CN103946361B - 聚硅氧氮烷氢氧化物薄膜清洗溶液及使用其的聚硅氧氮烷氢氧化物薄膜图案形成方法 - Google Patents

聚硅氧氮烷氢氧化物薄膜清洗溶液及使用其的聚硅氧氮烷氢氧化物薄膜图案形成方法 Download PDF

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CN103946361B
CN103946361B CN201280055366.8A CN201280055366A CN103946361B CN 103946361 B CN103946361 B CN 103946361B CN 201280055366 A CN201280055366 A CN 201280055366A CN 103946361 B CN103946361 B CN 103946361B
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silicones azane
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金奉焕
郭泽秀
裴镇希
尹熙灿
林相学
金相均
李真旭
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Abstract

提供一种聚硅氧氮烷氢氧化物薄膜清洗溶液，相对于清洗溶液整体包括0.01wt％至7wt％之间的选自由醇类溶剂、酯类溶剂、硅烷醇类溶剂、烷氧基硅烷类溶剂、和烷基硅氮烷类溶剂以及它们的组合组成的组中的添加剂。

Description

聚硅氧氮烷氢氧化物薄膜清洗溶液及使用其的聚硅氧氮烷氢 氧化物薄膜图案形成方法
技术领域
本公开内容涉及一种用于氢化聚硅氧氮烷(聚硅氧硅氮烷，polysiloxazane)薄膜的清洗溶液(冲洗溶液，rinse solution)以及使用其图案化氢化聚硅氧氮烷薄膜的方法。
背景技术
氢化聚硅氧氮烷在被涂覆在具有凸起和凹陷的基板上并被加热时转变为致密的膜，从而填充凸起和凹陷之间的间隙并使凸起和凹陷平面化，并且因此正在进行它作为绝缘层、分离膜、硬涂层等的用途的研究。例如，这种二氧化硅膜被广泛用作用于诸如LSI、TFT液晶显示器(LCD)等的半导体器件的层间绝缘层、平面化层、钝化膜、器件绝缘中间层等。
一般采用以下方法在半导体器件等中形成二氧化硅膜。即，将氢化聚硅氧氮烷溶液旋涂在其上根据需要形成有半导体、配线、电极等的基板上，并且因此具有阶差(stepdifference)或无阶差，将其加热以去除其中的溶剂，并且随后在大于或等于350℃下烘烤使得氢化聚硅氧氮烷溶液可以转变为二氧化硅膜，并且将二氧化硅膜用作绝缘中间层、平面化层、钝化膜、器件之间的绝缘中间层等。
然而，当以这种方法将氢化聚硅氧氮烷溶液旋涂在基板上时，在基板周围形成珠状物，并且同时氢化聚硅氧氮烷溶液环流至基板的后侧周围。为了防止膜由于基板周围的珠状物而具有不均匀的厚度，在涂覆氢化聚硅氧氮烷溶液之后，通过在形成在基板的表面上的膜周围涂覆或喷涂处理溶剂来进行边缘珠状物去除处理(在下文中为EBR)，并且此外，清洗基板的后侧以去除并清洁在表面周围移动和附着于其的氢化聚硅氧氮烷。
取决于后处理可能需要从基板剥离以上述方法形成的氢化聚硅氧氮烷膜，或者可能需要清洁和去除附着于诸如旋涂机等的涂覆装置的氢化聚硅氧氮烷。
通过常规的清洗溶液或剥离剂不能充分地清洗或去除这种聚硅氧氮烷，并且因此，当进行EBR处理时可以在基板的切边区域中在去除膜的部分与未去除膜的另一部分之间的边界处形成称为隆起(hump)的膜厚度差。在烘烤的过程中，该隆起可能造成膜的开裂或剥离，并且因此，需要能够在EBR处理之后在切边区域上获得具有更好形状的膜的用于EBR处理的溶剂。
发明内容
技术问题
本发明的一个实施方式提供一种用于氢化聚硅氧氮烷薄膜的清洗溶液，该清洗溶液能够精确地剥离在基板边缘上的氢化聚硅氧氮烷薄膜。
本发明的另一个实施方式提供一种使用用于氢化聚硅氧氮烷薄膜的清洗溶液来图案化氢化聚硅氧氮烷薄膜的方法。
本发明的又一个实施方式提供一种通过使用用于氢化聚硅氧氮烷薄膜的清洗溶液形成的绝缘层。
技术方案
根据本发明的一个实施方式，用于氢化聚硅氧氮烷薄膜的清洗溶液基于清洗溶液的总重量包括以0.01wt％至7wt％的量的选自醇类溶剂、酯类溶剂、硅烷醇类溶剂(silanol-based solvent)、烷氧基硅烷类溶剂、烷基硅氮烷类溶剂(alkylsilazane-basedsolvent)以及它们的组合中的添加剂。
基于用于氢化聚硅氧氮烷薄膜的清洗溶液的总重量可以以0.02wt％至5wt％的量包括添加剂。
添加剂可以选自正丁醇、辛醇、三甲基硅烷醇(trimethylsilanol)、三乙基硅烷醇、六甲基二硅氮烷、六乙基二硅氮烷、四乙氧基硅烷、四甲氧基硅烷以及它们的组合。
