www.advmat.de www.MaterialsViews.com RGESREPORT PROGRESS Inkjet Printing—Process and Its Applications

By Madhusudan Singh, Hanna M. Haverinen, Parul Dhagat, and Ghassan E. Jabbour*

processes, and inkjet printing provides an In this Progress Report we provide an update on recent developments in ideal capability for initial process develop- inkjet printing technology and its applications, which include organic thin- ment (Section 5). This will be followed by a summary of recent developments in print- film transistors, light-emitting diodes, solar cells, conductive structures, ing of magnetic nanoparticles (Section 6) memory devices, sensors, and biological/pharmaceutical tasks. Various for memory and other related applications. classes of materials and device types are in turn examined and an opinion is All devices, organic thin film transistors offered about the nature of the progress that has been achieved. (OTFTs), LEDs, and solar cells, require contactsandconductivestructures(Section7) as part of larger circuits that integrate them. Sensors and detectors are an integral part of many aspects of 1. Introduction modern life, such as light detectors, safety, and security applications such as toxic gas sensors, etc. Many of these The organic electronics roadmap identifies organic and printed applications require inexpensive, often single-use devices that are electronics market to exceed $300 billion over the next 20 years.[1] ideally suited to inkjet printing. We will present a discussion of Print technology borrowed from the graphic arts and newspaper notable reports of progress in this field (Section 8). Finally, we will industry can be adapted in principle to the production of large make a very brief survey of progress in printed biological and volume organic electronics. In particular, digital inkjet printing, pharmaceutical devices and applications (Section 9), and the use which has been used as a low cost research tool, is facilitating of inkjet printing as a patterning process (Section 10), concluding initial explorations of various aspects of printed electronics in a with a concise summary. This Progress Report is not intended to laboratory setting. The appeal of this technology lies in it being a be exhaustive in nature, but we choose particular applications of non-contact, additive patterning and maskless approach. Direct inkjet printing, which in our opinion, offer the greatest advance write attribute of inkjet printing allows for deposition of versatile in their respective fields in recent years, and most promise for thin films, the designs of which can be changed with ease from forthcoming work of a significant nature. batch to batch. Other attractive features of this technology are: reduced material wastage, low cost, and scalability to large area manufacturing. 2. Inkjet Printing Process In the sections that follow, we will attempt to present a brief overview of recent progress in the understanding of inkjet Inkjet printing is a material-conserving deposition technique printing process (Section 2). A section on progress in organic used for liquid phase materials. These materials, or inks, consist thin-film transistors (Section 3) will be followed by a review of of a solute dissolved or otherwise dispersed in a solvent. The printed light-emitting devices (LEDs, Section 4). The develop- process essentially involves the ejection of a fixed quantity of ink ment of economically viable solar cells requires high throughput in a chamber, from a nozzle through a sudden, quasi-adiabatic reduction of the chamber volume via piezoelectric action. A [*] Prof. G. E. Jabbour, Dr. M. Singh, P. Dhagat chamber filled with liquid is contracted in response to application School of Materials, Arizona State University of an external voltage. This sudden reduction sets up a shockwave Tempe, AZ 85287 (USA) in the liquid, which causes a liquid drop to eject from the nozzle. E-mail: [email protected] This process has been analyzed at some length and the reader is Prof. G. E. Jabbour, Dr. M. Singh referred to recent review papers.[2] The ejected drop falls under Advanced Photovoltaics Center, Arizona State University Tempe, AZ 85287 (USA) action of gravity and air resistance until it impinges on the substrate, spreads under momentum acquired in the motion, and Prof. G. E. Jabbour, H. M. Haverinen [3] Flexible Display Center, Arizona State University surface tension aided flow along the surface. The drop then Tempe, AZ 85284 (USA) dries through solvent evaporation,[4] as shown in Figure 1. Recent [5] H. M. Haverinen studies show that drop spreading and the final printed shape Optoelectronics and Measurement Techniques Laboratory strongly depend on the viscosity, which in turn is a function of the Department of Electrical and Information Engineering molar mass of the polymer. More interestingly, the aforemen- University of Oulu Oulu 90014 (Finland) tioned group also found a printing height dependence of the final dried-drop diameter, which was a function of the polymer DOI: 10.1002/adma.200901141 concentration.[6]

Adv. Mater. 2010, 22, 673–685 ß 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 673 674 PROGRESS REPORT o atrs hc a eciia o rnigapiain.Hill applications. printing for al. critical et is fluid be of approach can measurements which an patterns, direct flow lacks such it However, as a substrate. approximate a the necessarily of interaction with with as well drop as coupled process falling flow the study interest, to (ANSYS), used Fluent been as have of such software using substrate modeling dynamics computational fluid and printing the tension, surface viscosity, a inkjet the on of by measurement of presented drop angle development contact single as the such Measurements for processes. interest the immediate to prevented polymer even flexible of or amount controlled small be solvent. a can of drop addition the through of rebound the opooyo h nlpit novsteueo silica of use the the involves affects print, which final size, the nanoparticles dried-drop of the the morphology avoiding of measuring method sophisticated for of less reliably reduction A process. criteria for printing responsible the are developed in resolution that drops liquid authors satellite the of The of formation stretching etc. satellites, and and formation drop, drop streak, primary fluid, the of of of the breakup breakup of stretching streak, recoil liquid nozzle, and from falling streaks freely ejection liquid of of pinch-off and processes necking the measure used water, were DI to alcohol isopropyl including and water, fluids, of mixtures Several imaging glycerin-based drops. direct for the resolution time in of good brightness as measurements well sufficient as obtain view of to field setup the photography laser flash pulsed a a with and conjunction in used was system printing inkjet rne rp fe h etn cin hs aln rp are drops falling These action. jetting the after drop. drops sessile printed the of size the to size dried-drop relate netgto fdpnec ffloecnefo poly[2- from fluorescence of dependence methoxy-5-(2 the involves of method The field. investigation shear a in polymers fluorescent of h usrt safnto fnra tesa h otc line contact the substrate. at the stress and normal fluid of the function an with between a fluid developed as non-Newtonian al. a substrate printing et of the a interaction Bartolo on the impact energy. a of upon surface understanding as fluid low a ink with of in fluid ‘‘rebound’’ substrate especially the the invalid, of of often case is the flow assumption the This fluid. assuming Newtonian on depends process yDn tal. et reported been Dong has technique by a such of development The patterns. relationship the of the printed. weight of molecular being the study species and the stress shear permits optimal in it the involve on between pattern, handle properties direct flow does from a actual ejection offer not flow its the that does to technique this prior the situation While shearing nozzle. and the on a fluid the hence, impact of printing, and, compression critical weight inkjet molecular length, a piezoelectric the segment segment has to in Polymer related changes viscosity, polymer. infer directly to is conjugated studied which the is in fluid, a length in applied the force on depending shear peak fluorescence which which the Rheochromism, in cylinders, shift force. a two shear involves a between generate situation to relatively flow rotate Couette a in PPV) www.advmat.de h o rpriso iueplmrsltosaeof are solutions polymer dilute of properties flow The njtpitn eed rtclyo h eairo ejected of behavior the on critically depends printing Inkjet otcnetoa nesadn