WO2017206386A1 - 多分散大粒径硅溶胶及其制备方法 - Google Patents

多分散大粒径硅溶胶及其制备方法 Download PDF

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WO2017206386A1
WO2017206386A1 PCT/CN2016/097876 CN2016097876W WO2017206386A1 WO 2017206386 A1 WO2017206386 A1 WO 2017206386A1 CN 2016097876 W CN2016097876 W CN 2016097876W WO 2017206386 A1 WO2017206386 A1 WO 2017206386A1
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silica sol
diameter
particle size
polydisperse
seed crystal
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English (en)
French (fr)
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孔慧
刘卫丽
宋志棠
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上海新安纳电子科技有限公司
中国科学院上海微系统与信息技术研究所
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Publication of WO2017206386A1 publication Critical patent/WO2017206386A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/145—Preparation of hydroorganosols, organosols or dispersions in an organic medium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
    • C09K3/1463—Aqueous liquid suspensions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

  • the invention relates to a silica sol and a preparation method thereof, in particular to a polydisperse large-diameter silica sol and a preparation method thereof, and belongs to the field of chemical engineering.
  • the polishing liquid product mainly uses monodisperse silicon oxide as the abrasive, and the conventional silicon oxide abrasive has two kinds: sintered silicon oxide and colloidal silicon oxide.
  • the sintered silicon oxide has a high polishing rate but the surface quality of the material to be polished is poor, and the scratch is severe; the surface quality of the colloidal silica is good but the polishing rate is slow. How to improve the polishing rate without damaging the surface quality is a major problem for CMP polishing fluids.
  • many researchers have made useful attempts, such as the preparation of non-spherical silicon oxide.
  • a silica particle having an elongated shape and a method for producing the same are provided, which have a large friction coefficient and a high polishing rate during polishing.
  • the preparation of non-spherical silica generally introduces a divalent or trivalent metal salt solution, which may cause the stability of the silica sol system to be deteriorated; or the organic alkali solution is used in the preparation process, and the organic alkali is not easily removed in the silica sol system, which is easy to cause Environmental pollution.
  • the object of the present invention is to provide a polydisperse large-diameter silica sol and a preparation method thereof, the silica sol having a wide particle size distribution, and a large-grain silica sol diameter for polishing a semiconductor material
  • the small particle size silica sols cooperate with each other, have a large friction coefficient, strong chemical activity and high polishing efficiency. It has been verified that the use of the silica sol of the present invention can increase the polishing rate by more than 37%, while the polishing sheet is less scratched.
  • the present invention provides a polydisperse large particle size preparation method, wherein polydispersion means that the silica sol is not a single particle size distribution, but a mixed state of a plurality of particle sizes, where the maximum The difference between the particle size and the minimum particle size is 75 nm, and the particle size is from 20 nm to 95 nm. Between the distribution; the large particle size refers to a silica sol having a particle size of 20 nm or more.
  • the preparation method comprises the following steps: using a monodisperse spherical silica sol having a particle diameter of 20 nm to 30 nm as a seed crystal, stirring and heating at the same time, and continuously adding a monodisperse spherical silica sol seed crystal having a particle diameter of 20 nm to 30 nm to the reaction system; Active silicic acid, in the whole reaction process, the heating liquid concentration method is used to maintain the constant liquid level, and the inorganic alkali dilute solution is added dropwise to keep the pH value of the system at 9.5-10.5. After the reaction, the temperature is kept and cooled.
  • the preparation method specifically comprises the following steps:
  • Step (1) Preparation of active silicic acid:
  • the concentrated water glass is diluted with water to a solution having a silica content of 2-6 wt%, stirred uniformly, and then added to a strong acid type cation exchange resin for cation exchange to obtain a pH of 2.0-4.0.
  • the cation exchange resin is regenerated
  • the strongly acidic cationic resin may be selected from a polybenzenesulfonic acid type resin.
  • Step (2) Preparation of monodisperse small-diameter silica sol seed crystal: stirring 0.1-1.0 wt% of the inorganic alkali solution and heating to 90-100 ° C, and then preparing 2-4 times the volume of the step (1)
  • the active silicic acid is gradually added, and after the end of the feeding, the heat preservation is continued, and the mixture is naturally cooled to room temperature to obtain a monodisperse spherical silica sol having a particle diameter of 20 nm to 30 nm as a seed crystal;
  • the inorganic alkali solution mainly uses an inorganic alkali solution in which the solvent is water.
