JP2011136402A - Polishing particle dispersion liquid comprising aggregate of organic particle and silica particle, and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polishing particle used for polishing a semiconductor wafer, a glass hard disk, an alumina hard disk or the like and capable of reducing generation of scratch on a surface to be polished when it is used at a practical polishing speed. <P>SOLUTION: The polishing particle is made to a polishing particle by preparing a composite particle (hetero-aggregate) of an organic particle and an inorganic particle having the size equal or more to that of the organic particle. In the polishing particle, the particle is deformed when a polishing pressure becomes high, generation of scratch is suppressed by maintaining the polishing speed, and sufficient polishing performance can be exhibited. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a polishing particle dispersion suitable for polishing semiconductor wafers, glass hard disks, alumina hard disks, and the like, and a method for producing the same.

  Conventionally, aqueous dispersions containing inorganic particles such as silica sol or alumina sol have been used as polishing agents used for polishing semiconductor wafers, glass hard disks, alumina hard disks, and the like. However, the aqueous dispersion containing the inorganic particles may cause a linear mark (hereinafter also referred to as “scratch”) on the surface to be polished due to an agglomerate or the like. In order to solve this problem, various methods have been proposed such as adding a surfactant to the aqueous dispersion and removing coarse particles with a filter. However, these methods do not improve the polishing agent itself, and may cause problems such as a reduction in polishing rate and contamination of the surface to be polished by metal ions.

  Further, Patent Document 1 (Japanese Patent Laid-Open No. 7-86216) discloses a method of polishing a film to be processed of a semiconductor device with an abrasive containing not only inorganic particles but also abrasive particles mainly composed of an organic polymer compound or the like. It is disclosed. According to this method, after polishing, the abrasive particles remaining on the surface to be polished can be burned and removed, and the occurrence of defects in products such as semiconductor devices due to the remaining particles can be suppressed. However, since the particles made of an organic polymer compound have a lower hardness than inorganic particles such as silica and alumina, there is a problem that it is difficult to increase the polishing rate.

  Patent Document 2 (Japanese Patent Publication No. 6-40951) discloses a method of producing composite particles by mixing particles whose zeta potential has an opposite sign. However, in this method, since each particle adheres only by electrostatic force, there is a possibility that the particle is separated when a large shear stress is applied to the composite particle.

  Patent Document 3 (Japanese Patent Laid-Open No. 2001-152135) describes an aqueous dispersion A of polymer particles and an aqueous dispersion B of inorganic particles, wherein the zeta potential of the polymer particles and the zeta potential of the inorganic particles are as follows. After mixing in the pH range having the same sign to prepare an aqueous dispersion C containing the polymer particles and the inorganic particles, the pH of the aqueous dispersion C is changed to the zeta potential of the polymer particles and the inorganic particles. Disclosed is a method for producing an aqueous dispersion for chemical mechanical polishing, wherein the composite particles comprising the polymer particles and the inorganic particles are formed by changing the zeta potential of the particles to have an opposite sign. Yes. The abrasive particles obtained by this production method are intended to form a coating layer with a large number of inorganic particles adhering to the surface of the polymer particles. When the inorganic particles are larger than the polymer particles, There is a description that it is not preferable such that scratches are likely to occur.

In Patent Document 4 (Japanese Patent Laid-Open No. 11-114808), by using an abrasive in which a composite abrasive in which child particles are supported on the surface of mother particles is added as abrasive grains and dispersed as a slurry, a glass material or Regarding polishing of semiconductor devices and the like, it is described that it does not contain contaminants, maintains a surface processing state equivalent to that of current silica abrasives, and can improve the polishing rate over silica abrasives. This abrasive has a structure in which child particles such as silica adhere to mother particles made of an organic resin.

  Patent Document 5 (Japanese Patent Application Laid-Open No. 2002-97456) discloses abrasive particles composed of mother particles and a plurality of child particles fixedly attached to the surface of the mother particles, and has an average particle diameter having elasticity as the mother particles. The present invention relates to abrasive particles in which spherical polymer particles of 1 to 100 μm are used, and silica or the like selected from hard particles having an average particle diameter of 1/500 to 1/10 of an average particle diameter of mother particles is used as a child particle. The invention is disclosed. The abrasive particles also have a structure in which child particles such as silica adhere to mother particles made of an organic resin, as in Patent Document 4.

  Although abrasive particles as described in the above patent documents have been proposed, there has been a demand for abrasive particles that can further suppress the occurrence of scratches.

JP-A-7-86216 Japanese Patent Publication No. 6-40951 JP 2001-152135 A Japanese Patent Laid-Open No. 11-114808 JP 2002-97456 A

  The present invention solves the above-described conventional problems, and is a polishing particle dispersion in which an aggregate composed of organic particles and silica particles having a size equal to or larger than the organic particles is dispersed in a dispersion medium. The purpose is to provide.

A first invention according to the present application is a polishing particle dispersion in which polishing particles having an average particle diameter (Dm) of 10 to 300 nm made of an aggregate of silica particles and organic particles are dispersed in a dispersion medium. The following conditions are satisfied.
(1) The average particle diameter (Da) of the silica particles is in the range of 15 to 240 nm (2) The average particle diameter (Db) of the organic particles is in the range of 5 to 80 nm (3) (Da) / (Db) Values range from 1.0 to 3.0

  2nd invention in this application is the said particle | grain dispersion liquid whose mass ratio of the silica particle in the said particle | grain for polishing and organic type particle | grains is the range of 100: 1-100: 50.

  According to a third invention of the present application, the organic particles are selected from acrylic resins, epoxy resins, urethane resins, polyester resins, amide resins, or copolymers thereof. It is a particle dispersion.

  According to a fourth aspect of the present application, the polishing particle dispersion and at least one additive selected from the group consisting of a polishing accelerator, a surfactant, a heterocyclic compound, a pH adjuster, and a pH buffer, and It is an abrasive | polishing agent composition containing this.

