Systems containing gas analysis devices and their control methods

Abstract

The present invention provides a system (100) having an analytical device (1) for analyzing the components contained in a gas (9). The analytical device includes: a filter (25) for selecting and passing the components contained in the gas; a detector (26) for detecting the components that have passed through the filter; and a control device (36). The system is configured such that the filter (25) causes the detector (26) to detect the presence of a lower concentration of the isotope 21Ne, which replaces the presence of a higher concentration of the isotope 20Ne as the main component contained in the gas.

Description

System with Gas Analysis Device and Its Control Method The present invention relates to a system with a gas analysis device and its control method. In Japanese Patent Laid-Open No. 2006-145295, an on-line GC / MS trace gas detection and analysis system is described, which captures and accumulates trace gas samples, transports the samples to a GC column for separation and retention, separates the samples into sample components through the GC column, and instantaneously analyzes all sample components using a mass spectrometer. In this system, the gas flow distribution system accumulates the carrier gas samples from a super-small accumulator, uses this as the carrier gas and transports it to the gas chromatography column, and supplies the carrier gas to the gas chromatography column to easily separate the sample components instantaneously, and transports the sample components to the mass spectrometer for trace gas detection, analysis or testing. Japanese Patent Laid-Open No. 2021-154240 discloses a rare gas (such as krypton) recovery system that can recover and refine rare gases from exhaust gas containing rare gases at a concentration of 100 ppm to 1% (preferably with a maximum volume concentration of less than 500 ppm) discharged from a semiconductor manufacturing device. This system includes: an impurity removal unit that removes specified impurities from the exhaust gas containing rare gases; a rare gas separation membrane module that separates a concentrated exhaust gas containing a high concentration of rare gas (krypton) with a higher rare gas concentration and an exhaust gas with a lower rare gas concentration compared to the exhaust gas containing rare gases from which specified impurities have been removed; and a rare gas adsorption unit that selectively adsorbs rare gases from the concentrated exhaust gas. Japanese Patent Laid-Open No. 2019-141752 discloses a laser gas recovery system and method that can obtain purified gas from which specified impurities have been removed from the exhaust gas discharged from an excimer laser oscillation device. This laser gas recovery system is used to obtain a purified gas mainly composed of high-purity neon gas by removing certain impurities from the exhaust gas discharged from an excimer laser oscillation device or an excimer laser oscillation chamber. It includes a separation membrane device that performs membrane separation of the rare gas for excitation other than neon from the gas to be treated, and an impurity removal device that removes specific impurities from the treated gas that has passed through (or not passed through) the separation membrane device. Japanese Patent Laid-Open No. 2005-123528 discloses a system including: an oscillation laser device having an oscillation chamber filled with a first laser gas containing F 2 gas, Ar gas and a first buffer gas, and an oscillation chamber filled with a first laser gas containing F 2An amplification chamber for a second laser gas of a gas, an Ar gas, and a second buffer gas, and an amplification device that widens and emits a laser beam emitted from a laser device for oscillation. In an exposure ArF excimer laser device operating at an oscillation frequency of 4 kHz or more, the first buffer gas is He gas or a mixed gas of He gas and Ne gas, and the second buffer gas is composed of Ne gas. Most processes involve treating gases containing a main component and trace components in the range of several percent to the ppm level or sub-ppm (ppb) level relative to the main component, and there are also many applications that require high-precision determination of the content of trace components. The gas laser field is one such area, and helium-neon lasers, argon lasers, krypton lasers, carbon dioxide lasers, excimer lasers, etc. are known. In particular, excimer lasers that generate laser light using mixed gases of noble gases or halogens are widely used in machining, semiconductor manufacturing, ophthalmic treatment, etc. Not only in gas lasers, but also in processes using gases, in order to increase the yield and precision of products, it is always desirable to monitor the composition of the gases used in the process (including the gases supplied to the process, the gases generated by the process, the gases released by the process, or the by-produced gases, etc., hereinafter referred to as process gases). Based on this, there is a need to manage the devices (processing devices) and processes (parameter management) that execute the process. Furthermore, from the viewpoints of resource conservation and circular economy, etc., the demand for reusing gases that have been used in the process, discarded (waste gas), or contain impurities is increasing. Even in such treatments, it is also strongly desired to monitor the gas composition at each stage of the recovery and / or regeneration process. Conventional gas trace component measurement devices such as GC / MS are large in size, have a long measurement time, and consume carrier gases such as helium. Therefore, there is a need for a device and method that can accurately analyze trace components on-site using a simple mechanism. One aspect of the present invention is a system having an analysis device for analyzing the components contained in a gas. The analysis device includes: a filter that selects and allows a component contained in the gas to pass through; a detector that detects the component that has passed through the filter; and a first control device that is configured to set the filter such that the filter replaces at least any one of the isotopes with a lower abundance ratio of the first component detected by the detector with an isotope having a higher abundance ratio of the first component as the first component contained in the gas. The first control device can set the filter such that the detector only detects any one of the isotopes with a lower abundance ratio of the first component. When the first component is the main component of the gas to be analyzed or one of them, the detection intensity is several times, dozens of times, hundreds of times, or even more than that of the trace components relative to the trace components. It is very difficult to measure the first component and its trace components with the same accuracy. On the other hand, the isotope with a lower abundance ratio of the first component is one fraction, one tenth, one hundredth, or less of the isotope with a higher abundance ratio of the first component. Therefore, conventionally, the isotope with a higher abundance ratio has been the main measurement target, while the isotope with a lower abundance ratio has been submerged in noise and difficult to measure, or only exists unnoticed during the measurement. In the present invention, as the first component, the isotope with a higher abundance ratio is replaced, that is, at least the isotope with a higher abundance ratio of the first component is not measured (detected), and at least any one of the isotopes with a lower abundance ratio of the first component is selected by a filter, or at least any one of the isotopes with a lower abundance ratio of the first component is measured (detected) through a