CN103443901B - 选择性沉积外延锗合金应力源的方法与设备 - Google Patents

选择性沉积外延锗合金应力源的方法与设备 Download PDF

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CN103443901B
CN103443901B CN201180069589.5A CN201180069589A CN103443901B CN 103443901 B CN103443901 B CN 103443901B CN 201180069589 A CN201180069589 A CN 201180069589A CN 103443901 B CN103443901 B CN 103443901B
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germanium
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埃罗尔·安东尼奥·C·桑切斯
戴维·K·卡尔森
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Abstract

描述形成异质结应力源层的方法与设备。将锗前驱物与金属前驱物提供至腔室，并在基板上形成锗‑金属合金的外延层。金属前驱物通常是金属卤化物，可由升华固态金属卤化物或通过卤素气体接触纯金属来提供金属卤化物。可通过喷头或通过侧进入点来提供前驱物，并可分开地加热耦接至腔室的排气系统以管理排气成分的凝结。

Description

选择性沉积外延锗合金应力源的方法与设备
发明背景
发明所属的技术领域
本文所述技术涉及半导体器件的制造。更具体地来说，描述利用应变材料(strained material)形成场效晶体管的方法。
相关技术的描述
锗是首先用于诸如CMOS晶体管的半导体应用的材料之一。然而，由于硅相对于锗的巨大含量，硅已经成为CMOS制造的压倒性半导体材料的选择。随着器件的几何尺寸根据摩尔定律减少，晶体管部件的尺寸对努力使器件更小、更快、利用更低功率并产生更低热量的工程师提出挑战。例如，随着晶体管尺寸减少，晶体管的沟道区域变得更小，并且因为沟道具有更高的电阻率与更高的阈值电压，沟道的电特性变得更不易维持。正如某些制造商已经对45纳米节点所做的那样，通过利用嵌在源极/漏极区中的硅-锗应力源（stressor）来提高硅沟道区中的载流子迁移率。然而，对于未来的节点来说，还是需要更高迁移率的器件。因此，持续需要用来形成高迁移率半导体器件的方法与设备。
发明概述
提供在半导体基板上形成应力源层的方法与设备。可通过以下步骤将锗应力源层形成于基板上：将基板置于处理腔室中；将锗前驱物流入处理腔室中；在处理腔室外形成应力源前驱物；将应力源前驱物流入处理腔室中；以及在基板上外延地生长锗应力源层。形成这些层的设备包括：旋转的基板支撑件，所述旋转的基板支撑件设置在封围件中；多个气体入口，所述多个气体入口形成于封围件的壁中；至少一个气体出口，所述至少一个气体出口形成于封围件的壁中；用以产生应力源前驱物的反应性或非反应性源，所述反应性或非反应性源由第一导管耦接至气体入口；用以提供锗前驱物的非反应性源，所述非反应性源由第二导管耦接至气体入口；以及经加热的排气系统。所述经加热的排气系统可具有用来降低排气成分附着的涂层，并且所述经加热的排气系统可包括凝结阱。
锗前驱物可以是氢化物，而应力源前驱物可以是金属卤化物。反应混合物中可包括选择性控制物种(例如，卤化物气体)，以控制基板的半导电与介电区域上的沉积选择性。
附图简要说明
可参照实施方式(某些实施方式描绘于附图中)来详细理解本发明的上述特征结构以及以上简要概述的有关本发明更特定的描述。然而，需注意附图仅描绘本发明的典型实施方式，因此不被视为本发明范围的限制因素，因为本发明可允许其他等效实施方式。
图1是概述根据一个实施方式的方法的流程图。
图2是概述根据另一个实施方式的方法的流程图。
图3是根据另一个实施方式的设备的示意图。
为了便于理解，已尽可能地应用相同的参考数字来标示各图示共有的相同的元件。预期一个实施方式中披露的元件可有利地用于其他实施方式而不需特别详述。
详细描述
