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| United States Patent Application |
20090200266
|
| Kind Code
|
A1
|
|
Doyle; Gary F.
;   et al.
|
August 13, 2009
|
Template Pillar Formation
Abstract
Materials for forming an imprint lithography template may be etched at
different rates based on physical properties of the layers. Additionally,
reflectance of the materials may be monitored to provide substantially
uniform erosion of the materials.
| Inventors: |
Doyle; Gary F.; (Round Rock, TX)
; Schmid; Gerard M.; (Austin, TX)
; Miller; Michael N.; (Austin, TX)
; Resnick; Douglas J.; (Austin, TX)
; LaBrake; Dwayne L.; (Cedar Park, TX)
|
| Correspondence Address:
|
MOLECULAR IMPRINTS
PO BOX 81536
AUSTIN
TX
78708-1536
US
|
| Assignee: |
MOLECULAR IMPRINTS, INC.
Austin
TX
|
| Serial No.:
|
367661 |
| Series Code:
|
12
|
| Filed:
|
February 9, 2009 |
| Current U.S. Class: |
216/60 |
| Class at Publication: |
216/60 |
| International Class: |
G01L 21/30 20060101 G01L021/30 |
Claims
1. A method comprising:identifying a first physical property of a first
material to determine a first estimated erosion rate of the first
material, the first material having a first reflectance;identifying a
second physical property of a second material to determine a second
estimated erosion rate of the second material, the first material
disposed on the second material;selecting a process pressure for a
reactive ion etching process for etching the first material and the
second material;adjusting the process pressure during the reactive ion
etching process based on the first estimated erosion rate and the second
estimated erosion rate; and,monitoring a reflectance of the second
material to provide substantially uniform erosion of the second material.
2. The method of claim 1, further comprising:selecting a RF power for the
reactive ion etching process; and,adjusting the RF power during the
reactive ion etching process based on the first estimated erosion rate
and the second estimated erosion rate.
3. The method of claim 1, further comprising:selecting a gas flow rate for
the reactive ion etching process; and,adjusting the gas flow rate during
the reactive ion etching process based on the first estimated erosion
rate and the second estimated erosion rate.
4. The method of claim 1, wherein the first physical property is a
thickness of the first material.
5. The method of claim 1, wherein the second physical property is a
thickness of the second material.
6. The method of claim 1, wherein the erosion rate of the first material
is less than the erosion rate of the second material.
7. The method of claim 1, wherein the first material is a hard mask layer.
8. The method of claim 7, wherein the second material is a conducting
layer.
9. The method of claim 8, further comprising:identifying a third physical
property of a third material to evaluate a depth for pattern transfer,
the second material disposed on the third material; and,monitoring the
reflectance of the second material and a reflectance of the third
material to determine a targeted etch time for etching the third material
based on the evaluated depth for pattern transfer.
10. The method of claim 9, wherein the third physical property is a
thickness of the third material.
11. The method of claim 9, wherein the third material is a substrate
layer.
12. The method of claim 9, wherein etching of the third material provides
an imprint lithography template.
13. A method comprising:identifying a first erosion rate of a first
material;identifying a second erosion rate of a second material, the
first material disposed on the second material;identifying a third
erosion rate of a third material, the second material disposed on the
third material;etching the first material and the second material using a
reactive ion etching process;adjusting pressure and gas flow rate of the
reactive ion etching process based on the first erosion rate and the
second erosion rate; and,monitoring reflectance of the second material
and the third material to provide substantially uniform erosion of the
second material and the third material resulting in an imprint
lithography template.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001]This application claims the benefit under 35 U.S.C. .sctn. 119(e)(1)
of U.S. Provisional No. 61/027,150, filed on Feb. 8, 2008, which is
hereby incorporated by reference herein.
