ruoff graphene npg workshop may 2011.pdf

7/27/2019 Ruoff Graphene NPG Workshop May 2011.pdf

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GrapheneGraphene Materials and OpportunitiesMaterials and Opportunities

Rodney S.Rodney S. RuoffRuoff

http://buckyhttp://bucky--central.me.utexas.edu/central.me.utexas.edu/[email protected]@mail.utexas.edu

THANK YOU FOR THE INVITATION TO PRESENT AT:

Funding from the W.M. Keck Foundation, the Texas Nanotechnology Research

:

Superiority Initiative (TNRSI)/SWAN, DARPA-iMINTCenter, DARPA CERACenter, ONR, ARO, NSF (4), DoE, DARPA (for transparent conductiveelectrodes), Graphene Energy, Inc., Graphene Materials LLC., and prior

Rod Ruoff NanotechnologyThe University of Texas at Austin

suppor rom an , s apprec a e .


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Graphene: Why, and for what. But when, and forhow much $? Brief history of experimental work on graphene

Large-area graphene grown on metal substrates Passivation of bare metal surfaces by graphene Thermal properties

Chemically modified graphene and derivatives:

paper-like materials electrodes for supercapacitors (EES)

Concluding Remarks



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us n ma n campus


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Ruoff research group Oct 2010

Left to ri ht: Niel Quarles, Drew Munson, Eric Ou, Iskandar Kholmanov, Charles Amos, Shanthi Murali, Jin An, Mer l Stoller, Shanshan Chen, JiWon Suk, Richard Piner, Carl Magnuson, Hyung Wook Ha, Rod Ruoff, Colin Beal, Aruna Velamakanni, Matthew Charlton, Columbia Mishra,Joono Park, Hengxing Ji, Jon Edgeworth, Jeff Potts, Yujie Ren, Xianjun Zhu, Yanwu Zhu, Huifeng Li and Weiwei Cai. Not pictured: AlanCovacevich, Cornelio Morales, Orlando Salmon, Yufeng Hao, Qingzhi Wu, Yaping Wu, Xin Zhao

Senior research scientist

Postdoctoral fellows

Ph.D. candidates

Visiting scholars

Undergraduate researchers

Note: We have a very stringent test that team members must pass before theycan work in the lab: Memorize the Periodic Table of the Elements



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Ruoffs Periodic Table



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WhyWhy GrapheneGraphene??

~1100 GPa modulus, fracture strength ~130 GPa

Low density ~2 g/cm3

Thermal conductivity ~3000 W/m-K in planebut highly

anisotropic; ~ 2 W/m-K out of plane

Electrical conductivity: ballistic electron transfer; high

mobilit

High specific surface area (limit: 2630 m2/g)

Physical properties can be chemically tuned

Barrier materialimpermeable if defect-free?

or neutral conditions)

Gra hene is thus a material of reat interest and also multila er


graphene and ultrathin graphite, such as


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us ness peop e an e r response o pe an cus ness peop e an e r response o pe an c

professors arguing about theirprofessors arguing about their pet definitionspet definitions forfor

nanotechnolo at a MEMS/NEMS meetin about 7 ears a onanotechnolo at a MEMS/NEMS meetin about 7 ears a o::

,, ,,

just want to make money!just want to make money!



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Application possibilities (among others, not a prioritized list)

.aerospace; transportation; high power transmission lines; many others)

2. Electrical energy storage (electrode material in ultracaps, batteries)

3. Thermal management (nanoscale, microscale, macroscale for HVAC, giant

4. Flexible electronics (plastic electronics)

5. Nanoelectronic devices (logic, memory)

6. Lightweight electrical conductor (electric grid, high tension wire?)

. ,

8. Transparent conductive films (image display, solar PV, other)

9. Impermeable films; barrier resistance (passivate Cu; food packaging, OPV, etc.)

10. Polymer, ceramic matrix composites; as paper-like materials but with unusual

11. Sensors: Chem- and bio-sensors; pressure sensors, strain gauge, others

12. Electric power generation: Fuel cells, possibly solar thermal; as transparent

conductive electrode; electron or hole sponge in OPVs

13. As a hi h s ecific surface area su ort material adsorbent for catal sts

14. As a compliant substrate that can also work at high temperature15. As a substrate or template for new materials

16. Textiles, clothing, others?



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Graphite: Inexpensive andGraphite: Inexpensive and Relatively PlentifulRelatively Plentiful

2008 USGS survey:

, ,

750,000 metric tons of natural graphite mined, processed, and used in 2008250,000 metric tons of synthetic graphite made and used in 2008#

.

