CN102099897A - 在从多液态前体沉积的多孔低k薄膜和阻障层间提升黏着性的方法 - Google Patents
在从多液态前体沉积的多孔低k薄膜和阻障层间提升黏着性的方法 Download PDFInfo
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Classifications
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
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- H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
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Abstract
在此提出处理基板的方法,其中第一有机硅前体、第二有机硅前体、成孔剂和氧源供应至处理腔室。第一有机硅前体包含整体而言碳含量较低的化合物。第二有机硅前体包含碳含量较高的化合物。成孔剂包含碳氢化合物。施加RF功率以沉积膜层至基板上,并调整各种反应物气流的流速以改变部分沉积膜的碳含量。在一实施例中,沉积膜的起始部分具低碳含量,因而类似氧化物,后继部分则具高碳含量,而类似碳氧化物。另一实施例的特征在于没有类似氧化物的起始部分。后续处理将于膜的高碳含量部分内产生细孔。
Description
技术领域
本发明的实施例大体上是关于集成电路制造。更明确而言,本发明的实施例是关于沉积用于集成电路的低介电常数膜的工艺。
背景技术
自从数十年前集成电路问世以来,此类装置的尺寸已大幅缩小。集成电路一般依循每两年尺寸减半的规则(通常称为摩尔定律(Moore’s Law)),其意指芯片上的组件数量每两年即增加一倍。目前的生产设施惯常制造特征尺寸为90纳米(nm)、甚至65nm的组件,很快地,未来设施将制造更小特征尺寸的组件。
随着组件几何尺寸不断缩小,以致需要使用更低介电常数(k)的薄膜,才能降低相邻金属线之间的电容耦合效应及进一步缩小集成电路上的组件尺寸。特别是希望绝缘体的介电常数能小于约4.0。具有低介电常数的绝缘体例子包括旋涂玻璃、掺杂氟的硅玻璃(FSG)、掺杂碳的氧化物和聚四氟乙烯(PTFE),其皆为商业上可取得。
近来已发展出介电常数小于约3.0、甚至小于约2.5的低介电常数有机硅膜。一种用来形成低介电常数有机硅膜的方法为,使用包含有机硅化合物和包含热不稳定物种(thermally labile species)或挥发性基团的化合物所构成的气体混合物来沉积薄膜,接着后续处理沉积膜以移除沉积膜中的热不稳定物种或挥发性基团(例如,有机基团)。移除沉积膜中的热不稳定物种或挥发性基团会于膜内形成纳米级空隙,这些空隙会降低膜的介电常数,空气的介电常数约为1。
尽管已开发出上述具有期望低介电常数的低介电常数有机硅膜,然而,一些低介电常数膜的机械性质仍不如预期,例如机械强度不佳,以致于在后续的半导体处理步骤期间,该些膜易遭破坏。可能破坏低介电常数膜的半导体处理步骤包括等离子式蚀刻工艺,其用来图案化低介电常数膜。用以从介电膜上移除光阻或底部抗反射涂层(BARC)的灰化工艺和湿蚀刻工艺也会破坏该些膜。
因此,仍需制造低介电常数膜的工艺,其具有改善的机械性质且能抵抗后续基板处理步骤的破坏。
发明内容
本发明的实施例提出处理基板的方法,包含将基板放到处理腔室内的支撑件上,以第一流速提供第一有机硅前体至该腔室,以第二流速提供第二有机硅前体至该腔室,以第三流速提供碳氢化合物混合物至该腔室,以第四流速提供氧化剂至该腔室,提高第二有机硅前体的流速至第五流速,提高氧化剂的流速成为第六流速,以及在基板正进行处理时的至少部分时间内,引导碳氢化合物混合物改道绕(bypass)过该腔室。在一些实施例中,亦提高第一有机硅前体和碳氢化合物混合物的流速。在一些实施例中,反应混合物中的碳原子与硅原子比率从约6∶1提高到约20∶1。
