TW201720947A - 形成矽鍺錫膜的方法和包括該膜的結構與裝置 - Google Patents
形成矽鍺錫膜的方法和包括該膜的結構與裝置 Download PDFInfo
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- TW201720947A TW201720947A TW105129977A TW105129977A TW201720947A TW 201720947 A TW201720947 A TW 201720947A TW 105129977 A TW105129977 A TW 105129977A TW 105129977 A TW105129977 A TW 105129977A TW 201720947 A TW201720947 A TW 201720947A
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- 238000000034 method Methods 0.000 title claims abstract description 69
- KAJBHOLJPAFYGK-UHFFFAOYSA-N [Sn].[Ge].[Si] Chemical compound [Sn].[Ge].[Si] KAJBHOLJPAFYGK-UHFFFAOYSA-N 0.000 title abstract 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 37
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 28
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 81
- 239000002243 precursor Substances 0.000 claims description 68
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 239000000758 substrate Substances 0.000 claims description 47
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 27
- 229910052707 ruthenium Inorganic materials 0.000 claims description 27
- 239000013078 crystal Substances 0.000 claims description 12
- 239000011159 matrix material Substances 0.000 claims description 11
- 230000008878 coupling Effects 0.000 claims description 3
- 238000010168 coupling process Methods 0.000 claims description 3
- 238000005859 coupling reaction Methods 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- SFFUHUGVJGVRCJ-UHFFFAOYSA-N CCCCCCCCCC.[Ru] Chemical compound CCCCCCCCCC.[Ru] SFFUHUGVJGVRCJ-UHFFFAOYSA-N 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 125000005402 stannate group Chemical group 0.000 claims 1
- 229910052718 tin Inorganic materials 0.000 abstract description 31
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- 239000002019 doping agent Substances 0.000 description 17
- 239000007789 gas Substances 0.000 description 16
- 229910005898 GeSn Inorganic materials 0.000 description 14
- 230000008569 process Effects 0.000 description 13
- 239000012159 carrier gas Substances 0.000 description 11
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 4
