JP2015193486A - Polishing metal-carrying metal oxide particle, and polisher - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metal-carrying metal oxide particle which can be used suitably for polishing an aluminum disk, a silicon semiconductor wafer, and a compound semiconductor wafer or the like, and a production method thereof.SOLUTION: This invention provides a metal-carrying metal oxide particle in which a metal oxide particle with an average particle diameter in the range of 7-600 nm carries at least one metal selected from Ag, Pd, Au, Pt, Cu, and Fe in the range of 0.01-1200 pts. wt. as metal relative to the metal oxide particle of 100 pts. wt.

Description

  The present invention relates to a metal-supporting metal oxide particle for polishing in which a metal is supported on metal oxide particles, and an abrasive containing the particle.

  In the manufacture of a substrate with a semiconductor integrated circuit, for example, when an aluminum wiring is formed on a silicon wafer and an oxide film such as silica is provided thereon as an insulating film, irregularities are caused by the wiring. It is done to flatten. In the polishing of such a substrate, the surface after polishing is required to be flat with no steps or irregularities, smooth without microscopic scratches, etc., and the polishing rate must be high.

Conventionally, silica sol, fumed silica, fumed alumina, or the like is used as the abrasive particles.
The abrasive used in chemical mechanical polishing (CMP) is usually polishing particles having an average particle diameter of about 200 nm made of a metal oxide such as silica, alumina, and ceria, and the polishing rate of metal for wiring and circuits. It is composed of an oxidizer, an organic acid additive, and a solvent such as pure water.

For example, Japanese Patent Laid-Open No. 2001-150334 (Patent Document 1) discloses an active silicic acid having a SiO ₂ concentration of about _{2 to} 6% by weight obtained by decation treatment of an aqueous solution of an alkali metal silicate such as water glass. An alkaline earth metal such as a salt of Ca, Mg, Ba or the like is added to the acidic aqueous solution at a weight ratio of 100 to 1500 ppm with respect to SiO ₂ of the above active silicic acid in terms of its oxide, and SiO ₂ / M ₂ O (M represents an alkali metal atom, NH ₄ or a quaternary ammonium group.) The liquid obtained by adding the same alkali substance in an amount that the molar ratio is 20 to 150 is the initial heel liquid, 2-6 wt% of _SiO 2 / _{M 2} O of SiO ₂ concentration of 20 to 150 obtained in the same manner as in (M is as defined above) of the active silicic acid aqueous solution having a molar ratio as charged liquid, The charge liquid the initially heel solution at 0 to 150 ° C., per hour, the charge liquid SiO ₂ / initial 0. As the weight ratio of the heel solution SiO ₂ 05-1. 0 rate, evaporative removal of water from the liquid While (or without), a method for producing a silica sol having a distorted shape is described.

In JP-A-8-279480 (Patent Document 2), (1) a method in which an alkali silicate aqueous solution is neutralized with a mineral acid and an alkaline substance is added and heated to age, (2) a cation exchange treatment of the alkali silicate aqueous solution is performed. (3) A method of heating and aging active silicic acid obtained by hydrolyzing an alkoxysilane such as ethyl silicate, or (4) Fine silica powder Colloidal silica aqueous solution produced by, for example, a method of directly dispersing in an aqueous medium usually contains colloidal silica particles having a particle diameter of 4 to 1,000 nm (nanometer), preferably 7 to 500 nm. is obtained by dispersing 0.5 to 50% by weight SiO _2, preferably has a concentration of 0.5 to 30 wt%. It is described that the particle shape of the silica particles includes a spherical shape, a distorted shape, a flat shape, a plate shape, an elongated shape, and a fibrous shape.

  Japanese Patent Publication No. 2003-52962 (Patent Document 3) discloses a polishing agent containing spherical, separated silica particles which are not connected to each other by a bond, and a) a silica particle having a size of 5-50 nm, 5-95 weight. And b) an abrasive comprising 95-5% by weight of silica particles of size 50-200 nm, but with the entire particle having a bimodal particle size distribution is disclosed to provide a high polishing rate.

  Further, the applicant of the present invention has a degree of irregularity in the range of 1.55 to 4, and in the particle size distribution by the dynamic light scattering method, the particle size distribution peaks in a particle size range of 30 to 70 nm and a particle size range of 71 to 150 nm. It is disclosed that an excellent polishing rate can be achieved when a polishing silica sol having a particle size difference between both peaks in the range of 50 to 100 nm is used (Japanese Patent Laid-Open No. 2007-137972: Patent Document 4). .

  Further, the applicant of the present application is a polishing composition containing spherical particles having a sphericity of 0.9 or more and non-spherical particles that do not correspond to the spherical particles in a predetermined weight ratio, even if the surface to be polished has irregularities. It is disclosed that the subsequent surface is excellent in flatness, and deterioration in polishing performance can be suppressed even when subjected to long-time polishing (Japanese Patent Laid-Open No. 2006-80406: Patent Document 5).

Further, the applicant of the present application comprises non-spherical silica fine particles and a plurality of protrusions formed from a metal oxide other than silica formed on the surface thereof, and the average particle diameter measured by a dynamic scattering method is 3 to 150 nm. Sol in which non-spherical composite silica fine particles having a short diameter / long diameter ratio in the range of 0.01 to 0.8 and a specific surface area in the range of 10 to 800 m ² / g are dispersed in a dispersion medium and a method for producing the same It is disclosed that it is useful as an abrasive (Japanese Patent Laid-Open No. 2009-137771: Patent Document 6).

In addition, the applicant of the present application discloses a confetti-like silica-based fine particle having a plurality of ridge-like protrusions on the surface of the spherical silica-based fine particle and having a surface roughness in the range of 1.7 to 10, and an abrasive containing the fine particle. (JP 2013-47180 A: Patent Document 7).
Furthermore, JP 2010-188487A (Patent Document 8) describes the surface smoothness of a non-processed material such as a SiC substrate when a compounding polishing liquid based on transition metal fine particles, oxide fine particles and hydrogen peroxide is used. It is disclosed that the polishing rate is greatly improved without loss.

JP 2001-150334 A JP-A-8-279480 Japanese translation of PCT publication No. 2003-52962 JP 2007-137972 A JP 2006-80406 A JP 2009-137791 A JP2013-47180A JP 2010-188487 A

However, when irregularly shaped particles such as the flat gold silica-based fine particles of Patent Document 7 are used as polishing particles, the polishing rate is improved compared to spherical particles having a smooth surface, but scratches may occur due to surface irregularities or the surface In some cases, the smoothness of the film was lacking. In addition, agglomerated particles having a large particle size are produced during production, which may cause scratches. Moreover, there has been a problem that productivity and economy are reduced when the aggregated particles are removed.
Therefore, when the above-mentioned irregularly shaped particles (non-spherical particles) and transition metal fine particles were mixed and used as in Patent Document 8, the polishing rate was improved, but the transition metal fine particles and spherical particles were mixed. The effect of using a mixture of irregularly shaped particles (non-spherical particles) was not obtained.
As a result of intensive investigations for further improvement of the polishing rate and surface smoothness, the present inventors have found that the use of metal-supported particles further improves the polishing rate and also improves the surface smoothness. The present invention has been completed.
The subject of this invention is providing the metal oxide particle which can be used suitably for grinding | polishing of an aluminum disk, a silicon semiconductor wafer, a compound semiconductor wafer, etc., and its manufacturing method.

