CN102928154A - Method for reducing error in polar altitude vacuum measurement of ESD (Electro Simulated Desorption) neutral particles - Google Patents
Method for reducing error in polar altitude vacuum measurement of ESD (Electro Simulated Desorption) neutral particles Download PDFInfo
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- CN102928154A CN102928154A CN2012104904167A CN201210490416A CN102928154A CN 102928154 A CN102928154 A CN 102928154A CN 2012104904167 A CN2012104904167 A CN 2012104904167A CN 201210490416 A CN201210490416 A CN 201210490416A CN 102928154 A CN102928154 A CN 102928154A
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Abstract
The invention discloses a method for reducing error in polar altitude vacuum measurement of ESD (Electro Simulated Desorption) neutral particles, and belongs to the field of measurement. Devices adopted in the method include a vacuum valve, an ionization gauge, a vacuum chamber, a vacuum pump group and a quadrupole mass spectrograph, wherein the vacuum valve, the ionization gauge, the vacuum pump group and the quadrupole mass spectrograph are respectively connected with the vacuum chamber; the quadrupole mass spectrograph is capable of separating electron excitation desorption ions and gas-phase ions and an energy analyzer is installed between an ion source and a quadrupole rod; the vacuum valve is of a full metal structure; and the lower measurement limit of the ionization gauge is 10-10Pa magnitude. By utilizing the method, the problem that in the full-pressure measurement, the ionization gauge and the like can effectively separate ESD ions and gas phase ions but cannot discriminate ions generated from ESD neutral particles doped in the gas phase ions is solved; the error in polar altitude vacuum measurement is reduced; and the lower limit in accurate measurement is extended.
Description
Technical field
The present invention relates to a kind of Electron Excitation desorption (Electron stimulated desorption that reduces, ESD) the extra-high vacuum measuring method of neutral particle error, particularly adopt to have the vacuum measurement method that energy analyzer structure quadrupole mass spectrometer is realized superelevation/extra-high vacuum system, belong to fields of measurement.
Background technology
The gate surface ESD effect of hot cathode ioization gauge can produce ESD ion and ESD neutral particle, and ESD ion and gaseous ion have energy difference.Document " development of extra-high vacuum technology, " aerospace instrumentation technology " the 29th volume, the 5th phase in 2009, the 71st page～76 pages " has been introduced multiple effective separation ESD ion, reduces the extra-high vacuum ionization gauge that extra-high vacuum Restriction of the Measuring factor is the ESD effect.The document is pointed out, in extra-high vacuum is measured, ESD effect and soft x-ray effect, the negative electrode effect of giving vent to anger together is considered to affect the key constraints of hot cathode ioization gauge extra-high vacuum measurement lower limit, usually the extra-high vacuum ionization gauge of different structure utilizes the energy difference of ESD ion and gaseous ion to realize two kinds of ion isolation, reaches the purpose of extending measurement lower limit and improving accuracy of measurement.
The advantage that adopts this type of extra-high vacuum ionization gauge to measure is effectively to avoid the measuring error of ESD ion introducing.Weak point is to work as the extreme pressure of vacuum system less than 10
-8During Pa, the ion that the ESD neutral particle produces has identical energy with gaseous ion, and ESD neutral particle component is much larger than ESD ion component usually, and this type of extra-high vacuum ionization gauge can't be distinguished ion and the gaseous ion that the ESD neutral particle produces, and can't realize the extra-high vacuum Measurement accuracy.
Summary of the invention
The object of the present invention is to provide a kind of extra-high vacuum measuring method that reduces Electron Excitation desorption neutral particle error, described method solved total pressure measure in extractor gauge etc. can effective separation ESD ion and gaseous ion, but can not distinguish the problem that the ESD neutral particle that mixes in the gaseous ion produces ion; Reduce the error that extra-high vacuum is measured, extended the lower limit of Measurement accuracy.
