Modification of Graphene Films by Laser-Generated High ... E--Modification... · • Probability of...
Transcript of Modification of Graphene Films by Laser-Generated High ... E--Modification... · • Probability of...
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ATF Program Advisory and ATF Users’ Meeting April 2-3, 2009, Berkner Hall, Room B, BNL
Department of Chemistry Center for Electron Transport in Molecular Nanostructures, Columbia University, New York
Elena Stolyarova (Polyakova), Ph.D.
Modification of Graphene Films by Laser-Generated High Energy Particles
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• The world of sp2 carbon• What is graphene?• Graphene: the thinnest impermeable membrane
Modification of Graphene Films by Laser-Generated High Energy Particles
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N CR39 plate
Magnet Aluminum foil
parabolic focusing
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Spectrometer slit
Graphene sample
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• High energy particles and nanotechnology•Possible applications and future plans
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Carbon: remarkable elementCarbon: remarkable element
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Carbon: remarkable elementCarbon: remarkable element
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SP2 Carbon: 0-D to 3-D
Fullerenes Carbon Nanotubes
Atomic orbital sp2s
p
GraphiteGraphene
0D 1D 2D 3D
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STM image of graphene
Graphene: a novel exciting material
•One atom thick crystal•Conductive (High Mobility)•Unusual electronic properties•Stable, chemically inert•Stiff•Gas-impermeable
kx' ky'
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Science 306, 666 (2004)
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Graphene Field-Effect Transistors Graphene Field-Effect Transistors
http://en.wikipedia.org/wiki/History_of_the_transistor
1947
A replica of the first transistor
20 µm
Single layer graphene device
www.hfml.ru.nl/highlights/RT_QHeffect.shtml
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Resistance vs Gate Voltage
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Mechanical Exfoliation of Graphene
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1 mm
AFM Image
A Few Layer Graphene on SiO2/Si Substrate
0.8 nm
0.4 nm1.2 nm
Optical microscope images
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Raman Spectroscopy is a reliable tool for single layer Raman Spectroscopy is a reliable tool for single layer identificationidentification
Ferrari, A.C., et al., Phys. Rev. Lett., 2006. 97(18)
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Observation of graphene bubbles and effective mass Observation of graphene bubbles and effective mass transport under graphene filmstransport under graphene films
Bombardment with high energy protons
Chemical Reaction (HF/H2O etching)
•Can we insert molecules under the graphene film?
•Can a molecule penetrate through a graphene?
•Do molecules move across graphene-silicon dioxide interface?
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“Chemical” method for making bubbles
2 4 24 2waterSiO HF SiF H O+ → +
HF
Heat Heat
HF/H2O vapor
grapheneSi/SiO
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HF/H2O vapor
Stable for months Raman spectrum is similar to supported graphene Can be destroyed by AFM tip Formed only if SiO2 is etched completely
Huge graphene bubbles
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Ion energy ~ 0.5MeV
CR39 track density vs deflection distance
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N CR39 plate
Magnet Aluminum foil
parabolic focusing
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Spectrometer slit
Graphene sample
particles
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mirror
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Proton Irradiation of Graphene FlakesProton Irradiation of Graphene Flakes
ATF TNSA Source
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3 ML
AFM Images of irradiated graphene samples: Nanoscale bubbles
1 ML
•Small gas bubbles are formed•Gas molecules are trapped between graphene and SiO2
1 ML
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Propagation of a proton through the solid targetPropagation of a proton through the solid target
Probability of nuclear knock-off
•Protons are only weakly deviated from the straight path•Nuclear knock-off damage is significant only in the end of the track•Energy loss per distance traveled is nearly uniform
Applications of proton beams
•Cancer therapy•3D lithography•Magnetic carbon
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• Probability of the defect formation in graphene is extremely low
• 99.9% of proton's kinetic energy is deposited in electronic excitations
• The 0.5 MeV protons stops deep inside the Si wafer
• Gas is expected to be released from the substrate
• Irradiation causes desorption / rearrangement of surface impurities
Propagation of a proton through the graphene sample
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STM and Raman study of graphene samples exposed to high energy protons
STM imaging of the samples exposed to high energy protons shows no atomic scale defects
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• G band is blue-shifted by 10 cm-1, indicating significant chemical doping
• There is no signature of the D “defect” band no →structural damage
Raman SpectroscopySTM Imaging
D
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Mobility of the graphene bubbles
• The center region marked by a dashed square was scanned previously with a lower value of set point in the tapping mode (stronger tip-sample interactions)
• Bubbles can be moved by the AFM tip
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Before annealing After annealing (12 h at 350°C)
• Annealing causes coalescence of the bubbles
• Transport is possible underneath a graphene film
Coalescence of the Bubbles
1 ML
AFM images of irradiated graphene flakes
1 ML3 ML
3 ML
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Summary
Graphene, being only one atom thick, is stable and stiff material.
Graphene membranes can capture mesoscopic volumes of gas.
Graphene acts as an impermeable membrane
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Advantages of laser-driven ion source for applications in nanotechnology
Target Normal Sheath Acceleration
a0 ≥1
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electron cloud
aluminum foil
accelerated
ponderomotive force
incident laser beam
plasma
electric field
positive ions
●Material modification under extreme conditions (New physics and chemistry)
●Reimaging/ion writing
●3D lithography
Compact and inexpensive source of high-energy ions.
Easy switching between different ions by changing the target material.
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Material modification under extreme conditions
●Defect generation●Chemical modification of irradiated ares●Local doping
Ions
Polyakova (Stolyarova), et. al. unpublished
Protons
●Ultrafast heating●Irradiation with pulsed beams
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Reimaging target structure
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3D proton-beam lithography
High aspect ratio structures:
p-beam writing in SU-8 negative resist showing 60 nm wall structures that are 10 μm deep
True 3D structures:
Microsized copy of Stonehenge in the UK fabricated using p-beam writing in SU8 resist.
0.5 MeV
2 MeV
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Thanks
• Prof. George Flynn, Dr. Kwang Rim, Dr. Daejin Eom, Dr. Li Liu (Columbia)
• Prof. Philip Kim, Dr. Kirill Bolotin, Melinda Han, Meninder
• Prof. Horst Stormer, Dr. Etienne De Poortere (Intel), Dr. Erik Henriksen (Caltech)
• Prof. Hone, Martin Klima, • Prof. Louis Brus , Dr. Sunmin
Ryu (Columbia), Prof. Tony Heinz, Dr. Janina Maultzsch
• Dr. Mark S. Hybertsen (CFN, BNL)
• Dr. D. Stolyarov, Dr. I. Pogorelsky, Dr. I. Pavlishin, K. Kusche, Dr. V. Yakimenko (ATF, BNL)