Title of Invention

A METHOD OF MAKING A MICROSTRUCTURE

Abstract A method of making a microstructure, comprising: selectively activating an exposed portion of a surface of a silicon-containing elastomer by irradiating the exposed portion with UV radiation through a mask, while covering a protected portion of the surface with the mask, where during the irradiating the exposed portion is in contact with an atmosphere containing oxygen, and the mask is in contact with the protected portion; removing the mask from the surface of the silicon-containing elastomer; contacting the surface of the silicon-containing elastomer with a substrate; and bonding the activated portion and the substrate, such that the activated portion and a portion of the substrate in contact with the activated portion are irreversibly attached.
Full Text FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0001] The subject matter of this application was in part funded by the
National Science Foundation (NSF) Grant no. CHE 0097096; by the Defense
. Advanced Research Projects Agency (DARPA) Grant no. FA8650-04-C-7101;
and by the Department of Energy (DOE) Grant no. DEFG02-91ER45439. The
government may have certain rights in this invention.
BACKGROUND
[0002] Soft lithography is a versatile patterning technique for use in
microfabrication to produce microstructures. This technique uses a patterned
elastomer to transfer a pattern from a master to a substrate. The patterned
elastomer may be used, for example, as a stamp to transfer a substance, as a mold
to be filled by a substance, or as a mask to provide for selective deposition onto a
substrate and/or selective removal of material from the substrate. See, for
example, Xia, Y. and Whitesides, GM. Annu. Rev. Mater. Sci. (1998) 28:153-184.
[0003] In contrast, conventional photolithography utilizes rigid photomasks to
pattern photoresist layers, and the patterned photoresist then protects the material
beneath the pattern during subsequent etching and deposition steps. Soft
lithography provides a number of advantages over conventional photolithography.
Soft lithography can yield three-dimensional structures and non-planar structures
in a single deposition step, rather than requiring the stepwise assembly of
individual layers. Due to the mechanical flexiblility of the elastomer, non-planar
substrates can be patterned. The various soft lithographic techniques can also be
used with a more diverse range of materials than are available with
photolithography, and the materials and techniques used in soft lithography are
typically much lower in cost. Because of these advantages, soft lithography has
proven useful for applications including integrated optics, microelectromechanical

systems (MEMS), microfluidics, and patterning of biological material such as
proteins, nucleic acids and cells.
[0004] In one example, a patterned elastomeric stamp can be contacted with a
substrate to form channels which can exhibit a pattern in two or three dimensions.
The channels can then be filled with a liquid precursor for a solid substance, such
as a polymer or a ceramic. The channels can also be used to mix different fluid
substances, thus functioning as a microreactor or a microanalytical tool. The
formation of solid patterned structures with this technique is referred to as
Micromolding In Capillaries, or "MIMIC." Drawbacks to this technique include
the need for the pattern to be continuous to allow the entire pattern to be filled.
Also, the channels must be large enough to accommodate the viscosity of the
liquid used to fill the pattern, which can limit the resolution that can be obtained.
[0005] In another example, a patterned elastomeric stamp can be coated with a
substance and then contacted with a substrate. Removal of the stamp results in a
deposition of the substance onto the substrate in the pattern of the stamp. The
substance which is transferred thus functions as an ink which is printed onto the
substrate. This technique, referred to as microcontact printing or "µCP," can be
used to form discontinuous patterns, and can form patterns with higher resolution
than MIMIC. Applications of microcontact printing typically involve additive
lithography, which is the selective deposition of another substance on either the
patterned ink or on the exposed substrate. Drawbacks to this technique include the
limited range of materials which can be used as the substrate and as the ink.
[0006] In yet another example, a patterned elastomeric membrane can be
applied to a substrate. This membrane can then function as a mask for selective
removal of the exposed substrate (subtractive lithography), or for additive
lithography. Depending on the materials used for the membrane and the substrate,
reversible bonding between the two can be used to stabilize the membrane during
the desired microfabrication and to remove the membrane once it has served its
intended purpose. Drawbacks to this technique include the extreme difficulty in
applying, removing, and manipulating the thin elastomeric membrane. Also, the

membrane must be continuous and cannot be used for imaging discrete forms
and patterns.
[0007] It is thus desirable to provide an improved soft lithographic technique that
can be used to form patterns that are continuous or discrete, two dimensional or
three dimensional, on planar and non-planar substrates, and that may be in the
form of channels or masks for additive and subtractive lithography. It is also
desirable that these patterns can be formed on and with a wide range of
substances, without the need for delicate handling of the materials involved.
BRIEF SUMMARY
In a first embodiment of the invention, there is provided a method of making a
microstructure, comprising: selectively activating an exposed portion of a surface
of a silicon-containing elastomer by irradiating the exposed portion with UV
radiation through a mask, while covering a protected portion of the surface with
the mask, where during the irradiating the exposed portion is in contact with an
atmosphere containing oxygen, and the mask is in contact with the protected
portion; removing the mask from the surface of the silicon-containing elastomer;
contacting the surface of the silicon-containing elastomer with a substrate; and
bonding the activated portion and the substrate, such that the activated portion
and a portion of the substrate in contact with the activated portion are irreversibly
attached.

[0009] These embodiments may include a method wherein the selectively
activating comprises partially covering the surface to provide a protected portion
of the surface and an unprotected portion of the surface, and applying an
activating treatment to the unprotected portion. These embodiments may further
include a method wherein the applying an activating treatment comprises
irradiating the unprotected portion with UV radiation. These embodiments may
further include a method wherein the partially covering the surface comprises
positioning a mask on the surface of the silicon-containing elastomer. The mask
comprises a pattern of UV-opaque portions and UV-transparent portions and
comprises a spacer material under the UV-opaque portions, and the unprotected
portion of the surface is below and spaced apart from the UV-transparent
portions.
[0010] In a second embodiment of the invention, there is provided a method of
making a microstructure, comprising positioning a mask on an unpatterned
surface

of a silicon-containing elastomer. The mask comprises a pattern of UV-opaque
portions and UV-transparent portions and comprises a spacer material under the
UV-opaque portions, and the unpatterned surface comprises an exposed portion
below and spaced apart from the UV-transparent portions. The method further
comprises irradiating the exposed portion of the unpatterned surface with UV
radiation, removing the mask from the surface, contacting the surface with a
substrate, and separating the silicon-containing elastomer and the substrate, such
that the substrate and the exposed portion of the surface remain in contact.
[0011] In a third embodiment of the invention, there is provided a method of
making a microstructure, comprising positioning a mask on a surface of a silicon-
containing elastomer comprising a pattern of raised areas and lowered areas. The
mask comprises a pattern of UV-opaque portions and UV-transparent portions and
comprises a spacer material under the UV-opaque portions, and the surface
comprising an exposed portion of raised areas below and spaced apart from the
UV-transparent portions. The method further comprises irradiating the exposed
portion of raised areas with UV radiation, removing the mask from the surface,
contacting the raised areas with a substrate, and separating the silicon-containing
elastomer and the substrate, such that the substrate and the exposed portion of the
raised areas remain in contact.
[0012] These embodiments may include a method further comprising, after the
separating, applying an etching agent to the substrate to remove a portion of the
substrate which is not in contact with the exposed portion of the surface; and
removing the silicon-containing elastomer from the substrate.
[0013] These embodiments may include a method further comprising, after the
separating, depositing a material on the substrate; and removing the silicon-
containing elastomer from the substrate to provide a pattern of the deposited
material.
[0014] In a fourth embodiment of the invention, there is provided a method of
making a microstructure, comprising positioning a mask on a surface of a silicon-
containing elastomer. The mask comprises a pattern of UV-opaque portions and

