WO2013020351A1 - Chemical mechanical polishing solution - Google Patents
Chemical mechanical polishing solution Download PDFInfo
- Publication number
- WO2013020351A1 WO2013020351A1 PCT/CN2012/000764 CN2012000764W WO2013020351A1 WO 2013020351 A1 WO2013020351 A1 WO 2013020351A1 CN 2012000764 W CN2012000764 W CN 2012000764W WO 2013020351 A1 WO2013020351 A1 WO 2013020351A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polishing liquid
- cerium oxide
- liquid according
- chemical mechanical
- abrasive
- Prior art date
Links
- 238000005498 polishing Methods 0.000 title claims abstract description 34
- 239000000126 substance Substances 0.000 title claims abstract description 8
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 19
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 13
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 6
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 5
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 claims description 5
- 239000003002 pH adjusting agent Substances 0.000 claims description 4
- LMHAGAHDHRQIMB-UHFFFAOYSA-N 1,2-dichloro-1,2,3,3,4,4-hexafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(Cl)C1(F)Cl LMHAGAHDHRQIMB-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 13
- 238000002955 isolation Methods 0.000 abstract description 8
- 229910052581 Si3N4 Inorganic materials 0.000 abstract description 7
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000377 silicon dioxide Substances 0.000 abstract description 6
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 4
- 239000012530 fluid Substances 0.000 abstract description 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
- 238000000034 method Methods 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 239000005562 Glyphosate Substances 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 229940097068 glyphosate Drugs 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009924 canning Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229960002449 glycine Drugs 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000013517 stratification 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
-
- 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
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/31051—Planarisation of the insulating layers
- H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
Definitions
- the present invention relates to an abrasive material, and more particularly to a chemical mechanical polishing fluid.
- COMS chips are typically fabricated by integrating hundreds of millions of active devices (including NMOS and PMOS) on silicon substrate materials, and then designing various circuits to implement complex logic and analog functions. To ensure electrical isolation between different devices, insulation is used to isolate them. Shallow trench isolation (STI) is an industrial method of forming isolation regions between active devices. The isolation method is to grow a silicon dioxide layer on the substrate, and then deposit a silicon nitride film, the typical thickness of which is 10-20 nm and 50-100 nm, respectively, and then apply the glue, Exposure and development, as shown in Figure 1.
- STI Shallow trench isolation
- the 5-6 step requires a CMP planarization process that requires rapid removal of silicon dioxide and stops on the silicon nitride, which requires a higher HDP/SIN selectivity ratio for the polishing solution.
- the dish-shaped depressions in different density areas can not differ by 200 angstroms, the surface is smooth and clean, and the particle contaminants and defects are smaller than the process requirements.
- the widely used chip factory is a cerium oxide polishing liquid.
- This type of polishing liquid has a high polishing speed and a relatively high selection of silicon nitride. It is a relatively mature industrial product, but this type of polishing liquid is prone to sedimentation and stratification. The equipment requirements are high, and the price is expensive. In the context of reducing the efficiency of the global chip industry, reducing the cost is also one of the requirements of the polishing liquid. Summary of invention
- the present invention discloses a chemical mechanical polishing composition suitable for shallow trench isolation planarization, the polishing liquid containing at least one cerium oxide abrasive, an organic phosphonic acid, A pH adjuster, and carrier water.
- the cerium oxide abrasive has a particle size of 20-500 nm and a solid content of 0.1% to 10% by weight. Preferably at 60-250 nm, the abrasive action is to remove HDP silica.
- the cerium oxide abrasive selected for the polishing solution is an aqueous dispersion of nano cerium oxide powder having a pH of 8-11.
- the organic phosphonic acid is one or more selected from the group consisting of 2-hydroxyphosphonoacetic acid, hydroxyethylidene diphosphonic acid (HEDP) and N-(phosphonomethyl)glycine, at a concentration of 0.05% by weight. -lwt%.
- the role of the organic phosphonic acid is to inhibit the removal rate of silicon nitride. Among them, N-(phosphonomethyl)aminoacetic acid is also known as glyphosate.
- the pH adjuster is KOH or an organic amine, and the pH of the polishing solution is 7-12.
- This paper uses a basic particle size distribution of basic cerium oxide particles with a high HDP removal rate, selected from the group consisting of 2-hydroxyphosphonoacetic acid, hydroxyethylidene diphosphonic acid (HEDP) and N- (phosphine).
