CN101182633A - 低温原子层沉积二氧化硅 - Google Patents

低温原子层沉积二氧化硅 Download PDF

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CN101182633A
CN101182633A CNA2007101703305A CN200710170330A CN101182633A CN 101182633 A CN101182633 A CN 101182633A CN A2007101703305 A CNA2007101703305 A CN A2007101703305A CN 200710170330 A CN200710170330 A CN 200710170330A CN 101182633 A CN101182633 A CN 101182633A
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梅特伊·马哈贾尼
黄宜乔
布伦登·麦克杜格尔
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Applied Materials Inc
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Abstract

本发明主要包括二氧化硅原子层沉积方法。通过提供吡啶作为催化剂,在低温沉积时水可以用作氧化源。在将衬底暴露于水之前,可将衬底暴露于吡啶浸泡工艺。另外,水可以与吡啶通过单独的管道协流入腔室以减少在进入腔室之前的互相作用。可选地,吡啶可以与不与吡啶反应的硅前驱物协流。

Description

低温原子层沉积二氧化硅
技术领域
本发明的实施方式主要涉及用于通过原子层沉积(ALD)沉积二氧化硅的方法。
背景技术
在半导体处理、平板显示器处理或其他电子器件处理领域,气相沉积工艺在将材料沉积到衬底上占有重要的作用。随着电子器件的几何结构不断缩小以及器件的密度不断增加,部件的尺寸和孔径比变得更加严格。因此,用于形成这些器件的材料的共形沉积变得越来越重要。
虽然传统的化学气相沉积(CVD)已证实成功用于小至约0.15μm器件几何结构和孔径比,但更严格的器件几何结构需要替代的沉积技术。受到普遍关注的一种技术是ALD。在ALD工艺期间,反应气体顺序导入包含衬底的腔室中。通常,第一反应物脉冲至工艺腔室中并在衬底表面上吸收。第二反应物随后脉冲入工艺腔室并与第一反应物反应而形成所沉积的材料。清洗步骤可在每个反应气体的输送之间执行。清洗步骤可以是采用载气连续清洗或在反应气体输送之间脉冲清洗。
由ALD形成二氧化硅是现有技术公知的工艺。在通过ALD形成二氧化硅中,硅前驱物可脉冲进入腔室,接着导入氧化源。当水用作氧化源时,ALD工艺由于水的中性反应性通常需要高温和较长的暴露时间。
因此,需要一种用于在低温的ALD中使用水沉积二氧化硅的方法和装置。
发明内容
本发明主要包括一种二氧化硅ALD方法。通过提供吡啶作为催化剂,在低温沉积时,水可用作氧化源。在将衬底暴露于水之前,衬底可暴露于吡啶浸泡工艺中。另外,水可与吡啶在进入腔室之前通过单独的管道协流到腔室减少相互反应。可选地,吡啶可与不用吡啶反应的硅前驱物协流。
在一个实施方式中,本发明包括二氧化硅沉积方法,该方法包括在腔室中放置衬底,将衬底暴露于硅前驱物中,将衬底暴露于吡啶浸泡中,以及将衬底暴露于氧化源中。
在另一实施方式中,本发明包括二氧化硅沉积方法,该方法包括在腔室中放置衬底,将衬底暴露于硅前驱物中,以及将衬底暴露于氧化源和吡啶中,通过独立的管道吡啶和氧化源流入腔室。
