KR20200028236A - Silica Particles for CMP and Preparation Method thereof - Google Patents

Abstract

The present invention relates to silica particles for chemical mechanical polishing (CMP) and to a production method thereof. The silica particles for CMP of the present invention can quickly etch a copper-based film without dicing due to the selective etching at a pad friction part and simplifies facilities because the etching is possible with only a one-step process.

Description

Silica particles for CMP and manufacturing method thereof {Silica Particles for CMP and Preparation Method thereof}

The present invention relates to a silica particle for CMP and a method for manufacturing the same, and more particularly, to a silica particle for CMP and a method for manufacturing the same, which can rapidly etch a copper-based film without a dishing phenomenon in one step.

Recently, copper or copper alloys have been used as wiring materials due to high integration of semiconductor devices. However, since copper is very difficult to etch by dry etching, a damascene process is used. The damascene process is a method of forming a pattern on a silicon wafer in advance and depositing copper using an electroplating method or the like, and removing unnecessary parts by a chemical mechanical planarization (CMP) process.

The CMP process is a process of placing a wafer to be subjected to a flattening treatment on a rotating plate, contacting a pad on the wafer surface, and rotating both of the turntable and the pad while supplying a polishing composition between the wafer and the pad to perform polishing.

In the case of forming the copper or copper alloy wiring through the CMP process, most of the metal film quality is removed using a primary polishing slurry composition having a high polishing amount with respect to the metal film quality, and the polishing rate is equal to the metal buried portion and the dielectric film. It uses a two-step process using a secondary polishing slurry composition having, in this case there is a problem that the equipment is complicated because two types of chemicals must be used.

In addition, the conventional polishing slurry composition has a problem in that surface defects such as dishing occur, and a method of modifying the surface of silica particles used in the polishing slurry composition with a water-soluble polymer to suppress such surface defects is attempted. [Refer to Korean Patent Registration No. 10-1427883].

Therefore, in order to increase the efficiency of the process, there is a need to develop a technology for a slurry composition for CMP that can rapidly etch a copper-based film in a one-step process and does not cause surface defects such as dishing.

Republic of Korea Registered Patent No. 10-1427883

One object of the present invention is to provide silica particles for CMP capable of rapidly etching a copper-based film without a dishing phenomenon in a one-step process.

Another object of the present invention is to provide a method for producing the silica particles for CMP.

Another object of the present invention is to provide a CMP slurry composition comprising the silica particles for CMP.

Meanwhile, the present invention provides silica particles for CMP in which one or more functional groups selected from the group consisting of phosphoric acid groups, phosphonic acid groups, sulfuric acid groups, sulfonic acid groups and ammonium groups are introduced on the surface.

In one embodiment of the present invention, the silica particles for CMP are prepared by a sol-gel reaction of a silane coupling agent having at least one functional group selected from the group consisting of phosphoric acid groups, phosphonic acid groups, sulfuric acid groups, sulfonic acid groups and ammonium groups, or phosphoric acid groups, phosphates It may be prepared by binding and reacting a silica particle with a silane coupling agent having at least one functional group selected from the group consisting of a phonic acid group, a sulfuric acid group, a sulfonic acid group, and an ammonium group.

In one embodiment of the present invention, the silane coupling agent having at least one functional group selected from the group consisting of the phosphoric acid group, phosphonic acid group, sulfuric acid group, sulfonic acid group and ammonium group may include one or more of the compounds of Formulas 1 to 5 .

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In the above formula,

R ¹ is each independently hydrogen or an alkyl group of C ₁ -C ₆ ,

R ² are each independently a C ₁ -C ₆ alkyl group,

R ³ to R ⁶ are each independently hydrogen, an alkyl group or an aryl group of C ₁ -C ₆ ,

L are each independently a linking group,

M is a hydrogen atom or an alkali metal ion or is absent,

X is a halogen atom,

n is an integer from 1 to 3.

In one embodiment of the present invention, L is each independently one or more of the chain carbon is oxygen, nitrogen substituted with one or two C ₁ -C ₆ alkyl groups, or C ₁ -C unsubstituted or substituted with arylene. _It may be an alkylene group of ₆ .

In one embodiment of the present invention, the silane coupling agent having one or more functional groups selected from the group consisting of the phosphoric acid group, phosphonic acid group, sulfuric acid group, sulfonic acid group and ammonium group may include one or more of the compounds of the following formulas 12 to 17 .

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

In one embodiment of the present invention, the silica particles for CMP may be prepared by reacting one or more of the following compounds of Formulas 6 to 10 with silica particles having an acryloxy group introduced on the surface.

