A vacuum rectification device and method for electronic-grade metal organic precursors

Abstract

The application discloses a kind of electronic grade metal organic precursor vacuum rectification device and method, it is related to rectification technical field, device includes raw material tank, rectification tower, crude product tank, product tank, sampling filling glove box, vacuum pump and cold trap;The raw material tank production pipe is connected with rectification tower kettle;The rectification tower top product sampling outlet is connected with production pipeline, and production pipeline is connected with crude product tank and product tank import, and the crude product tank and product tank are connected with nitrogen and vacuum pipeline;The vacuum pipeline is connected with cold trap, and cold trap is connected with vacuum pump;The product tank feed pipeline is connected with sampling filling glove box;Method ensures that the pressure in crude product tank is lower than the pressure of crude product tank material sampling outlet and the pressure in product tank is lower than the pressure of product tank material sampling outlet.The application can effectively solve the problem that metal organic precursor is difficult to be industrialized and continuously produced in the process of rectification, with higher operating temperature, faster decomposition, lower product purity and greater difficulty in vacuum rectification.

Description

Technical Field

[0001] This invention relates to the field of distillation technology, and more specifically, to a vacuum distillation apparatus and method for electronic-grade organometallic precursors. Background Technology

[0002] As chip manufacturing processes continue to shrink, the thickness of the gate dielectric layer in metal-oxide-semiconductor field-effect transistors (MOSFETs) is constantly decreasing. Using silicon dioxide thin films as the gate dielectric layer presents a problem where electrons tunnel directly through the interface barrier between the silicon dioxide film and the substrate. Replacing silicon dioxide-deposited films with high-dielectric-constant materials as the gate dielectric layer can significantly reduce this phenomenon, while also meeting the demands for increased transistor switching speed and smaller transistor fabrication. Zirconium-based and hafnium-based materials have become key choices for gate dielectric materials, with significant market potential. Metal-organic precursors can be deposited on substrate materials using processes such as chemical vapor deposition (CVD) and atomic layer deposition (ALD), and can be applied in semiconductor, microelectronics, optoelectronics, and lithium-ion battery electrode manufacturing. Transistor gate dielectric film fabrication is an important downstream market for these precursors.

[0003] As a "bottleneck" material in semiconductor manufacturing, the technological breakthroughs and market expansion of metal-organic precursors directly affect the competitiveness of the global semiconductor industry. However, the high boiling point and easy decomposition of metal-organic precursors mean that traditional atmospheric distillation methods consume a lot of energy and have a rapid decomposition rate, affecting the purity and yield of the product.

[0004] By employing vacuum distillation, the operating pressure of the system is reduced, thereby lowering the distillation temperature, reducing product decomposition, ensuring product purity, and reducing energy consumption. For example, patent number CN114669071A mentions a vacuum distillation apparatus and method for silicon-based electronic products, including a raw material tank, a distillation unit, a product tank, and a recooling unit. This invention can solve problems in existing technologies such as high operating temperatures, high consumption of heating media during production, long process flows in traditional vacuum distillation devices, and unstable control. Another example is patent number CN201949674U, which mentions a chemical vacuum distillation apparatus, comprising a distillation kettle, a packed tower, a condenser, a buffer tank, and a balance tank. This apparatus can effectively reduce oxidation and polymerization during distillation, ensuring stable operation of the distillation separation process.

[0005] However, traditional vacuum distillation in the chemical industry has disadvantages such as long equipment process, high energy consumption, and difficulty in control, which makes it difficult to maintain the purity and stability of electronic-grade organometallic precursors. Therefore, how to provide a solution to overcome or alleviate the above-mentioned defects is still a problem that needs to be solved by those skilled in the art. Summary of the Invention

[0006] The purpose of this application is to provide a vacuum distillation apparatus and method for electronic-grade organometallic precursors, which reduces the instability and easy decomposition of organometallic precursor products during the distillation process and effectively improves the distillation efficiency of the products.