detector. Thereby, for trace components that are one fraction, one tenth, one hundredth, or less of the main component, and the first component belonging to the main component, they can be measured with the same or similar accuracy. Therefore, the components contained in the gas can be measured with high accuracy including trace components, and the components of the gas can be analyzed with high accuracy. Moreover, since it is not necessary to detect a signal with an extremely high intensity corresponding to the main component, deterioration of the detector can be suppressed. The controller may also include the following device: a second control device (second coordination function, second coordination device, second coordination control device) that selects the second component contained in the gas by a filter with a resolution energy lower than the resolution energy for selecting any one of the isotopes with a lower abundance ratio of the first component and detects it with a detector. When the amount of the second component is smaller, the detection intensity related to the second component can be increased by reducing the resolution energy of the filter for high-intensity components. Therefore, even if the content of the second component is lower than the content of the isotope with a lower abundance ratio of the first component, the second component belonging to the trace components and the first component belonging to the main component can be measured with the same or similar accuracy through the isotope with a lower abundance ratio of the first component. The analysis device may have an ionization device that ionizes the components contained in the gas upstream of the filter. The ionization device can be set to suppress the ionization of the first component with the ionization energy. Saturation of the ion source in the analysis device due to the ionization of the first component with a higher abundance ratio can be suppressed, and the influence on the measurement of other trace components including impurities can be suppressed. The analysis device may include a third control device that sets the ionization energy of the ionization device to suppress the ionization of the first component. An example of the ionization device includes a filament that emits thermoelectrons. The system may have a chamber for temporarily storing the composition of the gas upstream of the analysis device and an exhaust system for controlling the amount of gas flowing into the chamber. Further, the exhaust system may be configured to maintain the pressure P in the chamber under the following condition (1). 0.005 Pa < P < 0.05 Pa ··· (1) The lower limit of condition (1) may be 0.008, and the upper limit may be 0.03. The gas pressure introduced into the mass spectrometry analysis device filtered by mass-to-charge ratio (m / z) is controlled to be below mPa (10 -3 Pa), thereby controlling the influence of components with a high abundance (abundance ratio) more. In this system, instead of measuring the isotope of the first component with the largest abundance (abundance ratio), an isotope with a relatively small (lower) abundance ratio of the first component is measured. In addition, ionization of the main first component can also be suppressed. Therefore, when the pressure in the chamber is increased, although the abundances of the main first component and trace components in the chamber increase, it is not easily affected by the increase in the main first component during measurement. Therefore, by increasing the pressure in the chamber, the abundance of trace components increases, and the effect of higher measurement (detection) sensitivity of trace components can be obtained. An example of the first component is an inert gas such as neon (Ne) or argon (Ar). If it is an inert gas, the ionization energy is high. Therefore, ionization of the main component can be suppressed, while the ionization energy can be easily set without causing problems in the ionization of trace components. Further, even if the pressure in the chamber is increased, only inert components increase, for example, filament oxidation increases, thereby reducing the possibility of deterioration of the analysis device. The filter may include a quadrupole filter. The system may have: a processing device for flowing in or discharging a process gas, a supply device for supplying a gas to be analyzed, which is at least one of the input, intermediate, and output process gases of the processing device, to the analysis device, and a management device for managing the processing device and / or the process executed by the processing device according to the analysis result of the analysis device. Another aspect of the present invention is a control method for a system having an analysis device for analyzing components contained in a gas. The analysis device has: a filter for selecting a component contained in the gas and allowing the component to pass through, and a detector for detecting the component that has passed through the filter. The method includes: the controller of the analysis device selects, by the filter, any one of the isotopes with a low abundance ratio of the first component contained in the gas to replace the isotope with a high abundance ratio of the first component. The controller can control the analysis device such that only any one of the isotopes with a low abundance ratio of the first component is selected by the filter and detected by the detector. This method may further include a controller that uses the filter to select the second component contained in the gas in a state of reducing the resolution energy and detects it using the detector. The analysis device may have an ionization device that ionizes the components contained in the gas upstream of the filter. The method may further include the controller setting the ionization energy to suppress the ionization of the first component. The system may have a chamber that temporarily holds the gas upstream of the analysis device and an exhaust system that controls the amount of gas flowing into the chamber. The method may further include the controller maintaining the pressure P in the chamber under the above condition (1). The system may have a processing device for flowing process gas in or out and a supply device for supplying the process gas of at least any one of the input, intermediate, and output of the processing device to the analysis device. The management device of the system may have: managing the processing device and / or the process based on the analysis result of the analysis device. One of the other aspects of the present invention is a method for analyzing the components contained in a gas by an analysis device. The analysis device has a filter that selects the components contained in the gas and allows the components to pass through, and a detector that detects the components that have passed through the filter. The method includes selecting any one of the isotopes with a low abundance ratio of the first component to replace the isotope with a high abundance ratio of the first component as the components contained in the gas and detecting with the detector. One of the other aspects of the present invention is a control program (program product) for a system having an analysis device for analyzing the components contained in a gas, which can be recorded on a suitable recording medium and provided. The analysis device has a filter that selects the components contained in the gas and allows the components to pass through, and a detector that detects the components that have passed through the filter. The control program includes: the controller of the analysis device commands to select any one of the isotopes with a low abundance ratio of the first component to replace the isotope with a high abundance ratio of the first component as the first component