Cerium oxide polishing powder and preparation and use thereof

Abstract

The present application relates to a kind of preparation methods of cerium oxide polishing powder that can be used in fine polishing process, specifically relates to the mixed solution of cerium salt and polyol is atomized and mixed with precipitant solution simultaneously, form atomized precipitate, after drying and calcining, the cerium oxide polishing powder obtained in the method, in the cerium oxide polishing powder obtained, the average primary particle size of cerium oxide particle is 3±1nm, can be used in fine polishing process, under the optimization condition, the surface roughness of workpiece can be polished to 0.1nm below.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of surface polishing technology, and particularly relates to a preparation of cerium oxide polishing powder for fine polishing process and a use method thereof. BACKGROUND

[0002] The cerium oxide polishing liquid is widely used in the fields of ordinary glass, optical glass, high-precision optical instruments, crystal surfaces, semiconductor elements and the like. However, the cerium oxide abrasive particles in the commercially available cerium oxide polishing liquid are mostly in the range of 10-200 nm, and the preparation of cerium oxide with smaller particle size has many challenges.

[0003] The preparation methods of CeO2 mainly include gas phase method, liquid phase method and solid phase method. The gas phase method is to synthesize CeO2 by the reaction of 2 or more than 2 simple substances or compounds in a gas. Generally, the cerium oxide prepared by the gas phase method has small particle size, uniform distribution and stable properties, and is not easy to agglomerate. However, the gas phase method has a complex preparation process, expensive equipment and cannot realize industrialized mass production, so it is generally not adopted. For example, Guillou N et al.

Guillou N, et al. 1997, 8(5): 545-557

[0004] The liquid phase method is simple to operate and has strong adaptability, and is widely used in industrial production. It mainly includes precipitation method, sol-gel method, microemulsion method and electrochemical method.

[0005] The precipitation method uses a precipitant to precipitate and synthesize a precursor in a metal soluble salt solution, and then the precursor is dried and calcined to obtain cerium oxide material. By controlling the reaction conditions, the particle size and morphology of the cerium oxide material can be changed. This process is simple and easy to operate, and is widely used in the synthesis and preparation of cerium oxide. However, since this method is usually carried out in an aqueous solution, the presence of water can cause agglomeration between particles, so the key of this method is how to prevent the agglomeration between particles and obtain cerium oxide particles with uniform distribution and small size. Yin L et al.

Yin L, et al. 2002, 246(1): 78-84

Chu X, et al. 1993, 76

[0006] Sol-gel method is to prepare sol after raw material solution is hydrolyzed, alcoholized, polymerized and other series of chemical reactions, and then form gel through aging or drying. Hou Wenhua et al.

Hou Wenhua et al. 2000

[0007] Electrochemical method is to form the required substance on the electrode surface by electrolysis of solution with suitable electrode material. The CeO2 particles prepared by electrochemical method are not easy to agglomerate and the reaction process can be controlled by controlling the electrode point, but the product yield of this method is low and the cost is high, which is difficult to be applied in industry at present. Pan Zhanchang et al. prepared spherical CeO2 particles with grain size of 10 nm by electrolyzing cerium salt.

[0008] Solid phase method is to synthesize precursor by solid reaction, and then to obtain CeO2 by calcination. The CeO2 particles prepared by solid phase method have large particle size and uneven distribution, and low cerium content, which is only suitable for occasions with low performance requirement of cerium oxide. F. Bondioli et al. synthesized cerium oxide with particle size of 10-20 nm by solid phase synthesis method, and Zhuo et al.

Zhuo et al. 2004, 22(005): 641-646

[0009] In the present application, the polyol mixed solution of cerium salt and the precipitator solution are directly atomized and mixed, the atomized mixed precipitate is obtained, and then it is directly dried and calcined to prepare cerium oxide polishing powder which can be used for precision polishing, wherein the cerium oxide is granular material with average primary particle size of 3±1 nm. The preparation process is simple and efficient, easy to be industrialized, and has important application prospect. SUMMARY

[0010] The problem to be solved by the present application is to provide a preparation method of cerium oxide polishing powder which can be used in precision polishing process, in particular to the mixed solution of cerium salt and polyol and the precipitator solution are simultaneously atomized and mixed to form atomized precipitate, and cerium oxide polishing powder is obtained after drying and calcination.

[0011] The technical scheme is:

[0012] The soluble cerium salt is dissolved in the mixed solution of water and polyol to form a cerium salt solution, and the solid precipitator is dissolved to form a solution. The cerium salt solution and the precipitator solution are simultaneously atomized and contacted and mixed, the obtained atomized precipitate is dried to obtain a powder-like precipitate, and the cerium oxide polishing powder which can be used for precision polishing is obtained after calcination; wherein the cerium oxide is granular material with average primary particle size of 3±1 nm.

[0013] A scheme is provided:

[0014] The soluble salt of cerium includes one or more of cerium ammonium nitrate, cerium acetate, cerium fluoride, and cerium ammonium sulfate.

[0015] The concentration of Ce ions in the cerium salt solution is 0.02-1.5 mol / L;

[0016] The polyhydric alcohol is one or more of propylene glycol, butylene glycol, hexylene glycol, and neopentyl glycol;

[0017] The molar ratio of Ce ions to polyhydric alcohol is 5:1-1:20.

[0018] The solid precipitant is one or more of NaOH, KOH, and Ba(OH)2;

[0019] The concentration of the precipitant in the precipitant solution is 0.2-4.0 mol / L;

[0020] The spraying pressure (using a high-pressure pump to obtain pressure spraying atomization of the solution) is in the range of 6-20 MPa;

[0021] The molar ratio of Ce ions to precipitant is adjusted by adjusting the atomization feeding rate of the cerium salt and precipitant solution to be 1:2-1:20.

