CN115166103A - System and method for analyzing impurities in diborane-containing feed gas - Google Patents
System and method for analyzing impurities in diborane-containing feed gas Download PDFInfo
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- CN115166103A CN115166103A CN202210998740.3A CN202210998740A CN115166103A CN 115166103 A CN115166103 A CN 115166103A CN 202210998740 A CN202210998740 A CN 202210998740A CN 115166103 A CN115166103 A CN 115166103A
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The embodiment of the invention relates to a system and a method for analyzing impurities in diborane-containing feed gas. The system comprises a detector, a data acquisition unit, a data processing unit and a data processing unit, wherein the detector is used for detecting the content of each impurity in the raw material gas to be analyzed, the raw material gas to be analyzed comprises diborane and impurities, and the impurities comprise carbon dioxide; the first channel comprises a quantitative ring, a first selection valve, a second selection valve, a third selection valve, a first chromatographic column, a second chromatographic column and a third chromatographic column, the quantitative ring is used for containing a fixed volume of feed gas to be analyzed, and the first selection valve, the second selection valve and the third selection valve are respectively provided with a first state and a second state which can be switched; a second passageway for providing a carrier gas; by switching the states of the first selector valve, the second selector valve and the third selector valve, carbon dioxide, diborane and other impurities are sequentially separated by using the first chromatographic column, the second chromatographic column and the third chromatographic column, and the content of each gas is detected by using a detector. The analysis system can accurately analyze the content of each impurity in the raw material gas containing diborane.
Description
Technical Field
The embodiment of the invention relates to the technical field of gas analysis, in particular to a system and a method for analyzing impurities in diborane-containing feed gas.
Background
Diborane is an inorganic compound, is the simplest borane which can be separated at present and has the chemical formula B 2 H 6 Colorless gas at normal temperature. Diborane is used as an important raw material and widely applied to various industries, for example, diborane can be used as a doping source and is used in the semiconductor industry.
In the semiconductor industry, raw material gas containing diborane is required to be doped into a silicon wafer, and if the purity of the diborane in the raw material gas does not meet the requirement, the product of the whole production line is scrapped, and huge loss is caused. Therefore, the method for accurately obtaining the purity of the diborane in the raw material gas has important significance for industrial production. However, it is also difficult to accurately analyze the content of each impurity in the diborane-containing raw material gas in the related art.
Therefore, there is a need for a system and a method for analyzing impurities in diborane-containing raw material gas to solve the above technical problems.
Disclosure of Invention
The embodiment of the invention provides a system and a method for analyzing impurities in a raw material gas containing diborane, which can accurately analyze the content of each impurity in the raw material gas containing diborane.
In a first aspect, an embodiment of the present invention provides a system for analyzing impurities in a diborane-containing raw material gas, including:
the device comprises a detector, a data acquisition unit, a data processing unit and a data processing unit, wherein the detector is used for detecting the content of each impurity in a raw material gas to be analyzed, the raw material gas to be analyzed comprises diborane and impurities, and the impurities comprise carbon dioxide;
a first channel comprising a dosing ring, a first selection valve, a second selection valve, a third selection valve, a first chromatography column, a second chromatography column and a third chromatography column, wherein the dosing ring is used for containing a fixed volume of feed gas to be analyzed, and the first selection valve, the second selection valve and the third selection valve respectively have a first state and a second state which can be switched; the first chromatographic column is used for separating carbon dioxide from the feed gas to be analyzed to obtain a feed gas without carbon dioxide, and the second chromatographic column and the third chromatographic column are used for separating diborane and other impurities in the feed gas without carbon dioxide;
a second passageway connected to the first selector valve, the second selector valve, the third selector valve, and the detector, the second passageway for providing a carrier gas;
and sequentially separating the carbon dioxide, the diborane and other impurities by using the first chromatographic column, the second chromatographic column and the third chromatographic column by switching the states of the first selector valve, the second selector valve and the third selector valve, and detecting the content of each impurity by using the detector.
In one possible design, the first selector valve is a ten-way valve, and the second selector valve and the third selector valve are both four-way valves;
the ten-way valve comprises ten interfaces, and each four-way valve comprises four interfaces.
