CN112010318B - Preparation method of nano water-based silica sol for semiconductor polishing - Google Patents
Preparation method of nano water-based silica sol for semiconductor polishing Download PDFInfo
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Abstract
The invention provides a preparation method of nano aqueous silica sol for semiconductor polishing. In a dust-free laboratory, adding an analytically pure catalyst and high-purity water into the analytically pure mixed alcohol solvent, and uniformly stirring to prepare a solution A; adding analytically pure organic silicon source into the solution A according to the amount on time, and controlling the adding amount of the silicon source to gradually decrease along with the reaction time; stirring and reacting for 5-15 h at 25-45 ℃, adding high-purity water after the reaction is finished, and carrying out evaporation concentration to obtain the high-purity nano water-based silica sol. Controlling the growth of the silica sol in the range of target grain diameter +/-5 nm by controlling the addition amount of the catalyst and the proportion of the mixed alcohol; by controlling the addition of the organic silicon source to gradually decrease, the silica sol particles uniformly and stably grow, and the obtained aqueous silica sol has stable performance. According to the requirements of the chemical mechanical polishing solution for semiconductors, the polishing solution can be adjusted to be acidic or alkaline, specifically, the acidity is 2-4, the alkalinity is 8-11, and after the pH is adjusted, the stability of the silica sol cannot be influenced.
Description
Technical Field
The invention relates to a nano water-based silica sol for semiconductor polishing and a preparation method thereof.
Background
The nano aqueous silica sol material is an important component of the semiconductor polishing solution. The semiconductor polishing solution requires that the polishing material has no organic matter and no metal impurity ions, and the particles are uniformly dispersed. The particle size, particle size distribution, concentration, ph value and impurity content of silica directly affect the balance between the removal rate and the surface roughness or waviness of the surface of the polished material, thereby affecting the polishing quality of the surface of the material.
Semiconductor chemical mechanical polishing is a mechanical polishing process mainly based on chemical reaction, and in order to obtain good polished wafer quality, a chemical corrosion effect and a mechanical grinding effect in the polishing process must be balanced. Therefore, the polishing solution not only needs the nano-aqueous silica sol as an abrasive to perform mechanical grinding, but also needs to be added with a pH regulator, an oxidant, a catalyst and the like to perform chemical reaction with silicon atoms on the surface of the semiconductor. Therefore, the added nano-aqueous silica sol raw material is required to be stable under acidic or alkaline conditions.
A series of factors that affect the stability of silica sols include pH, particle size, electrolyte, dispersant, etc. Silica sols with very low electrolyte concentrations are relatively stable and do not gel for months or even years. In order to prepare a more stable silica sol, the electrolyte content of the silica sol needs to be reduced to a certain value. The particle size is another important factor influencing the stability of the silica sol, and the more uniform the particle size and narrower the distribution range, the better the stability of the silica sol, the particle size is within a certain range. The high molecular organic dispersant can generate repulsive force between silica particles to prevent the particles from aggregating. However, with the addition of the dispersant, interaction between the silica particles and the processing surface occurs to form surface active molecules, resulting in a decrease in friction and a decrease in polishing efficiency.
Therefore, the preparation of the aqueous nano silica sol material which has no metal impurity ions, no organic matter, low electrolyte content, uniform particle dispersion and stable existence under acidic or alkaline conditions is the best choice as the abrasive of the semiconductor chemical mechanical polishing solution.
CN103030151A relates to a neutral silica sol with large particle size, high concentration and high purity, a preparation method and application thereof, but the silica sol cannot be used as a good choice for a semiconductor polishing material because a polymer dispersant is added in the preparation process. CN102390838A relates to a preparation method of non-spherical silica sol, but because ethyl orthosilicate (silicon source) added in the preparation process is too little, the content of the obtained silica sol is too low, the silica sol is not suitable for industrial production, and alcohol solvent in the silica sol product cannot be completely removed, so that the alcohol solvent cannot be directly used for polishing semiconductors.
