WO2022135607A1 - Synthesis method and use method for cerium oxide - Google Patents

Synthesis method and use method for cerium oxide Download PDF

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WO2022135607A1
WO2022135607A1 PCT/CN2021/142294 CN2021142294W WO2022135607A1 WO 2022135607 A1 WO2022135607 A1 WO 2022135607A1 CN 2021142294 W CN2021142294 W CN 2021142294W WO 2022135607 A1 WO2022135607 A1 WO 2022135607A1
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cerium
synthetic method
aqueous solution
raw material
cerium oxide
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PCT/CN2021/142294
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尹先升
刘同君
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安集微电子（上海）有限公司
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    • 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
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
    • C01F17/224—Oxides or hydroxides of lanthanides
    • C01F17/235—Cerium oxides or hydroxides
    • 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
    • C01F17/10—Preparation or treatment, e.g. separation or purification
    • 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
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM

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  • the invention relates to the field of chemical mechanical polishing, in particular to a method for synthesizing cerium oxide and a method for using the same.
  • Cerium oxide is an important polishing abrasive that is widely used in integrated circuit CMP.
  • the high polishing effect can be achieved at a low solid content, which makes it attract much attention as an abrasive in the field of chemical mechanical polishing fluids.
  • STI shallow trench isolation
  • the chemical mechanical polishing liquid using cerium oxide as the abrasive has greater application prospects and market advantages in terms of performance and cost than the polishing liquid using traditional silicon oxide or aluminum oxide as the abrasive.
  • cerium oxide when used as an abrasive, its own particle characteristics are very important to the polishing effect.
  • particle size and morphology of cerium oxide have an important influence on the generation of defects and the selection ratio of polishing rate during the polishing process.
  • the valence state distribution of Ce ions on the surface of cerium oxide particles plays a key role in the polishing characteristics.
  • the invention realizes the controlled synthesis of the surface valence state composition of the cerium oxide particles by synthesizing the cerium oxide nanoparticles of all tetravalent cerium.
  • the synthesized cerium oxide was applied in CMP polishing and showed unique CMP polishing characteristics.
  • the purpose of the present invention is to provide a synthesis of cerium oxide
  • the method includes adding a cerium source aqueous solution to a precipitant aqueous solution to generate a raw material solution; fully stirring the raw material solution to carry out a precipitation reaction; filtering the raw material solution to obtain gel state cerium hydroxide; configuring the gel state oxidation A cerium dispersion liquid, an oxidizing liquid is added to the dispersion liquid, and the reaction is heated in a closed container.
  • the cerium source aqueous solution is added to the precipitant aqueous solution under a nitrogen protective atmosphere to generate a raw material solution.
  • the precipitation reaction is carried out by fully stirring the raw material solution at a temperature of 30°C-90°C.
  • the precipitation reaction is carried out by fully stirring the raw material solution at a temperature of 50°C-70°C.
  • the raw material solution is fully stirred for 30 min to carry out the precipitation reaction.
  • the molar ratio of the cerium source to the precipitant is (1.0/4.0) ⁇ (1.0/6.0).
  • the cerium source is a soluble cerium salt.
  • the soluble cerium salt is one or more of cerium nitrate, cerium chloride and cerium acetate.
  • the soluble cerium salt is cerium nitrate.
  • the concentration of the cerium source aqueous solution is 0.1M-1.0M.
  • the concentration of the cerium source aqueous solution is 0.2M-0.6M.
  • the precipitant is a soluble base.
  • the soluble alkali is one or more of sodium hydroxide, potassium hydroxide and ammonia water.
  • the soluble base is ammonia water.
  • the concentration of the precipitant aqueous solution is 0.1M-3.0M.
  • the concentration of the precipitant aqueous solution is 0.5M to 1.5M.
  • the dispersion is placed in a closed container and heated to 120°C-250°C for reaction.
  • the dispersion is placed in a closed container and heated to 180°C-200°C for reaction.
  • the dispersion is placed in a closed container for heating and reaction for 2.0-8.0 hours.
  • the dispersion is placed in a closed container for heating and reaction for 4.0-6.0 hours.
  • the molar ratio of the oxidant to the cerium ions in the cerium source aqueous solution is 1/1-2/1.
  • the oxidant is selected from one or more of H 2 O 2 , potassium permanganate and potassium bromate.
  • the oxidant is H 2 O 2 .
