APPLIED PHYSICS LETTERS 97, 133301 s2010d

Graphene and graphene oxide nanogap electrodes fabricated by atomic

force microscopy nanolithography
Yudong He,1,2 Huanli Dong,1 Tao Li,1,2 Chengliang Wang,1,2 Wei Shao,1,2 Yajie Zhang,1,2
Lang Jiang,1,2 and Wenping Hu1,a!
1
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Organic Solids, Institute
of Chemistry, Chinese Academy of Sciences, Beijing 100190, People’s Republic of China
2
Graduate University of Chinese Academy of Sciences, Beijing 100190, People’s Republic of China
sReceived 8 August 2010; accepted 5 September 2010; published online 27 September 2010d
Nanogap electrodes have been studied intensively both as ideal research tools for molecular
electronics and fundamental building blocks for nanodevices. Here, graphene and graphene oxide
nanogap electrodes with gap width below 10 nm were fabricated by atomic force microscopy
sAFMd nanolithography. It provides a simple and convenient way to fabricate nanogap electrodes
and transfer the nanogap electrodes onto any required substrate. As a preliminary demonstration,
organic field-effect transistors and organic photoswitchers based on the nanogap electrodes were
fabricated, which all exhibited high performance, indicating the great prospect of the nanogap
electrodes and the AFM nanolithography technique for molecular electronics. © 2010 American
Institute of Physics. fdoi:10.1063/1.3493647g

Nanogap electrodes are ideal candidates for integrating tend the nanogap electrodes for high performance organic
nanostructures or even single molecule into circuits for the optoelectronic devices.
next generation of electronics with promisingly higher effi- The direct etching graphene on SiO2 / Si substrates by
ciency and lower power dissipation, and therefore have at- AFM tips is found almost impossible because graphene
tracted worldwide attention in the past several years.1–3 tends to fold itself when the AFM tip scratches on it.
However, the fabrication of electrodes with well-defined Attractively, the etching of GO on SiO2 / Si substrates by
nanogaps sespecially less than 20 nmd is still a highly chal- AFM tips is easy fFigs. 1sad and 1sbdg. The difference to etch
lenging task because it goes beyond the capability of tradi- graphene and GO by AFM on SiO2 / Si substrates is due to
tional microfabrication technologies. Various strategies have the different weak interactions between graphene/GO and
been accordingly developed including mechanical break SiO2 substrates.16 Fortunately, we find when a thin layer of
junctions,2 electromigration,4 electrochemical plating,5 etc., polymethyl methacrylate sPMMAd s8 nm thickd is inserted
between graphene and SiO2 substrate to enhance the interac-
among which atomic force microscope sAFMd nanolithogra-
tion between graphene and SiO2 substrates, the AFM tip does
phy is attractive for us because comparing with other tech-
not move the graphene layer any more, and on which nan-
niques it is much more effective, economy and easy to be
ogap electrodes can be fabricated easily fFig. 1scdg. It is note-
realized.6,7 worthy that the PMMA sor other organic materialsd layer
Meanwhile, graphene has attracted the world’s attention could be used as dielectric materials too, which is a great
recently, which is considered as ideal candidate because of advantage to pattern the graphene nanogap electrodes on the
its superior stability and conductivity.8 It has been proved polymer insulator for potential applications. Definitely, the
that higher mobility can be obtained by using graphene elec- graphene nanogap electrodes also could be transferred to
trodes in organic field-effect transistors because of its similar other surfaces just by dissolving PMMA away with organic
structure and the highest occupied molecular orbital/lowest solvents.
unoccupied molecular orbit energy levels matching well with
organic materials.9 However, the patterning of graphene
sheets into electrodes with desirable configurations is still an
important and a challenging issue. Up to date, there have
been some methods to tailor graphene layers into desired
geometries, such as electron beam lithography, plasma etch-
ing, or chemical procedures by using nanometer-sized nickel
or iron particles as catalyst,10–15 but most of them suffer
harsh conditions or complex steps. The preparation of
graphene electrodes with nanogaps is much more challeng-
ing and therefore rarely reports have been addressed on it.
Here, we proposed two methods to use AFM tips as knives to
tailor the geometries of graphene and graphene oxide sGOd
to generate well-defined nanogap electrodes and further ex-
FIG. 1. sColord Schematic diagrams of sad etching graphene on SiO2, sbd
ad
Author to whom correspondence should be addressed. Electronic mail: etching GO nanogap electrodes on SiO2 and scd etching graphene nanogap
huwp@iccas.ac.cn. electrodes on PMMA.

