CN113125372B - Impurity gas detection device and method for electronic grade boron trichloride purification system - Google Patents
Impurity gas detection device and method for electronic grade boron trichloride purification system Download PDFInfo
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- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 238000001514 detection method Methods 0.000 title claims abstract description 80
- 239000012535 impurity Substances 0.000 title claims abstract description 56
- 238000000746 purification Methods 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title abstract description 9
- 238000002329 infrared spectrum Methods 0.000 claims abstract description 53
- 239000000047 product Substances 0.000 claims abstract description 45
- 239000003513 alkali Substances 0.000 claims abstract description 30
- 239000012043 crude product Substances 0.000 claims abstract description 25
- 238000003860 storage Methods 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims description 96
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 claims description 33
- 239000001307 helium Substances 0.000 claims description 24
- 229910052734 helium Inorganic materials 0.000 claims description 24
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 24
- 230000003287 optical effect Effects 0.000 claims description 16
- 238000010521 absorption reaction Methods 0.000 claims description 15
- 238000005259 measurement Methods 0.000 claims description 15
- 238000001228 spectrum Methods 0.000 claims description 13
- 229910016036 BaF 2 Inorganic materials 0.000 claims description 10
- 238000004445 quantitative analysis Methods 0.000 claims description 8
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 7
- 229910003910 SiCl4 Inorganic materials 0.000 claims description 7
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims description 7
- 229910003818 SiH2Cl2 Inorganic materials 0.000 claims description 6
- 230000005855 radiation Effects 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- 238000000411 transmission spectrum Methods 0.000 claims description 4
- 238000000862 absorption spectrum Methods 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 claims description 2
- 238000012886 linear function Methods 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- 230000003595 spectral effect Effects 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 13
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 13
- 230000009102 absorption Effects 0.000 description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 8
- 239000004327 boric acid Substances 0.000 description 8
- 238000011084 recovery Methods 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000011897 real-time detection Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3504—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing gases, e.g. multi-gas analysis
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/06—Boron halogen compounds
- C01B35/061—Halides
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
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Abstract
The invention discloses an impurity gas detection device and method of an electronic grade boron trichloride purification system, comprising a crude product storage tank, a first pipeline, a second pipeline, a first Fourier infrared spectrum detection system, a first buffer tank, a first vacuum pump, a boron trichloride purification system, a third pipeline, a second Fourier infrared spectrum detection system, a second buffer tank, a second vacuum pump and an alkali liquor cylinder. The first Fourier infrared spectrum detection system can detect impurity gas in the crude boron trichloride, the second Fourier infrared spectrum detection system can detect impurity gas in an electronic grade boron trichloride finished product generated by the boron trichloride purification system, the two systems can work simultaneously, the simultaneous detection of the impurity gas in the crude boron trichloride and the finished product is realized, and the detected crude boron trichloride and the detected finished product can be neutralized and absorbed by the alkali liquor tube.
Description
Technical Field
The invention relates to the technical field of special gas detection, in particular to an impurity gas detection device and method of an electronic grade boron trichloride purification system.
Background
Boron trichloride is a gas or colorless fuming liquid, and has a pungent odor. The electronic grade boron trichloride is mainly used in the technical field of IC, OLED, LED and other semiconductors, and is a high-purity semiconductor material with excellent performance. Boron trichloride is taken as a basic material with high consumption and high purity requirement in the fields of integrated circuits and electronic devices, is a product and industry which are emphasized and encouraged to develop in China, and accords with the national medium-and-long-term technological development planning (2021-2035) and the 'fourteen-five' technological innovation planning.
With the technical progress of integrated circuits, the technology nodes reach 7 nanometers, the wafer manufacturing reaches 12 inches, the purity requirement on the electronic grade boron trichloride is higher and higher, the corresponding requirement on the detection of impurity gas in the electronic grade boron trichloride is also provided, and no mature detection technology exists in the related field in China at present, and the method is subject to people. CH 4、CO、CO2、HCl、COCl2、SiCl4 and SiH 2Cl2 in boron trichloride impurity gas have obvious infrared fingerprint characteristic absorption, and patent CN108821302A discloses a purification method and device of boron trichloride, comprising a decomposition section, a rectification section, a storage and filling section and a recovery section, wherein the recovery section is as follows: the device is provided with a recovery tank, the recovery tank can collect waste gas discharged from the rectification section, the bottom of the recovery tank is provided with a three-way pipe, one discharge port of the three-way pipe is communicated with a waste gas treatment tower, and the waste gas treatment tower comprises an alkaline washing section and a water washing section which are arranged in series; during the continuous collection process of the recovery tank, some gas impurities including a small amount of CO, cl 2, N 2 and the like are gradually enriched at the bottom and the top of the recovery tank respectively, and then the gas impurities are discharged periodically. The problems with this technique are as follows: only the heavy component and the light component discharged from the rectification section are recovered, and the real-time detection of impurity gas in the crude boron trichloride product and the finished product cannot be realized.