fteike printing inkjet the of understanding conventional Most ietiaigofr oedrc esrmn fikflow ink of measurement direct more a offers imaging Direct [8] aeitoue hoursettcnqefrtestudy the for technique rheofluorescent a introduced have 0 [10] ehlhxlx)(,-hnln iyee](MEH- vinylene)] -ethyl-hexyloxy)-(1,4-phenylene [9] nodrt a h pedn ftedo and drop the of spreading the map to order in ee rpo-ead(O)piezoelectric (DOD) drop-on-demand a Here, [7] hydmntae that demonstrated They ß 00WLYVHVra mH&C.Ka,Weinheim KGaA, Co. & GmbH Verlag WILEY-VCH 2010 neato fpitddo ihapeatre ufc a been has al. surface et prepatterned Khatavkar of by a Modeling treated with substrate. simple drop flat a printed the on of more to impinging interaction drop compared in printed a when result of patterns cases) case situations flow many Such fluid (in at complicated materials. potentially substrates and multiple prepatterned processing, of involving of use levels the multiple involves printing inkjet water. DI bare to of compared point those pinch-off where lower different, had was suspensions never solutions powder both bias; silver for that pulse point the pinch-off surface; droplets the of (v) independent separated the and is time in hitting generated applying break-off (iv) resulted before were recombined; by voltages recombined droplets higher (ii) they two (iii) but droplets; inks, jetting both small a after created to and and bias bias onset column intermediate higher a liquid droplet had ink longer nozzle, viscous found They more control. as the (i) water that: DI pure from using water, DI nanoparticles time in silver dispersed of size breakup droplet and velocity, drop droplet morphology, on voltage ozedaee sdsrbe uhapoeshsbeen has process a Chandra Such the and than desirable. Goghari smaller by is features demonstrated produce diameter can a and nozzle of that reliability development the process the Hence, reducing printing process. more jetting thereby involves the clog, of it to repeatability easier but smaller are Further, possible cost. nozzles increasing is smaller thereby size, cartridges of processes, drop complicated Machining inkjet the conditions. in on jetting nozzles bound unusual lower any fundamental barring the form diameter nozzle should the Intuitively, energy diameter. surface nozzle and ink, substrate, the of conditions, jetting on ultimately depends drop. for printed to the critical that of is indicated barrier spreading the of results of determination the wettability geometry, surprisingly, barrier Not constant width barrier. and barrier the the of wettability of of effect the consider to model fetdb eea atr nldn etn odtosand conditions jetting including al. et Tsai factors ambient. the of several properties by affected n photonics. and nanoelectronics, and flexible energy, are materials, interests electronic research stretchable His Finland, of Finland. Prof. of Distinguished a Academy and fellow Prof. SPIE Engineering. a is and Jabbour Science Electrical Materials Physics, and in Engineering, degrees bachelor’s his received nms ae,fbiaino ucinldvc tutrswith structures device functional of fabrication cases, most In rnigo hnlnsi iie ytesz ftedo,which drop, the of size the by limited is lines thin of Printing [12] h uhr sdadfueinterface diffuse a used authors The nvriyo rzn.He Arizona. of University and MIT, University, Arizona Northern attended at He Materials ASU. of School the Professor of a and (FDC), Display Center Flexible the at devices and materials optoelectronic research of director a (ASU), University State Arizona at Center Photovoltaics Advanced the of director Jabbour E. Ghassan [11] tde h fet fpulse of effects the studied d.Mater. Adv. [13] www.MaterialsViews.com o water–glycerin for 2010 sthe is , 22, 673–685 PROGRESS REPORT 675 [16] and display www.advmat.de [17] investigated packing of inkjet m. The authors also attempted to [10] The height of the single drop m, while printing of a complete m m [3] Polymers and other solutions and suspen- sions lend themselves readilying. to Fabrication inkjet print- species of other structures thancules/macromolecules polymers that that are easily or dissolved involve smallin mole- solvents presents aFor new instance, set suspensions ofticles of challenges. tend metal to nanopar- beand unstable in can ordinary require solvents ifications complicated chemical that mod- Printed nanoparticles involve behave differentlyprinted from use polymers and other of solutions owingtheir to stabilizers. higherlikelihood specific gravity forassembly and phase of increased separation. such nanoparticles The on final the sub- We will now discuss significant accomplishments [18] m. m Inkjet printing of homogenous polymer solutions is common. We have thus attempted to address the gamut of features and strate depends onenergy properties. Perelaer surface et al. treatments which change surface A key activeOTFT. element for Use implementingapplications, organic of which circuits OTFTs is doand the has not require switching been significantly speeds, high demonstrated mobility such in as low-end RFID tags Using white light interferometry,higher the solute authors contents found reduces thatfrom print use non-uniformities the of that arise coffee-ring effect. 3. Thin-Film Transistors in the area of printedall-printed and organic hybrid transistors. devices We (where will conventional lithography focus is on both printed spherical silicadifferent nanoparticles. nanoparticle The sizes studysurface stabilized involved groups with four in hydroxylsurface a treatments, or the 1 authors wt silanol found that %closer larger aqueous particles to packed solution. the center Usinghigh, while of different smaller particles the under the dropletcloser same to conditions when the migrated the contact line contactthe at angle use the edge was of of highly thenanoparticles, hydrophobic droplet. avoiding Furthermore, substrates coffee-ring assisted formation. in packing of However, the use of colloidal suspensionsof expands polymer/solvent the combinations repertoire that can beis printed. This particularly ability vitalprocess in to designing fabricatePrinting a multiple of pure layers aqueous inkjetsuspension with inks in printing-based orthogonal water containing was solvents. demonstrated a by van 40 wt den Berg % et polyurethane al. deposited was found to be 3 issues unique to themeasurement inkjet of printing process. rheologicalsubstrate These interactions, properties post-jetting involve behavior of the of printedflight droplets the in and inks, aftersurveyed droplet– recent collision work on with methods usedof to the enhance the substrate. device resolution Wenanoparticles. structures have We briefly now composedprinting. turn of to various polymers applications and of inkjet metallic layer revealed a thickness of 10 print a step87 structure resulting in a pyramid with a height of backplanes. (1) ink. Thermally 2 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim The authors used a resulting in feature C, along with the ß 8 [14] [15] m. The reader is referred to this m are the viscosity, density, and surface tension of 673–685 s 22, , s , and d r 2010 ffiffiffiffiffiffiffiffi r m The process of drop drying after deposition with inkjet printing. Reproduced with , p m ¼ At high integration densities, such as for electrophoretic Other methods to increase resolution of printed features Adv. Mater. where Oh the ink, while d is the nozzlesuch diameter, is conditions a good are predictor of satisfied. when backplanes, the tolerances onlinetight. non-uniformities Thus, can it be isinteraction very between desirable the to ink and directlyfor substrate. instance, The control arises coffee-ring the in effect, part naturedrying from of of interaction the of solvent, the resultant multiple changes effectstransport in of of the the viscosity solute of via the motion ink, arising of from the surface solvent, tension the interaction latterthe motion between the substrate, solvent etc. and Itgeometry and would layout of be ink advantageousperiod drops on to the of arrest substrate in thepolymers time a final very is short after onePrinting deposition. of method continuous polymer that lines Use using gelatingbeen can polymers of demonstrated has help by van thermally ensure den Berg this gelating et al. outcome. mixtures with intermediatecustom drop concentrations. generator that They exploits fluiddroplets. developed instability to This form a small instabilitysatisfying depends on certain theOhnesorge conditions. number, material parameters The authors found that the Figure 1. permission from [4]. Copyright 2008, Wiley-VCH. www.MaterialsViews.com diblock copolymer poly(vinyl4-butyric methyl ether)-block-poly(vinyloxy- acid) colloidally stabilizing a TiO gelating materials exhibit strongauthors found temperature a dependence. temperature-dependent increase The inwhich ink viscosity, increased dramatically above 37 corresponding increase inlines. print fidelity for printed drops and involve bypassing thermal/acoustic printingelectric altogether fields and to use drivenamic the printing jetting process.resolutions An (EHJ) was electrohydrody- developed technique by Park to et al. achieve sub-micrometer sizes in the range of 240 nm to 5 paper for more details onof printing very processes high that involve electric thecone fields use at to the propel tip ink ofbiological drops, the systems forming capillary. An a will application Taylor be of presented this approach in to Section 9. 