U.S. patent application number 12/331962 was filed with the patent office on 2009-05-14 for fibrillar microstructure and processes for the production thereof.
This patent application is currently assigned to E. I. DU PONT DE NEMOURS AND COMPANY. Invention is credited to Anand Jagota, Jinsoo Kim.
Application Number | 20090121383 12/331962 |
Document ID | / |
Family ID | 34316489 |
Filed Date | 2009-05-14 |
United States Patent
Application |
20090121383 |
Kind Code |
A1 |
Jagota; Anand ; et
al. |
May 14, 2009 |
Fibrillar Microstructure and Processes for the Production
Thereof
Abstract
This invention relates to a fibrillar microstructure and
processes for the manufacture thereof. These processes involve
micromachining and molding, and can prepare sub-micron dimensioned
fibrillar microstructures of any shape from polymeric as well as
other materials.
Inventors: |
Jagota; Anand; (Bethlehem,
PA) ; Kim; Jinsoo; (Kennett Square, PA) |
Correspondence
Address: |
E I DU PONT DE NEMOURS AND COMPANY;LEGAL PATENT RECORDS CENTER
BARLEY MILL PLAZA 25/1122B, 4417 LANCASTER PIKE
WILMINGTON
DE
19805
US
|
Assignee: |
E. I. DU PONT DE NEMOURS AND
COMPANY
Wilmington
DE
|
Family ID: |
34316489 |
Appl. No.: |
12/331962 |
Filed: |
December 10, 2008 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10933725 |
Sep 2, 2004 |
7479318 |
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12331962 |
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60501522 |
Sep 8, 2003 |
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60501524 |
Sep 8, 2003 |
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Current U.S.
Class: |
264/219 |
Current CPC
Class: |
G03F 7/0002 20130101;
B81C 1/00111 20130101; Y10T 428/23993 20150401; Y10T 428/23943
20150401; Y10T 428/23936 20150401; B82Y 40/00 20130101; Y10T
428/23929 20150401; Y10T 428/23957 20150401; G03F 7/0017 20130101;
B82Y 10/00 20130101 |
Class at
Publication: |
264/219 |
International
Class: |
B29C 51/00 20060101
B29C051/00 |
Claims
1. A process for making a fibrillar microstructure, comprising (a)
applying a first layer of photoresist material to a substrate
wherein the layer has a pre-selected thickness; (b) removing
material from the first layer at a plurality of locations to create
at each location a channel through the first layer wherein each
channel has a pre-selected cross-sectional shape and size, and
wherein the substrate is exposed at the location of each channel;
(c) creating in the substrate at each location a corresponding
channel having a pre-selected depth and having the same
cross-sectional shape and size of the channel in the first layer at
that location; (d) removing the remainder of the first layer of
photoresist material from the substrate; (e) applying a second
layer of photoresist material on the substrate and in the channels
of the substrate wherein the second layer has a pre-selected
thickness; (f) removing material from the second layer at a
plurality of locations to create at each location a channel through
the second layer wherein each channel has a pre-selected
cross-sectional shape and size, and wherein a plurality of channels
in the substrate are exposed at the location of each channel in the
second layer; (g) removing from each channel in the substrate
exposed by a channel in the second layer the photoresist material
of the second layer; (h) applying a flowable microstructure
material to the second layer of photoresist material to fill the
exposed channels of the substrate and of the second photoresist
layer and to create a layer of flowable material on the second
photoresist layer; (i) hardening the flowable microstructure
material to form a fibrillar microstructure; and (j) separating the
fibrillar microstructure from the channels of the second layer and
the substrate.
2. A process according to claim 1 wherein a channel is created in a
layer of photoresist material having a cross-sectional shape that
is selected from the group consisting of circular, elliptical and
polygonal; and a channel is created in the substrate having a
different cross-sectional shape that is selected from the group
consisting of circular, elliptical and polygonal.
3. A process according to claim 1 wherein a channel having a
circular cross-sectional shape is created in the second layer of
photoresist material; and a channel having a cross-sectional shape
selected from triangular and diamond is created in the
substrate.
4. A process according to claim 1 wherein the pre-selected
thickness of the second photoresist layer is in the range of about
10 to about 150 microns.
5. A process according to claim 1 wherein the cross-sectional size
of the channels created in the second photoresist layer is in the
range of about 2 to about 10 microns.
6. A process according to claim 1 wherein the depth of the channels
in the substrate is in the range of about 0.5 to about 15
microns.
7. A process according to claim 1 wherein the cross-sectional size
of the channels created in the substrate is in the range of about
0.1 to about 1 microns.
8. A process according to claim 1 wherein the channels created in
the second photoresist layer are spaced to give fibrils secured to
a foundation of the fibrillar microstructure an areal density in
the range of about 3 to about 30 percent.
9. A process according to claim 1 wherein the flowable
microstructure material is selected from the group consisting of
polyamide, poly(ether/amide), polyester, poly(ether/ester),
polypropylene, polyacrylate, polystyrene, polyethylene,
polypropylene, polydimethyl siloxane and polyvinylidine
chloride.
10. A process for making a fibrillar microstructure, comprising (a)
applying a first layer of photoresist material to a substrate
wherein the layer has a pre-selected thickness; (b) removing
material from the first layer at a plurality of locations to create
at each location a channel through the first layer wherein each
channel has a pre-selected cross-sectional shape and size, and
wherein the substrate is exposed at the location of each channel;
(c) creating in the substrate at each location a corresponding
channel having a pre-selected depth and having the same
cross-sectional shape and size of the channel in the first layer at
that location; (d) applying a second layer of photoresist material
on the first layer and in the channels of the first layer and in
the channels of the substrate wherein the second layer has a
pre-selected thickness; (e) removing material from the second layer
at a plurality of locations to create at each location a channel
through the second layer wherein each channel has a pre-selected
cross-sectional shape and size, and wherein a plurality of channels
in the first layer are exposed at the location of each channel in
the second layer; (f) removing from each channel in the first layer
exposed by a channel in the second layer, and removing from each
corresponding channel in the substrate, the photoresist material of
the second layer; (g) applying a flowable microstructure material
to the second layer of photoresist material to fill the exposed
channels in the second layer, the first layer and the substrate and
to create a layer of flowable material on the second photoresist
layer; (h) hardening the flowable microstructure material to form a
fibrillar microstructure; and (i) separating the fibrillar
microstructure from the channels of the first and second layers and
the substrate.
