.5, y is from 0 to 1, and Z is M is deficient to M' refers to a composition or formula in from 0 to 1, V is from 0.5 to 1.5, and w is from 2 to 6. which there are fewer atoms of M than M. For example, for 0329. In some embodiments, the empirical formula of a a compound having the empirical formula (Cu, Ag) polymeric precursor is Ag(In-Ga,), (S1-Se..)R), where R (M'M',), (S'il Se...)R), the compound would be defi is as defined above, u is from 0.5 to 1.5, y is from 0 to 1, and cient in a Group 11 atom when u is less than V. Z is from 0 to 1, V is from 0.5 to 1.5, and w is from 2 to 6. US 2011/0034667 A1 Feb. 10, 2011
0330. In some embodiments, the empirical formula of a 0339. In further aspects, the crosslinking of a polymeric polymeric precursor is Ag(In-Ga,), ((Si,Se)R), where R precursor composition may be used to control the variation of is as defined above, u is from 0.7 to 1.2, y is from 0 to 1, and properties of thin films made with the precursor. Z is from 0 to 1, V is from 0.7 to 1.2, and w is from 2 to 6. 0340 Examples of a crosslinking agent include E(Si (CH)), where E is as defined above, which can link poly 0331. In some embodiments, the empirical formula of a merchains via an M-E-M crosslink. polymeric precursor is Ag(Ini-Ga,), (S1-Se...)R), where R 0341 Examples of a crosslinking agent include HEREH, is as defined above, u is from 0.7 to 1.1, y is from 0 to 1, and M'(ERE)H and M'(ERE)M', where M', E, and R are as Z is from 0 to 1, V is from 0.7 to 1.1, and w is from 2 to 6. defined above. 0332. In some embodiments, the empirical formula of a 0342. A crosslinking agent can be made by reacting Cu2O with HEREH to form Cu(ERE)H or Cu(ERE)Cu. polymeric precursor is Ag(Ini-Ga,), (S1-Se...)R), where R 0343 Examples of a crosslinking agent include dithiols is as defined above, u is from 0.7 to 1.1, y is from 0 to 1, and and diselenols, for example, HEREH, where E and Rare as Z is from 0.5 to 1, V is from 0.7 to 1.1, and w is from 2 to 6. defined above. A diselenol can react with two ER groups of 0333. In some embodiments, the empirical formula of a different polymeric precursor chains to link the chains polymeric precursor is Ag(Ini-Ga,), (S1-Se...)R), where R together. is as defined above, u is from 0.8 to 0.95, y is from 0.5 to 1, and 0344 An example of crosslinking using HEREH is shown Z is from 0.5 to 1, v is from 0.95 to 1.05, and w is from 3.6 to in Reaction Scheme 14. In Reaction Scheme 14, two chains of 4.4. a polymeric precursor are linked by the diselenol with elimi 0334. In further aspects, a mixture of polymeric precursor nation of 2 HER. compounds may advantageously be prepared with any desired stoichiometry with respect to the number of different metal atoms and Group 13 elements and their respective REACTION SCHEME 14 ratios. R 0335. As shown in Reaction Scheme 12, a polymeric pre l ER 2 HER cursor compound may be prepared by contacting X equiva 2 M1 Y + HEREH --> lents of M'(ER"), y equivalents of M’(ER), and Z NE1 K equivalents of M'(ER), where M' and M' are different ER atoms of Group 13, X is from 0.5 to 1.5, y is from 0.5 to 1.5, R and Z is from 0.5 to 1.5. A polymeric precursor compound R may have the empirical formula Ag, In, Gal(ER'),(ER)s. (ER), where R', Rand Rare the same or each different from each other.
REACTION SCHEME 12: x MP (ER) + y M2(ER2) + z M (ER) Her MMP, MP,(ER),(ER2)3(ER). polymeric precursor
Crosslinking Polymeric Precursors 0336 Embodiments of this invention encompass methods 0345. In another example, Cu(ERE)Cu can be used dur and compositions for crosslinking polymeric precursors and ing synthesis of a polymeric precursor to form crosslinks. compositions. 0346 Embodiments of this invention may further provide a crosslinking agent having the formula (RE)M(ERE)M' 0337. In some aspects, a crosslinked polymeric precursor (ER), where M', E, R' and R are as defined above. A may be used to control the Viscosity of a precursor composi crosslinking agent of this kind may be used either during tion, or a polymeric precursor ink composition. The synthesis of a polymeric precursor to form crosslinks, or in crosslinking of a polymeric precursor can increase its formation of an ink or other composition. molecular weight. The molecular weight of a polymeric pre 0347 In some embodiments, a polymeric precursor may cursor can be varied over a wide range by incorporating incorporate crosslinkable functional groups. A crosslinkable crosslinking into the preparation of the precursor. The Viscos functional group may be attached to a portion of the R groups ity of an ink composition can be varied over a wide range by of one or more kinds in the polymeric precursor. using a crosslinked precursor to prepare an ink composition. 0348 Examples of crosslinkable functional groups 0338. In some embodiments, the crosslinking of a poly include vinyl, vinylacrylate, epoxy, and cycloaddition and meric precursor composition may be used to control the vis Diels-Alder reactive pairs. Crosslinking may be performed cosity of the composition, or of a polymeric precursor ink by methods known in the art including the use of heat, light or composition. A polymeric precursor component of a compo a catalyst, as well as by Vulcanization with elemental Sulfur. sition can be crosslinked by adding a crosslinking agent to the composition. The viscosity of an ink composition may be Dopants varied over a wide range by adding a crosslinking agent to the 0349. In some embodiments, a polymeric precursor com ink composition. position may include a dopant. A dopant may be introduced US 2011/0034667 A1 Feb. 10, 2011 into a polymeric precursor in the synthesis of the precursor, or through 6, where one or more capping compounds are added alternatively, can be added to a composition or ink containing to the reactions. A capping compound may control the extent the polymeric precursor. of polymer chain formation. A capping compound may also 0350 A semiconductor material or thin film of this disclo be used to control the Viscosity of an ink containing the Sure made from a polymeric precursor may contain atoms of polymeric precursor compound or composition, as well as its one or more dopants. Methods for introducing a dopant into a solubility and ability to from a suspension. Examples of cap photovoltaic absorber layer include preparing the absorber ping compounds include inorganic or organometallic com layer with a polymeric precursor of this invention containing plexes which bind to repeating units A or B, or both, and the dopant. prevent further chain propagation. Examples of capping com 0351. The quantity of a dopant in an embodiment of this pounds include RM’ER, and RM'(ER). disclosure can be from about 1x107 atom percent to about 5 atom percent relative to the most abundant Group 11 atom, or Ligands greater. In some embodiments, a dopant can be included at a level of from about 1x10" cm to about 1x10 cm. A 0366 As used herein, the term ligand refers to any atom or dopant can be included at a level of from about 1 ppm to about chemical moiety that can donate electron density in bonding 10,000 ppm. or coordination. 0352. In some embodiments, a dopant may be an alkali 0367. A ligand can be monodentate, bidentate or multi metal atom including Li, Na, K, Rb, and a mixture of any of dentate. the foregoing. 0368 As used herein, the term ligand includes Lewis base 0353 Embodiments of this invention may further include ligands. a dopant being an alkaline earth metal atom including Be, Mg, 0369. As used herein, the term organic ligand refers to an Ca, Sr., Ba, and a mixture of any of the foregoing. organic chemical group composed of atoms of carbon and 0354. In some embodiments, a dopant may be a transition hydrogen, having from 1 to 22 carbon atoms, and optionally metal atom from Group 3 through Group 12. containing oxygen, nitrogen, Sulfuror other atoms, which can 0355. In some embodiments, a dopant may be a transition bind to another atom or molecule through a carbon atom. An metal atom from Group 5 including V, Nb, Ta, and a mixture organic ligand can be branched or unbranched, Substituted or of any of the foregoing. unsubstituted. 0356. In some embodiments, a dopant may be a transition 0370. As used herein, the term inorganic ligand refers to metal atom from Group 6 including Cr, Mo, W. and a mixture an inorganic chemical group which can bind to another atom of any of the foregoing. or molecule through a non-carbon atom. 0357. In some embodiments, a dopant may be a transition 0371 Examples of ligands include halogens, water, alco metal atom from Group 10 including Ni, Pd, Pt, and a mixture hols, ethers, hydroxyls, amides, carboxylates, chalcogeny of any of the foregoing. lates, thiocarboxylates, selenocarboxylates, tellurocarboxy 0358. In some embodiments, a dopant may be a transition metal atom from Group 12 including Zn, Cd, Hg, and a lates, carbonates, nitrates, phosphates, Sulfates, perchlorates, mixture of any of the foregoing. oxalates, and amines. 0359. In some embodiments, a dopant may be an atom 0372. As used herein, the term chalcogenylate refers to from Group 14 including C, Si, Ge. Sn, Pb, and a mixture of thiocarboxylate, selenocarboxylate, and tellurocarboxylate, any of the foregoing. having the formula RCE, where E is S, Se, or Te. 0360. In some embodiments, a dopant may be an atom 0373. As used herein, the term chalcocarbamate refers to from Group 15 including P. As, Sb, Bi, and a mixture of any thiocarbamate, selenocarbamate, and tellurocarbamate, hav of the foregoing. ing the formula R'R''NCE, where E is S, Se, or Te, and R' 0361. In some aspects, a polymeric precursor composition and Rare the same or different and are hydrogen, alkyl, aryl, may advantageously be prepared to incorporate alkali metal or an organic ligand. ions as dopants. For example, a polymeric precursor compo 0374 Examples of ligands include F, Cl, HO, ROH, sition may be prepared using an amount of Na(ER), where E RO, OH, RO, NR, RCO, RCE, CO., NO., is S or Se and R is alkyl or aryl. In certain embodiments, a PO, SO, CIO, CO, NH, NR, R-NH, and RNH, polymeric precursor composition may be prepared using an where R is alkyl, and E is chalcogen. amount of NaIn(ER), NaGa(ER), LiIn(ER), LiGa(ER). 0375 Examples of ligands include azides, heteroaryls, KIn(ER), KGa(ER), or mixtures thereof, where E is S or Se thiocyanates, arylamines, arylalkylamines, nitrites, and and R is alkyl or aryl. A polymeric precursor compound of sulfites. this kind can be used to control the level of alkali metal ions. 0376 Examples of ligands include Br, N., pyridine, 0362. A dopant may be provided in a precursor as a coun SCN-I, ArNH, NO, and SO, where Ar is aryl. terion or introduced into a thin film by any of the deposition 0377 Examples of ligands include cyanides or nitriles, methods described herein. A dopant may also be introduced isocyanides or isonitriles, alkylcyanides, alkylnitriles, alkyl into a thin film by methods known in the art including ion isocyanides, alkylisonitriles, arylcyanides, arylnitriles, aryl implantation. isocyanides, and aryllisonitriles. 0363 A dopant of this disclosure may be p-type or n-type. 0378 Examples of ligands include hydrides, carbenes, 0364 Any of the foregoing dopants may be used in an ink carbon monoxide, isocyanates, isonitriles, thiolates, alkylthi of this invention. olates, dialkylthiolates, thioethers, thiocarbamates, phos phines, alkylphosphines, arylphosphines, arylalkylphos Capping Compounds phines, arsenines, alkylarsenines, arylarsenines, 0365. In some embodiments, a polymeric precursor com arylalkylarsenines, stilbines, alkylstilbines, arylstilbines, and position may be formed as shown in Reaction Schemes 1 arylalkylstilbines. US 2011/0034667 A1 Feb. 10, 2011 20
0379 Examples of ligands include I, H, R, CN, Ag), In,(S. Sel), where x is from 0.001 to 0.999, Z is from CO, RNC, RSH, RS, RS, SCN, R.P. RAs, RSb, 0 to 1, V is from 0.7 to 1.1, and w is from 1.5 to 2.5. alkenes, and aryls, where each R is independently alkyl, aryl, 0393. In some embodiments, one or more polymeric pre or heteroaryl. cursor compounds may be used to prepare a CAIS layer on a 0380 Examples of ligands include trioctylphosphine, tri substrate, wherein the layer has the empirical formula (Cu, methylvinylsilane and hexafluoroacetylacetonate. Ag), In,(S. Sel), where x is from 0.001 to 0.999, Z is from 0381 Examples of ligands include nitric oxide, silyls, 0.5 to 1, v is from 0.7 to 1.1, and w is from 1.5 to 2.5. alkylgermyls, arylgermyls, arylalkylgermyls, alkylstannyls, 0394. In some embodiments, one or more polymeric pre arylstannyls, arylalkylstannyls, selenocyanates, selenolates, cursor compounds may be used to prepare a CAIS layer on a alkylselenolates, dialkylselenolates, selenoethers, selenocar substrate, wherein the layer has the empirical formula (Cu, bamates, tellurocyanates, tellurolates, alkyltellurolates, Ag), In,(SSe), wherex is from 0.001 to 0.999, Z is from dialkyltellurolates, telluroethers, and tellurocarbamates. 0.5 to 1, v is from 0.7 to 1.1, and w is from 1.5 to 2.5. 0382 Examples of ligands include chalcogenates, thiothi 0395. In some embodiments, one or more polymeric pre olates, selenothiolates, thioselenolates, selenoselenolates, cursor compounds may be used to prepare an CAIS material alkyl thiothiolates, alkyl selenothiolates, alkyl thioseleno having a quantity of Ag atoms of from 1 to 37.5 mol %, or lates, alkyl selenoselenolates, aryl thiothiolates, aryl sele from 2 to 37.5 mol %, or from 3 to 37.5 mol %, or from 5 to nothiolates, aryl thioselenolates, aryl Selenoselenolates, ary 37.5 mol %, or from 7 to 37.5 mol %, or from 10 to 37.5 mol lalkyl thiothiolates, arylalkyl selenothiolates, arylalkyl %, or from 12 to 37.5 mol%. thioselenolates, and arylalkyl selenoselenolates. 0396. In some embodiments, one or more polymeric pre 0383 Examples of ligands include selenoethers and tel cursor compounds may be used to prepare a CAIGSlayer on luroethers. a substrate, wherein the layer has the empirical formula (Cu, 0384 Examples of ligands include NO, O, NHRs. Ag),(In-Ga,), (S1-Se...), where x is from 0.001 to 0.999, PHR SiR, GeR, SnRT, SR, SeR, TeR, SSR, y is from 0 to 1, Z is from 0 to 1, u is from 0.5 to 1.5, V is from SeSR, SSeR, SeSeR, and RCN, where n is from 1 to 3, and 0.5 to 1.5, and w is from 1 to 3. In certain embodiments, X is each R is independently alkyl or aryl. from 0.001 to 1, or from 0.01 to 1, or from 0.02 to 1, or from 0385 As used herein, the term transition metals refers to 0.03 to 1, or from 0.05 to 1, or from 0.07 to 1, or from 0.1 to atoms of Groups 3 though 12 of the Periodic Table of the 1, or from 0.15 to 1, or from 0.2 to 1, or from 0.25 to 1, or from elements recommended by the Commission on the Nomen 0.3 to 1, or from 0.35 to 1, or from 0.4 to 1. In certain clature of Inorganic Chemistry and published in IUPAC embodiments, x is from 0.001 to 1 andy is from 0.001 to 1, or Nomenclature of Inorganic Chemistry, Recommendations X is from 0.01 to 1 and y is from 0.01 to 1, or x is from 0.02 to 2005. 