A method of filling a phosphine gas mixture

Abstract

The application discloses a phosphine mixed gas filling method, and relates to the technical field of mixed gas, which comprises instrument pretreatment, step-by-step filling, post-vacuum treatment, quality detection and safety monitoring. The phosphine mixed gas filling method has the advantages that: by adding a mixing accelerator in the filling pipeline during the filling of phosphine and argon, a large number of active sites and unique gas diffusion channels are provided to accelerate the uniform mixing of phosphine and argon, and the uniformity and accuracy of the mixed gas ratio are improved. During the action of the accelerator and the gas, the argon molecules fully contact and collide with the dissociated and adsorbed phosphorus atoms under the guidance of the special structure of the nano-porous material, the uniform mixing of the two is promoted, and the stable and accurately-proportioned phosphine mixed gas is formed. During the whole process, the mixing accelerator continuously plays a role, so that the uniform mixing efficiency of the mixed gas during the filling process is greatly improved compared with the traditional method.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of mixed gas, in particular to a phosphine mixed gas filling method. BACKGROUND

[0002] In the field of semiconductor manufacturing, optoelectronic device production and some specific chemical processes, phosphine mixed gas has extremely important application. As a key electronic special gas, phosphine (PH3) is often mixed with other inert gases in a precise ratio to form a phosphine mixed gas, which is used in various process links, such as the chemical vapor deposition (CVD) process in the semiconductor chip manufacturing process, the phosphine mixed gas can participate in the formation of thin film materials with specific electrical properties.

[0003] With the expansion of production scale and the gradual increase of filling accuracy requirements, some enterprises begin to use automatic control system to fill phosphine gas mixture. This system generally installs electronic flow regulating valve, pressure sensor and other equipment on the gas filling pipeline, transmits the data collected by these sensors to a programmable logic controller (PLC), and automatically controls the flow and filling time of each gas according to the preset program and mixture ratio parameters, so as to realize the filling process. In order to improve production efficiency and ensure the accuracy of filling to a certain extent, some enterprises use this kind of way. For manual metering and filling method, due to the complete dependence on the operation proficiency of the operator and the reading and judgment of the instrument data by the naked eye, it is inevitable that there will be human error. For example, when adjusting the gas flow valve, it is difficult to accurately control. Even a small flow deviation will cause a large difference between the actual ratio of the final mixture and the theoretical ratio in the long-term filling process or in the case of high-precision mixture ratio requirements, which will affect the process effect of using the mixture subsequently. For example, in semiconductor chip manufacturing, it may cause unstable film performance and other quality problems. Whether it is manual metering and filling or simple automatic control system filling, it often needs to be stopped several times during the filling process for data monitoring and adjustment. Especially for manual filling, each adjustment of the valve and reading of the data takes time, and the overall filling time of a bottle of mixture is long. Although the simple automatic filling is relatively faster than the manual filling, its filling efficiency still cannot meet the requirements of high-efficiency production when facing large quantities and rapid turnover of filling demand. For example, in large-scale semiconductor production lines, the filling efficiency cannot keep up with the production rhythm. Phosphine is a highly toxic and flammable and explosive gas. The existing technology has deficiencies in gas leakage detection and emergency treatment during the filling process. When filling manually, the operator may not be able to find the small gas leakage in time due to focusing on the metering operation. In the automatic filling system, although there are some basic leakage alarm devices, the accuracy and timeliness of leakage detection under complex working conditions (such as electromagnetic interference in the filling site) are not ideal. Therefore, we propose a phosphine gas mixture filling method. SUMMARY

[0004] The purpose of the present application is to provide a phosphine gas mixture filling method.

[0005] To solve the problems raised in the above background art, the present application provides the following technical solution: a phosphine gas mixture filling method, comprising instrument pretreatment, step-by-step filling, post-vacuum treatment, quality detection and safety monitoring. The specific operation steps of the phosphine gas mixture filling method are as follows:

[0006] Step one, prepare the filling instrument, which contains micro-nano level flow sensor, high precision mass flow controller and in-situ gas composition analyzer, connect the filling instrument with the gas cylinder and perform vacuum degassing treatment on it;

[0007] Step two, open the argon filling channel, fill argon into the gas cylinder to 60% of the target volume, continuously monitor the filling flow during the filling process, and stop filling after the filling is completed;

