Microelectronic Engineering 70 (2003) 131–136

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A soft-imprint technique for direct fabrication of submicron scale

patterns using a surface-modified PDMS mold
Won Mook Choi, O. Ok Park*
Center for Advanced Functional Polymers, Department of Chemical & Biomolecular Engineering, Korea Advanced Institute of Science
and Technology, 373 -1, Gusong-Dong, Yuseong-Gu, Daejon 305 -701, South Korea

Received 12 June 2003; received in revised form 21 July 2003; accepted 22 July 2003

Abstract

A novel soft-imprint technique for fabrication of submicron scale polymer structures is proposed. The proposed technique,
which can be performed at room temperature with very low pressure, is based on UV polymerization of a monomer that is
patterned by application of an elastomeric polydimethylsiloxane (PDMS) mold. To prevent the swelling of the PDMS mold
by the monomer during the polymerization procedure, the mold surface is coated with an amorphous fluoropolymer, Teflon
AF. By using the surface-modified PDMS mold, the submicron scale polymer structures are successfully generated with
good pattern fidelity, and are also fabricated over large areas through the UV-based soft-imprint technique.
 2003 Elsevier B.V. All rights reserved.

Keywords: Soft-imprint; Microfabrication; Modified PDMS mold; Teflon AF

1. Introduction conventional lithography is nanoimprint lithography

(NIL) [1–4], which has attracted much attention
The semiconductor industry requires reliable because it can be used to fabricate submicron
lithography techniques for fabricating micro- and structures at a lower cost and in less time than
nanometer-scale devices. At present, lithography is electron-beam writing. NIL generates resist patterns
usually carried out using photoresists; however, this in a thin thermoplastic layer such as polymethyl-
method cannot produce features smaller than the methacrylate (PMMA) by physically compressing
wavelength of the applied light and hence an alter- the resist at a temperature above its glass transition
native technique is needed to fabricate nanometer- temperature (T g ). The resist and the Si stamp are
scale features. Electron-beam writing is one option then cooled to a temperature below the T g of the
for creating features smaller than the wavelength of resist, and the Si stamp is released. After release of
light, but its sequential nature makes it very time- the stamp, an anisotropic etching process such as
consuming and expensive. Another alternative to reactive ion etching (RIE) is used to remove the
residual resist in the compressed region. The clean
release of the resist from the Si stamp is critical to
*Corresponding author. Tel.: 182-42-869-3923; fax: 182-42-
869-3910. the success of NIL. Usually, anti-adhesion agents are
E-mail addresses: [email protected] (W.M. Choi), used to achieve clean release. An additional factor
[email protected] (O. Ok. Park). that diminishes the precision of NIL is distortion of

0167-9317 / 03 / $ – see front matter  2003 Elsevier B.V. All rights reserved.
doi:10.1016 / S0167-9317(03)00436-2
132 W.M. Choi, O. .O. Park / Microelectronic Engineering 70 (2003) 131–136

the imprinted structure or stamp features due to the photolithography or the e-beam method [7]. After the
thermal cycle of heating followed by cooling. PDMS mold has been prepared, it is spin-coated at
To overcome these problems, step-and-flash im- 2000 rev. / min for 60 s with a 0.05 wt.% solution of
print lithography (SFIL) [5,6] was developed, which an amorphous fluoropolymer (Teflon AF, Dupont) in
uses photocurable monomers that are polymerized FC-77 (3M), which generates a few tens nm thick
during the imprint process. However, this procedure film of Teflon AF on the PDMS surface. To prepare
uses transparent quartz stamps that require a complex the substrate, a clean Si or glass substrate is spin-
fabrication process and then become more expensive coated with a mixture of styrene monomer (Aldrich)
than the usual silicon stamps. and 2 wt.% of UV initiator (2-methyl-4-(methylthio)-
PDMS has been used in a number of non-photo- 2-morpholino-propiophenone). The modified PDMS
lithography techniques, which are often collectively mold is then placed onto the monomer mixture. We
referred to as ‘soft lithography’ [7–10] techniques. chose polystyrene (PS) as the polymer for patterning
PDMS stamps give conformal contact over large because it has excellent etch-resistance, which is
areas, even for substrates with uneven surfaces, and essential to transfer patterns into the substrate.
are transparent, reusable and very cheap. In addition, Afterwards the polymerization of the styrene mono-
PDMS has a very low reactivity and interfacial mer, and before the PDMS mold is removed from
energy toward the polymeric materials and is suffi- the substrate, is performed through the irradiation of
ciently elastic that it can be separated from the UV light. Fig. 1 shows a schematic illustration of the
polymeric structure without destruction or distortion. experiment process. During the polymerization step,
One critical disadvantage of PDMS is its tendency to a small pressure is applied onto the PDMS mold
absorb organic solvents [7]. using a light and transparent weight (e.g. a slide
Here we present a modified UV-based ‘soft-im- glass). This pressure prevents the PDMS mold from
print’ lithography process that makes possible the floating on the monomer mixture, thereby ensuring
direct patterning of polymers with features in the patterned polymer features of homogeneous height.
submicron range. The proposed technique uses an
elastomeric PDMS mold and does not involve tem-
perature cycling or high pressure during processing. 3. Results and discussion
In this technique, a PDMS mold with submicron
scale relief is placed on a low viscosity monomer, A key feature of soft-imprint-based UV polymeri-
which is then polymerized by exposure to UV light zation is the use of a low viscosity monomer, which
at room temperature. The use of PDMS as the mold enables the monomer to quickly and completely fill
material ensures the clean release of the mold from the relief of the PDMS mold during the imprint step
the patterned polymer; thus the release process does and significantly reduces the required imprint pres-
not produce defects or distortion in the patterned sure. The residual polymer thickness can be easily
polymer, as has been found in NIL and SFIL. controlled by varying the amount of monomer and
However, the one problem in the proposed technique the applied pressure. Therefore, the process con-
is the swelling of PDMS for organic solvent as ditions of soft-imprint, such as very low imprint
mentioned above; it is particularly problematic with pressure and room temperature, are favorable for
the styrene monomer used in the present work. To pattern transfer to the substrate and for the step and
overcome it, we applied the surface-modified PDMS repeat applications. In addition, the use of a PDMS
mold by Teflon AF coating. mold, which has a low surface energy at the polymer
interface, eliminates the problem of the polymer
sticking to the surface of the mold during detach-
2. Experimental ment, which has proved a critical defect of NIL and
SFIL. The Teflon AF coating prevents the swelling
The PDMS molds are fabricated by casting a and deformation of the PDMS mold and enables the
PDMS precursor (Sylgard姠 184, Dow Corning) creation of large area patterns with good fidelity. The
against a complete relief structure prepared by either effect of Teflon AF coating in soft-imprint lithog-
 W.M. Choi, O. .O. Park / Microelectronic Engineering 70 (2003) 131–136 133

