CN117191986A - Electronic-grade germane analysis method - Google Patents
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- CN117191986A CN117191986A CN202311154597.0A CN202311154597A CN117191986A CN 117191986 A CN117191986 A CN 117191986A CN 202311154597 A CN202311154597 A CN 202311154597A CN 117191986 A CN117191986 A CN 117191986A
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- 238000004458 analytical method Methods 0.000 title claims abstract description 49
- 229910000078 germane Inorganic materials 0.000 title claims abstract description 38
- 239000007789 gas Substances 0.000 claims abstract description 58
- 239000012535 impurity Substances 0.000 claims abstract description 25
- 238000000926 separation method Methods 0.000 claims abstract description 22
- 239000012159 carrier gas Substances 0.000 claims abstract description 21
- 101100328886 Caenorhabditis elegans col-2 gene Proteins 0.000 claims abstract description 14
- 238000002347 injection Methods 0.000 claims abstract description 13
- 239000007924 injection Substances 0.000 claims abstract description 13
- 101100328883 Arabidopsis thaliana COL1 gene Proteins 0.000 claims abstract description 11
- QUZPNFFHZPRKJD-UHFFFAOYSA-N germane Chemical compound [GeH4] QUZPNFFHZPRKJD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052986 germanium hydride Inorganic materials 0.000 claims abstract description 11
- 238000010926 purge Methods 0.000 claims abstract description 6
- 239000010935 stainless steel Substances 0.000 claims description 20
- 229910001220 stainless steel Inorganic materials 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 15
- 238000007664 blowing Methods 0.000 claims description 3
- 231100000614 poison Toxicity 0.000 abstract description 2
- 230000007096 poisonous effect Effects 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 41
- 238000001514 detection method Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007728 cost analysis Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 230000005693 optoelectronics Effects 0.000 description 1
- 238000000918 plasma mass spectrometry Methods 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
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- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
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- 239000010409 thin film Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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Abstract
The invention provides an electronic-grade germane analysis method, which comprises the following steps: setting a V1 valve, a V2 valve, a V3 valve and a V4 valve, and placing the set valves in a gas path; v1 valve CCW, V2 valve CW, and V3 valve CW purge samples of LOOP1 and LOOP2; during sample injection, the carrier gas 3 of the CW-CCW of the V2 valve carries a LOOP1 sample to enter the PRECOL1 for pre-separation and then enter the COL1 for re-analysis: after the impurity component in the sample flows out of the PRECOL1, the V2 valve CCW-CW reversely blows the main component GeH4; the carrier gas 5 of the CW-CCW valve carries LOOP2 samples to enter the pre COL2 for pre-separation and then enter the COL2 for re-analysis; impurity component CO in a sample 2 After exiting PRECOL1, the V3 valve CCW-CW blowback of the main component GeH4; and the time for the impurity components to enter the detector is controlled respectively through the sample injection time and the flow rate, and the COL1/COL2 switching is selected through the V4 column selection valve, so that the impurity peaks are collected on the spectrogram. GermaneThe germanium tetrahydride is a poisonous, combustible and colorless gas at normal temperature and normal pressure, and has special pungent odor.
Description
Technical Field
The invention belongs to the field of germane analysis, and particularly relates to an electronic-grade germane analysis method.
Background
Currently, electronic grade germanes refer to raw materials and intermediates used in the production of electronic components, electronic devices, semiconductors, and the like. Currently, the germane analysis methods commonly used in the market mainly comprise gas chromatography, plasma mass spectrometry, neutron activation and the like, and the methods belong to chemical-grade germane analysis methods. The chemical grade germane analysis method has the following problems: the detection lower limit is low: the detection lower limit of the chemical-grade germane analysis method is generally lower than 10-10g/L, and the detection requirement of the micro-germane cannot be met. Pretreatment is needed: in the chemical-grade germane analysis method, the sample needs to be pretreated, such as degassing, distillation and the like, in the pretreatment process, so as to remove impurities and gases in the sample. A large amount of solvents and reagents are required: chemical grade germane analysis methods require large amounts of solvents and reagents, such as solvents and reagents, etc. These substances can interfere with the test results and affect the accuracy of the analysis results. Requiring complex equipment and maintenance: the electronic grade germane analysis method requires the use of complex equipment and maintenance such as chromatographic columns, mass spectrometry probes, sample injectors, etc., which are costly.
