JP7345787B2 - 選択成膜方法 - Google Patents
選択成膜方法 Download PDFInfo
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- JP7345787B2 JP7345787B2 JP2020080178A JP2020080178A JP7345787B2 JP 7345787 B2 JP7345787 B2 JP 7345787B2 JP 2020080178 A JP2020080178 A JP 2020080178A JP 2020080178 A JP2020080178 A JP 2020080178A JP 7345787 B2 JP7345787 B2 JP 7345787B2
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- film
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- alcohol gas
- selectively
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- 238000000034 method Methods 0.000 title claims description 68
- 230000015572 biosynthetic process Effects 0.000 title claims description 47
- 239000007789 gas Substances 0.000 claims description 99
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 51
- 150000003333 secondary alcohols Chemical class 0.000 claims description 36
- 150000003509 tertiary alcohols Chemical class 0.000 claims description 35
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 16
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 15
- 239000012044 organic layer Substances 0.000 claims description 15
- 150000003138 primary alcohols Chemical class 0.000 claims description 12
- 230000000903 blocking effect Effects 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000012495 reaction gas Substances 0.000 claims description 9
- 238000000137 annealing Methods 0.000 claims description 8
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 7
- 238000009832 plasma treatment Methods 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 5
- 229910010282 TiON Inorganic materials 0.000 claims description 3
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 239000010408 film Substances 0.000 description 153
- 239000002243 precursor Substances 0.000 description 24
- 239000000376 reactant Substances 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 230000008569 process Effects 0.000 description 16
- 238000001179 sorption measurement Methods 0.000 description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 15
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- 238000000354 decomposition reaction Methods 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 150000002894 organic compounds Chemical class 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006557 surface reaction Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- BXCQGSQPWPGFIV-UHFFFAOYSA-N carbon monoxide;cobalt;cobalt(2+);methanone Chemical compound [Co].[Co+2].O=[CH-].O=[CH-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] BXCQGSQPWPGFIV-UHFFFAOYSA-N 0.000 description 1
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical group [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- -1 that is Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—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
- 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
- H01L21/0228—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 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
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- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic System
- H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic System by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
- H01L21/28562—Selective deposition
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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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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76877—Filling of holes, grooves or trenches, e.g. vias, with conductive material
- H01L21/76883—Post-treatment or after-treatment of the conductive material
Description
<第1の実施形態>
