CN102280522B - 在半导体上形成电流迹线的方法 - Google Patents
在半导体上形成电流迹线的方法 Download PDFInfo
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- CN102280522B CN102280522B CN201110177596.9A CN201110177596A CN102280522B CN 102280522 B CN102280522 B CN 102280522B CN 201110177596 A CN201110177596 A CN 201110177596A CN 102280522 B CN102280522 B CN 102280522B
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Classifications
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- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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Abstract
公开了一种制造半导体电流迹线的方法。所述方法包括在涂覆半导体的二氧化硅或氮化硅层上选择性沉积包含松香树脂和蜡的热熔油墨抗蚀剂,随后使用无机酸刻蚀剂以刻蚀二氧化硅或氮化硅层未涂覆盖的部分以暴露半导体,并同时抑制热熔油墨抗蚀剂的侧蚀。被刻蚀的部分随后可被金属化以形成多条基本均匀的电流迹线。
Description
技术领域
本发明涉及一种在半导体上形成尺寸大致均匀的电流迹线的方法。更具体地,本发明涉及一种使用热熔抗蚀剂和包含多元醇的无机酸蚀刻剂的组合以抑制侧蚀从而在半导体上形成尺寸大致均匀的电流迹线的方法。
背景技术
例如光伏器件和太阳能电池的半导体器件的制造包括在半导体的正面和背面上形成导电接触件或电流迹线。金属涂层必须能与半导体形成稳定的欧姆接触以便确保电荷载流子从半导体形成且无阻碍地进入导电接触件。为了避免电流损耗,金属化接触格栅必须具有足够的电流导电性,也即高导电率或足够高的导体迹线横截面积。
存在多种满足上述要求的工艺以在太阳能电池的背面涂覆金属。例如,为了改善太阳能电池背面处的电流传导,增强在背面上的直接p掺杂。为此目的通常使用铝。例如通过气相沉积来施加铝,或通过印刷背面且驱入或者分别合金入背面来施加铝。采用厚膜技术的金属涂敷是用于金属化导体迹线的传统方法。使用的糊料包括金属颗粒并因此能导电。通过丝网印刷、掩膜、移印或涂胶来施加糊料。通常使用的工艺是丝网印刷工艺,其中形成具有80μm至100μm最小线宽的指状金属涂层线。即使在这种栅宽度下,与纯金属结构相比,电导率损耗也是明显的。这可对串联电阻以及太阳能电池的填充系数和效率形成不利影响。因为此种工艺使得导体迹线变得更平,所以在更小的印制导体迹线宽度处这种影响被增强。金属颗粒之间的非导电性氧化物和玻璃组分成为这种降低导电性的主要原因。
