U.S. patent application number 16/389097 was filed with the patent office on 2019-08-08 for composition and method for polishing silicon carbide.
The applicant listed for this patent is Cabot Microelectronics Corporation. Invention is credited to Fernando HUNG LOW, Roman IVANOV, Cheng-Yuan KO, Glenn WHITENER.
Application Number | 20190241783 16/389097 |
Document ID | / |
Family ID | 62711177 |
Filed Date | 2019-08-08 |
United States Patent
Application |
20190241783 |
Kind Code |
A1 |
IVANOV; Roman ; et
al. |
August 8, 2019 |
COMPOSITION AND METHOD FOR POLISHING SILICON CARBIDE
Abstract
The invention provides a chemical-mechanical polishing
composition comprising (a) silica particles, (b) a polymer
comprising sulfonic acid monomeric units, (c) optionally, a
buffering agent, and (d) water, wherein the polishing composition
has a pH of about 2 to about 5. The invention further provides a
method of chemically-mechanically polishing a substrate with the
inventive chemical-mechanical polishing composition. Typically, the
substrate comprises silicon carbide and silicon nitride.
Inventors: |
IVANOV; Roman; (Aurora,
IL) ; HUNG LOW; Fernando; (Aurora, IL) ; KO;
Cheng-Yuan; (New Taipei City, TW) ; WHITENER;
Glenn; (Batavia, IL) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Cabot Microelectronics Corporation |
Aurora |
IL |
US |
|
|
Family ID: |
62711177 |
Appl. No.: |
16/389097 |
Filed: |
April 19, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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15398933 |
Jan 5, 2017 |
10294399 |
|
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16389097 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C09K 3/1409 20130101;
C09G 1/02 20130101; C09K 3/1463 20130101; H01L 21/31053
20130101 |
International
Class: |
C09K 3/14 20060101
C09K003/14; H01L 21/3105 20060101 H01L021/3105; C09G 1/02 20060101
C09G001/02 |
Claims
1. A chemical-mechanical polishing composition comprising: (a)
silica particles containing aluminum ions, wherein the aluminum
ions are uniformly distributed within the silica particles, and
wherein the silica particles have an average particle size of about
40 nm to about 80 nm, (b) a polymer comprising sulfonic acid
monomeric units, (c) a buffering agent, and (d) water, wherein the
polishing composition has a pH of about 2 to about 5.
2. The polishing composition of claim 1, wherein the silica
particles have an average particle size of about 40 nm to about 60
nm.
3. The polishing composition of claim 1, wherein the silica
particles are substantially spherical.
4. The polishing composition of claim 1, wherein the polymer
comprising sulfonic acid monomeric units has an average molecular
weight of about 75,000 g/mole to about 200,000 g/mole.
5. The polishing composition of claim 1, wherein the polymer
comprising sulfonic acid monomeric units is selected from
polystyrenesulfonic acid,
poly(2-acrylamido-2-methyl-1-propanesulfonic acid), and
poly(styrenesulfonic acid-co-maleic acid).
6. The polishing composition of claim 1, wherein the buffering
agent is selected from formic acid, malonic acid, acetic acid,
oxalic acid, citric acid, and phosphoric acid.
7. The polishing composition of claim 1, wherein the polishing
composition further comprises an oxidizing agent.
8. The polishing composition of claim 7, wherein the oxidizing
agent is hydrogen peroxide.
9. The polishing composition of claim 1, wherein the polishing
composition does not contain a piperazine compound, a 4-morpholine
compound, an amino sulfonic acid compound, a substituted amine
compound, a tertiary amine compound, or a bis-amine compound, or
salts thereof.
Description
BACKGROUND OF THE INVENTION
[0001] Compositions and methods for planarizing or polishing the
surface of a substrate are well known in the art. Polishing
compositions (also known as polishing slurries) typically contain
an abrasive material in a liquid carrier and are applied to a
surface by contacting the surface with a polishing pad saturated
with the polishing composition. Typical abrasive materials include
silicon dioxide, cerium oxide, aluminum oxide, zirconium oxide, and
tin oxide. Polishing compositions are typically used in conjunction
with polishing pads (e.g., a polishing cloth or disk). Instead of,
or in addition to, being suspended in the polishing composition,
the abrasive material may be incorporated into the polishing
pad.
[0002] The next generation of semiconductor devices incorporates
the use of materials with greater hardness and other desirable
properties for high power, high temperature, and high frequency
operation applications. Such materials include silicon carbide and
silicon nitride. Silicon carbide is a material with a desirable
combination of electrical and thermo-physical properties, including
high practical operating temperature, good corrosion resistance,
and high thermal properties. Silicon nitride is a high strength
hard material having utility as an etch stop mask, an electrical
insulator, a chemical diffusion barrier, or as a dielectric
material in capacitors. However, silicon carbide and silicon
nitride are significantly harder and more chemically inert than
other materials comprising integrated circuits.
[0003] In addition, known polishing compositions and methods do not
provide the ability to selectively remove silicon carbide from a
semiconductor wafer without removing materials such as silicon
dioxide from the same wafer at unacceptably high levels. As the
technology for integrated circuit devices advances, traditional
materials are being used in new and different ways to achieve the
level of performance needed for advanced integrated circuits. In
particular, silicon nitride, silicon carbide, and silicon dioxide
are being used in various combinations to achieve new and even more
complex device configurations. In general, the structural
complexity and performance characteristics vary across different
applications.
[0004] Accordingly, there is an ongoing need to develop new
polishing methods and compositions that provide relatively high
rates of removal of silicon carbide and to selectively remove
silicon carbide in preference to other materials present on the
surface of the semiconductor wafer.
BRIEF SUMMARY OF THE INVENTION
[0005] The invention provides a method of chemically mechanically
polishing a substrate comprising (i) providing a substrate, wherein
the substrate comprises a silicon carbide layer on a surface of the
substrate; (ii) providing a polishing pad; (iii) providing a
polishing composition comprising (a) silica particles, (b) a
polymer comprising sulfonic acid monomeric units, and (c) water,
wherein the polishing composition has a pH of about 2 to about 5;
(iv) contacting the substrate with the polishing pad and the
polishing composition; and (v) moving the polishing pad and the
polishing composition relative to the substrate to abrade at least
a portion of the silicon carbide layer on a surface of the
substrate to polish the substrate.
