CN114621832A - 高分子处理用工艺溶液 - Google Patents

高分子处理用工艺溶液 Download PDF

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CN114621832A
CN114621832A CN202111501590.2A CN202111501590A CN114621832A CN 114621832 A CN114621832 A CN 114621832A CN 202111501590 A CN202111501590 A CN 202111501590A CN 114621832 A CN114621832 A CN 114621832A
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chemical formula
group
process solution
disulfide
polymer
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房淳洪
姜韩星
金圣植
金泰熙
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Dongwoo Fine Chem Co Ltd
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Dongwoo Fine Chem Co Ltd
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Abstract

本发明提供一种高分子处理用工艺溶液，其包含极性非质子性溶剂、氟系化合物和含硫化合物，其保管稳定性优异，能够在提高对于残留在半导体晶圆电路面的粘接聚合物的去除力的同时使金属层的损伤最小化。

Description

高分子处理用工艺溶液
技术领域
本发明涉及能够提高对于粘接聚合物的去除力的同时使金属层的损伤最小化的高分子处理用工艺溶液。
背景技术
半导体元件的制造工序中，在半导体晶圆(以下，也称为“晶圆”)的表面形成电子电路等后，为了使晶圆的厚度变薄，有时实施晶圆的背面研磨(back grinding)。该情况下，为了保护晶圆电路面、固定晶圆等，通常在晶圆的电路面经由有机硅高分子等粘接聚合物来附着支撑体。如果将支撑体附着于晶圆的电路面，则能够加固晶圆的背面研磨后厚度变薄的晶圆，也能够在晶圆的研磨面形成背面电极等。
如果上述晶圆的背面研磨、背面电极形成等工序结束，则会从晶圆的电路面将支撑体去除，将粘接聚合物剥离而去除，将晶圆切割而制作芯片。
另一方面，近年来，开发了利用贯穿晶圆而设置的贯穿电极(例如，硅贯穿电极)的芯片层叠技术。根据该芯片层叠技术，利用贯穿电极来代替以往的线材将多个芯片的电子电路进行电连接，因此能够实现芯片的高集成化、运行的高速化。在利用该芯片层叠技术的情况下，为了使多个芯片层叠而成的集合体的厚度变薄，多数情况会进行晶圆的背面研磨，因此利用支撑体或粘接聚合物的机会增加。
但是，通常在晶圆的电路面经由粘接聚合物附着支撑体后，为了上述晶圆与支撑体的牢固附着，会实施热固化，因此在将粘接聚合物剥离时，发生固化的粘接聚合物残留在支撑体和晶圆的电路面的情况。因此，需要能够将残留在上述晶圆电路面的固化的粘接聚合物有效去除，同时防止对于晶圆或金属膜的损伤的方法。
另一方面，韩国公开专利第10-2014-0060389号是涉及粘接聚合物去除用组合物的发明，但存在对于网状高分子的去除速度慢或线形高分子去除性下降、发生金属层损伤的问题。
