CN109652785B - 通过循环沉积在衬底上沉积金属硫族化物的方法 - Google Patents

通过循环沉积在衬底上沉积金属硫族化物的方法 Download PDF

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CN109652785B
CN109652785B CN201811177161.2A CN201811177161A CN109652785B CN 109652785 B CN109652785 B CN 109652785B CN 201811177161 A CN201811177161 A CN 201811177161A CN 109652785 B CN109652785 B CN 109652785B
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tin
metal
deposition
substrate
phase reactant
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CN109652785A (zh
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M·马蒂内恩
M·瑞塔拉
M·雷斯克拉
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ASM IP Holding BV
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Abstract

公开了一种通过循环沉积在衬底上沉积金属硫族化物的方法。所述方法使所述衬底与至少一种含金属的气相反应物接触，所述气相反应物包括由式M‑O‑C表示的部分化学结构，其中金属(M)原子键结至氧(O)原子，并且所述氧(O)原子键结至碳(C)原子；并使所述衬底与至少一种含硫族元素的气相反应物接触。还提供了包含由本公开的方法沉积的金属硫族化物的半导体装置结构。

Description

通过循环沉积在衬底上沉积金属硫族化物的方法
联合研究协议的合作对象
本文中要求的本发明是根据或代表和/或结合赫尔辛基大学(the University ofHelsinki)与ASM微量化学公司(ASM Microchemistry Oy.)之间的联合研究协议进行的。所述协议在作出所要求的本发明的日期当天和之前有效，并且所要求的本发明是作为在所述协议的范围内进行的活动的结果而作出。
技术领域
本公开大体上涉及通过循环沉积在衬底上沉积金属硫族化物的方法，且尤其涉及二硫化锡或二硫化锗的循环沉积。本公开还涉及包含通过循环沉积形成的金属硫族化物薄膜的半导体装置结构。
背景技术
近年来，二维(2D)材料由于在改善新一代电子装置的性能方面的潜力而引起广泛关注。例如，石墨烯是迄今研究最多的2D材料并且展现出高迁移率、透射率、机械强度和可挠性。不过，纯石墨烯中带隙的缺乏限制了其在半导体装置结构，如晶体管中的性能。石墨烯的此类限制激励了作为石墨烯类似物的替代性2D材料的研究。近来，以过渡金属硫族化物，且尤其是过渡金属二硫族化物作为石墨烯的替代选择引起了相当大的研究关注。过渡金属二硫族化物可以具有MX2的化学计算量，其描述过渡金属被夹在两层硫族原子之间，并且在金属-硫族元素之间具有较强的平面内共价键且在各层之间具有较弱的平面外范德华键。
然而，用于制造2D材料的可缩放的低温方法极少。目前，机械剥离块状晶体是最常用的形成方法，不过，尽管这种方法制造出质量良好的晶体，但所述方法无法制造出连续膜并且劳动量非常大，使得此类方法不适用于工业制造。化学气相沉积(CVD)已被用于沉积2D材料，但目前用于金属硫族化物，如二硫化锡(SnS2)的CVD工艺的操作温度超过600℃，而且无法制造出连续的大面积2D材料。因此，需要能够在较低沉积温度且在原子水平上控制膜厚度下制造出具有适合带隙的2D材料的方法。
发明内容
提供本概述是为了以简化的形式引入一系列概念。下文在本公开示例实施例的详细描述中将更详细地描述这些概念。本概述不打算标识所要求的主题的关键特征或必要特征，也不打算用于限制所要求的主题的范围。
在一些实施例中，提供了一种通过循环沉积在衬底上沉积金属硫族化物的方法。所述方法可以包括：使所述衬底与至少一种含金属的气相反应物接触，所述气相反应物包括由化学式M-O-C表示的部分化学结构，其中金属原子键结至一个氧原子(O)，并且所述氧(O)原子键结至碳(C)原子；并且使所述衬底与至少一种含硫族元素的气相反应物接触。本公开的实施例还提供了半导体装置结构，其包括由本文中所描述的方法沉积的金属硫族化物。
出于概述本发明以及所实现的优于现有技术的优势的目的，上文中描述了本发明的某些目的和优势。当然，应理解，未必所有这些目的或优势都可以根据本发明的任一特定实施例实现。因此，例如，本领域的技术人员将认识到，本发明可以按实现或优化如本文中所教示或建议的一种优势或一组优势，但不一定实现如本文中可能教示或建议的其它目的或优势的方式来实施或进行。
所有这些实施例都意欲在本文中所公开的本发明的范围内。本领域的技术人员从以下参照附图的某些实施例的详细描述将对这些和其它实施例显而易见，本发明不限于所公开的任何特定实施例。
附图说明
虽然本说明书以具体地指出并明确地要求保护被视为本发明实施例的内容的权利要求书结束，但在结合附图阅读时，可以从本公开的实施例的某些实例的描述中更容易地确定本公开的实施例的优势，在附图中：
图1是工艺流程图，示出了根据本公开的实施例的示范性循环沉积方法；
图2示出了根据本公开的实施例沉积的锡二硫族化物薄膜的掠入射x射线衍射(grazing incidence x-ray diffraction，GIXRD)数据；
图3也示出了根据本公开的实施例沉积的锡二硫族化物薄膜的掠入射x射线衍射(GIXRD)数据；
图4是包括根据本公开的实施例沉积的锡二硫族化物2D材料的结构的高角度环形暗场扫描透射电子显微镜检(HAADF-STEM)图像；
