A metal complex, its preparation method and application, and a zirconium oxide film.

Abstract

This invention belongs to the field of organic compound technology and discloses a metal complex, its preparation method and application, and a zirconia film. The metal complex is shown in formula (1), wherein R1-R2 and each R3 are independently selected from alkyl groups having 1-5 carbon atoms. By coordinating the cyclopentadienyl and dimethylamino groups with the central metal zirconium, and simultaneously connecting the cyclopentadienyl group with a phosphorus-containing group with strong coordination ability, the resulting electronic effect can increase the electron density of the central metal zirconium, making the coordination interaction between the cyclopentadienyl ligand and the central metal zirconium stronger, thereby improving the thermal stability of the metal complex. When this metal complex is used as a precursor material to prepare a zirconia film, it can improve the purity and uniformity of the zirconia film.

Description

Technical Field

[0001] This invention belongs to the field of organic compound technology, and in particular relates to metal complexes, their preparation methods and applications, and zirconium oxide films. Background Technology

[0002] In recent years, zirconium oxide (ZrO2), a high-k dielectric material, has been increasingly widely used in the semiconductor field. Zirconia possesses high permittivity, good thermal stability, and a significant bandgap with silicon, making it considered one of the high-k materials capable of replacing silicon-based gate insulators. Zirconia films are typically obtained using zirconium source precursors through deposition techniques such as CVD (chemical vapor deposition) or ALD (atomic layer deposition) for application in semiconductor devices. To ensure successful production, the zirconium source precursor must possess sufficient chemical reactivity and thermal stability to guarantee operational safety, while minimizing the negative impact of impurities on the oxide film performance. These factors are the main determinants of zirconium oxide film performance.

[0003] However, as semiconductor devices become smaller and lighter, the performance requirements of zirconium oxide films for semiconductor devices such as gate dielectrics of dynamic random access memory (DRAM) or capacitor dielectric films are becoming increasingly stringent. This places higher and higher demands on the thermal stability of zirconium source precursors, which traditional zirconium source precursors cannot meet.

[0004] Therefore, traditional technologies still need improvement. Summary of the Invention

[0005] The purpose of this invention is to provide a metal complex, its preparation method and application, and a zirconia film. The metal complex has excellent thermal stability. When the metal complex is used as a precursor material to prepare a zirconia film, it can improve the purity, uniformity and thermal stability of the zirconia film.

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

[0007] A first aspect of this application provides a metal complex as shown in formula (1):

[0008]

[0009] R1 to R2 and each of R3 are independently selected from alkyl groups having 1 to 5 carbon atoms.

[0010] The aforementioned metal complexes have a specific structure. By coordinating the cyclopentadienyl and dimethylamino groups with the central zirconium metal and simultaneously connecting the cyclopentadienyl group with a phosphorus-containing group that has a strong coordination ability, the resulting electronic effect can increase the electron density of the central zirconium metal, making the coordination effect between the cyclopentadienyl ligand and the central zirconium metal stronger, thereby improving the thermal and chemical stability of the metal complexes.

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

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

[0013] Each R3 is independently selected from an 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 formulas (1-2):

[0017]

[0018] A second aspect of this application provides a method for preparing a metal complex, comprising the following steps:

[0019] Compound (a) and compound (b) were subjected to a first substitution reaction to prepare intermediate (c);

[0020] Compound (d) and compound (e) were subjected to a second substitution reaction to prepare intermediate (f);

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

[0022] The compounds (a), (b), (c), (d), (e), (f), and the metal complex are respectively shown below:

[0023]

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

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

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

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

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

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

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

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

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

[0033] At -40°C, NaH was added to a tetrahydrofuran solution of compound (d), and then compound (e) was added at -10°C to 0°C to carry out the reaction. After the reaction was completed, the reaction product of the second substitution reaction was obtained by quenching with alkaline ice water.

[0034] The reaction product of the second substitution reaction was separated into liquid and liquid phase products to obtain organic phase products;

[0035] The organic phase product was subjected to drying and vacuum distillation in sequence to obtain the intermediate (f).

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

[0037] The process for preparing the metal complex shown in formula (1) includes the following steps:

[0038] Under conditions of 0℃-5℃, the intermediate (f) is added dropwise to a hexane solution of the intermediate (c) and mixed, and then the mixture is heated to reflux to carry out the reaction to obtain the reaction product of the third substitution reaction;

[0039] The reaction product of the third substitution reaction is subjected to solid-liquid separation treatment to obtain filtrate;

[0040] The filtrate was purified to obtain the metal complex shown in formula (1).

