CN113348532A - 金属硅化物的选择性沉积和选择性氧化物移除 - Google Patents
金属硅化物的选择性沉积和选择性氧化物移除 Download PDFInfo
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- CN113348532A CN113348532A CN201980074914.3A CN201980074914A CN113348532A CN 113348532 A CN113348532 A CN 113348532A CN 201980074914 A CN201980074914 A CN 201980074914A CN 113348532 A CN113348532 A CN 113348532A
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- silicon
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- 229910052751 metal Inorganic materials 0.000 title abstract description 8
- 239000002184 metal Substances 0.000 title abstract description 8
- 229910021332 silicide Inorganic materials 0.000 title abstract description 8
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Abstract
本公开内容的实施方式涉及选择性金属硅化物沉积方法。在一个实施方式中,加热具有含硅表面的基板,并且含硅表面被氢封端。将基板暴露于MoF6前驱物和Si2H6前驱物的顺序循环,随后进行额外的Si2H6过量暴露,以选择性地在基板的含硅表面上沉积包含MoSi2的MoSix材料。本文描述的方法亦提供了选择性的原生氧化物移除,此能够在不蚀刻主体氧化物材料的情况下移除原生氧化物材料。
Description
技术领域
本公开内容的实施方式大体涉及金属硅化物沉积和选择性原生(native)氧化硅蚀刻的方法。
背景技术
材料在纳米级装置上的精确定位对于控制下一代纳米电子的原子尺度特性至关重要。对于半导体制造,利用具有优异保形性和化学计量的材料的详细定位用于满足成本、产率和产量的需求。随着金属氧化物半导体场效应晶体管(metal-oxide-semiconductorfield effect transistor;MOSFET)的沟道长度不断缩小,需要克服源于自上而下(top-down)工艺的约束性,诸如反应离子蚀刻的损伤和三维(three-dimension;3D)表面上结构对准的结构复杂性。
最近,随着MOSFET装置在三维结构(FinFET)中的制造,人们对保持保形膜品质的同时的纳米级区域选择性沉积越来越感兴趣。区域选择性沉积的一种方法是结合原子层沉积(atomic layer deposition;ALD)工艺使用自组装单层(self-assembled monolayer;SAM)作为钝化层。钝化层阻挡或消除对ALD前驱物具有反应性的表面官能基团,从而可获得选择性;然而,SAM方法仍然利用钝化层的选择性沉积。此外,在选择性沉积之后,选择性地移除钝化层,此迫使产生了额外的工艺复杂性和产量的降低。
此外,为了实现进阶(advanced)选择性区域沉积,要移除原生氧化物材料,以暴露下层的材料,以用于在其上进行选择性沉积。然而,在进阶节点,原生氧化物移除变得越来越复杂,并且当基板上存在除了原生氧化物材料之外的其他氧化物材料时,选择性变得困难。
因此,本领域需要的是用于选择性材料沉积和选择性氧化物移除的改进方法。
发明内容
在一个实施方式中,提供了一种基板处理方法。所述方法包括将具有含硅表面的基板加热到第一温度,将基板暴露于包含氢的等离子体,将基板暴露于第一剂量的MoF6前驱物,并将基板暴露于第二剂量的Si2H6前驱物。将基板暴露于第一剂量和将基板暴露于第二剂量是顺序循环的,并且在顺序循环之后,将基板暴露于第三剂量的Si2H6前驱物。
在另一个实施方式中,提供了一种基板处理方法。所述方法包括将基板定位在具有腔室壁的反应腔室中的加热器上,将加热器上的基板加热到第一温度,将腔室壁保持在低于第一温度的第二温度,并将基板的含硅表面暴露于氢气。将基板暴露于第一剂量的MoF6前驱物,将基板暴露于第二剂量的Si2H6前驱物,将基板暴露于第一剂量和将基板暴露于第二剂量是顺序循环的,并且在顺序循环之后,将基板暴露于第三剂量的Si2H6前驱物。
在又一实施方式中,提供了一种基板处理方法。所述方法包括将基板加热到第一温度,将基板的含硅表面暴露于含氢等离子体,将基板暴露于第一剂量的MoF6前驱物,并将基板暴露于第二剂量的Si2H6前驱物。将基板暴露于第一剂量和将基板暴露于第二剂量是顺序循环的,在顺序循环之后,将基板暴露于第三剂量的Si2H6前驱物,并且在约500℃与约550℃之间的第二温度下将基板暴露于第三剂量之后,对基板进行退火。