图1是概述根据一个实施方式的方法100的流程图。在102时，将半导体基板置于处理腔室中。半导体基板可以是上面即将形成有应力源层的任何半导电材料。一个实例中，可以使用上面即将形成有晶体管构造的硅基板。在一些实施方式中，半导体基板的一个表面上可形成有介电区。例如，硅基板可具有邻近半导电源极/漏极区域形成的晶体管栅极构造以及介电间隔物，所述半导电源极/漏极区域可为掺杂硅的区域或者上面即将形成有源极/漏极材料的区域。因此，除了掺杂硅层以外，源极/漏极区域可包括本文所述的应力源层，或者源极/漏极区域可包括本文所述的应力源层来取代掺杂硅层。
本文所述的应力源层通常包括设置于锗基质中的金属原子GexMy。大金属原子(例如，大于锗的IV族金属，比如锡与铅)对添加压缩应力(compressivestress)至锗基质是有用的。锗晶体通常具有单位晶胞(unit cell)大小约为570皮米的立方体构造。各个锗原子的半径约为125皮米，而锡原子的半径约为145皮米、而铅的半径在155与180皮米之间。添加较大的金属原子至锗晶体基质导致较大的晶格尺寸，所述较大的晶格尺寸施加单轴压缩应力至侧边的锗原子和/或施加双轴拉伸应力至覆盖的锗原子。与未应变的锗相比，这样的应变提高局部电子的能量并降低锗的带隙，而导致较高的载流子迁移率。
在一个方面中，硅基板可具有锗沟道层，所述锗沟道层附近有应力源层，且应力源层即将形成为晶体管栅极构造的一部分。此情况下的GexMy应力源施加单轴应力至邻近的锗层上。在另一个方面中，在应力源层之上沉积锗沟道层，以致对锗沟道层施加双轴拉伸应力。
在104处，提供锗前驱物至包含半导体基板的处理腔室。锗前驱物通常为锗氢化物，比如锗烷(GeH4)、二锗烷(Ge2H6)或较高级的氢化物(GexH2x+2)，或上述的组合。锗前驱物可与载气混合，所述载气可为非反应性气体(例如，氮气、氢气)或惰性气体(例如，氦或氩)或上述的组合。锗前驱物体积流率与载气流率的比例可用来控制通过腔室的气体流速。根据所期望的流速，上述比例可以是约1%至约99%间的任何比例。在一些实施方式中，相对高的速度可改善形成的层的均匀性。在300毫米的单一晶片实施方式中，锗前驱物的流率可在约0.1sLm与约2.0sLm之间。对于体积约为50L的腔室来说，在上述锗前驱物的流率，约5sLm与约40sLm间的载气流率下提供均匀的层厚度。
在106处，提供金属卤化物至处理腔室以与锗前驱物反应并沉积金属掺杂的锗层。金属卤化物可为锡或铅卤化物气体(比如，SnCl4、SnCl2、PbCl4或PbCl2)或分子式为RxMCly的有机金属氯化物，其中R是甲基或叔丁基(t-butyl)，x是1或2，M是Sn或Pb，并且y是2或3，以致形成的层主要由IV族元素所构成。
邻近的锗层中实现的迁移率增强程度取决于晶格失配（mismatch）以及应力源层所施加的后续应力。所述晶格失配以及所述应力源层所施加的后续应力大致线性取决于应力源基质中金属原子的浓度。随着应力源中金属浓度的提高，由于轨道的弯曲与应变，邻近的受应力锗中的价电子能量提高，并且传导带(conduct band)的能量降低。在足够高的浓度下，半导体-金属合金变成直接带隙材料(即，金属的)。在一些实施方式中，限制金属浓度可有用于让合金保持间接带隙材料。晶体管应用中，在源极/漏极区域中维持间接带隙材料可降低泄漏。
在约10sccm与约300sccm之间(诸如约50sccm与约200sccm之间，例如约100sccm)的流率下提供金属卤化物至处理腔室。金属卤化物也可以与载气混合，以达到处理腔室中所期望的空间速度和/或混合性能。金属卤化物可源自升华进入流动载气流(例如，N2、H2、Ar或He)中的金属卤化物晶体的固态源，或者可将卤素气体(选择性地搭配上述载气之一)在接触腔室中在固态金属之上通过来产生金属卤化物，在接触腔室中进行反应M+2Cl2→MCl4，其中M为Sn或Pb。接触腔室可邻近于处理腔室，接触腔室由导管耦接至处理腔室，导管较佳是短的以降低金属卤化物微粒沉积于导管中的可能性。
