CN110376272B - On-line measuring device and method for gas partial pressure - Google Patents
On-line measuring device and method for gas partial pressure Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000002347 injection Methods 0.000 claims abstract description 32
- 239000007924 injection Substances 0.000 claims abstract description 32
- 230000006837 decompression Effects 0.000 claims abstract description 25
- 230000035945 sensitivity Effects 0.000 claims abstract description 12
- 230000003749 cleanliness Effects 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 325
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 53
- 229910052757 nitrogen Inorganic materials 0.000 claims description 26
- 238000005070 sampling Methods 0.000 claims description 25
- 238000005259 measurement Methods 0.000 claims description 21
- 238000004949 mass spectrometry Methods 0.000 claims description 12
- 238000005086 pumping Methods 0.000 claims description 12
- 230000001105 regulatory effect Effects 0.000 claims description 10
- 238000004364 calculation method Methods 0.000 claims description 8
- 238000005192 partition Methods 0.000 claims description 8
- 238000000691 measurement method Methods 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 4
- 238000007689 inspection Methods 0.000 claims description 3
- 238000012544 monitoring process Methods 0.000 claims description 3
- 230000001276 controlling effect Effects 0.000 claims description 2
- 238000001228 spectrum Methods 0.000 claims description 2
- 238000001819 mass spectrum Methods 0.000 abstract description 8
- 238000009530 blood pressure measurement Methods 0.000 abstract description 4
- 238000004868 gas analysis Methods 0.000 description 4
- 238000001900 extreme ultraviolet lithography Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000012864 cross contamination Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229910000619 316 stainless steel Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to an online measuring device and an online measuring method of gas partial pressure, wherein the online measuring device comprises a gas source cavity to be measured, a calibration gas source cavity, a decompression cavity, a constant pressure cavity, a vacuum gauge and a mass spectrum analysis module, wherein a high-pressure gas sample injection channel to be measured and a medium-pressure gas sample injection channel to be measured are arranged between a first gas inlet valve and the decompression cavity; the measuring method comprises the steps of determining standard sample gas, checking cleanliness, obtaining sensitivity of the mass spectrometer, vacuumizing to remove residual gas and measuring gas partial pressure on line. The online measuring device and the method mainly aim at the analysis of rough and low vacuum gas, select the optimal sample feeding channel according to the pressure of the gas to be measured, and have more accurate partial pressure measurement.
Description
Technical Field
The invention relates to the technical field of measurement, in particular to an online measurement device and an online measurement method for gas partial pressure.
Background
In the field of industrial production, it is often necessary to divideThe composition and concentration of the various process gases are analyzed. An extreme ultraviolet lithography machine (EUVL) vacuum system needs to carry out online tight monitoring on gas partial pressure of each vacuum microenvironment, and if the vacuum microenvironments are in a rough vacuum in starting and stopping processes, the partial pressure of each gas component needs to be monitored; in the working process (the vacuum microenvironment is low vacuum with the magnitude of several Pa), the N of the vacuum micro-environment needs to be strictly controlled2、O2、H2O and CxHyPartial pressure of the ingredients. Quadrupole mass spectrometer is the only device suitable for residual gas analysis measurement in vacuum, but it must be at 10-2The operation was carried out under Pa vacuum. Meanwhile, the characteristics of the semiconductor industry require that the extreme ultraviolet lithography machine cannot be stopped and overhauled frequently, and frequent disassembly of the quadrupole mass spectrometer for calibration is not allowed. Chinese patent CN201610168958 "an online gas analysis device and method" authorizes an online gas analysis device and method in a high pressure environment (> 2 atmospheres). The device for measuring the partial pressure of the rough and low vacuum gas has the problems of insufficient sensitivity and inaccurate measuring result.
Disclosure of Invention
The present invention is directed to solving the above problems, and provides an online measurement device and an online measurement method for partial pressure of gas.
According to one aspect of the invention, an online measuring device for gas partial pressure is provided, which comprises a gas source chamber to be measured, a calibration gas source chamber, a decompression chamber for shunting sample gas, a constant pressure chamber for keeping the pressure of the sample gas constant, a vacuum gauge and a mass spectrometry module.
