WO2011102117A1 - 四重極型質量分析計 - Google Patents
四重極型質量分析計 Download PDFInfo
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- WO2011102117A1 WO2011102117A1 PCT/JP2011/000834 JP2011000834W WO2011102117A1 WO 2011102117 A1 WO2011102117 A1 WO 2011102117A1 JP 2011000834 W JP2011000834 W JP 2011000834W WO 2011102117 A1 WO2011102117 A1 WO 2011102117A1
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- mass spectrometer
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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
- H01J49/42—Stability-of-path spectrometers, e.g. monopole, quadrupole, multipole, farvitrons
- H01J49/4205—Device types
- H01J49/421—Mass filters, i.e. deviating unwanted ions without trapping
- H01J49/4215—Quadrupole mass filters
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- the present invention relates to a quadrupole mass spectrometer used for analyzing (partial pressure measurement) a gas component in a test body such as a vacuum vessel.
- the quadrupole mass spectrometer is composed of a sensor unit that is detachably attached to a test body and a control unit. With the mounting direction of the sensor unit with respect to the test body as the upper direction, the sensor unit is a disk-shaped support provided at the lower end, an ion detection unit provided on the support and collecting ions, and the ion detection unit.
- a quadrupole part which is provided above and has four cylindrical electrodes arranged at predetermined intervals in the circumferential direction, and is provided on the quadrupole part and has a filament and a grid to ionize the gas.
- a device provided with an ion source is conventionally used (see, for example, Patent Document 1).
- the filament and grid of the ion source, the quadrupole part, etc. are connected terminals provided on the support for applying an ionization voltage between the filament and the grid or forming an electric field at the quadrupole part.
- the wiring between the filament, grid or quadrupole portion and the connection terminal a wire in which a metal element wire such as copper is covered with a ceramic cover is used in order to ensure insulation. For this reason, if the ion detector, the quadrupole part, and the ion source are arranged in this order from the support side as in the conventional example, a plurality of long wires are required, resulting in an increase in manufacturing cost. In addition, there is a problem that the assembly of the sensor unit becomes troublesome.
- an electron collision method is applied in which a voltage (about 300 V) is applied between the filament and the grid to cause electrons to collide with the grid surface and remove molecules and atoms attached to the surface.
- a so-called energization heating method is known in which an electric current is passed through a grid and molecules and atoms attached to the surface are removed by Joule heat by evaporation (see, for example, Patent Document 2).
- the present invention provides a low-cost quadrupole mass spectrometer capable of realizing energization heating of a grid and capable of analyzing a gas component with high accuracy by preventing a decrease in sensitivity. It is to be an issue.
- the quadrupole mass spectrometer is a quadrupole mass spectrometer capable of analyzing a gas component in a test body, and is detachable from the test specimen.
- the sensor unit has a predetermined shape provided at the lower end, and a filament and a grid provided on the support.
- An ion source that ionizes the gas, and a quadrupole portion formed on the ion source by arranging four columnar electrodes at predetermined intervals in the circumferential direction, and on the quadrupole portion
- an ion detector that collects predetermined ions that have passed through the quadrupole part by applying a DC voltage and an AC voltage between the opposing electrodes.
- the length of the expensive wiring for the ion source can be shortened by positioning the ion source on the support side.
- the wiring to the ion detection unit is longer than that of the conventional example, but only one wiring for detecting the ion current is sufficient. Therefore, as compared with the conventional example, the structure can be simplified and the assembly is facilitated, and the cost can be reduced.
- the ion detection unit when the ion detection unit is located at the position farthest from the support, that is, at the position in contact with the atmosphere in the test object to be analyzed, the gas components present in the test object are detected. Even ions may be detected by the ion detector, and depending on the specimen, there is a possibility that high-precision analysis cannot be performed. For this reason, it is preferable to employ
- a cylindrical wall that extends to above the ion source so as to surround the ion source is provided, and a flange that can be fixed to the specimen is provided at the upper end of the cylindrical wall.