当金属涂覆正面或光入射面时,目的在于使有源半导体表面的遮蔽达到最小量以便使用尽可能多的表面来捕捉光子。用于制造正面接触的复杂工艺使用用于限定导体迹线结构的激光器和其它成像技术。晶片的正面可优选地经受晶体取向纹理刻蚀以便使表面具有降低反射的改进的光入射几何结构。为了制造半导体结,磷扩散或离子注入发生在晶片的正面上以制造n掺杂(n+或n++)区域并对晶片提供一PN结。n掺杂区域可称作发射层。
抗反射层施加在晶片的正面或发射层。此外,抗反射层可作为钝化层。合适的抗反射层包括如为SiOx的氧化硅层,如为Si3N4的氮化硅层,或氧化硅和氮化硅层的组合。在前述分子式中,x是氧原子的数目,通常x是整数2。这种抗反射层可通过多种技术沉积,例如通过各种气相沉积方法,例如化学气相沉积和物理气相沉积。
随后在正面上限定开口或图案。图案穿过抗反射层以暴露晶片的半导体主体表面。可使用多种工艺来形成图案,例如但不限于激光烧蚀、机械方法、化学和光刻工艺。这种机械方法包括锯切和刨削。通常的光刻工艺包括在晶片表面上设置可成像材料,图案化可成像材料以在抗反射层中形成开口,将图案转移至晶片,在开口中沉积金属层并移除可成像材料。在正面上形成开口的化学方法的一个例子是使用刻蚀混合物来刻蚀,例如缓冲氧化物刻蚀剂。这种缓冲氧化物刻蚀剂可以包括一种或多种无机酸与如为铵类化合物的缓冲剂的组合。在刻蚀步骤之前,将抵抗刻蚀剂的刻蚀活性的掩模应用为与电流迹线的位置相反的负片图案。在刻蚀之后,通常在金属化电流迹线之前移除掩模。
在电流迹线形成期间经常引发的主要问题是侧蚀。这导致半导体器件的缺陷和低效。当使用结合掩模的刻蚀方法来形成电流迹线时,该问题是普遍的。对于将刻蚀剂应用到被选择性掩蔽的半导体,刻蚀剂可能不仅仅移除未被掩模覆盖的抗反射层部分,而且通过毛细作用渗到位于掩模和抗反射层的界面处的掩模下,从而导致被掩模覆盖的部分抗反射层被不符要求地刻蚀掉。这导致电流迹线具有不规则宽度,其中不规则宽度导致最终的金属化器件的不规则和非均匀的电流。此外,这种侧蚀可形成邻近相邻电流迹线的支流从而导致电短路。
因为业界寻求使用更薄和更精细半导体晶片来制造半导体器件,且同时增加在晶片正面上的电流迹线数量以增大电输出,所以使用更小和更精细材料的困难使得该问题变得复杂化。此外,具有更小尺寸的电流迹线减少了遮蔽。当半导体用作收集入射辐射的装置时,例如光伏器件和太阳能电池,大电流迹线可阻挡入射光照射在抗反射层上,因此减少了由半导体吸收的入射光的量,导致光伏器件或太阳能电池效率受损。因此,需要一种方法能基本减少或消除在半导体晶片上形成电流迹线时的侧蚀问题并允许精细线路电流迹线的形成。
发明内容
在一个实施例中,方法包括:a)提供包括正面和背面的半导体,正面包括由SiOx、氮化硅或其组合构成的抗反射层;b)选择性地将热熔油墨抗蚀剂施加至抗反射层,所述热熔油墨抗蚀剂包括一种或多种具有酸性官能团的氢化松香树脂,和一种或多种脂肪酸,所述热熔油墨抗蚀剂具有至少190的酸值;以及c)将包含一种或多种无机酸的刻蚀组合物施加至半导体以蚀刻去除半导体抗反射层的暴露部分且同时抑制侧蚀。
在另一个实施例中,方法包括:a)提供包括正面和背面的半导体,所述正面包括掺杂的发射层;b)选择性地施加热熔油墨抗蚀剂至所述掺杂的发射层,所述热熔油墨抗蚀剂包括一种或多种具有酸性官能团的氢化松香树脂,和一种或多种脂肪酸,所述热熔油墨抗蚀剂具有至少190的酸值;以及c)施加包含一种或多种无机酸的刻蚀组合物至半导体以蚀刻去除掺杂的发射层的暴露部分且同时抑制侧蚀。
