JP2010141288A - Slurry and polishing solution set, substrate, substrate polishing method using chemical mechanical polishing solution (cmp) obtained from the polishing solution set - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a slurry containing a tetravalent metal hydroxide improved in variation in handling operability, usable period of time, and polishing speed, a polishing solution set containing the slurry and an additive solution, and a substrate polishing method using a CMP solution obtained by mixing the polishing solution set with respect to a CMP technology to flatten a shallow-trench separated insulating film, a premetal insulating film, an interlayer insulating film, and the like. <P>SOLUTION: The polishing solution set comprises the slurry containing water and a tetravalent metal hydroxide, and the additive solution containing water and an additive agent. This solution set is mixed to be used as a CMP solution. In this set, the slurry has a conductivity of 1 mS or below when the concentration of the tetravalent metal hydroxide is 1 mass%. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polishing liquid set and a slurry used in a substrate surface flattening step, which is a semiconductor element manufacturing technique, and a substrate polishing method using a CMP polishing liquid obtained therefrom. In particular, the present invention relates to a polishing liquid set and a slurry used in a planarization process of a shallow trench isolation insulating film, a premetal insulating film, an interlayer insulating film, and the like, and a substrate polishing method using a CMP polishing liquid obtained therefrom.

  In recent semiconductor device manufacturing processes, the importance of processing technology for higher density and miniaturization is increasing. One of these, CMP (Chemical Mechanical Polishing) technology, is used to form shallow trench isolations, planarize premetal insulating films and interlayer insulating films, plugs and buried metal wiring in the manufacturing process of semiconductor devices. It has become an essential technology for formation.

  Fumes are used to planarize an insulating film such as a silicon oxide film formed by a chemical vapor deposition (CVD) method or a spin coating method in a semiconductor device manufacturing process. Dosilica-based CMP polishing liquid has been generally studied. The fumed silica-based CMP polishing liquid is produced by growing grains by a method such as thermal decomposition of tetrachlorosilicic acid and adjusting pH.

  In recent years, a CMP polishing liquid for semiconductors using cerium oxide abrasive has been used. For example, this technique is disclosed in Patent Document 1.

  It is also known to add an additive to control the polishing rate of the cerium oxide-based CMP polishing liquid and improve global flatness. For example, this technique is disclosed in Patent Document 2.

  In recent years, the semiconductor element manufacturing process has been further miniaturized, and polishing scratches generated during polishing have become a problem. In order to solve this problem, attempts have been made to reduce the average particle size of the cerium oxide particles. However, if the average particle size is reduced, the mechanical action is lowered, and therefore the polishing rate is lowered.

  To solve this problem, a CMP polishing liquid using tetravalent metal hydroxide particles has been studied, and this technique is disclosed in Patent Document 3. This technology makes use of the chemical action of tetravalent metal hydroxide particles and minimizes the mechanical action, thereby achieving both reduction of polishing scratches caused by the particles and improvement of the polishing rate. . Also disclosed here is the addition of a pH stabilizer.

  Since polishing characteristics such as the polishing rate greatly depend on the pH of the CMP polishing liquid, it is necessary to adjust the pH. In general, an acid or alkali component is added to adjust the pH. Further, Patent Document 4 discloses a method of using a nitrogen-containing heterocyclic compound such as imidazole when adjusting pH in a CMP polishing liquid using tetravalent metal hydroxide particles.

Japanese Patent Laid-Open No. 10-106994 Japanese Patent Application Laid-Open No. 08-022970 International Publication No. 02/067309 JP 2007-311779 A

  CMP polishing liquid using tetravalent metal hydroxide particles has a good polishing rate in the flattening process of shallow trench isolation insulating film, premetal insulating film, interlayer insulating film, etc., and further reduces polishing scratches It is very effective. However, there has been a problem of storage stability that pH tends to fluctuate during long-term storage. When the pH fluctuates, the polishing rate varies depending on when the CMP polishing liquid is used.

  In order to improve the storage stability, the slurry and the additive solution containing the acid component, alkali component, nitrogen-containing heterocyclic compound and the like described above are stored separately and mixed immediately before polishing or at the time of polishing with a CMP polishing solution. It is effective to do. However, even if the slurry and the additive solution are stored separately, the variation in the polishing rate is not completely eliminated, and improvement has been demanded.

  An object of this invention is to suppress effectively the dispersion | variation in the characteristic of CMP polishing liquid containing a tetravalent metal hydroxide particle. More specifically, an object of the present invention is to improve polishing rate variation in a CMP polishing liquid containing tetravalent metal hydroxide particles. Improving the variation in the polishing rate leads to an improvement in handleability and an extension of the pot life.

  The present inventors considered the following as the reason why the polishing rate varies even when the slurry and the additive liquid are stored separately. That is, in general, a tube pump (roller pump) is frequently used as the liquid feed pump of the polishing apparatus, but ± 10 to 10% of the target mixing ratio due to a change in the inner diameter of the tube and a change in the remaining amount of the supply tank. A 20% change in the amount of liquid delivered can occur.

  The pH of the CMP polishing liquid varies depending on the mixing ratio of the slurry and the additive liquid. Therefore, as described above, it was considered that the mixing ratio inevitably varies, thereby causing variations in pH of the obtained CMP polishing liquid and variations in the final polishing rate. Therefore, it was considered effective to stabilize the polishing characteristics even when the mixing ratio changes by about ± 10 to 20% with respect to the target mixing ratio.

  In order to prevent the pH from fluctuating even when the mixing ratio fluctuates, it is effective to include a pH buffer component in the additive solution. However, the present inventors have found that when the slurry has a high conductivity (that is, when there are many ionic components), the amount of the buffer component required to achieve a predetermined pH increases. And when the buffer component was used in large quantities, it was found that the charge of the abrasive grains was neutralized, so that the particles easily aggregated and settled, and the usable time of the CMP polishing liquid after mixing was shortened.

  As a result of intensive studies, the present inventors have found that the amount of the buffer component added to achieve a predetermined pH can be reduced by controlling the conductivity of the slurry low. As a result, it has been found that even if there is a variation in the mixing ratio of about ± 25% without causing the abrasive grains to aggregate, it can be suppressed to a target variation of about ± 0.1. That is, it has been found that a CMP polishing liquid can be obtained that can suppress variations in polishing rate without shortening the pot life of the CMP polishing liquid.

