Metal complex, preparation method and application thereof and zirconium oxide film

Abstract

The invention belongs to the technical field of organic compounds, and discloses a metal complex as well as a preparation method and application thereof and a zirconium oxide film, the metal complex is shown in a formula (1), and R1-R2 and each R3 are independently selected from alkyl with the carbon atom number of 1-5. According to the invention, cyclopentadienyl and dimethylamino are coordinated with central metal zirconium, and cyclopentadienyl is connected with a phosphorus-containing group with strong coordination ability, so that the electron density of the central metal zirconium can be increased by the generated electron effect, and the coordination effect of a cyclopentadienyl ligand and the central metal zirconium is stronger; therefore, the thermal stability of the metal complex can be improved. When the metal complex is used as a precursor material to prepare the zirconium oxide film, the purity and the uniformity of the zirconium oxide film can be improved.

Description

Technical Field

[0001] The invention belongs to the technical field of organic compounds, and in particular relates to a metal complex and a preparation method and application thereof, and a zirconium oxide film. Background Art

[0002] In recent years, zirconium oxide, as a high dielectric material (also known as high-k material), has been increasingly used in the semiconductor field. Zirconium oxide (ZrO2) has a high dielectric constant, good thermal stability, and a large energy band offset to silicon. It is considered to be one of the high-k materials that can replace silicon-based gate insulators. Zirconium oxide films are often obtained by using zirconium source precursors through deposition techniques such as CVD (chemical vapor deposition) or ALD (atomic layer deposition), and then applied to semiconductor devices. In order to ensure successful use in production, the zirconium source precursor must have sufficient chemical reactivity and sufficient thermal stability to ensure safe operation. At the same time, reducing the negative impact of impurities on the performance of the oxide film is the main factor that determines the performance of the zirconium oxide film.

[0003] However, with the development of semiconductor devices towards miniaturization and lightweight, semiconductor devices such as dynamic random access memory (DRAM) gate dielectrics or capacitor dielectric films have increasingly higher performance requirements for zirconium oxide films, which in turn puts higher and higher requirements on the thermal stability of zirconium source precursors, which traditional zirconium source precursors are difficult to meet.

[0004] Therefore, the traditional technology still needs to be improved. Summary of the invention

[0005] The purpose of the present invention is to provide a metal complex and its preparation method and application, and a zirconium oxide film. The metal complex has excellent thermal stability. When the metal complex is used as a precursor material to prepare the zirconium oxide film, the purity, uniformity and thermal stability of the zirconium oxide film can be improved.

[0006] The technical solution of this application is as follows.

[0007] In a first aspect of the present application, a metal complex is provided, wherein the metal complex is as shown in formula (1):

[0008]

[0009] Here, R1 to R2 and each R3 are independently selected from an alkyl group having 1 to 5 carbon atoms.

[0010] The above-mentioned metal complex has a specific structure. By coordinating the cyclopentadienyl group and the dimethylamino group with the central metal zirconium, and at the same time connecting the cyclopentadienyl group with a phosphorus-containing group with strong coordination ability, the electronic effect produced can increase the electron density of the central metal zirconium, making the coordination effect between the cyclopentadienyl ligand and the central metal zirconium stronger, thereby improving the thermal stability and chemical stability of the metal complex.

[0011] When the metal complex is used as a precursor material to prepare zirconium oxide film, good thermal stability means that the probability of adverse side reactions can be reduced, which helps to form a high-purity and uniform film. In addition, the precursor with good thermal stability can be tightly connected to the substrate, which helps to form a dense and pore-free film, thereby improving the uniformity and stability of the zirconium oxide film.

[0012] In some embodiments, R1-R2 are independently selected from chain alkyl groups having 1 to 3 carbon atoms; and / or

[0013] Each R3 is independently selected from a chain alkyl group having 1 to 3 carbon atoms; and / or

[0014] The metal complex is shown in formula (1-1):

[0015]

[0016] In some embodiments, the metal complex is as shown in formula (1-2):

[0017]

[0018] In a second aspect of the present application, a method for preparing a metal complex is provided, comprising the following steps:

[0019] subjecting compound (a) to a first substitution reaction with compound (b) to prepare intermediate (c);

[0020] subjecting compound (d) to a second substitution reaction with compound (e) to prepare intermediate (f);

[0021] The intermediate (c) and the intermediate (f) are subjected to a third substitution reaction to prepare a metal complex represented by formula (1);

[0022] Wherein, the compound (a), the compound (b), the intermediate (c), the compound (d), the compound (e), the intermediate (f) and the metal complex are respectively as follows:

[0023]

[0024] R1 to R2 and each R3 are independently selected from an alkyl group having 1 to 5 carbon atoms.

[0025] The preparation method can obtain high-purity metal complexes with high yield.

[0026] In some embodiments, the mass ratio of the compound (b) to the compound (a) is (2-10):(2-10); and / or

[0027] The first substitution reaction is carried out in a solvent under reflux conditions for 3 h to 5 h; and / or

[0028] The process for preparing the intermediate (c) further comprises the following steps:

[0029] The reaction product of the first substitution reaction is filtered to obtain a filtrate, and then the filtrate is subjected to reduced pressure distillation to obtain the intermediate (c).

[0030] In some embodiments, the second substitution reaction is carried out under the action of NaH, and the mass ratio of NaH to the compound (d) is (2-10):(2-10).

[0031] In some embodiments, the mass ratio of the compound (e) to the compound (d) is (2-10):(2-10); and / or

[0032] The process for preparing intermediate (f) comprises the following steps:

[0033] At -40°C, adding the NaH to a tetrahydrofuran solution of the compound (d), and then adding the compound (e) at -10°C to 0°C to carry out a reaction, and after the reaction is completed, quenching with alkaline ice water to obtain a reaction product of the second substitution reaction;

[0034] subjecting the reaction product of the second substitution reaction to a liquid separation treatment to obtain an organic phase product;

[0035] The organic phase product is sequentially dried and distilled under reduced pressure to obtain the intermediate (f).

[0036] In some embodiments, the molar ratio of the intermediate (f) to the intermediate (c) is (1-1.3):1; and / or

[0037] The process for preparing the metal complex represented by formula (1) comprises the following steps:

[0038] At 0°C-5°C, the intermediate (f) is added dropwise into the n-hexane solution of the intermediate (c) to mix, and then the mixture is heated to reflux to react, thereby obtaining a reaction product of the third substitution reaction;

[0039] performing solid-liquid separation on the reaction product of the third substitution reaction to obtain a filtrate;

[0040] The filtrate is purified to obtain the metal complex represented by formula (1).