5th invention which concerns on this application is 100 mass parts (solid content conversion) of the silica particle dispersion of the following (a), 1-50 mass parts (solid content conversion) of the organic type particle dispersion of the following (b), Are mixed in a pH range in which the difference between the zeta potentials is 10 mV or more, and maintained in a range of 5 to 70 ° C., thereby producing a polishing particle dispersion liquid that is heteroaggregated.
(A) A silica particle dispersion (solid content) in which silica particles having an average particle diameter (Da) in the range of 15 to 240 nm and a zeta potential (Za) in the range of −20 to −60 mV are dispersed in a dispersion medium. (Concentration 10-40% by mass)
(B) An organic particle dispersion in which organic particles having an average particle diameter (Db) in the range of 5 to 80 nm and a zeta potential (Zb) in the range of −3 to −30 mV are dispersed in a dispersion medium ( (Solid content concentration of 1 to 20% by mass) (however, (Da) / (Db) = limited to a range of 1.0 to 3.0)

  In the polishing particle dispersion according to the present invention, the polishing pressure is high because the polishing particles are aggregates (heteroaggregates) of organic particles and inorganic particles having a size equal to or larger than the organic particles. Then, the particles are deformed, the polishing rate is maintained, the generation of scratches is suppressed, and good polishing performance can be exhibited.

(1) Polishing particle dispersion The polishing particle dispersion according to the present invention uses, as a dispersion medium, an aggregate (heteroaggregate) of organic particles and silica particles having a size equal to or larger than the organic particles. More specifically, an abrasive particle dispersion in which abrasive particles having an average particle diameter (Dm) of 10 to 300 nm composed of an aggregate of silica particles and organic particles are dispersed in a dispersion medium. The liquid is characterized by satisfying the following conditions.
(1) The average particle diameter (Da) of the silica particles is in the range of 15 to 240 nm (2) The average particle diameter (Db) of the organic particles is in the range of 5 to 80 nm (3) (Da) / (Db) Values range from 1.0 to 3.0

  The average particle diameter of the abrasive particles is preferably in the range of 10 to 300 nm as measured by an image analysis method. When the average particle size is less than 10 nm, a practical polishing rate may not be obtained. When the average particle diameter exceeds 300 nm, it may not be easy to prepare by the production method according to the present invention. The average particle diameter of the abrasive particle diameter is preferably 50 to 290 nm, and more preferably 70 to 260 nm.

  Regarding the relationship between the size of the silica particles and the organic particles, it is necessary to satisfy the relationships (1), (2), and (3). In particular, it is desirable that the organic particles are in a range equal to or more than three times that of the silica particles. When in this range, the abrasive particles are deformed by the load received from the polishing cloth or the like during the polishing process, and thus the generation of scratches on the surface to be polished can be suppressed. However, when the value of (Da) / (Db) exceeds 3.0, the ratio of silica particles becomes excessive, and the effect of the present invention tends to be difficult to occur. The range of (Da) / (Db) is more preferably in the range of 1.5 to 2.5, and still more preferably in the range of 1.6 to 2.0. If it is less than 1.0, the desired polishing performance cannot be obtained.

  The range of the average particle size (Da) of the silica particles (15 to 240 nm) and (2) the range of the average particle size (Db) of the organic particles (5 to 80 nm) are the values of (Da) / (Db). It is required to meet the range (1.0 to 3.0) and the average particle size range (10 to 300 nm) of the abrasive particles. When the average particle diameter (Da) of the silica particles is less than 15 nm, the polishing rate tends to decrease when such polishing particles are used. Similarly, when (Da) exceeds 240 nm, when such abrasive particles are used, the occurrence of scratches on the polished surface tends to increase.

  When the average particle diameter (Db) of the organic particles is less than 5 nm, such polishing particles tend to have difficulty in obtaining a practical polishing rate. Similarly, when (Db) exceeds 80 nm, heteroaggregation may hardly occur.

In the polishing particles, the mass ratio of silica particles to organic particles is preferably in the range of 100: 1 to 100: 50. In the method for producing a polishing particle dispersion according to the present invention described later, silica particles and organic particles used as raw materials are mixed in a pH range such that the difference in zeta potential is 10 mV or more. The total amount formed can form aggregates by heteroaggregation. In the polishing particles, when the mass ratio of the organic particles to 100 parts by mass of the silica particles is less than 1 part by mass, the formation of aggregates is extremely small, and the performance improvement regarding the polishing rate and the scratch generation suppression is can not see. When the mass ratio of the organic particles with respect to 100 parts by mass of the silica particles exceeds 50 parts by mass, the ratio of the organic particles having a large specific gravity with respect to the silica becomes excessive, and the polishing rate tends to decrease. The mass ratio between the silica particles and the organic particles is preferably in the range of 100: 15 to 100: 45, more preferably in the range of 100: 20 to 100: 40.
The solid content concentration of the abrasive particle dispersion according to the present invention is not particularly limited, but a range of 0.5 to 50% by mass is usually recommended. When importance is attached to the efficiency of the polishing treatment, a range of 3 to 30% by mass is recommended.

Silica Particles As the silica particles used in the present invention, known silica particles having an average particle diameter measured by an image analysis method in the range of 15 to 240 nm can be used. In the production method according to the present invention, the silica particles are used as a silica particle dispersion having a silica concentration of 1 to 50% by mass. Examples of the method for preparing such a silica particle dispersion include the following production methods (1) to (4), but are not limited thereto.

(1) A silicic acid solution obtained by dealkalizing a water-soluble silicate selected from alkali metal silicate, tertiary ammonium silicate, quaternary ammonium silicate or guanidine silicate is heated in the presence of alkali. A method for producing a silica sol comprising a step of polymerizing silicic acid as an example of this production method includes diluting an alkali silicate aqueous solution with water to a silica concentration of 3 to 10% by weight, and then bringing it into contact with an H-type strongly acidic cation exchange resin. Then, it is dealkalized and, if necessary, brought into contact with an OH type strongly basic anion exchange resin to deanion to prepare active silicic acid. An example is a method for producing a silica sol having an average particle diameter of 60 nm or less by adding an alkaline substance so that the pH is 8 or more and heating to 50 ° C. or more.

(2) Manufacturing method of silica sol for growing core particles by adding acidic silicic acid solution to the core particle dispersion In this manufacturing method, the core particle dispersion is not particularly limited as long as it functions as core particles. Conventionally known fine particle dispersions such as silica, alumina, zirconia, ceria, titania, silica-alumina, silica-zirconia, silica-ceria, silica-titania can be used. Among them, the silica sol and the silica-based composite oxide sol disclosed in Japanese Patent Application Laid-Open Nos. 5-132309 and 7-105522 by the applicant of the present application have a uniform particle size distribution, and polishing with a uniform particle size distribution. Since silica particles for use are obtained, it is preferable.