1 and y is from 0.02 to 1, or x is from 0.03 to 1 and y is from 0.03 to 1, or x is from 0.05 to 1 and y is from 0.05 to 1, or x is Photovoltaic Absorber Layer Compositions from 0.07 to 1 and y is from 0.07 to 1, or x is from 0.1 to 1 and y is from 0.1 to 1, or x is from 0.15 to 1 and y is from 0.15 to 0386 A polymeric precursor may be used to prepare a 1, or x is from 0.2 to 1 and y is from 0.2 to 1, or x is from 0.25 material for use in developing semiconductor products. to 1 and y is from 0.25 to 1, or x is from 0.3 to 1 and y is from 0387. The polymeric precursors of this invention may 0.3 to 1, or x is from 0.35 to 1 and y is from 0.35 to 1, or x is advantageously be used in mixtures to prepare a material with from 0.4 to 1 and y is from 0.4 to 1. controlled or predetermined stoichiometric ratios of the metal 0397. In some embodiments, one or more polymeric pre atoms in the material. cursor compounds may be used to prepare a CAIGSlayer on 0388. In some aspects, processes for solar cells that avoid a Substrate, wherein the layer has the empirical formula (Cu, additional Sulfurization or selenization steps may advanta Ag),(In-Ga,), (S1-Se...), where x is from 0.001 to 0.999, geously use polymeric precursor compounds and composi y is from 0 to 1, Z is from 0 to 1, u is from 0.7 to 1.2, v is from tions of this invention. 0.7 to 1.2, and w is from 1 to 3. 0389. The absorber material may be either an n-type or a 0398. In some embodiments, one or more polymeric pre p-type semiconductor, when Such compound is known to cursor compounds may be used to prepare a CAIGSlayer on exist. a Substrate, wherein the layer has the empirical formula (Cu, 0390. In some embodiments, one or more polymeric pre Ag),(In-Ga,), (S1-Se...), where x is from 0.001 to 0.999, cursor compounds may be used to prepare a CAIS layer on a y is from 0 to 1, Z is from 0 to 1, u is from 0.7 to 1.1, V is from substrate, wherein the layer has the empirical formula (Cu 0.7 to 1.1, and w is from 1.5 to 2.5. Ag), In,(SSe), where x is from 0.001 to 0.999, Z is from 0399. In some embodiments, one or more polymeric pre 0 to 1, V is from 0.5 to 1.5, and w is from 1 to 3. In certain cursor compounds may be used to prepare a CAIGSlayer on embodiments, X is from 0.001 to 1, or from 0.01 to 1, or from a Substrate, wherein the layer has the empirical formula (Cu, 0.02 to 1, or from 0.03 to 1, or from 0.05 to 1, or from 0.07 to Ag),(In-Ga,), (S1-Se...), where x is from 0.001 to 0.999, 1, or from 0.1 to 1, or from 0.15 to 1, or from 0.2 to 1, or from y is from 0 to 1, Z is from 0.5 to 1, u is from 0.7 to 1.1, V is from 0.25 to 1, or from 0.3 to 1, or from 0.35 to 1, or from 0.4 to 1. 0.7 to 1.1, and w is from 1.5 to 2.5. 0391. In some embodiments, one or more polymeric pre 0400. In some embodiments, one or more polymeric pre cursor compounds may be used to prepare a CAIS layer on a cursor compounds may be used to prepare a CAIGSlayer on substrate, wherein the layer has the empirical formula (Cu, a Substrate, wherein the layer has the empirical formula (Cu, Ag), In,(SSe), where x is from 0.001 to 0.999, Z is from Ag),(In Ga),(S,Se), where x is from 0.001 to 0.999, 0 to 1, V is from 0.7 to 1.2, and w is from 1 to 3. y is from 0 to 1, Z is from 0.5 to 1, u is from 0.8 to 0.95, V is 0392. In some embodiments, one or more polymeric pre from 0.7 to 1.1, and w is from 1.5 to 2.5. cursor compounds may be used to prepare a CAIS layer on a 04.01. In some embodiments, one or more polymeric pre substrate, wherein the layer has the empirical formula (Cu, cursor compounds may be used to prepare anCAIGS material US 2011/0034667 A1 Feb. 10, 2011 having a quantity of Ag atoms of from 1 to 37.5 mol %, or 0413. In certain variations, one or more polymeric precur from 2 to 37.5 mol %, or from 3 to 37.5 mol %, or from 5 to sors may be used to prepare a CAIGS, AIGS, CAIS, CAGS, 37.5 mol %, or from 7 to 37.5 mol %, or from 10 to 37.5 mol AIS, or AGS material using nanoparticles prepared with the %, or from 12 to 37.5 mol%. polymeric precursors. 0402. A polymeric precursor may be used to prepare an 0414. In certain embodiments, one or more polymeric pre absorber material for a solar cell product. The absorber mate cursors may be used to prepare a CAIGS, AIGS, CAIS, rial may have the empirical formula M' (M.M.),(S. CAGS, AIS, or AGS material as a layer that may be processed -Se...), where M' is Ag, M” and M are Ga and In, respec at relatively low temperatures to achieve a solar cell. tively, u is from 0.5 to 1.5, y is from 0 to 1, and Z is from 0 to 0415. In some aspects, one or more polymeric precursors 1, V is from 0.5 to 1.5, and w is from 1.5 to 2.5. may be used to prepare a CAIGS, AIGS, CAIS, CAGS, AIS, 0403. In some embodiments, one or more polymeric pre or AGS material as a photovoltaic layer. cursor compounds may be used to prepare a AIGS layer on a 0416. In some variations, one or more polymeric precur Substrate, wherein the layer has the empirical formula Ag, sors may be used to prepare a chemically and physically (In Ga),(S1-Se), where u is from 0.5 to 1.5, y is from 0 uniform semiconductor CAIGS, AIGS, CAIS, CAGS, AIS, or to 1, and Z is from 0 to 1, V is from 0.5 to 1.5, and w is from 1 AGS layer on a variety of substrates, including flexible sub to 3. In certain embodiments, u is from 0.5 to 1, or u is from Strates. 0.5 to 0.95, or u is from 1 to 1.5, or u is from 1.05 to 1.5, or u 0417 Examples of an absorber material include AgGaS, is from 1.1 to 1.5. AgInS, AgTIS, AgGaSea, AgInSea, AgT1Sea, AgGaTe, 0404 In some aspects, one or more polymeric precursor AgInTe and AgTTe. compounds may be used to prepare a AIGS layer on a Sub 0418. Examples of an absorber material include AgIn strate, wherein the layer has the empirical formula Ag(In GaSSe, AgInT1 SSe. AgGaTl SSe, AgInGaSeTe, AgInTl Ga),(S,Se), where u is from 0.7 to 1.2, y is from 0 to 1, SeTe. AgGaTl SeTe, AgInGaSTe, AgInT1 STe, and AgGaTl and Z is from 0 to 1, V is from 0.7 to 1.2, and w is from 1 to 3. STe. 0405. In some variations, one or more polymeric precursor 0419 An. CAIGS, AIGS, CAIS, CAGS, AIS, or AGSlayer compounds may be used to prepare a AIGS layer on a Sub may be used with various junction partners to produce a solar strate, wherein the layer has the empirical formula Ag(In cell. Examples of junction partner layers are known in the art Ga),(S,Se), where u is from 0.7 to 1.1, y is from 0 to 1, and include CdS, ZnS, ZnSe, and CdZnS. See, for example, and Z is from 0 to 1, V is from 0.7 to 1.1, and w is from 2 to 2.4. Martin Green, Solar Cells Operating Principles, Technology 0406. In certain embodiments, one or more polymeric pre and System Applications (1986); Richard H. Bube, Photovol cursor compounds may be used to prepare a AIGS layer on a taic Materials (1998); Antonio Luque and Steven Hegedus, Substrate, wherein the layer has the empirical formula Ag, Handbook of Photovoltaic Science and Engineering (2003). (In Ga),(S1-Se), where u is from 0.7 to 1.1, y is from 0 0420. In some aspects, the thickness of an absorber layer to 1, and Z is from 0.5 to 1, V is from 0.7 to 1.1, and w is from may be from about 0.001 to about 100 micrometers, or from 2 to 2.4. about 0.001 to about 20 micrometers, or from about 0.01 to 0407. In certain embodiments, one or more polymeric pre about 10 micrometers, or from about 0.05 to about 5 cursor compounds may be used to prepare a AIGS layer on a micrometers, or from about 0.1 to about 4 micrometers, or Substrate, wherein the layer has the empirical formula Ag, from about 0.1 to about 3.5 micrometers, or from about 0.1 to (In Ga),(S,Se), where u is from 0.8 to 0.95, y is from about 3 micrometers, or from about 0.1 to about 2.5 microme 0.5 to 1, and Z is from 0.5 to 1, v is from 0.95 to 1.05, and w ters. is from 1.8 to 2.2. 0408. In certain embodiments, one or more polymeric pre Substrates cursor compounds may be used to prepare a AIGS layer on a 0421. The polymeric precursors of this invention can be Substrate, wherein the layer has the empirical formula Ag, used to form a layer on a substrate. The substrate can be made (In Ga),(S1-Se), where u is from 0.8 to 0.95, y is from of any Substance, and can have any shape. Substrate layers of 0.5 to 1, and Z is from 0.5 to 1, v is from 0.95 to 1.05, and w polymeric precursors can be used to create a photovoltaic is from 2.0 to 2.2. layer or device. 04.09. In some embodiments, one or more polymeric pre 0422 Examples of substrates on which a polymeric pre cursor compounds may be used to prepare an AIGS material cursor of this disclosure can be deposited or printed include having a quantity of Ag atoms of from 1 to 37.5 mol %, or semiconductors, doped semiconductors, silicon, gallium ars from 2 to 37.5 mol %, or from 3 to 37.5 mol %, or from 5 to enide, insulators, glass, molybdenum glass, silicon dioxide, 37.5 mol %, or from 7 to 37.5 mol %, or from 10 to 37.5 mol titanium dioxide, Zinc oxide, silicon nitride, and combina %, or from 12 to 37.5 mol%. tions thereof. 0410 Embodiments of this invention may further provide 0423. A substrate may be coated with molybdenum or a polymeric precursors that can be used to prepare a CAIGS, molybdenum-containing compound. AIGS, CAIS, CAGS, AIS, or AGS material for a solar cell 0424. In some embodiments, a substrate may be pre product. treated with a molybdenum-containing compound, or one or 0411. In some aspects, one or more polymeric precursors more compounds containing molybdenum and selenium. may be used to prepare a CAIGS, AIGS, CAIS, CAGS, AIS, 0425 Examples of substrates on which a polymeric pre or AGS material as a chemically and physically uniform layer. cursor of this disclosure can be deposited or printed include 0412. In some variations, one or more polymeric precur metals, metal foils, molybdenum, aluminum, beryllium, cad sors may be used to prepare a CAIGS, AIGS, CAIS, CAGS, mium, cerium, chromium, cobalt, copper, gallium, gold, lead, AIS, or AGS material wherein the stoichiometry of the metal manganese, nickel, palladium, platinum, rhenium, rhodium, atoms of the material can be controlled. silver, stainless Steel, Steel, iron, strontium, tin, titanium, US 2011/0034667 A1 Feb. 10, 2011 22 tungsten, Zinc, Zirconium, metal alloys, metal silicides, metal may be a Suspension of the polymeric precursors in an organic carbides, and combinations thereof. carrier. In some variations, the ink is a solution of the poly 0426 Examples of substrates on which a polymeric pre meric precursors in an organic carrier. The carrier can be an cursor of this disclosure can be deposited or printed include organic liquid or solvent. polymers, plastics, conductive polymers, copolymers, poly 0440 An ink can be made by providing one or more poly mer blends, polyethylene terephthalates, polycarbonates, meric precursor compounds and solubilizing, dissolving, Sol polyesters, polyester films, mylars, polyvinyl fluorides, poly Vating, or dispersing the compounds with one or more carri vinylidene fluoride, polyethylenes, polyetherimides, poly ers. The compounds dispersed in a carrier may be etherSulfones, polyetherketones, polyimides, polyvinylchlo nanocrystalline, nanoparticles, microparticles, amorphous, rides, acrylonitrile butadiene Styrene polymers, silicones, or dissolved molecules. epoxys, and combinations thereof. 0441 The concentration of the polymeric precursors in an 0427 Examples of substrates on which a polymeric pre ink of this disclosure can be from about 0.001% to about 99% cursor of this disclosure can be deposited or printed include (w/w), or from about 0.001% to about 90%, or from about roofing materials. 0.1% to about 90%. 0428 Examples of substrates on which a polymeric pre 0442 A polymeric precursor may exist in a liquid or flow cursor of this disclosure can be deposited or printed include able phase under the temperature and conditions used for papers and coated papers. deposition, coating or printing. 0429. A substrate of this disclosure can be of any shape. 0443) In some variations of this invention, polymeric pre Examples of Substrates on which a polymeric precursor of cursors that are partially soluble, or are insoluble in a particu this disclosure can be deposited include a shaped substrate lar carrier can be dispersed in the carrier by high shear mixing. including a tube, a cylinder, a roller, a rod, a pin, a shaft, a 0444 AS used herein, the term dispersing encompasses plane, a plate, a blade, a vane, a curved Surface or a spheroid. the terms solubilizing, dissolving, and Solvating. 0430. A substrate may be layered with an adhesion pro 0445. The carrier for an ink of this disclosure may be an moter before the deposition, coating or printing of a layer of organic liquid or solvent. a polymeric precursor of this invention. 0446. Examples of a carrier for an ink of this disclosure 0431 Examples of adhesion promoters include a glass include one or more organic solvents, which may contain an layer, a metal layer, a titanium-containing layer, a tungsten aqueous component. containing layer, a tantalum-containing layer, tungsten 0447 Embodiments of this invention further provide poly nitride, tantalum nitride, titanium nitride, titanium nitride meric precursor compounds having enhanced solubility in silicide, tantalum nitride silicide, a chromium-containing one or more carriers for preparing inks. The solubility of a layer, a vanadium-containing layer, a nitride layer, an oxide polymeric precursor compound can be selected by variation layer, a carbide layer, and combinations thereof. 0432 Examples of adhesion promoters include organic of the nature and molecular size and weight of one or more adhesion promoters such as organofunctional silane coupling organic ligands attached to the compound. agents, silanes, hexamethyldisilaZanes, glycol ether acetates, 0448. An ink composition of this invention may contain ethylene glycol bis-thioglycolates, acrylates, acrylics, mer any of the dopants disclosed herein, or a dopant known in the captains, thiols, selenols, tellurols, carboxylic acids, organic art. phosphoric acids, triazoles, and mixtures thereof. 0449 Ink compositions of this disclosure can be made by 0433 Substrates may be layered with a barrier layer methods known in the art, as well as methods disclosed before the deposition of printing of a layer of a polymeric herein. 