WO2023125884A1 - Method for synthesizing cerium oxide, and chemical mechanical polishing solution - Google Patents
Method for synthesizing cerium oxide, and chemical mechanical polishing solution Download PDFInfo
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- WO2023125884A1 WO2023125884A1 PCT/CN2022/143700 CN2022143700W WO2023125884A1 WO 2023125884 A1 WO2023125884 A1 WO 2023125884A1 CN 2022143700 W CN2022143700 W CN 2022143700W WO 2023125884 A1 WO2023125884 A1 WO 2023125884A1
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- cerium
- cerium oxide
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- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 48
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 30
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 22
- 238000005498 polishing Methods 0.000 title claims description 22
- 239000000126 substance Substances 0.000 title claims description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 30
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 27
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000002425 crystallisation Methods 0.000 claims abstract description 13
- 230000008025 crystallization Effects 0.000 claims abstract description 13
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 11
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000003795 chemical substances by application Substances 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 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- 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 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 11
- 235000012431 wafers Nutrition 0.000 abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052710 silicon Inorganic materials 0.000 abstract description 4
- 239000010703 silicon Substances 0.000 abstract description 4
- 238000005273 aeration Methods 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- 238000001308 synthesis method Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 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 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
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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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
Definitions
- the invention relates to the field of chemical mechanical polishing, in particular to a method for synthesizing cerium oxide and a chemical mechanical polishing liquid.
- cerium oxide abrasives have been widely used in the chemical mechanical polishing (CMP) polishing field of integrated circuit manufacturing, especially the shallow trench isolation (STI) process, mainly because it has a high polishing rate for silicon oxide substrates. Moreover, good polishing activity can be achieved under the condition that the particle content of the polishing liquid is low. Among them, the doping synthesis of cerium oxide particles plays a key role in its polishing chemical activity and particle morphology, especially when the particle morphology is nearly spherical, it can effectively control and reduce the suppression of defects in the polishing process.
- CMP chemical mechanical polishing
- STI shallow trench isolation
- the prior art CN106927495A discloses a method for preparing cerium oxide, in which cerium oxide is prepared by heating precipitation and high-temperature roasting of cerium carbonate precursor.
- the preparation method of such traditional cerium oxide nanoparticles requires high-temperature roasting, resulting in large grain size of the product, serious agglomeration, and easy scratches on the surface of the silicon wafer; even after ball milling and dispersion processes, it is difficult to completely avoid the finished product containing A certain amount of large-sized grains affects product quality.
- the present invention provides a method for cerium oxide, which can produce cerium oxide with uniform particle size without high-temperature roasting, and, after making polishing liquid
- the method can effectively reduce scratches on the surface of the silicon wafer, and has wide popularization and application value.
- the present invention provides a method for synthesizing cerium oxide, comprising:
- S1 configuring a cerium source aqueous solution, and doping rare earth elements into the cerium source aqueous solution;
- the raw materials involved in the S1-S3 are all aerated with inert gas, and the S1-S3 are all completed in an inert gas protective atmosphere.
- the rare earth element is selected from one or more of lanthanum, praseodymium, neodymium, yttrium and kang.
- the molar ratio of the rare earth element to the cerium element in the cerium source aqueous solution is 0.1/100-20/100.
- the molar ratio of the rare earth element to the cerium element in the cerium source aqueous solution is 1/100-10/100.
- the cerium source is selected from one or more of cerium chloride, cerium nitrate, cerium acetate, cerium ammonium nitrate, and cerium sulfate.
- the molar concentration of the cerium source aqueous solution is 0.1-1.0M.
- the molar concentration of the cerium source aqueous solution is 0.2-0.6M.
- the precipitating agent is selected from one or more of sodium hydroxide, potassium hydroxide and ammonia water.
- the molar concentration of the aqueous precipitation agent solution is 0.1-3.0M.
- the molar concentration of the aqueous precipitation agent solution is 0.5-1.5M.
- the reaction temperature of the crystallization reaction is 60°C-180°C, and the reaction time is 1.0-24.0 hours.
- the reaction temperature of the crystallization reaction is 80°C-120°C, and the reaction time is 3.0-8.0 hours.
- Another aspect of the present invention also provides a chemical mechanical polishing solution, comprising cerium oxide synthesized by any one of the methods for synthesizing cerium oxide described above.
- the method for synthesizing cerium oxide of the present invention finally obtains cerium oxide particles with a uniform particle size, can effectively reduce scratches on the surface of silicon wafers, and has wide popularization and application value.