contained in the gas through the filter and detect with the detector. FIG. 1 shows a schematic configuration of a process monitoring system 100 as an example of a system including a gas analysis device 1. The illustrated exemplary system 100 is a system that manages a gas regeneration device (recycling device, processing device) 101 and a gas regeneration process 101p performed by the gas regeneration device 101. The system 100 includes: the gas 109a of the process 101p supplied to the gas regeneration device 101 as the process gas, the gas 109b processed and output via the process 101p, and the gas 109c switched in the process 101p, or a supply device 102 that supplies the gas (sample gas) 9 to be analyzed in parallel to the gas analysis device 1, and a management device (process controller) 105 that manages the gas regeneration device 101 and / or the process 101p with reference to the analysis result of the gas analysis device 1. The supply device 102 in this example includes switching valves 103a, 103b, and 103c that switch the gases 109a, 109b, and 109c and supply them to the gas analysis device 1. The processing device for the process gas 109 that flows into or out of the gas analysis device 1 and is the analysis target is not limited to the gas regeneration device 101. The processing device can be a device used in semiconductor processes to perform processes including forming various types of films or layers on a substrate or etching the substrate, such as a device that performs processes including CVD (Chemical Vapor Deposition) or PVD (Physical Vapor Deposition). The processing device is not limited to processes related to semiconductor manufacturing. It can be a device that performs a process of laminating various types of thin films using optical parts such as lenses and filters as substrates. It can be a device that mixes, regenerates, and recovers the gases used in semiconductor manufacturing. It can also be a processing device for processing gases for other purposes. An example of the gas regeneration device 101 is disclosed in Japanese Patent Application Laid-Open No. 2019-141752. An example of the gas regeneration device 101 is a device (laser gas recirculation system) that obtains a purified gas with predetermined impurities removed from the exhaust gas discharged from an excimer laser oscillation device. An example of the exhaust gas (process gas) 109a to be processed has neon as the main component, and the amount of rare gases (krypton, xenon, argon) is 1% to 10% of the total amount, preferably 1% to 8%. And the impurities in the exhaust gas can be exemplified by, for example, CF4 (CF 4 ), N2 (N 2 ), He, etc. It is recorded that the concentration of CF4 in the exhaust gas is expected to be in the range of 1 ppm to 500 ppm. As an example of a laser gas with neon as the main component, Japanese Patent Application Laid-Open No. 2005-123528 discloses that one type of ArF gas is a mixed gas of 3.5% argon Ar, 10 ppm (0.001%) xenon Xe, and the remaining neon Ne, that is, 96.499%. Therefore, when the device 101 that processes such gases is the monitoring target and the components of the gas to be processed and the recycled gas are monitored, it is preferable for the gas analysis device 1 to be able to monitor in real time on-site the trace components or impurity components present in concentrations (mixing ratios) from the % level to below the ppm level relative to the main component. The process monitoring system 100 of the gas analysis device 1 in this example can provide innovative process control by instantaneously monitoring the gas 9 to be analyzed and providing highly reliable measurement results (analysis results). For example, the gas analysis device 1 can instantaneously monitor the gas components used in various processes or steps related to semiconductor manufacturing, thereby significantly increasing the yield in semiconductor wafer manufacturing and maximizing the product yield, thus serving as an overall solution platform. In addition, by combining with a gas generation, recovery, and regeneration system, from the perspectives of resource conservation and circular economy, etc., it also serves as a platform for reviewing each process and maximizing resource utilization efficiency. The gas analysis device 1 in this example is generally an extremely small mass analysis device and can be directly connected or integrated into the device to be analyzed. Moreover, the gas analysis device 1 can install standard protocols mainly adopted in semiconductor manufacturing process devices, such as the EtherCat (registered trademark) protocol 51, and can be integrated with process machine control systems such as the process monitoring system 100. The gas analysis device 1 is a device for analyzing the components contained in a gas (sample gas) 9. The gas analysis device 1 includes: a chamber 10 configured to temporarily store the sample gas 9 supplied from the process side by a supply device 102; an ionization device 22 configured to generate ions (ion current) 17 of the sample gas 9; a filter 25 configured to select the components contained in the gas and allow the components to pass through; and a detector 26 configured to detect the components that have passed through the filter. An example of the gas analysis device 1 is a mass analysis type detector (mass spectrometer, MS). The filter 25 can include a filter unit (typically a mass filter, a quadrupole filter in this example) 25, and the filter unit 25 filters (selects, classifies, switches) the ionized sample gas (sample gas ions) 17 supplied from the ionization device 22 according to the mass-to-charge ratio. The detector 26 can be a detector for detecting the filtered ions (ion intensity, ion current). The gas analysis device 1 further includes a vacuum container (housing) 40 that houses the filter unit 25 and the detector 26, and an exhaust system 60 that can maintain the inside of the housing 40 and the chamber 10 connected to the housing 40 under appropriate negative pressure conditions (vacuum conditions). The chamber 10 is important as a place for controlling the conditions (pressure) of the sample gas 9 flowing into the gas analysis device 1, but in order to perform instant measurement, the chamber 10 has a minimum capacity, for example, it can be 1 to several tens of cm 3 or has a container or buffer with a capacity of 1 to several tens of cm 3 or so, and can also be constituted by a part of the pipe that also serves as the supply device 102. The exhaust system 60 of this example includes a turbo molecular pump (TMP) 61 and a Roots pump (dry pump) 62, and controls the internal pressure of the chamber 10 through the housing 40 with the built-in filter 25 and detector 26. The dry pump 62 can be set as an option. Other types of pumps that can be used in the exhaust system 60 can be a single-stage exhaust system or a multi-stage exhaust system with three or more stages. The exhaust system 60 can be provided with an exhaust passage 65 that exhausts from the sample chamber 10 around the housing 40. In addition to the filtered gas flow, sample gas 9 can be introduced into the sample chamber 10 to control the internal pressure of the sample chamber 10. When analyzing the gas to be discarded or discharged, a large amount of sample gas 9 can be inhaled into the sample chamber 10 from the process relative to the amount of gas (ion amount) supplied to the filter 25, and a gas analysis device 1 that can monitor the state (variation) of the process 101p in real time can be provided. An example of the filter 25 is a mass filter, which includes four cylindrical or columnar electrodes (HyperQuad) 25a, and the interior is processed into a hyperboloid to form a hyperbolic electric field for filtering based on the mass-to-charge ratio. The quadrupole mass filter 25 can be one that arranges a large number of, for