[0022] The atmosphere of the closed container is an inert atmosphere selected from one or more of N2, Ar, and He;

[0023] The drying temperature is 80-220°C;

[0024] The calcination temperature is 300-700°C;

[0025] The calcination atmosphere is one or more of air, an oxygen-containing inert atmosphere (O2 volume content 1%-95%, the rest being an inert atmosphere, and the inert atmosphere gas being one or more of N2, Ar, or He);

[0026] The calcination time is 4-24 h.

[0027] A solution is provided:

[0028] The soluble salt of cerium includes one or both of cerium nitrate and cerium ammonium sulfate;

[0029] The concentration of Ce ions in the cerium salt solution is 0.03-1.0 mol / L;

[0030] The polyhydric alcohol is one or both of propylene glycol and neopentyl glycol;

[0031] The molar ratio of Ce ions to polyhydric alcohol is 3:1-1:10.

[0032] The solid precipitant is one or both of NaOH and Ba(OH)2;

[0033] The concentration of the precipitant in the precipitant solution is 0.5-3.0 mol / L.

[0034] The spraying pressure (pressure spraying atomization of the solution by using a high-pressure pump) ranges from 7 to 14 MPa.

[0035] The molar ratio of Ce ions to the precipitant is adjusted by adjusting the atomization feeding rate of the cerium salt and the precipitant solution, and the molar ratio is 1:5-1:10.

[0036] The atmosphere of the closed container is an inert atmosphere selected from one or more of N2 and Ar.

[0037] The drying temperature is 100-200 DEG C.

[0038] The calcination temperature is 350-550 DEG C.

[0039] The calcination atmosphere is one or more of air, an oxygen-containing inert atmosphere (O2 volume content 5%-70%, the rest being an inert atmosphere, and the inert atmosphere gas being one or more of N2, Ar or He).

[0040] The calcination time is 8-12 h.

[0041] The cerium oxide polishing powder can be prepared into a chemical mechanical polishing liquid and applied to a fine polishing process.

[0042] Beneficial technical effects

[0043] Compared with the prior art, the present application has the following advantages: the cerium oxide polishing powder prepared by the present application has a small average primary particle size (3±1 nm), a narrow particle size distribution, good polishing performance, and can achieve a low surface roughness and few surface defects and scratches. BRIEF DESCRIPTION OF DRAWINGS

[0044] Figure 1 TEM image and particle size statistical diagram of the cerium oxide polishing powder prepared in Example 12 of the present application. DETAILED DESCRIPTION

[0045] In order to further illustrate the present application, several specific implementation cases are given below, but the present application is not limited to these examples.

[0046] Example 1

[0047] Ce-acetate was dissolved in a mixture of water and 1,3-propanediol to form a salt solution of cerium with a Ce-ion concentration of 0.02 mol / L and a molar ratio of Ce-ion to 1,3-propanediol of 5 / 1. NaOH was dissolved in water to form a 0.2 mol / L solution. The two salt solutions were simultaneously atomized and mixed. The molar ratio of Ce-ion to NaOH was controlled at 1:2 by adjusting the feed rate of the two salt solutions. The pressure during atomization was 6 MPa, and the atmosphere in the closed vessel was N2. The resulting atomized precipitate was directly dried at 80°C. The resulting powder was calcined in air at 300°C for 4 h to obtain ceria polishing powder. Electron microscopy characterization showed that the ceria was a granular material with an average primary particle size of 3 ± 1 nm.

[0048] Example 2

[0049] Ce-fluoride was dissolved in a mixture of water and 1,3-propanediol to form a salt solution of cerium with a Ce-ion concentration of 0.02 mol / L and a molar ratio of Ce-ion to 1,3-propanediol of 5 / 1. NaOH was dissolved in water to form a 0.2 mol / L solution. The two salt solutions were simultaneously atomized and mixed. The molar ratio of Ce-ion to NaOH was controlled at 1:2 by adjusting the feed rate of the two salt solutions. The pressure during atomization was 6 MPa, and the atmosphere in the closed vessel was N2. The resulting atomized precipitate was directly dried at 80°C. The resulting powder was calcined in air at 300°C for 4 h to obtain ceria polishing powder. Electron microscopy characterization showed that the ceria was a granular material with an average primary particle size of 3 ± 1 nm.

[0050] Example 3

[0051] Ce-ammonium nitrate was dissolved in a mixture of water and 1,3-propanediol to form a salt solution of cerium with a Ce-ion concentration of 0.02 mol / L and a molar ratio of Ce-ion to 1,3-propanediol of 5 / 1. NaOH was dissolved in water to form a 0.2 mol / L solution. The two salt solutions were simultaneously atomized and mixed. The molar ratio of Ce-ion to NaOH was controlled at 1:2 by adjusting the feed rate of the two salt solutions. The pressure during atomization was 6 MPa, and the atmosphere in the closed vessel was N2. The resulting atomized precipitate was directly dried at 80°C. The resulting powder was calcined in air at 300°C for 4 h to obtain ceria polishing powder. Electron microscopy characterization showed that the ceria was a granular material with an average primary particle size of 3 ± 1 nm.

[0052] Example 4

[0053] Ce(N03)3.6H20 was dissolved in a mixture of water and 1,3-propanediol to form a salt solution of cerium, with a Ce ion concentration of 0.02 mol / L and a molar ratio of Ce ion to 1,3-propanediol of 5 / 1. NaOH was dissolved in water to form a 0.2 mol / L solution. The two salt solutions were simultaneously atomized and mixed. The molar ratio of Ce ion to NaOH was controlled at 1:2 by adjusting the feed rates of the two salt solutions. The atomization pressure was 6 MPa, and the atmosphere in the closed vessel was N2. The resulting atomized precipitate was directly dried at a temperature of 80°C. The resulting powder was calcined in air at 300°C for 4 h to obtain ceria polishing powder. Electron microscopy characterization showed that the ceria was a granular material with an average primary particle size of 3 ± 1 nm.

