JP2017075226A - Method for producing polishing liquid, polishing liquid and polishing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polishing liquid having an excellent ratio of a polishing speed of an insulation material to that of a stopper material.SOLUTION: The present invention provides a polishing liquid for removing at least part of an insulation material by CMP, comprising an abrasive grain comprising cerium oxide, a glycine compound having a structure represented by general formula (1), a polymer compound having at least one selected from the group consisting of a carboxylic acid group and a carboxylate group, and water, where Rand Rindependently represent a hydrogen atom or a monovalent substituent.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a polishing liquid, a polishing liquid, and a polishing method. More specifically, the present invention relates to a planarization process of a substrate surface, in particular, a planarization process of an interlayer insulating film, a BPSG film (boron, phosphorus-doped silicon dioxide film), etc., which is a semiconductor element manufacturing technique, and a shallow trench. The present invention relates to a polishing liquid manufacturing method, a polishing liquid, and a polishing method used in an isolation (STI: shallow trench isolation) formation process.

  In the current manufacturing process of ULSI semiconductor elements, processing techniques for increasing the density and miniaturization of semiconductor elements are being researched and developed. One of the processing techniques, planarization by CMP (Chemical Mechanical Polishing), is a process of semiconductor element manufacturing, planarization of an interlayer insulating film, STI formation process, plug formation process, embedded metal wiring. It has become an indispensable technique when performing a forming process (damascene process) and the like. In the CMP process (planarization process using CMP technology), the polishing material is generally polished while supplying a polishing slurry for CMP between the polishing cloth (polishing pad) and the polishing material on the substrate. Is done by.

  Various polishing liquids for CMP used in the CMP are known. When the polishing liquid for CMP is classified according to the type of abrasive grains (polishing particles) contained in the polishing liquid, it contains ceria-based polishing liquid containing cerium oxide (ceria) particles as abrasive grains, and silicon oxide (silica) particles as abrasive grains. Known are silica-based polishing liquids, alumina-based polishing liquids containing aluminum oxide (alumina) particles as abrasive grains, and resin particle-based polishing liquids containing organic resin particles as abrasive grains.

  As a polishing liquid for polishing an insulating material such as silicon oxide in a manufacturing process of a semiconductor element, a ceria-based polishing liquid has attracted attention from the viewpoint of a higher polishing rate of an inorganic insulating material than a silica-based polishing liquid. Yes.

  As a ceria-based polishing liquid, the following Patent Document 1 describes a CMP polishing liquid for semiconductors using high-purity cerium oxide abrasive grains. Patent Document 2 listed below describes a technique of adding a polymer additive to control the polishing rate of a ceria-based polishing liquid and improve global flatness. Patent Document 3 below discloses a polymer obtained by polymerizing a monomer containing at least one of a carboxylic acid having an unsaturated double bond and a salt thereof using a reducing inorganic acid salt and oxygen as a redox polymerization initiator. It is described that by using coalescence as an additive, it is possible to achieve uniform polishing with little influence due to the difference in density of wiring patterns.

Japanese Patent Laid-Open No. 10-106994 Japanese Patent No. 3278532 International Publication No. 2008/032794

  In the CMP process, the insulating material may be selectively polished using a stopper material. In this case, if the polishing rate ratio of the insulating material to the stopper material (polishing selection ratio: polishing rate of the insulating material / polishing speed of the stopper material) is insufficient, it is difficult to stop polishing when the stopper material is exposed. Thus, the polishing of the insulating material proceeds excessively.

  The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a polishing liquid production method capable of obtaining a polishing liquid having an excellent polishing rate ratio of an insulating material to a stopper material. To do. Another object of the present invention is to provide a polishing liquid having an excellent polishing rate ratio of an insulating material to a stopper material, and a polishing method using the polishing liquid.

  In order to solve the above-mentioned problems, the present inventors have intensively studied on additives to be added to the polishing liquid. The inventors prepared a number of polishing liquids using various organic compounds as additives. The polishing characteristics were evaluated by polishing the insulating material using these polishing liquids. As a result, by using a specific compound as an additive, the present inventors can obtain a polishing liquid having a large polishing rate ratio of the insulating material to the stopper material (for example, a polishing rate ratio of silicon oxide to silicon nitride). As a result, the present invention was completed.

［式中、Ｒ^１及びＲ^２は、それぞれ独立に水素原子又は１価の置換基である。］ A method for producing a polishing liquid according to the present invention is a method for producing a polishing liquid for removing at least a part of an insulating material by CMP, and is represented by abrasive grains containing cerium oxide and the following general formula (1). A glycine compound having a structure, a polymer compound having at least one selected from the group consisting of a carboxylic acid group (hereinafter also referred to as “carboxyl group”) and a carboxylic acid group, and water. A step of obtaining a polishing liquid;

[Wherein, R ¹ and R ² each independently represent a hydrogen atom or a monovalent substituent. ]

  According to the method for producing a polishing liquid according to the present invention, a polishing liquid having an excellent polishing rate ratio of an insulating material to a stopper material can be obtained. According to the polishing liquid manufacturing method of the present invention, the CMP technique for polishing an insulating material (interlayer insulating film, BPSG film, STI film, etc.) formed on the surface of a substrate has an excellent polishing rate of the insulating material. However, the polishing rate ratio of the insulating material (silicon oxide or the like) to the stopper material (silicon nitride or the like) can be increased.

［式中、Ｒ^１及びＲ^２は、それぞれ独立に水素原子又は１価の置換基である。］ A polishing liquid according to the present invention is a polishing liquid for removing at least a part of an insulating material by CMP, and is a glycine system having abrasive grains containing cerium oxide and a structure represented by the following general formula (1) A compound, a polymer compound having at least one selected from the group consisting of a carboxylic acid group and a carboxylic acid group, and water are contained.

[Wherein, R ¹ and R ² each independently represent a hydrogen atom or a monovalent substituent. ]

  According to the polishing liquid of the present invention, an excellent polishing rate ratio of the insulating material to the stopper material can be obtained. According to the polishing liquid according to the present invention, in the CMP technique for polishing an insulating material (interlayer insulating film, BPSG film, STI film, etc.) formed on the surface of the substrate, while having an excellent polishing rate of the insulating material, The polishing rate ratio of the insulating material (silicon oxide or the like) to the stopper material (silicon nitride or the like) can be increased.