Graphite sells for dollars per kilogram

But: How to disassemble graphite into individual sheets?

How about makin ra hene owder from methane?


Or by the kilometer and in meter widths from growth on metal substrates?


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Graphite Oxide and its exfoliation to yield Graphite Oxide and its exfoliation to yield graphenegraphene oxideoxideplatelets thus a colloidalplatelets thus a colloidal dispersion (one route to exfoliateddispersion (one route to exfoliated

Oxidant

Graphite oxide exfoliated/suspended in water


as n v ua p a e e s o grap ene ox e


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IUPAC nomenclature: Graphene

It is interestin to see how the different disci lines view ra hene


Chemists/carbon scientists have defined it as above


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1999. Ruoff & team: micromechanical exfoliation

Multilayer graphene

X. K. Lu, H. Huang, N. Nemchuk and R. S. Ruoff,

Patterning of highly oriented pyrolytic graphite by oxygen

plasma etching, Appl. Phys. Lett., 75, 193-195 (1999).

Lu, Xuekun; Yu, Minfeng; Huang, Hui; Ruoff, Rodney S..

Tailoring graphite with the goal of achieving single sheets.

Nanotechnology (1999), 10(3), 269-272.



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Since graphite can be easily cleaved along the basal

plane, the islands can be transferred to flat surfaces of other

substrates, such as mica or Si, simply by rubbing the HOPGsurface against the surface of other substrates. Figure 2 shows

islands transferred onto a Si(001) substrate. The original

islands were 6 m in height. After being transferred to

a Si(001) substrate, all the islands were fanned out into

. -

plates were found on the surface, as shown in figure 2. It

was noticed that some very thin plates were created by this

method of transferring from the patterned HOPG surface onto

the Si surface. This implies that more extensive rubbing of the

patterned (island) HOPG surface against other flat surfaces

might be a way to get multiple or even single atomic layers

of graphite plates. These thin plates of multiple or single

graphite layers can be used as building blocks for fabricating

Ebbesen and Hiura (1995).



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Reviews of the history of the experimental synthesis of

ra hene are rovided, e. ., in:

Zhu, Yanwu; Murali, Shanthi; Cai, Weiwei; Li, Xuesong;uk, Ji Won; Potts, Je rey R.; Ruo , Rodney

S. Graphene and Graphene Oxide: Synthesis,, .

(2010), DOI: 10.1002/adma.201001068 (cover article)

Dreyer, Daniel R.; Ruoff, Rodney S.; Bielawski,Christopher W. From Conception to Realization: An

Historical Account of Graphene and SomePerspectives for Its Future.Angewandte Chemie


, , , - .


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1969. Discoveryassignment of theretofore unassigned LEED patterns (May)

1970s-present. Surface science studies on many substratesepitaxy (Blakely, Ohshima,others)

1975. Growth and electrical isolation on an insulating substrate (SiC; Van Bommelet al.)

1999. Multilayer, single crystal, micromechanical exfoliation (Ruoff)

2004. (a) Transfer of multilayer graphene from pillars to- -

(b) Preparation monolayer graphene on SiC;electrical measurements (J Phys Chem; de Heer)

Note: Ruoff home page: Talk given.

2009. Large area monolayer on Cu-not

at Harvard April 2011, posted on-line,provides further details of the history ofexperimental work on graphene



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and the history continues, as emphasized by newsarticles in the journal Nature:

January 18, 2011 Nature (news article by Eugenie Samuel Reich*)January 25, 2011 Nature (news article by Eugenie Samuel Reich*)

*Author ofPlastic Fantastic: How the Biggest Fraud in Physics Shook

the Scientific World



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Ruoffs dream*: To make n-la er ra hene in kilometerlengthsand roll it up (something like the Cu foil shown above

or as is done with plastic foil). Endless length, meter-wide, roll--

Lets turn now to n=1, or monolayer graphene.

And on Cu!Founded in 2010 b Rod Ruoff: Gra hene Materials LLC.



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Li, X. S.;Li, X. S.; CaiCai, W. W.; An, J. H.; Kim, S.; Nah, J.; Yang, D. X.;, W. W.; An, J. H.; Kim, S.; Nah, J.; Yang, D. X.; PinerPiner, R. D.;, R. D.;VelamakanniVelamakanni, A.; Jung, I.;, A.; Jung, I.; TutucTutuc, E.;, E.; BanerjeeBanerjee, S. K.; Colombo, L.;, S. K.; Colombo, L.; RuoffRuoff, R. S., R. S.

