CN101802984A - 在基板上形成氧化硅层的方法 - Google Patents

在基板上形成氧化硅层的方法 Download PDF

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CN101802984A
CN101802984A CN200880107123A CN200880107123A CN101802984A CN 101802984 A CN101802984 A CN 101802984A CN 200880107123 A CN200880107123 A CN 200880107123A CN 200880107123 A CN200880107123 A CN 200880107123A CN 101802984 A CN101802984 A CN 101802984A
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silicon
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described method
annealing
oxide layer
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CN101802984B (zh
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斯里尼瓦斯·D·内曼尼
阿布海杰特·巴苏·马利克
怡利·Y·叶
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Applied Materials Inc
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Abstract

一种在基板上沉积氧化硅层的方法，包括提供基板至沉积室。第一含硅前驱物、第二含硅前驱物与氨气(NH3)等离子体反应以形成氧化硅层。第一含硅前驱物包括Si-H和Si-Si键的至少其中之一。第二含硅前驱物包括至少一Si-N键。沉积的氧化硅层经过退火处理。

Description

在基板上形成氧化硅层的方法
相关申请的交叉引用
本申请涉及共同转让的美国临时专利申请No.60/803,499、其由Lubomirsky等人提出，于2006年5月30日申请，名称为“PROCESSCHAMBER FOR DIELECTRIC GAPFILL”。本申请涉及共同转让的美国专利No.6,387,207，其由Janakiraman等人提出，于2002年5月14日申请，名称为等离子体“INTEGRATION OF REMOTE PLASMA GENERATOR WITHSEMICONDUCTOR PROCESSING CHAMBER”。本申请涉及共同转让的美国专利No.6,830,624，其由Janakiraman等人提出，于2004年12月14日申请，名称为等离子体“BLOCKER PLATE BY-PASS FOR REMOTE PLASMACLEAN”。本申请还涉及共同转让的美国专利No.5,558,717，其由Zhao等人提出，名称为“CVD PROCESSING CHAMBER”。这些相关申请案将一并引用供作参考。
发明背景
自从数十年前半导体器件问世以来，其几何形状已大幅缩小。现今半导体制造设备惯常制造特征结构(feature)尺寸为250纳米(nm)、180nm与65nm的器件，很快即发展新设备来制造更小几何尺寸的器件。然而尺寸缩小意味着器件元件必须靠得更近，以致增加电干扰的机会，包括串扰(cross-talk)和寄生电容(parasitic capacitance)。
为降低电干扰的程度，使用介电绝缘材料来填充间隙、沟槽、和器件元件、金属线与其它器件特征结构间的其它空间。介电材料的选择针对其容易在器件特征结构间的空间内形成且其介电常数(即“k值”)低。k值越低的介电质越能使串扰和RC时间延迟最小，及降低器件的整体功率消耗。传统介电材料包括氧化硅，其以传统化学气相沉积(CVD)技术沉积时，平均k值为4.0-4.2。
尽管传统CVD氧化硅的k值适用于许多器件结构，但随着尺寸不断缩减且器件元件的密度不断增加，半导体制造者仍持续寻找k值更低的介电材料。方法之一为将氟掺入氧化硅而产生掺氟氧化硅膜(即“FSG”膜)，其介电常数为约3.4-3.6。另一方法为旋涂(spin-on)玻璃技术，其将如氢基硅倍半氧烷(hydrogen silsesquioxane；HSQ)的高流动性前驱物涂到基板上而形成多孔的低k膜。