676 PROGRESS REPORT prahbsduo efainn lcrds eutn in developed. resulting was electrodes, lengths, cost-effective self-aligning channel more A upon nm cost. 100 production based in increase approach an to lead to device. the ergto ftesratn otesrae hscetsa creates This repels surface. which the droplet, the to surrounding layer surfactant tension to low-surface the due droplet of drying separation the of segregation self-aligned surface the the a from on groups accumulate created tail surfactant hydrophilic also The electrodes. ink printed between surfactant PEDOT:PSS a of the addition that to demonstrated also authors The mer. dioctylfluorene- f20n wihdfie h hne egh nodrt confine to order droplets. in length) channel printed the separation defined a (which nm with 250 (PMMA) create of to methacrylate lithography polymethyl nanoimprint in of trenches use the demonstrated they ici ein iiigtesicigsed o110Hz. 1–100 to speeds switching the the on limiting implications has design, This circuit achieved. be can that length channel en endb h it fteSMmesa. SAM the channel of the width of the length by the defined with electrodes being S/D self- separate droplet inkjet-printed two an split into hydrophobic substrate the and mesa a 20 the between varied from pattern which width structure, in to mesa-like (SAM) lithography monolayer assembled e-beam possible was lengths using channel the in reduction Further separation. eursike rnigfis e fPDTPSeetoe and electrodes (CF tetrafluoride PEDOT:PSS carbon of a with set them treating first printing inkjet requires h aeeetoe(EO:S)wspitdo o fthe of top on 1 of printed accuracy semi- registration was a organic with (PEDOT:PSS) layer The dielectric electrode material. gate finally electrode and the spin-coated, S/D were material dielectric the the and conductor as used (PEDOT:PSS) was ethylenedioxythiophene):poly(styrenesulfonate) njtpitdsuc–ri SD lcrdso hydrophilic a the on substrate electrodes from (S/D) glass of lengths lithographically source–drain spread the printed used channel contain inkjet to They create banks polyimide range. hydrophobic to nm patterned sub-100 approach to hybrid micrometer a of ihmblt auso .0 cm 0.002 of values the transistors mobility in being resulted solvent approach with this with of device, Use wasted. the material semiconductor only complete organic electrode of gate printing and Additive electrodes. in between drying two (SAG) before gap the self-aligned electrodes, nm of sub-100 a set forming first vicinity the the second from the repelled from Ink is set. print first the overlapping partially electrodes printed PEDOT:PSS are of set second a Next, surface. hydrophobic hne eghi re ooecm h wthn speed switching the overcome to order al. et Sirringhaus in limitation. length channel ici eed pnmblt n h hne egh( length channel the a of and speed mobility switching upon be the depends can Additionally, circuit electronics. problems case the flexible simple, as These substrates, for nonplanar appears on printing. printing orthogonality OTFT when layer-by-layer solvent compounded material. an and with organic registration of to issues active due structure and arises dielectric basic complexity of the each gate) Although the layer and drain, one (source, material and electrode of device layers four-layer a two is with OTFT An printing). with conjunction in used rnigofr resolution a offers printing ( width channel www.advmat.de oee,teueo ovninlltorpytosi expected is tools lithography conventional of use the However, oto h eetefrshv enfcsdo euigthe reducing on focused been have efforts recent the of Most co [20] W btipee FT) iudcytliepoly- crystalline liquid a (F8T2), -bithiophene) [22] ai ftetasso.I otcss inkjet cases, most In transistor. the of ratio ) m raigcanlfaue with features channel creating o20n.Sraeeeg differences energy Surface nm. 250 to m o eie etoe bv,poly(3,4- above, mentioned devices For [20] ucsflydmntae h use the demonstrated successfully 20 m m, 2 [1] V u iistesmallest the limits but 1 ß [23] 4 s 00WLYVHVra mH&C.Ka,Weinheim KGaA, Co. & GmbH Verlag WILEY-VCH 2010 lsat raea create to plasma ) 1 [21] m hstechnique This ,t complete to m, ihpoly(9,9- with Furthermore, [19] 5 L )to m m oee,i hscs,pitdgl lcrds( electrodes gold printed case, this in However, ipasuigPT1 steatv aeil hsrsle in resulted This cm material. 0.06–0.2 active of the values electrophoretic mobility as for PQT-12 backplanes using has create and displays OTFTs to gate used bottom coplanar successfully a been in electrodes three the all shg s16MHz. 1.6 as to high nm 60 as from second lengths the channel repel in 4 to resulting used to were electrode SAM printed hydrophobic a with treated lcrd einpeet ag ekg urnsadcrosstalk and currents leakage large prevents region electrode organic of successive patterning between layers. registration simple good This offers layer areas. for semiconductor hydrophilic allow regions hydrophobic the to the the from onto removed solution exposing the gradually an of removed dewetting and in selective dipped solution then is polymer substrate is The organic it. wax underneath region The hydrophilic hydrophobic. uncovered the making area SAM to exposed is substrate wax the with which covered after is region channel the electrodes, S/D predefined xd nanoparticles oxide tlzda oeta candidates. potential as been utilized have inks nanoparticle copper and gold inks, nanoparticle silver PEDOT:PSS, as such transistor. materials Electrode a in layers active 30–50 o OTFTs. for cielyrik ogncsmcnutr isle nvarious in dissolved semiconductors (organic poly[5,5 as such solvents) inks layer active a a o nybe sdt en rtcldvcsfaue but features process. devices patterning critical selective define for to used used also been Printed only 7. not Section has in wax length greater at structures conductive such ohwxadsbtae eutn ncanllntsrnigfrom ranging lengths 40to400 channel in resulting substrate, of and temperature wax by both controlled is size drop The removal. photoresist and etching metal as such processes lithographic subsequent from derivatives, (PQT-12), iharssiiyo 5 of resistivity a with ooti epcal oiiyvle f0102cm 0.1–0.2 of values mobility respectable semiconductor obtain a organic to to mobility able high were a poly(2,5-bis(3-dodecylth they with recently, SAG More the combine droplet. printed second the pentacene), tae sn etcn rcrosadpl--iypeo (PVP) poly-4-vinylphenol dielectric; and precursors pentacene using demon- in strated been difficulties have transistors the all-printed layers. Despite conditions, these printed. ensuring subsequent previously been have of of that dissolution prevent layers processing to order in inkjet required are solvents Orthogonal the with compatible ru a eosrtdteueo a sapooeitto photoresist a metal as blanket wax on films. of pattern thin electrodes use S/D PARC the define The lithographically device. demonstrated printable the minimum has of the length group channel that the such defines masks size create feature to order in tool aebe eosrtd eety abnnntbs(mobili- nanotubes carbon Recently, ty demonstrated. been have ihapitdbackplane printed a with m h cuaepaeeto h ciemtra ihntegate the within material active the of placement accurate The nodrt arct l-rne TT,tedeetishv obe to have dielectrics the OTFTs, all-printed fabricate to order In et efcso sn njtpitn sadgtllithography digital a as printing inkjet using on focus we Next, .Ivresbsdo hs rnitr xiie frequencies exhibited transistors these on based Inverters m. .7cm 0.07 m m. m [26] [24] [31] m.Digitallithographyusingwaxhasbeenusedtodefine [27,38] [26] [28] [29] 2 n oyyrl n PVP-K60. and polypyrrole and V te nrai pce uha polysilicon as such species inorganic Other F8T2, h aegopdmntae iia performance similar demonstrated group same The te etcn rcrosadoligothophenes