0450 Examples of a carrier for an ink of this disclosure precursor of this invention. include alcohol, methanol, ethanol, isopropyl alcohol, thiols, 0434 Examples of a barrier layer include a glass layer, a butanol, butanediol, glycerols, alkoxyalcohols, glycols, metal layer, a titanium-containing layer, a tungsten-contain 1-methoxy-2-propanol, acetone, ethylene glycol, propylene ing layer, a tantalum-containing layer, tungsten nitride, tan glycol, propylene glycol laurate, ethylene glycol ethers, talum nitride, titanium nitride, titanium nitride silicide, tan diethylene glycol, triethylene glycol monobutylether, propy talum nitride silicide, and combinations thereof. lene glycol monomethylether, 1.2-hexanediol, ethers, diethyl 0435 A substrate can be of anythickness, and can be from ether, aliphatic hydrocarbons, aromatic hydrocarbons, pen about 20 micrometers to about 20,000 micrometers or more in tane, hexane, heptane, octane, isooctane, decane, cyclohex thickness. ane, p-Xylene, m-Xylene, o-Xylene, benzene, toluene, Xylene, Ink Compositions tetrahydrofuran, 2-methyltetrahydrofuran, siloxanes, cyclosiloxanes, silicone fluids, halogenated hydrocarbons, 0436 Embodiments of this invention further provide ink dibromomethane, dichloromethane, dichloroethane, trichlo compositions which contain one or more polymeric precursor roethane chloroform, methylene chloride, acetonitrile, esters, compounds. The polymeric precursors of this invention may acetates, ethyl acetate, butyl acetate, acrylates, isobornyl be used to make photovoltaic materials by printing an ink acrylate, 1.6-hexanediol diacrylate, polyethylene glycol dia onto a Substrate. crylate, ketones, acetone, methyl ethyl ketone, cyclohex 0437. An ink of this disclosure advantageously allows pre anone, butyl carbitol, cyclopentanone, lactams, N-meth cise control of the Stoichiometric ratios of certain atoms in the ylpyrrolidone, N-(2-hydroxyethyl)-pyrrolidone, cyclic ink because the ink can be composed of a mixture of poly acetals, cyclic ketals, aldehydes, amides, dimethylforma meric precursors. mide, methyl lactate, oils, natural oils, terpenes, and mixtures 0438 Inks of this disclosure can be made by any methods thereof. known in the art. 0451 An ink of this disclosure may further include com 0439. In some embodiments, an ink can be made by mix ponents such as a surfactant, a dispersant, an emulsifier, an ing a polymeric precursor with one or more carriers. The ink anti-foaming agent, a dryer, a filler, a resin binder, a thickener, US 2011/0034667 A1 Feb. 10, 2011 a viscosity modifier, an anti-oxidant, a flow agent, a plasti polycarboxylic acids, carboxymethylcelluloses, hydroxyeth cizer, a conductivity agent, a crystallization promoter, an ylcelluloses, methylcelluloses, methyl hydroxyethyl cellulo extender, a film conditioner, an adhesion promoter, and a dye. ses, methyl hydroxypropyl celluloses, silicas, gellants, alu Each of these components may be used in an ink of this minates, titanates, gums, clays, waxes, polysaccharides, disclosure at a level of from about 0.001% to about 10% or starches, and mixtures thereof. more of the ink composition. 0462 Examples of anti-oxidants include phenolics, phos 0452 Examples of surfactants include siloxanes, poly alkyleneoxide siloxanes, polyalkyleneoxide polydimethylsi phites, phosphonites, thioesters, Stearic acids, ascorbic acids, loxanes, polyester polydimethylsiloxanes, ethoxylated non catechins, cholines, and mixtures thereof. ylphenols, nonylphenoxy polyethyleneoxyethanol, 0463 Examples of flow agents include waxes, celluloses, fluorocarbon esters, fluoroaliphatic polymeric esters, fluori butyrates, Surfactants, polyacrylates, and silicones. nated esters, alkylphenoxy alkyleneoxides, cetyl trimethyl 0464 Examples of a plasticizer include alkyl benzyl ammonium chloride, carboxymethylamylose, ethoxylated phthalates, butyl benzyl phthalates, dioctyl phthalates, acetylene glycols, betaines, N-n-dodecyl-N,N-dimethylbe diethyl phthalates, dimethyl phthalates, di-2-ethylhexy-adi taine, dialkyl SulfoSuccinate salts, alkylnaphthalenesulfonate pates, diisobutyl phthalates, diisobutyladipates, dicyclohexyl salts, fatty acid salts, polyoxyethylene alkylethers, polyoxy phthalates, glycerol tribenzoates. Sucrose benzoates, ethylene alkylallylethers, polyoxyethylene-polyoxypropy polypropylene glycol dibenzoates, neopentyl glycol diben lene block copolymers, alkylamine salts, quaternary ammo Zoates, dimethyl isophthalates, dibutyl phthalates, dibutyl nium salts, and mixtures thereof. sebacates, tri-n-hexyltrimellitates, and mixtures thereof. 0453 Examples of surfactants include anionic, cationic, amphoteric, and nonionic Surfactants. Examples of Surfac 0465 Examples of a conductivity agent include lithium tants include SURFYNOL, DYNOL, ZONYL, FLUORAD, salts, lithium trifluoromethanesulfonates, lithium nitrates, and SILWET Surfactants. dimethylamine hydrochlorides, diethylamine hydrochlo 0454. A surfactant may be used in an ink of this disclosure rides, hydroxylamine hydrochlorides, and mixtures thereof. at a level of from about 0.001% to about 2% of the ink 0466. Examples of a crystallization promoter include cop composition. per chalcogenides, alkali metal chalcogenides, alkali metal 0455 Examples of a dispersant include a polymer dispers salts, alkaline earth metal salts, Sodium chalcogenates, cad ant, a Surfactant, hydrophilic-hydrophobic block copolymers, mium salts, cadmium Sulfates, cadmium Sulfides, cadmium acrylic block copolymers, acrylate block copolymers, graft selenides, cadmium tellurides, indium sulfides, indium polymers, and mixtures thereof. Selenides, indium tellurides, gallium sulfides, gallium 0456. Examples of an emulsifier include a fatty acid Selenides, gallium tellurides, molybdenum, molybdenum Sul derivative, an ethylene Stearamide, an oxidized polyethylene fides, molybdenum selenides, molybdenum tellurides, wax, mineral oils, a polyoxyethylene alkyl phenol ether, a molybdenum-containing compounds, and mixtures thereof. polyoxyethylene glycol ether block copolymer, a polyoxy ethylene Sorbitan fatty acid ester, a Sorbitan, an alkyl siloxane 0467. An ink may contain one or more components polyether polymer, polyoxyethylene monostearates, poly selected from the group of a conducting polymer, silver oxyethylene monolaurates, polyoxyethylene monooleates, metal, silver selenide, silver Sulfide, copper metal, indium and mixtures thereof. metal, gallium metal, Zinc metal, alkali metals, alkali metal 0457. Examples of an anti-foaming agent include polysi salts, alkaline earth metal salts, Sodium chalcogenates, cal loxanes, dimethylpolysiloxanes, dimethyl siloxanes, sili cium chalcogenates, cadmium sulfide, cadmium selenide, cones, polyethers, octyl alcohol, organic esters, ethyleneox cadmium telluride, indium sulfide, indium selenide, indium ide propyleneoxide copolymers, and mixtures thereof. telluride, gallium Sulfide, gallium selenide, gallium telluride, 0458 Examples of a dryer include aromatic sulfonic Zinc sulfide, Zinc selenide, Zinc telluride, copper Sulfide, cop acids, aromatic carboxylic acids, phthalic acid, hydroxy per selenide, copper telluride, molybdenum sulfide, molyb isophthalic acid, N-phthaloylglycine, 2-Pyrrolidone 5-car denum selenide, molybdenum telluride, and mixtures of any boxylic acid, and mixtures thereof. of the foregoing. 0459 Examples of a filler include metallic fillers, silver 0468. An ink of this disclosure may contain particles of a powder, silver flake, metal coated glass spheres, graphite metal, a conductive metal, oran oxide. Examples of metaland powder, carbon black, conductive metal oxides, ethylene oxide particles include silica, alumina, titania, copper, iron, vinyl acetate polymers, and mixtures thereof. steel, aluminum and mixtures thereof. 0460) Examples of a resin binder include acrylic resins, 0469. In certain variations, an ink may contain a biocide, a alkyd resins, vinyl resins, polyvinyl pyrrolidone, phenolic sequestering agent, a chelator, a humectant, a coalescent, or a resins, ketone resins, aldehyde resins, polyvinylbutyral resin, viscosity modifier. amide resins, amino resins, acrylonitrile resins, cellulose res 0470. In certain aspects, an ink of this disclosure may be ins, nitrocellulose resins, rubbers, fatty acids, epoxy resins, formed as a solution, a suspension, a slurry, or a semisolidgel ethylene acrylic copolymers, fluoropolymers, gels, glycols, or paste. An ink may include one or more polymeric precur hydrocarbons, maleic resins, urea resins, natural rubbers, sors solubilized in a carrier, or may be a solution of the natural gums, phenolic resins, cresols, polyamides, polybuta polymeric precursors. In certain variations, a polymeric pre dienes, polyesters, polyolefins, polyurethanes, isocynates, cursor may include particles or nanoparticles that can be polyols, thermoplastics, silicates, silicones, polystyrenes, and Suspended in a carrier, and may be a suspension or paint of the mixtures thereof. polymeric precursors. In certain embodiments, a polymeric 0461) Examples of thickeners and viscosity modifiers precursor can be mixed with a minimal amount of a carrier, include conducting polymers, celluloses, urethanes, polyure and may be a slurry or semisolid gel or paste of the polymeric thanes, styrene maleic anhydride copolymers, polyacrylates, precursor. US 2011/0034667 A1 Feb. 10, 2011 24
0471. The viscosity of an ink of this disclosure can be from 0482 Examples of methods for depositing a polymeric about 0.5 centipoises (cP) to about 50 cp, or from about 0.6 to precursor onto a Surface or Substrate include all forms of about 30 cp, or from about 1 to about 15 cB, or from about 2 to spraying, coating, and printing. about 12 cF. 0483 Solar cell layers can be made by depositing one or 0472. The viscosity of an ink of this disclosure can be from more polymeric precursors of this disclosure on a flexible about 20 cp to about 2x10 cp, or greater. The viscosity of an Substrate in a high throughput roll process. The depositing of ink of this disclosure can be from about 20 cP to about 1x10° polymeric precursors in a high throughput roll process can be cP, or from about 200 cP to about 200,000 cP, or from about done by spraying or coating a composition containing one or 200 cp to about 100,000 cP, or from about 200 cP to about more polymeric precursors, or by printing an ink containing 40,000 cP, or from about 200 cp to about 20,000 cP. one or more polymeric precursors of this disclosure. 0473. The viscosity of an ink of this disclosure can be 0484 Examples of methods for depositing a polymeric about 1 cB, or about 2 cB, or about 5 cB, or about 20 cB, or about precursor onto a Surface or Substrate include spraying, spray 100 cP or about 500 cP, or about 1,000 cP, or about 5,000 cP. coating, spray deposition, spray pyrolysis, and combinations or about 10,000 cP, or about 20,000 cP, or about 30,000 cP or thereof. about 40,000 cP. 0485 Examples of methods for printing using an ink of 0474. In some embodiments, an ink may contain one or this disclosure include printing, screen printing, inkjet print more components from the group of a surfactant, a dispersant, ing, aerosoljet printing, ink printing, jet printing, stamp/pad an emulsifier, an anti-foaming agent, a dryer, a filler, a resin printing, transfer printing, pad printing, flexographic print binder, a thickener, a viscosity modifier, an anti-oxidant, a ing, gravure printing, contact printing, reverse printing, ther flow agent, a plasticizer, a conductivity agent, a crystalliza mal printing, lithography, electrophotographic printing, and combinations thereof. tion promoter, an extender, a film conditioner, an adhesion 0486 Examples of methods for depositing a polymeric promoter, and a dye. In certain variations, an ink may contain precursor onto a surface or Substrate include electrodeposit one or more compounds from the group of cadmium sulfide, ing, electroplating, electroless plating, bath deposition, coat cadmium selenide, cadmium telluride, Zinc sulfide, Zinc ing, dip coating, wet coating, spin coating, knife coating, Selenide, Zinc telluride, copper Sulfide, copper selenide, and roller coating, rod coating, slot die coating, meyerbarcoating, copper telluride. In some aspects, an ink may contain par lip direct coating, capillary coating, liquid deposition, Solu ticles of a metal, a conductive metal, or an oxide. tion deposition, layer-by-layer deposition, spin casting, and 0475 An ink may be made by dispersing one or more solution casting. polymeric precursor compounds of this disclosure in one or 0487. Examples of methods for depositing a polymeric more carriers to form a dispersion or solution. precursor onto a Surface or Substrate include chemical vapor 0476 A polymeric precursor ink composition can be pre deposition, aerosol chemical vapor deposition, metal-organic pared by dispersing one or more polymeric precursors in a chemical vapor deposition, organometallic chemical vapor Solvent, and heating the solvent to dissolve or disperse the deposition, plasma enhanced chemical vapor deposition, and polymeric precursors. The polymeric precursors may have a combinations thereof. concentration of from about 0.001% to about 99% (w/w), or 0488. Examples of methods for depositing a polymeric from about 0.001% to about 90%, or from about 0.1% to precursor onto a Surface or Substrate include atomic layer about 90%, or from about 0.1% to about 50%, or from about deposition, plasma-enhanced atomic layer deposition, 0.1% to about 40%, or from about 0.1% to about 30%, or from vacuum chamber deposition, sputtering, RF sputtering, DC about 0.1% to about 20%, or from about 0.1% to about 10% sputtering, magnetron Sputtering, evaporation, electronbeam in the Solution or dispersion. evaporation, laser ablation, gas-source polymeric beam epit axy, vapor phase epitaxy, liquid phase epitaxy, and combina Processes for Films of Polymeric Precursors on Substrates tions thereof. 0477 The polymeric precursors of this invention can be 0489. In certain embodiments, a first polymeric precursor used to make photovoltaic materials by depositing a layer may be deposited onto a substrate, and Subsequently a second onto a Substrate, where the layer contains one or more poly polymeric precursor may be deposited onto the Substrate. In meric precursors. The deposited layer may be a film or a thin certain embodiments, several different polymeric precursors film. Substrates are described above. may be deposited onto the Substrate to create a layer. 0490. In certain variations, different polymeric precursors 0478 As used herein, the terms “deposit,” “depositing.” may be deposited onto a substrate simultaneously, or sequen and “deposition” refer to any method for placing a compound tially, whether by spraying, coating, printing, or by other or composition onto a Surface or Substrate, including spray methods. The different polymeric precursors may be con ing, coating, and printing. tacted or mixed before the depositing step, during the depos 0479. As used herein, the term “thin film” refers to a layer iting step, or after the depositing step. The polymeric precur of atoms or molecules, or a composition layer on a substrate sors can be contacted before, during, or after the step of having a thickness of less than about 300 micrometers. transporting the polymeric precursors to the Substrate surface. 0480. A deposited layer of this disclosure advantageously 0491. The depositing of polymeric precursors, including allows precise control of the stoichiometric ratios of certain by spraying, coating, and printing, can be done in a controlled atoms in the layer because the layer can be composed of a orinert atmosphere. Such as in dry nitrogen and otherinert gas mixture of polymeric precursors. atmospheres, as well as in a partial vacuum atmosphere. 0481. The polymeric precursors of this invention, and 0492 Processes for depositing, spraying, coating, or print compositions containing polymeric precursors, can be depos ing polymeric precursors can be done at various temperatures ited onto a substrate using methods known in the art, as well including from about -20°C. to about 650° C., or from about as methods disclosed herein. -20°C. to about 600° C., or from about -20°C. to about 400° US 2011/0034667 A1 Feb. 10, 2011