The gas source cavity to be tested is controlled to be discharged through the first gas inlet valve, the calibration gas source cavity is controlled to be discharged through the sixth gas inlet valve, a high-pressure gas sample introduction channel to be tested and a medium-pressure gas sample introduction channel to be tested are arranged between the first gas inlet valve and the pressure reduction cavity, a low-pressure gas sample introduction channel to be tested is arranged between the first gas inlet valve and the pressure reduction cavity, a calibration gas sample introduction channel is arranged between the sixth gas inlet valve and the pressure reduction cavity, the high-pressure gas sample introduction channel to be tested, the medium-pressure gas sample introduction channel to be tested, the low-pressure gas sample introduction channel to be tested and the calibration gas sample introduction channel are respectively provided with a primary gas inlet valve, a gas circulation channel is arranged between the pressure reduction cavity and the pressure reduction cavity, and a secondary gas inlet valve is arranged inside the gas circulation channel.
The section between the first air inlet valve and the first air inlet valve inside each of the high-pressure gas sampling channel to be detected, the medium-pressure gas sampling channel to be detected and the low-pressure gas sampling channel to be detected is connected with a first air pump set together, the first air pump set is controlled to be communicated through a first isolating valve, the section between the sixth air inlet valve of the calibration gas sampling channel and the first air inlet valve inside the calibration gas sampling channel is connected with a third air pump set, and the third air pump set is controlled to be communicated through a second isolating valve.
The vacuum gauge is used for measuring the vacuum degrees of the gas source chamber to be measured, the calibration gas source chamber, the decompression chamber and the constant pressure chamber, and is accurately calibrated; the mass spectrometry module is used for carrying out online measurement on the sample injection gas in the constant-pressure chamber.
The constant pressure chamber comprises a cavity and a second air pump set for pumping air to the cavity, the second air pump set is communicated with the cavity through a first adjusting valve, the pressure reduction chamber comprises another cavity and a fourth air pump set for pumping air to the other cavity, and the fourth air pump set is communicated with the other cavity through a second adjusting valve.
The online measuring device further comprises a data acquisition control module, the data acquisition control module is used for controlling and opening all air pumping pump sets, a first air inlet valve, a sixth air inlet valve, all primary air inlet valves, secondary air inlet valves, a first partition valve, a second partition valve, a first adjusting valve, a second adjusting valve, a vacuum gauge and a mass spectrometry module according to requirements, and acquiring and displaying vacuum degree data and mass spectrogram data, automatically selecting and opening corresponding valves according to the vacuum degree data of the to-be-measured air source cavity, and selecting matched gas sampling channels to realize online monitoring of gas.
Wherein, flow-limiting small holes are arranged between the secondary air inlet valve of the gas circulation channel and the constant pressure chamber and between the primary air inlet valve of the low-pressure gas sample injection channel to be detected and the constant pressure chamber, and the flow-limiting small holes are of a double-hole structure with the diameter of each hole being less than 2 mm.
The mass spectrometry module comprises a quadrupole mass spectrometer and a decimal gas valve, one end of the decimal gas valve is connected with the constant pressure chamber, the outer part of the other end of the decimal gas valve is connected with a flange of the quadrupole mass spectrometer, and the inner part of the other end of the decimal gas valve is connected with a closed ion source of the quadrupole mass spectrometer through a metal thin tube.
The calibration gas sample introduction channel and the high-pressure gas sample introduction channel to be detected are mirror image channels which are symmetrical about a connecting line between the decompression chamber and the constant-pressure chamber.
The online measuring device further comprises a nitrogen filling air channel, the nitrogen filling air channel is communicated with the gas sample injection channel to be measured through an eighth air inlet valve, and the nitrogen filling air channel is communicated with the calibration gas sample injection channel through a ninth air inlet valve.
The number of the gas source chambers to be detected is one or more, and each gas source chamber to be detected is correspondingly provided with an air inlet valve control and a gas sample introduction channel to be detected.
The high-pressure gas sample injection channel to be detected and the calibration gas sample injection channel both comprise a section of the same capillary pipeline.
According to another aspect of the present invention, there is provided an online measurement method of partial pressure of gas, comprising the steps of:
s1: determining standard sample gas: concentration in gas of interest i is CiThe standard sample gas is decompressed to 1 atmosphere and is introduced into a calibration gas source chamber.
S2: and (3) cleanliness inspection: respectively carrying out vacuum pumping on the calibration gas sample introduction channel and the high, medium and low gas sample introduction channels to be detected, and carrying out cleanliness check on the calibration gas sample introduction channel and the three gas sample introduction channels to be detected by adopting a quadrupole mass spectrometer, so that the spectral peak of the gas i is ensured to be careless, and the gas source to be detected is not polluted.