该方法使得在半导体上形成多个电流迹线,该半导体在抗反射层或掺杂发射层的涂覆部分中具有减小的或无法探测到的侧蚀。这使得金属电流迹线与许多采用传统方法制造的传统半导体器件相比,具有均匀尺寸并为半导体器件提供均匀电流和增大的电输出。由互连支流产生的相邻电流迹线之间的短路被减少或消除。该方法也使得电流迹线形成为具有精细线条尺寸,因此增加了半导体上电流迹线的数量同时使得能在更小尺寸晶片上形成电流迹线。此外,通过减小电流迹线的尺寸可减少或消除不需要的遮蔽,因而减少了遮蔽且增大由半导体器件吸收的入射光。热熔油墨抗蚀剂具有的组成能在与抗反射层或发射层的界面处提供足够的粘附力以抑制刻蚀剂由于毛细作用渗入热熔油墨抗蚀剂下方。此外,通过使用碱性水溶液来溶解而不是膨胀和提起,可容易并快速地从抗反射层或掺杂发射层上移除热熔油墨抗蚀剂,而不会造成任何可阻碍金属电镀或污染最终器件的残余物。因为溶解的抗蚀剂可通过中和而沉淀出,这允许简易的废料处理。此外,这允许设备较少的周期性维护。
用于选择性移除抗反射层的刻蚀剂与热熔油墨抗蚀剂是相容的,使其不会与油墨抗蚀剂发生化学反应且不会在油墨抗蚀剂和抗反射层或发射层的界面处渗入热熔油墨抗蚀剂下。在温和条件下施加刻蚀剂,因此减少了对使用刻蚀剂的工人的危害。
具体实施方式
如在本说明书全文中使用的,术语“沉积”和“电镀”可互换。术语“电流迹线”和“电流线路”可互换。术语“组合物”和“浴”可互换。不定冠词“一种”和“一个”意在包括单数以及复数。术语“选择性沉积”意味着在基材上特别的指定区域中发生材料的沉积。术语“抗蚀剂”意味着不会以物理或化学方式受到包含无机或有机酸的刻蚀剂作用的组合物。术语“氢化”意味着化合物部分或全部的不饱和化学键(-C=C-)已被化学处理以打断或用氢饱和化学键(-CH2-CH2-)。
下述缩写词具有下面的含义,除非上下文清楚地指出其它含义:℃=摄氏度;g=克;mg=毫克;cp=厘泊,1cp=1x10-3帕(Pas)=0.01泊=1.02x10-4千泊/米2;A=安培;dm=分米;μm=微米;nm=纳米;以及UV=紫外线。
除非有其它指示,所有的百分比和比率均为重量比。除非清楚记载数值范围被限定至增至100%,否则所有的范围均包含任意顺序和任意顺序组合。
光电器件和太阳能电池可由单晶或多晶或无定形硅半导体晶片构成。尽管以下记载涉及硅半导体晶片,也可使用其它合适的半导体晶片,例如砷化镓、锗化硅和锗。当使用硅晶片时,其通常具有p型基本掺杂。
晶片的正面可任选地经受晶体取向纹理刻蚀以便使表面具有降低反射的改善的光入射几何结构。为了制造半导体结,在晶片的正面发生磷扩散或离子注入以制造n掺杂(n+或n++)区域并为晶片提供PN结。n掺杂区域可称作发射层。
在一个实施例中,抗反射层加至晶片的正面或发射层。此外,抗反射层可作为钝化层。合适的抗反射层包括但不限于如为SiOx的氧化硅层,如为Si3N4的氮化硅层,或氧化硅和氮化硅层的组合。在前述分子式中,x是氧原子的数目,通常x是整数2,也即二氧化硅。这种抗反射层可通过多种技术沉积,例如通过多种气相沉积方法,例如化学气相沉积和物理气相沉积。尽管氧化硅和氮化硅的厚度没有限定,通常其厚度为100nm至250nm。