现有技术文献
专利文献
专利文献1：韩国公开专利第10-2014-0060389号
发明内容
解决课题的方法
本发明用于改善上述以往技术的问题，其目的在于，提供能够在提高半导体制造工序中残留在晶圆电路面的粘接聚合物的去除力的同时使金属层的损伤最小化的高分子处理用工艺溶液。
但是，本申请所要解决的课题不受以上提及的课题的限制，通过以下的记载本领域的技术人员将能够明确理解未提及的其他课题。
解决课题的方法
为了实现上述目的，本发明提供包含极性非质子性溶剂、氟系化合物和含硫化合物的高分子处理用工艺溶液。
发明效果
本发明通过包含极性非质子性溶剂、氟系化合物和含硫化合物，从而提供能够在提高半导体制造工序中残留在晶圆电路面的粘接聚合物的去除力的同时防止金属层的损伤的高分子处理用工艺溶液。
具体实施方式
本发明涉及包含极性非质子性溶剂、氟系化合物和含硫化合物的高分子处理用工艺溶液，其能够在提高残留在半导体晶圆电路面或金属层上的粘接聚合物的去除力的同时防止金属层的损伤。
上述粘接聚合物包含硅树脂，不仅可以包含线形的非反应性聚二甲基硅氧烷系高分子，还可以包含通过固化形成网状高分子的聚有机硅氧烷树脂。
本发明中，高分子处理用工艺溶液包含高分子清洗液、高分子剥离液以及高分子蚀刻液，最优选为高分子清洗液。
本申请说明书上下文中，烷基的含义是通过单键连接的烃基。
<高分子处理用工艺溶液>
本发明的高分子处理用工艺溶液可以包含极性非质子性溶剂、氟系化合物和含硫化合物，可以进一步包含其他添加剂。
此外，本发明的高分子处理用工艺溶液没有人为地加入水，优选实质不包含水。但是，视需要可以使用氟系化合物的水合物，因此最终可能会包含少量的水。该情况下，上述少量的水的含量相对于组合物总重量可以小于4重量％，在任意加入水的情况下，可能发生对于硅树脂等高分子的去除性降低，金属膜的损伤增加的问题。
此外，本发明的高分子处理用工艺溶液优选不包含如醇系化合物等那样在分子结构内含有羟基(-OH)的化合物。在分子结构内含有羟基的情况下，可能发生使氟系化合物的活性下降而降低硅树脂的去除性的问题。
(A)极性非质子性溶剂
本发明的高分子处理用工艺溶液包含一种以上的极性非质子性溶剂，视需要可以将两种以上的极性非质子性溶剂一同使用，上述极性非质子性溶剂起到使有机硅高分子溶胀、且使氟系化合物和被分解的有机硅高分子溶解的作用。
本发明的极性非质子性溶剂可以包含选自由酮系、乙酸酯系、酰胺系、吡啶系、吗啉系、吡咯烷酮系、脲系、磷酸酯系、亚砜系、腈系、碳酸酯系、
Figure BDA0003402672630000031
唑烷酮系、哌嗪系和呋喃系溶剂所组成的组中的一种以上。
另一方面，作为通常已知的溶剂的水或醇系化合物(例如，二乙二醇单甲醚、乙二醇、异丙醇等)的情况下，由于与氟离子形成氢键而难以去除高分子，因此本发明的高分子处理用工艺溶液的溶剂优选实质不包含水和醇系化合物。
上述酮系溶剂可以包含以下化学式7-1所表示的化合物：
[化学式7-1]
Figure BDA0003402672630000032
上述化学式7-1中，R23和R24各自独立地为C1～C18的直链或支链的脂肪族烃基，R23和R24的碳原子数之和优选为2个以上且小于30个。
例如，作为上述酮系溶剂，可以为2-庚酮、3-庚酮、4-庚酮、3-戊酮、2-己酮、3-己酮、4-甲基-2-戊酮、5-甲基-2-己酮或2,6-二甲基-4-己酮等，但不限于此。