0003-6951/2010/97~13!/133301/3/$30.00 97, 133301-1 © 2010 American Institute of Physics

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 133301-2 He et al. Appl. Phys. Lett. 97, 133301 ~2010!

FIG. 2. sColord Schematic diagrams of etching HOPG by AFM and trans-

ferring the patterned graphene nanogap electrodes from HOPG to other
substrates.

Another method to get patterned graphene nanogap elec-

trodes is to etch highly oriented pyrolytic graphite sHOPGd
directly sFig. 2d. The steps can be described as follows: sid a
piece of HOPG is roughly patterned by optical lithography in
microscale so that the outshoot of the patterned part is easier
to be transferred later, siid the patterns could be etched in
submicroscale or nanoscale by AFM lithography, and siiid the
rough and fine graphene patterns on top can be easily trans-
ferred to any other substrates using some techniques such as
stamping and lift off15,17,18 for further applications. A great
advantage of this technique is its extremely high reproduc- FIG. 3. sColord SEM images of fabricated nanogap electrodes: sad squares
arrays, sbd linear arrays, AFM image of scd squares arrays, sdd linear arrays,
ibility. It is dependable to etch different HOPG substrates at sed magnified nanogap electrodes and sfd magnified nanogap electrode arrays
the same etching conditions. Moreover, the same etched na- of graphene on PMMA.
nogap electrodes on HOPG can be used for many times be-
cause only one or several layers of graphene on the top of the
etched HOPG surface are transferred to desired substrates in at 1.0 Vd, which display two following distinct states: sid
one time transferring process. “low” current state at dark condition and siid “high” current
The exemplified patterned graphene and GO nanogap state at light condition. In order to further clear the properties
electrodes were shown in Fig. 3 sGO electrodes can be re- of the graphene nanogap electrodes, the back Si substrate of
duced to graphene electrodes easilyd. The gap width of the the switcher is connected ohmicly as gate electrode, shifting
nanogaps could be tuned by the diameter of the used AFM the switchers into nanometer scale transistors. The output
tips and applied force during etching process. The smallest characteristics of the transistors suggest which work as
gap width could be down to 10 nm using AFM tips made of p-type transistors under an accumulated model fFig. 4sddg.
silicon nitride instead of silicon. Certainly, more complicate
patterns could be also easily prepared by this AFM
nanolithography.6,16
The well-patterned graphene nanogap electrodes indi-
cated their potential applications in devices. As preliminary
demonstration, thin film transistors of the nanogap electrodes
were fabricated by using bottom-contact drain/source elec-
trodes. The devices are fabricated via following five steps
sFig. 4d: sid a thin PMMA layer is spin coated onto the SiO2
substrate, siid graphene sheet is transferred to the PMMA
layer mechanically, siiid nanogap electrodes are fabricated by
AFM nanolithography, sivd Au pads are deposited by the
“organic ribbon mask” technique,19 and then the mask was
peeled off leaving the Au pads as the contacted pads, and svd
copper phthalocyanine sCuPcd is vacuum deposited in and
around the graphene nanogap electrodes.
The devices with graphene nanogap electrodes showed
obvious photoresponse characteristics20 fFig. 4scdg. With FIG. 4. sColord sad Schematic diagram of graphene nanogap electrodes; sbd
schematic structure of CuPc devices based on graphene nanogap electrodes;
light on/off the nanogap devices are capable to switch be- scd photoswitching characteristics of the nanogap devices swhite light, light
tween low/high impedance states as a nanometer scale photo density 5.76 mw/ cm2, V = 1.0 Vd; sdd output characteristics of the CuPc
switcher sthe voltage between two electrodes is kept constant nanogap OFETs.
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 133301-3 He et al.
The on/off ratio of the transistors is as high as 800. Interest-
ing, some devices with short gap width se.g., 10–50 nmd are
observed short-channel effect.
In summary, two methods are introduced to fabricate na-
nogap electrodes of graphene and GO by AFM nanolithog-
raphy. The gap width of the nanogap electrodes could be
down to 10 nm by the techniques. Based on these graphene
nanogap electrodes, bottom-contact thin film devices of
CuPc showed high device performance indicating the pro-
spective application of graphene nanogap electrodes for or-
ganic optoelectronic devices.
The authors acknowledge financial support from Na-
tional Natural Science Foundation of China sGrant Nos.
20721061, 20872146, 50725311, and 60801037d, the China-
Denmark Coproject, TRR61 sNSFC-DFG Transregio
Projectd, the Ministry of Science and Technology of
China sGrant Nos. 2006CB806200, 2006CB932100, and
2009CB930400d, and the Chinese Academy of Sciences.
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