In one possible design, when the first selector valve is in the first state, the first interface of the first selector valve is connected with the second interface, the third interface is connected with the fourth interface, the fifth interface is connected with the sixth interface, the seventh interface is connected with the eighth interface, and the ninth interface is connected with the tenth interface; when the first selector valve is in a second state, a second interface of the first selector valve is connected with a third interface, a fourth interface of the first selector valve is connected with a fifth interface, a sixth interface of the first selector valve is connected with a seventh interface, an eighth interface of the first selector valve is connected with a ninth interface, and a tenth interface of the first selector valve is connected with a first interface;
when the second selector valve is in a first state, a first interface of the second selector valve is connected with a fourth interface, and a second interface of the second selector valve is connected with a third interface; when the second selector valve is in a second state, the first interface of the second selector valve is connected with the second interface, and the third interface of the second selector valve is connected with the fourth interface;
when the third selector valve is in a first state, a first interface of the third selector valve is connected with a fourth interface, and a second interface of the third selector valve is connected with a third interface; when the third selector valve is in a second state, the first interface of the third selector valve is connected with the second interface, and the third interface of the third selector valve is connected with the fourth interface.
In a possible design, when the first selector valve is in the first state, the inlet end of the first passage is connected to the second port of the first selector valve, the first port of the first selector valve is connected to one end of the dosing ring, the other end of the dosing ring is connected to the fourth port of the first selector valve, and the third port of the first selector valve is communicated with the outside.
In a possible design, when the first selector valve and the second selector valve are in the second state, the tenth port of the first selector valve is connected to the second passage, the first port of the first selector valve is connected to one end of the dosing ring, the other end of the dosing ring is connected to the fourth port of the first selector valve, the fifth port of the first selector valve is connected to the inlet port of the first chromatography column, the outlet port of the first chromatography column is connected to the ninth port of the first selector valve, the eighth port of the first selector valve is connected to the first port of the second selector valve, and the second port of the second selector valve is connected to the inlet port of the detector.
In a possible design, when the first selector valve is in the second state, and the second selector valve and the third selector valve are in the first state, the tenth port of the first selector valve is connected to the second passage, the first port of the first selector valve is connected to one end of the quantitative ring, the other end of the quantitative ring is connected to the fourth port of the first selector valve, the fifth port of the first selector valve is connected to the inlet end of the first chromatographic column, the outlet end of the first chromatographic column is connected to the ninth port of the first selector valve, the eighth port of the first selector valve is connected to the first port of the second selector valve, the fourth port of the second selector valve is connected to the first port of the third selector valve, and the fourth port of the third selector valve is connected to the first exhaust line.
In a possible design, when the first selector valve and the third selector valve are in the second state and the second selector valve is in the first state, the tenth port of the first selector valve is communicated with the carrier gas, the first port of the first selector valve is connected with one end of the quantitative ring, the other end of the quantitative ring is connected with the fourth port of the first selector valve, the fifth port of the first selector valve is connected with the inlet end of the first chromatographic column, the outlet end of the first chromatographic column is connected with the ninth port of the first selector valve, the eighth port of the first selector valve is connected with the first port of the second selector valve, the fourth port of the second selector valve is connected with the first port of the third selector valve, and the second port of the third selector valve is connected with the detector.
In one possible design, the second path includes five carrier lines; wherein the content of the first and second substances,
the outlet end of the first gas carrying pipeline is connected with a tenth interface of the first selector valve;
the outlet end of the second gas carrying pipeline is connected with a seventh interface of the first selector valve;
the outlet end of the third gas carrying pipeline is connected with a third interface of the second selector valve;
the outlet end of the fourth gas carrying pipeline is connected with a third interface of the third selector valve;
the outlet end of the fifth gas-carrying line is connected to the detector.
In a second aspect, embodiments of the present invention further provide a method for analyzing impurities in a diborane-containing raw material gas, which is applied to a system for analyzing impurities in a raw material gas in any one of the above possible designs, where the method includes:
when the first selector valve is placed in a first state, the feed gas to be analyzed is fed into the quantitative ring through the first selector valve;
when the first selector valve and the second selector valve are placed in a second state, performing: introducing the feed gas to be analyzed in the quantitative ring into the first chromatographic column by using the carrier gas; separating the carbon dioxide and the feed gas without carbon dioxide in sequence by using the first chromatographic column; sending the separated carbon dioxide to the detector for detection;
placing the second selector valve and the third selector valve in the first state after the first selector valve and the second selector valve are placed in the second state for a first set time to introduce the carbon dioxide-free feed gas from the first chromatography column into the second chromatography column; sequentially separating diborane and other impurities by using the second chromatographic column; discharging the separated diborane to the outside;
placing the third selector valve in a second state after the second selector valve and the third selector valve are placed in the first state for a second set time to introduce the remaining gas in the second chromatography column into the third chromatography column; sequentially separating each gas in the residual gas by using the third chromatographic column; and introducing each separated gas into the detector for detection.
