CN1127569A - 在液体中处理半导体片的方法和装置 - Google Patents
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Abstract
本发明提供了一种从半导体片上去除有机物质的方法。该方法包括使用吸收有臭氧的低于室温的去离子水。臭氧化的水流过半导体片,臭氧将半导体片上的有机物质氧化成不溶性气体。通过在盛有半导体片和低于室温的去离子水的处理槽中扩散臭氧,可就地制备臭氧化的水。本发明还提供了一种用液体处理半导体片(14)的处理槽(13)以及在处理槽(13)中的液体中直接扩散气体的气体扩散器(4)。
Description
本发明涉及半导体加工领域。更具体地说,本发明涉及一种改进的在加工半导体片的湿式浸蚀/冲洗步骤中从半导体片上除去有机物质的方法。本发明还涉及一种用于实施在半导体片的加工过程中用液体处理半导体片的方法和其它方法的装置。
在半导体片的加工中,几个工艺步骤都需要使半导体片与液体接触。这些工艺步骤的例子是浸蚀、除去光敏抗蚀剂和预扩散清洗。通常这些步骤使用的化学试剂往往是有毒的,它们可能是强酸、强碱或挥发性溶剂。
常规的使半导体片与处理液相接触的装置是一组处理槽或池,将装有半导体片的盒浸没在这种槽中。这种常规的湿式处理装置存在几个困难问题。
首先,半导体片在从一个槽转移入另一个槽时会造成沾染,沾染物对加工处理所产生的微电路是非常有害的。其次,所使用的有毒化学试剂和去离子水一般要用新溶液替换,而通常要通过用瓶倒入槽中或用试剂分配装置将新溶液引入处理槽中,或者在使用去离子水的情况下从一个固定设备将去离子水引入处理槽。一般来说化学试剂是由化学公司生产的,然后运送到半导体加工厂。因此,化学试剂的纯度要受化学生产厂所使用的水的水质限制,还要受到运输和贮存该化学药品的容器以及处理该化学药品的容器的影响。
此外,当试剂长时期放置时,它们会受到来自空气和半导体片的杂质的污染。在更换液体之前,半导体片的最后一批处理也许不会象在新溶液对半导体片的第一批处理那样有效。处理不均一是半导体生产中主要关注的问题。
半导体加工的液体接触步骤包括从半导体片表面除去有机物质和杂质。例如,在生产集成电路中,加工过程的一部分就是通常在硅片上烘焙一种光敏抗蚀剂涂层。在处理之后该光敏抗蚀剂或有机物质层必须除掉。
通常,用硫酸溶液采用湿式剥离法除去光敏抗蚀剂层,要么用过氧化氢作为氧化剂,要么用臭氧作为氧化剂来增强硫酸溶液的作用。在授予CFM Technologies的美国专利第4,899,767和4,917,123中提到过这种方法。然而,在半导体加工过程中,使用一种含有硫酸和氧化剂的溶液从半导体片上除去光敏抗蚀剂存在许多缺点。首先,当用过氧化氢作为氧化剂时,剥去抗蚀剂层反应的副产物是水,水会稀释浴槽中溶液的浓度,从而降低了剥去光敏抗蚀剂的能力。其次,该过程要在高温条件下进行,通常在80°~150℃之间,一般在大约130℃以上,为了盛放、循环和过滤该溶液就要求使用特殊的耐热材料和部件,为了进行清洗过程还需要额外的能量。第三,这种溶液的输送和处置都是危险的,生产、运输和贮存费用都很昂贵。
此外,由于在处理槽中溶解的和不溶解的杂质的逐渐积累,因此溶液必须定期更换。通常,化学试剂的更换间隔时间是大约每八小时一次。由于该化学药品对排水管道有有害的影响,所以在处置之前,必须将溶液冷却到低于大约90℃。因此,采用这种剥去光敏抗蚀剂的方法,要么需要使用附加的槽子来盛放热溶液,要么在更换化学试剂期间需要停止运行,这样做减少了半导体片的产量,增加了经营费用。
最后,在用硫酸溶液除去光敏抗蚀剂之后,要用热的去离子水冲洗半导体片,因为在处理过程中,由于残留的硫酸盐会在半导体片上结晶,从而产生处理疵点。
“RCA清洗”法是另一种经常使用的除去有机的和金属表面沾染物的方法,它用氢氧化铵、过氧化氢和水作为第一溶液,用盐酸、过氧化氢和水作为第二溶液。通常将RCA清洗液在独立的处理槽中混合。首先用氢氧化铵溶液清洗半导体片,然后送到漂洗槽,然后再放到含有盐酸清洗液的槽中,最后再放入最后漂洗槽。与硫酸洗相似,该方法也有使用强化学药剂的缺点。此外,在将半导体片从一个槽转移到另一个槽的过程中,由于半导体片暴露在空气中而可能受到沾染。最后,由于在高pH值的氢氧化铵溶液中铝会沉淀,因此使用过氧化物会使半导体片受到铝的沾染,这些沾染物在盐酸溶液中不可能全部除去。