  • Another aspect of the present invention provides a method for using cerium oxide, wherein any one of the cerium oxides described above is used for chemical mechanical polishing.
  • the cerium oxide synthesized by the synthesis method of the present invention has excellent polishing performance, has a higher polishing selection ratio for different materials, and effectively reduces the defects on the surface of the polished material.
  • Example 1 is a scanning electron microscope image of a cerium oxide product corresponding to Example 1 in accordance with the present invention
  • FIG. 2 is a scanning electron microscope image of the cerium oxide product corresponding to Comparative Example 2.
  • FIG. 2 is a scanning electron microscope image of the cerium oxide product corresponding to Comparative Example 2.
  • the synthesis conditions were corresponding to the synthesis of cerium oxide in Examples 1-6 and Comparative Examples 1-2.
  • the specific synthesis steps are as follows: respectively prepare the cerium source aqueous solution and the precipitant aqueous solution; under nitrogen protection atmosphere, add the cerium source aqueous solution to the precipitant aqueous solution; fully stir for 30 min to carry out the precipitation reaction; It is configured into a gel state cerium oxide dispersion liquid, and an oxidant is added to the dispersion liquid, and is synthesized at the corresponding synthesis temperature for a certain period of time.
  • the synthesis temperature and synthesis time of each embodiment and comparative example are shown in Table 1.
  • Example 1 and Comparative Example 2 were made into samples taken by scanning electron microscope. After the samples were diluted, they were directly dropped on the slide, and after natural drying, gold spraying treatment was performed, and then SEM analysis was performed.
  • the specific shooting conditions are: Hitachi High-tech Cold Field SU-8220, voltage 15KV, current 10umA.
  • FIG. 1 and FIG. 2 are SEM images of cerium oxide particles corresponding to Example 1 and Comparative Example 2, respectively. It can be seen that the particle size distribution of the corresponding product of Example 1 is uniform, the particle morphology is regular, and the corresponding particle characteristics are significantly better than that of Comparative Example 2.
  • the polishing properties of the examples and comparative examples were further tested.
  • the corresponding cerium oxide product is washed and dispersed to obtain a cerium oxide dispersion.
  • the cerium oxide dispersions corresponding to the examples and comparative examples in Table 1 were prepared as polishing liquids, which were respectively prepared as 0.25wt% aqueous dispersions with a solid content of pH 4.5, and the polishing of TEOS and SiN blank wafers were measured under different pressure conditions. Removal rate (RR), polishing selectivity ratio of the two (TEOS/SiN) and TEOS surface roughness.
  • the specific polishing conditions were as follows: the polishing machine was Mirra, the IC1010 polishing pad, the Platten and Carrier speeds were 93 rpm and 87 rpm, respectively, the pressure was 3 psi, the polishing liquid flow rate was 150 mL/min, and the polishing time was 60 seconds.
  • the surface scratch measurement equipment is OM, and the 4um x 4um area of the central area of the TEOS wafer surface after polishing is selected for surface measurement.
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Example 6 Comparative Example 1 Comparative Example 2
  • the cerium oxide particles synthesized without adding an oxidant during the synthesis process are uneven, and even if they have a high polishing rate and selectivity, they will cause great damage to the surface of the polishing material and are likely to cause more surface scratches. Can not meet the actual production needs.
  • the cerium oxide synthesized in the present invention not only has excellent polishing effect, but also can effectively reduce defects on the surface of the material after polishing, and has broad application prospects in the field.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)

Abstract

A synthesis method for cerium oxide, comprising: adding a cerium source aqueous solution into a precipitant aqueous solution to generate a raw material solution; fully stirring the raw material solution, and carrying out a precipitation reaction; filtering the raw material solution to obtain gel state hydrogen cerium oxide; and preparing a gel state cerium oxide dispersion liquid, adding an oxidizing agent into the dispersion liquid, and placing the mixture in a closed container for a heating reaction. The synthesized cerium oxide has excellent polishing performance, and has a higher polishing selection ratio for different materials, and a defect of the surface of a polished material is effectively reduced.

Description

一种氧化铈的合成方法及其使用方法A kind of synthetic method of cerium oxide and use method thereof 技术领域technical field
本发明涉及化学机械抛光领域，尤其涉及一种氧化铈的合成方法及其使用方法。The invention relates to the field of chemical mechanical polishing, in particular to a method for synthesizing cerium oxide and a method for using the same.
