TWI607110B - 形成包括鍺錫之膜的方法及包括膜的結構及裝置 - Google Patents
形成包括鍺錫之膜的方法及包括膜的結構及裝置 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims description 73
- IWTIUUVUEKAHRM-UHFFFAOYSA-N germanium tin Chemical compound [Ge].[Sn] IWTIUUVUEKAHRM-UHFFFAOYSA-N 0.000 title description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 93
- 239000002243 precursor Substances 0.000 claims description 91
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 69
- 239000000758 substrate Substances 0.000 claims description 58
- 238000006243 chemical reaction Methods 0.000 claims description 38
- GVFOJDIFWSDNOY-UHFFFAOYSA-N antimony tin Chemical compound [Sn].[Sb] GVFOJDIFWSDNOY-UHFFFAOYSA-N 0.000 claims description 35
- JWVAUCBYEDDGAD-UHFFFAOYSA-N bismuth tin Chemical compound [Sn].[Bi] JWVAUCBYEDDGAD-UHFFFAOYSA-N 0.000 claims description 28
- GSJBKPNSLRKRNR-UHFFFAOYSA-N $l^{2}-stannanylidenetin Chemical compound [Sn].[Sn] GSJBKPNSLRKRNR-UHFFFAOYSA-N 0.000 claims description 18
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 14
- 229910052715 tantalum Inorganic materials 0.000 claims description 14
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 14
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 13
- 229910052707 ruthenium Inorganic materials 0.000 claims description 13
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 claims description 12
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- UYVWNPAMKCDKRB-UHFFFAOYSA-N 1,2,4,5-tetraoxane Chemical compound C1OOCOO1 UYVWNPAMKCDKRB-UHFFFAOYSA-N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- 229910052746 lanthanum Inorganic materials 0.000 claims 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims 1
- 125000005402 stannate group Chemical group 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 description 25