[0041] The third aspect of the present application provides the use of the metal complex of the first aspect in preparing a zirconium oxide film.

[0042] In a fourth aspect of the present application, a zirconium oxide film is provided. The zirconium oxide film is obtained by deposition treatment of a precursor material, wherein the precursor material includes the metal complex of the first aspect. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 is a thermogravimetric analysis curve of the metal complex prepared in Example 1;

[0044] Figure 2 is a thermogravimetric analysis curve of the metal complex prepared in Example 3;

[0045] Figure 3 This is a thermogravimetric analysis curve of the metal complex prepared in Example 6. DETAILED DESCRIPTION

[0046] The present invention will be described in detail below through examples.

[0047] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application belongs. The terms used herein in the specification of this application are only for the purpose of describing specific embodiments and are not intended to limit this application.

[0048] In the description of the embodiments of the present application, the technical terms "first", "second", etc. are only used to distinguish different objects, and cannot be understood as indicating or implying relative importance or implicitly indicating the number, specific order or primary and secondary relationship of the indicated technical features. In the description of the embodiments of the present application, the meaning of "multiple" is two or more, unless otherwise clearly and specifically defined.

[0049] In this application, "optionally", "optional", and "optional" mean optional, that is, any one of the two parallel schemes of "yes" or "no". If there are multiple "options" in a technical solution, unless otherwise specified and there is no contradiction or mutual restriction, each "option" is independent.

[0050] In the present application, the term "alkyl" refers to a group formed when an alkane loses a hydrogen, for example, methane loses a hydrogen to form a methyl group; "alkyl" includes chain alkyl and cycloalkyl, the former refers to a group formed when an alkane whose carbon atoms are all connected by a carbon-carbon single bond and are not ring-forming is lost after a hydrogen is lost, and the latter refers to a ring-forming alkyl; optionally, chain alkyl may also include straight-chain alkyl and branched-chain alkyl.

[0051] In the present application, a single bond connected to a substituent runs through the corresponding ring, indicating that the substituent can be connected to any position of the ring, for example In the above formula, R is connected to any substitutable position of the ring.

[0052] In one embodiment of the present application, a metal complex is provided, and the metal complex is shown in formula (1):

[0053]

[0054] Here, R1 to R2 and each R3 are independently selected from an alkyl group having 1 to 5 carbon atoms.

[0055] The above-mentioned metal complex has a specific structure. By coordinating the cyclopentadienyl group and the dimethylamino group with the central metal zirconium, and at the same time connecting the cyclopentadienyl group with a phosphorus-containing group with strong coordination ability, the electronic effect produced can increase the electron density of the central metal zirconium, making the coordination effect between the cyclopentadienyl ligand and the central metal zirconium stronger, thereby improving the thermal stability and chemical stability of the metal complex.

[0056] When the metal complex is used as a precursor material to prepare zirconium oxide film, good thermal stability means that the probability of adverse side reactions can be reduced, which helps to form a high-purity and uniform film. In addition, the precursor with good thermal stability can be tightly connected to the substrate, which helps to form a dense and pore-free film, thereby improving the uniformity and stability of the zirconium oxide film.

[0057] It is understood that R1 and R2 may be the same or different, and each R3 may be the same or different.

[0058] In some embodiments, R1-R2 are independently selected from chain alkyl groups with 1 to 5 carbon atoms; alternatively, R1-R2 are independently selected from straight-chain alkyl groups with 1 to 5 carbon atoms.

[0059] In some embodiments, R1-R2 are independently selected from chain alkyl groups with 1 to 3 carbon atoms; alternatively, R1-R2 are independently selected from straight-chain alkyl groups with 1 to 3 carbon atoms.

[0060] In some embodiments, R1-R2 are independently selected from any one of methyl, ethyl, n-propyl and isopropyl.

[0061] In some embodiments, R1 and R2 are selected from the same group.

[0062] In one specific example, R1 and R2 are both ethyl.

[0063] In some embodiments, each R3 is independently selected from a chain alkyl group having 1 to 5 carbon atoms; alternatively, R1 to R2 are independently selected from a straight-chain alkyl group having 1 to 5 carbon atoms.

[0064] In some embodiments, each R3 is independently selected from a chain alkyl group having 1 to 3 carbon atoms; alternatively, R1 to R2 are independently selected from a straight-chain alkyl group having 1 to 3 carbon atoms.

[0065] In some embodiments, each R3 is independently selected from any one of methyl, ethyl, n-propyl, and isopropyl.

[0066] In some embodiments, each R3 is selected from the same group.

[0067] In one specific example, each R3 is methyl.

[0068] In some embodiments, the metal complex is as shown in formula (1-1):

[0069]

[0070] In some embodiments, the metal complex is shown in formula (1-2):

[0071]

[0072] One embodiment of the present application provides a method for preparing a metal complex, comprising the following steps S10 to S30.

[0073] S10: Compound (a) and compound (b) undergo a first substitution reaction to prepare intermediate (c).

[0074] S20: Compound (d) and compound (e) undergo a second substitution reaction to prepare intermediate (f).

[0075] S30: subjecting the intermediate (c) to a third substitution reaction with the intermediate (f) to prepare a metal complex represented by formula (1).

[0076] Among them, compound (a) and compound (b), intermediate (c), compound (d) and compound (e), intermediate (f) and metal complex are respectively as follows:

[0077]

[0078] R1 to R2 and each R3 are independently selected from an alkyl group having 1 to 5 carbon atoms.

[0079] The further optional ranges of R1 to R2 and each R3 are the same as above and will not be described in detail here.

[0080] In some of the embodiments, the mass ratio of compound (b) to compound (a) is (2-10):(2-10).

[0081] In a specific example, the molar ratio of compound (a) to compound (b) is 4.2:1.

[0082] In some of the embodiments, the first substitution reaction is carried out in a solvent under reflux conditions for 3 h to 5 h; optionally, the solvent is n-hexane.

[0083] In some of the embodiments, the process for preparing the intermediate (c) further comprises the following step S11.

[0084] S11: Filter the reaction product of the first substitution reaction to obtain a filtrate, and then perform vacuum distillation on the filtrate to obtain an intermediate (c). Specifically, the vacuum distillation first removes the solvent, and then continues the vacuum distillation to separate the intermediate (c).

[0085] In some embodiments, the first substitution reaction is carried out under oxygen-free and water-free conditions.

[0086] In some embodiments, the mass ratio of compound (e) to compound (d) is (2-10):(2-10).