热熔油墨抗蚀剂可通过喷墨印刷、气溶胶喷涂或丝网印刷来选择性沉积。选择性施加热熔油墨抗蚀剂以形成与电流迹线相反的负片图案。WO2005/013323和WO2005/011979公开了在光伏器件的制造中丝网印刷抗蚀剂的方法。优选地,热熔油墨抗蚀剂通过喷墨印刷或气溶胶喷涂来选择性施加至抗反射层。更优选地,通过喷墨印刷来选择性施加。在通过喷墨印刷或气溶胶喷涂期间,热熔油墨抗蚀剂的粘度范围为7cp至21cp,优选为9cp至15cp。更优选地,在施加热熔油墨的时候,其粘度为10cp至12cp。
在另一个实施例中,在施加任何抗反射层之前,通过喷墨印刷、气溶胶喷涂或丝网印刷将热熔油墨抗蚀剂直接选择性沉积至掺杂发射层。这称为选择性发射层实施例。在选择性发射层实施例中,热熔油墨抗蚀剂形成与电流迹线相反的负片图案。通常在该实施例中,发射层为重度掺杂,例如n++掺杂。
喷墨印刷方法可为连续喷墨方法或按需喷墨方法。连续方法是当使用泵连续喷出油墨抗蚀剂时,通过改变电磁场来调整油墨抗蚀剂方向的印刷方法。按需喷墨方法是根据电信号,仅在需要时才分配油墨抗蚀剂的方法。按需喷墨方法可被划分为压电喷墨方法和热喷墨方法,其中压电喷墨方法通过使用由电引发机械改变的压电板来产生压力,热喷墨方法通过由热产生的气泡膨胀来产生压力。
与喷墨印刷方法不同,气溶胶喷涂方法首先形成油墨抗蚀剂的气溶胶。气溶胶通过安装至印刷头的加压喷嘴而导至半导体基材。气溶胶与会聚的气体混合并以会聚状态输送至加压喷嘴。使用会聚气体以分配油墨抗蚀剂,这减少了喷嘴堵塞的可能性并也使得能形成比使用喷墨设备更精细的电流迹线、更大的纵横比。
在95℃或更低的温度,优选在65℃至90℃的温度下将热熔油墨抗蚀剂施加至抗反射层或掺杂发射层的表面。更优选地,在70℃至80℃的温度下施加热熔油墨抗蚀剂。这种低的喷墨温度允许油墨用于大多数喷墨印刷头组件或气溶胶喷雾器。此外,油墨抗蚀剂在低温下具有更长的寿命。热熔油墨抗蚀剂在施加后可快速硬化并粘合至抗反射层或掺杂发射层的表面,使得配方中无需硬化剂或交联剂。因此,此方法可消除UV使用步骤和其它传统的硬化步骤。
热熔油墨抗蚀剂通常被施加至包括抗反射层或掺杂发射层而没有金属组分的半导体基材。尽管方法对于电流线路的厚度没有限定,但是通常热熔油墨抗蚀剂被选择性施加至SiOx或氮化硅涂层或掺杂发射层以形成电流线路,电流线路具有100μm或更窄的宽度,或例如80μm至20μm,或例如70μm至30μm。
热熔油墨抗蚀剂包括一种或多种氢化松香树脂,其包括作为主要组分的氢化或部分氢化松香酸或其盐,松香酸或其盐来源于松香或海松型松香酸,松香或海松型松香酸的通式为具有菲核的C19H29COOH。异构体包括但不限于左旋海松酸、新松香酸、长叶松酸、去氢松香酸、二氢松香酸(也可是三氢)以及四氢松香酸。重均分子量从300至308,或例如302至306。酸值至少为150,或例如155至200,或例如170至190(mgKOH/g)。松香由松树(主要为松属沼泽松(Pinuspalustris)和松属湿地松(Pinuselliotii))得到。松香是在从活树上抽取的松节油蒸馏形成油性树脂之后得到的残余物。木松香是通过从松树树桩提取石脑油并蒸馏去除挥发性成分后得到的。