WO2011079512A1 - 一种化学机械抛光液 - Google Patents
一种化学机械抛光液 Download PDFInfo
- Publication number
- WO2011079512A1 WO2011079512A1 PCT/CN2010/002114 CN2010002114W WO2011079512A1 WO 2011079512 A1 WO2011079512 A1 WO 2011079512A1 CN 2010002114 W CN2010002114 W CN 2010002114W WO 2011079512 A1 WO2011079512 A1 WO 2011079512A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polishing
- polishing liquid
- edge
- silica
- silica sol
- Prior art date
Links
- 238000005498 polishing Methods 0.000 title claims abstract description 74
- 239000007788 liquid Substances 0.000 title claims abstract description 35
- 239000000126 substance Substances 0.000 title claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims description 31
- 239000003989 dielectric material 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
- 238000007517 polishing process Methods 0.000 claims description 5
- 239000003002 pH adjusting agent Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical compound OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 claims description 2
- 230000003247 decreasing effect Effects 0.000 abstract description 2
- 230000001668 ameliorated effect Effects 0.000 abstract 1
- 235000012431 wafers Nutrition 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002002 slurry Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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 a chemical mechanical polishing liquid, and more particularly to a chemical mechanical polishing liquid containing a mixed abrasive and a P H modifier, and a polishing process for removing the edge of the silica dielectric material by the chemical mechanical polishing liquid.
- Silica is currently the most widely used interlayer dielectric in IC production.
- CMP chemical mechanical polishing
- Sex is a few important evaluation indicators of dielectric material CMP. Because silicon dioxide is tetravalent silicon, it is difficult to remove by redox method. Microscopically, it is necessary to form surface hydration layer to deform the abrasive particles and wafer surface.
- silica dielectric material usually adopts a polishing liquid having a higher solid content, and the gas phase method is commonly used.
- Silica and silica sol particles using a polishing solution of a fumed silica aqueous dispersion, due to the irregular shape of the particles, tends to be agglomerated into larger particles, resulting in surface micro-scratches.
- silica sol as a polishing liquid can reduce the surface micro-scratch and better stability in addition to the better surface pollutant index, but the thickness of the edge film is low due to the forward CVD silica.
- the removal rate at the edge of the wafer during polishing is much lower than in the middle region (see Figure 1), which is a common problem with silica sol-based silica polishing fluids, and currently commercially available products such as Rohm and Haas R1501 has a problem of slow edge rate (see Table 2), especially in the polishing of 200mm wafers, which has a great influence on the effective edge slicing.
- the industry mainly adopts the design of the improved polishing head, or adjusts the pressure of the retaining ring.
- silica sol as an abrasive
- a polishing liquid using a vapor phase aqueous silica dispersion due to the shape of the particles. Irregular, it is easy to go into larger particles, resulting in micro scratches on the surface.
- the use of silica sol as a polishing liquid can reduce the surface micro-scratch and better stability in addition to the better surface pollutant index, while the silica sol-based polishing solution has a disadvantage in the wafer.
- the removal rate at the edge is much lower than that in the middle region, which is a problem that is difficult to solve with such a polishing liquid.
- the invention adopts two methods of increasing the pH of the polishing liquid or adopting the mixed abrasive, which can effectively improve the shape of the edge and meet the process requirements. Summary of invention
- the technical problem to be solved by the present invention is to improve the edge of the polishing process of the silica dielectric material.
- the removal rate improves the morphology at the edge of the wafer and adjusts the polishing selectivity of the silicon dioxide to other materials.
- the chemical mechanical polishing liquid of the present invention contains a composite abrasive and a P H conditioner.
- the composite abrasive is composed of two different particle diameter silica sol particles mixed in different proportions.
- the two different particle diameter silica sol particles are: a silica sol particle having a particle diameter of 30 to 100 nm and a silica sol particle having a particle diameter of 100 to 200 nm.
- the content of the silica sol particles having a particle diameter of 30 to 100 nm is 1 to 20%, and the content of the silica sol particles having a particle diameter of 100 to 200 nm is 1 to 20%.
- the polishing liquid has a pH of 10 to 12.
