CN115703931A - Modified colloidal silicon dioxide and preparation method and application thereof - Google Patents
Modified colloidal silicon dioxide and preparation method and application thereof Download PDFInfo
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- CN115703931A CN115703931A CN202110884902.6A CN202110884902A CN115703931A CN 115703931 A CN115703931 A CN 115703931A CN 202110884902 A CN202110884902 A CN 202110884902A CN 115703931 A CN115703931 A CN 115703931A
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Abstract
The invention belongs to the technical field of inorganic nano materials, and particularly relates to modified colloidal silicon dioxide and a preparation method and application thereof. A preparation method of modified colloidal silica comprises the following steps: and under an acidic condition, modifying the colloidal silica by adopting a hydrolyzed silane coupling agent to obtain the modified colloidal silica. Under the acidic condition, the hydrolyzed silane coupling agent is adopted to modify the colloidal silica, so that the phenomenon of floccule, precipitate or gelation generated by the silane coupling agent during and after addition can be effectively inhibited, the Zeta potential of the modified colloidal silica obtained by the method is 10-65mV at the pH value of 1.0-5.0, the stability of the colloidal silica under the acidic condition is improved, the pH area of the colloidal silica is expanded, and the method is very suitable for polishing under the acidic condition.
Description
Technical Field
The invention belongs to the technical field of inorganic nano materials, and particularly relates to modified colloidal silicon dioxide and a preparation method and application thereof.
Background
Chemical Mechanical Polishing (CMP) planarization techniques are key processes in the fabrication of integrated circuit chips. The polishing solution is a key material in the CMP process. With the continuous reduction of the integrated circuit technology nodes, the continuous increase of the number of interconnection layers and the application of new materials and new processes, the use times and the importance of CMP in the chip process are continuously increased, the use amount of the polishing solution is increased, the reduction of the technology nodes puts higher quality requirements on the CMP polishing solution, and the requirement cost is lower and lower. The polishing liquid is mainly composed of abrasive particles and a chemical additive, the abrasive particles are particles having a function of cutting a surface of an object to be polished by a physical action, and colloidal silica is generally used as an abrasive for high-end applications.
Colloidal silica has a problem of aggregation and poor stability under acidic conditions, and there has been a demand for a silica dispersion having excellent stability over a wide pH range.
As the colloidal silica having improved stability under acidic conditions, a modification method such as aluminum modification, in which colloidal silica is treated with basic aluminum chloride to obtain aluminum-modified silica, is commonly used. Although the stability under acidic conditions can be improved by the aluminum modification method, metal impurities such as aluminum and the like are introduced, so that the use of the aluminum in the polishing solution for integrated circuits is limited.
The silane coupling agent is used for modifying the colloidal silica, so that the metal impurities can be effectively prevented from being mixed. Chinese patent CN109071238a discloses a method for producing a cation-modified silica, which comprises adding a silane coupling agent having a cationic group to a silica raw material exhibiting a negative value with respect to Zeta potential, and reacting the mixture to obtain a cation-modified silica having a positive Zeta potential region at a pH of 7 or more, and a cation-modified silica dispersion. Chinese patent CN106575614a discloses a method of making a chemical-mechanical polishing composition comprising growing colloidal silica abrasive particles in a liquid comprising an aminosilane compound such that the aminosilane compound becomes incorporated in the abrasive particles to form a "core-shell" structure, thereby resulting in a chemical-mechanical polishing composition comprising colloidal silica particles having incorporated therein the aminosilane compound. In the prior art, silane coupling agent modified silica is carried out under a neutral or alkaline system, but has the following problems: during and after the addition of the silane coupling agent, flocs or precipitates may be generated, and gelation may occur.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, it is an object of the present invention to provide a modified colloidal silica, a method for preparing the same, and a use thereof, which solve the problems of the prior art.
To achieve the above objects and other related objects, the present invention is achieved by the following technical solutions.
One of the purposes of the invention is a preparation method of modified colloidal silicon dioxide, which comprises the following steps:
and under an acidic condition, modifying the colloidal silica by adopting a hydrolyzed silane coupling agent to obtain the modified colloidal silica.
Preferably, the colloidal silica has a pH of 2.0 to 5.0.
Preferably, the content of silica in the colloidal silica is 10 to 40wt%.
Preferably, the particle size of the colloidal silica is 30 to 100nm.
Preferably, the colloidal silica is obtained by exchanging a silica raw material with a cation exchange resin.
More preferably, the content of silica in the colloidal silica raw material is 10 to 40wt%.
More preferably, the colloidal silica raw material has a pH of 7 to 14.
More preferably, the particle size of the colloidal silica raw material is 30 to 100nm.
More preferably, the cation exchange resin is a strong acid type cation exchange resin.
Preferably, the pH value of the acidic condition is 1.0 to 5.0.
Preferably, the temperature at the time of modification is 20 to 100 ℃.
Preferably, the mass ratio of silica to the silane coupling agent in the colloidal silica is 100: (0.2-10).
