CN115160935A - Octahedral cerium oxide abrasive particle polishing solution and preparation method and application thereof - Google Patents
Octahedral cerium oxide abrasive particle polishing solution and preparation method and application thereof Download PDFInfo
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- 239000002245 particle Substances 0.000 title claims abstract description 63
- 238000005498 polishing Methods 0.000 title claims abstract description 60
- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 58
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000006061 abrasive grain Substances 0.000 claims abstract description 39
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000008367 deionised water Substances 0.000 claims abstract description 23
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 23
- 239000004094 surface-active agent Substances 0.000 claims abstract description 18
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 13
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 25
- 239000000725 suspension Substances 0.000 claims description 23
- 239000000047 product Substances 0.000 claims description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 7
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 3
- 150000004677 hydrates Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 11
- 230000003746 surface roughness Effects 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000004381 surface treatment Methods 0.000 abstract description 2
- 238000002835 absorbance Methods 0.000 description 16
- 239000006185 dispersion Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 235000012431 wafers Nutrition 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
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- 239000000463 material Substances 0.000 description 7
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- 239000002002 slurry Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
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- 238000004566 IR spectroscopy Methods 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 239000012695 Ce precursor Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 241000722270 Regulus Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
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Images
Classifications
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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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to the technical field of surface treatment, in particular to octahedral cerium oxide abrasive grain polishing solution and a preparation method and application thereof. The invention uses Ce 3+ And polyvinylpyrrolidone is used as a raw material, and the molar ratio of cerium nitrate hexahydrate to polyvinylpyrrolidone is controlled to be 2:1, the volume ratio of the absolute ethyl alcohol to the deionized water is 3:1,Ce 3+ The concentration is 0.1mol/L, and the octahedral cerium oxide abrasive particles with octahedral appearance, particle size of about 150nm and uniform particle size distribution are successfully prepared. Based on the specific octahedral cerium oxide abrasive particles of the invention, 0.05mol/L KMnO is combined by selecting Cetyl Trimethyl Ammonium Bromide (CTAB) or Sodium Dodecyl Benzene Sulfonate (SDBS) with specific concentration and specific type of surfactant 4 And the polishing solution prepared by controlling the pH value of the polishing solution to be 2 finally realizes the technical effects that the polished SiC wafer is not less than 800nm/h, and the surface roughness of the wafer is not more than 0.28 nm.
Description
Technical Field
The invention relates to the technical field of surface treatment, in particular to the field of chemical mechanical polishing, and specifically relates to an octahedral cerium oxide abrasive grain polishing solution, and a preparation method and application thereof.
Background
In optical glass, glass halfThe abrasive particles most commonly used in the chemical mechanical polishing process of conductor wafers and the like include colloidal Silica (SiO) 2 ) Aluminum oxide (Al) 2 O 3 )、CeO 2 And the like. Colloidal SiO 2 The abrasive particles are spherical, the particle size is about 100nm, the particle size distribution is uniform, good surface quality can be obtained, and the material removal rate of hard and brittle workpieces is low. Al (aluminum) 2 O 3 The abrasive grains have irregular surface shapes and high hardness, and are liable to cause scratches on the surface of a workpiece. CeO (CeO) 2 The abrasive particles have strong surface chemical activity, can generate chemical teeth which are easy to remove on the surface of a workpiece, and are easy to obtain excellent polishing performance, but the production process is not mature.
