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NanoMas Technologies, Inc NanoMas Technologies, Inc Nanoparticle Inks Nanoparticle Inks for Printed Electronics for Printed Electronics Zhihao Zhihao Yang Yang President & CTO President & CTO NanoMas Technologies, Inc. NanoMas Technologies, Inc. [email protected] [email protected]

Nanoparticle Inks for Printed · PDF fileNanoparticle Inks for Printed Electronics ... • Nanoparticles can be stabilized in ink solutions by ... • Also curable by laser or UV light

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NanoMas Technologies, IncNanoMas Technologies, Inc

Nanoparticle Inks Nanoparticle Inks

for Printed Electronicsfor Printed Electronics

ZhihaoZhihao YangYangPresident & CTOPresident & CTO

NanoMas Technologies, Inc.NanoMas Technologies, [email protected]@nanomastech.com

Technology 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 revolution.for the last 40 years without major technology revolution.

MooreMoore’’s Laws Law: The number of transistors per unit area is : The number of transistors per unit area is doubling every 1.5 years. doubling every 1.5 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 Silicon

Pentacene organic circuits on polymeric or cloth substrates

Polymeric substrate AMLCD

a-Si:H active matrix Gamma ray detector on polyimide substrate

a-Si:H strain bridge array

Plastic solar cell

LowLow--Cost ICs on Arbitrary SubstratesCost ICs on Arbitrary Substrates

Large Area & Flexible DisplaysLarge Area & Flexible Displays

World'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 Electronics

Current cost: 7Current cost: 7--10 cents per tag10 cents per tag

Target cost: 1Target cost: 1--2 cents per tag2 cents per tag

Printed Electronics ManufacturingPrinted Electronics Manufacturing

Tremendous Market Growth Potential for Tremendous Market Growth Potential for

Printed Electronics in Next 20 YearsPrinted Electronics in Next 20 Years

Recent report by Recent report by IDTechExIDTechEx predicts the PE market will reach $300B in 2027predicts the PE market will reach $300B in 2027

$0.0

$2,000.0

$4,000.0

$6,000.0

$8,000.0

$10,000.0

$12,000.0

$14,000.0

2006 2007 2008 2009 2010 2011

Year

$ 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 and displaysdisplays

Market 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 screens

Printed ConductorsPrinted Conductors

NanoMas Solutions:Make conducting patterns using metal nanoparticle inks!

Technology Comparison for Printed ConductorsTechnology Comparison for Printed Conductors

10 100 10-1

10010-1

10-610-510-410-310-2

10 102 103 104 105 106

Conductive Polymers

Carbon Nanotubes

Sputtered ITO

Resistivity

Conductivity

(Ohm-cm)

(S/cm)

Silver Micro-Powder Pastes

Evaporated Metals

Metal Nanoparticle InksPrintable

Vacuum Processed

SizeSize--Dependent Melting Point of NanoparticlesDependent Melting Point of Nanoparticles

232

b m s

s l

m s s l

T T

T L R

ργ γ

ρ ρ

− = −

Ph. Ph. BuffatBuffat and 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 films.into conducting films.

Nanoparticle Inks for Printed ElectronicsNanoparticle Inks for Printed Electronics

200 nm

Deposited 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. 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 temperatures.films at low temperatures.

100-150°C70-90°C

150°C

NanoMas Proprietary Technology: Producing High Quality NanoMas Proprietary Technology: Producing High Quality

NanoparticlesNanoparticles with Largewith Large--Scale and LowScale and Low--Cost ProcessesCost Processes

A 50L pilot production A 50L pilot production reactor at NanoMasreactor at NanoMas

NanoMas 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 inks

NanoMas 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), 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 ~2.3 Low resistivity (as low as ~2.3 µΩµΩ--ccm, 1.5x of pure Ag) m, 1.5x of pure Ag) •• Low process temperature (as low as ~90Low 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 temperature

Nano-Au (4 nm) nanoparticle solution in cyclohexane

Nano-Ag (5 nm) nanoparticle solution in cyclohexane

Ag nanoparticles in cyclohexane(λmax ~ 416 nm)

Au nanoparticles in cyclohexane

UV-Vis Absorption Spectra of Au and Ag Nanoparticle Solutions

UVUV--visvis Characterization of NanoMas Characterization of NanoMas

Gold and Silver NanoparticlesGold and Silver Nanoparticles

Nano-Ag

Nano-Au

NanoMas Au Nanoparticles (<5 nm)NanoMas Au Nanoparticles (<5 nm)

TEMDSC

• DSC: exothermic sintering between 180ºC and 210ºC

• TGA: ~10-15% weight loss between 180ºC and 250ºC due to loss of surface capping agent

• Resistivity: ~8 µΩ-cm (annealed at 200°C, 3x of bulk Au)

• DSC: exothermic sintering between 110ºC and 160ºC• TGA: ~10% weight loss between 100ºC and 200ºC due to loss of surface capping agent• Resistivity: 2.4 µΩ-cm (annealed at 150°C, 1.5x of bulk Ag)

ECD Distribution of ZHY-050616 by TEM

-0.05

0.00

0.05

0.10

0.15

0.20

0.25

0.30

1 10 100

ECD [nm]

Frequency

Frequency Data Lognormal Fit

Metric ValueMean ECD [nm] 5.72Std Dev ECD [nm] 1.79Count 726GMD ECD [nm] 5.43GSD 1.41Fit GMD [nm] 5.98Fit GSD [nm] 1.24

TEM

NanoMas Ag Nanoparticles NanoMas Ag Nanoparticles

Particle size: 6 ±1 nm

DSC

sintering

Core radius: 23 ± 1 ǺCore radius σ: 5.5 ǺShell thickness: 6 ±1 Ǻsample

θ

detector

Incident neutron

Scattered neutron

Small 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 4.6 ±1.1 nm and a 0.6 ±0.1 nm thick shell in solvent or a 0.3 nm shell in packed (solid) state.