[0008] Step three, after the argon filling is completed, pause for 2 minutes, use the in-situ gas composition analyzer to confirm the argon state in the cylinder, then open the phosphane and argon filling channel, set the initial filling rate of both through the high precision mass flow controller, the micro-nano level flow sensor monitors the flow in real time, and the in-situ gas composition analyzer feeds back the mixed gas composition and pressure every 2-3 seconds, when the volume ratio of phosphane and argon deviates from the target value by 0.02%, the flow is dynamically adjusted to accurately control the mixed gas ratio;

[0009] Step four, after the filling is completed, close all gas filling valves, use a vacuum pump to perform post-vacuum treatment on the gas cylinder and connecting pipeline, and use a helium mass spectrometer leak detector to detect the airtightness of the filling device;

[0010] Step five, use a high-precision spectrum analyzer to finally detect the mixed gas composition filled in the gas cylinder, determine that the actual volume ratio of phosphane and argon is within ±0.02% of the target volume ratio, and the filling process is completed.

[0011] As a further scheme of the present application: in step one, detect each component of the filling instrument to ensure that the micro-nano level flow sensor, high precision mass flow controller and in-situ gas composition analyzer are functioning normally, set the initial parameters, and prepare the 30L gas cylinder to be filled, ensure that the gas cylinder passes the appearance inspection and pressure test, and the valve connection parts are sealed perfectly.

[0012] As a further scheme of the present application: in step one, connect the gas cylinder with the filling instrument through high-pressure and corrosion-resistant pipeline, perform vacuum degassing treatment on the pipeline in advance to ensure that the inside is clean and free of impurities, after the connection is completed, start the pre-vacuum treatment step, open the vacuum pump to vacuumize the gas cylinder and connecting pipeline, the evacuation rate is set to 5-8 L / min, after 15-20 min of evacuation and three times of argon filling for purging, the vacuum degree of the filling instrument and the gas cylinder is controlled below 0.00133 Pa.

[0013] As a further scheme of the present application: in the step two, the argon filling channel and the valve are opened, a high-precision mass flow controller is used to set the argon filling rate to 6L / min-8L / min, argon is filled into the gas cylinder to 60% of the target volume, that is, 18L of argon is filled into a 30L capacity gas cylinder, a micro-nano level flow sensor is used to monitor the argon flow in real time during the filling process, and an in-situ gas composition analyzer feeds back the gas composition and pressure in the gas cylinder every 2s, and the time for filling argon into the gas cylinder is 3min-5min.

[0014] As a further scheme of the present application: in the step three, after the argon filling is completed, a pause of 2min is given to allow the argon filled in the gas cylinder to stabilize and the gas to be evenly distributed, after the pause, the in-situ gas composition analyzer is used to analyze the argon state in the gas cylinder, including argon purity, impurity content and pressure range in the gas cylinder, after confirming that the argon state is qualified, the filling channels of phosphine and argon are opened, a high-precision mass flow controller is used to set the initial filling rate of phosphine and argon respectively, the initial filling rate of phosphine is set to 0.4L / min-0.6L / min, and the initial filling rate of argon is set to 1.3L / min-1.7L / min, and a new type of gas uniform mixing promoter made of a special nano-porous material loaded with an active metal catalyst with a chemical formula of Pd(Al2O3) is added in the filling pipeline for uniform mixing and promotion, during the filling process, a micro-nano level flow sensor continuously monitors the real-time flow of phosphine and argon with high precision, and an in-situ gas composition analyzer feeds back the composition and pressure of the mixed gas in the gas cylinder every 2s, when the volume ratio of phosphine and argon deviates from the target value by 0.02% through spectral analysis monitoring, a control system dynamically adjusts the flow according to the real-time data.

[0015] As a further scheme of the present application: the action principle of the mixed promoter and the gas is that during the filling process, phosphine (PH3) molecules are adsorbed on the Pd active sites to undergo dissociative adsorption process, and the reaction equation is as follows:

[0016] ;

[0017] ;

[0018] ;

[0019] The generated atomic state can be uniformly mixed with argon, and hydrogen can diffuse out of the porous material, and the filling continues until the mixed gas filled in the gas cylinder reaches the target volume, for a 30L gas cylinder, the total volume of the mixed gas to be filled is 12L, that is, 2.4L of phosphine and 9.6L of argon.

