CN115160935B - 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 96
- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 65
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000005498 polishing Methods 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000008367 deionised water Substances 0.000 claims abstract description 22
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004094 surface-active agent Substances 0.000 claims abstract description 14
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 12
- 238000009826 distribution Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 50
- 239000000725 suspension Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 230000001105 regulatory effect Effects 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
- 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
- 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
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims 1
- 229910010271 silicon carbide Inorganic materials 0.000 claims 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 abstract description 13
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 abstract description 13
- 230000003746 surface roughness Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 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
- 239000002904 solvent Substances 0.000 abstract description 2
- 238000004729 solvothermal method Methods 0.000 abstract description 2
- 238000004381 surface treatment Methods 0.000 abstract description 2
- 238000002835 absorbance Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 13
- 239000006185 dispersion Substances 0.000 description 12
- 235000012431 wafers Nutrition 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000006061 abrasive grain Substances 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
- 238000010532 solid phase synthesis reaction Methods 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
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 241000722270 Regulus Species 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 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
- 238000001514 detection method 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
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 230000010355 oscillation Effects 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
- 230000035484 reaction time Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
The invention relates to the technical field of surface treatment, in particular to octahedral cerium oxide abrasive particle polishing solution, and a preparation method and application thereof. The invention uses Ce 3+ And taking polyvinylpyrrolidone as a raw material, and controlling the molar ratio of cerium nitrate hexahydrate to polyvinylpyrrolidone to be 2 by adopting a solvothermal method at a lower temperature and under the self pressure of a solvent: 1, the volume ratio of absolute ethyl alcohol to deionized water is 3:1, ce 3+ The concentration is 0.1mol/L, and the octahedral cerium oxide abrasive particles with the octahedral morphology, the 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, by selecting Cetyl Trimethyl Ammonium Bromide (CTAB) or Sodium Dodecyl Benzene Sulfonate (SDBS) with specific concentration and specific kind of surfactant, 0.05mol/L KMnO is combined 4 The polishing solution prepared when the PH value of the polishing solution is controlled to be 2 finally realizes the technical effects that the polished SiC wafer is not lower than 800nm/h and the surface roughness of the wafer is not higher 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 octahedral cerium oxide abrasive particle polishing solution, and a preparation method and application thereof.
Background
In the chemical mechanical polishing process of optical glass, semiconductor wafers, etc., the most commonly used abrasive grains include colloidal silica (SiO 2 ) Alumina (Al) 2 O 3 )、CeO 2 Etc. Colloid SiO 2 The abrasive particles are spherical, have the particle size of about 100nm, have uniform particle size distribution, can obtain better surface quality, and have smaller material removal rate on hard and brittle workpieces. Al (Al) 2 O 3 The abrasive grains have irregular surface shapes and high hardness, and scratches are easily generated on the surface of the 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 workerThe art is not very mature.
Currently, in CeO 2 Some preparation methods are also presented in the application field of abrasive particles, mainly gas phase methods, solid phase methods and liquid phase methods. The gas phase method refers to a process of reacting two or more simple substances or compounds in a gas to obtain CeO 2 Abrasive particles tend to be more stable in nature, smaller in particle size, and more uniformly distributed, however, the process of preparation is more complex, and equipment is more expensive and less commonly employed. The solid phase method refers to a process of synthesizing a precursor through a solid reactant and 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, uneven particle size distribution and low purity, thus being only applicable to CeO 2 And the quality 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 synthesized products, and is used for preparing CeO in industrial production 2 The most commonly used method of particles, but the morphology, the size and the particle size distribution of abrasive particles are uncontrollable, and the abrasive particles are also uneven, so that the abrasive particles are used for preparing polishing liquid and are easy to agglomerate, have larger influence on polishing performance and are unfavorable for CeO 2 The application of the particles in polishing solution. Developing 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 a technical problem to be solved in the art.
Disclosure of Invention
Technical problems:
a cerium oxide polishing solution is developed, wherein the material removal rate is not lower than 800nm/h, and the surface roughness of a wafer is not higher than 0.28 nm.
