CN115448954B - ALD precursor molybdenum complex and preparation method thereof - Google Patents
ALD precursor molybdenum complex and preparation method thereof Download PDFInfo
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 62
- 239000011733 molybdenum Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000002243 precursor Substances 0.000 title abstract description 20
- 238000010668 complexation reaction Methods 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 9
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 9
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 9
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 9
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011684 sodium molybdate Substances 0.000 claims description 5
- 235000015393 sodium molybdate Nutrition 0.000 claims description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims description 5
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 238000000231 atomic layer deposition Methods 0.000 abstract description 19
- 229910000476 molybdenum oxide Inorganic materials 0.000 abstract description 8
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000000151 deposition Methods 0.000 abstract description 4
- 230000008021 deposition Effects 0.000 abstract description 4
- 238000007740 vapor deposition Methods 0.000 abstract description 4
- 238000002474 experimental method Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 31
- 239000010409 thin film Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000012263 liquid product Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229910052594 sapphire Inorganic materials 0.000 description 3
- 239000010980 sapphire Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical group [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- GPBUGPUPKAGMDK-UHFFFAOYSA-N azanylidynemolybdenum Chemical compound [Mo]#N GPBUGPUPKAGMDK-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910016021 MoTe2 Inorganic materials 0.000 description 1
- 229910007161 Si(CH3)3 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000000277 atomic layer chemical vapour deposition Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000572 ellipsometry Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000012705 liquid precursor Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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 System
-
- 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
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
Abstract
The invention belongs to the technical field of molybdenum-containing film precursors, and particularly relates to an ALD precursor molybdenum complex and a preparation method thereof. The invention discloses a novel molybdenum complex, which has a structure shown in a formula (I), is liquid at room temperature, has good volatility and high thermal stability, can be used as a precursor of vapor deposition to realize the deposition of a molybdenum-containing film, and is particularly suitable for preparing a molybdenum oxide film by Atomic Layer Deposition (ALD). In addition, the preparation method of the molybdenum complex has the advantages of simple reaction steps and easiness in implementation, the reaction process is free from heating, the reaction is gentle and free from severe phenomenon, potential safety hazards are avoided, and the repeated experiment stability is good. The required reaction raw materials are cheap and easy to purchase, and the final prepared product has higher yield, thereby being beneficial to industrial quantitative production.
Description
Technical Field
The invention belongs to the technical field of molybdenum-containing film precursors, and particularly relates to an ALD precursor molybdenum complex and a preparation method thereof.
Background
Molybdenum, molybdenum oxide, and molybdenum nitride are widely used in various fields due to low resistance, large work function (workfunction), and excellent thermal/chemical stability. The metallic molybdenum has a low specific resistance of 15 μΩ·cm or less, and thus can be suitably used for wiring of display devices, molybdenum oxide exhibits excellent metalloid conductivity and can be suitably used for hydrocarbon oxidation catalysts, solid Oxide Fuel Cell (SOFC) anodes, and high-capacity reversible lithium ion cell (LIB) anodes, and molybdenum trioxide (MoO 3) exhibits electrochromic (electrochromic) characteristics and catalyst characteristics, and can be suitably used for nanostructured gas sensors and solid state lithium ion cells.
The molybdenum-containing thin film can be used in organic light emitting diodes, liquid crystal displays, plasma display panels, field emission displays, thin film solar cells, low resistance ohmic (ohmic), other electronic devices, and semiconductor devices, and is mainly used as an electronic component such as a barrier film. Among them, the molybdenum trioxide (MoO 3) film has various excellent characteristics such as electrochromic, gasochromic, photochromic and the like, and also has good electrochemical characteristics, so that the MoO 3 film is widely used in various fields, such as gas sensors, organic optoelectronic devices, lithium ion batteries and the like, and MoO 3 is also a raw material for synthesizing two-dimensional materials such as MoS 2、MoSe2、MoTe2 and the like.