为了改进用液体处理半导体片的方法和设备已经付出了各种各样的努力。这些改进现有方法的尝试通常是要么改变设备,要么变换处理药剂。
在美国专利第4,778,532、4,795,497、4,899,767和4,917,123中公开了在进行液体处理过程中解决半导体片的沾染的一条途径。这些专利描述了一种封闭式全流方法和装置,该方法使处理液依次连续地流过半导体片,而不必在处理步骤之间转移或搬运半导体片。然而,这些专利仍然使用危险的化学药品进行液体处理和清洗半导体片。此外,封闭式设备所用的装置限制了半导体片的产量,因为,所有处理过程都要在装有浓溶液的同一容器中进行。
美国专利第4,899,767提出使用单独的混合槽来制备硫酸和氧化剂的溶液,然后再将该溶液输送到处理槽中。使用单独槽的原因是由于过氧化氢在分解成氧和水时产生了压力,这样做消除了爆炸的可能性。
授予SubMicron Systems股份有限公司的美国专利第5,082,518描述了另一种改进清洗半导体片的硫酸和氧化剂法的途径。该专利的系统提供了一种气体分布系统,该系统有一个带有扩散孔的喷雾板,以便在槽中的整个浴池内分布气体。因此,与美国专利第4,899,767中使用单独混合槽的情况不同,SubMicron专利提供了一种直接在含有硫酸的处理槽中分布臭氧的装置。然而,已经发现这种扩散系统有几个不足之处。首先,该装置放出的大气泡臭氧降低了臭氧的分布效率和水对臭氧的吸收率。臭氧的吸收量对于它与硫酸的反应以便从半导体片上去除有机物质的能力是至关重要的。此外,美国专利第5,082,518描述的扩散部件被认为不能均匀地在整个槽中分布臭氧。最后,就象先前改进半导体片的清洗方法的尝试一样,该方法仍然需要用有害的化学试剂,依然存在输送和处置问题。
在Ohmi等人的J.Electrochem.Soc.第140卷,第3期,1993年3月,第804~810页中阐述了解决使用有害化学药品问题的一条途径,文章描述到使用注有臭氧的超纯水在室温条件下从硅片上清洗掉有机杂质。然而,该方法也存在一些不足之处。Ohmi等人只提出了一种除去很薄的一层有机物质,也就是金属板印刷残留的一层表面活性剂的方法。Ohmi等人描述的方法在合理的时间范围内不能去除光敏抗蚀剂。计划将该方法用于有机污染层的厚度小于50埃的情况。当有机污染层的厚度为50~250密耳时,该方法太慢不能适用。因此,在本技术领域中还仍然没有一种无需使用有害化学试剂便可从半导体片上快速有效地去除所有厚度的有机物质的方法。
如果能提出一种在半导体加工过程中去除有机物质的方法,该方法不仅克服了前面提到的问题,而且还能有效地去除有机物质,那么该方法对半导体工业就能具有很大的价值。此外,无需使用多个处理槽便可实施该方法的装置对工业也具有很高实用价值。
因此,本发明的一个目的是提供一种无需使用有害的化学试剂便可从半导体片上除去光敏抗蚀剂或其它有机物质的方法。
本发明的另一个目的是提供一种无需将槽子冷却或者不会由于更换化学药剂而产生停机状况的方法。
本发明的再一个目的是提供一种对半导体片进行液体处理的系统,该系统无需将半导体片转移到一个独立的槽便可进行多种处理。
根据下文的说明和后附的权利要求,本发明的这些目的和其它目的将会变得显而易见。
通过采用本发明的从半导体片上去除有机物质的方法能够实现上述目的,该方法包括在大约1~15℃的温度下,使半导体片与臭氧溶液和水相接触。最好使半导体片与溶液有足够的接触时间,以便从半导体片上氧化有机物质。
在本发明的另一实施方案中,提供了这样一种去除有机物质的方法,该方法包括将半导体片放在盛有去离子水的槽中,用足够的时间在去离子水中扩散臭氧以便从半导体片上氧化有机物质,将去离子水维持在大约1~15℃的温度范围内,用去离子水漂洗半导体片。在一个最佳实施方案中,被去除的有机物质是光敏抗蚀剂。
在本发明的另一实施方案中,提供了这样一种去除有机物质的方法,该方法包括将半导体片放置在盛有去离子水的槽中,在去离子水中扩散臭氧,当臭氧被去离子水吸收和形成气泡穿过去离子水时,与扩散臭氧同时地用紫外光照射臭氧,使之生成氧自由基和氧分子,它们能将有机物质氧化成不溶性气体,半去离子水维持在大约1~15℃的温度范围内,用去离子水漂洗半导体片。