[0007] The technical solution of the present invention: A vacuum distillation apparatus for electronic-grade organometallic precursors includes a feed tank, a distillation column, a crude product tank, a product tank, a sampling and filling glove box, a vacuum pump, and a cold trap. The raw material tank is equipped with a first nitrogen inlet and a material outlet; the material outlet is connected to the reboiler of the distillation column via a pipeline; the top of the distillation column is equipped with a second nitrogen inlet and a vacuum pipeline; the material outlet at the top of the distillation column is connected to the crude product tank inlet via a pipeline, and the material outlet at the top of the distillation column is also connected to the product tank inlet via a pipeline; the crude product tank is equipped with a third nitrogen inlet and a vacuum pipeline; the product tank is also equipped with a fourth nitrogen inlet and a vacuum pipeline; the product tank is connected to a sampling and filling glove box; the vacuum pipelines of the distillation column, the crude product tank, and the product tank are all connected to a cold trap; the cold trap is connected to a vacuum pump.

[0008] Preferably, the first nitrogen inlet is equipped with a raw material tank nitrogen regulating valve, the material outlet is equipped with a raw material tank material discharge valve, the pipe connecting the material outlet and the bottom of the distillation column is equipped with a distillation column material feed valve, and the second nitrogen inlet is equipped with a distillation column nitrogen regulating valve.

[0009] Preferably, the reboiler of the distillation column is equipped with a jacketed heat exchanger, the heat exchange medium is heat transfer oil, and the heat exchange temperature is 90~150℃; the reboiler of the distillation column is equipped with a stirrer with a rotation speed of 1~1000 rpm; the top of the distillation column is equipped with a tubular heat exchanger, the heat exchange medium is cooling oil, and the heat exchange temperature is -20~40℃; the theoretical number of plates in the distillation column is 20~50; the reboiler, column section connections, and top material outlet of the distillation column are all equipped with temperature and pressure detection devices.

[0010] Preferably, the first nitrogen inlet, the second nitrogen inlet, the third nitrogen inlet and the fourth nitrogen inlet are all connected to nitrogen cylinders or nitrogen pipelines, and the nitrogen is 9N high-purity nitrogen.

[0011] Preferably, the distillation column is equipped with a liquid phase outlet and a liquid phase outlet pipe. The liquid phase outlet is connected to the feed inlet of the crude product tank and the feed inlet of the product tank through the pipe respectively. A crude product outlet valve is installed on the pipe between the liquid phase outlet and the feed inlet of the crude product tank, and a product outlet valve is installed on the pipe between the liquid phase outlet and the feed inlet of the product tank. A nitrogen regulating valve for the crude product tank is provided on the third nitrogen inlet, a crude product tank feed valve is provided on the crude product tank feed inlet, a crude product tank material outlet is provided on the pipeline between the crude product outlet valve and the crude product tank feed valve, and a crude product tank discharge valve is provided on the crude product tank material outlet. The fourth nitrogen inlet is equipped with a nitrogen regulating valve for the product tank, the product tank feed inlet is equipped with a product tank feed valve, the pipeline between the product outlet valve and the product tank feed valve is equipped with a product tank material outlet, the product tank material outlet is equipped with a product tank discharge valve, and the product tank discharge valve is connected to the sampling and filling glove box.

[0012] Preferably, pressure detection devices are installed on the vacuum lines of the distillation column, the crude product tank, and the product tank.

[0013] Preferably, the vacuum pump and the cold trap are connected by a pipeline, and a vacuum pump inlet valve is installed on the pipeline between the vacuum pump and the cold trap; a distillation column vacuum regulating valve is installed at the end of the distillation column vacuum pipeline, a crude product tank vacuum regulating valve is installed on the crude product tank vacuum pipeline, and a product tank vacuum regulating valve is installed on the product tank vacuum pipeline; the ultimate vacuum of the vacuum pump is 1~20 Pa, and the pumping speed is 5~30 m / s². 3 / h.

[0014] Preferably, the cold trap is equipped with a jacketed heat exchanger, the heat exchange medium is cooling oil, and the heat exchange temperature is -120~-60℃.

