CN117164618A - Preparation method of metal complex precursor and metal oxide film - Google Patents
Preparation method of metal complex precursor and metal oxide film Download PDFInfo
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- CN117164618A CN117164618A CN202311142920.2A CN202311142920A CN117164618A CN 117164618 A CN117164618 A CN 117164618A CN 202311142920 A CN202311142920 A CN 202311142920A CN 117164618 A CN117164618 A CN 117164618A
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- 239000002243 precursor Substances 0.000 title claims abstract description 67
- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 14
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 34
- 150000004795 grignard reagents Chemical class 0.000 claims abstract description 34
- 150000003973 alkyl amines Chemical class 0.000 claims abstract description 33
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 23
- 229910052718 tin Inorganic materials 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims description 44
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 36
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- UGVPKMAWLOMPRS-UHFFFAOYSA-M magnesium;propane;bromide Chemical compound [Mg+2].[Br-].CC[CH2-] UGVPKMAWLOMPRS-UHFFFAOYSA-M 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 12
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- OZPUDFCGMLVMJY-UHFFFAOYSA-M [Cl-].CC=C[Mg+] Chemical compound [Cl-].CC=C[Mg+] OZPUDFCGMLVMJY-UHFFFAOYSA-M 0.000 claims description 3
- YSMZEMQBSONIMJ-UHFFFAOYSA-M magnesium;2-methanidylpropane;chloride Chemical compound [Mg+2].[Cl-].CC(C)[CH2-] YSMZEMQBSONIMJ-UHFFFAOYSA-M 0.000 claims description 3
- CQRPUKWAZPZXTO-UHFFFAOYSA-M magnesium;2-methylpropane;chloride Chemical compound [Mg+2].[Cl-].C[C-](C)C CQRPUKWAZPZXTO-UHFFFAOYSA-M 0.000 claims description 3
- JAUWOQLHLFMTON-UHFFFAOYSA-M magnesium;but-1-ene;bromide Chemical compound [Mg+2].[Br-].[CH2-]CC=C JAUWOQLHLFMTON-UHFFFAOYSA-M 0.000 claims description 3
- LWLPYZUDBNFNAH-UHFFFAOYSA-M magnesium;butane;bromide Chemical compound [Mg+2].[Br-].CCC[CH2-] LWLPYZUDBNFNAH-UHFFFAOYSA-M 0.000 claims description 3
- WSHFRLGXCNEKRX-UHFFFAOYSA-M magnesium;butane;bromide Chemical compound [Mg+2].[Br-].CC[CH-]C WSHFRLGXCNEKRX-UHFFFAOYSA-M 0.000 claims description 3
- QUXHCILOWRXCEO-UHFFFAOYSA-M magnesium;butane;chloride Chemical compound [Mg+2].[Cl-].CCC[CH2-] QUXHCILOWRXCEO-UHFFFAOYSA-M 0.000 claims description 3
- YNLPNVNWHDKDMN-UHFFFAOYSA-M magnesium;butane;chloride Chemical compound [Mg+2].[Cl-].CC[CH-]C YNLPNVNWHDKDMN-UHFFFAOYSA-M 0.000 claims description 3
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 claims description 3
- VFZXMEQGIIWBFJ-UHFFFAOYSA-M magnesium;cyclopropane;bromide Chemical compound [Mg+2].[Br-].C1C[CH-]1 VFZXMEQGIIWBFJ-UHFFFAOYSA-M 0.000 claims description 3
- YCCXQARVHOPWFJ-UHFFFAOYSA-M magnesium;ethane;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C YCCXQARVHOPWFJ-UHFFFAOYSA-M 0.000 claims description 3
- RMGJCSHZTFKPNO-UHFFFAOYSA-M magnesium;ethene;bromide Chemical compound [Mg+2].[Br-].[CH-]=C RMGJCSHZTFKPNO-UHFFFAOYSA-M 0.000 claims description 3
- IJMWREDHKRHWQI-UHFFFAOYSA-M magnesium;ethene;chloride Chemical compound [Mg+2].[Cl-].[CH-]=C IJMWREDHKRHWQI-UHFFFAOYSA-M 0.000 claims description 3
- LROBJRRFCPYLIT-UHFFFAOYSA-M magnesium;ethyne;bromide Chemical compound [Mg+2].[Br-].[C-]#C LROBJRRFCPYLIT-UHFFFAOYSA-M 0.000 claims description 3
- GWGVDNZFTPIGDY-UHFFFAOYSA-M magnesium;ethyne;chloride Chemical compound [Mg+2].[Cl-].[C-]#C GWGVDNZFTPIGDY-UHFFFAOYSA-M 0.000 claims description 3
- LZFCBBSYZJPPIV-UHFFFAOYSA-M magnesium;hexane;bromide Chemical compound [Mg+2].[Br-].CCCCC[CH2-] LZFCBBSYZJPPIV-UHFFFAOYSA-M 0.000 claims description 3
- UZNGRHDUJIVHQT-UHFFFAOYSA-M magnesium;prop-1-ene;bromide Chemical compound [Mg+2].[Br-].C[C-]=C UZNGRHDUJIVHQT-UHFFFAOYSA-M 0.000 claims description 3
- WQMNNHNWITXOAH-UHFFFAOYSA-M magnesium;prop-1-ene;bromide Chemical compound [Mg+2].[Br-].CC=[CH-] WQMNNHNWITXOAH-UHFFFAOYSA-M 0.000 claims description 3
- QBNOPZJAURRQCE-UHFFFAOYSA-M magnesium;prop-1-yne;bromide Chemical compound [Mg+2].[Br-].CC#[C-] QBNOPZJAURRQCE-UHFFFAOYSA-M 0.000 claims description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 22
- 239000000047 product Substances 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 19
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 18
- 230000008569 process Effects 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 238000000231 atomic layer deposition Methods 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 11
- 239000006227 byproduct Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 9
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 9
- 239000000543 intermediate Substances 0.000 description 9
- 229910052749 magnesium Inorganic materials 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 9
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 8
- -1 salt compound Chemical class 0.000 description 8