妥尔油(talloil)是分馏妥尔油的共产物。氢化松香树脂可从其自然原产地购买或提取得到并可依照本文中公开的方法精炼。商业可购买的部分氢化松香树脂的例子是皮诺瓦有限公司(PinovaIncorporated)的STAYBELITE氢化松香。另一种可商业购买的部分氢化松香树脂是STAYBELITEResin-E。一种可商业购得的全氢化松香是FORALTMAX-E。通常,热熔油墨抗蚀剂中含有的氢化松香树脂可以具有大于或等于10重量%的量、或例如10重量%至40重量%的量、或例如20重量%至30重量%的量。
热熔油墨抗蚀剂也可包括一种或多种脂肪酸或其盐,所述脂肪酸或其盐具有通式R1COO-M,其中R1是具有7至48个碳原子、优选具有12至24个碳原子的直连、支链或环状烷基或烯烃基团,而M是氢或抗衡离子,例如纳、钾、钙、铵或NHy(CH2CH2OH)z,其中y和z是从0至4的整数且其和为4。这种脂肪酸包括但不限于羊脂酸、羊蜡酸、月桂酸、亚油酸、肉豆蔻酸、油酸、棕榈酸和硬脂酸或其盐。通常,脂肪酸选自月桂酸、亚油酸、肉豆蔻酸、棕榈酸、硬脂酸及其盐。优选地,脂肪酸选自肉豆蔻酸、棕榈酸及其盐。这种脂肪酸及其盐具有200或更大的酸值,通常为215至250(mgKOH/g)。许多这种脂肪酸及其盐可由天然油脂得到,例如海产油(marine)、菜籽油、动物油、妥尔油、大豆油、棉籽油和花生油。这种脂肪酸、盐和混合物或者可商业购得或者可由现有技术制造。通常,在热熔油墨抗蚀剂中含有的这种脂肪酸及其盐的含量为至少60重量%、或例如65重量%至90重量%、或例如70重量%至80重量%的量。
任选地,热熔油墨抗蚀剂包括一种或多种光学增白剂。可使用传统的光学增白剂,例如荧光增白剂。这种光学增白剂包括但不限于4,4’-双[2-(2-甲氧苯基)乙烯基]-1,1’-联苯;1,4-双(2-氰基苯乙烯基)苯;2,2’-(1,4-萘亚基)双苯并噁唑;2,2’-(2,5-噻吩亚基)双[5-(1,1-二甲基乙基)]-苯并噁唑;2,5-噻吩亚基双(5-叔丁基-1,3-苯并噁唑);以及2,2’-(1,2-乙烯亚基二-4,1-亚苯基)双苯并噁唑。商业可购得的荧光增白剂的例子为瑞士汽巴(Ciba)公司的UVITEXTMFP和UVITEXTMOB、以及德国拜耳公司(BayerA.G.)公司的BLANKOPHORTMER。热熔油墨抗蚀剂中含有的这种光学增白剂可以具有0.01重量%至1重量%,或例如0.05重量%至0.1重量%的量。
通过本领域公知的任何合适的方法将刻蚀剂施加至具有选择性地施加热熔油墨抗蚀剂使其覆盖抗反射层或掺杂发射层的半导体基材。这种方法包括但不限于将半导体基材浸没在刻蚀剂浴中,通过喷墨印刷、气溶胶喷涂或是采用传统喷涂设备来选择性施加。与许多传统刻蚀工艺相反,在温和温度下施加刻蚀剂。温和温度有助于减少或防止对抗蚀剂的侵蚀,因此油墨抗蚀剂在刻蚀期间保持其完整性并抑制了刻蚀剂的侧蚀。刻蚀温度范围从室温至50℃、或例如从25℃至40℃。
刻蚀剂包括一种或多种无机酸,并任选地为具有余量的水的一种或多种多元醇。刻蚀剂以80秒或更短周期施加,通常从5秒至60秒,最通常地从20秒至40秒。
无机酸包括但不限于氢氟酸、盐酸、硫酸、硝酸和磷酸。通常无机酸以水溶形式提供,作为浓缩液或稀释水溶液。最通常地,无机酸为氢氟酸。刻蚀剂中含有的无机酸具有1重量%至20重量%的量。
