CN112680187A - Surface-modified silicon dioxide and abrasive composition containing same - Google Patents
Surface-modified silicon dioxide and abrasive composition containing same Download PDFInfo
- Publication number
- CN112680187A CN112680187A CN202110004108.8A CN202110004108A CN112680187A CN 112680187 A CN112680187 A CN 112680187A CN 202110004108 A CN202110004108 A CN 202110004108A CN 112680187 A CN112680187 A CN 112680187A
- Authority
- CN
- China
- Prior art keywords
- acid
- solvent
- silica
- abrasive composition
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention discloses surface-modified silicon dioxide and an abrasive composition containing the same. The invention provides surface modified silicon dioxide, which is characterized by being prepared by the following preparation method: in a solvent, reacting silicon dioxide with a silane coupling agent to obtain surface modified silicon dioxide; the silane coupling agent is octaaminophenyl-POSS and/or octachloropropyl-POSS. The surface modified silicon dioxide can greatly improve the grinding selectivity of polysilicon relative to silicon nitride, improve the grinding rate of Si-containing materials and obviously improve the grinding rate of ruthenium.
Description
Technical Field
The present invention relates to a surface-modified silica and an abrasive composition containing the same.
Background
In recent years, with the high Integration and high performance of LSI (Large Scale Integration), new microfabrication technology has been developed. Chemical Mechanical Polishing (CMP) is also one of the techniques frequently used in the LSI production process, particularly in the planarization of an interlayer insulating film, the formation of a metal plug (plug), and the formation of a damascene wiring in the multilayer wiring formation process. This technique is disclosed in, for example, patent document 1 (specification of U.S. patent No. 4944836).
In recent years, CMP is increasingly applied to each step in semiconductor manufacturing, and one embodiment thereof is applied to a gate formation step in transistor fabrication, for example.
In the fabrication of transistors, Si-containing materials such as polysilicon (polysilicon) and silicon nitride (silicon nitride) are sometimes polished, and it is required to control the polishing rate of each Si-containing material. For example, patent document 2 (jp 2010-041037 a) discloses the following polishing composition: the composition contains colloidal silica and an organic acid having a sulfonic acid group or a phosphonic acid group, and has a pH of 2.5 to 5. According to patent document 2, for example, when a Si-containing material different from silicon nitride, polysilicon, or the like is polished, by using the polishing composition, the polishing rate of a layer containing silicon nitride can be increased, and polishing of a layer containing a silicon-based compound such as polysilicon, modified polysilicon, silicon oxide, silicon carbide, and silicon carbide oxide can be selectively suppressed.
However, with the polishing composition described in patent document 2, the polishing rate of the Si-containing material cannot be sufficiently controlled, and therefore, further improvement of the polishing composition is demanded.
Disclosure of Invention
The present invention has been made to solve the problem that the conventional polishing composition cannot sufficiently control the polishing rate of a Si-containing material, and therefore, the present invention provides a surface-modified silica having a preferable polishing rate for a Si-containing material, and an abrasive composition containing the same.
The invention provides surface modified silicon dioxide, which is prepared by the following preparation method: in a solvent, reacting silicon dioxide with a silane coupling agent to obtain surface modified silicon dioxide; the silane coupling agent is octaaminophenyl-POSS (CAS: 518359-82-5) and/or octachloropropyl-POSS (CAS: 161678-38-2).
In the surface-modified silica, the solvent may be conventional in the art, and is preferably water and/or an organic solvent in the preparation method thereof.
In the surface-modified silica, in the preparation method thereof, the organic solvent may be conventional in the art, and is preferably one or more of an alcohol solvent, a ketone solvent, an ether solvent, an amide solvent, and a sulfoxide solvent, and more preferably an alcohol solvent.
In the surface-modified silica, the alcoholic solvent may be conventional in the art, and is preferably one or more of methanol, ethanol, n-propanol and isopropanol, and more preferably methanol.
In the surface-modified silica, the ketone solvent may be conventional in the art, and is preferably acetone and/or methyl ethyl ketone in the preparation method thereof.
In the surface-modified silica, the ether solvent may be conventional in the art, and is preferably one or more of diethyl ether, dioxane and tetrahydrofuran, in the preparation method thereof.
In the surface-modified silica, the amide-based solvent may be conventional in the art, and is preferably N, N-dimethylformamide, in the preparation method thereof.
In the surface-modified silica, the sulfoxide-based solvent may be conventional in the art, and is preferably dimethyl sulfoxide in the preparation method thereof.
In the surface-modified silica, in the method for producing the same, the silica is preferably colloidal silica.
In the surface-modified silica, in the production method thereof, the average primary particle diameter of the silica is preferably 35 nm. The value of the average primary particle diameter is calculated based on the specific surface area measured by the BET method.
In the surface-modified silica, in the production method thereof, the average secondary particle diameter of the silica is preferably 68 nm. The value of the average secondary particle diameter is calculated based on the specific surface area measured by a light scattering method using a laser beam.