UV-transparent portions and comprises a spacer material under the UV-opaque
portions, and the surface comprises an exposed portion below and spaced apart
from the UV-transparent portions. The method further comprises irradiating the
exposed portion with UV radiation; removing the mask from the surface,
contacting the surface with a discrete material, and removing unbound discrete
material from the surface, such that the exposed portion and the discrete material
in contact with the exposed portion remain attached.
[0015] In a fifth embodiment of the invention, there is provided a method of
making a microstructure, comprising positioning a mask on a surface of a silicon-
containing elastomer. The mask comprises a pattern of UV-opaque portions and
UV-transparent portions and comprises a spacer material under the UV-opaque
portions, and the surface comprises an exposed portion below and spaced apart
from the UV-transparent portions. The method further comprises irradiating the
exposed portion with UV radiation, removing the mask from the surface,
contacting the surface with a chemical compound, and rinsing the silicon-
containing elastomer, such that the silicon-containing elastomer and the chemical
compound in contact with the activated portion of the surface remain attached.
[0016] In a sixth embodiment of the invention, there is provided a method of
selectively activating a surface, comprising positioning a mask on a surface of a
silicon-containing elastomer. The mask comprises a pattern of UV-opaque
portions and UV-transparent portions and comprises a spacer material under the
UV-opaque portions, and the surface comprises an exposed portion below and
spaced apart from the UV-transparent portions. The method further comprises
irradiating the exposed portion of the surface with UV radiation.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] Figure 1 is a diagram of a pattern transfer method using Photodefined
Cohesive Mechanical Failure (P-CMF);
[0018] Figure 2 is a diagram of a pattern transfer method using direct
lithography;

[0019] Figure 3 is a diagram of a method of patterning a discrete material;
[0020] Figure 4 is a diagram of a method of patterning a chemical compound;
[0021] Figures 5A and 5B are an optical micrograph and an atomic force
microscopy (AFM) line scan, respectively, of an elastomer pattern formed using
P-CMF;
[0022] Figures 6A-D are optical micrographs (A & C) and an AFM line scan
(B) of an elastomer pattern formed using P-CMF, and an optical micrograph (D)
of a gold pattern derived from the elastomer pattern;
[0023] Figures 7A-D are an AFM image (A) and line scan (B) of an elastomer
pattern formed using direct lithography, and an AFM image (C) and line scan (D)
of the elastomer after the patterning process;
[0024] Figures 8A and 8B are an AFM image and line scan, respectively, of a
sub-micron elastomer pattern formed using direct lithography; and
[0025] Figures 9A-B are an optical micrograph (A) and an AFM image (A,
inset) of an elastomer pattern formed using direct lithography, and an optical
micrograph (B) of a gold pattern formed from the elastomer pattern.
[0026] Figures 10A-B are an optical micrograph (A) and an AFM image (B) of
an elastomer pattern formed using direct lithography.
[0027] Figures 11A-D are optical micrographs of a SOI wafer (A-B) and of the
corresponding silicon-containing elastomer (C-D), each of which have a pattern of
silicon wires.
DETAILED DESCRIPTION
[0028] In a first aspect of the invention, a method of making a microstructure
includes selectively activating a portion of a surface of a silicon-containing
elastomer, contacting the activated portion with a substance, and bonding the
activated portion and the substance. The activated portion of the surface and the
substance in contact with the activated portion are irreversibly attached.

[0029] These aspects may include a method wherein the selectively activating
includes partially covering the surface to provide a protected portion of the surface
and an unprotected portion of the surface, and applying an activating treatment to
the unprotected portion. These aspects may further include a method wherein the
applying an activating treatment includes irradiating the unprotected portion with
UV radiation. These aspects may further include a method wherein the partially
covering the surface includes positioning a mask on the surface of the silicon-
containing elastomer. The mask has a pattern of UV-opaque portions and UV-
transparent portions and includes a spacer material under the UV-opaque portions.
The unprotected portion of the surface is below and spaced apart from the UV-
transparent portions.
[0030] In a second aspect of the invention, a method of making a
microstructure includes positioning a mask as described above on an unpatterned
surface of a silicon-containing elastomer, such that the unpatterned surface has an
exposed portion below and spaced apart from the UV-transparent portions,
irradiating the exposed portion of the unpatterned surface with UV radiation,
removing the mask from the surface, contacting the surface with a substrate, and
separating the silicon-containing elastomer and the substrate. The substrate and
the exposed portion of the surface remain in contact.
[0031] In a third aspect of the invention, a method of making a microstructure
includes positioning a mask as described above on a surface of a silicon-
containing elastomer having a pattern of raised areas and lowered areas, such that
the surface has an exposed portion of raised areas below and spaced apart from the
UV-transparent portions, irradiating the exposed portion of raised areas with UV
radiation, removing the mask from the surface, contacting the raised areas with a
substrate, and separating the silicon-containing elastomer and the substrate. The
substrate and the exposed portion of the raised areas remain in contact.
[0032] These aspects may also include a method where, after the separating, an
etching agent is applied to the substrate to remove a portion of the substrate which
is not in contact with the exposed portion of the surface. The silicon-containing

elastomer may then be removed from the substrate. These embodiments may also
include a method where, after the separating, a material is deposited on the
substrate. The silicon-containing elastomer may then be removed from the
substrate to provide a pattern of the deposited material.
[0033] In a fourth aspect of the invention, a method of making a microstructure
includes positioning a mask as described above on a surface of a silicon-
containing elastomer, such that the surface has an exposed portion below and
spaced apart from the UV-transparent portions, irradiating the exposed portion
with UV radiation; removing the mask from the surface, contacting the surface
with a discrete material, and removing unbound discrete material from the surface.
The exposed portion and the discrete material in contact with the exposed portion
remain attached.
[0034] In a fifth aspect of the invention, a method of making a microstructure
includes positioning a mask as described above on a surface of a silicon-
containing elastomer, such that the surface has an exposed portion below and
spaced apart from the UV-transparent portions, irradiating the exposed portion
with UV radiation, removing the mask from the surface, contacting the surface
with a chemical compound, and rinsing the silicon-containing elastomer. The
silicon-containing elastomer and the chemical compound in contact with the
activated portion of the surface remain attached.
[0035] In a sixth aspect of the invention, a method of selectively activating a
surface includes positioning a mask as described above on a surface of a silicon-
containing elastomer, such that the surface has an exposed portion below and
spaced apart from the UV-transparent portions, and irradiating the exposed portion
of the surface with UV radiation.
[0036] The term "microstructure," as used herein, is defined as a structure or
pattern containing features which are 1,000 micrometers (urn) or smaller. The
formation of microstructures is referred to herein as "microfabrication" and
includes, but is not limited to, techniques such as microlithography, soft
lithography, MIMIC, and self-assembly.

