A filling device and a filling method of high-purity germanium tetrafluoride gas

Abstract

The application discloses a kind of high-purity germanium tetrafluoride gas filling equipment and filling method, by first cooling platform, second cooling platform, vacuum pump, first storage container, second storage container, low-temperature refrigerant unit and normal-temperature refrigerant unit composition;The first storage container is set on the first cooling platform;The second storage container is set on the second cooling platform;First storage container is connected with valve b1 and valve b2, valve b3 and vacuum pump by valve;Valve b2 is connected with second storage container;Normal-temperature refrigerant unit is connected with valve a1 and first cooling platform by valve a4;Valve a1 is connected with valve a2 and low-temperature refrigerant unit;Normal-temperature refrigerant unit is connected with valve a3 and first cooling platform by valve a5;Valve a3 is connected with low-temperature refrigerant unit and second cooling platform;Valve a2 is connected with second cooling platform.In the process of filling, there is no high-pressure buffer tank, high-pressure gas cylinder and other dangerous sources, which guarantees the safety and simplicity in the process of filling, and also guarantees the purity of gas.

Description

Technical Field

[0001] This invention belongs to the field of inorganic chemical process technology, specifically relating to a filling device and method for high-purity germanium tetrafluoride gas. Background Technology

[0002] Germanium tetrafluoride (GDF) is a fluoride of germanium, generally prepared by the reaction of fluorine gas with metals. Alternatively, it can be obtained by reacting high-purity germanium dioxide with hydrogen fluoride to prepare barium fluorogermanate, followed by thermal decomposition at 800°C. GDF possesses unique physicochemical properties: completely dry germanium tetrafluoride gas is colorless at room temperature and pressure; it becomes solid below -36.5°C. When germanium tetrafluoride reacts with water in air, it produces a large amount of white fumes; it hydrolyzes in water to form germanium dioxide and fluorogermanic acid. GDF is primarily used to produce stable germanium-72 and germanium-76 isotopes, mainly as a chemical dopant and ion implant in the semiconductor industry. The germanium-72 isotope of electronic-grade germanium tetrafluoride is used as a chemical reagent for etching and performance optimization in the production of DRAM chips within the 10nm range, while germanium-76 isotope single crystals can be used as tracer atoms for high-energy physics dark matter detection.

[0003] Currently, the most common high-purity gas filling system in China uses low-temperature, low-pressure liquefied gas, which is vaporized into high-pressure gas by a vaporizer and then filled into steel cylinders by a high-pressure pump. This method has been reported in many documents, such as Chinese patent documents CN114183689A, CN210662295U, and CN114893713A. This type of filling method is suitable for filling gases that exist in liquid form and have relatively stable chemical properties under low-temperature and high-pressure conditions. However, due to the special chemical properties of germanium tetrafluoride, it generally exists in solid form under low-temperature, high-pressure, and low-temperature, normal-pressure conditions. Therefore, this type of filling method is not suitable for filling germanium tetrafluoride. Moreover, germanium tetrafluoride exists in gaseous form at room temperature and high pressure. Therefore, we provide a safe, simple filling equipment and method that can guarantee product quality for filling high-purity germanium tetrafluoride gas. Summary of the Invention

[0004] The purpose of this invention is to provide a novel, safe, simple, and quality-assured germanium tetrafluoride gas equipment and method to solve the problems of filling and storing germanium tetrafluoride gas under normal pressure and to ensure that germanium tetrafluoride is not contaminated during the filling process. To achieve the above objectives, this invention provides the following technical solutions.

[0005] To address the aforementioned problems, a first aspect of the present invention provides a filling device for high-purity germanium tetrafluoride gas, comprising a first cooling platform, a second cooling platform, a vacuum pump, a first storage container, a second storage container, a cryogenic refrigerant unit, and a room-temperature refrigerant unit; the first storage container is disposed on the first cooling platform; the second storage container is disposed on the second cooling platform; the first storage container is connected to the vacuum pump via valve b1, valve b2, valve b3, and the vacuum pump; valve b2 is connected to the second storage container; the room-temperature refrigerant unit is connected to valve a1 and the first cooling platform via valve a4; valve a1 is connected to valve a2 and the cryogenic refrigerant unit; the room-temperature refrigerant unit is connected to the first cooling platform via valve a5, valve a3; valve a3 is connected to the cryogenic refrigerant unit and the second cooling platform; and valve a2 is connected to the second cooling platform.

