CN100467224C - Polishing cloth, polishing device and method for producing semiconductor equipment - Google Patents

Abstract

The present invention discloses a polishing cloth having a polishing layer comprising a polymeric material that is hydrolyzable in an aqueous medium and capable of exhibiting relatively long-term stable polishing performance without necessary reconditioning treatments .

Description

Polishing cloth, polishing device and method for producing semiconductor equipment

This application is a divisional application of the application with the filing date of October 3, 2001, the application number of 01818564.9, and the invention titled "Polishing Cloth, Polishing Device and Preparation Method of Semiconductor Equipment".

technical field

The invention relates to a polishing cloth, a polishing device and a preparation method of semiconductor equipment.

Background technique

When it is desired to mirror-polish a semiconductor substrate (such as a semiconductor wafer), smooth an insulating film placed on a semiconductor wafer, or perform back etching of a metal film to form buried wiring, a polishing device equipped with a polishing cloth is usually used for Fabricate semiconductor devices.

The polishing device is generally composed of a turntable; a feed pipe for supplying the polishing slurry containing abrasive grains to the polishing cloth; Consisting of a base layer and a polishing cloth, the lower layer consisting of rigid polyurethane foam or of a double-layer structure consisting of a layer of rigid polyurethane foam and a layer of polyurethane non-woven fabric, the polishing cloth has a rough surface and covers the base layer . For example, when it is desired to smooth an insulating film placed on wiring formed on the surface of a semiconductor wafer, the polishing apparatus can operate as follows. First, the semiconductor wafer is fixed with a jig in such a way that the insulating film to be polished faces the polishing cloth, and while the polishing slurry containing abrasive grains is fed onto the polishing cloth, a desired amount of load is applied to the semiconductor wafer by means of the jig. The semiconductor wafer is brought into contact with the polishing cloth. In this case, the gripper and the turntable keep rotating in the same direction as each other.

In this polishing operation, the open spaces (usually 40-50 microns in diameter) of the polishing cloth are filled with abrasive grains with a diameter of 0.2 microns included in the polishing slurry, whereby the abrasive grains can be uniformly dispersed between the polishing cloth and the semiconductor wafer on the contact surface between them. At the same time, the abrasive grains can also remain at the portion of the polishing cloth located between the open spaces. Therefore, the insulating film can be mechanically polished, whereby smoothing of the insulating film surface is achieved.

However, when the polishing operation continues for a long time, abrasive grains accumulate in the open spaces, thereby increasing the amount of abrasive grains on the portion of the polishing cloth located between the open spaces. That is, the polishing ability of the abrasive grains will be increased. Therefore, the polishing rate at this time will increase compared to the initial polishing rate, thereby causing so-called fluctuations in polishing performance.

Polishing cloths that fluctuate in polishing performance as described above are usually regenerated by using a dressing apparatus equipped with a dressing tool having many diamond particles electrodeposited on a metal substrate. However, it is difficult to avoid such fluctuations in the polishing performance of the polishing cloth unless the above-mentioned conditioning treatment is performed after each polishing operation is completed. This makes the polishing operation cumbersome since it involves the above-mentioned finishing process.

Contents of the invention

It is an object of the present invention to provide a polishing cloth capable of exhibiting stable polishing performance over a relatively long period of time without necessary reconditioning.

Another object of the present invention is to provide a polishing cloth having an automatic feeding capability of abrasive grains and capable of exhibiting stable polishing performance over a relatively long period of time without necessary conditioning treatment.

Another object of the present invention is to provide a polishing apparatus equipped with the above-mentioned polishing cloth capable of exhibiting stable polishing performance.

Another object of the present invention is to provide a method of manufacturing a semiconductor device, which makes it possible to reliably form a conductive member, such as a buried wiring layer, with high precision in at least one buried portion, said buried portion selected from: grooves and openings formed in an insulating film that has been deposited on a semiconductor substrate.

According to the present invention there is provided a polishing cloth comprising a polishing layer comprising a polymeric material which is hydrolyzable with an aqueous medium.

According to the present invention, there is also provided a polishing cloth comprising a polishing layer comprising a polymer material and at least one abrasive grain selected from the group consisting of cerium oxide, manganese oxide , silica, alumina and zirconia, abrasive grains dispersed in polymer material.

According to the present invention there is also provided a polishing cloth comprising a polishing layer comprising a polymeric material which is soluble in an aqueous medium.

According to the present invention there is also provided a polishing cloth comprising a polishing layer comprising a polymeric material which is soluble in an aqueous medium and at least one abrasive grain selected from the group consisting of From ceria, manganese oxide, silica, alumina and zirconia, the abrasive grains are dispersed in the polymer material.

According to the present invention, there is also provided a polishing cloth comprising a polishing layer in which at least one abrasive particle selected from the group consisting of cerium oxide, manganese oxide, silicon dioxide, aluminum oxide and zirconium oxide is dispersed, wherein , before the polishing layer is subjected to frictional stress, the surface part of the polishing layer is prohibited from elution in the presence of an aqueous medium; and when the polishing layer is subjected to frictional stress, elution is allowed in the presence of an aqueous medium, while making the abrasive grains Can be supplied to the surface of the buffing layer.

According to the present invention, a kind of polishing device is also provided in addition, comprising:

a turntable having a surface covered with a polishing cloth having a buffing layer comprising a polymeric material that is hydrolyzable with an aqueous medium;

rotatably and vertically movable clamping mechanism arranged on the turntable, which is designed to hold the object part being polished; the clamping mechanism is also designed to apply a desired amount of load to the object part, whereby the object part The buffing cloth of the turntable is in pressurized contact; additionally designed to rotate in the same direction as the turntable; and

Feed mechanism for delivering polishing slurry containing abrasive grains to the polishing cloth.

According to the present invention, a kind of polishing device is also provided in addition, comprising:

A turntable having a surface covered with a polishing cloth having a buffing layer comprising a polymeric material and at least one abrasive grain selected from the group consisting of Cerium oxide, manganese oxide, silicon dioxide, aluminum oxide and zirconium oxide, the abrasive grains are dispersed in a polymeric material.

rotatably and vertically movable clamping mechanism arranged on the turntable, which is designed to hold the object part being polished; the clamping mechanism is also designed to apply a desired amount of load to the object part, whereby the object part The buffing cloth of the turntable is in pressurized contact; additionally designed to rotate in the same direction as the turntable; and

A feed mechanism for delivering a polishing composition comprising at least water and no abrasive particles to a polishing cloth.

According to the present invention, a kind of polishing device is also provided in addition, comprising:

a turntable having a surface covered with a polishing cloth having a buffing layer comprising a polymeric material that is soluble in an aqueous medium;

rotatably and vertically movable clamping mechanism arranged on the turntable, which is designed to hold the object part being polished; the clamping mechanism is also designed to apply a desired amount of load to the object part, whereby the object part The buffing cloth of the turntable is in pressurized contact; additionally designed to rotate in the same direction as the turntable; and

Feed mechanism for delivering polishing slurry containing abrasive grains to the polishing cloth.

According to the present invention, a kind of polishing device is also provided in addition, comprising:

A turntable having a surface covered with a polishing cloth having a buffing layer comprising a polymeric material soluble in an aqueous medium and at least one abrasive grain selected from the group consisting of grains selected from ceria, manganese oxide, silica, alumina and zirconia, the abrasive grains are dispersed in the polymeric material;

rotatably and vertically movable clamping mechanism arranged on the turntable, which is designed to hold the object part being polished; the clamping mechanism is also designed to apply a desired amount of load to the object part, whereby the object part The buffing cloth of the turntable is in pressurized contact; additionally designed to rotate in the same direction as the turntable; and

A feed mechanism for delivering a polishing composition comprising at least water and no abrasive particles to a polishing cloth.

According to the present invention, a kind of polishing device is also provided in addition, comprising:

a turntable having a surface covered with a polishing cloth comprising a buffing layer, a surface portion of the buffing layer capable of being eluted in the presence of an aqueous medium when the buffing layer is subjected to frictional stress;

rotatably and vertically movable clamping mechanism arranged on the turntable, which is designed to hold the object part being polished; the clamping mechanism is also designed to apply a desired amount of load to the object part, whereby the object part The buffing cloth of the turntable is in pressurized contact; additionally designed to rotate in the same direction as the turntable; and

Feed mechanism for delivering polishing slurry containing abrasive grains to the polishing cloth.

According to the present invention, a kind of polishing device is also provided in addition, comprising:

A turntable having a surface covered with a polishing cloth comprising a buffing layer dispersed therein of at least one abrasive grain selected from the group consisting of cerium oxide, manganese oxide, silica, aluminum oxide and zirconia, wherein, when the polishing layer is subjected to frictional stress, the surface portion of the polishing layer is allowed to elute in the presence of an aqueous medium while enabling abrasive grains to be supplied to the surface of the polishing layer;

rotatably and vertically movable clamping mechanism arranged on the turntable, which is designed to hold the object part being polished; the clamping mechanism is also designed to apply a desired amount of load to the object part, whereby the object part The buffing cloth of the turntable is in pressurized contact; additionally designed to rotate in the same direction as the turntable; and

A feed mechanism for delivering a polishing composition comprising at least water and no abrasive particles to a polishing cloth.

According to the present invention, also provide a kind of preparation method of semiconductor device, described method comprises:

In the insulating film deposited on the semiconductor substrate, at least one buried portion is formed, and the buried portion is selected from the group consisting of: a groove corresponding to a wiring layer configuration, and a groove corresponding to a filling via (via-fill) (filled The opening of the configuration of the passage);

forming a wiring material film made of copper or copper alloy on the surface of the insulating film including the inner surface of the buried portion; and

polishing the wiring material film with a polishing device, thereby forming at least one conductive member selected from a filled via in the buried portion and a wiring layer;

wherein the polishing apparatus comprises a turntable having a surface covered with a polishing cloth having a buffing layer comprising a polymer material that is hydrolyzable in an aqueous medium; rotatable and vertically movable The clamp mechanism is arranged above the turntable and is designed to fix the object part to be polished, and the clamp mechanism is also designed to apply a desired amount of load to the object part, thereby enabling the object part to press contact with the polishing cloth of the turntable, It is also designed to rotate in the same direction as the turntable; and a feeding mechanism for delivering the polishing slurry containing abrasive grains to the polishing cloth.

According to the present invention, also provide a kind of preparation method of semiconductor device, described method comprises:

In the insulating film deposited on the semiconductor substrate, at least one buried portion is formed, the buried portion is selected from: a groove corresponding to the configuration of the wiring layer, and an opening corresponding to the configuration of the filled via;

forming a wiring material film made of copper or copper alloy on the surface of the insulating film including the inner surface of the buried portion; and

polishing the wiring material film with a polishing device, thereby forming at least one conductive member selected from a filled via in the buried portion and a wiring layer;

Wherein, the polishing device comprises a turntable having a surface covered with a polishing cloth having a polishing layer comprising a polymer material and at least one abrasive grain selected from the group consisting of the polymer material being hydrolyzable in an aqueous medium The abrasive grains are selected from ceria, manganese oxide, silica, alumina and zirconia, and the abrasive grains are dispersed in the polymer material; the rotatable and vertically movable clamp mechanism is arranged above the turntable and designed to Fixing the object part to be polished, the fixture mechanism is also designed to apply a desired amount of load to the object part, thereby enabling the object part to come into pressurized contact with the buffing cloth of the turntable, and is also designed to rotate in the same direction as the turntable and a feed mechanism for delivering a polishing composition to the polishing cloth, the composition comprising at least water and no abrasive particles.