- NNEUCPRHEGXIDG-UHFFFAOYSA-N helium;methane Chemical compound [He].C NNEUCPRHEGXIDG-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000007833 carbon precursor Substances 0.000 description 3
- -1 decane compound Chemical class 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical class CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000000407 epitaxy Methods 0.000 description 2
- UDNUMJGZDOKTFU-UHFFFAOYSA-N germanium;methane Chemical compound C.[Ge] UDNUMJGZDOKTFU-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- QCAWEPFNJXQPAN-UHFFFAOYSA-N methoxyfenozide Chemical compound COC1=CC=CC(C(=O)NN(C(=O)C=2C=C(C)C=C(C)C=2)C(C)(C)C)=C1C QCAWEPFNJXQPAN-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000001451 molecular beam epitaxy Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- GSJBKPNSLRKRNR-UHFFFAOYSA-N $l^{2}-stannanylidenetin Chemical compound [Sn].[Sn] GSJBKPNSLRKRNR-UHFFFAOYSA-N 0.000 description 1
- UYVWNPAMKCDKRB-UHFFFAOYSA-N 1,2,4,5-tetraoxane Chemical compound C1OOCOO1 UYVWNPAMKCDKRB-UHFFFAOYSA-N 0.000 description 1
- FQERLIOIVXPZKH-UHFFFAOYSA-N 1,2,4-trioxane Chemical compound C1COOCO1 FQERLIOIVXPZKH-UHFFFAOYSA-N 0.000 description 1
- 229910000927 Ge alloy Inorganic materials 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910000681 Silicon-tin Inorganic materials 0.000 description 1
- 229910008310 Si—Ge Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- JWVAUCBYEDDGAD-UHFFFAOYSA-N bismuth tin Chemical compound [Sn].[Bi] JWVAUCBYEDDGAD-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- IWTIUUVUEKAHRM-UHFFFAOYSA-N germanium tin Chemical compound [Ge].[Sn] IWTIUUVUEKAHRM-UHFFFAOYSA-N 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- LQJIDIOGYJAQMF-UHFFFAOYSA-N lambda2-silanylidenetin Chemical compound [Si].[Sn] LQJIDIOGYJAQMF-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 description 1
- FOAZAXXZMUVOGS-UHFFFAOYSA-N methane;tin Chemical class C.[Sn] FOAZAXXZMUVOGS-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 238000000038 ultrahigh vacuum chemical vapour deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02524—Group 14 semiconducting materials