通过采用一种用液体处理半导体片的槽能够进一步实现本发明的目的,该槽包括与槽相连通并向槽提供液体的部件,在处理槽内至少支承一片半导体片以使其与液体相接触的支承部件,与槽连通的向槽喷入气体的部件,以及在槽中扩散气体的部件,使液体吸收气体并与槽中放置的每一片半导体片的表面相接触。扩散部件是一个带有可渗透部件和不可渗透部件的复合元件,可渗透部件有一个顶部和底部,一个在可渗透部件的中心部分限定了一个敞开区域的部件,以及一个位于可渗透部件的顶部,在可渗透部件的外表面与限定敞开区域的部件之间,限定一沟槽的部件。不可渗透的部件在其中心部分具有一个限定敞开区域的部件,该部件与在可渗透部件中心部分限定敞开区域的部件相对应,将可渗透部件与不可渗透部件接合在一起,使沟槽在可渗透部件的顶部敞开,并用不可渗透的部件遮盖住。要这样设置复合元件,使可渗透部件的底部与槽的底部相连。
在一个最佳实施方案中,槽有一个第一侧壁和一个第二侧壁,第一侧壁在槽的顶部是垂直部分,在槽的底部是向里渐缩的部分,渐缩的部分比垂直部分长,第二侧壁在槽的顶部是一垂直部分,在槽的底部是一向里渐缩的部分,渐缩部分比垂直部分短。
通过使用本发明的气体扩散器可以进一步实现本发明的目的。
图1是本发明的用液体处理半导体片装置的侧视截面示意图。
图2是本发明处理槽的前视截面示意图。
图3是本发明气体扩散器最佳实施方案的分解的三维示意图。
本发明的方法是在半导体片的加工过程中无需使用有毒的化学物质便可从半导体片中除去有机物。尽管在室温或较高的温度下,臭氧在去离子水中的溶解度很低,但本申请人还是惊奇地发现,无需使用其它化学试剂,在低于室温的去离子水溶液中扩散臭氧便能快速而有效地从半导体片中去除有机物质,如光敏抗蚀剂。尽管出乎意料,但是本申请人还是相信,降低溶液的温度,臭氧的浓度仍能基本上将半导体片上的所有有机物质氧化为不溶性气体。
在除去光敏抗蚀剂的过程中,本发明的方法可将存在的有机物质氧化为不溶性气体,如COx和NOx。这些气体逸出溶液从系统中排出,通常进入排气罩或其它排气装置中。
为了在去离子水中得到足够高的臭氧浓度,通常使浴槽的温度保持在大约1°~15℃。低于1℃,浴槽会结冰。由于这些半导体处理槽通常由石英制成,冰会使石英破裂并且阻止硅片进出处理槽。此外,由于水从液态到固态改变了物理状态,该系统将不起作用,并且不能均匀地吸收气体。高于15℃,去离子水不能吸收足够多的臭氧,从而不能及时地除去半导体片上的有机物质。在最佳实施方案中,浴槽的温度大约为5~9℃。
可以采用任何本专业技术人员公知的方法维持适宜的温度,包括冷却浴槽本身,或者最好给浴槽连续提供新鲜的低于室温的去离子水。在最佳实施方案中,用水作为处理试剂,在进入处理区域之前,使所有水或一部分水穿过冷却器。
可将半导体片直接放入盛有冷却臭氧化水的槽中,或者最好将半导体片放入去离子水槽中,并且使臭氧扩散到槽中。最好将臭氧扩散到低于室温的水溶液中一段足够时间,以使半导体片上的所有有机物质基本上氧化。把臭氧扩散到水中所需的时间取决于要去除的有机物质的性质和数量。具体的水槽温度也影响所需的臭氧扩散时间,因为扩散到水中的臭氧的吸收量取决于水的温度,并且水溶液的氧化能力取决于吸收的臭氧量。
一般地,臭氧扩散到去离子水中的时间大约为1~15分钟。在最佳实施方案中,臭氧扩散到去离子水中的时间大约为5~10分钟。在另一个实施方案中,为了生成用于氧化半导体片上的有机物质或光敏抗蚀剂所需的氧自由基和氧分子,将臭氧扩散到水溶液中,并且用来自紫外光源的紫外光进行照射。
当有机物质被水溶液中的臭氧充分氧化之后,用新鲜的去离子水对半导体片漂洗大约1~5分钟。该漂洗步骤通常在室温下进行。在本发明的一个最佳实施方案中,为了从半导体片表面除去水溶性金属,如钠和钾,对半导体片的第二次漂洗使用大约65℃~85℃的热去离子水。这些碱和碱土金属来自光敏抗蚀剂中的杂质。
可以在任何类型的半导体片清洗槽或半导体片清洗装置中使用本发明的方法去除有机物质。然而,本发明的臭氧化水方法是通过使臭氧与每一个半导体片在溶液中相接触而将光敏抗蚀剂或其它有机物质氧化。因此,在清洗槽中臭氧必须充分分散,以使每一个半导体片都能与臭氧相接触。