  In the polishing liquid and the method for producing the same according to the present invention, the polishing liquid may contain at least one organic acid component selected from the group consisting of an organic acid and an organic acid salt (excluding the glycine compound). Good.

  In the polishing liquid and the method for producing the same according to the present invention, the content of the polymer compound in the polishing liquid is preferably 0.001 to 2% by mass based on the total mass of the polishing liquid.

  In the polishing liquid and the method for producing the same according to the present invention, the glycine compound is preferably at least one selected from the group consisting of glycine, glycylglycine and glycosylamine. Thereby, a further excellent polishing rate ratio of the insulating material to the stopper material (for example, a polishing rate ratio of silicon oxide to silicon nitride) can be obtained.

  In the polishing liquid and the production method thereof according to the present invention, the pH of the polishing liquid is preferably 4.0 to 6.0. Thereby, it is possible to obtain excellent storage stability while having an excellent polishing rate of the insulating material.

  The polishing liquid according to the present invention is a two-part polishing liquid composed of a first liquid containing the abrasive grains and water and a second liquid containing the glycine compound, the polymer compound, and water. It may be saved. Thereby, since the dispersion stability of the abrasive grains can be kept better until just before using the polishing liquid, an excellent polishing rate and flatness can be obtained more effectively.

  The present invention also relates to a polishing method in which at least a part of an insulating material is removed by CMP using the polishing liquid. According to the polishing method of the present invention, an excellent polishing rate ratio of the insulating material to the stopper material can be obtained. According to the polishing method of the present invention, in the CMP technique for polishing an insulating material (interlayer insulating film, BPSG film, STI film, etc.) formed on the surface of the substrate, while having an excellent polishing rate of the insulating material, The polishing rate ratio of the insulating material (silicon oxide or the like) to the stopper material (silicon nitride or the like) can be increased.

  According to the present invention, an excellent polishing rate ratio of the insulating material to the stopper material can be obtained. According to the present invention, in a CMP technique for polishing an insulating material (an interlayer insulating film, a BPSG film, an STI film, etc.) formed on the surface of a substrate, a stopper material (nitriding) has an excellent polishing rate of the insulating material. The polishing rate ratio of the insulating material (silicon oxide or the like) to silicon or the like can be increased.

  According to the present invention, in the step of planarizing a substrate surface, which is a semiconductor element manufacturing technique, in particular, in a CMP technique for planarizing an interlayer insulating film, a BPSG film, and an STI film, the insulating material has an excellent polishing rate. The polishing rate ratio of the insulating material (silicon oxide, etc.) to the stopper material (silicon nitride, etc.) can be increased.

It is a schematic cross section which shows the grinding | polishing method which concerns on one Embodiment of this invention.

  Hereinafter, embodiments of the present invention will be described in detail.

<Polishing liquid>
The polishing liquid according to the present embodiment is a polishing liquid (CMP polishing liquid) for removing at least a part of the insulating material by CMP. The polishing liquid according to the present embodiment includes an abrasive grain containing cerium oxide, a glycine compound having a specific structure, and a polymer compound A having at least one selected from the group consisting of a carboxylic acid group and a carboxylic acid group, And water. The polishing liquid according to this embodiment may further contain at least one organic acid component B selected from the group consisting of an organic acid and an organic acid salt (excluding the glycine compound).

(Abrasive grains)
The polishing liquid according to this embodiment contains abrasive grains containing cerium oxide. The abrasive grains contain, for example, cerium oxide particles. There is no restriction | limiting in particular as a cerium oxide particle, A well-known thing can be used. Among these, cerium oxide particles are preferably obtained by oxidizing cerium salts such as carbonates, nitrates, sulfates, and oxalates. Examples of the oxidation method include a baking method of baking the cerium salt at 600 to 900 ° C., a chemical oxidation method of oxidizing the cerium salt using an oxidizing agent such as hydrogen peroxide, and the like. As a method for producing the cerium oxide particles, a firing method is preferable from the viewpoint of easily obtaining a high polishing rate of the insulating material, and a chemical oxidation method is preferable from the viewpoint that polishing scratches are hardly generated on the surface after polishing.

  When cerium oxide particles are used for polishing an insulating material, high-speed polishing is possible as the crystallite diameter (crystallite diameter) of the cerium oxide particles is larger and the crystal distortion is smaller (that is, the crystallinity is better). However, there is a tendency that polishing scratches are likely to enter the material to be polished. From the above viewpoint, preferable cerium oxide particles include particles composed of two or more crystallites and having a crystal grain boundary. Among these, particles having a crystallite diameter of 5 to 300 nm are more preferable. Another preferable cerium oxide particle includes colloidal ceria particles having a crystallite diameter of 5 to 300 nm (for example, colloidal ceria manufactured by Rhodia).

  The average particle size of the abrasive grains is preferably 10 to 500 nm, more preferably 20 to 400 nm, and still more preferably 50 to 300 nm. If the average particle size of the abrasive grains is 10 nm or more, a better polishing rate of the insulating material tends to be obtained, and if it is 500 nm or less, the material to be polished tends not to be damaged.

  Here, the average particle size of the abrasive grains is a laser diffraction particle size distribution meter (for example, Mastersizer Microplus (Malvern, trade name (“Mastersizer” is a registered trademark)), refractive index: 1.93, light source: He-Ne. It means the value of D50 (median diameter of volume distribution, cumulative median value) measured by laser, absorption 0. For the measurement of average particle diameter, for example, the appropriate content (for example, when measuring with He-Ne laser) A sample in which the polishing liquid is diluted to a transmittance (H content of 60 to 70%) is used, and the polishing liquid containing abrasive grains is a cerium oxide slurry in which abrasive grains containing cerium oxide are dispersed in water. When the cerium oxide slurry is stored separately from the additive solution, it can be measured by diluting the cerium oxide slurry to an appropriate content.

  The abrasive grains may contain components other than cerium oxide. Examples of constituents of such particles include silica, alumina, and zirconia.

  The content of abrasive grains in the polishing liquid is preferably 0.1 to 20% by mass, more preferably 0.1 to 15% by mass, and further 0.2 to 13% by mass based on the total mass of the polishing liquid. Preferably, 0.3 to 10% by mass is particularly preferable. If the content of the abrasive grains is 0.1% by mass or more, there is a tendency that a better polishing rate of the insulating material is obtained, and if it is 20% by mass or less, aggregation of the abrasive grains is suppressed and the material to be polished. There is a tendency to be hard to be scratched.

