JP2022062709A - 表面保護物質を用いた薄膜形成方法 - Google Patents
表面保護物質を用いた薄膜形成方法 Download PDFInfo
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- JP2022062709A JP2022062709A JP2021166344A JP2021166344A JP2022062709A JP 2022062709 A JP2022062709 A JP 2022062709A JP 2021166344 A JP2021166344 A JP 2021166344A JP 2021166344 A JP2021166344 A JP 2021166344A JP 2022062709 A JP2022062709 A JP 2022062709A
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- 239000000126 substance Substances 0.000 title claims abstract description 170
- 239000010409 thin film Substances 0.000 title claims abstract description 70
- 230000001681 protective effect Effects 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 51
- 230000015572 biosynthetic process Effects 0.000 title abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 76
- 239000010408 film Substances 0.000 claims abstract description 46
- 239000000758 substrate Substances 0.000 claims abstract description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 159
- 125000000217 alkyl group Chemical group 0.000 claims description 48
- 125000003118 aryl group Chemical group 0.000 claims description 33
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 33
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 18
- 125000003282 alkyl amino group Chemical group 0.000 claims description 15
- 239000000376 reactant Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 125000005264 aryl amine group Chemical group 0.000 claims description 9
- 125000005265 dialkylamine group Chemical group 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 150000003974 aralkylamines Chemical group 0.000 claims description 3
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 125000005241 heteroarylamino group Chemical group 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 11
- 238000004140 cleaning Methods 0.000 abstract 2
- 239000007789 gas Substances 0.000 description 23
- 239000006227 byproduct Substances 0.000 description 14
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 229910052814 silicon oxide Inorganic materials 0.000 description 8
- 229910000449 hafnium oxide Inorganic materials 0.000 description 7
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 7
- 239000011261 inert gas Substances 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 3
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- MXKUPMZUKJUXOW-UHFFFAOYSA-N C(O)(O)O.C(OC)(OC)OC Chemical compound C(O)(O)O.C(OC)(OC)OC MXKUPMZUKJUXOW-UHFFFAOYSA-N 0.000 description 2
- JIGXARPLYFNBCG-UHFFFAOYSA-N C1(C=CC=C1)[Hf](N(C)C)(N(C)C)N(C)C Chemical compound C1(C=CC=C1)[Hf](N(C)C)(N(C)C)N(C)C JIGXARPLYFNBCG-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- SBEQWOXEGHQIMW-UHFFFAOYSA-N silicon Chemical compound [Si].[Si] SBEQWOXEGHQIMW-UHFFFAOYSA-N 0.000 description 2
- VBXQPQJYKGAVKV-UHFFFAOYSA-N C(C)(C)N(C(C)C)[SiH3].C(C)(C)N(C(C)C)[SiH3] Chemical compound C(C)(C)N(C(C)C)[SiH3].C(C)(C)N(C(C)C)[SiH3] VBXQPQJYKGAVKV-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
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- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
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- H01L21/02142—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 containing silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides
