Nanoparticle Inks for Printed Electronics

(1)

NanoMas Technologies, Inc

Nanoparticle Inks

for Printed Electronics

Zhihao

Yang

President & CTO

NanoMas Technologies, Inc.

Technology Revolutions in Electronics

for the Past 100 Years

•

• Vacuum Tube Transistors: 1906

Vacuum Tube Transistors: 1906

by Lee De Forest

•

• Solid State Transistors: 1947 by

Solid State Transistors: 1947 by

John Bardeen and Walter

Brattain (Bell Telephone

Laboratories)

•

• Integrated Circuits: 1958 by Jack

Integrated Circuits: 1958 by Jack

Kilby

(3)

What Next?

The industry has followed the prediction of Moore

’

s Law

for the last 40 years without major technology revolution.

Moore

’

s Law

: The number of transistors per unit area is

_{: The number of transistors per unit area is}

doubling every 1.5 years.

--

Gordon Moore (founder of

Intel Corporation).

Moore

’

s Law is reaching its physical limit in next 5 to 10

years.

What will be the next technology revolution in the

electronics industry?

(4)

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

Low

(5)

Large 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)

(6)

Low

-

cost RFIDs and Disposable Electronics

Current cost: 7

Current cost: 7--10 cents per tag10 cents per tag Target cost: 1

(7)

Printed Electronics Manufacturing

(8)

Tremendous Market Growth Potential for

Printed 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 $ i n M il li o n

(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

(9)

Highly conductive and high resolution patterns fabricated using

Highly conductive and high resolution patterns fabricated using lowlow--cost and cost and roll

roll--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 and

critical technology components in making printed electronics and displaysdisplays

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 Conductors

NanoMas Solutions:

Make conducting patterns using

metal nanoparticle inks!

(10)

Technology Comparison for Printed Conductors

10 100 ₁₀-1 100 10-1 10-6 10-5 10-4 10-3 10-2 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 Inks

Printable

(11)

Size

-

Dependent Melting Point of Nanoparticles

2 3

2

b m s s l m s s l

T

L

R

ρ

γ

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)

significantly reduces the melting

temperature of NPs from the bulk

melting point, allowing for very low

processing temperatures (based on

surface melting) for sintering NPs

into conducting films.

(12)

Nanoparticle Inks for Printed Electronics

200 nm

Deposited Ag nanoparticles

Conductive 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

ligand

shells, which can be removed after printing.

•

• Nanoparticles can be further cured or sintered to highly conduct

Nanoparticles can be further cured or sintered to highly conduct

ive

films at low temperatures.

100-150°C 70-90°C

(13)

NanoMas Proprietary Technology: Producing High Quality

Nanoparticles

with Large

-

Scale and Low

-

Cost Processes

A 50L pilot production A 50L pilot production reactor at NanoMas reactor at NanoMas NanoMas NanoMas silver silver nanoparticles nanoparticles with 5 with 5--6 nm 6 nm in size (SEM) in size (SEM)

NanoMas Ag nanoparticle powders and inks

(14)

NanoMas Proprietary Printable Metal

Nanoparticle 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

production processes in the chemical industry

•

• Low cost and fully scalable to large scale mass production

Low cost and fully scalable to large scale mass production

–

Scaled up to pilot production with a 50 litter reactor

•

• Ultra

Ultra

-

small nanoparticle size (2 to 10 nm) with specially

designed surface chemistry allows low annealing

temperature, short process time, and high conductivity

•

• Variety of surface chemistry for different solvent dispersion

Variety of surface chemistry for different solvent dispersion

and applications

•

• Low resistivity (as low as ~2.3 µΩ

Low resistivity (as low as ~2.3

µΩ

-

c

m, 1.5x of pure Ag)

•

• Low process temperature (as low as ~90

Low process temperature (as low as ~90

°

C) compatible with

most plastic substrates

•

(15)

Nano-Au (4 nm) nanoparticle solution in cyclohexane Nano-Ag (5 nm) nanoparticle solution in cyclohexane Ag nanoparticles in cyclohexane (λ_max~ 416 nm) Au nanoparticles in cyclohexane

UV-Vis Absorption Spectra of Au and Ag Nanoparticle Solutions

UV

-

vis

Characterization of NanoMas

Gold and Silver Nanoparticles

Nano-Ag

(16)

NanoMas Au Nanoparticles (<5 nm)

TEM

DSC

• DSC: exothermic sintering between 180ºC and 210ºC

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

(17)

• 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] F re q u e n c y

Frequency Data Lognormal Fit

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

TEM

NanoMas Ag Nanoparticles

Particle size: 6 ±1 nm

DSC

sintering

(18)

Core radius: 23 ± 1 Ǻ Core radius σ: 5.5 Ǻ Shell thickness: 6 ±1 Ǻ sample

θ

detector Incident neutron Scattered neutron

Small Angle Neutron Scattering (SANS)

Characterization of NanoMas Nano

-

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 In te n s it y ( c m -1 ) Log (Q) [A] SANS Data

Core-Shell Model Fitting

Core radius: 23 ± 1 Ǻ Core radius σ: 5.5 Ǻ Shell thickness: 6 ±1 Ǻ

SANS on Nano

SANS on Nano--Ag Solutions Ag Solutions (10 wt% in d (10 wt% in d--Toluene)Toluene) 0.05 0.10 0.15 0.20 0.25 0 1 2 3 4 5 In te n s it y ( c m -1 ) Q (A) Q_max= 0.120 Ǻ-1 interparticle distance ~ 5.2 nm