11. A process according to claim 10 wherein a channel is created in
a layer of photoresist material having a cross-sectional shape that
is selected from the group consisting of circular, elliptical and
polygonal; and a channel is created in the substrate having a
different cross-sectional shape that is selected from the group
consisting of circular, elliptical and polygonal.
12. A process according to claim 10 wherein a channel having a
circular cross-sectional shape is created in the second layer of
photoresist material; and a channel having a cross-sectional shape
selected from triangular and diamond is created in the
substrate.
13. A process according to claim 10 wherein the pre-selected
thickness of the second photoresist layer is in the range of about
10 to about 150 microns.
14. A process according to claim 10 wherein the cross-sectional
size of the channels created in the second photoresist layer is in
the range of about 2 to about 10 microns.
15. A process according to claim 10 wherein the depth of the
channels in the substrate added to the pre-selected thickness of
the first photoresist layer is in the range of about 0.5 to about
15 microns.
16. A process according to claim 10 wherein the cross-sectional
size of the channels created in the first photoresist layer, and
the corresponding channels in the substrate, is in the range of
about 0.1 to about 1 microns.
17. A process according to claim 10 wherein the channels created in
the second photoresist layer are spaced to give fibrils secured to
a foundation of the fibrillar microstructure an areal density in
the range of about 3 to about 30 percent.
18. A process according to claim 10 wherein the flowable
microstructure material is selected from the group consisting of
polyamide, poly(ether/amide), polyester, poly(ether/ester),
polypropylene, polyacrylate, polystyrene, polyethylene,
polypropylene, polydimethyl siloxane and polyvinylidine
chloride.
19. A process for making a fibrillar microstructure, comprising (a)
applying a layer of photoresist material to a surface of a
substrate wherein the layer has a pre-selected thickness; (b)
removing material from the photoresist layer at a plurality of
locations to create at each location a channel through the layer
wherein each channel has a pre-selected cross-sectional shape and
size, and wherein the substrate is exposed at the location of each
channel; (c) creating in the substrate at each location a
corresponding channel having a pre-selected depth and having in a
portion of the substrate channel proximal to the surface the same
cross-sectional shape and size of the channel in the photoresist
layer at that location, and having in a portion of the substrate
channel distal from the surface a different cross-sectional shape
and size than the channel in the photoresist layer at that
location; (d) filling the channels in the substrate with a flowable
microstructure material; (e) hardening the flowable microstructure
material to form a fibrillar microstructure; and (f) separating the
fibrillar microstructure from the channels of the substrate.
20. A process according to claim 19 wherein the length of the
portion of the substrate channel that is proximal to the surface of
the substrate, and that has the same cross-sectional shape and size
of the corresponding channel in the photoresist layer at that
location, is more than about 90% of the length of the channel; and
the length of the portion of the substrate channel that is distal
from the surface of the substrate, and that has a different
cross-sectional shape and size than the corresponding channel in
the photoresist layer at that location, is less than about 10% of
the length of the channel.
21. A process according to claim 19 wherein one or more channels is
created having a cross-sectional shape that is selected from the
group consisting of circular, elliptical and polygonal; and one or
more channels is created having a different cross-sectional shape
that is selected from the group consisting of circular, elliptical
and polygonal.
22. A process according to claim 19 further comprising a step of
removing the photoresist before filling the channels.
23. A process according to claim 22 wherein the pre-selected depth
of the channels created is in the range of about 10 to about 150
microns.
24. A process according to claim 19 wherein the cross-sectional
size of the channels created is in the range of about 2 to about 10
microns.
25. A process according to claim 19 wherein the channels created
are spaced to give fibrils secured to a foundation of the fibrillar
microstructure an areal density in the range of about 3 to about 30
percent.
26. A process according to claim 19 wherein the flowable
microstructure material is selected from the group consisting of
polyamide, poly(ether/amide), polyester, poly(ether/ester),
polypropylene, polyacrylate, polystyrene, polyethylene,
polypropylene, polydimethyl siloxane and polyvinylidine
chloride.
27. A process according to claim 19 wherein the flowable
microstructure material is hardened by the removal of a solvent.
Description
[0001] This application is a division of and claims the benefit of
U.S. patent application Ser. No. 10/993,725, filed Sep. 2, 2004,
which is incorporated in its entirety as a part hereof for all
purposes, which claims the benefit of U.S. Provisional Application
No. 60/501,522, filed Sep. 8, 2003, and U.S. Provisional
Application No. 60/501,524, filed Sep. 8, 2003.
FIELD OF THE INVENTION
[0002] This invention relates to a fibrillar microstructure and
processes for the manufacture thereof. These processes involve
micromachining and molding, and can prepare sub-micron dimensioned
fibrillar microstructures of any shape from polymeric as well as
other materials.
BACKGROUND OF THE INVENTION
[0003] Many organisms have evolved a fibrillated interface for
controlled contact and adhesion. As discussed in WO 01/49776, for
example, the Gecko lizard appears to have evolved the ability to
create dry, re-applicable adhesion to a variety of surfaces by
relying only on weak van der Waals forces.
Despite the low intrinsic energy of separating surfaces held
together by van der Waals forces, these organisms are able to
achieve remarkably strong adhesion. The microstructure employed by
the Gecko, consisting of fibrils called setae and spatulae, plays a
critical role in this ability.
[0004] Processes disclosed in WO 01/49776 describe replicating the
natural structure of the gecko's foot by casting the structure,
generally from a mold. This involves creating a template on a micro
scale, placing the material from which the structure is to be
fabricated into the mold, and then either extracting the structure,
or dissolving the mold away.
[0005] A need remains, however, for processes that are more
versatile than those known in the art by which a fibrillar
microstructure may be prepared. The improved processes of this
invention enable the production of new kinds of fibrillar
microstructures.
