CN219456066U - Analysis device for trace impurities in germane - Google Patents
Analysis device for trace impurities in germane Download PDFInfo
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- CN219456066U CN219456066U CN202320216081.3U CN202320216081U CN219456066U CN 219456066 U CN219456066 U CN 219456066U CN 202320216081 U CN202320216081 U CN 202320216081U CN 219456066 U CN219456066 U CN 219456066U
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Abstract
The utility model provides an analysis device for trace impurities in germane. The analysis device includes: the sample injection system is used for inputting a germane sample; the first separation column is communicated with the sample injection system and is used for separating first-class impurities, germane and second-class impurities from the germane sample successively; a second separation column in communication with the first separation column for separating the first type of impurities from the first separation column; a third separation column in communication with the first separation column for separating the second type of impurities from the first separation column; the first detector is communicated with the second separation column through a pipeline and is used for detecting the content of each component in the first impurities; and the second detector is communicated with the third separation column through a pipeline and is used for detecting the content of each component in the second type of impurities. The analysis device provided by the utility model can realize the full analysis of impurities in germane by one sample injection, and has the advantages of simplicity, easiness in operation and high analysis speed.
Description
Technical Field
The utility model belongs to the field of gas analysis, and particularly relates to an analysis device for analyzing trace impurities in germane.
Background
Germane is used as an important raw material in chemical vapor deposition process, and is mainly applied to manufacturing electronic components such as integrated circuits, photoelectric devices and the like. In addition, germane can also be used as an important precursor gas of the solar cell, so that the efficiency of the silicon-based thin film solar cell is improved.
At present, the purity of germane applied to the electronic industry is up to 5N (99.999%) or more, and along with the development of the electronic industry, the requirements of precise electronic components on raw materials are more severe, so that the content of each impurity gas in germane needs to be more strictly controlled. It is therefore a critical issue how to accurately, comprehensively and reliably detect the content of individual trace impurities in germane.
The semiconductor industry is not limited to the H related in national standard (GB/T31987-2015) 2 \O 2 \N 2 \Ar\CH 4 \CO\CO 2 The impurities are defined in terms of the impurities such as digermane and trigermane in germaneIs also increasingly stringent. In the prior art, H in germane is realized without one sample injection 2 、O 2 、N 2 、Ar、CH 4 、CO、CO 2 And a method for the total quantitative analysis of all impurities such as digermane and trigermane.
Disclosure of Invention
In view of the above problems in the prior art, the present utility model provides an analysis device for trace impurities in germane.
According to the present utility model, there is provided an analysis device for trace impurities in germane, comprising:
the sample injection system is used for inputting a germane sample;
the first separation column is communicated with the sample injection system and is used for separating first-class impurities, germane and second-class impurities from the germane sample successively; the first type of impurities comprises one or more impurities selected from the group consisting of hydrogen, nitrogen, oxygen, argon, methane, carbon monoxide and carbon dioxide, and the second type of impurities comprises one or more impurities selected from the group consisting of digermane and trigermane;
a second separation column in communication with the first separation column for separating the first type of impurities from the first separation column;
a third separation column in communication with the first separation column for separating the second type of impurities from the first separation column;
the first detector is communicated with the second separation column through a pipeline and is used for detecting the content of each component in the first impurities;
and the second detector is communicated with the third separation column through a pipeline and is used for detecting the content of each component in the second type of impurities.
Preferably, the sample injection system comprises:
a sample inlet;
the first multi-way valve is communicated with the sample inlet through a pipeline;
one end of the quantitative pipe is communicated with the first multi-way valve through a pipeline, and the other end of the quantitative pipe is communicated with the first separation column through a pipeline.
Preferably, the first separation column is in communication with the second separation column via a conduit via a second multi-way valve; the first separation column and the third separation column are communicated through a pipeline sequentially through a second multi-way valve and a third multi-way valve; the interfaces of the second multi-way valve comprise interfaces for introducing carrier gas, and the interfaces of the third multi-way valve comprise interfaces for venting and interfaces for introducing carrier gas; by controlling the second multi-way valve and the third multi-way valve, the first-class impurities separated by the first separation column can enter the second separation column, the germane separated by the first separation column is discharged from the third multi-way valve, and the second-class impurities separated by the first separation column can enter the third separation column.