近年来，已开发出k值为3.0或更低的硅-氧-碳(Si-O-C)膜。这些低k膜通常利用化学气相沉积碳硅前驱物与氧前驱物而沉积于基板上。虽然Si-O-C膜的k值比纯氧化硅和掺氟氧化硅膜低，但也容易变得多孔，而造成其它负面影响。多孔膜易增加水分吸收，导致膜的k值增加。多孔膜还具有较大的“湿式蚀刻速率比(WERR)”，使得膜较易被侵蚀及受压破裂。因此需要新方法来沉积低k碳基(carbon-based)膜，该膜有较低的孔隙度(porosity)、较小的WERR值，且较不易破裂。本发明的实施例将着重于这些以及其它课题。
发明内容
本发明的实施例包括在基板上沉积氧化硅层的方法。方法包括提供基板至沉积室。使第一含硅前驱物、第二含硅前驱物与NH3等离子体反应以形成氧化硅层。第一含硅前驱物包括Si-H键和Si-Si键的至少其中之一。第二含硅前驱物包括至少一Si-N键。沉积的氧化硅层经过退火处理。
本发明的实施例还包括在基板上沉积氧化硅层的方法。方法包括提供基板至沉积室。在沉积室外面产生原子氧前驱物并将其引入腔室。硅前驱物被引进沉积室。硅前驱物的C∶Si原子比为约8或以下。硅前驱物和原子氧前驱物可先在腔室内混合。硅前驱物与原子氧前驱物反应，以在基板上形成氧化硅层。沉积的氧化硅层经过退火处理。
本发明的实施例更包括在基板上沉积氧化硅层的方法。方法包括提供基板至沉积室。在沉积室外面通过等离子体解离含臭氧的前驱物而产生原子氧前驱物并将其引入腔室。硅前驱物被引进沉积室。硅前驱物的C∶Si原子比为约8或以下。硅前驱物和原子氧前驱物可先在腔室内混合。硅前驱物与原子氧前驱物在约100托耳至约760托耳的处理压力下反应，以在基板上形成氧化硅层。沉积的氧化硅层经过退火处理。
其它实施例和特征将部分说明于下，且其在本领域技术人员知晓了说明书或实践本发明后将变得明显易懂。通过说明书所述的手段、组合和方法可实现并获得本发明的特征与优点。
附图简要说明
本发明的本质和优点在参阅说明书其余部分与附图后将更清楚易懂，其中，各附图中相同的组件符号表示类似的组件。在某些例子中，与组件符号相关的下标(sublabel)与连字号(hyphen)代表多个类似组件的其中一个。若文中指称组件符号，而未特定指出存在的下标，则表示其是指所有此类的类似组件。
图1为在基板上形成氧化物层的示例性方法100的流程图；
图2A-2D绘示在基板上形成氧化物层的示例性方法的横截面视图；
图3为根据另一示例性实施例的形成氧化硅层的方法的流程图；
图4A绘示示例性薄膜沉积系统的垂直剖面视图；以及
图4B为示例性薄膜沉积系统的系统监视器/控制器部件的简化示意图。
发明详细说明
在此描述用于沉积具有期望流动性的氧化硅层的系统和方法，该氧化硅层接着经退火处理(即固化)成具有期望质量的氧化物层或填充层。最初形成的氧化物所具有的期望流动性可使其填满高深宽比的间隙和沟槽(如深宽比大于5∶1)，且不会形成空隙或裂缝。退火步骤接着驱除水气而留下密实的氧化物膜，其湿式蚀刻速率比(WERR)接近氧化硅膜的实际极限(例如，WERR降为约1.8至约1.4)。
示例性方法包括在沉积室/反应室外远程产生反应性(reactive)原子氧。原子氧先在沉积室内与C∶Si原子比为约8或以下的硅前驱物混合，在此即便是在低温低压下，二者仍会反应并在基板上沉积氧化硅。形成的氧化物具有期望量的与硅键结的羟基，使得氧化物具可流动性。一旦沉积，于填充间隙或沟槽期间，即便在低温下，氧化物仍将如期望地流动而填充初生的空隙与裂缝。沉积后，退火步骤将一定量的Si-OH基团转化成二氧化硅和待驱离沉积膜的水蒸气。
形成氧化物层的示例方法
图1示出在基板上形成氧化物层的示例性方法100的流程图。方法100可以包括在步骤102中，向沉积室提供基板200。基板200可为硅基板、III-V族化合物基板、硅/锗(SiGe)基板、外延(epi-)基板、绝缘物上覆硅(SOI)基板、显示基板，例如液晶显示器(LCD)、等离子体显示器、电致发光(EL)灯显示器或发光二极管(LED)基板。在一些实施例中，基板200可包括至少一个结构，例如沟槽结构、井(well)、结、二极管、晶体管、金属氧化物半导体场效晶体管(MOSFET)、层间介电层(ILD)结构、金属间介电层(IMD)结构、电路、其它半导体结构、或其多种组合。基板200可为半导体晶圆(如200毫米(mm)、300mm、400mm等硅晶圆)。在一些实施例中，基板200可具有至少一个沟槽，例如图2A的沟槽210。在一些实施例中，基板200可为半导体晶圆(如200mm、300mm、400mm等硅晶圆)，且包括先前工艺形成的结构、器件部件等。例如，基板可包括具高的高度与宽度比的沟槽210(如高深宽比为5∶1或以上、6∶1或以上、7∶1或以上、8∶1或以上、9∶1或以上、10∶1或以上、11∶1或以上、12∶1或以上等)。
在一些实施例中，方法100包括在步骤104中，于沉积室外的位置远程产生原子氧前驱物。原子氧前驱物可通过解离含氧前驱物而产生，该含氧前驱物例如分子氧(O2)、臭氧(O3)、氮氧化合物(如NO、NO2、N2O等)、氢氧化合物(如H2O、H2O2等)、碳氧化合物(如CO、CO2等)、和其它含氧前驱物及前驱物组合。