附图说明
专利或申请文件包含至少一幅彩色绘图。本专利或专利申请公开的彩色附图副本将在请求及支付必要的费用后由专利局提供。
为了详细理解本公开内容的上述特征的方式,可参照实施方式对以上简要概述的本公开内容进行更具体的描述,其中一些实施方式在附图中示出。然而,应当注意,附图仅示出了示例性实施方式,因此不被认为是对其范围的限制,可允许其他同等有效的实施方式。
图1A示出了根据本文所述一实施方式的硅基板上MoSix膜选择性的X射线光电子光谱法(X-ray photoelectron spectroscopy;XPS)数据。
图1B示出了根据本文所述一实施方式的氮氧化硅基板上MoSix膜选择性的XPS数据。
图2A示出了根据本文所述一实施方式的硅基板上硅和Mo的XPS氧化态数据。
图2B示出了根据本文所述一实施方式的硅基板上硅和Mo的XPS氧化态数据。
图3A示出了根据本文所述一实施方式,在ALD处理之前,存在于不同基板类型上的各种元素的XPS化学组成数据。
图3B示出了根据本文所述一实施方式,在5次ALD循环之后,存在于不同基板类型上的各种元素的XPS化学组成数据。
图3C示出了根据本文所述一实施方式,在额外ALD循环之后,存在于不同基板类型上的各种元素的XPS化学组成数据。
图4A示出了根据本文所述一实施方式,在ALD处理之前,存在于不同基板类型上的各种元素的XPS化学组成数据。
图4B示出了根据本文所述一实施方式,在5次ALD循环之后,存在于不同基板类型上的各种元素的XPS化学组成数据。
图4C示出了根据本文所述一实施方式的在退火工艺之后图4B的基板的XPS化学组成数据。
图5A示出了根据本文所述一实施方式的氩溅射后MoSix膜的XPS深度剖面(depthprofiling)数据。
图5B示出了根据本文所述一实施方式的MoSix膜的XPS化学组成数据。
图5C示出了根据本文所述一实施方式的代表MoSix膜的化学组成相对于时间的数据。
图6A示出了根据本文所述一实施方式的氩溅射后MoSix膜的XPS深度剖面数据。
图6B示出了根据本文所述一实施方式的MoSix膜的表面组成数据。
图6C示出了根据本文所述一实施方式的图6B的MoSix膜的主体(bulk)组成数据。
图6D示出了根据本文所述一实施方式的代表MoSix膜的化学组成相对于时间的数据。
图7是根据本文所述一实施方式的优先于存在于基板上的其他材料而选择性沉积在硅上的MoSix膜的截面隧道电子显微照片(tunneling electron micrograph;TEM)。
图8是示出根据本文所述一实施方式的将原生氧化硅选择性蚀刻成主体氧化硅的图表。
图9是根据本文所述一实施方式的接触结构的一部分的截面示意图。
为了便于理解,尽可能使用相同的元件符号来标识附图中相同的元件。可设想,一个实施方式的元件和特征可有利地结合到其他实施方式中,而无需进一步叙述。
具体实施方式
本文描述的实施方式包括利用ALD前驱物的基板依赖反应性进行区域选择性沉积的方法。更具体而言,本公开内容的实施方式涉及通过使用MoF6和Si2H6的基板选择性,在硅上优先于SiO2、SiON和SiNx选择性沉积MoSix。为了获得化学计量的MoSi2膜,在MoF6和Si2H6ALD循环之后,通过将Si2H6给送到富含Mo的MoSix膜上,将额外的硅掺入膜中。本文描述的方法亦提供了选择性的原生氧化物移除,这使得能够在不蚀刻主体氧化物材料的情况下移除原生氧化物材料。
在约120℃的温度下,通过使用MoF6和Si2H6前驱物的原子层沉积(ALD),实现了在硅上MoSix优先于SiO2和SiNx的高选择性沉积。沉积选择性是由于反应物(MoF6和Si2H6)与含SiO2和SiNx的基板之间缺乏化学反应而实现的。相反,MoF6在氢封端硅上以自限方式成核,随后的Si2H6暴露将MoFx还原为Mo0,此与Mo-Si键的形成一致。
X射线光电子光谱法(XPS)显示,MoF6和Si2H6的5次ALD循环选择性地在硅基板上沉积了亚化学计量的MoSi2膜。在ALD工艺中,MoF6和Si2H6前驱物重复顺序循环,在每次连续的前驱物暴露之间进行净化。亚化学计量MoSi2膜上的额外Si2H6剂量在不干扰对于SiO2和SiNx的沉积选择性的情况下将更多的硅掺入膜中。在一个实施方式中,主体MoSix膜具有约1.7与约1.9之间的Si∶Mo比,并且具有小于约10%的F和O杂质。相信此处描述的实施方式对于硅化物材料的形成,例如在源极/漏极接触结构的形成,优于传统的高压硅ALD循环。
根据本文描述的实施方式,在包含三维纳米级SiO2和SiNx特征的图案化硅基板上,分析了MoSix的沉积选择性。截面透射电子显微镜(transmission electron microscopy;TEM)显示在纳米级的三维结构上实现了选择性的MoSix沉积。在一个实施方式中,SiO2上存在少于约10个晶核(nuclei)/μm2;由于SiO2具有约107/μm2的羟基,此对应于SiO2上的羟基和硅上的Si-H基之间约107∶1的选择性。因此,相信硅化物沉积的基板依赖选择性能够消除钝化(即SAM)的利用。