Currently, reported methods for preparing MoO 3 thin films mainly include spray pyrolysis, pulsed laser deposition, sol-gel, sputtering, atomic Layer Deposition (ALD), and the like. However, most of these methods have problems of complex technical parameters, severe process conditions, etc., which results in great restrictions on their application. The thin film prepared by atomic layer deposition can realize good step coverage, large-area uniformity and accurate thickness controllability, so that the thin film is applied to preparing a high-quality MoO 3 thin film, but the ALD precursor for preparing the MoO 3 thin film is extremely lack, especially the precursor with high volatility, good evaporation rate and high thermal stability. Therefore, it is necessary to synthesize a molybdenum precursor with high volatility and high thermal stability.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention designs and synthesizes a novel molybdenum complex which has high volatility and high thermal stability and can be applied to growing a molybdenum-containing film (such as MoO 3 film) in ALD.
In order to achieve the above purpose, the present invention is realized by the following technical scheme:
the invention provides a molybdenum complex, which has a structure represented by a formula (I):
In formula (i), R 1 and R 2 are independently hydrogen, or a linear or branched alkyl group having 1 to 10 carbon atoms; r 3 and R 4 are independently hydrogen, or a straight or branched alkyl group having 1 to 10 carbon atoms; r 5 is a linear or branched alkyl group each independently having 1 to 10 carbon atoms; n is an integer from 1 to 5.
Preferably, in formula (i), each R 1、R2 is independently selected from any one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl; r 3 and R 4 are each independently selected from any one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl; r 5 is independently selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl; n is an integer from 1 to 5. More preferably, R 1、R2 is H, R 3、R4 and R 5 are Me, n=1.
Preferably, the molybdenum complex is selected from any one of the following structural formulas:
More preferably, the molybdenum complex has the structural formula shown below:
The molybdenum complex of the invention is liquid at room temperature, has good volatility and high thermal stability, and comprises N-tBu ligand in the structure, and the Mo complex containing the N-tBu ligand can be used for preparing Mo related films by atomic layer deposition. The complex of the invention has similar structure and presumably similar properties, is expected to be used for preparing films such as molybdenum oxide by Atomic Layer Deposition (ALD), and can be used as a precursor of vapor deposition to realize the deposition of molybdenum-containing films (such as molybdenum oxide, molybdenum nitride, molybdenum sulfide, metallic molybdenum and the like).
The invention also provides a preparation method of the molybdenum complex, which comprises the following steps:
S1, under the inert gas atmosphere, carrying out heating reflux reaction on sodium molybdate, ethylene glycol dimethyl ether, triethylamine, tert-butylamine and trimethylchlorosilane to obtain (tBuN) 2Mo(Cl2) -dme;
S2, dissolving (tBuN) 2Mo(Cl2) -dme in an organic solvent under an inert gas atmosphere, adding pyridine, and stirring at room temperature to react to obtain (tBuN) 2Mo(Cl2)py2 which is marked as a Mo-0.5 intermediate;
S3, dissolving the Mo-0.5 intermediate in an organic solvent in an inert gas atmosphere, adding an alkane solution of (R 1-C-R2)nSiR3R4R5 -M salt), stirring at room temperature for reaction, removing the solvent, adding an alkane extraction product, filtering to remove insoluble precipitate, and drying the obtained filtrate to obtain the molybdenum complex, wherein the values of R 1、R2、R3、R4、R5 and n are the same as those of claim 1 or claim 2.
Preferably, in the step S1, the dosage ratio of the sodium molybdate, the ethylene glycol dimethyl ether, the triethylamine, the tert-butylamine and the trimethylchlorosilane is 20g:300-500mL:54mL:24mL:112mL.
Preferably, in step S3, M in the (R 1-C-R2)nSiR3R4R5 -M salt is selected from any one of Li, na, K. More preferably, M is Li, R 3,R4,R5 is CH 3,R1,R2 is H, n is 1. The (R 1-C-R2)nSiR3R4R5 -M salt is more preferably trimethyllithium methyl).
Preferably, in step S2, the molar ratio of (tBuN) 2Mo(Cl2) -dme to pyridine is 1:20-30.
Preferably, in step S3, the molar ratio of the Mo-0.5 intermediate to the (R 1-C-R2)nSiR3R4R5 -M salt) is 1:2 to 1:2.2.
Preferably, in step S1, the heating reflux time is 12-24 hours.