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

In the above formula,

Z are each independently a thiol, amino or C ₁ -C ₆ alkylamino group,

R ³ to R ⁶ are each independently hydrogen, an alkyl group or an aryl group of C ₁ -C ₆ ,

L are each independently a linking group,

M is a hydrogen atom or an alkali metal ion or is absent,

X is a halogen atom.

In one embodiment of the present invention, L is each independently one or more of the chain carbon is oxygen, nitrogen substituted with one or two C ₁ -C ₆ alkyl groups, or C ₁ -C unsubstituted or substituted with arylene. _It may be an alkylene group of ₆ .

In one embodiment of the present invention, silica particles having an acryloxy group introduced on the surface may be prepared by a sol-gel reaction of a compound of Formula 11, or may be prepared by binding a compound of Formula 11 to silica particles.

[Formula 11]

In the above formula,

R ¹ is each independently hydrogen or an alkyl group of C ₁ -C ₆ ,

R ² are each independently a C ₁ -C ₆ alkyl group,

Y is a linking group,

n is an integer from 1 to 3.

In one embodiment of the invention, Y is a chain one or more oxygen, one of the carbon or two C ₁ -C ₆ alkyl group substituted with a nitrogen, or an arylene or substituted alkyl, unsubstituted C ₁ -C ₆ It can be Rengi.

In one embodiment of the present invention, the silica particles for CMP include silica particles having an acryloxy group introduced on the surface, 2-mercaptoethanesulfonic acid, 2-aminoethanesulfonic acid, 2-aminoethyl hydrogen sulfate and 2- It can be prepared by reacting one or more selected from the group consisting of aminoethyl dihydrogen phosphate.

On the other hand, the present invention provides a method for producing silica particles for CMP comprising the step of sol-gel reacting a silane coupling agent comprising at least one of the compounds of Formulas 1 to 5 below.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In the above formula,

R ¹ is each independently hydrogen or an alkyl group of C ₁ -C ₆ ,

R ² are each independently a C ₁ -C ₆ alkyl group,

R ³ to R ⁶ are each independently hydrogen, an alkyl group or an aryl group of C ₁ -C ₆ ,

L are each independently a linking group,

M is a hydrogen atom or an alkali metal ion or is absent,

X is a halogen atom,

n is an integer from 1 to 3.

On the other hand, the present invention provides a method for producing silica particles for CMP comprising the step of binding and reacting a silane coupling agent comprising at least one of the compounds of Formulas 1 to 5 below with silica particles.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In the above formula,

R ¹ is each independently hydrogen or an alkyl group of C ₁ -C ₆ ,

R ² are each independently a C ₁ -C ₆ alkyl group,

R ³ to R ⁶ are each independently hydrogen, an alkyl group or an aryl group of C ₁ -C ₆ ,

L are each independently a linking group,

M is a hydrogen atom or an alkali metal ion or is absent,

X is a halogen atom,

n is an integer from 1 to 3.

On the other hand, the present invention provides a method for producing silica particles for CMP comprising the step of reacting one or more of the compounds of Formulas 6 to 10 with silica particles having an acrylicoxy group introduced on the surface.

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

In the above formula,

Z are each independently a thiol, amino or C ₁ -C ₆ alkylamino group,

R ³ to R ⁶ are each independently hydrogen, an alkyl group or an aryl group of C ₁ -C ₆ ,

L are each independently a linking group,

M is a hydrogen atom or an alkali metal ion or is absent,

X is a halogen atom.

On the other hand, the present invention provides a CMP slurry composition comprising the silica particles for the CMP and an oxidizing agent.

In one embodiment of the present invention, the oxidizing agent may include hydrogen peroxide.

In one embodiment of the present invention, the silica particles for CMP may be included in an amount of 0.01 to 20% by weight based on 100% by weight of the total composition.

The silica particles for CMP according to the present invention can rapidly etch a copper-based film without a dishing phenomenon due to selective etching at the pad friction portion. In addition, when the copper-based film is etched using the silica particles for CMP according to the present invention, etching can be performed only in a one-step process using one kind of chemical solution, thereby simplifying equipment.

Hereinafter, the present invention will be described in more detail.

One embodiment of the present invention relates to silica particles for CMP in which one or more functional groups selected from the group consisting of phosphoric acid groups, phosphonic acid groups, sulfuric acid groups, sulfonic acid groups and ammonium groups are introduced on the surface.

In one embodiment of the present invention, the silica particles for CMP are prepared by a sol-gel reaction of a silane coupling agent having at least one functional group selected from the group consisting of phosphoric acid groups, phosphonic acid groups, sulfuric acid groups, sulfonic acid groups and ammonium groups, or phosphoric acid groups, phosphates It may be prepared by binding and reacting a silica particle with a silane coupling agent having at least one functional group selected from the group consisting of a phonic acid group, a sulfuric acid group, a sulfonic acid group, and an ammonium group.

