Nanoparticle Inks for Printed Electronics

1 NanoMas Technologies, IncNanoMas Technologies, IncNanoparticle inks Nanoparticle inks for Printed Electronicsfor Printed ElectronicsZhihaoZhihaoYangYangPresident & CTOP resident & CTONanoMas Technologies, Technologies, Revolutions in Electronics Technology Revolutions in Electronics for the Past 100 Yearsfor the Past 100 Years Vacuum Tube Transistors: 1906 Vacuum Tube Transistors: 1906 by Lee De Forest by Lee De Forest Solid State Transistors: 1947 by Solid State Transistors: 1947 by John Bardeen and Walter John Bardeen and Walter Brattain (Bell Telephone Brattain (Bell Telephone Laboratories)Laboratories) Integrated Circuits: 1958 by Jack Integrated Circuits: 1958 by Jack KilbyKilby(Texas Instruments)(Texas Instruments)What Next?What Next? The industry has followed the prediction of MooreThe industry has followed the prediction of Moore s Law s Law for the last 40 years without major technology the last 40 years without major technology revolution.

2 MooreMoore s Laws Law: The number of transistors per unit area is : The number of transistors per unit area is doubling every years. doubling every years. >>>>Gordon Moore (founder of Gordon Moore (founder of Intel Corporation).Intel Corporation). MooreMoore s Law is reaching its physical limit in next 5 to 10 s Law is reaching its physical limit in next 5 to 10 years. years. What will be the next technology revolution in the What will be the next technology revolution in the Electronics industry? Electronics industry?Look beyond the SiliconPentacene organic circuits on polymeric or cloth substrates Polymeric substrate AMLCDa"Si:H active matrix Gamma ray detector on polyimide substrate a"Si:H strain bridge arrayPlastic solar cellLowLow--Cost ICs on Arbitrary SubstratesCost ICs on Arbitrary SubstratesLarge Area & Flexible DisplaysLarge Area & Flexible DisplaysWorld's thinnest flexible active"matrix display (Philips)Flexible active matrix e"paper SVGA display (Plastic Logic)World's first 3mm thick flexible digital watch (Citizen)The plastic TFT"LCD display (Samsung)LowLow--cost RFIDs and Disposable Electronicscost RFIDs and Disposable ElectronicsCurrent cost: 7 Current cost: 7""10 cents per tag10 cents per tagTarget cost: 1 Target cost.

3 1""2 cents per tag2 cents per tagPrinted Electronics ManufacturingPrinted Electronics ManufacturingTremendous Market Growth Potential for Tremendous Market Growth Potential for Printed Electronics in Next 20 YearsPrinted Electronics in Next 20 YearsRecent report by Recent report by IDTechExIDTechExpredicts the PE market will reach $300B in 2027predicts the PE market will reach $300B in 2027$ $2, $4, $6, $8, $10, $12, $14, $ in Million(Data from NanoMarkets LLC)2011 Total PE Reveue $12,385 (in Million)Printable Display, $3,801 RFID, $2,557 Printable Signage, $1,250 Printable Backplanes, $1,134 Printable Photovoltaic, $1,042 Other (21% Overall), $2,601 (Data from NanoMarkets LLC)Highly conductive and high resolution patterns fabricated using Highly conductive and high resolution patterns fabricated using lowlow>>cost and cost and rollroll>>toto>>roll processes (such as inkjet and gravure printing) are one of roll processes (such as inkjet and gravure printing) are one of the most the most critical technology components in making Printed Electronics andcritical technology components in making Printed Electronics anddisplaysdisplaysMarket of Applications: Market of Applications: Flat panel display backplanes (TFT electrodes and busFlat panel display backplanes (TFT electrodes and bus>>bars) bars) EMI Shielding : plasma display, LCD, etc EMI Shielding : plasma display, LCD, etc RFID tagsRFID tags Electroluminescent lighting Electroluminescent lighting Printed circuit boards (PCBs) Printed circuit boards (PCBs) Touch screensTouch screensPrinted ConductorsPrinted ConductorsNanoMas Solutions:Make conducting patterns using metal Nanoparticle inks !

4 Technology Comparison for Printed ConductorsTechnology Comparison for Printed Conductors1010010>110010>110>610>510>410 >310>210 102103104105106 conductive PolymersCarbon NanotubesSputtered ITOR esistivityConductivity(Ohm>cm)(S/cm)Silv er Micro>Powder PastesEvaporated MetalsMetal Nanoparticle InksPrintableVacuum ProcessedSizeSize--Dependent Melting Point of NanoparticlesDependent Melting Point of Nanoparticles232b mss lms slT TT L R = Ph. Ph. BuffatBuffatand Jand J>>P. P. BorelBorel, , Phys. Phys. Rev. A,Rev. A,1313, 1976, 1976, 2287, 2287 Small particle size (in nanometers) Small particle size (in nanometers) significantly reduces the melting significantly reduces the melting temperature of NPs from the bulk temperature of NPs from the bulk melting point, allowing for very low melting point, allowing for very low processing temperatures (based on processing temperatures (based on surface melting) for sintering NPs surface melting) for sintering NPs into conducting conducting inks for Printed ElectronicsNanoparticle inks for Printed Electronics200 nmDeposited Ag nanoparticlesConductive Ag film on PET cured from Printed Nanoparticle inks nanoparticles can be stabilized in ink solutions by organic nanoparticles can be stabilized in ink solutions by organic ligandligandshells, which can be removed after printing.