Disclosure of Invention
The invention aims to solve the technical problem that the existing boron trichloride purification system cannot realize real-time detection of impurity gases in crude boron trichloride products and finished products.
In order to solve the technical problems, the invention provides the following technical scheme: an impurity gas detection device of an electronic grade boron trichloride purification system comprises a crude product storage tank, a first pipeline, a second pipeline, a first Fourier infrared spectrum detection system, a first buffer tank, a first vacuum pump, a boron trichloride purification system, a third pipeline, a second Fourier infrared spectrum detection system, a second buffer tank, a second vacuum pump and an alkali liquor barrel; the first pipeline and the second pipeline are arranged in parallel, and the inlet of the first pipeline and the inlet of the second pipeline are communicated with the discharge port of the crude product storage tank through a three-way valve; the first Fourier infrared spectrum detection system comprises a first sample tank, wherein a feed inlet of the first sample tank is communicated with an outlet of a first pipeline, a feed inlet of the first buffer tank is communicated with a discharge outlet of the first sample tank, a feed inlet of the first vacuum pump is communicated with a discharge outlet of the first buffer tank, and a discharge outlet of the first vacuum pump is communicated into the alkali liquor barrel; the feed inlet of the boron trichloride purification system is communicated with the outlet of the second pipeline; the inlet of the third pipeline is communicated with the discharge port of the boron trichloride purification system; the second Fourier infrared spectrum detection system comprises a second sample tank, a feed inlet of the second sample tank is communicated with an outlet of the third pipeline, a feed inlet of the second buffer tank is communicated with a discharge outlet of the second sample tank, a feed inlet of the second vacuum pump is communicated with a discharge outlet of the second buffer tank, and a discharge outlet of the second vacuum pump is communicated into the alkali liquor barrel;
The optical path length of the first sample cell is 60mm, and the optical path length of the second sample cell is 10m.
According to the invention, through the arrangement of the first Fourier infrared spectrum detection system and the second Fourier infrared spectrum detection system, the first Fourier infrared spectrum detection system can detect the impurity gas of the crude boron trichloride, the second Fourier infrared spectrum detection system can detect the impurity gas in the electronic grade boron trichloride finished product generated by the boron trichloride purification system, the two systems can work simultaneously, the simultaneous detection of the impurity gas in the crude boron trichloride and the finished product is realized, and the alkaline liquid cylinder can be used for neutralizing and absorbing the crude boron trichloride and the finished product simultaneously.
Because the concentration of impurity gas in the boron trichloride crude product is higher, the infrared fingerprint characteristic absorption is stronger, therefore, the optical path of the first sample cell is designed to be 60mm, the concentration of impurity gas in the electronic grade boron trichloride finished product is lower, and the infrared fingerprint characteristic absorption is weaker, therefore, the optical path of the second sample cell is designed to be 10m.
Preferably, the window sheets on the left and right sides of the first sample cell and the window sheets on the left and right sides of the second sample cell are BaF 2 window sheets; the window sheets on the left side and the right side of the first sample cell and the window sheets on the left side and the right side of the second sample cell are designed to be BaF 2 window sheets, and the BaF 2 window sheets do not react with boron trichloride to avoid corrosion.
Preferably, temperature and pressure control systems are arranged in the first sample cell and the second sample cell, the temperature of gas in the first sample cell and the temperature of gas in the second sample cell are both constant at 42+/-0.2 ℃, and the pressure of gas in the first sample cell and the second sample cell is both constant at 1+/-0.1 standard atmospheric pressure.
Preferably, the first fourier infrared spectrum detection system further comprises a first detector, a first FTIR spectrometer, a first infrared light source, and first control analysis software; the first detector is arranged at one side of the first sample cell; the first FTIR spectrometer is arranged on the other side of the first sample cell; the first infrared light source is arranged on the other side of the first FTIR spectrometer; the first control analysis software is electrically connected with the first detector, the first FTIR spectrometer and the first infrared light source.
Preferably, the first Fourier infrared spectrum detection system detects impurity gas components and concentration ranges ：CH4：100-200ppm、CO：100-150ppm、CO2：100-200ppm,HCl：100-300ppm、COCl2：1-200ppm、SiCl4：100-300ppm、SiH2Cl2：1-200ppm.
Preferably, the second fourier infrared spectrum detection system further comprises a second detector, a second FTIR spectrometer, a second infrared light source, and second control analysis software; the second detector is arranged at one side of the second sample cell; the second FTIR spectrometer is arranged on the other side of the second sample cell; the second infrared light source is arranged on the other side of the second FTIR spectrometer; the second control analysis software is electrically connected with the second detector, the second FTIR spectrometer and the second infrared light source.
