Phosphorane mixed gas filling method

Abstract

The invention discloses a phosphorane mixed gas filling method, and relates to the technical field of mixed gases, the phosphorane mixed gas filling method comprises instrument pretreatment, step-by-step filling, post-vacuum treatment, quality detection and safety monitoring, and the phosphorane mixed gas filling method has the advantages that a mixed accelerant is added into a filling pipeline in the phosphorane and argon filling process, so that the filling efficiency is improved; by providing a large number of active sites and unique gas diffusion channels, uniform mixing of phosphorane and argon can be accelerated, the uniformity and accuracy of mixed gas matching are improved, in the process of action of an accelerant and gas, argon molecules are fully contacted and collided with dissociated and adsorbed phosphorus atoms under the guidance of a special structure of a nano-porous material, and the phosphorus atoms are separated and adsorbed. The mixed accelerant is added to promote rapid and uniform mixing of the phosphorus and the alkane, stable and accurate-proportion phosphorus and alkane mixed gas is formed, and in the whole process, the mixed accelerant continuously plays a role, so that the uniform mixing efficiency of the mixed gas in the filling process is greatly improved compared with a traditional mode.

Description

Technical Field

[0001] This invention relates to the field of mixed gas technology, specifically a method for filling a phosphine mixed gas. Background Technology

[0002] Phosphine mixtures have extremely important applications in semiconductor manufacturing, optoelectronic device production, and some specific chemical processes. Phosphine (PH3), as a key electronic specialty gas, is often mixed with other inert gases in precise proportions to form phosphine mixtures, which are used in various process steps. For example, in the chemical vapor deposition (CVD) process in semiconductor chip manufacturing, phosphine mixtures can participate in the formation of thin film materials with specific electrical properties. With the expansion of production scale and the gradual increase in requirements for filling accuracy, some enterprises have begun to adopt automated control systems for filling phosphine mixtures. These systems typically involve installing electronic flow control valves, pressure sensors, and other equipment on the gas filling pipeline. The data collected by these sensors is transmitted to a programmable logic controller (PLC). The PLC automatically controls the flow rate of each gas and the filling time according to a preset program and mixture ratio parameters. Some enterprises have adopted this method to improve production efficiency and ensure filling accuracy to a certain extent. However, manual metering and filling methods rely entirely on the operator's skill and visual judgment of instrument data, inevitably leading to human error. For example, precise control is difficult when adjusting gas flow valves. Even a small flow deviation, over a long filling process or under conditions requiring high-precision mixture ratios, can cause a significant difference between the actual and theoretical mixture ratios, thus affecting the subsequent process effects using the mixture. This is particularly problematic in semiconductor chip manufacturing. The filling process can lead to quality problems such as unstable film performance. Whether it is manual metering and filling or filling with a simple automated control system, multiple pauses are often required during the filling process for data monitoring and adjustment. Especially in manual filling, each valve adjustment and data reading takes time, and the overall filling time for a bottle of mixed gas is relatively long. Although simple automated filling is faster than manual filling, its filling efficiency still cannot meet the requirements of high-efficiency production when facing the filling needs of large-volume and rapid turnover. For example, in large-scale semiconductor production lines, the filling efficiency cannot keep up with the production rhythm. Phosphine itself is a highly toxic gas with flammable and explosive properties. In the filling process, the existing technology has shortcomings in gas leak detection and emergency handling. In manual filling, operators may not be able to detect small gas leaks in time due to their focus on metering operations. Although there are some basic leak alarm devices in automated filling systems, the accuracy and timeliness of leak detection under complex working conditions (such as electromagnetic interference at the filling site) are not ideal. Therefore, we propose a phosphine mixed gas filling method. Summary of the Invention

[0003] The purpose of this invention is to provide a method for filling phosphine mixed gas.

[0004] To address the problems mentioned in the background section, the present invention provides the following technical solution: a method for filling a phosphine mixed gas, comprising instrument pretreatment, step-by-step filling, post-vacuum treatment, quality inspection, and safety monitoring. The specific operation steps of the phosphine mixed gas filling method are as follows: Step 1: Prepare the filling instrument, which includes a micro-nano-level flow sensor, a high-precision mass flow controller, and an in-situ gas composition analyzer. Connect the filling instrument to the gas cylinder and perform vacuum degassing on it. Step 2: Open the argon filling channel and fill the gas cylinder with argon to 60% of the target volume. Continuously monitor the filling flow rate during the filling process, and stop filling after the filling is completed. Step 3: After the argon filling is completed, pause for 2 minutes. After confirming the state of the argon in the bottle with an in-situ gas composition analyzer, open the filling channels for phosphine and argon. Set the initial filling rate of both through a high-precision mass flow controller. Monitor the flow rate in real time with a micro-nano level flow sensor. The in-situ gas composition analyzer provides feedback on the composition and pressure of the mixed gas every 2-3 seconds. When the volume ratio of phosphine and argon deviates from the target value by 0.02%, dynamically adjust the flow rate to accurately control the mixed gas ratio. Step 4: After filling is complete, close all gas filling valves, use a vacuum pump to perform post-vacuum treatment on the gas cylinder and connecting pipes, and use a helium mass spectrometer leak detector to check the airtightness of the filling device. Step 5: Use a high-precision spectrometer to perform final testing on the mixed gas composition in the gas cylinder, and determine that the error between the actual volume ratio of phosphine and argon and the target volume ratio is within ±0.02%. The filling process is then complete.