SUMMARY OF THE INVENTION
[0006] One embodiment of this invention is a process for making a
fibrillar microstructure by
[0007] (a) applying a first layer of photoresist material to a
substrate wherein the layer has a pre-selected thickness;
[0008] (b) removing material from the first layer at a plurality of
locations to create at each location a channel through the first
layer wherein each channel has a pre-selected cross-sectional shape
and size, and wherein the substrate is exposed at the location of
each channel;
[0009] (c) creating in the substrate at each location a
corresponding channel having a pre-selected depth and having the
same cross-sectional shape and size of the channel in the first
layer at that location;
[0010] (d) removing the remainder of the first layer of photoresist
material from the substrate;
[0011] (e) applying a second layer of photoresist material on the
substrate and in the channels of the substrate wherein the second
layer has a pre-selected thickness;
[0012] (f) removing material from the second layer at a plurality
of locations to create at each location a channel through the
second layer wherein each channel has a pre-selected
cross-sectional shape and size, and wherein a plurality of channels
in the substrate are exposed at the location of each channel in the
second layer;
[0013] (g) removing from each channel in the substrate exposed by a
channel in the second layer the photoresist material of the second
layer;
[0014] (h) applying a flowable microstructure material to the
second layer of photoresist material to fill the exposed channels
of the substrate and of the second photoresist layer and to create
a layer of flowable material on the second photoresist layer;
[0015] (i) hardening the flowable microstructure material to form a
fibrillar microstructure; and
[0016] (j) separating the fibrillar microstructure from the
channels of the second layer and the substrate.
[0017] Another embodiment of this invention is a process for making
a fibrillar microstructure by
[0018] (a) applying a first layer of photoresist material to a
substrate wherein the layer has a pre-selected thickness;
[0019] (b) removing material from the first layer at a plurality of
locations to create at each location a channel through the first
layer wherein each channel has a pre-selected cross-sectional shape
and size, and wherein the substrate is exposed at the location of
each channel;
[0020] (c) creating in the substrate at each location a
corresponding channel having a pre-selected depth and having the
same cross-sectional shape and size of the channel in the first
layer at that location;
[0021] (d) applying a second layer of photoresist material on the
first layer and in the channels of the first layer and in the
channels of the substrate wherein the second layer has a
pre-selected thickness;
[0022] (e) removing material from the second layer at a plurality
of locations to create at each location a channel through the
second layer wherein each channel has a pre-selected
cross-sectional shape and size, and wherein a plurality of channels
in the first layer are exposed at the location of each channel in
the second layer;
[0023] (f) removing from each channel in the first layer exposed by
a channel in the second layer, and removing from each corresponding
channel in the substrate, the photoresist material of the second
layer;
[0024] (g) applying a flowable microstructure material to the
second layer of photoresist material to fill the exposed channels
in the second layer, the first layer and the substrate and to
create a layer of flowable material on the second photoresist
layer;
[0025] (h) hardening the flowable microstructure material to form a
fibrillar microstructure; and
[0026] (i) separating the fibrillar microstructure from the
channels of the first and second layers and the substrate.
[0027] A further embodiment of this invention is a process for
making a fibrillar microstructure by
[0028] (a) applying a layer of photoresist material to a surface of
a substrate wherein the layer has a pre-selected thickness;
[0029] (b) removing material from the photoresist layer at a
plurality of locations to create at each location a channel through
the layer wherein each channel has a pre-selected cross-sectional
shape and size, and wherein the substrate is exposed at the
location of each channel;
[0030] (c) creating in the substrate at each location a
corresponding channel having a pre-selected depth and [0031] having
in a portion of the substrate channel proximal to the surface the
same cross-sectional shape and size of the channel in the
photoresist layer at that location, and [0032] having in a portion
of the substrate channel distal from the surface a different
cross-sectional shape and size than the channel in the photoresist
layer at that location;
[0033] (d) filling the channels in the substrate with a flowable
microstructure material;
[0034] (e) hardening the flowable microstructure material to form a
fibrillar microstructure; and
[0035] (f) separating the fibrillar microstructure from the
channels of the substrate.
[0036] Yet another embodiment of this invention is a fibrillar
microstructure that includes (a) a foundation, (b) a plurality of
first-tier fibrils, each of which is attached at a first end to the
foundation, and (c) a plurality of second-tier fibrils, each of
which is attached to a second end of a first-tier fibril;
[0037] wherein each first-tier fibril has a cross-sectional shape
that is selected from the group consisting of circular, elliptical
and polygonal; and
[0038] wherein each second-tier fibril has a cross-sectional shape
that is selected from the group consisting of circular, elliptical
or polygonal but that is different from the cross-sectional shape
of the first-tier fibril to which it is attached.
BRIEF DESCRIPTION OF THE DRAWINGS
[0039] FIG. 1 is an illustration of the operation of a negative
photoresist.
[0040] FIG. 2 is an illustration of the operation of a positive
photoresist.
[0041] FIG. 3 is an illustration of a mold for a fibrillar
microstructure, a fibrillar microstructure being molded, and a
fibrillar microstructure separated from a mold.
[0042] FIG. 4 is micrograph of a fibrillar microstructure having
two tiers of fibrils.
[0043] FIG. 5 is micrograph of a fibrillar microstructure having a
single tier of fibrils.
[0044] FIG. 6 is an illustration of an exemplary spacing and shape
of openings or transparent spots in a photomask.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS OF THE INVENTION
[0045] The fabrication processes of this invention can generate a
mat-like fibrillar microstructure from virtually any polymeric,
oligomeric or ceramic material, or from any other material that has
sufficient mechanical stability to undergo formation into a fibril.
The fibrillar microstructure is referred to as fibrillar because it
is constituted of fibrils, which may be considered to be very fine
filaments, and a foundation in which each of the fibrils is an
individual nano to micro-dimensioned protrusion that is secured to
the foundation and extends or is projected therefrom. The
foundation is generally planar in its dimensions, but is often
prepared from material that gives it flexibility and thus the
capability of being formed into a variety of shapes.
[0046] One method for making the fibrillar microstructure of this
invention is by molding a suitable material into the form of a
substrate having fibrils attached thereto. The molding operation
utilizes a master mold form prepared by photolithographic means.
Using the master mold form, fibrils can be fabricated that have the
shapes and sizes, and have the dimensions and other properties, as
set forth herein. A variety of lithographic methods that provide
for a cutting or etching process in accordance with a patterning
system is suitable for use herein, including but not limited to
contact photolithography, proximity photolithography, projection
photolithography, interference photolithography, immersion
projection photolithography, immersion interference
photolithogrpahy, nanoimprint of thermal type, nanoimprint of
optical type (step and flash), and soft lithography.
