A method for producing an amine-metal precursor

Abstract

The present invention discloses a method for producing an amine-based metal precursor, belonging to the technical field of semiconductor precursor materials. The production method comprises the following steps: step S1, mixing a metal oxide, an organic solvent, a trialkylsilane halide, and a protic reactant, and reacting to obtain a reaction solution A1; step S2, adding a dialkylamine to the reaction solution A1 to obtain a reaction solution A2; and step S3, distilling or adding a cyclopentadiene monomer to react. In the present invention, by adopting a reaction route of a metal oxide, a trialkylsilane halide, and a protic reactant, the safety issues of high production costs and difficult storage and production of raw materials are fully resolved. This not only effectively controls costs at the source, successfully avoids the commonly used but highly dangerous butyllithium reagent in traditional processes, greatly improves the safety of the entire process, reduces potential safety risks, and effectively improves process efficiency and shortens process time.

Description

Technical Field

[0001] The present invention belongs to the technical field of semiconductor precursor materials, and in particular relates to a method for producing an amine-based metal precursor. Background Art

[0002] Tetrakis(dialkylamino)metal precursors and tris(dialkylamino)cyclopentadienylmetal precursors such as Hf(NMe2)4, Zr(NMe2)4, CpZr(NMeEt)4, CpTi(NMe2)3, CpHf(NMe2)3, CpZr(NMe2)3, etc. not only have good stability and high vapor pressure, but also show quite high reactivity. They are one of the best choices for preparing high dielectric constant (K) films. They can stably form high-quality metal element-containing films and have broad application potential in the semiconductor market.

[0003] The traditional process routes for preparing tetrakis(dialkylamino)metal precursors and tris(dialkylamino)cyclopentadienylmetal precursors are basically the same (except that the preparation of the latter requires the additional addition of Cp). For example, the existing preparation route for tris(dialkylamino)cyclopentadienylhafnium is: first react butyllithium with dialkylamine to obtain dialkylamide lithium, then react it with hafnium tetrachloride to obtain tetrakis(dialkylamino)hafnium, and finally react tetrakis(dialkylamino)hafnium with cyclopentadiene to obtain tris(dialkylamino)cyclopentadienylhafnium. Another commonly used process route is: hafnium halide HfX4 reacts with cyclopentadienylmetal compound RCpM1 to prepare intermediate trihalocyclopentadienylhafnium RCpHfX3, and then react the intermediate with dialkylamide lithium LiNR 1 R 2 Reaction preparation R 3 CpHf(NR 1 R 2 3. The butyl lithium / dialkyl lithium amide used in the traditional process route has extremely high reactivity and strong alkalinity, which not only makes the reaction level difficult to control, but also requires a strict anhydrous and oxygen-free reaction environment. In addition, the LiCl solid waste generated in the above route is difficult to filter. These factors greatly increase the difficulty of experimental operation and raw material storage costs, and reduce reaction efficiency.

[0004] Patent application publication number CN117105991A discloses a method and apparatus system for preparing tetrakis(dialkylamino)metal complexes and tris(dialkylamino)cyclopentadienylmetal complexes. The process synthesis route disclosed in the application is:

[0005] (1) MX4+Me3SiNR 1 R 2 →M(NR 1 R 2 )4+Me3SiX;

[0006] (2) M(NR 1 R 2 )4+R 3 CpH→R 3 CpM(NR 1 R 2 )3+HNR 1 R 2 ;

[0007] This application combines the regulation and control of reaction conditions to promote reactions that are beneficial to the formation of products, reduce the occurrence of side reactions, avoid the defects of using n-butyl lithium to introduce metal impurities, and avoid the production of components such as lithium salts that are not convenient for subsequent separation, thereby facilitating the purification of the product. However, the reaction efficiency is low, it is time-consuming, and the raw material cost is high. Summary of the Invention

[0008] The object of the present invention is to provide a method for producing an amine metal precursor to solve the problems of strict environmental requirements, low safety, low reaction efficiency and high process cost in the production of amine metal precursors.

