CN100555580C - 前段工序中用于清洁离子注入的光致抗蚀剂的组合物 - Google Patents
前段工序中用于清洁离子注入的光致抗蚀剂的组合物 Download PDFInfo
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- CN100555580C CN100555580C CNB2006800111224A CN200680011122A CN100555580C CN 100555580 C CN100555580 C CN 100555580C CN B2006800111224 A CNB2006800111224 A CN B2006800111224A CN 200680011122 A CN200680011122 A CN 200680011122A CN 100555580 C CN100555580 C CN 100555580C
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- acid
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Classifications
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- 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
- H01L21/302—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
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- G03F7/423—Stripping or agents therefor using liquids only containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D7/04—Water-soluble compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D7/5004—Organic solvents
- C11D7/5009—Organic solvents containing phosphorus, sulfur or silicon, e.g. dimethylsulfoxide
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
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- G—PHYSICS
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/426—Stripping or agents therefor using liquids only containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides
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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
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Abstract
用于从晶片基板去除非灰化的离子注入的光致抗蚀剂的前段(FEOL)剥离和清洁的组合物,包括:a)至少一种有机剥离溶剂,b)至少一种选自氟化铵,氟化氢铵或氟化氢的氟离子,c)至少一种选自无机酸或有机酸的酸化剂,d)水,组合物中还可任选地含有氧化剂。
Description
技术领域
本发明涉及用于清洁制造微电子器件过程中前段工序中经历晶片掺杂工艺的晶片的清洁组合物。本发明提供了在前段工序中用于除去注入的大量光致抗蚀剂和清洁晶片的组合物和方法。
发明背景
在集成电路制造中,通过抗蚀剂涂布的晶片进行离子注入以控制掺杂水平。近几年来,用于前段工序(front end of the line,FEOL)半导体制造工艺的光致抗蚀剂清洁或剥离步骤的数量有很大增长。在器件制造工艺中所需的不断增长的离子注入步骤推动了这种增长。目前,高电流或高能量注入操作(大剂量注入或HDI)是最为苛刻的,因为这些操作要求在减少或消除光致抗蚀剂爆裂、表面残余、以及金属污染时,获得高度的晶片清洁度,同时要求基本上没有基板/结(junction)损耗或者氧化物损耗。