respectively. When the Teflon AF coating is not used

(Fig. 2a), only part of the PDMS mold pattern is
transferred onto the substrate, and the mold becomes
white after imprinting. The poor pattern transfer is
caused by swelling and deformation of the PDMS
mold due to absorption of monomer to the bare mold
during the soft-imprint process, and the polymeri-
zation of the monomer absorbed causes the mold to
become white. However, when the mold is coated
with Teflon AF (Fig. 2b), the entire area of the mold
pattern is transferred to the polymer surface, and no
whitening or deformation of the mold is observed.
Notably, we successfully fabricated defect-free poly-
mer patterns covering areas as large as 5 cm34 cm.
Fig. 3 shows optical micrographs and scanning
electron microscopy (SEM) images of a pattern of
dots (800 nm diameter and 5 mm period) that was
fabricated using a Teflon AF-coated PDMS mold.
The pattern feature of a 2 mm33 mm field is
uniformly imprinted by a single imprint with the
surface-modified PDMS mold. Detailed observation
of each area of the patterned field (Fig. 3a–d) reveals
that the imprinted dots are of identical size and
shape. In addition, no evidence of destruction or
distortion is observed, indicating uniform pattern
Fig. 1. Schematic diagram of the soft-imprint technique: (a) transfer over the entire pattern area. Thus, Teflon AF
preparing the PDMS mold coated with Teflon AF, (b) placing the
mold onto a substrate coated with monomer, (c) performing
coating makes possible uniform and precise pattern
polymerization at room temperature by exposure to UV light, and transfer over a large area with good fidelity, which is
(d) release. crucial to successful lithography.
Fig. 4 shows SEM and atomic force microscopy
raphy is depicted in Fig. 2a and b, which shows the (AFM) images of various polymer patterns. Fig. 4a
substrate and the PDMS mold after soft-imprint shows an SEM image of a positive polymer line
lithography without and with the Teflon AF coating, pattern of width 1 mm, height 1 mm and period 1.5

Fig. 2. Photographs of the patterned polymer on the substrate and the PDMS mold after soft-imprint (a) without, and (b) with Teflon AF
coating.
134 W.M. Choi, O. .O. Park / Microelectronic Engineering 70 (2003) 131–136

Fig. 3. Optical microscope image (center) of the patterned polymer structure (2 mm33 mm) and SEM images (corners) of zones (a)–(d).

mm that was imprinted using a Teflon AF-coated precisely transferred, indicating that the Teflon AF-
mold. The ability of the proposed technique to give a coated PDMS mold gives good pattern transfer over
clean interface is clearly shown in this image. a large area at room temperature.
Because low viscosity styrene monomer can effi-
ciently fill the cavities in the PDMS mold and be
polymerized by UV light, positive microstructures 4. Conclusion
such as that shown in Fig. 4a are easily generated,
even for high aspect ratios, which is difficult by NIL. In summary, we have demonstrated a novel soft-
Moreover, the Teflon AF coating prevents swelling imprint technique that uses a Teflon AF-coated
of the PDMS mold and guarantees defect-free pattern PDMS mold to fabricate submicron-scale polymer
transfer, and a clean interface of patterned polymer is patterns at room temperature with very low imprint
produced due to the low reactivity of PDMS to PS. pressures. The use of a low viscosity monomer and
Fig. 4b shows an SEM image of a polymer pattern of PDMS mold in the proposed technique enables the
lines of various scales. In this pattern, we successful- fabrication of a wide range of polymer structures,
ly created lines as small as 170 nm in width, and even structures containing high aspect ratio features,
even smaller polymer structures can be imprinted with good pattern fidelity over large areas. The
using the proposed soft-imprint technique. Further proposed soft-imprint technology has the potential to
examples are given in the AFM (Nanoscope, tapping be exploited as a direct and inexpensive method for
mode) images shown in Fig. 4c and d. These images fabricating patterned materials for use in various
again show that the patterned polymer structures applications, especially microelectronics and inte-
have clean interfaces and that the pattern has been grated circuits.
 W.M. Choi, O. .O. Park / Microelectronic Engineering 70 (2003) 131–136 135

Fig. 4. Micrographs of patterned polymer structures fabricated using Teflon AF-coated PDMS molds: (a) cross-sectional and (b) plane-view
SEM images of patterned polymer lines, and AFM images of (c) a line structure and (d) a dot structure.
136 W.M. Choi, O. .O. Park / Microelectronic Engineering 70 (2003) 131–136

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