JP6952620B2 - シリコン膜またはゲルマニウム膜またはシリコンゲルマニウム膜を成膜する方法および装置 - Google Patents
シリコン膜またはゲルマニウム膜またはシリコンゲルマニウム膜を成膜する方法および装置 Download PDFInfo
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- JP6952620B2 JP6952620B2 JP2018030576A JP2018030576A JP6952620B2 JP 6952620 B2 JP6952620 B2 JP 6952620B2 JP 2018030576 A JP2018030576 A JP 2018030576A JP 2018030576 A JP2018030576 A JP 2018030576A JP 6952620 B2 JP6952620 B2 JP 6952620B2
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- silicon
- amorphous
- germanium
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- 229910000577 Silicon-germanium Inorganic materials 0.000 title claims description 74
- 229910052710 silicon Inorganic materials 0.000 title claims description 58
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims description 55
- 239000010703 silicon Substances 0.000 title claims description 55
- 238000000034 method Methods 0.000 title claims description 48
- 229910052732 germanium Inorganic materials 0.000 title claims description 40
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims description 40
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 title claims description 30
- 239000007789 gas Substances 0.000 claims description 198
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 57
- 229910052736 halogen Inorganic materials 0.000 claims description 57
- 150000002367 halogens Chemical class 0.000 claims description 57
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 52
- 239000013078 crystal Substances 0.000 claims description 51
- 239000002994 raw material Substances 0.000 claims description 40
- 238000011282 treatment Methods 0.000 claims description 34
- 230000007246 mechanism Effects 0.000 claims description 26
- 239000011261 inert gas Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 238000000137 annealing Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910021419 crystalline silicon Inorganic materials 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 2
- 235000012431 wafers Nutrition 0.000 description 46
- 239000000460 chlorine Substances 0.000 description 44
- 239000008186 active pharmaceutical agent Substances 0.000 description 13
- 230000008569 process Effects 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 238000002425 crystallisation Methods 0.000 description 11
- 230000008025 crystallization Effects 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 230000003746 surface roughness Effects 0.000 description 11
- 239000000758 substrate Substances 0.000 description 9
- 239000002184 metal Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000010453 quartz Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 229910017817 a-Ge Inorganic materials 0.000 description 6
- 229910021332 silicide Inorganic materials 0.000 description 6
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- QUZPNFFHZPRKJD-UHFFFAOYSA-N germane Chemical compound [GeH4] QUZPNFFHZPRKJD-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000002019 doping agent Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- VXGHASBVNMHGDI-UHFFFAOYSA-N digermane Chemical compound [Ge][Ge] VXGHASBVNMHGDI-UHFFFAOYSA-N 0.000 description 2
- 230000003028 elevating effect Effects 0.000 description 2
- 238000011066 ex-situ storage Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 101000735417 Homo sapiens Protein PAPPAS Proteins 0.000 description 1
- 102100034919 Protein PAPPAS Human genes 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011553 magnetic fluid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- LXEXBJXDGVGRAR-UHFFFAOYSA-N trichloro(trichlorosilyl)silane Chemical compound Cl[Si](Cl)(Cl)[Si](Cl)(Cl)Cl LXEXBJXDGVGRAR-UHFFFAOYSA-N 0.000 description 1