[0005] As a further aspect of the present invention: In step one, each component of the filling instrument is tested to ensure that the micro-nano level flow sensor, high-precision mass flow controller and in-situ gas composition analyzer are functioning normally, initial parameters are set, and a 30L gas cylinder to be filled is prepared to ensure that the appearance inspection and pressure test of the gas cylinder are qualified, and that the connection parts of each valve are sealed properly.

[0006] As a further aspect of the present invention: In step one, the gas cylinder and the filling instrument are connected through a high-pressure resistant and corrosion-resistant pipe. The pipe is pre-vacuum degassed to ensure that it is clean and free of impurities. After the connection is completed, the pre-vacuum treatment step is started, and the vacuum pump is turned on to evacuate the gas cylinder and the connecting pipe. The pumping rate is set to 5L / min-8L / min. After evacuation for 15min-20min and purging with argon three times, the vacuum degree of the filling instrument and the gas cylinder is controlled below 0.00133Pa.

[0007] As a further aspect of the present invention: In step two, the argon filling channel and valve are opened, and the argon filling rate is set to 6L / min-8L / min using a high-precision mass flow controller. Argon is filled into the gas cylinder to 60% of the target volume, that is, 18L of argon is filled into a 30L gas cylinder. During the filling process, a micro-nano-level flow sensor is used to monitor the argon flow rate in real time, and an in-situ gas composition analyzer provides feedback on the gas composition and pressure in the gas cylinder every 2 seconds. The filling time of argon into the gas cylinder is 3min-5min.

[0008] As a further aspect of the present invention: In step three, after the argon filling is completed, a 2-minute pause is allowed to give the argon in the cylinder sufficient time to stabilize and distribute the gas evenly. After the pause, an in-situ gas composition analyzer is used to analyze the state of the argon in the cylinder, including argon purity, impurity content, and pressure range within the cylinder. After confirming that the argon state is qualified, the filling channels for phosphine and argon are opened. A high-precision mass flow controller is used to set the initial filling rates for phosphine and argon respectively. The initial filling rate for phosphine is set to 0.4 L / min-0.6 L / min, and the initial filling rate for argon is set to... The filling rate is 1.3L / min-1.7L / min. A novel gas uniform mixing promoter is added to the filling pipeline. It is made of a special nanoporous material loaded with an active metal catalyst and has the chemical formula Pd(Al2O3). During the filling process, a micro-nano-level flow sensor continuously monitors the real-time flow of phosphine and argon with high precision. The in-situ gas composition analyzer provides feedback on the composition and pressure of the mixed gas in the cylinder every 2 seconds. When the volume ratio of phosphine and argon deviates from the target value by 0.02% through spectral analysis, the control system dynamically adjusts the flow rate based on the real-time data.

[0009] As a further aspect of the present invention: the interaction principle between the mixing accelerator and the gas is as follows: during the filling process, phosphine (PH3) molecules adsorb onto the active sites of Pd and undergo a dissociation adsorption process, as shown in the following reaction equation: ; ; ; The generated atomic state It can be uniformly mixed with argon, while hydrogen can diffuse out from the porous material. It can be continuously filled until the mixed gas in the cylinder reaches the target volume. For a 30L cylinder, the total volume of the mixed gas to be filled is 12L, namely 2.4L of phosphine and 9.6L of argon.

[0010] As a further aspect of the present invention: In step four, after closing all gas filling valves, the vacuum pump is connected to the gas cylinder and filling instrument via a high-pressure resistant and corrosion-resistant pipe, ensuring that the connection is well sealed and there is no risk of leakage. After the connection is completed, the entire connection line is checked again to ensure its stability and sealing. The vacuum pump is turned on, and the pumping rate is set to 5L / min. The pumping process lasts for 12-15 minutes. During the pumping process, a high-precision vacuum measuring instrument is used to detect the vacuum degree in the system in real time to ensure that the final vacuum degree is controlled below 0.00133Pa.

[0011] As a further aspect of the present invention: In step four, after vacuum treatment is completed, the helium mass spectrometer leak detector is moved to a suitable position so that its detection probe can be easily connected to the key detection part of the filling system. After connection, the helium mass spectrometer leak detector is turned on, and its detection sensitivity is set to 10 on the operation panel. -2 Using a helium filling device, a small amount of helium is slowly injected into the filling system at a flow rate of 0.15 L / min, with the filling time controlled between 1.5 min and 3 min. After the helium is injected, the detection program of the helium mass spectrometer leak detector is started to perform a comprehensive scan and detection of all connection parts and the entire filling system, collecting and analyzing helium information in real time. If no helium leak is detected, it indicates that the filling device has good airtightness.