- H01L21/02535—Group 14 semiconducting materials including tin
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- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
- H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
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Abstract
經揭示者為形成矽鍺錫(SixGe1-xSny)膜的方法。例示性方法包括在外延化學氣相沉積反應器中生長含有矽、鍺及錫的膜,且例示性方法適用於大量製造;亦經揭示者為包括矽鍺錫膜的結構與裝置。
Description
本發明揭示概括而言係關於形成含有矽鍺錫層之膜的技術,以及包括此等層的結構與裝置;更特別的是,經揭示的各種具體實例係關於:使用鍺烷及/或矽烷來形成矽鍺錫膜的方法、形成包括此等層之結構與裝置的方法、形成該層與結構的系統,以及包括該層的結構與裝置。
在各種電子裝置(如半導體裝置)與光子裝置(如雷射與太陽能裝置)中含有、或在預期中可含有矽鍺錫層,例如:能將SixGe1-xSny層用於形成直接能帶隙裝置、多量子井結構,及/或可將其用於(例如)對相鄰的鍺層提供形變以增加該鍺層的載子遷移率,亦能將SixGe1-xSny層用於形成可調節式能帶隙裝置,以及具有可調節式光學性質的光學裝置。為了得到所需的裝置性質,該SixGe1-xSny層通常具有晶體結構,其通常遵循著在下層(如緩衝層)的晶體結構。
可使用多種技術來沉積或生長SixGe1-xSny層,例如已將包括分子束外延與超高真空化學氣相沉積的真空製程用於形成SixGe1-xSny膜,不幸地是,此等技術慢、昂貴,且因而通常並不適用於大量製造。
此等製程中的鍺前驅物典型地包括二鍺烷(Ge2H6)或三鍺
烷(Ge3H8);當膜含有矽時,該矽前驅物典型地包括二矽烷(Si2H6)、三矽烷(Si3H8)或其它更高階的矽烷化合物,或者是通式為(H3Ge)xSiH4-x(x=1-4)、(H3Si)xGeH4-x(x=1-4)的異核Si-Ge化合物。
雖然對沉積或生長晶體SixGe1-xSny層而言,此等製程通常是可行的,但從某幾方面來看,使用二鍺烷、三鍺烷或更高階的鍺烷前驅物,及/或二矽烷或三矽烷是有問題的。例如:當與前驅物共同使用的是某些載流氣體(例如氫氣)及/或摻雜物(例如p型摻雜物)時,使用二鍺烷或如三鍺烷之更高階鍺烷前驅物來形成含有SixGe1-xSny的膜或層會沒有選擇性。
此外,二鍺烷處於濃縮形式時相對不穩定(有爆炸性),所以可能要限制容器中所含的前驅物數量,通常為少於154克,其依序導致使用此前驅物之製程的產率相對低;同樣地,更高階的矽烷相對昂貴,且可導致相對低的生長速率。因此,需要有用於形成SixGe1-xSny的經改善製程,此外,需要有適用於大量製造包括一層SixGe1-xSny之結構與裝置的經改善製程。
本發明揭示的各種具體實例係關於形成SixGe1-xSny膜的方法、包括SixGe1-xSny膜的結構與裝置,以及形成SixGe1-xSny膜的系統。可將本文所述之方法用在形成適用於多種應用的SixGe1-xSny膜,包括例如:半導體裝置中的壓力源膜與光子裝置中的可調節式能帶隙層。通常,當經揭示之各種具體實例所提出的點,關於先前技術方法、膜、結構、裝置及系統的缺點於下文中被更詳細討論時,該揭示會提供使用矽烷及/或鍺烷作為前驅物以形成SixGe1-XSny的方法,可將例示性方法用於以節省成本之方式來形成含有SixGe1-XSny的膜、結構及/或裝置,及/或以節省時間之方式來形成此等
膜、結構及/或裝置,本文所述的各種方法極特別適用於大量製造含有SixGe1-XSny膜的結構與裝置。
如本文中所用,SixGe1-XSny膜(在本文中也被稱為層)為可包含元素矽、鍺及錫之層。根據經揭示的各種具體實例,該SixGe1-XSny膜為晶體,且係覆蓋一晶體基質或層而外延形成,該膜可為合金形式,例示性SixGe1-XSny膜包含從0或多於0%至約15%、或約2%至約15%的錫;從0或多於0%至約30%、或約1%至約30%的矽;或者是約55%至約65%、或約75%至約95%的鍺;該層可包含額外元素,如碳(例如GeSnSiC合金)及/或其它元素,如:磷、硼,或者是其它元素,其平時被用來作為摻雜物及/或痕量的其它元素。
根據經揭示的某些例示性具體實例,在基質上形成SixGe1-XSny層的方法包括下列步驟:提供具有反應空間的反應器、在反應空間內提供基質、提供耦合至反應空間中的矽烷、提供耦合至反應空間中的鍺前驅物(例如鍺烷)、提供耦合至反應空間中的錫前驅物,以及在基質的表面外延形成一層SixGe1-XSny。可在反應腔室的入口或其附近(例如:在反應器的入口或注入岐管)將一或多種前驅物加以混合;根據進一步的態樣,可將交叉流動反應器用於形成SixGe1-XSny層;根據再進一步的態樣,矽烷與錫前驅物的流速比(不包含載流氣體)範圍為約2至約5、約2至約10,或者是約2至約15。例示性方法可進一步包括將如碳前驅物及/或摻雜物前驅物的額外前驅物提供至反應空間中,可在反應腔室的入口或其附近、及/或進一步在反應器的上游將此等額外前驅物與一或多種其它前驅物加以混合。