背景技术Background technique
氧化铈是一种重要的抛光磨料，在集成电路CMP中有着广泛应用。在较低的固含量下就可达到高的抛光效果，使其作为磨料在化学机械抛光液领域备受关注。比如，以氧化铈作为磨料应用于浅沟槽隔离(STI)工艺抛光已有大量报道(如ZL201310495424.5，ZL200510069987.3)。同时，以氧化铈为磨料的化学机械抛光液，在性能和成本上相比于使用传统的氧化硅或氧化铝材料作为磨料的抛光液具有更大的应用前景和市场优势。Cerium oxide is an important polishing abrasive that is widely used in integrated circuit CMP. The high polishing effect can be achieved at a low solid content, which makes it attract much attention as an abrasive in the field of chemical mechanical polishing fluids. For example, the application of cerium oxide as an abrasive in shallow trench isolation (STI) process polishing has been widely reported (eg ZL201310495424.5, ZL200510069987.3). At the same time, the chemical mechanical polishing liquid using cerium oxide as the abrasive has greater application prospects and market advantages in terms of performance and cost than the polishing liquid using traditional silicon oxide or aluminum oxide as the abrasive.
研究表明，以氧化铈作为磨料时，其自身的颗粒特性对抛光效果的影响至关重要。如在STI抛光应用中，有文献报道氧化铈颗粒尺寸、形貌特征对抛光过程中缺陷的产生和抛光速率选择比均有着重要影响。同时，氧化铈颗粒表面Ce离子价态分布对抛光特性起着关键影响。Studies have shown that when cerium oxide is used as an abrasive, its own particle characteristics are very important to the polishing effect. For example, in the application of STI polishing, it has been reported that the particle size and morphology of cerium oxide have an important influence on the generation of defects and the selection ratio of polishing rate during the polishing process. Meanwhile, the valence state distribution of Ce ions on the surface of cerium oxide particles plays a key role in the polishing characteristics.
本发明通过合成全四价铈的氧化铈纳米颗粒，实现对氧化铈颗粒表面价态组成的控制合成。所合成的氧化铈应用于CMP抛光，显示出独特的CMP抛光特性。The invention realizes the controlled synthesis of the surface valence state composition of the cerium oxide particles by synthesizing the cerium oxide nanoparticles of all tetravalent cerium. The synthesized cerium oxide was applied in CMP polishing and showed unique CMP polishing characteristics.
发明内容SUMMARY OF THE INVENTION
为了提高本领域中氧化铈的抛光效果，提高氧化铈对不同材料，尤其是TEOS和SiN材料的抛光选择比，以及减少抛光后材料表面的缺陷，本发明的目的在于提供一种氧化铈的合成方法，包括将铈源水溶液添加至沉淀剂水溶液中，生成原料溶液；充分搅拌所述原料溶液，进行沉淀反应；过滤所述原料溶液，得到凝胶态氢氧化铈；配置所述凝胶态氧化铈分散液，向所述分散液中添加氧化剂，并置于密闭容器内加热反应。In order to improve the polishing effect of cerium oxide in the field, improve the polishing selection ratio of cerium oxide to different materials, especially TEOS and SiN materials, and reduce the defects on the surface of the material after polishing, the purpose of the present invention is to provide a synthesis of cerium oxide The method includes adding a cerium source aqueous solution to a precipitant aqueous solution to generate a raw material solution; fully stirring the raw material solution to carry out a precipitation reaction; filtering the raw material solution to obtain gel state cerium hydroxide; configuring the gel state oxidation A cerium dispersion liquid, an oxidizing liquid is added to the dispersion liquid, and the reaction is heated in a closed container.
优选的，在氮气保护氛围下，将铈源水溶液添加至沉淀剂水溶液中，生成原料溶液。Preferably, the cerium source aqueous solution is added to the precipitant aqueous solution under a nitrogen protective atmosphere to generate a raw material solution.
优选的，在30℃-90℃温度条件下，充分搅拌所述原料溶液，进行沉淀反应。Preferably, the precipitation reaction is carried out by fully stirring the raw material solution at a temperature of 30°C-90°C.
优选的，在50℃-70℃温度条件下，充分搅拌所述原料溶液，进行沉淀反应。Preferably, the precipitation reaction is carried out by fully stirring the raw material solution at a temperature of 50°C-70°C.
