liquid phase exfoliation of graphene and inorganic … nitride metal oxides metal chalcogenides bi 2...
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Liquid Phase Exfoliation of Graphene and Inorganic Layered Compounds
– a Route to Diverse Applications
Dr. Mustafa Lotya on behalf of Prof. Jonathan Coleman
School of Physics & CRANN, Trinity College Dublin
[email protected], [email protected]
NSF/AFORSF Workshop May 30, 2012
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Graphene! How much do we need?
Graphite ~ $/kg
Mechanical props: Composites - ????kg
Electronic props: wafer scale - ~10-7 kg/m2
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Graphene! How much do we need?
Need large scale production!
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Key – Solvent exfoliation of graphene
Nature Nano, 3, 563 ACS Nano, 4, 3455
Small , 6, 864 Small, 6, 458
New J. Phys. 12, 125008 Langmuir, 26, 3208
JACS, 131, 3611 Adv. Func. Mater. 19, 3680
NMP
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What about oxides/defects?
0 1 2 30.0
0.2
0.4
0.6
0.8
<I D
/IG>
1/<L> (m-1)
Powder
1000 1500 2000 2500 3000
G2D
Raman shift (cm-1)
D284 286 288
282 284 286 288 290
Binding energy (eV)
Graphene
C=OC-N
CRing
C-C
•XPS says no oxides
Hernandez, Nature Nanotechnology 2008, 3, (9), 563-568 Khan, SMALL 2010, 6, (7), 864-871
•Raman suggests few basal plane defects
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Can we extend liquid exfoliation to layered compounds?
Boron Nitride Metal oxides
Metal chalcogenides
Bi2Te3 Sb2Te3
Bi2Se3 Sb2Se3
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Transition metal dichalcogenides (TMDs)
2
METALLIC
SEMICONDUCTING
BOTH, depends on X
Mechanically Exfoliated MoS2
Transistors (Ion/Ioff ~ 108) 1
Photocurrent effect 2
1 B. Radisavljevic et. al. Nature Nanotechnology 2011, 6, (3), 147-150 2 Z. Yin et. al. ACS Nano 2011
Liquid Phase MoS2/WS2
Li-ion intercalation in water Distortion: 2H -> 1T octahedral
Semiconductor ->metallic
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WS
2 (N
MP
) B
N (IP
A)
10 µm
MoS2
5 µm
WS2
5 µm
BN
100 nm
500 nm
500 nm J. Coleman, M. Lotya, A. O’Neill, S. Bergin,
V. Nicolosi et. al., Science, 331, 568-571, 2011
MoS
2 (N
MP
)
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Other inorganic materials…
Mo
Se2
Mo
Te2
TaSe
2
Nb
Se2
Bi 2T
e 3
NiT
e 2
MoSe2MoTe2 TaSe2
NbSe2 Bi2Te3 NiTe2
A
C
400 600 800 1000 1200 1400 1600
TaSe2
MoSe2
NbSe2
MoTe2
Bi2Te
3
Absorb
ance (
au)
Wavelength (nm)
NiTe2
B
Mo
Se2
Mo
Te2
TaSe
2
Nb
Se2
Bi 2T
e 3
NiT
e 2
MoSe2MoTe2 TaSe2
NbSe2 Bi2Te3 NiTe2
A
C
400 600 800 1000 1200 1400 1600
TaSe2
MoSe2
NbSe2
MoTe2
Bi2Te
3
Absorb
ance (
au)
Wavelength (nm)
NiTe2
B
Bi2Te3
200 nm
Bi2Te3
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What governs dispersion?
22
, NSSE
atomV
atomV/1
Hamaker approach: extended monatomic systems, solely London interactions….
Polarisability
Atom density
2
,,
,
2
8exp NSSSS
NSS
NS EEkTE
DC
Simple, crude model:
• Depends on surface energy ES
• Solvent and nanosheet values
must match • Why similar?
0.0
0.5
1.0
MoTe2
MoSe2
MoS2
WS2
0.0
0.5
1.0
Co
nce
ntr
atio
n (
au
)
0.0
0.5
1.0
50 60 70 80 900.0
0.5
1.0
Solvent surface tension (mJ/m2)
Cunningham, ACS Nano 2012, 6, (4), 3468-3480
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Increase concentration?
More starting material
Longer sonication
10 1001
10
100
C (
mg/m
l)
tSonic
(hrs)
C (
mg/m
l)
600 700 800 900
103
104
20 mg/ml
Wavelength (nm)
A/l (
m-1)
-2.7
10 mg/ml
100 mg/ml
50 mg/ml
600 700 800 900
140 hrs
94 hrs
A/l (
m-1)
Wavelength (nm)
-4.2
72 hrs
10 100
0.1
1
CI (mg/ml)
200 nm 200 nm 200 nm
E) 23 hr F) 70 hrs G) 106 hrs
MoS2
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Hybrid materials
Sufficiently good properties of inorganic material alone? e.g. MoS2 – poor electrical conductor Hybrid materials -> new/unusual properties? Much potential for devices Easy with liquid dispersions….