- the pH adjusting agent is one or more selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium ethoxide, potassium ethoxide, or triethanolammonium.
- a polishing method comprising: polishing with a chemical mechanical polishing liquid of the present invention in a polishing process removed from the edge of a silica dielectric material.
- the positive progress of the invention is as follows: by increasing the pH of the polishing liquid and using the polishing liquid mixed with the abrasive, the removal rate of the edge after polishing is lower than that of the intermediate portion, thereby effectively improving the possibility of chip damage in the wafer edge region. Sex.
- Figure 1 shows the thickness profile of a silica wafer before polishing.
- Figure 2 shows the removal rate profile of the wafer edge to the center after polishing.
- Table 1 shows the formulations of the chemical mechanical polishing liquids of the present invention in Examples 1 to 11 and Comparative Examples 1-2, according to the components listed in Table 1 and their contents, uniformly mixed in deionized water, and adjusted with a pH adjusting agent.
- a chemical mechanical polishing solution can be prepared at the desired pH.
- Polishing conditions Polishing machine: MIRRA
- Polishing conditions Main pressure: 4.6 psi
- Polishing head speed 103 rpm
- Polishing plate speed 107 rpm
- Polishing pad IC1010 Table 1 Chemical mechanical polishing liquid preparation Examples 1 to 11 and Comparative Examples 1-2
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (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)
- Materials Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Description
一种化学机械抛光液 技术领域
本发明涉及一种化学机械抛光液， 具体涉及一种含有混合研磨剂和 PH 调节剂的化学机械抛光液， 以及所述的化学机械抛光液用于二氧化硅介质材 料边沿去除的抛光过程。 技术背景
二氧化硅是目前 IC生产中应用最广泛的层间介质，为满足光刻的要求， 必须采用化学机械抛光（CMP)工艺对介质表面进行平整化加工，抛光速率， 表面污染物指标， 抛光均一性， 是介质材料 CMP几个重要的评价指标， 由 于二氧化硅是四价硅， 很难通过氧化还原的方法去除， 微观上还是要通过形 成表面水合层， 使得磨料颗粒和晶圆表面发生形变， 形成颗粒表面的羟基与 硅片表面的水合层之间的化学键，再在机械力的作用下去除， 所以二氧化硅 介质 料的抛光通常采用固含量较高的抛光液，常用的有气相法二氧化硅和 硅溶胶颗粒， 采用气相法二氧化硅水分散体的抛光液， 由于颗粒的形状不规 则， 容易团去成较大颗粒， 从而产生表面微划伤。 而采用硅溶胶为抛光液， 除具有比较好的表面污染物指标，还可以减少表面微划伤，和较好的稳定性， 但由于前程 CVD二氧化硅时存在边沿薄膜的厚度偏低， 造成在抛光过程中 在晶圆边沿处的去除速率比中间区域要低较多（见图 1 )，这是硅溶胶基氧化 硅抛光液普遍存在的问题，目前市售的产品例如罗门哈斯的 R1501就存在边 沿速率慢的问题（见表 2)，尤其在 200毫米晶圆的抛光中对边沿有效切片的 影响较大， 目前工业界主要是采用改进抛光头的设计， 或者调整保持环的压
