WO2016108451A2 - 비행시간 질량분석기 - Google Patents
비행시간 질량분석기 Download PDFInfo
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- WO2016108451A2 WO2016108451A2 PCT/KR2015/013252 KR2015013252W WO2016108451A2 WO 2016108451 A2 WO2016108451 A2 WO 2016108451A2 KR 2015013252 W KR2015013252 W KR 2015013252W WO 2016108451 A2 WO2016108451 A2 WO 2016108451A2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/10—Ion sources; Ion guns
- H01J49/14—Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers
- H01J49/147—Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers with electrons, e.g. electron impact ionisation, electron attachment
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/08—Electron sources, e.g. for generating photo-electrons, secondary electrons or Auger electrons
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/10—Ion sources; Ion guns
- H01J49/14—Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers
- H01J49/142—Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers using a solid target which is not previously vapourised
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J43/00—Secondary-emission tubes; Electron-multiplier tubes
- H01J43/04—Electron multipliers
- H01J43/06—Electrode arrangements
- H01J43/18—Electrode arrangements using essentially more than one dynode
- H01J43/24—Dynodes having potential gradient along their surfaces
- H01J43/246—Microchannel plates [MCP]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/26—Mass spectrometers or separator tubes
- H01J49/34—Dynamic spectrometers
- H01J49/40—Time-of-flight spectrometers
Definitions
- the present invention relates to a mass spectrometer, specifically to a time-of-flight mass spectrometer using a cold electron beam as an ionization source.
- the time-of-flight mass spectrometer can ionize molecules of different masses in a sample and measure the current of ions generated. Mass spectrometers can be classified into various forms depending on the method of separating ions.
- the time-of-flight mass spectrometer can analyze the mass using the flight time of the ions. For accuracy of mass spectrometry, electrons collide with the sample by minimizing the difference in ionization time.
- One object of the present invention is to provide an accurate time-of-flight mass spectrometer.
- One problem to be solved by the present invention is to provide a time-of-flight mass spectrometer suitable for miniaturization.
- the time-of-flight mass spectrometer of the present invention for solving the above problems includes an ionizer which receives an electron beam and emits ions; A cold electron supply unit injecting the electron beam into the ionization unit; An ion detector configured to sense the ions emitted from the ionizer; And an ion separation unit connecting the ionization unit and the ion detection unit, wherein the cold electron supply unit includes a microchannel plate that receives ultraviolet rays and emits the electron beams. Ions pass through the ion separation unit to reach the ion detection unit, and the ion separation unit may have a straight tube shape.
- the cold electron supply unit may further include a UV diode emitting the ultraviolet rays to the microchannel plate.
- the microchannel plate comprises a front plate for receiving the ultraviolet rays to generate electrons; And a backplane emitting the electron beam, wherein the electron beam may be the electrons multiply within the microchannel plate.
- the multiplication may be 10 4 times to 10 9 times.
- the cold electron supply unit may further include a channeltron electron multiplier that multiply the electron beam emitted from the microchannel plate.
- the channeltron electron multiplier may multiply the electron beam emitted from the microchannel plate by 10 4 to 10 9 times.
- the cold electron supply unit may further include an ion lens configured to focus the electron beam multiplied through the channeltron electron multiplier and emit the electron beam to the ionizer.
- the cold electron supply unit may further include a gate electrode that blocks or allows the electron beam emitted from the ion lens to be injected into the ionizer.
- the ion detector may receive the ions to generate, amplify, and detect electrons, and the ion detector may include a microchannel plate or a channeltron electron multiplier that amplifies the electrons.
- the interior space may be a vacuum.
- the pressure in the internal space may be 10 -10 ⁇ 10 -4 Torr.
- the ionization unit collides with the electron beam
- the sample unit is disposed a sample generating the ions; And it may include a sample supply unit for supplying the sample on the sample unit.
- the sample supply unit may spray a gas sample on the sample unit, the gas sample may be adsorbed on the upper surface of the sample unit.
- the sample supply unit may provide the gas sample on the sample unit in a pulse manner.
- the sample supply unit may spray a liquid sample onto the sample unit, and the liquid sample may be adsorbed onto the sample unit.
- a flight time mass spectrometer having a small difference in ionization time of ions may be provided. Accordingly, the accuracy of the time-of-flight mass spectrometer may be high.
- a time-of-flight mass spectrometer with low power consumption and high accuracy may be provided. Accordingly, a time-of-flight mass spectrometer suitable for miniaturization can be provided.
