JP2009289886A - Polishing liquid and polishing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polishing liquid that is used for CMP to a body to be polished with a layer containing polysilicon or the like, has rapid polishing speed for a layer containing a silicon-based material other than polysilicon, and can selectively suppress the polishing of a layer containing polysilicon or the like; and to provide a polishing method using the polishing liquid. <P>SOLUTION: In a planarization step when manufacturing a semiconductor integrated circuit, the polishing liquid is used for CMP to a body to be polished at least having a first layer containing polysilicon or the like and a second layer containing at least one selected from a group comprising silicon oxide, silicon nitride and the like, contains each constituent shown by a colloidal silicon particle (1), an organic acid (2), and at least one nonionic additive selected from a nonionic surfactant and a nonionic hydrophilic resin (3), has a<SB>P</SB>H of 1.5-7.0, and can selectively polish the second layer to the first layer. In the polishing method, the polishing liquid is used. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polishing liquid used in a manufacturing process of a semiconductor integrated circuit and a polishing method using the same. More specifically, the present invention relates to a polishing liquid that can be suitably used for gate formation in a semiconductor substrate, and a polishing method using the same, and in particular, a semiconductor substrate having a layer containing polysilicon or modified polysilicon is polished by chemical mechanical polishing. The present invention relates to a polishing liquid and a polishing method using the same.

  In the development of semiconductor devices represented by semiconductor integrated circuits (hereinafter sometimes referred to as “LSI”), in recent years, in order to reduce the size and increase the speed, higher density and higher integration have been achieved by miniaturization and lamination of wiring. Is required. Various techniques such as chemical mechanical polishing (hereinafter sometimes referred to as “CMP”) have been used as techniques for this purpose. This CMP is an indispensable technique for performing surface planarization of a film to be processed such as an interlayer insulating film, plug formation, formation of embedded metal wiring, etc., and smoothing the substrate.

  A general method of CMP is to apply a polishing pad on a circular polishing platen (platen), immerse the polishing pad surface with a polishing liquid, and press the surface of the substrate (wafer) against the pad (surface to be polished) In a state where a predetermined pressure (polishing pressure) is applied from the back surface, both the polishing platen and the substrate are rotated, and the surface of the substrate is flattened by the generated mechanical friction.

In recent years, CMP has been applied to each step in semiconductor manufacturing, and one example thereof is application to a gate formation step in transistor fabrication.
Here, in the conventional transistor, a gate mainly made of modified polysilicon in which impurities such as B are implanted into polysilicon is manufactured. However, in a transistor of 45 nm generation and later, power consumption is reduced and high current driving is performed in standby. In order to achieve both capabilities, application of a high dielectric constant gate insulating film (High-k film) and a metal gate electrode in place of conventional polysilicon is being studied. Several techniques have been proposed as techniques to which these are applied. For example, after forming a dummy gate insulating film and a dummy gate electrode, implanting impurities in a polycrystalline silicon film in a self-aligned manner to form a source / drain diffusion layer, removing the dummy gate insulating film and the dummy gate electrode, A method of forming a high dielectric constant gate insulating film and a metal gate electrode has been proposed (see, for example, Patent Documents 1 to 3).

  Several methods for forming the metal gate electrode have been proposed. One candidate is a fully silicided gate (hereinafter referred to as “FUSI gate”). The FUSI gate is formed by siliciding the gate electrode formed of polysilicon as in the conventional CMOS process. Conventionally, only the upper part of the gate electrode is silicidized, whereas in FUSI, the gate electrode is The whole is silicided. FUSI has a large merit in process construction compared to a technique of forming a metal gate electrode by a damascene process because the know-how of the conventional CMOS process becomes useful.

In recent years, in the formation of a gate using such polysilicon or modified polysilicon (hereinafter sometimes simply referred to as “polysilicon etc.”), the second and third layers covering the polysilicon etc. and its periphery are formed. It has been proposed to perform CMP selectively on these materials (for example, silicon-based materials other than polysilicon or the like) (see, for example, Patent Document 4). However, there is a problem that when a polishing object containing polysilicon or the like is polished by CMP using a conventionally known polishing liquid, polysilicon or the like to be left as a gate material is excessively polished. It was also a factor of the performance degradation of the obtained LSI.
JP 2006-339597 A JP 2006-344836 A JP 2007-12922 A JP 2005-93816 A

  An object of the present invention is to use a silicon-based material other than polysilicon or modified polysilicon, which can be used for chemical mechanical polishing of an object to be polished having a layer containing polysilicon or modified polysilicon in the production of a semiconductor integrated circuit. It is an object of the present invention to provide a polishing liquid that has a rapid polishing rate for a layer containing silicon and that can selectively suppress polishing of a layer containing polysilicon or modified polysilicon, and a polishing method using the same.

Specific means for solving the above problems are as follows.
<1> In a planarization step when manufacturing a semiconductor integrated circuit, a first layer containing polysilicon or modified polysilicon, silicon oxide, silicon nitride, silicon carbide, silicon carbonitride, silicon oxide carbide, and silicon oxynitride And a second layer containing at least one selected from the group consisting of the following: (1), (2) and (3) A polishing liquid comprising: each component represented by the above formula, having a pH of 1.5 to 7.0, and capable of selectively polishing the second layer with respect to the first layer.
(1) Colloidal silica particles (2) Organic acid (3) Nonionic surfactant and at least one nonionic additive selected from nonionic hydrophilic resins

<2> When the polishing rate of the first layer is RR (p-Si) and the polishing rate of the second layer is RR (other), it is expressed as RR (other) / RR (p-Si). The polishing liquid according to <1>, wherein the polishing target can be polished within a polishing rate ratio of 1.5 to 200.

<3> The polishing liquid according to <1> or <2>, wherein the concentration of the colloidal silica is 0.1% by mass to 10% by mass with respect to the total mass of the polishing liquid.

<4> Any one of <1> to <3>, wherein the colloidal silica has an average primary particle size of 5 nm to 100 nm and an average secondary particle size of 10 nm to 300 nm. The polishing liquid described in 1.

<5> The polishing liquid according to any one of <1> to <4>, wherein the organic acid is an organic acid containing at least one carboxyl group in the molecular structure.

<6> The polishing liquid according to any one of <1> to <5>, wherein the organic acid is a compound represented by the following general formula (I).

  In general formula (I), R represents an alkylene group having 1 to 20 carbon atoms, an alkynylene group, a cycloalkylene group, an arylene group, or a group formed by combining two or more of these groups. These groups may be further substituted with other functional groups.

<7> The polishing according to any one of <1> to <6>, wherein the concentration of the organic acid is 0.001% by mass to 3% by mass with respect to the total mass of the polishing liquid. liquid.

<8> The nonionic additive is represented by the following nonionic surfactant represented by the following general formula (II), nonionic surfactant represented by the general formula (III), and general formula (IV). Selected from the group consisting of a nonionic surfactant, a hydrophilic resin containing a structural unit represented by general formula (V), and a hydrophilic resin containing a structural unit represented by general formula (VI) The polishing liquid according to any one of <1> to <7>, wherein the polishing liquid is at least one nonionic additive.

