JP2019035147A - 金属酸化膜形成方法及びプラズマ強化化学気相蒸着装置 - Google Patents
金属酸化膜形成方法及びプラズマ強化化学気相蒸着装置 Download PDFInfo
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- JP2019035147A JP2019035147A JP2018152563A JP2018152563A JP2019035147A JP 2019035147 A JP2019035147 A JP 2019035147A JP 2018152563 A JP2018152563 A JP 2018152563A JP 2018152563 A JP2018152563 A JP 2018152563A JP 2019035147 A JP2019035147 A JP 2019035147A
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- plasma
- oxide film
- metal oxide
- organometallic compound
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- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 78
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 59
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 title claims description 40
- 239000000758 substrate Substances 0.000 claims abstract description 56
- 239000007800 oxidant agent Substances 0.000 claims abstract description 50
- 238000001179 sorption measurement Methods 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 125000004429 atom Chemical group 0.000 claims abstract description 10
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 150000002902 organometallic compounds Chemical class 0.000 claims description 75
- 238000009792 diffusion process Methods 0.000 claims description 51
- 230000001590 oxidative effect Effects 0.000 claims description 24
- 230000004044 response Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 230000000087 stabilizing effect Effects 0.000 claims 1
- 238000007740 vapor deposition Methods 0.000 claims 1
- 239000012808 vapor phase Substances 0.000 claims 1
- 230000008021 deposition Effects 0.000 abstract description 4
- 150000002736 metal compounds Chemical class 0.000 abstract description 3
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 28
- 238000010586 diagram Methods 0.000 description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 12
- 229940125810 compound 20 Drugs 0.000 description 12
- 238000000231 atomic layer deposition Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 5
- 230000006641 stabilisation Effects 0.000 description 5
- 238000011105 stabilization Methods 0.000 description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 description 5
- 239000003446 ligand Substances 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
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- 230000007423 decrease Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- -1 N 2 O or NO 2 Chemical class 0.000 description 1
- 229910004013 NO 2 Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229940126086 compound 21 Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
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Abstract
Description
他方では、プラズマオン区間は前記プラズマオフ区間より長い設定時間を有してもよく、複数のプラズマオン区間において、プラズマ強度は一定の値を有してもよい。
プラズマオン区間は、前記サイクルの反復序数の増加に対応して漸進的に長い設定時間を有してもよい。
他方では、プラズマオフ区間とプラズマオン区間は同一の設定時間を有してもよく、複数のプラズマオン区間において、プラズマ強度はサイクルの反復序数の増加に対応して漸進的に高まってもよい。
他方では、複数のプラズマオン区間はサイクル数の増加に比例して漸進的に長い設定時間を有してもよく、複数のプラズマオン区間において、プラズマ強度はサイクルの反復序数の増加に比例して漸進的に高まってもよい。
有機金属化合物と酸化剤は各自の配管によってチェンバの内部に注入され、有機金属化合物は少なくとも一つの拡散板を通過した後に基板上に提供され得る。