example, nine cylindrical electrodes in a matrix (array) to form a plurality of pseudo-hyperbolic electric fields. Examples of the detector 26 include a Faraday cup (FC: Faraday Cap), a secondary electron multiplier (SEM: Secondary Electron Multiplier), etc. The detectors 26 can be used in combination or switched. The detector 26 can be other types such as a channel electron multiplier (CEM) or a microchannel plate (MP). The ionization device 22 includes an electron ionization device (filament, EI ion source) 23, and this electron ionization device 23 ionizes (electron ionization) the sample gas 9 supplied from the process 101p through the gas supply device 102 and the chamber 10 through electron collision (thermal electrons). The EI ion source 23 usually operates under a high vacuum of 10 -3 Pa or less. In this example, when the main component of the sample gas 9 is an inert gas, it can operate under a low vacuum of 10 -2 Pa or more. The gas analysis device 1 can be provided with one or a plurality of lenses (ion lenses, electrostatic ion lenses) 24, which are configured to guide the ionized gas 9 as an ion current (ion beam) 17 to the filter 25. The gas analysis device 1 includes a controller (control box, control module) 30 that controls each module of the analysis device 1, and an interface device 50 with the outside. The controller 30 includes computer resources such as a CPU and a memory, and controls the gas analysis device 1 by loading and executing a program (program product) 39. The program 39 can be provided by being recorded on a computer-readable medium. The interface device 50 includes a power input I / F 52 and a communication I / F 51 according to Ethernet control automation technology. The control module (controller) 30 has the functions of: controlling the ionization device 22 (ionization control device) 31, controlling the filter 25 (filter control device) 32, detecting ions (ion current) reaching through the detector 26 (detector control device) 33, and controlling the exhaust system 60 to control the pressure in the chamber 10 (pressure control device) 34. These control devices 31 to 34 can have the function of controlling each device (unit) of each control object to maintain set values or conditions. In addition, the controller 30 can have the function of performing a predetermined measurement function (coordinated control device) 35 by coordinately controlling a plurality of devices (units) of the gas analysis device 1. The coordinated control device can include, for example, the function of the controller 30 setting a predetermined condition in the filter 25 and causing the detector 26 to detect the components selected according to this condition. The ionization control device 31 that controls the ionization device 22 can include the function of an ionization energy control device (filament control device) that controls the filament current and / or voltage supplied to the filament 23. FIG. 2 shows an example of measuring the process gas (first mixed gas) 109b regenerated by the gas regeneration process 101p of the above gas regeneration device 101 as the sample gas 9. The first mixed gas 109b is an ArF gas and contains, for example, 3.5% argon Ar, 10 ppm (0.001%) xenon Xe, and 96.499% neon Ne. FIG. 2 shows an example of the result of measuring the first mixed gas 109b as the sample gas using a conventional mass spectrometer (MS: Mass Spectrometer). The mass analysis result is obtained in the form of the relationship between intensity and mass-to-charge ratio (m / z). Neon, argon, xenon, helium, krypton, etc. all belong to chemically stable noble gases. Neon is an element with an atomic number of 10, and its stable isotopes include 20Ne with a mass-to-charge ratio of 20 at 90.48%, 21Ne with a mass-to-charge ratio of 21 at 0.27%, and 22Ne with a mass-to-charge ratio of 22 at 9.25%. Argon is an element with an atomic number of 18. As a stable isotope, 40Ar with a mass-to-charge ratio of 40 is 99.6%, 38Ar with a mass-to-charge ratio of 38 is 0.063%, and 36Ar with a mass-to-charge ratio of 36 is 0.337%. Xenon is an element with an atomic number of 54. As stable isotopes, 132Xe with a mass-to-charge ratio of 132 is 26.9%, 131Xe with a mass-to-charge ratio of 131 is 21.2%, 130Xe with a mass-to-charge ratio of 130 is 4.07%, 129Xe with a mass-to-charge ratio of 129 is 26.4%, 128Xe with a mass-to-charge ratio of 128 is 1.91%, and 126Xe with a mass-to-charge ratio of 126 is 0.089%. When measuring this mixed gas 109b using an existing mass analysis device, neon accounts for more than 96% of the components contained in the mixed gas 109b. Compared with neon, the concentration (content rate) of xenon is approximately reduced to 10 -6 or so. Therefore, it is difficult to simultaneously detect neon and xenon using a detector under the same conditions. In particular, it is difficult to simultaneously measure each component with high precision, and the ion current is huge when measuring neon, making it difficult to ensure the service life of the detector. In addition, even if an attempt is made to simultaneously measure argon, in fact, the majority neon gas in the gas is ionized, causing the ionization device to be in a saturated state, and it is expected that the ionization of argon is hindered. Therefore, it is considered that such a sample gas 9 cannot be measured using a mass spectrometry type gas analysis device. Figure 3 shows an example of the intensity of argon obtained when the pressure in the chamber 10 is set to 10 -2 Pa, the ionization energy (thermoelectron energy) of the ionization device 22 is changed, and the mixed gas 109b is measured. In conventional mass analysis devices, the ionization energy in the ionization device is set to 70 eV because the mass spectra registered in existing databases such as NIST are measured at 70 eV. However, in this case, when the ionization energy is increased, the argon ions increase, and this increasing trend has a peak near the ionization energy of 37 eV. Then, it can be seen that when the ionization energy is increased to 70 eV, the intensity of argon decreases. Therefore, when the ionization energy exceeds approximately 37 eV, it is considered that the interior of the ionization device 22 is saturated with ionized neon, which accounts for the majority of the mixed gas 109b, and the ionization of argon is prevented. Therefore, it is understood that in a gas in which the main component (the first component) such as the mixed gas 109b accounts for several 10%, the ionization of other components can be promoted by suppressing the ionization of the main component. FIG. 4 shows the relationship between the pressure in chamber 10 and the measured argon intensity when the ionization energy is set to 35 eV during measurement of the mixed gas 109b. By increasing the pressure inside the chamber, more argon will be introduced into the filter 25 and the intensity measured by the detector 26 should increase. From the measurement results, it can be confirmed that even when the ionization energy is set lower than the value set in conventional mass spectrometers, the measured intensity (detection intensity) of argon increases almost proportionally to the chamber pressure. The ionization energies of these components belonging to inert gases are relatively high. The ionization energy of neon is about 21.6 eV, the ionization energy of argon is about 15.8 eV, and the ionization energy of xenon is about 12.1 eV. Therefore, it can be seen that in the ionization device 22, ionizing with an energy exceeding the ionization energy of each component has the advantage of increasing the amount of ions, but there is an influence of an excessive increase in the ion content. In particular, for the mixed gas 109b in this example, when the ionization energy of the main component (first component) in the gas is relatively high, by reducing the ionization