At present, in CeO 2 Some methods of making abrasive particles have also emerged in the field of abrasive particle applications, mainly gas phase, solid phase and liquid phase methods. The gas phase method refers to a process of reacting two or more simple substances or compounds in gas to prepare CeO 2 The abrasive particles tend to be more stable in properties, smaller in particle size and more uniform in distribution, however, the preparation process is more complicated, and the equipment is more expensive and is not easy to be adopted frequently. The solid phase method refers to a process of synthesizing a precursor by a solid reactant and then calcining the precursor to obtain a final product, and the method has simpler equipment and operation process, but the prepared CeO 2 Large particle size, nonuniform particle size distribution and low purity, thus being only suitable for CeO 2 When the quality requirement of the particles is not high. The liquid phase method synthesizes the cerium precursor by directly controlling the reaction conditions such as reactant concentration, dispersant concentration, stirring speed, reaction time, reaction temperature and the like. Compared with other synthesis methods, the liquid phase method has simple production equipment, easily controlled process and high purity of the synthesized product, and is suitable for industrial production and preparation of CeO 2 The most common method for the particles is that the shape, the size and the particle size distribution of the abrasive particles are not controllable, the abrasive particles are not uniform, the abrasive particles are easy to agglomerate when being used for manufacturing polishing solution, the influence on the polishing performance is large, and the abrasive particles are not beneficial to CeO 2 Use of particles in a polishing slurry. The development of a cerium oxide polishing solution with a material removal rate of not less than 800nm/h and a wafer surface roughness of not more than 0.28nm is an urgent technical problem to be solved in the field.
Disclosure of Invention
The technical problem is as follows:
developing a cerium oxide polishing solution with a material removal rate not less than 800nm/h and a wafer surface roughness not more than 0.28 nm.
The technical scheme is as follows:
the first purpose of the invention is to provide a preparation process of octahedral cerium oxide abrasive grain polishing solution, which sequentially comprises the following steps:
(1) Preparing octahedral cerium oxide abrasive particles:
a. adding Ce 3+ The source and polyvinylpyrrolidone (PVP) were dissolved in a mixed solution of anhydrous ethanol and deionized water at a molar ratio of 2 3+ Uniformly mixing the solution with the concentration of 0.1mol/L until the solution is clear and transparent; wherein the volume ratio of the absolute ethyl alcohol to the deionized water in the mixed solution of the absolute ethyl alcohol and the deionized water is 3;
b. transferring the solution into a closed reaction kettle, heating to 120 ℃, reacting for 20 hours, and naturally cooling to room temperature;
c. centrifugally cleaning the obtained product by using deionized water and absolute ethyl alcohol respectively; then the obtained precipitate is dried in vacuum;
d. slowly heating the obtained product to 500 ℃, calcining for 1h, naturally cooling to room temperature, and fully grinding to obtain octahedral cerium oxide abrasive particles; the octahedral cerium oxide abrasive particles are CeO with a cubic fluorite structure 2 The microcosmic appearance is octahedron shape, the grain diameter is 100-200 nm, and the grain diameter distribution is uniform;
(2) Preparing a polishing solution:
s1, dissolving a surfactant in deionized water to ensure that the concentration of the surfactant is 0.005-0.020 wt%; adding the octahedral cerium oxide abrasive particles prepared in the step (1) into the mixture, and performing ultrasonic dispersion to form CeO with the concentration of 2wt% 2 A suspension; wherein the surfactant is cetyl trimethylammonium bromide (CTAB) or Sodium Dodecyl Benzene Sulfonate (SDBS);
s2, adding into CeO 2 KMnO is added into the suspension 4 Mixing to obtain KMnO 4 The concentration is 0.05mol/L;
and S3, adjusting the pH value of the system to be 2 to obtain the octahedral cerium oxide abrasive grain polishing solution.
As a preferred embodiment of the present invention, in step S1, the surfactant is cetyltrimethylammonium bromide (CTAB) and the surfactant concentration is 0.015wt%.
As a preferred embodiment of the present invention, in step S1, the surfactant is Sodium Dodecylbenzenesulfonate (SDBS) with a surfactant concentration of 0.005wt%.
As a preferred embodiment of the present invention, in the step c, vacuum drying: vacuum drying at 60 deg.C for 12h.
As a preferred embodiment of the present invention, ce 3+ The source comprises Ce (NO) 3 ) 3 And/or hydrates thereof.