力来改善这一问题， 这在已有许多文献中己有报道， " Study on Polishing Profile at Wafer Edge by CMP Using Floating Head ", 精密工学会志， 2000vol.66 (no.9), "wafer edge challanges", TETSUO FUKUDA, Fujitsu, semicon.06等。 但 8寸晶圆的抛光机台的抛光头只有主压力区 （membering ring)和保持环（trtaining ring)两个区域调节压力， 改善的能力是很有限的， 通过抛光液配方的设计， 来改善边沿速度慢的专利还未见报道， 本专利旨在 通过抛光液的磨料和 pH值的改变来改善这一问题， 取得了较好的结果， 能 够达到工艺要求。 、
已有文献均集中在改善抛光头的压力分布，或改进抛光头设计等工艺条 件来改善边沿速率慢的问题，本专利首次对边沿速率慢进行了浆液配方方面 的尝试， 效果比较明显。
在介质材料二氧化硅的化学机械抛光中，通常采用除采用气相法二氧化 硅外， 也有采用硅溶胶为磨料的抛光液， 采用气相法二氧化硅水分散体的抛 光液， 由于颗粒的形状不规则，容易团去成较大颗粒，从而产生表面微划伤。 而采用硅溶胶为抛光液， 除具有比较好的表面污染物指标， 还可以减少表面 微划伤， 和较好的稳定性， 而硅溶胶基的抛光液却存在着一个缺点， 就是在 晶圆边沿处的去除速率比中间区域要低较多，这是该类抛光液较难解决的问 题。 本发明采用升高抛光液 pH值， 或采用混合磨料两种方法， 可以有效改 善边沿的形貌， 达到工艺要求。 发明概要
本发明所要解决的技术问题是提高二氧化硅介质材料抛光过程中边沿
去除速率，改善晶圆边沿处的形貌以及调节二氧化硅对其它材料的抛光选择 比。
本发明的化学机械抛光液， 含有复合研磨剂和 PH调节剂。
本发明中，所述的复合研磨剂由两种不同粒径的硅溶胶颗粒以不同比例 混合而成。
本发明中， 所述的两种不同粒径的硅溶胶颗粒为： 一种粒径为 30〜 lOOnm的硅溶胶颗粒和一种粒径为 100〜200nm的硅溶胶颗粒。
本发明中， 所述的粒径为 30〜100nm的硅溶胶颗粒的含量为 1〜20%， 所述的粒径为 100〜200nm的硅溶胶颗粒的含量为 1〜20%。
本发明中， 所述的抛光液的 pH值为 10〜12。
本发明中， 所述的 pH调节剂选自氢氧化钠， 氢氧化钾， 氢氧化铵， 乙 醇钠， 乙醇钾， 或三乙醇铵中的一种或多种。
一种抛光方法， 所述抛光方法包括： 在二氧化硅介质材料边沿去除的抛 光过程中， 用本发明的化学机械抛光液进行抛光。
本发明的积极进步效果在于： 通过提高抛光液的 pH， 以及采用混和磨 料的抛光液， 降低了抛光后边沿的去除速率较中间区域低的现象， 有效改善 了晶圆边沿区域芯片受损的可能性。
通过改变浆料的 pH以及采用复合磨料改善了二氧化硅介质材料抛光后 晶圆表面均一性以及边沿去除速率慢的现象。
解决了硅溶胶基的抛光液在二氧化硅抛光过程中普遍存在的边沿速率 快速下跌的问题， 提高抛光均一性。
附图说明
图 1 二氧化硅晶片抛光前的厚度分布图。
图 2 抛光后晶圆边沿到中心的去除速率分布图。 发明内容 制备实施例
下面用实施例来进一步说明本发明， 但本发明并不受其限制。下述实施 例中， 百分比均为质量百分比。
表 1给出了本发明的化学机械抛光液实施例 1〜11以及对比例 1-2的配 方， 按表 1中所列组分及其含量， 在去离子水中混合均匀， 用 pH调节剂调 到所需 pH值， 即可制得化学机械抛光液。
抛光条件： 抛光机台： MIRRA
抛光条件： 主压力： 4.6psi
保持环压力： 6psi
抛光头转速： 103转 /分钟
抛光盘转速： 107转 /分钟
晶圆： 8英寸 PETEOS硅片
浆料流速： 150毫升 /分钟
钻石盘压力： 6磅
抛光时间 1分钟
抛光垫： IC1010
表 1化学机械抛光液制备实施例 1~11以及对比例 1-2
TEOS去除速率 边沿与中心厚度差 （埃）
R1501 >1000
对比例 1 3190 1124 对比例 2 3665 996 实施例 1 3556 525 实施例 2 3854 512 实施例 3 3795 498 实施例 4 3689 532 实施例 5 3625 428
实施例 6 3456 412
实施例 7 4050 505
实施例 8 3385 254
实施例 9 3354 468
实施例 10 3556 750
实施例 11 3295 325
由图 1以及表 1中数据可以看出，采用复合研磨剂后能够有效改善边沿 速率下降较快的问题， 增加浆料的 PH值也能降低边沿速率下降的速度， 改 善抛光均一性。
Claims
权利要求 、 一种化学机械抛光液， 含有复合研磨剂和 pH调节剂。
、 根据权利要求 1所述的抛光液， 所述的复合研磨剂由两种不同粒径的硅 溶胶颗粒以不同比例混合而成。
、 根据权利要求 2所述的抛光液， 所述的两种不同粒径的硅溶胶颗粒为： 一种粒径为 30〜100nm的硅溶胶颗粒和一种粒径为 100〜200nm的硅溶 胶颗粒。