Preferably, the silane coupling agent is a silane coupling agent containing an amino group.
More preferably, the amino group-containing silane coupling agent is selected from one or more of primary aminosilanes, secondary aminosilanes and tertiary aminosilanes. The Zeta potential of silica is varied in this application by grafting the amino groups of the silane coupling agent onto the surface of the silica particles.
Further preferably, the silane coupling agent containing an amino group is selected from one or more of N- (β -aminoethyl) - γ -aminopropylmethyldimethoxysilane, N- (β -aminoethyl) - γ -aminopropylmethyldiethoxysilane, N- (β -aminoethyl) - γ -aminopropyltrimethoxysilane, N- (β -aminoethyl) - γ -aminopropyltriethoxysilane, γ -aminopropyltrimethoxysilane, diethylaminomethyltriethoxysilane, (N, N-dimethyl-3-aminopropyl) trimethoxysilane, N-diethyl-3-aminopropyltrimethoxysilane, cyclohexylaminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, anilinomethyltrimethoxysilane, anilinomethyltriethoxysilane, γ -aminoethylaminoethylaminopropyltrimethoxysilane and bis (3-trimethoxysilylpropyl) amine.
Still more preferably, the silane coupling agent having an amino group is selected from one or more of N- (β -aminoethyl) - γ -aminopropyltrimethoxysilane, N- (β -aminoethyl) - γ -aminopropyltriethoxysilane, and γ -aminopropyltrimethoxysilane.
Preferably, the hydrolyzed silane coupling agent is prepared by the following method: an aqueous solution of the silane coupling agent is adjusted to be acidic with an acid, and then hydrolyzed.
More preferably, the acid is selected from one or more of nitric acid, sulfuric acid, hydrochloric acid, formic acid, acetic acid and citric acid.
More preferably, the concentration of the aqueous solution of the silane coupling agent is 1 to 10wt%.
More preferably, the acidic pH is 1.0 to 5.0.
More preferably, the time of hydrolysis is 0.5 to 24. The hydrolysis time in the application can not be too long or too short, the hydrolysis time is too short, the hydrolysis is incomplete, and the reaction efficiency is not high; the silane coupling agent is self-polymerized after a long time, and the stability is poor.
The second object of the present invention is to provide modified colloidal silica prepared by the above-mentioned preparation method.
Preferably, the content of silica in the modified colloidal silica is not less than 5wt%.
Preferably, the Zeta potential is 10-65mV when the pH value of the modified colloidal silica is 1.0-5.0.
The invention also aims to provide the application of the modified colloidal silica as a polishing solution in integrated circuits.
Compared with the prior art, the invention has the following beneficial effects:
1) The preparation method is simple and convenient, and the hydrolyzed silane coupling agent is adopted to modify the colloidal silica under the acidic condition, so that the phenomenon of floccule, precipitate or gelation generated when and after the silane coupling agent is added can be effectively inhibited; easy operation and suitability for industrial production.
2) When the pH value of the modified colloidal silica is 1.0-5.0, the Zeta potential is 10-65mV, so that the stability of the colloidal silica under an acidic condition is improved, the pH area of the colloidal silica is expanded, and the modified colloidal silica is very suitable for polishing under an acidic condition.
3) The modified colloidal silicon dioxide can improve the polishing rate by more than 25 percent and has better surface quality.
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure.
Before the present embodiments are further described, it is to be understood that the scope of the invention is not to be limited to the specific embodiments described below; it is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention. Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the respective manufacturers.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition to the specific methods, devices, and materials used in the examples, any methods, devices, and materials similar or equivalent to those described in the examples may be used in the practice of the invention in addition to the specific methods, devices, and materials used in the examples, in keeping with the knowledge of one skilled in the art and with the description of the invention.
The embodiment of the application provides a preparation method of modified colloidal silica, which solves the problems that floccules or precipitates are generated sometimes and gelation sometimes occurs sometimes during and after adding a silane coupling agent when modifying the colloidal silica in the prior art. The preparation method of the modified colloidal silica comprises the following steps: and under an acidic condition, modifying the colloidal silica by adopting a hydrolyzed silane coupling agent to obtain the modified colloidal silica. According to the preparation method, the silane coupling agent is hydrolyzed under an acidic condition, so that an amino group of the silane coupling agent is grafted on the surface of the silica particle, the Zeta potential of the silica is changed, the imagination that flocculation or precipitation occurs when or after the silane coupling agent is added can be avoided, meanwhile, the modified colloidal silica obtained by the preparation method is high in dispersity under the acidic condition, and the pH range of the silica is expanded.
In a preferred embodiment, the colloidal silica has a pH of 2.0 to 5.0.
In a preferred embodiment, the colloidal silica has a silica content of 10 to 40wt%.
In a preferred embodiment, the particle size of the colloidal silica is 30 to 100nm.