According to the present invention, also provide a kind of preparation method of semiconductor device, described method comprises:

In the insulating film deposited on the semiconductor substrate, at least one buried portion is formed, the buried portion is selected from: a groove corresponding to the configuration of the wiring layer, and an opening corresponding to the configuration of the filled via;

A wiring material film made of copper or copper alloy is formed on: the surface of the insulating film including the inner surface of the buried portion; and

polishing the wiring material film with a polishing device, thereby forming at least one conductive member selected from a filled via in the buried portion and a wiring layer;

wherein the polishing apparatus comprises a turntable having a surface covered with a polishing cloth having a buffing layer comprising a polymer material soluble in an aqueous medium, a rotatable and vertically movable holder A mechanism is arranged above the turntable and designed to hold the object part being polished, the clamp mechanism is also designed to apply a desired amount of load to the object part, thereby enabling the object part to come into pressurized contact with the polishing cloth of the turntable, and Also designed to rotate in the same direction as the turntable; feeding mechanism for feeding slurry containing abrasive grains to the polishing cloth.

According to the present invention, also provide a kind of preparation method of semiconductor device, described method comprises:

In the insulating film deposited on the semiconductor substrate, at least one buried portion is formed, the buried portion is selected from: a groove corresponding to the configuration of the wiring layer, and an opening corresponding to the configuration of the filled via;

A wiring material film made of copper or copper alloy is formed on: the surface of the insulating film including the inner surface of the buried portion; and

polishing the wiring material film with a polishing device, thereby forming at least one conductive member selected from a filled via in the buried portion and a wiring layer;

Wherein, the polishing device comprises a turntable having a surface covered with a polishing cloth having a buffing layer comprising a polymer material soluble in an aqueous medium and at least one abrasive grain, The abrasive grains are selected from ceria, manganese oxide, silica, alumina and zirconia, and the abrasive grains are dispersed in the polymer material; the rotatable and vertically movable clamp mechanism is arranged above the turntable and is designed to be fixed Polished object parts, the fixture mechanism is also designed to apply a desired amount of load to the object part, whereby the object part can be brought into pressurized contact with the polishing cloth of the turntable, and is additionally designed to rotate in the same direction as the turntable; A feed mechanism for delivering the polishing composition to the polishing cloth, the composition comprising at least water and no abrasive particles.

According to the present invention, also provide a kind of preparation method of semiconductor device, described method comprises:

In the insulating film deposited on the semiconductor substrate, at least one buried portion is formed, the buried portion is selected from: a groove corresponding to the configuration of the wiring layer, and an opening corresponding to the configuration of the filled via;

A wiring material film made of copper or copper alloy is formed on: the surface of the insulating film including the inner surface of the buried portion; and

polishing the wiring material film with a polishing device, thereby forming at least one conductive member selected from a filled via in the buried portion and a wiring layer;

Wherein, the polishing device comprises a turntable with a surface covered with a polishing cloth, and the polishing cloth includes a polishing layer, and when the polishing layer is subjected to frictional stress, its surface part allows elution in the presence of an aqueous medium; it can be rotated and vertically a moving clamping mechanism arranged above the turntable and designed to hold the object part being polished and additionally designed to apply a desired amount of load to the object part, thereby enabling the object part to come into pressurized contact with the polishing cloth of the turntable, It is also designed to rotate in the same direction as the turntable; and a feeding mechanism for delivering the polishing slurry containing abrasive grains to the polishing cloth.

According to the present invention, also provide a kind of preparation method of semiconductor device, described method comprises:

In the insulating film deposited on the semiconductor substrate, at least one buried portion is formed, the buried portion is selected from: a groove corresponding to the configuration of the wiring layer, and an opening corresponding to the configuration of the filled via;

A wiring material film made of copper or copper alloy is formed on: the surface of the insulating film including the inner surface of the buried portion; and

polishing the wiring material film with a polishing device, thereby forming at least one conductive member selected from a filled via in the buried portion and a wiring layer;

Wherein the polishing device comprises a turntable having a surface covered with a polishing cloth comprising a buffing layer having dispersed therein at least one abrasive grain selected from the group consisting of cerium oxide, manganese oxide, silicon dioxide , alumina and zirconia, wherein, when the polishing layer is subjected to frictional stress, its surface portion allows elution in the presence of an aqueous medium while enabling abrasive grains to be supplied to the surface of the polishing layer; capable of rotational and vertical movement The clamp mechanism is arranged above the turntable and is designed to hold the object part to be polished, the clamp mechanism is also designed to apply the desired amount of load to the object part, thereby enabling the main part to be in pressurized contact with the polishing cloth of the turntable , additionally designed to rotate in the same direction as the turntable; and a feeding mechanism for delivering a polishing agent composition to the polishing cloth, said composition comprising at least water and no abrasive grains.

Description of drawings

Figure 1 is a schematic diagram illustrating an embodiment of the polishing apparatus of the present invention;

Fig. 2 is to illustrate: when utilizing the polishing apparatus of embodiment 1 and comparative example 1 to polish silicon dioxide film, the graph of the relation between polishing time and polishing rate; With

3A, 3B and 3C respectively show: illustrate the cross-sectional view of the semiconductor device manufacturing steps in Embodiment 8 of the present invention.

Best Mode for Carrying Out the Invention

Next, the present invention will be explained in detail.

First, six kinds of polishing cloths of the present invention will be explained in detail.

(1) Polishing cloth:

The polishing cloth comprises a polishing layer comprising a polymeric material that is hydrolyzable with an aqueous medium. Specific examples of such polishing cloths include: those consisting only of a buffing layer which can be molded by injection molding of the polymeric materials described above; or comprising a substrate made of a material such as Those polishing cloths having a polishing layer deposited on said substrate by casting of the polymeric material described above, wherein said material forming the substrate is selected from a wide variety of materials such as metals.

The polymeric material is preferably selected from those comprising a main chain with branches having a structure hydrolyzable with an aqueous medium.

As structures hydrolyzable with an aqueous medium, those represented by the following formula (I) or (II):

In the formula, R ¹ , R ² and R ³ can be the same or different, and each is a hydrogen atom, an alkyl group or an aryl group:

In the formula, R ⁴ , R ⁵ and R ⁶ may be the same or different, and each is a hydrogen atom or an organic group of 1-18 carbon atoms; R ⁷ is an organic group of 1-18 carbon atoms; and R ⁶ and R ⁷ may be linked together to form a heterocyclic ring with Y ¹ (hetero atom), and Y ¹ is an oxygen atom or a sulfur atom.

In the above formula (I), R ¹ , R ² and R ³ are each a hydrogen atom, an alkyl group or an aryl group. In this case, the alkyl group is preferably selected from: alkyl groups with 1-18 carbon atoms, more preferably linear alkyl groups, most preferably linear alkyl groups with 1-4 carbon atoms.

Specific examples of the alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, n-pentyl, isopentyl, sec-pentyl base, n-pentyl, n-octyl, dodecyl, cetyl, stearyl, etc.

As the above-mentioned aryl group, it is possible to use phenyl, substituted phenyl, naphthyl, substituted naphthyl, and the like.

In the case where the branch chain attached to its main chain consists of the structure represented by the above formula (I), as an example of the polymer material hydrolyzable with an aqueous medium, it is possible to use Homopolymers or copolymers obtained by homopolymerization or copolymerization of α, β-unsaturated carboxylic acid esters, which can be obtained by carboxyl-containing α, β-unsaturated monomers and trialkylmethane chloride prepared by the reaction between silanes. As specific examples of the carboxyl group-containing α,β-unsaturated monomer used here, it is possible to use acrylic acid, methacrylic acid, itaconic acid, methyl fumaric acid, maleic acid, fumaric acid, and the like. In addition, as specific examples of trialkylsilyl chloride, it is possible to use trimethyl, triethyl, tri-n-propyl, tri-isopropyl, tri-n-butyl, tri-sec-butyl base, tri-isobutyl, tri-n-pentyl, tri-isopentyl, tri-sec-pentyl, tri-n-pentyl, tri-n-octyl, tridecyl, tricetyl , triphenyl, tri-p-methylphenyl, tribenzyl, etc. silyl chloride.

In the case where the branch chain attached to its main chain consists of the structure represented by the above formula (I), as a specific example of the polymer material hydrolyzable with an aqueous medium, it is possible to use α,β-unsaturated Homopolymers or copolymers each having repeating units of monomers represented by the following formula (III) or (IV):

In the formula, R ¹ , R ² and R ³ can be the same or different, and each is a hydrogen atom, an alkyl group or an aryl group:

As specific examples of the trialkylsilyl α,β-unsaturated carboxylic acid ester (silyl acrylate) corresponding to the weight unit of the monomer represented by the above formula (III), there can be cited the following formula ( Compounds represented by III-1) to (III-22). As specific examples of the trialkylsilyl α,β-unsaturated carboxylic acid ester (silyl methacrylate) corresponding to the weight unit of the monomer represented by the above formula (IV), the following Compounds represented by formulas (IV-1) to (IV-22).

Trimethylsilyl Acrylate:

Triethylsilyl Acrylate:

Tri-n-propylsilyl acrylate:

Tri-iso-propylsilyl acrylate:

Tri-n-butylsilyl acrylate:

Tri-iso-butylsilyl acrylate:

Tri-sec-butylsilyl acrylate:

Tri-n-pentylsilyl acrylate:

Tri-n-hexylsilyl acrylate:

Tri-n-octylsilyl acrylate:

Tri-n-dodecylsilyl acrylate:

Triphenylsilyl Acrylate:

Tris-p-methylphenyl acrylate:

Tribenzylsilyl Acrylate:

Ethyldimethylsilyl acrylate:

n-Butyldimethylsilyl acrylate:

Di-iso-propyl-n-butylsilyl acrylate:

n-octyl-di-n-butylsilyl acrylate:

Di-iso-propylstearylsilyl acrylate:

Dicyclohexylphenyl acrylate:

tert-Butylphenylsilyl Acrylate:

Lauryl diphenylsilyl acrylate:

Trimethylsilyl methacrylate:

Triethylsilyl methacrylate:

Tri-n-propylsilyl methacrylate:

Tri-iso-propylsilyl methacrylate:

Tri-n-butylsilyl methacrylate:

Tri-iso-butylsilyl methacrylate:

Tri-sec-butylsilyl methacrylate:

Tri-n-pentylsilyl methacrylate:

Tri-n-hexylsilyl methacrylate:

Tri-n-octylsilyl methacrylate:

Tri-n-dodecylsilyl methacrylate:

Triphenylsilyl methacrylate:

Tris-p-methylphenyl methacrylate:

Tribenzylsilyl methacrylate:

Ethyldimethylsilyl methacrylate:

n-Butyldimethylsilyl methacrylate:

Di-iso-propyl-n-butylsilyl methacrylate:

n-octyl-di-n-butylsilyl methacrylate:

Di-iso-propylstearylsilyl methacrylate:

Dicyclohexylphenyl methacrylate:

tert-Butylphenylsilyl methacrylate:

Lauryl diphenylsilyl methacrylate:

In addition, preferable examples of trialkylsilyl α,β-unsaturated carboxylic acid esters are represented by the following formulas (VII-1) to (VII-10).

Tri-iso-propylsilylmethyl maleate:

Tri-isopropylsilylpentyl maleate:

Tri-n-butylsilyl-n-butyl maleate:

tert-Butyldiphenylsilylmethyl maleate:

tert-Butyldiphenylsilyl-n-butyl maleate:

Tri-iso-propylsilylmethyl fumarate:

Tri-iso-propylsilylpentyl fumarate:

Tri-n-butylsilyl-n-butyl fumarate:

tert-Butyldiphenylsilylmethyl fumarate:

tert-Butyldiphenylsilyl-n-butyl fumarate:

If the above-mentioned polymer material is formed of a copolymer, it can be obtained by copolymerization of a trialkylsilyl α,β-unsaturated carboxylic acid ester with another monomer. As a specific example of the monomer used here, it is possible to use an α,β-unsaturated monomer. As specific examples of such α,β-unsaturated monomers, it is possible to use: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate , n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ( Lauryl meth)acrylate, stearyl (meth)acrylate, styrene, alpha-methylstyrene, p-vinyltoluene, acrylonitrile, 2-hydroxyethyl (meth)acrylate, or polyethylene Adduct of diol or polypropylene glycol with 2-hydroxyethyl (meth)acrylate, or its methyl or diethyl ether.