[0006] The invention also provides a chemical-mechanical polishing
composition comprising (a) silica particles containing aluminum
ions, wherein the aluminum ions are uniformly distributed within
the silica particles, and wherein the silica particles have an
average particle size of about 40 nm to about 80 nm, (b) a polymer
comprising sulfonic acid monomeric units, (c) a buffering agent,
and (d) water, wherein the polishing composition has a pH of about
2 to about 5.
DETAILED DESCRIPTION OF THE INVENTION
[0007] The invention provides a chemical-mechanical polishing
composition comprising (a) silica particles, (b) a polymer
comprising sulfonic acid monomeric units, (c) optionally, a
buffering agent, and (d) water, wherein the polishing composition
has a pH of about 2 to about 5.
[0008] The polishing composition comprises silica particles. The
silica particles can be any suitable silica particles. The silica
particles can be precipitated silica particles or
condensation-polymerized silica particles. In some embodiments, the
silica particles comprise precipitated silica, such as Snowtex.TM.
silica particles from Nissan Chemical. Non-limiting examples of
Snowtex.TM. silica particles include the ST-OL-40, ST-OZL-35, and
ST-PMSO products. In some embodiments, the silica particles
comprise anionic silica particles prepared by condensation of
silica particles with a mercaptosilane such as a
mercaptoalkyltrialkoxysilane, followed by oxidation of the
mercaptan group to sulfate or sulfonate. Non-limiting examples of
suitable anionic silica particles are the PL-3D from Fuso Chemical
and WL 83A, a colloidal silica particle that has been surface
modified with aluminum ions, as described in U.S Published
Application 2016/0222254. In some embodiments, the silica particles
contain aluminum ions, wherein the aluminum ions are uniformly
distributed within the silica particles. Silica particles
containing aluminum ions can be prepared by a precipitation process
using an aqueous silicate solution containing aluminum ions. The
aluminum ions can be added to the aqueous silicate solution, or can
occur as impurities or low level components of the silicate
resulting from the raw materials used to prepare the silicate. In
this embodiment, because the particles are formed from a
homogeneous solution, the aluminum ions are uniformly distributed
through the silica particles. This is distinct from aluminum doping
of silica particles, wherein already formed silica particles are
contacted with a solution containing aluminum ions such that the
aluminum ions become associated with the surface of the silica
particles. A non-limiting example of suitable silica particles
containing aluminum ions is the TX13573 product from Nalco.
[0009] The silica particles can have any suitable average particle
size (i.e., average particle diameter). For spherical silica
particles, the size of the particle is the diameter of the
particle. For non-spherical silica particles, the size of the
particle is the diameter of the smallest sphere that encompasses
the particle. The particle size of the silica can be measured using
any suitable technique, for example, using laser diffraction
techniques. Suitable particle size measurement instruments are
available from, for example, Malvern Instruments (Malvern, UK). If
the average silica particle size is too small, the polishing
composition may not exhibit sufficient removal rate. In contrast,
if the average silica particle size is too large, the polishing
composition may exhibit undesirable polishing performance such as,
for example, poor substrate defectivity.
[0010] Accordingly, the silica particles can have an average
particle size of about 40 nm or more, for example, about 45 nm or
more, or about 50 nm or more. Alternatively, or in addition, the
silica particles can have an average particle size of about 80 nm
or less, for example, about 75 nm or less, about 70 nm or less,
about 65 nm or less, or about 60 nm or less. Thus, the silica
particles can have an average particle size bounded by any two of
the aforementioned endpoints. For example, the silica particles can
have an average particle size of about 40 nm to about 80 nm, about
40 nm to about 75 nm, about 40 nm to about 70 nm, about 40 nm to
about 65 nm, about 40 nm to about 60 nm, about 45 nm to about 80
nm, about 45 nm to about 75 nm, about 45 nm to about 70 nm, about
45 nm to about 65 nm, about 45 nm to about 60 nm, about 50 nm to
about 80 nm, about 50 nm to about 75 nm, about 50 nm to about 70
nm, about 50 nm to about 65 nm, or about 50 nm to about 60 nm.
[0011] The silica particles preferably are colloidally stable in
the inventive polishing composition. The term colloid refers to the
suspension of silica particles in the liquid carrier (e.g., water).
Colloidal stability refers to the maintenance of that suspension
through time. In the context of this invention, silica particles
are considered colloidally stable if, when the silica particles are
placed into a 100 mL graduated cylinder and allowed to stand
unagitated for a time of 2 hours, the difference between the
concentration of particles in the bottom 50 mL of the graduated
cylinder ([B] in terms of g/mL) and the concentration of particles
in the top 50 mL of the graduated cylinder ([T] in terms of g/mL)
divided by the initial concentration of silica particles in the
composition ([C] in terms of g/mL) is less than or equal to 0.5
(i.e., {[B]-[T]}/[C]<0.5). More preferably, the value of
[B]-[T]/[C] is less than or equal to 0.3, and most preferably is
less than or equal to 0.1.
[0012] The polishing composition can comprise any suitable amount
of silica particles. If the polishing composition of the invention
comprises too little silica, the composition may not exhibit a
sufficient removal rate. In contrast, if the polishing composition
comprises too much silica, then the polishing composition may
exhibit undesirable polishing performance, may not be cost
effective, and/or may lack stability. The polishing composition can
comprise about 10 wt. % or less of silica particles, for example,
about 9 wt. % or less, about 8 wt. % or less, about 7 wt. % or
less, about 6 wt. % or less, about 5 wt. % or less, about 4 wt. %
or less, about 3 wt. % or less, about 2 wt. % or less, about 1 wt.