[0087] In a specific example, the molar ratio of compound (e) to compound (d) is 1.15:1.

[0088] In some embodiments, the second substitution reaction is carried out under oxygen-free and anhydrous conditions.

[0089] In some embodiments, the second substitution reaction is carried out under the action of NaH, and the mass ratio of NaH to compound (d) is (2-10):(2-10).

[0090] In one specific example, the molar ratio of NaH to compound (d) is 1.1:1.

[0091] In some embodiments, the process of preparing the intermediate (f) comprises the following steps S21 to S23.

[0092] S21: NaH is added to a tetrahydrofuran solution of compound (d) at -40°C, and then compound (e) is added at -10°C to 0°C for reaction. After the reaction is completed, alkaline ice water is used to quench the reaction to obtain a reaction product of the second substitution reaction.

[0093] In a specific example, compound (e) is added at -10°C to 0°C, the reaction is stirred for 1 hour, and then the reaction is returned to room temperature and quenched with alkaline ice water.

[0094] In some embodiments, the alkaline substance in the alkaline ice water includes an alkali metal salt, specifically including but not limited to at least one of sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.

[0095] S22: subjecting the reaction product of the second substitution reaction to liquid separation treatment to obtain an organic phase product.

[0096] S23: The organic phase product is sequentially dried and distilled under reduced pressure to obtain an intermediate (f).

[0097] It is understood that the drying process may be carried out using dehydrating agents commonly used in the art, including but not limited to magnesium sulfate and calcium chloride.

[0098] In some embodiments, the third substitution reaction is carried out under oxygen-free and anhydrous conditions.

[0099] In some of the embodiments, the molar ratio of intermediate (f) to intermediate (c) is (1-1.3):1.

[0100] In a specific example, the molar ratio of intermediate (f) to intermediate (c) is 1.1:1.

[0101] In some of the embodiments, the process of preparing the metal complex represented by formula (1) includes the following steps S31 to S33.

[0102] S31: At 0°C-5°C, the intermediate (f) is added dropwise into the n-hexane solution of the intermediate (c) to mix, and then the mixture is heated to reflux to react, thereby obtaining a reaction product of the third substitution reaction.

[0103] In a specific example, the intermediate (f) is dropped into the n-hexane solution of the intermediate (c), mixed and stirred for 1.5 hours, and then the temperature is raised to reflux conditions for 2 hours of reaction.

[0104] S32: subjecting the reaction product of the third substitution reaction to solid-liquid separation to obtain a filtrate.

[0105] The solid-liquid separation process can adopt the solid-liquid separation process commonly used in the art, such as suction filtration or filtration.

[0106] S33: Purify the filtrate to obtain the metal complex represented by formula (1).

[0107] In a specific example, the specific steps of the purification process include: removing the solvent from the filtrate by reduced pressure distillation, and purifying the remaining material by rectification.

[0108] Another embodiment of the present application further provides the use of the above-mentioned metal complex in the preparation of zirconium oxide film.

[0109] In a fourth aspect of the present application, a zirconium oxide film is provided. The zirconium oxide film is obtained by deposition treatment of a precursor material, wherein the precursor material includes the above-mentioned metal complex.

[0110] In some of these embodiments, the deposition process includes, but is not limited to, CVD (chemical vapor deposition) or ALD (atomic layer deposition).

[0111] In one specific example, the preparation of the zirconium oxide film includes the following steps:

[0112] The metal complex is introduced as a precursor material into a reaction chamber of a PE-MOCVD device, and metal organic chemical vapor deposition is performed with plasma gas at a deposition temperature, thereby forming a zirconium oxide film on the surface of a substrate.

[0113] Specifically, the process conditions of metal organic chemical vapor deposition include: (1) heating the substrate to a deposition temperature in a reaction chamber; (2) introducing a metal complex and an inert gas into the reaction chamber; (3) introducing a plasma gas into the reaction chamber to react with the metal complex to form a zirconium oxide film; (4) introducing an inert gas to purge and remove unreacted metal complexes and by-products; and (5) repeating steps (2) to (4) until a zirconium oxide film of a target thickness is obtained.

[0114] In some embodiments, the deposition temperature is 100°C-400°C.

[0115] In some embodiments, the plasma gas is oxygen.

[0116] In some embodiments, the inert gas is selected from at least one of helium, neon, argon and nitrogen.

[0117] The following are specific embodiments.

[0118] Example 1

[0119] Step (1): Prepare (diethylphosphinocyclopentadienyl)tris(dimethylamino)zirconium. The synthesis route is as follows:

[0120]

[0121] The specific steps are as follows

[0122] In an anhydrous and oxygen-free glove box environment, using a dry three-necked flask and a dry condenser, set up an experimental apparatus: add 150g of dry n-hexane and lithium dimethylamide (13.4g, 0.257mol) into the three-necked flask, cool to 0℃±0.5℃, slowly add zirconium tetrachloride (15g, 0.064mol) in 5 batches, after the addition is complete, heat to reflux and stir to react for 4h, then cool to room temperature, use a dry sand core funnel to filter the reaction product to obtain a filtrate, at room temperature, distill the filtrate under reduced pressure to remove the solvent, and continue to distill the residual liquid under reduced pressure at 0.1torr and 70℃ to purify it to obtain the first intermediate (tetrakis(dimethylamino)zirconium), about 15.4g, with a yield of about 90%.

[0123] The first intermediate obtained was identified by nuclear magnetic hydrogen spectrum, and the specific data are as follows:

[0124] 1 H NMR (400MHz, C6D6): (2.978,24H).

[0125] Analysis of the H-NMR spectrum data showed that the target product was successfully obtained.

[0126] (2) Add 60 ml of tetrahydrofuran solution to a 200 ml three-necked flask, add 6 g (0.0907 mol) of the prepared cyclopentadiene, cool to -40°C, add NaH (2.29 g, 0.095 mol) in 5 batches, maintain the temperature during the addition, maintain the temperature and stir for 1 hour after the addition is completed; then slowly increase the temperature to -10°C ± 0.5°C, slowly add 15.64 g (0.0998 mol) of diethylphosphite chloride dropwise, and maintain the temperature at -10°C ± 0.5 during the addition. ℃, after the addition is completed, stir at -10-0℃ for 1h, and after naturally returning to room temperature, add NaHCO3 ice water dropwise for quenching, use a separatory funnel to separate the reaction solution to obtain an organic phase, and then use NaSO4 to dry the organic phase and filter to obtain a dry filtrate; then, at room temperature, the filtrate is subjected to reduced pressure distillation to remove the solvent, and the residual liquid is further subjected to reduced pressure distillation at 10torr, 40℃ to obtain the second intermediate (diethylphosphinocyclopentadiene), about 14.35g, with a yield of about 85%.

