U.S. patent application number 12/635730 was filed with the patent office on 2010-06-24 for stamper for transferring fine pattern and method for manufacturing thereof.
Invention is credited to Satoshi ISHII, Akihiro Miyauchi, Kyoichi Mori, Masahiko Ogino, Noritake Shizawa.
Application Number | 20100155989 12/635730 |
Document ID | / |
Family ID | 42264851 |
Filed Date | 2010-06-24 |
United States Patent
Application |
20100155989 |
Kind Code |
A1 |
ISHII; Satoshi ; et
al. |
June 24, 2010 |
STAMPER FOR TRANSFERRING FINE PATTERN AND METHOD FOR MANUFACTURING
THEREOF
Abstract
An object of the present invention is to provide a stamper for
transferring fine pattern and a method for manufacturing the
stamper, the stamper has a fine structure layer to improve a
continuous transferring property of the resinous stamper, and to
allow accurate and continuous transferring. In order to achieve the
above object, the present invention provides a stamper for
transferring fine pattern, including: a fine structure layer on a
supporting substrate, in which the fine structure layer is a
polymer of a resinous compound whose principal component is
silsesquioxane derivative having a plurality of polymerizable
functional groups.
Inventors: |
ISHII; Satoshi; (Hitachi,
JP) ; Ogino; Masahiko; (Hitachi, JP) ;
Shizawa; Noritake; (Ninomiya, JP) ; Mori;
Kyoichi; (Oiso, JP) ; Miyauchi; Akihiro;
(Hitachi, JP) |
Correspondence
Address: |
ANTONELLI, TERRY, STOUT & KRAUS, LLP
1300 NORTH SEVENTEENTH STREET, SUITE 1800
ARLINGTON
VA
22209-3873
US
|
Family ID: |
42264851 |
Appl. No.: |
12/635730 |
Filed: |
December 11, 2009 |
Current U.S.
Class: |
264/225 ;
425/174.4; 425/177 |
Current CPC
Class: |
B29C 2035/0827 20130101;
G03F 7/0002 20130101; B82Y 10/00 20130101; B29C 2059/023 20130101;
B82Y 40/00 20130101; B29C 35/02 20130101; B29C 59/022 20130101;
B29C 35/0888 20130101 |
Class at
Publication: |
264/225 ;
425/177; 425/174.4 |
International
Class: |
B29C 59/16 20060101
B29C059/16; B28B 1/10 20060101 B28B001/10 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 11, 2008 |
JP |
2008-315142 |
Claims
1. A stamper for transferring a fine pattern, comprising: a fine
structure layer on a supporting substrate, wherein the fine
structure layer is a polymer of a resinous compound whose principal
component is silsesquioxane derivative having a plurality of
polymerizable functional groups.
2. The stamper according to claim 1, wherein the silsesquioxane
derivative content in the resinous compound is 80 weight percent or
more.
3. The stamper according to claim 1, wherein the silsesquioxane
derivative has three or more polymerizable functional groups.
4. The stamper according to claim 1, wherein the supporting
substrate and the fine structure layer are light-transmissive.
5. The stamper according to claim 1, wherein the polymerizable
functional group of the silsesquioxane derivative is at least one
selected from a vinyl group, an epoxy group, an oxetanyl group, a
vinyl ether group, and a (metha)acrylate group.
6. The stamper according to claim 1, wherein the resinous compound
further includes a photo-curing polymerization initiator.
7. The stamper according to claim 6, wherein the photo-curing
polymerization initiator is a cationic polymerizable catalyst which
initiates curing by ultraviolet light.
8. The stamper according to claim 1, wherein all of the components
of the resinous compound, except the photo-curing polymerization
initiator, are resins having the polymerizable functional
groups.
9. The stamper according to claim 1, wherein the supporting
substrate is composed of two or more kinds of layers whose elastic
coefficients differ one another.
10. The stamper according to claim 9, wherein the supporting
substrate includes a first hard layer, a first soft layer, a second
hard layer, and a second soft layer in order of the above
description, elastic coefficients of the first soft layer and the
second soft layer are less than those of the first hard layer and
the second hard layer, and the fine structure layer is formed on a
surface of the second soft layer.
11. The stamper according to claim 9, wherein the supporting
substrate includes the first hard layer, a soft layer, and the
second hard layer in order of the above description, and an elastic
coefficient of the soft layer 1e is less than those of the first
hard layer and the second hard layer, the fine structure layer is
formed on a surface of the second hard layer.
12. A stamper for transferring a fine pattern on a curable resinous
material provided on a transferred substrate, comprising: a fine
structure layer on a supporting substrate, wherein the fine
structure layer is a polymer of a resinous compound whose principal
component is silsesquioxane derivative having a plurality of
polymerizable functional groups, and a curing mechanism of the
silsesquioxane derivative differs from that of the curable resinous
material.
13. The stamper according to claim 12, wherein the silsesquioxane
derivative content in the resinous compound is 80 weight percent or
more.
14. The stamper according to claim 12, wherein the silsesquioxane
derivative has three or more polymerizable functional groups.
15. The stamper according to claim 12, wherein the supporting
substrate and the fine structure layer are light-transmissive.
16. The stamper according to claim 12, wherein the polymerizable
functional group of the silsesquioxane derivative is at least one
selected from a vinyl group, an epoxy group, an oxetanyl group, a
vinyl ether group, and a (metha)acrylate group.
