WO2007138679A1 - 質量分析装置 - Google Patents
質量分析装置 Download PDFInfo
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- WO2007138679A1 WO2007138679A1 PCT/JP2006/310775 JP2006310775W WO2007138679A1 WO 2007138679 A1 WO2007138679 A1 WO 2007138679A1 JP 2006310775 W JP2006310775 W JP 2006310775W WO 2007138679 A1 WO2007138679 A1 WO 2007138679A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/0004—Imaging particle spectrometry
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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
- H01J49/06—Electron- or ion-optical arrangements
- H01J49/061—Ion deflecting means, e.g. ion gates
Definitions
- the present invention relates to a mass spectrometer that performs mass analysis by ionizing one or more substances existing in a two-dimensional range on a sample.
- a mass spectrometer according to the present invention is a mass spectrometer that obtains two-dimensional qualitative information and quantitative information by performing a mass analysis of a substance existing in the observation region, and a microscope that specifically observes a two-dimensional range on a sample. It is suitable for a micro-mass spectrometer combined with an analyzer.
- a mass spectrometer ionizes molecules and atoms of sample components contained in a gaseous, liquid, or solid sample, and separates and detects the ions for each mass number to detect the sample components. It is a device for identifying and quantifying the amount of its components, and is currently widely used for various purposes such as identification of biological samples and analysis of proteins or peptides.
- Non-Patent Document 1 generates ions in a two-dimensional form to reflect the two-dimensional distribution of the substance on the sample, and this is generated as a time-of-flight (TOF) mass component.
- TOF time-of-flight
- a method has been proposed in which mass separation is performed by a separator and detection is performed by a two-dimensional detector.
- measurement circuits such as amplifiers and digitizers in parallel as many as the number of detectors, resulting in a great cost.
- the position resolution spatial resolution
- an imaging element with a special structure called a pixel peripheral recording type imaging device is used as a two-dimensional array detector, and for example, ions subjected to mass separation with a TOF type mass separator are microchanneled.
- the light is incident on a Nel plate (MCP), and a larger amount of electrons are emitted than the amount of ions.
- MCP Nel plate
- the electrons are converted into light by the fluorescent plate, and the light is converted into an electrical signal by the pixel peripheral recording type imaging device.
- the electrical signal corresponding to the original ion amount is taken out.
- the pixel peripheral recording type image pickup element is disclosed in detail in existing documents such as Patent Documents 1 and 2, for example, and thus will not be described in detail.
- Each photodiode serving as a light receiving unit Each has a storage CCD that doubles as many as the number of recordings (frames), and the pixel signals photoelectrically converted by the photodiode are sequentially transferred to the storage CCD during shooting.
- the pixel signals for the stored number of recordings are read together and the images for the number of recordings are reproduced outside the element. Pixel signals that exceed the number of records during shooting are discarded in chronological order, so that the pixel signals for the latest number of records are always stored in the storage CCD.
- This type of two-dimensional array detector has a structural upper limit on the number of force-captured images that can acquire images at extremely high speed. For example, when a detector capable of acquiring 100 frames at a speed of 1 million frames Z seconds is used, mass spectrometry data can be obtained over a time range of 100 seconds at 1 ⁇ s intervals. 10 million frames at a higher speed 10 When a detector capable of acquiring 0 frames is used, mass spectrometry data can be obtained over a time range of 10 seconds at 100 eta-second intervals. In any case, the number of mass spectrometry data points is limited by the number of frames that can be continuously acquired by the two-dimensional array detector.
- the time interval for repeatedly acquiring mass spectrometry data is as short as possible.
- the range of mass numbers that can be measured in one analysis is as wide as possible. To that end, it is necessary to acquire as many mass spectrometry data as possible.
