CN112778970A - Method for preparing surface-modified cerium oxide particles and polishing solution containing same - Google Patents
Method for preparing surface-modified cerium oxide particles and polishing solution containing same Download PDFInfo
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- CN112778970A CN112778970A CN202110003323.6A CN202110003323A CN112778970A CN 112778970 A CN112778970 A CN 112778970A CN 202110003323 A CN202110003323 A CN 202110003323A CN 112778970 A CN112778970 A CN 112778970A
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1436—Composite particles, e.g. coated particles
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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
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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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
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
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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
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- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
Abstract
The invention discloses a method for preparing surface-modified cerium oxide particles and a polishing solution containing the same. The preparation method of the surface modified cerium oxide particles comprises the following steps of modifying cerium oxide under the action of a modifier shown as a formula I to obtain the surface modified cerium oxide particles. The modified cerium oxide particles prepared by the preparation method can be used as abrasive particles of polishing solution, can selectively polish silicon oxide films, and have small surface roughness after polishing.
Description
Technical Field
The invention belongs to the technical field of abrasives for chemical mechanical polishing, and particularly relates to a method for preparing surface-modified cerium oxide particles and a polishing solution containing the same.
Background
Cerium oxide has a long history as a polishing abrasive for precision glass polishing and polishing of silicon dioxide dielectric layers of very large scale integrated circuits, and because the cerium oxide abrasive can chemically react with silicon oxide, the polishing rate of the cerium oxide is about three times that of silicon oxide under the same conditions, especially a high removal rate in a neutral polishing solution is maintained, and the polishing selectivity between silicon oxide and silicon nitride is high. However, the performance of the nano cerium oxide polishing depends on the dispersion condition, and the nano cerium oxide is easy to agglomerate like other nano particles due to the extremely high surface energy of the nano cerium oxide, so that the surface of a workpiece after polishing is damaged, specifically, the defects of large surface roughness, scratches and the like after polishing are shown. Therefore, the dispersion of the cerium oxide becomes one of the most critical technologies for preparing the cerium oxide polishing solution at present, and the dispersion by adopting a surface modification method is one of the methods for improving the polishing performance of the cerium oxide polishing solution. The invention aims to improve the performances of the cerium oxide polishing solution in the aspects of surface roughness, polishing selectivity and polishing defect reduction.
Disclosure of Invention
The invention aims to solve the problem that the surface of a polished workpiece is damaged due to the fact that existing cerium oxide abrasive particles are easy to agglomerate, and particularly the defect that the surface roughness is large after polishing is solved by the invention, and provides a method for preparing surface-modified cerium oxide particles and polishing solution containing the same. The modified cerium oxide particles prepared by the preparation method can be used as abrasive particles, can selectively polish a silicon oxide film, and have small surface roughness after polishing.
The invention provides a modification method of cerium oxide particles, which comprises the following steps of modifying cerium oxide under the action of a modifier shown as a formula I to obtain surface-modified cerium oxide particles;
wherein each R is independently C1-C8Alkyl, amino, hydroxy, glycidyl, "substituted with one or more R1Substituted C1-C6Alkyl radical ", C2-C6Alkenyl, "substituted with one or more R4Substituted silicon group ", C3-C8Cycloalkyl radicals, substituted by one or more R2Substituted C3-C8Cycloalkyl "," by one or two R3Substituted acryloyl "," substituted with one or more R5Substituted siloxy ", C6-C10Aryl, 3-propoxy, (2, 3-propanediol) propoxy, 1-propyl methacrylate, 3-tosyloxypropyl, or 3-glycidyl) propoxy;
each R1Independently halogen, hydroxy, amino, mercapto, 2- (aminoethyl) amino, (chloromethyl) phenyl, 3, 4-epoxycyclohexyl, C2-C6Alkenyl, propoxy, propylmethacryloyl, trans-3, 4-cyclohexanediol, chlorodimethylsilyl or trichlorosilyl;
each R2Independently is C1-C6Alkyl or C2-C6An alkenyl group;
each R3Independently is C1-C6An alkyl group;
each R4Independently is C1-C6An alkyl group;
each R5Independently is C1-C6Alkyl radical, C2-C6Alkenyl, 1, 2-epoxy-4-ethylcyclohexyl, 3-glycidoxypropyl, cyclohexenyl, 2- (4-cyclohexenyl) ethyl, hydroxypropyl, biphenyl or cyanoAnd (4) propyl.