In one possible design, the first setting time is set according to the following:
all carbon dioxide separated by the first chromatographic column flows out of the second selector valve, and the carbon dioxide-free feed gas does not flow into the second selector valve; and/or
The second setting time is set according to the following steps:
the diborane separated from the second chromatographic column partially or completely flows out of the third selection valve, and other impurities except the diborane do not flow into the third selection valve.
The application provides an analytic system of impurity in feed gas, includes detector, first route and second route. In the system, the feed gas comprises diborane, the impurity comprises carbon dioxide, and the first path comprises a dosing ring, a first selector valve, a second selector valve, a third selector valve, a first chromatography column, a second chromatography column, and a third chromatography column; the quantitative ring is used for containing a fixed volume of raw material gas to be analyzed, and the first selection valve, the second selection valve and the third selection valve respectively have a first state and a second state which can be switched. The system is based on different sequences of separating carbon dioxide, diborane and other impurities from the chromatographic column, and the gases separated from the chromatographic column are sequentially introduced into a detector for detection by switching the states of the first selector valve, the second selector valve and the third selector valve. Specifically, when the first selector valve and the second selector valve are set in the second state, the feed gas to be analyzed enters the first chromatographic column, the first chromatographic column first separates carbon dioxide, the separated carbon dioxide is introduced into the detector for detection, after the carbon dioxide completely flows out, the second selector valve and the third selector valve are set in the first state, at this time, the gas flowing out from the first chromatographic column enters the second chromatographic column, the second chromatographic column first separates diborane, and as the content of diborane is far higher than that of each impurity, if the separated diborane is directly introduced into the detector for detection, the generated peak value can submerge the peak value generated by each impurity, so that the detection fails. Therefore, the system can accurately analyze the content of each impurity in the raw material gas containing diborane.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic diagram of a system for analyzing impurities in a diborane-containing feed gas according to one embodiment of the present invention;
FIG. 2 is a schematic flow chart of a method for analyzing impurities in a diborane-containing feed gas according to an embodiment of the present invention;
FIG. 3 is a chromatogram of various impurities in a diborane-containing feed gas obtained using the analysis system and method provided herein according to an embodiment of the present invention;
fig. 4 is a chromatogram of each impurity in a helium gas mixture obtained by using the analysis system and the analysis method provided by the present application according to an embodiment of the present invention.
Reference numerals:
1-a detector;
2-a first pathway;
21-a quantification loop;
22-a first selector valve;
23-a second selector valve;
24-a third selector valve;
25-a first chromatography column;
26-a second chromatography column;
27-third chromatography column;
3-a second pathway;
31-a first carrier gas line;
32-a second carrier gas line;
33-a third carrier gas line;
34-a fourth carrier gas line;
35-fifth carrier gas line.
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present invention clearer and more complete, the technical solutions in the embodiments of the present invention will be described below with reference to the drawings in the embodiments of the present invention, it is obvious that the described embodiments are some, but not all embodiments of the present invention, and based on the embodiments of the present invention, all other embodiments obtained by a person of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
As shown in fig. 1, an embodiment of the present invention provides a system for analyzing impurities in a diborane-containing raw material gas, including:
the detector 1 is used for detecting the content of each impurity in the raw material gas to be analyzed, wherein the raw material gas to be analyzed comprises diborane and impurities, and the impurities comprise carbon dioxide;
a first path 2, which comprises a quantitative ring 21, a first selector valve 22, a second selector valve 23, a third selector valve 24, a first chromatographic column 25, a second chromatographic column 26 and a third chromatographic column 27, wherein the quantitative ring 21 is used for containing a fixed volume of feed gas to be analyzed, and the first selector valve 22, the second selector valve 23 and the third selector valve 24 respectively have a first state and a second state which can be switched; the first chromatographic column 25 is used for separating carbon dioxide from a feed gas to be analyzed to obtain a feed gas without carbon dioxide, and the second chromatographic column 26 and the third chromatographic column 27 are used for separating diborane and other impurities from the feed gas without carbon dioxide;
a second path 3 connected to the first selector valve 22, the second selector valve 23, the third selector valve 24, and the detector 1, the second path 3 being used for supplying a carrier gas;
by switching the states of the first selector valve 22, the second selector valve 23, and the third selector valve 24, carbon dioxide, diborane, and other impurities are sequentially separated by the first chromatography column 25, the second chromatography column 26, and the third chromatography column 27, and the content of each gas is detected by the detector 1.