作为上述乙酸酯系溶剂，例如，可以为乙酸甲酯、乙酸乙酯(EA)、乙酸丙酯、乙酸异丙酯、乙酸正丁酯、乙酸异丁酯、乙酸仲丁酯、乙酸戊酯、乙酸异戊酯、乙酸辛酯、乙酸苄酯、乙酸苯酯、乙氧基乙酸乙酯、甲氧基乙酸丁酯(MBA)、丙二醇单甲醚乙酸酯(PGMEA)、乙酸乙烯酯或乙氧基丙酸乙酯(EEP)等，但不限于此。
作为上述酰胺系溶剂，例如，可以为N,N-二甲基甲酰胺、N,N-二乙基甲酰胺、N,N-二甲基乙酰胺、N,N-二乙基乙酰胺、N,N-二丙基乙酰胺、N-乙基-N-甲基乙酰胺、N,N-二甲基丙酰胺、N,N-二甲基丁酰胺、N,N-二甲基异丁酰胺、N,N-二甲基戊酰胺、N,N-二乙基丙酰胺或N,N-二丁基丙酰胺等，但不限于此。
上述吡啶系溶剂可以包含以下化学式7-2所表示的化合物：
[化学式7-2]
Figure BDA0003402672630000041
上述化学式7-2中，R25～R27各自独立地可以为氢、C1～C10的直链或支链的脂肪族烃基、卤素(例如，F、Cl、Br或I)、醛基(-CHO)、乙醛基(-COCH3)、C1～C4的烷氧基、乙烯基、乙炔基、氰基(-CN)或甲基硫醚基(-SCH3)。
例如，作为上述吡啶系溶剂，可以为吡啶、2-甲基吡啶、3-甲基吡啶、4-甲基吡啶、4-乙基吡啶、4-丙基吡啶、4-异丙基吡啶、4-戊基吡啶、2,3-二甲基吡啶、2,4-二甲基吡啶、2,5-二甲基吡啶、3,4-二甲基吡啶、3,5-二甲基吡啶或2,4,6-三甲基吡啶等，但不限于此。
上述吗啉系溶剂可以包含以下化学式7-3所表示的化合物：
[化学式7-3]
Figure BDA0003402672630000042
上述化学式7-3中，R28为氢；C1～C6的直链或支链的脂肪族烃基；乙烯基；氰基(-CN)；被叔胺取代的C1～C4的脂肪族烃基；被C1～C4的烷基、氰基(-CN)、卤素基(例如，F、Cl、Br或I)或醛基(-CHO)取代的苯基或吡啶基，X为氧或-NR29-，R29为C1～C4的脂肪族烃基。
例如，作为上述吗啉系溶剂，可以为N-甲基吗啉、N-乙基吗啉、N-芳基吗啉、N-丁基吗啉或N-异丁基吗啉等，但不限于此。
作为上述吡咯烷酮系溶剂，例如，可以为N-甲基吡咯烷酮(NMP)、N-乙基吡咯烷酮(NEP)或N-乙烯基吡咯烷酮(NVP)等，但不限于此。
上述脲系溶剂可以包含以下化学式7-4所表示的化合物：
[化学式7-4]
Figure BDA0003402672630000051
上述化学式7-4中，X为氧或-NR29-，R29和R30各自独立地为C1～C6的直链、支链或环状脂肪族烃基；或被乙烯基、苯基、乙炔基、甲氧基或二甲基氨基取代的C1～C4的脂肪族烃基。
例如，作为上述脲系溶剂，可以为四甲基脲、四乙基脲或四丁基脲等，但不限于此。
上述磷酸酯系溶剂可以包含以下化学式7-5所表示的化合物：
[化学式7-5]
Figure BDA0003402672630000052
上述化学式7-5中，R31～R33各自独立地为C1～C8的直链或支链的脂肪族烃基；与邻接的氧一起形成环的C3～C8的2价的脂肪族烃基；非取代或被C1～C4的脂肪族烃基取代的苯基；被卤素(例如，F、Cl、Br或I)取代的C2～C4的脂肪族烃基或被卤素取代的苯基。
例如，作为上述磷酸酯系溶剂，可以为磷酸三乙酯、磷酸三丁酯、磷酸三戊酯或磷酸三烯丙酯(triallyl phosphate)等，但不限于此。
作为上述亚砜系溶剂，例如，可以为二甲基亚砜(DMSO)、二丁基亚砜、二苯基亚砜、二苄基亚砜或甲基苯基亚砜等，但不限于此。
作为上述腈系溶剂，例如，可以为丙腈、丁腈、异丁腈、乙腈、三甲基乙腈或苯基乙腈等，但不限于此。
