KR102738996B1 - novel tungsten precursor compounds - Google Patents
novel tungsten precursor compounds Download PDFInfo
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- KR102738996B1 KR102738996B1 KR1020190098584A KR20190098584A KR102738996B1 KR 102738996 B1 KR102738996 B1 KR 102738996B1 KR 1020190098584 A KR1020190098584 A KR 1020190098584A KR 20190098584 A KR20190098584 A KR 20190098584A KR 102738996 B1 KR102738996 B1 KR 102738996B1
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- alkyl
- tungsten
- chemical formula
- thin film
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- 229910052721 tungsten Inorganic materials 0.000 title claims description 37
- 239000010937 tungsten Substances 0.000 title claims description 37
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims description 33
- 150000001875 compounds Chemical class 0.000 title claims description 19
- 239000002243 precursor Substances 0.000 title description 17
- 239000000126 substance Substances 0.000 claims description 54
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 36
- 150000003658 tungsten compounds Chemical class 0.000 claims description 33
- 125000003282 alkyl amino group Chemical group 0.000 claims description 30
- 239000010409 thin film Substances 0.000 claims description 27
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 12
- 238000000427 thin-film deposition Methods 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000000231 atomic layer deposition Methods 0.000 claims description 7
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 238000007740 vapor deposition Methods 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims 1
- -1 tungsten nitride Chemical class 0.000 description 27
- 125000000217 alkyl group Chemical group 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- 239000010408 film Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- PPJPTAQKIFHZQU-UHFFFAOYSA-N bis(tert-butylimino)tungsten;dimethylazanide Chemical compound C[N-]C.C[N-]C.CC(C)(C)N=[W]=NC(C)(C)C PPJPTAQKIFHZQU-UHFFFAOYSA-N 0.000 description 4
- 235000011089 carbon dioxide Nutrition 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002367 halogens Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- NXHILIPIEUBEPD-UHFFFAOYSA-H tungsten hexafluoride Chemical compound F[W](F)(F)(F)(F)F NXHILIPIEUBEPD-UHFFFAOYSA-H 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- 125000005916 2-methylpentyl group Chemical group 0.000 description 2
- 125000003469 3-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000005917 3-methylpentyl group Chemical group 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- FQNHWXHRAUXLFU-UHFFFAOYSA-N carbon monoxide;tungsten Chemical group [W].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] FQNHWXHRAUXLFU-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 2
- 238000005121 nitriding Methods 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- 125000003562 2,2-dimethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003660 2,3-dimethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003764 2,4-dimethylpentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004336 3,3-dimethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004337 3-ethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- IVHJCRXBQPGLOV-UHFFFAOYSA-N azanylidynetungsten Chemical compound [W]#N IVHJCRXBQPGLOV-UHFFFAOYSA-N 0.000 description 1
- 125000003828 azulenyl group Chemical group 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000001712 tetrahydronaphthyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
-
- 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
- C23C16/44—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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
본 발명의 신규한 텅스텐 전구체 화합물, 이의 제조방법 및 이를 포함하는 박막증착용 조성물을 제공하는 것으로, 본 발명의 텅스텐함유 박막증착용 조성물은 상온에서 액체로 취급이 용이하고 열안정성이 우수하며, 휘발성이 높은 본 발명의 텅스텐 화합물을 포함함으로써 양질의 박막을 제조할 수 있다.The present invention provides a novel tungsten precursor compound, a method for producing the same, and a composition for thin film deposition comprising the same. The tungsten-containing thin film deposition composition of the present invention is easy to handle as a liquid at room temperature, has excellent thermal stability, and can produce a high-quality thin film by including the tungsten compound of the present invention with high volatility.
Description
본 발명은 신규 텅스텐 전구체 화합물에 관한 것으로, 보다 상세하게는 텅스텐 함유 박막증착용 전구체로 유용한 텅스텐 화합물, 이의 제조방법, 이를 포함하는 텅스텐함유 박막증착용 조성물 및 이를 이용하는 텅스텐함유 박막의 제조방법에 관한 것이다.The present invention relates to a novel tungsten precursor compound, and more specifically, to a tungsten compound useful as a precursor for tungsten-containing thin film deposition, a method for producing the same, a composition for tungsten-containing thin film deposition comprising the same, and a method for producing a tungsten-containing thin film using the same.
반도체 산업에서의 신기술 및 재료의 개발로 인해 반도체 집적회로와 같은 소자의 미세화, 고신뢰화, 고속화, 고기능화, 고집적화 등이 가능해졌다.The development of new technologies and materials in the semiconductor industry has made possible the miniaturization, high reliability, high speed, high functionality, and high integration of components such as semiconductor integrated circuits.
이에 따라 박막을 형성하기위한 전구체에 요구되는 특성도 변화되어 왔다. 일반적으로 박막증착용 전구체에 요구되는 특성은 증기압이 높고 열 안정성이 우수하며 증착 챔버로의 이송이 쉬운 기체 또는 액체상의 화합물이어야 하고, 나아가 제조되는 박막의 종류에 따라 사용되는 반응 가스들과의 반응성도 우수해야한다.Accordingly, the characteristics required for precursors for forming thin films have also changed. In general, the characteristics required for precursors for thin film deposition are that they should be gaseous or liquid compounds with high vapor pressure, excellent thermal stability, and easy transport to the deposition chamber, and furthermore, they should have excellent reactivity with the reaction gases used depending on the type of thin film being manufactured.
한편 텅스텐 박막은 반도체 소자의 제조 공정에 있어서 다양하게 사용되고 있다. 구체적으로, 텅스텐, 특히 텅스텐 질화물(W-N)은 저항성이 비교적 낮고, 우수한 접착성을 가질 뿐만 아니라, 우수한 확산 방지막 성질을 갖고 있기 때문에, 기존의 Ti/TiN을 대체할 수 있는 소재로 많은 관심을 받고 있다.Meanwhile, tungsten thin films are being used in various ways in the manufacturing process of semiconductor devices. Specifically, tungsten, especially tungsten nitride (W-N), has relatively low resistivity, excellent adhesiveness, and excellent diffusion barrier properties, so it is receiving much attention as a material that can replace existing Ti/TiN.