Preferably, the second Fourier infrared spectrum detection system detects impurity gas components and concentration ranges ：CH4：0.01-0.5ppm、CO：0.1-0.5ppm、CO2：0.1-2ppm、HCl：0.1-1ppm、COCl2：0.1-1ppm、SiCl4：0.05-2ppm、SiH2Cl2：0.1-1ppm.
Preferably, the device also comprises a helium tank, wherein an air outlet of the helium tank is respectively communicated with the first pipeline and the third pipeline through a three-way valve to form an air path system, and the air path system is constant at 42+/-0.2 ℃ for heat tracing; the boron trichloride is easy to hydrolyze when meeting water, hydrogen chloride and boric acid are generated, the hydrogen chloride is extremely strong in corrosiveness and easy to corrode various parts on the instrument, and the boric acid is extremely easy to block pipelines, so that a helium tank is designed to be respectively communicated with the first pipeline and the third pipeline through three-way valves to form an air path system, and the whole air path system is purged by high-purity helium; in order to prevent boron trichloride from being adsorbed, the whole gas path system is constant at 42+/-0.2 ℃ with heat.
Preferably, the first pipeline and the third pipeline are provided with a pressure reducing valve and a flowmeter.
The invention also discloses a detection method of the impurity gas detection device of the electronic grade boron trichloride purification system, which comprises the following steps: starting a first vacuum pump, filling a part of crude boron trichloride in a crude product storage tank into a first sample pool of a first Fourier infrared spectrum detection system through a first pipeline, detecting and analyzing, and then introducing the crude boron trichloride into an alkali liquor cylinder after passing through an outlet of the first sample pool and a first buffer tank, wherein the alkali liquor cylinder neutralizes the detected crude boron trichloride; starting a second vacuum pump, introducing the other part of the crude boron trichloride in the crude product storage tank into a boron trichloride purification system through a second pipeline to generate a high-purity electronic grade boron trichloride finished product, filling the electronic grade boron trichloride finished product into a second sample cell of a second Fourier infrared spectrum detection system through a third pipeline, introducing the electronic grade boron trichloride finished product into an alkali liquor cylinder after passing through an outlet of the second sample cell and a second buffer tank, and neutralizing the detected electronic grade boron trichloride finished product by the alkali liquor cylinder; or simultaneously starting the first vacuum pump and the second vacuum pump to realize the simultaneous detection of impurity gases in the crude boron trichloride product and the finished product, and simultaneously neutralizing the detected crude boron trichloride product and the detected finished product by the alkali liquor cylinder.
Compared with the prior art, the invention has the beneficial effects that:
1. According to the invention, through the arrangement of the first Fourier infrared spectrum detection system and the second Fourier infrared spectrum detection system, the first Fourier infrared spectrum detection system can detect impurity gas in the crude boron trichloride, the second Fourier infrared spectrum detection system can detect impurity gas in the electronic grade boron trichloride finished product generated by the boron trichloride purification system, the two systems can work simultaneously, so that the simultaneous detection of the impurity gas in the crude boron trichloride and the finished product is realized, and the detected crude boron trichloride and the detected finished product can be neutralized and absorbed by the alkali liquor barrel.
2. Because the concentration of impurity gas in the boron trichloride crude product is higher, the infrared fingerprint characteristic absorption is stronger, therefore, the optical path of the first sample cell is designed to be 60mm, the concentration of impurity gas in the electronic grade boron trichloride finished product is lower, and the infrared fingerprint characteristic absorption is weaker, therefore, the optical path of the second sample cell is designed to be 10m.
3. According to the invention, the window sheets on the left and right sides of the first sample cell and the window sheets on the left and right sides of the second sample cell are designed to be BaF 2 window sheets, and the BaF 2 window sheets do not react with boron trichloride to avoid corrosion.
4. The boron trichloride is easy to hydrolyze when meeting water, hydrogen chloride and boric acid are generated, the hydrogen chloride is extremely strong in corrosiveness and easy to corrode various parts on an instrument, and the boric acid is extremely easy to block pipelines, so that the helium tank is designed and is respectively communicated with the first pipeline and the third pipeline through the three-way valve to form an air path system, and the whole air path system is purged by high-purity helium; in order to prevent boron trichloride from being adsorbed, the whole gas path system is constant at 42+/-0.2 ℃ with heat.
Drawings
FIG. 1 is a schematic diagram of an impurity gas detection device of an electronic grade boron trichloride purification system;
FIG. 2 is a chart showing an infrared absorption standard spectrum of an impurity gas according to an embodiment of the present invention.
Reference numerals illustrate:
1. A crude product storage tank; 2. a first pipeline; 3. a second pipeline; 4. a first fourier infrared spectrum detection system; 401. a first sample cell; 402. a first detector; 403. a first FTIR spectrometer; 404. a first infrared light source; 405. first control analysis software; 5. a first buffer tank; 6. a first vacuum pump; 7. a boron trichloride purification system; 8. a third pipeline; 9. a second fourier infrared spectrum detection system; 901. a second sample cell; 902. a second detector; 903. a second FTIR spectrometer; 904. a second infrared light source; 905. second control analysis software; 10. a second buffer tank; 11. a second vacuum pump; 12. an alkali liquor cylinder; 13. helium tanks.
