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Home , Cadmium phosphide, Gallium antimonide, Germanium telluride, Indium antimonide, Indium gallium arsenide, Indium gallium phosphide

USO09517936 B2

(12) United States Patent (10) Patent No.: US 9,517,936 B2 Jeong et al. (45) Date of Patent: Dec. 13, 2016

(54) STABILIZED BY HALOGEN (2013.01); COIB 21/06 (2013.01); COIB SALT AND METHOD FOR 21/0632 (2013.01); COIB 21/072 (2013.01); MANUFACTURING THE SAME C07C 51/418 (2013.01); C07C 57/12 (2013.01); B82Y 30/00 (2013.01); B82Y 40/00 (71) Applicant: KOREA INSTITUTE OF (2013.01); COIP 2004/64 (2013.01); Y10S MACHINERY & MATERIALS, 977/774 (2013.01); Y10S 977/896 (2013.01) Daejeon (KR) (58) Field of Classification Search CPC ...... C01B 19/002: C07C 51/418 (72) Inventors: Sohee Jeong, Daejeon (KR); Ju Young USPC ...... 55.6/105 Woo, Gyeonggi-do (KR); Doh Chang See application file for complete search history. Lee, Daejeon (KR); Won Seok Chang, Daejeon (KR); Duck Jong Kim, Daejeon (KR) (56) References Cited KOREA INSTITUTE OF (73) Assignee: PUBLICATIONS MACHINERY & MATERIALS, Daejeon (KR) Traub et al., J. Am. Chem. Soc. 2008, 130,955-964.* Peng et al., J. Am. Chem. Soc. 1997, 119, 7019-7029.* (*) Notice: Subject to any disclaimer, the term of this Bae et al., J. Am. Chem. Soc. 2012, 134, 20160-20168.* patent is extended or adjusted under 35 Wan Ki Bae et al., “Highly Effective Surface Passivation of PbSe U.S.C. 154(b) by 0 days. Quantum Dots through Reaction with Molecular Chlorine,” J. Am. Chem.Soc., 2012, 134, pp. 20160-20168. (21) Appl. No.: 14/677.999 Aaron T. Fafarman et al., “Air-Stable, Nanostructured Electronic and Plasmonic Materials from Solution-Processable, Silver Filed: Apr. 3, 2015 Nanocrystal Building Blocks.” American Chemical Society, 2014. (22) vol. 8, No. 3, pp. 2746-2754. www.acsnano.org. Prior Publication Data (65) * cited by examiner US 2015/0291422 A1 Oct. 15, 2015 Primary Examiner — Porfirio Nazario Gonzalez (30) Foreign Application Priority Data Assistant Examiner — Kofi Adzamli Apr. 11, 2014 (KR) ...... 10-2014-0043.638 (74) Attorney, Agent, or Firm — Hauptman Ham, LLP (51) Int. C. (57) ABSTRACT C07F 7/00 (2006.01) COIB 9/00 (2006.01) A quantum dot stabilized by a halogen salt includes a C07C 57/12 (2006.01) compound of Group 13 and Group 15, a compound of Group CD7C5L/4I (2006.01) 12 and Group 16 or a compound of Group 14 and Group 16. COIB 2/06 (2006.01) The quantum dot has a crystalline structure and at least a COB 21/072 (2006.01) portion of a surface of the quantum dot is combined with a B82Y 4O/OO (2011.01) halogen salt. Thus, the quantum dot has a high Stability in an B82Y 3O/OO (2011.01) a1. (52) U.S. C. CPC ...... COIB 19/002 (2013.01); COIB 19/007 6 Claims, 7 Drawing Sheets U.S. Patent Dec. 13, 2016 Sheet 1 of 7 US 9,517,936 B2

- X /10xygen X X-Pb Se202,sey SeO2

X X X U.S. Patent Dec. 13, 2016 Sheet 2 of 7 US 9,517,936 B2

F. G. 2

REACTING FIRST PRECURSOR WITH ORGANIC ACD S10

REACTING SECOND PRECURSOR WITH REACT ON PRODUCT OF THE FIRST PRECURSOR AND THE ORGANIC ACID

PROVIDING HALOGEN COMPOUND STABILIZE QUANTUM DOT S30 U.S. Patent Dec. 13, 2016 Sheet 3 of 7 US 9,517,936 B2

U.S. Patent Dec. 13, 2016 Sheet 4 of 7 US 9,517,936 B2

FIG 4A

Pb 4f, AS prepared NH4C treated

155 150 145 140 135 130 Binding Energy (eV)

FG. 4B

Pb 4f, AS prepared PriStine

155 150 145 140 135 130 Binding Energy (eV) U.S. Patent Dec. 13, 2016 Sheet 5 of 7 US 9,517,936 B2

FG 5A

Se 3d NH4C treated

AS prepared

70 65 60 55 50 45 Binding Energy (eV)

FIG 5B

Se 3d PriStine

AS prepared

70 65 60 55 50 45 Binding Energy (eV) U.S. Patent Dec. 13, 2016 Sheet 6 of 7 US 9,517,936 B2

F.G. 6A

-100 -- Pristine -150- -O-NH4F -A-NH4C - V - NH4Br

O 7 14. Time (day)