Disclosure of Invention
The invention aims to provide a preparation method of a nano aqueous silica sol material for semiconductor polishing, the silica sol prepared by the method has controllable particle size, narrow particle size distribution, no metal impurity ions and no organic matters, can stably exist under acidic or alkaline conditions, has simple preparation process, and can be used for chemical mechanical polishing of semiconductor materials.
The preparation method of the water-based silicon dioxide material for polishing the semiconductor has the following specific technical scheme:
(1) in a dust-free laboratory, adding an analytically pure catalyst and high-purity water into an analytically pure mixed alcohol solvent, uniformly stirring, and preparing a solution A;
(2) adding analytically pure organic silicon source into the solution A according to the amount on time, and controlling the adding amount of the silicon source to gradually decrease along with the reaction time;
(3) stirring and reacting at 25-45 ℃, adding a certain mass of high-purity water after the reaction is finished, evaporating and concentrating, and removing the alcohol solvent to obtain the high-purity aqueous nano silica sol.
The grade of the dust-free laboratory is one hundred thousand.
The alcohol solvent is a mixture of two of methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol, the proportion of mixed alcohol is 1: 10-1: 0.1, and the mass fraction of the mixed alcohol in a reaction system is 60-90 wt%.
The catalyst is one or a mixture of two of ammonia water, monoethanolamine, triethanolamine, tetramethylammonium hydroxide and tetraethylammonium hydroxide, preferably the ammonia water, and the mass fraction of the ammonia water in the reaction system is 1-8 wt%.
The mass fraction of the water in the reaction system is 2-8 wt%. The water is high-purity water, namely water with the conductivity of less than 0.1us/cm, the pH value of 6.8-7.0 and the capability of removing other impurities and bacteria at the temperature of 25 ℃.
The organic silicon source is one of tetraethoxysilane and methyl orthosilicate, preferably tetraethoxysilane, the content of silicon dioxide is more than 28%, the mass fraction of the silicon dioxide in a reaction system is 5-25 wt%, the adding times are 3-5 times, the adding amount of the silicon dioxide is 1-5 wt% each time, the adding amount gradually decreases along with the reaction time, the decreasing amount of each time is 0.10-0.75 wt%, and the reaction time is 2-5 hours each time.
The reaction temperature is 25-45 ℃, the total reaction time is 6-15 h, and the stirring speed in the reaction process is 150-300 r/min.
And adding high-purity water for concentration and evaporation to remove the alcohol solvent, wherein the using amount of the high-purity water is 100-200% of the total mass of the reaction system.
The temperature of the evaporation concentration is 85-120 ℃, and the evaporation concentration is carried out until the total mass of the reaction system is 12.5-50 wt%.
The nanometer aqueous silica sol is added with one of pH regulators of nitric acid, hydrochloric acid, sulfuric acid, citric acid, tartaric acid, oxalic acid, sodium hydroxide, potassium hydroxide and ammonia water, and can be adjusted to be acidic or alkaline, specifically 2-4, and when the alkalinity is 8-11, the stability of the silica sol is not affected.
The invention aims to provide a nano aqueous silica sol material for polishing a semiconductor, which is prepared by the method. The particle size of the nano water-based silica sol obtained by the method is within the range of +/-5 nm of a target particle size, the content of various metal impurities is controlled at a ppb level, the nano water-based silica sol does not contain high-molecular organic matters, the nano water-based silica sol has stable performance, can be adjusted to be acidic or alkaline, specifically acidic 2-4, and alkaline 8-11, and after the pH is adjusted, the stability of the silica sol cannot be influenced. Can be used for chemical mechanical polishing of semiconductor materials.