In the surface-modified silica, in the preparation method thereof, when the solvent is water and an organic solvent, the silica and the water may be added in the form of an aqueous silica solution.
In the surface-modified silica, in the preparation method thereof, the mass concentration of the silica in the aqueous silica solution may be conventional in the art, for example, 19.5%, and the mass concentration refers to a ratio of the mass of the silica to the total mass of the aqueous silica solution.
In the surface-modified silica, in the preparation method thereof, when the solvent is water and an organic solvent, the silane coupling agent and the organic solvent may be added in the form of a mixed solution of the silane coupling agent and the organic solvent.
In the surface-modified silica, in the method for producing the same, preferably, a mixed solution of the silane coupling agent and the organic solvent is added to an aqueous solution of the silica to form a mixture.
In the surface-modified silica, in the production method thereof, the mixed solution is preferably added dropwise to an aqueous solution of the silica to form a mixture. The rate of the dropwise addition may be conventional in the art, for example 1 mL/min.
In the surface-modified silica, when the solvent is water and an organic solvent in the preparation method thereof, the water and the organic solvent are preferably miscible with each other.
In the surface-modified silica, in the preparation method thereof, the mass ratio of the silane coupling agent to the silica may be 1 (260 to 300), for example, 1: 267.
In the surface-modified silica, in the preparation method thereof, when the solvent is water and an organic solvent, the silane coupling agent and the organic solvent may be added in a form of a mixed solution of the silane coupling agent and the organic solvent, and the mass ratio of the silane coupling agent to the organic solvent may be 1 (60-80), for example, 1:68 or 1: 77.
In the surface-modified silica, the reaction temperature may be conventional in the art, for example, 25 ℃ in the preparation method thereof.
In the surface-modified silica, the reaction is preferably carried out under stirring in the preparation process thereof. The rotational speed of the stirring may be 600 rpm.
In the surface-modified silica, the post-treatment of the reaction in the preparation method thereof comprises the steps of: adjusting pH, standing, and concentrating.
In the surface-modified silica, the preparation method thereof, the pH adjustment may be performed by adding a pH adjuster in the post-treatment of the reaction. The pH adjusting agent is preferably an alkali, such as potassium hydroxide and/or sodium hydroxide.
In the surface-modified silica, in the preparation method thereof, in the post-treatment of the reaction, after a pH regulator is added, the pH value of the mixture is preferably 7.0 to 11.0, and more preferably 8.0 to 9.0.
In the surface-modified silica, in the preparation method thereof, after the pH of the mixture is adjusted in the post-treatment of the reaction, the mixture is preferably left to stand in an air bath at 40 ℃ for 8 hours.
In the surface-modified silica, in the preparation method thereof, after standing for 8 hours in the post-treatment of the reaction, preferably, the mixture is left to stand in an air bath at 60 ℃ for 12 hours.
In the surface-modified silica, in the method for producing the same, in certain preferred embodiments, the solvent is water and an organic solvent, and the silica and the water are added in the form of an aqueous silica solution; the silicon dioxide aqueous solution is colloidal silicon dioxide aqueous solution; the mass concentration of the silicon dioxide aqueous solution is 19.5%; the silane coupling agent and the organic solvent are added in the form of a mixed solution formed by the silane coupling agent and the organic solvent; the mass ratio of the silane coupling agent to the organic solvent is 1 (68-77); the mass ratio of the silane coupling agent to the silicon dioxide is 1 (267-300).
In the surface modified silicon dioxide, in the preparation method, potassium hydroxide is added to adjust the pH value to 8.0-9.0 in the post-treatment of the reaction; after the pH value is adjusted, standing the reacted mixture in an air bath at 40 ℃ for 8 hours; after standing for 8 hours, the mixture was left standing in an air bath at 60 ℃ for 12 hours.
The invention provides an abrasive composition, which comprises the following components in percentage by mass: 0.05-50% of the surface modified silicon dioxide, a pH regulator and a dispersion medium, wherein the pH value of the abrasive composition is 0.5-12.
In the abrasive composition, the abrasive in the abrasive composition is preferably a CMP abrasive.
In the abrasive composition, the sum of the mass fractions of 0.05% to 50% of the surface-modified silica, the pH adjuster, and the dispersion medium may be 100%.
In the abrasive composition, the object to be ground by the abrasive may be an object to be ground including a layer, and the layer may be a Si-containing material and/or a noble metal-containing layer.
In the abrasive composition, the Si-containing material may include one or more of single crystal silicon, polycrystalline silicon, silicon oxide, and silicon nitride, preferably includes polycrystalline silicon or silicon nitride, more preferably includes silicon nitride, and further preferably includes polycrystalline silicon and silicon nitride.
In the abrasive composition, the noble metal may be one or more of gold (Au), silver (Ag), platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru), iridium (Ir), and osmium (Os), preferably ruthenium, for example: ruthenium monomer, ruthenium alloy, and ruthenium compound.