17. The stamper according to claim 12, wherein the resinous
compound further includes a photo-curing polymerization
initiator.
18. The stamper according to claim 17, wherein the photo-curing
polymerization initiator is a cationic polymerizable catalyst which
initiates curing by ultraviolet light.
19. The stamper according to claim 12, wherein all of the
components of the resinous compound, except the photo-curing
polymerization initiator, are resins having the polymerizable
functional groups.
20. The stamper according to claim 12, wherein the supporting
substrate is composed of two or more kinds of layers whose elastic
coefficients differ one another.
21. The stamper according to claim 20, wherein the supporting
substrate includes a first hard layer, a first soft layer, a second
hard layer, and a second soft layer in order of the above
description, elastic coefficients of the first soft layer and the
second soft layer are less than those of the first hard layer and
the second hard layer, and the fine structure layer is formed on a
surface of the second soft layer.
22. The stamper according to claim 20, wherein the supporting
substrate includes the first hard layer, a soft layer, and the
second hard layer in order of the above description, and an elastic
coefficient of the soft layer 1e is less than those of the first
hard layer and the second hard layer, the fine structure layer is
formed on a surface of the second hard layer.
23. A method for manufacturing a stamper for transferring fine
pattern, comprising the steps of: applying a resinous compound
whose principal component is silsesquioxane derivative having a
plurality of polymerizable functional groups on a supporting
substrate; pressing a master mold on which a fine pattern is formed
against the resinous compound applied on the supporting substrate;
curing the resinous compound with the master mold being pressed;
and peeling the master mold from the cured resinous compound.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims benefit of the filing date of
Japanese Patent Application No. 2008-315142 filed on Dec. 11, 2008
which is incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to a stamper for transferring
a fine pattern on a surface of a transferred object by pressing the
stamper against the surface, and to a method for manufacturing the
stamper.
DESCRIPTION OF THE RELATED ART
[0003] Conventionally, a photolithography technology is frequently
used as the technology for processing a fine pattern needed in
semiconductor devices, etc. Because, however, the pattern has been
shrunk and a required process dimension has been shrunk as small as
a light source wave length which is used for an exposure, it
becomes difficult to process the fine pattern by the
photolithography technology. For this reason, instead of the
photolithography technology, an electron beam lithography apparatus
which is a kind of a charged particle beam apparatus has been
used.
[0004] A pattern formation method of the electron beam lithography
apparatus is a direct drawing method of a mask pattern, which is
different from a pattern formation method of a one-shot exposure
method using a light source such as i-line and an excimer laser.
Therefore, there is a disadvantage that an exposure time (drawing
time) increases as a number of patterns to be drawn increases.
Accordingly, a long time is required for completing the patterns.
As a result, in proportion to a degree of integration of a
semiconductor integrated circuit, a time required for the pattern
formation increases, thereby resulting in reduction of a
throughput.
[0005] Then, for speeding up the electron beam lithography
apparatus, a technology of one-shot drawing radiation method is
developing, in which method various shapes of masks are combined
and the electron beam is irradiated in one-shot, thereby resulting
in a complex-shaped beam. However, because a degree of requirement
for fine pattern has progressed, there are many factors which raise
a fabrication cost, for example, growing in size of the electron
beam apparatus and increase in accuracy of mask alignment.
[0006] In contradistinction to the above, a nanoimprint technology
is well known as a technology for forming a fine pattern at low
cost. In this nanoimprint technology, the fine pattern can be
formed on a resinous layer of a transferred object by pressing the
stamper having a concavity and convexity (a surface configuration)
corresponding to a concavity and convexity of a pattern to be
formed against, for example, a transferred object obtained by
forming a resinous layer on a predetermined substrate. Also, this
nanoimprint technology is considered to apply to formation of a
memory bit in a large volume storage medium, and pattern formation
in a semiconductor integrated circuit.
[0007] At present, a hard stamper (e.g., quartz, etc.) used in a
prior art nanoimprint technology has a disadvantage that the hard
stamper can not follow warps and projections of the transferred
substrate at the time of transferring, thereby resulting in
widespread transferring failure regions. In order to reduce the
transferring failure regions, it is necessary to absorb both of
warps and projections of the substrate. For this reason, a soft
resinous stamper which follows both of warps and projections of the
substrate is considered (see Hong H. Lee, Chem. Mater., vol. 16, p.
5000 (2004)). Further, a multi-layer type resinous stamper having a
flexible resinous layer called a buffer layer between a substrate
and a fine structure layer is reported (see B. Michel et al.,
Macromolecules, vol. 33, p. 3042 (2000)). Also, in the nanoimprint
technology, because peeling of the transferred object from the fine
structure layer has a considerable influence on a transferring
accuracy, mold releasing properties of both of the transferred
object and the fine structure layer are important. Conventionally,
the stamper (e.g., quartz, etc.) used in the nanoimprint is given
the mold releasing property by treating its surface with a
fluorinated mold release agent (see JP 2004-351693 A). At present,
a surface of a soft stamper is likewise releasing-treated to be
used for transferring.
[0008] However, in the prior art stamper, accuracy in the pattern
tends to decrease owing to uneven thickness of the applied mold
release agent, and the transferring failure occurs owing to
degradation of a mold releasing layer caused by repeated
transferring.
[0009] Therefore, an object of the present invention is to provide
a stamper for transferring fine pattern and a method for
manufacturing the stamper, the stamper has a fine structure layer
to improve a continuous transferring property of the resinous
stamper, and to allow accurate and continuous transferring.