Preferably, in steps S2 and S3, the organic solvent is selected from n-hexane, n-pentane, n-heptane, toluene or tetrahydrofuran. The organic solvents used all need to be subjected to the operation of removing water and oxygen.
Preferably, in steps S2 and S3, the reaction is stirred at room temperature for not less than 5 hours. More preferably, the reaction is stirred at room temperature for a period of 12 to 24 hours.
Preferably, in step S3, the alkane is n-pentane or n-hexane.
Preferably, the filtrate obtained in the step S3 is dried to obtain a molybdenum complex as a crude product, and the crude product is rectified to obtain the high-purity molybdenum complex. The rectification is vacuum rectification, the vacuum degree of the rectification is 0.2-0.3 torr, and the rectification temperature is 90-120 ℃.
The invention also provides application of the molybdenum complex in preparing a molybdenum-containing film, namely, the molybdenum complex is used as an ALD precursor to grow to obtain the molybdenum-containing film.
Preferably, the molybdenum-containing film is a MoO 3 film.
Compared with the prior art, the invention has the beneficial effects that:
Few Mo precursors exist that are suitable for ALD or CVD, especially the lack of liquid precursors with high volatility, good evaporation rate and high thermal stability. Therefore, the invention discloses a novel molybdenum complex, which has a structure shown in a formula (I), is liquid at room temperature, has good volatility and high thermal stability, contains an N-tBu ligand, can be used as a precursor of vapor deposition to realize the deposition of a molybdenum-containing film, is beneficial to preparing molybdenum-containing films with higher quality, such as molybdenum oxide, and is particularly suitable for ALD to prepare the molybdenum oxide film. In addition, the preparation method of the molybdenum complex has simple reaction steps, the crude product can be obtained only by one-step reaction after the Mo-0.5 intermediate is prepared, the high-purity molybdenum complex can be obtained by simple post-treatment of the crude product, the operation is simple and easy to implement, the reaction process is not required to be heated, the reaction is gentle and free from severe phenomenon, potential safety hazards are avoided, and the repeated experiment stability is good. The required reaction raw materials are cheap and easy to purchase, and the final prepared product has higher yield, thereby being beneficial to industrial quantitative production.
Drawings
FIG. 1 is a physical diagram of a molybdenum complex;
FIG. 2 is a nuclear magnetic hydrogen spectrum of a molybdenum complex;
FIG. 3 is an AFM 3D topography of a MoO 3 film;
FIG. 4 is a TGA curve of molybdenum complex.
Detailed Description
The following describes the invention in more detail. The description of these embodiments is provided to assist understanding of the present invention, but is not intended to limit the present invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The experimental methods in the following examples are conventional methods unless otherwise specified, and the experimental materials used in the following examples are commercially available from conventional commercial sources unless otherwise specified.
The invention provides a molybdenum complex, which has a structure represented by a formula (I):
In the formula (I), R 1、R2 is independently selected from any one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl; r 3 and R 4 are each independently selected from any one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl; r 5 is independently selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl; n is an integer from 1 to 5.
