Byung Hee HONG Technology Roadmap for the graphene industry in Korea PhD in Experimental Physical Chemistry, Nanochemistry, at Pohang University of Science and Technology (2002). Post doc at Nanoscale Science and Engineering Center and Department of Physics, Columbia University, with Philip Kim Now Assistant Professor, Department of Chemistry and Sungkyunkwan Advanced Institute of Nanotechnology (SAINT) Current research interests: - Chemical vapor deposition (CVD) of single-/multi-walled CNTs and graphene. - Self-assembled organic nanomaterials (nanotubes, lenses, and spheres) - Nanowires & metal-organic core-shell nanostructures (Au, Ag, Pt, Pd).
Transcript
Byung Hee HONG Technology Roadmap for the graphene industry in Korea
PhD in Experimental Physical Chemistry, Nanochemistry, at Pohang University of Science and Technology (2002). Post doc at Nanoscale Science and Engineering Center and Department of Physics, Columbia University, with Philip Kim Now Assistant Professor, Department of Chemistry and Sungkyunkwan Advanced Institute of Nanotechnology (SAINT) Current research interests: - Chemical vapor deposition (CVD) of single-/multi-walled CNTs and graphene. - Self-assembled organic nanomaterials (nanotubes, lenses, and spheres) - Nanowires & metal-organic core-shell nanostructures (Au, Ag, Pt, Pd).
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Technology Roadmap ofGraphene Industry in Korea
March 21, 2011
ByungByung HeeHee HongHong
Department of Chemistry and SKKU Advanced Institute of
Nanotechnology, SungKyunKwan University, Suwon, Korea
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Industrial Collaborators
Samsung Techwin, Electronics,Mobile Display, LED
Substrate Films
Composites
Wire Applications
Energy Applications
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1st SKKU Graphene Team
60 collaborators including Prof. B. Oezylimaz at NUS
Rutgers, Prof. M. Chhowalla Stanford, Prof. H. Dai
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CVD Growth of Large-Scale Graphene on Ni
Nano Lett. 9, 30-35 (2009) MIT Prof. Kong Nature 457, 706 (2009) SKKU & Samsung
CNT Graphene
Temperature 800~950 °C 1000~1030 °C
Catalyst Fe, Co, Ni, Au...Nanoparticles
Ni, Cu Film(Fe, Ge, Al, Sapphire..)
Source Gas C2H2, CH4 … C2H2, CH4
Growth Time 10min ~ 1hrs < 10 min
Appl. Phys. Lett. 93, 113103 (2008) Purdue Prof. Chen
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Large-Area Synthesis of High-Quality and Uniform Graphene Films on Copper Foils
MonolayerCoverage>95%
Li, X. et al. Science 324, 1312-1314 (2009).
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Y. Lee et al. Nano Lett. 10 490-493 (2010)
Wafer-Scale Synthesis and Transfer
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Roll-to-Roll Production of Ultra-Large-Scale Graphene Films
Graphene on Cu foil
Polymer support
Cu etchant
Graphene on
polymer support
Target substrateGraphene on target
Released
polymer support
S. Bae et al. Nature Nanotech. 5, 574 (2010)
Collaboration with Prof. J. Ahn (SKKU), Prof. B. Oezylimaz (NUS), Prof. Iijima
Comments by Prof. R. Ruoff (UT Austin) and Prof. P. Kim (Columbia)
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Roll-to-Roll Production of Ultra-Large-Scale Graphene Films
S. Bae et al. (2010)
b
Fig. 2
c
1st
2nd
Before heating
Afterheating
a
8 inch
f
d
e
Stencil mask
Screenprinter
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Low-T Synthesis by ICP CVD
SputterICP-CVD
-Fully automated programmable 6-inch graphene-growth system-Oxidation-free process for Fe/Cr/Co/Al /Cu/Ni… and alloys-Various source gases (CH4/C2H2/NH3/B2H6…)-Will be commercially available soon by SNtek
Load-lock
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Transfer-Free Synthesis on Polymer Substrates
- Sheet Resistance ~ a few kOhm/sq- Transmittance ~ 80% (Ni) ~90% (Cu)- Growth T ~300 C° (on Polyimide ) - Target T~200 C° on Polyethersulfone (PES), T~120 C° on PC, PET
S. Bae et al. (submitted)
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Pattern Growth of Graphene on PI film
- Pattern growth of graphene by ICP-CVD- Strain gauge pattern formation by lift-off process.