- 229910052726 zirconium Inorganic materials 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 7
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 7
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 238000000572 ellipsometry Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- GMEFXBFKMIZRMO-UHFFFAOYSA-N aminogermanium Chemical compound [Ge]N GMEFXBFKMIZRMO-UHFFFAOYSA-N 0.000 description 3
- SJZKDQIEKKDKQA-UHFFFAOYSA-N hexane;n-methylmethanamine Chemical compound CNC.CCCCCC SJZKDQIEKKDKQA-UHFFFAOYSA-N 0.000 description 3
- YDGSUPBDGKOGQT-UHFFFAOYSA-N lithium;dimethylazanide Chemical compound [Li+].C[N-]C YDGSUPBDGKOGQT-UHFFFAOYSA-N 0.000 description 3
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 description 3
- 238000005580 one pot reaction Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000013341 scale-up Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- ZRLCXMPFXYVHGS-UHFFFAOYSA-N tetramethylgermane Chemical compound C[Ge](C)(C)C ZRLCXMPFXYVHGS-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- OOOQRCWUVOFYFN-UHFFFAOYSA-M [Br-].CCC[Mg+].C1CCOC1 Chemical compound [Br-].CCC[Mg+].C1CCOC1 OOOQRCWUVOFYFN-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 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
- JKUUTODNPMRHHZ-UHFFFAOYSA-N n-methyl-n-[tris(dimethylamino)germyl]methanamine Chemical compound CN(C)[Ge](N(C)C)(N(C)C)N(C)C JKUUTODNPMRHHZ-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
The application relates to a preparation method of a metal complex precursor and a metal oxide film. The preparation method of the metal complex precursor comprises the following steps: reacting Grignard reagent with alkylamine, and adding MCl into the reaction system after the reaction is finished 4 Continuing the reaction to prepare a metal complex precursor; wherein the structural formula of the alkylamine is HNR 1 R 2 ，R 1 And R is 2 Each independently includes C 1 ～C 3 Alkyl, M comprises one or more of Ge and Sn, and the structural formula of the metal complex precursor is M (NR 1 R 2 ) 4 . The preparation method can improve the reaction safety and the yieldAnd purity, easy industrialization and large-scale production.
Description
Technical Field
The application relates to the field of organic metal compounds, in particular to a preparation method of a metal complex precursor and a metal oxide film.
Background
With the development of the very large scale integrated circuit industry, semiconductor materials are being developedThe properties and the preparation process thereof put more stringent requirements. According to moore's law, as the size of individual electronic devices is reduced, integrated circuit technology is continually evolving and the thickness of the gate dielectric layer is one of the determining factors affecting the size of the electronic devices. SiO is commonly used in the integrated circuit industry at present 2 As gate dielectric material for electronic devices, but as device feature sizes decrease, siO 2 When the thickness of the gate dielectric layer is reduced to the nanometer level, the silicon oxide film is formed by SiO 2 Leakage current with SiO 2 The reduction of the thickness of the gate dielectric layer increases exponentially, so that the huge leakage current not only seriously affects the performance of the device, but also finally leads to SiO 2 And cannot play an insulating role. Searching for high dielectric constant materials (high-K materials) to replace traditional SiO 2 The tunneling effect is reduced by increasing the physical thickness of the dielectric layer, which is an effective technical means for improving the stability of the electronic device. It is therefore important to find high K and metal gate material precursors suitable for ALD (atomic layer deposition) and CVD (chemical vapor deposition) use. Based on this, in recent years, germanium complex precursors and tin complex precursors have gradually come into the field of view of developers. For example, tetra (dimethylamino) germanium is a liquid at normal temperature, is a compound very sensitive to air and water vapor, can be dissolved in organic solvents such as hydrocarbons, carbon tetrachloride and the like, has better stability and higher vapor pressure, and also has quite high reactivity.
However, the existing preparation methods of the germanium complex precursor and the tin complex precursor are few, the highly inflammable raw materials butyl lithium and intermediate dimethyl amino lithium are generally needed in the preparation process, and a great potential safety hazard exists.
Disclosure of Invention
Based on the above, some embodiments of the present application provide a method for preparing a metal complex precursor, which can improve the reaction safety and the yield and purity, and is easy for industrial mass production.
In addition, other embodiments of the application also provide a preparation method of the metal oxide film.