SUMMARY OF THE INVENTION
[0010] In order to achieve the above object, the present invention
provides a stamper for transferring fine pattern, including: a fine
structure layer on a supporting substrate, in which the fine
structure layer is a polymer of a resinous compound whose principal
component is silsesquioxane derivative having a plurality of
polymerizable functional groups.
[0011] Also, in order to achieve the above object, the present
invention provides a method for manufacturing the stamper for
transferring fine pattern, including the steps of: applying a
resinous compound whose principal component is silsesquioxane
derivative having a plurality of polymerizable functional groups on
a supporting substrate; pressing a master mold on which a fine
pattern is formed against the resinous compound applied on the
supporting substrate; curing the resinous compound with the master
mold being pressed; and peeling the master mold from the cured
resinous compound.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] FIG. 1A is a schematic view showing a stamper for
transferring a fine pattern of an embodiment according to the
present invention;
[0013] FIG. 1B is a partial enlarged view showing a supporting
substrate of the stamper shown in FIG. 1A;
[0014] FIG. 1C is a partial enlarged view showing a modified
embodiment of the supporting substrate shown in FIG. 1B;
[0015] FIGS. 2A-2C are schematic views showing manufacturing
process of the stamper; and
[0016] FIG. 3 is a schematic view showing a mechanism of
transferring a fine pattern of the stamper to the transferred
object.
DETAILED DESCRIPTION OF THE INVENTION
[0017] Next, with reference to FIGS. 1-3, embodiments according to
the present invention will be explained in detail. FIG. 1A is a
schematic view showing a stamper for transferring a fine pattern of
an embodiment according to the present invention, FIG. 1B is a
partial enlarged view showing a supporting substrate of the stamper
shown in FIG. 1A, and FIG. 1C is a partial enlarged view showing a
modified embodiment of the supporting substrate shown in FIG.
1B.
[0018] As shown in FIG. 1A, the stamper 3 according to this
embodiment has a fine structure layer 2 on a supporting substrate
1. Here, the term "fine structure" means a structure which is
formed on the order of nanometer or micrometer units.
[0019] The supporting substrate 1 is not limited in material, size,
and method for manufacturing as long as the supporting substrate 1
has a function to support the fine structure layer 2. For example,
the supporting substrate 1 may be made of materials having strength
and workability such as a silicon wafer, various metallic
materials, a glass, a quartz, ceramics, and a resin, etc. More
specifically, Si, SiC, SiN, polycrystalline Si, Ni, Cr, Cu, and a
material including one or more of Si, SiC, SiN, polycrystalline Si,
Ni, Cr, and Cu are shown as examples. Especially, it is preferable
that the fine structure layer 2 and the buffer layer (not shown)
which may be disposed between the fine structure layer 2 and the
supporting substrate 1 are made of a photo-curable material because
the quartz and the glass are highly transparent and light is
irradiated into the resin efficiently.
[0020] Also, for example, phenol-formaldehyde resin (PF),
urea-formaldehyde resin (UF), melamine-formaldehyde resin (MF),
polyethylene terephthalate (PET), unsaturated polyester resin (UP),
alkyd resin, vinylester resin, epoxy resin (EP), polyimide resin
(PI), polyurethane (PUR), polycarbonate (PC), polystyrene (PS),
acrylic resin (PMMA), polyamide resin (PA), ABS resin, AS resin,
AAS resin, polyvinyl alcohol, polyethylene (PE), polypropylene
(PP), polytetrafluoroethylene (PTFE), polyarylate resin, cellulose
acetate, polypropylene, polyethylene naphthalate (PEN),
polybutylene terephthalate (PBT), polyphenylene sulfide (PPS),
polyphenylene oxide, cycloolefin polymer, polylactic resin,
silicone resin, and diallyl phthalate resin, etc. are given as
examples of the resin. These resins, either individually or in
combination, may be used. Also, these resins may include a filler
such as an inorganic filler, and an organic filler, etc.
[0021] Also, the supporting substrate 1 may has a flexible resinous
layer called a buffer layer (not shown) between the supporting
substrate 1 and the fine structure layer 2. Also, in order to
strengthen adhesion between the fine structure layer 2 and the
buffer layer, a surface of the buffer layer may be
coupling-treated.
[0022] The supporting substrate 1 may be made of a single or a
plurality of materials.
[0023] The supporting substrate 1 shown in FIG. 1B includes a first
hard layer 1a, a first soft layer 1b, a second hard layer 1c, and a
second soft layer 1d in order of the above description. Also,
elastic coefficients of the first soft layer 1b and the second soft
layer 1d are less than those of the first hard layer 1a and the
second hard layer 1c. Incidentally, the fine structure layer 2 is
formed on a surface of the second soft layer 1d. Each of the first
soft layer 1b, the second soft layer 1d, the first hard layer 1a,
and the second hard layer 1c can be made of materials selected from
the above described materials so as to keep the relation among the
above described elastic coefficients.
[0024] Also, the supporting substrate 1 may have another
configuration which is composed of two or more kinds of layers
whose elastic coefficients differ one another. The supporting
substrate 1 shown in FIG. 1C includes the first hard layer 1a, a
soft layer 1e, and the second hard layer 1c in order of the above
description, and an elastic coefficient of the soft layer 1e is
less than those of the first hard layer 1a and the second hard
layer 1c.