图5示出了从根据本公开的实施例沉积的锡二硫族化物薄膜获得的拉曼光谱；
图6示出了包含根据本公开的实施例沉积的金属硫族化物薄膜的示范性半导体装置结构；
图7示出了可以根据本公开的实施例用于沉积金属硫族化物薄膜的示范性反应系统。
具体实施方式
尽管下文公开了某些实施例和实例，但本领域的技术人员将理解，本发明延伸超出了本发明具体公开的实施例和/或用途和显而易见的修改以及其等效物。因此，希望所公开的本发明的范围不应受下文所描述的特定公开实施例的限制。
本文中呈现的图解不打算作为任何特定材料、结构或装置的实际视图，而仅仅是用以描述本公开的实施例的理想化图示。
如本文中所使用，术语“衬底”可以指可以用于，或在上面可以形成装置、电路或膜的任何底层材料。
如本文所使用，术语“循环沉积”可以指将前体(反应物)依序引入反应室中以在衬底上方沉积膜并且包含沉积技术，如原子层沉积和循环化学气相沉积。
如本文中所使用，术语“原子层沉积(ALD)”可以指在处理室中进行沉积循环，优选地多个连续沉积循环的气相沉积工艺。通常，在每个循环期间，将前体用化学方法吸附到沉积表面(例如衬底表面或先前沉积的底层表面，如来自先前ALD循环的材料)，由此形成不易与额外前体反应的单层或亚单层(即，自限性反应)。此后，必要时，可以随后将反应物(例如另一种前体或反应气体)引入到处理室中以用于将用化学方法吸附的前体转化成沉积表面上的所需材料。通常，此反应物能够与前体进一步反应。此外，在每个循环期间，还可以利用冲洗步骤以在转化用化学方法吸附的前体之后从处理室去除过量前体和/或从处理室去除过量反应物和/或反应副产物。此外，当使用前体组合物、反应性气体和冲洗(例如惰性载体)气体的交替脉冲进行时，如本文所使用的术语“原子层沉积”还意图包括由相关术语如“化学气相原子层沉积”、“原子层外延”(ALE)、分子束外延(MBE)、气体源MBE或有机金属MBE和化学束外延所指定的工艺。
如本文所使用，术语“循环化学气相沉积”可以指使衬底依序暴露于两种或多于两种挥发性前体的任何工艺，所述挥发性前体在衬底上反应和/或分解以产生所需沉积。
如本文所使用，术语“含硫族元素的气相反应物”可以指含有硫族元素的反应物(前体)，其中硫族元素是来自周期表第VI族的元素，包含硫、硒和碲。
如本文所使用，术语“膜”和“薄膜”可以指由本文所公开的方法沉积的任何连续或非连续结构和材料。例如，“膜”和“薄膜”可以包含2D材料、纳米棒、纳米管或纳米粒子，或甚至部分或完整分子层或者部分或完整原子层或原子和/或分子簇。“膜”和“薄膜”可以包括具有针孔的材料或层，但仍然是至少部分连续的。
如本文所使用，术语“部分化学结构”可以指化合物的一部分的化学结构，即少于完整化合物的化学结构。
如本文所使用，术语“2D材料”或“二维材料”可以指一个、两个或三个原子厚度的纳米级结晶材料。此外，“2D材料”或“二维材料”还可以指由每个单层约三个原子厚度的多个单层的结晶材料构成的有序纳米级结晶结构。
本公开的实施例可以包含通过循环沉积在衬底上沉积金属硫族化物的方法，且尤其是通过原子层沉积工艺沉积二硫化锡(SnS2)薄膜或二硫化锗(GeS2)薄膜的方法。作为非限制性实例，二硫化锡是一种新兴的材料，具有2D晶体结构，类似于众所周知的过渡金属二硫族化物(TMDC)，例如二硫化钼(MoS2)。相较于研究最多的2D材料石墨烯，二硫化锡具有相当大的带隙(块体约1.8-2.2eV，单层2.8eV)，使得二硫化锡更适用于半导体装置结构，例如场效应晶体管(FET)中。涉及二硫化锡作为FET装置中的通道材料的初始研究显示出与二硫化钼类似的电特性，例如多达50-200cm2V-1s-1的迁移率和106到108的开/关比，以及100AW-1的较强光响应度。二硫化锡薄膜的其它可能的应用领域包含但不限于催化、能量存储和光伏装置。
当前用于形成二硫化锡薄膜的方法不适于形成高质量、共形、低温薄膜。二硫化锡晶体可以通过机械剥离块体二硫化锡晶体形成，但此类方法不适于在适合衬底上形成二硫化锡达到原子级厚度准确度。此外，已展示二硫化锡的化学气相沉积，但此类工艺上在高沉积温度(大于600℃)下操作并且不适合制造纳米级共形薄膜。
循环沉积方法，如循环化学气相沉积和原子层沉积技术，本质上是可缩放的并且提供原子级准确膜厚度控制，这对于沉积高质量2D材料至关重要。此外，循环沉积方法，如原子层沉积，具有共形特征，由此能够均匀地涂布三维结构。Ham等人在《美国化学会-应用材料与界面(ACS Applied Material Interfaces)》,5,(2013)8880中展示了利用Sn(NMe2)4和H2S分别作为锡和硫族化物前体进行的二硫化锡原子层沉积。不过，此类用于形成二硫化锡的现有技术原子层沉积工艺可能有问题。例如，二硫化锡可能需要在较窄温度范围内进行沉积并且需要沉积后退火处理以使二硫化锡结晶。此外，Sn(NMe2)4前体还可能有些不稳定，这可能在大面积衬底，例如200mm或300mm衬底上产生质量较差的膜。
因此，需要能够在低温下，保形地且以原子级厚度准确度沉积金属二硫族化物膜的方法。此外，包括金属二硫族化物膜的半导体装置结构也是合乎需要的。
循环沉积工艺的非限制性示例实施例可以包含ALD，其中ALD通常是基于自限性反应，由此按照沉积循环，使用反应物的依序和交替脉冲沉积材料的约一个原子(或分子)单层。沉积条件和前体的选择通常应提供自饱和反应，使得一种反应物的吸附层留下不与同一反应物的气相反应物反应的表面终止状态(termination)。随后，使衬底与不同的反应物接触，所述不同的反应物与先前的终止状态反应而实现继续沉积。因此，交替脉冲的反应物的每个循环通常留下所需材料的不多于约一个单层。然而，如上文所提到的，熟练技术人员应认识到，在一个或多个ALD循环中可以沉积材料的不止一个单层，例如，如果发生了一些气相反应的话，而不管工艺的交替性如何。
在用于沉积过渡金属硫族化物膜的ALD型工艺中，一个沉积循环可以包括：使衬底暴露于第一反应物，从反应空间去除任何未反应的第一反应物和反应副产物，并且使衬底暴露于第二反应物，随后进行另一去除步骤。第一反应物可以包括含金属的前体，如含锡或锗的前体，并且第二反应物可以包括含硫族元素的前体。