The metal-supported metal oxide particles for polishing according to the present invention are characterized in that a metal is supported on the metal oxide particles.
The average particle diameter (D _A ) is preferably in the range of 7 to 600 nm.
The metal is at least one selected from Ag, Pd, Au, Pt, Cu, and Fe, and the amount of the metal supported is in the range of 0.01 to 1200 parts by weight as a metal with respect to 100 parts by weight of the metal oxide particles. It is preferable.
The shape of the metal oxide particles is preferably irregularly shaped particles (non-spherical).
It is preferable that at least a part of the metal is supported on the outer surface of the metal oxide particles.
The metal oxide particles are at least one selected from SiO ₂ , Al ₂ O ₃ , Sb ₂ O ₅ , ZrO ₂ , TiO ₂ , Fe ₂ O ₃ , CeO ₂ and complex oxides thereof, or a mixture thereof. It is preferable.

The abrasive | polishing agent which concerns on this invention is characterized by including one of the said metal supporting metal oxide particles for grinding | polishing.
The abrasive preferably further contains an oxidizing agent.
The object to be polished is preferably at least one selected from Si, SiC, GaN, Al, AlN, Cu, TiN, and SiN.

  The metal-supported metal oxide particles for polishing of the present invention are excellent in polishing performance and surface smoothness, and the abrasive containing the metal-supported metal oxide particles for polishing includes aluminum disks, silicon semiconductor wafers, compound semiconductor wafers, and the like. It can be suitably used for polishing.

Hereinafter, the metal-supported metal oxide particles for polishing, in which the metal according to the present invention is supported on the metal oxide particles, will be described first.
[Polished metal-supported metal oxide particles]
The metal-supported metal oxide particles for polishing according to the present invention are characterized in that a metal is supported on the metal oxide particles.
The metal oxide particles are not particularly limited as long as they can carry a metal effective for polishing, which will be described later, and conventionally known metal oxide particles can be used. SiO ₂ , Al ₂ O ₃ , Sb It is preferably at least one selected from ₂ O ₅ , ZrO ₂ , TiO ₂ , Fe ₂ O ₃ , CeO ₂ and a composite oxide thereof, or a mixture thereof.
Since these metal oxide particles have high hardness, are chemically stable and have excellent polishing performance, they can be suitably used.

The shape of the metal oxide particles used in the present invention is not particularly limited as long as it has polishing performance, and may be spherical, but preferably non-spherical or irregularly shaped particles having irregularities on the surface.
Here, examples of the irregularly shaped particles include particles having various shapes such as a fibrous shape, a chain shape, a plate shape, a dice shape, a confetti shape, a sunflower shape, and a cluster shape.
The chain particles are particles in which primary particles are connected in a chain, and the gold flat sugar particles, the sunflower particles, and the cluster particles are particles having fine hook-like projections (convex portions) on the outer surface of the particles.

Examples of the confetti particles include the confetti particles disclosed in Japanese Patent Application Laid-Open No. 2009-78935 filed by the present applicant.
Examples of the method for producing the gold-plated sugar-like metal oxide particles include a seed particle dispersion in which silica particles having a particle diameter of 3 to 140 nm are dispersed in a solvent having a pH of 8 to 12 and a temperature in the range of about 60 to 200 ° C. And a metal oxide precursor excluding silica or a predetermined amount of the metal oxide precursor and silicic acid solution can be added continuously or intermittently.
As another method for producing the gold flat sugar-like metal oxide particles, the pH and temperature of the seed silica sol in which silica fine particles are dispersed in a solvent are adjusted to a predetermined range, and the metal peroxide or the metal peroxide and the silicic acid solution are mixed. It can also be prepared by adding a predetermined amount all at once.

A cluster-like particle is a secondary particle in which a large number of primary particles of metal oxide particles are aggregated, and has a structure similar to that of a confetti particle.
Examples of the method for producing cluster particles include a method in which an aqueous dispersion of metal oxide particles having an average primary particle diameter in the range of about 10 to 150 nm is hydrothermally treated in the presence of a salt.
At this time, as a salt, salts such as magnesium sulfate, magnesium chloride, magnesium nitrate, calcium chloride, and calcium nitrate can be preferably used. Moreover, it is preferable that the density | concentration of the metal oxide particle aqueous dispersion at this time exists in the range of about 2 to 20 weight%, and the hydrothermal treatment temperature exists in the range of about 80-120 degreeC.

The sunflower-like particle means a metal oxide particle in which a coating metal oxide particle having a small particle size is coated with a single layer on the outer surface of a metal oxide particle for a substrate having a large particle size.
As a method for producing sunflower-like particles, a metal oxide particle for a substrate having a positive or negative surface potential and an average particle diameter in the range of about 40 to 600 nm and a positive or negative surface potential different from this are used. Then, a mixed dispersion liquid with coating metal oxide particles having an average particle diameter of approximately 4 to 60 nm is prepared, and then the pH of the mixed dispersion liquid is adjusted to 6 to 10 by treatment with an anion exchange resin. Then, the coating particles are attached to the surface of the substrate particles, and then heated and aged to join the coating metal oxide particles to the substrate metal oxide particles, and if necessary, dried and heat-treated. can do.

  If the outer surface has fine irregular-shaped projections (projections), the metal described later is supported in the recesses, but the metal is supported in the recesses as fine particles, and this metal is OH radical. On the other hand, it is considered that the convex portions of the metal oxide particles exhibit polishing ability due to collision with the substrate to be polished, and both of these effectively contribute.

The average particle diameter (D _A ) of the metal oxide particles is preferably 7 to 600 nm, more preferably 10 to 400 nm, and particularly preferably 10 to 100 nm.
When the average particle diameter (D _A ) of the metal oxide particles is less than 7 nm, the metal may not be supported, and even if it can, sufficient polishing performance may not be obtained.
If the average particle diameter (D _A ) of the metal oxide particles exceeds 600 nm, scratching may occur during polishing and surface accuracy, surface smoothness, etc. may be insufficient.
In the present invention, the average particle diameter (D _A ) of the metal oxide particles is measured with a laser-type particle size distribution analyzer (manufactured by Nikkiso Co., Ltd .: Microtrac UPA).

The metal metal is not particularly limited as long as it can react with hydrogen peroxide to generate OH radicals, but is preferably at least one selected from Ag, Pd, Au, Pt, Cu, and Fe.
Especially, since Ag, Au, Pt, Pd activity is high and radical generating ability is high, it can employ | adopt suitably.
The amount of the metal supported is in the range of 0.01 to 1200 parts by weight, more preferably 0.1 to 800 parts by weight, particularly 0.1 to 600 parts by weight as metal with respect to 100 parts by weight of the metal oxide particles. It is preferable.