S3: obtaining the sensitivity of the mass spectrometer: standard sample gas is introduced through a calibration gas sample introduction channel, and regulating valves of a decompression chamber and a constant pressure chamber are regulated to enable the vacuum degree data of the constant pressure chamber to be close to 5.0 multiplied by 10-4Pa, found is denoted as P0Recording the mass spectrogram by using a mass spectrometry module, and determining the sensitivity S of the quadrupole mass spectrometeriThe formula (A/Pa) is given by equation 1:
wherein IiThe ion current of gas i shown in the mass spectrum after the calibration gas was introduced is given as A.
S4: vacuumizing to remove residual gas: and vacuumizing the calibration gas sample introduction channel and the constant pressure chamber to ensure that no calibration gas remains.
S5: on-line measurement of gas partial pressure: recording the total pressure of the gas source chamber to be measured as P by using a vacuum gauge, selecting a matched high-pressure, medium-pressure or low-pressure gas sample introduction channel to be measured according to the total pressure of the gas source chamber to be measured, and adjusting two adjusting valves to ensure that the pressure in the constant-pressure chamber is still P0Recording the mass spectrogram at the moment by using a quadrupole mass spectrometer, and measuring the partial pressure P of the gas i in the gas source chamber to be measurediThe calculation formula is formula 2:
wherein Ii' is the ion flow of the gas i displayed in the mass spectrogram after the gas to be detected is introduced. The partial pressure of the gas other than the gas i in the gas source chamber to be measured can still be calculated by the formula 2, and the calculation result is equivalent partial pressure with respect to the gas i.
Wherein, the steps S3 and S5 include that if the calibration gas sample injection channel and the high-pressure and medium-pressure gas sample injection channels to be detected are used, the pressure of the decompression chamber needs to be adjusted to be less than 10 Pa.
Wherein, the online measurement method further comprises a step after step S5 of: closing the sample injection valve of the tested gas source chamber to be tested, and repeating the step S4; and opening the sample injection valve of the other gas source chamber to be measured, and repeating the step S5 to measure the partial pressure of the concerned gas in the other gas source chamber.
The invention has the following beneficial effects:
1) the invention relates to an on-line measuring device and an on-line measuring method for gas partial pressure, which mainly aim at gas analysis of rough vacuum and low vacuum.
2) According to the online measuring device and the online measuring method, the optimal sample feeding channel is selected according to the pressure of the gas to be measured, and the partial pressure measurement is more accurate.
3) The design of the flow-limiting double holes of the on-line measuring device avoids the selectivity of the molecules to the gas molecules under the molecular flow state, and effectively ensures the authenticity of the sampled gas.
4) The calibration gas sample injection channel and the high-pressure gas sample injection channel to be measured are completely symmetrically arranged, so that on one hand, calibration of calibration gas under the condition that the pressure of the calibration gas is equal to that of the gas to be measured can be guaranteed, and the accuracy of partial pressure measurement is effectively guaranteed; on the other hand, the sample introduction channels of the calibration gas and the gas to be detected are special, so that the cross contamination of the two gases is avoided.
5) According to the device, the metal thin tube is welded in the airflow inlet valve, and the gas in the constant-pressure chamber is directly introduced into the closed ion source of the quadrupole mass spectrometer, so that the interference of the background of the chamber is avoided, and the accuracy of partial pressure measurement is effectively ensured.
6) The device can carry out on-line calibration on the quadrupole mass spectrum, does not need to disassemble the quadrupole mass spectrum to other devices for calibration, and can further ensure the regular calibration.
7) The device can be provided with a plurality of gas source chambers to be measured, and the gas partial pressure of the other gas source chambers to be measured can be measured on line by switching the gas inlet valves without disassembling and modifying the device.