일례로 구리(Cu)의 확산 방지막으로 질화 텅스텐(WN)막, 금속과 금속층을 연결해 주는 접전 재료(contact material)로 텅스텐 금속막 등이 있다. 이와 같은 텅스텐 막을 얻기위해 육불화텅스텐(WF6)과 반응 가스(NH3 및 H2)를 사용하여 CVD 방법으로 증착을 하여왔다. 그러나 육불화텅스텐과 반응 가스의 반응 부산물로 HF 및 HF salt 가 발생되어 기판에 결함을 유도하는 단점을 가진다. 이러한 단점을 극복하기 위한 많은 텅스텐 전구체들이 제안되어왔다. 일례로 텅스텐 헥사카르보닐(Tungsten hexacrbonyl, W(CO)6)이 제안되었으나, 텅스텐 헥사카르보닐은 고체 소스로 증착 챔버로의 이송 및 CO기에 의한 독성 때문에 박막증착용 전구체로 사용하기 어려운 단점을 가진다.For example, there is a tungsten nitride (WN) film as a diffusion barrier for copper (Cu), and a tungsten metal film as a contact material connecting metal and metal layers. In order to obtain such a tungsten film, deposition has been performed using tungsten hexafluoride (WF 6 ) and reaction gases (NH 3 and H 2 ) by the CVD method. However, HF and HF salt are generated as reaction byproducts of tungsten hexafluoride and the reaction gas, which has the disadvantage of inducing defects in the substrate. Many tungsten precursors have been proposed to overcome this disadvantage. For example, tungsten hexacarbonyl (W(CO) 6 ) has been proposed, but tungsten hexacarbonyl has the disadvantages of being difficult to use as a precursor for thin film deposition due to the difficulty in transporting it to the deposition chamber as a solid source and the toxicity of CO radicals.
더구나 텅스텐 질화막의 경우 육불화텅스텐을 전구체로 사용하여 텅스텐 금속막을 형성한 후 형성된 텅스텐 금속막을 다시 질화시키는 별도의 단계가 필요함으로 공정이 복잡한 문제점을 가진다.Moreover, in the case of a tungsten nitride film, the process is complicated because a separate step is required to form a tungsten metal film using tungsten hexafluoride as a precursor and then nitriding the formed tungsten metal film again.
따라서 박막 전구체로서 향상된 특성을 가지는 동시에 간단한 공정으로 다양한 텅스텐막을 형성할 수 있는 텅스텐 전구체의 개발이 여전히 요구되고 있다.Therefore, there is still a need for the development of a tungsten precursor that has improved properties as a thin film precursor and can form various tungsten films through a simple process.
본 발명은 텅스텐함유 박막의 제조가 가능한 전구체로 신규한 텅스텐 화합물 및 이의 제조방법을 제공한다.The present invention provides a novel tungsten compound as a precursor capable of producing a tungsten-containing thin film and a method for producing the same.
또한 본 발명은 본 발명의 텅스텐 화합물을 포함하는 텅스텐함유 박막증착용 조성물을 제공한다.The present invention also provides a composition for deposition of a tungsten-containing thin film comprising the tungsten compound of the present invention.
또한 본 발명은 본 발명의 텅스텐함유 박막증착용 조성물을 이용하는 텅스텐함유 박막의 제조방법을 제공한다.In addition, the present invention provides a method for manufacturing a tungsten-containing thin film using the tungsten-containing thin film deposition composition of the present invention.
본 발명은 놀랍도록 향상된 열안정성 및 휘발성을 가져 텅스텐함유 박막의 전구체로 매우 유용한 텅스텐 화합물을 제공하는 것으로, 본 발명의 텅스텐 화합물은 하기 화학식 1로 표시된다.The present invention provides a tungsten compound having surprisingly improved thermal stability and volatility and being very useful as a precursor of a tungsten-containing thin film, the tungsten compound of the present invention being represented by the following chemical formula 1.
[화학식 1][Chemical Formula 1]
(상기 화학식 1에서,(In the above chemical formula 1,
R1 및 R2는 서로 독립적으로 (C1-C10)알킬이며,R 1 and R 2 are independently (C1-C10) alkyl,
R3은 (C1-C10)알킬 또는 (C6-C12)아릴(C1-C10)알킬이며;R 3 is (C1-C10)alkyl or (C6-C12)aryl(C1-C10)alkyl;
R4는 모노(C1-C10)알킬아미노 또는 디(C1-C10)알킬아미노이다.)R 4 is mono(C1-C10)alkylamino or di(C1-C10)alkylamino.)
바람직하게 본 발명의 상기 화학식 1에서 R1 및 R2는 서로 독립적으로 (C1-C4)알킬이며, R3은 (C1-C4)알킬 또는 (C6-C12)아릴(C1-C4)알킬이며, R4는 모노(C1-C4)알킬아미노 또는 디(C1-C4)알킬아미노일 수 있다.Preferably, in the chemical formula 1 of the present invention, R 1 and R 2 are independently (C1-C4) alkyl, R 3 is (C1-C4) alkyl or (C6-C12) aryl (C1-C4) alkyl, and R 4 may be mono (C1-C4) alkylamino or di (C1-C4) alkylamino.
열안정성 및 휘발성 측면에서 바람직하게 본 발명의 상기 화학식 1은 하기 화학식 2로 표시될 수 있다.In terms of thermal stability and volatility, the chemical formula 1 of the present invention can preferably be represented by the following chemical formula 2.
[화학식 2][Chemical formula 2]
(상기 화학식 2에서(In the above chemical formula 2
R11은 (C1-C10)알킬이며,R 11 is (C1-C10) alkyl,
R3은 (C1-C10)알킬 또는 (C6-C12)아릴(C1-C10)알킬이며;R 3 is (C1-C10)alkyl or (C6-C12)aryl(C1-C10)alkyl;
R4는 모노(C1-C10)알킬아미노 또는 디(C1-C10)알킬아미노이다.)R 4 is mono(C1-C10)alkylamino or di(C1-C10)alkylamino.)
본 발명의 일 실시예에 따른 화학식 2에서 R11은 tert-부틸이며, R3은 (C1-C4)알킬 또는 (C6-C12)아릴(C1-C4)알킬이며, R4는 디(C1-C4)알킬아미노일 수 있으며, 바람직하게 R11은 tert-부틸이며, R3은 (C1-C4)알킬 또는 (C6-C12)아릴(C1-C4)알킬이며, R4는 디(C1-C4)알킬아미노일 수 있다.In chemical formula 2 according to one embodiment of the present invention, R 11 is tert-butyl, R 3 is (C1-C4)alkyl or (C6-C12)aryl(C1-C4)alkyl, and R 4 may be di(C1-C4)alkylamino, preferably R 11 is tert-butyl, R 3 is (C1-C4)alkyl or (C6-C12)aryl(C1-C4)alkyl, and R 4 may be di(C1-C4)alkylamino.
