NanoMas Technologies, Inc
Nanoparticle Inks
for Printed Electronics
Zhihao Yang
President & CTO
NanoMas Technologies, Inc.
zhihao.yang@nanomastech.com
Technology Revolutions in Electronics
for the Past 100 Years
• Vacuum Tube Transistors: 1906
by Lee De Forest
• Solid State Transistors: 1947 by
John Bardeen and Walter
Brattain (Bell Telephone
Laboratories)
• Integrated Circuits: 1958 by Jack
Kilby (Texas Instruments)
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
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?
Look beyond the Silicon
Low-Cost ICs on Arbitrary Substrates
Polymeric substrate AMLCD
a-Si:H strain bridge array
Pentacene organic circuits on
polymeric or cloth substrates
Plastic solar cell
a-Si:H active matrix
Gamma ray detector on
polyimide substrate
Large Area & Flexible Displays
Flexible active matrix e-paper
SVGA display (Plastic Logic)
World's thinnest flexible activematrix display (Philips)
The plastic TFT-LCD
display (Samsung)
World's first 3mm thick
flexible digital watch
(Citizen)
Low-cost RFIDs and Disposable Electronics
Current cost: 7-10 cents per tag
Target cost: 1-2 cents per tag
Printed Electronics Manufacturing
Tremendous Market Growth Potential for
Printed Electronics in Next 20 Years
2011 Total PE Reveue $12,385 (in Million)
$14,000.0
$12,000.0
$ in Million
$10,000.0
(Data from NanoMarkets LLC)
(Data from NanoMarkets LLC)
Other (21% Overall),
$2,601
Printable Display,
$3,801
$8,000.0
$6,000.0
Printable
Photovoltaic, $1,042
$4,000.0
$2,000.0
Printable Backplanes,
$1,134
$0.0
Printable Signage,
2006
2007
$1,250
2008
RFID, $2,557
2009
2010
2011
Year
Recent report by IDTechEx predicts the PE market will reach $300B in 2027
Printed Conductors
Highly conductive and high resolution patterns fabricated using low-cost and
roll-to-roll processes (such as inkjet and gravure printing) are one of the most
critical technology components in making printed electronics and displays
NanoMas Solutions:
Make conducting patterns using
metal nanoparticle inks!
Market of Applications:
Flat panel display backplanes (TFT electrodes and bus-bars)
EMI Shielding : plasma display, LCD, etc
RFID tags
Electroluminescent lighting
Printed circuit boards (PCBs)
Touch screens
Technology Comparison for Printed Conductors
Vacuum Processed
Evaporated Metals
Sputtered ITO
Printable
Metal Nanoparticle Inks
Silver Micro-Powder Pastes
Carbon
Nanotubes
Conductive
Polymers
Resistivity
10
100
Conductivity 10-1 100
10-1
10-2
10-3
10-4
10-5
10-6 (Ohm-cm)
10
102
103
104
105
106
(S/cm)
Size-Dependent Melting Point of Nanoparticles
2

 ρs  3 
Tb − Tm
2 
=
γs −γl   
Tm
L ρ s Rs 
ρl  



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.
Ph. Buffat and J-P. Borel, Phys.
Rev. A, 13, 1976, 2287
Nanoparticle Inks for Printed Electronics
• 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 conductive
films at low temperatures.
70-90°C
100-150°C
Deposited Ag nanoparticles
Conductive Ag film on PET cured
from printed nanoparticle inks
150°C
200 nm
NanoMas Proprietary Technology: Producing High Quality
Nanoparticles with Large-Scale and Low-Cost Processes
NanoMas
silver
nanoparticles
with 5-6 nm
in size (SEM)
A 50L pilot production
reactor at NanoMas
NanoMas Ag nanoparticle powders and inks
NanoMas Proprietary Printable Metal
Nanoparticle Conductive Inks 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
– Scaled up to pilot production with a 50 litter reactor
• 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
and applications
• Low resistivity (as low as ~2.3 µΩ-cm, 1.5x of pure Ag)
• Low process temperature (as low as ~90°C) compatible with
most plastic substrates
• Also curable by laser or UV light at room temperature
UV-vis Characterization of NanoMas
Gold and Silver Nanoparticles
Ag nanoparticles in cyclohexane
(λmaxNano-Ag
~ 416 nm)
Au nanoparticles in
cyclohexane
Nano-Au
Nano-Au (4 nm)
nanoparticle
solution in
cyclohexane
Nano-Ag (5 nm)
nanoparticle
solution in
cyclohexane
UV-Vis Absorption Spectra of Au and Ag
Nanoparticle Solutions
NanoMas Au Nanoparticles (<5 nm)
DSC
TEM
• 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)
NanoMas Ag Nanoparticles
DSC
TEM
sintering
ECD Distribution of ZHY-050616 by TEM
0.30
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
0.25
• 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)
Frequency
0.20
0.15
0.10
0.05
0.00
-0.05
1
10
ECD [nm]
Frequency Data
Particle
size:Lognormal
6 ±1 Fitnm
100
Small Angle Neutron Scattering (SANS)
Characterization of NanoMas Nano-Ag
SANS of Packed Nano-Ag (Solid)
SANS on Nano-Ag Solutions
(10 wt% in d-Toluene)
1.0
SANS Data
Core-Shell Model Fitting
Scattered neutron
-1
Intensity (cm )
0.5
0.0
Incident neutron
5
sample-1.0
-1
Intensity (cm )
4
Qmax= 0.120 Ǻ-1
-2.0
Core radius:
radius: 23
23 ±± 11 Ǻ
Ǻ
Core
Core radius
radius σ:
σ: 5.5
5.5 Ǻ
Ǻ
Core
Shell thickness:
thickness: 66 ±1
±1 Ǻ
Ǻ
Shell
θ
-1.5
-1.0
-0.5
Log (Q) [A]
3
detector
2
1
interparticle distance ~ 5.2 nm
0
-0.5
0.05
0.10
0.15
Q (A)
0.20
0.25
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.