与硫酸方法不同,硫酸方法剥掉了半导体片上的抗蚀剂,并把它溶解在用于氧化的化学试剂中,本发明的臭氧化水方法不会破坏半导体片上的抗蚀剂,而是仅仅通过使臭氧与半导体片相接触而氧化光敏抗蚀剂。如果臭氧未在槽中充分扩散,或者装盛半导体片的容器将半导体片屏蔽住,则抗蚀剂无法除去。因此,最好使槽中的水充分吸收臭氧,并在处理区域与每一半导体片的表面均匀接触。采用这种方法,可直接将有机光敏抗蚀剂氧化成不溶性气体,避免了在清洗槽内积累颗粒物质以及需要过滤装置的问题。
在一个最佳实施方案中,图1所示的装置中是实施本发明方法的装置。在一个具有通风罩和湿法排气条件并且安装了适宜的臭氧监测装置和催化破坏装置的场所进行处理。将带有抗蚀剂的半导体片或者要从其上除去有机物质的半导体片放入处理槽13中,处理槽13中装有低于室温的去离子水(1~15℃)。处理过程按低流量(大约0.5gpm)级联方式进行,在处理过程中,进水管7穿过冷却器8,便连续提供冷却后的去离子水。来自臭氧发生器6的臭氧通过导管5再通过一个原地扩散器4扩散到槽中。在关掉臭氧并连续用高流量(大约10~15gpm)的去离子水漂洗半导体片之后,确定抗蚀剂的剥落时间。排水管12连接到去离子水回收装置10,并接通漂洗用的新去离子水。在用去离子水漂洗一段时间之后,可任选热的去离子水漂洗半导体片。
在本发明的另一个最佳实施方案中,在图2所示的槽中实施本发明的方法,该槽中装有图3所示的气体扩散器。然而,尽管图1所示的装置、图2所示的处理槽和图3所示的气体扩散器特别适用于本发明的臭氧水处理方法,但是这些装置还可用于半导体片的任何处理中。特别是,先前公知的从半导体片上除去有机物质的方法也可以使用本发明的处理装置和处理槽。本申请人还发现,在本发明的装置上实施先前的公知方法无需使用多个处理槽。此外,本发明的装置还具有就地生成化学制剂的能力,从而避免了化学制剂的老化或从远处运输有毒化学药品的问题。
用液体处理半导体片的优选装置是设置在具备通风罩和湿法排气条件的场所中的处理槽。该处理槽通常要带有与该槽连通的、向槽中提供液体的部件,在槽中支承至少一个半导体片与液体相接触的部件,与槽连通的向槽喷入气体的部件,以及将气体扩散到槽中的部件,这样气体可被吸收到液体中并在处理槽中与放置的每一半导体片表面相接触。
图1表示的是本发明的一个最佳实施方案。槽13盛的是处理半导体片用的液体。
通常为处理槽13提供液体的部件是一个与槽连通的导管,但是可以采用任何本专业技术人员公知的向槽内提供流动液体的设备或者装置。例如,可以用全氟烷氧基乙烯醚(PFA)管或管道、聚四氟乙烯(PTFE)管或管子、聚偏氟乙烯(PVDF)管或管子、或者石英管向处理槽输送液体。优选用PFA管或管道。在一个最佳实施方案中,借助于一个喇叭口状的连接部件将PFA管连接到槽上。
在图1所示的最佳实施方案中,穿过槽底部的进液管7是提供液体的部件,液体向上流动流入槽13中。通常,槽要以连续溢流方式运行,来自液体提供部件的液体向上流动并到达槽的顶部,液体溢流流出处理槽后流入溢流堰1中,新的液体从槽底部再注入到槽中。这种将液体导入和排出处理槽的方法在半导体加工领域是众所周知的。
溢流堰1中的流体流入回流管12中。一个三向阀门11要么通过管线9回流液体,要么通过排放管10排放液体。
向槽喷入气体的部件可以是任何本专业普通技术人员公知的向半导体片处理槽提供气体的部件。例如,借助于PFA管或PTFE管或管子将气体通到扩散器中。最好采用带有一喇叭口的PFA管将气体喷入槽中。
图1显示的向槽喷入气体的部件是部件5,它在槽底部与槽相连,并位于扩散气体的部件之下。导管5直接向扩散器4提供气体,以便向槽提供均匀流动的气体。
在槽内支承至少一片半导体片与液体相接触(如图2所示)的部件可以是任何本专业技术人员公知的部件,它用来放置与处理液相接触的半导体片。众所周知用于这种用途的部件有半导体片盘和盒。
最好,当在槽中实施本发明的方法时,盘和盒能够使液体均匀流过槽中的每一半导体片。在一个最佳实施方案中,为了使液体有最大的自由度流经半导体片,在槽中使用了一个无盒系统支撑半导体片。最佳支承系统是四杆端部操纵装置15(见图2),它只在两点接触支承半导体片。图2显示的是固定在端板上支承部件的四轨道的端视图。接触点是在5点和7点的位置上,片槽的深度不大于大约2mm。在一个最佳实施方案中,片支承系统牢固地支承着硅片,它们以一个微小的角度在各半导体片之间保持均匀的间隙。
