Sulfur-containing zirconium compounds, precursor compositions containing them, their preparation methods and applications

Abstract

This invention belongs to the field of semiconductor technology, specifically relating to a sulfur-containing zirconium compound, a precursor composition containing the same, and its preparation and application. A sulfur-containing zirconium compound has the chemical formula shown in Formula 1, wherein R1, R2, and R3 are each independently selected from methyl, ethyl, propyl, or butyl, and R4 is selected from hydrogen, methyl, ethyl, propyl, or butyl. The molecular structure of the zirconium compound of this application contains alkyl thiol substituents and cyclopentadienyl substituents. Compared to the (cyclopentadienyl)tris(dimethylamino)zirconium precursor, the zirconium compound of this application exhibits significantly improved thermal stability and low-temperature reactivity. Applying this zirconium compound to the preparation of zirconium oxide thin films is beneficial for improving film uniformity and purity.

Description

Technical Field

[0001] This invention belongs to the field of semiconductor technology, specifically relating to a sulfur-containing zirconium compound, a precursor composition containing the same, and its preparation and application. 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] Despite some progress in currently used zirconium precursor compounds, existing zirconium precursors still face severe challenges in terms of thermal stability and low-temperature reactivity as advanced semiconductor processes move toward 5nm and new functional devices demand increasingly higher thin film quality. Summary of the Invention

[0005] Therefore, the technical problem to be solved by this invention is to provide a sulfur-containing zirconium compound that combines high thermal stability with excellent volatility and low-temperature reactivity. When used in the preparation of zirconium oxide thin films, it can improve the uniformity and purity of the films.

[0006] To address the aforementioned technical problems, the present invention provides the following technical solution: In a first aspect, this application provides a sulfur-containing zirconium compound having the structural formula shown in Formula 1. Formula 1; R1, R2, and R3 are each independently selected from one of methyl, ethyl, propyl, or butyl, and R4 is selected from one of hydrogen, methyl, ethyl, propyl, or butyl.

[0007] In some embodiments of this application, the sulfur-containing zirconium compound is one of the following compounds: .

[0008] Secondly, this application provides a method for preparing the sulfur-containing zirconium compound described in the first aspect above, comprising the following steps: S1. Alkyl mercaptan zirconium is prepared by reacting alkoxy zirconium with alkyl mercaptan alkali metal salt under conditions of anhydrous and oxygen-free environment and in the presence of organic solvent; S2. Under anhydrous, oxygen-free, and organic solvent-free conditions, alkyl thiozirconium thiolate is reacted with an unsubstituted cyclopentadienyl alkali metal salt or an alkyl cyclopentadienyl alkali metal salt to prepare the compound shown in Formula 1, wherein the structural formula of the alkyl cyclopentadienyl alkali metal salt is shown in Formula 2: Formula 2 Where M is an alkali metal, and R5 is selected from H, methyl, ethyl, propyl or butyl.

[0009] In some embodiments of this application, the reaction in step S1 is carried out under reflux conditions, wherein the organic solvent is selected from n-hexane or tetrahydrofuran, and the reaction time is preferably 3-6 h; and / or, The reaction temperature in step S2 is -5 to 5°C, the organic solvent is selected from n-hexane or tetrahydrofuran, and the reaction time is preferably 1-3 hours.

[0010] In some embodiments of this application, step S1 further includes the step of obtaining alkylthiol zirconium by filtering and vacuum distilling the product of the reaction between alkoxyzirconium and alkylthiol alkali metal salt; and / or, Step S2 further includes filtering, vacuum distilling, and fractional distilling the reaction product of alkyl thiozirconium with unsubstituted cyclopentadienyl alkali metal salt or alkyl cyclopentadienyl alkali metal salt to obtain the compound shown in Formula 1.

[0011] In some embodiments of this application, the molar ratio of the unsubstituted cyclopentadienyl alkali metal salt or alkylthiol alkali metal salt to alkoxyzirconium is 4-5:1; and / or, The molar ratio of alkylcyclopentadienyl alkali metal salt to alkylthiozirconium mercaptan is 1.1-1.3:1.

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

[0013] Fourthly, the application 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 as described in the third aspect above.

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

[0016] Beneficial effects: This application presents a zirconium compound with a specific structure, synthesized through molecular design. The molecular structure of this zirconium compound contains alkyl thiol substituents and cyclopentadienyl substituents. Compared to the (cyclopentadienyl)tris(dimethylamino)zirconium precursor, the zirconium compound of this application exhibits improved thermal stability and low-temperature reactivity. Applying this zirconium compound to the preparation of zirconium oxide thin films is beneficial for improving film uniformity and purity. Simultaneously, the alkyl substituents maintain the good volatility of the zirconium compound, facilitating industrial production. 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] In a first aspect, in one specific embodiment of this application, this application provides a sulfur-containing zirconium compound having the structural formula shown in Formula 1.