This embodiment provides an analysis system for impurities in a raw material gas, including a detector 1, a first path 2, and a second path 3. Wherein the raw material gas contains diborane and the impurities contain carbon dioxide, and the system sequentially introduces the gases separated from the chromatographic column into the detector 1 for detection by switching the states of the first selector valve 22, the second selector valve 23 and the third selector valve 24 based on different orders of separating carbon dioxide, diborane and other impurities from the chromatographic column. Specifically, when the first selector valve 22 and the second selector valve 23 are set in the second state, the raw material gas to be analyzed enters the first chromatographic column 25, the first chromatographic column 25 first separates carbon dioxide, the separated carbon dioxide is introduced into the detector 1 for detection, and after the carbon dioxide is completely discharged, the second selector valve 23 and the third selector valve 24 are set in the first state, at this time, the gas discharged from the first chromatographic column 25 enters the second chromatographic column 26, the second chromatographic column 26 first separates diborane, because the content of diborane is much higher than that of each impurity, if the separated diborane is directly introduced into the detector 1 for detection, the generated peak value will flood the peak value generated by each impurity, resulting in detection failure, therefore, the present application discharges most diborane separated from the second chromatographic column 26 to the atmosphere by setting the third selector valve 24 in the first state, and then sets the third selector valve 24 in the second state, so that the remaining diborane and other impurities are introduced into the third chromatographic column 27, the third selector valve 27 sequentially discharges most diborane separated from the second chromatographic column 26 and the remaining diborane and the remaining impurities in the third chromatographic column 27, and thus the content of each raw material gas is less accurately detected than that the remaining diborane is detected by the detector 1. Therefore, the system can accurately analyze the content of each impurity in the raw material gas containing diborane.
It should be noted that, in this embodiment, most of the diborane separated from the second chromatographic column 26 is discharged to the atmosphere, and most of the diborane is at least 80% contained in the raw material gas, so that the detection accuracy of other impurities can be ensured. Of course, the user may also choose to discharge more or less diborane to the atmosphere as long as the peak generated by the remaining diborane does not overwhelm the peak generated by each impurity, and the application does not specifically limit the proportion of diborane discharged to the outside. The impurities in the raw material gas may include gases such as oxygen, argon, nitrogen, methane, and carbon monoxide in addition to carbon dioxide, as long as the separation order of the gases in the column is after diborane.
In some embodiments, the first selector valve 22 is a ten-way valve, and the second selector valve 23 and the third selector valve 24 are four-way valves;
the ten-way valve includes ten ports, and each four-way valve includes four ports.
In this embodiment, by rotating the selector valve, the passage state inside the selector valve is switched, for example, the selector valve is changed from the first state to the second state. In addition, the first selector valve 22 is a ten-way valve, and the second selector valve 23 and the third selector valve 24 are four-way valves, which is only a preferred way, and the user may select valves with other interface numbers, and the application is not limited in particular.
In some embodiments, when the first selector valve 22 is in the first state, the first port of the first selector valve 22 is connected to the second port, the third port is connected to the fourth port, the fifth port is connected to the sixth port, the seventh port is connected to the eighth port, and the ninth port is connected to the tenth port; when the first selector valve 22 is in the second state, the second port of the first selector valve 22 is connected with the third port, the fourth port is connected with the fifth port, the sixth port is connected with the seventh port, the eighth port is connected with the ninth port, and the tenth port is connected with the first port;
when the second selector valve 23 is in the first state, the first port of the second selector valve 23 is connected with the fourth port, and the second port is connected with the third port; when the second selector valve 23 is in the second state, the first port of the second selector valve 23 is connected with the second port, and the third port is connected with the fourth port;
when the third selector valve 24 is in the first state, the first port and the fourth port of the third selector valve 24 are connected, and the second port and the third port are connected; when the third selector valve 24 is in the second state, the first port and the second port of the third selector valve 24 are connected, and the third port and the fourth port are connected.
In some embodiments, when the first selector valve 22 is in the first state, the inlet end of the first passage 2 is connected to the second port of the first selector valve 22, the first port of the first selector valve 22 is connected to one end of the dosing ring 21, the other end of the dosing ring 21 is connected to the fourth port of the first selector valve 22, and the third port of the first selector valve 22 is communicated with the outside. In this connection, the first path 2 allows the feed gas to be analyzed to be fed into the dosing ring 21 through the first selection valve 22.
In some embodiments, when the first selector valve 22 and the second selector valve 23 are in the second state, the tenth port of the first selector valve 22 is connected to the second path 3, the first port of the first selector valve 22 is connected to one end of the dosing ring 21, the other end of the dosing ring 21 is connected to the fourth port of the first selector valve 22, the fifth port of the first selector valve 22 is connected to the inlet of the first chromatographic column 25, the outlet of the first chromatographic column 25 is connected to the ninth port of the first selector valve 22, the eighth port of the first selector valve 22 is connected to the first port of the second selector valve 23, and the second port of the second selector valve 23 is connected to the inlet of the detector 1. In this connection, the first path 2 can realize: introducing the feed gas to be analyzed in the quantification ring 21 into the first chromatographic column 25 by using a carrier gas; separating carbon dioxide and a carbon dioxide-free feed gas in sequence by using a first chromatographic column 25; the separated carbon dioxide is sent to the detector 1 for detection.