Detailed Description
In order to facilitate the understanding of the technical scheme of the present invention by those skilled in the art, the technical scheme of the present invention will be further described with reference to the accompanying drawings.
The terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present application, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
Example 1
As shown in fig. 1, the embodiment discloses an impurity gas detection device of an electronic grade boron trichloride purification system, which comprises a crude product storage tank 1, a first pipeline 2, a second pipeline 3, a first fourier infrared spectrum detection system 4, a first buffer tank 5, a first vacuum pump 6, a boron trichloride purification system 7, a third pipeline 8, a second fourier infrared spectrum detection system 9, a second buffer tank 10, a second vacuum pump 11, an alkali liquor barrel 12 and a helium tank 13.
As shown in fig. 1, a crude boron trichloride crude product is stored in a crude product storage tank 1 in the embodiment, a discharge port of the crude product storage tank 1 is respectively communicated with an inlet of a first pipeline 2 and an inlet of a second pipeline 3 through a three-way valve, a feed port of the three-way valve is connected with a discharge port of the crude product storage tank 1 through a pipeline, one port of the pipeline is fixedly welded and communicated with the discharge port of the crude product storage tank 1, and the other port of the pipeline is fixedly welded and communicated with the feed port of the three-way valve; one of the discharge ports of the three-way valve is fixedly welded and communicated with the inlet of the first pipeline 2, and the other discharge port of the three-way valve is fixedly welded and communicated with the inlet of the second pipeline 3; the first pipeline 2 and the second pipeline 3 of the embodiment are both provided with electromagnetic valves, and the first pipeline 2 is also provided with a pressure reducing valve and a flowmeter.
As shown in fig. 1, and specifically referring to the orientation of fig. 1, the first fourier infrared spectrum detection system 4 includes a first sample cell 401, a first detector 402, a first FTIR spectrometer 403, a first infrared light source 404, and first control analysis software 405;
The feed inlet of the first sample pool 401 is welded and fixed with and communicated with the outlet of the first pipeline 2; the first detector 402 is mounted on the left side of the first sample cell 401; a first FTIR spectrometer 403 is fitted to the right of the first sample cell 401; the first infrared light source 404 is mounted to the right of the first FTIR spectrometer 403; the first control analysis software 405 is electrically connected to the first detector 402, the first FTIR spectrometer 403, the first infrared light source 404;
as shown in FIG. 1, the optical path of the first sample cell 401 in this embodiment is 60mm, the window sheets on the left and right sides of the first sample cell 401 are BaF 2 window sheets, a temperature and pressure control system is also installed in the first sample cell 401 in this embodiment, the gas temperature in the first sample cell 401 is constant at 42+ -0.2 ℃, the gas pressure is constant at 1+ -0.1 standard atmosphere, and the detected impurity gas components and concentration ranges are ：CH4：100-200ppm、CO：100-150ppm、CO2：100-200ppm,HCl：100-300ppm、COCl2：1-200ppm、SiCl4：100-300ppm、SiH2Cl2：1-200ppm.
As shown in fig. 1, the feed inlet of the first buffer tank 5 is communicated with the discharge outlet of the first sample tank 401 through a pipeline, two ends of the pipeline are respectively welded and fixed with and communicated with the feed inlet of the first buffer tank 5 and the discharge outlet of the first sample tank 401, and an electromagnetic valve is further arranged on the pipeline.
As shown in fig. 1, the feed inlet of the first vacuum pump 6 is communicated with the discharge outlet of the first buffer tank 5 through a pipeline, the pipeline and two ends are respectively welded and fixed with the feed inlet of the first vacuum pump 6 and the discharge outlet of the first buffer tank 5 and are communicated with each other, an electromagnetic valve is assembled on the pipeline, the discharge outlet of the first vacuum pump 6 is communicated into the alkali liquor barrel 12 through a pipeline, one port of the pipeline is welded and fixed with the discharge outlet of the first vacuum pump 6 and is communicated with each other, and the other port of the pipeline directly extends into the alkali liquor of the alkali liquor barrel 12.
As shown in fig. 1, the feed port of the boron trichloride purification system 7 of the present embodiment is welded and fixed to and in communication with the discharge port of the second pipe 3.