[0054] Example 5

[0055] Ce(N03)3.6H20 was dissolved in a mixture of water and 1,3-propanediol to form a salt solution of cerium, with a Ce ion concentration of 0.02 mol / L and a molar ratio of Ce ion to 1,3-propanediol of 5 / 1. NaOH was dissolved in water to form a 0.2 mol / L solution. The two salt solutions were simultaneously atomized and mixed. The molar ratio of Ce ion to NaOH was controlled at 1:2 by adjusting the feed rates of the two salt solutions. The atomization pressure was 6 MPa, and the atmosphere in the closed vessel was N2. The resulting atomized precipitate was directly dried at a temperature of 80°C. The resulting powder was calcined in air at 300°C for 4 h to obtain ceria polishing powder. Electron microscopy characterization showed that the ceria was a granular material with an average primary particle size of 3 ± 1 nm.

[0056] Example 6

[0057] Ce(N03)3.6H20 was dissolved in a mixture of water and 1,3-propanediol to form a salt solution of cerium, with a Ce ion concentration of 0.02 mol / L and a molar ratio of Ce ion to 1,3-propanediol of 5 / 1. NaOH was dissolved in water to form a 0.2 mol / L solution. The two salt solutions were simultaneously atomized and mixed. The molar ratio of Ce ion to NaOH was controlled at 1:2 by adjusting the feed rates of the two salt solutions. The atomization pressure was 6 MPa, and the atmosphere in the closed vessel was N2. The resulting atomized precipitate was directly dried at a temperature of 80°C. The resulting powder was calcined in air at 300°C for 4 h to obtain ceria polishing powder. Electron microscopy characterization showed that the ceria was a granular material with an average primary particle size of 3 ± 1 nm.

[0058] Example 7

[0059] Dissolve cerium acetate in a mixture of water and neopentyl glycol to form a salt solution of cerium, in which the concentration of Ce ions is 0.02 mol / L and the molar ratio of Ce ions to neopentyl glycol is 5 / 1; dissolve NaOH in water to form a 0.2 mol / L solution; simultaneously atomize and mix the two salt solutions. By adjusting the feeding rate of the two salt solutions, control the molar ratio of Ce ions to NaOH to be 1:2, the pressure during atomization is 6 MPa, and the atmosphere in the closed container is N2. The obtained atomized precipitate directly enters drying, the drying temperature is 80°C, the obtained powder-like precipitate is calcined in air at 300°C for 4 h, and cerium oxide polishing powder is obtained. Electron microscope characterization shows that the cerium oxide is a granular material with an average primary particle size of 3±1 nm.

[0060] Example 8

[0061] Dissolve cerium acetate in a mixture of water and neopentyl glycol to form a salt solution of cerium, in which the concentration of Ce ions is 0.02 mol / L and the molar ratio of Ce ions to neopentyl glycol is 5 / 1; dissolve NaOH in water to form a 0.2 mol / L solution; simultaneously atomize and mix the two salt solutions. By adjusting the feeding rate of the two salt solutions, control the molar ratio of Ce ions to NaOH to be 1:2, the pressure during atomization is 6 MPa, and the atmosphere in the closed container is N2. The obtained atomized precipitate directly enters drying, the drying temperature is 80°C, the obtained powder-like precipitate is calcined in air at 300°C for 4 h, and cerium oxide polishing powder is obtained. Electron microscope characterization shows that the cerium oxide is a granular material with an average primary particle size of 3±1 nm.

[0062] Example 9

[0063] Dissolve cerium acetate in a mixture of water and neopentyl glycol to form a salt solution of cerium, in which the concentration of Ce ions is 0.02 mol / L and the molar ratio of Ce ions to neopentyl glycol is 5 / 1; dissolve NaOH in water to form a 0.2 mol / L solution; simultaneously atomize and mix the two salt solutions. By adjusting the feeding rate of the two salt solutions, control the molar ratio of Ce ions to NaOH to be 1:2, the pressure during atomization is 6 MPa, and the atmosphere in the closed container is N2. The obtained atomized precipitate directly enters drying, the drying temperature is 80°C, the obtained powder-like precipitate is calcined in air at 300°C for 4 h, and cerium oxide polishing powder is obtained. Electron microscope characterization shows that the cerium oxide is a granular material with an average primary particle size of 3±1 nm.

[0064] Example 10

[0065] Ce-acetate was dissolved in a mixture of water and neopentyl glycol to form a salt solution of cerium, in which the concentration of Ce ions was 1.5 mol / L and the molar ratio of Ce ions to neopentyl glycol was 5 / 1. NaOH was dissolved in water to form a 0.2 mol / L solution. The two salt solutions were simultaneously atomized and mixed. The molar ratio of Ce ions to NaOH was controlled to be 1:2 by adjusting the feeding rate of the two salt solutions. The pressure during atomization was 6 MPa and the atmosphere in the closed container was N2. The obtained atomized precipitate was directly dried at 80°C. The obtained powder-like precipitate was calcined in air at 300°C for 4 h to obtain ceria polishing powder. Electron microscopy characterization showed that the ceria was a granular material with an average primary particle size of 3±1 nm.