구체적으로 본 발명의 일 실시예에 따른 텅스텐 화합물은 하기 화합물에서 선택되는 것일 수 있으나, 이에 한정이 있는 것은 아니다.Specifically, the tungsten compound according to one embodiment of the present invention may be selected from the following compounds, but is not limited thereto.
또한 본 발명은 본 발명의 텅스텐 화합물의 제조방법을 제공하는 것으로, 본 발명의 텅스텐 화합물의 제조방법은 하기 화학식 3의 화합물과 하기 화학식 4의 화합물을 반응시켜 하기 화학식 2의 화합물을 제조하는 단계를 포함한다.In addition, the present invention provides a method for producing a tungsten compound of the present invention, wherein the method for producing a tungsten compound of the present invention includes a step of reacting a compound of the following chemical formula 3 with a compound of the following chemical formula 4 to produce a compound of the following chemical formula 2.
[화학식 2][Chemical formula 2]
[화학식 3][Chemical Formula 3]
[화학식 4][Chemical Formula 4]
(상기 화학식 2 내지 4에서,(In the above chemical formulas 2 to 4,
R11 및 R21 내지 R22는 서로 독립적으로 (C1-C10)알킬이며,R 11 and R 21 to R 22 is independently (C1-C10) alkyl,
R3은 (C1-C10)알킬 또는 (C6-C12)아릴(C1-C10)알킬이며;R 3 is (C1-C10)alkyl or (C6-C12)aryl(C1-C10)alkyl;
R4는 모노(C1-C10)알킬아미노 또는 디(C1-C10)알킬아미노이며;R 4 is mono(C1-C10)alkylamino or di(C1-C10)alkylamino;
X는 할로겐이다.)X is a halogen.)
또한 본 발명은 하기 화학식 5로 표시되는 텅스텐 화합물을 포함하는 박막증착용 조성물 및 본 발명의 박막증착용 조성물을 이용하여 텅스텐함유 박막의 제조방법을 제공한다.In addition, the present invention provides a composition for thin film deposition comprising a tungsten compound represented by the following chemical formula 5 and a method for producing a tungsten-containing thin film using the composition for thin film deposition of the present invention.
[화학식 5][Chemical Formula 5]
(상기 화학식 5에서,(In the above chemical formula 5,
R1a 및 R2a는 서로 독립적으로 (C1-C10)알킬이며,R 1a and R 2a are independently (C1-C10) alkyl,
R3a은 (C1-C10)알킬 또는 (C6-C12)아릴(C1-C10)알킬이며;R 3a is (C1-C10)alkyl or (C6-C12)aryl(C1-C10)alkyl;
R4a는 (C1-C10)알킬, (C6-C12)아릴(C1-C10)알킬, 모노(C1-C10)알킬아미노 또는 디(C1-C10)알킬아미노이다.)R 4a is (C1-C10)alkyl, (C6-C12)aryl(C1-C10)alkyl, mono(C1-C10)alkylamino or di(C1-C10)alkylamino.)
본 발명의 일 실시예에 따른 박막은 유기금속 화학기상 증착법, 원자층 증착법공정, 저압 기상 증착법, 플라즈마 강화 기상 증착법 또는 플라즈마 강화 원자층 증착법에 의해 수행되는 것일 수 있다.The thin film according to one embodiment of the present invention may be formed by a metalorganic chemical vapor deposition method, an atomic layer deposition process, a low pressure vapor deposition method, a plasma enhanced vapor deposition method, or a plasma enhanced atomic layer deposition method.
본 발명의 텅스텐 화합물은 텅스텐함유 박막의 전구체로 우수한 열안정성 및 휘발성을 가짐으로써 양질의 텅스텐함유 박막을 제조할 수 있다.The tungsten compound of the present invention has excellent thermal stability and volatility as a precursor of a tungsten-containing thin film, thereby enabling the production of a high-quality tungsten-containing thin film.
또한 본 발명의 텅스텐 화합물은 상온에서 액체로 취급이 매우 용이하며, 저장안정성이 매우 높다.In addition, the tungsten compound of the present invention is very easy to handle as a liquid at room temperature and has very high storage stability.
또한 본 발명의 텅스텐 화합물은 화합물 내 질소를 포함함으로써 별도의 금속박막의 질화단계가 필요치 않아 간단한 공정으로 텅스텐 질화막을 제조할 수 있다.In addition, since the tungsten compound of the present invention includes nitrogen in the compound, a separate nitriding step of a metal thin film is not required, so a tungsten nitride film can be manufactured through a simple process.
따라서 본 발명의 텅스텐함유 박막증착용 조성물은 본 발명의 텅스텐 화합물을 전구체로 사용함으로써 다양한 공정으로 양질의 박막을 제조할 수 있다.Therefore, the tungsten-containing thin film deposition composition of the present invention can produce a high-quality thin film through various processes by using the tungsten compound of the present invention as a precursor.
도 1은 본 발명의 실시예 1에서 제조된 텅스텐 화합물의 TGA 분석 결과를 나타낸 그래프이다.Figure 1 is a graph showing the results of TGA analysis of a tungsten compound manufactured in Example 1 of the present invention.