[0012] As a further aspect of the present invention: In step five, the high-precision spectrometer is placed in a stable and easily operable location, with the temperature controlled between 20℃ and 25℃ and the humidity maintained between 40% and 60%. The spectrometer is connected to the computer control system using a data transmission line, and the detection data is transmitted and recorded in real time. The high-precision spectrometer is calibrated using a calibration gas. The calibration gas is a standard mixture with known precise components and a composition similar to the phosphine mixture to be detected. Following the procedures specified in the operation manual, the key parameters of the spectrometer, such as wavelength range and resolution, are adjusted sequentially to achieve optimal detection accuracy. The gas inlet of the high-precision spectrometer is connected to the valve outlet of the 30L gas cylinder to be detected using a gas sampling pipeline. During the connection process, all interfaces are ensured to be tightly sealed.

[0013] Compared with the prior art, the beneficial effects of the present invention by adopting the above technical solution are as follows: This invention introduces a mixing accelerator into the filling pipeline during the filling process of phosphine and argon. By providing numerous active sites and unique gas diffusion channels, it accelerates the uniform mixing of phosphine and argon, improving the uniformity and accuracy of the mixed gas ratio. During the interaction between the accelerator and the gas, argon molecules, guided by the special structure of the nanoporous material, fully contact and collide with the dissociated and adsorbed phosphorus atoms, promoting rapid and uniform mixing to form a stable and precisely proportioned phosphine mixture. Throughout the process, the mixing accelerator continuously plays a role, significantly improving the uniform mixing efficiency of the mixed gas compared to traditional methods, greatly enhancing the quality of the final mixed gas. By using a step-by-step filling method and refilling after the first filling pause, unnecessary long-term monitoring interruptions are avoided, significantly reducing the overall time spent filling the phosphine mixture and better meeting the high filling efficiency requirements of semiconductor production lines, etc. This invention employs a post-filling vacuum treatment followed by real-time monitoring with a high-precision vacuum gauge to ensure the final vacuum level is controlled below a specific value. This effectively removes residual mixed gases and impurities from the system, reducing safety hazards. By slowly filling a small amount of helium followed by a comprehensive scan, it can promptly and accurately detect gas leaks in the filling device. Compared to manual filling where operators struggle to detect minute leaks, and the less accurate and timely leak detection in automated filling systems under complex conditions, this invention significantly improves leak detection capabilities. Furthermore, pre-processing the instruments before filling, including inspecting each component of the filling equipment, further enhances this capability. From the initial testing of the gas cylinder's appearance and pressure resistance, to the vacuum degassing and pre-vacuum treatment of the pipeline, to the strict monitoring and control of the flow rate and state of each gas during the step-by-step filling process, and then to the post-vacuum treatment, quality inspection, and safety monitoring, every filling of phosphine mixture gas consistently meets high-quality standards. Its key indicators such as composition, purity, and airtightness are effectively guaranteed, avoiding fluctuations in filling quality caused by human factors, equipment factors, and environmental factors. This ensures that the filled mixture gas can be reliably applied in process fields with stringent gas quality requirements, such as semiconductor manufacturing and optoelectronic device production, under different batches and operating conditions. Attached Figure Description

[0014] Figure 1 This is a schematic diagram of the phosphine mixed gas filling process in an embodiment of the present invention. Detailed Implementation

[0015] The specific embodiments of the present invention will be further described below with reference to the accompanying drawings. It should be noted that these descriptions are for the purpose of aiding understanding the present invention, but do not constitute a limitation thereof. Furthermore, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0016] This invention discloses a method for filling a phosphine mixed gas, comprising instrument pretreatment, step-by-step filling, post-vacuum treatment, quality inspection, and safety monitoring. The specific operation steps of the phosphine mixed gas filling method are as follows: Step 1: Prepare the filling instrument, which includes a micro-nano-level flow sensor, a high-precision mass flow controller, and an in-situ gas composition analyzer. Connect the filling instrument to the gas cylinder and perform vacuum degassing on it. Step 2: Open the argon filling channel and fill the gas cylinder with argon to 60% of the target volume. Continuously monitor the filling flow rate during the filling process, and stop filling after the filling is completed. Step 3: After the argon filling is completed, pause for 2 minutes. After confirming the state of the argon in the bottle with an in-situ gas composition analyzer, open the filling channels for phosphine and argon. Set the initial filling rate of both through a high-precision mass flow controller. Monitor the flow rate in real time with a micro-nano level flow sensor. The in-situ gas composition analyzer provides feedback on the composition and pressure of the mixed gas every 2-3 seconds. When the volume ratio of phosphine and argon deviates from the target value by 0.02%, dynamically adjust the flow rate to accurately control the mixed gas ratio. Step 4: After filling is complete, close all gas filling valves, use a vacuum pump to perform post-vacuum treatment on the gas cylinder and connecting pipes, and use a helium mass spectrometer leak detector to check the airtightness of the filling device. Step 5: Use a high-precision spectrometer to perform final testing on the mixed gas composition in the gas cylinder, and determine that the error between the actual volume ratio of phosphine and argon and the target volume ratio is within ±0.02%. The filling process is then complete.