实验
各种基板类型被用于此处描述的MoSix硅化物形成工艺。使用了四种类型的基板:P型硅(100)、在硅(100)上热生长的SiO2、SiON、和在单个基板上具有硅、SiO2及SiNx材料表面的图案化基板。除非另有说明,否则本文所述的SiON(氮氧化硅)是Si3N4,其在制造期间在氧中经受了反应性离子蚀刻和等离子体灰化。因此,SiON基板含有氧,所述氧类似于集成3D纳米级装置中处理后的Si3N4的状态。
将基板切成12mm×3mm的块,用丙酮、甲醇和去离子化(deionized;DI)H2O脱脂。通过将脱脂的基板浸入0.5%氢氟酸(水溶液)中30秒,移除硅上的原生氧化物。为了清洁过程的一致性,SiO2、SiON和图案化基板经受相同的清洁过程。在某些实施方式中,原生氧化物移除工艺是可从美国加利福尼亚州圣克拉拉市应用材料公司获得的预清洁工艺。
亦设想可利用基于等离子体的原生氧化物移除工艺。例如,NF3/H2和/或NF3/NH3等离子体清洁工艺可用于清洁基板的含硅表面并对其进行氢封端。在SiON基板上,相信NF3等离子体处理通过钝化活性羟基成核位点来防止或显著降低沉积选择性损失。
图8是曲线图800,示出了在等离子体处理期间随时间变化的原生氧化硅和主体氧化硅厚度的选择性蚀刻速率。数据802代表当暴露于NF3/NH3等离子体时的主体氧化硅厚度。数据804代表当暴露于NF3/NH3等离子体时的原生氧化硅厚度。时间806代表NF3/NH3等离子体何时开启,而时间808代表NF3/NH3等离子体何时关闭。
在一个实施方式中,用于选择性地将原生氧化硅选择性蚀刻成主体氧化硅的等离子体在处理腔室中原位形成。或者,在输送到处理腔室之前,例如通过远程等离子体源远程形成用于选择性地将原生氧化硅选择性蚀刻到主体氧化硅的等离子体。用于形成等离子体的前驱物包括NF3和NH3。在一个实施方式中,使用惰性载气,诸如氩气,来促进活性物种向基板的输送,以选择性地移除原生氧化硅。
在一个实施方式中,NF3∶NH3的比例在约1∶5与约1∶20之间,诸如约1∶10。在利用氩(Ar)载气的实施方式中,氩的提供量大于NF3但小于NH3。例如,NF3∶NH3∶Ar的比例是1∶10∶1.5。在其中执行选择性原生氧化物移除工艺的处理腔室环境的压力在约10毫托与约1000毫托之间,诸如在约100毫托与约500毫托之间,例如约200毫托。在一个实施方式中,压力为约190毫托。用于产生等离子体的功率在约10W与约500W之间,例如在约50W与约250W之间,诸如约100W。执行原生氧化物移除工艺的环境温度在约30℃与约70℃之间,诸如在约40℃与约50℃之间,例如约45℃。
在时间806处,等离子体被激发,并且原生氧化硅804发生厚度减小,此由原生氧化硅材料的厚度减小来示出。在一个实施方式中,等离子体工艺执行时长少于一分钟,例如少于40秒,诸如在约15秒与约30秒之间。在等离子体暴露的第一分钟或更短时间内,原生氧化硅804被蚀刻,而主体氧化硅实质上没有发生厚度减小,此表明比起主体氧化硅,更优先移除原生氧化硅的高度选择性。亦可设想,原生氧化物移除工艺对氮化硅材料也是选择性的,使得原生氧化硅优先于氮化硅被移除。
选择性移除原生氧化硅后对基板的原子力显微镜分析显示,暴露的硅表面(移除了原生氧化硅的地方)显示出亚埃的表面粗糙度。此种粗糙度符合移除原生氧化物后没有或实质上未蚀刻下层硅材料,因为硅材料的蚀刻预期会使表面变粗糙。
在某些实施方式中,在执行选择性原生氧化物移除工艺之后,残留材料,如(NH4)2)SiF6盐可保留在基板上。为了除去盐,执行可选的退火工艺。在一个实施方式中,退火工艺在约80℃与约160℃之间,诸如在约100℃与约140℃之间,例如约120℃。相信退火是例如藉由从基板的表面(诸如硅表面)挥发盐来移除盐的。
图9是根据本文所述一实施方式的其上形成有接触结构910的基板900的截面示意图。基板900包括硅材料膜902和形成在硅材料膜902上的主体氧化硅材料904。接触结构910形成在硅材料膜902的表面906上。在选择性移除原生氧化物之前,表面906上形成有原生氧化物薄膜。利用上述实施方式,从表面906移除原生氧化物,而实质上不改变或移除主体氧化硅904或下层的硅膜材料902。
形成在表面906上的接触结构910包括栅极916,其由栅极氧化物914、间隔件918和封盖920界定。在一个实施方式中,栅极916是含金属材料。间隔件918和封盖920包括含氮化物的材料,诸如氮化硅材料。在形成接触结构910之前或之后,利用此处描述的选择性原生氧化物移除工艺,能够实现表面906的准备以进行随后的金属沉积。在相邻接触结构910之间形成的通道912中的金属沉积从表面906向封盖920延伸。通过从表面906选择性地移除原生氧化物,提高了对下层的硅材料膜902的金属粘附力。
在移除原生氧化物后,使用高纯度N2气体吹干基板。将硅、SiO2、SiON和图案化基板一起装载在单个基板保持器上,以将基板暴露在同一ALD条件下。将基板装载到由涡轮分子泵泵送并由机械泵支撑的装载锁定腔室中。装载锁定的基础压力为约2.0x10-7托。随后,基板被原位转移到由离子泵和钛升华泵泵送的基础压力为约3.0x10-10托的超高真空腔室中。超高真空腔室装有单色XPS设备、扫描隧道显微镜(scanning tunneling microscope;STM)和使用热解氮化硼(pyrolytic boron nitride;PBN)加热器的退火系统。
