CN102816530B - 一种化学机械抛光液 - Google Patents

一种化学机械抛光液 Download PDF

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CN102816530B
CN102816530B CN201110153087.2A CN201110153087A CN102816530B CN 102816530 B CN102816530 B CN 102816530B CN 201110153087 A CN201110153087 A CN 201110153087A CN 102816530 B CN102816530 B CN 102816530B
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polishing
polishing fluid
triazole
silicon
present
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CN102816530A (zh
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王晨
何华锋
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Anji microelectronic technology (Shanghai) Limited by Share Ltd
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Anji Microelectronics Shanghai Co Ltd
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Priority to KR1020137029860A priority patent/KR101924668B1/ko
Priority to PCT/CN2012/000763 priority patent/WO2012167607A1/zh
Priority to SG2013086707A priority patent/SG195120A1/en
Priority to TW101120379A priority patent/TWI510605B/zh
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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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • 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
    • C09G1/04—Aqueous dispersions
    • 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
    • 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
    • H01L21/02002—Preparing wafers
    • H01L21/02005—Preparing bulk and homogeneous wafers
    • H01L21/02008—Multistep processes
    • H01L21/0201—Specific process step
    • H01L21/02024—Mirror polishing
    • 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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]

Abstract

本发明公开了一种化学机械抛光液，其包含：研磨颗粒、水、唑类化合物和哌嗪。本发明的抛光液实现了硅的高速抛光，且该体系具有非常高的稳定性，降低了半导体加工的综合成本。

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。
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。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(polishingtable)，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。
在新兴的TSV(ThroughSiliconVia)技术中，尤其是在晶背减薄(backsidethinning)时，对硅要求具有非常高的抛光速度。提高硅抛光速度的方法有很多种，通常以加强化学作用为主。
US2002032987公开了一种用醇胺作为添加剂的抛光液，以提高多晶硅(Polysilicon)的去除速率(removalrate)，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(Polysilicon)的去除速率(removalrate)，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。
US7452481B2公开了用氧化锆、四元以上的羧酸、季铵碱的组合物提高硅的抛光速度的方法。
CN101492592A公开了用唑提高硅的抛光速度的方法。由于该方法中唑的盐类为钠盐和钾盐，使得抛光液体系存在稳定性差的问题。因为为了使酸性的唑(例如TAZ)pH值调到碱性，实施例中用氢氧化钾或氢氧化钠调节pH值，引入的钠离子和钾离子会造成胶体稳定性下降。同时这些金属离子会造成半导体的金属离子污染。降低元器件的可靠性。
以上方法提高硅的抛光速度有限，尤其在新兴的TSV(ThroughSiliconVia)技术中，难以满足对硅要有非常高的抛光速度的要求。
发明内容
本发明解决的技术问题是提供一种化学机械抛光液，实现了很高的硅抛光速度。
本发明的化学机械抛光液，其包含研磨颗粒、水、唑类化合物和哌嗪。本发明发现唑类化合物和哌嗪的组合对硅(无论是单晶硅，还是多晶硅)都具有非常高的抛光速度。不仅如此，该抛光液系统还具有非常高的胶体稳定性。本发明的组合还可以继续包含四甲基氢氧化铵(TMAH)，用于进一步提高抛光速度。
在本发明中，唑类化合物选自三氮唑和四氮唑及其衍生物中的一种或多种。
在本发明中，唑类化合物为1，2，4-三氮唑，3-氨基-1，2，4-三氮唑，5-氨基-1，2，4-三氮唑，5-羧基-3-氨基-1，2，4-三氮唑和苯并三氮唑、1-H四氮唑、5-氨基四氮唑中的一种或多种。
在本发明中，唑类化合物的质量百分比浓度为1～8％。
在本发明中，研磨颗粒选自SiO2、Al2O3、CeO2、SiC和Si3N4中的一种或多种。
在本发明中，研磨颗粒的质量百分比浓度为1～20％。
在本发明中，哌嗪的质量百分比浓度为1～10％。
在本发明中，四甲基氢氧化铵的质量百分比浓度为1～10％。
在本发明中，抛光液的pH值为9～12。
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：
1)解决了硅的抛光速度低，并且胶体不稳定的问题；
2)实现了很高的硅抛光速度。大幅提高了TSV(ThroughSiliconVia)技术中，硅的抛光能力，提高了产能；
3)降低了半导体加工的综合成本。
具体实施方式
下面通过具体实施例进一步阐述本发明的优点，但本发明的保护范围不仅仅局限于下述实施例。
制备实施例
表1给出了本发明的化学机械抛光液实施例1～13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。
表1本发明的化学机械抛光液实施例1～13的配方
效果实施例
抛光条件：抛光机台为Logitech(英国)1PM52型，polytex抛光垫，4cm×4cm正方形晶圆(Wafer)，研磨压力3psi，研磨台转速70转/分钟，研磨头自转转速150转/分钟，抛光液滴加速度100ml/分钟。
表2对比例1～2及实施例1～13抛光效果对比
对比例1表明：单一的二氧化硅抛硅的速度不高，只有2100A/min。对比例2表明：在同样条件下，抛光液中加入TAZ(1，2，4-三氮唑)，可以将硅的抛光速度提高2倍。但是，该体系由于含有金属离子(钾离子)，体系很不稳定，15分钟后就会出现抛光颗粒变成凝胶、沉淀。伴随着沉淀现象的发生，抛光液也逐渐失效。
对比例2和实施例2比较后表明，加入哌嗪可使抛光速度提高2倍。
实施例3、4表明，进一步含有四甲基氢氧化铵，抛光速度会进一步提高。
实施例1～7表明，在用二氧化硅做研磨剂时，不同的唑类和哌嗪的组合都可以显著提高硅的抛光速度。
实施例8～13表明，选用Al2O3、CeO2、SiC和Si3N4作为研磨剂时，不同的唑类和哌嗪的组合也可以显著提高硅的抛光速度。
实施例1～13同时还表明，唑类和哌嗪的组合使得抛光液体系由原先的不稳定(5分钟后分层，沉淀)变得十分稳定(30天内研磨剂颗粒平均粒径没有变化)。稳定效果十分显著。
由以上数据表明，本发明的化学机械抛光液具有以下优点：
1)解决了硅的抛光速度低，并且胶体不稳定的问题；
2)实现了很高的硅抛光速度。大幅提高了TSV(ThroughSiliconVia)技术中，硅的抛光能力，提高了产能；
3)降低了半导体加工的综合成本。
以上对本发明的具体实施例进行了详细描述，但其只是作为范例，本发明并不限制于以上描述的具体实施例。对于本领域技术人员而言，任何对本发明进行的等同修改和替代也都在本发明的范畴之中。因此，在不脱离本发明的精神和范围下所作的均等变换和修改，都应涵盖在本发明的范围内。

