CN110189982A - 膜形成方法和基板处理装置 - Google Patents

膜形成方法和基板处理装置 Download PDF

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CN110189982A
CN110189982A CN201910126154.8A CN201910126154A CN110189982A CN 110189982 A CN110189982 A CN 110189982A CN 201910126154 A CN201910126154 A CN 201910126154A CN 110189982 A CN110189982 A CN 110189982A
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film
organic matter
gas
oxidation film
forming method
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林宽之
兼村瑠威
高木聪
冈田充弘
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Tokyo Electron Ltd
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Abstract

本发明涉及膜形成方法和基板处理装置。[课题]提供能形成具有良好的表面粗糙度的膜的膜形成方法。[解决方案]一实施方式的膜形成方法具备如下工序:有机物去除工序,向基底供给含氢气体和含氧气体,将有机物去除,所述有机物附着于在前述基底的表面产生的氧化膜;氧化膜去除工序,在前述有机物去除工序后,向前述基底供给含卤素气体和碱性气体,将形成于前述基底的表面的氧化膜去除;和,成膜工序,在前述氧化膜去除工序后,在前述基底的表面成膜为规定的膜。

Description

膜形成方法和基板处理装置
技术领域
本发明涉及膜形成方法和基板处理装置。
背景技术
以往,已知有如下膜形成方法:使用包含卤素元素的气体和碱性气体,将在硅膜的表面产生的氧化膜去除后,在露出的硅膜的表面上形成硅锗膜(例如参照专利文献1)。
现有技术文献
专利文献
专利文献1:国际公开第2007/049510号
发明内容
发明要解决的问题
然而,上述膜形成方法中,如果在氧化膜的表面附着了有机物,则氧化膜的去除变得不完全,在之后的成膜中,有时产生表面粗糙度的恶化等异常生长。
因此,本发明的一方案中,目的在于,提供:能形成具有良好的表面粗糙度的膜的膜形成方法。
用于解决问题的方案
为了达成上述目的,本发明的一方案的膜形成方法具备如下工序:有机物去除工序,向基底供给含氢气体和含氧气体,将有机物去除,所述有机物附着于在前述基底的表面产生的氧化膜;氧化膜去除工序,在前述有机物去除工序后,向前述基底供给含卤素气体和碱性气体,将形成于前述基底的表面的氧化膜去除;和,成膜工序,在前述氧化膜去除工序后,在前述基底的表面成膜为规定的膜。
发明的效果
根据公开的膜形成方法,可以形成具有良好的表面粗糙度的膜。
附图说明
图1为示出本发明的实施方式的立式热处理装置的一例的剖视图
图2为示出本发明的实施方式的膜形成方法的一例的流程图
图3为示出本发明的实施方式的膜形成方法的一例的工序剖视图
图4为示出基于TOF-SIMS的评价结果的图
图5为示出有机物去除工序中的温度与硅基板上的氧化膜的膜厚的关系的图
图6为示出基于AFM的评价结果的图
附图标记说明
101 硅基板
102 硅氧化膜
103 有机物
104 硅膜
具体实施方式
以下,参照附图对用于实施本发明的方式进行说明。需要说明的是,本说明书和附图中,对于实质上同一构成,标注同一符号,从而省略重复的说明。
〔基板处理装置的整体构成〕