- 239000002019 doping agent Substances 0.000 description 18
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 17
- 229910052732 germanium Inorganic materials 0.000 description 16
- 239000012159 carrier gas Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 229910005898 GeSn Inorganic materials 0.000 description 10
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical class CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 4
- 229910000078 germane Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052703 rhodium Inorganic materials 0.000 description 4
- 239000010948 rhodium Substances 0.000 description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 4
- 238000011010 flushing procedure Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WMLOOYUARVGOPC-UHFFFAOYSA-N [Ta].[Sn] Chemical compound [Ta].[Sn] WMLOOYUARVGOPC-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 239000013590 bulk material Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- FQERLIOIVXPZKH-UHFFFAOYSA-N 1,2,4-trioxane Chemical compound C1COOCO1 FQERLIOIVXPZKH-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910008310 Si—Ge Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- MRPWWVMHWSDJEH-UHFFFAOYSA-N antimony telluride Chemical compound [SbH3+3].[SbH3+3].[TeH2-2].[TeH2-2].[TeH2-2] MRPWWVMHWSDJEH-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- -1 decane compound Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-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
- 125000005843 halogen group Chemical group 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
- 150000004678 hydrides Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 230000007723 transport mechanism Effects 0.000 description 1
- 238000000038 ultrahigh vacuum chemical vapour deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- 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