F.G. 6B

5 O

-100

-150 -- Pristine -200

-250- 7 14 21 Time(day) U.S. Patent Dec. 13, 2016 Sheet 7 Of 7 US 9,517,936 B2

FG 60

-- Pristine -O-NH4Br/MeOH -A- TBABr/MeOH - V - CTAB/MeOH -(- TBABr/MeCN

O 2 4 6 8 10 Time(day) US 9,517,936 B2 1. 2 QUANTUM DOT STABILIZED BY HALOGEN Sulfide (GeS), (GeSe), ger SALT AND METHOD FOR manium (GeTe), selenium sulfide (SnSeS), tin MANUFACTURING THE SAME selenium telluride (SnSeTe), tin sulfide telluride (SnSTe), selenium sulfide (PbSeS), lead selenium telluride (Pb CROSS-REFERENCE TO RELATED SeTe), lead sulfide telluride (PbSTe), tin lead sulfide (Sn APPLICATIONS PbS), tin (SnPbSe), tin (SnPbTe), tin oxide sulfide (SnOS), tin oxide selenide (SnOSe), tin This application claims priority under 35 U.S.C. S 119 to oxide telluride (SnOTe), germanium oxide sulfide (GeOS), Korean Patent Application No. 10-2014-0043638, filed on germanium oxide selenide (GeOSe), germanium oxide tel Apr. 11, 2014, and all the benefits accruing therefrom, the 10 luride (GeOTe), tin lead sulfide selenide (SnPbSSe), tin lead content of which is herein incorporated by reference in its selenium telluride (SnPbSeTe) and tin lead sulfide telluride entirety. (SnRbSTe). In an exemplary embodiment, the compound of Group 13 BACKGROUND and Group 15 includes at least one selected from the group 15 consisting of (GaP), 1. Field (GaAs), (GaSb), (GaN), Exemplary embodiments relate to a quantum dot. More aluminum phosphide (AlP), aluminum arsenide (AlAS), particularly, exemplary embodiments relate to a quantum aluminum antimonide (AISb), aluminum nitride (AIN), dot stabilized by a halogen salt and a method for manufac phosphide (InP), (InAs), indium turing the quantum dot. antimonide (InSb), (InN), 2. Description of the Related Art arsenide (GaPAs), gallium phosphide antimonide (GaPSb), A quantum dot is a nano-particle having semiconductive gallium phosphide nitride (GaPN), gallium arsenide nitride properties and having a size less than tens of nanometers. (GaAsN), gallium antimonide nitride (GaSbN), aluminum The quantum dot has properties different from a bulk particle phosphide arsenide (AlPAS), aluminum phosphide anti due to quantum confinement effect. For example, the quan 25 monide (AlPSb), aluminum phosphide nitride (AlPN), alu tum dot can change a wavelength of a light, which the minum arsenide nitride (AlASN), aluminum antimonide quantum dot absorbs, according to a size thereof. Further nitride (AISbN), arsenide (InPAs), indium more, the quantum dot has novel optical, electrical and phosphide antimonide (InPSb), indium phosphide nitride physical properties that the bulk particle does not have. (InPN), indium arsenide nitride (InAsN), Thus, researches are being conducted for manufacturing a 30 nitride (InSbN), aluminum gallium phosphide (AlGaP), alu photoelectric conversion device Such as a Solar cell, a minum gallium arsenide (AlGaAs), aluminum gallium anti light-emitting diode or the like. monide (AlGaSb), aluminum gallium nitride (AlGaN), alu Recently, a colloidal chemosynthesis has been developed minum arsenide nitride (AlASN), aluminum antimonide for controlling a size and a shape of the quantum dot. nitride (AISbN), (InGaP), indium However, the quantum dot manufactured by the colloidal 35 gallium arsenide (InGaAs), indium gallium antimonide (In chemosynthesis has a low stability in an air. A core-shell GaSb), (InGaN), indium arsenide quantum dot having a thick skin may be relatively stable in nitride (InAsN), indium antimonide nitride (InSbN), alumi an air. However, the core-shell quantum dot is hardly num indium phosphide (AlInP), aluminum indium arsenide applicable for the photoelectric conversion device, and (AlInAs), aluminum indium antimonide (AlInSb), alumi manufacturing processes for the core-shell quantum dot are 40 num indium nitride (AlInN), aluminum arsenide nitride complicated. (AlAsN), aluminum antimonide nitride (AISbN), aluminum phosphide nitride (AlPN), gallium aluminum phosphide SUMMARY arsenide (GaAlPAS), gallium aluminum phosphide anti monide (GaAlPSb), gallium indium phosphide arsenide Exemplary embodiments provide a quantum dot stable in 45 (GalinPAS), gallium indium aluminum arsenide (GanAlAS), an air. gallium aluminum phosphide nitride (GaAlPN), gallium Exemplary embodiments also provide a method for manu aluminum arsenide nitride (GaA1ASN), gallium aluminum facturing the quantum dot. antimonide nitride (GaA1SbN), gallium indium phosphide According to an exemplary embodiment, a quantum dot nitride (GainPN), gallium indium arsenide nitride (Gain stabilized by a halogen salt includes a compound of Group 50 ASN), gallium indium aluminum nitride (GanAIN), gallium 13 and Group 15, a compound of Group 12 and Group 16 or antimonide phosphide nitride (GaSbPN), gallium arsenide a compound of Group 14 and Group 16. The quantum dot phosphide nitride (GaAsPN), gallium arsenide antimonide has a crystalline structure, and at least a portion of a surface nitride (GaAsSbN), gallium indium phosphide antimonide of the quantum dot is combined with a halogen salt. (GalnPSb), gallium indium phosphide nitride (GalnPN), In an exemplary embodiment, a diameter of the quantum 55 gallium indium antimonide nitride (GainSbN), gallium dot is 1 nm to 20 nm. phosphide antimonide nitride (GaPSbN), indium aluminum In an exemplary embodiment, the quantum dot has a first phosphide arsenide (InAlPAS), indium aluminum phosphide Surface combined with the halogen salt and a second Surface nitride (InAlPN), indium phosphide arsenide nitride (In combined with an organic ligand. PASN), indium aluminum antimonide nitride (InAlSbN), In an exemplary embodiment, a (100) surface is combined 60 indium phosphide antimonide nitride (InPSbN), indium with the halogen salt, and a (111) surface is combined with arsenide antimonide nitride (InAsSb.N) and indium alumi the organic ligand. num phosphide antimonide (InAlPSb). In an exemplary embodiment, the compound of Group 14 In an exemplary embodiment, the compound of Group 12 and Group 16 includes at least one selected from the group and Group 16 includes at least one selected from the group consisting of tin oxide (SnO), tin sulfide (SnS), 65 consisting of Sulfide (CdS), (SnSe), tintelluride (SnTe), lead sulfide (PbS), lead selenide (CdSe), (CdTe), (ZnS), Zinc (PbSe), lead telluride (PbTe), germanium oxide (GeO), selenide (ZnSe), (ZnTe), sulfide US 9,517,936 B2 3 4 (HgS), (HgSe), (HgTe). BRIEF DESCRIPTION OF THE DRAWINGS (ZnO), (CdC), mercury oxide (HgC), cadmium selenium sulfide (CdSeS), cadmium sele The above and other features and advantages will become nium telluride (CdSeTe), telluride (CdSTe), more apparent by describing exemplary embodiments cadmium Zinc sulfide (CdZnS), cadmium thereof with reference to the accompanying drawings, in (CdZnSe), cadmium sulfide selenide (CdSSe), cadmium which: Zinc telluride (CdZnTe), cadmium (CdHgS), FIG. 1 is a schematic view illustrating a structure of a cadmium mercury selenide (CdFIgSe), cadmium mercury quantum dot according to an exemplary embodiment of the telluride (CdHgTe), zinc selenium sulfide (ZnSeS), Zinc present invention. selenium telluride (ZnSeTe), zinc sulfide telluride (ZnSTe). 