作为上述碳酸酯系溶剂，例如，可以为碳酸二甲酯(DMC)、碳酸二乙酯、碳酸二苯酯、碳酸二苄酯、碳酸亚乙酯、碳酸亚丙酯(PC)或碳酸亚乙烯酯等，但不限于此。
作为上述
Figure BDA0003402672630000061
唑烷酮系溶剂，例如，可以为2-
Figure BDA0003402672630000062
唑烷酮、3-甲基-2-
Figure BDA0003402672630000063
唑烷酮等，但不限于此。
作为上述哌嗪系溶剂，例如，可以为二甲基哌嗪、二丁基哌嗪等，但不限于此。
上述呋喃系溶剂可以包含以下化学式7-6或7-7所表示的化合物：
Figure BDA0003402672630000064
上述化学式7-6和7-7中，R34～R39各自独立地可以为氢；或者被烷氧基、氰基或卤素取代或非取代的C1～C5的直链或支链的脂肪族烃基、或被烷氧基、氰基或卤素取代的C1～C5的烷基。
例如，作为上述呋喃系溶剂，可以为四氢呋喃、2-甲基四氢呋喃、3-甲基四氢呋喃、2,5-二甲基四氢呋喃、(四氢呋喃-2-基)乙腈、四氢糠氯、2,5-二甲氧基四氢呋喃、呋喃、2-甲基呋喃、2-乙基呋喃、2-丙基呋喃、2-丁基呋喃、2-戊基呋喃、3-甲基呋喃、2,3-二甲基呋喃、2,5-二甲基呋喃、2-氰基呋喃或2,5-二氰基呋喃等，但不限于此。
相对于高分子处理用工艺溶液总重量，上述极性非质子性溶剂的含量为66～99.89重量％，优选为70～99.45重量％。如果上述极性非质子性溶剂的含量小于66重量％，则可能发生金属膜受到损伤的问题，在大于99.89重量％的情况下，可能发生无法有效去除附着于电子部件的有机硅系树脂的问题。
(B)氟系化合物
本发明的高分子处理用工艺溶液包含一种以上的氟系化合物，上述氟系化合物起到将有机硅高分子的环断开而使分子量减小的作用。
本发明的氟系化合物可以包含一种以上的选自由烷基氟化铵、烷基氟化
Figure BDA0003402672630000065
和烷基氟化锍所组成的组中的化合物。
上述烷基氟化铵可以包含以下化学式4-1或4-2所表示的化合物：
[化学式4-1]
Figure BDA0003402672630000071
上述化学式4-1中，R9～R12各自独立地为碳原子数3～10的烷基。在上述R9～R12为碳原子数2以下的烷基的情况下，氟系化合物对于溶剂的溶解度下降而发生混合后立即析出、或经过一段时间后析出的问题。
[化学式4-2]
Figure BDA0003402672630000072
上述化学式4-2中，R13～R15各自独立地为碳原子数1～10的烷基。
例如，作为上述烷基氟化铵，可以为四丁基二氟化铵(TBAF·HF)、四丁基氟化铵(TBAF)、四辛基氟化铵(TOAF)或苄基三甲基氟化铵(BTMAF)等，但不限于此。
此外，上述烷基氟化铵如烷基氟化铵·n(H2O)那样可以以水合物形态存在，这里，n为5以下的整数。作为其例子，可以为四正丁基氟化铵水合物、四正丁基氟化铵三水合物或苄基三甲基氟化铵水合物等，但不限于此。
此外，上述烷基氟化
Figure BDA0003402672630000074
可以包含以下化学式5所表示的化合物：
[化学式5]
Figure BDA0003402672630000073
上述化学式5中，R16～R19各自独立地为碳原子数1～22的脂肪族烃基或碳原子数6～20的芳香族烃基。
例如，作为上述烷基氟化
Figure BDA0003402672630000079
可以为四丁基氟化
Figure BDA00034026726300000710