Preferably, the first detector and the second detector are both helium ionization detectors with a detection limit of 1-10ppb.
Preferably, the carrier gas is high purity helium.
Preferably, the first separation column is a packed column with a length of 3-5 m, and the chromatographic column packing is a porous polymer.
Preferably, the second separation column is a packed column with a length of 3-4 m, and the chromatographic column packing is a carbon molecular sieve.
Preferably, the third separation column is a capillary column with the length of 20-60 m, and the chromatographic column filler is porous polymer.
Preferably, the tubing in contact with the germane sample is 316L and electropolished, and the tubing is 1/16 inch in size.
Preferably, in order to ensure that the sampling pressure is the same, a diaphragm valve is arranged on a pipeline between the sampling port and the first multi-way valve.
Preferably, the multi-way valve provided in the pipeline is a pneumatic valve.
The beneficial effects are that:
the analysis device provided by the utility model can be used for detecting the content of conventional impurities in the germane sample, further analyzing the content of trace impurity components such as the digermane, the trigermane and the like of the high-purity germane, and realizing the full quantitative analysis of various impurities such as hydrogen, nitrogen, oxygen, argon, methane, carbon monoxide, carbon dioxide, digermane, the trigermane and the like in the germane by one-time sample injection, and has the advantages of simplicity, easiness in operation and high analysis speed.
Drawings
Fig. 1 is a schematic diagram showing an analysis apparatus for trace impurities in germane according to example 1 of the present utility model.
1: a diaphragm valve;
2: a first multi-way valve;
3: a second multi-way valve;
4: a third multi-way valve;
5: a metering tube;
6: a first separation column;
7: a second separation column;
8: a third separation column;
9: a first detector;
10: and a second detector.
Detailed Description
The utility model is illustrated by the following examples with process conditions in use including but not limited to the following examples.
As shown in fig. 1, the analysis device for trace impurities in germane provided by the utility model mainly comprises: the sample injection system, the first separation column 6, the second separation column 7, the third separation column 8, the first detector 9 and the second detector 10. The sample injection system is used for inputting a germane sample to be analyzed. The first separation column 6 is communicated with the sample injection system and is used for separating the germane sample and separating and flowing out the first-class impurities, the germane and the second-class impurities in sequence; specifically, the first type of impurities comprises one or more impurities selected from the group consisting of hydrogen, nitrogen, oxygen, argon, methane, carbon monoxide and carbon dioxide, and the second type of impurities comprises one or more impurities selected from the group consisting of digermane and trigermane. The second separation column 7 is in communication with the first separation column 6 for separating the components of the first type of impurities separated from the first separation column 6. The third separation column 8 is in communication with the first separation column 6 for separating the components of the second type of impurities separated from the first separation column 6.
Further specifically, the sample injection system comprises a sample injection port, a first multi-way valve 2 and a dosing tube 5. The first multi-way valve 2 is in communication with the sample inlet via a pipeline, and the first multi-way valve 2 has a plurality of ports, for example, 6 ports, including a port for introducing carrier gas and a port for venting. One end of the metering tube 5 is communicated with the first multi-way valve 2 through a pipeline, and the other end is communicated with the first separation column 6 through a pipeline.
Further specifically, the first separation column 6 and the second separation column 7 are communicated by a pipe via the second multi-way valve 3; the first separation column 6 and the third separation column 8 are communicated with each other through the second multi-way valve 3 and the third multi-way valve 4 in sequence through pipelines. The second multi-way valve 3 and the third multi-way valve 4 each have a plurality of ports, for example, 4 ports each. The interfaces of the second multi-way valve 3 comprise interfaces for introducing carrier gas, and the interfaces of the third multi-way valve 4 comprise interfaces for venting and interfaces for introducing carrier gas. By controlling the second multi-way valve 3, the first separation column 6 and the second separation column 7 can be placed in a communication state, so that the first type impurities separated by the first separation column 6 can enter the second separation column 7 for continuous separation; by controlling the second multi-way valve 3 and the third multi-way valve 4, the first separation column 6 can be communicated with the interface of the third multi-way valve 4 for emptying, so that the germane separated in the first separation column 6 is discharged from the third multi-way valve 4; by controlling the second multi-way valve 3 and the third multi-way valve 4, the first separation column 6 and the third separation column 8 can be communicated, so that the second type of impurities separated by the first separation column 6 enter the third separation column 8 for continuous separation.
