Field of the art
This invention relates to a polishing body, and to be more
specific, relates to a polishing body wherein abrasive in the polishing body are
extremely dispersed well. The polishing body in the invention can be used favorably
as a polishing pad and the like for the polishing of the surfaces of semiconductor
wafers and the like.
Background art
Chemical mechanical polishing, also referred to as CMP,
has been conventionally used for polishing the surfaces of semiconductor wafers
and the like. In CMP, polishing is performed by sliding while pressing a surface
to be polished of the wafer and the like against a disk-like polishing pad and at
the same time, pouring a slurry (aqueous dispersion) wherein abrasive is dispersed,
onto the polishing pad. However, it is difficult to supply the slurry, which is
poured from above, between the surface to be polished and the polishing surface
of the polishing pad, which are pressed against each other at high pressure, and
it is said that the actual amount of functioning polishing agent is less than 1%
of the total amount supplied. Moreover, this slurry is expensive and furthermore,
vast costs are required for the treatment of used slurry.
Polishing body and the like that contain abrasive have
been disclosed in
Japanese Unexamined Patent Publication No. Hei-5-222356
,
Japanese Unexamined Patent Publication No. Hei-8-294869
,
Japanese Unexamined Patent Publication No. Hei-10-329032
,
Japanese Unexamined Patent Publication No. Hei-11-151659
,
Japanese Unexamined Patent Publication No. Hei-11-188647
and the like. However, with all of these cases, adequate prevention of
scratching on the surface to be polished is considered to be difficult to achieve.
EP 1 036 836 A1
which is prior art pursuant to Article 54(3) EPC discloses a CMP aqueous
dispersion used for the manufacture of semiconductor devices which contains polymer
particles, inorganic particles and water, wherein the zeta potential of the polymer
particles and the zeta potential of the inorganic particles are of opposite sign.
The polymer particles and the inorganic particles are electrostatically bonded to
form composite particles.
WO 99/24218
discloses a method of chemical-mechanical polishing of one or more substrates
in the manufacture of semiconductor devices, in which an aqueous fluid is placed
between a substrate and a fixed abrasive pad. The pad has a three dimensional fixed
abrasive polishing layer having a matrix material as a continuous phase and particles
as a discontinuous phase. The polishing layer is created by solidifying a flowable
material into a hydrophilic, polishing layer matrix. Bonded within or onto the polishing
layer matrix is a plurality of particulate matter.
GB 2 316 414 A
discloses an abrasive shaped article used for polishing a substrate material
such as a silicon wafer and an oxide substrate. The abrasive shaped article is made
by shaping an ultrafine silica powder into a shaped article, and sintering the shaped
article. In order to enhance the shapability of the silica powder, a binder or a
wax may be added into the silica powder.
Disclosure of the invention
The present invention solves the above problems. And it
is intended to provide a polishing body wherein abrasive is extremely dispersed
well, which provides stable polishing performance in the polishing process, and
which can effectively reduce the occurrence of scratches on the surface to be polished.
The present invention attains the object described above
by a polishing body as defined in claim 1.
Preferred embodiments are defined in the subclaims.
According to the polishing body in the invention, since
abrasive is extremely dispersed well even in the case where a large amount of abrasive
is contained, the polishing performance is stable and the occurrence of scratches
can be reduced effectively.
In another mode of the invention, the polishing body that
has a polishing part having a crosslinked structure shows excellent removal rate
even with a cutting product since deterioration of the polishing body due to heat
during a cutting process is not likely to occur. Thus this polishing body makes
processing of a required small distribution of thickness and cutting such as grooving
easier without lowering the polishing performance.
Furthermore according to the polishing body in another
mode of the invention, the particle size distribution of a powder that is a granular
product produced by spray drying, can be made narrow and uniform. The filled amount
in a mold in the process of powder molding is thus made stable, thereby reducing
the distribution of the weights of individual molded products, denseness distribution
within a polishing body may be reduced, and a stable polishing performance for each
polishing process will be obtained.
The present invention will now be described in more detail.
A polishing body in the invention is characterized in having
a polishing part formed by solidifying an aqueous dispersion containing dispersed
composite particles wherein abrasive is attached to a matrix material. This aqueous
dispersion containing composite particles may furthermore have a matrix material
and/or abrasive dispersed and contained therein.
That is, the polishing body in the invention is formed
by solidifying any aqueous dispersion among (1) an aqueous dispersion wherein composite
particles are contained and dispersed, (2) an aqueous dispersion wherein composite
particles and abrasive are contained and dispersed, (3) an aqueous dispersion wherein
composite particles and a matrix material are contained and dispersed, and (4) an
aqueous dispersion wherein composite particles, a matrix material, and abrasive
are contained and dispersed.
