JP2023072896A - Additive for chemical mechanical polishing and method for producing the same, and polishing liquid composition - Google Patents

Abstract

To provide an additive for chemical mechanical polishing which has high polishing speed of a projection and can reduce dishing on an uneven surface of a polishing object.SOLUTION: In a copolymer of an additive, a content of a structural unit represented by formula (1) is 50-99 mass% of the whole copolymer. Formula (1): CH2=CR1-C(=O)O-(LO)n-R2. In the formula (1), R1 is a hydrogen atom or a methyl group, R2 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, L is an alkylene group having 4 or less carbon atoms, and n is 3-150, and a content of a structural unit represented by formula (2) is 1-50 mass%. Formula (2): CH2=CR1-C(=O)NR3R4. In the formula (2), R1 is a hydrogen atom or a methyl group, R3 and R4 are each independently a hydrogen atom or a monovalent hydrocarbon group, or R3 and R4 are bonded to each other to form a ring together with a nitrogen atom to which R3 and R4 are bonded, and the total of the carbon atoms of R3 and R4 is 1-12.SELECTED DRAWING: None

Description

The present invention relates to an additive for chemical mechanical polishing, a method for producing the same, and a polishing composition. More specifically, the present invention relates to an additive for chemical mechanical polishing (CMP), which is important in the manufacturing process of semiconductor devices and the like, and a method for producing the same. and a polishing composition.

Semiconductor devices are used in almost all electronic devices around us, such as information communication devices and home electric appliances, and have become indispensable to modern life. In recent years, the role played by semiconductor devices has become even greater due to the spread of IoT, utilization of cloud computing, and the like. Although high integration and large capacity of semiconductor chips have been achieved at a remarkable speed so far, the demand for high performance continues, and the importance of microfabrication technology is increasing more and more. In particular, chemical mechanical polishing (CMP) technology is extremely important in realizing high-precision multilayer wiring formation. Used frequently.
In CMP, a polishing liquid is used to improve the polishing speed and processing accuracy. The polishing liquid generally contains abrasive grains, a polishing accelerator, a water-soluble polymer, a surfactant, and the like. Among these, water-soluble polymers, surfactants, and the like are added to the polishing liquid for the purpose of improving the flatness of the object to be polished and suppressing surface defects. It also has an effect of contributing to suppression of excessive polishing action. However, if the adsorption to the polishing film is too strong, there is a problem that a sufficient polishing rate cannot be obtained.

JP-A-2000-017195 Japanese Patent Application Laid-Open No. 2007-318072 WO2009/104334

Patent Document 1 discloses a polishing composition containing a copolymer of an ammonium acrylate salt and methyl acrylate and cerium oxide particles. It is said that the use of this polishing liquid composition improves the flatness of the polished surface as compared with the case of using a polishing liquid that does not contain an acrylic copolymer. However, its flatness is not sufficient. For example, when the above-mentioned polishing liquid composition is used for polishing a polishing film having an uneven surface, not only the convex portions but also the concave portions are polished at the same time. A bending phenomenon occurs. This phenomenon is called dishing, and there is a problem that it tends to occur when the ratio of the total area of the concave portions that can be seen when the concave-convex surface is viewed from above is large.
In order to suppress dishing as described above and obtain a highly flat polished surface, Patent Document 2 discloses a polishing liquid composition containing dihydroxyethylglycine and polyoxyalkylene alkyl ether as additives as a polishing liquid composition containing ceria particles. Liquid compositions have been proposed. It is proposed that the two compounds adsorb to the abrasive grains and the polishing film respectively, protect the concave portions of the polishing film, prevent excessive polishing, and obtain a flat surface. Adsorption to the polishing film is weak, and the protective effect is not sufficient.
Patent Document 3 proposes a graft polymer containing an anionic functional group in the trunk polymer and polyalkylene glycol in the branches as a copper dishing reducing agent. It is proposed that the anionic functional group of the stem adsorbs to the copper surface and adjusts the polishing speed, resulting in a smooth surface.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a chemical mechanical polishing method capable of polishing convex portions (oxide films) at a sufficiently high rate and significantly reducing dishing on an uneven surface to be polished. The object of the present invention is to provide an additive for polishing, a method for producing the same, and a polishing composition.

As a result of intensive studies aimed at solving the above problems, the present inventors have found that the above problems can be solved by using an additive containing a polymer having a specific structural unit. The present invention has been completed based on this finding. According to this specification, the following means are provided.

[1] A chemical mechanical polishing additive containing a copolymer (P),
In the copolymer (P), the content of structural units derived from a vinyl monomer represented by the following formula (1) is 50 to 99% by mass of the entire copolymer P,
CH2=CR ¹ -C(=O)O-(LO)n-R ² (1)
(In formula (1), R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and L is an alkylene group having 4 or less carbon atoms. and n is an integer from 3 to 150.)
An additive characterized in that the content of structural units derived from a vinyl monomer represented by the following formula (2) is 1 to 50% by mass of the entire copolymer (P).
CH2=CR ¹ -C(=O)NR ³ R ⁴ (2)
(In formula (2), R ¹ is a hydrogen atom or a methyl group. R ³ and R ⁴ are each independently a hydrogen atom or a monovalent hydrocarbon group, or R ³ and R ⁴ is a group that bonds with each other to form a ring together with the nitrogen atom to which R ³ and R ⁴ bond, and the total number of carbon atoms of R ³ and R ⁴ is 1 to 12.)
[2] The additive according to [1] above, wherein the polymer (P) has a number average molecular weight (Mn) of 1,000 to 100,000.
[3] Among the structural units contained in the copolymer (P), a unit containing a carboxylic acid group, a phosphoric acid group, a phosphonic acid group, a sulfuric acid group, a sulfonic acid group, and/or a salt thereof as a functional group The additive according to any one of [1] to [3], wherein the total content of structural units derived from the polymer is 0 to 0.6% by mass based on the total copolymer (P). .
[4] The vinyl monomer represented by the above formula (2) is a monomer having an SP value of 17 to 25 (J/cm ³ ) ^0.5 calculated by the Fedors estimation method [1] to [ 3] The additive according to any one of the above items.
[5] The copolymer (P) has a molecular weight dispersity (Mw/Mn) represented by the ratio of the number average molecular weight Mn to the weight average molecular weight Mw of 2.0 or less [1] to [4] The additive according to any one of.
[6] The additive according to any one of [1] to [5], wherein the polymer (P) is a block polymer.
[7] The copolymer (P) contains a polymer block A and a polymer block B,
The polymer block A has a structural unit derived from the vinyl monomer represented by the formula (1),
The additive according to any one of [1] to [6], wherein the polymer block B has a structural unit UB derived from the vinyl monomer represented by the formula (2).
[8] The ratio (A/B) between the polymer block A and the polymer block B in the polymer (P) is 50/50 to 99.9/0.1 in mass ratio, [7 ] The additive as described in .
[9] A polishing liquid composition for chemical mechanical polishing used for planarizing the surface of at least one of an insulating layer and a wiring layer, the additive according to any one of [1] to [8] and cerium oxide and/or silica.
[10] A method for producing an additive for a chemical mechanical polishing liquid containing a copolymer, comprising:
In the copolymer, the content of structural units derived from a vinyl monomer represented by the following formula (1) is 50 to 99% by mass of the entire copolymer,
CH2=CR ¹ -C(=O)O-(LO)n-R ² (1)
(In formula (1), R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and L is an alkylene group having 4 or less carbon atoms. and n is an integer from 3 to 150.)
And the content of the structural unit derived from the vinyl monomer represented by the following formula (2) is 1 to 50% by mass of the entire copolymer (P), the copolymer is prepared by a living radical polymerization method. A manufacturing method characterized by passing through a process of manufacturing by.
CH2=CR ¹ -C(=O)NR ³ R ⁴ (2)
(In Formula (2), R ¹ is a hydrogen atom or a methyl group. R ³ and R ⁴ are each independently a hydrogen atom or a monovalent hydrocarbon group, or R ³ and R ⁴ is a group that bonds with each other to form a ring together with the nitrogen atom to which R ³ and R ⁴ bond, and the total number of carbon atoms of R ³ and R ⁴ is 1 to 12.)