- Fig. 1 is the scanning electron microscope (SEM) picture of the cerium oxide that makes according to the synthetic method of embodiment 1 of the present invention
- SEM scanning electron microscope
- SEM scanning electron microscope
- Figure 4 is a scanning electron microscope (SEM) image of cerium oxide prepared according to the synthesis method of Comparative Example 2 of the present invention.
- Examples 1-8 of the present invention and comparative examples 1-2 synthesize cerium oxide according to the following steps:
- S1 configuring a cerium source aqueous solution, and doping rare earth elements into the cerium source aqueous solution;
- the raw materials involved in the S1-S3 are all aerated with inert gas, and the S1-S3 are all completed in an inert gas protective atmosphere.
- Fig. 1 is the SEM photo of the cerium oxide obtained by the method for synthesizing cerium oxide in Example 1 of the present invention. Observing Fig. 1 and 2, it can be known that the synthesis method in the present invention can produce cerium oxide with nearly spherical particle morphology, and the dispersibility better.
- Figure 3 and Figure 4 are SEM photographs of cerium oxide synthesized according to the synthesis methods of Comparative Example 1 and Comparative Example 2. It can be observed that the cerium oxide synthesized in Comparative Example 1 and Comparative Example 2 is seriously agglomerated, and the particle size is uneven and the shape different.
- the polishing performance of the cerium oxide was further tested: respectively prepared as aqueous dispersions with a solid content of 1 wt % and a pH of about 4.5, and measured the polishing removal rate (RR) of TEOS blank wafers under different pressure conditions.
- the specific polishing conditions are as follows: the polishing machine is Mirra, IC1010 polishing pad, the rotation speed of Platten and Carrier are 93rpm and 87rpm respectively, the pressure is 3psi, the flow rate of polishing solution is 150mL/min, and the polishing time is 60 seconds.
- Example 1 3620 Example 2 3750 Example 3 4400 Example 4 3950 Example 5 4550 Example 6 4110 Example 7 2700 Example 8 3990 Comparative example 1 1800 Comparative example 2 1500
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention provides a method for synthesizing cerium oxide, comprising: S1, preparing a cerium source aqueous solution, and doping the cerium source aqueous solution with a rare earth element; S2, preparing a precipitant aqueous solution, and adding the cerium source aqueous solution into the precipitant aqueous solution in a reactor to prepare a mixed solution; and S3, crystallization reaction: thoroughly stirring the mixed solution, and sealing the reactor for high-temperature crystallization reaction, wherein the raw materials involved in S1-S3 have all been subjected to aeration by an inert gas, and S1-S3 are all completed in an inert gas protection atmosphere. By means of the method for synthesizing cerium oxide in the present invention, cerium oxide particles finally obtained are uniform in particle size, scratches on the surface of silicon wafers can be effectively reduced, and the present invention is worthy of wide popularization and application.
Description
本发明涉及化学机械抛光领域，尤其涉及一种合成氧化铈的方法及一种化学机械抛光液。The invention relates to the field of chemical mechanical polishing, in particular to a method for synthesizing cerium oxide and a chemical mechanical polishing liquid.
目前，氧化铈磨料在集成电路制造的化学机械抛光(CMP)抛光领域，特别是浅沟槽隔离(STI)工序已经得到广泛应用，主要原因是其对于氧化硅基材具有较高的抛光速率，且在抛光液颗粒含量较低的情况下便可达到很好的抛光活性。其中，氧化铈颗粒掺杂合成对其抛光化学活性和颗粒形貌起着关键影响，特别是当颗粒形貌近球形，会对其抛光过程中缺陷的抑制实现有效调控和减少。At present, cerium oxide abrasives have been widely used in the chemical mechanical polishing (CMP) polishing field of integrated circuit manufacturing, especially the shallow trench isolation (STI) process, mainly because it has a high polishing rate for silicon oxide substrates. Moreover, good polishing activity can be achieved under the condition that the particle content of the polishing liquid is low. Among them, the doping synthesis of cerium oxide particles plays a key role in its polishing chemical activity and particle morphology, especially when the particle morphology is nearly spherical, it can effectively control and reduce the suppression of defects in the polishing process.