The above-mentioned "matrix material" is a material comprising
a matrix phase that holds the abrasive in the polishing body in the invention, and
is comprised of one component or two or more components. A homopolymer or a copolymer
(rubber, resin, thermoplastic elastomer and the like) may be used as the matrix
material. The matrix material may be crosslinked or uncrosslinked (a crosslinkable
material is included.). Examples of the matrix material may include diene-based
copolymers, styrene-based copolymers, (meth)acrylic-based resins, acrylic-based
copolymers, polyolefin-based resins, olefin-based copolymers, epoxy-based resins,
phenol-based resins, polyimide-based resins and the like. Among these, thermoplastic
resins such as (meth)acrylic-based resins, acrylic-based copolymers, polyolefin-based
resins, olefin-based copolymers and the like are normally used without crosslinking.
Also, epoxy-based resins, phenol-based resins, polyimide-based resins, diene-based
copolymers and the like prior to curing, are crosslinkable and are uncrosslinked
matrix materials. Furthermore, crosslinked products obtained by crosslinking such
crosslinkable materials [for example, cured thermoplastic resins (cured epoxy-based
resins, cured phenol-based resins, cured polyimide-based resins), crosslinked diene-based
copolymers and the like] are crosslinked matrix materials. Any of the matrix material
is preferably dispersed in the aqueous dispersion as particles with average particle
diameter of 10µm or less (and more preferably 0.3 to 3µm).
In particular, the above-mentioned "matrix material" preferably
is comprised of a crosslinkable polymer (including oligomers) and the above-mentioned
polishing part preferably has formed therein a crosslinked structure, in which the
crosslinkable polymer is crosslinked. In this case, the crosslinkable matrix material
may be dispersed in the uncrosslinked state in the aqueous dispersion and the matrix
material may be crosslinked during the process of solidifying the aqueous dispersion
or after solidification of the aqueous dispersion. In performing this crosslinking,
a crosslinkable oligomer and the like may be crosslinked without crosslinking agent,
or a crosslinking agent may be blended in the aqueous dispersion to perform crosslinking.
In these cases, crosslinking may be carried out by reaction under room temperature
or by heating. Also, an uncrosslinked thermoplastic resin may be crosslinked by
irradiation of radiation and the like. Such a polishing part having crosslinking
structure gives little surface deterioration due to heat during a cutting process.
Thus this polishing body makes processing of a required small distribution of thickness
and cutting such as grooving easier without lowering the polishing performance.
A non-crosslinking component as the matrix material may
be used in combination with a crosslinkable component. In this case, the amount
of the crosslinkable component is 15% by mass or more, more preferably 40% by mass
or more with respect to the total amount of the crosslinkable component and the
non-crosslinking component. The amount less than 15% by mass of the crosslinkable
component makes the effect of restraining the deterioration of the surface of the
polishing body lower.
In the process of solidifying the aqueous dispersion, if
integration by heating and the like is difficult due to the matrix material being
a crosslinking polymer, a crosslinking copolymer or the like, the matrix material
may be adhered by use of a binder. As this binder, the same copolymer and/or resin
as the above-mentioned matrix material may be used. It is especially preferable
to select components wherein the affinity of the matrix material and the binder
is good. Examples of the binder include epoxy-based resins, phenol-based resins,
polyimide-based resins, styrene-based resins, acrylic-based resins, olefin-based
resins and the like.
The above-mentioned matrix material having crosslinked
structure is also preferably dispersed in the aqueous dispersion as particles with
average particle diameter of 10µm or less (and more preferably 0.3 to 3µ
m).
The above-mentioned "abrasive" is a particle that mainly
exhibits mechanical polishing action and/or chemical polishing action. Examples
of such abrasive include particles comprised of cerium oxide, silica, alumina, titanium
oxide, chromium oxide, manganese dioxide, dimanganese trioxide, iron oxide, zirconium
oxide, silicon carbide, boron carbide, diamond, barium carbonate and the like. Among
these, cerium oxide, silica, alumina and the like, which have good affinity for
water, are preferable. In particular, cerium oxide is more preferable for its good
dispersion property in an emulsion.
The average particle diameter of the above-mentioned abrasive
is favorably 0.001 to 100µm (preferably 0.005 to 50µm, more preferably
0.005 to 10 µ m, and most preferably 0.01 to 1µm). If the average particle
diameter is less than 0.001µm, the polishing effect tends to be low. Meanwhile,
if the average particle diameter is exceeding 100µm, scratch tends to cause
since the abrasive are large. It is also preferable for the abrasive to have a particle
diameter in the preferable range given above even in the polishing body.