Further specifically, the first detector 9 and the second detector 10 may each be a helium ionization detector, and the detection limit is preferably 1 to 10ppb.
Preferably, the first separation column 6 is a packed column with a length of 3-5 m, wherein the chromatographic column packing is porous polymer; the second separation column 7 is a packed column with the length of 3-4 m, wherein the chromatographic column packing is a carbon molecular sieve; the third separation column 8 is a capillary column with the length of 20-60 m, wherein the chromatographic column filler is porous polymer.
Fig. 1 is a schematic structural diagram of an analysis apparatus for trace impurities in germane according to an embodiment of the present utility model.
In fig. 1, a diaphragm valve 1 is arranged on a pipeline between a sample inlet of a sample injection system and a first multi-way valve 2. The first multi-way valve 2 is a six-way valve, the second multi-way valve 3 is a four-way valve, and the third multi-way valve 4 is a four-way valve.
The first multi-way valve 2 is sequentially provided with a first interface (1), a second interface (2), a third interface (3), a fourth interface (4), a fifth interface (5) and a sixth interface (6) along the clockwise direction; the second interface (2) is a sample inlet, and the first interface (1) is a vent hole. The fourth interface (4) is a carrier gas inlet, the third interface (3) is connected with one end of the quantitative pipe 5, the sixth interface (6) is connected with the other end of the quantitative pipe 5, and the fifth interface (5) is connected with one end of the first separation column;
a seventh interface (7), an eighth interface (8), a ninth interface (9) and a tenth interface (a) are sequentially arranged on the second multi-way valve 3 along the clockwise direction; the seventh interface (7) is a carrier gas inlet, the ninth interface (9) is connected with the other end of the first separation column (6), the eighth interface (8) is connected with one end of the second separation column (7), the other end of the second separation column (7) is connected with the first detector (9) (helium ionization detector), and the tenth interface is connected with the third multi-way valve (4);
the third multi-way valve 4 is provided with an eleventh port in sequence along the clockwise directionTwelfth interface->Thirteenth interface->Fourteenth interface->Wherein the eleventh interface->Is connected with the tenth interface, the twelfth interface is +.>For the vent, thirteenth interface->For carrier gas inlet, fourteenth interface->Is connected to one end of the third separation column 8, and the other end of the third separation column 8 is connected to a second detector 10 (which is a helium ionization detector).
The analysis device shown in fig. 1, when performing analysis of trace impurities in a germane sample, may comprise the following steps:
and (3) sample injection: evacuating the sample inlet pipeline in the analysis device to 10 by an air extractor -5 Under Pa, purging with high purity helium (purity is above 6.5N) and negative pressure replacement, and after the concentration of residual gas, nitrogen and oxygen in the last sample is reduced to below 10ppb, inputting germane sample through a sample inlet and filling into a quantitative tube;
separating: the high-purity helium gas is used as carrier gas to be introduced into a first multi-way valve 2, a sample in a quantitative pipe 5 is sent into a first separation column 6 for separation, first impurities, germane and second impurities are separated and flow out successively, and the first impurities are sent into a second separation column 7 through a control valve; then the control valve is used for discharging most germane from the vent hole of the third multi-way valve 4; then the second type of impurities and possibly small amounts of germane enter a third separation column 8 through a control valve;
the detection step comprises: the sample separated by the second separation column 7 and the third separation column 8 is sent to a first detector 9 and a second detector 10, respectively, wherein the first detector 9 is used for detecting and analyzing the content of each component in the first type of impurities separated in the second separation column 7, and the second detector 10 is used for detecting and analyzing the content of each component in the small amount of germane and the second type of impurities possibly existing separated in the third separation column 8.
When the analysis device performs analysis of trace impurities in a germane sample, the analysis conditions thereof include, for example: quantitative tube volume: 25uL-1mL;
the pressure of the carrier gas is 6.5-8 bar;
the column temperature of the first separation column is 40-60 ℃;
the column temperature of the second separation column is 70-90 ℃;
the column temperature of the third separation column is 120-180 ℃;
the temperature of the helium ionization detector is 100-150 ℃.