The technical scheme of the invention proves that the change of the concentration of the catalyst can control the nucleation speed and the hydrolysis speed of the organic silicon source, and the particle size of the silicon dioxide particles is increased along with the increase of the concentration of the ammonia water. The variety of the solvent alcohol has very obvious influence on the particle size and the dispersity of the silica sol, the alcohol molecular weight is increased along with the growth of a carbon chain of the monohydric alcohol, the viscosity of the alcohol solvent is also increased, the diffusion rate of reactant molecules is reduced, the nucleation rate is reduced, the number of formed initial nuclei is small, and more reactants remained in a system can be gradually deposited on the surfaces of the nuclei to grow so as to increase the particle size of the silica; however, no silica sol with good dispersibility could be formed in the polyol system. Therefore, the size of the silica sol particle diameter can be controlled by controlling the concentration of the catalyst and the type and proportion of the monohydric alcohol solvent. Because the growth activity of the silicon dioxide particles is gradually reduced along with the increase of the particle size, in order to ensure that the concentration of the monomer obtained by hydrolyzing the organic silicon source is lower than the critical nucleation concentration, a stepwise gradual and gradual feeding mode is adopted, so that the formation of new crystal nuclei in the solution is avoided, the monomer is ensured to have sufficient time to select the deposited spheres, the particle size distribution of the silica sol is narrowed, the method is more favorable for the generation of high-quality silicon dioxide particles compared with the traditional sol-gel method, the specific surface area of the silica sol is reduced, and the uniformity of the particle size is improved.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method controls the growth of the silica sol in the range of target grain diameter +/-5 nm by controlling the adding amount of the catalyst and the proportion of the mixed alcohol;
(2) by controlling the purity of the raw materials, the method does not introduce any metal impurities and macromolecular organic matters in the preparation process, and the content of various metal impurities can be controlled at ppb level; the obtained nano water-based silica sol belongs to a semiconductor polishing material with excellent performance;
(3) according to the method, the silica sol particles uniformly and stably grow in a mode that the adding amount of the organic silicon source is gradually decreased, the performance of the obtained aqueous silica sol is stable, the aqueous silica sol can be adjusted to be acidic or alkaline according to the requirement of the semiconductor material chemical mechanical polishing solution, specifically, the pH value is 2-4, the pH value is 8-11, and the stability of the silica sol cannot be influenced after the pH value is adjusted.
Drawings
FIG. 1 shows the electron microscope images of the nano-sized aqueous silica sol particles prepared in example 1 of the present invention.
FIG. 2 shows the electron microscope images of the nano-sized aqueous silica sol particles prepared in example 2 of the present invention.
FIG. 3 shows an electron microscope image of the nano-sized aqueous silica sol particles prepared in embodiment 3 of the present invention.
FIG. 4 shows an electron microscope image of the nano-sized aqueous silica sol particles prepared in example 4 of the present invention.
FIG. 5 shows an electron microscope image of the nano-sized aqueous silica sol particles prepared in example 5 of the present invention.
FIG. 6 shows an electron microscope image of the nano-sized aqueous silica sol particles prepared in example 6 of the present invention.
FIG. 7 shows the electron microscope images of the nano-sized aqueous silica sol particles prepared in example 7 of the present invention.
FIG. 8 is an electron microscope image of 10-20 nm acidic non-spherical aqueous silica sol particles prepared in example 8 of the present invention.
FIG. 9 shows an electron microscope image of 40-50 nm acidic non-spherical aqueous silica sol particles prepared in example 9 of the present invention.
FIG. 10 shows an electron microscope image of a 70-80 nm alkaline spherical aqueous silica sol particle prepared in example 10 of the present invention.
FIG. 11 is an electron microscope image of the 150-160 nm alkaline spherical aqueous silica sol particles prepared in example 11 of the present invention.
Detailed Description
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
In a dust-free laboratory, 4.66g of analytically pure ammonia water, 150.3g of analytically pure methanol, 16.7g of analytically pure ethanol and 12.8g of high-purity water are weighed, added into a three-neck flask, uniformly mixed, added with 22.86g of analytically pure ethyl silicate at one time at 40 ℃ and a stirring speed of 300r/min, and reacted for 9 hours. And (3) in the reaction process, the pH is 8.0-8.5, after the reaction is finished, 200g of high-purity water is added, the mixture is heated to 98 ℃, the alcohol solvent is evaporated and recovered, the solution is concentrated until the volume of the solution is 50mL, high-purity nano water-based silica sol is obtained, and the metal ion content of the high-purity nano water-based silica sol is detected by ICP-MS.