A method for preparing a metal complex precursor, comprising the steps of:
reacting Grignard reagent with alkylamine, and adding MCl into the reaction system after the reaction is finished 4 Continuing the reaction to prepare a metal complex precursor;
wherein the structural formula of the alkylamine is HNR 1 R 2 ，R 1 And R is 2 Each independently includes C 1 ～C 3 Alkyl, M comprises one or more of Ge and Sn, and the structural formula of the metal complex precursor is M (NR 1 R 2 ) 4 。
In some of these embodiments, the grignard reagent comprises one or more of ethynylmagnesium bromide, vinyl magnesium bromide, n-propylmagnesium bromide, 1-propynylmagnesium bromide, isopropenylmagnesium bromide, propenyl magnesium bromide, cyclopropylmagnesium bromide, n-butylmagnesium bromide, sec-butylmagnesium bromide, 3-butenylmagnesium bromide, hexylmagnesium bromide, methylmagnesium chloride, ethylmagnesium chloride, ethynylmagnesium chloride, vinyl magnesium chloride, propenyl magnesium chloride, n-butylmagnesium chloride, isobutylmagnesium chloride, sec-butylmagnesium chloride, and tert-butylmagnesium chloride;
optionally, the grignard reagent comprises n-propyl magnesium bromide.
In some of these embodiments, the molar ratio of the grignard reagent to the alkylamine is 1 (1 to 1.5).
In some of these embodiments, the alkylamine comprises one or more of dimethylamine, diethylamine, and methylethylamine.
In some of these embodiments, the step of reacting the grignard reagent with the alkylamine comprises: firstly, adding the alkylamine into the Grignard reagent and the anhydrous hydrocarbon solvent at the temperature of between-15 and 0 ℃ under the protective atmosphere, and reacting for 6 to 10 hours at the temperature of between 20 and 30 ℃ after the addition is finished.
In some of these embodiments, the anhydrous hydrocarbon solvent comprises anhydrous n-hexane.
In some of these embodiments, MCl is added to the reaction system 4 The step of continuing the reaction comprises: the reaction system is reduced to-15 ℃ to 0 ℃, and the MCl is added into the reaction system under the protection atmosphere 4 After the addition is finished, stirring and reacting for 10 to 14 hours at the temperature of between 20 and 30 ℃.
In some of these embodiments, the alkylamine is the same as the MCl 4 The molar ratio of (4) to (5) is 1.
In some of these embodiments, the MCl is added 4 After the step of continuing the reaction, a step of filtering and distilling is also included.
A preparation method of a metal oxide film comprises the following steps:
preparing a metal complex precursor by adopting the preparation method;
and (3) reacting the metal complex precursor with an oxygen source to form a film, so as to prepare the metal oxide film.
The preparation method of the metal complex precursor comprises the steps of firstly reacting a Grignard reagent with alkylamine, and then adding MCl 4 And continuing the reaction to prepare a metal complex precursor, wherein the electronegativity of germanium and tin is much higher than that of magnesium, and the intermediate after the Grignard reagent reacts with alkylamine and the salt compound of the metal are used for carrying out an exchange reaction, so that the metal complex precursor is obtained, and the Grignard reagent is used for replacing the butyllithium reagent, so that the reaction process is mild and the safety is high. In addition, the reaction process does not need intermediate separation, a one-pot method is adopted to obtain a target product, and the particles of the byproducts obtained by the method are larger than those of lithium chloride, so that the particles are easy to remove by filtration, the metal purity of the product is high, the requirement of the semiconductor industry is easy to meet, the product yield is high, and the industrial production is easy to realize.
Drawings
FIG. 1 is a process flow diagram of a method for preparing a metal complex precursor according to one embodiment.
Detailed Description
In order that the application may be readily understood, a more complete description of the application will be rendered by reference to specific embodiments that are now described. Preferred embodiments of the application are given in the detailed description. This application may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
Unless otherwise indicated or contradicted, terms or phrases used in the present application have the following meanings:
in the present application, "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature.
In the description of the present application, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
In the present application, "one or more" means any one, any two or more of the listed items. Wherein "several" means any two or more.
In the present application, the percentage concentrations referred to refer to the final concentrations unless otherwise specified. The final concentration refers to the ratio of the additive component in the system after the component is added.
The word "preferably" or the like in the present application refers to embodiments of the application that may provide certain benefits in certain circumstances. However, other embodiments may be preferred under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the application.
When a range of values is disclosed in the present application, the range is considered to be continuous and includes the minimum and maximum values of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein.
In the application, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.
The terms "comprising" and "having" and any variations thereof in embodiments of the present application are intended to cover a non-exclusive inclusion. For example, a process, method, system, article, or apparatus that comprises a list of steps or elements is not limited to only those listed steps or elements but may alternatively include other steps or elements not listed or inherent to such process, method, article, or apparatus.
Reference in the specification to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment may be included in at least one embodiment of the application. The appearances of such phrases in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. Those of skill in the art will explicitly and implicitly appreciate that the described embodiments of the application may be combined with other embodiments.
As used herein, room temperature refers to a temperature of 20℃to 30℃unless otherwise specified.
In a first aspect of the present application, referring to fig. 1, a method for preparing a metal complex precursor is provided, which includes the following steps:
step S110: the grignard reagent is reacted with an alkylamine.
In some embodiments, the grignard reagent comprises one or more of ethynylmagnesium bromide, vinyl magnesium bromide, n-propylmagnesium bromide, 1-propynylmagnesium bromide, isopropenylmagnesium bromide, propenyl magnesium bromide, cyclopropylmagnesium bromide, n-butylmagnesium bromide, sec-butylmagnesium bromide, 3-butenylmagnesium bromide, hexylmagnesium bromide, methylmagnesium chloride, ethylmagnesium chloride, ethynylmagnesium chloride, vinyl magnesium chloride, propenyl magnesium chloride, n-butylmagnesium chloride, isobutylmagnesium chloride, sec-butylmagnesium chloride, and tert-butylmagnesium chloride.