In a preferred embodiment, the colloidal silica is obtained by exchanging a silica raw material with a cation exchange resin. The silica raw material is preferably colloidal silica, and the colloidal silica can be produced by a sol-gel method. Colloidal silica produced by the sol-gel method is preferable because it contains less metal impurities having diffusibility in semiconductors and less corrosive ions such as chloride ions. The raw material colloidal silica may be produced by a method other than the sol-gel method. The average particle diameter of the silica raw material is not particularly limited, and is preferably 30 to 100nm. The silica concentration in the silica raw material is not particularly limited, but is preferably 10 to 40wt% from the practical viewpoint. The cation exchange resin is not particularly limited, and a strong acid type cation exchange resin is preferably selected. In the research of the applicant, the silica raw material is adjusted to be acidic by using acid, and then modified colloidal silica is prepared, but the stability of the obtained modified colloidal silica in an acidic environment is not good by using cation resin exchange to obtain the modified colloidal silica prepared again.
In a preferred embodiment, the silane coupling agent is a silane coupling agent containing an amino group, so that the amino group of the silane coupling agent is grafted on the surface of the silica particles, thereby changing the Zeta potential of the silica. Specifically, the silane coupling agent having an amino group is not particularly limited, and includes one or more of primary aminosilane, secondary aminosilane, and tertiary aminosilane. More specifically, the silane coupling agent is selected from one or more of N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldiethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, diethylaminomethyltriethoxysilane, (N, N-dimethyl-3-aminopropyl) trimethoxysilane, N-diethyl-3-aminopropyltrimethoxysilane, cyclohexylaminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, anilinomethyltrimethoxysilane, anilinomethyltriethoxysilane, gamma-aminoethylaminoethylaminopropyltrimethoxysilane and bis (3-trimethoxysilylpropyl) amine. Among them, N- (β -aminoethyl) - γ -aminopropyltrimethoxysilane, N- (β -aminoethyl) - γ -aminopropyltriethoxysilane, or γ -aminopropyltrimethoxysilane are preferably used from the viewpoint of good reactivity with the silica raw material. In the present invention, only 1 kind of silane coupling agent may be used alone, or 2 or more kinds may be used in combination.
In a preferred embodiment, the silane coupling agent is further subjected to a prehydrolysis step, which comprises: an aqueous solution of the silane coupling agent is adjusted to be acidic with an acid, and then hydrolysis is performed. Specifically, the acid is not particularly limited, such as nitric acid, sulfuric acid, hydrochloric acid, formic acid, acetic acid, or citric acid; the acid may be used alone in 1 kind, or may be used in combination in 2 or more kinds. Specifically, the concentration of the aqueous solution of the silane coupling agent is 1 to 10wt%; the pH value of the acidity is 1.0-5.0; the hydrolysis time is 0.5 to 24 hours.
In a preferred embodiment, the amount of the silane coupling agent to be added is changed to an optimum amount in consideration of the specific surface area of the raw material silica, the molecular weight of the silane coupling agent, and the like, and therefore, it is difficult to specify the amount, and it is preferable that the ratio of the mass of silica to the mass of the silane coupling agent in the colloidal silica is 100: (0.2-10).
In a preferred embodiment, the pH of the acidic condition is 1.0 to 5.0.
In a preferred embodiment, the temperature at which the silica modification is carried out by adding the silane coupling agent is not limited, but is preferably from room temperature such as 20 ℃ to 100 ℃. The reaction time is not limited, and is preferably 0.5 to 24 hours.
In a preferred embodiment, the silane coupling agent may be added in one portion, may be added in divided portions, or may be added continuously, but it is preferable to carry out the dropping in one portion at a constant dropping rate.
The embodiment of the application also provides the modified colloidal silicon dioxide prepared by the preparation method. When the pH value of the modified colloidal silicon dioxide is 1.0-5.0, the Zeta potential is a positive value and is 10-65 mV; and the content of silica is not less than 5wt%. The modified colloidal silica of the present application exhibits an effect of stably dispersing for a long period of time in a wide pH range (particularly, even under acidic conditions), and is very suitable for various polishing liquids which require polishing under acidic conditions.
The water used in the specific examples described below in this application is ultra-pure water having a resistivity of >18 megaohms.
For convenience of example, the colloidal silica raw materials used in the examples described below in this application are commercially available.
In the examples described below, the modified colloidal silica and the colloidal silica were used in the average particle size by a dynamic light scattering method using a laser particle size analyzer model Nicomp (TM) 380/ZLS manufactured by PSS of the United states.
In the examples described below, the Zeta potential of the modified colloidal silica and the colloidal silica was measured by the electroacoustic method, and the instrument used was a high-concentration Zeta potential analyzer of type Zeta Finder ZF400 manufactured by MAS corporation of usa. Note that the Zeta test can be performed as it is without dilution.
In the following examples of the present application, the stability test was evaluated by the modified colloidal silica at 45 ℃ and the time when the colloidal silica gelled.