8) By adopting the online measurement and calibration method of the gas partial pressure, the accurate value of the partial pressure of the concerned gas can be continuously measured online, and the partial pressure equivalent value of other gases relative to the gas can be obtained simultaneously.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
FIG. 1 is a schematic diagram of an apparatus for on-line measurement of partial gas pressures in accordance with an embodiment of the present invention;
FIG. 2 is a schematic view of another apparatus for on-line measurement of partial gas pressure according to an embodiment of the present invention;
FIG. 3 is a flow chart of a method for on-line measurement of partial gas pressures according to an embodiment of the present invention;
fig. 4 is a graph showing the results of measuring the gas components and partial pressures of air by using an on-line measuring apparatus and an on-line measuring method for the partial pressures of gases according to the embodiment of the present invention.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below according to examples. While exemplary embodiments of the present disclosure have been shown in the specification, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
As shown in FIG. 1, the present invention provides an online measurement and calibration device for gas partial pressure, which comprises a vacuum chamber, a sample introduction channel, a nitrogen charging channel, a gas pump set, a mass spectrometry module, a valve assembly and a data acquisition control module. The vacuum chambers include 4 vacuum chambers, which are respectively a to-be-tested gas source chamber 101, a calibration gas source chamber 102, a decompression chamber and a constant pressure chamber. The sampling channel includes 4, is high pressure gas sampling channel, the gas sampling channel that the middling pressure awaited measuring and low pressure gas sampling channel and calibration gas sampling channel that awaits measuring respectively, and the passageway that fills nitrogen includes 2, is first nitrogen channel and second nitrogen channel that fills respectively. The constant pressure chamber includes cavity body 104 and a second pump stack 402 that pumps cavity body 104, and the decompression chamber includes another cavity body 103 and a fourth pump stack 404 that pumps another cavity body 103. The pump set further comprises a first pump set 401 for pumping three gas sample inlet channels to be tested, and a third pump set 403 for pumping a standard gas sample inlet channel.
Wherein, the gas source chamber 101 to be measured can pass through the high pressure gas sample introduction channel to be measured or the medium pressure gas sample introduction channel to be measured respectivelyThe gas to be measured is introduced into the decompression chamber for decompression and then enters the constant pressure chamber through the gas circulation channel, or the gas to be measured is directly introduced into the constant pressure chamber 104 through the low-pressure gas sample introduction channel to be measured, and the calibration gas source chamber 102 can introduce the calibration gas into the decompression chamber for decompression through the calibration gas sample introduction channel and then introduced into the constant pressure chamber 104. The gas source chamber 101 to be tested is uniformly controlled by the first air inlet valve 301 to be communicated with the three gas sampling channels to be tested. The high-pressure gas sample injection channel to be tested comprises a first capillary 201 and a second gas inlet valve 302, the medium-pressure gas sample injection channel to be tested is provided with a fourth gas inlet valve 304, the low-pressure gas sample injection channel to be tested is provided with a fifth gas inlet valve 305, the calibration gas sample injection channel comprises a second capillary 202 and a seventh gas inlet valve 307, and the second gas inlet valve 302, the fourth gas inlet valve 304, the fifth gas inlet valve 305 and the seventh gas inlet valve 307 are collectively called as a first-stage gas inlet valve. The gas circulation channel is internally provided with a secondary air inlet valve 303, the online measuring device is also provided with a flow-limiting small hole structure 700, and the fifth air inlet valve 305 of the low-pressure gas sample introduction channel to be measured and the secondary air inlet valve 303 of the gas circulation channel are communicated with the constant-pressure chamber through the flow-limiting small hole structure. The calibration gas sample introduction channel and the high-pressure gas sample introduction channel to be detected are symmetrically arranged, so that the sample introduction channel of the calibration gas and the sample introduction channel of the gas to be detected are respectively special, and cross contamination is avoided. By arranging three sample introduction channels suitable for the gas to be measured with different pressures, the sample introduction channels can be selected according to the total pressure of the gas to be measured, the background interference and the selectivity of gas molecules are reduced, and the accuracy and the authenticity of a measurement result are effectively ensured. Total pressure of gas to be measured is 103Pa～105When Pa is needed, a high-pressure gas sample introduction channel to be detected is selected, and the total pressure of the gas to be detected is 10 Pa-103And when the total pressure of the gas to be detected is less than 10Pa, selecting a low-pressure gas to be detected sample introduction channel.
The flow-limiting small hole structure 700 comprises two circular flow-limiting holes connected in series and used for communicating the fifth air inlet valve 305 or the secondary air inlet valve with the constant pressure chamber, the diameter of each flow-limiting hole is less than 2mm, and the gas fluid passing through each flow-limiting hole is molecular flow; the design of the flow-limiting double holes is to avoid the selectivity of gas molecules under the molecular flow and ensure the authenticity of the measuring result.
Wherein, the sample introduction channel consists of a 316 stainless steel pipe and can be electrically heated and baked to at least 100 ℃.
