JP6029916B2 - Polishing composition - Google Patents

Description

  The present invention relates to a polishing composition. The present invention also relates to a polishing method and a substrate manufacturing method using the polishing composition.

  In recent years, downsizing, high integration, and high performance of semiconductor elements and hard disks have been remarkable. Along with this, a new fine processing technique has been developed, and a chemical mechanical polishing (hereinafter simply referred to as “CMP”) method is one of them. This CMP method is a technique frequently used in silicon wafer and hard disk manufacturing processes, LSI manufacturing processes, particularly in the formation of interlayer insulation films, metal plugs, and embedded wiring (damascene wiring) in multilayer wiring forming processes. .

  Abrasives used in CMP generally contain abrasive grains and chemicals. The CMP by the CMP abrasive comprises a combination of a mechanical friction action by abrasive grains on the object to be polished and a chemical action by chemicals on the object to be polished. A general method of CMP is to apply a polishing pad on a circular polishing surface plate (platen), immerse the polishing pad surface with a CMP abrasive, press the surface of the object to be polished, Rotate the polishing platen under pressure (hereinafter also referred to simply as polishing pressure), and remove part of the surface of the polishing object by mechanical friction and chemical action between the CMP abrasive and the surface of the polishing object. To do.

  In general, CMP requires a high polishing rate, a stable polishing rate, and a low defect density on the polishing surface. Among these, with respect to the polishing rate, for example, it is known that the polishing rate is improved by adjusting the polishing composition to an alkaline pH or increasing the electrical conductivity of the polishing composition by adding a salt. On the other hand, if the amount of the alkali compound added is too large or the electrical conductivity is increased too much, the abrasive grains agglomerate in the polishing composition, resulting in a change in the grain size of the abrasive grains, instability of the polishing rate, There are disadvantages such as a decrease in storage stability and generation of defects on the surface of the object to be polished after polishing. In order to eliminate such disadvantages, for example, Patent Document 1 proposes a polishing composition for silicon wafers containing silica abrasive particles, water, a basic substance, and an inorganic salt. Further, Patent Document 2 proposes a polishing composition for a barrier containing silica abrasive particles and dicarboxylic acid and having a pH adjusted to near neutral and the electric conductivity of the polishing liquid adjusted to a certain value or less. .

Republished 2005-090511 JP 2007-116090 A

  However, in the polishing composition described in Patent Document 1, a solution has been found in reducing the amount of alkali added, but there is room for improvement in terms of a decrease in storage stability of the polishing composition accompanying the addition of salt. There is. Further, the polishing assembly described in Patent Document 2 requires further improvement for increasing the polishing rate.

  Therefore, the present invention provides a polishing composition that can achieve both improvement in storage stability at alkaline pH and improvement in polishing rate when polishing a substrate, in a polishing composition used for polishing a substrate. For the purpose.

  In order to solve the above-mentioned problems, the present inventors have intensively studied. As a result, it discovered that the said subject could be solved by using the polishing composition containing an anion modified abrasive grain, an alkali compound, and water. In particular, as disclosed in JP 2010-269985 A, anion-modified abrasive grains that have been conventionally used to improve the dispersion stability of abrasive grains under acidic conditions can be obtained under alkaline conditions. The present invention has been completed based on the new knowledge that the above-mentioned problems can be solved by using it.

  That is, the present invention includes abrasive grains, an alkali compound, and water, the abrasive grains carry an anionic functional group, and the polishing composition has a pH of 7.0 or more. It is a composition.

  According to the present invention, a polishing composition used for polishing a substrate is provided with a polishing composition capable of achieving both improved storage stability at alkaline pH and improved polishing rate when polishing the substrate. Can be done.

  The present invention is a polishing composition comprising abrasive grains carrying an anionic functional group, an alkali compound, and water, and having a pH of 7.0 or more. By adopting such a configuration, it is possible to improve both the storage stability at alkaline pH and the throughput.

  Although the detailed reason for improving the polishing rate while maintaining high storage stability at an alkaline pH by using the polishing composition of the present invention is unknown, the affinity between the anionic functional group on the abrasive grain surface and the alkali compound is unknown. Is high, the effective alkali concentration of the abrasive grain surface is increased. As a result, it is considered that the alkali contributing to the polishing action (etching) is efficiently provided to the surface of the object to be polished, and the polishing rate is improved. In addition, the negatively charged portion of the abrasive grain surface added by modification reacts or adsorbs preferentially with the alkali compound and salt, thereby reducing the influence on the abrasive grain itself. It is considered that the agglomeration of abrasive grains does not occur even when added in a higher concentration than usual. In addition, the said mechanism is based on estimation and this invention is not limited to the said mechanism at all.

[Polishing object]
First, the substrate as a polishing object according to the present invention is not particularly limited, and the polishing composition of the present invention can be used for CMP of a silicon wafer substrate and a hard disk substrate. On the other hand, the polishing composition of the present invention is used for CMP of a metal wiring layer, a barrier layer, and an interlayer insulating film layer in a semiconductor device, and a substrate containing a low dielectric constant material or a material containing a noble metal as necessary. I can do it.

  The metal contained in the metal wiring layer is not particularly limited, and examples thereof include substances whose main component is metal, such as copper, copper alloy, copper oxide, copper alloy oxide, tungsten, tungsten alloy, silver, and gold. A metal wiring layer mainly composed of copper such as copper, copper alloy, copper oxide, copper alloy oxide or the like is preferable. As the metal wiring layer, a film formed by depositing the substance by a known sputtering method or plating method can be used.

  The barrier layer is formed to prevent diffusion of the metal wiring layer into the insulating film and to improve the adhesion between the insulating film and the metal wiring layer. The conductor used for the barrier layer is selected from tungsten, tungsten nitride, tungsten alloys, other tungsten compounds, titanium, titanium nitride, titanium alloys, other titanium compounds, tantalum, tantalum nitride, tantalum alloys, other tantalum compounds, and noble metals. It is preferable that 1 or more types included are included. The barrier layer may be a single layer made of one kind or a laminated film of two or more kinds.

