COMMUNICATION
DOI: 10.1002/adma.200701725
Well-Positioned Metallic Nanostructures Fabricated
by Nanotransfer Edge Printing**
By Mianqi Xue, Yanlian Yang, and Tingbing Cao*
Metallic nanowires have drawn continuous research atten-
tion because of their unique electrical, optical, and magnetic
properties and potential applications in mesoscopic research
and nanodevices.[1] Although 1D nanostructures can be easily
synthesized with a “bottom-up” strategy using wet-chemical
methods, precise control and manipulation of these nano-
structures on functional devices remains a great challenge and
interest to academia and industrial fields.[2,3] New methods for
nanowire fabrication and positioning are required to comple-
ment the conventional “top-down” means, such as expensive
photo- or electron-beam lithography.[4]
In recent years some unconventional methods have been
explored for fabricating metal nanostructures to get cost-ef-
fective devices. For example, metal nanowires with controlla-
ble dimensions have been fabricated by electrodepositing
metals within nanoporous membranes,[5–7] and evaporating
and transferring from a selectively etched GaAs/AlGaAs
superlattice.[8] Metal evaporation onto dominos results in
pseudo-3D structures with critical dimensions of < 15 nm.[9]
Edge-spreading lithography generates 30 to 50 nm nanostruc-
tures by using the outer profile of silica beads deposited on
Au or other metal films.[10,11] Whitesides and co-workers have
reported a simple and experimentally convenient method to
fabricate noble metal nanowires and nanorings using the
nanoskiving technique.[12–14] Those free-standing nanostruc-
tures have uniform, controlled dimensions after sectioning
with microtome, and the technique provides a simple alter-
native to fabricate and position the nanostructures onto
prototype devices such as plasmonics. Rogers and co-work-
ers[15–18] and later Delamarche[19] have developed a technique
to pattern metals using an elastomeric stamp. The technique,
nanotransfer printing (nTP), is a very useful new form of soft
lithography by evaporation of thin metal films onto poly(di-
methylsiloxane) (PDMS) stamps that were generated by repli-
ca molding from photolithographically fabricated masters.
–
[*] Prof. T. B. Cao, M. Q. Xue
Department of Chemistry
Renmin University of China
59 Zhongguancun street, Beijing 100872 (P.R. China)
E-mail: tcao@chem.ruc.edu.cn
Dr. Y. L. Yang
National Center for Nanoscience and Technology
Beijing 100080 (P.R. China)
[**] This research was supported by NSF of China under No. 20674096,
20733001, and 50773092.
596 © 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
These metal-coated stamps, when brought into contact with a
second substrate having appropriate surface chemistry, selec-
tively transfers the metal film from the raised features of the
PDMS to the substrate. The transfer depends on weak adhe-
sion of the metal to original stamp, strong adhesion to the
substrate to which the metal transfers, and conformal contact
accomplished by the elastomeric stamp.
We have fabricated thin, electrically conductive, metal films
on the sidewalls of a relief patterns on a PDMS stamp using a
combination of thin-film metal deposition and nTP, and used
these PMDS edged stamps to generate patterns of charge in
thin films of dielectrics by using electrical microcontact print-
ing.[20] Herein we improved this procedure to generate nano-
meter-scale metallic structures on hard substrates in two steps:
first, transfer of the metal from the PDMS stamp, and
then printing of the metallic nanowire onto a silicon wafer
from the sharp edge left on the sidewall of the PDMS stamp;
we refer to this method as nanotransfer edge printing, or
nTEP.
Figure 1 shows the procedure used to fabricate metal nano-
wire arrays by nTEP, which is a combination of thin-film
deposition, nanotransfer printing and edge lithography. The
process contains two nanotransfer printing steps: after the first
nTP step, we discard the silicon wafer with transferred metal
but retain the PDMS stamp with sharp edges; in the second
nTP step, we focus our attention on the transferred material
Figure 1. Schematic diagram showing the fabrication of gold nanostruc-
tures on a silicon wafer using nTEP. The procedure contains two separat-
ed nTP processes: A–C) production of metal edges along the sidewall of
a PDMS stamp, and D–F) production of nanometer-scale (10–50 nm)
metal nanowire arrays positioned on the Si wafer.
Adv. Mater. 2008, 20, 596–600
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from the stamps. We first evaporated a thin film of Au
(10–50 nm) onto the PDMS stamp, as shown in Figure 1B.
Then we deposited (3-mercaptopropyl)-trimethoxysilane onto
a piranha-solution-treated silicon wafer from a 10 mM etha-
nol solution at 60 °C for less than 1 hour, resulting in a self-as-
sembled monolayer (SAM)-coated silicon wafer. The metal-