HDI带来特别具有挑战性的FEOL清洁操作的原因在于后注入的抗蚀剂的物理结构,该抗蚀剂硬化并且难以除去,因为该清洁操作必须在图案化操作步骤之前,其中不同的光致抗蚀剂用于线图案化。该离子注入工艺有效地耗尽抗蚀剂表面的氢且使用注入物来注入该抗蚀剂膜。由于注入物渗入抗蚀剂,抗蚀剂转变成两个相异的层,外部是硬化的碳化外壳层,内部是体氢化层。由于外部碳化层已经基本上耗尽了氢,它能够比内部体光致抗蚀剂层的灰化慢大约75%。另外,该内部体层包括了比较高水平的化学键合的氮和余量水平的原始浇注溶剂,当提高灰化温度时快速释气和膨胀。当外部碳化外壳层的膨胀速率远低于内层挥发溶剂的速率时造成外壳破裂或“暴裂”,这种现象导致光致抗蚀剂的爆裂。光致抗蚀剂爆裂可能是等离子体灰化体系中工艺缺陷的最大来源。爆裂残余物的效应为:注入晶片上较高水平的粒子,需要攻击性的灰化后湿法清洁的高度氧化的表面残余物,和更频繁的腔体清洁和预防性维护程序。而且,当残余物积聚在工艺腔体时,粒子再沉积在其它晶片上的概率也增加。另一个因素是HDI能够溅射来自晶片基板的硅或二氧化硅,并且将残余物沉积在抗蚀剂的顶部上。
因此,在离子注入步骤之后,抗蚀剂和不希望的残余物应被彻底除去,使晶片表面无任何残余物,否则无效的残余物清除潜在地会产生高水平的工艺缺陷,且清洁步骤的质量可以直接影响电学良率。干法灰化后用湿法化学清洗,例如,氧等离子体和硫酸-过氧化氢洗液(piranha)湿法清洁操作,硫酸和过氧化氢或臭氧的混合物,通常被用于除去硬化的抗蚀剂和残余物。这种工艺昂贵且危险,且同样未有效地除去无机残余物,例如注入物、硅、二氧化硅和抗蚀剂添加物,因此,就需要更进一步的湿法化学清洁来去除无机残余物。而且,这种干法灰化且接着进行湿法化学清洁造成不希望地损伤掺杂的晶片,即,损伤该掺杂的晶片的源极区和漏极区。因此存在对FEOL清洁组合物的需求,该组合物能够有效地且高效率地从离子注入的晶片剥离-清洁光致抗蚀剂和离子注入残余物,并且对这种剥离-清洁组合物存在下述要求:不引起腐蚀,即,改变就该掺杂的晶片的源极区和漏极区而言的晶片结构。
发明概述
本发明提供用于在FEOL操作中从离子注入的晶片清除光致抗蚀剂和其它残余物的FEOL剥离和清洁组合物,以及使用这些组合物来FEOL清洁离子注入的晶片表面的方法,该组合物包括:至少一种有机剥离溶剂,至少一种选自氟化铵、氟化氢铵或氟化氢的氟离子,至少一种无机或有机酸,和水。本发明的FEOL剥离-清洁组合物优选地还包括氧化剂,所述氧化剂在使用前添加。本发明的FEOL剥离-清洁组合物基本上排除了在湿法化学清洁之前对任何灰化步骤的需要,使用本发明的化合物,取而代之允许用单个步骤剥离/清洁光致抗蚀剂和残余物。
本发明的用于剥离-清洁离子注入晶片基板的FEOL剥离和清洁组合物包含以下组分:
a)至少一种有机剥离溶剂,
b)至少一种选自氟化铵、氟化氢铵或氟化氢的氟离子,
c)至少一种选自无机或有机酸的酸化剂,和
d)水。
本发明的FEOL剥离-清洁组合物还包含以下组分:
a)至少一种有机剥离溶剂,
b)至少一种选自氟化铵、氟化氢铵或氟化氢的氟离子,
c)至少一种选自无机或有机酸的酸化剂,
d)水,和
e)氧化剂。
在后述组合物中,氧化剂通常就在该组合物的期望使用前一次加入到其他组分的前述组合物中。本发明的FEOL组合物还另外包含一种或多种组分,例如金属络合物/抗蚀化合物、其他腐蚀抑制剂和表面活性剂。
根据本发明的用于FEOL剥离-清洁离子注入晶片基板的方法包含清洁离子注入的晶片基板而不产生任何实质性金属侵蚀的方法,该方法包括将本发明的FEOL剥离-清洁组合物以足以清洁离子注入的晶片基板的时间接触该离子注入的晶片基板,其中该FEOL剥离-清洁组合物包含:
a)至少一种有机剥离溶剂,
b)至少一种选自氟化铵、氟化氢铵或氟化氢的氟离子,
c)至少一种选自无机或有机酸的酸化剂,和
d)水。
在本发明的剥离-清洁方法中使用的FEOL剥离-清洁组合物还包含以下组分:
a)至少一种有机剥离溶剂,
b)至少一种选自氟化铵、氟化氢铵或氟化氢的氟离子,
c)至少一种选自无机或有机酸的酸化剂,
d)水,和
e)氧化剂。
在后述组合物中,氧化剂通常就在该组合物的期望使用前一次加入到其他组分的前述组合物中。本发明的剥离-清洁方法中使用的FEOL组合物可另外包含一种或多种组分,例如金属络合物/耐腐蚀化合物、其他防腐剂和表面活性剂。