[0041] A third aspect of this application provides the application of the metal complex of the first aspect in the preparation of zirconia films.

[0042] In a fourth aspect of this application, a zirconia film is provided, the zirconia film being prepared by deposition of a precursor material, the precursor material comprising the metal complex of the first aspect. Attached Figure Description

[0043] Figure 1 Thermogravimetric analysis curve of the metal complex obtained in Example 1;

[0044] Figure 2 Thermogravimetric analysis curve of the metal complex obtained in Example 3;

[0045] Figure 3 Thermogravimetric analysis curve of the metal complex obtained in Example 6. Detailed Implementation

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

[0047] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.

[0048] In the description of the embodiments of this application, technical terms such as "first" and "second" are used only to distinguish different objects and should not be construed as indicating or implying relative importance or implicitly specifying the number, specific order, or primary and secondary relationship of the indicated technical features. In the description of the embodiments of this application, "multiple" means two or more, unless otherwise explicitly defined.

[0049] In this application, "optionally," "optionally," and "optional" mean that something is optional, that is, it means that it is selected from either "with" or "without." If there are multiple "optional" entries in a technical solution, unless otherwise specified and there are no contradictions or mutual constraints, each "optional" entry shall be independent.

[0050] In this application, the term "alkyl" refers to a group formed by the loss of one hydrogen atom from an alkane, such as methyl formed by the loss of one hydrogen atom from methane; "alkyl" includes chain alkyl and cycloalkyl, the former refers to a group formed by the loss of one hydrogen atom from an alkane in which all carbon atoms are connected by carbon-carbon single bonds and do not form a ring, and the latter refers to a cyclic alkyl; optionally, chain alkyl may also include straight-chain alkyl and branched-chain alkyl.

[0051] In this application, the single bond attached to the substituent extends through the corresponding ring, indicating that the substituent can be attached to any position on the ring, for example... The symbol R indicates that it is connected to any substituted site of the loop.

[0052] One embodiment of this application provides a metal complex as shown in formula (1):

[0053]

[0054] R1 to R2 and each of R3 are independently selected from alkyl groups having 1 to 5 carbon atoms.

[0055] The aforementioned metal complexes have a specific structure. By coordinating the cyclopentadienyl and dimethylamino groups with the central zirconium metal and simultaneously connecting the cyclopentadienyl group with a phosphorus-containing group that has a strong coordination ability, the resulting electronic effect can increase the electron density of the central zirconium metal, making the coordination effect between the cyclopentadienyl ligand and the central zirconium metal stronger, thereby improving the thermal and chemical stability of the metal complexes.

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

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

[0058] In some embodiments, R1 to R2 are each independently selected from alkyl groups having 1 to 5 carbon atoms; optionally, R1 to R2 are each independently selected from linear alkyl groups having 1 to 5 carbon atoms.

[0059] In some embodiments, R1 to R2 are each independently selected from alkyl groups having 1 to 3 carbon atoms; optionally, R1 to R2 are each independently selected from linear alkyl groups having 1 to 3 carbon atoms.

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

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

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

[0063] In some embodiments, each R3 is independently selected from a chain alkyl group having 1 to 5 carbon atoms; optionally, 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; optionally, 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 of these embodiments, each R3 is selected from the same group.

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

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

[0069]

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

[0071]

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

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

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

[0075] S30: The intermediate (c) and intermediate (f) are subjected to a third substitution reaction to prepare the metal complex shown in formula (1).

[0076] The compounds (a) and (b), intermediate (c), (d) and (e), intermediate (f), and metal complexes are shown below:

[0077]

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

[0079] The further selectable ranges of R1 to R2 and each of R3 are the same as above, and will not be repeated 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 embodiments, the first substitution reaction is carried out in a solvent under reflux for 3 to 5 hours; optionally, the solvent is n-hexane.

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

[0084] S11: The reaction product of the first substitution reaction is filtered to obtain a filtrate, which is then subjected to vacuum distillation to obtain intermediate (c). Specifically, the solvent is removed by vacuum distillation first, and then intermediate (c) is separated by vacuum distillation.

[0085] In some of these embodiments, the first substitution reaction is carried out under anaerobic and anhydrous conditions.

[0086] In some of the 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 of these embodiments, the second substitution reaction is carried out under anaerobic and anhydrous conditions.

[0089] In some of these embodiments, the second substitution reaction is carried out in the presence of NaH, with a mass ratio of NaH to compound (d) of (2-10):(2-10).

