U.S. patent application number 17/136948 was filed with the patent office on 2021-10-21 for methods for increasing the refractive index of high-index nanoimprint lithography films.
This patent application is currently assigned to Applied Materials, Inc.. The applicant listed for this patent is Applied Materials, Inc.. Invention is credited to Andrew CEBALLOS, Rami HOURANI, Amita JOSHI, Yuriy MELNIK, Kenichi OHNO.
Application Number | 20210325777 17/136948 |
Document ID | / |
Family ID | 1000005371191 |
Filed Date | 2021-10-21 |
United States Patent
Application |
20210325777 |
Kind Code |
A1 |
CEBALLOS; Andrew ; et
al. |
October 21, 2021 |
METHODS FOR INCREASING THE REFRACTIVE INDEX OF HIGH-INDEX
NANOIMPRINT LITHOGRAPHY FILMS
Abstract
Embodiments of the present disclosure generally relate to
optically densified nanoimprint films and processes for making
these optically densified nanoimprint films, as well as optical
devices containing the optically densified nanoimprint films. In
one or more embodiments, a method of forming a nanoimprint film
includes positioning a substrate containing a porous nanoimprint
film within a processing chamber, where the porous nanoimprint film
contains nanoparticles and voids between the nanoparticles, and the
porous nanoimprint film has a refractive index of less than 2. The
method also includes depositing a metal oxide on the porous
nanoimprint film and within at least a portion of the voids to
produce an optically densified nanoimprint film during an atomic
layer deposition (ALD) process.
Inventors: |
CEBALLOS; Andrew; (Santa
Clara, CA) ; HOURANI; Rami; (Santa Clara, CA)
; OHNO; Kenichi; (Sunnyvale, CA) ; MELNIK;
Yuriy; (San Jose, CA) ; JOSHI; Amita;
(Fremont, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Applied Materials, Inc. |
Santa Clara |
CA |
US |
|
|
Assignee: |
Applied Materials, Inc.
Santa Clara
CA
|
Family ID: |
1000005371191 |
Appl. No.: |
17/136948 |
Filed: |
December 29, 2020 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
63012691 |
Apr 20, 2020 |
|
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63012688 |
Apr 20, 2020 |
|
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C23C 16/45527 20130101;
G03F 7/2004 20130101; G03F 7/0005 20130101; C23C 16/45553 20130101;
C23C 16/045 20130101; G03F 7/0002 20130101 |
International
Class: |
G03F 7/00 20060101
G03F007/00; G03F 7/20 20060101 G03F007/20; C23C 16/455 20060101
C23C016/455; C23C 16/04 20060101 C23C016/04 |
Claims
1. A method of forming a nanoimprint film, comprising: positioning
a substrate comprising a porous nanoimprint film within a
processing chamber, wherein the porous nanoimprint film comprises
nanoparticles and voids between the nanoparticles, and wherein the
porous nanoimprint film has a refractive index of less than 2; and
depositing a metal oxide on the porous nanoimprint film and within
at least a portion of the voids to produce an optically densified
nanoimprint film during an atomic layer deposition (ALD)
process.
2. The method of claim 1, wherein the metal oxide has a refractive
index greater than the refractive index of the porous nanoimprint
film.
3. The method of claim 1, wherein the metal oxide has a refractive
index less than the refractive index of the porous nanoimprint
film.
4. The method of claim 1, wherein the optically densified
nanoimprint film has a refractive index greater than the refractive
index of the porous nanoimprint film.
5. The method of claim 4, wherein the refractive index of the
optically densified nanoimprint film is about 0.5% to about 30%
greater than the refractive index of the porous nanoimprint
film.
6. The method of claim 5, wherein the refractive index of the
optically densified nanoimprint film is about 1% to about 6%
greater than the refractive index of the porous nanoimprint
film.
7. The method of claim 1, wherein the refractive index of the
porous nanoimprint film is about 1.5 to about 1.95.
8. The method of claim 1, wherein the refractive index of the
optically densified nanoimprint film is about 1.8 or greater.
9. The method of claim 1, wherein the metal oxide comprises
aluminum oxide, titanium oxide, zirconium oxide, niobium oxide,
tantalum oxide, indium oxide, indium tin oxide, hafnium oxide,
chromium oxide, scandium oxide, tin oxide, zinc oxide, yttrium
oxide, praseodymium oxide, magnesium oxide, silicon oxide, silicon
nitride, silicon oxynitride, or any combination thereof.
10. The method of claim 1, wherein the nanoparticles comprise
titanium oxide, zirconium oxide, niobium oxide, tantalum oxide,
hafnium oxide, chromium oxide, indium tin oxide, silicon nitride,
or any combination thereof.
11. The method of claim 1, wherein the ALD process comprises
sequentially exposing the porous nanoimprint film to a metal
precursor and an oxidizing agent during an ALD cycle to deposit the
metal oxide.
12. The method of claim 11, wherein the ALD cycle is repeated from
1 time to about 50 times while depositing the metal oxide during
the ALD process.
13. The method of claim 1, wherein about 20% to about 90% of the
volume occupied by the voids is filled with the metal oxide by the
ALD process.
14. A method of claim 1, wherein the porous nanoimprint film is
formed on the substrate by an imprint process, comprising:
disposing an imprint composition comprising the nanoparticles on
the substrate; contacting the imprint composition with a stamp
having a pattern; converting the imprint composition to a porous
nanoimprint film; and removing the stamp from the porous
nanoimprint film.
15. The method of claim 14, wherein the imprint composition is
converted to the porous nanoimprint film by exposing the imprint
composition to heat, ultraviolet light, infrared light, visible
light, microwave radiation, or any combination thereof.
16. The method of claim 14, wherein converting the imprint
composition to the porous nanoimprint film further comprises
exposing the imprint composition to a light source having a
wavelength of about 300 nm to about 365 nm.
17. The method of claim 14, wherein converting the imprint
composition to the porous nanoimprint film further comprises
heating the imprint composition to a temperature of about
30.degree. C. to about 100.degree. C. for a time period of about 30
seconds to about 1 hour.
18. A method of forming a nanoimprint film, comprising: disposing
an imprint composition comprising nanoparticles on a substrate;
contacting the imprint composition with a stamp having a pattern;
converting the imprint composition to a porous nanoimprint film;
removing the stamp from the porous nanoimprint film; positioning
the substrate comprising the porous nanoimprint film within a
processing chamber, wherein the porous nanoimprint film comprises
nanoparticles and voids between the nanoparticles, and wherein the
porous nanoimprint film has a refractive index of less than 2; and
depositing a metal oxide on the porous nanoimprint film and within
at least a portion of the voids to produce an optically densified
nanoimprint film during an atomic layer deposition (ALD) process,
wherein the optically densified nanoimprint film has a refractive
index greater than the refractive index of the porous nanoimprint
film.
19. An optically densified nanoimprint film, comprising: a base
nanoimprint film comprising nanoparticles and voids between the
nanoparticles, and wherein the base nanoimprint film has a
refractive index of less than 2; and a metal oxide disposed on the
base nanoimprint film and contained within at least a portion of
the voids; wherein the optically densified nanoimprint film has a
refractive index greater than the refractive index of the base
nanoimprint film; wherein about 20% to about 90% of the volume
occupied by the voids in the base nanoimprint film contains the
metal oxide; and wherein the refractive index of the optically
densified nanoimprint film is about 1 to about 6% greater than the
refractive index of the base nanoimprint film.
20. The optically densified nanoimprint film of claim 19, wherein:
the metal oxide comprises aluminum oxide, titanium oxide, zirconium
oxide, niobium oxide, tantalum oxide, indium oxide, indium tin
oxide, hafnium oxide, chromium oxide, scandium oxide, tin oxide,
zinc oxide, yttrium oxide, praseodymium oxide, magnesium oxide,
silicon oxide, silicon nitride, silicon oxynitride, or any
combination thereof; the nanoparticles comprise titanium oxide,
zirconium oxide, niobium oxide, tantalum oxide, hafnium oxide,
chromium oxide, indium tin oxide, silicon nitride, or any
combination thereof; the refractive index of the base nanoimprint
film is about 1.5 to about 1.95; and the refractive index of the
optically densified nanoimprint film is about 1.8 to about 2.05.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims benefit to U.S. Prov. Appl. No.
63/012,688, filed on Apr. 20, 2020, and U.S. Prov. Appl. No.
63/012,691, filed on Apr. 20, 2020, which are herein incorporated
by reference.
BACKGROUND
Field
[0002] Embodiments of the present disclosure generally relate to
micro-device processing, and more specifically to nanoimprint
lithography (NIL) films and processes to make the same.