三乙基辛基氟化
Figure BDA0003402672630000077
或十六烷基三甲基氟化
Figure BDA0003402672630000078
等，但不限于此。
此外，上述烷基氟化锍可以包含以下化学式6所表示的化合物：
[化学式6]
Figure BDA0003402672630000081
上述化学式6中，R20～R22各自独立地为碳原子数1～22的脂肪族烃基、碳原子数6～20的芳香族烃基。
例如，作为上述烷基氟化锍，可以为三丁基氟化锍、三辛基氟化锍或正辛基二甲基氟化锍等，但不限于此。
相对于高分子处理用工艺溶液总重量，上述氟系化合物的含量为0.1～20重量％，优选为0.5～17重量％。在上述氟系化合物的含量小于0.1重量％的情况下，可能发生无法有效去除附着于电子部件等的有机硅系树脂的问题，在大于20重量％的情况下，由于水分含量虽时间增加反而可能发生硅树脂的去除性能下降以及由氟化物的增加导致金属膜受损。
(C)含硫化合物
本发明的高分子处理用工艺溶液包含一种以上的含硫化合物以减小对于粘接剂下部所露出的金属膜质的损伤，上述含硫化合物优选包含硫醇基(-SH)。此外，含硫化合物能够在不阻碍高分子处理用工艺溶液的高分子去除性能的同时提供金属防蚀效果。
本发明中，在含硫化合物脱离后述的化学式1～3的结构的情况下，例如在包含-OH或-NH-、NH2的情况下，会发生与氟系化合物形成氢键而高分子的去除性能快速下降的问题，从而不符合本发明的目的。
本发明的含硫化合物可以为本发明的组合物所包含的极性非质子性溶剂和氟系化合物以外追加包含的成分。
上述含硫化合物可以包含一种以上的以下化学式1-1～3中任一个所表示的化合物。
Figure BDA0003402672630000082
上述化学式1-1或上述化学式1-2中，R1为被硫醇基取代或非取代的碳原子数3～12的直链或支链烷基、被硫醇基或卤素取代或非取代的碳原子数3～12的环状烃基，上述卤素为氟、氯、溴或碘。
例如，作为上述化学式1-1所表示的含硫化合物，可以为丙烷-1-硫醇、丁烷-1-硫醇、戊烷-1-硫醇、己烷-1-硫醇、庚烷-1-硫醇、辛烷-1-硫醇、癸烷-1-硫醇、十二烷-1-硫醇、2-甲基丙烷-1-硫醇、2-甲基丙烷-2-硫醇、3-甲基-2-丁硫醇、3-甲基-1-丁硫醇、2-乙基-1-己硫醇、1,3-丙二硫醇、环戊硫醇、环己硫醇、苯基甲硫醇(phenylmethanethiol)、2-苯基乙硫醇、4-(叔丁基)苯基甲硫醇或糠基硫醇等，但不限于此。
例如，作为上述化学式1-2所表示的含硫化合物，可以为二乙基二硫醚、二丙基二硫醚、二异丙基二硫醚、二异戊基二硫醚、二戊基二硫醚、二丁基二硫醚、二异丁基二硫醚、二叔丁基二硫醚、甲基丙基二硫醚、二苯基二硫醚、二十二烷基二硫醚、双(1,1,3,3-四甲基丁基)二硫醚或二叔十二烷基二硫醚等，但不限于此。上述化学式1-2所表示的含硫化合物可以通过含硫醇基的化合物(例如，上述化学式1-1所表示的化合物)的氧化而形成。
[化学式2]
Figure BDA0003402672630000091
上述化学式2中，R2～R4和R6各自独立地为氢原子、碳原子数1～5的烷基、碳原子数1～5的烷氧基、或包含双键的碳原子数2～5的不饱和烃基，R5为直接连接或碳原子数1～5的亚烷基。
例如，作为上述化学式2所表示的含硫化合物，可以为(3-巯基丙基)三甲氧基硅烷、2-(三甲基甲硅烷基)乙硫醇、三甲基(2-甲基硫烷基乙基)硅烷(trimethyl(2-methylsulfanylethyl)silane)、(3-巯基丙基)甲基二甲氧基硅烷或(乙硫基)三甲基硅烷等，但不限于此。