The above-mentioned "composite particles" are particles
wherein the abrasive is attached to the matrix material (the attachment is not limited
to the surface of the matrix material). The attaching method is not restricted in
particular, and for example the abrasive may be attached electrostatically by varying
the zeta potential with adjustment of the pH, etc. In this case, the zeta potentials
of the matrix material and the abrasive are opposite in sign and the potential difference
is 5mV or more (more preferably 10mV or more, even more preferably 20mV or more
and especially preferably 30mV or more). For this purpose, a matrix material and
the abrasive, which can exhibit the above-mentioned preferable zeta potential signs
and potential difference, should be selected. Also, the zeta potential of the matrix
material may be made closer to the desired value (a more negative value) by the
introduction of at least one type of group among the carboxyl group, sulfonic acid
group, amino group, sulfuric ester group, phosphoric ester group, ether-bonded part,
ester-bonded part and the like. In other words, though most zeta potentials of the
matrix material are negative over all pH range or over a wide range except for a
low pH range, the matrix material having a carboxyl group, sulfonic acid group and
the like may have definitely a negative zeta potential. And, the matrix material
having an amino group and the like can be the one having a positive zeta potential
within a specific pH range. Meanwhile, the zeta potential of abrasive highly depends
on pH, and has an isoelectric point at which this zeta potential becomes 0, and
the signs of the zeta potential change around this isoelectric point. Thus by choosing
a specific matrix material and abrasive, and mixing them in a pH range wherein their
zeta potentials will be opposite in sign, the matrix material and the abrasive may
be made into composite particles electrostatically. Also, even if the zeta potentials
are the same in sign during mixing, by changing the pH thereafter so that the zeta
potentials will be opposite in sign, the matrix material and the abrasive may be
made integral.
Furthermore, after attaching the abrasive, the composite
particle surface may be covered by a polycondensate of a silane coupling agent and
the like preventing from eliminating of the attached abrasive. This polycondensate
does not necessarily bond chemically to the composite particles, and, in particular,
a polycondensate that has grown three-dimensionally may be physically held on the
composite particle surface. Examples of such coated composite particles include
one composited by bonding polysiloxane and the like at least on the surface of the
particle after polycondensating a specific silane coupling agent and a specific
alkoxysilane, aluminum alkoxide, titanium alkoxide and the like in the presence
of particles that have been made into composite particles by electrostatically.
The dispersion medium of the above-mentioned "aqueous dispersion"
may be just a water or a mixed dispersion medium containing other dispersion medium
besides water. In the case of the mixed dispersion medium, the water content is
preferably 10% by mass or more (more preferably 20 mass % or more). Examples of
the dispersion medium besides water include non-protonic polar solvents, esters,
ketones, phenols, alcohols, amines, and other dispersion media. The dispersion medium
with a boiling point of 60 to 200°C (preferably 60 to 160°C) is used preferably
so that excessive evaporation will not occur in the preparation of the aqueous dispersion
and yet the removal of the dispersion medium can be performed readily.
The solid content of the aqueous dispersion is preferably
1 to 80% by mass (more preferably 10 to 60% by mass). Exceeding 80% by mass may
lower the dispersion stability of the aqueous dispersion and precipitation may occur.
The aqueous dispersion is preferably one wherein abrasive
is dispersed in an emulsion in which the matrix material is dispersed. Dispersing
abrasive in the emulsion makes a polishing body with well-dispersed abrasive. The
method of dispersing abrasive is not restricted in particular, and for example,
the dispersion may be obtained by mixing an emulsion containing a matrix material
which has been prepared by emulsion polymerization, suspension polymerization and
the like, and a dispersion wherein the abrasive is dispersed. Furthermore, the aqueous
dispersion may be obtained by dispersing the abrasive directly in the emulsion.
The method of producing an emulsion in which a matrix material
is dispersed is not restricted in particular, for example, the emulsion may be obtained
by emulsion polymerization, suspension polymerization and the like. The emulsion
may also be obtained by dissolving a priorly obtained matrix material in a solvent
or the like, and then dispersing the resulting solution.
Besides the dispersion medium, matrix material, abrasive
and composite particles, the aqueous dispersion may contain, as option, a binder
mentioned above, a surfactant, a vulcanizing agent, a vulcanization accelerator,
a crosslinking agent, a crosslinking promotor, a filler, a foaming agent, hollow
particles (expanding or non-expanding), which form voids, a softening agent, an
antioxidant, an ultraviolet absorber, an antistatic agent, a plasticizer and the
like. An oxidizing agent, a hydroxide of alkali metal, an acid, a pH adjuster, a
multivalent metal ion (chelating agent), a scratch prevention agent and the like
which have been conventionally contained in a slurry used in CMP, may also be contained
in the aqueous dispersion.