通常通过不同路径提供金属卤化物与锗前驱物至处理腔室。通过第一路径提供锗前驱物，并通过第二路径提供金属卤化物。所述两个路径通常是不同的，且保持分离直到进入处理腔室的位置。在一个实施方式中，两个流通过邻近基板支撑件边缘的腔室侧壁进入，由一侧移动横跨基板支撑件至上述侧的相对侧并进入排气系统。基板支撑件可在应力层形成过程中旋转以改善均匀性。第一路径通常连通于进入处理腔室的第一进入点，所述第一进入点可包括腔室壁中或耦接至腔室壁的气体分配器(例如，喷头)中的一个或更多个开口。所述一个或更多个开口可如上面所描述地邻近基板支撑件的边缘，或者可以是双路径或多路径气体分配器中的入口。同样地，第二路径连通于第二进入点(与第一进入点相似)。所述第一与第二进入点经设置，以使两个流在基板支撑件上方的区域中混合并提供沉积或层生长混合物。在一些实施方式中，使用气体分配器可降低或消除处理过程中对旋转基板的需求。
对高结构品质而言，应力源层的生长通常是外延的。处理腔室中的压力被维持在约5Torr与约200Torr之间，诸如约20Torr与约80Torr之间，例如约40Torr。温度是在约150℃与约500℃之间，诸如约200℃与约400℃之间，例如约300℃。将温度维持在金属卤化物前驱物的分解温度(通常为约600℃或更低)以下。在一些实施方式中，压力可在约5Torr以下，但降低的压力也会降低沉积速率。在这些条件下，沉积速率是在约50埃/分与约500埃/分之间。
在108处，根据以下反应形成锗应力源层或锗金属合金层：
MCl4+GeH4→MH2Cl2+GeH2Cl2
MH2Cl2+H2→M+2HCl+H2
GeH2Cl2+H2→Ge+2HCl+H2
其中M为Sn或Pb。相似反应发生于上述的有机金属氯化物。较高阶的锗烷产生氯化锗烷中间物的混合物，所述氯化锗烷中间物的混合物会相似地分解成锗沉积物。可提供氢气至腔室以促进沉积反应。约5sLm与约40sLm之间的氢气流率可包含于任何或所有的前驱物以提供环境氢气浓度。
层的通常沉积厚度是在约300埃与约800埃之间。根据方法100，锗基质中的锡原子浓度可在约1%与约12%之间，诸如约3%与约9%之间，例如约6%。若使用铅的话，锗基质中的铅原子浓度可在约0.2%与约5%之间，诸如约1%与约3%之间，例如约2%。如果需要的话，可使用铅与锡的混合物。比起锡而言，铅可在较低剂量下实现较高的带隙降低，且在一些实施方式中，利用铅与锡的混合物可有利地提供具有带隙降低的某些增强的可加工性（processability）(即，在提高的温度下，锡卤化物比铅卤化物更稳定)。
图2是概述根据另一个实施方式的方法200的流程图。方法200在许多方面与方法100相似，且在处理具有半导电与介电区域的基板时可用来实现相似结果。在202处，将具有半导电与介电特征结构的基板置入具有参照图1如上所述的特征的处理腔室中。在204处，通过第一路径将锗前驱物(可以是参照图1所述的任何锗前驱物)提供至处理腔室。在206处，可通过第二路径将锡前驱物或铅前驱物，或锡前驱物与铅前驱物的混合物提供至处理腔室，锡与铅前驱物可以是参照图1如上所述的任何锡或铅前驱物。
在208处，将沉积控制物种提供至处理腔室。提供沉积控制物种以控制基板表面上锗、锡和/或铅的沉积。比起半导电区域，沉积控制物种自基板的介电区域更快速地选择性地移除沉积物种。因此，沉积控制物种可以是选择性控制物种，因为在一些实施方式中，可通过调整反应混合物中选择性控制物种相对于反应物种的数量来控制选择性。
沉积控制物种通常是含卤素物种，例如卤化物(比如，HCl、HF或HBr)。在一个实施方式中，沉积控制物种是HCl。可在约10sccm与约1000sccm间的流率下提供沉积控制物种，所述流率是在诸如约100sccm与约500sccm之间，例如约200sccm。可通过调整沉积控制物种与锗前驱物的体积比来控制层生长选择性与沉积速率。较高的比例降低整体的沉积速率但改善了选择性。对大部分实施方式来说，沉积控制物种与锗前驱物的体积流率比的范围是在约0.01与约0.1之间，诸如约0.02与约0.06之间，例如约0.04。在范围的最顶端处，沉积速率约为50埃/分，而在范围的最低处，沉积速率为约500埃/分。然而，在范围的最顶端处，并没有发现基板的介电区域上的膜生长，而在范围的最低处，半导电区域上的沉积速率是介电区域上的沉积速率的约50倍。
通过改变并入应力源基质中的金属浓度而在低金属浓度下可以控制由应力源层引入的压缩应力的量。可通过调整反应混合物中金属前驱物与锗前驱物的比例来控制金属浓度。对大部分实施方式而言，提供至处理腔室的金属前驱物与锗前驱物的体积流率的比例将在约1%与约20%之间，诸如约4%与约12%之间，例如约8%。