5 Shells, which can be removed after printing. nanoparticles can be further cured or sintered to highly conductNanoparticles can be further cured or sintered to highly conductive ive films at low at low >150 C70>90 C150 CNanoMas Proprietary Technology: Producing High Quality NanoMas Proprietary Technology: Producing High Quality NanoparticlesNanoparticleswith Largewith Large--Scale and LowScale and Low--Cost ProcessesCost ProcessesA 50L pilot production A 50L pilot production reactor at NanoMasreactor at NanoMasNanoMas NanoMas silver silver nanoparticles nanoparticles with 5with 5>>6 nm 6 nm in size (SEM)in size (SEM)NanoMas Ag Nanoparticle powders and inksNanoMas Ag Nanoparticle powders and inksNanoMas Proprietary Printable Metal NanoMas Proprietary Printable Metal Nanoparticle conductive inks TechnologyNanoparticle conductive inks Technology Unique all solution based Nanoparticle synthesis technology Unique all solution based Nanoparticle synthesis technology (patent pending), widely compatible with the low cost (patent pending)

6 , widely compatible with the low cost production processes in the chemical industryproduction processes in the chemical industry Low cost and fully scalable to large scale mass productionLow cost and fully scalable to large scale mass production Scaled up to pilot production with a 50 litter reactorScaled up to pilot production with a 50 litter reactor UltraUltra>>small Nanoparticle size (2 to 10 nm) with specially small Nanoparticle size (2 to 10 nm) with specially designed surface chemistry allows low annealing designed surface chemistry allows low annealing temperature, short process time, and high conductivitytemperature, short process time, and high conductivity Variety of surface chemistry for different solvent dispersion Variety of surface chemistry for different solvent dispersion and applicationsand applications Low resistivity (as low as ~ Low resistivity (as low as ~ OPOP>>ccm, of pure Ag) m, of pure Ag) Low process temperature (as low as ~90 Low process temperature (as low as ~90 C) compatible with C) compatible with most plastic substratesmost plastic substrates Also curable by laser or UV light at room temperatureAlso curable by laser or UV light at room temperatureNano>Au (4 nm) Nanoparticle solution in cyclohexaneNano>Ag (5 nm) Nanoparticle solution in cyclohexaneAg nanoparticles in cyclohexane( max~ 416 nm)Au nanoparticles in cyclohexaneUV>Vis Absorption Spectra of Au and Ag Nanoparticle SolutionsUVUV--visvisCharacterization of NanoMas Characterization of NanoMas Gold and Silver NanoparticlesGold and Silver NanoparticlesNano-AgNano-AuNanoMas Au nanoparticles (<5 nm)NanoMas Au nanoparticles (<5 nm)TEMDSC DSC: exothermic sintering between 180 C and 210 C TGA: ~10>15% weight loss between 180 C and 250 C due to loss of surface capping agent Resistivity: ~8 OP>cm (annealed at 200 C, 3x of bulk Au) DSC.

7 Exothermic sintering between 110 C and 160 C TGA: ~10% weight loss between 100 C and 200 C due to loss of surface capping agent Resistivity: BC"cm (annealed at 150 C, of bulk Ag)ECD Distribution of ZHY>050616 by TEM> [nm]FrequencyFrequency DataLognormal FitMetricValueMean ECD [nm] Dev ECD [nm] ECD [nm] GMD [nm] GSD [nm] Ag nanoparticles NanoMas Ag nanoparticles Particle size: 6 1 nmDSCsinteringCore radius: 23 1 Core radius : Shell thickness: 6 1 sample detectorIncident neutronScattered neutronSmall Angle Neutron Scattering (SANS) Small Angle Neutron Scattering (SANS) Characterization of NanoMas NanoCharacterization of NanoMas Nano--Ag Ag SANS spectra confirmed that the Nano>Ag has an Ag core diameter of nm and a nm thick shell in solvent or a nm shell in packed (solid) state.> > > > > > Intensity (cm>1)Log (Q) [A] SANS Data Core>Shell Model FittingCore radius: 23 1 Core radius : Shell thickness: 6 1 SANS on NanoSANS on Nano>>Ag Solutions Ag Solutions (10 wt% in d(10 wt% in d>>Toluene)Toluene) (cm>1)Q (A) Qmax= >1interparticle distance ~ nmSANS of Packed NanoSANS of Packed Nano>>Ag (Solid)Ag (Solid)Cabot PED (20>30 nm)Cima NanoTech(80>100 nm)NovaCentrix(~20 nm broad distribution)ManoMas (~ 5 nm)Superior Performance of NanoMas Superior Performance of NanoMas NanoSilverNanoSilverInks inks due to the Ultradue to the Ultra--Small Nanoparticle SizeSmall Nanoparticle Size2520151050 Resistivity ( >cm)250200150100 Annealing Temperature (C)NanoMas NanoAg (5 nm)NanoAg (~25 nm)from competitors Ag bulk resistivityPETK aptonPrinted conductive Patterns on Plastic MHz RFID antenna Printed on PET and polyimideMiniature RF coil Printed on PETP rinted flex circuit on polyimideInkjet Printed Inkjet Printed NanoSilverNanoSilverContacts in Contacts in Fabricating aFabricating a--Si:HSi.