In the abrasive composition, the abrasive composition can further comprise 0.01-20% of an oxidizing agent; the mass fraction of the oxidizing agent is preferably 0.1% to 10%, more preferably 0.3% to 4%, for example 0.34%.
In the abrasive composition, the sum of the mass fractions of 0.05% to 50% of the surface-modified silica, the pH adjuster, the oxidizing agent, and the dispersion medium may be 100%.
In the abrasive composition, the mass fraction of the surface-modified silica is preferably 0.1% to 25%, more preferably 0.5% to 20%, for example 10%.
In the abrasive composition, the pH value of the abrasive composition is preferably 1 to 11.5, more preferably 2 to 11, such as 3 or 10.
In the abrasive composition, the dispersion medium may be an organic solvent or water, and is preferably water. The water may be pure water, ultrapure water or distilled water, preferably ultrapure water.
In the abrasive composition, the pH adjusting agent may be conventional in the art, such as an acid or a base, and the acid may be an inorganic acid and/or an organic acid, preferably an inorganic acid; the base may be one or more of an amine, a quaternary ammonium salt and a metal hydroxide, preferably a metal hydroxide.
In the abrasive composition, the inorganic acid may be conventional in the art, and is preferably one or more of sulfuric acid, nitric acid, boric acid, carbonic acid, hypophosphorous acid, phosphorous acid, and phosphoric acid, more preferably sulfuric acid and/or nitric acid, and further preferably nitric acid.
In the abrasive composition, the organic acid may be conventional in the art, and is preferably a carboxylic acid and/or an organic sulfuric acid.
In the abrasive composition, the carboxylic acid may be conventional in the art, and is preferably one or more of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexanoic acid, 3-dimethylbutyric acid, 2-ethylbutyric acid, 4-methylpentanoic acid, n-heptanoic acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycolic acid, salicylic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, malic acid, tartaric acid, citric acid, and lactic acid.
In the abrasive composition, the organic sulfuric acid may be conventional in the art, and is preferably one or more of methanesulfonic acid, ethanesulfonic acid, and isethionic acid.
In the abrasive composition, the amine may be conventional in the art, and is preferably one or more of ammonia, ethylenediamine, and piperazine.
In the abrasive composition, the quaternary ammonium salt may be conventional in the art, and is preferably tetramethylammonium and/or tetraethylammonium.
In the abrasive composition, the metal hydroxide may be conventional in the art, and is preferably potassium hydroxide and/or sodium hydroxide, more preferably potassium hydroxide.
In the abrasive composition, the pH adjuster is used in an amount to bring the abrasive composition to the pH.
In the abrasive composition, the oxidizing agent may be conventional in the art, and is preferably a peroxide and/or a perhalogenic acid, more preferably a peroxide.
In the abrasive composition, the peroxide may be conventional in the art, and is preferably one or more of hydrogen peroxide, peracetic acid, percarbonate, persulfate, and urea peroxide, more preferably persulfate and/or hydrogen peroxide, and further preferably hydrogen peroxide.
In the abrasive composition, the persulfate salt may be conventional in the art, and is preferably one or more of sodium persulfate, potassium persulfate, and ammonium persulfate.
In the abrasive composition, the perhalogenic acid may be conventional in the art, and is preferably perchloric acid and/or periodic acid.
In the abrasive composition, the abrasive composition may further comprise a preservative, and the preservative may be one or more of isothiazoline preservatives, parabens and phenoxyethanol. The isothiazoline preservative can be 2-methyl-4-isothiazoline-3-ketone and/or 5-chloro-2-methyl-4-isothiazoline-3-ketone.
In the abrasive composition, the abrasive composition may further include one or more of a mildewcide, a complexing agent, a metal anticorrosive agent, a reducing agent, and a surfactant.
In the present invention, the abrasive composition may be any one of the following:
scheme 1: the abrasive material composition comprises the following components in percentage by mass: 10% of the surface-modified silica as described above, nitric acid and ultrapure water, the abrasive composition having a pH of 3;
scheme 2: the abrasive material composition comprises the following components in percentage by mass: 10% of the surface-modified silica as described above, nitric acid as a pH adjusting agent, 0.34% of hydrogen peroxide, and ultrapure water, the abrasive composition having a pH of 3;
scheme 3: the abrasive material composition comprises the following components in percentage by mass: 10% of the surface-modified silica as described above, a pH adjuster potassium hydroxide, and ultrapure water, the abrasive composition having a pH of 10;
scheme 4: the abrasive material composition comprises the following components in percentage by mass: 10% of the surface-modified silica described above, a pH adjuster of potassium hydroxide, 0.34% of hydrogen peroxide, and ultrapure water, the abrasive composition having a pH of 10.