优选的，充分搅拌所述原料溶液30min，进行沉淀反应。Preferably, the raw material solution is fully stirred for 30 min to carry out the precipitation reaction.
优选的，所述铈源与所述沉淀剂的摩尔比为(1.0/4.0)～(1.0/6.0)。Preferably, the molar ratio of the cerium source to the precipitant is (1.0/4.0)˜(1.0/6.0).
优选的，所述铈源为可溶性铈盐。Preferably, the cerium source is a soluble cerium salt.
优选的，所述可溶性铈盐为硝酸铈，氯化铈，醋酸铈中的一种或多种。Preferably, the soluble cerium salt is one or more of cerium nitrate, cerium chloride and cerium acetate.
优选的，所述可溶性铈盐为硝酸铈。Preferably, the soluble cerium salt is cerium nitrate.
优选的，所述铈源水溶液的浓度为0.1M～1.0M。Preferably, the concentration of the cerium source aqueous solution is 0.1M-1.0M.
优选的，所述铈源水溶液的浓度为0.2M～0.6M。Preferably, the concentration of the cerium source aqueous solution is 0.2M-0.6M.
优选的，所述沉淀剂为可溶性碱。Preferably, the precipitant is a soluble base.
优选的，所述可溶性碱为氢氧化钠，氢氧化钾，氨水中的一种或多种。Preferably, the soluble alkali is one or more of sodium hydroxide, potassium hydroxide and ammonia water.
优选的，所述可溶性碱为氨水。Preferably, the soluble base is ammonia water.
优选的，所述沉淀剂水溶液的浓度为0.1M～3.0M。Preferably, the concentration of the precipitant aqueous solution is 0.1M-3.0M.
优选的，所述沉淀剂水溶液的浓度为0.5M～1.5M。Preferably, the concentration of the precipitant aqueous solution is 0.5M to 1.5M.
优选的，将所述分散液置于密闭容器内加热至120℃-250℃反应。Preferably, the dispersion is placed in a closed container and heated to 120°C-250°C for reaction.
优选的，将所述分散液置于密闭容器内加热至180℃-200℃反应。Preferably, the dispersion is placed in a closed container and heated to 180°C-200°C for reaction.
优选的，将所述分散液置于密闭容器内加热反应2.0-8.0小时。Preferably, the dispersion is placed in a closed container for heating and reaction for 2.0-8.0 hours.
优选的，将所述分散液置于密闭容器内加热反应4.0-6.0小时。Preferably, the dispersion is placed in a closed container for heating and reaction for 4.0-6.0 hours.
优选的，所述氧化剂与所述铈源水溶液中铈离子的摩尔比为1/1-2/1。Preferably, the molar ratio of the oxidant to the cerium ions in the cerium source aqueous solution is 1/1-2/1.
优选的，所述氧化剂选自H 2O 2、高锰酸钾、溴酸钾中一种或多种。 Preferably, the oxidant is selected from one or more of H 2 O 2 , potassium permanganate and potassium bromate.
优选的，所述氧化剂为H 2O 2。 Preferably, the oxidant is H 2 O 2 .
本发明的另一方面提供一种氧化铈的使用方法，将如上所述的中任一氧化铈用于化学机械抛光。Another aspect of the present invention provides a method for using cerium oxide, wherein any one of the cerium oxides described above is used for chemical mechanical polishing.
使用本发明的合成方法合成出的氧化铈具有优异的抛光性能，对不同材料具有较高的抛光选择比，且有效减少了抛光后材料表面的缺陷。The cerium oxide synthesized by the synthesis method of the present invention has excellent polishing performance, has a higher polishing selection ratio for different materials, and effectively reduces the defects on the surface of the polished material.
附图说明Description of drawings
图1为符合本发明的实施例1对应的氧化铈产物的扫描电子显微镜图像；1 is a scanning electron microscope image of a cerium oxide product corresponding to Example 1 in accordance with the present invention;
图2为对比例2对应的氧化铈产物的扫描电子显微镜图像。FIG. 2 is a scanning electron microscope image of the cerium oxide product corresponding to Comparative Example 2. FIG.
具体实施方式Detailed ways
以下结合具体实施例进一步阐述本发明的优点。The advantages of the present invention are further described below with reference to specific embodiments.