[0025] In addition, the supporting substrate 1 according to the
present invention is not limited in the order and combination of
the hard layers and the soft layers, and the layer at which the
fine structure layer 2 is disposed. That is, the supporting
substrate 1 is not limited to the number of layers, the order of
layers, and configuration.
[0026] The fine structure layer 2 is made of a polymer (cured
material) of a resinous compound whose principal component is
silsesquioxane derivative having a plurality of polymerizable
functional groups. The silsesquioxane derivative content in the
resinous compound is preferably 80 weight percent or more.
[0027] The silsesquioxane derivative (monomer) has preferably three
or more polymerizable functional groups.
[0028] The polymerizable functional group is preferably at least
one selected from a vinyl group, an epoxy group, an oxetanyl group,
a vinyl ether group, and a (metha)acrylate group.
[0029] In such a silsesquioxane derivative, a curing mechanism of a
curable resinous material selected by a method described below for
transferring using the stamper for transferring a fine pattern of
the present invention preferably differs from that of the
silsesquioxane derivative. More specifically, if the curable
resinous material for transferring is a radical polymerizable
material, a photo-cationic polymerizable silsesquioxane derivative
is preferred. On the contrary, if the curable resinous material for
transferring is a photo-cationic polymerizable material, a
photo-radical polymerizable silsesquioxane derivative is
preferred.
[0030] The resinous compound, of which the fine structure layer 2
is composed, may include other cured resin than the silsesquioxane
derivative as a principal component.
[0031] As the other cured resin, a resinous monomer which is cured
by the same mechanism as that of the polymerizable functional group
included in the silsesquioxane derivative is desired.
[0032] As the other cured resin having the epoxy group, for
example, a bisphenol A epoxy resin, a hydrobisphenol A epoxy resin,
a bisphenol F epoxy resin, a novolac-type epoxy resin, an alicyclic
epoxy resin, a naphthalene-type epoxy resin, a biphenyl-type epoxy
resin, and bifunctional alcohol ether-type epoxy resin, etc. are
given.
[0033] As the other cured resin having the oxetanyl group, for
example, 3-ethyl-3-hydroxymethyloxetane,
1,4-bis[(3-ethyl-3-oxetanylmethoxy) methyl]benzene,
3-ethyl-3-(phenoxymethyl)oxetane, di
[1-ethyl(3-oxetanyl)]methylether,
3-ethyl-3-(2-ethylhexyloxymethyl)oxetane,
3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane, oxetanyl
silsesquioxane, phenol novolac oxetane, etc. are given.
[0034] As the other cured resin having the vinyl ether group, for
example, ethylene glycol divinylether, diethylene glycol
divinylether, triethylene glycol divinylether, tetraethylene glycol
divinylether, butanedioldivinylether, hexanedioldivinylether,
cyclohexanedimethanoldivinylether, isophthalic acid di (4-vinyloxy)
butyl, glutaric acid di (4-vinyloxy)butyl, succinic acid di
(4-vinyloxy)butyl trimethylol propane trivinyl ether,
2-hydroxyethylvinylether, hydroxybutylvinylether,
hydroxyhexylvinylether, etc. are given.
[0035] While organic components having any one functional group of
the epoxy group, the oxetanyl group, and the vinyl ether group were
provided above, the present invention is not limited to the organic
components. Any organic component having a polymerizable functional
group such as the epoxy group, the oxetanyl group, and the vinyl
ether group, etc. in the organic component's chain can be basically
used for the present invention.
[0036] Also, the resinous compound, of which the fine structure
layer 2 is composed, preferably further includes a photo-curing
polymerization initiator.
[0037] This photo-curing polymerization initiator is appropriately
selected depending on the silsesquioxane derivative included in the
resinous compound and the polymerizable functional group included
in the other cured resin. Especially, the cationic polymerization
initiator is desirable because the cationic polymerization
initiator prevents bad curing caused by oxygen inhibition.
[0038] The cationic polymerization initiator is not limited as long
as the cationic polymerization initiator is an electrophilic
reagent, has a cation source, and cures the organic component by
heat or light. Well known cationic polymerization initiator may be
used. Especially, a cationic polymerizable catalyst which initiates
curing by ultraviolet light is desirable because the cationic
polymerizable catalyst allows concavity and convexity pattern
formation at room temperature, and allows replica formation from a
master mold with high precision.
[0039] As the cationic polymerizable catalyst, for example, an
iron-allene complex compound, an aromatic diazonium salt, an
aromatic iodonium salt, an aromatic sulfonium salt, a pyridinium
salt, an aluminum complex/silylether, a proton acid, and Lewis
acid, etc. are given.