% or less, about 0.9 wt. % or less, about 0.8 wt. % or less, about
0.7 wt. % or less, about 0.6 wt. % or less, or about 0.5 wt. % or
less of silica particles. Alternatively, or in addition, the
polishing composition can comprise about 0.05 wt. % or more of
silica particles, for example, about 0.1 wt. % or more, about 0.2
wt. % or more, about 0.3 wt. % or more, about 0.4 wt. % or more,
about 0.5 wt. % or more, or about 1 wt. % or more of silica
particles. Thus, the polishing composition can comprise silica
particles in an amount bounded by any two of the aforementioned
endpoints. For example, the polishing composition can comprise
about 0.05 wt. % to about 10 wt. % of silica particles, for
example, 0.1 wt. % to about 10 wt. %, about 0.1 wt. % to about 9
wt. %, about 0.1 wt. % to about 8 wt. %, about 0.1 wt. % to about 7
wt. %, about 0.1 wt. % to about 6 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 0.2 wt. % to about 2 wt. %, about 0.2 wt. % to about 1
wt. %, about 0.2 wt. % to about 0.6 wt. %, or about 0.3 wt. % to
about 0.5 wt. % of silica particles. In an embodiment, the
polishing composition comprises about 0.5 wt. % to about 3 wt. % of
silica particles (e.g., about 1 wt. % to about 3 wt. % of silica
particles, or about 1 wt. % to about 2 wt. % of silica
particles).
[0013] The polishing composition comprises a polymer comprising
sulfonic acid monomeric units, referred to hereinafter as a
sulfonic acid polymer or copolymer. The sulfonic acid monomeric
units can be any suitable sulfonic acid monomeric units comprising
one or more groups of the formula: --SO.sub.3H. Non-limiting
examples of suitable sulfonic acid (homo)polymers include
polyvinylsulfonic acid, polystyrenesulfonic acid (e.g.,
poly(4-styrenesulfonic acid)), polyallylsulfonic acid, poly ethyl
acrylate sulfonic acid, poly butyl acrylate sulfonic acid, poly
isoprenesulfonic acid, and the like. Suitable sulfonic acid
copolymers include copolymers comprising sulfonic acid monomeric
units and monomers comprising carboxylic acid groups or derivatives
of carboxylic acid groups such as amides. Non-limiting examples of
suitable sulfonic acid copolymers include
poly(2-acrylamide-2-methylpropanesulfonic acid),
poly(4-styrenesulfonic acid-co-maleic acid), and the like. In a
preferred embodiment, the sulfonic acid polymer is
polystyrenesulfonic acid. The sulfonic acid polymer can be provided
in its free acid form, as a salt thereof, or as a partial salt
thereof.
[0014] The sulfonic acid polymer or copolymer can have any suitable
molecular weight. The sulfonic acid polymer or copolymer can have
an average molecular weight of about 50,000 g/mol or more, for
example, about 55,000 g/mol or more, about 60,000 g/mol or more,
about 65,000 g/mol or more, about 70,000 g/mol or more, about
75,0000 g/mol or more, about 80,000 g/mol or more, about 85,000
g/mol or more, about 90,000 g/mol or more, about 95,000 g/mol or
more, about 100,000 g/mol or more, about 110,000 g/mol or more,
about 120,000 g/mol or more, about 130,000 g/mol or more, about
140,000 g/mol or more, or about 150,000 g/mol or more.
Alternatively, or in addition, the sulfonic acid polymer or
copolymer can have an average molecular weight of about 200,000
g/mol or less, for example, about 195,000 g/mol or less, about
190,000 g/mol or less, about 185,000 g/mol or less, about 180,000
g/mol or less, about 175,000 g/mol or less, about 170,000 g/mol or
less, about 165,000 g/mol or less, about 160,000 g/mol or less,
about 155,000 g/mol or less, or about 150,000 g/mol or less. Thus,
the sulfonic acid polymer or copolymer can have an average
molecular weight bounded by any two of the aforementioned
endpoints. For example, the sulfonic acid polymer or copolymer can
have an average molecular weight of about 50,000 g/mol to about
200,000 g/mol, about 60,000 g/mol to about 200,000 g/mol, about
70,000 g/mol to about 200,000 g/mol, about 75,000 g/mol to about
200,000 g/mol, about 80,000 g/mol to about 200,000 g/mol, about
90,000 g/mol to about 200,000 g/mol, about 100,000 g/mol to about
200,000 g/mol, about 50,000 g/mol to about 190,000 g/mol, about
50,000 g/mol to about 180,000 g/mol, about 50,000 g/mol to about
170,000 g/mol, about 50,000 g/mol to about 160,000 g/mol, about
50,000 g/mol to about 150,000 g/mol, or about 75,000 g/mol to about
150,000 g/mol.
[0015] The polishing composition comprises any suitable amount of
the sulfonic acid polymer or copolymer. The amount of sulfonic acid
polymer or copolymer refers to the total amount of sulfonic acid
polymer or copolymer present in the polishing composition. The
polishing composition can comprise about 1 ppm or more of the
sulfonic acid polymer or copolymer, for example, about 5 ppm or
more, about 10 ppm or more, about 20 ppm or more, about 30 ppm or
more, about 40 ppm or more, or about 50 ppm or more. Alternatively,
or in addition, the polishing composition can comprise about 500
ppm or less of the sulfonic acid polymer or copolymer, for example,
about 450 ppm or less, about 400 ppm or less, about 350 ppm or
less, about 300 ppm or less, about 250 ppm or less, about 200 ppm
or less, about 150 ppm or less, or about 100 ppm or less. Thus, the
polishing composition can comprise the sulfonic acid polymer or
copolymer in an amount bounded by any two of the aforementioned
endpoints. For example, the polishing composition can comprise
about 1 ppm to about 500 ppm of the sulfonic acid polymer or
copolymer, about 5 ppm to about 450 ppm, about 10 ppm to about 400
ppm, about 10 ppm to about 350 ppm, about 10 ppm to about 300 ppm,
about 10 ppm to about 250 ppm, about 10 ppm to about 200 ppm, about
20 ppm to about 300 ppm, about 20 ppm to about 250 ppm, about 20
ppm to about 200 ppm, about 20 ppm to about 150 ppm, about 20 ppm
to about 100 ppm, about 10 ppm to about 100 ppm, about 10 ppm to
about 90 ppm, about 10 ppm to about 80 ppm, about 10 ppm to about
70 ppm, about 10 ppm to about 60 ppm, about 10 ppm to about 50 ppm,
or about 10 ppm to about 40 ppm.
[0016] In certain embodiments, the polishing composition further
comprises an oxidizing agent. The oxidizing agent can be any
suitable oxidizing agent. Desirably, the oxidizing agent increases
the removal rate of silicon carbide when used to polish a substrate
comprising the same. A non-limiting example of a suitable oxidizing
agent is hydrogen peroxide.