图3是根据另一个实施方式的设备300的示意图。设备300能用来执行本文所述形成应力层的方法。处理腔室302具有基板支撑件308，所述基板支撑件308可以是旋转的基板支撑件，且所述基板支撑件308设置在所述处理腔室302的内部中。面对所述基板支撑件308的一侧来设置加热源306。或者，加热源可嵌于所述基板支撑件308中。2007年2月6日核发的共同受让美国专利第7172792号(名称为“Method for forming a high quality lowtemperature silicon nitride film”)中描述的具有经加热基板支撑件的腔室可适于构建本文所述的设备并执行本文所述的方法。2008年3月27日公开的共同受让美国专利公开文献第2008/0072820号(名称为“Modular CVD Epi 300mm Reactor”)中描述的具有灯加热模组的腔室也可以适于构建本文所述的设备并执行本文所述的方法。EpiTM300mm反应器或300mm xGenTM腔室(两个均可自California(加利福尼亚)州Santa Clara（圣克拉拉）的Applied Mterials,Inc.(应用材料公司)取得)可适以进行并使用本文所述的实施方式。所述处理腔室302可具有让气体进入腔室的喷头304。或者，可通过侧进入点320将气体提供至处理腔室，所述侧进入点320耦接至所述腔室302的侧壁360。
馈送系统328(包括化学输送系统310与金属前驱物接触腔室312)通过多个导管耦接至所述腔室302。第一导管322与第二导管324可耦接所述馈送系统328至选择性的喷头304。为了执行本文所述的方法，所述喷头304可以是双-路径喷头(dual-pathwayshowerhead)，以避免在进入所述腔室302之前的前驱物混合。示范性双-路径喷头描述于2006年1月10日核发的共同受让美国专利第6,983,892号(名称为“Gas distributionshowerhead for semiconductor processing”)。
可选地或额外地，可通过提供第一与第二横流式（cross-flow）气体导管316与318至所述侧进入点320来执行横流式气体注入。横流式注入构造的实例描述于美国专利第6,500,734号中。所述设备300可包括喷头构造与横流式注入构造两者，或仅有一个构造或另一个构造。
所述化学输送系统310输送锗前驱物(选择性与载气(比如氮气和/或氢气)一起)至所述腔室302。所述化学输送系统310也可以输送沉积或选择性控制物种至所述腔室302。所述化学输送系统310可包括液态或气态源与控制器(未图示)，所述化学输送系统310可构造于气体面板中。
所述接触腔室312可通过导管314耦接所述侧进入点320或所述喷头304中的任一个，所述导管314被设置用来携带金属前驱物至所述腔室302。可将所述导管314、316与322加热至约50℃与约200℃间的温度，以控制或避免金属卤化物物种凝结于所述导管314、316与322中。所述接触腔室312通常包含固态金属或金属卤化物晶体的床。通过气体馈送导管362与364之一或两者提供载气，而金属卤化物晶体可升华进入载气。通过所述气体馈送导管362与364之一或两者提供卤素气体源，而固态金属可接触卤素气体源。在一个实施方式中，通过第一气体馈送导管362提供卤素气体源，而通过第二气体馈送导管364提供载气。可将用于升华或反应任一个的气体流过粉末状的金属或金属卤化物流体化床以增进接触。网孔过滤器（mesh strainer）或滤件可用来避免夹带颗粒进入所述腔室302。或者，气体可流过固定的固态金属或金属卤化物床。
排气系统330耦接至所述腔室302。所述排气系统330可在任何方便位置耦接至腔室，方便位置可取决于气体进入腔室的位置。针对通过所述喷头304气体而言，排气系统可例如通过一个或更多个入口或通过环形开口围绕所述加热源306耦接至腔室的底部壁。在一些实施方式中，环形歧管可设置在基板支撑件的边缘附近并耦接至所述排气系统330。对横流式实施方式来说，所述排气系统330可耦接至与所述侧进入点320相对的腔室侧壁。