[0015] A method for vacuum distillation of electronic-grade organometallic precursors includes the following steps: The organometallic precursor in the feed tank is conveyed to the distillation column via nitrogen pressurization. The material is then purified by distillation. The pressure in the distillation column is stabilized by controlling the nitrogen and vacuum regulating valves. The column is heated by controlling the temperature of the heat transfer oil in the reboiler jacket. The material in the reboiler is stirred by the agitator. The vaporized material rises through the packing to the top tube heat exchanger. The rising vapor is cooled and condensed into a liquid phase by controlling the temperature of the cooling oil, then refluxed and collected. Initially, the crude product collection valve and the crude product tank feed valve are opened to allow the collected product to be collected. The light components are collected into the crude product tank. When the absolute pressure at the material outlet of the crude product tank is 100~500Pa and the temperature reaches 80~120℃, the crude product outlet valve and the crude product tank feed valve are closed, and the product outlet valve and the product tank feed valve are opened to collect the material into the product tank. By controlling the opening of the nitrogen regulating valves of the crude product tank and the product tank, the pressure inside the crude product tank is lower than the pressure at the material outlet of the crude product tank and the pressure inside the product tank is lower than the pressure at the material outlet of the product tank, ensuring that the material is collected into the crude product tank and the product tank respectively. Once the crude product tank is full, close the crude product discharge valve and the crude product tank vacuum regulating valve, open the crude product tank nitrogen regulating valve, control the pressure inside the crude product tank to 0.01 MPa~0.1 MPa, open the crude product tank discharge valve, and transfer the material in the crude product tank to a pressure cylinder or other container for further distillation and purification; once the product tank is full, close the product discharge valve and the product tank vacuum regulating valve, open the product tank nitrogen regulating valve, control the pressure inside the product tank to 0.01 MPa~0.1 MPa, open the product tank discharge valve, and transfer the product in the product tank to the sampling and filling glove box for sampling and analysis. After the results are qualified, with a main content ≥99.5% and metal ions meeting 6N (99.9999%), the product cylinder will be filled. The vacuum regulating valves of the distillation column, crude product tank, and product tank are all connected to the bottom pipe of the cold trap. The temperature of the cold trap is controlled by cooling oil, and the pressure in the cold trap is controlled by a vacuum pump between 5 and 100 Pa. The exhaust gas from the vacuum pump is collected and treated.

[0016] Furthermore, the organometallic precursor includes any one of other thermosensitive organometallic precursors such as (n-propylcyclopentadienyl)tris(dimethylamino)zirconium, (cyclopentadienyl)tris(dimethylamino)zirconium, and (cyclopentadienyl)tris(dimethylamino)hafnium.

[0017] The beneficial effects of this invention are: The raw materials of this invention, such as (n-propylcyclopentadienyl)tris(dimethylamino)zirconium, (cyclopentadienyl)tris(dimethylamino)zirconium, and (cyclopentadienyl)tris(dimethylamino)hafnium, and other thermosensitive organometallic precursors, all possess high boiling points and are easily decomposed. The method of this invention enables vacuum distillation of organometallic precursors, improving distillation efficiency and stability. The product in the product tank is pressurized into a sampling filling glove box for sampling and analysis, avoiding sample contamination that could affect the analytical results. The material in the crude product tank is further purified by distillation, increasing the yield. This invention effectively solves the problems of high operating temperatures, rapid decomposition, low product purity, and the difficulty of vacuum distillation in the continuous industrial production of organometallic precursors during distillation. Attached Figure Description

[0018] Figure 1 This is a schematic diagram of the structure of the device of the present invention; In the attached diagram, 1-raw material tank, 2-raw material tank nitrogen regulating valve, 3-raw material tank material discharge valve, 4-distillation column material feed valve, 5-distillation column, 6-distillation column nitrogen regulating valve, 7-crude product discharge valve, 8-crude product tank discharge valve, 9-crude product tank nitrogen regulating valve, 10-crude product tank feed valve, 11-crude product tank, 12-product discharge valve, 13-product tank nitrogen regulating valve, 14-product tank feed valve, 15-product tank, 16-product tank discharge valve, 17-sampling and filling glove box, 18-crude product tank vacuum regulating valve, 19-product tank vacuum regulating valve, 20-distillation column vacuum regulating valve, 21-cold trap, 22-vacuum pump inlet valve, 23-vacuum pump. Detailed Implementation

[0019] To enable those skilled in the art to better understand the technical solutions of this application, the application will be further described in detail below with reference to the accompanying drawings and specific embodiments.

