CN116324025A - Film forming method using upper surface modifier - Google Patents
Film forming method using upper surface modifier Download PDFInfo
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- CN116324025A CN116324025A CN202180067978.8A CN202180067978A CN116324025A CN 116324025 A CN116324025 A CN 116324025A CN 202180067978 A CN202180067978 A CN 202180067978A CN 116324025 A CN116324025 A CN 116324025A
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- surface modifier
- compound
- film
- film forming
- pentyl
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- 239000003607 modifier Substances 0.000 title claims abstract description 127
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims description 64
- 239000002243 precursor Substances 0.000 claims description 51
- 229940125782 compound 2 Drugs 0.000 claims description 28
- 229940125898 compound 5 Drugs 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 18
- 238000000231 atomic layer deposition Methods 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 238000010926 purge Methods 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 7
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 7
- -1 dimethylamino, ethylmethylamino, diethylamino, methylpropylamino, ethylpropylamino Chemical group 0.000 claims description 6
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 229940125904 compound 1 Drugs 0.000 claims description 5
- 229940126214 compound 3 Drugs 0.000 claims description 5
- 125000004663 dialkyl amino group Chemical class 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 3
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 3
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 3
- 125000004914 dipropylamino group Chemical group C(CC)N(CCC)* 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 239000010408 film Substances 0.000 description 82
- 238000000151 deposition Methods 0.000 description 55
- 230000008021 deposition Effects 0.000 description 55
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 22
- 230000000694 effects Effects 0.000 description 13
- 229910000449 hafnium oxide Inorganic materials 0.000 description 13
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 13
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 11
- 229910052735 hafnium Inorganic materials 0.000 description 7
- 230000001965 increasing effect Effects 0.000 description 7
- 230000001603 reducing effect Effects 0.000 description 7
- 241000252506 Characiformes Species 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 239000012159 carrier gas Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 5
- 239000012495 reaction gas Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- UOCJDOLVGGIYIQ-PBFPGSCMSA-N cefatrizine Chemical group S([C@@H]1[C@@H](C(N1C=1C(O)=O)=O)NC(=O)[C@H](N)C=2C=CC(O)=CC=2)CC=1CSC=1C=NNN=1 UOCJDOLVGGIYIQ-PBFPGSCMSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000000051 modifying effect Effects 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
Images
Classifications
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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
- C23C16/44—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
- C23C16/45534—Use of auxiliary reactants other than used for contributing to the composition of the main film, e.g. catalysts, activators or scavengers
-
- 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
- C23C16/40—Oxides
-
- 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
- C23C16/40—Oxides
- C23C16/405—Oxides of refractory metals or yttrium
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Chemical Vapour Deposition (AREA)
- Formation Of Insulating Films (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The present application relates to an upper surface modifier, an upper surface modifier composition comprising the upper surface modifier, and a film forming method using the upper surface modifier composition.
Description
Technical Field
The present application relates to an upper surface modifier, an upper surface modifier composition comprising the upper surface modifier, and a film forming method using the upper surface modifier composition.
Background
Currently, a memory device such as a DRAM (dynamic random access memory) in a memory area and a system IC device such as a logic memory (logic memory) in a non-memory area have reached physical limits by miniaturization (scaling). With the increasing miniaturization of semiconductor devices, the chip size per unit area is smaller, and with the increase of integration, the problem of leakage current is increasing, and the required film thickness is also decreasing. Therefore, in order to secure a high capacity battery capacity, it is necessary to control the thickness of the oxide film for effectively blocking the leakage current. There is a need to develop a new process technology: even for a DRAM having a high aspect ratio (high aspect ratio), a 3D NAND flash memory having a three-dimensional structure, a logic device having a full All Around Gate (GAA) and fin field effect transistor (FinFET) structure, oxide and metal films can be uniformly formed in upper and lower regions. Accordingly, many researches are being conducted to develop an improved process aimed at ensuring excellent step coverage.
Disclosure of Invention
Technical problem
The present application is directed to an upper surface modifier, an upper surface modifier composition comprising the upper surface modifier, and a method of forming a film using the upper surface modifier composition.
The present application aims to form a stable dielectric or metal film having excellent step coverage even on a pattern having a high aspect ratio (aspect ratio) by forming the film using an upper surface modifier.
However, the problems to be solved by the present application are not limited to the above-described problems, and other non-mentioned problems will be clearly understood by those skilled in the art from the following description.
Technical proposal
A first aspect of the present application provides an upper surface modifier represented by the following formula I:
[ formula I ]
In the case of the formula I described above,
R 1 and R is 2 Each independently is hydrogen, or a straight or branched chain C 1-5 Alkyl, or C being linear or branched 1-5 Alkyl-substituted dialkylamino; or R is 1 And R is 2 Is a substituted or unsubstituted C linked to each other 2-6 A cyclic alkyl group,
R 3 and R is 4 Each independently is a straight or branched chain C 1-5 An alkyl group; or R is 3 And R is 4 Is a substituted or unsubstituted C linked to each other 2-6 A cyclic alkyl group,
x is-O-, -S-or-NH.