其它在基質上形成SixGe1-XSny層的例示性方法包括下列步驟:提供具有反應空間的反應器(例如交叉流動反應器)、在反應空間內提供基質、提供耦合至反應空間中的矽來源(例如矽烷)、提供耦合至反應空間中的鍺烷、提供耦合至反應空間中的錫前驅物,以及在基質的表面外延形成一層SixGe1-XSny;矽烷與錫前驅物的流速比範圍為約2至約15,或者是本文所述之其它矽烷:錫前驅物比例。例示性方法可進一步包括將如碳前驅物及/或摻雜物前驅物的額外前驅物提供至反應空間中,可在反應腔室的入口或其附近,或者是進一步在反應器的上游將此等額外前驅物與一或多種其它前驅物加以混合。
本文所述之方法的反應空間溫度可從範圍為約200℃至約500℃、約275℃至約475℃,或者是約300℃至約420℃。在此步驟期間的例示性反應腔室壓力範圍為約500托至約760托、約600托至約760托,或者是約700托至約760托,相對低溫及/或相對高壓會使得製造含一或多層SixGe1-XSny(如本文所述而形成)之結構與裝置的生產時間會變短。
根據所揭示之各種具體實例的例示性態樣,前驅物的流速比或分壓可經選擇以在大量製造條件下促進高品質膜形成。
根據所揭示的額外具體實例,結構中包括了一或多層SixGe1-XSny膜,例如使用本文中所揭示之方法而形成者;構中亦可包括額外層,如典型地用於形成裝置之層,例如:結構中可包括能形成緩衝層的鍺層,及/或作為FinFET裝置一部分的fin層。
根據所揭示的又一額外例示性具體實例,裝置中包括了含有一或多層SixGe1-XSny膜的結構,或者是係使用該結構來形成一種裝置。
而且根據所揭示的又一額外例示性具體實例,用於形成一或多層SixGe1-XSny膜的系統包括含有反應空間的氣相反應器(例如交叉流動反應器)、耦合至反應空間中的鍺前驅物(例如鍺烷)來源、耦合至反應空間中的錫前驅物,以及耦合至反應空間中的矽前驅物(例如矽烷)來源。可將系統進行配置,以在反應腔室(例如注入岐管)的入口或其附近將一或多種前驅物(例如所有前驅物)加以混合(例如具有經配置的操作控制機制來導致其混合)。
上述摘要和以下詳細敘述皆為例示性與說明性的,且並非本發明揭示之限制性內容。
當考慮到將詳細敘述與申請專利範圍連結至以下說明性圖示時,可得到對本發明揭示之例示性具體實例的更完整理解。
圖1說明了根據所揭示之例示性具體實例,用於形成一或多層SixGe1-XSny膜的系統。
圖2說明了根據所揭示之進一步例示性具體實例,用於形成SixGe1-XSny膜的方法。
圖3說明了一張XRD圖,其顯示各種組成物的SixGe1-XSny層,該層係在固定的SiH4、GeH4及SnCl4流之下,根據所揭示之例示性具體實例而形成。
圖4說明了一張RBS圖,其顯示例示性SixGe1-XSny層,該層係在經5%Sn與8%Si緩衝的Ge上方,根據所揭示之例示性具體實例而形成。
圖5說明了SixGe1-XSny膜的拉曼光譜,其根據所揭示之例示
性具體實例而形成。
圖6-13說明了根據本發明揭示之額外例示性具體實例所形成的例示性結構。
應了解的是,圖中成分之說明方式是為了簡單與清楚,並不需要依比例繪製。例如:相對於其它成分,可誇大圖中某些成分的尺寸,以助於改善對本發明揭示之說明性具體實例的理解。
以下所提供之方法、系統、結構及裝置的例示性具體實例敘述僅只是例示性的,且僅係用於說明之目的;接下來的說明並非用於限制揭示內容與請求項之範圍,此外,具有所宣稱特徵的多種具體實例之記載並非用於排除具有額外特徵的其它具體實例,或者是其它具體實例,其併入了經宣稱特徵的不同組合。
本發明揭示概括而言係關於形成層(如含有覆蓋基質之矽、鍺及錫的晶體合金層)的方法,該矽鍺錫(SixGe1-XSny)層可含有額外元素,如和矽鍺錫層形成晶格一部份的碳,及/或摻雜物(例如:如硼(B)的p型摻雜物及/或如磷(P)與砷(As)的n型摻雜物)。
例示性SixGe1-XSny層包含從0或多於0%至約15%的錫、約2%至約15%的錫,或者是約3%至約12%的錫,SixGe1-XSny可包含多於0%的錫、多於2%的錫,或者是多於3%的錫;該SixGe1-XSny層可額外或替代性地包含從0或多於0%至約30%的矽,或者是約1%至約30%的矽,或者是約3%至約25%的矽。例示性SixGe1-XSny層可額外或替代性地包含約55%至約65%的鍺,或者是約60%至約70%的鍺,或者是約80%至約90%的鍺。當該
等層包含碳時,該SixGe1-XSny層可包含從0或多於0%至約1%的碳,或者是約2%至約3%的碳,或者是約4%至約5%的碳。
可將該SixGe1-XSny層用於形成適合多種應用的結構與裝置,包括:形成應變層以增加在半導體裝置之其它層中的載子遷移率、作為量子阱結構和裝置的一部分,及/或作為光子裝置中之層,以下將討論例示性的結構與裝置。