[0066] Example 11

[0067] Ce-acetate was dissolved in a mixture of water and neopentyl glycol to form a salt solution of cerium, in which the concentration of Ce ions was 0.03 mol / L and the molar ratio of Ce ions to neopentyl glycol was 3 / 1. NaOH was dissolved in water to form a 0.2 mol / L solution. The two salt solutions were simultaneously atomized and mixed. The molar ratio of Ce ions to NaOH was controlled to be 1:2 by adjusting the feeding rate of the two salt solutions. The pressure during atomization was 6 MPa and the atmosphere in the closed container was N2. The obtained atomized precipitate was directly dried at 80°C. The obtained powder-like precipitate was calcined in air at 300°C for 4 h to obtain ceria polishing powder. Electron microscopy characterization showed that the ceria was a granular material with an average primary particle size of 3±1 nm.

[0068] Example 12

[0069] Ce-acetate was dissolved in a mixture of water and neopentyl glycol to form a salt solution of cerium, in which the concentration of Ce ions was 0.03 mol / L and the molar ratio of Ce ions to neopentyl glycol was 1 / 10. NaOH was dissolved in water to form a 0.2 mol / L solution. The two salt solutions were simultaneously atomized and mixed. The molar ratio of Ce ions to NaOH was controlled to be 1:2 by adjusting the feeding rate of the two salt solutions. The pressure during atomization was 6 MPa and the atmosphere in the closed container was N2. The obtained atomized precipitate was directly dried at 80°C. The obtained powder-like precipitate was calcined in air at 300°C for 4 h to obtain ceria polishing powder. Electron microscopy characterization showed that the ceria was a granular material with an average primary particle size of 3±1 nm.

[0070] Example 13

[0071] Ce-acetate was dissolved in a mixture of water and neopentyl glycol to form a salt solution of cerium, in which the concentration of Ce ion was 0.03 mol / L and the molar ratio of Ce ion to neopentyl glycol was 1 / 20; NaOH was dissolved in water to form a 0.2 mol / L solution; the above two salt solutions were simultaneously atomized and mixed. By adjusting the feeding rate of the two salt solutions, the molar ratio of Ce ion to NaOH was controlled to be 1:2, the pressure during atomization was 6 MPa, and the atmosphere in the closed container was N2. The obtained atomized precipitate directly entered drying, the drying temperature was 80°C, the obtained powder-like precipitate was calcined in air at 300°C for 4 h, and cerium oxide polishing powder was obtained. Electron microscope characterization showed that the cerium oxide was a granular material with an average primary particle size of 3±1 nm.

[0072] Example 14

[0073] Ce-acetate was dissolved in a mixture of water and neopentyl glycol to form a salt solution of cerium, in which the concentration of Ce ion was 0.03 mol / L and the molar ratio of Ce ion to neopentyl glycol was 3 / 1; KOH was dissolved in water to form a 0.2 mol / L solution; the above two salt solutions were simultaneously atomized and mixed. By adjusting the feeding rate of the two salt solutions, the molar ratio of Ce ion to NaOH was controlled to be 1:2, the pressure during atomization was 6 MPa, and the atmosphere in the closed container was N2. The obtained atomized precipitate directly entered drying, the drying temperature was 80°C, the obtained powder-like precipitate was calcined in air at 300°C for 4 h, and cerium oxide polishing powder was obtained. Electron microscope characterization showed that the cerium oxide was a granular material with an average primary particle size of 3±1 nm.

[0074] Example 15

[0075] Ce-acetate was dissolved in a mixture of water and neopentyl glycol to form a salt solution of cerium, in which the concentration of Ce ion was 0.03 mol / L and the molar ratio of Ce ion to neopentyl glycol was 3 / 1; Ba(OH)2 was dissolved in water to form a 0.2 mol / L solution; the above two salt solutions were simultaneously atomized and mixed. By adjusting the feeding rate of the two salt solutions, the molar ratio of Ce ion to NaOH was controlled to be 1:2, the pressure during atomization was 6 MPa, and the atmosphere in the closed container was N2. The obtained atomized precipitate directly entered drying, the drying temperature was 80°C, the obtained powder-like precipitate was calcined in air at 300°C for 4 h, and cerium oxide polishing powder was obtained. Electron microscope characterization showed that the cerium oxide was a granular material with an average primary particle size of 3±1 nm.

[0076] Example 16

[0077] Ce-acetate was dissolved in a mixture of water and neopentyl glycol to form a salt solution of cerium with a Ce-ion concentration of 0.03 mol / L and a molar ratio of Ce-ion to neopentyl glycol of 3 / 1. Ba(OH)2was dissolved in water to form a 0.5 mol / L solution. The two salt solutions were simultaneously atomized and mixed. The molar ratio of Ce-ion to NaOH was controlled to be 1:2 by adjusting the feed rate of the two salt solutions. The pressure during atomization was 6 MPa and the atmosphere in the closed vessel was N2. The resulting atomized precipitate was directly dried at a temperature of 80 °C. The resulting powder was calcined in air at 300 °C for 4 h to obtain ceria polishing powder. Electron microscopy characterization showed that the ceria was a particulate material with an average primary particle size of 3 ± 1 nm.

[0078] Example 17

[0079] Ce-acetate was dissolved in a mixture of water and neopentyl glycol to form a salt solution of cerium with a Ce-ion concentration of 0.03 mol / L and a molar ratio of Ce-ion to neopentyl glycol of 3 / 1. Ba(OH)2was dissolved in water to form a 3 mol / L solution. The two salt solutions were simultaneously atomized and mixed. The molar ratio of Ce-ion to NaOH was controlled to be 1:2 by adjusting the feed rate of the two salt solutions. The pressure during atomization was 6 MPa and the atmosphere in the closed vessel was N2. The resulting atomized precipitate was directly dried at a temperature of 80 °C. The resulting powder was calcined in air at 300 °C for 4 h to obtain ceria polishing powder. Electron microscopy characterization showed that the ceria was a particulate material with an average primary particle size of 3 ± 1 nm.