[0127] The obtained second intermediate was identified by nuclear magnetic hydrogen spectrum, and the specific data are as follows: 1 HNMR (400MHz, CCl3D): (6.50, 2H), (6.40,2H), (3.85,4H), (2.9,1H), (1.25,6H).

[0128] Analysis of the H-NMR spectrum data showed that the target product was successfully obtained.

[0129] (3) In a water-free and oxygen-free glove box, prepare a dry three-necked flask, a dry condenser, and set up the experimental apparatus: add 150 g of dry n-hexane, add 15.4 g (0.057 mol) of the first intermediate tetrakis(dimethylamino)zirconium, stir evenly and cool to 0°C±0.5°C, slowly drop the second intermediate (diethylphosphinocyclopentadiene) into the three-necked flask, and maintain the temperature unchanged during the dropwise addition. After the dropwise addition is completed, maintain the temperature at 0°C±0.5°C and stir for 1.5 h, then raise the temperature to 70°C to reach reflux, stir and react for 2 h, return to room temperature, filter the reaction product with a dry PTFE filter element to obtain a filtrate, distill the filtrate under reduced pressure to remove the solvent, and then continue to distill under reduced pressure at 0.1 torr and 100°C to obtain 18.12 g of a light yellow liquid, namely (diethylphosphinocyclopentadienyl)tris(dimethylamino)zirconium.

[0130] The obtained light yellow liquid was identified by nuclear magnetic hydrogen spectrum, and the specific data are as follows: 1 HNMR (400MHz, C6D6): (6.0061H), (5.920,2H), (3.57,4H), (2.96,18H), (2.45,1H), (1.25,6H).

[0131] Analysis of the H-NMR spectrum data showed that the target product was successfully obtained.

[0132] The total yield of (diethylphosphinocyclopentadienyl)tris(dimethylamino)zirconium (abbreviated as CpZr) was calculated using the following formula:

[0133] Total yield = actual yield of CpZr / theoretical yield of CpZr × 100%;

[0134] The theoretical yield of CpZr = input mass of zirconium tetrachloride / molar mass of zirconium tetrachloride × molar mass of CpZr. See Table 1 for specific results.

[0135] Step (ii): prepare a zirconium oxide film, as follows.

[0136] The reaction substrate was placed in a PE-MOCVD device, the deposition temperature was set at 250°C, (diethylphosphinocyclopentadienyl) tris(dimethylamino) zirconium was injected into the substrate of the reaction chamber together with nitrogen as a precursor material, oxygen plasma was introduced into the reaction chamber, and (diethylphosphinocyclopentadienyl) tris(dimethylamino) zirconium was reacted to form zirconium oxide which was deposited on the substrate, and nitrogen was introduced again after the oxide layer was formed to remove the unreacted precursor material and byproducts. The deposition step was repeated 4 times to obtain a zirconium oxide film on the substrate.

[0137] ICP-MS (LabMS 3000) was used to test the metal purity in the zirconium oxide film, AFM (ParkFX40) was used to test the surface uniformity of the zirconium oxide film, and thermogravimetric (TGA 550) was used to test the thermal stability of (diethylphosphinocyclopentadienyl)tris(dimethylamino)zirconium. The specific results are shown in Table 1. The thermogravimetric analysis curve of the metal complex (diethylphosphinocyclopentadienyl)tris(dimethylamino)zirconium is shown in Figure 1. Figure 1 shown.

[0138] Example 2

[0139] Step (1): Prepare (diethylphosphinocyclopentadienyl) tris(dimethylamino) zirconium. The synthesis route is the same as that in Example 1. The specific synthesis steps are as follows:

[0140] (1) In a water-free and oxygen-free glove box environment, using a dry three-necked flask and a dry condenser, set up an experimental device: 150 g of dry n-hexane and lithium dimethylamide (13.4 g, 0.257 mol) were added to the three-necked flask, the temperature was lowered to between 1±0.5°C, and zirconium tetrachloride (15 g, 0.064 mol) was slowly added in 5 batches. After the addition was completed, the temperature was raised to reflux and stirred for reaction for 4 h, and then cooled to room temperature. The reaction product was filtered using a dry sand core funnel to obtain a filtrate. The filtrate was subjected to reduced pressure distillation at room temperature to remove the solvent. The residual liquid was further purified by reduced pressure distillation under the conditions of 0.1 torr and 70°C to obtain the first intermediate (tetrakis(dimethylamino)zirconium), about 15.05 g, with a yield of about 88%.

[0141] The first intermediate obtained was identified by nuclear magnetic hydrogen spectrum, and the specific data are as follows:

[0142] 1 H NMR (400MHz, C6D6): (2.978,24H).

[0143] Analysis of the H-NMR spectrum data showed that the target product was successfully obtained.

[0144] (2) Add 60 ml of tetrahydrofuran solution to a 200 ml three-necked flask, add 6 g (0.0907 mol) of the prepared cyclopentadiene, cool to -40°C, add NaH (2.29 g, 0.095 mol) in 5 batches, maintain the temperature during the addition, maintain the temperature and stir for 1 hour after the addition is completed; then slowly increase the temperature to -3±0.5°C, slowly add 15.64 g (0.0998 mol) of diethylphosphite chloride dropwise, maintain the temperature at -3±0.5°C during the addition, After the addition is completed, stir at -3±0.5℃ for 1h, and after naturally returning to room temperature, add NaHCO3 ice water dropwise for quenching, use a separatory funnel to separate the reaction solution to obtain an organic phase, and then use NaSO4 to dry the organic phase and filter to obtain a dry filtrate; the filtrate is then subjected to reduced pressure distillation at room temperature to remove the solvent, and the residual liquid is further subjected to reduced pressure distillation at 10torr, 40℃ to obtain the second intermediate (diethylphosphinocyclopentadiene), about 14.85g, with a yield of about 88%.

[0145] The obtained second intermediate was identified by nuclear magnetic hydrogen spectrum, and the specific data are as follows:

[0146] 1 H NMR (400MHz, CCl3D): (6.50,2H), (6.40,2H), (3.85,4H), (2.9,1H), (1.25,6H).

[0147] Analysis of the H-NMR spectrum data showed that the target product was successfully obtained.