A second aspect of the present application provides an upper surface modifier composition comprising an upper surface modifier represented by the following formula I:
[ formula I ]
In the case of the formula I described above,
R 1 and R is 2 Each independently is hydrogen, or a straight or branched chain C 1-5 Alkyl, or C being linear or branched 1-5 Alkyl-substituted dialkylamino; or R is 1 And R is 2 Is a substituted or unsubstituted C linked to each other 2-6 A cyclic alkyl group,
R 3 and R is 4 Each independently is a straight or branched chain C 1-5 An alkyl group; or R is 3 And R is 4 Is a substituted or unsubstituted C linked to each other 2-6 A cyclic alkyl group,
x is-O-, -S-or-NH.
A third aspect of the present application provides a film forming method, wherein a film is formed by an atomic layer deposition method using the upper surface modifier composition according to the second aspect and a precursor for film formation.
Effects of the invention
When the film is formed using the upper surface modifier according to the embodiment of the present application, the film can be uniformly formed in the upper region and the lower region, so that the device problem caused by the leakage current can be solved.
When the upper surface modifier according to the embodiment of the present application is used, an effect of a reduction in thickness of about 30% or more, about 40% or more, or about 50% or more, or a reduction in deposition rate of about 30% or more, about 40% or more, about 50% or more, or about 60% or more can be exhibited.
When the film is formed using the upper surface modifier according to the embodiment of the present application, even in a process requiring a three-dimensional structure and a high aspect ratio, it is possible to uniformly and stably form the film not only in the upper and lower regions but also to perform fine thickness adjustment. Therefore, it is an indispensable material for memory devices and non-memory devices having a high aspect ratio, and can be applied to a new process requiring fine thickness adjustment.
Drawings
Fig. 1 is a graph comparing the film thickness reduction rate of hafnium oxide based on the supply amount when using the upper surface modifiers of compounds 1 to 4 according to an embodiment of the present application.
Fig. 2 is a graph showing a reduction rate of hafnium oxide film thickness based on temperature when using the upper surface modifiers of compound 2 and compound 4 according to an embodiment of the present application.
Fig. 3 is a graph comparing the reduction rate of the thickness of the aluminum oxide film based on the supply amount thereof when the upper surface modifier of the compound 2 according to an embodiment of the present application is used.
Fig. 4 is a graph comparing the reduction rate of the thickness of the aluminum oxide film based on the supply amount thereof when the upper surface modifier of the compound 5 according to an embodiment of the present application is used.
Fig. 5 is a graph comparing the reduction rate of the thickness of the aluminum oxide film based on temperature when the upper surface modifiers of the compound 2 and the compound 5 according to an embodiment of the present application are used and when the upper surface modifier is not used.
Fig. 6 is a graph comparing the zirconia film deposition rate based on temperature when the upper surface modifier of the compound 2 according to an embodiment of the present application was used and when the upper surface modifier was not used.
Fig. 7 is a graph comparing the deposition rates of hafnium oxide films based on temperature when using the upper surface modifiers of compound 2 and compound 5 according to an embodiment of the present application and when not using the upper surface modifiers.
Fig. 8 is a graph comparing the magnesium oxide film deposition rates based on temperature when the upper surface modifiers of compound 2 and compound 5 according to an embodiment of the present application are used and when the upper surface modifier is not used.
Detailed Description
Hereinafter, embodiments and examples of the present application will be described in detail with reference to the accompanying drawings so that those skilled in the art to which the present invention pertains can easily implement the present invention. However, the present application may be embodied in many different forms and is not limited to the embodiments and examples described herein. In addition, in order to clearly illustrate the present invention in the drawings, parts irrelevant to the description are omitted, and like reference numerals are used for like parts throughout the specification.
Throughout this specification, when reference is made to one part being "connected" to another part, this includes not only the case of "direct connection" but also the case of "electrical connection" with other elements being interposed therebetween.
Throughout the specification, when reference is made to one element being "on" another element, this includes not only the case where one element is in contact with the other element, but also the case where there is another element between the two elements.
Throughout the specification, when a portion is referred to as "comprising" an element, it means that the other element can be further included, but is not excluded, unless expressly stated otherwise.
To the extent that the terms "about," "basic," and the like are used in this specification, when given manufacturing and material tolerances inherent to the mentioned meaning, these terms are used to denote or approximate the value and are intended to prevent improper use by a malicious infringer of the disclosure referring to an exact or absolute value to aid in understanding the present application.
The terms "step of performing" or "step of" are used throughout the specification to the extent that they do not mean "step of".
Throughout the specification, the term "one or more combinations thereof" included in the Ma Kushi type expression means at least one mixture or combination selected from the group consisting of the elements described in the Ma Kushi type expression, and is meant to include at least one selected from the group consisting of the elements.
Throughout the specification, the description of "a and/or B" means "a or B, or a and B".
Throughout the specification, the term "film" refers to "film or membrane".
Throughout the specification, the term "alkyl" or "alkyl group" includes straight or branched chain alkyl groups having 1 to 12 carbon atoms, 1 to 10 carbon atoms, 1 to 8 carbon atoms or 1 to 5 carbon atoms, as well as all possible isomers thereof. For example, the alkyl or alkyl group may include methyl (Me), ethyl (Et), n-propyl n Pr, isopropyl i Pr, n-butyl ] n Bu) and isobutyl% i Bu), t-butyl (ter-Bu, t bu), sec-butyl (sec-Bu, sec bu) n-pentyl n Pe, isopentyl% iso Pe, sec-amyl% sec Pe), t-amyl group t Pe, neopentyl% neo Pe), 3-pentyl, n-hexyl, isohexyl, heptyl, 4-dimethylpentyl, octyl, 2, 4-trimethylpentyl, nonyl, decyl, undecyl, dodecyl, isomers thereof, and the like.