The technical scheme is as follows:
the first aim of the invention is to provide a preparation process of octahedral cerium oxide abrasive particle polishing solution, which sequentially comprises the following steps:
(1) Preparing octahedral cerium oxide abrasive particles:
a. ce is prepared from 3+ Source and polyvinylpyrrolidone (PVP) at a 2:1 molar ratioThe molar ratio is dissolved in the mixed solution of absolute ethyl alcohol and deionized water to obtain Ce 3+ 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 3:1;
b. transferring the solution into a closed reaction kettle, heating to 120 ℃ for reaction for 20 hours, and then naturally cooling to room temperature;
c. respectively centrifugally cleaning the obtained product with deionized water and absolute ethyl alcohol; then vacuum drying the obtained precipitate;
d. slowly heating the obtained product to 500 ℃ for calcination 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 cubic fluorite structure 2 The microcosmic appearance is octahedral, the grain diameter is 100-200 nm, and the grain diameter is distributed uniformly;
(2) Preparing polishing solution:
s1, dissolving a surfactant in deionized water to enable the concentration of the surfactant to be 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, ceO 2 Adding KMnO into the suspension 4 Mixing to obtain KMnO 4 The concentration is 0.05mol/L;
s3, regulating the pH value of the system to 2 to obtain the octahedral cerium oxide abrasive particle 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 Dodecyl Benzene Sulfonate (SDBS) having a surfactant concentration of 0.005wt%.
As a preferred embodiment of the present invention, in the step c, vacuum drying: vacuum drying at 60℃for 12h.
As a preferred embodiment of the present invention, ce 3+ The source includes Ce (NO) 3 ) 3 And/or hydrates thereof.
As a preferred embodiment of the present invention, in the step S1, ultrasonic dispersion is performed: and (5) performing ultrasonic dispersion for 10-20 min. Further preferably 10min.
As a preferred embodiment of the present invention, in the 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, in the step a, the step S2 or the step S3, the mixing is performed by stirring at a stirring speed of 200 to 600r/min.
The second object of the present invention is to provide an octahedral cerium oxide abrasive particle polishing liquid prepared by the aforementioned method.
A third object of the present invention is to provide the use of the above octahedral cerium oxide abrasive particle polishing solution in the chemical mechanical polishing field.
The beneficial effects are that:
(1) The invention uses Ce to optimize the preparation method of cerium oxide abrasive particles 3+ The polyvinyl pyrrolidone is used as a raw material, ethanol-water with a specific proportion is used as a solvent, and a solvothermal method is adopted, so that the molar ratio of cerium nitrate hexahydrate to the polyvinyl pyrrolidone is mainly required to be controlled to be 2:1, the volume ratio of absolute ethyl alcohol to deionized water is 3:1, control Ce 3+ The concentration is 0.1mol/L, the octahedral cerium oxide abrasive particles with the octahedral morphology, the particle size of about 150nm and uniform particle size distribution are successfully prepared, and the technical barriers that the shape and the size of the cerium oxide abrasive particles synthesized by a liquid phase method in the prior art are uncontrollable, the particle size distribution is also uneven, and the octahedral cerium oxide abrasive particles are easy to agglomerate and the like are overcome.
(2) Based on the specific octahedral cerium oxide abrasive particles of the invention, by selecting Cetyl Trimethyl Ammonium Bromide (CTAB) or Sodium Dodecyl Benzene Sulfonate (SDBS) with specific concentration and specific kind of surfactant, 0.05mol/L KMnO is combined 4 The polishing solution prepared when the PH value of the polishing solution is controlled to be 2 finally realizes that the polished SiC wafer is not lower than 800nm/h,and meanwhile, the surface roughness of the wafer is not higher than 0.28nm, and unexpected technical effects are obtained.
(3) According to the preparation method of the octahedral cerium oxide abrasive particle polishing solution, when the concentration of added hexadecyl 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 the polished SiC wafer can reach 916nm/h, and the surface roughness is 0.269nm.
Drawings
Fig. 1 is a FTIR image of octahedral cerium oxide abrasive particles prepared in example 1.
Fig. 2 is an XRD pattern of the octahedral cerium oxide abrasive particles prepared in example 1.
Fig. 3 is an SEM image of octahedral cerium oxide abrasive particles prepared in example 1.
FIG. 4 is a graph showing the absorbance of octahedral cerium oxide abrasive particles prepared in example 1 with pH.
FIG. 5 is a graph showing the absorbance of the polishing liquid of the octahedral cerium oxide abrasive particles prepared in example 1 according to the concentration of CTAB.