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
- C30B25/183—Epitaxial-layer growth characterised by the substrate being provided with a buffer layer, e.g. a lattice matching layer
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- C—CHEMISTRY; METALLURGY
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- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/52—Alloys
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02524—Group 14 semiconducting materials
- H01L21/02532—Silicon, silicon germanium, germanium
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- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/0257—Doping during depositing
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Description
本發明一般係關於沈積包括鍺錫之膜的技術且關於包括該等膜之結構及裝置。更特定言之,本發明係關於使用鍺烷作為前驅物形成包含鍺錫之膜的方法,關於形成包括膜之結構及裝置的方法,且關於包括膜之結構及裝置。
各種電子裝置(諸如半導體裝置及光子裝置(諸如雷射及太陽裝置))可包括或可能需要包括鍺錫層,諸如GeSn、GeSiSn及其類似物。舉例而言,GeSn層可用於形成直接帶隙裝置及/或可用於在相鄰鍺層中提供應力以增強在鍺層中之活動性。類似地,GeSiSn層可用於形成可調諧帶隙裝置以及具有可調諧光學特性之光學裝置。為獲得所要裝置特性,鍺錫膜一般具有結晶結構,其一般遵循下伏層之結晶結構。
可使用各種技術使GeSn層沈積或生長。舉例而言,使用真空製程(包括分子束磊晶及超高真空化學氣相沈積)形成GeSn膜。用於該等製程之鍺前驅物典型地包括二鍺烷(Ge2H6)或三鍺烷(Ge3H8)。當膜包括矽時,矽前驅物可包括二矽烷、三矽烷或其他更高級矽烷化合物,或具有通式(H3Ge)xSiH4-x(x=1-4)、(H3Si)xGeH4-x(x=1-4)之異核Si-Ge化合物。
儘管該等製程已用於使結晶GeSn層及GeSiSn層沈積或生長,但使用二鍺烷、三鍺烷或更高級鍺烷前驅物在數個方面具有問題。舉
例而言,當某些載氣(例如氫氣)及/或摻雜劑(例如p型摻雜劑)與前驅物一起使用時,使用二鍺烷或更高級鍺烷前驅物(諸如三鍺烷)形成包括GeSn之膜或層不具選擇性。此外,濃縮形式之二鍺烷相對不穩定(具爆炸性);因此,容器中所含前驅物之量可能典型地限於低於154公克,其又使得使用該前驅物之製程的產量相對低。此外,二鍺烷及更高級鍺烷相對昂貴。因此,需要用於形成包括GeSn之結晶膜的改良製程。
本發明之各種具體實例係關於形成GeSn膜之方法,且關於包括膜之結構及裝置。使用本文所述方法形成之膜可用於例如半導體、直接帶隙、光子或任何包括膜之裝置。在下文更詳細論述本發明各種具體實例解決先前技術方法之缺點的方式的同時,本發明一般提供使用鍺烷(GeH4)前驅物在包括該等膜之基板、結構及裝置的表面上形成鍺錫層(例如結晶)的方法。
如本文所使用,鍺錫(GeSn)層(在本文中亦稱為膜)或包括鍺及錫之層為包括元素鍺及錫之層。該等層可包括其他元素,諸如矽(例如GeSnSi)。