The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: the surface modified silicon dioxide can greatly improve the grinding selectivity of polysilicon relative to silicon nitride, improve the grinding rate of Si-containing materials and obviously improve the grinding rate of ruthenium.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1 Synthesis of silica D
195g of colloidal silica (having an average primary particle size of 35nm and an average secondary particle size of 68nm) was weighed and dissolved in a certain amount of water to form an aqueous colloidal silica solution having a mass concentration of 19.5%. 0.63mmol (0.73g) of octaaminophenyl-POSS (CAS: 518359-82-5) was separately weighed out and dissolved in 50g of methanol.
The colloidal silica aqueous solution was stirred at 25 ℃ in an air atmosphere at a rotation speed of 600rpm of a stirring blade, and a methanol solution of the silane coupling agent was added dropwise at a rate of 1 mL/min. After dropwise adding, adjusting the pH value with KOH to make the pH value of the solution be 8.0-9.0.
After the pH adjustment, the solution was allowed to stand in an air bath at 40 ℃ for 8 hours and then in an air bath at 60 ℃ for 12 hours. Then, water and methanol were removed by a rotary evaporator to obtain silica D.
Comparative example 1 Synthesis of silica E
195g of colloidal silica (having an average primary particle size of 35nm and an average secondary particle size of 68nm) was weighed and dissolved in a certain amount of aqueous solution to form an aqueous colloidal silica solution having a mass concentration of 19.5%. Separately, 5mmol (1.07g) of aminophenyltrimethoxysilane was weighed out and dissolved in 50g of methanol.
The colloidal silica aqueous solution was stirred at 25 ℃ in an air atmosphere at a rotation speed of 600rpm of a stirring blade, and a methanol solution of the silane coupling agent was added dropwise at a rate of 1 mL/min. After dropwise adding, adjusting the pH value by using a pH adjusting agent (KOH) to enable the pH value of the solution to be 8.0-9.0.
After the pH adjustment, the solution was allowed to stand in an air bath at 40 ℃ for 8 hours and then in an air bath at 60 ℃ for 12 hours. Then, water and methanol were removed by a rotary evaporator to obtain silica E.
Example 2 Synthesis of silica F
195g of colloidal silica (having an average primary particle size of 35nm and an average secondary particle size of 68nm) was weighed and dissolved in a certain amount of aqueous solution to form an aqueous colloidal silica solution having a mass concentration of 19.5%. 0.63mmol (0.65g) of octachloropropyl-POSS (CAS: 161678-38-2) was separately weighed out and dissolved in 50g of methanol.
The colloidal silica aqueous solution was stirred at 25 ℃ in an air atmosphere at a rotation speed of 600rpm of a stirring blade, and a methanol solution of the silane coupling agent was added dropwise at a rate of 1 mL/min. After dropwise adding, adjusting the pH value by using a pH adjusting agent (KOH) to enable the pH value of the solution to be 8.0-9.0.
After the pH adjustment, the solution was allowed to stand in an air bath at 40 ℃ for 8 hours and then in an air bath at 60 ℃ for 12 hours. Then, water and methanol were removed by a rotary evaporator to obtain silica F.
Comparative example 2 Synthesis of silica G
195g of colloidal silica (having an average primary particle size of 35nm and an average secondary particle size of 68nm) was weighed and dissolved in a certain amount of aqueous solution to form an aqueous colloidal silica solution having a mass concentration of 19.5%. Separately, 5mmol (0.99g) of chloropropyltrimethoxysilane was weighed out and dissolved in 50g of methanol.
The colloidal silica aqueous solution was stirred at 25 ℃ in an air atmosphere at a rotation speed of 600rpm of a stirring blade, and a methanol solution of the silane coupling agent was added dropwise at a rate of 1 mL/min. After dropwise adding, adjusting the pH value by using a pH adjusting agent (KOH) to enable the pH value of the solution to be 8.0-9.0.
After the pH adjustment, the solution was allowed to stand in an air bath at 40 ℃ for 8 hours and then in an air bath at 60 ℃ for 12 hours. Then, water and methanol were removed by a rotary evaporator to obtain silica G.
Effect examples evaluation of polishing Properties
The surface-modified silicas prepared in examples 1 and 2 and comparative examples 1 and 2, a pH adjuster, and an oxidizing agent were mixed in ultrapure water according to the composition shown in table 1 below, thereby preparing CMP abrasive compositions (mixing temperature: about 25 ℃, mixing time: about 10 minutes). The pH of the CMP abrasive composition was confirmed using a pH meter.
Using the obtained CMP abrasive composition, the polishing rate when the object to be polished was polished under the following polishing conditions was measured.
The polishing rate column in table 1 shows the results of measuring the polishing rate of silicon nitride (SiN), polysilicon (Poly-Si), or ruthenium (Ru).
Grinding conditions are as follows:
grinding machine: 200mm single side CMP grinder;
cushion: making a polyurethane cushion;
pressure: 2.5psi (17.2 KPa);
plate rotation speed: 60 rpm;
rotating speed of the loader: 40 rpm;
flow rate of CMP abrasive composition: 100 mL/min;
grinding time: for 1 minute.