对于能实施本发明的实施方式的膜形成方法的基板处理装置,列举间歇式的立式热处理装置为例进行说明。图1为示出本发明的实施方式的立式热处理装置的一例的剖视图。
立式热处理装置1作为整体具有沿纵深的垂直方向延伸的形状。立式热处理装置1在纵深上具有沿垂直方向延伸的处理容器10。
处理容器10例如由石英形成。处理容器10例如具有:圆筒体的内管11;和,在内管11的外侧以同心的方式载置的有顶部的外管12这双重管结构。处理容器10的下端部例如由不锈钢制的歧管20气密地保持。
歧管20例如固定于底板(未作图示)。歧管20具有注射器30和气体排气部40。
注射器30为向处理容器10内导入各种气体的气体供给部。各种气体包含处理气体和吹扫气体。处理气体包含后述的有机物去除工序、氧化膜去除工序、和成膜工序中使用的气体。有机物去除工序中使用的气体例如可以为含氢气体和含氧气体。作为含氢气体,例如可以举出氢(H2)气体、氨(NH3)气体、甲烷(CH4)气体、乙烯(C2H4)气体。作为含氧气体,例如可以举出氧(O2)气体、一氧化二氮(N2O)气体、一氧化氮(NO)气体、水蒸气(H2O)、过氧化氢(H2O2)、一氧化碳(CO)气体、二氧化碳(CO2)气体。氧化膜去除工序中使用的气体例如可以为含卤素气体和碱性气体。作为含卤素气体,例如可以举出氟化氢(HF)气体。作为碱性气体,例如可以举出氨(NH3)气体。成膜工序中使用的气体可以根据要成膜的膜的种类等由本领域技术人员适宜选择。例如成膜为硅膜的情况下,可以为含硅气体。作为含硅气体,例如可以举出作为氢化硅气体(SinH2n+2)的硅烷(SiH4)气体、二硅烷(Si2H6)、三硅烷(Si3H8)气体、四硅烷(Si4H10)气体。另外,例如可以举出作为含氯的化合物气体的单氯硅烷(SiH3Cl)、二氯硅烷(SiH2Cl2)、三氯硅烷(SiHCl3)、四氯化硅(SiCl4)、六氯二硅烷(Si2Cl6)。例如成膜为锗膜的情况下,可以为含锗气体。作为含锗气体,例如可以举出作为氢化锗气体(GenH2n+n)的锗烷(GeH4)、二锗烷(Ge2H6)。另外,例如可以举出作为含氯的化合物气体的单氯锗烷(GeH3Cl)、二氯锗烷(GeH2Cl2)、三氯锗烷(GeHCl3)、四氯化锗(GeCl4)、六氯二锗烷(Ge2Cl6)。例如,成膜为硅锗膜的情况下,可以将上述含硅气体和含锗气体适宜组合。吹扫气体例如可以为氮(N2)气体、氩(Ar)气体等非活性气体。
注射器30上连接有用于导入各种气体的配管31。配管31上,夹设有用于调整气体流量的质量流量控制器等流量调整部(未作图示)、阀(未作图示)等。注射器30可以为1根也可以为多根。需要说明的是,图1中示出注射器30为1根的情况。
气体排气部40将处理容器10内排气。气体排气部40上连接有配管41。配管41上,夹设有能减压控制处理容器10内的开度可变阀42、真空泵43等。
在歧管20的下端部形成有炉口21。炉口21上设有例如不锈钢制的圆盘状的盖体50。
盖体50以能利用升降机构51升降的方式设置,以能气密地密封炉口21的方式构成。在盖体50上设有例如石英制的保温筒60。
在保温筒60上载置有以水平状态具有规定间隔地分多级保持多张晶片W的、例如石英制的晶舟70。
晶舟70通过使用升降机构51,使盖体50上升,从而向处理容器10内输入,并收纳于处理容器10内。另外,晶舟70通过使盖体50下降,从而从处理容器10内输出。晶舟70在长度方向上具有具备多个槽(支撑槽)的槽结构,晶片W分别以水平状态在上下隔着间隔地堆叠于槽中。载置于晶舟70的多个晶片构成1批,以批单位实施各种热处理。
在处理容器10的外侧设有加热器80。加热器80例如具有圆筒形状,将处理容器10加热至规定的温度。
在立式热处理装置1中,例如设有由计算机构成的控制部100。控制部100具备由程序、存储器、CPU构成的数据处理部等。对于程序,从控制部100向立式热处理装置1的各部传送控制信号,以使后述的各处理工序进行的方式,输入命令(各步骤)。程序存储于计算机存储介质例如软盘、压缩盘、硬盘、MO(光磁盘)和存储器卡等存储介质而安装于控制部100。