[0037] The term "activate," as used herein with respect to silicon-containing
elastomers, is defined as converting an inert surface into a reactive surface. For
example, a surface in its normal, unactivated state may not adhere to a substrate;
however, activation of this surface provides for strong adhesion between the
surface and the same substrate.
[0038] The term "selectively activate," as used herein, is defined as activating
a specific portion of a surface, while maintaining the rest of the surface in an
unactivated state.
[0039] The term "irreversibly attached," as used herein, means that the
bonding between two substances is sufficiently strong that the substances cannot
be mechanically separated without damaging or destroying one or both of the
substances. Substances which are irreversibly attached may be separated by
exposure to an appropriate chemical environment, such as chemical reagents or
irradiation.
[0040] The term "on" is defined as "above" and is relative to the orientation
being described. For example, if a first element is positioned over at least a
portion of a second element, the first element is said to be "positioned on" the
second. In another example, if a first element is present above at least a portion of
a second element, the first element is said to be "on" the second. The use of the
term "on" does not exclude the presence of substances between the upper and
lower elements being described. For example, a first element may have a coating
over its top surface, yet a second element over at least a portion of the first
element and its top coating can be described as "on" the first element. Thus, the
use of the term "on" may or may not mean that the two elements being related are
in physical contact with each other.
[0041] Similarly, the term "under" is defined as "below" relative to the
orientation being described. The use of the term "under" does not preclude the
presence of substances between the elements being described, and may or may not
mean that the elements are in physical contact with each other.

[0042] The term "elastomer," as used herein, is defined as a polymer which
can return to its initial dimensions when deformed by an external force. A
polymer is considered an elastomer when it meets the following standard. A
sample of the polymer in its solid state and having an initial linear dimension D° is
subjected to a force such that the dimension is changed by 10%. Once the force is
no longer applied, the dimension assumes a value of De, where De = D° ± 0.0lD0.
[0043] The term "silicon-containing elastomer," as used herein, is an elastomer
which contains silicon (Si) atoms. Examples of silicon-containing elastomers
include, but are not limited to, polysiloxanes, such as poly(dimethyl siloxane),
poIy(methyl siloxane), partially alkylated poly(methyl siloxane), poly(aIkyl
methyl siloxane) and poly(phenyl methyl siloxane); block copolymers containing
segments of a polysiloxane and another polymer; silicon-modified elastomers,
such as silicon-modified natural rubber, silicon-modified polyolefins (including
silicon-modified polyisoprene, silicon-modified polybutadiene, and silicon-
modified polyisobutylene), silicon-modified polyimides, silicon-modified
crosslinked phenol-formaldehyde resins (Si-modified NOVOLAC), and silicon-
modified polyurethane elastomers. Silicon modification of elastomers may be
carried out by reactions with silanes and siloxanes, including hydrosilation and
condensation. Preferably the silicon-containing elastomer is a polysiloxane. More
preferably, the silicon-containing elastomer is poly(dimethyl siloxane), referred to
as "PDMS."
[0044] Further examples of silicon-containing elastomers include block
copolymers of polysiloxanes with other polymers. For example, block copolymers
containing polysiloxanes may be formed with polyolefins such as polyethylene
(U.S. Pat. No. 5,618,903, incorporated herein by reference), poly(isobutylene)
(U.S. Pat. No. 5,741,859, incorporated herein by reference), polypropylene (U.S.
Pat. No. 5,744,541, incorporated herein by reference), polystyrene and various
polydienes (U.S. Pat. No. 5,932,649, incorporated herein by reference), and
polyisoprene and polybutadiene (U.S. Pat. No. 6,362,288, incorporated herein by
reference). In another example, block copolymers containing polysiloxanes may

be formed with acrylates (U.S. Pat. No. 6,090,902, incorporated herein by
reference), with a wide variety of polymers formed by polymerization of
unsaturated monomers (U.S. Pat. No. 6,124,411, incorporated herein by
reference), and with a variety of types of siloxanes (U.S. Pat. No. 5,637,668,
incorporated herein by reference). In another example, block copolymers
containing polysiloxanes may be formed with condensation polymers such as
polycarbonates (U.S. Pat. No. 6,072,011, incorporated herein by reference) and
poly(arylene ethers) (U.S. Pat. No. 6,339,131, incorporated herein by reference)
and may also be formed with polyethers such as polyethylene oxide and
polypropylene oxide (U.S. Pat. No. 6,013,711, incorporated herein by reference).
Further examples of silicon-containing elastomers include copolymers containing
polysiloxane repeat units in combination with polyester and/or polycarbonate
repeat units (U.S. Pat. No. 6,407,193, incorporated herein by reference), and also
include blends of polysiloxanes with polyamides (U.S. Pat. No. 6,344,521,
incorporated herein by reference) and blends of polysiloxanes with polyolefins,
polyurethanes, or styrenic polymers (U.S. Pat. No. 6,153,691, incorporated herein
by reference). Further examples of silicon-containing elastomers include
polymers modified to contain silicon by treatment with silane compounds (U.S.
Pat. No. 6,136,926, incorporated herein by reference).
[0045] Microstructures containing a silicon-containing elastomer can be
prepared by irreversibly bonding an activated silicon-containing elastomer and
another material. For example, activation of a portion of a silicon-containing
elastomer, followed by contacting and bonding the surface of the activated portion
with a monolithic substrate can form an irreversible attachment between the
activated portion of the elastomer and the substrate. When the elastomer is pulled
away or otherwise separated from the substrate, the elastomer can undergo
cohesive failure, separating the bulk portion from the activated portion.
Preferably, the cohesive failure is such that a film of elastomer material remains
bonded to the substrate only in regions where the elastomer surface has been
activated and then placed in contact with the substrate. In another example,

contacting and bonding of a silicon-containing elastomer having an activated
portion with a chemical compound or a discrete material can provide for a pattern
of the compound or material on the elastomer surface.
[0046] The selective activation of a portion of a silicon-containing elastomer
may be accomplished by protecting a portion of a silicon-containing elastomer,
and then applying an activating treatment to the unprotected portion. For example,
a hard mask may be formed on a surface of a silicon-containing elastomer, and the
exposed portions of the elastomer surface can be subjected to an activating
treatment. The hard mask must then be removed before the elastomer can be
bonded to another material. In another example, a free-standing mask can be
positioned on the surface of the silicon-containing elastomer, such that the mask
and elastomer can be separated readily after the activating treatment.
[0047] The activating treatment can be any of a variety of treatments known in
the art, provided the desired portions of the elastomer can be protected from the
treatment. In one method, for example, the elastomer can be exposed to an
oxygenated plasma to activate the exposed elastomer surface. This activation can
be carried out by converting a stream of oxygen into a plasma at a temperature as
low as 40°C. In another method, the silicon-containing elastomer is activated by
oxidation through a UV/Ozone treatment. This treatment process, referred to as
"UVO," is described, for example in co-pending U.S. Patent Application
10/230,882 (U.S. Patent No. 6,805,809), which is incorporated herein by
reference. The UVO process involves oxidation of the surface of a silicon-
containing elastomer by exposing the surface to ultraviolet radiation sufficient to
generate ozone and/or other oxidizing species, such as singlet oxygen, from an
ambient atmosphere. Activation by UVO can also include exposing the surface to
an atmosphere enriched in either molecular oxygen (O2) or ozone (O3). One
advantage of the activation by UVO is that the silicon-containing elastomer can
become sufficiently activated under mild conditions.
[0048] The amount of UVO treatment may be varied depending on the type of
silicon-containing elastomer and the type of material to which the elastomer is to