FIG. 6 is a graph showing the change in absorbance of a polishing solution of octahedral cerium oxide abrasive particles prepared in example 1 with SDBS concentration.
FIG. 7 is a graph showing the absorbance of the polishing solution of the octahedral cerium oxide abrasive particles prepared in example 1 according to the concentration of PEG-2000.
Fig. 8 is a graph showing the material removal rate and surface roughness values of SiC after polishing using the octahedral cerium oxide abrasive particle polishing solutions prepared in comparative example 1 and preferred examples 2 to 4.
Detailed Description
Example 1
The preparation process of the octahedral cerium oxide abrasive particles comprises the following steps:
(1) 40mmol of Ce (NO) 3 ) 3 ·6H 2 O and 20mmol of polyvinylpyrrolidone (PVP) are dissolved in 400mL of a mixed solution of absolute ethyl alcohol and deionized water (the volume ratio of absolute ethyl alcohol to deionized water is 3:1) to obtain Ce 3+ Magnetically stirring the solution with the concentration of 0.10mol/L 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 ℃ for reaction for 20h, and then naturally cooling to room temperature;
(3) Respectively centrifugally cleaning the obtained product with deionized water and absolute ethyl alcohol for 3 times; and vacuum drying the obtained precipitate at 60 ℃ for 12 hours;
(4) Slowly heating the obtained product to 500 ℃ for calcination for 1h, then naturally cooling to room temperature, and fully grinding to obtain CeO 2 Particles (octahedral cerium oxide abrasive particles).
Characterization of octahedral cerium oxide abrasive particles and dispersion stability performance test:
1. infrared spectrum detection of octahedral cerium oxide abrasive particles prepared in example 1 by Fourier infrared spectrometer (ALPHA) with wavelength range of 4000-450 cm -1 。
The absorption peaks of the samples are shown in FIG. 1 to occur at about 3410, 1660, 1560, 480cm -1 Where it is located. 3410cm -1 The absorption peak at this point is caused by the stretching vibration of the OH-group, indicating that free water is contained in the product. 1560cm -1 、1660cm -1 The absorption peaks at these were each caused by vibration of the C-N, C =o group, indicating that the sample coordinated to the-NH-c=o group in PVP during the reaction. The sample is 400-500 cm -1 Absorption peaks appear in the range, indicating that CeO is formed by hydrothermal reaction 2 And (3) particles.
2. The octahedral cerium oxide abrasive particle sample phase obtained in example 1 was analyzed by an X-ray diffractometer (D8 advance), a copper target (incidence wavelength λ= 0.15406 mm) was set as a radiation source, a scanning speed was 8 °/min, and a scanning angle range was 20 to 90 °.
FIG. 2 shows that the sample has obvious diffraction peaks near 2θ=28.5°, 33.1 °, 47.5 ° and 56.3 °, corresponding to (111), (200), (220) and (311) crystal planes, respectively, and the positions and intensities of the diffraction peaks are the same as CeO 2 Standard atlas (#PDF34-0394) is identical, no other impurity peak exists, and the CeO with the cubic fluorite structure is obtained through the reaction 2 Particles, consistent with fourier infrared spectroscopy test results.
3. The morphology and particle size of the octahedral cerium oxide abrasive particle sample prepared in example 1 were observed by using a field emission scanning electron microscope (Regulus 8100).
CeO of FIG. 3 2 The particles are octahedral, have the particle size of about 150nm and are uniformly distributed.
4. The influence of the physical dispersion manner on the dispersion stability of the octahedral cerium oxide abrasive particles prepared in example 1 was investigated by absorbance test. The octahedral cerium oxide abrasive particles prepared in example 1 were dissolved in deionized water to prepare CeO 2 Suspension with abrasive particle concentration of 0.02 wt%. To explore the ultrasonic oscillation time to CeO 2 The dispersion stability was affected by shaking the suspension at an ultrasonic power of 240w for various times, and absorbance test was performed by taking the upper suspension.
The results showed that the dispersion stability of the suspension was optimal at about 10min of ultrasonic vibration, and then the absorbance tended to be stable.