In general formula (II), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 6 to 30 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkylcarbonyl group, or a polyoxy group. Represents an ethylene chain, R ¹ and R ² may be bonded to each other; a represents an integer of 1 to 10.

In the general formula (III), R ³ represents an alkyl group having 6 to 20 carbon atoms, an alkynyl group, a cycloalkyl group, an aryl, or a group formed by combining two or more of these groups. b represents an integer of 1 to 10.

In general formula (IV), R ⁴ represents an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, an arylene group, or an aralkylene group, and R ⁵ , R ⁶ , and R ⁷ are each independently a hydrogen atom, An alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, or an aralkyl group is represented. R ⁸ represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or an aralkyl group. c represents an integer of 1 to 10. m represents an integer of 1 to 100, and n represents an integer of 1 to 100.

In general formula (V), R ⁹ represents an alkylene group having 1 to 20 carbon atoms, an alkynylene group, a cycloalkylene group, an arylene group, or a group formed by combining two or more of these groups.
p represents an integer of 5 or more.

In General Formula (VI), R ¹⁰ represents an alkylene group having 1 to 20 carbon atoms, an alkynylene group, a cycloalkylene group, an arylene group, or a group formed by combining two or more of these groups.
q represents an integer of 5 or more.

<9> The concentration of the nonionic additive is 0.001% by mass to 1% by mass with respect to the total mass of the polishing liquid, according to any one of <1> to <8 < Polishing fluid.

<10> The polishing liquid according to any one of <1> to <9> is supplied to a polishing pad on a polishing surface plate, and the polishing surface plate is rotated to rotate the polishing pad. A polishing method, wherein polishing is performed by making a relative movement while contacting with a surface to be polished.

  According to the present invention, a silicon-based material other than polysilicon or modified polysilicon can be used for chemical mechanical polishing of an object to be polished having a layer containing polysilicon or modified polysilicon in the production of a semiconductor integrated circuit. It is possible to provide a polishing liquid that has a rapid polishing rate for a layer containing, and can selectively suppress polishing of a layer containing polysilicon or modified polysilicon, and a polishing method using the same.

  Hereinafter, the polishing liquid of the present invention and the polishing method using the same will be described in detail.

[Polishing liquid]
The polishing liquid of the present invention includes a first layer containing polysilicon or modified polysilicon, a silicon oxide, a silicon nitride, a silicon carbide, a silicon carbonitride, a silicon oxide carbide, in a planarization step when manufacturing a semiconductor integrated circuit. And a second layer containing at least one selected from the group consisting of silicon oxynitride, and used for chemical mechanical polishing of an object to be polished comprising at least one of the following (1), (2) And each component represented by (3), having a pH of 1.5 to 7.0, and capable of selectively polishing the second layer with respect to the first layer. Polishing fluid.
(1) Colloidal silica particles (2) Organic acid (3) Nonionic surfactant and at least one nonionic additive selected from nonionic hydrophilic resins

  In the present invention, the “polishing liquid” means not only a polishing liquid used for polishing (that is, a polishing liquid diluted as necessary) but also a concentrated liquid of the polishing liquid. The concentrated liquid or the concentrated polishing liquid means a polishing liquid adjusted to have a higher solute concentration than the polishing liquid used for polishing, and is diluted with water or an aqueous solution when used for polishing. And used for polishing. The dilution factor is generally 1 to 20 volume times. In this specification, “concentration” and “concentrated liquid” are used in accordance with conventional expressions meaning “thick” and “thick liquid” rather than the state of use, and generally involve physical concentration operations such as evaporation. The term is used in a different way from the meaning of common terms.

  The polishing liquid of the present invention is suitably used when applying polysilicon or modified polysilicon as an electrode material and forming a gate electrode in a semiconductor integrated circuit by CMP. More specifically, the polishing liquid of the present invention includes a first layer containing polysilicon or modified polysilicon, silicon oxide, silicon nitride, silicon carbide, carbonitriding in a planarization step when manufacturing a semiconductor integrated circuit. And a second layer containing at least one selected from the group consisting of silicon, silicon oxide carbide, and silicon oxynitride, and a polishing liquid used for chemical mechanical polishing of an object to be polished. is there.

  The polishing liquid of the present invention is characterized by containing each of the components (1), (2) and (3), and having a pH of 1.5 to 7.0. Or a second layer containing at least one selected from the group consisting of silicon oxide, silicon nitride, silicon carbide, silicon carbonitride, silicon oxide carbide, and silicon oxynitride with respect to the first layer containing modified polysilicon. Can be selectively polished.

  For selective polishing of the second layer with respect to the first layer, the polishing liquid of the present invention sets the polishing rate of the first layer to RR (p-Si) and sets the polishing rate of the second layer to RR (other). ), It is preferable that the object to be polished can be polished within a polishing rate ratio represented by RR (other) / RR (p-Si) in the range of 1.5 to 200. The polishing rate ratio represented by RR (other) / RR (p-Si) is more preferably in the range of 3-100. When the polishing rate ratio represented by RR (other) / RR (p-Si) is within such a range, undesired polishing with respect to the first layer can be suppressed, and the first layer and its underlayer are polished during polishing. It is also possible to effectively suppress non-uniform peeling of the first layer caused by excessive stress applied to the film interface.

  Therefore, by using the polishing liquid of the present invention, even in the case of forming a gate electrode comprising polysilicon or modified polysilicon by CMP in the manufacture of LSI, the gate electrode is overpolished. On the other hand, a layer containing a silicon-based material other than polysilicon or modified polysilicon that requires rapid polishing can be polished quickly.

  Hereinafter, each component which comprises the polishing liquid of this invention is demonstrated in detail.

[(1) Colloidal silica particles]
The polishing liquid of the present invention contains colloidal silica particles as at least a part of the abrasive grains. The colloidal silica particles are preferably colloidal silica particles obtained by hydrolysis of alkoxysilane that do not contain impurities such as alkali metals inside the particles. On the other hand, although colloidal silica particles produced by a method of removing alkali from an aqueous alkali silicate solution can also be used, in this case, there is a concern that the alkali metal remaining in the particles gradually elutes and affects the polishing performance. is there. From such a viewpoint, a material obtained by hydrolysis of alkoxysilane is more preferable as a raw material.

The particle size of the colloidal silica particles is appropriately selected according to the purpose of use. As the particle size of the colloidal silica particles, the average primary particle size (volume basis) is preferably in the range of 5 nm to 100 nm, more preferably in the range of 10 nm to 100 nm, and still more preferably in the range of 10 nm to 80 nm. .
Moreover, it is preferable that the average secondary particle diameter of colloidal silica particle is the range of 10 nm-300 nm, More preferably, it is the range of 20 nm-200 nm, More preferably, it is the range of 20 nm-150 nm.
As the colloidal silica particles in the present invention, those having an average primary particle size in the range of 5 nm to 100 nm and an average secondary particle size in the range of 10 nm to 300 nm are particularly preferable.
Generation | occurrence | production of an abrasion flaw can be effectively suppressed because the particle size of colloidal silica particle satisfy | fills said range.
Here, the average primary particle diameter of the colloidal silica particles in the present invention means a particle diameter cumulative curve on a volume basis and means a particle diameter at a point where the cumulative frequency of this curve is 50%.
The average primary particle diameter of the colloidal silica particles can be measured with an electron microscope (transmission type) or the like.
Moreover, the average particle diameter (average secondary particle diameter) of the secondary particles formed by associating some colloidal silica particles represents the average particle diameter determined in the particle size distribution obtained from the dynamic light scattering method. For example, LB-500 manufactured by HORIBA, Ltd. is used as a measuring device for obtaining the particle size distribution.