BACKGROUND INFORMATION
[0002]Nano-fabrication includes the fabrication of very small structures
that have features on the order of 100 nanometers or smaller. One
application in which nano-fabrication has had a sizeable impact is in the
processing of integrated circuits. The semiconductor processing industry
continues to strive for larger production yields while increasing the
circuits per unit area formed on a substrate, therefore nano-fabrication
becomes increasingly important. Nano-fabrication provides greater process
control while allowing continued reduction of the minimum feature
dimensions of the structures formed. Other areas of development in which
nano-fabrication has been employed include biotechnology, optical
technology, mechanical systems, and the like.
[0003]An exemplary nano-fabrication technique in use today is commonly
referred to as imprint lithography. Exemplary imprint lithography
processes are described in detail in numerous publications, such as U.S.
Patent Publication No. 2004/0065976, U.S. Patent Publication No.
2004/0065252, and U.S. Pat. No. 6,936,194, all of which are hereby
incorporated by reference herein.
[0004]An imprint lithography technique disclosed in each of the
aforementioned U.S. patent publications and patent includes formation of
a relief pattern in a formable (polymerizable) layer and transferring a
pattern corresponding to the relief pattern into an underlying substrate.
The substrate may be coupled to a motion stage to obtain a desired
positioning to facilitate the patterning process. The patterning process
uses a template spaced apart from the substrate and a formable liquid
applied between the template and the substrate. The formable liquid is
solidified to form a rigid layer that has a pattern conforming to a shape
of the surface of the template that contacts the formable liquid. After
solidification, the template is separated from the rigid layer such that
the template and the substrate are spaced apart. The substrate and the
solidified layer are then subjected to additional processes to transfer a
relief image into the substrate that corresponds to the pattern in the
solidified layer.
BRIEF DESCRIPTION OF DRAWINGS
[0005]So that the present invention may be understood in more detail, a
description of embodiments of the invention is provided with reference to
the embodiments illustrated in the appended drawings. It is to be noted,
however, that the appended drawings illustrate only typical embodiments
of the invention, and are therefore not to be considered limiting of the
scope.
[0006]FIG. 1 illustrates a simplified side view of a lithographic system
in accordance with an embodiment of the present invention.
[0007]FIG. 2 illustrates a simplified side view of the substrate shown in
FIG. 1 having a patterned layer positioned thereon.
[0008]FIGS. 3-12 illustrate an exemplary method of forming an imprint
lithography template.
[0009]FIG. 13 illustrates a flow chart of an exemplary method for etching
a first material while substantially maintaining a second material.
[0010]FIGS. 14A and 14B illustrate exemplary graphs showing variation of
reflectance intensity as an RIE etch process proceeds through layers of
material.
DETAILED DESCRIPTION
[0011]Referring to the figures, and particularly to FIG. 1, illustrated
therein is a lithographic system 10 used to form a relief pattern on
substrate 12. Substrate 12 may be coupled to substrate chuck 14. As
illustrated, substrate chuck 14 is a vacuum chuck. Substrate chuck 14,
however, may be any chuck including, but not limited to, vacuum,
pin-type, groove-type, electrostatic, electromagnetic, and/or the like.
Exemplary chucks are described in U.S. Pat. No. 6,873,087, which is
hereby incorporated by reference herein.
[0012]Substrate 12 and substrate chuck 14 may be further supported by
stage 16. Stage 16 may provide motion along the x, y, and z axes. Stage
16, substrate 12, and substrate chuck 14 may also be positioned on a base
(not shown).
[0013]Spaced-apart from substrate 12 is template 18. Template 18 may
include mesa 20 extending therefrom towards substrate 12, mesa 20 having
a patterning surface 22 thereon. Further, mesa 20 may be referred to as
mold 20. Alternatively, template 18 may be formed without mesa 20.
[0014]Template 18 and/or mold 20 may be formed from such materials
including, but not limited to, fused-silica, quartz, silicon, organic
polymers, siloxane polymers, borosilicate glass, fluorocarbon polymers,
metal, hardened sapphire, and/or the like. As illustrated, patterning
surface 22 comprises features defined by a plurality of spaced-apart
recesses 24 and/or protrusions 26, though embodiments of the present
invention are not limited to such configurations. Patterning surface 22
may define any original pattern that forms the basis of a pattern to be
formed on substrate 12.