[0009] The purpose of the present invention can be achieved through the following technical solutions:

[0010] A method for producing an amine metal precursor comprises the following steps:

[0011] Step S1, mixing a metal oxide, an organic solvent, a trialkylsilane halide and a protic reactant and reacting them to obtain a reaction solution A1; the metal oxide is denoted as MO2; the trialkylsilane halide is denoted as SiR3X;

[0012] Step S2, adding dialkylamine to the reaction solution A1 to react and obtain reaction solution A2; the dialkylamine is denoted as NHR'R";

[0013] Step S3: distilling the reaction solution A2 to obtain a tetrakis(dialkylamino)metal precursor; or adding cyclopentadiene monomer to the reaction solution A2, reacting at room temperature, filtering, and distilling after the reaction to obtain a tris(dialkylamino)cyclopentadienylmetal precursor.

[0014] In some embodiments, the metal oxide MO2 is selected from one of TiO2, ZrO2, and HfO2; and / or the organic solvent is one of alkanes, aromatic hydrocarbons, chlorinated alkanes, ether solvents and mixtures thereof; and / or the protic reactant is at least one of water, alcohol and phenol; and / or, R in the SiR3X is a straight or branched alkyl group of C1-C6; and X is one of Cl, Br, and I.

[0015] In some implementations, the protic reactant is an alcohol, which can be selected from at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, n-hexanol, etc., preferably at least one of methanol, ethanol, and isopropanol.

[0016] In some implementations, the protic reactant is phenol, and optional compounds include phenol, hydroquinone, and the like.

[0017] In some embodiments, the SiR3X includes but is not limited to at least one of trimethylchlorosilane, ethyldimethylchlorosilane, propyldimethylchlorosilane, diethylisopropylchlorosilane, triethylchlorosilane, triisopropylchlorosilane, trimethylbromosilane, and triethylbromosilane; preferably at least one of trimethylchlorosilane, triethylchlorosilane, and triisopropylchlorosilane; more preferably trimethylchlorosilane.

[0018] In some implementations, R' and R" in NHR'R" are independently selected from C1-C5 alkyl, further independently selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, and tert-butyl, and are preferably independently selected from any one of methyl, ethyl, and isopropyl.

[0019] In some implementations, the organic solvent is an alkane, which can be selected from at least one of n-pentane, isopentane, n-hexane, tert-butylmethane, n-heptane, n-octane, cyclohexane, methylcyclohexane, and dodecane, preferably n-hexane.

[0020] In some implementations, the organic solvent is an aromatic hydrocarbon, which can be selected from at least one of benzene, toluene, xylene, and ethylbenzene.

[0021] In some implementations, the organic solvent is a chlorinated alkane, which may be selected from at least one of dichloromethane, chloroform, carbon tetrachloride, and 1-chlorooctane.

[0022] In some implementations, the organic solvent is an ether solvent, which can be selected from at least one of diethyl ether, isopropyl ether, tert-butyl ether, ethylene glycol methyl ether, ethylene glycol butyl ether, triethylene glycol monobutyl ether, propylene glycol methyl ether, and tetrahydrofuran, preferably tetrahydrofuran.

[0023] In some implementations, the equivalent ratio of SiR3X to MO2 is 8-20:1, and may be selected from 8:1, 8.2:1, 8.5:1, 9:1, 9.3:1, 9.5:1, 10:1, 10.5:1, 11:1, 11.5:1, 12.0:1, 12.5:1, 13:1, 13.5:1, 14:1, 14.5:1, 15:1, 15. 5:1, 16:1, 16.5:1, 17:1, 17.5:1, 18:1, 18.5:1, 19:1, 19.5:1, 20:1, etc., preferably 8-12:1, more preferably 8-9:1; and / or, the equivalent ratio of the protic reactant to MO2 is 0.01-4:1, optionally 0.01:1, 0.03:1, 0.05:1, 0.07:1 , 0.08:1, 0.09:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1.0:1, 1.5:1, 2.0:1, 2.5:1, 3.0:1, 3.5:1, 4.0:1, etc., preferably 0.05-2:1, more preferably 0.08-1:1; And / or, the equivalent ratio of NHR'R" to MO2 is 5-15:1, and can be selected from 5:1, 6:1, 7:1, 8:1, 8.5:1, 9:1, 9.5:1, 10:1, 10.5:1, 11:1, 11.5:1, 12:1, 12.5:1, 13:1, 13.5:1, 14:1, 14.5:1, 15:1, etc., preferably 8-12:1.

[0024] The mass ratio of the organic solvent to MO2 is 1:1-100.