  The content (concentration) of the colloidal silica particles in the polishing liquid of the present invention is preferably 0.1% by mass to 10% by mass, more preferably based on the total mass of the polishing liquid when used for polishing. It is 0.5 mass%-10 mass%, More preferably, it is 1 mass%-8 mass%. That is, the content of colloidal silica particles is preferably 0.1% by mass or more in terms of achieving a sufficient polishing rate ratio, and is preferably 10% by mass or less in terms of effectively suppressing the generation of polishing flaws.

  In the polishing liquid of the present invention, abrasive grains other than colloidal silica particles can be used in combination as long as the effects of the present invention are not impaired, but even in that case, the content ratio of colloidal silica particles in all abrasive grains is , Preferably it is 50 mass% or more, Most preferably, it is 80 mass% or more. All of the abrasive grains contained in the polishing liquid may be colloidal silica particles.

  In the polishing liquid of the present invention, examples of abrasive grains that can be used in combination with colloidal silica particles include abrasive grains such as fumed silica, ceria, alumina, and titania. The size of these combination abrasive grains is preferably equal to or more than that of colloidal silica particles, and preferably twice or less.

[(2) Organic acid]
The polishing liquid of the present invention contains at least one organic acid. The organic acid here is not a metal oxidizing agent, but has an action of promoting oxidation, adjusting pH, and buffering agent. As an organic acid, a water-soluble thing is desirable, for example, a water-soluble organic acid or an amino acid is mentioned. As examples of the organic acid or amino acid, for example, those selected from the following group are more suitable.

  That is, examples of the organic acid 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, Maleic acid, phthalic acid, malic acid, tartaric acid, citric acid, lactic acid, hydroxyethyliminodiacetic acid, iminodiacetic acid, acedamidoiminodiacetic acid, nitrilotripropanoic acid, nitrilotrimethylphosphonic acid, dihydroxyethylglycine, tricine, and Examples thereof include salts such as ammonium salts and alkali metal salts, and mixtures thereof.

  Examples of amino acids include glycine, L-alanine, β-alanine, L-2-aminobutyric acid, L-norvaline, L-valine, L-leucine, L-norleucine, L-isoleucine, L-alloisoleucine, L-phenylalanine, L-proline, sarcosine, L-ornithine, L-lysine, taurine, L-serine, L-threonine, L-allothreonine, L-homoserine, L-tyrosine, 3,5-diiodo-L-tyrosine , Β- (3,4-dihydroxyphenyl) -L-alanine, L-thyroxine, 4-hydroxy-L-proline, L-cysteine, L-methionine, L-ethionine, L-lanthionine, L-cystathionine, L- Cystine, L-cysteic acid, L-aspartic acid, L-glutamic acid, S- (carboxymethyl) -L -Cystine, 4-aminobutyric acid, L-asparagine, L-glutamine, azaserine, L-arginine, L-canavanine, L-citrulline, delta-hydroxy-L-lysine, creatine, L-quinurenin, L-histidine, 1- Examples include methyl-L-histidine, 3-methyl-L-histidine, ergothioneine, L-tryptophan, actinomycin C1, apamin, angiotensin I, angiotensin II and antipine.

  Among organic acids, an organic acid having at least one carboxyl group in the molecular structure is preferable from the viewpoint of achieving a sufficient polishing rate ratio. Among these, compounds represented by the following general formula (I) are preferable.

  In general formula (I), R represents an alkylene group having 1 to 20 carbon atoms, an alkynylene group, a cycloalkylene group, an arylene group, or a group formed by combining two or more of these groups.

  Specific examples of the alkylene group having 2 to 20 carbon atoms represented by R include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, and an octylene group. Among them, an ethylene group , Propylene group and butylene group are preferable.

  As the alkynylene group represented by R, those having 2 to 10 carbon atoms are preferable, and specific examples thereof include an ethynylene group and a propynylene group.

  Specific examples of the cycloalkylene group represented by R include a cyclohexylene group and a cyclopentylene group, and among them, a cyclohexylene group is preferable.

  Specific examples of the arylene group represented by R include a phenylene group and a naphthylene group, and among them, a phenylene group is preferable.

  Each group represented by R may further have a substituent, and examples of the substituent that can be introduced include a hydroxyl group, an amino group, a carboxyl group, a phosphoric acid group, an imino group, a thiol group, a sulfo group, a nitro group. Groups and the like.

  Each group represented by R may further have a substituent, and examples of the substituent that can be introduced include a hydroxyl group, an amino group, a carboxyl group, a phosphoric acid group, an imino group, a thiol group, a sulfo group, a nitro group. Groups and the like.

  Specific examples of the compound represented by the general formula (I) include nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalate Acid, malic acid, tartaric acid, citric acid, diglycolic acid, 2-furancarboxylic acid, 2,5-furandicarboxylic acid, 3-furancarboxylic acid, 2-tetrahydrofurancarboxylic acid, diglycolic acid, methoxyacetic acid, methoxyphenylacetic acid , Phenoxyacetic acid or a mixture thereof. Among these, ethylenediaminetetraacetic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, malic acid, tartaric acid, citric acid, di-acid from the point of achieving a good selectivity. Glycolic acid is preferred, and oxalic acid, adipic acid, pimelic acid, maleic acid, malic acid, tartaric acid, citric acid, and diglycolic acid are more preferred.

  The organic acid contained in the polishing liquid may be only one kind, or two or more kinds may be used in combination.

  The content of the organic acid in the polishing liquid is preferably 0.0001% by mass to 10% by mass, more preferably 0.001% by mass to 1% by mass, based on the mass of the polishing liquid used for polishing. More preferably, the content is 0.01% by mass to 1% by mass. That is, the content of the organic acid is preferably 0.0001% by mass or more from the viewpoint of achieving a sufficient polishing rate, and is preferably 10% by mass or less from the viewpoint of maintaining good flatness.

[(3) At least one nonionic additive selected from nonionic surfactants and hydrophilic resins]
The polishing liquid of the present invention contains at least one nonionic additive selected from a nonionic surfactant and a nonionic hydrophilic resin.

  Examples of the nonionic surfactant that can be applied as the nonionic additive include surfactants such as a surfactant containing a linear polyalkylene chain and a branched polyalkylene chain.

  Examples of nonionic hydrophilic resins that can be applied as nonionic additives include hydrophilic resins that do not have a leaving group in the structure, such as polyvinyl alcohol resins and polyvinylpyrrolidone resins. These hydrophilic resins are included.