[0015]Template 18 may be coupled to chuck 28. Chuck 28 may be configured
as, but not limited to, vacuum, pin-type, groove-type, electrostatic,
electromagnetic, and/or other similar chuck types. Exemplary chucks are
further described in U.S. Pat. No. 6,873,087, which is hereby
incorporated by reference herein. Further, chuck 28 may be coupled to
imprint head 30 such that chuck 28 and/or imprint head 30 may be
configured to facilitate movement of template 18.
[0016]System 10 may further comprise fluid dispense system 32. Fluid
dispense system 32 may be used to deposit polymerizable material 34 on
substrate 12. Polymerizable material 34 may be positioned upon substrate
12 using techniques such as drop dispense, spin-coating, dip coating,
chemical vapor deposition (CVD), physical vapor deposition (PVD), thin
film deposition, thick film deposition, and/or the like. For example,
polymerizable material 34 may be positioned upon substrate 12 using
techniques such as those described in U.S. Patent Publication No.
2005/0270312 and U.S. Patent Publication No. 2005/0106321, both of which
are hereby incorporated by reference herein. Polymerizable material 34
may be disposed upon substrate 12 before and/or after a desired volume is
defined between mold 20 and substrate 12 depending on design
considerations. Polymerizable material 34 may comprise a monomer mixture
as described in U.S. Pat. No. 7,157,036 and U.S. Patent Publication No.
2005/0187339, both of which are hereby incorporated by reference herein.
[0017]Referring to FIGS. 1 and 2, system 10 may further comprise energy
source 38 coupled to direct energy 40 along path 42. Imprint head 30 and
stage 16 may be configured to position template 18 and substrate 12 in
superimposition with path 42. System 10 may be regulated by processor 54
in communication with stage 16, imprint head 30, fluid dispense system
32, and/or source 38, and may operate on a computer readable program
stored in memory 56.
[0018]Either imprint head 30, stage 16, or both vary a distance between
mold 20 and substrate 12 to define a desired volume therebetween that is
filled by polymerizable material 34. For example, imprint head 30 may
apply a force to template 18 such that mold 20 contacts polymerizable
material 34. After the desired volume is filled with polymerizable
material 34, source 38 produces energy 40, e.g., ultraviolet radiation,
causing polymerizable material 34 to solidify and/or cross-link
conforming to a shape of surface 44 of substrate 12 and patterning
surface 22, defining patterned layer 46 on substrate 12. Patterned layer
46 may comprise a residual layer 48 and a plurality of features shown as
protrusions 50 and recessions 52, with protrusions 50 having a thickness
t.sub.1 and residual layer having a thickness t.sub.2.
[0019]The above-mentioned system and process may be further employed in
imprint lithography processes and systems referred to in U.S. Pat. No.
6,932,934, U.S. Patent Publication No. 2004/0124566, U.S. Patent
Publication No. 2004/0188381, and U.S. Patent Publication No.
2004/0211754, all of which are hereby incorporated by reference herein.
[0020]FIGS. 3-12 illustrate an exemplary method of forming imprint
lithography template 18 for use in system 10. Generally, template 18 may
be formed by disposing a conducting layer 62 on a substrate layer 60. A
resist layer 64 may be disposed over conducting layer 62 and patterned
(e.g., electron-beam lithography). A hard mask layer 66 may then be
disposed over resist layer 64A. Additionally, a planarizing layer 68 may
be disposed over resist layer 64 and/or hard mask layer 66 to provide a
substantially planar top surface. Plasma etching processes may then be
used to transfer the pattern into substrate layer 60.
[0021]Referring to FIG. 3, conducting layer 62 may be disposed on
substrate layer 60. Substrate layer 60 may be formed of materials
including, but not limited to quartz, silicon, organic polymers, siloxane
polymers, borosilicate glass, fluorocarbon polymers, metal, hardened
sapphire, and/or the like. Generally, substrate layer 60 may be formed
with a high quality optical surface with low roughness and/or defects.