  Examples of the interlayer insulating film include a silicon material film and an organic polymer film. Examples of the silicon material film include silica-based films such as silicon dioxide, fluorosilicate glass, organosilicate glass, silicon oxynitride, silsesquioxane hydride, silicon carbide, and silicon nitride. Examples of the organic polymer film include a wholly aromatic low dielectric constant interlayer insulating film. In particular, organosilicate glass is preferable. These films are formed by a CVD method, a spin coating method, a dip coating method, or a spray method.

It can also be used for polishing the polysilicon simultaneously with the interlayer insulating film.
Specific examples of the low dielectric constant material include those generally abbreviated as Low-k having a relative dielectric constant of about 3.5 to 2.0, such as silicon carbide oxide (SiOC) (for example, applied). Black diamond (registered trademark) manufactured by Material Co., Ltd.), fluorine-containing silicon oxide (SiOF), organic polymer, and the like.

  Examples of the material containing a noble metal include barrier layers and capacitor electrode materials, such as gold, silver, platinum, palladium, rhodium, ruthenium, iridium, and osmium. These noble metals may be contained in a layer containing the noble metal in the form of an alloy or a noble metal compound.

  Among these polishing objects, silicon-containing materials such as silicon dioxide, fluorosilicate glass, organosilicate glass, silicon oxynitride, hydrogenated silsesquioxane, silicon carbide and silicon nitride, gold, silver , Platinum, palladium, rhodium, ruthenium, iridium, a substrate containing a noble metal such as osmium. With these polishing objects, the effects of the present invention can be obtained more efficiently.

Next, the structure of the polishing composition of the present invention will be described in detail.
[Abrasive grain]
The abrasive grains contained in the polishing composition have an action of mechanically polishing the object to be polished, and improve the polishing rate of the object to be polished by the polishing composition.

  The abrasive used may be any of inorganic particles, organic particles, and organic-inorganic composite particles. Specific examples of the inorganic particles include particles made of metal oxides such as silica, alumina, ceria, titania, silicon nitride particles, silicon carbide particles, and boron nitride particles. Specific examples of the organic particles include polymethyl methacrylate (PMMA) particles. These abrasive grains may be used alone or in combination of two or more. The abrasive grains may be commercially available products or synthetic products.

  Among these abrasive grains, silica is preferable, and colloidal silica is particularly preferable.

  The surface of the abrasive grain is anion-modified. “Anion modification” in the present invention means that the abrasive grains directly or indirectly carry an anionic functional group. Although there is no restriction | limiting in particular in the kind of anionic functional group, As a specific example, carboxylic acid, a sulfonic acid, phosphonic acid, an aluminate is mentioned, for example. The method for supporting an anionic functional group is not particularly limited, and specific examples include a method of reacting abrasive grains with a silane coupling agent having an anionic functional group at the terminal.

  Of these, colloidal silica having an organic acid immobilized thereon is particularly preferable. The organic acid is immobilized on the surface of the colloidal silica contained in the polishing composition, for example, by chemically bonding a functional group of the organic acid to the surface of the colloidal silica. If the colloidal silica and the organic acid are simply allowed to coexist, the organic acid is not fixed to the colloidal silica. For immobilizing sulfonic acid, which is a kind of organic acid, on colloidal silica, see, for example, “Sulphonic acid-functionalized silica through quantitative oxides of thiol groups”, Chem. Commun. 246-247 (2003). Specifically, a silane coupling agent having a thiol group such as 3-mercaptopropyltrimethoxysilane is coupled to colloidal silica, and then the sulfonic acid is immobilized on the surface by oxidizing the thiol group with hydrogen peroxide. The colloidal silica thus obtained can be obtained. Alternatively, if the carboxylic acid is to be immobilized on colloidal silica, for example, “Novel Silene Coupling Agents Containing a Photolabile 2 Nitrobenzyl Ester for Induction of the Carbon Group” -229 (2000). Specifically, colloidal silica having a carboxylic acid immobilized on the surface can be obtained by irradiating light after coupling a silane coupling agent containing a photoreactive 2-nitrobenzyl ester to colloidal silica. .

  The lower limit of the average primary particle diameter of the abrasive grains is preferably 5 nm or more, more preferably 7 nm or more, and further preferably 10 nm or more. Further, the upper limit of the average primary particle diameter of the abrasive grains is preferably 500 nm or less, more preferably 100 nm or less, and further preferably 70 nm or less. Within such a range, the polishing rate of the object to be polished by the polishing composition is improved, and the surface of the object to be polished after polishing with the polishing composition has defects such as steps and polishing scratches. It is possible to further suppress the occurrence. In addition, the average primary particle diameter of an abrasive grain is calculated based on the specific surface area of the abrasive grain measured by BET method, for example.

  The lower limit of the content of the abrasive grains in the polishing composition is preferably 0.005% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more. Most preferably, it is 3 mass% or more. Further, the upper limit of the content of the abrasive grains in the polishing composition is preferably 50% by mass or less, more preferably 30% by mass, and further preferably 15% by mass or less. Within such a range, the polishing rate of the object to be polished can be improved, the cost of the polishing composition can be reduced, and a level difference can be formed on the surface of the object to be polished after polishing with the polishing composition. And the occurrence of defects such as polishing scratches can be further suppressed.

  The abrasive grains in the polishing composition preferably have a zeta potential of -20 mV or less, more preferably -30 mV or less, and most preferably -40 mV or less in an alkaline region having a pH of 7.0 or higher. If it is such a range, the dispersion stability of the abrasive grain in polishing composition will improve.

  The lower limit of the product of the zeta potential on the surface of the abrasive grains in the polishing composition and the zeta potential on the surface of the substrate as the object to be polished is preferably 1000 mV, more preferably 2000. The upper limit of the product of the zeta potential on the surface of the abrasive grains in the polishing composition and the zeta potential on the surface of the substrate as the object to be polished is preferably 3000 mV. Within such a range, the dispersion stability of the abrasive grains in the polishing composition is improved, and the adsorption of the abrasive grains to the substrate is controlled due to the electrostatic repulsive force generated between the substrate surface and the abrasive grain surface. It becomes easy to do. As a result, it is possible to add abrasive grains and other additives (alkali compounds, inorganic salts, etc.) at a high concentration as compared with the prior art, and the polishing rate can be stabilized and improved.