依照表1中所示的反应物种类及其浓度，合成条件相应合成实施例1-6和对比例1-2中的氧化铈。具体合成步骤为：分别配置铈源水溶液和沉淀剂水溶液；在氮气保护氛围下，将铈源水溶液添加至沉淀剂水溶液中；充分搅拌30min，进行沉淀反应；过滤，清洗沉淀物后，将沉淀物配置成凝胶态氧化铈分散液，向所述分散液中添加氧化剂，并在相应的合成温度下合成一定时间，各实施例及对比例的合成温度及合成时间如表1所示。According to the types of reactants and their concentrations shown in Table 1, the synthesis conditions were corresponding to the synthesis of cerium oxide in Examples 1-6 and Comparative Examples 1-2. The specific synthesis steps are as follows: respectively prepare the cerium source aqueous solution and the precipitant aqueous solution; under nitrogen protection atmosphere, add the cerium source aqueous solution to the precipitant aqueous solution; fully stir for 30 min to carry out the precipitation reaction; It is configured into a gel state cerium oxide dispersion liquid, and an oxidant is added to the dispersion liquid, and is synthesized at the corresponding synthesis temperature for a certain period of time. The synthesis temperature and synthesis time of each embodiment and comparative example are shown in Table 1.
表1实施例1-6与对比例1-2的反应物种类及浓度、合成条件The species and concentration of reactants and synthesis conditions of Table 1 Example 1-6 and Comparative Example 1-2
Figure PCTCN2021142294-appb-000001
Figure PCTCN2021142294-appb-000001
将实施例1及对比例2的氧化铈产物制成扫描电子显微镜拍摄样品，将样品稀释后，直接滴在载物片上，自然干燥后，喷金处理，然后进行SEM分析。The cerium oxide products of Example 1 and Comparative Example 2 were made into samples taken by scanning electron microscope. After the samples were diluted, they were directly dropped on the slide, and after natural drying, gold spraying treatment was performed, and then SEM analysis was performed.
具体拍摄条件为：日立高新冷场SU-8220，电压15KV，电流10umA。The specific shooting conditions are: Hitachi High-tech Cold Field SU-8220, voltage 15KV, current 10umA.
图1和图2分别为实施例1和对比例2对应氧化铈颗粒的SEM图像。可以看出，实施例1对应产物颗粒尺寸分布均一，颗粒形貌规整，对应颗粒特性明显优于对比例2。FIG. 1 and FIG. 2 are SEM images of cerium oxide particles corresponding to Example 1 and Comparative Example 2, respectively. It can be seen that the particle size distribution of the corresponding product of Example 1 is uniform, the particle morphology is regular, and the corresponding particle characteristics are significantly better than that of Comparative Example 2.
进一步测试实施例及对比例样品的抛光性能。对相应的氧化铈产物进行洗涤、分散处理，得到氧化铈分散液。将表1中实施例和对比例对应氧化铈分散液配制为抛光液，分别调配为0.25wt％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、SiN空白晶圆的抛光去除速率(RR)、二者抛光选择比(TEOS/SiN)和TEOS表面粗糙度。The polishing properties of the examples and comparative examples were further tested. The corresponding cerium oxide product is washed and dispersed to obtain a cerium oxide dispersion. The cerium oxide dispersions corresponding to the examples and comparative examples in Table 1 were prepared as polishing liquids, which were respectively prepared as 0.25wt% aqueous dispersions with a solid content of pH 4.5, and the polishing of TEOS and SiN blank wafers were measured under different pressure conditions. Removal rate (RR), polishing selectivity ratio of the two (TEOS/SiN) and TEOS surface roughness.
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 were as follows: the polishing machine was Mirra, the IC1010 polishing pad, the Platten and Carrier speeds were 93 rpm and 87 rpm, respectively, the pressure was 3 psi, the polishing liquid flow rate was 150 mL/min, and the polishing time was 60 seconds.
表面划痕测量设备为OM，选取抛光后TEOS晶圆表面中心区域4um x 4um区域进 行表面测量。The surface scratch measurement equipment is OM, and the 4um x 4um area of the central area of the TEOS wafer surface after polishing is selected for surface measurement.