Germane is colorless and extremely toxic gas with unpleasant and irritating odor at normal temperature and normal pressure, is used as an important electronic industrial gas, and is mainly used as an epitaxial growth raw material gas for forming a germanium-silicon film in the manufacturing process of semiconductor materials, and the purity of the germane is directly related to the quality of finished semiconductor devices. Along with the development of the domestic electronic industry, germane is increasingly widely applied, and units for domestic production and application of germane are increasingly increased.
At present, the high-purity gas is analyzed, the traditional TCD or FID detectors are generally adopted in China, the sensitivity of the detectors is mostly low, and the impurities required by analysis can be completely analyzed by using a plurality of chromatographs. The equipment for high purity germane gas analysis is more scarce. Specific standards for germane products and detection methods are not established in China or even in the world. Due to the lack of related detection methods, domestic users have blind spots on the imported germane gas quality control.
Thus, there is a need for an electronic grade germane analysis method.
Disclosure of Invention
The invention provides an electronic-grade germane analysis method, which solves the problem that the prior art cannot have a complete method for analyzing H in germane 2 、O 2 、N 2 、CO、CH 4 And CO 2 Conduct qualitative and quantitative analysisAnalysis of the quantity detects problems of the job.
The technical scheme of the invention is realized as follows: a method of electronic grade germane analysis, the method comprising the steps of:
setting a V1 valve, a V2 valve, a V3 valve and a V4 valve, and placing the set valves in a gas path;
v1 valve CCW, V2 valve CW, and V3 valve CW purge samples of LOOP1 and LOOP2;
during sample injection, the carrier gas 3 of the CW-CCW of the V2 valve carries a LOOP1 sample to enter the PRECOL1 for pre-separation and then enter the COL1 for re-analysis: after the impurity component in the sample flows out of the PRECOL1, the V2 valve CCW-CW reversely blows the main component GeH4;
the carrier gas 5 of the CW-CCW valve carries LOOP2 samples to enter the pre COL2 for pre-separation and then enter the COL2 for re-analysis; impurity component CO in a sample 2 After exiting PRECOL1, the V3 valve CCW-CW blowback of the main component GeH4;
and the time for the impurity components to enter the detector is controlled respectively through the sample injection time and the flow rate, and the COL1/COL2 switching is selected through the V4 column selection valve, so that the impurity peaks are collected on the spectrogram.
Germane is a poisonous, flammable and colorless gas with special pungent odor under normal temperature and normal pressure. Germane is used for deposition of epitaxial silicon and amorphous silicon, germanium, alloys and as a component of (Si, ge) 02 thin film plasma enhanced chemical vapor deposition, providing a controllable refractive index for optoelectronic applications. The tightness is very important because of the toxicity of germane and its spontaneous combustion in air.
The scheme mainly utilizes a specific gas path system of the helium ionization gas chromatograph, designs an analysis and detection method of electronic-grade germane, and realizes qualitative and quantitative analysis and detection of H2, O2, N2, CO, CH 4 and CO2 in germane.
As a preferred implementation manner, the gas circuit is arranged in a gas chromatograph, the gas chromatograph adopts a GOW-MAC 592 gas chromatograph for analysis, and the gas circuit structure is a double back-flushing gas circuit.
As a preferred implementation mode, the gas circuit is arranged in the gas chromatograph, a VCR interface is adopted as an interface between a sample and a chromatographic column, an airtight ring is arranged on the interface of the chromatographic column in a ring mode, and the chromatographic column is made of stainless steel.
As a preferred embodiment, the column uses a SLICA GEL stainless steel tube with a diameter of 4mm and a wall thickness of 0.125mm with a VCR fitting.
As a preferred embodiment, the chromatographic column uses a stainless steel tube of Moreieve 13X with a diameter of 8mm and a wall thickness of 0.125mm and a VCR connector.
As a preferred embodiment, the chromatographic column uses a Hayesep Q stainless steel tube with a VCR connector having a diameter of 10mm and a tube wall thickness of 0.125 mm.