Specific embodiments of the present invention include the following (1) to (18).
(1) A polishing liquid set comprising a slurry containing water and tetravalent metal hydroxide particles, and an additive liquid containing water and an additive,
The polishing liquid set is mixed and used as a CMP polishing liquid,
The slurry is a polishing liquid set in which the conductivity when the concentration of tetravalent metal hydroxide particles is 1% by mass is 1 mS or less.
(2) The polishing liquid set according to (1), wherein the average particle diameter of the tetravalent metal hydroxide particles in the slurry is 1 nm or more and 400 nm or less.
(3) The polishing liquid set according to (1) or (2), wherein the slurry has a pH of 3.0 or more and 6.0 or less.
(4) The content of the tetravalent metal hydroxide particles in the slurry is any one of the above (1) to (3), which is 0.2 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the slurry. The polishing liquid set according to 1.
(5) The polishing liquid set according to any one of (1) to (4), wherein the zeta potential of the tetravalent metal hydroxide particles in the slurry is +10 mV or more.
(6) The polishing liquid set according to any one of (1) to (5), which is used for polishing a surface to be polished containing silicon oxide at least on the surface.
(7) The polishing liquid set according to any one of (1) to (6), wherein the tetravalent metal hydroxide particles are at least one of rare earth metal hydroxide particles and zirconium hydroxide particles.
(8) mixing the polishing liquid set according to any one of (1) to (7) to obtain a CMP polishing liquid;
The substrate on which the film to be polished is formed is pressed against the polishing cloth of the polishing surface plate and pressurized, and the substrate and the polishing surface plate are relatively moved while supplying the CMP polishing liquid between the film to be polished and the polishing cloth. A method for polishing a substrate, comprising: polishing a film to be polished.
(9) A substrate polished by the polishing method according to (8).
(10) A slurry containing water and tetravalent metal hydroxide particles,
The slurry is mixed with an additive liquid containing water and an additive to form a CMP polishing liquid.
A slurry having a conductivity of 1 mS or less when the concentration of the tetravalent metal hydroxide particles is 1% by mass.
(11) The slurry according to (10), wherein the average particle diameter of the tetravalent metal hydroxide particles in the slurry is 1 nm or more and 400 nm or less.
(12) The slurry according to (10) or (11), wherein the slurry has a pH of 3.0 or more and 6.0 or less.
(13) The content of tetravalent metal hydroxide particles in the slurry is any one of (10) to (12), which is 0.2 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the slurry. The slurry described in.
(14) The slurry according to any one of (10) to (13), wherein the zeta potential of the tetravalent metal hydroxide particles in the slurry is +10 mV or more.
(15) The slurry according to any one of (10) to (14), wherein the CMP polishing liquid is used to polish a surface to be polished containing silicon oxide at least on a surface.
(16) The slurry according to any one of (10) to (15), wherein the tetravalent metal hydroxide particles are at least one of rare earth metal hydroxide particles and zirconium hydroxide particles.
(17) Step of obtaining a CMP polishing liquid by mixing at least the slurry according to any one of (10) to (16) above and an additive liquid containing water and an additive liquid;
The substrate on which the film to be polished is formed is pressed against the polishing cloth of the polishing surface plate and pressurized, and the substrate and the polishing surface plate are relatively moved while supplying the CMP polishing liquid between the film to be polished and the polishing cloth. And polishing the film to be polished.
(18) A substrate polished by the polishing method according to (17).

  According to the present invention, in CMP technology for planarizing a shallow trench isolation insulating film, a premetal insulating film, an interlayer insulating film, and the like, it is possible to suppress variations in polishing speed without shortening the pot life of the CMP polishing liquid. A polishing liquid set and slurry for obtaining a CMP polishing liquid, and a method for polishing a substrate using a CMP polishing liquid obtained therefrom can be provided.

The relationship between the shift | offset | difference of the addition amount of the addition liquid of the CMP polishing liquid of the Example of this invention and a comparative example, and the pH of CMP polishing liquid is shown. The relationship between the shift of the additive amount of the CMP polishing liquid used in FIG. 1 and the polishing rate is shown.

  The present invention provides a polishing liquid set that is stored in at least a slurry and an additive liquid, and finally mixed to be a CMP polishing liquid. Here, the CMP polishing liquid is a composition containing water, tetravalent metal hydroxide particles, and an additive, and touching the film to be polished during polishing. And it is obtained by mixing the polishing liquid set of this invention, or is obtained by mixing the slurry of this invention and an additive liquid at least.

  The slurry is a composition containing water and tetravalent metal hydroxide particles, and the additive liquid is a composition containing water and an additive.

  Hereinafter, each component contained in the slurry and the additive solution and components that can be optionally added will be described in order.

(I. Slurry)
(Tetravalent metal hydroxide particles)
As described above, the slurry of the present invention contains tetravalent metal hydroxide particles and water as abrasive grains. The tetravalent metal hydroxide particles may be contained only in the slurry, or may be contained in both the slurry and the additive solution. From the viewpoint of storage stability, the tetravalent metal hydroxide particles are contained only in the slurry. Preferably it is.

  As the tetravalent metal hydroxide particles, it is preferable to use at least one of rare earth metal hydroxide particles and zirconium hydroxide particles. Two or more kinds of rare earth metal hydroxide particles and zirconium hydroxide particles may be selected and used. Among these, the use of cerium hydroxide particles is preferable in that polishing scratches can be suppressed and the polishing rate is high.

  As a method for producing tetravalent metal hydroxide particles, a method of mixing a tetravalent metal salt and an alkali solution can be used. This method is described in, for example, “Science of Rare Earth” (Adachi Ginya, edited by Kagaku Dojin, 1999), pages 304-305.

As a tetravalent metal salt, for example, M (SO ₄ ) ₂ , M (NH ₄ ) ₂ (NO ₃ ) ₆ , M (NH ₄ ) ₄ (SO ₄ ) ₄ (wherein M represents a rare earth element). Zr (SO ₄ ) ₂ .4H ₂ O is preferred. In particular, chemically active Ce is more preferable.

  As the alkaline solution, aqueous ammonia, potassium hydroxide, or sodium hydroxide can be used. Ammonia water is preferable. The tetravalent metal hydroxide particles synthesized by the above method can be washed to remove metal impurities. For washing the metal hydroxide particles, a method of repeating solid-liquid separation several times by centrifugation or the like can be used.

  Since the tetravalent metal hydroxide particles obtained above are agglomerated, they are preferably dispersed in water by an appropriate method. As a method of dispersing the tetravalent metal hydroxide particles in water, which is a main dispersion medium, a homogenizer, an ultrasonic disperser, a wet ball mill, or the like can be used in addition to the dispersion treatment with a normal stirrer. As for the dispersion method and the particle size control method, for example, the method described in “The Complete Collection of Dispersion Technologies” (Information Organization Co., Ltd., July 2005) can be used.