It is preferable that an alkali silicate is added to the core particle dispersion before addition of the acidic silicate solution. When the alkali silicate is added, when the acidic silicate solution for particle growth is added next, the SiO ₂ concentration dissolved in the dispersion medium is increased in advance, so that precipitation of silicic acid on the core particles occurs quickly, The pH of the dispersion can be adjusted to about 8 to 12, preferably 9.5 to 11.5. As the alkali silicate used here, it is preferable to use a solution in which silica is dissolved in an organic base such as potassium silicate (potassium water glass), silicate alkali other than sodium silicate (sodium water glass), or quaternary amine. Moreover, alkali metal hydroxides other than NaOH, ammonium, and quaternary ammonium hydride can be added as needed. Furthermore, alkali metal hydroxides such as Mg (OH) ₂ , Ca (OH) ₂ , Sr (OH) ₂ , and Ba (OH) ₂ can be preferably used.

Even if the core particles are not dispersed in advance, the core particles are generated when the silica concentration is increased when an acidic silicic acid solution described later is added to the alkali silicate aqueous solution. Therefore, such a core particle dispersion is also preferably used. be able to. The concentration of the core particle dispersion varies depending on the size of the core particles, but is preferably in the range of 0.005 to 20 wt%, more preferably 0.01 to 10 wt% as SiO ₂ .

When the concentration of the core particles is less than 0.005% by weight, some or all of the core particles may be dissolved when the temperature is increased to perform particle growth. If the effect of using the liquid is not obtained, and part of the core particles is dissolved, the particle diameter of the silica particles obtained tends to be non-uniform, and the effect of using the core particle dispersion may not be obtained is there. On the other hand, when the concentration of the core particles exceeds 20% by weight, the addition rate of the silicic acid solution is increased in order to make the addition ratio of the acidic silicic acid solution per core particle the same as the low concentration. Precipitation of the acidic silicic acid solution on the surface of the core particles cannot follow, and the acidic silicic acid solution may gel.
The average particle diameter of the core particles is not particularly limited as long as the silica particles described above can be obtained.

(3) A method for producing a silica sol comprising a step of washing a silica hydrogel obtained by neutralizing a silicate with an acid, removing salts, adding an alkali, and heating the silica hydrogel by heating. The production method is called a peptization method. Usually, a silica hydrogel is prepared by neutralizing an aqueous solution of silicate with an acid, and the silica hydrogel is slurried or dispersed by chemical or mechanical means. It is known as a method of making a solution.
Here, as a chemical means, the method of adding an alkali to a silica hydrogel and heating as desired is mentioned. Moreover, as a mechanical means, the method of using apparatuses, such as a stirrer, can be mentioned. These chemical means and mechanical means may be used in combination.

Specifically, silica hydrogel obtained by neutralizing silicate with acid is washed, salts are removed, alkali is added, and the silica hydrogel is peptized by heating in the range of 60 to 200 ° C. Then, a silica sol is prepared.
The silicate used as a raw material in this production method is preferably one or more silicates selected from alkali metal silicates, ammonium silicates, and organic base silicates. Examples of the alkali metal silicate include sodium silicate (water glass) and potassium silicate, and examples of the organic base include quaternary ammonium salts such as tetraethylammonium salt, amines such as monoethanolamine, diethanolamine, and triethanolamine. In addition, the ammonium silicate or the organic base silicate includes an alkaline solution obtained by adding ammonia, a quaternary ammonium hydroxide, an amine compound, or the like to a silicic acid solution.

(4) Method for producing silica sol comprising the step of hydrolyzing a silicon compound having a hydrolyzable group and polymerizing the resulting silicic acid As an example of this production method, water-organic in which seed particles are dispersed A method of producing monodispersed silica particles by adding tetraethoxysilane to a solvent-based dispersion, hydrolyzing the tetraethoxysilane, attaching silica onto the seed particles, and performing particle growth. Are known.
About the solid content density | concentration of the silica type sol used as a raw material, the thing of the range of 10-50 mass% is used.
Further, a silica-based sol is preferably in a monodispersed state in order to make the particle diameter uniform in a later step. Of course, a commercially available silica sol can be applied as a raw material. In that case, it is economical to use a commercially available product having a high silica concentration of 20 to 50%. Further, before use, ion exchange, filtration, concentration adjustment, etc. may be performed as desired.

Organic Particles The organic particles used in the present invention are particles made of an organic resin having an average particle diameter in the range of 5 to 80 nm by an image analysis method. The type of organic resin is not particularly limited, but is usually selected from acrylic resins, epoxy resins, urethane resins, polyester resins, amide resins, or copolymers thereof. Are preferably used.

Production Method The production method of the abrasive particle dispersion according to the present invention comprises 100 parts by mass (in terms of solid content) of silica particle dispersion (a) below, and 1 to 50 parts by mass of organic particle dispersion (b) below. (In terms of solid content) are mixed in a pH range in which the difference in zeta potential is 10 mV or more, and held in a range of 5 to 70 ° C. to cause heteroaggregation.
(A) A silica particle dispersion (solid content) in which silica particles having an average particle diameter (Da) in the range of 15 to 240 nm and a zeta potential (Za) in the range of −20 to −60 mV are dispersed in a dispersion medium. (Concentration 10-40% by mass)
(B) An organic particle dispersion in which organic particles having an average particle diameter (Db) in the range of 5 to 80 nm and a zeta potential (Zb) in the range of −3 to −30 mV are dispersed in a dispersion medium ( (Solid content concentration of 1 to 20% by mass) (however, (Da) / (Db) = limited to a range of 1.0 to 3.0)

  Specifically, a silica particle dispersion having a silica concentration of 1 to 50% by mass is diluted with ion-exchanged water or pure water as necessary to adjust the silica concentration to 10% by mass or less. Further, an organic particle dispersion having a solid concentration of 1 to 50% by mass is diluted with ion-exchanged water or pure water as necessary, and the silica concentration is adjusted to 10% by mass or less.