Hereinafter, embodiments of the present application have been described in detail, but the present application may not be limited thereto.
A first aspect of the present application provides an upper surface modifier represented by the following formula I:
[ formula I ]
In the case of the formula I described above,
R 1 and R is 2 Each independently is hydrogen, or a straight or branched chain C 1-5 Alkyl, or C being linear or branched 1-5 Alkyl-substituted dialkylamino; or R is 1 And R is 2 Is a substituted or unsubstituted C linked to each other 2-6 A cyclic alkyl group,
R 3 and R is 4 Each independently is a straight or branched chain C 1-5 An alkyl group; or R is 3 And R is 4 Is a substituted or unsubstituted C linked to each other 2-6 A cyclic alkyl group,
x is-O-, -S-or-NH.
In one embodiment of the present application, only R 1 And R is 2 Or only R 3 And R is 4 May be substituted or unsubstituted C 2-6 Cyclic alkyl groups, but may not be limited thereto.
In one embodiment of the present application, R 1 And R is 2 Can each independently be hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl, 3-pentyl, dimethylamino, ethylmethylamino, diethylamino, methylpropylamino, ethylpropylamino or dipropylamino, or R 1 And R is 2 May be linked to each other to form a cyclic alkyl group having a central carbon, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or cycloheptyl, but may not be limited thereto. Here, the "central carbon" means a carbon atom located at R represented by the following formula I 1 R 2 -C-(XR 3 )(XR 4 ) Is a carbon at the center of (2).
In one embodiment of the present application, R 3 And R is 4 May each be independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl or 3-pentyl, but may not be limited thereto. Furthermore, in one embodiment of the present application, R 3 And R is 4 Can be linked to each other to form a polymer comprising a central carbon and a hetero-structureHeterocyclic structures of atoms, and may be cyclic polyethers as non-limiting examples.
In one embodiment of the present application, the upper surface modifier may be selected from the following compounds 1 to 5:
[ Compound 1]
[ Compound 2]
[ Compound 3]
[ Compound 4]
[ Compound 5]
A second aspect of the present application provides an upper surface modifier composition comprising an upper surface modifier represented by the following formula I:
[ formula I ]
In the case of the formula I described above,
R 1 and R is 2 Each independently is hydrogen, or a straight or branched chain C 1-5 Alkyl, or C being linear or branched 1-5 Alkyl substituted dialkylAn amino group; or R is 1 And R is 2 Is a substituted or unsubstituted C linked to each other 2-6 A cyclic alkyl group,
R 3 and R is 4 Each independently is a straight or branched chain C 1-5 An alkyl group; or R is 3 And R is 4 Is a substituted or unsubstituted C linked to each other 2-6 A cyclic alkyl group,
x is-O-, -S-or-NH.
Although detailed descriptions of portions overlapping with the first aspect of the present application are omitted, the matters described with respect to the first aspect of the present application may be equally applicable to the second aspect of the present application, even though descriptions thereof are omitted in the second aspect of the present application.
In one embodiment of the present application, only R 1 And R is 2 Or only R 3 And R is 4 May be substituted or unsubstituted C 2-6 Cyclic alkyl groups, but may not be limited thereto.
In one embodiment of the present application, R 1 And R is 2 Each independently is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl, 3-pentyl, dimethylamino, ethylmethylamino, diethylamino, methylpropylamino, ethylpropylamino or dipropylamino, or R 1 And R is 2 May be linked to each other to form a cyclic alkyl group having a central carbon, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or cycloheptyl, but may not be limited thereto. Here, the "central carbon" means a carbon atom located at R represented by the following formula I 1 R 2 -C-(XR 3 )(XR 4 ) Is a carbon at the center of (2).
In one embodiment of the present application, R 3 And R is 4 Each independently is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl or 3-pentyl, but may not be limited thereto. Furthermore, in one embodiment of the present application, R 3 And R is 4 Can be connected with each other to formIn a heterocyclic structure including a central carbon and heteroatoms, and may be a cyclic polyether as a non-limiting example.
In one embodiment of the present application, the upper surface modifier may include at least one selected from the following compounds 1 to 5:
[ Compound 1]
[ Compound 2]
[ Compound 3]
[ Compound 4]
And [ Compound 5]
A third aspect of the present application provides a film forming method, wherein a film is formed by an atomic layer deposition method using the upper surface modifier composition according to the second aspect and a precursor for film formation.
Although detailed descriptions of portions overlapping with the first and second aspects of the present application are omitted, the matters described with respect to the first and second aspects of the present application may be equally applicable to the third aspect of the present application, even though descriptions thereof are omitted in the third aspect of the present application.
In one embodiment of the present application, the film may be selected from the group consisting of a metal film, an oxide film, a nitride film, a carbide film, and combinations thereof, but may not be limited thereto. In one embodiment of the present application, the film may be a metal film or an oxide film.