- FIG. 1 is a cross-sectional view of a time-of-flight mass spectrometer according to an embodiment of the present invention.
- FIG. 2 is a cross-sectional view of the cold electron supply unit and the ionization unit of the time-of-flight mass spectrometer according to the embodiment of the present invention.
- 3 to 5 are cross-sectional views of a cold electron supply unit and an ionization unit of a time-of-flight mass spectrometer according to an embodiment of the present invention.
- 1 is a cross-sectional view of a time-of-flight mass spectrometer according to an embodiment of the present invention.
- 2 is a cross-sectional view of the cold electron supply unit and the ionization unit of the time-of-flight mass spectrometer according to the embodiment of the present invention.
- the cold electron supply unit 100 may be provided.
- the cold electron supply unit 100 may emit cold electrons using ultraviolet rays, not hot electrons.
- the cold electron supply unit 100 includes an ultraviolet diode 110 emitting ultraviolet light and a microchannel plate 120 that generates, multiplies, and emits an electron beam e using the ultraviolet light. ), A channeltron electron multiplier (130) that multiplies and emits the electron beam (e), and an inlet electrode (140) which emits the electron beam (e) from the channeltron electron multiplier without loss. It may include an ion lens 150 for integrating the electron beam (e), and a gate electrode 160 for controlling whether the electron beam (e) is emitted.
- the inner space of the cold electron supply unit 100 may be substantially vacuum. In one example, the internal space of the cold electron supply unit 100 may have a pressure of about 10 -10 to 10 -4 Torr.
- the ultraviolet diode 110 may emit ultraviolet rays toward the microchannel plate 120. Since the ultraviolet diode 110 uses a current of several to several hundred mA for a short time for several nanoseconds to several hundred microseconds, power consumption may be low.
- the microchannel plate 120 facing the ultraviolet diode 110 may be provided.
- the microchannel plate 120 may generate, amplify, and emit an electron beam e using ultraviolet rays.
- the microchannel plate 120 may have a front plate 122 facing the ultraviolet diode 110 and a back plate 124 disposed opposite the front plate 122.
- the front plate 122 may receive the ultraviolet light supplied from the ultraviolet diode 110 to generate optoelectronics.
- the front plate 122 may have a negative voltage. For example, the voltage of the front plate 122 may be about -3000V to -1000V.
- Optoelectronics can be multiplied in the microchannel plate.
- the multiplied photoelectrons may be referred to as the electron beam e.
- the electron beam e can be multiplied by about 10 4 to 10 9 times than the optoelectronics.
- Backplate 124 may emit a multiplied electron beam e.
- the back plate 124 may have a negative voltage.
- the voltage of the backplane 124 may be about -3000V to -1000V.
- the backplate 124 may emit an electron beam e to the channeltron electron multiplier 130.
- the channeltron electron multiplier 130 may multiply the electron beam e supplied from the microchannel plate 120.
- the channeltron electron multiplier 130 may include an inlet 132, a first electrode 133, a multiplier 136, a second electrode 134, and an outlet 138 sequentially arranged.
- the electron beam e may be multiplied through the inlet 132, the multiplier 136, and the outlet 138. In one example, the electron beam e can be multiplied by 10 4 times to 10 9 times.
- the injection hole 132 may be disposed adjacent to the rear plate 124 of the microchannel plate 120.
- the injection hole 132 may have a cone shape.
- the injection hole 132 may receive the electron beam e from the microchannel plate 120 and multiply it.
- the first electrode 133 may apply a negative voltage to the injection hole 132.
- the first electrode 133 may apply a voltage substantially equal to the voltage of the back plate 124 of the microchannel plate 120 to the injection hole 132.
- the voltage applied by the first electrode 133 to the injection hole 132 may be about -3000V to -1000V.
- the multiplier 136 and the outlet 138 may multiply the electron beam e.
- the second electrode 134 may apply a negative voltage to the outlet 138.
- the second electrode 134 may apply a voltage higher than the voltage of the back plate 124 to the outlet 138.
- the voltage applied by the second electrode 134 to the outlet 138 may be about ⁇ 200 V to 0 V.
- the inlet electrode 140 may increase the straightness of the electron beam e in the channeltron electron multiplier 130 so that the electron beam e may face the outlet 138. Accordingly, the electron beam e in the channeltron electron multiplier 130 can be emitted without loss out of the outlet 138.