In some embodiments, when each R is independently C1-C8When alkyl, said C1-C8Alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, octyl, isooctyl, primary butyl, isobutyl or tertiary butyl, preferably methyl, isooctyl, isobutyl or n-propyl.
In some embodiments, when each R is independently "substituted with one or more R1Substituted C1-C6When alkyl is mentioned, said C1-C6Alkyl is C1-C4An alkyl group; for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, primary butyl or tertiary butyl, preferably methyl, ethyl or n-propyl.
In some embodiments, when each R is independently C2-C6When alkenyl, said C2-C6Alkenyl is C2-C4An alkenyl group; for example
Preferably, it is
(vinyl group) or
In some embodiments, when each R is independently C3-C8When there is a cycloalkyl group, said C3-C8Cycloalkyl being C3-C6Cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, preferably cyclopentyl or cyclohexyl.
In some embodiments, when each R is independently "substituted with one or more R2Substituted C3-C8Cycloalkyl "said C3-C8Cycloalkyl being C3-C6Cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, is preferably cyclohexyl.
In some embodiments, when each R is independently "C6-C10Aryl group isSaid C is6-C10Aryl is phenyl.
In some embodiments, when each R is1When independently halogen, said halogen is fluorine, chlorine, bromine or iodine; chlorine is preferred.
In some embodiments, when each R is1Independently is C2-C6When alkenyl, said C2-C6Alkenyl is C2-C4An alkenyl group; for example
Preferably, it is
(vinyl group) or
In some embodiments, when each R is2Independently is C1-C6When alkyl, said C1-C6Alkyl is C1-C4An alkyl group; for example methyl, n-butyl, isobutyl or tert-butyl, preferably methyl, ethyl, n-propyl or isopropyl.
In some embodiments, when each R is2Independently is C2-C6When alkenyl, said C2-C6Alkenyl is C2-C4An alkenyl group; for example
Preferably, it is
(vinyl group) or
In some embodiments, when each R is4Independently is C1-C6When alkyl, said C1-C6Alkyl is C1-C4An alkyl group; for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isopropylButyl, primary butyl or tertiary butyl, preferably methyl.
In some embodiments, when each R is3Independently is C1-C6When alkyl, said C1-C6Alkyl is C1-C4An alkyl group; for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, primary butyl or tertiary butyl, preferably methyl.
In some embodiments, when each R is5Independently is C1-C6When alkyl, said C1-C6Alkyl is C1-C4An alkyl group; for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, primary butyl or tertiary butyl, preferably methyl.
In some embodiments, when each R is5Independently is C2-C6When alkenyl, said C2-C6Alkenyl is C2-C4An alkenyl group; for example
Preferably, it is
(vinyl group) or
In certain embodiments, preferably each R is independently amino, hydroxy, methyl, vinyl, propyl, isooctyl, phenyl, chloropropyl, allyl, cyclohexyl, cyclopentyl, isobutyl, 3-hydroxypropyl, dimethylsilyl
3-propoxy, propylmethacryloyl, 2- [ (chloromethyl) phenyl]Ethyl, 2- (3, 4-epoxycyclohexyl) ethyl, [3- (2-aminoethyl) amino]Propyl, 1-propyl methacrylate, (2, 3-propanediol) propoxy, 2- (trans-3, 4-cyclohexanediol) ethyl, 3-cyclohexenyl, (3-mercapto) propyl, 3-tosyloxypropyl, (3-glycidyl) propoxy, 4- (chloromethyl) phenyl, trivinylSiloxy, (3-hydroxypropyl) dimethylsiloxy, 2- (chlorodimethylsilyl) ethyl, 2-trichlorosilylethyl, cyanopropyldimethylsiloxy, methacryloyl, glycidyl, biphenylvinylsiloxy, (1, 2-epoxy-4-ethylcyclohexyl) dimethylsiloxy, (3-glycidoxypropyl) dimethylsiloxy or 2- (4-cyclohexenyl) ethyldimethylsiloxy; preferably amino or chloropropyl
Dimethylsilyl, vinyl or methacryloyl.