and precursors pentacene other ,3bstispoyslltyy)pnaee(TIPs pentacene 6,13-bis(triisopropylsilylethynyl) 1 ra htaecvrdb h a r protected are wax the by covered are that Areas s [33] [27] 1 [19] aebe njtpitda h ciematerial active the as printed inkjet been have ) iophene-2-yl)thieno[3, aeas enscesul njtpitdas inkjet-printed successfully been also have 10 i-tbepl(-eytipee (P3HT) poly(3-hexylthiophene) air-stable 0 -bis(3-dodecyl-2-thienyl)-2, 2 [39] 6 ossigo ivrnnpril lines nanoparticle silver of consisting V [28,34–37] m ewl drs h rnigof printing the address will We cm. 2 V 1 s 1 d.Mater. Adv. [40] -]hohn)(pBTTT) 2-b]thiophene) o hne egh of lengths channel for [25] www.MaterialsViews.com nasbtaewith substrate a On diiepitn of printing Additive s 2010 ¼ 0 -bithiophene] 10 2 [32] , 4 22, V Scm andzinc 673–685 1 s [30] 1 1 ) . PROGRESS REPORT 677 of various www.advmat.de [47,48] 99% on flexible porous > nanoparticles, and 90-nm-diameter 3 -dichlorobenzene are also shown. Reproduced with o have demonstrated the feasibility of using blended -dichlorobenzene, and d) dodecane. (Scale bar represents o [46] However, before the commercialization of TFT and FET-based perovskite films through60-nm-diameter inkjet printing. BaTiO The authors printed 4. Light-Emitting Devices Inkjet printing does not require thedirect use writing of shadow process. masks This as property itsuitable of is inkjet a printing technique makes it for a combinatorial studies metallic nickel particles with purity acetate sheetsdisperse using the nanoparticles a in ethanol–isopropanol solvent propylene blend. glycol-basedproducts, surfactant there are road to blocksand that require significant immediate attention amountdifferent layers of of print work.inkjet has printing. The Registration to solvents need be to of besubsequent resolved compatible layers features for when and printing yet high be at environmentally throughput safescale for production. use Additionally, passivation in of large thealso printed device important is for longArias lifetime et operation al. capabilities. Recently, active and encapsulationprinting in material the channel thatactive region. polymer There phase to is ambient limited separate conditionsresulted exposure in during of cost upon effective the the printing print of both cyclelayer active and in and encapsulation a single step. -Ni 3 Optical microscopy and polarized images of the inkjet-printed droplets of TIPS m with m m) The profilometery images of single dots using chlorobenzene mixed with 25% minor m 50 Figure 2. pentacene using chlorobenzene asa) the chlorobenzene, major b) solvent hexane, mixed c) with 25% of the minor solvent, solvents, e) chlorobenzene, f)permission hexane, from g) [4]. Copyright 2008, Wiley-VCH. can be used to 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim [44] 3 ß [41,42] , which is comparable with 1 s 1 cm were obtained in this manner. V m). This also benefits the bottom 2 m mV 5 demonstrated use of demonstrated the deposition of BaTiO ¼ 25 [4] L . ( [45] 1 1 673–685 s s 1 22, , 1 V and polar materials like LiNbO 2 V 2010 2 [43] 3 High integration densities of field-effect transistors (FETs) and Inkjet printing of OTFTs has been limited to Adv. Mater. Ability to control the dropamount volume of to picoliter organic values, solventAnother limited dispensed advantage the on of reduced top dropletsintering of volume temperature the for was active metallic a layer. nanoparticles decreaseelectrodes that in formed preventing the subsequentorganic layer. Continuous damage metallic lines to as narrow the as 1 underlying resistivity values of between TFT pixels, asRecently, well as Lim conserves et ink. al. www.MaterialsViews.com contact geometry whereobtained without much the use smallerfor of miniaturization conventional feature lithographic of processes sizes printed circuits. can be TFTs require device structuresarea with to a maintain high proper capacitanceBaTiO control per of unit the channel. Perovskites like bottom contactelectrodes were S/D architecture electrodes were deposited before wherein the organic active layer. the damage This to prevented the organic active layersolvent, from the ink preserving theAlso, the device registration issues were performance. limited toprinting the of gate electrode for top gate.there Recently, have been developments with topOTFT contact geometry, where the metaldes S/D are electro- printed on top of the active layer. solvent mixtures to balance the Marangoniconvective and flows in acontrolling drying morphology droplet, of thereby (Fig. the 2). dried The droplet using a evaporation high surface rate tensionpoint and is solvent high boiling controlled (majorlower boiling solvent) point solvent (minor mixed solvent) and surface with tension a lesscomponent. than A that convectivefrom of flow the is the center toward established major thedroplet drying as edge the of evaporation the periphery; rate is driven faster atgradient the by between the thethe edge surface center. ofgradient the However, tension creates drop an this opposing and Marangoniwhich surface flow, results in tension in recirculation the droplet. of The the driedin droplet solvent then resulted largepentacene self which provided organizedas 0.12 mobility cm crystals as high of TIPs enhance such control throughunit enhancement area, of in addition capacitance toinduction. per more exotic It polar effects istechnique such as thus for charge deposition desirablechannel. of Tseng et to such al. develop materials accurately an over inkjet the printing those ofdemonstrated evaporated on anfluorophthalocyanine electrodes. (F16CuPc) n-type resulting This semiconductor in0.02 cm mobility copper technique values of hexadeca- was also Further details ofMobility this obtained for report pentacene will OTFTselectrodes fabricated was be using 0.1–0.3 printed presented cm in Section 7. 678 PROGRESS REPORT ec fike rne nrai eiodco nanoparticles group semiconductor same the Photolumines- inorganic by demonstrated thicknesses. printed was device inkjet the of and cence on chemistry depend the turn a in both which in interactions, thicknesses inter-chain emission the on poly- film of wavelength dependence strong and a different found chains They manner. six side parallel different of with properties polymers (PPE-PPV)-based emission the (phenylene-ethynylene)/PPV on influence etlvrain,adrsligucranisivle in involved uncertainties structures. device resulting different of processing and environ- sequential process, solar variations, the organic reduce as mental such considerably devices, and other etc. PVA OTFTs, for cells, used in be method This embedded can 3). (Fig. principle were study PDDA in of case dots the in emission Photoluminescence when weakened but emission spectroscopy. strong showed characterized fluorescence with and printed (PDDA) with were concentrations chloride) weight different luminescence poly(diallyldimethylammonium PVA investigate matrix, polymer and to embedded in order nanocrystals the of In properties rather separately. mixture the printed in used than was PVA or when formed Smoother only drastically. were wt formation 2 films ring acid with the suppressing occurred glycol, formation of drop observed % authors and thioglycolic The morphology glass. best and the ITO that on of concentrations printed glycol was varying %) with vol and (0–20 (PVA) mixture nanoparticles alcohol polyvinyl CdTe % wt 1 stabilized aqueous acid 3-mercaptopropionic An study. Pmxue.TeP pcr ntebto ee otesm library. same the to refer Wiley-VCH. 2007, bottom Copyright the [50]. red–green on from various permission with spectra with red PL to Reproduced green The from mixtures. change color NP a reveals part top 3. Figure al. material et and Tekin time-consuming once intensive. at and is of which experiments properties devices, electroluminescent different multiple the entails of measurements often repeated process of (OLEDs). use This device involves diodes optimal designs. of often determination and emitting structures thicknesses, device device different light OLED of organic Optimization including devices, www.advmat.de obntra td fpitdrdadgennnprils The nanoparticles. green and red printed of study Combinatorial [49] sdike rnigt xmn the examine to printing inkjet used [50] spr facombinatorial a of part as ß 00WLYVHVra mH&C.Ka,Weinheim KGaA, Co. & GmbH Verlag WILEY-VCH 2010 p -conjugated unu fcec f01%adbihns f31c m cd 381 external of an brightness showed and results 0.19% was ITO Preliminary of cathode. anode. efficiency LiF/Al a quantum the of as deposition the used by a with followed capped layer was QDs printed condi- the 