在一些实施例中，原子氧前驱物可通过解离含臭氧的前驱物而产生。含臭氧的前驱物可为氧气与臭氧的混合气体。例如，可向臭氧产生器供应氧气。在臭氧产生器内，至少一部分的氧气经臭氧化而变成臭氧。在一些实施例中，氧气的流速为每分钟约3标准升(slm)至约20slm。臭氧化后，氧气中的臭氧占约6重量％至约20重量％。
在一些实施例中，解离含氧前驱物来产生原子氧的方法可通过热解离、紫外光解离、和/或等离子体解离等方法完成。等离子体解离可包括在远程等离子体产生室中点燃来自氦气、氩气等的等离子体、及引进氧前驱物至等离子体中以产生原子氧前驱物。
在步骤106中，将原子氧前驱物引到沉积室，在此其可与与引入腔室的硅前驱物(步骤108)第一次混合。在步骤110中，原子氧前驱物会在约-10℃至约200℃的温度和总室压约10托耳至约760托耳的压力下，与硅前驱物(和反应室内的其它沉积前驱物)反应形成氧化硅膜220(图2B)。氧化硅膜220可将沟槽210的深宽比降至沟槽2lOa的深宽比。
硅前驱物的C∶Si原子比为约8或以下(如C∶Si的比例为7、6、5、4、3、2、1或以下)。这意味着硅前驱物分子中，每一硅原子搭配8个以下的碳原子。
在一些实施例中，硅前驱物可为硅氧烷(siloxane)化合物，例如三乙氧基硅氧烷(TRIES)、四甲氧基硅氧烷(TMOS)、三甲氧基硅氧烷(TRIMOS)、六甲氧基二硅氧烷(HMODS)、八甲氧基三硅氧烷(OMOTS)、和/或八甲氧基十二硅氧烷(OMODDS)、和其它硅氧化合物等：
Figure GPA00001052903300051
Figure GPA00001052903300061
在其它实施例中，硅前驱物也可为硅氮烷(silazoxane)化合物，其包括一或多个氮基。硅氮烷包括六甲氧基二硅氮烷(HMDS-H)、甲基六甲氧基二硅氮烷(HMDS-CH3)、氯代六甲氧基二硅氮烷(HMDS-Cl)、六乙氧基二硅氮烷(HEDS-H)、九甲氧基三硅氮烷(NMTS)、八甲氧环硅氮烷(OMCS)、和其它硅氮化合物等：
Figure GPA00001052903300062
Figure GPA00001052903300071
在另些实施例中，硅前驱物可为卤化硅氧烷化合物，其包括一或多种卤素基团(如氟化物、氯化物、溴化物或碘化物基团)。例如，卤化硅氧烷可为氯化硅氧烷化合物，例如四氯硅烷(TECS)、二氯二乙氧基硅氧烷(DCDES)、氯代三乙氧基硅氧烷(CTES)、六氯代二硅氧烷(HCDS)、和/或八氯代三硅氧烷(OCTS)、和其它氯化硅氧化合物等：
Figure GPA00001052903300072
硅前驱物的O∶Si比可为约0、0.5、1、2、3、4、5、6等或以上。例如，TMOS的O∶Si原子比为约4。其它如TRIES与TRIMOS的硅前驱物的O∶Si比为约3。其它如HCDS的O∶Si比为0.5，TECS的O∶Si比为0。
硅前驱物可包括Si-O-Si键(见HMODS、OMOTS、OMODDS、HCDS、OCTS、或其它有机硅化合物)。硅前驱物的此键有利于形成具有降低的碳基和羟基污染的SiOx膜。
在一些实施例中，硅前驱物包括氨基硅烷，例如三硅烷胺(TSA)、六甲基二硅氮烷(HMDS)、杂氮硅三环(silatrane)、四(二甲氨基)硅烷、双(二乙氨基)硅烷、双-叔-丁氨基硅烷、双(二甲氨基)硅烷(BDMAS)、三(二甲氨基)氯代硅烷、甲基杂氮硅三环、和其它化合物等：
Figure GPA00001052903300081
在其它实施例中，硅前驱物包括二硅烷，包括烷氧基二硅烷、烷氧基烷基二硅烷、和烷氧基乙酰氧基二硅烷。烷氧基二硅烷可包括：
其中R1-6可各自为C1-3的烷氧基。例如，烷氧基二硅烷可包括六甲氧基二硅烷、六乙氧基二硅烷、和其它烷氧基二硅烷等。
烷氧基二硅烷可包括烷氧基与Si单元键结的环二硅烷化合物。例如，烷氧基环硅烷可包括八乙氧基环丁硅烷、十丁氧基环戊硅烷、和十二甲氧基环己硅烷等。烷氧基二硅烷的部分例子如下所示：
烷氧基烷基二硅烷可包括：
Figure GPA00001052903300092
其中R7-12可各自为C1-3的烷基或C1-3的烷氧基，且R7-12的至少其一为烷基，R7-12的至少其一为烷氧基。烷氧基烷基二硅烷还可包括环二硅烷，该环二硅烷具有与至少一个烷基和烷氧基键结的烷基与烷氧基单元，例如丁硅烷、戊硅烷、己硅烷、庚硅烷、辛硅烷等。例子包括八甲基-1，4-二氧杂-2，3，5，6-四硅环己烷、1，4-二氧杂-2，3，5，6-四硅环己烷、1，2，3，4，5，6-六甲氧基-1，2，3，4，5，6-六甲基环己硅烷、和其它烷氧基烷基环硅烷等。烷氧基烷基二硅烷的部分例子如下所示：
Figure GPA00001052903300093
烷氧基乙酰氧基二硅烷可包括：
Figure GPA00001052903300102
其中R13-17可各自为C1-3的烷基、C1-3的烷氧基或乙酰氧基，且R13-17的至少其一为烷氧基，R13-17的至少其一为乙酰氧基。
