Langmuir 2003, 19, 5475-5483 5475

Silicone Transfer during Microcontact Printing

Karin Glasmästar,* Julie Gold, Ann-Sofie Andersson, Duncan S. Sutherland, and
Bengt Kasemo
Department of Applied Physics, Chalmers University of Technology,
SE-412 96 Göteborg, Sweden

Received September 16, 2002. In Final Form: April 14, 2003

Microcontact printing (µCP) is a widely used method to make miniaturized patterns on surfaces. In this
work, the issue of the possible transfer of stamp material from the stamp to the substrate during stamping
was addressed. Poly(dimethylsiloxane) was used to stamp Milli-Q water or buffer on substrates of SiOx,
TiO2, and Au. X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry
(ToF-SIMS) were used to measure and characterize the substrate before and after stamping to detect the
possible transfer of stamp-related material to the substrates. Both the XPS and the ToF-SIMS analyses
show that silicone-related material is transferred from flat stamps and that even more material is transferred
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from patterned stamps. Interestingly, a UV/ozone treatment (essentially oxidation of the surface) of the
stamps before inking and stamping significantly reduces the silicone transfer. Two application examples
are used to illustrate the importance of silicone transfer to the substrates during µCP: water condensation
patterns and supported lipid bilayer formation.
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Introduction layers function as a diffusion barrier and are reported to

Microcontact printing (µCP), or soft lithography, was
introduced by Kumar et al. in the early 1990s1,2 as a means
for fast and low-cost pattern transfer onto gold films
supported on silicon substrates. The technique has since
become widely used to pattern surfaces for a variety of
research and technical applications.1-6 During µCP, an
elastomeric stamp, having relief structures covered (inked)
with molecules, is brought into contact with a solid
substrate and then removed, leaving a pattern of the “ink”
in the areas where the stamp was in contact with the
substrate. The conformal contact between the stamp and
the surface is ascertained by the interfacial forces and
flexibility of the stamp material. Depending on the
intended application, the ink used for printing varies from,
for example, alkanethiols1-3 to proteins,4-6 and the
substrate varies from glass5,6 to metal surfaces.1-4,7 The
most common surfaces are gold, glass/SiO2, and silver.
Despite the broad variation of inks and substrates, there
is one common feature: the stamp is made of an elastomer,
usually poly(dimethylsiloxane) (PDMS).
PDMS is a hydrophobic polymer known to be very
dynamic in terms of the mobility of the polymer chains at
the surface.8 This mobility enables hydrophobic or more
hydrophilic side groups to be exposed at the surface
depending on the environment. The surface of PDMS can
be modified by UV/ozone treatment, creating a thin (20-
30-nm) glassy layer on the surface.9 Such thin glasslike
* To whom correspondence should be addressed. E-mail:
karing@fy.chalmers.se.
(1) Kumar, A.; Whitesides, G. M. Appl. Phys. Lett. 1993, 63, 2002.
(2) Kumar, A.; Biebuyck, H. A.; Whitesides, G. M. Langmuir 1994,
10, 1498.
(3) Biebuyck, H. A.; Larsen, N. B.; Delamarche, E.; Michel, B. IBM
J. Res. Dev. 1997, 41, 159.
(4) Tan, J. L.; Tien, J.; Chen, C. S. Langmuir 2002, 18, 519.
(5) Wheeler, B. C.; Branch, D. W.; Corey, J. M.; Weyhenmeyer, J. A.;
Brewer, G. J. Proceedings of the 19th International Conference-IEEE/
EMBS; Chicago, IL, 1997.
(6) Kung, L. A.; Kam, L.; Hovis, J. S.; Boxer, S. G. Langmuir 2000,
16, 6773.
(7) Xia, Y.; Kim, E.; Whitesides, G. M. J. Electrochem. Soc. 1996,
143, 1070.
(8) Mark, J. E.; Allock, H. R.; West, R. In Inorganic polymers; Prentice
Hall Inc.: Englewood Cliffs, NJ, 1992, 141.
be quite brittle10,11 compared to bulk PDMS.
The use of hydrophobic inks such as alkanethiols in
µCP do not normally require any pretreatment of the
stamps.2,12 However, if the ink is hydrophilic, for example,
water-soluble proteins,13-15 phospholipids,16 or amines,17
the stamp i often oxidized.13,17 The oxidized stamp is
claimed to have a higher protein adsorption capability13
and to give higher coupling yields when stamping amines17
than the untreated stamp.
A matter of concern, in some situations where µCP is
used, is the risk of the transfer of molecules or fragments
from the stamp material to the patterned surface. In the
case of PDMS, these fragments could be low-molecular-
weight residues, molecules, molecular fragments, etc. Such
transfer could compromise the end result by contaminating
the surface, changing the wetting and adhesion properties.
There are surprisingly few studies of these aspects in the
literature. A few publications report PDMS contamination
on the printed substrates,18-20 but these studies were not
aiming at studying the transfer process as such or a
solution to the problem. In one of these publications,18 a
slightly different process than the standard µCP procedure
was used (1-6 bar overpressure during the printing of
thiols). PDMS was detected, by X-ray photoelectron
spectroscopy (XPS) and infrared reflection absorption
(9) Ouyang, M.; Yuan, C.; Muisener, R. J.; Boulares, A.; Koberstein,
J. T. Chem. Mater. 2000, 12, 1591.
(10) Chaudhury, M. K.; Whitesides, G. M. Science 1992, 255, 1230.
(11) Hillborg, H.; Gedde, U. W. Polymer 1998, 39, 1991.
(12) Delamarche, E.; Schmid, H.; Bietsch, A.; Larsen, N. B.; Rothuizen,
H.; Michel, B.; Biebuyck, H. J. Phys. Chem. B 1998, 102, 3324.
(13) St. John, P. M.; Davis, R.; Cady, N.; Czajka, J.; Batt, C. A.;
Craighead, H. G. Anal. Chem. 1998, 70, 1108.