首先在超高真空腔室中于120℃退火基板,并使用XPS测定基板的化学组成。将基板原位转移到基础压力为约5.0×10-7托的反应腔室中。对于MoSix沉积,使用MoF6(99%纯度)和Si2H6(99.99%纯度)前驱物。
在ALD循环期间,使用恒定的N2净化(80毫托),使用泄漏阀控制所述净化的压力。使用气动阀调节MoF6和Si2H6的给送。将膨胀体积用于MoF6和Si2H6给送。膨胀体积的利用包括用MoF6或Si2H6填充第二体积,并从其各自的第二体积来给送前驱物。MoF6的填充时间在约10毫秒与约10毫秒之间,诸如约40毫秒。MoF6的给送时间在约10毫秒与约100毫秒之间,诸如约50毫秒。Si2H6的填充时间在约1毫秒与约50毫秒之间,诸如约18毫秒。Si2H6的给送时间在约1毫秒与约50毫秒之间,诸如约18毫秒
MoF6和Si2H6的暴露是根据朗缪尔(Langmuirs,L)计算的,其中1L=1×10-6托×1秒。暴露期间的压力峰值使用反应腔室中的对流压力计(convectron gauge)进行监控。MoF6的剂量为约1.8MegaL,Si2H6的剂量为约4.2MegaL,两次给送之间的等待时间为2分钟。使用PBN加热器加热基板,并将温度保持在约100℃与约150℃之间,诸如约120℃。腔室壁保持在约65℃与约85℃之间的温度下。在一个实施方式中,MoF6剂量在约1.0MegaL与约10MegaL之间。在另一个实施方式中,Si2H6剂量在约1.0MegaL与约10MegaL之间。
在沉积循环之后,将基板原位转移至超高真空腔室进行XPS及STM分析。对于XPS测量,X射线是由Al Kα阳极(1486.7电子伏)产生的。XPS数据是使用恒定能量分析仪(constant analyzer-energy;CAE)获得的,步长(step width)为0.1eV,通能(passenergy)为50eV。将XPS检测器定位在与基板法线成60°的位置(与基板表面成30°的出射角),检测器接收角为7°。使用Casa XPS v.2.3程序用各自的相对灵敏度系数校正每个峰面积后,分析XPS光谱。此项工作中的所有化学组成皆标准化为所有组分的总和。扫描隧道显微镜是在-1.8V的基板偏压和200pA的恒定电流下进行的。
为了研究主体膜的元素组成,结合XPS进行氩离子溅射。采用5kV的透镜电压,在6.0x10-7托氩气下的束流(beam current)为1.2μA;由于光栅(raster)用于覆盖整个基板面积,因此电流密度为约1.2μA/50mm2。溅射过程中,将MoSix基板保持在25℃,以尽量减少任何热解吸。
结果
图1A显示了在120℃下连续给送MoF6和Si2H6之前及之后经HF清洁的硅表面的XPS化学组成数据。在120℃下,两组5.4MegaL的MoF6被给送在HF清洁的硅基板上。XPS显示Mo的饱和度为16%。随后,在120℃下,将4.2MegaL的Si2H6及额外42MegaL的Si2H6给送到MoF6饱和的硅表面上,导致硅达到饱和59%。在一个实施方式中,给送约1MegaL与约10MegaL之间的MoF6。在另一个实施方式中,给送约1MegaL与约10MegaL之间的Si2H6。在另一个实施方式中,额外给送约20MegaL与约50MegaL之间的Si2H6。
在HF清洁后,所有硅都处于0氧化态,含9%的O及12%C的污染物。相信污染由基板转移到真空过程中的偶然碳氢化合物吸附引起的。HF(水溶液)用于消除硅上的原生氧化物,使得硅表面以氢封端。应当注意,图1中的硅2p数据表示硅的总量,而硅(0)数据表示氧化态为0的硅的量。
在120℃下5.4MegaL的MoF6之后,14%Mo及38%氟沉积在HF清洁的硅表面上。在120℃下再加入5.4MegaL的MoF6后,Mo的浓度从14%增加到16%,F的浓度从38%增加到42%。Mo及F含量在额外增加5.4MegaL的MoF6后的此种微小增加表明MoF6对经HF清洁的硅的反应是自限的。硅表面的MoFx饱和后,F/Mo比为2.6,且所有硅都处于0氧化态。顺序给送4.2MegaL的Si2H6及42MegaL的Si2H6,表明Si2H6反应亦在MoFx覆盖的硅表面上达到饱和。相信,对于较厚的亚化学计量的MoSi2膜,可在表面上掺入额外的硅。然而,Si2H6在较薄(单层)Mo膜上以自限方式反应。
Si2H6饱和后,硅含量为59%,F含量降至10%。由于基板是硅,在给送Si2H6后硅含量的这种增加可部分归因于基板,因为发生了F解吸。然而,观察到Si2H6给送后Mo的衰减,此与硅的沉积一致。MoF6及Si2H6在氢封端硅上的反应证实了MoSixALD在Si-H封端硅上的潜力。