[0047] Lithography is a method for preparation of the master form
used to mold the fibrils of an apparatus of this invention.
Photolithography is a specific form of lithography where light is
used as a degrading force. In a photolithographic method, a
photoresist is exposed to electromagnetic radiation, such as
ultraviolet light (UV), deep ultraviolet light (DUV), extreme
ultraviolet light (EUV) or X-ray. This exposure introduces a latent
image on the photoresist, for example, a pattern with difference in
solubility. This results from chemical changes in the molecular
structure of the resist. The latent image is subsequently developed
into relief structures through etching. Electron beam irradiation,
or ion-beam irradiation can be used instead of electromagnetic
radiation to introduce an image on the photoresist.
[0048] The exposure of the photoresist is usually patterned either
by interposing a mask between the source of radiation and the
material of the photoresist, or by scanning a focused spot of the
radiation source across the surface of the material. When masks are
used, the lithographic process yields a replica (reduced in size if
desired) of the pattern on the mask. A lithographic mask or
photomask is master mask that defines the pattern of radiation
incident on the photoresist. A photomask may include a flexible
sheet element having areas, which are transparent to radiation
incident on the photosensitive layer and complementary areas which
are effectively opaque to that radiation; the opaque and
transparent area defining the complementary image features to be
transferred to the photosensitive layer. Typically the photomask is
in a projection lithography stepper, where the projection lens is
located between the photomask and the photoresist coated substrate.
In the case of proximity or contact lithography, the photomask is
proximate to (i.e. sufficiently close so as to be in the line of
photons thereby effecting a pattern on the resist) or in contact
with the resist layer of the cutting device.
[0049] Negative or positive resist materials comprise two families
of photoactive or radiation-sensitive material. Negative resists
become less soluble after exposure to radiation, and thus the
unexposed areas can be removed by treatment with an appropriate
solvent or developer. Positive resists, on the other hand, increase
in solubility upon exposure, enabling the exposed regions to be
removed in the solvent or developers. The areas of resist that
remain following the imaging and development processes are used to
mask the underlying substrate for subsequent etching or other
image-transfer steps. If, for example, the underlying substrate or
base were SiO.sub.2, immersion of the structure into an etchant
such as buffered hydrofluoric acid would result in selective
etching of the SiO2 in those areas that were bared during the
development step. Resist material can be classified as positive or
negative on the basis of their radiation response [Thompson et al.,
Introduction to Microlithography, American Professional Reference
Book, pages 14-15 and 155-156, American Chemical Society,
Washington, D.C., (1994)].
[0050] Where typical photoresist technology is used, either a
negative or positive resist method may be employed for the cutting
process. The negative resist method is illustrated in FIG. 1. As
shown in FIG. 1, a photomask (10) is set proximate to a negative
resist (20), which in turn is in contact with a mold layer (40).
The photomask (10) is comprised of light transmitting (12) and
light non-transmitting (14) regions.
[0051] The mold layer (40) is positioned on a solid substrate (50).
The shape and/or spacing of the light non-transmitting regions of
the photomask (14) determine the image created on the photoresist
and, ultimately the design of the pattern. The layout of the mask
is thus derived from the dimensions desired to be produced in the
fibrils of the adhesive apparatus.
[0052] The method proceeds when the negative resist is selectively
exposed to electromagnetic radiation via a light transmitting
section of the photomask (12) and crosslinks the exposed section of
the negative resist material (20). Optionally the noncrosslinked
material may be removed by the application of a negative resist
developer (60), revealing a portion of the mold layer (40).
[0053] After removal of the noncrosslinked negative resist, a
cutting means (70), (typically irradiation with ions, plasma or
electrons), is applied to the exposed mold layer (40) which results
in the cutting of the mold layer (40) in the form of a pattern that
will enable molding of an apparatus of this invention containing
fibrils in the desired size and shape.
[0054] In another embodiment, this method makes use of a positive
resist as opposed to a negative resist. Referring to FIG. 2, the
method proceeds essentially as with the negative resist method
except a positive resist layer (80) is included in the place of the
negative resist. Exposure of the photomask (10) to light results in
degradation of the positive photoresist material in the light
transmitting region of the photomask (12), while in the non-light
transmitting regions (90) the photoresist persists without
degradation. A positive photoresist developer (100) is then applied
which removes the degraded portion of the positive photoresist
(80). When the cutting means (70), (typically irradiation with
ions, plasma or electrons) is applied, the pattern layer is again
cut in the form of a pattern that will enable molding of an
apparatus of this invention containing fibrils in the desired size
and shape.
[0055] The resist composition may be applied by spin coating or the
like to form a resist film which is then pre-baked on a hot plate
at 60.degree. C. to 200.degree. C. for 10 seconds to 10 minutes,
and preferably at 80.degree. C. to 150.degree. C. for 1/2 to 5
minutes. In the contact, proximity or projection lithography
approach a patterning mask having the desired pattern may then be
placed over the resist film and the film exposed through the mask
to an electron beam or to high-energy radiation having a wavelength
below 300 nm such as deep-UV rays, excimer laser light, or x-rays
in a dose of about 1 to 200 mJ/cm.sup.2, and preferably about 10 to
100 mJ/cm.sup.2, then post-exposure baked (PEB) on a hot plate at
60.degree. C. to 150.degree. C. for 10 seconds to 5 minutes, and
preferably at 80.degree. C. to 130.degree. C. for 1/2 to 3 minutes.
Finally, development may be carried out using a developer such as
TMAH.
[0056] Typical photoresist materials include acrylates,
phenol/formaldehyde condensates, polyalkylaldehyde,
ortho-diazoketone and isoprene.
[0057] Subsequently, the latent pattern on the photoresist is
etched out to remove those sections of the mold layer that are not
protected by the photoresist. Following the etching process, the
resist is removed for example, by stripping, hydrolysis,
dissolution, or reaction. Developers useful in the present
invention may include for example, aqueous alkali solution, such as
0.1 to 5%, and preferably 2 to 3%, tetramethylammonium hydroxide
(TMAH). Developers may be applied by a conventional method such as
dipping, puddling, or spraying for a period of 10 seconds to 3
minutes, and preferably 30 seconds to 2 minutes.
