CN102093816B - 一种化学机械抛光液 - Google Patents
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- 238000005498 polishing Methods 0.000 title claims abstract description 39
- 239000007788 liquid Substances 0.000 title claims abstract description 13
- 239000000126 substance Substances 0.000 title claims abstract description 13
- 239000007800 oxidant agent Substances 0.000 claims abstract description 18
- 230000001590 oxidative effect Effects 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000003093 cationic surfactant Substances 0.000 claims description 10
- 239000012530 fluid Substances 0.000 claims description 8
- -1 polyoxyethylene Polymers 0.000 claims description 5
- 229910002012 Aerosil® Inorganic materials 0.000 claims description 2
- 239000012425 OXONE® Substances 0.000 claims description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 2
- 239000008119 colloidal silica Substances 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- HJKYXKSLRZKNSI-UHFFFAOYSA-I pentapotassium;hydrogen sulfate;oxido sulfate;sulfuric acid Chemical compound [K+].[K+].[K+].[K+].[K+].OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-] HJKYXKSLRZKNSI-UHFFFAOYSA-I 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- AQZSPJRLCJSOED-UHFFFAOYSA-M trimethyl(octyl)azanium;chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(C)C AQZSPJRLCJSOED-UHFFFAOYSA-M 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- OYINQIKIQCNQOX-UHFFFAOYSA-M 2-hydroxybutyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCC(O)C[N+](C)(C)C OYINQIKIQCNQOX-UHFFFAOYSA-M 0.000 claims 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims 1
- AJXBTRZGLDTSST-UHFFFAOYSA-N amino 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)ON AJXBTRZGLDTSST-UHFFFAOYSA-N 0.000 claims 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 1
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 claims 1
- 239000003082 abrasive agent Substances 0.000 abstract 1
- 150000001768 cations Chemical class 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 10
- 229910052721 tungsten Inorganic materials 0.000 description 10
- 239000010937 tungsten Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000005210 alkyl ammonium group Chemical group 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- FZGRPBJBMUNMQH-UHFFFAOYSA-N trimethyl-$l^{3}-chlorane Chemical compound CCl(C)C FZGRPBJBMUNMQH-UHFFFAOYSA-N 0.000 description 1
- BYGOPQKDHGXNCD-UHFFFAOYSA-N tripotassium;iron(3+);hexacyanide Chemical compound [K+].[K+].[K+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] BYGOPQKDHGXNCD-UHFFFAOYSA-N 0.000 description 1
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
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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
- 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
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- 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
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
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- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
本发明公开了一种化学机械抛光液,含有水,研磨剂,氧化剂和水溶性阳离子表面活性剂。本发明的化学机械抛光液可降低并消除抛光噪音,改善操作环境,降低抛光垫的摩擦,延长抛光垫的使用寿命。
Description
技术领域
本发明涉及一种用于钨化学机械抛光液,具体涉及一种含有阳离子表面活性剂的化学机械抛光液。
背景技术