1,3,5-tris(2- of ambient monolayer a under Nearly tions. layer (poly-TPD) bis(phenyl)benzidine) eedsesdi hooezn n njtpitdonto poly( printed inkjet cross-linked and optically chlorobenzene in an dispersed (QDs) dots were a quantum transport CdSe/ZnS and electron stabilized polymer Octadecylamine molecule layer. small transport organic hole evaporated coated thermally spin between nanoparticles embedded semiconductor inorganic printed inkjet from cence to fteCDcmr thg brightness. high at satur- camera slight the CCD to from due the arises round of region perfectly ation not bluish-white is The device non-uniformities. the printing of region shape The illuminated nm. the 520 of of wavelength peak a at emitting macromolecules POSS --etuy-hnl134oaizl PD.Teauthors m cd The 6000 than more 2-4-biphenylyl- of luminance polymer, peak (PBD). a ink achieved transporting polymer electron a 5-4-tertbutyl-phenyl-1,3,4-oxadiazole an poly(9-vinylcarbazole) in polymer, molecular and dye transporting (PVK) (POSS) hole phosphorescent a a silsesquioxane containing as used oligomeric scaffolding polyhedral on anchored a macromolecules phosphorescent Ir-based on based rn opooy h uhr eeal oaheeapeak a achieve to able were rough authors from luminance and the chemistry quenching morphology, dye which of in print improvements spite determining layers, Through in in contacts. chemistry printed cathode brightness, ink the device suitable of overall for role the nm) (51 underscores roughness large revealed interface measurements interferometry light White 1.4%. of o uno otg 68Vfr5c m cd 5 for V (6.8 voltage turn-on low iue4. Figure pixel the regard, this In pixel. per drops optimizing printed by study of color the number emitted addition, the the under In of surface. control operating layer simple polycrystalline QDs demonstrated format, printed demonstrated the QVGA also of study packing of The pixels cathode. substrate common 243 prepatterned a about on printing having display by to QDs shown of was inkjet of applications extension the Furthermore, V). 15.9 (at eety aeie tal. et Haverinen Recently, ig tal. et Singh htgaho 00 dm cd 10000 a of Photograph [52] N peybniiaoy TB)eeto transport electron (TPBi) -phenylbenzimidazolyl f100c m cd 10000 of [51] eosrtdbih njtpitdOLEDs printed inkjet bright demonstrated 2 [53] Fg 4). (Fig. eosrtdelectrolumines- demonstrated N 2 2 , N ,adaqatmefficiency quantum a and ), LDpitduigIr-based using printed OLED 0 -bis(4-butylphenyl)- d.Mater. Adv. www.MaterialsViews.com 2010 2 relatively a , , 22, 673–685 N , N 0 2 - PROGRESS REPORT 679 m In has m [67] [65] www.advmat.de and smaller companies in [66] the absence of a cost-effective [64] ], 65–80 nm in diameter, were In addition to etched structures of ISET, 4 O [16] 3 [63] ) and Fe 3 O 2 -Fe g , 3 O 2 It has been mentioned previously that the coffee-ring effect is Inkjet etching of polymer microstructures was demonstrated 7. Contacts and Conductive Structures Metals and conductive polymersinterconnections form the necessary basis of forcircuits, contacts which can and the be composed functioningserve of as building logic/backplanes of blocks for like electro-optic electronic photovoltaics) FETs, devices or (like and LEDs memory and components.and Conventional conductive contacts lines aretechniques. traditionally However, the defined maskless using direct write lithography printing property of can inkjet becomplexity. used Though these to structures define typicallysilver involve conductive and printing gold lines of nanoparticles, ofinvolve some significant of the the use presentedpolymer of references nanoparticles as mixed well metal as nanoparticles organometallic inks. andone conductive of the majorsame reasons for considerations non-uniform apply film to deposition. The nanoparticle-based solutions, or However, the process has traditionallypotentially involved toxic deposition precursors from inWhile a there exist low-volume, material high limitationsindium for cost and sustained fashion. gallium availability worldwide, of 6. Memory and Magnetic Applications The use of inkjetstorage printing has applications. been[(Fe extended Magnetic to magnetic nanoparticles data of iron oxide polystyrene with applicable solventsCr/Au and etching films, of magnetic polystyrene/ periphery nanoparticles of were etching depositeddroplet droplet onto drying. via Superparamagnetic the migration magnetitewere particles dispersed of in (1 toluene, wt particles stabilized %) with during Detection lauric of acid and nanoparticles printed. at thescanning ring force surface microscope. was Further executedusing consideration with inkjet of printing-based patterning techniques is provided in Section 10. synthesized and subsequently inkjet printed by Voit et al. environmentally soundshort-term process limitation in the hasmaterial way for of been more commercial widespread CIGS use solar a of cells. this Nanosolar more Inc. serious developed a nanoparticle inkprocess consisting to print of it. CIGS Othercomes and from commercial HelioVolt interest an Inc., in inkjet this technology the US and Europe. order to stabilize the nanoparticles, dextran orwas polystyrene applied. coating Dextran coated particles50 wt were % mixed glycerol while into polystyrene water coatedin particles and were dispersed diprolylene glycol.device Superconducting (SQUID) quantumcoercivity interference magnetometery of 15 measurementsnanoparticles. Polystyrene Oe coated revealed particles at dispersedlene glycol a room in were dipropy- reported temperature to havewas similar for magnetic properties. jetted Ink dextran using coated glass, a plastic, Xaar and piezoelectric paper printer substrates. (XJ128-360) Line onto widths of 40–200 were achieved. Furtherfilms magnetic were investigated properties using magnetic of force microscopy ink (MFM). jet printed by Schubert and coworkers. 2 1 [61–63] (CIGS) 2 Se ) 30% with a x (1 Ga 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim x printing have been . Furthermore, the A current at 1100 V. ß 1 m -dichlorobenzene and [56] o sq V from Konarka Technologies Inc. 1.1 k [59] 0.2 and 0.8 V, the color changed from . Upon increasing the number of printed 1 Pa) and resulted in an 8 sq 1.4%) utilizing a blend of P3HTand PCBM in a 673–685 5 Hoth et al. V ¼ reported a custom-built electrostatic inkjet setup 22, 10 , 5k [54] [57,58] printed water soluble multi-wall carbon nanotube demonstrated inkjet printed polymer:fullerene blend 2010 [55] [60] m away from the cathode. Field emission was measured in m Single-wall carbon nanotubes (SWCNTs) are notoriously Inkjet printing can be used to deposit materials for inorganic In contrast to LEDs, electrochromic devices exhibit large Use of bulk heterojunction structures in inkjet printed solar Adv. Mater. and anconversion open-circuit efficiency (PCE) voltageet of al. of 2.9%. More 0.54 V recently, Aernouts with device power 5. Solar Cells Solar cells offer thedrive power promise systems, of transportation systems, harnessing etc.not the Solar yet cells Sun’s energy have achieved to widespreadcomparison against use fossil owing fuel-based energy to sources.affairs This the state is of unfavorable a cost processing result methods, of: and (i) (iii)more relatively more cost low effective expensive solution efficiencies processable materials, materials with suchsmall the as (ii) molecules organic and costlier polymers. Evertion since of the screen initial printed demonstra- organic solar cells, concentration was deposited on a polyethylenesubstrate terephtalate (PET) and resultedresistance in a transmittance of 68% and sheet emission can be tuned from blueof to emission orange from due to the a QDs combination and the organicdifficult layers. to dispersenon-conductive uniformly mixtures in duematsu solvents et to al. and aggregate tend formation. to Shige- form www.MaterialsViews.com (MWCNT) inMWCNT a loading factor. polyaniline Nanotube dispersion (PANI) with 10 composite mg mL with a 32% 1:1 ratio. While the present efficiencycommercial values are not applications, very highpromising. for the progress madeand hybrid organic/inorganic thus solar cells. CuIn far is solar cells (PCE used a blend of P3HT and PCBM in mesitylene to demonstrate inkjet printed organic solarCa:Ag cells top with cathode a on PEDOT:PSS coatedfactor ITO. of They 64% achieved coupled with fill short circuit currents of 8.4 mA cm and demonstrated an ability toJetting print parameters aqueous SWCNT were solutions. viscosity. investigated Nanotubes were as dispersed in a amixture. water:isopropanol:glycol function The of printed solution emission layer setup, where was ITO25 used coated with as a a phosphor cathode was placed in a field vacuum (5 changes in observed color aset a function of al. applied voltage. Small decreasing sheet resistivity layers (from 1 to 3), transmittance dropped to seen to offer the promiseeffective of processes. developing industrially scalable cost cells has beencoworkers. shown to be effective by the Schubert and yellow to green, and ultimately to blue. printed layers showedPANI blend electrochromic was behavior. printed(PVDF) on A and gold platinum nanotube/ coated coated ITO polyvinylidenethe substrates. fluoride potential With a between variation of has been used as a material for high-efficiency solar cells. 