ADVANTAGE OF THE INVENTION According to the present invention, it is possible to provide an additive for chemical mechanical polishing capable of polishing a convex portion (oxide film) at a sufficiently high rate and significantly reducing dishing on an uneven surface to be polished. Further, it is possible to provide a polishing composition containing the additive and cerium oxide and/or silica. Furthermore, it is possible to provide a method for producing a chemical mechanical polishing liquid additive containing a copolymer.

The present invention will be described in detail below. In this specification, "(meth)acryl" means acryl and/or methacryl, and "(meth)acrylate" means acrylate and/or methacrylate. A "(meth)acryloyl group" means an acryloyl group and/or a methacryloyl group.

According to the present invention, an additive for chemical mechanical polishing capable of sufficiently increasing the polishing rate of convex portions (oxide film) on an uneven surface to be polished and significantly reducing dishing, and the additive and oxidation A polishing composition containing cerium and/or silica is provided. Furthermore, a method for producing a chemical mechanical polishing liquid additive containing a copolymer is provided.
The additive for chemical mechanical polishing provided by the present invention, the method for producing the water-soluble polymer for polishing liquid additive, and the method for producing the additive for chemical mechanical polishing liquid containing the copolymer are described in detail below. do.

≪Additives for chemical mechanical polishing≫
The chemical mechanical polishing additive provided by the present invention is a chemical mechanical polishing additive containing a copolymer (P),
In the copolymer (P), the content of structural units derived from a vinyl monomer represented by the following formula (1) is 50 to 99% by mass of the entire copolymer P,
CH2=CR ¹ -C(=O)O-(LO)n-R ² (1)
(In formula (1), R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and L is an alkylene group having 4 or less carbon atoms. and n is an integer from 3 to 150.)
Further, the content of the structural unit derived from the vinyl monomer represented by the following formula (2) is 1 to 50% by mass of the entire copolymer (P). .
CH2=CR ¹ -C(=O)NR ³ R ⁴ (2)
(In formula (2), R ¹ is a hydrogen atom or a methyl group. R ³ and R ⁴ are each independently a hydrogen atom or a monovalent hydrocarbon group, or R ³ and R ⁴ is a group that bonds with each other to form a ring together with the nitrogen atom to which R ³ and R ⁴ bond, and the total number of carbon atoms of R ³ and R ⁴ is 1 to 12.)

<Copolymer (P)>
In the copolymer (P) used in the present invention, the content of structural units derived from the vinyl monomer represented by the formula (1) is 50 to 99% by mass of the total copolymer (P). and the content of the structural unit derived from the vinyl monomer represented by the formula (2) is 1 to 50% by mass of the entire copolymer (P), It is a coalescence.
L in the formula (1) includes a methylene group, an ethylene group, a -CHMe- group, an n-propylene group, a -CHEt- group, a -CHMeCH2- group, a -CH2CHMe- group, an n-butylene group, -CH(n -Pr)- group, -CH(i-Pr)- group, -CHEtCH2- group, -CH2CHEt- group, -CHMeCH2CH2- group, -CH2CHMeCH2- group, -CH2CH2CHMe- group, etc., and 2 of these A mixture of more than one species may also be used. Ethylene group, -CHMeCH2- group, or -CH2CHMe- group is preferable, and ethylene group is more preferable, considering the ease of industrial raw material availability and the solubility in water of the copolymer (P). is.

n in the formula (1) is an arbitrary integer from 3 to 150. Considering that the -(LO)nR group contained in the copolymer (P) participates in the reduction of dishing by adsorption to the oxide film, protection of the oxide film, and high responsiveness to changes in the polishing pressure. , n is preferably 100 or less, more preferably 50 or less, still more preferably 30 or less, and even more preferably 15 or less. The lower limit of n is preferably 4 or more, more preferably 5 or more, even more preferably 6 or more, and even more preferably 7 or more. A preferred range of n can be indicated by arbitrarily combining the numerical values exemplified for the upper and lower limits above.
When L is composed of only one type of group, n is any integer within the above range. On the other hand, when L is composed of two groups, the -(LO)n-R group can be represented as -(L ¹ O)n ¹ -(L ² O)n ² -R group. In this case, the sum of ⁿ¹ and ⁿ² is an arbitrary integer within the above range. A similar consideration can be given to the case where the L is composed of three or more groups.

R2 in the formula (1) is a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms. Examples of monovalent hydrocarbon groups having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group and tert-butyl group. etc. are exemplified. Considering the availability of industrial raw materials and the solubility of the copolymer (P) in water, R2 in the formula (1) is preferably a hydrogen atom or a methyl group, more preferably a methyl group. .

Although the details of the method for producing the copolymer (P) will be described later, for example, by polymerizing the monomer represented by the above formula (1) and the monomer represented by the above formula (2), the above A copolymer (P) can be produced.

Specific examples of the monomer represented by the formula (1) that can be used in the present invention include polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polytetramethylene glycol mono(meth) Acrylates, poly(ethylene glycol-propylene glycol) mono(meth)acrylate, poly(ethylene glycol-tetramethylene glycol) mono(meth)acrylate, poly(ethylene glycol-propylene glycol-tetramethylene glycol) mono(meth)acrylate, mono Methoxypolyethylene glycol mono(meth)acrylate, monomethoxypolypropylene glycol mono(meth)acrylate, monomethoxypolytetramethylene glycol mono(meth)acrylate, monomethoxypoly(ethylene glycol-propylene glycol) mono(meth)acrylate, monomethoxypoly (Ethylene glycol-tetramethylene glycol) mono (meth) acrylate, monomethoxypoly (ethylene glycol-propylene glycol-tetramethylene glycol) mono (meth) acrylate, mono ethoxy polyethylene glycol mono (meth) acrylate, mono n-propoxy polyethylene glycol Mono (meth)acrylate, mono i-propoxy polyethylene glycol mono (meth) acrylate, mono n-butoxy polyethylene glycol mono (meth) acrylate, mono t-butoxy polyethylene glycol mono (meth) acrylate and the like can be exemplified. Among these, polyethylene glycol mono(meth)acrylate and monomethoxypolyethylene glycol mono(meth)acrylate are preferable, polyethylene glycol monoacrylate and monomethoxypolyethylene glycol monoacrylate are more preferable, and monomethoxypolyethylene glycol monoacrylate is more preferable. .
One type of these monomers may be used, or a plurality of types may be used in combination.
In addition, as commercial products, NOF Corporation Blenmer AE series, AME series, AP series, PE series, PME series, PP series, 50PEP series, Shin-Nakamura Chemical Industry Co., Ltd. AM series, and Kyoeisha Chemical Examples include Light Acrylate MTG-A and Light Acrylate 130A manufactured by Co., Ltd.