As a preferred embodiment of the present invention, in the step S1, ultrasonic dispersion: ultrasonic dispersion is carried out for 10-20 min. More preferably 10min.
In a preferred embodiment of the present invention, in step S3, the pH of the system is adjusted by using a potassium hydroxide solution and/or a dilute nitric acid solution.
In a preferred embodiment of the present invention, the kneading is performed by stirring in step a, step S2 or step S3 at a stirring speed of 200 to 600r/min.
The second objective of the invention is to provide the octahedral cerium oxide abrasive grain polishing solution prepared by the method.
The third objective of the present invention is to provide an application of the aforementioned octahedral cerium oxide abrasive grain polishing solution in the chemical mechanical polishing field.
Has the beneficial effects that:
(1) The invention optimizes the preparation method of the cerium oxide abrasive particles, and adopts Ce 3+ The method mainly comprises the following steps of taking polyvinylpyrrolidone as a raw material, taking ethanol-water with a specific ratio as a solvent, and controlling the molar ratio of cerium nitrate hexahydrate to polyvinylpyrrolidone to be 2:1, the volume ratio of the absolute ethyl alcohol to the deionized water is 3:1, control of Ce 3+ The concentration is 0.1mol/L, and the octahedron shape and the grain diameter are successfully preparedThe octahedral cerium oxide abrasive particles with the size of about 150nm and uniform particle size distribution overcome the technical obstacles that the cerium oxide abrasive particles synthesized by a liquid phase method in the prior art are uncontrollable in morphology and size and uneven in particle size distribution, and are easy to agglomerate when used for manufacturing polishing solution.
(2) Based on the specific octahedral cerium oxide abrasive particles, 0.05mol/L KMnO (sodium dodecyl benzene sulfonate) is combined by selecting Cetyl Trimethyl Ammonium Bromide (CTAB) or Sodium Dodecyl Benzene Sulfonate (SDBS) with specific concentration and specific type of surfactant 4 And the polishing solution prepared by controlling the pH value of the polishing solution to be 2 finally realizes that the surface roughness of the polished SiC wafer is not less than 800nm/h, and the surface roughness of the wafer is not more than 0.28nm, thereby obtaining unexpected technical effects.
(3) According to the preparation method of the octahedral cerium oxide abrasive grain polishing solution, provided by the invention, when the concentration of Cetyl Trimethyl Ammonium Bromide (CTAB) is 0.015wt% and the pH value is 2, the absorbance value of the polishing solution is larger, the dispersion stability is highest, the material removal rate of a polished SiC wafer can reach 916nm/h, and the surface roughness is 0.269nm.
Drawings
FIG. 1 is a FTIR plot of octahedral cerium oxide abrasive grains made in example 1.
Fig. 2 is an XRD pattern of the octahedral cerium oxide abrasive grains prepared in example 1.
Fig. 3 is an SEM image of the octahedral cerium oxide abrasive grains prepared in example 1.
FIG. 4 is a graph of absorbance versus pH for the octahedral cerium oxide abrasive particles of example 1.
FIG. 5 is a plot of absorbance as a function of CTAB concentration for polishing solutions of octahedral cerium oxide abrasive grains prepared in example 1.
FIG. 6 is a graph of the absorbance of polishing slurry with SDBS concentration for the octahedral cerium oxide abrasive grains prepared in example 1.
FIG. 7 is a graph of the absorbance of polishing slurry with PEG-2000 concentration for the octahedral ceria abrasive particles prepared in example 1.
Fig. 8 is a graph showing the material removal rate and surface roughness value of SiC after polishing using the octahedral cerium oxide abrasive grain polishing solutions prepared by the methods of comparative example 1 and preferred examples 2 to 4.