The above-mentioned surfactant may be a cationic surfactant,
an anionic surfactant or a nonionic surfactant. Examples of the cationic surfactant
include aliphatic amine salts, aliphatic ammonium salts and the like. Examples of
the anionic surfactant include fatty acid soaps, carboxylic acid salts such as salts
of alkyl ether carboxylic acids, alkylbenzenesulfonates. Examples of the nonionic
surfactant include ether type nonionic surfactants such as polyoxyethylene alkyl
ethers, ether ester type nonionic surfactants such as polyoxyethylene ether of glycerin
ester, and ester type nonionic surfactants such as polyethylene glycol fatty acid
esters, glycerin ester and sorbitan ester. The nonionic surfactant is preferable
in preventing the scratches occurrence on the surface effectively.
Examples of the above-mentioned oxidizing agent include
organic peroxides such as peracetic acid, perbenzoic acid and tert-butylhydroperoxide,
permanganic acid compounds such as potassium permanganate, dichromic acid compounds
such as potassium dichromate, halogenic acid compounds such as potassium iodate,
nitric acid compounds such as nitric acid, iron nitrate, perhalogenic acid compounds
such as perchloric acid, transition metal salts such as potassium ferricyanide,
persulfates, such as ammonium persulfate, heteropolyacids and the like.
Examples of the above-mentioned vulcanizing agent include
sulfur (powder sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur,
highly dispersible sulfur and the like), sulfur compounds (sulfur monochloride,
sulfur dichloride and the like) and the like.
Examples of the above-mentioned crosslinking agent include
peroxides (dicumyl peroxide, di-t-butyl peroxide and the like), oximes (p-quinone
dioxime, p,p'-dibenzoylquinone dioxime and the like), polyamines (triethylene tetramine,
hexamethylenediamine carbamate, 4,4'-methylene-bis-o-chloroaniline and the like),
modified phenol resins (alkylphenol resins with methylol group and the like) and
the like.
An organic acid is preferable as the above-mentioned acid.
Examples of the organic acid include p-toluenesulfonic acid, dodecylbenzenesulfonic
acid, isoprenesulfonic acid, gluconic acid, lactic acid, citric acid, tartaric acid,
malic acid, glycolic acid, malonic acid, formic acid, oxalic acid, succinic acid,
fumaric acid, maleic acid, phthalic acid and the like. One type of the organic acid
may be used alone or in combination of two or more. An inorganic acid such as nitric
acid, hydrochloric acid, sulfuric acid and the like may also be given as examples
of the above-mentioned acid.
Examples of the above-mentioned pH adjuster include inorganic
acids such as hydrochloric acid and sulfuric acid, and basic agents such as sodium
hydroxide and potassium hydroxide.
Examples of the above-mentioned multivalent metal ions
include ions of metal such as aluminum, titanium, vanadium, chromium, manganese,
iron, cobalt, nickel, copper, zinc, germanium, zirconium, molybdenum, tin, antimony,
tantalum, tungsten, lead and cerium. One type of such multivalent metal ions may
be used alone or in combination of two or more.
Examples of the above-mentioned scratch prevention agent
include biphenol, bipyridyl, 2-vinylpyridine, 4-vinylpyridine, salicylaldoxime,
o-phenylenediamine, m-phenylenediamine, catechol, o-aminophenol, thiourea, N-alkyl-group-containing
(meth)acrylamide, N-aminoalkyl-group-containing (meth)acrylamide, heterocyclic compounds,
which have a penta-heterocyclic ring and does not have a skeleton-forming aromatic
ring (7-hydroxy-5-methyl-1,3,4-triazaindolizine, etc.), heterocyclic compounds,
which have a penta-heterocyclic ring and have a skeleton-forming aromatic ring (5-methyl-1H-benzotriazole,
etc.), phthalazine, compounds, which have a hexa-heterocyclic ring containing three
nitrogen atoms (melamine, 3-amino-5,6-dimethyl-1,2,4-triazine, etc.), and various
derivatives of the compounds given above. 7-hydroxy-5-methyl-1,3,4-triazaindolizine
is especially preferable as the scratch prevention agent. A surfactant may also
be used as a scratch prevention agent.
The above-mentioned "solidification" normally requires
a dispersion medium elimination (drying) process and a molding process. These two
processes may be carried out simultaneously or separately. Or, after eliminating
the dispersion medium to some extent, molding may be performed and thereafter, complete
elimination of the dispersion medium may be performed. The method maybe selected
as suitable in accordance with the properties of the matrix material and the like.
Also, after elimination of the dispersion medium, a process of crushing the dried
product further may be provided, and thereafter, the finely crushed powder may be
molded.