The polishing rate was calculated by the following formula:
the silicon nitride and the polysilicon were evaluated by determining the film thickness using an optical interference film thickness measuring apparatus and dividing the difference by the polishing time. Ruthenium was evaluated by determining the film thickness from the sheet resistance measurement by the dc 4 probe method and dividing the difference by the polishing time.
The results of the measurement of the polishing rate are shown in table 1 below.
TABLE 1 results of determination of polishing Rate of CMP abrasive composition
From the results of the polishing rates in table 1 above, it can be seen that: when effect examples 1 and 3 are compared with comparative effect examples 1 and 3, the polishing rate for silicon nitride is suppressed in effect examples 1 and 3, and in particular, effect examples 1 and 3 show that the polishing selectivity of polysilicon with respect to silicon nitride is high. Likewise, when effect examples 5 and 7 are compared with comparative effect examples 5 and 7, the polishing selectivity of polysilicon to silicon nitride is high in effect examples 5 and 7. Therefore, it is shown that the CMP abrasive composition using silica D and silica F as abrasive particles can significantly improve the polishing selectivity of polysilicon to silicon nitride in the Si-containing material and increase the polishing rate of the Si-containing material, compared to the CMP abrasive composition using silica E and silica G as abrasive particles.
Further, when effect examples 2 and 4 are compared with comparative effect examples 2 and 4, the polishing rate of ruthenium in effect examples 2 and 4 is increased. Likewise, when effect examples 6 and 8 are compared with comparative effect examples 6 and 8, the polishing rate of ruthenium in effect examples 6 and 8 is increased. Thus, it was shown that the CMP abrasive composition in which silica D and silica F were used as abrasive grains can significantly increase the polishing rate for ruthenium, compared to the CMP abrasive composition in which silica E and silica G were used as abrasive grains.
Claims (10)
1. Surface-modified silica, characterized in that it is prepared by the following preparation method: in a solvent, reacting silicon dioxide with a silane coupling agent to obtain surface modified silicon dioxide; the silane coupling agent is octaaminophenyl-POSS and/or octachloropropyl-POSS.
2. The surface-modified silica according to claim 1, wherein the solvent in the process for preparing the surface-modified silica is water and/or an organic solvent;
and/or, the silica is colloidal silica;
and/or the silica has an average primary particle diameter of 35nm, the value of the average primary particle diameter being calculated based on a specific surface area measured by a BET method;
and/or the silica has an average secondary particle diameter of 68nm, the value of the average secondary particle diameter being calculated based on a specific surface area measured by a light scattering method using a laser beam;
and/or the mass ratio of the silane coupling agent to the silicon dioxide is 1 (260-300), such as 1: 267;
and/or the temperature of the reaction is 25 ℃;
and/or the reaction is carried out under stirring, wherein the stirring speed is 600 rpm;
and/or the post-treatment of the reaction comprises the following steps: adjusting pH, standing, and concentrating.
3. The surface-modified silica according to claim 2, wherein the surface-modified silica is prepared by a method in which, when the solvent is water and an organic solvent, the water and the organic solvent are miscible with each other; said silica and said water are added in the form of an aqueous silica solution; the silane coupling agent and the organic solvent are added in the form of a mixed solution formed by the silane coupling agent and the organic solvent;
and/or, when the solvent is water and an organic solvent, the mass ratio of the silane coupling agent to the organic solvent can be 1 (60-80), such as 1:68 or 1: 77;
and/or, in the preparation method of the surface modified silicon dioxide, when the solvent comprises an organic solvent, the organic solvent is one or more of an alcohol solvent, a ketone solvent, an ether solvent, an amide solvent and a sulfoxide solvent, and preferably is an alcohol solvent; the alcohol solvent is preferably one or more of methanol, ethanol, n-propanol and isopropanol, and is more preferably methanol;
the ketone solvent is preferably acetone and/or methyl ethyl ketone;
the ether solvent is preferably one or more of diethyl ether, dioxane and tetrahydrofuran;
the amide solvent is preferably N, N-dimethylformamide;
the sulfoxide-based solvent is preferably dimethyl sulfoxide.
4. The surface-modified silica according to claim 3, wherein in the method for producing the surface-modified silica, when the solvent is water or an organic solvent, the silica has a mass concentration of 19.5% in the aqueous silica solution, the mass concentration being a ratio of the mass of the silica to the total mass of the aqueous silica solution;
and/or when the solvent is water and an organic solvent, adding a mixed solution formed by the silane coupling agent and the organic solvent into the aqueous solution of the silicon dioxide to form a mixture; preferably, the mixed solution is dropwise added into the aqueous solution of the silicon dioxide to form a mixture; the dropping rate is preferably 1 mL/min.