In some embodiments, when the first selector valve 22 is in the second state and the second selector valve 23 and the third selector valve 24 are in the first state, the tenth port of the first selector valve 22 is connected to the second passage 3, the first port of the first selector valve 22 is connected to one end of the dosing ring 21, the other end of the dosing ring 21 is connected to the fourth port of the first selector valve 22, the fifth port of the first selector valve 22 is connected to the inlet end of the first chromatographic column 25, the outlet end of the first chromatographic column 25 is connected to the ninth port of the first selector valve 22, the eighth port of the first selector valve 22 is connected to the first port of the second selector valve 23, the fourth port of the second selector valve 23 is connected to the first port of the third selector valve 24, the fourth port of the third selector valve 24 is connected to the first exhaust line, and the first exhaust line is provided with an exhaust valve, the exhaust valve is opened when exhaust is not required, and the exhaust valve is closed to prevent air from entering through the third selector valve 24. In this connection, the first path 2 can realize: introducing a carbon dioxide-free feed gas from the first chromatography column 25 to a second chromatography column 26; diborane and other impurities are separated sequentially by means of a second chromatographic column 26; the separated diborane is discharged to the outside.
In some embodiments, when the first selector valve 22 and the third selector valve 24 are in the second state and the second selector valve 23 is in the first state, the tenth port of the first selector valve 22 is communicated with the carrier gas, the first port of the first selector valve 22 is connected to one end of the dosing ring 21, the other end of the dosing ring 21 is connected to the fourth port of the first selector valve 22, the fifth port of the first selector valve 22 is connected to the inlet of the first chromatographic column 25, the outlet of the first chromatographic column 25 is connected to the ninth port of the first selector valve 22, the eighth port of the first selector valve 22 is connected to the first port of the second selector valve 23, the fourth port of the second selector valve 23 is connected to the first port of the third selector valve 24, and the second port of the third selector valve 24 is connected to the detector 1. In this connection, the first path 2 can realize: introducing the remaining gas in the second chromatography column 26 into a third chromatography column 27; the third chromatographic column 27 is used for sequentially separating each gas in the residual gas, including diborane and other impurities; each separated gas is introduced into the detector 1 to be detected.
In some embodiments, the second path 3 comprises five carrier gas lines; wherein, the first and the second end of the pipe are connected with each other,
the outlet end of the first carrier gas line 31 is connected to the tenth port of the first selector valve 22;
the outlet end of the second carrier gas pipeline 32 is connected with the seventh port of the first selector valve 22;
the outlet end of the third carrier gas pipeline 33 is connected with the third interface of the second selector valve 23;
the outlet end of the fourth carrier gas line 34 is connected to the third port of the third selector valve 24;
the outlet end of the fifth gas-carrying line 35 is connected to the detector 1.
In this embodiment, five carrier gas lines are connected in parallel, and the five carrier gas lines may be independently connected to the carrier gas supply device, or the inlet ends of the five carrier gas lines may be connected together to form a common line, which is then connected to the carrier gas supply device.
In some embodiments, valves are provided on each of the carrier gas line and the common line, as shown in fig. 1, to facilitate the switching of the carrier gas.
It should be noted that, in this embodiment, each valve is a flow stabilizing valve to ensure that the flow of the gas path is kept stable when the gas resistance at the outlet of the valve changes.
In some embodiments, detector 1 is a helium ion detector.
In addition, fig. 1 only shows the necessary equipment for analyzing the content of each impurity in the raw material gas, and besides, the system may further include other equipment such as valves, pipelines, thermometers, pressure gauges, and sensors, which are required for normal operation, and thus, the details are not repeated herein.
As shown in fig. 2, an embodiment of the present invention provides a method for analyzing impurities in a diborane-containing raw material gas, the method comprising:
when the first selector valve 22 is set in the first state, the feed gas to be analyzed is fed into the quantitative loop 21 through the first selector valve 22;
when the first selector valve 22 and the second selector valve 23 are placed in the second state, the following are performed: introducing the feed gas to be analyzed in the quantification ring 21 into the first chromatographic column 25 by using a carrier gas; separating carbon dioxide and a carbon dioxide-free feed gas in sequence by using a first chromatographic column 25; sending the separated carbon dioxide into a detector 1 for detection;
after the first selector valve 22 and the second selector valve 23 are placed in the second state for a first set time, the second selector valve 23 and the third selector valve 24 are placed in the first state to introduce the carbon dioxide-free feed gas from the first chromatography column 25 into the second chromatography column 26; diborane and other impurities are separated sequentially by means of a second chromatographic column 26; discharging the separated diborane to the outside;
after the second selector valve 23 and the third selector valve 24 are placed in the first state for a second set time, the third selector valve 24 is placed in the second state to introduce the remaining gas in the second column 26 into the third column 27; the third chromatographic column 27 is used for sequentially separating each gas in the residual gas; each separated gas is introduced into the detector 1 to be detected.