As shown in fig. 1, and specifically referring to the orientation of fig. 1, the second fourier infrared spectrum detection system 9 includes a second sample cell 901, a second detector 902, a second FTIR spectrometer 903, a second infrared light source 904, and second control analysis software 905;
The feed inlet of the second sample tank 901 is communicated with the discharge outlet of the boron trichloride purification system 7 through a third pipeline 8, one port of the third pipeline 8 is welded and fixed with and communicated with the feed inlet of the second sample tank 901, the other port of the third pipeline 8 is welded and fixed with and communicated with the feed inlet of the second sample tank 901, and the third pipeline 8 of the embodiment is further provided with a pressure reducing valve and a flowmeter; the second detector 902 is mounted on the left side of the second sample cell 901; a second FTIR spectrometer 903 is fitted to the right of the second sample cell 901; a second infrared light source 904 is mounted to the right of the second FTIR spectrometer 903; the second control analysis software 905 is electrically connected to the second detector 902, the second FTIR spectrometer 903, the second infrared light source 904;
As shown in fig. 1, the optical path of the second sample cell 901 in this embodiment is 10m, the window sheets on the left and right sides of the second sample cell 901 are BaF 2 window sheets, a temperature and pressure control system is arranged in the second sample cell 901, the gas temperature in the second sample cell 901 is constant at 42±0.2 ℃, the gas pressure is constant at 1±0.1 standard atmospheric pressure, and the detected impurity gas components and concentration ranges are ：CH4：0.01-0.5ppm、CO：0.1-0.5ppm、CO2：0.1-2ppm、HCl：0.1-1ppm、COCl2：0.1-1ppm、SiCl4：0.05-2ppm、SiH2Cl2：0.1-1ppm.
As shown in fig. 1, the feeding port of the second buffer tank 10 is communicated with the discharging port of the second sample tank 901 through a pipeline, two ports of the pipeline are respectively welded and fixed with and communicated with the feeding port of the second buffer tank 10 and the discharging port of the second sample tank 901, and an electromagnetic valve is further arranged on the pipeline.
As shown in fig. 1, the feeding port of the second vacuum pump 11 is communicated with the discharging port of the second buffer tank 10 through a pipeline, the pipeline and two ends are respectively welded and fixed with and communicated with the feeding port of the second vacuum pump 11 and the discharging port of the second buffer tank 10, an electromagnetic valve is assembled on the pipeline, the discharging port of the second vacuum pump 11 is communicated into the alkali liquor barrel 12 through a pipeline, one port of the pipeline is welded and fixed with and communicated with the discharging port of the second vacuum pump 11, and the other port of the pipeline directly extends into the alkali liquor of the alkali liquor barrel 12.
As shown in fig. 1, the air outlet of the helium tank 13 is respectively communicated with the first pipeline 2 and the third pipeline 8 through a three-way valve to form an air path system, the air inlet of the three-way valve is connected with the air outlet of the helium tank 13 through a pipeline, two ports of the pipeline are respectively welded and fixed with the air outlet of the helium tank 13 and the air inlet of the three-way valve, one air outlet of the three-way valve is communicated with the interior of the first pipeline 2 through a pipeline, the other air outlet of the three-way valve is communicated with the interior of the third pipeline 8 through a pipeline, and electromagnetic valves are assembled on the two pipelines; the constant 42+/-0.2 ℃ heat tracing of the gas circuit system is realized, as boron trichloride is extremely easy to hydrolyze when meeting water, hydrogen chloride and boric acid are generated, the hydrogen chloride is extremely strong in corrosiveness and is easy to corrode various parts on an instrument, and the boric acid is extremely easy to block pipelines, so that the helium tank 13 is respectively communicated with the first pipeline 2 and the third pipeline 8 through a three-way valve to form the gas circuit system, the whole gas circuit system is purged by high-purity helium, and the constant 42+/-0.2 ℃ heat tracing of the gas circuit system is used for preventing boron trichloride from being adsorbed.
The invention also discloses a method of the impurity gas detection device of the electronic grade boron trichloride purification system, which comprises the following steps: starting the first vacuum pump 6 and the second vacuum pump 11 respectively, and vacuumizing the two gas paths by the first vacuum pump 6 and the second vacuum pump 11; controlling a part of boron trichloride crude product in a crude product storage tank 1 through a flowmeter on a first pipeline 2, filling the boron trichloride crude product into a first sample tank 401 of a first Fourier infrared spectrum detection system 4 through the first pipeline 2, detecting and analyzing, ensuring that the temperature and pressure of the gas filled into the first sample tank 401 are constant through temperature control and pressure control after the boron trichloride crude product is detected and analyzed, further improving the measurement accuracy, starting a first vacuum pump 6 again to pump the measurement gas into an alkali liquor cylinder 12 and drop the measurement gas after the measurement is finished, opening an electromagnetic valve on a helium tank 13 and a passage of the first pipeline 2, introducing high-purity helium gas into a gas circuit system for purging, and then flushing the gas circuit and the first sample tank 401 with the high-purity helium gas to prevent gas adsorption; similarly, another part of the boron trichloride crude product in the crude product storage tank 1 is introduced into the boron trichloride purification system 7 through the second pipeline 3, so that a high-purity electronic grade boron trichloride finished product is generated, the electronic grade boron trichloride finished product is controlled by a flowmeter on the third pipeline 8 to be filled into a second sample tank 901 of the second Fourier infrared spectrum detection system 9 through the third pipeline 8, after detection and analysis, the electronic grade boron trichloride finished product is ensured to be filled into the second sample tank 901 to be constant in temperature and pressure through the outlet of the second sample tank 901 by temperature control and pressure control, the measurement accuracy is further improved, after measurement is finished, the second vacuum pump 11 is started again to pump the measurement gas into the alkali liquor barrel 12 for neutralization, after the measurement is finished, the electromagnetic valve on the passage of the helium tank 13 and the third pipeline 8 is opened, the high-purity helium gas is introduced into the gas circuit system for purging, and then the gas circuit and the second sample tank 901 are flushed by the high-purity helium gas, so that gas adsorption is prevented from being formed.