在另些实施例中，硅前驱物包括有机环硅烷，例如环丁硅烷、环戊硅烷、环己硅烷、环庚硅烷、环辛硅烷等。
在一些实施例中，硅前驱物可在引入沉积室前或期间与载气混合。载气可为实质上不会干扰在基板200上形成氧化硅层210的非活性气体(inactivegas)。载气的例子包括氦气、氖气、氩气、氢气(H2)、和其它气体等。
在方法100的实施例中，原子氧前驱物与硅前驱物在引进沉积室前先不混合。前驱物可经由设于反应室周围的单独的空间上间隔开的前驱物入口进入腔室。例如，原子氧前驱物可从腔室顶部且位于基板正上方的入口进入。入口引导氧前驱物以基本垂直于基板沉积面的方向流动。同时，硅前驱物可从沉积室侧边附近的一或多个入口进入。入口可引导硅前驱物以近乎平行沉积面的方向流动。
在一些实施例中，可透过多口喷洒头(multi-port showerhead)的单独的口输送原子氧前驱物和硅前驱物。例如，位于基板上方的喷洒头可包括供前驱物进入沉积室的开口图案。一开口副组(subset)可供原子氧前驱物使用，而第二开口副组可供硅前驱物使用。流经不同组开口的前驱物在进入沉积室前互相隔离。前驱物操作设备相关的类型与设计细节描述于共同转让的美国临时专利申请No.60/803,499、其由Lubomirsky等人提出，于2006年5月30日申请、名称为“PROCESS CHAMBER FOR DIELECTRIC GAPFILL”，其一并引用供作参考。
由于原子氧前驱物可与硅前驱物在沉积室内反应，其在基板沉积面上形成氧化硅层210(步骤110)。此初始氧化物层具有期望的流动性，并可如期望地流入沉积面的结构中的间隙、沟槽、空隙、裂缝等。如此，方法100可提供氧化物填充，其会基本上使得在间隙、沟槽、和其它具高深宽比(AR)(如AR为约5∶1、6∶1、6∶1、8∶1、9∶1、10∶1、11∶1、和12∶1、或以上)的表面结构不会产生空隙与裂缝。
再次参照图1，沉积的氧化硅层220(图2B)的沉积后退火处理112可在一步或多步中进行。一步退火方法例如可包括在基本干燥的氛围(如干燥氮气、氦气、氩气等)中加热沉积层达约300℃至约1000℃(如约600℃至约900℃)。退火处理可以移除沉积层的水气，且将Si-OH基团转化成氧化硅。经退火处理的氧化硅层具有改进的膜质量(如WERR为约6至约3、或以下)和介电性质(如k值近似或等于纯二氧化硅)。在一些实施例中，退火步骤112可在氮气环境下以约900℃进行约1小时。
在一些实施例中，多步退火方法可包括二步退火，其中膜层先进行湿式退火阶段，例如在水蒸气存在下加热膜层达约650℃。接着进行干式退火阶段，此时在基本上不含水气的氛围(如干燥N2)中加热膜层至更高温度(如约900℃)。
除了湿式和干式热退火外，其它退火技术(单独或结合使用)皆可用来退火处理氧化硅层114。其包括水蒸气退火(steam anneal)、热退火、感应耦合等离子体(ICP)退火、紫外光退火、电子束退火、酸性蒸汽催化退火、碱性蒸汽催化退火、和/或微波退火等。
图2D为示例的STI结构的横截面图。在图2D中，在经退火处理后的氧化硅层220a上形成如高密度等离子体化学气相沉积(HDP-CVD)层的介电层230。由于经退火处理的氧化硅层220a在沟槽210底部的厚度比在沟槽210侧壁的厚度厚，因此可如期望地降低沟槽210a的深宽比。故可形成介电层230并用其填入沟槽210a，且基本上又不会在介电层230中形成裂缝、间隙或空隙。在一些实施例中，若氧化硅层220可如期望地填满沟槽210(图2A)，则不必须形成介电层230。
在一些实施例中，介电层230经过热处理，例如退火工艺(未示出)。热处理可如期望地使介电层230变得密实(densify)。在一些实施例中，形成介电层230和热处理的方法是非必须的。可形成氧化硅层220(图2B)且基本上用其填充沟槽210。
形成氧化物层的另一示例方法
图3为根据另一实施例的形成氧化硅层的方法流程图。参照图3，形成氧化硅层的方法300包括步骤302、304和306。步骤302为向沉积室中提供基板(未示出)。基板类似上述参照图1所说明的基板。
在步骤304中，第一含硅前驱物、第二含硅前驱物与氨气(NH3)等离子体反应形成氧化硅层。在一些实施例中，第一含硅前驱物包括Si-H键和Si-Si键的至少其中之一。在其它实施例中，第一含硅前驱物可与NH3等离子体反应。在另些实施例中，第一含硅前驱物包括TMDSO、三甲氧硅氧(TRIMOS)、六氯代二硅氧(HCDS)、DMTMDS、SAM24、TMCTS、和BTBAS的至少其中之一。在一些实施例中，第一含硅前驱物的C∶Si原子比为约8或以下。
在一些实施例中，第二含硅前驱物包括至少一个Si-N键。第二含硅前驱物可如期望地降低氧化硅层的收缩。在一些实施例中，第二含硅前驱物可扩张氧化硅层的原子结构。例如，氧化硅层的收缩可为约32％或以下。在一些实施例中，第二含硅前驱物可将氧化硅层扩张11％或以下。
在一些实施例中，第二含硅前驱物包括TSA。在一些实施例中，TSA的至少一各Si-H键被Si-CH3键取代。例如，每个SiH3的Si-H键被Si-CH3键取代。