  • the incubation time is 0.5-2 hours
  • the rate of addition of the active silicic acid is from 2 to 20 ml/min.
  • Step (3) Preparation of polydisperse large-diameter silica sol: taking the seed crystal prepared in the step (2) as a mother liquid, stirring and heating to boiling, and then adding the above-mentioned to the reaction system at a rate of 4-10 ml/min.
  • the active silicic acid prepared in the step (1) is continuously added to the reaction system at a rate of 0.85-1.85 ml/min to continuously maintain the seed crystal prepared in the step (2), maintaining a constant liquid level, and simultaneously adding an inorganic base.
  • the solution was maintained at a pH of 9.50 to 10.50 throughout the system. After the end of the addition, the temperature was maintained and allowed to cool to room temperature.
  • the incubation time is from 0.5 to 2 hours.
  • the lye is selected from any one or a mixture of a potassium hydroxide solution, a sodium hydroxide solution.
  • Another aspect of the invention provides a polydisperse large particle size silica sol.
  • the polydisperse large-diameter silica sol has a particle diameter of 20 nm to 95 nm.
  • Another aspect of the present invention provides the use of a polydisperse large particle size silica sol for making a polishing liquid.
  • the polydisperse large-diameter silica sol of the present invention and the preparation method thereof have the following beneficial effects:
  • the silica sol prepared by the invention has a wide particle size distribution, and is between 20 nm and 95 nm, and can effectively improve the polishing efficiency when used as a polishing liquid.
  • the process of the invention is simple and efficient, and has great advantages over the conventional preparation method.
  • Figure 1 shows an electron micrograph of a polydisperse large particle size silica sol prepared in Example 1.
  • Figure 2 shows an electron micrograph of a polydisperse large particle size silica sol prepared in Example 2.
  • Figure 3 shows an electron micrograph of a polydisperse large particle size silica sol prepared in Example 3.
  • the electron microscope used in the observation of the silica sol in the following examples was a focused ion beam system manufactured by FEI Corporation of the United States under the model Helios NanoLab 600.
  • Example 1 Polydisperse large particle size silica sol and preparation method thereof
  • Step (1) diluting the concentrated water glass with pure water to a silica content of 4%, stirring uniformly, and adding it to the regenerated treated strong acid type cation exchange resin (polyphenylsulfonic acid type) for cation exchange.
  • the active silicic acid, the active silicic acid had a pH of 2.85 and a silica content of 4%.
  • Step (2) 1000 mL of a 1 wt% potassium hydroxide solution was taken, stirred and heated to 98 ° C, and 4000 ml of the active silicic acid prepared in the above step (1) was pumped through a peristaltic pump at a rate of 8 ml/min. After the end of the active silicic acid addition, the incubation was continued for 0.5 hours. Naturally cooled to room temperature, a monodisperse spherical silica sol having a particle diameter of 20 nm to 30 nm was obtained as a seed crystal.
  • Step (3) Weigh 800 ml of the seed crystal prepared in the above step (2) as a mother liquid, stir and heat to boiling, and add the active silicic acid prepared in the above step (1) at a rate of 6.5 ml/min while passing 0.92 ml through a peristaltic pump. At a rate of /min, 2760 ml of the seed crystal prepared in the step (2) was continuously added, during which a 1 wt% diluted solution of potassium hydroxide was added dropwise to maintain the pH of the entire system between 9.50 and 0.50. After the completion of the reaction, the temperature was kept at 100 ° C for 2 hours, and naturally cooled to room temperature to prepare a polydisperse large particle size silica sol spherical silica sol.
  • the particle size of the polydisperse large-diameter silica sol is distributed between 20 nm and 85 nm, and the average particle diameter measured by a laser particle size analyzer (dynamic light scattering method) is 78.9 nm, pH. The value was 9.96 and the concentration was 22.4% by weight.
  • Step (1) The concentrated water glass is diluted with pure water to a silica content of 2%, stirred uniformly, and then added to a regenerated, strong acid type cation exchange resin (polyphenylsulfonic acid type) to carry out cation exchange to obtain activity.
  • the pH of the silicic acid, active silicic acid is 3.0.