energy in the ionization device 22 to a predetermined range, conditions for the ionization energy can be found that can suppress the ionization of the main component and hardly affect the ionization of trace components. For example, the target value of the ionization energy of the ionization device 22 can be set to a value that is insufficient or inadequate for the ionization energy of the main component (a value that ionizes but is not sufficient to ionize all molecular ions), and this value can be set to be sufficiently higher than the ionization energy of the trace component. The ionization control device 31 of the controller 30 of the gas analysis device 1 in this example may include a function of maintaining the ionization energy of the ionization device 22 at a set value 22a that satisfies the above conditions. The controller 30 may include a third control device 31a that sets the ion energy of the ionization device 22 to a value 22a that suppresses the ionization of the first component. When the above mixed gas 109b is analyzed as the sample gas 9, the third control device 31a can set the set value 22a of the ionization energy to 35 eV or around it. The coordinated control function 35 of the controller 30 includes a first control device 36 that is configured to set the filter 25 so that the detector 26 detects the first component contained in the gas (sample gas) 9 in which at least any one of the isotopes with a lower abundance ratio of the first component replaces the isotope with a higher abundance ratio of the first component as the measurement target. The first control device 36 includes a first coordination function (first coordinated control device), and this first coordination function selects at least any one of the isotopes with a lower abundance ratio in the first component by the filter 25 and detects it with the detector 26. The first control device is configured to set the filter 25 so that the detector 26 only detects any one of the isotopes with a lower abundance ratio in the first component. The controller 30 may further include a second control device 37, which sets the filter 25 such that the detector 26 detects the trace second component contained in the sample gas 9 with a decomposition energy lower than that of the isotope with a lower decomposition energy than the presence ratio of the first component selected. The second control device 37 includes a second coordination function (second coordination control device), which uses the filter 25 to select the trace second component with a low decomposition energy and uses the detector 26 for detection. The controller 30 may include a pressure control device 34, which maintains the pressure P in the chamber 10 via the exhaust system 60 under the following conditions. 0.005 Pa < P < 0.05 Pa...(1) The lower limit of condition (1) may be 0.008, and the upper limit may be 0.03. FIG. 5 shows the results of a simulation measurement using the gas analysis device 1 of this example with the above-mentioned ArF gas (first mixed gas) 109b as the sample gas 9. First, via the first control device 36, as the first component (neon) of the main component in the sample gas 9, the isotope with a high presence ratio (20Ne) is replaced, that is, the isotope with a high presence ratio (20Ne) of the first component is not measured (detected). At least any one of the isotopes with a low presence ratio of the first component. In this example, the filter 25 is set to select only 21Ne. At this time, the ion current passing through the filter 25 is measured (detected) by the detector 26. The first control device 36 can be set such that 20Ne does not pass through the filter 25 (there is no timing set for it to pass), or the detector 26 can be turned off when 20Ne passes through the filter 25. In the gas analysis device 1, the first control device 36 causes the filter 25 to select 21Ne with an intensity of about 0.27% of neon gas (10 -4 ) to replace 20Ne and is detected by the detector 26. Therefore, neon gas, which is the main component of the sample gas 9 and accounts for more than 90%, can be detected with an intensity close to that of trace components in the ppm order. Therefore, in the gas analysis device 1, the main components and trace components contained in the gas 9 can be measured with high precision, and the components containing trace components in the gas 9 can be analyzed with high precision. Moreover, in the gas analysis device 1, there is no need to detect a signal with an extremely high intensity corresponding to the main component, so the deterioration of the detector 26 can be suppressed. In the gas analysis device 1 of this example, even for argon gas with the second highest mixing ratio in the ArF gas 109b, the first control device 36 can select only 36Ar with a low presence ratio to replace 40Ar with a high presence ratio via the filter 25 and detect it via the detector 26. Therefore, in the gas analysis device 1, even for argon, which is the second highest in content in the sample gas 9 after neon, it can be detected with an intensity the same as or close to that of other trace components. In addition, compared with existing filament-type mass spectrometers, the gas analysis device 1 uses the pressure control function 34 to set the pressure P in the chamber 10 to be more than one order of magnitude higher than that of conventional filament-type mass spectrometers, increasing the amount of sample gas 9 flowing into the gas analysis device 1. On the other hand, the ionization energy control function 31a of the ionization control device 31 reduces the set value 22a of the ionization energy to 35 eV to suppress the ionization of neon isotopes, which are the main components of the sample gas 9. Therefore, the ion amount of trace components other than neon can be relatively increased, and the detection sensitivity of trace components can be improved. In addition, the main component of the mixed gas (ArF) 109b to be measured is neon, an inert gas, and it is considered that increasing the inflow amount has almost no effect on the life of the filament 23. In addition, there may be impurities from the chamber 10 or the supply device 102 of the chamber 10, etc. However, by increasing the amount of gas 9 flowing into the chamber 10, the amount of impurities from the gas regeneration device 101 or the process 101p can be increased, and there is also the advantage of being able to improve the detection sensitivity of trace components that are elements of the management device 101 or the process 101p. In the gas analysis device 1, a trace second component (xenon) contained in the sample gas 9 from the process gas (ArF gas) 109b is selected by the filter 25 and detected by the detector 26 with a decomposition energy lower than that of the isotope (21Ne) with a lower abundance ratio than that of the selected first component (neon). The second control device 37 controls the scanning unit (decomposition energy, mass-to-charge ratio m / z) of the gas analysis device 1 to control the filter 25 and the detector 26 to detect only the isotope 21Ne with a decomposition energy of 1 AMU or more when measuring neon. On the other hand, when measuring xenon, the second control device 37 controls the filter 25 and the detector 26 to detect in a wide range of multiple isotopes including xenon. When measuring xenon, the second control device 37 can also control the filter 25 and use the set (integration) of the measurement results of the detector 26 detected with a decomposition energy of 1 AMU or more as the detection result of xenon. The second control device 37 sets the filter 25 to detect all the stable isotopes 132Xe, 131Xe, 130Xe, 129Xe, 128Xe, and 126Xe as the intensity of xenon in xenon and detects them with the detector 26. With these controls and settings, in the gas analysis device 1, it is possible to detect ppm-level xenon