- the flight time of an ion with a mass number of 10000 [amu] is 144.47 ⁇ sec, and there is a difference of 100 ⁇ sec between 1000 [amu] and 10000 [amu]. If this is measured with a two-dimensional array detector capable of acquiring 100 frames simultaneously, the time difference (time resolution) per frame is 1 second. As mentioned above, the flight time of ions of 1000 [amu] is about 45.69 ⁇ s, and the mass number of ions reaching 46.69 ⁇ s after 1 ⁇ s time resolution is 1044 [amu]. It becomes. Therefore, the mass resolution of this mass spectrometer is only about 44 [amu].
- Patent Document 1 Japanese Patent Laid-Open No. 2001-345441
- Patent Document 2 JP 2004-235621 A
- Non-Patent Document 1 Yasuhide Naito, “Mass Microscope for Biological Samples”, Journal of Japan Society for Mass Spectrometry, Vol. 53, No. 3, 2005
- the present invention has been made in order to solve the above-mentioned problems, and the object of the present invention is to perform a mass analysis of a two-dimensional range on a sample, and as a two-dimensional array detector.
- the object of the present invention is to perform a mass analysis of a two-dimensional range on a sample, and as a two-dimensional array detector.
- ionization means for ionizing all components contained in a predetermined two-dimensional range on the sample simultaneously
- Mass separation means for separating the ions generated by the ionization means so that the emission time differs according to the mass number while maintaining the two-dimensional relative positional relationship in which each ion is generated.
- the detectors are arranged in two dimensions, and the electrical signals obtained by each of the micro detectors can be held for a predetermined number of frames.
- Pixel peripheral recording type with built-in memory Two-dimensional detection means comprising a two-dimensional array detector as an image sensor as one set, and a plurality of sets arranged in parallel in the extending direction of the detection unit;
- an ion deflecting means that is arranged in a space between the ion exit port of the mass separating means and the converting means, and that forms an electric field and a Z or magnetic field that exerts a force that bends the flight trajectory on the passing ions.
- the ions that have passed through the ion deflecting means at different time points in the two-dimensional detecting means It is also characterized by being detected by a two-dimensional array detector.
- the two-dimensional array detector in the present invention is a force that is a normal pixel peripheral recording type imaging device having a detection unit in which micro detection elements that perform photoelectric conversion are arranged in a two-dimensional form, or a detection unit is formed.
- This is one of the back-side pixel peripheral recording image sensors that captures and detects electrons incident on the detection surface (usually the back surface of the substrate) on the opposite surface.
- each of the two-dimensionally arranged micro detection elements is equipped with a storage CCD or the like that also serves as the transfer unit for N (N: an integer of 2 or more) frames.
- N an integer of 2 or more
- the electrical signals obtained by the micro-detection elements are sequentially transferred to the storage unit, and after the completion of imaging, the electrical signals stored in the storage unit are read at once to collect the N-frame pixel signals together ( In other words, it can be acquired one frame at a time).
- the electrical signals that exceed N frames during shooting are discarded in the oldest order, the latest N frames of electrical signals are always stored in the storage unit. For this reason, for example, if the transfer of the electrical signal to the storage CCD is stopped at the end of shooting, the latest N frames of images from the time point N frames in time can be obtained.
- each two-dimensional array detector can hold N frames of image signals internally and can stop the transfer of new electrical signals to the storage unit at any point in time, so each N corresponds to a different time range. High-speed acquisition of frame images is possible.
- Mass separation means have different mass numbers at different times. Since mass separation is performed so that ON is emitted, the ions with different mass numbers that are generated at the same position on the sample due to bending of the flight trajectory by the ion deflection means reach different sets of conversion means. It is detected by a two-dimensional array detector corresponding to the conversion means.
- the control means for controlling the storing operation of the electrical signal to the storage unit in each two-dimensional array detector corresponds to the conversion means corresponding to a plurality of sets of two-dimensional array detectors. If each storage operation is controlled in accordance with the timing of ion incidence on the two-dimensional array, two-dimensional substance distribution images (mass masses) corresponding to different mass number ranges are applied to different sets of two-dimensional array detectors. Analysis image). As a result, if the number of pairs of the conversion means and the two-dimensional array detector is increased and the amount of bending of the flight trajectory by the ion deflection means can be increased accordingly, the measurement target in each pair can be increased. Even if the mass number range is narrow, the mass number range to be measured can be expanded as a whole. The mass resolution is determined by the transfer time interval of the electric signal to the storage unit in each two-dimensional array detector.