根據本發明之各種具體實例,形成包括GeSn之層的方法包括以下步驟:提供氣相反應器,提供耦接於氣相反應器之鍺烷前驅物源,提供耦接於氣相反應器之錫前驅物源,在氣相反應器之反應室內提供基板,向反應室提供鍺烷前驅物及錫前驅物,及在基板之表面上形成(例如,磊晶生長)鍺錫之結晶層。根據此等具體實例之各種態樣,向反應室提供鍺烷前驅物及錫前驅物之步驟包括提供錫前驅物與鍺烷前驅物之混合物,其中錫前驅物與鍺烷之體積比為約0.001至約0.1、約0.005至約0.05、低於約0.1或低於約0.05。在形成鍺錫之結晶層的步驟期間,反應室溫度及壓力可根據各種因素變化。例示性反應室溫度在約200℃至約500℃範圍內,在
約250℃至約450℃範圍內,或在約300℃至約420℃範圍內。在此步驟期間例示性反應室壓力在約1托(Torr)至約760托範圍內,在約10托至約760托範圍內,或在約50托至約760托範圍內。根據此等具體實例之其他態樣,鍺錫層包括矽。在此等情況下,方法進一步包含向反應室提供矽源前驅物的步驟。例示性矽源前驅物包括二矽烷、三矽烷、四矽烷、新戊矽烷及更高級矽烷化合物。併入結晶鍺錫層中之錫之量可為約大於1at%、大於2at%或大於5at%,或在約0at%至約15at%錫範圍內、在約在2at%至約15at%錫範圍內、在約0.2at%至約5at%錫範圍內或在約0.2at%至約15at%錫範圍內。當結晶鍺錫之層包括矽時,該層可包括大於0at%矽、大於約1at%矽,或約1at%至約20at%矽、約2at%至約16at%矽或約4at%至約12at%矽。根據此等具體實例之其他態樣,基板包括矽。根據其他態樣,基板包括鍺之層-例如覆蓋矽。此等具體實例之例示性方法另外包括以下步驟:形成覆蓋基板之絕緣層,在絕緣層內形成通孔,及在通孔內形成(例如選擇性形成)鍺錫之(例如結晶)層及覆蓋基板,其可包括一或多個先前形成之層。
根據本發明之其他例示性具體實例,形成包含鍺錫(例如結晶)層之結構的方法包括以下步驟:提供氣相反應器,在氣相反應器之反應室內提供基板,及使用一或多種包含鍺烷(GeH4)之前驅物在基板之表面上形成包含鍺錫(例如,結晶)之層。根據此等具體實例之各種態樣,形成包含鍺錫之層的步驟包括提供錫前驅物與鍺烷之混合物,其中錫前驅物與鍺烷之體積比為約0.001至約0.1、約0.005至約0.05、低於約0.1或低於約0.05。根據其他態樣,在形成包含鍺錫之結晶層的步驟期間,反應室溫度在約200℃至約500℃範圍內、在約250℃至約450℃範圍內或在約300℃至約420℃範圍內。根據其他態樣,在形成包含鍺錫之層的步驟期間,反應室壓力在約1托至約760托範圍內、在約10托至約760托範圍內或在約50托至約760托範圍內。根據此等具體實例之其他態樣,形成包含鍺錫之層
的步驟包括形成包含矽鍺錫之層。在此等情況下,向反應室提供矽前驅物。例示性矽源前驅物包括二矽烷、三矽烷、四矽烷、新戊矽烷及更高級矽烷化合物。併入鍺錫層中之錫之量可為約大於1at%、大於2at%或大於5at%,或在約0at%至約15at%錫範圍內、在約2at%至約15at%錫範圍內、在約0.2at%至約5at%錫範圍內或在約0.2at%至約15at%錫範圍內。當結晶鍺錫層之層包括矽時,層可包括大於0at%矽、大於約1at%矽,或約1at%至約20at%矽、約2at%至約16at%矽或約4at%至約12at%矽。根據此等具體實例之各種態樣,基板包括矽。根據其他態樣,基板包括鍺之層,例如覆蓋矽。此等具體實例之例示性方法另外包括以下步驟:形成覆蓋基板之絕緣層,在絕緣層內形成通孔,及在通孔內形成(例如選擇性形成)鍺錫之層及覆蓋基板。
根據本發明之其他具體實例,結構包括根據本發明方法形成之結晶鍺錫層。該結構可用於形成電子(例如,半導體)或光子(例如,太陽或發光)裝置。
且根據本發明之其他例示性具體實例,裝置包括根據本發明方法形成之結晶鍺錫層。
100‧‧‧系統
102‧‧‧反應器
104‧‧‧鍺烷前驅物源
106‧‧‧錫前驅物源/源
108‧‧‧視情況選用之第三前驅物源
110‧‧‧沖洗及/或載氣源
112‧‧‧視情況選用之混合器
114‧‧‧視情況選用之進氣空間
116‧‧‧真空源
118-132‧‧‧管線
134-140‧‧‧閥門
142‧‧‧基板
144‧‧‧反應室
200‧‧‧方法
202-212‧‧‧步驟
300‧‧‧方法
302-310‧‧‧步驟
400‧‧‧結構
402‧‧‧矽基板