(14) Kam, L.; Boxer, S. G. J. Biomed. Mater. Res. 2001, 55, 487.
(15) James, C. D.; Davis, R. C.; Kam, L.; Craighead, H. G.; Isaacson,
M.; Turner, J. N.; Shain, W. Langmuir 1998, 14, 741.
(16) Hovis, J. S.; Boxer, S. G. Langmuir 2001, 17, 3400.
(17) Lahiri, J.; Ostuni, E.; Whitesides, G. M. Langmuir 1999, 15,
2055.
(18) Böhm, I.; Lampert, A.; Buck, M.; Eisert, F.; Grunze, M. Appl.
Surf. Sci. 1999, 141, 237.
(19) Yang, Z. P.; Belu, A. M.; Liebmann-Vinson, A.; Sugg, H.; Chilkoti,
A. Langmuir 2000, 16, 7482.
(20) Jud, P. P. Semester thesis. ETH Zürich, Zürich, Switzerland,
2001.

10.1021/la026558x CCC: $25.00 © 2003 American Chemical Society

Published on Web 05/20/2003
5476 Langmuir, Vol. 19, No. 13, 2003
spectroscopy, as a contamination on the printed surface.
In another report, Yang et al.19 printed biotinylated amino-
terminated oligoethyleneglycol on activated poly(ethylene
terephthalate) (PET) surfaces, using stamps treated by
oxygen plasma for 10 min. They found silicone in the
regions where the stamp had been in contact with the
substrate (by time-of-flight secondary ion mass spectrom-
etry, ToF-SIMS). In the third report, nonoxidized stamps
were used to print poly(ethylene glycol)-peptide deriva-
tives with flat stamps on TiO2, where the transfer of an
Si-containing species to the substrate was shown with
XPS.20
To the best of our knowledge, there is only one previous
study in the literature, by Graham et al., that examines
in any detail the issue of PDMS being transferred to the
substrate during the µCP procedure.21 They demonstrate
PDMS contamination on gold by XPS [Si(2s)] and
ToF-SIMS (positive and negative spectra) after the µCP
of thiols. The study was carried out using flat stamps.
The authors propose a 1-week-long cleaning process for
the stamps to lower the amount of transfer to below the
detection limit of XPS. This treatment was suggested to
remove low-molecular-weight fragments.
There are several pending questions regarding the
possible transfer of molecules/fragments from PDMS
stamps to the substrate. To what extent does the amount
of the transferred contaminant material depend on the
pretreatment of the stamp or material onto which the
pattern is stamped? Does the type of ink molecules used
or size of the pattern affect the amount being transferred?
Does the transfer influence the quality of the stamped
patterns? Such questions, some of them arising during an
application of µCP in our laboratory, motivated us to make
a more detailed study of this issue, focusing on the role
of the treatment of the stamp preceding inking and
stamping. Questions regarding the influence of the type
of ink molecules (e.g., competitive adsorption) were not
addressed in this work.
We used XPS and ToF-SIMS to measure the amount
and character of PDMS transfer from flat and patterned
stamps to substrate surfaces of gold, TiO2, and SiOx. The
µCP process was performed using water or buffer as the
ink and without external pressure. We explored whether
a UV/ozone pretreatment of the PDMS stamp could reduce
the amount of transferred material. The choice of SiOx as
one of the substrates was motivated by the many ap-
plications of µCP on glass substrates. TiO2 and gold
surfaces were chosen for two reasons. First, there was a
desire to have more than one surface (chemistry) for
comparative purposes, and second, XPS detection of Si-
containing molecules (transferred from PDMS) is much
easier on a surface not containing Si as an element.
Materials and Methods
Surface Preparation. All substrates for µCP were prepared
from (100)-oriented polished silicon wafers (Siltronix, Archamps,
France). Wafers protected by a sacrificial poly(methyl meth-
acrylate) (PMMA) layer were partially cut using a diamond saw
(Loadpoint Microace 3+). PMMA was then removed by sequential
ultrasonic agitation in acetone, 2-propanol, and Milli-Q water.
Thin films of TiO2 and Au were deposited on some of the wafers
by electron-beam-induced thermal evaporation (AVAC HVC-600).
The TiO2 surfaces were prepared by first evaporating a 40-nm-
thick film, which was then oxidized to saturation by active oxygen
treatment (O2 RF plasma: 0.5 Torr; 200 W; 120 s).22 The gold
(21) Graham, D. J.; Price, D. D.; Ratner, B. D. Langmuir 2002, 18,
1518.
(22) Aronsson, B. O.; Lausmaa, J.; Kasemo, B. J. Biomed. Mater.
Res. 1997, 35, 49.
Glasmästar et al.
Figure 1. Schematic of the procedure of µCP used in this work.
A stamp is cast from a master. The stamp is soaked in ink
(Milli-Q or PBS) for 1 min, rinsed (Milli-Q only or PBS followed
by Milli-Q), and dried in a stream of N2. The stamp is “rolled”
over the sample and left in contact for 3 min before it is rolled
off. No external pressure is applied.
coatings were produced by first covering the surface with a thin
adhesion layer of Ti, followed by the evaporation of 30 or 40 nm
of Au. Uncoated silicon wafer substrates (with thin native oxide
layers of ∼1-2 nm) were used as the model SiO2 substrates,
hereafter referred to as SiOx. The individual samples were
released from the wafer by breaking along the partially cut lines.
Before use, all the samples were blown with nitrogen gas to
remove particulate contaminations, which was followed by
exposure to UV/ozone for 5 min to remove hydrocarbon con-
taminations.
µCP. Stamps for µCP were formed by curing PDMS (Sylgard
184, Dow Corning, Brussels, or Rhodorsil RTV 1556 A+B, Sikema
AB, Stockholm) against a master (room temperature, >24 h).
The Sylgard 184 was chosen because it is the most common PDMS
in the µCP community. The master for the flat stamps was an
Au-coated silicon wafer. Patterned masters (lines or squares)
were made by standard photolithography techniques. The line
patterns were 5-µm-wide lines (in contact during stamping)
separated by 15-µm-wide spaces. The square patterns were a
grid of 10-µm-wide, elevated lines. The squares between the lines
were 10 by 10 µm and were not in contact with the surface during
stamping.