  • Step (2) A 1500 mL of a 0.3 wt% sodium hydroxide solution was taken, stirred and heated to 100 ° C, and 3500 ml of the active silicic acid prepared in the above step (1) was pumped through a peristaltic pump at a rate of 3.5 ml/min. After the end of the silicic acid addition, the insulation was continued for 1.5 hours. Naturally cooled to room temperature, a monodisperse small-diameter spherical silica sol having a particle diameter of 20 nm to 30 nm was obtained as a seed crystal.
  • Step (3) Weigh 1000 ml of the seed crystal prepared in the above step (2) as a mother liquid, stir and heat to boiling, and add the activity prepared in the above step (1) by a peristaltic pump at a rate of 5.8 ml/min.
  • the seed crystal 3847m prepared in the above step (2) was continuously supplied by a peristaltic pump at a rate of 1 ml/min.
  • a 1 wt% dilute solution of sodium hydroxide was added dropwise to maintain the pH of the entire system between 9.50-10.50.
  • the temperature was kept at 100 ° C for 0.5 hour, and naturally cooled to room temperature to prepare a polydisperse large particle size silica sol spherical silica sol.
  • the particle size of the polydisperse large-diameter silica sol is distributed between 20 nm and 95 nm, and the average particle diameter measured by a laser particle size analyzer (dynamic light scattering method) is 82.2 nm.
  • the pH was 10.10 and the concentration was 20.41% by weight.
  • Step (1) diluting the concentrated water glass with pure water to a silica content of 6%, stirring uniformly, and adding it to the regenerated volatile acid-type cation exchange resin (polyphenylsulfonic acid type) for cation exchange to obtain activity.
  • the pH of the silicic acid, active silicic acid is 2.74.
  • Step (2) A 1500 mL of a 0.3 wt% sodium hydroxide solution was taken, stirred and heated to 100 ° C, and 3500 ml of the active silicic acid prepared in the above step (1) was pumped through a peristaltic pump at a rate of 3.5 ml/min. After the end of the silicic acid addition, the insulation was continued for 2 hours. Naturally cooled to room temperature, a monodisperse small-diameter spherical silica sol having a particle diameter of 20 nm to 30 nm was obtained as a seed crystal.
  • Step (3) Weigh 800 ml of the seed crystal prepared in the above step (2) as a mother liquid, stir and heat to boiling, and the peristaltic pump is added to the active silicic acid prepared in the above step (1) at a rate of 4.4 ml/min, and the entire silicic acid is fed.
  • 9969 ml of the seed crystal prepared in the above step (2) was continuously added by a peristaltic pump at a rate of 1.85 ml/min.
  • 2 wt% of a dilute solution of sodium hydroxide and potassium hydroxide was added dropwise to maintain the pH of the entire system between 9.50-10.50.
  • the temperature was kept at 100 ° C for 1.2 hours, and naturally cooled to room temperature to prepare a polydisperse large particle size silica sol spherical silica sol.
  • the particle size of the polydisperse large-diameter silica sol is distributed between 20 nm and 85 nm, and the average particle diameter measured by a laser particle size analyzer (dynamic light scattering method) is 68.4 nm.
  • the pH was 10.32 and the concentration was 30.90% by weight.
  • the polydisperse large-diameter silica sol prepared in the above Examples 1-3 was configured as a polishing liquid for rough polishing of sapphire sheets.
  • the slurry is prepared by diluting the polydisperse large-diameter silica sol prepared by the invention to a silica content of 15% by weight, adjusting the pH to 10.50 with a 5 wt% aqueous sodium hydroxide solution, and stirring uniformly. Weigh 1kg, which is the polishing liquid.
  • Polishing experiment A 2 inch C phase sapphire piece was adhered to the polishing head by a back film adsorption method.
  • the polishing parameters were set as follows: polishing pressure was 6 psi; polishing pad rotation speed was 100 rpm; polishing pad rotation speed was 90 rpm; polishing liquid flow rate was 125 ml/min; polishing time was 30 min.
  • polishing pad was repaired with a 4 inch diamond repair disk for 5 minutes, and the polished sapphire sheet was ultrasonically washed in a washing liquid for 10 minutes and then dried with nitrogen.
  • the surface quality of the polished sapphire sheet was observed by a metallographic microscope.