Example 1
In the embodiment, the silicon dioxide raw material is PL-2 type silicon sol produced by FUSO chemical company by a sol-gel method, wherein the content of the silicon dioxide in the silicon dioxide raw material is 20wt%; the average particle size of the silicon dioxide raw material is 36nm; the silica raw material had a pH of 7.51.
The preparation method of the modified colloidal silicon dioxide comprises the following steps:
(1) The silicon dioxide raw material is modified by strong acid type cation exchange resin to obtain the colloidal silicon dioxide with the pH value of 4.0.
(2) Hydrolysis of silane coupling agent: diluting N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane (KH-791 for short) with water to a concentration of 1wt%, adjusting pH to 3.0 with 20wt% sulfuric acid aqueous solution, and hydrolyzing for 24h to obtain hydrolyzed silane coupling agent, which is marked as KH-791 solution;
adding the KH-791 solution into the colloidal silica under stirring, and reacting at room temperature for 0.5 hour to obtain modified colloidal silica. Wherein the mass ratio of the silicon dioxide to the silane coupling agent in the colloidal silicon dioxide is 100.
The modified colloidal silica obtained in this example was found to have a silica content of 16.2wt%; at a pH of 4.50, the Zeta potential is +23.46mV.
Stability test, the modified colloidal silica obtained in this example was placed in an oven at 45 ℃ and observed, and no gelation was observed even after it was left for at least 2 months.
Example 2
In the embodiment, the silicon dioxide raw material is PL-2 type silicon sol produced by FUSO chemical company by a sol-gel method, wherein the content of the silicon dioxide in the silicon dioxide raw material is 20wt%; the average particle size of the silicon dioxide raw material is 36nm; the pH was 7.51.
The preparation method of the modified colloidal silica comprises the following steps:
(1) The silica raw material is modified by strong acid type cation exchange resin to obtain the colloidal silica with the pH value of 5.0.
(2) Hydrolysis of silane coupling agent: diluting N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane (KH-792) with water to a concentration of 1wt%, adjusting pH to 2.5 with 20wt% sulfuric acid aqueous solution, and hydrolyzing for 12h to obtain hydrolyzed silane coupling agent labeled as KH-792 solution;
the KH-792 solution is added to the colloidal silica under stirring, and the mixture is reacted at room temperature for 2 hours to obtain modified colloidal silica. Wherein the mass ratio of the silicon dioxide to the silane coupling agent in the colloidal silicon dioxide is 100.
The modified colloidal silica obtained in this example was found to have a silica content of 15.1wt%; at a pH of 4.70, the Zeta potential was +33.46mV.
Stability test, the modified colloidal silica obtained in this example was placed in an oven at 45 ℃ and observed, and gelation was not observed even when the modified colloidal silica was left to stand for at least 2 months.
Example 3
In the embodiment, the silicon dioxide raw material is PL-3 type silicon sol produced by FUSO chemical company by a sol-gel method, wherein the content of the silicon dioxide in the silicon dioxide raw material is 20wt%; the average particle size of the silicon dioxide raw material is 60nm; the pH was 7.30.
The preparation method of the modified colloidal silica comprises the following steps:
(1) The silica raw material is modified by strong acid type cation exchange resin to obtain the colloidal silica with the pH value of 4.0.
(2) Hydrolysis of silane coupling agent: diluting gamma-aminopropyltrimethoxysilane (KH-540 for short) with water to the concentration of 5wt%, adjusting the pH value to 3.5 by using 10wt% nitric acid aqueous solution, and hydrolyzing for 0.5h to obtain a hydrolyzed silane coupling agent, which is marked as KH-540 solution;
adding the KH-540 solution into the colloidal silica under stirring, and reacting at 30 ℃ for 4 hours to obtain the modified colloidal silica. Wherein the mass ratio of the silicon dioxide to the silane coupling agent in the colloidal silicon dioxide is 100:0.6.
the modified colloidal silica obtained in this example was found to have a silica content of 17.4wt%; at a pH of 5.0, the Zeta potential was +29.19mV.
Stability test, the modified colloidal silica obtained in this example was placed in an oven at 45 ℃ and observed, and no gelation was observed even after it was left for at least 2 months.
Example 4
In the embodiment, the silicon dioxide raw material is PL-2 type silicon sol produced by FUSO chemical company by a sol-gel method, wherein the content of the silicon dioxide in the silicon dioxide raw material is 20wt%; the average particle size of the silicon dioxide raw material is 36nm; the pH was 7.51.
The preparation method of the modified colloidal silicon dioxide comprises the following steps:
(1) The silica raw material is modified by strong acid type cation exchange resin to obtain the colloidal silica with the pH value of 4.5.
(2) Hydrolysis of silane coupling agent: diluting gamma-aminopropyltriethoxysilane (KH-550 for short) with water to 5wt%, adjusting pH to 3.0 with 10wt% hydrochloric acid water solution, and hydrolyzing for 12 hr to obtain hydrolyzed silane coupling agent, which is marked as KH-550 solution;
adding the KH-550 solution into colloidal silica under stirring, and reacting at 50 deg.C for 12 hr to obtain modified colloidal silica. Wherein the mass ratio of the silicon dioxide to the silane coupling agent in the colloidal silicon dioxide is 100:3.5.
the modified colloidal silica obtained in this example was found to have a silica content of 16.8wt%; at a pH of 3.5, the Zeta potential was +64.67mV.