coated PDMS stamp and SAM-coated silicon wafer were
brought into conformal contact and separated, as shown in
Figure 1C; during the separation, the gold thin-film is trans-
ferred to the SAM-coated silicon wafer because of the cova-
lent bond between gold and sulfur in the SAM, but only from
the raised plateaus. After the separation indicated in Fig-
ure 1D, the PDMS stamp retained the metal film along its
sidewalls and trenches. The metal edge along the sidewalls is
thin (the thickness of the evaporated film is 10 to 50 nm) and
sharp, and the nanometer-scale metal edges ensure us another
fresh PDMS stamp to conduct the nTEP process.
The nTEP process is almost identical to the nTP process,
except that the stamp has variations: as shown in Figure 1E, a
PDMS stamp with sharp Au edges along its sidewall is
brought into conformal contact with SAM-coated silicon
wafers and peeled; after the separation, arrays of metal nano-
wires are permanently left onto SAM-coated silicon substrate
because of the covalent bonds between sulfur from SAM and
Au from metal edges. As shown in Figure 1F, the raised pla-
Figure 2. SEM images of the Au nanostructures on Si wafer. A) Au nano-
teau part in the stamp is plain PDMS that does not react with structures fabricated using nTEP. The original PDMS stamp has 2 lm
sulfur, thus, they separated the adjacent metal nanowires. column features spaced by 3 lm, thus the resulting nanostructures are
Figure 2 shows a set of scanning electron microscopy spaced by 2 lm and 3 lm, respectively. B) Parallel Au nanowires having
(SEM) images of the metal nanowire arrays on a silicon wafer dimensions at 20 nm in width, 5000 lm in length, and 5 lm spacing.
C) Magnified view of a single Au nanowire with a width of 20 nm. The
by transferring gold using nTEP. The shapes and spacing of sample was tilted 20° with respect to the plane to decrease electron scat-
the metal nanostructures are determined by the PDMS stamp; tering. D) Crosshatched nanowire arrays by sequential depositions of Au
as shown in Figure 2A, the straight lines are fabricated from a nanostructures from PDMS stamp with 90° orientation. E) Magnified
PDMS stamp with 2 lm column features spaced by 3 lm, and view of the cross-hatched nanowires.
the resulting nanowire arrays are spaced by 2 lm and 3 lm,
respectively, because the metal film was deposited onto both often resulted in non-uniform metal nanowires, as shown in
sides of the column features. The widths of the nanowires are Figure 3A and C. Therefore, it is extremely difficult to control
determined by the thickness of metal film deposited on the aspect ratio of the metal nanostructure by this way be-
PDMS stamp. The Au nanowires can be extended to more cause of the uncontrollable crack position of the metal film
than 5000 lm in Figure 2B, as measured by SEM. We have during peeling and tearing. A magnified view of nanowire ar-
evaporated 20 nm gold onto the PDMS stamp, and after the rays shown in Figure 3C clearly shows the morphology of a
nanotransfer edge printing process we obtained Au nanowires single metal nanowire located on silicon wafer with very
with thickness very close to 20 nm, with variations of ± 2 nm, rough surface compared with solution-based synthetic metal
as shown in Figure 2C. The magnified view of Au nanowires nanostructures. This may be attributed to the gold clusters
clearly shows that the thickness of the metal film determines grown during metal evaporation by magnetic sputtering, how-
the thickness of the resulting metal nanowire arrays. We have ever, the tearing of the film does affect the morphology of
created crosshatched nanowire arrays by sequential deposi- metal nanowires. In order to control the metal nanowire as-
tion of Au nanostructures from PDMS stamps with Au metal pect ratio and improve the surface quality of resulting nano-
edges, as shown in Figure 2D and E. After positioning Au structures, we adjusted the direction of metal sputtering from
nanowire arrays on SAM-coated Si substrates by nTEP, with perpendicular to an angle of 30 degree relative to the plane of
90° orientations, we placed another freshly peeled metal- the PDMS substrate. Through evaporating metal film with
edge-coated PDMS stamp with the same features and sizes, small angle, as shown in Figure 3B and D, the metal film can’t
the SAM on Si wafer reacted with gold and peeled the reach the trench bottom of PDMS stamp but stay on the
nanowires from the stamp in same manner as shown in Fig- raised plateaus and one single side of the PDMS sidewall, and
ure 1. the height of metal film on the sidewall is determined by the
The quality of nanowire arrays fabricated by nTEP is angle of magnetic sputtering. After peeling the metal film
strongly dependent on the tearing of the metallic film, which from the raised plateaus of PDMS stamp, the metal film left