If the amount of metal supported is less than 0.01 parts by weight as metal with respect to 100 parts by weight of metal oxide particles, the catalytic action of the metal cannot be sufficiently exhibited and sufficient polishing characteristics may not be obtained.
Even if the amount of the metal supported exceeds 1200 parts by weight as metal with respect to 100 parts by weight of the metal oxide particles, the polishing performance is not further improved, and the economical efficiency decreases due to an increase in the amount of expensive metal used.
In particular, if the amount of metal supported is in the range of 0.1 to 600 parts by weight with respect to 100 parts by weight of metal oxide particles, it varies depending on the type of metal, the shape of the metal oxide particles, the particle diameter, The metal oxide particles are not completely coated, and the metal-supported metal oxide particles for polishing having excellent polishing performance can be obtained by the synergistic effect of the catalytic action of the metal and the polishing action of the metal oxide particles exposed on the surface. .

It is preferable that at least a part of such a metal is supported on the outer surface of the metal oxide particles.
When the metal is present on the outer surface of the metal oxide particle, particularly in the case of irregularly shaped particles, as described above, the generation of OH radicals by the metal is promoted, and at the same time, due to the collision between the convex part and the substrate to be polished. Due to a synergistic effect with the polishing ability, metal-supporting metal oxide particles for polishing excellent in polishing performance can be obtained.

The metal loading method is not particularly limited as long as a predetermined amount of metal can be loaded on the metal oxide particles, and differs depending on the type of metal and the type of metal oxide particles. For example, JP 2012-116699 A The method for producing metal-coated metal oxide fine particles disclosed in the publication can be employed.
Specifically, a metal complexing agent is added to the metal oxide particle dispersion as a solid component so that the weight of the metal oxide fine particles is within a predetermined range, and a metal such as polyvinylpyrrolidone is added to the metal oxide fine particles. Examples include a method of adsorbing a complexing agent, then adding an aqueous metal salt solution, and then adding a reducing agent such as hydrogen or sodium borohydride to reduce the metal salt.

Moreover, the manufacturing method of the metal particle carrying catalyst disclosed by Unexamined-Japanese-Patent No. 2012-30149 can also be employ | adopted.
Specifically, there may be mentioned a method in which a predetermined one or more metal ions are added to and supported on a suspension in which a carrier substance having a primary particle size of 1 to 500 nm including an ion exchanger is dispersed in a solvent.

Also, a method according to the method for producing conductive silica particles disclosed in JP-A-2009-96661 can be employed.
In addition, a method according to the method for producing a rod-shaped conductive fine particle group disclosed in JP 2010-103109 A can be employed.
For example, after dispersing fibrous metal oxide particles such as alumina in a water / alcohol mixed solvent, and adding a metal salt such as silver nitrate or palladium nitrate thereto, a predetermined amount of trisodium citrate, ferrous sulfate, etc. It can be produced by adding a reducing agent and stirring under a nitrogen atmosphere.

Next, the abrasive according to the present invention will be described.
[Abrasive]
The abrasive according to the present invention is characterized by comprising the above-described metal-supporting metal oxide particles for polishing.
Polishing metal-supporting metal oxide particles The polishing metal-supporting metal oxide particles described above are used as the polishing metal-supporting metal oxide particles.
Furthermore, the polishing agent of the present invention contains an oxidizing agent, and examples of the oxidizing agent include hydrogen peroxide, ozone, hypochlorite, and perchlorate. Among these, hydrogen peroxide can be suitably used because it easily generates OH radicals and does not accompany agglomeration of abrasive grains.

When using an oxidant loaded with a metal other than Pt or Au, if the oxide is present in the abrasive, the metal ionization by oxidation proceeds and the metal dissolves. If added separately, the metal does not dissolve and polishing becomes possible.
The reason for this is not clear, but it is presumed that the oxidizing agent pulls electrons from the metal and ionizes them, but the metal takes electrons from the base material and prevents them from being oxidized. The substrate is deprived of electrons, is ionized (polished), and is deposited outside the substrate as an oxide by an oxidizing agent. Based on this principle (catalytic action), it is presumed that the substrate is polished and a highly smooth base material is obtained.

Further, it is preferable that the polishing object of the present invention is at least one selected from Si, SiC, GaN, Al, AlN, Cu, TiN, and SiN.
For these objects to be polished, the polishing rate is high, and a smooth and finely polished surface can be obtained.
Furthermore, examples of other components used in the polishing agent of the present invention together with the metal-supported metal oxide particles for polishing and the oxidizing agent of the present invention are listed below, but are not limited thereto.

As a polishing accelerator, in alkaline systems, metal hydroxides such as potassium hydroxide and sodium hydroxide, metal carbonates such as sodium carbonate and ammonium carbonate, amines such as ammonia, monoethanolamine and piperazine, tetramethylammonium and the like Examples of oxides such as quaternary ammonium hydroxides include chlorine compounds and hydrofluoric acid. In particular, hydrofluoric acid can be suitably used to promote dissolution of the SiO ₂ surface generated by the catalytic reaction during polishing. When hydrofluoric acid uses silica as a metal oxide, if the amount of metal supported is small, dissolution may occur when mixed with an abrasive. Therefore, it is preferable not to add it to the abrasive but to add it separately on the substrate during polishing.
As the surfactant, anionic, cationic, nonionic or amphoteric surfactants can be used.

  As ions used as a buffering agent, although depending on the pH range to be adjusted, the cation is at least one of quaternary ammonium ion and alkali metal ion, and the anion is carbonate ion, bicarbonate ion, boron. It is preferable that it is at least 1 type or more of an acid ion and phenol. Particularly preferred are a mixture of carbonate ions and bicarbonate ions, borate ions, and the like.

Examples of the stabilizer include celluloses such as carboxymethyl cellulose and hydroxyethyl cellulose, water-soluble polymers such as polyvinyl alcohol, water-soluble alcohols such as ethanol, ethylene glycol, propylene glycol and glycerin, and sodium alkylbenzene sulfonate. Examples thereof include surfactants, organic polyanionic substances such as polyacrylates, inorganic salts such as magnesium chloride and potassium acetate.
The concentration of the metal-supported metal oxide particles in the abrasive is usually 1 to 20% by weight, but is not necessarily limited to this range.
The concentration of the oxidizing agent is generally in the range of 0.1 to 30% by weight although it varies depending on the type of oxidizing agent, the concentration of metal-supported metal oxide particles, the type and amount of other additives, etc. It is not limited to this range.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
[Example 1]
Preparation of metal oxide particles for polishing (1) Silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid SI-45P, average particle size 45 nm, solid content concentration 40% by weight, specific surface area 61 m ² / g) as metal oxide fine particles 0.084 g was dispersed in 400 g of water to prepare 4000.08 g of a silica fine particle dispersion having a solid content concentration of 0.0084 wt%.
Separately, 0.032 g of polyvinylpyrrolidone (made by ARDRICH: MW55000) as a metal complexing agent was dissolved in 42.45 g of water to prepare 42.77 g of a polyvinylpyrrolidone aqueous solution having a concentration of 0.075% by weight.
Next, 42.77 g of a metal complexing agent (polyvinylpyrrolidone) aqueous solution was added to a dispersion of silica fine particles having a solid content concentration of 0.0084% by weight and stirred at 20 ° C. for 1 hour to adsorb the metal complexing agent to the silica fine particles. It was. The metal complexing agent / metal oxide fine particle weight ratio at this time was 0.95.