As a preferred embodiment, the V1 valve is a carrier gas/sample switching valve, the V2 valve and the V3 valve are blowback valves, and the V4 valve is a column selection valve.
After the technical scheme is adopted, the invention has the beneficial effects that: the analysis efficiency is improved, samples can be rapidly and efficiently analyzed by arranging the V1 valve, the V2 valve, the V3 valve and the V4 valve, and the analysis time is shortened; the analysis precision is improved, and the analysis precision can be effectively controlled by reasonably selecting a V2 valve, a CW-CCW carrier gas 3, a V3 valve CW-CCW carrier gas 5 and COL1/COL 2; analysis cost is reduced, and low-cost analysis is realized; the analysis stability is enhanced, the sample is effectively prevented from being adsorbed and oxidized, and the service life of the sample is prolonged.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained according to these drawings without inventive faculty for a person skilled in the art.
FIG. 1 is a flow chart of the method of the present invention;
FIG. 2 is a diagram of a dual blowback gas circuit of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Examples:
as shown in fig. 1-2, a method for analyzing electronic grade germane, the method comprising the steps of:
setting a V1 valve, a V2 valve, a V3 valve and a V4 valve, and placing the set valves in a gas path;
v1 valve CCW, V2 valve CW, and V3 valve CW purge samples of LOOP1 and LOOP2;
during sample injection, the carrier gas 3 of the CW-CCW of the V2 valve carries a LOOP1 sample to enter the PRECOL1 for pre-separation and then enter the COL1 for re-analysis: after the impurity component in the sample flows out of the PRECOL1, the V2 valve CCW-CW reversely blows the main component GeH4;
the carrier gas 5 of the CW-CCW valve carries LOOP2 samples to enter the pre COL2 for pre-separation and then enter the COL2 for re-analysis; impurity component CO in a sample 2 After exiting PRECOL1, the V3 valve CCW-CW blowback of the main component GeH4;
and the time for the impurity components to enter the detector is controlled respectively through the sample injection time and the flow rate, and the COL1/COL2 switching is selected through the V4 column selection valve, so that the impurity peaks are collected on the spectrogram.
As a preferred implementation manner, the gas circuit is arranged in a gas chromatograph, the gas chromatograph adopts a GOW-MAC 592 gas chromatograph for analysis, and the gas circuit structure is a double back-flushing gas circuit.
The electronic-grade germane analysis method mainly comprises the following steps: setting a V1 valve, a V2 valve, a V3 valve and a V4 valve, and placing the set valves in a gas path: the purpose of these valves is to control the direction and path of the gas flow. They are positioned in the air path and adjusted to ensure proper operation.
V1 valve CCW, V2 valve CW, and V3 valve CW purge samples from LOOP1 and LOOP2: by adjusting the states of the V1 valve, the V2 valve, and the V3 valve, the carrier gas 3 carries the samples in LOOP1 and LOOP2 to purge.
During sample injection, the carrier gas 3 of the CW-CCW of the V2 valve carries a LOOP1 sample to enter the PRECOL1 for pre-separation and then enter the COL1 for re-analysis: in the sample injection process, a carrier gas 3 carrying LOOP1 sample is introduced into the pre-column 1 for pre-separation by switching the state of the V2 valve, and then enters the column 1 for re-analysis. In the sample, after the impurity component flows out from the pre-column 1, the main component GeH4 is pushed out from the column 1 by the back-blowing operation of the V2 valve.
The V3 valve CW-CCW carrier gas 5 carries LOOP2 sample into PRECOL2 for pre-separation and then into COL2 for re-analysis: in the sample injection process, a carrier gas 5 carrying LOOP2 sample is introduced into the pre-column 2 for pre-separation by switching the state of the V3 valve, and then enters the column 2 for re-analysis. In the sample, after the impurity component CO2 flows out from the pre-column 2, the main component GeH4 is pushed out from the column 2 by the back-blowing operation of the V3 valve.
And the time for impurity components to enter the detector is controlled by the sample injection time and the flow rate respectively: by adjusting the sample injection time and the flow rate, the time for different impurity components to enter the detector can be controlled, so that the separation and analysis of the impurity components are realized.