扩散气体的部件可以是任何能向处理槽提供臭氧或其它气体的微小气泡,并在整个槽内均匀分布气体的部件,这样就可确保每一片半导体片都能与吸收在液体中的气体相接触。最好,扩散器所提供的气泡的初始直径大约为25~40微米。
扩散气体的部件可以用于向液体处理槽中输送任何气体,如氯化氢气体、氨气、氟化氢气体、氯气或溴。要么通过扩散部件单独输送这些气体,要么混合起来输送这些气体,或者没有臭氧来与处理槽中不同的化合物起作用。
最好,扩散气体的部件含有一个既有可渗透部件又有外渗透部件的复合元件。可渗透部件有一顶部和底部,一个在可渗透部件的中心部分限定了一个敞开区域的部件,以及一个在可渗透部件的外表面与限定敞开区域的部件之间限定一沟槽的部件,该沟槽位于可渗透部件的顶部。不可渗透部件有一个在其中心部分限定一敞开区域的部件,该部件对应于在可渗透部件的中心部分限定敞开区域的部件。可渗透部件和不可渗透部件要这样连接,使可渗透部件顶部的沟槽正好位于可渗透部件和不可渗透部件之间。最好这样放置复合元件,使可渗透部件的底部与处理槽的底部相连。这样,复合元件的可渗透部件朝向处理槽底部,而复合元件的不可渗透部件则朝向处理槽顶部。沟槽的开口部分位于两部件之间复合元件的内侧。
本发明的气体扩散器4使气体进入扩散器,再穿过可渗透部件的小孔扩散到溶液中。气体首先流入可渗透部件的沟槽中,因为该区域的气体流动阻力最小。当提高气体压力时,流入沟槽的气体穿过可渗透部件的小孔扩散到槽中。因为可渗透部件顶部的不可渗透部件会阻止气体流出扩散器的顶部,气体从扩散器的底部和侧面流出,并向下流动。当提供液体的部件位于槽底部时,向下流动的气体与液体逆向流动,使向上流动进入槽中的液体能更好地吸收气体。
最好扩散器是疏水的,以防止水倒流进入气体管道,水会使气体调节盒中的金属腐蚀。此外,扩散器应与臭氧是化学相容的并且是化学纯的,以防止阳离子、阴离子或颗粒进入处理槽中。
最好气体扩散管由聚四氟乙烯(PTFE)和全氟烷氧基乙烯醚(PFA)的混合物制成。在制备混合物时用本专业技术人员公知的方法改变温度和压力,可制成多孔的和无孔的部件。不可渗透部件和可渗透部件最好由大约95%的PTFE和大约5%的PFA组成。可以用任何方法将可渗透部件与不可渗透部件接合在一起,只要得到的复合元件在槽中剪切力的作用下不会分开就行。最好,将复合元件热封在一起,用碳—碳键基本上将复合元件熔融或融合在一起。
一旦制成了可渗透部件,就在元件顶部的PTFE上镗出一个沟槽。得到的扩散器大约有100,000个小孔,孔的直径大约为25~40微米,气体可以穿过这些小孔扩散到处理池中。在扩散器中开一个沟槽使气体以非常细小的气泡扩散到槽中,这些细小的气泡易被液体吸收,并能均匀分布在整个槽中。
图3显示的是本发明扩散器的最佳实施方案。不可渗透部件30位于复合元件的顶部。可渗透部件31位于复合元件的底部,它有一个镗出的沟槽32,使气体在整个槽中能够均匀地分布。扩散器的形状最好是如图3所示的矩形。然而,对方形或矩形槽来说还可以使用不同形状的扩散器,如平行棒,或者对圆形或锥形槽来说使用圆形扩散器。在一个最佳实施方案中,扩散器占槽底面积的大约四分之一。
扩散器要设置在槽的底部,可以用任何合适的方式将其固定在槽上。最好,用未使用过的端塞将扩散器固定到槽上。首先将塞子插入扩散器,然后将整个部件安装到槽中。导管5从槽的底部直接向扩散器供给气体。这样气体进入沟槽后再从可渗透部件的底部和侧壁均匀扩散出来。
图2展示了处理槽的最佳实施方案(标号与图1相对应),最佳支承部件15将半导体片14固定在槽13中。槽13至少有两个向里渐缩的侧壁,以便减少处理半导体片所需的化学药剂的量。其中的一个侧壁在槽顶部有一垂直部分,在槽的底部是一向里渐缩的部分,且渐缩部分比垂直部分长,槽的第二侧壁也有一个位于槽顶部的垂直部分和位于槽底部的向里渐缩部分,但渐缩部分比垂直部分短。槽的这种结构可将处理过程所需的化学试剂量减小大约27%,并能迅速更换槽中溶液的化学成份。