现有技术CN106927495A公开了一种氧化铈的制备方法，通过加热沉淀和高温焙烧碳酸铈前驱体制备氧化铈。这类传统氧化铈纳米颗粒的制备方法需经过高温焙烧，导致产物晶粒尺寸大，团聚现象严重，容易造成硅晶圆表面划伤；即便经过球磨和分散工艺后也很难完全避免成品中含有一定量的大尺寸晶粒，影响了产品质量。The prior art CN106927495A discloses a method for preparing cerium oxide, in which cerium oxide is prepared by heating precipitation and high-temperature roasting of cerium carbonate precursor. The preparation method of such traditional cerium oxide nanoparticles requires high-temperature roasting, resulting in large grain size of the product, serious agglomeration, and easy scratches on the surface of the silicon wafer; even after ball milling and dispersion processes, it is difficult to completely avoid the finished product containing A certain amount of large-sized grains affects product quality.
因此，需要一种能够合成制得形貌均匀、活性高的氧化铈合成方法。Therefore, there is a need for a method for synthesizing cerium oxide with uniform morphology and high activity.
发明内容Contents of the invention
为了解决制得的氧化铈粒径尺寸大、团聚严重的技术问题，本发明提供一种氧化铈的方法，无需高温焙烧即可制得颗粒粒径均匀的氧化铈，并且，制成抛光液后能够有效降低对硅晶圆表面的划伤，具有广泛的推广应用价值。In order to solve the technical problems of large particle size and serious agglomeration of the prepared cerium oxide, the present invention provides a method for cerium oxide, which can produce cerium oxide with uniform particle size without high-temperature roasting, and, after making polishing liquid The method can effectively reduce scratches on the surface of the silicon wafer, and has wide popularization and application value.
具体的，本发明提供一种合成氧化铈的方法，包括：Specifically, the present invention provides a method for synthesizing cerium oxide, comprising:
S1：配置铈源水溶液，并向所述铈源水溶液中掺杂稀土元素；S1: configuring a cerium source aqueous solution, and doping rare earth elements into the cerium source aqueous solution;
S2：配置沉淀剂水溶液，在反应釜中将所述铈源水溶液添加至所述沉淀剂水溶液中，制得混合溶液；S2: configuring a precipitant aqueous solution, adding the cerium source aqueous solution to the precipitant aqueous solution in a reaction kettle to prepare a mixed solution;
S3：晶化反应：充分搅拌所述混合溶液，密闭所述反应釜进行高温晶化反应。S3: crystallization reaction: fully stir the mixed solution, seal the reaction kettle to carry out high temperature crystallization reaction.
所述S1-S3中涉及原料均经惰性气体曝气处理，所述S1-S3均在惰性气体保护氛围中完成。The raw materials involved in the S1-S3 are all aerated with inert gas, and the S1-S3 are all completed in an inert gas protective atmosphere.
优选的，所述稀土元素选自镧、镨、钕、钇、炕中的一种或多种。Preferably, the rare earth element is selected from one or more of lanthanum, praseodymium, neodymium, yttrium and kang.
优选的，所述稀土元素与所述铈源水溶液中铈元素的摩尔之比为0.1/100-20/100。Preferably, the molar ratio of the rare earth element to the cerium element in the cerium source aqueous solution is 0.1/100-20/100.
优选的，所述稀土元素与所述铈源水溶液中铈元素的摩尔之比为1/100-10/100。Preferably, the molar ratio of the rare earth element to the cerium element in the cerium source aqueous solution is 1/100-10/100.
优选的，所述铈源选自氯化铈、硝酸铈、醋酸铈、硝酸铈铵、硫酸铈中的一种或多种。Preferably, the cerium source is selected from one or more of cerium chloride, cerium nitrate, cerium acetate, cerium ammonium nitrate, and cerium sulfate.
优选的，所述铈源水溶液的摩尔浓度为0.1～1.0M。Preferably, the molar concentration of the cerium source aqueous solution is 0.1-1.0M.
优选的，所述铈源水溶液的摩尔浓度为0.2～0.6M。Preferably, the molar concentration of the cerium source aqueous solution is 0.2-0.6M.
优选的，所述沉淀剂选自氢氧化钠、氢氧化钾、氨水中的一种或多种。Preferably, the precipitating agent is selected from one or more of sodium hydroxide, potassium hydroxide and ammonia water.
优选的，所述沉淀剂水溶液的摩尔浓度为0.1～3.0M。Preferably, the molar concentration of the aqueous precipitation agent solution is 0.1-3.0M.