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

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

[0092] S21: At -40℃, NaH is added to a tetrahydrofuran solution of compound (d), and then compound (e) is added at -10℃ to 0℃ to carry out the reaction. After the reaction is completed, the reaction is quenched with alkaline ice water to obtain the reaction product of the second substitution reaction.

[0093] In one specific example, after adding compound (e) at -10℃ to 0℃, the reaction was stirred for 1 hour, and then quenched with alkaline ice water after being restored to room temperature.

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

[0095] S22: Separate the reaction product of the second substitution reaction to obtain the organic phase product.

[0096] S23: The organic phase product is subjected to drying and vacuum distillation in sequence to obtain intermediate (f).

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

[0098] In some of these embodiments, the third substitution reaction is carried out under anaerobic and anhydrous conditions.

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

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

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

[0102] S31: At 0℃-5℃, intermediate (f) is added dropwise to a hexane solution of intermediate (c) and mixed. Then, the mixture is heated to reflux to carry out the reaction and obtain the reaction product of the third substitution reaction.

[0103] In one specific example, intermediate (f) was added dropwise to a hexane solution of intermediate (c) and stirred for 1.5 h, then heated to reflux for 2 h.

[0104] S32: The reaction product of the third substitution reaction is subjected to solid-liquid separation treatment to obtain filtrate.

[0105] Solid-liquid separation can be achieved using commonly used solid-liquid separation processes in this field, such as vacuum filtration or filtration.

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

[0107] In a specific example, the purification process includes: removing the solvent by vacuum distillation of the filtrate, and purifying the remaining material by distillation.

[0108] Another embodiment of this application also provides the application of the above-mentioned metal complex in the preparation of zirconia films.

[0109] In a fourth aspect, this application provides a zirconia film, which is prepared by deposition of a precursor material, the precursor material including the aforementioned metal complex.

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

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

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

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

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

[0115] In some of these 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 examples.

[0118] Example 1

[0119] Step (I): Preparation of (diethylphosphine-cyclopentadienyl)tris(dimethylamino)zirconium, the synthetic 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, the experimental setup was constructed as follows: 150g of dry n-hexane and lithium dimethylamino (13.4g, 0.257mol) were added to the three-necked flask, and the temperature was lowered to 0℃±0.5℃. Zirconium tetrachloride (15g, 0.064mol) was slowly added in 5 batches. After the addition was completed, the temperature was raised to reflux and the reaction was stirred for 4 hours. Then, the temperature was lowered to room temperature, and the reaction product was filtered using a dry sintered glass funnel to obtain the filtrate. At room temperature, the filtrate was subjected to vacuum distillation to remove the solvent. The residue was further purified by vacuum distillation at 0.1 torr and 70℃ to obtain the first intermediate (tetra(dimethylamino)zirconium), approximately 15.4g, with a yield of approximately 90%.

[0123] The first intermediate was identified by 1H NMR spectroscopy, and the specific data are as follows:

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

[0125] Analysis of the 1H NMR data shows that the target product was successfully obtained.

[0126] (2) Add 60 ml of tetrahydrofuran solution to a 200 ml three-necked flask, then add 6 g (0.0907 mol) of prepared cyclopentadiene. After cooling to -40 °C, add NaH (2.29 g, 0.095 mol) in 5 batches, maintaining a constant temperature during the addition process. After the addition is complete, maintain the temperature and stir for 1 h. Then slowly raise the temperature to -10 °C ± 0.5 °C, and slowly add 15.64 g (0.0998 mol) of diethylphosphorous chloride dropwise, maintaining the temperature at -10 °C ± 0.5 °C during the dropwise addition process. After the addition of the solution was completed, the mixture was stirred at -10 to 0°C for 1 hour. After naturally returning to room temperature, NaHCO3 ice water was added dropwise for quenching. The reaction solution was separated using a separatory funnel to obtain the organic phase. The organic phase was then dried with NaSO4 and filtered to obtain a dry filtrate. The filtrate was then subjected to vacuum distillation at room temperature to remove the solvent. The residue was further subjected to vacuum distillation at 10 torr and 40°C to obtain the second intermediate (diethylphosphine cyclopentadiene), approximately 14.35 g, with a yield of approximately 85%.

[0127] The obtained second intermediate was identified by 1H NMR spectroscopy, 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 1H NMR data shows that the target product was successfully obtained.