10 FIG. 2 is a flow chart illustrating a method for manufac mercury selenium sulfide (HgSeS), mercury selenium tellu turing a quantum dot according to an exemplary embodi ride (HgSeTe), mercury sulfide telluride (HgSTe), mercury ment of the present invention. Zinc sulfide (HgZnS), mercury Zinc selenide (HgZnSe), FIG. 3A is a TEM picture of Example 1. cadmium Zinc oxide (CdZnO), cadmium mercury oxide 15 FIG. 3B is a TEM picture of Comparative Example 1. (CdHgO), zinc mercury oxide (ZnHgO), Zinc selenium FIG. 4A is a graph showing XPS analysis of lead in the oxide (ZnSeO), Zinc oxide (ZnTeC), Zinc sulfide quantum dot of Example 1. oxide (ZnSO), cadmium selenium oxide (CdSeO), cadmium FIG. 4B is a graph showing XPS analysis of lead in the tellurium oxide (CdTeC), cadmium sulfide oxide (CdSO), quantum dot of Comparative Example 1. mercury selenium oxide (HgSeO), mercury tellurium oxide FIG. 5A is a graph showing XPS analysis of selenium in (HgTeC), mercury sulfide oxide (HgSO), cadmium zinc the quantum dot of Example 1. selenium sulfide (CdZnSeS), cadmium zinc selenium tellu FIG. 5B is a graph showing XPS analysis of selenium in ride (CdZnSeTe), cadmium zinc sulfide telluride (CdZn the quantum dot of Comparative Example 1. STe), cadmium mercury selenium sulfide (CdHgSeS), cad FIG. 6A is a graph showing absorption wavelength varia mium mercury selenium telluride (CdHgSeTe), cadmium 25 tion of the quantum dots of Examples 1 to 4 and Compara mercury sulfide telluride (CdHgSTe), mercury Zinc selenium tive Example 1 with respect to time. sulfide (HgZnSeS), mercury Zinc selenium telluride (Hg FIG. 6B is a graph showing absorption wavelength varia ZnSeTe), mercury Zinc sulfide telluride (HgZnSTe), cad tion of the quantum dots of Examples 5 to 7 and Compara mium zinc selenium oxide (CdZnSeO), cadmium zinc tel tive Example 1 with respect to time. lurium oxide (CdZnTeC), cadmium zinc sulfide oxide 30 FIG. 6C is a graph showing absorption wavelength varia (CdZnSO), cadmium mercury selenium oxide (CdhgSeO), tion of the quantum dots of Examples 2, 8 and 10 and cadmium mercury tellurium oxide (CdHgTeC), cadmium Comparative Example 1 with respect to time. mercury sulfide oxide (CdHgSO), Zinc mercury selenium DETAILED DESCRIPTION oxide (ZnHgSeO), Zinc mercury tellurium oxide (ZnHgTeO) 35 and zinc mercury sulfide oxide (ZnHgSO). Example embodiments are described more fully herein According to an exemplary embodiment, a method for after with reference to the accompanying drawings. The manufacturing a quantum dot includes forming a quantum inventive concept may, however, be embodied in many dot particle including a compound of Group 13 and Group different forms and should not be construed as limited to the 15, a compound of Group 12 and Group 16 or a compound 40 example embodiments set forth herein. In the drawings, the of Group 14 and Group 16, and providing a halogen com sizes and relative sizes of layers and regions may be exag pound to the quantum dot particle to stabilize the quantum gerated for clarity. It will be understood that, although the dot particle. terms first, second, third etc. may be used herein to describe In an exemplary embodiment, forming the quantum dot various elements, components, regions, layers, patterns and/ particle includes reacting a first precursor with an organic 45 or sections, these elements, components, regions, layers, acid, and reacting a second precursor with a reaction product patterns and/or sections should not be limited by these terms. of the first precursor and the organic acid. These terms are only used to distinguish one element, In an exemplary embodiment, the first precursor includes component, region, layer pattern or section from another an element of Group 12, Group 13 or group 14. region, layer, pattern or section. Thus, a first element, In an exemplary embodiment, the organic acid includes at 50 component, region, layer or section discussed below could least one selected from the group consisting of formic acid, be termed a second element, component, region, layer or acetic acid, propionic acid, Valeric acid, butyric acid, section without departing from the teachings of example hexanoic acid, caprylic acid, capric acid and lauric acid. embodiments. In an exemplary embodiment, the second precursor Example embodiments are described herein with refer includes an element of Group 15 or group 16. 55 ence to cross sectional illustrations that are schematic illus In an exemplary embodiment, the halogen compound trations of illustratively idealized example embodiments includes at least one selected from the group consisting of a (and intermediate structures) of the inventive concept. As chloride, a bromide and an iodide. Such, variations from the shapes of the illustrations as a In an exemplary embodiment, the halogen compound result, for example, of manufacturing techniques and/or includes at least one selected from the group consisting of 60 tolerances, are to be expected. Thus, example embodiments tetrabutylammonium bromide, cetyltrimethylammonium should not be construed as limited to the particular shapes of bromide, ammonium chloride, ammonium bromide, ammo regions illustrated herein but are to include deviations in nium iodide, potassium chloride, potassium bromide, potas shapes that result, for example, from manufacturing. The sium iodide, , Sodium bromide, sodium regions illustrated in the figures are schematic in nature and iodide, indium chloride, indium bromide and indium iodide. 