본 발명에 기재된 "알킬"은 탄소수 1 내지 10, 바람직하게 탄소수 1 내지 6, 보다 바람직하게 탄소수 1 내지 4를 가진 포화된 직쇄상 또는 분지상의 비-고리(cyclic) 탄화수소를 의미한다. "저급 알킬"은 탄소수가 1 내지 4인 직쇄상 또는 분지상 알킬을 의미한다. 대표적인 포화 직쇄상 알킬은 -메틸, -에틸, -n-프로필, -n-부틸, -n-펜틸, -n-헥실, -n-헵틸, -n-옥틸, -n-노닐 과 -n-데실을 포함하고, 반면에 포화 분지상 알킬은 -이소프로필, -sec-부틸, -이소부틸, -tert-부틸, 이소펜틸, 2-메틸헥실, 3-메틸부틸, 2-메틸펜틸, 3-메틸펜틸, 4-메틸펜틸, 2-메틸헥실, 3-메틸헥실, 2-메틸펜틸, 3-메틸펜틸, 4-메틸펜틸, 2-메틸헥실, 3-메틸헥실, 4-메틸헥실, 5- 메틸헥실, 2,3-디메틸부틸, 2,3-디메틸펜틸, 2,4-디메틸펜틸, 2,3-디메틸헥실, 2,4-디메틸헥실, 2,5-디메틸헥실, 2,2-디메틸펜틸, 2,2-디메틸헥실, 3,3-디메틸펜틸, 3,3-디메틸헥실, 4,4-디메틸헥실, 2-에틸펜틸, 3-에틸펜틸, 2-데틸헥실, 3-에틸헥실, 4-에틸헥실, 2-메틸-2-에틸펜틸, 2-메틸-3-에틸펜틸, 2-메틸-4-에틸펜틸, 2-메틸-2-에틸헥실, 2-메틸-3-에틸헥실, 2-메틸-4-에틸헥실, 2,2-디에틸펜틸, 3,3-디에틸헥실, 2,2-디에틸헥실, 및 3,3-디에틸헥실을 포함한다."Alkyl" as used herein means a saturated straight-chain or branched non-cyclic hydrocarbon having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. "Lower alkyl" means a straight-chain or branched alkyl having 1 to 4 carbon atoms. Representative saturated straight-chain alkyls include -methyl, -ethyl, -n-propyl, -n-butyl, -n-pentyl, -n-hexyl, -n-heptyl, -n-octyl, -n-nonyl and -n-decyl, whereas saturated branched alkyls include -isopropyl, -sec-butyl, -isobutyl, -tert-butyl, isopentyl, 2-methylhexyl, 3-methylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 2,3-dimethylbutyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 2,3-dimethylhexyl, 2,4-Dimethylhexyl, 2,5-dimethylhexyl, 2,2-dimethylpentyl, 2,2-dimethylhexyl, 3,3-dimethylpentyl, 3,3-dimethylhexyl, 4,4-dimethylhexyl, 2-ethylpentyl, 3-ethylpentyl, 2-deethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-methyl-2-ethylpentyl, 2-methyl-3-ethylpentyl, 2-methyl-4-ethylpentyl, 2-methyl-2-ethylhexyl, 2-methyl-3-ethylhexyl, 2-methyl-4-ethylhexyl, 2,2-diethylpentyl, 3,3-diethylhexyl, 2,2-diethylhexyl, and 3,3-diethylhexyl.
본 명세서에서 "C1-C10"와 같이 기재된 경우, 이는 탄소수가 1 내지 10개임을 의미한다. 예를 들어, C1-C4알킬은 탄소 수가 1 내지 4인 알킬을 의미한다. 구체적인 일례로 메틸(methyl), 에틸(ethyl), 프로필(propyl), 이소프로필(iso-propyl), 부틸(butyl), 이소부틸(iso-butyl) 또는 tert-부틸(tert-butyl)일 수 있다.When it is described as "C1-C10" in this specification, it means that it has 1 to 10 carbon atoms. For example, C1-C4 alkyl means alkyl having 1 to 4 carbon atoms. Specific examples thereof include methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, or tert-butyl.
본 명세서에 기재된 "할로겐"은 플루오린, 클로린, 브로민 또는 아이오딘을 의미한다.“Halogen” as used herein means fluorine, chlorine, bromine or iodine.
본 명세서에서 기재된 "아릴"은 5 내지 10의 고리 원자를 함유하는 탄소고리 방향족 그룹을 의미한다. 대표적인 예는 페닐, 톨일(tolyl), 자이릴(xylyl), 나프틸, 테트라하이드로나프틸, 안트라세닐(anthracenyl), 플루오레닐(fluorenyl), 인데닐(indenyl), 아주레닐(azulenyl) 등을 포함하나 이에 한정되는 것은 아니다. 탄소고리 방향족 그룹은 선택적으로 치환될 수 있다.The term "aryl" as used herein refers to a carbon ring aromatic group containing 5 to 10 ring atoms. Representative examples include, but are not limited to, phenyl, tolyl, xylyl, naphthyl, tetrahydronaphthyl, anthracenyl, fluorenyl, indenyl, azulenyl, and the like. The carbon ring aromatic group can be optionally substituted.
본 명세서에서 기재된 "모노알킬아미노"는 -NHCH3, -NHCH2CH3, -NH(CH2)2CH3, -NH(CH2)3CH3, -NH(CH2)4CH3, -NH(CH2)5CH3, 및 이와 유사한 것을 포함하는, -NH(알킬)을 의미하며, 여기에서 알킬은 위에서 정의된 것과 같다.The term "monoalkylamino" as used herein means -NH(alkyl), including -NHCH 3 , -NHCH 2 CH 3 , -NH(CH 2 ) 2 CH 3 , -NH(CH 2 ) 3 CH 3 , -NH(CH 2 ) 4 CH 3 , -NH(CH 2 ) 5 CH 3 , and the like, wherein alkyl is as defined above.
본 명세서에서 기재된 "디알킬아미노"는 -N(CH3)2, -N(CH2CH3)2, -N((CH2)2CH3)2, -N(CH3)(CH2CH3), 및 이와 유사한 것을 포함하는 -N(알킬)(알킬)을 의미하며, 여기에서 각 알킬은 서로 독립적으로 위에서 정의된 알킬이다.As used herein, "dialkylamino" means -N(alkyl)(alkyl), including -N(CH 3 ) 2 , -N(CH 2 CH 3 ) 2 , -N( ( CH 2 ) 2 CH 3 ) 2 , -N(CH 3 )(CH 2 CH 3 ), and the like, wherein each alkyl is independently an alkyl as defined above.
본 명세서에 기재된 “아릴알킬”은 알킬의 하나의 수소가 아릴로 치환된 것을 의미하며, 아릴 및 알킬은 위에서 정의된 알킬이다.“Arylalkyl” as used herein means that one hydrogen of alkyl is replaced by aryl, and aryl and alkyl are alkyl as defined above.
본 발명은 텅스텐함유 박막의 전구체로 매우 유용한 텅스텐 화합물을 제공하는 것으로, 본 발명의 텅스텐 화합물은 하기 화학식 1로 표시된다.The present invention provides a tungsten compound that is very useful as a precursor of a tungsten-containing thin film, and the tungsten compound of the present invention is represented by the following chemical formula 1.
[화학식 1][Chemical Formula 1]
(상기 화학식 1에서,(In the above chemical formula 1,
R1 및 R2는 서로 독립적으로 (C1-C10)알킬이며,R 1 and R 2 are independently (C1-C10) alkyl,
R3은 (C1-C10)알킬 또는 (C6-C12)아릴(C1-C10)알킬이며;R 3 is (C1-C10)alkyl or (C6-C12)aryl(C1-C10)alkyl;
R4는 모노(C1-C10)알킬아미노 또는 디(C1-C10)알킬아미노이다.)R 4 is mono(C1-C10)alkylamino or di(C1-C10)alkylamino.)