发明详述和优选实施方案
用于剥离-清洁离子注入的晶片基板的本发明的FEOL剥离和清洁组合物包含以下组分:
a)至少一种有机剥离溶剂,
b)至少一种选自氟化铵、氟化氢铵或氟化氢的氟离子,
c)至少一种选自无机或有机酸的酸化剂,和
d)水。
本发明的FEOL剥离-清洁组合物还包含以下组分:
a)至少一种有机剥离溶剂,
b)至少一种选自氟化铵、氟化氢铵或氟化氢的氟离子,
c)至少一种选自无机或有机酸的酸化剂,
d)水,和
e)氧化剂。
在后述组合物中,氧化剂通常就在该组合物的期望使用前一次加入到其他组分的前述组合物中。本发明的FEOL组合物可另外包含一种或多种组分,例如金属络合物/抗蚀化合物、其它腐蚀抑制剂和表面活性剂。
根据本发明的用于离子注入晶片基板的FEOL剥离-清洁的方法包含清洁离子注入的晶片基板而不产生任何实质性金属侵蚀的方法,该方法包括用本发明的FEOL剥离-清洁组合物以足以清洁离子注入的晶片基板的时间接触离子注入的晶片基板,其中的FEOL剥离-清洁组合物包含:
a)至少一种有机剥离溶剂,
b)至少一种选自氟化铵、氟化氢铵或氟化氢的氟离子,
c)至少一种选自无机或有机酸的酸化剂,和
d)水。
本发明用于剥离-清洁方法的FEOL剥离-清洁组合物还包含以下组分:
a)至少一种有机剥离溶剂,
b)至少一种选自氟化铵、氟化氢铵或氟化氢的氟离子,
c)至少一种选自无机或有机酸的酸化剂,
d)水,和
e)氧化剂。
在后述组合物中,氧化剂通常就在该组合物的期望使用前一次加入到其他组分的前述组合物中。本发明用于剥离-清洁方法的FEOL组合物可另外包含一种或多种组分,例如金属络合物/抗蚀化合物、其他腐蚀抑制剂和表面活性剂。
组合物中的至少一种有机剥离溶剂通常含有以组合物的总重量计约8-90重量%,优选约25-85重量%,更优选约45-82重量%。有机剥离溶剂通常为有机极性溶剂,所述有机剥离溶剂可包含一种或多种这样的溶剂。合适的溶剂包括,但不局限于,二烷基砜(化学式为R1-S(O)(O)-R2,其中R1和R2为碳原子数为1-4的烷基),二甲亚砜(DMSO),四氢噻吩-1-,1-二氧化物,例如环丁砜,甲基环丁砜和烷基环丁砜,二甲基乙酰胺和二甲基甲酰胺。最优选的溶剂是环丁砜。
本发明组合物中的组分提供的氟离子以组合物总重量计约为0.1-2.0重量%,优选约0.1-1.5重量%,更优选约0.1-0.8重量%。氟离子的来源可以包括氢氟酸,氟化铵和氟化氢铵,但不包括季铵氟化物。
本发明组合物中包含无机或有机酸的酸化剂以组合物总重量计通常约为0.4-7重量%,优选约为0.6-5重量%,更优选约为0.8-3重量%。组合物中合适的无机或有机酸包括,但不局限于,盐酸,磷酸,硫酸,醋酸或柠檬酸,并且所述无机或有机酸生成的总的酸性溶液(pH<5)。酸的选择既影响注入聚合体清洁也影响全部的材料的可混用性,因此,酸的选择能够缩短清洁时间或降低操作温度。
本发明组合物中包含的水以组合物总重量计约为8-90重量%,优选约10-75重量%,更优选约15-50重量%。
当氧化剂加入到本发明的组合物中,其余组分总重量和氧化剂的重量比通常为约1∶1-20∶1,优选重量比为约1∶1-10∶1,更优选重量比为约2∶1-5∶1,最优选重量比约为3∶1,任何合适的氧化剂可以加入到本发明的FEOL剥离/清洁组合物,例如合适的氧化剂包括,但不局限于,过氧化氢,过氧酸,有机过氧化物例如苯甲酰过氧化次氯酸盐(benzoyl peroxide hypochlorates),重铬酸盐,高锰酸盐,或硝酸。氧化剂优选过氧化氢。
本发明的组合物还可以任选地包含其它的组分,这种任选的其它组分包括络合剂和多种表面活性剂。
有机或无机螯合剂或金属络合剂/腐蚀抑制剂不是必需的,但可以任选性地包含于本发明的组合物,但是可以带来可观的效益,例如当混合到本发明的水性清洁组合物时,可以改善产品的稳定性。例如合适的螯合剂或络合剂包括,但不局限于,反-1,2-环己二铵四乙酸(CyDTA),乙二铵四乙酸(EDTA),锡酸盐,焦磷酸盐,亚烷基-二膦酸衍生物(例如乙烷-1-羟基-1,1-二膦酸酯(ethane-1-hydroxy-1,1-diphosphonate)),包含乙二胺、二亚乙基三胺或三亚乙基四胺官能团部分的膦酸酯,例如乙二胺四(亚甲膦酸(methylene phosphonic acid))(EDTMP),二亚乙基三胺五(亚甲基膦酸),三亚乙基四胺六(亚甲基膦酸)。螯合剂在组合物中以组合物总重量计约为0-5重量%,优选约为0.1-2重量%.
