CN109216158A - 形成硅锗锡层的方法和相关的半导体器件结构 - Google Patents
形成硅锗锡层的方法和相关的半导体器件结构 Download PDFInfo
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- CN109216158A CN109216158A CN201810651690.5A CN201810651690A CN109216158A CN 109216158 A CN109216158 A CN 109216158A CN 201810651690 A CN201810651690 A CN 201810651690A CN 109216158 A CN109216158 A CN 109216158A
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- BLMUAVFFONATJG-UHFFFAOYSA-L dipotassium;4-[4-(4-sulfonatophenyl)hexan-3-yl]benzenesulfonate Chemical compound [K+].[K+].C=1C=C(S([O-])(=O)=O)C=CC=1C(CC)C(CC)C1=CC=C(S([O-])(=O)=O)C=C1 BLMUAVFFONATJG-UHFFFAOYSA-L 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 68
- 239000004065 semiconductor Substances 0.000 title claims abstract description 21
- 230000015572 biosynthetic process Effects 0.000 title claims description 8
- 239000000758 substrate Substances 0.000 claims abstract description 92
- 230000008021 deposition Effects 0.000 claims abstract description 65
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims abstract description 44
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims abstract description 44
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 39
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000010703 silicon Substances 0.000 claims abstract description 35
- 239000002243 precursor Substances 0.000 claims abstract description 34
- 229910000078 germane Inorganic materials 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 14
- QUZPNFFHZPRKJD-UHFFFAOYSA-N germane Chemical compound [GeH4] QUZPNFFHZPRKJD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052986 germanium hydride Inorganic materials 0.000 claims abstract description 12
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 7
- 238000000151 deposition Methods 0.000 claims description 71
- 229910052732 germanium Inorganic materials 0.000 claims description 41
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 38
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 20