[Alkali compounds]
The alkali compound contained in the polishing composition plays a role of promoting polishing of the surface of the object to be polished by chemical action such as corrosion, etching and oxidation.

  Specific examples of alkali compounds that can be used include inorganic alkali compounds such as potassium hydroxide, sodium hydroxide, potassium bicarbonate, potassium carbonate, sodium bicarbonate, sodium carbonate; ammonia; tetramethylammonium hydroxide (TMAH), carbonate Ammonium salts such as ammonium hydrogen carbonate and ammonium carbonate; methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, monoethanolamine, N- (β-aminoethyl) ethanolamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine And amines such as anhydrous piperazine, piperazine hexahydrate, 1- (2-aminoethyl) piperazine, N-methylpiperazine. Alkaline compounds have a weak amine odor, so potassium hydroxide, sodium hydroxide, potassium bicarbonate, potassium carbonate, sodium bicarbonate, sodium carbonate, ammonia, tetramethylammonium hydroxide (TMAH), ammonium bicarbonate, ammonium carbonate , Ethylenediamine, monoethanolamine, N- (β-aminoethyl) ethanolamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, anhydrous piperazine, piperazine hexahydrate, 1- (2-aminoethyl) piperazine, and N- Methylpiperazine is preferred and has a weak amine odor and does not inhibit the action of the chelating agent. Therefore, potassium hydroxide, sodium hydroxide, potassium bicarbonate, potassium carbonate, sodium bicarbonate, sodium carbonate, Near, tetramethylammonium hydroxide (TMAH), ammonium hydrogen carbonate, ammonium carbonate, anhydrous piperazine, piperazine hexahydrate, 1- (2-aminoethyl) piperazine, and N- methylpiperazine more preferable. These alkali compounds may be used alone or in combination of two or more.

  Alkaline compounds such as potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide (TMAH), ammonium bicarbonate, ammonium carbonate, potassium bicarbonate, potassium carbonate, sodium bicarbonate, sodium carbonate, ammonia, methylamine, dimethylamine , Trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, monoethanolamine, N- (β-aminoethyl) ethanolamine, hexamethylenediamine, diethylenetriamine or triethylenetetramine, the content of the alkali compound in the polishing composition The upper limit of is preferably 6% by weight, more preferably 5% by weight, and most preferably 4% by weight. Further, when the alkaline compound is, for example, anhydrous piperazine, 1- (2-aminoethyl) piperazine or N-methylpiperazine, the upper limit of the content of the alkaline compound in the polishing composition is preferably 10% by weight, more preferably Is 9% by weight, most preferably 8% by weight. When the alkali compound is, for example, piperazine hexahydrate, the upper limit of the content of the alkali compound in the polishing composition is preferably 20% by weight, more preferably 18% by weight, and most preferably 16% by weight.

  Alkaline compounds such as potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide (TMAH), ammonium bicarbonate, ammonium carbonate, potassium bicarbonate, potassium carbonate, sodium bicarbonate, sodium carbonate, ammonia, methylamine, dimethylamine , Trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, monoethanolamine, N- (β-aminoethyl) ethanolamine, hexamethylenediamine, diethylenetriamine or triethylenetetramine, the content of the alkali compound in the polishing composition Is preferably 0.01% by weight, more preferably 0.5% by weight, and most preferably 1% by weight. When the alkali compound is, for example, anhydrous piperazine, 1- (2-aminoethyl) piperazine or N-methylpiperazine, the lower limit of the content of the alkali compound in the polishing composition is preferably 0.01% by weight, more preferably Is 1% by weight, most preferably 3% by weight. When the alkali compound is, for example, piperazine hexahydrate, the lower limit of the content of the alkali compound in the polishing composition is preferably 0.01% by weight, more preferably 2% by weight, and most preferably 5% by weight. is there. Within such a range, the polishing rate of the polishing object can be improved, and the cost of the polishing composition can be reduced, and the surface on the surface of the polishing object after polishing with the polishing composition can be reduced. The occurrence of defects such as roughening and polishing scratches can be further suppressed.

[PH of polishing composition]
The polishing composition of the present invention has a pH of 7.0 or higher. This is to maximize the polishing promoting effect on the object to be polished in the combination of the anion-modified abrasive grains of the present invention and the alkali compound. The pH is preferably 8.0 or more, more preferably 8.5 or more, and even more preferably 9.0 or more.

  A pH adjusting agent may be used to adjust the pH of the polishing composition to a desired value. The pH adjuster to be used may be either acid or alkali, and may be any of inorganic and organic compounds. In addition, a pH adjuster can be used individually or in mixture of 2 or more types. Moreover, when using what has pH adjustment function (for example, various alkalis etc.) as another additive (an alkali compound etc.), you may utilize the said additive as at least one part of a pH adjuster. .

[water]
The polishing composition of the present invention contains water as a dispersion medium or solvent for dispersing or dissolving each component. From the viewpoint of suppressing the inhibition of the action of other components, water containing as little impurities as possible is preferable. Specifically, after removing impurity ions with an ion exchange resin, pure water from which foreign matters are removed through a filter is used. Water, ultrapure water, or distilled water is preferred.

[Other ingredients]
The polishing composition of the present invention dissolves a polishing accelerator, a metal anticorrosive, an antiseptic, an antifungal agent, an oxidizing agent, a reducing agent, a water-soluble polymer, a surfactant, and a poorly soluble organic substance as necessary. It may further include other components such as an organic solvent. Hereinafter, preferable other components, which are a polishing accelerator, a metal anticorrosive, and an oxidizing agent, will be described.

[Polishing accelerator]
The polishing composition according to this embodiment may contain a polishing accelerator as an optional component. The polishing accelerator functions to improve the polishing rate of the polishing object by the polishing composition by complexing and bonding to the surface of the polishing object and forming an insoluble brittle film on the surface of the polishing object. . Specific examples of the polishing accelerator include carboxylic acid compounds, phosphorus-containing compounds, sulfonic acid compounds, and the like.