The µCP procedure used is illustrated in Figure 1. The stamps
were used either as prepared or after UV/ozone treatment for 10
min. Because the prime interest in this work was to investigate
the possible transfer of material from the PDMS stamp during
the patterning of water-soluble molecules, such as proteins, the
ink chosen should be representative of the bulk solutions used
in such µCP processes. The two model “inks” were Milli-Q water
and phosphate buffer saline (PBS, Sigma-Aldrich).
XPS Analysis. All the samples for the XPS analysis were
mounted in the vacuum chamber within 20 min after preparation
(i.e., after stamping or surface pretreatment). All the XPS spectra
were recorded using monochromatic Al KR radiation, with a take-
off angle of 45° from the sample surface normal (PHI 5500C
MultiTechnique system). The survey spectra were recorded at
a pass energy of 187.85 eV, and detailed spectra of the individual
elements were recorded at 5.85 eV. The survey spectra from two
spots on each sample were used for the calculation of their atomic
composition at the surface, and one detailed spectrum was
recorded to obtain chemical-shift information (at least two
samples). The X-ray-beam spot diameter was about 1 mm.
In one experiment, flat stamps (untreated or UV/ozone
pretreated) were covered with a thin Al foil (approximately 13-
µm thick), which had a square (5 × 5 mm) hole. A gold sample
was positioned on top of the foil for 3 min, ensuring noncontact
between the stamp and the surface but allowing possible vapors
from the PDMS stamp to reach the gold surface. This experiment
was performed to control any transfer of molecules from the
PDMS stamp to the substrate via the gas phase, that is, from
the regions of the stamp that are not in direct contact with the
substrate.
Silicone Transfer
Figure 2. High-resolution XPS Si(2p) spectra from PDMS
stamps (Sylgard 184 elastomer), untreated or UV/ozone-treated.
The curves are displaced along the y axis for clarity and are
normalized with respect to the total signal. The spectra were
recorded using an electron gun to compensate for the charging
and were later shifted to C(1s) ) 284.4 eV for a charging
reference. The arrow points at a shoulder, indicating the
presence of more oxidized species.
The XPS analysis of PDMS (Sylgard 184 elastomer) stamps
were performed using equipment and settings the same as those
described previously, with the addition of an electron flood gun
to compensate for the charging. The electron gun was adjusted
so that the O(1s) signal of PDMS was at about 532 eV. A result
of the charging neutralization process was that the total intensity
varied between the samples. Therefore, we chose to normalize
the curves of Figure 2 with respect to the total signal.
The spectra shown in Figures 2 and 3 were corrected for
charging effects by shifting the peaks as follows: PDMS spectra
were shifted so that the binding energy (BE) for C(1s) was 284.4
eV; spectra from the Au samples were shifted to Au(4f7/2) ) 84.0
eV; spectra from the SiOx samples were shifted to Si(2p3/2) ) 99.3
eV; and spectra from the TiO2 samples were shifted to Ti(2p3/2)
) 458.8 eV.
ToF-SIMS Analysis. The ToF-SIMS analyses were performed
using a ToF-SIMS IV (ION-TOF GmbH) system in static mode,23
that is, the ion dose was below 1013 ions/cm2. Gallium ions (25
kV; 1 pA) were used as the primary beam. Both high mass
resolution spectra (m/∆m ) 7000) and high lateral resolution
images (<1 µm) were recorded. Flat stamps and stamps with
line patterns, with and without UV/ozone pretreatment, were
used to stamp Milli-Q water on Au substrates. The analyses
started at about 80 min after preparation.
Light Microscopy. Dark-field light microscopy was used to
inspect certain aspects of the quality of the stamped patterns.
The microscope used was a Zeiss Axiotech microscope equipped
with a digital camera. Water condensation patterns were made
by placing the sample on an ice-cooled piece of copper, under the
microscope objective, in an environment of humid air and by
letting water condense on the sample surface.
Another useful control system, sensitive to the chemical state
of the surface, that has been extensively studied in our group,
is the formation of supported phospholipid bilayers by vesicle
adsorption and rupture (see, e.g., ref 24). A lipid bilayer will
form on a clean glass surface if it is exposed to lipid vesicles.
Fluorescently labeled unilamellar lipid vesicles were made by
extrusion (11 × 100 nm followed by 11 × 30 nm polycarbonate
membranes, Whatman, U.S.A.) of a 5 mg/mL lipid mixture in a
Tris buffer of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine
(POPC; Avanti Polar Lipids, AL) and 0.5% (w/w) of 2-[12-(7-
(23) Vickerman, J. C., Briggs, D., Eds.; ToF-SIMS: Surface analysis
by mass spectrometry; IM Publications and SurfaceSpectra Limited:
Huddersfield, U.K., 2001.
(24) Keller, C. A.; Glasmästar, K.; Zhdanov, V. P.; Kasemo, B. Phys.
Rev. Lett. 2000, 84, 5443.
Langmuir, Vol. 19, No. 13, 2003 5477
Table 1. Atomic Composition by XPS Survey Spectra of
PDMS Stampsa
PDMS sample C(1s) O(1s) Si(2p)
untreated 42.8 ( 0.3 31.4 ( 1.0 25.8 ( 0.7
treated 36.4 ( 0.1 38.5 ( 0.5 25.1 ( 0.6
a Mean values are noted in percent plus or minus the standard
deviation from two data points per sample type. PDMS was Sylgard
184 elastomer, untreated or UV/ozone-treated (10 min).
nitrobenz-2-oxa-1,3-diazol-4-yl)amino]dodecanoyl-1-hexadecanoyl-
sn-glycero-3-phosphocholine (NBD-HPC; Molecular Probes,
U.S.A.). Vesicles produced by this method have an average
diameter of 40-60 nm (by dynamic light scattering). Glass
coverslips (Merck) were cleaned by sequential ultrasonic agitation
in acetone, 2-propanol, and Milli-Q water, dried, and UV/ozone-
treated for 10 min. The cleaned coverslips were then stamped
and subsequently incubated in a solution of vesicles (30 µL in 1
mL of buffer) for 10 min, rinsed with buffer, and imaged using
an Axioplan 2 Imaging epifluorescence microscope (Zeiss).