[0040] Also, as concrete examples of cationic polymerization
catalysts which initiate curing by ultraviolet light, IRGACURE261
(Ciba-Geigy Ltd.), OPTOMER SP-150 (Asahi Denka Corporation),
OPTOMER SP-151 (Asahi Denka Corporation), OPTOMER SP-152 (Asahi
Denka Corporation), OPTOMER SP-170 (Asahi Denka Corporation),
OPTOMER SP-171 (Asahi Denka Corporation), OPTOMER SP-172 (Asahi
Denka Corporation), UVE-1014 (General Electric Company), CD-1012
(Sartomer Co., Inc.), San-Aid SI-60L (Sanshin Chemical Industry
Co., Ltd.), San-Aid SI-80L (Sanshin Chemical Industry Co., Ltd.),
San-Aid SI-100L (Sanshin Chemical Industry Co., Ltd.), San-Aid
SI-110 (Sanshin Chemical Industry Co., Ltd.), San-Aid SI-180
(Sanshin Chemical Industry Co., Ltd.), CI-2064 (Nippon Soda Co.,
Ltd.), CI-2639 (Nippon Soda Co., Ltd.), CI-2624 (Nippon Soda Co.,
Ltd.), CI-2481 (Nippon Soda Co., Ltd.), Uvacure 1590 (Daicel-Cytec
Company, Ltd.), Uvacure 1591 (Daicel-Cytec Company, Ltd.),
RHODORSIL Photo Initiator 2074 (Rhone-Poulenc), UVI-6990 (Union
Carbide Corporation), BBI-103 (Midori Kagaku Co., Ltd.), MPI-103
(Midori Kagaku Co., Ltd.), TPS-103 (Midori Kagaku Co., Ltd.),
MDS-103 (Midori Kagaku Co., Ltd.), DTS-103 (Midori Kagaku Co.,
Ltd.), DTS-103 (Midori Kagaku Co., Ltd.), NAT-103 (Midori Kagaku
Co., Ltd.), NDS-103 (Midori Kagaku Co., Ltd.), CYRAURE UVI6990
(Union Carbide Japan Corporation), etc. are given. These
polymerization initiators, either individually or in combination,
may be used. Also, these polymerization initiators may be applied
in combination with well known polymerization accelerator and
sensitizer, etc.
[0041] It is desirable that all of the components of such a
resinous compound, except the photo-curing polymerization
initiator, are resins having the polymerizable functional
groups.
[0042] However, if a solvent component having no reactive
functional group, which solvant is unintentionally mixed in a
manufacturing process, is included in the resinous compound, the
effect of the present invention is not inhibited. Also, the
resinous compound may include a surfactant to improve an adhesion
between the supporting substrate 1 and the resinous compound within
the scope in which the object of the present invention is not
limited. Also, an additive such as a polymerization inhibitor, etc.
may be added if necessary.
[0043] In the stamper 3 for transferring fine pattern as described
above, it is desirable that the supporting substrate 1 and the fine
structure layer 2 are light-transmissive (e.g., ultraviolet
light-transmissive). By such a stamper 3 for transferring fine
pattern, a photo-curable resin can be used as a curable resinous
material 6 (see FIG. 3) of a transferred object described below.
That is, this stamper 3 for transferring fine pattern can be used
as a replica mold for photo nanoimprint technology.
[0044] Next, a method for manufacturing the stamper 3 according to
this embodiment will be explained. FIGS. 2A-2C are schematic views
showing a manufacturing process of the stamper for transferring
fine pattern.
[0045] First, in this manufacturing process, as shown in FIG. 2A, a
master mold 4 on which a fine pattern 4a is formed is prepared. On
the other hand, a resinous compound 2a whose principal component is
the silsesquioxane derivative is applied on a supporting substrate
1.
[0046] Next, as shown in FIG. 2B, the master mold 4 on which the
fine pattern 4a is formed is pressed against the resinous compound
2a. Also, by curing the resinous compound 2a with the master mold 4
being pressed, the fine pattern 4a of the master mold 4 is
transferred to the resinous compound 2a. In this connection, curing
of this resinous compound 2a may be performed by photoradiation,
heating, or combination thereof.
[0047] Also, as shown in FIG. 2C, by peeling the master mold 4 from
the cured resinous compound 2a (see FIG. 2B), the stamper 3
according to this embodiment, in which stamper 3 the fine structure
layer 2 is formed on the supporting substrate 1, can be
obtained.
[0048] Next, a method for transferring fine pattern using this
stamper 3 will be explained. FIG. 3 is a schematic view showing a
mechanism of transferring a fine pattern of the stamper to the
transferred object.
[0049] In this method for transferring, as shown in FIG. 3, a
transferred object 5, in which a curable resinous material 6 is
disposed on a transferred substrate 7, is used.
[0050] The transferred substrate 7 is not particularly limited, and
can be set depending on application of a fine structure obtained by
transferring the fine pattern. More specifically, as the
transferred substrate 7, for example, silicon wafers, various
metallic materials, glasses, quartz, ceramics, and resins, etc. are
given.
[0051] As the curable resinous material 6, for example,
photo-curable resins, heat-curable resins, and thermoplastic
resins, etc. are given. In addition, if at least one of the
photo-curable resin and the heat-curable resin is used as the
curable resinous material 6, as described above, the photo-curable
resin and the heat-curable resin whose curing mechanisms differ
from that of the silsesquioxane derivative which is the principal
component of the resinous compound are desirable.
[0052] In this method for transferring, by pressing the stamper 3
against the curable resinous material 6 of the transferred object
5, the fine pattern 4a is transferred to the curable resinous
material 6, and the fine structure can be obtained. In addition, as
described above, if a light whose wavelength is 365 nanometers or
more transmits through the supporting substrate 1 and fine
structure layer 2 of the stamper 3, the photo-curable resin can be
used as the curable resinous material 6.
[0053] As described above, in the stamper 3 according to this
embodiment, because the supporting substrate 1 is disposed on the
fine structure layer 2 which is made of the polymer (cured
material) of the resinous compound whose main component is the
silsesquioxane derivative, accurate and continuous transferring to
the transferred object 5 is allowed without releasing treatment. At
that time, by forming the fine structure layer 2 with a
silsesquioxane derivative whose curing mechanism differs from that
of the curable resinous material 6 of the transferred object 5, the
mold releasing property of the stamper 3 is still improved.