[0129] (3) In an anhydrous and oxygen-free glove box, prepare a dry three-necked flask and a dry condenser, and set up the experimental apparatus: add 150g of dry n-hexane, add 15.4g (0.057mol) of the first intermediate tetra(dimethylamino)zirconium, stir evenly and cool to 0℃±0.5℃, slowly add the second intermediate (diethylphosphine cyclopentadiene) dropwise into the three-necked flask, keeping the temperature constant during the dropwise addition. After the dropwise addition is completed, maintain the temperature at 0℃±0.5℃ and stir for 1.5h, then raise the temperature to 70℃ to reach reflux state, stir the reaction for 2h, and after returning to room temperature, use a dry PTFE filter to filter the reaction product to obtain the filtrate. Remove the solvent by vacuum distillation of the filtrate, and then continue vacuum distillation at 0.1tor and 100℃ to obtain 18.12g of pale yellow liquid, which is (diethylphosphine cyclopentadienyl)tri(dimethylamino)zirconium.

[0130] The obtained pale yellow liquid was identified by 1H NMR spectroscopy, 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 1H NMR data showed that the target product was successfully obtained.

[0132] The overall yield of (diethylphosphine-cyclopentadienyl)tris(dimethylamino)zirconium (CpZr) was calculated using the following formula:

[0133] Overall yield = Actual yield of CpZr / Theoretical yield of CpZr × 100%;

[0134] The theoretical yield of CpZr is calculated as: (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 zirconia film, as detailed below.

[0136] The reaction substrate was placed in a PE-MOCVD apparatus, and the deposition temperature was set to 250°C. (Diethylphosphonocyclopentadienyl)tris(dimethylamino)zirconia, used as a precursor material, was injected into the substrate along with nitrogen gas into the reaction chamber. Oxygen plasma was then introduced into the reaction chamber to react with (diethylphosphonocyclopentadienyl)tris(dimethylamino)zirconia, forming zirconia that was deposited on the substrate. After the oxide layer was formed, nitrogen gas was introduced again to remove unreacted precursor material and byproducts. This deposition step was repeated four times to obtain a zirconia film on the substrate.

[0137] The metal purity of the zirconia film was tested using ICP-MS (LabMS 3000), the surface uniformity of the zirconia film was tested using AFM (ParkFX40), and the thermal stability of (diethylphosphine-cyclopentadienyl)tris(dimethylamino)zirconia was tested using thermogravimetric analysis (TGA 550). Specific results are shown in Table 1. The thermogravimetric analysis curves of the metal complex (diethylphosphine-cyclopentadienyl)tris(dimethylamino)zirconia are shown in the figure below. Figure 1 As shown.

[0138] Example 2

[0139] Step (I): Preparation of (diethylphosphine-cyclopentadienyl)tris(dimethylamino)zirconium, the synthetic route is the same as in Example 1, and the specific synthetic steps are as follows:

[0140] (1) In an anhydrous and oxygen-free glove box environment, using a dry three-necked flask and a dry condenser, the experimental setup was set up: 150g of dry n-hexane and lithium dimethylamino (13.4g, 0.257mol) were added to the three-necked flask, and the temperature was lowered to between 1±0.5℃. Zirconium tetrachloride (15g, 0.064mol) was slowly added in 5 batches. After the addition was completed, the temperature was raised to reflux and stirred for 4h. Then the temperature was lowered to room temperature, and the reaction product was filtered using a dry sintered glass funnel to obtain the filtrate. At room temperature, the filtrate was subjected to vacuum distillation to remove the solvent. The residual liquid was further purified by vacuum distillation at 0.1 torr and 70℃ to obtain the first intermediate (tetra(dimethylamino)zirconium), about 15.05g, with a yield of about 88%.

[0141] The first intermediate was identified by 1H NMR spectroscopy, and the specific data are as follows:

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

[0143] Analysis of the 1H NMR 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 prepared cyclopentadiene, cool to -40 °C, and then add NaH (2.29 g, 0.095 mol) in 5 batches, maintaining the temperature constant during the addition. After the addition is complete, maintain the temperature and stir for 1 h; then slowly raise the temperature to -3 ± 0.5 °C, and slowly add 15.64 g (0.0998 mol) of diethylphosphorous chloride dropwise, maintaining the temperature at -3 ± 0.5 °C during the dropwise addition. After the addition was complete, the mixture was stirred at -3±0.5℃ for 1 hour. After naturally returning to room temperature, NaHCO3 ice water was added dropwise for quenching. The reaction mixture was separated using a separatory funnel to obtain the organic phase. The organic phase was then dried with NaSO4 and filtered to obtain a dry filtrate. The solvent was then removed by vacuum distillation at room temperature. The residue was further distilled under vacuum at 10 torr and 40℃ to obtain the second intermediate (diethylphosphine cyclopentadiene), approximately 14.85 g, with a yield of approximately 88%.