Results
XPS Analyses of Stamps. To be able to trace the
contaminations coming from PDMS used in this study,
XPS analyses of untreated and UV/ozone-treated flat
PDMS stamps were performed (Sylgard 184 elastomer).
Figure 2 shows the high-resolution XPS spectra of the
Si(2p) region for untreated and UV/ozone-treated PDMS.
For both untreated and UV/ozone-treated PDMS, the Si-
(2p) peak is asymmetric. This is much more pronounced
for the untreated stamp. The most dominant peak at 101.9
eV of the untreated PDMS corresponds well to the
reference spectra for PDMS (101.8 eV).25 The shoulder at
a higher BE, at the arrow in Figure 2, indicates the
presence of more oxidized species. After UV/ozone treat-
ment, the peak at 101.9 eV is shifted toward a higher BE
(102.5 eV), which is in agreement with the literature.9,26,27
However, the peak is not shifted completely to the SiO2
value (103.3 eV),28 indicating that the surfaces of the UV/
ozone-treated stamps have a surface chemistry somewhere
between PDMS and SiO2. The atomic composition of the
stamp surface (Table 1) shows a decrease in carbon and
an increase in oxygen content upon UV/ozone treatment.
XPS Analyses Using Flat Stamps. The first set of
stamping experiments was made with untreated and UV/
ozone-pretreated stamps, using Milli-Q water and buffer
solutions, to stamp SiOx, TiO2, and gold surfaces. Parts
A-F of Figure 3 present, for each surface type, the XPS
spectra taken before stamping, after stamping with
untreated stamps, and after stamping with UV/ozone
pretreated stamps, using Milli-Q water as the ink. The
main observations are that (i) the transfer of material
occurs from untreated stamps on all the surface types
examined and (ii) a pretreatment of the stamp with UV/
ozone lowers the amount of PDMS (Sylgard 184, Dow
Corning) transferred from flat stamps to substrates of
Au, SiOx, and TiO2.
The XPS analysis of PDMS transfer to the SiOx substrate
is complicated by the fact that the substrate itself has a
strong Si signal. The transfer from untreated PDMS
stamps is, however, still detectable by the Si(2p) signal
in the XPS spectra (Figure 3A), although a quantification
is not possible without extensive (and often unreliable)
(25) Beamson, G.; Briggs, D. High resolution XPS of organic polymers;
John Wiley & Sons: Chichester, U.K., 1992.
(26) Bar, G.; Delineau, L.; Hafele, A.; Whangbo, M. H. Polymer 2001,
42, 3627.
(27) Murakami, T.; Kuroda, S.; Osawa, Z. J. Colloid Interface Sci.
1998, 202, 37.
(28) Chastain, J., Ed.; Handbook of X-ray Photoelectron Spectroscopy;
Perkin-Elmer Corporation: Eden Prairie, MN, 1992.
5478 Langmuir, Vol. 19, No. 13, 2003 Glasmästar et al.

Figure 3. High-resolution XPS spectra from samples not stamped or stamped with untreated or UV/ozone-treated flat stamps
(Sylgard 184 elastomer) using Milli-Q water as the ink. All the spectra from the SiOx samples were shifted to a BE for Si(2p3/2)
of 99.3 eV, the TiO2 samples to a BE for Ti(2p3/2) of 458.8 eV, and the Au samples to a BE for Au(4f7/2) of 84.0 eV. For clarity, the
curves are displaced on the y axis. (A) Si(2p) spectra of SiOx samples. (B) C(1s) spectra of SiOx samples. (C) Si(2p) spectra of TiO2
samples. (D) O(1s) spectra of TiO2 samples. (E) Si(2s) spectra of Au samples. (F) O(1s) spectra of Au samples.

curve fitting. Inorganic silica (SiO2) has a peak at 103.3 BE (∼102 eV), which is not observed on the samples where
eV,28 which is clearly visible on all the SiOx samples. UV/ozone-treated stamps were used. The XPS spectra from
However, for the samples that were stamped with an the untreated PDMS stamps themselves (Figure 2) show
untreated stamp, this peak shows a shoulder at a lower a nice correlation with this shoulder observed at 102 eV
Silicone Transfer
Table 2. Atomic Composition by XPS Survey Spectra of the Samples Stamped with Flat PDMS Stampsa
substrateb stamp C(1s)
Au untreated stamp 29.3 ( 5.7
treated stamp 34.5 (5.5
not stamped 32.3 ( 8.8
TiO2 untreated stamp 24.3 ( 4.8
treated stamp 15.0 ( 0.9
not stamped 21.7 ( 7.4
SiOx untreated stamp 16.9 ( 2.1
treated stamp 13.9 ( 2.0
not stamped 12.9 ( 0.6
a Mean values are noted in percent plus or minus the standard deviation of at least four data points per sample type. b For some of the
Au samples, a contamination of Cu was found (max 4%), probably a result of a contamination of the evaporation source. All the Ti samples
had fluorine contamination (max 2%) from the oxygen plasma equipment. c The Si(2p) peak was used for all but the Au substrates, where
the Si(2s) peak was used. The ink used was Milli-Q water; the contact time was 3 min. The stamps were made of Sylgard 184 elastomer,
untreated or UV/ozone-treated (10 min).
on the samples stamped with untreated stamps. Hence,
PDMS material is transferred from untreated stamps to
SiOx substrates during µCP.