In the above formula (II), the groups R ⁴ , R ⁵ and R ⁶ may be the same or different and each is a hydrogen atom or an organic group of 1-18 carbon atoms such as an alkyl group, an aryl group, an alkanol, etc.; R ⁷ is an alkyl group, aryl ^group or alkanol with or without substituents, respectively having 1-18 carbon atoms; and R ⁶ and R ⁷ may be connected together to form Substituents of heterocyclic rings. As specific examples of the alkyl group, preferably used: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, n-pentyl, isopentyl, sec-pentyl, n-pentyl, n-octyl, dodecyl, cetyl, stearyl, etc.

The compound represented by the above formula (II) and having a structure hydrolyzable with an aqueous medium, for example, can be obtained by a compound having a carboxyl group (for example, a compound having one or more, preferably 1 to 120 carboxyl groups per molecule) and a compound selected from the group consisting of It can be easily obtained by reacting a compound of a vinyl ether compound represented by formula (VII), a vinyl sulfide compound, and a compound of a heterocyclic compound having an ethylenic double bond and a heteroatom composed of an oxygen atom or a sulfur atom.

In the formula, R ⁴ , R ⁵ and R ⁶ may be the same or different, and each is a hydrogen atom or an organic group of 1-18 carbon atoms; R ⁷ is an organic group of 1-18 carbon atoms; and R ⁶ and R ⁷ may be linked together to form a heterocyclic ring with Y ¹ (hetero atom), and Y ¹ is an oxygen atom or a sulfur atom.

In the above formula (VIII), the groups R ⁴ , R ⁵ and R ⁶ may be the same or different and each is a hydrogen atom or an organic group of 1-18 carbon atoms such as an alkyl group, an aryl group, an alkanol, etc.; R ⁷ is an alkyl group, aryl ^group or alkanol with or without substituents, respectively having 1-18 carbon atoms; and R ⁶ and R ⁷ may be connected together to form Substituents of heterocyclic rings.

Specific examples of the compound represented by the above formula (VIII) are: aliphatic vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n- Butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, etc.; aliphatic vinyl sulfide compounds corresponding to any of the aforementioned ethers; cyclovinyl Ether compounds such as 2,3-dihydrofuran, 3,4-dihydro-2H-pyran and the like; and cyclovinylsulfide compounds corresponding to any of the above-mentioned cyclovinyl ethers.

Specific examples of polymer materials having at least one carboxyl group per molecule include, for example, polyester resins, acrylic resins, maleic polybutadiene resins, and the like.

The reaction between the compound having at least one carboxyl group per molecule and the compound represented by the above formula (VIII) is usually carried out in the presence of an acid catalyst at a temperature of room temperature to 100°C.

In the case where the branch chain attached to its main chain is composed of the structure represented by the above formula (II), as an example of the polymer material hydrolyzable with an aqueous medium, it is possible to use a carboxyl group-containing α, β-not A homopolymer or copolymer obtained by homopolymerization or copolymerization of a reaction product produced by a reaction between a saturated monomer and a compound represented by the above formula (VIII). As specific examples of the carboxyl group-containing α,β-unsaturated monomer used here, it is possible to use acrylic acid, methacrylic acid, itaconic acid, methyl fumaric acid, maleic acid, fumaric acid, and the like.

In the case where the branch chain attached to its main chain consists of the structure represented by the above formula (II), as a specific example of the polymer material hydrolyzable with an aqueous medium, it is possible to use α,β-unsaturated Homopolymers or copolymers each having a repeating unit of a monomer represented by the following formula (V) or (VI):

In the formula, R ⁴ , R ⁵ and R ⁶ may be the same or different, and each is a hydrogen atom or an organic group of 1-18 carbon atoms; R ⁷ is an organic group of 1-18 carbon atoms; and R ⁶ and R ⁷ may be linked together to form a heterocyclic ring with Y ¹ (hetero atom), and Y ¹ is an oxygen atom or a sulfur atom.

The following formulas (V-1) to (V-8) are specific examples of the reaction product (hemiacetal acrylate), which can be obtained by carboxyl group-containing α corresponding to the repeating unit of the monomer represented by the above formula (V). Obtained by the reaction between the β-unsaturated monomer and the compound represented by the above formula (VIII). In addition, the following formulas (V-1) to (V-8) are specific examples of reaction products (hemiacetal acrylate), which can be obtained by containing It is obtained by the reaction between a carboxy α β-unsaturated monomer and a compound represented by the above formula (VIII).

1-methoxyethyl acrylate:

1-Ethoxyethyl Acrylate:

1-n-propoxyethyl acrylate:

1-iso-propoxyethyl acrylate:

1-n-butoxyethyl acrylate:

1-iso-butoxyethyl acrylate:

1-(2-Ethylhexyloxy)ethyl acrylate:

Pyranyl Acrylate:

1-methoxyethyl methacrylate:

1-Ethoxyethyl methacrylate:

1-n-propoxyethyl methacrylate:

1-iso-propoxyethyl methacrylate:

1-n-butoxyethyl methacrylate:

1-iso-butoxyethyl methacrylate:

1-(2-Ethylhexyloxy)ethyl methacrylate:

Pyranyl Methacrylate:

Other preferable examples of the reaction product which can be obtained by the reaction between the carboxyl group-containing α β-unsaturated monomer and the compound represented by the above formula (VIII) are given by the following formulas (IX-1) to (IX-8) enumerate.

Di-1-methoxyethyl maleate:

Di-1-ethoxyethyl maleate:

Di-1-n-propoxyethyl maleate:

Di-1-iso-propoxyethyl maleate:

Di-1-n-butoxyethyl maleate:

Di-1-iso-butoxyethyl maleate:

Di-1-(2-ethylhexyloxy)ethyl maleate:

Pyranyl maleate:

If the above-mentioned polymer material is composed of a copolymer, it can be obtained by copolymerization of a reaction product obtained by a reaction between a carboxyl group-containing α β-unsaturated monomer and a compound represented by the above formula (VIII) with another monomer And get. As a specific example of the monomer used here, it is possible to use an α,β-unsaturated monomer. As specific examples of such α,β-unsaturated monomers, it is possible to use: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate , n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ( Lauryl meth)acrylate, stearyl (meth)acrylate, styrene, alpha-methylstyrene, p-vinyltoluene, acrylonitrile, 2-hydroxyethyl (meth)acrylate, or polyethylene Adduct of diol or polypropylene glycol with 2-hydroxyethyl (meth)acrylate, or its methyl or diethyl ether.

The content of the repeating unit of the monomer represented by the above formula (III), (IV), (V) or (VI) in the above-mentioned polymer material is preferably limited to a range of 20-100% by weight, more preferably 40-100% by weight. 100% by weight. If the content of monomeric repeating units is less than 20% by weight, the amount of carboxyl groups regenerated when the polymer material is hydrolyzed will become too small, thereby reducing the solubility of the polymer material in aqueous media, thus making the polishing cloth poor polishing performance.

The polymeric material is preferably selected from those having a number average molecular weight from 500-500,000, more preferably from 500-100,000, and a glass transition temperature from 30-100°C, more preferably from 40-80°C. In addition, a polishing cloth comprising a polymer material having the above-mentioned specified number average molecular weight and glass transition temperature range can further stabilize the polishing performance when polishing an object part to be polished.

The aforementioned buffing layer should preferably be constructed such that particles of a substance having a higher solubility than the polymer material are dispersed in the polymer material.

As examples of the substance, it is possible to use rosin, cellulose, polyvinyl alcohol and the like. The particles of the substance should preferably be dispersed at a ratio of 1 to 50% by volume, based on the polymer material. This is because, if the amount of the dispersed particles is less than 1% by volume, it may be difficult to sufficiently increase the effect of these dispersed particles (the effect of promoting the dissolution of the polishing layer in the polishing step). On the other hand, if the amount of dispersed particles is higher than 50% by volume, the polishing layer may be decomposed as soon as it is immersed in an aqueous solution, thereby rendering the polishing cloth inoperative.

(2) Polishing cloth:

The polishing cloth comprises a polishing layer containing a polymer material and at least one abrasive grain selected from the group consisting of; the polymer material is hydrolyzable in an aqueous medium; the abrasive grain is selected from the group consisting of cerium oxide, manganese oxide, silicon dioxide, Aluminum oxide and zirconium oxide, the abrasive grains are dispersed in a polymeric material. Specific examples of the polishing cloth include: those consisting only of a polishing layer which can be molded by injection molding the above-mentioned polymer material; or comprising a substrate made of Those polishing cloths for the casting of the polymeric materials described above to deposit a buffing layer on said substrate, wherein said material from which the substrate is made is selected from a wide variety of materials such as metals.

The polymer material used in this case may be the same as that used in the above-mentioned polishing cloth (1).

The abrasive grains are preferably uniformly incorporated and dispersed in the polymer material at a ratio of 0.5-20% by weight.

The abrasive grains should preferably be spherical or nearly spherical with an average particle size in the range of 0.02-0.1 microns.

(3) Polishing cloth:

The polishing cloth comprises a buffing layer comprising a polymeric material that is soluble in an aqueous medium. Specific examples of the polishing cloth include: those consisting only of a polishing layer which can be molded by injection molding the above-mentioned polymer material; or comprising a substrate made of Those polishing cloths for the casting of the above polymeric materials to deposit a polishing layer on said substrate, wherein said substrate is made from a material selected from a wide variety of materials such as metals.

When the relative velocity between the buffing layer and the object part to be polished is set at 1.0 m/sec under the condition that the buffing layer is brought into contact with the buffing layer by applying a load of 300 gf/ ^cm2 to the object part, it is preferable that , the polymeric material is selected from those materials that are soluble in an aqueous medium at a rate of 0.01-10.0 mg/min. When the dissolution rate of the polymer material is lower than 0.01 mg/min, when the buffing layer and the object part are rotated with each other, while applying a desired load to the object part and simultaneously delivering the polishing slurry containing abrasive grains and water To the buffing layer, when the object part being polished is subjected to polishing, it may be difficult to satisfactorily restore the surface of the buffing layer, thus possibly resulting in localized accumulation of abrasive grains on the buffing layer. On the other hand, when the dissolution rate of the polymer material is higher than 10.0 mg/min, the polishing slurry may be forcibly removed from the layer, thereby making it difficult to adequately transport the abrasive grains of the polishing slurry to the interface between the buffing layer and the object part.

The polymer material can be: at least one selected from acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, N-vinyl- Homopolymer or copolymer obtained by polymerization of monomers of 2-pyrrolidone, methyl vinyl ether, N-vinylformamide and N,N-dimethylacrylamide.

(4) Polishing cloth:

The polishing cloth comprises a buffing layer comprising a polymeric material soluble in an aqueous medium and at least one abrasive grain selected from the group consisting of ceria, manganese oxide, silica, alumina and zirconia , the abrasive grains are dispersed in the polymer material. Specific examples of the polishing cloth include: those consisting only of a polishing layer which can be molded by injection molding the above-mentioned polymer material; or comprising a substrate made of Those polishing cloths for the casting of the above polymeric materials to deposit a polishing layer on said substrate, wherein said substrate is made from a material selected from a wide variety of materials such as metals.

The polymer material used in this case may be the same as that used in the above-mentioned polishing cloth (3).

The abrasive grains are preferably uniformly incorporated and dispersed in the polymer material at a ratio of 0.5-20% by weight.

The abrasive grains should preferably be spherical or nearly spherical with an average particle size in the range of 0.02-0.1 microns.

(5) Polishing cloth:

The polishing cloth comprises a buffing layer whose surface prohibits elution in the presence of an aqueous medium until the buffing layer is subjected to frictional stress, and permits elution in the presence of an aqueous medium when the buffing layer is subjected to frictional stress .