- 229910052718 tin Inorganic materials 0.000 claims description 20
- 229910000577 Silicon-germanium Inorganic materials 0.000 claims description 7
- 238000005229 chemical vapour deposition Methods 0.000 claims description 5
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 claims description 5
- -1 germanium Alkane Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 229910005898 GeSn Inorganic materials 0.000 claims 3
- 229910005096 Si3H8 Inorganic materials 0.000 claims 1
- 239000010410 layer Substances 0.000 description 83
- IWTIUUVUEKAHRM-UHFFFAOYSA-N germanium tin Chemical compound [Ge].[Sn] IWTIUUVUEKAHRM-UHFFFAOYSA-N 0.000 description 9
- 238000005253 cladding Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- VXGHASBVNMHGDI-UHFFFAOYSA-N digermane Chemical compound [Ge][Ge] VXGHASBVNMHGDI-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 210000001367 artery Anatomy 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000010349 pulsation Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 210000003462 vein Anatomy 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910020751 SixGe1-x Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- KAJBHOLJPAFYGK-UHFFFAOYSA-N [Sn].[Ge].[Si] Chemical compound [Sn].[Ge].[Si] KAJBHOLJPAFYGK-UHFFFAOYSA-N 0.000 description 1
- 210000002659 acromion Anatomy 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
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- H01L21/02518—Deposited layers
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- H01L21/02532—Silicon, silicon germanium, germanium
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- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
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- H01L29/16—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only elements of Group IV of the Periodic System
- H01L29/161—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only elements of Group IV of the Periodic System including two or more of the elements provided for in group H01L29/16, e.g. alloys