在再一实施方式中,本发明包括二氧化硅沉积方法,该方法包括将衬底放置在腔室中,将衬底暴露于六氯乙硅烷,以及将衬底暴露于H2O和吡啶,吡啶和H2O通过独立的管道流入腔室。
附图说明
因此为了详细了解本发明的以上所述特征,参照实施方式将对以上简要概述的本发明进行更具体描述,部分实施方式在附图中示出。然而,应当注意,附图仅示出本发明典型的实施例,因为本发明可允许其他等同的有效实施例,因此不能认为是本发明范围的限定。
图1A是根据本发明的一个实施方式的装置100的示意表示图;
图1B是根据本发明的一个实施方式的注射送气室108a-c的示意表示图;
图2是根据本发明的一个实施方式的沉积方法的流程图200;
图3是根据本发明的另一实施方式的沉积方法的流程图300;
图4是根据本发明的又一实施方式的沉积方法的流程图400;
图5是根据本发明的再一实施方式的沉积方法的流程图500。
为了便于理解,尽可能使用相同的附图标记表示附图共同的相同元件。可以预期一个实施方式公开的元件可以有利地在其他实施方式中使用而不具体叙述。
具体实施方式
本发明主要包括二氧化硅ALD方法。通过提供吡啶作为催化剂,在低温沉积时水可用作氧化源。在将衬底暴露于水之前,衬底可暴露于吡啶浸泡工艺。另外,水与吡啶在进入腔室之前可通过独立的管道协流到腔室,以减少相互作用。可选地,吡啶可与不与吡啶反应的硅前驱物协流。
图1A是根据本发明的一个实施方式的装置100的示意表示图。装置100包括真空腔室102。装置100可以是包含一个或多个基座106的批处理装置100,其中衬底104可以放置在基座上。在一个实施方式中,装置100可以是单一衬底104装置。为了增加产量同时处理多个衬底104是有益的。批处理处理存在的一个困难在于维持晶圆到晶圆的均匀性。
前驱物可以通过注射送气室108送入装置100。注射送气室108可包括气室壁110和注入板114,它们一起围绕并限定注射送气腔122。注入板114具有多个孔116,其中前驱气体、清洗气体以及载气经过该多个孔可流入120真空腔室102。注入板114使注射送气室108和真空腔室102分隔以便真空腔室102是注射送气室108的低压侧部112。前驱物、清洗气体和载气可通道管道118a-118c导入注射送气室108。
装置100可通过排气室124排气。排气室可包括排气板126和气室壁130,它们包围并限定排气腔128。多个孔132可存在于排气板126中。气体通过排气口136从排气腔室124排出。
附加气体可通过管道134导入排气室124。附加气体可去除或转化反应副产物,否则其可能在排气室124和真空腔室102的表面上聚集。节流阀138可控制真空腔室102压力。
当通过ALD形成二氧化硅时,硅前驱物可输送到装置100。用于沉积含硅材料的示例性硅前驱物包括硅烷、烷基硅烷、氨基硅烷、烷基氨基硅烷、硅烷醇或烷氧基硅烷。例如,硅前驱物可包括(Me2N)4Si、(Me2N)3SiH、(Me2N)2SiH2、(Me2N)SiH3、(Et2N)4Si、(Et2N)3SiH、(MeEtN)4Si、(MeEtN)3SiH、Si(NCO)4、MeSi(NCO)3、SiH4、Si2H6、SiCl4、Si2Cl6、MeSiCl3、HSiCl3、Me2SiCl2、H2SiCl2、MeSi(OH)3、Me2Si(OH)2、(MeO)4Si、(EtO)4Si或其衍生物。用作硅前驱物的其他烷基氨基硅烷化合物包括(RR’N)4-nSiHn,其中R或R’是独立的氢、甲基、乙基、丙基或丁基以及n=0~3。其他烷氧基硅烷可以用通用化学式(RO)4-nSiLn描述,其中R=甲基、乙基、丙基或丁基以及L=H、OH、F、Cl、Br或I及其混合物。另外,本发明的实施方式中更高的硅烷可用作硅前驱物。在共同转让的美国专利公开No.US2004/0224089A1中公开了更高的硅烷,在此引入其全部内容作为参考。在一些实施方式中,硅前驱物可包括三(二甲基氨基)硅烷((Me2N3)SiH或三-DMAS),四(二甲基氨基)硅烷((Me2N)4Si或TDMAS)或其他二烷基氨基硅烷,而在其他实施方式中硅前驱物可包括硅烷(SiH4)。在再一实施方式中,硅前驱物可包括六氯乙硅烷(HCDS)。