[0006] Furthermore, the first cooling platform comprises a first insulation cover, a first silicone oil outlet, a first scale, a first silicone oil inlet, a first silicone oil jacket, and a first insulation sleeve; the first insulation sleeve is disposed on the first scale; the first silicone oil jacket is disposed inside the first insulation sleeve; the first insulation cover is disposed on the first insulation sleeve and the first silicone oil jacket; the first silicone oil inlet passes through the first insulation sleeve and is disposed on the lower part of one side of the first silicone oil jacket, and the first silicone oil outlet is disposed on the upper part of the other side of the first silicone oil jacket, the first silicone oil outlet passing through the first insulation sleeve; a first storage container is disposed inside the first silicone oil jacket, and the first insulation cover is provided with a passage that cooperates with the first storage container. The second cooling platform consists of a second insulation cover, a second silicone oil outlet, a second scale, a second silicone oil inlet, a second silicone oil jacket, and a second insulation sleeve. The second insulation sleeve is mounted on the second scale. The second silicone oil jacket is located inside the second insulation sleeve. A second insulation cover is mounted on the second insulation sleeve and the second silicone oil jacket. The second silicone oil inlet passes through the second insulation sleeve and is located at the lower part of one side of the second silicone oil jacket. A second silicone oil outlet is located at the upper part of the other side of the second silicone oil jacket and passes through the second insulation sleeve. A second storage container is located inside the second silicone oil jacket, and the second insulation cover has a through hole that mates with the second storage container.

[0007] According to another aspect of the present invention, a method for filling a high-purity germanium tetrafluoride gas filling device is provided, comprising: placing a first storage container and a second storage container in a first cooling platform and a second cooling platform, respectively; turning on a vacuum pump to evacuate the first and second storage containers at room temperature; when the vacuum level of the containers is below 0.008 MPa, closing connecting valves b1 and b2, and then turning off the vacuum pump; injecting helium gas into the evacuated first and second storage containers until the gas pressure inside the two containers returns to normal atmospheric pressure, and then evacuating again to below 0.008 MPa, repeating this process. The process is repeated 2 to 3 times; the cryogenic refrigerant unit is turned on and the set temperature is between -50℃ and -60℃. When the silicone oil temperature reaches the required level, valves a1, a2, and a3 are opened to inject silicone oil into the first and second cooling platforms, so that the temperature of the first and second cooling platforms is between -50℃ and -60℃; the spare first and second storage containers are cooled in the first and second cooling platforms for 40 to 60 minutes respectively, ensuring that the temperature inside the first and second storage containers reaches below -50℃; valves b1 and b3 are opened to inject four... Germanium tetrafluoride gas should be injected at a rate not exceeding 20 L / min. When the reading on the first scale reaches 25 kg to 30 kg, close valves b1 and b3 and maintain the temperature for 30 to 60 minutes to ensure that the gaseous germanium tetrafluoride completely changes from a gaseous state to a solid state. Open valve b1 to evacuate the first storage container. Stop evacuating when the vacuum pump pressure reading no longer changes, and close valve b1. Close valves a1 and a3 to stop injecting silicone oil between -50°C and -60°C into the first cooling platform. Open valves a4 and a5 to inject room temperature silicone oil into the first cooling platform, so that the silicone oil in the first cooling platform... The temperature of the first storage container rises, causing germanium tetrafluoride inside to vaporize. Once the pressure in the first storage container reaches 0.8 MPa to 0.1 MPa, valves b1 and b2 are opened, and germanium tetrafluoride is injected into the second storage container. The injection rate should not exceed 15 L / min. When the scale reading on the second cooling platform reaches 10 kg to 13 kg, valve b1 is closed, and the second storage container is kept warm for 30 min to 60 min. Finally, the second storage container is evacuated. After filling, the second storage container is removed and replaced with a new one. This process can be repeated 2 to 3 times.

[0008] The above-mentioned technical solution of the present invention has the following beneficial technical effects: A high-purity germanium tetrafluoride filling equipment is a germanium tetrafluoride storage container cooling platform. This device is mainly used for cooling the germanium tetrafluoride storage container. The internal temperature of the germanium tetrafluoride storage container reaches between -50°C and -60°C, so that the germanium tetrafluoride is transformed from gaseous sublimation into solid state in the storage container. Then, the container storing germanium tetrafluoride is evacuated, which can remove impurities such as nitrogen and oxygen mixed with the high-purity germanium tetrafluoride gas during the filling process, thereby ensuring the quality of high-purity germanium tetrafluoride.