Stability test, the modified colloidal silica obtained in this example was placed in an oven at 45 ℃ and observed, and no gelation was observed even after it was left for at least 2 months.
Example 5
In the embodiment, the silicon dioxide raw material is colloidal silicon dioxide which is purchased from commercial channels and prepared by an ion exchange method, wherein the content of silicon dioxide in the silicon dioxide raw material is 10wt%; the average particle size of the silicon dioxide raw material is 30nm; the pH was 9.82.
The preparation method of the modified colloidal silica comprises the following steps:
(1) The silica raw material is modified by strong acid type cation exchange resin to obtain the colloidal silica with the pH value of 2.0.
(2) Hydrolysis of silane coupling agent: diluting N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane (KH-792 for short) with water to a concentration of 10wt%, adjusting pH to 1.0 with 5wt% sulfuric acid aqueous solution, and hydrolyzing for 4h to obtain hydrolyzed silane coupling agent, labeled as KH-792 solution;
adding the KH-792 solution into colloidal silica under stirring, and reacting at room temperature for 24h to obtain modified colloidal silica. Wherein the mass ratio of the silicon dioxide to the silane coupling agent in the colloidal silicon dioxide is 100:10.
the modified colloidal silica obtained in this example was found to have a silica content of 5.4wt%; at a pH of 1.0, the Zeta potential was +41.45mV.
Stability test, the modified colloidal silica obtained in this example was placed in an oven at 45 ℃ and observed, and no gelation was observed even after it was left for at least 2 months.
Example 6
In the embodiment, the silicon dioxide raw material is colloidal silicon dioxide which is purchased from commercial channels and prepared by an ion exchange method, wherein the content of silicon dioxide in the silicon dioxide raw material is 21wt%; the average particle size of the silicon dioxide raw material is 40nm; the pH was 10.01.
The preparation method of the modified colloidal silicon dioxide comprises the following steps:
(1) The silica raw material is modified by strong acid type cation exchange resin to obtain the colloidal silica with the pH value of 2.5.
(2) Hydrolysis of silane coupling agent: diluting gamma-aminopropyltriethoxysilane (KH-550 for short) with water to 3wt%, adjusting pH to 2.0 with 20wt% hydrochloric acid water solution, and hydrolyzing for 4 hr to obtain hydrolyzed silane coupling agent labeled as KH-550 solution;
and adding the KH-550 solution into the colloidal silica under the stirring state, and reacting at room temperature for 8 hours to obtain the modified colloidal silica. Wherein the mass ratio of the silicon dioxide to the silane coupling agent in the colloidal silicon dioxide is 100:0.3.
the modified colloidal silica obtained in this example was found to have a silica content of 19.9wt%; at a pH of 3.0, the Zeta potential was +10.87mV.
Stability test, the modified colloidal silica obtained in this example was placed in an oven at 45 ℃ and observed, and no gelation was observed even after it was left for at least 2 months.
Example 7
In the embodiment, the silicon dioxide raw material is colloidal silicon dioxide which is purchased from commercial channels and prepared by an ion exchange method, wherein the content of silicon dioxide in the silicon dioxide raw material is 21wt%; the average particle size of the silicon dioxide raw material is 40nm; the pH was 10.01.
The preparation method of the modified colloidal silicon dioxide comprises the following steps:
(1) The silicon dioxide raw material silicon is modified by strong acid type cation exchange resin to obtain the colloidal silicon dioxide with the pH value of 2.5.
(2) Hydrolysis of silane coupling agent: diluting gamma-aminopropyltrimethoxysilane (KH-540 for short) with water to a concentration of 10wt%, adjusting pH to 1.0 with 20wt% hydrochloric acid aqueous solution, and hydrolyzing for 1h to obtain hydrolyzed silane coupling agent, which is marked as KH-540 solution;
adding the KH-540 solution into colloidal silica under stirring, and reacting at 100 ℃ for 2h to obtain the modified colloidal silica. Wherein the mass ratio of the silicon dioxide to the silane coupling agent in the colloidal silicon dioxide is 100:1.5.
the modified colloidal silica obtained in this example was found to have a silica content of 18.1wt%; at a pH of 2.0, the Zeta potential was +41.91mV.
Stability test, the modified colloidal silica obtained in this example was placed in an oven at 45 ℃ and observed, and no gelation was observed even after it was left for at least 2 months.
Example 8
In the embodiment, the silicon dioxide raw material is colloidal silicon dioxide which is purchased from commercial channels and prepared by an ion exchange method, wherein the content of silicon dioxide in the silicon dioxide raw material is 40wt%; the average grain diameter of the silicon dioxide raw material is 100nm; the pH was 9.85.
