JP7449928B2 - 基板上にモリブデン膜を形成するための方法 - Google Patents
基板上にモリブデン膜を形成するための方法 Download PDFInfo
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- JP7449928B2 JP7449928B2 JP2021521480A JP2021521480A JP7449928B2 JP 7449928 B2 JP7449928 B2 JP 7449928B2 JP 2021521480 A JP2021521480 A JP 2021521480A JP 2021521480 A JP2021521480 A JP 2021521480A JP 7449928 B2 JP7449928 B2 JP 7449928B2
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- molybdenum
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims description 81
- 229910052750 molybdenum Inorganic materials 0.000 title claims description 79
- 239000011733 molybdenum Substances 0.000 title claims description 79
- 239000000758 substrate Substances 0.000 title claims description 71
- 238000000034 method Methods 0.000 title claims description 55
- 238000000151 deposition Methods 0.000 claims description 59
- 230000008021 deposition Effects 0.000 claims description 51
- 239000000463 material Substances 0.000 claims description 45
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 28
- CXPRFXGGNPUHAL-UHFFFAOYSA-N [Mo].ClOOCl Chemical compound [Mo].ClOOCl CXPRFXGGNPUHAL-UHFFFAOYSA-N 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 238000005229 chemical vapour deposition Methods 0.000 claims description 18
- 239000004065 semiconductor Substances 0.000 claims description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 3
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 3
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 229910052581 Si3N4 Inorganic materials 0.000 claims 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims 4
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 claims 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 2
- 239000002243 precursor Substances 0.000 description 17
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000003708 ampul Substances 0.000 description 8
- 238000005530 etching Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 7
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 7
- 238000007740 vapor deposition Methods 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- ASLHVQCNFUOEEN-UHFFFAOYSA-N dioxomolybdenum;dihydrochloride Chemical compound Cl.Cl.O=[Mo]=O ASLHVQCNFUOEEN-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910015686 MoOCl4 Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- SFPKXFFNQYDGAH-UHFFFAOYSA-N oxomolybdenum;tetrahydrochloride Chemical compound Cl.Cl.Cl.Cl.[Mo]=O SFPKXFFNQYDGAH-UHFFFAOYSA-N 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 238000005019 vapor deposition process Methods 0.000 description 2
- 229910017083 AlN Inorganic materials 0.000 description 1
- 229910015711 MoOx Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- 238000001208 nuclear magnetic resonance pulse sequence Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- H01L2924/049—Nitrides composed of metals from groups of the periodic table
- H01L2924/0494—4th Group
- H01L2924/04941—TiN
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Description
一般手順:
半導体デバイスは、以下のプロセスステップの順序で、二酸化ケイ素ベース層上に窒化チタンバリア層を含む基板上に製作することができる。
ステップ2:基板のバリア層(TiN層)をモリブデンジオキシジクロリド(MoO2Cl2)蒸気のパルスと、水素(H2)またはアルゴン(Ar)または不活性ガスの存在下、例えば500℃程度の温度で接触させること;
ステップ3;システムをH2または不活性ガス(例えば、Ar)下でパージして、MoO2Cl2前駆体とH2共反応体および基板との完全な反応を可能にする。
ステップ4:所望の特性のモリブデン膜層を形成するために、ステップ1~3(任意選択)を繰り返すこと。
以下の範囲のプロセスパラメーター;
1)毎分1標準立方センチメートル(sccm)から1000sccmの範囲の前駆体流。
2)1~10000sccmの範囲の不活性前駆体キャリヤガス流
3)25sccm~25000sccmの範囲のH2共反応体流
4)0.1T~250Tの範囲の圧力
5)300~1000℃の基板温度
6)a)0.1秒~120秒間の前駆体パルス「オン」時間、b)1秒~120秒間の前駆体パルス「オフ」時間を含むパルスCVDサイクル時間
7)1~10000サイクルの堆積サイクル
400°~700℃の基板温度、1秒「オン」および39秒「オフ」の20~200堆積サイクル、4000sccm(4lpm)H2流、チャンバー圧力80TでのパルスCVD Mo堆積;Mo金属堆積速度は、0.1~5オングストローム/サイクルであり、抵抗率は10~33μΩ・cmであった。2~3オングストロームのAl2O3エッチングは、主に部分的にMo最上層でのXRFシグナルの損失によって測定され、Al2O3の実際のエッチングに起因しない可能性が高い。
450°~700℃の基板温度、1秒「オン」および39秒「オフ」の20~200堆積サイクル、4lpm H2流、チャンバー圧力80TでのパルスCVD Mo堆積;Mo金属堆積速度は、0.4~6オングストローム/サイクルであり、抵抗率は10~70μΩ・cmであった。SiO2エッチング速度は測定されなかった。
360°~700℃の基板温度、1秒「オン」および39秒「オフ」の25~200堆積サイクル、4lpm H2流、チャンバー圧力80TでのパルスCVD Mo堆積;Mo金属堆積速度は、0.2~2.8オングストローム/サイクルであり、抵抗率は12~1200μΩ・cmであった。0~2.3オングストロームのTiNエッチングを測定した。
Claims (9)
- 基板上にモリブデン含有材料を形成するための方法であって、約300℃~約400℃の温度における蒸着条件下で基板をモリブデンジオキシジクロリド(MoO2Cl2)蒸気と接触させて、基板上にモリブデン含有材料を堆積させることを含み、基板が、窒化チタン(TiN)、窒化タンタル(TaN)、窒化アルミニウム(AlN)、酸化アルミニウム(Al2O3)、酸化ジルコニウム(ZrO2)、酸化ハフニウム(HfO2)、二酸化ケイ素(SiO2)、窒化ケイ素(SiN)、酸化ランタン(La2O3)、酸化ルテニウム(RuO2)、酸化イリジウム(IrO2)、酸化ニオブ(Nb2O5)、および酸化イットリウム(Y2O3)から選択される、方法。
- 基板が窒化チタンであり、モリブデンジオキシジクロリド蒸気との窒化チタン基板の接触が、約350℃~約400℃の温度で実施される、請求項1に記載の方法。
- 基板が酸化アルミニウムであり、モリブデンジオキシジクロリド蒸気との酸化アルミニウム基板の接触が、約350℃~約400℃の温度で実施される、請求項1に記載の方法。
- 基板が二酸化ケイ素であり、モリブデンジオキシジクロリド蒸気との二酸化ケイ素基板の接触が、約350℃~約400℃の温度で実施される、請求項1に記載の方法。
- 蒸着条件が、堆積されたモリブデン含有材料の抵抗率が約20μΩ・cm未満であるように選択される、請求項1に記載の方法。
- 蒸着条件がH2をさらに含む、請求項1に記載の方法。
- 蒸着条件がパルス化学蒸着条件である、請求項1に記載の方法。
- モリブデン含有材料が、75%~100%の段差被覆で基板上に堆積される、請求項1に記載の方法。
- モリブデン膜を基板上に堆積させた半導体デバイスであって、前記膜が、99%超のモリブデン、1%未満の酸素、99%超のコンフォーマリティを含み、膜厚35Åで抵抗率が20μΩ・cm未満であり、基板が、窒化チタン(TiN)、窒化タンタル(TaN)、窒化アルミニウム(AlN)、酸化アルミニウム(Al2O3)、酸化ジルコニウム(ZrO2)、酸化ハフニウム(HfO2)、二酸化ケイ素(SiO2)、窒化ケイ素(SiN)、酸化ランタン(La2O3)、酸化ルテニウム(RuO2)、酸化イリジウム(IrO2)、酸化ニオブ(Nb2O5)、および酸化イットリウム(Y2O3)から選択され、半導体デバイスが、2:1~40:1の範囲の深さ対横寸法のアスペクト比(L/W)を有する、半導体デバイス。
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PCT/US2019/056435 WO2020086344A1 (en) | 2018-10-24 | 2019-10-16 | Method for forming molybdenum films on a substrate |
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JP7433132B2 (ja) * | 2020-05-19 | 2024-02-19 | 東京エレクトロン株式会社 | 成膜方法及び成膜装置 |
KR20230033721A (ko) | 2020-07-09 | 2023-03-08 | 엔테그리스, 아이엔씨. | Vi족 전구체 화합물 |
EP4019470A1 (de) * | 2020-12-23 | 2022-06-29 | UMICORE AG & Co. KG | Herstellung von moo2cl2 |
US11932935B2 (en) | 2021-05-07 | 2024-03-19 | Entegris, Inc. | Deposition process for molybdenum or tungsten materials |
KR20230091807A (ko) | 2021-12-16 | 2023-06-23 | 에스케이트리켐 주식회사 | 몰리브데넘 전구체 및 이를 이용한 몰리브데넘 함유 박막의 형성 방법 및 상기 몰리브데넘 함유 박막을 포함하는 반도체 소자. |
KR20230102083A (ko) | 2021-12-30 | 2023-07-07 | 에스케이트리켐 주식회사 | 신규한 몰리브데넘 함유 전구체 및 이를 이용한 몰리브데넘 함유 박막의 형성 방법 및 상기 몰리브데넘 함유 박막을 포함하는 소자. |
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