  • the thickness polishing speed was calculated by measuring the difference in mass before and after polishing of the sapphire sheet, and the results are shown in Table 1.
  • the polydisperse large-diameter silica sol prepared by the invention is compared with the conventional ion exchange method for the monodisperse large-diameter silica sol (90 nm), and the polishing rate of the former is more than 37% faster than the latter polishing rate.
  • the polishing rate of Example 1-3 After the polishing of Example 1-3, the surface quality of the sapphire sheet was good, and there were no defects such as scratches and pits.

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Abstract

提供一种多分散大粒径硅溶胶、其制备方法及用于制作抛光液的用途。该制备方法为：以粒径为20nm-30nm的单分散球形硅溶胶为晶种，搅拌并加热，同时向反应体系不断的滴加粒径为20nm-30nm的单分散球形硅溶胶晶种和活性硅酸，在整体反应过程中采用加热浓缩法维持恒液位，期间，滴加无机碱稀溶液以保持体系的pH值在9.5-10.5，保温后冷却。采用该方法制备的硅溶胶能够有效地提高抛光速度，同时减少划痕产生。

Description

多分散大粒径硅溶胶及其制备方法 技术领域
本发明涉及一种硅溶胶及其制备方法，特别是涉及一种多分散大粒径硅溶胶及其制备方法，属于化学工程领域。
背景技术
随着集成电路技术的高度发展，对所用衬底材料的表面质量要求越来越高。由于器件尺寸的缩小，光学光刻设备焦深的减小，要求晶片表面可接受的分辨率的平整度达到纳米级。为解决这一问题，能够实现全局平坦化的化学机械抛光(Chemical Mechanical Polishing，CMP)技术，一举成为半导体制造重要关键工艺之一。目前抛光液产品主要以单分散的氧化硅作为磨料，而传统的氧化硅磨料有两种：烧结氧化硅和胶体氧化硅。烧结氧化硅抛光速率快但是被抛光材料表面质量差，划伤严重；胶体氧化硅表面质量好但是抛光速率慢。如何在不损害表面质量的前提下提高抛光速率，是CMP抛光液面临的一大难题。为了克服现有技术的不足，许多科研工作者作出了有益的尝试，比如制备非球形氧化硅。在专利CN 101626979A提供了一种呈细长形状的二氧化硅颗粒及其制备方法，抛光时摩擦系数大，抛光速率高。非球形氧化硅的制备一般会引入二价或三价的金属盐溶液，会造成硅溶胶体系稳定性变差；或者制备过程使用有机碱溶液，有机碱在硅溶胶体系中不容易去除，容易造成环境污染。
发明内容
鉴于以上所述现有技术的缺点，本发明的目的在于提供一种多分散大粒径硅溶胶及其制备方法，硅溶胶具有很宽的粒径分布，给半导体材料抛光时大粒硅溶胶径和小粒径硅溶胶相互配合，摩擦系数大，化学活性强，抛光效率高。经验证，使用本发明的硅溶胶可将抛光速率提升37％以上，同时抛光片较少有划痕产生。
为实现上述目的及其他相关目的，本发明提供一种多分散大粒径制备方法，其中多分散是指硅溶胶不是单一的一种粒径分布，而是多种粒径的混合状态，这里最大粒径和最小粒径差值达到75nm，粒径从20nm到95nm 之间分布；大粒径是指硅溶胶的粒径达到20nm以上的硅溶胶。