基于清洗溶液的总重量，清洗溶液可以进一步包括以93wt％至99.9wt％的量的选自芳烃类溶剂、醚类溶剂、萜品类溶剂以及它们的组合中的溶剂。
芳烃类溶剂可以选自二甲苯、乙苯、丙苯、丁苯、均三甲苯以及它们的组合。
醚类溶剂可以选自二正丁醚、茴香醚以及它们的组合。
萜品类溶剂可以选自对烷(萜烷，p-menthane)、对戊烷、对伞花烃(p-cymene，对异丙基苯甲烷)、蒎烯、松脂(松节油，turpentine)以及它们的组合。
根据本发明的另一个实施方式，提供一种通过使用用于氢化聚硅氧氮烷薄膜的清洗溶液来图案化氢化聚硅氧氮烷薄膜的方法。
根据本发明的又一个实施方式，提供一种通过使用用于氢化聚硅氧氮烷薄膜的清洗溶液形成的绝缘层(隔离层，insulation layer)。
在具体实施方式中描述了本发明的其他实施方式。
有益效果
提供一种用于氢化聚硅氧氮烷薄膜的清洗溶液，该清洗溶液能够精确地剥离在基板边缘上的氢化聚硅氧氮烷薄膜。
附图说明
图1示出了评估用于氢化聚硅氧氮烷薄膜的清洗溶液的剥离特性的方法。
具体实施方式
在下文中详细描述了本发明的实施方式。然而，这些实施方式是示例性的，并且本公开内容不限于此。
在本说明书中，当没有另外提供定义时，“取代的”是指用选自卤素原子(F、Cl、Br、或I)、羟基、硝基、氰基、亚氨基(＝NH、＝NR，其中，R是C1至C10烷基)、氨基(-NH2、-NH(R')和-N(R")(R"')，其中，R'至R"'独立地是C1至C10烷基)、脒基、肼基或腙基、羧基、C1至C10烷基、C6至C20芳基、C3至C20环烷基、C1至C10杂烷基、C3至C20杂芳基和C2至C20杂环烷基中的至少一个取代基取代，代替官能团中的至少一个氢；是指用选自＝O、＝S、＝NR(其中，R是C1至C10烷基)、＝PR(其中，R是C1至C10烷基)和＝SiRR'(其中，R和R'独立地是C1至C10烷基)中的至少一个取代基取代，代替官能团中的至少两个氢；或者，是指用选自≡N、≡P、和≡SiR(其中，R是C1至C10烷基)的至少一个取代基取代，代替官能团中的至少三个氢。
根据本发明的一个实施方式，用于氢化聚硅氧氮烷薄膜的清洗溶液包括选自醇类溶剂、酯类溶剂、硅烷醇类溶剂、烷氧基硅烷类溶剂、烷基硅氮烷类溶剂以及它们的组合中的添加剂。
醇类溶剂包括C1至C10醇，例如C3至C10醇，并且具体地，正丁醇、辛醇等。
酯类溶剂可以是由RC(＝O)OR'(其中，R和R'独立地是取代或未取代的C1至C10烷基或者取代或未取代的C6至C18芳基)表示的酯化合物。
硅烷醇类溶剂的具体实例包括三烷基硅烷醇，例如三甲基硅烷醇、三乙基硅烷醇等。本文中，烷基可以是取代或未取代的C1至C10烷基。
烷氧基硅烷类溶剂的具体实例可以包括四烷氧基硅烷，例如四乙氧基硅烷、四甲氧基硅烷等。本文中，烷氧基可以是取代或未取代的C1至C10烷氧基。
烷基硅氮烷类溶剂的具体实例可以包括六甲基二硅氮烷、六乙基二硅氮烷等。烷基可以是取代或未取代的C1至C10烷基。
添加剂可以抑制被认为是氢化聚硅氧氮烷的聚合部分的Si-H基团与Si-N基团的反应，并且因此当氢化聚硅氧氮烷与清洗溶液混合时抑制它们的固化或凝胶化。
基于用于氢化聚硅氧氮烷薄膜的清洗溶液的总重量可以以0.01wt％至7wt％并且具体地0.02wt％至5wt％的量包括添加剂。当在此范围内包括添加剂时，可以以用于与氢化聚硅氧氮烷反应的合适的量包括添加剂并且由于在氢化聚硅氧氮烷中优异的可溶性而对固化或凝胶化产生较高稳定性作用和充分的剥离特性。
用于氢化聚硅氧氮烷薄膜的清洗溶液极好地溶解在氢化聚硅氧氮烷中。可以通过适当地混合诸如二甲苯、乙苯、丙苯、丁苯、均三甲苯等的芳烃类溶剂，诸如二正丁醚、茴香醚等的醚类溶剂，以及诸如对烷(萜烷，p-menthane)、对戊烷、对伞花烃、蒎烯、松脂等的萜品类溶剂，并且进一步将选自醇类溶剂、酯类溶剂、硅烷醇类溶剂、烷氧基硅烷类溶剂、烷基硅氮烷类溶剂以及它们的组合中的添加剂添加入其中来制备用于氢化聚硅氧氮烷薄膜的清洗溶液。
基于清洗溶液的总重量，清洗溶液可以进一步包括以93wt％至99.9wt％的量的选自芳烃类溶剂、醚类溶剂、萜品类溶剂以及它们的组合中的溶剂。
用于氢化聚硅氧氮烷薄膜的清洗溶液可以用来图案化氢化聚硅氧氮烷薄膜。构成氢化聚硅氧氮烷薄膜的氢化聚硅氧氮烷不具有特别限制的特性，但是重均分子量可以在1,000至10,000的范围内，并且在分子中Si-H3基团可以在所有Si-H基团中的15mol％至35mol％的范围内。氢化聚硅氧氮烷具有在0.2wt％至3wt％的范围内的氧含量。
图案化的氢化聚硅氧氮烷薄膜可以用作用于半导体器件等的绝缘层。
用于实施发明的形式
在下文中，参考实施例更详细地示出本发明，但是在任何情况下都不能将这些实施例解释为限制本发明的范围。
(合成例1：氢化聚硅氧氮烷的合成)