[0017] In one embodiment of the present invention: In step one, each component of the filling instrument is tested to ensure that the micro-nano level flow sensor, high-precision mass flow controller and in-situ gas composition analyzer are functioning normally, initial parameters are set, and a 30L gas cylinder to be filled is prepared to ensure that the appearance inspection and pressure test of the gas cylinder are qualified, and that the connection parts of each valve are sealed properly.

[0018] In one embodiment of the present invention: In step one, the gas cylinder and the filling instrument are connected through a high-pressure resistant and corrosion-resistant pipe. The pipe is pre-vacuum degassing to ensure that the inside is clean and free of impurities. After the connection is completed, the pre-vacuum treatment step is started. The vacuum pump is turned on to evacuate the gas cylinder and the connecting pipe. The pumping rate is set to 5L / min-8L / min. After evacuation for 15min-20min and purging with argon three times, the vacuum degree of the filling instrument and the gas cylinder is controlled below 0.00133Pa.

[0019] In one embodiment of the present invention: In step two, the argon filling channel and valve are opened, and the argon filling rate is set to 6L / min-8L / min using a high-precision mass flow controller. Argon is filled into the gas cylinder to 60% of the target volume, that is, 18L of argon is filled into a 30L gas cylinder. During the filling process, a micro-nano-level flow sensor is used to monitor the argon flow rate in real time, and an in-situ gas composition analyzer provides feedback on the gas composition and pressure in the gas cylinder every 2 seconds. The filling time of argon into the gas cylinder is 3min-5min.

[0020] In one embodiment of the present invention: In step three, after argon filling is completed, a 2-minute pause is allowed to give the argon in the cylinder sufficient time to stabilize and distribute the gas evenly. After the pause, an in-situ gas composition analyzer is used to analyze the state of the argon in the cylinder, including argon purity, impurity content, and pressure range within the cylinder. After confirming that the argon state is qualified, the filling channels for phosphine and argon are opened. A high-precision mass flow controller is used to set the initial filling rates for phosphine and argon respectively. The initial filling rate for phosphine is set to 0.4 L / min-0.6 L / min, and the initial filling rate for argon is set to... The filling rate is 1.3L / min-1.7L / min. A novel gas uniform mixing promoter is added to the filling pipeline. It is made of a special nanoporous material loaded with an active metal catalyst and has the chemical formula Pd(Al2O3). During the filling process, a micro-nano-level flow sensor continuously monitors the real-time flow of phosphine and argon with high precision. The in-situ gas composition analyzer provides feedback on the composition and pressure of the mixed gas in the cylinder every 2 seconds. When the volume ratio of phosphine and argon deviates from the target value by 0.02% through spectral analysis, the control system dynamically adjusts the flow rate based on the real-time data.

[0021] In one embodiment of the present invention: the interaction principle between the mixing accelerator and the gas is as follows: during the filling process, phosphine (PH3) molecules adsorb onto the active sites of Pd and undergo a dissociation adsorption process, as shown in the following reaction equation: ; ; ; The generated atomic state It can be uniformly mixed with argon, while hydrogen can diffuse out from the porous material. It can be continuously filled until the mixed gas in the cylinder reaches the target volume. For a 30L cylinder, the total volume of the mixed gas to be filled is 12L, namely 2.4L of phosphine and 9.6L of argon.

[0022] In one embodiment of the present invention: In step four, after closing all gas filling valves, the vacuum pump is connected to the gas cylinder and the filling instrument through a high-pressure resistant and corrosion-resistant pipe, ensuring that the connection is well sealed and there is no risk of leakage. After the connection is completed, the entire connection line is checked again to ensure its stability and sealing. The vacuum pump is turned on and the pumping rate is set to 5L / min. The pumping process lasts for 12min-15min. During the pumping process, a high-precision vacuum measuring instrument is used to detect the vacuum degree in the system in real time to ensure that the final vacuum degree is controlled below 0.00133Pa.

[0023] In one embodiment of the present invention: In step four, after the vacuum treatment is completed, the helium mass spectrometer leak detector is moved to a suitable position so that its detection probe can be easily connected to the key detection part of the filling system. After the connection is completed, the helium mass spectrometer leak detector is turned on, and its detection sensitivity is set to 10 on the operation panel. -2 Using a helium filling device, a small amount of helium is slowly injected into the filling system at a flow rate of 0.15 L / min, with the filling time controlled between 1.5 min and 3 min. After the helium is injected, the detection program of the helium mass spectrometer leak detector is started to perform a comprehensive scan and detection of all connection parts and the entire filling system, collecting and analyzing helium information in real time. If no helium leak is detected, it indicates that the filling device has good airtightness.

[0024] In one embodiment of the present invention: In step five, the high-precision spectrometer is placed in a stable and easily operable location, with the temperature controlled between 20°C and 25°C and the humidity maintained between 40% and 60%. The spectrometer is connected to the computer control system using a data transmission line, and the detection data is transmitted and recorded in real time. The high-precision spectrometer is calibrated using a calibration gas. The calibration gas is a standard mixture with known precise components and a composition similar to the phosphine mixture to be detected. Following the procedure specified in the operation manual, the key parameters of the spectrometer, such as wavelength range and resolution, are adjusted sequentially to achieve optimal detection accuracy. The gas inlet of the high-precision spectrometer is connected to the valve outlet of the 30L gas cylinder to be detected using a gas sampling pipeline. During the connection process, all interfaces are ensured to be tightly sealed.