[0020] As a further scheme of the present application: in step four, after closing all gas filling valves, connect the vacuum pump to the connecting pipeline of the gas cylinder and the filling instrument through a high-pressure and corrosion-resistant pipeline, ensure that the connection part is sealed well and there is no risk of gas leakage, and then detect the entire connection line again to ensure its stability and sealing, turn on the vacuum pump and set the pumping rate to 5 L / min, the pumping process lasts for 12-15 min, and in the pumping process, use a high-precision vacuum degree measuring instrument to detect the vacuum degree in the system in real time to ensure that the final vacuum degree is controlled below 0.00133 Pa.

[0021] As a further scheme of the present application: in step four, after completing the post-vacuum treatment, move the helium mass spectrometer leak detector 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, turn on the helium mass spectrometer leak detector and set its detection sensitivity to 10 -2 mbar·L / s on the operation panel, slowly fill a small amount of helium into the filling system through the helium filling device at a flow rate of 0.15 L / min, the filling time is controlled to be 1.5-3 min, after filling helium, start the detection program of the helium mass spectrometer leak detector to perform comprehensive scanning detection on each connection part and the entire filling system, collect and analyze helium information in real time, and if no helium leakage is detected, it indicates that the filling device has good airtightness.

[0022] As a further scheme of the present application: in step five, place the high-precision spectrum analyzer in a stable and easy-to-operate position, control the temperature to be between 20-25 DEG C, and maintain the humidity to be between 40-60%, use a data transmission line to connect the spectrum analyzer with the computer control system and transmit and record the detection data in real time, use calibration gas to calibrate the high-precision spectrum analyzer, the calibration gas is a standard mixed gas with known accurate composition and similar composition to the phosphane mixed gas to be detected, according to the process specified in the operation manual, adjust the wavelength range, resolution and other key parameters of the spectrum analyzer in sequence to achieve the best detection accuracy, use the gas sampling pipeline to connect the gas inlet of the high-precision spectrum analyzer with the outlet of the 30L cylinder valve to be detected, and ensure that each interface is sealed tightly during the connection process.

[0023] Compared with the prior art, the technical scheme has the advantages that:

[0024] The application can accelerate the uniform mixing of phosphine and argon, improve the uniformity and accuracy of the mixed gas ratio by providing a large number of active sites and unique gas diffusion channels, and improve the uniform mixing efficiency of the mixed gas during the filling process compared with the traditional method, greatly improve the quality of the final mixed gas, and better meet the high requirements of the semiconductor production line and the like on the filling efficiency, by adding a mixing promoter in the filling pipeline during the filling of phosphine and argon with argon, and the special structure of the nanoporous material guides the collision of argon molecules with dissociated and adsorbed phosphorus atoms during the interaction of the promoter and the gas, promotes the rapid and uniform mixing of the two, and forms a stable and accurately-proportioned phosphine mixed gas, the mixing promoter continuously plays a role during the whole process, so that the uniform mixing efficiency of the mixed gas during the filling process is greatly improved compared with the traditional method, the quality of the final mixed gas is greatly improved, and by using a step-by-step filling method and re-filling after the first filling pause, unnecessary long-time pause monitoring is avoided, the time spent on filling the phosphine mixed gas is greatly shortened as a whole, and the high requirements of the semiconductor production line and the like on the filling efficiency can be better met;

[0025] The application can ensure that the final vacuum degree in the system is controlled below a specific value, effectively remove the residual mixed gas and impurity gas in the system, reduce the safety hidden danger, and timely and accurately find out whether the filling device has a gas leakage by slowly filling a small amount of helium and then comprehensively scanning and detecting, compared with the situation that the operator cannot timely find out the tiny leakage during manual filling and the leakage detection accuracy and timeliness of the automatic filling system are not ideal under complex working conditions, the leakage detection capability is greatly improved, and the instruments before filling are pretreated, including detection of each component of the filling instrument, appearance and pressure resistance test of the gas cylinder, vacuum degassing treatment and pre-vacuum treatment of the pipeline, strict monitoring and control of the gas flow and state during the step-by-step filling process, and the links of post-vacuum treatment, quality detection and safety monitoring, so that the phosphine mixed gas filled each time can stably reach the high quality standard, the key indicators such as composition, purity and air tightness can be effectively guaranteed, the filling quality fluctuation caused by human factors, equipment factors and environmental factors is avoided, and it is ensured that the mixed gas filled under different batches and different working conditions can be reliably applied to the process field such as semiconductor manufacturing and optoelectronic device production which has high requirements on the gas quality. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 It is a phosphine mixed gas filling process schematic diagram in the embodiment of the application. DETAILED DESCRIPTION