本发明的其它实施例提出处理基板的方法,包含提供数个含硅、碳、氧和氢的气体混合物至处理腔室,且该些气体混合物的其中至少二种气体混合物为硅源,通过施加射频(RF)功率于处理腔室来提供等离子处理条件,使至少一部分的该些气体混合物反应而沉积膜层于基板上,以及在施加RF功率期间,调整处理腔室中的碳原子与硅原子比率,藉以调整沉积膜的多个部分中的碳含量。
本发明的另些实施例提出在处理腔室内沉积低介电常数(k)介电膜至基板上的方法,包含提供第一气体混合物至处理腔室,该第一气体混合物包含一或多种具有-Si-Cx-Si-或-Si-O-Cx-O-Si-键结且碳原子与硅原子比率小于约6∶1的化合物;伴随第一气体混合物,提供第二气体混合物至处理腔室,第二气体混合物包含一或多种具有-Si-Cx-Si-或-Si-O-Cx-O-Si-键结且碳原子与硅原子比率大于约8∶1的化合物;提供包含一或多种碳氢化合物的第三气体混合物至处理腔室,该一或多种碳氢化合物中的至少其中一种碳氢化合物具有热不稳定基团;提供包含氧源的第四气体混合物至处理腔室;施加RF功率,并在施加RF功率时,使至少一部分的该些气体混合物反应而沉积膜于基板上;调整该些含碳的气体混合物的其中一种或多种气体混合物,藉以改变膜中的碳沉积速度;以及后续处理该沉积膜以降低该膜的介电常数。
附图说明
为了详细了解本发明上述特征,可配合实施例概要整理本发明的进一步具体说明如下,部分实施例绘示于附图中。须注意的是,所附图式仅揭露本发明的典型实施例,其并非用以限定本发明范围,本发明允许做出其它等效实施例。
图1为根据本发明一实施例的方法的工艺流程图。
图2为根据本发明另一实施例的方法的工艺流程图。
图3A-3D为在本发明的不同实施例中,各种气体混合物的流速曲线图。
图4为根据本发明一实施例所做的薄膜的碳浓度曲线图。
为助于了解,各图中相同的组件符号代表相同的组件。应理解某一实施例揭露的组件当可有利地应用于其它实施例中,在此不另外详述。
具体实施方式
本发明提出沉积低介电常数膜的方法。该低介电常数膜包含硅、氧和碳。该膜还包含纳米级细孔。该低介电常数膜的介电常数为约3.0或更小,较佳约2.5或更小,例如介于约2.0至2.2之间。该低介电常数膜的弹性模数至少为约6GPa。该低介电常数膜例如可当作金属间介电层。根据本发明一实施例的沉积低介电常数膜的方法将参照图1详述于下。
图1概述根据本发明一实施例的方法100的工艺流程图。在步骤102中,将基板放到处理腔室内的基板支撑件上。在步骤104中,提供第一气体混合物至该腔室。第一气体混合物一般包含一或多种含硅和碳的化合物。在较佳实施例中,该些化合物为通式结构以-Si-Cx-Si-表示的有机硅化合物,其中x介于1至4之间;或者该些化合物为通式结构以-Si-O-(CH2)n-O-Si-表示的有机硅化合物,其中n介于1至4之间。在步骤106中,提供第二气体混合物至该腔室,第二气体混合物包含一或多种含硅与碳的化合物。第二气体混合物中的含硅与碳的化合物也可为具有上述通式结构的有机硅化合物。在多数实施例中,第二气体混合物的碳含量最好比第一气体混合物要多。在一些实施例中,第二气体混合物所含化合物的碳原子与硅原子比率比第一气体混合物所含的化合物要高。在步骤108中,提供包含一或多种成孔剂(porogen)化合物的第三气体混合物至该腔室。该些成孔剂化合物通常为碳氢化合物(hydrocarbons),且该些碳氢化合物的至少其中一者具有一或多个热不稳定基团。热不稳定基团一般为环状基团,例如不饱和环状有机基团。在步骤110中,提供包含一或多种氧化剂的第四气体混合物至该腔室。
