A zirconium compound, a precursor composition comprising the same, and a thin film and a method of manufacturing the same

Abstract

The present application belongs to the technical field of semiconductors, and particularly relates to a zirconium compound, a precursor composition containing the same, a thin film and a preparation method thereof. The zirconium compound has a chemical formula shown in formula 1, wherein R1, R2, R3 and R4 are each independently selected from one of H, methyl, ethyl or propyl. In the present application, nucleophilic substitution occurs between a pyrrole alkali metal salt and zirconium tetrachloride, and then the zirconium compound containing a cyclopentadiene and a pyrrole group is formed by reacting with cyclopentadiene. Compared with (cyclopentadienyl)tris(dimethylamino)zirconium, the zirconium compound has excellent thermal stability and excellent reactivity and volatility, which is helpful to form a high-purity low-impurity and uniform thin film, and greatly improves the quality of the thin film.

Description

Technical Field

[0001] This invention belongs to the field of semiconductor technology, specifically relating to a zirconium compound, a precursor composition containing the same, a thin film thereof, and a method for preparing the same. Background Technology

[0002] Semiconductor precursor materials are core materials in the thin film deposition process of integrated circuit manufacturing. They are mainly used in the thin film deposition process of the front-end process of integrated circuit wafer manufacturing. During the vapor deposition process, they form various thin film layers that meet the requirements of integrated circuit manufacturing. These films are the main "skeleton" that constitutes the microstructure of integrated circuits. In recent years, zirconium oxide (ZrO2), as a high-dielectric material (also known as a high-k material), has been increasingly widely used in the semiconductor field. Zirconia has high permittivity, good thermal stability, and a large band shift relative to silicon. It is considered one of the high-k materials that can replace silicon-based gate insulators. Zirconia 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 in semiconductor devices.

[0003] In deposition processes, the performance of the zirconium precursor largely determines deposition efficiency, film purity, and the electrical reliability of the final device. An ideal zirconium precursor typically requires high thermal stability, good volatility, and excellent reactivity. High thermal stability ensures the precursor remains stable during long-term heating and transport, preventing gaseous decomposition and avoiding the generation of solid particulate contaminants in pipelines and reaction chambers, thus guaranteeing long-term process stability and yield. Good volatility allows the precursor to be stably transported to the reaction chamber in gaseous form under mild heating conditions. Excellent reactivity enables the precursor to react rapidly with co-reactants, improving growth efficiency and achieving high-purity film growth at low temperatures.

[0004] Although some progress has been made in the zirconium precursor compounds currently in use, with the miniaturization and lightweighting of semiconductor devices, the performance requirements of zirconium oxide films for semiconductor devices such as DRAM gate dielectrics or capacitor dielectric films are becoming increasingly stringent. This places increasingly higher demands on the thermal stability of zirconium source precursors, which traditional zirconium source precursors cannot meet. Summary of the Invention

[0005] Therefore, the technical problem to be solved by this invention is to develop a novel zirconium precursor compound with high thermal stability, while maintaining volatility and reactivity comparable to or even exceeding that of existing zirconium precursors. This is of great significance for solving particulate contamination problems in high-temperature processes, broadening the process window, and improving film quality.

[0006] To address the aforementioned technical problems, the present invention provides the following technical solution: In a first aspect, this application provides a zirconium compound having the chemical formula shown in Formula 1. Formula 1 R1, R2, R3 and R4 are each independently selected from H, methyl, ethyl or propyl.

[0007] In some embodiments of this application, in the zirconium compound, R1, R2, R3, and R4 are one of the following formulas (i)-(iii): (i) R1, R2, R3 and R4 are all hydrogen; (ii) Any one of R1, R2, R3 and R4 is a substituent, and the rest are hydrogen; (iii) Any two of R1, R2, R3 and R4 are substituents, and the rest are hydrogen; Each of the substituents is independently selected from methyl, ethyl, or propyl.

[0008] In some embodiments of this application, the zirconium compound represented by Formula 1 is selected from compounds with the following structural formulas. .

[0009] Secondly, this application provides a method for preparing the zirconium compound described in the first aspect above, comprising the following steps: Step S1: Under conditions of anhydrous and oxygen-free environment and in the presence of organic solvent, an alkyl alkali metal salt is reacted with a pyrrole compound to prepare a pyrrole alkali metal salt, wherein the pyrrole compound is selected from pyrrole or substituted pyrrole. Step S2. Under conditions of anhydrous and oxygen-free environment and in the presence of organic solvent, pyrrole alkali metal salt is reacted with zirconium tetrachloride to prepare compound 2; Compound 2 has the structural formula shown in Formula 2 below: Formula 2 R1, R2, R3 and R4 are each independently selected from H, methyl, ethyl or propyl; Step S3. Compound 2 is reacted with cyclopentadiene under anhydrous, oxygen-free, and organic solvent conditions to obtain the compound shown in Formula 1.

[0010] In some embodiments of this application, the reaction in step S2 is carried out under reflux conditions, preferably for a reaction time of 4-6 hours; and / or, The reaction temperature in step S3 is -5 to 5°C, and the preferred reaction time is 1-3 hours; and / or, The reaction temperature in step S1 is -5 to -15°C, and the preferred reaction time is 1-3 hours.

[0011] In some embodiments of this application, the molar ratio of the alkyl alkali metal salt to the pyrrole compound is 1:1.0-1.2; and / or, The molar ratio of alkyl alkali metal salt to zirconium tetrachloride is 4-5:1; and / or, The molar ratio of compound 2 to cyclopentadiene is 1:1-1.2.

[0012] Thirdly, this application provides a zirconium-containing precursor composition for preparing thin films, comprising the zirconium compound described in the first aspect or the zirconium compound prepared by any of the preparation methods described in the second aspect.

[0013] Fourthly, this application provides the use of the zirconium-containing precursor composition described in the third aspect above in the preparation of zirconium oxide thin films.

[0014] Fifthly, this application provides a zirconium-containing thin film, which is prepared by deposition using a zirconium-containing precursor composition comprising the zirconium-containing precursor composition described in the third aspect above.

[0015] Sixthly, the application of the zirconium-containing thin films described in the fifth aspect in the semiconductor industry and / or microelectronics field.

[0016] Beneficial effects: This application describes a zirconium compound containing cyclopentadiene and pyrrole groups, formed by nucleophilic substitution of a pyrrole alkali metal salt with zirconium tetrachloride, followed by a reaction with cyclopentadiene. Compared to (cyclopentadienyl)tris(dimethylamino)zirconium, this zirconium compound exhibits excellent thermal stability, superior reactivity, and volatility, which facilitates the formation of high-purity, low-impurity, and uniform films, significantly improving film quality. Detailed Implementation

[0017] The present invention will now be described in detail with reference to embodiments. The principles and features of the present invention are described below with reference to embodiments. It should be noted that, unless otherwise specified, the embodiments and features described in these embodiments can be combined with each other. The embodiments given are only for explaining the present invention and are not intended to limit the scope of the present invention.