[0025] In some implementations, the reaction time for adding the protic reactant in step S1 is 12-24 hours;

[0026] In step S2, when the temperature is 0 Next, NHR'R" is added to the reaction solution A1, more preferably at a temperature of -20 to 0 Under the following conditions, NHR'R" was added to the reaction solution A1;

[0027] The reaction temperature in step S2 to obtain the reaction solution A2 is 60 ~100 .

[0028] In some implementations, the tetrakis(dialkylamino)metal precursor is denoted as M(NR'R")4, where M is Ti, Zr, or Hf, and R' and R" are as defined above.

[0029] In some implementations, the tris(dialkylamino)cyclopentadienyl metal precursor is denoted as CpM(NR'R")3, the cyclopentadiene monomer is denoted as Cp, and M, R' and R" are as defined above.

[0030] In some implementations, the equivalent ratio of Cp to MO2 is 0.8-2:1, optionally including but not limited to 0.8:1, 0.9:1, 1.0:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2.0:1, etc., preferably 1.0-1.4:1; and / or, the temperature of the dropwise addition of Cp to the reaction solution A2 is 25 ~50 .

[0031] In some implementations, Cp is substituted or unsubstituted cyclopentadiene, and the substituent in the substituted cyclopentadiene is one of a C1-C5 alkyl group, a C1-C5 alkoxy group, a silicon group, and a siliconoxy group, and the number of the substituents is 1-5.

[0032] Beneficial effects of the present invention:

[0033] (1) The present invention fully considers production costs and production safety. Metal oxides, which are cheaper and easier to store, are selected as starting materials for the reaction. Compared to the high-cost and difficult-to-store metal halide raw materials used in existing processes, metal oxides are readily available in the market and offer a high cost-effectiveness, effectively controlling costs from the source.

[0034] (2) The present invention designs a process route for preparing intermediates by reacting metal oxides, trialkylsilane halides, and protic reactants. This innovative industrial reaction route successfully avoids the use of butyllithium reagents, which are commonly used in traditional processes but are extremely dangerous. Butyllithium is extremely chemically active and flammable when exposed to air, posing many safety hazards during storage, transportation, and use. The method of the present invention greatly improves the safety of the entire process and reduces potential safety risks. In addition, it avoids the production of lithium salts during the reaction, saves a large amount of process time consumed by filtering lithium salts, and significantly improves reaction / process efficiency.

[0035] (3) The process of the present invention achieves a significant improvement in raw material utilization. By optimizing the reaction conditions, steps, and various links, the raw materials are more fully utilized throughout the entire reaction route, avoiding unnecessary waste. This improvement in raw material utilization not only reduces raw material consumption but also lowers subsequent processing costs, making the process of the present invention have higher economic benefits and industrial application value. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] The present invention will be further described below with reference to the accompanying drawings.

[0037] Figure 1 This is the H NMR spectrum of the product CpHf(NMe2)3 in Example 1 of the present invention;

[0038] Figure 2 is the H NMR spectrum of the product CpZr(NMe2)3 in Example 5 of the present invention;

[0039] Figure 3 is the H NMR spectrum of the product Hf(NMe2)4 in Example 7 of the present invention;

[0040] Figure 4 is the H NMR spectrum of the product Zr(NMeEt)4 in Example 8 of the present invention;

[0041] Figure 5 This is the H NMR spectrum of the product Ti(NMe2)4 in Example 9 of the present invention. DETAILED DESCRIPTION

[0042] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0043] The present invention provides a method for producing an amine metal precursor, comprising the following steps:

[0044] Step S1, mixing a metal oxide (MO2), an organic solvent, a trialkylsilane halide (SiR3X) and a protic reactant and reacting them to obtain a reaction solution A1;

[0045] Step S2: When the temperature is less than or equal to 0 Under the following conditions, dialkylamine (NHR'R") is added to the reaction solution A1 to react to obtain the reaction solution A2;

[0046] Step S3: distilling the reaction solution A2 to obtain a tetrakis(dialkylamino)metal precursor; or adding cyclopentadiene monomer to the reaction solution A2, reacting at room temperature, filtering, and distilling after the reaction to obtain a tris(dialkylamino)cyclopentadienylmetal precursor.

[0047] In some embodiments, the reaction time of adding the protic reactant in step S1 is 12-24 hours;

[0048] In step S2, the temperature is -20 ~0 Under the following conditions, dialkylamine (NHR'R") was added to the reaction solution A1;

[0049] The reaction temperature in step S2 to obtain the reaction solution A2 is 60 ~100 .