The sol-gel reaction is performed by hydrolyzing the alkoxy group of the starting material silane coupling agent with water to form a hydroxyl group, and forming a siloxane bond by condensation reaction with the alkoxy group or hydroxyl group of another silane coupling agent, wherein the binding reaction is The alkoxy group of the silane coupling agent is hydrolyzed with water to form a hydroxyl group, and is performed by forming a siloxane bond by condensation reaction with an alkoxy group or hydroxyl group present on the surface of the silica particles.

The sol-gel reaction and the binding reaction can be carried out in the presence of an acid catalyst.

As the catalyst, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, chlorosulfonic acid, para-toluic acid, trichloroacetic acid, polyphosphoric acid, pyrophosphoric acid, iodic acid, tartaric acid, perchloric acid, and the like can be used. The amount of the catalyst is not particularly limited and may be added to 0.0001 to 10 parts by weight based on 100 parts by weight of the silane coupling agent.

The sol-gel reaction may be performed by stirring at room temperature for 6 to 144 hours, and may be performed at 60 to 80 ° C. for 12 to 36 hours to promote the reaction rate and complete condensation reaction.

The binding reaction may be performed at a temperature of 50 to 80 ° C for 1 to 3 hours.

In one embodiment of the present invention, the silane coupling agent having at least one functional group selected from the group consisting of the phosphoric acid group, phosphonic acid group, sulfuric acid group, sulfonic acid group and ammonium group may include one or more of the compounds of Formulas 1 to 5 .

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In the above formula,

R ¹ is each independently hydrogen or an alkyl group of C ₁ -C ₆ ,

R ² are each independently a C ₁ -C ₆ alkyl group,

R ³ to R ⁶ are each independently hydrogen, an alkyl group or an aryl group of C ₁ -C ₆ ,

L are each independently a linking group,

M is a hydrogen atom or an alkali metal ion or is absent,

X is a halogen atom,

n is an integer from 1 to 3.

As used herein, the alkyl group of C ₁ -C _{6 means} a straight chain or branched monovalent hydrocarbon composed of 1 to 6 carbon atoms, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl , i-butyl, t-butyl, n-pentyl, n-hexyl, and the like.

The aryl group used herein includes both an aromatic group and a heteroaromatic group and their partially reduced derivatives. The aromatic group is a 5- to 15-membered simple or fused cyclic, and the heteroaromatic group means an aromatic group containing one or more oxygen, sulfur or nitrogen. Examples of typical aryl groups are phenyl, naphthyl, pyridinyl, furanyl, thiophenyl, indolyl, quinolinyl, imidazolinyl, Oxazolyl, thiazolyl, tetrahydronaphthyl, and the like, but is not limited thereto.

In one embodiment of the present invention, R ³ to R ⁶ may each independently be a C ₁ -C ₆ alkyl group.

In one embodiment of the invention, L is each independently one or more of the chain carbon is oxygen, nitrogen substituted with one or two C ₁ -C ₆ alkyl group, or C ₁ -C substituted or unsubstituted with an arylene group _It may be an alkylene group of ₆ .

In one embodiment of the invention, M may or may not be a hydrogen atom, sodium ion or potassium ion.

In one embodiment of the invention, X may be chlorine.

In one embodiment of the invention, n may be 3.

As used herein, the C ₁ -C ₆ alkylene group means a straight chain or branched divalent hydrocarbon composed of 1 to 6 carbon atoms, and includes, but is not limited to, methylene, ethylene, propylene, butylene, and the like. It does not work.

The arylene group used in the present specification means a divalent aromatic hydrocarbon, and includes, but is not limited to, phenylene, naphthylene, and the like.

In one embodiment of the present invention, the silane coupling agent having one or more functional groups selected from the group consisting of the phosphoric acid group, phosphonic acid group, sulfuric acid group, sulfonic acid group and ammonium group may include one or more of the compounds of the following formulas 12 to 17 .

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

In one embodiment of the present invention, the silica particles for CMP may be prepared by reacting one or more of the following compounds of Formulas 6 to 10 with silica particles having an acryloxy group introduced on the surface.

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

In the above formula,

Z are each independently a thiol, amino or C ₁ -C ₆ alkylamino group,

R ³ to R ⁶ are each independently hydrogen, an alkyl group or an aryl group of C ₁ -C ₆ ,

L are each independently a linking group,

M is a hydrogen atom or an alkali metal ion or is absent,

X is a halogen atom.

In one embodiment of the present invention, R ³ to R ⁶ may each independently be a C ₁ -C ₆ alkyl group.