Purpose of the present invention is realized by following technical scheme:
A kind of extra-high vacuum measuring method that reduces Electron Excitation desorption neutral particle error, the device that described method adopts comprises: vacuum valve, ionization gauge, vacuum chamber, vacuum pump group and quadrupole mass spectrometer; Wherein, vacuum valve, ionization gauge, vacuum pump group, quadrupole mass spectrometer link to each other with vacuum chamber respectively;
Described four-electrode spectrum is counted separable Electron Excitation desorption ion that energy analyzer is housed between ion gun and the quadrupole rod and the quadrupole mass spectrometer of gaseous ion;
Described vacuum valve is all-metal construction;
The measurement lower limit of described ionization gauge is 10
-10The Pa magnitude;
Described method step is as follows:
(1) keeping vacuum valve is closed condition, opens the vacuum pump group, and vacuum chamber is bled;
(2) be down to 10 when the vacuum tightness of vacuum chamber
-6During the Pa magnitude, whole device is carried out bakeout degassing, vacuum valve, ionization gauge, vacuum chamber and quadrupole mass spectrometer rise to respectively separately the highest baking temperature with 30 ℃/h uniform speed respectively, kept 60～80 hours, wherein, the highest baking temperature of vacuum valve, ionization gauge and quadrupole mass spectrometer is 150 ℃, and the highest baking temperature of vacuum chamber is 350 ℃; After vacuum chamber is down to 150 ℃ gradually with 30 ℃/h uniform speed, to ionization gauge and quadrupole mass spectrometer degasification 3～5 minutes, vacuum valve, ionization gauge, vacuum chamber and quadrupole mass spectrometer are down to room temperature with 30 ℃/h uniform speed simultaneously, then continuous air extraction, measure vacuum tightness in the vacuum chamber with ionization gauge, until the final vacuum in the vacuum chamber reaches 10
-9The Pa order of magnitude is closed the vacuum pump group;
(3) open quadrupole mass spectrometer, stablize more than 1～3 hour;
(4) reflector voltage is the gaseous ion corresponding voltage in the energy analyzer of setting quadrupole mass spectrometer, so that the ion that only has gaseous ion and Electron Excitation desorption neutral particle to produce can pass through, ion flow valuve corresponding to record different quality number spectrum peak, and the gas componant in definite vacuum chamber;
(5) reflector voltage is Electron Excitation desorption ion corresponding voltage in the energy analyzer of setting quadrupole mass spectrometer, so that only have Electron Excitation desorption ion to pass through, and Electron Excitation desorption ion flow valuve corresponding to record different quality number spectrum peak; And the vacuum chamber composition of gases within of determining in the refer step (4) determines wherein may cause the gas componant of Electron Excitation desorption ion and neutral particle generation;
(6) gas componant that may cause Electron Excitation desorption ion and neutral particle to produce of determining according to step (5), provide gas componant spectrum peak each fragment peak relative abundance coefficient with reference to the quadrupole mass spectrometer handbook, calculate the vacuum chamber composition of gases within to the contribution amount of each fragment peak ion flow valuve;
(7) utilize the ion flow valuve of mass number fragment peak corresponding with step (6) in the step (4) to deduct the result of calculation of step (6), obtain the ion flow valuve that actual Electron Excitation desorption neutral particle produces;
(8) each partial pressure ion flow valuve sum of quadrupole mass spectrometer deducts the ion flow valuve that actual Electron Excitation desorption neutral particle produces in the step (7) in the step (4), obtains accurate extra-high vacuum measurement result.
Principle:
The method of the invention is utilized the energy difference between ESD ion and the gaseous ion, realizes the separation of the two, when reflector voltage in the energy analyzer is set as ESD ion corresponding voltage, only has the ESD ion to pass through; When reflector voltage in the energy analyzer was set as the gaseous ion corresponding voltage, the ion that only has gaseous ion and ESD neutral particle to produce can pass through.
Beneficial effect
(1) the present invention measures the ion current that the ESD neutral particle produces by the quadrupole mass spectrometer quadrupole mass spectrometer that utilization has the energy analyzer structure, solved total pressure measure in extractor gauge etc. can effective separation ESD ion and gaseous ion, but can not distinguish the problem that the ESD neutral particle that mixes in the gaseous ion produces ion.
(2) the method for the invention has reduced the error that extra-high vacuum is measured, and has extended the lower limit of Measurement accuracy.