Examples of the monomer represented by formula (2) include tert-butyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, ) Acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, (meth)acrylamide derivatives such as (meth)acryloylmorpholine, N-vinylamide units such as N-vinylacetamide, N-vinylformamide, N-vinylisobutyramide mers, etc., and one or more of these can be used. Among these are tert-butyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide ) acrylamide and (meth)acrylamide derivatives such as (meth)acryloylmorpholine are preferred. Furthermore, ^the SP value calculated by the Fedors estimation method (see pages 147-154 of Polymer Engineering & Science, Vol. 14, No. 2, published in 1974) is 17 to 25 (J/cm ³ ) A monomer is more preferred, and a monomer of 18 to 21.8 (J/cm ³ ) ^0.5 is even more preferred. Specifically, tert-butylacrylamide and N-isopropylacrylamide are particularly preferred.

The polydispersity index (PDI) represented by weight average molecular weight (Mw)/number average molecular weight (Mn) of the copolymer (P) is 2.0 or less. It is believed that the size of the molecular weight of a polymer that has a dispersing function for abrasive grains affects the rate of adsorption and desorption to and from the object to be polished. Conceivable. Further, it is considered that a polymer having a large molecular weight tends to form an aggregated structure of abrasive grains due to shearing force. Therefore, it is preferable that the polymer having the function of dispersing abrasive grains has a narrow molecular weight distribution. From this point of view, the PDI of the copolymer (P) is preferably 1.8 or less, more preferably 1.5 or less, even more preferably 1.3 or less, and still more preferably 1.3. 2 or less. The lower limit of PDI is typically 1.0. In addition, in this specification, the number average molecular weight (Mn) and weight average molecular weight (Mw) of a polymer are values measured by gel permeation chromatography (GPC) in terms of polystyrene. Details of the molecular weight measurement are described in the Examples section.

The copolymer (P) preferably has a number average molecular weight (Mn) of 1,000 to 100,000. An Mn of 1,000 or more is preferable because it is possible to suppress a decrease in the polishing rate while sufficiently ensuring the wettability of the surface of the object to be polished. Further, when Mn is 100,000 or less, aggregation of abrasive grains due to shear force can be sufficiently suppressed, and the occurrence of defects such as scratches during polishing can be sufficiently suppressed, which is preferable. From such a viewpoint, Mn of the copolymer (P) is more preferably 1,500 or more, still more preferably 2,000 or more, and still more preferably 2,500 or more. The upper limit of Mn of the copolymer (P) is more preferably 60,000 or less, still more preferably 30,000 or less, still more preferably 10,000 or less, and even more preferably 6,000 or less. A preferred range of the number average molecular weight can be shown by arbitrarily combining the numerical values exemplified for the above upper and lower limits.

The content of structural units derived from the monomer represented by formula (1) is 50% by mass or more relative to the entire copolymer (P). It is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 85% by mass or more, still more preferably 90% by mass or more, and even more preferably 93% by mass or more. The upper limit is 100% by mass, preferably 99% by mass or less, more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 96% by mass or less. A preferred range can be indicated by arbitrarily combining the numerical values exemplified for the above upper and lower limits.
When the content of the structural unit derived from the monomer represented by the formula (1) is within the above range, the responsiveness to changes in the polishing pressure is high, and when the oxide film is a convex portion (high polishing pressure However, when polishing progresses and the nitride film is exposed and the object to be polished becomes a concave portion (polishing pressure is low), it adheres to the interface of the oxide film and suppresses excessive polishing. tend to These effects make it easier to obtain a good polished surface with reduced dishing without lowering the polishing rate.

The content of structural units derived from the monomer represented by formula (2) is 1% by mass or more relative to the entire copolymer (P). It is preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 4% by mass or more, and even more preferably 5% by mass or more. Also, the upper limit is preferably 50% by mass or less. More preferably 20% by mass or less, still more preferably 15% by mass or less, still more preferably 10% by mass or less, and even more preferably 7% by mass or less. A preferred range can be expressed by any combination of the above lower and upper limits.
When the content of the structural unit derived from the monomer represented by the formula (2) with respect to the entire copolymer (P) is within the above range, it is easy to obtain a good polished surface with reduced dishing. Become.

The anionic (co)polymer is adsorbed on the surface of the nitride film, which is usually positively charged, so that the selectivity of polishing the oxide film on the protrusions is increased, resulting in a flat surface. However, when the nitride film is exposed and nearing the end of polishing, the polishing rate of the oxide film increases, which may cause dishing. In addition, an anionic additive may change the stability of the polishing liquid composition due to a change in pH, and may cause polishing scratches due to coarsening of abrasive grains. In consideration of these points, monomers containing carboxylic acid groups, phosphoric acid groups, phosphonic acid groups, sulfuric acid groups, sulfonic acid groups, and / or salts thereof as functional groups for the entire copolymer (P) The total content of structural units derived from the body is preferably 0 to 0.6% by mass. More preferably 0 to 0.5% by mass, still more preferably 0 to 0.4% by mass, still more preferably 0 to 0.3% by mass, still more preferably 0 to 0.2% by mass.

The copolymer (P) may contain other copolymerizable monomers as structural units in addition to the monomer represented by the formula (1) or the formula (2).
Specific examples thereof include vinyl esters such as vinyl acetate and vinyl propionate: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. , n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, amyl (meth)acrylate, n-hexyl (meth)acrylate , n-octyl (meth)acrylate, ethylhexyl (meth)acrylate, and n-decyl (meth)acrylate (meth)acrylic acid alkyl esters; cyclohexyl (meth)acrylate, methyl (meth)acrylate Cyclohexyl, tert-butylcyclohexyl (meth)acrylate, cyclododecyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentenyl (meth)acrylate and dicyclo(meth)acrylate Aliphatic cyclic esters of (meth)acrylic acid such as pentanyl; phenyl methacrylate, benzyl (meth)acrylate, phenoxymethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate and (meth)acryl Aromatic esters of (meth)acrylic acid such as 3-phenoxypropyl acid; 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate ( Hydroxyalkyl meth)acrylates; N-[2-(methylamino)ethyl](meth)acrylate, N-[2-(dimethylamino)ethyl](meth)acrylate, N-[2-(ethylamino)ethyl ] (meth)acrylate and (di)alkylaminoalkyl (meth)acrylates such as N-[2-(diethylamino)ethyl](meth)acrylate; glycidyl (meth)acrylate, glycidyl 4-hydroxybutyl (meth)acrylate Ether and epoxy group-containing (meth)acrylic acid esters such as 3,4-epoxycyclohexylmethyl (meth)acrylate; 2-methoxyethyl (meth)acrylate, 2-(2-methoxyethoxy)ethyl (meth)acrylate, methoxy Alkoxyalkyl (meth)acrylates such as dipropylene glycol (meth)acrylate; etc. Methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, n-hexyl vinyl ether, 2 - alkyl vinyl ethers such as ethylhexyl vinyl ether, n-octyl vinyl ether, n-nonyl vinyl ether, and n-decyl vinyl ether; vinyl alcohols such as vinyl alcohol, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether; styrene , vinyltoluene, and vinylxylene; α-olefins such as ethylene, propylene, butylene, N-[2-[2-(2-methoxyethoxy)ethoxy]ethyl](meth)acrylamide, 1 -[(meth)acryloylamino]-3,6,9,12,15,18,21-heptaoxadocosane, (meth)acrylamide and the like can be mentioned, respectively. As other copolymerizable monomers, one or more of these may be used in combination.
The content of the structural unit derived from the other copolymerizable monomer is preferably 10% by mass or less with respect to the entire copolymer (P). It may be 8% by mass or less, 5% by mass or less, 3% by mass or less, or 1% by mass or less.