所述制备方法：以粒径为20nm-30nm的单分散球形硅溶胶为晶种，搅拌并同时加热，同时向反应体系不断的滴加粒径为20nm-30nm的单分散球形硅溶胶晶种和活性硅酸，在整体反应过程中采用加热浓缩法维持恒液位，同时滴加无机碱稀溶液以保持体系的pH值在9.5-10.5，反应结束后保温，冷却。
优选地，所述制备方法具体包括以下步骤：
步骤(1)活性硅酸制备：将浓水玻璃用水稀释至二氧化硅含量为2-6wt％的溶液，搅拌均匀后加入到强酸型阳离子交换树脂内进行阳离子交换，得到pH为2.0-4.0的活性硅酸；
优选地，阳离子交换树脂是经过再生处理的，
强酸性阳离子树脂可以选自聚苯磺酸型树脂，
步骤(2)单分散小粒径硅溶胶晶种的制备：取0.1-1.0wt％的无机碱溶液搅拌并加热至90-100℃，再将2-4倍体积的所述步骤(1)制备的活性硅酸逐渐加入，加料结束后，继续保温，自然冷却至室温，制得粒径为20nm-30nm的单分散球形硅溶胶作为晶种；
所述无机碱溶液主要采用溶剂为水的无机碱溶液。
优选地，保温的时间为0.5-2小时，
优选地，加活性硅酸的速度为2-20ml/min。
步骤(3)多分散大粒径硅溶胶制备：取所述步骤(2)制备的晶种作为母液，搅拌并加热至沸，然后向反应体系中以4-10ml/min的速度滴加所述步骤(1)制备的活性硅酸，同时向反应体系中以0.85-1.85ml/min的速度连续不断地补加所述步骤(2)制备的晶种，维持恒液位，同时滴加无机碱溶液以保持整个体系的pH值维持在9.50-10.50，加料结束后，继续保温，自然冷却至室温。
优选地，保温时间为0.5-2小时。
优选地，碱液选自氢氧化钾溶液、氢氧化钠溶液中的任意一种或者两者的混合物。
本发明的另一个方面是提供了一种多分散大粒径硅溶胶。
优选地，所述多分散大粒径硅溶胶的粒径为20nm-95nm。
本发明的另一个方面是提供了多分散大粒径硅溶胶用于制作做抛光液的用途。
如上所述，本发明的多分散大粒径硅溶胶及其制备方法，具有以下有益效果：
本发明制备的硅溶胶粒径范围分布较广，在20nm-95nm之间，作为抛光液使用时能够有效的提高抛光效率。
同时本发明工艺简单，高效，相对于传统的制备方法具有很大的优势。
附图说明
图1显示为实施例1制备的多分散大粒径硅溶胶电镜图片。
图2显示为实施例2制备的多分散大粒径硅溶胶电镜图片。
图3显示为实施例3制备的多分散大粒径硅溶胶电镜图片。
具体实施方式
以下通过特定的具体实例说明本发明的实施方式，本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用，本说明书中的各项细节也可以基于不同观点与应用，在没有背离本发明的精神下进行各种修饰或改变。须知，下列实施例中未具体注明的工艺设备或装置均采用本领域内的常规设备或装置。此外应理解，本发明中提到的一个或多个方法步骤并不排斥在所述组合步骤前后还可以存在其他方法步骤或在这些明确提到的步骤之间还可以插入其他方法步骤，除非另有说明；而且，除非另有说明，各方法步骤的编号仅为鉴别各方法步骤的便利工具，而非为限制各方法步骤的排列次序或限定本发明可实施的范围，其相对关系的改变或调整，在无实质变更技术内容的情况下，当亦视为本发明可实施的范畴。
在下述实施例中观测硅溶胶所采用的电镜为聚焦离子束系统，美国FEI公司生产，型号为Helios NanoLab 600型号。
实施例1 多分散大粒径硅溶胶及其制备方法
步骤(1)将浓水玻璃用纯水稀释至二氧化硅含量为4％，搅拌均匀后加入到经过再生处理过的强酸型阳离子交换树脂(聚苯磺酸型)内，进行阳离子交换，得到活性硅酸，活性硅酸的pH为2.85，二氧化硅含量为4％。
步骤(2)取1wt％的氢氧化钾溶液1000mL，搅拌并加热至98℃，将上述步骤(1)制备的活性硅酸4000ml以8ml/min速度通过蠕动泵泵入进去。活性硅酸加料结束后，继续保温0.5小时。自然冷却至室温，制得粒径为20nm-30nm单分散球形硅溶胶作为晶种。