[0050] In some embodiments, the MO2 is selected from one of TiO2, ZrO2, and HfO2.

[0051] In some embodiments, the organic solvent is an alkane, an aromatic hydrocarbon, a chlorinated alkane, an ether solvent or a mixture thereof; the mass ratio of the organic solvent to MO2 is 1:1-100.

[0052] In some embodiments, the protic reactant is one of water, alcohol, and phenol. Preferably, the protic reactant is at least one of methanol, ethanol, and isopropanol, more preferably ethanol.

[0053] In some embodiments, R in the SiR3X is a C1-C6 straight or branched alkyl group, which may be at least one of trimethyl, triethyl, tripropyl, tri-n-butyl, tri-n-pentyl, tri-n-hexyl, methyldiethyl, dimethylpropyl, diethylpropyl, dimethylbutyl, etc.; X is a halogen selected from Cl, Br, I;

[0054] In some embodiments, the SiR3X is trimethylchlorosilane, triethylchlorosilane, or triisopropylchlorosilane; more preferably trimethylchlorosilane.

[0055] In some embodiments, R' and R" in NHR'R" are independently selected from C1-C5 alkyl.

[0056] In some embodiments, the equivalent ratio of SiR3X to MO2 is 8-20:1; preferably, the equivalent ratio of SiR3X to MO2 is 8-12:1, at which a more suitable production cost and a higher yield can be obtained; more preferably, the equivalent ratio of SiR3X to MO2 is 8-9:1.

[0057] In some embodiments, the equivalent ratio of the protic reactant to MO2 is 0.01-4:1, preferably the equivalent ratio of the protic reactant to MO2 is 0.05-2:1, further preferably 0.08-1:1, and more preferably the equivalent ratio of the protic reactant to MO2 is 0.1:1.

[0058] In some embodiments, the equivalent ratio of NHR'R" to MO2 is 5-15:1, preferably 8-12:1. If too much NHR'R" is added, side reactions may occur.

[0059] In some embodiments, the reaction solution A2 is distilled to obtain a tetrakis(dialkylamino)metal precursor (M(NR'R")4, where M is Ti, Zr, or Hf, and R' and R" are as defined above). An exemplary reaction principle is as follows:

[0060]

[0061] In some embodiments, cyclopentadiene monomer (Cp) is added to reaction solution A2, reacted at room temperature, filtered, and then distilled to remove tris(dialkylamino)cyclopentadienyl metal precursor (CpM(NR'R")3, where M is Ti, Zr, or Hf, and R', R", and Cp are as defined above). An exemplary reaction principle is as follows:

[0062]

[0063] In some embodiments, the temperature of adding cyclopentadiene monomer (Cp) to the reaction solution A2 is 25 ~50 .

[0064] In some embodiments, the equivalent ratio of cyclopentadiene monomer (Cp) to MO2 is 0.8-2:1. Preferably, the equivalent ratio of cyclopentadiene monomer Cp to MO2 is 1.0-1.4:1.

[0065] The following describes the details in conjunction with specific embodiments.

[0066] Example 1

[0067] This embodiment provides a method for producing an amine metal precursor, comprising the following steps:

[0068] Hafnium oxide (100.0 g, 0.475 mol, 1.0 eq) was added to the reaction flask and the inert gas was replaced three times with N2. 1 L of ethylene glycol dimethyl ether and trimethylsilyl chloride (439 g, 4.041 mol, 8.5 eq) were added and stirred. Ethanol (2.2 g, 0.048 mol, 0.1 eq) was added dropwise at room temperature. The temperature did not exceed 60°C during the addition of ethanol. After the addition of ethanol was complete, the reaction was continued at room temperature for 12 h until hafnium oxide was converted into hafnium tetrachloride. The temperature of the reaction system was lowered to 0 , slowly introduce dimethylamine gas (182.1g, 4.039mol, 8.5eq), and the reaction temperature is not higher than 30 After the dimethylamine is introduced, 70 The reaction was continued for 6 h. Finally, cyclopentadiene (44.0 g, 0.665 mol, 1.4 eq) was added dropwise at room temperature. After the addition was complete, the reaction was allowed to proceed for 12 h at room temperature. The reaction solution was filtered, and the filtrate was collected, concentrated, and distilled under reduced pressure to obtain 161.2 g of a light yellow liquid (tris(dimethylamino)cyclopentadienylhafnium, chemical formula: CpHf(NMe2)3) with a yield of 90.3%.