[0148] (3) In a water-free and oxygen-free glove box, prepare a dry three-necked flask, a dry condenser, and set up an experimental device: add 150 g of dry n-hexane, add 15.4 g (0.057 mol) of the first intermediate tetrakis(dimethylamino)zirconium, stir evenly and cool to 1°C±0.5°C, slowly drop the second intermediate (diethylphosphinocyclopentadiene) into the three-necked flask, and maintain the temperature unchanged during the dropwise addition. After the dropwise addition is completed, maintain the temperature at 1°C±0.5°C and stir for 1.5 h, then raise the temperature to 70°C to reach a reflux state, stir and react for 2 h, and after returning to room temperature, use a dry PTFE filter element to filter the reaction product to obtain a filtrate, distill the filtrate under reduced pressure to remove the solvent, and then continue to distill under reduced pressure at 0.1 torr and 100°C to obtain 18.6 g of a light yellow liquid, namely (diethylphosphinocyclopentadienyl)tris(dimethylamino)zirconium, with a yield of about 79%.

[0149] The obtained light yellow liquid was identified by nuclear magnetic hydrogen spectrum, and the specific data are as follows: 1HNMR (400MHz, C6D6): (6.006,1H), (5.920,2H), (3.57,4H), (2.96,18H), (2.45,1H), (1.25,6H).

[0150] Analysis of the H-NMR spectrum data showed that the target product was successfully obtained.

[0151] The total yield of (diethylphosphinocyclopentadienyl)tris(dimethylamino)zirconium was calculated in the same manner as in Example 1. Please see Table 1 for specific results.

[0152] Step (ii): refer to step (ii) of Example 1. For specific results, see Table 1.

[0153] Example 3

[0154] Step (1): Prepare (diethylphosphinocyclopentadienyl)tris(dimethylamino)zirconium. The synthesis route is the same as that in Example 1. The specific synthesis steps are as follows:

[0155] (1) In a water-free and oxygen-free glove box environment, using a dry three-necked flask and a dry condenser, set up an experimental device: 150 g of dry n-hexane and lithium dimethylamide (13.4 g, 0.257 mol) were added to the three-necked flask, the temperature was lowered to between 3±0.5°C, and zirconium tetrachloride (15 g, 0.064 mol) was slowly added in 5 batches. After the addition was completed, the temperature was raised to reflux and stirred for reaction for 4 h, and then cooled to room temperature. The reaction product was filtered using a dry sand core funnel to obtain a filtrate. The filtrate was subjected to reduced pressure distillation at room temperature to remove the solvent. The residual liquid was further purified by reduced pressure distillation at 0.1 torr and 70°C to obtain the first intermediate (tetrakis(dimethylamino)zirconium), about 14.7 g, with a yield of about 86%.

[0156] The first intermediate obtained was identified by nuclear magnetic hydrogen spectrum, and the specific data are as follows:

[0157] 1 HNMR(400MHz, C6D6): (2.978,24H).

[0158] Analysis of the H-NMR spectrum data showed that the target product was successfully obtained.

[0159] (2) Add 60 ml of tetrahydrofuran solution to a 200 ml three-necked flask, add 6 g (0.0907 mol) of the prepared cyclopentadiene, cool to -40°C, add NaH (2.29 g, 0.095 mol) in 5 batches, maintain the temperature during the addition, maintain the temperature and stir for 1 hour after the addition is completed; then slowly increase the temperature to -5±0.5°C, slowly add 15.64 g (0.0998 mol) of diethylphosphite chloride dropwise, maintain the temperature at -5±0.5°C during the addition, After the addition is completed, stir at -5±0.5℃ for 1h, and after naturally returning to room temperature, add NaHCO3 ice water dropwise for quenching, use a separatory funnel to separate the reaction solution to obtain an organic phase, and then use NaSO4 to dry the organic phase and filter to obtain a dry filtrate; the filtrate is then subjected to reduced pressure distillation at room temperature to remove the solvent, and the residual liquid is further subjected to reduced pressure distillation at 10torr, 40℃ to obtain the second intermediate (diethylphosphinocyclopentadiene), about 15.18 g, with a yield of 90%.

[0160] The obtained second intermediate was identified by nuclear magnetic hydrogen spectrum, and the specific data are as follows:

[0161] 1 H NMR (400MHz, CCl3D): (6.50,2H), (6.40,2H), (3.85,4H), (2.9,1H), (1.25,6H).

[0162] Analysis of the H-NMR spectrum data showed that the target product was successfully obtained.

[0163] (3) In an anhydrous and oxygen-free glove box, prepare a dry three-necked flask, a dry condenser, and set up an experimental device: add 150 g of dry n-hexane, add 15.4 g (0.057 mol) of the first intermediate tetrakis(dimethylamino)zirconium, stir evenly and cool to 2°C±0.5°C, slowly drop the second intermediate (diethylphosphinocyclopentadiene) into the three-necked flask, and maintain the temperature unchanged during the dropwise addition. After the dropwise addition is completed, maintain the temperature at 2°C±0.5°C and stir for 1.5 h, then raise the temperature to 70°C to reach a reflux state, stir and react for 2 h, return to room temperature, filter the reaction product using a dry PTFE filter element to obtain a filtrate, distill the filtrate under reduced pressure to remove the solvent, and then continue to distill under reduced pressure at 0.1 torr and 100°C to obtain 17.89 g of a light yellow liquid, namely (diethylphosphinocyclopentadienyl)tris(dimethylamino)zirconium, with a yield of about 76%.

[0164] The obtained light yellow liquid was identified by nuclear magnetic hydrogen spectrum, and the specific data are as follows: 1HNMR (400MHz, C6D6): (6.006,1H), (5.920,2H), (3.57,4H), (2.96,18H), (2.45,1H), (1.25,6H).

[0165] Analysis of the H-NMR spectrum data showed that the target product was successfully obtained.

[0166] The total yield of (diethylphosphinocyclopentadienyl)tris(dimethylamino)zirconium was calculated in the same manner as in Example 1. Please see Table 1 for specific results.

[0167] Step (ii): refer to step (ii) of Example 1. The specific results are shown in Table 1. The thermogravimetric analysis curve of the metal complex (diethylphosphinocyclopentadienyl) tris(dimethylamino)zirconium is shown in Figure 2 shown.