In one embodiment of the present application, the film-forming precursor may include at least one selected from Be, mg, ca, sr, ba, al, ga, in, sc, Y, la, si, ge, sn, P, as, sb, S, se, te, ti, zr, hf, V, ta, nb, cr, mo, W, mn, tc, re, fe, ru, os, co, rh, ir, ni, pd, pt, cu, ag and Au. In one embodiment of the present application, the film-forming precursor may comprise a precursor selected from group Be, mg, ca, sr, ba from group 2A; al, ga, in from group 3A; sc, Y, la from group 3B; si, ge, sn from group 4A; p, as, sb from group 5A; s, se, te from group 6A; ti, zr, hf from group 4B; v, ta, nb from group 5B; cr, mo, W from group 6B; mn, tc, re from group 7B; fe, ru, os, co, rh, ir, ni, pd, pt from group 8; and at least one of Cu, ag, au from group 1B. In one embodiment of the present application, the film-forming precursor may contain Mg, zr, or Hf.
In one embodiment of the present application, the film forming process may be performed at about 200 ℃ to about 500 ℃. For example, the film forming method may be performed at about 200 ℃ to about 500 ℃, about 200 ℃ to about 450 ℃, about 200 ℃ to about 400 ℃, about 200 ℃ to about 350 ℃, about 200 ℃ to about 300 ℃, about 200 ℃ to about 250 ℃, about 250 ℃ to about 500 ℃, about 250 ℃ to about 450 ℃, about 250 ℃ to about 400 ℃, about 250 ℃ to about 350 ℃, about 250 ℃ to about 300 ℃, about 300 ℃ to about 500 ℃, about 300 ℃ to about 450 ℃, about 300 ℃ to about 400 ℃, about 300 ℃ to about 350 ℃, about 350 ℃ to about 500 ℃, about 350 ℃ to about 450 ℃, about 350 ℃ to about 400 ℃, about 400 ℃ to about 500 ℃, about 400 ℃ to about 450 ℃, or about 450 ℃ to about 500 ℃.
In one embodiment of the present application, the film forming method may include: providing a substrate in a reaction chamber; providing a source material comprising the film-forming precursor and the upper surface modifier composition on the substrate; purging the interior of the reaction chamber; and providing a reactant capable of reacting with the source material to form a film, but may not be limited thereto.
In one embodiment of the present application, the step of providing the upper surface modifier composition may be performed simultaneously with or overlapping in time with the step of providing the source material including the precursor for film formation, or may be performed before or after the step of providing the source material including the precursor for film formation, but may not be limited thereto.
In one embodiment of the present application, the reactant may be at least one selected from the group consisting of ammonia, nitrogen, hydrazine, dimethylhydrazine, water vapor, oxygen, and ozone.
In one embodiment of the present application, a film forming method using the upper surface modifier according to one embodiment of the present application is a method of forming a thin film by supplying a precursor after supplying an upper surface modifier composition into a reaction chamber so as to be adsorbed on a wafer surface, which is capable of ensuring good step coverage by uniformly forming a thin film of uniform thickness from the surface to the bottom by inducing a chemical reaction on the surface.
In one embodiment of the present application, the film forming method using the upper surface modifier according to one embodiment of the present application can precisely control the thickness and composition of a thin film, and thus a thin film having excellent coverage can be formed even on a substrate having a complex shape, and thickness uniformity and physical properties of the thin film can be improved.
In one embodiment of the present application, when the film is formed using the upper surface modifier according to one embodiment of the present application, the thickness reduction ratio can be made to be about 30% or more, about 40% or more, or about 50% or more.
In one embodiment of the present application, the upper surface modifier according to one embodiment of the present application, when used to form a film, can reduce the deposition rate by about 30% or more, about 40% or more, about 50% or more, or about 60% or more.
Hereinafter, the present application will be described in more detail using examples, but the following examples are only for aiding in understanding the present application, and the contents of the present application are not limited to the following examples.
Examples (example)
<Experimental example 1>Using an upper surface modifier and (C) 5 H 5 )Hf(N(CH 3 ) 2 ) 3 [CpHf(NMe 2 ) 3 ]Comparison of the characteristics of oxide films deposited with precursor Compounds
Using the precursors (C) 5 H 5 )Hf(N(CH 3 ) 2 ) 3 [CpHf(NMe 2 ) 3 ](hereinafter also referred to as "Cp-Hf") and the upper surface modifiers of Compounds 1 to 4 performed an atomic layer deposition (ALD; atomic Layer Deposition) process.
To compare the different types of deposition characteristics based on the upper surface modifier, the known CpHf (NMe 2 ) 3 As hafnium precursor, and oxygen source O is used 3 As a reaction gas. First, a silicon wafer was mixed with sulfuric acid (H 2 SO 4 ) And hydrogen peroxide (H) 2 O 2 ) And the resulting Piranha (Piranha) solution was taken out after being immersed in the Piranha (Piranha) solution for 10 minutes, and then immersed in an HF aqueous solution for about 2 minutes, thereby forming a pure silicon surface, and then a hafnium oxide thin film was prepared by Atomic Layer Deposition (ALD).