[0069] The product hydrogen spectrum is as follows Figure 1 As shown: 1 HNMR(C6D6): δ2.96 (S,18H,N(CH3)2), 6.03(S,5H,C5H5).

[0070] After distillation, the CpHf(NMe2)3 product with a metal purity of 99.9999% can be obtained.

[0071] Example 2

[0072] This embodiment provides a method for producing an amine metal precursor, comprising the following steps:

[0073] Hafnium oxide (100.0 g, 0.475 mol, 1.0 eq) was added to the reaction flask and the inert gas was replaced three times with N2. 1.1 L of ethylene glycol dimethyl ether and triethylchlorosilane (588.5 g, 3.905 mol, 8.2 eq) were added as solvents and stirred. Ethanol (4.4 g, 0.1 mol, 0.2 eq) was added dropwise at room temperature. The temperature did not exceed 60°C during the addition of ethanol. After the addition of ethanol was complete, the reaction was continued at room temperature for 14 h until hafnium oxide was converted into hafnium tetrachloride. The temperature of the reaction system was lowered to 0 , slowly introduce dimethylamine gas (214.5g, 4.758mol, 10eq), and the reaction temperature is not higher than 30 After the dimethylamine is introduced, 60 The reaction was continued for 5.5 hours. Finally, cyclopentadiene (44.0 g, 0.665 mol, 1.4 eq) was added dropwise at room temperature. After the addition was complete, the reaction was allowed to proceed for 12 hours at room temperature. The reaction solution was filtered, and the filtrate was collected, concentrated, and distilled under reduced pressure to obtain 152.6 g of a light yellow liquid (tris(dimethylamino)cyclopentadienylhafnium, chemical formula: CpHf(NMe2)3) with a yield of 85.5%.

[0074] After distillation, the CpHf(NMe2)3 product with a metal purity of 99.9999% can be obtained.

[0075] Example 3

[0076] This embodiment provides a method for producing an amine metal precursor, comprising the following steps:

[0077] Hafnium oxide (100.0 g, 0.475 mol, 1.0 eq) was added to the reaction flask and the inert gas was replaced three times with N2. 1.6 L of ethylene glycol dimethyl ether and trimethylsilyl chloride (464.5 g, 4.276 mol, 9 eq) were added as solvents and stirred. Methanol (5.3 g, 0.165 mol, 0.35 eq) was added dropwise at room temperature. The temperature did not exceed 60°C during the addition of methanol. After the addition of methanol was complete, the reaction was continued at room temperature for 16 h until hafnium oxide was converted into hafnium tetrachloride. The temperature of the reaction system was lowered to 0 , slowly introduce dimethylamine gas (257.2g, 5.705mol, 12eq), and the reaction temperature is not higher than 30 After the dimethylamine is introduced, 75 The reaction was continued for 6 h. Finally, cyclopentadiene (44.0 g, 0.665 mol, 1.4 eq) was added dropwise at room temperature. After the addition was complete, the reaction was allowed to proceed for 12 h at room temperature. The reaction solution was filtered, and the filtrate was collected, concentrated, and distilled under reduced pressure to obtain 157.4 g of a light yellow liquid (tris(dimethylamino)cyclopentadienylhafnium, chemical formula: CpHf(NMe2)3) with a yield of 88.2%.

[0078] After distillation, the CpHf(NMe2)3 product with a metal purity of 99.9999% can be obtained.

[0079] Example 4

[0080] This embodiment provides a method for producing an amine metal precursor, comprising the following steps:

[0081] Hafnium oxide (100.0 g, 0.475 mol, 1.0 eq) was added to the reaction flask and the inert gas was replaced three times with N2. 1.2 L of ethylene glycol dimethyl ether and trimethylsilyl chloride (464.5 g, 4.276 mol, 9 eq) were added as solvents and stirred. Ethanol (2.2 g, 0.048 mol, 0.1 eq) was added dropwise at room temperature. The temperature did not exceed 60°C during the addition of ethanol. After the addition of ethanol was complete, the reaction was continued at room temperature for 12 h until hafnium oxide was converted into hafnium tetrachloride. The temperature of the reaction system was lowered to 0 , slowly introduce dimethylamine gas (182.1g, 4.039mol, 8.5eq), and the reaction temperature is not higher than 30 After the dimethylamine is introduced, 80 The reaction was continued for 6 hours. Finally, cyclopentadiene (31.4 g, 0.475 mol, 1.0 eq) was added dropwise at room temperature. After the addition was complete, the reaction was allowed to proceed for 12 hours at room temperature. The reaction solution was filtered, the filtrate was collected, concentrated, and distilled under reduced pressure to obtain 134.6 g of a pale yellow liquid (cyclopentadienyltris(dimethylamino)hafnium, chemical formula: CpHf(NMe2)3), with a yield of 79.4%. After rectification, the CpHf(NMe2)3 product with a metallic purity of 99.9999% was obtained.