［式中、Ｒ^１及びＲ^２は、それぞれ独立に水素原子又は１価の置換基である。］ (Glycine compounds)
The polishing liquid according to the present embodiment contains a glycine compound having a structure represented by the following general formula (1). Thereby, the polishing rate ratio of the insulating material (silicon oxide or the like) to the stopper material (silicon nitride or the like) can be increased while having an excellent polishing rate of the insulating material. A glycine type compound may be used individually by 1 type, and may use 2 or more types together.

[Wherein, R ¹ and R ² each independently represent a hydrogen atom or a monovalent substituent. ]

Examples of the monovalent substituent include a carbonyl group (aldehyde group, ketone group, etc.), hydroxy group (hydroxyl group), amino group, imino group, amide group, carboxyl group, sulfonic acid group, phosphoric acid group, bromine atom, chlorine. atom, an iodine atom, a fluorine atom, a nitro group, a hydrazine group, an alkyl group _{(OH, NH 2, NH,} CONH 2, NHCH 2 COOH, COOH, Br, Cl, may be substituted by I or NO _2), aryl group, an alkenyl _{group, COCH 2 NH 2, C (} = NH) NH 2 and the like. Carbon number of an alkyl group is 1-8, for example. Carbon number of an aryl group is 6-12, for example. Carbon number of an alkenyl group is 1-8, for example.

  Examples of the glycine compound include glycine, N-methylglycine, N-ethylglycine, N, N-dimethylglycine, N-formylglycine, N-acetylglycine, iminodiacetic acid, N-methyliminodiacetic acid, N- (2- Aminoethyl) glycine, ethylenediamine-N, N′-diacetic acid, 1,3-propylenediamine-N, N′-diacetic acid, nitrilotriacetic acid, N- (2-acetamido) iminodiacetic acid, glycylglycine, glycosamine Etc. As the glycine compound, at least one compound selected from the group consisting of glycine, glycylglycine and glycosamine from the viewpoint of obtaining a higher polishing rate of the insulating material and a better polishing rate ratio of the insulating material to the stopper material. Is preferred, and glycosylamine is more preferred. These compounds may be used individually by 1 type, and may use 2 or more types together. When these compounds are used in combination of two or more, the effect of further improving the polishing rate of the insulating material can be obtained.

  The glycine compound is preferably water-soluble. By using a compound having high solubility in water, it is possible to dissolve a desired amount of glycine compound in the polishing liquid satisfactorily, and the effect of improving the polishing rate can be obtained at a higher level. . The lower limit of the solubility of the glycine compound in 100 g of water at room temperature (25 ° C.) is preferably 0.001 g or more, more preferably 0.005 g or more, still more preferably 0.01 g or more, and particularly preferably 0.05 g or more. The upper limit of solubility is not particularly limited.

  The content of the glycine compound is preferably 0.001 to 1% by mass, more preferably 0.005 to 0.5% by mass, and 0.01 to 0.1% by mass based on the total mass of the polishing liquid. Further preferred. When the content is 0.001% by mass or more, a stable polishing rate tends to be easily achieved as compared to the case of less than 0.001% by mass. Tends to be suppressed.

(Polymer Compound A)
The polishing liquid according to this embodiment contains a polymer compound A having at least one selected from the group consisting of a carboxylic acid group and a carboxylic acid group. The high molecular compound A may be used individually by 1 type, and may use 2 or more types together. As the polymer compound A, a polymer obtained by polymerizing a monomer containing at least one selected from the group consisting of acrylic acid and methacrylic acid or a salt thereof (hereinafter referred to as “(meth) acrylic acid polymer”). Are generally referred to as “)”. The said monomer may contain the other monomer (except acrylic acid and methacrylic acid) copolymerizable with acrylic acid or methacrylic acid.

  As the polymer compound A, a homopolymer of acrylic acid (polyacrylic acid), a homopolymer of methacrylic acid (polymethacrylic acid), a copolymer of acrylic acid and methacrylic acid, acrylic acid or methacrylic acid and the above-mentioned others It may be at least one selected from the group consisting of copolymers of these monomers, copolymers of acrylic acid and methacrylic acid with the other monomers, and salts thereof. Among them, the (meth) acrylic acid polymer is selected from the group consisting of a homopolymer of acrylic acid (polyacrylic acid) and a salt thereof from the viewpoint of good adsorption to the material to be polished (insulating material, etc.). It is preferable that it is at least one kind. Examples of the polymer salt (polymer having a carboxylate group) include ammonium salts. Examples of the ammonium salt include ammonium polyacrylate. In addition, a (meth) acrylic-acid type polymer may be used individually by 1 type, and may use 2 or more types together.

  Examples of the other monomers (other monomers copolymerizable with acrylic acid or methacrylic acid) include, for example, crotonic acid, pentenoic acid, hexenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, and undecene. Examples thereof include unsaturated carboxylic acids such as acid, dodecenoic acid, tridecenoic acid, tetradecenoic acid, pentadecenoic acid, hexadecenoic acid and heptadecenoic acid; vinyl compounds such as ethylene, propylene and styrene.

  Although the weight average molecular weight of the high molecular compound A does not have a restriction | limiting in particular, 100-150,000 are preferable and 1000-80000 are more preferable. When the polymer compound A has a weight average molecular weight of 100 or more, a good polishing rate tends to be easily obtained when an insulating material (silicon oxide or the like) is polished. When the weight average molecular weight of the polymer compound A is 150,000 or less, the storage stability of the polishing liquid tends to be difficult to decrease.

The weight average molecular weight can be measured by the following method and reading the value obtained as “Mw”.
{Measuring method}
Equipment used (detector): Hitachi, Ltd., “L-3300” differential refractometer for liquid chromatograph Pump: Hitachi, Ltd., “L-7100” for liquid chromatograph
Degas equipment: None Data processing: GPC integrator “D-2520” manufactured by Hitachi, Ltd.
Column: “Shodex Asahipak GF-710HQ” manufactured by Showa Denko KK, inner diameter 7.6 mm × 300 mm
Eluent: 50 mM Na ₂ HPO ₄ aqueous solution / acetonitrile = 90/10 (v / v)
Measurement temperature: 25 ° C
Flow rate: 0.6 mL / min (L represents liter. The same applies hereinafter)
Measurement time: 30 minutes Sample: Sample prepared by adjusting the concentration with a solution having the same composition as the eluent so as to have a resin concentration of 2% by mass, and filtering through a 0.45 μm polytetrafluoroethylene filter Injection amount: 0 .4 μL
Reference material: Polymer Laboratories, narrow molecular weight sodium polyacrylate

  The content of the polymer compound A in the polishing liquid is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and still more preferably 0.1% by mass or more, based on the total mass of the polishing liquid. The content of the polymer compound A is preferably 2% by mass or less, more preferably 1% by mass or less, and still more preferably 0.5% by mass or less, based on the total mass of the polishing liquid. When the content of the polymer compound A is 0.001% by mass or more and 2% by mass or less, the dishing amount, wiring density dependency, and the like can be reduced, and the surface flatness after polishing can be improved.