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Abstract
公开了一种形成硅锗锡(SiGeSn)层的方法。所述方法可包括:在反应室内提供衬底,暴露衬底于包含四氯化锡(SnCl4)的预沉积前体脉冲,暴露衬底于包含氢化硅源、甲锗烷(GeH4)和四氯化锡(SnCl4)的沉积前体气体混合物,和在衬底的表面上方沉积硅锗锡(SiGeSn)层。还提供了半导体器件结构,其包含通过本公开的方法形成的硅锗锡(SiGeSn)层。
Description
相关专利申请的交叉引用
本公开要求2017年7月5日提交并且标题为“形成硅锗锡层的方法及相关的半导体器件结构(METHODS FOR FORMING A SILICON GER MANIUM TIN LAYER AND RELATEDSEMICONDUCTOR DEVICE STRUCTURES)”的美国临时专利申请第62/528,818号的权益,该临时专利申请以引用方式并入本文。
技术领域
本公开一般涉及形成硅锗锡(SiGeSn)层的方法和含有一个或多个硅锗锡(SiGeSn)层的相关器件。本公开还一般涉及用于沉积硅锗锡(SiGeSn)外延层的化学气相沉积方法。
背景技术
人们对用于许多应用的含锡半导体材料如锗锡(GeSn)和硅锗锡(SiGeSn)越来越感兴趣,如用于先进微电子器件的高迁移率沟道和应变工程、用于光子器件的直接带隙IV族材料或用于光伏器件的SiGeSn合金。
已发现硅锗锡(SiGeSn)在某些衬底表面上的沉积可能极其困难。作为一个非限制性实例,硅衬底的表面上或锗衬底的表面上硅锗锡(SiGeSn)的形成可能极其困难,并且可能高度依赖于若干因素,包括但不限于用于沉积工艺的反应物前体。因此,需要采用优化的化学前体和条件来形成(例如,沉积)硅锗锡(SiGeSn)层的方法。
发明内容
根据本公开的至少一个实施方案,公开了一种形成硅锗锡(SiGeSn)层的方法。所述方法可包括:在反应室内提供衬底,暴露衬底于包含四氯化锡(SnCl4)的预沉积前体脉冲,暴露衬底于包含氢化硅源、甲锗烷(GeH4)和四氯化锡(SnCl4)的沉积前体气体混合物,和在衬底的表面上方沉积硅锗锡(SiGeSn)层。本公开的实施方案还可包括半导体器件结构,其可包含通过本公开的方法形成的硅锗锡(SiGeSn)层。
为了概述本发明和所取得的优于现有技术的优点,本发明的某些目的和优点已在上文描述。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何特定实施方案来实现。因此,举例来说,本领域技术人员应认识,本发明可以将取得或优化如本文所教导或建议的一个优点或一组优点的方式实施或进行而不一定取得如本文可能教导或建议的其他目的或优点。
所有这些实施方案均意在包括在所公开的本发明的范围内。通过下文结合附图对某些实施方案的详细描述,这些及其他实施方案对于本领域技术人员将是显而易见的,本发明不限于所公开的任何特定实施方案。
附图说明
尽管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方案的内容的权利要求书结束,但是在结合附图阅读时,可从本发明实施方案的某些实例的描述中更容易地确定本发明实施方案的优势,在附图中:
图1示意了工艺流程图,该图示意了根据本公开的实施方案的一种示例性沉积方法;
图2示意了通过本公开的实施方案形成的实例硅锗锡层的二(2)θx-射线衍射(XRD)扫描;
图3示意了包含通过本公开的实施方案形成的硅锗锡层的半导体器件结构;
图4示意了包含通过本公开的实施方案形成的硅锗锡层的又一半导体器件结构;和
图5示意了根据本公开的实施方案形成的硅锗锡层的二次离子质谱(SIMS)深度剖面扫描。
应理解,图中的元件仅为简单和清晰起见示意而不一定按比例绘制。例如,图中的一些元件的尺寸可能相对于其他元件放大,以有助于改善对本公开所说明实施方案的理解。
具体实施方式
尽管下文公开了某些实施方案和实施例,但本领域技术人员应理解,本发明延伸到所具体公开的实施方案和/或本发明用途以及显而易见的修改和其等同物之外。因此,预期本发明所公开的范围不应受下文描述的具体公开实施方案的限制。
如本文所用,术语“衬底”可指可使用的或上面可形成器件、电路或膜的任何一种或多种下层材料。
如本文所用,术语“外延层”可以指在底层大致上单晶衬底上的大致上单晶层。
如本文所用,术语“氢化硅源”可指其中引入了氢的硅源。
如本文所用,术语“化学气相沉积”可以指其中衬底暴露于一种或多种挥发性前体的任何方法,所述前体在衬底表面上反应和/或分解产生所期望沉积。
如本文所用,术语“硅锗锡”可指包含硅、锗和锡的材料并可表示为SixGe1-xSny,其中1≥x≥0并且其中1≥y≥0。