排气导管340通过节流阀366耦接排气盖332至真空泵352。护套368自所述排气盖332至所述真空泵352的入口350围绕所述排气导管340与所述节流阀366。所述护套368允许热控制所述排气导管340以避免排气物种凝结于管线中。任何加热媒介(比如，蒸气或热空气、水或其他热流体)可用来维持排气导管的温度在排气气体的露点(dew point)以上。或者，护套可包括电阻式加热元件(即，电热毯)。如果需要的话，凝结阱(condensation trap)336可通过阀338耦接至所述排气导管340，以进一步增强所述排气系统330中任何凝结物的获取。所述真空泵352通过减弱（abatement）导管354清理(pay off)至减弱系统356，所述减弱导管354通常是未加热或不具护套的，且清洁后的气体在358处排放。为了进一步降低所述排气导管340中的潮湿或成核作用，所述排气导管340可涂覆有石英或惰性聚合物材料。
可通过活性源334将等离子体或紫外光活化的清洁剂耦接进入所述排气系统330，所述活性源334可耦接至微波或RF腔室以产生活性清洁物种。清洁气体管线326可从所述化学输送系统310提供清洁气体至所述排气导管340，如果需要的话，可让清洁气体前进通过所述活性源334。使用活性物种进行清洁使得清洁能在降低的温度下进行。
清洁腔室的方法包括提供卤素气体至腔室、转换残余物成可挥发卤化物，所述腔室是用来执行本文所述方法的腔室(例如，所述腔室302)或任何用以执行方法100与200的腔室。在清洁过程中通常将腔室的温度维持在约600℃以下，并且将金属沉积物转换成MClx，通常为SnClx或PbClx。所述卤素气体可以是氯气、氟气、HCl或HF。可将腔室加热至不需要独立加热排气导管的程度，特别是在隔离排气导管的情况下。或者，如果需要的话，可将腔室温度维持在约400℃以下，并加热所述排气导管340以避免凝结。
形成应力源层的替代实施方式可包括形成实质纯外延锗层并接着形成金属-掺杂外延锗层的循环处理，通常根据上述方案通过在维持锗前驱物的流动时开始与结束金属前驱物的流动来形成纯层与掺杂层。其他实施方式中，可通过下述步骤来形成具有分级应力的层：建立锗前驱物的流动达一时间周期以形成实质纯锗的外延初始层；在初始流率下开始金属前驱物的流动；然后根据任何所期望的模式(线性或非线性的)提高金属前驱物的流率至最终流率。这样的分级应力层可更强力地附着至下层同时提供增加的电子迁移率。
虽然上述是针对本发明的实施方式，但可以在不悖离本发明的基本范围下设计出本发明的其他以及更多实施方式。

Claims (10)

1.一种在基板上形成数个锗应力源层的方法，所述方法包括：
将所述基板置于处理腔室中；
将锗前驱物流入所述处理腔室中；
在反应空间中形成金属卤化物应力源前驱物，所述反应空间耦接至所述处理腔室，其中在所述金属卤化物应力源前驱物是有机锡氯化物，并且其中形成所述金属卤化物应力源前驱物包括升华金属卤化物晶体的固态源进入流动载气流，且所述流动载气流包括N2、H2、Ar或He；
将所述金属卤化物应力源前驱物流入所述处理腔室中；以及
在所述基板上外延生长锗应力源层，其中所述锗应力源层包括设置于锗基质中的金属原子，其中在所述锗基质中的金属原子浓度在1％与12％之间，且其中所述金属原子来自所述金属卤化物应力源前驱物。
2.如权利要求1所述的方法，进一步包括将选择性控制物种流入所述处理腔室中。
3.如权利要求2所述的方法，其中所述基板包括数个介电区域与数个半导电区域，且所述选择性控制物种控制所述锗应力源层在所述介电区域与半导电区域上的相对生长速率。
4.如权利要求1所述的方法，其中所述金属卤化物应力源前驱物包括具有通式RxSnCly的有机锡氯化物，其中R是甲基或叔丁基、x是1或2且y是2或3。
5.如权利要求1所述的方法，其中所述锗前驱物是锗烷或二锗烷。
6.如权利要求1所述的方法，其中所述锗前驱物与所述金属卤化物应力源前驱物从所述腔室的一侧流动横跨所述腔室而至所述腔室的相对侧。
7.如权利要求1所述的方法，其中所述锗前驱物与所述金属卤化物应力源前驱物通过喷头流入所述腔室中。
8.如权利要求3所述的方法，其中所述选择性控制物种选择性地移除所述基板的所述介电区域上沉积的材料。
9.如权利要求2所述的方法，其中在所述基板上外延生长所述锗应力源层的步骤包括维持所述处理腔室在5Torr与80Torr之间的压力下，且维持所述处理腔室在150℃与400℃之间的温度下。
10.如权利要求9所述的方法，其中所述金属卤化物应力源前驱物与所述选择性控制物种的流率比例是在2：1与100：1之间。
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