For example, substrate layer 60 may be formed having a 20/10 scratch/dig
ratio. Substrate layer 60 may have a thickness t.sub.3. Thickness t.sub.3
of substrate layer 60 may be substantially uniform. The magnitude of
thickness t.sub.3 may be between approximately 0.1 to 10 mm. A lesser
magnitude of thickness t.sub.3 of substrate layer 60 may provide for
substrate layer 60 and/or template 18 to be capable of flexing and/or
deforming during the imprinting process. For example, thickness t.sub.3
may be approximately 1 mm.
[0022]Conducting layer 62 may be disposed on substrate layer 60 and is
generally capable of being etched by a plasma etching process. Conducting
layer 62 may have a thickness t.sub.4. Thickness t.sub.4 may be between
approximately 1 to 10 nm. For example, conducting layer 62 may have a
thickness t.sub.4 of 5 nm. Conducting layer 62 may be formed of materials
including, but not limited to, tantalum, tantalum nitride, tantalum
silicide, tungsten, tungsten nitride, silicon carbide, amorphous silicon,
chromium, chromium nitride, molybdenum, molybdenum silicide, titanium,
titanium nitride, and/or the like.
[0023]Referring to FIG. 4, resist layer 64 may be disposed on substrate
layer 60 and/or conducting layer 62. Resist layer 64 may have a thickness
t.sub.5. Thickness t.sub.5 may be between approximately 5 to 150 nm. For
example, resist layer 64 may have a thickness t.sub.5 of 45 nm. Thickness
t.sub.5 may be selected to obtain a desired patterning resolution. For
example, the magnitude of thickness t.sub.5 of resist layer 64 may be
approximately 100 nm in circumstances that may be suitable for patterning
structures with lateral dimensions of 50 nm. Alternatively, the magnitude
of thickness t.sub.5 of resist layer 64 may be approximately 50 nm in
circumstances that may be suitable for patterning structures with lateral
dimensions of 25 nm.
[0024]Resist layer 64 may be formed of materials including, but not
limited to, imprint resist material, novolac-type p
hotoresists, acrylate
p
hotoresists, epoxy p
hotoresists, bilayer resist materials, and/or the
like. Generally, resist layer 64 may be formed of positive-tone electron
beam resist such as, for example, ZEP520A manufactured by Zeon
Corporation, with an office located in Tokyo, Japan, or 950k MW PMMA
electron beam resist, and/or the like.
[0025]Resist layer 64 may be patterned to provide one or more features 70.
For example, resist layer 64 may be exposed in an electron beam
lithography tool to pattern features 70. An exemplary electron beam
lithography tool is the VB6HR, manufactured by Vistec Lithography, Inc.,
with an office located in Watervliet, N.Y. The exposure pattern may
consist of 25 nm diameter dots on a pitch of 50 nm. Resist layer 64 may
be developed to obtain optimal resolution and/or process window. After
development, un-exposed regions of resist layer 64 form features 70.
[0026]In one example, using ZEP520A, resist layer 64 may be developed and
features 70 formed by immersing resist layer 64 in amyl acetate at a
temperature between approximately -15 to 25 degrees Celsius for
approximately 5 to 90 seconds.
[0027]In another example, using PMMA, resist layer 64 may be developed and
features 70 formed by immersing resist layer 64 in a mixture of isopropyl
alcohol and water at a temperature between approximately -15 to 25
degrees Celsius for approximately 5 to 90 seconds. It should be noted
that ultrasonic agitation (e.g., approximately 30 to 50 kHz) may be used
during development.
[0028]Referring to FIGS. 5A and 5B, hard mask layer 66 may be disposed on
resist layer 64 by processes including, but not limited to, sputtering,
evaporation, and the like. For example, thermal evaporation and e-beam
evaporation may be used. Hard mask layer may be disposed on portions of
resist layer 64 as illustrated in FIG. 5A or disposed on the entire
resist layer 64 as illustrated in FIG. 5B.