〔膜形成方法〕
对本发明的实施方式的膜形成方法进行说明。本发明的实施方式的膜形成方法例如通过控制部100控制立式热处理装置1的各部的动作而实施。图2为示出本发明的实施方式的膜形成方法的一例的流程图。图3为示出本发明的实施方式的膜形成方法的一例的工序剖视图。
本发明的实施方式的膜形成方法的特征在于,依次进行有机物去除工序S1、氧化膜去除工序S2和成膜工序S3。本实施方式中,首先,将具有规定间隔且保持了多张硅基板的晶舟70输入处理容器10内,所述硅基板在表面形成了附着有有机物的氧化膜。接着,在作为同一处理室的处理容器10内,在真空气氛下,连续地进行有机物去除工序S1、氧化膜去除工序S2和成膜工序S3,从而将硅基板的表面的有机物和氧化膜去除,然后成膜为硅膜。另外,在各工序之间,可以进行置换处理容器10内的气体的吹扫工序。接着,从处理容器10内输出保持了成膜为硅膜的硅基板的晶舟70。
需要说明的是,有机物去除工序S1、氧化膜去除工序S2和成膜工序S3可以在不同的处理装置中进行。但是,优选在同一处理装置内连续地进行。在同一处理装置内连续地进行是指,例如包括:在间歇式处理装置的1个处理室内连续地进行处理;在具有多处理室且搬送室经气氛控制的装置内,边每个工序地改变处理室边连续地进行处理。通过在同一处理装置内连续地进行,从而不会受到有机物再次附着于由有机物去除工序S1而露出的氧化膜等的影响,因此,无需严格的气氛管理、时间管理。由此,无需复杂的生产线管理。气氛管理例如是指,将卷取成膜前的处理(有机物去除工序S1和氧化膜去除工序S2)后的晶片W的气氛维持为非活性气氛。时间管理例如是指,Q-time管理。Q-time是指,在一系列的基板处理中,设置于工序之间的限制时间。
有机物去除工序S1为如下工序:向基底供给含氢气体和含氧气体,将有机物去除(原位有机气体去除(IOR:In-situ Organic Removal)),所述有机物附着于在基底的表面产生的氧化膜。本实施方式中,向稳定化为规定温度的处理容器10内,从注射器30导入H2气体和O2气体,将附着于在硅基板101的表面产生的硅氧化膜102的有机物103去除(参照图3的(a)和图3的(b))。作为规定温度,例如优选200℃~350℃。通过使规定温度为200℃以上,从而H2气体和O2气体跟有机物103的反应性提高,可以缩短去除有机物103的时间。通过使规定温度为350℃以下,从而可以抑制因H2气体和O2气体导致硅基板101发生氧化。
氧化膜去除工序S2为将形成于基底的表面的氧化膜去除的工序。本实施方式中,通过化学氧化物去除处理(化学氧化去除(COR:Chemical Oxide Removal))处理,将在硅基板101的表面产生的硅氧化膜102去除(参照图3的(c))。此时,有机物去除工序S1中,附着于硅氧化膜102的表面的有机物103被去除,因此,可以抑制硅氧化膜102的去除变得不完全。COR处理是指如下处理:使含卤素气体和碱性气体吸附于氧化膜,与氧化膜进行化学反应,变质为作为反应产物的氟硅酸铵((NH4)2SiF6),通过加热,使氟硅酸铵升华而将氧化膜去除。例如向稳定化为规定温度的处理容器10内,从注射器30导入HF气体和NH3气体,使HF气体和NH3气体吸附于硅氧化膜102,与硅氧化膜102反应变质为(NH4)2SiF6。作为变质的温度,例如优选25℃(室温)~200℃。通过设为室温以上,从而无需用于冷却处理容器10内的冷却机构。通过设为200℃以下,从而可以抑制氟(F)向硅基板101中扩散。接着,通过将处理容器10内加热至规定温度(例如300℃~400℃),从而使(NH4)2SiF6升华。需要说明的是,成膜工序S3中,加热至(NH4)2SiF6升华的温度的情况下,氧化膜去除工序S2中可以不进行加热。