65 their shapes are not intended to illustrate the actual shape of According to the exemplary embodiments, a quantum dot a region of a device and are not intended to limit the scope having increased stability in an air may be obtained. of the inventive concept. US 9,517,936 B2 5 6 The terminology used herein is for the purpose of describ In the embodiment, the quantum dot includes PbSE, and ing particular example embodiments only and is not the (111) Surface is combined with the organic ligand, and intended to be limiting of the invention. As used herein, the the (100) surface is combined with the halogen salt. How singular forms “a,” “an and “the are intended to include ever, exemplary embodiments of the present invention are the plural forms as well, unless the context clearly indicates not limited thereto, and may change according to elements otherwise. It will be further understood that the terms and crystalline structures. Exemplary embodiments of the “comprises and/or "comprising,” when used in this speci present invention may include various quantum dot includ fication, specify the presence of Stated features, integers, ing a first Surface combined with an organic ligand, and a steps, operations, elements, and/or components, but do not second Surface, which is not combined with the organic preclude the presence or addition of one or more other 10 ligand, combined with a halogen salt. features, integers, steps, operations, elements, components, The quantum dot may include various combinations of and/or groups thereof. materials besides PbSe. For example, the quantum dot may Unless otherwise defined, all terms (including technical include a compound of Group 14 and Group 16 (in the and Scientific terms) used herein have the same meaning as periodic table). For example, the quantum dot may include commonly understood by one of ordinary skill in the art to 15 tin oxide (SnO), tin sulfide (SnS), tin selenide (SnSe), tin which this inventive concept belongs. It will be further telluride (SnTe), lead sulfide (PbS), lead selenide (PbSe), understood that terms, such as those defined in commonly lead telluride (PbTe), germanium oxide (GeO), germanium used dictionaries, should be interpreted as having a meaning Sulfide (GeS), germanium selenide (GeSe), germanium tel that is consistent with their meaning in the context of the luride (GeTe), tin selenium sulfide (SnSeS), tin selenium relevant art and will not be interpreted in an idealized or telluride (SnSeTe), tin sulfide telluride (SnSTe), lead sele overly formal sense unless expressly so defined herein. nium sulfide (PbSeS), lead selenium telluride (PbSeTe), lead Quantum Dot Stabilized by a Halogen Salt sulfide telluride (PbSTe), tin lead sulfide (SnPbS), tin lead A quantum dot according to an exemplary embodiment of selenide (SnPbSe), tin lead telluride (SnPbTe), tin oxide the present invention has a crystalline structure and includes sulfide (SnOS), tin oxide selenide (SnOSe), tin oxide tellu at least two elements. At least a portion of a surface of the 25 ride (SnOTe), germanium oxide sulfide (GeOS), germanium quantum dot is covered by a halogen salt. The quantum dot oxide selenide (GeOSe), germanium oxide telluride may include a bond of a metal and a semi-metal or a bond (GeOTe), tin lead sulfide selenide (SnPbSSe), tin lead sele of a metal and a non-metal. The halogen salt may include an nium telluride (SnPbSeTe), tin lead sulfide telluride (SnPb ionic bond of a metal atom that belongs to the quantum dot STe) or the like. Theses may be used each alone or in a and a halogen atom. 30 combination thereof. FIG. 1 is a schematic view illustrating a structure of a In another embodiment, the quantum dot may include a quantum dot according to an exemplary embodiment of the compound of Group 12 and Group 16. For example, the present invention. Referring to FIG. 1, a quantum dot may quantum dot may include cadmium sulfide (CdS), cadmium include lead selenide (PbSe). For example, PbSe quantum selenide (CdSe), cadmium telluride (CdTe), Zinc sulfide dot may have a rock-salt cubic crystalline structure. The 35 (ZnS), Zinc selenide (ZnSe), Zinc telluride (ZnTe), mercury quantum dot has a (100) Surface and a (111) Surface. Lead sulfide (HgS), mercury selenide (HgSe), mercury telluride atoms are arranged at the (111) Surface, and are combined (HgTe). Zinc oxide (ZnO), cadmium oxide (CdO), mercury with a ligand to be stabilized. Since lead atoms and selenium oxide (HgC), cadmium selenium sulfide (CdSeS), cadmium atoms are arranged at the (100) surface, the (100) surface has selenium telluride (CdSeTe), cadmium sulfide telluride (Cd relatively low stability in an air. Thus, if the (100) surface is 40 STe), cadmium zinc sulfide (CdZnS), cadmium zinc selenide not protected, the selenium atoms of the (100) surface may (CdZnSe), cadmium sulfide selenide (CdSSe), cadmium be oxidized or separated thereby causing deterioration or Zinc telluride (CdZnTe), cadmium mercury sulfide (CdHgS), damage of a quantum dot. However, the quantum dot cadmium mercury selenide (CdFIgSe), cadmium mercury according to an exemplary embodiment of the present telluride (CdHgTe), zinc selenium sulfide (ZnSeS), Zinc invention includes a halogen salt combined with the (100) 45 selenium telluride (ZnSeTe), zinc sulfide telluride (ZnSTe), Surface. Thus, the quantum dot may have increased Stability mercury selenium sulfide (HgSeS), mercury selenium tellu in an air. ride (HgSeTe), mercury sulfide telluride (HgSTe), mercury The halogen salt may be halogenated lead (PbX) includ Zinc sulfide (HgZnS), mercury Zinc selenide (HgZnSe), ing a halogen atom combined with a lead atom. The halogen cadmium Zinc oxide (CdZnO), cadmium mercury oxide salt may form a mono-layered structure or a multiple 50 (CdHgO), zinc mercury oxide (ZnHgO), zinc selenium layered structure on the (100) surface. The quantum dot may oxide (ZnSeO), Zinc tellurium oxide (ZnTeC), Zinc sulfide have a diameter of about 1 nm to about 100 nm, preferably oxide (ZnSO), cadmium selenium oxide (CdSeO), cadmium about 1 nm to about 20 nm. tellurium oxide (CdTeC), cadmium sulfide oxide (CdSO), Examples of the halogen may include fluorine, chlorine, mercury selenium oxide (HgSeO), mercury tellurium oxide bromine, iodine or the like. For example, the halogen salt 55 (HgTeO), mercury sulfide oxide (HgSO), cadmium zinc may include lead chloride, lead bromide, lead iodide, lead selenium sulfide (CdZnSeS), cadmium zinc selenium tellu fluoride or combination thereof. Since lead fluoride (PbF2) ride (CdZnSeTe), cadmium zinc sulfide telluride (CdZn has a relatively large bond energy, applicability of a quantum STe), cadmium mercury selenium sulfide (CdHgSeS), cad dot including lead fluoride may be reduced. Thus, lead mium mercury selenium telluride (CdHgSeTe), cadmium chloride, lead bromide, lead