在步骤112中,在射频(RF)功率存在的情况下,该些气体混合物反应而沉积低介电常数膜至腔室内的基板上。第三气体混合物的成孔剂可与第一和第二气体混合物的含硅和碳的化合物反应。该些气体反应沉积出的膜中保留有热不稳定基团。如步骤116所示,后续处理该膜,以分解及释出膜中的成孔剂及/或热不稳定基团,进而于膜内形成空隙或纳米级细孔。
在步骤114中,调整该些气体混合物的流速,以调整膜的碳与氧含量。在一实施例中,第一气体混合物的流速保持不变,并提高第二气体混合物的流速。如此将增加可用于沉积膜的碳量,故产生的碳含量会随着膜成长而平稳增加。在另一实施例中,提高第三气体混合物的流速以在反应中增加碳。在又一实施例中,降低第四气体混合物的流速。由于调整该膜的多个部分的碳与氧含量可提供类氧化物(oxide-like)的组成来与氧化物膜接合而改善界面处的膜黏着性,同时膜的碳含量随着至氧化物界面的距离平稳增加。
在步骤116中,后续处理该膜,藉以实质移除低介电常数膜中的成孔剂。
图2为根据本发明另一实施例的方法200的工艺流程图。在步骤202中,将基板放到处理腔室内的基板支撑件上。在步骤204中,以第一流速提供第一气体混合物至该腔室,第一气体混合物包含一或多种具有-Si-Cx-Si-键结的化合物。在步骤206中,以第二流速提供第二气体混合物至该腔室,第二气体混合物包含一或多种具有-Si-Cx-Si-键结的化合物。第二气体混合物的组成通常与第一气体混合物不同。在一些实施例中,第二气体混合物含有的碳原子与硅原子比率高于第一气体混合物。在步骤208中,以第三流速提供包含一或多种碳氢化合物的第三气体混合物至该腔室。第三气体混合物中的至少一种碳氢化合物具有如本文它处所述的一或多个热不稳定基团。在步骤210中,以第四流速提供包含一或多种氧化剂的第四气体混合物至该腔室。
在步骤212中,改变第二气体混合物的流速至第五流速,第五流速可大于第二流速。提高第二气体混合物的流速通常增加膜中沉积的碳。第五流速可大于或小于第一流速。
在步骤214中,引导第三气体混合物改道绕过该腔室。使第三气体混合物改道可减少反应混合物的碳含量,因而降低膜中的碳沉积速度,使得在该膜中由该少碳的反应混合物沉积而得的部分中具有较低碳含量。此有助于形成该膜的类氧化物部分(oxide-like portion),来牢固地接合至氧化物介电质。形成该膜的类氧化物部分之后,使改道的第三气体混合物回到该腔室,以增加反应混合物的碳量。增加碳可加快膜中的碳沉积速度,进而使得膜的该些部分中具有较高碳含量。以此方式,可平稳地将该沉积膜的碳含量从类氧化物部分(oxide-like portion)调整成类碳氧化物部分(oxycarbide-like portion)。
在步骤216中,将第四气体混合物的流速变成第六流速,第六流速可小于第四流速。降低第四气体混合物的流速通常会减少膜中的氧沉积作用,导致碳的沉积速度相对较快,并且使得该膜中由少氧的反应混合物沉积而得的部分具有较高碳含量。
图3A~3D显示在不同实施例中,上述各种气体混合物的流速曲线图。在图3A的曲线图所描述的实施例中,第一气体混合物的流速在整个工艺中保持不变。起初,只有第一、第二和第四气体混合物流入腔室。第三气体混合物在最初时不流进腔室,而是改道绕过腔室。RF功率施加至起始的气体混合物,以于初始期间302沉积一起始膜。在第一过渡期间304,提高第二气体混合物的流速,同时持续施加RF功率。在第一过渡期间304,改变反应混合物中的元素浓度,藉以改变沉积膜的组成。第一沉积期间306所沉积的膜组成不同于初始期间302所沉积的膜组成。尽管RF功率持续施加至反应混合物,但膜组成平稳地(smoothly)变化,因此不会在膜内形成界面。避免产生界面可提高膜的黏着强度。在第二过渡期间310,到目前为止一直绕过腔室的第三气体混合物恢复流入腔室,并提高第三气体混合物的流速,以增加反应混合物和沉积膜中的碳。在此期间,降低第四气体混合物的流速,以维持反应器压力及提高反应混合物中的碳原子与硅原子比率,进而提高膜中的碳沉积速度。也可通过调整伴随各种前体流入的载气来维持反应器压力。第二过渡期间310之后,在最终沉积期间,该些前体达到其最终流速。在第三过渡期间308,改变第四气体混合物的流速;因开始和结束的速度不同,故第三过渡期间308可能比第三气体混合物的第二过渡期间310要长或短。