[0026] R1, R2, and R3 are each independently selected from one of methyl, ethyl, propyl, or butyl, and R4 is selected from one of hydrogen, methyl, ethyl, propyl, or butyl.

[0027] In some embodiments of this application, the sulfur-containing zirconium compound is one of the following compounds: .

[0028] The sulfur-containing zirconium compound of this application contains sulfur substituents and cyclopentadienyl substituents, which improves the stability and low-temperature reactivity of the zirconium compound and is beneficial for uniform film formation when preparing zirconium oxide films.

[0029] When using this sulfur-containing zirconium compound as a precursor to prepare zirconium oxide thin films, its excellent thermal stability and high low-temperature reactivity can reduce the occurrence of side reactions, contributing to the formation of high-purity and uniform films. Furthermore, the zirconium precursor maintains high reactivity at lower temperatures, enabling atomic deposition processes to deposit high-purity, dense zirconium dioxide thin films without damaging temperature-sensitive substrates, thus avoiding material deformation, diffusion, or device performance degradation that may occur with high-temperature processes.

[0030] Secondly, this application provides a method for preparing the zirconium compound shown in Formula 1 above, comprising the following steps: Step S1. Alkyl mercaptan zirconium is prepared by reacting alkoxy zirconium with alkyl mercaptan alkali metal salt under conditions of anhydrous and oxygen-free environment and in the presence of organic solvent; Step S2. Under anhydrous, oxygen-free, and organic solvent-free conditions, alkyl thiozirconium thiolate is reacted with an unsubstituted cyclopentadienyl alkali metal salt or an alkyl cyclopentadienyl alkali metal salt to prepare the compound shown in Formula 1, wherein the structural formula of the alkyl cyclopentadienyl alkali metal salt is shown in Formula 2: Formula 2 Where M is an alkali metal, and R5 is selected from H, methyl, ethyl, propyl or butyl.

[0031] It should be noted that, in this application, the structural formula of alkoxyzirconium is as follows: R6 is selected from one of methyl, ethyl, propyl or butyl.

[0032] It should be noted that in this application, the structural formula of the alkylthiol alkali metal salt is MS-R7, where M is an alkali metal and R7 is selected from methyl, ethyl, or propyl. In some embodiments, M is selected from one or more of lithium, sodium, potassium, rubidium, or cesium.

[0033] It should be noted that, in this application, the structural formula of alkylthiol zirconium is as follows: R8 is selected from one of methyl, ethyl, propyl or butyl.

[0034] In some embodiments of this application, the exemplary chemical reaction equations for the sulfur-containing zirconium compounds represented by Formula 1 are as follows:

[0035] In some embodiments of this application, the reaction in step S1 is carried out under reflux conditions, preferably for a reaction time of 3-6 hours.

[0036] In some embodiments of this application, the mixing temperature of the alkoxyzirconium and the alkylthiol alkali metal salt in step S1 is 15-30°C, and preferably the alkylthiol alkali metal salt is added to the alkoxyzirconium in batches for mixing.

[0037] In some embodiments of this application, the reaction temperature in step S2 is -5 to 5°C, and the reaction time is preferably 1-3 hours. Preferably, the reaction is carried out by a method comprising adding an unsubstituted cyclopentadienyl alkali metal salt or an alkylcyclopentadienyl alkali metal salt dropwise to alkylthiozirconium thiolate.

[0038] In some embodiments of this application, step S1 further includes filtering and vacuum distilling the product of the reaction between alkoxyzirconium and alkylthiol alkali metal salt to obtain alkylthiolzirconium.

[0039] In some embodiments of this application, step S2 further includes filtering the reaction product of alkyl thiozirconium with unsubstituted cyclopentadienyl alkali metal salt or alkyl cyclopentadienyl alkali metal salt, followed by vacuum distillation and fractional distillation to obtain the compound shown in Formula 1.

[0040] In some embodiments of this application, the molar ratio of the alkylthiol alkali metal salt to the alkoxyzirconium is 4-5:1.

[0041] In some embodiments of this application, the molar ratio of unsubstituted cyclopentadienyl alkali metal salt or alkylcyclopentadienyl alkali metal salt to alkyl thiolate zirconium is 1.1-1.3:1.