优选的，所述沉淀剂水溶液的摩尔浓度为0.5～1.5M。Preferably, the molar concentration of the aqueous precipitation agent solution is 0.5-1.5M.
优选的，所述晶化反应的反应温度为60℃-180℃，反应时间为1.0-24.0小时。Preferably, the reaction temperature of the crystallization reaction is 60°C-180°C, and the reaction time is 1.0-24.0 hours.
优选的，所述晶化反应的反应温度为80℃-120℃，反应时间为3.0-8.0小时。Preferably, the reaction temperature of the crystallization reaction is 80°C-120°C, and the reaction time is 3.0-8.0 hours.
本发明的另一方面，还提供一种化学机械抛光液，包含由以上任一所述的合成氧化铈的方法合成的氧化铈。Another aspect of the present invention also provides a chemical mechanical polishing solution, comprising cerium oxide synthesized by any one of the methods for synthesizing cerium oxide described above.
本发明合成氧化铈的方法最终得到的氧化铈颗粒粒径均匀，能够有效降低对硅晶圆表面的划伤，具有广泛的推广应用价值。The method for synthesizing cerium oxide of the present invention finally obtains cerium oxide particles with a uniform particle size, can effectively reduce scratches on the surface of silicon wafers, and has wide popularization and application value.
图1为根据本发明实施例1合成方法制得的氧化铈的电子扫描显微镜(SEM)图；Fig. 1 is the scanning electron microscope (SEM) picture of the cerium oxide that makes according to the synthetic method of embodiment 1 of the present invention;
图2为根据本发明实施例2合成方法制得的氧化铈的电子扫描显微镜(SEM)图；2 is a scanning electron microscope (SEM) figure of cerium oxide prepared according to the synthesis method of Example 2 of the present invention;
图3为根据本发明对比例1合成方法制得的氧化铈的电子扫描显微镜(SEM)图；3 is a scanning electron microscope (SEM) figure of cerium oxide prepared according to the synthetic method of Comparative Example 1 of the present invention;
图4为根据本发明对比例2合成方法制得的氧化铈的电子扫描显微镜(SEM)图.。Figure 4 is a scanning electron microscope (SEM) image of cerium oxide prepared according to the synthesis method of Comparative Example 2 of the present invention.
以下结合具体实施例及附图进一步阐述本发明的优点。The advantages of the present invention will be further described below in conjunction with specific embodiments and accompanying drawings.
本发明实施例1-8及对比例1-2依照下列步骤，合成氧化铈：Examples 1-8 of the present invention and comparative examples 1-2 synthesize cerium oxide according to the following steps:
S1：配置铈源水溶液，并向所述铈源水溶液中掺杂稀土元素；S1: configuring a cerium source aqueous solution, and doping rare earth elements into the cerium source aqueous solution;
S2：配置沉淀剂水溶液，在反应釜中将所述铈源水溶液添加至所述沉淀剂水溶液中，制得混合溶液；S2: configuring a precipitant aqueous solution, adding the cerium source aqueous solution to the precipitant aqueous solution in a reaction kettle to prepare a mixed solution;
S3：晶化反应：充分搅拌所述混合溶液，密闭所述反应釜进行高温晶化反应。S3: crystallization reaction: fully stir the mixed solution, seal the reaction kettle to carry out high temperature crystallization reaction.
所述S1-S3中涉及原料均经惰性气体曝气处理，所述S1-S3均在惰性气体保护氛围中完成。The raw materials involved in the S1-S3 are all aerated with inert gas, and the S1-S3 are all completed in an inert gas protective atmosphere.
其中，所述铈源、沉淀剂的具体物质及其水溶液浓度、稀土元素的具体物质及浓度、晶化反应的具体参数如表1所示。Wherein, the specific substance of the cerium source, the precipitating agent and the concentration of its aqueous solution, the specific substance and concentration of the rare earth element, and the specific parameters of the crystallization reaction are shown in Table 1.