(Organic acid component B)
The polishing liquid according to this embodiment may contain at least one organic acid component B selected from the group consisting of organic acids and organic acid salts. Thereby, still better flatness can be obtained. The organic acid component B is considered to suppress the dissociation of the carboxyl group in the polymer compound A. Thereby, it is considered that the hydrophobicity of the polymer compound A is increased and the polymer compound A is more easily adsorbed to the material to be polished (insulating material or the like).

The organic acid component B, selected from the group consisting of -COOM group, a phenolic -OM group, -SO ₃ M group, -O · SO ₃ M group, _-PO 4 _{M 2} group and _-PO 3 _{M 2} group A compound (such as a water-soluble organic compound) having at least one (M represents a cation) is preferred.

M is H; alkali metal such as NH ₄ ; Na and K; alkaline earth metal such as Ca and Mg; metal capable of taking trivalent such as Al, Fe and Cr; rare earth metal such as Ce and the like .

  The organic acid component B is considered to interact with the polymer compound A to form a firm film on the surface to be polished. More specifically, for example, the carboxyl group (anionic) possessed by the polymer compound A is electrostatically attracted to the cation (M or the like) in the organic acid component B, and the cation serves as a nucleus. It is considered that the polymer compound A is in a “rounded state” and is adsorbed on the surface to be polished to form a protective film. This protective film is considered to be stronger than the protective film formed by the polymer compound A “not rounded” and has a high flatness improving effect. The organic acid moiety in the organic acid component B is considered to suppress the dissociation of the carboxyl group in the polymer compound A. Thereby, it is thought that the hydrophobicity of the high molecular compound A increases, and it becomes easy to adsorb | suck to a to-be-polished surface.

Specific examples of the organic acid include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, o-methoxybenzoic acid. , M-methoxybenzoic acid, p-methoxybenzoic acid, acrylic acid, methacrylic acid, crotonic acid, pentenoic acid, hexenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, undecenoic acid, dodecenoic acid, tridecenoic acid, tetradecene Acid, pentadecenoic acid, hexadecenoic acid, heptadecenoic acid, isobutyric acid, isovaleric acid, cinnamic acid, quinaldic acid, nicotinic acid, 1-naphthoic acid, 2-naphthoic acid, picolinic acid, vinylacetic acid, phenylacetic acid, phenoxyacetic acid, 2-furancarboxylic acid, mercaptoacetic acid, levulinic acid, oxalic acid, malonic acid, succinic acid, glucose Phosphoric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,15-pentadecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, quinolinic acid Quinic acid, naphthalic acid, phthalic acid, isophthalic acid, terephthalic acid, glycolic acid, lactic acid, 3-hydroxypropionic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 3-hydroxyvaleric acid, 5- Hydroxyvaleric acid, quinic acid, kynurenic acid, salicylic acid, tartaric acid, aconi Tolic acid, ascorbic acid, acetylsalicylic acid, acetylmalic acid, acetylenedicarboxylic acid, acetoxysuccinic acid, acetoacetic acid, 3-oxoglutaric acid, atropic acid, atrolactic acid, anthraquinone carboxylic acid, anthracene carboxylic acid, caproic acid, isocaproic acid, Isocamphoric acid, isocrotonic acid, 2-ethyl-2-hydroxybutyric acid, ethylmalonic acid, ethoxyacetic acid, oxaloacetic acid, oxydiacetic acid, 2-oxobutyric acid, camphoric acid, citric acid, glyoxylic acid, glycidic acid, glyceric acid, glucar Acid, gluconic acid, croconic acid, cyclobutanecarboxylic acid, cyclohexanedicarboxylic acid, diphenylacetic acid, di-O-benzoyltartaric acid, dimethylsuccinic acid, dimethoxyphthalic acid, tartronic acid, tannic acid, thiophenecarboxylic acid , Tiglic acid, desoxosaric acid, tetrahydroxysuccinic acid, tetramethylsuccinic acid, tetronic acid, dehydroacetic acid, terephthalic acid, tropic acid, vanillic acid, paraconic acid, hydroxyisophthalic acid, hydroxycinnamic acid, hydroxynaphthoic acid, o -Hydroxyphenylacetic acid, m-hydroxyphenylacetic acid, p-hydroxyphenylacetic acid, 3-hydroxy-3-phenylpropionic acid, pivalic acid, pyridinedicarboxylic acid, pyridinetricarboxylic acid, pyruvic acid, α-phenylcinnamic acid, phenylglycine Sidic acid, phenylsuccinic acid, phenylacetic acid, phenyllactic acid, propiolic acid, sorbic acid, 2,4-hexadienedioic acid, 2-benzylidenepropionic acid, 3-benzylidenepropionic acid, benzylidenemalonic acid, benzylic acid, benzenetricarboxylic acid 1,2-benzenediacetic acid, benzoyloxyacetic acid, benzoyloxypropionic acid, benzoylformic acid, benzoylacetic acid, O-benzoyllactic acid, 3-benzoylpropionic acid, gallic acid, mesooxalic acid, 5-methylisophthalic acid, 2-methylcroton Acid, α-methylcinnamic acid, methylsuccinic acid, methylmalonic acid, 2-methylbutyric acid, o-methoxycinnamic acid, p-methoxycinnamic acid, mercaptosuccinic acid, mercaptoacetic acid, O-lactoyllactic acid, malic acid, leucon Acid, leucine acid, rosin acid, rosoleic acid, α-ketoglutaric acid, L-alcorbic acid, iduronic acid, galacturonic acid, glucuronic acid, pyroglutamic acid, ethylenediaminetetraacetic acid, triacetic acid acetic acid, aspartic acid, glutamic acid, N′- Hydroxyethyl-N, N, N'-triacetic acid Carboxylic acids such as nitrilotriacetic acid;
phenols such as o-aminophenol, m-aminophenol, p-aminophenol;
Methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, hexanesulfonic acid, heptanesulfonic acid, octanesulfonic acid, nonanesulfonic acid, decanesulfonic acid, undecanesulfonic acid, dodecanesulfonic acid, tridecane Sulfonic acid, tetradecanesulfonic acid, pentadecanesulfonic acid, hexadecanesulfonic acid, heptadecanesulfonic acid, octadecanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, toluenesulfonic acid (eg p-toluenesulfonic acid), hydroxyethanesulfonic acid, hydroxy Sulfonic acids such as phenol sulfonic acid and anthracene sulfonic acid;
Phosphonic acids such as decylphosphonic acid and phenylphosphonic acid are preferred.