[0029]Hard mask layer 66 may be formed of materials including, but not
limited to, chromium, chromium nitride, nickel, platinum, vanadium,
and/or the like. Hard mask layer 66 may have a thickness t.sub.6.
Thickness t.sub.6 may be between approximately 1-20 nm. For example, hard
mask layer 66 may have a thickness t.sub.6 of approximately 5 nm.
[0030]Referring to FIG. 6, planarizing layer 68 may be disposed on resist
layer 64 and/or hard mask layer 66 to provide for a substantially planar
top surface. Planarizing layer 68 may be disposed by processes including,
but not limited to, spin-coating, evaporation, sputtering, chemical vapor
deposition (CVD), and the like. Alternatively, planarizing layer 68 may
be disposed in an imprint step such that a planar topography may be
molded from an unpatterned surface of template 18. Imprint techniques may
provide for planar surfaces with minimal dependence on pattern density of
underlying features 70.
[0031]Materials used to form planarizing layer 68 are generally selected
to provide little or no significant alterations to resist layer 66 and/or
features 70 of resist layer 66. Planarizing layer 68 may be formed of
materials including, but not limited to, organic imprint resist material,
silicon-containing imprint resist material, spin-on dielectric materials,
silsesquioxane materials, sol-gel materials, siloxane materials, bilayer
resist materials, and/or the like. Planarizing layer 68 may have a
thickness t.sub.7. Thickness t.sub.7 may be between approximately 20 to
200 nm or other suitable range in order to provide for a substantially
planar top surface. For example, planarizing layer 68 may have a
thickness t.sub.7 of approximately 100 nm.
[0032]Referring to FIG. 7, planarizing layer 68 may be etched until
planarizing layer 68 is substantially removed in un-patterned regions.
Etching may be performed in plasma containing oxygen, argon, and/or
fluorocarbon.
[0033]Referring to FIG. 8, hard mask layer 66 may be plasma etched until
hard mask layer 66 is substantially removed in un-patterned regions. In
one example, hard mask layer 66 may be etched in plasma containing
chlorine and/or oxygen. It should be noted that the etching of
planarizing layer 68 and the etching of hard mask layer 66 may be
performed in a single step process.
[0034]Etching of hard mask layer 66 and/or planarizing layer 68 may be
monitored. For example, etching of hard mask layer 66 and/or planarizing
layer 68 may be monitored by a reflectance probe (e.g., laser reflectance
probe). The reflectance probe may measure reflectance loss as hard mask
layer 66 and/or planarizing layer 68 are removed.
[0035]Referring to FIGS. 9A-C, resist layer 64 may be removed. For
example, resist layer 64 may be removed by dissolution in a solvent as
illustrated in FIG. 9A. Additionally, as shown in FIGS. 9B and 9C,
removal of resist layer 64 may result in removal of planarizing layer 68.
[0036]Exemplary solvents for dissolution of resist layer 64 include, but
are not limited to, dichloromethane, diemthylacetamide,
N-methylpyrrolidone, and the like. In one example, resist layer 64 is
removed using a plasma etch. For example, resist layer 64 may be removed
in plasma containing oxygen and/or argon.
[0037]Plasma etching of fused silica, silicon dioxide, and refractory
metals is generally an ion-enhanced process. As such, the process may
provide for etching of the surface of such materials to provide surface
chemical reactions that may result in the removal of these materials.
Generally, plasma conditions that produce this effect may involve high RF
power and/or lower process chamber pressure. These conditions may result
in unwanted erosion or a higher rate of erosion of materials than may be
needed. For example, in certain circumstances, hard mask layer 66 may
have a thickness t.sub.6 substantially less than 15 nm. Application of
high RF power and/or lower pressure may substantially erode hard mask
layer 66 and may result in deformation during pattern transfer (e.g.,
pattern critical dimension consistencies and/or poor profile control).