[0009] A high-purity germanium tetrafluoride (GDF) filling method is designed based on the unique properties of germanium tetrafluoride gas. At temperatures below -36.5℃, germanium tetrafluoride changes from a gaseous state to a solid state. By evacuating the germanium tetrafluoride storage container to create a negative pressure state, germanium tetrafluoride at atmospheric and medium pressures (0.1MPa-3MPa) can automatically flow into the storage container. Currently, the common high-pressure filling pressure is 15MPa, and some methods use 20MPa-30MPa. This method eliminates the presence of hazardous sources such as high-pressure buffer tanks and high-pressure cylinders during the filling process. Furthermore, cooling the germanium tetrafluoride storage container causes the germanium tetrafluoride to change from a gaseous state to a solid state upon entering the container. Residual gas in the cylinder is then extracted, achieving a further purification effect. This method ensures safety, simplicity, and gas purity during the filling process. Attached Figure Description

[0010] Figure 1 A schematic diagram of the layout of a filling equipment for high-purity germanium tetrafluoride gas. Figure 2 This is a schematic diagram of the first cooling platform structure; Figure 3 This is a schematic diagram of the second cooling platform.

[0011] Figure label: 1: Vacuum pump; 2: First cooling platform; 3: Second cooling platform; 4: First storage container; 5: Second storage container; 6: Low-temperature refrigerant unit; 7: Normal-temperature refrigerant unit; 21: First insulation cover; 22: First silicone oil outlet; 23: First scale; 24: First silicone oil inlet; 25: First silicone oil jacket; 26: First insulation sleeve assembly; 31: First insulation cover; 32: First silicone oil outlet; 33: First scale; 34: First silicone oil inlet; 35: First silicone oil jacket; 36: First insulation sleeve assembly. Detailed Implementation

[0012] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to specific embodiments and the accompanying drawings. It should be understood that these descriptions are merely exemplary and not intended to limit the scope of the invention. Furthermore, descriptions of well-known structures and techniques are omitted in the following description to avoid unnecessarily obscuring the concept of the invention.

[0013] like Figure 1As shown, a filling device for high-purity germanium tetrafluoride gas is provided, comprising a first cooling platform 2, a second cooling platform 3, a vacuum pump 1, a first storage container 4, a second storage container 5, a cryogenic refrigerant unit 6, and a normal-temperature refrigerant unit 7. The first storage container 4 is disposed on the first cooling platform 2; the second storage container 5 is disposed on the second cooling platform 3; the first storage container is connected to the vacuum pump via valve b1, valve b2, valve b3, and the vacuum pump; valve b2 is connected to the second storage container; the outlet of the normal-temperature refrigerant unit is connected to valve a1 and the first cooling platform via valve a4; valve a1 is connected to valve a2 and the outlet of the cryogenic refrigerant unit; the inlet of the normal-temperature refrigerant unit is connected to valve a3 and the first cooling platform via valve a5; valve a3 is connected to the inlet of the cryogenic refrigerant unit and the second cooling platform; and valve a2 is connected to the second cooling platform.

[0014] like Figure 2 and Figure 3 As shown, the first cooling platform consists of a first insulation cover 21, a first silicone oil outlet 22, a first scale 23, a first silicone oil inlet 24, a first silicone oil interlayer 25, and a first insulation sleeve 26. The first insulation sleeve is mounted on the first scale. The first silicone oil interlayer is located inside the first insulation sleeve. The first insulation cover is mounted on the first insulation sleeve and the first silicone oil interlayer. The first silicone oil inlet passes through the first insulation sleeve and is located at the lower part of one side of the first silicone oil interlayer. The first silicone oil inlet is connected to valves a4 and a1. The first silicone oil outlet is located at the upper part of the other side of the first silicone oil interlayer. The first silicone oil outlet is connected to valves a3 and a5. The first silicone oil outlet passes through the first insulation sleeve. A first storage container is located inside the first silicone oil interlayer. The first insulation cover has a through hole that mates with the first storage container. The second cooling platform consists of a second insulation cover 31, a second silicone oil outlet 32, a second scale 33, a second silicone oil inlet 34, a second silicone oil interlayer 35, and a second insulation sleeve 36. The second insulation sleeve is installed on the second scale. The second silicone oil interlayer is installed inside the second insulation sleeve. A second insulation cover is installed on the second insulation sleeve and the second silicone oil interlayer. The second silicone oil inlet passes through the second insulation sleeve and is located at the lower part of one side of the second silicone oil interlayer. The second silicone oil inlet is connected to valve a2. A second silicone oil outlet is located at the upper part of the other side of the second silicone oil interlayer. The second silicone oil inlet is connected to valve a3 and the inlet of the low-temperature refrigerant unit. The second silicone oil outlet passes through the second insulation sleeve. A second storage container is installed inside the second silicone oil interlayer. The second insulation cover has a through hole that matches the second storage container.