[0145] The obtained second intermediate was identified by 1H NMR spectroscopy, 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 1H NMR data showed that the target product was successfully obtained.

[0148] (3) In an anhydrous and oxygen-free glove box, prepare a dry three-necked flask and a dry condenser, and set up the experimental apparatus: add 150g of dry n-hexane, add 15.4g (0.057mol) of the first intermediate tetra(dimethylamino)zirconium, stir evenly and cool to 1℃±0.5℃, slowly add the second intermediate (diethylphosphine cyclopentadiene) dropwise into the three-necked flask, keeping the temperature constant during the dropwise addition. After the dropwise addition is complete, maintain the temperature at 1℃±0.5℃ and stir for 1.5h, then raise the temperature to 70℃ to reach reflux, stir the reaction for 2h, and after returning to room temperature, filter the reaction product using a dry PTFE filter to obtain the filtrate. Remove the solvent from the filtrate by vacuum distillation, and then continue vacuum distillation at 0.1tor and 100℃ to obtain 18.6g of pale yellow liquid, which is (diethylphosphine cyclopentadienyl)tri(dimethylamino)zirconium, with a yield of about 79%.

[0149] The obtained pale yellow liquid was identified by 1H NMR spectroscopy, 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 1H NMR data showed that the target product was successfully obtained.

[0151] The total yield of (diethylphosphine-cyclopentadienyl)tri(dimethylamino)zirconium was calculated in the same way as in Example 1. The specific results are shown in Table 1.

[0152] Step (II): Refer to Step (II) of Example 1. For specific results, please see Table 1.

[0153] Example 3

[0154] Step (I): Preparation of (diethylphosphine-cyclopentadienyl)tris(dimethylamino)zirconium, the synthetic route is the same as in Example 1, and the specific synthetic steps are as follows:

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

[0156] The first intermediate was identified by 1H NMR spectroscopy, and the specific data are as follows:

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

[0158] Analysis of the 1H NMR 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 prepared cyclopentadiene, cool to -40 °C, and then add NaH (2.29 g, 0.095 mol) in 5 batches, maintaining the temperature constant during the addition. After the addition is complete, maintain the temperature and stir for 1 h; then slowly raise the temperature to -5 ± 0.5 °C, and slowly add 15.64 g (0.0998 mol) of diethylphosphorous chloride dropwise, maintaining the temperature at -5 ± 0.5 °C during the dropwise addition. After the addition was complete, the mixture was stirred at -5±0.5℃ for 1 hour. After naturally returning to room temperature, NaHCO3 ice water was added dropwise for quenching. The reaction mixture was separated using a separatory funnel to obtain the organic phase. The organic phase was then dried with NaSO4 and filtered to obtain a dry filtrate. The solvent was then removed by vacuum distillation at room temperature. The residue was further distilled under vacuum at 10 torr and 40℃ to obtain the second intermediate (diethylphosphine cyclopentadiene), approximately 15.18 g, with a yield of 90%.

[0160] The obtained second intermediate was identified by 1H NMR spectroscopy, 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 1H NMR 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 and a dry condenser, and set up the experimental apparatus: add 150g of dry n-hexane, add 15.4g (0.057mol) of the first intermediate tetra(dimethylamino)zirconium, stir evenly and cool to 2℃±0.5℃, slowly add the second intermediate (diethylphosphine cyclopentadiene) dropwise into the three-necked flask, keeping the temperature constant during the dropwise addition. After the dropwise addition is complete, maintain the temperature at 2℃±0.5℃ and stir for 1.5h, then raise the temperature to 70℃ to reach reflux state, stir the reaction for 2h, and after returning to room temperature, filter the reaction product using a dry PTFE filter to obtain the filtrate. Remove the solvent from the filtrate by vacuum distillation, and then continue vacuum distillation at 0.1tor and 100℃ to obtain 17.89g of pale yellow liquid, which is (diethylphosphine cyclopentadienyl)tri(dimethylamino)zirconium, with a yield of about 76%.

[0164] The obtained pale yellow liquid was identified by 1H NMR spectroscopy, 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 1H NMR data showed that the target product was successfully obtained.

[0166] The total yield of (diethylphosphine-cyclopentadienyl)tri(dimethylamino)zirconium was calculated in the same way as in Example 1. The specific results are shown in Table 1.