如本文中所用,「基質」意指具有表面上可沉積材料的任何材料。基質可包含如矽(例如單晶矽、單晶鍺或其它半導體晶圓)的整體材料,或者是可包含覆蓋在整體材料上的一或多層,此外,該基質可包括各種拓撲結構,如在基質中某層之至少一部分或上方所形成的溝槽、通孔、線形及其類似結構,例示性基質包括矽晶圓、覆蓋矽的含鍺層及覆蓋鍺的含矽層。
現在回到圖式,圖1說明了適合用本文所述之方法在基質上形成SixGe1-XSny層的系統100,在說明性實例中,系統100包括了反應器102、矽來源104、鍺(例如鍺烷)前驅物106來源、錫前驅物來源108、吹洗及/或載流氣體來源110、選用混合器112、選用進氣室114及排氣(例如真空)源116。可用管路118-132與閥門134-140將來源104-110耦合至混合器112或反應器102。雖然未經說明,但如系統100之系統可為了其它前驅物〔如碳前驅物及/或摻雜物(例如:如磷或砷的n型摻雜物,或者是如硼的p型摻雜物及/或)〕而包括額外來源與相對應的傳送管路;額外或替代性地,在一或多種前驅物來源102-108中可含有一或多種摻雜物。
該來源可能相對純-例如:約99.999%或更純,或者是可與
載體混合,在是矽烷的情況下,矽烷來源104可在載體中包含約1至10%的矽烷或是約100%的矽烷;同樣地,鍺前驅物來源106(例如鍺烷)可在載體中包含約1.5%至約5%或約10%的鍺烷。此外,例示性系統可含有本文中所提到的前驅物、可基本上由其所組成,或者是由其所組成。
反應器102可為獨立反應器或群集工具的一部分,此外,可將反應器102用於如沉積製程的特定製程,或者是可將反應器102用於其它製程,例如:用於層的鈍化、清潔及/或蝕刻製程。舉例而言:反應器102中可包括通常用於外延化學氣相沉積(CVD)製程的反應器,如可從ASM獲得的Epsilon®2000 Plus、Epsilon®3200或Intrepid XP,並可包括直接電漿及/或遙控電漿裝置(圖中未說明),及/或各種加熱系統,如:輻射、感應及/或電阻加熱系統(圖亦未說明)。使用電漿可增強一或多種前驅物的反應性,圖中所說明的反應器是一種單基質、水平流動(交叉流動)反應器,其能使反應物層流以低滯留時間蓋過基質142,其依序促進相對快速的連續基質處理,適用於系統100的例示性CVD反應器經描述於2009年1月13日頒給Pomarede等等的美國專利案號7,476,627中,其內容在不與本發明揭示相衝突的程度下,以引用方式併入本文中。在適用於大量、相對低成本製造的條件下,會發現交叉流動反應器中的基質表面上將產生高品質的SixGe1-xSny層。
反應器102之反應腔室144的操作壓力可根據各種因子而變化,反應器102可經配置以在近乎環境壓力或較低壓力下進行操作,與例如:超高真空或分子束外延技術相較之下,其可使SixGe1-xSny層的形成相對快速。作為實例,在層形成期間的反應器102操作壓力範圍為約500Torr
至約760Torr、約600Torr至約760Torr,或者是約700Torr至約760Torr;反應空間溫度的範圍可為約200℃至約500℃、約275℃至約475℃,或是約300℃至約420℃。
矽烷來源104包含矽甲烷(SiH4),且可視需要包含載體。矽烷來源104可視需要包含一或多種摻雜物化合物,如典型用於組裝光子及/或半導體裝置之化合物,例示性p型摻雜物化合物包含B2H6,而例示性n型摻雜物化合物包含PH3與AsH3;因為矽甲烷相對較不昂貴且更容易取得,所以使用矽甲烷比使用更高階矽烷化合物〔如二矽烷、三矽烷、四矽烷(Si4H10)、新五矽烷(Si5H12)及更高階矽烷〕來得有利。本發明人發現使用本文中所揭示之壓力、交叉流動反應器及/或反應物比可使高品質SixGe1-xSny層形成,其使用矽甲烷而非高階矽烷。
鍺前驅物來源106可包含鍺甲烷(GeH4),且可視需要包含一或多種載流氣體及/或摻雜物化合物,如典型用於組裝光子及/或半導體裝置之化合物,例如:B2H6、PH3及/或AsH3。
因為當鍺甲烷與各種載流氣體(例如:氫、氮或其類似物)混合後相對具有選擇性,且即便當摻雜物與該前驅物一起使用時亦相對具有選擇性,所以使用鍺甲烷比使用其它過去用來形成SixGe1-xSny層的前驅物(如二鍺烷、三鍺烷及更高階矽烷)來得有利;另外,鍺甲烷與更高階的二鍺烷相較之下相對安全,且因而與更高階的鍺烷相較之下可被大量使用及/或輸送;另外,鍺甲烷可用作其它層(如鍺)的前驅物,且與更高階的鍺烷化合物相較之下更容易取得且相對較不昂貴。
錫前驅物來源108包含適合對SixGe1-xSny層提供錫的任何化
合物,例示性錫前驅物包含氯化錫(SnCl4)、氘化錫甲烷(SnD4),以及甲基及/或鹵化物取代的錫甲烷,如具有下列分子式的化合物:Sn(CH3)4-nXn,其中X為H、D(氘)、Cl或Br,且n為0、1、2或3;ZSn(CH3)3-nXn,其中Z為H或D、X為Cl或Br,且n為0、1或2;Z2Sn(CH3)2-nXn,其中Z為H或D、X為Cl或Br,且n為0或1;或者是SnBr4。適用於本發明揭示的某些例示性錫前驅物經更詳細地在2013年3月4日所申請的專利案號13/783,762(標題為TIN PRECURSORS FOR VAPOR DEPOSITION AND DEPOSITION PROCESSES)中進行討論,其內容在不與本發明揭示相衝突的程度下,以引用方式併入本文中。