步骤(3)称取上述步骤(2)制备的晶种800ml作为母液，搅拌并加热至沸，6.5ml/min的速度加入上述步骤(1)制备的活性硅酸，同时通过蠕动泵以0.92ml/min的速度连续不断地补加所述步骤(2)制备的晶种2760ml，期间，滴加1wt％的氢氧化钾稀溶液以保持整个体系的pH值维持在9.50-10.50之间。反应结束后，在100℃下继续保温2小时，自然冷却至室温，制得多分散大粒径硅溶胶球形二氧化硅溶胶。
如图1所示，根据扫描电镜图片可知多分散大粒径硅溶胶的粒径在20nm到85nm之间分布，激光粒度分析仪(动态光散射法)测得的平均粒径为78.9nm，pH值9.96，浓度为22.4wt％。
实施例2 多分散大粒径硅溶胶及其制备方法
步骤(1)将浓水玻璃用纯水稀释至二氧化硅含量为2％，搅拌均匀后加入到经过再生处理的强酸型阳离子交换树脂(聚苯磺酸型)内，进行阳离子交换，得到活性硅酸，活性硅酸的pH为3.0。
步骤(2)取0.3wt％的氢氧化钠溶液1500mL，搅拌并加热至100℃，将上述步骤(1)制备的活性硅酸3500ml以3.5ml/min速度通过蠕动泵泵入进去。硅酸加料结束后，继续保温1.5小时。自然冷却至室温，制得粒径为20nm-30nm单分散小粒径球形硅溶胶作为晶种。
步骤(3)称取上述步骤(2)制备的晶种1000ml作为母液，搅拌并加热至沸，通过蠕动泵以5.8ml/min的速度加入上述步骤(1)制备的活 性硅酸，硅酸加料整个过程中同时通过蠕动泵以1ml/min的速度连续不断地补加的所述步骤(2)制备的晶种3847m。期间，滴加1wt％的氢氧化钠稀溶液以保持整个体系的pH值维持在9.50-10.50之间。反应结束后，在100℃下继续保温0.5小时，自然冷却至室温，制得多分散大粒径硅溶胶球形二氧化硅溶胶。
如图2所示，根据扫描电镜图片所述多分散大粒径硅溶胶的粒径在20nm到95nm之间分布，激光粒度分析仪(动态光散射法)测得的平均粒径为82.2nm，pH值10.10，浓度为20.41wt％。
实施例3 多分散大粒径硅溶胶及其制备方法
步骤(1)将浓水玻璃用纯水稀释至二氧化硅含量为6％，搅拌均匀后加入到经过再生处理的强酸型阳离子交换树脂(聚苯磺酸型)内，进行阳离子交换，得到活性硅酸，活性硅酸的pH为2.74。
步骤(2)取0.3wt％的氢氧化钠溶液1500mL，搅拌并加热至100℃，将上述步骤(1)制备的活性硅酸3500ml以3.5ml/min速度通过蠕动泵泵入进去。硅酸加料结束后，继续保温2小时。自然冷却至室温，制得粒径为20nm-30nm单分散小粒径球形硅溶胶作为晶种。
步骤(3)称取上述步骤(2)制备的晶种800ml作为母液，搅拌并加热至沸，蠕动泵以4.4ml/min的速度加入上述步骤(1)制备的活性硅酸，硅酸加料整个过程中同时通过蠕动泵以1.85ml/min的速度连续不断地补加上述步骤(2)制备的晶种9969ml。期间，滴加2wt％的氢氧化钠和氢氧化钾混合稀溶液以保持整个体系的pH值维持在9.50-10.50之间。反应完毕后，在100℃下继续保温1.2小时，自然冷却至室温，制得多分散大粒径硅溶胶球形二氧化硅溶胶。
如图3所示，根据扫描电镜图片所述多分散大粒径硅溶胶的粒径在20nm到85nm之间分布，激光粒度分析仪(动态光散射法)测得的平均粒径为68.4nm，pH值10.32，浓度为30.90wt％。
实施例4 硅溶胶抛光实验
将上述实施例1-3制备的多分散大粒径硅溶胶配置成抛光液用于蓝宝石片粗抛光。
抛光液配置方法：将本发明所制备的多分散大粒径硅溶胶用纯水稀释至二氧化硅含量为15wt％，用5wt％的氢氧化钠水溶液将pH值调为10.50，搅拌均匀后，称取1kg，即为抛光液。