In certain embodiments, each R is amino, "substituted with one or more C1-C4Alkyl-substituted silyl group "," C substituted by one halogen1-C4Alkyl radical ", C2-C4Alkenyl or "substituted by one or two C1-C4Alkyl substituted acryloyl ".
In certain embodiments, said plurality is 2,3, 4, or 5; preferably 2 or 3.
In the invention, the modifier shown in the formula I is any one of the following compounds,
in the present invention, preferably, the modification comprises the following steps: in water, the modifier shown as the formula I, cerium oxide and a polymer additive are mixed, the pH value is adjusted to 4-7 by using a pH regulator, and the mixture reacts at the temperature of 30-100 ℃ to obtain the surface modified cerium oxide particles.
In the modification, the cerium oxide is cerium oxide particles, the particle size of which can be conventional in the art, and preferably, the particle size (D90) of the cerium oxide particles is 20-50 nm.
In the modification, the cerium oxide is preferably 2 to 10% by mass, for example 2%, 10% or 5%, preferably 2 to 5%. Wherein, the mass percent of the cerium oxide is the percentage of the cerium oxide in the total mass of all the raw materials in the modification process.
In the modification, preferably, the mass ratio of the modifier shown in the formula I to the cerium oxide is 1: (1-20), for example 1: 2. 1: 10. 2: 5 or 1: 5, preferably 1: (2-10); more preferably 1: (5-10).
In the modification, preferably, the polymer auxiliary agent is one or more of polyitaconic acid, polymaleic acid, polyacrylic acid and polymethacrylic acid, and is preferably polyitaconic acid.
In the modification, the polymer auxiliary preferably has a weight average molecular weight (Mw) of 5000.
In the modification, the amount of the polymer auxiliary agent can be conventional in the art, and preferably, the mass ratio of the polymer auxiliary agent to the cerium oxide is 1: (10-50), for example, 1: 10. 1: 25 or 1: 50, preferably 1: 25.
in the modification, the pH regulator is a conventional pH regulator, preferably one or more of acetic acid, hydrochloric acid, nitric acid, phosphoric acid and a buffer solution, and preferably acetic acid; more preferably 10% by mass of an aqueous acetic acid solution.
In the modification, the pH is preferably 5.5 to 6.5, such as 5.5, 6 or 6.5, preferably 6.5.
In the modification, the reaction temperature is preferably 50-100 ℃; for example 50 deg.C, 60 deg.C or 100 deg.C, preferably 60 deg.C.
In the modification, the reaction time for the modification may be a reaction time conventional in the art, and the reaction time is generally related to the scale of the reaction, and is preferably 4 to 12 hours, for example, 5 hours, 4 hours or 12 hours, and more preferably 5 hours.
In the modification, the mixing method can be one or more of mechanical stirring, magnetic stirring, ultrasound, megasonic, oscillation and the like.
In the invention, the water can be pure water; the pure water is selected from one or more of deionized water, distilled water and ultrapure water.
In the present invention, the modification reaction further comprises a post-treatment after the end of the modification reaction, and the post-treatment preferably comprises the following steps: after the reaction, the reaction solution is subjected to solid-liquid separation (for example, filtration, centrifugation, ultrafiltration, or the like), washing, and drying.