404‧‧‧鍺緩衝層
406‧‧‧鍺錫層
500‧‧‧搖擺掃描(rocking scan)
600‧‧‧結構
602‧‧‧基板
604‧‧‧絕緣層
606‧‧‧通孔
608‧‧‧鍺層
610‧‧‧鍺錫層
700‧‧‧結構
702‧‧‧基板
704‧‧‧鍺矽錫層
706‧‧‧鍺錫層
708‧‧‧鍺矽錫層
藉由參考實施方式及申請專利範圍,當結合以下說明性圖式考慮時,可獲得對本發明例示性具體實例之更完全理解。
圖1說明用於根據本發明之例示性具體實例形成結晶鍺錫之層的系統。
圖2說明根據本發明之其他例示性具體實例形成包含鍺錫之層的方法。
圖3說明根據本發明之例示性具體實例形成包含鍺錫之層的另一方法。
圖4說明本發明例示性具體實例之結構。
圖5說明本發明例示性具體實例之結構的搖擺掃描。
圖6說明本發明其他例示性具體實例之另一結構。
圖7說明本發明其他例示性具體實例之另一結構。
應瞭解,圖式中之元件僅出於簡單及明晰之目的而說明且未必按比例繪製。舉例而言,圖式中一些元件之尺寸可相對於其他元件放大以有助於改良對本發明之所說明具體實例的理解。
下文所提供之方法、結構及裝置的例示性具體實例的描述僅為例示性的且僅欲用於說明目的;以下描述不欲限制本發明及申請專利範圍之範疇。此外,敍述具有所述特徵的多個具體實例並不意欲排除具有其他特徵之其他具體實例或併有所述特徵之不同組合的其他具體實例。
本發明大體上係關於形成層之方法,諸如覆蓋基板之結晶層,其包括鍺及錫。鍺錫層可包括其他元素,諸如矽,其形成具有鍺錫層之結晶晶格的一部分。
如本文所使用,「基板(substrate)」係指具有可沈積材料之表面的任何材料。基板可包括塊狀材料,諸如矽(例如,單晶矽,單晶鍺或其他半導體晶圓)或可包括一或多個覆蓋塊狀材料之層。此外,基板可包括各種拓撲結構,諸如在基板層內或在基板層之至少一部分上形成的溝槽、通孔、管線及其類似物。例示性基板包括矽晶圓、包含覆蓋矽之鍺的層及包含覆蓋矽之鍺矽錫的層。
圖1說明適用於使用本文所述方法形成鍺錫之系統100。在所說明之實施例中,系統100包括反應器102、鍺烷前驅物源104、錫前驅物源106、視情況選用之第三前驅物源108(例如,用於在所形成之層中包括矽或其他元素)、沖洗及/或載氣源110、視情況選用之混合器112、視情
況選用之進氣空間114及真空源116。源104-110可使用管線118-132及閥門134-140耦接於混合器112或反應器102。儘管未說明,但系統(諸如系統100)可包括摻雜劑(例如n型摻雜劑,諸如磷或砷;或p型摻雜劑,諸如硼)之其他源及相應傳輸管線。另外或可替代地,摻雜劑可包括在一或多種前驅物源102-108中。
反應器102可為獨立反應器或工具組之一部分。此外,反應器102可用於特定製程(諸如沈積製程),或反應器102可用於其他製程(例如用於層鈍化及/或蝕刻處理)。舉例而言,反應器102可包括典型地用於磊晶化學氣相沈積(CVD)處理之反應器(諸如Epsilon® 2000 Plus(購自ASM))且可包括直接電漿及/或遠端電漿設備(未說明)及/或各種加熱系統(諸如輻射、感應及/或電阻加熱系統)(亦未說明)。使用電漿可增強一或多種前驅物的活性。所說明之反應器為單基板、水平流反應器,其使反應物可在基板142上以短滯留時間層狀流動,從而又便於進行相對快速依序基板處理。適用於系統100之例示性CVD反應器描述於2009年1月13日頒予Pomarede等人之美國專利第7,476,627號中,該專利之內容在其不會與本發明矛盾之程度上以引用的方式併入本文中。儘管以水平流反應器形式說明,但替代具體實例之反應器102可包括垂直流,例如,自蓮蓬頭發散且實質上向下流於基板上之流。
反應器102之反應室144的操作壓力可根據各種因素變化。
反應器102可經組態以在幾乎大氣壓或在更低壓力下操作。舉例而言,在層形成步驟期間,反應器102之操作壓力在約1托至約760托範圍內、在約10托至約760托範圍內或在約50托至約760托範圍內。
源104包括鍺烷(GeH4)且可視情況包括一或多種摻雜劑化合物,諸如典型地用於製造光子及/或半導體裝置之化合物。例示性p型摻雜劑化合物包括B2H6,且例示性n型摻雜劑化合物包括AsH3。