表2实施例1-6及对比例1-2对应氧化铈分散液抛光实验结果Table 2 Examples 1-6 and Comparative Examples 1-2 correspond to the experimental results of cerium oxide dispersion polishing
样品sample 实施例1Example 1 实施例2Example 2 实施例3Example 3 实施例4Example 4 实施例5Example 5 实施例6Example 6 对比例1Comparative Example 1 对比例2Comparative Example 2
TEOS RR(A/min)TEOS RR(A/min) 23502350 22102210 27502750 24402440 25512551 25472547 27462746 26352635
SiN RR(A/min)SiN RR(A/min) 224224 205205 240240 194194 189189 175175 210210 332332
TEOS/SiNTEOS/SiN 10.510.5 10.810.8 11.511.5 12.612.6 13.513.5 14.614.6 13.113.1 7.97.9
TEOS表面划痕Scratches on the TEOS surface 22 11 00 22 22 33 1515 44
综上可知，在合成过程中不添加氧化剂合成的氧化铈颗粒不均，即便其具有较高的抛光速率及选择性，但对抛光材料表面的伤害较大，容易造成较多的表面划痕，不能够满足实际生产需求。而本发明中合成的氧化铈不仅具有优异的抛光效果，同时能够有效减少抛光后材料表面的缺陷，在本领域具有广阔的应用前景。In summary, the cerium oxide particles synthesized without adding an oxidant during the synthesis process are uneven, and even if they have a high polishing rate and selectivity, they will cause great damage to the surface of the polishing material and are likely to cause more surface scratches. Can not meet the actual production needs. The cerium oxide synthesized in the present invention not only has excellent polishing effect, but also can effectively reduce defects on the surface of the material after polishing, and has broad application prospects in the field.
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 practicability, and do not limit the present invention in any form, and any person skilled in the art may use the technical contents disclosed above to change or modify into 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 fall within the scope of the technical solution of the present invention.

Claims (24)

  1. 一种氧化铈的合成方法，其特征在于，包括A kind of synthetic method of cerium oxide, is characterized in that, comprises
    将铈源水溶液添加至沉淀剂水溶液中，生成原料溶液；adding the cerium source aqueous solution to the precipitant aqueous solution to generate a raw material solution;
    充分搅拌所述原料溶液，进行沉淀反应；Fully stirring the raw material solution to carry out precipitation reaction;
    过滤所述原料溶液，得到凝胶态氢氧化铈；filtering the raw material solution to obtain gel-state cerium hydroxide;
    配置所述凝胶态氧化铈分散液，向所述分散液中添加氧化剂，并置于密闭容器内加热反应。The gel state cerium oxide dispersion is prepared, an oxidant is added to the dispersion, and the solution is placed in a closed container for heating and reaction.
  2. 如权利要求1所述的合成方法，其特征在于，synthetic method as claimed in claim 1, is characterized in that,
    在氮气保护氛围下，将铈源水溶液添加至沉淀剂水溶液中，生成原料溶液。Under a nitrogen protective atmosphere, the cerium source aqueous solution was added to the precipitant aqueous solution to generate a raw material solution.
  3. 如权利要求1所述的合成方法，其特征在于，synthetic method as claimed in claim 1, is characterized in that,
    在30℃-90℃温度条件下，充分搅拌所述原料溶液，进行沉淀反应。Under the temperature condition of 30°C-90°C, the raw material solution is fully stirred to carry out the precipitation reaction.
  4. 如权利要求3所述的合成方法，其特征在于，synthesis method as claimed in claim 3, is characterized in that,
    在50℃-70℃温度条件下，充分搅拌所述原料溶液，进行沉淀反应。Under the temperature condition of 50°C-70°C, the raw material solution is fully stirred to carry out the precipitation reaction.
  5. 如权利要求1所述的合成方法，其特征在于，synthetic method as claimed in claim 1, is characterized in that,
    充分搅拌所述原料溶液30min，进行沉淀反应。The raw material solution was fully stirred for 30 min to carry out the precipitation reaction.
  6. 如权利要求1所述的合成方法，其特征在于，synthetic method as claimed in claim 1, is characterized in that,
    所述铈源与所述沉淀剂的摩尔比为(1.0/4.0)-(1.0/6.0)。The molar ratio of the cerium source to the precipitant is (1.0/4.0)-(1.0/6.0).
  7. 如权利要求1所述的合成方法，其特征在于，synthetic method as claimed in claim 1, is characterized in that,
    所述铈源为可溶性铈盐。The cerium source is a soluble cerium salt.