Description of the Related Art
[0003] Nano and micro-patterning of nanoparticle imprint provides
opportunities for developing nanomaterial-based optics,
electronics, displays, energy devices, sensors, and other types of
devices with nanometer scale resolution. The imprint materials
currently available contain either organic (high index polymers) or
inorganic-organic hybrid materials (sol-gel). The majority of the
imprint materials have low refractive index (<1.7), along with
multiple problems associated with optical transparency in visible
region, optical resolution, processability, high shrinkage of
imprinted features and cost effectiveness. In addition, many of the
imprint materials have relatively low hardness, fracture strain,
yield strength, and/or etch resistance, which if increased, would
be beneficial. Some imprint materials have relatively high modulus
of elasticity, which if decreased, would also be beneficial.
[0004] Therefore, improved nanoimprint films with a beneficial
physical properties and related processes for making these
nanoimprint films are needed.
SUMMARY
[0005] Embodiments of the present disclosure generally relate to
densified nanoimprint films and related processes for making these
densified nanoimprint films. The densified nanoimprint films are
typically also optically densified nanoimprint films relative to
the base or porous nanoimprint film from which they are formed. The
densified nanoimprint films can be useful as nanoimprint
lithography (NIL) films. The densified nanoimprint films and/or
optically densified nanoimprint films typically have a relatively
high refractive index (>1.9 or >2), as well as relatively
high hardness, fracture strain, yield strength, and/or etch
resistance (e.g., reduced etch rate), and also relatively low
modulus of elasticity.
[0006] In one or more embodiments, a method of forming a
nanoimprint film includes positioning a substrate containing a
porous nanoimprint film within a processing chamber, where the
porous nanoimprint film contains nanoparticles and voids between
the nanoparticles, and the porous nanoimprint film has a refractive
index of less than 2. The method also includes depositing a metal
oxide on the porous nanoimprint film and within at least a portion
of the voids to produce an optically densified nanoimprint film
during an atomic layer deposition (ALD) process.
[0007] In some embodiments, a method of forming a nanoimprint film
includes disposing an imprint composition containing nanoparticles
on a substrate, contacting the imprint composition with a stamp
having a pattern, converting the imprint composition to a porous
nanoimprint film, and removing the stamp from the porous
nanoimprint film. The method also includes positioning the
substrate containing the porous nanoimprint film within a
processing chamber, where the porous nanoimprint film contains
nanoparticles and voids between the nanoparticles, and the porous
nanoimprint film has a refractive index of less than 2. The method
further includes depositing a metal oxide on the porous nanoimprint
film and within at least a portion of the voids to produce an
optically densified nanoimprint film during an ALD process, where
the optically densified nanoimprint film has a refractive index
greater than the refractive index of the porous nanoimprint
film.
[0008] In other embodiments, an optically densified nanoimprint
film contains a base nanoimprint film having nanoparticles and
voids between the nanoparticles, and where the base nanoimprint
film has a refractive index of less than 2. The optically densified
nanoimprint film also contains a metal oxide disposed on the base
nanoimprint film and contained within at least a portion of the
voids. The metal oxide increases the refractive index of the base
nanoimprint film.
[0009] In one or more embodiments, an optical device with gratings
containing an optically densified nanoimprint film is provided and
discussed herein. Any of the optically densified nanoimprint films
and/or methods for producing optically densified nanoimprint films
described and discussed herein can be used to produce the optical
device. For example, the optically densified nanoimprint film
contains a base nanoimprint film and a metal oxide disposed on the
base nanoimprint film and in between the nanoparticles, where the
base nanoimprint film has a refractive index of less than 2, as
described and discussed herein.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] So that the manner in which the above recited features of
the present disclosure can be understood in detail, a more
particular description of the disclosure, briefly summarized above,
may be had by reference to embodiments, some of which are
illustrated in the appended drawings. It is to be noted, however,
that the appended drawings illustrate only exemplary embodiments
and are therefore not to be considered limiting of its scope, may
admit to other equally effective embodiments.
[0011] FIGS. 1A-1F depict cross-sectional views of a workpiece
being processed through multiple operations while preparing a
nanoimprint film containing nanoparticles, according to one or more
embodiments described and discussed herein.
[0012] FIGS. 2A-2B depict cross-sectional views of a workpiece
being processed to prepare an optically densified nanoimprint film,
according to one or more embodiments described and discussed
herein.
[0013] FIG. 3 depicts a front view of an optical device, according
to one or more embodiments described and discussed herein.
[0014] To facilitate understanding, identical reference numerals
have been used, where possible, to designate identical elements
that are common to the Figures. It is contemplated that elements
and features of one or more embodiments may be beneficially
incorporated in other embodiments.
DETAILED DESCRIPTION
[0015] In one or more embodiments, a method of forming a
nanoimprint film includes positioning a substrate containing a base
or porous nanoimprint film within a processing chamber, where the
porous nanoimprint film contains nanoparticles and voids between
the nanoparticles, and the porous nanoimprint film has a refractive
index of less than 2. The voids, such as the spaces disposed
between the nanoparticles, can contain ambient air, residual
organic materials (e.g., one or more hydrocarbons and/or other
organic compounds), particulates, and/or one or more other
contaminants which can have a relatively low refractive index, such
as from about 1, about 1.2, or about 1.3 to about 1.4 or about
1.5.
[0016] The method also includes depositing one or more metal oxides
on the porous nanoimprint film and within at least a portion of the
voids to produce an optically densified nanoimprint film during an
atomic layer deposition (ALD) process. The voids can be at least
partially filled, substantially filled, or completely filled. For
example, at least 3%, at least 5%, or at least 10% of the volume
occupied by the voids is filled with the metal oxide by the ALD
process. In other examples, from about 20% to about 90% of the
volume occupied by the voids is filled with the metal oxide by the
ALD process. In some examples, greater than 90%, such as about 95%
to 100%, of the volume occupied by the voids is filled with the
metal oxide by the ALD process. The optically densified nanoimprint
film has a refractive index greater than the refractive index of
the base or porous nanoimprint film.
[0017] In one or more embodiments, the refractive index of the
optically densified nanoimprint film is greater than the refractive
index of the porous nanoimprint film by about 0.5%, about 0.75%,
about 1%, about 2%, about 4%, or about 5% to about 6%, about 8%,
about 10%, about 12%, about 15%, about 20%, about 25%, about 30%,
or more. For example, the refractive index of the optically
densified nanoimprint film is about 0.5% to about 30% greater than
the refractive index of the porous nanoimprint film. In other
examples, the refractive index of the optically densified
nanoimprint film is about 0.65% to about 20% greater than the
refractive index of the porous nanoimprint film. In other examples,
the refractive index of the optically densified nanoimprint film is
about 0.75% to about 10% greater than the refractive index of the
porous nanoimprint film. In some examples, the refractive index of
the optically densified nanoimprint film is about 1% to about 6%
greater than the refractive index of the porous nanoimprint
film.
[0018] The refractive index of the porous nanoimprint film is about
1.50, about 1.65, or about 1.75 to about 1.80, about 1.85, about
1.90, about 1.95, about 197, about 1.99, or less than 2. In one or
more examples, the refractive index of the porous nanoimprint film
is about 1.5 to about 1.95 or about 1.75 to about 1.95. The
refractive index of the optically densified nanoimprint film is
greater than the refractive index of the porous nanoimprint film.
In some examples, the refractive index of the optically densified
nanoimprint film is about 1.8 or greater. For example, the
refractive index of the optically densified nanoimprint film is
about 1.8 to about 2.2, about 1.85 to about 2.15, or about 1.9 to
about 2.1.
[0019] Any densified nanoimprint film and/or optically densified
nanoimprint film can have an increased mass per unit volume and/or
can have an increased refractive index over the porous nanoimprint
film and/or the base nanoimprint film, as described and discussed
herein. In one or more embodiments, the densified nanoimprint film
has a greater value of hardness, a greater value of fracture
strain, a greater value of yield strength, and/or a greater value
of etch resistance than the porous nanoimprint film or the base
nanoimprint film. In some embodiments, the densified nanoimprint
film has a lesser value of modulus of elasticity than the porous
nanoimprint film or the base nanoimprint film.
[0020] In one or more embodiments, the nanoparticles can be or
include titanium oxide, zirconium oxide, niobium oxide, tantalum
oxide, hafnium oxide, chromium oxide, indium tin oxide, silicon
nitride, or any combination thereof. Any nanoparticle described and
discussed here can be used be prepare the porous nanoimprint film.
The metal oxide can be or include one or more aluminum oxide,
titanium oxide, zirconium oxide, niobium oxide, tantalum oxide,
indium oxide, indium tin oxide, hafnium oxide, chromium oxide,
scandium oxide, tin oxide, zinc oxide, yttrium oxide, praseodymium
oxide, magnesium oxide, or any combination thereof. Instead of a
metal oxide or along with a metal oxide, one or more silicon oxides
and or silicon nitrides can be deposited on and/or in the porous
nanoimprint film. Exemplary silicon oxides can be or include
silicon monoxide, silicon dioxide, one or more silicon oxide of
SiO.sub.x (where 2>x>1), one or more silicates, silicon
nitride, silicon oxynitride, or any combination thereof. The metal
oxide can have a refractive index greater than, equal to, or less
than the refractive index of the nanoparticles and/or the porous
nanoimprint film. Even if the refractive index of the metal oxide
is equal to or less than the refractive index of the nanoparticles
and/or the porous nanoimprint film, the metal oxide has a greater
refractive index than the one or more materials which is being
replaced in the voids, such as air, organic compounds,
particulates, and/or one or more other contaminants.