COL1/COL2 switching is selected through a V4 column selection valve, and impurity peaks are collected on a spectrogram: by adjusting the state of the V4 column selector valve, it is possible to selectively connect to column 1 or column 2, thereby collecting impurity peaks on the spectrogram, facilitating analysis and observation.
The gas circuit is arranged in the gas chromatograph, a VCR interface is adopted as an interface between the sample and the chromatographic column, an airtight ring is annularly arranged on the interface of the chromatographic column, and the chromatographic column is made of stainless steel. The gas circuit comprises a gas chromatograph and a sample, and the interface of the gas chromatograph and the sample adopts a VCR interface, namely an airtight chromatographic tube interface. The chromatographic column interface is provided with the airtight ring, and because the chromatographic column interface is made of metal and is easy to be corroded by external gas, the airtight ring is arranged at the interface, so that the external gas can be prevented from entering the chromatographic column. The chromatographic column is made of stainless steel, has good corrosion resistance and strength, can bear larger gas pressure and temperature change, and ensures the stability and reliability of the chromatographic column. In addition, the chromatographic column is made of stainless steel, so that the problems of pollution, corrosion and the like caused by contact between a metal material and a sample can be avoided. When the gas circuit is operated in a gas chromatograph, the sample passes through the column from the sample tube, and gas pressure is generated when the sample contacts the column. In order to avoid errors caused by gas pressure fluctuation, an airtight ring is arranged at the interface of the chromatographic column, so that external gas can be sealed in the chromatographic column, and the stability and the reliability of a gas circuit are ensured. In summary, the gas circuit is made of stainless steel, and has the advantages of good corrosion resistance, high strength, good pollution resistance and the like.
The chromatographic column adopts a SLICA GEL stainless steel tube with a diameter of 4mm and a tube wall thickness of 0.125mm and a VCR joint. The chromatographic column can be used for gas chromatography, and can realize high-precision separation and detection of various substances because of good separation performance and high sensitivity. Firstly, the chromatographic column is made of stainless steel, has good corrosion resistance and strength, can bear larger gas pressure and temperature changes, and ensures the stability and reliability of the chromatographic column. And secondly, the chromatographic column adopts a VCR connector, so that the pollution to the chromatographic column caused by the sample flowing out of the chromatographic column can be avoided, and the separation efficiency is improved. In addition, the chromatographic column has good sealing performance and stability, and can prevent external gas from entering the chromatographic column, thereby improving the accuracy of detection results. In summary, the chromatographic column adopts the SLICA GEL stainless steel tube with the diameter of 4mm and the tube wall thickness of 0.125mm and the VCR joint, and can realize high-precision separation and detection of various substances, thereby meeting the requirements of practical application.
The chromatographic column adopts a Molesieve13X stainless steel tube with a diameter of 8mm and a tube wall thickness of 0.125mm and a VCR joint. A Molesieve13X stainless steel tube with a VCR joint and a diameter of 8mm and a tube wall thickness of 0.125mm is adopted. Such chromatography columns may be used to separate and purify various types of compounds, such as proteins, polysaccharides, lipids, and the like. The special connector is adopted and can be connected into a Molesieve13X stainless steel pipe with a VCR connector, so that the reliability and stability of separation can be ensured. In addition, such columns have a high wall thickness to prevent clogging of materials within the column. The higher wall thickness also ensures that the column can be used for a long period of time without separation failure due to damage or aging. At the same time, it has higher pipe wall thickness and better durability.
The chromatographic column adopts a Hayesep Q stainless steel tube with a VCR joint, the diameter of which is 10mm, and the thickness of the tube wall of which is 0.125 mm. Hayesep Q stainless steel tube with VCR joint and 10mm diameter and 0.125mm wall thickness was used. Such a column can be used for separating complex substances and has high efficiency and high stability. First, the column uses a special connection, i.e., a VCR joint. Such a fitting may be attached to one end of the column so that the column may prevent leakage of gases and liquids to some extent. Second, such columns also have a high wall thickness to ensure adequate separation of the drug in the column. Finally, the column also has a nozzle with a diameter of 8mm, which can be easily cleaned and maintained.
