CN100351179C - Preparation of monodisperse spherical cerium oxide and its application in high precision polishing - Google Patents
Preparation of monodisperse spherical cerium oxide and its application in high precision polishing Download PDFInfo
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- CN100351179C CN100351179C CNB2005100404595A CN200510040459A CN100351179C CN 100351179 C CN100351179 C CN 100351179C CN B2005100404595 A CNB2005100404595 A CN B2005100404595A CN 200510040459 A CN200510040459 A CN 200510040459A CN 100351179 C CN100351179 C CN 100351179C
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- powder
- urea
- preparation
- cerium
- polishing
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- 238000005498 polishing Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229910000420 cerium oxide Inorganic materials 0.000 title claims description 10
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims description 10
- 239000000843 powder Substances 0.000 claims abstract description 23
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004202 carbamide Substances 0.000 claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- 239000012153 distilled water Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims abstract 5
- 239000011259 mixed solution Substances 0.000 claims abstract 2
- 239000002244 precipitate Substances 0.000 claims abstract 2
- 150000000703 Cerium Chemical class 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 5
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 4
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims 2
- 238000000034 method Methods 0.000 claims 2
- 239000002245 particle Substances 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 4
- 239000012530 fluid Substances 0.000 abstract description 4
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 abstract 2
- 235000012431 wafers Nutrition 0.000 abstract 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 1
- 239000002344 surface layer Substances 0.000 abstract 1
- 230000032683 aging Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 239000003082 abrasive agent Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- 241000233805 Phoenix 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
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention relates to a preparation method of superfine powder and an application area thereof. In the preparation method, a certain amount of cerate and urea are weighed to be respectively dissolved in distilled water, and the two solutions are mixed and uniformly stirred by an electric stirrer, wherein the Ce<3+> has the concentration range of 0.005 to 0.1 mol/l corresponding to the total concentration range of the solutions, the molar ratio of urea and cerate is 10:1 to 100:1, the mixed solution is sealed and heated at the temperature of 70 DEG C to 90 DEG C for 1 to 3h, then taken out for standing, aged at the room temperature for 0.5 to 12 hours and filtered, the precipitates are washed, dried and calcined at the temperature of 200 DEG C to 800 DEG C for 0.5 to 3h, and CeO2 powder is obtained. The prepared powder is taken to be prepared into polishing fluid, and a polishing machine is adopted to polish silicon wafers. Since the prepared particles are spherical and the particle size is small (in submicron order), the powder has great superiority in silicon wafer polishing which has high requirements of surface quality, the superiority is manifested as surface layer and sublayer damage as little as possible, extremely little surface residual stress and integral crystal structure of the crystal surface.
Description
Technical field
The present invention relates to superfine powder preparation and Application Areas thereof, refer in particular to the preparation method of monodisperse spherical cerium oxide and the purposes in high precision polishing thereof.
Background technology
CeO
2Use as polishing material has had very long history, is widely used in the chemically machinery polished of precision glass polishing and super large-scale integration silica dioxide medium layer, than Al
2O
3Abrasive material and SiO
2Abrasive material, CeO
2Abrasive material has that the glazed surface roughness is low, the polishing efficiency advantages of higher.In high precision polishing, the granularity of powder, pattern and distributing homogeneity thereof have played significant feature, and particle is thin more, and be subsphaeroidal more, and it is even more to distribute, and then polishing effect is good more.The superfine powder technology of preparing, reaches its maturity making significant progress aspect preparation high pure and ultra-fine, the high reactivity powder through years of development simultaneously.Along with development of science and technology, at present the ultra-fine powder technology direction that begun to surpass pattern and controllable particle size distribution develops, but the pattern of superfine powder and size distribution are controlled in theory and also have difficulties with technical, relevant submicron order spherical rare-earth oxide compound CeO
2The preparation method yet there are no report.
