JP6302081B2 - ゲルマニウムまたは酸化ゲルマニウムの原子層堆積 - Google Patents
ゲルマニウムまたは酸化ゲルマニウムの原子層堆積 Download PDFInfo
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- JP6302081B2 JP6302081B2 JP2016549415A JP2016549415A JP6302081B2 JP 6302081 B2 JP6302081 B2 JP 6302081B2 JP 2016549415 A JP2016549415 A JP 2016549415A JP 2016549415 A JP2016549415 A JP 2016549415A JP 6302081 B2 JP6302081 B2 JP 6302081B2
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- 229910052732 germanium Inorganic materials 0.000 title claims description 43
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims description 26
- 238000000231 atomic layer deposition Methods 0.000 title claims description 25
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 title claims description 12
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 title claims description 6
- 239000002243 precursor Substances 0.000 claims description 67
- 238000000151 deposition Methods 0.000 claims description 54
- 239000000758 substrate Substances 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 43
- 230000008021 deposition Effects 0.000 claims description 42
- 238000010926 purge Methods 0.000 claims description 19
- 239000011261 inert gas Substances 0.000 claims description 18
- -1 alkyl germanium Chemical compound 0.000 claims description 15
- JKUUTODNPMRHHZ-UHFFFAOYSA-N n-methyl-n-[tris(dimethylamino)germyl]methanamine Chemical group CN(C)[Ge](N(C)C)(N(C)C)N(C)C JKUUTODNPMRHHZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000004065 semiconductor Substances 0.000 claims description 4
- 238000006557 surface reaction Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000009738 saturating Methods 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 150000002290 germanium Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 17
- 229910005793 GeO 2 Inorganic materials 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000003877 atomic layer epitaxy Methods 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 229940119177 germanium dioxide Drugs 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000005234 chemical deposition Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000012713 reactive precursor Substances 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
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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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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C16/40—Oxides
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- C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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Description
a.Ge含有前駆体パルス
b.不活性ガスによるパージ
c.還元パルスまたは酸化パルス
d.不活性ガスによるパージ
[(CH3)2N]4Ge+O3→GeO2+副生成物
[(CH3)2N]4Ge+H*→Ge+副生成物
ゲルマニウムを基板に堆積させるプロセスは、少なくとも1つの堆積サイクルにおいて、室内の基板を、Ge含有前駆体および還元前駆体または酸化前駆体に順次暴露することを含む。
実施形態1によるプロセスであって、前記少なくとも1つの堆積サイクルに以下のことが含まれる。
a.Ge含有前駆体パルス
b.不活性ガスによるパージ
c.還元パルスまたは酸化パルス
d.不活性ガスによるパージ
実施形態1または2によるプロセスであって、ステップcにおいて、還元前駆体はH2および水素プラズマからなる群から選択される。
実施形態1から3のいずれかによるプロセスであって、前記堆積サイクルのステップcにおける還元パルスとして、不活性ガスとの混合物に約4〜100%、好ましくは約5〜50%、最も好ましくは約15%(容積/容積)の量のH2が用いられる。
実施形態1または2によるプロセスであって、ステップcにおいて、酸化前駆体はO2、O3、H2O2、酸素プラズマ、水、および水プラズマから選択される。
実施形態1から5のいずれかによるプロセスであって、前記堆積サイクルは、約50℃〜約800℃、好ましくは約100℃〜約500℃、より好ましくは約300℃〜約400℃、最も好ましくは約350℃の温度で実行される。
実施形態1から6のいずれかによるプロセスであって、前記不活性ガスは窒素またはアルゴンであり、プラズマ前駆体が用いられる場合の前記不活性ガスはアルゴンである。
実施形態1から7のいずれかによるプロセスであって、前記Ge含有前駆体は、室温から200℃の温度範囲で少なくとも1hPaの揮発性を有する。
実施形態1から8のいずれかによるプロセスであって、前記Ge含有前駆体は、アルキルゲルマニウム、アルキルアミノゲルマニウム、テトラキス(ジメチルアミノ)ゲルマニウム、ジケトナートゲルマニウム、ゲルマニウムハロゲン化物、およびゲルマニウムアルコキシドからなる群から選択される。
実施形態1から9のいずれかによるプロセスであって、前記基板は、シリコン基板、ゲルマニウム基板、III‐V族半導体、酸化シリコン、または酸化ゲルマニウム基板、あるいは無機および有機/ポリマー材料をベースとする基板である。
実施形態1から10のいずれかによるプロセスであって、前記プロセスは、自己飽和表面反応に基づく。
実施形態1から11のいずれかによるプロセスであって、前記堆積サイクルは、堆積層の厚さが10〜100nmになるまで繰り返される。