就图3A所示的实施例而言,以下反应条件和流速普遍有所帮助:
在不同过渡时期,第一和第二气体混合物的变化速度一般介于500mgm/秒至1000mgm/秒之间,第三和第四气体混合物的变化速度一般介于100mgm/秒至500mgm/秒之间。对改道的气流来说,最好在提高流速之前,先让气流流入腔室,以免反应器的压力发生震荡。或者,可于气流返回反应器的同时或恰恢复流入之前,开始提高该改道气流的流速。
第一沉积期间306与最终沉积期间的时间历程(time interval)将视在不同条件下沉积该膜的二部分的预定厚度而定。沉积具有较多碳且最终具有较高孔隙度的膜将会使该膜具有较小的整体介电常数。第一沉积期间306必须够长以确保整个膜的凝聚性(cohesion)。
图3B为根据另一实施例的流速曲线图。如前所述,初始期间312之后接着第一过渡期间314、第一沉积期间316、第二过渡期间320和最终沉积期间。在图3B的实施例中,在第一过渡期间314中改变第一气体混合物的流速和第二气体混合物的流速。在此实施例中,在第一过渡期间314同时改变第一和第二气体混合物的流速。在此实施例中的第二过渡期间类似于图3A实施例的整体计划,其中在整个过渡期间320改变第三气体混合物的流速,并在较短的过渡期间318改变第四气体混合物的流速。
就图3B所示的实施例而言,以下反应条件和流速普遍有所帮助:
变化速度类似上述,但也可视沉积膜的预定浓度分布而采取不同的变化速度。
图3C显示又一实施例。在此实施例中,在初始期间334,使第一气体混合物改道,仅让第二和第四气体混合物流入反应器。以第一流速使第一气体混合物返回反应器,然后于第一过渡期间326将其变成第二流速(如线324所示),或者使第一气体混合物以第二流速返回反应器而不变化流速(如线322所示)。在此期间亦改变第二气体混合物的流速。如前所述,第一沉积期间328之后接着第二过渡期间332,此时使第三和第四气体混合物变成最终流速,并在整个第三过渡期间330改变第四气体混合物的流速,第三过渡期间330可比第二过渡期间332要长或短。
就图3C所示的实施例而言,以下反应条件和流速普遍有所帮助:
变化速度类似上述,但也可视沉积膜的预定浓度分布而采取不同的变化速度。
在图3D所示的最后示例实施例中,第一气体混合物的流速保持不变,同时在两个不同过渡期间改变第四气体混合物的流速两次。在初始期间334之后,改变第一过渡期间338的第二气体混合物流速。在第一沉积期间340后,改变第二过渡期间342的第四气体混合物流速。如图3D所示,改变整个第二过渡期间342和第三过渡期间344的第三气体混合物流速。在第二沉积期间346后,再次于第四过渡期间348改变第四气体混合物的流速,其后接着最终沉积期间。
就图3D所示的实施例而言,以下反应条件和流速普遍有所帮助:
变化速度类似上述,但也可视沉积膜的预定浓度分布而采取不同的变化速度。
上述各期间的时间取决于特定实施例的需求。在一些实施例中,初始期间可持续0~10秒。初始期间为0秒表示气流引进腔室时立即改变气流流速。故在此包含无初始期间的实施例。在此实施例中,工艺始于第一过渡期间和第一沉积期间,随后可接着其它过渡期间和沉积期间,并且在后续过渡与沉积期间通常增加反应混合物和沉积膜中的碳含量。在其它实施例中,第一过渡期间持续1~10秒。在一些实施例中,各沉积期间持续1~180秒。在一些实施例中,第二过渡期间持续1~180秒。在另一些实施例中,第三和第四过渡期间(若有)持续1~60秒。