多元醇通常在室温下是可溶于水的并与无机酸相容,使得不存在稳定性问题。这种多元醇包括但不限于二醇、例如多元醇、例如乙二醇、聚乙二醇、丙二醇、聚丙二醇、丁二醇、聚丁二醇、二丙二醇、三丙二醇、以及丙三醇。优选地,多元醇选自乙二醇和丙二醇。刻蚀剂中含有的这种多元醇可以具有20体积%至80体积%、或例如40体积%至70体积%、或例如50体积%至60体积%的量。
除了无机酸和多元醇之外,刻蚀剂中也可包含铵化合物。通常,刻蚀剂包括一种或多种铵化合物。铵化合物包括但不限于氟化铵和二氟化铵。通常铵化合物为氟化铵。通常铵化合物作为水性浓缩液或稀溶液来提供。刻蚀剂中含有的这种铵化合物可以具有10重量%至40重量%的量。
通常当铵化合物包含在刻蚀剂中时,铵化合物与无机酸的体积比为10∶1至4∶1。优选的刻蚀剂为具有40体积%至60体积%的一种或多种多元醇的氟化铵水溶液和氟化氢水溶液,所述氟化铵水溶液和氟化氢水溶液的体积比为10∶1至4∶1。配方的余量可为水。
热熔油墨抗蚀剂和刻蚀剂的组合抑制了侧蚀,使得电流线路具有大致均匀的宽度并在相邻电流导线之间基本没有支流形成。热熔油墨抗蚀剂和刻蚀剂的组合抑制了热熔油墨抗蚀剂和抗反射层或被涂敷的发射层的界面处的毛细作用,该毛细作用通常导致刻蚀剂渗入热熔油墨抗蚀剂下,导致侧蚀并最终使得电流线路具有不规则尺寸和低效的电流传导。
当完成刻蚀时,可用水冲洗半导体以去除任何刻蚀剂。随后从半导体基材剥离热熔油墨抗蚀剂。整个热熔油墨抗蚀剂的酸值至少为190,或例如为190至250,或例如为200至230(mgKOH/g)。采用稀释的碱性水溶液来剥除热熔油墨抗蚀剂,例如使用氢氧化钾或氢氧化钠。氢氧化物的浓度可从0.1重量%至5重量%。在从室温至50℃的温度下施加这种温和的碱性水溶液。剥除是迅速的,可耗时一分钟或更短。基本完全剥除抗蚀剂。抗蚀剂从SiOx或氮化硅层或发射层的表面溶解,与许多传统抗蚀剂的提升或浮脱不同。少量的残留物可使用水从半导体清洗移除。
刻蚀和剥除之后,随后完成基材的金属化。但是,在选择性发射层实施例中,可使用如前所述形成抗反射层的材料和方法而将抗反射层沉积在发射层的被刻蚀部分上。涂敷有热熔油墨抗蚀剂的那部分发射层具有比被刻蚀部分更高的掺杂量,且是在半导体的正面上电镀金属以形成电流迹线的那部分。
在任一实施例的正面金属化之前,金属化半导体晶片的背面,例如采用铝金属化,以形成低阻抗的晶片。可使用任何传统方法。通常,半导体晶片的表面电阻,也称为薄膜电阻,范围可从40至90欧姆/平方。
随后在正面电流线路上沉积一层金属。通常将银糊料施加至电流线路上并烧制。通常随后进行光引发金属电镀。金属包括但不限于银、铜和镍。如果金属源是无电镀浴,则不施加外部电流而完成镀覆。如果金属源是电镀浴,则施加背侧电势(整流器)至半导体晶片基材。商业可购得的无电镀镍浴的例子为DURAPOSITTM、SMT88和NIPOSITTMPM980和PM988。商业可购得的镍电镀浴的例子为NICKELGLEAMTM系列电解产品。商业可购得的铜镀浴为COPPERGLEAMTMST901和901。商业可购得的银镀浴的例子为ENLIGHTTM620银板。所有上述商业可购得的槽浴可从美国马萨诸塞州的LLC马尔伯勒的罗门哈斯电子材料公司(RohmandHaasElectronicMaterials,LLCMarlborough,Massachusetts)购得。