be bonded. For example, for polysiloxanes containing alkyl or aryl organic side
groups which are less volatile than the methyl groups of PDMS, the UVO may
need to be applied for longer periods of time. Also, for silicon-modified
elastomers and polysiloxane-containing block copolymers, an increased duration
of UVO may be needed, since the silicon atoms are less concentrated than in
PDMS. The UV source for the UVO treatment may be any of a variety of UV
sources. Examples of UV sources include mercury discharge lamps, and
deuterium discharge lamps. Preferably the UV source is a deuterium discharge
lamp.
[0049] A silicon-containing elastomer can be selectively activated using UVO
by applying the UVO treatment to an elastomer that has been covered with a
mask. The mask for UVO treatment preferably provides both for transmission of
UV radiation to the exposed regions of the elastomer and for contact of the
exposed regions with an atmosphere containing oxygen. The oxygen present in
this atmosphere, in combination with UV radiation, can serve to activate the
exposed portion of the elastomer.
[0050] The general design of a mask 100 for selective UVO activation is
shown in Figures 1-4, in which a UV-transparent lens 110 is partially covered with
a UV-opaque layer 120. The patterned UV-opaque layer is covered with a spacer
material 130. The gap 140 defined by the UV-transparent material 110, the
exposed portion 152 of the silicon-containing elastomer 150, and the spacers 130
allows the elastomer to be in contact with an atmosphere during the UVO
treatment. In a specific example of a UVO mask, the UV-transparent lens is a
quartz lens, and the UV-opaque film is a patterned gold film. It may be desirable
to provide a titanium layer between the quartz and the gold film, in which case the
titanium preferably has the same pattern as the gold film.
[0051] Preferably, the spacer material is the photoresist material that was used
to pattern the UV-opaque film. Although a photoresist material is typically
removed after the underlying layer or layers have been patterned, the use of the
photoresist as the spacer material can provide a number of advantages.

Photoresists are typically deposited in a layer of uniform, controllable thickness,
thus the resulting spacer material will likewise have a uniform thickness that can
be varied as needed. In addition, since the photoresist is originally used to pattern
the UV-opaque layer, the spacer material is already in alignment with the UV-
opaque portions of the mask, providing for precise definition of the UV-
transparent openings in the mask. Photoresist material can be selected to constrain
the UV radiation and possibly to inhibit the migration of photogenerated reactive
species. A specific example of a photoresist that can also be used as the spacer
material is the SU-8 series of photoresists, which can allow for patterning of
features from 1 µm or less to 200 µm or greater.
[0052] The thickness of the spacer material can be varied. In the example of
photoresist material as the spacer, the thickness can be controlled at the outset of
the patterning process by controlling the initial thickness of the photoresist that is
deposited on the UV-opaque layer. Preferably, the spacer material is sufficiently
thick to allow for adequate amounts of oxygen in the gap region between the
elastomer and the UV-transparent portion of the mask. Preferably the thickness of
the spacer is at least 100 nanometers, more preferably at least 0.5 microns, and
even more preferably at least 3 microns.
[0053] Selective activation of a silicon-containing elastomer can be used to
deposit a pattern of the elastomer on a substrate. The activated surface of a
silicon-containing elastomer can be irreversibly attached to the surface of a
substrate material by contacting the activated surface and the substrate and
bonding together the surface and the substrate. Suitable substrates include, but are
not limited to, silicon; ceramic materials such as silicon oxide, quartz and glass;
polymers such as polystyrene and silicon-containing elastomers, including PDMS;
and metals such as titanium, chromium, tungsten, and gold. Preferably, the
surface of the silicon-containing elastomer is treated with UVO at ambient
temperature for an appropriate length of time and is then immediately contacted
with a substrate that has been recently cleaned.

[0054] The elastomer and substrate are kept in contact to allow the formation
of an irreversible bond. The contacted elastomer and substrate may be subjected
to heating and/or supplemental ultraviolet radiation to assist the formation of the
bond. For example, after contacting UVO treated PDMS with a silicon substrate,
the irreversible bond can be obtained by maintaining the contact for about 16
hours at ambient temperature, by maintaining the materials at 70°C for at least 20
minutes, or by applying UV radiation to the PDMS for at least 30 minutes.
Exposure of unoxidized silicon-containing elastomers to only one of heat, ozone
or UV radiation will not typically provide irreversible adhesion to substrates.
[0055] The initial contact between the UVO-activated surface of the silicon-
containing elastomer and the substrate surface typically will not result in an
irreversible bond. This phenomenon allows for the precise positioning of the
elastomer and the substrate. Thus, any patterns in the elastomer and/or the
substrate can be aligned or registered prior to the formation of an irreversible
bond. The use of an optically transparent silicon-containing elastomer (such as
PDMS) may also be desirable, in that alignment or registration of films and
patterns can be done using optical observation.
[0056] It may be desirable to clean the surface of the substrate prior to
contacting the substrate with the UVO-activated silicon-containing elastomer.
Substrates may be cleaned by conventional methods. For example, substrates of
silicon or silicon oxide can be rinsed with solvents such as hexanes and ethanol
and dried under an inert gas such as nitrogen. In another example, glass and
quartz can be rinsed with reagents such as piranha (sulfuric acid and hydrogen
peroxide). The substrate may also be cleaned and/or activated by exposure to
UVO, to a plasma such as an argon plasma or other plasma, or to other chemical
treatments. It may also be desirable to treat the surface of the substrate with UVO
immediately prior to contacting it with the activated elastomer. The treatment of
the substrate may conveniently be carried out by subjecting the elastomer surface
and the substrate surface to the same UVO exposure. For metal substrates such as
gold, it may be useful to apply an adhesion promoter such as a thiol compound to

the metal surface and/or the elastomer surface. Examples of thiol compounds
include thiol-silane compounds such as (thiolpropyl)-trimethoxysilane.
[0057] Referring to Figure 1, the selective activation of a silicon-containing
elastomer can be used to deposit a portion of a pre-formed pattern of an elastomer
onto a substrate. This process, referred to as "Photodefined Cohesive Mechanical
Failure" (P-CMF), uses a patterned stamp 160 to provide the basic pattern of the
silicon-containing elastomer. This basic pattern is then further defined by
selective activation of the raised portions of the pattern in the stamp. The
patterned stamp 160 is placed into contact with the patterned side of a UVO
photomask 100, and is then irradiated through the mask by a UV source. After
UV irradiation, the stamp is peeled away from the UVO photomask, and the
patterned face of the stamp is placed promptly into contact with a substrate
material 180. Preferably the time between the end of the irradiation and the
contact with the substrate is less than one minute. While maintaining contact, the
stamp and substrate are subjected to the conditions necessary to form an
irreversible bond between the elastomer and the substrate. Starting from any
corner, tweezers are used to peel the stamp away to leave a patterned film 190 on
the substrate.
[0058] Referring to Figure 2, the selective activation of a silicon-containing
elastomer can be used to deposit a portion of an unpatterned elastomer onto a
substrate. This process, referred to as "direct lithography," uses a planar blank of
elastomer 250, such that all patterning is a result of the selective activation
process. The elastomer blank is placed into contact with the patterned side of a
UVO photomask 100, and is then irradiated through the mask by a UV source.
After UV irradiation, the elastomer is peeled away from the UVO photomask, and
the irradiated surface of the blank is placed promptly into contact with a substrate
material 280. Preferably the time between the end of the irradiation and the
contact with the substrate is less than one minute. While maintaining contact, the
elastomer and substrate are subjected to the conditions necessary to form an
irreversible bond between the elastomer and the substrate. Starting from any