Superior Performance of NanoMas NanoSilver Inks
due to the Ultra-Small Nanoparticle Size
25
PET
Cabot PED (20-30 nm)
ManoMas (~ 5 nm)
NanoAg (~25 nm)
from competitors
Resistivity ( µΩ-cm)
20
15
Kapton
NanoMas
NanoAg (5 nm)
10
5
Ag bulk resistivity
0
NovaCentrix
100
150
(~20 nm broad distribution)
Annealing
200
Cima NanoTech
(80-100 nm) (C)
Temperature
250
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 NanoSilver Contacts in
Fabricating a-Si:H TFTs on Glass
Probes
Source
Drain
L (µm)
µ
(cm2/Vs)
VT (V)
110
140
~ 0.91
~ 0.97
~ 1.68
~ 1.41
* Data curtsey of Dr. Yongtaek Hong of
Seoul National University, Korea
VDS = 40 V
L = 110 um
L = 140 um
200
100
-5
10
-6
10
0
-10
0
10
20
VGS (V)
30
40
IDS (uA)
-4
10
IDS (A)
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
Printed NanoSilver Contacts in
Fabricating Organic TFTs
Ag
PQT
Ag
Silicon dioxide gate dielectric
Single crystal silicon gate
• Organic Semiconductor: poly(3,3 didodecyl-quaterthiophene) or PQT-12
• Source and drain printed with NanoMas
NanoSilver inks and annealed at 145ºC
• Device channel length of ~43 um and
width of ~300 um
• No obvious contact resistance
* Data curtsey of Dr. Jurgen Daniel of PARC
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
Log(Id)
ZnO TFT with printed Ag contacts
1.0E-04
1.0E-05
1.0E-06
1.0E-07
1.0E-08
1.0E-09
1.0E-10
8.0E-03
6.0E-03
4.0E-03
2.0E-03
0.0E+00
-30
Mobilities: 0.1-0.15 cm2/Vs
On/Off: ~105
-10
10
Vg
30
50
About Cost…
• 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
processes.
• NanoMas makes sure all the nano-materials it makes can
be mass produced with LOW COST processes.
Lab
Pilot Production
Mass Production
NanoMas Technology and Product Roadmap
• NanoMas current products include NanoSilver™ and NanoGold™
conductive inks.
• Under development with its proprietary technology, NanoMas will also
provide inorganic nanoparticle and polymer semiconductor inks, as well
as electroluminescent (EL or LED) inks for PE applications.
• NanoMas also has the technologies to mass produce high quality carbon
nanotubes and carbon nanofibers.
NanoMas Product Portfolio
Printable Electronics & Displays
• Silver nanoparticle inks
• Gold nanoparticle inks
• EL nanoparticle inks
• Semiconductor nanoparticle inks
• Polymer semiconductor inks
• Inorganic dielectric inks
• Polymer dielectric inks
Functional Nanomaterials
• Silver nanoparticles
• Gold nanoparticles
• Carbon nanotubes
• Carbon nanofibers
• Decorated carbon nanotubes
• Magnetic nanoparticles
• Novel catalysts for making
carbon nanomaterials
Other Nanomaterials Developed at
NanoMas Technologies, Inc.
NanoMas Technologies, Inc
NanoMas Technologies, Inc. is an early stage start-up company,
located in the Innovative Technologies Complex (ITC) on the campus of
Binghamton University (SUNY) in Binghamton, New York, where is also
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: 607-821-4208
Fax: 866-367-1128 (toll-free)
Website: www.nanomastech.com