Preferably, the grignard reagent comprises n-propyl magnesium bromide.
In some embodiments, the alkylamine has the formula HNR 1 R 2 ，R 1 And R is 2 Each independently includes C 1 ～C 3 An alkyl group. In some of these embodiments, the alkylamine comprises one or more of dimethylamine, diethylamine, and methylethylamine.
In some of these embodiments, the molar ratio of Grignard reagent to alkylamine is 1 (1 to 1.5). For example, the molar ratio of grignard reagent to alkylamine may be, but is not limited to, 1:1, 1:1.05, 1:1.1, 1:1.15, 1:1.2, 1:1.3, 1:1.35, 1:1.4, 1:1.45, 1:1.5, or a range consisting of any two of these values.
In some embodiments, step S110 includes: firstly, under the protective atmosphere of-15 ℃ to 0 ℃, adding alkylamine into Grignard reagent and anhydrous hydrocarbon solvent, and then, after the addition is finished, reacting for 6h to 10h at 20 ℃ to 30 ℃.
Alternatively, the temperature of the addition of the alkylamine may be, but is not limited to, a range of-15 ℃, -14 ℃, -13 ℃, -12 ℃, -11 ℃, -10 ℃, -9 ℃, -8 ℃, -7 ℃, -6 ℃, -5 ℃, -4 ℃, -3 ℃, -2 ℃, -1 ℃,0 ℃ or any two of these values. Because the boiling point of the alkylamine is lower, the volatilization of the alkylamine is reduced by adopting a low-temperature adding mode, and the reaction of the alkylamine and the Grignard reagent is facilitated.
Optionally, the protective atmosphere comprises nitrogen or argon.
Alternatively, the anhydrous hydrocarbon solvent comprises anhydrous n-hexane.
Alternatively, the grignard reagent is added in the form of a tetrahydrofuran solution of the grignard reagent.
Alternatively, in step S110, the temperature of the reaction may be, but is not limited to, 20 ℃, 22 ℃, 25 ℃, 28 ℃, 30 ℃ or a range consisting of any two of these values.
Optionally, in step S110, the reaction time may be, but is not limited to, 6h, 7h, 8h, 9h, 10h or a range consisting of any two of these values.
Step S120: after the reaction, MCl is added into the reaction system 4 And continuing the reaction to prepare the metal complex precursor.
Wherein M comprises one or more of Ge and Sn. The metal complex precursor has the structural formula M (NR) 1 R 2 ) 4 。
Similar to tetradimethylamino germanium and tetradimethylamino tin, the traditional synthesis process of tetradimethylamino zirconium is to prepare a lithium dimethyl amide intermediate first and then react the lithium dimethyl amide intermediate with zirconium tetrachloride, and the process is tried to be applied to the preparation of tetradimethylamino zirconium, and experiments show that as the electronegativity (2.01) of germanium is much greater than that of magnesium (1.31), the electronegativity (1.96) of tin is much greater than that of magnesium (1.31), and exchange reaction is carried out between the intermediate after Grignard reagent and alkylamine and a salt compound of the metal, so that another metal organic compound can be obtained. Zirconium, however, has a small electronegativity (1.33) compared to magnesium (1.31), so that zirconium tetradimethylamino cannot be prepared in this way.
In some embodiments, alkylamine is combined with MCl 4 The molar ratio of (4) to (5) is 1. For example, alkylamine with MCl 4 The molar ratio of (c) may be, but is not limited to, 4:1, 4.1:1, 4.2:1, 4.3:1, 4.4:1, 4.5:1, 4.6:1, 4.7:1, 4.8:1, 4.9:1, 5:1, or a range consisting of any two of these values.
In some embodiments, step S120 includes: the reaction system is reduced to-15 ℃ to 0 ℃, and MCl is added into the reaction system under the protection atmosphere 4 After the addition is finished, stirring and reacting for 10 to 14 hours at the temperature of between 20 and 30 ℃.
Optionally, add MCl 4 The temperature of (c) may be, but is not limited to, -15 ℃, -14 ℃, -13 ℃, -12 ℃, -11 ℃, -10 ℃, -9 ℃, -8 ℃, -7 ℃, -,-6 ℃, -5 ℃, -4 ℃, -3 ℃, -2 ℃, -1 ℃ and 0 ℃ or a range of any two of these values.
Optionally, the protective atmosphere comprises nitrogen or argon.
Alternatively, in step S120, the temperature of the reaction may be, but is not limited to, 20 ℃, 22 ℃, 25 ℃, 28 ℃, 30 ℃ or a range consisting of any two of these values.
Optionally, in step S120, the reaction time may be, but is not limited to, 10h, 11h, 12h, 13h, 14h or any two of these values.
In some embodiments, MCl is directly added to the reaction system without separation and purification after the reaction of step S110 is completed 4 The reaction was continued.
In some embodiments, after step S120, a step of filtering and distilling is also included. Insoluble byproducts were removed by filtration, and solvents and other byproducts were removed by distillation.
