CN101970595B - 一种化学机械抛光液 - Google Patents
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- 238000005498 polishing Methods 0.000 title claims abstract description 53
- 239000000126 substance Substances 0.000 title claims abstract description 8
- 239000007788 liquid Substances 0.000 title claims abstract description 7
- 229940123208 Biguanide Drugs 0.000 claims abstract description 15
- 150000004283 biguanides Chemical class 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims abstract description 3
- 239000012530 fluid Substances 0.000 claims description 34
- 239000006061 abrasive grain Substances 0.000 claims description 8
- MOFINMJRLYEONQ-UHFFFAOYSA-N [N].C=1C=CNC=1 Chemical class [N].C=1C=CNC=1 MOFINMJRLYEONQ-UHFFFAOYSA-N 0.000 claims description 7
- -1 biguanide compound Chemical class 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- 150000003536 tetrazoles Chemical class 0.000 claims description 3
- 150000003852 triazoles Chemical class 0.000 claims description 3
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 2
- KJHOZAZQWVKILO-UHFFFAOYSA-N N-(diaminomethylidene)-4-morpholinecarboximidamide Chemical compound NC(N)=NC(=N)N1CCOCC1 KJHOZAZQWVKILO-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 claims description 2
- 229960005389 moroxydine Drugs 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- ICFJFFQQTFMIBG-UHFFFAOYSA-N phenformin Chemical compound NC(=N)NC(=N)NCCC1=CC=CC=C1 ICFJFFQQTFMIBG-UHFFFAOYSA-N 0.000 claims description 2
- 229960003243 phenformin Drugs 0.000 claims description 2
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 claims 1
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims 1
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims 1
- 150000003851 azoles Chemical class 0.000 abstract 2
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 23
- 229920005591 polysilicon Polymers 0.000 description 22
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003002 pH adjusting agent Substances 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- OETHQSJEHLVLGH-UHFFFAOYSA-N metformin hydrochloride Chemical compound Cl.CN(C)C(=N)N=C(N)N OETHQSJEHLVLGH-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
-
- 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]
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Power Engineering (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
一种化学机械抛光液,其含有研磨颗粒和水,其还同时含有双胍类化合物和氮唑类化合物。抛光液中同时含有的双胍类物质和氮唑类物质具有协同作用,可显著提高多晶硅的去除速率。
Description
技术领域
本发明涉及半导体制造工艺中的一种化学机械抛光液。
技术背景
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。由IBM公司二十世纪80年代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)由化学作用和机械作用和两种作用结合而成。它的设备通常由一个带有抛光垫(pad)的研磨台(polishing table),及一个用于承载芯片(wafer)的研磨头(carrier)组成。其中研磨头固定住芯片,然后将芯片的正面压在研磨垫上。当进行化学机械研磨时,研磨头在抛光垫(pad)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(slurry)被滴到抛光垫(pad)上,并因离心作用平铺在抛光垫(pad)上。芯片(wafer)表面在机械和化学的双重作用下实现全局平坦化。
根据化学机械抛光所要解决的具体问题的不同,对多晶硅(Poly silicon)的去除速率(removal rate)有两种不同的要求。
一种要求是要降低多晶硅的去除速率,如:US 20050130428报道了一种含环氧乙烷或环氧丙烷的均聚或共聚物的抛光液,以抑制多晶硅去除速率。聚合物的疏水性基团被认为是吸附在多晶硅表面上,形成了钝化层,从而降低了多晶硅的去除速率。
另一类是提高多晶硅的去除速率:
US2002032987公开了一种用醇胺作为添加剂的抛光液,以提高多晶硅(Poly silicon)的去除速率(removal rate),其中添加剂优选2-(二甲氨基)-2-甲基-1-丙醇。
US2002151252公开了一种含具有多个羧酸结构的络合剂的抛光液,用于提高多晶硅去除速率,其中优选的络合剂是EDTA(乙二胺四乙酸)和DTPA(二乙基三胺五乙酸)。
