Future Trends in Nanocarbon Materials Nanohiilet ja painettava elektroniikka
Prof. Dr. Esko I. Kauppinen NanoMaterials Group
Department of Applied Physics
Aalto University School of Science
New Carbon Materials Research Initiative
October 26, 2012 @TEKES, Helsinki, Finland
Allotropes of carbon
diamond graphite
C — C
fullerene
Nanobud (CNB) Graphene – NO band gap
carbon nanotube –
YES has band gap
Nanocarbon FUTURE in Finland: develop PRINTING-based manufacturing & engineer novel flexible electronics applications of nanocarbon thin films
Proposal for Large Strategic Research Opening 2013-2020
Already developed for SWCNT
To be developed for graphene
Future technology to be developed
1atm,
continuous, fast
formation
Room temp. process
Onto any substrate
High
Performance
Touch Sensors,
Flexible ICs &
Other
Applications
Finland
Conference chairs
Prof. Esko I. Kauppinen (chair) Prof. Risto Nieminen (co-chair)
Prof. Pertti Hakonen (co-chair)
Co-organizer Prof. David Tomanek
National committee Albert G. Nasibulin (Aalto, chair), Hua Jiang (Aalto), Markus Ahlskog (U. Jyväskylä),
Arkady Krasheninnikov (U. Helsinki), Harri Lipsanen (Aalto), Kai Nordlund (U.
Helsinki), Yutaka Ohno (Aalto & Nagoya U. Japan), Mika Pettersson (U. Jyväskylä), Yuri Svirko (U. Eastern Finland)
Local organizing committee Toma Susi (chair), Marita Halme, Alexander Savin, Antti-Pekka Eskelinen
Supported by NT Steering Committee and International Advisory Board
NT 13 Organizers
• Metrology, biomedical
• Modeling
• Graphene
• Thin films
• Composites
Satellite Meetings June 29-30, 2012 In Tallin, Estonia (80 km from Helsinki)
WORLD LEADING EXPERTS contacted • Prof. Morinobu Endo, Shinshu University/Showa Denko, Nagano, Japan
• Prof. Sumio Iijima, Meijo University, Nagoya U., AIST, NEC, Japan
• Prof. Daniel E. Resasco, Oklahoma University/SWeNT, Norman, OH, USA
• Dr. Tapani Ryhänen, Nokia Research Center, Cambridge, UK
• Dr. Jong Min Kim, Samsung Electronics Co, Korea
• Dr. Patrice Gaillard, Arkema, France
• Dr. Y. Awano, Fujitsu/Selete, Japan (now Keio Univ.)
• Prof. Young-Hee Lee, Sungkyunkwang University/Samsung, Korea
• Prof. Richard Martel, Montreal University, Canada (earlier IBM, USA)
• Dr. Yoon Soo Park, Rensselear Polytechnic Institute, USA
• Dr. Christoph J. Brabec, Konarka, USA
• Prof. Yueh-Lin Loo, Princeton University, NJ, USA
• Prof. Iain McCulloch, Imperial Collage, London, UK
• Dr. Vladimir Serikov, Nippon Sheet Glass America, USA
• Dr. Martin Schmidt, Bayer Baytubes, Germany
• Pasi Keinänen, Amroy Oy, Lahti, Finland
• Paul Glatkowski, Eikos, MA, USA
• Sean Olson, Unidym, CA, USA
• Prof. Ray Baughman, UTD, TX, USA
• Prof. Dr. Janos B. Naby, NanoCyl/NANOPART, Belgium
• Prof. Liming Dai, U. Dayton, OH, USA
• Dr. Michael J. Bronikowski, Atomate, CA, USA
• Dr. Marcelo Motta, Thomas Swan Co., UK, England
BLUE = has answered the questionaire GREEN = has been discussed
KYSYMYKSET:
Mitkä ovat
nanoputkien
tärkeimmät
sovellukset
2020 ja 2030 -
Mikä
on niiden
sovelluksiin
tuoma
arvonlisä
CNT application areas 2020 and 2030 – additional business value from CNTs
Committee for Future / House of Parliament study published March 24, 2010
Sovellus Hiilinanoputkien
tuottama arvonlisä
miljardia $
Yksiseinäisiin hiilinanoputkiin perustuvien
sovellusten osuus arvonlisästä
2020 2030 2020 2030
1. Akut ja paristot * 4 10-20 20% 50%
2. Taipuisien ja läpinäkyvien johtavien/puolijohtavien
kalvojen sekä transistoreiden sovellukset mm. näytöt
3 8-20 75% lähes 100%
3. Aurinkopaneelit ym. valosähkölaitteet* 2 10 20% 50%
4. Valaisulaitteet (mm. kenttäemissio)* 2 5 50% lähes 100%
5. Autojen ja lentokoneiden materiaalit* 2 15 Hyvin vähän 25%
6.Muut komposiitit (mm. urheilu, tuulienergia)* 2 5 Hyvin vähän 50%
7. Aistimet tms. sensorisovellukset 1,5 5 lähes 100% lähes 100%
8. Johtimet integroiduissa piireissä 0,5 3 20% 25%
9. Elektrostaattinen suojaus* 0,5 2-4 20% 25%
10. Superkapasitaattorit* 0,3 5 20% 50%
11. Lääkkeiden kuljetus kehossa tms. lääketieteen
sovellukset
0,3 3 50% lähes 100%
12. Polttokennojen elektrodit* 0,2 1-8 Hyvin vähän 50%
13. Suodattimet 0,2 0,2- 3
14. Elektromekaaniset muistit 0,2 2 lähes 100% lähes 100%
15. Laser 0,1 2
16. Muut sovellukset 0,4 3
Yhteensä 19,2 90-110
FNTG Research Society Japan –chair: prof. S. Maruyama,
Tokyo U.