In addition, the organic acid component B includes one or more protons in the main chain of the carboxylic acid, sulfonic acid, and phosphonic acid, and atoms or atoms such as F, Cl, Br, I, OH, CN, and NO ₂ It may be a derivative substituted with a group.

  The pKa of the organic acid component B is preferably less than 9, more preferably less than 8, further preferably less than 7, particularly preferably less than 6, and extremely less than 5. preferable. If the pKa of the organic acid component B is less than 9, at least part of the organic acid component becomes an organic acid ion in the polishing liquid, and hydrogen ions are released, so that the pH is easily maintained in a desired pH range. In addition, the effect of suppressing the dissociation of the carboxyl group in the polymer compound A is further enhanced, which is effective for improving the flatness.

  The organic acid component B may be used alone or in combination of two or more.

  The content of the organic acid component B is preferably 0.001 to 2% by mass, more preferably 0.005 to 1% by mass, and still more preferably 0.01 to 0.5% by mass, based on the total mass of the polishing liquid. preferable. If the content of the organic acid component B is 0.001% by mass or more, the flatness of the insulating material (for example, silicon oxide) after polishing tends to be improved. There is a tendency that the polishing rate of the material is sufficiently improved.

(water)
Although it does not restrict | limit especially as water, Deionized water, ion-exchange water, ultrapure water, etc. are preferable. The water content is not particularly limited as long as it is the remainder of the content of each of the above-described components and is contained in the polishing liquid. The polishing liquid may further contain a solvent other than water, for example, a polar solvent such as ethanol or acetone, as necessary.

(PH adjuster)
The polishing liquid according to the present embodiment can contain a pH adjuster as necessary. Thereby, it can adjust to desired pH. The pH adjuster is not particularly limited, and examples thereof include inorganic acid components such as nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid and boric acid; and base components such as sodium hydroxide, ammonia, potassium hydroxide and calcium hydroxide. It is done. The pH can also be adjusted using an organic acid component. When the polishing liquid is used for semiconductor polishing, ammonia and an acid component are preferably used.

(PH)
The pH (25 ° C.) of the polishing liquid is preferably 4.0 to 6.0, and more preferably 4.5 to 5.5. When the pH is 4.0 to 6.0, it is possible to obtain excellent storage stability while having an excellent polishing rate of the insulating material, and also to flatten the surface after polishing such as dishing amount and wiring density dependency Can be improved.

  The pH of the polishing liquid can be measured using a pH meter (for example, Model PH81 (trade name) manufactured by Yokogawa Electric Corporation). For example, after calibrating two points using a standard buffer (phthalate pH buffer pH: 4.01 (25 ° C.) and neutral phosphate pH buffer pH: 6.86 (25 ° C.)), the electrode Is put into a polishing liquid, and the value after being stabilized at 25 ° C. for 2 minutes or more is measured.

(Dispersant)
The polishing liquid according to this embodiment can contain a dispersant (excluding the polymer compound A) as necessary. The content of the dispersant is preferably 0.001 to 4% by mass based on the total mass of the abrasive grains. Examples of the dispersant include a water-soluble cationic compound, a water-soluble anionic compound, a water-soluble nonionic compound, and a water-soluble amphoteric compound. Among them, the electrostatic repulsion force is large and the dispersibility is good. From this viewpoint, a water-soluble anionic compound is preferable. The polymer compound A can also be used for dispersing the abrasive grains.

  Examples of the water-soluble cationic compound include polyvinyl pyrrolidone, coconut amine acetate, stearyl amine acetate and the like.

  Examples of the water-soluble anionic compound include lauryl sulfate triethanolamine, ammonium lauryl sulfate, polyoxyethylene alkyl ether sulfate triethanolamine, and a special polycarboxylic acid type polymer compound.

  Examples of water-soluble nonionic compounds include polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene alkylamine, polyoxyethylene hydrogenated castor oil, 2-hydroxyethyl Methacrylate, alkyl alkanolamide and the like can be mentioned.

  Examples of the water-soluble amphoteric compound include lauryl betaine, stearyl betaine, lauryl dimethylamine oxide, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine and the like.

(Other additives)
The polishing liquid according to this embodiment can contain a component other than the glycine compound, the polymer compound A, the organic acid component B, the pH adjuster, the dispersant, and water as an additive. Examples of such additives include water-soluble polymer compounds (excluding the polymer compound A). When the polishing liquid is stored separately in the cerium oxide slurry and the additive liquid, these other additives are preferably included in the additive liquid.

  Examples of water-soluble polymer compounds include polysaccharides such as alginic acid, pectic acid, carboxymethylcellulose, agar, curdlan, and pullulan; polyaspartic acid, polyglutamic acid, polylysine, polyamic acid, polyamic acid ammonium salt, polyamic acid sodium salt, poly Examples thereof include polycarboxylic acids such as glyoxylic acid and salts thereof; vinyl polymers such as polyvinyl alcohol and polyacrolein;

  These additives may be used alone or in combination of two or more.

  The content of the other additives is preferably 0.01 to 5% by mass based on the total mass of the polishing liquid.

  The constituent components of the polishing liquid according to the present embodiment may be stored in two or more liquids so as to be the polishing liquid. For example, a cerium oxide slurry containing abrasive grains and water (first liquid), and other additives (for example, glycine-based compound and polymer compound A) and an additive liquid (second liquid) containing water, It is possible to obtain a polishing liquid by storing it as a two-component polishing liquid composed of The organic acid component B and each component described in the “other additives” are preferably included in the additive solution.