前体可以用如氩气(Ar)或氮气(N2)等惰性气体分离，以防止反应物之间发生气相反应并实现自饱和表面反应。然而，在一些实施例中，可以移动衬底以分别接触第一气相反应物和第二气相反应物。由于所述反应自饱和，故通常不需要对衬底进行严格的温度控制以及对前体进行精确的剂量控制。不过，衬底温度优选地使得附带的气体物种既不冷凝成单层，也不在衬底表面上分解。在使衬底与下一反应化学品接触之前，如通过冲洗反应空间或通过移动衬底，从衬底表面去除剩余的化学品和反应副产物(如果存在的话)。可以借助于惰性冲洗气体从反应空间中有效地排出不合需要的气态分子。可以使用真空泵来辅助冲洗程序。
能够用于沉积或生长薄膜的反应器可以被用来进行沉积。此类反应器包含ALD反应器，以及配备有适当设备和构件以提供前体的CVD反应器。根据一些实施例，可以使用喷淋头反应器。
可以使用的适合反应器的实例包含可商购的单衬底(或单晶片)沉积设备，如购自美国亚利桑那州菲尼克斯(Phoenix,Arizona)的ASM America,Inc.和荷兰阿尔梅勒(Almere,Netherlands)的ASM Europe B.V.的
Figure BDA0001823067340000061
反应器(如
Figure BDA0001823067340000062
和
Figure BDA0001823067340000063
以及
Figure BDA0001823067340000064
)，以及
Figure BDA0001823067340000065
和
Figure BDA0001823067340000066
反应器。其它可商购的反应器包含以商品名
Figure BDA0001823067340000067
和XP8得自ASM Japan K.K(日本东京(Tokyo,Japan))的那些。在一些实施例中，反应器是空间ALD反应器，在所述反应器中，衬底在处理期间移动或旋转。
在一些实施例中，可以使用间歇反应器。适合的间歇反应器包含但不限于可购自ASM Europe B.V.(荷兰阿尔梅勒)的商品名为A400和A412PLUS的
Figure BDA0001823067340000068
系列反应器。在一些实施例中，利用了供舟皿在处理期间旋转的立式间歇反应器，如A412。因此，在一些实施例中，晶片在处理期间旋转。在其它实施例中，间歇反应器包括被配置成容纳10个或更少晶片、8个或更少晶片、6个或更少晶片、4个或更少晶片或2个晶片的小型间歇反应器。在使用间歇反应器的一些实施例中，晶片间的不均匀性小于3％(1西格玛)、小于2％、小于1％或甚至小于0.5％。
本文中所描述的沉积工艺可以任选地在连接到丛集工具的反应器或反应空间中进行。在丛集工具中，由于每个反应空间专用于一种类型的工艺，故每个模块中反应空间的温度可以保持恒定，与在每次操作前将衬底加热到工艺温度的反应器相比，这改进了生产量。另外，在丛集工具中，有可能减少将反应空间用泵增压到衬底之间所需的工艺压力水平的时间。
独立反应器可以配备有装载锁。在所述情况下，不必在每一操作之间冷却反应空间。在一些实施例中，用于沉积包括金属二硫族化物薄膜的薄膜的沉积工艺可以包括多个沉积循环，例如ALD循环。
在一些实施例中，使用循环沉积工艺在衬底上形成金属硫族化物薄膜，并且循环沉积工艺可以是ALD型工艺。在一些实施例中，循环沉积可以是混合式ALD/CVD或循环CVD工艺。例如，在一些实施例中，相较于CVD工艺，ALD工艺的沉积或生长速率可能较低。增大生长速率的一种方法可以是在比ALD工艺中通常所采用的温度高的衬底温度下操作，引起化学气相沉积工艺，但仍利用依序引入前体的优势的方法，此类工艺可以称作循环CVD。
根据本公开的一些实施例，使用ALD工艺在如集成电路工件等衬底上形成金属硫族化物薄膜。在一些实施例中，每一个ALD循环可以包括两个不同的沉积步骤或阶段。在沉积循环的第一阶段(“金属阶段”)中，使期望在上面进行沉积的衬底表面与包括用化学方法吸附到衬底表面上的第一气相反应物接触，由此在衬底的表面上形成反应物物种的不多于约一个单层，所述第一气相反应物包括至少一种含锡(Sn)的气相反应物或至少一种含锗(Ge)的气相反应物。在沉积循环的第二阶段(“硫族元素阶段”)中，使期望在上面进行沉积的衬底表面接触与先前用化学方法吸附的物种反应的第二气相反应物，以形成锡二硫族化物薄膜，所述第二气相反应物包括至少一种含硫族元素的气相反应物。
在一些实施例中，所述至少一种含金属的气相反应物，此处又称为“金属化合物”，可以包括由下式表示的部分化学结构：
M-O-C
其中金属(M)键结至氧(O)原子，并且所述氧(O)原子键结至碳(C)原子。在一些实施例中，各原子之间的键可以包括一个或多个单键，而在其它实施例中，各原子之间的键可以包括一个或多个双键。在本公开的一些实施例中，含金属的气相反应物包括含锡(Sn)的气相反应物或含锗(Ge)的气相反应物中的至少一种。
在一些实施例中，含锡(Sn)的气相反应物或锡(Sn)前体，此处又称为“锡化合物”，可以包括具有由下式表示的部分化学结构的至少一种含锡(Sn)的气相反应物：
Sn-O-C
其中锡(Sn)原子键结至一个氧(O)原子，并且所述氧(O)原子键结至碳(C)原子，其中所公开的原子之间的键可以包括单键或双键。在本公开的一些实施例中，所述至少一种含锡(Sn)的气相反应物由化学式Sn(OR)x表示，其中R是C1-C5烷基，或R是OCCH3基团，并且x是2-6的整数。作为非限制性实例，在一些实施例中，含锡(Sn)的气相反应物可以包括乙酸锡(IV)(Sn(OAc)4)。作为另一个非限制性实例，在一些实施例中，含锡(Sn)的气相反应物可以包括叔丁醇锡(IV)(Sn(OtBu)4)。
在一些实施例中，锡(Sn)前体，此处又称为“锡化合物”，可以包括具有由下式表示的部分化学结构的至少一种含锡(Sn)的气相反应物：
Figure BDA0001823067340000081