  Specific examples of the carboxylic acid compound include acetic acid, lactic acid, propionic acid, butyric acid, glycolic acid, gluconic acid, salicylic acid, isonicotinic acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, hydroangelic acid, caproic acid, 2-methylpentanoic acid, 4-methylpentanoic acid, 2,3-dimethylbutanoic acid, 2-ethylbutanoic acid, 2,2-dimethylbutanoic acid, 3,3-dimethylbutanoic acid, heptanoic acid, octanoic acid, nonanoic acid, Examples thereof include saturated monocarboxylic acids such as decanoic acid, polyvalent carboxylic acids such as oxalic acid, malonic acid, tartaric acid, maleic acid and citric acid, and salts of these carboxylic acids. Of these, saturated monocarboxylic acids are preferred. The saturated monocarboxylic acid preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms. Specific examples of the saturated monocarboxylic acid having 2 to 6 carbon atoms include acetic acid, lactic acid, propionic acid, butyric acid, glycolic acid, gluconic acid, salicylic acid, isonicotinic acid, isobutyric acid, valeric acid, isovaleric acid, and pivalic acid. , Hydroangelic acid, caproic acid, 2-methylpentanoic acid, 4-methylpentanoic acid, 2,3-dimethylbutanoic acid, 2-ethylbutanoic acid, 2,2-dimethylbutanoic acid, 3,3-dimethylbutanoic acid It is done. These saturated monocarboxylic acids having 2 to 6 carbon atoms are easily complexed with the object to be polished. Two or more carboxylic acid compounds may be used in combination.

  The phosphorus-containing compound may be an organic phosphorus compound having a carbon-phosphorus bond or an inorganic phosphorus compound. Specific examples of the organic phosphorus compound include trivalent organic phosphorus compounds such as phosphine, phosphine oxide, phosphine sulfide, and diphosphane, phosphonium salts, phosphonic acids, phosphinic acids, and salts and derivatives thereof. Of these, phosphonic acid or phosphinic acid is preferred. Specific examples of phosphonic acid include 2-aminoethylphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), Ethane-1,1, -diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, ethane-1-hydroxy-1,1,2-triphosphonic acid, ethane -1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, α-methylphosphonosucci Examples include acids and phenylphosphonic acid. These phosphonic acids and phosphinic acids are particularly easily complexed with the object to be polished. Two or more organic phosphorus compounds may be used in combination.

  Specific examples of inorganic phosphorus compounds include orthophosphoric acid, hypophosphoric acid, peroxomonophosphoric acid, peroxodiphosphoric acid, polyphosphoric acid (diphosphoric acid, triphosphoric acid, tetraphosphoric acid), metaphosphoric acid, diamidophosphoric acid, and amidophosphoric acid. , Hexafluorophosphoric acid, hexachlorophosphoric acid, phenylphosphoric acid, apatite, phosphomolybdic acid, phosphotungstic acid, diphosphomolybdic acid, diphosphotungstic acid, ultraphosphoric acid, phosphorous tribromide, phosphorous pentabromide, Phosphorus dibromide nitride, phosphorous trichloride, phosphorous pentachloride, phosphorous tetrachloride, phosphorous dichloride, phosphorous trichloride, phosphorous dinitride, phosphorous tetrachloride, tetrachlorophosphoric acid, tricyan Phosphorus trioxide, phosphorous trifluoride, phosphorous pentafluoride, phosphorous tetrafluoride, phosphorous triiodide, phosphorous tetraiodide, phosphorous nitride, phosphorous oxide (phosphorous monoxide, phosphorous dioxide, phosphorous trioxide) , Phosphorous pentoxide, phosphorous hexaoxide, phosphorous tetraoxide), phosphoryl bromide, phosphoryl chloride, phosphoryl fluoride, phosphoryl nitride, diphosphoryl tetraamide, phosphorous sulfide (diphosphorus pentasulfide, phosphorous trisulfide, Tetraphosphorus pentasulfide, tetraphosphorous heptasulfide), thiophosphoryl bromide, thiophosphoryl chloride, phosphorus hydride, phosphorous tris (isocyanate), phosphorous tris (isocyanate), phosphorous tris (isothiocyanate), tris (isothiocyanate) Phosphoryl, phosphorus selenide, diphosphorus triselenide, tetralin triselenide, diphosphorus pentaselenide, thiophosphoryl fluoride, thiophosphoryl iodide, phosphorylamide, thiophosphoryl nitride, thiophosphorylamide, phosphoryl isothiocyanate, phosphorous Phosphides (zinc phosphide, aluminum phosphide, yttrium phosphide, phosphorus Iridium, potassium phosphide, gallium phosphide, calcium phosphide, osmium phosphide, cadmium phosphide, gold phosphide, indium phosphide, uranium phosphide, chromium phosphide, silicon phosphide, silver phosphide, germanium phosphide, Cobalt phosphide, zirconium phosphide, mercury phosphide, scandium phosphide, tin phosphide, thallium phosphide, tungsten phosphide, tantalum phosphide, titanium phosphide, iron phosphide, copper phosphide, thorium phosphide, phosphide Sodium, niobium phosphide, nickel phosphide, neptium phosphide, platinum phosphide, vanadium phosphide, hafnium phosphide, palladium phosphide, barium phosphide, plutonium phosphide, beryllium phosphide, boron phosphide, magnesium phosphide, Manganese phosphide, molybdenum phosphide, lanthanum phosphide, lithium phosphide, Ruthenium phosphide, rhenium phosphide, rhodium phosphide), and salts thereof. Among them, orthophosphoric acid, hypophosphoric acid, peroxomonophosphoric acid, peroxodiphosphoric acid, polyphosphoric acid (diphosphoric acid, triphosphoric acid, tetraphosphoric acid), metaphosphoric acid, diamidophosphoric acid, amidophosphoric acid, hexafluorophosphoric acid, hexachlorophosphorus Acid and phenylphosphoric acid are preferable, and orthophosphoric acid or phenylphosphoric acid is particularly preferable. These inorganic phosphorus compounds are particularly easily complexed with the object to be polished. Two or more kinds of inorganic phosphorus compounds may be used in combination.