Description of drawings
Fig. 1 is the apparatus structure schematic diagram that the method for the invention adopts;
Wherein, 1-vacuum valve, 2-ionization gauge, 3-vacuum chamber, 4-vacuum pump group, 5-quadrupole mass spectrometer.
Embodiment
Below in conjunction with the drawings and specific embodiments in detail the present invention is described in detail, but is not limited to this.
A kind of extra-high vacuum measuring method that reduces Electron Excitation desorption neutral particle error, the device that described method adopts comprises: vacuum valve 1, ionization gauge 2, vacuum chamber 3, vacuum pump group 4 and quadrupole mass spectrometer 5; Wherein, vacuum valve 1, ionization gauge 2, vacuum pump group 4, quadrupole mass spectrometer 5 link to each other with vacuum chamber 3 respectively, as shown in Figure 1;
Described quadrupole mass spectrometer 5 is for being equipped with the separable Electron Excitation desorption ion of energy analyzer and the quadrupole mass spectrometer 5 of gaseous ion between ion gun and the quadrupole rod;
Described vacuum valve 1 is all-metal construction;
The measurement lower limit of described ionization gauge 2 is 10
-10The Pa magnitude;
Described method step is as follows:
(1) keeping vacuum valve 1 is closed condition, opens vacuum pump group 4, and vacuum chamber 3 is bled;
(2) be down to 10 when the vacuum tightness of vacuum chamber 3
-6During the Pa magnitude, whole device is carried out bakeout degassing, vacuum valve 1, ionization gauge 2, vacuum chamber 3 and quadrupole mass spectrometer 5 rise to respectively separately the highest baking temperature with 30 ℃/h uniform speed respectively, kept 72 hours, wherein, the highest baking temperature of vacuum valve 1, ionization gauge 2 and quadrupole mass spectrometer 5 is 150 ℃, and the highest baking temperature of vacuum chamber 3 is 350 ℃; After vacuum chamber 3 is down to 150 ℃ gradually with 30 ℃/h uniform speed, utilize the control module of the two to remove airway dysfunction degasification 3 minutes to ionization gauge 2 and quadrupole mass spectrometer 5, vacuum valve 1, ionization gauge 2, vacuum chamber 3 and quadrupole mass spectrometer 5 are down to room temperature with 30 ℃/h uniform speed simultaneously, then continuous air extraction is 48 hours, measure vacuum chamber 3 interior vacuum tightnesss with ionization gauge 2, until the final vacuum in the vacuum chamber 3 reaches 8.26 * 10
-9Pa closes vacuum pump group 4, and corresponding quadrupole mass spectrometer 5 gaseous ion streams are 9.32 * 10
-12A;
(3) open quadrupole mass spectrometer 5, stablized 1 hour;
(4) setting quadrupole mass spectrometer 5 energy analyzer reflector voltages is gaseous ion corresponding voltage, i.e. V
D=105V carries out simulated spectrum scanning in the mass range of (1～50) amu, record corresponding gaseous ion flow valuve, and is as shown in table 1:
Table 1
| Gaseous ion | H + | H 2 + | C + | O + | OH + | H 2O + | CO + | O 2 + |
| Ion flow valuve ion current value (* 10 -11A） | 1.97 | 83.02 | 0.56 | 2.53 | 0.66 | 1.40 | 2.63 | 0.47 |
(5) setting quadrupole mass spectrometer 5 energy analyzer reflector voltages is ESD ion corresponding voltage, i.e. V
D=60V carries out simulated spectrum scanning in the mass range of (1～50) amu, record corresponding ESD ion flow valuve, and is as shown in table 2:
Table 2
| The ESD ion | H + | H 2 + | O + |
| Ion flow valuve (* 10 -11A） | 0.09 | 0.05 | 0.28 |
(6) determine that according to step (4), (5) measurement result vacuum chamber 3 interior main gas componants are H
2, O
2, H
2O, CO;
(7) determine gas componant according to step (6), provide gas componant spectrum peak each fragment peak relative abundance coefficient with reference to quadrupole mass spectrometer 5 handbooks, for example, H
2It is H:0.008, H2:1.00 that correspondence is respectively composed the peak relative coefficient.Can calculate the gas with various molecule to the contribution amount of the ion flow valuve of corresponding ion;
(8) utilize the gaseous ion flow valuve that comprises ESD neutral particle component to deduct gas molecule contribution amount in the step (7), obtain the corresponding ion flow valuve of ESD neutral particle, as shown in table 3:
Table 3
| The ESD neutral particle | H | C | O | OH |
| Ion flow valuve ion current value (* 10 -11A） | 1.17 | 0.42 | 2.28 | 0.26 |
(9) quadrupole mass spectrometer 5 each partial pressure ion flow valuve sum deduct ESD neutral ion flow valuve in the step (8) in the step (5), obtain extra-high vacuum and measure ion current I=8.91 * 10
-12A.