EP1072662公开了一种含孤对电子和双键产生离域结构的有机物的抛光液,以提高多晶硅(Poly silicon)的去除速率(removal rate),优选化合物是胍类的化合物及其盐。
US2006014390公开了一种用于提高多晶硅的去除速率的抛光液,其包含重量百分比为4.25%~18.5%研磨剂和重量百分比为0.05%~1.5%的添加剂。其中添加剂主要选自季铵盐、季胺碱和乙醇胺等有机碱。此外,该抛光液还包含非离子型表面活性剂,例如乙二醇或丙二醇的均聚或共聚产物。
发明概要
本发明所要解决的技术问题是提供一种可显著提高多晶硅去除速率的化学机械抛光液。
本发明的抛光液含有研磨颗粒和水,其还同时含有双胍类化合物和氮唑类化合物。
其中,所述的双胍类化合物较佳的选自双胍、二甲双胍、苯乙双胍、吗啉胍、1,1’-己基双[5-(对氯苯基)双胍]及上述化合物的酸加成盐中的一种或多种。所述的酸较佳的为盐酸、磷酸、硝酸、醋酸、葡萄糖酸或磺酸。所述的双胍类化合物的含量较佳的为质量百分比0.01~7%。
其中,所述的氮唑类化合物较佳的选自三氮唑和四氮唑及其衍生物中的一种或多种。所述的氮唑类化合物的含量较佳的为质量百分比0.01~15%。
其中,所述的研磨颗粒较佳的选自SiO2、Al2O3、ZrO2、CeO2、SiC、Fe2O3、TiO2和Si3N4中的一种或多种。所述的研磨颗粒的含量较佳的为质量百分比0.1~30%。所述的研磨颗粒的粒径较佳的为20~150nm,更佳的为30~120nm。
本发明的抛光液还可含有本领域常规添加剂,如pH调节剂和/或分散剂。所述的pH调节剂可选自NaOH、KOH、氨和有机碱中的一种或多种;所述的分散剂可选自聚乙烯醇、聚丙烯酸、聚丙烯酰胺和聚环氧乙烷中的一种或多种;所述的分散剂的含量较佳的为质量百分比0.01%~1%。
本发明的抛光液的pH范围较佳的为8~12。
将上述成分简单混和均匀,用pH调节剂调节至合适pH值,静置即可制得本发明的抛光液。本发明所用试剂及原料均市售可得。
本发明的积极进步效果在于:本发明的抛光液中同时含有的双胍类物质和氮唑类物质具有协同作用,可显著提高多晶硅的去除速率。
发明内容
下面通过实施例的方式进一步说明本发明,但并不因此将本发明限制在所述的实施例范围之中。
实施例1~11
表1给出了本发明的抛光液1~11,按表中配方,将各成分简单混和均匀,余量为水,用pH调节剂调节至合适pH值,静置30分钟即可制得各抛光液。
表1本发明的抛光液实施例1~11配方
效果实施例
表2给出了对比抛光例8以及本发明的抛光液1~6,按表中配方,将各成分简单混和均匀,余量为水,用四甲基氢氧化铵调节至pH=11,静置30分钟即可制得各抛光液。将各抛光液用于多晶硅抛光。抛光条件为:抛光机台为Logitech(英国)1PM52型,12英寸politex抛光垫(pad),4cm*4cm正方形Wafer,研磨压力3psi,研磨台(polishing table)转速70转/分钟,研磨头(carrier)自转转速150转/分钟,抛光液滴加速度100ml/min。抛光结果见表2。
表2对比抛光例8以及本发明的抛光液1~6配方及多晶硅去除速率
由对比抛光液2,3,4表明:随着盐酸二甲双胍含量的不断提高,多晶硅的去除速率趋向饱和,最大值在2390A/min左右。继续增加盐酸二甲双胍含量,对提高多晶硅的去除速率没有帮助。
由对比抛光液5,6,7表明:随着1,2,4-三氮唑(TAZ)含量的不断提高,多晶硅的去除速率趋向饱和,最大值在2163A/min左右。继续增加TAZ的含量,对提高多晶硅的去除速率没有帮助。
由本发明的抛光液1~5与对比抛光液1、5~7表明:双胍类物质和三氮唑存在着明显的协同作用,可以显著地提高多晶硅的去除速率。
由本发明的抛光液6和对比抛光液8表明:双胍类物质和四氮唑存在着明显的协同作用,可以显著地提高多晶硅的去除速率。
Claims (9)
1.一种化学机械抛光液,其含有研磨颗粒和水,其特征在于:其还同时含有双胍类化合物和氮唑类化合物,其中所述的氮唑类化合物为三氮唑和四氮唑及其衍生物中的一种或多种,为1,2,4-三氮唑、3-氨基-1,2,4-三氮唑、5-羧基-3-氨基1,2,4-三氮唑和5-氨基四氮唑中的一种或多种。
2.如权利要求1所述的抛光液,其特征在于:所述的双胍类化合物选自双胍、二甲双胍、苯乙双胍、吗啉胍、1,1’-己基双[5-(对氯苯基)双胍]及上述化合物的酸加成盐中的一种或多种。
3.如权利要求2所述的抛光液,其特征在于:所述的酸为盐酸、磷酸、硝酸、醋酸、葡萄糖酸或磺酸。
4.如权利要求1所述的抛光液,其特征在于:所述的双胍类化合物的含量为质量百分比0.01~7%。
5.如权利要求1所述的抛光液,其特征在于:所述的氮唑类化合物的含量为质量百分比0.01~15%。
6.如权利要求1所述的抛光液,其特征在于:所述的研磨颗粒选自SiO2、Al2O3、ZrO2、CeO2、SiC、Fe2O3、TiO2和Si3N4中的一种或多种。
7.如权利要求1所述的抛光液,其特征在于:所述的研磨颗粒的含量为质量百分比0.1~30%。
8.如权利要求1所述的抛光液,其特征在于:所述的研磨颗粒的粒径为30~120nm。
9.如权利要求1所述的抛光液,其特征在于:所述的抛光液的pH范围为8~12。
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CN200980103153.6A CN101970595B (zh) | 2008-01-30 | 2009-01-19 | 一种化学机械抛光液 |
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CN200810033260.3 | 2008-01-30 | ||
CNA2008100332603A CN101497765A (zh) | 2008-01-30 | 2008-01-30 | 一种化学机械抛光液 |
PCT/CN2009/000071 WO2009097737A1 (zh) | 2008-01-30 | 2009-01-19 | 一种化学机械抛光液 |
CN200980103153.6A CN101970595B (zh) | 2008-01-30 | 2009-01-19 | 一种化学机械抛光液 |
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CN102477261B (zh) * | 2010-11-26 | 2015-06-17 | 安集微电子(上海)有限公司 | 一种化学机械抛光液 |
CN102533119A (zh) * | 2010-12-21 | 2012-07-04 | 安集微电子(上海)有限公司 | 一种含氮胺类化合物的化学机械抛光液 |
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CN104371552B (zh) * | 2013-08-14 | 2017-09-15 | 安集微电子(上海)有限公司 | 含硅有机化合物在延长化学机械抛光液中研磨颗粒稳定性中的应用 |
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CN111378973A (zh) * | 2018-12-28 | 2020-07-07 | 安集微电子科技(上海)股份有限公司 | 一种化学机械抛光液及其应用 |
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