Detailed Description
Example 1
A preparation process of octahedral cerium oxide abrasive particles comprises the following steps:
(1) 40mmol of Ce (NO) 3 ) 3 ·6H 2 O and 20mmol of polyvinylpyrrolidone (PVP) were dissolved in 400mL of a mixed solution of anhydrous ethanol and deionized water (the volume ratio of the anhydrous ethanol to the deionized water was 3 3+ The solution with the concentration of 0.10mol/L is magnetically stirred for about 0.5h until the solution is clear and transparent;
(2) Transferring the solution into a stainless steel reaction kettle with the volume of 500mL, heating to 120 ℃, reacting for 20h, and naturally cooling to room temperature;
(3) Centrifugally cleaning the obtained product for 3 times by using deionized water and absolute ethyl alcohol respectively; and the obtained precipitate is dried in vacuum for 12 hours at the temperature of 60 ℃;
(4) Slowly heating the obtained product to 500 ℃, calcining for 1h, naturally cooling to room temperature, and fully grinding to obtain CeO 2 Particles (octahedral ceria abrasive grains).
Characterization and dispersion stability performance test of the octahedral cerium oxide abrasive particles:
1. infrared spectroscopic examination of the octahedral cerium oxide abrasive grains obtained in example 1 by means of a Fourier Infrared Spectroscopy (ALPHA) set at a wavelength ranging from 4000 to 450cm -1 。
The absorption peaks for the samples are shown in FIG. 1 to occur at about 3410, 1660, 1560, 480cm -1 To (3). 3410cm -1 The absorption peak at (a) is caused by stretching vibration of the OH-group, indicating that free water is contained in the product. 1560cm -1 、1660cm -1 The absorption peaks at (a) are due to the vibration of the C-N, C = O groups, respectively, indicating that the sample coordinates to the-NH-C = O group in the PVP during the reaction. The sample is 400-500 cm -1 The absorption peak appears in the range, indicating that CeO is formed by hydrothermal reaction 2 And (3) particles.
2. The phase of the sample of octahedral cerium oxide abrasive grains obtained in example 1 was analyzed by an X-ray diffractometer (D8 advance), a copper target (incident wavelength λ =0.15406 mm) was set as a radiation source, the scanning speed was 8 °/min, and the scanning angle range was 20 to 90 °.
Fig. 2 shows that the sample has distinct diffraction peaks near 2 θ =28.5 °, 33.1 °, 47.5 °, and 56.3 °, corresponding to the (111), (200), (220), and (311) crystal planes, respectively, and the positions and intensities of the diffraction peaks are the same as those of CeO 2 The standard patterns (# PDF 34-0394) are identical without other miscellaneous peaks, which indicates that the reaction obtains CeO with cubic fluorite structure 2 Particles, consistent with the results of the Fourier Infrared Spectroscopy test.
3. The morphology and particle size of the octahedral cerium oxide abrasive grain sample prepared in example 1 were observed using a field emission scanning electron microscope (Regulus 8100).
CeO of FIG. 3 2 The particles are octahedral, the particle size is about 150nm, and the particle size distribution is uniform.
4. An absorbance test was used to investigate the effect of the physical dispersion pattern on the dispersion stability of the octahedral cerium oxide abrasive grains prepared in example 1. The octahedral cerium oxide abrasive grains prepared in example 1 were dissolved in deionized water to prepare CeO 2 Suspension with abrasive grain concentration of 0.02 wt%. For exploring ultrasonic oscillation time to CeO 2 Effect of Dispersion stability the suspension was shaken at 240w of ultrasonic power for various times and the upper suspension was taken for absorbance test.
The results show that the ultrasonic oscillation is about 10min, the dispersion stability of the suspension is optimal, and then the absorbance tends to be stable.
5. An absorbance test was used to characterize the effect of pH on the dispersion stability of the octahedral cerium oxide abrasive particles prepared in example 1. The octahedral cerium oxide abrasive grains obtained in example 1 were dissolved in deionized water under magnetic stirring to make CeO 2 The abrasive grain concentration is 0.02wt%, and the ultrasonic dispersion is carried out for 10min. Regulating pH value with potassium hydroxide solution and dilute nitric acid solution to obtain CeO with different pH values 2 (ii) a suspension. The suspension was subjected to ultrasonic dispersion before the test, and the upper suspension was taken for absorbance test.