  Next, the pH of the diluted silica particle dispersion and the organic particle dispersion is changed, and the zeta potential is measured, respectively. At the same pH value, the pH at which the difference between the zeta potentials of both dispersions is 10 mV or more is found. Then, the pH of each of the silica particle dispersion and the organic particle dispersion is adjusted so that the zeta potential difference is 10 mV or more. An acid or a base is used for pH adjustment, but it is usually preferable to use hydrochloric acid in order to adjust to the acidic side.

The silica particle dispersion and the organic particle dispersion whose pH has been adjusted are maintained at 5 to 70 ° C., and both dispersions are mixed. About mixing operation, it is preferable to mix gradually rather than rapid mixing. Usually, it is desirable to mix for 10 minutes to 60 minutes. By this operation, hetero-aggregation of silica particles and organic particles occurs, and the polishing particle dispersion according to the present invention is generated.
The blending ratio of the silica particle dispersion and the organic particle dispersion essentially corresponds to the respective component ratios in the intended polishing particle dispersion.
Regarding the zeta potential range of the silica particle dispersion, it can be said that the zeta potential range of a normal silica particle dispersion corresponds. Moreover, it can be said that the zeta potential range of the normal organic particle dispersion also corresponds to the zeta potential range of the organic particle dispersion.

Abrasive Composition The abrasive particle dispersion according to the present invention can be used as an abrasive by itself, but if desired, as an additive, a polishing accelerator, a surfactant, a heterocyclic compound, pH adjustment One or more additives selected from the group consisting of an agent and a pH buffer may be added and used. In the present invention, a mixture obtained by adding these components to the polishing particle dispersion is referred to as “polishing composition”.

Polishing Accelerator The abrasive composition according to the present invention may be a conventionally known polishing accelerator, if necessary, depending on the type of material to be polished. Examples of such include hydrogen peroxide, peracetic acid, urea peroxide and mixtures thereof. When such an abrasive composition containing a polishing accelerator such as hydrogen peroxide is used, the polishing rate can be effectively improved when the material to be polished is a metal.

  As another example of the polishing accelerator, there can be mentioned acids such as sulfuric acid, nitric acid, phosphoric acid, oxalic acid and hydrofluoric acid, or sodium salts, potassium salts, ammonium salts and mixtures thereof. In the case of a polishing composition containing these polishing accelerators, when polishing a material to be polished consisting of composite components, the polishing rate is accelerated for a specific component of the material to be polished, thereby finally achieving flat polishing. You can get a plane.

  When the abrasive composition according to the present invention contains a polishing accelerator, the content thereof is preferably 0.1 to 10% by mass, and more preferably 0.5 to 5% by mass. In order to improve the dispersibility and stability of the surfactant and / or hydrophilic compound polishing composition, a cationic, anionic, nonionic or amphoteric surfactant or hydrophilic compound can be added.

  Both the surfactant and the hydrophilic compound have an action of reducing a contact angle to the surface to be polished and an action of promoting uniform polishing. As the surfactant and / or the hydrophilic compound, for example, those selected from the following groups can be used.

  Examples of the anionic surfactant include carboxylate, sulfonate, sulfate ester salt and phosphate ester salt. As the carboxylate salt, soap, N-acyl amino acid salt, polyoxyethylene or polyoxypropylene alkyl ether carboxyl Acid salt, acylated peptide; as sulfonate, alkyl sulfonate, alkyl benzene and alkyl naphthalene sulfonate, naphthalene sulfonate, sulfosuccinate, α-olefin sulfonate, N-acyl sulfonate; sulfate ester Salts include sulfated oil, alkyl sulfates, alkyl ether sulfates, polyoxyethylene or polyoxypropylene alkyl allyl ether sulfates, alkyl amide sulfates; phosphate ester salts such as alkyl phosphates, polyoxyethylene or polyoxy B pyrene alkyl allyl ether phosphate can be exemplified.

  As cationic surfactant, aliphatic amine salt, aliphatic quaternary ammonium salt, benzalkonium chloride salt, benzethonium chloride, pyridinium salt, imidazolinium salt; as amphoteric surfactant, carboxybetaine type, sulfobetaine type, Mention may be made of aminocarboxylates, imidazolinium betaines, lecithins, alkylamine oxides.

Nonionic surfactants include ether type, ether ester type, ester type and nitrogen-containing type. Ether type includes polyoxyethylene alkyl and alkylphenyl ether, alkylallyl formaldehyde condensed polyoxyethylene ether, polyoxyethylene poly Examples include oxypropylene block polymer, polyoxyethylene polyoxypropylene alkyl ether, ether ester type, glycerin ester polyoxyethylene ether, sorbitan ester polyoxyethylene ether, sorbitol ester polyoxyethylene ether, ester type, Polyethylene glycol fatty acid ester, glycerin ester, polyglycerin ester, sorbitan ester, propylene glycol ester Le, sucrose esters, nitrogen-containing type, fatty acid alkanolamides, polyoxyethylene fatty acid amides, polyoxyethylene alkyl amide, and the like. In addition, a fluorine-type surfactant etc. are mentioned.

  As the surfactant, an anionic surfactant or a non-ionic surfactant is preferable, and as the salt, ammonium salt, potassium salt, sodium salt and the like can be mentioned, and ammonium salt and potassium salt are particularly preferable.