5. The surface-modified silica according to claim 1, wherein the surface-modified silica is produced by a method in which the solvent is water and an organic solvent, and the silica and the water are added in the form of an aqueous silica solution;
the silicon dioxide aqueous solution is colloidal silicon dioxide aqueous solution;
the mass concentration of the silicon dioxide aqueous solution is 19.5%;
the silane coupling agent and the organic solvent are added in the form of a mixed solution formed by the silane coupling agent and the organic solvent;
the mass ratio of the silane coupling agent to the organic solvent is 1 (68-77);
the mass ratio of the silane coupling agent to the silicon dioxide is 1 (267-300).
6. The surface-modified silica according to claim 2, wherein in the preparation method of the surface-modified silica, potassium hydroxide is added to adjust the pH to 8.0 to 9.0 in the post-treatment of the reaction; after the pH value is adjusted, standing the reacted mixture in an air bath at 40 ℃ for 8 hours; after standing for 8 hours, the mixture was left standing in an air bath at 60 ℃ for 12 hours.
7. An abrasive composition is characterized by comprising the following components in percentage by mass: 0.05% to 50% of the surface-modified silica according to any one of claims 1 to 6, a pH adjusting agent and a dispersion medium, wherein the abrasive composition has a pH of 0.5 to 12.
8. The abrasive composition according to claim 7, wherein the abrasive in the abrasive composition is a CMP abrasive;
and/or the grinding object of the grinding material is a grinding object containing a layer, and the layer can be a Si-containing material and/or a layer containing precious metal;
and/or, the abrasive composition further comprises 0.01-20% of an oxidizing agent; the mass fraction of the oxidizing agent is preferably 0.1% to 10%, more preferably 0.3% to 4%, for example 0.34%;
and/or the surface-modified silica is present in a mass fraction of 0.1% to 25%, preferably 0.5% to 20%, for example 10%;
and/or the abrasive composition has a pH of from 1 to 11.5, preferably from 2 to 11, for example 3 or 10;
and/or the dispersion medium is an organic solvent or water, preferably water; the water can be pure water, ultrapure water or distilled water, and is preferably ultrapure water;
and/or the pH regulator is acid or alkali, and the acid can be inorganic acid and/or organic acid, preferably inorganic acid; the base may be one or more of an amine, a quaternary ammonium salt and a metal hydroxide, preferably a metal hydroxide;
and/or, the abrasive composition further comprises a preservative, which may be one or more of isothiazoline preservatives, parabens, and phenoxyethanol; the isothiazoline preservative can be 2-methyl-4-isothiazoline-3-ketone and/or 5-chloro-2-methyl-4-isothiazoline-3-ketone;
and/or, the abrasive composition further comprises one or more of a mildew inhibitor, a complexing agent, a metal corrosion inhibitor, a reducing agent, and a surfactant.
9. The abrasive composition according to claim 8, wherein when the layer is a layer of a Si-containing material, the Si-containing material comprises one or more of single crystal silicon, polycrystalline silicon, silicon oxide and silicon nitride, preferably comprises polycrystalline silicon or silicon nitride, more preferably comprises silicon nitride, further preferably comprises polycrystalline silicon and silicon nitride;
and/or, when the layer is a noble metal-containing layer, the noble metal is one or more of gold, silver, platinum, palladium, rhodium, ruthenium, iridium, and osmium, preferably ruthenium, for example: ruthenium monomers, ruthenium alloys, and ruthenium compounds;
and/or, when the pH adjuster is an inorganic acid, the inorganic acid is one or more of sulfuric acid, nitric acid, boric acid, carbonic acid, hypophosphorous acid, phosphorous acid, and phosphoric acid, preferably sulfuric acid and/or nitric acid, more preferably nitric acid;
and/or, when the pH regulator is an organic acid, the organic acid is a carboxylic acid and/or an organic sulfuric acid; the carboxylic acid is preferably one or more of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexanoic acid, 3-dimethylbutyric acid, 2-ethylbutyric acid, 4-methylpentanoic acid, n-heptanoic acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycolic acid, salicylic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, malic acid, tartaric acid, citric acid, and lactic acid; the organic sulfuric acid is preferably one or more of methanesulfonic acid, ethanesulfonic acid and isethionic acid;
and/or, when the pH adjuster is an amine, the amine is one or more of ammonia, ethylenediamine, and piperazine;
and/or, when the pH regulator is a quaternary ammonium salt, the quaternary ammonium salt is tetramethylammonium and/or tetraethylammonium;
and/or, when the pH regulator is a metal hydroxide, the metal hydroxide is potassium hydroxide and/or sodium hydroxide, preferably potassium hydroxide;
and/or, when the abrasive composition further comprises an oxidizing agent, the oxidizing agent is a peroxide and/or a perhalogenated acid, preferably a peroxide; the peroxide is preferably one or more of hydrogen peroxide, peracetic acid, percarbonate, persulfate and urea peroxide, more preferably persulfate and/or hydrogen peroxide, and further preferably hydrogen peroxide; the persulfate is preferably one or more of sodium persulfate, potassium persulfate and ammonium persulfate; the perhalogenic acid is preferably perchloric acid and/or periodic acid.