[0017] The polishing composition can comprise any suitable amount
of the oxidizing agent. For example, the polishing composition can
comprise about 0.1 wt. % to about 5 wt. % of the oxidizing agent
(e.g., about 0.5 wt. % to about 3 wt. % of the oxidizing
agent).
[0018] The polishing composition comprises water. The water can be
any suitable water and can be, for example, deionized water or
distilled water. In some embodiments, the polishing composition can
further comprise one or more organic solvents in combination with
the water. For example, the polishing composition can further
comprise a hydroxylic solvent such as methanol or ethanol, a
ketonic solvent, an amide solvent, a sulfoxide solvent, and the
like. Preferably, the polishing composition comprises pure
water.
[0019] The polishing composition has a pH of about 2 to about 5.
Thus, the polishing composition can have a pH of about 2 or more,
e.g., about 2.2 or more, about 2.4 or more, about 2.6 or more,
about 2.8 or more, about 3.0 or more, about 3.2 or more, or about
3.4 or more. Alternatively, or in addition, the polishing
composition can have a pH of about 5 or less, e.g., about 4.8 or
less, about 4.6 or less, about 4.4 or less, about 4.2 or less, or
about 4.0 or less. Thus, the polishing composition can have a pH
bounded by any two of the aforementioned endpoints. For example the
polishing composition can have a pH of about 2 to about 5, e.g.,
about 2.2 to about 5, about 2.2 to about 4.8, about 2.4 to about
4.8, about 2.4 to about 4.6, about 2.4 to about 4.4, about 2.4 to
about 4.2, or about 2.6 to about 4.0.
[0020] The pH of the polishing composition can be adjusted using
any suitable acid or base. Non-limiting examples of suitable acids
include nitric acid, sulfuric acid, phosphoric acid, and organic
acids such as formic acid and acetic acid. Non-limiting examples of
suitable bases include sodium hydroxide, potassium hydroxide, and
ammonium hydroxide.
[0021] The polishing composition optionally further comprises a
buffering agent. The buffering agent can be any suitable buffering
agent capable of maintaining the polishing composition at a pH as
recited herein. Non-limiting examples of suitable buffering agents
include formic acid, malonic acid, acetic acid, oxalic acid, citric
acid, and phosphoric acid.
[0022] The chemical-mechanical polishing composition optionally
further comprises one or more additives. Illustrative additives
include conditioners, acids (e.g., sulfonic acids), complexing
agents (e.g., anionic polymeric complexing agents), chelating
agents, biocides, scale inhibitors, dispersants, etc.
[0023] A biocide, when present, can be any suitable biocide and can
be present in the polishing composition in any suitable amount. A
suitable biocide is an isothiazolinone biocide. The amount of
biocide in the polishing composition typically is about 1 ppm to
about 500 ppm, preferably about 10 ppm to about 125 ppm.
[0024] In certain embodiments, the polishing composition does not
contain a piperazine compound, a 4-morpholine compound, an amino
sulfonic acid compound, a substituted amine compound, a tertiary
amine compound, or a bis-amine compound, or salts thereof. As used
herein, the phrase "does not contain" means that the polishing
composition includes no more than trace contaminant amounts of the
recited compounds, which amounts are insufficient to affect any
SiC, SiN, or SiO removal rates obtainable with the polishing
composition during polishing. In certain embodiments, the polishing
composition does not contain a substituted 4-morpholine derivative
such as 3-(N-morpholino)propanesulfonic acid (MOPS),
4-morpholineethanesulfonic acid (MES),
.beta.-hydroxy-4-morpholinepropanesulfonic acid (MOPSO), and
combinations thereof. In certain embodiments, the polishing
composition does not contain an amino sulfonic acid such as
2-[(2-hydroxy-1,1-bis(hydroxymethyl)ethyl)amino]ethanesulfonic acid
(TES), N-[tris(hydroxymethyl)methyl]-3-aminopropanesulfonic acid
(TAPS), N-tris(hydroxymethyl)methyl-4-aminobutanesulfonic acid
(TABS), N-(2-acetamido)-2-aminoethanesulfonic acid (ACES),
N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid (BES),
3-(cyclohexylamino)-1-propanesulfonic acid (CAPS),
2-(cyclohexylamino)ethanesulfonic acid (CHES), and combinations
thereof. In certain embodiments, the polishing composition does not
contain a substituted amine compound such as
2-hydroxy-3-[tris(hydroxymethyl)methylamino]-1-propanesulfonic acid
(TAPSO), N-[tris(hydroxymethyl)methyl]glycine (TRICINE),
N,N-bis(2-hydroxyethyl)glycine (BICINE),
N-(2-acetamido)iminodiacetic acid (ADA),
2,2-bis(hydroxymethyl)-2,2',2''-nitrilotriethanol (BIS-TRIS),
3-(cyclohexylamino)-2-hydroxy-1-propanesulfonic acid (CAPSO),
3-(N,N-bis[2-hydroxyethyl]amino)-2-hydroxypropanesulfonic acid
(DIPSO), and combinations thereof. In certain embodiments, the
polishing composition does not contain a substituted bis-amine
compound such as 1,3-bis[tris(hydroxymethyl)methylamino]propane
(BIS-TRIS PROPANE).
[0025] The polishing composition can be prepared by any suitable
technique, many of which are known to those skilled in the art. The
polishing composition can be prepared in a batch or continuous
process. Generally, the polishing composition can be prepared by
combining the components thereof in any order. The term "component"
as used herein includes individual ingredients (e.g., silica
particles, sulfonic acid polymer or copolymer, optional buffering
agent, optional oxidizing agent, optional pH adjustor, etc.) as
well as any combination of ingredients (e.g., silica particles,
sulfonic acid polymer or copolymer, optional buffering agent,
optional oxidizing agent, optional pH adjustor, etc.).
[0026] For example, the silica particles can be dispersed in water.
The sulfonic acid polymer or copolymer, optional buffering agent,
and optional oxidizing agent can then be added and mixed by any
method that is capable of incorporating the components into the
polishing composition. The oxidizing agent can be added at any time
during the preparation of the polishing composition. The polishing
composition can be prepared prior to use, with one or more
components, such as the oxidizing agent, added to the polishing
composition just before use (e.g., within about 1 minute before
use, or within about 1 hour before use, or within about 7 days
before use). The polishing composition also can be prepared by
mixing the components at the surface of the substrate during the
polishing operation.