[0025] In one embodiment of the present invention: the filling instrument is further equipped with an intelligent adaptive safety protection device, an adaptive environmental monitoring module, and a graded emergency response system. During the entire filling process, the intelligent adaptive safety protection device operates continuously, and the adaptive environmental monitoring module monitors parameters such as temperature, humidity, and electromagnetic environment of the filling environment in real time, and automatically adjusts the gas leak detection sensitivity. When any abnormal situation is detected, the graded emergency response system will immediately activate the corresponding emergency measures according to the set rules to ensure the safety of the filling process.

[0026] In one embodiment of the present invention: in step four, during the vacuum treatment process, a nano-composite anti-corrosion coating is applied to the inner wall of the gas cylinder and the connecting pipe. The main component of the coating is... The nanocomposite material, prepared via the sol-gel method, is coated onto the inner wall of a filling device and then cured to form a dense protective layer with a thickness of 100nm-200nm. This layer prevents phosphine gas from directly contacting the metal cylinder and pipeline inner walls, providing physical isolation. Even if trace amounts of phosphine molecules come into contact with the coating surface, the active ingredients in the coating can chemically react with the phosphine to inhibit further decomposition and the generation of more corrosive substances or other harmful reactions. The reaction with phosphine is as follows:

[0027] The generated products are relatively stable and will not cause corrosion or damage to the system, thus ensuring the long-term stable operation of the entire filling system.