iodide may be preferred to lead 60 mercury sulfide telluride (CdHgSTe), mercury Zinc selenium fluoride. sulfide (HgZnSeS), mercury Zinc selenium telluride (Hg Combination of the ligand and a lead atom may form a ZnSeTe), mercury Zinc sulfide telluride (HgZnSTe), cad bond of Pb-O on the (111) surface. The ligand may be an mium zinc selenium oxide (CdZnSeO), cadmium zinc tel organic ligand or an inorganic ligand. Preferably, the ligand lurium oxide (CdZnTeC), cadmium zinc sulfide oxide may be an organic ligand provided by an organic acid Such 65 (CdZnSO), cadmium mercury selenium oxide (CdhgSeO), as oleic acid. The organic ligand may include carbon atoms cadmium mercury tellurium oxide (CdHgTeC), cadmium equal to or less than 20. mercury sulfide oxide (CdHgSO), Zinc mercury selenium US 9,517,936 B2 7 8 oxide (ZnHgSeO), Zinc mercury tellurium oxide (ZnHg For example, the first precursor including an element of TeC), Zinc mercury sulfide oxide (ZnHgSO) or the like. Group 12 may include cadmium acetate dihydrate, dimethyl Theses may be used each alone or in a combination thereof. cadmium, diethyl cadmium, cadmium acetate, cadmium In another embodiment, the quantum dot may include a acetylacetonate, cadmium acetylacetonate hydrate, cad compound of Group 13 and Group 15. For example, the mium iodide, cadmium bromide, cadmium chloride, cad quantum dot may include gallium phosphide (GalP), gallium mium chloride hydrate, cadmium fluoride, cadmium carbon arsenide (GaAs), gallium antimonide (GaSb), gallium ate, cadmium nitrate, cadmium nitrate tetrahydrate, nitride (GaN), aluminum phosphide (AlP), aluminum cadmium oxide, cadmium perchlorate, cadmium perchlorate arsenide (AIAS), aluminum antimonide (AlSb), aluminum hexahydrate, , cadmium sulfate, cad nitride (AIN), indium phosphide (InP), indium arsenide 10 mium naphthenate, cadmium Stearate, dimethyl Zinc, diethyl (InAs), indium antimonide (InSb), indium nitride (InN), Zinc, Zinc acetate, Zinc acetate dihydrate, Zinc acetylaceto gallium phosphide arsenide (GalPAS), gallium phosphide nate, Zinc acetylacetonate hydrate, Zinc iodide, Zinc bro antimonide (GaPSb), gallium phosphide nitride (GaPN), mide, , Zinc fluoride, zinc fluoride tetrahydrate, gallium arsenide nitride (GaAsN), gallium antimonide Zinc carbonate, Zinc cyanide, Zinc nitrate, Zinc nitrate hexa nitride (GaSbN), aluminum phosphide arsenide (AlPAs), 15 hydrate, Zinc oxide, Zinc , Zinc perchlorate, Zinc aluminum phosphide antimonide (AlPSb), aluminum phos perchlorate hexahydrate, Zinc sulfate, diphenyl Zinc, Zinc phide nitride (AlPN), aluminum arsenide nitride (AlAsN), naphthenate, Zinc Stearate, mercury acetate, mercury iodide, aluminum antimonide nitride (AISbN), indium phosphide mercury bromide, mercury chloride, mercury fluoride, mer arsenide (InPAs), indium phosphide antimonide (InPSb), cury cyanide, mercury nitrate, mercury nitrate monohydrate, indium phosphide nitride (InPN), indium arsenide nitride mercury oxide, mercury perchlorate, mercury perchlorate (InAsN), indium antimonide nitride (InSbN), aluminum tetrahydrate, mercury perchlorate trihydrate, mercury Sul gallium phosphide (AlGaP), aluminum gallium arsenide fate, dimethyl mercury, diethyl mercury, diphenyl mercury, (AlGaAs), aluminum gallium antimonide (AlGaSb), alumi mercury Sulfate, mercury trifluoromethane Sulfonate, meth num gallium nitride (A1GaN), aluminum arsenide nitride ylmercury chloride, iodide, phenylmercury (AlAsN), aluminum antimonide nitride (AlSbN), indium 25 acetate, phenylmercury chloride or the like. Theses may be gallium phosphide (InGaP), (In used each alone or in a combination thereof. GaAs), indium gallium antimonide (InGaSb), indium gal For example, the first precursor including an element of lium nitride (InGaN), indium arsenide nitride (InAsN), Group 13 may include aluminum acetate, aluminum iodide, indium antimonide nitride (InSbN), aluminum indium phos aluminum bromide, aluminum chloride, aluminum chloride phide (AlInP), aluminum indium arsenide (AlInAs), alumi 30 hexahydrate, aluminum fluoride, aluminum nitrate, alumi num indium antimonide (AlInSb), aluminum indium nitride num oxide, aluminum perchlorate, aluminum carbide, alu (AlInN), aluminum arsenide nitride (AlAsN), aluminum minum stearate, aluminum sulfate, di-i-butylaluminum chlo antimonide nitride (AISbN), aluminum phosphide nitride ride, diethylaluminum chloride, tri-i-butylaluminum, (AlPN), gallium aluminum phosphide arsenide (GaAlPAs), triethylaluminum, triethyl(tri-sec-butoxy)dialuminum, trim gallium aluminum phosphide antimonide (GaAlPSb), gal 35 ethylaluminum, gallium acetylacetonate, gallium chloride, lium indium phosphide arsenide (GalnPAS), gallium indium gallium fluoride, gallium fluoride trihydrate, gallium oxide, aluminum arsenide (GanAIAS), gallium aluminum phos , gallium nitrate hydrate, gallium sulfate, phide nitride (GaAlPN), gallium aluminum arsenide nitride gallium iodide, triethyl gallium, trimethyl gallium, indium (GaA1ASN), gallium aluminum antimonide nitride chloride, indium chloride tetrahydrate, indium oxide, indium (GaA1SbN), gallium indium phosphide nitride (GalnPN), 40 nitrate, indium nitrate hydrate, indium sulfate, indium Sul gallium indium arsenide nitride (GanASN), gallium indium fate hydrate, indium acetate, indium acetylacetonate, indium aluminum nitride (GanAIN), gallium antimonide phosphide bromide, indium fluoride, indium fluoride trihydrate, trim nitride (GaSbPN), gallium arsenide phosphide nitride ethyl indium or the like. Theses may be used each alone or (GaAsPN), gallium arsenide antimonide nitride (GaAsSbN), in a combination thereof. gallium indium phosphide antimonide (GalnPSb), gallium 45 For example, the first precursor including an element of indium phosphide nitride (GainPN), gallium indium anti Group 14 may include lead acetate, lead acetate trihydrate, monide nitride (GainSbN), gallium phosphide antimonide lead bromide, lead chloride, lead fluoride, lead oxide, lead nitride (GaPSbN), indium aluminum phosphide arsenide perchlorate, lead nitrate, lead Sulfate, lead carbonate, lead (InAlPAs), indium aluminum phosphide nitride (InAlPN), acethylacetonate, lead citrate, lead bromide, lead naphthen indium phosphide arsenide nitride (InPASN), indium alumi 50 ate, tin acetate, tin bisacetylacetonate, tin bromide, tin num antimonide nitride (InAlSbN), indium phosphide anti chloride, tin chloride dihydrate, tin chloride pentahydrate, monide nitride (InPSbN), indium arsenide antimonide tin fluoride, tin oxide, tin sulfate, tin iodide, diphenyltin nitride (InAsSbN), indium aluminum phosphide antimonide dichloride, , germanium oxide, ger (InAlPSb) or the like. Theses may be used each alone or in manium ethoxide, germanium bromide, germanium iodide, a combination thereof. 