In some embodiments, the first setting time is set according to:
all the carbon dioxide separated by the first chromatographic column 25 flows out of the second selector valve 23, and the feed gas containing no carbon dioxide does not flow into the second selector valve 23; and/or
The second setting time is set according to the following steps:
the diborane separated from the second column 26 partially or completely flows out of the third selection valve 24, and other impurities except the diborane do not flow into the third selection valve 24.
In this embodiment, the first set time is set to ensure that all carbon dioxide in the raw material gas enters the detector 1, so as to accurately detect the content of carbon dioxide, and at the same time, other gases in the raw material gas enter the second chromatographic column 26 for further separation, for example, in some embodiments, the first set time is 2.97 minutes.
In addition, since the diborane in the raw material gas is background and has very high content, if the separated diborane is directly fed into the detector 1, an overlarge peak value is generated, so that the peak value of other gases is submerged, and the content of other gases cannot be detected. Therefore, by setting the second setting time, most (for example, more than 80%) of the diborane separated from the second chromatographic column 26 may be discharged to the outside, or of course, all of the diborane may be discharged (but the actual operation is difficult, and if the time control is not good, other impurities may be discharged together), and then the remaining gas may be introduced into the third chromatographic column 27, and since the content of the diborane entering the third chromatographic column 27 is relatively low, the detection accuracy of other impurities may not be affected, for example, in some embodiments, the second setting time is 5 minutes.
It can be understood that the method for analyzing impurities in a raw material gas provided in this embodiment and the system for analyzing impurities in a raw material gas provided in the foregoing embodiment have the same beneficial effects, and are not described in detail herein.
The following example illustrates an embodiment of the present application for the purpose of separating and detecting impurities in a diborane-containing feed gas.
In this embodiment, the feed gas comprises diborane, carbon dioxide, oxygen, argon, nitrogen, methane and carbon monoxide. The first selector valve 22 is a ten-way valve, the second selector valve 23 and the third selector valve 24 are four-way valves, the first chromatographic column 25 is a capillary chromatographic column PLOT-Q with the specification of 30m × 0.53mm × 20um, and the first chromatographic column 25 is arranged at the position of the auxiliary column box; the second chromatographic column 26 and the third chromatographic column 27 are molecular sieve chromatographic columns with the specification of 25m multiplied by 0.53mm, and the second chromatographic column 26 and the third chromatographic column 27 are arranged at the position of the main column box.
(II) when gas analysis is performed, the operating temperature of each device is shown in Table 1:
TABLE 1 working temp. METER for EQUIPMENT
(III) cutting off the valve control time
The first set time is 2.97 minutes, i.e., the second selector valve 23 and the third selector valve 24 are placed in the first state 2.97 minutes after the first selector valve 22 and the second selector valve 23 are placed in the second state.
The second set time is 5 minutes, and the third selector valve 24 is placed in the second state 5 minutes after the second selector valve 23 and the third selector valve 24 are placed in the first state.
The analysis results of each impurity in the diborane-containing raw material gas obtained by the analysis system and the analysis method under the above parameters are shown in table 2, and the obtained chromatogram is shown in fig. 3.
As can be seen from table 2 and fig. 3, the impurities such as carbon dioxide, oxygen, argon, nitrogen, methane, carbon monoxide, etc. in the feed gas are well separated, the influence of diborane on the impurities is eliminated, the separation effect and the peak shape are good, and the qualitative and quantitative requirements can be completely met. That is, the system can accurately analyze the content of each impurity in the raw material gas containing diborane.
Table 2 analysis results of respective impurities in diborane-containing raw material gas
In addition, the inventors have verified the accuracy and precision of the analysis system and the analysis method provided in the present application.