In order to confirm the optimal deposition conditions using the upper surface modifier, deposition experiments were performed using compounds 1 to 4, respectively. Deposition was performed by fixing the ALD cycle 100 times, fixing the substrate temperature at 320 ℃, and adjusting the exposure time of the upper surface modifier to 1, 5, 10, and 30 seconds. Thereafter, the exposure time of the upper surface modifier was selected and the temperature of the substrate was changed so that the deposition rate was 50% or less as compared with the case where the hafnium oxide film was deposited without using the upper surface modifier, thereby confirming the deposition characteristics. To confirm the temperature-based deposition characteristics, deposition was performed by heating the substrate from 300 ℃ to 360 ℃ at intervals of 20 ℃. CpHf (NMe) 2 ) 3 The precursor compound and the upper surface modifiers of compounds 1 to 4 were used by heating to 100 ℃ and room temperature, respectively, in a container made of stainless steel material. At this time, the process pressure of the reactor was 1 Torr, and the flow rate was 300sccm of argon (Ar) gas was used as a carrier gas for the hafnium precursor and the surface modifier, which was then vaporized. ALD cycle for forming oxide film using upper surface modifier and hafnium precursor is performed with vaporized surface modifier supply, surface modifier purge, precursor supply, precursor purge, O 3 Supply and O 3 The order of purging was set to ≡seconds/5 seconds/10 seconds. Fig. 1 shows hafnium oxide film deposition results based on the exposure time of the surface modifier, and fig. 2 shows hafnium oxide film deposition results based on temperature after the selection of the exposure time of the surface modifier.
As can be seen from fig. 1, when the surface modifier of compound 2 is used, the thickness reduction rate of the hafnium oxide film is highest, and the thickness reduction rates are reduced in the order of the surface modifiers of compound 4, compound 1 and compound 3. It was also confirmed that the thickness of the hafnium oxide film decreased as the exposure time of the surface modifier increased, but the same deposition rates were exhibited at 5 seconds and 10 seconds in the case of compounds 2 and 4, respectively.
The effect of the reduction in thickness based on temperature of compounds 2 and 4, which is the greatest effect of the reduction rate in thickness among compounds 1 to 4, was confirmed in fig. 2. The reaction period of the surface modifier was chosen to be 5 seconds because the same thickness ratio was exhibited between 5 seconds and 10 seconds. The surface modifiers of compounds 2 and 4 also showed a reduction in thickness of 50% or more. As can be confirmed from fig. 2, the thickness reduction rate increases with an increase in temperature. It can thus be seen that the surface modifier does not undergo surface desorption in the deposition temperature range, and as the temperature increases, the activity of the surface modifier increases, thus improving the modifying effect and thus the thickness reduction rate.
<Experimental example 2>Using an upper surface modifier and TMA [ Al (CH) 3 ) 3 ]Comparison of oxide film Properties of precursor Compound deposition
In order to confirm the effect of reducing the deposition rate based on the use or absence of the upper surface modifier, compound 2 and compound 5 were used as the upper surface modifiers, respectively, and known Trimethylaluminum (TMA) [ Al (CH) 3 ) 3 ]Precursor compound and ozone (O) as oxygen source reaction gas 3 ) By passing throughAtomic layer deposition (ALD-Atomic Layer Deposition) forms an aluminum oxide film. All substrates used for deposition for determining deposition rate were mixed with sulfuric acid (H 2 SO 4 ) And hydrogen peroxide (H) 2 O 2 ) And the obtained piranha solution was taken out after being immersed for about 10 minutes, and after being immersed in an HF aqueous solution for about 2 minutes, was washed with distilled water, thereby forming a pure silicon surface from which a natural oxide film was removed, and then an aluminum oxide film was deposited.
The upper surface modifiers of compound 2 and compound 5 and TMA precursor compound were placed in a stainless steel vessel and vaporized at 30 ℃. In order to move the vaporized upper surface modifier and precursor compound into the reactor in a state where condensation does not occur, the temperature of the moving space from the vessel to the reactor is sequentially heated up from 120 ℃ to 150 ℃. Argon (Ar) gas having a flow rate of 200sccm to 500sccm was used as a carrier gas for moving the upper surface modifier compounds of compound 2 and compound 5 to the reactor. Argon gas at a flow rate of 500sccm to 2000sccm was then used to flow out the upper surface modifier remaining in the reactor. Then, argon (Ar) gas having a flow rate of 200sccm to 500sccm was used as a carrier gas for moving the TMA precursor compound to the reactor. Then, argon gas at a flow rate of 500sccm to 2000sccm was used to flow out the TMA precursor compound remaining in the reactor. Then, the oxygen source O is made 2 Flowing into an ozone generator at a flow rate of 500sccm to 1000sccm to produce a concentration of about 180g/m 3 -220g/m 3 Is used as the reaction gas. Thereafter, argon gas having a flow rate of 500sccm to 2000sccm was used to flow out the upper surface modifier, TMA precursor compound, ozone, reaction by-products, and the like, which were left in the reactor. At this time, the process pressure of the reactor was measured to be 0.9 torr to 1.2 torr, and the supply time of the vaporized upper surface modifier compound was set to about 1 to 30 seconds, the purge time in the reactor was set to about 5 to 30 seconds, the supply time of the vaporized TMA precursor compound was set to about 1 to 5 seconds, the purge time in the reactor was set to about 5 to 30 seconds, the ozone supply time was set to about 5 to 30 seconds, and the purge time in the reactor was set to about 5 to 30 seconds. In all processes, the deposition cycle was repeated 100 timesAn aluminum oxide film was deposited, and the thickness and deposition rate were checked using an ellipsometer. In order to confirm the temperature-based deposition characteristics, an aluminum oxide film was deposited while increasing the substrate temperature from 250 to 400 ℃ in units of 10 to 25 ℃.