C., or from about 20° C. to about 360° C., or from about 20° AIS, or AGS layer may be used as a junction partner with a C. to about 300° C., or from about 20° C. to about 250° C. layer of, for example, cadmium Sulfide, cadmium selenide, 0493 Processes for making a solar cell involving a step of cadmium telluride, Zinc sulfide, Zinc selenide, or Zinc tellu transforming a polymeric precursor compound into a material ride. The absorber layer may be adjacent to a layer of MgS. or semiconductor can be performed at various temperatures MgSe, MgTe, HgS, HgSe, HgTe. AlN, AlP, AlAs. AlSb, GaN. including from about 100° C. to about 650° C., or from about GaP. GaAs, GaSb, InN, InP, InAs, InSb, or combinations 150° C. to about 650° C., or from about 250° C. to about 650° thereof. C., or from about 300° C. to about 650° C., or from about 400° 0505. In certain variations, a solar cell of this disclosure is C. to about 650° C., or from about 300° C. to about 600° C., a multijunction device made with one or more stacked solar or from about 300° C. to about 550°C., or from about 300° C. cells. to about 500° C., or from about 300° C. to about 450° C. 0506. As shown in FIG. 7, a solar cell device of this dis 0494. In certain aspects, depositing of polymeric precur closure may have a substrate 10, an electrode layer 20, an sors on a substrate can be done while the substrate is heated. absorber layer 30, a window layer 40, and a transparent con In these variations, a thin-film material may be deposited or ductive layer (TCO) 50. The substrate 10 may be metal, formed on the substrate. plastic, glass, or ceramic. 0495. In some embodiments, a step of converting a pre 0507. The electrode layer 20 can be a molybdenum-con cursor to a material and a step of annealing can be done taining layer. The absorber layer 30 may be a CAIGS, AIGS, simultaneously. In general, a step of heating a precursor can CAIS, CAGS, AIS, or AGS layer. The window layer 40 may be done before, during or after any step of depositing the be a cadmium sulfide layer. The transparent conductive layer precursor. 50 can be an indium tin oxide layer or a doped zinc oxide 0496. In some variations, a substrate can be cooled after a layer. step of heating. In certain embodiments, a Substrate can be 0508 A solar cell device of this disclosure may have a cooled before, during, or after a step of depositing a precursor. Substrate, an electrode layer, an absorber layer, a window A substrate may be cooled to return the substrate to a lower layer, an adhesion promoting layer, a junction partner layer, a temperature, or to room temperature, or to an operating tem transparent layer, a transparent electrode layer, a transparent perature of a deposition unit. Various coolants or cooling conductive oxide layer, a transparent conductive polymer methods can be applied to cool a Substrate. layer, a doped conductive polymer layer, an encapsulating 0497. The depositing of polymeric precursors on a sub layer, an anti-reflective layer, a protective layer, or a protec strate may be done with various apparatuses and devices tive polymer layer. In certain variations, an absorber layer known in art, as well as devices described herein. includes a plurality of absorber layers. 0498. In some variations, the depositing of polymeric pre 0509. In certain variations, solar cells may be made by cursors can be performed using a spray nozzle with adjustable processes using polymeric precursor compounds and compo noZZle dimensions to provide a uniform spray composition sitions of this invention that advantageously avoid additional and distribution. Sulfurization or selenization steps. 0499 Embodiments of this disclosure further contemplate 0510. In certain variations, a solar cell device may have a articles made by depositing a layer onto a Substrate, where the molybdenum-containing layer, or an interfacial molybde layer contains one or more polymeric precursors. The article num-containing layer. may be a Substrate having a layer of a film, or a thin film, 0511 Examples of a protective polymer include silicon which is deposited, sprayed, coated, or printed onto the Sub rubbers, butyryl plastics, ethylene vinyl acetates, and combi strate. In certain variations, an article may have a substrate nations thereof. printed with a polymeric precursor ink, where the ink is 0512 Substrates can be made of a flexible material which printed in a pattern on the Substrate. can be handled in a roll. The electrode layer may be a thin foil. 0513. Absorber layers of this disclosure can be made by Photovoltaic Devices depositing or printing a composition containing nanopar 0500. The polymeric precursors of this invention can be ticles onto a Substrate, where the nanoparticles can be made used to make photovoltaic materials and Solar cells of high with polymeric precursor compounds of this invention. In efficiency. Some processes, nanoparticles can be made with, or formed 0501. As shown in FIG. 6, embodiments of this invention from polymeric precursor compounds and deposited on a may further provide optoelectronic devices and energy con Substrate. Deposited nanoparticles can Subsequently be trans version systems. Following the synthesis of polymeric pre formed by the application of heat or energy. cursor compounds, the compounds can be sprayed, depos 0514. In some embodiments, the absorber layer may be ited, or printed onto substrates and formed into absorber formed from nanoparticles or semiconductor nanoparticles materials and semiconductor layers. Absorber materials can which have been deposited on a substrate and Subsequently be the basis for optoelectronic devices and energy conversion transformed by heat or energy. systems. 0515. In some embodiments, a thin film photovoltaic 0502. In some embodiments, the solar cell is a thin layer device may have a transparent conductor layer, a buffer layer, solarcell having a CAIGS, AIGS, CAIS, CAGS, AIS, or AGS a p-type absorber layer, an electrode layer, and a Substrate. absorber layer deposited or printed on a substrate. The transparent conductor layer may be a transparent con 0503 Embodiments of this invention may provide ductive oxide (TCO) layer such as a zinc oxide layer, or zinc improved efficiency for solar cells used for light to electricity oxide layer doped with aluminum, or a carbon nanotube layer, conversion. oratin oxide layer, or a tin oxide layer doped with fluorine, or 0504. In some embodiments, a solar cell of this disclosure an indium tin oxide layer, or an indium tin oxide layer doped is a heterojunction device made with a CAIGS, AIGS, CAIS, with fluorine, while the buffer layer can be cadmium sulfide, CAGS, AIS, or AGS cell. The CAIGS, AIGS, CAIS, CAGS, or cadmium sulfide and high resistivity Zinc oxide. The p-type US 2011/0034667 A1 Feb. 10, 2011 26 absorber layer can be a CAIGS, AIGS, CAIS, CAGS, AIS, or be done in spray coating, spray deposition, jet deposition, or AGS layer, and the electrode layer can be molybdenum. The spray pyrolysis. The Substrate may be glass, metal, polymer, transparent conductor layer can be up to about 0.5 microme plastic, or silicon. ters in thickness. The buffer layer can also be a cadmium 0523. In certain variations, methods for making a photo Sulfide n-type junction partner layer. In some embodiments, Voltaic absorber layer may include heating the compounds to the buffer layer may be a silicon dioxide, an aluminum oxide, a temperature of from about 20° C. to about 400° C. while a titanium dioxide, or a boron oxide. depositing, spraying, coating, or printing the compounds onto 0516. Some examples of transparent conductive oxides the substrate. are given in K. Elmer et al., Transparent Conductive Zinc 0524 Methods for making a photovoltaic absorber layer Oxide, Vol. 104, Springer Series in Materials Science (2008). on a Substrate include providing one or more polymeric pre 0517. In some aspects, a solar cell can include a molybde cursor compounds, providing a substrate, depositing the com num selenide interface layer, which may be formed using pounds onto the Substrate, and heating the Substrate at a various molybdenum-containing and selenium-containing temperature of from about 100° C. to about 650° C., or from compounds that can be added to an ink for printing, or depos about 100° C. to about 600° C., or from about 100° C. to about ited onto a Substrate. 400° C., or from about 100° C. to about 300° C. in an inert 0518. A thin film material photovoltaic absorber layer can atmosphere, thereby producing a photovoltaic absorberlayer be made with one or more polymeric precursors of this inven having a thickness of from 0.001 to 100 micrometers. The tion. For example, a polymeric precursor ink can be sprayed depositing can be done in electrodepositing, electroplating, onto a stainless steel Substrate using a spray pyrolysis unit in electroless plating, bath deposition, liquid deposition, Solu a glovebox in an inert atmosphere. The spray pyrolysis unit tion deposition, layer-by-layer deposition, spin casting, or may have an ultrasonic nebulizer, precision flow meters for Solution casting. The Substrate may be glass, metal, polymer, inert gas carrier, and a tubular quartz reactor in a furnace. The plastic, or silicon. spray-coated Substrate can be heated at a temperature of from 0525 Methods for making a photovoltaic absorber layer about 25°C. to about 650° C. in an inert atmosphere, thereby on a Substrate include providing one or more polymeric pre producing a thin film material photovoltaic absorber layer. cursor inks, providing a Substrate, printing the inks onto the 0519 In some examples, a thin film material photovoltaic Substrate, and heating the Substrate at a temperature of from absorber layer can be made by providing a polymeric precur about 100° C. to about 600° C., or from about 100° C. to about sor ink which is filtered with a 0.45 micron filter, or a 0.3 650° C. in an inert atmosphere, thereby producing a photo micron filter. The ink can be deposited onto an aluminum voltaic absorberlayer having a thickness of from 0.001 to 100 Substrate using a spin casting unit in a gloveboxin inert argon micrometers. The printing can be done in screen printing, atmosphere. The substrate can be spin coated with the poly inkjet printing, transfer printing, flexographic printing, or meric precursor ink to a film thickness of about 0.1 to 5 gravure printing. The Substrate may be glass, metal, polymer, microns. The Substrate can be removed and heated at a tem plastic, or silicon. The method may further include adding to perature of from about 100° C. to about 600°C., or from about the ink an additional indium-containing compound, such as 100° C. to about 650° C. in an inert atmosphere, thereby In(SeR), wherein R is alkyl or aryl. producing a thin film material photovoltaic absorber layer. 0520. In further examples, a thin film material photovol Electrical Power Generation and Transmission taic absorber layer can be made by providing a polymeric 0526. This disclosure contemplates methods for produc precursor ink which is filtered with a 0.45 micron filter, or a ing and delivering electrical power. A photovoltaic device of 0.3 micron filter. The ink may be printed onto a polyethylene this invention can be used, for example, to convert Solar light terephthalate Substrate using a inkjet printer in a glovebox in to electricity which can be provided to a commercial power an inert atmosphere. A film of about 0.1 to 5 microns thick grid. ness can be deposited on the substrate. The substrate can be removed and heated at a temperature of from about 100°C. to 0527. As used herein, the term “solar cell refers to indi about 600° C., or from about 100° C. to about 650° C. in an vidual Solar cell as well as a Solar cell array, which can inert atmosphere, thereby producing a thin film material pho combine a number of solar cells. 0528 Solar cell devices can be manufactured in modular tovoltaic absorber layer. panels. 0521. In some examples, a solar cell can be made by pro viding an electrode layer on a polyethylene terephthalate 0529. The power systems of this disclosure can be made in substrate. A thin film material photovoltaic absorberlayer can large or Small scale, including power for a personal use, as be coated onto the electrode layer as described above. A well as on a megawatt Scale for a public use. window layer can be deposited onto the absorber layer. A 0530. An important feature of the solar cell devices and transparent conductive oxide layer can be deposited onto the power systems of this disclosure is that they can be manufac window layer, thereby forming an embodiment of a solar cell. tured and used with low environmental impact. 0522 Methods for making a photovoltaic absorber layer 0531. A power system of this disclosure may utilize a solar on a Substrate include providing one or more polymeric pre cell on a movable mounting, which may be motorized to face cursor compounds, providing a Substrate, spraying the com the solar cell toward the light. Alternatively, a solar cell may pounds onto the Substrate, and heating the Substrate at a be mounted on a fixed object in an optimal orientation. temperature of from about 100° C. to about 600° C., or of 0532 Solar cells can be attached in panels in which vari from about 100° C. to about 650° C. in an inert atmosphere, ous groups of cells are electrically connected in series and in thereby producing a photovoltaic absorber layer having a parallel to provide Suitable Voltage and current characteris thickness of from 0.001 to 100 micrometers. The spraying can tics. US 2011/0034667 A1 Feb. 10, 2011 27