(Particle size)
The average particle diameter of the tetravalent metal hydroxide particles is preferably 1 nm or more, more preferably 2 nm or more, and further preferably 10 nm or more, in order to avoid the polishing rate becoming too low. preferable. In addition, the upper limit is preferably 400 nm or less, more preferably 300 nm or less, and further preferably 250 nm or less in that the film to be polished is less likely to be damaged.

  The average particle diameter of the tetravalent metal hydroxide particles described in the present invention refers to Z-average Size obtained by cumulant analysis using a dynamic light scattering method. For the measurement, for example, trade name: Zetasizer Nano S manufactured by Spectris Co., Ltd. can be used. As a more specific example, the concentration of the tetravalent metal hydroxide particles is diluted with water so as to be 0.2 parts by mass, and about 1 ml is placed in a 1 cm square cell and installed in an apparatus. The dispersion medium has a refractive index of 1.33 and a viscosity of 0.887, and measurement is performed at 25 ° C., and a value displayed as Z-average Size is read.

  The average particle size (hereinafter referred to as primary particle size) of the primary particles of the metal hydroxide particles is preferably 50 nm or less, more preferably 0.1 to 50 nm, still more preferably 1 to 30 nm, and particularly preferably 3 to 10 nm. .

  In the present invention, when a transmission electron microscope (TEM) photograph is taken and a primary particle (crystallite) is sandwiched between two parallel lines, the value of the portion with the smallest interval is the minor axis, and the value of the largest portion is The major axis was taken, and the average of the minor axis and the major axis was taken as the crystallite size. And 100 crystallite size is measured and let the arithmetic mean be a primary particle size. If the primary particle size is larger than 50 nm, the probability of occurrence of fine scratches is increased, and if it is smaller than 0.1 nm, the polishing rate tends to be low.

(Other characteristics)
The specific surface area of the tetravalent metal hydroxide particles is preferably 100 m ² / g or more from the viewpoint of increasing the chemical action with the film to be polished and improving the polishing rate. The specific surface area of the particles can be measured by the BET method (for example, product name autosorb or product name auto scrub-1 manufactured by Cantachrome).

The density of the tetravalent metal hydroxide particles is preferably 3 g / cm ³ or more 6 g / cm ³ or less. If the density is 3 g / cm ³ or more, the action of particles on the film to be polished tends to be improved and the polishing rate tends to be improved. In this respect, 4 g / cm ³ or more is more preferable. Moreover, if the density is 6 g / cm ³ or less, there is a tendency that the generation of polishing flaws can be suppressed, and in this respect, it is more preferably 5 g / cm ³ or less. The density of the particles is measured by a gas displacement method (for example, measuring device manufactured by Cantachrome Co., Ltd., product name: Ultrapycnometer 1000).

  Since the zeta potential of the tetravalent metal hydroxide particles has an influence on storage stability, it is preferably charged to a positive charge of +10 mV or more, and more preferably in the range of +10 to +70 mV. For the zeta potential measurement, for example, a product name: Zetasizer 3000HS manufactured by Spectris Co., Ltd. can be used. For example, the slurry can be measured by diluting with water so that the amount of scattered light recommended for the Zetasizer 3000HS is obtained. .

(concentration)
The concentration of the tetravalent metal hydroxide particles in the slurry is preferably 0.2 parts by mass or more, based on 100 parts by mass of the slurry, from the viewpoint of reducing the cost during transportation, and 0.5 parts by mass More preferably, it is more preferably 1 part by mass or more. Moreover, from a viewpoint which can make high the storage stability of CMP polishing liquid after mixing with an additive liquid, 20 mass parts or less are preferable, 10 mass parts or less are more preferable, and 5 mass parts or less are still more preferable.

  The concentration of the tetravalent metal hydroxide particles in the slurry can be measured by heating and drying the slurry. More specifically, about 5 g of slurry can be put into a glass petri dish having a diameter of 50 mm, dried by heating in an oven at 80 ° C. for 3 hours, and the mass / slurry mass after drying can be obtained.

(Conductivity of slurry)
The polishing liquid set and slurry of the present invention are characterized in that the conductivity when the concentration of tetravalent metal hydroxide particles contained in the slurry is adjusted to 1% by mass is 1 mS or less. By doing so, it is possible to reduce the amount of the buffer component added to obtain a predetermined pH, and it is possible to prevent the abrasive grains (tetravalent metal hydroxide particles) from aggregating. Further, even if the mixing ratio of the slurry and the additive liquid varies by about ± 25%, it can be suppressed to the target fluctuation of about ± 0.1. Therefore, a CMP polishing liquid can be obtained that can suppress variations in polishing rate without shortening the pot life of the CMP polishing liquid.

  From this viewpoint, the conductivity is 1 mS (= 1000 μS) or less, preferably 900 μS or less, more preferably 800 μS or less, still more preferably 700 μS or less, and particularly preferably 600 μS or less. Preferably, it is most preferably 500 μS or less.

  For measurement of the conductivity of the slurry, a conductivity meter (for example, a product name: CyberScan PC300 manufactured by Eutech Instruments Pte Ltd.) can be used. More specifically, the conductivity meter can be calibrated using a 1413 μS standard solution, and then an electrode is placed in the slurry, and the value displayed as the conductivity after 1 minute is read. All measurements are performed at 25 ° C.

  When measuring the conductivity of the slurry, if the concentration of the tetravalent metal hydroxide particles in the slurry is higher than 1% by mass, it is 1% by mass with pure water (electric resistivity of 18 MΩ · cm or more). Dilute to make a measurement. Further, when the concentration of the tetravalent metal hydroxide particles in the slurry is lower than 1% by mass, water is distilled off by a rotary evaporator to once the concentration is 1% by mass or more. Dilute to mass% and perform measurement.

  As a method for reducing the conductivity of the slurry, specifically, for example, a method of repeatedly washing when synthesizing the tetravalent metal hydroxide particles, a method of treating the slurry with an ion exchange resin, an electric type A method using a desalting apparatus, a method using an electrodialyzer, a dialysis method, or the like can be used.