Figure 3B shows the C(1s) spectra for the different SiOx
samples. The peak at 285.5 eV, most likely arising from
ambient hydrocarbons, is clearly shifted to a lower BE
(285.1 eV) for the samples stamped with untreated stamps
as compared to that of the samples that were not stamped
or stamped with UV/ozone-treated stamps. This is prob-
ably a mixed peak of atmospheric hydrocarbons and carbon
from PDMS, the latter having a peak at 284.4 eV.25
For the stamped TiO2 samples, the results were similar
to the ones described for the SiOx samples previously. An
intensity change of the Si(2p) peak (Figure 3C) was
observed on the samples stamped with untreated stamps.
The Si(2p) peak (Figure 3C) shows that some Si-containing
species are also present on the sample that was not
stamped. The latter probably originates from wafer dust
(remember that Ti was deposited on a Si wafer) produced
when snapping the chips or maybe from the reactive ion
etcher used to oxidize the TiO2 samples. The atomic
compositions, as were calculated from the survey spectra
(Table 2), show a significantly higher Si content for the
stamped samples than that for the not stamped ones.
Furthermore, the UV/ozone treatment of the stamp seems
to reduce the transfer of Si-containing species to the TiO2
surface.
The “normal” shape of the O(1s) peak for TiO2 surfaces
is observed for the sample that was not stamped (Figure
3D). The tail at a higher BE is assigned to the organic
compounds bound to the surface.29 An additional peak at
532.3 eV is found for the samples stamped with the
untreated stamps, which corresponds to the O(1s) peak
for PDMS (532.4 eV, not shown). Also, the fact that the
intensity of the TiO2 oxygen peak is reduced when
stamping with an untreated stamp supports the conclusion
of a transferred adlayer.
For the Au samples, the Si(2p) signal cannot be used
to identify the PDMS transfer because it is hidden in the
large background of the Au(4f) peak. However, the Si(2s)
signal (Figure 3E and Table 2) clearly shows that
Si-containing species are transferred to the gold surface
from untreated stamps whereas the UV/ozone-treated
stamps transfer only trace amounts (if any). A shape
change and shift of the O(1s) signal were also observed
(Figure 3F). For not-stamped, UV/ozone-treated Au, a
double peak is observed in the BE range of 529-531 eV.
According to the literature,30 these peaks correspond to
chemisorbed oxygen (529.1 eV) and gold oxide (530.1 eV)
(29) Lausmaa, J.; Kasemo, B.; Mattsson, H. Appl. Surf. Sci. 1990,
44, 133.
(30) Krozer, A.; Rodahl, M. J. Vac. Sci. Technol., A 1997, 15, 1704.
Langmuir, Vol. 19, No. 13, 2003 5479
O(1s) Si(2p/2s)c Au(4f) Ti(2p)
22.3 ( 2.4 6.2 ( 1.6 41.5 ( 3.4
14.0 ( 2.0 0.2 ( 0.4 50.3 ( 4.9
16.2 ( 3.8 0 48.8 ( 4.8
50.7 ( 3.7 7.4 ( 3.4 15.6 ( 3.4
58.1 ( 0.6 3.6 (0.5 20.7 ( 1.1
55.5 ( 4.3 1.5 ( 0.1 19.1 ( 2.9
38.8 ( 0.7 44.3 ( 1.4
40.3 ( 0.5 45.6 ( 1.4
40.9 ( 1.1 46.1 (0.7
Table 3. Atomic Composition by XPS Survey Spectra of
the Au Samples Stamped with Patterned Stampsa
stamp C(1s) O(1s) Si(2s) Au(4f)
untreated stamp 30.5 ( 2.2 23.2 ( 1.8 10.0 ( 1.2 35.9 ( 1.4
UV/O3-treated stamp 27.0 ( 1.9 19.3 ( 1.5 3.1 ( 2.2 49.8 ( 1.8
a Mean values are noted in percent plus or minus the standard
deviation. To be compared to when flat stamps were used, see Table
2. Patterned stamps were 5-µm-wide lines separated by 15-µm
spaces. The ink used was Milli-Q water; the contact time was 3
min. The stamps were made of Sylgard 184 elastomer, untreated
or UV/ozone-treated (10 min).
deposited on the surface as a result of the ozone treatment.
(Our BE values are slightly higher than those reported
by Krozer and Rodahl.) The O(1s) signal from the samples
stamped with untreated PDMS results in a dominant peak
at a higher BE (531.8 eV), which can be associated with
the presence of PDMS (532 eV).25
When the observations in Figure 3A-F are summarized,
the most important result is that the UV/ozone-treated
stamps transfer less PDMS-derived material than the
untreated ones. This result is further supported by the
following description of the ToF-SIMS results. If we
compare the different surface types, we find that the UV/
ozone pretreatment is more efficient in lowering the
transfer to gold surfaces than that to TiO2 surfaces (Table
2). Unfortunately, it is hard to perform a quantification
of the transfer to SiOx surfaces because the silicon peaks
from PDMS and the substrate overlap.
That PDMS sticks less to Au than to TiO2 substrates
is actually supported by observations from the casting
process: PDMS cured on masters of plain SiOx or TiO2-
coated wafers was extremely hard to release. In contrast,
when Au-coated wafers were used as masters, PDMS was
quite easily released after the curing. Hence, it appears
that the direct chemical interaction between PDMS and
the substrate is stronger for the two oxide surfaces
compared to that of gold.
All the data presented here are from the µCP of Milli-Q
water using the Sylgard 184 elastomer. Trends the same
as those described previously were found when stamping
PBS and also when using another brand of PDMS that is
less commonly used for µCP: Rhodorsil RTV 1556 (data
not shown).
XPS Analyses Using Patterned Stamps. Types of
experiments the same as those described previously were
performed using the gold samples and patterned stamps
having 5-µm-wide lines separated by 15-µm-wide spaces
(depth 10 µm). The elemental concentration from the XPS
survey spectra of gold surfaces stamped with patterned
stamps are shown in Table 3. These stamps seem to
transfer more Si-containing species to gold substrates than
the flat stamps do. This conclusion is drawn from the
5480 Langmuir, Vol. 19, No. 13, 2003
Figure 4. ToF-SIMS images for selected fragments characteristic of PDMS. The chemical formula of each fragment is marked
under the respective image. (A) A gold surface stamped with an untreated PDMS stamp (Sylgard 184; Milli-Q water as the ink).