[0028] The phosphine mixed gas filling method was used to fill a 30L gas cylinder, verify the operation process and parameter settings of each step, achieve a high-precision, high-efficiency and safe and reliable filling effect, and ensure that the mixed gas meets the quality requirements after filling. Carefully inspect each component of the micro-nano-level flow sensor, high-precision mass flow controller, and in-situ gas composition analyzer. Through standard calibration procedures and testing processes, ensure that each instrument functions normally, responds sensitively, and measures accurately. Set the initial accuracy parameters of the micro-nano-level flow sensor. Set the control accuracy of the high-precision mass flow controller to be able to accurately adjust the gas flow rate according to the set value, with the error range controlled within a very small range. Set the in-situ gas composition analyzer to automatically collect and feedback data every 2 seconds. At the same time, prepare a 30L gas cylinder to be filled and conduct a comprehensive visual inspection of the cylinder to check for scratches, deformation, or other abnormalities. Then conduct a pressure test. The test pressure is set to 1.5 times the rated pressure of the gas cylinder. If the rated pressure of the gas cylinder is set to 15MPa, then the test pressure is set to 22.5MPa and held at the pressure for 30 minutes to confirm that there is no leakage or deformation in the gas cylinder and that all valve connections are sealed with special sealing gaskets. Connect the gas cylinder and filling instrument through a high-pressure and corrosion-resistant pipe. The pipe is degassed under vacuum and placed in a vacuum environment. The pumping rate is set to 6L / min and the pumping time is 30min to ensure that the inside is clean and free of impurities. After the connection is completed, start the pre-vacuum treatment step. Turn on the vacuum pump to evacuate the gas cylinder and connecting pipe. The pumping rate is set to 6L / min. After 18min of pumping and three argon gas fillings for purging, the argon gas flow rate is 2L / min and the filling time is 2min each time. Use a high-precision vacuum degree measuring instrument to detect the vacuum degree of the system to ensure that the vacuum degree of the filling instrument and the gas cylinder is controlled below 0.00133Pa. Open the argon filling channel and valve, and set the argon filling rate to 7L / min using a high-precision mass flow controller. During the filling process, a micro-nano-level flow sensor monitors the argon flow rate in real time, and the in-situ gas composition analyzer provides feedback on the gas composition and pressure in the cylinder every 2 seconds. The operator can view the data changes in real time through the monitoring terminal connected to the instrument and confirm whether the filling process is normal based on the feedback information. Continue filling until the argon gas filled into the cylinder reaches 60% of the target volume, that is, 18L of argon gas is filled into a 30L cylinder. The high-precision mass flow controller calculates the volume of argon gas filled in real time. When it reaches 18L, the argon filling operation is automatically stopped. This process takes about 4 minutes. During the filling process, the pressure in the cylinder gradually rises from the initial near-vacuum state to about 8MPa. After argon filling is completed, a strict 2-minute pause is required to allow the argon in the cylinder to fully stabilize and distribute evenly. After the pause, an in-situ gas composition analyzer is used to perform a detailed analysis of the argon state, focusing on argon purity (requiring a purity of 99.999% or higher), impurity content (all impurities must be below 1 ppm), and the cylinder pressure range (pressure fluctuations controlled within ±0.1 MPa). Once all argon state indicators are confirmed to be within acceptable limits, preparation for mixed gas filling begins. The phosphine and argon filling channels are opened, and a high-precision mass flow controller is used to set the initial filling rate of phosphine to 0.5 L / min and the initial filling rate of argon to 1.5 L / min. Simultaneously, a novel gas homogenization promoter is added to the filling pipeline. This promoter is made of a special nanoporous material supporting an active metal catalyst Pd(Al2O3). The amount added is ensured to ensure even distribution within the filling pipeline and to fully exert its effect during the filling process. Micro-nano-scale flow sensors continuously monitor the real-time flow rates of phosphine and argon with high precision. The in-situ gas composition analyzer provides feedback on the composition and pressure of the mixed gas in the cylinder every 2 seconds. Once the volume ratio of phosphine and argon deviates from the target value (1:4) by 0.02% through spectral analysis, if the phosphine ratio is too low, the control system immediately adjusts the phosphine flow rate by increasing it by 0.01 L / min based on real-time data, while simultaneously fine-tuning the argon flow rate by decreasing it by 0.04 L / min to accurately control the mixed gas ratio. The filling continues until the mixed gas in the cylinder reaches the target volume. For a 30L cylinder, the remaining total volume of mixed gas to be filled is 12L (i.e., 2.4L of phosphine and 9.6L of argon). By calculating the total volume of the filled mixed gas in real time, the filling operation of phosphine and argon is automatically stopped when the calculation is completed, thus completing this stage of the filling process. The entire mixed gas filling stage takes about 8 minutes, and the final pressure in the cylinder rises to about 12MPa. After filling, the operator closes all gas filling valves sequentially according to the operating procedure. Then, the vacuum pump is connected to the gas cylinder and filling instrument via high-pressure and corrosion-resistant pipes. During the connection process, sealing tape is used to supplement the seal at the interface to ensure a good seal and no risk of leakage. After the connection is completed, each connection is visually inspected and manually checked to ensure its stability and sealing. The vacuum pump is then turned on, and the pumping rate is set to 5L / min. The pumping process lasts for 13 minutes. During the pumping process, a high-precision vacuum gauge is used to monitor the vacuum level within the system. Real-time monitoring is conducted to closely observe changes in the vacuum level, ensuring the final vacuum level is controlled below 0.00133 Pa. This effectively removes residual mixed gases, impurities, and moisture from the system. After vacuum treatment, the helium mass spectrometer leak detector is moved to a suitable location, allowing its probe to be easily connected to key detection points in the filling system, including cylinder valve interfaces, pipe connections, and bends in the gas filling channels. Sealing connectors are used for these connections to ensure a tight, leak-free fit. Once connected, the helium mass spectrometer leak detector is turned on, and its detection sensitivity is set to 10 on the control panel. -2 Using a helium filling device, a small amount of helium is slowly added to the filling system at a filling rate of 0.15 L / min, with the filling time controlled within 2 minutes, to ensure a uniform and appropriate amount of helium distribution within the system. After the helium is added, the detection program of the helium mass spectrometer leak detector is started, which performs a comprehensive scan and detection of all connection parts and the entire filling system, collecting and analyzing helium information in real time. The detection process lasts for about 5 minutes. If no helium leak is detected, it indicates that the filling device is airtight and the next step can be carried out. If a helium leak is detected, the leak detector will accurately locate the leak and issue an alarm to alert the operator. At this time, subsequent operations must be stopped immediately, and the leaking part must be thoroughly inspected and repaired. Then, the entire process of post-vacuum treatment and airtightness detection is repeated until the airtightness of the entire filling system is fully qualified. The high-precision spectrometer was placed in a stable and easily accessible location with an ambient temperature controlled at 23°C and humidity maintained at 50%. A data transmission cable was used to connect the spectrometer to the computer control system to ensure real-time data transmission and accurate recording. Next, the high-precision spectrometer was calibrated using a calibration gas (a standard mixture with known precise components and a composition similar to the phosphine mixture to be detected, wherein the volume ratio of phosphine to argon was 1:4, and the purity of each component was above 99.999%). Following the procedures specified in the operation manual, the wavelength range of the spectrometer was adjusted sequentially (the infrared band was set to 800 cm⁻¹). -1 -3000cm -1 The ultraviolet wavelength was set to 100nm-400nm, and the resolution was set to 0.1cm. -1Key parameters such as phosphine and argon are selected to achieve optimal detection accuracy. A gas sampling pipe made of polytetrafluoroethylene is used to connect the inlet of the high-precision spectrometer to the valve outlet of the 30L gas cylinder to be tested. During the connection process, all interfaces are ensured to be tightly sealed. After the connection is completed, the detection program of the spectrometer is started to perform real-time spectral scanning on the incoming mixed gas. Spectral data is collected once every 1 second. Through the built-in data analysis algorithm, based on the characteristic spectral peak intensity and peak position of phosphine and argon, the actual volume ratio of the two in the mixed gas is calculated. The detection results are transmitted to the computer control system in real time for recording and display. The operator can view the detection results fed back by the high-precision spectrometer through the computer control system and pay attention to the actual volume ratio data of phosphine and argon. The computer control system has a built-in error calculation program that automatically compares the measured volume ratio with the target volume ratio (1:4) to calculate the error value. If the error between the actual volume ratio of phosphine and argon and the target volume ratio is within ±0.02%, and the measured volume ratio is 1:4.002 or 1:3.998 (the calculated error is within the specified range), it indicates that the mixed gas composition meets the quality requirements and the filling process is successfully completed. If the detected error exceeds ±0.02%, it indicates that there is a deviation in the mixed gas ratio. It is necessary to conduct a retrospective analysis of the filling process to check the links that may cause the error, including whether the gas flow control is accurate and whether the gas uniformity promotion agent is functioning properly. Corresponding corrective measures should be taken, which may involve readjusting the mixed gas in the gas cylinder or refilling the operation until the final test result meets the error requirements. Throughout the filling process, the intelligent adaptive safety protection device installed in the filling instrument operates continuously. Its internal adaptive environmental monitoring module monitors parameters such as temperature (monitoring accuracy ±0.5℃), humidity (accuracy ±2%), and electromagnetic environment (detectable electromagnetic intensity changes within the range of 0uT-1000uT) in real time. Based on these parameters, it automatically adjusts the gas leak detection sensitivity. When the ambient temperature rises to 30℃, the adaptive environmental monitoring module, based on its built-in algorithm, determines that it may affect gas leak detection and automatically increases the detection sensitivity of the helium mass spectrometer leak detector by one level (from 10). -2 mbar·L / s adjusted to 10 -3mbar·L / s is used to ensure accurate detection of gas leaks even in complex environments. Upon detection of any anomaly, including gas leaks (such as helium leaks detected by a helium mass spectrometer or abnormally high phosphine concentrations detected by other sensors) or abnormal pressure fluctuations, the tiered emergency response system will immediately activate corresponding emergency measures according to pre-set rules. For minor anomalies, such as small helium leaks, an audible and visual alarm will be issued to alert operators, and local ventilation equipment (adjustable to 5m³ / s) will be automatically activated. 3 The system will control the concentration of leaked gas within a safe range (at a rate of 2 kg / s). If a serious anomaly is detected, such as a large gas leak that poses a risk of fire or explosion, in addition to ventilation, the system will immediately activate the fire extinguishing device (using a dry powder extinguishing agent suitable for phosphine fire extinguishing, with a spray rate of 2 kg / s and spray time automatically controlled according to actual conditions), cut off all gas and power sources, and remotely notify relevant safety management departments to ensure the safety of the filling process in all aspects.