、 根据权利要求 3所述的抛光液， 所述的粒径为 30〜100nm的硅溶胶颗粒 的含量为 1〜20%，所述的粒径为 100〜200nm的硅溶胶颗粒的含量为 1〜 20%。
、 根据权利要求 1所述的抛光液， 所述的抛光液的 pH值为 10〜12。
、根据权利要求 1所述的抛光液， 所述的 pH调节剂选自氢氧化钠，氢氧化 钾， 氢氧化铵， 乙醇钠， 乙醇钾， 或三乙醇铵中的一种或多种。
、 一种抛光方法， 所述抛光方法包括： 在二氧化硅介质材料边沿去除的抛 光过程中， 用权利要求 1-6中任一项所述的化学机械抛光液进行抛光。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910247654.3 | 2009-12-30 | ||
| CN2009102476543A CN102115633A (zh) | 2009-12-30 | 2009-12-30 | 一种化学机械抛光液 |
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| WO2011079512A1 true WO2011079512A1 (zh) | 2011-07-07 |
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| CN (1) | CN102115633A (zh) |
| WO (1) | WO2011079512A1 (zh) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372273B (zh) * | 2011-08-23 | 2014-10-08 | 江苏天恒纳米科技股份有限公司 | 双粒径二氧化硅溶胶及其制备方法 |
| JPWO2013069623A1 (ja) * | 2011-11-08 | 2015-04-02 | 株式会社フジミインコーポレーテッド | 研磨用組成物 |
| CN103897605A (zh) * | 2012-12-27 | 2014-07-02 | 天津西美半导体材料有限公司 | 单面抛光机用蓝宝石衬底抛光液 |
| CN103484024B (zh) * | 2013-09-13 | 2014-10-15 | 上海新安纳电子科技有限公司 | 一种二氧化硅介电材料用化学机械抛光液及其制备方法 |
| CN104893587A (zh) * | 2015-03-09 | 2015-09-09 | 江苏中晶科技有限公司 | 高效c向蓝宝石抛光液及其制备方法 |
| CN105153943B (zh) * | 2015-09-10 | 2017-08-04 | 盐城工学院 | 氧化镓晶片抗解理抛光液及其制备方法 |
| CN108949034B (zh) * | 2018-08-17 | 2020-10-09 | 无锡易洁工业介质有限公司 | 一种蓝宝石化学机械抛光液及其制备方法 |
| CN111662642B (zh) * | 2020-07-13 | 2021-07-23 | 万华化学集团电子材料有限公司 | 一种蓝宝石抛光组合物及其制备方法 |
| CN112621557B (zh) * | 2020-12-17 | 2022-08-09 | 江苏集萃精凯高端装备技术有限公司 | Yag晶片的抛光方法 |
| CN113789127B (zh) * | 2021-10-20 | 2023-07-28 | 博力思(天津)电子科技有限公司 | 一种硅通孔铜膜抛光液 |
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| US20070148978A1 (en) * | 2005-12-22 | 2007-06-28 | Eui-Jin Han | Slurry compositions, methods of polishing polysilicon layers using the slurry compositions and methods of manufacturing semiconductor devices using the slurry compositions |
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| CN1683465A (zh) * | 2004-04-12 | 2005-10-19 | 捷时雅株式会社 | 化学机械研磨用水性分散剂及其化学机械研磨方法 |
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| US20070148978A1 (en) * | 2005-12-22 | 2007-06-28 | Eui-Jin Han | Slurry compositions, methods of polishing polysilicon layers using the slurry compositions and methods of manufacturing semiconductor devices using the slurry compositions |
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