较佳地,初始期间沉积得到该膜的一薄部分。在多数实施例中,此部分的厚度小于约10埃(Angstroms)。透过低沉积速度和相对短的期间可达成该膜的薄起始部分的沉积。初始沉积速度较佳为约500埃/分钟至约1000埃/分钟,例如约600埃/分钟,在稍后的沉积期间,沉积速度随着反应气体流速增加而提高到约3000埃/分钟。
前述实施例显示示范的操作处理条件可用以制造黏着性良好的多孔低k介电膜。利用本发明实施例沉积的膜大致具有在整个膜中呈现平稳变化的碳浓度。图4为示例膜的碳浓度曲线图。膜的部分402是具有相对低碳浓度的类氧化物部分。虽然在一些实施例中,类氧化物部分的碳浓度可能趋近于零,但非零的低浓度允许在整体膜沉积过程中更佳地控制工艺。在膜的过渡部分404中碳浓度于开始上升,其通常是在上述过渡期间和中间沉积期间所沉积而得,接着碳浓度在最后部分406达到最大值。最后部分406一般沉积有最多碳,且经后续处理之后具有最大的孔隙度而提供低介电常数膜。
第一和第二气体混合物含有的较佳化合物包括化学通式为(R1)3SiR2Si(R1)3的化合物,其中R1为烷基、烷氧基或烯基且个别选自由CH3、OCH3、OC2H5、C=CH2、H和OH组成的群组,R2选自由(CH2)a、C≡C、C=C、C6H4、C=O、(CF2)b和其组合物所组成的群组,其中a和b为1~4。其它较佳化合物是以环状结构取代-SiR2Si-结构,其中硅占据碳环中的一位置,该碳环还可包含氧原子。具有此通式结构的示例化合物包括双硅基烷烃(bis-sylylalkanes)、二硅环烷烃(disilacycloalkanes)、二硅氧杂环烷烃(disilaoxacycloalkanes)和二硅呋喃(disilafurans)。一些示例化合物包括双(三乙氧硅基)甲烷(bis(triethoxysilyl)methane,C13H32O6Si2)、四甲基-1,3-二硅环丁烷(tetramethyl-1,3-disilacyclobutane,C6H16Si2)、四甲基-2,5-二硅-1-氧杂环戊烷(tetramethyl-2,5-disila-1-oxacyclopentane)和四甲基二硅呋喃(tetramethyldisilafuran,C6H16OSi2)。其它种类的示例化合物具有化学通式为(R6)3SiO(CH2)fOSi(R6)3,其中每个R6个别选自由CH3、OCH3、OC2H5、C=CH2、H和OH所组成的群组,f为1至4。此类的化合物例如包括双烷基硅氧烷烃(bis-alkylsiloxyalkanes)。此种化合物的其中一范例为双(三甲基硅氧)乙烷(bis(trimethylsiloxy)ethane,C8H22O2Si2)。
一或多个含硅与碳的化合物还可包括不具有上述通式结构的有机硅化合物。例如,该些一或多种化合物包括甲基二乙氧硅烷(methyldiethoxysilane,MDEOS)、四甲基环四硅氧烷(tetramethylcyclotetrasiloxane,TMCTS)、八甲基环四硅氧烷(octamethylcyclotetrasiloxane,OMCTS)、三甲基硅烷(trimethylsilane,TMS)、五甲基环戊硅氧烷(pentamethylcyclopentasiloxane)、六甲基环三硅氧烷(hexamethylcyclotrisiloxane)、二甲基二硅氧烷(dimethyldisiloxane)、四甲基二硅氧烷(tetramethyldisiloxane)、六甲基二硅氧烷(hexamethyldisiloxane,HMDS)、1,3-双(硅烷基伸甲基)二硅氧烷(1,3-bis(silanomethylene)disiloxane)、双(1-甲基二硅氧基)甲烷(bis(1-methyldisiloxanyl)methane)、双(1-甲基二硅氧基)丙烷(bis(1-methyldisiloxanyl)propane)、六甲氧基二硅氧烷(hexamethoxydisiloxane,HMDOS)、二甲基二甲氧基硅烷(dimethyldimethoxysilane,DM