[0027] The polishing composition can be supplied as a one-package
system comprising silica particles, sulfonic acid polymer or
copolymer, optional buffering agent, optional oxidizing agent,
optional pH adjustor, and water. Alternatively, the silica
particles can be supplied as a dispersion in water in a first
container, and the sulfonic acid polymer or copolymer, optional
buffering agent, optional oxidizing agent, and optional pH adjustor
can be supplied in a second container, either in dry form, or as a
solution or dispersion in water. The oxidizing agent desirably is
supplied separately from the other components of the polishing
composition and is combined, e.g., by the end-user, with the other
components of the polishing composition shortly before use (e.g., 1
week or less prior to use, 1 day or less prior to use, 1 hour or
less prior to use, 10 minutes or less prior to use, or 1 minute or
less prior to use). The components in the first or second container
can be in dry form while the components in the other container can
be in the form of an aqueous dispersion. Moreover, it is suitable
for the components in the first and second containers to have
different pH values, or alternatively to have substantially
similar, or even equal, pH values. Other two-container, or three or
more-container, combinations of the components of the polishing
composition are within the knowledge of one of ordinary skill in
the art.
[0028] The polishing composition of the invention also can be
provided as a concentrate which is intended to be diluted with an
appropriate amount of water prior to use. In such an embodiment,
the polishing composition concentrate can comprise the silica
particles, sulfonic acid polymer or copolymer, optional buffering
agent, optional pH adjustor, with or without the optional oxidizing
agent, in amounts such that, upon dilution of the concentrate with
an appropriate amount of water, and the oxidizing agent if not
already present in an appropriate amount, each component of the
polishing composition will be present in the polishing composition
in an amount within the appropriate range recited above for each
component. For example, the silica particles, sulfonic acid polymer
or copolymer, optional buffering agent, and optional pH adjustor
can each be present in the concentration in an amount that is about
2 times (e.g., about 3 times, about 4 times, or about 5 times)
greater than the concentration recited above for each component so
that, when the concentrate is diluted with an equal volume of water
(e.g., 2 equal volumes of water, 3 equal volumes of water, or 4
equal volumes of water, respectively), along with the optional
oxidizing agent in a suitable amount, each component will be
present in the polishing composition in an amount within the ranges
set forth above for each component. Furthermore, as will be
understood by those of ordinary skill in the art, the concentrate
can contain an appropriate fraction of the water present in the
final polishing composition in order to ensure that other
components are at least partially or fully dissolved in the
concentrate.
[0029] The invention also provides a method of chemically
mechanically polishing a substrate comprising (i) providing a
substrate, wherein the substrate comprises a silicon carbide layer
on a surface of the substrate; (ii) providing a polishing pad;
(iii) providing a polishing composition comprising (a) silica
particles, (b) a polymer comprising sulfonic acid monomeric units,
and (c) water, wherein the polishing composition has a pH of about
2 to about 5; (iv) contacting the substrate with the polishing pad
and the polishing composition; and (v) moving the polishing pad and
the polishing composition relative to the substrate to abrade at
least a portion of the silicon carbide layer on a surface of the
substrate to polish the substrate.
[0030] The chemical-mechanical polishing composition can be used to
polish any suitable substrate and is especially useful for
polishing substrates comprising at least one layer (typically a
surface layer) comprised of silicon carbide. Suitable substrates
include wafers used in the semiconductor industry. The wafers
typically comprise or consist of, for example, a metal, metal
oxide, metal nitride, metal composite, metal alloy, a low
dielectric material, or combinations thereof. The method of the
invention is particularly useful for polishing substrates
comprising silicon carbide, silicon nitride, and/or silicon oxide,
e.g., any one, two, or especially all three of the aforementioned
materials. In a preferred embodiment, the chemical-mechanical
polishing composition can be used to polish a substrate comprising
a silicon carbide layer on a surface of the substrate.
[0031] In certain embodiments, the substrate comprises silicon
carbide in combination with silicon nitride and/or silicon oxide.
The silicon carbide can be any suitable silicon carbide, many forms
of which are known in the art. The silicon carbide can have any
suitable polytype. The silicon nitride can be any suitable silicon
nitride. The silicon oxide similarly can be any suitable silicon
oxide, many forms of which are known in the art. Suitable types of
silicon oxide include, but are not limited to, TEOS,
borophosphosilicate glass (BPSG), PETEOS, thermal oxide, undoped
silicate glass, and HDP oxide.
[0032] The chemical-mechanical polishing composition of the
invention desirably exhibits a high removal rate when polishing a
substrate comprising silicon carbide according to a method of the
invention. For example, when polishing silicon wafers comprising
silicon carbide in accordance with an embodiment of the invention,
the polishing composition desirably exhibits a silicon carbide
removal rate of about 500 .ANG./min or higher, about 700 .ANG./min
or higher, about 800 .ANG./min or higher, about 900 .ANG./min or
higher, about 1,000 .ANG./min or higher, about 1,100 .ANG./min or
higher, about 1,250 .ANG./min or higher, about 1,500 .ANG./min or
higher, about 1,750 .ANG./min or higher, or about 2,000 .ANG./min
or higher.
[0033] The chemical-mechanical polishing composition of the
invention desirably exhibits a low removal rate when polishing a
substrate comprising silicon nitride according to a method of the
invention. For example, when polishing silicon wafers comprising
silicon nitride in accordance with an embodiment of the invention,
the polishing composition desirably exhibits a removal rate of the
silicon nitride of about 200 .ANG./min or lower, for example, about
150 .ANG./min or lower, about 100 .ANG./min or lower, about 90
.ANG./min or lower, about 80 .ANG./min or lower, about 70 .ANG./min
or lower, about 60 .ANG./min or lower, about 50 .ANG./min or lower,
about 40 .ANG./min or lower, or even about 30 .ANG./min or lower.