8 HTFTsTFTson Glasson GlassSourceDrainAg (~ 30 nm)Cr (~ 5 nm)n+ a-Si:H (~ 50 nm)a-Si:H (~ 200 nm)a-SiNx:H (~ 300 nm)Cr (~ 35 nm)Glass SubstrateProbes>10 0 10 20 30 4010>610>510>4 IDS (A)VGS (V)VDS = 40 V L = 110 um L = 140 um0100200 IDS (uA)~ ~ ~ ~ (V)(V)~ ~ ~ ~ ((cmcm22/Vs/Vs))140140110110L (L ( m)m)* Data curtsey of Dr. * Data curtsey of Dr. YongtaekYongtaekHong of Hong of Seoul National University, Korea Seoul National University, Korea Single crystal silicon gateSilicon dioxide gate dielectricAgAgPQTP rinted Printed NanoSilverNanoSilverContacts in Contacts in Fabricating Organic Fabricating Organic TFTsTFTs Organic Semiconductor: poly(3,3 Organic Semiconductor: poly(3,3 >>didodecyldidodecyl>>quaterthiophenequa terthiophene) or PQT) or PQT>>1212 Source and drain Printed with NanoMas Source and drain Printed with NanoMas NanoSilverNanoSilverinks and annealed at 145inks and annealed at 145 CC Device channel length of ~43 um and Device channel length of ~43 um and width of ~300 umwidth of ~300 um No obvious contact resistance No obvious contact resistance * Data curtsey of Dr.

9 * Data curtsey of Dr. JurgenJurgenDaniel of PARC Daniel of PARC Inkjet Printed Inkjet Printed TFTsTFTswith with ZnOZnOand Ag and Ag Nanoparticle InksNanoparticle inks Print or coat with ZnO Nanoparticle ink Heat step at 200 C to anneal Print silver nanoparticles for source/drain, and annealed at 150 CMobilities: cm2/Vs On/Off: ~ > > > > > > >04>30 >10 10 30 50 VgLog(Id) + > > > >03 ZnO TFT with Printed Ag contactsAbout CostAbout What Printed Electronics should shoot for are high What Printed Electronics should shoot for are high productivity, large size and volume, high flexibility, and productivity, large size and volume, high flexibility, and ultimately the LOW the LOW COST. The Nanoparticle inks should also be made by LOW COST The Nanoparticle inks should also be made by LOW COST NanoMas makes sure all the nanoNanoMas makes sure all the nano>>materials it makes can materials it makes can be mass produced with LOW COST mass produced with LOW COST ProductionMass ProductionPilot ProductionPilot ProductionFunctional Functional NanomaterialsNanomaterials Silver Silver nanoparticlesnanoparticles Gold Gold nanoparticlesnanoparticles Carbon Carbon nanotubesnanotubes Carbon Carbon nanofibersnanofibers Decorated carbon Decorated carbon nanotubesnanotubes Magnetic Magnetic nanoparticlesnanoparticles Novel catalysts for making Novel catalysts for making carbon carbon nanomaterialsnanomaterialsNanoMas Technology and Product RoadmapNanoMas Technology and Product Roadmap NanoMas current products include NanoMas current products include NanoSilverNanoSilver and and NanoGoldNanoGold conductive inks .

10 conductive inks . Under development with its proprietary technology, NanoMas will Under development with its proprietary technology, NanoMas will also also provide inorganic Nanoparticle and polymer semiconductor inks , aprovide inorganic Nanoparticle and polymer semiconductor inks , as well s well as electroluminescent (EL or LED) inks for PE applications. as electroluminescent (EL or LED) inks for PE applications. NanoMas also has the technologies to mass produce high quality cNanoMas also has the technologies to mass produce high quality carbon arbon nanotubesnanotubesand carbon and carbon Electronics & DisplaysPrintable Electronics & Displays Silver Nanoparticle inksSilver Nanoparticle inks Gold Nanoparticle inksGold Nanoparticle inks ELEL Nanoparticle inksnanoparticle inks Semiconductor Nanoparticle inksSemiconductor Nanoparticle inks Polymer semiconductor inks Polymer semiconductor inks Inorganic dielectric inksInorganic dielectric inks Polymer dielectric inks Polymer dielectric inks NanoMas Product PortfolioOther Other NanomaterialsNanomaterialsDeveloped at Developed at NanoMas Technologies, Technologies, Technologies, IncNanoMas Technologies, IncNanoMas Technologies, Inc.