[0080] Example 18

[0081] Ce-acetate was dissolved in a mixture of water and neopentyl glycol to form a salt solution of cerium with a Ce-ion concentration of 0.03 mol / L and a molar ratio of Ce-ion to neopentyl glycol of 3 / 1. Ba(OH)2was dissolved in water to form a 4 mol / L solution. The two salt solutions were simultaneously atomized and mixed. The molar ratio of Ce-ion to NaOH was controlled to be 1:2 by adjusting the feed rate of the two salt solutions. The pressure during atomization was 6 MPa and the atmosphere in the closed vessel was N2. The resulting atomized precipitate was directly dried at a temperature of 80 °C. The resulting powder was calcined in air at 300 °C for 4 h to obtain ceria polishing powder. Electron microscopy characterization showed that the ceria was a particulate material with an average primary particle size of 3 ± 1 nm.

[0082] Example 19

[0083] Ce-acetate was dissolved in a mixture of water and neopentyl glycol to form a salt solution of cerium, in which the concentration of Ce ion was 0.03 mol / L and the molar ratio of Ce ion to neopentyl glycol was 3 / 1. Ba(OH)2 was dissolved in water to form a 0.5 mol / L solution. The two salt solutions were simultaneously atomized and mixed. The molar ratio of Ce ion to NaOH was controlled to be 1:5 by adjusting the feeding rate of the two salt solutions. The pressure during atomization was 6 MPa and the atmosphere in the closed container was N2. The obtained atomized precipitate was directly dried at 80°C. The obtained powder-like precipitate was calcined in air at 300°C for 4 h to obtain ceria polishing powder. Electron microscope characterization showed that the ceria was granular material with an average primary particle size of 3±1 nm.

[0084] Example 20

[0085] Ce-acetate was dissolved in a mixture of water and neopentyl glycol to form a salt solution of cerium, in which the concentration of Ce ion was 0.03 mol / L and the molar ratio of Ce ion to neopentyl glycol was 3 / 1. Ba(OH)2 was dissolved in water to form a 0.5 mol / L solution. The two salt solutions were simultaneously atomized and mixed. The molar ratio of Ce ion to NaOH was controlled to be 1:10 by adjusting the feeding rate of the two salt solutions. The pressure during atomization was 6 MPa and the atmosphere in the closed container was N2. The obtained atomized precipitate was directly dried at 80°C. The obtained powder-like precipitate was calcined in air at 300°C for 4 h to obtain ceria polishing powder. Electron microscope characterization showed that the ceria was granular material with an average primary particle size of 3±1 nm.

[0086] Example 21

[0087] Ce-acetate was dissolved in a mixture of water and neopentyl glycol to form a salt solution of cerium, in which the concentration of Ce ion was 0.03 mol / L and the molar ratio of Ce ion to neopentyl glycol was 3 / 1. Ba(OH)2 was dissolved in water to form a 0.5 mol / L solution. The two salt solutions were simultaneously atomized and mixed. The molar ratio of Ce ion to NaOH was controlled to be 1:20 by adjusting the feeding rate of the two salt solutions. The pressure during atomization was 6 MPa and the atmosphere in the closed container was N2. The obtained atomized precipitate was directly dried at 80°C. The obtained powder-like precipitate was calcined in air at 300°C for 4 h to obtain ceria polishing powder. Electron microscope characterization showed that the ceria was granular material with an average primary particle size of 3±1 nm.

[0088] Example 22

[0089] Ce-acetate was dissolved in a mixture of water and neopentyl glycol to form a salt solution of cerium, in which the concentration of Ce ion was 0.03 mol / L and the molar ratio of Ce ion to neopentyl glycol was 3 / 1; Ba(OH)2 was dissolved in water to form a 0.5 mol / L solution; the two salt solutions were simultaneously atomized and mixed. By adjusting the feeding rate of the two salt solutions, the molar ratio of Ce ion to NaOH was controlled to be 1:5, the pressure during atomization was 7 MPa, and the atmosphere in the closed container was N2. The obtained atomized precipitate directly entered drying, the drying temperature was 80°C, the obtained powder-like precipitate was calcined in air at 300°C for 4 h, and cerium oxide polishing powder was obtained. Electron microscope characterization showed that the cerium oxide was a granular material with an average primary particle size of 3±1 nm.

[0090] Example 23

[0091] Ce-acetate was dissolved in a mixture of water and neopentyl glycol to form a salt solution of cerium, in which the concentration of Ce ion was 0.03 mol / L and the molar ratio of Ce ion to neopentyl glycol was 3 / 1; Ba(OH)2 was dissolved in water to form a 0.5 mol / L solution; the two salt solutions were simultaneously atomized and mixed. By adjusting the feeding rate of the two salt solutions, the molar ratio of Ce ion to NaOH was controlled to be 1:5, the pressure during atomization was 14 MPa, and the atmosphere in the closed container was N2. The obtained atomized precipitate directly entered drying, the drying temperature was 80°C, the obtained powder-like precipitate was calcined in air at 300°C for 4 h, and cerium oxide polishing powder was obtained. Electron microscope characterization showed that the cerium oxide was a granular material with an average primary particle size of 3±1 nm.