Adv. Mater. 2008, 20, 596–600 © 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.advmat.de 597
COMMUNICATION
Figure 3. The morphology of Au nanostructures fabricated by different tearing angles.
A,C) show 45° tilted view of SEM and AFM images of Au nanostructures with metal
evaporation perpendicular to the PDMS stamp. B) and D) show a 45° tilted view of
SEM and AFM images of Au nanostructures with metal evaporation 30° to the PDMS
stamp.
on the sidewall of the stamp can be completely transferred
onto silicon wafer by nTEP since there was no metal film in
the trench bottom of PDMS stamp for connection, and the
metal nanowire arrays fabricated under this way have control-
lable aspect ratio and good surface morphology. From a mag-
nified view of Au nanowire by a side-on tilt of SEM image
(45° to the Si substrate), as shown in Figure 2B and AFM im-
age in Figure 2D, we clearly observed much higher aspect ra-
tio and smoother nanowire arrays than the Au nanowire fabri-
cated without adjusting the sputtering direction as shown in
Figure 3A and C.
Using these techniques, we can tune the aspect ratio of the
metallic nanostructures through adjusting the evaporation an-
gle, and thereby have a means by which to obtain the resulting
1D Au nanostructures as nanowires, nanobelts, or nanosheets,
since we have the ability to control their lengths, widths and
thicknesses.
Figure 4 shows the conductance measurements of Au nano-
wire arrays fabricated by nTEP. As schematically illustrated
in Figure 4A, Au nanowire arrays were connected into a close
circuit for conductance measurements. Figure 4B shows the
corresponding current–voltage curve, which is almost linear
and suggests metallic conduction behavior of the Au nano-
structures. Figure 4C and D show the tapping mode and
conductive-mode AFM images of the Au nanowire arrays,
598 www.advmat.de © 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
the continuous linear behavior of Au nanostruc-
tures in conductive AFM image indicates the
metallic conduction property of every single nano-
wire. Further I–V measurements of single nano-
wires by conductive AFM are in good accordance
with the resistances of the nanowire arrays, as
shown in Figure 4B, and their resistance is in the
same order of bulk gold film (10–7 Xm). The long-
range-ordered conductive Au nanowire arrays
have potential applications in field-effect transis-
tors sensors and electronics, and we will conduct
further investigations to explore their applications
in these areas.
There are many ways to grow thin films with
well-controlled thickness between 1 and 50 nm
over large surface areas, for example, thermal
evaporation, magnet sputtering, e-beam evapora-
tion, and chemical/physical vapor deposition.[21]
Edge lithography can take advantage of the capa-
bility to fabricate nanostructures by converting
these structures-which are thin along the z-axis-in-
to structures that are thin along the x-axis. 22 Nano-
transfer edge printing, nTEP, reported in this
manuscript combines the advantage of edge lithog-
raphy and nTP, and has shown its ability to fabri-
cate metallic nanostructures and control the di-
mensions of resulting nanowire arrays. Besides
metal, other materials such as some semiconduc-
tors or insulators can also be deposited through
thin-film evaporation, and these materials usually
have characteristics between bulk films and nano-
scale 1D geometry. For example, SnO2 is an n-type semicon-
ductor with a wide band gap, and the gas-sensing characteris-
tics of SnO2 can be dramatically altered by morphological and
microstructural features such as shape, surface-to-volume ra-
tio, and particle size, etc.[23–25] Here we show another applic-
able demonstration of nanotransfer edge printing: fabrication
of SnO2 nanostructure by nTEP and showing its unusual gas
sensing properties.
Figure 5A shows a schematic diagram of the SnO2 nano-
wire fabrication process. Different from the Au nanowire fab-
rication process, the nTEP process for making SnO2 nano-
wires is adjusted so that a 5 nm Au layer was deposited onto
PDMS stamp prior to 50 nm SnO2 film deposition. In the first
step of nTEP, the SnO2 film and Au layer were peeled from
raised plateaus of PDMS stamp by a plasma-treated fresh
PDMS slab, and this process is identical to nTP developed by
Rogers.[16] In the second step of nTEP, because we could not
find a suitable self-assembled monolayer to directly react with
SnO2 film from silicon wafer, we use a 5 nm Au layer to assist
the removal of SnO2 film from the sidewall of PDMS stamp,
since the SnO2 film was firmly connected with Au layer. The
SEM image shown in Figure 5B clearly shows the morphology
of SnO2 nanowire arrays, which indicates the successful nTEP
fabrication process. Figure 5C and D show the sensing behav-
iors of SnO2 nanowires towards ethanol gas, and from Fig-
Adv. Mater. 2008, 20, 596–600

