JP6340251B2 - SiCN膜の成膜方法 - Google Patents
SiCN膜の成膜方法 Download PDFInfo
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- JP6340251B2 JP6340251B2 JP2014112439A JP2014112439A JP6340251B2 JP 6340251 B2 JP6340251 B2 JP 6340251B2 JP 2014112439 A JP2014112439 A JP 2014112439A JP 2014112439 A JP2014112439 A JP 2014112439A JP 6340251 B2 JP6340251 B2 JP 6340251B2
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- triazole
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- 238000000034 method Methods 0.000 title claims description 61
- 239000007789 gas Substances 0.000 claims description 54
- 238000005121 nitriding Methods 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 14
- -1 ethyl-1,2,3-triazole 1,4-diethyl-1,2,3-triazole Chemical group 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 2
- VVELGWMBFXAFTA-UHFFFAOYSA-N 1,4,5-triethyltriazole Chemical compound CCC=1N=NN(CC)C=1CC VVELGWMBFXAFTA-UHFFFAOYSA-N 0.000 claims 1
- QSCBDGSZPLQSGX-UHFFFAOYSA-N CN1N=NC(=C1C)C.CN1N=NC(=C1)C.CN1N=NC=C1.N1N=NC=C1 Chemical compound CN1N=NC(=C1C)C.CN1N=NC(=C1)C.CN1N=NC=C1.N1N=NC=C1 QSCBDGSZPLQSGX-UHFFFAOYSA-N 0.000 claims 1
- 235000012431 wafers Nutrition 0.000 description 36
- 230000015572 biosynthetic process Effects 0.000 description 29
- 229910004298 SiO 2 Inorganic materials 0.000 description 17
- 238000005530 etching Methods 0.000 description 15
- 239000011261 inert gas Substances 0.000 description 12
- 238000000151 deposition Methods 0.000 description 11
- 230000008021 deposition Effects 0.000 description 10
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 7
- LXEXBJXDGVGRAR-UHFFFAOYSA-N trichloro(trichlorosilyl)silane Chemical compound Cl[Si](Cl)(Cl)[Si](Cl)(Cl)Cl LXEXBJXDGVGRAR-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000003776 cleavage reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000007017 scission Effects 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 0 *c1c(*)nn[n]1* Chemical compound *c1c(*)nn[n]1* 0.000 description 1
- 150000000177 1,2,3-triazoles Chemical class 0.000 description 1
- FPNQKZFYYHRTHF-UHFFFAOYSA-N C(C)N1N=NC(=C1CC)CC.C(C)N1N=NC(=C1)CC.C(C)N1N=NC=C1.CN1N=NC(=C1C)C.CN1N=NC(=C1)C.CN1N=NC=C1.N1N=NC=C1 Chemical compound C(C)N1N=NC(=C1CC)CC.C(C)N1N=NC(=C1)CC.C(C)N1N=NC=C1.CN1N=NC(=C1C)C.CN1N=NC(=C1)C.CN1N=NC=C1.N1N=NC=C1 FPNQKZFYYHRTHF-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000005446 heptyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011553 magnetic fluid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000003466 welding Methods 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
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- 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
- H01L21/02112—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 characterised by the material of the layer
- H01L21/02123—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 characterised by the material of the layer the material containing silicon