FIG. 4 shows that the absorbance value is the greatest at pH 2, at which the dispersion stability of the suspension is the best.
Example 2
A preparation process of octahedral cerium oxide abrasive grain polishing solution comprises the following steps:
(a) Cetyl Trimethyl Ammonium Bromide (CTAB) was dissolved in 800mL of deionized water to give CTAB concentrations of 0.005, 0.010, 0.015 and 0.020% by weight, 16g of the octahedral cerium oxide abrasive grains obtained in example 1 were added, and ultrasonic dispersion was carried out for 10min to give 2% by weight CeO 2 A suspension;
(b) Under the action of magnetic stirring, ceO is added 2 Adding KMnO into the suspension 4 To make it KMnO 4 The concentration is 0.05mol/L;
(c) And (3) regulating the pH value of the system to 2 by using a potassium hydroxide solution and a dilute nitric acid solution, and continuing to stir for 10min by magnetic force to obtain the octahedral cerium oxide abrasive grain polishing solution.
Example 3
A process for preparing an octahedral ceria abrasive polishing solution, with reference to example 2, except that cetyltrimethylammonium bromide (CTAB) is replaced with Sodium Dodecylbenzenesulfonate (SDBS).
Example 4
A process for preparing a polishing slurry of octahedral cerium oxide abrasive grains, with reference to example 2, except that cetyltrimethylammonium bromide (CTAB) is replaced with polyethylene glycol (PEG-2000, value 2000 represents the average molecular weight of polyethylene glycol).
Comparative example 1
A process for preparing an octahedral ceria abrasive grain polishing solution, with reference to example 2, except that the addition of cetyltrimethylammonium bromide (CTAB) is omitted.
Comparing the performance of the octahedral cerium oxide abrasive grain polishing solution:
1. an absorbance test was used to characterize the effect of the type and concentration of the surfactant on the dispersion stability of the octahedral cerium oxide abrasive particles prepared in example 1. And (3) diluting 1mL of the suspension at the same liquid level height by 100 times to obtain the octahedral cerium oxide abrasive particle suspension. The suspension was ultrasonically dispersed before the measurement, and the upper suspension was taken for absorbance test.
FIG. 5 shows that the absorbance value is maximal at a CTAB concentration of 0.015wt%, at which the dispersion stability of the suspension is optimal.
FIG. 6 shows that the absorbance value is maximal at a concentration of 0.005wt% SDBS, where the dispersion stability of the suspension is optimal.
FIG. 7 shows that the absorbance value is maximal at a PEG-2000 concentration of 0.010wt%, at which the dispersion stability of the suspension is optimal.
2. The octahedral cerium oxide abrasive particles prepared by the method of the present invention have a particle size of about 150nm and a uniform particle size distribution, and then octahedral cerium oxide abrasive particle polishing solutions were prepared according to the method of the foregoing comparative example 1 and preferred examples 2 to 4 (comparative example 1: no surfactant was added; ctab concentration 0.015wt% in example 2; sdbs concentration 0.005wt% in example 3; peg-2000 concentration 0.010wt% in example 4; and sequentially named as groups 1 to 4). The Si-side of the 6H-SiC wafer was subjected to a chemical mechanical polishing test using a polisher (UNIPOL-1200S). The roughness of the Si-face surface of the 6H-SiC wafer before polishing was 0.98nm. The polishing pad selects IC-1000, the polishing pressure is 30N, the upper/lower disc rotating speed is 80/120rpm, the flow rate of the polishing solution is 80ml/min, after 10min of polishing, the polishing is continued for 1min by using deionized water, particles possibly remained on the polishing surface are removed, and each group of tests are repeated for 3 times.