The elimination of the dispersion medium may for example
be performed by leaving in an open system and eliminating the dispersion medium
naturally by evaporation. The evaporation of the dispersion medium may furthermore
be promoted by heating, depressurizing and the like.
The dispersion medium may also be eliminated by the spray
drying method. By this method, the dispersion medium can be evaporated rapidly and
granulation can be performed at the same time. This spray drying method is the one
the prescribed aqueous dispersion is made into a fine mist which is then ejected
into hot air or vacuum to obtain a powdery dry powder (granulated product) instantaneously.
Using this spray drying method, the crushing process after the drying process can
be omitted, the particle size distribution of the powder can be made narrow and
uniform, and as result, the amount filled into a mold in the process of performing
powder molding can be stabilized and the distribution of the weights of individual
molded products can be reduced. Furthermore, since a granular powder that is more
uniformly dispersed than a crushed product can be obtained, a molded product of
higher strength can be obtained by the use of a powder obtained by spray drying.
Furthermore, the denseness distribution of the interior of the polishing body can
be small and the polishing performance for each polishing process can be stabilized.
The above-mentioned molding process can be formed a residue
(in the form of lump, flake, powder, pellet and the like) from which the dispersion
medium has been eliminated to some extent, or a dried powder (including a granular
product) from which the dispersion medium has been substantially eliminated nearly
completely, by performing press molding, extrusion molding, injection molding and
the like.
In the case where the elimination of the dispersion medium
and molding are to performed simultaneously, the aqueous dispersion may be charged
into a desired mold and solidification to the shape of the mold may be performed
by eliminating the dispersion medium in the same manner as described above. Also,
without using a mold, the aqueous dispersion may be developed across the surface
of a layer and the like, which is to be the base material, and thereafter the dispersion
medium may be eliminated in the same manner as described above. Various additives,
such as those mentioned above, may be added in the molding process.
The above-mentioned "polishing part" exhibits a mechanical
and/or chemical polishing effect. The entirety of the polishing body (which for
example is of a plate-like shape and particularly of a disk-like shape) in the invention
may be comprised of the polishing part. And the polishing body may be the one equipped
with the polishing part on the surface of a plate-like body as a supporting part
(the shape thereof is not limited and may be disk-like or square-shaped), or the
one whose thin polishing part in predetermined shape is arranged in a regular manner
on the surface of the polishing body. The material of the supporting part is not
particularly restricted and a polyurethane resin (foamed or unfoamed), metal, nonwoven
fabric and the like may be used. Among these, a flexible polyurethane resin or a
metal (in particular, stainless steel, etc.) is especially preferable.
With the polishing body in the invention, the volume ratio
of the abrasive in the polishing body may be 1 to 99% by volume (more preferably
10 to 70% by volume and especially preferably 15 to 50% by volume). The polishing
body in the invention is preferably used in the polishing of a semiconductor. Objects
to be polished that can be polished by the polishing body include glass, silicon
oxide layer, amorphous silicon layer, polycrystalline silicon layer, monocrystalline
silicon layer, silicon nitride layer, pure tungsten layer, pure aluminum layer,
pure copper layer and the like, as well as layers of an alloy of tungsten, aluminum,
copper, and another metal. Objects that can be polished by this polishing body also
include layers of oxides and nitrides of such metals as tantalum, titanium.
Preferred Embodiments of the Invention
This invention will be described more specifically by way
of examples and comparative examples. However, this invention is not limited to
these examples.
< A > Examples of use of thermoplastic resin as the matrix
material
[1] Preparation of non-crosslinked type polishing bodys
(1) Preparation of aqueous dispersions A to C and non-aqueous
dispersion D
① Aqueous dispersion A, having a matrix material and
abrasive dispersed therein
The respective components shown in Table 1 were charged
at the respective proportions into a temperature-adjustable autoclave, equipped
with a stirrer, and were reacted for 16 hours at 75°C. As a result, the polymerization
conversion was 95.8% and an aqueous thermoplastic resin emulsion was obtained in
which a copolymer (thermoplastic resin), with a glass transition temperature of
50°C and an average particle diameter of 166nm, was dispersed. The particle
diameter was measured using a laser particle size analysis system made by Otsuka
Electronics Co., Ltd. (in the description that follows, the particle diameter was
measured by the same method).
Table 1
Component
Amount (parts)
Ion-exchanged water
240
Butadiene
14.00
Styrene
71.00
Methylene methacrylate
12.15
Itaconic acid
1.85
Acrylic acid
1.00
á-Methylstyrene dimer
0.10
t-Dodecylmercaptan
0.40
The emulsion that was obtained as described above was adjusted
to pH8.5 by means of a 25% aqueous solution of potassium hydroxide. Thereafter,
water (ion-exchanged water) was added and stirring was performed under room temperature
using a "Three-One Motor." After incorporating a cerium oxide (CeO2)
powder with a particle diameter of 0.3µm prior to processing, stirring at 1,500
rotations/minute was carried out for 3 minutes to obtain an aqueous dispersion A.