The molecular structure of the copolymer (P) is preferably a block copolymer.

Among the block copolymers, the copolymer (P) is a polymer block A having a structural unit UA derived from the monomer represented by the formula (1), and the polymer block A represented by the formula (2). It is preferably a block copolymer containing a polymer block B having a structural unit UB derived from a monomer.
Conventionally, homopolymers or random copolymers have been used as water-soluble polymers used in chemical mechanical polishing (CMP) additives. However, a polymer with a structure in which the functional groups that adsorb to the substrate surface are arranged throughout the polymer structure does not have the ability to protect the surface of the object to be polished because the adsorption sites are not arranged collectively. Overpolishing may occur. On the other hand, in the case of a block copolymer, it is considered that the functional groups that adsorb to the substrate surface are grouped together, so that the block copolymer exerts sufficient adsorption properties and can prevent excessive polishing of the object to be polished.

<Block copolymer>
A block copolymer that can be preferably used in the present invention is a block copolymer containing polymer block A and polymer block B.
・Polymer block A
Polymer block A has a structural unit UA derived from the monomer represented by formula (1). The polymer block A may be a homopolymer of the monomer represented by the formula (1), or a polymer using a plurality of types of the monomer represented by the formula (1). can be In addition, the polymer block A is selected from the group consisting of the monomer represented by the formula (1) and the monomer represented by the formula (2) as long as the effect of the present invention is not impaired. and/or a copolymer with the other copolymerizable monomer.

The content of the structural unit UA derived from the monomer represented by the formula (1) is preferably 80% by mass or more with respect to the entire polymer block A. More preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 97% by mass or more, and still more preferably 99% by mass or more. The upper limit is 100% by mass.
When the content of the structural unit derived from the monomer represented by the formula (1) is within the above range, the responsiveness to changes in the polishing pressure is high, and when the oxide film is a convex portion (high polishing pressure However, when polishing progresses and the nitride film is exposed and the object to be polished becomes a recess (polishing pressure is low), it adheres to the interface of the oxide film and suppresses excessive polishing. tend to These effects make it easier to obtain a good polished surface with reduced dishing without lowering the polishing rate.

The weight average molecular weight of the polymer block A is preferably 500 or more, more preferably 900 or more, still more preferably 1,500 or more, still more preferably 2,100 or more, and still more preferably 2,700 or more. The upper limit of the weight average molecular weight is preferably 100,000 or less, more preferably 60,000 or less, still more preferably 30,000 or less, still more preferably 10,000 or less, and still more preferably 6,000 or less. A preferred range can be represented by any combination of these lower and upper limits.
When the weight average molecular weight of the polymer block A is within the above range, it is possible to sufficiently ensure the wettability of the surface of the object to be polished while suppressing a decrease in the polishing rate. In addition, it is preferable in that it can sufficiently suppress aggregation of abrasive grains due to shearing force, and sufficiently suppress the occurrence of defects such as scratches during polishing.

・Polymer block B
Polymer block B has a structural unit UB derived from the monomer represented by the formula (2). The polymer block B may be a homopolymer of the monomer represented by the formula (2), and at least one selected from the group consisting of the monomers represented by the formula (2). A polymer using a plurality of types of seed monomers may also be used. Further, as long as the effects of the present invention are not impaired, the polymer block B comprises at least one monomer selected from the group consisting of the monomers represented by the formula (2) and the ) and/or a copolymer with the other copolymerizable monomer.

The content of the structural unit UB derived from the monomer represented by the formula (2) is preferably 35% by mass or more with respect to the entire polymer block B. may be 40% by mass or more, may be 45% by mass or more, may be 50% by mass or more, may be 55% by mass or more, may be 60% by mass or more, It may be 70% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more. An upper limit is 100 mass % or less.

The weight average molecular weight of the polymer block B is preferably 100 or more, more preferably 120 or more, even more preferably 130 or more, even more preferably 140 or more, and even more preferably 150 or more. The upper limit of the weight average molecular weight is preferably 50,000 or less, more preferably 10,000 or less, still more preferably 5,000 or less, still more preferably 1,000 or less, and even more preferably 500 or less. is. A preferred range can be expressed by any combination of the above lower and upper limits.

The block copolymer that can be preferably used in the present invention may have one or more of each of the polymer block A and the polymer block B. For example, the polymer block A and the polymer block AB diblock copolymer consisting of B, ABA triblock copolymer or BAB triblock copolymer consisting of polymer block A/polymer block B/polymer block A, and the like. Further, the block copolymer may be a multi-block copolymer having 4 or more polymer blocks, including a polymer block C other than the polymer block A and the polymer block B, ABC or It may be a block copolymer having a structure such as ABCA. Above all, the block copolymer preferably has an AB structure from the viewpoint of reducing the possibility of contamination with various impurities because of fewer production steps compared to the ABC structure and the like, and from the viewpoint of being able to produce high-purity products.

The mass ratio of the polymer block A and the polymer block B in the block copolymer is preferably 50/50 to 99.9/0.1, more preferably 80/20 to 99/ 1, more preferably 90/10 to 98/2, even more preferably 93/7 to 97/3. If the mass ratio is within this range, it tends to adsorb to the oxide film and exhibit a protective effect. In addition, it has high responsiveness to changes in polishing pressure, and when the oxide film is a convex portion (state of high polishing pressure), it does not adhere and the polishing rate does not decrease, but as the polishing progresses, the nitride film is exposed and the object to be polished is damaged. When it becomes a concave portion (when the polishing pressure is low), it tends to adhere to the oxide film interface and suppress excessive polishing. It is believed that these effects make it easier to obtain a good polished surface with reduced dishing without lowering the polishing rate.

Further, when the block copolymer contains a polymer block C other than the polymer block A and the polymer block B, the ratio of the polymer block A and the polymer block B to the entire block copolymer The total mass ratio is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 98% by mass or more, and still more preferably 99% by mass or more.

The chemical mechanical polishing additive provided by the present invention is a chemical mechanical polishing additive containing a copolymer (P), wherein the copolymer (P) is represented by the formula (1). The content of the structural unit derived from the vinyl monomer is 50 to 99% by mass of the entire copolymer P, and the structural unit derived from the vinyl monomer represented by the formula (2) is 1 to 50% by mass of the total copolymer (P). Therefore, the chemical mechanical polishing additive provided by the present invention may be in the form of a single component containing only the copolymer (P), or may be in the form of a single component containing the copolymer (P), A form containing a component different from the copolymer (P) (hereinafter also referred to as “other component”) may be used.