[0029] The complete operation steps and corresponding data examples in the above embodiments fully demonstrate the specific implementation of the phosphine mixed gas filling method in practical applications and the synergistic effect of each link, achieving the goal of high precision, high efficiency and safe and reliable filling.

[0030] The embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited to the described embodiments. For those skilled in the art, various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and these variations still fall within the protection scope of the present invention.

[0031] In the description of this specification, the references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the 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.

[0032] The above description is merely an example and illustration of the present invention. Any modifications, additions, or substitutions made by those skilled in the art to the specific embodiments described, as long as they do not deviate from the invention or exceed the scope defined in the claims, shall fall within the protection scope of the present invention.

[0033] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A method for filling a phosphine mixed gas, comprising instrument pretreatment, step-by-step filling, post-vacuum treatment, quality inspection, and safety monitoring, characterized in that: The specific operating steps of the phosphine mixed gas filling method are as follows: Step 1: Prepare the filling instrument, which includes a micro-nano-level flow sensor, a high-precision mass flow controller, and an in-situ gas composition analyzer. Connect the filling instrument to the gas cylinder and perform vacuum degassing on it. Step 2: Open the argon filling channel and fill the gas cylinder with argon to 60% of the target volume. Continuously monitor the filling flow rate during the filling process, and stop filling after the filling is completed. Step 3: After the argon filling is completed, pause for 2 minutes. After confirming the state of the argon in the bottle with an in-situ gas composition analyzer, open the filling channels for phosphine and argon. Set the initial filling rate of both through a high-precision mass flow controller. Monitor the flow rate in real time with a micro-nano level flow sensor. The in-situ gas composition analyzer provides feedback on the composition and pressure of the mixed gas every 2-3 seconds. When the volume ratio of phosphine and argon deviates from the target value by 0.02%, dynamically adjust the flow rate to accurately control the mixed gas ratio. Step 4: After filling is complete, close all gas filling valves, use a vacuum pump to perform post-vacuum treatment on the gas cylinder and connecting pipes, and use a helium mass spectrometer leak detector to check the airtightness of the filling device. Step 5: Use a high-precision spectrometer to perform final testing on the mixed gas composition in the gas cylinder, and determine that the error between the actual volume ratio of phosphine and argon and the target volume ratio is within ±0.02%. The filling process is then complete.

2. The method for filling a phosphine mixed gas according to claim 1, characterized in that: In step one, each component of the filling instrument is tested to ensure that the micro-nano level flow sensor, high-precision mass flow controller and in-situ gas composition analyzer are functioning properly, initial parameters are set, and a 30L gas cylinder to be filled is prepared to ensure that the appearance inspection and pressure test of the gas cylinder are qualified, and that all valve connections are properly sealed.