[0020] Device Examples Please refer to Figure 1 This is a schematic diagram of the apparatus structure for vacuum distillation of organometallic precursors according to an embodiment of the present invention; a vacuum distillation apparatus for electronic-grade organometallic precursors includes a raw material tank 1, a distillation column 5, a crude product tank 11, a product tank 15, a sampling and filling glove box 17, a vacuum pump 23, and a cold trap 21. The raw material tank 1 is equipped with a first nitrogen inlet and a material outlet. A nitrogen regulating valve 2 is installed on the first nitrogen inlet, and a material outlet valve 3 is installed on the material outlet. A material feed valve 4 is installed on the pipeline connecting the material outlet to the reboiler of the distillation column 5. A second nitrogen inlet and a vacuum pipeline are installed at the top of the distillation column 5. A nitrogen regulating valve 6 is installed on the second nitrogen inlet. The material outlet is connected to the reboiler of the distillation column 5. The distillation column 5 has a jacketed heat exchanger in its reboiler, with heat transfer oil as the heat exchange medium and a heat exchange temperature of 90~150℃. A stirrer is installed inside the reboiler of the distillation column 5, with a stirrer speed of 1~1000 rpm. A tubular heat exchanger is installed at the top of the distillation column 5, with cooling oil as the heat exchange medium and a heat exchange temperature of -20~40℃. The distillation column 5 has 20~50 theoretical plates. Temperature and pressure detection devices are installed at the reboiler, column section connections, and material outlet at the top of the distillation column 5. The top material outlet of the distillation column 5 is connected to the crude product tank inlet of the crude product tank 11 via a pipeline. The distillation column 5 is equipped with a liquid phase outlet and a liquid phase outlet pipeline. The liquid phase outlet is connected to the crude product tank inlet and the product tank inlet via pipelines respectively. A crude product outlet valve 7 is installed on the pipeline between the liquid phase outlet and the crude product tank inlet. The crude product tank 11 is also equipped with a third nitrogen inlet and a crude product tank vacuum pipeline. A crude product tank nitrogen regulating valve 9 is installed on the third nitrogen inlet. A crude product tank inlet valve 10 is installed on the crude product tank inlet. A crude product tank material outlet is installed on the pipeline between the crude product outlet valve 7 and the crude product tank inlet valve 10. A crude product tank discharge valve 8 is installed on the crude product outlet. The top material outlet of the distillation column 5 is also connected to the product tank inlet of the product tank 15 via a pipeline. A product outlet valve 12 is installed on the pipeline between the liquid phase outlet and the product tank inlet. The product tank 15 is also equipped with a fourth nitrogen inlet and a product tank vacuum pipeline. A product tank nitrogen regulating valve 13 is installed on the fourth nitrogen inlet, and a product tank feed valve 14 is installed on the product tank inlet. A product tank material outlet is installed on the pipeline between the product outlet valve 12 and the product tank feed valve 14. A product tank discharge valve 16 is installed on the product tank material outlet, and the product tank discharge valve 16 is connected to the sampling and filling glove box 17. The product tank 15 and the sampling and filling glove box 17 are connected. The first nitrogen inlet, the second nitrogen inlet, the third nitrogen inlet and the fourth nitrogen inlet are all connected to nitrogen cylinders or nitrogen pipelines, and the nitrogen is 9N high-purity nitrogen. Pressure detection devices are installed on the vacuum lines of the distillation column, crude product tank, and product tank. All three lines are connected to the cold trap 21. The cold trap 21 is connected to the vacuum pump 23 via a pipeline. A vacuum pump inlet valve 22 is installed on the pipeline between the vacuum pump 23 and the cold trap 21. A distillation column vacuum regulating valve 20 is installed at the end of the distillation column vacuum line, a crude product tank vacuum regulating valve 18 is installed on the crude product tank vacuum line, and a product tank vacuum regulating valve 19 is installed on the product tank vacuum line. The ultimate vacuum of the vacuum pump 23 is 1~20 Pa, and the pumping speed is 5~30 m / s². 3 / h, the cold trap 23 is equipped with a jacketed heat exchanger, the heat exchange medium is cooling oil, and the heat exchange temperature is -120~-60℃.