And (3) dropwise adding 10wt% of analytically pure sodium hydroxide solution into the high-purity nano aqueous silica sol solution, adjusting the pH to 9.8, and checking the stability. The TESCAN MIRA3 field emission scanning electron microscope is used for detection, and the electron microscope picture is shown in figure 1.
Example 2
In a dust-free laboratory, 4.65g of analytically pure ammonia water, 150.3g of analytically pure methanol, 16.7g of analytically pure ethanol and 12.8g of high-purity water are weighed, added into a three-neck flask, uniformly mixed, and reacted for 3 hours by adding 9.52g of analytically pure ethyl silicate for the first time, adding 7.23g of analytically pure ethyl silicate for the second time and reacting for 3 hours by adding 5.34g of analytically pure ethyl silicate for the third time at the stirring speed of 300r/min at 40 ℃. And (3) in the reaction process, the pH is 8.6-9.0, after the reaction is finished, 200g of high-purity water is added, the mixture is heated to 98 ℃, the alcohol solvent is evaporated and recovered, the solution is concentrated until the volume of the solution is 50mL, high-purity aqueous silica sol is obtained, and the metal ion content of the high-purity aqueous silica sol is detected by ICP-MS.
And (3) dropwise adding 10wt% of analytically pure potassium hydroxide solution into the high-purity nano aqueous silica sol solution, adjusting the pH value to 10.5, and checking the stability. The detection is carried out by using TESCAN MIRA3 field emission scanning electron microscope, and an electron microscope image is shown in figure 2.
Example 3
In a dust-free laboratory, 6.42g of analytically pure ammonia water, 76.5g of analytically pure ethanol, 76.5g of analytically pure isopropanol and 12.8g of high-purity water are weighed and added into a three-neck flask, the mixture is uniformly mixed, 6.51g of analytically pure ethyl silicate is added for the first time to react for 2 hours at the temperature of 40 ℃ and at the stirring speed of 300r/min, 5.53g of analytically pure ethyl silicate is added for the second time to react for 2 hours, 4.56g of analytically pure ethyl silicate is added for the third time to react for 2 hours, 3.52g of analytically pure ethyl silicate is added for the fourth time to react for 2 hours, and 2.05g of analytically pure ethyl silicate is added for the fifth time to react for 2 hours. And (3) in the reaction process, the pH is 9.1-9.5, after the reaction is finished, 200g of high-purity water is added, the mixture is heated to 98 ℃, the alcohol solvent is evaporated and recovered, the solution is concentrated until the volume of the solution is 50mL, high-purity nano water-based silica sol is obtained, and the metal ion content of the high-purity nano water-based silica sol is detected by ICP-MS.
And (3) dropwise adding 10wt% of analytically pure tartaric acid solution into the high-purity nano aqueous silica sol solution, adjusting the pH to 2.5, and checking the stability. The TESCAN MIRA3 field emission scanning electron microscope is used for detection, and an electron microscope picture is shown in figure 3.
Example 4
In a dust-free laboratory, 8.35g of analytically pure ammonia water, 135.7g of analytically pure isopropanol, 15.3g of analytically pure isobutanol and 12.8g of highly pure water are weighed and added into a three-neck flask, the mixture is uniformly mixed, 4.85g of analytically pure ethyl silicate is added for the first time to react for 2 hours at the temperature of 40 ℃ and the stirring speed of 300r/min, 4.32g of analytically pure ethyl silicate is added for the second time to react for 2 hours, 3.82g of analytically pure ethyl silicate is added for the third time to react for 2 hours, 3.31g of analytically pure ethyl silicate is added for the fourth time to react for 2 hours, 2.81g of analytically pure ethyl silicate is added for the fifth time to react for 2 hours, 2.35g of analytically pure ethyl silicate is added for the sixth time to react for 2 hours, and 1.83g of analytically pure ethyl silicate is added for the seventh time to react for 2 hours. And in the reaction process, the pH is 9.6-10.0, after the reaction is finished, 200g of high-purity water is added, the mixture is heated to 98 ℃ and evaporated to recover the alcohol solvent, the alcohol solvent is concentrated until the volume of the solution is 50mL, high-purity nano water-based silica sol is obtained, and the metal ion content of the high-purity nano water-based silica sol is detected by ICP-MS.