光可以是连续的或脉冲的。半导体被浸入金属镀浴中,并将光施加至半导体,使得在电流线路上镀覆金属。光源包括但不限于白炽灯、LED光源(发光二极管)、红外线灯、荧光灯、水银灯、卤素灯和激光器。
通常的电流密度为0.1A/dm2至5A/dm2。特定的电流需求取决于所使用晶片的特定尺寸。所用的电镀工艺为常规工艺。通常,这种金属层厚度范围从1μm至50μm,更通常的从5μm至25μm。
以下实例用于说明本发明的各个方面,但并不意味着限定本发明的范围。
实施例1(比较例)
制备具有下述表格中公开的配方的热熔喷墨抗蚀剂。抗蚀剂在室温下为固体。
组分 | 含量 |
部分氢化松香树脂1 | 24.9重量% |
肉豆蔻酸 | 75重量% |
2,5-噻吩亚基双(5-叔丁基-1,3-苯并噁唑)2 | 0.1重量% |
1STAYBELITE通常组成和特性:松香酸<3重量%,去氢松香酸6-10重量%,二氢松香酸60-80重量%,四氢松香酸5-15重量%,其它树脂酸和中性物10-15重量%,软化点,Ring&Ball,℃=65-69,酸值158-160
2UVITEXOBTM光学增白剂
热熔物放置在DirectMaskTMDoD65喷墨印刷机(可从德国弗仑登斯坦的舒米德公司购得(SchmidGmbH,Freudenstadt,Germany))的贮液器中。贮液器中的温度升高至75℃以溶解热熔抗蚀剂。抗蚀剂在室温下被选择性印刷在十二个单晶硅晶片的二氧化硅涂层上以在晶片上形成“H”的图案。
随后使用从MIS有限公司(美国田纳西州苏果威尔(SurgoinsvilleTN))购得的捆绑有PAX-it图像分析软件的PAXcam数字显微镜照相机来测量被刻蚀过的晶片的线宽。沿着抗蚀剂沉积的边缘来测量线宽。对于十二个晶片而言,平均线宽测定为54.2μm±3.2。
刻蚀水溶液由氟化铵和氟化氢构成,两者体积比为6∶1,刻蚀水溶液由40重量%氟化铵水溶液和49重量%的氟化氢水溶液制备得到。通过将晶片浸没在刻蚀液中,在30℃下将刻蚀剂施加至单晶硅晶片。晶片与溶液保持接触25秒。随后将晶片从刻蚀液移出并在室温下用水清洗以移除刻蚀剂和刻蚀残余物。
随后通过在40℃下将晶片浸没在剥除溶液中,使用0.5重量%的氢氧化钾碱性水溶液从晶片上剥除热熔抗蚀剂。使用捆绑有PAX-it图像分析软件的PAXcam数字显微镜照相机来测定剥除之后的晶片的线宽。平均线宽测定为79.9μm±4.4。宽度的增加是由于刻蚀剂对热熔抗蚀剂的侧蚀造成的。测定的侧蚀为12.8μm/每侧(剥除之后的线宽-剥除之前的线宽/2)。
实施例2(比较例)
使用另一组具有二氧化硅涂层的十二个晶片来重复实施例1中所述的方法。使用相同的热熔喷墨抗蚀剂以在晶片上形成“H”图案,且用相同刻蚀液刻蚀晶片。使用实施例1中的相同的捆绑有PAX-it图像分析软件的PAXcam数字显微镜来测定线宽。印刷制得的晶片的平均线宽为58.5μm±4.4,而刻蚀和剥除之后测得的平均线宽为69.7μm±2.5。测定的侧蚀为5.6μm/每侧。
实施例3