[0021] Method Implementation Examples A method for vacuum distillation of electronic-grade organometallic precursors includes the following steps: The organometallic precursor in raw material tank 1 is conveyed to distillation column 5 via nitrogen pressurization. The material is then purified by distillation in column 5. The pressure in distillation column 5 is stabilized by controlling the nitrogen regulating valve 6 and the vacuum regulating valve 20. The distillation column 5 is heated by controlling the temperature of the heat transfer oil in the reboiler jacket. The material in the reboiler of column 5 is stirred by the agitator. The vaporized material rises through the packing to the top tube heat exchanger. The rising vapor is cooled and condensed into a liquid phase by controlling the temperature of the cooling oil for reflux and collection. Initially, the crude product collection valve 7 and the crude product tank feed valve 10 are opened to collect the collected light components. In the crude product tank 11, when the absolute pressure at the material outlet of the crude product tank is 100~500Pa and the temperature reaches 80~120℃, the crude product outlet valve 7 and the crude product tank feed valve 10 are closed, and the product outlet valve 12 and the product tank feed valve 14 are opened to collect the material into the product tank 15. By controlling the opening of the nitrogen regulating valves of the crude product tank 11 and the product tank 15, the nitrogen regulating valve of the crude product tank 9, the nitrogen regulating valve of the product tank 13, the vacuum regulating valve of the crude product tank 18, and the vacuum regulating valve of the product tank 19, it is ensured that the pressure in the crude product tank 11 is lower than the pressure at the material outlet of the crude product tank and the pressure in the product tank 15 is lower than the pressure at the material outlet of the product tank, so as to ensure that the material is collected into the crude product tank 11 and the product tank 15 respectively. Once the crude product tank 11 is full, close the crude product discharge valve 7 and the crude product tank vacuum regulating valve 18, open the crude product tank nitrogen regulating valve 9, control the pressure inside the crude product tank 11 to 0.01 MPa~0.1 MPa, open the crude product tank discharge valve 8, and transfer the material in the crude product tank 11 to a pressure cylinder or other container for further distillation and purification; once the product tank 15 is full, close the product discharge valve 12 and the product tank vacuum regulating valve 19, open the product tank nitrogen regulating valve 13, control the pressure inside the product tank 15 to 0.01 MPa~0.1 MPa, open the product tank discharge valve 16, and transfer the product in the product tank 15 to the sampling and filling glove box 17 for sampling and analysis. After the results are qualified, with a main content ≥99.5% and metal ions meeting 6N, the product cylinder is filled; The vacuum regulating valve 20 of the distillation column, the vacuum regulating valve 18 of the crude product tank, and the vacuum regulating valve 19 of the product tank are all connected to the bottom pipe of the cold trap 21. The temperature of the cold trap 21 is controlled by cooling oil, and the pressure in the cold trap 21 is controlled by a vacuum pump 23, which is kept between 5 and 100 Pa. The exhaust gas of the vacuum pump is collected and treated.

[0022] Method Example 1 The raw material is (cyclopentadienyl)tris(dimethylamino)zirconium, derived from the upstream synthesis process, with a purity of 92 wt%. The remainder consists of n-hexane, toluene, other light and heavy components, and metal ion impurities. The operating pressure of raw material tank 1 is 0.03 MPaG, forcing the material into distillation column 5. The temperature of the heat transfer oil in the bottom of distillation column 5 is 110°C, the stirring frequency is 300 rpm, the temperature of the refrigerant at the top of the column is 20°C, the operating pressure of distillation column 5 is 300 PaA, and the theoretical number of plates is 35. During the collection process, the operating pressure of crude product tank 11 and product tank 15 is 150 PaA to ensure smooth product collection. During the discharge process, the operating pressure of crude product tank 11 and product tank 15 is 0.05 MPaG. The pressure of product tank 15 entering the sampling and filling glove box 17 is significantly higher than the pressure of the inert gas inside the glove box. The cooling oil temperature of cold trap 21 is -90℃ to ensure that impurities can be completely condensed in the cold trap. The ultimate vacuum of vacuum pump 23 is 5 Pa, and the pumping speed is 10 m / s. 3 / h. Under these conditions, the purity of (cyclopentadienyl)tris(dimethylamino)zirconium produced by distillation was 99.8% according to NMR spectroscopy, and the total metal ion impurities met the 6N index requirements. The organometallic precursors produced using this vacuum distillation method have high purity, high yield, stable product quality, and controllable parameters.