他の一実施形態による金属酸化膜形成方法は、吸着安定段階とプラズマ成膜段階を含む。吸着安定段階において、チェンバの内部に有機金属化合物と酸化剤が注入され、基板上に二層以上の厚さの原子層の有機金属化合物からなる物理化学的吸着層が形成される。プラズマ成膜段階において、チェンバの内部にプラズマが生成されて物理化学的吸着層内の金属原子と酸化剤内の酸素原子の化学反応によって二層以上の厚さの原子層からなる金属酸化膜が形成される。吸着安定段階とプラズマ成膜段階が一つのサイクルを成して反復遂行され得る。
有機金属化合物と酸化剤は、各自の配管によってチェンバの内部に注入される。有機金属化合物は、少なくとも一つの拡散板を通過した後に基板上に提供され得る。
制御部は、高周波電源のオン−オフ動作と、オン−オフ時間と、出力電圧を制御することができる。
プラズマ強化化学気相蒸着装置は、蓋板と基板の間に相互間距離をおいて位置する第1拡散板と第2拡散板をさらに含んでもよく、第1拡散板は第2拡散板より蓋板にさらに近く配置されてもよい。
第1拡散板と第2拡散板は金属から製作され、蓋板に固定されて蓋板を介して通電され得る。
第1配管は蓋板の中央に接続され、第1拡散板に複数の開口が配置され、第1拡散板の単位面積当り開口率は、第1配管との距離によって異なってもよい。
第1拡散板は、第1配管と対向する中央領域と、中央領域の外側に位置する中間領域と、中間領域の外側に位置する外郭領域とに区分され、第1拡散板の単位面積当り開口率は、外郭領域、中間領域、及び中央領域の順に高くてもよい。
複数の開口は放射形に配置されてもよい。
第2配管は、側壁中の第2拡散板と基板の間に対応する部分に接続されてもよい。
第2配管は、側壁の周り方向に沿って複数個備えられてもよい。
20 有機金属化合物
21 中心金属
22 リガンド
30 酸化剤
40 吸着層、物理化学的吸着層
50 金属酸化膜
100、200 プラズマ強化化学気相蒸着(PECVD)装置
110 チェンバ
120 蓋板
130 基板支持部
141 第1配管
142 第2配管
145 第1ガス供給部
146 第2ガス供給部
151 高周波電源
152 制御部
161 第1拡散板
162 第2拡散板
164、165 開口
Claims (20)
- チェンバの内部に有機金属化合物と酸化剤が持続的に注入される間、プラズマオフ(off)区間とプラズマオン(on)区間が一つのサイクルを成して反復遂行され、
前記プラズマオフ区間において、基板上に二層以上の原子層の有機金属化合物からなる物理化学的吸着層が形成され、
前記プラズマオン区間において、前記物理化学的吸着層内の金属原子と前記酸化剤内の酸素原子の化学反応によって二層以上の厚さの原子層からなる金属酸化膜が形成される、ことを特徴とする金属酸化膜形成方法。 - 前記プラズマオフ区間と前記プラズマオン区間は、同一の設定時間を有し、
前記複数のプラズマオン区間において、プラズマ強度は一定の値を有する、ことを特徴とする請求項1に記載の金属酸化膜形成方法。 - 前記プラズマオン区間は、前記プラズマオフ区間より長い設定時間を有し、
前記複数のプラズマオン区間において、プラズマ強度は一定の値を有する、ことを特徴とする請求項1に記載の金属酸化膜形成方法。 - 前記プラズマオン区間は、前記サイクルの反復序数の増加に対応して漸進的に長い設定時間を有する、ことを特徴とする請求項3に記載の金属酸化膜形成方法。
- 前記プラズマオフ区間と前記プラズマオン区間は、同一の設定時間を有し、
前記複数のプラズマオン区間において、プラズマ強度は前記サイクルの反復序数の増加に対応して漸進的に高まる、ことを特徴とする請求項1に記載の金属酸化膜形成方法。 - 前記複数のプラズマオン区間は、前記サイクルの反復序数の増加に対応して漸進的に長い設定時間を有し、
前記複数のプラズマオン区間において、プラズマ強度は前記サイクルの反復序数の増加に対応して漸進的に高まる、ことを特徴とする請求項1に記載の金属酸化膜形成方法。 - 前記有機金属化合物と前記酸化剤は、各自の配管によって前記チェンバの内部に注入され、
前記有機金属化合物は、少なくとも一つの拡散板を通過した後に前記基板上に提供される、ことを特徴とする請求項1に記載の金属酸化膜形成方法。 - チェンバの内部に有機金属化合物と酸化剤が注入され、基板上に二層以上の原子層の有機金属化合物からなる物理化学的吸着層が形成される吸着安定段階、及び
前記チェンバの内部にプラズマが生成されて前記物理化学的吸着層内の金属原子と前記酸化剤内の酸素原子の化学反応によって二層以上の厚さの原子層からなる金属酸化膜が形成されるプラズマ成膜段階を含み、
前記吸着安定段階と前記プラズマ成膜段階が一つのサイクルを成して反復遂行される、ことを特徴とする金属酸化膜形成方法。 - 前記有機金属化合物と前記酸化剤は、各自の配管によって前記チェンバの内部に注入される、ことを特徴とする請求項8に記載の金属酸化膜形成方法。
- 前記有機金属化合物は、少なくとも一つの拡散板を通過した後に前記基板上に提供される、ことを特徴とする請求項9に記載の金属酸化膜形成方法。
- 底板と側壁を含み、内部空間に基板を受容するチェンバと、
前記チェンバの上側に結合され、金属から製作された蓋板と、
前記蓋板に電気的に連結され、制御部によってオン−オフ動作が制御される高周波電源と、
前記チェンバの内部において前記基板を支持し、接地された基板支持部と、
前記蓋板に接続され、前記チェンバの内部に有機金属化合物を供給する第1配管と、
前記側壁に接続され、前記チェンバの内部に酸化剤を供給する第2配管と
を含む、ことを特徴とするプラズマ強化化学気相蒸着装置。 - 前記チェンバの内部に前記有機金属化合物と前記酸化剤が持続的に供給される間、前記高周波電源は前記制御部によってターン−オンとターン−オフが交互に繰り返される、ことを特徴とする請求項11に記載のプラズマ強化化学気相蒸着装置。
- 前記制御部は、前記高周波電源のオン−オフ動作と、オン−オフ時間と、出力電圧を制御する、ことを特徴とする請求項12に記載のプラズマ強化化学気相蒸着装置。
- 前記蓋板と前記基板の間に相互間距離をおいて位置する第1拡散板と第2拡散板をさらに含み、
前記第1拡散板が前記第2拡散板より前記蓋板にさらに近く位置する、ことを特徴とする請求項11に記載のプラズマ強化化学気相蒸着装置。 - 前記第1拡散板と前記第2拡散板は金属から製作され、前記蓋板に固定されて前記蓋板を介して通電される、ことを特徴とする請求項14に記載のプラズマ強化化学気相蒸着装置。
- 前記第1配管は、前記蓋板の中央に接続され、
前記第1拡散板に複数の開口が位置し、
前記第1拡散板の単位面積当り開口率は、前記第1配管との距離によって異なる、ことを特徴とする請求項14に記載のプラズマ強化化学気相蒸着装置。 - 前記第1拡散板は、前記第1配管と対向する中央領域と、前記中央領域の外側に位置する中間領域と、前記中間領域の外側に位置する外郭領域とに区分され、
前記第1拡散板の単位面積当り開口率は、前記外郭領域、前記中間領域、及び前記中央領域の順に高い、ことを特徴とする請求項16に記載のプラズマ強化化学気相蒸着装置。 - 前記複数の開口は、放射形に配置される、ことを特徴とする請求項17に記載のプラズマ強化化学気相蒸着装置。
- 前記第2配管は、前記側壁中の前記第2拡散板と前記基板の間に対応する部分に接続される、ことを特徴とする請求項14に記載のプラズマ強化化学気相蒸着装置。
- 前記第2配管は、前記側壁の周り方向に沿って複数個備えられる、ことを特徴とする請求項19に記載のプラズマ強化化学気相蒸着装置。
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