The invention also provides a preparation method of the polishing solution containing the surface modified cerium oxide particles, which comprises the following steps: mixing the surface-modified cerium oxide particles obtained by the modification method with water.
In the method for preparing the polishing solution, the mass percentage of the surface-modified cerium oxide particles in the polishing solution is 0.1% -10%, and preferably, the mass percentage of the surface-modified cerium oxide particles in the polishing solution is 0.5%.
In the preparation method of the polishing solution, the water is pure water; preferably, the water is selected from one or more of deionized water, distilled water and ultrapure water.
In the invention, the polishing solution prepared by the polishing solution preparation method can be used in the field of chemical mechanical polishing; furthermore, the polishing solution can be used for polishing silicon dioxide dielectric layers of integrated circuits; further, when the silicon oxide film and the silicon nitride film are polished at the same time, the silicon oxide film is polished at a high selectivity ratio.
The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: the cerium oxide particles prepared by the surface modification method can be used as CMP abrasive particles, and the cerium oxide particles subjected to surface modification can reduce the agglomeration of cerium oxide abrasives, improve the dispersibility of the cerium oxide abrasives in water, be applied to chemical mechanical polishing and improve the surface quality of polished workpieces. The polishing solution prepared by the preparation method of the polishing solution containing the surface modified cerium oxide particles has high polishing selectivity on a silicon oxide film and a silicon nitride film, low Dishing removal amount of a groove part and small roughness Root Mean Square (RMS).
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
In the following examples, water refers to deionized water.
Preparation of surface modified cerium oxide particles
Examples 1 to 20
Mixing a modifier shown as a formula I, cerium oxide particles with the diameter of 20-50nm (D90), a polymer additive and water, and stirring and dispersing; subsequently, the pH was adjusted with a dilute aqueous acetic acid solution (10% by mass), followed by stirring to obtain a cerium oxide dispersion. And (3) reacting the dispersion under the condition of heating. After the reaction is finished, centrifugally separating and drying to finally obtain the modified surface modified cerium oxide particles. In the following examples, the specific operation temperature is not limited, and it is meant to be carried out at room temperature (20 to 35 ℃ C.).
The kinds of the raw material components of examples 1 to 20 are shown in Table 1.
TABLE 1
The contents (mass percentages) of the respective raw material components of examples 1 to 20 and the reaction conditions for preparing the surface-modified cerium oxide abrasives are shown in table 2.
TABLE 2
Comparative example 1
The contents of the respective components and reaction conditions of comparative example 1 were the same as those of example 1 except that the modifier of comparative example 1 had a structure of
Secondly, preparing polishing solution and measuring polishing effect
Polishing effect experiment:
the polishing conditions were as follows
1. A polishing device: AP-300(CTS)
2. Gasket: IC1000
3. Polishing time: 60s
4. Platen speed (flaten speed): 110rpm
5. Spindle speed (spindle speed): 108rpm
6. Wafer pressure: 3.5psi
7. Slurry flow rate (flow rate): 200ml/min
8. Wafer: PE-TEOS (thickness)
) (ii) a Silicon nitride wafer (thickness)
) (ii) a Patterned wafer
The RMS test method is as follows: the 10 μm by 10 μm area of the PE-TEOS wafer surface was tested using an AFM atomic force microscope (Rootmean Square).
Silicon oxide film polishing rate (RR): the film thickness is measured by a Filmetrics F54 film thickness measuring instrument
Polishing rate of silicon nitride film: the film thickness is measured by a Filmetrics F54 film thickness measuring instrument
Selection ratio: silicon oxide film RR/silicon nitride film RR
Amount of Dishing (dispersing) in the groove portion of 100 μm/100 μm region: determination using a stylus type step meter (manufactured by model P16 KLA-tencor)
Application examples 1 to 20
Preparing a polishing solution:
the modified cerium oxide abrasive grains prepared in examples 1 to 20 and deionized water were respectively used to prepare polishing solutions with a mass percentage of 0.5%. The polishing solutions were used to polish under the above-mentioned conditions, and the polishing effects are shown in table 3.