  Specific examples of the sulfonic acid compound include sulfuric acid, alkyl sulfuric acid, allyl sulfuric acid, taurine, isethionic acid, benzenesulfonic acid, and salts thereof. Of these, benzenesulfonic acid is preferred. Benzenesulfonic acid forms a complex easily with the object to be polished. Two or more kinds of sulfonic acid compounds may be used in combination.

  A preferable form of the polishing accelerator is a complexing agent. When a complexing agent is added to the polishing composition, the polishing rate of the object to be polished by the polishing composition is improved by the etching action of the complexing agent in addition to the function of the polishing accelerator described above. There is an advantageous effect. In the following specific examples, those overlapping with the compound group already mentioned as the polishing accelerator are also described, but when such a compound is contained in the polishing composition, the compound is It should be included as a complexing agent.

  As the complexing agent, for example, inorganic acids, organic acids, amino acids, nitrile compounds, chelating agents and the like can be used. Specific examples of the inorganic acid include sulfuric acid, nitric acid, boric acid, carbonic acid, hypophosphorous acid, phosphorous acid, phosphoric acid and the like. Specific examples of organic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexanoic acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, 4-methylpentanoic acid, n- Heptanoic acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycolic acid, salicylic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, malein Examples include acid, phthalic acid, malic acid, tartaric acid, citric acid, and lactic acid. Organic sulfuric acids such as methanesulfonic acid, ethanesulfonic acid and isethionic acid can also be used. A salt such as an alkali metal salt of an inorganic acid or an organic acid may be used instead of the inorganic acid or the organic acid or in combination with the inorganic acid or the organic acid. Specific examples of amino acids include glycine, α-alanine, β-alanine, N-methylglycine, N, N-dimethylglycine, 2-aminobutyric acid, norvaline, valine, leucine, norleucine, isoleucine, phenylalanine, proline, sarcosine, Ornithine, lysine, taurine, serine, threonine, homoserine, tyrosine, bicine, tricine, 3,5-diiodo-tyrosine, β- (3,4-dihydroxyphenyl) -alanine, thyroxine, 4-hydroxy-proline, cysteine, methionine , Ethionine, lanthionine, cystathionine, cystine, cysteic acid, aspartic acid, glutamic acid, S- (carboxymethyl) -cysteine, 4-aminobutyric acid, asparagine, glutamine, azaserine, arginine, canavanine, cytosine Phosphorus, .delta.-hydroxy - lysine, creatine, histidine, 1-methyl - histidine, 3-methyl - histidine and tryptophan. Of these, glycine, alanine, malic acid, tartaric acid, citric acid, glycolic acid, isethionic acid or salts thereof are preferred.

  Specific examples of the nitrile compound include acetonitrile, aminoacetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, glutaronitrile, methoxyacetonitrile, and the like.

  Specific examples of chelating agents include nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ′, N′-tetramethylenesulfonic acid, transcyclohexane Diamine tetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, ethylenediamine disuccinic acid (SS form), N- (2-carboxylateethyl) -L-aspartic acid, β -Alanine diacetate, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid 1,2-dihydroxybenzene-4,6 Such as disulfonic acid and the like.

  A preferred form of the polishing accelerator is an inorganic salt. When an inorganic salt is added to the polishing composition, in addition to the functions of the polishing accelerator and complexing agent described above, the electrical conductivity of the polishing composition can be increased. As a result, the polishing composition There is an advantageous effect that the polishing rate of the object to be polished by the object is improved. In addition, in the following specific examples, those overlapping with the compound group already mentioned as the polishing accelerator and the complexing agent are also described, but when such a compound is included in the polishing composition The compound is included as an inorganic salt.

  Examples of inorganic salts include alkali metal inorganic salts and ammonium salts. Examples of the inorganic salt of alkali metal include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, potassium nitrate, sodium nitrate and the like. Examples of the ammonium salt include ammonium hydroxide, ammonium carbonate, ammonium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium chloride, and tetraethylammonium chloride.

  When the polishing composition according to this embodiment contains a polishing accelerator, the lower limit of the content of the polishing accelerator in the polishing composition is 0.001% by mass or more with respect to 100% by mass of the total amount of the composition. Preferably, it is 0.01% by mass or more, more preferably 0.1% by mass or more. As the content of the polishing accelerator increases, the polishing rate of the object to be polished by the polishing composition is improved. On the other hand, when the polishing composition according to this embodiment contains a polishing accelerator, the upper limit of the content of the polishing accelerator in the polishing composition is 10% by mass or less with respect to 100% by mass of the total amount of the composition. More preferably, it is 8 mass% or less, More preferably, it is 5 mass% or less. As the content of the polishing accelerator decreases, the material cost of the polishing composition can be reduced.

  When the polishing composition according to this embodiment includes a polishing accelerator as a preferred form, when the complexing agent is included, the lower limit of the content of the complexing agent in the polishing composition is 100 mass of the total amount of the composition. % Is preferably 0.01% by mass or more, and more preferably 0.1% by mass or more. As the content of the complexing agent increases, the polishing rate of the object to be polished by the polishing composition is improved. On the other hand, the upper limit of the content of the complexing agent in the polishing composition from the viewpoint of reducing the possibility that the polishing object is easily excessively etched by adding the complexing agent (preventing excessive etching). Is preferably 10% by mass or less, more preferably 1% by mass or less, with respect to 100% by mass of the total amount of the composition.

  Moreover, as a preferable form when the polishing composition according to the present embodiment contains a polishing accelerator, when the inorganic salt is contained, the lower limit of the content of the inorganic salt in the polishing composition is 100 mass of the total amount of the composition. % Is preferably 0.01% by mass or more, and more preferably 0.1% by mass or more. As the content of the inorganic salt increases, the polishing rate of the object to be polished by the polishing composition is improved. On the other hand, from the viewpoint of reducing the possibility of agglomeration of abrasive grains due to excessive addition of inorganic salt, the upper limit of the content of the inorganic salt in the polishing composition is based on 100% by mass of the total amount of the composition, It is preferable that it is 10 mass% or less, More preferably, it is 1 mass% or less.