[0018] 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 invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0019] Unless otherwise stated or in case of contradiction, the terms or phrases used herein shall have the following meanings: As used herein, the term "and / or" includes any and all combinations of one or more of the related listed items.

[0020] In this application, terms such as "preferred," "better," "more suitable," and "ideal" are merely used to describe implementation methods or embodiments that achieve better results, and should be understood not to limit the scope of protection of this application.

[0021] In this application, terms such as "further," "even further," and "particularly" are used to describe purposes and indicate differences in content, but should not be construed as limiting the scope of protection of this application.

[0022] In this invention, the terms "first aspect," "second aspect," "third aspect," and "fourth aspect," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first," "second," "third," and "fourth," etc., serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on quantity.

[0023] In this application, the technical features described in an open-ended manner include both closed technical solutions consisting of the listed features and open technical solutions that include the listed features.

[0024] In this application, numerical intervals (i.e., numerical ranges) are involved. Unless otherwise specified, the selected numerical distributions within the aforementioned numerical intervals are considered continuous and include the two endpoints (i.e., the minimum and maximum values) of the numerical range, as well as every value between these two endpoints. Unless otherwise specified, when a numerical interval refers only to integers within that interval, it includes the two endpoint integers of the numerical range, as well as every integer between the two endpoints. In this document, this is equivalent to directly listing every integer. For example, if t is an integer selected from 1 to 10, it means that t is any integer selected from the group of integers consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. Furthermore, when multiple ranges are provided to describe features or characteristics, these ranges can be merged. In other words, unless otherwise specified, the ranges disclosed herein should be understood to include any and all subranges to which they are included.

[0025] Unless otherwise specified, the temperature parameters in this application are permitted to be either constant-temperature treatment or variations within a certain temperature range. It should be understood that the constant-temperature treatment allows temperature fluctuations within the precision range of the instrument control, such as ±5℃, ±4℃, ±3℃, ±2℃, or ±1℃.

[0026] In a first aspect, in one specific embodiment of this application, a zirconium compound having the chemical formula shown in Formula 1 is provided. Formula 1 R1, R2, R3 and R4 are each independently selected from H, methyl, ethyl or propyl.

[0027] In some embodiments of this application, in the zirconium compound, R1, R2, R3, and R4 are one of the following formulas (i)-(iii): (i) R1, R2, R3 and R4 are all hydrogen; (ii) Any one of R1, R2, R3 and R4 is a substituent, and the rest are hydrogen; (iii) Any two of R1, R2, R3 and R4 are substituents, and the rest are hydrogen; Each of the substituents is independently selected from methyl, ethyl, or propyl.

[0028] In some embodiments of this application, in order to better balance thermal stability and reactivity, the zirconium compound of formula 1 is selected from one of the following structural compounds, preferably compound 11.

[0029] .

[0030] The chemical formula shown for compound 11 is also known as (cyclopentadienyl)tripyrrolezirconium.

[0031] It is particularly important to note that, generally speaking, modifications to the molecular structure of precursor compounds aimed at improving thermal stability inevitably lead to changes in intermolecular forces, often resulting in a decrease in volatility and reactivity. Therefore, how to improve the thermal stability of precursor compounds while maintaining or even enhancing their reactivity and volatility is a significant challenge in this field. The inventors of this application have creatively introduced cyclopentadiene and pyrrole groups into zirconium compounds to obtain the zirconium compound shown in Formula 1. Experimental verification shows that, compared to (cyclopentadienyl)tris(dimethylamino)zirconium, the zirconium compound of this application exhibits excellent thermal stability, while also possessing superior reactivity and volatility. This contributes to the formation of high-purity, low-impurity, and uniform films, significantly improving the quality of the films.

[0032] Secondly, this application provides a method for preparing the zirconium compound shown in Formula 1 above, comprising the following steps: Step S1. Under conditions of anhydrous and oxygen-free environment and in the presence of organic solvent, an alkyl alkali metal salt is reacted with a pyrrole compound to prepare a pyrrole alkali metal salt, wherein the pyrrole compound is selected as pyrrole or substituted pyrrole; Step S2. Under conditions of anhydrous and oxygen-free environment and in the presence of organic solvent, pyrrole alkali metal salt is reacted with zirconium tetrachloride to prepare compound 2; Step S3. Under conditions of anhydrous and oxygen-free environment and in the presence of organic solvent, compound 2 is reacted with cyclopentadiene to obtain the compound shown in Formula 1; Compound 2 has the structural formula shown in Formula 2 below: Formula 2 R1, R2, R3 and R4 are each independently selected from H, methyl, ethyl or propyl.

[0033] In some embodiments of this application, R1, R2, R3, and R4 may have one or two that are not hydrogen, while the rest are hydrogen. In some embodiments, R1, R2, R3, and R4 may have one and only one that is an alkyl group, while the rest are hydrogen, wherein the alkyl group is selected from methyl, ethyl, or propyl.

[0034] In some embodiments of this application, the compound of Formula 2 is selected from one of the following structural formulas.

[0035] .

[0036] It should be noted that the preparation method of the pyrrole alkali metal salt described in this application includes: reacting an alkyl metal reagent with pyrrole or substituted pyrrole in an anhydrous and oxygen-free organic solvent; wherein, when pyrrole is used as a starting material, an unsubstituted pyrrole alkali metal salt is obtained; and when substituted pyrrole is used as a starting material, a substituted pyrrole alkali metal salt is obtained. In some embodiments, the substituted pyrrole is a compound that substitutes for a carbon atom on the pyrrole ring, such as, but not limited to, 2-methylpyrrole, 2-ethylpyrrole, 2-propylpyrrole, 2,3-dimethylpyrrole, 2,5-dimethylpyrrole, etc. It is understood that in the substituted pyrrole alkali metal salt, the substituent on the pyrrole ring is also attached to a carbon atom of the pyrrole ring, rather than to a nitrogen atom.

[0037] It should be noted that the term pyrrole alkali metal salt includes both substituted and unsubstituted forms.

[0038] In this application, the alkyl alkali metal salt has the structural formula M-R5, where M is an alkali metal and R5 is selected from methyl, ethyl, propyl, or butyl. In some embodiments, M is selected from one or more of lithium, sodium, potassium, rubidium, or cesium.