The preparation method of the modified colloidal silicon dioxide comprises the following steps:
(1) The silica raw material is modified by strong acid type cation exchange resin to obtain the colloidal silica with the pH value of 3.0.
(2) Hydrolysis of silane coupling agent: diluting gamma-aminopropyltriethoxysilane (KH-550 for short) with water to 1wt%, adjusting pH to 3.0 with 20wt% acetic acid water solution, and hydrolyzing for 8 hr to obtain hydrolyzed silane coupling agent labeled as KH-550 solution;
and adding the KH-550 solution into the colloidal silica under the stirring state, and reacting at room temperature for 24 hours to obtain the modified colloidal silica. Wherein the mass ratio of the silicon dioxide to the silane coupling agent in the colloidal silicon dioxide is 100:0.2.
the modified colloidal silica obtained in this example was found to have a silica content of 38.5wt%; at a pH of 4.5, the Zeta potential was +35.11mV.
Stability test, the modified colloidal silica obtained in this example was placed in an oven at 45 ℃ and observed, and no gelation was observed even after it was left for at least 2 months.
Example 9
In the embodiment, the silicon dioxide raw material is colloidal silicon dioxide which is purchased from commercial channels and prepared by an ion exchange method, wherein the content of the silicon dioxide in the silicon dioxide raw material is 10wt%; the average particle size of the silicon dioxide raw material is 30nm; the pH was 9.82.
The preparation method of the modified colloidal silicon dioxide comprises the following steps:
(1) The silica raw material is modified by strong acid type cation exchange resin to obtain the colloidal silica with the pH value of 2.0.
(2) Hydrolysis of silane coupling agent: diluting N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane (KH-792) with water to a concentration of 10wt%, adjusting pH to 5.0 with 1wt% sulfuric acid aqueous solution, and hydrolyzing for 24h to obtain hydrolyzed silane coupling agent, which is marked as KH-550 solution;
and adding the KH-550 solution into the colloidal silica under the stirring state, and reacting at room temperature for 24 hours to obtain the modified colloidal silica. Wherein the mass ratio of the silicon dioxide to the silane coupling agent in the colloidal silicon dioxide is 100:0.6.
the modified colloidal silica obtained in this example was found to have a silica content of 8.8wt%; at a pH of 4.5, the Zeta potential was +21.15mV.
Stability test, the modified colloidal silica obtained in this example was placed in an oven at 45 ℃ and observed, and gelation was not observed even when the modified colloidal silica was left to stand for at least 2 months.
Comparative example 1
The silica raw material in this comparative example 1 was the same as that in example 1.
The preparation method of the colloidal silicon dioxide comprises the following steps:
the pH of the above silica raw material was adjusted to 4.50 with a 5wt% sulfuric acid solution and water to obtain colloidal silica having a concentration of 16.2 wt%.
The colloidal silica obtained in comparative example 1 was tested to have a Zeta potential of-13.23 mV at a pH of 4.5.
Stability test, the colloidal silica was placed in an oven at 45 ℃ and observed to gel at 3 days.
Comparative example 2
The silica raw material in this comparative example 2 was the same as that in example 2.
The preparation method of the colloidal silicon dioxide comprises the following steps:
the pH of the above silica raw material was adjusted to 4.70 with a 5wt% sulfuric acid solution and water to obtain colloidal silica having a concentration of 15.1 wt%.
The colloidal silica obtained in comparative example 2 was tested to have a Zeta potential of-14.13 mV at a pH of 4.7.
Stability test, the colloidal silica was placed in an oven at 45 ℃ and observed to gel at 2.5 days.
Comparative example 3
The silica raw material in this comparative example 3 is the same as that in example 3.
The preparation method of the colloidal silicon dioxide comprises the following steps:
the pH of the above silica raw material was adjusted to 5.0 with a 5wt% nitric acid solution and water to obtain colloidal silica having a concentration of 17.4 wt%.
The colloidal silica obtained in comparative example 3 was tested to have a Zeta potential of-15.43 mV at a pH of 5.0.
Stability test, the colloidal silica was placed in an oven at 45 ℃ for observation, and gelation was observed at 3 days.
Comparative example 4
The silica raw material in this comparative example 4 was the same as that in example 4.
The preparation method of the colloidal silicon dioxide comprises the following steps:
the pH of the above silica raw material was adjusted to 3.5 with a 5wt% hydrochloric acid solution and water to obtain colloidal silica having a concentration of 16.8 wt%.
The colloidal silica of comparative example 4 was tested to have a Zeta potential of-9.45 mV at a pH of 3.5.
Stability test, the colloidal silica was placed in an oven at 45 ℃ and observed to gel at 8 days.
Comparative example 5
The silica raw material in this comparative example 5 was the same as that in example 5.
The preparation method of the colloidal silicon dioxide comprises the following steps:
the pH of the above silica raw material was adjusted to 1.0 with a 5wt% sulfuric acid solution and water to obtain colloidal silica having a concentration of 5.4 wt%.