Grignard reagent is n-propyl magnesium bromide and MCl 4 Is GeCl 4 For example, the synthetic route for the metal complex precursor is as follows:
CH 3 CH 2 CH 2 MgBr+HNR 1 R 2 →MgBrNR 1 R 2 +CH 3 CH 2 CH 3
MgBrNR 1 R 2 +GeCl 4 →Ge(NR 1 R 2 ) 4 +MgClBr。
it will be appreciated that the grignard reagent is other reagent, MCl 4 Is SnCl 4 In this case, the synthetic route can be adjusted accordingly, and will not be described in detail.
The preparation method of the metal complex precursor has at least the following advantages:
(1) The preparation method of the metal complex precursor comprises the steps of firstly reacting a Grignard reagent with alkylamine, and then adding MCl 4 Continuing the reaction to prepare a metal complex precursor, wherein the reaction process does not need intermediate separation, a one-pot method is adopted to obtain a target product, and a Grignard reagent is used for replacing a butyl lithium reagent, so that the reaction process is mild and safeHigh integrity. In addition, compared with lithium chloride, the byproduct prepared by the method is easier to remove, the purity of the product metal is high, the requirement of the semiconductor industry is easily met, the product yield is high, and the industrial production is easy.
(2) The preparation method of the metal complex precursor has the advantages of simple and easily obtained reaction raw materials, convenient operation, safety and environmental protection, avoiding the use of n-butyllithium required in the conventional process, and simultaneously, directly adding MCl into a reaction system without separating intermediates 4 The target product is obtained by a one-pot method, the process is simple, byproducts are easy to remove, the post-treatment process is simple, the product yield is high, and the method is suitable for industrial scale-up production.
(3) In the traditional preparation method, butyl lithium is generally used, on one hand, certain potential safety hazard exists, on the other hand, butyl lithium products are generally diluted in alkane solvents, a large amount of waste liquid is generated in the use process, the environment is not protected enough, the hazardous waste disposal cost is increased, and in the preparation method, a Grignard reagent is used for replacing the butyl lithium reagent, so that the hazardous waste disposal cost is reduced.
The second aspect of the present application provides a method for producing a metal oxide thin film, comprising the steps of:
preparing a metal complex precursor by adopting the preparation method;
and (3) reacting the metal complex precursor with an oxygen source to form a film, so as to prepare the metal oxide film.
In some embodiments, the metal complex precursor is reacted with an oxygen source to form a film by chemical vapor deposition or atomic layer deposition. Specific chemical vapor deposition or atomic layer deposition processes may be conventional in the art.
In some of these embodiments, the oxygen source may be, but is not limited to, water.
In some of these embodiments, the metal oxide thin film preparation steps include: and heating the atomic layer deposition chamber to 250-350 ℃ by adopting an atomic layer deposition process, vacuumizing, then pulsing the metal complex precursor into the atomic layer deposition chamber through argon, and continuously introducing argon after the metal complex precursor is introduced, so as to clean the residual metal complex precursor and reaction byproducts. And then, utilizing argon to pulse water into the atomic layer deposition chamber, and continuously introducing argon after the water is introduced, so as to clean residual water and reaction byproducts. Repeating the steps to prepare the metal oxide film.
Alternatively, the pulse time of the metal complex precursor may be, but is not limited to, 0.2s and the pulse time of the water may be, but is not limited to, 0.3s.
Alternatively, the argon may be continued for a period of time, but is not limited to 10 seconds.
Experiments prove that the metal oxide film prepared by the method has good quality and high uniformity.
In order to make the objects and advantages of the present application more apparent, the following more detailed description of the preparation method and effects of the metal complex precursor of the present application will be given in connection with the specific examples, which are to be construed as merely illustrative, and not limitative of the present application. The following examples, unless otherwise specified, do not include other components than the unavoidable impurities. The drugs and apparatus used in the examples are all routine choices in the art, unless specifically indicated. The experimental methods without specific conditions noted in the examples were carried out according to conventional conditions, such as those described in the literature, books, or recommended by the manufacturer.
Example 1
The embodiment provides a preparation method of a germanium complex precursor, which comprises the following steps:
a solution of 2 mol/L of n-propylmagnesium bromide in tetrahydrofuran (400 mL,0.8 mol) and 400mL of n-hexane were added to a 2000 mL Schlenk flask under a nitrogen atmosphere, the temperature was lowered to about 0℃and then a solution of 20% by mass of dimethylamine-n-hexane (180.4 g,0.8 mol) was added dropwise thereto, and the reaction was allowed to proceed to room temperature for 8 hours. After the reaction, the reaction solution was cooled to 0℃again, germanium tetrachloride (42.8 g,0.2 mol) was slowly added dropwise under nitrogen protection, the temperature was returned to room temperature after the completion of the dropwise addition, and stirring was continued for 12 hours, filtration was performed, the solvent was dried by suction, and the residue was distilled under reduced pressure to give 41.8g of tetramethylgermanium amino with a yield of 84%. The characterization data for tetramethylamino germanium are as follows:
1 HNMR(C 6 D 6 ):2.66(s,24H)；
the purity of the product was checked by inductively coupled plasma mass spectrometry (ICP-MS) analysis, and the result showed that the magnesium content was 0.3ppm and the metal purity of the product was 5N.