present in the first mixed gas (ArF gas) 109b with intensities close to 100% of neon and several percent of argon. Therefore, the gas analysis device 1 can simultaneously perform real-time measurement, analysis, and monitoring of trace components and main components in the process gas 109b. Similarly, in addition to the components of the predetermined mixed gas (ArF gas), the process gas 109 also contains, for example, helium (He), methane (CH 4 )、 Nitrogen (N 2 )、 Oxygen (O 2 )、 Carbon dioxide (CO 2 ) and carbon tetrafluoride (CF 4 ), etc., these impurities can be measured in real time with high precision and used for managing process 101p. In addition, system 100 is equipped with a calibration device 70, which pre-measures a standard gas (test gas) 71 containing a known concentration by setting the measurement conditions of gas analysis device 1 as described above, and corrects the detection intensity of trace components such as argon and xenon and the detection intensity of the main component neon. The controller (control module) 30 of gas analysis device 1 stores the calibration result 38a, and when measuring the sample gas 9 on-site, based on the ratio of the detection intensity of other components to the detection intensity of the main component (first component) neon, a mixing ratio output device (calculation function, calculation device, output device) 38 can obtain the mixing ratio of trace components based on the calibration result 38a. Gas analysis device 1 can measure trace components or impurities with high precision on-site. Therefore, the measurement results (analysis results) of gas analysis device 1 can be used in the control, management, and monitoring of process 101p. The function of obtaining the mixing ratio can be installed in an external device such as process controller 105. The gas to be measured by gas analysis device 1 can be other gases, such as KrF gas. As a gas for xenon lasers, a krypton-containing gas (KrF gas) is known to replace xenon. Krypton (Kr) is an element with an atomic number of 36. As stable isotopes, 86Kr with a mass-to-charge ratio of 86 accounts for 17.3%, 84Kr with a mass-to-charge ratio of 84 accounts for 57%, 83Kr with a mass-to-charge ratio of 83 accounts for 11.5%, 82Kr with a mass-to-charge ratio of 82 accounts for 11.6%, 80Kr with a mass-to-charge ratio of 80 accounts for 2.25%, and 78Kr with a mass-to-charge ratio of 78 accounts for 0.35%. Therefore, even in system 100 where a mixed gas containing Kr from ppm to about several percent is used as the measurement object, the gas analysis device 1 in this example can detect and analyze a mixed gas of Kr containing other trace impurities with high precision, just like a mixed gas containing xenon. The analysis result of the gas analysis device 1 can be supplied to the process controller 105 through the communication interface 51 such as the Ethernet control automation technology of the interface device 50. The analysis result can provide the process 101p to other external devices for monitoring via the cloud. The process controller 105 can be equipped with computer resources such as a CPU and a memory, and can be operated by a control program (program product) 108. An example of the process 101p controlled and / or monitored by the process controller 105 is a process executed by the processing device 101 for the inflow or discharge of gas used in the semiconductor process. At least any one of the input, intermediate, and output process gases 109a to 109c of the processing device 101 is supplied to the gas analysis device 1 through the supply device 102 for analysis. Based on the result, the processing device 101 and the process 101p can be controlled and monitored. Figure 6 shows an example of the control process (control method, control program) in the process monitoring system 100 including the gas analysis device 1. In stage 81, at least any one of the process gases 109a to 109c at the input, intermediate, and output of the processing device 101 for the inflow or discharge of the process gas is selected through the supply device 102 and supplied to the gas analysis device 1 as the sample gas 9. In stage 82, the gas analysis device 1 starts gas analysis. First, in stage 83, the gas analysis device 1 uses the ionization control device (third control device) 31a to set the ionization energy 22a of the ionization device 22 to a value suitable for the measurement target gas 9. In this example, when measuring a mixed gas mainly composed of neon (first component), the ionization energy 22a that can suppress the ionization of neon is set to, for example, 35 eV. Then, in stage 84, the gas analysis device 1 uses the pressure control device 34 to set the pressure in the chamber 10 to a range higher than the normal condition (1) to increase the amount of trace components supplied to the gas analysis device 1. In stage 86, when measuring neon, the main component (first component) with a very high content, in stage 87, the first control device 36 selects the isotope 21Ne with a low abundance ratio through the filter 25 to replace the isotope 20Ne with a high abundance ratio (20Ne is not measured), and detects it with the detector 26. A plurality of isotopes with low abundance ratios can be selected and detected. However, when attempting to detect the main component with the same intensity as the trace component, especially the extremely trace component in the ppm order, any one of the isotopes with a low abundance ratio can be selected (limited to any one) by the filter 25 and detected with the detector 26. In stage 88, then, when measuring argon with a high content. In stage 89, the first control device 36 selects the isotope 36Ar with a low abundance ratio through the filter 25 to replace the isotope 40Ar with a high abundance ratio (40Ar is not measured), and detects it with the detector 26. In step 90, when measuring xenon (the second component) which is a trace component, in step 91, the second control device 37 uses the filter 25 to select the isotopes of xenon, and uses the detector 26 to detect the isotopes with a resolution lower than that of the isotopes 21Ne or 36Ar with a lower abundance ratio in the selected main components. For example, all the targets of 126Xe, 128Xe, 129Xe, 130Xe, 131Xe and 132Xe which belong to the isotopes of xenon are selected by the filter 25 and detected by the detector 26, and the sum (integral value) of these is used as the measured value of xenon. In step 92, the gas analysis device 1 can output the mixing ratio to the process controller 105 based on the calibration result 38a by using the mixing ratio output device 38. In addition, information on impurities such as helium (He), methane (CH 4 )、nitrogen (N 2 )、oxygen (O 2 )、carbon dioxide (CO 2 )、carbon tetrafluoride (CF 4 ) etc. at the ppm or sub-ppm level obtained during the gas analysis process is output to the process controller 105. In step 93, the process controller 105, as a process management device, manages the processing device (gas regeneration device) 101 or the process (gas regeneration process) 101p executed by the processing device based on the measurement result (analysis result) of the gas analysis device 1. As described above, as an embodiment of the present invention, a method for rapidly analyzing impurities in Ne gas for excimer lasers using the gas analysis device 1 can be provided. For Ne gas used in excimer lasers, the concentrations of Ar, Xe, Kr, etc. in the gas must be maintained within a certain range. In addition, it is also necessary to ensure that components unsuitable for lasers such as N 2 、O 2 、CO etc. are below a certain concentration. Moreover, considering the analysis time, space, consumption of carrier gas, etc., the Ne gas can be directly introduced into the mass spectrometer and the impurities in the Ne gas can be measured immediately without using a gas