Next, 7.01 g of an aqueous chloroplatinic acid solution having a concentration of 6.65% by weight was added as an aqueous metal salt solution. The metal salt / metal complexing agent molar ratio (M _MS ) / (M _MC ) at this time was 3.95. Since polyvinylpyrrolidone is a polymer, the molar ratio (M _MS ) / (M _MC ) was calculated using the molecular weight of N-vinyl-2-pyrrolidone: 111.14.
Next, 17.21 g of a sodium borohydride aqueous solution having a concentration of 0.1% by weight as a reducing agent was added in 30 seconds, and then stirring was continued at 50 ° C. for 1 hour. At this time, the color changed to black.
The reducing agent / metal salt molar ratio at this time was 0.4.
Subsequently, it was washed with sufficient ion-exchanged water by the ultrafiltration membrane method, and concentrated to a total solid concentration of 20% by weight to prepare a metal oxide particle (1) dispersion for polishing, which was metal-coated silica particles. .
With respect to the obtained metal oxide particles for polishing (1), the average particle diameter was measured, and the results are shown in the table. Moreover, the coating state was observed with a scanning electron microscope (manufactured by Hitachi, Ltd .: S-2000 type), and it was confirmed whether it was a complete coating state or a partial coating state.

Preparation of polishing slurry (1) To a dispersion of polishing metal oxide particles (1) having a total solid concentration of 20% by weight, acetic acid and ultrapure water having a concentration of 1% by weight are added to obtain a total solid concentration of 10.0% by weight. A polishing slurry (1) having a pH of 5.0 adjusted to a hydrogen peroxide concentration of 5% with a hydrogen peroxide concentration of 5% and a concentration of 35% was prepared.

Polished substrate (SiC)
Final polishing of the surface of a 4H—SiC single crystal wafer having a diameter of 2 inches was performed. The orientation of the wafer surface is a Si surface inclined by 8 ° in the (1-210) direction from the Si (0001) surface. The surface state of the SiC wafer was mechanically polished with diamond free abrasive grains, and the unevenness of the wafer surface was Ra = 0.8 nm as a result of measurement by AFM.

Polishing test The substrate to be polished is set in a polishing apparatus (Nippon Eggins Co., Ltd. EJ-380IN), and “Suba800” manufactured by Nitta Haas is used as a polishing pad. For polishing at a substrate load of 26 KPa and a table rotation speed of 60 rpm. The slurry (1) was polished at a rate of 10 g / min and an aqueous HF solution having a concentration of 3% by weight was separately supplied at a rate of 10 g / min for 4 hours. The polishing rate was calculated by determining the weight change of the substrate to be polished before and after polishing. Further, Ra was measured for surface smoothness with an atomic force microscope (AFM) (manufactured by Hitachi High-Tech Science Co., Ltd.). The results are shown in the table.

[Example 2]
Preparation of Metal Oxide Particles for Polishing (2) As a metal oxide fine particle, Kompei silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid CO45A, average particle size 45 nm, solid content concentration 40% by weight, specific surface area 67 m ² / g) 0.084 g was dispersed in 400 g of water to prepare 4000.08 g of a silica fine particle dispersion having a solid content concentration of 0.0084 wt%.
Separately, 0.032 g of polyvinylpyrrolidone (made by ARDRICH: MW55000) as a metal complexing agent was dissolved in 42.45 g of water to prepare 42.77 g of a polyvinylpyrrolidone aqueous solution having a concentration of 0.075% by weight.
Next, 42.77 g of a metal complexing agent (polyvinylpyrrolidone) aqueous solution was added to a dispersion of silica fine particles having a solid content concentration of 0.0084% by weight and stirred at 20 ° C. for 1 hour to adsorb the metal complexing agent to the silica fine particles. It was.
The metal complexing agent / metal oxide fine particle weight ratio at this time was 0.95.

Next, 3.17 g of a chloroplatinic acid aqueous solution having a concentration of 6.65% by weight was added as an aqueous metal salt solution.
The metal salt / metal complexing agent molar ratio (M _MS ) / (M _MC ) at this time was 1.8.
Next, 7.82 g of a sodium borohydride aqueous solution having a concentration of 0.1% by weight as a reducing agent was added in 30 seconds, and then stirring was continued at 50 ° C. for 1 hour. At this time, the color changed to black.
The reducing agent / metal salt molar ratio at this time was 0.4.
Next, it is washed with sufficient ion exchange water by an ultrafiltration membrane method and concentrated to a total solid concentration of 20% by weight to prepare a metal oxide particle (2) dispersion for polishing which is a metal-coated silica particle. did.
Thereafter, the average particle diameter was measured and the coating state was observed in the same manner as in Example 1. The results are shown in the table.

Preparation of Polishing Slurry (2) A polishing slurry (2) was prepared in the same manner as in Example 1 except that a dispersion of polishing metal oxide particles (2) having a total solid concentration of 20% by weight was used.
Polishing test A polishing test was conducted in the same manner as in Example 1 except that the polishing slurry (2) was used. The results are shown in the table.

[Example 3]
Preparation of metal oxide particles (3) for polishing
As a metal oxide fine particle, 0.084 g of gold flat sugar-like silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid CO45A, average particle diameter 45 nm, solid content concentration 40 wt%, specific surface area 67 m ² / g) is dispersed in 400 g of water and solid. 400.08 g of a silica fine particle dispersion having a partial concentration of 0.0084% by weight was prepared.
Separately, 0.032 g of polyvinylpyrrolidone (made by ARDRICH: MW55000) as a metal complexing agent was dissolved in 42.45 g of water to prepare 42.77 g of a polyvinylpyrrolidone aqueous solution having a concentration of 0.075% by weight.
Next, 42.77 g of a metal complexing agent (polyvinylpyrrolidone) aqueous solution was added to a dispersion of silica fine particles having a solid content concentration of 0.0084% by weight and stirred at 20 ° C. for 1 hour to adsorb the metal complexing agent to the silica fine particles. It was.
The metal complexing agent / metal oxide fine particle weight ratio at this time was 0.95.

Next, 0.11 g of a chloroplatinic acid aqueous solution having a concentration of 6.65% by weight was added as an aqueous metal salt solution.
The metal salt / metal complexing agent molar ratio (M _MS ) / (M _MC ) at this time was 0.06.
Next, 0.26 sodium borohydride aqueous solution having a concentration of 0.1% by weight as a reducing agent was added in 30 seconds, and then the stirring was continued at 50 ° C. for 1 hour. At this time, the color changed to black.
The reducing agent / metal salt molar ratio at this time was 0.4.
Next, it is washed with sufficient ion exchange water by an ultrafiltration membrane method and concentrated to a total solid concentration of 20% by weight to prepare a metal oxide particle (3) dispersion for polishing which is a metal-coated silica particle. did.
Thereafter, the average particle diameter was measured and the coating state was observed in the same manner as in Example 1. The results are shown in the table.

Preparation of polishing slurry (3) A polishing slurry (3) was prepared in the same manner as in Example 1 except that a dispersion of polishing metal oxide particles (3) having a total solid concentration of 20% by weight was used.
Polishing test A polishing test was conducted in the same manner as in Example 1 except that the polishing slurry (3) was used. The results are shown in the table.