吹洗及/或載流氣體來源110可包含任何適合的吹洗或載流氣體。適合作為載流或吹洗氣體的例示性氣體包含氮、氬、氦及氫。
系統100亦可包括配氣系統。能在氣體間(例如在來源104-110間)快速切換的例示性配氣系統如Schmidt等人在2012年4月10日所授權的美國專利案號8,152,922(標題為「Gas Mixer andManifold Assembly for ALD Reactor」)中所述,其內容在不與本發明揭示相衝突的程度下,以引用方式併入本文中。可將配氣系統用於例如:在氣體到達充氣部位114或反應器102之前,先混合一或多種前驅物氣體與載流氣體(其可與來自於氣體來源108之吹洗氣體相同或不同)。
現在回到圖2,其說明了形成SixGe1-xSny層的例示性方法200。方法200包括下列步驟:提供氣相反應器(步驟202)、在氣相反應器內提供基質(步驟204)、對反應器中的反應空間提供前驅物(步驟206),以及形成蓋過基質的SixGe1-xSny層(步驟208),方法200可視需要含有一或
多次地形成蓋過基質的絕緣層(步驟210),及/或在絕緣層內形成通路(步驟212)。
在步驟202進行期間,提供了適用於外延生長的CVD反應器,該反應器可為一種單基質、水平流動(交叉流動)反應器,適合的反應器可從ASM獲得的,其名為Epsilon®2000 Plus、Epsilon®3200及Intrepid XP。
在步驟204進行期間,於反應器的反應腔室內提供了基質該基質可被反應系統的裝載負載鎖定(loading load lock)給接收,並將其透過適合的輸送機制輸送至如反應腔室的反應空間中;在此步驟進行期間,可在反應空間中引入適合SixGe1-xSny層形成的壓力與溫度,如本文中所提到的壓力與溫度。
在步驟206中,將矽烷、鍺前驅物及錫前驅物提供至反應器的反應空間裡,前驅物可含有這些前驅物、可基本上由其所組成,或者是由其所組成。可在該矽烷、鍺前驅物及錫前驅物進入腔室前(例如在混合器112中)先將其進行混合,可在該矽烷、鍺前驅物及錫前驅物進入腔室之前,先將其獨自或以各種組成物形式與一或多種載流氣體進行混合,可將任何組成物形式的一或多種前驅物與反應腔室中的載體上升氣流進行混合,如在混合器中、在混合器的上升氣流中,及/或在其各自的來源內;在此步驟進行期間,矽烷的分壓範圍可為約5Torr至約20Torr、鍺前驅物(如鍺烷)的分壓範圍可為約300Torr至約450Torr,或者是錫前驅物(如氯化錫)的分壓範圍可為約1Torr至約3Torr。
在步驟208中,SixGe1-xSny的晶體層(例如:外延層)係形成
於基質上。如先前所指出的,在層形成期間的反應空間操作壓力範圍可為約500Torr至約760Torr、約600Torr至約760Torr,或者是約700Torr至約760Torr,而且反應空間溫度範圍可為約200℃至約500℃、約275℃至約475℃,或者是約300℃至約420℃。
在步驟210中,可在基質上沉積任何適合的絕緣層,如氧化矽或氮化矽;接著,在步驟212中,會在絕緣層內形成一或多個通孔。可使用反應性離子蝕刻法或其它適合技術來形成一或多個通孔。
在執行完步驟210與212的情況下,於步驟206中所形成的SixGe1-xSny層會選擇性地在通孔內形成。如先前所指出的,鍺甲烷前驅物之使用為有利,因為當使用到各種載流氣體(如氫),及/或該層含有一或多種摻雜物(如p型摻雜物)時,它相對具有選擇性。
圖3說明了一張X光繞射(XRD)圖,其顯示各種組成物的SixGe1-XSny層,該層係在固定的矽烷、鍺烷及氯化錫流速之下,生長於覆蓋在矽基質的鍺層上,該膜沉積期間的反應空間溫度在300℃與375℃間變化;該圖說明SixGe1-XSny層之組成可經調整以跟鍺晶格相匹配,或可經逐步應變。
圖4說明了對準與隨機產出的拉塞福回向散射光譜,其顯示於覆蓋在矽基質的鍺層上所形成的SixGe1-XSny層,該層包含約5%的錫與約8%的矽,且係在約320℃之溫度下生長。相較於隨機光譜而言,對準光譜的低產出指出了該SixGe1-XSny層為置換性合金。
圖5說明了各種組成物之SixGe1-XSny層的拉曼光譜,其說明了膜的三元鍵結及該膜為置換性合金。
圖6-12說明了例示性結構600-1200,可用本文中所描述的例示性系統及/或方法來使其形成。
結構600包括基質602、緩衝層604及SixGe1-XSny層606(例如:經外延形成而覆蓋過層604)。基質602可包含例如矽基質,基質602可包含用於形成電子或光子裝置的額外材料層;緩衝層604可包含(或其本身可為)例如經外延形成而覆蓋過基質602的鍺層;可使用例如方法200來形成SixGe1-XSny層606;可用結構600來形成各種電子或光子裝置。