  Furthermore, as hydrophilic compounds, esters such as glycerin ester, sorbitan ester and alanine ethyl ester; polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene glycol alkyl ether, polyethylene glycol alkenyl ether, alkyl polyethylene glycol, alkyl polyethylene glycol Alkyl ether, alkyl polyethylene glycol alkenyl ether, alkenyl polyethylene glycol, alkenyl polyethylene glycol alkyl ether, alkenyl polyethylene glycol alkenyl ether, polypropylene glycol alkyl ether, polypropylene glycol alkenyl ether, alkyl polypropylene glycol, alkyl Polyethers such as polypropylene glycol alkyl ethers, alkyl polypropylene glycol alkenyl ethers, alkenyl polypropylene glycols; polysaccharides such as alginic acid, pectic acid, carboxymethylcellulose, curdlan and pullulan; amino acid salts such as glycine ammonium salt and glycine sodium salt; polyaspartic acid , Polyglutamic acid, polylysine, polymalic acid, polymethacrylic acid, polymethacrylic acid ammonium salt, polymethacrylic acid sodium salt, polyamic acid, polymaleic acid, polyitaconic acid, polyfumaric acid, poly (p-styrenecarboxylic acid), polyacrylic acid, Polyacrylamide, aminopolyacrylamide, polyacrylic acid ammonium salt, polyacrylic acid sodium salt, polyamic acid, poly Polycarboxylic acids and salts thereof such as ammonium ammonium mate, sodium polyamic acid and polyglyoxylic acid; vinyl polymers such as polyvinyl alcohol, polyvinyl pyrrolidone and polyacrolein; ammonium methyl taurate, sodium methyl taurate, methyl sulfate Sodium salt, ethylammonium sulfate salt, butylammonium sulfate salt, vinylsulfonic acid sodium salt, 1-allylsulfonic acid sodium salt, 2-allylsulfonic acid sodium salt, methoxymethylsulfonic acid sodium salt, ethoxymethylsulfonic acid ammonium salt, 3 -Sulfonic acids such as ethoxypropyl sulfonic acid sodium salt and salts thereof; amides such as propionamide, acrylamide, methylurea, nicotinamide, succinic acid amide and sulfanilamide And the like.

  In addition, when the substrate to be polished is a glass substrate or the like, any surfactant can be suitably used. However, in the case of a silicon substrate for a semiconductor integrated circuit or the like, alkali metal, alkaline earth When the influence of contamination by metals or halides is disliked, it is desirable to use an acid or an ammonium salt surfactant.

  When the polishing composition according to the present invention contains a surfactant and / or a hydrophilic compound, the total content is preferably 0.001 to 10 g in 1 L of the polishing composition, It is more preferably 0.01 to 5 g, and particularly preferably 0.1 to 3 g.

In order to obtain a sufficient effect, the content of the surfactant and / or the hydrophilic compound is preferably 0.001 g or more in 1 L of the polishing composition, and preferably 10 g or less from the viewpoint of preventing the polishing rate from being lowered.
Only one type of surfactant or hydrophilic compound may be used, two or more types may be used, and different types may be used in combination.

Heterocyclic Compound For the abrasive composition of the present invention, when a metal is contained in the substrate to be polished, the metal is formed with a passivating layer or a dissolution suppressing layer to suppress erosion of the substrate to be polished. A heterocyclic compound may be contained. Here, the “heterocyclic compound” is a compound having a heterocyclic ring containing one or more heteroatoms. A hetero atom means an atom other than a carbon atom or a hydrogen atom. A heterocycle means a cyclic compound having at least one heteroatom. A heteroatom means only those atoms that form part of a heterocyclic ring system, either external to the ring system, separated from the ring system by at least one non-conjugated single bond, Atoms that are part of a further substituent of are not meant. Preferred examples of the hetero atom include, but are not limited to, a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom. As examples of the heterocyclic compound, imidazole, benzotriazole, benzothiazole, tetrazole, and the like can be used. More specifically, 1,2,3,4-tetrazole, 5-amino-1,2,3,4-tetrazole, 5-methyl-1,2,3,4-tetrazole, 1,2,3- Triazole, 4-amino-1,2,3-triazole, 4,5-diamino-1,2,3-triazole, 1,2,4-triazole, 3-amino1,2,4-triazole, 3,5 -Diamino-1,2,4-triazole can be mentioned, but is not limited thereto.

  About content in the case of mix | blending a heterocyclic compound with the abrasive | polishing agent composition which concerns on this invention, it is preferable that it is 0.001-1.0 mass%, and it is 0.001-0.7 mass%. More preferably, the content is 0.002 to 0.4% by mass.

pH adjuster In order to enhance the effect of each of the above additives, an acid or a base can be added as necessary to adjust the pH of the polishing composition.

  When adjusting the abrasive composition to pH 7 or higher, an alkaline one is used as the pH adjuster. Desirably, amines such as sodium hydroxide, aqueous ammonia, ammonium carbonate, ethylamine, methylamine, triethylamine, tetramethylamine are used.

  When adjusting the abrasive composition to less than pH 7, an acidic one is used as the pH adjuster. For example, hydroxy acids such as lactic acid, citric acid, malic acid, tartaric acid and glyceric acid are used.

pH buffering agent A pH buffering agent may be used to maintain a constant pH value of the polishing composition. Examples of pH buffering agents that can be used include phosphates and borates such as ammonium dihydrogen phosphate, diammonium hydrogen phosphate, and ammonium tetraborate tetrahydrate, and organic acids.

Solvent About the abrasive | polishing agent composition which concerns on this invention, a solvent can be used as needed. As the solvent, water is usually used, but alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol can be used as necessary, and water-soluble organic solvents such as ethers, esters, and ketones are also used. be able to. Further, it may be a mixed solvent composed of water and an organic solvent.

Concentration of abrasive particles The concentration of abrasive particles in the abrasive composition is preferably in the range of 2 to 50 wt%, more preferably 5 to 30 wt%. If the concentration is less than 2% by weight, the concentration may be too low depending on the type of substrate or insulating film, resulting in a slow polishing rate and productivity. If the concentration of silica particles exceeds 50% by weight, the stability of the abrasive will be insufficient, the polishing rate and the polishing efficiency will not be further improved, and the dried product will be removed in the step of supplying the dispersion for polishing treatment. It may be generated and attached, which may cause scratches.

The measurement method or calculation method applied to the examples and comparative examples of the present invention will be described below.
[1] Method for measuring average particle diameter by image analysis Using a transmission electron microscope (H-800, manufactured by Hitachi, Ltd.), a silica fine particle dispersion, an organic fine particle dispersion, or an organic-inorganic aggregated particle dispersion is multiplied by 250,000. The maximum diameter of any 50 particles in a photographic projection obtained by taking a photograph at a magnification was measured, and the average value was taken as the average particle diameter.
In this specification, the average particle diameter of silica fine particles in the silica fine particle dispersion is Da, the average particle diameter of organic fine particles in the organic fine particle dispersion is Db, and the average particle diameter of abrasive particles in the abrasive particle dispersion is Dm.