当使用大功率声波发射器时,槽13的这种结构还有优点。可在槽13上安装一个或多个大功率声波发射器2,以搅拌溶液。最好使声波发射器排列在垂直壁和与垂直气体流向偏离30°角的侧壁之间,半导体片的排列方向与大功率声波波束相平行。
在一个最佳实施方案中,将声波发射器安装在较长的一个锥面上。与该锥面相对的是较短的渐缩面。渐缩的侧壁具有两个功能。第一个功能是保证大功率声波能量不会被远槽壁反射回到声波发射器中,这种反射能量会烧坏声波发射器,缩短换能器的使用寿命。选用渐缩壁的第二个原因是使大功率声波能量穿过硅片处理区,并使大功率声波从远壁反射回来,第二次穿过硅片处理区。这样做,每一个大功率声波脉冲都能两次穿过半导体区,增加了微粒的去除效率。
槽13还安装有一个紫外光源3,用紫外光照射溶液。可以将紫外光源安装在槽的外侧,或者最好在如图1和图2中所示的位置3处,把它浸没在槽中,放置在扩散器4的上面。在本发明的臭氧化水方法运行过程中,为了去除半导体片14上的有机物质,利用紫外光可使直接鼓入处理槽的臭氧产生氧自由基和氧分子。
在另一个实施方案中,槽安装了一个盖住槽的盖子,在盖子上安装了一个红外光源。红外光用来在处理之后帮助干燥半导体片。红外光源设置在罩子上,使光源位于槽中液体之上,当盖子盖下时光向下照射到液体中。在本发明的一个最佳实施方案中,红外光与一种溶剂干燥工艺结合使用,其中将一种合适的烃溶剂引入槽中液体的顶部,使半导体片缓慢地穿过溶剂层升起,以便使溶剂层置换掉半导体片上的水。采用红外灯将半导体片加热到大约150℃±30℃,从而蒸发掉半导体片上残留的任何溶剂,并通入臭氧气体氧化有机残留物。干燥半导体片的其它方法在本技术领域是公知的,本发明可以使用任何这类方法。
虽然本文阐述的用液体处理半导体片的装置、槽和扩散器最适用于本发明的臭氧化水处理方法,但这种结构也适用于其它处理方法。该装置通过就地设置一个生成化学药剂的部件,无需使用多个处理槽,不用移动半导体片就可以在一个处理槽中进行几个处理步骤。因此,用扩散器向处理槽通入任何液体处理所需要的气体,或者通入为生成处理半导体片液体所需要的气体。本专业普通技术人员熟知当使用各种不同的气体时处理槽必需的材料。
例如,上文所述的硫酸清洗过程和RCA清洗过程都可以快速而有效地在本装置中进行,无需多个处理槽或单独的混合槽。
对硫酸方法而言,酸穿过溢流堰中的输送管进入槽中,在进入槽中处理区域之前,首先进入过滤装置。穿过槽的底部从再循环单元输送酸。当带有光敏抗蚀剂的半导体片被放到槽的处理区域之后,将臭氧扩散到槽中并启动大功率声波发射器。采用臭氧的另一种硫酸清洗方法是随着带抗蚀剂的半导体片的放入,穿过扩散管向处理槽扩散臭氧(O3),随后打开红外光源。红外光能够产生氧自由基,它直接与硅片上的有机物质反应,并作为氧化剂与硫酸反应生成常规与光敏抗蚀剂相反应的过一硫酸。该反应与双频率声波发射的声能同步。
对RCA清洗方法而言,处理槽以溢流方式运行。去离子水以变化的流速(0.5、1.5和10gpm)按级联方式连续流动,或者处理槽以静止方式运行。首先漂洗半导体片,然后关掉水级联装置。在槽中产生了臭氧化水,和/或将臭氧化水泵入处理槽,然后将氨气(NH3)扩散到槽中以生成SC1溶液。任选地,臭氧可以与紫外线照射一起使用,以产生氧自由基。启动大功率声波发射器,以双频率方式运行,交替起动声波发射器,以防止晶体过热。处理之后,打开水级联装置将SC1溶液从槽中冲洗走(从槽的底部)。用水冲洗/漂洗一段时间。排水管上还有一个在线电阻率监测器。当漂洗槽和半导体片时,打开热的去离子水水管,以升高处理槽的温度。当槽的温度达到70℃时,关掉溢流管,处理槽回到静止状态。然后将臭氧气体扩散到处理槽中,紧接着通入氯化氢气体,生成了SC2溶液。任选地,臭氧与紫外线照射一起使用,以产生氧自由基。启动大功率声波发射器,处理后打开级联的水流,根据时间和电阻率冲洗处理槽并漂洗半导体片。再用热的去离子水最终漂洗一段时间。
在不背离本发明范围和精神的情况下,本发明的各种改进和变形对本专业技术人员来说是显而易见的,应当知道本发明并不局限于本文所阐述的这些实施方案。
Claims (24)
1.一种从半导体片上除去有机物质的方法,该方法包括在大约1℃~15℃的温度下使半导体片与臭氧的水溶液相接触。
2.如权利要求1所述的方法,其特征在于上述有机物质是光敏抗蚀剂。