Methods for Preparing an Imprinted Surface of the Base or Porous
Nanoimprint Film
[0021] In one or more embodiments, methods for preparing an
imprinted surface, such as a nanoimprint lithography (NIL) film,
are provided. The imprinted surface is one or more exposed surfaces
of the base or porous nanoimprint film described and discussed
herein. The method includes disposing, coating, or otherwise
placing an imprint composition on one or more substrates,
contacting the imprint composition with a stamp having a pattern,
converting the imprint composition to an imprint material (e.g., a
porous nanoimprint film), and removing the stamp from the imprint
material. In some examples, the substrate (e.g., wafer) can be or
include glass, quartz, silicon oxide, such as a glass substrate or
a glass wafer. In other examples, the substrate can be or include
silicon, silicon-germanium, plastic, and/or other materials. The
imprint composition and/or material can have a refractive index of
about 1.7 to about 2.0, or about 1.7 to less than 2, such as about
1.9, 1.85, or 1.80. The pattern on the stamp and transferred to the
imprinted surface can be a 1-dimension pattern, a 2-dimension
pattern, or a 3-dimension pattern.
[0022] FIGS. 1A-1F depict cross-sectional views of a workpiece
being processed through multiple operations while preparing a
nanoimprint film containing nanoparticles, such as the base or
porous nanoimprint film, according to one or more embodiments
described and discussed herein. The porous nanoimprint film is
formed on the substrate by an imprint process. The imprint process
includes disposing an imprint composition 104 containing
nanoparticles on a substrate 102 and aligning a stamp 120 above or
adjacent to the imprint composition 104 (FIG. 1A). The imprint
composition 104 is impressed or otherwise contacted with the stamp
120 having a pattern (FIGS. 1B-1C). The imprint composition 104 is
converted to a porous nanoimprint film 106 (FIG. 1D). In some
examples, a curing process with heat and/or radiation (UV light) is
used to convert the imprint composition 104 to the porous
nanoimprint film 106. The stamp 120 is removed from the porous
nanoimprint film 106, which is left disposed on the substrate 102
(FIGS. 1E-1F). The pores of the porous nanoimprint film 106 may
have some residual organic material, such as a minimal organic
matrix that exists because of imperfect packing of
nanoparticles.
[0023] In some examples, the imprint composition is disposed on the
substrate by spin coating, drop casting, blade coating, and/or
other coating processes. The imprint composition is disposed on the
substrate as a film or a layer having a predetermined thickness.
The thickness of the imprint composition is about 50 nm, about 80
nm, about 100 nm, about 120 nm, about 150 nm, or about 200 nm to
about 250 nm, about 300 nm, about 400 nm, about 500 nm, about 600
nm, about 800 nm, about 1,000 nm, about 1,200 nm, or thicker. For
example, the thickness of the imprint composition is about 50 nm to
about 1,000 nm, about 100 nm to about 1,000 nm, about 200 nm to
about 1,000 nm, about 400 nm to about 1,000 nm, about 500 nm to
about 1,000 nm, about 600 nm to about 1,000 nm, about 800 nm to
about 1,000 nm, about 50 nm to about 600 nm, about 100 nm to about
600 nm, about 200 nm to about 600 nm, about 400 nm to about 600 nm,
about 500 nm to about 600 nm, about 50 nm to about 400 nm, about
100 nm to about 400 nm, about 200 nm to about 400 nm, or about 300
nm to about 400 nm.
[0024] The imprint composition is converted to the imprint material
(e.g., the porous nanoimprint film) by exposing the imprint
composition to heat, ultraviolet light, infrared light, visible
light, microwave radiation, and/or any combination thereof. In one
or more examples, when converting the imprint composition to the
imprint material, the imprint composition is exposed to a light
source having a wavelength of about 300 nm to about 365 nm. In
other examples, when converting the imprint composition to the
imprint material, the imprint composition is exposed to heat and
maintained at a temperature of about 30.degree. C. to about
100.degree. C. for a time period of about 30 seconds to about 1
hour. In some examples, the imprint composition is exposed to heat
and maintained at a temperature of about 50.degree. C. to about
60.degree. C. for a time period of about 1 minute to about 15
minutes.
ALD of Metal Oxide to Prepare Optically Densified Nanoimprint
Film
[0025] In one or more embodiments, one or more metal oxides are
deposited or otherwise formed by ALD or another vapor deposition
process on and within the base or porous nanoimprint film. Voids,
or portions of voids, within the porous nanoimprint film are at
least partially filled with the metal oxide to produce the
optically densified nanoimprint film. As discussed above, the voids
can be at least partially filled, substantially filled, or
completely filled by the metal oxide during the ALD process.
[0026] FIGS. 2A-2B depict cross-sectional views of a workpiece
being processed to convert a porous nanoimprint film to be an
optically densified nanoimprint film, according to one or more
embodiments described and discussed herein. The porous nanoimprint
film 106 containing features 130 is left disposed on the substrate
102, as depicted in FIG. 2A. The porous nanoimprint film 106
contains a plurality of nanoparticles 108 separated by a plurality
of spaces or voids 110. An ALD process or another vapor deposition
process is used to deposit metal oxide 112 between the
nanoparticles 108 and into the voids 110 to produce the optically
densified nanoimprint film 116, as depicted in FIG. 2B. The
features 130 formed in the porous nanoimprint film 106 are at least
substantially, if not completely, preserved in the optically
densified nanoimprint film 116.
[0027] The ALD process includes sequentially exposing the porous
nanoimprint film to a metal precursor and an oxidizing agent (and
or other reagent) during an ALD cycle to deposit the metal oxide.
The ALD cycle also includes exposures of purge gas between each
exposure of the precursors. For example, the ALD process includes
sequentially exposing the porous nanoimprint film to a metal
precursor, a purge gas, an oxidizing agent (and or other reagent),
and the purge gas during the ALD cycle. The purge gas can be or
include nitrogen (N.sub.2), argon, helium, or any combination
thereof.
[0028] In some instances, the ALD cycle can be performed a single
time to deposit the metal oxide while producing the optically
densified nanoimprint film. In other examples, the ALD cycle can be
performed two or more times to deposit the metal oxide while
producing the optically densified nanoimprint film. For example,
the ALD cycle can be repeated from 2, 3, 4, 5, 6, 7, 8, 9, 10, 12,
or 15 times to about 18, about 20, about 25, about 30, about 40,
about 50, about 60, about 80, about 100, or more times to deposit
the metal oxide while producing the optically densified nanoimprint
film.
[0029] In one or more examples, if the metal oxide is or contains
aluminum oxide, then the metal precursor is one or more aluminum
precursors, such as an alkyl aluminum compound, for example,
trimethylaluminum, triethylaluminum, tripropylaluminum,
tributylaluminum, or the like. The oxidizing agent can be or
include water, oxygen (O.sub.2), ozone, atomic oxygen, nitrous
oxide, hydrogen peroxide, one or more organic peroxides, plasma
thereof, or any combination thereof.
[0030] In one or more embodiments, an optically densified
nanoimprint film contains a base nanoimprint film containing
nanoparticles and optionally voids between the nanoparticles, and
where the base nanoimprint film has a refractive index of less than
2. The optically densified nanoimprint film also contains a metal
oxide disposed on the base nanoimprint film and contained within at
least a portion of the voids. The optically densified nanoimprint
film has a refractive index greater than the refractive index of
the base nanoimprint film.
Imprint Compositions for Preparing NIL Films
[0031] Embodiments of the present disclosure generally relate to
imprint compositions and imprint materials (e.g., base or porous
nanoimprint films) useful for nanoimprint lithography (NIL). The
imprint composition can be converted to the imprint material by
applying heat and/or one or types of radiation, such as light or
microwave. In one or more embodiments, the imprint composition
contains one or more types of nanoparticles, one or more surface
ligands, one or more solvents, one or more additives, and one or
more acrylates.
[0032] Each of the nanoparticles can be a single particle (bare
particle) or can be a coated particle, such as containing a core
and one or more shells disposed around the core. In some examples,
the nanoparticles can contain one or more types of surface ligands
coupled to the outer surface of the particle (e.g., ligated NPs or
stabilized NPs). The nanoparticles can have one or more different
shapes or geometries, such as spherical, oval, rod, cubical, wire,
cylindrical, rectangular, or combinations thereof.