- a time-of-flight (TOF) mass analyzer is typically used as the mass separation means.
- TOF time-of-flight
- various ions generated at the same time by laser irradiation for a short time can be detected separately in time according to the mass number without being wasted, so that high detection sensitivity can be obtained. be able to.
- the ion deflecting means includes one or a plurality of sets of deflecting electrodes disposed across an ion passage region, and a voltage is applied to the deflecting electrodes.
- Voltage application means for changing the amount of bending of the flight trajectory of ions by changing the applied voltage.
- the amount of bending of the flight trajectory can be arbitrarily controlled according to the magnitude of the voltage applied to the deflection electrode.
- Arbitrary projection positions for mass analysis image images such as allowing ions in different mass number ranges to be incident, or gradually shifting the incident position of ions as the mass number increases to span multiple sets of conversion means Can be decided. Further, it is possible to easily cope with a difference in the size of the ion incident surface of the conversion means.
- the ion deflecting means is a set of magnetic poles arranged across an ion passage region, and a constant magnetic field formed by the magnetic poles. A configuration in which the bending amount of the flight trajectory changes according to the change in the mass number of ions passing through the field may be used.
- Ions passing through the magnetic field receive a force from the magnetic field and bend according to the mass number of the ions. Therefore, even when the magnetic force of the magnetic field is constant, the flight trajectory curve increases as the mass number of ions passing through increases, and the projection position of the mass analysis image image can be moved.
- a detection that has a limited number of measurable frames although it is possible to repeatedly acquire images at high speed, such as a pixel peripheral recording type imaging device as a two-dimensional array detector.
- a vessel When a vessel is used, two-dimensional distribution information (mass analysis image image) of a substance over a wide mass number range can be acquired with a high mass resolution by a single measurement.
- FIG. 1 is a configuration diagram of a main part of a micro mass spectrometer according to one embodiment (first embodiment) of the present invention.
- FIG. 2 is a schematic configuration diagram of a pixel peripheral recording type image sensor used in the micro mass spectrometer of the first embodiment.
- FIG. 3 is a functional configuration diagram of one pixel of the pixel peripheral recording type image pickup device shown in FIG.
- FIG. 4 is a diagram showing a voltage waveform applied to a deflection electrode in the micromass spectrometer of the first embodiment.
- FIG. 5 is a schematic cross-sectional view showing a configuration of a detection unit when a normal pixel peripheral recording image sensor and a back surface pixel peripheral recording image sensor are used.
- FIG. 6 is a diagram showing another example of a voltage waveform applied to the deflection electrode in the micromass spectrometer of the first embodiment.
- FIG. 7 is a schematic diagram for explaining the operation of the two-dimensional detection unit in the micro mass spectrometer of the first embodiment.
- FIG. 8 is a configuration diagram of a main part of a micro mass spectrometer according to a second embodiment.
- FIG. 9 is a configuration diagram of a main part of a micro mass spectrometer according to a third embodiment.
- FIG. 10 is a configuration diagram of a main part of a micro mass spectrometer according to a fourth embodiment.
- FIG. 11 is a configuration diagram of a main part of a micro mass spectrometer according to a fifth embodiment.
- FIG. 1 is a block diagram of the main part of the micromass spectrometer of the first embodiment.
- a laser desorption ionization (LDI) method is used to ionize sample components contained in the sample all at once, that is, the sample S placed on the sample stage 2 is applied to the sample S.
- LIDI laser desorption ionization
- a laser beam 1 for ionic ions having a two-dimensional spread is irradiated for a short time.