緩衝層604的厚度範圍可為例如:約0.5至約0.7或約0.8至約0.9微米,或者是其厚度可為約一微米厚;SixGe1-XSny層606的厚度範圍可為約1至約9或約10至100nm之厚度。
除了結構700包括一層額外的層708之外,結構700與結構600相似。結構700包括基質702、緩衝層704、SixGe1-XSny層706及鍺層708,基質702、緩衝層704及SixGe1-XSny層706可和圖6所描述之相對應基質與層相同,且可具有相同厚度;鍺層708的厚度範圍可為約1至約3或約4至約9nm,或者是其厚度可為約10奈米厚,可經外延形成鍺層708而覆蓋過SixGe1-XSny層706,其使用例如以鍺作為前驅物之外延加工。
結構800包括基質802、緩衝層804、SixGe1-XSny層806及經外延形成而覆蓋過SixGe1-XSny層806的鍺錫(GeSn)層808。基質802與層802-806可和先前圖6與7所描述之相對應層相同或相似,且可具有相同厚度;GeSn層808可具有約1至約3或約4至約9nm之厚度,或者是其厚度可為約10nm,可使用鍺烷與如氯化錫之錫前驅物來形成GeSn層808,GeSn層808可含有約1%至約8%或約9%至約15%的錫。
結構900包括基質902、鍺層904、GeSn層906及SixGe1-XSny層908,該層之組成可和先前圖8所描述之相對應層相同(鍺層904相對應於緩衝層804),在用作說明之實例中,緩衝層904可具有與緩衝層604-804相同之厚度;GeSn層的厚度範圍可為約100nm至約400nm或約500nm至約900nm,或者是其厚度可為約1000nm;SixGe1-XSny層908可具有與SixGe1-XSny層606、706及806相同之厚度;除了GeSn層906與SixGe1-XSny層908是以相反的順序(相較於圖8所說明的結構)形成之外,結構900與結構800相似。
適合用來作為多量子井結構與裝置的結構1000包括基質1002、緩衝層1004、第一SixGe1-XSny層1006、GeSn層1008及第二SixGe1-XSny層1006。可用先前所描述之方法來形成各層,緩衝層1004、第一與第二SixGe1-XSny層1006與1010和GeSn層1008可具有等同於先前所指明之厚度,作為實例,緩衝層1004可為約1微米厚,第一SixGe1-XSny層1006與第二SixGe1-XSny層1010可各自為約50nm厚,且GeSn層1008可為約10nm厚,可依所需次數重複層1008-1010以形成多量子井結構。
圖11說明了適合用來作為多量子井結構或裝置的另一結構1100。結構1100包括基質1102、緩衝層1104、第一SixGe1-XSny層1106、第一Ge層1008、GeSn層1110、第二Ge層1112及第二SixGe1-XSny層1114;緩衝層1104、第一與第二SixGe1-XSny層1106與1114、第一與第二Ge層1008與1112及GeSn層1110可具有等同於先前所指明之厚度,作為實例,緩衝層1104可為約1微米厚,第一SixGe1-XSny層1106可為約50nm厚,第一Ge層1008與第二Ge層1112可為約50nm厚,GeSn層1110可為約10nm厚,
且第二SixGe1-XSny層1114可為約10nm厚,可依所需次數重複層1106-1114以形成多量子井結構。
圖12說明了根據本發明揭示之各種具體實例的又一結構1200。結構1200包括基質1202、第一SixGe1-XSny層1204、GeSn層1206及第二SixGe1-XSny層1208;除了結構1200不包括緩衝層1004之外,結構1200與結構1000相似,可使用被拿來形成結構1000的相同技術來形成結構1200之層,且該層可具有相同或相似厚度。
圖13說明了根據本發明揭示之額外例示性具體實例的再一結構1300。結構1300包括基質1302、絕緣層1304、在絕緣層1304內所形成之通孔1306、鍺層1308(例如其經外延形成而覆蓋過基質1302)及SixGe1-XSny層1310(例如其經外延形成而覆蓋過層1308);可使用例如方法200而在通孔1306內選擇性地形成層1308及/或1310;基質1302、Ge層1308及SixGe1-XSny層1310可與先前所描述之各層相同或相似,且可具有相同或相似厚度;絕緣層1304之厚度範圍可為約1至約10 nm或約10至約100nm。
要了解本文中所述之組態及/或做法在本質上是例示性的,且並非要將這些特定具體實例或實例視作具有限制性意味。在例示性方法之情況下,本文中所述之特定常規或步驟可代表加工策略(任何數量)中的一或多個,因此,經說明的各種行動可用經說明之順序來進行、用其它順序來進行、同時進行或在某些情況下被省略。
本發明揭示之主題包含各種加工、層、系統及組態的所有新穎及非顯而易組合與次組合,還有本文中所揭示之其它特徵、功能、行動及/或性質,以及其任何和所有等同者。
100‧‧‧系統