5. The effect of pH on the dispersion stability of the octahedral cerium oxide abrasive particles prepared in example 1 was characterized by absorbance test. Under the action of magnetic stirring, the octahedral cerium oxide abrasive particles prepared in the example 1 are dissolved in deionized water to enable CeO 2 The concentration of the abrasive particles 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 A suspension. The suspension was subjected to ultrasonic dispersion prior to testing, and the upper suspension was subjected to absorbance testing during the test.
FIG. 4 shows that the absorbance is maximum at pH 2, at which time the dispersion stability of the suspension is optimal.
Example 2
The preparation process of the octahedral cerium oxide abrasive particle 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 0.020wt%, respectively, 16g of the octahedral cerium oxide abrasive particles prepared in example 1 were added, and ultrasonic dispersion was performed for 10min to give CeO concentration of 2wt% 2 A suspension;
(b) Under the action of magnetic stirring, ceO is added to 2 Adding KMnO to the suspension 4 Make KMnO thereof 4 The concentration is 0.05mol/L;
(c) And regulating the pH value of the system to 2 by using a potassium hydroxide solution and a dilute nitric acid solution, and continuing to magnetically stir for 10min to obtain the octahedral cerium oxide abrasive particle polishing solution.
Example 3
A process for preparing octahedral cerium oxide abrasive particle polishing solution, referring to example 2, except that cetyltrimethylammonium bromide (CTAB) was replaced with Sodium Dodecyl Benzene Sulfonate (SDBS).
Example 4
The preparation process of octahedral cerium oxide abrasive particle polishing solution, referring to example 2, differs only in that cetyl trimethylammonium bromide (CTAB) is replaced with polyethylene glycol (PEG-2000, the number 2000 representing the average molecular weight of the polyethylene glycol).
Comparative example 1
A process for preparing octahedral cerium oxide abrasive particle polishing solution, referring to example 2, except that addition of cetyl trimethylammonium bromide (CTAB) was omitted.
Performance comparison of octahedral cerium oxide abrasive particle polishing solution:
1. the influence of the kind and concentration of the surfactant on the dispersion stability of the octahedral cerium oxide abrasive particles prepared in example 1 was characterized by using an absorbance test. 1mL of the suspension at the same liquid level was diluted 100 times to prepare an octahedral cerium oxide abrasive particle suspension. The suspension was subjected to ultrasonic dispersion prior to measurement, and the upper suspension was subjected to absorbance test at the time of the test.
FIG. 5 shows that the absorbance was maximum at a CTAB concentration of 0.015wt% at which the dispersion stability of the suspension was optimal.
FIG. 6 shows that the absorbance value is maximum at an SDBS concentration of 0.005wt% when the dispersion stability of the suspension is optimal.
FIG. 7 shows that the absorbance was maximized at a PEG-2000 concentration of 0.010wt% at which the dispersion stability of the suspension was 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 (comparative example 1: no surfactant added; example 2: CTAB concentration of 0.015wt%, example 3: SDBS concentration of 0.005wt%, example 4: PEG-2000 concentration of 0.010wt%, and designated as groups 1 to 4 in order) were prepared according to the method of comparative example 1 and preferred examples 2 to 4. A chemical mechanical polishing test was performed on the Si surface of the 6H-SiC wafer using a polisher (UNIPL-1200S). The roughness of the Si surface of the 6H-SiC wafer before polishing was 0.98nm. The polishing pad is selected from IC-1000, polishing pressure is 30N, rotating speed of upper disc/lower disc is 80/120rpm, flow rate of polishing solution is 80ml/min, polishing is carried out for 10min, then deionized water is continuously used for polishing for 1min, 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: as a result of comparison, the polishing performance of the polishing liquid prepared by adding CTAB at a concentration of 0.015 wt.% was the best: the material removal rate of the polished SiC wafer is 916nm/h, and the surface roughness is 0.269nm.
Comparative example 2
A process for preparing cerium oxide abrasive particles, referring to example 1, differs only in that Ce in step (1) is used 3+ The concentration of the solution is regulated to be 0.05mol/L, and the method specifically comprises the following steps of:
(1) 20mmol of Ce (NO) 3 ) 3 ·6H 2 O and 10mmol of polyvinylpyrrolidone (PVP) are dissolved in 400mL of a mixed solution of absolute ethyl alcohol and deionized water (the volume ratio of absolute ethyl alcohol to deionized water is 3:1) to obtain Ce 3+ Magnetically stirring the solution with the concentration of 0.05mol/L 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 ℃ for reaction for 20h, and then naturally cooling to room temperature;
(3) Respectively centrifugally cleaning the obtained product with deionized water and absolute ethyl alcohol for 3 times; vacuum drying the obtained precipitate at 60deg.C for 12 hr;
(4) Slowly heating the obtained product to 500 ℃ for calcination for 1h, then naturally cooling to room temperature, and fully grinding to obtain CeO 2 Particles (spheroidal cerium oxide abrasive particles).