- the voltage of the inlet electrode 140 may be about ⁇ 200 V to 0 V.
- the ion lens 150 may focus the electron beam e emitted from the outlet 138.
- the ion lens 150 may have a negative voltage. In one example, the ion lens 150 may have a voltage higher than the voltage applied to the back plate 124 of the microchannel plate 120.
- the gate electrode 160 may block or allow the electron beam e passing through the ion lens 150 to be injected into the ionizer 200.
- the gate electrode 160 may have an on / off state. In the on state of the gate electrode 160, the electron beam e passing through the ion lens 150 may pass through the gate electrode 160 and be injected into the ionizer 200. In the off state of the gate electrode 160, the electron beam e having passed through the ion lens 150 may not be injected into the ionizer 200.
- An ionizer 200 in which ions I are generated may be provided. Ions I may be formed using the electron beam e injected from the cold electron supply unit 100.
- the ionizer 200 may share an internal space with the cold electron supply unit 100. Accordingly, the ionizer 200 may have a vacuum state substantially the same as that of the cold electron supply unit 100.
- the inner space of the ionization part (200) is about 10 -10 to 10 may have a pressure of 4 Torr.
- the ionization unit 200 may include a sample unit 210 in which a sample is disposed, and a mesh unit 220 spaced apart in a direction perpendicular to the surfaces of the sample unit 210 and the sample unit 210.
- the mesh unit 220 may allow the ions I emitted from the sample unit 210 to have straightness.
- the mesh unit 220 may have a grid shape. Ions I may pass through the mesh unit 220.
- a positive voltage may be applied to the sample unit 210 and a negative voltage may be applied to the mesh unit 220. Accordingly, an electric field may be formed between the sample part 210 and the mesh part 220. The electric field may have a direction from the sample part 210 toward the mesh part 220.
- the electron beam e injected into the ionization unit 200 may be bent toward the sample unit 210 by receiving a force toward the sample unit 210 by the electric field.
- the sample on the sample unit 210 may collide with the electron beam e to emit ions I.
- the gas sample G may be injected onto the sample unit 210.
- the gas sample G may be sprayed onto the sample unit 210 in a pulsed manner.
- the gas sample G may be adsorbed on the surface of the sample unit 210.
- the sample adsorbed on the surface of the sample unit 210 may collide with the electron beam e injected from the cold electron supply unit 100.
- ions I can be released from the sample.
- the ions I may include ions I having different masses according to the composition of the sample.
- the ions I may be positively charged and may receive a force from the sample portion 210 toward the mesh portion 220. Ions I may move through the mesh unit 220 to the ion separator 300.
- the mesh unit 220 may be two or more. In this case, the mesh units 220 may be disposed in parallel to each other.
- An ion separator 300 may be provided to receive the ions I passing through the mesh unit 220.
- the ion separator 300 may have a straight tube shape.
- the ion separator 300 may share an internal space with the ionizer 200 and the cold electron supply unit 100 to have a vacuum state.
- the inner space of the ion separator 300 may have a pressure of about 10 -10 to 10 -4 Torr.
- the ions I generated by the ionizer 200 may move to the ion detector 400 through the ion separator 300.
- the ion separation unit 300 may extend in a direction perpendicular to the surface of the sample unit 210.
- the moving speed of the ions I having a relatively small mass may be faster than the moving speed of the ions I having a relatively large mass.
- Ions I having different masses may have different passage times of the ion separator 300.
- An ion detector 400 that detects the ions I passing through the ion separator 300 may be provided.
- the ion detector 400 may have a vacuum state by sharing an internal space with the ion separator 300, the ionizer 200, and the cold electron supply unit 100.
- the inner space of the ion detector 400 is about 10 -10 to 10 may have a pressure of 4 Torr.
- the ion detector 400 may include a microchannel plate (not shown) and / or a channeltron electron multiplier (not shown). In this case, the microchannel plate and the channeltron electron multiplier may be substantially the same as the microchannel plate 120 and the channeltron electron multiplier 130 included in the cold electron supply unit 100.
- ions I may be implanted in the microchannel plate and / or channeltron electron multiplier to induce electrons. Electrons can be amplified in the microchannel plate and / or channeltron electron multiplier and sensed by a detection circuit (not shown).
- ions (I) having a relatively small mass and ions (I) having a relatively large mass enter the ion separator 300 at the same time, ions (I) having a relatively small mass have a relatively large mass.