Thus, when used to polish a substrate comprising a silicon carbide
layer and a silicon nitride layer, the polishing composition
desirably exhibits selectivity for the polishing of the silicon
carbide layer over the silicon nitride layer. Selectivity for the
polishing of a first material over a second material can be defined
as the ratio of removal rates of the first material and the second
material. When the removal rate of the first material is greater
than the removal rate of the second material, the polishing
composition can be considered to exhibit selectivity for the
removal of the first material.
[0034] The chemical-mechanical polishing composition of the
invention desirably exhibits a low removal rate when polishing a
substrate comprising silicon oxide according to a method of the
invention. For example, when polishing silicon wafers comprising
silicon oxide in accordance with an embodiment of the invention,
such as high density plasma (HDP) oxides, plasma-enhanced
tetraethyl orthosilicate (PETEOS), and/or tetraethyl orthosilicate
(TEOS), the polishing composition desirably exhibits a removal rate
of the silicon oxide of about 200 .ANG./min or lower, for example,
about 150 .ANG./min or lower, about 100 .ANG./min or lower, about
90 .ANG./min or lower, about 80 .ANG./min or lower, about 70
.ANG./min or lower, about 60 .ANG./min or lower, about 50 .ANG./min
or lower, about 40 .ANG./min or lower, or even about 30 .ANG./min
or lower. Thus, when used to polish a substrate comprising a
silicon carbide layer and a silicon oxide layer, the polishing
composition desirably exhibits selectivity for the polishing of the
silicon carbide layer over the silicon oxide layer.
[0035] The chemical-mechanical polishing composition of the
invention can be tailored to provide effective polishing at the
desired polishing ranges selective to specific thin layer
materials, while at the same time minimizing surface imperfections,
defects, corrosion, erosion, and the removal of stop layers. The
selectivity can be controlled, to some extent, by altering the
relative concentrations of the components of the polishing
composition. When desirable, the chemical-mechanical polishing
composition of the invention can be used to polish a substrate with
a silicon carbide to silicon nitride polishing selectivity of about
5:1 or higher (e.g., about 10:1 or higher, about 15:1 or higher,
about 25:1 or higher, about 50:1 or higher, about 100:1 or higher,
or about 150:1 or higher). Also, the chemical-mechanical polishing
composition of the invention can be used to polish a substrate with
a silicon carbide to silicon oxide polishing selectivity of about
5:1 or higher (e.g., about 10:1 or higher, about 15:1 or higher,
about 25:1 or higher, about 50:1 or higher, about 100:1 or higher,
or about 150:1 or higher). Thus, in embodiments, when used to
polish substrates comprising at least one layer of silicon carbide
and at least one layer of silicon nitride and/or at least one layer
of silicon oxide, the polishing composition and polishing method
allow for the preferential removal of silicon carbide as compared
with the removal of silicon nitride and/or silicon oxide.
[0036] The chemical-mechanical polishing composition and method of
the invention are particularly suited for use in conjunction with a
chemical-mechanical polishing apparatus. Typically, the apparatus
comprises a platen, which, when in use, is in motion and has a
velocity that results from orbital, linear, or circular motion, a
polishing pad in contact with the platen and moving with the platen
when in motion, and a carrier that holds a substrate to be polished
by contacting and moving the substrate relative to the surface of
the polishing pad. The polishing of the substrate takes place by
the substrate being placed in contact with the polishing pad and
the polishing composition of the invention, and then the polishing
pad moving relative to the substrate, so as to abrade at least a
portion of a surface of the substrate to polish the substrate.
[0037] A substrate can be polished with the chemical-mechanical
polishing composition using any suitable polishing pad (e.g.,
polishing surface). Suitable polishing pads include, for example,
woven and non-woven polishing pads. Moreover, suitable polishing
pads can comprise any suitable polymer of varying density,
hardness, thickness, compressibility, ability to rebound upon
compression, and compression modulus. Suitable polymers include,
for example, polyvinylchloride, polyvinylfluoride, nylon,
fluorocarbon, polycarbonate, polyester, polyacrylate, polyether,
polyethylene, polyamide, polyurethane, polystyrene, polypropylene,
coformed products thereof, and mixtures thereof. Soft polyurethane
polishing pads are particularly useful in conjunction with the
inventive polishing method. Typical pads include but are not
limited to SURFIN.TM. 000, SURFIN.TM. SSW1, SPM3100 (commercially
available from, for example, Eminess Technologies), POLITEX.TM.,
and Fujibo POLYPAS.TM. 27 (Fujibo H7000, H800, H600, H804 etc. not
sure if these examples are really needed).
[0038] Desirably, the chemical-mechanical polishing apparatus
further comprises an in situ polishing endpoint detection system,
many of which are known in the art. Techniques for inspecting and
monitoring the polishing process by analyzing light or other
radiation reflected from a surface of the substrate being polished
are known in the art. Such methods are described, for example, in
U.S. Pat. Nos. 5,196,353, 5,433,651, 5,609,511, 5,643,046,
5,658,183, 5,730,642, 5,838,447, 5,872,633, 5,893,796, 5,949,927,
and 5,964,643. Desirably, the inspection or monitoring of the
progress of the polishing process with respect to a substrate being
polished enables the determination of the polishing end-point,
i.e., the determination of when to terminate the polishing process
with respect to a particular substrate.
[0039] The following examples further illustrate the invention but,
of course, should not be construed as in any way limiting its
scope.
Example 1
[0040] This example compares the removal rates of silicon carbide
(SiC) and silicon nitride (SiN) exhibited by polishing compositions
comprising silica particles containing aluminum ions and sulfonic
acid polymers or copolymers.
[0041] Separate substrates comprising blanket layers of SiC and SiN
were polished with nine different polishing compositions, i.e.,
Polishing Compositions 1A-1I. Each of Polishing Compositions 1A-1I
comprised 1.0 wt. % of Nalco TX13573 silica, 120 ppm of a buffering
agent, 2 wt. % of hydrogen peroxide, and 15 ppm Kordek.TM. biocide
(Dow Chemical, Midland, Mich.) in water at a pH of 3.5. Polishing
Compositions 1A-1I also included a sulfonic acid polymer or
copolymer and buffering agent set forth in Table 1.