[0042] Specifically, 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 solvents, alkoxyzirconium is mixed with alkylthiol alkali metal salt, and then heated to reflux and reacted for 4-6 hours to obtain alkylthiolzirconium. Step S2. Under anhydrous, oxygen-free, and organic solvent-free conditions, an unsubstituted cyclopentadienyl alkali metal salt or an alkylcyclopentadienyl alkali metal salt is added dropwise to alkyl thiozirconium thiolate, and the reaction is stirred for 1-3 hours to obtain the compound shown in Formula 1, wherein the structural formula of the alkylcyclopentadienyl alkali metal salt is shown in Formula 2: Formula 2 Where M is an alkali metal, and R5 is selected from H, methyl, ethyl, propyl or butyl.

[0043] In some embodiments of this application, the unsubstituted cyclopentadienyl alkali metal salt is selected from cyclopentadienyl sodium, cyclopentadienyl lithium, or cyclopentadienyl potassium.

[0044] In some embodiments of this application, the organic solvent is selected from n-hexane or tetrahydrofuran.

[0045] Thirdly, this application provides a zirconium-containing precursor composition for preparing thin films, comprising the sulfur-containing zirconium compound of Formula 1 or the sulfur-containing zirconium compound obtained by the above preparation method.

[0046] 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.

[0047] Fifthly, this application provides a zirconium-containing thin film, which is prepared by deposition using a zirconium-containing precursor composition comprising the one described in the third aspect.

[0048] In a sixth 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] In some implementations, the flow rate of the carrier in step (2) is 100-500 sccm.

[0057] 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.

[0058] In some embodiments, during step (2), when the zirconium-containing precursor composition undergoes chemisorption with the substrate, the temperature of the reaction chamber is 200-450°C. Preferably, the temperature of the reaction chamber is 200-240°C.

[0059] 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.

[0060] In some embodiments of this application, the flow rate of the oxygen source plasma gas is 100-500 sccm.

[0061] 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.

[0062] In some embodiments of this application, the temperature of the reaction in step (3) is 200-450°C. Preferably, the temperature of the reaction chamber is 200-240°C.

[0063] The seventh aspect concerns the application of the zirconium-containing thin films described in the fifth aspect in the semiconductor industry and / or the microelectronics field.

[0064] The beneficial effects of the zirconium compounds and their preparation methods described in this application will be illustrated below through specific examples.

[0065] 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.

[0066] 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. Zirconium n-propoxide Purity: 70% Shanghai Aladdin Biochemical Technology Co., Ltd. Zirconium ethanol Purity: 97% Sigma Aldrich (Shanghai) Trading Co., Ltd. Sodium propanethium phosphate Purity: 98% Anhui Zesheng Technology Co., Ltd. Sodium cyclopentadiene Purity: 99% Shanghai Fuyi Biotechnology Co., Ltd. Sodium methanethiol Purity: 99% Shanghai McLean Biochemical Technology Co., Ltd. Sodium ethanethiol Purity: 99% Shanghai McLean Biochemical Technology Co., Ltd. Sodium methylcyclopentadiene Purity: 99% Shanghai Fuyi Biotechnology Co., Ltd. (cyclopentadienyl)tris(dimethylamino)zirconium Purity: 99% Beijing Huawi Ruike Chemical Technology Co., Ltd. Example 1

[0067] 1. Preparation of Zirconium Compounds S1. In an anhydrous and oxygen-free glove box environment, a dry three-necked flask was used to set up the experimental apparatus. 200g of dry n-hexane was added to the three-necked flask. At 20°C, 35.05g of n-propoxide zirconium was added, and the temperature was maintained at 20°C. A total of 48.2g of sodium propanethiolate (9.64g per batch) was slowly added to the three-necked flask in five separate batches. After the addition was complete, the temperature was raised to reflux, and the reaction was stirred for 4 hours. After filtration, the solvent was removed by vacuum distillation. 40.6g of tetrapropylzirconium thiolate was obtained, with a yield of 97.3%.

[0068] The obtained tetrapropylthiol zirconium was identified by 1H NMR, and the specific data are as follows: 1H NMR (400MHz, C6D6): δ2.54 (8H, t); δ1.31 (8H, sext); δ0.99 (12H, t).

[0069] S2. In an anhydrous and oxygen-free glove box environment, a dry three-necked flask was used to set up the experimental apparatus. 300g of dry n-hexane was added to the three-necked flask. At 0°C, 40g of tetrapropylzirconium mercaptan was added to the three-necked flask. While maintaining 0°C, 10.8g of sodium cyclopentadiene was slowly added dropwise. After the addition was complete, the mixture was stirred for 1 hour and then brought to room temperature. The solvent was removed by filtration and vacuum distillation to obtain 35.6g of crude product. The crude product was purified by distillation at 0.1 torr and 100°C to obtain 27.8g of white liquid, with a yield of 71%.