成膜工序S3为在基底的表面成膜为规定的膜的工序。本实施方式中,向稳定化为规定温度(例如400℃)的处理容器10内,从注射器30导入Si2H6气体,在硅基板101的表面成膜为硅膜104(参照图3的(d))。此时,硅基板101的表面通过有机物去除工序S1去除了有机物,通过氧化膜去除工序S2,氧化膜被去除,成为清洁的表面,因此,能成膜为硅基板101的表面具有良好的表面粗糙度的硅膜104。
吹扫工序为置换处理容器10内的气体的工序。本实施方式中,向处理容器10内从注射器30导入N2气体,将残留于处理容器10内的H2气体和O2气体、HF气体和NH3气体置换为N2气体。
如以上说明那样,本发明的实施方式的膜形成方法依次进行有机物去除工序S1、氧化膜去除工序S2和成膜工序S3。由此,可以在有机物和氧化膜被去除后的清洁的表面形成规定的膜,因此,可以形成具有良好的表面粗糙度的膜。
另外,本发明的实施方式的膜形成方法中,向基底供给含氢气体和含氧气体,将前述基底的表面的有机物去除。由此,即使在基底的表面形成有沟槽图案、孔图案等凹凸图案的情况下,也可以抑制图案坍塌,且去除附着于氧化膜的表面的有机物。需要说明的是,作为去除有机物的方法,也考虑了进行氨过氧化氢水(APM:Ammonium Hydrogen-peroxideMixture)清洗等湿式清洗。然而,如果进行湿式清洗,则在基底的表面形成有凹凸图案的情况下,有产生图案坍塌的担心。
〔实施例〕
对确认了本发明的实施方式的膜形成方法的作用·效果的实施例进行说明。
<实施例1>
实施例1中,使作为有机物的邻苯二甲酸二辛酯(DOP:Dioctyl phthalate)附着在硅基板的表面后,制作不进行有机物去除工序S1的试样(样品A)和进行了有机物去除工序S1的试样(样品B)。需要说明的是,有机物去除工序S1中,向稳定化为300℃的处理容器10内,从注射器30导入H2气体和O2气体30分钟。
接着,利用飞行时间二次离子质谱(TOF-SIMS:Time-of-Flight Secondary IonMass Spectrometry),对样品A和样品B的表面污染进行评价。
图4为示出基于TOF-SIMS的评价结果的图。图4中,对于样品A和样品B,分别表示源自DOP的质量数m/z=57、104、149(m:分子质量、z:电荷数)下的TOF-SIMS计数。
如图4所示那样,可知,样品B中,与样品A相比,在m/z=57、104、149下,TOF-SIMS计数均变小。换言之,可知,通过进行有机物去除工序S1,从而可以去除附着于硅基板的表面的DOP。由该结果认为,通过有机物去除工序S1,可以将附着于在基底的表面产生的氧化膜的有机物去除。
<实施例2>
实施例2中,对在稳定化为300℃、350℃、400℃、500℃、600℃、650℃、750℃的处理容器10内实施了有机物去除工序S1后的硅基板的表面的氧化膜的膜厚进行评价,从而关于对硅基板的影响进行评价。需要说明的是,有机物去除工序S1中,向处理容器10内,从注射器30导入H2气体和O2气体30分钟。
图5为示出有机物去除工序S1中的温度与硅基板上的氧化膜的膜厚的关系的图。图5中,横轴表示有机物去除工序S1中的处理容器10内的温度(℃),纵轴表示氧化膜的膜厚另外,图5中,虚线表示在实施有机物去除工序S1前形成于硅基板的氧化膜的膜厚(约)。
如图5所示那样,可知,通过使有机物去除工序S1中的温度为350℃以下,从而可以特别抑制硅基板被H2气体和O2气体氧化。另外可知,通过使有机物去除工序S1中的温度为300℃,从而可以防止硅基板被H2气体和O2气体氧化。由该结果认为,有机物去除工序S1中的温度优选350℃以下、更优选300℃。
<实施例3>
实施例3中,对于表面形成有附着了有机物的氧化膜的硅基板,依次实施有机物去除工序S1、氧化膜去除工序S2和成膜工序S3,从而在硅基板上形成硅膜(样品C)。另外,为了比较,依次实施氧化膜去除工序S2和成膜工序S3而不实施有机物去除工序S1,从而在硅基板上形成硅膜(样品D)。有机物去除工序S1、氧化膜去除工序S2和成膜工序S3的工艺条件如以下所述。