[0082] Example 5

[0083] This embodiment provides a method for producing an amine metal precursor, comprising the following steps:

[0084] Zirconium oxide (75.0 g, 0.609 mol, 1.0 eq) was added to the reaction flask and the inert gas was replaced three times with N2. 2.0 L of ethylene glycol dimethyl ether and trimethylsilyl chloride (665.0 g, 6.121 mol, 10.1 eq) were added as solvents and stirred. Ethanol (7.8 g, 0.169 mol, 0.28 eq) was added dropwise at room temperature. The temperature did not exceed 60°C during the addition of ethanol. After the addition of ethanol was complete, the reaction was continued at room temperature for 12 h until zirconium oxide was converted into zirconium tetrachloride. The temperature of the reaction system was lowered to 0 , slowly introduce dimethylamine gas (400g, 8.873mol, 14.6eq), and the reaction temperature is not higher than 30 After the dimethylamine is introduced, 100 The reaction was continued under reflux for 6 h. Finally, cyclopentadiene (80.0 g, 1.210 mol, 2.0 eq) was added dropwise at room temperature. After the addition was complete, the reaction was allowed to proceed at room temperature for 12 h. The reaction solution was filtered, and the filtrate was collected, concentrated, and distilled under reduced pressure to obtain 135.7 g of a light yellow liquid (cyclopentadienyl tris(dimethylamino) zirconium, chemical formula: CpZr(NMe2)3), with a yield of 77.3%.

[0085] The product hydrogen spectrum is as follows Figure 2 As shown: 1 HNMR(C6D6): δ2.92 (S,18H,N(CH3)2), 6.06(S,5H,C5H5).

[0086] Example 6

[0087] This embodiment provides a method for producing an amine metal precursor, comprising the following steps:

[0088] Hafnium oxide (100.0 g, 0.475 mol, 1.0 eq) was added to the reaction flask and the inert gas was replaced three times with N2. 1.8 L of ethylene glycol dimethyl ether and trimethylsilyl chloride (620 g, 5.707 mol, 12 eq) were added as solvents and stirred. Ethanol (2.2 g, 0.048 mol, 0.1 eq) was added dropwise at room temperature. The temperature did not exceed 60°C during the addition of ethanol. After the addition of ethanol was complete, the reaction was continued at room temperature for 12 h until hafnium oxide was converted into hafnium tetrachloride. The temperature of the reaction system was lowered to 0 , slowly introduce methylethylamine gas (225g, 3.806mol, 8.0eq), and the reaction temperature is not higher than 30 After the addition of methylethylamine, 70 The reaction was continued for 6 hours. Finally, cyclopentadiene (44.0 g, 0.665 mol, 1.4 eq) was added dropwise at room temperature. After the addition was complete, the reaction was allowed to proceed for 12 hours at room temperature. The reaction solution was filtered, the filtrate was collected, concentrated, and distilled under reduced pressure to obtain 166.2 g of a light yellow liquid (cyclopentadienyltrimethylethylamino hafnium, chemical formula: CpHf(NMeEt)3), with a yield of 83.7%. Product hydrogen spectrum data: 1 HNMR(C6D6): δ1.0 (t, 9H,CH3), 2.9 (s,9H, NCH3), 3.2 (q, 6H, NCH2), 6.1 (s, 5H, C5H5).