[0070] The obtained white liquid was identified by 1H NMR spectroscopy, and the specific data are as follows: 1 ¹H NMR (400 MHz, C6D6): δ 6.50 (2H, s); δ 6.40 (2H, s); δ 2.90 (1H, s); δ 2.54 (6H, t); δ 1.31 (6H, sext); δ 0.99 (9H, t). The results indicate that compound 13 was successfully obtained.

[0071] Preparation of zirconia thin films: (1) Place the silicon wafer in the reaction chamber of the PE-ALD equipment and set the deposition temperature to 200°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).

[0072] Example 2 1. Preparation of Zirconium Compounds S1. In an anhydrous and oxygen-free glove box environment, an experimental setup was constructed using a dry three-necked flask. 200g of dry n-hexane was added to the three-necked flask. At 15°C, 35.05g of n-propoxide zirconium was added, and the temperature was maintained at 15°C. A total of 48.2g of sodium propanethiolate (9.64g per batch) was slowly added to the three-necked flask in five separate batches. After the addition was complete, the temperature was raised to reflux, and the reaction was stirred for 5 hours. After filtration, the solvent was removed by vacuum distillation. 38.3g of tetrapropylzirconium thiolate was obtained, with a yield of 92%.

[0073] The obtained tetrapropylthiol zirconium was identified by 1H NMR, and the specific data are as follows: 1H NMR (400MHz, C6D6): δ2.54 (8H, t); δ1.31 (8H, sext); δ0.99 (12H, t).

[0074] S2. In an anhydrous and oxygen-free glove box environment, a dry three-necked flask was used to set up the experimental apparatus. 300g of dry n-hexane was added to the three-necked flask. At 0°C, 35g of tetrapropylzirconium mercaptan was added to the three-necked flask. While maintaining 0°C, 9.5g of sodium cyclopentadiene was slowly added dropwise to the three-necked flask. After stirring for 3 hours, the mixture was brought to room temperature. The solvent was removed by filtration and vacuum distillation to obtain 30.1g of crude product. The crude product was purified by distillation at 0.1 torr and 100°C to obtain 24.3g of white liquid, with a yield of 71.3%.

[0075] The obtained white liquid was identified by 1H NMR spectroscopy, and the specific data are as follows: 1 ¹H NMR (400 MHz, C6D6): δ 6.50 (2H, s); δ 6.40 (2H, s); δ 2.90 (1H, s); δ 2.54 (6H, t); δ 1.31 (6H, sext); δ 0.99 (9H, t). The results indicate that compound 13 was successfully obtained.

[0076] Preparation of zirconia thin films: (1) Place the silicon wafer in the reaction chamber of the PE-ALD equipment and set the deposition temperature to 200°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).

[0077] Example 3 1. Preparation of Zirconium Compounds S1. In an anhydrous and oxygen-free glove box environment, an experimental setup was constructed using a dry three-necked flask. 200g of dry n-hexane was added to the three-necked flask. At 25°C, 35.05g of n-propoxide zirconium was added, and the temperature was maintained at 25°C. A total of 48.2g of sodium propanethiolate (9.64g per batch) was slowly added to the three-necked flask in five separate batches. After the addition was complete, the temperature was raised to reflux, and the reaction was stirred for 6 hours. After filtration, the solvent was removed by vacuum distillation. 38.7g of tetrapropylzirconium thiolate was obtained, with a yield of 93%.

[0078] The obtained tetrapropylthiol zirconium was identified by 1H NMR, and the specific data are as follows: 1H NMR (400MHz, C6D6): δ2.54 (8H, ); δ1.31 (8H, sext ); δ0.99 (12H, t).

[0079] S2. In an anhydrous and oxygen-free glove box environment, a dry three-necked flask was used to set up the experimental apparatus. 300g of dry n-hexane was added to the three-necked flask. At 5°C, 37g of tetrapropylzirconium mercaptan was added to the three-necked flask. While maintaining the temperature at 5°C, 10g of sodium cyclopentadiene was slowly added dropwise to the three-necked flask. After stirring for 2 hours, the mixture was brought to room temperature. The solvent was removed by filtration and vacuum distillation to obtain 31.6g of crude product. The crude product was purified by distillation at 0.1 torr and 100°C to obtain 26g of white liquid, with a yield of 72.1%.