Fullerene
Single-Walled Carbon Nanotubes
(SWNTs)
Peapod
Multi-Walled Carbon Nanotubes Graphene
Nano-Diamond
Bundle of SWNTs
Double-Walled Carbon Nanotubes
Metallofullerene
http://fullerene-jp.org/
The Fullerenes, Nanotubes and Graphene Research Society
1990 2000 20100
100
200
100
102
104
Year
Num
ber
of
Pre
senta
tions
Sapporo
Nagano
Earth Quake
Tokyo40th
Shinohara
Maruyama
Num
ber
of
Web o
f S
cie
nce P
apers
fullerene
nanotubes
graphene
Osawa
FullereneNobelPrize
GrapheneNobelPrize
MWCT real applications in China developed by Tsinghua University
Yang Wei Yang Wu
Peng Liu
Qunqing Li
Qiang Zhang Rong Xiang
S. Maruyama
Fei Wei Shoushan Fan
Kaili Jiang
Yan Li
Kaili Jiang Rong Xiang
Shoushan Fan
S. Maruyama
Yan Li
Fei Wei
Qiang Zhang
Jin Zhang
Recent Developments in USA (IBM)
Nokia phone with
CNTs ?
Samsung phone
with Graphene or
CNTs
?
Products based on flexible electronics ?
CNTs and graphene for flexible electronics
Swiss, Empa
E-paper Smart phone Flexible solar cell
Flexible electronics:
Carbon nanotube: Electrical properties, Mechanical properties, Optical properties, Thermal properties, …
(www.photon.t.u-tokyo.ac.jp)
Carbon nanotube thin-film: High carrier mobility, Flexibility and stiffness, Simple and fast process.
RFID tag
Sunchon Nat. Univ.
& Rice Univ.
(Radio Frequency Identification)
Requirements to material and devices for flexible electronics
Fabrication on plastic substrate Low temperature process Low-cost fabrication Atmospheric pressure process High-speed printing method Roll-to-roll manufacturization
Silicon and ITO：Hard, Fragile Plastic: Flexible, Elastic
Hewlett-Packard
Comparison of various traditional thin-film transistors for display applications
Material Mobility (cm2/Vs)
Method (Process temp.)
Flexibility Large area
Cost Stability
Poly-Si 30~300 Vac. CVD (500C)
Bad Fair High Very good
Amorphous-Si 0.5~1 Vac. CVD (> 200C)
Bad Fair High Very good
Oxide (InGaZnO)
1~10 Vac. Sputter (R.T.~200C)
Good Fair Moderate Very good
Organic 0.01~10 Solution,
Sublimation (R.T.)
Good Very good
Low Bad
Additional important parameter: on/off ratio – must be larger than 1 000 000 = 106
(ratio of transistor on-current to off-current)
Comparison of SWCNT and graphene for for flexible electronics applications
Material Mobility (cm2/Vs)
On/off ratio
Manuf. method (Process temp.)