The additive for chemical mechanical polishing provided by the present invention may contain a solvent as another component. Examples of the solvent include water, organic solvents, mixed solvents of water and organic solvents, and the like. Among these, a solvent capable of dissolving the copolymer (P) is preferred, water or a mixed solvent of water and an organic solvent soluble in water is more preferred, and water is particularly preferred. Examples of organic solvents used with water include alcohols such as methanol, ethanol, propanol and butanol; ketones such as acetone and methyl ethyl ketone; alkylene glycols such as ethylene glycol and propylene glycol; ethylene glycol monomethyl ether and propylene glycol. Ethers such as monomethyl ether, ethylene glycol dimethyl ether, and tetrahydrofuran; Esters such as ethylene glycol monomethyl ether acetate and ethyl acetate; Amide solvents such as N,N-dimethylformamide and N,N-dimethylacetamide; Nitrile solvents such as acetonitrile A solvent etc. are mentioned. As the organic solvent, one type can be used alone or two or more types can be used in combination.

When the additive for chemical mechanical polishing provided by the present invention contains the copolymer (P) and a solvent, the copolymer (P) is sufficiently brought into contact with the surface of the object to be polished and the polishing pad. From the viewpoint of performing the reaction, the content of the copolymer (P) is preferably 1% by mass or more, more preferably 5% by mass or more, relative to the total mass of the copolymer (P) and the solvent. and more preferably 10% by mass or more. Further, regarding the upper limit of the content of the copolymer (P), from the viewpoint of suppressing the deterioration of handleability due to excessive viscosity increase, the total mass of the copolymer (P) and the solvent On the other hand, it is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less. A preferred range can be represented by any combination of these lower and upper limits.

<<Method for producing polymer for polishing liquid additive>>
The method for producing the polymer for polishing liquid additives, that is, the copolymer (P) that can be preferably used in the present invention is not particularly limited as long as the effects of the present invention are not impaired. For example, it can be produced by adopting a known radical polymerization method such as a solution polymerization method or bulk polymerization to polymerize the above-described monomers. In the solution polymerization method, for example, a solvent and monomers are charged into a reactor, a polymerization initiator is added, and the desired polymer can be obtained by heating and polymerizing.

By subjecting the copolymer (P) produced as described above to a known polymer purification method such as a reprecipitation method or a method using a porous material, the weight average molecular weight (Mw)/number average molecular weight (Mn) You may refine|purify so that a dispersion index (PDI) represented by may be set to 2.0 or less.

Suitable methods for producing the copolymer (P) include various controlled polymerization methods such as living radical polymerization and living anion polymerization. Among these, the controllability of the molecular weight dispersity (PDI) is high, it is possible to produce a polymer with excellent dispersion stability of abrasive grains, and the operation is simple and applicable to a wide range of monomers. A living radical polymerization method is preferred in that it is possible. When adopting the living radical polymerization method, the polymerization form is not particularly limited, and various modes such as bulk polymerization, solution polymerization, emulsion polymerization, miniemulsion polymerization, and suspension polymerization can be used.

For example, when a living radical polymerization method is employed to produce the copolymer (P) by solution polymerization, a solvent and monomers are charged into a reactor, a radical polymerization initiator is added, and preferably heated. The desired copolymer (P) can be obtained by polymerization. Polymerization may employ any process such as a batch process, a semi-batch process, a dry continuous polymerization process, a continuous stirred tank process (CSTR), or the like.

In the production of the copolymer (P), a known polymerization method can be employed as the living radical polymerization method. Specific examples of the living radical polymerization method to be used include a living radical polymerization method using an exchange chain mechanism, a living radical polymerization method using a bond-dissociation mechanism, and a living radical polymerization method using an atom transfer mechanism. Specific examples thereof include reversible addition-fragmentation chain transfer polymerization method (RAFT method), iodine transfer polymerization method, polymerization method using organic tellurium compound (TERP method), and organic antimony compound as living radical polymerization of exchange chain mechanism. (SBRP method), a polymerization method using an organic bismuth compound (BIRP method), etc.; A transfer radical polymerization method (ATRP method) and the like can be mentioned, respectively. Among these, the living radical polymerization method of the exchange chain mechanism is preferable because it can be applied to the widest range of vinyl monomers and has excellent controllability of polymerization. The RAFT method or the NMP method is preferred from the viewpoint of avoiding contamination, and the RAFT method is particularly preferred from the viewpoint of facilitating synthesis in an aqueous system that does not require high temperatures.

In the RAFT method, polymerization proceeds via a reversible chain transfer reaction in the presence of a polymerization controller (RAFT agent) and a radical polymerization initiator. As the RAFT agent, various known RAFT agents such as dithioester compounds, xanthate compounds, trithiocarbonate compounds and dithiocarbamate compounds can be used. Among these, trithiocarbonate compounds and dithiocarbamate compounds are preferable in that a polymer having a smaller molecular weight dispersity can be obtained. The RAFT agent may be a monofunctional compound having only one active site, or a polyfunctional compound having two or more active sites. The amount of the RAFT agent used is appropriately adjusted depending on the type of monomer and RAFT agent used.

As the polymerization initiator used for polymerization by the RAFT method, known radical polymerization initiators such as azo compounds, organic peroxides and persulfates can be used. Among these, an azo compound is preferable because it is easy to handle safely and hardly causes a side reaction during radical polymerization. Specific examples of azo compounds include 2,2′-azobis(isobutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 4,4′-azobis(4-cyanovaleric acid) , 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl-2,2′-azobis(2-methylpropionate), 2,2′-azobis(2-methylbutyro nitrile), 1,1′-azobis(cyclohexane-1-carbonitrile), 2,2′-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2′-azobis(N-butyl -2-methylpropionamide) and the like. As the radical polymerization initiator, only one type may be used, or two or more types may be used in combination.

The amount of the radical polymerization initiator to be used is not particularly limited, but from the viewpoint of obtaining a polymer with a smaller molecular weight dispersity, it is preferably 0.5 mol or less, such as 0.2 mol, per 1 mol of the RAFT agent. More preferably: From the viewpoint of stably conducting the polymerization reaction, the lower limit of the amount of the radical polymerization initiator to be used is preferably 0.01 mol or more, preferably 0.05 mol or more, with respect to 1 mol of the RAFT agent. is more preferable. The amount of the radical polymerization initiator to be used is preferably 0.01 to 0.5 mol, more preferably 0.05 to 0.2 mol, per 1 mol of the RAFT agent.

When a solvent is used in the living radical polymerization, the polymerization solvent includes aromatic compounds such as benzene, toluene, xylene and anisole; ester compounds such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate; ketone compounds such as acetone and methyl ethyl ketone. ; dimethylformamide, acetonitrile, dimethylsulfoxide, alcohol, water and the like. As the polymerization solvent, one of these may be used alone, or two or more thereof may be used in combination.