随着半导体技术的不断发展,以及大规模集成电路互连层的不断增加,导电层和绝缘介质层的平坦化技术变得尤为关键。二十世纪80年代,由IBM公司首创的化学机械研磨(CMP)技术被认为是目前全局平坦化的最有效的方法。
化学机械研磨(CMP)由化学作用、机械作用以及这两种作用结合而成。它通常由一个带有抛光垫的研磨台,及一个用于承载芯片的研磨头组成。其中研磨头固定住芯片,然后将芯片的正面压在抛光垫上。当进行化学机械研磨时,研磨头在抛光垫上线性移动或是沿着与研磨台一样的运动方向旋转。与此同时,含有研磨剂的浆液被滴到抛光垫上,并因离心作用平铺在抛光垫上。芯片表面在机械和化学的双重作用下实现全局平坦化。
对金属层CMP的主要机制被认为是:氧化剂先将金属表面氧化成膜,以二氧化硅和氧化铝为代表的研磨剂将该层氧化膜机械去除,产生新的金属表面继续被氧化,这两种作用协同进行。
作为化学机械研磨(CMP)对象之一的金属钨,在高电流密度下,抗电子迁移能力强,并且能够与硅形成很好的欧姆接触,所以可作为接触窗及介层洞的填充金属及扩散阻挡层。
针对钨的化学机械研磨(CMP),常用的氧化剂主要有含铁金属的盐类,碘酸盐,双氧水等。
1991年,F.B.Kaufman等报道了铁氰化钾用于钨的化学机械研磨(CMP)技术。(″Chemical Mechanical Polishing for Fabricating Patterned W MetalFeatures asChip Interconnects″,Journal of the Electrochemical Society,Vol.138,No.11,1991年11月)。
美国专利5340370公开了一种用于钨化学机械研磨(CMP)的配方,其中含有0.1M铁氰化钾,5%氧化硅,同时含有醋酸盐作为pH缓冲剂。
美国专利5980775,5958288,6068787公开了用铁离子作催化剂、双氧水作氧化剂进行钨化学机械研磨(CMP)方法。在这种催化机制中,铁离子的含量被降至了200ppm左右,但由于铁离子催化双氧水分解,所以催化剂要和氧化剂分开存放,在化学机械研磨(CMP)之前进行混合。另外,和氧化剂混合好之后的研磨液不稳定,会缓慢分解失效。
美国专利5527423,6008119,6284151等公开了Fe(NO3)3、氧化铝体系进行钨的化学机械研磨(CMP)方法。该抛光体系在静态腐蚀速率(static etchrate)上具有优势,但是在产品缺陷(defect)上存在显著不足。
以上用于钨化学机械抛光液都是通过氧化剂先将钨表面氧化成膜,然后通过二氧化硅和氧化铝为代表的研磨剂将氧化膜机械去除。由于机械摩擦,会抛光时产生摩擦噪音。
发明内容
本发明所要解决的技术问题是降低并消除抛光噪音,改善操作环境,降低抛光垫的摩擦,延长抛光垫的使用寿命。
本发明的化学机械抛光液,含有水,研磨剂,氧化剂和水溶性阳离子表面活性剂。
本发明中,所述的研磨剂为气相二氧化硅(fumed silica)和/或硅溶胶(colloidal silica)。
本发明中,所述的氧化剂为含铁氧化剂或含铁氧化剂和其他氧化剂的组合物。
本发明中,所述的含铁氧化剂为硝酸铁,所述的含铁氧化剂和其他氧化剂的组合物为硝酸铁和单过硫酸氢钾的组合物。
本发明中,所述的水溶性阳离子表面活性剂为长链烷基氯化铵、长链烷基溴化铵、末端含硅氧键的长链烷基氯化铵、吉米奇类型季铵盐、聚合型季铵盐中的一种或多种。
本发明中,所述的水溶性阳离子表面活性剂优选为十二烷基三甲基氯化铵、十二烷基三甲基溴化铵、苄基三甲基氯化铵、辛基三甲基氯化铵、3-三乙氧基硅基丙基三甲基氯化铵、十八烷基胺聚氧乙烯醚双季铵盐和/或聚季铵盐-10中的一种或多种。
本发明中,所述的研磨剂的质量百分比为0.2%~4%。
本发明中,所述的硝酸铁的质量百分比为0.05%~1.5%。
本发明中,所述的水溶性阳离子表面活性剂的浓度为100-500ppm。
本发明中,所述的抛光液的pH值为1.5-2.5。
本发明的积极进步效果在于:通过在用于钨化学机械抛光液中加入阳离子表面活性剂,显著降低并消除抛光噪音,改善操作环境,降低抛光垫的摩擦,延长抛光垫的使用寿命。
具体实施方式
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。
抛光条件:抛光机台mirra,8英寸晶圆(inch wafer),研磨压力4psi,抛光液流量100ml/min。
表1给出了本发明的化学机械抛光液实施例1~10和对比例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,用氢氧化钾或稀硝酸调到所需pH值,即制得化学机械抛光液。
表1化学机械抛光液实施例1~12以及对比例1~2
从对比例1和对比例2中可以发现,在没有本发明所述的阳离子表面活性剂存在的情况下,无论抛光液使用单氧化剂,还是使用双氧化剂,都会产生很高的噪音。
从实施例1~10中可以发现,当加入本专利所述的阳离子表面活性剂之后,在不同的研磨剂、氧化剂、稳定剂的种类和含量的情况下,抛光噪音都消失了。
Claims (6)
1.一种化学机械抛光液,含有水,研磨剂,氧化剂和水溶性阳离子表面活性剂,其中所述的水溶性阳离子表面活性剂为十二烷基三甲基氯化铵、十二烷基三甲基溴化铵、苄基三甲基氯化铵、辛基三甲基氯化铵、3-三乙氧基硅基丙基三甲基氯化铵、十八烷基胺聚氧乙烯醚双季铵盐和/或聚季铵盐-10中的一种或多种,所述的氧化剂为含铁氧化剂或含铁氧化剂和其他氧化剂的组合物,且所述抛光液的pH值为1.5-2.5,所述的水溶性阳离子表面活性剂的浓度为100-500ppm。
2.根据权利要求1所述的抛光液,所述的研磨剂为气相二氧化硅(fumed silica)和/或硅溶胶(colloidal silica)。
3.根据权利要求1所述的抛光液,所述的含铁氧化剂为硝酸铁。
4.根据权利要求1所述的抛光液,所述的含铁氧化剂和其他氧化剂的组合物为硝酸铁和单过硫酸氢钾的组合物。
5.根据权利要求1所述的抛光液,所述的研磨剂的质量百分比为0.2%~4%。
6.根据权利要求3或4所述的抛光液,所述的硝酸铁的质量百分比为0.05%~1.5%。
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TWI463002B (zh) * | 2011-12-01 | 2014-12-01 | Uwiz Technology Co Ltd | 研漿組成物 |
US9238754B2 (en) * | 2014-03-11 | 2016-01-19 | Cabot Microelectronics Corporation | Composition for tungsten CMP |
US9275899B2 (en) * | 2014-06-27 | 2016-03-01 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Chemical mechanical polishing composition and method for polishing tungsten |
US9631122B1 (en) * | 2015-10-28 | 2017-04-25 | Cabot Microelectronics Corporation | Tungsten-processing slurry with cationic surfactant |
CN108624234A (zh) * | 2017-03-21 | 2018-10-09 | 安集微电子科技(上海)股份有限公司 | 一种化学机械抛光液 |
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