本公开的实施方案可包括形成硅锗锡(SiGeSn)层、特别是通过化学气相沉积法沉积硅锗锡(SiGeSn)层的方法。作为本公开的实施方案的一个非限制性实例,所述方法可包括用包含甲锗烷(GeH4)的沉积前体气体混合物作为锗源(或锗前体)来沉积硅锗锡(SiGeSn)层。如本文所述的化学气相沉积硅锗锡(SiGeSn)层的方法因此避免了与采用乙锗烷(Ge2H6)作为锗源相关的缺点,所述缺点包括更复杂的挥发性源包装、增加的成本和与采用乙锗烷(Ge2H6)的化学气相沉积工艺的选择性有关的限制。
另外,在形成硅锗锡(SiGeSn)时,可采用高级硅烷作为硅源。例如,已知采用甲硅烷(SiH4)作为硅源、乙锗烷(Ge2H6)作为锗源和四氯化锡作为锡的源来沉积硅锗锡(SiGeSn)。然而,硅锗锡(SiGeSn)的沉积优选在降低的衬底温度下进行,例如,在低于450℃的衬底温度下,而在这样的低温下,乙硅烷可能不会充分分解产生足够的反应性硅物种,从而限制了可被引入到硅锗锡(SiGeSn)层中的硅原子百分数。另外,由于前体的挥发性性质、前体的成本和采用乙锗烷(Ge2H6)可实现的选择性的缺乏,故使用乙锗烷(Ge2H6)是不理想的。因此,本公开的实施方案提供了沉积硅锗锡(SiGeSn)的方法,其采用替代的前体如高级硅烷作为硅源并采用甲锗烷(GeH4)作为锗源。
然而,采用替代的前体如高级硅烷和甲锗烷沉积硅锗锡(SiGeSn)不是直截了当的,而是需要新型加工阶段来实现高质量沉积。例如,采用包括暴露经加热衬底于作为硅源的乙硅烷(Si2H6)、作为锗源的甲锗烷(GeH4)和四氯化锡(SnCl4)的沉积方法可能导致衬底表面上硅锗锡(SiGeSn)的几乎不沉积到不沉积和/或延迟沉积,同时可能在衬底和沉积的硅锗锡(SiGeSn)之间额外形成锗(Ge)的夹层。
因此,在本公开的特定实施方案中,本公开的方法可包括暴露衬底于可包含四氯化锡(SnCl4)或者可既包含四氯化锡(SnCl4)又包含甲锗烷(GeH4)的预沉积前体脉冲。预沉积前体脉冲的采用将实质性地减少或甚至消除硅锗锡(SiGeSn)沉积中的延迟,并实质性地减少或甚至消除衬底与沉积的硅锗锡(SiGeSn)之间锗(Ge)的夹层的形成,从而允许在许多衬底表面上方沉积硅锗锡(SiGeSn),所述许多衬底表面包括但不限于硅衬底表面和锗衬底表面。
可结合图1理解本公开的方法,该图示意了用于形成硅锗锡(SiGeSn)层的方法的一个非限制性示例实施方案。例如,图1可示意用于形成硅锗锡(SiGeSn)层的方法100,其可包括工艺模块110,其中可向反应室中提供衬底并可在所述反应室内加热衬底至工艺温度。作为非限制性实例,反应室可包括化学气相沉积系统的反应室。本公开的实施方案可在可以名称IntrepidTM XP或得自ASM International N.V.的化学气相沉积系统中进行。然而,还预期也可采用其他反应室和来自其他制造商的替代的化学气相沉积系统来执行本公开的实施方案。
在本公开的一些实施方案中,衬底可包括平面衬底或图案化衬底。图案化衬底可包括这样的衬底,其可包含形成于衬底中或衬底表面上的半导体器件结构,例如图案化衬底可包含部分制造半导体器件结构如晶体管和存储元件。衬底可以含有单晶表面和/或一个或多个次表面,所述次表面可以包含非单晶表面,如多晶表面和非晶表面。单晶表面可包含例如硅(Si)、硅锗(SiGe)、锗锡(GeSn)或锗(Ge)中的一种或多种。多晶或非晶表面可包含电介质材料,如氧化物、氮氧化物或氮化物,例如氧化硅和氮化硅。
在本公开的一些实施方案中,衬底可包括“虚拟衬底,”其中虚拟衬底可包含设置于彼此之上的两种或更多种材料。例如,锗虚拟衬底可包含最上面的暴露的锗生长表面,其中所述虚拟衬底可包含沉积于另一材料例如硅衬底上的锗层。
继续参考图1,方法100可通过在反应室内加热衬底至所需工艺温度来继续。在本公开的一些实施方案中,方法100可包括加热衬底至低于大约450℃的温度、或至低于大约400℃的温度、或至低于大约350℃的温度、或至低于大约300℃的温度、或甚至至低于大约250℃的温度。在本公开的一些实施方案中,可能需要保持衬底于降低的沉积温度下,因为硅锗锡(SiGeSn)层在较高的沉积温度下不稳定并且这样的较高沉积温度可能导致低质量的相分离硅锗锡(SiGeSn)层,即高度缺陷的SiGeSn材料。