TABLE-US-00001 TABLE 1 Components of Polishing Compositions 1A-1I
Polish- Amount of ing Sulfonic Acid Composi- Sulfonic Acid Polymer
Or Polymer Or Buffering tion Copolymer Copolymer Agent 1A None 0
Formic Acid 1B Poly(4-styrenesulfonic acid) 25 ppm Formic (MW
75,000) acid 1C Poly(4-styrenesulfonic acid-co- 25 ppm Formic
maleic acid), sodium salt (3:1) acid 1D Poly(4-styrenesulfonic
acid-co- 25 ppm Formic maleic acid), sodium salt (1:1) acid (MW
15,000) 1E Poly(4-styrenesulfonic acid), 25 ppm Formic ammonium
salt (MW 200,000) acid 1F Poly(4-styrenesulfonic acid-co- 25 ppm
Formic maleic acid), sodium salt (1:1) acid (MW 20,000) 1G
Poly(2-acrylamide-2- 25 ppm Formic methylpropanesulfonic acid) acid
1H Dioctylsulfosuccinate 25 ppm Formic acid 1I
Dioctylsulfosuccinate 250 ppm Formic acid
[0042] Following polishing, the removal rates were determined, and
the results are set forth in Table 2.
TABLE-US-00002 TABLE 2 Removal Rates of SiC and SiN as a Function
of Type of Sulfonic Acid Polymer or Copolymer Polish- SiC SiN ing
Removal Removal SiC/SiN Composi- Rate Rate Selec- tion (.ANG./min)
(.ANG./min) tivity 1A (control) 1138 729 1.6 1B (inventive) 1062 48
22.1 1C (inventive) 1046 208 5.0 1D (inventive) 706 35 20.2 1E
(inventive) 1100 34 32.4 1F (inventive) 953 42 22.7 1G (inventive)
1082 67 16.1 1H (comparative) 889 775 1.1 1I (comparative) 158 30
5.3
[0043] As is apparent from the results set forth in Table 2,
inventive Polishing Compositions 1B-1G desirably exhibited good SiC
removal rates and SiC/SiN selectivities of approximately 5.0 to
32.4. The selectivities are calculated by determining the ratio of
SiC to SiN removal rates. Polishing Composition 1H, which contained
dioctylsulfosuccinate, exhibited a lower SiC removal rate and a
lower SiC/SiN selectivity than control Polishing Composition 1A.
Increasing the amount of dioctylsulfosuccinate in comparative
Polishing Composition 1I to 250 ppm (i.e., increasing the amount of
a monomeric sulfonic acid) improved the SiC/SiN selectivity as
compared to comparative Polishing Composition 1H, but significantly
reduced the SiC removal rate as well.
Example 2
[0044] This example demonstrates the effect of the amount of
polystyrenesulfonic acid (i.e., a sulfonic acid polymer) on SiC,
SiN, and silicon oxide (SiO) removal rates exhibited by polishing
compositions comprising silica particles containing aluminum ions
and hydrogen peroxide.
[0045] Separate substrates comprising blanket layers of SiC, SiN
and SiO were polished with five different polishing compositions,
i.e., Polishing Compositions 2A-2E. Each of Polishing Compositions
2A-2E comprised 1.0 wt. % of Nalco TX13573 silica, 120 ppm of a
formic acid (i.e., a buffering agent), 2 wt. % of hydrogen
peroxide, and 15 ppm Kordek.TM. biocide in water at a pH of 3.5.
Polishing Compositions 2B-2E also contained polystyrenesulfonic
acid (PSA) in the amounts set forth in Table 3.
[0046] Following polishing, the removal rates of SiC, SiN and SiO
were determined, and the results are set forth in Table 3.
TABLE-US-00003 TABLE 3 Removal Rates of SiC, SiO, and SiN as a
Function of Polystyrenesulfonic Acid (PSA) Concentration Polish-
PSA SiC SiO SiN ing Concen- Removal Removal Removal SiC/SiN
Composi- tration Rate Rate Rate Selec- tion (ppm) (.ANG./min)
(.ANG./min) (.ANG./min) tivity 2A (control) 0 1138 86 729 1.6 2B
(inventive) 5 1076 100 378 2.8 2C (inventive) 15 1057 107 64 16.5
2D (inventive) 25 1062 104 48 22.1 2E (inventive) 35 813 77 14
58.1
[0047] As is apparent from the results set forth in Table 3, the
addition of polystyrenesulfonic acid to Polishing Compositions
2B-2E had little effect on the removal rate of SiO. Increasing the
concentration of polystyrenesulfonic acid from 0 ppm to 25 ppm
resulted in an increase in the SiC/SiN selectivity from
approximately 1.6 to approximately 22.1, while the SiC removal rate
decreased approximately 6.7%. Increasing the concentration of
polystyrenesulfonic acid to 35 ppm resulted in a SiC/SiN
selectivity of approximately 58.1, but a reduction in the SiC
removal rate of approximately 71.4% the removal rate exhibited by
control Polishing Composition 2A, which did not comprise any
polystyrenesulfonic acid. Thus, the presence of 5-35 ppm of
polystyrenesulfonic acid resulted in a desirable increase in the
SiC/SiN selectivity while maintaining good SiC removal rates. When
the amount of polystyrenesulfonic acid was increased to 35 ppm, the
SiC/SiN selectivity increased, but the SiC removal rate
decreased.
Example 3
[0048] This example demonstrates the effect of pH on SiC, SiN, and
SiO removal rates exhibited by polishing compositions comprising
silica particles containing aluminum ions and sulfonic acid
polymers or copolymers.
[0049] Separate substrates comprising blanket layers of SiC, SiN
and SiO were polished with seven different polishing compositions,
i.e., Polishing Compositions 3A-3G. Each of Polishing Compositions
3A-3G comprised 1.0 wt. % of Nalco TX13573 silica, 25 ppm of
polystyrenesulfonic acid (i.e., a sulfonic acid polymer), 120 ppm
of formic acid (i.e., a buffering agent), 2 wt. % of hydrogen
peroxide, and 15 ppm Kordek.TM. biocide in water. The pH values of
Polishing Compositions 3A-3G are reported in Table 4.
[0050] Following polishing, the removal rates of SiC, SiN and SiO
were determined, and the results are set forth in Table 4.