[0023] Method Example 2 The raw material is (n-propylcyclopentadienyl)tris(dimethylamino)zirconium, derived from the upstream synthesis process, with a purity of 93 wt%. The remainder consists of n-hexane, toluene, other light and heavy components, and metal ion impurities. The operating pressure of raw material tank 1 is 0.05 MPaG, forcing the material into distillation column 5. The temperature of the heat transfer oil in the bottom of distillation column 5 is 115°C, the stirring frequency is 500 rpm, the temperature of the refrigerant at the top of the column is 30°C, the operating pressure of distillation column 5 is 260 PaA, and the theoretical number of plates is 20. During the extraction process, the operating pressure of crude product tank 11 and product tank 15 is approximately 100 PaA to ensure smooth product entry. During the discharge process, the operating pressure of crude product tank 11 and product tank 15 is 0.07 MPaG. The pressure of product tank 15 entering the sampling and filling glove box 17 is significantly higher than the pressure of the inert gas inside the glove box. The cooling oil temperature of cold trap 21 is -90℃ to ensure that impurities can be completely condensed in the cold trap. The ultimate vacuum of vacuum pump 23 is 5 Pa, and the pumping speed is 10 m / s. 3 / h. Under these conditions, the purity of (n-propylcyclopentadienyl)tris(dimethylamino)zirconium produced by distillation was 99.6% according to NMR spectroscopy, and the total metal ion impurities met the 6N index requirements. The organometallic precursors produced using this vacuum distillation method have high purity, high yield, stable product quality, and controllable parameters.

[0024] Method Example 3 The raw material is (cyclopentadienyl)tris(dimethylamino)hafnium, derived from the upstream synthesis process, with a purity of 91 wt%. The remainder consists of n-hexane, toluene, other light and heavy components, and metal ion impurities. The operating pressure of feed tank 1 is 0.1 MPaG, forcing the material into distillation column 5. The temperature of the heat transfer oil in the bottom of distillation column 5 is 110°C, the stirring frequency is 800 rpm, the refrigerant temperature at the top of the column is -10°C, the operating pressure of distillation column 5 is 200 PaA, and the theoretical number of plates is 50. During the extraction process, the operating pressure of crude product tank 11 and product tank 15 is approximately 100 PaA to ensure smooth product entry. During the discharge process, the operating pressure of crude product tank 11 and product tank 15 is 0.1 MPaG. The pressure in product tank 15 entering the sampling and filling glove box 17 is significantly higher than the pressure of the inert gas inside the glove box. The cooling oil temperature of cold trap 21 is -90℃ to ensure that impurities can be completely condensed in the cold trap. The ultimate vacuum of vacuum pump 23 is 5 Pa, and the pumping speed is 10 m / s. 3 / h. Under these conditions, the purity of (cyclopentadienyl)tris(dimethylamino)hafnium produced by distillation was 99.7% according to NMR spectroscopy, and the total impurities of metal ions met the 6N index requirements. The organometallic precursors produced using this vacuum distillation method have high purity, high yield, stable product quality, and controllable parameters.

[0025] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the invention by those skilled in the art. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the invention should be included within the scope of protection of the invention.