[0027] The specific embodiments of the present application will be further described below with reference to the drawings. It should be noted that the description of these embodiments is used to help understand the present application, but does not constitute a limitation on the present application. In addition, the technical features involved in the various embodiments of the present application described below can be combined with each other as long as they do not conflict with each other.

[0028] The present application is a phosphine gas filling method, including instrument pretreatment, step-by-step filling, post-vacuum treatment, quality detection and safety monitoring, the specific operation steps of the phosphine gas filling method are as follows:

[0029] Step one, prepare the filling instrument, the instrument includes micro-nano level flow sensor, high precision mass flow controller and in-situ gas composition analyzer, connect the filling instrument with the gas cylinder, and perform vacuum degassing treatment on it;

[0030] Step two, open the argon filling channel, fill argon into the gas cylinder to 60% of the target volume, continuously monitor the filling flow during the filling process, and stop filling after the filling is completed;

[0031] Step three, after the argon filling is completed, pause for 2 minutes, use the in-situ gas composition analyzer to confirm the argon state in the bottle, then open the phosphine and argon filling channel, set the initial filling rate of both through the high precision mass flow controller, the micro-nano level flow sensor monitors the flow in real time, and the in-situ gas composition analyzer feeds back the mixed gas composition and pressure every 2-3 seconds, when the volume ratio of phosphine and argon deviates from the target value by 0.02%, the flow is dynamically adjusted, and the mixed gas ratio is accurately controlled;

[0032] Step four, after the filling is completed, close all gas filling valves, use a vacuum pump to perform post-vacuum treatment on the gas cylinder and connecting pipeline, and use a helium mass spectrometer leak detector to detect the airtightness of the filling device;

[0033] Step five, use a high-precision spectral analyzer to finally detect the mixed gas composition filled in the gas cylinder, determine that the actual volume ratio of phosphine and argon is within ±0.02% of the target volume ratio, and the filling process is completed.

[0034] In one embodiment of the present application: in step one, detect each component of the filling instrument to ensure that the micro-nano level flow sensor, high precision mass flow controller and in-situ gas composition analyzer are functioning properly, set the initial parameters, and prepare a 30L gas cylinder to be filled, ensure that the gas cylinder passes the appearance inspection and pressure test, and the valve connection parts are sealed perfectly.

[0035] In an embodiment of the present application: in step one, the gas cylinder is connected with the filling instrument through a high-pressure and corrosion-resistant pipeline, the pipeline is subjected to vacuum degassing treatment in advance to ensure the internal cleanliness and no impurities, after the connection is completed, the pre-vacuum treatment step is started, the vacuum pump is started to pump the gas cylinder and the connecting pipeline, the pumping rate is set to 5L / min-8L / min, after 15min-20min of pumping and three times of argon filling for purging, the vacuum degree of the filling instrument and the gas cylinder is controlled below 0.00133Pa.

[0036] In an embodiment of the present application: in step two, the argon filling channel and the valve are opened, 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, i.e. 18L of argon is filled into a 30L capacity gas cylinder, the argon flow is monitored in real time using a micro-nano level flow sensor, the in-situ gas composition analyzer feeds back the gas composition and pressure in the gas cylinder every 2s, and the time for filling argon into the gas cylinder is 3min-5min.