[0080] The obtained white liquid was identified by 1H NMR spectroscopy, and the specific data are as follows: 1 ¹H NMR (400 MHz, C6D6): δ 6.50 (2H, s); δ 6.40 (2H, s); δ 2.90 (1H, s); δ 2.54 (6H, t); δ 1.31 (6H, sext); δ 0.99 (9H, t). The results indicate that compound 13 was successfully obtained.

[0081] Preparation of zirconia thin films: (1) Place the silicon wafer in the reaction chamber of the PE-ALD equipment and set the deposition temperature to 200°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).

[0082] Example 4 1. Preparation of Zirconium Compounds S1. In an anhydrous and oxygen-free glove box environment, an experimental setup was constructed using a dry three-necked flask. 200g of dry n-hexane was added to the three-necked flask. At 10°C, 35.05g of n-propoxide zirconium was added, and the temperature was maintained at 10°C. A total of 48.2g of sodium propanethiolate (9.64g per batch) was slowly added to the three-necked flask in five separate batches. After the addition was complete, the temperature was raised to reflux, and the reaction was stirred for 3 hours. After filtration, the solvent was removed by vacuum distillation. 37.9g ​​of tetrapropylzirconium thiolate was obtained, with a yield of 91%.

[0083] The obtained tetrapropylthiol zirconium was identified by 1H NMR, and the specific data are as follows: 1H NMR (400MHz, C6D6): δ2.54 (8H, t); δ1.31 (8H, sext); δ0.99 (12H, t).

[0084] S2. In an anhydrous and oxygen-free glove box environment, a dry three-necked flask was used to set up the experimental apparatus. 300g of dry n-hexane was added to the three-necked flask. At -5℃, 37g of tetrapropylzirconium mercaptan was added to the three-necked flask. While maintaining the -5℃ condition, 10.8g of sodium cyclopentadiene was slowly added dropwise to the three-necked flask. After stirring the reaction for 3h, the mixture was raised to room temperature. The solvent was removed by filtration and vacuum distillation to obtain 30.5g of crude product. The crude product was purified by distillation at 0.1 torr and 100℃ to obtain 25.5g of white liquid, with a yield of 70.6%.

[0085] The obtained white liquid was identified by 1H NMR spectroscopy, and the specific data are as follows: 1 ¹H NMR (400 MHz, C6D6): δ 6.50 (2H, s); δ 6.40 (2H, s); δ 2.90 (1H, s); δ 2.54 (6H, t); δ 1.31 (6H, sext); δ 0.99 (9H, t). The results indicate that compound 13 was successfully obtained.

[0086] Preparation of zirconia thin films: (1) Place the silicon wafer in the reaction chamber of the PE-ALD equipment and set the deposition temperature to 200°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).

[0087] Example 5 1. Preparation of Zirconium Compounds S1. In an anhydrous and oxygen-free glove box environment, an experimental setup was constructed using a dry three-necked flask. 200g of dry n-hexane was added to the three-necked flask. At 20°C, 30g of zirconium ethoxide was added, and the temperature was maintained at 20°C. A total of 31.8g of sodium methanethiol (6.4g per batch) was slowly added to the three-necked flask in five separate batches. After the addition was complete, the temperature was raised to reflux, and the reaction was stirred for 4 hours. After filtration, the solvent was removed by vacuum distillation. 28.6g of tetramethylzirconium mercaptan was obtained, with a yield of 93%.

[0088] The obtained tetramethylthiol zirconium was identified by 1H NMR, and the specific data are as follows: 1H NMR (400MHz, C6D6): δ2.00 (12H, s).

[0089] S2. In an anhydrous and oxygen-free glove box environment, a dry three-necked flask was used to set up the experimental apparatus. 300g of dry n-hexane was added to the three-necked flask. At 0°C, 25g of tetramethylzirconium mercaptan was added to the three-necked flask. While maintaining 0°C, 9.4g of sodium cyclopentadiene was slowly added dropwise to the three-necked flask. After stirring for 1 hour, the mixture was brought to room temperature. The solvent was removed by filtration and vacuum distillation to obtain 23.4g of crude product. The crude product was purified by distillation at 0.1 torr and 100°C to obtain 19.5g of white liquid, with a yield of 73.5%.

[0090] The obtained white liquid was identified by 1H NMR spectroscopy, and the specific data are as follows: 1 ¹H NMR (400 MHz, C6D6): δ7.26 (2H, d⁻); δ6.28 (2H, d⁻); δ2.90 (1H, s⁻); δ2.00 (9H, s⁻). The results indicate that compound 11 was successfully obtained.