680 PROGRESS REPORT odnnprilscnas eue o rnigconductive printing Zhao width, for line al. possible used minimal et reduce be to order also In structures. can nanoparticles Gold aoatce n 1.7 and nanoparticles n agdbten8 n 184 and 84 layers) (1–3 between thicknesses layer ranged various and for measured was 55 and length to 25 were waveform, platen lines nozzle sample silver the printed and modified cartridge nozzle, the pL heated 10 a al. et used Meier by They demonstrated recently was substrates untreated on njtpitn fA aoatce ihlwrsintering lower with case, this nanoparticles In substrates. plastic Au to applied been of has temperatures printing inkjet itrn,floe yasletws ormv remnant and remove uniform to in results 1–2 wash a with technique patterns solvent high-resolution This a particles. by unsintered followed sintering, itrn rcs.I hsmto,hxntilcpe Au capped ( hexanethiol laser ion Ar method, by followed this printed laser first selective are In a particles with process. printing combines sintering that technique hybrid atn fe itrn t200 and PET, at A, Teflon sintering LP, After Teflon on polyarylate, nozzle, Kapton. pL as 1 such a with substrates equipped printer materials Dimatix using a40 rprinlt iethickness. line to proportional n rcia ierssiiyo esta 25 than less of resistivity line practical and contact k small complicated (5 relatively resistivity or a reported treatment Authors surface technique. patterning prior any without technique. fabrication EHJ an 1 employing observed by The nanoparticles gold of printing rniggl aoatce 14n ndaee)i xylene/ in conductivity diameter) high with ( in features gold nm (1–4 Printed cyclohexylbenzene. nanoparticles gold printing nitrs nvrosgop.Rcnl,vnOc tal. et Osch van Recently, groups. various in interest an 10 of width and the on pL tolerances tight interconnects. 300 integration, requires printed density between backplanes, High in varied expected. as such as drop, volume, the with increasing of volume on illk orn rfiefrain(e i.5,rsligi poor in by resulting 5), Fig. good work, that this (see from In quality. formation in predicted changed film profile formation ring be which to film hill-like to data, temperature, drying found theoretical increasing and with profilometer agreement using determined 400 at 60 vacuum to dried nm), 12 and 30 from slides temperatures glass (diameter different on at printed nanoparticles first were silver ethanol, in case suspended this In formation. pce.Te sdasml -on ehdt siaethe estimate to method 2-point 7.3 case: simple each molecular in silver a precursor of conductivity used Ag They organometallic species. an and nanoparticles rne odnnpril tutrs oe al. et Ko structures, nanoparticle gold printed eemn rtcldyn temperature, to drying films critical of a properties determine morphological and droplets nanoparticle upnin.L tal. et Li suspensions. odciiywsmaue ob 32%o ukconductivity, bulk of 13–23% 63 be is which to measured was conductivity www.advmat.de 2 eiaie l ucsflydmntae u-etltrinkjet sub-femtoliter demonstrated successfully al. et Sekitani fottwr piie rne ie ihsle n a been has ink silver with lines printed optimized toward Effort ekn ute mrvmnsi h eouino inkjet of resolution the in improvements further Seeking al. et Gamerith m [71] iewdhfrike rne ivrnnpril n by ink nanoparticle silver printed inkjet for width line m 10 xeddteueo efaindpitn prahto approach printing aligned self a of use the extended 4 Scm V 10 m 8 m swl ssalprstccpctne( pF) (6 capacitance parasitic small as well as cm) 1 eouinealdsotcanllnt TFT length channel short enabled resolution m .Temrhlg fdpstdfim was films deposited of morphology The C. eereported. were ) 6 Sm [37] [68] 10 1 rne lcrdsmd fAg–Cu of made electrodes printed T ute mrvmn o iewidths line for improvement Further . 5 c tde rigcniin fsilver of conditions drying studied Scm m a hw ob togydependent strongly be to shown was nwdh Crssac e unit per resistance DC width. in m [70] 1 8 o nhu,sle line silver hour, an for C m o h uesle electrodes. silver pure the for iewdh Furthermore, width. line m V 8 10 ,adfial itrdin sintered finally and C, cm 3 Scm ß T mV c 1 00WLYVHVra mH&C.Ka,Weinheim KGaA, Co. & GmbH Verlag WILEY-VCH 2010 [28] o pia film optimal for , en inversely being , 8 .Tereported The C. cm. eosrtda demonstrated 1 o h Ag–Cu the for l [41] ¼ [69] 1. nm) 514.5 reported m L, odciiyo 8 had which of layer conductivity casted drop a thicker much with comparison good rne lswsrpre s4 as reported was films of conductivity printed Furthermore, system. inkjet in with ability them the depositing proving shown were dodecylbenzene- nanoparticles PANI using conductive PANI patterns Printed spherical nanoparticles. (PANI-DBSA) acid the sulfonic of and tension properties surface of rheological optimization upon possible was materials eotdt euiom ls o8 mi diameter. in nm 82 to close uniform, be to reported . t15kzfra1 a for kHz 135 at in nanoparticles 0.5 Au yielded structure with multilayer dielectrics nanopar- inductor/interconnect polyimide an Au of using use by The ticles. (RFIDs) devices identification frequency ukvalue. bulk eitnewssont erae sepce,fo 9 to respectively. 191 from steps, expected, as overwriting decrease, to 1–8 shown to was Resistance 1295 correspond to 170 from properties which widths, line carrier different Charge for investigated nanotubes. were carbon the drying of faster that distribution shown on was It (60 printed conditions. drying and substrates various 10 polymer as with dimethylforamide well and as glass in diameter plasma-treated and precleaned dispersed nm 5 were of SWCNTs length SWCNTs. of patterns atce a eosrtdb gmae al. et Ngamna by demonstrated was particles ihpriso rm[8.Cprgt20,TeJpnSceyo Applied formation. of Society ‘‘ring’’ 60 Japan The c) a 2007, and to Copyright Physics. 35, [68]. ‘‘hill-like’’ from b) permission a 30, with from a) are change Temperatures formation a reveals 5. Figure njtpitdgl ie ih1 with 0.03 lines of gold resistance printed inkjet oge al. et Song njtpitn fauosnndsesoso AInano- PANI of nanodispersions aqueous of printing Inkjet 8 s omtmeaue nbe oeee density even more a enabled temperature) room vs. C rs-etoso rpeswt hnigdyn temperatures drying changing with droplets of Cross-sections [72] [74,75] h aegoprpre h njtpitdradio printed inkjet the reported group same The V tde h lcrclpoete fprinted of properties electrical the studied sq 10 m hc conductor. thick m 1 4 euigcnutvt o7%o the of 70% to conductivity reducing , Scm 1 atcesz itiuinwas distribution size Particle . 10 m hcns a sheet a had thickness m 4 8 ,rsetvl.Reproduced respectively. C, Scm d.Mater. Adv. www.MaterialsViews.com [36] [73] 1 rnigo these of Printing bl)adi in is and (bulk) 2010 Q , 22, ausof values 673–685 m m m, m PROGRESS REPORT 681 M is [81] [80] N 3, where www.advmat.de > N for top-contact and 1 s 1 V reported a convenient method ) resulting in a calculated detection M 2 m [82] 0.21 cm in bottom-contact geometry. Due to their for developingPANI-PSS an nanoparticles aqueoustheir and use as dispersion an demonstrated inkjet printedThe ammonia of sensor. nanoparticlessynthesized (diameter using 30merization, nm) chemical-oxidation dispersed were poly- with in ethylene water glycol andadjust and the isopropyl viscosity and mixed alcohol surface tension to priorprinting. to The device structureprinted consisted PANI-PSS of film a nesses and with two copper varioustivity electrodes. thick- The of sensi- Figure the 6. An resulting ultralow concentrationwas sensor of reported. 