其中锡(Sn)原子与两个氧(O)原子键结或配位，并且所述氧(O)原子通过一个单键和一个双键键结至碳原子(C)，并且R可以是被取代或未被取代的烃基，如C1-C3烷基，例如-CH3。
在一些实施例中，锡(Sn)前体，此处又称为“锡化合物”，可以包括单齿配体。在一些实施例中，锡(Sn)前体，此处又称为“锡化合物”，可以包括双齿配体。在一些实施例中，锡(Sn)前体，此处又称为“锡化合物”，可以包括多齿配体。在一些实施例中，锡(Sn)前体可以不包括单齿配体。在一些实施例中，锡(Sn)前体不是由单齿配体组成。在一些实施例中，锡(Sn)前体可以不包括β二酮配体，如乙酰丙酮(acac)或2,2,6,6-四甲基-3,5-庚二酮(thd)配体。在一些实施例中，锡(Sn)前体可以不包括超过两种β二酮配体，如乙酰丙酮(acac)或2,2,6,6-四甲基-3,5-庚二酮(thd)配体。在一些实施例中，锡(Sn)前体可以不包括加合物配体，而在其它实施例中，锡(Sn)前体可以包括一种或多种加合物配体。在一些实施例中，锡(Sn)前体中的Sn具有+IV氧化态。在一些实施例中，锡(Sn)前体中的Sn具有+II氧化态。在一些实施例中，锡(Sn)前体中的Sn不具有+II氧化态。
在一些实施例中，锡(Sn)前体，此处又称为“锡化合物”，可以包括具有由下式表示的部分化学结构的至少一种含锡(Sn)的气相反应物：
Figure BDA0001823067340000091
其中锡(Sn)原子与两个氧(O)原子键结或配位，并且所述氧(O)原子通过一个单键和一个双键键结至碳原子(C)，并且R可以是被取代或未被取代的烃基，如C1-C3烷基，例如-CH3，且其中L是烃基，如烷基，其中所述烃可以含有或可以不含杂原子(即，不是C或H)。
在一些实施例中，锡(Sn)前体，此处又称为“锡化合物”，可以包括具有由下式表示的部分化学结构的至少一种含锡(Sn)的气相反应物：
L-Sn-O-C
其中锡(Sn)原子与一个氧(O)原子键结或配位，并且所述氧(O)原子键结至碳原子(C)，且其中L是烃基，如烷基，其中所述烃可以含有或可以不含杂原子(即，不是C或H)。在一些实施例中，锡(Sn)前体，此处又称为“锡化合物”，可以包括具有由下式表示的部分化学结构的至少一种含锡(Sn)的气相反应物：
X-Sn-L
其中X是卤基，如Cl，或不是含烃的配体，并且L是烃基，如烷基，其中所述烃可以含有或可以不含杂原子(即，不是C或H)。
在一些实施例中，锡(Sn)前体，此处又称为“锡化合物”，可以包括具有由下式表示的部分化学结构的至少一种含锡(Sn)的气相反应物：
Xy-Sn-Lw-y
其中X是卤基，如Cl，或不是含烃的配体，y是0到w或1到w-1，w是2到4并且L是烃基，如烷基，其中所述烃可以含有或可以不含杂原子(即，不是C或H)。
在一些实施例中，锡(Sn)前体，此处又称为“锡化合物”，可以包括具有由下式表示的部分化学结构的至少一种含锡(Sn)的气相反应物：
Xy-Sn-L4-y
其中X是卤基，如Cl，或不是含烃的配体，y是0到4或1到3，并且L是烃基，如烷基，其中所述烃可以含有或可以不含杂原子(即，不是C或H)。
在一些实施例中，金属前体，此处又称为金属化合物，可以包括具有由下式表示的部分化学结构的含Sn或Ge的气相反应物中的至少一种：
-M-O-C-
其中金属原子M(Sn或Ge)键结至一个氧(O)原子，并且所述氧(O)原子键结至碳(C)原子。为简单起见，在本文件中，将Ge前体或Ge分别称为“金属化合物”或“金属”，不过，它也可以分别被视为半金属前体或半金属。在本公开的一些实施例中，所述至少一种含金属的气相反应物由化学式M(OR)x表示，其中R是C1-C5烷基并且x是2-6的整数，且M是Ge或Sn。作为非限制性实例，在一些实施例中，含金属的气相反应物可以包括金属(IV)乙酸盐(M(OAc)4)。作为另一非限制性实例，在一些实施例中，含金属的气相反应物可以包括金属(IV)叔丁醇盐(M(OtBu)4)。
在一些实施例中，金属前体，此处又称为金属化合物，可以包括具有由下式表示的部分化学结构的至少一种含金属(Sn或Ge)的气相反应物：
Figure BDA0001823067340000101
其中金属原子M(Sn、Ge)与两个氧(O)原子键结或配位，并且所述氧(O)原子通过一个单键和一个双键键结至碳原子(C)，并且R可以是被取代或未被取代的烃基，如C1-C3烷基，例如-CH3。
在一些实施例中，金属前体，此处又称为金属化合物，可以包括单齿配体。在一些实施例中，金属前体，此处又称为金属化合物，可以包括双齿配体。在一些实施例中，金属前体，此处又称为金属化合物，可以包括多齿配体。在一些实施例中，金属前体，此处又称为金属化合物，可以不包括单齿配体。在一些实施例中，金属前体，此处又称为金属化合物，不是由单齿配体组成。在一些实施例中，金属前体，此处又称为金属化合物，可以不包括β二酮配体，如乙酰丙酮(acac)或2,2,6,6-四甲基-3,5-庚二酮(thd)配体。在一些实施例中，金属前体，此处又称为金属化合物，可以不包括超过两种β二酮配体，如乙酰丙酮(acac)或2,2,6,6-四甲基-3,5-庚二酮(thd)配体。在一些实施例中，金属前体，此处又称为金属化合物，可以不包括加合物配体，而在其它实施例中，金属前体，此处又称为金属化合物，可以包括一种或多种加合物配体。在一些实施例中，金属前体中的Sn或Ge具有+IV氧化态。在一些实施例中，金属前体中的Sn或Ge具有+II氧化态。在一些实施例中，金属前体中的Sn或Ge不具有+II氧化态。
在一些实施例中，使衬底暴露于所述至少一种含金属的气相反应物可以包括在衬底上方对金属前体进行脉冲，持续在约0.01秒与约60秒之间、在约0.05秒与约10秒之间或在约0.1秒与约5.0秒之间的时段。此外，在衬底上方对金属前体进行脉冲期间，金属前体的流动速率可以小于2000sccm，或小于500sccm，或甚至小于100sccm。此外，在衬底上方对金属前体进行脉冲期间，金属前体的流动速率可以是约1到约2000sccm、约5到约1000sccm或约10到约500sccm。