<Manufacturing method of polishing liquid>
The method for producing a polishing liquid according to the present embodiment is a method for producing a polishing liquid for removing at least a part of an insulating material by CMP. The manufacturing method of the polishing liquid according to the present embodiment includes at least a polishing liquid manufacturing step for obtaining a polishing liquid by mixing abrasive grains, a glycine compound, a polymer compound A, and water. In the polishing liquid production process, each component may be mixed simultaneously, or each component may be mixed sequentially. The manufacturing method of the polishing liquid according to this embodiment may include a step of obtaining abrasive grains containing cerium oxide and a step of obtaining the polymer compound A before the polishing liquid manufacturing step.

  The method for producing a polishing liquid according to this embodiment preferably includes a dispersion step of dispersing abrasive grains in water. A dispersion | distribution process is a process of mixing an abrasive grain and a dispersing agent, for example. In this case, the dispersant is preferably added in the step of obtaining the cerium oxide slurry. That is, the cerium oxide slurry preferably contains a dispersant. In the dispersion step, for example, abrasive grains, a dispersant, and water are mixed, and the abrasive grains are dispersed in water to obtain a cerium oxide slurry.

<Polishing method>
The polishing method according to the present embodiment includes a polishing step of removing at least a part of the insulating material by CMP using the polishing liquid according to the present embodiment. For example, the polishing method according to the present embodiment may be a polishing method for polishing a substrate having an insulating material on the surface (substrate polishing method). The polishing method according to the present embodiment includes, for example, a substrate preparation process, a substrate arrangement process, and a polishing process. In the substrate preparation step, for example, a substrate having an insulating material on the surface is prepared. In the substrate placement step, for example, the substrate is placed so that the insulating material faces the polishing cloth. In the polishing step, for example, at least a part of the insulating material is removed. In the polishing step, for example, in a state where the insulating material of the substrate having the insulating material is pressed against the polishing cloth of the polishing surface plate, a polishing liquid is supplied between the polishing cloth and the insulating material, Is moved relatively to polish and remove at least a portion of the insulating material.

  The polishing step may be a step of selectively (preferentially) polishing the insulating material with respect to the stopper material. The polishing step may be a step of selectively (preferentially) polishing silicon oxide with respect to silicon nitride. The polishing step may be a step of polishing silicon oxide using silicon nitride as a stopper material.

  The substrate may be an insulating material (for example, an inorganic insulating material) on a semiconductor substrate such as a substrate related to semiconductor element manufacture, for example, a semiconductor substrate at a stage where a circuit element and a wiring pattern are formed, or a semiconductor substrate at a stage where a circuit element is formed. ) Is formed.

  Examples of the insulating material include inorganic insulating materials and organic insulating materials. Examples of inorganic insulating materials include silicon-based insulating materials. Examples of the silicon-based insulating material include silica-based materials such as silicon oxide, fluorosilicate glass, organosilicate glass, and hydrogenated silsesquioxane; silicon carbide; silicon nitride. Examples of the organic insulating material include a wholly aromatic low dielectric constant insulating material. The insulating material (silicon oxide or the like) may be doped with an element such as phosphorus or boron. Examples of the stopper material include silicon nitride. The insulating material is an insulating material excluding silicon nitride. The shape of the insulating material is not particularly limited, and is, for example, a film shape (insulating film). The shape of the stopper material is not particularly limited, and is, for example, a film shape (a stopper film, such as a silicon nitride film).

  By polishing the insulating material formed on such a semiconductor substrate with the polishing liquid according to the present embodiment, unevenness on the surface of the insulating material can be eliminated, and a smooth surface can be obtained over the entire surface of the semiconductor substrate. . The polishing method according to this embodiment can be used for, for example, an interlayer insulating film, a BPSG film planarization process, a shallow trench isolation (STI) formation process, and the like.

  Hereinafter, the polishing method according to the present embodiment will be described in more detail by taking the case of a semiconductor substrate on which an insulating material is formed as an example. FIG. 1 is a schematic cross-sectional view showing an example of a polishing method. First, as shown in FIG. 1 (A), a substrate 100 having a wafer 1 having concave and convex portions formed on its surface and a silicon nitride film 2 formed on the convex portion of the wafer 1. Prepare. Next, as shown in FIG. 1B, a silicon oxide film 3 is deposited by plasma TEOS or the like so as to fill the irregularities on the surface of the wafer 1 to obtain a substrate 200.

  Then, by using the polishing liquid, the silicon oxide film 3 is polished and removed until the silicon nitride film 2 on the convex portion of the wafer 1 is exposed, thereby obtaining a substrate 300 as shown in FIG. . In the substrate 300 after polishing, it is preferable that the dishing amount 6 which is a value obtained by subtracting the thickness 5 of the silicon oxide film 3 in the trench portion from the depth 4 of the trench portion is small.

  The polishing apparatus generally includes a holder for holding a semiconductor substrate or the like on which a material to be polished is formed, and a polishing surface plate to which a motor capable of changing the number of rotations is attached and a polishing cloth can be attached. A simple polishing apparatus can be used. As the polishing apparatus, for example, model number: EPO-111 manufactured by Ebara Manufacturing Co., Ltd., and product names: MIRRA, Reflexion (“MIRRA” and “Reflexion” are registered trademarks) manufactured by APPLIED MATERIALS can be used.

  As the polishing cloth, a general nonwoven fabric, foamed polyurethane, porous fluororesin and the like can be used without particular limitation. Moreover, it is preferable that the polishing cloth is subjected to groove processing so that the polishing liquid is accumulated.

Although there is no limitation on polishing conditions, the rotation speed of the surface plate is preferably low rotation of 200 min ⁻¹ or less so that the semiconductor substrate does not pop out, and the pressure (working load) applied to the semiconductor substrate does not cause scratches after polishing. Thus, 100 kPa or less is preferable. During polishing, the polishing liquid can be continuously supplied to the polishing cloth with a pump or the like. Although there is no restriction | limiting in this supply amount, it is preferable that the surface of polishing cloth is always covered with polishing liquid.

  The semiconductor substrate after polishing is preferably washed in running water and then dried by removing water droplets adhering to the semiconductor substrate using a spin dryer or the like.