  As a suitable embodiment of the nonionic additive contained in the polishing liquid, from the viewpoint of achieving a sufficient polishing rate, a nonionic surfactant represented by the following general formula (II), represented by the general formula (III): Nonionic surfactant represented by general formula (IV), nonionic surfactant represented by general formula (IV), hydrophilic resin containing a structural unit represented by general formula (V), and general formula (VI) And at least one nonionic additive selected from the group consisting of hydrophilic resins containing structural units represented by: Here, the compounds represented by the following general formula (II), general formula (III), and general formula (IV) are nonionic surfactants that can be used as nonionic additives, and the following general formula (V) and The compound represented by the general formula (VI) is a nonionic hydrophilic resin that can be used as a nonionic additive.

In general formula (II), each of R ¹ and R ² independently represents a hydrogen atom, an alkyl group having 6 to 30 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkylcarbonyl group, or polyoxyethylene. Represents a chain, and R ¹ and R ² may be bonded to each other.
a represents an integer of 1 to 10.

Specific examples of the alkyl group having 6 to 30 carbon atoms represented by R ¹ or R ² include a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, an icosyl group, and a triacontyl group. Among them, a dodecyl group, a tetradecyl group, a hexadecyl group, or an octadecyl group is preferable.

As the alkenyl group represented by R ¹ or R ² , those having 6 to 30 carbon atoms are preferable. Specifically, for example, a decel group, a dodecel group, a tetradecel group, a hexadecel group, an octadecel group, an icocel group, a triacontell Group, etc. are mentioned, and among these, a dodecel group, a tetradecel group, a hexadecel group, or an octadecel group is preferable.

Specific examples of the cycloalkyl group represented by R ¹ or R ² include a cyclohexyl group and an alkyl-substituted cyclohexyl group.

The alkylcarbonyl group represented by R ¹ or R ² is preferably an alkylcarbonyl group having 6 to 30 carbon atoms. Specifically, for example, a decylcarbonyl group, a dodecylcarbonyl group, a tetradecyldecylcarbonyl group, a hexadecyldecylcarbonyl group. Group, octadecyldecylcarbonyl group, icosyldecylcarbonyl group, triacontyldecylcarbonyl group, etc., among others, dodecyldecylcarbonyl group, tetradecyldecylcarbonyl group, hexadecyldecylcarbonyl group, or octadecyldecylcarbonyl group It is preferable that

Specific examples of the aryl group represented by R ¹ or R ² include a phenyl group and a naphthyl group. Among them, a phenyl group is preferable.

As the aralkyl group represented by R ¹ or R ² , those having 8 to 20 carbon atoms are preferred, and specific examples include a benzyl group.

The polyoxyethylene chain (EO chain) represented by R ¹ or R ² is preferably an EO chain having a molecular weight of 50 to 1,000, and more preferably an EO chain having a molecular weight of 50 to 500.

R ¹ and R ² may further have a substituent, and examples of the substituent that can be introduced include a hydroxy group, an amino group, a carboxyl group, a phosphate group, an imino group, a thiol group, a sulfo group, A nitro group etc. are mentioned.

  A in the general formula (II) is an integer of 1 to 10, more preferably an integer of 1 to 10 and more preferably an integer of 2 or more and 10 or less from the viewpoint of the stability of the polishing liquid. preferable.

  Preferred specific examples of the compound represented by the general formula (II) are shown below, but the compound represented by the general formula (II) that can be applied to the present invention is not limited thereto.

In general formula (III), R ³ represents an alkyl group having 1 to 20 carbon atoms, an alkynyl group, a cycloalkyl group, an aryl, or a group formed by combining two or more of these groups. b represents an integer of 1 to 10.

Specific examples of the alkyl group having 1 to 20 carbon atoms represented by R ³ include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a decyl group. , Dodecyl group, icosyl group, and the like. Among them, octyl group, decyl group, dodecyl group, hexyl, icosyl group are preferable.

The alkynyl group represented by R ³ is preferably an alkynyl group having 2 to 20 carbon atoms. Specifically, for example, ethynyl group, propynyl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octynyl group, decynyl Group, dodecinyl group, icosinyl group, etc., among which octyl group, decyl group, dodecyl group, hexyl, icosyl group, etc. are mentioned, among which octynyl group, decynyl group, dodecynyl group, hexynyl group, icosinyl group are preferable. .

As the cycloalkyl group represented by R ³ , those having 5 to 8 carbon atoms are preferable, and specific examples include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like. Of these, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group are preferable.

Specific examples of the aryl group represented by R ³ include a phenyl group and a naphthyl group. Among them, a phenyl group is preferable.

  B in the general formula (III) is an integer of 1 to 10, and is more preferably an integer of 1 to 10 and more preferably an integer of 2 or more and 10 or less from the viewpoint of the stability of the polishing liquid. preferable.

  Preferable specific examples of the compound represented by the general formula (III) are shown below, but the compound represented by the general formula (III) that can be applied to the present invention is not limited thereto.

In general formula (IV), R ⁴ represents an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, an arylene group, or an aralkylene group, and R ⁵ , R ⁶ , and R ⁷ are each independently a hydrogen atom. Represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, or an aralkyl group. R ⁸ represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or an aralkyl group. c represents an integer of 1 to 10. m represents an integer of 1 to 100, and n represents an integer of 1 to 100.

The alkylene group represented by R ⁴ is preferably an alkylene group having 2 to 20 carbon atoms. Specifically, for example, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene Group, decylene group, dodecylene group or icosylene group.
The alkenylene group represented by R ⁴ is preferably an alkenylene group having 2 to 20 carbon atoms, specifically, for example, ethenylene group, propenylene group, butenylene group, pentenylene group, hexenylene group, heptenylene group, octenylene group, decenylene group. Group, dodecenylene group, icosenylene group and the like.
The alkynylene group represented by R ³ is preferably one having 2 to 20 carbon atoms. Specifically, for example, ethynylene group, propynylene group, butynylene group, pentynylene group, hexynylene group, heptynylene group, octynylene group, decynylene group Group, dodecynylene group, icosinylene group and the like.
As the cycloalkylene group represented by R ⁴ , those having 5 to 8 carbon atoms are preferable, and specifically, for example, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, or a cyclooctylene group. Etc.
Specific examples of the arylene group represented by R ⁴ include a phenylene group and a naphthylene group.

The alkyl group represented by R ⁵ , R ⁶ , or R ⁷ is preferably an alkyl group having 1 to 20 carbon atoms, specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group. , Heptyl group, octyl group, decyl group, dodecyl group, hexyl group, icosyl group and the like.
The alkenyl group represented by R ⁵ , R ⁶ , or R ⁷ is preferably an alkenyl group having 2 to 20 carbon atoms. Specifically, for example, an ethenylene group, a propenylene group, a butenylene group, a pentenylene group, a hexenylene group, A heptenylene group, an octenylene group, a decenylene group, a dodecenylene group, an icosenylene group, or the like can be given.
The alkynyl group represented by R ⁵ , R ⁶ , or R ⁷ is preferably an alkynyl group having 2 to 20 carbon atoms. Specifically, for example, an ethynyl group, a propynyl group, a butynyl group, a pentynyl group, a hexynyl group, A heptynyl group, an octynyl group, a decynyl group, a dodecinyl group, an icosinyl group, etc. are mentioned, Among them, an octyl group, a decyl group, a dodecyl group, a hexyl, an icosyl group etc. are mentioned.
The cycloalkyl group represented by R ⁵ , R ⁶ , or R ⁷ is preferably one having 5 to 8 carbon atoms, and specifically, for example, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene. Group, a cyclooctylene group, or the like.
Specific examples of the aryl group represented by R ⁵ , R ⁶ , or R ⁷ include a phenyl group and a naphthyl group.
The aralkyl group represented by R ⁵ , R ⁶ , or R ⁷ is preferably an aralkyl group having 8 to 20 carbon atoms, and specifically includes, for example, a benzyl group.