The stamp was in contact with the gold surface at 5-µm-wide lines separated by 15-µm-wide spaces. The scan size was 101 × 101
µm2. (B) Same as part A except that the stamp in this case was UV/ozone-treated for 10 min before stamping. The scan size was
101 × 101 µm2.
Table 4. ToF-SIMS Signals from the Au Samples
Stamped with Flat or Patterned Stamps
flat stamp patterned stamp
UV/O3 UV/O3
signal untreated treated untreated treated
gold/total 249 814 89 487
ion count
a The numbers given are averages over the whole image (101 ×
101 µm). The lower the gold signal, the more adsorbates on the
surface. For comparison, the gold/total ion count signal is 917 for
a sample that was not stamped. Patterned stamps were 5-µm-wide
lines separated by 15-µm spaces. The ink used was Milli-Q water;
the contact time was 3 min. The stamps were made of Sylgard 184
elastomer, untreated or UV/ozone-treated (10 min).
comparison of the data in Table 3 with the corresponding
values for flat stamps on gold in Table 2. Apart from the
peak intensities, no qualitative differences (such as
differences in the relative peak heights or peak shapes)
were observed between the spectra from surfaces stamped
with flat or patterned stamps.
There is a possibility that silicone monomers/fragments
were transferred through the vapor phase in the regions
where the patterned stamp was not in contact with the
surface during stamping. To test this hypothesis, the XPS
analyses were performed for the gold samples exposed to
vapors from the untreated or UV/ozone-treated flat stamps
(see Materials and Methods for details). No silicon was
detected in either case [Si(2s); pass energy 5.85 eV;
acquisition time 17 min over 10 eV].
ToF-SIMS Analyses Using Flat Stamps. The ToF-
SIMS analyses of the gold samples, stamped with flat
stamps, showed a trend the same as that in the XPS
analyses: less PDMS is transferred if the stamp is
pretreated with UV/ozone than if it is untreated. The
intensity of the gold peak (m/z ) 197+ normalized to the
total ion intensity) is lower for the samples stamped with
untreated stamps than those stamped with UV/ozone-
treated stamps; see Table 4. This suggests that more
material is transferred to the sample from an untreated
stamp than from a UV/ozone-treated stamp, that is, the
lower the gold intensity, the thicker the layer of adsorbed
molecules. There is also a lower gold signal after stamping
with a patterned stamp compared to that of a flat one,
indicating that more material is transferred from a
patterned stamp than from a flat.
ToF-SIMS Analyses Using Patterned Stamps. Pat-
terned stamps were used to stamp Milli-Q water on the
Glasmästar et al.
gold samples. The Au (m/z ) 197+) signal is used as an
intensity reference, and we focus on the signals charac-
teristic for PDMS in the low-mass-range spectra,31 that
is, m/z ) 73+, 147+, 207+, 221+, and 281+. The contact
area between the stamp and the gold surface consists of
5-µm-wide, elevated lines, separated by 15-µm-wide
spaces. A Au substrate stamped with an untreated stamp
and analyzed by ToF-SIMS in image mode shows the
expected pattern (Figure 4A). Most of the silicone transfer
has occurred in the regions where the stamp was in contact
with the surface during stamping (i.e., the 5-µm-wide lines
are the brightest). However, when the stamp was pre-
treated with UV/ozone, the ToF-SIMS image shows more
intensity from the PDMS-related fragments (relative to
the Au signal) in the areas of noncontact (see Figure 4B),
which is surprising.
The surface topography influences the probability of
ionization of the surface molecules when imaging with
ToF-SIMS.23 To rule out the possibility of such effects as
the cause of the unexpected ToF-SIMS images obtained
with UV/ozone-treated stamps, tapping mode atomic force
microscopy was used to image a gold sample stamped with
patterned, untreated PDMS stamps (lines). No lines were
detected in the height image (0-10 nm), but lines of
dimensions the same as those of the contact area were
clearly seen in the phase contrast image (not shown). The
latter observation suggests that there is a chemical pattern
on the surface.32
The most important conclusions from the ToF-SIMS
analysis are: (i) It supports the conclusion from the XPS
results that UV/ozone pretreatment of the stamp is
efficient in lowering the PDMS transfer from the stamp
to the substrate. (ii) When PDMS transfer occurs from
UV/ozone-treated stamps, transferred PDMS is not located
only in the areas where the stamp and substrate were in
direct contact. (iii) There is more transfer from patterned
than from flat stamps.
These samples were also investigated by dark-field
microscopy. We found that on both the TiO2 and the SiOx
surfaces, PDMS transferred from patterned, untreated
stamps could be seen as brighter lines with dark-field
microscopy. Nothing could be seen when the stamp was
UV/ozone-treated before stamping or on the Au surfaces
that were stamped with untreated stamps.
(31) Dong, X.; Proctor, A.; Hercules, D. M. Macromolecules 1997, 30,
63.
(32) Pang, G. K. H.; Baba-Kishi, K. Z.; Patel, A. Ultramicroscopy
2000, 81, 35.
Silicone Transfer
Figure 5. (A) Dark-field light microscopy (20× objective) of a
gold sample stamped with a UV/ozone-treated stamp (Sylgard
184; Milli-Q water as the ink) having a 10 by 10 µm grid pattern
(the squares were not in contact). Water was subsequently
allowed to condense on the surface, producing this pattern. (B)
Fluorescence microscopy image of NBD-labeled phospholipid
vesicles backfilled onto a glass surface “pre-stamped” with an
untreated PDMS stamp (Sylgard 184; Milli-Q water as the ink)
of a design the same as that in part A. The upper left corner
shows a black area where the sample dried during the
experiment and, thus, is free of lipid.