用干燥氮气内部置换配有搅拌装置和温度控制器的2L反应器。随后，将4.0g纯水注入1,500g的干吡啶中并与之充分混合，将生成物放入反应器中，并将反应器保温在5℃。然后，将混合物搅拌同时经1小时将100g的二氯硅烷缓慢地注入反应器中。随后，经3小时将70g的氨缓慢地添加至反应器中。然后，用30分钟将干燥氮气注入反应器中，并且去除残留在反应器中的氨。
通过1μm特氟隆(TEFLON)(四氟乙烯)过滤器在干燥的氮气氛下过滤获得的白色浆状产物，获得1,000g的过滤的溶液。随后，将1,000g的干二正丁醚添加至过滤的溶液中，通过三次将混合物中的溶剂从吡啶替换成二正丁醚来将混合物的固体浓度调节成20wt％，并且通过具有0.03μm的孔径的特氟隆过滤器过滤生成物。
获得的氢化聚硅氧氮烷显示出1.6wt％的氧含量、2,100的聚苯乙烯折合的(polystyrene-reduced)重均分子量、和0.2的(总)SiH3/SiH之间的摩尔比。
本文中，使用FlashEA1112设备(Thermo Fisher Scientific Inc.)测量氧含量，使用Avance DPX-300的1H-NMR分析仪(Bruker Co.)和CDC13作为锁定溶剂来测量(总)SiH3/SiH的摩尔比，通过使用GPC：HPLC泵1515、RI检测器2414(Waters Co.)和柱：KF801、KF802、KF803(Shodex Inc.)测量重均分子量。
(实施例1至6和比较例1至4：用于氢化聚硅氧氮烷薄膜的清洗溶液)
制备根据实施例1至6和比较例1至4的用于氢化聚硅氧氮烷薄膜的清洗溶液以具有如在以下表1中的组成。
(表1)
评价1：稳定性
在将磁性搅拌器(magnetic churner)放入500L玻璃烧瓶中并用氮气干燥烧瓶内部以后，将20cc的包括根据合成例1的氢化聚硅氧氮烷的各个二正丁醚溶液注入烧瓶中。随后，将300cc的根据实施例1至6和比较例1至4的用于氢化聚硅氧氮烷薄膜的清洗溶液分别添加至氢化聚硅氧氮烷中，并且以200rpm搅拌混合物。在40％的相对湿度下在22℃下使得搅拌的溶液静置，并且检查溶液的状态。直至烧瓶中的溶液被凝胶化所需的时间(凝胶化天数)被认为是稳定性指数，并且结果提供在以下表2中。
评价2：剥离特性
将3cc的包括根据合成例1的氢化聚硅氧氮烷的二正丁醚溶液滴在设置在旋涂机中的具有8英寸直径的裸硅晶片的中心，并以1500rpm旋涂20秒，并且随后在晶片的外周从3mm的高度以10ml/min的流动速率持续5秒喷涂如表1中所示的根据实施例1至6和比较例1至4的用于氢化聚硅氧氮烷薄膜的各清洗溶液。随后，在100℃的加热板上加热并干燥晶片3分钟。
图1示出了评估用于氢化聚硅氧氮烷薄膜的清洗溶液的剥离特性的方法。图1示出了在将清洗溶液喷涂在硅晶片上的氢化聚硅氧氮烷薄膜上之后氢化聚硅氧氮烷薄膜的形状。当氢化聚硅氧氮烷薄膜的端部变凸并产生高度变化ΔT时，从剥离区域(即，从外晶片周围)去除3mm的膜，从而检查膜是否残留。通过使用光谱反射膜厚度测量计ST-4000(K-MAC)和SEM S-4800(2型，Hitachi Ltd.)从外晶片周围至约10mm扫描膜而测量高度变化ΔT(仅在高度变化ΔT周围使用SEM)，并且通过使用光学显微镜LV100D(Nikon Inc.)检查膜残留物。结果提供在以下表2中。
(表2)
凝胶化天数 ΔT(μm) 膜残留物
实施例1 9 0.3 否
实施例2 12 0.2 否
实施例3 14 0.6 否
实施例4 10 0.4 否
实施例5 16 0.4 否
实施例6 12 0.2 否
比较例1 2(NG(不好)) 0.4 否
比较例2 2(NG(不好)) 0.4 否
比较例3 >20 0.4 是(NG(不好))
比较例4 >3(NG(不好)) >1(NG(不好)) 是(NG(不好))
如表2中所示，根据实施例1至6的包括选自醇类溶剂、酯类溶剂、硅烷醇类溶剂、烷氧基硅烷类溶剂、烷基硅氮烷类溶剂以及它们的组合中的添加剂的用于氢化聚硅氧氮烷薄膜的清洗溶液显示出优异的结果，例如直至凝胶化的更多的天数、低ΔT、并且无膜残余物。相反，根据比较例1和2的以在参考值之外的不足的量包括选自醇类溶剂、酯类溶剂、硅烷醇类溶剂、烷氧基硅烷类溶剂、烷基硅氮烷类溶剂以及它们的组合中的添加剂或者没有添加剂的用于氢化聚硅氧氮烷薄膜的清洗溶液显示出小于或等于5天的直至凝胶化的较少数的天数，而根据比较例3的以过多的量包括六甲基二硅氮烷作为烷基硅氮烷类溶剂的清洗溶液显示出膜残留物并可能污染设备或损坏装置特性。另一方面，根据比较例4的使用丙二醇单甲醚乙酸酯(PGMEA)作为常规添加剂的清洗溶液显示出较少的直至凝胶化的天数、高ΔT和膜残留物，并且可能污染设备或损坏装置特性。
虽然已经结合目前被认为是实用的示例性实施方式对本发明进行了描述，但是应当理解，本发明并不限于所公开的实施方式，而是相反，旨在涵盖包括在所附权利要求书的精神和范围内的各种变更和等同设置。