As the alkyl group, alkenyl group, cycloalkyl group, aryl group or aralkyl group represented by R ⁸ , specifically, an alkyl group or alkenyl group represented by R ⁵ , R ⁶ or R ⁷ Specific examples of cycloalkyl group, aryl group, and aralkyl group include the groups described above.

  C in general formula (IV) is an integer of 1-100, and it is more preferable that it is an integer of 1-50.

  m represents 1-100, and it is more preferable that it is 1-20. n represents 1-100, and it is more preferable that it is 1-20.

  The molecular weight (Mw) of the compound represented by the general formula (IV) is preferably 1500 to 3000.

  Although the preferable specific example of a compound represented by general formula (IV) is shown below, the compound represented by general formula (IV) which can be applied to this invention is not limited to this.

In general formula (V), R ⁹ represents an alkylene group having 1 to 20 carbon atoms, an alkynylene group, a cycloalkylene group, an arylene group, or a group formed by combining two or more of these groups. pp represents an integer of 5 or more.

Specifically, the alkylene group having 1 to 20 carbon atoms represented by R ⁹ is preferably, for example, a methylene group or an ethylene group.
The alkynylene group represented by R ⁹ is preferably an alkynylene group having 2 to 20 carbon atoms, specifically, for example, ethynylene group, propynylene group, butynylene group, pentynylene group, hexynylene group, heptynylene group, octynylene group, decynylene group. Group, dodecynylene group, icosinylene group and the like.
As the cycloalkylene group represented by R ⁹ , those having 5 to 8 carbon atoms are preferable, and specifically, for example, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, and the like. Is mentioned.
Specific examples of the arylene group represented by R ⁹ include a phenylene group and a naphthylene group.
When R ⁹ is a group formed by combining two or more of the groups described above, specific examples of such groups include groups formed by combining the groups described above as examples of these groups.

R ⁹ may further have a substituent when it can be introduced.

  p is an integer of 5 or more, and from the viewpoint of dispersion stability, it is more preferably an integer of 5 to 10000, and more preferably an integer of 10 to 5000.

  The molecular weight (Mw) of the compound represented by the general formula (V) is preferably 200 to 200000, and more preferably 500 to 50000.

  Preferred specific examples of the hydrophilic resin containing the structural unit represented by the general formula (V) are shown below, but the hydrophilic resin containing the structural unit represented by the general formula (V) that can be applied to the present invention is as follows. However, it is not limited to these.

In General Formula (VI), R ¹⁰ represents an alkylene group having 1 to 20 carbon atoms, an alkynylene group, a cycloalkylene group, an arylene group, or a group formed by combining two or more of these groups. q represents an integer of 5 or more. * Represents a linking site with an adjacent structural unit.

The alkylene group having 1 to 20 carbon atoms represented by R ^10, specifically, for example, a methylene group or an ethylene group is preferred.
The alkynylene group represented by R ¹⁰ is preferably one having 2 to 20 carbon atoms. Specifically, for example, ethynylene group, propynylene group, butynylene group, pentynylene group, hexynylene group, heptynylene group, octynylene group, decynylene group, etc. Group, dodecynylene group, hexynylene group, icosinylene group, etc., among which octylene group, decylene group, dodecylene group, hexylene, icosinylene group, etc. are mentioned. Groups are preferred. .
As the cycloalkylene group represented by R ¹⁰ , those having 5 to 8 carbon atoms are preferable, and specifically, for example, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, and the like. Among them, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, and a cycloheptylene group are preferable.
Specific examples of the arylene group represented by R ¹⁰ include a phenylene group and a naphthylene group.
When R ¹⁰ is a group formed by combining two or more of the above-described groups, specific examples of such groups include groups formed by combining the above-described groups.

R ¹⁰ may further have a substituent when it can be introduced.

  p is an integer of 5 or more, and from the viewpoint of dispersion stability, it is more preferably an integer of 5 to 10000, and more preferably an integer of 10 to 5000.

  The molecular weight (Mw) of the compound represented by the general formula (VI) is preferably 200 to 200000, and more preferably 500 to 50000.

Preferable specific examples of the hydrophilic resin containing the structural unit represented by the general formula (VI)) are shown below, but the hydrophilic resin containing the structural unit represented by the general formula (VI)) that can be applied to the present invention. Is not limited to these.

  Only one type of nonionic additive contained in the polishing liquid may be used, or two or more types may be used in combination. Moreover, when using together 2 or more types of nonionic additives, either one of a nonionic surfactant and hydrophilic resin may be contained, and both may be contained.

  The total amount of the nonionic additive contained in the polishing liquid is preferably 0.0001% by mass to 1% by mass, and 0.001% by mass to 0.5% by mass with respect to the total mass of the polishing liquid when used for polishing. % Is more preferable, and 0.005 mass% to 0.5 mass% is still more preferable.

[Other ingredients]
(PH adjuster)
The polishing liquid of the present invention needs to have a pH of 1.5 to 7.0, and is preferably in the range of pH 1.5 to 5.0. The polishing liquid of the present invention exhibits an excellent effect when the pH is within this range.
In order to adjust the pH of the polishing liquid to the above range, an alkali / acid or a buffer is used.
Examples of alkali / acid or buffering agents include non-metallic alkaline agents such as organic ammonium hydroxides such as ammonia, ammonium hydroxide and tetramethylammonium hydroxide, alkanolamines such as diethanolamine, triethanolamine and triisopropanolamine. Alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, inorganic acids such as nitric acid, sulfuric acid and phosphoric acid, carbonates such as sodium carbonate, phosphates such as trisodium phosphate, boric acid Preferable examples include salts, tetraborate and hydroxybenzoate. Particularly preferred alkali agents are ammonium hydroxide, potassium hydroxide, lithium hydroxide and tetramethylammonium hydroxide.

  The addition amount of the alkali / acid or the buffer may be an amount that maintains the pH within a preferable range, and is preferably 0.0001 mol to 1.0 mol in 1 L of the polishing liquid when used for polishing. More preferably, it is 0.003 mol to 0.5 mol.

(Corrosion inhibitor)
The polishing liquid of the present invention contains a corrosion inhibitor that adsorbs to the surface to be polished to form a film and controls the corrosion of the metal surface. As a corrosion inhibitor in this invention, it is preferable to contain the hetero aromatic ring compound which has a 3 or more nitrogen atom in a molecule | numerator, and has a condensed ring structure. Here, the “three or more nitrogen atoms” are preferably atoms constituting a condensed ring. As such a heteroaromatic ring compound, benzotriazole and various substituents are introduced into the benzotriazole. It is preferable that the derivative is

  Corrosion inhibitors include benzotriazole, 1,2,3-benzotriazole, 5,6-dimethyl-1,2,3-benzotriazole, 1- (1,2-dicarboxyethyl) benzotriazole, 1- [ N, N-bis (hydroxyethyl) aminomethyl] benzotriazole, 1- (hydroxymethyl) benzotriazole and the like, among others, 1,2,3-benzotriazole, 5,6-dimethyl-1,2,3 -Benzotriazole, 1- (1,2-dicarboxyethyl) benzotriazole, 1- [N, N-bis (hydroxyethyl) aminomethyl] benzotriazole, and 1- (hydroxymethyl) benzotriazole More preferred.