Condensation Figures and Bilayer Formation. To
test for differences in chemistry between the underlying
substrate and any transferred material, water from humid
air was allowed to condense on the gold samples stamped
with patterned, UV/ozone-treated or untreated stamps
(with Milli-Q water as the “ink”). The pattern of the stamp
was a square grid of 10-µm-wide, elevated lines. The
squares between the lines were 10 by 10 µm and were not
in contact with the surface during stamping. Upon
condensation, clear patterns were formed. The details of
the patterns varied from run to run because the conden-
sation is very sensitive to minor variations in the
condensation conditions, primarily the humidity level and
temperature. One condensation pattern is shown in Figure
5A for a UV/ozone-treated stamp. A clear pattern of the
expected dimensions was observed, demonstrating a
contrast in hydrophobicity/hydrophilicity between the
contact/noncontact areas. The patterns were also seen with
untreated stamps (not shown).
In another “application example”, fluorescently labeled,
extruded unilamellar vesicles of POPC were adsorbed on
glass surfaces “pre-stamped”, as in the condensation
experiment previously described, using the same types of
stamps, that is, untreated or UV/ozone-treated. It is known
that lipid bilayers are formed by the adsorption and
subsequent rupture of vesicles on clean glass surfaces24
and that they can be studied using fluorescence imaging
and fluorescence recovery after photobleaching.33 The first
test results show that the fluorescent patterns formed on
the surface when the stamp was both untreated (Figure
5B) and UV/ozone-treated (not shown). Homogeneous
fluorescence indicates that the lipid film on the surface
is continuous and of the same thickness everywhere. On
the basis of the intensity variations, one could attribute
the bright areas to bilayers and the less bright areas to
monolayers.
(33) Boxer, S. G. Curr. Opin. Chem. Biol. 2000, 4, 704.
Langmuir, Vol. 19, No. 13, 2003 5481
Discussion
µCP Using Flat Stamps. There is clear evidence from
the present study for a transferred overlayer of molecules
derived from PDMS, on substrates subjected to µCP with
untreated PDMS stamps (both flat and patterned), when
buffer or Milli-Q water is used as the ink. This conclusion
is based on the XPS and ToF-SIMS data of the present
study.
Surprisingly few studies in the literature have aimed
at elucidating the problem of transferral of stamp material.
Graham et al.21 recently published the only (to our
knowledge) more detailed study on this issue. They
compared the self-assembled monolayers on gold made
by either adsorption from ethanolic solution or µCP with
flat stamps. They found that PDMS is transferred to the
surface by the µCP process (using XPS, ToF-SIMS, and
mulitvariate analyses). The authors present an extensive
cleaning protocol for the PDMS stamps, including extrac-
tion in hexane and sonication in an ethanol/water mixture
to avoid the transfer. The cleaning protocol takes about
1 week to perform according to Graham et al.21 Addition-
ally, they blotted the stamp on a cleaned piece of silicon
before stamping and claim that this was an effective way
to remove residual silicone that had migrated to the surface
during cleaning. By using this cleaning protocol, they were
able to lower the PDMS transfer from flat stamps during
printing in ethanol to levels below that of XPS detection,
although PDMS was still found by ToF-SIMS analysis.
Comparing our data for the samples stamped with
untreated, flat stamps with the corresponding data for
samples stamped with UV/ozone-treated stamps (Figure
3A-F and Table 2), we find that 10 min of UV/ozone
treatment reduces the transfer significantly. We, thus,
show that the simple and fast UV/ozone treatment of the
stamp, for the present conditions, significantly reduces
the amount of PDMS transferred during µCP to levels at
or below that of XPS detection. The same trends were
found for a second brand of PDMS elastomer: Rhodorsil
RTV 1556 (only XPS data).
µCP Using Patterned Stamps. The combined results
from XPS and ToF-SIMS indicate that PDMS is trans-
ferred both in the noncontact and in the contact regions
between the untreated stamp and the gold substrate
(Tables 2-4). This is despite only one-fourth of the stamped
surface being in contact with the patterned stamp, which
intuitively would suggest less transfer. The XPS values
are mean values over the analyzed area and, thus, a mean
over the areas that were in contact with the stamp and
the areas of noncontact. (These experiments were only
performed on the gold samples.) It is likely that the
mechanism of transfer of PDMS is different in the areas
of contact versus the areas of noncontact.
As for flat stamps, the transfer of PDMS from patterned
stamps is reduced by a UV/ozone pretreatment of the
stamp. However, the overall reduction of PDMS transfer
is smaller for patterned stamps compared to flat stamps
(Tables 2-3). The distribution of the transferred PDMS
on the stamped surface, which for UV/ozone-treated
stamps is predominantly detected in the regions of
noncontact, may indicate that the majority of the material
is not transferred across the contact interface. Some
possible mechanisms for the transfer of PDMS onto the
portions of the surface not in contact with the stamp are
shown schematically in Figure 6. One mechanism that
may involve volatile PDMS fragments from the “ceiling”
above the areas of noncontact being transported across
the vapor phase during the stamping process (option 1 in
Figure 6) seems to be ruled out by the XPS experiment
5482 Langmuir, Vol. 19, No. 13, 2003
Figure 6. Schematic illustration of the possible mechanisms
of transport of PDMS onto the noncontact areas. (1) Volatile
fragments from the “ceiling” (contradicted by the XPS control
experiment). (2) Diffusion from the contact areas (should be
seen as fuzzy edges in ToF-SIMS images for both untreated
and UV/ozone-treated but is not). (3) Transfer from the side
walls caused by the mechanical stresses during printing. PDMS
material diffuses (or flows) during the printing process along
the wall and out in the space between the contact areas.
of using a flat stamp, distanced from the gold surface by
a thin Al foil (∼13-µm thick), which showed that this
transfer mechanism is negligible (no Si detected by XPS).