[0033] The nanoparticle or the core can have a size or a diameter
of about 2 nm, about 5 nm, about 8 nm, about 10 nm, about 12 nm,
about 15 nm, about 20 nm, about 25 nm, about 30 nm, or about 35 nm
to about 40 nm, about 50 nm, about 60 nm, about 80 nm, about 100
nm, about 150 nm, about 200 nm, about 250 nm, about 300 nm, about
400 nm, about 500 nm, or larger. For example, the nanoparticle or
the core can have a size or a diameter of about 2 nm to about 500
nm, about 2 nm to about 300 nm, about 2 nm to about 200 nm, about 2
nm to about 150 nm, about 2 nm to about 100 nm, about 2 nm to about
80 nm, about 2 nm to about 60 nm, about 2 nm to about 50 nm, about
2 nm to about 40 nm, about 2 nm to about 30 nm, about 2 nm to about
20 nm, about 2 nm to about 15 nm, about 2 nm to about 10 nm, about
10 nm to about 500 nm, about 10 nm to about 300 nm, about 10 nm to
about 200 nm, about 10 nm to about 150 nm, about 10 nm to about 100
nm, about 10 nm to about 80 nm, about 10 nm to about 60 nm, about
10 nm to about 50 nm, about 10 nm to about 40 nm, about 10 nm to
about 30 nm, about 10 nm to about 20 nm, about 10 nm to about 15
nm, about 50 nm to about 500 nm, about 50 nm to about 300 nm, about
50 nm to about 200 nm, about 50 nm to about 150 nm, about 50 nm to
about 100 nm, about 50 nm to about 80 nm, or about 50 nm to about
60 nm.
[0034] The nanoparticle can be or contain one or more metal oxides,
one or more non-metal oxides, one or more non-metal nitrides,
and/or diamond materials. The nanoparticle can contain titanium
oxide, zirconium oxide, niobium oxide, tantalum oxide, hafnium
oxide, chromium oxide, indium tin oxide, silicon nitride, diamond,
or any combination thereof. In some embodiments, if the
nanoparticle one or more shells disposed around the core, the core
and shell can be the same material or different materials. In one
or more examples, the core contains titanium oxide and the shell
contains silicon oxide, zirconium oxide, niobium oxide, or any
combination thereof. In other examples, the core contains niobium
oxide and the shell contains silicon oxide, zirconium oxide, or any
combination thereof. In some examples, the core contains zirconium
oxide and the shell contains silicon oxide.
[0035] In some examples, the core has a diameter of about 2 nm to
about 500 nm and the shell has a thickness of about 0.1 nm to about
100 nm. In other examples, the core has a diameter of about 5 nm to
about 200 nm and the shell has a thickness of about 0.5 nm to about
60 nm. In some examples, the core has a diameter of about 10 nm to
about 100 nm and the shell has a thickness of about 1 nm to about
15 nm.
[0036] In one or more embodiments, the imprint composition contains
about 0.1 wt %, about 0.5 wt %, about 1 wt %, about 2 wt %, about 3
wt %, about 5 wt %, about 6 wt %, about 8 wt %, or about 10 wt % to
about 12 wt %, about 15 wt %, about 18 wt %, about 20 wt %, about
22 wt %, about 24 wt %, about 25 wt %, about 28 wt %, about 30 wt
%, about 32 wt %, about 35 wt %, about 38 wt %, or about 40 wt % of
the nanoparticles. For example, the imprint composition contains
about 0.1 wt % to about 40 wt %, about 0.5 wt % to about 40 wt %,
about 0.5 wt % to about 35 wt %, about 0.5 wt % to about 32 wt %,
about 0.5 wt % to about 30 wt %, about 0.5 wt % to about 28 wt %,
about 0.5 wt % to about 25 wt %, about 0.5 wt % to about 22 wt %,
about 0.5 wt % to about 20 wt %, about 0.5 wt % to about 18 wt %,
about 0.5 wt % to about 15 wt %, about 0.5 wt % to about 12 wt %,
about 0.5 wt % to about 10 wt %, about 0.5 wt % to about 8 wt %,
about 0.5 wt % to about 6 wt %, about 0.5 wt % to about 5 wt %,
about 0.5 wt % to about 4 wt %, about 0.5 wt % to about 3 wt %,
about 0.5 wt % to about 2 wt %, about 0.5 wt % to about 1.5 wt %,
about 0.5 wt % to about 1 wt %, about 2 wt % to about 40 wt %,
about 2 wt % to about 35 wt %, about 2 wt % to about 32 wt %, about
2 wt % to about 30 wt %, about 2 wt % to about 28 wt %, about 2 wt
% to about 25 wt %, about 2 wt % to about 22 wt %, about 2 wt % to
about 20 wt %, about 2 wt % to about 18 wt %, about 2 wt % to about
15 wt %, about 2 wt % to about 12 wt %, about 2 wt % to about 10 wt
%, about 2 wt % to about 8 wt %, about 2 wt % to about 6 wt %,
about 2 wt % to about 5 wt %, about 2 wt % to about 4 wt %, about 2
wt % to about 3 wt %, about 5 wt % to about 40 wt %, about 5 wt %
to about 35 wt %, about 5 wt % to about 32 wt %, about 5 wt % to
about 30 wt %, about 5 wt % to about 28 wt %, about 5 wt % to about
25 wt %, about 5 wt % to about 22 wt %, about 5 wt % to about 20 wt
%, about 5 wt % to about 18 wt %, about 5 wt % to about 15 wt %,
about 5 wt % to about 12 wt %, about 5 wt % to about 10 wt %, about
5 wt % to about 8 wt %, or about 5 wt % to about 6 wt % of the
nanoparticles.
[0037] In other embodiments, the imprint composition contains about
40 wt %, about 50 wt %, about 55 wt %, about 60 wt %, about 62 wt
%, or about 65 wt % to about 68 wt %, about 70 wt %, about 75 wt %,
about 80 wt %, about 85 wt %, about 88 wt %, about 90 wt %, about
92 wt %, about 93 wt %, about 94 wt %, about 95 wt %, about 96 wt
%, about 97 wt %, about 98 wt %, or more of the nanoparticles. For
example, the imprint composition contains about 40 wt % to about 98
wt %, about 50 wt % to about 95 wt %, about 50 wt % to about 90 wt
%, about 50 wt % to about 80 wt %, about 50 wt % to about 75 wt %,
about 50 wt % to about 70 wt %, about 50 wt % to about 65 wt %,
about 50 wt % to about 60 wt %, about 50 wt % to about 55 wt %,
about 60 wt % to about 95 wt %, about 60 wt % to about 90 wt %,
about 60 wt % to about 80 wt %, about 60 wt % to about 75 wt %,
about 60 wt % to about 70 wt %, about 60 wt % to about 65 wt %,
about 70 wt % to about 95 wt %, about 70 wt % to about 90 wt %,
about 70 wt % to about 80 wt %, or about 70 wt % to about 75 wt %
of the nanoparticles.
[0038] The surface ligand can be or include one or more carboxylic
acids, one or more esters, one or more amines, one or more
alcohols, one or more silanes, salts thereof, complexes thereof, or
any combination thereof. Exemplary surface ligands can be or
include oleic acid, stearic acid, propionic acid, benzoic acid,
palmitic acid, myristic acid, methylamine, oleylamine, butylamine,
benzyl alcohol, oleyl alcohol, butanol, octanol, dodecanol,
octeyltriethoxy silane, octeyltrimethoxy silane,
3-(trimethoxysilyl)propyl methacrylate, propyltriethoxy silane,
salts thereof, esters thereof, complexes thereof, or any
combination thereof. In some example, the surface ligand is at a
concentration of about 8 wt % to about 50 wt %, based on the weight
of the nanoparticles.
[0039] The imprint composition contains about 0.5 wt %, about 1 wt
%, about 2 wt %, about 3 wt %, about 5 wt %, about 7 wt %, about 8
wt %, or about 10 wt % to about 12 wt %, about 15 wt %, about 18 wt
%, about 20 wt %, about 25 wt %, about 30 wt %, about 35 wt %,
about 40 wt %, about 45 wt %, or about 50 wt % of the surface
ligand. For example, the imprint composition contains about 0.5 wt
% to about 50 wt %, about 1 wt % to about 50 wt %, about 3 wt % to
about 50 wt %, about 5 wt % to about 50 wt %, about 5 wt % to about
40 wt %, about 5 wt % to about 35 wt %, about 5 wt % to about 30 wt
%, about 5 wt % to about 25 wt %, about 5 wt % to about 20 wt %,
about 5 wt % to about 15 wt %, about 5 wt % to about 10 wt %, about
10 wt % to about 50 wt %, about 10 wt % to about 40 wt %, about 10
wt % to about 35 wt %, about 10 wt % to about 30 wt %, about 10 wt
% to about 25 wt %, about 10 wt % to about 20 wt %, about 10 wt %
to about 15 wt %, about 15 wt % to about 50 wt %, about 15 wt % to
about 40 wt %, about 15 wt % to about 35 wt %, about 15 wt % to
about 30 wt %, about 15 wt % to about 25 wt %, or about 15 wt % to
about 20 wt % of the surface ligand.