图1B说明了上文针对图1A所述的同一MoF6及Si2H6饱和给送系列的XPS化学组成数据,但在SiON基板上。如图所示,没有观察到反应。应该注意的是,尽管SiON基板名义上是SiON,但XPS在表面上仅显示出含量可忽略不计的N,因此所述基板主要是离子损伤的SiOx。在前3次MoF6脉冲后,观察到8%的F及可忽略不计的Mo(<1%)。对于剩余的饱和给送,SiON表面对MoF6及Si2H6都没有反应。尽管本研究中使用的SiON受到离子损伤,但硅处于+3及+4的氧化态,且数据与Si-O、Si-N、SiO-H强键一致,因此实质上杜绝了Si与Mo形成键。
图2A和图2B示出了HF清洁的硅基板的Si 2p及Mo 3d的XPS光谱,以比较每个实验操作中的氧化态。图2A示出了顺序给送MoF6及Si2H6后的Si 2p峰,显示了在120℃下给送10.8MegaL的MoF6(蓝线)后,硅保持在0氧化态,此符合Mo-Si键的形成及没有氟对硅的蚀刻。在120℃下给送4.2MegaL的Si2H6(红线)后,大部分硅保持在0氧化态。此符合MoSi2单层的形成。在较高的键合能时出现一个氧化硅小峰,表面可能是SiHxF4-x(x=2或3)或SiOx。图2B示出了顺序给送MoF6及Si2H6后的Mo 3d峰,表明MoF6饱和给送后Mo 3d峰存在于多个氧化态(黑线及蓝线)。在Si2H6给送(红线)后,所有Mo都被还原,峰以227.4eV为中心,此符合MoSi2的形成。
在首次给送5.4MegaL的MoF6之后,Si 2p峰保持0氧化态,此符合Si-Mo键的形成。Mo 3d峰出现多个氧化态,表明表面物种是MoFx,其中x=4、5及6(黑线)。额外5.4MegaL的MoF6没有改变Si 2p或Mo 3d峰(蓝线)的氧化态。数据表明在表面形成Si-Mo-Fx。注意,当Mo处于4-6的氧化态时,在MoF6饱和给送之后,F/Mo比是2.6(图1A XPS数据);因此,相信存在一些Mo-O键的形成。在4.2MegaL的Si2H6给送(红线)后,在Si 2p XPS峰上出现一个较高键合能(103电子伏)的小肩峰。此符合Si-F或Si-O的形成。Mo 3d光谱显示,在单次Si2H6给送后,所有的Mo都还原成键合能为227.4eV的Mo0。此符合MoSix的单层形成及任何残留的O或F以Si-O键及Si-F键的形式从Mo转移到Si。MoF6及Si2H6的简化反应(simplified reaction)可描述如下:
MoF6(g)+1.5Si2H6(g)→MoSi2(s)+SiF4(g)+3.5H2(g)+2HF(g)
硅基板上的MoSix的ALD特性及相对于SiO2及SiNx基板的选择性经由在图案化基板上的MoSix沉积的XPS来验证。图3A示出了一组三个基板的化学组成:HF清洁的硅、HF清洁的SiO2和HF清洁的图案化基板。图3B示出了在120℃下MoF6及Si2H6的5次ALD循环之后,图3A中每个基板的化学组成。数据表明缺硅的MoSix选择性地沉积在硅上而不是SiO2上。图案化样品的Si0组分亦通过MoSix沉积被选择性地衰减。图3C示出了在添加25.2MegaL(3次脉冲与10次脉冲之间)的Si2H6后,每个图3B基板的化学组成。额外的Si2H6将硅掺入MoSix表面。在额外的Si2H6脉冲期间,保持了对SiO2的选择性(在整个ALD过程中,SiO2具有0%Mo及0%Si0)。
将三个基板一起装载在单个基板保持器上,以确保其暴露在相同的沉积条件下。硅及SiO2基板允许在沉积期间于图案化基板上验证选择性。图案化基板在硅基板顶部具有被SiNx夹住的SiO2层。注意,图案化基板上的SiNx实际上是SiON,因为其在制造过程中在O2中被离子损坏及灰化。如图3A所示,30秒HF清洁移除了硅上的原生氧化物。热生长的SiO2厚度为300纳米,且30秒的HF清洁不会改变SiO2的元素组成或氧化态。HF清洁的图案化基板由SiNx、SiOx及Si0的混合物组成。
在120℃下,在MoF6及Si2H6的5次ALD循环后进行XPS,如图3B所示。XPS显示硅基板上的表面组成为32%的Mo及10%的Si,此对应于高度缺硅的MoSix。符合高选择性ALD的SiO2基板上没有MoSix沉积。在图案化的基板上,XPS显示沉积了5%的Mo,Si0衰减到1%。在图案化基板上的ALD过程中,表面N及O的占比没有显著变化。该数据与对图案化基板上的6%Si0具有选择性的缺硅MoSix被沉积一致。
图案化基板上的沉积选择性符合本文所述实施方式的三个方面:(1)MoSix沉积发生在硅基板上,但不发生在SiO2基板上。(2)MoSix沉积后,Si0(不是Si-N及Si-O中更高的氧化态Si峰)在图案化基板上衰减。(3)数值上,在具有6%Si0的图案化基板上沉积约4%的Mo与在HF清洁的基板上具有54%Si0的硅基板上沉积32%的Mo成比例。
即使在图1和图2中描述的ALD饱和实验中能够在硅上沉积单层MoSi2,连续的ALD循环也不会产生化学计量的MoSi2。相信,缺硅MoSix的形成是由于氟硅烷消除过程中表面Si-H物种解吸及残余Mo-F键,这些键不易藉由标准Si2H6给送移除。对于最初的1-3个单层,存在过量的来自基板的硅来帮助氟解吸,但是对于较厚的膜,Mo-F表面键可能会留存,因为唯一可用的硅来自气态的Si2H6。使用MoF6及Si2H6的整体氟硅烷消除化学作用符合以下两种化学反应之一:
1:
MoF6(g)+Si2H6(g)→Mo(s)+2SiHF3(g)+2H2(g)
2:
2MoF6(g)+1.5Si2H6(g)→2Mo(s)+2SiF4(g)+SiHF3(g)+3.5H2(g)+2HF(g)
为了形成MoSi2,在120℃下,将三个基板暴露于额外的25.2MegaL(在3次脉冲与10次脉冲之间,诸如6次脉冲)的Si2H6(参见图3C)。在额外的Si2H6暴露后,硅基板上的硅增加到20%,与硅被结合到膜中或基板表面上一致。额外的Si2H6给送没有降低相对于SiO2在硅上沉积的选择性。
图4A-4C示出了沉积后退火在HF清洁Si、SiO2及SiOH上选择性MoSix沉积的XPS化学组成数据。图4A示出了HF清洁后Si、SiO2及SiOH基板的XPS化学组成。图4B示出了XPS化学组成数据,该数据显示在5次MoSix ALD循环之后,再在120℃下额外进行6次Si2H6脉冲(25.2MegaL),MoSix仅选择性地沉积在硅上。图4C示出了在520℃下进行3分钟沉积后退火(post-deposition anneal;PDA)的基板的XPS化学组成数据。如图所示,PDA从MoSix膜中移除F,并将Mo还原为Mo0。
图4A示出了HF清洁后的SiON表面,所述表面主要由SiNx组成。在5次MoSix ALD循环之后,再额外加25.2MegaL的Si2H6,在HF清洁过的硅上有24%Mo及18%硅,而在SiOx及SiNx表面上检测到的Mo不到1%,如图4B所示。随后,三个基板在520℃下退火3分钟,此将硅基板上的F从25%降低到3%。520℃的PDA亦将硅基板上的Mo还原成Mo0,并将表面上的Si∶Mo比从约0.75降低到约0.5。此符合表面F以SiHF3或SiF4的形式解吸。PDA的XPS分析表明,PDA从膜中移除了F,此降低了F扩散到相邻MOSFET装置结构中的可能性。
利用原位STM及离位(ex-situ)原子力显微镜(atomic force microscopy;AFM),研究了硅及SiO2基板上沉积及PDA后的表面构形。在MoF6及Si2H6循环20次后,准备了用于原位STM的单独的HF清洁的硅基板。STM数据表明,MoSix膜是原子级平坦且保形的,均方根粗糙度为约2.8埃。将上述基板在超高真空腔室中于500℃下在约5.0×10-10托的压力下原位退火3分钟。在500℃退火后,膜变得更平坦,均方根粗糙度为约1.7埃。
在120℃下进行5次ALD循环,随后进行原位550℃退火之后,将另一个MoSix/HF清洁的硅基板放入到与N2平衡的5%H2的900℃尖峰退火的离位炉中。900℃尖峰退火后,使用AFM获得表面形貌。所述膜保持了4.75埃的亚纳米级均方根粗糙度,证实MoSix膜在高达约900℃时具有高的热稳定性。
在120℃下给送5次ALD循环,随后进行原位550℃退火3分钟,以确认通过对基板表面上的晶核进行计数来执行的选择性之后,SiO2基板表面的离位AFM图像数据。晶核密度为约9个晶核/μm2,证实硅沉积优于SiO2。相信,通过控制反应腔室的壁温,及通过使用短的高压Si2H6脉冲及较长的净化循环来促进ALD并避免化学气相沉积机制,会进一步改良本文所述实施方式的高沉积选择性。
亦进行了深度剖面研究,以确定MoSix膜的内部组成。图5A示出了在120℃下MoF6及Si2H6的5次循环之后,在HF清洁的硅上进行Ar+溅射之后的XPS化学组成数据。图5B示出了顺序Ar+溅射之后的Si 2p的XPS峰,其结果显示主体MoSix膜主要由Si0组成。图5C示出了在120℃下MoF6及Si2H6的5次循环后,针对Ar+在硅上的溅射时间绘制的沉积膜的化学组成数据。
图5A中所示的XPS数据来自于在120℃下使用MoF6及Si2H6的5次ALD循环沉积在HF清洁的硅基板上的MoSix膜,而没有额外的Si2H6掺入。随着溅射时间的增加,MoSix膜变薄,直到下层的硅基板暴露出来。溅射的前10分钟将F从35%降低到8%,同时来自氧化Mo及Mo0混合物的Mo转变成了纯Mo0。数据与主要键合在Mo上的表面F相一致。
连续溅射循环后,硅的量增加,Mo的量减少。此外,Si0的量与总硅一起增加,并且在100分钟总溅射时长后达到最大值43%。使用Si0与Mo0之比来区分纯MoSix相,因为在纯MoSix相中,Mo及硅都彼此结合并且氧化态都为0。移除基板表面的氧化硅及MoFx物种后,Si0的百分数超过Mo0。主体MoSix膜中的Si0∶Mo0比率为1.41,此对应于缺硅MoSix膜。注意,在膜的中心,硅与Mo的比率是1.77,因此,在没有背景O2/H2O的情况下,Si0∶Mo0的比可能更接近于2。
图5B示出了对应于图5A的每次XPS测量的Si 2p的原始XPS光谱。在第四次溅射循环后,99.2eV处的硅峰增加并加宽到更高的键合能。相比之下,在每个溅射循环之后,Mo峰的能量对应于Mo0。因此,相信主体MoSix膜主要是MoSix形式的Si0及Mo0,而顶表面及底界面富含SiOx。顶部SiO2与来自腔室环境的污染一致,而底部界面氧化物与不完全的(imperfect)离位HF清洁一致。