Collaboration with Prof. J. Ahn (SKKU)
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Roll-to-Roll Production of Ultra-Large-Scale Graphene Films
S. Bae et al. (Patented)Collaboration with Samsung Techwin
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Future Plan: Low-T, Transfer-free, Roll-to-Roll Production of Graphene on Polymer Films
Low-cost synthesis can be realized by mass-production
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by Wet Chemical Doping/Etching by Wet Chemical Doping/Etching
by Multilayer Stackingby Multilayer Stacking
by Grain Size by Grain Size ControlControl
by Nonvolatile Ferroelectric Gatingby Nonvolatile Ferroelectric Gating
by Substrate Engineeringby Substrate Engineering
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Charge carrier density proportional to doping level
ρ= 1/σ = 1/neμ
1R s
neµ=
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1 2 3 4 5 6 7 8 9 100
20
40
60
80
100
Decrease of Rs (%)
Doping materials
Nitromethane
HNO3+Nitro-
Methane(0.02 M)
Aucl 3+Nitro-
Methane(0.02M)
HNO3(16M)
HAucl 4+DI+
Nitromethane(0.02M)
H2SO4(12M)
H2SO4+
Nitromethane(0.02M)
HAucl 4+DI(80 mM)
HCl(16M)
HCl+
Nitromethane(0.02M)
Wet Doping Agent (p-type)
Wet Chemical Doping
Ferro-Electric Gating / Substrate Engineering
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Polymer Ferroelectric P(VDF-TrFE)
PVDF PTrFE
+
Spin coating, 135 annealing
Ferro phase
Amorphous/Non-ferro phase (~20%)
Non-Ferro
phase
Ferro phase
I. Preparation & structure II. Ferroelectric reversal
60 rigid dipole rotating
T. Furukawa, T. Nakajima and Y.
Takahashi, IEEE Trans. Dielect.
Electr. Insul. 13, 1130 (2006)
H
F
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Non-volatile high doping using organic ferroelectric gating
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Annealing at 950 C° with H2/Ar
1h 30min 2 hrs 5 hrs
200µm200µm 200µm
Grain Size Control by Pre-Annealing
Suggested by X. Li et al. Science 324, 1312–1314 (2009).
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Graphene growth depending on Cu Crystallinity
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EBSD Analysis of Cu Domains
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Ultra-large Graphene Domains
X. Li et al. arXv:1010.3903 (2010)
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43J. An et al. JACS (2011)
TEM Analysis of Grain Boundaries
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44P. Y. Huang et Nature (2010)
TEM Analysis of Grain Boundaries
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45P. Y. Huang et al. Nature (2010)
TEM Analysis of Grain Boundaries
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Q. Yu et al. arXv:1011.4690 (2010) 46
Graphene Growth at Ambient Pressure
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Raman Analysis of Grain Boundaries
Q. Yu et al. arXv:1011.4690 (2010)
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The sheet resistance of cm scale graphene films
seems to be affected more by the nanoripples of
graphene (induced by Cu step edges) rather than
the grain boundaries of graphene.
The lattice mismatch between Cu and graphene The lattice mismatch between Cu and graphene
doesn't look important in graphene growth.doesn't look important in graphene growth.
What does limit the conductivity of
CVD graphene?
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by Wet Chemicals Doping/Etching by Wet Chemicals Doping/Etching
by Multilayer Stackingby Multilayer Stacking
by Surface Treatmentby Surface Treatment
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-0.10 -0.05 0.00
0.0
2.0x10-5
4.0x10-5
6.0x10-5
8.0x10-5
1.0x10-4
1.2x10-4
1.4x10-4
1.6x10-4
1 ML
2 ML
3 ML
4 ML
Current density (A/cm
2)
Bias (V)0 1000 2000 3000 4000
0.00
0.05
0.10
0.15
0.20
Voc (V)
Time (sec)
1 ML
2 ML
Under simulated 100mW AM 1.5G illumination, a power conversion dfficiency (η, all uncertified) of 0.32 % with an open-circuit voltage (Voc) of 0.56 V, short-current density (Jsc) of 2.5 mA cm-2, and a fill factor (FF) of 0.23 were obtained.