过量金属前体，如锡(Sn)前体和反应副产物(如果存在的话)，可以例如通过泵送惰性气体从衬底表面去除。例如，在本公开的一些实施例中，所述方法可以包括冲洗循环，其中冲洗衬底表面不到约2.0秒的时段。可以借助于由泵送系统产生的真空来去除过量的金属前体和任何反应副产物。
在沉积循环的第二阶段(“硫族元素阶段”)中，使衬底与包括至少一种含硫族元素的气相反应物的第二气相反应物接触。在本公开的一些实施例中，所述至少一种含硫族化物的气相反应物可以包括硫化氢(H2S)、硒化氢(H2Se)、甲硫醚((CH3)2S)或二甲基碲(CH3)2Te。
本领域的技术人员应了解，在本文所公开的循环沉积工艺中可以使用多种硫族元素前体。在一些实施例中，硫族元素前体选自以下清单：H2S、H2Se、H2Te、(CH3)2S,(NH4)2S、二甲亚砜((CH3)2SO)、(CH3)2Se、(CH3)2Te、元素或原子S、Se、Te、含有硫族元素-氢键的其它前体，如H2S2、H2Se2、H2Te2或具有式R-Y-H的硫族醇，其中R可以是被取代或未被取代的烃，优选地是C1-C8烷基或被取代的烷基，如烷基硅烷基，更优选地是直链或分支链C1-C5烷基，并且Y可以是S、Se或Te。在一些实施例中，硫族元素前体是具有式R-S-H的硫醇，其中R可以是被取代或未被取代的烃，优选地是C1-C8烷基，更优选直链或分支链C1-C5烷基。在一些实施例中，硫族元素前体具有式(R3Si)2Y，其中R3Si是烷基硅烷基并且Y可以是Se或Te。在一些实施例中，硫族元素前体包括S或Se。在一些实施例中，硫族元素前体包括S。在一些实施例中，硫族元素前体可以包括硫族元素，如元素硫。在一些实施例中，硫族元素前体不包括Te。在一些实施例中，硫族元素前体包括Se。在一些实施例中，硫族元素前体选自包括S、Se或Te的前体。在一些实施例中，硫族元素前体包括H2Sn，其中n是4到10。
适合硫族元素前体可以包含多种含硫族元素的化合物，只要其包含至少一个硫族元素-氢键即可。在一些实施例中，硫族元素前体可以包括硫族元素等离子体、硫族元素原子或硫族元素自由基。在需要高能硫族元素前体的一些实施例中，可以在反应室中或反应室上游产生等离子体。在一些实施例中，硫族元素前体不包括高能硫族元素前体，如等离子体、原子或自由基。在一些实施例中，硫族元素前体可以包括由如H2S等含硫族元素-氢键的硫族元素前体形成的硫族元素等离子体、硫族元素原子或硫族元素自由基。在一些实施例中，硫族元素前体可以包括硫族元素等离子体、硫族元素原子或硫族元素自由基，如包括硫、硒或碲的等离子体，优选包括硫的等离子体。在一些实施例中，所述等离子体、原子或自由基包括碲。在一些实施例中，所述等离子体、原子或自由基包括硒。在一些实施例中，硫族元素前体不包括碲前体。
在一些实施例中，使衬底暴露于含硫族元素的气相反应物可以包括在衬底上方对硫族元素前体(例如硫化氢)进行脉冲，持续在0.1秒与2.0秒之间或约0.01秒到约10秒或不到约20秒、不到约10秒或不到约5秒的时段。在衬底上方对硫族元素前体进行脉冲期间，被取代的硫族元素前体的流动速率可以小于50sccm，或小于25sccm，或小于15sccm，或甚至小于10sccm。
包括含硫族元素的前体的第二气相反应物可以与留在衬底上的含金属的分子反应。在一些实施例中，第二阶段硫族元素前体可以包括硫化氢并且反应可以在衬底的表面上沉积金属二硫化物。
可以例如通过冲洗气体脉冲和/或由泵送系统产生的真空，从衬底表面去除过量的第二源化学品和反应副产物(如果存在的话)。冲洗气体优选地是任何惰性气体，如但不限于氩气(Ar)、氮气(N2)或氦气(He)。如果冲洗(即，冲洗气体脉冲)或其它反应物去除步骤介于两个阶段之间，那么一个阶段一般被视为紧接着另一阶段。
使衬底替代地与第一气相反应物(即，含金属的前体)和第二气相反应物(即，含硫族元素的前体)接触的沉积循环可以重复两次或多于两次，直至沉积所需厚度的金属硫族化物。应了解，在本公开的一些实施例中，衬底与第一气相反应物和第二气相反应物接触的次序可以是这样的：先使衬底与第二气相反应物接触，随后与第一气相反应物接触。此外，在一些实施例中，循环沉积工艺可以包括使衬底与第一气相反应物(即，含金属的前体)接触一次或多次，随后使衬底与第二气相反应物(即，含硫族元素的前体)接触一次或多次，并且类似地，可以替代地包括使衬底与第二气相反应物接触一次或多次，随后使衬底与第一气相反应物接触一次或多次。此外，本公开的一些实施例可以包括非等离子体反应物，例如第一和第二气相反应物大体上不含离子化反应性物种。在一些实施例中，第一和第二气相反应物大体上不含离子化反应性物种、受激物种或自由基物种。例如，第一气相反应物和第二气相反应物可以包括非等离子体反应物以防止底层衬底的离子化损坏和由此产生的相关缺陷。
本文所描述的利用含金属的前体和含硫族元素的前体形成金属硫族化物薄膜的循环沉积工艺可以在ALD或CVD沉积系统中，在加热的衬底存在下进行。例如，在一些实施例中，方法可以包括将衬底加热到在约80℃与约150℃之间的温度，或甚至将衬底加热到在约80℃与约120℃之间的温度。当然，用于任何给定循环沉积工艺，如用于ALD反应的适当温度范围将取决于所涉及的表面终止状态和反应物物种。此处，温度取决于所用前体而变化并且一般处于或低于约700℃。在一些实施例中，对于气相沉积工艺，沉积温度一般处于或高于约100℃，在一些实施例中，沉积温度是在约100℃与约250℃之间，并且在一些实施例中，沉积温度在约120℃与约200℃之间。在一些实施例中，沉积温度低于约500℃、低于约400℃或低于约300℃。在一些情况下，例如，如果在所述工艺中使用另外的反应物或还原剂，则沉积温度可以低于约200℃、低于约150℃或低于约100℃。在一些情况下，沉积温度可以高于约20℃、高于约50℃并且高于约75℃。在本公开的一些实施例中，沉积温度，即沉积期间衬底的温度，是约150℃。
在一些实施例中，金属硫族化物薄膜的生长速率是约
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/循环到约