図1は第1の実施形態に係る選択成膜方法を示すフローチャート、図2A~図2Cは図1に示す各工程を示す工程断面図である。
(1)膜41の材料:Ru
プリカーサ:Ru(EtCp)2
リアクタント:O2
温度:300℃以下
(2)膜41の材料:AlO
プリカーサ:TMA(トリメチルアルミニウム)
リアクタント:H2O
温度:450℃以下
(3)膜41の材料:Co
プリカーサ:Co2(CO)8
リアクタント:なし
温度:300℃以下
(4)膜41の材料:TiOx
プリカーサ:Ti(NMe2)4
リアクタント:H2O
温度:50~250℃
(5)膜41の材料:HfOx
プリカーサ:Hf(NMe2)4
リアクタント:H2O
温度:50~400℃
(6)膜41の材料:SiOx
プリカーサ:SiH(NMe 2 ) 3
リアクタント:H2O
温度:~400℃
図3は第2の実施形態に係る選択成膜方法を示すフローチャート、図4は図3に示す各工程を示す工程断面図である。
次に、実験例について説明する。
ここでは、エタノール、1-プロパノール、IPA、1-ブタノールのSiO配管上での分解特性を調査した。SiO配管を450℃で2時間のArガスベーキングを行った後、温度を上昇させながら各ガスを供給した。
以上、実施形態について説明したが、今回開示された実施形態は、全ての点で例示であって制限的なものではないと考えられるべきである。上記の実施形態は、添付の特許請求の範囲およびその主旨を逸脱することなく、様々な形態で省略、置換、変更されてもよい。
10;基体
11;第1の膜
12;第2の膜
21,61;第1の表面
22,62;第2の表面
31;吸着層
41;膜
51;金属膜
52;絶縁膜
Claims (30)
- 第1の表面を有する第1の膜と、第2の表面を有する前記第1の膜とは異なる第2の膜とを含む基板を準備する工程と、
第2級アルコールガスおよび/または第3級アルコールガスを前記第2の表面に選択的に吸着させる工程と、
少なくとも原料ガスを供給して前記第1の表面に選択的に膜を形成する工程と、
を有し、
前記第2級アルコールガスおよび前記第3級アルコールガスは、第1級アルコールガスよりも低温で脱水素反応が生じて、前記第1級アルコールガスよりも低温で前記第2の表面に吸着する、選択成膜方法。 - 前記第1の膜は金属膜であり、前記第2の膜は絶縁膜である、請求項1に記載の選択成膜方法。
- 前記第1の膜を構成する前記金属膜は、Cu、Ru、Co、Ti、TiNの少なくとも一種であり、前記第2の膜を構成する前記絶縁膜は、SiOx、SiOC、SiOCN、SiNの少なくとも一種である、請求項2に記載の選択成膜方法。
- 表面に自然酸化膜が形成された金属膜と、絶縁膜とを有する基板を準備する工程と、
前記自然酸化膜を還元除去し、前記金属膜の第1の表面を露出させる工程と、
第2級アルコールガスおよび/または第3級アルコールガスを前記絶縁膜の第2の表面に選択的に吸着させる工程と、
少なくとも原料ガスを供給して前記第1の表面に選択的に膜を形成する工程と、
を有し、
前記第2級アルコールガスおよび前記第3級アルコールガスは、第1級アルコールガスよりも低温で脱水素反応が生じて、前記第1級アルコールガスよりも低温で前記第2の表面に吸着する、選択成膜方法。 - 前記自然酸化膜を還元除去する工程は、水素アニール処理または水素プラズマ処理により行われる、請求項4に記載の選択成膜方法。
- 前記水素アニール処理または前記水素プラズマ処理は、500℃以下の温度で行われる、請求項5に記載の選択成膜方法。
- 前記水素アニール処理は250~400℃の温度で行われ、前記水素プラズマ処理は400℃以下の温度で行われる、請求項6に記載の選択成膜方法。
- 前記自然酸化膜を還元除去する工程は、前記第2級アルコールガスおよび/または第3級アルコールガスを前記第2の表面に選択的に吸着させる工程の際に同時に実施する、請求項4に記載の選択成膜方法。
- 前記金属膜は、Cu、Ru、Co、Ti、TiNの少なくとも一種であり、前記絶縁膜は、SiOx、SiOC、SiOCN、SiNの少なくとも一種である、請求項4から請求項8のいずれか一項に記載の選択成膜方法。
- 前記第2級アルコールガスおよび/または第3級アルコールガスを前記第2の表面に選択的に吸着させる工程により吸着された有機層は、前記少なくとも原料ガスによる前記第2の表面への膜形成をブロックする機能を有する、請求項1から請求項9のいずれか一項に記載の選択成膜方法。
- 前記第2級アルコールガスおよび/または第3級アルコールガスを前記第2の表面に選択的に吸着させる工程は、100~350℃の範囲の温度で行われる、請求項10に記載の選択成膜方法。
- 前記第2級アルコールガスおよび/または第3級アルコールガスを前記第2の表面に選択的に吸着させる工程は、100~250℃の範囲の温度で行われる、請求項11に記載の選択成膜方法。
- 前記第2級アルコールは、イソプロピルアルコールおよび/または2-ブタノールである、請求項1から請求項12のいずれか一項に記載の選択成膜方法。
- 前記第2級アルコールガスおよび/または第3級アルコールガスを前記第2の表面に選択的に吸着させる工程は、前記第2級アルコールガスおよび/または第3級アルコールガスとしてイソプロピルアルコールを用いる場合に、100~150℃の範囲の温度で行う、請求項13に記載の選択成膜方法。
- 前記第3級アルコールは、ターシャリブチルアルコールおよび/または2-メチル-2-ブタノールである、請求項1から請求項14のいずれか一項に記載の選択成膜方法。
- 前記第2級アルコールガスおよび/または第3級アルコールガスを前記第2の表面に選択的に吸着させる工程と、前記第1の表面に選択的に膜を形成する工程は、2回以上交互に繰り返す、請求項1から請求項15のいずれか一項に記載の選択成膜方法。
- 前記第1の表面に選択的に膜を形成する工程により形成された膜は、金属膜または絶縁膜である、請求項1から請求項16のいずれか一項に記載の選択成膜方法。
- 前記第1の表面の前記金属膜は、Ru、Cu、Co、Ti、TiNの少なくとも一種であり、前記第1の表面の前記絶縁膜は、SiOx、SiOC、SiOCN、SiN、AlxOy、HfOx、ZrOx、TiOx、TiONの少なくとも一種である、請求項17に記載の選択成膜方法。
- 前記第1の表面に選択的に膜を形成する工程は、原料ガスおよび反応ガスを供給することにより行われる、請求項1から請求項18のいずれか一項に記載の選択成膜方法。
- 前記第1の表面に選択的に膜を形成する工程は、ALDまたはCVDにより行われる、請求項19に記載の選択成膜方法。
- 前記第1の表面に選択的に膜を形成する工程は、450℃以下の温度で行われる、請求項19または請求項20に記載の選択成膜方法。
- 反応ガスとしてH2O、H2、O2のいずれかを用いる、請求項19から請求項21のいずれか一項に記載の選択成膜方法。
- 前記第1の表面に選択的に膜を形成する工程は、原料ガスとしてRu(EtCp)2を用い、反応ガスとしてO2ガスを用いて、Ru膜を形成する、請求項22に記載の選択成膜方法。
- 前記第1の表面に選択的に膜を形成する工程は、原料ガスとしてTMAを用い、反応ガスとしてH2Oを用いて、AlxOy膜を形成する、請求項22に記載の選択成膜方法。
- 前記第1の表面に選択的に膜を形成する工程は、原料ガスとしてTi(NMe2)4を用い、反応ガスとしてH2Oを用いて、TiOx膜を形成する、請求項22に記載の選択成膜方法。
- 前記第1の表面に選択的に膜を形成する工程は、原料ガスとしてHf(NMe2)4を用い、反応ガスとしてH2Oを用いて、HfOx膜を形成する、請求項22に記載の選択成膜方法。
- 前記第1の表面に選択的に膜を形成する工程は、原料ガスとしてSiH(NMe 2 ) 3 を用い、反応ガスとしてH2Oを用いて、SiOx膜を形成する、請求項22に記載の選択成膜方法。
- 前記第1の表面に選択的に膜を形成する工程は、原料ガスを供給し、熱分解させることにより行われる、請求項1から請求項18のいずれか一項に記載の選択成膜方法。
- 前記第1の表面に選択的に膜を形成する工程は、CVDにより行われる、請求項28に記載の選択成膜方法。
- 前記第1の表面に選択的に膜を形成する工程は、原料ガスとしてCo2(CO)8を用い、熱分解させることによりCo膜を形成する、請求項29に記載の選択成膜方法。
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