photons
p-Si
Graphene
Al
A
G. Lim et al. Submitted
Work-function engineering of GrapheneBy Layer-by-Layer Stacking
K. Ihm et al. APL 77, 032113 (2010)
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Work-function engineering of GrapheneBy Layer-by-Layer Stacking
.whencontact,SchottkysiGφφ <
EF
Ei
p-Si Graphene
eVSi
02.061.4 ±=φGφ
0.30 eV
.whencontact,Ohmic siG φφ >
EF
Ei
eVSi
02.061.4 ±=φGφ
p-Si Graphene
1L
4L
n-Si n-Si
K. Ihm et al. APL 77, 032113 (2010)
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Si
OOO
N
HH
Si
O
Si
OOO
NH
H
N
HH
SiO2/Si
(a)
(b) (c)
10µm
NH2-SAMs
SiO2
Work-function Control of Grapheneby Self-Assembled Monolayers
Collaboration with Prof. K. Cho (POSTECH)
J. Phys. Chem. Lett. (in press)
J. S. Park et al. (Submitted)
GG-- ShiftShift
2D Intensity2D Intensity
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-40 -20 0 20 40 60 8010
-15
10-13
10-11
10-9
10-7
10-5
0.000
0.001
0.002
0.003
0.004
0.005
0 20 40 60 80
0.0
0.2
0.4
0.6
0.8
1.0
1.2
Drain current, (-ID)1/2(A
1/2)
Gate voltage, VG (V)
Drain current, I D(µA)
(a)
Drain current, I D(µA)
Drain voltage, VD (V)
- 0, 20V
-40V
-60V
(b)
(c) (d)
- 0, 20V
-40V
-60V
VG= -80V
Drain current, I D(µA)
Drain voltage, VD (V)
Graphenedoped by SAMs
PTCDI-C13
HMDS treated-SiO2/Si
Graphene on
SiO2
NH2 -SAMsLUMO 3.6 eV
HOMO 6.1 eV
EVPTCDI-C13
Φ=3.9eV
Φ=4.5eV
GrapheneOn Bare SiO2
GrapheneOn NH2-SAM
VG= -80V
0 20 40 60 80
0
5
10
15
20
Work-function Control of Grapheneby Self-Assembled Monolayers
- ITO high cost- Complex fabrication processes- Slow thermal response
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57.0
Zn/Fe plate
Graphene on Zn/Fe plate (ICP-CVD growth at 300 )
0 5 10 20 30 min
54.9
Graphene Composite for Thermal Spreading
0 5 10 20 30 min
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Graphene-Inorganic QD LEDs
SNU SKKU
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•Front plnae: Touch Screen, OLED
•Back Plane : TFTs
• Substrates: Gas Barrier Films
Substrate
Touch Screen
Graphene for Flexible OLED Display
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- LED (light-emitting diode)
Flexible light emitting sheets
EL pastes
LED keyboard “Torre Agbar” LED building
Graphene-Based Full-Color QD LEDs
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Graphene Gas Barriers for Organic Electronics- Oxygen and water molecules are fatal for organic devices.- Short lift time of OLED/OTFT/OPV- Gas permeability of typical polymer films, 1~10 g/m2day- Water Vapor Transmission Rate (WVTR)
- The best record: Barix (Dupont) Film ~ 10-4 g/m2day
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Flexible OLED
Transparent OLED
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gy Flexibility of Cu substrates and polymerFlexibility of Cu substrates and polymer--supported etching/transfer supported etching/transfer
enable the rollenable the roll--toto--roll production of graphene films. roll production of graphene films.
Sheet resistance of graphene electrodes can be enhanced by Sheet resistance of graphene electrodes can be enhanced by
chemical doping or multilayer stacking.chemical doping or multilayer stacking.
WorkWork--function tuning of graphene electrodes is very important for function tuning of graphene electrodes is very important for
OTFTs and PV cells, which can be carried out by surface treatment, OTFTs and PV cells, which can be carried out by surface treatment,
polypoly--electrolyte coating, wetelectrolyte coating, wet--chemical doping and strain.chemical doping and strain.
Considering the outstanding scalability/Considering the outstanding scalability/processibilityprocessibility of rollof roll--toto--roll roll
and CVD methods and the extraordinary flexibility/conductivity/ and CVD methods and the extraordinary flexibility/conductivity/
tunabilitytunability of graphene films, we expect the commercial production of graphene films, we expect the commercial production
and application for largeand application for large--scale transparent electrodes replacing the scale transparent electrodes replacing the
use of ITO can be realized in near future.use of ITO can be realized in near future.