- TOF time-of-flight
- the TOF-type mass separation unit 4 may be another form of TOF such as a force-reflectron type or circular type that is a linear type TOF. What is important is that the relative positional relationship at the time of extraction from the sample S is maintained so that ions emitted from different site forces on the sample S do not enter during mass separation.
- the positions of various ions are moved back and forth according to the mass number. Specifically, ions with different mass numbers emitted simultaneously from a certain point on the sample S pass through the same flight trajectory, but ions with a small mass number do not travel while flying through the flight space of the TOF type mass separator 4. The earlier the ions with higher mass numbers, the longer the delay. In this manner, the ions are emitted from the TOF-type mass separation unit 4 while being temporally mass-separated, pass through the projection lens 5 and pass between the two deflection electrodes 61 and 62 arranged to face each other. A two-dimensional detector 7 is arranged in front of the ion travel.
- the two-dimensional detection unit 7 includes three sets of detection units 7a, 7b, and 7c arranged side by side in the X-axis direction.
- One set of detection units 7a includes a microchannel plate (MCP) 8a, a fluorescent plate 9a, and a two-dimensional array detector 10a, and the other detection units 7b and 7c have the same configuration.
- FIG. 5 (a) is a schematic cross-sectional view schematically showing an ion detection operation in one set of detection units 7a.
- the MCP8a converts each two-dimensionally incident ion into an electron and multiplies the amount, and the fluorescent screen 9a receives the electron increased in the preceding MCP8a and converts it into a photon.
- the two-dimensional array detector 10a is an image pickup device having a structure called a pixel peripheral recording type image pickup device.
- FIG. 2 is a diagram schematically showing the structure of this image sensor
- FIG. 3 is a functional configuration diagram of one pixel of the image sensor shown in FIG.
- a large number of photodiodes 21 that are micro-detection elements for photoelectric conversion are two-dimensionally arranged on the detection surface, and the signal charges generated by each photodiode 21 are fed forward.
- a storage CCD array 25 as a storage unit to be held is provided in or around the pixel.
- the signal charges generated by the photodiodes 21 are sent to the respective storage CCD columns 25 through the write gates 22, and the ends of the storage CCD columns 25 connected to the plurality of photodiodes 21 arranged in the vertical direction are The ends of a plurality of vertical charge transfer units 23 connected to the common vertical charge transfer unit 23 and arranged in the horizontal direction are connected to one horizontal charge transfer unit 24.
- the storage CCD array 25 can hold a detection signal for a predetermined frame (a pixel signal when one photodiode 21 is regarded as a pixel), the detection signal is not read in the middle of the predetermined frame. A few minutes of pixel signals can be acquired continuously at high speed, and after the acquisition is completed, the stored pixel signals can be read out and processed.
- the control unit 11 includes a CPU and the like, and controls the operation of the two-dimensional array detectors 10a, 10b, and 10c, and controls the flight of ions in the TOF type mass separation unit 4.
- the voltage generator 14 is controlled, and the deflection voltage generator 15 that applies a deflection voltage to the deflection electrodes 61 and 62 is controlled.
- the control unit 11 changes the deflection voltage applied to the deflection electrode 61 in three steps in steps with time after laser irradiation, that is, Va ⁇ 0 ⁇ Va.
- the deflection voltage generator 15 is controlled so that the deflection voltage applied to the deflection electrode 62 changes from Va ⁇ 0 ⁇ ⁇ Va as indicated by the dotted line in FIG.
- Various ions are generated almost simultaneously in the two-dimensional range of sample S by irradiation with laser beam 1 for a short time, and enter TOF-type mass separator 4 through focusing lens 3 as described above.
- a negative deflection voltage Va is applied to the deflection electrode 61 and a positive deflection voltage + Va is applied to the deflection electrode 62. Due to the negative deflection electric field, ions with a relatively small mass number that pass through in the initial stage are greatly bent in the negative direction along the X axis in Fig. 1 (to the right in Fig. 1). The ions are then introduced into the MCP 8a of the detection unit 7a.