The present invention includes but be not limited to above embodiment, every any being equal to of carrying out under the principle of spirit of the present invention, replace or local improvement, all will be considered as within protection scope of the present invention.
Claims (5)
1. extra-high vacuum measuring method that reduces Electron Excitation desorption neutral particle error, it is characterized in that: described method step is as follows:
(1) opens vacuum pump group (4), vacuum chamber (3) is bled;
(2) be down to 10 when the vacuum tightness of vacuum chamber (3)
-6During the Pa magnitude, whole device is carried out bakeout degassing, vacuum valve (1), ionization gauge (2), vacuum chamber (3) and quadrupole mass spectrometer (5) rise to respectively separately the highest baking temperature with 30 ℃/h uniform speed respectively, kept 60～80 hours, wherein, the highest baking temperature of vacuum valve (1), ionization gauge (2) and quadrupole mass spectrometer (5) is 150 ℃, and the highest baking temperature of vacuum chamber (3) is 350 ℃; After vacuum chamber (3) is down to 150 ℃ gradually with 30 ℃/h uniform speed, to ionization gauge (2) and quadrupole mass spectrometer (5) degasification 3～5 minutes, vacuum valve (1), ionization gauge (2), vacuum chamber (3) and quadrupole mass spectrometer (5) are down to room temperature with 30 ℃/h uniform speed simultaneously, then continuous air extraction, measure the interior vacuum tightness of vacuum chamber (3) with ionization gauge (2), until the final vacuum in the vacuum chamber (3) reaches 10
-9The Pa order of magnitude is closed vacuum pump group (4);
(3) open quadrupole mass spectrometer (5), stablize more than 1～3 hour;
(4) reflector voltage is the gaseous ion corresponding voltage in the energy analyzer of setting quadrupole mass spectrometer (5), so that the ion that only has gaseous ion and Electron Excitation desorption neutral particle to produce can pass through, ion flow valuve corresponding to record different quality number spectrum peak, and the gas componant in definite vacuum chamber (3);
(5) reflector voltage is Electron Excitation desorption ion corresponding voltage in the energy analyzer of setting quadrupole mass spectrometer (5), so that only have Electron Excitation desorption ion to pass through, and Electron Excitation desorption ion flow valuve corresponding to record different quality number spectrum peak; And vacuum chamber (3) composition of gases within of determining in the refer step (4) determines wherein may cause the gas componant of Electron Excitation desorption ion and neutral particle generation;
(6) gas componant that may cause Electron Excitation desorption ion and neutral particle to produce of determining according to step (5), provide gas componant spectrum peak each fragment peak relative abundance coefficient with reference to quadrupole mass spectrometer (5) handbook, calculate vacuum chamber (3) composition of gases within to the contribution amount of each fragment peak ion flow valuve;
(7) utilize the ion flow valuve of mass number fragment peak corresponding with step (6) in the step (4) to deduct the result of calculation of step (6), obtain the ion flow valuve that actual Electron Excitation desorption neutral particle produces;
(8) each partial pressure ion flow valuve sum of quadrupole mass spectrometer (5) deducts the ion flow valuve that actual Electron Excitation desorption neutral particle produces in the step (7) in the step (4), obtains accurate extra-high vacuum measurement result.