Example 2
This example provides a method for preparing a germanium complex precursor, which is similar to example 1 in terms of preparation steps, except that the amount of dimethylamine-n-hexane solution in example 1 is changed to 225.4 g, and the specific steps are as follows:
2 mol/L of n-propyl magnesium bromide tetrahydrofuran solution (400 ml,0.8 mol) and 400ml of n-hexane were added to a 2000 ml Schlenk flask under a nitrogen atmosphere, the temperature was lowered to about 0 ℃, then a 20% by mass n-hexane solution (225.4 g, 1.0 mol) of dimethylamine was added dropwise, the temperature was gradually returned to room temperature after the addition was completed and reacted for 8 hours, the reaction solution was again cooled to 0 ℃, germanium tetrachloride (42.8 g,0.2 mol) was slowly added dropwise under nitrogen protection, the temperature was returned to room temperature, and stirring was continued for 12 hours, the solvent was filtered, and the residue was distilled under reduced pressure to obtain 43.8 g of tetramethylgermanium, the yield of which was 88%. The characterization of tetramethylammonium germanium is the same as in example 1 and is not repeated.
Example 3
The present example provides a method for preparing a germanium complex precursor, which has similar preparation steps to those of example 2, except that the reaction temperature in example 2 is changed to-10 ℃, and the specific steps are as follows:
2 mol/L of tetrahydrofuran solution (400 ml,0.8 mol) of n-propyl magnesium bromide and 400ml of n-hexane are added into a 2000 ml Schlenk bottle under the nitrogen atmosphere, the temperature is reduced to about minus 10 ℃, then n-hexane solution (225.4 g, 1.0 mol) of dimethylamine with the mass fraction of 20% is dropwise added, the room temperature is slowly restored after the dropwise addition and the reaction is carried out for 8 hours, the reaction solution is cooled to minus 10 ℃ again, germanium tetrachloride (42.8 g,0.2 mol) is slowly dropwise added under the protection of nitrogen, the temperature is restored to the room temperature, the stirring is continued for 12 hours, the solvent is filtered, the solvent is pumped out, and the residue is distilled under reduced pressure, thus obtaining 46.3 g of tetramethylgermanium with the yield of 93%. The tetradimethylamino germanium is characterized as follows:
the purity of the product was checked by inductively coupled plasma mass spectrometry (ICP-MS) analysis, and the result showed that the magnesium content was 0.22ppm and the metal purity of the product was 5N.
Example 4
This example provides a method for preparing a germanium complex precursor, which has similar preparation steps to example 3, with the difference that in this example, dimethylamine in example 3 is merely changed to equivalent diethylamine, and the specific steps are as follows:
2 mol/L of n-propylmagnesium bromide in tetrahydrofuran (400 ml,0.8 mol) and 400ml of n-hexane were added to a 2000 ml Schlenk flask under a nitrogen atmosphere, the temperature was lowered to about-10℃and then diethylamine (73.14 g, 1.0 mol) was added dropwise, the temperature was slowly returned to room temperature after the addition was completed and reacted for 8 hours, the reaction solution was again cooled to-10℃and germanium tetrachloride (42.8 g,0.2 mol) was slowly added dropwise under nitrogen protection, the temperature was returned to room temperature and stirring was continued for 12 hours, the solvent was filtered, the residue was distilled under reduced pressure to obtain 63.6 g of tetraethyl amino germanium with a yield of 88%. The characterization data for tetraethyl amino germanium are as follows:
1 HNMR(C 6 D 6 ):3.34(q,16H),1.15(t,24H)；
the purity of the product was checked using ICP-MS analysis, and the result showed that the metal purity of the product was 5N.
Example 5
This example provides a method for preparing a germanium complex precursor, which has similar preparation steps to those of example 3, except that dimethylamine in example 3 is merely changed to equivalent methylethylamine, and the specific steps are as follows:
a solution of 2 mol/l of n-propylmagnesium bromide in tetrahydrofuran (400 ml,0.8 mol) and 400ml of n-hexane were added to a 2000 ml Schlenk flask under a nitrogen atmosphere, cooled to about-10℃and then methylethylamine (59.1 g, 1.0 mol) was added dropwise thereto, and the mixture was allowed to slowly return to room temperature and reacted at room temperature for 8 hours. After the reaction, the reaction solution was cooled to-10 ℃ again, germanium tetrachloride (42.8 g,0.2 mol) was slowly added dropwise under nitrogen protection, the reaction solution was returned to room temperature after the completion of the dropwise addition, and stirring was continued for 12 hours, filtration was performed, the solvent was dried by suction, and the residue was distilled under reduced pressure to obtain 51.9 g of tetramethylgermanium amino with a yield of 85%. The characterization data for tetramethylethylamino germanium are as follows:
1 HNMR(C 6 D 6 ):3.24(q,8H),2.97(s,12H),1.15(t,12H)；
the purity of the product was checked using ICP-MS analysis, and the result showed that the metal purity of the product was 5N.
Example 6
This example provides a method for preparing a germanium complex precursor, the preparation steps of which are similar to those of example 3, except that in this example, the tetrahydrofuran solution of n-propyl magnesium bromide in example 3 is changed to an equivalent tetrahydrofuran solution of ethyl magnesium bromide, and the preparation steps are as follows:
1 mol/L of ethyl magnesium bromide in tetrahydrofuran (800 ml,0.8 mol) and 400ml of n-hexane are added into a 2000 ml Schlenk bottle under the nitrogen atmosphere, the temperature is reduced to about minus 10 ℃, then dimethylamine n-hexane solution (225.4 g, 1.0 mol) with the mass fraction of 20% is dropwise added, the room temperature is slowly restored after the dropwise addition and the reaction is carried out for 8 hours, the reaction solution is cooled to minus 10 ℃ again after the reaction is finished, germanium tetrachloride (42.8 g,0.2 mol) is slowly dropwise added under the protection of nitrogen, the temperature is returned to the room temperature after the dropwise addition, the stirring is continued for 12 hours, the solvent is filtered, the solvent is pumped out, and the residue is distilled under reduced pressure, thus obtaining 44.3 g of tetramethyl amino germanium with the yield of 89%. The characterization of tetramethylammonium germanium is the same as in example 1 and is not repeated.