[0039] In this application, the pyrrole alkali metal salt has the following general formula: X - Y + , where X - Y is a pyrrole anion or a pyrrole anion substituted with at least one C1-4 alkyl substituent. + It is an alkali metal ion.

[0040] In some embodiments of this application, the pyrrole alkali metal salt is selected from one or more of lithium pyrrole, sodium pyrrole, or potassium pyrrole.

[0041] It is understandable that when R1, R2, R3 and R4 in Formula 2 are each independently selected from H, compound 2 is compound 21, also known as tetrapyrrolidinium zirconium.

[0042] In some embodiments of this application, in order to control the reaction rate, suppress side reactions, and improve selectivity, the pyrrole or substituted pyrrole in step S1 is added in batches to an organic solvent containing an alkyl alkali metal salt, preferably in 4-6 batches.

[0043] For the same reason, the zirconium tetrachloride described in step S2 is added in batches to an organic solvent containing pyrrole alkali metal salt.

[0044] For example, the chemical reaction equation for the zirconium compound shown in Formula 1 can be as follows:

[0045] In some embodiments of this application, the reaction described in step S2 is carried out under reflux conditions, preferably for a reaction time of 4-6 hours.

[0046] In some embodiments of this application, the temperature of the reaction in step S3 is -5 to 5°C, and the preferred reaction time is 2-4 hours.

[0047] In some embodiments of this application, the temperature of the reaction in step S1 is -5 to -15°C, and the preferred reaction time is 1-3 hours.

[0048] In some embodiments of this application, step S2 further includes filtering the product of the reaction between the pyrrole alkali metal salt and zirconium tetrachloride and distilling it under reduced pressure to obtain compound 2.

[0049] In some embodiments of this application, step S3 further includes filtering the product after reacting compound 2 with cyclopentadiene, vacuum distilling, and fractional distillation to obtain the compound shown in Formula 1.

[0050] In some embodiments of this application, the molar ratio of the alkyl alkali metal salt to the pyrrole compound is 1:1.0-1.2.

[0051] In some embodiments of this application, the molar ratio of alkyl alkali metal salt to zirconium tetrachloride is 4-5:1. In some embodiments of this application, the molar ratio of zirconium tetrachloride to cyclopentadiene is 1:1-1.2.

[0052] In some embodiments of this application, the organic solvent is selected from n-hexane or tetrahydrofuran.

[0053] Thirdly, this application provides a zirconium-containing precursor composition for preparing thin films, comprising the zirconium compound of Formula 1 or the zirconium compound of Formula 1 obtained by the above preparation method.

[0054] In some embodiments of this application, the zirconium compound content in the zirconium-containing precursor composition is 1-100 wt%.

[0055] Fourthly, this application provides an application of the zirconium compound of the first aspect or the zirconium compound prepared by the second aspect in the preparation of zirconium oxide thin films.

[0056] Fifthly, this application provides the use of the zirconium-containing precursor composition described in the third aspect above in the preparation of zirconium oxide thin films.

[0057] In a sixth aspect, this application provides a zirconium-containing thin film, which is prepared by deposition using a zirconium-containing precursor composition as described in the third aspect.

[0058] In some embodiments of this application, the carbon content in the zirconium-containing film is less than or equal to 500 ppm, preferably 400-500 ppm.

[0059] In a seventh aspect, this application provides a method for preparing a zirconium-containing thin film, which includes the step of depositing the zirconium-containing precursor composition described in the third aspect on a substrate.

[0060] In this application, specific examples of deposition include, but are not limited to, one or more of the following: thermal atomic layer deposition, thermochemical vapor deposition, plasma-enhanced atomic layer deposition, or plasma-enhanced chemical vapor deposition.

[0061] In some embodiments of this application, the preparation method includes the following steps: (1) Provide a substrate in the reaction chamber; (2) Introduce a zirconium-containing precursor composition into the reaction chamber, so that it chemically adsorbs onto the substrate surface to form a first reaction product on the substrate surface; (3) Introduce oxygen source plasma gas into the reaction chamber to react with the first reaction product to obtain a zirconium oxide film.

[0062] In some embodiments of this application, the above preparation method includes repeating steps (2) to (3) at least twice; preferably repeating steps (2) to (3) 2-100 times. It should be noted that in the above repeated cyclic operation, after the first cycle, in subsequent repeated operations, the zirconium-containing precursor composition described in step (1) undergoes chemical adsorption with the zirconium oxide film obtained in the previous cycle step (3) to form a first reaction product. By controlling the number of cycles, a zirconium oxide film of a predetermined thickness is obtained.

[0063] In some embodiments of this application, the substrate is a type of material commonly used in the semiconductor industry and microelectronics field. Those skilled in the art can make adaptive choices from the prior art according to actual needs. This invention is not particularly limited, and specific examples include, but are not limited to, one or more of silicon wafers, quartz, glass, and resin.

[0064] In some embodiments of this application, step (2) of introducing the zirconium-containing precursor composition into the reaction chamber for chemical adsorption specifically includes: using a gas carrier to introduce the zirconium-containing precursor composition into the reaction chamber in a pulsed manner, wherein the zirconium-containing precursor composition contacts the substrate surface for chemical adsorption to obtain the first reaction product. Further, the pulse period is as follows: the zirconium-containing precursor composition is introduced into the reaction chamber using a carrier gas for 5-10 seconds, followed by purging with a carrier gas for 30-40 seconds.

[0065] It should be noted that the methods used in this application to transport the zirconium precursor composition using a gas carrier are all prior art and will not be described in detail here. For example, the zirconium precursor composition can be placed in a stainless steel source bottle, which is connected to the reaction chamber of the deposition equipment via pipeline. The temperature of the source bottle is controlled, and a carrier gas is introduced. The temperature of the source bottle is controlled to be 50-100°C.

[0066] In some embodiments of this application, the carrier gas specifically includes, but is not limited to, one or more of nitrogen, argon, helium, or krypton.

[0067] In some implementations, the flow rate of the carrier in step (2) is 100-500 sccm.

[0068] In some embodiments, the zirconium-containing precursor composition undergoes chemisorption with the substrate surface for 2-10 seconds. It is understood that the substrate surface in this application may be the surface of a substrate material, or it may include the surface of a previously deposited material layer.

[0069] In some embodiments, during step (2), when the zirconium-containing precursor composition is chemically adsorbed onto the substrate, the temperature of the reaction chamber is 250-450°C.

[0070] In some embodiments of this application, in step (3), the oxygen source plasma refers to reactive oxygen-containing gas generated in situ or remotely by a plasma generator, and specific examples include, but are not limited to, oxygen plasma gas and / or ozone plasma.