TABLE-US-00004 TABLE 4 Removal Rates of SiC, SiO, and SiN as a
Function of Polishing Composition pH SiC SiO SiN Removal Removal
Removal Polishing Rate Rate Rate SiC/SiN SiC/SiO Composition pH
(.ANG./min) (.ANG./min) (.ANG./min) Selectivity Selectivity 3A
(inventive) 2.5 1117 293 46 24.3 3.8 3B (inventive) 3.0 966 128 40
24.2 7.5 3C (inventive) 3.5 819 92 27 30.3 8.9 3D (inventive) 4.0
1077 78 25 43.1 13.8 3E (inventive) 4.5 1129 76 24 47.0 14.9 3F
(inventive) 5.0 1071 80 25 42.8 13.4 3G (comparative) 6.0 487 81 27
18.0 6.0
[0051] As is apparent from the results set forth in Table 4, the
SiC removal rate remained high from pH 2.5 to pH 5.0, but the SiC
removal rate at pH 6.0 was approximately 45% of the removal rate at
pH 5.0. The SiC/SiN selectivity ranged from 24.3 at pH 2.5 to 47.0
at pH 4.5, but was 18.0 at pH 6.0. The SiC/SiO selectivity
increased from 3.8 at pH 2.5 to 7.5 at pH 3.0 and decreased from
13.4 at pH 5.0 to 6.0 at pH 6.0. Thus, in these embodiments, the
SiC/SiN selectivity was optimized in a pH range of 3.0 and 5.0. At
a pH value of 2.5, the SiO removal rate was more than twice the
removal rate observed at a pH value of 3.0. At a pH value of 6.0,
the SiN removal rate was less than half the SiN removal rate
observed at a pH of 5.0.
Example 4
[0052] This example demonstrates the effect of silica particles on
the SiC, SiN, and SiO removal rates exhibited by polishing
compositions further comprising sulfonic acid polymers or
copolymers and a buffering agent.
[0053] Separate substrates comprising blanket layers of SiC, SiN
and SiO were polished with seven different polishing compositions,
i.e., Polishing Compositions 4A-4G. Each of Polishing Compositions
4A-4G comprised 25 ppm of polystyrenesulfonic acid (i.e., a
sulfonic acid polymer), 120 ppm of formic acid (i.e., a buffering
agent), 2 wt. % of hydrogen peroxide, and 15 ppm Kordek.TM. biocide
in water at a pH of 3.5. Each of Polishing Compositions 4A-4G
further comprised 1.0 wt. % of the type of silica listed in Table
5. CMC WL-83A is a colloidal silica particle that has been surface
modified with aluminum ions, as described in U.S. Published
Application 2016/0222254.
[0054] Following polishing, the removal rates of SiC, SiN and SiO
were determined, and the results are set forth in Table 5.
TABLE-US-00005 TABLE 5 Removal Rates of SiC, SiN and SiO as a
Function of Silica Particles SiC SiN SiO Removal Removal Removal
Polishing Silica Rate Rate Rate SiC/SiN SiC/SiO Composition
Particles (.ANG./min) (.ANG./min) (.ANG./min) Selectivity
Selectivity 4A Nalco 1002 62 25 16.2 40.1 (inventive) TX13573 4B
Nissan 863 254 70 3.4 12.3 (inventive) ST-OYL 4C Fuso PL- 666 168
29 4.0 23.0 (inventive) 3D 4D CMC 1048 137 12 7.6 87.3 (inventive)
WL-83A 4E Nissan 631 124 38 5.1 16.6 (inventive) ST-OL-40 4F Nissan
1264 216 73 5.9 17.3 (inventive) ST-OZL-35 4G Nissan 927 183 7 5.1
132.4 (inventive) ST-PSMO
[0055] As is apparent from the results set forth in Table 5,
Polishing Composition 4A, which contained Nalco TX13573 silica
particles, exhibited the highest SiC/SiN selectivity. Polishing
Composition 4F, which contained Nissan ST-OZL-35 silica particles,
exhibited the highest SiC removal rate. Polishing Composition 4G,
which contained the Nissan ST-PSMO silica, exhibited the highest
SiC/SiO selectivity. These results demonstrate that removal rates
of SiC, SiN, and SiO and the SiC/SiN and SiC/SiO selectivities can
be tailored through the use of particular silica particles.
[0056] All references, including publications, patent applications,
and patents, cited herein are hereby incorporated by reference to
the same extent as if each reference were individually and
specifically indicated to be incorporated by reference and were set
forth in its entirety herein.
[0057] The use of the terms "a" and "an" and "the" and "at least
one" and similar referents in the context of describing the
invention (especially in the context of the following claims) are
to be construed to cover both the singular and the plural, unless
otherwise indicated herein or clearly contradicted by context. The
use of the term "at least one" followed by a list of one or more
items (for example, "at least one of A and B") is to be construed
to mean one item selected from the listed items (A or B) or any
combination of two or more of the listed items (A and B), unless
otherwise indicated herein or clearly contradicted by context. The
terms "comprising," "having," "including," and "containing" are to
be construed as open-ended terms (i.e., meaning "including, but not
limited to,") unless otherwise noted. Recitation of ranges of
values herein are merely intended to serve as a shorthand method of
referring individually to each separate value falling within the
range, unless otherwise indicated herein, and each separate value
is incorporated into the specification as if it were individually
recited herein. All methods described herein can be performed in
any suitable order unless otherwise indicated herein or otherwise
clearly contradicted by context. The use of any and all examples,
or exemplary language (e.g., "such as") provided herein, is
intended merely to better illuminate the invention and does not
pose a limitation on the scope of the invention unless otherwise
claimed. No language in the specification should be construed as
indicating any non-claimed element as essential to the practice of
the invention.
[0058] Preferred embodiments of this invention are described
herein, including the best mode known to the inventors for carrying
out the invention. Variations of those preferred embodiments may
become apparent to those of ordinary skill in the art upon reading
the foregoing description. The inventors expect skilled artisans to
employ such variations as appropriate, and the inventors intend for
the invention to be practiced otherwise than as specifically
described herein. Accordingly, this invention includes all
modifications and equivalents of the subject matter recited in the
claims appended hereto as permitted by applicable law. Moreover,
any combination of the above-described elements in all possible
variations thereof is encompassed by the invention unless otherwise
indicated herein or otherwise clearly contradicted by context.
* * * * *