抛光实验：将2英寸C相蓝宝石片通过背膜吸附法粘于抛光头上。抛光参数设置如下：抛光压力为6psi；抛光垫转速为100rpm；抛光片转速为90rpm；抛光液流速为125ml/min；抛光时间为30min。每次抛光结束后，用4英寸金刚石修复盘修复抛光垫5分钟，抛光后的蓝宝石片在清洗液中超声清洗10分钟后用氮气吹干。通过金相显微镜来观察抛光后蓝宝石片表面质量状况。通过测定蓝宝石片抛光前后质量差，计算厚度抛光速度，结果列于表1。
表1抛光实验对比结果
Figure PCTCN2016097876-appb-000001
将本发明所制备的多分散大粒径硅溶胶与传统离子交换法制备的单分散大粒径硅溶胶(90nm)进行抛光速率对比实验，前者抛光速率比后者抛光速率快37％以上。实施例1-3抛光后蓝宝石片表面质量均良好，没有明显划伤、pits等缺陷。
以上所述，仅为本发明的较佳实施例，并非对本发明任何形式上和实质上的限制，应当指出，对于本技术领域的普通技术人员，在不脱离本发明方法的前提下，还将可以做出若干改进和补充，这些改进和补充也应视为本发明的保护范围。凡熟悉本专业的技术人员，在不脱离本发明的精神和范围的情况下，当可利用以上所揭示的技术内容而做出的些许更动、修饰与演变的等同变化，均为本发明的等效实施例；同时，凡依据本发明 的实质技术对上述实施例所作的任何等同变化的更动、修饰与演变，均仍属于本发明的技术方案的范围内。

Claims (10)

  1. 一种多分散大粒径硅溶胶的制备方法，其特征在于，所述制备方法：以粒径为20nm-30nm的单分散球形硅溶胶为晶种，搅拌并同时加热，同时向反应体系不断的滴加粒径为20nm-30nm的单分散球形硅溶胶晶种和活性硅酸，在整体反应过程中采用加热浓缩法维持恒液位，同时滴加无机碱溶液以保持体系的pH值在9.5-10.5，反应结束后保温，冷却。
  2. 根据权利要求1所述的多分散大粒径硅溶胶的制备方法，其特征在于，所述制备方法具体包括以下步骤：
    步骤(1)活性硅酸制备：将二氧化硅含量为2-6wt％的水玻璃溶液，加入到强酸型阳离子交换树脂内进行阳离子交换，得到pH为2.0-4.0的活性硅酸；
    步骤(2)单分散小粒径硅溶胶晶种的制备：取0.1-1.0wt％的无机碱溶液搅拌并加热至90-100℃，再将2-4倍体积的所述步骤(1)制备的活性硅酸逐渐加入，加料结束后，继续保温，自然冷却至室温，制得粒径为20nm-30nm的单分散球形硅溶胶作为晶种；
    步骤(3)多分散大粒径硅溶胶制备：取所述步骤(2)制备的晶种作为母液，搅拌并加热至沸，然后向反应体系中以4-10ml/min的速度滴加所述步骤(1)制备的活性硅酸，同时向反应体系中以0.85-1.85ml/min的速度连续不断地补加所述步骤(2)制备的晶种，维持恒液位，同时滴加无机碱溶液以保持整个体系的pH值维持在9.50-10.50，加料结束后，继续保温，自然冷却至室温。
  3. 根据权利要求1所述的多分散大粒径硅溶胶的制备方法，其特征在于：所述步骤(1)中阳离子交换树脂是经过再生处理的。
  4. 根据权利要求1所述的多分散大粒径硅溶胶的制备方法，其特征在于：所述步骤(2)中保温的时间为0.5-2小时。
  5. 根据权利要求1所述的多分散大粒径硅溶胶的制备方法，其特征在于；所述步骤(2)中加活性硅酸的速度为2-20ml/min。
  6. 根据权利要求1所述的多分散大粒径硅溶胶的制备方法，其特征在于：所述步骤(3)中的保温时间为0.5-2小时。
  7. 根据权利要求1所述的多分散大粒径硅溶胶的制备方法，其特征在 于：所述步骤(3)中的碱液选自氢氧化钾溶液、氢氧化钠溶液中的任意一种或者两者的混合物。
  8. 采用权利要求1-7任一项所述的多分散大粒径硅溶胶的制备方法制备的多分散大粒径硅溶胶。
  9. 根据权利要求8所述的一种多分散大粒径硅溶胶，其特征在于：所述多分散大粒径硅溶胶的粒径分布范围为20nm-95nm。
  10. 如权利要求8所述的多分散大粒径硅溶胶用于制作抛光液的用途。
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