[0168] Example 4

[0169] Step (1): Prepare (diethylphosphinocyclopentadienyl) tris(dimethylamino) zirconium. The synthesis route is the same as that in Example 1. The specific synthesis steps are as follows:

[0170] (1) In a water-free and oxygen-free glove box environment, using a dry three-necked flask and a dry condenser, set up an experimental device: 150 g of dry n-hexane and lithium dimethylamide (13.4 g, 0.257 mol) were added to the three-necked flask, the temperature was lowered to 5±0.5°C, and zirconium tetrachloride (15 g, 0.064 mol) was slowly added in 5 batches. After the addition was completed, the temperature was raised to reflux and stirred for reaction for 4 h, and then cooled to room temperature. The reaction product was filtered using a dry sand core funnel to obtain a filtrate. The filtrate was subjected to reduced pressure distillation at room temperature to remove the solvent. The residual liquid was further purified by reduced pressure distillation at 0.1 torr and 70°C to obtain the first intermediate (tetrakis(dimethylamino)zirconium), about 15.5 g, with a yield of about 91%.

[0171] The first intermediate obtained was identified by nuclear magnetic hydrogen spectrum, and the specific data are as follows:

[0172] 1 HNMR(400MHz, C6D6): (2.978,24H).

[0173] Analysis of the H-NMR spectrum data showed that the target product was successfully obtained.

[0174] (2) Add 60 ml of tetrahydrofuran solution to a 200 ml three-necked flask, add 6 g (0.0907 mol) of the prepared cyclopentadiene, cool to -40°C, add NaH (2.29 g, 0.095 mol) in 5 batches, maintain the temperature during the addition, maintain the temperature and stir for 1 hour after the addition is completed; then slowly increase the temperature to -6±0.5°C, slowly add 15.64 g (0.0998 mol) of diethylphosphite chloride dropwise, maintain the temperature at -6±0.5°C during the addition, After the addition is completed, the mixture is stirred at -6±0.5°C for 1h, and after naturally returning to room temperature, NaHCO3 ice water is added dropwise for quenching, and the reaction solution is separated using a separatory funnel to obtain an organic phase, which is then dried with NaSO4 and filtered to obtain a dry filtrate; the filtrate is then subjected to reduced pressure distillation at room temperature to remove the solvent, and the residual liquid is further subjected to reduced pressure distillation at 10 torr and 40°C to obtain the second intermediate (diethylphosphinocyclopentadiene), about 14.67 g, with a yield of about 87%.

[0175] The obtained second intermediate was identified by nuclear magnetic hydrogen spectrum, and the specific data are as follows:

[0176] 1 H NMR (400MHz, CCl3D): (6.50,2H), (6.40,2H), (3.85,4H), (2.9,1H), (1.25,6H).

[0177] Analysis of the H-NMR spectrum data showed that the target product was successfully obtained.

[0178] (3) In a water-free and oxygen-free glove box, prepare a dry three-necked flask, a dry condenser, and set up an experimental device: add 150 g of dry n-hexane, add 15.4 g (0.057 mol) of the first intermediate tetrakis(dimethylamino)zirconium, stir evenly and cool to 4°C±0.5°C, slowly drop the second intermediate (diethylphosphinocyclopentadiene) into the three-necked flask, and maintain the temperature unchanged during the dropwise addition. After the dropwise addition is completed, maintain the temperature at 4°C±0.5°C and stir for 1.5 h, then raise the temperature to 70°C to reach a reflux state, stir and react for 2 h, return to room temperature, use a dry PTFE filter element to filter the reaction product to obtain a filtrate, distill the filtrate under reduced pressure to remove the solvent, and then continue to distill under reduced pressure at 0.1 torr and 100°C to obtain 18.83 g of a light yellow liquid, namely (diethylphosphinocyclopentadienyl)tris(dimethylamino)zirconium, with a yield of about 80%.

[0179] The obtained light yellow liquid was identified by nuclear magnetic hydrogen spectrum, and the specific data are as follows: 1HNMR (400MHz, C6D6): (6.006,1H), (5.920,2H), (3.57,4H), (2.96,18H), (2.45,1H), (1.25,6H).

[0180] Analysis of the H-NMR spectrum data showed that the target product was successfully obtained.

[0181] The total yield of (diethylphosphinocyclopentadienyl)tris(dimethylamino)zirconium was calculated in the same manner as in Example 1. Please see Table 1 for specific results.

[0182] Step (ii): refer to step (ii) of Example 1. For specific results, see Table 1.

[0183] Example 5

[0184] Step (1): Prepare (diethylphosphinocyclopentadienyl)tris(dimethylamino)zirconium. The synthesis route is the same as that in Example 1. The specific synthesis steps are as follows:

[0185] (1) In a water-free and oxygen-free glove box environment, using a dry three-necked flask and a dry condenser, set up an experimental device: 150 g of dry n-hexane and lithium dimethylamide (13.4 g, 0.257 mol) were added to the three-necked flask, the temperature was lowered to between 7±0.5°C, and zirconium tetrachloride (15 g, 0.064 mol) was slowly added in 5 batches. After the addition was completed, the temperature was raised to reflux and stirred for reaction for 4 h, and then cooled to room temperature. The reaction product was filtered using a dry sand core funnel to obtain a filtrate. The filtrate was subjected to reduced pressure distillation at room temperature to remove the solvent. The residual liquid was further purified by reduced pressure distillation at 0.1 torr and 70°C to obtain the first intermediate (tetrakis(dimethylamino)zirconium), about 15.03 g, with a yield of about 88%.

[0186] The first intermediate obtained was identified by nuclear magnetic hydrogen spectrum, and the specific data are as follows:

[0187] 1 HNMR(400MHz, C6D6): (2.978,24H).

[0188] Analysis of the H-NMR spectrum data showed that the target product was successfully obtained.

[0189] (2) Add 60 ml of tetrahydrofuran solution to a 200 ml three-necked flask, add 6 g (0.0907 mol) of the prepared cyclopentadiene, cool to -40°C, add NaH (2.29 g, 0.095 mol) in 5 batches, maintain the temperature during the addition, maintain the temperature and stir for 1 hour after the addition is completed; then slowly increase the temperature to -7±0.5°C, slowly add 15.64 g (0.0998 mol) of diethylphosphite chloride dropwise, and maintain the temperature at -7±0.5°C during the addition. After the addition is completed, stir at -7±0.5℃ for 1h, and after naturally returning to room temperature, add NaHCO3 ice water dropwise for quenching, use a separatory funnel to separate the reaction solution to obtain an organic phase, and then use NaSO4 to dry the organic phase, and filter to obtain a dry filtrate; then, at room temperature, the filtrate is subjected to reduced pressure distillation to remove the solvent, and the residual liquid is further subjected to reduced pressure distillation at 10torr, 40℃ to obtain the second intermediate (diethylphosphinocyclopentadiene), about 14.5g, with a yield of about 86%.