In one embodiment of the invention, L is each independently one or more of the chain carbon is oxygen, nitrogen substituted with one or two C ₁ -C ₆ alkyl group, or C ₁ -C substituted or unsubstituted with an arylene group _It may be an alkylene group of ₆ .

In one embodiment of the invention, M may or may not be a hydrogen atom, sodium ion or potassium ion.

In one embodiment of the invention, X may be chlorine.

The reaction of at least one of the silica particles having an acryloxy group introduced on the surface and a compound of Formulas 6 to 10 may be performed for 1 to 12 hours at a reaction temperature of 0 to 50 ° C.

In one embodiment of the present invention, silica particles having an acryloxy group introduced on the surface may be prepared by a sol-gel reaction of a compound of Formula 11, or may be prepared by binding a compound of Formula 11 to silica particles.

[Formula 11]

In the above formula,

R ¹ is each independently hydrogen or an alkyl group of C ₁ -C ₆ ,

R ² are each independently a C ₁ -C ₆ alkyl group,

Y is a linking group,

n is an integer from 1 to 3.

In one embodiment of the invention, Y is oxygen, nitrogen in which one or more of the chain carbons is substituted with one or two C ₁ -C ₆ alkyl groups, or C ₁ -C ₆ alkyl substituted or unsubstituted with an arylene group. It can be Rengi.

The sol-gel reaction and the binding reaction may be performed in the same manner as the sol-gel reaction and the binding reaction using a silane coupling agent having at least one functional group selected from the group consisting of the above-described phosphoric acid group, phosphonic acid group, sulfuric acid group, sulfonic acid group and ammonium group.

In one embodiment of the present invention, the silica particles for CMP include silica particles having an acryloxy group introduced on the surface, 2-mercaptoethanesulfonic acid, 2-aminoethanesulfonic acid, 2-aminoethyl hydrogen sulfate and 2- It can be prepared by reacting one or more selected from the group consisting of aminoethyl dihydrogen phosphate.

The silica particles for CMP according to the present invention have a structure in which at least one functional group selected from the group consisting of a phosphoric acid group, a phosphonic acid group, a sulfuric acid group, a sulfonic acid group and an ammonium group, which can serve as a copper complexing agent on the surface, is introduced into the pad friction part. Only with the mechanical polishing of the copper-based film, chemical polishing is possible, and etching is suppressed in the pad non-friction portion. Therefore, the silica particles for CMP according to the present invention can prevent the dishing phenomenon due to the selective etching. In addition, the silica particles for CMP according to the present invention has a high etching rate, and thus the copper-based film can be etched in only one step using one chemical solution.

One embodiment of the present invention relates to a method for producing silica particles for CMP comprising the step of sol-gel reacting a silane coupling agent comprising one or more of the compounds of Formulas 1 to 5 below.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In the above formula,

R ¹ is each independently hydrogen or an alkyl group of C ₁ -C ₆ ,

R ² are each independently a C ₁ -C ₆ alkyl group,

R ³ to R ⁶ are each independently hydrogen, an alkyl group or an aryl group of C ₁ -C ₆ ,

L are each independently a linking group,

M is a hydrogen atom or an alkali metal ion or is absent,

X is a halogen atom,

n is an integer from 1 to 3.

Since the compounds of Formulas 1 to 5 and the sol-gel reaction are the same as described in the silica particles for CMP, detailed descriptions are omitted to avoid overlap.

One embodiment of the present invention relates to a method for producing silica particles for CMP comprising the step of binding and reacting a silane coupling agent comprising at least one of the compounds of Formulas 1 to 5 below with silica particles.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In the above formula,

R ¹ is each independently hydrogen or an alkyl group of C ₁ -C ₆ ,

R ² are each independently a C ₁ -C ₆ alkyl group,

R ³ to R ⁶ are each independently hydrogen, an alkyl group or an aryl group of C ₁ -C ₆ ,

L are each independently a linking group,

M is a hydrogen atom or an alkali metal ion or is absent,

X is a halogen atom,

n is an integer from 1 to 3.

Since the compound of Formulas 1 to 5 and the binding reaction are the same as described in the silica particles for CMP, a detailed description is omitted to avoid overlap.

One embodiment of the present invention relates to a method for producing silica particles for CMP comprising the step of reacting one or more of the compounds of Formulas 6 to 10 with silica particles having an acryloxy group introduced on the surface.

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

In the above formula,

Z are each independently a thiol, amino or C ₁ -C ₆ alkylamino group,

R ³ to R ⁶ are each independently hydrogen, an alkyl group or an aryl group of C ₁ -C ₆ ,

L are each independently a linking group,

M is a hydrogen atom or an alkali metal ion or is absent,

X is a halogen atom.