corner, tweezers are used to peel the elastomer away to leave a patterned film 290
on the substrate.
[0059] The elastomer pattern transfers of these P-CMF and direct lithography
methods involve contributions of chemically activated adhesive bonding and
cohesive material failure processes. The yield strength of the patterned elastomer
as it is peeled from the substrate can be affected both by the total elastomer
contact area and by the feature sizes. Thus, the patterning method based on
cohesive failure is especially useful for transferring patterns with small feature
sizes (100 µm or smaller) over relatively large areas. One advantage of this
method is that it can transfer patterns in a manner that allows registration of
multiple patterns and that enables micron scale patterning over large areas. The
locus of the cohesive failure of the elastomer progressively approaches that of the
surface of the features as their sizes approach the 1 micron level. Pattern transfers
in a thickness range of 10-100 run can be attained for a 1.0 µm minimum feature
size, based on a master with a 1 µm feature height as a specific example. The
removal of the bulk elastomer for these small features sizes also tends to require a
lower amount of force.
[0060] The direct lithography process in particular can provide for the
formation of patterns at the sub-micron scale. Although the gap formed between
the elastomer and the mask at these dimensions is extremely small (on the order of
nanoliters), there is sufficient oxygen present to provide for effective UVO
activation. An example of a sub-micron patterned structure is shown in the
Atomic Force Microscopy (AFM) images of Figure 8 A and 8B. The line pattern
shown contains lines having widths and separations of approximately 300 nm.
[0061] The P-CMF process in particular can provide for the formation of
arrays of patterns. If the minimum dimensions of the mask pattern are larger than
the minimum dimensions of the pattern in the initial elastomer stamp, then a
subset of the pattern in the stamp can be transferred to the substrate. An example
of an array of a cylindrical pattern is shown in the optical micrograph of Figure
5 A. An example of an array of a pattern of lines is shown in the optical

micrographs of Figures 6A and 6C. This pattern of lines is illustrated as
transferred to a pattern of gold lines in Figure 6D.
[0062] The decal transfer methods allow the deposition of precisely designed
polymer thin-films with a remarkable range of feature sizes. Minimum feature
sizes in these patterns may be less than 100 micrometers. Preferably, minimum
feature sizes are from 1 nanometer to 100 micrometers, and more preferably from
10 nanometers to 10 micrometers. In one example, the minimum feature size is
less than 1 micrometer.
[0063] Selective activation of a silicon-containing elastomer can be used to
form a pattern of another material. For example, an etching agent can be applied
to the substrate so as to remove the portion of the substrate that is not attached to
the patterned elastomer. Subsequent removal of the elastomer can provide a
pattern in the substrate. In another example, a separate material can be deposited
onto the substrate and the patterned elastomer. Subsequent removal of the
elastomer can provide a pattern of the deposited material. In addition to these
lithographic techniques, patterning of other materials can be accomplished by
attaching the activated surface of a silicon-containing elastomer to individual
chemical compounds, to discrete materials, or to monolithic materials having a
cohesive force weaker than that of the elastomer.
[0064] Referring to Figure 3, the selective activation of a silicon-containing
elastomer can be used to remove a portion of discrete material from another
substrate. Although a planar blank 350 of elastomer is pictured, a patterned stamp
could also be used. The elastomer is placed into contact with the patterned side of
a UVO photomask 100, and is then irradiated through the mask by a UV source.
After UV irradiation, the elastomer is peeled away from the UVO photomask, and
the irradiated surface of the blank is placed promptly into contact with the layer of
discrete material 370 on the substrate 380. While maintaining contact, the
elastomer, discrete material and substrate are subjected to the conditions necessary
to form an irreversible bond between the elastomer and the discrete material. The
elastomer can then be lifted away from the substrate to provide a substrate having

a pattern 390 of discrete material on its surface. This process also provides a
pattern 360 of the discrete material on the silicon-containing elastomer.
[0065] The discrete material can be in a variety of forms. For example, the
discrete material may contain powders, particles, platelets, nanotubes, fibers or
wires of materials such as silicon; ceramic materials such as silicon oxide, quartz
and glass; polymers such as polystyrene and silicon-containing elastomers,
including PDMS; and metals such as titanium, chromium, tungsten, and gold.
[0066] Referring to Figure 4, the selective activation of a silicon-containing
elastomer can be used to form a pattern of a compound on the surface of the
silicon-containing elastomer. Again, either a planar blank 450 of elastomer or a
patterned stamp could be used. The elastomer is placed into contact with the
patterned side of a UVO photomask 100, and is then irradiated through the mask
by a UV source. After UV irradiation, the elastomer is peeled away from the
UVO photomask, and the irradiated surface of the blank is promptly contacted
with the compound, either neat or in a liquid carrier. In some cases, the compound
will rapidly adsorb to the activated portions of the elastomer. In other cases, the
elastomer and compound must undergo a post-treatment to maintain the compound
in the pattern 490. Examples of compounds that can be adsorbed onto an activated
surface of a silicon-containing elastomer include alcohols, carbonyl-containing
compounds, and compounds having one or more silicon-halogen bonds.

[0067] EXAMPLES
[0068] Polydimethylsiloxane (PDMS) precursor was obtained from DOW
CORNING (Midland, MI) as SYLGARD 184. Boron doped silicon wafers
() were obtained from SILICON SENSE, INC. (Nashua, NH). Quartz slides
were obtained from CHEMGLASS, INC. (Vineland, NJ). (Tridecafluoro-1,1,2,2-
tetrahydrooctyl) trichlorosilane (TFOTS) was obtained from GELEST
(Morrisville, PA). Tetrabutylammonium fluoride (TBAF, 1 molar in
tetrahydrofuran), (mercaptopropyl)trimethoxysilane (MPTMS), and 2,2,2-
trifluoroethanol were obtained from ALDRICH (Milwaukee, WI). Buffered
hydrofluoric acid (6:1, NH4F/HF) was obtained from ASHLAND (Dublin, OH).
Gold etchant was obtained as TFA from TRANSENE (Danvers, MA). Sulfuric
acid, hydrofluoric acid (49%), and hydrogen peroxide (30%) were obtained from
FISHER (Springfield, NJ). Solvents were obtained from Fisher and from Aldrich.
[0069] Silicon oxides were grown on silicon wafers under an ambient
atmosphere by heating them to around 800°C for several hours to give a ~2500A
thick oxide layer. Masters were produced as described in Deng et al., Anal. Chem.
73:3176-3180 (2000) and in Deng et al., Langmuir 15:6575-6581 (1999). Contact
photolithography was used to make master patterns by patterning either AZ 5214
(CLARIANT, Sommerville, NJ) or SU-8 5 (MCROCHEM, Newton, MA)
photoresists, using 5080 dpi transparencies as an exposure mask. All photoresist
masters used as molds were cleaned using a UVO treatment and treated with
TFOTS (as a mold release agent) in a closed container at around ~150 mTorr for
two hours. Solvents used in processing the samples were of analytical grade or
higher and used without purification.
[0070] The UV source used for UVO treatments was either a low-pressure
mercury lamp (BHK, Claremont, CA) or a deuterium lamp (Hamamatsu D101BS).
The intensities for each bulb, measured from 230-250 nm using a MIMIR Optical
Powermeter Model 100 were determined to be 100 µW/cm2 at 3 cm distance from
the mercury bulb and 530 µW/cm2 at 1 cm from the deuterium bulb. A 03V5-5