[0071] In some embodiments of this application, the flow rate of the oxygen source plasma gas is 100-500 sccm.

[0072] In some embodiments of this application, the reaction time between the oxygen source plasma gas and the first reaction product is 10-60 s, preferably 20-30 s.

[0073] In some embodiments of this application, the temperature of the reaction in step (3) is 250-450°C.

[0074] Eighth aspect, the application of the zirconium-containing thin films described in the sixth aspect in the semiconductor industry and / or microelectronics field.

[0075] The beneficial effects of the zirconium compounds and their preparation methods described in this application will be illustrated below through specific examples.

[0076] All raw materials and reagents used in this invention were purchased from mainstream manufacturers on the market. Those without specified manufacturers or concentrations are all analytical grade raw materials or reagents that are routinely available. There are no particular restrictions as long as they achieve the intended effect. The instruments and equipment used in this embodiment were all purchased from major manufacturers on the market. There are no particular limitations as long as they achieve the intended effect. Where specific techniques or conditions are not specified in this embodiment, they shall be performed in accordance with the techniques or conditions described in the literature in this field or according to the product instructions.

[0077] The reagents and instruments used in the embodiments and comparative examples of this application are shown in Table 1. Table 1. Reagents and instruments used in the embodiments and comparative examples of this application. name Model / Specification Manufacturer for sale Zirconium tetrachloride Z109459 Shanghai Aladdin Biochemical Technology Co., Ltd. n-Butyllithium B107554 Shanghai Aladdin Biochemical Technology Co., Ltd. Pyrrole Shanghai Aladdin Biochemical Technology Co., Ltd. 2-Methylpyrrole 1062417 Shanghai Haohong Biomedical Technology Co., Ltd. 2-Ethylpyrrole 002567 Beijing Bailingwei Technology Co., Ltd. 2-Propylpyrrole Sigma Aldrich (Shanghai) Trading Co., Ltd. 2,5-Dimethylpyrrole D183601 Sigma Aldrich (Shanghai) Trading Co., Ltd. (cyclopentadienyl)tris(dimethylamino)zirconium Beijing Huawirui Chemical Technology Co., Ltd. Example 1

[0078] 1. Preparation of Zirconium Compounds S1. In an anhydrous and oxygen-free glove box environment, set up the experimental apparatus using a dry three-necked flask. Add 150g of dry n-hexane to the three-necked flask. At -10℃, add 95.52g of n-butyllithium n-hexane solution (23.6wt%) to the three-necked flask. Maintain the temperature at -10℃, and slowly add a total of 25.86g of pyrrole (5.172g per batch) to the three-necked flask in 5 batches. After the addition is complete, stir the reaction for 1 hour.

[0079] S2. The reaction solution from step S1 was heated to room temperature, and a total of 20 g of zirconium tetrachloride was added in portions to a three-necked flask. The mixture was heated to reflux and stirred for 5 h. After filtration, the solvent was removed by vacuum distillation. 26.8 g of tetrapyrrolidinium zirconium (compound 21) was obtained, with a yield of approximately 88% and a purity of 97%.

[0080] The obtained tetrapyrrolidinium zirconium was identified by 1H NMR, with the following data: 1H NMR (400 MHz, C6D6): δ7.26 (8H,t), δ6.28 (8H,t). The results indicate that the target product was successfully obtained.

[0081] S3. In an anhydrous and oxygen-free glove box environment, using a dry three-necked flask, the experimental setup was constructed. At 0°C, 150g of dry n-hexane and 26.8g of tetrapyrrolidinium zirconium were added to the three-necked flask. The mixture was stirred thoroughly, and the temperature was maintained at 0°C. 5.48g of cyclopentadiene was slowly added to the three-necked flask, and the reaction was stirred for 1 hour. The temperature was then slowly raised to room temperature, and the solvent was removed by vacuum distillation. 24.25g of crude product was obtained. After purification by distillation at 0.1 torr and 100°C, 19.88g of a white liquid with a purity of 99.99% and a yield of 74% was obtained.

[0082] The obtained white liquid was identified by 1H NMR, with the following data: 1H NMR (400 MHz, C6D6): δ7.26 (6H, t); δ6.5 (2H, t); δ6.4 (2H, t); δ6.28 (6H, t); δ2.9 (1H, s). The results indicate that compound 11, namely (cyclopentadienyl)tripyrrolezirconium, was successfully obtained.

[0083] 2. Preparation of zirconia thin films: (1) Place the silicon wafer in the reaction chamber of the ALD equipment and set the deposition temperature to 250°C; (2) Nitrogen carrier gas is introduced into the reaction chamber at a flow rate of 200 sccm. (Cyclopentadienyl)tripyrrolidinium is introduced into the reaction chamber in a pulsed manner for 6 s to allow (cyclopentadienyl)tripyrrolidinium to chemically adsorb onto the substrate. Nitrogen gas is then introduced for 30 s to purge. (3) Introduce oxygen plasma gas into the reaction chamber at a flow rate of 200 sccm for 30 s to obtain a zirconia film. After the zirconia film is formed, introduce nitrogen gas again to remove unreacted precursor materials and byproducts. Repeat steps (2)-(3) above 4 times to obtain a zirconia film on the substrate. After the first cycle, the substrate in step (2) is the zirconia film obtained in the previous cycle step (3).

[0084] Example 2 1. Preparation of Zirconium Compounds S1. In an anhydrous and oxygen-free glove box environment, set up the experimental apparatus using a dry three-necked flask. Add 150g of dry n-hexane to the three-necked flask. At -5℃, add 95.6g of n-butyllithium n-hexane solution (23.6wt%) to the three-necked flask. Maintain the temperature at -5℃, and slowly add a total of 23.6g of pyrrole (4.717g per batch) in 5 batches. After the addition is complete, stir the reaction for 3 hours.

[0085] S2. The reaction solution from step S1 was heated to room temperature, and a total of 18.2 g of zirconium tetrachloride was added in portions to a three-necked flask. The mixture was heated to reflux and stirred for 4 hours. After filtration, the solvent was removed by vacuum distillation. 22.70 g of tetrapyrrolidinium zirconium was obtained, with a yield of 82% and a purity of 97%.

[0086] The obtained tetrapyrrolidinium zirconium was identified by 1H NMR, with the following data: 1H NMR (400 MHz, C6D6): (7.26, 8H, 6.28, 8H). The results indicate that the target product was successfully obtained.