-- -- ,,ScienceScience (2009),(2009), 324324, 1312, 1312--1314.1314.

Gra hene Growth Process

25 m thick 99.8% pure Cu foil

Load Cu foil in furnace

Evacuate furnace

Heat to T ~ 1040oC under H2 gas Introduce CH4 at a flow rate of 35

sccm and P = 500 mTorr

Grow graphene for 1 to 20 min

Cool to room temperature



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Transfer ofTransfer of GrapheneGraphene FilmsFilmsgraphene

e 3 3

Cu

ce one

Glass

substrate

Graphene


PDMS


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GrapheneGraphene on Cu Process Flow: Con Cu Process Flow: C--isotope Labelingisotope Labeling

Evolution of ra hene rowth on Ni and Cu b carbon isoto e labelin Xueson Li Weiwei


Cai, Luigi Colombo, and Rodney S. Ruoff, Nano Letters, (2009) 9, 4268.


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GrapheneGraphene Growth on Cu: MechanismGrowth on Cu: Mechanism

Coverage: 44 %/minrea: m m n

Linear: 1~6 m/min

Evolution of graphene growth on Niand Cu by carbon isotope labeling

Xuesong Li, Weiwei Cai, Luigi Colombo,and Rodney S. Ruoff, Nano Letters,(2009) 9, 4268.


Witec Micro-Raman imaging

system (AFOSR DURIP)


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Pure13

C-labeled ra hite ure12

C-labeled ra hite andisotopically labeled graphenes

thermal, electrical conductivity, electron-phonon coupling,measurements related to spintronics for12C-pure material vs 13C-a e e ,etc. upercon uct v ty n grap te nterca at oncompounds (study isotope effect, electron-phonon coupling)

Skyrmion physics (suggested by Allan MacDonald, UT Austin;expert on 2-DEGs)



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Copper enclosure

A copper pocket is made by folding a piece of copper foil (99.8% Alfa Aesar) and

.

The copper enclosure is placed in the tube furnace for graphene growth via CVD.

fH2 = 2 sccm (p=3.0 E-2 mbar). fCH4 = 0.5 sccm(p=4.0 E-2 mbar). T = 1035 C. t = 90 mins.

Li, X. S.; Magnuson, C. W.; Venugopal, A.; Tromp, R. M.; Hannon, J. B.; Vogel, E; Colombo, L; Ruoff, R.S., Large Area Graphene Single Crystals Grown by Low Pressure Chemical Vapor Deposition of


Methane on Copper. JACS, (2011), 133, 28162819.


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SEM images of graphene domains inside the enclosure

Graphene

0.2 mmgrowth frontb c

20 m 20 mGraphene domains show dendritic growth and can be over 0.5 mm across


Li, X. S.; Magnuson, C. W.; Venugopal, A.; Tromp, R. M.; Hannon, J. B.; Vogel, E; Colombo, L; Ruoff, R. S., Large Area Graphene SingleCrystals Grown by Low Pressure Chemical Vapor Deposition of Methane on Copper. JACS, (2011), 133, 28162819.


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Letter abstractNature NanotechnologyPublished online: 20 June 2010 | Corrected online:25 June 2010 | doi:10.1038/nnano.2010.132Roll-to-roll production of 30-inch graphene films

for transparent electrodes

Sukang Bae1,9, Hyeongkeun Kim1,3,9, Youngbin Lee1,Xiangfan Xu5, Jae-Sung Park7, Yi Zheng5,Jayakumar Balakrishnan5, Tian Lei1, Hye Ri Kim2,Young Il Song6, Young-Jin Kim1,3, Kwang S. Kim7,Barbaros zyilmaz5, Jong-Hyun Ahn1,4, Byung Hee

Hong1,2 & Sumio Iijima1,8



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Measurement of mechanical properties of suspendedMeasurement of mechanical properties of suspendedgraphenegraphene membranesmembranes

Ji Won Suk, Carl W. Magnuson, Richard D. Piner,

, .



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Mechanical testing ofMechanical testing of graphenegraphene membranesmembranes

,the graphene membranes were tested by applying uniform

pressure and detecting their deflections.