[0092] Example 24

[0093] Ce-acetate was dissolved in a mixture of water and neopentyl glycol to form a salt solution of cerium, in which the concentration of Ce ion was 0.03 mol / L and the molar ratio of Ce ion to neopentyl glycol was 3 / 1; Ba(OH)2 was dissolved in water to form a 0.5 mol / L solution; the two salt solutions were simultaneously atomized and mixed. By adjusting the feeding rate of the two salt solutions, the molar ratio of Ce ion to NaOH was controlled to be 1:5, the pressure during atomization was 20 MPa, and the atmosphere in the closed container was N2. The obtained atomized precipitate directly entered drying, the drying temperature was 80°C, the obtained powder-like precipitate was calcined in air at 300°C for 4 h, and cerium oxide polishing powder was obtained. Electron microscope characterization showed that the cerium oxide was a granular material with an average primary particle size of 3±1 nm.

[0094] Example 25

[0095] Ce-acetate was dissolved in a mixture of water and neopentyl glycol to form a salt solution of cerium, in which the concentration of Ce ion was 0.03 mol / L and the molar ratio of Ce ion to neopentyl glycol was 3 / 1; Ba(OH)2 was dissolved in water to form a 0.5 mol / L solution; the two salt solutions were simultaneously atomized and mixed. By adjusting the feeding rate of the two salt solutions, the molar ratio of Ce ion to NaOH was controlled to be 1:5, the pressure during atomization was 7 MPa, and the atmosphere in the closed container was Ar. The obtained atomized precipitate directly entered drying, the drying temperature was 80°C, the obtained powder-like precipitate was calcined in air at 300°C for 4 h, and cerium oxide polishing powder was obtained. Electron microscope characterization showed that the cerium oxide was a granular material with an average primary particle size of 3±1 nm.

[0096] Example 26

[0097] Ce-acetate was dissolved in a mixture of water and neopentyl glycol to form a salt solution of cerium, in which the concentration of Ce ion was 0.03 mol / L and the molar ratio of Ce ion to neopentyl glycol was 3 / 1; Ba(OH)2 was dissolved in water to form a 0.5 mol / L solution; the two salt solutions were simultaneously atomized and mixed. By adjusting the feeding rate of the two salt solutions, the molar ratio of Ce ion to NaOH was controlled to be 1:5, the pressure during atomization was 7 MPa, and the atmosphere in the closed container was N2. The obtained atomized precipitate directly entered drying, the drying temperature was 100°C, the obtained powder-like precipitate was calcined in air at 300°C for 4 h, and cerium oxide polishing powder was obtained. Electron microscope characterization showed that the cerium oxide was a granular material with an average primary particle size of 3±1 nm.

[0098] Example 27

[0099] Ce-acetate was dissolved in a mixture of water and neopentyl glycol to form a salt solution of cerium, in which the concentration of Ce ion was 0.03 mol / L and the molar ratio of Ce ion to neopentyl glycol was 3 / 1; Ba(OH)2 was dissolved in water to form a 0.5 mol / L solution; the two salt solutions were simultaneously atomized and mixed. By adjusting the feeding rate of the two salt solutions, the molar ratio of Ce ion to NaOH was controlled to be 1:5, the pressure during atomization was 7 MPa, and the atmosphere in the closed container was N2. The obtained atomized precipitate directly entered drying, the drying temperature was 200°C, the obtained powder-like precipitate was calcined in air at 300°C for 4 h, and cerium oxide polishing powder was obtained. Electron microscope characterization showed that the cerium oxide was a granular material with an average primary particle size of 3±1 nm.

[0100] Example 28

[0101] Ce-acetate was dissolved in a mixture of water and neopentyl glycol to form a salt solution of cerium, in which the concentration of Ce ion was 0.03 mol / L and the molar ratio of Ce ion to neopentyl glycol was 3 / 1; Ba(OH)2 was dissolved in water to form a 0.5 mol / L solution; the two salt solutions were simultaneously atomized and mixed. By adjusting the feeding rate of the two salt solutions, the molar ratio of Ce ion to NaOH was controlled to be 1:5, the pressure during atomization was 7 MPa, and the atmosphere in the closed container was N2. The obtained atomized precipitate directly entered drying, the drying temperature was 220 °C, the obtained powder-like precipitate was calcined in air at 300 °C for 4 h, and cerium oxide polishing powder was obtained. Electron microscope characterization showed that the cerium oxide was a granular material with an average primary particle size of 3±1 nm.

[0102] Example 29

[0103] Ce-acetate was dissolved in a mixture of water and neopentyl glycol to form a salt solution of cerium, in which the concentration of Ce ion was 0.03 mol / L and the molar ratio of Ce ion to neopentyl glycol was 3 / 1; Ba(OH)2 was dissolved in water to form a 0.5 mol / L solution; the two salt solutions were simultaneously atomized and mixed. By adjusting the feeding rate of the two salt solutions, the molar ratio of Ce ion to NaOH was controlled to be 1:5, the pressure during atomization was 7 MPa, and the atmosphere in the closed container was N2. The obtained atomized precipitate directly entered drying, the drying temperature was 100 °C, the obtained powder-like precipitate was calcined in air at 350 °C for 4 h, and cerium oxide polishing powder was obtained. Electron microscope characterization showed that the cerium oxide was a granular material with an average primary particle size of 3±1 nm.

[0104] Example 30

[0105] Ce-acetate was dissolved in a mixture of water and neopentyl glycol to form a salt solution of cerium, in which the concentration of Ce ion was 0.03 mol / L and the molar ratio of Ce ion to neopentyl glycol was 3 / 1; Ba(OH)2 was dissolved in water to form a 0.5 mol / L solution; the two salt solutions were simultaneously atomized and mixed. By adjusting the feeding rate of the two salt solutions, the molar ratio of Ce ion to NaOH was controlled to be 1:5, the pressure during atomization was 7 MPa, and the atmosphere in the closed container was N2. The obtained atomized precipitate directly entered drying, the drying temperature was 100 °C, the obtained powder-like precipitate was calcined in air at 550 °C for 4 h, and cerium oxide polishing powder was obtained. Electron microscope characterization showed that the cerium oxide was a granular material with an average primary particle size of 3±1 nm.