② Aqueous dispersion B, having composite particles wherein
abrasive is attached to a matrix material dispersed
The respective components shown in Table 2 were charged
at the respective proportions into a flask of 2-liter volume and were made to undergo
polymerization under a nitrogen atmosphere by stirring at 70°C for 6 hours.
An emulsion, containing polymethyl methacrylate polymer particles, having an amino
group of a cationic functional group, and a functional group with a polyethylene
glycol chain, was thereby obtained. The polymerization yield was 95%.
The product of the trade name, "NK Ester M-90G #400", made
by Shin-Nakamura Chemical Co., Ltd., was used as the methoxypolyethylene glycol
methacrylate in Table 2, and the product of the trade name, "V50", made by Wako
Pure Chemicals Industries, Ltd., was used as the azo-based initiator.
Table 2
Component
Amount (parts)
Ion-exchanged water
400
Methyl methacrylate
90.00
Methoxypolyethylene glycol methacrylate
5.00
4-Vinylpyridine
5.00
Azo-based initiator
2.00
The obtained emulsion containing 10% by mass of polymethyl
methacrylate polymer particles, was then adjusted to pH10 by means of potassium
hydroxide. The zeta potential of the polymethyl methacrylate polymer particles in
this emulsion was +17mV. Meanwhile, the dispersion, which was prepared to contain
10% by mass of a cerium oxide powder with a particle diameter of 0.3µm prior
to processing, was adjusted likewise to pH10. The zeta potential of the cerium oxide
in this dispersion was -18mV. The difference of the zeta potentials of the two components
was thus 35mV.
Thereafter, the above emulsion and dispersion were charged
at a mass ratio of 1:1 into a flask of 2-liter volume and then mixed by stirring.
3 parts by mass of tetraethoxysilane were then added into the flask and then stirring
for 1 hour at 25°C, followed by stirring for 3 hours at 40°C, was performed.
The mixture was then cooled to obtain an aqueous dispersion B wherein composite
particles were dispersed. Cerium oxide was attached to 95% of the surface of these
composite particles.
③ Aqueous dispersion C, having composite particles wherein
abrasive is attached to a matrix material dispersed
The respective components shown in Table 3 were charged
at the respective proportions into a flask of 2-liter volume and were made to undergo
polymerization under a nitrogen atmosphere by stirring at 70°C for 6 hours.
An emulsion, containing carboxy-modified polystyrene particles, having a carboxyl
group and a hydroxyl group, was thereby obtained. The polymerization yield was 95%,
and the carboxyl group content as measured by the conductometric titration method
was 40% for the carboxy-modified polystyrene particle interior, 50% for the surface,
and 10% for the aqueous phase part.
Table 3
Component
Amount (parts)
Ion-exchanged water
400
Styrene
92.00
Methacrylic acid
4.00
Hydroxyethyl acrylate
4.00
Ammonium lauryl sulfate
0.10
Ammonium persulfate
0.50
The obtained emulsion containing 10% by mass of carboxy-modified
polystyrene particles, was then adjusted to pH4 by means of nitric acid. The zeta
potential of the carboxy-modified polystyrene particles in this emulsion was -40mV.
Meanwhile, the dispersion, which was prepared to contain 10% by mass of cerium oxide
powder with an average particle diameter of 0.3 µm prior to processing, was
adjusted likewise to pH4. The zeta potential of the cerium oxide in this dispersion
was +20mV. The difference of the zeta potentials of the two components was thus
60mV.
Thereafter, the above emulsion and dispersion were charged
at a mass ratio of 1:1 into a flask of 2-liter volume and then mixed by stirring.
3 parts by mass of tetraethoxysilane was then added into the flask and then stirring
for 1 hour at 25°C, followed by stirring for 3 hours at 40°C, was performed.
The mixture was then cooled to obtain an aqueous dispersion C wherein composite
particles were dispersed. Cerium oxide was attached to 90% of the surface of these
composite particles.
④ Non-aqueous dispersion D, having a matrix material
and abrasive dispersed therein
The aqueous dispersion medium of an emulsion obtained in
the same manner as ins was evaporated and dried. Thereafter, the same amount of
toluene as the amount of the evaporated and dried aqueous dispersion medium was
added and mixing by stirring was performed. The same amount of cerium oxide powder
as that used in ① was mixed by stirring into the liquid to thereby obtain
non-aqueous dispersion D. As cerium oxide was added, the viscosity of the dispersion
increased and it became impossible to continue stirring during the process.