[0167] Step (II): Refer to Step (II) of Example 1. Specific results are shown in Table 1. The thermogravimetric analysis curves of the metal complex (diethylphosphine-cyclopentadienyl)tris(dimethylamino)zirconium are shown below. Figure 2 As shown.

[0168] Example 4

[0169] Step (I): Preparation of (diethylphosphine-cyclopentadienyl)tris(dimethylamino)zirconium, the synthetic route is the same as in Example 1, and the specific synthetic steps are as follows:

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

[0171] The first intermediate was identified by 1H NMR spectroscopy, and the specific data are as follows:

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

[0173] Analysis of the 1H NMR 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 prepared cyclopentadiene, cool to -40 °C, and then add NaH (2.29 g, 0.095 mol) in 5 batches, maintaining the temperature constant during the addition. After the addition is complete, maintain the temperature and stir for 1 h; then slowly raise the temperature to -6 ± 0.5 °C, and slowly add 15.64 g (0.0998 mol) of diethylphosphorous chloride dropwise, maintaining the temperature at -6 ± 0.5 °C during the dropwise addition. After the addition was complete, the mixture was stirred at -6±0.5℃ for 1 hour. After naturally returning to room temperature, NaHCO3 ice water was added dropwise for quenching. The reaction mixture was separated using a separatory funnel to obtain the organic phase. The organic phase was then dried with NaSO4 and filtered to obtain a dry filtrate. The solvent was then removed by vacuum distillation at room temperature. The residue was further distilled under vacuum at 10 torr and 40℃ to obtain the second intermediate (diethylphosphine cyclopentadiene), approximately 14.67 g, with a yield of approximately 87%.

[0175] The obtained second intermediate was identified by 1H NMR spectroscopy, 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 1H NMR data showed that the target product was successfully obtained.

[0178] (3) In an anhydrous and oxygen-free glove box, prepare a dry three-necked flask and a dry condenser, and set up the experimental apparatus: add 150g of dry n-hexane, add 15.4g (0.057mol) of the first intermediate tetra(dimethylamino)zirconium, stir evenly and cool to 4℃±0.5℃, slowly add the second intermediate (diethylphosphine cyclopentadiene) dropwise into the three-necked flask, keeping the temperature constant during the dropwise addition. After the dropwise addition is complete, maintain the temperature at 4℃±0.5℃ and stir for 1.5h, then raise the temperature to 70℃ to reach reflux state, stir the reaction for 2h, and after returning to room temperature, filter the reaction product using a dry PTFE filter to obtain the filtrate. Remove the solvent from the filtrate by vacuum distillation, and then continue vacuum distillation at 0.1tor and 100℃ to obtain 18.83g of pale yellow liquid, which is (diethylphosphine cyclopentadienyl)tri(dimethylamino)zirconium, with a yield of about 80%.

[0179] The obtained pale yellow liquid was identified by 1H NMR spectroscopy, 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 1H NMR data showed that the target product was successfully obtained.

[0181] The total yield of (diethylphosphine-cyclopentadienyl)tri(dimethylamino)zirconium was calculated in the same way as in Example 1. The specific results are shown in Table 1.

[0182] Step (II): Refer to Step (II) of Example 1. For specific results, please see Table 1.

[0183] Example 5

[0184] Step (I): Preparation of (diethylphosphine-cyclopentadienyl)tris(dimethylamino)zirconium, the synthetic route is the same as in Example 1, and the specific synthetic steps are as follows:

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

[0186] The first intermediate was identified by 1H NMR spectroscopy, and the specific data are as follows:

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

[0188] Analysis of the 1H NMR 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 prepared cyclopentadiene, cool to -40 °C, and then add NaH (2.29 g, 0.095 mol) in 5 batches, maintaining a constant temperature during the addition. After the addition is complete, maintain the temperature and stir for 1 h; then slowly raise the temperature to -7 ± 0.5 °C, and slowly add 15.64 g (0.0998 mol) of diethylphosphorous chloride dropwise, maintaining the temperature at -7 ± 0.5 °C during the dropwise addition. After the addition was complete, the mixture was stirred at -7±0.5℃ for 1 hour. After naturally returning to room temperature, NaHCO3 ice water was added dropwise for quenching. The reaction mixture was separated using a separatory funnel to obtain the organic phase. The organic phase was then dried with NaSO4 and filtered to obtain a dry filtrate. The solvent was then removed by vacuum distillation at room temperature. The residue was further distilled under vacuum at 10 torr and 40℃ to obtain the second intermediate (diethylphosphine cyclopentadiene), approximately 14.5 g, with a yield of approximately 86%.