To compare the deposition rate reducing effect of the upper surface modifier compounds of compound 2 and compound 5 based on exposure time, an alumina film was first deposited using no upper surface modifier but only TMA compound at 250 ℃. Further, by using the upper surface modifier compounds of compound 2 and compound 5, respectively, an aluminum oxide film was deposited while increasing the exposure time, thereby confirming the deposition rate reducing effect. The deposition rates based on the exposure time of the upper surface modifier are compared and are shown in fig. 3 and 4.
Further, the results of comparison of the deposition rate of the aluminum oxide film deposited without using the upper surface modifier at 250 ℃ to 400 ℃ and using only TMA and the deposition rate of the aluminum oxide film when the upper surface modifier compounds of compound 2 and compound 5 were used are shown in fig. 5.
From FIG. 3, it can be confirmed that the deposition rate of the alumina film was 1.17 Angstrom/cycle when only TMA precursor compound was used at 250 ℃
The deposition rate of the alumina film deposited while increasing the exposure time of the upper surface modifier of compound 2 from 5 seconds to 30 seconds was +.>
To->
I.e., the effect of a reduction in deposition rate of about 35%.
From FIG. 4, it can be confirmed that the deposition rate of the alumina film at 250℃using only TMA precursor compound was
And on the upper surface of the compound 5The aluminum oxide film deposition rate at which the agent was deposited while increasing the exposure time from 1 second to 15 seconds was +.>
To->
I.e., the effect of reducing the deposition rate by about 71%, and it was confirmed that the deposition rate was constant when the exposure time of the upper surface modifier of the compound 5 was 1 second or more.
From fig. 5, it can be confirmed that the deposition rate of TMA precursor compound was reduced by about 36.7% to about 53.4% when the upper surface modifier of compound 2 was used, and by about 66.5% to 74.0% when the upper surface modifier of compound 5 was used.
Experimental example 3> oxide film deposition Property of precursor Compound having high dielectric constant (high-k) when Using the upper surface modifier
In order to confirm the effect of reducing the deposition rate based on the use or absence of the upper surface modifier, compound 2 and compound 5 were used as the upper surface modifier, and (C 5 H 5 )Zr(N(CH 3 ) 2 ) 3 [CpZr(NMe2)3](hereinafter also referred to as "Cp-Zr"), (C) 5 H 5 )Hf(N(CH 3 ) 2 ) 3 [CpHf(NMe 2 ) 3 ]Precursor compound and Mg Et Cp) 2 [(CH 3 CH 2 (C 5 H 4 )) 2 Mg]Precursor compound and ozone (O) as oxygen source reaction gas 3 ) The zirconium oxide film, the hafnium oxide film, and the magnesium oxide film are formed by an atomic layer deposition method, respectively. All substrates for deposition used for measuring deposition rate were mixed with sulfuric acid (H 2 SO 4 ) And hydrogen peroxide (H) 2 O 2 ) And the resulting piranha solution was immersed for about 10 minutes and in an HF aqueous solution for about 2 minutes and taken out, and then washed with distilled water, thereby forming a pure silicon surface from which a natural oxide film was removed, and then an oxide film was deposited.
The upper surface modifier compound of the compound 2 and the compound 5 and Cp-Zr, cp-Hf and Mg Et Cp) 2 The precursor compounds were placed in stainless steel containers and allowed to vaporize at 30 ℃, 100 ℃ and 60 ℃, respectively. In order to move the vaporized upper surface modifier and precursor compound into the reactor in a state where condensation does not occur, the moving space from the vessel to the reactor is heated up sequentially from 120 ℃ to 150 ℃. Argon (Ar) gas having a flow rate of 200sccm to 500sccm was used as a carrier gas for moving the upper surface modifier compounds of compound 2 and compound 5 to the reactor. Thereafter, argon gas having a flow rate of 500sccm to 2000sccm was used to flow out the upper surface modifier compound remaining in the reactor. Thereafter, argon (Ar) gas having a flow rate of 200sccm to 500sccm was used as a gas for introducing Cp-Zr, cp-Hf and Mg [ (] Et Cp) 2 The precursor compound is moved to the carrier gas in the reactor. Thereafter, the upper surface modifier remaining in the reactor and Cp-Zr, cp-Hf and [ { CH ] were reacted with argon at a flow rate of 500sccm to 2000sccm 3 CH 2 (C 5 H 4 )} 2 Mg]The precursor compound flows out. Thereafter, the oxygen source O is turned on 2 Flowing into an ozone generator at a flow rate of 500sccm to 1000sccm, and generating a concentration of about 180g/m 3 To 220g/m 3 And is used as a reaction gas. Thereafter, argon gas at a flow rate of 500sccm to 2000sccm was used to make the remaining upper surface modifier, cp-Zr, cp-Hf and Mg [. Sup. Et Cp) 2 Precursor compounds, ozone and reaction by-products flow out. At this time, the process pressure of the reactor was measured to be 0.9 to 1.2 Torr, the supply time of the vaporized upper surface modifier compound was set to about 1 to 30 seconds, the purge time in the reactor was set to about 5 to 30 seconds, and the vaporized Cp-Zr, cp-Hf and Mg [ ] Et Cp) 2 The supply time of the precursor compound was set to about 5 to 20 seconds, the purge time in the reactor was set to about 5 to 30 seconds, the ozone supply time was set to about 5 to 30 seconds, and the purge time in the reactor was set to about 5 to 30 seconds. In all the processes, a zirconium oxide film, a hafnium oxide film and a magnesium oxide film were deposited by repeating the deposition cycle 100 times, and respective thicknesses were confirmed using an ellipsometerAnd deposition rate.