Morphology characterization: characterization by field emission scanning electron microscope to obtain CeO prepared in comparative example 2 2 The particles are sphere-like, have the particle size of about 150nm and are uniformly distributed.
Comparative example 3
A preparation process of a spherical cerium oxide abrasive particle-like 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 particles prepared in comparative example 2 were added, and ultrasonic dispersion was carried out for 10min to form CeO having a concentration of 2wt% 2 A suspension;
(b) Under the action of magnetic stirring, ceO is added to 2 Adding KMnO to the suspension 4 Make KMnO thereof 4 The concentration is 0.05mol/L;
(c) And regulating the pH value of the system to 2 by using a potassium hydroxide solution and a dilute nitric acid solution, and continuing to magnetically stir for 10min to obtain the spheroidal cerium oxide abrasive particle polishing solution.
A chemical mechanical polishing test was performed on the Si surface of a 6H-SiC wafer using a polishing machine (UNIPL-1200S) in the same test method as in example 2 using the spheroidal cerium oxide abrasive polishing solution of comparative example 3. As a result, it was found that, with respect to the spheroidal cerium oxide abrasive particles of comparative example 2, a polishing liquid prepared by adding CTAB at a concentration of 0.015wt% was added, and the material removal rate of the polished SiC wafer was 703nm/h and the surface roughness was 0.281nm.
While the invention has been described in terms of preferred embodiments, it is not limited thereto, and various changes and modifications can be made by those skilled in the art without departing from the spirit and scope of the invention.
Claims (6)
1. Use of an octahedral cerium oxide abrasive particle polishing solution in chemical mechanical polishing, wherein the polishing solution is used for polishing a silicon carbide wafer, and the preparation of the polishing solution comprises the following steps:
(1) Preparing octahedral cerium oxide abrasive particles:
a. ce is prepared from 3+ The source and polyvinylpyrrolidone are dissolved in a mixed solution of absolute ethyl alcohol and deionized water in a molar ratio of 2:1 to obtain Ce 3+ Mixing the solution with the concentration of 0.1mol/L until the solution is clear and transparent; wherein the volume of the absolute ethyl alcohol and the deionized water in the mixed solution of the absolute ethyl alcohol and the deionized waterThe ratio is 3:1;
b. transferring the solution into a closed reaction kettle, heating to 120 ℃ for reaction for 20 hours, and then naturally cooling to room temperature;
c. respectively centrifugally cleaning the obtained product with deionized water and absolute ethyl alcohol; then vacuum drying the obtained precipitate;
d. slowly heating the obtained product to 500 ℃ for calcination 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 cubic fluorite structure 2 The microcosmic appearance is octahedral, the grain diameter is 150-200 nm, and the grain diameter distribution is uniform;
(2) Preparing polishing solution:
s1, dissolving a surfactant in deionized water to enable the concentration of the surfactant to be 0.015wt%; 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;
s2, ceO 2 Adding KMnO into the suspension 4 Mixing to obtain KMnO 4 The concentration is 0.05mol/L;
s3, regulating the pH value of the system to 2 to obtain the octahedral cerium oxide abrasive particle polishing solution.
2. The use according to claim 1, wherein in step c the vacuum drying is at 60 ℃ for 12 hours.
3. The use according to claim 1, wherein Ce 3+ The source includes Ce (NO) 3 ) 3 And/or hydrates thereof.
4. Use according to claim 1, characterized in that in step S3 the pH of the system is adjusted with a potassium hydroxide solution and/or a dilute nitric acid solution.
5. The use according to claim 1, wherein in step a, step S2, the mixing is performed by stirring at a speed of 200-600 r/min.
6. An octahedral cerium oxide abrasive particle polishing liquid, which is characterized by being prepared by the method for preparing the polishing liquid according to claim 1.
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