-2.0 -1.5 -1.0 -0.5

-1.0

-0.5

0.0

0.5

1.0

Intensity (cm

-1)

Log (Q) [A]

SANS Data Core-Shell Model Fitting

Core radius: 23 ± 1 ǺCore radius σ: 5.5 ǺShell thickness: 6 ±1 Ǻ

SANS on NanoSANS on Nano--Ag Solutions Ag Solutions (10 wt% in d(10 wt% in d--Toluene)Toluene)

0.05 0.10 0.15 0.20 0.250

1

2

3

4

5

Intensity (cm

-1)

Q (A)

Qmax= 0.120 Ǻ-1

interparticle distance ~ 5.2 nm

SANS 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 NanoSilverNanoSilver Inks Inks

due to the Ultradue to the Ultra--Small Nanoparticle SizeSmall Nanoparticle Size

25

20

15

10

5

0

Resistivity (µΩ-cm)

250200150100

Annealing Temperature (C)

NanoMas NanoAg (5 nm)

NanoAg (~25 nm)from competitors

Ag bulk resistivity

PET Kapton

Printed Conductive Patterns on Plastic Substrates

13.56 MHz RFID antenna printed on PET and polyimide

Miniature RF coil printed on PET Printed flex circuit on polyimide

Inkjet Printed Inkjet Printed NanoSilverNanoSilver Contacts in Contacts in

Fabricating aFabricating a--Si:HSi:H TFTsTFTs on Glasson Glass

Source

Drain

Ag (~ 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 Substrate

Probes

-10 0 10 20 30 40

10-6

10-5

10-4

I DS (A)

VGS (V)

VDS = 40 V L = 110 um L = 140 um

0

100

200

I DS (uA)

~ 1.41~ 1.41~ 1.68~ 1.68VVTT (V)(V)

~ 0.97~ 0.97~ 0.91~ 0.91µµ ((cmcm22/Vs/Vs))

140140110110L (L (µµm)m)

* Data curtsey of Dr. * Data curtsey of Dr. YongtaekYongtaek Hong of Hong of Seoul National University, Korea Seoul National University, Korea

Single crystal silicon gate

Silicon dioxide gate dielectric

Ag AgPQT

Printed Printed NanoSilverNanoSilver Contacts in Contacts in

Fabricating Organic Fabricating Organic TFTsTFTs

•• Organic Semiconductor: poly(3,3 Organic Semiconductor: poly(3,3 --didodecyldidodecyl--quaterthiophenequaterthiophene) or PQT) or PQT--1212•• Source and drain printed with NanoMas Source and drain printed with NanoMas NanoSilverNanoSilver inks and annealed at 145inks and annealed at 145ººCC•• 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. * Data curtsey of Dr. JurgenJurgen Daniel of PARC Daniel of PARC

Inkjet Printed Inkjet Printed TFTsTFTs with with ZnOZnO and 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 150C

Mobilities: 0.1-0.15 cm2/Vs On/Off: ~105

1.0E-101.0E-091.0E-081.0E-071.0E-061.0E-051.0E-04

-30 -10 10 30 50

Vg

Log(Id)

0.0E+00

2.0E-03

4.0E-03

6.0E-03

8.0E-03ZnO TFT with printed Ag contacts

About CostAbout Cost……

•• 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 COST.ultimately the LOW COST.

•• The nanoparticle inks should also be made by LOW COST The nanoparticle inks should also be made by LOW COST processes.processes.

•• 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 processes.be mass produced with LOW COST processes.

LabLab Mass ProductionMass ProductionPilot ProductionPilot Production

Functional 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 nanomaterialsnanomaterials

NanoMas Technology and Product RoadmapNanoMas Technology and Product Roadmap

•• NanoMas current products include NanoMas current products include NanoSilverNanoSilver™™ and and NanoGoldNanoGold™™conductive inks. 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 nanotubesnanotubes and carbon and carbon nanofibersnanofibers..

Printable 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 Portfolio

Other Other NanomaterialsNanomaterials Developed at Developed at

NanoMas Technologies, Inc.NanoMas Technologies, Inc.

NanoMas Technologies, IncNanoMas Technologies, Inc

NanoMas Technologies, Inc. is an early stage startNanoMas Technologies, Inc. is an early stage start--up company, up company, located in the Innovative Technologies Complex (ITC) on the camplocated in the Innovative Technologies Complex (ITC) on the campus of us of Binghamton University (SUNY) in Binghamton, New York, where is aBinghamton University (SUNY) in Binghamton, New York, where is also lso the home of Center for Advanced Microelectronics Manufacturing the home of Center for Advanced Microelectronics Manufacturing (CAMM), funded by the USDC to lead the development of next (CAMM), funded by the USDC to lead the development of next generation rollgeneration roll--toto--roll (R2R) microelectronics manufacturing.roll (R2R) microelectronics manufacturing.

Innovative Technologies Complex Innovative Technologies Complex Suite 2109 Suite 2109 85 Murray Hill Road 85 Murray Hill Road Vestal, NY 13850Vestal, NY 13850

Phone: 607Phone: 607--821821--42084208Fax: 866Fax: 866--367367--1128 (toll1128 (toll--free)free)Website: Website: www.nanomastech.comwww.nanomastech.com