- the ion detector 400 may be detected before the excitation ion. As the length of the ion separator 300 is longer, a difference in time for detecting ions I having different masses may be greater.
- Molecules having different masses collide with the electron beam (e), so the smaller the difference in ionization time for emitting ions, the higher the accuracy of the time-of-flight mass spectrometer.
- the difference in ionization time of ions having different masses can range from several to several hundred nanoseconds. Accordingly, the flight time mass spectrometer including the cold electron supply unit 100 may have high accuracy.
- a time-of-flight mass spectrometer of desired accuracy can be obtained. Accordingly, a time-of-flight mass spectrometer suitable for miniaturization can be provided.
- the time-of-flight mass spectrometer of the present invention uses ultraviolet diodes, so that power consumption may be low.
- 3 to 5 are cross-sectional views of a cold electron supply unit and an ionization unit of a time-of-flight mass spectrometer according to an embodiment of the present invention.
- the description of what is substantially the same as that described with reference to FIGS. 1 and 2 may be omitted.
- a liquid sample L may be provided on the sample unit 210.
- the liquid sample L may be sprayed onto the sample part 210 through the sample supply nozzle 510.
- the liquid sample L may be adsorbed on the surface of the sample unit 210.
- the liquid sample L may collide with the electron beam e to generate ions I. Ions I may be detected at the ion detector by passing through the ion separator.
- a solid sample rod 520 may be used as a sample.
- the solid sample rod 520 may collide with the electron beam e to generate ions I.
- Ions I may be detected at the ion detector by passing through the ion separator.
- a matrix sample, a carbon nano tube (CNT), or graphene 530 may be provided on the sample unit 210.
- the matrix sample, carbon nanotubes, or graphene 530 may collide with the electron beam e to generate ions I.
- Ions I may be detected at the ion detector by passing through the ion separator.
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- Analytical Chemistry (AREA)
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- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Electron Tubes For Measurement (AREA)
Abstract
Description
Claims (15)
- 전자 빔을 수용하여, 이온을 방출하는 이온화부;상기 이온화부에 상기 전자 빔을 주입하는 냉전자 공급부;상기 이온화부로부터 방출된 상기 이온을 감지하는 이온 검출부; 및상기 이온화부와 상기 이온 검출부를 연결하는 이온 분리부를 포함하되,상기 냉전자 공급부는 자외선을 수용하여 상기 전자 빔을 방출하는 마이크로채널 플레이트(Microchannel Plate)를 포함하며,상기 이온화부에서 방출된 상기 이온은 상기 이온 분리부를 통과하여 상기 이온 검출부에 도달하고,상기 이온 분리부는 곧은 관(straight tube) 형상을 가지는 비행시간 질량분석기.
- 제 1 항에 있어서,상기 냉전자 공급부는 상기 마이크로채널 플레이트로 상기 자외선을 방출하는 자외선 다이오드를 더 포함하는 비행시간 질량분석기.
- 제 1 항에 있어서,상기 마이크로채널 플레이트는 상기 자외선을 수용하여 전자들을 생성하는 전면판; 및상기 전자 빔을 방출하는 후면판을 포함하고,상기 전자 빔은 상기 마이크로채널 플레이트 내에서 증배(multiply)된 상기 전자들인 비행시간 질량분석기.
- 제 3 항에 있어서,상기 증배는 104배 내지 109배인 비행시간 질량분석기.
- 제 1 항에 있어서,상기 냉전자 공급부는 상기 마이크로채널 플레이트에서 방출된 상기 전자 빔을 증배(multiply)하는 채널트론 전자 증배기(channeltron electron multiplier)를 더 포함하는 비행시간 질량분석기.
- 제 5 항에 있어서,상기 채널트론 전자 증배기는 상기 마이크로채널 플레이트에서 방출된 상기 전자 빔을 104배 내지 109배 증배하는 비행시간 질량분석기.
- 제 5 항에 있어서,상기 냉전자 공급부는 상기 채널트론 전자 증배기를 통해 증배된 상기 전자 빔을 집적(focusing)하여, 상기 이온화부로 방출하는 이온 렌즈를 더 포함하는 비행시간 질량분석기.
- 제 7 항에 있어서,상기 냉전자 공급부는 상기 이온 렌즈에서 방출된 상기 전자 빔이 상기 이온화부로 주입되는 것을 차단하거나 허용하는 게이트 전극을 더 포함하는 비행시간 질량분석기.