DMOS)或二甲氧基甲基乙烯基硅烷(dimethoxymethylvinylsilane,DMMVS)。
第三气体混合物一般包含一或多种成孔剂化合物。成孔剂为包含热不稳定基团的化合物。热不稳定基团可为环状基团,例如不饱和环状有机基团。“环状基团(cyclic group)”在此意指环状结构。环状结构最少含有三个原子。该些原子例如包括碳、氮、氧、氟和其组合。环状基团可包括一或多个单键、双键、三键和其组合。例如,环状基团包括一或多个芳香基(aromatics)、芳香羟基(aryl)、苯基、环己烷基(cyclohexanes,)、环己二烯基(cyclohexadienes)、环庚二烯基(cycloheptadienes)和其组合物。环状基团亦可为二环或三环。在一实施例中,环状基团连结至一直链或支链的官能基。直链或支链的官能基较佳包括烷基或乙烯基烷基,且具有1~20个碳原子。直链或支链的官能基还可包括氧原子,例如酮、醚和酯。成孔剂可包含环状碳氢化合物。一些可用的示例成孔剂包括二联环七二烯(BCHD,bicycle(2.2.1)hepta-2,5-diene)、α-萜品烯(alpha-terpinene,ATP)、乙烯基环己烷(vinylcyclohexane,VCH)、苯乙酸盐/酯(phenylacetate)、丁二烯(butadiene)、异戊二烯(isoprene)、环己二烯(cyclohexadiene)、1-甲基-4-(1-甲基乙基)-苯(异丙甲苯)(1-methyl-4-(1-methylethyl)-benzene(cymene))、3-蒈烯(3-carene)、葑酮(fenchone)、薴烯(limonene)、环氧环戊烷(cyclopentene oxide)、乙烯基-1,4-二恶英醚(Vinyl-1,4-dioxinyl ether)、乙烯基呋喃醚(vinyl furyl ether)、乙烯基-1,4-戴奥辛(Vinyl-1,4-dioxin)、乙烯基呋喃(vinyl furan)、糠酸甲酯(methyl furoate)、甲酸呋喃酯(furyl formate)、乙酸呋喃酯(furyl acetate)、糠醛(furaldehyde)、二呋喃酮(difuryl ketone)、二呋喃醚(difuryl ether)、二糠醚(difurfuryl ether)、呋喃(furan)和1,4-戴奥辛(1,4-dioxin)。
引进各种气体混合物的腔室可为等离子增强化学气相沉积(PECVD)腔室。利用固定式射频(RF)功率、脉冲式RF功率、高频RF功率、双频RF功率或其组合可产生用于沉积工艺的等离子。可用的PECVD腔室一例为腔室,其取自美国加州圣塔克拉拉市的应用材料公司。然而,其它腔室也可用来沉积低介电常数膜。腔室一般包含设有气体分配板的气体分配组件,例如喷头。RF功率施加至电极(如喷头)而产生等离子处理条件。基板通常置于基板支撑件上,其与气体分配板一同定义出反应区域。节流阀设在排放管在线来维持腔室压力。流速改变时,调整节流阀以控制腔室压力。