- HEDP hydroxyethylidene diphosphonic acid
- N- (phosphine) One or more organic phosphonic acids in acylmethyl)glycine at a polishing rate of a suitable HDP silica, greatly reducing the removal rate of silicon nitride to achieve a high selectivity ratio, isolated in shallow trenches During the canning process, the silicon nitride layer is stopped to achieve planarization.
- FIG. 1 is a schematic view of an industrialization method for forming an isolation region in the prior art.
- the polishing liquid was prepared according to the ratio in Table 1, and several components were simply mixed.
- the selectivity of silicon dioxide, the removal rate of silicon oxide (HDP) will decrease to some extent with the addition of Glyphosate, and the selection ratio is still adjustable.
- the STI polishing solution prepared using the oxidized abrasive has a higher removal rate than the silica sol-based polishing liquid, and the selection ratio also has a larger control interval. Demonstrated a certain technical advantage in the flattening of STI.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
Disclosed is a chemical mechanical polishing solution for shallow trench isolation. The polishing fluid at least comprises an abrasive containing cerium dioxide, an organic phosphonic acid, a pH regulator, and carrier water, and has a high rate in removing high-density plasma silicon dioxide and a low rate in removing silicon nitride. The polished surface is planar and smooth, and has good stability. The present invention is applicable to chemical mechanical planarization for shallow trench isolation.
Description
一种化学机械抛光液 技术领域 Chemical mechanical polishing liquid
本发明涉及一种研磨材料, 尤其涉及一种化学机械抛光液。 The present invention relates to an abrasive material, and more particularly to a chemical mechanical polishing fluid.
技术背景 technical background
COMS芯片的制造通常是在硅衬底材料上集成数以亿计的有源器件(包 括 NMOS和 PMOS), 进而设计各种电路实现复杂的逻辑功能和模拟功能。 要确保不同器件之间的电学隔离, 就要采用绝缘材料将其隔离, 浅槽隔离 (STI) 就是在有源器件之间形成隔离区的工业化方法。 这种隔离方法, 是 在衬底上生长一层二氧化硅层, 然后再淀积一层氮化硅薄膜, 二者的典型厚 度分别为 10-20nm和 50-100nm, 然后进行涂胶,、曝光和显影, 如图 1所示。 COMS chips are typically fabricated by integrating hundreds of millions of active devices (including NMOS and PMOS) on silicon substrate materials, and then designing various circuits to implement complex logic and analog functions. To ensure electrical isolation between different devices, insulation is used to isolate them. Shallow trench isolation (STI) is an industrial method of forming isolation regions between active devices. The isolation method is to grow a silicon dioxide layer on the substrate, and then deposit a silicon nitride film, the typical thickness of which is 10-20 nm and 50-100 nm, respectively, and then apply the glue, Exposure and development, as shown in Figure 1.
在图 1中看出 5— 6的步骤需要用 CMP平坦化工艺,要求快速去除二氧 化硅并停止在氮化硅上面, 这就要求其抛光液要具有较高的 HDP/SIN的选 择比, 通常要大于 10, 并且在不同密度区域的碟形凹陷不能相差 200埃, 表 面光滑洁净, 颗粒污染物和缺陷等均小于工艺要求的指标。 It is seen in Figure 1 that the 5-6 step requires a CMP planarization process that requires rapid removal of silicon dioxide and stops on the silicon nitride, which requires a higher HDP/SIN selectivity ratio for the polishing solution. Usually greater than 10, and the dish-shaped depressions in different density areas can not differ by 200 angstroms, the surface is smooth and clean, and the particle contaminants and defects are smaller than the process requirements.
目前芯片厂广泛应用的是二氧化铈抛光液, 该类抛光液抛光速度快, 对 氮化硅的选择比较高, 是较为成熟的工业化产品, 但该类抛光液容易产生沉 淀分层, 对在线的设备要求较高, 另外价格昂贵, 在全球芯片行业降耗增效 的背景下, 降低成本也是抛光液的要求之一。 发明概要 At present, the widely used chip factory is a cerium oxide polishing liquid. This type of polishing liquid has a high polishing speed and a relatively high selection of silicon nitride. It is a relatively mature industrial product, but this type of polishing liquid is prone to sedimentation and stratification. The equipment requirements are high, and the price is expensive. In the context of reducing the efficiency of the global chip industry, reducing the cost is also one of the requirements of the polishing liquid. Summary of invention
本发明的目的是提供一种能够克服上述现有技术中缺陷的化学机械抛 光液。 本发明的技术方案如下:本发明公开一种适合于浅槽隔离平坦化的化学 机械抛光组合物, 该抛光液至少含有一种二氧化铈的磨料, 一种有机膦酸,
一种 pH调节剂, 和载体水。 It is an object of the present invention to provide a chemical mechanical polishing liquid which overcomes the above-mentioned drawbacks of the prior art. The technical scheme of the present invention is as follows: The present invention discloses a chemical mechanical polishing composition suitable for shallow trench isolation planarization, the polishing liquid containing at least one cerium oxide abrasive, an organic phosphonic acid, A pH adjuster, and carrier water.