The first air-pump group 401 is connected with the air source chamber 101 to be tested sequentially through the first partition valve 501 and the first partition valve 301, and can be used for vacuumizing a pipeline before the second air inlet valve 302 of the high-pressure gas sample injection channel to be tested, a pipeline before the fourth air inlet valve 304 of the medium-pressure gas sample injection channel to be tested and a pipeline before the fifth air inlet valve 305 of the low-pressure gas sample injection channel to be tested, and the ultimate vacuum of the first air-pump group can reach 5 multiplied by 10-7Pa. The second pump-down set 402 is connected to the chamber body 104 of the constant pressure chamber through the first adjustment valve 601 for evacuating the chamber body 104, and the ultimate vacuum of the chamber body 104 can reach 5 × 10-8Pa; the pumping speed of the second pump-down set 402 can be controlled by adjusting the conductance of the first adjustment valve 601 so that the chamber 104 can maintain a constant pressure. The third pump-out set 403 is connected to the calibration gas chamber 102 through the second block valve 502 and the sixth block valve 306, and can be used for evacuating the pipeline before the seventh gas inlet valve 307 of the calibration gas sample channel, and the ultimate vacuum of the third pump-out set can reach 5 × 10-7Pa. The sampling channels of the high-pressure gas to be detected, the medium-pressure gas to be detected and the calibration gas intersect with each other in the decompression chamber 103, the cavity 103 of the decompression chamber is connected with a fourth air-bleed pump unit 404 for shunting the sampling gas, so that a large part of the sampling gas is pumped away through the fourth air-bleed pump unit 404, the rest small amount of gas sequentially passes through a third air-bleed valve 303 and a flow-limiting small hole 700 and enters the constant-pressure chamber 104, and the ultimate vacuum of the cavity 103 of the decompression chamber is 10-1Pa. The main pumps of the four pump sets have no obvious selectivity on the pumping speed of various gases.
The first nitrogen charging channel is charged with nitrogen through the eighth air inlet valve 308, and is used for nitrogen charging protection or nitrogen charging cleaning of a pipeline before the second air inlet valve 302 of the high-pressure gas to be detected sample channel, a pipeline before the fourth air inlet valve 304 of the medium-pressure gas to be detected sample channel and a pipeline before the fifth air inlet valve 305 of the low-pressure gas to be detected sample channel; the second nitrogen charging channel is charged with nitrogen through a ninth air inlet valve 309, and is used for nitrogen charging protection or nitrogen charging cleaning of a pipeline before a seventh air inlet valve 307 of the calibration gas sample feeding channel.
The mass spectrometry module mainly comprises an airflow inlet valve 310 on the constant pressure chamber and a quadrupole mass spectrometer 800. The quadrupole mass spectrometer 800 can be used for analyzing various gas components and measuring gas partial pressure and concentration by obtaining a mass spectrogram, and adopts a closed ion source with the mass number range of 1-200 amu; the air inlet valve 310 can be opened or closed, a metal thin tube is welded in the air inlet valve, and air flow can be directly introduced into the closed ion source of the quadrupole mass spectrometer 800. The vacuum gauge is not shown in fig. 1, and is mainly used for measuring the vacuum degrees of the gas source chamber 101 to be measured, the calibration gas source chamber 102, the decompression chamber 103 and the constant pressure chamber 104, and the vacuum gauge is accurately calibrated and obtains the correction coefficient of the vacuum gauge for various gases.
The data acquisition control module comprises start-stop control of a gas-pumping pump set, switch control of partial valves, vacuum gauge switch control and switch control of the quadrupole mass spectrometer 800, and also comprises the functions of vacuum degree data acquisition and display, mass spectrogram data acquisition and display and simple calculation; and the module can automatically open the corresponding sample introduction channel according to the vacuum degree of the gas source chamber to be measured, thereby realizing the online measurement of the gas partial pressure of the vacuum chamber.
Wherein, the pressure of the gas source chamber 101 to be measured is one atmosphere or less than one atmosphere; the gas source chambers to be tested can be multiple (such as 101, 105 and 106 in fig. 2), and the gas partial pressure of the rest gas source chambers to be tested can be measured on line by switching the gas inlet valves without changing the device.
Wherein the calibration gas source chamber 102 uses a calibration gas source having a known concentration at standard atmospheric pressure.