[0089] Example 7

[0090] This embodiment provides a method for producing an amine metal precursor, comprising the following steps:

[0091] Hafnium oxide (100.0 g, 0.475 mol, 1.0 eq) was added to the reaction flask and the inert gas was replaced three times with N2. 1 L of ethylene glycol dimethyl ether and trimethylsilyl chloride (439 g, 4.041 mol, 8.5 eq) were added to the reaction flask and stirred. Ethanol (2.2 g, 0.048 mol, 0.1 eq) was added dropwise at room temperature. The temperature did not exceed 60°C during the addition of ethanol. After the addition of ethanol was complete, the reaction was continued at room temperature for 12 h until hafnium oxide was converted into hafnium tetrachloride. The temperature of the reaction system was lowered to 0 , slowly introduce dimethylamine gas (182.1g, 4.039mol, 8.5eq), and the reaction temperature is not higher than 30 After the dimethylamine is introduced, 70 The reaction was continued for 6 h, the reaction solution was filtered, the filtrate was collected, and the filtrate was concentrated and distilled under reduced pressure to obtain 156.5 g of a low-melting-point solid (tetrakis(dimethylamino)hafnium, chemical formula: Hf(NMe2)4) with a yield of 92.8%.

[0092] The product hydrogen spectrum is as follows Figure 3 As shown: 1 HNMR(C6D6): δ2.99 (S,24H,N(CH3)2).

[0093] Example 8

[0094] Zirconium oxide (75.0 g, 0.609 mol, 1.0 eq) was added to the reaction flask and the inert gas was replaced three times with N2. 2.0 L of ethylene glycol dimethyl ether and trimethylsilyl chloride (665.0 g, 6.121 mol, 10.1 eq) were added as solvents and stirred. Ethanol (7.8 g, 0.169 mol, 0.28 eq) was added dropwise at room temperature. The temperature did not exceed 60°C during the addition of ethanol. After the addition of ethanol was complete, the reaction was continued at room temperature for 12 h until zirconium oxide was converted into zirconium tetrachloride. The temperature of the reaction system was lowered to 0 , slowly introduce methylethylamine gas (400g, 6.767mol, 11.1eq), and the reaction temperature is not higher than 30 After the addition of methylethylamine, 90 The reaction was continued under reflux for 6 h. Finally, the reaction solution was filtered, the filtrate was collected, concentrated, and distilled under reduced pressure to obtain 168.2 g of a yellow liquid (tetrakis(methylethylamino)zirconium, chemical formula: Zr(NMeEt)4) with a yield of 85.3%.

[0095] The product hydrogen spectrum is as follows Figure 4 As shown: 1 HNMR(C6D6): δ1.17 (t, 9H,CH3), 2.99 (s,9H, NCH3), 3.25 (q, 6H, NCH2).

[0096] Example 9

[0097] Titanium oxide (37.9 g, 0.475 mol, 1.0 eq) was added to the reaction flask and the inert gas was replaced three times with N2. 1 L of ethylene glycol dimethyl ether and trimethylsilyl chloride (439 g, 4.041 mol, 8.5 eq) were added as solvents and stirred. Ethanol (2.2 g, 0.048 mol, 0.1 eq) was added dropwise at room temperature. The temperature did not exceed 60°C during the addition of ethanol. After the addition of ethanol was complete, the reaction was continued at room temperature for 12 h until titanium oxide was converted into titanium tetrachloride. The temperature of the reaction system was lowered to 0 , slowly introduce dimethylamine gas (182.1g, 4.039mol, 8.5eq), and the reaction temperature is not higher than 30 After the dimethylamine is introduced, 60 The reaction was continued for 6 h, the reaction solution was filtered, the filtrate was collected, and the filtrate was concentrated and distilled under reduced pressure to obtain 90.6 g of yellow liquid (tetrakis(dimethylamino)titanium, chemical formula: Ti(NMe2)4) with a yield of 85.1%.

[0098] The product hydrogen spectrum is as follows Figure 5 As shown: 1 HNMR(C6D6): δ3.11 (S,24H,N(CH3)2).

[0099] Comparative Example 1

[0100] Hafnium oxide (100.0 g, 0.475 mol, 1.0 eq) was added to the reaction flask and the inert gas was replaced three times with N2. 1 L of ethylene glycol dimethyl ether and trimethylsilyl chloride (361.3 g, 3.325 mol, 7 eq) were added to the reaction flask and stirred. Methanol (1.5 g, 0.047 mol, 0.1 eq) was added dropwise at room temperature. The temperature did not exceed 60°C during the addition of methanol. After the addition of methanol was complete, the reaction was continued at room temperature for 12 h until hafnium oxide was converted into hafnium tetrachloride. The temperature of the reaction system was lowered to 0 , slowly introduce dimethylamine gas (182.1g, 4.039mol, 8.5eq), and the reaction temperature is not higher than 30 After the dimethylamine is introduced, 70 The reaction was continued for 6 h. Finally, cyclopentadiene (44.0 g, 0.665 mol, 1.4 eq) was added dropwise at room temperature. After the addition was complete, the reaction was allowed to proceed at room temperature for 12 h. The reaction solution was filtered, and the filtrate was collected and concentrated. The filtrate was distilled under reduced pressure to obtain 111.5 g of a light yellow liquid with a yield of 62.5%.