- the control unit 11 gives a control signal to each of the detection units 7a, 7b, and 7c so that the signal charges are transferred to the storage CCD array 25 at a predetermined equal time interval.
- Fig. 7 shows the history of mass spectrometry images obtained with the two-dimensional array detectors 10a, 10b, and 10c.
- the number of frames that can be held in one two-dimensional array detector 1 Oa, 10b, 10c is five.
- the two-dimensional array detector 10a is capable of obtaining a 5-frame mass analysis image.
- Other two-dimensional array detectors 10b and 10c Then, the mass spectrometry image obtained at that time is a no-signal image (or noise image).
- the control unit 11 transfers the deflection voltage applied to the deflection electrode 61 from Va to 0, and the deflection voltage applied to the deflection electrode 62 from + Va to 0. Stop operation only. Then, the image signal representing the mass analysis image images F1 to F5 corresponding to the mass numbers Ml,..., M5 is held in the storage CCD array 25 inside the two-dimensional array detector 10a.
- the transfer operation in the two-dimensional array detector 10b is also performed. Stop. Then, in the CCD array 25 for accumulation inside the two-dimensional array detector 10b, the image signals representing the five mass analysis image images F6 to F10 corresponding to the mass numbers M6,. Become.
- the control unit 11 also stops the transfer operation in the two-dimensional array detector 10c. Then, the storage CCD array 25 inside the two-dimensional array detector 10c holds five mass analysis image images F 11 to F 15 corresponding to the mass numbers Ml l,..., M 15. It is done.
- the data processing unit 12 executes predetermined processing on the data stored in the data memory 13. For example, it is possible to create a gray scale display image showing the signal intensity in shades for each mass number, and obtain distribution information of a substance corresponding to the mass number.
- the display color may be changed according to the magnitude of the signal intensity, or a three-dimensional graph display with the signal intensity as another axis may be used.
- the analysis result as described above can be displayed on the display unit 16 in any display format, for example, by displaying contour lines by connecting lines of similar signal intensity, that is, concentration positions.
- the three detection units 7a, 7b, and 7c including the two-dimensional array detectors 10a, 10b, and 10c are arranged in parallel, and the TOF type mass separation unit
- the ions separated in time according to the mass number in Fig. 4 are distributed to the three detection units 7a, 7b, 7c in order by changing the flight trajectory with the deflection electric field as time passes.
- mass numbers M1 to M15 mass numbers M1 to M15. It is possible to acquire mass analysis image images in a wide mass range. Since the signal transfer time interval is mass resolution, the mass range of the measurement target can be expanded while maintaining the same mass resolution. In addition, if the mass number range to be measured is the same as the conventional one, the mass resolution can be increased by narrowing the time interval.
- the deflection voltage may be swept in a slope shape as shown in FIG.
- ions with a small mass number that first reach the deflection electric field are bent largely by the strong negative deflection electric field and reach the detection unit 7a.
- the mass number of ions that reach the deflection electric field gradually increases, but the negative deflection electric field gradually weakens accordingly, and the bending amount of the flight trajectory decreases and approaches the straight direction. Then, when the deflection voltage becomes 0, the ions go straight.
- a positive deflection voltage is applied to the deflection electrode 61 and a negative deflection voltage is applied to the deflection electrode 62, and the value (absolute value) gradually increases. Therefore, the positive deflection electric field gradually increases. Along with this, ions are bent in the positive direction of the X axis, and the amount of bending increases.
- the projection image gradually moves in the positive direction of the X axis on the ion entrance surfaces of the MCPs 8a, 8b, and 8c of the two-dimensional detection unit 7 as the deflection voltage changes. Therefore, in this case, the signal transfer of each of the two-dimensional array detectors 10a, 10b, and 10c is stopped so that the projected image that shifts as described above is stopped when the detection image is removed from each of the detection units 7a and 7b. That's fine. Also, since the shift amount of the projected image per unit time can be obtained in advance, by correcting the shift amount at the data processing stage, the same mass analysis image as when the deflection voltage changes stepwise. An image can be created.