底部界面的亚化学计量氧化物不影响沉积及膜品质,此表明MoSix ALD的选择性对SiO2的品质十分灵敏。图5C示出了从图5A中的XPS测量获得的化学组分的百分比。在第二个溅射循环(总溅射时间中占40分钟)后,F降至3%以下,最终达到0%。膜主体中的O含量小于10%,但在MoSix-Si界面处缓慢增加到15%,此与界面氧化物层的存在一致。
为了理解额外的Si2H6给送对MoSix膜中Si∶Mo比的影响,对掺有额外硅的MoSix膜进行了XPS深度剖析。在MoF6及Si2H6在120℃下的5次ALD循环结束时,给送另外6次(25.2MegaL)Si2H6脉冲,随后在干式清洁的硅上在530℃下退火3分钟。本文所述退火后干式清洁工艺利用NF3及NH3的等离子体,以Ar作为载气。
图6A-6D示出了MoSix膜在暴露于额外的Si2H6给送后的XPS剖面数据。图6A示出了在120℃下,在MoF6及Si2H6的5次循环之后进行Si2H6的另外6次脉冲(25.2MegaL),随后的Ar+溅射干式清洁硅之后的XPS化学组成数据。图6B示出了MoF6及Si2H6的5次ALD循环之后,有及没有额外的Si2H6脉冲的XPS表面组成数据。5次ALD的Si∶Mo比为0.33,5次ALD+6次Si2H6脉冲后的Si∶Mo比为0.89,此与表面上硅的掺入一致。图6C示出了在使用Ar+溅射移除表面污染物之后,具有及不具有额外Si2H6脉冲的MoSix的XPS主体组成数据。5次ALD的Si∶Mo比为1.77,5次ALD+6次Si2H6脉冲后的Si∶Mo比为1.96。图6D示出了在MoF6及Si2H6的5次循环之后,随后在120℃下额外进行Si2H6脉冲,相对于在硅上的Ar+溅射时间绘制的MoSix膜的XPS化学组成数据。
图6A示出了在干式清洁的基板上进行每次操作后的一系列深度剖面XPS。在6次Si2H6/5次ALD循环后,基板表面有28%的F、20%的Si及28%的Mo。在530℃退火后,表面上的F大部分被移除,Mo全部被还原成Mo0,此符合图4C所示的表面上的F解吸。在此操作中,Si∶Mo比为0.89。相比之下,没有额外Si2H6给送的MoSix膜的Si∶Mo比仅为0.33,如图6B所示。
在移除表面氧化物污染后,对于进行了额外Si2H6脉冲的MoSix主体中的Si0∶Mo0为1.32(Si∶Mo=1.96)。如图6C所示,在没有额外掺入Si2H6的情况下,此相当于主体MoSix中Si0∶Mo0=1.41(Si∶Mo=1.77)。因此,相信在ALD循环之后,额外的Si2H6脉冲增加了缺硅的MoSix表面上的硅含量。相比之下,主体MoSix膜中的Si∶Mo比接近化学计量的MoSi2。图6D显示了每种化学组分在Ar+溅射时间函数中的XPS百分数,此符合主体MoSix膜中的MoSix形成。
在一个实施方式中,使用气动阀在6秒钟的持续时间内将4.2MegaL的Si2H6引入反应腔室。Si2H6工艺特性在比传统Si2H6给送参数短约10倍的给送持续时间内使用了大约3倍的Si2H6暴露量。因此,与传统给送方案相比,本文描述的实施方式在ALD给送期间利用了30倍高的分压。相信给送期间30倍高的瞬时压力能够使前驱物介导的Si2H6化学吸附层在表面上保持足够长的时间,以与Mo反应,从而将更多的硅掺入MoSix膜中。也相信硅的掺入是自限的,此能够使MoSix的生长速率达到约1.2纳米/循环。
使用四点探针测量法测量MoSix膜的电阻。在电学测量时,使用电阻大于10000欧姆·公分(ohm·cm)的向上掺杂的Si(001)作为基板。对于电学测量,在120℃下,在HF清洁的本征(intrinsic)(半绝缘)硅基板上沉积10次MoSix的ALD循环,随后进行原位550℃退火3分钟及在N2中平衡的5%H2下进行900℃尖峰退火。Ni点沉积作为探针触点。电阻为110欧姆,且使用无限薄层近似法(infinite sheet approximation),电阻率计算如下:
ρ=ktRmax=(4.53)×(10×10-7)×(110)=498μΩcm
其中k是常数,t是厚度,且Rmax是测得的最大电阻。
在图案化基板上进行截面TEM研究,以确认MoSix在纳米结构图案上的选择性。图7是MoSix/HF清洁的图案化基板的截面TEM图像。在HF清洁的图案化基板上,在120℃下进行5次MoSix ALD循环给送,随后再加入25.2MegaL的Si2H6。该基板在每个沉积步骤中的元素组成如图3A-3C所示。TEM图像显示MoSix在硅上,而不在SiNx或SiO2上沉积的完全选择性。在5次ALD循环之后,沉积在硅上的MoSix膜的厚度为约6.3纳米,随后是额外的25.2MegaL,其实现了约1.2纳米/循环的生长速率。由于MoSix ALD的每个循环的生长速率,相信5次ALD循环足以用于接触材料及接触装置结构。