[0101] Comparative Example 2

[0102] The reaction was basically the same as in Example 3, except that 310 g (2.853 mol, 6 eq) of trimethylchlorosilane was added to obtain 75.2 g of crude product with a yield of 42.1%.

[0103] Comparative Example 3

[0104] The reaction was basically the same as in Example 1, except that 91 g (2.018 mol, 4.2 eq) of dimethylamine was added to obtain 46.2 g of crude product with a yield of 25.9%.

[0105] Comparative Example 4:

[0106] Reference is made to Comparative Example 2 in CN111303197A. The yield is 73%.

[0107] Comparative Example 5:

[0108] Reference is made to Comparative Example 1 in CN111303197A. The yield is 75%.

[0109] It should be noted that, in this document, relational terms such as first and second, etc., are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "comprises," "comprising," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that includes a list of elements includes not only those elements but also other elements not explicitly listed, or elements inherent to such process, method, article, or apparatus.

[0110] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A method for producing an amine metal precursor, characterized in that: The steps include: Step S1, mixing a metal oxide, an organic solvent, a trialkylsilane halide, and a protic reactant and reacting them to obtain a reaction solution A1; the organic solvent is ethylene glycol dimethyl ether, and the protic reactant is methanol or ethanol; the reaction time of adding the protic reactant to react is 12-24 hours; Step S2, adding dialkylamine to reaction solution A1 to react to obtain reaction solution A2; adding dialkylamine to reaction solution A1 at a temperature below 0°C; the reaction temperature in step S2 to obtain reaction solution A2 is 60°C to 100°C; Step S3, distilling the reaction solution A2 to obtain a tetrakis(dialkylamino)metal precursor; or adding cyclopentadiene monomer to the reaction solution A2, reacting at room temperature, filtering, and distilling after the reaction to obtain a tris(dialkylamino)cyclopentadienylmetal precursor; The metal oxide is selected from one of TiO2, ZrO2 and HfO2; the trialkylsilane halide is recorded as SiR3X; R in the SiR3X is a C1-C6 straight-chain or branched alkyl group; X is one of Cl, Br and I; the dialkylamine is recorded as NHR'R", and R' and R" in the NHR'R" are independently selected from C1-C5 alkyl groups; the equivalent ratio of the trialkylsilane halide to the metal oxide is 8-20:1; the equivalent ratio of the protic reactant to the metal oxide is 0.01-4:1; the equivalent ratio of the dialkylamine to the metal oxide is 5-15:1; and the equivalent ratio of the cyclopentadiene monomer to the metal oxide is 0.8-2:

1.

2. The method for producing an amine metal precursor according to claim 1, characterized in that: The trialkylsilyl halide is selected from at least one of trimethylsilyl chloride, triethylsilyl chloride and triisopropylsilyl chloride.

3. The method for producing an amine metal precursor according to claim 1, wherein: The equivalent ratio of the trialkylsilane halide to the metal oxide is 8-12:1; and / or the equivalent ratio of the protic reactant to the metal oxide is 0.05-2:1; and / or the equivalent ratio of the dialkylamine to the metal oxide is 8-12:

1.

4. The method for producing an amine metal precursor according to claim 1, wherein: The tetrakis(dialkylamino)metal precursor is denoted as M(NR'R")4, where M is Ti, Zr, or Hf, and R' and R" are independently selected from C1-C5 alkyl groups.

5. The method for producing an amine metal precursor according to claim 1, characterized in that: The tris(dialkylamino)cyclopentadienyl metal precursor is denoted as CpM(NR'R")3, where M is Ti, Zr, or Hf, R' and R" are independently selected from C1-C5 alkyl groups, and Cp is an unsubstituted cyclopentadiene.

6. The method for producing an amine metal precursor according to claim 5, characterized in that: The dropwise addition temperature of cyclopentadiene monomer to reaction solution A2 is 25°C to 50°C.

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