其中, 二氧化铈磨料粒径为 20-500nm, 固含量从 0.1\^%到 10wt%。 最 好在 60-250nm, 磨料作用是去除 HDP二氧化硅。 该抛光液选用的氧化铈磨料为 pH 8-11的纳米氧化铈粉的水分散体。 其中, 有机膦酸为选自 2-羟基膦酰基乙酸、羟基亚乙基二膦酸(HEDP) 和 N- (膦酰基甲基) 氨基乙酸中的一种或多种, 其浓度为 0.05wt%-lwt%。 有机膦酸的作用是抑制氮化硅的去除速率。 其中 N- (膦酰基甲基) 氨基乙 酸又名草甘膦(Glyphosate)。 The cerium oxide abrasive has a particle size of 20-500 nm and a solid content of 0.1% to 10% by weight. Preferably at 60-250 nm, the abrasive action is to remove HDP silica. The cerium oxide abrasive selected for the polishing solution is an aqueous dispersion of nano cerium oxide powder having a pH of 8-11. Wherein the organic phosphonic acid is one or more selected from the group consisting of 2-hydroxyphosphonoacetic acid, hydroxyethylidene diphosphonic acid (HEDP) and N-(phosphonomethyl)glycine, at a concentration of 0.05% by weight. -lwt%. The role of the organic phosphonic acid is to inhibit the removal rate of silicon nitride. Among them, N-(phosphonomethyl)aminoacetic acid is also known as glyphosate.
其中, pH调节剂为 KOH或者有机胺, 抛光液的 pH值为 7-12。 Wherein, the pH adjuster is KOH or an organic amine, and the pH of the polishing solution is 7-12.
本发明的有益效果是: The beneficial effects of the invention are:
本文采用一种一定粒径分布的碱性的二氧化铈颗粒, 具有较高的 HDP 去除速率, 采用选自 2-羟基膦酰基乙酸、 羟基亚乙基二膦酸(HEDP)和 N- (膦酰基甲基) 氨基乙酸中的一种或多种的有机膦酸在合适的 HDP氧化硅 的抛光速率下, 大幅度降低氮化硅的去除速率, 以达到高的选择比, 在浅槽 隔离的坦化过程中停止在氮化硅层, 实现平坦化。 附图说明 This paper uses a basic particle size distribution of basic cerium oxide particles with a high HDP removal rate, selected from the group consisting of 2-hydroxyphosphonoacetic acid, hydroxyethylidene diphosphonic acid (HEDP) and N- (phosphine). One or more organic phosphonic acids in acylmethyl)glycine at a polishing rate of a suitable HDP silica, greatly reducing the removal rate of silicon nitride to achieve a high selectivity ratio, isolated in shallow trenches During the canning process, the silicon nitride layer is stopped to achieve planarization. DRAWINGS
图 1为现有技术中形成隔离区的工业化方法示意图。 1 is a schematic view of an industrialization method for forming an isolation region in the prior art.
发明内容 Summary of the invention
下面通过具体实施方式来进一步阐述本发明。 The invention is further illustrated by the following detailed description.
按照表 1中的配比制备抛光液, 几种组分简单混合即可。 The polishing liquid was prepared according to the ratio in Table 1, and several components were simply mixed.
抛光条件: Polishing conditions:
下压力: 4psi
抛光垫: IC1000抛光垫 抛光条件: 70/90rpm
Downforce: 4psi Polishing pad: IC1000 polishing pad polishing conditions: 70/90rpm
化硅的选择比, 氧化硅 (HDP) 的去除速率随着 Glyphosate添加量会有一定 程度的降低, 选择比仍然可调。 使用氧化饰的磨料制备的 STI抛光液, 比硅 溶胶基的抛光液氧化硅去除速率要高, 选择比也有较大的调控区间。 在 STI 的平坦化中表现出了一定的技术优势。
The selectivity of silicon dioxide, the removal rate of silicon oxide (HDP) will decrease to some extent with the addition of Glyphosate, and the selection ratio is still adjustable. The STI polishing solution prepared using the oxidized abrasive has a higher removal rate than the silica sol-based polishing liquid, and the selection ratio also has a larger control interval. Demonstrated a certain technical advantage in the flattening of STI.