Example 1 molybdenum Complex and method for preparing the same
The molybdenum complex has a structure represented by formula (i), wherein n=1, R 1、R2 is H, and R 3、R4 and R 5 are Me. The structure of the molybdenum complex is as follows:
the synthesis method of the molybdenum complex comprises the following steps:
(1) Under the nitrogen atmosphere, adding 20g of sodium molybdate into a 1L Schlenk bottle, adding 400mL of ethylene glycol dimethyl ether, sequentially adding 54mL of triethylamine, 24mL of tert-butylamine and 112mL of trimethylchlorosilane, heating and refluxing at 80 ℃ for 24 hours, filtering to remove precipitate, evaporating the solvent from the obtained filtrate under reduced pressure, and reacting to obtain yellow solid (tBuN) 2Mo(Cl2) -dme 33.31g with the yield of 86%;
(2) 10.65g (tBuN) 2Mo(Cl2 -dme, 200mL toluene, 50mL pyridine and stirring at room temperature (400-700 rpm) are added into a 500mL Schlenk bottle under nitrogen atmosphere to react overnight, and 11.93g of Mo-0.5 orange solid (intermediate) is obtained after the solvent is evaporated under reduced pressure, the yield is 96%;
(3) Mo-0.5 intermediate (10.43 g,22.3 mmol) and toluene (200 mL) were added to a 500mL Schlenk flask under nitrogen atmosphere, and a solution of trimethyllithium methyllithium n-hexane (82 mL,45.1 mmol) at a concentration of 0.55M/L was added dropwise to the reaction solution via a constant pressure dropping funnel, followed by stirring overnight (400-700 rpm) at room temperature, evaporating the solvent under reduced pressure, then adding 150mL n-hexane, followed by filtration through celite, evaporating the filtrate to dryness to obtain a crude black reddish liquid product, and subjecting the obtained crude liquid product to reduced pressure rectification at a vacuum of 0.2torr at a rectification temperature of 120℃to obtain a yellow liquid product (5.83 g,14.13 mmol) at a yield of 63%. As can be seen from fig. 1, the product molybdenum complex is liquid at room temperature. The nuclear magnetic hydrogen spectrum of the product is shown in figure 2, and the data of the nuclear magnetic hydrogen spectrum are as follows:
1H NMR(400MHz,C6D6,ppm):δ1.40(s,18H,C(CH3)3),1.10(s,4H,CH2),0.23(s,18H,Si(CH3)3).
experimental example 1 application of molybdenum Complex as ALD precursor to preparation of molybdenum-containing thin film
The film was prepared using the molybdenum complex prepared in example 1 as a Mo precursor by the following method:
The p-type Si or sapphire is used as a substrate, the Mo precursor of the embodiment 1 is used as a metal source, the heating temperature of a source bottle is 120 ℃, the co-reactant is ozone, the process temperature is 300 ℃, the Mo source pulse time is 2s, the N 2 carrier gas flow is 150sccm, the ozone pulse time is 20s, the N 2 purging time between the two pulses is 5s, the growth cycle number is 1000, and finally the thickness of the prepared film is 48nm measured by an ellipsometry.
In order to determine the components of the deposited film, XPS test is performed on the film deposited on the sapphire substrate, and the element content on the surface of the film and the element content etched in the depth of 20nm are respectively tested and collected, and the test results are shown in Table 1.
As can be seen from table 1, the element content of the film etched at 20nm depth can more accurately reflect the composition of the film, specifically O: mo=3.1:1, indicating that the deposited film is a MoO 3 film with a stoichiometric ratio of 3:1.
TABLE 1 XPS measurement of elemental content of ALD films
| Si2p | Mo3d | C1s | N1s | O1s | |
| Atomic％ | Atomic％ | Atomic％ | Atomic％ | Atomic％ | |
| Surface of the body | 2.69582 | 10.0462 | 20.383 | 33.5495 | 33.3255 |
| Etching 20nm | 2.89192 | 11.0816 | 15.7305 | 35.8439 | 34.4521 |
Meanwhile, in order to observe the surface morphology of the thin film, the thin film deposited on the sapphire substrate was selected for AFM test, and the test result is shown in fig. 3. From the graph, the film is obtained by successful growth, and the crystal grains are uniform and the roughness is lower.
In addition, to investigate the volatility and thermal stability of the precursor, thermal characterization of the molybdenum complex precursor was performed.
As shown in the TGA curve of FIG. 4, the thermal curve of the molybdenum complex belongs to a single step drop, and has no obvious thermal decomposition behavior, which indicates that the molybdenum complex has better volatility and thermal stability.
Therefore, the novel molybdenum complex provided by the invention is liquid at room temperature, has good volatility and high thermal stability, can be used as a precursor of vapor deposition to realize the deposition of a molybdenum-containing film, and is particularly suitable for ALD to prepare a molybdenum oxide film (MoO 3 film).
The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, and yet fall within the scope of the invention.