[化学式3]
Figure BDA0003402672630000101
上述化学式3中，R7和R8可以彼此连接而形成脂环族或芳香族的单环或多环，上述单环或多环可以包含选自氮(N)、氧(O)或硫(S)中的一种以上的杂原子，且可以被一个以上的取代基取代。
此外，上述化学式3所表示的含硫化合物通过R7和R8彼此连接而形成环，从而可以具有与硫原子的共振结构，由于上述共振结构，会包含硫醇基。
例如，作为上述化学式3所表示的含硫化合物，可以为2-巯基噻唑啉、2-氨基-5-巯基-1,3,4-噻二唑、2-巯基苯并
Figure BDA0003402672630000102
唑或2-巯基苯并噻唑等，但不限于此。
相对于高分子处理用工艺溶液总重量，上述含硫化合物的含量为0.01～10重量％，优选为0.05～7重量％。在上述含硫化合物的含量小于0.01重量％的情况下，会发生无法充分抑制对于下部所露出的金属膜质的损伤的问题，在大于10重量％的情况下，可能发生上述粘接剂的去除性降低的问题。
(D)其他添加剂
在不损害本发明的高分子处理用工艺溶液的高分子去除性能的范围内，除了上述成分以外，可以进一步包含本领域通常使用的防腐蚀剂、表面活性剂等成分。
上述防腐蚀剂是为了在去除树脂时有效抑制含金属下部膜的腐蚀而使用的，一般可以从各种供应商商购获得，可以无追加精制地使用。
上述表面活性剂可以为了增强清洗特性而使用。例如，可以利用阴离子表面活性剂、阳离子表面活性剂、非离子表面活性剂，其中，尤其优选使用润湿性优异且气泡产生较少的非离子性表面活性剂，它们可以使用一种或将两种以上混合使用。
此外，本发明提供利用本发明的高分子处理用工艺溶液从器件去除高分子的方法。本发明的高分子去除方法可以适用针对本发明的高分子处理用工艺溶液描述的全部内容，对于重复的部分省略了详细说明，但是即使省略也可以同样地适用。
具体而言，上述高分子去除方法用于去除在使器件晶圆变薄的工序中所使用的有机硅粘接剂之类的高分子，使器件晶圆变薄的工序包括在载体晶圆和器件晶圆之间形成有机硅粘接剂和有机硅脱模层而使半导体基板变薄的工序。上述有机硅脱模层不会导致在工序后将载体晶圆去除的过程中器件晶圆在发生分离的位置破损。上述有机硅粘接剂将器件晶圆和载体晶圆粘接，经历固化过程。将这样的工序后固化的高分子利用本发明的高分子处理用工艺溶液去除。
以下，通过实施例来更加详细说明本发明。但是，以下实施例用于更具体地说明本发明，本发明的范围不受以下实施例的限定。
实施例1～26和比较例1～5：高分子处理用工艺溶液的制造
按照以下表1和2中记载的成分和组成比来制造高分子处理用工艺溶液。
[表1]
Figure BDA0003402672630000121
[表2]
Figure BDA0003402672630000131
上述表1和2中使用的氟系化合物如下。
A)TBAF·HF：四丁基二氟化铵
B)TBAF：四丁基氟化铵三水合物
C)BTMAF：苄基三甲基氟化铵水合物
D)四丁基氟化
Figure BDA0003402672630000132
E)三丁基氟化锍
实验例1：薄膜基板的去除性评价–网状高分子
将以50μm的厚度涂布有固化的有机硅高分子的晶圆切割成2X2cm2的大小后使用，在使25℃的组合物溶液以400rpm旋转的同时将所准备的样品浸渍1分钟，异丙醇(isopropyl alcohol，IPA)清洗后干燥。评价后，利用SEM测定固化的有机硅高分子的膜厚度。接着，利用扫描电子显微镜(scanning electron microscope，SEM)测定残留的有机硅系树脂的膜厚度，算出去除速度并整理在以下表3和4中。