TABLE 3
From the application results of examples 1 to 20, it is understood that when the surface-modified cerium oxide CMP abrasive grains prepared by the present invention were used to prepare polishing solutions, the RMS value was 3.001nm to 3.680nm, and the selection ratio of silicon oxide film RR/silicon nitride film RR was 19.1 to 13.3; the amount of Dishing (dispersing) in the groove portion of the 100 μm/100 μm region was set to
Comparative application example
Comparative application example 1
The modified cerium oxide abrasive grain prepared in comparative example 1 and deionized water were used to prepare a polishing solution having a mass percentage of 0.5%.
Comparative application example 2
And (3) preparing 0.5 mass percent of polishing solution by taking the non-modified cerium oxide abrasive particles (the diameter (D90) is 20-50nm) and deionized water.
The polishing solutions were used to polish under the above-mentioned conditions, and the polishing effects are shown in table 4.
TABLE 4
When a polishing liquid was prepared from the cerium oxide CMP abrasive grains obtained in comparative example 1, the RMS value was 3.134nm, and the selectivity of the silicon oxide film RR/silicon nitride film RR was 10.9; the amount of Dishing (dispersing) in the groove portion of the 100 μm/100 μm region was set to
When the specific modifier is not used, the prepared abrasive particles can achieve better RMS value, but the selection ratio of the silicon oxide film to the silicon nitride film can only achieve 10.9, and the quantity of the polishing exceeds the quantity of the polishing
As can be seen from the application of the polishing slurry prepared without any modified cerium oxide CMP abrasive grains, the RMS was 5.016nm without modification, the silicon oxide film to silicon nitride selectivity was 8.9, and the Dishing (sinking) amount of the groove portion in the 100 μm/100 μm region was set to be
Claims (10)
1. A modification method of cerium oxide particles is characterized by comprising the following steps of modifying cerium oxide under the action of a modifier shown as a formula I to obtain surface-modified cerium oxide particles;
wherein each R is independently C1-C8Alkyl, amino, hydroxy, glycidyl, "substituted with one or more R1Substituted C1-C6Alkyl radical ", C2-C6Alkenyl, "substituted with one or more R4Substituted silicon group ", C3-C8Cycloalkyl radicals, substituted by one or more R2Substituted C3-C8Cycloalkyl "," by one or two R3Substituted acryloyl "," substituted with one or more R5Substituted siloxy ", C6-C10Aryl, 3-propoxy, (2, 3-propanediol) propoxy, 1-propyl methacrylate, 3-tosyloxypropyl, or 3-glycidyl) propoxy;
each R1Independently halogen, hydroxy, amino, mercapto, 2- (aminoethyl) amino, (chloromethyl) phenyl, 3, 4-epoxycyclohexyl, C2-C6Alkenyl, propoxy, propylmethacryloyl, trans-3, 4-cyclohexanediol, chlorodimethylsilyl or trichlorosilyl;
each R2Independently is C1-C6Alkyl or C2-C6An alkenyl group;
each R3Independently is C1-C6An alkyl group;
each R4Independently is C1-C6An alkyl group;
each R5Independently is C1-C6Alkyl radical, C2-C6Alkenyl, 1, 2-epoxy-4-ethylcyclohexyl, 3-glycidoxypropyl, cyclohexenyl, 2- (4-cyclohexenyl) ethyl, hydroxypropyl, biphenyl or cyanopropyl.