55 tetramethyl germanium, trimethyl germanium chloride, The quantum dot may be stable in an air even without a trimethyl germanium bromide, triethyl germanium chloride thick skin layer. Thus, applicability and electric properties or the like. Theses may be used each alone or in a combi may be improved. nation thereof. Method for Manufacturing a Quantum Dot In an exemplary embodiment, the organic acid may FIG. 2 is a flow chart illustrating a method for manufac 60 include oleic acid. turing a quantum dot according to an exemplary embodi In another exemplary embodiment, the organic acid may ment of the present invention. include a low molecular weight organic acid. For example, Referring to FIG. 2, a first precursor reacts with an the low molecular weight organic acid may include formic organic acid (S10). For example, the first precursor and the acid, acetic acid, propionic acid, Valeric acid, butyric acid, organic acid are dispersed in a solvent. The first precursor 65 hexanoic acid, caprylic acid, capric acid, lauric acid or the may include at least one element selected from Groups 12, like. Theses may be used each alone or in a combination 13 and 14. thereof. US 9,517,936 B2 9 10 In another exemplary embodiment, the organic acid may Preferably, the reaction of the second precursor and the include a mixture of the low molecular weight organic acid reaction product of the first precursor and the organic acid and oleic acid. A mole ratio of the low molecular weight may be rapidly terminated by quenching. For example, the organic acid and oleic acid may be about 10:1 to about 1:1, reaction may be terminated by hexane, ice water or the like. preferably about 9:1 to about 7:3. When the organic acid Thereafter, a halogen compound is provided for stabiliz includes only the low molecular weight organic acid, or ing the quantum dot (S30). The reaction of the halogen when the ratio of the low molecular weight organic acid to compound and the quantum dot may be performed at a oleic acid is excessively large, a size of the quantum dot may temperature higher than a room temperature, for example, at increase to deteriorate photoelectric properties. When the about 40° C. to about 80° C. Thus, the reaction solution ratio of the low molecular weight organic acid to oleic acid 10 cooled by quenching may be heated again to have an is excessively small, stability of the quantum dot in an air appropriate temperature. The halogen compound is not limited to a particular may be decreased. compound, and may include any compound that may gen Furthermore, when the organic acid includes a mixture of erate a halogen . Preferably, the halogen compound may the low molecular weight organic acid and oleic acid, a size 15 include chlorine, bromine or iodine in view of bond energy. and a shape of the quantum dot may be easily controlled by For example, the halogen compound may include a haloge adjusting the mole ratio of the low molecular weight organic nated metal, an organic halide or the like. Particularly, the acid and oleic acid. halogen compound may include tetrabutylammonium bro In another exemplary embodiment, the organic acid may mide, cetyltrimethylammonium bromide, ammonium chlo include a mixture of oleic acid and a halogen compound. The ride, ammonium bromide, ammonium iodide, potassium halogen compound may react with the first precursor to form chloride, potassium bromide, potassium iodide, Sodium a halogen ligand. For example, the halogen compound may chloride, Sodium bromide, Sodium iodide, indium chloride, include ammonium chloride, ammonium bromide or the indium bromide, indium iodide, or the like. Theses may be like. used each alone or in a combination thereof. The solvent may be an organic solvent. For example, the 25 The halogen compound may be used with a solvent. For Solvent may include a hydrocarbon, an amine or the like. example, the solvent may include methanol, acetonitril, For example, the hydrocarbon may include hexane, dode ethanol or the like. cane, decane, undecane, tetradecane, hexadecane, 1-hexa Thereafter, unreacted monomers are removed (S40). A decyne, 1-octadecyne, diphenylether or the like. Theses may non-solvent such as alcohol is provided to the reaction be used each alone or in a combination thereof. 30 Solution to cause aggregation. Then, centrifugation is per For example, the amine may include oleylamine, dodecyl formed for precipitation. The precipitate is dispersed in a amine, lauryl amine, octyl amine, trioctyl amine, dioctyl solvent to remove unreacted monomers. As a result, a amine, hexadecyl amine or the like. Theses may be used stabilized quantum dot is obtained. The quantum dot may each alone or in a combination thereof. have a diameter of about 1 nm to about 100 nm, preferably Reaction of the first precursor and the organic acid may be 35 about 1 nm to about 20 nm. processed by heating. For example, the reaction of the first According to the exemplary embodiments of the present precursor and the organic acid may be performed at a invention, a passivation layer is formed on a surface of a temperature of about 80° C. to about 150° C. Preferably, the quantum dot by using a halogen salt. Thus, stability of the reaction may be performed in a vacuum or in an inert quantum dot in an air may be increased. condition including nitrogen gas, argon gas or the like. 40 Hereinafter, examples of the present invention will be Degassing may be further performed for promoting the explained with reference to synthetic examples of a quantum reaction of the first precursor and the organic acid. Degas dot. sing may remove by-products of the reaction thereby mov ing reaction equilibrium of the first precursor and the organic Example 1 acid. Thus, the reaction of the first precursor and the organic 45 acid may be promoted. The degassing may be performed for About 0.46 g of PbO was provided to a mixture solution about 1 hour to about 5 hours. including about 1.4 ml of oleic acid and about 10 ml of Thereafter, a second precursor reacts with a reaction octadecyne. Then the mixture solution was heated at about product of the first precursor and the organic acid to form a 120° C. to prepare a precursor solution. After a temperature quantum dot (S20). The second precursor may