[0015] Another aspect of the present invention provides a filling method for a filling device for high-purity germanium tetrafluoride gas, characterized by comprising: placing a first storage container and a second storage container in a first cooling platform and a second cooling platform, respectively; turning on a vacuum pump to evacuate the first and second storage containers at room temperature; when the vacuum level of the containers is below 0.008 MPa, closing connecting valves b1 and b2, and then turning off the vacuum pump; injecting helium gas into the evacuated first and second storage containers until the gas pressure inside the two containers returns to normal atmospheric pressure, and then evacuating again to below 0.008 MPa. Repeat this process 2 to 3 times; turn on the cryogenic refrigerant unit and set the temperature to between -50℃ and -60℃. Once the silicone oil temperature reaches the required level, open valves a1, a2, and a3 to inject silicone oil into the first and second cooling platforms, ensuring that the temperatures of the first and second cooling platforms are between -50℃ and -60℃; cool the spare first and second storage containers in the first and second cooling platforms for 40 to 60 minutes respectively, ensuring that the temperatures inside the first and second storage containers reach below -50℃; open valves b1 and b3 to inject silicone oil into the first storage container. Introduce germanium tetrafluoride gas at a rate not exceeding 20 L / min. When the reading on the first scale reaches 25 kg to 30 kg, close valves b1 and b3 and maintain the temperature for 30 to 60 minutes to ensure that the gaseous germanium tetrafluoride completely changes from a gaseous state to a solid state. Open valve b1 to evacuate the first storage container. Stop evacuating when the vacuum pump pressure reading no longer changes, and close valve b1. Close valves a1 and a3 to stop injecting silicone oil between -50°C and -60°C into the first cooling platform. Open valves a4 and a5 to inject room temperature silicone oil into the first cooling platform, so that the silicone oil in the first cooling platform is at room temperature. The temperature of the first storage container rises, causing germanium tetrafluoride in the container to vaporize. When the pressure in the first storage container reaches 0.8MPa to 0.1MPa, valves b1 and b2 are opened to inject germanium tetrafluoride into the second storage container, and the injection rate should not exceed 15L / min. When the scale reading on the second cooling platform reaches 10kg to 13kg, valve b1 is closed, and the second storage container is kept warm for 30min to 60min. Finally, the second storage container is evacuated. After filling, the second storage container is removed and replaced with a new second storage container. It can be filled 2 to 3 times continuously.

[0016] Vacuuming the germanium tetrafluoride storage container to create a negative pressure environment allows germanium tetrafluoride at atmospheric and medium pressures (0.1 MPa-3 MPa) to automatically flow into the container. Currently, the common high-pressure filling pressure is 15 MPa, and there are also 20 MPa-30 MPa methods. This method eliminates the presence of hazardous sources such as high-pressure buffer tanks and high-pressure gas cylinders during the filling process. Secondly, cooling the germanium tetrafluoride storage container causes the germanium tetrafluoride to change from a gaseous state to a solid state upon entering the container. The remaining gas in the cylinder is then extracted, as shown in Table 1, achieving a further purification effect. This ensures the safety and simplicity of the filling process while also guaranteeing the purity of the gas.

[0017] Table 1. Gas Chromatography Detection Results of Three Groups of Samples It should be understood that the specific embodiments described above are merely illustrative or explanatory of the principles of the invention and do not constitute a limitation thereof. Therefore, any modifications, equivalent substitutions, improvements, etc., made without departing from the spirit and scope of the invention should be included within the protection scope of the invention. Furthermore, the appended claims are intended to cover all variations and modifications falling within the scope and boundaries of the appended claims, or equivalent forms of such scope and boundaries.