Silica particles having an acryloxy group introduced on the surface, compounds of formulas 6 to 10, and reactions therebetween are the same as those described for the silica particles for CMP, so a detailed description is omitted to avoid overlap.

One embodiment of the present invention relates to a CMP slurry composition comprising the silica particles for CMP and an oxidizing agent.

In one embodiment of the present invention, the silica particles for CMP perform a physical polishing action while chemical polishing action due to at least one functional group selected from the group consisting of phosphoric acid groups, phosphonic acid groups, sulfuric acid groups, sulfonic acid groups and ammonium groups introduced to the surface. You can also do

The silica particles for CMP according to the present invention may be spherical.

The average particle diameter (D50) of the silica particles for CMP according to the present invention may be 10 to 500 nm, preferably 20 to 100 nm.

The silica particles for CMP may be included in an amount of 0.01 to 20% by weight, preferably 0.05 to 15% by weight based on 100% by weight of the total CMP slurry composition. When the silica particles for CMP are included in an amount of less than 0.01% by weight, the polishing rate for the copper film may be lowered, and when it is included in an amount of more than 20% by weight, dispersion stability of the slurry composition may be deteriorated.

CMP slurry composition according to an embodiment of the present invention may further include other abrasive particles other than the silica particles for the CMP.

The other abrasive particles may be inorganic particles, organic particles, or a combination thereof.

As the inorganic particles, metal oxides such as alumina (Al ₂ O ₃ ), ceria (CeO ₂ ), zirconia (ZrO ₂ ), titania (TiO ₂ ), and molybdenum oxide (MoO ₃ ) may be used. As the furnace, particles made of polystyrene, polymethyl methacrylate, polyvinyl chloride, polyacetal, polyester, polyamide, polyimide or copolymers thereof can be used.

The other abrasive particles may be included in an amount of 10% by weight or less based on 100% by weight of the total CMP slurry composition.

In one embodiment of the present invention, the oxidizing agent serves to chemically etch the surface of the copper film to be polished.

As the oxidizing agent, those commonly used in copper polishing CMP slurries can be used without limitation. Specifically, the oxidizing agent includes hydrogen peroxide, nitric acid, peroxic acid, potassium peroxate, lithium peroxate, sodium peroxate, potassium permanganate, lithium permanganate, sodium permanganate, dichromic acid, potassium dichromate, lithium dichromate, sodium dichromate, Perchloric acid, perchlorate (alkali metal salt, ammonium salt, etc.), hypochlorous acid, hypochlorite (alkali metal salt, ammonium salt, etc.), persulfuric acid, persulfate (alkali metal salt, ammonium salt, etc.), peracetic acid, t-butyl hydroperoxide, perbenzoic acid And ozone. These may be used alone or in combination of two or more. In particular, hydrogen peroxide may be used as the oxidizing agent.

The oxidizing agent may be added in an amount of 0.01 to 10% by weight based on 100% by weight of the total slurry composition, preferably 0.1 to 5% by weight. In the above range, an appropriate polishing rate for the copper film can be obtained.

The CMP slurry composition according to the present invention may further include a corrosion inhibitor, a solvent, a surfactant, a pH adjusting agent, a modifier, a polymer compound, and a dispersant.

In one embodiment of the present invention, the corrosion inhibitor retards the chemical reaction of the oxidizing agent to suppress corrosion in a low stepped region where physical polishing does not occur while being removed by physical action of abrasive particles in a high stepped region where polishing occurs. It serves as a polishing regulator that enables polishing.

As the corrosion inhibitor, a nitrogen-containing compound may be used, for example, ammonia, alkylamines, amino acids, imines, azoles, and the like. These may be used alone or in combination of two or more.

Corrosion inhibitors are more effective compounds containing cyclic nitrogen compounds and derivatives thereof, and include benzoquinone, benzyl butyl phthalate, and benzyl dioxolane. The compound to be used can be used.

Among these, triazole compounds such as 1,2,3-triazole, 1,2,4-triazole, and benzotriazole, tetrazol compounds such as aminotetrazole, or mixtures thereof are particularly preferred.

The corrosion inhibitor may be included in 0.001 to 10% by weight relative to 100% by weight of the total slurry composition, preferably, 0.001 to 5% by weight, more preferably, 0.001 to 3% by weight. Within this range, an excellent corrosion inhibiting effect and an appropriate polishing rate can be obtained.

The solvent is for preparing a CMP slurry composition in a slurry state, for example, it may be water, preferably deionized water.