- a general pixel peripheral recording type imaging device is used as the two-dimensional array detectors 10a, 10b, and 10c.
- a back surface type pixel peripheral recording type imaging device is used. Can also be used.
- the basic structure of this back surface type element is the same as that of the normal element described above, but it is equivalent to a photodiode by making the substrate incident on the back surface easier by making the substrate thinner. It captures the electrons incident on each microdetection element and uses the current that flows by this instead of the photocurrent. Therefore, electrons can be directly incident on the two-dimensional array detector, and a pixel signal corresponding to the amount of electrons can be extracted. it can.
- the MCP8a converts each two-dimensionally incident ion to an electron and multiplies it, as shown in Fig. 6 (b).
- the increased amount of electrons is incident on the detection surface on the back surface of the two-dimensional array detector 40a.
- the relative positional relationship of the part where each ion exits on the sample S is also maintained on the detection surface of the two-dimensional array detector 4 Oa.
- This configuration has the advantage of reducing the cost by eliminating the need for a fluorescent screen. By eliminating the fluorescent screen, the MCP8a and the detection surface of the two-dimensional array detector 40a are brought close to each other, so This is effective in reducing blur. Accordingly, the spatial resolution of the mass spectrometry image can be improved.
- FIG. 8 is a configuration diagram of the main part of the micro mass spectrometer of the second embodiment.
- the same components as those in the first embodiment are denoted by the same reference numerals and description thereof is omitted.
- the description of the block configuration of the electric circuit of the control system and the processing system is omitted.
- the other two deflection electrodes 301 and 302 are arranged to face each other in the direction orthogonal to the two opposing deflection electrodes 61 and 62.
- the detection units 7a, 7b, 7c, 7d, 7e, 7f, 7g, 7h, 7i are not only arranged in the X-axis direction but also arranged in the Y-axis direction.
- the ion flight trajectory is bent in the X-axis direction by the deflection electric field formed by the deflection electrode 6, and the ion flight trajectory is formed by the deflection electric field formed by the additional deflection electrodes 301 and 302. Bend in the direction.
- the detection units 7a to 7i that acquire the mass spectrometry image images are sequentially distributed with time, that is, with an increase in the mass number of ions emitted from the TOF type mass separation unit 4.
- the mass number range to be measured can be further expanded as compared with the first embodiment.
- FIG. 9 is a block diagram of the main part of the micro mass spectrometer according to the third embodiment.
- the same components as those in the first embodiment are designated by the same reference numerals and the description thereof is omitted. Avoid drawing clutter Therefore, the description of the block configuration of the electric circuit of the control system and the processing system is omitted.
- an electric field is used to deflect ions.
- ions are deflected by a magnetic field. That is, a pair of parallel plate magnetic poles 311 and 312 are disposed in the space between the projection lens 5 and the two-dimensional detection unit 7 instead of the deflection electrode. A static magnetic field is formed between the parallel plate magnetic poles 31.
- ions accelerated by voltage E rotate at a radius of rotation R expressed by the following equation.
- the radius of rotation differs depending on the mass of the ions, so the orbits of ions passing through the magnetic field change for each mass.
- FIG. 10 is a block diagram of the principal part of the micromass spectrometer of the fourth embodiment.
- the same components as those in the first embodiment are denoted by the same reference numerals and description thereof is omitted.
- the description of the block configuration of the electric circuit of the control system and the processing system is omitted.
- an electric field formed by two opposing deflection electrodes 61 and 62 and a magnetic field formed by two opposing parallel plate magnetic poles 311 and 312 are combined.
- a mass separator that combines an electric field and a magnetic field is generally known as an E X B type mass separator. In this mass separator, the force due to the magnetic field is applied in the opposite direction to the force due to the electric field. For an ion of a certain mass number m, these two forces are balanced and go straight.