0533 Solar cells can be installed on rooftops, as well as 0546 A sulfurization or selenization step can also be done outdoor, sunlighted surfaces of all kinds. Solar cells can be with co-deposition of another metal Such as copper, indium, combined with various kinds of roofing materials such as or gallium. roofing tiles or shingles. 0534. A power system can include a solar cell array and a Chemical Definitions battery storage system. A power system may have a diode 0547 As used herein, the term (X,Y) when referring to containing circuit and a Voltage-regulating circuit to prevent compounds or atoms indicates that either X or Y, or a combi the battery storage system from draining through the Solar nation thereof may be found in the formula. For example, cells or from being overcharged. (S,Se) indicates that atoms of either sulfur or selenium, or any 0535 A power system can be used to provide power for combination thereof may be found. Further, using this nota lighting, electric Vehicles, electric buses, electric airplanes, tion the amount of each atom can be specified. For example, pumping water, desalinization of water, refrigeration, mill when appearing in the chemical formula of a molecule, the ing, manufacturing, and other uses. notation (0.75 In,0.25 Ga) indicates that the atom specified by the symbols in the parentheses is indium in 75% of the com Sources of Elements pounds and gallium in the remaining 25% of the compounds, 0536 Sources of silver include silver metal, Ag(I), silver regardless of the identity any other atoms in the compound. In nitrates, silver halides, silver chlorides, silver acetates, silver the absence of a specified amount, the term (X,Y) refers to alkoxides, and mixtures thereof. approximately equal amounts of X and Y. 0537 Sources of copper include copper metal, Cu(I), (0548. The atoms S, Se, and Te of Group 16 are referred to Cu(II), copper halides, copper chlorides, copper acetates, as chalcogens. copper alkoxides, copper alkyls, copper diketonates, copper 0549. As used herein, the letter “S” in CIGS, AIGS, 2.2.6.6.-tetramethyl-3,5,-heptanedionate, copper 2.4-pen CAIGS, refers to Sulfur or selenium or both. The letter “C” in tanedionate, copper hexafluoroacetylacetonate, copper CIGS and CAIGS refers to copper. The letter“A” in AIGS and acetylacetonate, copper dimethylaminoethoxide, copper CAIGS which appears before the letters I and G refers to ketoesters, and mixtures thereof. silver. The letter “I” in CIGS, AIGS, and CAIGS refers to 0538 Sources of indium include indium metal, trialkylin indium. The letter “G” in CIGS, AIGS, and CAIGS refers to dium, trisdialkylamineindium, indium halides, indium chlo gallium. rides, dimethylindium chlorides, trimethylindium, indium 0550. As used herein, the terms CIGS, AIGS, and CAIGS acetylacetonates, indium hexafluoropentanedionates, indium include the variations C(I.G)S, A(IG)S, and CA(I,G)S, methoxyethoxides, indium methyltrimethylacetylacetates, respectively, and CIS, AIS, and CAIS, respectively, as well as indium trifluoropentanedionates, and mixtures thereof. CGS, AGS, and CAGS, respectively, unless described other 0539 Sources of gallium include gallium metal, trialkyl W1S. gallium, trisdialkylamine gallium, gallium halides, gallium 0551. As used herein, the term CIGS includes the terms fluorides, gallium chlorides, gallium iodides, diethylgallium CIGSSe and CIGSe, and these terms refer to compounds or chlorides, gallium acetate, gallium 2.4-pentanedionate, gal materials containing copper/indium/gallium/sulfur/sele lium ethoxide, gallium 2.2.6,6,-tetramethylheptanedionate, nium, which may contain sulfur or selenium or both. The term trisdimethylaminogallium, and mixtures thereof. AIGS includes the terms AIGSSe and AIGSe, and these terms 0540 Some sources of gallium and indium are described refer to compounds or materials containing silver/indium/ in International Patent Publication No. WO2008.057119. gallium/sulfur/selenium, which may contain Sulfur or sele nium or both. The term CAIGS includes the terms CAIGSSe and CAIGSe, and these terms refer to compounds or materials Additional Sulfurization or Selenization containing copper/silver/indium/gallium/sulfur/selenium, 0541. In various processes of this disclosure, a composi which may contain sulfur or selenium or both. tion or material may optionally be subjected to a step of 0552. As used herein, the term “chalcogenide” refers to a Sulfurization or selenization. compound containing one or more chalcogen atoms bonded 0542 Sulfurization with HS or selenization with HSe to one or more metal atoms. may be carried out by using pure HS or HSe, respectively, or 0553. The term “alkyl as used herein refers to a hydro may be done by dilution in hydrogen or in nitrogen. Seleni carbyl radical of a saturated aliphatic group, which can be a zation can also be carried out with Sevapor, or other source of branched or unbranched, substituted or unsubstituted ali elemental selenium. phatic group containing from 1 to 22 carbon atoms. This 0543. A sulfurization or selenization step can be done at definition applies to the alkyl portion of other groups such as, any temperature from about 200° C. to about 650° C., or at for example, cycloalkyl, alkoxy, alkanoyl, aralkyl, and other temperatures below 200° C. One or more steps of sulfuriza groups defined below. The term “cycloalkyl as used herein tion and selenization may be performed concurrently, or refers to a saturated, substituted or unsubstituted cyclic alkyl sequentially. ring containing from 3 to 12 carbonatoms. As used herein, the 0544 Examples of sulfurizing agents include hydrogen term “C(1-5)alkyl includes C(1)alkyl, C(2)alkyl, C(3)alkyl, sulfide, hydrogen sulfide diluted with hydrogen, elemental C(4)alkyl, and C(5)alkyl. Likewise, the term “C(3-22)alkyl sulfur, sulfur powder, carbon disulfide, alkyl polysulfides, includes C(1)alkyl, C(2)alkyl, C(3)alkyl, C(4)alkyl, C(5) dimethylsulfide, dimethyl disulfide, and mixtures thereof. alkyl, C(6)alkyl, C(7)alkyl, C(8)alkyl, C(9)alkyl, C(10)alkyl, 0545 Examples of selenizing agents include hydrogen C(11)alkyl, C(12)alkyl, C(13)alkyl, C(14)alkyl, C(15)alkyl, Selenide, hydrogen selenide diluted with hydrogen, elemental C(16)alkyl, C(17)alkyl, C(18)alkyl, C(19)alkyl, C(20)alkyl, Selenium, selenium powder, carbon diselenide, alkyl polyse C(21)alkyl, and C(22)alkyl. lenides, dimethyl selenide, dimethyl diselenide, and mixtures 0554. The term “alkenyl as used herein refers to an unsat thereof. urated, branched or unbranched, substituted or unsubstituted US 2011/0034667 A1 Feb. 10, 2011 28 alkyl or cycloalkyl having 2 to 22 carbon atoms and at least cyclic variations, and groups having a Substituent or Substitu one carbon-carbon double bond. The term “alkynyl as used ents replacing one or more hydrogens attached to any carbon herein refers to an unsaturated, branched or unbranched, Sub atom of the group. Substituents that may be attached to a stituted or unsubstituted alkyl or cycloalkyl having 2 to 22 carbon atom of the group include alkyl, cycloalkyl, alkenyl, carbon atoms and at least one carbon-carbon triple bond. alkynyl, alkoxy, alkanoyl, alkanoyloxy, alkylamino, alky 0555. The term “alkoxy” as used herein refers to an alkyl, laminoalkyl, aryl, heteroaryl, heterocycle, aroyl, aralkyl, cycloalkyl, alkenyl, or alkynyl group covalently bonded to an acyl, hydroxyl, cyano, halo, haloalkyl, amino, aminoacyl, oxygen atom. The term “alkanoyl as used herein refers to alkylaminoacyl, acyloxy, aryloxy, aryloxyalkyl, mercapto, —C(=O)-alkyl, which may alternatively be referred to as nitro, carbamyl, carbamoyl, and heterocycle. For example, “acyl. The term “alkanoyloxy” as used herein refers to the term ethyl includes without limitation —CHCH —O C(=O)-alkyl groups. The term “alkylamino” as used CHFCH, CFCH, CHFCHF, -CHFCHF, herein refers to the group —NRR", where R and R' are each - CHFCF, CFCHF, CFCHF, CFCF, and other either hydrogen or alkyl, and at least one of R and R' is alkyl. variations as described above. In general, a Substituent may Alkylamino includes groups such as piperidino wherein R itself be further substituted with any atom or group of atoms. and R' form a ring. The term “alkylaminoalkyl refers to 0562 Some examples of a substituent for a substituted -alkyl-NRR'. alkyl include halogen, hydroxyl, carbonyl, carboxyl, ester, 0556. The term “aryl” as used herein refers to any stable aldehyde, carboxylate, formyl, ketone, thiocarbonyl, monocyclic, bicyclic, or polycyclic carbon ring system of thioester, thioacetate, thioformate, selenocarbonyl, sele from 4 to 12 atoms in each ring, wherein at least one ring is noester, selenoacetate, selenoformate, alkoxyl, phosphoryl, aromatic. Some examples of an aryl include phenyl, naphthyl, phosphonate, phosphinate, amino, amido, amidine, imino, tetrahydro-naphthyl, indanyl, and biphenyl. Where an aryl cyano, nitro, azido, carbamato, Sulfhydryl, alkylthio. Sulfate, Substituent is bicyclic and one ring is non-aromatic, it is Sulfonate, Sulfamoyl, Sulfonamido, Sulfonyl, silyl, heterocy understood that attachment is to the aromatic ring. An aryl clyl, aryl, aralkyl, aromatic, and heteroaryl. may be substituted or unsubstituted. 0563. It will be understood that “substitution' or “substi 0557. The term “heteroaryl” as used herein refers to any tuted with refers to such substitution that is in accordance stable monocyclic, bicyclic, or polycyclic carbon ring system with permitted valence of the substituted atom and the sub of from 4 to 12 atoms in each ring, wherein at least one ring is stituent. As used herein, the term "substituted” includes all aromatic and contains from 1 to 4 heteroatoms selected from permissible substituents. oxygen, nitrogen and sulfur. Phosphorous and selenium may 0564. In general, a compound may contain one or more be a heteroatom. Some examples of a heteroaryl include chiral centers. Compounds containing one or more chiral acridinyl, quinoxalinyl, pyrazolyl, indolyl, benzotriazolyl, centers may include those described as an "isomer,” a “stere furanyl, thienyl, benzothienyl, benzofuranyl, quinolinyl, iso oisomer,” a “diastereomer, an “enantiomer, an “optical iso quinolinyl, oxazolyl, isoxazolyl, pyrazinyl, pyridazinyl, mer” or as a “racemic mixture.” Conventions for stere pyridinyl, pyrimidinyl, pyrrolyl, and tetrahydroquinolinyl. A ochemical nomenclature, for example the stereoisomer heteroaryl includes the N-oxide derivative of a nitrogen-con naming rules of Cahn, Ingold and Prelog, as well as methods taining heteroaryl. for the determination of stereochemistry and the separation of 0558. The term “heterocycle” or “heterocyclyl as used stereoisomers are known in the art. See, for example, Michael herein refers to an aromatic or nonaromatic ring system of B. Smith and Jerry March, March's Advanced Organic Chem from five to twenty-two atoms, wherein from 1 to 4 of the ring istry, 5th edition, 2001. The compounds and structures of this atoms are heteroatoms selected from oxygen, nitrogen, and disclosure are meant to encompass all possible isomers, Ste Sulfur. Phosphorous and selenium may be a heteroatom. reoisomers, diastereomers, enantiomers, and/or optical iso Thus, a heterocycle may be a heteroaryl or a dihydro or mers that would be understood to exist for the specified com tetrathydro version thereof. pound or structure, including any mixture, racemic or 0559 The term “aroyl” as used herein refers to an aryl otherwise, thereof. radical derived from an aromatic carboxylic acid, Such as a 0565. This invention encompasses any and all tautomeric, substituted benzoic acid. The term “aralkyl as used herein solvated or unsolvated, hydrated or unhydrated forms, as well refers to an aryl group bonded to an alkyl group, for example, as any atom isotope forms of the compounds and composi a benzyl group. tions disclosed herein. 0560. The term “carboxyl as used herein represents a 0566. This invention encompasses any and all crystalline group of the formula –C(=O)CH or - C(=O)Cl. The polymorphs or different crystalline forms of the compounds terms “carbonyl and “acyl as used herein refer to a group in and compositions disclosed herein. which an oxygen atom is double-bonded to a carbon atom >C=O. The term “hydroxyl” as used herein refers to OH Additional Embodiments or —O. The term "nitrile' or “cyano” as used herein refers to 0567 All publications, references, patents, patent publi —CN. The term “halogen' or “halo” refers to fluoro ( F), cations and patent applications cited herein are each hereby chloro (—Cl), bromo ( Br), and iodo (—I). specifically incorporated by reference in their entirety for all 0561. The term “substituted” as used herein refers to an purposes. atom having one or more Substitutions or Substituents which 0568 While this invention has been described in relation can be the same or different and may include a hydrogen to certain embodiments, aspects, or variations, and many Substituent. Thus, the terms alkyl, cycloalkyl, alkenyl, alky details have been set forth for purposes of illustration, it will nyl, alkoxy, alkanoyl, alkanoyloxy, alkylamino, alkylami be apparent to those skilled in the art that this invention noalkyl, aryl, heteroaryl, heterocycle, aroyl, and aralkyl as includes additional embodiments, aspects, or variations, and used herein refer to groups which include substituted varia that some of the details described herein may be varied con tions. Substituted variations include linear, branched, and siderably without departing from this invention. This inven US 2011/0034667 A1 Feb. 10, 2011 29 tion includes such additional embodiments, aspects, and 0578. In an inert atmosphere glovebox, a Schlenktube was variations, and any modifications and equivalents thereof. In charged with 0.64 g (1.22 mmol) of IncSeBu), 0.15 g (0.61 particular, this invention includes any combination of the mmol) of AgSe'Bu and 0.12 g (0.60 mmol) of CuSe'Bu. features, terms, or elements of the various illustrative com Benzene (15 mL) was added, and the reaction mixture was ponents and examples. stirred at 25°C. for min. An orange solution was obtained. 0569. The use herein of the terms “a,” “an,” “the and This solution was filtered through a filter cannula and the similar terms in describing the invention, and in the claims, mother liquor was collected. The solvent was then removed are to be construed to include both the singular and the plural. under dynamic vacuum. 0.88 g (97%) of orange solid was 0570. The terms “comprising,” “having,” “include.” recovered. “including and “containing are to be construed as open (0579 Elemental analysis: C, 25.3, H, 4.61. NMR: (1H) ended terms which mean, for example, “including, but not 1.03 (br), 1.72 (br), 1.80 (br), 2.05 (br), 3.72 (br), 3.95 (br) in limited to.” Thus, terms such as “comprising,” “having.” CDs. “include.” “including and “containing are to be construed 0580. The TGA for this MPP-CAIGS polymeric precursor as being inclusive, not exclusive. showed a transition beginning at about 146° C., having a 0571 Recitation of a range of values herein refers indi midpoint at about 211°C., and ending at 220°C. vidually to each and any separate value falling within the 0581. The yield for the transition was 49.6% (w/w), as range as if it were individually recited herein, whether or not compared to a theoretical yield for the formula CusAgo, some of the values within the range are expressly recited. For sInSea of 48.1% (w/w). Thus, the TGA showed that this example, the range “4 to 12 includes without limitation any polymeric precursor can be used to prepare CusAgos InSea whole, integer, fractional, or rational value greater than or layers and materials, and can be used as a component to equal to 4 and less than or equal to 12, as would be understood prepare other semiconductor layers, crystals, and materials. by those skilled in the art. Specific values employed herein will be understood as exemplary and not to limit the scope of Example 2 the invention. 