10 is ppb shown in 1 . Such sensor was reported to be stable within s M m 1 for more than 10 layers. The authors also fabricated V 1 2 sq V Development of aqueous-based inks of functional materials is Nanoparticles composed of organic compounds can be used as 4 introduced an ammonia sensor based onby amperometric detection using inkjet printed dodecylbenzene sulfonatePANI (DBSA)–doped nanoparticles on screenresponse printed as carbon electrode. a Sensor printing function one of to filmsensor four was thickness PANI studied layers. was withammonium The a chloride investigated (0–80 variety sensitivity by of limit different of concentrations this of (ammonium). of critical importance for inkjetsuch printing endeavors applications. Success will of allowtechnology. a In wider this entry sense,laboratory and a tool adoption for desktop of materials inkjetAlong inkjet discovery can and truly device these fabrication. become lines, a Jang 8. Sensors and Detectors Sensors play an importantand role safety-based in applications. industrial,sensors transport There including security are photodetectors, gas numerousstress sensors. sensors, classes In and this of mechanical section,sensors we fabricated will examine using different inkjet types printing. of organic active materials dispersedapplications in lie aqueous in solutions. food Typical but and these drug industry, special as compoundscatalysis well have as in also cosmetics, been all used kinds in chemical of application areas. Crowley et al. pentacene transistorshigh on these mobilities substrates and found fairly limit of 2.58 intrinsically higher current densities, OLED applicationsrequire typically lower sheet resistances thanHowever, the with one appropriate found selection indesign of this of work. the the material injecting andthe contact, injection proper it barrier sufficiently, is as well potentially asacross possible reduce the to the voltage lower drop contact toapplications. use this technology in OLEDs and OTFT the number of10 printed layers). Sheet resistances were close to and cannot be depositedelevated using temperatures. thermal evaporative Thedependence methods of at authors the found resultingderivatives on sheet the an number resistance of inverse printed of layers printed (for linear TCNQ 0.12 cm 15 days of testing period and with a response level of 1 m 4 at ¼ ¼ 1 sq -TCNQ) -TCNQ fabricated , and 70% 14 V 14 1 (C [79] showed sheet 9 sq 4M [77] m thick polyethy- > V 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim m r at 30 prints). On the ß 1 carboxyl functionalized sq at 100 kHz. Based on their V [76] V (minimum of 30 prints) when 115 k 1 r sq V m long, were mixed with PEDOT:PSS and m reported on fabrication of photonic bandgap [78] 673–685 22, , ), with an inkjet printing process. They chose a 1 2010 Sensitivity of PANI-PSS films as a function of NH3 concentration (a). Increasing bis ethylenedioxy tetrathiafulvalene and C . Impedance analysis exhibited a similar trend: an increase V ¼ Inkjet printing can be employed at room temperature. Hence, Oyhenart, et al. As reported by Mustonen et al. thickness and decreasingReproduced with sensing permission area from [82]. has Copyright 2007, a Wiley-VCH. positive impact on sensorAdv. Mater. sensitivity (b,c). Figure 6. (BO 5.7 k www.MaterialsViews.com it can address a larger classbeing of chemical otherwise compounds, which, well-suited while tobe desired device deposited structures, cannot Further, using plastic-based more electronicsinexpensive conventional offer and flexible deposition the substrates. methods. prospect Hiraoka, et of al. using relatively conductive polymer asexhibit enhanced conductive absorption at species optical like frequencies.in With metals increase the number ofauthors printed found an layers increase of inwell-defined the the transparency frequencies patterned of up structure, the to structureresult the at 100 of GHz. multilayer While interference, thissignature the of could authors the be claim onset a this of photonic to bandgap be behavior. a printed on paper or plastic substrates. resistivity values of 40 k 12 S cm structures using a conductive polymer (PANI: conductivity other hand, for thick layersink, of there composite was ink no significant versus difference just inwere polymer conductivity. Both shorted films with sheet resistance about 1 k transparency in theMWCNT visible (MWCNT-COOH) suspended spectrum. in water Similarly, functionalized patterned thin films of conductive compounds: BO in the numberimpedance values from of 517 to printedobservations, 7.4 k these layers printed resultedfrequency SWCNTs in electronic could abandwidth devices be in decrease Ohmic due used characteristics. in in to high the measured 10 MHz SWCNT (SWCNT-COOH),composites and patterns were PEDOT:PSS/SWCNT-COOH fabricatedcase, they by aimed at inkjet printing printing.photo conductive and paper, In transparent as this films well on diameter and as 0.5–1.5 on PET substrates. Nanotubes, 4–5 nm 50 prints).reasonable However, sheet resistance ( printed patterns on photo paper had lene naphthalate (PEN) base films.the Inkjet printing deposition was method chosen as as the compound is thermally unstable tetradecyltetracyano-quinodimethane) on 125 printed using a desktop printerDMP-2831 (CanonBJC-4550), and materials a Dimatix printer.poor Bare adhesion nanotubes and on PET high showed sheet resistance ( 682 PROGRESS REPORT geP msindcesssgicnl hnemission when significantly 2 decreases than larger is emission wavelength PL HgTe 3 to up for detector wavelengths a of demonstration reported authors the Interestingly, hwdsniiiyo 5mAW device 65 layer find of six sensitivity to A showed light. order incident absorb in to investigated thickness film were sufficient layers nanocrystal printed Differ- were electrodes. ent Ti/Au detectors interdigitated The evaporating glass. by on completed printed and %) wt (2 chlorobenzene 1.4 estvt nrae iery ecig60m W mA 600 reaching linearly, increased sensitivity on htterssac ftecmoiefl to fell they composite the Surprisingly, of apparatus). resistance the the below measurement that reported found the was of (current sensitivity atmosphere nitrogen measured when a conductivity under low very found a They on substrate. films PET composite transparent printed and SWCNTs distribute ae nike rne gennprils tteroom the At nanoparticles. HgTe of detectivity printed a inkjet temperature, on based nrae safnto ficesn rne aes(,) erdcdwt emsinfo [80]. from permission with Reproduced (d,e). layers Wiley-VCH. 42 printed 2007, increasing and Copyright of 1 function with a photodetectors as layer increases 6 the of characteristics 7. Figure h l a xoe oabet h eitneo biopolymer a of resistance The ambient. to exposed was film the www.advmat.de ahi tal. et Panhuis Bo m ¨ aeeghwsosre.HT rsaswr ipre in dispersed were crystals HgTe observed. was wavelength m br tal. et rberl )1 genncytlsrpswt nedgttdeetoe.Lna n oaihi IV logarithmic and Linear electrodes. interdigitated with stripes nanocrystal HgTe 16 a) [83] [84] eosrtdahgl estv photodetector sensitive highly a demonstrated m sdcie ofrainbooyesto biopolymers conformation coiled used ,wihi eakbecnieigthat considering remarkable is which m, m Fg 7). (Fig. m D 1 * t1 .I swrhntn htthe that noting worth is It V. 10 at ¼ 3.9 10 ß 10 00WLYVHVra mH&C.Ka,Weinheim KGaA, Co. & GmbH Verlag WILEY-VCH 2010 mHz cm 2M 12 m bc.Sniiiyo h detectors the of Sensitivity (b,c). W 12 1 V t7 V. 70 at W when 1 at rget—ycaigtecnieeswt ho-ikdsingle build additively to thiol-linked method a with reported They oligomers. cantilevers DNA strand the in gene coating pH of detection and for fragments—by approach concentrations similar a ionic used authors to The liquids. cantilevers the the enhance of layers sensitivity SAM These structures. cantilever gold-coated usinginkjetprinting.SAMlayersofalkanethiolsweredepositedon demonstratedthefabricationofnanoscalecantilever-basedsensors )bsdsnosivletedpsto ffntoa aesto layers al. et functional Bietsch tasks. of sensing biochemical deposition and chemical the perform involve sensors S)-based sensor. humidity a this use as to device possible is printed the it enhance when enhancement, of conductivity this Regardless also electrolytes of behavior. origins other observed or aqueous this can for consider 8). explanations not of do candidate vapor authors (Fig. The presence ambient. water the matrix to to exposed nanotube– of biopolymer due the the presence conductivity in of the due pathways is swelling However, vapor the water conductivity mechanical of in in to presence in change change junctions a M biopolymernanotube The 350 to was conditions. one attributed composite ambient the as under geometry similar with film o oeapiain,mcoeetoehnclsse (MEM- system micro-electromechanical applications, some For eetatceo i-rnigb Derby. by bio-printing on article recent mle ipne rp flvn systems, living achieve al. et To of Jayasinghe level. drops industrial dispensed an smaller can to this shape. scaled process, and be printing a size involves it defined reproducible Since tightly of of fabrication vesicles is precursors for such important of