And (3) dropwise adding 10wt% of analytically pure nitric acid solution into the high-purity nano aqueous silica sol solution, adjusting the pH to 3.8, and checking the stability. The TESCAN MIRA3 field emission scanning electron microscope is used for detection, and the electron microscope picture is shown in figure 4.
Example 5
In a dust-free laboratory, 8.39g of analytically pure ammonia water, 135.7g of analytically pure isopropanol, 15.3g of analytically pure isobutanol and 12.8g of highly pure water are weighed and added into a three-neck flask, the mixture is uniformly mixed, 6.48g of analytically pure ethyl silicate is added for the first time to react for 2 hours at the temperature of 40 ℃ and the stirring speed of 300r/min, 5.55g of analytically pure ethyl silicate is added for the second time to react for 2 hours, 4.52g of analytically pure ethyl silicate is added for the third time to react for 2 hours, 3.51g of analytically pure ethyl silicate is added for the fourth time to react for 2 hours, and 2.02g of analytically pure ethyl silicate is added for the fifth time to react for 2 hours. And in the reaction process, the pH is 9.6-10.0, after the reaction is finished, 200g of high-purity water is added, the mixture is heated to 98 ℃ and evaporated to recover the alcohol solvent, the alcohol solvent is concentrated until the volume of the solution is 50mL, high-purity nano water-based silica sol is obtained, and the metal ion content of the high-purity nano water-based silica sol is detected by ICP-MS.
And (3) dropwise adding 10wt% of analytically pure oxalic acid solution into the high-purity nano water-based silica sol solution, adjusting the pH to 5.6, checking the stability, and detecting by using an TESCAN MIRA3 field emission scanning electron microscope, wherein an electron microscope image is shown in figure 5.
Example 6
In a dust-free laboratory, 4.71g of analytically pure ammonia water, 115.5g of analytically pure 1, 4-butanediol, 49.5g of analytically pure ethylene glycol and 12.8g of highly pure water are weighed, added into a three-neck flask, uniformly mixed, and at the temperature of 40 ℃ and the stirring speed of 300r/min, 9.49g of analytically pure ethyl silicate is added for the first time, reacted for 3 hours, 7.26g of analytically pure ethyl silicate is added for the second time, reacted for 3 hours, 5.31g of analytically pure ethyl silicate is added for the third time, and the reaction time is 3 hours, wherein the pH value is 8.6-9.0 in the reaction process. Obtaining high-purity silica sol, and detecting the metal ion content of the high-purity silica sol by ICP-MS.
And (3) dropwise adding 10wt% of analytically pure citric acid solution into the high-purity nano aqueous silica sol solution, adjusting the pH to 3.5, and checking the stability. The TESCAN MIRA3 field emission scanning electron microscope is used for detection, and an electron microscope picture is shown in figure 6.
Example 7
In a dust-free laboratory, 4.68g of analytically pure ammonia water, 115.5g of analytically pure 1, 4-butanediol, 49.5g of analytically pure glycerol and 12.8g of high purity water are weighed, added into a three-neck flask, uniformly mixed, and at the temperature of 40 ℃ and the stirring speed of 300r/min, 9.51g of analytically pure ethyl silicate is added for the first time, the mixture is reacted for 3 hours, 7.25g of analytically pure ethyl silicate is added for the second time, the mixture is reacted for 3 hours, 5.36g of analytically pure ethyl silicate is added for the third time, and the pH value is 8.6-9.0 in the reaction process. Obtaining high-purity silica sol, and detecting the metal ion content of the high-purity silica sol by ICP-MS.
And (3) dropwise adding 10wt% of analytical pure hydrochloric acid solution into the high-purity nano aqueous silica sol solution, adjusting the pH value to 3.5, and checking the stability. The TESCAN MIRA3 field emission scanning electron microscope is used for detection, and the electron microscope picture is shown in figure 7.