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Figure BDA00018230673400001314
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Figure BDA00018230673400001315
/循环。在本公开的一些实施例中，金属硫族化物的生长速率是约
Figure BDA00018230673400001316
/循环。
本公开的实施例可以包括循环沉积，所述循环沉积可以通过图1的方法100更详细地示出。方法100可以由工艺框110开始，所述工艺框包括将衬底提供到反应室中并将衬底加热到沉积温度，例如，所述衬底可以包括块体硅衬底，所述反应室可以包括原子层沉积反应室并且所述衬底可以被加热到约150℃的沉积温度。方法100可以由工艺框120继续，所述工艺框包括使衬底与含金属的气相反应物接触，例如，可以使所述衬底与乙酸锡(IV)(Sn(OAc)4)接触约1秒时段。在使衬底与含金属的前体接触后，可以通过冲洗/泵处理从反应室去除过量的含金属前体和任何副产物。方法100可以由工艺框130继续，所述工艺框包括使衬底与含硫族元素的气相反应物接触，例如，可以使所述衬底与硫化氢(H2S)接触约4秒时段。在使衬底与含硫族元素的前体接触后，可以通过冲洗/泵处理从反应室去除过量的含硫族元素的前体和任何副产物。
使衬底交替并依序与至少一种含金属的气相反应物接触并与至少一种含硫族元素的气相反应物接触的方法可以构成一个沉积循环。在本公开的一些实施例中，沉积金属硫族化物(例如金属二硫族化物)的方法可以包括重复所述沉积循环两次或多于两次。例如，方法100可以由决定门(decision gate)140继续，以确定方法100是继续还是退出。工艺框140的决定门是基于沉积的金属硫族化物膜的厚度确定，例如，如果金属硫族化物膜的厚度不足以用于所需装置结构，则方法100可以返回到工艺框120并且使衬底与含金属的气相反应物接触和使衬底与含硫族元素的气相反应物接触的工艺可以重复两次或多于两次。在沉积金属硫族化物膜达到所需厚度后，所述方法就可以退出150并且金属硫族化物膜可以经历另外的工艺以形成装置结构。
在本公开的一些实施例中，所沉积的金属硫族化物薄膜可以是至少部分结晶的。例如，图2示出了在约150℃沉积温度下，采用乙酸锡(IV)(Sn(OAc)4)作为含锡前体且硫化氢(H2S)作为含硫族元素的前体，利用所公开的原子层沉积方法沉积的二硫化锡薄膜的三(3)个非限制性实例的掠入射x射线衍射(GIXRD)数据。图2中所示的GIXRD数据展示了用不同Sn(OAc)4脉冲时间段沉积的二硫化锡薄膜，例如，标记为202的数据示出了用0.2秒的Sn(OAc)4脉冲时间段沉积的二硫化锡薄膜，标记为204的数据示出了用1秒的Sn(OAc)4脉冲时间段沉积的二硫化锡薄膜并且标记为206的数据示出了用2秒的Sn(OAc)4脉冲时间段沉积的二硫化锡薄膜。所述三(3)个二硫化锡薄膜的GIXRD数据的峰对应于(001)结晶取向。因此，在本公开的一些实施例中，沉积锡二硫族化物薄膜包括以主要(001)结晶取向沉积二硫化锡。
图3示出了在约150℃沉积温度下，采用乙酸锡(IV)(Sn(OAc)4)作为含锡前体且硫化氢(H2S)作为含硫族元素的前体，利用所公开的原子层沉积方法沉积的二硫化锡薄膜的三(3)个非限制性实例的GIXRD数据。图3中示出的GIXRD数据展示了用不同H2S脉冲时间段沉积的二硫化锡薄膜，例如，标记为302的数据示出了用8秒的H2S脉冲时间段沉积的二硫化锡膜，标记为304的数据示出了用4秒的H2S脉冲时间段沉积的二硫化锡膜并且标记为306的数据示出了用2秒的H2S脉冲时间段沉积的二硫化锡膜。如先前所展示，所述三(3)个二硫化锡薄膜的GIXRD数据的峰对应于(001)结晶取向。此外，GIXRD峰的强度随H2S脉冲时间段增加而增加，展示二硫化锡薄膜的结晶度随H2S脉冲时间的增加而增加。因此，在本公开的一些实施例中，二硫化锡薄膜的沉积包括对含硫族元素的前体(例如H2S)进行脉冲，持续超过约2秒，或超过约4秒，或甚至超过约8秒的时段。
尽管所沉积的金属硫族化物薄膜可以是至少部分结晶的，但金属硫族化物薄膜的结晶可以在沉积工艺期间缓慢地进行，使得较薄膜的结晶度可以小于较厚膜。当金属硫族化物薄膜包括厚度小于约10纳米的2D材料时，这可能会有问题。因此，在本公开的一些实施例中，所沉积的金属硫族化物薄膜可以经历沉积后退火处理以改善金属硫族化物薄膜的结晶度。例如，在一些实施例中，沉积金属硫族化物的方法还可以包括在约150℃与约300℃之间的温度下，对金属硫族化物进行沉积后退火。在一些实施例中，金属硫族化物的退火可以包括将金属硫族化物加热到约低于800℃、或约低于600℃、或约低于500℃、或甚至约低于400℃的温度。在一些实施例中，金属硫族化物薄膜的沉积后退火可以在包括硫族元素的氛围中执行，例如，沉积后退火处理可以在包括硫族化物，例如含硫化合物，如硫化氢(H2S)氛围的环境中执行。在一些实施例中，金属硫族化物薄膜的沉积后退火可以执行不到1小时、或不到30分钟、或不到15分钟、或甚至是不到5分钟的时段。在一些实施例中，金属硫族化物薄膜，如锡二硫族化物薄膜的沉积后退火可以在不含硫族元素，如S、Se或Te的氛围中，例如在惰性气体环境如N2，或稀有气体如Ar或He中，或在含氢气环境，如H2或H2/N2环境中执行。
包括根据一些本文所述的实施例沉积的金属硫族化物膜的薄膜，如二硫化锡薄膜可以是包括2D材料的连续薄膜。在一些实施例中，包括根据一些本文所述的实施例沉积的金属硫族化物膜的薄膜可以是厚度小于约100nm、小于约60nm、小于约50nm、小于约40nm、小于约30nm、小于约25nm，或小于约20nm，或小于约15nm，或小于约10nm，或小于约5nm或更小的连续薄膜。本文中提到的连续性可以是物理连续性或电连续性。在一些实施例中，使膜可以具有物理连续性的厚度可能与使膜具有电连续性的厚度不相同，并且使膜可以具有电连续性的厚度可能与使膜具有物理连续性的厚度不相同。