本发明的组合物还可以选择性地包含任何合适的水溶两性的,非离子的,阳离子的或阴离子表面活性剂。表面活性剂的加入能够降低制剂的表面张力以及改善被清洁表面的湿润性,因此,改善组合物的清洁作用。如果有进一步对铝抑制腐蚀的要求,表面活性剂的加入还可以降低铝的腐蚀速率。在本发明的组合物中使用的两性表面活性剂包括甜菜碱和磺基甜菜碱例如烷基甜菜碱,酰氨基烷基甜菜碱,烷基磺基甜菜碱和酰氨基烷基磺基甜菜碱;氨基羧酸衍生物例如两性甘氨酸盐(amphoglycinates),两性丙酸盐(amphopropionates),两性二甘氨酸盐(amphodiglycinates),和两性二丙酸盐(amphodipropionates);亚氨基二酸例如烷氧基烷基亚氨基二酸或烷氧基烷基亚氨基二酸;氧化胺例如烷基胺氧化物和烷基酰氨基烷基胺氧化物;氟烷基磺酸盐和氟化烷基两性表面活性剂;和它们的混合物。两性表面活性剂优选为椰油酰氨基丙基甜菜碱,椰油酰氨基丙基二甲基甜菜碱,椰油酰氨基丙基羟基磺基甜菜碱,辛酰两性二丙酸盐(capryloamphodipropionate),椰油酰氨基二丙酸盐,椰油两性丙酸盐,椰油两性羟基乙基丙酸盐,异癸烷氧基丙基亚氨基二丙酸,月桂基亚氨基二丙酸盐,椰油酰氨基丙基胺氧化物和椰油胺氧化物和氟化烷基两性表面活性剂。在本发明组合物中使用的非离子表面活性剂包括炔烃二醇,乙氧基化炔烃二醇,氟化烷基烷氧化物,氟化烷基酯,氟化聚氧乙烯烷醇,多元醇的脂肪酸酯,聚氧乙烯单烷基醚,聚氧乙烯二醇,硅氧烷类表面活性剂,和亚烷基二醇单烷基醚。优选地,非离子表面活性剂是炔烃二醇或乙氧基化炔烃二醇。在本发明组合物中使用的阴离子表面活性剂包括羧酸盐,N-酰基肌氨酸盐,磺酸盐,硫酸盐,和正磷酸的单和二酯,例如癸基磷酸酯。优选地,阴离子表面活性剂是不含金属的表面活性剂。在本发明组合物中使用的阳离子表面活性剂包括乙氧基化胺,二烷基二甲基铵盐,二烷基吗啉鎓盐,烷基苄基二甲基铵盐,烷基三甲基铵盐,和烷基吡啶鎓盐。优选地,阳离子表面活性剂不含卤素。例如,尤其合适的表面活性剂包括,但不局限于,3,5-二甲基-1-己炔-3-醇(Surfynol-61),乙氧基化2,4,7,9-四甲基-5-癸炔-4,7-二醇(Surfynol-465),聚四氟乙烯十六烷氧基丙基甜菜碱(ZonylFSK),Zonyl FSH,Triton X-100,即辛基苯氧基聚乙氧基乙醇等。表面活性剂的含量按组合物总重量计通常约为0-5重量%,优选约0.001-3重量%。
本发明的不含氧化剂的FEOL剥离清洁组合物的例子包括,但不局限于,下面表1-3所述组合物,其中组分的含量分别以重量计。
表1
组合物编号 | 环丁砜 | 水 | HCl | NH<sub>4</sub>F |
1 | 49 | 47.2 | 3 | 0.8 |
2 | 81.7 | 17 | 1 | 0.3 |
3 | 16.3 | 77.4 | 5 | 1.3 |
4 | 32.7 | 62.3 | 4 | 1 |
5 | 65.3 | 32.2 | 2 | 0.5 |
表2
组合物编号 | 环丁砜 | 水 | HCl | NH<sub>4</sub>F |
6 | 81.7 | 11.2 | 1 | 0.3 |
7 | 81.7 | 16.5 | 0.5 | 0.3 |
8 | 81.7 | 16.6 | 1 | 0.1 |
表3
组合物编号 | 环丁砜 | 水 | 酸的种类 | 酸 | NH<sub>4</sub>F |
9 | 81.7 | 15.3 | 冰醋酸 | 2.7 | 0.3 |
10 | 81.7 | 15.7 | 磷酸 | 2.3 | 0.3 |
11 | 81.7 | 10 | 磷酸 | 8.2 | 0.1 |
12 | 81.7 | 16 | 硫酸 | 2.0 | 0.3 |