[Metal anticorrosive]
The polishing composition according to this embodiment may contain a metal anticorrosive as an optional component. In the case where the object to be polished is a semiconductor device substrate including a metal wiring layer, a barrier layer, an interlayer insulating film layer, etc., by adding a metal anticorrosive to the polishing composition, the side of the wiring is removed by polishing using the polishing composition. It is possible to further suppress the occurrence of dents. Moreover, it can suppress more that dishing arises on the surface of the grinding | polishing target object after grind | polishing using a polishing composition.

  The metal anticorrosive that can be used is not particularly limited, but is preferably a heterocyclic compound or a surfactant. The number of heterocyclic rings in the heterocyclic compound is not particularly limited. The heterocyclic compound may be a monocyclic compound or a polycyclic compound having a condensed ring. These metal anticorrosives may be used alone or in combination of two or more. In addition, as the metal anticorrosive, a commercially available product or a synthetic product may be used.

  Specific examples of heterocyclic compounds that can be used as metal anticorrosives include, for example, pyrrole compounds, pyrazole compounds, imidazole compounds, triazole compounds, tetrazole compounds, pyridine compounds, pyrazine compounds, pyridazine compounds, pyridine compounds, indolizine compounds, indoles. Compound, isoindole compound, indazole compound, purine compound, quinolidine compound, quinoline compound, isoquinoline compound, naphthyridine compound, phthalazine compound, quinoxaline compound, quinazoline compound, cinnoline compound, buteridine compound, thiazole compound, isothiazole compound, oxazole compound, iso Examples thereof include nitrogen-containing heterocyclic compounds such as oxazole compounds and furazane compounds.

  More specific examples include pyrazole compounds such as 1H-pyrazole, 4-nitro-3-pyrazolecarboxylic acid, 3,5-pyrazolecarboxylic acid, 3-amino-5-phenylpyrazole, 5 -Amino-3-phenylpyrazole, 3,4,5-tribromopyrazole, 3-aminopyrazole, 3,5-dimethylpyrazole, 3,5-dimethyl-1-hydroxymethylpyrazole, 3-methylpyrazole, 1-methyl Pyrazole, 3-amino-5-methylpyrazole, 4-amino-pyrazolo [3,4-d] pyrimidine, allopurinol, 4-chloro-1H-pyrazolo [3,4-D] pyrimidine, 3,4-dihydroxy-6 -Methylpyrazolo (3,4-B) -pyridine, 6-methyl-1H-pyrazolo [3,4-b] pyridine - amine.

  Examples of imidazole compounds include, for example, imidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 1,2-dimethylpyrazole, 2-ethyl-4-methylimidazole, 2-isopropylimidazole, benzimidazole, 5,6-dimethylbenzimidazole, 2-aminobenzimidazole, 2-chlorobenzimidazole, 2-methylbenzimidazole, 2- (1-hydroxyethyl) benzimidazole, 2-hydroxybenzimidazole, 2-phenylbenzimidazole, 2 , 5-dimethylbenzimidazole, 5-methylbenzimidazole, 5-nitrobenzimidazole, 1H-purine and the like.

  Examples of triazole compounds include, for example, 1,2,3-triazole, 1,2,4-triazole, 1-methyl-1,2,4-triazole, methyl-1H-1,2,4-triazole-3. -Carboxylate, 1,2,4-triazole-3-carboxylic acid, methyl 1,2,4-triazole-3-carboxylate, 1H-1,2,4-triazole-3-thiol, 3,5-diamino -1H-1,2,4-triazole, 3-amino-1,2,4-triazole-5-thiol, 3-amino-1H-1,2,4-triazole, 3-amino-5-benzyl-4H -1,2,4-triazole, 3-amino-5-methyl-4H-1,2,4-triazole, 3-nitro-1,2,4-triazole, 3-bromo-5-nitro-1, , 4-tri Sol, 4- (1,2,4-triazol-1-yl) phenol, 4-amino-1,2,4-triazole, 4-amino-3,5-dipropyl-4H-1,2,4-triazole 4-amino-3,5-dimethyl-4H-1,2,4-triazole, 4-amino-3,5-dipeptyl-4H-1,2,4-triazole, 5-methyl-1,2,4 -Triazole-3,4-diamine, 1H-benzotriazole, 1-hydroxybenzotriazole, 1-aminobenzotriazole, 1-carboxybenzotriazole, 5-chloro-1H-benzotriazole, 5-nitro-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 5-methyl-1H-benzotriazole, 5,6-dimethyl-1H-benzotriazo 1- (1 ′, 2′-dicarboxyethyl) benzotriazole, 1- [N, N-bis (hydroxyethyl) aminomethyl] benzotriazole, 1- [N, N-bis (hydroxyethyl) aminomethyl ] -5-methylbenzotriazole, 1- [N, N-bis (hydroxyethyl) aminomethyl] -4-methylbenzotriazole, and the like.

  Examples of the tetrazole compound include 1H-tetrazole, 5-methyltetrazole, 5-aminotetrazole, and 5-phenyltetrazole.

  Examples of indazole compounds include, for example, 1H-indazole, 5-amino-1H-indazole, 5-nitro-1H-indazole, 5-hydroxy-1H-indazole, 6-amino-1H-indazole, 6-nitro-1H -Indazole, 6-hydroxy-1H-indazole, 3-carboxy-5-methyl-1H-indazole and the like.

  Examples of indole compounds include 1H-indole, 1-methyl-1H-indole, 2-methyl-1H-indole, 3-methyl-1H-indole, 4-methyl-1H-indole, 5-methyl-1H- Indole, 6-methyl-1H-indole, 7-methyl-1H-indole, 4-amino-1H-indole, 5-amino-1H-indole, 6-amino-1H-indole, 7-amino-1H-indole, 4-hydroxy-1H-indole, 5-hydroxy-1H-indole, 6-hydroxy-1H-indole, 7-hydroxy-1H-indole, 4-methoxy-1H-indole, 5-methoxy-1H-indole, 6- Methoxy-1H-indole, 7-methoxy-1H-indole, 4-chloro-1H- Ndole, 5-chloro-1H-indole, 6-chloro-1H-indole, 7-chloro-1H-indole, 4-carboxy-1H-indole, 5-carboxy-1H-indole, 6-carboxy-1H-indole, 7-carboxy-1H-indole, 4-nitro-1H-indole, 5-nitro-1H-indole, 6-nitro-1H-indole, 7-nitro-1H-indole, 4-nitrile-1H-indole, 5- Nitrile-1H-indole, 6-nitrile-1H-indole, 7-nitrile-1H-indole, 2,5-dimethyl-1H-indole, 1,2-dimethyl-1H-indole, 1,3-dimethyl-1H- Indole, 2,3-dimethyl-1H-indole, 5-amino-2,3-dimethyl-1H- Ndole, 7-ethyl-1H-indole, 5- (aminomethyl) indole, 2-methyl-5-amino-1H-indole, 3-hydroxymethyl-1H-indole, 6-isopropyl-1H-indole, 5-chloro -2-methyl-1H-indole and the like.