chromatograph (GC). Therefore, it is necessary to improve the detection of Xe and impurities in Ne gas (such as N in Ne 2 、O 2 、CO、CO 2The analysis sensitivity of (etc.). In the gas analysis device 1, more gas than normal (for example, with an upper limit of 10 -3 Pa) (for example, around 10 -2 Pa) is introduced into the mass analysis chamber 10 through the pressure control device 34. Thereby, more impurities are introduced into the mass analysis chamber 10. In particular, in addition to those derived from Ne gas, impurities such as N 2 , O 2 always exist in the mass analysis chamber as background components in a certain amount. Therefore, it is necessary to distinguish whether the gas is from the chamber or neon. As much as possible, by introducing a large amount of Ne gas into the mass analysis chamber and increasing the amount of impurities from Ne gas relative to the background in the vacuum, the concentration of impurities can be measured with higher sensitivity. In addition, Ne gas is an inert gas, and even if more gas than normal is introduced into the mass analysis chamber 10, the filament 23 is not easily damaged. Next, the ionization energy is controlled by the ionization energy control device (the third control device) 31a. If only a large amount of Ne gas is introduced into the mass analysis chamber 10, the ion source will be saturated with Ne ions, which will have an adverse effect on the accuracy of the impurity concentration analysis. Therefore, the ionization energy (the energy when the thermoelectrons released from the filament 23 collide with molecules and atoms) is adjusted to suppress the ionization of Ne. In this example, 35 eV is used. Since the energy required for the ionization of Ne is much higher than the ionization energy of other atoms or molecules, by adjusting the ionization energy, other atoms or molecules can be fully ionized while only the ionization of Ne can be suppressed. In addition, when there is no possibility of overlap of other components in the mass region of the object to be measured (for example, Xe), the second control device 37 performs the measurement with sensitivity prioritized over resolution. Specifically, higher ion intensity can be obtained by thickening the peak. In addition, via the first control device 36, ionization of Ne (20Ne) is suppressed and the isotope 21Ne is used, thereby reducing the intensity of the Ne peak used for quantification by several orders of magnitude. In the excimer laser gas, it is necessary to keep the concentrations of Xe, Ar, Kr, etc. in the Ne gas within a certain concentration range. However, in order to maintain these concentrations within a certain range, it is necessary to be able to monitor these concentrations with high precision. Via the first control device 36, the intensity of the Ne peak used for quantification can be reduced by several orders of magnitude, and the ratio of each peak of Ne / Ar / Xe (for example, in the case of the ArF laser gas) can be approximated. For Ar, by using the isotope 36Ar, the intensity of the Ar peak used for quantification can be reduced by several orders of magnitude. By carefully selecting the isotopes of each component contained in the gas, the intensity of these peaks can be approximated more closely, thereby improving the accuracy of concentration calculation. In addition, by detecting 21Ne and 36Ar with relatively low isotopes and calculating the concentrations of each component, it is not necessary to detect ions with large peak currents such as 20Ne and 40Ar. Therefore, a gas analysis device 1 that can suppress the deterioration of the detector 26 and can be used for a long time can be provided. In addition, via the mixing ratio output device 38, the concentration (mixing ratio) can always be calculated based on the peak intensity of Ne and the ratio of the peak intensity of Ne to the peak intensity of other components. Usually, the impurity concentration is directly calculated based on the peak intensity. At this time, the peak intensity changes according to the amount of gas introduced into the mass spectrometer. Therefore, when performing quantification in a system with a pressure change in the measurement environment, the amount of gas introduced into the mass analysis device must be kept constant. In this method, by calculating the concentration based on the Ne peak, even if there is some change in the pressure inside the mass spectrometer, this change can be offset. In addition, the example of a mass filter using a quadrupole type as the filter 25 has been described above. The filter 25 can select, classify, and turn on / off components of molecules and / or atoms including TOF, ion trap, Wien filter, etc. according to the mass-to-charge ratio m / z, and can be of other types. In addition, although specific embodiments of the present invention have been described above, those with ordinary knowledge in the technical field can design various other embodiments and modification examples without departing from the scope and spirit of the present invention. Such other embodiments and deformations become the subject of the following patent application scope, and the present invention is defined by the following patent application scope. 1: Gas analysis device 9: Gas (sample gas) 10: Chamber 17: Ion current (ion beam) 22: Ionization device 22a: Ionization energy 23: Electron ionization device 24: Lens (ion lens, electrostatic ion lens) 25: Filter 25a: Cylindrical electrode (HyperQuad) 26: Detector 30: Controller 31: Ionization control device 31a: Third control device 32: Filter control device 33: Detector control device 34: Pressure control device 35: Coordination control device 36: First control device 37: Second control device 38: Mixing ratio output device 38a: Calibration result 39: Program product 40: Housing 50: Interface device 51: Communication I / F for Ethernet control automation technology 52: Power input I / F 60: Exhaust system 61: Turbo molecular pump (TMP) 62: Dry pump 65: Exhaust passage 70: Calibration device 71: Standard gas (test gas) 100: System 101: Gas regeneration device 101p: Gas regeneration process 102: Supply device 103a: Switching valve 103b: Switching valve 103c: Switching valve 105: Management device (process controller) 108: Control program (program product) 109a: Gas 109b: Gas 109c: Gas [Fig. 1] A block diagram showing the system overview including the gas analysis device. [Fig. 2] An example of the measurement result of the gas. [Fig. 3] A graph showing how the detection intensity changes according to the ionization energy. [Fig. 4] A graph showing how the detection intensity changes according to the chamber pressure. [Fig. 5] An example of the measurement result of the gas. [Fig. 6] A flowchart showing the overview of system control. 1: Gas analysis device 9: Gas (sample gas) 10: Chamber 17: Ion current (ion beam) 22: Ionization device 22a: Ionization energy 23: Electron ionization device 24: Lens (ion lens, electrostatic ion lens) 25: Filter 25a: Cylindrical electrode (HyperQuad) 26: Detector 30: Controller 31: Ionization control device 31a: Third control device 32: Filter control device 33: Detector control device 34: Pressure control device 35: Coordination control device 36: First control device 37: Second control device 38: Mixture ratio output device 38a: Calibration result 39: Program product 40: Housing 50: Interface device 51: Communication I / F for Ethernet control automation technology 52: Power input I / F 60: Exhaust system 61: Turbo molecular pump (TMP) 62: Dry pump 65: Exhaust passage 70: Calibration device 71: Standard gas (test gas) 100: System 101: Gas regeneration device 101p: Gas regeneration process 102: Supply device 103a: Switching valve 103b: Switching valve 103c: Switching valve 105: Management device (process controller) 108: Control program (program product) 109a: Gas 109b: Gas 109c: Gas