- the trajectory bends in the positive direction of the X axis, and the mass Since ions with a large number are less affected by the magnetic field, they are more strongly affected by the electric field, and in Fig. 10, the trajectory bends in the negative direction of the X axis. Even in this case, since the arrival position of the ion moves as the mass number increases, mass analysis in different mass number ranges is performed by each of the two-dimensional array detectors 10a, 10b, and 10c as in the above embodiments. The image mass can be acquired to widen the mass range.
- FIG. 11 is a configuration diagram of the main part of the micromass spectrometer of the fifth embodiment.
- the same components as those in the first embodiment are denoted by the same reference numerals and description thereof is omitted.
- the description of the block configuration of the electric circuit of the control system and the processing system is omitted.
- the projection lens 5 is disposed immediately behind the ion emission port of the TOF type mass separation unit 4, and the projection lens 5 and the two-dimensional detection unit 7 are disposed between the projection lens 5 and the two-dimensional detection unit 7.
- the projection lens 5 may be disposed between the deflecting electric field (or the deflecting magnetic field) and the two-dimensional detection unit 7 as in the configuration of the fifth embodiment. . Even with this configuration, it is possible to realize the change of the arrival position and the projection of the image according to the mass number of ions as described above.
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JP2008517739A JP4973659B2 (ja) | 2006-05-30 | 2006-05-30 | 質量分析装置 |
US12/303,037 US7858937B2 (en) | 2006-05-30 | 2006-05-30 | Mass spectrometer |
PCT/JP2006/310775 WO2007138679A1 (ja) | 2006-05-30 | 2006-05-30 | 質量分析装置 |
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GB201810273D0 (en) * | 2018-06-22 | 2018-08-08 | Thermo Fisher Scient Bremen Gmbh | Structural analysis of ionised molecules |
WO2020001954A1 (en) | 2018-06-25 | 2020-01-02 | Carl Zeiss Smt Gmbh | Inspection system and inspection method to qualify semiconductor structures |
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GB201901411D0 (en) | 2019-02-01 | 2019-03-20 | Micromass Ltd | Electrode assembly for mass spectrometer |
CN110265282B (zh) * | 2019-06-10 | 2024-03-01 | 融智生物科技(青岛)有限公司 | 基质辅助激光解吸电离飞行时间质谱仪及样品检测方法 |
AU2022389627A1 (en) * | 2021-11-18 | 2024-06-06 | Autobio Labtec Instruments Co., Ltd. | Ion screening method and system for mass spectrometer, high-voltage pulse circuit, and selection circuit |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000231901A (ja) * | 1999-02-12 | 2000-08-22 | Japan Atom Energy Res Inst | 画像解析法による質量分析計又はそれを使用した質量分析方法 |
JP2001345441A (ja) * | 2000-03-28 | 2001-12-14 | Hideki Muto | 高速撮像素子及び高速撮影装置 |
JP2002116184A (ja) * | 2000-10-10 | 2002-04-19 | Hitachi Ltd | 半導体デバイス異物分析装置およびシステム |
JP2002367558A (ja) * | 2001-06-12 | 2002-12-20 | Jeol Ltd | マルチディテクター付飛行時間型質量分析計 |
JP2004235621A (ja) * | 2003-01-06 | 2004-08-19 | Koji Eto | 裏面照射型撮像素子 |