[0040] The solvent can be or include one or more nanoparticle
dispersion solvents, one or more imprinting solvents, other types
of solvents, or any combination thereof. The nanoparticle
dispersion solvent can be or include one or more glycol ethers,
alcohols, acetates, esters thereof, salts thereof, derivatives
thereof, or any combination thereof. In some examples, the
nanoparticle dispersion solvent can be or include one or more
p-series glycol ethers, one or more e-series glycol ethers, or any
combination thereof. In one or more examples, the nanoparticle
dispersion solvent contains propylene glycol methyl ether acetate
(PGMEA). The imprinting solvent can be or include one or more
alcohols, one or more esters, salts thereof, or any combination
thereof. In one or more examples, the imprinting solvent contains
ethyl lactate.
[0041] In one or more embodiments, the imprint composition contains
about 50 wt %, about 55 wt %, about 60 wt %, about 62 wt %, about
65 wt %, about 68 wt %, about 70 wt %, about 72 wt %, about 75 wt
%, or about 80 wt % to about 83 wt %, about 85 wt %, about 87 wt %,
about 88 wt %, about 90 wt %, about 92 wt %, about 94 wt %, about
95 wt %, about 97 wt %, or about 98 wt % of one or more solvents.
For example, the imprint composition contains about 50 wt % to
about 98 wt %, about 60 wt % to about 98 wt %, about 60 wt % to
about 95 wt %, about 60 wt % to about 90 wt %, about 60 wt % to
about 88 wt %, about 60 wt % to about 85 wt %, about 60 wt % to
about 83 wt %, about 60 wt % to about 80 wt %, about 60 wt % to
about 78 wt %, about 60 wt % to about 75 wt %, about 60 wt % to
about 72 wt %, about 60 wt % to about 70 wt %, about 60 wt % to
about 68 wt %, about 60 wt % to about 65 wt %, about 60 wt % to
about 63 wt %, about 70 wt % to about 98 wt %, about 70 wt % to
about 95 wt %, about 70 wt % to about 90 wt %, about 70 wt % to
about 88 wt %, about 70 wt % to about 85 wt %, about 70 wt % to
about 83 wt %, about 70 wt % to about 80 wt %, about 70 wt % to
about 78 wt %, about 70 wt % to about 75 wt %, about 70 wt % to
about 72 wt %, about 80 wt % to about 98 wt %, about 80 wt % to
about 95 wt %, about 80 wt % to about 90 wt %, about 80 wt % to
about 88 wt %, about 80 wt % to about 85 wt %, about 80 wt % to
about 83 wt %, or about 80 wt % to about 82 wt % of one or more
solvents.
[0042] In some embodiments, the imprint composition contains about
0.5 wt %, about 0.8 wt %, about 1 wt %, about 1.5 wt %, about 2 wt
%, about 2.5 wt %, about 3 wt %, about 3.5 wt %, about 4 wt %,
about 5 wt %, or about 6 wt % to about 7 wt %, about 8 wt %, about
10 wt %, about 12 wt %, about 14 wt %, about 15 wt %, about 18 wt
%, about 20 wt %, or about 25 wt % of the nanoparticle dispersion
solvent. For example, the imprint composition contains about 0.5 wt
% to about 20 wt %, about 1 wt % to about 20 wt %, about 1 wt % to
about 18 wt %, about 1 wt % to about 15 wt %, about 1 wt % to about
13 wt %, about 1 wt % to about 12 wt %, about 1 wt % to about 11 wt
%, about 1 wt % to about 10 wt %, about 1 wt % to about 8 wt %,
about 1 wt % to about 7 wt %, about 1 wt % to about 6 wt %, about 1
wt % to about 5 wt %, about 1 wt % to about 4 wt %, about 1 wt % to
about 3 wt %, about 5 wt % to about 20 wt %, about 5 wt % to about
18 wt %, about 5 wt % to about 15 wt %, about 5 wt % to about 13 wt
%, about 5 wt % to about 12 wt %, about 5 wt % to about 11 wt %,
about 5 wt % to about 10 wt %, about 5 wt % to about 8 wt %, about
5 wt % to about 7 wt %, about 5 wt % to about 6 wt %, about 8 wt %
to about 20 wt %, about 8 wt % to about 18 wt %, about 8 wt % to
about 15 wt %, about 8 wt % to about 13 wt %, about 8 wt % to about
12 wt %, about 8 wt % to about 11 wt %, about 8 wt % to about 10 wt
%, or about 8 wt % to about 9 wt % of the nanoparticle dispersion
solvent.
[0043] In other embodiments, the imprint composition contains about
50 wt %, about 55 wt %, about 60 wt %, about 62 wt %, about 65 wt
%, about 68 wt %, or about 70 wt % to about 72 wt %, about 75 wt %,
about 78 wt %, about 80 wt %, about 82 wt %, about 83 wt %, about
85 wt %, about 87 wt %, about 88 wt %, about 90 wt %, or about 95
wt % of the imprinting solvent. For example, the imprint
composition contains about 50 wt % to about 95 wt %, about 60 wt %
to about 95 wt %, about 60 wt % to about 90 wt %, about 60 wt % to
about 88 wt %, about 60 wt % to about 85 wt %, about 60 wt % to
about 83 wt %, about 60 wt % to about 80 wt %, about 60 wt % to
about 78 wt %, about 60 wt % to about 75 wt %, about 60 wt % to
about 72 wt %, about 60 wt % to about 70 wt %, about 60 wt % to
about 68 wt %, about 60 wt % to about 65 wt %, about 60 wt % to
about 63 wt %, about 70 wt % to about 98 wt %, about 70 wt % to
about 95 wt %, about 70 wt % to about 90 wt %, about 70 wt % to
about 88 wt %, about 70 wt % to about 85 wt %, about 70 wt % to
about 83 wt %, about 70 wt % to about 80 wt %, about 70 wt % to
about 78 wt %, about 70 wt % to about 75 wt %, about 70 wt % to
about 72 wt %, about 75 wt % to about 98 wt %, about 75 wt % to
about 95 wt %, about 75 wt % to about 90 wt %, about 75 wt % to
about 88 wt %, about 75 wt % to about 85 wt %, about 75 wt % to
about 83 wt %, about 75 wt % to about 80 wt %, or about 75 wt % to
about 78 wt % of the imprinting solvent.
[0044] The additive can be or include one or more perfluoroalkyl
ethers, one or more polyglycols, one or more fatty acids, one or
more silanes, one or more siloxanes, or any combination thereof.
Exemplary additives can be or include fluorosurfactant,
fluoro-additive, and/or fluorocarbon (e.g., CAPSTONE.RTM. FS-66 or
FS-68 fluorosurfactant, available from DuPont), glycolic acid
ethoxylate oleyl ether, polyethylene glycol, polypropylene glycol,
lauric acid, myristic acid, stearic acid, palmitic acid,
dimethyldiethoxysilane, polydimethylsiloxane, polydiphenylsiloxane,
hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, silanol
terminated polydimethylsiloxane, vinyl terminated
polydimethylsiloxane, 1,2-propanediol, salts thereof, esters
thereof, complexes thereof, or any combination thereof. The
additive can be or include one or more diols, one or more alcohols
with three or more alcohol groups, or any combination thereof. In
one or more examples, the additive contains 1,2-propanediol. In
some examples, the additive is at a concentration of about 0.01 wt
% to about 2.5 wt %, based on the weight of the nanoparticles.
[0045] The imprint composition contains about 0.01 wt %, about 0.05
wt %, about 0.1 wt %, about 0.2 wt %, about 0.3 wt %, about 0.5 wt
%, about 0.8 wt %, or about 1 wt % to about 1.2 wt %, about 1.5 wt
%, about 1.8 wt %, about 2 wt %, about 2.5 wt %, about 3 wt %,
about 3.5 wt %, about 4 wt %, about 5 wt %, about 6 wt %, about 8
wt %, or about 10 wt % of the additive. For example, the imprint
composition contains about 0.01 wt % to about 10 wt %, about 0.01
wt % to about 8 wt %, about 0.01 wt % to about 5 wt %, about 0.01
wt % to about 4 wt %, about 0.01 wt % to about 3 wt %, about 0.01
wt % to about 2 wt %, about 0.01 wt % to about 1 wt %, about 0.01
wt % to about 0.5 wt %, about 0.01 wt % to about 0.1 wt %, about
0.01 wt % to about 0.05 wt %, about 0.1 wt % to about 10 wt %,
about 0.1 wt % to about 8 wt %, about 0.1 wt % to about 5 wt %,
about 0.1 wt % to about 4 wt %, about 0.1 wt % to about 3 wt %,
about 0.1 wt % to about 2 wt %, about 0.1 wt % to about 1 wt %,
about 0.1 wt % to about 0.5 wt %, about 1 wt % to about 10 wt %,
about 1 wt % to about 8 wt %, about 1 wt % to about 5 wt %, about 1
wt % to about 4 wt %, about 1 wt % to about 3 wt %, about 1 wt % to
about 2 wt %, or about 1 wt % to about 1.5 wt % of the
additive.