SANS of Packed Nano

(19)

Cabot PED (20-30 nm) Cima NanoTech (80-100 nm) NovaCentrix (~20 nm broad distribution) ManoMas (~ 5 nm)

Superior Performance of NanoMas

NanoSilver

Inks

due to the Ultra

-

Small Nanoparticle Size

25 20 15 10 5 0

R

e

si

st

iv

ity

(

µΩ

-c

m

)

250 200 150 100

Annealing Temperature (C)

NanoMas

NanoAg (5 nm)

NanoAg (~25 nm)

from competitors

Ag bulk resistivity PET Kapton

(20)

Printed Conductive Patterns on Plastic Substrates

13.56 MHz RFID antenna printed on PET and polyimide

(21)

Inkjet Printed

NanoSilver

Contacts in

Fabricating a

-

Si:H

TFTs

on 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 ) V_GS (V) V_DS = 40 V L = 110 um L = 140 um 0 100 200 I D S ( u A ) ~ 1.41 ~ 1.41 ~ 1.68 ~ 1.68 V V_T_T (V)(V) ~ 0.97 ~ 0.97 ~ 0.91 ~ 0.91 µ µ ((cmcm22_/Vs_/Vs₎₎ 140 140 110 110 L ( L (µµm)m) * Data curtsey of Dr.

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

(22)

Single crystal silicon gate Silicon dioxide gate dielectric

Ag

PQT

Ag

Printed

NanoSilver

Contacts in

Fabricating Organic

TFTs

•

• Organic Semiconductor: poly(3,3 Organic Semiconductor: poly(3,3 - -didodecyl

didodecyl--quaterthiophenequaterthiophene) or PQT) or PQT--1212 •

• Source and drain printed with NanoMas Source and drain printed with NanoMas NanoSilver

NanoSilver 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 um

width of ~300 um

•

• No obvious contact resistance No obvious contact resistance

* Data curtsey of Dr.

(23)

Inkjet Printed

TFTs

with

ZnO

and Ag

Nanoparticle 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 cm

2

_/Vs

On/Off: ~10

5 1.0E-10 1.0E-09 1.0E-08 1.0E-07 1.0E-06 1.0E-05 1.0E-04 -30 -10 10 30 50 Vg L o g (I d ) 0.0E+00 2.0E-03 4.0E-03 6.0E-03 8.0E-03

(24)

About 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

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.

•

• NanoMas makes sure all the nano

NanoMas makes sure all the nano

-

materials it makes can

be mass produced with LOW COST processes.

Lab

(25)

Functional

Functional Nanomaterials

Nanomaterials

•

• Silver

Silver

nanoparticles

•

• Gold

Gold

nanoparticles

•

• Carbon

Carbon

nanotubes

•

• Carbon

Carbon

nanofibers

•

• Decorated carbon

Decorated carbon

nanotubes

•

• Magnetic

Magnetic

nanoparticles

•

• Novel catalysts for making

Novel catalysts for making

carbon

nanomaterials

NanoMas Technology and Product Roadmap

•

• NanoMas current products include

NanoMas current products include

NanoSilver

™

and

NanoGold

™

conductive inks.

•

• Under development with its proprietary technology, NanoMas will

Under development with its proprietary technology, NanoMas will

also

provide inorganic nanoparticle and polymer semiconductor inks, a

s well

as electroluminescent (EL or LED) inks for PE applications.

•

• NanoMas also has the technologies to mass produce high quality c

NanoMas also has the technologies to mass produce high quality c

arbon

nanotubes

and carbon

nanofibers

.

Printable Electronics & Displays

•

• Silver nanoparticle inks

Silver nanoparticle inks

•

• Gold nanoparticle inks

Gold nanoparticle inks

•

• EL

EL

nanoparticle inks

•

• Semiconductor nanoparticle inks

Semiconductor nanoparticle inks

•

• Polymer semiconductor inks

Polymer semiconductor inks

•

• Inorganic dielectric inks

Inorganic dielectric inks

•

• Polymer dielectric inks

Polymer dielectric inks

(26)

Other

Nanomaterials

Developed at

NanoMas Technologies, Inc.

(27)

NanoMas Technologies, Inc

NanoMas Technologies, Inc. is an early stage start

-

up company,

located in the Innovative Technologies Complex (ITC) on the camp

us of

Binghamton University (SUNY) in Binghamton, New York, where is a

lso

the home of Center for Advanced Microelectronics Manufacturing

(CAMM), funded by the USDC to lead the development of next

generation roll

-

to

-

roll (R2R) microelectronics manufacturing.

Innovative Technologies Complex

Suite 2109

85 Murray Hill Road

Vestal, NY 13850

Phone: 607

Phone: 607--821821--42084208 Fax: 866

Fax: 866--367367--1128 (toll1128 (toll--free)free) Website:

Nanoparticle Inks for Printed Electronics

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]

Technology Revolutions in Electronics

Technology Revolutions in Electronics

for the Past 100 Years

for 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

Kilby

What Next?

What Next?

The industry has followed the prediction of Moore

The 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.

Moore

Moore

’

’

s Law

s 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).

Moore

Moore

’

’

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?

_{: The number of transistors per unit area is}

_

_

_

_

_{− }

_

_

_