The principle of measurement and analysis of the crude boron trichloride product and the electronic grade boron trichloride finished product in the first Fourier infrared spectrum detection system 4 and the second Fourier infrared spectrum detection system 9 respectively is as follows:
taking the detection and analysis of impurity gas of crude boron trichloride as an example.
1. Spectral measurement:
(1) Charging the crude boron trichloride into a first sample cell 401 with multiple reflections;
(2) The first infrared light source 404 is collimated by the optical system and then led into the first FTIR spectrometer 403, and the infrared radiation signal is led into the multi-reflection first sample cell 401 after being subjected to interference modulation by the first FTIR spectrometer 403;
(3) The infrared radiation signals which are led out from the first sample pool 401 and are subjected to interference modulation carry the absorption information of the sample to be detected and are converged on the first detector 402;
(4) The first control analysis software 405 converts the interferogram obtained by the first detector 402 into a spectrogram, thereby obtaining an absorption spectrum of the infrared absorption feature of the contaminant gas to be detected.
2. Quantitative analysis
(1) And (3) establishing a characteristic spectrum database: a database of characteristic spectra of gases (impurity gases to be measured) adapted to the measurement parameters of the FTIR device is established (different gases have different infrared characteristic absorptions, which are given in fig. 2). And establishing an infrared spectrum database which accords with the measurement parameters (spectrum resolution, field angle and apodization function) of the developed equipment and can correct the temperature and the air pressure by utilizing a high-resolution infrared spectrum database, and performing quantitative analysis.
(2) Multicomponent quantitative analysis algorithm based on synthetic calibration spectrum: extracting absorption line parameters of target gas by using the established infrared spectrum database; by correcting the ambient temperature and the air pressure, inputting the optical path length, the preset gas components and the preset concentration, generating an atmospheric transmittance spectrum in an ideal state according to a single-layer atmospheric radiation transmission model, and convolving the atmospheric transmittance spectrum with an instrument linear function ILS of measuring equipment to generate a quantitative analysis calibration spectrum.
(3) And (3) applying a nonlinear least square fitting quantitative inversion algorithm to perform repeated iterative fitting on the synthesized calibration spectrum and the measured spectrum to obtain the optimal value of the concentration of the gas to be measured.
Compared with the prior art, the invention has the following advantages: according to the invention, through the arrangement of the first Fourier infrared spectrum detection system 4 and the second Fourier infrared spectrum detection system 9, the first Fourier infrared spectrum detection system 4 can detect impurity gas in the crude boron trichloride, the second Fourier infrared spectrum detection system 9 can detect impurity gas in an electronic grade boron trichloride finished product generated by the boron trichloride purification system 7, the two systems can work simultaneously, so that the simultaneous detection of the impurity gas in the crude boron trichloride and the finished product is realized, and the alkali liquor barrel 12 can be utilized to neutralize and absorb the impurity gas in the crude boron trichloride and the finished product; secondly, as the concentration of the impurity gas in the boron trichloride crude product is higher, the infrared fingerprint characteristic absorption is stronger, the optical path of the first sample cell 401 is designed to be 60mm, the concentration of the impurity gas in the electronic grade boron trichloride finished product is lower, and the infrared fingerprint characteristic absorption is weaker, so the optical path of the second sample cell 901 is designed to be 10m; thirdly, the window sheets on the left and right sides of the first sample cell 401 and the window sheets on the left and right sides of the second sample cell 901 are designed to be BaF 2 window sheets, and the BaF 2 window sheets do not react with boron trichloride to avoid corrosion; fourthly, as boron trichloride is extremely easy to hydrolyze when meeting water, hydrogen chloride and boric acid are generated, the hydrogen chloride is extremely strong in corrosiveness and is easy to corrode various parts on an instrument, and the boric acid is extremely easy to block pipelines, the invention designs the helium tank 13, and the helium tank 13 is respectively communicated with the first pipeline 2 and the third pipeline 8 through the three-way valve to form a gas circuit system, and the whole gas circuit system is purged by high-purity helium; in order to prevent boron trichloride from being adsorbed, the whole gas path system is constant at 42+/-0.2 ℃ with heat.