[0091] Preparation of zirconia thin films: (1) Place the silicon wafer substrate in the reaction chamber of the PE-ALD equipment and set the deposition temperature to 200°C; (2) Nitrogen carrier gas is introduced into the reaction chamber at a flow rate of 200 sccm. Compound 11 is introduced into the reaction chamber in a pulsed manner for 6 s to allow compound 11 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).

[0092] Example 6 1. Preparation of Zirconium Compounds S1. In an anhydrous and oxygen-free glove box environment, a dry three-necked flask was used to set up the experimental apparatus. 200g of dry n-hexane was added to the three-necked flask. At 20°C, 35.05g of n-zirconium propoxide was added, and the temperature was maintained at 20°C. A total of 37.34g of sodium ethanethiol (7.46g per batch) was slowly added to the three-necked flask in five batches. After the addition was complete, the temperature was raised to reflux, and the reaction was stirred for 4 hours. After filtration, the solvent was removed by vacuum distillation. 33g of tetraethylzirconium mercaptan was obtained, with a yield of 92%.

[0093] The obtained tetraethylthiol zirconium was identified by 1H NMR, and the specific data are as follows: 1H NMR (400MHz, C6D6): δ2.60 (8H, q); δ1.39 (12H, t).

[0094] S2. In an anhydrous and oxygen-free glove box environment, a dry three-necked flask was used to set up the experimental apparatus. 300g of dry n-hexane was added to the three-necked flask. At 0°C, 30g of tetraethylzirconium mercaptan was added to the three-necked flask. While maintaining 0°C, 9.4g of sodium cyclopentadiene was slowly added dropwise to the three-necked flask. After stirring the reaction for 1 hour, the mixture was brought to room temperature. The solvent was removed by filtration and vacuum distillation to obtain 27.7g of crude product. The crude product was purified by distillation at 0.1 torr and 100°C to obtain 22.5g of white liquid, with a yield of 74%.

[0095] The obtained white liquid was identified by 1H NMR spectroscopy, and the specific data are as follows: 1 ¹H NMR (400 MHz, C6D6): δ7.26 (2H, d⁻); δ6.28 (2H, d⁻); δ2.90 (1H, s⁻); δ2.60 (6H, q⁻); δ1.39 (9H, t⁻). The results indicate that compound 12 was successfully obtained.

[0096] Preparation of zirconia thin films: (1) Place the silicon wafer in the reaction chamber of the PE-ALD equipment and set the deposition temperature to 200°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).

[0097] Example 7 1. Preparation of Zirconium Compounds S1. In an anhydrous and oxygen-free glove box environment, a dry three-necked flask was used to set up the experimental apparatus. 200g of dry n-hexane was added to the three-necked flask. At 20°C, 35.05g of n-propoxide zirconium was added, and the temperature was maintained at 20°C. A total of 48.2g of sodium propanethiolate (9.64g per batch) was slowly added to the three-necked flask in five separate batches. After the addition was complete, the temperature was raised to reflux, and the reaction was stirred for 4 hours. After filtration, the solvent was removed by vacuum distillation. 40.6g of tetrapropylzirconium thiolate was obtained, with a yield of 97.3%.

[0098] The obtained tetrapropylthiol zirconium was identified by 1H NMR, and the specific data are as follows: 1H NMR (400MHz, C6D6): δ2.54 (8H, t); δ1.31 (8H, sext); δ0.99 (12H, t).

[0099] S2. In an anhydrous and oxygen-free glove box environment, a dry three-necked flask was used to set up the experimental apparatus. 300g of dry n-hexane was added to the three-necked flask. At 0°C, 40g of tetrapropylzirconium mercaptan was added to the three-necked flask. While maintaining 0°C, 11.5g of sodium methylcyclopentadiene was slowly added dropwise to the three-necked flask. After stirring for 1 hour, the mixture was brought to room temperature. The solvent was removed by filtration and vacuum distillation to obtain 36.5g of crude product. The crude product was purified by distillation at 0.1 torr and 100°C to obtain 29.3g of white liquid, with a yield of 72.3%.

[0100] The obtained white liquid was identified by 1H NMR spectroscopy, and the specific data are as follows: 1¹H NMR (400 MHz, C6D6): δ 6.50 (¹H, s); δ 6.40 (¹H, s); δ 6.28 (¹H, d); δ 2.9 (¹H, s); δ 2.54 (⁶H, t); δ 1.79 (⁃H, s); δ 1.31 (⁶H, sext); δ 0.99 (⁹H, t). The results indicate that compound 14 was successfully obtained.