Claims

1. A vacuum distillation apparatus for electronic-grade organometallic precursors, characterized in that, It includes a raw material tank (1), a distillation column (5), a crude product tank (11), a product tank (15), a sampling and filling glove box (17), a vacuum pump (23), and a cold trap (21). The raw material tank (1) is provided with a first nitrogen inlet and a material outlet; the material outlet and the bottom of the distillation column (5) are connected by a pipeline; the top of the distillation column (5) is provided with a second nitrogen inlet and a distillation column vacuum pipeline; the top material outlet of the distillation column (5) is connected by a pipeline to the crude product tank inlet of the crude product tank (11); the top material outlet of the distillation column (5) is also connected by a pipeline to the product tank inlet of the product tank (15); the crude product tank (11) is provided with a third nitrogen inlet and a crude product tank vacuum pipeline; the product tank (15) is provided with a fourth nitrogen inlet and a product tank vacuum pipeline; the product tank (15) is connected to the sampling and filling glove box (17); the distillation column vacuum pipeline, the crude product tank vacuum pipeline and the product tank vacuum pipeline are all connected to the cold trap (21); the cold trap (21) is connected to the vacuum pump (23).

2. The vacuum distillation apparatus for an electronic-grade organometallic precursor according to claim 1, characterized in that, A nitrogen regulating valve (2) for the raw material tank is provided on the first nitrogen inlet, a material discharge valve (3) for the raw material tank is provided on the material outlet, a material feed valve (4) for the distillation column is provided on the pipeline connecting the material outlet and the bottom of the distillation column (5), and a nitrogen regulating valve (6) for the distillation column is provided on the second nitrogen inlet.

3. The vacuum distillation apparatus for an electronic-grade organometallic precursor according to claim 1, characterized in that, The distillation column (5) is equipped with a jacketed heat exchanger in the reboiler, with heat transfer oil as the heat exchange medium and a heat exchange temperature of 90~150℃. The distillation column (5) is equipped with a stirrer in the reboiler, with a stirrer speed of 1~1000 rpm. The distillation column (5) is equipped with a tubular heat exchanger at the top, with cooling oil as the heat exchange medium and a heat exchange temperature of -20~40℃. The distillation column (5) has 20~50 theoretical plates. The distillation column (5) is equipped with temperature and pressure detection devices at the reboiler, column section connection, and top material outlet.

4. The vacuum distillation apparatus for an electronic-grade organometallic precursor according to claim 1, characterized in that, The first nitrogen inlet, the second nitrogen inlet, the third nitrogen inlet and the fourth nitrogen inlet are all connected to nitrogen cylinders or nitrogen pipelines, and the nitrogen is 9N high-purity nitrogen.

5. The vacuum distillation apparatus for an electronic-grade organometallic precursor according to claim 1, characterized in that, The distillation column (5) is equipped with a liquid phase outlet and a liquid phase outlet pipe. The liquid phase outlet is connected to the crude product tank inlet and the product tank inlet through the pipe respectively. A crude product outlet valve (7) is installed on the pipe between the liquid phase outlet and the crude product tank inlet. A product outlet valve (12) is installed on the pipe between the liquid phase outlet and the product tank inlet. A nitrogen regulating valve (9) for the crude product tank is provided on the third nitrogen inlet, a crude product tank feed valve (10) is provided on the crude product tank feed inlet, a crude product tank material outlet is provided on the pipeline between the crude product outlet valve (7) and the crude product tank feed valve (10), and a crude product tank discharge valve (8) is provided on the crude product tank material outlet. The fourth nitrogen inlet is equipped with a nitrogen regulating valve (13) for the product tank, and a product tank feed valve (14) is equipped on the product tank feed inlet. A product tank material outlet is provided on the pipeline between the product outlet valve (12) and the product tank feed valve (14). A product tank discharge valve (16) is provided on the product tank material outlet. The product tank discharge valve (16) is connected to the sampling and filling glove box (17).

6. The vacuum distillation apparatus for an electronic-grade organometallic precursor according to claim 5, characterized in that, Pressure detection devices are installed on the vacuum lines of the distillation column, the crude product tank, and the product tank.