(有机物去除工序S1)
处理容器10内的温度:300℃
处理容器10内的压力:0.35Torr(46.7Pa)
气体流量:H2/O2=1000sccm/1700sccm
气体供给时间:180分钟
(氧化膜去除工序S2)
处理容器10内的温度:50℃
处理容器10内的压力:0.2Torr(26.7Pa)
气体流量:HF/NH3=40sccm/1000sccm
气体供给时间:35分钟
(成膜工序S3)
处理容器10内的温度:380℃
处理容器10内的压力:1.0Torr(133.3Pa)
气体流量:Si2H6=350sccm
接着,利用原子力显微镜(AFM:Atomic Force Microscope),对样品C和样品D的表面粗糙度进行评价。
图6为示出基于AFM的评价结果的图。图6的(a)示出样品C的硅膜的表面的AFM图像和算术平均粗糙度Ra,图6的(b)示出样品D的硅膜的表面的AFM图像和算术平均粗糙度Ra。
如图6的(a)所示那样,样品C中,硅膜的表面粗糙度小,算术平均粗糙度Ra为0.072nm。另一方面,如图6的(b)所示那样,样品D中,硅膜的表面粗糙度大,算术平均粗糙度Ra为0.112nm。即,可知,通过实施有机物去除工序S1,从而硅膜的表面粗糙度变小,算术平均粗糙度Ra成为2/3左右。换言之,可知,通过实施有机物去除工序S1,从而可以形成具有良好的表面粗糙度的硅膜。由该结果认为,通过依次实施有机物去除工序S1、氧化膜去除工序S2和成膜工序S3,从而可以形成具有良好的表面粗糙度的膜。
以上,对用于实施本发明的方式进行了说明,但上述内容不限定发明的内容,可以在本发明的范围内进行各种变形和改良。
上述实施方式中,作为基板处理装置,列举一次性对多张晶片进行处理的间歇式的立式热处理装置为例进行了说明,但本发明不限定于此。例如可以为对各1张晶片进行处理的张叶式的装置。另外,例如可以为如下半间歇式的装置:使配置于处理容器内的旋转台上的多张晶片利用旋转台公转,依次通过供给原料气体的区域、和供给与原料气体反应的反应气体的区域,在晶片的表面成膜。

Claims (7)

1.一种膜形成方法,其具备如下工序:
有机物去除工序,向基底供给含氢气体和含氧气体,将有机物去除,所述有机物附着于在所述基底的表面产生的氧化膜;
氧化膜去除工序,在所述有机物去除工序后,将形成于所述基底的表面的氧化膜去除;和,
成膜工序,在所述氧化膜去除工序后,在所述基底的表面成膜为规定的膜。
2.根据权利要求1所述的膜形成方法,其中,
所述有机物去除工序、所述氧化膜去除工序和所述成膜工序在同一装置内连续进行。
3.根据权利要求1或2所述的膜形成方法,其中,
所述有机物去除工序在200℃~350℃的温度下进行。
4.根据权利要求1至3中任一项所述的膜形成方法,其中,
所述氧化膜去除工序在25℃~200℃的温度下进行。
5.根据权利要求1至3中任一项所述的膜形成方法,其中,
所述氧化膜去除工序具备如下步骤:
使所述氧化膜、跟含卤素气体和碱性气体进行化学反应,使所述氧化膜变质为反应产物的步骤;和,
将所述反应产物加热并去除的步骤。
6.根据权利要求1至5中任一项所述的膜形成方法,其中,
在所述基底上形成有凹凸图案。
7.一种基板处理装置,其具备:
处理容器,其用于收纳基板;
气体供给部,其能向所述处理容器内供给含氢气体和含氧气体;和,
控制部,其用于控制所述气体供给部,
所述控制部以实施如下工序的方式进行控制:
有机物去除工序,向所述处理容器内供给含氢气体和所述含氧气体,将有机物去除,所述有机物附着于在所述基板上产生的氧化膜;
氧化膜去除工序,在所述有机物去除工序后,将在所述基板上产生的氧化膜去除;和,
成膜工序,在所述氧化膜去除工序后,在所述基板上成膜为规定的膜。
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