[Example 4]
Preparation of metal oxide particles (4) for polishing
As a metal oxide fine particle, 0.084 g of gold flat sugar-like silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid CO45A, average particle diameter 45 nm, solid content concentration 40 wt%, specific surface area 67 m ² / g) is dispersed in 400 g of water and solid. 400.08 g of a silica fine particle dispersion having a partial concentration of 0.0084% by weight was prepared.
Separately, 0.032 g of polyvinylpyrrolidone (made by ARDRICH: MW55000) as a metal complexing agent was dissolved in 42.45 g of water to prepare 42.77 g of a polyvinylpyrrolidone aqueous solution having a concentration of 0.075% by weight.
Next, 42.77 g of a metal complexing agent (polyvinylpyrrolidone) aqueous solution was added to a dispersion of silica fine particles having a solid content concentration of 0.0084% by weight and stirred at 20 ° C. for 1 hour to adsorb the metal complexing agent to the silica fine particles. It was.
The metal complexing agent / metal oxide fine particle weight ratio at this time was 0.95.

Next, 8.50 g of an aqueous chloroplatinic acid solution having a concentration of 6.65% by weight was added as an aqueous metal salt solution.
The metal salt / metal complexing agent molar ratio (M _MS ) / (M _MC ) at this time was 4.8.
Next, 20.9 g of a sodium borohydride aqueous solution having a concentration of 0.1% by weight as a reducing agent was added in 30 seconds, and then stirring was continued at 50 ° C. for 1 hour. At this time, the color changed to black.
The reducing agent / metal salt molar ratio at this time was 0.4.
Next, it is washed with sufficient ion-exchanged water by an ultrafiltration membrane method and concentrated to a total solid content of 20% by weight to prepare a metal oxide particle (4) dispersion for polishing which is a metal-coated silica particle. did.
Thereafter, the average particle diameter was measured and the coating state was observed in the same manner as in Example 1. The results are shown in the table.

Preparation of polishing slurry (4) A polishing slurry (4) was prepared in the same manner as in Example 1 except that a dispersion of polishing metal oxide particles (4) having a total solid concentration of 20% by weight was used.
Polishing Test A polishing test was conducted in the same manner as in Example 1 except that the polishing slurry (4) was used. The results are shown in the table.

[Example 5]
Preparation of metal oxide particles (5) for polishing Silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid SI-80P, average particle diameter 80 nm, surface potential -60 mV, SiO ₂ concentration 20 wt%, pH 10.2) positive to 750 g 150 g of an ion exchange resin (ROHMHARS Co., Ltd .: Duolite) was mixed and stirred for 0.5 hour.
Next, after separating the cation exchange resin, 135 g of an anion exchange resin (Mitsubishi Chemical Co., Ltd .: SUNUP-C) was mixed and stirred for 0.5 hour, and then the anion exchange resin was separated, 750 g of purified silica sol having a SiO ₂ concentration of 20% by weight was prepared.
Next, 5.1 g of polyaluminum chloride (manufactured by Taki Chemical Co., Ltd .: Takibaine # 1000, Al ₂ O ₃ concentration 23.55 wt%) was added to 750 g of purified silica sol, and the mixture was stirred at room temperature for 0.5 hour. Subsequently, 2903 g of pure water was added and diluted to prepare 3659 g of a dispersion of metal oxide particles for substrate (A-1) made of silica having a SiO ₂ concentration of 4.1 wt%. The pH of the metal oxide particle (A-1) dispersion for the substrate was 3.7.

Next, 3659 g of the substrate metal oxide particle (A-1) dispersion composed of silica having a SiO ₂ concentration of 4.1% by weight was added to the silica sol (JGC Catalysts & Chemicals Co., Ltd.) as the coating metal oxide particle (B-1). Manufactured by Cataloid SN-350, average particle diameter 7 nm, surface potential -23 mV, SiO ₂ concentration 16.6 wt%, pH 3.7) 367 g. At this time, the SiO ₂ concentration of the mixed dispersion was 4.8% by weight and the pH was 3.5. Next, 135 g of an anion exchange resin (manufactured by Mitsubishi Chemical Co., Ltd .: SUNUP-C) was mixed in the mixed dispersion, and the mixture was stirred for 0.5 hour. Then, the anion exchange resin was separated, and the SiO ₂ concentration was separated by a rotary evaporator. A dispersion composed of 10% by weight of silica was prepared. The pH of the dispersion was 9.0. (Process (b))
Next, the mixture was aged at 93 ° C. for 3 hours, and then concentrated by a rotary evaporator to prepare a dispersion having a SiO ₂ concentration of 10% by weight. The pH of the dispersion was 9.0. (Process (c))
Next, an aqueous acetic acid solution having a concentration of 3% by weight was added to adjust the pH of the dispersion to 5.5, and then concentrated by a rotary evaporator to prepare a dispersion composed of silica having a SiO ₂ concentration of 10% by weight. (Process (d))
The obtained dispersion was dried at 120 ° C. for 15 hours, and then fired at 1000 ° C. for 2 hours to prepare metal oxide particles made of silica. (Process (f))
Next, the metal oxide particles are dispersed in pure water to obtain a dispersion having a SiO ₂ concentration of 10% by weight, and pulverized for 180 minutes at 2160 rpm in a sand mill (manufactured by Shinmaru Enterprises Co., Ltd .: glass beads 0.5 mmφ1100 g). Thus, a metal oxide particle dispersion was prepared. (Process (g))
Next, the dispersion from which the beads have been separated is separated at 2000 rpm for 3 minutes by a centrifuge (manufactured by Hitachi, Ltd .: high-speed cooling centrifuge), concentrated on a rotary evaporator, and oxidized with a SiO ₂ concentration of 40% by weight. A product particle (5) dispersion was produced.

The average particle diameter and specific surface area of the obtained metal oxide particles (5) are shown in the table, and the SEM photograph is shown in FIG.
Next, a metal oxide particle (5) dispersion for polishing, which is metal-coated silica particles having a total solid content of 20% by weight, was prepared in the same manner as in Example 2 except that the metal oxide particle (5) dispersion was used. did.
Thereafter, the average particle diameter was measured and the coating state was observed in the same manner as in Example 1. The results are shown in the table.

Preparation of polishing slurry (5) A polishing slurry (5) was prepared in the same manner as in Example 1 except that a polishing metal oxide particle (5) dispersion having a total solid content of 20% by weight was used.
Polishing Test A polishing test was conducted in the same manner as in Example 1 except that the polishing slurry (5) was used. The results are shown in the table.

[Example 6]
Preparation of metal oxide particles (6) for polishing 37.5 g of cerium (III) sulfate octahydrate and 1765.8 g of distilled water were placed in a 5 L container and dissolved by stirring. Subsequently, the temperature was raised to 93 ° C. while stirring, and 1255 g of a 1.0% aqueous sodium hydroxide solution was added all at once, and the temperature was maintained at 93 ° C. for 6 hours with stirring. Next, when it cooled to 30 degrees C or less, white precipitate was obtained. The pH of this solution was 10.0. This solution was treated at 14000 rpm for 10 minutes using a centrifugal separator, and then the supernatant was removed. Distilled water (2884.5 g) was added to the white precipitate, and the mixture was further treated with a centrifugal separator at 14000 rpm for 10 minutes. This operation was performed three times in total, and the precipitate was washed to prepare a ceria fine particle dispersion (CeO ₂ concentration 2.1 wt%, pH 10.0). The obtained ceria fine particles were monodispersed and the average particle size was 13 nm.
Next, 75.0 g of cation exchange resin (ROHMHARS Co., Ltd .: Duolite) was mixed with 3571.4 g of ceria fine particle dispersion, and stirred for 0.5 hour to disperse the metal oxide particles (B-2) for coating. A liquid was prepared.
The pH of the coating metal oxide particle (B-2) dispersion was 3.0.