Claims (5)

1.一种化学机械抛光液，其由研磨颗粒、水、唑类化合物和哌嗪组成，其中，
所述的研磨颗粒选自SiO2、Al2O3、CeO2、SiC和Si3N4中的一种或多种，所述的研磨颗粒的质量百分比浓度为1～20％，
所述的唑类化合物选自三氮唑和四氮唑及其衍生物中的一种或多种，所述的唑类化合物的质量百分比浓度为1～8％，
所述的哌嗪的质量百分比浓度为1～10％，
所述抛光液的pH值为9～12。
2.如权利要求1所述的抛光液，其特征在于：所述的唑类化合物为1,2,4-三氮唑，3-氨基-1,2,4-三氮唑，5-氨基-1,2,4-三氮唑，5-羧基-3-氨基-1,2,4-三氮唑、苯并三氮唑、1-H四氮唑、5-氨基四氮唑中的一种或多种。
3.如权利要求1所述的抛光液，其特征在于：所述抛光液还含有四甲基氢氧化铵。
4.如权利要求3所述的抛光液，其特征在于：所述的四甲基氢氧化铵的质量百分比浓度为1～10％。
5.如权利要求1-4任一项所述的抛光液，其特征在于：所述抛光液用于抛光单晶硅或多晶硅。
CN201110153087.2A 2011-06-08 2011-06-08 一种化学机械抛光液 Active CN102816530B (zh)

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KR1020137029860A KR101924668B1 (ko) 2011-06-08 2012-06-04 화학적 기계 연마액
PCT/CN2012/000763 WO2012167607A1 (zh) 2011-06-08 2012-06-04 一种化学机械抛光液
SG2013086707A SG195120A1 (en) 2011-06-08 2012-06-04 Chemical-mechanical polishing liquid
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US8801959B1 (en) * 2013-04-11 2014-08-12 Rohm And Haas Electronic Materials Cmp Holdings, Inc. Stable, concentratable silicon wafer polishing composition and related methods
US8795548B1 (en) * 2013-04-11 2014-08-05 Rohm And Haas Electronic Materials Cmp Holdings, Inc. Silicon wafer polishing composition and related methods
US9150759B2 (en) * 2013-09-27 2015-10-06 Rohm And Haas Electronic Materials Cmp Holdings, Inc Chemical mechanical polishing composition for polishing silicon wafers and related methods
CN106189873A (zh) * 2016-07-22 2016-12-07 清华大学 一种抛光组合物
CN111378384A (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

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CN101463227B (zh) * 2007-12-21 2013-06-12 安集微电子（上海）有限公司 一种用于阻挡层抛光的化学机械抛光液
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