Since it is difficult to prepare a standard gas containing carbon dioxide, oxygen, argon, nitrogen, methane and carbon monoxide in diborane in actual work, the inventors have used helium as the balance gas to prepare a mixed gas containing fixed contents of carbon dioxide, oxygen, argon, nitrogen, methane and carbon monoxide, i.e., a content of 5.00 × 10 -6 The multi-component gas mixture with mol/mol concentration is used for carrying out repeatability tests, the peak area result obtained in each test is shown in table 3, and the chromatogram generated by using one test is shown in fig. 4:
TABLE 3 peak area for repeatability test
As can be seen from Table 3, the repeatability of the peak area of each component is less than 2%, that is, the content of each impurity obtained by using the system has no chance, so that the system can be determined to have good precision and completely meet the requirement of quantitative accuracy. As can be seen from fig. 4, compared with the chromatogram of each impurity in the raw material gas containing diborane, the degree of conformity is high, which indicates that the analysis system and the analysis method provided by the application have higher precision.
In addition to the above experiments, the inventors have also studied the detection limit of the analysis system provided in the present application.
In the experiment, the inventor adopts 5.05X 10 -6 The detection limit of argon standard gas in helium with mol/mol concentration is calculated, the baseline noise of a chromatograph is 0.0002nA, the response peak height of argon is 0.27nA, and the detection limit is calculated by adopting 10 times of noise as follows: 5.05X 10 -6 mol/mol×0.0002×10/0.27＝0.037×10 -6 mol/mol, it can be seen that the analytical system provided by the present application can meet the detection requirement of diborane with the purity of 6N.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising a …" does not exclude the presence of additional like elements in a process, method, article, or apparatus that comprises the element.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, and not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. An analysis system for impurities in a diborane-containing feed gas, comprising:
the device comprises a detector (1) and a control unit, wherein the detector is used for detecting the content of each impurity in a raw material gas to be analyzed, the raw material gas to be analyzed comprises diborane and impurities, and the impurities comprise carbon dioxide;
a first channel (2) comprising a quantitative ring (21), a first selector valve (22), a second selector valve (23), a third selector valve (24), a first chromatographic column (25), a second chromatographic column (26) and a third chromatographic column (27), wherein the quantitative ring (21) is used for containing a fixed volume of feed gas to be analyzed, and the first selector valve (22), the second selector valve (23) and the third selector valve (24) respectively have a first state and a second state which can be switched; the first chromatographic column (25) is used for separating carbon dioxide from the feed gas to be analyzed to obtain a carbon dioxide-free feed gas, and the second chromatographic column (26) and the third chromatographic column (27) are used for separating diborane and other impurities from the carbon dioxide-free feed gas;
a second passage (3) connected to the first selector valve (22), the second selector valve (23), the third selector valve (24), and the detector (1), the second passage (3) being for supplying a carrier gas;
by switching the states of the first selector valve (22), the second selector valve (23), and the third selector valve (24), the carbon dioxide, diborane, and other impurities are sequentially separated by the first chromatography column (25), the second chromatography column (26), and the third chromatography column (27), and the content of each impurity is detected by the detector (1).
2. The system according to claim 1, wherein the first selector valve (22) is a ten-way valve, and the second selector valve (23) and the third selector valve (24) are both four-way valves;
the ten-way valve comprises ten interfaces, and each four-way valve comprises four interfaces.
3. The system of claim 2, wherein when the first selector valve (22) is in the first state, the first port of the first selector valve (22) is connected to the second port, the third port is connected to the fourth port, the fifth port is connected to the sixth port, the seventh port is connected to the eighth port, and the ninth port is connected to the tenth port; when the first selector valve (22) is in a second state, a second interface of the first selector valve (22) is connected with a third interface, a fourth interface is connected with a fifth interface, a sixth interface is connected with a seventh interface, an eighth interface is connected with a ninth interface, and a tenth interface is connected with the first interface;
when the second selector valve (23) is in a first state, a first interface and a fourth interface of the second selector valve (23) are connected, and a second interface and a third interface of the second selector valve are connected; when the second selector valve (23) is in a second state, a first interface of the second selector valve (23) is connected with the second interface, and a third interface of the second selector valve is connected with the fourth interface;
when the third selector valve (24) is in the first state, the first interface and the fourth interface of the third selector valve (24) are connected, and the second interface and the third interface are connected; when the third selector valve (24) is in the second state, the first interface and the second interface of the third selector valve (24) are connected, and the third interface and the fourth interface are connected.
4. A system according to claim 3, characterized in that when the first selector valve (22) is in the first state, the inlet end of the first passage (2) is connected to the second port of the first selector valve (22), the first port of the first selector valve (22) is connected to one end of the dosing ring (21), the other end of the dosing ring (21) is connected to the fourth port of the first selector valve (22), and the third port of the first selector valve (22) is open to the outside.