[2] Zeta potential measurement The zeta potential measurement was performed with an ultrasonic zeta potential measurement device (manufactured by MAtec, ESA8000). As measurement conditions, the pH of the silica fine particle dispersion, organic fine particle dispersion or organic inorganic aggregated particle dispersion is adjusted to 5 in advance with a diluted hydrochloric acid aqueous solution, the solid content concentration of each dispersion is 5 mass%, and the temperature is 25. The zeta potential was measured at 0 ° C.

[3] pH measurement The pH was measured at room temperature by inserting a glass electrode of a pH meter F22 manufactured by Horiba, Ltd., which had been corrected with standard solutions of pH 4, 7, and 9.

[4] Mass ratio measurement The mass ratio of the silica particles to the organic particles in the polishing particles is 100 g of a polishing particle dispersion (solid content 30% by mass), dried at 200 ° C. for 2 hours, did. After the mass (a) of this measurement sample was weighed, it was baked in an electric furnace at 600 ° C. for 2 hours to remove the organic resin component, and the mass (b) of the sample remaining after cooling was measured. The value of (a) / (b) × 100 is calculated, this value is defined as the ratio (mass%) of silica particles in the abrasive particles, and 100 − [(a) / (b) × 100] is the abrasive particles. It was made into the ratio (mass%) of the organic type particle | grains in.

[5] Polishing property evaluation method Polishing composition The solid content concentration of the organic-inorganic agglomerated particle dispersion obtained in each Example and each Comparative Example was adjusted to 12% by mass, and a 10% potassium hydroxide aqueous solution was added. The pH was adjusted to 10 to obtain a polishing composition.
Substrate to be polished An aluminum disk substrate was used as the substrate to be polished. This aluminum disk substrate is a substrate (95 mmΦ / 25 mmΦ-1.27 mmt) obtained by electrolessly plating Ni-P to a thickness of 10 μm (a hard Ni-P plating layer having a composition of Ni88% and P12%) on an aluminum substrate. It is. This substrate was first polished and the surface roughness (RA) was 0.17 nm.
Polishing test Set the substrate to be polished in a polishing apparatus (manufactured by Nano Factor Co., Ltd .: NF300) and use a polishing pad ("Apollon" manufactured by Rodel) for polishing at a substrate load of 0.05 MPa and a table rotation speed of 30 rpm. Polishing was performed by supplying the slurry at a rate of 20 g / min for 5 minutes.
The change in weight of the substrate to be polished before and after polishing was determined to calculate the polishing rate [nm / min].
Scratch (Linear Mark) Measurement Regarding the occurrence of scratches, after polishing an aluminum disk substrate in the same manner as described above, an ultra-fine defect / visualization macro device (product name: Micro-MAX) manufactured by VISION PSYTEC Co., Ltd. was used. The entire surface was observed with a Zoom 15, and the number of scratches (linear traces) present on the polished substrate surface corresponding to 65.97 cm ² was counted and totaled.

Example 1
Silica fine particle dispersion (silica concentration 48% by mass, average particle size [image analysis method] 50 nm, Cataloid [registered trademark] Si-45P, manufactured by JGC Catalysts & Chemicals Co., Ltd.) 83 g and ion exchange water 900 g at room temperature over 30 minutes. Mixed to prepare a mixed solution. Hydrochloric acid (concentration 5%) was added so that the pH of the mixed solution was 5.0 to prepare solution A. The zeta potential was −50 mV.
20 g of Takelac W-5030 (polyurethane 40% concentration, particle size: 50 nm) manufactured by Mitsui Chemicals Polyurethane Co., Ltd. and 980 g of ion-exchanged water were mixed at room temperature for 30 minutes to prepare a mixed solution. Hydrochloric acid (concentration 5%) was added so that the pH of the mixed solution was 5.0 to prepare solution B. The zeta potential was −20 mV.
The liquid A and liquid B were each heated to a temperature of 55 ° C. and mixed for 30 minutes to prepare an organic-inorganic composite particle dispersion. This organic-inorganic composite particle dispersion was concentrated to 400 g with an ultrafiltration membrane. The obtained dispersion had a solid content concentration of 12% by mass and an average particle size [image analysis method] of 250 nm. Hereinafter, Table 1 shows each numerical value and polishing test result of each example, and Table 2 shows each comparative example.

Example 2
Silica fine particle dispersion (silica concentration 48% by mass, average particle size [image analysis method] 50 nm, Cataloid [registered trademark] Si-45P, manufactured by JGC Catalysts & Chemicals Co., Ltd.) 83 g and ion exchange water 900 g at room temperature over 30 minutes. Mixed to prepare a mixed solution. Hydrochloric acid (concentration 5%) was added so that the pH of the mixed solution was 5.0 to prepare solution A. The zeta potential was −50 mV.
30 g of polyurethane resin particle dispersion (solid content 40% concentration, particle size: 30 nm) and 970 g of ion-exchanged water were mixed at room temperature for 30 minutes to prepare a mixed solution. Hydrochloric acid (concentration 5%) was added so that the pH of the mixed solution was 5.0 to prepare solution B. The zeta potential was −20 mV.
The liquid A and liquid B were each heated to a temperature of 55 ° C. and mixed for 30 minutes to prepare an organic-inorganic composite particle dispersion. This organic-inorganic composite particle dispersion was concentrated to 400 g with an ultrafiltration membrane. The obtained dispersion had a solid content concentration of 12% by mass and an average particle size [image analysis method] of 250 nm.

Example 3
Silica fine particle dispersion (silica concentration 48% by mass, average particle size [image analysis method] 50 nm, Cataloid [registered trademark] Si-45P, manufactured by JGC Catalysts & Chemicals Co., Ltd.) 83 g and ion exchange water 900 g at room temperature over 30 minutes. Mixed to prepare a mixed solution. Hydrochloric acid (concentration 5%) was added so that the pH of the mixed solution was 5.0 to prepare solution A. The zeta potential was −50 mV.
20 g of polyurethane resin particle dispersion (solid content: 40% by mass, particle size: 25 nm) and 980 g of ion-exchanged water were mixed at room temperature for 30 minutes to prepare a mixed solution. Hydrochloric acid (concentration 5%) was added so that the pH of the mixed solution was 5.0 to prepare solution B. The zeta potential was −25 mV.
The liquid A and liquid B were each heated to a temperature of 55 ° C. and mixed for 30 minutes to prepare an organic-inorganic composite particle dispersion. This organic-inorganic composite particle dispersion was concentrated to 400 g with an ultrafiltration membrane. The obtained dispersion had a solid content concentration of 12% by mass and an average particle size [image analysis method] of 260 nm.