表1实施例1-8及对比例1-2的合成氧化铈的方法的具体反应物及其浓度Concrete reactant and its concentration of the method for the synthesis of cerium oxide of table 1 embodiment 1-8 and comparative example 1-2
图1为通过本发明实施例1合成氧化铈的方法制得的氧化铈SEM照片，观察图1、2可知，本发明中的合成方法能够制得具有近球形颗粒形貌氧化铈，并且分散性较好。图3、图4为依据对比例1及对比例2的合成方法合成出的氧化铈SEM照片，可以观察到对比例1及对比例2合成出的氧化铈团聚严重，且颗粒大小不均匀，形状各异。Fig. 1 is the SEM photo of the cerium oxide obtained by the method for synthesizing cerium oxide in Example 1 of the present invention. Observing Fig. 1 and 2, it can be known that the synthesis method in the present invention can produce cerium oxide with nearly spherical particle morphology, and the dispersibility better. Figure 3 and Figure 4 are SEM photographs of cerium oxide synthesized according to the synthesis methods of Comparative Example 1 and Comparative Example 2. It can be observed that the cerium oxide synthesized in Comparative Example 1 and Comparative Example 2 is seriously agglomerated, and the particle size is uneven and the shape different.
进一步测试所述氧化铈的抛光性能：分别调配为1wt％固含量pH为4.5左右水分散液，并进行不同压力条件下测量TEOS空白晶圆的抛光去除速率(RR)。The polishing performance of the cerium oxide was further tested: respectively prepared as aqueous dispersions with a solid content of 1 wt % and a pH of about 4.5, and measured the polishing removal rate (RR) of TEOS blank wafers under different pressure conditions.
具体抛光条件为，抛光机台为Mirra，IC1010抛光垫，Platten和Carrier转速分别为93rpm和87rpm，压力3psi，抛光液流速为150mL/min，抛光时间为60秒。The specific polishing conditions are as follows: the polishing machine is Mirra, IC1010 polishing pad, the rotation speed of Platten and Carrier are 93rpm and 87rpm respectively, the pressure is 3psi, the flow rate of polishing solution is 150mL/min, and the polishing time is 60 seconds.
表2实施例1-8及对比例1-2对应氧化铈分散液的抛光实验结果Table 2 Example 1-8 and comparative example 1-2 corresponding to the polishing experimental results of the cerium oxide dispersion
| 分散液Dispersions | TEOS RR(A/min)TEOS RR(A/min) |
| 实施例1Example 1 | 36203620 |
| 实施例2Example 2 | 37503750 |
| 实施例3Example 3 | 44004400 |
| 实施例4Example 4 | 39503950 |
| 实施例5Example 5 | 45504550 |
| 实施例6Example 6 | 41104110 |
| 实施例7Example 7 | 27002700 |
| 实施例8Example 8 | 39903990 |
| 对比例1Comparative example 1 | 18001800 |
| 对比例2Comparative example 2 | 15001500 |
根据表2中的测试结果可知，由本发明的合成方法制得的氧化铈具有较好的抛光性能。对比例1-2在合成过程中并未掺杂稀有元素，结合图3、图4可知，对比例1及对比例2中合成制得的氧化铈由于形貌不均匀，其抛光性质也不理想。According to the test results in Table 2, it can be seen that the cerium oxide prepared by the synthesis method of the present invention has better polishing performance. Comparative examples 1-2 were not doped with rare elements during the synthesis process. Combining with Figure 3 and Figure 4, it can be seen that the cerium oxide synthesized in Comparative Examples 1 and 2 was not ideal in polishing properties due to its uneven morphology. .
应当注意的是，本发明的实施例有较佳的实施性，且并非对本发明作任何形式的限制，任何熟悉该领域的技术人员可能利用上述揭示的技术内容变更或修饰为等同的有效实施例，但凡未脱离本发明技术方案的内容，依据本发明的技术实质对以上实施例所作的任何修改或等同变化及修饰，均仍属于本发明技术方案的范围内。It should be noted that the embodiments of the present invention have better implementability and are not intended to limit the present invention in any form. Any person skilled in the art may use the technical content disclosed above to change or modify equivalent effective embodiments However, any modifications or equivalent changes and modifications made to the above embodiments according to the technical essence of the present invention without departing from the content of the technical solution of the present invention still belong to the scope of the technical solution of the present invention.
Claims (13)
- 一种合成氧化铈的方法，其特征在于，包括：A method for synthesizing cerium oxide, comprising:S1：配置铈源水溶液，并向所述铈源水溶液中掺杂稀土元素；S1: configuring a cerium source aqueous solution, and doping rare earth elements into the cerium source aqueous solution;S2：配置沉淀剂水溶液，在反应釜中将所述铈源水溶液添加至所述沉淀剂水溶液中，制得混合溶液；S2: configuring a precipitant aqueous solution, adding the cerium source aqueous solution to the precipitant aqueous solution in a reaction kettle to prepare a mixed solution;S3：晶化反应：充分搅拌所述混合溶液，密闭所述反应釜进行高温晶化反应；S3: crystallization reaction: fully stir the mixed solution, seal the reaction kettle to carry out high temperature crystallization reaction;所述S1-S3中涉及原料均经惰性气体曝气处理，所述S1-S3均在惰性气体保护氛围中完成。The raw materials involved in the S1-S3 are all aerated with inert gas, and the S1-S3 are all completed in an inert gas protective atmosphere.