13 | 81.7 | 14.9 | 柠檬酸 | 3.1 | 0.3 |
本发明的含有氧化剂的FEOL剥离清洁组合物的例子包括,但不局限于下文表4、5、6和7所述的组合物,其中组分含量以重量计。表4组合物为表1的组合物1以不同比率与30%的过氧化氢(不稳定的)混合。表5组合物为表1的组合物2以不同比率与30%过氧化氢(不稳定的)混合。表6组合物为表2的组合物6,7和8与30%的过氧化氢(不稳定)混合。表7组合物为表3的组合物9至组合物13与30%的过氧化氢(不稳定)混合。
表4
组合物编号 | 组合物1∶H<sub>2</sub>O<sub>2</sub>的比率 |
14 | 2∶1 |
15 | 5∶1 |
16 | 10∶1 |
表5
组合物编号 | 组合物2∶H<sub>2</sub>O<sub>2</sub>的比率 |
17 | 2∶1 |
18 | 5∶1 |
19 | 10∶1 |
20 | 1∶5 |
表6
组合物编号 | 组合物∶H<sub>2</sub>O<sub>2</sub>的比率 |
21 | 组合物6∶H<sub>2</sub>O<sub>2</sub> 3∶1 |
22 | 组合物7∶H<sub>2</sub>O<sub>2</sub> 3∶1 |
23 | 组合物8∶H<sub>2</sub>O<sub>2</sub> 3∶1 |
表7
组合物编号 | 组合物∶H<sub>2</sub>O<sub>2</sub>的比率 |
24 | 组合物9∶H<sub>2</sub>O<sub>2</sub> 3∶1 |
25 | 组合物10∶H<sub>2</sub>O<sub>2</sub> 3∶1 |
26 | 组合物11∶H<sub>2</sub>O<sub>2</sub> 3∶1 |
27 | 组合物12∶H<sub>2</sub>O<sub>2</sub> 3∶1 |
28 | 组合物13∶H<sub>2</sub>O<sub>2</sub> 3∶1 |
剥离/清洁实施例
表1中所述组合物1到组合物5被用于清洁未灰化离子注入的光致抗蚀剂。就一切情况而论,清洁的条件为65℃下30分钟,然后用DI水清洗1分钟,再用氮气烘干。样品用SEM分析以测定光致抗蚀剂的去除水平,结果列于表8。就一切情况而论,增加接触时间或升高温度能够获得更好的清洁。
表8
实施例编号 | 化合物编号 | 清洁效果 |
1 | 1 | 80% |
2 | 2 | 90% |
3 | 3 | 20% |
4 | 4 | 40% |
5 | 5 | 60% |
将前述表4中所述组合物14到组合物16被用于清洁未灰化离子注入的光致抗蚀剂。就一切情况而论,清洁的条件为65℃下30分钟,然后用DI水清洗1分钟,再用氮气烘干。样品用SEM分析以测定光致抗蚀剂的去除水平,结果列于表9。
表9
实施例编号 | 化合物编号 | 清洁效果 |
6 | 14 | 60% |
7 | 15 | 80% |
8 | 16 | 100% |
将前述表5中所述组合物17到组合物20被用于清洁未灰化的离子注入的光致抗蚀剂。就一切情况而论,清洁的条件为65℃下30分钟,然后用DI水清洗1分钟,再用氮气烘干。样品用SEM分析以测定光致抗蚀剂的去除水平,结果列于表10。
表10
实施例编号 | 化合物编号 | 清洁效果 |
9 | 17 | 100% |
10 | 18 | 100% |
11 | 19 | 100% |
12 | 20 | 70% |
将前述表6中所述组合物21到组合物23用于清洁未灰化的离子注入的光致抗蚀剂。就一切情况而论,清洁的条件为55℃下30分钟,然后用DI水清洗1分钟,再用氮气烘干。样品用SEM分析以测定光致抗蚀剂的去除水平,结果列于表11。
表11