본 발명의 일 실시예에 따른 화학식 1의 텅스텐 화합물은 중심금속인 텅스텐이 반드시 하나이상의 알킬기를 가짐으로써 열안정성이 현저하게 향상되는 동시에 휘발성이 높아 양질의 박막을 제조할 수 있다.The tungsten compound of chemical formula 1 according to one embodiment of the present invention has significantly improved thermal stability and high volatility by having at least one alkyl group in the central metal tungsten, enabling the production of a high-quality thin film.
뿐만 아니라 본 발명의 일 실시예에 따른 화학식 1의 텅스텐 화합물은 상온에서 액체로 존재하여 취급이 용이하며 저장안정성 또한 우수하다.In addition, the tungsten compound of chemical formula 1 according to one embodiment of the present invention exists as a liquid at room temperature, making it easy to handle and also having excellent storage stability.
바람직하게 본 발명의 일 실시예에 따른 상기 화학식 1에서 R1 및 R2는 서로 독립적으로 (C1-C4)알킬이며, R3은 (C1-C4)알킬 또는 (C6-C12)아릴(C1-C4)알킬이며, R4는 모노(C1-C4)알킬아미노 또는 디(C1-C4)알킬아미노일 수 있으며, 보다 바람직하게는 R1 및 R2는 서로 독립적으로 분지쇄 (C3-C4)알킬이며, R3은 (C1-C4)알킬 또는 (C6-C10)아릴(C1-C4)알킬이며, R4는 모노(C1-C4)알킬아미노 또는 디(C1-C4)알킬아미노일 수 있다.Preferably, in the chemical formula 1 according to one embodiment of the present invention, R 1 and R 2 are each independently (C1-C4) alkyl, R 3 is (C1-C4) alkyl or (C6-C12) aryl (C1-C4) alkyl, and R 4 may be mono (C1-C4) alkylamino or di (C1-C4) alkylamino, more preferably, R 1 and R 2 are each independently branched (C3-C4) alkyl, R 3 is (C1-C4) alkyl or (C6-C10) aryl (C1-C4) alkyl, and R 4 may be mono (C1-C4) alkylamino or di (C1-C4) alkylamino.
박막 전구체로 향상된 특성을 가지기위한 측면에서 바람직하게 본 발명의 일 실시예에 따른 화학식 1은 하기 화학식 2로 표시될 수 있다.In terms of having improved properties as a thin film precursor, chemical formula 1 according to one embodiment of the present invention may be preferably represented by the following chemical formula 2.
[화학식 2][Chemical formula 2]
(상기 화학식 2에서(In the above chemical formula 2
R11은 (C1-C10)알킬이며,R 11 is (C1-C10) alkyl,
R3은 (C1-C10)알킬 또는 (C6-C12)아릴(C1-C10)알킬이며;R 3 is (C1-C10)alkyl or (C6-C12)aryl(C1-C10)alkyl;
R4는 모노(C1-C10)알킬아미노 또는 디(C1-C10)알킬아미노이다.)R 4 is mono(C1-C10)alkylamino or di(C1-C10)alkylamino.)
보다 좋기로는 본 발명의 일 실시예에 따른 화학식 2에서 R11은 분지쇄(C3-C4)알킬이며, R3은 (C1-C4)알킬 또는 (C6-C12)아릴(C1-C4)알킬이며, R4는 디(C1-C4)알킬아미노일 수 있으며, 더욱 좋기로는 R11은 tert-부틸이며, R3은 (C1-C4)알킬 또는 페닐(C1-C4)알킬이며, R4는 디(C1-C4)알킬아미노일 수 있다.More preferably, in the chemical formula 2 according to one embodiment of the present invention, R 11 may be branched-chain (C3-C4) alkyl, R 3 may be (C1-C4) alkyl or (C6-C12) aryl (C1-C4) alkyl, and R 4 may be di (C1-C4) alkylamino, and even more preferably, R 11 may be tert-butyl, R 3 may be (C1-C4) alkyl or phenyl (C1-C4) alkyl, and R 4 may be di (C1-C4) alkylamino.
구체적으로 본 발명의 일 실시예에 따른 텅스텐 화합물은 하기 화합물에서 선택될 수 있으나, 이에 한정이 있는 것은 아니다.Specifically, the tungsten compound according to one embodiment of the present invention may be selected from the following compounds, but is not limited thereto.
또한 본 발명은 본 발명의 텅스텐 화합물을 제조하는 방법을 제공한다.The present invention also provides a method for producing the tungsten compound of the present invention.
본 발명의 텅스텐 화합물의 제조방법은 하기 화학식 3과 화학식 4의 화합물을 반응시켜 하기 화학식 2의 화합물을 제조하는 단계;를 포함한다. The method for producing a tungsten compound of the present invention includes a step of reacting compounds of the following chemical formulas 3 and 4 to produce a compound of the following chemical formula 2.
[화학식 2][Chemical formula 2]
[화학식 3][Chemical Formula 3]
[화학식 4][Chemical Formula 4]
(상기 화학식 2 내지 4에서,(In the above chemical formulas 2 to 4,
R11 및 R21 내지 R22는 서로 독립적으로 (C1-C10)알킬이며,R 11 and R 21 to R 22 is independently (C1-C10) alkyl,
R3은 (C1-C10)알킬 또는 (C6-C12)아릴(C1-C10)알킬이며;R 3 is (C1-C10)alkyl or (C6-C12)aryl(C1-C10)alkyl;
R4는 모노(C1-C10)알킬아미노 또는 디(C1-C10)알킬아미노이며;R 4 is mono(C1-C10)alkylamino or di(C1-C10)alkylamino;
X는 할로겐이다.)X is a halogen.)
본 발명의 텅스텐 화합물의 제조방법은 일례로 상기와 같은 방법으로 제조될 수 있으나, 이외에 당업자가 인식할 수 있는 범위내에서 가능한 방법이라면 모두 가능하다.The method for producing the tungsten compound of the present invention can be produced by, for example, the method described above, but any other method that is possible within the scope recognized by those skilled in the art is also possible.
본 발명의 일 실시예에 따른 상기 화학식 4의 화합물은 화학식 3의 화합물, 1몰에 대하여 1.00 내지 5.00몰로 사용될 수 있으며, 바람직하게 1.0 내지 2.5몰로 사용될 수 있다.According to one embodiment of the present invention, the compound of chemical formula 4 can be used in an amount of 1.00 to 5.00 moles per mole of the compound of chemical formula 3, and preferably, can be used in an amount of 1.0 to 2.5 moles.
