JP2022546822A - 金属窒化物薄膜の形成方法 - Google Patents
金属窒化物薄膜の形成方法 Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 57
- 239000002184 metal Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 41
- 150000004767 nitrides Chemical class 0.000 title claims abstract description 40
- 239000010409 thin film Substances 0.000 title claims abstract description 36
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 18
- 150000002367 halogens Chemical class 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000008021 deposition Effects 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 9
- 229910001507 metal halide Inorganic materials 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- -1 metal halide compound Chemical class 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 45
- 229910052758 niobium Inorganic materials 0.000 claims description 19
- 229930195733 hydrocarbon Natural products 0.000 claims description 16
- 150000002430 hydrocarbons Chemical class 0.000 claims description 16
- 229910052715 tantalum Inorganic materials 0.000 claims description 16
- 229910052801 chlorine Inorganic materials 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 229910052721 tungsten Inorganic materials 0.000 claims description 13
- 229910052720 vanadium Inorganic materials 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 229910052794 bromium Inorganic materials 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- 229910052740 iodine Inorganic materials 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 9
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000012159 carrier gas Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000005121 nitriding Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000010955 niobium Substances 0.000 description 15
- 239000000460 chlorine Substances 0.000 description 11
- 238000000151 deposition Methods 0.000 description 11
- 239000010408 film Substances 0.000 description 8
- 238000000231 atomic layer deposition Methods 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 125000006165 cyclic alkyl group Chemical group 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CFJRGWXELQQLSA-UHFFFAOYSA-N azanylidyneniobium Chemical compound [Nb]#N CFJRGWXELQQLSA-UHFFFAOYSA-N 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 229910019804 NbCl5 Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000012705 liquid precursor Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 150000002822 niobium compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- ASRAWSBMDXVNLX-UHFFFAOYSA-N pyrazolynate Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(=O)C=1C(C)=NN(C)C=1OS(=O)(=O)C1=CC=C(C)C=C1 ASRAWSBMDXVNLX-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- FNKQXYHWGSIFBK-RPDRRWSUSA-N sapropterin Chemical compound N1=C(N)NC(=O)C2=C1NC[C@H]([C@@H](O)[C@@H](O)C)N2 FNKQXYHWGSIFBK-RPDRRWSUSA-N 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003482 tantalum compounds Chemical class 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 238000007736 thin film deposition technique Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- 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
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- 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
- C23C16/02—Pretreatment of the material to be coated
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- 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