Summary of the invention
The present invention is a raw material with cerium salt and urea, adopts sluggish precipitation technology to synthesize, by optimization cerium salt concn, and the molar ratio of urea and cerium salt, processing parameters such as reaction, calcination condition are controlled CeO
2The pattern of powder and size-grade distribution, thus obtain that monodispersity is good, granularity is at the cerium oxide powder particle of submicron order, and it is configured to the chemically machinery polished that polishing fluid is used for silicon single crystal flake, obtained the extremely low super-smooth surface of roughness.
Specific embodiment of the present invention is: take by weighing a certain amount of cerium salt and urea and be dissolved in respectively in the distilled water, stir with two kinds of solution mixing and with electric mixer.Ce wherein
3+Concentration range with respect to total solution is 0.005～0.1mol/l, urea and cerium salt mol ratio are between 10: 1～100: 1, under 70 ℃～90 ℃ temperature, heat 1～3h behind the mixing solutions good seal, take out cooling and leave standstill, ageing at room temperature 0.5～12 hour is filtered, throw out is after washing, carry out drying, at 200 ℃～800 ℃ calcining 0.5～3h, obtain CeO again
2Powder.
Cerium salt be in cerous nitrate, cerous sulfate, the cerous carbonate any.
Described Ce
3+Between 0.01～0.08md/l, urea and cerium salt mol ratio effect between 20: 1～80: 1 are better with respect to the concentration range of total solution.
Get the powder that makes and be mixed with polishing fluid, the controlling quality percentage concentration transfers to 9～11 with ammoniacal liquor with the polishing fluid pH value between 1wt%～3wt%, adopts polishing machine that silicon wafer is polished.
The present invention has adopted comparatively simple chemical technology to prepare the goodish cerium oxide powder of monodispersity, need not complex apparatus, required chemical feedstocks kind is few, favorable repeatability, bigger industrial promotional value is arranged, simultaneously because its granule-morphology is spherical, and granulometric facies are when little (at submicron order), the quite high silicon wafer polishing of surperficial specification of quality had bigger superiority, show as the damage of as far as possible little top layer and sublayer, surface residual stress is minimum, and plane of crystal has complete crystalline structure.
Description of drawings
Fig. 1 is the sem photograph in the 1um scale scope
Fig. 2 is the sem photograph in the 0.5um scale scope
Fig. 3 is polishing back two-dimensional surface figure
Fig. 4 is a 3 dimensional drawing
Embodiment
The present invention is described in further detail below in conjunction with embodiment:
Embodiment 1: each disposes Ce (NO
3)
3With urea soln 500ml, wherein [Ce
3+]=0.04mol/l, urea and cerous nitrate mol ratio are 40: 1, two kinds of solution are mixed and stir, put into 85 ℃ of waters bath with thermostatic control and heat 2h, take out cooling and leave standstill, ageing 2h under the room temperature, throw out distilled water wash 3 times, absolute ethanol washing 1 time is put into baking oven and is dried, put into 600 ℃ of calcining furnaces again and calcine 2h, grind fully to powder the cooling back.Get the solution that certain powder is configured to 100ml, the solute mass concentration is 1wt%, add ammoniacal liquor and regulate pH value to 9, at certain polish pressure (2N), rotating speed (200rmp) with under the time (25min), use U.S. Buehler PHOENIX BETA type polishing machine polishes silicon wafer.Polished the back silicon wafer surface has been cleaned, got small pieces and under atomic force microscope, observe.
The CeO that makes by the processing parameter of embodiment 1
2The sem photograph of powder sample as shown in Figure 1 and Figure 2, wherein Fig. 1 is the SEM figure in the 1um scale scope, Fig. 2 be that the SEM in the 0.5um scale scope schemes.Therefrom as can be seen, particle size distribution is very even, is the sphere of rule, and median size is about 300nm.
Silicon wafer polishing rear surface atomic power microgram such as Fig. 3, Fig. 4.Wherein Fig. 3 is polishing back two-dimensional surface figure, and Fig. 4 is a 3 dimensional drawing.Test result shows that surperficial 2 mu m range inside surface roughness Ra values are 0.204nm, and roughness root mean square value RMS value is 0.308nm.