  By polishing the insulating material as the material to be polished with the polishing liquid in this way, surface irregularities are eliminated, and a smooth surface can be obtained over the entire surface of the semiconductor substrate. After the planarized shallow trench is formed, aluminum wiring or the like is formed on the insulating material, the insulating material is formed again between the wirings and on the wiring, and then the insulating material is polished using the polishing liquid. And get a smooth surface. By repeating this step a predetermined number of times, a semiconductor substrate having a desired number of layers can be manufactured.

  Examples of the material to be polished by the polishing liquid according to this embodiment include silicon oxide and silicon nitride. Silicon oxide may be doped with an element such as phosphorus or boron. Examples of a method for manufacturing the material to be polished include a low pressure CVD method and a plasma CVD method.

In forming the silicon oxide film by the low pressure CVD method, monosilane: SiH ₄ can be used as the Si source, and oxygen: O ₂ can be used as the oxygen source. A silicon oxide film is obtained by performing this SiH ₄ —O ₂ -based oxidation reaction at a low temperature of 400 ° C. or lower. In some cases, the silicon oxide film obtained by CVD is heat-treated at a temperature of 1000 ° C. or lower. In order to planarize the surface by high-temperature reflow, when doping silicon: P with phosphorus: P, it is preferable to use a SiH ₄ —O ₂ —PH ₃ -based reactive gas.

The plasma CVD method has an advantage that a chemical reaction requiring a high temperature can be performed at a low temperature under normal thermal equilibrium. There are two plasma generation methods, capacitive coupling type and inductive coupling type. The reaction gases, SiH ₄ as an Si source, _SiH 4 -N ₂ O-containing gas using _{N 2} O as an oxygen source, TEOS-O-based gas using tetraethoxysilane (TEOS) as an Si source (TEOS-plasma CVD method). The substrate temperature is preferably 250 to 400 ° C., and the reaction pressure is preferably 67 to 400 Pa.

Formation of the silicon nitride film by the low pressure CVD method can use dichlorosilane: SiH ₂ Cl ₂ as the Si source and ammonia: NH ₃ as the nitrogen source. A silicon nitride film is obtained by performing this SiH ₂ Cl ₂ —NH ₃ -based oxidation reaction at a high temperature such as 900 ° C. Examples of a reactive gas in forming a silicon nitride film by plasma CVD include SiH ₄ —NH ₃ based gas using SiH ₄ as a Si source and NH ₃ as a nitrogen source. The substrate temperature is preferably 300 to 400 ° C.

  The polishing liquid and the polishing method according to the present embodiment can be applied not only to the insulating material formed on the semiconductor substrate but also to various semiconductor device manufacturing processes. The polishing liquid and the polishing method according to the present embodiment include, for example, an inorganic insulating material such as silicon oxide and glass formed on a wiring board having predetermined wiring, polysilicon, Al, Cu, Ti, TiN, W, Ta, Optical integrated circuits, optical switching elements, and optical elements composed of films mainly containing TaN, optical glass such as photomasks, lenses, and prisms, inorganic conductive films such as ITO (indium tin oxide), glass, and crystalline materials Polishing optical waveguides, optical fiber end faces, optical single crystals such as scintillators, solid state laser single crystals, sapphire substrates for blue laser LEDs, semiconductor single crystals such as SiC, GaP, and GaAs, glass substrates for magnetic disks, magnetic heads, etc. It can also be applied to.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.

<Preparation of cerium oxide powder>
40 kg of commercially available cerium carbonate hydrate was placed in an alumina container and baked in air at 830 ° C. for 2 hours to obtain 20 kg of yellowish white powder. When the phase of this powder was identified by the X-ray diffraction method, it was confirmed to be cerium oxide. 20 kg of the obtained cerium oxide powder was dry-ground using a jet mill to obtain a cerium oxide powder containing cerium oxide particles.

<Preparation of polymer compound A (polyacrylic acid)>
250 g of deionized water was charged into a 1 L synthesis flask equipped with a stirrer, a thermometer, and a nitrogen inlet. The temperature was raised to 90 ° C. with stirring in a nitrogen gas atmosphere. A solution prepared by dissolving 130 g of acrylic acid and 14 g of 2,2′-azobis [2- (2-imidazolin-2-yl) propane] sulfate in 130 g of methanol was poured into the flask over 2 hours. After keeping at 90 ° C. for 3 hours, the solution was cooled to 40 ° C. or lower. Deionized water was added to obtain a 40% by mass aqueous solution of polyacrylic acid (a homopolymer of acrylic acid). The molecular weight of the obtained polyacrylic acid was measured by size exclusion chromatography using a calibration curve prepared with a sodium polyacrylate standard substance manufactured by Polymer Laboratories. The weight average molecular weight was 2500 (polyacrylic acid). Sodium equivalent value).

<Preparation of CMP polishing liquid>
Example 1
200.0 g of the cerium oxide powder prepared above and 795.0 g of deionized water are mixed, and 5 g of an aqueous ammonium polyacrylate solution (weight average molecular weight: 8000, 40% by mass) is added, and ultrasonic waves are stirred. Dispersion was performed to obtain a cerium oxide dispersion. Ultrasonic dispersion was performed at an ultrasonic frequency of 400 kHz and a dispersion time of 20 minutes.

  Thereafter, 1 kg of cerium oxide dispersion was placed in a 1 L container (height: 170 mm) and allowed to stand, and sedimentation classification was performed. After 15 hours of classification time, the supernatant above a depth of 130 mm from the water surface was pumped up. The obtained supernatant cerium oxide dispersion was diluted with deionized water to a solid content of 5% by mass to obtain a cerium oxide slurry.

  In order to measure the average particle diameter (D50) of cerium oxide in the cerium oxide slurry, the slurry was diluted so that the measurement transmittance (H) with respect to the He-Ne laser was 60 to 70% to obtain a measurement sample. . Using a laser diffraction particle size distribution meter Mastersizer Microplus (Malvern, trade name ("Mastersizer" is a registered trademark)), the refractive index is 1.93, the absorption is 0, and the D50 of the measurement sample is measured. Was 150 nm.

  A polyacrylic compound containing 0.3 g of p-toluenesulfonic acid as an organic acid component, 0.5 g of glycine as a glycine compound, and 800 g of deionized water, and having a weight average molecular weight of 2500 and 40% by mass as the polymer compound A 3.75 g of an acid aqueous solution was added, and aqueous ammonia (25% by mass) was added to adjust the pH to 4.5. Further, deionized water was added to obtain an additive solution having a total amount of 850 g.