The polishing results are shown in FIG. 8: in comparison, the polishing performance of the polishing solution prepared by adding CTAB with the concentration of 0.015wt% is best: the material removal rate of the polished SiC wafer was 916nm/h, and the surface roughness was 0.269nm.
Comparative example 2
A process for preparing cerium oxide abrasive grains, referring to example 1, the difference is only that Ce in step (1) 3+ The solution with the concentration adjusted to 0.05mol/L specifically comprises the following steps:
(1) 20mmol of Ce (NO) 3 ) 3 ·6H 2 O and 10mmol of polyvinylpyrrolidone (PVP) were dissolved in 400mL of a mixed solution of anhydrous ethanol and deionized water (the volume ratio of the anhydrous ethanol to the deionized water was 3 3+ The solution with the concentration of 0.05mol/L is magnetically stirred for about 0.5h until the solution is clear and transparent;
(2) Transferring the solution into a stainless steel reaction kettle with the volume of 500mL, heating to 120 ℃, reacting for 20h, and naturally cooling to room temperature;
(3) Centrifugally cleaning the obtained product for 3 times by using deionized water and absolute ethyl alcohol respectively; then the obtained precipitate is dried in vacuum for 12 hours at the temperature of 60 ℃;
(4) Slowly heating the obtained product to 500 ℃, calcining for 1h, naturally cooling to room temperature, and fully grinding to obtain CeO 2 Particles (spheroidal ceria abrasive particles).
And (3) morphology characterization: characterization by field emission scanning electron microscope to obtain CeO prepared in comparative example 2 2 The particles are in a sphere-like shape, the particle size is about 150nm, and the particle size distribution is uniform.
Comparative example 3
A preparation process of sphere-like cerium oxide abrasive grain polishing solution comprises the following steps:
(a) Cetyl Trimethyl Ammonium Bromide (CTAB) was dissolved in 800mL of deionized water to a CTAB concentration of 0.015wt%, 16g of the spheroidal cerium oxide abrasive grain prepared in comparative example 2 was added, and ultrasonic dispersion was carried out for 10min to form 2wt% CeO 2 A suspension;
(b) Under the action of magnetic stirring, ceO is added 2 Adding KMnO into the suspension 4 To make it KMnO 4 The concentration is 0.05mol/L;
(c) And (3) regulating the pH value of the system to be 2 by using a potassium hydroxide solution and a dilute nitric acid solution, and continuing to magnetically stir for 10min to obtain the sphere-like cerium oxide abrasive grain polishing solution.
The chemical mechanical polishing test was performed on the Si-side of the 6H-SiC wafer using the polishing liquid of the spheroidal ceria abrasive grain of comparative example 3 by a polishing machine (UNIPOL-1200S) in accordance with the same test method as in example 2. The results show that, in the case of the spherical-like cerium oxide abrasive grain of comparative example 2, the polishing liquid prepared by adding CTAB at a concentration of 0.015wt%, the material removal rate of the SiC wafer after polishing was 703nm/h, and the surface roughness was 0.281nm.