需注意NH3等离子体可由外部等离子体产生器产生或于沉积室内产生。第一含硅前驱物和第二含硅前驱物可先混合或分别引进沉积室，以与NH3等离子体反应。
在一些采用TMDSO与TSA的实施例中，步骤304的处理温度为约0℃或以上。在一些实施例中，处理温度介于约10℃至约25℃之间。TSA的流速为约10每分钟标准毫升(sccm)至约550sccm。在一些实施例中，TSA的流速为约400sccm至约430sccm。TMDSO的流速为每分钟约10毫克(mgm)至约1500mgm。在一些实施例中，TMDSO的流速为约1000mgm。在一些实施例中，产生NH3等离子体的前驱物的流速介于约1000sccm至约1250sccm之间。在一些实施例中，NH3的流速介于约1000sccm至约1250sccm之间。
再次参照图3，步骤306为固化该沉积的氧化硅层。在一些实施例中，步骤306类似上述参照图1说明的步骤112。
在一些形成氧化硅层的实施例中，TSA的流速为约400sccm。TMDSO的流速为约1000mgm。产生NH3等离子体的前驱物的流速为约1250sccm。处理温度为约10℃。处理压力为约1.5托耳。在一些实施例中，可省略固化步骤306。可向沉积的氧化硅层施退火工艺(未示出)用。退火工艺可为二步蒸汽退火。其一步的处理温度为约600℃，另一步的处理温度为约850℃。
示例的基板处理系统
可用于本发明实施例的沉积系统包括高密度等离子体化学气相沉积(HDP-CVD)系统、等离子体增强化学气相沉积(PECVD)系统、次大气压化学气相沉积(SACVD)系统、热化学气相沉积系统、和其它类型的系统等。可用于本发明实施例的CVD系统实例包括CENTURA ULTIMATMHDP-CVD室/系统和PRODUCERTM PECVD室/系统，其皆可购自美国加州圣克拉拉市的应用材料公司(Applied Materials，Inc.)。
可施行本发明示例性方法的基板处理系统的例子包括共同转让美国临时专利申请No.60/803,499，其由Lubomirsky等人提出，于2006年5月30日申请，名称为“PROCESS CHAMBER FOR DIELECTRIC GAPFILL”所述的系统，其一并引用供作参考。其它系统实例包括美国专利No.6,387,207与6,830,624所述的系统，其也一并引用供作参考。
参照图4A，其绘示CVD系统10的垂直剖面，CVD系统10包括具有腔室壁15a和腔室盖组件15b的真空室或处理室15。CVD系统10包含气体分配歧管11，用以分散工艺气体至放置在处理室15中间的加热基座12上的基板(未示出)。气体分配歧管11可由导电材料组成，以作为形成电容性等离子体的电极。处理时，将基板(如半导体晶圆)置于基座12的平坦(或稍许凸起)的表面12a上。基座12在较低的装载/卸载位置(如图4A所示)与较高的处理位置(以图4A的虚线14表示)之间可控制地移动，而处理位置14邻近歧管11。中央板(未示出)包括传感器，用以提供晶圆位置的信息。
沉积气体和载气透过常规平的环形气体分配面板13a的穿孔13b引进处理室15。特别是，沉积工艺气体经由入口歧管11、常规穿孔阻隔板42、和气体分配面板13a的穿孔13b流入腔室。
到达歧管11前，沉积气体与载气自气源7经由气体供应管线8输入到混合系统9，沉积气体与载气在此结合再输送到歧管11。各工艺气体的供应管线一般包括(i)数个安全关闭阀(未示出)，其可用来自动或手动停止工艺气体流入腔室、及(ii)质流控制器(亦未示出)，用以测量气体流经供应管线的流量。若工艺使用有毒气体，则按常规配置将数个安全关闭阀设在各气体供应管线。
CVD系统10执行的沉积工艺可为热工艺或等离子体增强工艺。就等离子体增强工艺而言，RF功率供应器44向气体分配面板13a与基座12之间施加功率，以激发工艺混合气体而在面板13a与基座12间的圆柱形区域(此区域将称为“反应区域”)形成等离子体。等离子体的组成进行反应以在基座12上所支撑的半导体晶圆的表面上沉积期望膜。RF功率供应器44为混频射频(RF)功率供应器，其一般以13.56MHz的RF高频(RF1)与360kHz的RF低频(RF2)供应功率来促进被引入真空室15的反应性物种的分解。就热工艺而言，不采用RF功率供应器44，且工艺混合气体将进行热反应而在支撑在基座12上的半导体晶圆的表面上沉积期望膜，基座12为电阻式加热来提供反应热能。
等离子体增强沉积工艺期间，等离子体加热整个处理室10，包括围住排气通道23与关闭阀24的腔室主体壁15a。当未开启等离子体或进行热沉积工艺时，热液体循环遍及处理室15的壁15a，以保持腔室的升温状态。壁15a中的其它通道则未示出。用来加热腔室壁15a的流体包括典型的流体类型，即基于水的乙二醇、或基于油的传热流体。此加热方式(指通过“热交换器”进行加热)可有利地降低或消除不期望存在的反应产物凝结，并有助于减少工艺气体的挥发性产物与其它污染物，倘若其凝结在冷却真空通道壁且在未通入气体时流回处理室，则可能会污染工艺。