The surfactant plays a role in imparting polishing suppression, dissolution or dispersion stability of each component, antifoaming, and the like. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and betaine surfactants, and these may be used alone or in combination of two or more. Specifically, examples of the surfactant include higher fatty acid salts, higher alcohol sulfate ester salts, sulfide olefin salts, higher alkyl sulfonates, and the like.

The surfactant may be included in 0.0001 to 10% by weight based on 100% by weight of the total slurry composition. In the above range, a sufficient effect is exhibited, and the polishing rate may not be lowered.

As the pH adjusting agent, a basic compound or an acidic compound may be used. Examples of the basic compound include lithium hydroxide, sodium hydroxide, potassium hydroxide, and ammonia, and the acidic compound includes hydrochloric acid and nitric acid.

The CMP slurry composition of the present invention may have a pH of 5 to 9, preferably 6 to 8. It is excellent in the corrosion prevention effect of the copper film in the above range.

The CMP slurry composition according to the present invention can be advantageously used to polish a metal film such as copper wiring.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. It is apparent to those skilled in the art that these examples and experimental examples are only for describing the present invention, and the scope of the present invention is not limited to them.

Synthetic example  1: surface Modified  Preparation of silica particles

3.24 g of 10% phosphoric acid was added to 1000 g of silica sol (Inochem) under stirring to adjust the pH to 4.5.

As a silane coupling agent, 10.05 g of 70% nitric acid was added to 800 g of a 10% aqueous solution of the compound of Formula 12 to adjust the pH to 3.5.

1000 g of the pH-adjusted silica sol was added to a 1 L reaction vessel, heated to 60 ° C., and 100 g of the pH-adjusted silane coupling agent aqueous solution was added and reacted with stirring for 2 hours to prepare surface-modified silica particles.

Synthetic example  2: surface Modified  Preparation of silica particles

Surface-modified silica particles were prepared in the same manner as in Synthesis Example 1, except that the compound of Formula 13 was used instead of the compound of Formula 12.

Synthetic example  3: surface Modified  Preparation of silica particles

Surface-modified silica particles were prepared in the same manner as in Synthesis Example 1, except that the compound of Formula 14 was used instead of the compound of Formula 12.

Synthetic example  4: surface Modified  Preparation of silica particles

Surface-modified silica particles were prepared in the same manner as in Synthesis Example 1, except that the compound of Formula 15 was used instead of the compound of Formula 12.

Synthetic example  5: Surface Modified  Preparation of silica particles

Surface-modified silica particles were prepared in the same manner as in Synthesis Example 1, except that the compound of Formula 16 was used instead of the compound of Formula 12.

Synthetic example  6: Surface Modified  Preparation of silica particles

Surface-modified silica particles were prepared in the same manner as in Synthesis Example 1, except that the compound of Formula 17 was used instead of the compound of Formula 12.

Synthetic example  7: surface Modified  Preparation of silica particles

[Formula 18]

Silica particles having an acryloxy group introduced thereon were prepared in the same manner as in Synthesis Example 1, except that the compound of Formula 18 was used instead of the compound of Formula 12.

The surface-modified silica particles were prepared by reacting 2-mercaptoethanesulfonic acid with silica particles having an acrylicoxy group introduced on the surface.

Synthetic example  8: surface Modified  Preparation of silica particles

Surface modified silica particles were prepared in the same manner as in Synthesis Example 7, except that 2-aminoethyl dihydrogen phosphate was used instead of 2-mercaptoethanesulfonic acid.

Example  1 to 10 and Comparative example  1 to 2: CMP Slurry  Preparation of the composition

Each component was mixed with the composition of Table 1 to prepare a CMP slurry composition (unit: wt%).

Example Comparative example One 2 3 4 5 6 7 8 9 10 One 2 Silica particles A-1 1.0 - - - - - - - 6.0 0.5 - - A-2 - 1.0 - - - - - - - - - - A-3 - - 1.0 - - - - - - - - - A-4 - - - 1.0 - - - - - - - - A-5 - - - - 1.0 - - - - - - - A-6 - - - - - 1.0 - - - - - - A-7 - - - - - - 1.0 - - - - - A-8 - - - - - - - 1.0 - - - - Specific surface modified silica particles - - - - - - - - - - 1.0 1.0 Hydrogen peroxide 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 0.5 1.5 1.0 1.0 Phosphoric acid - - - - - - - - - - - 1.0 Deionized water Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance

A-1: Surface-modified silica particles of Synthesis Example 1

A-2: Surface-modified silica particles of Synthesis Example 2

A-3: surface-modified silica particles of Synthesis Example 3

A-4: surface-modified silica particles of Synthesis Example 4

A-5: Surface-modified silica particles of Synthesis Example 5

A-6: Surface-modified silica particles of Synthesis Example 6

A-7: Surface-modified silica particles of Synthesis Example 7

A-8: surface-modified silica particles of Synthesis Example 8

Experimental Example  One:

The CMP slurry compositions prepared in Examples and Comparative Examples were measured for polishing rate and dishing inhibition evaluation in the following manner, and the results are shown in Table 2 below. The polishing conditions were as follows.