In order to confirm the deposition characteristics of the Cp-Zr precursor compound based on the temperature change and the use or non-use of the upper surface modifier, first, the Cp-Zr compound was used alone without using the upper surface modifier, the zirconia film was deposited while being raised from 250℃to 340℃at intervals of 10℃to 25℃and then the upper surface modifier compound of compound 2 was used, the zirconia film was deposited while being raised from 250℃to 340℃at intervals of 10℃to 25℃and the result thereof is shown in FIG. 6.
In order to confirm the deposition characteristics of the Cp-Hf precursor compound based on the temperature change and the use or non-use of the upper surface modifier, first, the Cp-Hf compound was used alone without using the upper surface modifier, and a hafnium oxide film was deposited while being raised from 250 to 400℃at intervals of 10 to 25 ℃. Further, in order to confirm the deposition characteristics based on the type of the upper surface modifier, the upper surface modifier compounds of compound 2 and compound 5 were used, respectively, and a hafnium oxide film was deposited while being raised from 250 to 400 at intervals of 10 to 25 ℃, the deposition results of which are shown in fig. 7.
To confirm Mg Et Cp) 2 Deposition characteristics of the precursor Compound based on temperature Change and the use or absence of the Upper surface modifier, first, mg was used alone without the upper surface modifier Et Cp) 2 A compound, a magnesium oxide film was deposited while being raised from 250 ℃ to 340 ℃ at intervals of 10 ℃ to 25 ℃. In addition, in order to confirm the deposition characteristics based on the kind of the upper surface modifier, the upper surface modifier compounds of compound 2 and compound 5 were used, respectively, and a magnesium oxide film was deposited while being raised from 250 to 340 at intervals of 10 to 25 ℃, and the experimental results are shown in fig. 8.
As can be confirmed from fig. 6, when the upper surface modifier of compound 2 is used, the effect that the deposition rate of the Cp-Zr precursor compound is reduced by about 34.3% to 61.2% is exhibited.
From fig. 7, it can be confirmed that the effect of reducing the deposition rate of the Cp-Hf precursor compound by about 38.7 to 56.0% is exhibited when the upper surface modifier of compound 2 is used, and that the effect of reducing the deposition rate of the Cp-Hf precursor compound by about 37.7 to 75.4% is exhibited when the upper surface modifier of compound 5 is used.
As can be confirmed from FIG. 8, when the upper surface modifier of Compound 2 was used, it exhibited Mg # Et Cp) 2 The deposition rate of the precursor compound was reduced by about 2.1 to 48.6% and Mg was shown when the upper surface modifier of compound 5 was used Et Cp) 2 The deposition rate of the precursor compound is reduced by about 74.8% to 81.4% effect.
The foregoing description of the present application is exemplary, and it will be appreciated by those of ordinary skill in the art that other specific forms may be readily modified without altering the technical spirit or essential features of the present application. Accordingly, it should be understood that the above-described embodiments are illustrative in all respects, rather than restrictive. For example, each component described as a single type may be implemented in a distributed manner, and components described as distributed may also be implemented in a combined form.
The scope of the present application is indicated by the following claims rather than the detailed description, and should be construed as being derived from the meaning and scope of the claims and their equivalents.
Claims (15)
1. An upper surface modifier represented by the following formula I:
[ formula I ]
In the case of the formula I described above,
R 1 and R is 2 Each independently is hydrogen, or a straight or branched chain C 1-5 Alkyl, or C being linear or branched 1-5 Alkyl-substituted dialkylamino; or R is 1 And R is 2 Is a substituted or unsubstituted C linked to each other 2-6 A cyclic alkyl group,
R 3 and R is 4 Each independently is a straight or branched chain C 1-5 An alkyl group; or R is 3 And R is 4 Is a substituted or unsubstituted C linked to each other 2-6 A cyclic alkyl group,
x is-O-, -S-or-NH.
2. The upper surface modifier of claim 1, wherein only R 1 And R is 2 Or only R 3 And R is 4 Is a substituted or unsubstituted C linked to each other 2-6 A cyclic alkyl group.
3. The upper surface modifier of claim 1, wherein R 1 And R is 2 Each independently is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl, 3-pentyl, dimethylamino, ethylmethylamino, diethylamino, methylpropylamino, ethylpropylamino or dipropylamino; or (b)
R 1 And R is 2 Are linked to each other to form a cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl group having a central carbon.
4. The upper surface modifier of claim 1, wherein R 3 And R is 4 Each independently is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl or 3-pentyl.