A B
0.05
Current (A)
0.00
-0.05
-0.10
-6 -4
Figure 4. Conductance properties of Au nanostructures. A) Schematic illustration of conductance
measurement for Au nanowire arrays. B) Current-voltage measurement of Au nanowire arrays. C)
Tapping mode AFM image of Au nanowires. D) Conductive-AFM image of the Au nanowires.
ure 5D we obviously find that SnO2 nanowires have a much
higher sensitivity towards volatile organic compounds (VOCs)
than SnO2 bulk films under the same concentration, which
agrees well with our prediction.
In conclusion, this Communication demonstrates a simple
and inexpensive procedure that generates free-standing metal
nanostructures on a solid substrate. The technique we de-
scribe here can be used to fabricate nanostructures that are
difficult to make by other techniques, and it is possible to
transfer the nanostructures onto a soft substrate for applica-
tion in flexible electronics. The shapes of these nanostructures
are not limited to simple lines since soft lithography can gen-
erate complex 3D structures, and the materials deposited onto
PDMS stamps can extend to most metals and some semicon-
ductors, depending on the pursued functions. The nanostruc-
tures fabricated by this technique can be easily printed and
positioned by manipulating the PDMS stamp, which will pro-
vide significant advantages in fabrication compared to con-
ventional techniques, and can readily find applications in
chemical or biological sensing, optical signal processing, and
nanoelectronic devices.
Experimental
All received materials were used without further purification.
Fabrication of Metal Nanowires on Si Wafer: Soft lithography and rap-
id prototyping were used to fabricate features in SU-8 (Microchem
Adv. Mater. 2008, 20, 596–600 © 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
COMMUNICATION
Corp.), which were subsequently replica
0.10 molded using PDMS pre-polymer to fabri-
cate the flexible stamps. The stamps were
coated with 10–50 nm of gold using a mag-
netic sputtering evaporator (Beijing Technol.
Corp., P.R. China). Silicon wafers were treat-
ed with 30 % H2O2 + 70 % H2SO4 and
washed with de-ionized water, and then coat-
ed (3-mercaptopropyl)-trimethoxysilane in
ethanol solution. The metal-coated PDMS
stamp and SAM-treated silicon wafer were
-2 0 2 4 6
brought into conformal contact and separat-
Applied voltage (V) ed to achieve the first nanotransfer printing
step, and then a PDMS stamp with metal
edges was brought into contact with another
SAM-Si to finish the second nTP, or nTEP.
The images of the gold nanowires were re-
corded by SEM (JEOL7401) and AFM (Vee-
co Bioscope III). Current–voltage measure-
ments were recorded by using a Keithley
4200 sourcemeter, and the conductivity of