(Slurry pH)
The pH of the slurry has an influence on the stability of the slurry, the ease of pH adjustment when preparing the CMP polishing liquid, and the pot life of the CMP polishing liquid. It is preferable that it exists in. The lower limit of the pH mainly affects the ease of pH adjustment when preparing the CMP polishing liquid and the pot life of the CMP polishing liquid, and is more preferably 3.2 or more, and 3.5 or more. More preferably it is. Further, the upper limit mainly affects the storage stability of the slurry, more preferably 5.5 or less, and still more preferably 5.0 or less.

  The pH of the slurry or CMP polishing liquid can be measured with a pH meter (for example, Yokogawa Electric Corporation, trade name: Model pH81). Specifically, for example, after calibrating two pH meters using a phthalate pH buffer solution (pH 4.01) and a neutral phosphate pH buffer solution (pH 6.86) as standard buffers, The pH meter electrode is put into a slurry or CMP polishing solution, and the value after 2 minutes has passed and stabilized is measured. At this time, all liquid temperatures shall be 25 degreeC.

(II. Additive solution)
Next, the additive liquid that is a component of the polishing liquid set of the present invention will be described. The additive liquid contains water and additives. Here, the additive refers to a substance contained other than water and tetravalent metal hydroxide particles in order to adjust the dispersibility, polishing characteristics, storage stability, and the like of the tetravalent metal hydroxide particles.

(Additive 1: Buffer component)
When the additive liquid is mixed with the slurry to prepare the CMP polishing liquid, the CMP polishing liquid is preferably adjusted to a predetermined pH. For this reason, it is preferable to contain a buffer component as an additive. As the buffer component, it is preferable to select a compound having a pKa within ± 1.5, more preferably within ± 1.0 with respect to the target pH, and specifically, for example, carboxylic acids, phosphoric acid, boric acid Amines, nitrogen-containing heterocyclic compounds, amino acids, amine oxides and the like, and salts thereof may be used. Moreover, a buffer component can be used individually or in combination of 2 or more types.

  The carboxylic acid is not particularly limited as long as it has solubility in water. For example, formic acid, acetic acid, propionic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid Citric acid, lactic acid, benzoic acid, butyric acid, valeric acid, caproic acid and the like can be used.

  Examples of amines include ethylenediamine, 2-aminopyridine, 3-aminopyridine, xanthosine, toluidine, picolinic acid, histidine, piperazine, 1-methylpiperazine, 2-bis (2-hydroxyethyl) amino-2- (hydroxy Methyl) -1,3-propanediol, morpholine, N-methylmorpholine, piperidine, 2-morpholinoethanesulfonic acid, piperidine-1,4-bis (2-ethanesulfonic acid), hydroxylamine, aniline, 2,5- Dimethylpyridine or the like can be used.

  As the nitrogen-containing heterocyclic compound, for example, pyridine, imidazole, benzimidazole, pyrazole, triazole, benzotriazole and the like can be used.

  Amino acids improve the dispersibility of the tetravalent metal hydroxide particles and improve the polishing rate. For example, arginine, lysine, aspartic acid, glutamic acid, asparagine, glutamine, histidine, proline, tyrosine, tryptophan, serine, threonine, glycine, alanine, β-alanine, methionine, cysteine, phenylalanine, leucine, valine, isoleucine can be used. .

  Of these, acetic acid, lactic acid, benzoic acid, and imidazole are more preferable from the viewpoint of easy pH adjustment and pot life of the CMP polishing liquid, and it is most preferable to use a combination of acetic acid and imidazole.

  The addition amount of the buffer component is preferably 0.01 parts by mass to 5 parts by mass with respect to 100 parts by mass of the CMP polishing liquid when used as a CMP polishing liquid. The lower limit of the addition amount is more preferably 0.02 parts by mass or more, and most preferably 0.05 parts by mass or more, from the viewpoint of suppressing variation in pH. The upper limit of the addition amount is more preferably 1 part by mass or less, and most preferably 0.5 part by mass or less from the viewpoint of the pot life of the CMP polishing liquid. In addition, when using a some compound as a buffer component, the said addition amount is those total. Moreover, since the addition amount of the buffer component in an addition liquid changes with concentration as mentioned later, there is no restriction | limiting in particular.

(Additive 2: Property modifier)
The additive solution may contain a property adjusting agent as an additive for the purpose of adjusting polishing properties. Examples of the property modifier include amphoteric surfactants, cationic surfactants, nonionic surfactants, anionic surfactants, cationic polymer compounds, nonionic polymer compounds, anionic polymer compounds, From the viewpoint of polishing rate, a cationic surfactant, a nonionic surfactant, a cationic polymer compound, and a nonionic polymer compound are preferable.

  The amphoteric surfactant has the effect of improving the dispersibility of the tetravalent metal hydroxide particles and improving the polishing rate. Specifically, for example, betaine, β-alanine betaine, lauryl betaine, stearyl betaine. Lauryldimethylamine oxide, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauric acid amidopropyl betaine, coconut oil fatty acid amidopropyl betaine, lauryl hydroxysulfobetaine, and the like. Among these, from the viewpoint of improving dispersibility and stability, betaine, β-alanine betaine, and lauric acid amidopropyl betaine are more preferable.

  Anionic surfactants have the effect of adjusting the flatness and in-plane uniformity of polishing characteristics. For example, lauryl sulfate triethanolamine, lauryl ammonium sulfate, polyoxyethylene alkyl ether sulfate triethanolamine, special polycarboxylic acid type Examples thereof include a polymer dispersant.

  Nonionic surfactants have the effect of adjusting the flatness and in-plane uniformity of polishing properties and controlling foaming to improve handling and cleaning properties. For example, polypropylene glycol ethylene oxide adducts (pluronic non-type surfactants) Ionic surfactant), polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene higher alcohol ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether , Polyoxyalkylene alkyl ether, polyoxyethylene derivatives, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan Nostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbite tetraoleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol di Examples include stearate, polyethylene glycol monooleate, polyoxyethylene alkylamine, polyoxyethylene hydrogenated castor oil, 2-hydroxyethyl methacrylate, and alkylalkanolamide.

  The cationic surfactant has an effect of adjusting the flatness and in-plane uniformity of the polishing characteristics, and examples thereof include coconut amine acetate and stearylamine acetate.

  The cationic polymer compound has an effect of suppressing the polishing rate of silicon nitride used as a polishing stopper film and improving the controllability of the polishing end point. For example, polyethyleneimine, polyallylamine, polylysine, polydimethylacrylamide, chitosan and These derivatives are mentioned, and may be a copolymer with another monomer. Most preferred are polyallylamine and chitosan.