0572 Recitation of a range of a number of atoms herein 0582. A polymeric precursor represented by the formula refers individually to each and any separate value falling {CuozAgo (Se'Bu)sGao Ino, was synthesized using the within the range as if it were individually recited herein, following procedure. whether or not some of the values within the range are 0583. In an inert atmosphere glovebox, a Schlenktube was expressly recited. For example, the term “C1-8 includes charged with 0.74 g (1.4 mmol) of InCSe'Bu), 0.28 g (0.59 without limitation the species C1, C2, C3, C4, C5, C6, C7, mmol) of Ga(Se'Bu), 0.28 g (1.4 mmol) of CuSe Bu and 48 and C8. mg (0.2 mmol) of AgSeBu. Benzene (15 mL) was added, and 0573. Definitions of technical terms provided herein the reaction mixture was stirred at 25° C. for 30 min. An should be construed to include without recitation those mean orange solution was obtained. This solution was filtered ings associated with these terms known to those skilled in the through a filter cannula and the mother liquor was collected. art, and are not intended to limit the scope of the invention. The solvent was then removed under dynamic vacuum. 1.27 Definitions of technical terms provided herein shall be con g (94%) of orange oil was recovered. strued to dominate over alternative definitions in the art or definitions which become incorporated herein by reference to 0584) Elemental analysis: C, 26.8, H, 4.04. NMR: (1H) the extent that the alternative definitions conflict with the 1.02 (br), 1.65 (br), 1.84 (br), 2.02 (br), 3.71 (br) in CD. definition provided herein. 0585. The TGA for this MPP-CAIGS polymeric precursor 0574. The examples given herein, and the exemplary lan showed a transition beginning at about 146° C., having a guage used herein are solely for the purpose of illustration, midpoint at about 212°C., and ending at 235°C. The yield for and are not intended to limit the scope of the invention. All the transition was 51.0% (w/w), as compared to a theoretical examples and lists of examples are understood to be non yield for the formula Cuo, Ago. Gao InoSea of 47.2% limiting. (w/w). Thus, the TGA showed that this polymeric precursor 0575. When a list of examples is given, such as a list of can be used to prepare Culo 7 Ago. Gao Ino, Sea layers and compounds, molecules or compositions suitable for this materials, and can be used as a component to prepare other invention, it will be apparent to those skilled in the art that semiconductor layers, crystals, and materials. mixtures of the listed compounds, molecules or compositions may also be suitable. Example 3 0586 A polymeric precursor represented by the formula EXAMPLES {Cuos Ago2(Se'Bu). In was synthesized using the following 0576. Thermogravimetric analysis (TGA) was performed procedure. using a Q50 Thermogravimetric Analyzer (TA Instruments, 0587. In an inert atmosphere glovebox, a Schlenktube was New Castle, Del.). NMR data were recorded using a Varian charged with 0.52 g (1.0 mmol) of IncSe'Bu), 0.16 g (0.8 400 MHz spectrometer. mmol) of CuSe Bu and 49 mg (0.2 mmol) of AgSe'Bu. Ben Zene (15 mL) was added, and the reaction mixture was stirred Example 1 at 25°C. for 30 min. An orange solution was obtained. This Preparation of Polymeric Precursor Compounds and solution was filtered through a filter cannula and the mother Compositions liquor was collected. The solvent was then removed under dynamic vacuum. 0.72 g (99%) of orange oil was recovered. 0577. A polymeric precursor represented by the formula 0588 Elemental analysis: C, 26.32, H, 4.87, In, 14.34, Ag, {Cuos Agos(Se'Bu). In was synthesized using the following 1.54, Cu, 7.94. NMR: (1H) 0.99 (br), 1.11 (br), 1.71 (br), 1.81 procedure. (br), 2.03 (br), 3.68 (br) in CD. US 2011/0034667 A1 Feb. 10, 2011 30
0589. In FIG. 8 is shown the TGA for this MPP-CAIGS 5Gaos Inos Sea layers and materials, and can be used as a polymeric precursor. The TGA showed a transition beginning component to prepare other semiconductor layers, crystals, at about 139° C., having a midpoint at about 212°C., and and materials. ending at 225° C. The yield for the transition was 46.2% (w/w), as compared to a theoretical yield for the formula Example 6 CusAgo, InSea of 47.2% (w/w). Thus, the TGA showed that 0599. A polymeric precursor represented by the formula this polymeric precursor can be used to prepare CusAgo, {Cuoss Ago (Se'Bu).sos Gaos Ino, was synthesized using 2InSe layers and materials, and can be used as a component the following procedure. to prepare other semiconductor layers, crystals, and materi 0600. In an inert atmosphere glovebox, a Schlenktube was als. charged with 0.74 g (1.4 mmol) of InCSe'Bu), 0.28 g (0.6 mmol) of Ga(Se'Bu), 0.34 g (1.7 mmol) of CuSe Bu and 48 Example 4 mg (0.2 mmol) of AgSeBu. Benzene (15 mL) was added, and the reaction mixture was stirred at 25° C. for 30 min. An 0590 A polymeric precursor represented by the formula orange solution was obtained. This solution was filtered {Cuo Agos(Se'Bu). In was synthesized using the following through a filter cannula and the mother liquor was collected. procedure. The solvent was then removed under dynamic vacuum. 1.39 0591. In an inert atmosphere glovebox, a Schlenktube was g (99%) of orange oil was recovered. charged with 0.52 g (1.0 mmol) of IncSe'Bu), 40 mg (0.2 0601 Elemental analysis: C, 26.64, H, 4.68, Ag, 1.49, Cu, mmol) of CuSe Bu and 0.2 g (0.8 mmol) of AgSe'Bu. Ben 7.88, In, 13.65, Ga. 3.02. NMR: (1H) 1.00 (br), 1.72 (br), 1.82 Zene (15 mL) was added, and the reaction mixture was stirred (br), 2.03 (br), 3.70 (br) in CD. at 25°C. for 30 min. An orange solution was obtained. This 0602. In FIG. 10 is shown the TGA for this MPP-CAIGS solution was filtered through a filter cannula and the mother polymeric precursor. The TGA showed a transition beginning liquor was collected. The solvent was then removed under at about 151° C., having a midpoint at about 21.6°C., and dynamic vacuum. 0.72 g (95%) of orange oil was recovered. ending at 230° C. The yield for the transition was 46.8% 0592 Elemental analysis: C, 24.87, H, 4.64, Ag, 9.38, Cu, (w/w), as compared to a theoretical yield for the formula 1.71, In, 14.83. NMR: (1H) 1.06 (br), 1.80 (br), 2.08 (br), 3.72 CussAgo, Gao. In Sea of 46.1% (w/w). Thus, the TGA (br) 3.95 (br) in CD. showed that this polymeric precursor can be used to prepare 0593. In FIG. 9 is shown the TGA for this MPP-CAIGS Cuoss Ago. Gao Ino,Se layers and materials, and can be polymeric precursor. The TGA showed a transition beginning used as a component to prepare other semiconductor layers, at about 142°C., having a midpoint at about 207 C., and crystals, and materials. ending at 220° C. The yield for the transition was 50.2% (w/w), as compared to a theoretical yield for the formula Example 7 Cuo AgonSea of 49.0% (w/w). Thus, the TGA showed that 0603 A polymeric precursor represented by the formula this polymeric precursor can be used to prepare Cuo Ago. {Cuos Agos (Se'Bu), Gaos Ino, was synthesized using the sInSe layers and materials, and can be used as a component following procedure. N prepare other semiconductor layers, crystals, and materi 0604. In an inert atmosphere glovebox, a Schlenktube was aS. charged with 0.74 g (1.4 mmol) of InCSe'Bu), 0.28 g (0.6 mmol) of Ga(Se'Bu), 0.20 g (1.0 mmol) of CuSe'Bu and Example 5 0.24 g (1.0 mmol) of AgSe'Bu. Benzene (15 mL) was added, and the reaction mixture was stirred at 25°C. for 30 min. An 0594. A polymeric precursor represented by the formula orange solution was obtained. This solution was filtered {CuosAgos(Se'Bu), Gaos Inos was synthesized using the through a filter cannula and the mother liquor was collected. following procedure. The solvent was then removed under dynamic vacuum. 1.38 0595. In an inert atmosphere glovebox, a Schlenktube was g (95%) of orange oil was recovered. charged with 0.26 g (0.5 mmol) of InCSe'Bu), 0.24 g (0.5 0605 Elemental analysis: C, 25.93, H, 4.82, Ag, 8.56, Cu, mmol) of Ga(Se'Bu), 0.10 g (0.5 mmol) of CuSe Bu and 3.79, In, 13.87, Ga, 2.89. NMR: (1H) 1.04 (br), 1.74 (br), 1.85 0.12 g (0.5 mmol) of AgSe'Bu. Benzene (15 mL) was added, (br), 2.06 (br), 3.74 (br), 3.94 (br) in CD. and the reaction mixture was stirred at 25°C. for 30 min. An 0606. In FIG. 11 is shown the TGA for this MPP-CAIGS orange solution was obtained. This solution was filtered polymeric precursor. The TGA showed a transition beginning through a filter cannula and the mother liquor was collected. at about 148° C., having a midpoint at about 213°C., and The solvent was then removed under dynamic vacuum. 0.72 ending at 225° C. The yield for the transition was 48.5% g (95%) of orange oil was recovered. (w/w), as compared to a theoretical yield for the formula Cuos AgosGao Ino, Sea of 47.2% (W/w). Thus, the TGA 0596 Elemental analysis: C, 26.09, H, 4.73, In, 13.79, Ga., showed that this polymeric precursor can be used to prepare 5.24, Ag, 7.53, Cu, 4.65. NMR: (1H) 1.04 (br), 1.72 (br), 1.82 Cuos AgosGao Ino, Se layers and materials, and can be (br), 2.06 (br), 3.75 (br), 3.93 (br) in CD. used as a component to prepare other semiconductor layers, 0597. The TGA for this MPP-CAIGS polymeric precursor crystals, and materials. showed a transition beginning at about 152 C., having a midpoint at about 21.6°C., and ending at 225°C. Example 8 0598. The yield for the transition was 47.8% (w/w), as compared to a theoretical yield for the formula CusAgo, 0607. A polymeric precursor represented by the formula sGas InoSea of 46.5% (w/w). Thus, the TGA showed that {Cuos Agoos (Se'Bu)sssGaos Ino, was synthesized using this polymeric precursor can be used to prepare CusAgo, the following procedure. US 2011/0034667 A1 Feb. 10, 2011
0608. In an inert atmosphere glovebox, a Schlenktube was 0618. The TGA for this MPP-AIGS polymeric precursor charged with 0.73 g (1.4 mmol) of InCSe'Bu), 0.29 g (0.6 showed a transition beginning at about 143° C., having a mmol) of Ga(Se'Bu), 0.32 g (1.6 mmol) of CuSe Bu and 24 midpoint at about 203°C., and ending at about 230°C. The mg (0.1 mmol) of AgSeBu. Benzene (15 mL) was added, and yield for the transition was 50.3% (w/w), as compared to a the reaction mixture was stirred at 25° C. for 30 min. An theoretical yield for the formula Ago,InSea of 50.4% (w/w). orange solution was obtained. This solution was filtered Thus, the TGA showed that this polymeric precursor can be through a filter cannula and the mother liquor was collected. used to prepare Ago,InSe layers and materials, and can be The solvent was then removed under dynamic vacuum. 1.29 used as a component to prepare other semiconductor layers, g (95%) of orange oil was recovered. crystals, and materials. 0609 NMR: (1H) 1.0 (br), 1.71 (br), 1.82 (br), 2.03 (br), 3.69 (br) in CD. 0610. The TGA for this MPP-CAIGS polymeric precursor Example 11 showed a transition beginning at about 140° C., having a midpoint at about 215°C., and ending at 230°C. The yield for 0619. A polymeric precursor represented by the formula the transition was 46.0% (w/w), as compared to a theoretical {Agos(Se'Bu)soIn} was synthesized using the following yield for the formula CusAgosGao. In Sea of 46.3% procedure. (w/w). Thus, the TGA showed that this polymeric precursor 0620. In an inert atmosphere glovebox, a Schlenktube was can be used to prepare CuosAgoosGao Ino, Se layers and charged with 0.36 g (0.69 mmol) of InCSe'Bu) and 0.15g materials, and can be used as a component to prepare other (0.61 mmol) of AgSeBu. Benzene (15 mL) was added, and semiconductor layers, crystals, and materials. the reaction mixture was stirred at 25°C. for 30 min. A light Example 9 yellow solution was obtained. This solution was filtered through a filter cannula and the mother liquor was collected. Preparation of Polymeric Precursor Compounds and The solvent was then removed under dynamic vacuum. 0.49 Compositions g (96%) of light yellow solid was recovered. 0611 A polymeric precursor represented by the formula 0621 Elemental analysis: C, 24.3, H, 4.45. NMR: (1H) {Ag(Se'Bu). In was synthesized using the following pro 1.06 (t, 12H, J, 6.8 Hz), 1.67 (br), 1.74 (br), 1.80 (br), 1.85 cedure. (d. J–6.8 Hz), 2.09 (br), 3.75 (q, Jr., 6.4 Hz), 3.95 (br) 0612. In an inert atmosphere glovebox, a Schlenktube was in CDs. charged with 0.52 g (1 mmol) of IncSe'Bu), and 0.24 g (1 0622. In FIG. 12 is shown the TGA for this MPP-AIGS mmol) of AgSe'Bu. Benzene (15 mL) was added, and the polymeric precursor. The TGA showed a transition beginning reaction mixture was stirred at 25° C. for 30 min. A light at about 151°C., having a midpoint at 203°C., and ending at yellow solution was obtained. This solution was filtered through a filter cannula and the mother liquor was collected. 220° C. The yield for the transition was 50.3% (w/w), as The solvent was then removed under dynamic vacuum. 0.52 compared to a theoretical yield for the formula Ago,InSea of g (68%) of light yellow solid was recovered. 49.8% (w/w). Thus, the TGA showed that this polymeric 0613 Elemental analysis: C, 24.59, H, 4.45, In, 15.21, Ag, precursor can be used to prepare Ago InSe layers and mate 15.71. NMR: (1H) 1.07 (t, 12H, J, 7.2 Hz), 1.81 (d. 12H, rials, and can be used as a component to prepare other semi J–6.8 Hz), 1.86-2.16 (m, 8H), 3.72-3.80 (m, 4H) in C.D. conductor layers, crystals, and materials. 0614. The TGA for this MPP-AIGS polymeric precursor showed a transition beginning at about 147 C., having a Example 12 midpoint at about 207 C., and ending at about 220°C. The yield for the transition was 49.8% (w/w), as compared to a 0623) A polymeric precursor represented by the formula theoretical yield for the formula AgInSes of 49.6% (w/w). {Agis (Se'Bu)as In} was synthesized using the following Thus, the TGA showed that this polymeric precursor can be procedure. used to prepare AgInSelayers and materials, and can be used 0624. In an inert atmosphere glovebox, a Schlenktube was as a component to prepare other semiconductor layers, crys charged with 0.31 g (0.59 mmol) of InCSe'Bu) and 0.22 g tals, and materials. (0.90 mmol) of AgSe'Bu. Benzene (15 mL) was added, and Example 10 the reaction mixture was stirred at 25°C. for 30 min. A dark brown solution was obtained. This solution was filtered 0615. A polymeric precursor represented by the formula through a filter cannula and the mother liquor was collected. {Ago (Se'Bu). In was synthesized using the following The solvent was then removed under dynamic vacuum. 0.49 procedure. g (92%) of dark brown oil was recovered. 0616) In an inert atmosphere glovebox, a Schlenktube was charged with 0.52 g (1 mmol) of IncSe'Bu), and 0.15 g (0.60 0625 Elemental analysis: C, 24.1, H, 4.35, Ag, 17.1, In, mmol) of AgSe'Bu. Benzene (15 mL) was added, and the 12.6. NMR: (1H) 1.06 (t, 12H, J, 6.8 Hz), 1.80 (d. 12H, reaction mixture was stirred at 25° C. for 30 min. A light J–6.4 Hz), 1.85-2.11 (m, 8H), 3.72-3.77 (m, 4H) in CD. yellow solution was obtained. This solution was filtered 0626. In FIG. 13 is shown the TGA for this MPP-AIGS through a filter cannula and the mother liquor was collected. polymeric precursor. The TGA showed a transition beginning The solvent was then removed under dynamic vacuum. 