2. The method for modifying cerium oxide particles according to claim 1, wherein when each R is independently C1-C8When alkyl, said C1-C8Alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, octyl, isooctyl, primary butyl, isobutyl or tertiary butyl, preferably methyl, isooctyl, isobutyl or n-propyl;
and/or, when each R is independently "substituted with one or more R1Substituted C1-C6When alkyl is mentioned, said C1-C6Alkyl is C1-C4An alkyl group; such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, primary butyl or tertiary butyl, preferably methyl, ethyl or n-propyl;
and/or the presence of a gas in the gas,when each R is independently C2-C6When alkenyl, said C2-C6Alkenyl is C2-C4An alkenyl group; for example
Preferably, it is
And/or, when each R is independently C3-C8When there is a cycloalkyl group, said C3-C8Cycloalkyl being C3-C6Cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, preferably cyclopentyl or cyclohexyl;
and/or, when each R is independently "substituted with one or more R2Substituted C3-C8Cycloalkyl "said C3-C8Cycloalkyl being C3-C6Cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, preferably cyclohexyl;
and/or, when each R is independently "C6-C10Aryl "is said to C6-C10Aryl is phenyl;
and/or, when each R is1When independently halogen, said halogen is fluorine, chlorine, bromine or iodine; preferably chlorine;
and/or, when each R is1Is C2-C6When alkenyl, said C2-C6Alkenyl is C2-C4An alkenyl group; for example
Preferably, it is
And/or, when each R is2Independently is C1-C6When alkyl, said C1-C6Alkyl is C1-C4An alkyl group; for example methyl, n-butyl, isobutyl or tert-butyl, preferably methyl, ethyl, n-propyl or isopropyl;
and/or, when each R is2Independently is C2-C6When alkenyl, said C2-C6Alkenyl is C2-C4An alkenyl group; for example
Preferably, it is
And/or, when each R is4Independently is C1-C6When alkyl, said C1-C6Alkyl is C1-C4An alkyl group; such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, primary butyl or tertiary butyl, preferably methyl;
and/or, when each R is3Independently is C1-C6When alkyl, said C1-C6Alkyl is C1-C4An alkyl group; such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, primary butyl or tertiary butyl, preferably methyl;
and/or, when each R is5Independently is C1-C6When alkyl, said C1-C6Alkyl is C1-C4An alkyl group; such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, primary butyl or tertiary butyl, preferably methyl;
and/or, when each R is5Independently is C2-C6When alkenyl, said C2-C6Alkenyl is C2-C4An alkenyl group; for example
Preferably, it is
And/or, said plurality is 2,3, 4 or 5; preferably 2 or 3.
3. The method of modifying cerium oxide particles according to claim 2, wherein each R is independently amino, hydroxyl, methyl, vinyl, propyl, isooctyl, phenyl, chloropropyl, allyl, cyclohexyl, cyclopentyl, isobutyl, 3-hydroxypropyl, dimethylsilyl, 3-propoxy, propylmethacryloyl, 2- [ (chloromethyl) phenyl ] ethyl, 2- (3, 4-epoxycyclohexyl) ethyl, [3- (2-aminoethyl) amino ] propyl, 1-propyl methacrylate, (2, 3-propanediol) propoxy, 2- (trans-3, 4-cyclohexanediol) ethyl, 3-cyclohexenyl, (3-mercapto) propyl, 3-toluenesulfonyloxypropyl, (3-glycidyl) propoxy, or the like, 4- (chloromethyl) phenyl, trivinylsiloxy, (3-hydroxypropyl) dimethylsiloxy, 2- (chlorodimethylsilyl) ethyl, 2-trichlorosilylethyl, cyanopropyldimethylsiloxy, methacryloyl, glycidyl, biphenylvinylsiloxy, (1, 2-epoxy-4-ethylcyclohexyl) dimethylsiloxy, (3-glycidoxypropyl) dimethylsiloxy or 2- (4-cyclohexenyl) ethyldimethylsiloxy; preferably amino, chloropropyl, dimethylsilyl, vinyl or methacryloyl.