Example 1
The analysis of high purity germane was performed using the analysis apparatus shown in fig. 1 according to the following procedure, and the description of the analysis apparatus shown in fig. 1 is referred to above, and will not be repeated here.
Step one: the germane sample to be measured is input from a sample inlet, enters the quantitative pipe 5 through a second interface (2) of the first multi-way valve 2 after passing through the diaphragm valve 1, and is output from the first interface (1) to purge and replace the quantitative pipe 5;
step two: after the replacement, the diaphragm valve 1 is opened, the state of the first multi-way valve 2 is switched from off to on, a sample in the carrier gas belt quantitative pipe 5 input from the fourth interface (4) sequentially passes through the third interface (3), the sixth interface (6), the fifth interface (5) enters the first separation column 6 for pre-separation, according to the outflow sequence, the first type of impurities (containing one or more impurities of hydrogen, oxygen, argon, nitrogen, methane, carbon monoxide and carbon dioxide) sequentially flows out of the first separation column 6, germane and the second type of impurities (containing one or more impurities of digermane and trigermane) sequentially flow out of the second multi-way valve 3 from off to on, and the first type of impurities which flow out of the first separation column 6 firstly enter the second separation column 7 from the ninth interface (9), the eighth interface (8) sequentially flows out of the first separation column 6; resetting the second multi-way valve 3, and carrying the first impurities into the second separation column 7 by carrier gas input from the seventh interface (7) for separation, and then entering the first detector 9 for detection;
step three: switching the state of the second multi-way valve 3 from on to off, and flowing germane out of the first separation column 6 through the ninth interface (9) to the tenth interface (d) and then through the eleventh interface (d)Twelfth interface>Large dischargePart of germane; then the state of the third multi-way valve 4 is switched from the closed state to the open state, and the impurities of the second type and the possible small amount of germane flowing out from the first separation column 6 flow out from the eleventh interface (9) to the tenth interface (d) and then flow out from the eleventh interface (d)>Fourteenth interface->Entering a third separation column 8; the third multi-way valve 4 is then reset, from thirteenth connection +.>The input carrier gas brings the second kind of impurities and possibly small amounts of germane into the third separation column 8 for separation, and then enters the second detector 10 for detection.
All valves were under high purity helium protection.
Pipeline valve system: all lines other than the chromatographic columns (i.e., first, second, and third separation columns) in contact with the germane sample gas were 316L and electropolished, with a line size of 1/16 inch; the first multi-way valve 2, the second multi-way valve 3 and the third multi-way valve 4 are under the protection of high-purity helium, so that no air is permeated to influence experimental results.
Chromatographic conditions: the volume of the metering tube 5 is 0.5mL, the carrier gas pressure is 7bar, the valve driving gas pressure is 5bar, the column temperature of the first separation column is 40 ℃, the column temperature of the second separation column is 80 ℃, the column temperature of the third separation column is 160 ℃, and the temperatures of the first detector 9 and the first detector 10 are 150 ℃.
First separation column 6: TENAX column 4m long and 1/8 inch outer diameter.
Second separation column 7: a carbon molecular sieve column 3m long and 1/8 inch in outer diameter.
Third separation column 8: MXT Q bond column 30m long and 0.53mm outer diameter.
The detection system comprises: detecting impurity content by helium ionization detector with detection limit of 1-10ppb.
Model of helium ionization detector: AGC NovaCHROM 1000.
Table 1: operating program
| Sequence number | Event 1 | Event 2 | Event 3 | Event 4 |
| 1 | 0min | 0min | 0.1min | 0.6～1.9min |
| 2 | 0.2min | 30min | 1.35～1.55min | 30min |
Note that: in the table, event 1 represents a diaphragm valve 1, event 2 represents a first multi-way valve 2, event 3 represents a second multi-way valve 3, and event 4 represents a third multi-way valve 4; the number 1 represents the valve opening, and the number 2 represents the valve closing; the times in the table represent the switching times of the valves.
The time of the first multi-way valve is opened, namely the formal sample injection time, is determined by the sample analysis requirement, and the time of the first multi-way valve is closed, namely the ending time of the sample analysis program, is determined by the sample analysis requirement.