亚化学计量MoSi2的选择性原子层沉积是藉由在氢封端Si上相对于热生长SiO2、离子损伤SiO2及SiNx的选择性工艺实现的。选择性基于MoF6及Si2H6对H-Si(而非SiO2或SiNx)的良好反应性,因为Si-O、Si-N、及SiO-H键足够强使得其在120℃下无法经受任一前驱物分解。MoF6及Si2H6都表现出自限行为,此允许沉积高保形的平滑膜,此膜的均方根粗糙度(root mean square;RMS)为2.8埃。在约500℃与550℃之间的温度下在超高真空中进行3分钟PDA,进一步将均方根粗糙度降至1.7埃。MoSix膜的品质在H2/N2环境中进行900℃尖峰退火后依然留存,此符合高热稳定性。
一项深度剖面XPS研究显示,主体MoSix膜接近化学计量的MoSi2(Si∶Mo=1.7-1.9),氧及氟含量小于10%。在5次ALD循环之后,MoSix膜的表面显示出Si∶Mo比为0.33的高度缺硅的MoSix表面,并且通过脉冲额外的Si2H6,所述表面处的Si∶Mo比改良至0.89。截面TEM成像显示,选择性保持在纳米级上,且MoSix可选择性地沉积在硅上而不消耗基板。
约1.2纳米/循环的MoSix膜生长速率能够实现少于10次ALD循环,诸如5次ALD循环,足以将MoSix膜用作接触材料。因此,当与传统的ALD工艺相比时,通过利用此处描述的实施方式,增大工艺生产量。相信,选择性MoSix沉积消除或实质减少了对复杂3D MOSFET结构(例如鳍状场效应晶体管)的光刻工艺的依赖。与SiO-H键相比,对Si-H键的选择性超过106。因此,即使不使用额外的钝化层,在纳米级上实现高选择性也是可能的。本文所描述的实施方式亦说明,通过在还原剂的ALD脉冲期间改变分压,可在保持选择性的同时,便利地切换硅化物相对于金属的ALD。
尽管上文针对本公开内容的实施方式,但是在不脱离本公开内容的基本范围的情况下,可设计本公开内容的其他及进一步的实施方式,并且本公开内容的范围由所附权利要求书确定。
Claims (15)
1.一种基板处理方法,包括以下步骤:
将包含主体氧化硅和原生氧化硅的含硅基板暴露于由NF3前驱物和NH3前驱物形成的等离子体,以选择性地从所述基板移除所述原生氧化硅,所述暴露步骤包括:
将所述基板加热至约40℃与约50℃之间的温度;和
将所述基板暴露于所述等离子体达少于约40秒的时间段。
2.如权利要求1所述的方法,其中所述NF3前驱物和所述NH3前驱物的NF3∶NH3比在约1∶5与约1∶20之间。
3.如权利要求2所述的方法,进一步包括以下步骤:
在暴露所述含硅基板期间,使Ar与所述等离子体一起流动。
4.一种基板处理方法,包括以下步骤:
将包含主体氧化硅和原生氧化硅的含硅基板暴露于由NF3前驱物和NH3前驱物形成的等离子体,以选择性地从所述基板移除所述原生氧化硅,所述暴露步骤包括:
将所述基板加热至约40℃与约50℃之间的温度;和
将所述基板暴露于所述等离子体达少于约40秒的时间段;
将基板加热到第一温度;
将所述基板暴露于包含氢的等离子体中;
将所述基板暴露于第一剂量的MoF6前驱物;
将所述基板暴露于第二剂量的Si2H6前驱物;
顺序循环将所述基板暴露于第一剂量和将所述基板暴露于第二剂量;和
在所述顺序循环之后,将所述基板暴露于第三剂量的所述Si2H6前驱物。
5.如权利要求4所述的方法,进一步包括以下步骤:
在约500℃与约550℃之间的第二温度下将所述基板暴露于第三剂量之后,退火所述基板。
6.如权利要求4的方法,其中所述第一温度在约100℃与约150℃之间。
7.如权利要求4所述的方法,其中所述顺序循环的执行少于10次。
8.如权利要求4的方法,其中包含氢的所述等离子体由选自NF3、NH3和H的组的前驱物形成。
9.如权利要求4所述的方法,其中在所述顺序循环期间执行利用N2的氮气净化工艺。
10.如权利要求4所述的方法,其中所述第一剂量在约10ms与约100ms之间的持续时间内进行。
11.如权利要求10所述的方法,其中所述第一剂量包括约1MegaL与约10MegaL之间的MoF6流量(flow rate)。
12.如权利要求10所述的方法,其中所述第二剂量在1约毫秒与约50毫秒之间的持续时间内进行。
13.如权利要求12所述的方法,其中所述第二剂量包括约1MegaL与约10MegaL之间的Si2H6流量。
14.如权利要求13所述的方法,其中所述第三剂量包括约20MegaL与约50MegaL之间的Si2H6流量。
15.一种基板处理方法,包括以下步骤:
将包含主体氧化硅和原生氧化硅的含硅基板放置在具有腔室壁的反应腔室中的加热器上;
将所述基板暴露于由NF3前驱物和NH3前驱物形成的等离子体,以选择性地从所述基板移除所述原生氧化硅,所述暴露步骤包括:
将所述基板加热至约40℃与约50℃之间的温度;和
将所述基板暴露于所述等离子体达少于约40秒的时间段;
将所述加热器上的所述基板加热到第一温度;
将所述腔室壁保持在低于所述第一温度的第二温度;
将所述基板的含硅表面暴露于氢中;
将所述基板暴露于第一剂量的MoF6前驱物;
将所述基板暴露于第二剂量的Si2H6前驱物;
顺序循环将所述基板暴露于第一剂量和将所述基板暴露于第二剂量;和
在所述顺序循环之后,将所述基板暴露于第三剂量的所述Si2H6前驱物。
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