使用鍺烷優於用於形成鍺錫層之其他前驅物(諸如二鍺烷、三鍺烷及其他高級鍺烷),因為在與各種載氣(例如氫氣、氮氣或其類似物)混合時鍺烷相對具有選擇性,且甚至在摻雜劑(例如p型摻雜劑)與前驅物一起使用時鍺烷亦相對具有選擇性。此外,鍺烷與更高級二鍺烷相比相對安全,且因此與更高級鍺烷相比其可以較高數量使用及/或運輸。此外,鍺烷作為其他層(諸如鍺)之前驅物使用,且與高級鍺烷化合物相比其較易於獲得且較便宜。
錫前驅物源106包括適用於向鍺錫層提供錫之任何化合物。例示性錫前驅物包括氯化錫(SnCl4)、氘化錫烷(SnD4)及經甲基及/或鹵基取代之錫烷,諸如具有式Sn(CH3)4-nXn之化合物,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SnBr4。適用於本發明之一些例示性錫前驅物更詳細論述於2013年3月4日申請之題為TIN PRECURSORS FOR VAPOR DEPOSITION AND DEPOSITION PROCESSES之申請案第13/783,762號中,該案之內容在其不會與本發明矛盾之程度上以引用的方式併入本文中。
視情況選用之第三前驅物源108在使用時包括可包括於沈積層中之其他元素或化合物之前驅物。舉例而言,前驅物源108可包括矽前驅物(諸如二矽烷、三矽烷、四矽烷、新戊矽烷及更高級矽烷),或可包括一或多種適用作摻雜劑前驅物/化合物之化合物。若源108包括矽前驅物,則如上所述,系統100可包括其他摻雜劑源及相應供應管線。
氣體源110可包括任何適合沖洗氣體或載氣。適用作載氣及沖洗氣體之例示性氣體包括氮氣、氬氣、氦氣及氫氣。
系統100可包括氣體分配系統。允許在氣體之間(例如源104-110)快速轉換之例示性氣體分配系統闡述於2012年4月10日頒予之
Schmidt等人之題為「Gas Mixer and Manifold Assembly for ALD Reactor」的美國專利第8,152,922號中,該專利之內容在其不會與本發明矛盾之程度上以引用的方式併入本文中。氣體分配系統可用於例如在氣體到達空間114或反應器102前將一或多種前驅物氣體與載氣(其可與氣體源108之沖洗氣體相同或不同)混合。
現轉向圖2,說明形成結晶鍺錫層之例示性方法200。方法200包括以下步驟:提供氣相反應器(步驟202),提供耦接於氣相反應器之鍺烷源(步驟204),提供耦接於氣相反應器之錫前驅物源(步驟206),在氣相反應器之反應室內提供基板(步驟208),向反應室中提供鍺烷及錫前驅物,其中,錫前驅物與鍺烷之比率低於0.1(步驟210),及在基板之表面上形成鍺錫之結晶層(步驟212)。
在步驟202期間,提供適用於磊晶生長之氣相反應器,諸如CVD反應器。反應器可為單基板、層狀流動反應器。該等反應器可購自ASM,諸如Epsilon® 2000 Plus。
在步驟204及206期間,適合鍺烷(GeH4)及錫前驅物源耦接於反應器。如上所述,鍺烷源可包括摻雜劑化合物,諸如p型摻雜劑化合物。或者,摻雜劑可由其他源供應(未說明)。錫前驅物源可包括例如氯化錫及/或氘化錫及/或本文所述之其他錫前驅物。
在步驟208期間,將基板裝載於反應器之反應室中。可自反應器系統之裝載用裝載鎖接收基板,且使用適合傳輸機構將基板運輸至反應室中。
在步驟210中,向反應器之反應室提供錫前驅物及鍺烷。錫前驅物及鍺烷可在進入反應室之前混合(例如在混合器112中)。另外,鍺烷及錫前驅物可單獨混合或與一或多種載氣組合混合。鍺烷及/或錫前驅物可與載體在反應室之上游(諸如在混合器中)或在混合器之上游混合。
如上所述,使用鍺烷優於使用用於形成包括鍺及錫之層的典型前驅物。驚訝且出乎意料地發現,相對於錫前驅物使用相對高分壓之鍺烷形成高品質結晶鍺錫層。根據本發明之例示性具體實例的各種態樣,向反應室提供鍺烷及錫前驅物之步驟包括提供錫前驅物與鍺烷之混合物,其中錫前驅物與鍺烷之體積比為約0.001至約0.1、約0.005至約0.05、低於約0.1或低於約0.05。
在步驟212期間,形成覆蓋基板之結晶層(例如磊晶層)。
在步驟212期間,例示性反應室溫度可在約200℃至約500℃範圍內、在約250℃至約450℃範圍內或在約300℃至約420℃範圍內。且此步驟期間之例示性反應室壓力可在約1托至約760托範圍內、在約10托至約760托範圍內或在約50托至約760托範圍內。