ALD工艺中用于形成二氧化硅的氧化源可包括氧气(O2)、臭氧(O3)、原子氧(O)、过氧化氢(H2O2)、一氧化二氮(N2O)、一氧化氮(NO)、五氧化二氮(N2O5)、二氧化氮(NO2)、水(H2O)及其衍生物或组合物。在示例的实施方式中,氧化源包括水(H2O)。
当使用水作为氧化源时,提供催化剂以使得ALD在比没有催化剂存在的情形以更快速率和更低温度下执行。可采用的催化剂的实施例包括氨和吡啶。吡啶和水可以互相作用。因此,当水和吡啶通过同一输入管道协流入腔室时,在到达腔室之前水和吡啶可互相作用。当水和吡啶互相作用时,吡啶不再有效地充当催化剂并因此,ALD沉积速率不会增加。
为了防止水和吡啶在到达腔室之前互相作用,吡啶和水可以使用单独的输送管道到分离的注射送气室而协流入腔室。图1B是根据本发明的一个实施方式的注射送气室108a-c的示意表示图,如图1B所示,每个管道118a-118c接入单独的注射送气室。因此,可防止吡啶-水相互作用直到吡啶和水到达腔室。
诸如HCDS的硅前驱物不与吡啶互相作用。因此,硅前驱物和吡啶可以使用同一管道和注射送气室协流入腔室。在一个实施方式中,吡啶和硅前驱物使用同一管道和注射送气室流到腔室。在另一实施方式中,吡啶和水可使用单独的管道和注射送气室流到腔室。
使用单独的注射送气室和管道将吡啶和水协流到腔室的另一选择是在将水导入腔室之前将衬底暴露于吡啶浸泡。吡啶浸泡可包括将衬底暴露于吡啶,而没有诸如水的其他前驱物或氧化剂的导入。衬底可暴露于吡啶足够长的时间以使衬底由吡啶饱和。在一个实施方式中,吡啶浸泡进行大于约10秒。通过执行吡啶浸泡,充足的催化剂可存在于腔室内和衬底表面上以确保当导入水前驱物时存在催化剂。由于吡啶已经存在于腔室中,通过在到达腔室之前与水互相作用不会消耗所有吡啶。当吡啶浸泡执行时,额外的吡啶可与氧化剂和硅前驱物协流。在一个实施方式中,当硅前驱物和随后的水输送到腔室时,执行吡啶浸泡并且吡啶继续流入腔室中。在另一实施方式中,在水输送和硅前驱物输送期间,执行吡啶浸泡并停止吡啶输送。吡啶允许反应在诸如从约室温到约160摄氏度的低温下进行。在一个实施方式中,温度是约75摄氏度。
图2是根据本发明的一个实施方式的沉积方法的流程图200。首先,将一个或多个衬底放入工艺腔室(步骤210)。衬底可随后暴露于吡啶浸泡(步骤220)。可进行吡啶浸泡至少约10秒。吡啶浸泡之后,可向腔室导入HCDS脉冲,同时吡啶继续流入腔室(步骤230)。可选地,在吡啶浸泡和随后与HCDS脉冲至腔室之后可以停止吡啶流动。
接着HCDS的脉冲,腔室可通过将清洗气体导入腔室进行清洗(步骤240)。可以使用的示例性清洗气体包括诸如氩的惰性气体。在一个实施方式中,清洗气体可包括氮。可抽吸腔室以去除腔室中可能存在的清洗气体和任何残留的HCDS和吡啶。在一个实施方式中,不执行抽吸以便仅执行清洗步骤。可选地,可以去除清洗步骤从而抽吸腔室以去除HCDS和吡啶。在一个实施方式中,抽吸可以在清洗气体导入之前和之后两种情形下执行。在另一实施方式中,清洗和抽吸都可以重复。抽吸和/或清洗可以多次执行。在再一实施方式中,清洗和抽吸可以结合为一个步骤。