  The addition amount of such a corrosion inhibitor is preferably 0.01% by mass to 0.2% by mass, and 0.05% by mass to 0.2% by mass with respect to the mass of the polishing liquid used for polishing. Is more preferable. That is, the addition amount of such a corrosion inhibitor is preferably 0.01% by mass or more from the viewpoint of not expanding dishing, and is preferably 0.2% by mass or less from the viewpoint of storage stability.

(Chelating agent)
The polishing liquid of the present invention preferably contains a chelating agent (that is, a hard water softening agent) as necessary in order to reduce adverse effects such as mixed polyvalent metal ions.
Chelating agents include general water softeners and related compounds that are calcium and magnesium precipitation inhibitors, such as nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-aminotrimethylenephosphone. Acid, ethylenediamine-N, N, N ′, N′-tetramethylenesulfonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, ethylenediamine disuccinic acid (SS form), N- (2-carboxylate ethyl) -L-aspartic acid, β-alanine diacetate, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N′-bis (2-hydroxy Benzyl) ethylenediamine -N, N'-diacetic acid, 1,2-dihydroxy-4,6-disulfonic acid.

Two or more chelating agents may be used in combination as necessary.
The addition amount of the chelating agent may be an amount sufficient to sequester metal ions such as mixed polyvalent metal ions, for example, 0.0003 mol to 0.07 mol in 1 L of a polishing liquid used for polishing. Add to be.

[Polishing target]
The polishing object to which the polishing liquid of the present invention is applied includes a group consisting of a first layer containing polysilicon or modified polysilicon, and silicon oxide, silicon nitride, silicon carbide, silicon carbonitride, silicon oxide carbide, and silicon oxynitride. And a second layer containing at least one selected from at least one kind. More specifically, it is preferably used when polysilicon or modified polysilicon is applied as an electrode material and a gate electrode is formed in a semiconductor integrated circuit by CMP.
The “modified polysilicon” in the present invention includes silicon obtained by doping polysilicon with an impurity element such as B or P.

Usually, when forming the gate electrode, a layer made of silicon oxide or the like is formed on the surface of the substrate, a recess is formed by etching or the like, and the formed recess is filled with polysilicon or modified polysilicon. Form. Next, the surface includes at least one selected from the group consisting of silicon oxide, silicon nitride, silicon carbide, silicon carbonitride, silicon oxide carbide, and silicon oxynitride for the purpose of polishing stop layer and etching stop layer. Laminate two layers.
In the CMP for forming the gate electrode, the polishing is started from the surface of the second layer, the polishing of the second layer proceeds, and when the surface of the first layer is exposed, the polishing rate is rapidly reduced to polish the second layer. Is detected, and overpolishing of the polysilicon or modified polysilicon surface used for the gate electrode is suppressed.
Thereafter, the gate electrode is formed by removing portions other than the polysilicon or modified polysilicon functioning as an electrode and the necessary silicon oxide layer in the periphery thereof by etching.

[Polishing method]
The polishing method of the present invention uses the polishing liquid of the present invention described above, and supplies the polishing pad to the polishing pad on the polishing surface plate, and rotates the polishing surface plate to remove the polishing pad from the object to be polished. Polishing is performed by making a relative movement while making contact with the surface to be polished.

  The polishing liquid of the present invention is 1. 1. A concentrated liquid which is diluted by adding water or an aqueous solution when used. 2. When each component is prepared in the form of an aqueous solution described in the next section, these are mixed, and if necessary diluted with water to make a working solution. It may be prepared as a working solution. In any of the polishing methods of the present invention, the polishing liquid in either case can be applied.

  As an apparatus used for polishing, a holder for holding an object to be polished (for example, a wafer on which a conductive material film is formed) having a surface to be polished and a polishing pad are attached (a motor capable of changing the number of rotations). Etc.) and a general polishing apparatus having a polishing surface plate. As the polishing pad, a general nonwoven fabric, foamed polyurethane, porous fluororesin, or the like can be used, and there is no particular limitation. The polishing conditions are not limited, but the rotation speed of the polishing surface plate is preferably a low rotation of 200 rpm or less so that the object to be polished does not pop out. The pressing pressure of the object to be polished having the surface to be polished (film to be polished) against the polishing pad is preferably 0.68 to 34.5 kPa, and the in-plane uniformity of the object to be polished at the polishing rate and the flatness of the pattern are preferable. In order to satisfy the properties, it is more preferably 3.40 to 20.7 kPa.

During polishing, the polishing liquid is continuously supplied to the polishing pad with a pump or the like.
After the polishing is finished, the object to be polished is thoroughly washed in running water, and then dried after removing water droplets adhering to the object to be polished using a spin dryer or the like.

In the present invention, the 1. When diluting the concentrated solution as in the above method, the following aqueous solutions can be used. The aqueous solution is water containing at least one of an organic acid, an additive, and a surfactant in advance, and the components contained in the aqueous solution and the components contained in the diluted concentrate And the component which totaled was made into the component of the polishing liquid (use liquid) used when grind | polishing.
Thus, when the concentrate is diluted with an aqueous solution and used, components that are difficult to dissolve can be added later in the form of an aqueous solution, so that a more concentrated concentrate can be prepared.

  In addition, as a method of diluting by adding water or an aqueous solution to the concentrated liquid, the pipe for supplying the concentrated polishing liquid and the pipe for supplying the water or the aqueous solution are joined together and mixed, and mixed and diluted. There is a method of supplying the used liquid to the polishing pad. Mixing of concentrated liquid with water or aqueous solution is a method in which liquids collide with each other through a narrow passage under pressure, filling the pipe with a filler such as a glass tube, and separating and separating the liquid flow. Ordinary methods such as a method of repeatedly performing and a method of providing a blade rotating with power in the pipe can be employed.

  The supply rate of the polishing liquid is preferably 10 to 1000 ml / min, and more preferably 170 to 800 ml / min in order to satisfy the in-surface uniformity of the polishing rate and the flatness of the pattern.

  Further, as a method of polishing while diluting the concentrated liquid with water or an aqueous solution, a pipe for supplying the polishing liquid and a pipe for supplying the water or the aqueous solution are provided independently, and a predetermined amount of liquid is respectively applied to the polishing pad. There is a method of supplying and polishing while mixing by the relative motion of the polishing pad and the surface to be polished. It is also possible to use a method in which a predetermined amount of concentrated liquid and water or an aqueous solution are mixed in one container and then the mixed polishing liquid is supplied to the polishing pad for polishing.