In this ^case , "frictional stress" means: when the polishing layer and The force applied to the polishing layer when the relative speed between the parts of the polishing object is set at 0.2-3.0m/sec.

Specific examples of the polishing cloth include those consisting of a polishing layer only, or those comprising a substrate made of a material selected from various materials such as metals and the above-mentioned polishing layer deposited on the substrate .

The polishing layer is formed of a material comprising a polymer material (in particular, a homopolymer or a copolymer each having a monomer repeating unit represented by the above formula (III), (IV), (V) or (VI), As described above for the polishing cloth (1), the polymeric material is hydrolyzable by an aqueous medium.

(6) Polishing cloth:

The polishing cloth comprises a buffing layer in which at least one abrasive grain selected from cerium oxide, manganese oxide, silicon dioxide, aluminum oxide and zirconia is dispersed, wherein, before the buffing layer is subjected to frictional stress , the surface portion of the polishing layer is prohibited from elution in the presence of an aqueous medium, and when the polishing layer is subject to frictional stress, it is allowed to elute in the presence of an aqueous medium, and advance simultaneously, so that the abrasive grains can be supplied to the polishing layer surface.

In this ^case , "frictional stress" means: when the polishing layer and The force applied to the polishing layer when the relative speed between the parts of the polishing object is set at 0.2-3.0m/sec.

Specific examples of the polishing cloth include: a polishing cloth consisting only of the polishing layer containing the above-mentioned abrasive grains; or those comprising a substrate made of a material selected from various materials such as metal, and the above-mentioned polishing layer containing the above-mentioned abrasive grains Polishing cloth, the polishing layer is deposited on the substrate.

The polishing layer is made of a material comprising a polymer material (in particular, a homopolymer or a copolymer each having a monomer repeating unit represented by the above formula (III), (IV), (V) or (VI)) and the above-mentioned Abrasive grains are formed, as described above for the polishing cloth (1), the polymeric material being hydrolyzable by an aqueous medium.

The abrasive grains are preferably uniformly incorporated and dispersed in the polishing layer at a rate of 0.5-20% by weight.

The abrasive grains should preferably be spherical or nearly spherical with an average particle size in the range of 0.02-0.1 microns.

Next, the polishing apparatus of the present invention will be explained with reference to FIG. 1 .

The turntable 1 is covered with a polishing cloth 2 . A feed pipe 3 is arranged above the polishing cloth 2, said feed pipe being used to convey a polishing slurry comprising abrasive grains and water and, if desired, surfactants and dispersants, or without water Abrasive grains and, if desired, polishing compositions with or without surfactants and dispersants. A substrate holder 5 having a support shaft 4 on its top surface is rotatably and vertically movable arranged above the polishing cloth 2 .

Examples of surfactants contained in the polishing slurry or in the polishing agent composition include: for example, nonionic surfactants such as polyethylene glycol phenyl ether, glycol aliphatic esters, etc.; amphoteric surfactants such as imidazole beet bases; anionic surfactants such as sodium lauryl sulfate; and cationic surfactants such as stearintrimonium chloride.

As the polishing cloth, it is possible to use those having the same structure as described in (1) to (6) above. However, when the above-mentioned polishing cloths (1), (3) and (5) are used for polishing treatment of object parts, the polishing slurry containing abrasive grains and water is delivered to the polishing cloths from the feed pipe 3 . On the other hand, when the above-mentioned polishing cloths (2), (4) and (6) are used for polishing treatment of object parts, a polishing composition comprising water but no abrasive grains and, if necessary, a surfactant and a dispersant The material is transported to the polishing cloth by the feed pipe 3. Next, a specific polishing method will be explained.

(a) Polishing treatment carried out by a polishing device equipped with a polishing cloth having any of the above-mentioned structures (1), (3) and (5):

First, an object part 6 to be polished, such as a substrate, is grasped by the jig 5 in such a manner that the surface to be polished faces the polishing cloth 2 . Then, when the polishing slurry comprising abrasive grains and water is continuously conveyed to the polishing cloth 2 from the feed pipe 3, a desired load is applied to the object part 6 by means of the support shaft 4, so that the object part 6 and the polishing cloth 2 touch. At the same time, the jig 5 and the turntable 1 are kept rotating in the same direction as each other. Thus, the surface of the object part 6 to be polished is polished by the abrasive grains in the polishing slurry delivered to the interface between the object part 6 and the polishing cloth 2 .

(b) Polishing using a polishing device equipped with a polishing cloth having any of the above-mentioned structures (2), (4) and (6):

First, an object part 6 to be polished, such as a substrate, is grasped by the jig 5 in such a manner that the surface to be polished faces the polishing cloth 2 . Then, while the polishing composition containing at least water and not containing abrasive grains is continuously conveyed to the polishing cloth 2 from the feed pipe 3, a desired amount of load is applied to the object part 6 by means of the support shaft 4, so that the object part 6 Contact with polishing cloth 2. At the same time, the jig 5 and the turntable 1 are kept rotating in the same direction as each other. In this case, the abrasive grains dispersed in the buffing layer of the polishing cloth can be transported to the interface between the surface of the object part 6 to be polished and the buffing layer due to the elution of the buffing layer material. Thus, the surface of the object part 6 to be polished is polished by means of the abrasive grains supplied by the buffing layer and in the presence of the polishing composition comprising water delivered by the feed pipe 3 .

Next, the method of manufacturing the semiconductor device of the present invention will be explained.

(first step)

At least one buried portion selected from grooves and openings is formed on the surface of the substrate, and a wiring material film made of copper or copper alloy is deposited on the entire surface including the buried portion of the substrate.

As the substrate, it is possible to use, for example, a semiconductor substrate or a glass substrate.

The buried portion can be formed in an insulating film formed on a base material. As specific examples of the insulating film, it is possible to use, for example, a silicon dioxide film, a boron-impregnated glass film (BPSG film), a phosphorus-impregnated glass film (PSG film) and the like. The insulating film may be covered on its surface with a polishing-stopper film formed of a material selected from silicon nitride, carbon, aluminum oxide, boron nitride, diamond, and the like.

As the copper-based metal, it is possible to use copper (Cu) or copper alloys such as Cu-Si alloys, Cu-Al alloys, Cu-Si-Al alloys, Cu-Ag alloys and the like.

The wiring material film can be formed by, for example, sputter deposition, vacuum deposition or electroplating.

The conductive barrier layer may be deposited on the insulating film including the buried portion formed on the surface of the semiconductor substrate before the wiring material film is deposited on the insulating film. When such a conductive barrier layer is deposited on an insulating film including a buried portion, at least one buried conductive member selected from a wiring layer and a filled via may be formed in the buried portion, the buried portion being After the thin film of wiring material is deposited, it is surrounded by a conductive barrier layer due to the polishing process performed as described later. Accordingly, copper used as a conductive member can be prevented from diffusing into the insulating film by the conductive barrier film, thus preventing the semiconductor substrate from being contaminated with copper.

The conductive barrier film may be formed of a single layer or multiple layers of materials selected from, for example, TiN, Ti, Nb, W, WN, TaN, TaSiN, Ta, Co, Zr, ZrN and CuTa. Preferably, the conductive barrier film is formed such that its thickness is from 15 to 50 nm.

(second step)

The thin film of wiring material formed on the substrate is subjected to a polishing process using a polishing device, whereby the copper-based metal is buried inside the embedded part, thereby forming a buried conductive part, such as a buried part composed of copper or a copper alloy wiring layer.

Specifically, the embedded conductive member can be formed by the following method.

(a) First, the semiconductor substrate 6 serving as a part of the object to be polished is fixed by the jig 5 in such a manner that the wiring material film made of copper or copper alloy can face the polishing cloth (having the above-mentioned structure (1), ( 3) and (5) any one of the polishing cloth) 2. Then, when the polishing slurry 7 comprising abrasive grains and water is continuously conveyed to the polishing cloth 2 from the feed pipe 3, a desired load is applied to the semiconductor substrate 6 by means of the support shaft 4, so that the semiconductor substrate 6 and the Polishing cloth 2 contacts. At the same time, the jig 5 and the turntable 1 are kept rotating in the same direction as each other. Therefore, the wiring material film of the semiconductor substrate 6 is mainly polished by the abrasive grains in the polishing slurry that have been delivered to the contact surface between the wiring material film and the polishing cloth 2, thereby forming a pattern in which copper or a copper alloy is embedded in the buried surface. A partially internal, embedded conductive component.

(b) First, the semiconductor substrate 6 serving as a part of the object to be polished is fixed by the jig 5 in such a manner that the wiring material film made of copper or copper alloy can face the polishing cloth (having the above-mentioned structure (2), ( 4) and (6) any one of the polishing cloth) 2. Then, when the polishing composition containing at least water and not containing abrasive grains is continuously conveyed from the feed pipe 3 to the polishing cloth 2, the desired load is applied to the semiconductor substrate 6 by means of the support shaft 4, so that the semiconductor substrate The material 6 is in contact with the polishing cloth 2. At the same time, the jig 5 and the turntable 1 are kept rotating in the same direction as each other. In this case, the abrasive grains dispersed in the polishing layer of the polishing cloth can enter the interface between the wiring material film of the substrate 6 and the polishing layer due to the elution of the polishing layer material. Accordingly, the wiring material film of the base material 6 is polished with the abrasive grains supplied from the polishing layer and in the presence of the polishing composition containing water delivered from the feed pipe 3, thereby forming a film in which copper or copper alloy is buried. A buried conductive component within a buried part.

The above-mentioned polishing slurry or polishing agent composition may additionally include: a water-soluble organic acid (the first organic acid) capable of reacting with copper to produce a copper complex, the complex being substantially insoluble in water and having a mechanical strength lower than that of Mechanical strength of copper and oxidizing agents.

Specific examples of the first organic acid include, for example, 2-quinolinecarboxylic acid (quinalidineic acid), 2-pyridinecarboxylic acid, 2,6-pyridinecarboxylic acid, quinolinic acid and the like.

The mixing ratio of the first organic acid in the polishing slurry or the polishing agent composition is preferably 0.1% by weight or higher. In addition, if the mixing ratio of the first organic acid is less than 0.1% by weight, it may be difficult to sufficiently produce a copper complex whose mechanical strength is lower than that of copper on the surface of the copper or copper alloy thin film. Therefore, it may be difficult to sufficiently promote the polishing rate of the copper or copper alloy thin film in its polishing stage. More preferably, the mixing ratio of the first organic acid is in the range of 0.3-1.2% by weight.

The oxidizing agent described above is effective in generating copper hydrate when the polishing slurry or polishing composition contacts a copper or copper alloy film. Specific examples of the oxidizing agent are hydrogen peroxide (H ₂ O ₂ ), sodium hypochlorite (NaClO) and the like.

In the polishing slurry or the polishing agent composition, the mixing ratio of the oxidizing agent is preferably at least ten times (by weight) that of the first organic acid. This is because, if the mixing ratio of the oxidizing agent is less than ten times (by weight) relative to the first organic acid, it may be difficult to sufficiently promote the generation of copper complexes on the surface of the copper or copper alloy thin film. With respect to the first organic acid, the mixing ratio of the oxidizing agent is preferably not less than 30 times (by weight), more preferably not less than 50 times (by weight) that of the first organic acid.

The above-mentioned polishing slurry or polishing agent composition may additionally include: an organic acid (second organic acid) having one carboxyl group and one hydroxyl group.

The above-mentioned second organic acid can effectively promote the above-mentioned action of the oxidizing agent to produce copper hydrate. Specific examples of the second organic acid include: lactic acid, tartaric acid, mandelic acid, malic acid, and the like. These acids may be used alone or in admixture of two or more. Among these acids, lactic acid is most preferred.