Embodiment 2: change solution parameter [Ce
3+] be 0.01mol/l, urea and cerous nitrate mol ratio are 15: 1, heat 3h in 70 ℃ of water-baths, ageing 0.5h calcines 3h down at 200 ℃.Get an amount of powder and be configured to solution, the solute mass concentration is 1.5wt%, adds ammoniacal liquor and regulates pH value to 10, follow-up glossing such as embodiment 1.
Embodiment 3: cerium salt is cerous sulfate, changes solution parameter [Ce
3+] be 0.1mol/l, urea and cerous sulfate mol ratio are 60: 1, heat 2.5h in 80 ℃ of water-baths, ageing 8h calcines 2.5h down at 400 ℃.Get an amount of powder and be configured to solution, the solute mass concentration is 2wt%, adds ammoniacal liquor and regulates pH value to 10.5, and follow-up glossing is the same.
Embodiment 4: cerium salt is cerous carbonate, changes solution parameter [Ce
3+] be 0.2mol/l, urea and cerous carbonate mol ratio are 100: 1, heat 1h in 90 ℃ of water-baths, ageing 12h calcines 0.5h down at 800 ℃.Get an amount of powder and be configured to solution, the solute mass concentration is 3wt%, adds ammoniacal liquor and regulates pH value to 11, and follow-up glossing is the same.
Claims (5)
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| CNB2005100404595A CN100351179C (en) | 2005-06-09 | 2005-06-09 | Preparation of monodisperse spherical cerium oxide and its application in high precision polishing |
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| CN1699282A CN1699282A (en) | 2005-11-23 |
| CN100351179C true CN100351179C (en) | 2007-11-28 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106590442A (en) * | 2017-01-22 | 2017-04-26 | 海城海美抛光材料制造有限公司 | Preparation method of cerium dioxide polishing powder liquid |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284983B (en) * | 2007-04-12 | 2011-10-19 | 北京有色金属研究总院 | Superfine and spheroidizing rare-earth polish and preparing process thereof |
| CN105251421A (en) * | 2015-11-19 | 2016-01-20 | 天津城建大学 | Low-temperature preparation method for micron cerium oxide micro-ball |
| CN106362657A (en) * | 2016-08-30 | 2017-02-01 | 虔东稀土集团股份有限公司 | Reaction device and method for preparing superfine rare earth compound through same |
| JP7074644B2 (en) * | 2018-10-31 | 2022-05-24 | 信越化学工業株式会社 | A method for manufacturing abrasive particles for polishing a synthetic quartz glass substrate, and a method for polishing a synthetic quartz glass substrate. |
| CN113120940B (en) * | 2019-12-30 | 2024-09-17 | 安集微电子科技（上海）股份有限公司 | Spherical cerium carbonate and synthetic method of cerium oxide |
| CN116409809A (en) * | 2021-12-30 | 2023-07-11 | 安集微电子科技（上海）股份有限公司 | A method for synthesizing cerium oxide, a cerium oxide and a chemical mechanical polishing solution |
| CN115849430B (en) * | 2022-12-29 | 2024-09-24 | 清华大学 | A method for preparing monodisperse nano-cerium oxide, nano-cerium oxide grinding liquid and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1368529A (en) * | 2000-05-29 | 2002-09-11 | 长兴化学工业股份有限公司 | Composition and method for synthesizing cerium oxide abrasive particles |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1368529A (en) * | 2000-05-29 | 2002-09-11 | 长兴化学工业股份有限公司 | Composition and method for synthesizing cerium oxide abrasive particles |
Non-Patent Citations (1)
| Title |
|---|
| 超细CE02磨料对硅片的抛光性能研究 陈建清等.中国机械工程，第15卷第8期 2004 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106590442A (en) * | 2017-01-22 | 2017-04-26 | 海城海美抛光材料制造有限公司 | Preparation method of cerium dioxide polishing powder liquid |
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| CN1699282A (en) | 2005-11-23 |
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