[0101] Preparation of zirconia thin films: (1) Place the silicon wafer in the reaction chamber of the PE-ALD equipment and set the deposition temperature to 200°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 compound 14 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] Comparative Example 1 Preparation of zirconia thin films: (1) Place the silicon wafer in the reaction chamber of the PE-ALD equipment and set the deposition temperature to 200°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).

[0103] Comparative Example 2 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 13.4g of lithium dimethylamino were added to the three-necked flask, and the temperature was lowered to 0℃±0.5℃. 15g of zirconium tetrachloride 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%.

[0104] The first intermediate was identified by 1H NMR spectroscopy, and the specific data are as follows: 1 1H NMR (400MHz, C6D6): (2.978, 24H). Analysis of the 1H NMR data indicates that the target product was successfully obtained.

[0105] Add 60 ml of tetrahydrofuran solution to a 200 ml three-necked flask, then add 6 g of prepared cyclopentadiene. After cooling to -40 °C, add 2.29 g of NaH in 5 batches, maintaining a constant temperature throughout the addition. After the addition is complete, maintain the temperature and stir for 1 hour. Then slowly raise the temperature to -10 °C ± 0 °C. 15.64 g of diethylphosphonic chloride was slowly added dropwise to a three-necked flask at -10℃ ± 0.5℃. After the addition was complete, the mixture was stirred at -10℃ ± 0℃ for 1 h. 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 Na2SO4 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℃ to obtain the second intermediate (diethylphosphonic cyclopentadiene), approximately 14.35 g, with a yield of approximately 85%.

[0106] The obtained second intermediate was identified by 1H NMR spectroscopy. The specific data is as follows: 1 1H NMR (400MHz, CCl3D): (6.50, 2H), (6.40, 2H), (3.85, 4H), (2.9, 1H), (1.25, 6H). Analysis of the 1H NMR data indicates that the target product was successfully obtained.

[0107] 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 and 15.4g 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 complete, maintain the temperature at 0℃±0.5℃ and stir for 1.5h. Then raise the temperature to 70℃ to reach reflux and stir the reaction for 2h. 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 18.12g of a pale yellow liquid, which is (diethylphosphine cyclopentadienyl)tri(dimethylamino)zirconium.

[0108] The obtained pale yellow liquid was identified by 1H NMR spectroscopy, and the specific data are as follows: 1 1H NMR (400 MHz, C6D6): (6.006, 1H), (5.920, 2H), (3.57, 4H), (2.96, 18H), (2.45, 1H), (1.25, 6H). Analysis of the 1H NMR data confirms the successful acquisition of the target product.

[0109] (1) Place the silicon wafer in the reaction chamber of the ALD equipment and set the deposition temperature to 200°C; (2) Nitrogen carrier gas is introduced into the reaction chamber at a flow rate of 200 sccm. (Diethylphosphine cyclopentadienyl)tri(dimethylamino)zirconium is introduced into the reaction chamber in a pulsed manner for 6 s, so that (diethylphosphine cyclopentadienyl)tri(dimethylamino)zirconium is chemically adsorbed 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).

[0110] 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.

[0111] 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.

[0112] 2. Volatility test: Thermogravimetric analysis (TGA 550) was performed on zirconium-containing compounds under the following conditions: temperature range of 50℃ to 450℃, heating rate of 15℃ / min. Volatility was considered excellent when the weight loss curve was smooth and without steps, and the residual weight was ≤0.5%.

[0113] 3. Test methods for reactivity: (1) Place the silicon wafer in the reaction chamber of the ALD equipment and set the deposition temperature to 200°C; (2) Introduce nitrogen carrier into the reaction chamber at a flow rate of 200 sccm, and introduce zirconium compound into the reaction chamber in a pulsed manner for 0.5 s to allow the zirconium compound to chemically adsorb onto the substrate. Then, purge with nitrogen for 10 s. (3) Water vapor plasma is introduced into the reaction chamber at a flow rate of 200 sccm and a time of 0.3 s to obtain a zirconia film. After the zirconia film is formed, nitrogen gas is introduced again to remove unreacted precursor materials and byproducts. 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).

[0114] 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.

[0115] 4. Metal purity test: The metal purity in the film was tested using ICP-MS (LabMS 3000).

[0116] 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%.

[0117] 5. 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.

[0118] 6. Test method for carbon content of thin film: The elemental composition of thin film was tested using 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.