[0046] The acrylate can be or include one or more methacrylates,
one or more ethylacrylates, one or more propylacrylates, one or
more butylacrylates, one or more mono-functional acrylates, one or
more di-functional acrylates, one or more tri-functional acrylates,
other multi-functional acrylates, or any combination thereof.
Exemplary acrylates can be or include 3-(trimethoxysilyl)propyl
methacrylate (3-MPS), 3-(trimethoxysilyl)propyl acrylate,
di(ethylene glycol) methyl ether methacrylate, ethylene glycol
methyl ether methacrylate, 2-ethylhexyl methacrylate, ethyl
methacrylate, hexyl methacrylate, methacrylic acid, vinyl
methacrylate, monomers thereof, polymers thereof, salts thereof,
complexes thereof, or any combination. In some examples, the
acrylate is at a concentration of about 0.05 wt % to about 10 wt %,
based on the weight of the nanoparticles.
[0047] The imprint composition contains about 0.1 wt %, about 0.2
wt %, about 0.3 wt %, about 0.5 wt %, about 0.8 wt %, about 1 wt %
to about 1.2 wt %, about 1.5 wt %, about 1.8 wt %, or about 2 wt %,
about 2.2 wt %, about 2.3 wt %, about 2.5 wt %, about 2.8 wt %,
about 3 wt %, about 3.2 wt %, about 3.5 wt %, about 3.8 wt %, about
4 wt %, about 5 wt %, about 6 wt %, about 8 wt %, about 10 wt %,
about 12 wt %, about 15 wt %, about 18 wt %, or about 20 wt % of
the acrylate. For example, the imprint composition contains about
0.1 wt % to about 20 wt %, about 0.1 wt % to about 15 wt %, about
0.1 wt % to about 10 wt %, about 0.1 wt % to about 8 wt %, about
0.1 wt % to about 5 wt %, about 0.1 wt % to about 4 wt %, about 0.1
wt % to about 3 wt %, about 0.1 wt % to about 2 wt %, about 0.1 wt
% to about 1 wt %, about 0.1 wt % to about 0.5 wt %, about 1 wt %
to about 20 wt %, about 1 wt % to about 15 wt %, about 1 wt % to
about 10 wt %, about 1 wt % to about 8 wt %, about 1 wt % to about
5 wt %, about 1 wt % to about 4 wt %, about 1 wt % to about 3.5 wt
%, about 1 wt % to about 3.2 wt %, about 1 wt % to about 3 wt %,
about 1 wt % to about 2.8 wt %, about 1 wt % to about 2.5 wt %,
about 1 wt % to about 2.3 wt %, about 1 wt % to about 2.2 wt %,
about 1 wt % to about 2 wt %, about 1 wt % to about 1.8 wt %, about
1 wt % to about 1.5 wt %, about 1.8 wt % to about 20 wt %, about
1.8 wt % to about 15 wt %, about 1.8 wt % to about 10 wt %, about
1.8 wt % to about 8 wt %, about 1.8 wt % to about 5 wt %, about 1.8
wt % to about 4 wt %, about 1.8 wt % to about 3.5 wt %, about 1.8
wt % to about 3.2 wt %, about 1.8 wt % to about 3 wt %, about 1.8
wt % to about 2.8 wt %, about 1.8 wt % to about 2.5 wt %, about 1.8
wt % to about 2.3 wt %, about 1.8 wt % to about 2.2 wt %, or about
1.8 wt % to about 2 wt % of the acrylate.
[0048] In one or more examples, the imprint composition contains
about 0.5 wt % to about 40 wt % of the nanoparticles, about 50 wt %
to about 90 wt % of one or more solvents, about 5 wt % to about 40
wt % of the surface ligand, about 0.01 wt % to about 5 wt % of the
additive, and about 0.1 wt % to about 10 wt % of the acrylate. In
other examples, the imprint composition contains about 1 wt % to
about 25 wt % of the nanoparticles, about 60 wt % to about 85 wt %
of one or more solvents, about 6 wt % to about 35 wt % of the
surface ligand, about 0.05 wt % to about 3 wt % of the additive,
and about 0.3 wt % to about 8 wt % of the acrylate. In some
examples, the imprint composition contains about 5 wt % to about 20
wt % of the nanoparticles, about 65 wt % to about 80 wt % of one or
more solvents, about 7 wt % to about 31 wt % of the surface ligand,
about 0.09 wt % to about 1.5 wt % of the additive, and about 0.5 wt
% to about 6 wt % of the acrylate.
[0049] The imprint composition can have a viscosity of about 1 cP,
about 2 cP, about 3 cP, about 5 cP, about 8 cP, or about 10 cP to
about 12 cP, about 15 cP, about 20 cP, about 25 cP, about 30 cP,
about 40 cP, about 50 cP, or about 70 cP. For example, the imprint
composition can have a viscosity of about 1 cP to about 70 cP,
about 1 cP to about 50 cP, about 1 cP to about 40 cP, about 1 cP to
about 30 cP, about 1 cP to about 20 cP, about 1 cP to about 10 cP,
about 1 cP to about 5 cP, about 10 cP to about 70 cP, about 10 cP
to about 50 cP, about 10 cP to about 40 cP, about 10 cP to about 30
cP, about 10 cP to about 20 cP, about 20 cP to about 70 cP, about
20 cP to about 50 cP, about 20 cP to about 40 cP, about 20 cP to
about 30 cP, or about 20 cP to about 25 cP.
[0050] In one or more embodiments, the one or more acrylates in the
imprint composition can be polymerized and/or oligomerized while
producing (e.g., curing or otherwise converting) the imprint
material, such as the porous nanoimprint film.
[0051] Below are several prophetic examples of imprint compositions
which can be produced by embodiments described and discussed
herein.
TABLE-US-00001 Generic Formulations Concentration Component (wt %)
NPs 0.5%-25% surface ligand 0.5%-20% dispersion solvent .sup.
5%-20% acrylate 0.5%-10% imprinting solvent 60%-80% diol additive
0.5%-8% surfactant additive 0.01%-1% Total 100
TABLE-US-00002 Prophetic Example 1 Concentration Amount Component
(wt %) (g) NPs (TiO.sub.2) 10% 10 surface ligand 2% 2 PGMEA 12% 12
3-MPS 2.3% 2.3 ethyl lactate 71% 71 1,2-propanediol 3% 3 surfactant
(FS66) 0.15%.sup. 0.15 Total 100 100
TABLE-US-00003 Prophetic Example 2 Concentration Amount Component
(wt %) (g) NPs (TiO.sub.2) 6.5% 6.5 surface ligand 1.5% 1.5 PGMEA
.sup. 8% 8 3-MPS 2.3% 2.3 ethyl lactate 79% 79 1,2-propanediol
2.55% 2.55 surfactant (FS66) 0.15% 0.15 Total 100 100
[0052] FIG. 3 depicts a front view of an optical device 300
containing an optically densified nanoimprint film 306, as depicted
in FIG. 2B, according to one or more embodiments described and
discussed herein. In any embodiment described herein, the optically
densified nanoimprint film 116, as depicted in FIG. 2B, can be the
same or used as the optically densified nanoimprint film 306, as
depicted in FIG. 3. It is to be understood that the optical device
300 described below is an exemplary optical device. In one or more
embodiments, the optical device 300 is a waveguide combiner, such
as an augmented reality waveguide combiner. In other embodiments,
the optical device 300 is a flat optical device, such as a
metasurface. The optical device 300 includes a plurality of device
structures 304. The device structures 304 may be nanostructures
having sub-micro dimensions, e.g., nano-sized dimensions, such as
critical dimensions less than 1 .mu.m. In one or more embodiments,
regions of the device structures 304 correspond to one or more
gratings 302, such as the grating areas 302a and 302b. In one or
more embodiments, the optical device 300 includes a first grating
area 302a and a second grating area 302b and each of the first
grating area 302a and 302b each contain a plurality of device
structures 304.
[0053] The depth of the gratings 302 may vary across the grating
areas 302a and 302b in embodiments described herein. In some
embodiments, the depth of the gratings 302 may vary smoothly over
the first grating area 302a and over the second grating area 302b.
In one or more examples, the depth may range from about 10 nm to
about 400 nm across one of the grating areas. The grating area
302a, in some examples, can range from approximately 20 mm to
approximately 50 mm on a given side. Therefore, as some examples,
the angle of the change in the depth of the gratings 302 may be on
the order of 0.0005 degrees.
[0054] In embodiments described herein, the device structures 304
may be created using laser ablation. Laser ablation, as used
herein, is used to produce three-dimensional microstructures in the
device material, or optionally to create a variable-depth structure
in a sacrificial layer overlaying the device material as part of a
variable-depth structure process. Using laser ablation to create
the optical structures 304 allows for fewer processing operations
and higher variable-depth resolution than existing methods.