在衬底被加热至所需工艺温度后,方法100可通过暴露衬底于预沉积脉冲来继续,如图1的工艺模块120所示意。在本公开的一些实施方案中,暴露衬底于预沉积脉冲可包括暴露衬底于可包含四氯化锡(SnCl4)的预沉积脉冲。作为本公开的一个非限制性示例实施方案,可使衬底暴露于四氯化锡(SnCl4)大约超过3秒、或超过5秒、或甚至超过7秒的时间段。在本公开的一些实施方案中,在预沉积脉冲过程中,可将反应室设置到低于或等于大约760毫托、或低于大约400毫托、或甚至低于大约100毫托的压力。在本公开的一些实施方案中,在预沉积脉冲过程中,可使衬底温度保持在大约低于大约450℃、或低于大约400℃、或低于大约350℃、或低于大约300℃或甚至低于大约250℃的温度下。在本公开的一些实施方案中,在预沉积脉冲过程中,四氯化锡的流率大于大约3mg/分钟、或大于大约5mg/分钟或甚至大于大约10mg/分钟。
不受理论束缚,但据信预沉积前体脉冲可改变反应室内衬底的表面能并从而允许衬底表面上的沉积。已发现本公开的实施方案会改变衬底的表面能使得随后可采用高级硅烷作为硅源、甲锗烷作为锗源、四氯化锡(SnCl4)作为锡源来进行硅锗锡(SiGeSn)沉积。
在本公开的替代的实施方案中,暴露衬底于预沉积前体脉冲可包括暴露衬底于既包含四氯化锡(SnCl4)又包含甲锗烷(GeH4)的预沉积前体脉冲。在本公开的此类实施方案中,方法可包括在衬底的表面上形成锗锡(GeSn)种子层,所述锗锡(GeSn)种子层通过预沉积前体脉冲中采用的四氯化锡(SnCl4)和甲锗烷(GeH4)之间的反应形成。
在本公开的一些实施方案中,暴露衬底于预沉积脉冲可包括暴露衬底于可既包含四氯化锡(SnCl4)又包含甲锗烷(GeH4)的预沉积脉冲。作为本公开的一个非限制性示例实施方案,可使衬底暴露于四氯化锡(SnCl4)和甲锗烷(GeH4)二者达大约超过5秒、或超过10秒、或甚至超过15秒的时间段。在本公开的一些实施方案中,在预沉积脉冲过程中,可将反应室设置到低于或等于大约760毫托、或低于大约400毫托、或甚至低于大约100毫托的压力。在本公开的一些实施方案中,在预沉积脉冲过程中,可使衬底温度保持在大约低于450℃、或低于400℃、或低于350℃、或低于300℃或甚至低于250℃的温度下。在本公开的一些实施方案中,在预沉积脉冲过程中,四氯化锡的流率可大约大于大约3mg/分钟、或大于大约5mg/分钟或甚至大于大约10mg/分钟。在本公开的一些实施方案中,在预沉积脉冲过程中,甲锗烷的流率可大约大于10sccm、或大于大约200sccm、或甚至大于大约300sccm。
同样,不受理论束缚,但据信锗锡(GeSn)种子层的形成会改变衬底的表面能并从而允许硅锗锡(SiGeSn)层随后在锗锡(GeSn)种子层上方的沉积。因此,在本公开的一些实施方案中,暴露衬底于预沉积前体脉冲可还包括在衬底上形成催化生长表面。在本公开的一些实施方案中,所述方法可包括形成厚度介于大约50埃和大约100埃之间的锗锡(GeSn)种子层。
在衬底已暴露于预沉积前体脉冲后,可使衬底进一步暴露于沉积气体混合物以在衬底的表面上方沉积硅锗锡(SiGeSn)的层。如图1的工艺模块130所示意,暴露衬底于沉积前体气体混合物可包括选择沉积前体气体混合物以包含氢化硅源、甲锗烷(GeH4)和四氯化锡(SnCl4)。例如,方法100、特别是工艺模块130可包括选择氢化硅源以包含以下中至少之一:乙硅烷(Si2H6)、丙硅烷(Si3H8)或丁硅烷(Si4H10)。另外,氢化硅源可包含通用经验式为SixH(2x+2)的高级硅烷。
在本公开的一些实施方案中,暴露衬底于沉积前体气体混合物还包括保持反应室于低于或等于大约760毫托、或低于大约400毫托、或甚至低于大约100毫托的压力下。在本公开的一些实施方案中,在暴露衬底于沉积前体气体混合物的过程中,可使衬底温度保持在大约低于450℃、或低于400℃、或低于350℃、或低于300℃或甚至低于250℃的温度下。在本公开的一些实施方案中,在暴露衬底于沉积前体气体混合物的过程中,四氯化锡的流率可大约大于大约3mg/分钟、或大于大约5mg/分钟或甚至大于大约10mg/分钟。在本公开的一些实施方案中,在暴露衬底于沉积前体气体混合物的过程中,甲锗烷的流率可大约大于100sccm、或大于大约200sccm、或甚至大于大约400sccm。在本公开的一些实施方案中,在暴露衬底于沉积前体气体混合物的过程中,氢化硅源(例如,乙硅烷)的流率可大约大于3sccm、或大于大约10sccm、或甚至大于大约20sccm。
在暴露衬底于沉积前体气体混合物时,方法100可包括工艺模块140,其中方法还包括在衬底上方沉积硅锗锡(SiGeSn)层。在本公开的一些实施方案中,硅锗锡(SiGeSn)层可沉积至大于大约100埃、或大于大约500埃或甚至大于大约1000埃的厚度。在本公开的一些实施方案中,采用本公开的方法,硅锗锡(SiGeSn)的生长速率可大于大约10埃/分钟、或大于大约25埃/分钟、或甚至大于大约50埃/分钟。