图4示出了包括根据本公开的实施例沉积的锡二硫族化物2D材料的结构的截面高角度环形暗场扫描透射电子显微镜检(HAADF-STEM)图像。HAADF-STEM图像示出的结构包括硅衬底、安置于硅衬底上的二氧化硅(SiO2)和安置于二氧化硅上的二硫化锡2D材料。所述结构还可以包括安置于二硫化锡上的碳(C)层，其中所述碳(C)层是作为成像程序的一部分施加。图4清楚地展示了具有2D晶体结构并且厚度小于约8纳米的结晶二硫化锡(SnS2)2D材料。
通过本公开的实施例沉积的锡二硫族化物薄膜可以包括二硫化锡并且可以呈SnSx形式，其中x可以在约0.75到约2.8范围内，或其中x可以在约0.8到约2.5范围内，或其中x可以在0.9到约2.3范围内，或替代地，其中x可以在约0.95到约2.2范围内。SnSx的元素组成范围可以包括约30原子％到约60原子％，或约35原子％到约55原子％或甚至是约40原子％到约50原子％的Sn。或者，SnSx的元素组成范围可以包括约25原子％到约75原子％、或约30原子％到约60原子％或甚至是约35原子％到约55原子％的S。
在本公开的一些实施例中，金属硫族化物，例如二硫化锡的相位可以利用拉曼光谱法测定。例如，图5示出了在250℃温度下退火之后，用325纳米激光器测量的7纳米厚的二硫化锡薄膜的拉曼光谱。图5中示出的拉曼光谱清楚地显示了在313cm-1处对应于SnS2峰的强度的峰。在测量中未检测到来自其它SnSx相，如SnS或Sn2S3的峰。因此，在本公开的一些实施例中，沉积锡二硫族化物包括沉积具有SnS2所提供的化学计算量的二硫化锡膜。
在另外的实施例中，SnSx可以包括低于约20原子％的氧、低于约10原子％的氧、低于约5原子％的氧或甚至是低于约2原子％的氧。在其它实施例中，SnSx可以包括低于约10原子％的氢，或低于约5原子％的氢，或低于约2原子％的氢，或甚至是低于约1原子％的氢。在又其它实施例中，SnSx可以包括低于约10原子％的碳，或低于约5原子％的碳，或低于约2原子％的碳，或低于约1原子％的碳，或甚至是低于约0.5原子％的碳。在本文概述的实施例中，元素的原子浓度可以利用卢瑟福背散射(Rutherford backscattering，RBS)测定。
在本公开的一些实施例中，可以将金属硫族化物薄膜沉积于三维结构上。在一些实施例中，在纵横比(高度/宽度)大于约2、大于约5、大于约10、大于约25、大于约50或甚至大于约100的结构中，金属硫族化物薄膜的阶梯覆盖率可以等于或大于约50％、大于约80％、大于约90％、约95％、约98％，或约99％或更高百分比。
在一些实施例中，根据一些本文所述的实施例沉积的金属硫族化物薄膜，如包括锡和硫族元素的锡二硫族化物薄膜，可以是结晶或多晶的。在一些实施例中，根据一些本文所述的实施例沉积的金属硫族化物薄膜的厚度可以是约20nm到约100nm。在一些实施例中，根据一些本文所述的实施例沉积的金属硫族化物薄膜的厚度可以是约20nm到约60nm。在一些实施例中，根据一些本文所述的实施例沉积的金属硫族化物薄膜的厚度可以大于约20、大于约30nm、大于约40nm、大于约50nm、大于约60nm、大于约100nm、大于约250nm、大于约500nm或更大。在一些实施例中，根据一些本文所述的实施例沉积的金属硫族化物薄膜的厚度可以小于约50nm、小于约30nm、小于约20nm、小于约15nm、小于约10nm、小于约5nm、小于约3nm、小于约2nm或甚至小于约1nm。
在一些实施例中，根据一些本文所述的实施例沉积的金属硫族化物薄膜，如锡或锗二硫族化物薄膜的厚度可以等于或小于约10个单层的金属硫族化物材料、等于或小于约7个单层的金属硫族化物材料、等于或小于约5个单层的金属硫族化物材料、等于或小于约4个单层的金属硫族化物材料、等于或小于约3个单层的金属硫族化物材料、等于或小于约2个单层的金属硫族化物材料，或甚至等于或小于约1个单层的硫族化物材料。
由本文所公开的循环沉积工艺沉积的金属硫族化物膜可以用于多种情形中，如用于形成半导体装置结构中。本领域的技术人员应认识到，本文所描述的工艺适用于许多情形，包含晶体管的制造。
作为非限制性实例，并且参看图6，半导体装置结构600可以包括场效应晶体管(FET)，其可以包含硅衬底602和安置于硅衬底602上的二氧化硅(SiO2)层604。半导体装置结构600还可以包括源极区606和漏极区608。在源极区与漏极区之间安置有根据本公开的实施例沉积的金属硫族化物薄膜610。金属硫族化物薄膜可以包括二硫化锡薄层并且可以由FET结构的通道区域组成。在本公开的一些实施例中，二硫化锡薄层的厚度可以小于10nm，或小于5nm，或甚至小于1nm。半导体装置结构600还可以包括安置于二硫化锡薄膜上的栅极电介质层612，其中所述栅极电介质层612可以包括二氧化铪(HfO2)。半导体装置结构600还可以包括安置于二硫化锡薄层610上的栅极电极614。
本公开的实施例还可以包含被配置成用于形成本公开的金属硫族化物膜的反应系统。更详细地，图7示意性地示出了包含反应室702的反应系统700，所述反应系统还包含用于将衬底(未图示)保持在预定压力、温度和环境条件下并且用于将衬底选择性暴露于各种气体的机构。前体反应物源704可以通过导管或其它适当的构件704A连接到反应室702，并且可以进一步连接到歧管、阀门控制系统、质量流量控制系统或用以控制来源于前体反应物源704的气态前体的机构。由前体反应物源704供应的前体(未图示)、反应物(未图示)在室温和标准大气压条件下可以是液态或固态的。可以在反应物源真空容器内汽化此类前体，所述反应物源真空容器可以维持处于或高于前体源腔室内的汽化温度。在此类实施例中，可以用载气(例如不活泼或惰性气体)输送汽化的前体，且接着通过导管704A将汽化的前体供给到反应室702中。在其它实施例中，在标准条件下，前体可以是蒸气。在此类实施例中，不需要汽化前体，并且前体可能不需要载气。例如，在一个实施例中，前体可以储存在气瓶中。反应系统700还可以包含额外的前体反应物源，如前体反应物源706，其也可以如上文所描述，通过导管706A连接到反应室。