Example two
The difference between this embodiment and the above embodiment is that: as shown in fig. 1, the feed inlet of the first buffer tank 5 of the embodiment may also be directly communicated with the outlet of the first pipeline 2 through a pipeline, two ends of the pipeline are respectively welded and fixed with and communicated with the feed inlet of the first buffer tank 5 and the outlet of the first pipeline 2, and the pipeline is also equipped with an electromagnetic valve;
The feed inlet of the second buffer tank 10 of this embodiment may also be directly connected to the outlet of the third pipeline 8 through a pipe, where two ports of the pipe are welded to and connected to the feed inlet of the second buffer tank 10 and the outlet of the third pipeline 8, respectively, and the pipe is further equipped with an electromagnetic valve.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
The above examples merely illustrate embodiments of the invention, the scope of the invention is not limited to the above examples, and it is obvious to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention.
Claims (8)
1. An impurity gas detection device of an electronic grade boron trichloride purification system is characterized in that: the system comprises a crude product storage tank, a first pipeline, a second pipeline, a first Fourier infrared spectrum detection system, a first buffer tank, a first vacuum pump, a boron trichloride purification system, a third pipeline, a second Fourier infrared spectrum detection system, a second buffer tank, a second vacuum pump and an alkali liquor cylinder; the first pipeline and the second pipeline are arranged in parallel, and the inlet of the first pipeline and the inlet of the second pipeline are communicated with the discharge port of the crude product storage tank through a three-way valve; the first Fourier infrared spectrum detection system comprises a first sample tank, wherein a feed inlet of the first sample tank is communicated with an outlet of a first pipeline, a feed inlet of the first buffer tank is communicated with a discharge outlet of the first sample tank, a feed inlet of the first vacuum pump is communicated with a discharge outlet of the first buffer tank, and a discharge outlet of the first vacuum pump is communicated into the alkali liquor barrel; the feed inlet of the boron trichloride purification system is communicated with the outlet of the second pipeline; the inlet of the third pipeline is communicated with the discharge port of the boron trichloride purification system; the second Fourier infrared spectrum detection system comprises a second sample tank, a feed inlet of the second sample tank is communicated with an outlet of the third pipeline, a feed inlet of the second buffer tank is communicated with a discharge outlet of the second sample tank, a feed inlet of the second vacuum pump is communicated with a discharge outlet of the second buffer tank, and a discharge outlet of the second vacuum pump is communicated into the alkali liquor barrel;
the first Fourier infrared spectrum detection system further comprises a first detector, a first FTIR spectrometer, a first infrared light source and first control analysis software; the first detector is arranged at one side of the first sample cell; the first FTIR spectrometer is arranged on the other side of the first sample cell; the first infrared light source is arranged on the other side of the first FTIR spectrometer; the first control analysis software is electrically connected with the first detector, the first FTIR spectrometer and the first infrared light source;
the optical path length of the first sample cell is 60mm, and the optical path length of the second sample cell is 10m;
The first Fourier infrared spectrum detection system and the second Fourier infrared spectrum detection system can respectively detect impurity gases in the crude boron trichloride product and the finished product simultaneously in real time;
the detection method of the impurity gas detection device of the electronic grade boron trichloride purification system comprises the following steps of: starting a first vacuum pump, filling a part of crude boron trichloride in a crude product storage tank into a first sample pool of a first Fourier infrared spectrum detection system through a first pipeline, detecting and analyzing, and then introducing the crude boron trichloride into an alkali liquor cylinder after passing through an outlet of the first sample pool and a first buffer tank, wherein the alkali liquor cylinder neutralizes the detected crude boron trichloride; starting a second vacuum pump, introducing the other part of the crude boron trichloride in the crude product storage tank into a boron trichloride purification system through a second pipeline to generate a high-purity electronic grade boron trichloride finished product, filling the electronic grade boron trichloride finished product into a second sample cell of a second Fourier infrared spectrum detection system through a third pipeline, introducing the electronic grade boron trichloride finished product into an alkali liquor cylinder after passing through an outlet of the second sample cell and a second buffer tank, and neutralizing the detected electronic grade boron trichloride finished product by the alkali liquor cylinder; or simultaneously starting the first vacuum pump and the second vacuum pump to realize the simultaneous detection of impurity gases in the crude boron trichloride product and the finished product, and simultaneously neutralizing the detected crude boron trichloride product and the detected finished product by the alkali liquor cylinder;
The first Fourier infrared spectrum detection system detects impurity gas in the crude boron trichloride, and comprises the following steps:
(1) Spectral measurement:
Charging the crude boron trichloride product into a first sample cell for multiple reflections;
The first infrared light source is collimated by the optical system and then is led into the first FTIR spectrometer, and the infrared radiation signal is led into the first sample pool for multiple reflections after being subjected to interference modulation by the first FTIR spectrometer;
The infrared radiation signals which are led out from the first sample pool and are subjected to interference modulation carry the absorption information of the sample to be detected and are converged on the first detector
The first control analysis software converts the interference pattern obtained by the first detector into a spectrogram to obtain an absorption spectrum of the infrared absorption characteristic of the pollution gas to be detected
(2) Quantitative analysis:
Utilizing a high-resolution infrared spectrum database to establish measurement parameters conforming to a first FTIR spectrometer, and carrying out temperature and air pressure correction on a characteristic spectrum database for quantitative analysis;
Extracting absorption line parameters of target gas by using the established characteristic spectrum database; by correcting the ambient temperature and the air pressure, inputting the optical path length, the preset gas components and the preset concentration, generating an atmospheric transmittance spectrum in an ideal state according to a single-layer atmospheric radiation transmission model, and convolving the atmospheric transmittance spectrum with an instrument linear function ILS of a first FTIR spectrometer to generate a quantitative analysis calibration spectrum;
and performing repeated iterative fitting on the quantitative analysis calibration spectrum and the measurement spectrum obtained by the first control analysis software by using a nonlinear least square fitting quantitative inversion algorithm to obtain an optimal value of the concentration of the gas to be detected.