[0037] In an embodiment of the present application: in step three, after the argon filling is completed, a pause of 2min is made to give the already filled argon in the gas cylinder sufficient time to stabilize and evenly distribute the gas, after the pause, the in-situ gas composition analyzer is used to analyze the argon state in the gas cylinder, including the argon purity, impurity content and pressure range in the gas cylinder, after confirming that the argon state is qualified, the filling channels of phosphine and argon are opened, the initial filling rates of phosphine and argon are set using a high-precision mass flow controller, the initial filling rate of phosphine is set to 0.4L / min-0.6L / min, the initial filling rate of argon is set to 1.3L / min-1.7L / min, and a new type of gas uniform mixing promoter made of a special nano-porous material loaded with an active metal catalyst with a chemical formula of Pd(Al2O3) is added in the filling pipeline, during the filling process, the micro-nano level flow sensor continuously monitors the real-time flow of phosphine and argon with high precision, and the in-situ gas composition analyzer feeds back the composition and pressure of the mixed gas in the gas cylinder every 2s, when the volume ratio of phosphine and argon deviates from the target value by 0.02% through spectral analysis monitoring, the control system dynamically adjusts the flow according to the real-time data.

[0038] In an embodiment of the present application: the action principle of the mixed promoter and the gas is that during the filling process, the phosphine (PH3) molecules are adsorbed on the Pd active sites to undergo dissociative adsorption process, the reaction equation is as follows:

[0039] ;

[0040] ;

[0041] ;

[0042] The generated atomic state The hydrogen gas can be uniformly mixed with argon gas, and the hydrogen gas can diffuse out of the porous material. The mixed gas is continuously filled until the mixed gas filled in the gas cylinder reaches the target volume. For a 30L gas cylinder, the total volume of the mixed gas to be filled is 12L, that is, 2.4L of phosphane and 9.6L of argon.

[0043] In an embodiment of the present application: in step four, after closing all gas filling valves, the vacuum pump is connected to the gas cylinder and the connecting pipeline of the filling instrument through a high-pressure and corrosion-resistant pipeline, and the connection part is ensured to be sealed well without the risk of gas leakage. After the connection is completed, the entire connection line is detected again to ensure its stability and sealing. The vacuum pump is started, and the gas extraction rate is set to 5L / min. The gas extraction process lasts for 12min-15min. During the gas extraction process, a high-precision vacuum degree 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.

[0044] In an embodiment of the present application: in step four, after the post-vacuum treatment is completed, the helium mass spectrometric leak detector is moved to a suitable position so that its detection probe can be conveniently connected to the key detection parts of the filling system. After the connection is completed, the helium mass spectrometric leak detector is started, and its detection sensitivity is set to 10 -2 mbar·L / s on the operation panel. A small amount of helium is slowly filled into the filling system through the helium filling device at a flow rate of 0.15L / min. The filling time is controlled within 1.5min-3min. After the helium is filled, the detection program of the helium mass spectrometric leak detector is started to comprehensively scan and detect each connection part and the entire filling system. The helium information is collected and analyzed in real time. If no helium leakage is detected, it indicates that the filling device has good airtightness.

[0045] In an embodiment of the present application: in step five, the high-precision spectral analyzer is placed in a stable and convenient position, and the temperature is controlled between 20℃-25℃, and the humidity is maintained between 40%-60%. The spectral analyzer 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 spectral analyzer is calibrated using a calibration gas. The calibration gas is a standard mixed gas with known accurate composition and similar composition to the phosphane mixed gas to be detected. According to the process specified in the operation manual, the wavelength range, resolution and other key parameters of the spectral analyzer are adjusted in sequence to achieve the best detection accuracy. The gas sampling pipeline is used to connect the gas inlet of the high-precision spectral analyzer to the outlet valve of the 30L gas cylinder to be detected. During the connection process, the interfaces are ensured to be sealed tightly.

[0046] In one embodiment of the present application: the filling instrument is additionally provided with an intelligent adaptive safety protection device, an adaptive environment monitoring module and a hierarchical emergency response system, during the entire filling process, the intelligent adaptive safety protection device operates throughout the process, the adaptive environment monitoring module monitors the temperature, humidity, electromagnetic environment and other parameters of the filling environment in real time, and automatically adjusts the gas leakage detection sensitivity, etc., and when any abnormal situation is detected, the hierarchical emergency response system will immediately start the corresponding emergency measures according to the set rules to ensure the safety of the filling process.