- 如权利要求1所述的合成氧化铈的方法，其特征在于，The method for synthesizing cerium oxide as claimed in claim 1, is characterized in that,所述稀土元素选自镧、镨、钕、钇、炕中的一种或多种。The rare earth element is selected from one or more of lanthanum, praseodymium, neodymium, yttrium and kang.
- 如权利要求1所述的合成氧化铈的方法，其特征在于，The method for synthesizing cerium oxide as claimed in claim 1, is characterized in that,所述稀土元素与所述铈源水溶液中铈元素的摩尔之比为0.1/100-20/100。The molar ratio of the rare earth element to the cerium element in the cerium source aqueous solution is 0.1/100-20/100.
- 如权利要求3所述的合成氧化铈的方法，其特征在于，The method for synthesizing cerium oxide as claimed in claim 3, is characterized in that,所述稀土元素与所述铈源水溶液中铈元素的摩尔之比为1/100-10/100。The molar ratio of the rare earth element to the cerium element in the cerium source aqueous solution is 1/100-10/100.
- 如权利要求1所述的合成氧化铈的方法，其特征在于，The method for synthesizing cerium oxide as claimed in claim 1, is characterized in that,所述铈源选自氯化铈、硝酸铈、醋酸铈、硝酸铈铵、硫酸铈中的一种或多种。The cerium source is selected from one or more of cerium chloride, cerium nitrate, cerium acetate, cerium ammonium nitrate, and cerium sulfate.
- 如权利要求1所述的合成氧化铈的方法，其特征在于，The method for synthesizing cerium oxide as claimed in claim 1, is characterized in that,所述铈源水溶液的摩尔浓度为0.1～1.0M。The molar concentration of the cerium source aqueous solution is 0.1-1.0M.
- 如权利要求6所述的合成氧化铈的方法，其特征在于，The method for synthesizing cerium oxide as claimed in claim 6, is characterized in that,所述铈源水溶液的摩尔浓度为0.2～0.6M。The molar concentration of the cerium source aqueous solution is 0.2-0.6M.
- 如权利要求1所述的合成氧化铈的方法，其特征在于，The method for synthesizing cerium oxide as claimed in claim 1, is characterized in that,所述沉淀剂选自氢氧化钠、氢氧化钾、氨水中的一种或多种。The precipitating agent is selected from one or more of sodium hydroxide, potassium hydroxide and ammonia water.
- 如权利要求1所述的合成氧化铈的方法，其特征在于，The method for synthesizing cerium oxide as claimed in claim 1, is characterized in that,所述沉淀剂水溶液的摩尔浓度为0.1～3.0M。The molar concentration of the precipitant aqueous solution is 0.1-3.0M.
- 如权利要求9所述的合成氧化铈的方法，其特征在于，The method for synthesizing cerium oxide as claimed in claim 9, is characterized in that,所述沉淀剂水溶液的摩尔浓度为0.5～1.5M。The molar concentration of the aqueous precipitation agent solution is 0.5-1.5M.
- 如权利要求1所述的合成氧化铈的方法，其特征在于，The method for synthesizing cerium oxide as claimed in claim 1, is characterized in that,所述晶化反应的反应温度为60℃-180℃，反应时间为1.0-24.0小时。The reaction temperature of the crystallization reaction is 60°C-180°C, and the reaction time is 1.0-24.0 hours.
- 如权利要求11所述的合成氧化铈的方法，其特征在于，The method for synthesizing cerium oxide as claimed in claim 11, is characterized in that,所述晶化反应的反应温度为80℃-120℃，反应时间为3.0-8.0小时。The reaction temperature of the crystallization reaction is 80°C-120°C, and the reaction time is 3.0-8.0 hours.
- 一种化学机械抛光液，其特征在于，A chemical mechanical polishing fluid, characterized in that,包括由权利要求1-12中任一所述的合成氧化铈的方法合成的氧化铈。It includes cerium oxide synthesized by the method for synthesizing cerium oxide described in any one of claims 1-12.
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