JP2013135176A - シリコン酸炭窒化膜の形成方法 - Google Patents
シリコン酸炭窒化膜の形成方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 94
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title abstract description 13
- 229910052814 silicon oxide Inorganic materials 0.000 title abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 270
- 239000010703 silicon Substances 0.000 claims abstract description 269
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 269
- 230000008569 process Effects 0.000 claims abstract description 35
- 238000010030 laminating Methods 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims description 78
- 229910052760 oxygen Inorganic materials 0.000 claims description 78
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 77
- 230000003647 oxidation Effects 0.000 claims description 18
- 238000007254 oxidation reaction Methods 0.000 claims description 18
- 238000003763 carbonization Methods 0.000 claims description 5
- 238000001039 wet etching Methods 0.000 abstract description 28
- 238000001312 dry etching Methods 0.000 abstract description 26
- 239000000758 substrate Substances 0.000 abstract description 5
- -1 silicon oxide nitride Chemical class 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 58
- 239000007789 gas Substances 0.000 description 52
- 239000010410 layer Substances 0.000 description 47
- 238000001179 sorption measurement Methods 0.000 description 35
- 229910052757 nitrogen Inorganic materials 0.000 description 26
- 239000011261 inert gas Substances 0.000 description 21
- 238000005121 nitriding Methods 0.000 description 20
- 235000012431 wafers Nutrition 0.000 description 20
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 14
- 229910052581 Si3N4 Inorganic materials 0.000 description 14
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 14
- 239000007800 oxidant agent Substances 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
- 230000008901 benefit Effects 0.000 description 10
- 230000001590 oxidative effect Effects 0.000 description 10
- 238000010000 carbonizing Methods 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 230000007246 mechanism Effects 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 150000004767 nitrides Chemical class 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000012886 linear function Methods 0.000 description 1
- 239000011553 magnetic fluid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
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Abstract
【解決手段】 下地上に、シリコン酸炭窒化膜を形成するシリコン酸炭窒化膜の形成方法であって、下地上に、シリコン炭窒化膜とシリコン酸窒化膜とを積層してシリコン酸炭窒化膜を形成する。
【選択図】図1
Description
図1はこの発明の第1の実施形態に係るシリコン酸炭窒化膜の形成方法の一例を示す流れ図、図2A〜図2Eは第1の実施形態に係るシリコン酸炭窒化膜の形成方法の一例における主要な工程を示す断面図である。
エッチャント : 希フッ酸(H2O:HF=100:1)
処 理 時 間: 60sec
また、ドライエッチングの条件は次の通りである。
エッチャント : CHF3、CF4、O2の混合ガス
処 理 時 間: 5sec
図3に示すように、シリコン炭窒化膜(SiCN膜)は、上記希フッ酸では、ほとんどエッチングされない。第1の実施形態のように意図的に酸素を導入してシリコン酸炭窒化膜4とし、その酸素濃度を上げていくと、上記希フッ酸によってエッチングされやすくなっていく。つまり、シリコン酸炭窒化膜4は、その酸素濃度が低いと、ウェットエッチング耐性が増す傾向が理解できる。