[0058] The exposed mold layer is irradiated with a source of ions,
through the photomask with a specific pattern, and cutting of the
mold layer takes place. In this fashion, a master mold is obtained
from which an apparatus having fibrils of the size and shape as
described herein can be produced.
[0059] Cutting is accomplished in a bath of etchant liquid, or by
dry etching. Dry etching includes the utilization of ionized
radiation including but not limited to photon irradiation utilizing
ionized radiation such as ultraviolet rays, X-rays, electron
irradiation, ion-beam irradiation, reactive ion etching, sputter
etching, vapor phase etching, and neutral atoms machining.
Specifically, deep-UV rays having a wavelength of 254 to 120 nm, an
excimer laser, especially ArF excimer laser (193 nm), F.sub.2
excimer laser (157 nm), Kr.sub.2 excimer laser (146 nm), KrAr
excimer laser (134 nm) or Ar excimer laser (121 nm), x-rays, or an
electron beam are particularly useful.
[0060] Etching by plasma, which is an assembly of ions, electrons,
neutral atoms and molecules in which particle motion is governed
primarily by electromagnetic forces, or a partially ionized gas
containing an approximately equal number of positive and negative
charges, as well as some other number of non-ionized gas species,
also has certain utilities in the processes of this invention. Deep
reactive ion etching ("DRIE") involves a series of alternating etch
and passivation cycles, each lasting only a few seconds, as more
fully described in U.S. Pat. No. 5,501,893. Each passivation step
coats the surface being etched with a polymer layer, preventing
lateral etching by radicals. A fluorocarbon polymer is often used
for passivation, and the rate of deposition of the polymer is
controlled by the ratio of fluorine-to-carbon in the source gas.
After a passivation step in which all exposed surfaces of the
channel being cut in the substrate are coated with polymer, ion
bombardment during the next etch step of the process removes the
polymer from the bottom of the channel normal to the direction of
ion motion, and an isotropically etched cavity is then created.
This process results in microscopic "scallops" on the channel
sidewalls being etched. The degree of sidewall scalloping may be
controlled by varying the length of each etch/passivation cycle. An
etch stop, a layer of oxide in the substrate, may be used if
desired to help prevent etching from exceeding a pre-selected depth
for the channel. The plasma in an ion etcher is typically generated
by radio frequency energy, and this if desired may be enhanced by
use of an inductively coupled plasma system in which the RF energy
is coupled into a low pressure gas by an inductive coil mounted on
the outside of a quartz window. ICP etchers produce relatively low
ion energies, and biasing of the substrate being etched may thus be
used to tailor ion bombardment energies tuning the degree of
anisotropy of the resulting etch.
[0061] In one embodiment of this invention, a process can be
performed to make a fibrillar microstructure by etching a mold from
a substrate using photolithographic techniques as described above.
A first layer of photoresist material is applied to a substrate
such as a silicon wafer. This first layer will have a pre-selected
thickness. Photoresist material is removed from the first layer at
a plurality of locations to create at each location a channel
through the first layer wherein each channel has a pre-selected
cross-sectional shape and size, and wherein the substrate is
exposed at the location of each channel. Photoresist material is
removed from the first layer, using techniques as described above,
by irradiating the first layer through a mask, and then dissolving
away the photoresist material at the selected locations. The
substrate is referred to as exposed in the sense that the areas
from which photoresist material of the first layer has been removed
may then be subjected to etching.
[0062] The cross-sectional shape of the channels created in the
first layer is determined by the design of the mask, and may be
selected from shapes such as circular, elliptical or polygonal such
as triangular, diamond, rectangular, hexagonal or octagonal; or the
cross-sectional shape may be irregular. The cross-sectional shape
of each channel may be selected independently from that of each of
the other channels. The cross-sectional size of each channel is the
length of the longest dimension of the cross-sectional shape of
each channel, such as the diameter of a circle, and each may
independently of each other be in the range of from about 0.1
micron to about 1 micron.
[0063] After the material of this first photoresist layer has been
removed at the selected locations, an etching means is employed to
create in the substrate at each location a corresponding channel
having a pre-selected depth and having the same cross-sectional
shape and size of the channel in the first layer at that location.
The remainder of the photoresist material of the first layer is
typically then removed from the substrate. In an optional
embodiment, however, the remaining photoresist material of the
first layer is not removed.
[0064] A second layer of photoresist material is then applied on
the substrate and in the channels of the substrate (or on the first
layer and in the channels of the first layer and in the channels of
the substrate if the first layer remains) wherein the second layer
has a pre-selected thickness. A preferred material to use for the
second layer of photoresist material is SU-8, which is an
epoxy-based photoresist that is polymerizable by cationic
photopolymerization and is further described in U.S. Pat. No.
4,882,245.
[0065] Photoresist material is removed from this second layer at a
plurality of locations to create at each location a channel through
the second layer wherein each channel has a pre-selected
cross-sectional shape and size. A plurality of channels in the
substrate (or in the first layer if it remains) are thereby exposed
at the location of each channel in the second layer. Photoresist
material is removed from the second layer, using techniques as
described above, by irradiating the second layer through a mask,
and then dissolving away the photoresist material at the selected
locations. Channels in the substrate (or in the first layer if it
remains) are referred to as exposed in the sense that, after all
necessary photoresist material of the second layer has been
removed, those channels may then be filled with a fibrillar
microstructure material.
[0066] The cross-sectional shape of the channels created in this
second layer is determined by the design of the mask, and may be
selected from shapes such as described above. The cross-sectional
shape of each second-layer channel may be selected independently
from that of each other channel. The cross-sectional shape of each
second-layer channel may be the same as or different from any one
or more of the channels in the substrate (and also in the first
layer if it remains) that are exposed by the creation of each
second-layer channel. The cross-sectional size of each channel is
the length of the longest dimension of the cross-sectional shape of
each channel, such as the diameter of a circle, and each may
independently of each other be in the range of from about 2 microns
to about 10 microns.