The colloidal silica obtained in comparative example 5 was tested to have a Zeta potential of +1.03mV at a pH of 1.0.
Stability test, the colloidal silica was placed in an oven at 45 ℃ and observed to gel at 20 days.
Comparative example 6
The silica raw material in this comparative example 6 is the same as that in example 6.
The preparation method of the colloidal silicon dioxide comprises the following steps:
the pH of the above silica raw material was adjusted to 3.0 with a 5wt% hydrochloric acid solution and water to obtain colloidal silica having a concentration of 19.9 wt%.
The colloidal silica obtained in comparative example 6 was tested to have a Zeta potential of-5.03 mV at a pH of 3.0.
Stability test, the colloidal silica was placed in an oven at 45 ℃ and observed to gel at 15 days.
Comparative example 7
The silica raw material in this comparative example 7 is the same as that in example 7.
The preparation method of the colloidal silicon dioxide comprises the following steps:
the pH of the above silica raw material was adjusted to 2.0 with a 5wt% hydrochloric acid solution and water to obtain colloidal silica having a concentration of 18.1 wt%.
The colloidal silica obtained in comparative example 7 was tested to have a Zeta potential of-1.68 mV at a pH of 2.0.
Stability test, the colloidal silica was placed in an oven at 45 ℃ and observed to gel at 12 days.
Comparative example 8
The silica raw material in this comparative example 8 is the same as that in example 8.
The preparation method of the colloidal silicon dioxide comprises the following steps:
the pH of the above silica raw material was adjusted to 4.5 with a 10wt% acetic acid solution and water to obtain colloidal silica having a concentration of 38.5 wt%.
The colloidal silica obtained in comparative example 8 was tested to have a Zeta potential of-14.80 mV at a pH of 4.5.
Stability test, the colloidal silica was placed in an oven at 45 ℃ and observed to gel at 18 days.
Comparative example 9
The silica raw material in this comparative example 9 was the same as that in example 9.
The preparation method of the colloidal silicon dioxide comprises the following steps:
the pH of the above silica raw material was adjusted to 4.5 with a 5wt% sulfuric acid solution and water to obtain colloidal silica having a concentration of 8.8 wt%.
The colloidal silica obtained in comparative example 9 was tested to have a Zeta potential of-10.03 mV at a pH of 4.5.
Stability test, the colloidal silica was placed in an oven at 45 ℃ and observed to gel at 17 days.
Comparative example 10
The silica raw material in this comparative example 10 was the same as that in example 1.
The preparation method of the modified colloidal silicon dioxide comprises the following steps:
under the stirring state, a silane coupling agent N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane (KH-791 for short) is directly added into the silicon dioxide raw material for reaction at the reaction temperature of 30 ℃ for 8h to obtain the modified colloidal silicon dioxide. The mass ratio of the silica to the silane coupling agent in the silica raw material is 0.3.
Flocs were found upon addition of the coupling agent.
Comparative example 11
The silica raw material in this comparative example 11 was the same as that in example 6.
The preparation method of the modified colloidal silicon dioxide comprises the following steps:
diluting a silane coupling agent gamma-aminopropyl triethoxysilane (KH-550 for short) with water to a concentration of 3wt% under stirring, and directly adding into the silica raw material for reaction at a reaction temperature of 80 ℃ for 8h to obtain the modified colloidal silica. The mass ratio of the silica to the silane coupling agent in the silica raw material is 0.3.
After the addition of the coupling agent, a precipitate was found to be obtained at the bottom.
Comparing examples 1 to 9 with comparative examples 10 to 11, it was found that examples 1 to 9 are all effective in suppressing the occurrence of floc, precipitate or gelation at the time of addition of the silane coupling agent or after the addition. In comparative examples 10 to 11, in which the silane coupling agent was not hydrolyzed under acidic conditions and reacted with colloidal silica to prepare modified colloidal silica, flocs and precipitates were generated during or after the addition of the coupling agent.
The properties of the modified colloidal silicas obtained in examples 1 to 9 and the colloidal silicas obtained in comparative examples 1 to 9 were compared and are shown in Table 1.
TABLE 1
As can be seen from table 1, the modified colloidal silica prepared in example 1 had a silica content of 16.2% as compared with the colloidal silica of comparative example 1; the pH value is 4.5, the Zeta potential is +23.46mV, the stability at 45 ℃ is greatly improved, the gelation time before modification is only 3 days, and the gelation time after modification is more than 60 days. This is also illustrated in examples 2, 3, 4, 5, 6, 7, 8, 9 in comparison with comparative examples 2, 3, 4, 5, 6, 7, 8, 9, respectively.
The polishing properties of the modified colloidal silica of example 1 and the colloidal silica of comparative example 1 were compared, and are shown in table 2.
The data of polishing rate and surface roughness of the polished wafer in table 2 were obtained by formulating the modified colloidal silica prepared in example 1 and the colloidal silica prepared in comparative example 1 described above into a polishing solution for polishing a silicon oxide dielectric layer.