[0055] Embodiments of the present disclosure further relate to any
one or more of the following paragraphs 1-68:
[0056] 1. A method of forming a nanoimprint film, comprising:
positioning a substrate comprising a porous nanoimprint film within
a processing chamber, wherein the porous nanoimprint film comprises
nanoparticles and voids between the nanoparticles, and wherein the
porous nanoimprint film has a refractive index of less than 2; and
depositing a metal oxide on the porous nanoimprint film and within
at least a portion of the voids to produce an optically densified
nanoimprint film during an atomic layer deposition (ALD)
process.
[0057] 2. The method according to paragraph 1, wherein the metal
oxide has a refractive index greater than the refractive index of
the porous nanoimprint film.
[0058] 3. The method according to paragraph 1 or 2, wherein the
metal oxide has a refractive index less than the refractive index
of the porous nanoimprint film.
[0059] 4. The method according to any one of paragraphs 1-3,
wherein the optically densified nanoimprint film has a refractive
index greater than the refractive index of the porous nanoimprint
film.
[0060] 5. The method according to paragraph 4, wherein the
refractive index of the optically densified nanoimprint film is
about 0.5% to about 30% greater than the refractive index of the
porous nanoimprint film.
[0061] 6. The method according to paragraph 5, wherein the
refractive index of the optically densified nanoimprint film is
about 0.75% to about 10% greater than the refractive index of the
porous nanoimprint film.
[0062] 7. The method according to paragraph 6, wherein the
refractive index of the optically densified nanoimprint film is
about 1% to about 6% greater than the refractive index of the
porous nanoimprint film.
[0063] 8. The method according to any one of paragraphs 1-7,
wherein the refractive index of the porous nanoimprint film is
about 1.5 to about 1.95.
[0064] 9. The method according to any one of paragraphs 1-8,
wherein the refractive index of the optically densified nanoimprint
film is about 1.8 or greater.
[0065] 10. The method according to any one of paragraphs 1-9,
wherein the metal oxide comprises aluminum oxide, titanium oxide,
zirconium oxide, niobium oxide, tantalum oxide, indium oxide,
indium tin oxide, hafnium oxide, chromium oxide, scandium oxide,
tin oxide, zinc oxide, yttrium oxide, praseodymium oxide, magnesium
oxide, silicon oxide, silicon nitride, silicon oxynitride, or any
combination thereof.
[0066] 11. The method according to any one of paragraphs 1-10,
wherein the nanoparticles comprise titanium oxide, zirconium oxide,
niobium oxide, tantalum oxide, hafnium oxide, chromium oxide,
indium tin oxide, silicon nitride, or any combination thereof.
[0067] 12. The method according to any one of paragraphs 1-11,
wherein the ALD process comprises sequentially exposing the porous
nanoimprint film to a metal precursor and an oxidizing agent during
an ALD cycle to deposit the metal oxide.
[0068] 13. The method according to paragraph 12, wherein the ALD
cycle is repeated from 1 time to about 50 times while depositing
the metal oxide during the ALD process.
[0069] 14. The method according to any one of paragraphs 1-13,
wherein at least 3% of the volume occupied by the voids is filled
with the metal oxide by the ALD process.
[0070] 15. The method according to any one of paragraphs 1-14,
wherein about 20% to about 90% of the volume occupied by the voids
is filled with the metal oxide by the ALD process.
[0071] 16. A method according to any one of paragraphs 1-15,
wherein the porous nanoimprint film is formed on the substrate by
an imprint process, comprising: disposing an imprint composition
comprising the nanoparticles on the substrate; contacting the
imprint composition with a stamp having a pattern; converting the
imprint composition to a porous nanoimprint film; and removing the
stamp from the porous nanoimprint film.
[0072] 17. The method according to paragraph 16, wherein the
imprint composition is converted to the porous nanoimprint film by
exposing the imprint composition to heat, ultraviolet light,
infrared light, visible light, microwave radiation, or any
combination thereof.
[0073] 18. The method according to paragraph 16, wherein converting
the imprint composition to the porous nanoimprint film further
comprises exposing the imprint composition to a light source having
a wavelength of about 300 nm to about 365 nm.
[0074] 19. The method according to paragraph 16, wherein converting
the imprint composition to the porous nanoimprint film further
comprises heating the imprint composition to a temperature of about
30.degree. C. to about 100.degree. C. for a time period of about 30
seconds to about 1 hour.
[0075] 20. The method according to paragraph 16, wherein converting
the imprint composition to the porous nanoimprint film further
comprises heating the imprint composition to a temperature of about
50.degree. C. to about 60.degree. C. for a time period of about 1
minute to about 15 minutes.
[0076] 21. The method according to paragraph 16, wherein the
imprint composition is disposed on the substrate by spin coating,
drop casting, or blade coating.
[0077] 22. The method according to paragraph 16, wherein the
imprint composition is disposed on the substrate as a layer having
a thickness of about 50 nm to about 1,000 nm.
[0078] 23. The method according to paragraph 16, wherein the
imprint composition is disposed on the substrate as a layer having
a thickness of about 100 nm to about 400 nm.
[0079] 24. The method according to paragraph 16, wherein the
pattern on the stamp is a 1-dimension pattern, a 2-dimension
pattern, or a 3-dimension pattern.
[0080] 25. A method of forming a nanoimprint film, comprising:
disposing an imprint composition comprising nanoparticles on a
substrate; contacting the imprint composition with a stamp having a
pattern; converting the imprint composition to a porous nanoimprint
film; removing the stamp from the porous nanoimprint film;
positioning the substrate comprising the porous nanoimprint film
within a processing chamber, wherein the porous nanoimprint film
comprises nanoparticles and voids between the nanoparticles, and
wherein the porous nanoimprint film has a refractive index of less
than 2; and depositing a metal oxide on the porous nanoimprint film
and within at least a portion of the voids to produce an optically
densified nanoimprint film during an atomic layer deposition (ALD)
process, wherein the optically densified nanoimprint film has a
refractive index greater than the refractive index of the porous
nanoimprint film.
[0081] 26. An optically densified nanoimprint film, comprising: a
base nanoimprint film comprising nanoparticles and voids between
the nanoparticles, and wherein the base nanoimprint film has a
refractive index of less than 2; and a metal oxide disposed on the
base nanoimprint film and contained within at least a portion of
the voids; wherein the optically densified nanoimprint film has a
refractive index greater than the refractive index of the base
nanoimprint film.
[0082] 27. The optically densified nanoimprint film according to
paragraph 26, wherein the refractive index of the optically
densified nanoimprint film is about 0.5% to about 30% greater than
the refractive index of the base nanoimprint film.
[0083] 28. The optically densified nanoimprint film according to
paragraph 27, wherein the refractive index of the optically
densified nanoimprint film is about 0.75% to about 10% greater than
the refractive index of the base nanoimprint film.
[0084] 29. The optically densified nanoimprint film according to
paragraph 28, wherein the refractive index of the optically
densified nanoimprint film is about 1% to about 6% greater than the
refractive index of the base nanoimprint film.
[0085] 30. The optically densified nanoimprint film according to
any one of paragraphs 26-29, wherein the refractive index of the
base nanoimprint film is about 1.5 to about 1.95.
[0086] 31. The optically densified nanoimprint film according to
any one of paragraphs 26-30, wherein the refractive index of the
optically densified nanoimprint film is about 1.8 to about
2.05.
[0087] 32. The optically densified nanoimprint film according to
any one of paragraphs 26-31, wherein the metal oxide comprises
aluminum oxide, titanium oxide, zirconium oxide, niobium oxide,
tantalum oxide, indium oxide, indium tin oxide, hafnium oxide,
chromium oxide, scandium oxide, tin oxide, zinc oxide, yttrium
oxide, praseodymium oxide, magnesium oxide, silicon oxide, silicon
nitride, silicon oxynitride, or any combination thereof.
[0088] 33. The optically densified nanoimprint film according to
any one of paragraphs 26-32, wherein the nanoparticles comprise
titanium oxide, zirconium oxide, niobium oxide, tantalum oxide,
hafnium oxide, chromium oxide, indium tin oxide, silicon nitride,
or any combination thereof.
[0089] 34. The optically densified nanoimprint film according to
any one of paragraphs 26-33, wherein at least 3% of the volume
occupied by the voids in the base nanoimprint film contains the
metal oxide.
[0090] 35. The optically densified nanoimprint film according to
any one of paragraphs 26-34, wherein about 20% to about 90% of the
volume occupied by the voids in the base nanoimprint film contains
the metal oxide.
[0091] 36. An optical device with gratings, comprising: the
optically densified nanoimprint film produced by the method
according to any one of paragraphs 1-25.
[0092] 37. An optical device with gratings, comprising: the
optically densified nanoimprint film according to any one of
paragraphs 26-35.
[0093] 38. An optical device with gratings, comprising: an
optically densified nanoimprint film, comprising: a base
nanoimprint film comprising nanoparticles and voids between the
nanoparticles, and wherein the base nanoimprint film has a
refractive index of less than 2; and a metal oxide disposed on the
base nanoimprint film and contained within at least a portion of
the voids; wherein the optically densified nanoimprint film has a
refractive index greater than the refractive index of the base
nanoimprint film.