The mixing ratio of the second organic acid in the polishing slurry or the polishing agent composition is preferably limited to 20 to 250% by weight based on the weight of the first organic acid. This is because, if the mixing ratio of the second organic acid is less than 20% by weight, it may be difficult to sufficiently promote the action of the oxidizing agent to generate copper hydrate. On the other hand, if the mixing ratio of the second organic acid exceeds 250% by weight, the wiring material film formed of copper or copper alloy may be etched away, thereby making it impossible to form a wiring pattern. More preferably, the mixing ratio of the second organic acid is in the range of 40-200% by weight based on the weight of the first organic acid.

As described above, the polishing cloth [polishing cloth (1)] according to the present invention comprises a polishing layer comprising a polymer material which is hydrolyzable with an aqueous medium.

When the polishing slurry comprising abrasive grains and water is delivered onto the polishing cloth constituted as described above, wherein the polishing cloth is kept rotating while pressing the object part against the polishing cloth, the polishing surface of the object part is mainly conveyed to the object Polishing of abrasive grains in the polishing slurry at the interface between the component and the polishing cloth. In this case, since the polishing cloth comprises a polymer material which is hydrolyzable with an aqueous medium, the region of the buffing layer to which a mechanical force is locally applied by sliding contact under pressure of the object part can be The water in the slurry it provides is hydrolyzed and dissolved, thus enabling the surface of the polishing cloth to always be renewed. Therefore, it is now possible to prevent the accumulation and growth of abrasive grains in the polishing slurry on the surface of the polishing cloth (buffing surface). As a result, the polishing cloth can exhibit satisfactory polishing performance almost equivalent to the initial polishing performance (compared with the polishing rate in the initial polishing stage, for a considerable period of time without carrying out the surface regeneration operation, more or less will be reduced), the surface regeneration operation is usually carried out after the polishing process of the object part and before the next polishing process by means of the dressing tool of the dressing device. Accordingly, it is now possible to provide a polishing cloth capable of stably polishing object parts for a relatively long period of time without necessary conditioning.

In particular, when the polymer material constituting the main component of the polishing layer is composed of homopolymerized monomer repeating units (silyl acrylate or silyl methacrylate) each having the above formula (III) or (IV), or a copolymer, or a homopolymer or a copolymer each having a monomer repeating unit (hemiacetal acrylate or hemiacetal methacrylate) represented by the above formula (V) or (VI), The solubility of the polishing cloth by hydrolysis can be further increased, thus making it possible to further improve the renewal efficiency of the polishing cloth surface.

That is, homopolymers or copolymers each having a monomer repeating unit represented by the above formula (III), (IV), (V) or (VI) have: a silyl ester group each bonded to its main chain Or hemiacetal ester groups so that, when these esters are hydrolyzed, free hydrophilic carboxyl groups will regenerate, thereby making it possible to more smoothly dissolve the surface of the polishing cloth and thus further promote the renewal of the surface of the polishing cloth.

In addition, when particles of substances more soluble than polymer materials (such as rosin) are dispersed in the polishing cloth, dissolution originating from these particles will proceed, thereby making it possible to further promote the renewal of the surface of the polishing cloth .

Another polishing cloth according to the invention [polishing cloth (2)] comprises a polishing layer comprising a polymer material hydrolyzable with an aqueous medium and at least one abrasive grain selected from the group consisting of Cerium, manganese oxide, silica, alumina and zirconia and dispersed in the polymer material.

When a polishing composition free of water and abrasive particles is delivered onto a polishing cloth constructed as described above, the polishing cloth is kept rotating while pressing the object part against the polishing cloth, since the polishing cloth contains a polymeric material that is hydrolyzable with an aqueous medium , under the pressure of the object part, the region of the buffing layer to which a mechanical force is locally applied by sliding contact, is hydrolyzed and eluted by means of water included in the polishing composition supplied thereto. As a result, the abrasive grains dispersed in the polishing cloth can enter the interface between the object part and the polishing cloth, thereby enabling the abrasive grains to be automatically transported to the above-mentioned interface, thereby enabling the polishing surface of the object part to be mainly polished by the abrasive grains. grain polish. In addition, since the polishing cloth can be dissolved by its hydrolysis and the surface of the polishing cloth can always be renewed, it is now possible to prevent abrasive grains from accumulating and growing on the surface of the polishing cloth. As a result, the polishing cloth can exhibit satisfactory polishing performance almost equivalent to the initial polishing performance (compared with the polishing rate in the initial polishing stage, for a considerable period of time without carrying out the surface regeneration operation, more or less will be reduced), the surface regeneration operation is usually carried out after the polishing process of the object part and before the next polishing process by means of the dressing tool of the dressing device. Accordingly, it is now possible to provide a polishing cloth capable of stably polishing object parts for a relatively long period of time without necessary conditioning.

In particular, when the polymer material constituting the main component of the polishing layer is composed of homogeneous monomers each having a monomer repeating unit (silyl acrylate or silyl methacrylate) represented by the above formula (III) or (IV), Formed from polymers or copolymers, or from homopolymers or copolymers each having a repeating unit of a monomer represented by the above formula (V) or (VI) (hemiacetal acrylate or hemiacetal methacrylate) , the solubility by hydrolysis of the polishing cloth can be further increased, thus making it possible to smoothly transport the abrasive grains from the polishing cloth, and at the same time, improve the renewal efficiency of the surface of the polishing cloth.

In addition, when particles of substances having a higher solubility than polymer materials (such as rosin) are dispersed in the polishing cloth, dissolution originating from these particles will proceed, thereby making it possible to more smoothly transport the Abrasive grains, while further promoting the renewal of the surface of the polishing cloth.

Another polishing cloth according to the invention [polishing cloth (3)] comprises a polishing layer comprising a polymer material which is soluble in an aqueous medium.

When the polishing slurry comprising abrasive grains and water is delivered onto the polishing cloth constituted as described above, wherein the polishing cloth is kept rotating while pressing the object part against the polishing cloth, the polishing surface of the object part is mainly conveyed to the object Polishing of abrasive grains in the polishing slurry at the interface between the component and the polishing cloth. In this case, since the polishing cloth comprises a polymer material soluble in an aqueous medium, the area of the buffing layer to which a mechanical force is locally applied by sliding contact under pressure of the object part can be included in the The water in the supplied polishing slurry dissolves so that the surface of the polishing cloth can always be renewed. Therefore, it is now possible to prevent the accumulation and growth of abrasive grains in the polishing slurry on the surface of the polishing cloth (buffing surface). As a result, the polishing cloth can exhibit satisfactory polishing performance almost equivalent to the initial polishing performance (compared with the polishing rate in the initial polishing stage, for a considerable period of time without carrying out the surface regeneration operation, more or less will be reduced), the surface regeneration operation is usually carried out after the polishing process of the object part and before the next polishing process by means of the dressing tool of the dressing device. Accordingly, it is now possible to provide a polishing cloth capable of stably polishing object parts for a relatively long period of time without necessary conditioning.

In particular, when the relative velocity between the buffing layer and the object part to be polished is set at 1.0 m/sec under the condition that it is brought into contact with the buffing layer by applying a load of 300 gf/ ^cm2 to the object part , when the polymer material constituting the main component of the polishing layer is formed of a material that can be dissolved at a rate of 0.01-10.0 mg/min in an aqueous medium, the solubility of the polishing cloth will be further increased in the polishing step, thus enabling it to Further improve the renewal efficiency of the polishing cloth surface.

Another polishing cloth according to the invention [polishing cloth (4)] comprises a polishing layer comprising a polymer material which is soluble in an aqueous medium and at least one abrasive grain selected from ceria, manganese oxide, silica, alumina and zirconia and dispersed in a polymeric material.

When a polishing composition free of water and abrasive grains is delivered onto a polishing cloth constructed as described above, the cloth is kept rotating while pressing the object part against the cloth, since the cloth contains polymeric particles soluble in an aqueous medium. The object material, the area of the buffing layer to which a mechanical force is applied by the sliding contact of the object parts, is eluted by means of water included in the polishing composition supplied thereto. As a result, the abrasive grains dispersed in the polishing cloth can enter the interface between the object part and the polishing cloth, thereby enabling the abrasive grains to be automatically transported to the above-mentioned interface, thereby enabling the polishing surface of the object part to be mainly polished by the abrasive grains. grain polish. In addition, since the polishing cloth can be dissolved in water and the surface of the polishing cloth can always be renewed, it is now possible to prevent accumulation and growth of abrasive grains on the surface of the polishing cloth. As a result, the polishing cloth can exhibit satisfactory polishing performance almost equivalent to the initial polishing performance (compared with the polishing rate in the initial polishing stage, for a considerable period of time without carrying out the surface regeneration operation, more or less will be reduced), the surface regeneration operation is usually carried out after the polishing process of the object part and before the next polishing process by means of the dressing tool of the dressing device. Accordingly, it is now possible to provide a polishing cloth capable of stably polishing object parts for a relatively long period of time without necessary conditioning.

In particular, when the relative velocity between the buffing layer and the object part to be polished is set at 1.0 m/sec under the condition that it is brought into contact with the buffing layer by applying a load of 300 gf/ ^cm2 to the object part , when the polymer material constituting the main component of the polishing layer is formed of a material that can be dissolved at a rate of 0.01-10.0 mg/min in an aqueous medium, the solubility of the polishing cloth will be further increased in the polishing step, thus enabling it to Smoother delivery of abrasive grains from the polishing cloth while making it possible to further improve the renewal efficiency of the polishing cloth surface.

Another polishing cloth according to the present invention [polishing cloth (5)] comprises a buffing layer whose surface is prohibited from elution in the presence of an aqueous medium until the buffing layer is subjected to frictional stress; when the buffing layer is subjected to frictional stress, Its surface allows elution in the presence of aqueous media.

When the polishing slurry containing abrasive grains and water is delivered onto the polishing cloth constituted as described above, wherein the polishing cloth is kept rotating while pressing the object part against the polishing cloth, the polishing surface of the object part is mainly transferred to the object part Abrasive grain polishing in the polishing slurry at the interface between the polishing cloth and the polishing cloth. In this case, the buffing layer area receiving the mechanical force (frictional force or frictional stress) applied by the pressurization of the object part and the sliding contact of the object part, in the water included in the polishing slurry supplied thereto, The elution is carried out in the presence of , thus, enabling the surface of the polishing cloth to be always renewed. Therefore, it is now possible to prevent the accumulation and growth of abrasive grains in the polishing slurry on the surface of the polishing cloth (buffing surface). As a result, the polishing cloth can exhibit satisfactory polishing performance almost equivalent to the initial polishing performance (compared with the polishing rate in the initial polishing stage, for a considerable period of time without carrying out the surface regeneration operation, more or less will be reduced), the surface regeneration operation is usually carried out after the polishing process of the object part and before the next polishing process by means of the dressing tool of the dressing device. Accordingly, it is now possible to provide a polishing cloth capable of stably polishing object parts for a relatively long period of time without necessary conditioning.

Another polishing cloth according to the invention [polishing cloth (6)] comprises: at least one buffing layer on one of its faces designed to come into contact with a part of an object to be polished, in which at least one buffing layer is dispersed. Abrasive grains selected from ceria, manganese oxide, silica, alumina and zirconia. The surface portion of the polishing layer prohibits elution in the presence of an aqueous medium until the polishing layer is subjected to frictional stress; and when the polishing layer is subjected to frictional stress, elution is allowed in the presence of an aqueous medium while allowing the abrasive grains to supplied to the surface of the buffing layer.