- 제 1 항에 있어서,상기 이온 검출부는 상기 이온을 수용하여, 전자를 생성, 증폭 및 감지하고,상기 이온 검출부는 상기 전자를 증폭하는 마이크로채널 플레이트 또는 채널트론 전자 증배기를 포함하는 비행시간 질량분석기.
- 제 1 항에 있어서,내부 공간이 진공인 비행시간 질량분석기.
- 제 1 항에 있어서,내부 공간의 압력이 10-10~10- 4Torr인 비행시간 질량분석기.
- 제 1 항에 있어서,상기 이온화부는 상기 전자 빔과 충돌하여, 상기 이온을 발생하는 시료가 배치되는 시료부; 및상기 시료부 상에 상기 시료를 공급하는 시료 공급부를 포함하는 비행시간 질량분석기.
- 제 12 항에 있어서,상기 시료 공급부는 기체 시료를 상기 시료부 상에 분사하고,상기 기체 시료는 상기 시료부 상면에 흡착되는 비행시간 질량분석기.
- 제 13 항에 있어서,상기 시료 공급부는 상기 기체 시료를 펄스(pulse) 방식으로 상기 시료부 상에 제공하는 비행시간 질량분석기.
- 제 13 항에 있어서,상기 시료 공급부는 액체 시료를 상기 시료부 상에 분무하고,상기 액체 시료는 상기 시료부 상에 흡착되는 비행시간 질량분석기.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US15/321,563 US10388506B2 (en) | 2014-12-30 | 2015-12-04 | Time-of-flight mass spectrometer using a cold electron beam as an ionization source |
| EP15875545.4A EP3147933A4 (en) | 2014-12-30 | 2015-12-04 | Time-of-flight mass spectrometer |
| JP2016575356A JP6346965B2 (ja) | 2014-12-30 | 2015-12-04 | 飛行時間質量分析計 |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20140194149 | 2014-12-30 | ||
| KR10-2014-0194149 | 2014-12-30 | ||
| KR10-2015-0171695 | 2015-12-03 | ||
| KR1020150171695A KR101786950B1 (ko) | 2014-12-30 | 2015-12-03 | 비행시간 질량분석기 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2016108451A2 true WO2016108451A2 (ko) | 2016-07-07 |
| WO2016108451A3 WO2016108451A3 (ko) | 2016-10-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/KR2015/013252 Ceased WO2016108451A2 (ko) | 2014-12-30 | 2015-12-04 | 비행시간 질량분석기 |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2016108451A2 (ko) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109461642A (zh) * | 2018-12-07 | 2019-03-12 | 中国烟草总公司郑州烟草研究院 | 一种离子引发电子轰击电离源 |
| RU225173U1 (ru) * | 2023-09-01 | 2024-04-15 | Федеральное государственное бюджетное учреждение науки Физико-технический институт им. А.Ф. Иоффе Российской академии наук | Времяпролетный масс-спектрометр |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2001241907A1 (en) * | 2000-04-12 | 2001-10-30 | The Regents Of The University Of California | Method of reducing ion fragmentation in mass spectrometry |
| US8686733B2 (en) * | 2007-12-19 | 2014-04-01 | Brooks Automation, Inc. | Ionization gauge having electron multiplier cold emission source |
| US8035081B2 (en) * | 2009-09-30 | 2011-10-11 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | High precision electric gate for time-of-flight ion mass spectrometers |
| US9230791B2 (en) * | 2011-11-28 | 2016-01-05 | Korea Basic Science Institute | Anion generating and electron capture dissociation apparatus using cold electrons |
| JP6163068B2 (ja) * | 2013-09-19 | 2017-07-12 | 浜松ホトニクス株式会社 | Mcpユニット、mcp検出器および飛行時間型質量分析器 |
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2015
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109461642A (zh) * | 2018-12-07 | 2019-03-12 | 中国烟草总公司郑州烟草研究院 | 一种离子引发电子轰击电离源 |
| CN109461642B (zh) * | 2018-12-07 | 2024-04-02 | 中国烟草总公司郑州烟草研究院 | 一种离子引发电子轰击电离源 |
| RU225173U1 (ru) * | 2023-09-01 | 2024-04-15 | Федеральное государственное бюджетное учреждение науки Физико-технический институт им. А.Ф. Иоффе Российской академии наук | Времяпролетный масс-спектрометр |
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