[0094] 39. A densified nanoimprint film, comprising: a base
nanoimprint film comprising nanoparticles, wherein the
nanoparticles comprise titanium oxide, zirconium oxide, niobium
oxide, tantalum oxide, hafnium oxide, chromium oxide, indium tin
oxide, silicon nitride, or any combination thereof; and a metal
oxide disposed on the base nanoimprint film and in between the
nanoparticles, wherein the metal oxide comprises aluminum oxide,
titanium oxide, zirconium oxide, niobium oxide, tantalum oxide,
indium oxide, indium tin oxide, hafnium oxide, chromium oxide,
scandium oxide, tin oxide, zinc oxide, yttrium oxide, praseodymium
oxide, magnesium oxide, silicon oxide, silicon nitride, silicon
oxynitride, or any combination thereof.
[0095] 40. The densified nanoimprint film according to paragraph
39, wherein the base nanoimprint film comprises voids disposed
between the nanoparticles, and wherein the metal oxide is disposed
at least partially within the voids.
[0096] 41. The densified nanoimprint film according to paragraph
40, wherein at least 3% of the volume occupied by the voids in the
base nanoimprint film contains the metal oxide.
[0097] 42. The densified nanoimprint film according to paragraph
41, wherein about 20% to about 90% of the volume occupied by the
voids in the base nanoimprint film contains the metal oxide.
[0098] 43. The densified nanoimprint film according to any one of
paragraphs 39-42, wherein the nanoparticles comprise titanium
oxide.
[0099] 44. The densified nanoimprint film according to paragraph
43, wherein the metal oxide comprises aluminum oxide.
[0100] 45. The densified nanoimprint film according to any one of
paragraphs 39-44, wherein the base nanoimprint film is a film by an
imprint process comprising a spin-coating process, and wherein the
metal oxide is a coating deposited by an atomic layer deposition
process.
[0101] 46. The densified nanoimprint film according to any one of
paragraphs 39-45, wherein the densified nanoimprint film has a
greater value of hardness, fracture strain, yield strength, and/or
etch resistance than the base nanoimprint film.
[0102] 47. The densified nanoimprint film according to any one of
paragraphs 39-46, wherein the densified nanoimprint film has a
lesser value of modulus of elasticity than the base nanoimprint
film.
[0103] 48. The densified nanoimprint film according to any one of
paragraphs 39-47, wherein the refractive index of the densified
nanoimprint film is about 0.5% to about 30% greater than the
refractive index of the base nanoimprint film.
[0104] 49. A method of forming a nanoimprint film, comprising:
positioning a substrate comprising a porous nanoimprint film within
a processing chamber, wherein the porous nanoimprint film comprises
nanoparticles and voids between the nanoparticles, and wherein the
nanoparticles comprise titanium oxide, zirconium oxide, niobium
oxide, tantalum oxide, hafnium oxide, chromium oxide, indium tin
oxide, silicon nitride, or any combination thereof; and depositing
a metal oxide on the porous nanoimprint film and within at least a
portion of the voids to produce an densified nanoimprint film
during an atomic layer deposition (ALD) process, wherein the metal
oxide comprises aluminum oxide, titanium oxide, zirconium oxide,
niobium oxide, tantalum oxide, indium oxide, indium tin oxide,
hafnium oxide, chromium oxide, scandium oxide, tin oxide, zinc
oxide, yttrium oxide, praseodymium oxide, magnesium oxide, silicon
oxide, silicon nitride, silicon oxynitride, or any combination
thereof.
[0105] 50. The method according to paragraph 49, wherein the ALD
process comprises sequentially exposing the porous nanoimprint film
to a metal precursor and an oxidizing agent during an ALD cycle to
deposit the metal oxide.
[0106] 51. The method according to paragraph 50, wherein the ALD
cycle is repeated from 2 times to about 50 times while depositing
the metal oxide during the ALD process.
[0107] 52. The method according to any one of paragraphs 49-51,
wherein at least 3% of the volume occupied by the voids is filled
with the metal oxide by the ALD process.
[0108] 53. The method according to any one of paragraphs 49-52,
wherein about 20% to about 90% of the volume occupied by the voids
is filled with the metal oxide by the ALD process.
[0109] 54. The method according to any one of paragraphs 49-53,
wherein the densified nanoimprint film has a greater value of
hardness, fracture strain, yield strength, and/or etch resistance
than the base nanoimprint film.
[0110] 55. The method according to any one of paragraphs 49-54,
wherein the densified nanoimprint film has a lesser value of
modulus of elasticity than the base nanoimprint film.
[0111] 56. The method according to any one of paragraphs 49-55,
wherein the refractive index of the densified nanoimprint film is
about 0.5% to about 30% greater than the refractive index of the
base nanoimprint film.
[0112] 57. A method according to any one of paragraphs 49-56,
wherein the porous nanoimprint film is formed on the substrate by
an imprint process, comprising: disposing an imprint composition
comprising the nanoparticles on the substrate; contacting the
imprint composition with a stamp having a pattern; converting the
imprint composition to a porous nanoimprint film; and removing the
stamp from the porous nanoimprint film.
[0113] 58. The method according to paragraph 57, wherein the
imprint composition is converted to the porous nanoimprint film by
exposing the imprint composition to heat, ultraviolet light,
infrared light, visible light, microwave radiation, or any
combination thereof.
[0114] 59. The method according to paragraph 57, wherein converting
the imprint composition to the porous nanoimprint film further
comprises exposing the imprint composition to a light source having
a wavelength of about 300 nm to about 365 nm.
[0115] 60. The method according to paragraph 57, wherein converting
the imprint composition to the porous nanoimprint film further
comprises heating the imprint composition to a temperature of about
30.degree. C. to about 100.degree. C. for a time period of about 30
seconds to about 1 hour.
[0116] 61. The method according to paragraph 57, wherein converting
the imprint composition to the porous nanoimprint film further
comprises heating the imprint composition to a temperature of about
50.degree. C. to about 60.degree. C. for a time period of about 1
minute to about 15 minutes.
[0117] 62. The method according to paragraph 57, wherein the
imprint composition is disposed on the substrate by spin coating,
drop casting, or blade coating.
[0118] 63. The method according to paragraph 57, wherein the
imprint composition is disposed on the substrate as a layer having
a thickness of about 50 nm to about 1,000 nm.
[0119] 64. The method according to paragraph 57, wherein the
imprint composition is disposed on the substrate as a layer having
a thickness of about 100 nm to about 400 nm.
[0120] 65. The method according to paragraph 57, wherein the
pattern on the stamp is a 1-dimension pattern, a 2-dimension
pattern, or a 3-dimension pattern.
[0121] 66. An optical device with gratings, comprising: the
densified nanoimprint film according to any one of paragraphs
39-48.
[0122] 67. An optical device with gratings, comprising: the
densified nanoimprint film produced by the method according to any
one of paragraphs 49-65.
[0123] 68. An optical device with gratings, comprising: a densified
nanoimprint film, comprising: a base nanoimprint film comprising
nanoparticles, wherein the nanoparticles comprise titanium oxide,
zirconium oxide, niobium oxide, tantalum oxide, hafnium oxide,
chromium oxide, indium tin oxide, silicon nitride, or any
combination thereof; and a metal oxide disposed on the base
nanoimprint film and in between the nanoparticles, wherein the
metal oxide comprises aluminum oxide, titanium oxide, zirconium
oxide, niobium oxide, tantalum oxide, indium oxide, indium tin
oxide, hafnium oxide, chromium oxide, scandium oxide, tin oxide,
zinc oxide, yttrium oxide, praseodymium oxide, magnesium oxide,
silicon oxide, silicon nitride, silicon oxynitride, or any
combination thereof.
[0124] While the foregoing is directed to embodiments of the
disclosure, other and further embodiments may be devised without
departing from the basic scope thereof, and the scope thereof is
determined by the claims that follow. All documents described
herein are incorporated by reference herein, including any priority
documents and/or testing procedures to the extent they are not
inconsistent with this text. As is apparent from the foregoing
general description and the specific embodiments, while forms of
the present disclosure have been illustrated and described, various
modifications can be made without departing from the spirit and
scope of the present disclosure. Accordingly, it is not intended
that the present disclosure be limited thereby. Likewise, the term
"comprising" is considered synonymous with the term "including" for
purposes of United States law. Likewise, whenever a composition, an
element, or a group of elements is preceded with the transitional
phrase "comprising", it is understood that the same composition or
group of elements with transitional phrases "consisting essentially
of", "consisting of", "selected from the group of consisting of",
or "is" preceding the recitation of the composition, element, or
elements and vice versa, are contemplated.
[0125] Certain embodiments and features have been described using a
set of numerical upper limits and a set of numerical lower limits.
It should be appreciated that ranges including the combination of
any two values, e.g., the combination of any lower value with any
upper value, the combination of any two lower values, and/or the
combination of any two upper values are contemplated unless
otherwise indicated. Certain lower limits, upper limits and ranges
appear in one or more claims below.
* * * * *