It can be seen from examples 6 and 3 that tetramethylgermanium amino is also obtained by using ethylmagnesium bromide instead of n-propylmagnesium bromide, but from the viewpoint of safety of the process, the explosion limit of propane, a reaction by-product of example 3, is 2.1% to 9.5%, and ethane, a reaction by-product of example 6, is 3.0% to 16.0%, and thus the preferred grignard reagent is n-propylmagnesium bromide.
Example 7
The difference between the preparation method of the tin complex precursor and the preparation method of the embodiment 3 is that the germanium tetrachloride in the embodiment 3 is only changed into tin tetrachloride with equivalent weight, and the specific preparation steps are as follows:
2 mol/L of tetrahydrofuran solution (400 ml,0.8 mol) of n-propyl magnesium bromide and 400ml of n-hexane are added into a 2000 ml Schlenk bottle under the nitrogen atmosphere, the temperature is reduced to about minus 10 ℃, then n-hexane solution (225.4 g, 1.0 mol) of dimethylamine with the mass fraction of 20% is dropwise added, the room temperature is slowly restored after the dropwise addition and the reaction is carried out for 8 hours, the reaction solution is cooled to minus 10 ℃ again after the completion of the reaction, tin tetrachloride (52.1 g,0.2 mol) is slowly dropwise added under the protection of nitrogen, the temperature is restored to the room temperature after the dropwise addition, the stirring is continued for 12 hours, the solvent is filtered, the solvent is pumped out, and the residue is distilled under reduced pressure to obtain 50.2 g of tetramine tin with the yield of 85%. The characterization data for tetradimethylaminotin are as follows:
1 HNMR(C 6 D 6 ):2.81(s,24H)；
the purity of the product was checked using ICP-MS analysis, and the result showed that the metal purity of the product was 5N.
Comparative example 1
Comparative example 1 provides a conventional method of preparing a germanium complex precursor comprising the steps of:
2.5 mol/L n-hexane solution (320 ml,0.8 mol) of n-butyllithium and 400ml of n-hexane were added to a 2000 ml Schlenk flask under a nitrogen atmosphere, the temperature was lowered to about-10 ℃, then, n-hexane solution (225.4 g, 1.0 mol) of dimethylamine having a mass fraction of 20% was added dropwise, the temperature was slowly returned to room temperature after the addition was completed and reacted for 8 hours, the reaction solution was cooled again to-10 ℃, germanium tetrachloride (42.8 g,0.2 mol) was slowly added dropwise under nitrogen protection, the temperature was returned to room temperature, and stirring was continued for 12 hours, the solvent was filtered, and the residue was distilled under reduced pressure to obtain 40.8 g of tetramethylgermanium amino having a yield of 82%.
The purity of the product was checked by inductively coupled plasma mass spectrometry (ICP-MS) analysis, and the result showed that the lithium content was 72ppm and the metal purity of the product was 4N.
As can be seen from the comparison of comparative example 1 and example 3, in the process of preparing the germanium complex precursor, the Grignard reagent is used for replacing butyl lithium, so that the reaction safety is improved, and the metal purity and the reaction yield of the germanium complex precursor are improved, thereby being beneficial to industrial scale-up production.
Comparative example 2
Comparative example 2 provides a method for preparing a zirconium precursor complex, which is different from example 3 in that in comparative example 2, only germanium tetrachloride in example 3 is changed to zirconium tetrachloride in equivalent amount, and the preparation steps are specifically as follows:
2 mol/L of n-propyl magnesium bromide in tetrahydrofuran (400 ml,0.8 mol) and 400ml of n-hexane were added to a 2000 ml Schlenk flask under a nitrogen atmosphere, the temperature was lowered to about-10 ℃, then a 20% by mass n-hexane solution (225.4 g, 1.0 mol) of dimethylamine was added dropwise, the temperature was gradually returned to room temperature after the addition was completed and the reaction was carried out for 8 hours, the reaction mixture was cooled again to-10 ℃ after the completion of the reaction, zirconium tetrachloride (46.6 g,0.2 mol) was slowly added under a nitrogen atmosphere, the temperature was returned to room temperature after the addition was completed, and stirring was continued for 12 hours, and the solvent was filtered and drained to obtain a brown residue, which was not zirconium tetradimethylamino by nuclear magnetic characterization.
As can be seen from examples 3, 7 and 2, the electronegativity of germanium (2.01) is much greater than that of magnesium (1.31), and the electronegativity of tin (1.96) is much greater than that of magnesium (1.31), and another metal organic compound can be obtained by exchange reaction of an intermediate obtained by reacting a Grignard reagent with an alkylamine and a salt compound of the metal. In contrast, zirconium (1.33) is not much different from magnesium (1.31), and zirconium tetradimethylamino cannot be obtained by the above method.