[0190] The obtained second intermediate was identified by nuclear magnetic hydrogen spectrum, and the specific data are as follows:

[0191] 1 H NMR (400MHz, CCl3D): (6.50,2H), (6.40,2H), (3.85,4H), (2.9,1H), (1.25,6H).

[0192] Analysis of the H-NMR spectrum data showed that the target product was successfully obtained.

[0193] (3) In a water-free and oxygen-free glove box, prepare a dry three-necked flask, a dry condenser, and set up an experimental device: add 150 g of dry n-hexane, add 15.4 g (0.057 mol) of the first intermediate tetrakis(dimethylamino)zirconium, stir evenly and cool to 0°C, slowly drop the second intermediate (diethylphosphinocyclopentadiene) into the three-necked flask, and maintain the temperature unchanged during the dropwise addition. After the dropwise addition is completed, maintain the temperature at 5°C and stir for 1.5 h, then raise the temperature to 70°C to reach a reflux state, stir and react for 2 h, and after returning to room temperature, use a dry PTFE filter element to filter the reaction product to obtain a filtrate, distill the filtrate under reduced pressure to remove the solvent, and then continue to distill under reduced pressure at 0.1 torr and 100°C to obtain 18.59 g of a light yellow liquid, namely (diethylphosphinocyclopentadienyl)tris(dimethylamino)zirconium, with a yield of about 79%.

[0194] The obtained light yellow liquid was identified by nuclear magnetic hydrogen spectrum, and the specific data are as follows: 1HNMR(400MHz,C6D6)(6.0061H),(5.920,2H),(3.57,4H),(2.96,18H),(2.45,1H),(1.25,6H).

[0195] Analysis of the H-NMR spectrum data showed that the target product was successfully obtained.

[0196] The total yield of (diethylphosphinocyclopentadienyl)tris(dimethylamino)zirconium was calculated in the same manner as in Example 1. Please see Table 1 for specific results.

[0197] Step (ii): refer to step (ii) of Example 1. For specific results, see Table 1.

[0198] Example 6

[0199] Step (1): Prepare (diethylphosphinocyclopentadienyl)tris(dimethylamino)zirconium. The synthesis route is the same as that in Example 1. The specific synthesis steps are as follows:

[0200] (1) In a water-free and oxygen-free glove box environment, using a dry three-necked flask and a dry condenser, set up an experimental device: 150 g of dry n-hexane and lithium dimethylamide (13.4 g, 0.257 mol) were added to the three-necked flask, the temperature was lowered to between 9°C and 10°C, and zirconium tetrachloride (15 g, 0.064 mol) was slowly added in 5 batches. After the addition was completed, the temperature was raised to reflux and stirred for reaction for 4 h, and then cooled to room temperature. The reaction product was filtered using a dry sand core funnel to obtain a filtrate. The filtrate was subjected to reduced pressure distillation at room temperature to remove the solvent. The residual liquid was further purified by reduced pressure distillation at 0.1 torr and 70°C to obtain the first intermediate (tetrakis(dimethylamino)zirconium), 14.85 g, with a yield of about 87%.

[0201] The first intermediate obtained was identified by nuclear magnetic hydrogen spectrum, and the specific data are as follows:

[0202] 1 H NMR (400MHz, C6D6): (2.978,24H).

[0203] Analysis of the H-NMR spectrum data showed that the target product was successfully obtained.

[0204] (2) Add 60 ml of tetrahydrofuran solution to a 200 ml three-necked flask, add 6 g (0.0907 mol) of cyclopentadiene, cool to -40°C, add NaH (2.29 g, 0.095 mol) in 5 batches, maintain the temperature during the addition, and stir for 1 hour after the addition is complete; then slowly increase the temperature to -0°C, slowly add 15.64 g (0.0998 mol) of diethylphosphite chloride dropwise, maintain the temperature at -0°C during the addition, and complete the addition. After that, it was stirred at -10°C-0°C for 1h, and after naturally returning to room temperature, NaHCO3 ice water was added dropwise for quenching, and the reaction solution was separated by a separatory funnel to obtain an organic phase, which was then dried with NaSO4 and filtered to obtain a dry filtrate; the filtrate was then subjected to reduced pressure distillation at room temperature to remove the solvent, and the residual liquid was further subjected to reduced pressure distillation at 10 torr and 40°C to obtain the second intermediate (diethylphosphinocyclopentadiene), about 14.33 g, with a yield of about 85%.

[0205] The obtained second intermediate was identified by nuclear magnetic hydrogen spectrum, and the specific data are as follows:

[0206] 1 H NMR (400MHz, CCl3D): (6.50,2H), (6.40,2H), (3.85,4H), (2.9,1H), (1.25,6H).

[0207] Analysis of the H-NMR spectrum data showed that the target product was successfully obtained.

[0208] (3) In a water-free and oxygen-free glove box, prepare a dry three-necked flask, a dry condenser, and set up the experimental apparatus: add 150 g of dry n-hexane, add 15.4 g (0.057 mol) of the first intermediate tetrakis(dimethylamino)zirconium, stir evenly and cool to 5°C, slowly drop the second intermediate (diethylphosphinocyclopentadiene) into the three-necked flask, and maintain the temperature unchanged during the dropwise addition. After the dropwise addition is completed, maintain the temperature at 5°C and stir for 1.5 h, then raise the temperature to 70°C to reach reflux state, stir and react for 2 h, and after returning to room temperature, use a dry PTFE filter element to filter the reaction product to obtain a filtrate, distill the filtrate under reduced pressure to remove the solvent, and then continue to distill under reduced pressure at 0.1 torr and 100°C to obtain 18.11 g of light yellow liquid, namely (diethylphosphinocyclopentadienyl)tris(dimethylamino)zirconium, with a yield of about 77%.

[0209] The obtained light yellow liquid was identified by nuclear magnetic hydrogen spectrum, and the specific data are as follows: 1HNMR (400MHz, C6D6): (6.0061H), (5.920,2H), (3.57,4H), (2.96,18H), (2.45,1H), (1.25,6H).

[0210] Analysis of the H-NMR spectrum data showed that the target product was successfully obtained.

[0211] The total yield of (diethylphosphinocyclopentadienyl)tris(dimethylamino)zirconium was calculated in the same manner as in Example 1. Please see Table 1 for specific results.