ozone generator (OREC, Akron, OH) was used as UV independent source of
ozone.
[0071] Optical micrographs were recorded using an OLYMPUS BH-2 optical
microscope (OLYMPUS AMERICA, Melville, NY) with PANASONIC GP-
KR222 digital color camera (PANASONIC USA, Seacaucus, NJ). Surface feature
heights and film thicknesses were determined by surface profilometry using a
SLOAN DEKTAK3 ST (VEECO INSTRUMENTS, Histon, Cambs, United
Kingdom). Atomic force microscopy (AFM) was performed using a Dimension
3100 (VEECO), and the images were processed by the manufacturer's V5.12r2
software. Area scans were recorded with unmodified silicon tips in tapping mode
with a tip velocity of 2 Hz or less.
[0072] Example 1 - Mask Preparation
[0073] Quartz slides were cleaned in a piranha solution (3:1 H2S04: hydrogen
peroxide 30%) for 10 min, washed with deionized water and dried with nitrogen.
A 30 A titanium layer and a 1000 A thick gold film were deposited onto the
surface of a quartz slide by evaporation using a TEMESCAL FC-1800 Electron
Beam Evaporator (BOC EDWARDS, Wilmington, MA). The deposited metal
layer was patterned into a square planar array of rectangular cavities having
dimensions of 45 microns by 55 microns. This patterning was carried out by
contact photolithography using SU8-5 photoresist. The patterned quartz slide was
cleaned in an oxygen plasma for 15 s, the exposed gold areas were etched in a
dilute (4:1) solution of TFA Gold Etch, and the exposed titanium layer etched by a
1% HF solution. The unstripped layer of the photoresist was retained as part of
the final mask, providing a spacer of SU8-5 resist, with a pitch of one. The resist
layer had a uniform thickness of 17 µm.

[0074] Example 2 - Patterning Using Photodefined Cohesive Mechanical
Failure (P-CMF)
[0075] A molded PDMS stamp was prepared as recommended by DOW
CORNING in the SYLGARD 184 kit, by mixing the oligomer and initiator in a
10:1 ratio. The recommended procedure was modified by reducing the pressure
(50 torr) at room temperature for several minutes with a vacuum oven to remove
entrained gas bubbles. The prepolymer mixture was cast onto a master, and, after
waiting 10 min for the mixture to level, the mixture was cured at 70°C for two
hours. The patterned PDMS elastomer was then extracted from the master,
washed with ethanol, and dried under a stream of high purity nitrogen to provide
the PDMS stamp. The final PDMS stamp had a pattern of a square array of posts,
2 urn in diameter with a center-to-center separation of 2.7 µm.
[0076] The PDMS stamp was placed into contact with the patterned side of the
UVO photomask of Example 1 and irradiated through the mask for 4 minutes
using a deuterium lamp. The mask was removed, and the PDMS pattern was
placed into contact with a glass substrate and heated to 70°C for 20 minutes. The
PDMS stamp was then removed from the glass substrate using tweezers by peeling
the stamp from a corner.
[0077] Figure 5A is an optical micrograph of the resulting microstructure, an
array of PDMS posts having the same pattern as the UV-transparent portions of
the mask. The inset of Figure 5A is an image, at the same magnification, of a UV-
transparent opening in the mask. The size and spacing of the domains of the
PDMS posts matched the 45 x 55 micron openings in the mask, with an edge
resolution below the 2.0 micron pixel size of the PDMS posts. Figure 5B is an
atomic force microscopy (AFM) line scan across a domain of posts, indicating that
essentially all the posts had a peak height of approximately 800 nm.

[0078] Example 3 - Use Of P-CMF Pattern As Resist
[0079] A PDMS stamp was formed as described in Example 2, except with an
unbroken pattern of lines 2 µm wide and separated by 2 µm spacings. The stamp
was placed into contact with the patterned side of the UVO photomask of Example
1 and irradiated through the mask for 4 minutes using a deuterium lamp. The
mask was removed, and the PDMS pattern was placed into contact with a MPTMS
silanized gold surface having a gold thickness of 100 nm and heated to 70°C for 20
minutes. The PDMS stamp was then removed from the substrate using tweezers
by peeling the stamp from a corner. Figures 6A and 6C are optical micrographs of
the resulting microstructure, in which each circular domain (45 x 55 microns) on
the gold surface contained a pattern of 2 µm wide lines of PDMS. The AFM line
scan of Figure 6B measured the height of the PDMS lines as approximately 1.6
µm.
[0080] The PDMS pattern was transferred into the gold film by wet etching the
exposed gold layer and the underlying titanium layer. Stripping of the PDMS
resist provided a pattern of gold lines, shown in the optical micrograph of Figure
6D. The gold lines were 2 µm wide and were separated by a pitch of one. These
lines were arranged within discrete domains, which matched the PDMS pattern of
Figures 6A and 6C.
[0081 ] Example 4 - Patterning Using Direct Lithography
[0082] A flat, unpatterned PDMS slab was formed by casting Sylgard 184 in a
Petri dish at a thickness of 3 mm, and then curing the prepolymer for a minimum
of 2 hrs at 70°C. A PDMS blank having approximate dimensions of 2 cm x 3 cm
was cut from this slab, washed with ethanol, and dried with nitrogen. A UVO
photomask was prepared as in Example 1, except that the metal layer was
patterned as 4 µm wide lines separated by 4 µm spacings. This patterning was
carried out by photolithography using Shipley 1805 resist having a uniform
thickness of 450 nm.

[0083] The planar PDMS blank was placed into contact with the patterned side
of the UVO exposure mask and irradiated through the mask for 6 minutes using a
deuterium lamp. The mask was removed, and the PDMS blank was placed into
contact with a glass substrate and heated to 70°C for 20 minutes. The PDMS was
removed from the glass substrate using tweezers by pulling the blank from a
corner.
[0084] Figures 7A is an AFM image of the resulting microstructure, with the
corresponding AFM line scan in Figure 7B. The microstructure is a pattern of
tapered PDMS lines 4 µm wide, approximately 700 run tall, with a separation of 4
urn. Figures 1C and 7D are the AFM image and corresponding AFM line scan of
the PDMS after its removal from the glass substrate. The PDMS blank has the
opposite pattern relative to the microstructure, with trenches approximately 800
nm deep and openings 4 µm wide with 4 µm spacing.
[0085] Example 5 - Sub-Micron Patterning Using Direct Lithography
[0086] A microstructure of PDMS on a glass substrate was formed as
described in Example 4, but using a different UVO photomask. The UVO
photomask was prepared as in Example 4, except that the metal layer was
patterned as 300 nm lines with 300 nm spacings. Figures 8A is an AFM image of
the resulting microstructure, with the corresponding AFM line scan in Figure 8B.
The microstructure is a pattern of tapered PDMS lines approximately 250 nm
wide, with a separation of 350 nm and a variable height.
[0087] Example 6 - Use Of Direct Lithography Pattern As Resist
[0088] A UVO photomask was prepared as in Example 4, except that the metal
layer was patterned as 4 µm wide lines separated by 10 urn spacings. A planar
PDMS blank was placed in contact with a UVO photomask and irradiated through
the mask for 6 minutes using a deuterium lamp. The blank was then placed into
contact with a MPTMS silanized gold surface having a gold thickness of 100 nm
and heated to 70°C for 20 minutes. The PDMS was removed from the substrate