In the polymerization reaction by the RAFT method, the reaction temperature is preferably 40° C. or higher and 100° C. or lower, more preferably 45° C. or higher and 90° C. or lower, and still more preferably 50° C. or higher and 80° C. or lower. A reaction temperature of 40° C. or higher is preferable in that the polymerization reaction can proceed smoothly. It is preferable that In addition, the reaction time can be appropriately set according to the monomers to be used and the like, but is preferably 1 hour or more and 48 hours or less, more preferably 3 hours or more and 24 hours or less. Polymerization may be carried out in the presence of a chain transfer agent (eg, an alkylthiol compound having 2 to 20 carbon atoms, etc.), if necessary. In the manufacturing process, especially in situations where monomers with acidic groups are used, if there is concern about metal contamination due to corrosion of the reactor, etc., use equipment whose surface is coated with fluorine resin, etc. Manufacturing is preferred. Further, in this case, it is preferable that the container for storing the product or the like is made of a corrosion-resistant resin container or the like. When a container made of resin is used, it is preferable that the container be made of a material that suppresses contamination with metal due to dissolution of filler or the like.

<<Polish composition>>
The polishing composition provided by the present invention contains at least the copolymer (P) and abrasive grains. At least one kind of particles selected from the group consisting of known inorganic particles, organic particles, and organic-inorganic composite particles can be used as the abrasive grains.

Specific examples of inorganic particles include cerium oxide (ceria), fumed silica, fumed alumina, fumed titania, and colloidal silica. Specific examples of organic particles include (meth)acrylic particles such as polymethyl methacrylate. polystyrene and polystyrene copolymers, polyacetals, polyamides, polycarbonates, polyolefins and polyolefin copolymers, phenoxy resins and the like. The organic-inorganic composite particles may be those in which the functional group of the organic component and the functional group of the inorganic component are chemically bonded, or the like, which are bonded or combined to such an extent that they do not decompose under the conditions used as the polishing composition. Good luck.
Among these, cerium oxide and/or silica are preferred because they have lower hardness than alumina and the like and have the advantage of being able to suppress the occurrence of defects on the polished surface. In particular, cerium oxide is more suitable because it can polish the polishing surface at a higher polishing rate than silica, alumina, or the like.

Although the average particle size of the abrasive grains is not particularly limited, it is generally 1 nm to 500 nm. From the viewpoint of ensuring a high polishing rate, the average particle size is preferably 2 nm or more, more preferably 3 nm or more. The upper limit of the average particle size is preferably 300 nm or less, more preferably 100 nm or less, from the viewpoint of suppressing the occurrence of scratches on the surface of the object to be polished. In this specification, the average particle size of abrasive grains is the primary particle size calculated using the specific surface area (m ² /g) calculated by the BET (nitrogen adsorption) method.

From the viewpoint of realizing a high polishing rate, the content of the abrasive grains in the polishing composition is preferably 1% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. The upper limit of the abrasive grain content is preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less, from the viewpoint of improving the smoothness of the object to be polished. A preferred range can be represented by any combination of these lower and upper limits.

The polishing composition may contain a solvent. The solvent is preferably a water-based solvent, and includes water, a mixed solvent of water and other solvents, and the like. As the other solvent, a solvent compatible with water is preferable, and examples thereof include alcohols such as ethanol. Further, the polishing liquid composition may further contain known additives such as polishing accelerators, pH adjusters, surfactants, chelating agents, anticorrosive agents, etc., within a range that does not impair the effects of the present invention. good.

The content of the copolymer (P) is preferably an amount such that the solid content concentration of the copolymer (P) is 0.001% by mass or more relative to the total amount of the polishing composition. It is more preferable to set the amount to be mass % or more. Regarding the upper limit of the content of the copolymer (P), it is preferable to set the solid content concentration of the copolymer (P) to 10% by mass or less with respect to the total amount of the polishing composition. It is more preferable to set the amount to 5% by mass or less. A preferred range can be represented by any combination of these lower and upper limits.

The polishing liquid composition is usually prepared as a slurry-like mixture by mixing each component by a known method. The viscosity of the polishing liquid composition at 25° C. can be appropriately selected according to the object to be polished, the shear rate during polishing, etc., but it is preferably in the range of 0.1 to 10 mPa·s. More preferably, it is in the range of 5 to 5 mPa·s.

Since the polishing liquid composition contains the copolymer (P) as an additive, the polishing rate of convex portions (oxide films) on the uneven surface to be polished is sufficiently high, and dishing is greatly reduced. It is possible to
Therefore, the polishing composition provided by the present invention can be used to planarize the surface of at least one of an insulating film and metal wiring in the manufacturing process of semiconductor devices, specifically, for example, shallow trench isolation (STI). Polishing liquid for flattening oxide films (silicon oxide films, etc.), flattening the surface of metal wiring made of copper, copper alloys, aluminum alloys, etc., flattening the surface of interlayer insulating films (oxide films), etc. is preferable in that the occurrence of defects can be reduced and an insulating film and metal wiring having excellent surface smoothness can be obtained.

EXAMPLES The present invention will be specifically described below based on examples. It should be noted that the present invention is not limited by these examples. In the following, "parts" and "%" mean parts by weight and % by weight unless otherwise specified.
The analysis methods and production methods of the polymers used in Examples and Comparative Examples are described below.

<Mass Composition Ratio of Polymer>
The mass composition ratio of the obtained polymer was calculated based on the reaction rate of the monomer calculated by 1H-NMR measurement or gas chromatography (GC).
Ascend TM400 nuclear magnetic resonance spectrometer manufactured by BRUKER was used as a 1H-NMR spectrometer, and measurements were performed at 25° C. using tetramethylsilane as a standard substance and deuterated chloroform as a solvent.
In addition, for GC, Agilent 7820A (manufactured by Agilent Technologies) was used as an apparatus, VARIAN CP-SIL 5CB (30 m × 0.32 mm, df = 3.0 µm) as a column, nitrogen as a carrier gas, and FID for detection. measurements were taken.

<Molecular weight measurement>
Using a gel permeation chromatograph (model name “HLC-8220”, manufactured by Tosoh Corporation), the number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of polystyrene were obtained under the following conditions. Also, the molecular weight distribution (Mw/Mn) was calculated from the obtained values.
○ Measurement conditions Column: TSKgel Super Multipore HxL-M × 4 columns manufactured by Tosoh Corporation Column temperature: 40 ° C.
Eluent: Tetrahydrofuran Detector: RI
Flow rate: 0.6mL/min

1. Polymer Synthesis <Synthesis Example 1>
150 g of pure water, 300 g of methoxypolyethylene glycol monoacrylate (manufactured by NOF, hereinafter also referred to as "AME-400"), 4,4 '-azobis (4-cyanovaleric acid) (manufactured by Fujifilm Wako Pure Chemical Industries, hereinafter also referred to as "V-501") 0.48 g, 3-((((1-carboxyethyl)thio)carbohydrate as a RAFT agent 26.8 g of nothioyl)thio)propanoic acid (manufactured by BORON MOLECULAR, hereinafter also referred to as "BM1429") was charged, degassed sufficiently by nitrogen bubbling, and polymerization was initiated in a constant temperature bath at 70°C. After 3 hours, the mixture was cooled with water to terminate the polymerization. The polymerization rate of AME-400 was determined by 1H-NMR measurement to be 95%. Subsequently, 15.6 g of N-isopropylacrylamide (hereinafter also referred to as "NIPAM") was added, the mixture was sufficiently degassed by nitrogen bubbling, and polymerization was initiated in a constant temperature bath at 70°C. After 3 hours, the mixture was cooled with water to terminate the polymerization. The polymerization rate of NIPAM was determined by GC measurement to be 90%. The resulting water-soluble block copolymer (referred to as "polymer A") had a molecular weight of Mn 3,120, Mw 3,430 and a PDI of 1.1 as measured by GPC.