[0047] In one embodiment of the present application: in step four, during the vacuum treatment, a nano-composite anti-corrosion coating is applied to the inner walls of the gas cylinder and the connecting pipeline, the main component of the coating is The nano-composite material is prepared by sol-gel method, after being coated on the inner wall of the filling device and subjected to solidification treatment, a dense protective layer with a thickness of 100-200 nm is formed on the surface, which can block the direct contact between phosphine gas and the inner wall of the metal gas cylinder and pipeline, and play a physical isolation role. Even if a small amount of phosphine molecules contact the surface of the coating, the active components in the coating can react with phosphine to inhibit the further decomposition of phosphine to produce substances with stronger corrosive properties or other harmful reactions. The reaction of the coating with phosphine is as follows:

[0048]

[0049] The generated product is relatively stable and will not cause corrosion damage to the system, which can ensure the long-term stable operation of the entire filling system.

[0050] The 30L gas cylinder is filled using the phosphine mixed gas filling method to verify the operation process and parameter setting of each step, achieve high-precision, high-efficiency and safe and reliable filling effect, and ensure that the mixed gas after filling meets the quality requirements;

[0051] Carefully detect the micro-nano level flow sensor, high-precision mass flow controller and in-situ gas composition analyzer, through standard calibration process and detection program, ensure that each instrument function is normal, response is sensitive and measurement is accurate, set the initial precision parameter of the micro-nano level flow sensor, the control precision of the high-precision mass flow controller is set to accurately adjust the gas flow according to the set value, the error range is controlled within a minimum value, the in-situ gas composition analyzer is set to automatically collect and feedback data every 2s, and the 30L gas cylinder to be filled is prepared, the gas cylinder is subjected to comprehensive appearance inspection to check whether there are scratches, deformation and other abnormal conditions on the cylinder body, then subjected to pressure resistance test, the test pressure is set to 1.5 times of the rated pressure of the gas cylinder, the rated pressure of the gas cylinder is set to 15MPa, the test pressure is set to 22.5MPa, and the pressure is maintained for 30min, it is confirmed that the gas cylinder has no leakage, no deformation and other conditions, and the valve connection parts are sealed with special sealing gaskets.

[0052] The gas cylinder is connected with the filling instrument through a high-pressure and corrosion-resistant pipeline, the pipeline is subjected to vacuum degassing treatment, the pipeline is placed in a vacuum environment, the evacuation rate is set to 6 L / min, the evacuation time is 30 min, the internal cleanliness is ensured, and the pre-vacuum treatment step is started after the connection is completed. The vacuum pump is started to evacuate and treat the gas cylinder and the connecting pipeline, the evacuation rate is set to 6 L / min, 18 min of evacuation and three times of argon filling for purging are performed, the argon filling flow rate is 2 L / min each time, the argon filling time is 2 min, a high-precision vacuum degree measuring instrument is used to detect the system vacuum degree, and the vacuum degree of the filling instrument and the gas cylinder is controlled to be below 0.00133 Pa;

[0053] The argon filling channel and the valve are opened, a high-precision mass flow controller is used to set the argon filling rate to 7 L / min, the micro-nano level flow sensor monitors the argon flow rate in real time during the filling process, the in-situ gas component analyzer feeds back the gas component and pressure in the gas cylinder every 2 s, the operator can view the data change in real time through the monitoring terminal connected with the instrument, whether the filling process is normal is confirmed according to the feedback information, and the filling is continued until the argon filled into the gas cylinder reaches 60% of the target volume, that is, 18 L of argon is filled into the 30 L capacity gas cylinder, the high-precision mass flow controller is used to calculate the volume of the filled argon in real time, when the volume reaches 18 L, the argon filling operation is automatically stopped, the process takes about 4 min, and the pressure in the gas cylinder gradually rises from the initial near-vacuum state to about 8 MPa during the filling process;

