Preparacin de grafeno por exfoliacin

micromecnica mediante sellos de

silicona
Nicols Agrat
Laboratorio de Bajas Temperaturas
Departmento de Fsica de la Materia Condensada, UAM
y
IMDEA-nanociencia
Simplest
Reliable
Higher quality
Micromechanical exfoliation
Graphene flake by
micromechanical exfoliation
Micromechanical exfoliation
Standard method of micromechanical
exfoliation: Scotch tape
Micromechanical exfoliation
Standard method of micromechanical
exfoliation: Scotch tape
Contamination due to adhesives in substrate and crystals
Contamination
affects transport
properties
Meitl 2006,
Nature Materials
PDMS (polydimethylsiloxane ) stamps
Soft lithography
Transfer process depends on
Pressure
Rate
Structure of stamp surface
viscoelastic
Clean sample fabrication procedure:
avoids eventual contamination of the 2D
flakes with the Scotch tape adhesive.
Micromechanical exfoliation of
graphene using PDMS stamps
5x
20x 50x
PDMS Stamp
Moreno-Moreno et al, Small 2009
Ribbon width down to 20 nm
Graphene Nanoribbons
24m long nanoribbon
Mechanical exfoliation is likely to produce edges and ribbons along well defined
crystalline directions.
Nanoribbons
Moreno-Moreno et al, Small 2009
Electrical characterization
Moreno-Moreno et al, Small 2009
Electrical characterization
1 - 1 - 2
2
1 2
s V cm 800 ~ mobility
500
d
d
w
(similar to values reported by
Kim group 2007)
Moreno-Moreno et al, Small 2009
MoS
2
Indirect gap semiconductor (1 eV)
NbSe
2
superconductor
Dichalcogenides: MoS
2
, NbSe
2
Optimal conditions for optical identification of 2D crystals
(Fresnel law + refractive index)
Calculated Contrast vs. Illumination wavelength vs. SiO2 thickness
Well known for graphene BUT NOT for other 2D crystals
Optical properties 2D crystals
Graphene MoS2 NbSe2
A.Castellanos-Gomez. et al. APL (2010)
Dichalcogenides: MoS
2
, NbSe
2
NbSe
2
MoS
2
MoS
2
for flexible semiconducting electronics
Bulk MoS
2
:
Dichalcogenide with layered structure
Semiconductor: Indirect gap 1 eV
Solid lubricant
Atomically thin MoS2:
Thickness dependent band structure.
Splendiani, et al. Nano letters. (2010)
Lee, et al. ACS Nano. (2010)
Ramakrishna, et al. Angewandte. (2010)
MoS2 based FET
30 nm thick: Ayari et al. J. Appl. Phys. (2007)
0.6 nm thick: Radisavljevic et al. Nature Nano. (2011)
Radisavljevic et al.
Nature Nano. (2011)
Mechanical Properties of
suspended MoS
2
membranes
Substrate matters
SiO
2
substrate
Trapped charges
Corrugation
Limited carrier mobility
Electron and hole puddles
(electron- and hole-doped
regions)
Limit device performance
Dirac point physics inaccesible
Standard
Convenient
Back gating
Suspended graphene
Large mobility enhancement (x 10)
but
Difficult to handle
Bolotin et al 2008 Solid State Com
Ultraflat graphene on hexagonal BN
Xue et al 2011 Nature Mat
Dean et al 2010 Nature Nano
225 pm on SiO
2
30 pm on hBN
Roughness:
hBN is very flat (thickness ~10nm)
and graphene conforms to it
~ 3 4
no surface charges
band gap ~ 6 eV
Xue et al 2011 Nature Mat
Ultraflat graphene on hexagonal BN
DOS of graphene
on hBN
DOS of graphene
on SiO
2
Energy of the
Dirac point
Enhanced mobility ( x 3)
Reduced carrier inhomogeneity
Reduced intrinsic doping
PMMA wet transfer method
BN on SiO
2
PMMA dissolved in acetone
Electrical leads are deposited using standard electron beam
lithography, after which all our samples are annealed in flowing
H2/Ar gas at 340 C for 3.5 hours to remove resist residues.
Dean et al 2010 Nature Nano
Xue et al 2011 Nature Mat
Ultraflat graphite on mica
Graphene roughness reflects substrate
roughness
Van der waals forces strongly suppress
ripples
Lui et al 2009, Nature
but
Bulk mica, NO GATE!
Transport experiments:
10-50 nm thick mica flakes
No mobility enhancement!
Ponomarenko 2009 PRL
Insulating atomically-thin layers:
mica (KF)
2
(Al
2
O
3
)
3
(SiO
2
)
6
(H
2
O)
Down to one monolayer (thickness 1.2 nm)
PDMS stamped
Identification by optical microscopy
SiO
2
thickness: 300 nm
Castellanos, et al 2011 Small
Insulating atomically-thin layers:
mica (KF)
2
(Al
2
O
3
)
3
(SiO
2
)
6
(H
2
O)
Down to one monolayer (thickness 1.2 nm)
PDMS stamped
Identification by optical microscopy
SiO
2
thickness: 300 nm
Castellanos, et al 2011 Small
Graphene on thin mica: all-dry transfer method
3 nm thick FLG on top of a 12 nm
thick mica flake.