[0067] Removal of photoresist material from the second layer at the
locations of the second-layer channels also results in removal of
the same photoresist material that was deposited in each channel in
the substrate corresponding to a first-layer channel. If the first
photoresist layer remains, removal of the photoresist material of
the second layer also result in removal of that same photoresist
material from the first-layer channels.
[0068] The longitudinal axis of each channel will typically be, if
not perpendicular, essentially perpendicular to (i.e. forming an
angle of less than 15.degree. off of normal with) a plane that is,
in each instance, represented by the substrate and the first and
second photoresist layers. Removal of photoresist material from all
channels thus creates a multi-layer mold composed of the substrate
and the second layer, and optionally the first layer, in which a
plurality of channels in the substrate (and also in the first layer
if it remains) is exposed by and accessible through each single
channel in the second layer. Such a mold is shown in FIG. 3(a).
[0069] The exposed channels in the second layer and the substrate
(and those in the first layer if it remains) are then filled with a
flowable microstructure material, and a layer of microstructure
material is also created on top of the second photoresist layer.
This arrangement is shown in FIG. 3(b). The flowable material can,
for example, be placed in and on the mold by melt coating or
solution coating. The microstructure material is then hardened (for
example, by cooling or devolatilization of solvent), and in its
hardened form is then separated from the channels in the second
layer and the substrate (and from those in the first layer if it
remains).
[0070] The microstructure material in its hardened form as
separated from the mold created from the multiple layers of
substrate and photoresist material is a fibrillar microstructure.
Its foundation is created by the layer of flowable microstructure
material that was formed on top of the second photoresist material
before hardening. A plurality of first-tier fibrils, each of which
is attached at a first end to the foundation is created by the
flowable material that was placed before hardening in the channels
of the second photoresist layer. A plurality of second tier
fibrils, each of which is attached to a second end of a first-tier
fibril, is created by the flowable material that was placed before
hardening in the channels of the substrate (and the channels in the
first photoresist layer if it remains). A graphical representation
of a fibrillar microstructure thus formed is shown in FIG. 3(c). A
photomicrograph of the first-tier fibrils, and the second-tier
fibrils located thereon, in a fibrillar microstructure actually
made by the process described above is shown in FIG. 4.
[0071] In an alternative embodiment of the process described above,
a first layer of photoresist material is applied to the substrate,
and material is removed from this first layer at a plurality of
locations to create at each location a channel through the first
layer wherein each channel has a pre-selected cross-sectional shape
and size, and wherein the substrate is exposed at the location of
each channel. Photoresist material is removed from the first layer,
using techniques as described above, by irradiating this first
layer through a mask, and then dissolving away the photoresist
material at the selected locations. The cross-sectional shape and
size of the channels created in the first layer of photoresist
material is determined by the design of the mask.
[0072] After the photoresist material of this first layer has been
removed at the selected locations, an etching means is employed to
create in the substrate at each location a corresponding channel
having a pre-selected depth and having the same cross-sectional
shape and size of the channel in the first layer at that location.
The remainder of the photoresist material of the first layer is
typically then removed from the substrate.
[0073] A second layer of photoresist material is then applied on
the substrate and in the channels of the substrate. Photoresist
material is removed from this second layer at a plurality of
locations to create at each location a channel through the second
layer wherein each channel has a pre-selected cross-sectional shape
and size. Photoresist material is removed from this second layer,
using techniques as described above, by irradiating this second
layer through a mask, and then dissolving away the photoresist
material at the selected locations. The substrate is exposed at the
location of each of the channels in the second layer, but a mask is
used that has a design such that each channel in the second layer
is smaller in cross-sectional size than any of the channels that
already exist in the substrate, the location of each channel in the
second photoresist layer falls within the location of a channel
that already exists in the substrate, and no channel in the second
photoresist layer has a location that falls outside of the location
of a channel that already exists in the substrate.
[0074] The substrate is then etched through the channels in the
second photoresist layer, which creates a subset of smaller
channels within each channel that already exists in the substrate,
with the depth of the channels in the subset being controlled by
the strength and duration of the etch. The material of the second
photoresist layer is then removed, and the substrate is used as
mold in the manner described above.
[0075] In a fibrillar microstructure prepared by the processes
described above, a first-tier fibril has a length L.sup.1 in the
range of about 10 to about 150 microns (or alternatively in the
range of about 15 to about 100 microns), and a second-tier fibril
has a length L.sup.2 in the range of about 0.5 to about 15 microns
(or alternatively in the range of about 0.75 to about 10 microns).
The length of the first-tier fibrils is determined by the
pre-selected thickness of the second photoresist layer, and the
length of the second-tier fibrils is determined by the pre-selected
depth to which the channels are etched in the substrate (together
with the pre-selected thickness of the first photoresist layer if
it remains). The first-tier fibrils have a characteristic width
a.sup.1 in the range of about 2 to about 10 microns (or
alternatively in the range of about 3 to about 5 microns), and the
second-tier fibrils have a characteristic width a.sup.2 in the
range of about 0.1 to about 1 microns (or alternatively in the
range of about 0.3 to about 0.5 microns). The characteristic width
of a fibril is the length of the longest dimension of the
cross-sectional shape of the fibril, such as the diameter of a
circle. The characteristic width of the first-tier fibrils is
determined by the cross-sectional size and shape of the channels in
the second photoresist layer, and the characteristic width of the
second-tier fibrils is determined by the cross-sectional size and
shape of the channels in the substrate (and those in the first
photoresist layer if it remains).
[0076] In an alternative embodiment of this invention, a fibrillar
microstructure may be made in which each fibril is larger at the
free end than at the end at which is secured to a foundation.
Fibrils characterized by such feature are shown in FIG. 5. In this
process, a layer of photoresist material is applied to a surface of
a substrate wherein the layer has a pre-selected thickness.
Material is then removed from the photoresist layer at a plurality
of locations to create at each location a channel through the layer
wherein each channel has a pre-selected cross-sectional shape and
size, and wherein the substrate is exposed at the location of each
channel. At each location, a corresponding channel having a
pre-selected depth is then created in the substrate.