include at 50 of the precursor solution was reduced to be about 90° C., a least one element selected from Groups 15 and 16. mixture including about 6 ml of trioctylphosphine selenide For example, the second precursor may include tri-n- (6 M) and octadecyne. A reaction of the solution was octylphosphine selenide, tri-n-butylphosphine selenide, quenched by hexane and ice water to form a quantum dot. diethyldiselenide, dimethylselenide, bis(trimethylsilyl)sele After a temperature of the solution was increased to be about nide, triphenylphosphine selenide (Se-TPP), tri-n-octyl 55 60° C., about 0.19 M of ammonium chloride dispersed in telluride, tri-n-butylphosphine telluride, bis(trim methanol was provided to the solution and stirred. There ethylsilyl) telluride, triphenylphosphine telluride (Te-TPP), after, providing hexane and ethanol in a ratio of 1:2 to the trioctylphosphine sulfide (S-TOP), tributylphosphine sulfide Solution and centrifuging were repeated three times to obtain (S-TEBP), triphenylphosphine sulfide (S-TPP), trioctylamine PbSe quantum dot precipitate. A diameter of the quantum sulfide (S-TOA), bis(trimethylsilyl) sulfide, trimethylsilyl 60 do, which was measured by transmission electron micros sulfide, ammonium sulfide, sodium sulfide or the like. The copy (TEM), was about 3 nm. ses may be used each alone or in a combination thereof. Reaction of the second precursor and the reaction product Example 2 of the first precursor and the organic acid may be processed by heating. For example, the reaction may be performed at 65 A quantum dot was obtained through a Substantially same a temperature of about 80° C. to about 350° C., preferably method as Example 1 except using ammonium bromide at a temperature of about 80° C. to about 150° C. instead of ammonium chloride. US 9,517,936 B2 11 12 Example 3 be noted that a passivation layer of a halogen salt was formed in the quantum dot of Example 1. In FIGS. 4A and A quantum dot was obtained through a substantially same 4B, Pb-O peaks represents a bond of Pb and a ligand at a method as Example 1 except using ammonium iodide (111) surface. instead of ammonium chloride. FIG. 5A is a graph showing XPS analysis of selenium in the quantum dot of Example 1. FIG. 5B is a graph showing Example 4 XPS analysis of selenium in the quantum dot of Compara tive Example 1. The XPS analysis were firstly performed A quantum dot was obtained through a substantially same immediately after synthesis (AS prepared), and second per method as Example 1 except using ammonium fluoride 10 formed after lapse of two weeks in an air (2 weeks). instead of ammonium chloride. Referring to FIGS.5A and 5B, an amount of selenium in the quantum dot of Comparative Example 1 was reduced after Example 5 lapse of two weeks in an air while an amount of selenium in the quantum dot of Example 1 was not substantially 15 changed. Thus, it can be noted that the quantum dot of A quantum dot was obtained through a substantially same Example 1 may have a higher stability in an air than the method as Example 1 except using potassium chloride quantum dot of Comparative Example 1. instead of ammonium chloride. FIG. 6A is a graph showing absorption wavelength varia Example 6 tion of the quantum dots of Examples 1 to 4 and Compara tive Example 1 with respect to time. Referring to FIG. 6A, an absorption wavelength of the quantum dot of Compara A quantum dot was obtained through a substantially same tive Example 1 were changed according to time lapse while method as Example 1 except using sodium chloride instead an absorption wavelength of the quantum dots of Examples of ammonium chloride. 1 to 3 was not Substantially changed. However, an absorp Example 7 25 tion wavelength of the quantum dot of Examples 4 using fluoride was substantially changed. A quantum dot was obtained through a substantially same FIG. 6B is a graph showing absorption wavelength varia method as Example 1 except using indium chloride instead tion of the quantum dots of Examples 5 to 7 and Compara of ammonium chloride. tive Example 1 with respect to time. Referring to FIG. 6B, 30 it can be noted that various halogen salts can be used for Example 8 stabilizing a quantum dot. FIG. 6C is a graph showing absorption wavelength varia A quantum dot was obtained through a substantially same tion of the quantum dots of Examples 2, 8 and 10 and method as Example 1 except using tetrabutylammonium Comparative Example 1 with respect to time. Referring to bromide instead of ammonium chloride. 35 FIG. 6C, it can be noted that various halogen salts and Solvents can be used for stabilizing a quantum dot. Example 9 Exemplary embodiments of the present invention may be used for various electric elements, a , a display A quantum dot was obtained through a substantially same device, a light source or the like. method as Example 1 except using cetyltrimethylammo 40 The foregoing is illustrative and is not to be construed as nium bromide instead of ammonium chloride. limiting thereof. Although a few exemplary embodiments have been described, those skilled in the art will readily Example 10 appreciate that many modifications are possible in the exem plary embodiments without materially departing from the A quantum dot was obtained through a substantially same 45 novel teachings, aspects, and advantages of the invention. method as Example 1 except using tetrabutylammonium Accordingly, all Such modifications are intended to be bromide and acetonitrile instead of ammonium chloride and included within the scope of this disclosure. methanol What is claimed is: 1. A quantum dot stabilized by a halogen salt, the quantum Comparative Example 1 50 dot comprising a compound of Group 13 and Group 15, a compound of Group 12 and Group 16 or a compound of A quantum dot was obtained through a substantially same Group 14 and Group 16, wherein the quantum dot has a method as Example 1 except not providing ammonium crystalline structure and at least a portion of a surface of the chloride. quantum dot is combined with a halogen salt, FIG.3A is a TEM picture of Example 1. FIG. 3B is a TEM 55 wherein the quantum dot has a first surface combined with picture of Comparative Example 1. Referring to FIGS. 3A the halogen salt and a second Surface combined with an and 3B, a size of the stabilized quantum of Example 1 is organic ligand. similar to the quantum dot of Comparative Example 1. Thus, 2. The quantum dot of claim 1, wherein a diameter of the it can be noted that a passivation layer formed