  8. 如权利要求7所述的合成方法，其特征在于，synthesis method as claimed in claim 7, is characterized in that,
    所述可溶性铈盐为硝酸铈，氯化铈，醋酸铈中的一种或多种。The soluble cerium salt is one or more of cerium nitrate, cerium chloride and cerium acetate.
  9. 如权利要求8所述的合成方法，其特征在于，synthesis method as claimed in claim 8, is characterized in that,
    所述可溶性铈盐为硝酸铈。The soluble cerium salt is cerium nitrate.
  10. 如权利要求1所述的合成方法，其特征在于，synthetic method as claimed in claim 1, is characterized in that,
    所述铈源水溶液的浓度为0.1M-1.0M。The concentration of the cerium source aqueous solution is 0.1M-1.0M.
  11. 如权利要求10所述的合成方法，其特征在于，The synthetic method of claim 10, wherein,
    所述铈源水溶液的浓度为0.2M-0.6M。The concentration of the cerium source aqueous solution is 0.2M-0.6M.
  12. 如权利要求1所述的合成方法，其特征在于，synthetic method as claimed in claim 1, is characterized in that,
    所述沉淀剂为可溶性碱。The precipitant is a soluble base.
  13. 如权利要求12所述的合成方法，其特征在于，The synthetic method of claim 12, wherein,
    所述可溶性碱为氢氧化钠，氢氧化钾，氨水中的一种或多种。The soluble alkali is one or more of sodium hydroxide, potassium hydroxide and ammonia water.
  14. 如权利要求13所述的合成方法，其特征在于，The synthetic method of claim 13, wherein,
    所述可溶性碱为氨水。The soluble base is ammonia water.
  15. 如权利要求1所述的合成方法，其特征在于，synthetic method as claimed in claim 1, is characterized in that,
    所述沉淀剂水溶液的浓度为0.1M-3.0M。The concentration of the precipitant aqueous solution is 0.1M-3.0M.
  16. 如权利要求15所述的合成方法，其特征在于，The synthetic method of claim 15, wherein,
    所述沉淀剂水溶液的浓度为0.5M-1.5M。The concentration of the precipitant aqueous solution is 0.5M-1.5M.
  17. 如权利要求1所述的合成方法，其特征在于，synthetic method as claimed in claim 1, is characterized in that,
    将所述分散液置于密闭容器内加热至120℃-250℃反应。The dispersion liquid is placed in a closed container and heated to 120°C-250°C for reaction.
  18. 如权利要求18所述的合成方法，其特征在于，The synthetic method of claim 18, wherein
    将所述分散液置于密闭容器内加热至180℃-200℃反应。The dispersion liquid is placed in a closed container and heated to 180°C-200°C for reaction.
  19. 如权利要求1所述的合成方法，其特征在于，synthetic method as claimed in claim 1, is characterized in that,
    将所述分散液置于密闭容器内加热反应2.0-8.0小时。The dispersion was placed in a closed container and heated for 2.0-8.0 hours.
  20. 如权利要求20所述的合成方法，其特征在于，The synthetic method of claim 20, wherein,
    将所述分散液置于密闭容器内加热反应4.0-6.0小时。The dispersion was placed in a closed container and heated for 4.0-6.0 hours.
  21. 如权利要求1所述的合成方法，其特征在于，synthetic method as claimed in claim 1, is characterized in that,
    所述氧化剂与所述铈源水溶液中铈离子的摩尔比为1/1-2/1。The molar ratio of the oxidant to the cerium ions in the cerium source aqueous solution is 1/1-2/1.
  22. 如权利要求1所述的合成方法，其特征在于，synthetic method as claimed in claim 1, is characterized in that,
    所述氧化剂选自H 2O 2、高锰酸钾、溴酸钾中一种或多种。 The oxidant is selected from one or more of H 2 O 2 , potassium permanganate and potassium bromate.
  23. 如权利要求23所述的合成方法，其特征在于，The synthetic method of claim 23, wherein
    所述氧化剂为H 2O 2。 The oxidant is H 2 O 2 .
  24. 一种氧化铈的使用方法，将如权利要求1-24中任一所述的氧化铈用于化学机械抛光。A method for using cerium oxide, wherein the cerium oxide according to any one of claims 1-24 is used for chemical mechanical polishing.
PCT/CN2021/142294 2020-12-25 2021-12-29 Synthesis method and use method for cerium oxide WO2022135607A1 (en)

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