[0077] Each channel in the substrate also has, in a portion of that
channel proximal to the surface the same cross-sectional shape and
size of the channel in the photoresist layer at that location. But
each channel in the substrate also has in a portion of that channel
distal from the surface a different cross-sectional shape and size
than the channel in the photoresist layer at that location. The
different size in the portion of the substrate channels distal from
the surface is usually a larger size. When that is the case, the
difference in size may be created, for example, by reducing or
eliminating passivation in a DRIE system at the bottom of the
channel, i.e. at a location close to the pre-selected depth, to
engage intentionally in isotropic etching and create an enlarged
scallop or notch in the substrate. The presence of an etch-stop,
e.g. a layer of oxide, in the substrate may assist in placing the
notch at the desired depth. A smaller size in the distal portion,
such as a tapered or cone shape, could be obtained by increasing
passivation at the bottom of the channel.
[0078] The channels in the substrate are then filled with a
flowable microstructure material, and the flowable microstructure
material is hardened to form a fibrillar microstructure as
described above. The fibrillar microstructure is then separated
from the channels of the substrate. In a preferred embodiment, the
photoresist layer is removed before the channels of the substrate
are filled with the fibrillar microstructure material, but the
photoresist layer may remain if desired.
[0079] The length of the portion of each channel that is proximal
to the surface of the substrate, and that has the same
cross-sectional shape and size of the corresponding channel in the
photoresist layer at that location, may be more than about 90% of
the length of the channel, and may in other embodiments be more
than about 95%, about 98% or about 99% of the length of the
channel. The length of the portion of each channel that is distal
from the surface of the substrate, and that has a different
cross-sectional shape and size than the corresponding channel in
the photoresist layer at that location, may be less than about 10%
of the length of the channel, and may in other embodiments be less
than about 5%, about 2% or about 1% of the length of the channel.
As a result, the length of the portion of each fibril that is
proximal to the foundation of the fibrillar microstructure, and
that has the same cross-sectional shape and size of the
corresponding channel in the photoresist layer at that location,
may be more than about 90% of the length of the fibril, and may in
other embodiments be more than about 95%, about 98% or about 99% of
the length of the fibril. The length of the portion of each fibril
that is distal from the foundation, and that has a different
cross-sectional shape and size than the corresponding channel in
the photoresist layer at that location, may be less than about 10%
of the length of the fibril, and may in other embodiments be less
than about 5%, about 2% or about 1% of the length of the
fibril.
[0080] As noted above, the cross-sectional shape of the portion of
each channel that is proximal to the surface of the substrate, and
correspondingly the cross-sectional shape of the portion of each
fibril that is proximal to the foundation of the fibrillar
microstructure, may be independently selected from among a variety
of shapes such as those described above.
[0081] In a fibrillar microstructure prepared by the process
described above, a fibril, including both the portions that are
proximal to and distal from the foundation, may have a length L in
the range of about 10 to about 150 microns (or alternatively in the
range of about 15 to about 100 microns). The length of the fibrils
is determined by the pre-selected depth to which the channels are
etched in the substrate (together with the pre-selected thickness
of the photoresist layer if it remains). The portion of each fibril
that is proximal to the foundation may have a characteristic width
a (as defined above) in the range of about 2 to about 10 microns
(or alternatively in the range of about 3 to about 5 microns). The
characteristic width of the portion of a fibril that is proximal to
the foundation is determined by the cross-sectional size and shape
of the portion of the channels that is proximal to the surface of
the substrate (and the channels in the photoresist layer if it
remains).
[0082] As noted above, the fibrils in a fibrillar microstructure of
this invention may have a variety of cross-sectional shapes. As a
result, a further embodiment of this invention is a fibrillar
microstructure that has (a) a foundation, (b) a plurality of
first-tier fibrils, each of which is attached at a first end to the
foundation, and (c) a plurality of second tier fibrils, each of
which is attached to a second end of a first-tier fibril; wherein
each first-tier fibril has a cross-sectional shape that is selected
from the group consisting of circular, elliptical and polygonal;
and wherein each second-tier fibril has a cross-sectional shape
that is selected from the group consisting of circular, elliptical
or polygonal but that is different from the cross-sectional shape
of the first-tier fibril to which it is attached. For example, a
first-tier fibril may have a circular cross-sectional shape, and a
second-tier fibril may have a triangular or diamond cross-sectional
shape.
[0083] In particular embodiments, each first-tier fibril may have
the same or a different cross-sectional shape, and each second-tier
fibril may have the same or a different cross-sectional shape than
the first-tier fibril to which it is attached. A polygonal shape
may be selected from the group consisting of triangular, diamond,
rectangular, hexagonal and octagonal. Variations in shape among the
first-tier fibrils as a group, and variations in shape between a
first-tier fibril and the second-tier fibrils attached thereto is
useful as an aid in reducing clumping among the fibrils that are
secured to a foundation to form a fibrillar microstructure.
[0084] FIG. 6 shows a schematic of a 15 mm.times.15 mm fraction of
the pattern on one of the many possible photomasks that may be used
for the process of making a fibrillar microstructure according to
this invention. UV light-transparent spots on the mask can be made
of any desired shape, for example, triangle, diamond or circle. The
shape of the openings or transparent spots in the mask determines
the shape of the fibrils in the fibrillar microstructure produced
therefrom, as described above. The separations of "1.times.",
"2.times." and "3.times." correspond to the distance between two
adjacent spots as measured in terms of the cross-sectional size of
the spot, which is the length of the longest dimension of the
cross-sectional shape of each channel, such as the diameter of a
circle. For example, "1.times." corresponds to a distance
equivalent to 1 unit of size between two spots, "2.times."
corresponds to a distance equivalent to 2 units of size between two
spots, and "3.times." corresponds to a distance equivalent to 3
units of size between two spots. Shape and spacings patterns such
as these can be repeated on the photomask as desired, and will
cause channels to be created in the photoresist layer, and etched
in the substrate, with the same pattern of shape and placement, and
thus cause the formation of fibrils in the microstructure with the
same pattern of shape and placement.