去除速度(μm/min)＝[评价前厚度(μm)-评价后厚度(μm)]/评价时间(min)
实验例2：薄膜基板的去除性评价–线形PDMS
将按照预定的质量比混合了聚二甲基硅氧烷的预聚物与固化剂的掺混物旋涂于硅晶圆上且切割成2X2cm2的大小后使用，在使25度(℃)的组合物溶液以400rpm旋转的同时将所准备的样品浸渍1分钟，IPA清洗后干燥。评价后，利用光学显微镜和SEM观察晶圆表面的残留物。根据有/无产生残留物按照如下基准标记于以下表3和4中。
<评价基准>
○：无残留物
×：有残留物
实验例3：金属损伤评价1
将形成有由Sn、Sn/Ag合金、Sn/Au合金、Sn/Ag/Cu合金等构成的1011个凸球(Bumpball)的晶圆切割成2X2cm2的大小后使用，在使25℃的组合物溶液以400rpm旋转的同时将所准备的样品浸渍30分钟，然后IPA清洗后干燥。评价后，利用SEM确认凸球损伤(Bump balldamage)个数，将发生损伤的个数整理在以下表3和4中。
实验例4：金属损伤评价2
此外，将形成有铝薄膜的晶圆切割成2X2cm2的大小后使用，在使25℃的组合物溶液以400rpm旋转的同时将所准备的样品浸渍30分钟，IPA清洗后干燥。并且，评价后，利用光学显微镜确认焊盘缺陷(Defect)，将根据以下评价基准的结果整理在以下表3和4中。
<评价基准>
○：没有表面形态变化和变色
△：存在变色
[表3]
Figure BDA0003402672630000151
[表4]
Figure BDA0003402672630000161
参照上述表3和4，可以确认到本申请的实施例1～26的高分子处理用工艺溶液由于包含含硫化合物，因而不仅对于有机硅系网状高分子和线形高分子的去除性优异，而且对于金属的损伤也显著下降。特别是，在使用含硫化合物中的满足化学式1-1～3的结构的含硫化合物的实施例1～23的情况下，高分子去除能力优异，同时凸球损伤为5个以下或者完全不发生，Al损伤也不发生，可以确认到金属损伤防止效果更为优异。
另一方面，利用仅使用氟系化合物而没有极性非质子性溶剂的比较例2不能进行高分子去除，在虽然包含氟系化合物和极性非质子性溶剂，但未使用含硫化合物或使用其他添加剂的情况下，凸球损伤个数显著增加，也确认到对于铝的损伤。

Claims (13)

1.一种高分子处理用工艺溶液，其包含极性非质子性溶剂、氟系化合物和含硫化合物。
2.根据权利要求1所述的高分子处理用工艺溶液，所述含硫化合物包含一种以上的以下化学式1-1～1-2、化学式2和3中任一个所表示的化合物，
Figure FDA0003402672620000013
所述化学式1-1或所述化学式1-2中，
R1为被硫醇基取代或非取代的碳原子数3～12的直链或支链烷基、被硫醇基或卤素取代或非取代的碳原子数3～12的环状烃基，
化学式2
Figure FDA0003402672620000011
所述化学式2中，
R2～R4和R6各自独立地为氢原子、碳原子数1～5的烷基、碳原子数1～5的烷氧基、或包含双键的碳原子数2～5的不饱和烃基，
R5为直接连接或碳原子数1～5的亚烷基，
化学式3
Figure FDA0003402672620000012
所述化学式3中，
R7和R8可以彼此连接而形成脂环族或芳香族的单环或多环，所述单环或多环可以包含选自氮、氧或硫中的一种以上的杂原子，且可以被一个以上的取代基取代。