步驟212可包括形成包含鍺矽錫之層。在此等情況下,向反應室提供矽前驅物。例示性矽源前驅物包括二矽烷、三矽烷、四矽烷、新戊矽烷及更高級矽烷化合物。矽前驅物或其他適合前驅物可與載氣混合且視情況與一或多種本文所述之其他前驅物混合。
方法200亦可包括形成覆蓋基板之絕緣層及在絕緣層內形成通孔之步驟。下文更詳細描述形成絕緣層及在絕緣層內形成通孔之例示性技術。在此等情況下,如下所述,可在基板上在通孔內選擇性形成鍺錫層。
圖3說明本發明之其他具體實例的另一方法300。方法300包括以下步驟:提供氣相反應器(步驟302),在氣相反應器之反應室內提供基板(步驟304),及使用一或多種包含鍺烷之前驅物在基板之表面上形成包含鍺錫之結晶層(步驟306)。
在步驟302期間,提供適用於使包含鍺錫之結晶層生長的反應器。反應器可包括本文所述之任何反應器,諸如水平流磊晶CVD反應器。
在步驟304期間,在反應器之反應室內提供基板。步驟304可與方法200之步驟208相同或類似。
在步驟308中,形成包含鍺錫之結晶層。根據本發明之例示性具體實例的各種態樣,形成包含鍺錫之層的步驟包括提供錫前驅物與鍺烷之混合物,其中錫前驅物與鍺烷之體積比為約0.001至約0.1、約0.005至約0.05、低於約0.1或低於約0.05。根據其他態樣,在形成包含鍺錫之結晶層的步驟期間,反應室溫度在約200℃至約500℃範圍內、在約250℃至約450℃範圍內或在約300℃至約420℃範圍內。且根據其他態樣,在形成包含鍺錫之層的步驟期間,反應室壓力在約1托至約760托範圍內、在約10托至約760托範圍內或在約50托至約760托範圍內。
步驟306可包括形成包含鍺矽錫之層。在此等情況下,向反應室提供矽前驅物。例示性矽源前驅物包括二矽烷、三矽烷、四矽烷、新戊矽烷及更高級矽烷化合物。
方法300亦可包括形成覆蓋基板之絕緣層(步驟308)及在絕緣層內形成通孔之視情況選用之步驟308及310。在步驟308期間,任何適合絕緣層(諸如氧化矽或氮化矽)可沈積於基板上。隨後,在步驟310期間,可在絕緣層內形成一或多個通孔。可使用活性離子蝕刻或其他適合技術形成一或多個通孔。
在執行步驟308及310之情況下,可在通孔內選擇性形成在步驟306期間形成之結晶層。如上所述,宜使用鍺烷前驅物,因為當使用各種載氣(諸如氫氣)時且當層包括一或多種摻雜劑(諸如p型摻雜劑)時,其相對具有選擇性。
使用方法200或方法300形成之層(例如在步驟212或306期間)可包括例如大於1at%、大於2at%或大於5at%、或約0at%至約15at%錫、約2at%至約15at%錫、約0.2at%至約5at%錫或約0.2at%至約15at%
錫。當結晶鍺錫之層包括矽時,該層可包括大於0at%矽、大於約1at%矽、或約1at%至約20at%矽、約2at%至約16at%矽或約4at%至約12at%矽。
圖4說明根據本發明之各種具體實例(諸如方法200或方法300)形成的結構400的透射電子顯微影像。結構400包括矽基板402、覆蓋基板402之鍺緩衝層404及使用鍺烷作為前驅物形成之鍺錫層406。在所說明之實例中,層406包括約8at%錫。在所說明之結構中未觀察到穿透缺陷。
圖5說明諸如結構400之結構的(004)搖擺掃描。掃描說明與鍺錫層、鍺層及矽基板相關之不連續峰。如所說明,鍺錫峰與Pendellosung條紋有關,表明在鍺錫層中有高結晶度。
現轉向圖6,說明本發明之其他例示性具體實例的結構600。結構600包括基板602、絕緣層604、在層604內形成之通孔606、鍺層608(例如藉由覆蓋基板602磊晶形成)及鍺錫層610(例如藉由覆蓋層608磊晶形成)。可例如使用方法200或方法300在通孔606內選擇性形成層608及/或610。
圖7說明本發明之其他具體實例另一結構700。結構700包括基板702、鍺矽錫層704、鍺錫層706及鍺矽錫層708。在所說明之實施例中,鍺錫層706介於兩個層鍺矽錫704與708之間。層704-708可根據本文所述方法形成。此外,儘管未說明,但一或多個層704-708可如上文結合圖6所述在絕緣材料之通孔內形成。
應瞭解,本文所述之組態及/或方法在本質上為例示性的,且此等特定具體實例或實施例不應認為具有限制意義。本文所述之特定途徑或方法可表示任何數目之處理策略中之一或多者。因此,所說明之各種操作可按所說明之順序執行、按其他順序執行、同時執行或在一些情況下省略。