3.如权利要求1所述的方法,其特征在于上述温度大约为5℃~9℃。
4.一种从半导体片上除去有机物质的方法,该方法包括:
将半导体片放置在盛有去离子水的槽中;
用足够的时间向去离子水中扩散臭氧,以将半导体片上的有机物质氧化成不溶性气体;
将去离子水的温度维持在大约1℃~15℃的范围内;以及
用去离子水漂洗半导体片。
5.如权利要求4所述的方法,进一步还包括从槽中排出不溶性气体。
6.如权利要求4所述的方法,其特征在于通过处理槽中每一半导体片的表面均匀扩散臭氧气体。
7.如权利要求4所述的方法,进一步还包括在用去离子水漂洗之后,再用温度大约为65℃~85℃的热去离子水漂洗半导体片。
8.如权利要求4所述的方法,其特征在于用大约1~15分钟使臭氧扩散到去离子水中。
9.如权利要求8所述的方法,其特征在于漂洗半导体片大约1~5分钟。
10.如权利要求4所述的方法,其特征在于上述有机物质是光敏抗蚀剂。
11.如权利要求4所述的方法,其特征在于去离子水的温度大约为5℃~9℃。
12.一种从半导体片上除去有机物质的方法,该方法包括:
将半导体片放置在盛有去离子水的槽中;
在去离子水中扩散臭氧;当臭氧被去离子水吸收和形成的气泡穿过去离子水时,与扩散臭氧同时地用紫外光照射臭氧,使之生成能将有机物质氧化成不溶性气体的氧自由基和氯分子;
将去离子水的温度维持在大约1~15℃的温度范围内;以及
用去离子水漂洗半导体片。
13.如权利要求12所述的方法,其特征在于上述有机物质是光敏抗蚀剂。
14.如权利要求12所述的方法,其特征在于从槽中排出不溶性气体。
15.一种用于液体处理半导体片的处理槽,该槽带有多个侧壁和一个底部,该槽还包括:
与槽相连通的向槽提供液体的部件;
在处理槽内支承至少一片半导体片与液体相接触的支承部件;
与槽有连通的用于向槽内通入气体的部件;以及
在槽中用于扩散气体的部件,使液体吸收气体并与槽中放置的每一片半导体片的表面相接触,
上述扩散气体的部件有一个带有可渗透部件和不可渗透部件的复合元件,上述可渗透部件有一个顶部和底部,一个在其中心部份限定了一个敞开区域的部件,以及一个位于可渗透部件的顶部,在可渗透部件的外表面与限定敞开区域的部件之间限定一沟槽的部件,上述不可渗透部件有一个在其中心部分限定一敞开区域的部件,该部件与在可渗透部件中心部分限定一敞开区域的部件相对应,将可渗透部件与不可渗透部件接合在一起,使沟槽在可渗透部件的顶部敞开,并用不可渗透部件遮盖住,复合元件的设置应使得可渗透部件的底部与槽的底部相连。
16.如权利要求15所述的处理槽,其特征在于可渗透部件和不可渗透部件含有聚四氟乙烯和全氟烷氧基乙烯醚的混合物。
17.如权利要求15所述的处理槽,其特征在于该处理槽有一个第一侧壁和一个第二侧壁,第一侧壁在槽的顶部是垂直部分,在槽的底部是向里渐缩的部分,该渐缩的部分比垂直部分长,第二侧壁在槽的顶部是一垂直部分,在槽的底部是一向里渐缩的部分,该渐缩部分比垂直部分短。
18.如权利要求17所述的处理槽,其特征在于进一步在槽第一侧壁的向里渐缩部分上有一个大功率声波发射器。
19.如权利要求18所述的处理槽,其特征在于进一步在槽内侧在扩散气体的部件之上还有一紫外光源。
20.如权利要求19所述的处理槽,其特征在于通入气体的部件设置在扩散气体的部件的下面,以使气体向上喷入扩散气体的部件。
21.如权利要求20所述的处理槽,其持征在于向槽提供液体的部件使液体沿第一方向流动,向槽中喷入气体的部件沿第二方向喷入气体,气体与液体逆流流动。
22.如权利要求15所述的处理槽,其特征在于向槽中喷入气体的部件要么单独喷入一种气体,要么与一种或多种不同的气体一起喷入。
23.一种在半导体片的液体处理槽中使用的气体扩散器,包括:
一个带有可渗透部件和不可渗透部件的复合元件,
上述可渗透部件具有一个顶部和底部,一个在其中心部分限定一个敞开区域的部件,以及一个位于可渗透部件的顶部,在可渗透部件的外表面与限定敞开区域的部件之间限定一沟槽的部件,
上述不可渗透部件具有一在其中心部分限定敞开区域的部件,该部件与在可渗透部件中心部件限定敞开区域的部件相对应,将可渗透部件与不可渗透部件接合在一起,使沟槽在可渗透部件的顶部敞开,并用不可渗透部件遮盖住,复合元件的设置应使得可渗透部件的底部与槽的底部相连。