(2) Molding
Each of the aqueous dispersions A to C and non-aqueous
dispersion D obtained in (1) was spread thinly across a polyethylene film and made
flake-like in form by leaving and drying for 48 hours under room temperature. Each
flake-like product thus obtained was then formed using a mold press to thereby obtain
disk-shaped polishing bodys A to D of 30cm diameter and 3mm thickness. The polishing
bodys A to C are in the invention while polishing body D is a comparative example.
[2] Evaluation of the dispersion property of the abrasive and
evaluation of the polishing bodys A to D
(1) Evaluation of the dispersion property of the abrasive
For each of the aqueous dispersions A to D, the dispersion
medium was eliminated, the resulting residue was magnified by a transmission electron
microscope, and the maximum diameters of 50 abrasive were measured respectively
using the electron microscope photograph that was taken, and the average maximum
diameter was calculated as the average value of the measured values. The results
are shown in Table 4.
(2) Evaluation of polishing performance
① Measurement of removal rate
Each of the polishing bodys A to D was adhered onto the
surface table of a polishing device (model "LM-15," made by Lapmaster STF Corp.)
and a 4cm-square thermally oxidized layer wafer was polished while supplying just
water at a rate of 150cc per minute. The other polishing conditions were; a table
rotation speed of 50rpm, head rotation speed of 50rpm, polishing pressure of 350g/cm2,
and polishing time of 2 minutes. The removal rate was then calculated from the results
by using the following formula (1).
② Evaluation of scratching
The surfaces of wafers polished in ① were observed
visually and evaluated. The results are shown in Table 4. In Table 4, "None" indicates
that no scratches whatsoever could be found by visual observation. "Numerous" indicates
that numerous scratches were observed by visual observation.
Table 4
Polishing body A (Example)
Polishing body B (Example)
Polishing body C (Example)
Polishing body D (Comparative example)
Primary particle diameter (µm)
0.3
Secondary particle diameter (µm)
0.3
0.3
0.4
2.0
Removal rate (Ĺ/minute)
2,000
1,800
1,700
1,800
Scratches
None
None
None
Numerous
According to the results in Table 4, whereas the particle
diameter of the abrasive prior to processing was 0.3µm, the particle diameter
became 0.3 to 0.4µm in the condition immediately prior to forming into the
polishing body. That is, the particle diameter became 1 to 1.3 time the average
particle diameter and it is thus predicted that the abrasive was contained in the
polishing body without changing in particle diameter from that prior to processing.
Meanwhile, whereas the particle diameter prior to processing was 0.3 µm in
regard to the polishing body D, which is not of the invention, the particle diameter
became 2.0µm in the condition immediately prior to forming into the polishing
body. That is, the particle diameter increased by 7.3 times the average particle
diameter and it is thus predicted that the abrasive was largely aggregated in the
polishing body D as well. Also, whereas visually recognizable scratches were not
seen on the wafers polished by the polishing bodys of the polishing bodys A to C,
numerous scratches were seen on the wafer polished by the polishing body D.
< B > Examples of use of thermosetting resin as the matrix
material
[1] Preparation of crosslinked type polishing bodys
(1) Preparation of aqueous dispersions E to G
(a) Aqueous thermosetting resin a
The aqueous epoxy resin "EM101-50," made by Asahi Denka
Kogyo K.K. (solid content; 50% by mass), was used.
(b) Aqueous thermoplastic resin b
The aqueous thermoplastic resin emulsion (solid content;
48% by mass) described above, was used.
① Aqueous dispersion E, having a thermosetting resin-based
matrix material and abrasive dispersed therein
The aqueous thermosetting resin a was adjusted to pH8.5
by means of a 25% aqueous solution of potassium hydroxide. Water (ion-exchanged
water) was then added and stirring was performed at room temperature using a "Three-One
Motor." After incorporating a cerium oxide (CeO2) powder with a particle
diameter of 0.3µm prior to processing, the curing agent "EH-3615S" was incorporated
and stirring at 600 rotations/minute was carried out for 3 minutes to obtain an
aqueous dispersion E.
② Aqueous dispersion F, having dispersed therein a matrix
material, in which a thermosetting resin-based is combined with a thermoplastic
resin-based, and abrasive
The aqueous thermoplastic resin b and water (ion-exchanged
water) were added to aqueous thermosetting resin a and stirring at room temperature
was performed. The proportions of the solid content of the aqueous thermosetting
resin a and the aqueous thermoplastic resin b were set so that the aqueous thermosetting
resin a will comprise 50% by mass based on the total of both resins.