Bulge/Burst testing using uniform pressure

PressureRegulator

Optical profiler

Reader

transmitter

Nitrogen

CVD-grown monolayer graphene

Si

Graphene

Pressure

Graphene



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Youngs modulus and prestressYoungs modulus and prestress

Youngs modulus = 1.11 0.21 TPa (mean value)- =

3

4

2

ts

3

nts

1

Cou

1

Cou

0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.80

Young's modulus (TPa)

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.40

Prestress (GPa)



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Fracture strengthFracture strength

os mem ranes ro e a very ow pressure excep one mem rane.This might be due to presence or absence of grain boundaries and the

type of GBs in the membranes.

4

Strength characteristics of tilt

grain boundaries1

2

3

un

tsThe supporting

structure failed

1

Co

0 2 4 6 8 10 12 14 16 180

Frature strength (GPa)


1. Grantab, Ruoff, Shenoy., Science (2010) 330, 946-948.


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Oxidation Resistance of Graphene- Coated Cu

and Cu/Ni Alloy

Shanshan Chen Lola Brown Mark Levendorf Weiwei Cai San -Yon Ju Jonathan Ed eworth Xueson Li


Carl Magnuson, Aruna Velamakanni, Richard D. Piner, Junyong Kang, Jiwoong Park, and Rodney S. RuoffACS Nano, 5, 13211327.(2011). (See this article for further details)

R M t f Th l T t i S d d M l G h


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Raman Measurements of Thermal Transport in Suspended Monolayer Graphene

of Variable Sizes in Vacuum and Gaseous Environments*

1.0*10-1

Torr

Optical absorption:~6% (Balandin group, Nano Lett. 2008, 8, 902-907)

2.30.1% at 550 nm (Geim group, Science 2008, 320, 1308)

3.31.1% at 532 nm (this work)


*Shanshan Chen, Arden L. Moore, Weiwei Cai, Ji Won Suk, Jinho An, Columbia Mishra,Charles Amos,Carl W. Magnuson,Junyong Kang,Li Shi, and Rodney S. Ruoff,ACS Nano, 5(1) 321328.


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Measured Thermal Conductivity of Suspended CVD Graphene

The measured in air is slightly higher than that measured in vacuum due to heat loss to the air.


The obtained thermal conductivity does not show clear dependence on the suspended graphenediameter, suggesting phonon m.f.p. < graphene radius.


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Graphite Oxide and its exfoliation to yield Graphite Oxide and its exfoliation to yield graphenegraphene oxideoxideplatelets thus a colloidal dispersionplatelets thus a colloidal dispersion

Oxidant

Graphite oxide exfoliated/suspended in water


as n v ua p a e e s o grap ene ox e


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Exfoliation/Reduction ApproachExfoliation/Reduction Approach

Graphene oxide sheets are not electrically conductive

Reduction (de-oxygenation) can be employed to partially restorethe graphene network

-[O]O O OOH OH

Graphene oxideGraphene

OHOO OH

Hydrazine


Reduction of graphene oxide with, e.g., hydrazine


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PS/PS/GrapheneGraphene Composite 1Composite 1 volvol %%

The reduced sheets have a crum led

2 m 200 nm

morphology

Even at 1% loading the polymerma r x appears comp e e y e w s ee s

Sasha Stankovich, Dmitriy A. Dikin, Geoffrey H. B. Dommett,Kevin M. Kohlhaas, Eric J. Zimney, Eric A. Stach, Richard D.Piner, SonBinh T. Nguyen and Rodney S. Ruoff, Graphene-


100 nmase compos e ma er a s, a ure - .


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Electrically ConductiveElectrically Conductive NanocompositesNanocomposites

Well exfoliated conductive sheets

Electrical percolation threshold rivals composites with carbon nanotubesSasha Stankovich, Dmitriy A. Dikin, Geoffrey H. B. Dommett, Kevin M. Kohlhaas, Eric J. Zimney, Eric A. Stach,Richard D. Piner, SonBinh T. Nguyen and Rodney S. Ruoff, Graphene-based composite materials, Nature 42


(2006) 282-285 .

G hG h id id


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GrapheneGraphene oxide paperoxide paper

Prepared by filtering a GO dispersion

Forms a layered film that can be peeled away from filter

Sheets interact through van der Waals interactions

Very large surface area

~20 m thick


~5 m thick

M h i f S ll Thi k PM h i f S ll Thi k P


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Mechanics of Small Thickness PaperMechanics of Small Thickness Paper

Dmitriy A. Dikin, Sasha Stankovich, Eric J. Zimney,Richard D. Piner Geoffre H. B. Dommett GuennadiEvmenenko, SonBinh T. Nguyen and Rodney S.

RuoffGraphene oxide paper: preparation andcharacterization. Nature 448, (2007), 457-460..