[0054] In this way, the stamper 3, which improves the continuous
transferring property without the releasing treatment, can reduce
running costs for manufacturing the fine structure.
EMBODIMENTS
[0055] Next, the present invention will be explained more
specifically with reference to the following examples. In the
following explanations, units "phr (per hundred resin)" and "%" are
based on weight unless otherwise stated.
Example 1
[0056] First, a silsesquioxane derivative OX-SQ SI-20 (Toagosei
Limited) (1 phr) having a plurality of oxetanyl groups is mixed
with an Adeka OPTOMER SP-172 (Asahi Denka Corporation) (0.06 phr)
which is a cationic polymerization initiator in order to prepare a
photo-curable resinous compound of a fine structure layer.
[0057] Next, a supporting substrate (20 millimeters*20 millimeters,
0.7 millimeters thick) whose surface is coupling-treated with a
KBM403 (Shin-Etsu Silicones Co., Ltd.) is prepared. A resinous
compound which will be a fine structure layer is dropped on the
coupling-treated surface of the supporting substrate. Next, a
ultraviolet light having wavelength of 365 nanometers is irradiated
for 120 seconds with a quartz master mold, in which hole patterns
(180 nanometers in diameter, 180 nanometers in spacing, and 200
nanometers in height) are formed on a releasing-treated surface
with a OPTOOL DSX (Daikin Industries, Ltd.), being pressed against
the photo-curable resinous compound. Next, the master mold is
peeled from the cured photo-curable resinous compound, the fine
structure layer is formed, and the stamper according to the present
invention is manufactured. Using this stamper, continuous
transferring is performed. A glass substrate is used for a
transferred substrate, and a photo-radical polymerizable resinous
compound whose principal component is an acrylate monomer is used
for a transferred object. A pattern configuration of the fine
structure layer is measured by an atomic force microscope (AFM)
(Veeco Instruments Inc.) after 50 times transferring in order to
evaluate an error compared to a pattern configuration of the fine
structure layer before transferring. A maximum dimensional-error in
height is on the order of 3%, and accurate and continuous
transferring can be performed by the stamper without releasing
treatment.
Example 2
[0058] The stamper having the fine structure layer is manufactured
by a similar method to that described in Example 1. At that time, a
silsesquioxane derivative Q-4OG (Toagosei Limited) (1 phr) having
eight epoxy groups is mixed with the Adeka OPTOMER SP-172 (Asahi
Denka Corporation) (0.06 phr) which is the cationic polymerization
initiator in order to manufacture the photo-curable resinous
compound of the fine structure layer. Using this photo-curable
resinous compound, by the similar method to that described in
Example 1, the stamper is manufactured, continuous transferring is
performed, measurement is performed by AFM, and an error is
evaluated. A maximum dimensional-error in height of the fine
structure pattern after 50 times transferring is on the order of
3%, and accurate and continuous transferring can be performed by
the stamper without releasing treatment.
Example 3
[0059] The stamper having the fine structure layer is manufactured
by a similar method to that described in Example 1. At that time, a
silsesquioxane derivative Tris
[(epoxypropoxypropyl)dimethylsilyloxy]-POSS (ALDRICH) (1 phr)
having three cationic polymerizable epoxy groups is mixed with the
Adeka OPTOMER SP-172 (Asahi Denka Corporation) (0.06 phr) which is
the photo-cationic polymerization initiator in order to manufacture
the photo-curable resinous compound. Using this photo-curable
resinous compound, by the similar method to that described in
Example 1, the resinous stamper is manufactured, continuous
transferring is performed, measurement is performed by AFM, and an
error is evaluated. A maximum dimensional-error in height of the
fine structure pattern after 50 times transferring is on the order
of 3%, and accurate and continuous transferring can be performed by
the stamper without releasing treatment.
Example 4
[0060] The stamper having the fine structure layer is manufactured
by a similar method to that described in Example 1. At that time, a
silsesquioxane derivative (90 phr) having eight photo-cationic
polymerizable epoxy groups is mixed with a polydimethylsiloxane (10
phr) having the same two photo-cationic polymerizable epoxy groups
and the Adeka OPTOMER SP-172 (Asahi Denka Corporation) (6 phr)
which is the photo-cationic polymerization initiator in order to
manufacture the photo-curable resinous compound. Using this
photo-curable resinous compound, by the similar method to that
described in Example 1, the stamper is manufactured, continuous
transferring is performed, measurement is performed by AFM, and an
error is evaluated. A maximum dimensional-error in height of the
fine structure pattern after 50 times transferring is on the order
of 3%, and accurate and continuous transferring can be performed by
the stamper without releasing treatment.
Example 5
[0061] The stamper having the fine structure layer is manufactured
by a similar method to that described in Example 1. At that time, a
silsesquioxane derivative (90 phr) having eight photo-cationic
polymerizable epoxy groups is mixed with a Epicoat 828 (Japan Epoxy
Resins Co., Ltd.) (10 phr) which has the same photo-cationic
polymerizable epoxy groups and is a bisphenol A epoxy resin, and
the Adeka OPTOMER SP-172 (Asahi Denka Corporation) (6 phr) which is
the photo-cationic polymerization initiator in order to manufacture
the photo-curable resinous compound. Using this photo-curable
resinous compound, by the similar method to that described in
Example 1, the stamper is manufactured, continuous transferring is
performed, measurement is performed by AFM, and an error is
evaluated. A maximum dimensional-error in height of the fine
structure pattern after 50 times transferring is on the order of
3%, and accurate and continuous transferring can be performed by
the stamper without releasing treatment.