[0106] Example 31

[0107] Ce-acetate was dissolved in a mixture of water and neopentyl glycol to form a salt solution of cerium with a Ce-ion concentration of 0.03 mol / L and a molar ratio of Ce-ion to neopentyl glycol of 3 / 1. Ba(OH)2was dissolved in water to form a 0.5 mol / L solution. The two salt solutions were simultaneously atomized and mixed. The molar ratio of Ce-ion to NaOH was controlled to be 1:5 by adjusting the feed rate of the two salt solutions. The pressure during atomization was 7 MPa and the atmosphere in the closed vessel was N2. The obtained atomized precipitate was directly dried at a temperature of 100 °C. The obtained powder-like precipitate was calcined at 350 °C in an atmosphere of 5 vol O2(nitrogen balance) for 12 h to obtain ceria polishing powder. Electron microscopy characterization showed that the ceria was a granular material with an average primary particle size of 3 ± 1 nm.

[0108] Example 32

[0109] Ce-acetate was dissolved in a mixture of water and neopentyl glycol to form a salt solution of cerium with a Ce-ion concentration of 0.03 mol / L and a molar ratio of Ce-ion to neopentyl glycol of 3 / 1. Ba(OH)2was dissolved in water to form a 0.5 mol / L solution. The two salt solutions were simultaneously atomized and mixed. The molar ratio of Ce-ion to NaOH was controlled to be 1:5 by adjusting the feed rate of the two salt solutions. The pressure during atomization was 7 MPa and the atmosphere in the closed vessel was N2. The obtained atomized precipitate was directly dried at a temperature of 100 °C. The obtained powder-like precipitate was calcined at 350 °C in an atmosphere of 5 vol O2(nitrogen balance) for 12 h to obtain ceria polishing powder. Electron microscopy characterization showed that the ceria was a granular material with an average primary particle size of 3 ± 1 nm.

[0110] Example 33

[0111] Ce-acetate was dissolved in a mixture of water and neopentyl glycol to form a salt solution of cerium with a Ce-ion concentration of 0.03 mol / L and a molar ratio of Ce-ion to neopentyl glycol of 3 / 1. Ba(OH)2was dissolved in water to form a 0.5 mol / L solution. The two salt solutions were simultaneously atomized and mixed. The molar ratio of Ce-ion to NaOH was controlled to be 1:5 by adjusting the feed rate of the two salt solutions. The pressure during atomization was 7 MPa and the atmosphere in the closed vessel was N2. The obtained atomized precipitate was directly dried at a temperature of 100 °C. The obtained powder-like precipitate was calcined at 350 °C in an atmosphere of 5 vol O2(nitrogen balance) for 12 h to obtain ceria polishing powder. Electron microscopy characterization showed that the ceria was a granular material with an average primary particle size of 3 ± 1 nm.

[0112] Example 34

[0113] Ce-acetate was dissolved in a mixture of water and neopentyl glycol to form a salt solution of cerium, in which the concentration of Ce ions was 0.03 mol / L and the molar ratio of Ce ions to neopentyl glycol was 3 / 1. Ba(OH)2 was dissolved in water to form a 0.5 mol / L solution. The two salt solutions were simultaneously atomized and mixed. The molar ratio of Ce ions to NaOH was controlled to be 1:5 by adjusting the feeding rate of the two salt solutions. The pressure during atomization was 7 MPa and the atmosphere in the closed container was N2. The obtained atomized precipitate was directly dried at 100°C. The obtained powder-like precipitate was calcined at 350°C for 8 h in an atmosphere of 70 vol O2 (nitrogen balance) to obtain ceria polishing powder. Electron microscope characterization showed that the ceria was granular material with an average primary particle size of 3±1 nm.

[0114] Example 35

[0115] Ce-acetate was dissolved in a mixture of water and neopentyl glycol to form a salt solution of cerium, in which the concentration of Ce ions was 0.03 mol / L and the molar ratio of Ce ions to neopentyl glycol was 3 / 1. Ba(OH)2 was dissolved in water to form a 0.5 mol / L solution. The two salt solutions were simultaneously atomized and mixed. The molar ratio of Ce ions to NaOH was controlled to be 1:5 by adjusting the feeding rate of the two salt solutions. The pressure during atomization was 7 MPa and the atmosphere in the closed container was N2. The obtained atomized precipitate was directly dried at 100°C. The obtained powder-like precipitate was calcined at 350°C for 8 h in an atmosphere of 70 vol O2 (nitrogen balance) to obtain ceria polishing powder. Electron microscope characterization showed that the ceria was granular material with an average primary particle size of 3±1 nm.

[0116] The ceria polishing powder obtained in the above Examples 1-35 was prepared into a polishing liquid with a concentration of 150 g / L. A KUKA (KR C4) numerical control precision lapping and polishing machine was used to polish fused silica glass (initial surface roughness 0.5±0.1 nm) of , automatic stirring and beating, the polishing agent shaft rotation speed was 150 r / min, the pressure was 0.1 MPa, the polishing skin was KSP90-0.8, the polishing time was 1.0 h, the mass of the glass after washing and drying was recorded every half hour, and the glass scratch was observed in a dark room after polishing. The following tests were performed: the removal rate was determined by weighing the mass change of the substrate before and after polishing on an analytical balance (nm / min); the surface roughness Ra was measured on the substrate surface using an AFM; and the surface defects and scratches were observed and checked using a differential interference microscope to represent the adhesion state and the number of scratches on the substrate surface.