<Polishing conditions>

Polishing machine: Mecatech 334 (manufactured by PRESI)

Polishing pad: BYM 1500 (manufactured by RION)

Platen speed: 50 rpm

Carrier rotation speed: 50rpm

Abrasive working pressure: 0.5daN

Abrasive feed rate: 170 ml / min

(1) Polishing speed

The polishing rate was measured by using a copper blanket 8-inch wafer with a 1500 nm film formed on a silicon substrate by electrolytic plating as an object to be polished. The polishing rate was evaluated according to the following evaluation criteria by measuring the time at which the film of 1500 nm was removed and converting the removal rate with time.

<Evaluation criteria>

○: 15000 A / min or more

△: 10000 A / min or more to less than 15000 A / min

×: 8000 A / min or more to less than 10000 A / min

××: less than 8000A / min

(2) Dishing  control

After forming a groove having a depth of 250 nm and a width of 50 μm with a space of 50 μm in a hard silica layer of a wafer having a 250 nm hard silica film formed by plasma CVD using tetrakisethoxysilane, a tantalum / tantalum nitride is formed by sputtering. After depositing a film of 15 nm / 15 nm and further depositing a copper seed layer of 100 nm by sputtering, the patterning 8-inch wafer having a copper film of 1000 nm formed by electrolytic plating was used as an object to be polished to evaluate dishing suppression. Dishing was measured by using the atomic force microscope (AFM) for the step difference between the first convex portion and the first concave portion of the 50 µm copper wiring, and evaluated according to the following evaluation criteria.

<Evaluation criteria>

○: less than 200 A / min

△: 200 A / min or more to less than 300 A / min

×: 300 A / min or more to less than 400 A / min

××: 400 A / min or more

Example Comparative example One 2 3 4 5 6 7 8 9 10 One 2 Polishing speed ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ×× × Dish suppression ○ ○ ○ ○ ○ ○ ○ ○ ○ △ ○ ×

As shown in Table 2, it was confirmed that the CMP slurry compositions of Examples 1 to 10 including the surface-modified silica particles according to the present invention had a high polishing rate and excellent dishing suppression. On the other hand, the CMP slurry composition of Comparative Example 1 containing unmodified silica particles has a significantly slower polishing rate, and the CMP slurry composition of Comparative Example 2 containing separate phosphoric acid together with the unmodified silica particles has a polishing rate. It was confirmed that the occurrence of dishing was slow and large.

Since the specific parts of the present invention have been described in detail above, it is obvious that for those skilled in the art to which the present invention pertains, this specific technology is only a preferred embodiment, and the scope of the present invention is not limited thereto. Do. Those skilled in the art to which the present invention pertains will be able to make various applications and modifications within the scope of the present invention based on the above.

Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims (17)

Silica particles for CMP in which one or more functional groups selected from the group consisting of phosphoric acid groups, phosphonic acid groups, sulfuric acid groups, sulfonic acid groups and ammonium groups are introduced on the surface. According to claim 1, Phosphoric acid group, phosphonic acid group, sulfuric acid group, sulfonic acid group and prepared by sol-gel reaction of a silane coupling agent having at least one functional group selected from the group consisting of ammonium groups, phosphoric acid groups, phosphonic acid groups, sulfuric acid groups, sulfonic acid groups and Silica particles for CMP produced by binding reaction of a silane coupling agent having at least one functional group selected from the group consisting of ammonium groups to silica particles. The silica particle for CMP according to claim 2, wherein the silane coupling agent having at least one functional group selected from the group consisting of a phosphoric acid group, a phosphonic acid group, a sulfuric acid group, a sulfonic acid group, and an ammonium group comprises one or more of the compounds of Formulas 1 to 5 below. :
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In the above formula,
R ¹ is each independently hydrogen or an alkyl group of C ₁ -C ₆ ,
R ² are each independently a C ₁ -C ₆ alkyl group,
R ³ to R ⁶ are each independently hydrogen, an alkyl group or an aryl group of C ₁ -C ₆ ,
L are each independently a linking group,
M is a hydrogen atom or an alkali metal ion or is absent,
X is a halogen atom,
n is an integer from 1 to 3. According to claim 3, L is each independently one or more of the chain carbon is oxygen, nitrogen substituted with one or two C ₁ -C ₆ alkyl group, or C ₁ -C ₆ substituted or unsubstituted with arylene. Silica particles for CMP which is an alkylene group. The silica particle for CMP according to claim 3, wherein the silane coupling agent having at least one functional group selected from the group consisting of a phosphoric acid group, a phosphonic acid group, a sulfuric acid group, a sulfonic acid group and an ammonium group comprises at least one of the following compounds of formulas 12 to 17: :
[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