5. The system according to claim 3, wherein, when the first selector valve (22) and the second selector valve (23) are in the second state, the tenth port of the first selector valve (22) is in communication with the carrier gas, the first port of the first selector valve (22) is connected to one end of the dosing ring (21), the other end of the dosing ring (21) is connected to the fourth port of the first selector valve (22), the fifth port of the first selector valve (22) is connected to the inlet port of the first chromatography column (25), the outlet port of the first chromatography column (25) is connected to the ninth port of the first selector valve (22), the eighth port of the first selector valve (22) is connected to the first port of the second selector valve (23), and the second port of the second selector valve (23) is connected to the inlet port of the detector (1).
6. A system according to claim 3, characterized in that when the first selector valve (22) is in the second state and the second selector valve (23) and the third selector valve (24) are in the first state, the tenth port of the first selector valve (22) is connected to the second passage (3), the first port of the first selector valve (22) is connected to one end of the dosing ring (21), the other end of the dosing ring (21) is connected to the fourth port of the first selector valve (22), the fifth port of the first selector valve (22) is connected to the inlet port of the first chromatography column (25), the outlet port of the first chromatography column (25) is connected to the ninth port of the first selector valve (22), the eighth port of the first selector valve (22) is connected to the first port of the second selector valve (23), and the fourth port of the second selector valve (23) is connected to the first port of the third selector valve (24), and the fourth port of the second selector valve (23) is connected to the third port of the third selector valve (24).
7. A system according to claim 3, characterized in that when the first selector valve (22) and the third selector valve (24) are in the second state and the second selector valve (23) is in the first state, the tenth port of the first selector valve (22) is connected to the second passage (3), the first port of the first selector valve (22) is connected to one end of the dosing ring (21), the other end of the dosing ring (21) is connected to the fourth port of the first selector valve (22), the fifth port of the first selector valve (22) is connected to the inlet port of the first chromatographic column (25), the outlet port of the first chromatographic column (25) is connected to the ninth port of the first selector valve (22), the eighth port of the first selector valve (22) is connected to the first port of the second selector valve (23), the fourth port of the second selector valve (23) is connected to the first port of the third selector valve (24), and the third port of the selector valve (24) is connected to the detector (1).
8. A system according to claim 3, characterized in that said second path (3) comprises five gas-carrying lines; wherein, the first and the second end of the pipe are connected with each other,
the outlet end of the first gas-carrying pipeline (31) is connected with the tenth interface of the first selector valve (22);
the outlet end of the second gas carrying pipeline (32) is connected with a seventh interface of the first selector valve (22);
the outlet end of the third gas carrying pipeline (33) is connected with a third interface of the second selector valve (23);
the outlet end of the fourth gas carrying pipeline (34) is connected with the third interface of the third selector valve (24);
the outlet end of the fifth gas-carrying line (35) is connected to the detector (1).
9. A method for analyzing impurities in a diborane-containing raw gas, when applied to the system for analyzing impurities in a diborane-containing raw gas according to any one of claims 1 to 8, the method comprising:
feeding the feed gas to be analyzed into the dosing ring (21) through the first selection valve (22) while the first selection valve (22) is placed in a first state;
when the first selector valve (22) and the second selector valve (23) are placed in a second state, performing: introducing the feed gas to be analyzed in the quantification ring (21) into the first chromatographic column (25) using the carrier gas; separating the carbon dioxide and the carbon dioxide-free feed gas in sequence by means of the first chromatographic column (25); sending the separated carbon dioxide to the detector (1) for detection;
after the first selector valve (22) and the second selector valve (23) are placed in the second state for a first set time, placing the second selector valve (23) and the third selector valve (24) in the first state to introduce the carbon dioxide-free feed gas from the first chromatography column (25) into the second chromatography column (26); sequentially separating diborane and other impurities by using the second chromatographic column (26); discharging the separated diborane to the outside;
after the second selector valve (23) and the third selector valve (24) are placed in the first state for a second set time, placing the third selector valve (24) in the second state to introduce the remaining gas in the second chromatography column (26) into the third chromatography column (27); sequentially separating each gas in the residual gas by using the third chromatographic column (27); and introducing each separated gas into the detector (1) for detection.
10. The method of claim 9, wherein the first setting time is set according to:
the whole carbon dioxide separated by the first chromatographic column (25) flows out of the second selector valve (23), and the carbon dioxide-free feed gas does not flow into the second selector valve (23); and/or
The second setting time is set according to the following steps:
the diborane separated from the second chromatographic column (26) partially or totally flows out of the third selection valve (24), and other impurities except the diborane do not flow into the third selection valve (24).
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| CN111380988A (en) * | 2020-03-17 | 2020-07-07 | 中国测试技术研究院化学研究所 | Gas chromatograph for measuring content of impurities in hydrogen and detection method |
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