Another aspect of the invention provides a method for on-line measurement and calibration of gas partial pressure. As shown in fig. 3, the method specifically includes the following steps:
step S1: determining standard sample gas: concentration of gas of interest i is CiThe standard sample gas is decompressed to 1 atmosphere and is introduced into a calibration gas source chamber.
Step S2: and (3) cleanliness inspection: and vacuumizing the calibration gas source sample inlet channel and the gas source sample inlet channel to be detected, and performing cleanliness check on the sample inlet channel by using the quadrupole mass spectrometer 800 to ensure that the spectrum peak of the gas i is not concerned and the gas source to be detected is not polluted.
Step S3: obtaining the sensitivity of the mass spectrometer: the calibration gas sample introduction channel is adopted to introduce standard sample gas, and the first regulating valve 601 and the second regulating valve 602 are regulated to ensure that the display reading of a vacuum gauge on the constant pressure chamber 104 is about 5.0 multiplied by 10-4Pa, found is denoted as P0The sensitivity S of the quadrupole mass spectrometer 800 is obtained by recording the mass spectrum at the moment by the quadrupole mass spectrometer 800i(A/Pa) is calculated as follows:
Si＝Ii/(Ci·P0) (1)
wherein IiThe ion flow of gas i, shown in the mass spectrum after the calibration gas was introduced, is given in A.
Step S4: vacuumizing to remove residual gas: the calibration gas sample inlet channel and the constant pressure chamber 104 are evacuated to ensure that no calibration gas remains.
Step S5: on-line measurement of gas partial pressure: recording the total pressure of the gas source chamber 101 to be measured as P by using a vacuum gauge, selecting a corresponding sample introduction channel according to the total pressure of the gas source chamber 101 to be measured, and adjusting a first adjusting valve 601 and a second adjusting valve 602 to ensure that the pressure in the constant pressure chamber 104 is still P0Recording the mass spectrogram at the moment by using the quadrupole mass spectrometer 800, and then measuring the partial pressure P of the gas i in the gas source chamber 101iThe calculation is as follows:
Pi＝(P·Ii’)/(P0·Si)(2)
wherein Ii' is the ion flow of the gas i displayed in the mass spectrogram after the gas to be detected is introduced. The partial pressure of the gas other than the gas i in the gas source chamber 101 to be measured can still be calculated by the formula 2, and the calculation result is the equivalent partial pressure with respect to the gas i.
It should be noted that in steps S3 and S5, the second adjustment valve 602 is adjusted according to the actual sample channel, and the pressure in the decompression chamber 103 is set to be less than 10Pa, so as to ensure that the gas enters the flow restriction orifice in the molecular flow state. When the gas source chamber 101 to be measured and the constant pressure chamber 104 are recorded by using calibrated vacuum gauges, the electronic units thereof need to be set to the correction coefficients of the respective gas i to be measured.
If the partial pressure of another to-be-measured gas source chamber 105 needs to be measured online, the first sample injection valve 301 is closed, step S4 is repeated, the eleventh sample injection valve 311 is opened, and step S5 is repeated.
If the above inventive apparatus is used, when the air source chamber 101 to be measured contains air with 1 standard atmospheric pressure as the gas to be measured, the gas components and partial pressure in the air can be measured. The quadrupole mass spectrometer 800 adopts a Faraday detector, the emission current of the Faraday detector is 2000 muA, the electron energy is 102eV, the scanning speed is 500ms/amu, and the mass number range is 1-50 amu.
Step S1: and determining standard sample gas. Since the nitrogen content in the air is the largest, nitrogen with a concentration of 99.99% can be used as a standard gas, and the pressure is reduced to 1 atmosphere.
Step S2: and (5) checking the cleanliness. And vacuumizing the high-pressure gas sample introduction channel to be detected and the calibration gas sample introduction channel to reach ultimate background vacuum respectively, and performing cleanliness check by adopting a quadrupole mass spectrometer 800 respectively to ensure that no obvious nitrogen or air peak exists.
Step S3: obtaining the sensitivity of the mass spectrometer: introducing standard nitrogen with the concentration of 99.99% into a calibration gas injection channel, and adjusting a first adjusting valve 601 and a second adjusting valve 602 to enable a vacuum gauge on the constant-pressure chamber 104 to display a reading P0＝5.0×10-4Pa, recording the mass spectrogram by using the quadrupole mass spectrometer 800, and calculating the sensitivity of the quadrupole mass spectrometer 800 according to the formula 1 to obtain SN2＝1.37×10-6A/Pa, the sensitivity SN2And inputting the data into a data acquisition control module.