(1) 特に、ウェットエッチング耐性に優れたシリコン酸炭窒化膜
(2) 特に、ドライエッチング耐性に優れたシリコン酸炭窒化膜
(3) 加工の容易性を有しつつ、ウェットエッチング耐性およびドライエッチング耐性の双方ともが実用に供し得る範囲となるシリコン酸炭窒化膜
を、それぞれ精度良く作り分けることができる、という利点を得ることができる。
図6に示すように、屈折率が約1.86のシリコン酸炭窒化膜4Aは、酸素濃度が約22at.%、窒素濃度が約33at.%の低酸素濃度、高窒素濃度(窒素リッチ)の膜組成である。同じく屈折率が約1.79のシリコン酸炭窒化膜4Bも、酸素濃度が約27at.%、窒素濃度が約31at.%の低酸素濃度、高窒素濃度(窒素リッチ)の膜組成である。
図7は第1の実施形態のステップ1に用いられるシリコン炭窒化膜の形成方法の一例を示す流れ図、図8はガスの吐出タイミングの一例を示すタイミングチャート、図9A〜図9Cはシリコン炭窒化膜の形成方法の一例における主要な工程を示す断面図である。
シリコン原料ガス : ジクロロシラン(SiH2Cl2:DCS)
シリコン原料ガス流量: 500〜3000sccm
処 理 時 間 : 0.05〜1.0min
処 理 温 度 : 450〜630℃
処 理 圧 力 : 13.3〜1064Pa(0.1〜8.0Torr)
上記処理条件では、シリコンウエハ1の被処理面上に、膜厚約0.3〜1.0nmのシリコン吸着層5が形成される。
炭化剤ガス : エチレン(C2H4)
炭化剤ガス流量: 3000sccm
処 理 時 間: 0.5〜1.5min
(炭化剤ガス供給時間:0.05〜0.2min ホールド時間:0.2〜1.3min)
処 理 温 度: 450〜630℃
処 理 圧 力: 133〜665Pa(1.0〜5.0Torr)
ステップ12が終了したら、不活性ガスを用いて処理室内をパージし、処理室の内部の雰囲気を不活性ガス雰囲気、本例では窒素ガス雰囲気に置換する。
窒化剤ガス : アンモニア(NH3)
窒化剤ガス流量: 5000〜10000sccm
処 理 時 間: 0.2〜1.0min
処 理 温 度: 450〜630℃
処 理 圧 力: 13.3〜66.5Pa(0.1〜0.5Torr)
ステップ13が終了したら、不活性ガスを用いて処理室内をパージし、処理室の内部の雰囲気を不活性ガス雰囲気、本例では窒素ガス雰囲気に置換する。ここまでで、シリコン炭窒化膜2の成膜シーケンスの1サイクルが終了する。
図10は第1の実施形態のステップ2に用いられるシリコン酸窒化膜の形成方法の第1例を示す流れ図、図11はガスの吐出タイミングの一例を示すタイミングチャート、図12A〜図12Cはシリコン炭窒化膜の形成方法の一例における主要な工程を示す断面図である。
シリコン原料ガス : ジクロロシラン(SiH2Cl2:DCS)
シリコン原料ガス流量: 500〜3000sccm
処 理 時 間 : 0.05〜1.0min
処 理 温 度 : 450〜630℃
処 理 圧 力 : 13.3〜1064Pa(0.1〜8.0Torr)
上記処理条件では、シリコン炭窒化膜2上に、膜厚約0.3〜1.0nmのシリコン吸着層7が形成される。
窒化剤ガス : アンモニア(NH3)
窒化剤ガス流量: 5000〜10000sccm
処 理 時 間: 0.2〜1.0min
処 理 温 度: 450〜630℃
処 理 圧 力: 133〜665Pa(0.1〜0.5Torr)
ステップ22が終了したら、不活性ガスを用いて処理室内をパージし、処理室の内部の雰囲気を不活性ガス雰囲気、本例では窒素ガス雰囲気に置換する。
酸化剤ガス : 酸素(O2)
酸化剤ガス流量: 1000〜10000sccm
処 理 時 間: 0.1〜1.0min
処 理 温 度: 450〜630℃
処 理 圧 力: 13.3〜133Pa(0.1〜1.0Torr)
ステップ23が終了したら、不活性ガスを用いて処理室内をパージし、処理室の内部の雰囲気を不活性ガス雰囲気、本例では窒素ガス雰囲気に置換する。ここまでで、シリコン酸窒化膜3の成膜シーケンスの1サイクルが終了する。
図13は第1の実施形態のステップ2に用いられるシリコン酸窒化膜の形成方法の第2例を示す流れ図である。
図16は第1の実施形態のステップ2に用いられる第1例に係るシリコン酸窒化膜の形成方法の変形例を示す流れ図である。
第2の実施形態は、第1の実施形態に係るシリコン酸炭窒化膜の形成方法を実施することが可能な成膜装置の一例に関する。
その他、この発明はその要旨を逸脱しない範囲で様々に変形することができる。
Claims (10)
- 下地上に、シリコン酸炭窒化膜を形成するシリコン酸炭窒化膜の形成方法であって、
下地上に、シリコン炭窒化膜とシリコン酸窒化膜とを積層してシリコン酸炭窒化膜を形成することを特徴とするシリコン酸炭窒化膜の形成方法。 - 前記シリコン炭窒化膜の形成と、前記シリコン酸窒化膜の形成とを繰り返すことを特徴とする請求項1に記載のシリコン酸炭窒化膜の形成方法。
- 前記シリコン炭窒化膜の形成が、シリコン膜の炭化工程および窒化工程を含み、
前記シリコン酸窒化膜の形成が、シリコン膜の酸化工程および窒化工程を含むことを特徴とする請求項1又は請求項2に記載のシリコン酸炭窒化膜の形成方法。 - 前記シリコン炭窒化膜の形成において、前記シリコン膜の炭化工程および窒化工程を繰り返すことを特徴とする請求項3に記載のシリコン酸炭窒化膜の形成方法。
- 前記シリコン酸窒化膜の形成において、前記シリコン膜の酸化工程および窒化工程を繰り返すことを特徴とする請求項3又は請求項4に記載のシリコン酸炭窒化膜の形成方法。
- 前記シリコン膜の酸化工程と窒化工程との順序を制御し、形成されるシリコン酸炭窒化膜の酸素濃度を制御することを特徴とする請求項3から請求項5のいずれか一項に記載のシリコン酸炭窒化膜の形成方法。
- 前記形成されるシリコン酸炭窒化膜の酸素濃度を20at.%以上35at.%以下の範囲に制御することを特徴とする請求項6に記載のシリコン酸炭窒化膜の形成方法。
- 前記形成されるシリコン酸炭窒化膜の屈折率(光の波長633nm)が、1.72以上1.90以下の範囲であることを特徴とする請求項1から請求項7のいずれか一項に記載のシリコン酸炭窒化膜の形成方法。
- 前記形成されるシリコン酸炭窒化膜の酸素濃度を20at.%以上30at.%以下の範囲に制御することを特徴とする請求項6に記載のシリコン酸炭窒化膜の形成方法。
- 前記形成されるシリコン酸炭窒化膜の屈折率(光の波長633nm)が、1.77以上1.90以下の範囲であることを特徴とする請求項1から請求項6、及び請求項9のいずれか一項に記載のシリコン酸炭窒化膜の形成方法。
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