In addition, as another polishing method, the component to be contained in the polishing liquid is divided into at least two components, and when these are used, water or an aqueous solution is added and diluted and supplied to the polishing pad on the polishing platen Then, there is a method in which the surface to be polished and the polishing pad are moved relative to each other and brought into contact with the surface to be polished for polishing.
In addition, the additive having low solubility is divided into two components (A) and (B). For example, the additive and the surfactant are the components (A), and the organic acid, the additive, the surfactant, and Water is used as the component (B), and when they are used, water or an aqueous solution is added to dilute the component (A) and the component (B).

In the case of the above example, three pipes for supplying the component (A), the component (B), and water or an aqueous solution are required, and dilution mixing supplies the three pipes to the polishing pad. There is a method of connecting to one pipe and mixing in the pipe. In this case, it is possible to connect two pipes and then connect another pipe. Specifically, this is a method in which a constituent component containing an additive that is difficult to dissolve is mixed with another constituent component, a mixing path is lengthened to ensure a dissolution time, and then a water or aqueous solution pipe is further coupled. .
As described above, the other mixing methods are as follows. The three pipes are directly guided to the polishing pad and mixed by the relative movement of the polishing pad and the surface to be polished, or the three components are mixed in one container. There is a method of supplying diluted polishing liquid to the polishing pad from there.

  In the above polishing method, when one constituent component containing an oxidizing agent is made 40 ° C. or lower and the other constituent components are heated in the range of room temperature to 100 ° C., one constituent component and another constituent component are mixed. Alternatively, when diluting by adding water or an aqueous solution, the liquid temperature can be set to 40 ° C. or lower. This method is a preferable method for increasing the solubility of the raw material having a low solubility of the polishing liquid by utilizing the phenomenon that the solubility becomes high when the temperature is high.

  The raw materials in which the above other components are dissolved by heating in the range of room temperature to 100 ° C. are precipitated in the solution when the temperature is lowered. It is necessary to dissolve the raw material deposited by heating. For this purpose, there are provided means for heating and feeding the other constituents in which the raw material is dissolved, and means for stirring and feeding the liquid containing the precipitate, and heating and dissolving the piping. Can be adopted. When the temperature of one constituent component containing an oxidizing agent is increased to 40 ° C. or higher, the other constituent components that have been heated may be decomposed. When two components are mixed, it is preferable that the temperature be 40 ° C. or lower.

Thus, in the present invention, the components of the polishing liquid may be divided into two or more parts and supplied to the surface to be polished. In this case, it is preferable to divide and supply the component containing an oxide and the component containing an organic acid. Alternatively, the polishing liquid may be a concentrated liquid and supplied to the surface to be polished separately from the dilution water.
In the present invention, in the present invention, when applying a method of dividing the polishing liquid components into two or more parts and supplying them to the surface to be polished, the supply amount represents the total supply amount from each pipe. It is.

〔pad〕
The polishing pad for polishing applicable to the polishing method of the present invention may be a non-foamed structure pad or a foamed structure pad. The former uses a hard synthetic resin bulk material like a plastic plate for a pad. Further, the latter further includes three types of a closed foam (dry foam system), a continuous foam (wet foam system), and a two-layer composite (laminated system), and a two-layer composite (laminated system) is particularly preferable. Foaming may be uniform or non-uniform.
Further, it may be one containing abrasive grains generally used for polishing (for example, ceria, silica, alumina, resin, etc.). In addition, the hardness may be either soft or hard, and either may be used. In the laminated system, it is preferable to use a different hardness for each layer. As the material, non-woven fabric, artificial leather, polyamide, polyurethane, polyester, polycarbonate and the like are preferable. Further, the surface contacting the surface to be polished may be subjected to processing such as lattice grooves / holes / concentric grooves / helical grooves.

[Wafer]
In the present invention, a wafer as an object to be subjected to CMP with the polishing liquid preferably has a diameter of 200 mm or more, particularly preferably 300 mm or more. The effect of the present invention is remarkably exhibited when the thickness is 300 mm or more.

[Polishing equipment]
An apparatus capable of performing polishing using the polishing liquid of the present invention is not particularly limited, but MA-300D (Musashino Electronics Co., Ltd.), Mira Mesa CMP, Reflexion CMP (Applied Materials), FREX200, FREX300 (Hagiwara Seisakusho) , NPS3301, NPS2301 (Nikon), A-FP-310A, A-FP-210A (Tokyo Seimitsu), 2300 TERES (Ram Research), Momentum (Speedfam IPEC), and the like.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof.

[Examples 1-1 to 1-4, Comparative Examples 1-1 to 1-2]
<Preparation of polishing liquid>
Each polishing liquid (the polishing liquid of Examples 1-1 to 1-4 and the polishing liquid of Comparative Examples 1-1 to 1-2) having the composition and pH shown below was prepared.
-Polishing liquid composition-
Colloidal silica particles: A1 200 g / L
・ Organic acid: Citric acid 0.5g / L
Nonionic surfactant: D9 0.05 g / L
Add pure water to make a total of 1,000mL
pH (adjusted with aqueous ammonia and nitric acid) pH shown in Table 2

  In addition, in each Example in this specification, the shape and particle size of the colloidal silica particles (A1 to A5) used as abrasive grains are as shown in Table 1 below.

[Evaluation]
CMP was performed using each polishing solution, and polishing evaluation was performed on the pH dependence of the polishing rate in polishing the polysilicon layer (p-Si layer). The evaluation method is as follows.

<Evaluation method>
-Polishing device-
Using the apparatus “MA-300D” manufactured by Musashino Electronics Co., Ltd. as a polishing apparatus, the wafer shown below was polished as an object to be polished while supplying slurry under the following conditions.
Table rotation speed: 112 rpm
Head rotation speed: 113 rpm
Polishing pressure: 18.4kPa
Polishing pad: Rodel Nitta Co., Ltd. IC1400 XY-K-Pad
Polishing liquid supply speed: 50 ml / min

-Polishing object-
As an object to be polished, a cut wafer obtained by cutting an 8-inch wafer having a polysilicon layer formed on a Si substrate into 6 cm × 6 cm was used.

-Polishing speed-
The polishing rate was calculated from the following formula by measuring the layer thickness (nm) before and after polishing of the polysilicon layer (p-Si layer).
Polishing rate (nm / min) = (layer thickness before polishing−layer thickness after polishing) / polishing time The layer thickness was measured with a non-contact type film thickness meter FE-33 (manufactured by Otsuka Electronics).
The obtained results are shown in Table 2. In addition, the graph which shows the pH dependence of the grinding | polishing speed | rate (nm / mim) at the time of implementing CMP using each polishing liquid of Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-4. It was shown in FIG.

  As shown in Table 2, the polishing liquids of Examples 1-1 to 1-4, which are the polishing liquids of the present invention, have a significantly reduced polishing rate for the polysilicon layer, while the pH of the polishing liquid of the present invention is low. It was confirmed that the polishing liquids of Comparative Examples 1-1 to 1-4, which were outside the range of the liquid, increased the polishing rate for the polysilicon layer in comparison with the polishing liquids of the respective examples. From this, it was confirmed that the pH of the polishing liquid of the present invention is in the range of 1.5 to 7 from the viewpoint of specific polishing suppression for the polysilicon layer.