Although the present invention has been described with reference to the preferred embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation process of octahedral cerium oxide abrasive grain polishing solution is characterized by sequentially comprising the following steps of:
(1) Preparing octahedral cerium oxide abrasive particles:
a. ce is mixed 3+ The source and polyvinylpyrrolidone (PVP) were dissolved in a mixed solution of anhydrous ethanol and deionized water at a molar ratio of 2 3+ Uniformly mixing the solution with the concentration of 0.1mol/L until the solution is clear and transparent; wherein the volume ratio of the absolute ethyl alcohol to the deionized water in the mixed solution of the absolute ethyl alcohol and the deionized water is 3;
b. transferring the solution into a closed reaction kettle, heating to 120 ℃, reacting for 20 hours, and naturally cooling to room temperature;
c. centrifugally cleaning the obtained product by using deionized water and absolute ethyl alcohol respectively; then the obtained precipitate is dried in vacuum;
d. slowly heating the obtained product to 500 ℃, calcining for 1h, naturally cooling to room temperature, and fully grinding to obtain octahedral cerium oxide abrasive particles; the octahedral cerium oxide abrasive particles are CeO with a cubic fluorite structure 2 The microcosmic appearance is octahedron, the grain diameter is 100-200 nm, and the grain diameter is distributed evenly;
(2) Preparing a polishing solution:
s1, dissolving a surfactant in deionized water to ensure that the concentration of the surfactant is 0.005-0.020 wt%; adding the octahedral cerium oxide abrasive particles prepared in the step (1) into the mixture, and performing ultrasonic dispersion to form CeO with the concentration of 2wt% 2 A suspension; wherein the surfactant is Cetyl Trimethyl Ammonium Bromide (CTAB) or Sodium Dodecyl Benzene Sulfonate (SDBS);
s2, adding into CeO 2 KMnO is added into the suspension 4 Mixing to obtain KMnO 4 The concentration is 0.05mol/L;
and S3, adjusting the pH value of the system to be 2 to obtain the octahedral cerium oxide abrasive grain polishing solution.
2. The process according to claim 1, wherein in step S1, the surfactant is Cetyl Trimethyl Ammonium Bromide (CTAB) and the surfactant concentration is 0.015wt%.
3. The process of claim 1, wherein in step S1, the surfactant is Sodium Dodecylbenzenesulfonate (SDBS) and the surfactant concentration is 0.005wt%.
4. The process according to claim 1, characterized in that in step c, vacuum drying: vacuum drying at 60 deg.C for 12h.
5. The process of claim 1, wherein Ce 3+ The source comprising Ce (NO) 3 ) 3 And/or hydrates thereof.
6. The process according to claim 1, characterized in that in said step S1, ultrasonic dispersion: ultrasonic dispersion is carried out for 10-20 min.
7. The process according to claim 1, wherein in the step S3, the pH value of the system is adjusted by using a potassium hydroxide solution and/or a dilute nitric acid solution.
8. The process according to claim 1, wherein in the step a, the step S2 or the step S3, the blending is performed by stirring at a speed of 200 to 600r/min.
9. The polishing solution of octahedral cerium oxide abrasive grains prepared by the method according to any one of claims 1 to 8.
10. Use of the octahedral ceria abrasive grain polishing solution according to claim 9 in the field of chemical mechanical polishing.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115064716A (en) * | 2022-06-29 | 2022-09-16 | 中国科学院过程工程研究所 | Cerium oxide-palladium/carbon catalyst for formic acid electrooxidation and preparation method thereof |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030093957A1 (en) * | 2001-11-16 | 2003-05-22 | Ferro Corporation | Process for producing abrasive particles and abrasive particles produced by the process |
| CN101264922A (en) * | 2008-04-21 | 2008-09-17 | 上海大学 | Method for preparing cerium oxide rhombus nano sheet-shaped material |
| CN102796493A (en) * | 2012-08-24 | 2012-11-28 | 内蒙古大学 | Spherical monodisperse high-cerium polishing powder and preparation method thereof |