Claims

1. A filling device for high-purity germanium tetrafluoride gas, characterized in that, It consists of a first cooling platform, a second cooling platform, a vacuum pump, a first storage container, a second storage container, a cryogenic refrigerant unit, and a normal temperature refrigerant unit. The first storage container is mounted on the first cooling platform; the second storage container is mounted on the second cooling platform. The first storage container is equipped with a valve b1 to control its on / off state, and the second storage container is equipped with a valve b2 to control its on / off state. Valve b1 is connected to valve b2, valve b3, and the vacuum pump. Valve b3 is used to connect to an external gas source to inject germanium tetrafluoride gas. The oil inlet of the first cooling platform is connected to the oil outlet of the low-temperature refrigerant unit through valve a3. The oil outlet of the first cooling platform is connected to the oil inlet of the low-temperature refrigerant unit through valve a1. The oil inlet of the first cooling platform is connected to the oil outlet of the normal temperature refrigerant unit through valve a5. The oil outlet of the first cooling platform is connected to the oil inlet of the normal temperature refrigerant unit through valve a4. The oil outlet of the second cooling platform is connected to the oil inlet of the low-temperature refrigerant unit through valve a2. The oil inlet of the second cooling platform is connected to the oil outlet of the low-temperature refrigerant unit.

2. The filling equipment for high-purity germanium tetrafluoride gas according to claim 1, characterized in that, The first cooling platform consists of a first insulation cover, a first silicone oil outlet, a first scale, a first silicone oil inlet, a first silicone oil interlayer, and a first insulation sleeve; the first insulation sleeve is disposed on the first scale; the first silicone oil interlayer is disposed inside the first insulation sleeve; the first insulation cover is disposed on the first insulation sleeve and the first silicone oil interlayer; the first silicone oil inlet passes through the first insulation sleeve and is disposed at the lower part of one side of the first silicone oil interlayer, and the first silicone oil outlet is disposed at the upper part of the other side of the first silicone oil interlayer, the first silicone oil outlet passing through the first insulation sleeve; a first storage container is disposed inside the first silicone oil interlayer, and the first insulation cover is provided with a through hole that mates with the first storage container; The second cooling platform consists of a second insulation cover, a second silicone oil outlet, a second scale, a second silicone oil inlet, a second silicone oil interlayer, and a second insulation sleeve. The second insulation sleeve is mounted on the second scale. The second silicone oil interlayer is located inside the second insulation sleeve. A second insulation cover is mounted on the second insulation sleeve and the second silicone oil interlayer. The second silicone oil inlet passes through the second insulation sleeve and is located at the lower part of one side of the second silicone oil interlayer. A second silicone oil outlet is located at the upper part of the other side of the second silicone oil interlayer and passes through the second insulation sleeve. A second storage container is located inside the second silicone oil interlayer, and the second insulation cover has a through hole that mates with the second storage container.

3. A filling method for a filling device based on the high-purity germanium tetrafluoride gas described in claim 2, characterized in that, include: The first storage container and the second storage container are placed in the first cooling platform and the second cooling platform, respectively; Turn on the vacuum pump and evacuate the first and second storage containers at room temperature. When the vacuum level of the containers is below 0.008 MPa, close the connecting valves b1 and b2, and then turn off the vacuum pump. Inject helium into the first and second storage containers that have been evacuated until the gas pressure inside the two containers returns to normal atmospheric pressure, and then evacuate them again to below 0.008 MPa. Repeat this process 2 to 3 times. Turn on the low-temperature refrigerant unit and set the temperature to between -50℃ and -60℃. When the silicone oil temperature reaches the required level, open valves a1, a2 and a3 to inject silicone oil into the first and second cooling platforms, so that the temperature of the first and second cooling platforms is between -50℃ and -60℃. The first and second storage containers are cooled in the first and second cooling platforms for 40 to 60 minutes respectively to ensure that the temperature inside the first and second storage containers reaches below -50°C. Open valves b1 and b3 to inject germanium tetrafluoride gas into the first storage container. The injection rate should not exceed 20 L / min. When the reading of the first scale reaches 25 kg to 30 kg, close valves b1 and b3 and keep it warm for 30 min to 60 min to ensure that the gaseous germanium tetrafluoride completely changes from gaseous to solid. Open valve b1 to evacuate the first storage container. Stop evacuating when the vacuum pump pressure reading no longer changes, and close valve b1. Close valves a1 and a3 to stop injecting silicone oil between -50°C and -60°C into the first cooling platform. Open valves a4 and a5 to inject room temperature silicone oil into the first cooling platform, causing the temperature of the first storage container in the first cooling platform to rise, causing germanium tetrafluoride in the container to vaporize. Once the pressure in the first storage container reaches 0.8 MPa to 0.1 MPa, open valves b1 and b2 to inject germanium tetrafluoride into the second storage container, adjusting the injection rate to not exceed 15 L / min; When the scale reading on the second cooling platform reaches 10kg to 13kg, close valve b1 and keep the second storage container warm for 30min to 60min. Finally, the second storage container is evacuated. After filling, the second storage container is removed and replaced with a new one. It can be filled 2 to 3 times in a row.

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