10. The abrasive composition according to claim 7, wherein the abrasive composition is any one of the following:
scheme 1: the abrasive material composition comprises the following components in percentage by mass: 10% of the surface-modified silica according to any one of claims 1 to 6, nitric acid and ultrapure water, the abrasive composition having a pH of 3;
scheme 2: the abrasive material composition comprises the following components in percentage by mass: 10% of the surface-modified silica according to any one of claims 1 to 6, nitric acid as a pH adjusting agent, 0.34% hydrogen peroxide, and ultrapure water, the abrasive composition having a pH of 3;
scheme 3: the abrasive material composition comprises the following components in percentage by mass: 10% of the surface-modified silica according to any one of claims 1 to 6, a pH adjuster potassium hydroxide, and ultrapure water, the abrasive composition having a pH of 10;
scheme 4: the abrasive material composition comprises the following components in percentage by mass: 10% of the surface-modified silica according to any one of claims 1 to 6, potassium hydroxide as a pH adjusting agent, 0.34% of hydrogen peroxide, and ultrapure water, the abrasive composition having a pH of 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110004108.8A CN112680187A (en) | 2021-01-04 | 2021-01-04 | Surface-modified silicon dioxide and abrasive composition containing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110004108.8A CN112680187A (en) | 2021-01-04 | 2021-01-04 | Surface-modified silicon dioxide and abrasive composition containing same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112680187A true CN112680187A (en) | 2021-04-20 |
Family
ID=75457090
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110004108.8A Pending CN112680187A (en) | 2021-01-04 | 2021-01-04 | Surface-modified silicon dioxide and abrasive composition containing same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112680187A (en) |
Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61159474A (en) * | 1984-12-29 | 1986-07-19 | Toshiba Silicone Co Ltd | Lustering agent composition |
| CN1367809A (en) * | 1999-07-07 | 2002-09-04 | 卡伯特微电子公司 | CMP composition containing silane modified abrasive particles |
| WO2011154508A1 (en) * | 2010-06-09 | 2011-12-15 | L'oreal | Cosmetic composition comprising a polymer and a 4-carboxy-2-pyrrolidinone derivative, cosmetic treatment process and compound |
| US9068110B2 (en) * | 2012-01-09 | 2015-06-30 | SK Hynix Inc. | Polishing slurry and chemical mechanical planarization method using the same |
| CN104927403A (en) * | 2015-06-18 | 2015-09-23 | 合肥工业大学 | Preparation method of high-performance lubricating oil additive |
| CN105555901A (en) * | 2013-09-20 | 2016-05-04 | 福吉米株式会社 | Polishing composition |
| CN106256801A (en) * | 2015-06-18 | 2016-12-28 | 捷恩智株式会社 | Spherical silicon oxide carbide bulk material and manufacture method, lubricant, grinding agent |
| CN106795422A (en) * | 2014-10-09 | 2017-05-31 | 信越化学工业株式会社 | The Ginding process of CMP abrasive and its manufacture method and substrate |
| CN107207268A (en) * | 2015-01-19 | 2017-09-26 | 福吉米株式会社 | Modified colloidal sifica and its manufacture method and use its grinding agent |
| CN107207945A (en) * | 2015-01-19 | 2017-09-26 | 福吉米株式会社 | Composition for polishing |
| CN107533967A (en) * | 2015-03-30 | 2018-01-02 | 福吉米株式会社 | Composition for polishing |
| CN108774413A (en) * | 2018-04-13 | 2018-11-09 | 太仓运通新材料科技有限公司 | Nano silicon dioxide dispersion and preparation method thereof |
| CN109021502A (en) * | 2018-07-06 | 2018-12-18 | 南雄市科鼎化工有限公司 | A kind of outer layer plug socket resin and preparation method thereof |
| CN109134904A (en) * | 2018-08-20 | 2019-01-04 | 蚌埠市维光塑胶制品有限公司 | A method of anti-droplet, which is prepared, with nano silica-cage-type silsesquioxane prevents adhesion plastic film |
| US20190185708A1 (en) * | 2017-12-19 | 2019-06-20 | Honeywell International Inc. | Crack-resistant silicon-based planarizing compositions, methods and films |
| CN111004506A (en) * | 2019-12-23 | 2020-04-14 | 哈尔滨工业大学 | Preparation method of modified cyanate ester resin with ultraviolet irradiation resistance |
| CN111748284A (en) * | 2019-03-27 | 2020-10-09 | 福吉米株式会社 | Polishing composition |
-
2021
- 2021-01-04 CN CN202110004108.8A patent/CN112680187A/en active Pending
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61159474A (en) * | 1984-12-29 | 1986-07-19 | Toshiba Silicone Co Ltd | Lustering agent composition |