- C23C16/44—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 method of coating
- C23C16/455—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 method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- 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
- C23C16/44—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 method of coating
- C23C16/455—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 method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
Abstract
Description
技術的課題
本発明の目的は,金属窒化物薄膜を効果的に形成することができる方法を提供することにある。
本発明の一実施形態によれば,金属窒化物薄膜を形成する方法は,基板に金属前駆体を供給して前記基板の表面に選択的に堆積させる堆積工程; 前記基板にハロゲンガスを供給して前記基板の表面に金属ハロゲン化合物を形成するハロゲン処理工程; 前記基板に窒素源を供給して前記金属ハロゲン化合物と反応させ,金属窒化物を形成する窒化工程を含む。
本発明の一実施形態によれば,前記金属前駆体は,金属窒化物(例えば,ニオブ薄膜)を蒸着に適していることを確認することができ,前記金属前駆体が持続的な加温でも特性が劣化しない高い熱的安定性とともに高い蒸気圧(vapor pressure)を有することにより,有機金属化学気相蒸着法(Metal Organic Chemical Vapor Deposition, MOCVD)及び原子層堆積法(Atomic Layer Deposition,ALD)を用いた金属窒化物薄膜を蒸着する半導体製造工程に有用に適用できることが分かる。
X=F,Cl,Br,Iを含む周期律表上の17族のうちの1つ。
R1,R2=それぞれ互いに独立して炭素数1~10の直鎖状のアルキル基,枝分かれ状のアルキル基又は,環状のアルキル基のうちの1つであり,互いに同じでも異なっていてもよい。
1≦n≦4
1≦a≦4
1≦b≦5
X=F,Cl,Br,Iを含む周期律表上の17族のうちの1つ。
R1,R2,R3=それぞれ互いに独立して炭素数1~10の直鎖状のアルキル基,枝分かれ状アルキル基又は,環状のアルキル基のうちの1つであり,互いに同じでも異なっていてもよい。
1≦n≦4
1≦a≦4
1≦b≦5
X=F,Cl,Br,Iを含む周期律表上の17族のうちの1つ。
R1,R2,R3=それぞれ互いに独立して炭素数1~10の直鎖状のアルキル基,枝分かれ状のアルキル基又は,環状のアルキル基のうちの1つであり,互いに同じでも異なっていてもよい。
1≦n≦4
1≦a≦4
1≦b≦5
X=F,Cl,Br,Iを含む周期律表上の17族のうちの1つ。
R1,R2,R3,R4=それぞれ互いに独立して炭素数1~10の直鎖線状のアルキル基,枝分かれ状のアルキル基又は,環状のアルキル基のうちの1つであり,互いに同じでも異なっていてもよい。
1≦n≦4
1≦a≦4
1≦b≦5
Claims (12)
- 金属窒化物薄膜を形成する方法において,
基板に金属前駆体を供給して前記基板の表面に選択的に堆積させる堆積工程;
前記基板にハロゲンガスを供給して前記基板の表面に金属ハロゲン化合物を形成するハロゲン処理工程;及び
前記基板に窒素源を供給して前記金属ハロゲン化合物と反応させ,金属窒化物を形成する窒化工程を含む,金属窒化物薄膜を形成する方法。 - 前記金属窒化物は,MaNb(MはV,Nb,Ta,Wのうちの1つ,1≦a≦4,1≦b≦5)である,請求項1記載の金属窒化物薄膜を形成する方法。
- 前記金属前駆体は,MXn(NR1R2)5-n(1≦n≦4),MX(NR1R2)2NR3,MX2(NR1R2)NR3及び,M(NR1R2)2(NR3)R4のいずれか一つ以上である,請求項1記載の金属窒化物薄膜を形成する方法。
- 前記MXn(NR1R2)5-nにおいて,MはV,Nb,Ta,Wのうちの1つであり,XはF,Cl,Br,Iを含む17族のうちの1つであり,R1,R2はそれぞれ互いに独立して炭素数1~10の直鎖状の炭化水素,枝分かれ状の炭化水素又は,環状の炭化水素のうちの1つであり,互いに同一又は異なる,請求項3記載の金属窒化物薄膜を形成する方法。
- 前記金属前駆体はキャリアガスと共に供給され,前記キャリアガスは窒素(N2),アルゴン(Ar),ヘリウム(He)を含む不活性ガスのうちの少なくとも1つである,請求項1~7いずれか1項記載の金属窒化物薄膜を形成する方法。
- 前記ハロゲンガスは,X2,HXのうちの少なくとも1つである,請求項1~7いずれか1項記載の金属窒化物薄膜を形成する方法。
- 前記窒素源は,NH3 ,NHR2 (RはC1 ~C5の直鎖状のアルキル基,枝分かれ状のアルキル基又は,芳香族アルキル基のうちの少なくとも1つ),NH2R(RはC1~C5の直鎖状のアルキル基 ,枝分かれ状のアルキル基又は,芳香族アルキル基のうちの少なくとも1つ),NR3(RはC1~C5の直鎖状のアルキル基,枝分かれ状のアルキル基又は,芳香族アルキル基のうちの少なくとも1つ),ヒドラジン(Hydrazine,H4N2),R-ヒドラジン(RはC1~C5の直鎖状のアルキル基,枝分かれ状のアルキル基又は,芳香族アルキル基のうちの少なくとも1つ),H2プラズマ,N2プラズマ又は,NH3プラズマのうちの1つ以上である,請求項1~7いずれか1項記載の金属窒化物薄膜を形成する方法。
- 前記堆積工程,前記ハロゲン処理工程及び,前記窒化工程は,250~600℃でそれぞれ進行させる,請求項1~7いずれか1項記載の金属窒化物薄膜を形成する方法。
- 前記堆積工程,前記ハロゲン処理工程及び,前記窒化工程は1サイクルを形成し,前記サイクルを繰り返す,請求項1~7いずれか1項記載の金属窒化物薄膜を形成する方法。
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KR1020190108609A KR20210027770A (ko) | 2019-09-03 | 2019-09-03 | 금속 질화물 박막의 형성 방법 |
PCT/KR2020/009806 WO2021045385A2 (ko) | 2019-09-03 | 2020-07-24 | 금속 질화물 박막의 형성 방법 |
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JP2010541276A (ja) * | 2007-10-04 | 2010-12-24 | アプライド マテリアルズ インコーポレイテッド | Mocvdとhvpeを用いたiii−v族窒化膜の成長における寄生粒子抑制 |
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KR102627456B1 (ko) * | 2015-12-21 | 2024-01-19 | 삼성전자주식회사 | 탄탈럼 화합물과 이를 이용한 박막 형성 방법 및 집적회로 소자의 제조 방법 |
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JP2010541276A (ja) * | 2007-10-04 | 2010-12-24 | アプライド マテリアルズ インコーポレイテッド | Mocvdとhvpeを用いたiii−v族窒化膜の成長における寄生粒子抑制 |
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