by Example quantum dot is 1 nm to 20 nm. 1 for stabilizing is very thin so that the passivation layer 60 3. The quantum dot of claim 1, wherein the first surface hardly increases a size of the quantum dot. combined with the halogen salt is a (100) surface, and the FIG. 4A is a graph showing XPS analysis of lead in the second Surface combined with the organic ligand is a (111) quantum dot of Example 1. FIG. 4B is a graph showing XPS Surface. analysis of lead in the quantum dot of Comparative Example 4. The quantum dot of claim 1, wherein the compound of 1. Referring to FIGS. 4A and 4B, it can be noted that the 65 Group 14 and Group 16 comprises at least one selected from quantum dot includes an ionic bond of Pb C1, which is not the group consisting of tin oxide (SnO), tin sulfide (SnS), tin shown in FIG. 4B for Comparative Example 1. Thus, it can selenide (SnSe), (SnTe), lead sulfide (PbS), lead US 9,517,936 B2 13 14 selenide (PbSe), lead telluride (PbTe), germanium oxide nitride (GaSbPN), gallium arsenide phosphide nitride (GeO). germanium sulfide (GeS), germanium selenide (GaAsPN), gallium arsenide antimonide nitride (GaAsSbN), (GeSe), (GeTe), tin selenium sulfide gallium indium phosphide antimonide (GalnPSb), gallium (SnSeS), tin selenium telluride (SnSeTe), tin sulfide telluride indium phosphide nitride (GainPN), gallium indium anti (SnSTe), lead selenium sulfide (PbSeS), lead selenium tel monide nitride (GainSbN), gallium phosphide antimonide luride (PbSeTe), lead sulfide telluride (PbSTe), tin lead nitride (GalPSbN), indium aluminum phosphide arsenide sulfide (SnPbS), tin lead selenide (SnPbSe), tin lead telluride (InAlPAs), indium aluminum phosphide nitride (InAlPN), (SnRbTe), tin oxide sulfide (SnOS), tin oxide selenide indium phosphide arsenide nitride (InPASN), indium alumi (SnOSe), tin oxide telluride (SnOTe), germanium oxide num antimonide nitride (InAISbN), indium phosphide anti sulfide (GeOS), germanium oxide selenide (GeOSe), ger 10 monide nitride (InPSbN), indium arsenide antimonide manium oxide telluride (GeOTe), tin lead sulfide selenide nitride (InAsSbN) and indium aluminum phosphide anti (SnRbSSe), tin lead selenium telluride (SnPbSeTe) and tin monide (InAlPSb). lead sulfide telluride (SnPbSTe). 6. The quantum dot of claim 1, wherein the compound of 5. The quantum dot of claim 1, wherein the compound of Group 12 and Group 16 comprises at least one selected from Group 13 and Group 15 comprises at least one selected from 15 the group consisting of cadmium sulfide (CdS), cadmium the group consisting of gallium phosphide (GaP), gallium selenide (CdSe), cadmium telluride (CdTe), zinc sulfide arsenide (GaAs), gallium antimonide (GaSb), gallium (ZnS), zinc selenide (ZnSe), zinc telluride (ZnTe), (GaN), aluminum phosphide (AlP), aluminum sulfide (HgS), mercury selenide (HgSe), mercury telluride arsenide (AlAs), aluminum antimonide (AlSb), aluminum (HgTe), zinc oxide (ZnO), cadmium oxide (CdO), mercury nitride (AlN), indium phosphide (InP), indium arsenide oxide (HgC), cadmium selenium sulfide (CdSeS), cadmium (InAs), indium antimonide (InSb), indium nitride (InN), selenium telluride (CdSeTe), cadmium sulfide telluride (Cd gallium phosphide arsenide (GalPAS), gallium phosphide STe), cadmium zinc sulfide (CdZnS), cadmium zinc selenide antimonide (GalPSb), gallium phosphide nitride (GaPN), (CdZnSe), cadmium sulfide selenide (CdSSe), cadmium gallium arsenide nitride (GaAsN), gallium antimonide Zinc telluride (CdZnTe), cadmium mercury sulfide (CdHgS), nitride (GaSbN), aluminum phosphide arsenide (AlPAs), 25 cadmium mercury selenide (CdFIgSe), cadmium mercury aluminum phosphide antimonide (AlPSb), aluminum phos telluride (CdHgTe), zinc selenium sulfide (ZnSeS), zinc phide nitride (AlPN), aluminum arsenide nitride (AlAsN), selenium telluride (ZnSeTe), zinc sulfide telluride (ZnSTe), aluminum antimonide nitride (AISbN), indium phosphide mercury selenium sulfide (HgSeS), mercury selenium tellu arsenide (InPAs), indium phosphide antimonide (InPSb), ride (HgSeTe), mercury sulfide telluride (HgSTe), mercury indium phosphide nitride (InPN), indium arsenide nitride 30 Zinc sulfide (HgZnS), mercury zinc selenide (HgZnSe), (InAsN), indium antimonide nitride (InSbN), aluminum cadmium Zinc oxide (CdZnO), cadmium mercury oxide gallium phosphide (AlGaP), aluminum gallium arsenide (CdHgO), Zinc mercury oxide (ZnHgO), zinc selenium (AlGaAs), aluminum gallium antimonide (AlGaSb), alumi oxide (ZnSeO), zinc tellurium oxide (ZnTeC), zinc sulfide num gallium nitride (AlGaN), aluminum arsenide nitride oxide (ZnSO), cadmium selenium oxide (CdSeO), cadmium (AlAsN), aluminum antimonide nitride (AlSbN), indium 35 tellurium oxide (CdTe0), cadmium sulfide oxide (CdSO), gallium phosphide (InGaP), indium gallium arsenide (In mercury selenium oxide (HgSeO), mercury tellurium oxide GaAs), indium gallium antimonide (InGaSb), indium gal (HgTeC), mercury sulfide oxide (HgSO), cadmium zinc lium nitride (InGaN), indium arsenide nitride (InAsN), selenium sulfide (CdZnSeS), cadmium zinc selenium tellu indium antimonide nitride (InSbN), aluminum indium phos ride (CdZnSeTe), cadmium zinc sulfide telluride (CdZn phide (AlInP), aluminum indium arsenide (AlInAs), alumi 40 STe), cadmium mercury selenium sulfide (CdHgSeS), cad num indium antimonide (AlInSb), aluminum indium nitride mium mercury selenium telluride (CdhgSeTe), cadmium (AlinN), aluminum arsenide nitride (AlAsN), aluminum mercury sulfide telluride (CdHgSTe), mercury zinc selenium antimonide nitride (AISbN), aluminum phosphide nitride sulfide (Hg/nSeS), mercury zinc selenium telluride (Hg (AlPN), gallium aluminum phosphide arsenide (GaAlPAs), ZnSeTe), mercury zinc sulfide telluride (HgZnSTe), cad gallium aluminum phosphide antimonide (GaAlPSb), gal 45 mium Zinc selenium oxide (CdZnSeO), cadmium zinc tel lium indium phosphide arsenide (GalnPAs), gallium indium lurium oxide (CdZnTeC), cadmium zinc sulfide oxide aluminum arsenide (Gain AlAs), gallium aluminum phos (CdZnSO), cadmium mercury selenium oxide (CdHgSeO), phide nitride (GaAlPN), gallium aluminum arsenide nitride cadmium mercury tellurium oxide (CdHgTe0), cadmium (GaAlAsN), gallium aluminum antimonide nitride mercury sulfide oxide (CdhgSO), zinc mercury selenium (GaAlSbN), gallium indium phosphide nitride (GainPN), 50 oxide (ZnHgSeO), zinc mercury tellurium oxide (ZnHgTeO) gallium indium arsenide nitride (GainAsN), gallium indium and zinc mercury sulfide oxide (ZnHgSO). aluminum nitride (GainAIN), gallium antimonide phosphide