Example 4
Silica fine particle dispersion (silica concentration 30% by mass, average particle size [image analysis method] 10 nm, Cataloid [registered trademark] Si-30, manufactured by JGC Catalysts & Chemicals Co., Ltd.) 133 g and ion-exchanged water 900 g at room temperature for 30 minutes. Mixed to prepare a mixed solution. Hydrochloric acid (concentration 5%) was added so that the pH of the mixed solution was 5.0 to prepare solution A. The zeta potential was −30 mV.
20 g of an acrylic resin particle dispersion (solid content 40% concentration, particle size: 10 nm) and 980 g of ion-exchanged water were mixed at room temperature for 30 minutes to prepare a mixed solution. Hydrochloric acid (concentration 5%) was added so that the pH of the mixed solution was 5.0 to prepare solution B. The zeta potential was −15 mV.
The liquid A and liquid B were each heated to a temperature of 55 ° C. and mixed for 30 minutes to prepare an organic-inorganic composite particle dispersion. This organic-inorganic composite particle dispersion was concentrated to 400 g with an ultrafiltration membrane. The obtained dispersion had a solid content concentration of 12% by mass and an average particle size [image analysis method] of 70 nm.

Example 5
Silica fine particle dispersion (silica concentration 40% by mass, average particle size [image analysis method] 30 nm, Cataloid [registered trademark] Si-50, manufactured by JGC Catalysts & Chemicals Co., Ltd.) 100 g and ion-exchanged water 900 g over 30 minutes at room temperature. Mixed to prepare a mixed solution. Hydrochloric acid (concentration 5%) was added so that the pH of the mixed solution was 5.0 to prepare solution A. The zeta potential was -41 mV.
20 g of polyurethane resin particle dispersion (solid content 40% by mass, particle size: 30 nm) and 980 g of ion-exchanged water were mixed at room temperature for 30 minutes to prepare a mixed solution. Hydrochloric acid (concentration 5%) was added so that the pH of the mixed solution was 5.0 to prepare solution B. The zeta potential was -11 mV.
The liquid A and liquid B were each heated to a temperature of 55 ° C. and mixed for 30 minutes to prepare an organic-inorganic composite particle dispersion. This organic-inorganic composite particle dispersion was concentrated to 400 g with an ultrafiltration membrane. The resulting dispersion had a solid content concentration of 12% by mass and an average particle size [image analysis method was 120 nm.

Comparative Example 1
Silica fine particle dispersion (silica concentration 48% by mass, average particle size [image analysis method] 50 nm, Cataloid [registered trademark] Si-45P, manufactured by JGC Catalysts & Chemicals Co., Ltd.) 83 g and ion exchange water 900 g at room temperature over 30 minutes. Mixed to prepare a mixed solution. Hydrochloric acid (concentration 5%) was added so that the pH of the mixed solution was 5.0 to prepare solution A. The zeta potential was −50 mV.
20 g of polyurethane resin particle dispersion (solid content 40% by mass, particle size: 5 nm) and 980 g of ion-exchanged water were mixed at room temperature for 30 minutes to prepare a mixed solution. Hydrochloric acid (concentration 5%) was added so that the pH of the mixed solution was 5.0 to prepare solution B. The zeta potential was −20 mV.
The liquid A and liquid B were each heated to a temperature of 55 ° C. and mixed for 30 minutes to prepare an organic-inorganic composite particle dispersion. This organic-inorganic composite particle dispersion was concentrated to 400 g with an ultrafiltration membrane. The obtained dispersion had a solid content concentration of 12% by mass and an average particle size [image analysis method] of 65 nm. The thing of the comparative example 1 has the difficulty that a grinding | polishing speed | rate is slow.

Comparative Example 2
Silica fine particle dispersion (silica concentration 48% by mass, average particle size [image analysis method] 50 nm, Cataloid [registered trademark] Si-45P, manufactured by JGC Catalysts & Chemicals Co., Ltd.) 83 g and ion exchange water 900 g at room temperature over 30 minutes. Mixed to prepare a mixed solution. Hydrochloric acid (concentration 5%) was added so that the pH of the mixed solution was 5.0 to prepare solution A. The zeta potential was −50 mV.
30 g of polyurethane resin particle dispersion (solid content 40% by mass, particle size: 250 nm) and 970 g of ion-exchanged water were mixed at room temperature for 30 minutes to prepare a mixed solution. Hydrochloric acid (concentration 5%) was added so that the pH of the mixed solution was 5.0 to prepare solution B. The zeta potential was −30 mV.
The liquid A and liquid B were each heated to a temperature of 55 ° C. and mixed for 30 minutes to prepare an organic-inorganic composite particle dispersion. This organic-inorganic composite particle dispersion was concentrated to 400 g with an ultrafiltration membrane. The obtained dispersion had a solid content concentration of 12% by mass and an average particle size [image analysis method] of 280 nm. A lot of linear marks are generated on the polished surface using Comparative Example 2.

Comparative Example 3
Silica fine particle dispersion (silica concentration 48% by mass, average particle size [image analysis method] 50 nm, Cataloid [registered trademark] Si-45P, manufactured by JGC Catalysts & Chemicals Co., Ltd.) 83 g and ion exchange water 900 g at room temperature over 30 minutes. Mixed to prepare a mixed solution. Hydrochloric acid (concentration 5%) was added so that the pH of the mixed solution was 5.0 to prepare solution A. The zeta potential was −50 mV.
Polyurethane resin particle dispersion (solid content 40% by mass, particle size: 50 nm) 0.01 g and ion-exchanged water 999.999 g were mixed at room temperature for 30 minutes to prepare a mixed solution. Hydrochloric acid (concentration 5%) was added so that the pH of the mixed solution was 5.0 to prepare solution B. The zeta potential was −30 mV.
The liquid A and liquid B were each heated to a temperature of 55 ° C. and mixed for 30 minutes to prepare an organic-inorganic composite particle dispersion. This organic-inorganic composite particle dispersion was concentrated to 400 g with an ultrafiltration membrane. The obtained dispersion had a solid content concentration of 12% by mass and an average particle size [image analysis method] of 51 nm. In Comparative Example 3, the polishing rate does not increase so much, and a considerable amount of linear traces are generated.