| CN1367809A (en) * | 1999-07-07 | 2002-09-04 | 卡伯特微电子公司 | CMP composition containing silane modified abrasive particles |
| WO2011154508A1 (en) * | 2010-06-09 | 2011-12-15 | L'oreal | Cosmetic composition comprising a polymer and a 4-carboxy-2-pyrrolidinone derivative, cosmetic treatment process and compound |
| US9068110B2 (en) * | 2012-01-09 | 2015-06-30 | SK Hynix Inc. | Polishing slurry and chemical mechanical planarization method using the same |
| CN105555901A (en) * | 2013-09-20 | 2016-05-04 | 福吉米株式会社 | Polishing composition |
| CN106795422A (en) * | 2014-10-09 | 2017-05-31 | 信越化学工业株式会社 | The Ginding process of CMP abrasive and its manufacture method and substrate |
| CN107207945A (en) * | 2015-01-19 | 2017-09-26 | 福吉米株式会社 | Composition for polishing |
| CN107207268A (en) * | 2015-01-19 | 2017-09-26 | 福吉米株式会社 | Modified colloidal sifica and its manufacture method and use its grinding agent |
| CN107533967A (en) * | 2015-03-30 | 2018-01-02 | 福吉米株式会社 | Composition for polishing |
| CN104927403A (en) * | 2015-06-18 | 2015-09-23 | 合肥工业大学 | Preparation method of high-performance lubricating oil additive |
| CN106256801A (en) * | 2015-06-18 | 2016-12-28 | 捷恩智株式会社 | Spherical silicon oxide carbide bulk material and manufacture method, lubricant, grinding agent |
| US20190185708A1 (en) * | 2017-12-19 | 2019-06-20 | Honeywell International Inc. | Crack-resistant silicon-based planarizing compositions, methods and films |
| CN108774413A (en) * | 2018-04-13 | 2018-11-09 | 太仓运通新材料科技有限公司 | Nano silicon dioxide dispersion and preparation method thereof |
| CN109021502A (en) * | 2018-07-06 | 2018-12-18 | 南雄市科鼎化工有限公司 | A kind of outer layer plug socket resin and preparation method thereof |
| CN109134904A (en) * | 2018-08-20 | 2019-01-04 | 蚌埠市维光塑胶制品有限公司 | A method of anti-droplet, which is prepared, with nano silica-cage-type silsesquioxane prevents adhesion plastic film |
| CN111748284A (en) * | 2019-03-27 | 2020-10-09 | 福吉米株式会社 | Polishing composition |
| CN111004506A (en) * | 2019-12-23 | 2020-04-14 | 哈尔滨工业大学 | Preparation method of modified cyanate ester resin with ultraviolet irradiation resistance |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6415439B2 (en) | Polishing composition | |
| TWI814030B (en) | Polishing composition, polishing method, and manufacturing method of substrate | |
| TW200914591A (en) | CMP slurry for polishing silicon film and polishing method | |
| TW201831642A (en) | Polishing composition | |
| JP2003059877A (en) | Polishing composition and polishing method using the same | |
| JP7152168B2 (en) | Polishing composition | |
| CN112680187A (en) | Surface-modified silicon dioxide and abrasive composition containing same | |
| CN112680186A (en) | Surface-modified silicon dioxide and preparation method of abrasive composition containing same | |
| US20210079264A1 (en) | Polishing composition, method for producing polishing composition, polishing method, and method for producing semiconductor substrate | |
| JP7409918B2 (en) | Polishing composition, method for producing polishing composition, polishing method, and method for producing semiconductor substrate | |
| CN112680185A (en) | Application of surface modified silicon dioxide as abrasive particles | |
| US20220306900A1 (en) | Polishing composition, polishing method and method for producing semiconductor substrate | |
| WO2005093802A1 (en) | Composition for polishing semiconductor | |
| TWI734803B (en) | Manufacturing method of polishing composition and polishing method | |
| JPWO2017057155A1 (en) | Polishing composition | |
| US11718768B2 (en) | Polishing composition, polishing method, and method of producing semiconductor substrate | |
| JP7261630B2 (en) | Polishing composition, method for producing polishing composition, polishing method, and method for producing semiconductor substrate | |
| JP2023042685A (en) | Polishing composition, polishing method, and manufacturing method for semiconductor substrate | |
| US11814294B2 (en) | Method of producing anionically modified colloidal silica | |
| KR20220133085A (en) | Polishing composition, polishing method, and manufacturing method of semiconductor substrate | |
| JP2022047860A (en) | Polishing composition, polishing method, and manufacturing method of semiconductor substrate | |
| JP2023050727A (en) | Polishing composition, polishing method, and method for manufacturing semiconductor substrate | |
| JP2020122144A (en) | Shallow trench isolation (sti) chemical mechanical planarization (cmp) polishing with tunable silicon oxide and silicon nitride removal rates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210420 |