其余未沉积成层的混合气体(包括反应副产物)由真空泵(未示出)排出处理室15。特别是，气体经由围绕反应区域的环状狭长孔16排放到环状排放气室(plenum)17。环状狭长孔16和气室17由圆柱形壁15a顶部(包括壁上的上介电内衬19)与圆形腔室盖20底部间的间隙所限定。360度环形对称且均匀配置的狭长孔16和气室17对于使工艺气体均匀流到晶圆上方以在晶圆上沉积出均匀的膜是重要的。
离开排放气室17后，气体流经排放气室17的侧向延伸部21下方、经过一观察口(未示出)，并流过向下延伸的气体通道23、经过真空关闭阀24(其主体整合于下腔室壁15a)，且流入透过前置管线(未示出)连接外部真空泵(未示出)的排放出口25。
基座12的晶圆支撑盘(优选铝、陶瓷、或其组合)利用单一循环的嵌设加热器元件来进行电阻式加热，该加热器元件以平行同心圆形式排列成两个全幅转弯(full turn)。加热器元件的外部毗邻支撑盘周围延伸，内部则沿着半径较小的同心圆延伸。加热器元件的接线穿过基座12的轴柄。
一般来说，任一或所有的腔室内衬、气体入口歧管面板、和各种反应器硬件是由诸如铝、阳极电镀(anodized)铝或陶瓷构成。此类CVD设备的例子描述于共同转让的美国专利No.5,558,717、其名称为“CVD PROCESSINGCHAMBER”、且授予Zhao等人，其一并引用供作参考。
当机械叶片(未示出)经由腔室10侧面的插入/移出开口26传送晶圆进出腔室15的主体时，升降机构与马达32(图4A)使加热基座组件12及其晶圆举升销12b升高和降低。马达32使基座12在处理位置14与较低的晶圆装载位置之间升高及降低。马达、连接供应管线8的阀或流量控制器、气体输送系统、节流阀、RF功率供应器44、和腔室与基板加热系统全受控于控制线路36上的系统控制器，图中仅示出部分。控制器34依据光学传感器的反馈信号判别可动式机构组件的位置，例如节流阀和基底(susceptor)，其由适当的马达在控制器34的控制下移动。
在此实施例中，系统控制器包括硬盘驱动(内存38)、软盘驱动和处理器37。处理器含有单板计算机(SBC)、模拟与数字输入/输出板、接口板、和步进马达控制器板。CVD系统10的各种零件皆符合规范板、卡片机架(cardcage)、和连接器尺寸与种类的Versa Modular European(VME)标准。VME标准也定义了具有16位数据总线与24位地址总线的总线结构。
系统控制器34控制CVD机器的所有动作。系统控制器执行系统控制软件，该软件为储存于计算机可读取介质(如内存38)的计算机程序。优选地，内存38为硬盘驱动，但内存38也可为其它类型的内存。计算机程序包括指定特定工艺的时序、混合气体、腔室压力、腔室温度、RF功率大小、基座位置、和其它参数的指令集。其它储存于它种内存装置(例如包括软盘或其它适合的驱动)的计算机程序也可用来操作控制器34。
在基板上沉积膜的工艺或清洁腔室15的工艺可使用控制器34所执行的计算机程序产品来进行。计算机程序码可以任一传统计算机可读取编程语言编写，例如68000汇编语言、C、C++、Pascal、Fortran、或其它语言。适当的程序代码利用传统文字编辑器输入单一文件或多个文件，并储存或收录在计算机可用介质中，如计算机的记忆系统。若输入码文本为高级语言，则对编码进行编译，产生的编译程序代码接着连结预先编译的MicrosoftWindows
Figure GPA00001052903300161
例程库的目标码。为执行连结的经编译的目标码，系统使用者启用目标码，因而使计算机系统加载内存中的编码。CPU接着读取并执行编码，以进行程序中所识别的任务。
如图4B所示，使用者与控制器34间的接口为CRT屏幕50a和光笔50b；图4B为基板处理系统的系统监视器和CVD系统10的示意图，其可包括一或多个腔室。在一优选实施例中为采用两个屏幕50a，其一放置于无尘室壁供操作员使用，另一个放置于壁后方供维修技师使用。二个屏幕50a同时显示相同的信息，但只有一个光笔50b有用。光笔50b利用笔尖的感光器监测CRT显示器发射的光线。为选择特定画面或功能，操作员触碰显示画面的指定区域，并按压光笔50b上的按钮。触碰区域改变其亮度、或显示新的选单或画面，以确定光笔与显示画面的沟通无碍。其它诸如键盘、鼠标、或其它点触或通信装置等输入装置也可附加使用或代替光笔50b，以联系使用者与控制器34。
图4A显示装设于处理室15的盖组件15b的远程等离子体产生器60，处理室15包括气体分配面板13a和气体分配歧管11。最佳如图4A所示，架设转接器64将远程等离子体产生器60装设在盖组件15b上。转接器64通常由金属构成。混合装置70耦接至气体分配歧管11的上游处(图4A)。混合装置70包括位于用于混合工艺气体的混合区块的狭缝74内的混合插入件72。陶瓷隔绝件66放置在架设转接器64与混合装置70之间(图6A)。陶瓷隔绝件66可由陶瓷材料组成，例如氧化铝(Al2O3)(纯度99％)、Teflon