본 발명의 일 실시예에 따른 화학식 2로 표시되는 텅스텐 화합물의 제조방법에 사용되는 용매는 바람직하게 n-헥산, 클로로벤젠, 톨루엔, 다이클로로에탄(DCE), 다이옥산, 디에틸에테르 및 디클로로메테인(MC)에서 선택되는 하나(단독용매) 또는 둘이상의 혼합용매가 사용될 수 있으며, 보다 바람직하게 수율 등의 반응효율을 높이기위한 측면에서 n-헥산, 에테르 또는 디에틸에테르 용매 하에서 화학식 2의 화합물을 제조하는 단계는 낮은 온도(-78℃이하)에서 화합물 4를 천천히 첨가한 후 상온(18 내지 30℃)에서 수행될 수 있으며, 바람직하게는 20 내지 25℃에서 8 내지 24시간동안 수행될 수 있다.The solvent used in the method for producing a tungsten compound represented by chemical formula 2 according to one embodiment of the present invention is preferably one (single solvent) or a mixed solvent of two or more selected from n-hexane, chlorobenzene, toluene, dichloroethane (DCE), dioxane, diethyl ether and dichloromethane (MC), and more preferably, in order to increase the reaction efficiency such as the yield, the step of producing the compound of chemical formula 2 in the presence of n-hexane, ether or diethyl ether solvent may be performed at room temperature (18 to 30°C) after slowly adding compound 4 at a low temperature (-78°C or lower), and preferably, may be performed at 20 to 25°C for 8 to 24 hours.
또한 본 발명은 하기 화학식 5로 표시되는 텅스텐 화합물을 포함하는 박막증착용 조성물 및 본 발명의 박막증착용 조성물을 이용하는 박막의 제조방법을 제공한다.In addition, the present invention provides a composition for thin film deposition comprising a tungsten compound represented by the following chemical formula 5 and a method for producing a thin film using the composition for thin film deposition of the present invention.
[화학식 5][Chemical Formula 5]
(상기 화학식 5에서,(In the above chemical formula 5,
R1a 및 R2a는 서로 독립적으로 (C1-C10)알킬이며,R 1a and R 2a are independently (C1-C10) alkyl,
R3a은 (C1-C10)알킬 또는 (C6-C12)아릴(C1-C10)알킬이며; R 3a is (C1-C10)alkyl or (C6-C12)aryl(C1-C10)alkyl;
R4a는 (C1-C10)알킬, (C6-C12)아릴(C1-C10)알킬, 모노(C1-C10)알킬아미노 또는 디(C1-C10)알킬아미노이다.)R 4a is (C1-C10)alkyl, (C6-C12)aryl(C1-C10)alkyl, mono(C1-C10)alkylamino or di(C1-C10)alkylamino.)
본 발명의 텅스텐함유 박막은 통상적인 방법으로 제조될 수 있으며, 일례로 유기금속 화학기상 증착법(MOCVD), 원자층 증착법(ALD) 공정, 저압 기상 증착법(LPCVD), 플라즈마 강화 기상 증착법 (PECVD) 또는 플라즈마 강화 원자층 증착법(PEALD)등을 들 수 있다.The tungsten-containing thin film of the present invention can be manufactured by a conventional method, and examples thereof include metalorganic chemical vapor deposition (MOCVD), atomic layer deposition (ALD) process, low pressure chemical vapor deposition (LPCVD), plasma enhanced chemical vapor deposition (PECVD), or plasma enhanced atomic layer deposition (PEALD).
본 발명의 텅스텐함유 박막은 본 발명의 텅스텐 화합물을 이용하여 제조되며, 한정이 있는 것은 아니나 바람직하게 텅스텐질화막일 수 있다.The tungsten-containing thin film of the present invention is manufactured using the tungsten compound of the present invention, and is preferably a tungsten nitride film, although there is no limitation thereto.
본 발명의 텅스텐함유 박막의 제조방법은 높은 휘발성과 높은 열적 안정성을 가지는 본 발명의 텅스텐 화합물을 전구체로 사용하여 제조됨으로써 제조된 텅스텐함유 박막은 물리적, 전기적, 화학적 특성이 극히 우수하다.The method for manufacturing a tungsten-containing thin film of the present invention is performed by using the tungsten compound of the present invention, which has high volatility and high thermal stability, as a precursor, so that the manufactured tungsten-containing thin film has extremely excellent physical, electrical, and chemical properties.
본 발명의 텅스텐함유 박막의 제조방법에서 본 발명의 텅스텐 화합물의 주입온도는 상온(25℃) 내지 120 ℃일 수 있으며, 본 발명의 텅스텐 화합물의 높은 휘발성으로 인해 텅스텐 화합물이 증착될 기판의 온도는 100 내지 450 ℃, 챔버내부 압력은 0.1 내지 10 torr일 수 있다.In the method for manufacturing a tungsten-containing thin film of the present invention, the injection temperature of the tungsten compound of the present invention may be room temperature (25°C) to 120°C, and due to the high volatility of the tungsten compound of the present invention, the temperature of the substrate on which the tungsten compound is to be deposited may be 100 to 450°C, and the pressure inside the chamber may be 0.1 to 10 torr.
본 발명의 텅스텐함유 박막의 제조방법에서 사용되는 반응가스는 한정이 있는 것은 아니나, 수소(H2), 히드라진(N2H4), 오존(O3), 산소(O2), 물(H2O), 암모니아(NH3), 질소(N2), 실란(SiH4), 보란(BH3), 디보란(B2H6) 및 포스핀(PH3)에서 선택되는 하나 또는 하나이상의 혼합기체일 수 있다.The reaction gas used in the method for manufacturing a tungsten-containing thin film of the present invention is not limited, but may be one or a mixture of one or more gases selected from hydrogen (H 2 ), hydrazine (N 2 H 4 ), ozone (O 3 ), oxygen (O 2 ), water (H 2 O), ammonia (NH 3 ), nitrogen (N 2 ), silane (SiH 4 ), borane (BH 3 ), diborane (B 2 H 6 ), and phosphine (PH 3 ).
이하, 실시예를 통하여 본 발명의 구성을 보다 구체적으로 설명하지만, 하기의 실시예들은 본 발명에 대한 이해를 돕기 위한 것으로서, 본 발명의 범위가 여기에 국한된 것은 아니다.Hereinafter, the composition of the present invention will be described more specifically through examples, but the following examples are intended to help understanding of the present invention, and the scope of the present invention is not limited thereto.