The dispersion was then adjusted to pH8.5 by means of a
25% aqueous solution of potassium hydroxide. After then incorporating a cerium oxide
(CeO2) powder with a particle diameter of 0.3µm prior to processing,
the above-mentioned curing agent "EH-3615S" was incorporated and stirring at 600
rotations/minute was carried out for 3 minutes to obtain an aqueous dispersion F.
③ Aqueous dispersion G, having a thermoplastic resin
and abrasive dispersed therein
Water (ion-exchanged water) was added to aqueous thermoplastic
resin b and stirring was performed at room temperature. The dispersion was then
adjusted to pH8.5 by means of a 25% aqueous solution of potassium hydroxide. After
then incorporating a cerium oxide (CeO2) powder with a particle diameter
of 0.3µm prior to processing, the above-mentioned curing agent "EH-3615S" was
incorporated and stirring at 600 rotations/minute was carried out for 3 minutes
to obtain an aqueous dispersion G.
(2) Molding
Each of the aqueous dispersions E to G obtained in (1)
was spread thinly across a polyethylene film and made flake-like products in form
by leaving and drying for 48 hours under room temperature. Each flake-like product
thus obtained was then formed using a mold press to thereby obtain disk-shaped polishing
bodys E to G of 30cm diameter and 3mm thickness. Polishing bodys E and F are in
the invention (examples) while polishing body G is a comparative example.
[2] Evaluation of machinability and evaluation of polishing
bodys E to G
(1) Cutting
Cutting of the surface was carried out in order to increase
the surface precision of each of the polishing bodys of 30cm diameter and 3mm thickness.
A machining center was used for cutting and an end mill was used as the cutting
tool. The cutting amount was set to 0.02mm and the feeding speed was set to 100mm/minute.
(2) Evaluation of machinability
The machinability was evaluated by comparison of the removal
rate before and after cutting. Each of the polishing bodys A to C was adhered onto
the surface table of a polishing device (model "LM-15," made by Lapmaster STF Corp.)
and a 4cm-square thermally oxidized layer wafer was polished while supplying just
water at a rate of 150cc per minute. The other polishing conditions were a table
rotation speed of 50rpm, head rotation speed of 50rpm, polishing pressure of 350g/cm2,
and polishing time of 2 minutes. The dressing conditions were; a dresser number
of #100, table rotation speed of 30rpm, head rotation speed of 30rpm, dressing pressure
of 300g/cm2, and dressing time of 10 minutes. The removal rate was then
calculated from the results by using the following formula (1).
The polishing results are shown in Table 5.
Table 5
Units
Polishing body E (thermosetting
resin)
Polishing body F (thermosetting
resin + thermoplastic resin)
Polishing body G (thermoplastic
resin)
Uncut
Cut
Uncut
Cut
Uncut
Cut
Distribution of thickness (maximum)
110
25
100
20
100
20
Removal rate ; without dressing
Ĺ/minute
1,100
1,300
1,000
1,300
1,000
250
Removal rate ; with dressing
Ĺ/minute
1,100
1,500
1,000
1,500
1,000
25
According to the results in Table 5, the distribution of
thickness of the polishing body as a whole were small as intended for all polishing
bodys E to G. With regard to the removal rate, those of the cutting products of
polishing bodys E and F was large in comparison to those of the uncutting products,
but the removal rate of the cutting product using the polishing body G became considerably
low. This is because with polishing bodys E and F, the distribution of the thickness
was made low by cutting. On the other hand, with the comparative example polishing
body G, though the distribution of thickness was made low, it is considered that
surface of the polishing body melted slightly due to the heat during cutting and
the surface thus became deteriorated somewhat. In contrast, deterioration of the
surface was not seen with the polishing bodys E and F of the invention.
<C> Example of employment of the spray drying method
Using the aqueous dispersion A described above, the spray
drying method was carried out under the following operation conditions to obtain
granular particles of an average particle diameter of 60µm.
[Spray drying method conditions]
Equipment used; "OC-16"; made by Ohkawara Kakohki Co.,
Ltd., spraying disk diameter; 65mm, inlet temperature; 160°C, outlet temperature;
65°C. spraying disk rotation speed; 15,000rpm, stock solution treatment rate;
12kg/h.
This dried powder was then molded using a powder press
to obtain a polishing body H.
As a result of testing the flexural strength of the polishing
body H by the method described below, it was found that whereas the flexural strength
of the polishing body E, measured in the same manner, was 130kgf/cm2,
that of the polishing body H was 330kgf/cm2. This comparison of the two
polishing bodys shows that the polishing body H excels in terms of flexural strength.
[Test method]
A test in compliance with ASTM 638 was performed using
the Instron Universal Material Tester 4204.