3.根据权利要求2所述的高分子处理用工艺溶液，所述化学式1-1所表示的化合物为选自由丙烷-1-硫醇、丁烷-1-硫醇、戊烷-1-硫醇、己烷-1-硫醇、庚烷-1-硫醇、辛烷-1-硫醇、癸烷-1-硫醇、十二烷-1-硫醇、2-甲基丙烷-1-硫醇、2-甲基丙烷-2-硫醇、3-甲基-2-丁硫醇、3-甲基-1-丁硫醇、2-乙基-1-己硫醇、1,3-丙二硫醇、环戊硫醇、环己硫醇、苯基甲硫醇、2-苯基乙硫醇、4-(叔丁基)苯基甲硫醇和糠基硫醇所组成的组中的一种以上。
4.根据权利要求2所述的高分子处理用工艺溶液，所述化学式1-2所表示的化合物为选自由二乙基二硫醚、二丙基二硫醚、二异丙基二硫醚、二异戊基二硫醚、二戊基二硫醚、二丁基二硫醚、二异丁基二硫醚、二叔丁基二硫醚、甲基丙基二硫醚、二苯基二硫醚、二十二烷基二硫醚、双(1,1,3,3-四甲基丁基)二硫醚和二叔十二烷基二硫醚所组成的组中的一种以上。
5.根据权利要求2所述的高分子处理用工艺溶液，所述化学式2所表示的化合物为选自由(3-巯基丙基)三甲氧基硅烷、2-(三甲基甲硅烷基)乙硫醇、三甲基(2-甲基硫烷基乙基)硅烷、(3-巯基丙基)甲基二甲氧基硅烷和(乙硫基)三甲基硅烷所组成的组中的一种以上。
6.根据权利要求2所述的高分子处理用工艺溶液，所述化学式3所表示的化合物为选自由2-巯基噻唑啉、2-氨基-5-巯基-1,3,4-噻二唑、2-巯基苯并
Figure FDA0003402672620000022
唑和2-巯基苯并噻唑所组成的组中的一种以上。
7.根据权利要求1所述的高分子处理用工艺溶液，所述氟系化合物包含选自由烷基氟化铵、烷基氟化
Figure FDA0003402672620000023
和烷基氟化锍所组成的组中的一种以上的化合物。
8.根据权利要求7所述的高分子处理用工艺溶液，所述烷基氟化铵包含以下化学式4-1或化学式4-2所表示的化合物，
Figure FDA0003402672620000021
所述化学式4-1中，
R9～R12各自独立地为碳原子数3～10的烷基，
所述化学式4-2中，
R13～R15各自独立地为碳原子数1～10的烷基。
9.根据权利要求7所述的高分子处理用工艺溶液，所述烷基氟化
Figure FDA0003402672620000033
包含以下化学式5所表示的化合物，
化学式5
Figure FDA0003402672620000031
所述化学式5中，
R16～R19各自独立地为碳原子数1～22的脂肪族烃基或碳原子数6～20的芳香族烃基。
10.根据权利要求7所述的高分子处理用工艺溶液，所述烷基氟化锍包含以下化学式6所表示的化合物，
化学式6
Figure FDA0003402672620000032
所述化学式6中，
R20～R22各自独立地为碳原子数1～22的脂肪族烃基、碳原子数6～20的芳香族烃基。
11.根据权利要求1所述的高分子处理用工艺溶液，所述极性非质子性溶剂包含选自由酮系、乙酸酯系、酰胺系、吡啶系、吗啉系、吡咯烷酮系、脲系、磷酸酯系、亚砜系、腈系、碳酸酯系、
Figure FDA0003402672620000034
唑烷酮系、哌嗪系和呋喃系溶剂所组成的组中的一种以上。
12.根据权利要求1所述的高分子处理用工艺溶液，相对于组合物总重量，包含：
所述极性非质子性溶剂66～99.89重量％；
所述氟系化合物0.1～20重量％；以及
所述含硫化合物0.01～10重量％。
13.根据权利要求1所述的高分子处理用工艺溶液，所述高分子处理用工艺溶液去除有机硅系高分子。
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