The performance test of the silica sol obtained in the embodiment 1 to 4 was performed, and the results are shown in table 1:
TABLE 1
From the detection results of the embodiment in table 1, the obtained high-purity nano-water-based silica sol can be controlled to grow in the range of target particle size +/-5 nm by controlling the concentration of ammonia water, the proportion of mixed monohydric alcohol and the gradual decrease adding mode of the organic silicon source; the metal ion content is extremely low, no macromolecular organic matter is contained, and the performance is stable. According to the requirements of the chemical mechanical polishing solution for semiconductors, the polishing solution can be adjusted to be acidic or alkaline, specifically, the acidity is 2-4, the alkalinity is 8-11, and after the pH is adjusted, the stability of the silica sol cannot be influenced. Can meet the chemical mechanical polishing requirement of semiconductor materials.
From the electron microscope image of the embodiment 1, the silica sol obtained by adding the organic silicon source once has poor dispersibility. From the electron microscope images of the implementation cases 2, 3, 4 and 5, the addition times of the organic silicon source are preferably 3-5 times, and silica sol with good dispersibility can be obtained after 7 times, but the addition times are large, the reaction time is prolonged, and more energy is consumed. As seen in the electron micrographs of examples 6 and 7, the spherical silica sol with good dispersibility could not be obtained by mixing the polyol.
Example 8
Weighing 6g of ammonia water, 167g of ethanol and 15g of high-purity water, adding the ammonia water, the 167g of ethanol and the 15g of high-purity water into a three-neck flask, uniformly mixing, adding 7g of tetraethoxysilane for the first time at 40 ℃ and at a stirring speed of 300r/min, reacting for 4 hours, adding 5g of tetraethoxysilane for the second time, and continuing to react for 5 hours. And after the reaction is finished, adding 200g of high-purity water, heating to 95 ℃, evaporating to recover ethanol, and concentrating until the volume of the solution is 50mL to obtain the non-spherical high-purity water-based silica sol with the mass fraction of 6.7% and the particle size of 10-20 nm.
And (3) dropwise adding 10wt% of nitric acid solution into the silica sol solution, and adjusting the pH to 3-4 to obtain 10-20 nm acidic non-spherical aqueous silica sol, wherein the stabilization period can reach 1 year. The detection is carried out by using TESCAN MIRA3 field emission scanning electron microscope, and an image of the electron microscope is shown in figure 8.
Example 9
Weighing 9g of ammonia water, 159g of ethanol and 15g of high-purity water, adding the ammonia water, the 159g of ethanol and the 15g of high-purity water into a three-neck flask, uniformly mixing, adding 7g of tetraethoxysilane for the first time at 40 ℃ and at a stirring speed of 300r/min, and reacting for 2.5 hours; adding 5g of tetraethoxysilane for the second time, and reacting for 2.5 hours; adding 3g of tetraethoxysilane for the third time, and reacting for 2.5 hours; 2g of tetraethoxysilane is added for the fourth time, and the reaction is carried out for 2.5 hours. And after the reaction is finished, adding 200g of high-purity water, heating to 95 ℃, evaporating to recover ethanol, concentrating until the volume of the solution is 50mL, and synthesizing the non-spherical high-purity water-based silica sol with the mass fraction of 9.5% and the particle size of 40-50 nm.
And (3) dropwise adding 10wt% of citric acid aqueous solution into the silica sol, and adjusting the pH to 3-4 to obtain 40-50 nm acidic non-spherical aqueous silica sol, wherein the stabilization period can reach 1 year. The TESCAN MIRA3 field emission scanning electron microscope is used for detection, and an electron microscope image is shown in FIG. 9.
Example 10
Weighing 13g of ammonia water, 155g of ethanol and 15g of high-purity water, adding the ammonia water, the ethanol and the high-purity water into a three-neck flask, uniformly mixing, adding 7g of tetraethoxysilane into the mixture for the first time at the temperature of 40 ℃ and the stirring speed of 300r/min for reaction for 2.5 hours, adding 5g of tetraethoxysilane into the mixture for the second time for reaction for 2.5 hours, adding 3g of tetraethoxysilane into the mixture for the third time for reaction for 2.5 hours, and adding 2g of tetraethoxysilane into the mixture for the fourth time for reaction for 2.5 hours. And after the reaction is finished, adding 200g of high-purity water, heating to 95 ℃, evaporating to recover ethanol, concentrating until the volume of the solution is 50mL, and synthesizing the spherical high-purity water-based silica sol with the mass fraction of 9.5% and the particle size of 80-90 nm.