Claims
1、 一种化学机械抛光液, 包括: 一种二氧化铈的磨料, 一种有机膦酸, 一种 pH调节剂, 和载体水。 A chemical mechanical polishing liquid comprising: an abrasive of cerium oxide, an organic phosphonic acid, a pH adjusting agent, and a carrier water.
2、 如权利要求 1所述的抛光液, 其特征在于, 所述二氧化铈磨料为碱 性氧化铈的水分散体, 所述碱性氧化铈的 pH为 8-11。 The polishing liquid according to claim 1, wherein the cerium oxide abrasive is an aqueous dispersion of basic cerium oxide, and the pH of the basic cerium oxide is 8-11.
3、 如权利要求 1所述的抛光液, 其特征在于, 所述二氧化铈磨料粒径 为 20-500腿。 The polishing liquid according to claim 1, wherein the cerium oxide abrasive has a particle diameter of 20 to 500 legs.
4、 如权利要求 3所述的抛光液, 其特征在于, 所述二氧化铈磨料粒径 为 60-200nm。 The polishing liquid according to claim 3, wherein the cerium oxide abrasive has a particle diameter of 60 to 200 nm.
5、 如权利要求 1所述的抛光液, 其特征在于, 所述二氧化铈磨料的固 含量从 0.1 ^%到 10wt%。 The polishing liquid according to claim 1, wherein the cerium oxide abrasive has a solid content of from 0.1% by mass to 10% by weight.
6、 如权利要求 1所述的抛光液, 其特征在于, 所述有机膦酸为选自 2- 羟基膦酰基乙酸、 羟基亚乙基二膦酸和 N- (膦酰基甲基) 氨基乙酸中的一 种或多种。 The polishing liquid according to claim 1, wherein the organic phosphonic acid is selected from the group consisting of 2-hydroxyphosphonoacetic acid, hydroxyethylidene diphosphonic acid, and N-(phosphonomethyl)glycine. One or more.
7、 如权利要求 1所述的抛光液, 其特征在于, 所述有机膦酸的浓度为 0.05wt%-lwt 7. The polishing liquid according to claim 1, wherein the concentration of the organic phosphonic acid is 0.05 wt% - 1 wt.
8、 如权利要求 1所述的抛光液, 其特征在于, 所述 pH调节剂为 KOH 或者有机胺。 The polishing liquid according to claim 1, wherein the pH adjuster is KOH or an organic amine.
9,如权利要求 1 所述的抛光液, 其特征在于, 所述抛光液的 pH值为 7-12。 The polishing liquid according to claim 1, wherein the polishing liquid has a pH of 7 to 12.
Applications Claiming Priority (2)
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CN201110223455.6 | 2011-08-05 | ||
CN2011102234556A CN102911605A (en) | 2011-08-05 | 2011-08-05 | Chemical mechanical polishing solution |
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WO2016140968A1 (en) * | 2015-03-05 | 2016-09-09 | Cabot Microelectronics Corporation | Polishing composition containing ceria abrasive |
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CN104745094B (en) * | 2013-12-26 | 2018-09-14 | 安集微电子(上海)有限公司 | A kind of chemical mechanical polishing liquid |
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- 2011-08-05 CN CN2011102234556A patent/CN102911605A/en active Pending
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- 2012-06-04 WO PCT/CN2012/000764 patent/WO2013020351A1/en active Application Filing
- 2012-06-07 TW TW101120381A patent/TW201307542A/en unknown
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CN1948418A (en) * | 2005-10-14 | 2007-04-18 | 花王株式会社 | Polishing composition for a semiconductor substrate |
CN1955239A (en) * | 2005-10-28 | 2007-05-02 | 安集微电子(上海)有限公司 | Chemical mechanical polishing material of copper |
CN101451044A (en) * | 2007-11-30 | 2009-06-10 | 安集微电子(上海)有限公司 | Chemico-mechanical polishing liquid |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2016140968A1 (en) * | 2015-03-05 | 2016-09-09 | Cabot Microelectronics Corporation | Polishing composition containing ceria abrasive |
Also Published As
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CN102911605A (en) | 2013-02-06 |
TW201307542A (en) | 2013-02-16 |
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