24.如权利要求23所述的气体扩散器,其特征在于可渗透部件和不可渗透部件两者都含有聚四氟乙烯和全氟烷氧基乙烯醚的混合物。
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- 1994-07-15 KR KR1019960700195A patent/KR100365529B1/ko not_active IP Right Cessation
- 1994-07-15 EP EP94923476A patent/EP0708981B1/en not_active Expired - Lifetime
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-
1995
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1996
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Cited By (5)
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CN101850344A (zh) * | 2010-05-28 | 2010-10-06 | 上海集成电路研发中心有限公司 | 半导体器件清洗装置及清洗方法 |
CN110168705A (zh) * | 2017-02-07 | 2019-08-23 | 栗田工业株式会社 | 半导体基板的清洗装置及半导体基板的清洗方法 |
CN110168705B (zh) * | 2017-02-07 | 2023-11-28 | 栗田工业株式会社 | 半导体基板的清洗装置及半导体基板的清洗方法 |
CN110709355A (zh) * | 2017-11-20 | 2020-01-17 | 深圳市柔宇科技有限公司 | 基板清洗装置及清洗基板的方法 |
CN111105996A (zh) * | 2020-01-03 | 2020-05-05 | 长江存储科技有限责任公司 | 待清洗工件的清洗方法及清洗设备 |
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US5727578A (en) | 1998-03-17 |
JP4054374B2 (ja) | 2008-02-27 |
KR960704348A (ko) | 1996-08-31 |
WO1995002895A1 (en) | 1995-01-26 |
ATE313855T1 (de) | 2006-01-15 |
CA2167283A1 (en) | 1995-01-26 |
AU8949998A (en) | 1999-01-14 |
AU699567B2 (en) | 1998-12-10 |
TW301465U (en) | 1997-03-21 |
US5776296A (en) | 1998-07-07 |
JPH09501017A (ja) | 1997-01-28 |
JP2005136377A (ja) | 2005-05-26 |
AU707359B2 (en) | 1999-07-08 |
AU7332994A (en) | 1995-02-13 |
EP0708981A1 (en) | 1996-05-01 |
EP0708981A4 (en) | 1997-03-12 |
DE69434583T2 (de) | 2006-07-20 |
KR100365529B1 (ko) | 2003-03-06 |
DE69434583D1 (de) | 2006-01-26 |
EP0708981B1 (en) | 2005-12-21 |
CN1079580C (zh) | 2002-02-20 |
US5464480A (en) | 1995-11-07 |
AU7887598A (en) | 1998-10-01 |
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