重复实施例1所述的方法,除了刻蚀剂包含50体积%的乙烯乙二醇、此外氟化铵溶液和氟化氢溶液的体积比为6∶1。
实施例1和2中所使用的带有二氧化硅涂层的类型的十二个单晶晶片被选择性地涂敷有实施例1表中公开的热熔喷墨抗蚀剂以形成“H”图案。使用PAXcam数字显微镜测量线宽。印刷之后第一组晶片的平均线宽为49.5μm±4.4,而第二组晶片印刷之后的平均线宽为52.0μm±3.3。刻蚀并使用碱性水溶液将热熔抗蚀剂从第一组晶片剥除之后的平均线宽为49.2μm±2.2,而第二组晶片为52.0μm±4.5。第一组晶片的侧蚀测定为0.15μm/侧,且第二组晶片侧蚀测定为0μm/侧。与实施例1和2对比,本发明的方法大大降低了涂敷在单晶晶片上的二氧化硅的侧蚀。
Claims (15)
1.一种在半导体上形成电流迹线方法,所述方法包括:
a)提供包括正面和背面的半导体,所述正面包括由SiOx或氮化硅构成的抗反射层;
b)将热熔油墨抗蚀剂选择性地施加至所述抗反射层,所述热熔油墨抗蚀剂包括一种或多种具有酸官能团的氢化松香树脂、和一种或多种脂肪酸,且所述热熔油墨抗蚀剂的酸值至少为190;以及
c)对所述半导体施加包含一种或多种无机酸和一种或多种多元醇的刻蚀组合物以刻蚀去除所述半导体抗反射层的暴露部分并同时抑制侧蚀。
2.权利要求1所述的方法,其特征在于,所述氢化松香树脂源自松香酸或海松酸。
3.权利要求1所述的方法,其特征在于,所述氢化松香树脂的含量至少为10重量%。
4.权利要求1所述的方法,其特征在于,所述脂肪酸含量至少为60重量%。
5.权利要求1所述的方法,其特征在于,所述无机酸选自氟化氢、硫酸或盐酸。
6.权利要求1所述的方法,其特征在于,所述刻蚀组合物进一步包括一种或多种铵化合物。
7.权利要求1所述的方法,其特征在于,所述一种或多种多元醇选自乙二醇、聚乙二醇、丙二醇、聚丙二醇、丁二醇、聚丁二醇、二丙二醇、三丙二醇以及丙三醇。
8.权利要求1所述的方法,其特征在于,在95℃或更低温度下选择性施加所述热熔油墨抗蚀剂。
9.权利要求1所述的方法,其特征在于,在室温至50℃的温度下施加所述刻蚀组合物。
10.权利要求1所述的方法,其特征在于,所述多元醇的含量为20体积%至80体积%。
11.一种在半导体上形成电流迹线方法,所述方法包括:
a)提供包括正面和背面的半导体,所述正面包括掺杂的发射层;
b)将热熔油墨抗蚀剂选择性地施加至所述掺杂的发射层,所述热熔油墨抗蚀剂包括一种或多种具有酸官能团的氢化松香树脂、和一种或多种脂肪酸,且所述热熔油墨抗蚀剂的酸值至少为190;以及
c)将包含一种或多种无机酸和一种或多种多元醇的刻蚀组合物施加至所述半导体以刻蚀移除所述掺杂的发射层的暴露部分并同时抑制侧蚀。
12.权利要求11所述的方法,其特征在于,所述氢化松香树脂源自松香酸或海松酸。
13.权利要求11所述的方法,其特征在于,所述无机酸选自氟化氢、硫酸或盐酸。
14.权利要求11所述的方法,其特征在于,所述刻蚀组合物进一步包含一种或多种铵化合物。
15.权利要求11所述的方法,其特征在于,所述一种或多种多元醇选自乙二醇、聚乙二醇、丙二醇、聚丙二醇、丁二醇、聚丁二醇、二丙二醇、三丙二醇以及丙三醇。
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