[0119] Table 2 Test results of zirconium compounds Example 1 196 269 excellent 1.0 Example 2 194 270 excellent 1.1 Example 3 195 268 excellent 1.0 Example 4 194 269 excellent 1.1 Example 5 188 261 excellent 0.9 Example 6 190 265 excellent 0.9 Example 7 198 272 excellent 1.1 Comparative Example 1 183 245 excellent 0.8 Comparative Example 2 189 253 excellent 0.8 Table 3 Test results of zirconium oxide thin films Example 1 7N excellent 383 Example 2 7N excellent 395 Example 3 7N excellent 392 Example 4 7N excellent 385 Example 5 7N excellent 378 Example 6 7N excellent 389 Example 7 7N excellent 387 Comparative Example 1 7N good 767 Comparative Example 2 7N excellent 465 As shown in Table 2, the initial temperatures of the zirconium compounds prepared in Examples 1-7 of this application are in the range of 188-196℃, and the temperatures reaching the exothermic peak are in the range of 261-272℃, both higher than those of Comparative Example 1 and Comparative Example 2. This indicates that the thermal stability of the zirconium compounds prepared in this application is significantly better than that of the prior art (cyclopentadienyl)tris(dimethylamino)zirconium and (diethylphosphine-cyclopentadienyl)tris(dimethylamino)zirconium. Furthermore, the volatility of the zirconium compounds in this application is comparable to that of (cyclopentadienyl)tris(dimethylamino)zirconium, and their low-temperature reactivity is superior to that of (cyclopentadienyl)tris(dimethylamino)zirconium and (diethylphosphine-cyclopentadienyl)tris(dimethylamino)zirconium.

[0120] 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 zirconium oxide films prepared using (cyclopentadienyl)tris(dimethylamino)zirconium precursor and (diethylphosphine-cyclopentadienyl)tris(dimethylamino)zirconium precursor.

[0121] 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.

[0122] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., refer to specific features, structures, materials, or characteristics described in connection with that embodiment or example, which are included in at least one embodiment or example of the present 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 different embodiments or examples.

[0123] 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 sulfur-containing zirconium compound, characterized in that, It has the structural formula shown in Equation 1. Formula 1; R1, R2, and R3 are each independently selected from one of methyl, ethyl, propyl, or butyl, and R4 is selected from one of hydrogen, methyl, ethyl, propyl, or butyl.

2. The sulfur-containing zirconium compound according to claim 1, characterized in that, The sulfur-containing zirconium compound is one of the following compounds: 。 3. The method for preparing the sulfur-containing zirconium compound according to claim 1 or 2, characterized in that, Includes the following steps: S1. Alkyl mercaptan zirconium is prepared by reacting alkoxy zirconium with alkyl mercaptan alkali metal salt under conditions of anhydrous and oxygen-free environment and in the presence of organic solvent; S2. Under anhydrous, oxygen-free, and organic solvent-free conditions, alkyl thiozirconium thiolate is reacted with an unsubstituted cyclopentadienyl alkali metal salt or an alkyl cyclopentadienyl alkali metal salt to prepare the compound shown in Formula 1, wherein the structural formula of the alkyl cyclopentadienyl alkali metal salt is shown in Formula 2: ； Where M is an alkali metal, and R5 is selected from methyl, ethyl, propyl or butyl.

4. The preparation method according to claim 3, characterized in that, The reaction in step S1 is carried out under reflux conditions, wherein the organic solvent is selected from n-hexane or tetrahydrofuran, and the reaction time is preferably 3-6 h; and / or, The reaction temperature in step S2 is -5 to 5°C, the organic solvent is selected from n-hexane or tetrahydrofuran, and the reaction time is preferably 1-3 hours.

5. The preparation method according to claim 3, characterized in that, Step S1 further includes obtaining alkylthiozirconium by filtering and vacuum distilling the product of the reaction between alkoxyzirconium and alkylthiols alkali metal salts; and / or, Step S2 further includes filtering, vacuum distilling, and fractional distilling the reaction product of alkyl thiozirconium with unsubstituted cyclopentadienyl alkali metal salt or alkyl cyclopentadienyl alkali metal salt to obtain the compound shown in Formula 1.

6. The preparation method according to claim 3, characterized in that, The molar ratio of alkylthiols alkali metal salts to alkoxyzirconium is 4-5:1; and / or, The molar ratio of unsubstituted cyclopentadienyl alkali metal salt or alkylcyclopentadienyl alkali metal salt to alkyl thiolate zirconium is 1.1-1.3:

1.

7. A zirconium-containing precursor composition for preparing thin films, characterized in that, It includes the sulfur-containing zirconium compound as described in claim 1 or 2, or the sulfur-containing zirconium compound prepared by any one of claims 3-6.

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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