[0087] S3. In an anhydrous and oxygen-free glove box environment, using a dry three-necked flask, set up the experimental apparatus. At -5°C, add 150g of dry n-hexane and 22.70g of tetrapyrrolidinium zirconium to the three-necked flask, stir until homogeneous, maintain the temperature at -5°C, and slowly add 4.22g of cyclopentadiene to the three-necked flask. Stir the reaction for 3 hours, then slowly raise the temperature to room temperature. Remove the solvent by vacuum distillation. 19.40g of crude product was obtained, which was purified by distillation at 0.1 torr and 100°C to obtain 16.15g of a white liquid, with a yield of 71%.

[0088] The obtained white liquid was identified by 1H NMR spectroscopy, with the following specific data: 1H NMR (400MHz, C6D6): (7.26, 6H; 6.5, 2H; 6.4, 2H; 6.28, 6H; 2.9, 1H). The results indicate that compound 11, namely (cyclopentadienyl)tripyrrolezirconium, was successfully obtained.

[0089] 2. Preparation of zirconia thin films: (1) Place the silicon wafer in the reaction chamber of the ALD equipment and set the deposition temperature to 250°C; (2) Nitrogen carrier gas is introduced into the reaction chamber at a flow rate of 200 sccm. (Cyclopentadienyl)tripyrrolidinium is introduced into the reaction chamber in a pulsed manner for 6 s to allow (cyclopentadienyl)tripyrrolidinium to chemically adsorb onto the substrate. Nitrogen gas is then introduced for 30 s to purge. (3) Introduce oxygen plasma gas into the reaction chamber at a flow rate of 200 sccm for 30 s to obtain a zirconia film. After the zirconia film is formed, introduce nitrogen gas again to remove unreacted precursor materials and byproducts. Repeat steps (2)-(3) above 4 times to obtain a zirconia film on the substrate. After the first cycle, the substrate in step (2) is the zirconia film obtained in the previous cycle step (3).

[0090] Example 3 1. Preparation of Zirconium Compounds S1. In an anhydrous and oxygen-free glove box environment, set up the experimental apparatus using a dry three-necked flask. Add 150g of dry n-hexane to the three-necked flask. At -15℃, add 95.55g of n-butyllithium hexane solution (23.6%) to the three-necked flask. Maintain the temperature at -15℃, and slowly add a total of 28.22g of pyrrole (5.64g per batch) to the three-necked flask in 5 batches. After the addition is complete, stir the reaction for 2 hours.

[0091] S2. The reaction solution from step S1 was heated to room temperature, and a total of 16.35 g of zirconium tetrachloride was added in portions to a three-necked flask. The mixture was heated to reflux and stirred for 6 hours. After filtration, the solvent was removed by vacuum distillation. 22.4 g of tetrapyrrolidinium zirconium was obtained, with a yield of 90% and a purity of 98%.

[0092] The obtained tetrapyrrolidinium zirconium was identified by 1H NMR, with the following data: 1H NMR (400 MHz, C6D6): (7.26, 8H, 6.28, 8H). The results indicate that the target product was successfully obtained.

[0093] S3. In an anhydrous and oxygen-free glove box environment, using a dry three-necked flask, set up the experimental apparatus. At 5°C, add 150g of dry n-hexane and 20g of tetrapyrrolidinium zirconium to the three-necked flask, stir until homogeneous, maintain the temperature at 5°C, and slowly add 4.5g of cyclopentadiene to the three-necked flask. Stir the reaction for 2 hours, then slowly raise the temperature to room temperature. Remove the solvent by vacuum distillation. 18.3g of crude product was obtained, which was purified by distillation at 0.1 torr and 100°C to obtain 14.8g of a white liquid, with a yield of 74%.

[0094] The obtained white liquid was identified by 1H NMR spectroscopy, with the following specific data: 1H NMR (400MHz, C6D6): (7.26, 6H; 6.5, 2H; 6.4, 2H; 6.28, 6H; 2.9, 1H). The results indicate that compound 11, namely (cyclopentadienyl)tripyrrolezirconium, was successfully obtained.

[0095] 2. Preparation of zirconia thin films: (1) Place the silicon wafer in the reaction chamber of the ALD equipment and set the deposition temperature to 250°C; (2) Nitrogen carrier gas is introduced into the reaction chamber at a flow rate of 200 sccm. (Cyclopentadienyl)tripyrrolidinium is introduced into the reaction chamber in a pulsed manner for 6 s to allow (cyclopentadienyl)tripyrrolidinium to chemically adsorb onto the substrate. Nitrogen gas is then introduced for 30 s to purge. (3) Introduce oxygen plasma gas into the reaction chamber at a flow rate of 200 sccm for 30 s to obtain a zirconia film. After the zirconia film is formed, introduce nitrogen gas again to remove unreacted precursor materials and byproducts. Repeat steps (2)-(3) above 4 times to obtain a zirconia film on the substrate. After the first cycle, the substrate in step (2) is the zirconia film obtained in the previous cycle step (3).

[0096] Example 4 1. Preparation of Zirconium Compounds S1. In an anhydrous and oxygen-free glove box environment, set up the experimental apparatus using a dry three-necked flask. Add 150g of dry n-hexane to the three-necked flask. At -10℃, add 95.52g of n-butyllithium n-hexane solution (23.6wt%) to the three-necked flask. Maintain the temperature at -10℃, and slowly add a total of 31.4g of 2-methylpyrrole (6.3g per batch) to the three-necked flask in 5 batches. After the addition is complete, stir the reaction for 1 hour.

[0097] S2. The reaction solution from step S1 was heated to room temperature, and a total of 20 g of zirconium tetrachloride was added in portions to a three-necked flask. The mixture was heated to reflux and stirred for 5 hours. After filtration, the solvent was removed by vacuum distillation. 31.4 g was obtained, with a yield of 89% and a purity of 97.8%.

[0098] Compound 22 was identified by 1H NMR, with the following data: 1H NMR (400MHz, C6D6): δ7.00 (4H, d), δ6.12 (4H, d); δ5.85 (4H, d); 2.12 (12H, s). The results indicate that the target product was successfully obtained.

[0099] S3. In an anhydrous and oxygen-free glove box environment, a dry three-necked flask was used to set up the experimental apparatus. At 0°C, 150g of dry n-hexane and 28.4g of compound 22 were added to the three-necked flask, stirred thoroughly, and the temperature was maintained at 0°C. 5.48g of cyclopentadiene was slowly added to the three-necked flask, and the reaction was stirred for 1 hour. The temperature was then slowly raised to room temperature, and the solvent was removed by vacuum distillation. 24.9g of crude product was obtained, which was purified by distillation at 0.1 torr and 100°C to obtain 19.4g of a white liquid with a purity of 99.9% and a yield of 70.2%.