  Among these, preferred heterocyclic compounds are triazole compounds, and in particular, 1H-benzotriazole, 5-methyl-1H-benzotriazole, 5,6-dimethyl-1H-benzotriazole, 1- [N, N-bis (hydroxy Ethyl) aminomethyl] -5-methylbenzotriazole, 1- [N, N-bis (hydroxyethyl) aminomethyl] -4-methylbenzotriazole, 1,2,3-triazole, and 1,2,4-triazole Is preferred. Since these heterocyclic compounds have high chemical or physical adsorptive power to the surface of the object to be polished, a stronger protective film can be formed on the surface of the object to be polished. This is advantageous in improving the flatness of the surface of the object to be polished after polishing using the polishing composition of the present invention.

  Further, the surfactant used as the metal anticorrosive may be any of an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant.

  Examples of anionic surfactants include, for example, polyoxyethylene alkyl ether acetic acid, polyoxyethylene alkyl sulfuric acid ester, alkyl sulfuric acid ester, polyoxyethylene alkyl ether sulfuric acid, alkyl ether sulfuric acid, alkylbenzene sulfonic acid, alkyl phosphoric acid ester , Polyoxyethylene alkyl phosphate ester, polyoxyethylene sulfosuccinic acid, alkyl sulfosuccinic acid, alkyl naphthalene sulfonic acid, alkyl diphenyl ether disulfonic acid, and salts thereof.

  Examples of the cationic surfactant include alkyl trimethyl ammonium salt, alkyl dimethyl ammonium salt, alkyl benzyl dimethyl ammonium salt, alkyl amine salt and the like.

  Examples of amphoteric surfactants include alkyl betaines and alkyl amine oxides.

  Examples of nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, and alkyl alkanolamide. Is mentioned.

  Among these, preferable surfactants are polyoxyethylene alkyl ether acetate, polyoxyethylene alkyl ether sulfate, alkyl ether sulfate, alkylbenzene sulfonate, and polyoxyethylene alkyl ether. Since these surfactants have a high chemical or physical adsorption force to the surface of the object to be polished, a stronger protective film can be formed on the surface of the object to be polished. This is advantageous in improving the flatness of the surface of the object to be polished after polishing using the polishing composition of the present invention.

  The lower limit of the content of the metal anticorrosive in the polishing composition is preferably 0.001 g / L or more, more preferably 0.005 g / L or more, and 0.01 g / L or more. Is more preferable. Further, the upper limit of the content of the metal anticorrosive in the polishing composition is preferably 10 g / L or less, more preferably 5 g / L or less, and further preferably 1 g / L or less. If it is such a range, the flatness of the surface of the grinding | polishing target object after grind | polishing using a polishing composition will improve, and the grinding | polishing speed | rate of the grinding | polishing target object by polishing composition will improve.

[Oxidant]
The polishing composition according to this embodiment may contain an oxidizing agent as an optional component. In this specification, an oxidizing agent means a compound that can function as an oxidizing agent for a metal contained in an object to be polished. Therefore, the oxidizing agent can be selected according to the criterion of whether or not it has a redox potential sufficient to exhibit such a function. For this reason, the extension of the oxidant is not necessarily unambiguously defined. For example, for example, hydrogen peroxide, nitric acid, chlorous acid, hypochlorous acid, periodic acid, persulfate, hydrogen oxide And adducts such as urea hydrogen peroxide and carbonates, organic peroxides such as benzoyl, peracetic acid, and di-t-butyl, sulfate (SO5), sulfate (S5O8), and sodium peroxide. Periodic acid, iodic acid, hypoiodic acid, iodic acid, perbromic acid, bromic acid, hypobromic acid, bromic acid, perchloric acid, chloric acid, perchloric acid, perboric acid, and their salts Can be mentioned.

  When the polishing composition according to this embodiment contains an oxidizing agent, the lower limit of the content of the oxidizing agent in the polishing composition is 0.1% by mass or more with respect to 100% by mass of the total amount of the composition. It is preferable that the content is 0.3% by mass or more. As the content of the oxidizing agent increases, the polishing rate for the object to be polished by the polishing composition tends to improve. On the other hand, when the polishing composition according to this embodiment contains an oxidizing agent, the upper limit of the content of the oxidizing agent in the polishing composition is 10% by mass or less with respect to 100% by mass of the total amount of the composition. Preferably, it is 5 mass% or less. As the content of the oxidizing agent decreases, the material cost of the polishing composition can be reduced, and the load on the processing of the polishing composition after polishing, that is, the waste liquid treatment can be reduced. Moreover, the advantageous effect that excessive oxidation of the object to be polished by the oxidizing agent can be prevented is also obtained.

[Method for producing polishing composition]
The manufacturing method in particular of the polishing composition of this invention is not restrict | limited, For example, it can obtain by stirring and mixing anion-modified abrasive grain, an alkali compound, and other components as needed in water.

  Although the temperature at the time of mixing each component is not specifically limited, 10-40 degreeC is preferable and you may heat in order to raise a dissolution rate. Further, the mixing time is not particularly limited.

[Polishing method and substrate manufacturing method]
As described above, the polishing composition of the present invention is suitably used for polishing a substrate. Therefore, the present invention provides a polishing method for polishing a substrate with the polishing composition of the present invention. Moreover, this invention provides the manufacturing method of a board | substrate including the process of grind | polishing a board | substrate with the said grinding | polishing method.