And (3) dropwise adding 10wt% of ammonia water solution into the silica sol, and adjusting the pH to 9-10 to obtain 80-90 nm alkaline spherical aqueous silica sol, wherein the stabilization period can reach 1 year. The detection is carried out by using TESCAN MIRA3 field emission scanning electron microscope, and an image of the electron microscope is shown in figure 10.
Example 11
Weighing 15g of ammonia water, 138g of ethanol and 15g of high-purity water, adding the ammonia water, the ethanol and the high-purity water into a three-neck flask, uniformly mixing, adding 9g of tetraethoxysilane into the mixture for the first time at the temperature of 40 ℃ and at the stirring speed of 300r/min for reaction for 1.5 hours, adding 7g of tetraethoxysilane into the mixture for the second time for reaction for 1.5 hours, adding 6g of tetraethoxysilane into the mixture for the third time for reaction for 1.5 hours, adding 5g of tetraethoxysilane into the mixture for the fourth time for reaction for 1.5 hours, adding 3g of tetraethoxysilane into the mixture for the fifth time for reaction for 1.5 hours, and adding 2g of tetraethoxysilane into the mixture for reaction for the sixth time for 1.5 hours. And after the reaction is finished, adding 200g of high-purity water, heating to 95 ℃, evaporating to recover ethanol, concentrating until the volume of the solution is 20mL, synthesizing the alkaline spherical high-purity water-based silica sol with the mass fraction of 44.8%, the particle size of 150-160 nm and the pH of 8-9, and enabling the stabilization period to be up to 1 year. The TESCAN MIRA3 field emission scanning electron microscope is used for detection, and the electron microscope picture is shown in figure 11.
The above description is only a detailed implementation of the present invention, and is not intended to limit the present invention in any way, and all simple modifications, equivalent variations and modifications made to the above embodiments according to the technical spirit of the present invention still belong to the technical scope of the present invention.
Claims (2)
1. A preparation method of a nano-water-based silica sol material for semiconductor polishing is characterized by comprising the following steps:
(1) in a dust-free laboratory, adding an analytically pure catalyst and high-purity water into an analytically pure mixed alcohol solvent, uniformly stirring, and preparing a solution A, wherein the alcohol solvent is a mixture of methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol, and the mass fraction of the mixed alcohol in a reaction system is 60-90 wt%; the catalyst comprises one or a mixture of two of ammonia water, monoethanolamine, triethanolamine, tetramethylammonium hydroxide and tetraethylammonium hydroxide, and the mass fraction of the catalyst in the reaction system is 1-8 wt%; the mass fraction of the water in the step (1) in the reaction system is 2-8 wt%;
(2) adding analytically pure organic silicon source into the solution A according to the amount on time, adding the organic silicon source for multiple times in an adding mode, wherein the adding times are 3-5 times, the adding amount is 1-5 wt% each time, the adding amount gradually decreases along with the reaction time, the decreasing amount for each time is 0.10-0.75 wt%, and the reaction time is 2-5 hours after the organic silicon source is added each time; the organic silicon source is one or a mixture of ethyl orthosilicate and methyl orthosilicate, the mass fraction of the organic silicon source in a reaction system is 5-25 wt%, and the content of silicon dioxide in the organic silicon source is more than 28%;
(3) stirring and reacting for 5-15 h at 25-45 ℃, stirring at a speed of 150-300 r/min, adding high-purity water after the reaction is finished, wherein the using amount of the high-purity water is 100% -200% of the total mass of the reaction system, evaporating and concentrating, and removing the alcohol solvent to obtain the nano water-based silica sol material for semiconductor polishing.
2. The method according to claim 1, wherein the temperature of the evaporation concentration in the step (3) is 85 to 100 ℃, and the evaporation concentration is carried out until the total mass of the reaction system is 12.5 to 50 wt%.
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