Figure GPA00001052903300162
等。安装时，混合装置70和陶瓷隔绝件66可构成部分盖组件15b。隔绝件66将金属转接器64和混合装置70与气体分配歧管11隔开，以减少盖组件15b中形成二次等离子体的可能性，这将进一步详述于下。三向阀77控制工艺气体直接或经由远程等离子体产生器60流入处理室15。
远程等离子体产生器60期望地为小型、独立的(self-contained)单元，其可方便地装设在盖组件15b上，又不费时费工即可更新安装至现有腔室。适合的单元之一为ASTRON
Figure GPA00001052903300171
产生器，其可购自美国马萨诸塞州Woburn的应用科技公司(Applied Science and Technology，Inc.)。ASTRON
Figure GPA00001052903300172
产生器利用低场超环面等离子体来解离工艺气体。在一实施例中，等离子体解离工艺气体(包括如NF3的含氟气体)和如氩气的载气，以产生游离的氟来清洁处理室15内的沉积膜。
根据上述数个实施例，本领域技术人员将可理解，各种修饰、更动和等效物皆不脱离本发明的精神与范围。此外，一些公知的工艺和元件并未提及是为了避免不必要的限制本发明。因此，以上说明不应局限本发明的保护范围。
应理解除非内文特别指明，提供的数值范围到下限单位的十分之一亦明确揭露出介于此范围上限与下限的中间值。论述范围内的任一论述值或中间值与其它论述值或中间值间的较小范围也包含在内。较小范围的上限与下限可各自涵盖在此范围内或排除在外，且本发明也包含每一种包含较小范围的上限及/或下限的范围，取决于论述范围中特别排除的限制。当论述范围包括限制之一或二者时，排除这些限制的范围亦包含在内。
除非文中另有清楚指明，在此和所附权利要求中使用的单数形式(“一”与“该”)包括复数。例如，指“一工艺”包括复数个此类工艺，“该前驱物”包括一或多个前驱物和本领域技术人员已知的等效物等。
再者，本说明书和以下申请专利范围采用的“包含”与“包括”等字词意指存在所述的特征、整体、组件或步骤，但并不排除另有一或多个其它特征、整体、组件、步骤、动作或群组。

Claims (38)

1.一种在基板上沉积氧化硅层的方法，该方法包括：
提供基板至沉积室；
使第一含硅前驱物、第二含硅前驱物与NH3等离子体反应以形成氧化硅层，该第一含硅前驱物包括Si-H键和Si-Si键的至少其中之一，该第二含硅前驱物包括至少一Si-N键；以及
对沉积的该氧化硅层进行退火处理。
2.权利要求1所述的方法，其中该第一含硅前驱物选自由TMDSO、三甲氧硅氧烷(TRIMOS)、六氯代二硅氧烷(HCDS)、DMTMDS、SAM24、TMCTS、和BTBAS所组成的组。
3.权利要求1所述的方法，其中该第一含硅前驱物为TMDSO。
4.权利要求1所述的方法，其中该第一含硅前驱物的C∶Si原子比为约8或以下。
5.权利要求1所述的方法，其中该第二含硅前驱物包含三硅烷胺(TSA)。
6.权利要求5所述的方法，其中该TSA的至少一Si-H键由Si-CH3键取代。
7.权利要求1所述的方法，其中该第二含硅前驱物为TSA，且该TSA的流速介于约400sccm至约430sccm之间。
8.权利要求7所述的方法，其中该使该第一含硅前驱物、该第二含硅前驱物与该NH3等离子体反应的步骤的处理温度介于约10℃至约25℃之间。
9.权利要求7所述的方法，其中使该第一含硅前驱物反应，该第一含硅前驱物为TMDSO，且该TMDSO的流速为约1000mgm。
10.权利要求7所述的方法，其中该NH3等离子体是由流速介于约1200sccm至约1250sccm之间的前驱物产生。
11.权利要求7所述的方法，其中对沉积的该氧化硅层进行退火处理的步骤包含下列至少其中之一：进行水蒸气退火、热退火、感应耦合等离子体(ICP)退火、紫外光退火、电子束退火、酸性蒸汽催化退火、碱性蒸汽催化退火和微波退火。
12.一种在基板上沉积氧化硅层的方法，该方法包括：
提供基板至沉积室；
由包含卤素气体的混合气体来形成等离子体；
利用该等离子体来离子化含臭氧的前驱物，以形成原子氧前驱物，并将该原子氧前驱物引入该沉积室中；
向该沉积室中引入C∶Si原子比为约8或以下的硅前驱物，该硅前驱物和该原子氧前驱物首先在该沉积室内混合；
使该硅前驱物与该原子氧前驱物反应，以在该基板上形成该氧化硅层；以及
对沉积的该氧化硅层进行退火处理。
13.权利要求12所述的方法，其中该含臭氧的前驱物为臭氧与氧气的混合气体，且该臭氧占约6重量％至约20重量％。
14.权利要求13所述的方法，其中该臭氧是由该氧气产生。
15.权利要求14所述的方法，其中该氧气的流速为约3slm至约20slm。
16.权利要求12所述的方法，其中该硅前驱物与该原子氧前驱物的摩尔比为约1∶10至约100∶1。