The V1 valve is a carrier gas/sample switching valve, the V2 valve and the V3 valve are blowback valves, and the V4 valve is a column selection valve. The V1 valve is a carrier gas/sample switching valve that can be switched between carrier gas and sample to ensure stability of the chromatographic column. The V2 valve and the V3 valve are blowback valves, which can prevent gas residue on the surface of the chromatographic column in the event of blowback. The V4 valve is a column selection valve which can be selected according to the type and size of the chromatographic column to ensure the stability and separation effect of the chromatographic column. The device realizes the switching between carrier gas and sample through the V1 valve to realize the blowback through V2 valve and V3 valve, prevent the gas residue on chromatographic column surface. In addition, the device also selects the chromatographic conditions most suitable for the chromatographic column through the V4 valve so as to improve the performance and the separation effect of the chromatographic column.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (7)
1. A method of electronic grade germane analysis, the method comprising the steps of:
setting a V1 valve, a V2 valve, a V3 valve and a V4 valve, and placing the set valves in a gas path;
v1 valve CCW, V2 valve CW, and V3 valve CW purge samples of LOOP1 and LOOP2;
during sample injection, the carrier gas 3 of the CW-CCW of the V2 valve carries a LOOP1 sample to enter the PRECOL1 for pre-separation and then enter the COL1 for re-analysis: after the impurity component in the sample flows out of the PRECOL1, the V2 valve CCW-CW reversely blows the main component GeH4;
the carrier gas 5 of the CW-CCW valve carries LOOP2 samples to enter the pre COL2 for pre-separation and then enter the COL2 for re-analysis; impurity component CO in a sample 2 After exiting PRECOL1, the V3 valve CCW-CW blowback of the main component GeH4;
and the time for the impurity components to enter the detector is controlled respectively through the sample injection time and the flow rate, and the COL1/COL2 switching is selected through the V4 column selection valve, so that the impurity peaks are collected on the spectrogram.
2. An electronic grade germane analysis method as claimed in claim 1, wherein: the gas circuit is arranged in a gas chromatograph, the gas chromatograph adopts a GOW-MAC 592 gas chromatograph for analysis, and the gas circuit structure is a double back blowing gas circuit.
3. An electronic grade germane analysis method as claimed in claim 1, wherein: the gas circuit is arranged in the gas chromatograph, a VCR interface is adopted as an interface between the sample and the chromatographic column, an airtight ring is annularly arranged on the interface of the chromatographic column, and the chromatographic column is made of stainless steel.
4. A method of electronic grade germane analysis as claimed in claim 3, wherein: the chromatographic column adopts a SLICAGEL stainless steel tube with a diameter of 4mm and a tube wall thickness of 0.125mm and a VCR joint.
5. A method of electronic grade germane analysis as claimed in claim 3, wherein: the chromatographic column adopts a Molesieve13X stainless steel tube with a diameter of 8mm and a tube wall thickness of 0.125mm and a VCR joint.
6. A method of electronic grade germane analysis as claimed in claim 3, wherein: the chromatographic column adopts a Hayesep Q stainless steel tube with a VCR joint, the diameter of which is 10mm, and the thickness of the tube wall of which is 0.125 mm.
7. An electronic grade germane analysis method as claimed in claim 1, wherein: the V1 valve is a carrier gas/sample switching valve, the V2 valve and the V3 valve are blowback valves, and the V4 valve is a column selection valve.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311154597.0A CN117191986A (en) | 2023-09-08 | 2023-09-08 | Electronic-grade germane analysis method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311154597.0A CN117191986A (en) | 2023-09-08 | 2023-09-08 | Electronic-grade germane analysis method |
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| Publication Number | Publication Date |
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| CN117191986A true CN117191986A (en) | 2023-12-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311154597.0A Pending CN117191986A (en) | 2023-09-08 | 2023-09-08 | Electronic-grade germane analysis method |
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| Country | Link |
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| CN (1) | CN117191986A (en) |
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2023
- 2023-09-08 CN CN202311154597.0A patent/CN117191986A/en active Pending
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