JP2013021301A - 成膜方法及び成膜装置 - Google Patents
成膜方法及び成膜装置 Download PDFInfo
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- 230000008021 deposition Effects 0.000 title description 4
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- 239000010408 film Substances 0.000 claims abstract description 162
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052796 boron Inorganic materials 0.000 claims abstract description 37
- 238000005121 nitriding Methods 0.000 claims abstract description 36
- 229910000077 silane Inorganic materials 0.000 claims abstract description 35
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 28
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 28
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000010703 silicon Substances 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
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- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims description 39
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 8
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- VOSJXMPCFODQAR-UHFFFAOYSA-N ac1l3fa4 Chemical compound [SiH3]N([SiH3])[SiH3] VOSJXMPCFODQAR-UHFFFAOYSA-N 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims description 4
- LXEXBJXDGVGRAR-UHFFFAOYSA-N trichloro(trichlorosilyl)silane Chemical compound Cl[Si](Cl)(Cl)[Si](Cl)(Cl)Cl LXEXBJXDGVGRAR-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- BIVNKSDKIFWKFA-UHFFFAOYSA-N N-propan-2-yl-N-silylpropan-2-amine Chemical compound CC(C)N([SiH3])C(C)C BIVNKSDKIFWKFA-UHFFFAOYSA-N 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- 229960001730 nitrous oxide Drugs 0.000 claims description 2
- 235000013842 nitrous oxide Nutrition 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 claims description 2
- CGRVKSPUKAFTBN-UHFFFAOYSA-N N-silylbutan-1-amine Chemical compound CCCCN[SiH3] CGRVKSPUKAFTBN-UHFFFAOYSA-N 0.000 claims 1
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- 239000006185 dispersion Substances 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 10
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- PPWPWBNSKBDSPK-UHFFFAOYSA-N [B].[C] Chemical compound [B].[C] PPWPWBNSKBDSPK-UHFFFAOYSA-N 0.000 description 1
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- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- C23C16/45529—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making a layer stack of alternating different compositions or gradient compositions
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Abstract
【解決手段】被処理体Wが収容されて真空引き可能になされた処理容器4内に、ボロン含有ガスと窒化ガスとシラン含有ガスと炭化水素ガスとを供給して被処理体の表面にボロンと窒素とシリコンと炭素を含む薄膜を形成する成膜方法において、ボロン含有ガスと窒化ガスとを交互に間欠的に供給するサイクルを1回以上行ってBN膜を形成する第1の工程と、シラン系ガスと炭化水素ガスと窒化ガスとを間欠的に供給するサイクルを1回以上行ってSiCN膜を形成する第2の工程とを有する。これにより、低誘電率化、ウェットエッチング耐性の向上及びリーク電流の低減化が達成されたボロンと窒素とシリコンと炭素とを含む薄膜を形成する。
【選択図】図4
Description
被処理体が収容されて真空引き可能になされた処理容器内に、ボロン含有ガスと窒化ガスとシラン含有ガスと炭化水素ガスとを供給して被処理体の表面にボロンと窒素とシリコンと炭素を含む薄膜を形成する成膜方法において、ボロンと窒素とシリコンと炭素とを含む薄膜(SiBCN膜)の低誘電率化、ウェットエッチング耐性の向上及びリーク電流の低減化を達成することができる。