JP2004281269A (ja) * | 2003-03-17 | 2004-10-07 | Anelva Corp | イオン付着質量分析装置 |
JP2006511912A (ja) * | 2002-12-20 | 2006-04-06 | パーセプティブ バイオシステムズ,インコーポレイテッド | 複数の飛行経路を有する飛行時間型質量分析器 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3819941A (en) * | 1973-10-15 | 1974-06-25 | Bendix Corp | Mass dependent ion microscope having an array of small mass filters |
US4785172A (en) * | 1986-12-29 | 1988-11-15 | Hughes Aircraft Company | Secondary ion mass spectrometry system and method for focused ion beam with parallel ion detection |
US7176972B2 (en) | 2000-03-28 | 2007-02-13 | Link Research Corporation | Fast imaging device and fast photographing device |
JP2001345411A (ja) | 2000-05-31 | 2001-12-14 | Matsushita Electric Ind Co Ltd | リードフレームとそれを用いた半導体装置及びその生産方法 |
EP1583149A4 (en) | 2003-01-06 | 2010-04-14 | Takeharu Etoh | REAR-LIGHTED ILLUSTRATION DEVICE |
EP1721330A2 (en) * | 2004-03-05 | 2006-11-15 | Oi Corporation | Focal plane detector assembly of a mass spectrometer |
JP2007242252A (ja) | 2006-03-06 | 2007-09-20 | Shimadzu Corp | 質量分析装置 |
-
2006
- 2006-05-30 WO PCT/JP2006/310775 patent/WO2007138679A1/ja active Application Filing
- 2006-05-30 US US12/303,037 patent/US7858937B2/en not_active Expired - Fee Related
- 2006-05-30 JP JP2008517739A patent/JP4973659B2/ja not_active Expired - Fee Related
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000231901A (ja) * | 1999-02-12 | 2000-08-22 | Japan Atom Energy Res Inst | 画像解析法による質量分析計又はそれを使用した質量分析方法 |
JP2001345441A (ja) * | 2000-03-28 | 2001-12-14 | Hideki Muto | 高速撮像素子及び高速撮影装置 |
JP2002116184A (ja) * | 2000-10-10 | 2002-04-19 | Hitachi Ltd | 半導体デバイス異物分析装置およびシステム |
JP2002367558A (ja) * | 2001-06-12 | 2002-12-20 | Jeol Ltd | マルチディテクター付飛行時間型質量分析計 |
JP2006511912A (ja) * | 2002-12-20 | 2006-04-06 | パーセプティブ バイオシステムズ,インコーポレイテッド | 複数の飛行経路を有する飛行時間型質量分析器 |
JP2004235621A (ja) * | 2003-01-06 | 2004-08-19 | Koji Eto | 裏面照射型撮像素子 |
JP2004281269A (ja) * | 2003-03-17 | 2004-10-07 | Anelva Corp | イオン付着質量分析装置 |
Non-Patent Citations (2)
Title |
---|
ABD EI RAHIM M. ET AL.: "Position sensitive detection coupled to high-resolution time-of-flight mass spectrometry:Imaging for moleclar beam deflection experiments", REVIEW OF SCIENTIFIC INSTRUMENTS, vol. 75, no. 12, December 2004 (2004-12-01), pages 5221 - 5227, XP012071952 * |
OGAWA K. ET AL.: "Kenbi Shitsuryo Bunseki Sochi no Kaihatsu (RESEARCH AND DEVELOPMENT OF MASS MICROSCOPE)", SHIMADZU REVIEW, vol. 62, no. 34, 31 March 2006 (2006-03-31), pages 125 - 135, XP003018513 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011528166A (ja) * | 2008-07-17 | 2011-11-10 | クラトス・アナリテイカル・リミテツド | 無非点収差イメージングのためのtof質量分析計および関連する方法 |
JP2010251174A (ja) * | 2009-04-17 | 2010-11-04 | Osaka Univ | イオン源、質量分析装置、制御装置、制御方法、制御プログラムおよび記録媒体 |
JP2014197555A (ja) * | 2014-07-10 | 2014-10-16 | 株式会社島津製作所 | 多重周回飛行時間型質量分析装置 |
US11222910B2 (en) | 2017-11-07 | 2022-01-11 | Takeharu Etoh | High-speed image sensor |
Also Published As
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JPWO2007138679A1 (ja) | 2009-10-01 |
US7858937B2 (en) | 2010-12-28 |
US20090272890A1 (en) | 2009-11-05 |
JP4973659B2 (ja) | 2012-07-11 |
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