原子層堆積におけるテトラキス(ジメチルアミノ)ゲルマニウムの使用である。
実施形態13による使用であって、前記原子層堆積は、シリコン基板を堆積させるためのものである。
実施形態13または14による使用であって、前記使用は、GeまたはGeO2を堆積させることを含む。
実施形態1から12のいずれかによるプロセスによって、基板としての非堆積物を被覆することで作成した、GeまたはGeO2の堆積物。
<実施例1>
ゲルマニウム元素の堆積
[(CH3)2N]4Geを1s / N2を2s / N2と15%のH2の混合物を1s / N2を1s
<実施例2>
二酸化ゲルマニウムの堆積
[(CH3)2N]4Geを1s / N2を2s / O3を1s / N2を1s
Claims (12)
- ゲルマニウム元素を基板に堆積させるプロセスであって、
少なくとも1つの堆積サイクルにおいて、室内の基板を、Ge含有前駆体および還元前駆体に順次暴露することを含み、
前記Ge含有前駆体は、テトラキス(ジメチルアミノ)ゲルマニウム、ゲルマニウムアミジナート類の誘導体、アルキルゲルマニウム、ハロゲン化アルキルゲルマニウム、テトラメチル‐Ge、(CH 3 ) 3 GeCl、ゲルマニウムβ−ジケトナート類、ゲルマニウムアセチルアセトナート類、ゲルマニウムハロゲン化物から選択され、
前記還元前駆体は、H 2 又は水素プラズマである、
むプロセス。 - 前記少なくとも1つの堆積サイクルに、
a.Ge含有前駆体パルス、
b.不活性ガスによるパージ、
c.還元パルス、および
d.不活性ガスによるパージ
が含まれる、請求項1に記載のプロセス。 - 前記堆積サイクルのステップcにおける前記還元パルスとして、不活性ガスとの混合物に約4〜100%(容積/容積)、好ましくは約5〜50%(容積/容積)、最も好ましくは約15%(容積/容積)の量のH2が用いられ、
ただし、前記不活性ガスが用いられない場合は、前記還元パルスは前記混合物ではなくH 2 を100%(容積/容積)含む、
請求項2に記載のプロセス。 - 前記堆積サイクルは、約50℃〜約800℃、好ましくは約100℃〜約500℃、より好ましくは約300℃〜約400℃、最も好ましくは約350℃の温度で実行される、請求項1から3のいずれかに記載のプロセス。
- プラズマプロセスである、請求項1から4のいずれかに記載のプロセスであって、前記不活性ガスはアルゴンである、プロセス。
- 前記Ge含有前駆体は、室温から200℃の温度範囲で少なくとも1hPaの揮発性を有する、請求項1から5のいずれかに記載のプロセス。
- 前記基板は、シリコン基板、ゲルマニウム基板、III‐V族半導体、酸化シリコン、または酸化ゲルマニウム基板、あるいは無機および有機/ポリマー材料をベースとする基板である、請求項1から6のいずれかに記載のプロセス。
- 前記プロセスは、自己飽和表面反応に基づく、請求項1から7のいずれかに記載のプロセス。
- 前記堆積サイクルは、堆積層の厚さが10〜100nmになるまで繰り返される、請求項1から8のいずれかに記載のプロセス。
- 原子層堆積における、テトラキス(ジメチルアミノ)ゲルマニウム、及び、H 2 および水素プラズマから選択される還元前駆体の使用。
- 前記原子層堆積は、シリコン基板に堆積させるためのものである、請求項10に記載の使用。
- Ge堆積物を製造する方法であって、請求項1から9のいずれかに記載のプロセスによって、基板としての非堆積物を被覆することを含む、方法。
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PCT/FI2014/050155 WO2015132445A1 (en) | 2014-03-04 | 2014-03-04 | Atomic layer deposition of germanium or germanium oxide |
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KR20170058820A (ko) * | 2015-11-19 | 2017-05-29 | 주식회사 유진테크 머티리얼즈 | 유기 4족 화합물을 포함하는 전구체 조성물 및 이를 이용한 박막 형성 방법 |
US10319588B2 (en) * | 2017-10-10 | 2019-06-11 | Asm Ip Holding B.V. | Method for depositing a metal chalcogenide on a substrate by cyclical deposition |
EP3585136A1 (en) | 2018-06-20 | 2019-12-25 | Masarykova Univerzita | A method and device for generating low-temperature electrical water-based plasma at near-atmospheric pressures and its use |
TW202225456A (zh) * | 2020-12-11 | 2022-07-01 | 美商應用材料股份有限公司 | 超保形氧化鍺膜 |
US11781218B2 (en) | 2020-12-11 | 2023-10-10 | Applied Materials, Inc. | Defect free germanium oxide gap fill |
CN113823555B (zh) * | 2021-09-03 | 2024-06-07 | 合肥安德科铭半导体科技有限公司 | 一种在绝缘体上制备锗薄膜的方法 |
CN115341276B (zh) * | 2022-08-23 | 2024-03-01 | 中国科学院微电子研究所 | 一种r-GeO2薄膜单晶及其生长方法 |
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US7312165B2 (en) * | 2004-05-05 | 2007-12-25 | Jursich Gregory M | Codeposition of hafnium-germanium oxides on substrates used in or for semiconductor devices |
US7579285B2 (en) * | 2005-07-11 | 2009-08-25 | Imec | Atomic layer deposition method for depositing a layer |
US20080023070A1 (en) * | 2006-07-28 | 2008-01-31 | Sanjai Sinha | Methods and systems for manufacturing polycrystalline silicon and silicon-germanium solar cells |
US7749879B2 (en) * | 2006-08-03 | 2010-07-06 | Micron Technology, Inc. | ALD of silicon films on germanium |
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US10041169B2 (en) | 2008-05-27 | 2018-08-07 | Picosun Oy | System and method for loading a substrate holder carrying a batch of vertically placed substrates into an atomic layer deposition reactor |
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US9171715B2 (en) * | 2012-09-05 | 2015-10-27 | Asm Ip Holding B.V. | Atomic layer deposition of GeO2 |
US9218963B2 (en) * | 2013-12-19 | 2015-12-22 | Asm Ip Holding B.V. | Cyclical deposition of germanium |
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US20170069490A1 (en) | 2017-03-09 |
EP3114248A4 (en) | 2017-03-01 |
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