200 nm 500 nm
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Hybrid materials
500 nm
MoS2
10s of nm thick to freestanding
25 mm
Gra/MoS2 SWNT/WS2
200 nm 500 nm
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Homogenous – Graphene/MoS2 hybrids
10 µm 10 µm
Graphene MoS2
Dispersion excellent on length scale of flake size
0 500 1000 1500 2000 2500 3000
Inte
nsity (
a.u
.)
Raman Shift (cm-1)
300 350 400 450 500
MoS2
Gra
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Electrical properties: Graphene/MoS2 hybrids
0.1 10.1
1
10
100
D
C (
S/m
)
-c
Below percolation
Above percolation
t
c
cGraDC
1
s
c
cMoSDC
2
s=5.3 t=2.1 c=22%
0.0 0.2 0.4 0.6 0.8 1.010
-7
10-5
10-3
10-1
101
103
DC (
S/m
)
Volume fraction,
0.3 0.2 0.110
-7
10-6
10-5
10-4
10-3
10-2
D
C (
S/m
)
c-
0.05
Cunningham, J Materials Chem, under review.
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Application: Supercaps, Thermoelectrics
0.0 0.5 1.0-2
0
2 MnO
2
MnO2/SWNT
I (m
A)
Voltage (V)
Super-cap electrodes
10 100
80
120
160
0 50 100
0
50
100
150
200
Mass fraction, (%)Mass fraction, (%)
D
C (
S/c
m)
Mass fraction, (%)
SWNTs
WS2/SWNT
WS2/SWNT
S2
DC (W
/K2m
)0 20 40 60 80 100
0
20
40
60
80
100
S (V
/K)
2
DCSzT T
Thermo-electric materials
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Application: Li-ion batteries Good energy density but poor stability: electrode cracks on cycling
Required:
• Good Li intercalation,
• Conductivity
• mechanical robustness
Devices tested at Uni Sydney by Prof A Minett
Solution: MoS2/Nanotube hybrid MoS2/SWNT hybrid cathode
Graphite anode
LiPF6 electrolyte
xLi+MoS2 ↔ LixMoS2
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Application: Polymer Composites
25 mm
PU Exfoliated layers easily formed into composites
Y=270 GPa, B=23 GPa
Reinforcement?
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MoS2/Polyvinylalcohol films
2.0
2.5
3.0
3.5
4.0
4.5
0.0 0.1 0.2 0.3 0.4 0.5100
120
140
160
180
Expected:
dB/dV
f=23 GPa
dY/dVf=700 GPa
Y (
GP
a)
Expected:
dY/dVf=270 GPa
Volume fraction (%)
B (
MP
a)
0 5 10 15 20 25 30
0
50
100
150
Str
ess (
MP
a)
Strain (%)
PVA
0.14%
0.24%
Stress transfer >5 MPa
Flake L/t~2000
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Solvents? Use Surfactant/water
0 2 4 6 8 10 12 14
-60
-40
-20
0
(
mV
)
pH
-100 -50 0
MoS2/SC
(mV)
SC
400 600 800 100010
-2
10-1
100
1500 rpm
1250 rpm
1000 rpm
A
Wavelength (nm)
750 rpm
600 700 800 900
0.00
0.05
0.10
MoS2/Sodium Cholate in H2O
Smith, Advanced Materials 2011, 23, (34), 3944-3948
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TEM & AADF-TEM
5 n m5 n m
200 nm 200 nm 50 nm 10 nm
100 nm
2 n m2 n m
2 nm
0 2 4 6 80
1
2
I (a
u)
nm
100 nm
Good quality few layer flakes
Smith, Advanced Materials 2011, 23, (34), 3944-3948
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Other materials in water?
BN
WS 2
Mo
Te2
Mo
Se2
TaSe
2
Nb
Se2
BN TaSe2 WS2
MoTe2 NbSe2 MoSe2
MoSe2
200 nm
NbSe2 TaSe2
MoTe2
WS2
200 nm
200 nm 200 nm
200 nm
BN
200 nm
~1g MoS2 in 1L water ~1015 flakes
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Next steps – layered oxides?
100 nm 500 nm
MoO3 TiO2 MnO2
100 nm
Supercaps, Li ion batteries etc
Surfactant / solvent exfoliation?
MoO3
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Acknowledgements
Collaborators: Prof. Valeria Nicolosi (CRANN, TCD) Prof. Andy Minett (Univ of Sydney)
Dr. Sukante De Dr. Umar Khan Dr. Phil Lyons Marguerite Hughes Karen Young Evelyn Doherty Paul King
Arlene O’Neill Sophie Sorel Peter May Ronan Smith Graeme Cunningham Conor Boland Sebastian Barwich
Chemical Physics of 1D Nanostructures Group
Prof. Jonathan Coleman