[0190] The obtained second intermediate was identified by 1H NMR spectroscopy, 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 1H NMR data showed that the target product was successfully obtained.

[0193] (3) In an anhydrous and oxygen-free glove box, prepare a dry three-necked flask and a dry condenser, and set up the experimental apparatus: add 150g of dry n-hexane, add 15.4g (0.057mol) of the first intermediate tetra(dimethylamino)zirconium, stir evenly and cool to 0℃, slowly add the second intermediate (diethylphosphine cyclopentadiene) dropwise into the three-necked flask, keeping the temperature constant during the dropwise addition. After the dropwise addition is complete, maintain the temperature at 5℃ and stir for 1.5h, then raise the temperature to 70℃ to reach reflux state, stir the reaction for 2h, and after returning to room temperature, filter the reaction product using a dry PTFE filter to obtain the filtrate. Remove the solvent from the filtrate by vacuum distillation, and then continue vacuum distillation at 0.1tor and 100℃ to obtain 18.59g of pale yellow liquid, which is (diethylphosphine cyclopentadienyl)tri(dimethylamino)zirconium, with a yield of about 79%.

[0194] The obtained pale yellow liquid was identified by 1H NMR spectroscopy, 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 1H NMR data showed that the target product was successfully obtained.

[0196] The total yield of (diethylphosphine-cyclopentadienyl)tri(dimethylamino)zirconium was calculated in the same way as in Example 1. The specific results are shown in Table 1.

[0197] Step (II): Refer to Step (II) of Example 1. For specific results, please see Table 1.

[0198] Example 6

[0199] Step (I): Preparation of (diethylphosphine-cyclopentadienyl)tris(dimethylamino)zirconium, the synthetic route is the same as in Example 1, and the specific synthetic steps are as follows:

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

[0201] The first intermediate was identified by 1H NMR spectroscopy, and the specific data are as follows:

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

[0203] Analysis of the 1H NMR 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 prepared cyclopentadiene, cool to -40 °C, and then add NaH (2.29 g, 0.095 mol) in 5 batches, maintaining the temperature constant during the addition. After the addition is complete, maintain the temperature and stir for 1 h; then slowly raise the temperature to -0 °C, and slowly add 15.64 g (0.0998 mol) of diethylphosphorous chloride dropwise, maintaining the temperature at -0 °C during the dropwise addition. Then, the mixture was stirred at -10℃ to 0℃ for 1 hour. After naturally returning to room temperature, NaHCO3 ice water was added dropwise for quenching. The reaction solution was separated using a separatory funnel to obtain the organic phase. The organic phase was then dried with NaSO4 and filtered to obtain a dry filtrate. The solvent was then removed by vacuum distillation at room temperature. The residue was further distilled under vacuum at 10 torr and 40℃ to obtain the second intermediate (diethylphosphine cyclopentadiene), approximately 14.33 g, with a yield of approximately 85%.

[0205] The obtained second intermediate was identified by 1H NMR spectroscopy, 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 1H NMR data showed that the target product was successfully obtained.

[0208] (3) In an anhydrous and oxygen-free glove box, prepare a dry three-necked flask and a dry condenser, and set up the experimental apparatus: add 150g of dry n-hexane, add 15.4g (0.057mol) of the first intermediate tetra(dimethylamino)zirconium, stir evenly and cool to 5℃, slowly add the second intermediate (diethylphosphine cyclopentadiene) dropwise into the three-necked flask, keeping the temperature constant during the dropwise addition. After the dropwise addition is complete, maintain the temperature at 5℃ and stir for 1.5h, then raise the temperature to 70℃ to reach reflux state, stir the reaction for 2h, and after returning to room temperature, filter the reaction product using a dry PTFE filter to obtain the filtrate. Remove the solvent by vacuum distillation of the filtrate, and then continue vacuum distillation at 0.1tor and 100℃ to obtain 18.11g of pale yellow liquid, which is (diethylphosphine cyclopentadienyl)tri(dimethylamino)zirconium, with a yield of about 77%.

[0209] The obtained pale yellow liquid was identified by 1H NMR spectroscopy, 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 1H NMR data showed that the target product was successfully obtained.

[0211] The total yield of (diethylphosphine-cyclopentadienyl)tri(dimethylamino)zirconium was calculated in the same way as in Example 1. The specific results are shown in Table 1.