using tweezers by peeling the blank from a corner. Figure 9A is an optical
micrograph of the resulting microstructure, having PDMS lines 4.1µm wide with
a peak height of 698 nm. The inset of Figure 9A is an AFM image of a single
PDMS line within this microstructure.
[00891 The PDMS pattern was transferred into the gold film by wet etching the
exposed gold layer and the underlying titanium layer. Stripping of the PDMS
resist provided a pattern of gold lines, shown by the optical micrograph of Figure
9B.
[0090] Example 7 - Use Of Direct Lithography For 3-Dimensional Patterning
[0091] A UVO photomask was prepared as in Example 4, except that the metal
layer was patterned as 3 µm wide lines separated by 3 urn spacings. A planar
PDMS blank was placed in contact with a UVO photomask and irradiated through
the mask for 30 minutes using a deuterium lamp. The blank was then placed into
contact with a glass substrate and heated to 70°C for 20 minutes. The PDMS was
removed from the substrate using tweezers by peeling the blank from a corner.
[0092] A second planar PDMS blank was placed in contact with the same
UVO photomask and irradiated through the mask for 15 minutes using a
deuterium lamp. The PDMS pattern on the glass substrate was also exposed to
UVO for 15 minutes, but without an intervening mask. The second treated blank
was placed into contact with the glass substrate having the PDMS pattern;
however, the second blank was oriented so that the activated lines on the surface
of the second blank were perpendicular to the PDMS lines already on the glass
surface. The entire assembly was heated to 140°C for 40 minutes, and the second
PDMS blank was removed using tweezers by peeling the blank from a corner.
Figure 10A is an optical micrograph of the resulting microstructure, having
perpendicular sets of PDMS lines approximately 3 µm wide. Figure 10B is an
AFM image of this microstructure, showing the doubled height of the
microstructure at the intersections of the lines.

[0093] Example 8 - Use Of Direct Lithography For Patterning Of Discrete
Material
[0094] A UVO photomask was prepared as in Example 4, except that the metal
layer was patterned as 100 µm x 100 µm squares separated by 100 µm spacings.
A silicon on insulator wafer (SOI, Janus) was patterned to form a rectangular array
of silicon structures approximately 10 µm x 3 µm on a silicon dioxide layer.
[0095] A planar PDMS blank was placed in contact with a UVO photomask
and irradiated through the mask for 6 minutes using a mercury lamp positioned
approximately 3 centimeters from the blank. During this irradiation time, the
patterned SOI wafer etched in a stirred 49% HF solution for 1 minute 35 seconds
to undercut the silicon structures and form single crystal silicon wires having
dimensions of approximately 10 µm x 3 µm. After removal from the HF solution,
the SOI wafer was rinsed with water and gently blown dry with nitrogen. The
etching step was timed to conclude 45 seconds prior to the end of the 6 minute
UVO exposure. This amount of time was sufficient to rinse, dry, and move the
sample into position for the contact step.
[0096] The blank was then placed into contact with the patterned face of the
SOI wafer and heated in an oven to 70°C for 30 minutes. The assembly was
removed from the oven and placed, with the SOI side down, on a hotplate set at
300°C for 20 seconds. The assembly was then submerged in liquid nitrogen for 10
seconds. After allowing the assembly to warm to room temperature for several
seconds, the PDMS was sufficiently flexible and was removed from the substrate
using tweezers by peeling the blank from a corner.
[0097] Figures 11A and 11B are optical micrographs of the SOI wafer after
patterning by direct lithography. The 100 µm x 100 µm squares correspond to
regions without any silicon wires. Figures 11C and 11D are optical micrographs
of the PDMS blank, having a pattern of 100 µm x 100 µm squares containing
arrays of single crystal silicon wires.

[0098J It is therefore intended that the foregoing detailed description be
regarded as illustrative rather than limiting, and that it be understood that it is the
following claims, including all equivalents, that are intended to define the spirit
and scope of this invention.

WE CLAIM:
1. A method of making a microstructure containing a silicon-containing
elastomer, comprising:
selectively activating a portion (160; 152) of a surface of a silicon-containing elastomer
(150), wherein the selectively activating comprises partially covering the surface to provide
a protected portion of the surface and an unprotected portion of the surface, and applying
an activating treatment to the unprotected portion;
contacting the activated portion (160) with a substrate (180;280); contacting
the activated portion (160) with a substrate (180;280); and
bonding the activated portion and the substrate, such that the activated
portion and a portion (190;290) of the substrate in contact with the activated portion are
irreversibly attached.
2. The method as claimed in claim 1, wherein the partially covering the surface
comprises forming a hard mask (120,130) on the protected portion of the surface.
3. The method as claimed in claim 1, wherein the partially covering the surface
comprises positioning a mask (120,130) on the surface of the silicon-containing elastomer.
4. The method as claimed in claim 1, wherein the applying an activating
treatment comprises irradiating the unprotected portion with UV radiation.
5. The method as claimed in claim 4, wherein
the partially covering the surface comprises positioning a mask (120,130) on
the surface of the silicon-containing elastomer (150); the mask comprising a pattern of UV-
opaque portions (120) and UV-transparent portions, and comprising a spacer material (130)
under the UV-opaque portions; and
the unprotected portion of the surface is below and spaced apart from the
UV-transparent portions.

6. The method as claimed in claim 4, wherein at least the unprotected portion is
in contact with an atmosphere enriched in molecular oxygen during the irradiation.
7. The method as claimed in claim 4, wherein at least the unprotected portion is
in contact with an atmosphere enriched in ozone during the irradiation.
8. The method as claimed in claim 1, wherein the bonding comprises heating the
silicon-containing elastomer (150) and the substrate (180;280).
9. The method as claimed in claim 1, wherein the surface of the silicon-containing
elastomer (150) is planar.
10. The method as claimed in claim 1, wherein the surface of the silicon containing
elastomer (150) comprises a pattern of raised areas and lowered areas.
11. The method as claimed in any of the preceding claims, further comprising
separating the silicon-containing elastomer (150) and the substrate (180;280).
12. The method as claimed in claim 11, wherein the substrate (180;280) and the
activated portion (190;290) of the surface remain in contact.
13. The method as claimed in claim 11, wherein the silicon-containing elastomer
(150) and the portion of the substrate (180;280) in contact with the activated portion of
the surface remain in contact.
14. The method as claimed in claim 1, wherein:
the selectively activating comprises positioning a mask (120,130) on an
unpatterned surface of a silicon-containing elastomer (150);

the mask comprising a pattern of UV-opaque portions (120) and UV-
transparent portions, and comprising a spacer material (130) under the UV-
opaque portions;
the surface comprising an exposed portion (152) below and spaced
apart from the UV-transparent portions;
the selectively activating further comprises irradiating the exposed portion of
the unpatterned surface with UV radiation to provide the activated portion (152);
the method further comprises removing the mask from the surface prior to the
contacting; and
the method further comprises separating the silicon-containing elastomer (150)
and the substrate;
wherein the substrate and the activated portion (190;290) of the surface remain
in contact.
15. The method as claimed in claim 14, wherein a layer (190;290) of silicon-
containing elastomer (150) remains connected to the activated portion of the surface after the
separating.
16. The method as claimed in claim 15, further comprising controlling the
thickness of the layer by adjusting the duration of the irradiating.
17. The method as claimed in any of claims 11, 12 or 14 to 16, wherein the
separating comprises inducing cohesive failure within the silicon-containing elastomer (150).
18. The method as claimed in any of claims 12 or 14 to 17, wherein a minimum
feature size of the activated portion of the surface on the substrate after the separating is
less than 1 micrometer.