- VEDJZFSRVVQBIL-UHFFFAOYSA-N trisilane Chemical compound [SiH3][SiH2][SiH3] VEDJZFSRVVQBIL-UHFFFAOYSA-N 0.000 description 1
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Description
まず、本発明の第1の実施形態に係る成膜方法について説明する。本実施形態は、単結晶上に同じ材料からなる非晶質膜を形成する場合について説明する。
図1は本発明の第1の実施形態に係る成膜方法の一例を示すフローチャート、図2はその際の被処理基板の状態を概略的に示す工程断面図である。
Cl2ガス流量:300〜5000sccm
処理時間 :0.5〜5min
処理温度 :50〜400℃
処理圧力 :1.33〜666.6Pa(0.01〜5Torr)
Si2H6ガス流量:10〜1000sccm
処理時間 :1min以上
処理温度 :350〜450℃
処理圧力 :13.3〜1333.3Pa(0.1〜10Torr)
表面の酸化膜が除去された清浄な単結晶シリコンの上に直接シリコン原料ガスを供給すると、下地の単結晶の格子定数を引きずってエピタキシャル成長しやすく、一般的に、ほぼ単結晶のSi膜が成膜される。
単結晶Siの酸化膜を除去した後の表面は、図4(a)に示すように水素終端(未結合手を含む)されているが、水素終端は結合が弱いため、その表面にシリコン原料ガスが供給されると、図4(b)に示すように、Hが容易にSiに置き換わり、Siがエピタキシャル成長していく。これに対し、ハロゲン元素であるClを単結晶シリコンの表面に吸着させると、図5(a)に示すように、水素終端の一部がハロゲン元素であるClに置き換わり、Cl終端が形成される。この状態でシリコン原料ガスが供給されると、ハロゲン元素であるClはHよりも下地のSiとの結合が強いため、図5(b)に示すように、Cl終端はSiに置き換わらず、格子のミスマッチが生じてエピタキシャル成長が阻害される。このため、単結晶Si面にハロゲン元素が吸着されることにより、その全面にほぼ完全にアモルファスのSi膜(a−Si膜)4を成膜することができる。
次に、本発明の第2の実施形態に係る成膜方法について説明する。本実施形態は、単結晶上に異なる材料からなる非晶質膜を形成する場合について説明する。
図11は本発明の第1の実施形態に係る成膜方法の一例を示すフローチャート、図12はその際の被処理基板の状態を概略的に示す工程断面図である。
SiH4ガス流量:0を超え〜5000sccm
Ge2H4ガス流量:0を超え〜5000sccm
処理時間 :5min以上
処理温度 :250〜450℃
処理圧力 :13.33〜533.2Pa(0.1〜4Torr)
表面の酸化膜が除去された清浄な単結晶シリコン上に直接シリコン原料ガスおよびゲルマニウム原料ガスを供給すると、下地の単結晶の格子定数を引きずってエピタキシャル成長しやすく、ほぼ単結晶のSiGe膜が成膜される。
次に、上記第1、第2の実施形態に係る成膜方法を実施することが可能な成膜装置の一例について説明する。
以上、本発明の実施の形態について説明したが、この発明は、上記の実施形態に限定されることはなく、その要旨を逸脱しない範囲で種々変形可能である。
2;酸化膜
3;ハロゲン元素
4;a−Si膜
5;残留酸素
6;ファセット
7;単結晶Si膜
8;a−SiGe膜
9;ミスフィット転移
10;単結晶SiGe膜
Claims (12)
- 被処理面として単結晶シリコンまたは単結晶ゲルマニウムまたは単結晶シリコンゲルマニウムを有する被処理体の前記被処理面上に、シリコン膜またはゲルマニウム膜またはシリコンゲルマニウム膜を成膜する方法であって、
前記被処理体を準備する第1工程と、
前記被処理体の被処理面にハロゲン元素を吸着させる第2工程と、
前記被処理体にシリコン膜またはゲルマニウム膜またはシリコンゲルマニウム膜を成膜するための原料ガスを供給し、前記被処理体の前記被処理面上に非晶質シリコン膜または非晶質ゲルマニウム膜または非晶質シリコンゲルマニウム膜を成膜する第3工程と
を備えることを特徴とする方法。 - 前記第2工程のハロゲン元素はCl、F、Br、およびIから選択される少なくとも一種であることを特徴とする請求項1に記載の方法。
- 前記第2工程は、前記被処理体にハロゲン元素含有ガスを供給することにより行われることを特徴とする請求項1または請求項2に記載の方法。
- 前記ハロゲン元素含有ガスは、Cl2ガス、HClガス、HBrガス、Br2ガス、HIガス、I2ガス、ClF3ガス、およびF2ガスから選択されたものであることを特徴とする請求項3に記載の方法。
- 前記第2工程の前に、前記被処理面から酸化膜を除去する第4工程をさらに有することを特徴とする請求項1から請求項4のいずれか1項に記載の方法。
- 前記第4工程は、水素を含む物質により行われることを特徴とする請求項5に記載の方法。
- 前記第4工程は、アンモニアガスとフッ化水素ガスを用いた化学的酸化膜除去処理により行われることを特徴とする請求項6に記載の方法。
- 前記第3工程の後に、前記非晶質シリコン膜または前記非晶質ゲルマニウム膜または前記非晶質シリコンゲルマニウム膜を結晶化する第5工程をさらに有することを特徴とする請求項1から請求項7のいずれか1項に記載の方法。
- 前記第5工程は、真空引きまたはアニールにより行われることを特徴とする請求項8に記載の方法。
- 前記第5工程は、前記第3工程の後、in−situで行われることを特徴とする請求項8または請求項9に記載の方法。
- 被処理面として単結晶シリコンまたは単結晶ゲルマニウムまたは単結晶シリコンゲルマニウムを有する被処理体の前記被処理面上に、シリコン膜またはゲルマニウム膜またはシリコンゲルマニウム膜を成膜する装置であって、
前記被処理体を収容する処理容器と、
前記処理容器内に、シリコン膜またはゲルマニウム膜またはシリコンゲルマニウム膜を成膜するための原料ガス、およびハロゲン元素含有ガス、および不活性ガスを供給するガス供給機構と、
前記被処理体を加熱する加熱装置と、
前記処理容器内を排気する排気装置と、
前記ガス供給機構、前記加熱装置、および前記排気装置を制御する制御部と
を備え、
前記制御部は、前記被処理体が前記処理容器内に配置された状態で、前記排気装置および前記加熱装置により前記処理容器内の圧力および温度を制御しつつ、前記ガス供給機構から前記処理容器内に前記ハロゲン元素含有ガスを供給させて前記被処理体の被処理面にハロゲン元素を吸着させ、次いで、前記ガス供給機構から前記被処理体に前記原料ガスを供給させて、前記被処理体の前記被処理面上に非晶質シリコン膜または非晶質ゲルマニウム膜または非晶質シリコンゲルマニウム膜を成膜させるように制御することを特徴とする装置。 - 前記制御部は、前記被処理体の前記被処理面上に非晶質シリコン膜または非晶質ゲルマニウム膜または非晶質シリコンゲルマニウム膜を成膜させた後、前記処理容器内を前記排気装置により真空引きさせるか、または、前記処理容器内で前記加熱装置により前記被処理体をアニール処理させることにより、前記非晶質シリコン膜または前記非晶質ゲルマニウム膜または前記非晶質シリコンゲルマニウム膜を結晶化するように制御することを特徴とする請求項11に記載の装置。
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TW108105543A TWI758587B (zh) | 2018-02-23 | 2019-02-20 | 矽膜、鍺膜或矽鍺膜之成膜方法及裝置 |
CN201910132739.0A CN110189983B (zh) | 2018-02-23 | 2019-02-22 | 对硅膜或锗膜或硅锗膜进行成膜的方法和装置 |
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