When the polishing composition free of water and abrasive grains is fed onto the polishing cloth constituted as described above, the polishing cloth keeps rotating while pressing the object part against the polishing cloth, accepting the sliding of the object part by pressing the object part The regions of the buffing layer that are in contact with the applied mechanical force (frictional stress) undergo elution in the presence of water included in the polishing composition supplied thereto. As a result, the abrasive grains dispersed in the polishing cloth can enter the interface between the object part and the polishing cloth, thereby enabling the abrasive grains to be automatically transported to the above-mentioned interface, thereby enabling the polishing surface of the object part to be mainly polished by the abrasive grains. grain polish. In addition, since the polishing cloth can be eluted in the presence of water due to the aforementioned frictional stress, and the surface of the polishing cloth can always be renewed, it is now possible to prevent accumulation and growth of abrasive grains on the surface of the polishing cloth. As a result, the polishing cloth can exhibit satisfactory polishing performance almost equivalent to the initial polishing performance (compared with the polishing rate in the initial polishing stage, for a considerable period of time without carrying out the surface regeneration operation, more or less will be reduced), the surface regeneration operation is usually carried out after the polishing process of the object part and before the next polishing process by means of the dressing tool of the dressing device. Accordingly, it is now possible to provide a polishing cloth capable of stably polishing object parts for a relatively long period of time without necessary conditioning.

A polishing apparatus according to an embodiment of the present invention includes: a turntable having a surface covered with a polishing cloth, and the polishing cloth has a polishing layer made of any one of the above structures (1), (3) and (5); rotatable and a fixture mechanism vertically movable, arranged on the turntable, designed to fix the body part being polished; the fixture mechanism is also designed to apply a desired amount of load to the body part, whereby a polishing cloth in pressurized contact; additionally designed to rotate in the same direction as the turntable; and a feeding mechanism for delivering polishing slurry containing abrasive grains to the polishing cloth. Owing to the effect of the polishing cloth having any one of the above-mentioned structures (1), (3) and (5), the polishing device can stably polish object parts for a long time without reconditioning.

A polishing apparatus according to another embodiment of the present invention includes: a turntable having a surface covered with a polishing cloth with a polishing layer, wherein the polishing layer is composed of any one of the above structures (2), (4) and (6) Consists of and contains at least one abrasive grain selected from the group consisting of ceria, manganese oxide, silica, alumina and zirconia; a fixed mechanism, rotatably and vertically movable, arranged above a turntable, designed to hold the polished the body part; the clamp mechanism is also designed to apply a desired amount of load to the body part, thereby bringing the body part into pressurized contact with the polishing cloth of the turntable; additionally designed to rotate in the same direction as the turntable; and A feed mechanism for delivering a polishing composition comprising at least water and no abrasive particles to a polishing cloth. Due to the effect of the polishing cloth having any one of the above-mentioned structures (2), (4) and (6), the polishing device can automatically feed abrasive grains to the polishing surface and can also stably polish object parts for a long time , without the need for refurbishment.

A method for preparing a polishing device according to another embodiment of the present invention includes the steps of: forming at least one buried portion in an insulating film deposited on a semiconductor substrate, the buried portion being selected from: corresponding to the configuration of the wiring layer grooves, and openings corresponding to the configuration of filling vias; a wiring material film made of copper or copper alloy is formed on the surface of the insulating film including the inner surface of the buried part; and the wiring is polished using a polishing device The material film is polished, and the device is equipped with a polishing cloth selected from any one of the above-mentioned structures (1)-(6), thereby forming at least one conductive material selected from the filling via and the wiring layer in the buried part. sex parts.

According to the present invention, since the wiring material thin film is designed to be polished by a simplified procedure using a polishing apparatus equipped with a polishing cloth capable of maintaining stable polishing performance without the above-mentioned conditioning, it is now possible to mass-produce such semiconductor devices , wherein a conductive member such as a wiring layer having a desired film thickness is buried in the buried portion.

Next, an embodiment of the present invention will be explained in detail.

Detailed ways

<Synthesis Example 1>

First, 40.0 parts by weight of xylene, and 10.0 parts by weight of butyl acetate were added to a flask equipped with a stirrer, and the resulting mixture was heated to a temperature of 134°C. Then, within 3 hours, under stirring, 60.0 parts by weight of tri-iso-propylsilyl acrylate (compound represented by the above formula (III-4)), 15.0 parts by weight of 2-ethoxymethacrylate methyl ethyl ester, 20.0 parts by weight methyl methacrylate, 5.0 parts by weight n-butyl methacrylate and 1.0 parts by weight polymerization catalyst or perbutyl I (trade name, NOF CORPOPATION; tert-butyl peroxy isopropyl carbonate) drops Add to the above mixture in the flask. After the addition was complete, the resulting mixture was kept at this temperature for 30 minutes to obtain a reaction mixture. Then, within 20 minutes, a mixture consisting of 10.0 parts by weight xylene and 1.0 parts by weight perbutyl I was added dropwise to the above reaction mixture, and the reaction mixture was stirred for 2 hours while maintaining the temperature to complete the polymerization reaction . Finally, the resulting reaction mixture was diluted by adding 48.0 parts by weight of xylene thereto, thereby obtaining a 50% xylene solution of a copolymer having a silyl acrylate repeating unit represented by the following formula (X) .

In addition, the number average molecular weight of the copolymer obtained in this way was 67,000, and its glass transition temperature was 56°C. The ratio of the silyl acrylate repeating unit was 60% by weight based on the total weight of the copolymer.

(The composition ratio shown in this structural formula X is by weight percentage)

<Synthesis Example 2>

First, 40.0 parts by weight of xylene, and 10.0 parts by weight of butyl acetate were added to a flask equipped with a stirrer, and the resulting mixture was heated to a temperature of 134°C. Then, within 3 hours, under stirring, 43.7 parts by weight of mono-iso-butoxyethyl methacrylate (compound represented by the above (VI-6)), 52.0 parts by weight of methyl methacrylate, 4.3 A mixed solution of parts by weight of 2-ethylhexyl acrylate and 1.0 parts by weight of a polymerization catalyst or perbutyl I was added dropwise to the above mixture in the flask. After the addition was complete, the resulting mixture was kept at this temperature for 30 minutes to obtain a reaction mixture. Then, within 20 minutes, a mixture consisting of 10.0 parts by weight xylene and 1.0 parts by weight perbutyl I was added dropwise to the above reaction mixture, and the reaction mixture was stirred for 2 hours while maintaining the temperature to complete the polymerization reaction . Finally, the resulting reaction mixture was diluted by adding 48.0 parts by weight of xylene thereto, thereby obtaining a 50% xylene solution of a copolymer having hemiacetal methacrylate having a structural formula represented by the following formula (XI) repeat unit.

In addition, the number average molecular weight of the copolymer obtained in this way was 38,000, and its glass transition temperature was 50°C.

The ratio of the hemiacetal methacrylate repeating unit was 43.7% by weight based on the total weight of the copolymer.

(The composition ratio shown in this structural formula XI is in weight percent)

<Synthesis Example 3>

First, 40.0 parts by weight of xylene, and 10.0 parts by weight of butyl acetate were added to a flask equipped with a stirrer, and the resulting mixture was heated to a temperature of 134°C. Then, within 3 hours, under stirring, a mixed solution containing 64.0 parts by weight of acrylic acid, 36.0 parts by weight of methoxyethyl acrylate and 1.0 parts by weight of a polymerization catalyst or perbutyl I was added dropwise to the above mixture in the flask. After the addition was complete, the resulting mixture was kept at this temperature for 30 minutes to obtain a reaction mixture. Then, within 20 minutes, a mixture consisting of 10.0 parts by weight xylene and 1.0 parts by weight perbutyl I was added dropwise to the above reaction mixture, and the reaction mixture was stirred for 2 hours while maintaining the temperature to complete the polymerization reaction .

Finally, the resulting reaction mixture was diluted by adding thereto 48.0 parts by weight of xylene to obtain a 50% xylene solution of the polymer, which was soluble in an aqueous medium.

In addition, the number average molecular weight of the copolymer obtained in this way was 21,000, and its glass transition temperature was 35°C.

<Synthesis Example 4>

First, 40.0 parts by weight of xylene, and 10.0 parts by weight of butyl acetate were added to a flask equipped with a stirrer, and the resulting mixture was heated to a temperature of 134°C. Then, within 3 hours, under stirring, a mixed solution containing 15.0 parts by weight of methyl methacrylate, 85.0 parts by weight of butyl methacrylate and 1.0 parts by weight of polymerization catalyst or perbutyl I was added dropwise to the above mixture in the flask . After the addition was complete, the resulting mixture was kept at this temperature for 30 minutes to obtain a reaction mixture. Then, within 20 minutes, a mixture consisting of 10.0 parts by weight xylene and 1.0 parts by weight perbutyl I was added dropwise to the above reaction mixture, and the reaction mixture was stirred for 2 hours while maintaining the temperature to complete the polymerization reaction .

Finally, the obtained reaction mixture was diluted by adding thereto 48.0 parts by weight of xylene, thereby obtaining a 50% xylene solution of a polymer whose surface could be eluted in an aqueous medium when subjected to frictional stress.

In addition, the number average molecular weight of the copolymer obtained in this manner was 17,000, and its glass transition temperature was 44°C.

(Example 1)

Cerium oxide abrasive grains having an average particle diameter of 0.2 µm were dispersed in pure water at a ratio of 0.5% by weight to prepare a polishing slurry.

In addition, a 50% xylene solution of the copolymer having the structural formula represented by the structure (X) synthesized in Synthesis Example 1 above was cast onto the surface of the turntable, and then dried to obtain Polishing cloth made of objects. Then, the turntable covered with the polishing cloth was assembled into the above-mentioned polishing device as shown in FIG. 1 .

Then, a 20 mm square silicon substrate having a silicon dioxide film thereon was prepared. Then, the silicon substrate 6 was fixed to the jig 5 of the polishing apparatus shown in FIG. 1 in such a manner that its silicon dioxide film faced the polishing cloth 2 formed on the surface of the turntable 1 . Thereafter, the silicon substrate 6 was brought into contact with the polishing cloth 2 formed on the turntable 1 by applying a load of about 300 g/cm ² to the silicon substrate 6 by means of the support shaft 4 of the jig 5, while the turntable 1 and the jig were brought into contact with each other. 5 rotate in the same direction as each other, and the rotation speeds are 100rpm and 103rpm respectively, and the polishing slurry is delivered to the polishing cloth 2 from the supply pipe 3 at a flow rate of 20mL/min, thereby forming on the surface of the silicon substrate 6. The silica film was polished for 60 min.

(comparative example 1)

The silicon dioxide film formed on the surface of the silicon substrate 6 was polished for 60 minutes under the same conditions as described in Example 1, except that a hard polyurethane foam (IC1000 (trade name); Rodel Co. ., Ltd) is used as a polishing cloth and assembled into a polishing device.

The polishing time and polishing rate of the silicon dioxide films in Example 1 and Comparative Example 1 were measured, and the results are shown in FIG. 2 .

As can be seen from FIG. 2, in the case of Comparative Example 1, that is, using a polishing apparatus equipped with a conventional polishing cloth formed of hard polyurethane foam to polish a silicon dioxide film formed on a silicon substrate, polishing The rate will increase proportionally with the elapse of polishing time. More precisely, when the polishing time lasts 60 min, the polishing rate will increase by 30% from the initial polishing rate, thus indicating the fluctuation of the polishing rate.

In contrast, in the case of Example 1, that is, in the case of polishing a silicon dioxide film formed on a silicon substrate using a polishing apparatus equipped with a polishing cloth, the polishing cloth is composed of The copolymers of the given structure form, although the polishing rate increases more or less proportionally with the passage of polishing time, when the polishing time lasts 60 minutes, its polishing rate only increases by 10% compared with the initial polishing rate, thus showing that Relatively stable polishing rate.

(Example 2)

A 50% xylene solution of a copolymer having a structural formula represented by the structure (XI) synthesized in Synthesis Example 2 above was cast onto the surface of the turntable, and then dried to obtain a 50-micrometer-thick and composed of the above-mentioned copolymer. polishing cloth. Then, the turntable covered with the polishing cloth was assembled into the above-mentioned polishing device as shown in FIG. 1 .