Comparative Example 4
Silica fine particle dispersion (silica concentration 48% by mass, average particle size [image analysis method] 50 nm, Cataloid [registered trademark] Si-45P, manufactured by JGC Catalysts & Chemicals Co., Ltd.) 83 g and ion exchange water 900 g at room temperature over 30 minutes. Mixed to prepare a mixed solution. Hydrochloric acid (concentration 5%) was added so that the pH of the mixed solution was 5.0 to prepare solution A. The zeta potential was −50 mV.
70 g of polyurethane resin particle dispersion (solid content 40% by mass, particle size: 50 nm) and 930 g of ion-exchanged water were mixed at room temperature for 30 minutes to prepare a mixed solution. Hydrochloric acid (concentration 5%) was added so that the pH of the mixed solution was 5.0 to prepare solution B. The zeta potential was −30 mV.
The liquid A and liquid B were each heated to a temperature of 55 ° C. and mixed for 30 minutes to prepare an organic-inorganic composite particle dispersion. This organic-inorganic composite particle dispersion was concentrated to 400 g with an ultrafiltration membrane. The obtained dispersion had a solid content concentration of 12% by mass and an average particle size [image analysis method] of 280 nm. In Comparative Example 4, the polishing rate cannot be increased.

Comparative Example 5
Silica fine particle dispersion (silica concentration 48% by mass, average particle size [image analysis method] 50 nm, Cataloid [registered trademark] Si-45P, manufactured by JGC Catalysts & Chemicals Co., Ltd.) 83 g and ion exchange water 900 g at room temperature over 30 minutes. Mixed to prepare a mixed solution. Hydrochloric acid (concentration 5%) was added so that the pH of the mixed solution was 5.0 to prepare solution A. The zeta potential was −50 mV.
20 g of polyurethane resin particle dispersion (solid content 40% by mass, particle size: 50 nm) and 980 g of ion-exchanged water were mixed at room temperature for 30 minutes to prepare a mixed solution. Hydrochloric acid (concentration 5%) was added so that the pH of the mixed solution was 5.0 to prepare solution B. The zeta potential was −45 mV.
The liquid A and liquid B were each heated to a temperature of 55 ° C. and mixed for 30 minutes to prepare an organic-inorganic composite particle dispersion. This organic-inorganic composite particle dispersion was concentrated to 400 g with an ultrafiltration membrane. The obtained dispersion had a solid content concentration of 12% by mass and an average particle size [image analysis method] of 50 nm. In Comparative Example 5, the polishing rate cannot be increased.

Comparative Example 6
Silica fine particle dispersion (silica concentration 48% by mass, average particle size [image analysis method] 50 nm, Cataloid [registered trademark] Si-45P, manufactured by JGC Catalysts & Chemicals Co., Ltd.) 83 g and ion exchange water 900 g at room temperature over 30 minutes. Mixed to prepare a mixed solution. Hydrochloric acid (concentration 5%) was added so that the pH of the mixed solution was 5.0 to prepare solution A. The zeta potential was −50 mV.
20 g of polyurethane resin particle dispersion (solid content 40% by mass, particle size: 50 nm) and 980 g of ion-exchanged water were mixed at room temperature for 30 minutes to prepare a mixed solution. Hydrochloric acid (concentration 5%) was added so that the pH of the mixed solution was 5.0 to prepare solution B. The zeta potential was −30 mV.
The liquid A and liquid B were each heated to a temperature of 55 ° C. and mixed for 30 minutes to prepare an organic-inorganic composite particle dispersion. This organic-inorganic composite particle dispersion was concentrated to 400 g with an ultrafiltration membrane. The obtained dispersion had a solid content concentration of 12% by mass and an average particle size [image analysis method] of 460 nm. In Comparative Example 6, many linear marks were generated.

The polishing particle dispersion or polishing composition according to the present invention can be suitably used for polishing applications such as semiconductor wafers, glass hard disks, and alumina hard disks.

Claims (5)

A polishing particle dispersion in which polishing particles having an average particle diameter (Dm) of 10 to 300 nm composed of an aggregate of silica particles and organic particles are dispersed in a dispersion medium, and the following (1) to (3) A polishing particle dispersion characterized by satisfying the following conditions.
(1) The average particle diameter (Da) of the silica particles is in the range of 15 to 240 nm (2) The average particle diameter (Db) of the organic particles is in the range of 5 to 80 nm (3) (Da) / (Db) Values range from 1.0 to 3.0   The polishing particle dispersion according to claim 1, wherein a mass ratio of silica particles to organic particles in the polishing particles is in a range of 100: 1 to 100: 50.   The organic particles are selected from an acrylic resin, an epoxy resin, a urethane resin, a polyester resin, an amide resin, or a copolymer thereof. A particle dispersion for polishing.   One or more additives selected from the group consisting of the particle dispersion for polishing according to claim 1, claim 2 or claim 3, and a polishing accelerator, a surfactant, a heterocyclic compound, a pH adjuster and a pH buffer. And an abrasive composition comprising: The difference in zeta potential between 10 parts by mass of the following (a) silica particle dispersion 100 parts by mass (in terms of solid content) and 1 to 50 parts by mass (in terms of solids) of the organic particle dispersion in the following (b). A method for producing a polishing particle dispersion, wherein the particles are mixed in a pH range as described above and held in a range of 5 to 70 ° C. to cause heteroaggregation.
(A) A silica particle dispersion (solid content) in which silica particles having an average particle diameter (Da) in the range of 15 to 240 nm and a zeta potential (Za) in the range of −20 to −60 mV are dispersed in a dispersion medium. (Concentration 10-40% by mass)
(B) An organic particle dispersion in which organic particles having an average particle diameter (Db) in the range of 5 to 80 nm and a zeta potential (Zb) in the range of −3 to −30 mV are dispersed in a dispersion medium ( (Solid content concentration of 1 to 20% by mass) (however, (Da) / (Db) = limited to a range of 1.0 to 3.0)