[Example 2-1]
<Preparation of polishing liquid>
A polishing liquid (polishing liquid of Example 2-1) having the composition and pH shown below was prepared.
-Polishing liquid composition-
Colloidal silica particles: A1 200 g / L
・ Organic acid: Citric acid 0.5g / L
Nonionic additive: D1 0.10 g / L
Add pure water to make a total of 1.000mL
pH (adjusted with ammonia water and nitric acid) 2.0

[Evaluation]
Polishing evaluation was performed using the polishing liquid of Example 2.
<Evaluation method>
-Polishing device-
A device “MA-300D” manufactured by Musashino Electronics Co., Ltd. was used as a polishing apparatus, and the wafer shown below was polished as a polishing target while supplying slurry under the following conditions.
Table rotation speed: 112 rpm
Head rotation speed: 113 rpm
Polishing pressure: 18.4kPa
Polishing pad: Rodel Nitta Co., Ltd. IC1400 XY-K-Pad
Polishing liquid supply speed: 50 ml / min

-Polishing object-
As an object to be polished, an 8-inch wafer in which a polysilicon layer (p-Si layer), a silicon oxide layer (SiO ₂ layer), and a silicon nitride layer (Si ₃ N ₄ layer) are formed on a Si substrate, A cut wafer cut to 6 cm × 6 cm was used.

-Polishing rate, polishing rate ratio-
The polishing rate was measured for the thickness (nm) of the polysilicon layer (p-Si layer), silicon oxide layer (SiO ₂ layer), and silicon nitride layer (Si ₃ N ₄ layer) before and after polishing, It was calculated by the following formula. The layer thickness was measured with a non-contact film thickness measuring device FE-33 (manufactured by Otsuka Electronics).
Polishing rate (nm / min) = (layer thickness before polishing−layer thickness after polishing) / polishing time Also, for the polishing rate ratio represented by RR (other) / RR (p-Si), p-Si layer And SiO ₂ layer, p-Si layer and Si ₃ N ₄ layer.
The obtained results are shown in Table 3.

[Examples 2-1 to 2-19, Comparative examples 2-1 to 2-4]
In the preparation of the polishing liquid of Example 2-1, except that colloidal silica particles (polishing particles), nonionic additives, and organic acids were changed to the components shown in Table 3 below, and the pH was changed as shown in Table 3. Prepared each polishing liquid of Examples 2-1 to 2-19 and Comparative Examples 2-1 to 2-4 in the same manner as in Example 2-1.
For each of the polishing liquids of Examples 2-1 to 2-19 and Comparative Examples 2-1 to 2-4, the polishing rate and the polishing rate ratio were evaluated in the same manner as in Example 2-1, and the evaluation results were shown. It was shown in 3.
The colloidal silica particles A1 to A5 used as the abrasive grains are as shown in Table 1 above.

As shown in Table 3, each polishing liquid of the example is a layer containing a silicon-based material other than the polysilicon layer (p-Si layer) when used for CMP in comparison with each polishing liquid of the comparative example. It has been found that the polishing rate is rapid for (SiO ₂ layer, Si ₃ N ₄ layer) and polishing of the polysilicon layer is selectively suppressed.

It is a graph which shows the pH dependence of the polishing rate with respect to the p-Si layer by the polishing liquid of an Example.

Claims (10)

A first layer containing polysilicon or modified polysilicon and a group consisting of silicon oxide, silicon nitride, silicon carbide, silicon carbonitride, silicon oxide carbide, and silicon oxynitride in a planarization step in manufacturing a semiconductor integrated circuit And a second layer containing at least one selected from the above, and used for chemical mechanical polishing of an object to be polished, which is represented by the following (1), (2) and (3) A polishing liquid comprising each component, having a pH of 1.5 to 7.0, and capable of selectively polishing the second layer with respect to the first layer.
(1) Colloidal silica particles (2) Organic acid (3) Nonionic surfactant and at least one nonionic additive selected from nonionic hydrophilic resins   A polishing rate represented by RR (other) / RR (p-Si) where the polishing rate of the first layer is RR (p-Si) and the polishing rate of the second layer is RR (other). The polishing liquid according to claim 1, wherein the object to be polished can be polished within a range of 1.5 to 200.   The polishing liquid according to claim 1 or 2, wherein the concentration of the colloidal silica is 0.1 mass% to 10 mass% with respect to the total mass of the polishing liquid.   4. The colloidal silica according to claim 1, wherein the colloidal silica has an average primary particle size of 5 nm to 100 nm and an average secondary particle size of 10 nm to 300 nm. Polishing fluid.   The polishing liquid according to any one of claims 1 to 4, wherein the organic acid is an organic acid containing at least one carboxyl group in its molecular structure. The polishing liquid according to any one of claims 1 to 5, wherein the organic acid is a compound represented by the following general formula (I).

[In General Formula (I), R represents an alkylene group having 1 to 20 carbon atoms, an alkynylene group, a cycloalkylene group, an arylene group, or a group formed by combining two or more of these groups. These groups may be further substituted with other functional groups. ]   7. The polishing liquid according to claim 1, wherein the concentration of the organic acid is 0.001 to 3% by mass with respect to the total mass of the polishing liquid. The nonionic additive is a nonionic surfactant represented by the following general formula (II), a nonionic surfactant represented by the general formula (III), or a nonionic interface represented by the general formula (IV) At least one selected from the group consisting of an activator, a hydrophilic resin containing a structural unit represented by general formula (V), and a hydrophilic resin containing a structural unit represented by general formula (VI) It is a seed | species nonionic additive, The polishing liquid of any one of Claims 1-7 characterized by the above-mentioned.

[In General Formula (II), each of R ¹ and R ² independently represents a hydrogen atom, an alkyl group having 6 to 30 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkylcarbonyl group, or a polyalkyl group. Represents an oxyethylene chain, and R ¹ and R ² may be bonded to each other; a represents an integer of 1 to 10. ]

[In General Formula (III), R ³ represents an alkyl group having 6 to 20 carbon atoms, an alkynyl group, a cycloalkyl group, an aryl group, or a group formed by combining two or more of these groups. b represents an integer of 1 to 10. ]

[In General Formula (IV), R ⁴ represents an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, an arylene group, or an aralkylene group, and R ⁵ , R ⁶ , and R ⁷ are each independently hydrogen. An atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, or an aralkyl group is represented. R ⁸ represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or an aralkyl group. c represents an integer of 1 to 10. m represents an integer of 1 to 100, and n represents an integer of 1 to 100. ]

[In General Formula (V), R ⁹ represents an alkylene group having 1 to 20 carbon atoms, an alkynylene group, a cycloalkylene group, an arylene group, or a group formed by combining two or more of these groups. p represents an integer of 5 or more. ]

[In General Formula (VI), R ¹⁰ represents an alkylene group having 1 to 20 carbon atoms, an alkynylene group, a cycloalkylene group, an arylene group, or a group formed by combining two or more of these groups.
q represents an integer of 5 or more. ]   The polishing liquid according to claim 1, wherein a concentration of the nonionic additive is 0.001% by mass to 1% by mass with respect to a total mass of the polishing liquid.   The polishing liquid according to any one of claims 1 to 9 is supplied to a polishing pad on a polishing surface plate, and the polishing pad is rotated to rotate the polishing surface plate. A polishing method, wherein polishing is performed by making a relative movement while being in contact with a surface.

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