Subsequently, the metal oxide particles for coating (B-2) were added to 3659 g of the substrate metal oxide particles (A-1) dispersion made of silica having a SiO ₂ concentration of 4.1 wt% prepared in the same manner as in Example 5. 3571.4 g of the dispersion was mixed. At this time, the pH of the mixed dispersion was 3.2. (Process (a))
Thereafter, steps (b) to (g) were carried out in the same manner as in Example 5 to produce a dispersion of metal oxide particles (6) having a SiO ₂ concentration of 40% by weight.
Next, a polishing metal oxide particle (6) dispersion, which is a metal-coated silica particle having a total solid concentration of 20% by weight, was prepared in the same manner as in Example 2 except that the metal oxide particle (6) dispersion was used. Prepared.
Thereafter, the average particle diameter was measured and the coating state was observed in the same manner as in Example 1. The results are shown in the table.

Preparation of polishing slurry (6) A polishing slurry (6) was prepared in the same manner as in Example 1 except that a dispersion of polishing metal oxide particles (6) having a total solid concentration of 20% by weight was used.
Polishing Test A polishing test was conducted in the same manner as in Example 1 except that the polishing slurry (6) was used. The results are shown in the table.

[Example 7]
Preparation of Polishing Metal Oxide Particles (7) 100 g of pure water, fibrous alumina fine particles (average length of 50 nm, average diameter of cross section of 10 nm), silver nitrate aqueous solution and palladium nitrate aqueous solution, with a total solid content of 1.0 It becomes _{wt%, Ag: Pd: Al 2} O 3 = 60: 20: mixed to prepare a fibrous alumina fine particles dispersed metal salt aqueous solution such that 20.
The total number of moles of silver nitrate and palladium nitrate in this aqueous solution containing trisodium citrate (an organic stabilizer and a reducing agent) in an amount of 0.01 parts by weight per 1 part by weight of Ag · Pd metal. An equimolar number of ferrous sulfate (reducing agent) aqueous solution was added and stirred for 1 hour under a nitrogen atmosphere to obtain a dispersion of composite metal fine particles.
The obtained dispersion is separated by a centrifuge, then acid washed with a 1% by weight HCl aqueous solution, then dispersed in pure water, and then polyacrylic acid is 0.0128 weight per 1 part by weight of the composite metal. And then concentrated by a rotary evaporator to prepare a dispersion having a total solid concentration of 20% by weight. Subsequently, the obtained dispersion was treated with a nanomizer system (Nanomizer Co., Ltd .: LA-33-S) to obtain a metal oxide particle (7) dispersion for polishing.

Preparation of polishing slurry (7) A polishing slurry (7) was prepared in the same manner as in Example 1 except that a dispersion of polishing metal oxide particles (7) having a total solid concentration of 20% by weight was used.
Polishing Test A polishing test was conducted in the same manner as in Example 1 except that the polishing slurry (7) was used. The results are shown in the table.

[Example 8]
Preparation of metal oxide particles for polishing (8)
As a metal oxide fine particle, 0.084 g of silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid SI-45P, average particle diameter 45 nm, solid content concentration 40 wt%, specific surface area 61 m ² / g) is dispersed in 400 g of water and solid. 400.08 g of a silica fine particle dispersion having a partial concentration of 0.0084% by weight was prepared.
Separately, 0.032 g of polyvinylpyrrolidone (made by ARDRICH: MW55000) as a metal complexing agent was dissolved in 42.45 g of water to prepare 42.77 g of a polyvinylpyrrolidone aqueous solution having a concentration of 0.075% by weight.
Next, 42.77 g of a metal complexing agent (polyvinylpyrrolidone) aqueous solution was added to a dispersion of silica fine particles having a solid content concentration of 0.0084% by weight and stirred at 20 ° C. for 1 hour to adsorb the metal complexing agent to the silica fine particles. It was.
The metal complexing agent / metal oxide fine particle weight ratio at this time was 0.95.

Next, 12.75 g of a chloroplatinic acid aqueous solution having a concentration of 6.65% by weight was added as an aqueous metal salt solution.
The metal salt / metal complexing agent molar ratio (M _MS ) / (M _MC ) at this time was 7.18.
Next, 31.23 g of an aqueous solution of sodium borohydride having a concentration of 0.1% by weight as a reducing agent was added in 30 seconds, and then stirring was continued at 50 ° C. for 1 hour. At this time, the color changed to black.
The reducing agent / metal salt molar ratio at this time was 0.4.
Next, it is washed with sufficient ion-exchanged water by an ultrafiltration membrane method, and concentrated to a total solid concentration of 20% by weight to prepare a metal oxide particle (8) dispersion for polishing which is a metal-coated silica particle. did.
Thereafter, the average particle diameter was measured and the coating state was observed in the same manner as in Example 1. The results are shown in the table.

Preparation of polishing slurry (8) A polishing slurry (8) was prepared in the same manner as in Example 1 except that a dispersion of polishing metal oxide particles (8) having a total solid concentration of 20% by weight was used.
Polishing Test A polishing test was conducted in the same manner as in Example 1 except that the polishing slurry (8) was used. The results are shown in the table.

[Example 9]
Preparation of metal oxide particles for polishing (9) Silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid SI-45P, average particle size 45 nm, solid content concentration 40 wt%, specific surface area 61 m ² / g) as metal oxide fine particles 0.084 g was dispersed in 400 g of water to prepare 4000.08 g of a silica fine particle dispersion having a solid content concentration of 0.0084 wt%.
Separately, 0.032 g of polyvinylpyrrolidone (made by ARDRICH: MW55000) as a metal complexing agent was dissolved in 42.45 g of water to prepare 42.77 g of a polyvinylpyrrolidone aqueous solution having a concentration of 0.075% by weight.
Next, 42.77 g of a metal complexing agent (polyvinylpyrrolidone) aqueous solution was added to a dispersion of silica fine particles having a solid content concentration of 0.0084% by weight and stirred at 20 ° C. for 1 hour to adsorb the metal complexing agent to the silica fine particles. It was.
The metal complexing agent / metal oxide fine particle weight ratio at this time was 0.95.

Next, 1.06 g of a chloroplatinic acid aqueous solution having a concentration of 6.65% by weight was added as an aqueous metal salt solution.
The metal salt / metal complexing agent molar ratio (M _MS ) / (M _MC ) at this time was 0.6.
Next, a sodium borohydride aqueous solution 2.61 having a concentration of 0.1% by weight as a reducing agent was added in 30 seconds, and then stirring was continued at 50 ° C. for 1 hour. At this time, the color changed to black.
The reducing agent / metal salt molar ratio at this time was 0.4.
Next, it is washed with sufficient ion-exchanged water by an ultrafiltration membrane method and concentrated to a total solid content concentration of 20% by weight to prepare a metal oxide particle (9) dispersion for polishing which is a metal-coated silica particle. did.
Thereafter, the average particle diameter was measured and the coating state was observed in the same manner as in Example 1. The results are shown in the table.