接着抽吸和/或清洗。衬底可暴露于第二吡啶浸泡(步骤250)。第二吡啶浸泡可以在用于以上所述的第一吡啶浸泡的相同处理条件下进行。接着该吡啶浸泡,H2O的脉冲可导入腔室,同时吡啶继续流入腔室中(步骤260)。可选地,在吡啶浸泡后可停止吡啶流动并且随后与H2O脉冲至腔室中。由于来自浸泡步骤的吡啶已存在于腔室内,因此存在足够的吡啶作为催化剂。接着衬底暴露于H2O,在如以上所述的条件下可以执行第二抽吸和/或清洗循环(步骤270)。
在腔室已经抽吸和/或清洗后,可以测量SiO2的厚度以确定SiO2的预定厚度是否已达到(步骤280)。如果预定的厚度还没达到,则可以重复沉积工序。如果预定的厚度已经达到,则工艺结束(步骤290)。
图3是根据本发明的另一实施方式的沉积方法的流程图300。首先,可将一个或多个衬底放置于工艺腔室中(步骤310)。衬底可随后暴露于吡啶浸泡(步骤320)。吡啶浸泡可执行约至少10秒。吡啶浸泡后,可导入HCDS脉冲同时没有任何吡啶输入腔室(步骤330)。可选地,在吡啶浸泡可以停止吡啶流动并随后与HCDS脉冲至腔室中或可继续输送吡啶。
HCDS脉冲之后,腔室可以进行如上所述的清洗和/或抽吸(步骤340)。接着抽吸和/或清洗,衬底可暴露于第二吡啶浸泡(步骤350)。第二吡啶浸泡可以在用于如上所述的第一吡啶浸泡的相同处理条件下执行。接着该吡啶浸泡,可以停止吡啶流动以及H2O脉冲可以导入腔室(步骤360)。将衬底暴露于H2O后,在如上所述的条件下执行第二抽吸和/或清洗循环(步骤370)。
在已经抽吸和/或清洗腔室之后,可以测量SiO2层的厚度以确定SiO2的预定厚度是否已达到(步骤380)。如果预定厚度没有达到,则可重复沉积步骤。如果预定厚度已达到,则工艺结束(步骤390)。
图4是根据本发明的又一实施方式的沉积方法的流程图400。首先,可将一个或多个衬底放置于腔室中(步骤410)。衬底可随后暴露于HCDS和吡啶的脉冲(步骤420)。接着脉冲的HCDS和吡啶,可通过如以上所述的方式向腔室导入清洗气体而清洗腔室。
抽吸和/或清洗之后,衬底可暴露于同步脉冲的H2O和吡啶(步骤440)。H2O和吡啶可经过不同管道协流并通过不同入口协流到腔室中。通过使用不同的管道和不同入口,可以使H2O和吡啶不彼此暴露直到它们到达腔室。如果吡啶和H2O通过同一管道协流,则吡啶和H2O可能在到达腔室前互相作用。当H2O和吡啶在进入腔室之前互相作用时,可能降低吡啶作为催化剂的有效性使得催化剂失效。
将衬底暴露于H2O之后,在如以上所述的条件下可以执行第二抽吸和/或清洗循环(步骤450)。在已抽吸和/或清洗腔室之后,可以测量SiO2层的厚度以确定SiO2的预定厚度是否已达到(步骤460)。如果预定厚度还没有达到,则可重复沉积步骤。如果预定厚度已经达到,则工艺结束(步骤470)。
图5是根据本发明的再一实施方式的沉积方法的流程图500。首先,可将一个或多个衬底放置于工艺腔室中(步骤510)。随后可将衬底暴露于吡啶浸泡(步骤520)。吡啶浸泡可执行至少10秒钟。吡啶浸泡之后,脉冲的HCDS可导入腔室,同时吡啶持续流入腔室中(步骤530)。可选地,在吡啶浸泡后,停止吡啶流动并随后与HCDS脉冲至腔室。接着脉冲的HCDS,可以如以上所述清洗和/或抽吸腔室(步骤540)。
抽吸和/或清洗之后,衬底可暴露于第二吡啶浸泡(步骤550)。第二吡啶浸泡可以在与用于以上所述的第一吡啶浸泡的相同处理条件下执行。接着吡啶浸泡,脉冲的H2O可导入腔室同时吡啶持续流入腔室中(步骤560)。可选地,在吡啶浸泡后,停止吡啶流动并随后与H2O脉冲至腔室中。在一个实施方式中,吡啶和H2O通过如以上所述关于图4的单独管道供应。将衬底暴露于H2O后,可以在如以上所述的条件下执行抽吸和/或清洗循环(步骤570)。