在本公开的一些实施方案中,硅锗锡(SiGeSn)层可包含大于大约2at-%、或大于大约10at-%、或甚至大于大约30at-%的硅原子百分数(at-%)。在本公开的一些实施方案中,硅锗锡(SiGeSn)层可包含大于大约80at-%、或大于大约90at-%、或甚至大于95at-%的锗原子百分数。在本公开的其他实施方案中,硅锗锡(SiGeSn)层可包含大于大约2at-%、或大于大约10at-%、或甚至大于大约20at-%的锡原子百分数。
在一些实施方案中,包含硅、锗和锡的硅锗锡(SiGeSn)层可包含小于约20at-%、或小于约10at-%、或小于约7at-%、或小于约5at-%、或小于约3at-%、或小于约2at-%、或小于约1at-%的杂质,即除Si、Ge或Sn以外的元素。在一些实施方案中,包含硅、锗和锡的硅锗锡层包含小于约20at-%、或小于约10at-%、或小于约5at-%、或小于约2at-%、或小于约1at-%的氢。在一些实施方案中,包含硅、锗和锡的硅锗锡层可包含小于约10at-%、或小于约5at-%、或小于约2at-%、或小于约1at-%、或甚至小于约0.5at-%的碳。在一些实施方案中,包含硅、锗和锡的硅锗锡层可包含小于约5at-%、或小于约2at-%、或小于约1at-%、或小于约0.5at-%、或甚至小于约0.2at-%的氮。在一些实施方案中,硅锗锡层可包含小于约15at-%、或小于约10at-%、或小于约5at-%、或小于约3at-%、或小于约2at-%、或甚至小于约1at-%的氧。在一些实施方案中,硅锗锡层可在表面处包含平均小于约30at-%、或小于约20at-%、或小于约20at-%、或小于约5at-%、或甚至小于约3at-%的氧,其中所述表面可理解为从最顶表面起小于约20nm的厚度。在一些实施方案中,包含硅、锗和锡的薄膜可包含多于约80at-%、或多于约90at-%、或多于约93at-%、或多于约95at-%、或多于约97at-%、或多于约99at-%的硅、锗和锡。
在一些实施方案中,硅锗锡(SiGeSn)层可沉积在三维结构上。在一些实施方案中,在高宽比(高度/宽度)大于约2、大于约5、大于约10、大于约25、大于约50或大于约100的结构中,包含硅、锗和锡的SiGeSn层的台阶覆盖性可等于或高于约50%、高于约80%、高于约90%、约95%、约98%或约99%或更高。如本文所用,术语“台阶覆盖性”定义为衬底的侧壁上SiGeSn膜的厚度对衬底的水平面上SiGeSn膜的厚度的百分比。
图2示意了曲线图200,其示出了通过本公开的方法形成的实例硅锗锡层的2θx-射线衍射(XRD)扫描。在此非限制性实例中,衬底包含虚拟衬底,所述虚拟衬底还包含沉积于下面的硅衬底上的锗的缓冲层。标记为202的XRD扫描示意了在不采用预沉积脉冲的情况下沉积硅锗锡(SiGeSn)的过程。如标记为202的XRD扫描所示意,锗缓冲层的XRD峰和下面的硅衬底的XRD峰均可见但没有可辨别的XRD峰来指示任何硅锗锡(SiGeSn)的沉积。因此,标记为202的XRD扫描示意,在不采用预沉积脉冲的情况下,衬底上很少或没有硅锗锡(SiGeSn)沉积。相比之下,标记为204的XRD扫描示意了根据本公开的实施方案的沉积,其包括预沉积脉冲。回顾标记为204的XRD扫描,可以看到锗缓冲层的XRD峰和下面的衬底的XRD峰,然而,还存在附加的标记为206的XRD肩峰,这表明衬底表面上存在硅锗锡。因此,图2中的曲线图200示意,锗虚拟衬底上硅锗锡(SiGeSn)的沉积可能需要在硅锗锡沉积之前进行预沉积脉冲工艺以确保硅锗锡(SiGeSn)层的成功沉积。
本公开的实施方案还可提供半导体器件结构,其包含通过本文描述的方法形成的一个或多个硅锗锡(SiGeSn)层。例如,图3示意了半导体器件结构300的一个非限制性实例,其中的半导体器件结构包含部分制造的双栅MOSFET,通常称为FinFET。半导体器件结构300可包含衬底302、初始鳍结构304和通过本公开的实施方案形成的辅助鳍层306。在本公开的一些实施方案中,辅助鳍层306可包含硅锗锡(SiGeSn)层并且初始鳍结构304可包含锗(Ge)。作为一个非限制性实例,锗(Ge)初始鳍结构304上硅锗锡(SiGeSn)层306的沉积可包括四氯化锡(SnCl4)的初始预沉积脉冲以允许硅锗锡(SiGeSn)层306的基本直接沉积而不像不使用预沉积脉冲工艺时可能发生的那样形成中间锗层。FinFET器件300的器件性能取决于器件的关键尺寸,特别是初始鳍结构304的关键尺寸,因此本公开的实施方案使得硅锗锡(SiGeSn)能够直接沉积在初始锗鳍结构304上而不沉积不合需要的锗层,所述锗层可能改变FinFET器件结构300的关键尺寸。