minute, quantities of introduction the controlled amphiphiles The solution. called from a into precursors The proceeds of solution. vesicles printing liquid of a assembly into entities these utyb n-e rnignnpril Au nanoparticle printing colloids. metal ink-jet by cir- cuitry electrical and MEMS three-dimensional noyoi n xctss Hauschild exocytosis. al. et and as endocytosis such processes an secretory in play role cells, important living in and such screening, drug applications as biomedical in used extensively are range size nanometer the in Vesicles Applications Pharmaceutical and Biological 9. oarve ntesbetb ue al. et Yu by subject the on scope review directed a is the to reader The pharmaceutical beyond work. this well of intent and and and vast is research prototyping, testing, drug rapid to technologies printing applica- of the tion on deposited literature the The to systems. living harmful high was to fields exposure electric the that evidence and no experiment found this variety for a The cells for as human living well of as suspensions. size cells, Jurkat in colloidal used authors micrometers of few formation a deposits [86] eosrtdamto oprint to method a demonstrated [87] sdEJt omdroplet form to EHJ used d.Mater. Adv. www.MaterialsViews.com 2010 , 22, [88] 673–685 n a and [89] [85] V PROGRESS REPORT 683 www.advmat.de However, in the [94] as reactive ion etching. 11. Summary Materials deposition processes for OTFTs, OLEDs, solar cells,the etc. use currently of involve eitherdeposition spin-coating approaches; or vacuum inkjet in printing aone was few or more utilized layers cases ofUnlike the to inkjet device structure. printing, deposit traditionaltion deposi- approaches involvewasted a material, greatuniform but deal deposition profiles result of over in the sub- a fairly case of polymercesses layers, are often too dry aggressive, leaving etchingetching wet methods pro- as a viable solutionfine to the etching problemUse for of these inkjetsolvent systems. printing helps to to simplifyprocess, dispense bypassing the etch the wet lithographic etching definition, mask exposuresteps. However, and much workseveral is development fronts needed including shrinking on pattern- ing dimensions, minimizingnozzle clogging region, and others, of before inkjet can be adopted in atronics wide manufacturing. range of microelec- There is significant scope for wider industrial application of strate. By contrast,deposition inkjet process printing that is lendsmaskless itself an processing. readily Given anisotropic the to inherent (localized) cost patternedin of writing/ lithography steps industrial manufacturenumber and and level of theprovides complication an imperative of attractive, such material-conserving to steps, alternativepatterning inkjet for applications. reduce However, several printing the the anisotropic natureprinting of inkjet also givesprocessing currently rise used in to industry.polymers The issues tendency of and not dissolved suspensions encountered other to in form nanoparticle planar coffee-ring-likeeffect of structures species the is surface-tension-driven transport in ansurface of with inevitable solutions an along solutions evaporating solvent. a Significant progressachieved and has been indrawbacks recent on film work uniformityplete to and coverage device minimize due performance.prepatterned Incom- to the substrates coma can impact formationpatterned be during deposition of obviated process spin-coating such such through on asinkjet the inkjet printing printing. use In is of closing, deposition also a of a alocations suitable on given a substrate process having material pre-existing in structuresthat and must devices situations would, occur where otherwise, invacuum be or predetermined spin-coating contaminated process were and/orrecent used. Given progress damaged the and impressive extension if ofmaterials inkjet a printing deposition, to novel areas wetechnology of in anticipate applied science a and engineering. strong futureinkjet printing for technologies. Current this trendstions in of research inkjet applica- printingthe yield the technology first may impression have that peaked. the However, use current of work using 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ß [90] An insulator layer of PVP [91] demonstrated such a patterning [92] 673–685 have also demonstrated similar capabilities. They 22, , . While conservation of OLED materials was not the [93] 2 2010 Response to water vapor with various printed film compositions are shown in (a,b). Inkjet printing offers resolutions in the micrometer range, and hence it is a potential technique forapplications dispensing etching like species, flat-panel in displays,various etc. elements The through ability inkjetwas to printed demonstrated integrate interconnects by Kawase and et vias al. Adv. Mater. 10. Inkjet Patterning It has been stressed before thatthe the use need of for inkjet printing conventionallayers. obviates It lithography is thus appropriate in at this depositionthis, point to of such consider the printed inverse as of etch-dispensing use process. Such of use of inkjetin inkjet situations printing printing is that beneficial involve aspredeposited the a material, removal such of patterning as very orin in small etching the fraction as of multi-step of an isolation standard a dielectrics CMOS process. Figure 8. Nanotube-gellan gum dispersionconductivity. c) is Printed MWCNTs hypothesizedReproduced and to with gellan permission gum lead from films [81]. to show Copyright no better 2007 response Wiley-VCH. responsivity to organic due compounds to better www.MaterialsViews.com focus of thisprocessing offered work, by use it of inkjetGans nevertheless printing et as demonstrates al. an etching flexibility tool. de in studied the dependence ofdrops, via radius as on well theprinted number as drops, of widths and printed of foundexperiment. good etched Generally, agreement grooves wet betweenresolution on etching theory than the is the and commonly density known used of to dry etching have processes, such a lower technique by printing solvent dropslayer to onto form a OLEDs. They spin-coated used insulator ethanola as layer a solvent, of printed PVP, on to and800 reported cd devices m with a brightness of around was successfully etcheddemonstrated inverter circuits by with frequencies printingrecently, of 250 drops Xia Hz. More of and ethanol. Friend They 684 PROGRESS REPORT 1]A .J a e eg .J mt,J eear .Sho,S Koltzenburg, S. Schrof, W. Perelaer, J. Smith, J. Perelaer, P. Berg, J. den van Smith, J. M. J. A. P. Mukhopadhyay, [16] K. Laat, D. Adair, d. K. Barton, M. K. Kang, W. J. S. Hardy, A. M. Park, Berg, J.-U. den [15] van J. M. A. [14] 1]A .Ggai .Chandra, S. Goghari, A. A. [13] 1]V .Kaakr .D nesn .C unvl,H .E Meijer, E. H. H. Duineveld, C. P. Anderson, D. P. Khatavkar, Hsieh, V. V. H. P. Chou, [12] H. H. Hwang, S. W. Tsai, Schubert, S. H. U. M. Berg, den [11] van J. M. A. Hendriks, E. C. Smith, J. P. Perelaer, J. [10] otakFJFL iai,Ic o hispot ..adG.E.J. and Optics the Modern and of School under Finland. Graduate P.D. Photonics, the Laboratory acknowl- and program like theirsupport. H.M.H FiDiPro Research the and edge Army for G.E.J. would W911NG-04-2-0005. the Inc. Agreement G.E.J. Cooperative from Denko Dimatix, Center. funding Nitto FUJIFILM from acknowledge Photovoltaics funding thank Advanced acknowledge to to and like would Technology G.E.J. and M.S. Acknowledgements field. further exciting facilitate to very printing this inkjet in during advances process of flow understanding fluid fundamental in great the the done be A address to printing. remains to work with of likely deal achievable are resolutions minimum field of this issue in developments interest, further great acquired and recently has techniques EHJ-based QDs. of as Use such systems low-dimensional for incorporating for superlattices PVs layers applications, hybrid OLED thin and active (NLO) with optically optics solutions of non-linear dilute deposition very times, from printing SAMs long better fluid of suitable to deposition of used of be the With can attempt reduction study amount This dimension. reduced. further for minimum be can vertical dispensable possibilities the the advancements, up in technological open growth of to deposited properties previously of controlled likely or flow is coverage substrate the the layers two-dimensional of with droplets understanding and interacting better uniformity A on substrates. been focus the that has suggests applications various across printing inkjet www.advmat.de 7 .Broo .Buau,G ac,D Bonn, D. 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