[0212] Step (ii): refer to step (ii) of Example 1. The specific results are shown in Table 1. The specific analysis results of the metal purity in the zirconium oxide film are shown in Table 2. The thermogravimetric analysis curve of the metal complex (diethylphosphinocyclopentadienyl) tris(dimethylamino)zirconium is shown in Table 2. Figure 3 shown.

[0213] Comparative Example 1

[0214] The specific steps for preparing the zirconium oxide film are as follows:

[0215] The reaction substrate was placed in a PE-MOCVD device, the deposition temperature was set at 250°C, (cyclopentadienyl) tris(dimethylamino) zirconium (CAS: 33271-88-4) was injected into the substrate of the reaction chamber together with nitrogen as a precursor material, oxygen plasma was introduced into the reaction chamber, and reacted with (cyclopentadienyl) tris(dimethylamino) zirconium to form zirconium oxide which was deposited on the substrate, and nitrogen was introduced again after the oxide layer was formed to remove unreacted precursor materials and by-products; the deposition step was repeated 4 times to obtain a zirconium oxide film on the substrate.

[0216] ICP-MS (LabMS 3000) was used to test the metal purity in the zirconium oxide film, AFM (ParkFX40) was used to test the surface uniformity of the zirconium oxide film, and thermogravimetry (TGA 550) was used to test the thermal stability of (cyclopentadienyl) tris(dimethylamino) zirconium. The specific results are shown in Table 1.

[0217] The total yield of (diethylphosphinocyclopentadienyl) tris(dimethylamino) zirconium obtained in Examples 1 to 6, the metal purity of the zirconium oxide films obtained in Examples 1 to 6 and Comparative Example 1, the surface uniformity of the zirconium oxide films and the thermal stability of the metal complex are shown in Table 1. Among them, when weight percent loss ≥ 99.8%, the thermal stability is judged to be excellent, and when weight percent loss ≥ 99.9%, the thermal stability is judged to be excellent; when the uniformity test is performed, the electron force microscope AFM (Park FX40) is equipped with a low-noise Z-axis detector with a significant noise bandwidth of 0.2nm, the test result is less than 2nm, the uniformity is judged to be excellent, and when the test result is 2-2.5nm, the uniformity is judged to be excellent.

[0218] Table 1

[0219]

[0220] Note: “6N” means the purity is 99.999%.

[0221] The specific analysis results of the metal purity of the zirconium oxide film in Example 6 are shown in Table 2.

[0222] Table 2

[0223]

[0224]

[0225] Note: “ppb” means parts per billion (parts per billion, 10 -9 ).

[0226] The data of Examples 1 to 6 and Comparative Example 1 in Table 1 and Figures 1 to 3 It can be seen from the thermogravimetric analysis diagram that: the synthesis route of the present application can successfully obtain the target metal complex, and when the experiment is repeated, a relatively high and stable yield level can be achieved. In addition, the metal complex provided by the present application has higher thermal stability. When used as a precursor material to prepare zirconium oxide film, the purity and uniformity of the zirconium oxide film can be improved, thereby improving the product performance stability at the back end of industrial application.

[0227] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations on the present invention. A person skilled in the art may change, modify, replace and modify the above embodiments within the scope of the present invention without departing from the principles and intent of the present invention.

Claims

1. A metal complex, characterized in that The metal complex is shown in formula (1): Here, R1 to R2 and each R3 are independently selected from an alkyl group having 1 to 5 carbon atoms.

2. The metal complex according to claim 1, characterized in that R1 to R2 are independently selected from chain alkyl groups having 1 to 3 carbon atoms; and / or Each R3 is independently selected from a chain alkyl group having 1 to 3 carbon atoms; and / or The metal complex is shown in formula (1-1):

3. The metal complex according to claim 1, characterized in that The metal complex is shown in formula (1-2):

4. A method for preparing a metal complex, characterized in that: The steps include: subjecting compound (a) to a first substitution reaction with compound (b) to prepare intermediate (c); subjecting compound (d) to a second substitution reaction with compound (e) to prepare intermediate (f); The intermediate (c) and the intermediate (f) are subjected to a third substitution reaction to prepare a metal complex represented by formula (1); Wherein, the compound (a), the compound (b), the intermediate (c), the compound (d), the compound (e), the intermediate (f) and the metal complex are respectively as follows: R1 to R2 and each R3 are independently selected from an alkyl group having 1 to 5 carbon atoms.

5. The method for preparing a metal complex according to claim 4, characterized in that: The mass ratio of the compound (b) to the compound (a) is (2-10):(2-10); and / or The first substitution reaction is carried out in a solvent under reflux conditions for 3 h to 5 h; and / or The process for preparing intermediate (c) further comprises the following steps: The reaction product of the first substitution reaction is filtered to obtain a filtrate, and then the filtrate is subjected to reduced pressure distillation to obtain the intermediate (c).

6. The method for preparing a metal complex according to any one of claims 4 to 5, characterized in that: The second substitution reaction is carried out under the action of NaH, and the mass ratio of the NaH to the compound (d) is (2-10):(2-10).

7. The method for preparing a metal complex according to claim 6, characterized in that: The mass ratio of the compound (e) to the compound (d) is (2-10):(2-10); and / or The process for preparing intermediate (f) comprises the following steps: At -40°C, adding the NaH to a tetrahydrofuran solution of the compound (d), and then adding the compound (e) at -10°C to 0°C to carry out a reaction, and after the reaction is completed, quenching with alkaline ice water to obtain a reaction product of the second substitution reaction; subjecting the reaction product of the second substitution reaction to a liquid separation treatment to obtain an organic phase product; The organic phase product is sequentially dried and distilled under reduced pressure to obtain the intermediate (f).

8. The method for preparing a metal complex according to any one of claims 4 to 5, characterized in that: The molar ratio of the intermediate (f) to the intermediate (c) is (1-1.3):1; and / or The process for preparing the metal complex represented by formula (1) comprises the following steps: At 0°C-5°C, the intermediate (f) is added dropwise into the n-hexane solution of the intermediate (c) to mix, and then the mixture is heated to reflux to react, thereby obtaining a reaction product of the third substitution reaction; performing solid-liquid separation on the reaction product of the third substitution reaction to obtain a filtrate; The filtrate is purified to obtain the metal complex represented by formula (1).

9. Use of the metal complex according to any one of claims 1 to 3 in the preparation of zirconium oxide film.

10. A zirconium oxide film, characterized in that: The zirconium oxide film is prepared by deposition of a precursor material, wherein the precursor material comprises the metal complex as claimed in any one of claims 1 to 3.

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