作为又一个非限制性的半导体器件结构实例,图4示意了包含硅锗锡(SiGeSn)层408的部分制造光电子器件400。半导体器件结构400包含衬底402和缓冲层404,衬底402可包括硅衬底,缓冲层404可包括设置于硅衬底402上方的锗缓冲层。半导体器件结构400还可包括设置于锗缓冲层上方的有源区412,所述有源区包括熔覆层406和熔覆层410,两个熔覆层之间设置有量子阱层408。在本公开的一些实施方案中,熔覆层406和410可包含锡组成为大约5at-%的锗锡(GeSn),量子阱层408可包含锡组成介于大约10-15at-%之间的硅锗锡(SiGeSn)层。
熔覆层406和410及量子阱层408之间的界面414和416的质量可能对由半导体器件结构400制造的光电子器件结构的质量有着直接影响。因此,本公开的方法确保在沉积硅锗锡(SiGeSn)量子阱层408之前,下面的熔覆层406的上表面经受预沉积脉冲,例如四氯化锡的脉冲,使得下面的熔覆层406与量子阱层408之间的界面可以是平滑的、明确的并且基本上不含在不使用本公开的方法时可能发生的中间锗层。
图5示意了根据本公开的实施方案形成的硅锗锡层的二次离子质谱(SIMS)深度剖面扫描。标记为502的数据示意了锗的原子百分数,标记为504的数据示意了锡的原子百分数。标记为506的SIMS深度剖面扫描区域(大约40纳米和大约60纳米深度之间的区域)示意了在不使用预沉积脉冲的情况下尝试沉积硅锗锡层的过程中锗和锡的浓度的变化。相比之下,标记为508的SIMS深度剖面扫描区域(大约110纳米和大约130纳米深度之间的区域)示意了在采用预沉积脉冲工艺的情况下沉积硅锗锡层的过程中锗和锡的浓度的变化。在SIMS深度剖面分析中,特定特征的厚度可通过对剖面扫描中的“倾角(dip)”区域积分来确定。如从图5可观察到,与区域508相比,区域506中锗浓度的“倾角”要远更明显。因此,图5中的数据示意,与无预沉积脉冲时得到的结果相比,在采用预沉积脉冲时,本公开的实施方案产生远更薄的不希望有的锗层。
上文描述的本公开的示例实施方案不限制本发明的范围,因为这些实施方案仅是本发明的实施方案的实例,本发明由附随的权利要求书及其法定等同物限定。任何等同的实施方案均意在包括在本发明的范围内。实际上,除本文中展示和描述的那些外,本公开的各种修改,如所述元件的替代的可用组合,本领域技术人员可从说明书显而易见。此类修改和实施方案也意在落在附随的权利要求书的范围内。
Claims (14)
1.一种形成硅锗锡(SiGeSn)层的方法,所述方法包括:
在反应室内提供衬底;
暴露所述衬底于包含四氯化锡(SnCl4)的预沉积前体脉冲;
暴露所述衬底于沉积前体气体混合物,所述沉积前体气体混合物包含:氢化硅源、甲锗烷(GeH4)和四氯化锡(SnCl4);和
在所述衬底的表面上方沉积所述硅锗锡(SiGeSn)层。
2.根据权利要求1所述的方法,其中在所述反应室内提供衬底还包括选择所述衬底以包含生长表面,所述生长表面包含硅、锗和硅锗(SiGe)中的至少之一。
3.根据权利要求1所述的方法,其中暴露所述衬底于所述预沉积前体脉冲可还包括在所述衬底上形成催化生长表面。
4.根据权利要求1所述的方法,其中暴露所述衬底于四氯化锡(SnCl4)还包括暴露所述衬底于四氯化锡(SnCl4)大约3秒至大约20秒之间的时间段。
5.根据权利要求1所述的方法,其中暴露所述衬底于四氯化锡(SnCl4)还包括暴露所述衬底于甲锗烷(GeH4)和形成GeSn种子层。
6.根据权利要求1所述的方法,其中形成GeSn种子层还包括形成厚度介于大约50埃和大约100埃之间的GeSn种子层。
7.根据权利要求1所述的方法,所述方法还包括选择所述氢化硅源以包含以下中的至少之一:乙硅烷(Si2H6)、丙硅烷(Si3H8)或丁硅烷(Si4H10)。
8.根据权利要求1所述的方法,其中所述硅锗锡(SiGeSn)层包含大于2at-%的硅原子百分数。
9.根据权利要求1所述的方法,其中所述硅锗锡(SiGeSn)层包含大于80at-%的锗原子百分数。
10.根据权利要求1所述的方法,其中所述硅锗锡(SiGeSn)层包含大于2at-%的锡原子百分数。
11.根据权利要求1所述的方法,其中所述硅锗锡(SiGeSn)层包含外延层。
12.根据权利要求1所述的方法,所述方法还包括加热所述衬底至大约低于450℃的温度。
13.根据权利要求1所述的方法,其中在所述衬底的表面上方沉积所述硅锗锡(SiGeSn)层还包括采用化学气相沉积来沉积所述硅锗(SiGeSn)层。
14.一种半导体器件结构,所述半导体器件结构包含通过根据权利要求1所述的方法形成的硅锗锡(SiGeSn)层。
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US10685834B2 (en) | 2020-06-16 |
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