Example 6
[0062] A silsesquioxane derivative OX-SQ SI-20 (Toagosei Limited)
(1 phr) having a plurality of oxetanyl groups is mixed with the
Adeka OPTOMER SP-172 (Asahi Denka Corporation) (0.06 phr) which is
the cationic polymerization initiator in order to manufacture the
photo-curable resinous compound of the fine structure layer. Also,
the supporting substrate (20 millimeters*20 millimeters, 0.7
millimeters thick) whose surface is coupling-treated with a KBM403
(Shin-Etsu Silicones Co., Ltd.) is prepared. The resinous compound
which will be the fine structure layer is dropped on the quartz
master mold in which hole patterns (180 nanometers in diameter, 180
nanometers in spacing, and 200 nanometers in height) are formed on
the releasing-treated surface with the OPTOOL DSX (Daikin
Industries, Ltd.). After spin coating, the ultraviolet light is
irradiated in order to form the fine structure layer.
[0063] Next, after pressing a coupling-treated high elastic
supporting substrate which will be a first supporting layer (a
second hard layer), the ultraviolet light is irradiated in order to
form the first supporting layer. A low elastic epoxy resin, which
will be a second supporting layer (soft layer), has a different
elastic coefficient from that of the resin used for the fine
structure layer, and is dropped. After spin coating, the
ultraviolet light is irradiated in order to form the second
supporting layer. After pressing the coupling-treated high elastic
supporting substrate which will be a third supporting layer (a
first hard layer), the ultraviolet light is irradiated in order to
form the third supporting layer. As a result, the supporting
substrate composed of the first supporting layer, the second
supporting layer and the third supporting layer is formed.
[0064] Next, the fine structure layer, the first supporting layer,
the second supporting layer, and the third supporting layer, which
are made of cured photo-curable resinous compounds, are peeled from
the master mold in order to manufacture the stamper according to
the present invention. Using the manufactured stamper, continuous
transferring is performed. A glass substrate is used for a
transferred substrate, and a photo-radical polymerizable resinous
compound whose principal component is an acrylate monomer is used
for a transferred object. A pattern configuration of the fine
structure layer is measured by an atomic force microscope (AFM)
(Veeco Instruments Inc.) after 50 times transferring in order to
evaluate an error compared to a pattern configuration of the fine
structure layer before transferring. A maximum dimensional-error in
height is on the order of 3%, and accurate and continuous
transferring can be performed by the stamper without releasing
treatment.
Example 7
[0065] A silsesquioxane derivative OX-SQ SI-20 (Toagosei Limited)
(1 phr) having a plurality of oxetanyl groups is mixed with the
Adeka OPTOMER SP-172 (Asahi Denka Corporation) (0.06 phr) which is
the cationic polymerization initiator in order to manufacture the
photo-curable resinous compound of the fine structure layer. Also,
the supporting substrate (20 millimeters*20 millimeters, 0.7
millimeters thick) whose surface is coupling-treated with a KBM403
(Shin-Etsu Silicones Co., Ltd.) is prepared. The resinous compound
which will be the fine structure layer is dropped on the quartz
master mold in which hole patterns (180 nanometers in diameter, 180
nanometers in spacing, and 200 nanometers in height) are formed on
the releasing-treated surface with the OPTOOL DSX (Daikin
Industries, Ltd.). After spin coating, the ultraviolet light is
irradiated in order to form the fine structure layer.
[0066] Next, a low elastic epoxy resin, which will be a first
supporting layer (second soft layer), has a different elastic
coefficient from that of the resin used for the fine structure
layer, and is dropped. After spin coating, the ultraviolet light is
irradiated in order to form the first supporting layer. After
pressing the coupling-treated high elastic supporting substrate
which will be a second supporting layer (a second hard layer), the
ultraviolet light is irradiated in order to form the second
supporting layer. Next, a unsaturated polyester resin which will be
a third supporting layer (a first soft layer) is dropped. After
spin coating, the ultraviolet light is irradiated in order to form
the third supporting layer. Next, after pressing the
coupling-treated high elastic supporting substrate which will be a
fourth supporting layer (a first hard layer), the ultraviolet light
is irradiated in order to form the fourth supporting layer.
[0067] Next, the fine structure layer, the first supporting layer,
the second supporting layer, the third supporting layer, and the
fourth supporting layer, which are made of cured photo-curable
resinous compounds, are peeled from the master mold in order to
manufacture the stamper according to the present invention. Using
the manufactured stamper, continuous transferring is performed. A
glass substrate is used for a transferred substrate, and a
photo-radical polymerizable resinous compound whose principal
component is an acrylate monomer is used for a transferred object.
A pattern configuration of the fine structure layer is measured by
an atomic force microscope (AFM) (Veeco Instruments Inc.) after 50
times transferring in order to evaluate an error compared to a
pattern configuration of the fine structure layer before
transferring. A maximum dimensional-error in height is on the order
of 2%, and accurate and continuous transferring can be performed by
the stamper without releasing treatment.