- H01L21/02167—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 characterised by the material of the layer the material containing silicon the material being a silicon carbide not containing oxygen, e.g. SiC, SiC:H or silicon carbonitrides
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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
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
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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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- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
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Description
<成膜方法>
図1はこの発明の第1の実施形態に係るSiCN膜の成膜方法の一例を示す流れ図、図2A〜図2Fは図1に示すシーケンス中の被処理体の状態を示す断面図である。
HCD 流 量: 100sccm
成 膜 時 間: 0.5min(1サイクル当たり)
成 膜 温 度: 550℃
成 膜 圧 力: 133.32Pa(1Torr)
メチル基
エチル基
n−プロピル基
イソプロピル基
n−ブチル基
イソブチル基
t−ブチル基
n−ペンチル基
イソペンチル基
t−ペンチル基
n−ヘキシル基
イソヘキシル基
t−ヘキシル基
n−ヘプチル基
イソヘプチル基
t−ヘプチル基
n−オクチル基
イソオクチル基
t−オクチル基
である。好ましくはメチル基、エチル基、n−プロピル基である。さらに好ましくはメチル基である。
モノメチルアミノ基
ジメチルアミノ基
モノエチルアミノ基
ジエチルアミノ基
モノプロピルアミノ基
モノイソプロピルアミノ基
エチルメチルアミノ基
である。好ましくはモノメチルアミノ基、ジメチルアミノ基である。さらに好ましくはジメチルアミノ基である。
メトキシ基
エトキシ基
プロポキシ基
ブトキシ基
ペントキシ基
ヘキシルオキシ基
ヘプチルオキシ基
オクチルオキシ基
である。好ましくは、メトキシ基、エトキシ基、プロポキシ基である。さらに好ましくは、メトキシ基である。
1H−1,2,3−トリアゾール
1−メチル−1,2,3−トリアゾール
1,4−ジメチル−1,2,3−トリアゾール
1,4,5−トリメチル−1,2,3−トリアゾール
1−エチル−1,2,3−トリアゾール
1,4−ジエチル−1,2,3−トリアゾール
1,4,5−トリエチル−1,2,3−トリアゾール
である。なお、これらの化合物は、単独又は二種以上を混合して使用しても良い。
トリアゾール流量: 100sccm
処 理 時 間 : 0.5min(1サイクル当たり)
処 理 温 度 : 550℃
処 理 圧 力 : 133.32Pa(1Torr)
図3はSiCN膜の原子組成を示す図である。図3には、第1の実施形態に係る成膜方法にて成膜したSiCN膜の原子組成の他、参考例として成膜温度630℃、Si原料ガスにジクロロシラン(DCS)、窒化剤にNH3、炭化剤にエチレン(C2H4)を用い、熱ALD法にて成膜したSiCN膜の原子組成を示す。
図4はSiN膜およびSiCN膜のエッチングレートを示す図である。図4には、エッチャントに0.5%DHFを用い、熱SiO2膜のエッチングレートを1.0(100%)の基準値としたときの、SiN膜およびSiCN膜のエッチングレートの割合が示されている。
成膜温度500℃、Si原料ガスにDCS、窒化剤にNH3を用いたプラズマALD法にて成膜したSiN膜の0.5%DHFに対するエッチングレートは、基準値に比較して0.47(47%)であり、熱SiO2膜のエッチングレートのおよそ半分である。しかし、成膜温度を450℃に下げると、0.5%DHFに対するエッチングレートは、基準値に比較して1.21(121%)となり、熱SiO2膜よりもエッチングレートが早くなってしまう。このように、プラズマALD法にて成膜したSiN膜は、薬液耐性、特に0.5%DHFに対する耐性が良好である、とはいえない。
図5はSiN膜およびSiCN膜の成膜温度と成膜レートとの関係を示す図である。
図5に示すように、Si原料ガスにDCS、窒化剤にNH3を用いたプラズマALD法は、成膜温度が低温であっても、成膜レートに0.02nm/min以上を確保することができ、低温成膜に有利である。
第2の実施形態は、第1の実施形態に係るSiCN膜の成膜方法を実施することが可能な成膜装置の例に関する。
図7は第1の実施形態に係るSiCN膜の成膜方法を実施することが可能な成膜装置の第1例を概略的に示す縦断面図である。
図8は第1の実施形態に係るSiCN膜の成膜方法を実施することが可能な成膜装置の第2例を概略的に示す水平断面図である。
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 (5)
- 被処理体の被処理面上にSiCN膜を成膜するSiCN膜の成膜方法であって、
前記被処理体が収容された処理室内にSi原料を含むSi原料ガスを供給する工程と、
前記Si原料ガスを供給する工程の後、前記処理室内に窒化剤を含むガスを供給する工程とを備え、
前記窒化剤として、下記一般式(1)で示される窒素と炭素との化合物を用い、200℃以上550℃以下の範囲の成膜温度で、前記化合物が開裂・分解して得られた分解物から炭素が膜中に取り込まれたSiCN膜を成膜することを特徴とするSiCN膜の成膜方法。
- R1、R2、R3の置換基が、炭素原子数1〜4の直鎖状又は分岐状のアルキル基で置換されているモノアルキルアミノ基又はジアルキルアミノ基であることを特徴とする請求項1に記載のSiCN膜の成膜方法。
- R1、R2、R3の置換基が、炭素原子数1〜8の直鎖状又は分岐状のアルコキシ基であることを特徴とする請求項1に記載のSiCN膜の成膜方法。
- 一般式(1)で示される化合物が、
1H−1,2,3−トリアゾール
1−メチル−1,2,3−トリアゾール
1,4−ジメチル−1,2,3−トリアゾール
1,4,5−トリメチル−1,2,3−トリアゾール
1−エチル−1,2,3−トリアゾール
1,4−ジエチル−1,2,3−トリアゾール、又は
1,4,5−トリエチル−1,2,3−トリアゾール
であることを特徴とする請求項1に記載のSiCN膜の成膜方法。 - 前記処理室内に窒化剤を含むガスを供給する工程は、プラズマを用いないで実施することを特徴とする請求項1から請求項4のいずれか一項に記載のSiCN膜の成膜方法。
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