实施例编号 | 化合物编号 | 蚀刻 | 清洁效果 |
13 | 21 | 没有 | 100% |
14 | 22 | 一些 | 100% |
15 | 23 | 没有 | 70% |
将表7中所述组合物24到组合物28被用于清洁未灰化的离子注入的光致抗蚀剂。将组合物与样品在下列的时间和温度下接触,然后用DI水清洗1分钟,再用氮气烘干。样品用SEM分析测定光致抗蚀剂的去除水平,结果列于表12。当蚀刻发生时,蚀刻结构根据使用配方的不同而不同。这妨碍了以确切数值表示蚀刻的测定,并且据报道:不仅仅是造成严重程度,而是会导致晶片的整个损坏。可通过降低温度、接触时间,或修正氧化剂溶液的比率来降低蚀刻(例如实施例18到20)。
表12
实施例编号 | 化合物编号 | 时间 | 温度 | 蚀刻程度 | 清洁效果 |
16 | 24 | 10分钟 | 45℃ | 轻微 | 100% |
17 | 25 | 10分钟 | 55℃ | 轻微 | 50% |
18 | 25 | 30分钟 | 55℃ | 剧烈 | 100% |
19 | 26 | 30分钟 | 55℃ | 无 | 70% |
20 | 27 | 30分钟 | 55℃ | 无 | 100% |
21 | 28 | 10分钟 | 35℃ | 严重 | 100% |
本发明的FEOL组合物是非临界组合物且不含超临界二氧化碳。
虽然在此以具体的实施方案描述本发明,但能够理解那些在不改变本文所披露的本发明构思的精神和范围的改变,修饰和变更,因此,其含义是包含在所附权利要求书的精神和范围内所有此类改变,修饰和变更。
Claims (9)
1.从晶片基板上剥离/清洁未灰化的离子注入的光致抗蚀剂的FEOL剥离和清洁方法,该方法包括在没有超临界CO2下进行该方法,且包括将晶片基板上未灰化的离子注入的光致抗蚀剂与FEOL剥离/清洁组合物接触足够的时间,以清洁具有未灰化的离子注入的光致抗蚀剂的晶片基板,其中所述FEOL剥离/清洁组合物包含:
a)至少一种有机剥离溶剂,
b)至少一种选自氟化铵、氟化氢铵和氟化氢的氟离子,
c)至少一种选自非HF的无机酸或有机酸的酸化剂,
d)水,和
e)至少一种氧化剂;
其中所述选自非HF的无机酸或有机酸的至少一种酸化剂以使得总的酸性溶液pH<5的量存在。
2.根据权利要求1的FEOL剥离和清洁方法,其中所述组合物中的至少一种氧化剂包括过氧化氢。
3.根据权利要求1的FEOL剥离和清洁方法,其中所述组合物中的至少一种有机剥离溶剂选自化学式为R1-S(O)(O)-R2的二烷基砜,其中R1和R2为1-4碳原子的烷基,二甲亚砜(DMSO),四氢噻吩-1,1-二氧化物,二甲基乙酰胺和二甲基甲酰胺。
4.根据权利要求2的FEOL剥离和清洁方法,其中所述组合物中的至少一种有机剥离溶剂选自化学式为R1-S(O)(O)-R2的二烷基砜,其中R1和R2为1-4碳原子的烷基,二甲亚砜(DMSO),四氢噻吩-1,1-二氧化物,二甲基乙酰胺和二甲基甲酰胺。
5.根据权利要求3的FEOL剥离和清洁方法,其中组合物中的至少一种有机剥离溶剂包括环丁砜。
6.根据权利要求4的FEOL剥离和清洁方法,其中组合物中的至少一种有机剥离溶剂包括环丁砜。
7.根据权利要求5的FEOL剥离和清洁方法,其中组合物中的至少一种酸包括盐酸。
8.根据权利要求6的FEOL剥离和清洁方法,其中组合物中的至少一种酸包括盐酸。
9.根据权利要求1的FEOL剥离和清洁方法,其中组合物包含45到82重量%的环丁砜,0.1至2.0重量%的氟化铵,0.8到3重量%的盐酸,15到50重量%的水,且过氧化氢以其余组分与过氧化氢组分的重量比为2∶1到5∶1的量存在。
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