まず、本発明方法の第1実施例について図3乃至図5も参照して説明する。図3は本発明の成膜方法の第1実施例を示すフローチャート、図4は本発明の成膜方法の第1実施例における各種ガスの供給のタイミングを示すタイミングチャート、図5は本発明の成膜方法の第1実施例によって形成される積層構造の薄膜を示す断面図である。まず、常温の多数枚、例えば50〜100枚の300mmのウエハWが載置された状態のウエハボート12を予め所定の温度になされた処理容器4内にその下方より上昇させてロードし、蓋部18でマニホールド8の下端開口部を閉じることにより容器内を密閉する。
次に、上述のように本発明の成膜方法によって形成された積層構造のSiBCN膜96について各種特性を求めたので、その評価結果について図6及び図7も参照して説明する。ここでは、先に説明した本発明の成膜方法の第1実施例を用いて積層構造のSiBCN膜を形成した。また、比較例として上記第1実施例においてC2 H4 ガスを用いないで炭素を含有させない積層構造のSiBN膜を形成し、各種特性を測定した。図6は各膜の希フッ化水素に対するエッチング量及び比誘電率とリーク電流を示すグラフであり、図6(A)は各膜のエッチング量と比誘電率を示し、図6(B)は各膜の電界強度とリーク電流との関係を示す。
次に、本発明方法の成膜レートの温度依存性について実験を行ったので、その評価結果について説明する。ここでは先に説明した成膜方法を用いてSiBCN膜を形成した。ただしプロセス温度を450℃から650℃の範囲内で変化させている。図8は成膜レートの温度依存性を示すグラフである。図8では横軸に成膜温度(℃と1000/T:T=273.1+℃)をとり、縦軸に1サイクルの成膜レートをとっている。
次に本発明の成膜方法の第2実施例について説明する。図9は本発明の成膜方法の第2実施例を示すフローチャート、図10は本発明の成膜方法の第2実施例における中間工程の各種ガスの供給のタイミングを示すタイミングチャート、図11は本発明の成膜方法の第2実施例によって形成される積層構造の薄膜を示す断面図である。尚、先に説明した図3乃至図5に示す部分と同一部分については同一参照符号を付してその説明を省略する。
4 処理容器
12 ウエハボート(保持手段)
28 窒化ガス供給手段
30 シラン系ガス供給手段
32 ボロン含有ガス供給手段
34 炭化水素ガス供給手段
36 パージガス供給手段
38,40,42,44 ガス分散ノズル
72 真空排気系
80 加熱手段
82 制御手段
88 BN膜
92 SiCN膜
96,100 SiBCN膜
98 SiN膜
W 半導体ウエハ(被処理体)
Claims (15)
- 被処理体が収容されて真空引き可能になされた処理容器内に、ボロン含有ガスと窒化ガスとシラン含有ガスと炭化水素ガスとを供給して前記被処理体の表面にボロンと窒素とシリコンと炭素を含む薄膜を形成する成膜方法において、
前記ボロン含有ガスと前記窒化ガスとを交互に間欠的に供給するサイクルを1回以上行ってBN膜を形成する第1の工程と、
前記シラン系ガスと前記炭化水素ガスと前記窒化ガスとを間欠的に供給するサイクルを1回以上行ってSiCN膜を形成する第2の工程とを有することを特徴とする成膜方法。 - 前記第2の工程では、前記シラン系ガスと前記炭化水素ガスと前記窒化ガスとが互いに異なるタイミングで供給されることを特徴とする請求項1記載の成膜方法。
- 前記第2の工程では、前記シラン系ガスが最初に供給されることを特徴とする請求項2記載の成膜方法。
- 前記第2の工程では、前記シラン系ガスが最初に供給されると共に、前記炭化水素ガスと前記窒化ガスの内のいずれか一方のガスが前記シラン系ガスと同時に供給されることを特徴とする請求項1記載の成膜方法。
- 前記第1の工程には、前記ボロン含有ガスの供給を行いつつ前記処理容器内の排気を停止させるホールド期間を有することを特徴とする請求項1乃至4のいずれか一項に記載の成膜方法。
- 前記各ガスの時間的に隣り合う供給期間の間には、前記処理容器内の残留ガスを排除するパージ工程が行われることを特徴とする請求項1乃至5のいずれか一項に記載の成膜方法。
- 前記第1の工程と前記第2の工程とよりなるサイクルを1回以上行うようにしたことを特徴とする請求項1乃至6のいずれか一項に記載の成膜方法。
- 前記第1の工程と前記第2の工程との間には、前記シラン系ガスと前記窒化ガスとを交互に供給するサイクルを1回以上行ってSiN膜を形成する中間工程を行うことを特徴とする請求項1乃至7のいずれか一項に記載の成膜方法。
- 前記各工程にけるプロセス温度は、500〜700℃の範囲内であることを特徴とする請求項1乃至8のいずれか一項に記載の成膜方法。
- 前記第1の工程内のサイクル数xと前記第2の工程内のサイクル数yとの関係が”1/2≦x/y≦2”の関係式を満たすことを特徴とする請求項1乃至9のいずれか一項に記載の成膜方法。
- 前記ボロン含有ガスは、BCl3 、B2 H6 、BF3 、B(CH3 )3 、TEB、TDMAB、TMABよりなる群より選択される1以上のガスであることを特徴とする請求項1乃至10のいずれか一項に記載の成膜方法。
- 前記窒化ガスは、アンモニア[NH3 ]、窒素[N2 ]、一酸化二窒素[N2 O]、一酸化窒素[NO]よりなる群より選択される1以上のガスであることを特徴とする請求項1乃至11のいずれか一項に記載の成膜方法。
- 前記シラン系ガスは、ジクロロシラン(DCS)、ヘキサクロロジシラン(HCD)、モノシラン[SiH4 ]、ジシラン[Si2 H6 ]、ヘキサメチルジシラザン(HMDS)、テトラクロロシラン(TCS)、ジシリルアミン(DSA)、トリシリルアミン(TSA)、ビスターシャルブチルアミノシラン(BTBAS)、ジイソプロピルアミノシラン(DIPAS)よりなる群より選択される1以上のガスであることを特徴とする請求項1乃至12のいずれか一項に記載の成膜方法。
- 前記炭化水素ガスは、アセチレン、エチレン、メタン、エタン、プロパン、ブタンよりなる群より選択される1以上のガスであることを特徴とする請求項1乃至13のいずれか一項に記載の成膜方法。
- 被処理体に対して所定の薄膜を形成するための成膜装置において、
真空引き可能になされた縦型の筒体状の処理容器と、
前記被処理体を複数段に保持して前記処理容器内に挿脱される保持手段と、
前記処理容器の外周に設けられる加熱手段と、
前記処理容器内へシラン系ガスを供給するシラン系ガス供給手段と、
前記処理容器内へ窒化ガスを供給する窒化ガス供給手段と、
前記処理容器内へボロン含有ガスを供給するボロン含有ガス供給手段と、
前記処理容器内へ炭化水素ガスを供給する炭化水素ガス供給手段と、
請求項1乃至14のいずれか一項に記載の成膜方法を実行するように制御する制御手段と、
を備えたことを特徴とする成膜装置。
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