| US20130327977A1 (en) * | 2012-06-11 | 2013-12-12 | Cabot Microelectronics Corporation | Composition and method for polishing molybdenum |
| CN104445340A (en) * | 2014-11-12 | 2015-03-25 | 太原理工大学 | Method for preparing octahedral cerium oxide self-assembled by nano blocks |
| CN105480999A (en) * | 2015-12-22 | 2016-04-13 | 南昌大学 | Preparation method of multilevel-structure nano cerium oxide octahedron |
| CN108285168A (en) * | 2018-05-02 | 2018-07-17 | 内蒙古科技大学 | Evengranular hexagon flake cerium carbonate particle and preparation method thereof |
| US20190153264A1 (en) * | 2017-11-15 | 2019-05-23 | Saint-Gobain Ceramics & Plastics, Inc. | Composition for conducting material removal operations and method for forming same |
| CN110354799A (en) * | 2019-07-24 | 2019-10-22 | 济南大学 | A kind of cerium dioxide nano material possessing good low temperature NOx storage capacity |
| CN111004581A (en) * | 2019-12-16 | 2020-04-14 | 天津理工大学 | Chemical mechanical polishing solution for phase-change material composite abrasive and application thereof |
| CN111592030A (en) * | 2020-06-10 | 2020-08-28 | 中南大学 | Spherical cerium oxide powder with uniform appearance and controllable granularity as well as preparation method and application thereof |
| CN114790367A (en) * | 2022-04-28 | 2022-07-26 | 广东粤港澳大湾区黄埔材料研究院 | Nano spheroidal cerium oxide polishing solution for monocrystalline silicon and polycrystalline silicon and application |
-
2022
- 2022-08-26 CN CN202211037067.3A patent/CN115160935B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030093957A1 (en) * | 2001-11-16 | 2003-05-22 | Ferro Corporation | Process for producing abrasive particles and abrasive particles produced by the process |
| CN101264922A (en) * | 2008-04-21 | 2008-09-17 | 上海大学 | Method for preparing cerium oxide rhombus nano sheet-shaped material |
| US20130327977A1 (en) * | 2012-06-11 | 2013-12-12 | Cabot Microelectronics Corporation | Composition and method for polishing molybdenum |
| CN102796493A (en) * | 2012-08-24 | 2012-11-28 | 内蒙古大学 | Spherical monodisperse high-cerium polishing powder and preparation method thereof |
| CN104445340A (en) * | 2014-11-12 | 2015-03-25 | 太原理工大学 | Method for preparing octahedral cerium oxide self-assembled by nano blocks |
| CN105480999A (en) * | 2015-12-22 | 2016-04-13 | 南昌大学 | Preparation method of multilevel-structure nano cerium oxide octahedron |
| US20190153264A1 (en) * | 2017-11-15 | 2019-05-23 | Saint-Gobain Ceramics & Plastics, Inc. | Composition for conducting material removal operations and method for forming same |
| CN108285168A (en) * | 2018-05-02 | 2018-07-17 | 内蒙古科技大学 | Evengranular hexagon flake cerium carbonate particle and preparation method thereof |
| CN110354799A (en) * | 2019-07-24 | 2019-10-22 | 济南大学 | A kind of cerium dioxide nano material possessing good low temperature NOx storage capacity |
| CN111004581A (en) * | 2019-12-16 | 2020-04-14 | 天津理工大学 | Chemical mechanical polishing solution for phase-change material composite abrasive and application thereof |
| CN111592030A (en) * | 2020-06-10 | 2020-08-28 | 中南大学 | Spherical cerium oxide powder with uniform appearance and controllable granularity as well as preparation method and application thereof |
| CN114790367A (en) * | 2022-04-28 | 2022-07-26 | 广东粤港澳大湾区黄埔材料研究院 | Nano spheroidal cerium oxide polishing solution for monocrystalline silicon and polycrystalline silicon and application |
Non-Patent Citations (2)
| Title |
|---|
| QIN WANG: ""Controllable Synthesis of Nearly Monodisperse Spherical Aggregates of CeO2 Nanocrystals and Their Catalytic Activity for HCHO Oxidation"", pages 2258 - 2267 * |
| XIGUANG HAN: "（\"Synthesis of monodisperse CeO2 octahedra assembled by nano-sheets with exposed {001} facets and catalytic property\"", vol. 14, no. 6, pages 1939 - 1941 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115064716A (en) * | 2022-06-29 | 2022-09-16 | 中国科学院过程工程研究所 | Cerium oxide-palladium/carbon catalyst for formic acid electrooxidation and preparation method thereof |
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