Example 8
[0068] A silsesquioxane derivative OX-SQ SI-20 (Toagosei Limited)
(1 phr) having a plurality of oxetanyl groups is mixed with the
Adeka OPTOMER SP-172 (Asahi Denka Corporation) (0.06 phr) which is
the cationic polymerization initiator in order to manufacture the
photo-curable resinous compound of the fine structure layer. Also,
the supporting substrate (20 millimeters*20 millimeters, 0.7
millimeters thick) whose surface is coupling-treated with a KBM403
(Shin-Etsu Silicones Co., Ltd.) is prepared. The resinous compound
which will be the fine structure layer is dropped on the quartz
master mold in which hole patterns (180 nanometers in diameter, 180
nanometers in spacing, and 200 nanometers in height) are formed on
the releasing-treated surface with the OPTOOL DSX (Daikin
Industries, Ltd.). After spin coating, the ultraviolet light is
irradiated in order to form the fine structure layer.
[0069] Next, a low elastic epoxy resin, which will be a first
supporting layer (a soft layer), has a different elastic
coefficient from that of the resin used for the fine structure
layer, is dropped. After pressing a coupling-treated high elastic
supporting substrate which will be a second supporting layer (a
hard layer), the ultraviolet light is irradiated in order to form
the supporting substrate composed of the first supporting layer,
and second supporting layer.
[0070] Next, the first supporting layer, the second supporting
layer, and the fine structure layer, which are made of cured
photo-curable resinous compounds, are peeled from the master mold
in order to manufacture the stamper according to the present
invention. Using the manufactured stamper, continuous transferring
is performed. A glass substrate is used for a transferred
substrate, and a photo-radical polymerizable resinous compound
whose principal component is an acrylate monomer is used for a
transferred object. A pattern configuration of the fine structure
layer is measured by an atomic force microscope (AFM) (Veeco
Instruments Inc.) after 50 times transferring in order to evaluate
an error compared to a pattern configuration of the fine structure
layer before transferring. A maximum dimensional-error in height is
on the order of 3%, and accurate and continuous transferring can be
performed by the stamper without releasing treatment.
Comparative Example 1
[0071] The stamper having the fine structure layer is manufactured
by a similar method to that described in Example 1. At that time, a
silsesquioxane derivative (1 phr) having eight radical
polymerizable acrylate groups is mixed with a DAROCURE 1173 (Ciba
Specialty Chemicals) (0.03 phr) which is the photo-radical
polymerization initiator in order to manufacture the photo-curable
resinous compound. Although a continuous transferring property is
evaluated by a similar method to that described in Example 1, the
fine structure can not be transferred because the stamper can not
be peeled from the transferred object.
Comparative Example 2
[0072] The stamper having the fine structure layer is manufactured
by a similar method to that described in Example 1. At that time, a
bifunctional polydimethylsiloxane is mixed with the Adeka OPTOMER
SP-172 (Asahi Denka Corporation) which is the photo-cationic
polymerization initiator as the cationic polymerization initiator
in order to manufacture a photo-curable resinous compound of a
pattern layer. Although a continuous transferring property is
evaluated by a similar method to that described in Example 1, a
transferring of the fine structure to the transferred object can
not be confirmed at 20 times continuous transferring. At the same
time, after 20 times continuous transferring, a broken pattern in
the fine structure layer of the stamper is observed. Also, with the
10 times transferred object, an accurate transferring can not be
performed because a pattern height is increased by 10-20% compared
to the transferred object which is not transferred yet.
Comparative Example 3
[0073] The stamper having the fine structure layer is manufactured
by a similar method to that described in Example 1. At that time, a
silsesquioxane derivative (7.5 phr) having eight photo-cationic
polymerizable epoxy groups is mixed with a polydimethylsiloxane (25
phr) having the same two photo-cationic polymerizable epoxy groups
and the Adeka OPTOMER SP-172 (Asahi Denka Corporation) (6 phr)
which is the photo-cationic polymerization initiator in order to
manufacture the photo-curable resinous compound. Although a
continuous transferring property is evaluated by a similar method
to that described in Example 1, a transferring of the fine
structure to the transferred object can not be confirmed at 20
times continuous transferring. At the same time, after 20 times
continuous transferring, a pattern buckling in the fine structure
layer of the stamper is observed. Also, with the 10 times
transferred object, an accurate transferring can not be performed
because a pattern height is increased by 10-20% compared to the
transferred object which is not transferred yet. Further,
widespread transferring failures are confirmed, and the fine
structure layer is broken after continuous transferring 10 times or
so.
Comparative Example 4
[0074] The stamper having the fine structure layer is manufactured
by a similar method to that described in Example 1. At that time, a
silsesquioxane derivative (7.5 phr) having eight photo-cationic
polymerizable epoxy groups is mixed with the Epicoat 828 (Japan
Epoxy Resins Co., Ltd.) (25 phr) which is a bisphenol A epoxy resin
having the same two photo-cationic polymerizable epoxy groups and
the Adeka OPTOMER SP-172 (Asahi Denka Corporation) (6 phr) which is
the photo-cationic polymerization initiator in order to manufacture
the photo-curable resinous compound. Although a continuous
transferring property is evaluated by a similar method to that
described in Example 1, a transferring of the fine structure to the
transferred object can not be confirmed at 20 times continuous
transferring. At the same time, after 20 times continuous
transferring, a pattern buckling in the fine structure layer of the
stamper is observed. Also, with the 10 times transferred object, an
accurate transferring can not be performed because a pattern height
is increased by 10-20% compared to the transferred object which is
not transferred yet. Further, transferring failures are confirmed
over a wide range, and the fine structure layer is broken after
continuous transferring 10 times or so.
* * * * *