102‧‧‧反應器
104‧‧‧矽烷來源
106‧‧‧鍺前驅物來源
108‧‧‧錫前驅物來源/氣體來源
110‧‧‧吹洗及/或載體氣體來源
112‧‧‧混合器
114‧‧‧進氣室
116‧‧‧排氣源
118‧‧‧管路
120‧‧‧管路
122‧‧‧管路
124‧‧‧管路
126‧‧‧管路
128‧‧‧管路
130‧‧‧管路
132‧‧‧管路
134‧‧‧閥門
136‧‧‧閥門
138‧‧‧閥門
140‧‧‧閥門
142‧‧‧基質
144‧‧‧反應腔室
Claims (20)
- 一種在基質上形成SixGe1-xSny層的方法,該方法包括下列步驟:提供具有反應空間的反應器、在反應空間內提供基質、提供耦合至反應空間中的矽烷、提供耦合至反應空間中的鍺前驅物、提供耦合至反應空間中的錫前驅物來源,以及在基質的表面外延形成一層SixGe1-XSny。
- 根據申請專利範圍第1項之形成SixGe1-xSny層的方法,其中該鍺前驅物含有鍺的鍺烷。
- 根據申請專利範圍第1項之形成SixGe1-xSny層的方法,其中,在基質的表面外延形成一層SixGe1-XSny之該步驟期間,反應空間中的操作壓力在約500Torr至約760Torr之間。
- 根據申請專利範圍第1項之形成SixGe1-xSny層的方法,其中該層SixGe1-xSny含有多於0至約15%的錫。
- 根據申請專利範圍第1項之形成SixGe1-xSny層的方法,其中該層SixGe1-xSny含有多於0至約30%的矽。
- 根據申請專利範圍第1項之形成SixGe1-xSny層的方法,其中該層SixGe1-xSny含有約55%至約65%的鍺。
- 根據申請專利範圍第1項之形成SixGe1-xSny層的方法,其中,在基質的表面外延形成一層SixGe1-XSny之該步驟期間,經提供至反應空間中的該矽烷與該鍺前驅物比例為約2至約15。
- 根據申請專利範圍第1項之形成SixGe1-xSny層的方法,其中,在基質的表面外延形成一層SixGe1-XSny之該步驟期間,經提供至反應空間中的該矽烷與該鍺前驅物比例為約3至約12。
- 根據申請專利範圍第1項之形成SixGe1-xSny層的方法,其中,在基質的表面外延形成一層SixGe1-XSny之該步驟期間,反應空間中的操作溫度為約275℃至約475℃。
- 根據申請專利範圍第1項之形成SixGe1-xSny層的方法,其中提供錫前驅物之該步驟包括提供選自以下群組中的一或多種錫前驅物:SnCl4、SnD4,以及甲基及/或鹵化物取代的錫酸鹽。
- 根據申請專利範圍第1項之形成SixGe1-xSny層的方法,其中在基質的表面外延形成一層SixGe1-XSny之該步驟包括生長一層晶體層,其含有約2%至約15%的錫。
- 根據申請專利範圍第1項之形成SixGe1-xSny層的方法,其中在基質的表面外延形成一層SixGe1-XSny之該步驟包括生長一層晶體層,其含有約1%至約30%的矽。
- 一種形成包含SixGe1-xSny層之結構的方法,該方法包括下列步驟:提供包含反應空間的交叉流動反應器,在反應空間內提供基質,以及用矽烷與鍺烷在基質的表面形成含有SixGe1-XSny的晶體層。
- 根據申請專利範圍第13項之形成包含SixGe1-xSny層之結構的方法,其中該基質包含一個層,其含有覆蓋過矽之鍺。
- 根據申請專利範圍第13項之形成包含SixGe1-xSny層之結構的方法,其中 該含有SixGe1-xSny之層含有多於0%的錫至約15%的錫。
- 根據申請專利範圍第13項之形成包含SixGe1-xSny層之結構的方法,其中該含有SixGe1-xSny之層含有多於0%的矽至約30%的矽。
- 根據申請專利範圍第13項之形成包含SixGe1-xSny層之結構的方法,其中該含有SixGe1-xSny之層含有約55%的鍺至約65%的鍺。
- 根據申請專利範圍第13項之形成包含SixGe1-xSny層之結構的方法,其進一步包括下列步驟:形成覆蓋過基質的絕緣層,在絕緣層內形成通孔,以及在通孔內選擇性地形成該含有SixGe1-xSny之層。
- 一種結構,其包括根據申請專利範圍第13項之方法所形成的SixGe1-xSny晶體層。
- 根據申請專利範圍第19項之結構,其中該結構包括一個層,其含有覆蓋過SixGe1-xSny晶體層的鍺。
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2016
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KR20170064463A (ko) | 2017-06-09 |
US20170154770A1 (en) | 2017-06-01 |
KR102544300B1 (ko) | 2023-06-15 |
US9905420B2 (en) | 2018-02-27 |
TWI751115B (zh) | 2022-01-01 |
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