[0085] The spacing of the openings or transparent spots on the mask
as described above controls the areal density of the fibrils (or
the first-tier fibrils when a second tier exists) on the
foundation, and the areal density of the second-tier fibrils on
each first-tier fibril. Areal density is defined as the percentage
of the area of a surface, either the foundation or the top of a
first-tier fibril, occupied by the point of junction between fibril
and foundation of the fibrils that are secured thereto. The areal
density of fibrils on the foundation, or the areal density on the
foundation of the first-tier fibrils when two tiers exist, may be
in the range of about 3 to about 30 percent (or alternatively in
the range of about 5 to about 10 percent). When they exist, the
areal density of second tier fibrils on a first-tier fibril may be
in the range of about 3 to about 15 percent (or alternatively in
the range of about 5 to about 10 percent).
[0086] As noted above, the longitudinal axis of each channel will
typically be, if not perpendicular, essentially perpendicular to
(i.e. forming an angle of less than 15.degree. off of normal with)
a plane that is, in each instance, represented by the substrate and
the first and second photoresist layers. As a consequence, in a
further alternative, one or more of fibrils will have a neutral
axis, passing through the centroid of the cross-sectional area of
the fibril, that has an orientation with the plane of the
foundation, at the point of intersection of the axis with the plane
of the foundation, in the range of greater than 75.degree. to about
90.degree.. It is more preferred that such orientation of the
neutral axis is in the range of about 80.degree. to about
90.degree., and it is most preferred that it be in the range of
about 85.degree. to about 90.degree.. Each second-tier fibril, when
it exists, will desirably have the same orientation of the neutral
axis thereof with the plane represented by the top of the
first-tier fibril to which it is secured. Methods for determination
of the orientation of a neutral axis are known in the art from
sources such as An Introduction to the Mechanics of Solids, R. R.
Archer et al, McGraw-Hill (1978), which is incorporated for such
purpose as a part hereof.
[0087] Any melt processable thermoplastic material can be used to
form the microstructure. Also, thermosetting materials can be used
by in-situ polymerization of the monomer on the silicon-based mold.
In this invention, the polymers from which the dispersed domains
and/or the matrix may be made include polymers and copolymers, and
blends of two or more of either or both that are amenable to
extrusion and spinning. Exemplary polymers and/or copolymers
include polyacetal, polyacetylene, polyacrylamide, polyacrylate,
polyacrylic acid, polyacrylonitrile, polyamide, polyaminotriazole,
polyaramid, polyarylate, polybenzimidazole, polybutadiene,
polybutylene, polycarbonate, polychloroprene, polyesters,
polyethers, polyethylenes (including halogenated polyethylenes),
polyethylene imine, polyethylene oxide, polyimide, polyisoprene,
polymethacrylate, polyoxadiazole, polyphenylene oxide,
polyphenylene sulfide, polyphenylene triazole, polypropylene,
polypropylene oxide, polysiloxanes (including polydimethyl
siloxane), polystyrene, polysulfone, polyurethane, poly(vinyl
acetal), poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl
butyral), poly(vinyl carbazole), poly(vinyl chloride), poly(vinyl
ether), poly(vinyl fluoride), acrylonitrile/butadiene/styrene
copolymer, acrylate copolymers (including ethylene/vinyl
acetate/glycidyl methacrylate copolymer), styrene/acrylonitrile
copolymer.
[0088] The polymers and/or copolymers from which a fibrillar
microstructure is made may be selected from a subgroup of the
foregoing formed by omitting any one or more members from the whole
group as set forth in the list above. As a result, the polymer
and/or copolymer may in such instance not only be one or more
members selected from any subgroup of any size that may be formed
from the whole group as set forth in the list above, but may also
be selected in the absence of the members that have been omitted
from the whole group to form the subgroup. The subgroup formed by
omitting various members from the whole group in the list above
may, moreover, be an individual member of the whole group such that
the polymer or copolymer is selected in the absence of all other
members of the whole group except the selected individual member.
The subgroup formed by omitting various members from the whole
group in the list above may, moreover, contain any number of the
members of the whole group such that those members of the whole
group that are excluded to form the subgroup are absent from the
subgroup.
[0089] Examples of polymers particularly suitable for use to make a
fibrillar microstructure include polyamide, poly(ether/amide),
polyester, poly(ether/ester), polypropylene, polyacrylate,
polystyrene, polyethylene, polypropylene, polydimethyl siloxane and
polyvinylidine chloride. Other non-polymeric materials such as
ceramics can also be used to generate the microstructures.
[0090] In an alternative embodiment, a solution of a polymer can be
applied to the mold cut from the substrate as the material from
which the microstructure is formed. Upon removal of solvent, a
microstructure can be generated having porosity in the structure. A
partially polymerized oligomeric species can also be used as the
microstructure material, with subsequent polymerization occurring
in the mold. Polymerizing an oligomeric that is admixed in its own
monomer can help control the viscosity of the material that is
transformed into the fibrillar microstructure. Selection of a
polymer, copolymer or blend thereof according to the molecular
weight distribution thereof can be utilized to control the
production of fibrils with varying degrees of tensile strength and
toughness.
[0091] The fibrillar microstructures made by the processes of this
invention may take the form or appearance of a piled, plush or
raised fabric similar to a velveteen, flannel or corduroy. These
fibrillar microstructures are useful to make fabrics or filters, to
make objects that have adhesive surfaces, and to make coverings for
solid objects such a wall paper. The objects that have adhesive
surfaces may be fabricated in the form of any type of sealing or
fastening device such as a fastener for apparel, for luggage, or
for a shoe.
[0092] Where an apparatus or method of this invention is stated or
described as comprising, including, containing, having, being
composed of or being constituted of or by certain components or
steps, it is to be understood, unless the statement or description
explicitly provides to the contrary, that one or more components or
steps other than those explicitly stated or described may be
present in the apparatus or method. In an alternative embodiment,
however, the apparatus or method of this invention may be stated or
described as consisting essentially of certain components or steps,
in which embodiment components or steps that would materially alter
the principle of operation or the distinguishing characteristics of
the apparatus or method would not be present therein. In a further
alternative embodiment, the apparatus or method of this invention
may be stated or described as consisting of certain components or
steps, in which embodiment components or steps other than those as
stated would not be present therein.
[0093] Where the indefinite article "a" or "an" is used with
respect to a statement or description of the presence of a
component in an apparatus, or a step in a method, of this
invention, it is to be understood, unless the statement or
description explicitly provides to the contrary, that the use of
such indefinite article does not limit the presence of the
component in the apparatus, or of the step in the method, to one in
numbe
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