2. a kind of extra-high vacuum measuring method that reduces Electron Excitation desorption neutral particle error according to claim 1 is characterized in that: the device that described method adopts comprises: vacuum valve (1), ionization gauge (2), vacuum chamber (3), vacuum pump group (4) and quadrupole mass spectrometer (5); Wherein, vacuum valve (1), ionization gauge (2), vacuum pump group (4), quadrupole mass spectrometer (5) link to each other with vacuum chamber (3) respectively.
3. a kind of extra-high vacuum measuring method that reduces Electron Excitation desorption neutral particle error according to claim 1 is characterized in that: described quadrupole mass spectrometer (5) is for being equipped with the separable Electron Excitation desorption ion of energy analyzer and the quadrupole mass spectrometer (5) of gaseous ion between ion gun and the quadrupole rod.
4. a kind of extra-high vacuum measuring method that reduces Electron Excitation desorption neutral particle error according to claim 1, it is characterized in that: described vacuum valve (1) is all-metal construction.
5. a kind of extra-high vacuum measuring method that reduces Electron Excitation desorption neutral particle error according to claim 1, it is characterized in that: the measurement lower limit of described ionization gauge (2) is 10
-10The Pa magnitude.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113378755A (en) * | 2021-06-24 | 2021-09-10 | 浙江大学 | Gas phase ion mobility spectrometry data spectral peak automatic identification method based on contour map |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030209666A1 (en) * | 2002-05-10 | 2003-11-13 | Hitachi, Ltd. | Ion source and mass spectrometric apparatus |
| CN1856651A (en) * | 2003-09-26 | 2006-11-01 | 英国氧气集团有限公司 | Detection of contaminants within fluid pumped by a vacuum pump |
| CN201152868Y (en) * | 2007-12-28 | 2008-11-19 | 中国航天科技集团公司第五研究院第五一〇研究所 | Relative response calibration system for four polar mass spectra gauge |
| CN101710017A (en) * | 2009-12-17 | 2010-05-19 | 中国航天科技集团公司第五研究院第五一○研究所 | Leak detection device and method of vacuum system |
| CN101713696A (en) * | 2009-12-17 | 2010-05-26 | 中国航天科技集团公司第五研究院第五一○研究所 | Device and method for calibrating flow-dividing vacuum leaking hole |
| CN101963596A (en) * | 2010-09-01 | 2011-02-02 | 中国科学院广州地球化学研究所 | Rare gas determination system based on quadrupole mass spectrometer |
| EP0932184B1 (en) * | 1998-01-22 | 2011-05-25 | Leybold Inficon, Inc. | Ion collector assembly |
-
2012
- 2012-11-27 CN CN201210490416.7A patent/CN102928154B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0932184B1 (en) * | 1998-01-22 | 2011-05-25 | Leybold Inficon, Inc. | Ion collector assembly |
| US20030209666A1 (en) * | 2002-05-10 | 2003-11-13 | Hitachi, Ltd. | Ion source and mass spectrometric apparatus |
| CN1856651A (en) * | 2003-09-26 | 2006-11-01 | 英国氧气集团有限公司 | Detection of contaminants within fluid pumped by a vacuum pump |
| CN201152868Y (en) * | 2007-12-28 | 2008-11-19 | 中国航天科技集团公司第五研究院第五一〇研究所 | Relative response calibration system for four polar mass spectra gauge |
| CN101710017A (en) * | 2009-12-17 | 2010-05-19 | 中国航天科技集团公司第五研究院第五一○研究所 | Leak detection device and method of vacuum system |
| CN101713696A (en) * | 2009-12-17 | 2010-05-26 | 中国航天科技集团公司第五研究院第五一○研究所 | Device and method for calibrating flow-dividing vacuum leaking hole |
| CN101963596A (en) * | 2010-09-01 | 2011-02-02 | 中国科学院广州地球化学研究所 | Rare gas determination system based on quadrupole mass spectrometer |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113378755A (en) * | 2021-06-24 | 2021-09-10 | 浙江大学 | Gas phase ion mobility spectrometry data spectral peak automatic identification method based on contour map |
| CN113378755B (en) * | 2021-06-24 | 2022-06-24 | 浙江大学 | Gas phase ion mobility spectrometry data spectral peak automatic identification method based on contour map |
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