[0117] Table 1 Polishing effect

[0118]

[0119]

[0120] Preferred ranges:

[0121] From Examples 1-4, it can be seen that polishing powder prepared from cerium acetate and cerium ammonium sulfate has better performance. From Examples 1, 5-7, it can be seen that using 1,3-propanediol and neopentyl glycol as polyols is better. From Examples 8-13, it can be seen that a moderate Ce ion concentration and a moderate molar ratio with polyols are better. From Examples 16-21, it can be seen that a moderate concentration of precipitant and a moderate molar ratio with precipitant are better. From Examples 26-31, it can be seen that moderate drying and calcination temperatures are better.

[0122] The above detailed description of the specific embodiments of the present application is only as an example, and the present application is not limited to the specific embodiments described above. Any equivalent modifications and substitutions made by those skilled in the art to the present application are also within the scope of the present application. Therefore, equivalent transformations and modifications made without departing from the spirit and scope of the present application should be encompassed within the scope of the present application.

Claims

1. The application of a cerium oxide polishing powder in a fine polishing process, characterized in that: Cerium oxide polishing powder is formulated into a chemical mechanical polishing slurry and applied to fine polishing processes. The preparation method of cerium oxide polishing powder is as follows: Cerium acetate is dissolved in a mixed solution of water and neopentyl glycol to form a cerium salt solution, wherein the Ce ion concentration is 0.03 mol / L and the molar ratio of Ce ions to neopentyl glycol is 3 / 1; Ba(OH)2 is dissolved in water to form a 0.5 mol / L solution; the two salt solutions are simultaneously atomized and mixed, and the molar ratio of Ce ions to precipitant is controlled to be 1:5 by adjusting the feed rate of the two salt solutions. The atomization pressure is 7 MPa, the atmosphere in the sealed container is N2, and the resulting atomized precipitate is directly dried at 100℃. The resulting powdered precipitate is calcined at 350℃ in an atmosphere with an oxygen volume content of 1% and the remainder being nitrogen for 24 h to obtain cerium oxide polishing powder. Electron microscopy characterization shows that cerium oxide is a particulate material with an average primary particle size of 3±1 nm.

2. The application of a cerium oxide polishing powder in a fine polishing process, characterized in that: Cerium oxide polishing powder is formulated into a chemical mechanical polishing slurry and applied to fine polishing processes. The preparation method of cerium oxide polishing powder is as follows: Cerium acetate is dissolved in a mixed solution of water and neopentyl glycol to form a cerium salt solution, wherein the Ce ion concentration is 0.03 mol / L and the molar ratio of Ce ions to neopentyl glycol is 3 / 1; Ba(OH)2 is dissolved in water to form a 0.5 mol / L solution; the two salt solutions are simultaneously atomized and mixed, and the molar ratio of Ce ions to precipitant is controlled to be 1:5 by adjusting the feed rate of the two salt solutions. The atomization pressure is 7 MPa, the atmosphere in the sealed container is N2, and the resulting atomized precipitate is directly dried at a drying temperature of 100℃. The resulting powdered precipitate is calcined at 350℃ in an atmosphere with an oxygen volume content of 5% and the remainder being nitrogen for 12 hours to obtain cerium oxide polishing powder. Electron microscopy characterization shows that cerium oxide is a particulate material with an average primary particle size of 3±1 nm.

3. The application of a cerium oxide polishing powder in a fine polishing process, characterized in that: Cerium oxide polishing powder is formulated into a chemical mechanical polishing slurry and applied to fine polishing processes. The preparation method of cerium oxide polishing powder is as follows: Cerium acetate is dissolved in a mixed solution of water and neopentyl glycol to form a cerium salt solution, wherein the Ce ion concentration is 0.03 mol / L and the molar ratio of Ce ions to neopentyl glycol is 3 / 1; Ba(OH)₂ is dissolved in water to form a 0.5 mol / L solution; the two salt solutions are simultaneously atomized and mixed, and the molar ratio of Ce ions to precipitant is controlled to be 1:5 by adjusting the feed rate of the two salt solutions. The atomization pressure is 7 MPa, the atmosphere in the sealed container is N₂, and the resulting atomized precipitate is directly dried at 100℃. The resulting powdered precipitate is then dried at 350℃. o C was calcined in an atmosphere with 70% oxygen by volume and the remainder nitrogen for 8 hours to obtain cerium oxide polishing powder. Electron microscopy characterization showed that cerium oxide was a particulate material with an average primary particle size of 3±1 nm.

4. The application of a cerium oxide polishing powder in a fine polishing process, characterized in that: Cerium oxide polishing powder is formulated into a chemical mechanical polishing slurry and applied to fine polishing processes. The preparation method of cerium oxide polishing powder is as follows: Cerium acetate is dissolved in a mixed solution of water and neopentyl glycol to form a cerium salt solution, wherein the Ce ion concentration is 0.03 mol / L and the molar ratio of Ce ions to neopentyl glycol is 3 / 1; Ba(OH)2 is dissolved in water to form a 0.5 mol / L solution; the two salt solutions are simultaneously atomized and mixed, and the molar ratio of Ce ions to precipitant is controlled to be 1:5 by adjusting the feed rate of the two salt solutions. The atomization pressure is 7 MPa, the atmosphere in the sealed container is N2, and the resulting atomized precipitate is directly dried at 100℃. The resulting powdered precipitate is calcined at 350℃ in an atmosphere with an oxygen volume content of 95% and the remainder being nitrogen for 4 hours to obtain cerium oxide polishing powder. Electron microscopy characterization shows that cerium oxide is a particulate material with an average primary particle size of 3±1 nm.

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