在上述工艺期间,基板的温度一般维持在约100℃至约400℃之间。腔室压力为约1托耳(Torr)至约20托耳,基板支撑件与腔室喷头之间之间距为约200密尔(mils)至约1500密尔。就300毫米(mm)的基板而言,功率密度为约0.14瓦/平方公分(W/cm2)至约2.8W/cm2,RF功率为约100W至约2000W。RF功率可以约0.01MHz至300MHz(如约13.56MHz)的频率提供。RF功率亦可以混频提供,例如约13.56MHz的高频和约350千赫(kHz)的低频。RF功率可循环或脉冲输入,藉以减少对基板的加热并提高沉积膜的孔隙度。RF功率也可为连续式或不连续式。
示例的紫外线(UV)后续处理条件包括腔室压力为约1托耳至约10托耳,基板支撑件温度介于约350℃至约500℃之间。利用诸如汞微波弧灯、脉冲式氙闪光灯或高效率UV发光二极管数组等任何UV源皆可提供UV幅射。UV幅射波长例如为约170nm至约400nm。UV腔室和处理条件的其它细节可参见共同让渡的美国专利申请案序号11/124,908、于2005年5月9日申请的申请案,其一并引用于此。用于UV后续处理的市售腔室一范例为取自应用材料公司的NanoCureTM腔室。
示例电子束条件包括腔室温度介于约200℃至约600℃,例如约350℃至约400℃。电子束能量为约0.5千电子伏特(KeV)至约30KeV。曝光剂量为约1微库仑/平方公分(μc/cm2)至约400微库仑/平方公分。腔室压力为约1毫托耳(mTorr)至约100毫托耳。腔室中的气体环境可由下列任何气体组成:氮气、氧气、氢气、氩气、氢气与氮气的混合物、氨气、氙气或这些气体的组合物。电子束电流为约0.15至约50毫安(mA)。电子束处理可进行约1至15分钟。一示例电子束腔室为EBkTM电子束腔室,其取自美国加州圣塔克拉拉市的应用材料公司,但也可采用任何其它电子束装置。
示例的热退火后续处理包括在腔室中以约200℃至约500℃的基板温度,退火处理该膜约2秒至约3小时,较佳约0.5至约2小时。诸如氦气、氢气、氮气或其混合物等非反应性气体可以约100至约10000sccm的流速引入腔室。腔室压力维持在约1毫托耳至约10托耳之间。较佳的基板间距为约300密尔至约800密尔。
应理解文中所述的有机硅化合物可用于不含成孔剂的气体混合物中,来化学气相沉积低介电常数膜。尽管相较于由包含其它有机硅化合物但不合成孔剂的混合物沉积而得的膜来说,由包含本文所述有机硅化合物且缺乏成孔剂的气体混合物沉积而得的膜具有较佳的机械性质,但一般仍加入成孔剂,以期提供较低的介电常数,例如2.4或更低。
虽然本发明已以较佳实施例揭露如上,然而在不脱离本发明基本范围的情况下,当可作出本发明的其它和进一步实施例,因此本发明的保护范围当视权利要求所界定者为准。
Claims (15)
1.一种处理基板的方法,其至少包含:
将该基板放到处理腔室内的支撑件上;
以第一流速提供第一有机硅前体至该腔室;
以第二流速提供第二有机硅前体至该腔室;
以第三流速提供碳氢化合物混合物至该腔室;
以第四流速提供氧化剂至该腔室;
改变该第二有机硅前体的该第二流速至更高流速;
改变该氧化剂的该流速至更高流速;以及
在处理该基板时的至少一部分时间内,引导该碳氢化合物混合物改道绕过(bypass)该腔室。
2.如权利要求1所述的方法,其中该第一有机硅前体的碳原子与硅原子比率小于该第二有机硅前体的碳原子与硅原子比率。
3.如权利要求1所述的方法,其中该碳氢化合物混合物包含一或多种具有环状基团的化合物。
4.如权利要求1所述的方法,其中改变该第二有机硅前体的该第二流速的步骤包括改变该第二有机硅前体的变化速度比改变该氧化剂的变化速度要快。
5.如权利要求1所述的方法,其中该第一有机硅前体、该第二有机硅前体、该碳氢化合物混合物和该氧化剂在该处理腔室中构成一反应混合物,在处理该基板期间,该反应混合物中的碳原子与硅原子比率从约3∶1提高到约20∶1。
6.一种处理基板的方法,其至少包含:
提供数个包含硅、碳、氧和氢的气体混合物至处理腔室,其中该些气体混合物的其中至少二气体混合物是硅源;
通过施加射频(RF)功率于该处理腔室来提供等离子处理条件;
使至少一部分的该些气体混合物反应而沉积一膜于该基板上;以及
在施加该RF功率期间,调整该处理腔室中的碳原子与硅原子比率,以调整该沉积膜的数个部分中的碳含量。
7.如权利要求6所述的方法,其中调整该处理腔室中的碳原子与硅原子比率的步骤包含引导一或多个气体混合物改道绕过该腔室。
8.如权利要求6所述的方法,其中该些气体混合物包含第一气体混合物,该第一气体混合物包含一或多种具有-Si-Cx-Si-键结的有机硅化合物。
9.如权利要求8所述的方法,其中该些气体混合物更包含一第二气体混合物,该第二气体混合物包含一或多种具有热不稳定基团的碳氢化合物。
10.如权利要求6所述的方法,更包含后续处理该基板,以于该沉积膜内产生多个细孔。
11.如权利要求9项所述的方法,其中调整该处理腔室中的碳原子与硅原子比率的步骤包含使该一或多种碳氢化合物改道绕过该处理腔室。
12.如权利要求6所述的方法,其中调整该沉积膜的碳含量的步骤包含沉积该膜的具有低碳含量的一类氧化物部分、平稳地增加该膜的一过渡部分中的碳含量,以及沉积该膜的具有最高碳含量的一类碳氧化物部分。
13.一种在置于处理腔室内的基板上沉积低介电常数(k)介电膜的方法,该方法包含:
提供第一气体混合物至该处理腔室,该第一气体混合物包含一或多种具-Si-Cx-Si-或-Si-O-Cx-O-Si-键结且碳原子与硅原子比率小于约6∶1的化合物;
伴随该第一气体混合物,提供一第二气体混合物至该处理腔室,该第二气体混合物包含一或多种具有-Si-Cx-Si-或-Si-O-Cx-O-Si-键结且碳原子与硅原子比率大于约8∶1的化合物;
提供包含一或多种碳氢化合物的一第三气体混合物至该处理腔室,该一或多种碳氢化合物的至少其中一化合物具有热不稳定基团;
提供包含多个氧源的一第四气体混合物至该处理腔室;
施加一射频(RF)功率,并且使至少一部分的该些气体混合物反应而沉积一膜于该基板上;
在施加该RF功率时,调整该些含碳的气体混合物中的一或多个气体混合物的量,藉以改变该膜中的碳沉积速度;以及
后续处理该沉积膜,以降低该膜的介电常数。
14.如权利要求13所述的方法,其中该一或多种具有-Si-Cx-Si-或-Si-O-Cx-O-Si-键结的化合物分别选自于由双(三乙氧硅基)甲烷(bis(triethoxysilyl)methane,C13H32O6Si2)、四甲基-1,3-二硅环丁烷(tetramethyl-1,3-disilacyclobutane,C6H16Si2)、四甲基-2,5-二硅-1-氧杂环戊烷(tetramethyl-2,5-disila-1-oxacyclopentane)、四甲基二硅呋喃(tetramethyldisilafuran,C6H16OSi2)和双(三甲基硅氧)乙烷(bis(trimethylsiloxy)ethane,C8H22O2Si2)组成的群组中。
15.如权利要求13所述的方法,其中后续处理该沉积膜的步骤将于该膜的具较高碳含量的部分内产生多个细孔。
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PCT/US2009/049216 WO2010008930A2 (en) | 2008-07-15 | 2009-06-30 | Methods to promote adhesion between barrier layer and porous low-k film deposited from multiple liquid precursors |
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