[0054] After the argon filling is completed, strictly stop for 2 min to make the argon filled in the cylinder fully stable and the gas distribution uniform. After the stop, use the in-situ gas composition analyzer to analyze the argon state in the cylinder in detail, focus on testing the argon purity (required to reach more than 99.999%), impurity content (the content of various impurities needs to be less than 1 ppm) and the pressure range in the cylinder (the pressure fluctuation is controlled within ±0.1 MPa), and confirm that all indicators of the argon state are qualified before preparing to fill the mixed gas, opening the filling channel of phosphine and argon, using a high-precision mass flow controller 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, and adding a new type of gas uniform mixing promoter in the filling pipeline. The promoter is made of a special nano-porous material loaded with an active metal catalyst Pd(Al2O3), and the addition amount is ensured to be uniformly distributed in the filling pipeline and can fully play a role. In the filling process, the micro-nano level flow sensor continuously monitors the real-time flow of phosphine and argon with high precision, and the in-situ gas composition analyzer feeds back the composition and pressure of the mixed gas in the cylinder every 2 s. Once the spectral analysis monitoring detects that the volume ratio of phosphine and argon deviates from the target value (1:4) by 0.02%, if the phosphine ratio is low, the control system will immediately adjust the phosphine flow to increase by 0.01 L / min according to the real-time data, and simultaneously fine-tune the argon flow to decrease by 0.04 L / min, to accurately control the mixed gas ratio. Continue to fill until the mixed gas filled in the cylinder reaches the target volume. For a 30L cylinder, the total volume of mixed gas remaining to be filled is 12L (i.e. 2.4L of phosphine and 9.6L of argon), through real-time cumulative calculation of the total volume of the mixed gas filled, when it is completed, the filling operation of phosphine and argon is automatically stopped, the filling process of this stage is completed, and the whole mixed gas filling stage takes about 8 min, and the final pressure in the cylinder rises to about 12 MPa.

[0055] After filling is completed, the operator closes all gas filling valves in sequence according to the operation sequence, and then connects the vacuum pump to the gas cylinder and the connecting pipeline of the filling instrument through high-pressure-resistant and corrosion-resistant pipelines. During the connection process, sealing tape is used to assist in sealing the interface to ensure that the connection part is well sealed and there is no risk of gas leakage. After the connection is completed, the connection part is observed and manually checked again to ensure its stability and sealing performance. The vacuum pump is started, and the gas extraction rate is set to 5 L / min. The gas extraction process lasts for 13 min. During the gas extraction process, a high-precision vacuum degree measuring instrument is used to detect the vacuum degree in the system in real time, and the vacuum degree value change is closely observed to ensure that the final vacuum degree is controlled below 0.00133 Pa, effectively removing the residual mixed gas, impurity gas and water vapor in the system. 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 conveniently connected to the key detection parts of the filling system, including the gas cylinder valve interface, the pipeline connection part and the gas filling channel bend, and a sealing joint is used to ensure that the connection is tight and leak-free. After the connection is completed, the helium mass spectrometer leak detector is started, and its detection sensitivity is set to 10 -2 mbar·L / s on the operation panel. A small amount of helium is slowly filled into the filling system at a filling rate of 0.15 L / min through the helium filling device. The filling time is controlled within 2 min to uniformly distribute the appropriate amount of helium in the system. After the helium is filled, the detection program of the helium mass spectrometer leak detector is started to comprehensively scan and detect each connection part and the entire filling system. The helium information is collected and analyzed in real time. The detection process lasts for about 5 min. If no helium leakage is detected, it indicates that the filling device has good airtightness, and the next operation can continue. If helium leakage is detected, the leak detector can accurately locate the leakage position and issue an alarm to prompt the operator. At this time, the subsequent operation needs to be stopped immediately, and the leakage part needs to be checked and repaired in detail. Then the whole process of vacuum treatment and airtightness detection is repeated again until the airtightness of the entire filling system is completely qualified.

[0056] The high-precision spectrum analyzer is placed in a stable and easy-to-operate position with the environmental temperature controlled at 23°C and the humidity maintained at 50%. The spectrum analyzer is connected to the computer control system using a data transmission line to ensure that the data can be transmitted and accurately recorded in real time. Then, the high-precision spectrum analyzer is calibrated using calibration gas (a standard mixed gas with known accurate composition and similar composition to the phosphane mixed gas to be detected, with a phosphane to argon volume ratio of 1:4, and a purity of each component above 99.999%). According to the process specified in the operation manual, the wavelength range of the spectrum analyzer is adjusted (the infrared waveband is set to 800 cm -1 -3000 cm -1 , and the ultraviolet waveband is set to 100 nm-400 nm), and the resolution is set to 0.1 cm-1 ) and other key parameters to achieve the best detection accuracy. The gas sampling pipeline made of polytetrafluoroethylene material is used to connect the gas inlet of the high-precision spectrum analyzer with the valve outlet of the 30L gas cylinder to be detected. During the connection process, the sealing of each interface is ensured to be tight. After the connection, the detection program of the spectrum analyzer is started, and the mixed gas entering is scanned in real time. The spectrum data is collected every 1s, and through the built-in data analysis algorithm, the actual volume ratio of phosphane and argon in the mixed gas is calculated according to the characteristic spectral peak intensity and peak position of phosphane and argon, and the detection results are transmitted to the computer control system in real time for recording and display. The operator checks the detection results fed back by the high-precision spectrum analyzer through the computer control system, and pays attention to the actual volume ratio data of phosphane and argon. The computer control system has a special error calculation program built in, which automatically compares the measured volume ratio with the target volume ratio (1:4) to obtain the error value.