The polishing solution preparation method comprises the following steps: the modified colloidal silica of example 1 and the colloidal silica of comparative example 1 were diluted with pure water as needed to concentrations of 15%, 10% and 5%, respectively, and then the pH of the solution was adjusted to 4.5 with a 5wt% sulfuric acid solution, and after stirring uniformly, 1kg was weighed, to obtain a polishing solution.
Polishing experiment: the silicon oxide dielectric layer used in the experiment is obtained by growing Tetraethoxysilane (TEOS) on a Si wafer by a Chemical Vapor Deposition (CVD) method, and the size of the silicon oxide dielectric layer is 4cm multiplied by 4cm. And adhering a silicon oxide dielectric layer with the thickness of 4cm multiplied by 4cm on a polishing head by a back film adsorption method for polishing. The polishing parameters were set as follows: polishing pressure was 4psi; the polishing pad rotating speed is 90rpm; the rotating speed of the polishing sheet is 90rpm; the flow rate of the polishing solution is 125ml/min; the polishing time was 1.5min. And after finishing each polishing, repairing the polishing pad for 5 minutes by using a 4-inch diamond repairing disc, ultrasonically cleaning the polished silicon oxide wafer in a cleaning solution for 10 minutes, and drying the silicon oxide wafer by using nitrogen. The surface roughness (Ra) of the silicon oxide wafer after polishing was observed by an atomic force microscope. The difference in thickness before and after polishing of the silicon oxide wafer was measured by a 13-point method with a film thickness meter, and the polishing rate was calculated, and the results are shown in table 2.
TABLE 2
As is clear from Table 2, in comparison with comparative example 1, the polishing rate was improved by 25% or more in the case of polishing with the modified colloidal silica of example 1 as a polishing liquid at the same silica concentration as in comparative example 1. Moreover, the polishing rate advantage of example 1 is 141nm/min at a low concentration of 5%, while that of comparative example 1 is only 37nm/min, which shows that the modified silicon dioxide has good polishing performance at a low concentration, and the cost of the polishing process can be reduced. In addition, after the modified colloidal silica and the unmodified colloidal silica polish the silicon oxide dielectric layer, the roughness of the surface of the wafer is not obviously different and is lower, which indicates that the modified colloidal silica has better surface quality while improving the polishing rate.
As can be seen from tables 1 and 2, the Zeta potential of the modified colloidal silica obtained by the preparation method of the present application is positive and 10 to 65mV when the pH value is 1.0 to 5.0. The modified colloidal silica obtained by the present invention has a greatly improved stability under acidic conditions, and exhibits an excellent effect of stably dispersing over a wide pH range, particularly under acidic conditions, for a long period of time. The polishing speed can be improved when the silicon oxide dielectric layer is polished under the acidic condition, the process cost is greatly reduced, and the polishing solution is very suitable for various polishing solutions with polishing requirements under the acidic condition.
Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A preparation method of modified colloidal silica is characterized by comprising the following steps:
and under an acidic condition, modifying the colloidal silica by adopting a hydrolyzed silane coupling agent to obtain the modified colloidal silica.
2. The method of claim 1, wherein the colloidal silica has a pH of 2.0 to 5.0;
and/or, the content of silicon dioxide in the colloidal silicon dioxide is 10-40 wt%;
and/or the particle size of the colloidal silicon dioxide is 30-100 nm;
and/or the colloidal silicon dioxide is obtained by exchanging a silicon dioxide raw material with cation exchange resin.
3. The method of claim 1, wherein the silane coupling agent is a silane coupling agent containing an amino group;
and/or the pH value of the acidic condition is 1.0-5.0;
and/or the temperature during modification is 20-100 ℃.
4. The method according to claim 1, wherein the mass ratio of silica to the silane coupling agent in the colloidal silica is 100: (0.2-10).
5. The method of claim 3, wherein the amino group-containing silane coupling agent is selected from one or more of primary aminosilanes, secondary aminosilanes, and tertiary aminosilanes.
6. The method of claim 1, wherein the hydrolyzed silane coupling agent is prepared by: an aqueous solution of the silane coupling agent is adjusted to be acidic with an acid, and then hydrolysis is performed.
7. The method of claim 6, wherein the acid is selected from one or more of nitric acid, sulfuric acid, hydrochloric acid, formic acid, acetic acid, and citric acid;
and/or the concentration of the aqueous solution of the silane coupling agent is 1-10 wt%;
and/or the hydrolysis time is 0.5-24 h.
8. The modified colloidal silica prepared by the preparation process according to any one of claims 1 to 7.
9. The modified colloidal silica of claim 8, wherein the modified colloidal silica has a silica content of not less than 5wt%;
and/or when the pH value of the modified colloidal silicon dioxide is 1.0-5.0, the Zeta potential is 10-65mV.
10. Use of the modified colloidal silica according to claim 8 or 9 as a polishing liquid in integrated circuits.
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