the nanowires was checked by the Conduct
AFM (Veeco Bioscope III).
Crosshatched nanowire arrays were ob-
tained by sequential depositions of Au nano-
structures from PDMS stamp with Au metal
edges with 90° orientation. The images of the
crosshatched nanowire arrays were recorded
by SEM (JEOL7401).
The direction of metal sputtering was ad-
justed from perpendicular to an angle of 30°
relative to the plane of the PDMS substrate.
After peeling the metal film from the raised
plateaus of PDMS stamp, the metal film left
on the sidewall of the stamp could be com-
pletely transferred onto silicon wafer by
nTEP, since there was no metal film in the trench of the PDMS stamp.
A magnified view of Au nanowire by a side-on tilt of SEM image (45°
to the Si substrate) and AFM image were recorded by SEM
(JEOL7401) and Veeco bioscope III.
Fabrication of SnO2 Nanowires and Thin-Film Gas Sensor: PDMS
stamps were coated with 5 nm gold and 50 nm SnO2 using a magnet
sputtering evaporator (Beijing Technol Corp., China). The Au and
SnO2 film coated PDMS stamp and another fresh PDMS are plasma
oxidized and then brought into contact, after separation, the stamp
with the remainder structures was brought into contact with another
SAM-Si substrate to prepare SnO2 nanowires gas sensor. The images
of the gold nanowires were recorded by SEM (JEOL7401). 5 nm gold
and 50 nm SnO2 are uniformly evaporated on a silicon substrate to
prepare SnO2 thin-film gas sensor.
Ethanol Gas Detection: Gas-sensing properties were measured
using a static test system including a test chamber and a data acquisi-
tion/processing system. Dry air was used as both a reference gas and a
diluting gas to obtain desired concentrations of analytics. The gas re-
sponse is defined as Rair/Rgas, where Rgas and Rair are the resistances
of the sensor upon exposure to an analytic and dry air at 220–300 °C,
respectively.
Received: July 16, 2007
Revised: September 5, 2007
Published online: January 17, 2008
–
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www.advmat.de 599
COMMUNICATION

PDMS

Au
PDMS (5nm)

SnO2
PDMS (50nm)

SAM of
PDMS SH(CH2)3Si(OCH3)3

Si Si

7
Conductance Response (Rair/Rgas)

6
C Conductance Response (Rair/Rgas)
12
D SnO2 nanowires
10
5
8
4
6
3
4
2 SnO2 films
2
1
0
0 20 40 60 80 100 120 140 0 10 20 30 40
Time (s) Time (s)

Figure 5. Gas sensing properties of SnO2 nanowires. A) Schematic illustration showing the fabrica-
tion of SnO2 nanowire arrays. B) SEM image showing the morphology of SnO2 nanowires. C) Dy-
namic response of SnO2 sensors at 220 °C to ethanol gas with concentration of 1 ppb–10 ppm. D)
Sensing behavior of bulk SnO2 film and nanoscale SnO2 structures towards ethanol gas with con-
centration of 1 ppb.

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