[실시예 1] W(Nt-Bu)2N(CH3)2CH(CH3)2의 합성[Example 1] Synthesis of W(Nt-Bu) 2 N(CH 3 ) 2 CH(CH 3 ) 2
250mL의 플라스크를 진공 건조하여 N2분위기를 만들어 주고, 비스(tert-부틸이미도)비스(디메틸아미도)텅스텐(BTBMW) 30g (72mmol)을 첨가하였다. 여기에 용매인 n-hexane 100mL를 넣어 녹여 주었다. Acetone/dry ice bath를 이용하여 플라스크의 온도를 -78˚C까지 냉각 시킨 후 iso-propylMgCl 75mL(150mmol)(2M in THF)를 천천히 넣어주었다. 그 후 상온까지 승온하여, 16시간 교반시켰다. 반응이 끝난 후 celite filter를 진행 후 20mL n-hexane으로 필터를 3회 씻어주고, 용액은 감압 농축하였다. 증류정제하여 표제 화합물, 22.3g(54mmol, 75%)을 얻었다(정제 조건 94˚C/0.904torr).A 250 mL flask was vacuum-dried to create a N 2 atmosphere, and 30 g (72 mmol) of bis(tert-butylimido)bis(dimethylamido)tungsten (BTBMW) was added. 100 mL of n -hexane as a solvent was added and dissolved. The temperature of the flask was cooled to -78˚C using an acetone/dry ice bath, and 75 mL (150 mmol) of iso- propylMgCl (2 M in THF) was slowly added. The temperature was then raised to room temperature and stirred for 16 hours. After the reaction was completed, celite filtration was performed, and the filter was washed three times with 20 mL of n -hexane, and the solution was concentrated under reduced pressure. The residue was purified by distillation to obtain the title compound, 22.3 g (54 mmol, 75%) (purification conditions 94˚C/0.904 torr).
1H NMR 400MHz(C6D6):δ 3.36(s, 6H), 2.41(m, 1H), 1.91(d, 6H), 1.37(s, 18H) 1 H NMR 400 MHz (C 6 D 6 ): δ 3.36 (s, 6H), 2.41 (m, 1H), 1.91 (d, 6H), 1.37 (s, 18H)
[실시예 2] W(Nt-Bu)2N(CH3)2bn의 합성[Example 2] Synthesis of W(Nt-Bu) 2 N(CH 3 ) 2 bn
250mL의 플라스크를 진공건조하여 N2분위기를 만들어 주고, BTBMW 30g(72mmol)을 첨가하였다. 여기에 용매인 diethyl ether 100mL를 넣어 녹여 주었다. Acetone/dry ice bath를 이용하여 플라스크의 온도를 -78˚C까지 냉각 시킨 후 benzylMgCl 145mL(145mmol)(1M in diethyl ether)를 천천히 넣어주었다. 그 후 상온까지 승온하여, 16시간 교반시켰다. 반응이 끝난 후 celite filter를 진행 후 20mL n-hexane으로 필터를 3회 씻어주고, 용액은 감압 농축하였다. 생성물을 증류 정제 하여 W(Nt-Bu)2N(CH3)2Bn, 24g(52mmol, 72%)을 얻었다(정제 조건 110˚C/0.820torr).A 250 mL flask was vacuum-dried to create an N 2 atmosphere, and 30 g (72 mmol) of BTBMW was added. 100 mL of diethyl ether as a solvent was added and dissolved. The temperature of the flask was cooled to -78˚C using an acetone/dry ice bath, and 145 mL (145 mmol) of benzylMgCl (1 M in diethyl ether) was slowly added. The temperature was then raised to room temperature and stirred for 16 hours. After the reaction was complete, celite filtration was performed, and the filter was washed three times with 20 mL of n -hexane, and the solution was concentrated under reduced pressure. The product was purified by distillation to obtain 24 g (52 mmol, 72%) of W(Nt-Bu) 2 N(CH 3 ) 2 Bn (purification conditions 110˚C/0.820 torr).
1H NMR 400MHz(C6D6):δ 7.19(m, 2H), 7.12(m, 1H), 7.03(m, 1H), 6.93(m, 1H), 3.28(s, 6H), 3.16(s, 2H), 1.39(s, 18H) 1 H NMR 400 MHz (C 6 D 6 ): δ 7.19 (m, 2H), 7.12 (m, 1H), 7.03 (m, 1H), 6.93 (m, 1H), 3.28 (s, 6H), 3.16 (s) , 2H), 1.39(s, 18H)
[실시예 3] W(Nt-Bu)2N(CH3)2n-Bu의 합성[Example 3] Synthesis of W(Nt-Bu) 2 N(CH 3 ) 2 n-Bu
250mL의 플라스크를 진공건조하여 N2분위기를 만들어 주고, BTBMW 30g(72mmol)을 넣어주었다. 여기에 용매인 ether 100mL를 넣어 녹여 주었다. Acetone/dry ice bath를 이용하여 플라스크의 온도를 -78˚C까지 냉각 시킨 후 n-BuMgCl 37mL(74mmol)(2M in THF)를 천천히 넣어주었다. 그 후 상온까지 승온하여, 16시간 교반시켰다. 반응이 끝난 후 celite filter를 진행 후 20mL n-hexane으로 필터를 3회 씻어주고, 용액은 감압 농축하였다. 반응물을 증류 정제 하여 W(Nt-Bu)2N(CH3)2n-Bu, 24.7g(57.8mmol, 80%)을 얻었다(정제 조건 110˚C/0.75torr).A 250 mL flask was vacuum-dried to create an N 2 atmosphere, and 30 g (72 mmol) of BTBMW was added. 100 mL of ether as a solvent was added and dissolved. The temperature of the flask was cooled to -78˚C using an acetone/dry ice bath, and 37 mL (74 mmol) of n -BuMgCl (2 M in THF) was slowly added. The temperature was then raised to room temperature and stirred for 16 hours. After the reaction was complete, celite filtration was performed, and the filter was washed three times with 20 mL of n -hexane, and the solution was concentrated under reduced pressure. The reactant was purified by distillation to obtain 24.7 g (57.8 mmol, 80%) of W(Nt-Bu) 2 N(CH 3 ) 2 n-Bu (purification conditions 110˚C/0.75 torr).