Flexibility Cost Stability
Individual SWCNT on the subtrate
50 000 – 200 000
108 CVD (600-900C)
Very good High Very good
SWCNT thin film on the subtrate
100 - 2000 105 - 107
Depositon from solution or gas phase (ambient)
Very good Low Very good
Free-standing graphene single
crystal
100 000 - 1 000 000
2-100
Exfoliation (not an industrial
manufacturing process)
Very good Very high Very good
Graphene thin film on the subtrate
1 000 – 5 000
2-100
CVD (900-1050C)
Very good High Very good
On/off ratio for digital electronics and display backplane must be larger than
1 000 000 = 106 – graphene is not suitable for these applications
Solid process - also for graphene:
Liquid process: Aalto/Canatu dry
gas-phase process :
DGU: Hersam group
Gel: Kataura group
Spin coating/ liquid printing
Direct Dry Printing (DPP)
e.g. Rogers group
Fabrication methods for flexible CNT device
Large-area synthesis of graphene by
CVD Set-up for the CVD growth 5 x 5 cm2 transferred graphene on Si
Raman and optical spectroscopy
Dept. of Micro- and
Nanosciences,
Aalto University
Prof. Harri Lipsanen
Micronova Research Center,
in collaboration with
VTT Nanoelectronics
1 µm
W. Kim, P. Pasanen, J. Riikonen, H.
Lipsanen Nanotechnology 23 (2012)
115201
Graphene rectifier
Transparent graphene on rigid or
flexible substrate Graphene transfer
to new substrate
Polymer
support film on
graphene
Graphene
on copper
Copper foil or
Cu/SiO2/Si wafer
Mobility ~ 2000
cm2/Vs
RF Field-effect transistor (on CVD graphene)
On/off ratio ≈ 2 Cut off frequency ≈ 80 MHz
(Measured by J. Anteroinen, Circuit design group)
7 x 5 graphene FETs array 1 µm x 50 µm channel dual gate FET
Inverter (on CVD graphene)
Implemented configuration
1 µm x 50 µm channel FETs
Graphene transistors on wafers & on flexible substrates
SWCNTs in the
reactor gas
Synthesis
Control of SWCNT
properties Patterned/non-
patterned
Deposition Thin Films
Aalto University Novel dry, direct CNT film deposition method: DPP – Direct Dry Printing
Industrial manufacturing – Canatu Oy
High Crystalliny as observed with 80 kV Cs-TEM: 2 individual tubes with (17,6) chirality –
diameter 1.60 nm, chiral angle 17.2 degrees - and with UHV-LT STM
Collaboration with
Prof. A. Kirkland
Oxford Univ. UK
25.1.2010
The Finnish nanotechnology based electronic component company Canatu Oy
was announced as one of the winners of the Red Herring Global 100 award at
the award ceremony in Laguna Niguel, California.
Canatu Oy's business is the production and sales of a new class of versatile carbon
based components based on carbon nanotubes and our novel NanoBud™
nanomaterial. These components improve the performance and reduce the cost of
optical, energy generation and storage and electrical devices while, simultaneously
reducing their environmental footprint.
© Canatu Ltd. | Tekniikantie 21 02150 Espoo Finland | info: www.canatu.com
Touch the Future
Canatu Thin Film manufacturing process
Canatu Production Facility, Helsinki
1 10 100 1000 100000
20
40
60
80
100
This work: NO2-doped SWNTs (Nasibulin et al.)
This work: pristine SWNTs (Nasibulin et al.)
Aerosol synthesised (Kaskela et al.)
Sorted DWCNTs + SOCl2 (Green & Hersam)
Sorted SWCNTs + SOCl2 (Green & Hersam)
Pristine SWCNTs (Green & Hersam)
Arc tubes (Geng & Lee)
Laser tubes (Geng & Lee)
HiPco tubes (Geng & Lee)
Tra
nsm
itta
nce
(%
)
Sheet resistance (/ )
ITO on flexible substrate
Record performance level of SWCNT-based transparent electrodes (1.7 nm tubes)
Nasibulin, Kaskela, Mustonen, Anisimov, Kauppinen, et al. (2011)
ACS Nano, 5(4), p.3214
84 / at Tr=90% ->
40 / at Tr=90%
World's first carbon nanotube based integrated circuits on plastic substrate
Inverters
Ring oscillators (3, 11, 21 stages)
NOR and NAND logic gates
RS- and D- flip-flops Sun et al,Nature Nanotechnology (2011) 6, 156–161
Long, straight CNTs
Clean network
Y-junction
Unique morphology of CNT network
Sun, Timmermans, Tian, Nasibulin, Kauppinen, Kishimoto, Mizutani and Ohno,
Nature Nanotechnology (2011) 6, 156–161.
World’s highest performance carbon nanotube TFTs - High mobility and high on/off achieved concurrently-
Let us together develop novel nanocarbon applications in Finland !
Fullerene
Single-Walled Carbon Nanotubes
(SWNTs)
Peapod
Multi-Walled Carbon Nanotubes Graphene
Nano-Diamond
Bundle of SWNTs
Double-Walled Carbon Nanotubes
Metallofullerene