  Polyallylamine and polyethyleneimine may be linear or have a branched structure. The amino group may be any of primary to quaternary, and a plurality of amino groups may be mixed in the molecule.

  Polyethyleneimine derivatives include, for example, aldehydes, ketones, alkyl halides, isocyanates, thioisocyanates, double bonds, epoxy compounds, cyanamides, guanidines, urea, carboxylic acids, acid anhydrides, acyl halides, and the like. What reacted is mentioned.

  Examples of chitosan derivatives include chitosan pyrrolidone carboxylate, cationized chitosan, hydroxypropyl chitosan, chitosan lactate, glycerylated chitosan, glycol chitosan, carboxymethyl chitosan (CM-chitosan), carboxymethyl chitosan succinamide and the like. It is done.

  The weight average molecular weight of polyallylamine or a derivative thereof is not particularly limited as long as it can be dissolved in water, preferably 100 or more, more preferably 300 or more and less than 1 million, and most preferably 1000 or more and less than 300,000. When the molecular weight is 100 or more, the polishing rate ratio between the silicon oxide film and the stopper film is good, and when it is less than 1,000,000, the viscosity is not too high, so that the handleability is good.

  For the same reason as polyallylamine, the molecular weight of polyethyleneimine or a derivative thereof is preferably 100 or more, more preferably 300 or more and less than 1 million, and most preferably 1000 or more and less than 200,000.

  Nonionic polymer compounds have an effect of improving flatness, for example, polysaccharides such as agar, curdlan and pullulan; vinyl polymers such as polyvinyl alcohol, polyvinylpyrrolidone and polyacrolein; polyacrylamide, polydimethylacrylamide, Acrylic polymers such as poly (N- (2-hydroxyethyl) acrylamide) and polyacryloylmorpholine, polyethylene glycol, polyoxypropylene, polyoxyethylene-polyoxypropylene condensate, polyoxyethylene-polyoxypropylene block of ethylenediamine Examples thereof include polymers. Polyvinyl alcohol is particularly preferable because it can improve flatness.

  Examples of the anionic polymer compound include alginic acid, pectinic acid, carboxymethylcellulose, polyaspartic acid, polyglutamic acid, polylysine, polymalic acid, polyamic acid, polymaleic acid, polyitaconic acid, polyfumaric acid, poly (p-styrenecarboxylic acid). And polycarboxylic acids such as polyamic acid ammonium salt, polyamic acid sodium salt and polyglyoxylic acid and salts thereof.

  The weight average molecular weight of these polymer compounds is preferably 500 or more from the viewpoint of obtaining the effect of adjusting the characteristics. The weight average molecular weight can be measured using a static light scattering method. In the present invention, the measurement is performed using Spectris Co., Ltd., trade name: Zetasizer Nano S, measuring the amount of scattered light of samples having different concentrations, and performing a Debye plot. At this time, the refractive index concentration increment (dn / dC) is measured using a differential refractometer (trade name: DRM-3000, manufactured by Otsuka Electronics Co., Ltd.). In all cases, the measurement is performed at 25 ° C. using water as a solvent.

  Specifically, for example, the polymer compound is dissolved so that the concentration is 0.01 mg / ml to 5 mg / ml, filtered through a 0.2 μm filter, and four or more sample solutions having different concentrations are prepared. To do. First, as a standard substance, about 1 ml of filtered toluene is put into a 1 cm square quartz cell, set in the sample chamber of the Zetasizer Nano S, and the amount of scattered light is measured. Water is measured by the same method, and the amount of scattered light of the solvent is measured. Next, the sample solution is sequentially measured, and the amount of scattered light of the sample solution is measured.

  On the other hand, 5 ml of water is injected into the sample injection portion of the differential refractometer DRM-3000, left for about 5 minutes, adjusted for zero point, and measured for 1 minute. Next, 3 ml of the sample solution is injected, and the sample solution is allowed to stand for about 5 minutes before measurement. Plot the refractive index against the concentration and read the value displayed as dn / dC.

  After a series of measurements, with the Zetasizer Nano S software, select the value obtained in the above measurement for dn / dC, Small Molecule for Shape Correction Model, perform Debye plot, and read the value displayed as Molecular Weight.

  The addition amount of these property modifiers is preferably in the range of 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the CMP polishing liquid when used as a CMP polishing liquid. If the amount added is too large, it tends to settle. In addition, when using a some compound as a characteristic regulator, the said addition amount is those total. Moreover, since the addition amount of the characteristic modifier in the additive solution changes with concentration as described later, there is no particular limitation.

  This polishing liquid set may be stored in two components, a slurry and an additive liquid. However, at least one of the slurry and the additive liquid in this polishing liquid set is stored after being concentrated by reducing the solvent content and polishing. Sometimes it may be diluted with a diluent. That is, you may preserve | save with three components of slurry, an addition liquid, and dilution liquids, such as water.

As the slurry and the solvent and diluent of the additive solution, water is mainly used, but in addition to this, a material selected from the following group may be included as long as the effect of the CMP polishing solution of the present invention is not impaired. That is, methanol, ethanol, 1-propanol, 2-propanol, 2-propyn-1-ol, allyl alcohol, ethylene cyanohydrin, 1-butanol, 2-butanol (S)-(+)-2-butanol, 2-methyl -1-propanol, t-butanol, perfluoro-t-butanol, t-pentyl alcohol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, glycerin, 2-ethyl-2- Alcohols such as (hydroxymethyl) -1,3-propanediol, 1,2,6-hexanetriol, furfuryl alcohol;
Dioxane, trioxane, tetrahydrofuran, diethylene glycol diethyl ether, 2-methoxyethanol, 2-ethoxyethanol, 2,2- (dimethoxy) ethanol, 2-isopropoxyethanol, 2-butoxyethanol, 1-methoxy-2-propanol, 1- Ethers such as ethoxy-2-propanol;
Examples include ketones such as acetone, methyl ethyl ketone, acetylacetone, and cyclohexanone.

  Among these, water, methanol, ethanol, 2-propanol, tetrahydrofuran, ethylene glycol, acetone, and methyl ethyl ketone are more preferable, and water is particularly preferable in that a high polishing rate can be obtained.

  The polishing liquid set of the present invention can adjust the polishing rate by arbitrarily changing the composition of the slurry and the additive liquid. When polishing using this polishing liquid set now, as a method of supplying the CMP polishing liquid onto the polishing surface plate, for example, the slurry and the additive liquid are fed through separate pipes, and these pipes are merged and mixed. A method of supplying the slurry, the slurry and the additive solution separately onto the polishing surface plate, a method of feeding the slurry, the additive solution, and water through separate pipes, and combining and mixing them, A method of mixing and supplying the slurry and additive liquid immediately before polishing, a method of mixing and supplying slurry, additive liquid, and water immediately before polishing can be used.