[0100] The obtained white liquid was identified by 1H NMR, with the following data: 1H NMR (400 MHz, C6D6): δ7.00 (3H, d), δ6.50 (2H, d), δ6.40 (2H, d), δ6.12 (3H, d); δ5.85 (3H, d); δ2.90 (1H, s), δ2.12 (9H, s). The results indicate that compound 12 was successfully obtained.

[0101] 2. Preparation of zirconia thin films: (1) Place the silicon wafer in the reaction chamber of the ALD equipment and set the deposition temperature to 250°C; (2) Nitrogen carrier gas is introduced into the reaction chamber at a flow rate of 200 sccm. Compound 12 is introduced into the reaction chamber in a pulsed manner for 6 s to allow compound 12 to chemically adsorb onto the substrate. Nitrogen gas is then introduced for 30 s to purge the mixture. (3) Introduce oxygen plasma gas into the reaction chamber at a flow rate of 200 sccm for 30 s to obtain a zirconia film. After the zirconia film is formed, introduce nitrogen gas again to remove unreacted precursor materials and byproducts. Repeat steps (2)-(3) above 4 times to obtain a zirconia film on the substrate. After the first cycle, the substrate in step (2) is the zirconia film obtained in the previous cycle step (3).

[0102] Example 5 1. Preparation of Zirconium Compounds S1. In an anhydrous and oxygen-free glove box environment, set up the experimental apparatus using a dry three-necked flask. Add 150g of dry n-hexane to the three-necked flask. At -10℃, add 95.52g of n-butyllithium n-hexane solution (23.6wt%) to the three-necked flask. Maintain the temperature at -10℃, and slowly add a total of 36.8g of 2-ethylpyrrole (7.36g per batch) to the three-necked flask in 5 batches. After the addition is complete, stir the reaction for 1h.

[0103] S2. The reaction solution from step S1 was heated to room temperature, and a total of 20 g of zirconium tetrachloride was added in portions to a three-necked flask. The mixture was heated to reflux and stirred for 5 h. After filtration, the solvent was removed by vacuum distillation. 36.5 g of compound 23 was obtained, with a yield of 98%.

[0104] Compound 23 was identified by 1H NMR, with the following data: 1H NMR (400MHz, C6D6): δ7.00 (4H, d), δ6.12 (4H, d); δ5.85 (4H, d); δ3.11 (8H, q); δ1.29 (12H, t). The results indicate that the target product was successfully obtained.

[0105] S3. In an anhydrous and oxygen-free glove box environment, using a dry three-necked flask, the experimental setup was constructed. At 0°C, 150g of dry n-hexane was added to the three-necked flask, followed by 32.3g of compound 23. The mixture was stirred thoroughly, and the temperature was maintained at 0°C. 5.48g of cyclopentadiene was slowly added to the three-necked flask, and the reaction was stirred for 1 hour. The temperature was then slowly raised to room temperature, and the solvent was removed by vacuum distillation. 32.5g of crude product was obtained. This crude product was purified by distillation at 0.1 torr and 100°C to obtain 26.6g of a white liquid with a purity of 99.9% and a yield of 74.5%.

[0106] The obtained white liquid was identified by 1H NMR, with the following data: 1H NMR (400MHz, C6D6): δ7.00 (3H, d), δ6.50 (2H, d), δ6.40 (2H, d), δ6.12 (3H, d); δ5.85 (3H, d); δ3.11 (4H, q), δ2.90 (1H, s), δ1.29 (9H, t). The results indicate that compound 13 was successfully obtained.

[0107] 2. Preparation of zirconia thin films: (1) Place the silicon wafer in the reaction chamber of the ALD equipment and set the deposition temperature to 250°C; (2) Nitrogen carrier gas is introduced into the reaction chamber at a flow rate of 200 sccm. Compound 13 is introduced into the reaction chamber in a pulsed manner for 6 s to allow compound 13 to chemically adsorb onto the substrate. Nitrogen gas is then introduced for 30 s to purge the mixture. (3) Introduce oxygen plasma gas into the reaction chamber at a flow rate of 200 sccm for 30 s to obtain a zirconia film. After the zirconia film is formed, introduce nitrogen gas again to remove unreacted precursor materials and byproducts. Repeat steps (2)-(3) above 4 times to obtain a zirconia film on the substrate. After the first cycle, the substrate in step (2) is the zirconia film obtained in the previous cycle step (3).

[0108] Example 6 1. Preparation of Zirconium Compounds S1. In an anhydrous and oxygen-free glove box environment, set up the experimental apparatus using a dry three-necked flask. Add 150g of dry n-hexane to the three-necked flask. At -10℃, add 95.52g of n-butyllithium n-hexane solution (23.6wt%) to the three-necked flask. Maintain the temperature at -10℃, and slowly add a total of 42.2g of 2-propylpyrrole (8.45g per batch) to the three-necked flask in 5 batches. After the addition is complete, stir the reaction for 1 hour.

[0109] S2. The reaction solution from step S1 was heated to room temperature, and a total of 20 g of zirconium tetrachloride was added in portions to a three-necked flask. The mixture was heated to reflux and stirred for 5 h. After filtration, the solvent was removed by vacuum distillation. 40 g of compound 24 was obtained, with a yield of 89% and a purity of 98%.

[0110] The obtained tetrapyrrolidinium zirconium was identified by 1H NMR, with the following data: 1H NMR (400 MHz, C6D6): δ7.00 (4H, d), δ6.12 (4H, d); δ5.85 (4H, d); δ2.48 (8H, q); δ1.66 (8H, m); δ0.95 (12H, t). The results indicate that the target product was successfully obtained.

[0111] S3. In an anhydrous and oxygen-free glove box environment, using a dry three-necked flask, the experimental setup was constructed. At 0°C, 150g of dry n-hexane was added to the three-necked flask, followed by 36.2g of compound 24. The mixture was stirred thoroughly, and the temperature was maintained at 0°C. 5.48g of cyclopentadiene was slowly added to the flask, and the reaction was stirred for 1 hour. The mixture was then slowly raised to room temperature, and the solvent was removed by vacuum distillation. 29.2g of crude product was obtained. This crude product was purified by distillation at 0.1 torr and 100°C to obtain 23.4g of a white liquid with a purity of 99.9% and a yield of 70.4%.

[0112] The obtained white liquid was identified by 1H NMR, with the following data: 1H NMR (400 MHz, C6D6): δ7.00 (3H, d), δ6.50 (2H, d), δ6.40 (2H, d), δ6.12 (3H, d); δ5.85 (3H, d); δ2.90 (1H, s); δ2.48 (6H, q); δ1.66 (6H, m); δ0.95 (9H, t). The results indicate that compound 14 was successfully obtained.