17.权利要求12所述的方法，其中使该硅前驱物与该原子氧前驱物反应的步骤的处理压力介于约100Torr至约760Torr之间。
18.权利要求12所述的方法，其中使该硅前驱物与该原子氧前驱物反应的步骤的处理温度介于约-10℃至约200℃之间。
19.权利要求12所述的方法，其中该硅前驱物的O∶Si比为约3或以上。
20.权利要求12所述的方法，其中该硅前驱物包含硅氧烷、硅氮烷和卤代硅氧烷的至少其中之一。
21.权利要求20所述的方法，其中该硅氧烷选自由三乙氧基硅氧烷、四甲氧基硅氧烷、三甲氧基硅氧烷、六甲氧基二硅氧烷、八甲氧基三硅氧烷、八甲氧基十二硅氧烷、和八甲氧基十二硅氧烷所组成的组。
22.权利要求20所述的方法，其中该硅氮烷选自由六甲氧基二硅氮烷、甲基六甲氧基二硅氮烷、氯代六甲氧基二硅氮烷、六乙氧基二硅氮烷、八甲氧基环硅氮烷、和九甲氧基三硅氮烷所组成的组。
23.权利要求20所述的方法，其中该卤代硅氧烷选自由四氯硅烷、二氯二乙氧基硅氧烷、氯代三乙氧基硅氧烷、六氯代二硅氧烷、和八氯代三硅氧烷所组成的组。
24.权利要求12所述的方法，其中该硅前驱物包含氨基硅烷、烷基二硅烷、烷氧基二硅烷、烷氧基烷基二硅烷、烷氧基乙酰氧基二硅烷、或环硅烷。
25.权利要求24所述的方法，其中该氨基硅烷选自由三硅烷胺(TSA)、六甲基二硅氮烷(HMDS)、杂氮硅三环、四(二甲氨基)硅烷、双(二乙氨基)硅烷、双(叔丁氨基)硅烷、双(二甲氨基)硅烷(BDMAS)、三(二甲氨基)氯硅烷、和甲基杂氮硅三环所组成的组。
26.权利要求12所述的方法，其中对沉积的该氧化硅层进行退火处理的步骤包含下列至少其中之一：进行水蒸气退火、热退火、感应耦合等离子体(ICP)退火、紫外光退火、电子束退火、酸性蒸汽催化退火、碱性蒸汽催化退火、和微波退火。
27.一种在基板上沉积氧化硅层的方法，该方法包括：
提供基板至沉积室；
由包含卤素气体的混合气体来形成等离子体；
利用该等离子体来离子化一前驱物而产生原子氧前驱物，该前驱物包括臭氧与氧气的混合气体；
通过在该沉积室外等离子体解离含臭氧的前驱物而产生原子氧前驱物，并将该原子氧前驱物引入该沉积室中；
向该沉积室中引入C∶Si原子比为约8或以下的硅前驱物，该硅前驱物和该原子氧前驱物首先在该沉积室内混合；
使该硅前驱物与该原子氧前驱物在约100托耳至约760托耳的处理压力下反应，以在该基板上形成该氧化硅层；以及
对沉积的该氧化硅层进行退火处理。
28.权利要求27所述的方法，其中该臭氧占约6重量％至约20重量％。
29.权利要求28所述的方法，其中该氧气的流速为约3slm至约20slm。
30.权利要求27所述的方法，其中该硅前驱物与该原子氧前驱物的摩尔比为约1∶10至约100∶1。
31.权利要求27所述的方法，其中使该硅前驱物与该原子氧前驱物反应的步骤的处理温度介于约-10℃至约200℃之间。
32.权利要求27所述的方法，其中该硅前驱物包含硅氧烷、硅氮烷和卤代硅氧烷的至少其中之一。
33.权利要求32所述的方法，其中该硅氧烷选自由三乙氧基硅氧烷、四甲氧基硅氧烷、三甲氧基硅氧烷、六甲氧基二硅氧烷、八甲氧基三硅氧烷、八甲氧基十二硅氧烷、和八甲氧基十二硅氧烷所组成的组。
34.权利要求32所述的方法，其中该硅氮烷选自由六甲氧基二硅氮烷、甲基六甲氧基二硅氮烷、氯代六甲氧基二硅氮烷、六乙氧基二硅氮烷、八甲氧基环硅氮烷、和九甲氧基三硅氮烷所组成的组。
35.权利要求32所述的方法，其中该卤代硅氧系选自由四氯硅烷、二氯二乙氧基硅氧烷、氯代三乙氧基硅氧烷、六氯代二硅氧烷、和八氯代三硅氧烷所组成的组。
36.权利要求27所述的方法，其中该硅前驱物包含氨基硅烷、烷基二硅烷、烷氧基二硅烷、烷氧基烷基二硅烷、烷氧基乙酰氧基二硅烷、或环硅烷。
37.权利要求27所述的方法，其中该氨基硅烷选自由三硅烷胺(TSA)、六甲基二硅氮烷(HMDS)、杂氮硅三环、四(二甲氨基)硅烷、双(二乙氨基)硅烷、双(叔丁氨基)硅烷、双(二甲氨基)硅烷(BDMAS)、三(二甲氨基)氯硅烷、和甲基杂氮硅三环所组成的组。
38.权利要求27所述的方法，其中对沉积的该氧化硅层进行退火处理的步骤包含下列至少其中之一：进行水蒸气退火、热退火、感应耦合等离子体(ICP)退火、紫外光退火、电子束退火、酸性蒸汽催化退火、碱性蒸汽催化退火、和微波退火。
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US20090104791A1 (en) 2009-04-23
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WO2009055340A1 (en) 2009-04-30
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US7943531B2 (en) 2011-05-17
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