[0057] If the error between the actual volume ratio of phosphane 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 calculation error is within the specified range), it indicates that the composition of the mixed gas filled this time 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 mixing of the mixed gas, and the filling process needs to be analyzed, including whether the gas flow control is accurate, whether the gas uniform mixing promoter is working normally, etc., and appropriate corrective measures are taken, which may involve re-mixing the mixed gas in the cylinder or re-filling operation until the final detection result meets the error requirement.

[0058] During the entire filling process, the intelligent adaptive safety protection device installed in the filling instrument is running all the time. The adaptive environment monitoring module inside it monitors the temperature (monitoring accuracy is ±0.5℃), humidity (accuracy is ±2%), electromagnetic environment (detectable electromagnetic intensity change range is 0uT-1000uT) and other parameters of the filling environment in real time, and automatically adjusts the gas leakage detection sensitivity according to these parameters. When the environmental temperature rises to 30℃, the adaptive environment monitoring module will automatically increase the detection sensitivity of the helium mass spectrometer leak detector by one level (from 10 -2 mbar·L / s to 10 -3mbar·L / s) to ensure that the gas leakage can be accurately detected in complex environment, and when any abnormal situation is detected, including gas leakage (helium leakage detected by helium mass spectrometer or abnormal increase of phosphane concentration detected by other sensors), abnormal pressure fluctuation, etc., the hierarchical emergency response system will immediately start the corresponding emergency measures according to the set rules. For slight abnormal situations, such as a small amount of helium leakage, an audible and visual alarm is first sent to the operator, and at the same time, the local ventilation equipment is automatically started (the ventilation volume can be adjusted to 5 m 3 / min), and the leakage gas concentration is controlled within a safe range. If a more serious abnormality is detected, such as a large amount of gas leakage with the risk of causing fire and explosion, in addition to ventilation, the fire extinguishing device (dry powder extinguishing agent suitable for phosphane fire extinguishing is selected as the extinguishing medium, the injection rate is 2 kg / s, and the injection time is automatically controlled according to the actual situation) is immediately started, all gas sources and power sources are cut off, and the relevant safety management departments are notified remotely, so as to comprehensively ensure the safety of the filling process.

[0059] Through the complete operation steps and corresponding data examples of the above embodiments, the specific implementation of the phosphane mixed gas filling method in actual application and the synergistic effect of each link are fully demonstrated, and the filling target of high precision, high efficiency and safety and reliability is achieved.

[0060] The embodiments of the present application are described in detail in combination with the drawings, but the present application is not limited to the described embodiments. For those skilled in the art, various changes, modifications, replacements and variations of the embodiments can be made without departing from the principles and spirits of the present application, and still fall within the protection scope of the present application.

[0061] In the description of the specification, the description of the terms "one embodiment", "example", "specific example" and the like means that the specific features, structures, materials or characteristics described in combination with the embodiment or example are contained in at least one embodiment or example of the present application. In the present specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0062] The above is only an example and description of the present application, and those skilled in the art can make various modifications or supplements or use similar ways to replace the described specific embodiments, as long as they do not deviate from the invention or exceed the scope defined by the present claims, and still fall within the protection scope of the present application.

[0063] The above merely describes preferred specific embodiments of the present application, but the protection scope of the present application is not limited thereto, and any person skilled in the art, according to the technical solution and inventive concept of the present application, makes equivalent replacement or change within the technical range disclosed by the present application, which should be covered within the protection scope of the present application.

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 composition of the mixed gas filling the 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. 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. 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.

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 mixture 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 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.

6. 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 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.

7. The 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 calibration gas. The calibration gas is a standard mixture with known precise components and composed of 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 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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