19. The method as claimed in any of claims 13 or 14 to 18, further comprising,
after the separating,
applying an etching agent to the substrate (180;280) to remove a portion of
the substrate which is not in contact with the exposed portion (190;290) of the surface; and
removing the silicon-containing elastomer (150) from the substrate.
20. The method as claimed in claim 1, wherein:
the selectively activating comprises positioning a mask (120,130) on a
surface of a silicon-containing elastomer comprising a pattern of raised areas and lowered
areas;
the mask comprising a pattern of UV-opaque portions (120) and UV-
transparent portions, and comprising a spacer material (130) under the UV-opaque
portions;
the surface comprising an exposed portion (152) of raised areas below
and spaced apart from the UV-transparent portions;
the selectively activating further comprises irradiating the exposed portion of
raised areas (152) with UV radiation to provide the activated portion;
the method further comprises removing the mask (120,130) from the surface
prior to the contacting; and
the method further comprises separating the silicon-containing elastomer
(190;290) and the substrate;
wherein the substrate and the activated portion of the raised areas remain in
contact.
21. The method as claimed in claim 20, further comprising forming the silicon-
containing elastomer (150) comprising a pattern of raised areas (152) and lowered areas.

22. The method as claimed in claim 20, wherein the separating comprises inducing
cohesive failure within the silicon-containing elastomer (150).
23. The method as claimed in claim 20, wherein a portion of the silicon-containing
elastomer (150) above the lowered areas remains connected to the activated portion of
the raised areas after the separating.
24. The method as claimed in claim 20, wherein the pattern of raised and
lowered areas is configured as an array.
25. The method as claimed in claim 20, further comprising, after the separating,
applying an etching agent to the substrate (180;280) to remove a portion of the
substrate which is not in contact with the activated portion of the raised areas; and
removing the silicon-containing elastomer from the substrate.
26. The method as claimed in any of claims 12 or 14 to 25, further comprising,
after the separating,
depositing a material on the substrate (180;280); and
removing the silicon-containing elastomer from the substrate to provide a
pattern of the deposited material.
27. The method as claimed in any of claims 11, 12 or 14 to 26, wherein the
substrate is non-planar.
28. The method as claimed in any of the preceding claims, wherein the silicon-
containing elastomer (150) comprises a member selected from the group consisting of
polysiloxanes; block copolymers comprising segments of a polysiloxane; and silicon-
modified elastomers, preferably wherein the silicon-containing elastomer comprises a
polysiloxane, or preferably wherein the silicon-containing elastomer comprises
poly(dimethyl siloxane).

29. The method as claimed in any of claims 1 to 27, wherein the substrate (180;
280) comprises a member selected from the group consisting of silicon, silicon oxide,
quartz, glass, a polymer, and a metal.


A method of making a microstructure, comprising: selectively activating an
exposed portion of a surface of a silicon-containing elastomer by irradiating the
exposed portion with UV radiation through a mask, while covering a protected
portion of the surface with the mask, where during the irradiating the exposed
portion is in contact with an atmosphere containing oxygen, and the mask is in
contact with the protected portion; removing the mask from the surface of the
silicon-containing elastomer; contacting the surface of the silicon-containing
elastomer with a substrate; and bonding the activated portion and the substrate,
such that the activated portion and a portion of the substrate in contact with the
activated portion are irreversibly attached.

Documents:

01438-kolnp-2007-abstract.pdf

01438-kolnp-2007-assignment.pdf

01438-kolnp-2007-claims.pdf

01438-kolnp-2007-correspondence others 1.1.pdf

01438-kolnp-2007-correspondence others 1.2.pdf

01438-kolnp-2007-correspondence others.pdf

01438-kolnp-2007-description complete.pdf

01438-kolnp-2007-drawings.pdf

01438-kolnp-2007-form 1.pdf

01438-kolnp-2007-form 2.pdf

01438-kolnp-2007-form 3.pdf

01438-kolnp-2007-form 5.pdf

01438-kolnp-2007-international publication.pdf

01438-kolnp-2007-international search report.pdf

01438-kolnp-2007-pct request.pdf

01438-kolnp-2007-priority document.pdf

1438-KOLNP-2007-(20-10-2011)-ABSTRACT.pdf

1438-KOLNP-2007-(20-10-2011)-AMANDED CLAIMS.pdf

1438-KOLNP-2007-(20-10-2011)-DESCRIPTION (COMPLETE).pdf

1438-KOLNP-2007-(20-10-2011)-DRAWINGS.pdf

1438-KOLNP-2007-(20-10-2011)-EXAMINATION REPORT REPLY RECIEVED.pdf

1438-KOLNP-2007-(20-10-2011)-FORM 1.pdf

1438-KOLNP-2007-(20-10-2011)-FORM 2.pdf

1438-KOLNP-2007-(20-10-2011)-FORM 3.pdf

1438-KOLNP-2007-(20-10-2011)-OTHERS.pdf

1438-KOLNP-2007-(20-10-2011)-PETITION UNDER SECTION 137.pdf

1438-KOLNP-2007-ASSIGNMENT.pdf

1438-KOLNP-2007-CORRESPONDENCE OTHERS 1.1.pdf

1438-KOLNP-2007-CORRESPONDENCE.pdf

1438-KOLNP-2007-EXAMINATION REPORT.pdf

1438-KOLNP-2007-FORM 18.pdf

1438-KOLNP-2007-FORM 26 1.1.pdf

1438-KOLNP-2007-FORM 26.pdf

1438-KOLNP-2007-FORM 3.pdf

1438-KOLNP-2007-FORM 5.pdf

1438-KOLNP-2007-GRANTED-ABSTRACT.pdf

1438-KOLNP-2007-GRANTED-CLAIMS.pdf

1438-KOLNP-2007-GRANTED-DESCRIPTION (COMPLETE).pdf

1438-KOLNP-2007-GRANTED-DRAWINGS.pdf

1438-KOLNP-2007-GRANTED-FORM 1.pdf

1438-KOLNP-2007-GRANTED-FORM 2.pdf

1438-KOLNP-2007-GRANTED-SPECIFICATION.pdf

1438-KOLNP-2007-OTHERS.pdf

1438-KOLNP-2007-REPLY TO EXAMINATION REPORT.pdf

abstract-01438-kolnp-2007.jpg


Patent Number 252303
Indian Patent Application Number 1438/KOLNP/2007
PG Journal Number 19/2012
Publication Date 11-May-2012
Grant Date 08-May-2012
Date of Filing 23-Apr-2007
Name of Patentee THE BOARD OF TRUSTEES OF THE UNIVERSITY OF ILLINOIS
Applicant Address 352 HENRY ADMINISTRATION BULDING 506 WRIGHT, URBANA, IL
Inventors:
# Inventor's Name Inventor's Address
1 NUZZO, RALPH, G 2413 NORTH NOTTINGHAM COURT, CHAMPAIGN, IL 61821
2 MOTALA, MICHAEL, J. 609 W. HEALEY ST., CHAMPAIGN, IL 61820
3 LEE, KEON, JAE 108 BURWASH AVE. APT. B SAVOY, IL 61874
4 CHILDS, WILLIAM, R. 1802 PEACH ST, CHAMPAIGN, IL 61820
PCT International Classification Number N/A
PCT International Application Number PCT/US2005/036812
PCT International Filing date 2005-10-14
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 10/965, 279 2004-10-14 U.S.A.