- H01L21/02148—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 containing silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides the material containing hafnium, e.g. HfSiOx or HfSiON
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Abstract
Description
R1はそれぞれ独立して炭素数1~10のアルキル基,炭素数1~5のアルコキシ基又は水素原子の中から選択され,
R2は,それぞれ独立して炭素数1~8のアルキル基,炭素数3~6のシクロアルキル基,炭素数6~12のアリール基の中から選択される。
R1又はR2は,それぞれ独立して炭素数1~8のアルキル基,炭素数3~6のシクロアルキル基,炭素数6~12のアリール基の中から選択される。
R1はそれぞれ独立して炭素数1~8のアルキル基又は水素原子の中から選択され,
R2は,それぞれ独立して炭素数1~8のアルキル基,炭素数3~6のシクロアルキル基,炭素数6~12のアリール基の中から選択される。
R1又はR2は,それぞれ独立して炭素数1~8のアルキル基,炭素数3~6のシクロアルキル基,炭素数6~12のアリール基の中から選択される。
Rは,それぞれ独立して炭素数1~10のアルキル基,炭素数3~10のシクロアルキル基,炭素数6~12のアリール基の中から選択される。
前記<化学式8>において, nはそれぞれ独立して0~8の整数であり,
R1乃至R3は,それぞれ独立して炭素数が1~8であるアルキル基であり,
R4は水素,炭素数が1~6であるアルキル基,炭素数が1~8であるアルコキシ基の中から選択される。
Lはハロゲン原子,水素原子,又はアジド基の中から選択される。
R6からR9は,それぞれ独立して,水素原子,炭素数1~4のアルキル基,炭素数1~4のアルキルアミン基,炭素数2~4のジアルキルアミン基,炭素数6~12のアリール基の中から選択される。
R1はそれぞれ独立して炭素数1~10のアルキル基,炭素数1~5のアルコキシ基又は水素原子の中から選択され,
R2は,それぞれ独立して炭素数1~8のアルキル基,炭素数3~6のシクロアルキル基,炭素数6~12のアリール基の中から選択される。
R1又はR2は,それぞれ独立して炭素数1~8のアルキル基,炭素数3~6のシクロアルキル基,炭素数6~12のアリール基の中から選択される。
R1はそれぞれ独立して炭素数1~8のアルキル基又は水素原子の中から選択され,
R2は,それぞれ独立して炭素数1~8のアルキル基,炭素数3~6のシクロアルキル基,炭素数6~12のアリール基の中から選択される。
R1又はR2は,それぞれ独立して炭素数1~8のアルキル基,炭素数3~6のシクロアルキル基,炭素数6~12のアリール基の中から選択される。
前記<化学式7>において, nはそれぞれ独立して0~5の整数であり,mはそれぞれ独立して1~5の整数であり,
Rは,それぞれ独立して炭素数1~10のアルキル基,炭素数3~10のシクロアルキル基,炭素数6~12のアリール基の中から選択される。
R1乃至R3は,それぞれ独立して炭素数が1~8であるアルキル基であり,
R4は水素,炭素数が1~6であるアルキル基,炭素数が1~8であるアルコキシ基の中から選択される。
Lはハロゲン原子,水素原子,又はアジド基の中から選択される。
R6からR9は,それぞれ独立して,水素原子,炭素数1~4のアルキル基,炭素数1~4のアルキルアミン基,炭素数2~4のジアルキルアミン基,炭素数6~12のアリール基の中から選択される。
図2は,本発明の比較例1による供給サイクルを概略的に示すグラフである。前述した表面保護物質を使用せずに,ドーピング用薄膜にシリコン酸化物,誘電膜にハフニウム酸化物を形成し,シリコン酸化物を形成するためのドーピング用前駆体としてジイソプロピルアミノシラン(Diisoprophylamino Silane:DIPAS)とハフニウム酸化物を形成するための誘電膜用前駆体としてトリス(ジメチルアミノ)シクロペンタジエニルハフニウム(iv)[CpHf(NMe2)3](HAC)を使用し, 工程温度は320℃,反応物質は,O3ガスを使用した。
2)反応チャンバ内にArガスを供給して未吸着ドーピング用前駆体又は副産物を除去
3)O3ガスを反応室に供給してドーピング用薄膜を形成
4)反応チャンバ内にArガスを供給して未反応物質又は副産物を除去
5) Arをキャリア(carrier)ガスとして,常温で誘電膜用前駆体(HAC)を反応チャンバに供給して,基板に誘電膜用前駆体を吸着
6)反応チャンバ内にArガスを供給して未吸着誘電膜用前駆体又は副産物を除去
7)O3ガスを反応室に供給して誘電膜を形成
8)反応チャンバ内にArガスを供給して未反応物質又は副産物を除去
表面保護物質でオルト蟻酸トリメチル(Trimethyl orthoformate)を使用して,シリコン基板上にアルミニウム酸化膜を形成した。 ALD工程を使用してアルミニウム酸化膜を形成し,ALD工程温度は250~390℃,反応物質は,O3ガスを使用した。
2)反応チャンバ内にArガスを供給して未吸着表面保護物質又は副産物を除去
3)Arをキャリアガスとして,常温でドーピング用前駆体(DIPAS)を反応チャンバに供給して,基板にドーピング用前駆体を吸着
4)反応チャンバ内にArガスを供給して未吸着ドーピング用前駆体又は副産物を除去
5)O3ガスを反応室に供給してドーピング用薄膜を形成
6)反応チャンバ内にArガスを供給して未反応物質又は副産物を除去
7)Arをキャリアガスとして,常温で誘電膜用前駆体(HAC)を反応チャンバに供給して,基板に誘電膜用前駆体を吸着
8)反応チャンバ内にArガスを供給して未吸着誘電膜用前駆体又は副産物を除去
9)O3ガスを反応室に供給して誘電膜を形成
10)反応チャンバ内にArガスを供給して未反応物質又は副産物を除去
Claims (21)
- 表面保護物質を用いた薄膜形成方法において,
基板が載置されたチャンバの内部に,前記表面保護物質を供給する表面保護物質供給工程;
前記チャンバの内部を浄化する工程;
前記チャンバの内部にドーピング用の前駆体を供給するドーピング用前駆体供給工程;
前記チャンバの内部を浄化する工程;
前記チャンバの内部に第1の反応物質を供給して吸着された前記ドーピング用前駆体と反応してドーピング用薄膜を形成するドーピング用薄膜形成工程;
前記チャンバの内部に誘電膜用前駆体を供給する誘電膜用前駆体供給工程;
前記チャンバの内部を浄化する工程;及び
前記チャンバの内部に第2の反応物質を供給して吸着された前記誘電膜用前駆体と反応して誘電膜を形成する誘電膜形成工程を含む,表面保護物質を用いた薄膜形成方法。 - 前記反応物質はO3,O2,H2O,H2O2,N2OとNH3の中から選択される請求項1記載の表面保護物質を用いた薄膜形成方法。
- 前記誘電膜用前駆体は,Ti,Zr及びHfを含む4価の金属の少なくとも1つを含む化合物である請求項1記載の表面保護物質を用いた薄膜形成方法。
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JP2014053371A (ja) * | 2012-09-05 | 2014-03-20 | Toshiba Corp | 不揮発性半導体記憶装置 |
JP2014187269A (ja) * | 2013-03-25 | 2014-10-02 | Hitachi Kokusai Electric Inc | 半導体装置の製造方法、基板処理装置及びプログラム |
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