Example 8
The embodiment provides a preparation method of a germanium oxide film, which comprises the following steps:
the tetradimethylaminogermanium of example 1 was used as a precursor for depositing germanium oxide films by an atomic layer deposition process. Heating the atomic layer deposition cavity to 300 ℃ from room temperature, and vacuumizing; the precursor molecules are sent into an atomic layer deposition chamber (pulse time is 0.2 s) by using high-purity argon, and after the introduction of germanium source molecules is finished, argon 1 is continuously introduced0s to clean residual germanium source and reaction byproducts. H with argon 2 The O pulse enters an atomic layer deposition chamber (pulse time is 0.3 s) to be pulsed H 2 After the O molecules are introduced, argon is continuously introduced for 10 seconds so as to clean residual H 2 O molecules and reaction byproducts. Repeating the above process, and obtaining the good germanium oxide film after 100 cycles. The thickness of the film was 5nm as measured by ellipsometry, and the non-uniformity of the film was 0.88%.
Example 9
This example provides a method for preparing a germanium oxide film, which differs from example 8 in that the precursor is tetraethyl amino germanium prepared in example 4.
The thickness of the germanium oxide film prepared in this example was 4.8nm and the non-uniformity of the film was 0.91% as measured by ellipsometry.
Example 10
This example provides a method for preparing a germanium oxide film, which differs from example 8 in that the precursor is tetramethylethylamino germanium prepared in example 5.
The thickness of the germanium oxide film prepared in this example was 5.1nm and the non-uniformity of the film was 0.85% as measured by ellipsometry.
Example 11
This example provides a method for preparing a tin oxide film, which differs from example 8 in that the precursor is tetradimethylamino tin prepared in example 7.
The thickness of the tin oxide film prepared in this example was 6.4nm and the non-uniformity of the film was 0.82% as measured by ellipsometry.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples merely represent a few embodiments of the present application, which facilitate a specific and detailed understanding of the technical solutions of the present application, but are not to be construed as limiting the scope of the application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. It should be understood that, based on the technical solutions provided by the present application, those skilled in the art can obtain technical solutions through logical analysis, reasoning or limited experiments, which are all within the protection scope of the appended claims. The scope of the patent is therefore intended to be covered by the appended claims, and the description and drawings may be interpreted as illustrative of the contents of the claims.
Claims (10)
1. The preparation method of the metal complex precursor is characterized by comprising the following steps of:
reacting Grignard reagent with alkylamine, and adding MCl into the reaction system after the reaction is finished 4 Continuing the reaction to prepare a metal complex precursor;
wherein the structural formula of the alkylamine is HNR 1 R 2 ，R 1 And R is 2 Each independently includes C 1 ～C 3 Alkyl, M comprises one or more of Ge and Sn, and the structural formula of the metal complex precursor is M (NR 1 R 2 ) 4 。
2. The method for preparing a metal complex precursor according to claim 1, wherein the grignard reagent comprises one or more of ethynylmagnesium bromide, vinylmagnesium bromide, n-propylmagnesium bromide, 1-propynylmagnesium bromide, isopropenylmagnesium bromide, propenyl magnesium bromide, cyclopropylmagnesium bromide, n-butylmagnesium bromide, sec-butylmagnesium bromide, 3-butenylmagnesium bromide, hexylmagnesium bromide, methylmagnesium chloride, ethylmagnesium chloride, ethynylmagnesium chloride, vinylmagnesium chloride, propenyl magnesium chloride, n-butylmagnesium chloride, isobutylmagnesium chloride, sec-butylmagnesium chloride and tert-butylmagnesium chloride;
optionally, the grignard reagent comprises n-propyl magnesium bromide.
3. The method of preparing a metal complex precursor according to claim 1, wherein the molar ratio of the grignard reagent to the alkylamine is 1 (1-1.5).
4. The method for preparing a metal complex precursor according to claim 1, wherein the alkylamine comprises one or more of dimethylamine, diethylamine and methylethylamine.
5. The method of preparing a metal complex precursor according to any one of claims 1 to 4, wherein the step of reacting a grignard reagent with an alkylamine comprises: firstly, adding the alkylamine into the Grignard reagent and the anhydrous hydrocarbon solvent at the temperature of between-15 and 0 ℃ under the protective atmosphere, and reacting for 6 to 10 hours at the temperature of between 20 and 30 ℃ after the addition is finished.
6. The method of preparing a metal complex precursor according to claim 5, wherein the anhydrous hydrocarbon solvent comprises anhydrous n-hexane.
7. The method for producing a metal complex precursor according to claim 1, wherein MCl is added to the reaction system 4 The step of continuing the reaction comprises: the reaction system is reduced to-15 ℃ to 0 ℃, and the MCl is added into the reaction system under the protection atmosphere 4 After the addition is finished, stirring and reacting for 10 to 14 hours at the temperature of between 20 and 30 ℃.
8. The method for producing a metal complex precursor according to claim 1 or 7, wherein the alkylamine and the MCl 4 The molar ratio of (4) to (5) is 1.
9. The method for preparing a metal complex precursor according to any one of claims 1 to 4 and 6 to 7, wherein, after adding MCl 4 After the step of continuing the reaction, a step of filtering and distilling is also included.
10. The preparation method of the metal oxide film is characterized by comprising the following steps:
preparing a metal complex precursor by the preparation method of any one of claims 1 to 9;
and (3) reacting the metal complex precursor with an oxygen source to form a film, so as to prepare the metal oxide film.
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