[0113] 2. Preparation of zirconia thin films: (1) Place the silicon wafer in the reaction chamber of the ALD equipment and set the deposition temperature to 250°C; (2) Nitrogen carrier gas is introduced into the reaction chamber at a flow rate of 200 sccm. Compound 14 is introduced into the reaction chamber in a pulsed manner for 6 s to allow zirconium compound 14 to chemically adsorb onto the substrate. Nitrogen gas is then introduced for 30 s to purge. (3) Introduce oxygen plasma gas into the reaction chamber at a flow rate of 200 sccm for 30 s to obtain a zirconia film. After the zirconia film is formed, introduce nitrogen gas again to remove unreacted precursor materials and byproducts. Repeat steps (2)-(3) above 4 times to obtain a zirconia film on the substrate. After the first cycle, the substrate in step (2) is the zirconia film obtained in the previous cycle step (3).

[0114] Example 7 1. Preparation of Zirconium Compounds S1. In an anhydrous and oxygen-free glove box environment, set up the experimental apparatus using a dry three-necked flask. Add 150g of dry n-hexane to the three-necked flask. At -10℃, add 95.52g of n-butyllithium n-hexane solution (23.6wt%) to the three-necked flask. Maintain the temperature at -10℃, and slowly add a total of 36.8g of 2,5-dimethylpyrrole (7.36g per batch) to the three-necked flask in 5 batches. After the addition is complete, stir the reaction for 1h.

[0115] S2. The reaction solution from step S1 was heated to room temperature, and a total of 20 g of zirconium tetrachloride was added in portions to a three-necked flask. The mixture was heated to reflux and stirred for 5 hours. After filtration, the solvent was removed by vacuum distillation. 35.3 g of compound 25 was obtained, with a yield of 88% and a purity of 98%.

[0116] Compound 25 was identified by 1H NMR spectroscopy, with the following data: 1H NMR (400 MHz, C6D6): δ5.69 (8H, d), δ2.12 (24H, s). The results indicate that the target product was successfully obtained.

[0117] S3. In an anhydrous and oxygen-free glove box environment, a dry three-necked flask was used to set up the experimental apparatus. At 0°C, 150g of dry n-hexane and 32.3g of compound 25 were added to the three-necked flask, stirred thoroughly, and the temperature was maintained at 0°C. 5.48g of cyclopentadiene was slowly added to the three-necked flask, and the reaction was stirred for 1 hour. The temperature was then slowly raised to room temperature, and the solvent was removed by vacuum distillation. 26.6g of crude product was obtained. After purification by distillation at 0.1 torr and 100°C, 21.6g of a white liquid with a purity of 99.9% and a yield of 71.3% was obtained.

[0118] The obtained white liquid was identified by 1H NMR, with the following data: 1H NMR (400MHz, C6D6): δ5.69 (6H, d), δ6.50 (2H, d), δ6.40 (2H, d), δ2.90 (1H, s), δ2.12 (18H, s). The results indicate that compound 15 was successfully obtained.

[0119] 2. Preparation of zirconia thin films: (1) Place the silicon wafer in the reaction chamber of the ALD equipment and set the deposition temperature to 250°C; (2) Nitrogen carrier gas is introduced into the reaction chamber at a flow rate of 200 sccm. Compound 15 is introduced into the reaction chamber in a pulsed manner for 6 s to allow compound 15 to chemically adsorb onto the substrate. Nitrogen gas is then introduced for 30 s to purge the mixture. (3) Introduce oxygen plasma gas into the reaction chamber at a flow rate of 200 sccm for 30 s to obtain a zirconia film. After the zirconia film is formed, introduce nitrogen gas again to remove unreacted precursor materials and byproducts. Repeat steps (2)-(3) above 4 times to obtain a zirconia film on the substrate. After the first cycle, the substrate in step (2) is the zirconia film obtained in the previous cycle step (3).

[0120] Comparative Example 1 Preparation of zirconia thin films: (1) Place the silicon wafer in the reaction chamber of the ALD equipment and set the deposition temperature to 250°C; (2) Nitrogen carrier gas is introduced into the reaction chamber at a flow rate of 200 sccm. (Cyclopentadienyl)tri(dimethylamino)zirconium is introduced into the reaction chamber in a pulsed manner for 6 s to allow (cyclopentadienyl)tri(dimethylamino)zirconium to chemically adsorb onto the substrate. Nitrogen gas is then introduced for 30 s to purge. (3) Introduce oxygen plasma gas into the reaction chamber at a flow rate of 200 sccm for 30 s to obtain a zirconia film. After the zirconia film is formed, introduce nitrogen gas again to remove unreacted precursor materials and byproducts. Repeat steps (2)-(3) above 4 times to obtain a zirconia film on the substrate. After the first cycle, the substrate in step (2) is the zirconia film obtained in the previous cycle step (3).

[0121] Experimental Example The zirconium compounds and zirconium oxide films prepared in the above examples and comparative examples were tested according to the following methods, and the results are shown in Tables 2 and 3.

[0122] 1. Thermal stability test: The thermal stability of zirconium compounds was analyzed according to ASTM E537-24, "Differential Scanning Calorimetry (DSC) Standard Test Method for Determining the Thermal Stability of Chemicals". The analysis conditions included a temperature range of 50℃ to 450℃ and a heating rate of 15℃ / min. The initial decomposition temperature and the peak exothermic temperature of the zirconium compounds were measured, and the results are shown in Table 2.

[0123] 2. Volatility test: Thermogravimetric analysis (TGA 550) was performed on zirconium compounds under the following conditions: temperature range of 50℃ to 450℃, heating rate of 15℃ / min. A smooth, stepless weight loss curve and a residual weight ≤0.5% were considered to indicate excellent volatility.

[0124] 3. Viscosity test: The viscosity of the zirconium compound was tested using an Anton Paar SVM 2001 kinematic viscometer. The test conditions were: measuring cell temperature 25℃, shear rate 583±1l / s, and shear force 5±0.005Pa.

[0125] 4. Test methods for reactivity: (1) Place the silicon wafer in the reaction chamber of the ALD equipment and set the deposition temperature to 250°C; (2) Nitrogen carrier gas is introduced into the reaction chamber at a flow rate of 200 sccm. Zirconium compound is introduced into the reaction chamber in a pulsed manner for 0.5 s to allow the zirconium compound to chemically adsorb onto the substrate. Nitrogen gas is then introduced for 10 s to purge. (3) Water vapor plasma is introduced into the reaction chamber at a flow rate of 200 sccm for 0.3 s to obtain a zirconia film. After the zirconia film is formed, nitrogen gas is introduced again to remove unreacted zirconium compound precursor materials and by-products. Repeat steps (2)-(3) above 200 times to obtain a zirconia film on the substrate. Use an ellipsometry to test the film thickness and calculate the film thickness per cycle (Å / cycle).