  As a polishing apparatus, a general holder having a polishing surface plate on which a holder for holding a substrate having a polishing object and a motor capable of changing the number of rotations are attached and a polishing pad (polishing cloth) can be attached. A polishing apparatus can be used.

  As the polishing pad, a general nonwoven fabric, polyurethane, porous fluororesin, or the like can be used without particular limitation. It is preferable that the polishing pad is grooved so that the polishing liquid accumulates.

  The polishing conditions are not particularly limited, and for example, the rotation speed of the polishing platen is preferably 10 to 500 rpm, and the pressure (polishing pressure) applied to the substrate having the object to be polished is preferably 0.5 to 10 psi. The method of supplying the polishing composition to the polishing pad is not particularly limited, and for example, a method of continuously supplying with a pump or the like is employed. Although the supply amount is not limited, it is preferable that the surface of the polishing pad is always covered with the polishing composition of the present invention.

  After the polishing is completed, the substrate is washed in running water, and water droplets adhering to the substrate are removed by a spin dryer or the like and dried to obtain a substrate.

  The present invention will be described in further detail using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples.

  As shown in Table 2, abrasive grains ("Abrasive grain" column in Table 2), alkali compounds ("Alkali compound" column in Table 2), and other additives as needed (in Table 2) The “Compound” column) was stirred and mixed in water (mixing temperature: about 25 ° C., mixing time: about 10 minutes) to prepare polishing compositions of Examples 1 to 13 and Comparative Examples 1 to 13. At this time, the type of the functional group supported on the abrasive grains by the surface modification is described in the column of “type of modification” in Table 2. Further, colloidal silica was used as the abrasive grain to be modified. The pH of the composition was adjusted by adding potassium hydroxide (KOH) or tetramethylammonium hydroxide (TMAH) as an alkali compound, and confirmed with a pH meter. In Table 2, “-” in the “modification type” column indicates that the surface is not modified. In addition, when an additive was added in addition to the abrasive grains and the alkali compound, the substance name was written in the column of “Compound” in Table 2, and when it was not added, “−” was written.

(Measurement of polishing rate for substrate)
Using the polishing compositions of Examples 1 to 13 and Comparative Examples 1 to 13 obtained above, the polishing rate for each substrate as an object to be polished was measured. The polishing rate was determined by dividing the difference in wafer thickness before and after polishing measured by using a sheet resistance measuring instrument based on the direct current four-probe method by the polishing time. The substrate used is a blanket wafer of each material (in the column “Polished object” in Table 2), “silicon” is a silicon wafer, “TEOS” is a TEOS blanket wafer, “SiN” is a SiN blanket wafer. "Poly-Si" indicates a polysilicon blanket wafer and "Ru" indicates a ruthenium blanket wafer. The polishing conditions are as shown in Table 1.

(Measurement of zeta potential of substrate and abrasive grains)
The abrasive grains used in the polishing compositions of Examples 1 to 20 and Comparative Examples 1 to 20 obtained and the zeta potential of the substrate polished using the same were electrophoresed with respect to the abrasive grains and the substrate before polishing. Measurement was performed using a measuring apparatus based on the light scattering method. The results obtained by the measurement are shown in the “potential” column of Table 2.

  The measurement results of the polishing rate and zeta potential for the substrate thus obtained are shown in Table 2 below. In addition, what is described as "-" in the column of "Polishing rate" in Table 2 indicates that the polishing rate could not be measured due to aggregation or gelation of abrasive grains in the polishing composition. .

Subsequently, the electrical conductivity of the polishing composition of Example 2 and Comparative Example 5 was adjusted, and the storage stability of each polishing composition was confirmed. The electric conductivity was adjusted by adding potassium nitrate (KNO ₃ ) as an inorganic salt and confirmed using an electric conductivity meter. As for stability, each polishing composition with adjusted electrical conductivity is allowed to stand at 23 degrees and visually confirmed at regular intervals, and the case where the polishing composition maintains a liquid state is “-”, The case where the abrasive grains in the polishing composition were aggregated or gelled was defined as “+” (“Stability” column in Table 3).

  The results of stability of each polishing composition thus obtained are shown in Table 3 below.

  From the results shown in Table 2, when the polishing compositions according to Examples 1 to 13 are used, various types of polishing objects are obtained as compared with the polishing compositions of Comparative Examples 1 to 13 that do not satisfy the conditions of the present invention. It can be seen that the polishing rate with respect to is significantly improved. Moreover, even when it contains many inorganic salts in polishing composition like Examples 14-20, compared with the polishing composition of Comparative Examples 14-20 containing the same amount of inorganic salt, the conditions of this invention are satisfy | filled. The polishing composition was found to have a significantly superior effect in stability.

Claims (9)

A polishing composition for use in polishing a substrate,
Abrasive grains,
An alkali compound;
water and,
Hints, the abrasive grains are colloidal silica carrying a sulfonic acid group as the anionic functional group, and Ri der pH is 7.0 or more of the polishing composition,
The polishing composition , wherein the support is a chemical bond .   The polishing composition according to claim 1, wherein the surface of the abrasive grain has a zeta potential of −20 mV or less.   The polishing composition according to claim 1, wherein the surface of the abrasive grain has a zeta potential of −40 mV or less.   Polishing composition as described in any one of Claims 1-3 whose product of the zeta potential of the said substrate surface and the zeta potential of the surface of the said abrasive grain is 1000-3000 mV.   Polishing composition as described in any one of Claims 1-4 whose content of the said alkali compound is 0.01 to 5.0 weight%.   The grinding | polishing method which grind | polishes the board | substrate which has a layer containing a noble metal using the polishing composition as described in any one of Claims 1-5.   A method for manufacturing a substrate, comprising the step of polishing a substrate having a layer containing a noble metal by the polishing method according to claim 6.   The grinding | polishing method of grind | polishing the board | substrate containing a silicon containing material using the polishing composition as described in any one of Claims 1-5.   The manufacturing method of a board | substrate including the process of grind | polishing the board | substrate containing a silicon containing material with the grinding | polishing method of Claim 8.