Then, a 20 mm square silicon substrate having a silicon dioxide film thereon was prepared. Then, the silicon substrate 6 was fixed to the jig 5 of the polishing apparatus shown in FIG. 1 in such a manner that its silicon dioxide film faced the polishing cloth 2 formed on the surface of the turntable 1 . Then, in the same manner as described in Example 1, the silicon dioxide film formed on the surface of the silicon substrate 6 was polished.

In addition, dressing for adjusting the surface state of the polishing cloth was performed using a #80 diamond electrodeposition dresser under the conditions of a load of 200 g/cm ² and a rotational speed of the turntable of 160 rpm.

As a result, it was demonstrated that it was possible to stably polish a silicon dioxide thin film at a polishing rate of about 40 nm/min by performing the above-mentioned conditioning for 5 minutes or longer in advance.

(Example 3)

Copolymer 50% xylene solution (copolymer of methyl methacrylate/butyl methacrylate) was applied to the polished surface of IC1000/Suba-400 (trade name, Rodel Co., Ltd), and then Dry to obtain a polishing cloth with a thickness of 85 μm; wherein the copolymer synthesized in Synthesis Example 4 above, that is, a polymer whose surface is eluted in an aqueous medium when it is subjected to frictional stress. Then, the turntable covered with the polishing cloth was assembled into the above-mentioned polishing device as shown in FIG. 1 .

Then, a 20 mm square silicon substrate having a silicon dioxide film (P-TEOS film) formed thereon was prepared. Then, the silicon substrate 6 was fixed to the jig 5 of the polishing apparatus shown in FIG. 1 in such a manner that its silicon dioxide film faced the polishing cloth 2 formed on the surface of the turntable 1 . Then, the silicon substrate 6 is brought into contact with the polishing cloth ² formed on the turntable 1 by applying a load of about 300 g/cm to the silicon substrate 6 through the support shaft 4 of the jig 5, and at the same time, the turntable 1 and the jig 5 are brought into contact with each other. Rotate with the rotating speed of 50rpm and 160rpm respectively on the same direction; With the flow velocity of 20mL/min, the polishing slurry that will comprise pure water and 1% weight cerium oxide abrasive grain is transported on the polishing cloth 2 by feed pipe 3, thereby The silicon dioxide film formed on the surface of the silicon substrate 6 is polished; wherein the abrasive grains have an average particle diameter of 0.2 μm and are dispersed in pure water.

In addition, dressing for adjusting the surface state of the polishing cloth was performed using a #80 diamond electrodeposition dresser under the conditions of a load of 200 g/cm ² and a rotational speed of the turntable of 160 rpm.

As a result, it was demonstrated that it was possible to stably polish a silicon dioxide thin film at a polishing rate of about 40 nm/min by performing the above-mentioned conditioning for 5 minutes or longer in advance.

<Example 4>

Copolymer 50% xylene solution (copolymer of acrylic acid/methoxy acrylate) was applied to the polished surface of IC1000/Suba-400 (trade name, Rodel Co., Ltd) at a thickness of 55 micrometers, Then it was dried to obtain a polishing cloth; wherein the copolymer was synthesized in Synthesis Example 3 above, that is, a polymer soluble in an aqueous medium. Then, the turntable covered with the polishing cloth was assembled into the above-mentioned polishing device as shown in FIG. 1 .

Then, a 25 mm square silicon substrate having a silicon dioxide film (P-TEOS film) formed thereon was prepared. Then, the silicon substrate 6 was fixed to the jig 5 of the polishing apparatus shown in FIG. 1 in such a manner that its silicon dioxide film faced the polishing cloth 2 formed on the surface of the turntable 1 . Thereafter, in the same manner as described in Example 3, the silicon dioxide film formed on the surface of the silicon substrate 6 was polished.

In addition, dressing for adjusting the surface state of the polishing cloth was performed using a #80 diamond electrodeposition dresser under the conditions of a load of 200 g/cm ² and a rotational speed of the turntable of 160 rpm.

As a result, it was demonstrated that it was possible to stably polish a silicon dioxide thin film at a polishing rate of about 50 nm/min by performing the above-mentioned conditioning for 5 minutes or longer in advance.

(Example 5)

50% xylene solution of the copolymer is applied to IC1000/Suba-400 (trade name, Rodel Co., Ltd.), the thickness is 70 microns, and then dried to obtain a polishing cloth; wherein the copolymer is described in Synthesis Example 2, that is, a copolymer with hemiacetal methacrylate repeating units. Then, the turntable covered with the polishing cloth was assembled into the above-mentioned polishing device as shown in FIG. 1 .

Then, a 25 mm square silicon substrate having a silicon dioxide film (P-TEOS film) formed thereon was prepared. Then, the silicon substrate 6 was fixed to the jig 5 of the polishing apparatus shown in FIG. 1 in such a manner that its silicon dioxide film faced the polishing cloth 2 formed on the surface of the turntable 1 . Thereafter, in the same manner as described in Example 3, the silicon dioxide film formed on the surface of the silicon substrate 6 was polished.

In addition, dressing for adjusting the surface state of the polishing cloth was performed using a #80 diamond electrodeposition dresser under the conditions of a load of 200 g/cm ² and a rotational speed of the turntable of 160 rpm.

As a result, it was demonstrated that it was possible to stably polish a silicon dioxide thin film at a polishing rate of about 50 nm/min by performing the above-mentioned conditioning for 5 minutes or longer in advance.

(Example 6)

Copolymer 50% xylene solution is coated on the polishing surface of IC1000/Suba-400 (trade name, Rodel Co., Ltd.) to a thickness of about 50 micrometers, and then dried to obtain a polishing cloth; wherein the copolymer The product has a silyl acrylate repeating unit and was synthesized in the above Synthesis Example 1. In addition, the xylene solution also contained 3% by weight (based on the weight of the copolymer) of cerium oxide abrasive grains with an average particle size of 0.2 microns. Then, the turntable covered with the polishing cloth was assembled into the above-mentioned polishing device as shown in FIG. 1 .

Then, a 25 mm square silicon substrate having a silicon dioxide film (P-TEOS film) formed thereon was prepared. Then, the silicon substrate 6 was fixed to the jig 5 of the polishing apparatus shown in FIG. 1 in such a manner that its silicon dioxide film faced the polishing cloth 2 formed on the surface of the turntable 1 . Thereafter, by means of the support shaft 4 of the jig 5, the silicon substrate 6 is brought into contact with the polishing cloth ² formed on the turntable 1 by applying a load of about 300 g/cm to the silicon substrate 6, and at the same time, the turntable 1 and the jig 5 are respectively Rotating in the same direction at 50 rpm and 160 rpm, a 4.3% by weight aqueous hydrogen peroxide solution (polishing agent composition) was delivered from the feed pipe 3 to the polishing cloth 2 at a flow rate of 20 mL/min. Thereby, the silicon dioxide thin film formed on the surface of the silicon substrate is polished.

In addition, dressing for adjusting the surface state of the polishing cloth was performed using a #80 diamond electrodeposition dresser under the conditions of a load of 200 g/cm ² and a rotational speed of the turntable of 160 rpm.

The results demonstrated that it was possible to polish a silicon dioxide film at a polishing rate of about 4 nm/min by preconditioning for 10 seconds, although the polishing composition contained no abrasive grains.

(Example 7)

Copolymer 50% xylene solution is coated on the polishing surface of IC1000/Suba-400 (trade name, Rodel Co., Ltd.) to a thickness of about 50 micrometers, and then dried to obtain a polishing cloth; wherein the copolymer The product has a silyl acrylate repeating unit and is synthesized in the above-mentioned Synthesis Example 1. In addition, the xylene solution also includes 3% by weight (calculated by the weight of the copolymer) dispersed therein. . Then, the turntable covered with the polishing cloth was assembled into the above-mentioned polishing device as shown in FIG. 1 .

Then, a 25 mm square silicon substrate having a copper thin film formed thereon was prepared. Then, the silicon substrate 6 was fixed to the jig 5 of the polishing apparatus shown in FIG. 1 in such a manner that its copper film faced the polishing cloth 2 formed on the surface of the turntable 1 . Thereafter, by means of the support shaft 4 of the jig 5, the silicon substrate 6 is brought into contact with the polishing cloth ² formed on the turntable 1 by applying a load of about 300 g/cm to the silicon substrate 6, and at the same time, the turntable 1 and the jig 5 are respectively Rotating in the same direction at 50rpm and 160rpm, the polishing agent composition was delivered from the supply pipe 3 to the polishing cloth 2 at a flow rate of 20mL/min, thereby polishing the copper film formed on the surface of the silicon substrate 6 . In addition, the polishing agent composition used herein was formed from an aqueous solution containing 0.5% by weight of quinaldixic acid, 0.6% by weight of lactic acid, 0.9% by weight of a surfactant, and 4.5% by weight of hydrogen peroxide.

In addition, dressing for adjusting the surface state of the polishing cloth was performed using a #80 diamond electrodeposition dresser under the conditions of a load of 200 g/cm ² and a rotational speed of the turntable of 160 rpm.

As a result, it was demonstrated that it was possible to polish the copper film at a polishing rate of about 11 nm/min by preliminarily performing conditioning for 10 seconds, although the polishing agent composition contained no abrasive grains.

(Embodiment 8)

At first, prepare by 3.6% by weight colloidal silicon dioxide, 1.1% by weight colloidal alumina, 0.6% by weight 2-quinolinecarboxylic acid (quinalidine acid), 0.35% by weight of lactic acid, 1.8% by weight of lauryl sulfate A polishing slurry consisting of ammonium, 3.9% by weight hydrogen peroxide, 0.5% by weight hydroxyethylcellulose, and a balance of water.

Then, by CVD method, as an interlayer insulating film, for example, a silicon dioxide film 22 with a thickness of 1000 nm is deposited on the surface of the silicon substrate 21 provided with a diffusion layer as shown in FIG. 3A . Thereafter, by photolithography, a plurality of grooves 23 each having a width of 100 micrometers, a depth of 8 micrometers and a configuration corresponding to the wiring layer are formed. In addition, as shown in FIG. 3B, on the entire surface of the silicon dioxide film 22 including the above-mentioned groove surface, in the mentioned order, are sequentially formed by the sputter deposition method, which is made of TiN and has a thickness of A barrier layer 24 of 15 nm and a copper film 25 with a thickness of 1.6 microns.

Then, using a polishing apparatus as shown in FIG. 1, the apparatus is equipped with a turntable whose surface is covered with a 0.8 mm thick polishing cloth formed of a copolymer having the same structural formula as used in Example 1, that is, the structural formula (X); In such a manner, the silicon substrate 21 having the copper film 25 formed thereon is reversely fixed to the jig 5 of the polishing apparatus so that the copper film 25 thereof faces the polished surface formed on the turntable 1 surface. cloth2. Thereafter, by means of the supporting shaft 4 of the jig 5, by applying a load of about 500 gf/cm to the silicon substrate ²¹ , it is pressed onto the polishing cloth formed on the turntable 1, while the turntable 1 and The fixture 5 rotates in the same direction, and the polishing slurry is delivered to the polishing cloth 2 by the feed pipe 3 at a flow rate of 50 mL/min, thereby polishing the copper film 25 and the barrier layer 24 for about 40 minutes until the silicon dioxide film 22 and barrier layer 24 are exposed, thus forming a buried copper wiring layer 26 surrounded by barrier layer 24, as shown in FIG. 3C. As a result, a semiconductor device having a buried copper wiring layer 26 was produced.

As described above, according to the present invention, it is now possible to provide a polishing cloth capable of exhibiting stable polishing performance over a relatively long period of time without necessary conditioning treatment.

In addition, according to the present invention, it is also possible to provide a polishing cloth which has an automatic feeding capability of abrasive grains and which can exhibit stable polishing performance over a relatively long period of time without necessary conditioning treatment.