2. The impurity gas detection device of an electronic grade boron trichloride purification system as set forth in claim 1, wherein: the window sheets at the left and right sides of the first sample cell and the window sheets at the left and right sides of the second sample cell are BaF 2 window sheets.
3. The impurity gas detection device of an electronic grade boron trichloride purification system as set forth in claim 2, wherein: the first sample cell and the second sample cell are internally provided with temperature control and pressure control systems, and the gas temperatures in the first sample cell and the second sample cell are constant at 42+/-0.2 ℃ and the gas pressures are constant at 1+/-0.1 standard atmospheric pressure.
4. The impurity gas detection device of an electronic grade boron trichloride purification system as set forth in claim 1, wherein: the first Fourier infrared spectrum detection system detects that the impurity gas component and the concentration range in the crude boron trichloride are ：CH4：100-200ppm、CO：100-150ppm、CO2：100-200ppm,HCl：100-300ppm、COCl2：1-200ppm、SiCl4：100-300ppm、SiH2Cl2：1-200ppm.
5. An impurity gas detection apparatus for an electronic grade boron trichloride purification system as defined in claim 3, wherein: the second Fourier infrared spectrum detection system further comprises a second detector, a second FTIR spectrometer, a second infrared light source and second control analysis software; the second detector is arranged at one side of the second sample cell; the second FTIR spectrometer is arranged on the other side of the second sample cell; the second infrared light source is arranged on the other side of the second FTIR spectrometer; the second control analysis software is electrically connected with the second detector, the second FTIR spectrometer and the second infrared light source.
6. The impurity gas detection device of an electronic grade boron trichloride purification system of claim 5, wherein: the second Fourier infrared spectrum detection system detects the impurity gas component and the concentration range in the finished boron trichloride product as follows ：CH4：0.01-0.5ppm、CO：0.1-0.5ppm、CO2：0.1-2ppm、HCl：0.1-1ppm、COCl2：0.1-1ppm、SiCl4：0.05-2ppm、SiH2Cl2：0.1-1ppm.
7. The impurity gas detection device of an electronic grade boron trichloride purification system as set forth in claim 1, wherein: the heat tracing device further comprises a helium tank, wherein an air outlet of the helium tank is respectively communicated with the first pipeline and the third pipeline through a three-way valve to form an air path system, and the air path system is constant at 42+/-0.2 ℃ and accompanies heat.
8. The impurity gas detection device of an electronic grade boron trichloride purification system of claim 7, wherein: the first pipeline and the third pipeline are respectively provided with a pressure reducing valve and a flowmeter.
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| CN208399472U (en) * | 2018-07-18 | 2019-01-18 | 和立气体（上海）有限公司 | Boron chloride analytical sampling device |
| CN212369904U (en) * | 2020-04-24 | 2021-01-19 | 无锡皮埃姆环保设备有限公司 | Double-tower purification system suitable for hazardous waste flue gas treatment |
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| JPH1033931A (en) * | 1996-07-29 | 1998-02-10 | I H I Plantec:Kk | Flow rate control method of hydrocarbon gas recovery apparatus and apparatus therefor |
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| CN105731481B (en) * | 2014-12-12 | 2018-07-06 | 广东先导稀材股份有限公司 | Method and equipment for purifying boron trichloride |
| CN108367229A (en) * | 2015-12-07 | 2018-08-03 | 昭和电工株式会社 | The manufacturing method of ammonia removal equipment, ammonia-removal method, hydrogen |
| CN108896689A (en) * | 2018-08-13 | 2018-11-27 | 朗析仪器（上海）有限公司 | A kind of chromatography sampling system for the analysis of Electronic Gases boron chloride |
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| CN212369904U (en) * | 2020-04-24 | 2021-01-19 | 无锡皮埃姆环保设备有限公司 | Double-tower purification system suitable for hazardous waste flue gas treatment |
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