Another option is lateral diffusion, or even flow during
the µCP process, of the fragments from the contact area
out into the space between the protruding features of the
stamp (option 2 in Figure 6). Such flow/diffusion should,
however, make the images of ToF-SIMS have “fuzzy” edges
of the lines, which is not the case (Figure 4). The third
and, as we see it, most realistic mechanism could involve
the escape of the PDMS-related fragments from the side
walls of the structures during the printing process and
their transport down into the area of noncontact (option
3 in Figure 6). This escape of material may be caused by
the increased forces (mechanical or capillary forces) at
the edges of the structures, as compared to the case of flat
stamps. Especially in the case of UV/ozone-treated stamps,
this mechanism seems likely. The thin SiOx layer formed
on the surface by UV/ozone treatment is quite brittle, and
cracks are likely to form in the layer upon mechanical
stress. Crack formation in thin SiOx films on PET has
been noted when they are subjected to tensile strain, and
the number of cracks increases with an increased applied
strain.34 The blotting of the stamps performed by Graham
et al.21 could be a good complement to the UV/ozone
treatment of the stamps.
One possible cause of the apparently inversed TOF-
SIMS images (Figure 4) is the so-called enhanced mono-
layer effect, or matrix effects,23,35 which under some
circumstances can give significantly higher ion intensities
at the thickness of around one monolayer than that for
thicker films. This means that brighter areas of the image
can actually have a lower coverage than darker areas.
Based on this phenomenon, we suggest that Figure 4B is
actually showing the correct contrast; that is, there is
more PDMS in the noncontact areas of a sample stamped
with a UV/ozone-treated stamp.
A recent article of Yang et al.19 mentions the transfer
of silicone in the areas of contact between the stamp and
the substrate during µCP and shows a ToF-SIMS image
where there is a higher ion intensity in the contact areas.
The substrate for µCP was in this case an activated PET
surface, the stamps were oxygen plasma-treated PDMS,
and the “ink” was a biotin-amine in ethanol (contact time
10 min). When it is assumed that UV/ozone treatment
and oxygen plasma treatment of PDMS gives a similar
surface chemistry of the stamps, the study of Yang et al.
(34) Hsueh, C. H. J. Am. Ceram. Soc. 2001, 84, 2955.
(35) Benninghoven, A.; Lange, W.; Jirikowsky, M.; Holtkamp, D. Surf.
Sci. Lett. 1982, 123, L721.
Glasmästar et al.
resembles ours, but the fact that we get a higher ToF-
SIMS intensity on the noncontact areas seems to be a
contradiction. However, the differences in the substrate
and printing conditions (contact time, solvent, etc.) might
explain why we get a different result. It has recently been
shown that the hydrophilicity of the stamp and surface
are important for the transfer of proteins from the stamp
to the surface (mixed thiols).4 It is also possible that
including molecules in the “ink” significantly changes the
situation. Maybe the molecules cover the walls or the
“ceiling” of the spaces of the features on the patterned
stamps, preventing PDMS fragments to come out in the
space of noncontact. Another possibility is that oxygen
plasma is more efficient than UV/ozone (10 min) in
producing a continuous and protective SiOx coating on
the stamp surface. On the other hand, oxygen plasma of
PDMS is said to produce low-molecular-weight frag-
ments27 on the surface, and it is possible that the UV/
ozone-treated PDMS has a different surface composition.
However, the XPS results of SiOx films formed from UV/
ozone treatment9 or oxygen plasma treatment27 are very
similar.
Influence of Material Properties on the Silicone
Transfer. The UV/ozone treatment reduces the PDMS
transfer. The likely mechanism is that the reactive oxygen
radicals formed by the UV light have two effects on the
surface of the stamp: (i) they oxidize the hydrocarbon
groups that could contaminate the stamped surface and
(ii) they reduce the hydrogen and carbon content in the
surface region and cause a larger number of Si-O bonds.
This glassy, SiOx-like surface is likely to reduce the PDMS
transfer to the stamped substrate.
Another factor that might influence the silicone transfer
to the substrate is the way PDMS is cured. There are
many different curing conditions for the Sylgard 184
elastomer reported in the µCP literature, ranging from
room temperature to 80 °C for various lengths of time. We
chose to cure PDMS in room temperature for at least 24
h. Because the curing conditions influence some material
properties of the stamp, it is possible that the amount of
transferred material during stamping is also influenced.
However, among the three previous studies similar to the
present study, one does not mention the temperature
(overnight in a vacuum desiccator),21 and the other two
used elevated temperatures (1-2 h a 60 °C19 or 70 °C for
at least 72 h).20 In all three cases, the transfer of silicone-
related material was detected.
What we have presented here is the worst case scenario
of silicone transfer during µCP. It is possible that, for
example, protein molecules from the ink could function
as a physical barrier to the adsorption of the silicone
fragments on the substrate. Furthermore, even if the
PDMS residues do adsorb, they might be displaced by the
proteins by competitive adsorption. Most likely, the
transfer is system-dependent and smaller biomolecules
in the ink, such as biotin or poly(lysine) derivatives, do
not prevent the silicone transfer.19,20
Conclusions
PDMS material is transferred from the stamp to the
stamped surface during µCP with flat and patterned
stamps (with water or buffer as the ink). UV/ozone
treatment of the PDMS stamp lowers the transfer
significantly upon stamping on SiOx, TiO2, and Au
substrates. More PDMS is transferred from patterned
stamps than from flat stamps. The water condensation
pattern and vesicle adsorption experiments (Figure 5A,B)
clearly show that molecules from PDMS affect the stamped
Silicone Transfer
pattern for both treated and untreated, patterned stamps.
The transfer of PDMS to the surface during µCP is relevant
to and calls for attention by those who are using this
method in applications where control of the surface
chemistry is of importance for the application.
Acknowledgment. The authors thank Peter Sjövall
at the SP Swedish National Testing and Research Institute
Langmuir, Vol. 19, No. 13, 2003 5483
in Borås, Sweden, for running the ToF-SIMS and for
fruitful discussions about the results. We also thank Sofia
Svedhem for making the fluorescently labeled vesicles
and Sarunas Petronis for producing the masters. Financial
support for this study was provided by the Swedish
Foundation for Strategic Research through the Screening
of Tissue Integrated Materials project.
LA026558X