[0038]FIG. 13 illustrates a flow chart of a method 80 for etching
conducting layer 62 (e.g., tantalum) while substantially maintaining hard
mask layer 66 (e.g., chromium). For example, method 80 may reduce erosion
rate of hard mask layer 66 (e.g., <1 nm/min) while maintaining a
suitable erosion rate for conducting layer 62 (e.g., >1 nm/min). In a
step 82, physical properties of hard mask layer 66 may be identified for
determination of an estimated erosion rate for hard mask layer 66. For
example, thickness t.sub.6 of hard mask layer 66 may be identified to
determine the estimated erosion rate for hard mask layer 66. In a step
84, physical properties of conducting layer 62 may be identified for
determination of an estimated erosion rate for conducting layer 62. For
example, thickness t.sub.4 may be identified for determination of the
estimated erosion rate for conducting layer 62. In a step 86, physical
properties of substrate layer 60 (e.g. quartz) may be identified for
evaluation of depth desired for pattern transfer (e.g., approximately
10-100 nm). In a step 88, RF power, process pressure, and/or gas flow
ratio (e.g., CF.sub.4/helium gas flow ratio) within a commercially
available reactive ion etch (RIE) plasma processing system may be
selected. In a step 90, RF power, process pressure, and/or gas flow ratio
may be adjusted based on the estimated erosion rate for hard mask layer
66 and/or conducting layer 62. In a step 92, etch rate of conducting
layer 62 may be monitored by a reflectance probe to provide substantially
consistent results in patterning of substrate layer 60.
[0039]The reflectance probe may be any apparatus that provides information
regarding surface reflectance of a material over time. For example,
reflectance probe may be a laser source that is integrated into a video
camera and/or reflectance sensor module. The etch rate of conducting
layer 62 may be monitored by the reflectance probe to provide a surface
reflectance graph. Exemplary reflectance graphs 120 are illustrated in
FIGS. 14A and 14B. Graphs 120 provide the surface reflectance of at least
two materials over time. Section A illustrates the surface reflectance of
a first material (e.g., conducting layer 62) at the beginning of the etch
process. Section B illustrates surface reflectance of the first material
as the etch process continues. Section C illustrates surface reflectance
of a second material (e.g., substrate layer 60) once the first material
is removed from the area being monitored. Surface reflectance between the
first material and the second material may differ substantially or
minimally. Additionally, the surface reflectance of the first material
may be more than the surface reflectance of the second material (as shown
in FIG. 14A) or less than the surface reflectance of the second material
(as shown in FIG. 14B). Additionally, a targeted etch time for substrate
layer 62 may be determined based on surface reflectance between Section B
and Section C of graph 120. For example, between samples, thickness
t.sub.4 of conducting layer 62 may vary. A standardized etch rate for
substrate layer 62 with multiple conducting layers 62 may result in
inconsistent etch depth within substrate layer 62. As such, a targeted
etch time may be developed for substrate layer 62 having a starting point
at the transition of Section B and Section C of graph 120. The targeted
etch time may remove thickness of conducting layer 62 in standardizing
the pattern depth in substrate layer 62.
[0040]The above identified method for etching conducting layer 62 while
substantially maintaining hard mask layer 66 and monitoring etching of
two or more materials may be used in additional processes such as those
described in U.S. Ser. No. 11/856,862 and U.S. Ser. No. 11/943,907, both
of which are hereby incorporated by reference herein.
[0041]Referring to FIG. 10, hard mask layer 66 may be used as an etch mask
to create topography in underlying substrate layer 60. Substrate layer 60
may be etched using a fluorocarbon plasma etch process. Etch time may be
determined by graph 120 of FIG. 14A, as described in further detail
herein.
[0042]Referring to FIG. 11, cleaning process may be performed to remove
residual resist layer 64, planarizing layer 68, and/or conducting layer
64. For example, substrate layer 60 may be immersed in a piranha solution
(e.g., H.sub.2SO.sub.4 and H.sub.2O.sub.2). Hard mask layer 66 may be
removed using an aqueous solution containing ceric ammonium nitride.
Conducting layer 64 may be removed using a vapor containing xenon
difluoride.
* * * * *