3. The method for filling a phosphine mixed gas according to claim 1, characterized in that: In step one, the gas cylinder and the filling instrument are connected through a high-pressure and corrosion-resistant pipe. The pipe is pre-vacuum degassed to ensure that it is clean and free of impurities. After the connection is completed, the pre-vacuum treatment step is started. The vacuum pump is turned on to evacuate the gas cylinder and the connecting pipe. The pumping rate is set to 5L / min-8L / min. After evacuation for 15min-20min and purging with argon three times, the vacuum degree of the filling instrument and the gas cylinder is controlled below 0.00133Pa.

4. The method for filling a phosphine mixed gas according to claim 1, characterized in that: In step two, the argon filling channel and valve are opened, and the argon filling rate is set to 6L / min-8L / min using a high-precision mass flow controller. Argon is filled into the cylinder to 60% of the target volume. During the filling process, a micro-nano flow sensor is used to monitor the argon flow rate in real time. The in-situ gas composition analyzer provides feedback on the gas composition and pressure in the cylinder every 2 seconds. The filling time for the cylinder is 3-5 minutes.

5. The method for filling a phosphine mixed gas according to claim 1, characterized in that: In step three, after argon filling is completed, pause for 2 minutes to allow the gas to distribute evenly. After the pause, use an in-situ gas composition analyzer to analyze the state of the argon in the cylinder, including argon purity, impurity content, and pressure range within the cylinder. Once the argon state is confirmed to be acceptable, open the phosphine and argon filling channels. Use a high-precision mass flow controller to set the initial filling rates for phosphine and argon respectively. Set the initial filling rate for phosphine to 0.4 L / min-0.6 L / min and the initial filling rate for argon to 1.3 L / min. -1.7L / min, and at the same time, a gas uniform mixing promoter is added to the filling pipeline. It is made of nanoporous material supported by an active metal catalyst, with the chemical formula Pd(Al2O3). During the filling process, micro-nano-level flow sensors continuously monitor the real-time flow of phosphine and argon with high precision. The in-situ gas composition analyzer provides feedback on the composition and pressure of the mixed gas in the gas cylinder every 2 seconds. When the volume ratio of phosphine and argon deviates from the target value by 0.02% through spectral analysis, the control system dynamically adjusts the flow rate based on the real-time data.

6. The method for filling a phosphine mixed gas according to claim 5, characterized in that: The interaction principle between the mixing accelerator and the gas is as follows: During the filling process, phosphine molecules adsorb onto the active sites of Pd and undergo a dissociation adsorption process. The reaction equation is as follows: ； ； ； The generated atomic state It is uniformly mixed with argon, while hydrogen can diffuse out from the porous material, and the filling continues until the mixed gas in the gas cylinder reaches the target volume.

7. The method for filling a phosphine mixed gas according to claim 1, characterized in that: In step four, after closing all gas filling valves, connect the vacuum pump to the gas cylinder and filling instrument via a high-pressure and corrosion-resistant pipe, ensuring a good seal at the connection point and no risk of leakage. After connection, retest the entire connection line to ensure its stability and sealing. Turn on the vacuum pump and set the pumping rate to 5L / min. The pumping process lasts for 12-15 minutes. During the pumping process, use a high-precision vacuum gauge to monitor the vacuum level in the system in real time to ensure that the final vacuum level is controlled below 0.00133Pa.

8. The method for filling a phosphine mixed gas according to claim 1, characterized in that: In step four, after vacuum treatment, the helium mass spectrometer leak detector is moved to a suitable position so that its detection probe can be easily connected to the key detection parts of the filling system. After connection, the helium mass spectrometer leak detector is turned on, and its detection sensitivity is set to 10 on the operation panel. -2 Using a helium filling device, a small amount of helium is slowly injected into the filling system at a flow rate of 0.15 L / min, with the filling time controlled between 1.5 min and 3 min. After the helium is injected, the detection program of the helium mass spectrometer leak detector is started to perform a comprehensive scan and detection of all connection parts and the entire filling system, collecting and analyzing helium information in real time. If no helium leak is detected, it indicates that the filling device has good airtightness.

9. A method for filling a phosphine mixed gas according to claim 1, characterized in that: In step five, the high-precision spectrometer is placed in a stable and easily operable location. The ambient temperature is controlled between 20℃ and 25℃, and the ambient humidity is maintained between 40% and 60%. The spectrometer is connected to the computer control system using a data transmission cable, and the detection data is transmitted and recorded in real time. The high-precision spectrometer is calibrated using a calibration gas. The calibration gas is a standard mixture with known precise components and similar composition to the phosphine mixture to be detected. Following the procedure specified in the operation manual, the wavelength range and resolution of the spectrometer are adjusted sequentially to achieve the set detection accuracy. The gas sampling pipeline is used to connect the gas inlet of the high-precision spectrometer to the valve outlet of the 30L gas cylinder to be tested, ensuring that all interfaces are tightly sealed during the connection process.

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