According to claim 1, CMP silica particles prepared by reacting at least one of the compounds of formulas 6 to 10 with silica particles having an acrylicoxy group introduced on the surface:
[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

In the above formula,
Z are each independently a thiol, amino or C ₁ -C ₆ alkylamino group,
R ³ to R ⁶ are each independently hydrogen, an alkyl group or an aryl group of C ₁ -C ₆ ,
L are each independently a linking group,
M is a hydrogen atom or an alkali metal ion or is absent,
X is a halogen atom. The method of claim 6, wherein L is each independently one or more of the chain carbon is oxygen, nitrogen substituted with one or two C ₁ -C ₆ alkyl groups, or C ₁ -C ₆ substituted or unsubstituted with arylene. Silica particles for CMP which is an alkylene group. The silica particles for CMP according to claim 6, wherein the silica particles in which the acryloxy group is introduced on the surface are prepared by a sol-gel reaction of the compound of Formula 11, or by binding a compound of Formula 11 to silica particles:
[Formula 11]

In the above formula,
R ¹ is each independently hydrogen or an alkyl group of C ₁ -C ₆ ,
R ² are each independently a C ₁ -C ₆ alkyl group,
Y is a linking group,
n is an integer from 1 to 3. The method of claim 8, Y is one or more of the chain carbon is oxygen, nitrogen substituted with one or two C ₁ -C ₆ alkyl group, or C ₁ -C ₆ alkylene group unsubstituted or substituted with arylene. Silica particles for CMP. The method of claim 6, wherein the surface is composed of silica particles having an acryloxy group introduced therein, 2-mercaptoethanesulfonic acid, 2-aminoethanesulfonic acid, 2-aminoethyl hydrogen sulfate and 2-aminoethyl dihydrogen phosphate. CMP silica particles prepared by reacting at least one selected from the group. Method for producing silica particles for CMP comprising the step of sol-gel reacting a silane coupling agent comprising at least one of the compounds of Formulas 1 to 5:
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In the above formula,
R ¹ is each independently hydrogen or an alkyl group of C ₁ -C ₆ ,
R ² are each independently a C ₁ -C ₆ alkyl group,
R ³ to R ⁶ are each independently hydrogen, an alkyl group or an aryl group of C ₁ -C ₆ ,
L are each independently a linking group,
M is a hydrogen atom or an alkali metal ion or is absent,
X is a halogen atom,
n is an integer from 1 to 3. Method for producing silica particles for CMP comprising the step of reacting a silane coupling agent containing at least one of the compounds of Formulas 1 to 5 to the silica particles:
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In the above formula,
R ¹ is each independently hydrogen or an alkyl group of C ₁ -C ₆ ,
R ² are each independently a C ₁ -C ₆ alkyl group,
R ³ to R ⁶ are each independently hydrogen, an alkyl group or an aryl group of C ₁ -C ₆ ,
L are each independently a linking group,
M is a hydrogen atom or an alkali metal ion or is absent,
X is a halogen atom,
n is an integer from 1 to 3. Method for producing silica particles for CMP comprising the step of reacting one or more of the compounds of Formulas 6 to 10 with silica particles having an acrylicoxy group introduced on the surface:
[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

In the above formula,
Z are each independently a thiol, amino or C ₁ -C ₆ alkylamino group,
R ³ to R ⁶ are each independently hydrogen, an alkyl group or an aryl group of C ₁ -C ₆ ,
L are each independently a linking group,
M is a hydrogen atom or an alkali metal ion or is absent,
X is a halogen atom. The method of claim 13, wherein the surface of the acrylic particle is introduced into the silica particles are prepared by the sol-gel reaction of the compound of formula 11, or the preparation of silica particles for CMP produced by binding reaction of the compound of formula 11 to the silica particles Way:
[Formula 11]

In the above formula,
R ¹ is each independently hydrogen or an alkyl group of C ₁ -C ₆ ,
R ² are each independently a C ₁ -C ₆ alkyl group,
Y is a linking group,
n is an integer from 1 to 3. A CMP slurry composition comprising the silica particles for CMP and an oxidizing agent according to any one of claims 1 to 10. 16. The CMP slurry composition of claim 15, wherein the oxidizing agent comprises hydrogen peroxide. The CMP slurry composition of claim 15, wherein the silica particles for CMP are contained in an amount of 0.01 to 20% by weight based on 100% by weight of the total composition.