[0126] Activity determination criteria: Thin film thickness per cycle of 1.2–1.3 Å: minor CVD and overreaction occur; A film thickness of 0.8–1.2 Å / cycle is considered good activity. Within this range, a larger film thickness per unit cycle indicates greater precursor activity. Thin film thickness of 0.5–0.8 Å / cycle: classified as poor activity; Thin film thickness per cycle < 0.5 Å / cycle: poor activity and difficult adsorption; Unit cycle film thickness > 1.3 Å: CVD and over-reaction occur.

[0127] 5. Metal purity test: The metal purity in the thin film was tested using ICP-MS (LabMS 3000).

[0128] Test conditions: atomizer flow rate 0.86 L / min, oxygen AMS flow rate: 0.05 L / min. Metal purity was assessed based on ICP-MS test results from each embodiment and comparative example. The metal purity of the zirconia film was calculated as (1 - the sum of the contents of all metals except Zr) * 100%, where "6N" indicates a purity of 99.9999%.

[0129] 6. Uniformity Test: The uniformity of the film surface is tested using AFM (Atomic Force Microscopy). The AFM is equipped with a low-noise Z-axis detector with a noise bandwidth of 0.2 nm. When the measured mean square roughness of the sample surface is less than 2 nm, the uniformity is judged as excellent; when the measured mean square roughness of the sample surface is 2-2.5 nm, the uniformity is judged as good.

[0130] 7. Test method for carbon content of thin films: The elemental composition of thin films was tested using an XPS instrument (ThermoFisher EscaLab Xi+). Since hydrogen and helium lack inner electron energy levels, XPS cannot detect hydrogen and helium. The carbon content measured by XPS in Table 3 is relative to the content of all elements except hydrogen and helium.

[0131] Table 2 Test results of zirconium compounds Example Initial decomposition temperature (°C) Reaching the peak heat release temperature (°C) volatility Viscosity, mPa·S Reactivity, Å / cycle Example 1 190 263 excellent 6.7 1.0 Example 2 193 262 excellent 6.7 1.0 Example 3 192 264 excellent 6.8 1.0 Example 4 198 266 excellent 6.9 1.0 Example 5 202 270 excellent 7.1 1.0 Example 6 207 272 excellent 7.4 1.0 Example 7 203 270 excellent 7.1 1.0 Comparative Example 1 182 243 excellent 8.4 0.8 Table 3 Test results of zirconium oxide thin films Metal purity Uniformity Carbon content of the film, ppm Example 1 7N excellent 423 Example 2 7N excellent 435 Example 3 7N excellent 452 Example 4 7N excellent 424 Example 5 7N excellent 437 Example 6 7N excellent 432 Example 7 7N excellent 424 Comparative Example 1 7N good 725 As shown in Table 2, the onset temperatures of the zirconium compounds prepared in Examples 1-7 of this application are in the range of 190-207℃, and the temperatures reaching the exothermic peak are in the range of 262-272℃, both higher than those in Comparative Example 1. This indicates that the thermal stability of the zirconium precursors prepared in this application is significantly better than that of (cyclopentadienyl)tris(dimethylamino)zirconium. Furthermore, the volatility of the zirconium compounds in this application is comparable to that of (cyclopentadienyl)tris(dimethylamino)zirconium, while their viscosity and reactivity are superior.

[0132] As shown in Table 3, the zirconium oxide films prepared using the zirconium compounds in Examples 1-7 of this application have better uniformity and purity than the (cyclopentadienyl)tris(dimethylamino)zirconium precursor.

[0133] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

[0134] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, Those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of the different embodiments or examples.

[0135] 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.

Claims

1. A zirconium compound, characterized in that, It has the chemical formula shown in Formula 1. ； R1, R2, R3 and R4 are each independently selected from H, methyl, ethyl or propyl.

2. The zirconium compound according to claim 1, characterized in that, In the zirconium compound, R1, R2, R3, and R4 are one of the following formulas (i)-(iii): (i) R1, R2, R3 and R4 are all hydrogen; (ii) Any one of R1, R2, R3 and R4 is a substituent, and the rest are hydrogen; (iii) Any two of R1, R2, R3 and R4 are substituents, and the rest are hydrogen; Each of the substituents is independently selected from methyl, ethyl, or propyl.

3. The zirconium compound according to claim 1, characterized in that, The zirconium compound shown in Formula 1 is selected from one of the compounds with the following structural formulas. 。 4. A method for preparing the zirconium compound according to any one of claims 1-3, characterized in that, Includes the following steps: Step S1. Under conditions of anhydrous and oxygen-free environment and in the presence of organic solvent, an alkyl alkali metal salt is reacted with a pyrrole compound to prepare a pyrrole alkali metal salt, wherein the pyrrole compound is selected from pyrrole or substituted pyrrole; Step S2. Under conditions of anhydrous and oxygen-free environment and in the presence of organic solvent, pyrrole alkali metal salt is reacted with zirconium tetrachloride to prepare compound 2; Compound 2 has the structural formula shown in Formula 2 below: Formula 2; R1, R2, R3 and R4 are each independently selected from H, methyl, ethyl or propyl; Step S3. Compound 2 is reacted with cyclopentadiene under anhydrous, oxygen-free, and organic solvent conditions to obtain the compound shown in Formula 1.

5. The preparation method according to claim 4, characterized in that, The reaction described in step S2 is carried out under reflux conditions, preferably for a reaction time of 4-6 hours; and / or, The reaction temperature in step S3 is -5 to 5°C, and the preferred reaction time is 1-3 hours; and / or, The reaction temperature in step S1 is -5 to -15°C, and the preferred reaction time is 1-3 hours.

6. The preparation method according to claim 4, characterized in that, The molar ratio of the alkyl alkali metal salt to the pyrrole compound is 1:1.0-1.2; and / or, The molar ratio of alkyl alkali metal salt to zirconium tetrachloride is 4-5:1; and / or, The molar ratio of compound 2 to cyclopentadiene is 1:1-1.

2.

7. A zirconium-containing precursor composition for preparing thin films, characterized in that, The zirconium compound comprising the zirconium compound of claim 1 or the zirconium compound prepared by any one of claims 4-6.

8. The use of the zirconium-containing precursor composition of claim 7 in the preparation of zirconium oxide thin films.

9. A zirconium-containing thin film, characterized in that, It is prepared by deposition using a zirconium-containing precursor composition as described in claim 7.

10. The application of the zirconium-containing thin film of claim 9 in the semiconductor industry and / or microelectronics field.

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