<Synthesis Examples 2-10, 12-16, Comparative Synthesis Examples 1-2>
Water-soluble block copolymers (Polymers B to J, L to P, S to T) were obtained in the same manner as in Synthesis Example 1, except that the starting materials were changed as shown in Tables 1 and 2. . Tables 1 and 2 show the molecular weights of polymers B to J, L to P, and S to T determined by GPC measurement.

<Synthesis Example 11>
150 g of pure water, 285 g of AME-400, 15 g of NIPAM, 0.48 g of V-501, and 25.4 g of BM1429 were charged into a 1 L four-necked eggplant-shaped flask equipped with a stirrer, a thermometer, and a nitrogen inlet tube, After sufficient degassing by nitrogen bubbling, polymerization was initiated in a constant temperature bath at 70°C. After 5 hours, the mixture was cooled with water to terminate the polymerization. The polymerization rate of AME-400 was determined by 1H-NMR measurement, and the polymerization rate of NIPAM was determined by GC to be 95% and 90%, respectively. The resulting water-soluble polymer (referred to as "polymer K") had a molecular weight of Mn 3,090, Mw 3,400 and a PDI of 1.1 as measured by GPC.

<Synthesis Example 17>
150 g of pure water, 300 g of AME-400, 0.48 g of V-501, and 26.8 g of BM1429 are charged in a 1 L four-necked eggplant-shaped flask equipped with a stirrer, thermometer, and nitrogen inlet tube, and nitrogen bubbling is sufficient. After degassing, polymerization was initiated in a constant temperature bath at 70°C. After 3 hours, the mixture was cooled with water to terminate the polymerization. When the polymerization rate of AME-400 was measured by NMR, it was 95%. Subsequently, 7.8 g of NIPAM was added, the mixture was sufficiently degassed by nitrogen bubbling, and polymerization was initiated in a constant temperature bath at 70°C. After 3 hours, the mixture was cooled with water to terminate the polymerization. When the reaction rate of NIPAM was measured by GC, it was 90%. Subsequently, 7.8 g of N-tert-butylacrylamide (hereinafter also referred to as "TBAM") was added, the mixture was sufficiently degassed by nitrogen bubbling, and polymerization was initiated in a constant temperature bath at 70°C. After 3 hours, the mixture was cooled with water to terminate the polymerization. , the polymerization rate of TBAM was determined from GC measurement to be 90%. The resulting water-soluble block copolymer (referred to as "Polymer Q") had a molecular weight of Mn 3,100, Mw 3,410 and a PDI of 1.1 as measured by GPC.

<Synthesis Example 18>
100 g of acetonitrile was added to a 1 L four-neck eggplant-shaped flask equipped with a stirrer, a thermometer, and a nitrogen inlet tube, and the mixture was kept at 75° C. and stirred. Initiator obtained by dissolving 0.10 g of 2,2′-azobis(2,4-dimethylvaleronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries, hereinafter also referred to as “V-65”) in 7.2 g of acetonitrile. solution was added. A monomer mixture of 410 g of AME-400 and 22 g of NIPAM, and a chain transfer agent solution obtained by dissolving 50 g of 3-methoxybutyl 3-mercaptopropionate (hereinafter also referred to as “MPMB”) in 64 g of acetonitrile were added to flasks for 3 hours. supplied over time. Simultaneously with the monomer mixed solution and the chain transfer agent solution, an initiator solution prepared by dissolving 0.40 g of V-65 in 40 g of acetonitrile was supplied to the flask over 5 hours. After the completion of the supply of the initiator solution, the mixture was further heated and stirred for 1.5 hours. After that, the mixture was cooled with water to terminate the polymerization. After that, the solvent was removed by an evaporator. The polymerization rates of AME-400 and NIPAM were determined by 1H-NMR measurement to be 99% and 95%, respectively. The resulting water-soluble polymer (referred to as "polymer R") had a molecular weight of Mn 2,670, Mw 5,870 and a PDI of 2.2 as measured by GPC.

The details of Tables 1-4 are as follows.
AME-400: methoxy polyethylene glycol monoacrylate (n = 9) (manufactured by NOF, trade name: Blemmer AME-400)
PME-400: Methoxy polyethylene glycol monomethacrylate (n = 9) (manufactured by NOF, trade name: Blenmer PME-400)
MTG-A: Methoxytriethylene glycol acrylate (manufactured by Kyoeisha Chemical, trade name: Light acrylate MTG-A)
AM-230G: Methoxy polyethylene glycol acrylate (n = 23) (manufactured by Shin-Nakamura Chemical Industry, trade name: NK Ester AM-230G)
AE-400: Polyalkylene glycol monoacrylate (n = 10) (manufactured by NOF, trade name: Blemmer AE-400)
NIPAM: N-isopropylacrylamide ACMO: N-acryloylmorpholine AA: Acrylic acid V-501: 4,4'-azobis(4-cyanovaleric acid) (manufactured by Fujifilm Wako Pure Chemical Industries)
V-65: 2,2′-azobis(2,4-dimethylvaleronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries)
BM1429: 3-((((1-carboxyethyl)thio)carbonothioyl)thio)propanoic acid (manufactured by BORON MOLECULAR)
MPMB: 3-methoxybutyl 3-mercaptopropionate TBAM: N-tert-butylacrylamide DMAA: N,N-dimethylacrylamide DEAA: N,N-diethylacrylamide HEAA: N-(2-hydroxyethyl)acrylamide XL-80: Polyoxyalkylene branched decyl ether (Daiichi Kogyo Seiyaku, trade name: Neugen XL-80)

2. Measurement and evaluation <Example 1>
500 parts of an aqueous polymer solution containing polymer A at a solid concentration of 0.5% by mass was prepared. Next, while stirring 500 parts of an aqueous dispersion of colloidal ceria (manufactured by NYACOL, trade name: NYACOL80/10, particle concentration: 10%, average particle diameter: 80 nm), the previously prepared polymer aqueous solution was added to obtain a polishing composition. got stuff

<Examples 2 to 18, Comparative Examples 3 to 5>
A polishing liquid composition was obtained in the same manner as in Example 1, except that polymer A was changed to a polymer shown in Tables 3 and 4.

<Example 19>
500 parts of an aqueous polymer solution containing polymer A at a solid concentration of 0.5% by mass was prepared. Next, while stirring 500 parts of an aqueous dispersion of colloidal silica (manufactured by Fuso Chemical Industries, trade name: Quartron PL-7, particle concentration: 23%, average particle diameter: 75 nm), the previously prepared polymer aqueous solution is added. and 28% aqueous ammonia to adjust the pH to 9 to obtain a polishing composition.

<Comparative Example 1>
500 parts of pure water was added to 500 parts of colloidal ceria aqueous dispersion (manufactured by NYACOL, trade name: NYACOL80/10, particle concentration: 10%, average particle diameter: 80 nm) while stirring to obtain a polishing composition.

<Comparative Example 2>
While stirring 500 parts of an aqueous dispersion of colloidal silica (manufactured by Fuso Chemical Industry, trade name: Quartron PL-7, particle concentration 23%, average particle diameter 75 nm), 500 parts of pure water was added, followed by 28% ammonia water. to obtain a polishing liquid composition.