0.31 at about 135° C., having a midpoint at about 194°C., and g (46%) of light yellow oil was recovered. ending at 215° C. The yield for the transition was 51.0% 0617 Elemental analysis: C, 26.2, H, 4.73. NMR: (1H) (w/w), as compared to a theoretical yield for the formula 1.03 (t, J–7.2 Hz), 1.10 (br), 1.71 (br), 1.83 (br), 1.95 (br), Ags InSea of 48.9% (w/w). Thus, the TGA showed that this 2.07 (br), 2.09 (br), 3.75 (br), 3.95 (br) in CD. polymeric precursor can be used to prepare Ags InSe layers US 2011/0034667 A1 Feb. 10, 2011 32 and materials, and can be used as a component to prepare and the mother liquor was collected. The solvent was then other semiconductor layers, crystals, and materials. removed under dynamic vacuum. 0.61 g (90%) of light yel low solid was recovered. Example 13 0637 Elemental analysis: C, 25.9, H, 4.7. NMR: (1H) 1.04 (br), 1.10 (br), 1.74 (br), 1.86 (br), 2.06 (br), 3.76 (br), 3.93 0627. A polymeric precursor represented by the formula (br) in CD. {Ag(Se'Bu)(Se'Bu).In was synthesized using the following 0638. In FIG. 15 is shown the TGA for this MPP-AIGS procedure. polymeric precursor. The TGA showed a transition beginning 0628. In an inert atmosphere glovebox, a Schlenktube was at about 159° C., having a midpoint at about 211° C., and charged with 0.26 g (0.50 mmol) of InCSe'Bu) and 0.12 g ending at 230° C. The yield for the transition was 49.7% (0.50 mmol) of AgSe'Bu. Benzene (15 mL) was added, and (w/w), as compared to a theoretical yield for the formula the reaction mixture was stirred at 25°C. for 30 min. A dark Agos Ino Gaosse of 47.3% (w/w). Thus, the TGA showed brown solution was obtained. This solution was filtered that this polymeric precursor can be used to prepare Agosno through a filter cannula and the mother liquor was collected. 2Gaosse layers and materials, and can be used as a compo The solvent was then removed under dynamic vacuum. 0.31 nent to prepare other semiconductor layers, crystals, and g (97%) of brown solid was recovered. materials. 0629 NMR: (1H) 1.07 (br), 1.83 (br), 1.88 (br), 2.12 (br), 3.79 (br) in CD. Example 16 0630. The TGA for this MPP-AIGS polymeric precursor 0639. A polymeric precursor represented by the formula showed transition onsets at about 117 and 174°C., and ending {Ag(Se'Bu). In Gao, was synthesized using the following at about 230° C. The yield for the transitions was 50.8% procedure. (w/w), as compared to a theoretical yield for the formula 0640. In an inert atmosphere glovebox, a Schlenktube was AgInSea of 49.6% (w/w). Thus, the TGA showed that this charged with 0.16 g (0.3 mmol) of IncSe'Bu), 0.33 g (0.7 polymeric precursor can be used to prepare AgInSe layers mmol) of Ga(Se'Bu) and 0.24 g (1 mmol) of AgSe'Bu. and materials, and can be used as a component to prepare Benzene (15 mL) was added, and the reaction mixture was other semiconductor layers, crystals, and materials. stirred at 25° C. for 30 min. A light yellow solution was obtained. This solution was filtered through a filter cannula Example 14 and the mother liquor was collected. The solvent was then 0631 A polymeric precursor represented by the formula removed under dynamic vacuum. 0.69 g (95%) of light yel {Ag(Se'Bu),Ga was synthesized using the following proce low solid was recovered. dure. (0641 Elemental analysis: C, 25.4, H, 4.56. NMR: (1H) 0632. In an inert atmosphere glovebox, a Schlenktube was 1.05 (br), 1.69 (br), 1.77 (br), 1.85 (br), 2.08 (br), 3.76 (br), charged with 0.96 g (2 mmol) of Ga(Se'Bu) and 0.49 g (2 3.93 (br) in CD. mmol) of AgSe'Bu. Benzene (15 mL) was added, and the 0642. In FIG. 16 is shown the TGA for this MPP-AIGS reaction mixture was stirred at 25° C. for 30 min. A light polymeric precursor. The TGA showed a transition beginning yellow solution was obtained. This solution was filtered at about 149° C., having a midpoint at about 209°C., and through a filter cannula and the mother liquor was collected. ending at 225° C. The yield for the transition was 50.6% The solvent was then removed under dynamic vacuum. 0.73 (w/w), as compared to a theoretical yield for the formula g (51%) of light yellow solid was recovered. AgIn Gao, Sea of 47.5% (w/w). Thus, the TGA showed that 0633 Elemental analysis: C, 25.8, H, 4.7, Ag, 15.4, Ga., this polymeric precursor can be used to prepare AgIn Gao 9.74. NMR: (1H) 1.07 (t, 12H, J, 7.6 Hz), 1.79 (d. 12H, 7Se layers and materials, and can be used as a component to J–6.8 Hz), 1.84-2.16 (m, 8H), 3.75-3.80 (m, 4H) in C.D. prepare other semiconductor layers, crystals, and materials. 0634. In FIG. 14 is shown the TGA for this MPP-AIGS Example 17 polymeric precursor. The TGA showed a transition beginning at about 139° C., having a midpoint at about 219 C., and 0643 A polymeric precursor represented by the formula ending at 235° C. The yield for the transition was 49.9% {Ag(Se'Bu). Ino, Gaos was synthesized using the following (w/w), as compared to a theoretical yield for the formula procedure. AgGaSea of 46.5% (w/w). Thus, the TGA showed that this 0644. In an inert atmosphere glovebox, a Schlenktube was polymeric precursor can be used to prepare AgGaSe layers charged with 0.37 g (0.7 mmol) of IncSe'Bu), 0.14 g (0.3 and materials, and can be used as a component to prepare mmol) of Ga(Se'Bu) and 0.24 g (1 mmol) of AgSe'Bu. other semiconductor layers, crystals, and materials. Benzene (15 mL) was added, and the reaction mixture was stirred at 25° C. for 30 min. A light yellow solution was Example 15 obtained. This solution was filtered through a filter cannula and the mother liquor was collected. The solvent was then 0635 A polymeric precursor represented by the formula removed under dynamic vacuum. 0.72 g (96%) of light yel {Agos(Se'Bu), sino Gaos was synthesized using the fol low solid was recovered. lowing procedure. 0645 Elemental analysis: C, 24.9, H, 4.53, Ag, 15.6, In, 0636. In an inert atmosphere glovebox, a Schlenktube was 10.88, Ga, 2.72. NMR: (1H) 1.06 (br), 1.68 (br), 1.79 (br), charged with 0.10 g (0.2 mmol) of IncSe'Bu), 0.38 g (0.8 1.86 (br), 2.09 (br), 3.76 (br), 3.93 (br) in CD. mmol) of Ga(Se'Bu) and 0.20 g (0.8 mmol) of AgSe'Bu. (0646. The TGA for this MPP-AIGS polymeric precursor Benzene (15 mL) was added, and the reaction mixture was showed a transition beginning at about 140° C., having a stirred at 25° C. for 30 min. A light yellow solution was midpoint at about 203°C., and ending at 220°C. The yield for obtained. This solution was filtered through a filter cannula the transition was 50.5% (w/w), as compared to a theoretical US 2011/0034667 A1 Feb. 10, 2011
yield for the formula AgIn Gao Sea of 48.7% (w/w). Thus, the reaction mixture was stirred at 25°C. for 30 min. A yellow the TGA showed that this polymeric precursor can be used to solution was obtained. The solvent was removed, and the oil prepare AgIno, Gao Sea layers and materials, and can be product was extracted with pentane. Upon removal of pen used as a component to prepare other semiconductor layers, tane, 2.62 g (94%) of bright yellow oil was obtained. crystals, and materials. 0657 NMR: (1H) 0.92 (br), 1.35 (br), 1.52 (br), 2.04 (br), 3.22 (br) in C.D. Example 18 0658. The TGA for this MPP-AIGS polymeric precursor 0647. A polymeric precursor represented by the formula showed a transition onset at about 127°C., ending at about {Ag(Se'Bu). InosGaos was synthesized using the following 236° C. The yield for the transition was 44.5% (w/w), as procedure. compared to a theoretical yield for the formula AgInSea of 0648. In an inert atmosphere glovebox, a Schlenktube was 43.3% (w/w). Thus, the TGA showed that this polymeric charged with 0.26 g (0.5 mmol) of InCSe'Bu), 0.24 g (0.5 precursor can be used to prepare AgInSe layers and materi mmol) of Ga(Se'Bu), and 0.24 g (1 mmol) of AgSe'Bu. als, and can be used as a component to prepare other semi Benzene (15 mL) was added, and the reaction mixture was conductor layers, crystals, and materials. stirred at 25° C. for 30 min. A light yellow solution was Example 21 obtained. This solution was filtered through a filter cannula and the mother liquor was collected. The solvent was then Preparation of Monomer Compounds removed under dynamic vacuum. 0.58 g (78%) of light yel 0659 A monomer compound represented by the formula low solid was recovered. Ga(Se'Bu) was synthesized using the following procedure. 0649 Elemental analysis: C, 25.1, H, 4.57, Ag, 14.94, In, 0660. To a 500-mL round bottom Schlenk flaskin an inert 7.77, Ga., 5.06. NMR: (1H) 1.04 (br), 1.77 (br), 1.85 (br), 2.08 atmosphere glovebox was added NaSe'Bu (28 g, 176 mmol) (br), 3.76 (br), 3.93 (br) in CD. and THF (200 mL). The flask was then transferred to a 0650. The TGA for this MPP-AIGS polymeric precursor Schlenkline and a solution of GaCl (10.3 g, 59 mmol) in 20 showed a transition beginning at about 149° C., having a mL of benzene was then added. The reaction mixture was midpoint at about 207°C., and ending at 225°C. The yield for stirred for 12 hand the volatiles were removed under reduced the transition was 50.5% (w/w), as compared to a theoretical pressure. The residue was extracted with toluene and filtered. yield for the formula AgInGaosse of 48.1% (w/w). Thus, The volatiles from the filtrate were then removed under the TGA showed that this polymeric precursor can be used to reduced pressure leaving a colorless oil (23 g, 48 mmol, 83% prepare AgIn Gao Se layers and materials, and can be yield). used as a component to prepare other semiconductor layers, 0661 NMR: (1H: C6D6): 0.85 (t, J–7.2 Hz, 9H, CH): crystals, and materials. 1.40 (m, 6H, —CH ); 1.77 (m, 6H, —CH ); 3.03 (brs, Example 19 6H, SeCH ). 0651 A polymeric precursor represented by the formula Example 22 {Ag(Se'Bu). (Se'Bu)Gao Ino, was synthesized using the 0662. A monomer compound represented by the formula following procedure. In(Se'Bu) was synthesized using the following procedure. 0652. In an inert atmosphere glovebox, a Schlenktube was 0663 To a 500-mL round bottom Schlenk flaskin an inert charged with 0.37 g (0.7 mmol) of IncSe'Bu), 0.14 g (0.3 atmosphere glove box was added InCls (6.95 g, 31 mmol), mmol) of Ga(Se'Bu) and 0.24 g (1.0 mmol) of AgSe'Bu. NaSe'Bu (15g, 94 mmol), and THF (200 mL). The reaction Benzene (15 mL) was added, and the reaction mixture was mixture was transferred to a Schlenkline and stirred for 12 h. stirred at 25°C. formin. A light yellow solution was obtained. The volatiles were subsequently removed under reduced This solution was filtered through a filter cannula and the pressure. The remaining Solid residue was dissolved in hot mother liquor was collected. The solvent was then removed toluene and filtered. The volatiles from the filtrate were under dynamic vacuum. 0.71 g (95%) of light yellow powder removed under reduced pressure and the resulting Solid was was recovered. washed with pentane. The final colorless solid was dried 0653 NMR: (1H) 1.06 (br), 1.83 (br), 2.12 (br), 3.79 (br) under reduced pressure and isolated (15g, 29 mmol, 92% in CDs. yield). 0654) The TGA for this MPP-Ag polymeric precursor 0664 NMR: (1H: C6D6): 0.913 (t, J–7.2 Hz, 9H, CH): showed transition onsets at about 94 and 177° C., ending at about 220°C. The yield for the transitions was 50.5% (w/w), 1.43 (m, 6H, —CH ); 1.72 (m, 6H, —CH ); 2.90 (t, as compared to a theoretical yield for the formula AgGao Ino. J–7.2 Hz, 6H, SecH ). 7Sea of 47.5% (w/w). Thus, the TGA showed that this poly Example 23 meric precursor can be used to prepare AgGao InoSe lay ers and materials, and can be used as a component to prepare 0665 A monomer compound represented by the formula other semiconductor layers, crystals, and materials. Ag(Se'Bu) was synthesized using the following procedure. 0666 BuSeH (5.8 mmol) and Et-N (1.1 mL) were slowly Example 20 added to a solution of AgNO (1.0g, 5.8 mmol) in CHCN (20 mL) at 0°C. A colorless solution with light yellow precipitate 0655. A polymeric precursor represented by the formula formed rapidly. The reaction mixture was allowed to warm to {Ag(Se"Hex) In was synthesized using the following pro 25° C. and stirred for 12 h. The excess BuSeH was removed cedure. under dynamic vacuum and a grey Solid was recovered. The 0656. In an inert atmosphere glovebox, a Schlenktube was solid was washed with CHCN (2x100 mL) to afford a grey charged with 1.93 g (3.2 mmol) of In(Se'Hex) and 0.86 g solid (1.23g, 87%). (3.2 mmol) of AgSe'Hex. Benzene (50 mL) was added, and 0667 NMR: (1H: CDC1): 1.73 (in presence of pyridine). US 2011/0034667 A1 Feb. 10, 2011 34