[0212] Step (II): Refer to Step (II) of Example 1. Specific results are shown in Table 1. The specific analytical results of the metal purity in the zirconium oxide film are shown in Table 2. The thermogravimetric analysis curve of the metal complex (diethylphosphine-cyclopentadienyl)tris(dimethylamino)zirconium is shown in Table 2. Figure 3 As 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 apparatus, and the deposition temperature was set to 250°C. (Cyclopentadienyl)tris(dimethylamino)zirconium (CAS: 33271-88-4) was used as a precursor material and injected into the substrate of the reaction chamber along with nitrogen gas. Oxygen plasma was introduced into the reaction chamber to react with (Cyclopentadienyl)tris(dimethylamino)zirconium to form zirconia, which was deposited on the substrate. After the oxide layer was formed, nitrogen gas was introduced again to remove unreacted precursor material and byproducts. This deposition step was repeated 4 times to obtain a zirconia film on the substrate.

[0216] The metal purity in the zirconia film was tested using ICP-MS (LabMS 3000), the surface uniformity of the zirconia film was tested using AFM (ParkFX40), and the thermal stability of (cyclopentadienyl)tris(dimethylamino)zirconia was tested using thermogravimetric analysis (TGA 550). The specific results are shown in Table 1.

[0217] The total yield of (diethylphosphine-cyclopentadienyl)tris(dimethylamino)zirconium prepared in Examples 1-6, the metal purity of the zirconia films prepared in Examples 1-6 and Comparative Example 1, the surface uniformity of the zirconia films, and the test results of the thermal stability of the metal complexes are shown in Table 1. Specifically, a weight percent loss ≥ 99.8% indicates excellent thermal stability, and a weight percent loss ≥ 99.9% indicates good thermal stability. For uniformity testing, an electron force microscope (AFM) equipped with a low-noise Z-axis detector with a significant 0.2 nm noise bandwidth was used. A test result less than 2 nm indicates good uniformity, and a test result between 2-2.5 nm indicates excellent uniformity.

[0218] Table 1

[0219]

[0220] Note: "6N" indicates a purity of 99.999%.

[0221] The specific analytical 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" represents parts per billion (parts per billion, 10⁻⁶). -9 ).

[0226] Based on the data from Examples 1-6 and Comparative Example 1 in Table 1, and Figures 1-3 The thermogravimetric analysis results show that the synthetic route of this application can successfully obtain the target metal complex, and the yield level can be achieved in repeated experiments. Furthermore, the metal complex provided by this application has higher thermal stability. When used as a precursor material to prepare zirconia films, it can improve the purity and uniformity of zirconia films, thereby improving the performance stability of downstream products in industrial applications.

[0227] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention without departing from the principles and spirit of the present invention.

Claims

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

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

3. The metal complex as described in 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, Includes the following steps: Compound (a) and compound (b) were subjected to a first substitution reaction to prepare intermediate (c); Compound (d) and compound (e) were subjected to a second substitution reaction to prepare intermediate (f); The intermediate (c) and the intermediate (f) are subjected to a third substitution reaction to prepare the metal complex shown in formula (1); The compounds (a), (b), (c), (d), (e), (f), and the metal complex are respectively shown below: R1 to R2 and each of R3 are independently selected from alkyl groups having 1 to 5 carbon atoms.

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

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

7. The method for preparing the metal complex according to claim 6, characterized in that, The mass ratio of compound (e) to compound (d) is (2-10):(2-10); and / or The process for preparing intermediate (f) includes the following steps: At -40°C, NaH was added to a tetrahydrofuran solution of compound (d), and then compound (e) was added at -10°C to 0°C to carry out the reaction. After the reaction was completed, the reaction product of the second substitution reaction was obtained by quenching with alkaline ice water. The reaction product of the second substitution reaction was separated into liquid and liquid phase products to obtain organic phase products; The organic phase product was subjected to drying and vacuum distillation in sequence to obtain the intermediate (f).

8. The method for preparing the metal complex according to any one of claims 4 to 5, characterized in that, The molar ratio of intermediate (f) to intermediate (c) is (1–1.3):1; and / or The process for preparing the metal complex shown in formula (1) includes the following steps: Under conditions of 0℃-5℃, the intermediate (f) is added dropwise to a hexane solution of the intermediate (c) and mixed, and then the mixture is heated to reflux to carry out the reaction to obtain the reaction product of the third substitution reaction; The reaction product of the third substitution reaction is subjected to solid-liquid separation treatment to obtain filtrate; The filtrate was purified to obtain the metal complex shown in formula (1).

9. The use of the metal complex as described in any one of claims 1 to 3 in the preparation of zirconia films.

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

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