在已经抽吸和/或清洗腔室之后,可以测量SiO2层的厚度以确定SiO2的预定厚度是否已达到(步骤580)。如果预定厚度还没有达到,则可重复沉积步骤。如果预定厚度已经达到,则工艺结束(步骤590)。
应当理解当提及处理一个衬底时,可以处理多个衬底。例如,在批处理腔室中可处理约2个衬底,约25个衬底,约50个衬底,或约100个衬底。另外,吡啶浸泡可执行约1秒钟到约90分钟或约1分钟到约20分钟的时间周期。可选地,吡啶浸泡可以进行约30秒钟到约60分钟或约20分钟到约40分钟。在再一替代例中,吡啶浸泡可进行约1分钟到约40分钟。
通过提供吡啶浸泡和/或通过单独管道协流吡啶和H2O,充分的吡啶到达腔室,并因此到达衬底表面,以保证吡啶充当为催化剂。通过在H2O氧化环境中使用吡啶作为催化剂,SiO2 ALD可以在低于160摄氏度下以增加的速率执行。
虽然前述涉及本发明的实施方式,但在不偏离本发明的基本范围下可以设计本发明的其他和进一步实施方式,并且其实施方式由以下权利要求书确定。

Claims (20)

1.一种二氧化硅沉积方法,包括:
(a)在腔室中放置至少一个衬底;
(b)将所述至少一个衬底暴露于硅前驱物中;
(c)将所述至少一个衬底暴露于吡啶浸泡;以及
(d)将所述至少一个衬底暴露于氧化源。
2.根据权利要求1所述的方法,其特征在于,所述沉积方法是原子层沉积方法。
3.根据权利要求1所述的方法,其特征在于,进一步包括:
将所述至少一个衬底暴露于清洗气体。
4.根据权利要求1所述的方法,其特征在于,将所述至少一个衬底暴露于硅前驱物中包括将所述至少一个衬底暴露于硅前驱物和吡啶中。
5.根据权利要求1所述的方法,其特征在于,进一步包括在将所述至少一个衬底暴露于所述硅前驱物之前将所述衬底暴露于吡啶浸泡。
6.根据权利要求1所述的方法,其特征在于,将所述至少一个衬底暴露于氧化源中包括将所述至少一个衬底暴露于所述氧化源和吡啶中。
7.根据权利要求6所述的方法,其特征在于,所述氧化源和吡啶通过单独的入口流入所述腔室中。
8.根据权利要求1所述的方法,其特征在于,所述硅前驱物包括六氯乙硅烷。
9.根据权利要求1所述的方法,其特征在于,所述氧化源包括H2O。
10.根据权利要求1所述的方法,其特征在于,进一步包括重复步骤(b)(d)至少一次。
11.一种二氧化硅沉积方法,包括:
(a)在腔室中放置至少一个衬底;
(b)将所述至少一个衬底暴露于硅前驱物中;以及
(c)将所述至少一个衬底暴露于氧化源和吡啶中,所述吡啶和氧化源通过单独的入口流入所述腔室中。
12.根据权利要求11所述的方法,其特征在于,所述沉积方法是原子层沉积方法。
13.根据权利要求11所述的方法,其特征在于,进一步包括:
将所述至少一个衬底暴露于清洗气体中。
14.根据权利要求11所述的方法,其特征在于,将所述至少一个衬底暴露于硅前驱物包括将所述至少一个衬底暴露于硅前驱物和吡啶中。
15.根据权利要求14所述的方法,其特征在于,所述硅前驱物和吡啶通过单独的入口流入腔室中。
16.根据权利要求11所述的方法,其特征在于,所述硅前驱物包括六氯乙硅烷。
17.根据权利要求11所述的方法,其特征在于,所述氧化源包括H2O。
18.根据权利要求11所述的方法,其特征在于,进一步包括重复步骤(b)和(c)至少一次。
19.根据权利要求11所述的方法,其特征在于,进一步包括在将所述至少一个衬底暴露于所述硅前驱物之前,将所述至少一个衬底暴露于吡啶浸泡。
20.一种二氧化硅沉积方法,包括:
(a)在腔室中放置至少一个衬底;
(b)将所述至少一个衬底暴露于六氯乙硅烷中;以及
(c)将所述至少一个衬底暴露于H2O和吡啶中,所述吡啶和H2O通过单独的进口流向腔室中。
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