1H NMR 400MHz(C6D6):δ 3.40(s, 6H), 2.17(m, 2H), 1.95(m, 2H), 1.53(m, 2H), 1.39(s, 18H), 1.02(t, 3H) 1 H NMR 400 MHz (C 6 D 6 ): δ 3.40 (s, 6H), 2.17 (m, 2H), 1.95 (m, 2H), 1.53 (m, 2H), 1.39 (s, 18H), 1.02 (t , 3H)
[실시예 4][(CH3CH2CH2CH2)2((CH3)3CN)2]W의 합성[Example 4]Synthesis of [(CH 3 CH 2 CH 2 CH 2 ) 2 ((CH 3 ) 3 CN) 2 ]W
250mL의 플라스크를 진공건조하여 N2분위기를 만들어 주고, BTBMW 30g(72mmol)을 넣어주었다. 여기에 용매인 n-hexane 100mL를 넣어 녹여 주었다. Acetone/dry ice bath를 이용하여 플라스크의 온도를 -78˚C까지 냉각 시킨 후 n-BuMgCl 75mL(150mmol)(2M in THF)를 천천히 넣어주었다. 그 후 상온까지 승온하여, 16시간 교반시켰다. 반응이 끝난 후 celite filter를 진행 후 20mL n-hexane으로 필터를 3회 씻어주고, 용액은 감압 농축하였다. 반응물 28g(64.1mol, 89%)을 증류 정제하여 W(Nt-Bu)2(n-Bu)2, 22.8g(51.7mmol, 71.8%)을 얻었다(정제 조건 110˚C/0.75torr). A 250 mL flask was vacuum-dried to create an N 2 atmosphere, and 30 g (72 mmol) of BTBMW was added. 100 mL of n -hexane as a solvent was added and dissolved. The temperature of the flask was cooled to -78˚C using an acetone/dry ice bath, and 75 mL (150 mmol) of n -BuMgCl (2 M in THF) was slowly added. The temperature was then raised to room temperature and stirred for 16 hours. After the reaction was complete, celite filtration was performed, and the filter was washed three times with 20 mL of n -hexane, and the solution was concentrated under reduced pressure. 28 g (64.1 mol, 89%) of the reactant was purified by distillation to obtain 22.8 g (51.7 mmol, 71.8%) of W(Nt-Bu) 2 (n-Bu) 2 (purification conditions 110˚C/0.75 torr).
1H NMR 400MHz(C6D6):δ 2.21(m, 2H), 1.96(m, 2H), 1.53(m, 6H), 1.42(s, 18H), 1.15(m, 4H), 1.05(m, 4H) 1 H NMR 400 MHz (C 6 D 6 ): δ 2.21 (m, 2H), 1.96 (m, 2H), 1.53 (m, 6H), 1.42 (s, 18H), 1.15 (m, 4H), 1.05 (m , 4H)
[실시예 5] 텅스텐 화합물의 물질 분석[Example 5] Material analysis of tungsten compounds
상기 실시예 1에서 제조된 W(Nt-Bu)2N(CH3)2CH(CH3)2의 열적 안정성 및 휘발성과 분해 온도를 측정하기 위해, 열무게 분석법(TGA)을 이용하였다(TGA 조건: 10℃/분의 속도로 500℃까지 가온 시키면서 1.5bar/분의 압력으로 아르곤 주입).To measure the thermal stability, volatility, and decomposition temperature of W(Nt-Bu) 2 N(CH 3 ) 2 CH(CH 3 ) 2 manufactured in Example 1, thermogravimetric analysis (TGA) was used (TGA conditions: heating to 500°C at a rate of 10°C/min while injecting argon at a pressure of 1.5 bar/min).
도 1에 나타낸 바와 같이 실시예 1에서 제조된 텅스텐 화합물은 75℃부근에서 질량 감소가 일어나기 시작하여 180℃에서 약98%의 질량감소를, 162℃에서 T1/2을 확인하였다. 이로부터 본 발명의 실시예가 열안정성이 매우 우수함을 알 수 있다.As shown in Fig. 1, the tungsten compound manufactured in Example 1 began to experience a mass loss around 75°C, and a mass loss of approximately 98% was confirmed at 180°C and T 1/2 at 162°C. From this, it can be seen that the example of the present invention has excellent thermal stability.
Claims (9)
[화학식 2]
[화학식 3]
[화학식 4]
(상기 화학식 2 내지 4에서,
R11 및 R21 내지 R22는 서로 독립적으로 (C1-C10)알킬이며,
R3은 (C1-C10)알킬 또는 (C6-C12)아릴(C1-C10)알킬이며;
R4는 모노(C1-C10)알킬아미노 또는 디(C1-C10)알킬아미노이며;
X는 할로겐이다.) A method for producing a tungsten compound, comprising the step of reacting a compound of the following chemical formula 3 with a compound of the following chemical formula 4 to produce a compound of the following chemical formula 2.
[Chemical formula 2]
[Chemical Formula 3]
[Chemical Formula 4]
(In the above chemical formulas 2 to 4,
R 11 and R 21 to R 22 is independently (C1-C10) alkyl,
R 3 is (C1-C10)alkyl or (C6-C12)aryl(C1-C10)alkyl;
R 4 is mono(C1-C10)alkylamino or di(C1-C10)alkylamino;
X is a halogen.)
[화학식 5]
(상기 화학식 5에서,
R1a 및 R2a는 서로 독립적으로 (C1-C10)알킬이며,
R3a은 (C1-C10)알킬 또는 (C6-C12)아릴(C1-C10)알킬이며;
R4a는 (C1-C10)알킬, (C6-C12)아릴(C1-C10)알킬, 모노(C1-C10)알킬아미노 또는 디(C1-C10)알킬아미노이다.) A composition for thin film deposition comprising a tungsten compound represented by the following chemical formula 5.
[Chemical Formula 5]
(In the above chemical formula 5,
R 1a and R 2a are independently (C1-C10) alkyl,
R 3a is (C1-C10)alkyl or (C6-C12)aryl(C1-C10)alkyl;
R 4a is (C1-C10)alkyl, (C6-C12)aryl(C1-C10)alkyl, mono(C1-C10)alkylamino or di(C1-C10)alkylamino.)
상기 박막은 유기금속 화학기상 증착법, 원자층 증착법공정, 저압 기상 증착법, 플라즈마 강화 기상 증착법 또는 플라즈마 강화 원자층 증착법에 의해 수행되는 것인 방법.In Article 8,
A method wherein the above thin film is formed by organic metal chemical vapor deposition, atomic layer deposition, low pressure vapor deposition, plasma enhanced vapor deposition or plasma enhanced atomic layer deposition.
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