本發明之標的物包括本文所揭示之各種製程、系統及組態與
其他特徵、功能、操作及/或特性之所有新穎及不明顯組合及子組合以及其任何及所有等效物。
100‧‧‧系統
102‧‧‧反應器
104‧‧‧鍺烷前驅物源
106‧‧‧錫前驅物源/源
108‧‧‧視情況選用之第三前驅物源
110‧‧‧沖洗及/或載氣源
112‧‧‧視情況選用之混合器
114‧‧‧視情況選用之進氣空間
116‧‧‧真空源
118-132‧‧‧管線
134-140‧‧‧閥門
142‧‧‧基板
144‧‧‧反應室
Claims (20)
- 一種形成結晶鍺錫層之方法,該方法包含以下步驟:提供氣相反應器;提供耦接於該氣相反應器之鍺烷源;提供耦接於該氣相反應器之錫前驅物源;在該氣相反應器之反應室內提供基板;向該反應室提供鍺烷及錫前驅物,其中該錫前驅物與該鍺烷之比率低於0.1;及在該基板之表面上形成鍺錫之結晶層。
- 如申請專利範圍第1項之形成結晶鍺錫層之方法,其中該鍺錫之結晶層進一步包含矽,且該方法進一步包含:提供矽源前驅物。
- 如申請專利範圍第2項之形成結晶鍺錫層之方法,其中提供矽源前驅物之步驟包含提供選自由二矽烷、三矽烷、四矽烷及新戊矽烷組成之群的前驅物。
- 如申請專利範圍第1項至第3項中任一項之形成結晶鍺錫層之方法,其中在該基板之表面上形成鍺錫之結晶層的步驟期間,該反應室之操作壓力為約1托(Torr)至約760托。
- 如申請專利範圍第1項至第3項中任一項之形成結晶鍺錫層之方法,其中在該基板之表面上形成鍺錫之結晶層的步驟期間,該反應室之操作壓力約為50托至約760托。
- 如申請專利範圍第1項至第3項中任一項之形成結晶鍺錫層之方法,其中在形成鍺錫之結晶層的步驟期間,該錫前驅物與該鍺烷之比率為約0.001至約0.1。
- 如申請專利範圍第1項至第3項中任一項之形成結晶鍺錫層之方法, 其中在形成鍺錫之結晶層的步驟期間,該錫前驅物與該鍺烷之比率為約0.005至約0.05。
- 如申請專利範圍第1項至第3項中任一項之形成結晶鍺錫層之方法,其中在該基板之表面上形成鍺錫之結晶層的步驟期間,該反應室內之操作溫度為約200℃至約500℃。
- 如申請專利範圍第1項至第3項中任一項之形成結晶鍺錫層之方法,其中在該基板之表面上形成鍺錫之結晶層的步驟期間,該反應室內之操作溫度為約250℃至約450℃。
- 如申請專利範圍第1項至第3項中任一項之形成結晶鍺錫層之方法,其中提供錫前驅物源之步驟包含提供選自由SnCl4、SnD4及經甲基及/或鹵素取代之錫酸鹽組成之群的錫前驅物源。
- 如申請專利範圍第1項至第3項中任一項之形成結晶鍺錫層之方法,其中該鍺錫之結晶層包含約2at%至約15at%錫。
- 如申請專利範圍第1項至第3項中任一項之形成結晶鍺錫層之方法,其中在形成鍺錫之結晶層的步驟期間,該錫前驅物與該鍺烷前驅物之比率低於0.05。
- 一種形成包含鍺錫層之結構的方法,該方法包含以下步驟:提供氣相反應器;在該氣相反應器之反應室內提供基板;及使用一或多種包含鍺烷之前驅物在該基板之表面上形成包含鍺錫之結晶層。
- 如申請專利範圍第13項之形成包含鍺錫層之結構的方法,其中該基板包含含有覆蓋矽之鍺之層。
- 如申請專利範圍第13項之形成包含鍺錫層之結構的方法,其中該包含鍺錫之結晶層包含約2at%錫至約15at%錫。
- 如申請專利範圍第13項至第15項中任一項之形成包含鍺錫層之結構的方法,其中該包含鍺錫之結晶層包含約1at%至約20at%矽。
- 如申請專利範圍第13項至第15項中任一項之形成包含鍺錫層之結構的方法,其中該基板包含含有覆蓋矽之鍺矽錫之層。
- 如申請專利範圍第13項至第15項中任一項之形成包含鍺錫層之結構的方法,其進一步包含以下步驟:形成覆蓋該基板之絕緣層;在該絕緣層內形成通孔,及在該通孔內選擇性形成該包含鍺錫之結晶層。
- 一種包含鍺錫之結晶層的結構,其包含根據申請專利範圍第13項至第15項中任一項之方法形成的鍺錫之結晶層。
- 如申請專利範圍第19項之包含鍺錫之結晶層的結構,其中該結構在鍺矽錫之兩個層之間包含鍺錫層。
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