The valve opening and closing time of the second multi-way valve is determined through repeated searching and finding for a plurality of experiments according to the retention time of each impurity. The "on" time is such that the first type of impurity (which comprises one or more of hydrogen, oxygen, argon, nitrogen, methane, carbon monoxide and carbon dioxide) exits the first separation column, i.e., will enter the second separation column, while the other components (germane and the second type of impurity (which comprises one or more of digermane, trigermane)) remain in the first separation column; the off time is when germane and a second type of impurity (which comprises one or more of digermane, trigermane) begin to flow out of the first separation column.
The valve opening and closing time of the third multi-way valve is determined experimentally according to the retention time of each impurity. The "on" time is such that a majority of the germane has been discharged and a small amount of the germane second type impurity (which comprises one or more of digermane, trigermane) is ready to enter the third separation column; the "off" time is the end time of the sample analysis program and is determined by the sample analysis requirements.
The analysis results are shown in table 2 below.
Table 2: analysis results
As shown above, the analysis device provided by the utility model can realize the complete analysis of impurities in germane by one sample injection, and has the advantages of simplicity, easiness in operation, low detection limit, good separation effect and high analysis speed.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While obvious variations or modifications are contemplated as falling within the scope of the present utility model.
Claims (9)
1. An analysis device for trace impurities in germane, the analysis device comprising:
the sample injection system is used for inputting a germane sample;
the first separation column is communicated with the sample injection system and is used for separating first-class impurities, germane and second-class impurities from the germane sample successively; the first type of impurities comprise one or more impurities selected from the group consisting of hydrogen, nitrogen, oxygen, argon, methane, carbon monoxide and carbon dioxide, and the second type of impurities comprise one or more impurities selected from the group consisting of digermane and trigermane;
a second separation column in communication with the first separation column for separating the first type of impurities from the first separation column;
a third separation column in communication with the first separation column for separating the second type of impurities from the first separation column;
a first detector in communication with the second separation column via a conduit for detecting the content of each component of the first type of impurity;
and the second detector is communicated with the third separation column through a pipeline and is used for detecting the content of each component in the second-class impurities.
2. The device for analyzing trace impurities in germane according to claim 1, wherein the device comprises a plurality of sensors,
the sample injection system comprises:
a sample inlet;
the first multi-way valve is communicated with the sample inlet through a pipeline;
and one end of the quantitative pipe is communicated with the first multi-way valve through a pipeline, and the other end of the quantitative pipe is communicated with the first separation column through a pipeline.
3. The device for analyzing trace impurities in germane according to claim 1 or 2, wherein,
the first separation column is communicated with the second separation column through a pipeline via a second multi-way valve; the first separation column and the third separation column are communicated with each other through a pipeline sequentially through the second multi-way valve and the third multi-way valve; the interfaces of the second multi-way valve comprise interfaces for introducing carrier gas, and the interfaces of the third multi-way valve comprise interfaces for venting and interfaces for introducing carrier gas; by controlling the second multi-way valve and the third multi-way valve, the first type of impurities separated by the first separation column can enter the second separation column, the germane separated by the first separation column is discharged from the third multi-way valve, and the second type of impurities separated by the first separation column can enter the third separation column.
4. The device for analyzing trace impurities in germane according to claim 1 or 2, wherein,
the first detector and the second detector are helium ionization detectors, and the detection limit is 1-10ppb.
5. The device for analyzing trace impurities in germane according to claim 3, wherein,
the carrier gas is high purity helium.
6. The device for analyzing trace impurities in germane according to claim 3, wherein,
the first separation column is a packed column with the length of 3-5 m, and the chromatographic column packing is porous polymer;
the second separation column is a packed column with the length of 3-4 m, and the chromatographic column filler is a carbon molecular sieve;
the third separation column is a capillary column with the length of 20-60 m, and the chromatographic column filler is porous polymer.
7. The device for analyzing trace impurities in germane according to claim 1, wherein the device comprises a plurality of sensors,
the tubing in contact with the germane sample was 316L and electropolished, with a tubing size of 1/16 inch.
8. The device for analyzing trace impurities in germane according to claim 2, wherein the device comprises a plurality of sensors,
and a diaphragm valve is arranged on a pipeline between the sample inlet and the first multi-way valve.
9. The device for analyzing trace impurities in germane according to claim 3, wherein,
the multi-way valve arranged in the pipeline is a pneumatic valve.
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