7. The vacuum distillation apparatus for an electronic-grade organometallic precursor according to claim 1, characterized in that, The vacuum pump (23) and the cold trap (21) are connected by a pipeline, and a vacuum pump inlet valve (22) is installed on the pipeline between the vacuum pump (23) and the cold trap (21); a distillation column vacuum regulating valve (20) is installed at the end of the distillation column vacuum pipeline, a crude product tank vacuum regulating valve (18) is installed on the crude product tank vacuum pipeline, and a product tank vacuum regulating valve (19) is installed on the product tank vacuum pipeline; the ultimate vacuum of the vacuum pump (23) is 1~20 Pa, and the pumping speed is 5~30 m. 3 / h.

8. The vacuum distillation apparatus for an electronic-grade organometallic precursor according to claim 7, characterized in that, The cold trap (21) is equipped with a jacketed heat exchanger, the heat exchange medium is cooling oil, and the heat exchange temperature is -120~-60℃.

9. A method for vacuum distillation of electronic-grade organometallic precursors, characterized in that, The vacuum distillation apparatus for electronic-grade organometallic precursors as described in any one of claims 1-8 is used to perform vacuum distillation on the raw materials of organometallic precursors, comprising the following steps: The metal-organic precursor in the raw material tank (1) is transported to the distillation column (5) by nitrogen pressure. The material is purified by distillation in the distillation column (5). The pressure of the distillation column (5) is stabilized by controlling the nitrogen regulating valve (6) and the vacuum regulating valve (20) of the distillation column. The distillation column (5) is heated by controlling the temperature of the heat transfer oil in the jacket of the distillation column (5). The material in the bottom of the distillation column (5) is stirred by the stirrer in the distillation column (5). The vaporized material rises to the top tube heat exchanger through the packing. The rising gas phase is cooled and condensed into liquid phase by controlling the temperature of the cooling oil. The liquid phase is then refluxed and collected. The crude product collection valve (7) and the crude product tank feed valve (10) are opened in the early stage to collect the collected light components into the crude product tank. In step 11), when the absolute pressure at the material outlet of the crude product tank is 100~500Pa and the temperature reaches 80~120℃, close the crude product outlet valve (7) and the crude product tank feed valve (10), open the product outlet valve (12) and the product tank feed valve (14), and collect the material into the product tank (15). By controlling the opening of the nitrogen regulating valves (9), (13), (18), and (19) of the crude product tank (11) and the product tank (15), ensure that the pressure in the crude product tank (11) is lower than the pressure at the material outlet of the crude product tank and the pressure in the product tank (15) is lower than the pressure at the material outlet of the product tank, and ensure that the material is collected into the crude product tank (11) and the product tank (15) respectively. Once the crude product tank (11) is full, close the crude product discharge valve (7) and the crude product tank vacuum regulating valve (18), open the crude product tank nitrogen regulating valve (9), control the pressure inside the crude product tank (11) to 0.01Mpa~0.1Mpa, open the crude product tank discharge valve (8), and transfer the material inside the crude product tank (11) into a pressure cylinder or other container for further distillation and purification; once the product tank (15) is full, close the product discharge valve (12) and the product tank vacuum regulating valve (19), open the product tank nitrogen regulating valve (13), control the pressure inside the product tank (15) to 0.01Mpa~0.1Mpa, open the product tank discharge valve (16), and press the product in the product tank (15) into the sampling and filling glove box (17) for sampling and analysis. After the results are qualified, the main content is ≥99.5%, and the metal ions meet 6N, and the product cylinder is filled. The vacuum regulating valve (20) of the distillation column, the vacuum regulating valve (18) of the crude product tank and the vacuum regulating valve (19) of the product tank are all connected to the bottom pipe of the cold trap (21). The temperature of the cold trap (21) is controlled by cooling oil. The pressure in the cold trap (21) is controlled by a vacuum pump (23) between 5 and 100 Pa. The exhaust gas of the vacuum pump is collected and treated.

10. The vacuum distillation method for an electronic-grade organometallic precursor according to claim 9, characterized in that, The organometallic precursor includes any one of (n-propylcyclopentadienyl)tris(dimethylamino)zirconium, (cyclopentadienyl)tris(dimethylamino)zirconium, (cyclopentadienyl)tris(dimethylamino)hafnium, or other thermosensitive organometallic precursors.

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