~1 m thick



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2007 USA DOE Workshop:2007 USA DOE Workshop:

Basic Research Needs of Electrical Ener Stora eBasic Research Needs of Electrical Ener Stora e

EDLCs with specific capacitances in excess of 200 F/g, cycle life > 1 x 106 are

es eciall noteworth 170-180 F/

Increasing energy density of EDLCs to the level of lead-acid batteries will have

enormous impact (20-22 W-h/Kg; Lead acid are about 24-30 W-h/Kg)

Major cross cutting themes (both batteries and ultracapacitors):

Need for developing novel materials tailored for optimal EES performance. (This

also requires that the fundamental principles that govern capacitive charge.

Need for new characterization tools that will provide insight into charge and

mass transfer within electro-active particles as well as across electrode-

electrolyte interfaces.

Need for innovations in electrolytes (the interaction of electrolytes with pores inECs may have vastly different capacitive performance as a function of pore

size).


Goodenough J. Basic Research Needs fo r Electrical Energy Storage. Report of the Basic Energy Sciences

Workshop on Electr ical Energy Storage, 2007.


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UltracapacitorUltracapacitor TechnologyTechnology


Adapted from Maxwell ppt ieee.scv Jan2005


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Stoller, Meryl D.; Park, Sungjin; Zhu, Yanwu; An, Jinho; Ruoff, Rodney S.. Graphene-

Based Ultracapacitors. Nano Letters 8, 3498-3502 (2008)

ABSTRACT

The surface area of a single graphene sheet is 2630 m2/g, substantially higher than values

derived from BET surface area measurements of activated carbons used in current electric doublelayer capacitors. Our group has pioneered a new carbon material that we call chemically

mo e grap ene . ma er a s are ma e rom -a om c s ee s o car on,

functionalized as needed, and here we demonstrate in an ultracapacitor cell their performance.

Specific capacitances of 135 F/g and 99 F/g in aqueous and organic electrolytes, respectively,

have been measured. In addition, hi h electrical conductivit ives these materialsconsistently good performance over a wide range of voltage scan rates. These encouraging

results illustrate the exciting potential for high performance, electrical energy storage devices

based on this new class of carbon material.

Graphene Energy, Inc. http://www.grapheneenergy.net


Graphene as a precursor to make other useful carbons that


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Graphene as a precursor to make otheruseful carbons thatare no longer graphenes

Using chemical activation of exfoliated graphite oxide, we synthesized a porous carbon with a BET surface area of up to 3100

square meters per gram, a high electrical conductivity, and a low O and H content. This sp2-bonded carbon has a continuous three-


, . - . -

cells constructed with this carbon yieldedhigh values of gravimetric capacitance (~170 F/g) and energy density (~20 W-h/kg) with

organic and ionic liquid electrolytes. The processes used to make this carbon are readily scalable to industrial levels. ( Published

online by Science on ScienceXpress May 12, 2011. Corrected galley proof version will appear soon. )


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Thank you for your kind attention!

Graphene on metals: Xuesong Li, Weiwei Cai, Jinho An, Shanshan Chen, Carl Magnuson,Drew Munson, Dr. Luigi Colombo (Texas Instruments Fellow), Richard Piner, Yufeng Hao,Huifeng Li, Hengxing Ji, Charles Amos, Ji Won Suk, Wi Hyoung Lee,

Colloidal G-O and RG-O: Sasha Stankovich (Milliken), Dima Dikin (Northwestern University),Sungjin Park (Inha University), SonBinh Nguyen (Northwestern University), Sung Jin An(Kumoh Institute), Sun Hwa Lee (KAIST), Chris Bielawski, Dan Dreyer, Richard Piner, IskandarKholmanov, Jinho An, Yanwu Zhu, Shanthi Murali

EES: Meryl Stoller, Yanwu Zhu, Shanti Murali, Jon Edgeworth, Hyung Wook Ha, Xianjun Zhu,

Dan Dreyer, Chris Bielawski, Sungjin An

Graphene membranes: Ji Won Suk, Richard Piner; Bennett Goldberg, Anna Swan and team(Boston University); Scott Bunch, Victor Bright (UC Boulder)

Thermal conductivity: Weiwei ai, hanshan hen; Li hi and his research group members

Many outside collaborators (Vikas Berry, Vivek Shenoy, Sangouk Kim, Eric Stach, Dong Su,Matthias Thommes, Bob Wallace, Adam Pirkle, the list is long, sincere apologies to those not


ste

ruoff graphene npg workshop may 2011.pdf

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