4. The method for modifying cerium oxide particles according to claim 2, wherein each R is an amino group, a "mono-or poly-C1-C4Alkyl-substituted silyl group "," C substituted by one halogen1-C4Alkyl radical ", C2-C4Alkenyl or "substituted by one or two C1-C4Alkyl substituted acryloyl ".
5. The method for modifying cerium oxide particles according to claim 1, wherein the modifier represented by formula I is any one of the following compounds,
6. the method of modifying cerium oxide particles according to claim 1, wherein in the modification, the cerium oxide is cerium oxide particles, preferably, the cerium oxide particles have a particle size of 20 to 50 nm; the particle size is D90;
and/or in the modification, the mass ratio of the modifier shown in the formula I to the cerium oxide is 1: (1-20), for example 1: 2. 1: 10. 2: 5 or 1: 5, preferably 1: (2-10); more preferably 1: (5-10).
7. The method for modifying cerium oxide particles according to claim 1, wherein the modification comprises the steps of: in water, the modifier shown as the formula I, cerium oxide and a polymer additive are mixed, the pH value is adjusted to 4-7 by using a pH regulator, and the mixture reacts at the temperature of 30-100 ℃ to obtain the surface modified cerium oxide particles.
8. The method for modifying cerium oxide particles according to claim 7, wherein the cerium oxide is present in an amount of 2% to 10%, such as 2%, 10% or 5%, preferably 2% to 5% by mass; wherein the mass percent of the cerium oxide is the percentage of the cerium oxide in the total mass of all the raw materials in the modification process;
and/or in the modification, the polymer auxiliary agent is one or more of polyitaconic acid, polymaleic acid, polyacrylic acid and polymethacrylic acid, preferably polyitaconic acid;
and/or in the modification, the weight average molecular weight of the polymer auxiliary agent is 5000;
and/or the mass ratio of the polymer auxiliary agent to the cerium oxide is 1: (10-50), for example, 1: 10. 1: 25 or 1: 50, preferably 1: 25;
and/or in the modification, the pH regulator is one or more of acetic acid, hydrochloric acid, nitric acid, phosphoric acid and a buffer solution, and preferably acetic acid; more preferably 10% by mass of an aqueous acetic acid solution;
and/or, in said modification, said pH is 5.5 to 6.5, such as 5.5, 6 or 6.5, preferably 6.5;
and/or, in the modification, the reaction temperature is 50-100 ℃; for example 50 ℃, 60 ℃ or 100 ℃, preferably 60 ℃;
and/or, in the modification, the reaction time of the modification is 4 to 12h, such as 5h, 4h or 12h, more preferably 5 h;
and/or the mixing method is one or more of mechanical stirring, magnetic stirring, ultrasound, megasonic and oscillation;
and/or the water is pure water; preferably, the water is selected from one or more of deionized water, distilled water and ultrapure water;
and/or, the modification reaction also comprises post-treatment after the end, and the post-treatment preferably comprises the following steps: and (3) carrying out solid-liquid separation, washing and drying on the reaction liquid after the reaction is finished.
9. A method for preparing a polishing solution containing surface-modified cerium oxide particles is characterized by comprising the following steps: mixing the surface-modified cerium oxide particles prepared by the modification method according to any one of claims 1 to 8 with water.
10. The method of claim 9, wherein the surface-modified cerium oxide particles are present in the polishing slurry in an amount of 0.1 to 10% by weight; preferably, the mass percentage of the surface-modified cerium oxide particles in the polishing solution is 0.5%;
and/or in the preparation method of the polishing solution, the water is pure water; preferably, the water is selected from one or more of deionized water, distilled water and ultrapure water;
and/or the polishing solution is used for polishing the silicon dioxide dielectric layer of the integrated circuit; further, when the silicon oxide film and the silicon nitride film are polished at the same time, the silicon oxide film is polished at a high selectivity ratio.
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