Preparation of polishing slurry (9) A polishing slurry (9) was prepared in the same manner as in Example 1 except that a dispersion of polishing metal oxide particles (9) having a total solid content of 20% by weight was used.
Polishing Test A polishing test was conducted in the same manner as in Example 1 except that the polishing slurry (9) was used. The results are shown in the table.

[Example 10]
Preparation of the polishing slurry (10) The polishing slurry (2) prepared in the same manner as in Example 2 was mixed with an HF aqueous solution so that the HF concentration was 0.5% by weight to prepare the polishing slurry (10). Prepared.
Polishing Test A polishing test was conducted in the same manner as in Example 1 except that the polishing slurry (10) was used. The results are shown in the table.

[Example 11]
Preparation of Metal Oxide Particles for Polishing (11) As a metal oxide fine particle, Kompei sugar silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid CO45A, average particle diameter 45 nm, solid content concentration 40% by weight, specific surface area 67 m ² / g) 0.084 g was dispersed in 400 g of water to prepare 4000.08 g of a silica fine particle dispersion having a solid content concentration of 0.0084 wt%.
Separately, 0.032 g of polyvinylpyrrolidone (made by ARDRICH: MW55000) as a metal complexing agent was dissolved in 42.45 g of water to prepare 42.77 g of a polyvinylpyrrolidone aqueous solution having a concentration of 0.075% by weight.
Next, 42.77 g of a metal complexing agent (polyvinylpyrrolidone) aqueous solution was added to a dispersion of silica fine particles having a solid content concentration of 0.0084% by weight and stirred at 20 ° C. for 1 hour to adsorb the metal complexing agent to the silica fine particles. It was.

Next, 1.58 g of an aqueous silver nitrate solution having a concentration of 10% by weight was added as an aqueous metal salt solution. Next, 9.0 g of a sodium borohydride aqueous solution having a concentration of 0.1% by weight as a reducing agent was added in 30 seconds, and then stirring was continued at 50 ° C. for 1 hour. At this time, the color changed to black.
Next, it is washed with sufficient ion-exchanged water by the ultrafiltration membrane method, and concentrated to a total solid concentration of 20% by weight to prepare a metal oxide particle (11) dispersion for polishing which is a metal-coated silica particle. did.
Thereafter, the average particle diameter was measured and the coating state was observed in the same manner as in Example 1. The results are shown in the table.

Preparation of polishing slurry (11) To a dispersion of polishing metal oxide particles (11) having a total solid concentration of 20% by weight, acetic acid and ultrapure water having a concentration of 1% by weight were added, and the SiO ₂ concentration was 10.0% by weight. A polishing slurry (11) having a pH of 5.0 adjusted to be prepared was prepared.
The SiC substrate to be used in the polishing test example 1 was set in a polishing apparatus (manufactured by Japan Eggins Co., Ltd .: EJ-380IN), and “Suba800” manufactured by Nitta Haas was used as a polishing pad, and the substrate load was 26 KPa. The polishing slurry (1) is 10 g / min at a table rotation speed of 60 rpm, the hydrogen peroxide solution having a concentration of 5% by weight is 10 g / min, and the aqueous HF solution having a concentration of 3% by weight is 10 g / min. Were separately supplied for 4 hours for polishing. The polishing rate was calculated by determining the weight change of the substrate to be polished before and after polishing. Further, Ra was measured for surface smoothness with an atomic force microscope (AFM) (manufactured by Hitachi High-Tech Science Co., Ltd.). The results are shown in the table.

[Example 12]
Preparation of metal oxide particles for polishing (12)
As a metal oxide fine particle, 0.084 g of gold flat sugar-like silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid CO45A, average particle diameter 45 nm, solid content concentration 40 wt%, specific surface area 67 m ² / g) is dispersed in 400 g of water and solid. 400.08 g of a silica fine particle dispersion having a partial concentration of 0.0084% by weight was prepared.
Separately, 0.032 g of polyvinylpyrrolidone (made by ARDRICH: MW55000) as a metal complexing agent was dissolved in 42.45 g of water to prepare 42.77 g of a polyvinylpyrrolidone aqueous solution having a concentration of 0.075% by weight.
Next, 42.77 g of a metal complexing agent (polyvinylpyrrolidone) aqueous solution was added to a dispersion of silica fine particles having a solid content concentration of 0.0084% by weight and stirred at 20 ° C. for 1 hour to adsorb the metal complexing agent to the silica fine particles. It was.

Next, 0.79 g of 10 wt% silver nitrate aqueous solution and 0.80 g of 10 wt% palladium nitrate aqueous solution were added as the metal salt aqueous solution. At this time, Ag: Pd = 1: 1. Next, 9.0 g of a sodium borohydride aqueous solution having a concentration of 0.1% by weight as a reducing agent was added in 30 seconds, and then stirring was continued at 50 ° C. for 1 hour. At this time, the color changed to black.
Next, it is washed with sufficient ion-exchanged water by an ultrafiltration membrane method and concentrated to a total solid content concentration of 20% by weight to prepare a metal oxide particle (12) dispersion for polishing which is a metal-coated silica particle. did.
Thereafter, the average particle diameter was measured and the coating state was observed in the same manner as in Example 1. The results are shown in the table.

Preparation of polishing slurry (12) A polishing slurry (12) was prepared in the same manner as in Example 11 except that a polishing metal oxide particle (12) dispersion having a total solid content of 20% by weight was used.
Polishing Test A polishing test was conducted in the same manner as in Example 11 except that the polishing slurry (12) was used. The results are shown in the table.

[Example 13]
Preparation of polishing slurry (13) Polishing slurry in the same manner as in Example 12 except that the dispersion of polishing metal oxide particles (2) having a total solid concentration of 20% by weight prepared in the same manner as in Example 2 was used. (13) was prepared.

Polished substrate (Si)
Final polishing of the surface of a 4 H-Si wafer having a diameter of 4 inches was performed. The surface roughness of the wafer was Ra = 1.2 nm as a result of measurement by AFM.
Polishing Test A polishing test was conducted in the same manner as in Example 12 except that the polishing slurry (13) was used and the substrate to be polished (Si wafer) was used. The results are shown in the table.

[Example 14]
Polishing Test A polishing test was conducted in the same manner as in Example 11 except that the polishing slurry (11) prepared in the same manner as in Example 11 was used and the substrate to be polished (Si) was used. The results are shown in the table.

[Comparative Example 1]
Preparation of polishing metal oxide particles (R1) As a polishing metal oxide particles (R1), silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid SI-45P, average particle size 45 nm, solid content concentration 48% by weight) is SiO. Dilution with pure water to a concentration of ₂ % by weight was performed to obtain a polishing metal oxide particle (R1) dispersion.
Preparation of polishing slurry (R1) A polishing slurry (R1) was prepared in the same manner as in Example 1 except that a dispersion of polishing metal oxide particles (R1) having a SiO ₂ concentration of 20% by weight was used.
Polishing Test A polishing test was conducted in the same manner as in Example 1 except that the polishing slurry (R1) was used. The results are shown in the table.