  66 g of the above cerium oxide slurry is added, and ammonia water (25% by mass) is added to adjust the pH to 5.4. Further, deionized water is added to bring the total amount to 1000 g, and a CMP polishing liquid (ceria-based polishing) is added. Liquid, cerium oxide solid content: 0.33 mass%).

  Further, a measurement sample was prepared in the same manner as described above, and the average particle size of the abrasive grains in the CMP polishing liquid was measured with a laser diffraction particle size distribution meter. As a result, the value of D50 was 150 nm.

(Examples 2-3 and Comparative Examples 1-3)
A polishing slurry for CMP was prepared in the same manner as in Example 1, except that the type and content of the glycine compound were changed as shown in Table 1. As a comparative example, a polishing slurry for CMP using acetic acid and propionic acid, which are monocarboxylic acids not containing amino groups, was prepared. Also in these polishing liquids for CMP, the average particle diameter of the particles in the polishing liquid for CMP was measured with a laser diffraction particle size distribution analyzer. As a result, the value of D50 was 150 nm. In Comparative Example 1, no glycine compound was used.

<Polishing property evaluation>
A blanket wafer (Blanket wafer) on which no pattern was formed was used as a test wafer for CMP evaluation. As a blanket wafer, a wafer having a silicon oxide film having a thickness of 1000 nm on a silicon (Si) substrate (diameter: 300 mm) and a wafer having a silicon nitride film having a thickness of 200 nm on a silicon (Si) substrate (diameter: 300 mm) And were used.

  A polishing apparatus (Reflexion manufactured by APPLIED MATERIALS) was used for polishing the test wafer for CMP evaluation. A test wafer for CMP evaluation was set in a holder to which a suction pad for attaching a substrate was attached. A polishing cloth made of porous urethane resin (Rohm and Haas Japan, model number IC1010) was attached to a polishing surface plate having a diameter of 600 mm of a polishing apparatus. The holder was placed on the polishing platen with the surface on which the insulating film (silicon oxide film) or silicon nitride film as the film to be polished was placed facing down, and the processing load was set to 3 psi (about 20.6 kPa).

While the CMP polishing liquid to the polishing platen was added dropwise at a rate of 250 mL / min, and the polishing plate and the CMP evaluation test wafer was rotated at respectively ^{93min -1, 87min} -1, two types of CMP Each test wafer for evaluation was polished for 60 seconds. The polished wafer was thoroughly washed with a chemical solution and pure water using a PVA brush (polyvinyl alcohol brush) and then dried.

  The polishing rate of the silicon oxide film or silicon nitride film on the blanket wafer was evaluated according to the following procedure. The evaluation results are shown in Table 1.

  Using an optical interference film thickness device (Dainippon Screen Mfg. Co., Ltd., trade name: RE-3000), the film thicknesses of the silicon oxide film and the silicon nitride film before and after polishing are measured, and the average of the film thickness change amount is measured. The polishing rate of the silicon oxide film and the silicon nitride film on the blanket wafer was calculated. The unit of the polishing rate is nm / min.

  From Table 1, the polishing liquid according to the present invention contains abrasive grains containing cerium oxide, a glycine-based compound, and a polymer compound A, so that an excellent polishing rate is exhibited and an oxide that is an insulating film. It has been clarified that the polishing rate ratio of the silicon film to the silicon nitride film as the stopper film is as large as 10 or more. Moreover, it can be seen from Comparative Examples 2 and 3 that the compound not having the structure represented by the formula (1) has a small polishing rate ratio, and a glycine compound containing an amino group is suitable.

  DESCRIPTION OF SYMBOLS 1 ... Wafer, 2 ... Silicon nitride film, 3 ... Silicon oxide film, 4 ... Depth of trench part, 5 ... Thickness of silicon oxide film in trench part after grinding | polishing, 6 ... Dishing amount, 100, 200, 300 ... substrate.

Claims (12)

A method for producing a polishing liquid for removing at least a part of an insulating material by CMP, comprising:
Abrasive grains containing cerium oxide;
A glycine compound having a structure represented by the following general formula (1);
A polymer compound having at least one selected from the group consisting of a carboxylic acid group and a carboxylic acid group;
A method for producing a polishing liquid, comprising a step of mixing with water to obtain a polishing liquid.

[Wherein, R ¹ and R ² each independently represent a hydrogen atom or a monovalent substituent. ]   The method for producing a polishing liquid according to claim 1, wherein the polishing liquid contains at least one organic acid component selected from the group consisting of an organic acid and an organic acid salt (excluding the glycine-based compound).   The method for producing a polishing liquid according to claim 1 or 2, wherein the content of the polymer compound in the polishing liquid is 0.001 to 2% by mass based on the total mass of the polishing liquid.   The method for producing a polishing liquid according to any one of claims 1 to 3, wherein the glycine-based compound is at least one selected from the group consisting of glycine, glycylglycine, and glycosylamine.   The manufacturing method of the polishing liquid as described in any one of Claims 1-4 whose pH of the said polishing liquid is 4.0-6.0. A polishing liquid for removing at least a part of an insulating material by CMP,
Abrasive grains containing cerium oxide;
A glycine compound having a structure represented by the following general formula (1);
A polymer compound having at least one selected from the group consisting of a carboxylic acid group and a carboxylic acid group;
A polishing liquid containing water.

[Wherein, R ¹ and R ² each independently represent a hydrogen atom or a monovalent substituent. ]   The polishing liquid according to claim 6, further comprising at least one organic acid component selected from the group consisting of an organic acid and an organic acid salt (excluding the glycine compound).   The polishing liquid according to claim 6 or 7, wherein the content of the polymer compound is 0.001 to 2 mass% based on the total mass of the polishing liquid.   The polishing liquid according to any one of claims 6 to 8, wherein the glycine-based compound is at least one selected from the group consisting of glycine, glycylglycine, and glycosylamine.   The polishing liquid according to any one of claims 6 to 9, wherein the pH is 4.0 to 6.0.   It is preserve | saved as a 2 liquid type polishing liquid comprised from the 1st liquid containing the said abrasive grain and water, and the 2nd liquid containing the said glycine type compound, the said high molecular compound, and water. The polishing liquid according to any one of 10.   A polishing method, wherein at least a part of an insulating material is removed by CMP using the polishing liquid according to claim 6.

Images