  In the polishing method of the present invention, a substrate on which a film to be polished is formed is pressed against a polishing cloth on a polishing platen and pressed, and a CMP polishing liquid obtained by mixing the polishing liquid set of the present invention is converted into a film to be polished. The film to be polished is polished by relatively moving the substrate and the polishing surface plate while supplying between the polishing cloth and the polishing cloth.

  Examples of the substrate include a substrate related to semiconductor element manufacture, for example, a substrate in which an insulating film is formed on a semiconductor substrate on which a shallow trench isolation pattern, a gate pattern, a wiring pattern and the like are formed. Examples of the film to be polished include an insulating film formed on these patterns, such as a silicon oxide film and a silicon nitride film.

  By polishing the silicon oxide film or silicon nitride film formed on such a semiconductor substrate with the above-described CMP polishing liquid, unevenness on the surface of the silicon oxide film layer is eliminated, and the entire surface of the semiconductor substrate is made smooth. Can do. As described above, the CMP polishing liquid prepared using the polishing liquid set of the present invention is preferably used for polishing a surface to be polished containing silicon oxide at least on the surface.

  Further, the CMP polishing liquid obtained by mixing the polishing liquid set of the present invention can be suitably used for shallow trench isolation. In order to use it for shallow trench isolation, the selection ratio is preferably 10 or more. When the selection ratio is less than 10, the difference between the silicon oxide film polishing rate and the stopper film polishing rate is small, and it becomes difficult to stop polishing at a predetermined position when performing shallow trench isolation. When the selection ratio is 10 or more, it is easy to stop polishing, which is more suitable for shallow trench isolation.

  In addition, for use in shallow trench isolation, it is preferable that scratches are less likely to occur during polishing. As the stopper film, for example, silicon nitride, polysilicon or the like can be used.

  Further, it can be used for polishing a premetal insulating film. As the premetal insulating film, in addition to silicon oxide, for example, phosphorus-silicate glass or boron-phosphorus-silicate glass is used, and silicon oxyfluoride, fluorinated amorphous carbon, or the like can also be used.

Hereinafter, the polishing method will be described by taking a semiconductor substrate on which an insulating film is formed as an example.
In the polishing method of the present invention, as a polishing apparatus, a general polishing apparatus having a holder capable of holding a substrate having a film to be polished, such as a semiconductor substrate, and a polishing surface plate to which a polishing cloth can be attached. Can be used.

  The substrate holder and the polishing surface plate are each provided with a motor or the like whose rotational speed can be changed. For example, a polishing apparatus manufactured by Ebara Corporation: model number EPO-111 can be used.

  As the polishing cloth, general nonwoven fabrics, foams, non-foams, etc. can be used, and the materials are polyurethane, acrylic, polyester, acrylic-ester copolymer, polytetrafluoroethylene, polypropylene, polyethylene, poly-4-methyl. Polyamide such as pentene, cellulose, cellulose ester, nylon and aramid, polyimide, polyimide amide, polysiloxane copolymer, oxirane compound, phenol resin, polystyrene, polycarbonate, epoxy resin and the like can be used. From the viewpoint of polishing rate and flatness, polyurethane foam and non-foamed polyurethane are particularly preferable.

  Further, it is preferable that the polishing cloth is subjected to a groove processing so that the CMP polishing liquid is accumulated. Although there is no limitation on polishing conditions, the rotation speed of the surface plate is preferably 200 rotations / minute or less so that the semiconductor substrate does not jump out, and the pressure (working load) applied to the semiconductor substrate is such that polishing scratches do not occur. 100 kPa or less is preferable. During polishing, a CMP polishing liquid is continuously supplied to the polishing cloth with a pump or the like. Although the supply amount is not limited, it is preferable that the surface of the polishing pad is always covered with a CMP polishing liquid.

  The semiconductor substrate after polishing is preferably washed well under running water to remove particles attached to the substrate. For cleaning, dilute hydrofluoric acid or ammonia water may be used in addition to pure water, and a brush may be used in combination to increase cleaning efficiency.

  In addition, after washing, it is preferable to dry after removing water droplets adhering to the semiconductor substrate using a spin dryer or the like.

  As a method for producing an insulating film in which the polishing liquid set of the present invention is used, a CVD method represented by a low pressure CVD (chemical vapor deposition) method, a quasi-atmospheric pressure CVD method, a plasma CVD method, etc. In addition, there is a spin coating method in which a liquid material is applied to a rotating substrate.

The silicon oxide film formed by the low pressure CVD method is obtained, for example, by causing a thermal reaction between monosilane (SiH ₄ ) and oxygen (O ₂ ).

The silicon nitride film formed by the low pressure CVD method can be obtained, for example, by thermally reacting dichlorosilane (SiH ₂ Cl ₂ ) and ammonia (NH ₃ ).

A silicon oxide film formed by a quasi-atmospheric pressure CVD method is obtained, for example, by thermally reacting tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ) and ozone (O ₃ ). A silicon oxide film formed by a plasma CVD method can be obtained, for example, by causing a plasma reaction between monosilane and nitrogen dioxide (NO ₂ ).

  As another example, a silicon oxide film can be similarly obtained even when tetraethoxysilane and oxygen are subjected to a plasma reaction.

A silicon nitride film formed by the plasma CVD method can be obtained by, for example, plasma reaction of monosilane, ammonia, and nitrogen (N ₂ ).

  A silicon oxide film formed by spin coating is obtained, for example, by applying a liquid raw material containing inorganic polysilazane, inorganic siloxane, or the like onto a substrate and causing a thermosetting reaction in a furnace body or the like.

  In order to stabilize the film quality of an insulating film such as a silicon oxide film or a nitrogen silicon film obtained by the above method, heat treatment may be performed at a temperature of 200 ° C. to 1000 ° C. as necessary.

  Further, the silicon oxide film obtained by the above method may contain a trace amount of boron (B), phosphorus (P), carbon (C), or the like in order to improve the embedding property.

  The polishing liquid set, slurry, and polishing method of the present invention can also be applied to films other than insulating films, such as silicon oxide films and nitrogen silicon films. For example, high dielectric constant films such as Hf-based, Ti-based, and Ta-based oxides, semiconductor films such as silicon, amorphous silicon, polysilicon, SiC, SiGe, Ge, GaN, GaP, GaAs, and organic semiconductors, phases such as GeSbTe Examples thereof include a change film, an inorganic conductive film such as ITO, a polymer resin film such as polyimide, polybenzoxazole, acrylic, epoxy, and phenol.