Example 24 meric precursor of Example 5 in THF to a concentration of 12% (w/w), and adding 0.1% (w/w) sodium relative to copper Preparation of Bulk CAIS Materials as NaIn(SeBu). 0668. A bulk CAIS material having the formula Cup. Example 31 o5Agos InSea was prepared by heating the polymeric precur sor Cuoios Agogs(Se'Bu), n} at 10°C. per minute to a final 0675. A polymeric precursor ink composition is prepared temperature of 500° C. and holding the temperature at 500° C. in a glovebox in an inert atmosphere by dissolving the poly for 30 minutes. The X-ray diffraction pattern of this material meric precursor of Example 3 in a toluene solution at 20% is shown in FIG. 17 and indicated the presence of a crystalline (w/w). To this solution is added 0.05% (w/w) sodium relative CAIS phase. to copper as NaIn(Se'Bu). Example 32 Example 25 0676 A polymeric precursor ink composition is prepared 0669 Abulk CAIS material having the formula Cuo Ago. in a glovebox in an inert atmosphere by dissolving the poly 9InSea was prepared by heating the polymeric precursor meric precursor of Example 4 in decane to a total concentra {Cuo. Ago (Se'Bu). In} at 10°C. per minute to a final tem tion of 20% (w/w). perature of 500° C. and holding the temperature at 500° C. for 30 minutes. The X-ray diffraction pattern of this material is Example 33 shown in FIG. 18 and indicated the presence of a crystalline 0677. A polymeric precursor ink composition is prepared CAIS phase. in a glovebox in an inert atmosphere by dissolving the poly meric precursor of Example 6 in decane to a total concentra Example 26 tion of 50% (w/w). Preparation of Bulk AIS Materials Example 34 0670) A bulk AIS material having the formula AgInSea Polymeric Precursor Ink Compositions was prepared by heating the polymeric precursor Ag(Se'Bu) 0678. A polymeric precursor ink composition is prepared In} at 10°C. per minute to a final temperature of 500° C. and in a glovebox in an inert atmosphere by dissolving the poly holding the temperature at 500° C. for 30 minutes. The X-ray meric precursor of Example 10 in THF to a concentration of diffraction pattern of this material is shown in FIG. 19 and 12% (w/w), and adding 0.1% (w/w) sodium relative to copper indicated the presence of a crystalline AIS phase. as NaIn(SeBu). Example 27 Example 35 0679. A polymeric precursor ink composition is prepared 0671 Abulk AIS material having the formula Ago InSea was prepared by heating the polymeric precursor Agos in a glovebox in an inert atmosphere by dissolving the poly (SeBu). In at 10° C. per minute to a final temperature of meric precursor of Example 10 in a toluene solution at 20% 500° C. and holding the temperature at 500° C. for 30 min (w/w). To this solution is added 0.05% (w/w) sodium relative utes. The X-ray diffraction pattern of this material is shown in to copper as NaIn(Se'Bu). FIG. 20 and indicated the presence of a crystalline AIS phase. Example 36 Example 28 0680 A polymeric precursor ink composition is prepared in a glovebox in an inert atmosphere by dissolving the poly Polymeric Precursor Ink Compositions meric precursor of Example 12 in decane to a total concen tration of 20% (w/w). 0672 A polymeric precursor ink was prepared by mixing Cuoss Agoos(SeBu) so Ino, Gao with Xylene (15% polymer Example 37 content, by weight) in an inert atmosphere glove box. An 0681 A polymeric precursor ink composition is prepared aliquot (0.3 mL) of the ink solution was filtered through a 0.2 in a glovebox in an inert atmosphere by dissolving the poly um PTFE syringe filter. meric precursor of Example 12 in decane to a total concen tration of 50% (w/w). Example 29 Example 38 0673 A polymeric precursor ink was made by mixing Culos-Agoos (Se'Bu)ass Ino, Gao with Xylene (15% polymer Spin Casting Deposition of Polymeric Precursor Ink content, by weight) in an inert atmosphere glove box. An Compositions aliquot (0.3 mL) of the ink solution was filtered through a 0.2 0682. A polymeric precursor ink was prepared by mixing um PTFE syringe filter. Cuoss Agoos(Se'Bu) so Ino, Gao with Xylene (15% polymer content, by weight) in an inert atmosphere glove box. An Example 30 aliquot (0.3 mL) of the ink solution was filtered through a 0.2 um PTFE syringe filter and deposited onto a piece of 1 inch by 0674) A polymeric precursor ink composition is prepared 1 inch Mo-coated glass substrate in a raster fashion. The in a glovebox in an inert atmosphere by dissolving the poly substrate was spun at 1200 rpm for 1 minute using a G3P-8 US 2011/0034667 A1 Feb. 10, 2011
Spin Coater (Specialty Coating Systems) in an inert atmo 0686. The substrate is removed and is heated at a tempera sphere glove box, allowed to sit for about 2 minutes, and ture of 350° C. in an inert atmosphere. A thin film material is placed in a pre-heated (300° C.) furnace for 30 minutes for produced which is a photovoltaic absorber layer. The final conversion of the polymer to a CAIGS material. This depo film thickness is 1 micron. sition process (filter/deposit/convert) was repeated 7 and 14 times, with the final deposition and conversion followed by Example 42 annealing in a furnace at 550°C. for 1 hour. The CAIGS film resulting from 7 depositions had a thickness of about 400 nm. 0687. A polymeric precursor ink composition is prepared The CAIGS film resulting from 14 depositions had a thick in a glovebox in an inert atmosphere by dissolving the poly ness of about 850 nm. meric precursor of Example 3 in a toluene solution at 20% (w/w). To this solution is added 0.05% (w/w) sodium relative Example 39 to copper as NaIn(Se'Bu). The ink is rod coated onto a molybdenum-coated glass substrate using a K CONTROL 0683. A polymeric precursor ink was made by mixing COATER MODEL 201 (R K Print-Coat Instr., Litlington, Culos-Agoos (Se'Bu)ass Ino, Gao with Xylene (15% polymer UK) in a glovebox in an inert atmosphere. content, by weight) in an inert atmosphere glove box. An aliquot (0.3 mL) of the ink solution was filtered through a 0.2 0688. The substrate is removed and is heated at a tempera um PTFE syringe filter and deposited onto a piece of 1 inch by ture of 380° C. in an inert atmosphere A thin film material is 1 inch Mo-coated glass substrate in a raster fashion. The produced which is a photovoltaic absorber layer. The final substrate was spun at 1200 rpm for 1 minute using a G3P-8 film thickness is 1.5 micron. Spin Coater (Specialty Coating Systems) in an inert atmo sphere glove box, allowed to sit for about 2 minutes, and Example 43 placed in a pre-heated (300° C.) furnace for 30 minutes for conversion of the polymer to a CAIGS material. This depo Dip Coating Deposition of Polymeric Precursor Ink sition process (filter/deposit/convert) was repeated 7 times, Compositions with the final deposition and conversion followed by anneal ing in a furnace at 550° C. for 1 hour. The CAIGS film 0689. A polymeric precursor ink composition is prepared resulting from this deposition had a thickness of about 400 in a glovebox in an inert atmosphere by dissolving the poly . meric precursor of Example 4 in decane to a total concentra tion of 20% (w/w). The ink is dip coated onto an aluminum Example 40 Substrate in an inert atmosphere. 0690. The substrate is removed and is heated at a tempera Spin Casting Deposition of Polymeric Precursor Ink ture of 340°C. in an inert atmosphere A thin film material is Compositions produced which is a photovoltaic absorber layer. The final 0684 An ink was prepared in an inert atmosphere glove film thickness is 2.5 micron. box by mixing AgIn(Se'Hex) with xylene (20% polymer content, by weight). An aliquot (0.3 mL) of the ink solution Example 44 was filtered through a 0.2 Lum PTFE syringe filter and depos ited onto a piece of 1 inch by 1 inch Mo-coated glass substrate Slot Die Coating Deposition of Polymeric Precursor in a raster fashion. The substrate was spun at 1200 rpm for 1 Ink Compositions minute using a G3P-8 Spin Coater (Specialty Coating Sys tems) in an inert atmosphere glove box, allowed to sit for 0691 A polymeric precursor ink composition is prepared about 2 minutes, and placed in a pre-heated (300°C.) furnace in a glovebox in an inert atmosphere by dissolving the poly for 30 minutes for conversion of the polymeric precursor to an meric precursor of Example 5 in THF to a concentration of AIS material. This deposition process (filter/deposit/convert) 12% (w/w), and adding 0.1% (w/w) sodium relative to copper was repeated 8 times, with the final deposition/conversion as NaIn(Se'Bu). The ink is slot die coated onto a Mo-coated followed by annealing in a furnace at 550°C. for 1 hour. The glass Substrate in an inert atmosphere. AIS film had a thickness of about 500 nm. 0692. The substrate is removed and is heated at a tempera ture of 300° C. in an inert atmosphere A thin film material is Example 41 produced which is a photovoltaic absorber layer. The final film thickness is 1.5 micron. Rod Coating Deposition of Polymeric Precursor Ink Compositions Example 45 0685. A polymeric precursor ink composition is prepared in a glovebox in an inert atmosphere by dissolving the poly 0693. A polymeric precursor ink composition is prepared meric precursor of Example 5 in THF to a concentration of in a glovebox in an inert atmosphere by dissolving the poly 12% (w/w), and adding 0.1% (w/w) sodium relative to copper meric precursor of Example 3 in a toluene solution at 20% as NaIn(Se'Bu). The ink is rod coated onto a molybdenum (w/w). To this solution is added 0.05% (w/w) sodium relative coated glass substrate using a K CONTROL COATER to copper as NaIn(SeBu). The ink is slot die coated onto a MODEL 201 (R K Print-Coat Instr., Litlington, UK) in a molybdenum-coated Stainless steel Substrate in an inert atmo glovebox in an inert atmosphere. sphere. US 2011/0034667 A1 Feb. 10, 2011 36
0694. The substrate is removed and is heated at a tempera 0703. The spray-coated substrate is heated at a tempera ture of 380° C. in an inert atmosphere A thin film material is ture of 350° C. in an inert atmosphere. A thin film material is produced which is a photovoltaic absorber layer. The final produced which is a photovoltaic absorber layer. The final film thickness is 2.0 micron. film thickness is 2 micron. Example 46 Example 50 Screen Printing Deposition of Polymeric Precursor Preparation of a Solar Cell Ink Compositions 0704. A solar cell is made by depositing an electrode layer on a polyethylene terephthalate substrate. 0695) A polymeric precursor ink composition is prepared 0705. A thin film material photovoltaic absorber layer is in a glovebox in an inert atmosphere by dissolving the poly coated onto the electrode layer according to the following meric precursor of Example 6 in decane to a total concentra procedure. A polymeric precursor ink composition is pre tion of 50% (w/w). The polymeric precursor ink is screen pared in a glovebox in an inert atmosphere by dissolving the printed onto a molybdenum-coated Stainless steel Substrate in polymeric precursor of Example 5 in THF to a concentration an inert atmosphere. of 12% (w/w), and adding 0.1% (w/w) sodium relative to 0696. The substrate is removed and is heated at a tempera copper as NaIn(SeBu). The ink is slot die coated onto a ture of 400°C. in an inert atmosphere. A thin film material is Mo-coated glass Substrate in an inert atmosphere. The Sub produced which is a photovoltaic absorber layer. strate is removed and is heated at a temperature of 300° C. in 0697. The final film thickness is 2.8 micron. an inert atmosphere A thin film material is produced which is a photovoltaic absorber layer. The final film thickness is 1.5 Example 47 micron. 0706. A CdS window layer is deposited on the absorber Printing Polymeric Precursor Ink Compositions layer. An aluminum-doped ZnOTCO layer is deposited onto the window layer. 0698. A polymeric precursor ink is prepared by mixing What is claimed is: Cuoss Agoos(SeBu) so Ino, Gao with Xylene (1% polymer 1. A method for making a precursor compound comprising: content, by weight) in an inert atmosphere glovebox. The ink a) providing monomer compounds M'(ER), M (ER), is printed onto a molybdenum-coated stainless steel substrate and M(ER); and using an M3D Aerosol Jet Deposition System (Optomec, b) contacting the monomer compounds; Albuquerque) in a glovebox in an inert atmosphere. wherein M' is In, M' is Ga, M is Ag, each Eis S, Se, or Te, 0699 The substrate is removed and is heated at a tempera and each R is independently selected, for each occurrence, ture of 375°C. in an inert atmosphere. A thin film material is from alkyl, aryl, heteroaryl, alkenyl, amido, silyl, and inor produced which is a photovoltaic absorber layer. The final ganic and organic ligands. film thickness is 500 nm. 2. The method of claim 1, wherein M' and Mare both In, or M' and Mare both Ga. Example 48 3. The method of claim 1, wherein the compound is an AIGS, AIS, or AGS precursor compound. 0700 A polymeric precursor ink is prepared by mixing 4. The method of claim 1, wherein the compound is defi Cuoss Agoos(SeBu) so Ino, Gao with Xylene (1% polymer cient or enriched in the quantity of a Group 11 atom. content, by weight) in an inert atmosphere glovebox. The ink 5. A compound made by a process comprising reacting is printed onto a molybdenum-coated glass Substrate using a monomers M'(ER), M’(ER), and M(ER), wherein M' DIMATIX DMP-2831 materials printer (Fujifilm Dimatix, is In, M' is Ga, M' is Ag, each E is S, Se, or Te, and each R Lebanon, N.H.) in a glovebox in an inert atmosphere. is independently selected, for each occurrence, from alkyl, 0701. The substrate is removed and is heated at a tempera aryl, heteroaryl, alkenyl, amido, silyl, and inorganic and ture of 400°C. in an inert atmosphere A thin film material is organic ligands. produced which is a photovoltaic absorber layer. The final 6. The compound of claim 5, wherein M' and M’ are film thickness is 750 nm. both In, or M' and M’ are both Ga. 7. The compound of claim 5, wherein each E is sulfur or Example 49 Selenium. 8. The compound of claim 5, wherein the compound is an Spray Pyrolysis Deposition of Polymeric Precursor AIGS, AIS, or AGS precursor compound. Ink Compositions 9. The compound of claim 5, wherein the compound has the empirical formula Ag,(M'M',), (S,Se)R), 0702. A polymeric precursor ink composition is prepared wherein M' and M’ are different atoms of Group 13, y is in a glovebox in an inert atmosphere by dissolving the poly from 0 to 1, Z is from 0 to 1, u is from 0.5 to 1.5, V is from 0.5 meric precursor of Example 5 in cyclohexanone to a concen to 1.5, w is from 2 to 6, and R represents R groups, of which tration of 5% (w/w), and adding 0.1% (w/w) sodium relative there are win number, which are independently selected from to copper as NaIn(Se'Bu). The ink is sprayed onto an alumi alkyl, aryl, heteroaryl, alkenyl, amido, silyl, and inorganic num Substrate using a spray pyrolysis unit in a glovebox in an and organic ligands. inert atmosphere, the spray pyrolysis unit having an ultra 10. The compound of claim 9, whereiny is from 0 to 1, Z is Sonic nebulizer, precision flow meters for inert gas carrier, from 0.5 to 1, u is from 0.5 to 1.5, v is from 0.5 to 1.5, w is and a tubular quartz reactor in a furnace. from 2 to 6. US 2011/0034667 A1 Feb. 10, 2011 37
11. The compound of claim 9, whereiny is from 0 to 1, Z is from 0.7 to 1, u is from 0.5 to 1.5, v is from 0.5 to 1.5, w is from 2 to 6. 12. The compound of claim 9, whereiny is from 0 to 1, Z is from 0.9 to 1, u is from 0.5 to 1.5, v is from 0.5 to 1.5, w is from 2 to 6. 13. The compound of claim 5, wherein the compound is deficient or enriched in the quantity of a Group 11 atom. 14. The compound of claim 5, wherein the compound is linear, branched, cyclic, an alternating copolymer, a block copolymer, a random copolymer, or a mixture of any of the foregoing. 15. The compound of claim 5, wherein each R is indepen dently selected, for each occurrence, from (C1-8)alkyl. 16. The compound of claim 5, wherein each R is indepen dently selected, for each occurrence, from (C1-4)alkyl. 17. The compound of claim 5, wherein the compound is an oil at a temperature below about 100° C. 18. The compound of claim 5, further comprising three or more repeating units {M (ER)(ER)}, or three or more repeat ing units M'(ER)(ER). 19. The compound of claim 5, wherein the compound has any one of the formulas: (RE)-BB(AB), (RE)-B(AB),B, (RE)-B(AB), B(AB) (RE)-(BA), BB, (RE)-B(BA),B, (RE)-(BA), B(BA), B, *(AB) '(BA), (RE)-(BB) (AABB), (RE)-(BB)(AABB),(AB), (RE)-(B)(AABB), (B)(AB) (RE)-B(AB), (RE)-(BA),B,
fE ER
MSCME ER
R is M1TYMBITYM1 YMB2
p MyMEITYM42"YME2. is N1 NE1 N1 N. R R R R p
0 00 000 ABAB2AB3 oooooo
(RE)-BB(AB),(AB), (RE)-BB(AB'),(AB),(AB'), (RE)-BB(AB'),(AB),(AB), (RE)-BB(A'B),(AB), (RE)-BB(AB),(AB),(AB), and a mixture of any of the foregoing, wherein A is the repeat unit {M'(ER)(ER), B is the repeat unit {M'(ER)(ER)}, p is one or more, n is one or more, and m is one or more. 20. The compound of claim 5, wherein the compound has any one of the repeat unit formulas: {Ag(Se'Bu). In}, {Ago. 6(Se'Bu). In}, {Ago (Se'Bu). In}, {Ags.(Se'Bu), In, {Ag(Se'Bu)(Se'Bu)In}, {Ag(Se'Bu),Ga}, {Agos(Se'Bu). sIno Gaos, Ag(Se'Bu), Ino, Gao,}, {Ag(Se'Bu), Ino.