Step S4: vacuumizing to remove residual gas: the calibration gas sample inlet channel and the constant pressure chamber 104 are evacuated to ensure that no calibration gas remains.
Step S5: on-line measurement of gas partial pressure: the total pressure of the air in the source chamber 101 to be measured was recorded by a vacuum gauge as 1.0 × 105And Pa, inputting the total pressure data into the data acquisition control module. Selecting a high-pressure gas sample introduction channel to be detected, and finely adjusting the first regulating valve 601 to make the pressure in the constant pressure chamber 104 still be P0＝5.0×10-4Pa, the mass spectrum at that time is recorded by the quadrupole mass spectrometer 800, as shown in fig. 4.
As can be seen from FIG. 4, the main gas component in the air has N in turn2(28amu)、O2(32amu)、H2O (18amu) and Ar (40 amu). Wherein the accurate measurement of the partial pressure of nitrogen is calculated as P according to equation 2N2＝7.90×104Pa. The calculation is still carried out by using the formula 2, and the calculated value is substituted into the gas of interest (N) displayed by the mass spectrum in the step 52External) ion current Ii' and the sensitivity S of the mass spectrometer to nitrogen calculated in step 3N2＝1.37×10-6A/Pa, then: equivalent partial pressure value P of oxygen relative to nitrogenO2＝1.90×104Pa, equivalent partial pressure value P of water gas relative to nitrogen gasH2O＝1.4×104Pa, equivalent partial pressure value P of argon gas relative to nitrogen gasAr＝1.7×104Pa。
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. The on-line measuring device for the gas partial pressure is characterized by comprising a gas source chamber (101) to be measured, a calibration gas source chamber (102), a decompression chamber for shunting the sample gas, a constant pressure chamber for keeping the pressure of the sample gas constant, a vacuum gauge and a mass spectrometry module;
wherein the gas source chamber (101) to be tested controls gas outlet through a first gas inlet valve (301), the calibrated gas source chamber (102) is controlled to vent gas through a sixth gas inlet valve (306), a high-pressure gas sample injection channel to be detected and a medium-pressure gas sample injection channel to be detected are arranged between the first air inlet valve (301) and the decompression chamber, a low-pressure gas sample introduction channel to be detected is arranged between the first air inlet valve (301) and the constant pressure chamber, a calibration gas sample inlet channel is arranged between the sixth gas inlet valve (306) and the decompression chamber, the high-pressure gas sample injection channel to be tested, the medium-pressure gas sample injection channel to be tested, the low-pressure gas sample injection channel to be tested and the calibration gas sample injection channel are respectively provided with a primary air inlet valve (302,304,305,307), a gas circulation channel is arranged between the pressure reduction chamber and the constant pressure chamber, and a secondary air inlet valve (303) is arranged in the gas circulation channel;
the section among the first-stage air inlet valves and the first air inlet valves (301) in the high-pressure gas sampling channel to be detected, the medium-pressure gas sampling channel to be detected and the low-pressure gas sampling channel to be detected is connected with a first air pump set (401) together, the first air pump set (401) is controlled to be communicated through a first partition valve (501), the section between a sixth air inlet valve (306) of the calibration gas sampling channel and the first-stage air inlet valve in the calibration gas sampling channel is connected with a third air pump set (403), and the third air pump set (403) is controlled to be communicated through a second partition valve (502);
the vacuum gauge is used for measuring the vacuum degrees of the gas source chamber (101) to be measured, the calibration gas source chamber (102), the decompression chamber and the constant pressure chamber, and is accurately calibrated; the mass spectrometry module is used for carrying out online measurement on the sample gas in the constant-pressure chamber.
2. The on-line measuring device of claim 1,
the constant-pressure chamber comprises a cavity body (104) and a second pump set (402) for pumping the cavity body (104), the second pump set (402) is communicated with the cavity body (104) through a first regulating valve (601), the pressure reduction chamber comprises another cavity body (103) and a fourth pump set (404) for pumping the other cavity body (103), and the fourth pump set (404) is communicated with the other cavity body (103) in a control mode through a second regulating valve (602).