Using each polishing composition prepared by the above method, a polishing test was conducted under the following conditions.
<Polishing conditions>
Polishing tester: Kemet Japan, product name: MAT-ARW-CMS
Polishing pad: manufactured by Rodel Nitta, trade name: IC-1000/Sub400
Platen rotation speed: 60 rpm Carrier rotation speed: 61 rpm
Amount of polishing liquid supplied: 150 (g/min)
Polishing pressure: 1, 3, 5 (psi)

Blanket wafer A 4-inch silicon substrate on which a silicon oxide film of 1.4 μm was deposited by CVD (blanket wafer) was used as the material to be polished, and was polished for 1 minute under the above polishing conditions. A rate (RR) (nm/min) was determined. The remaining film thickness was measured using an optical interference film thickness meter.
Regarding the RR of each polishing composition, the RR of the polishing compositions of Examples 1 to 18 and Comparative Examples 3 to 5 is the ratio of the RR of the polishing composition of Comparative Example 1 to the RR of the polishing composition of Example 19. RR was evaluated by the ratio to the RR of the polishing composition of Comparative Example 2 (at 3 psi for each). The evaluation criteria for RR were as follows. (The RR of Comparative Examples 1 and 2 is RRa, the RR of the polishing compositions of Examples 1 to 19 and Comparative Examples 3 and 5 is RRb, and the calculated values of RRb/RRa are shown in Tables 3 and 4.) , and the polishing liquid compositions of Comparative Examples 1 and 2 were set to RRb/RRa=1.00. Subsequently, dishing reduction performance was evaluated according to the following criteria for RR (RR1) at 1 psi and RR (RR3) at 3 psi, and the ratio of RR1 and RR (RR5) at 5 psi (RR3/RR1, RR5/RR1). When both criteria of RR and dishing reduction performance were satisfied, they were regarded as acceptable.
<RR Evaluation Criteria>
◎: RRb/RRa≧0.85
○: 0.85>RRb/RRa≧0.70
△: 0.70>RRb/RRa≧0.50
×: RRb/RRa<0.50
<Evaluation criteria for dishing reduction performance>
◎: RR3/RR1≧4.0 and RR5/RR1≧7.0
○: 4.0>RR3/RR1>3.5 or 7.0>RR5/RR1>6.5
△: 3.5≧RR3/RR1>2.8, or 6.5≧RR5/RR1>5.0
×: RR3/RR1 ≤ 2.8 and RR5/RR1 ≤ 5.0

<Evaluation results>
In the blanket wafer polishing performed using the polishing composition of each example, RR (RR1, RR3, RR5) at each polishing pressure, RRb/RRa value as an evaluation index of RR, evaluation index of dishing reduction performance Tables 3 and 4 show the values of RR3/RR1 and RR5/RR1.
A polishing liquid composition that has the property of suppressing RR at low polishing pressure and exhibiting high RR at high polishing pressure can provide a good polished surface with reduced dishing of patterned wafers without lowering RR.
Each of the polishing liquid compositions of the examples exhibited a suppressed RR at low polishing pressures, a high RR at high polishing pressures, and increased RR3/RR1 and RR5/RR1. Also, since the decrease in RR3 was small, RRb/RRa also increased. On the other hand, when the additives of Comparative Examples 1 and 2 were not added, the RR was almost proportional to the polishing pressure. In Comparative Example 3, although a high RR was exhibited at high polishing pressure, the suppression of RR at low polishing pressure was small, so the dishing reduction performance was insufficient. In Comparative Examples 4 and 5, the RR was greatly suppressed at all polishing pressures, and neither the RR nor the dishing reduction performance satisfied the acceptance criteria.

Claims (10)

A chemical mechanical polishing additive comprising a copolymer (P),
In the copolymer (P), the content of structural units derived from a vinyl monomer represented by the following formula (1) is 50 to 99% by mass of the entire copolymer P,
CH2=CR ¹ -C(=O)O-(LO)n-R ² (1)
(In formula (1), R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and L is an alkylene group having 4 or less carbon atoms. and n is an integer from 3 to 150.)
An additive characterized in that the content of structural units derived from a vinyl monomer represented by the following formula (2) is 1 to 50% by mass of the entire copolymer (P).
CH2=CR ¹ -C(=O)NR ³ R ⁴ (2)
(In formula (2), R ¹ is a hydrogen atom or a methyl group. R ³ and R ⁴ are each independently a hydrogen atom or a monovalent hydrocarbon group, or R ³ and R ⁴ is a group that bonds with each other to form a ring together with the nitrogen atom to which R ³ and R ⁴ bond, and the total number of carbon atoms of R ³ and R ⁴ is 1 to 12.) The additive according to claim 1, wherein the copolymer (P) has a weight average molecular weight of 1,000 to 100,000. Among the structural units contained in the copolymer (P), a monomer containing a carboxylic acid group, a phosphoric acid group, a phosphonic acid group, a sulfuric acid group, a sulfonic acid group, and/or a salt thereof as a functional group The additive according to any one of claims 1 to 3, wherein the total content of the derived structural units is 0 to 0.6 mass% of the entire copolymer (P). 4. The vinyl monomer represented by the formula (2) is a monomer having an SP value of 17 to 25 (J/cm ³ ) ^0.5 calculated by the Fedors estimation method. The additive according to item 1. 5. Any one of claims 1 to 4, wherein the copolymer (P) has a molecular weight dispersity (Mw/Mn) represented by the ratio of the number average molecular weight Mn to the weight average molecular weight Mw of 2.0 or less. Additives described in . Additive according to any one of claims 1 to 5, wherein the copolymer (P) is a block polymer. The copolymer (P) contains a polymer block A and a polymer block B,
The polymer block A has a structural unit derived from the vinyl monomer represented by the formula (1),
The additive according to any one of claims 1 to 6, wherein the polymer block B has a structural unit UB derived from the vinyl monomer represented by the formula (2). According to claim 7, wherein the ratio (A/B) of said polymer block A and said polymer block B in said copolymer (P) is 50/50 to 99.9/0.1 in mass ratio. Additives as described. A polishing liquid composition for chemical mechanical polishing used for planarizing the surface of at least one of an insulating layer and a wiring layer, comprising the additive according to any one of claims 1 to 8, cerium oxide and / Or a polishing composition containing silica. A method for producing a chemical mechanical polishing liquid additive containing a copolymer, comprising:
In the copolymer, the content of structural units derived from a vinyl monomer represented by the following formula (1) is 50 to 99% by mass of the entire copolymer,
CH2=CR ¹ -C(=O)O-(LO)n-R ² (1)
(In formula (1), R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and L is an alkylene group having 4 or less carbon atoms. and n is an integer from 3 to 150.)
And the content of the structural unit derived from the vinyl monomer represented by the following formula (2) is 1 to 50 mass% of the total copolymer (P), the copolymer (P) is prepared by living radical polymerization. A manufacturing method characterized by passing through a process of manufacturing by.
CH2=CR ¹ -C(=O)NR ³ R ⁴ (2)
(In formula (2), R ¹ is a hydrogen atom or a methyl group. R ³ and R ⁴ are each independently a hydrogen atom or a monovalent hydrocarbon group, or R ³ and R ⁴ is a group that bonds with each other to form a ring together with the nitrogen atom to which R ³ and R ⁴ bond, and the total number of carbon atoms of R ³ and R ⁴ is 1 to 12.)