[Comparative Example 2]
Preparation of Metal Oxide Particles (R2) for Polishing Gold Flat Sugar Silica Sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid CO45A, average particle size 45 nm, solid content concentration 40% by weight, specific surface area 67 m ² / g) with SiO ₂ concentration 20 A metal oxide particle (R2) dispersion for polishing was obtained by diluting with pure water to a weight percent.
Preparation of polishing slurry (R2) A polishing slurry (R2) was prepared in the same manner as in Example 1 except that a dispersion of polishing metal oxide particles (R2) having a SiO ₂ concentration of 20% by weight was used.
Polishing Test A polishing test was conducted in the same manner as in Example 1 except that the polishing slurry (R2) was used. The results are shown in the table.

[Comparative Example 3]
Preparation of metal oxide particles (R3) for polishing In the same manner as in Example 5, the dispersion of metal oxide particles (5) having a SiO ₂ concentration of 40% by weight as sunflower particles was adjusted to a SiO ₂ concentration of 20% by weight. Dilution with pure water gave a metal oxide particle (R3) dispersion for polishing.
Preparation of polishing slurry (R3) A polishing slurry (R3) was prepared in the same manner as in Example 1 except that a dispersion of polishing metal oxide particles (R3) having a SiO ₂ concentration of 20% by weight was used.
Polishing Test A polishing test was conducted in the same manner as in Example 1 except that the polishing slurry (R3) was used. The results are shown in the table.

[Comparative Example 4]
Preparation of metal oxide particles (R4) for polishing In the same manner as in Example 6, the dispersion of metal oxide particles (6) having a SiO ₂ concentration of 40% by weight as sunflower particles was adjusted to a SiO ₂ concentration of 20% by weight. Dilution with pure water gave a metal oxide particle (R4) dispersion for polishing.
Preparation of polishing slurry (R4) A polishing slurry (R4) was prepared in the same manner as in Example 1 except that a dispersion of polishing metal oxide particles (R4) having a SiO ₂ concentration of 20% by weight was used.
Polishing Test A polishing test was conducted in the same manner as in Example 1 except that the polishing slurry (R4) was used. The results are shown in the table.

[Comparative Example 5]
Preparation of polishing metal oxide particles (R5) Fibrous alumina fine particles (fibrous alumina fine particles having an average length of 50 nm and a cross-sectional average diameter of 10 nm) dispersed in pure water to obtain an abrasive concentration of 20 wt% alumina An oxide particle (R5) dispersion was obtained.
Preparation of polishing slurry (R5) A polishing slurry (R5) was prepared in the same manner as in Example 1 except that a dispersion of polishing metal oxide particles (R5) having an alumina concentration of 20% by weight was used.
Polishing Test A polishing test was conducted in the same manner as in Example 1 except that the polishing slurry (R5) was used. The results are shown in the table.

[Comparative Example 6]
Preparation of metal oxide particles (R6) for polishing
Preparation of metal fine particle dispersion A metal salt aqueous solution obtained by dissolving 25 g of chloroplatinic acid hexahydrate (9 g in terms of platinum metal) in 16,000 g of pure water has a concentration of 5.0% by weight as a complexing stabilizer. 1.660 g of trisodium citrate aqueous solution and 140 g of sodium borohydride aqueous solution having a concentration of 0.1% by weight as a reducing agent are added and stirred and mixed at 20 ° C. in a nitrogen atmosphere to disperse platinum fine particles in water. A platinum colloid solution was obtained. Next, the platinum colloid solution was washed and desalted using an ultrafilter (manufactured by ADVANTEC: Ultrafilter Q0500), concentrated, and a platinum colloid solution (R6-1) having a concentration of 20.0% by weight in terms of platinum metal. did. When the particle diameter of the obtained platinum colloid was measured with a scanning electron microscope (manufactured by Hitachi, Ltd .: S-5500), the average particle diameter was 2 nm.
Preparation of Polishing Slurry (R6) 100 g of a metal oxide particle (R1) dispersion having a SiO ₂ concentration of 20% by weight prepared in the same manner as in Comparative Example 1 and 300 g of a platinum colloid solution (R6-1) were mixed. Next, acetic acid having a concentration of 1% by weight and ultrapure water were added to prepare a polishing slurry (R6) having a total solid concentration of 10.0% by weight and a pH of 5.0.
Polishing test A polishing test was conducted in the same manner as in Example 11 except that the polishing slurry (R6) was used. The results are shown in the table.

[Comparative Example 7]
Preparation of Polishing Slurry (R7) 100 g of a metal oxide particle (R1) dispersion having a SiO ₂ concentration of 20% by weight prepared in the same manner as in Comparative Example 1 and Ag nanoparticles (JGC Catalysts & Chemicals, Inc .: ELCOM MK) -5001 SIV, concentration 10 wt%, average particle size 10 nm, pH 4.0) 600 g was mixed and concentrated to 20 wt% with a rotary evaporator, then 1 wt% acetic acid and ultrapure water were added to give a total solids concentration A polishing slurry (R7) of 10.0% by weight and pH 5.0 was prepared.
Polishing Test A polishing test was conducted in the same manner as in Example 11 except that the polishing slurry (R7) was used. The results are shown in the table.

[Comparative Example 8]
Polishing Test A polishing test of the Si substrate was conducted in the same manner as in Example 13 except that the polishing slurry (R1) prepared in the same manner as in Comparative Example 1 was used. The results are shown in the table.

6 is a SEM photograph taken of the metal oxide particles (5) obtained in Example 5.

Claims (10)

  A metal-supported metal oxide particle for polishing, wherein a metal is supported on the metal oxide particle. The metal-supported metal oxide particles for polishing according to claim 1, wherein the average particle diameter (D _A ) is in the range of 7 to 600 nm.   The metal is at least one selected from Ag, Pd, Au, Pt, Cu, and Fe, and the amount of the metal supported is in the range of 0.01 to 1200 parts by weight as a metal with respect to 100 parts by weight of the metal oxide particles. The metal-supported metal oxide particle for polishing according to claim 1 or 2,   The metal-supported metal oxide particles for polishing according to any one of claims 1 to 3, wherein the metal oxide particles have a non-spherical shape.   The metal-supported metal oxide particles for polishing according to any one of claims 1 to 4, wherein at least a part of the metal is supported on an outer surface of the metal oxide particles. The metal oxide particles are at least one selected from SiO ₂ , Al ₂ O ₃ , Sb ₂ O ₅ , ZrO ₂ , TiO ₂ , Fe ₂ O ₃ , CeO ₂ and complex oxides thereof, or a mixture thereof. The metal-supported metal oxide particles for polishing according to any one of claims 1 to 5. The metal oxide particles are at least one selected from SiO ₂ , Al ₂ O ₃ , CeO ₂ and a composite oxide thereof, or a mixture thereof, and the metal is at least one selected from Ag, Pd, and Pt. The metal-supported metal oxide particles for polishing according to claim 1 or 2.
  An abrasive comprising the metal-supported metal oxide particles for polishing according to any one of claims 1 to 7.   The abrasive according to claim 8, further comprising an oxidizing agent.   The polishing agent according to claim 8 or 9, wherein the polishing target is at least one selected from any of Si, SiC, GaN, Al, AlN, Cu, TiN, and SiN.