3. The on-line measuring device of claim 2,
the online measurement device further comprises a data acquisition control module, wherein the data acquisition control module is used for controlling and opening all the air pumping pump sets according to requirements, the first air inlet valve, the sixth air inlet valve, all the first-stage air inlet valve (302,304,305,307), the second-stage air inlet valve (303), the first partition valve (501), the second partition valve (502), the first adjusting valve (601), the second adjusting valve (602), the vacuum gauge and the mass spectrometry module, and acquiring and displaying vacuum degree data and mass spectrogram data, automatically selecting and opening corresponding valves according to the vacuum degree data of the air source cavity to be detected, selecting matched gas sample introduction channels, and realizing online monitoring of gas.
4. The on-line measuring device of claim 1,
the one-level air inlet valve of the low-pressure gas sampling channel to be tested and the constant-pressure chamber and the two-level air inlet valve of the gas circulation channel and the constant-pressure chamber are both provided with flow limiting holes, and the diameter of each flow limiting hole is less than 2 mm.
5. The on-line measuring device of claim 1,
the mass spectrometry module comprises a quadrupole mass spectrometer (800) and a decimal gas valve (310), one end of the decimal gas valve (310) is connected with the constant pressure chamber, and the inside of the other end of the decimal gas valve is connected with a closed ion source of the quadrupole mass spectrometer (800) through a metal thin tube.
6. The on-line measuring device of claim 1,
the calibration gas sampling channel and the high-pressure gas sampling channel to be detected are mirror image channels which are symmetrical about a connecting line between the decompression chamber and the constant-pressure chamber.
7. The on-line measuring device of claim 1,
the on-line measuring device further comprises a nitrogen charging air passage, the nitrogen charging air passage is communicated with a gas sampling passage to be measured through an eighth air inlet valve (308), and the nitrogen charging air passage is communicated with a calibration gas sampling passage through a ninth air inlet valve (309).
8. The on-line measuring device of claim 1,
the high-pressure gas sample introduction channel to be detected and the calibration gas sample introduction channel both comprise a section of the same capillary pipeline.
9. An on-line measurement method of a gas partial pressure for use in the on-line measurement apparatus of any one of claims 1 to 8, characterized by comprising the steps of:
s1: determining standard sample gas: concentration in gas of interest i is CiThe standard sample gas is decompressed to 1 atmosphere and is introduced into a calibration gas source chamber;
s2: and (3) cleanliness inspection: respectively vacuumizing a calibration gas sample introduction channel and high, medium and low to-be-detected gas sample introduction channels, and performing cleanliness check on the three to-be-detected gas sample introduction channels and the calibration gas sample introduction channel by adopting a quadrupole mass spectrometer to ensure that a spectrum peak of gas i is not concerned and the gas source to be detected is not polluted;
s3: obtaining the sensitivity of the mass spectrometer: standard sample gas is introduced through a calibration gas sample introduction channel, and regulating valves of a decompression chamber and a constant pressure chamber are regulated to enable the vacuum degree data of the constant pressure chamber to be close to 5.0 multiplied by 10-4Pa, found is denoted as P0Recording the mass spectrogram by using a mass spectrometry module, and determining the sensitivity S of the quadrupole mass spectrometeriThe formula (A/Pa) is given by equation 1:
wherein IiThe ion current of the gas i shown in the mass spectrogram after the calibration gas is introduced is A;
s4: vacuumizing to remove residual gas: vacuumizing the calibration gas sample introduction channel and the constant pressure chamber to ensure that no calibration gas remains;
s5: on-line measurement of gas partial pressure:recording the total pressure of the gas source chamber to be measured as P by using a vacuum gauge, selecting a matched high-pressure, medium-pressure or low-pressure gas sample introduction channel to be measured according to the total pressure of the gas source chamber to be measured, and adjusting two adjusting valves to ensure that the pressure in the constant-pressure chamber is still P0Recording the mass spectrogram at the moment by using a quadrupole mass spectrometer, and measuring the partial pressure P of the gas i in the gas source chamber to be measurediThe calculation formula is formula 2:
wherein Ii' is the ion current of the gas i displayed in the mass spectrogram after the gas to be detected is introduced, the partial pressure of the gas except the gas i in the gas source chamber to be detected can still be calculated by the formula 2, and the calculation result is the equivalent partial pressure relative to the gas i.
10. The on-line measuring method according to claim 9,
in steps S3 and S5, if the calibration gas injection channel and the high-pressure and medium-pressure gas injection channels to be tested are used, the pressure of the decompression chamber needs to be adjusted to be less than 10 Pa.
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