Claims (7)

1.一种用于氢化聚硅氧氮烷薄膜的清洗溶液，包括：基于所述清洗溶液的总重量以0.01wt％至7wt％的量的醇类溶剂的添加剂；以及基于所述清洗溶液的总重量以93wt％至99.9wt％的量的选自芳烃类溶剂、醚类溶剂、萜品类溶剂以及它们的组合中的溶剂。
2.根据权利要求1所述的清洗溶液，其中，基于所述清洗溶液的总重量以0.02wt％至5wt％的量包括所述添加剂。
3.根据权利要求1所述的清洗溶液，其中，所述添加剂选自正丁醇、辛醇以及它们的组合。
4.根据权利要求1所述的清洗溶液，其中，所述芳烃类溶剂选自二甲苯、乙苯、丙苯、丁苯、均三甲苯以及它们的组合。
5.根据权利要求1所述的清洗溶液，其中，所述萜品类溶剂选自对烷、对戊烷、对伞花烃、蒎烯、松脂以及它们的组合。
6.一种通过使用根据权利要求1至5中任一项所述的清洗溶液图案化氢化聚硅氧氮烷薄膜的方法。
7.一种通过使用根据权利要求1至5中任一项所述的清洗溶液形成的绝缘层。
CN201280055366.8A 2011-11-10 2012-10-31 聚硅氧氮烷氢氧化物薄膜清洗溶液及使用其的聚硅氧氮烷氢氧化物薄膜图案形成方法 Active CN103946361B (zh)

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