In addition, according to the present invention, it is possible to provide a polishing apparatus equipped with the above-mentioned polishing cloth capable of exhibiting stable polishing performance and suitable for forming a chemical-mechanical component that buries a conductive member such as a buried wiring layer of a semiconductor device. Polishing (CMP).

Furthermore, according to the present invention, it is also possible to provide a method of manufacturing a semiconductor device which makes it possible to reliably form a conductive member such as a high-precision buried wiring layer in at least one buried portion selected from From: Grooves and openings formed in an insulating film deposited on a semiconductor substrate.

Claims (8)

1. burnishing device comprises:

Turntable with the surface that is coated with polishing cloth, described polishing cloth comprises the polishing layer that contacts and contain polymeric material with polished main element, described polymeric material can be used the water-bearing media hydrolysis, wherein said polymeric material comprises the main chain that has side chain, described side chain has with the hydrolyzable structure of water-bearing media, and this structure is represented by following formula (I) or (II):

In the formula, R ¹, R ²And R ³Can be identical or different, and the hydrogen atom of respectively doing for oneself, alkyl or aryl:

In the formula, R ⁴, R ⁵And R ⁶Can be identical or different, and the organic group of respectively do for oneself hydrogen atom or 1-18 carbon atom; R ⁷Organic group for 1-18 carbon atom; And R ⁶And R ⁷Can be joined together to form and have hetero atom Y ¹Heterocycle, Y ¹Be oxygen atom or sulphur atom;

Rotatable and vertically move, be arranged in the clamp mechanism on the turntable, it is designed to fixing polished main element, this clamp mechanism also is designed to the load of hope is added on the main element, whereby, make the abrasive cloth of main element and turntable add press contacts, also be designed in addition on identical direction, rotate with turntable; With

The rubbing paste that is used for comprising abrasive grain is delivered to the feeder of polishing cloth.

2. the burnishing device of claim 1, wherein, described polymeric material is α, β-undersaturated homopolymers or copolymer, and they have by the following formula that has formula (I) separately (III) separately or (IV) or separately have the formula (V) of formula (II) or (VI) repetitive of monomer of expression:

In the formula, R ¹, R ²And R ³Can be identical or different, and the hydrogen atom of respectively doing for oneself, alkyl or aryl:

In the formula, R ¹, R ²And R ³Can be identical or different, and the hydrogen atom of respectively doing for oneself, alkyl or aryl:

In the formula, R ⁴, R ⁵And R ⁶Can be identical or different, and the organic group of respectively do for oneself hydrogen atom or 1-18 carbon atom; R ⁷Organic group for 1-18 carbon atom; And R ⁶And R ⁷Can be joined together to form and have hetero atom Y ¹Heterocycle, Y ¹Be oxygen atom or sulphur atom;

In the formula, R ⁴, R ⁵And R ⁶Can be identical or different, and the organic group of respectively do for oneself hydrogen atom or 1-18 carbon atom; R ⁷Organic group for 1-18 carbon atom; And R ⁶And R ⁷Can be joined together to form and have hetero atom Y ¹Heterocycle, Y ¹Be oxygen atom or sulphur atom.

3. burnishing device comprises:

Turntable with the surface that is coated with polishing cloth, described polishing cloth comprises and contacts with polished main element and contain polymeric material that can hydrolysis in water-bearing media and contain the polishing layer of at least a following abrasive grain, described abrasive grain is selected from cerium oxide, manganese oxide, silica, aluminium oxide and zirconia, this abrasive grain is scattered in the polymeric material, wherein said polymeric material comprises the main chain that has side chain, described side chain has with the hydrolyzable structure of water-bearing media, and this structure is represented by following formula (I) or (II):

In the formula, R ¹, R ²And R ³Can be identical or different, and the hydrogen atom of respectively doing for oneself, alkyl or aryl:

In the formula, R ⁴, R ⁵And R ⁶Can be identical or different, and the organic group of respectively do for oneself hydrogen atom or 1-18 carbon atom; R ⁷Organic group for 1-18 carbon atom; And R ⁶And R ⁷Can be joined together to form and have hetero atom Y ¹Heterocycle, Y ¹Be oxygen atom or sulphur atom;

Rotatable and vertically move, be arranged in the clamp mechanism on the turntable, it is designed to fixing polished main element, this clamp mechanism also is designed to the load of hope is added on the main element, whereby, make the abrasive cloth of main element and turntable add press contacts, also be designed in addition on identical direction, rotate with turntable; With

The polishing composition that is used for will comprising water at least and not contain abrasive grain is delivered to the feeder of polishing cloth.

4. the burnishing device of claim 3, wherein, described polymeric material is α, β-undersaturated homopolymers or copolymer, and they have by the following formula that has formula (I) separately (III) separately or (IV) or separately have the formula (V) of formula (II) or (VI) repetitive of monomer of expression:

In the formula, R ¹, R ²And R ³Can be identical or different, and the hydrogen atom of respectively doing for oneself, alkyl or aryl:

In the formula, R ¹, R ²And R ³Can be identical or different, and the hydrogen atom of respectively doing for oneself, alkyl or aryl:

In the formula, R ⁴, R ⁵And R ⁶Can be identical or different, and the organic group of respectively do for oneself hydrogen atom or 1-18 carbon atom; R ⁷Organic group for 1-18 carbon atom; And R ⁶And R ⁷Can be joined together to form and have hetero atom Y ¹Heterocycle, Y ¹Be oxygen atom or sulphur atom;

In the formula, R ⁴, R ⁵And R ⁶Can be identical or different, and the organic group of respectively do for oneself hydrogen atom or 1-18 carbon atom; R ⁷Organic group for 1-18 carbon atom; And R ⁶And R ⁷Can be joined together to form and have hetero atom Y ¹Heterocycle, Y ¹Be oxygen atom or sulphur atom.

5. the preparation method of a semiconductor devices, described method comprises the steps:

In the insulation film on being deposited on semiconductor substrate, form at least one inlet part, described inlet part is selected from: corresponding to the groove of wiring layer configuration with corresponding to the opening of the configuration of filling vias;

To be formed on by the wiring material film that copper or copper alloy are made on the surface of the insulation film that comprises the inlet part inner surface; With

Utilize burnishing device to polish this wiring material film, form at least one whereby and be selected from the filling vias in the inlet part and the conducting parts of wiring layer;

Wherein, described burnishing device comprises the turntable with the surface that is coated with polishing cloth, described polishing cloth comprises the polishing layer that contacts and contain polymeric material with wiring material film, described polymeric material is hydrolyzable in water-bearing media, wherein said polymeric material comprises the main chain that has side chain, described side chain has with the hydrolyzable structure of water-bearing media, and this structure is represented by following formula (I) or (II):

In the formula, R ¹, R ²And R ³Can be identical or different, and the hydrogen atom of respectively doing for oneself, alkyl or aryl:

In the formula, R ⁴, R ⁵And R ⁶Can be identical or different, and the organic group of respectively do for oneself hydrogen atom or 1-18 carbon atom; R ⁷Organic group for 1-18 carbon atom; And R ⁶And R ⁷Can be joined together to form and have hetero atom Y ¹Heterocycle, Y ¹Be oxygen atom or sulphur atom;

Rotatable and vertically move, be arranged in the clamp mechanism on the turntable, it is designed to fixing polished main element, this clamp mechanism also is designed to the load of hope is added on the main element, make main element add press contacts whereby, also be designed to the direction rotation identical in addition with turntable with the abrasive cloth of turntable; With

The rubbing paste that is used for comprising abrasive grain is delivered to the feeder of polishing cloth.

6. the semiconductor devices preparation method of claim 5, wherein, described polymeric material is α, β-undersaturated homopolymers or copolymer, they have by the following formula that has formula (I) separately (III) separately or (IV) or separately have the formula (V) of formula (II) or (VI) repetitive of monomer of expression:

In the formula, R ¹, R ²And R ³Can be identical or different, and the hydrogen atom of respectively doing for oneself, alkyl or aryl:

In the formula, R ¹, R ²And R ³Can be identical or different, and the hydrogen atom of respectively doing for oneself, alkyl or aryl:

In the formula, R ⁴, R ⁵And R ⁶Can be identical or different, and the organic group of respectively do for oneself hydrogen atom or 1-18 carbon atom; R ⁷Organic group for 1-18 carbon atom; And R ⁶And R ⁷Can be joined together to form and have hetero atom Y ¹Heterocycle, Y ¹Be oxygen atom or sulphur atom;

In the formula, R ⁴, R ⁵And R ⁶Can be identical or different, and the organic group of respectively do for oneself hydrogen atom or 1-18 carbon atom; R ⁷Organic group for 1-18 carbon atom; And R ⁶And R ⁷Can be joined together to form and have hetero atom Y ¹Heterocycle, Y ¹Be oxygen atom or sulphur atom.

7. the preparation method of a semiconductor devices, described method comprises the steps:

In the insulation film on being deposited on semiconductor substrate, form at least one inlet part, described inlet part is selected from: corresponding to the groove of wiring layer configuration with corresponding to the opening of the configuration of filling vias;

To be formed on by the wiring material film that copper or copper alloy are made: comprise on the surface of insulation film of inlet part inner surface; With

Utilize burnishing device to polish this wiring material film, form at least one whereby and be selected from the filling vias in the inlet part and the conducting parts of wiring layer;

Wherein, burnishing device comprises the turntable with the surface that is coated with polishing cloth, described polishing cloth comprises and contacts with wiring material film and contain polymeric material and at least a polishing layer that is selected from following abrasive grain, described polymeric material is hydrolyzable in water-bearing media, described abrasive grain is selected from cerium oxide, manganese oxide, silica, aluminium oxide and zirconia, this abrasive grain is scattered in the polymeric material, wherein said polymeric material comprises the main chain that has side chain, and described side chain has with the hydrolyzable structure of water-bearing media, and this structure is represented by following formula (I) or (II):

In the formula, R ¹, R ²And R ³Can be identical or different, and the hydrogen atom of respectively doing for oneself, alkyl or aryl:

In the formula, R ⁴, R ⁵And R ⁶Can be identical or different, and the organic group of respectively do for oneself hydrogen atom or 1-18 carbon atom; R ⁷Organic group for 1-18 carbon atom; And R ⁶And R ⁷Can be joined together to form and have hetero atom Y ¹Heterocycle, Y ¹Be oxygen atom or sulphur atom;

Rotatable and vertically move, be arranged in the clamp mechanism on the turntable, it is designed to fixing polished main element, this clamp mechanism also is designed to the load of hope is added on the main element, make main element add press contacts whereby, and also be designed to the direction rotation identical with turntable with the abrasive cloth of turntable; With

Be used for carrying moisture at least and not containing the feeder of the polishing agent combination of abrasive grain to polishing cloth.

8. the semiconductor devices preparation method of claim 7, wherein, described polymeric material is α, β-undersaturated homopolymers or copolymer, they have by the following formula that has formula (I) separately (III) separately or (IV) or separately have the formula (V) of formula (II) or (VI) repetitive of monomer of expression:

In the formula, R ¹, R ²And R ³Can be identical or different, and the hydrogen atom of respectively doing for oneself, alkyl or aryl:

In the formula, R ¹, R ²And R ³Can be identical or different, and the hydrogen atom of respectively doing for oneself, alkyl or aryl:

In the formula, R ⁴, R ⁵And R ⁶Can be identical or different, and the organic group of respectively do for oneself hydrogen atom or 1-18 carbon atom; R ⁷Organic group for 1-18 carbon atom; And R ⁶And R ⁷Can be joined together to form and have hetero atom Y ¹Heterocycle, Y ¹Be oxygen atom or sulphur atom;

In the formula, R ⁴, R ⁵And R ⁶Can be identical or different, and the organic group of respectively do for oneself hydrogen atom or 1-18 carbon atom; R ⁷Organic group for 1-18 carbon atom; And R ⁶And R ⁷Can be joined together to form and have hetero atom Y ¹Heterocycle, Y ¹Be oxygen atom or sulphur atom.

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