Castellanos, et al 2011 Small
12 nm mica flake on SiO
2
Bulk mica
Raman characterization
For mica flakes from 2 nm to 60 nm
thick Raman spectra showed only
features of the Si underneath.
PMMA wet-transfer
PDMS all-dry transfer
No defects (no Dband at 1344cm
-1
) resembles
spectra of the freshly cleaved, pristine few layer
graphene.
Linear background: contaminants.
ratio between G-band (~1580cm
-1
) and 2D-band
(~2680cm
-1
) is below 1, indicating high doping of
the flake.
D-band: lattice defects or adsorbates
Castellanos, et al 2011 Small
Preliminary
10 nm flake on 4 gold contacts
Contact resistance 15 Ohm
Few-layer Graphene on predefined contacts
No adhesives, no e-beam, no resist
Summary
- Adhesive-free procedure for micromechanical exfoliation of graphene
- All-dry procedure to transfer FLG onto atomically thin mica flakes
- Cleaner and higher quality flakes than wet transfer
- Atomically thin crystalline heterostructures
- All-dry no e-beam procedure to transfer atomically thin flakes onto
predefined electrodes
Acknowledgements
MT Gonzlez
E Leary
Ch Evangeli
S Sherif
CR Arroyo
(TU Delft)
G Rubio-Bollinger A Castellanos (TU Delft)
Nanoelectronics Group UAM-IMDEA
Univ Groningen
Bart J van Wees
Magdalena Wojtaszek
Nikolaos Tombros
UAM
Julio Gmez-Herrero
Miriam Moreno-Moreno
Fabrication and characterization
Raman characterization
Silicone stamps
Conventional tapping AFM
M Bryce (Durham)
H Riel (IBM Zurich)
DM Guldi (Erlangen)
T. Wandlowski (Bern)
CJ Lambert (Lancaster)
C Schnenberger (Basel)
N Martn (UCM)
JO Jeppesen (Southern Denmark)
N Agrat (UAM)
QinetiQ-Malvern
STREP
ELFOS
ELectric Field control Over Spin
in molecules
HSJ van der Zant (Delft)
T Bjrnholm (Copenhagen)
S Kubatkin (Chalmers)
E Coronado (Valencia)
D Loss (Basel)
N Agrat (UAM)
Micromechanical cleavage of graphene
Contamination due to adhesives in the graphene crystals
Electrostatic force
2009 Bachtold group
ANDRES
en el paper empleabamos el modo de
transmision, a traves del sello de PDMS que es
bastante grueso, por lo que no pude encontrar
copos de menos de 10 capas.
Durante la transferencia, normalmente se
deposita todo el copo que hay en el PDMS (no
suele ocurrir que deposites solo pocas capas
de un copo que inicialmente era mas grueso).
Hay otras posibilidades en las que estoy
trabajando ahora en TU Delft.Como por
ejemplo, usar fast scanning Raman
spectroscopy (nos vamos a comprar un
cacharrazo que barre 5x5 mm en unos 10
minutos y te da un mapa de los picos G y 2D).
Estoy luchando ahora para transferir
grafeno sobre substratos con
electrodos pre-definidos y asi evitar
la exposicion a resinas y el e-beam.
Te puedo adjuntar una micrografia
de un copo de 10 nm (unas 30
capas) transferido sobre cuatro
contactos de oro (100 nm de
espesor) y que tiene una resistencia
de contacto de SOLO 15 Ohms), que
he fabricado la semana pasada.
Few-layer Graphene on predefined contacts
8. New AFM/STM
1 cm
2 mm
Low Temperature STM/AFM setup
Homebuilt tuning-fork LT-AFM/STM
Resonant freq 30 kHz
Q factor 10
6
Quartz tuning fork (TF) + conductive tip:
STM + noncontact-AFM
driven at resonant frequency fo.
force gradient between tip and surface
shifts fo.
subnanometer tip oscillation amplitude
low temperature compatible (low
dissipation)
Combined dynamic STM/Non-Contact AFM microscope
Coming soon: LT-STM/AFM with GPS
Carbon fibre tips
Simultaneous STM and AFM images @ RT
STM topography Force gradient image
Andrs Castellanos
Gabino Rubio-Bollinger
Force and current during
tip-substrate approach
V
gate
V
bias
Target
molecules
Lateral gating of
molecules on atomically-
thin substrates
Graphene
Mechanical exfoliation using silicone
stamps
Suspended graphene
mobilities in excess of 200,000 cm2 V1 s1 at
electron densities of 2 1011 cm2 by
suspending single layer graphene.
cleaned in situ by employing current-induced
heating, directly resulting in a significant
improvement of electrical transport.
Concomitant with large mobility enhancement,
the widths of the characteristic Dirac peaks are
reduced by a factor of 10
compared to traditional, nonsuspended
devices. This advance should allow for
accessing the intrinsic transport properties of
graphene. Bolotin et al 2008 Solid State Com
Ultraflat graphite on mica
Suspended Graphene is not atomically flat
they exhibit intrinsic microscopic
roughening such that the surface normal
varies by several degrees and out-of-
plane deformations reach 1 nm.
Meyer et al, Nature 2007
ripples are critical for electronic properties:
Enhnce reativity of graphene
Charge inhomogeneities
Suppression of weak localization
Charge scattering