  The polishing liquid set, slurry and polishing method of the present invention are applicable not only to film-like materials but also to various substrate materials such as glass, silicon, SiC, SiGe, Ge, GaN, GaP, GaAs, sapphire, and plastic. it can.

  Furthermore, the polishing liquid set, slurry and polishing method of the present invention are not only for manufacturing semiconductor elements, but also for image display devices such as TFT and organic EL, photomasks, lenses, prisms, optical fibers, optical components such as single crystal scintillators, It can be used for manufacturing optical storage elements such as optical switching elements and optical waveguides, light emitting elements such as solid state lasers and blue laser LEDs, magnetic disks, and magnetic heads.

<Polishing of insulating film>
An evaluation wafer in which a silicon oxide film (SiO ₂ ) having a film thickness of 1000 nm is formed on the entire surface of a silicon (Si) substrate having a diameter of 200 mm on a substrate holder of a polishing apparatus (manufactured by Ebara Corporation, model number: EPO-111). On the other hand, a polishing cloth IC-1000 made of porous urethane resin (model number, groove shape: perforate) made of porous urethane resin was attached to a polishing surface plate having a diameter of 600 mm.

  The substrate holder was pressed onto the polishing cloth so that the silicon oxide film was in contact with the polishing cloth, and the processing load was set to 30 kPa. While the prepared CMP polishing liquid was dropped on the polishing cloth at a rate of 200 ml / min, the surface plate and the substrate holder were operated at 50 rpm, and the evaluation wafer was polished for 30 seconds.

The polished evaluation wafer was thoroughly washed with pure water and then dried. Then, the residual film thickness of the silicon oxide was measured using the optical interference type film thickness apparatus (Nanometrics Japan Co., Ltd. make, brand name: Nanospec AFT-5100). Here, the silicon oxide polishing rate per minute (RR: SiO ₂ ) was determined from (amount of decrease in silicon oxide film) / (polishing time).

(Preparation of slurry A)
38.4 g of Ce (NH ₄ ) ₂ (NO ₃ ) ₆ was dissolved in 1870 g of pure water, and then 20 g of ammonia water (25% by mass aqueous solution) was mixed and stirred to cerium hydroxide (yellowish white) Was synthesized. Solid-liquid separation was performed by centrifugation (8200G, 15 minutes). The liquid was removed, 100 g of pure water was newly added, and the mixture was again washed by centrifugation under the above conditions. Such washing operation was repeated 8 times.

  723 g of pure water was added to the obtained cerium hydroxide, and the mixture was stirred and irradiated with ultrasonic waves using an ultrasonic cleaner, and the average particle diameter measured using Spectris Co., Ltd., trade name: Zeta Sizer Nano S Dispersion treatment was performed until (Z-average Size) reached about 100 nm, and cerium hydroxide slurry (slurry A) was obtained.

  5.0 g of this slurry A was taken in a glass petri dish having a diameter of 50 mm and dried in an oven at 80 ° C. for 3 hours. When the concentration was determined from the mass after drying, the cerium hydroxide concentration of slurry A was 1.6% by mass.

(Slurry B: Preparation of slurry with conductivity of 800 μS)
A slurry (slurry B) was prepared by mixing 600 g of the slurry A and 360 g of pure water to a cerium hydroxide concentration of 1.0 mass%. For Slurry B, the conductivity and pH were measured using Eutech Instruments Pte Ltd. Product name: Measured with a CyberScan PC300, the conductivity was 800 μS and the pH was 3.01.

  Slurry B was diluted so that the cerium hydroxide concentration was 0.2% by mass, and the average particle diameter was measured using Zetasizer Nano S (trade name, manufactured by Spectris Co., Ltd.). there were.

  In addition, in order to measure the zeta potential of the particles in the slurry B, after being diluted with water to an appropriate concentration and measured using a Zeta Sizer 3000HS (trade name, manufactured by Spectris Co., Ltd.), it was +43 mV. All measurements were performed at 25 ° C.

(Slurry C: Preparation of slurry with conductivity of 160 μS)
Slurry B: 50 g obtained above was placed in a dialysis tube (Spectrum Laboratories, Inc., trade name: Spectra / Por 1), soaked in pure water, dialyzed for 4 days while exchanging pure water, and then slurryed. C was obtained. This slurry C had a cerium hydroxide concentration of 1.0 mass%, an electrical conductivity of 160 μS, and a pH of 3.67.

  Further, the slurry was diluted so that the cerium hydroxide concentration of slurry C was 0.2% by mass, and the average particle size was measured, and it was 105 nm.

(Comparison slurry: Preparation of slurry with electrical conductivity of 1.4 mS)
A cerium hydroxide slurry (slurry D) was obtained in the same manner as the preparation of slurry A, except that the washing operation was repeated 4 times instead of 8 times. The concentration of cerium hydroxide in slurry D was 1.7% by mass. This slurry D: 600 g and pure water: 420 g were mixed to prepare a slurry (comparative slurry) having a cerium hydroxide concentration of 1.0 mass%. The conductivity was 1.4 mS and the pH was 2.60. Moreover, it diluted to the cerium hydroxide density | concentration so that it might become 0.2 mass%, and it was 101 nm when the average particle diameter was measured.

<PH and polishing rate variation>
Hereinafter, when the pH of the CMP polishing liquid is set to 6.5, the superiority of the present invention is shown in terms of pH and polishing rate variations when the mixing ratio varies.

Example 1
As a buffer component, an additive solution A consisting of acetic acid: 2 g, imidazole: 3.3 g, and water: 94.7 g was prepared.

  The slurry C (cerium hydroxide concentration: 1.0% by mass, conductivity: 160 μS) prepared above was mixed with 4 g of water: 15.7 g and the above additive solution A: 0.30 g to obtain CMP polishing solution 1 Prepared. The pH of the CMP polishing liquid 1 was 6.50. Similarly, CMP polishing liquids were prepared in which the compounding amount of the additive liquid A was changed from -40% to + 40% based on 0.30 g, and the pHs thereof were measured. The result of the correlation between the additive liquid blending amount and pH is shown in FIG.