Claims (6)
1. A method for preparing a molybdenum complex, characterized in that the molybdenum complex has a structure represented by formula (i):
In the formula (I), R 1、R2 is independently selected from any one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl; r 3 and R 4 are each independently selected from any one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl; r 5 is independently selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl; n is an integer from 1 to 5;
the preparation method of the molybdenum complex comprises the following steps:
S1, under the inert gas atmosphere, carrying out heating reflux reaction on sodium molybdate, ethylene glycol dimethyl ether, triethylamine, tert-butylamine and trimethylchlorosilane to obtain (tBuN) 2Mo(Cl2) -dme;
S2, dissolving (tBuN) 2Mo(Cl2) -dme in an organic solvent under an inert gas atmosphere, adding pyridine, and stirring at room temperature to react to obtain (tBuN) 2Mo(Cl2)py2 which is marked as a Mo-0.5 intermediate;
S3, dissolving the Mo-0.5 intermediate in an organic solvent in an inert gas atmosphere, adding an alkane solution of (R 1-C-R2)nSiR3R4R5 -M salt), stirring at room temperature for reaction, removing the solvent, adding an alkane extraction product, filtering to remove insoluble precipitate, and drying the obtained filtrate to obtain the molybdenum complex, wherein the values of R 1、R2、R3、R4、R5 and n are the same as the formula (I), and M in the (R 1-C-R2)nSiR3R4R5 -M salt is selected from any one of Li, na and K).
2. The method of preparing a molybdenum complex according to claim 1, wherein the molybdenum complex is selected from any one of the following structural formulas:
3. The method for preparing a molybdenum complex according to claim 2, wherein the molybdenum complex has the structural formula shown below:
4. the method for preparing a molybdenum complex according to claim 1, wherein in step S1, the dosage ratio of sodium molybdate, ethylene glycol dimethyl ether, triethylamine, tert-butylamine and trimethylchlorosilane is 20g:300-500mL:54mL:24mL:112mL.
5. The method for producing a molybdenum complex according to claim 1, wherein in step S2, the molar ratio of (tBuN) 2Mo(Cl2) -dme to pyridine is 1:20-30.
6. The method of claim 1, wherein in step S3, the molar ratio of Mo-0.5 intermediate to (R 1-C-R2)nSiR3R4R5 -M salt) is 1:2 to 1:2.2.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106536641A (en) * | 2014-07-07 | 2017-03-22 | 乔治洛德方法研究和开发液化空气有限公司 | Molybdenum- and tungsten-containing precursors for thin film deposition |
| KR20210019682A (en) * | 2019-08-13 | 2021-02-23 | 주식회사 레이크머티리얼즈 | novel tungsten precursor compound comprising silicon |
| CN113652672A (en) * | 2015-05-27 | 2021-11-16 | Asm Ip 控股有限公司 | Synthesis and use of precursors for ALD of molybdenum-or tungsten-containing thin films |
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| CN113652672A (en) * | 2015-05-27 | 2021-11-16 | Asm Ip 控股有限公司 | Synthesis and use of precursors for ALD of molybdenum-or tungsten-containing thin films |
| KR20210019682A (en) * | 2019-08-13 | 2021-02-23 | 주식회사 레이크머티리얼즈 | novel tungsten precursor compound comprising silicon |
Non-Patent Citations (5)
| Title |
|---|
| Facile synthesis of M(=NtBu)2(CH2SiMe3)2 (M=Mo or W) as potential precursors for thin film deposition;Younian Tang 等;《Inorganic Chemistry Communications》;第151卷;第110284-110287页 * |
| Ligand-Assisted Volatilization and Thermal Stability of Bis(imido)dichloromolybdenum(VI) ([(t-BuN=)2MoCl2]2) and Its Adducts;Michael A. Land 等;《Organometallics》;第39卷;第916-927页 * |
| Synthesis and some properties of 14 group element-containing alkylidene complexes of molybdenum and tungsten;Leonid N. Bochkarev 等;《Journal of Organometallic Chemistry》;第690卷;第5720-5727页 * |
| Thermal Stability and Decomposition Pathways in Volatile Molybdenum(VI) Bis-imides;Michael A. Land 等;《Inorg. Chem.》;第61卷;第4980-4994页 * |
| 胡其图.《物理学与现代工程技术》.河南科学技术出版社,2000,(第1版),第439-430页. * |
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