5. The upper surface modifier of claim 1, wherein the upper surface modifier is selected from the following compounds 1 to 5:
[ Compound 1]
[ Compound 2]
[ Compound 3]
[ Compound 4]
And [ Compound 5]
6. An upper surface modifier composition comprising an upper surface modifier represented by the following formula I:
[ formula I ]
In the case of the formula I described above,
R 1 and R is 2 Each independently is hydrogen, or a straight or branched chain C 1-5 Alkyl, or C being linear or branched 1-5 Alkyl-substituted dialkylamino; or R is 1 And R is 2 Is a substituted or unsubstituted C linked to each other 2-6 A cyclic alkyl group,
R 3 and R is 4 Each independently is a straight or branched chain C 1-5 An alkyl group; or R is 3 And R is 4 Is a substituted or unsubstituted C linked to each other 2-6 A cyclic alkyl group,
x is-O-, -S-or-NH.
7. The watch according to claim 6Surface modifier composition wherein R alone 1 And R is 2 Or only R 3 And R is 4 Is a substituted or unsubstituted C linked to each other 2-6 A cyclic alkyl group.
8. The upper surface modifier composition of claim 6, wherein the upper surface modifier comprises at least one selected from the group consisting of compounds 1 to 5:
[ Compound 1]
[ Compound 2]
[ Compound 3]
[ Compound 4]
And [ Compound 5]
9. A film forming method, wherein a film is formed by an atomic layer deposition method using the upper surface modifier composition according to any one of claims 6 to 8 and a precursor for film formation.
10. The film forming method according to claim 9, wherein the film is selected from the group consisting of a metal film, an oxide film, a nitride film, a carbide film, and combinations thereof.
11. The film forming method according to claim 9, wherein the film forming precursor contains at least one selected from Be, mg, ca, sr, ba, al, ga, in, sc, Y, la, si, ge, sn, P, as, sb, S, se, te, ti, zr, hf, V, ta, nb, cr, mo, W, mn, tc, re, fe, ru, os, co, rh, ir, ni, pd, pt, cu, ag and Au.
12. The film forming method according to claim 9, wherein the film forming method is performed at 200 ℃ to 500 ℃.
13. The film forming method according to claim 9, comprising:
providing a substrate in a reaction chamber;
providing a source material comprising the film-forming precursor and the upper surface modifier composition on the substrate;
purging the interior of the reaction chamber; and
a reactant capable of reacting with the source material to form a film is provided.
14. The film forming method of claim 13, wherein the step of providing the upper surface modifier composition is performed simultaneously with or overlapping in time with the step of providing a source material comprising the film forming precursor, or before or after the step of providing a source material comprising the film forming precursor.
15. The film forming method according to claim 13, wherein the reactant is at least one selected from the group consisting of ammonia, nitrogen, hydrazine, dimethylhydrazine, water vapor, oxygen, and ozone.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20200182913 | 2020-12-24 | ||
| KR10-2020-0182913 | 2020-12-24 | ||
| PCT/KR2021/019788 WO2022139535A1 (en) | 2020-12-24 | 2021-12-24 | Thin film forming method using top-surface modifier |
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| Publication Number | Publication Date |
|---|---|
| CN116324025A true CN116324025A (en) | 2023-06-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202180067978.8A Pending CN116324025A (en) | 2020-12-24 | 2021-12-24 | Film forming method using upper surface modifier |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR20220092440A (en) |
| CN (1) | CN116324025A (en) |
| TW (1) | TW202231643A (en) |
| WO (1) | WO2022139535A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2024076218A1 (en) * | 2022-10-07 | 2024-04-11 | 솔브레인 주식회사 | Chalcogenide-based thin-film modifier, and semiconductor substrate and semiconductor device produced using same |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001234343A (en) * | 2000-02-17 | 2001-08-31 | Asahi Denka Kogyo Kk | Metallic compound solution and method for producing thin film using the same |
| KR100385194B1 (en) * | 2000-02-28 | 2003-05-27 | 도오꾜오까고오교 가부시끼가이샤 | Coating solutions for use in forming bismuth-based ferroelectric thin films and a method of forming bismuth-based ferroelectric thin films using the coating solutions |
| KR20070026658A (en) * | 2004-06-10 | 2007-03-08 | 미츠비시 마테리알 가부시키가이샤 | Solution raw material for organic metal chemical vapor deposition and complex oxide dielectric thin film formed by using such raw material |
| US8993072B2 (en) * | 2011-09-27 | 2015-03-31 | Air Products And Chemicals, Inc. | Halogenated organoaminosilane precursors and methods for depositing films comprising same |
| KR20190061877A (en) | 2017-11-28 | 2019-06-05 | 주식회사 원익아이피에스 | Method of depositing thin film |
| EP4065746A4 (en) * | 2019-12-27 | 2023-06-28 | Versum Materials US, LLC | Method for depositing a film |
-
2021
- 2021-12-23 TW TW110148528A patent/TW202231643A/en unknown
- 2021-12-24 KR KR1020210186684A patent/KR20220092440A/en not_active Application Discontinuation
- 2021-12-24 CN CN202180067978.8A patent/CN116324025A/en active Pending
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| KR20220092440A (en) | 2022-07-01 |
| WO2022139535A1 (en) | 2022-06-30 |
| TW202231643A (en) | 2022-08-16 |
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