冲洗气体源708还可以通过导管708A连接到反应室702，并且将各种惰性或稀有气体选择性供应到反应室702，以帮助从反应室去除前体气体或废气。可以供应的各种惰性或稀有气体可以来源于固态、液态或储存的气态形式。
图7的反应系统700还可以任选地包括退火台712，其中金属硫族化物可以经历生长后退火处理。在一些实施例中，生长后退火处理可以在反应室702中进行，而在一些实施例中，金属硫族化物薄膜可以被转移(例如在受控制的氛围下)到退火台712，其中所述生长后退火处理可以在所需的气态环境下执行。
图7的反应系统700还可以包括系统操作和控制机构710，所述系统操作和控制机构提供电子电路和机械组件以选择性操作包含在反应系统700中的阀门、歧管、泵和其它设备。此类电路和组件操作以从相应前体源704、706和冲洗气体源708引入前体、冲洗气体。系统操作和控制机构710还控制气体脉冲序列的时序、衬底和反应室的温度，及反应室的压力，以及实现反应系统700的适当操作所必需的各种其它操作。操作和控制机构710可以包含控制软件和电控制或气动控制的阀门，用以控制前体、反应物和冲洗气体进出反应室702的流动。控制系统可包含执行某些任务的模块，如软件或硬件组件，例如FPGA或ASIC。模块可以有利地配置成驻留在控制系统的可寻址存储媒体上，并且可以有利地被配置成执行一个或多个工艺。
相关领域的技术人员应了解，本发明的反应系统的其它配置是可能的，包含不同数目和种类的前体反应物源和冲洗气体源。此外，这些人还应了解，存在可以用于实现将气体选择性供给到反应室702中的目标的阀门、导管、前体源、冲洗气体源的许多布置。此外，作为反应系统的示意性图示，为了简化说明，省去了许多组件，并且此类组件可以包含例如各种阀门、歧管、纯化器、加热器、容器、通风孔和/或旁路。
上文所描述的本公开的示例实施例不限制本发明的范围，因为这些实施例仅仅是本发明实施例的实例，本发明由所附权利要求书和其合法等效物界定。任何等效实施例都意欲在本发明的范围内。实际上，除本文中所显示和描述的内容，如所描述元件的替代有用组合以外，本领域的技术人员从所述描述可以对本公开的各种修改显而易见。此类修改和实施例也意欲在所附权利要求书的范围内。

Claims (24)

1.一种通过循环沉积在衬底上沉积金属硫族化物的方法，所述方法包括：
使所述衬底与至少一种含金属的气相反应物接触，所述气相反应物包括由式M-O-C表示的部分化学结构，其中金属(M)原子键结至氧(O)原子，并且所述氧(O)原子键结至碳(C)原子，其中M选自锡(Sn)和锗(Ge)；并且
使所述衬底与至少一种含硫族元素的气相反应物接触。
2.根据权利要求1所述的方法，其中所述金属硫族化物包括金属二硫族化物。
3.根据权利要求1所述的方法，其中所述至少一种含硫族元素的气相反应物包括S、Se或Te。
4.根据权利要求1所述的方法，其中所述金属硫族化物包括低于10原子％的氧(O)含量。
5.根据权利要求1所述的方法，其中所述循环沉积包括原子层沉积。
6.根据权利要求1所述的方法，其中所述循环沉积包括循环化学气相沉积。
7.根据权利要求1所述的方法，其中所述含金属的气相反应物包括含锡(Sn)的气相反应物或含锗(Ge)的气相反应物中的至少一种。
8.根据权利要求7所述的方法，其中所述至少一种含锡(Sn)的气相反应物由化学式Sn(OR)x表示，其中R是C1-C5烷基并且x是2-6的整数。
9.根据权利要求7所述的方法，其中所述至少一种含锡(Sn)的气相反应物包括乙酸锡(IV)。
10.根据权利要求7所述的方法，其中所述至少一种含锡(Sn)的气相反应物由以下部分式表示：
Figure FDA0003795146090000011
其中锡(Sn)原子键结至两个氧(O)原子，并且所述氧(O)原子通过一个单键和一个双键键结至碳原子(C)，并且R包括烃基。
11.根据权利要求7所述的方法，其中所述至少一种含锡(Sn)的气相反应物由以下部分式表示：
Figure FDA0003795146090000021
其中锡(Sn)原子键结至两个氧(O)原子，并且所述氧(O)原子通过一个单键和一个双键键结至碳原子(C)，并且R是烃基，且L是另一烃基。
12.根据权利要求7所述的方法，其中所述至少一种含锡(Sn)的气相反应物由以下部分化学式表示：
L-Sn-O-C
其中锡(Sn)原子键结至氧(O)原子，并且所述氧(O)原子键结至碳原子(C)，且L是烃基。
13.根据权利要求1所述的方法，其中所述至少一种含硫族元素的气相反应物包括硫化氢(H2S)、硒化氢(H2Se)、甲硫醚((CH3)2S)或二甲基碲(CH3)2Te。
14.根据权利要求1所述的方法，其中所述方法包括至少一个沉积循环，其中所述衬底交替并依序与所述至少含金属的气相反应物和所述至少一种含硫族元素的气相反应物接触。
15.根据权利要求14所述的方法，其中所述沉积循环重复两次或多于两次。
16.根据权利要求1所述的方法，所述方法还包括将所述衬底加热到高于150℃的温度。
17.根据权利要求16所述的方法，所述方法还包括将所述衬底加热到低于500℃的温度。
18.根据权利要求1所述的方法，其中所述金属硫族化物包括二硫化锡。
19.根据权利要求1所述的方法，其中所述金属硫族化物包括二硫化锗。
20.根据权利要求1所述的方法，所述方法还包括在150℃与300℃之间的温度下，对所述金属硫族化物进行沉积后退火。
21.根据权利要求20所述的方法，其中所述金属硫族化物的沉积后退火是在硫化氢(H2S)氛围下执行。
22.一种半导体装置结构，其包括由根据权利要求1所述的方法沉积的金属硫族化物。
23.根据权利要求22所述的半导体装置结构，其中所述金属硫族化物包括晶体管结构中通道区域的至少一部分。
24.一种反应系统，其被配置成执行根据权利要求1所述的方法。
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