Claims

1. A monitoring system comprising an analytical device for analyzing components contained in a gas, the analytical device comprising: a filter for selecting and passing components contained in the gas; a detector for detecting components that have passed through the filter; a first control device configured such that the filter is configured such that the detector detects at least one isotope of the first component with a low presence ratio and obtains a first intensity, replacing the isotope of the first component with a high presence ratio as the first component contained in the gas; a second control device configured such that the filter is configured such that the detector detects a second component with a trace amount relative to the first component contained in the gas and obtains a second intensity; and an output device that, without detecting the isotope of the first component with a high presence ratio, calculates the mixing ratio of the second component and the first component based on the first intensity of at least one isotope of the first component with a low presence ratio and the second intensity of the second component, which is a trace amount relative to the first component.

2. The monitoring system of claim 1, wherein the first control device is configured such that the filter is configured such that the detector detects only any isotope with a lower presence of the first component to obtain the first intensity.

3. The monitoring system of claim 1, wherein the second control device is configured such that the filter is configured to detect the second component contained in the gas by means of the detector at a decomposition energy that is lower than that of any isotope with a lower presence ratio of the first component.

4. The monitoring system of claim 1, wherein the analytical device further comprises an ionization device that ionizes the components contained in the gas upstream of the filter, and the ionization energy suppresses the ionization of the first component.

5. The monitoring system of claim 1, wherein the analytical device further comprises an ionization device that ionizes the components contained in the gas upstream of the filter, and a third control device that sets the ionization energy of the ionization device to suppress the ionization of the first component.

6. The monitoring system as described in claim 4 or 5, wherein the ionization device comprises a filament that emits thermionic electrons.

7. A monitoring system as claimed in any of claims 1 to 5, comprising a chamber that temporarily maintains the composition of the gas upstream of the analytical apparatus and an exhaust system that controls the amount of gas flowing into the chamber and maintains the pressure P in the chamber in such a manner as 0.005 Pa < P < 0.05 Pa.

8. The monitoring system of any one of claims 1 to 5, wherein the first component mentioned above contains an inert gas.

9. The monitoring system as described in any of requests 1 to 5, wherein the aforementioned filter includes a quadruple filter.

10. A monitoring system according to any one of claims 1 to 5, comprising a processing device for causing process gas to flow into or out, a supply device for supplying at least one of the process gas inputs, intermediate and outputs of the processing device to the analysis device, a management device for managing the processing device or the process executed by the processing device based on the analysis results of the analysis device.

11. A control method for a monitoring system, the system comprising an analytical device for analyzing components contained in a gas, wherein the analytical device comprises a filter for selecting components contained in the gas and allowing them to pass through, and a detector for detecting components that have passed through the filter, the method comprising: a controller using the detector to detect at least one isotope with a low presence ratio of the first component selected as a first component contained in the gas via the filter, replacing an isotope with a high presence ratio of the first component, to obtain a first intensity; detecting a second component in the gas selected via the filter, which is present in trace amounts relative to the first component, via the detector, to obtain a second intensity; without detecting an isotope with a high presence ratio of the first component, and based on the first intensity of at least one of the isotopes with a low presence ratio of the first component, and the second intensity of the second component, which is present in trace amounts relative to the first component, to determine the mixing ratio of the second component to the first component.

12. As in request item 11, wherein, The first intensity is obtained by detecting at least one of the isotopes with a low presence ratio of the first component through the above-mentioned filter using the above-mentioned detector, which includes obtaining the second intensity by detecting only one of the isotopes with a low presence ratio of the first component through the above-mentioned filter.

13. The method of claim 11, wherein detecting the second intensity by the detector further comprises: the controller selecting the second component contained in the gas using the filter with a decomposition energy lower than that of any isotope with a lower presence ratio of the first component, and detecting the second intensity using the detector.

14. The method of claim 11, wherein the analytical apparatus comprises an ionizing device for ionizing components contained in the gas upstream of the filter, the method further comprising setting the ionization energy of the controller to suppress the ionization of the first component.

15. The method of any one of claims 11 to 14, wherein the method comprises a chamber for temporarily holding the gas upstream of the analytical apparatus and an exhaust system for controlling the amount of gas flowing into the chamber, the method further comprising the controller maintaining a pressure P in the chamber under the condition that 0.005 Pa < P < 0.05 Pa.

16. The method of any one of claims 11 to 14, wherein the first component comprises an inert gas.

17. The method of any one of claims 11 to 14, wherein the system comprises: a processing device for allowing process gas to flow in or out, and a supply device for supplying at least one of the process gas, an input, an intermediate, and an output of the processing device, to the analytical device, wherein the management device of the system is capable of managing the processing device or the process performed by the processing device based on the analytical results of the analytical device.

18. An analytical method for analyzing components contained in a gas using an analytical apparatus, the analytical apparatus comprising a filter for selecting components contained in the gas and allowing the components to pass through, and a detector for detecting components that have passed through the filter, the method comprising: selecting at least one of the isotopes with a lower presence ratio of the first component as a first component contained in the gas by the filter to replace the isotopes with a higher presence ratio of the first component, and detecting a first intensity by the detector; detecting a second component in the gas selected by the filter in a trace amount relative to the first component by the detector, and obtaining a second intensity; and without detecting the isotopes with a higher presence ratio of the first component, determining the mixing ratio of the second component and the first component based on the first intensity of the at least one of the isotopes with a lower presence ratio of the first component and the second intensity of the second component in a trace amount relative to the first component.

19. A control program is a control program for a monitoring system of an analytical apparatus for analyzing components contained in a gas, the analytical apparatus having a filter for selecting components contained in the gas and allowing the components to pass through, and a detector for detecting components that have passed through the filter, the control program comprising: a controller of the analytical apparatus commanding the filter to select at least one of the isotopes with a lower presence ratio of the first component as a first component contained in the gas to replace the isotopes with a higher presence ratio of the first component, and detecting a first intensity by the detector; detecting a second component in the gas selected by the filter that is present in a trace amount relative to the first component by the detector, and obtaining a second intensity; and without detecting the isotopes with a higher presence ratio of the first component, determining the mixing ratio of the second component and the first component based on the first intensity of at least one of the isotopes with a lower presence ratio of the first component and the second intensity of the second component that is present in a trace amount relative to the first component.

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