(Comparative Example 1)
Example 1 except that the comparative slurry prepared above (cerium hydroxide concentration: 1.0 mass%, conductivity: 1.4 mS) was used as the slurry, and an aqueous 5 mass% imidazole solution was used instead of the additive liquid A. Comparative CMP polishing liquid 1 was prepared in the same manner as described above. As in Example 1, the pH of various CMP polishing liquids that were changed from −40% to + 40% based on 0.30 g was measured. The result of the correlation between the additive liquid blending amount and pH is shown in FIG. In FIG. 1, the solid line indicates Example 1 and the dotted line indicates Comparative Example 1.

(Example 2)
Using the CMP polishing liquid 1 prepared in Example 1, the silicon oxide was polished as described above, and the silicon oxide polishing rate was determined. Similarly, the amount of additive liquid A added was changed from −40% to + 40% in the same manner as in Example 1 based on 0.3 g, and a CMP polishing liquid was prepared, and the silicon oxide polishing rate was determined. The result of the correlation between the additive liquid blending amount and the polishing rate is shown in FIG.

(Comparative Example 2)
A correlation between the amount added and the polishing rate was obtained in the same manner as in Example 2 except that the comparative CMP polishing liquid 1 was used. The results are shown in FIG. In FIG. 2, the solid line indicates Example 2 and the dotted line indicates Comparative Example 2.

  From the above Examples 1 and 2 and Comparative Examples 1 and 2, the present polishing liquid set consisting of slurry and additive liquid is insensitive to pH and polishing rate fluctuations with respect to the deviation of the additive liquid addition amount. It can be seen that this is effective in suppressing variations in the polishing rate.

<CMP polishing liquid pot life>
Hereinafter, when the pH of the CMP polishing liquid is set to 6.5, the superiority of the CMP polishing liquid usable time of this polishing liquid set will be described.

(Example 3)
The average particle diameter of the CMP polishing liquid 1 prepared in Example 1 was measured using Zetasizer Nano S (trade name, manufactured by Spectris Co., Ltd.), and the change with time was traced. The CMP polishing liquid was stored in a propylene screw tube (inner diameter 30 mm, height 55 mm), sealed with 20 g of CMP polishing liquid, and stored in air at 25 ° C. In addition, as a criterion for determining the pot life, the time until the average particle diameter becomes twice or more immediately after mixing is defined as the pot life.

Example 4
The slurry B (cerium hydroxide concentration: 1.0%, conductivity: 800 μS): 4 g, water: 15.65 g, additive liquid A prepared in Example 1: 0.35 g was mixed in CMP polishing liquid 2 Was prepared. The pH of the CMP polishing liquid 2 was 6.50.

  In the same manner as in Example 3, the time change of the average particle diameter was followed to determine the pot life.

(Comparative Example 3)
Comparative CMP by mixing the above comparative slurry (cerium hydroxide concentration: 1.0%, conductivity: 1.4 mS): 4 g, water: 15.55 g, and additive solution A: 0.45 g prepared in Example 1 A polishing liquid 2 was prepared. The pH of this CMP polishing liquid was 6.50.

  In the same manner as in Example 3, the time change of the average particle diameter was followed to determine the pot life.

  Table 1 shows the pot life of Examples 3 and 4 and Comparative Example 3. Apparently, when the conductivity of the slurry is 1 mS or less, the pot life of the CMP polishing liquid is improved, and the superiority of the polishing liquid set of the present invention is clear.

Claims (18)

A polishing liquid set comprising a slurry containing water and tetravalent metal hydroxide particles, and an additive liquid containing water and an additive,
The polishing liquid set is mixed and used as a CMP polishing liquid,
The slurry is a polishing liquid set in which the conductivity when the concentration of tetravalent metal hydroxide particles is 1% by mass is 1 mS or less.   The polishing liquid set according to claim 1, wherein an average particle diameter of the tetravalent metal hydroxide particles in the slurry is 1 nm or more and 400 nm or less.   The polishing liquid set according to claim 1 or 2, wherein the slurry has a pH of 3.0 or more and 6.0 or less.   The polishing liquid set according to any one of claims 1 to 3, wherein the content of the tetravalent metal hydroxide particles in the slurry is 0.2 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the slurry. .   The polishing liquid set according to any one of claims 1 to 4, wherein the zeta potential of the tetravalent metal hydroxide particles in the slurry is +10 mV or more.   The polishing liquid set according to any one of claims 1 to 5, which is used for polishing a surface to be polished containing silicon oxide at least on the surface.   The polishing liquid set according to any one of claims 1 to 6, wherein the tetravalent metal hydroxide particles are at least one of rare earth metal hydroxide particles and zirconium hydroxide particles. Mixing the polishing liquid set according to claim 1 to obtain a CMP polishing liquid;
The substrate on which the film to be polished is formed is pressed against the polishing cloth of the polishing surface plate and pressurized, and the substrate and the polishing surface plate are relatively moved while supplying the CMP polishing liquid between the film to be polished and the polishing cloth. A method for polishing a substrate, comprising: polishing a film to be polished.   A substrate polished by the polishing method according to claim 8. A slurry containing water and tetravalent metal hydroxide particles,
The slurry is mixed with an additive liquid containing water and an additive to form a CMP polishing liquid.
A slurry having a conductivity of 1 mS or less when the concentration of the tetravalent metal hydroxide particles is 1% by mass.   The slurry according to claim 10, wherein the average particle diameter of the tetravalent metal hydroxide particles in the slurry is 1 nm or more and 400 nm or less.   The slurry according to claim 10 or 11, wherein the pH of the slurry is 3.0 or more and 6.0 or less.   The slurry according to any one of claims 10 to 12, wherein the content of the tetravalent metal hydroxide particles in the slurry is 0.2 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the slurry.   The slurry according to any one of claims 10 to 13, wherein the zeta potential of the tetravalent metal hydroxide particles in the slurry is +10 mV or more.   The slurry according to any one of claims 10 to 14, wherein the polishing liquid is used to polish a surface to be polished containing silicon oxide on at least a surface.   The slurry according to any one of claims 10 to 15, wherein the tetravalent metal hydroxide particles are at least one of rare earth metal hydroxide particles and zirconium hydroxide particles. Mixing at least the slurry according to any one of claims 10 to 16 with an additive liquid containing water and an additive liquid to obtain a CMP polishing liquid;
The substrate on which the film to be polished is formed is pressed against the polishing cloth of the polishing surface plate and pressurized, and the substrate and the polishing surface plate are relatively moved while supplying the CMP polishing liquid between the film to be polished and the polishing cloth. And polishing the film to be polished.   A substrate polished by the polishing method according to claim 17.

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