- the configuration can be adopted.
- a quadrupole mass spectrometer is a quadrupole mass spectrometer capable of analyzing a gas component in a test body, A sensor unit that can be detachably attached is provided, and the sensor unit is disposed on the support body with a predetermined shape provided at the lower end, with the mounting direction of the sensor part with respect to the test body facing upward.
- An ion source having a filament and a grid to ionize the gas, and four cylindrical electrodes arranged adjacent to the ion source on the support are parallel to the direction perpendicular to the vertical direction and in the circumferential direction.
- the expensive wiring for the ion source is provided as in the first aspect.
- the length of the wiring to the ion detector can be made the same as that of the conventional example. Therefore, as compared with the conventional example, the structure can be simplified and the assembly is facilitated, and further cost reduction can be achieved.
- the sensor unit when the sensor unit is mounted on the test body, the sensor unit may be accommodated in the tube and mounted on the test body in this state.
- the length of the tubular body can be shortened compared to that of the first aspect, and thus, from the specimen when the specimen is attached to the specimen. The amount of protrusion is reduced, which is advantageous.
- the filament and the free end of the grid of the ion source are connected to a connection terminal fixed through the support in the vertical direction without wiring. .
- an expensive wiring for the ion source can be made unnecessary, and moreover, the wiring loss is eliminated and the grid is efficiently obtained. It is possible to realize a configuration in which current heating is performed. As a result, it is possible to eliminate the need for ion source wiring and reduce the effect of degassing from the wiring, and to prevent contamination of the grid efficiently by energization heating, and with high sensitivity and accuracy. Analysis of gas components (partial pressure measurement) can be performed.
- each electrode of the quadrupole unit is held by an insulating holder, and this holder is detachably attached to the support. It is advantageous.
- the ion detector is detachably attached to the holder or the support.
- a plate-like ion collector is provided on the support so as to be opposed to the ion detector with the grid of the ion source interposed therebetween so that the total pressure in the test body can be measured.
- a configuration in which a cylindrical ion collector arranged so as to surround an ion source having a filament and a grid is further provided on the support so that the total pressure in the test body can be measured can be adopted.
- a single quadrupole mass spectrometer can measure the total pressure of the test specimen in addition to analyzing the gas components, and the ion collector is directly attached to the connection terminal provided on the support. This eliminates the need for expensive wiring for ion current detection, and realizes a configuration for measuring total pressure at a low cost. If the configuration of the first aspect is adopted and the quadrupole part or ion detection part is detachable from the support, the total pressure of the test specimen can be measured simply by removing these parts. Therefore, it can be used as a vacuum gauge according to the application or as a quadrupole mass spectrometer equipped with a vacuum gauge.
- the ion collector When the ion collector is formed in a plate shape, the surface is easily contaminated and the sensitivity is likely to be lowered. On the other hand, when the ion collector is formed in a cylindrical shape, high accuracy is achieved up to a low pressure due to the influence of soft X-rays. There is a possibility that the total pressure cannot be measured. For this reason, it is necessary to select the kind of ion collector suitably according to a use.
- thermoelectrons can be emitted from the filament.
- a configuration further including a vacuum gauge capable of measuring pressure within a pressure range from atmospheric pressure to the time when thermoelectrons can be emitted from the filament.
- FIG. 6 is a sectional view taken along line VI-VI in FIG. 5.
- a specimen TP is a vacuum chamber and is mounted on a test port TP1 of the specimen TP to analyze a gas component in the specimen TP.
- the quadrupole mass spectrometer will be described.
- MA1 is a quadrupole mass spectrometer, and this quadrupole mass spectrometer MA1 includes a sensor unit M1 and a control unit C.
- the sensor unit M1 has a disk-like support 1.
- the support 1 is made of a metal such as aluminum or stainless steel, and an O-ring (seal means) 11 is provided on the outer peripheral edge of the upper surface.
- O-ring seal means
- An ion source 2 is provided on the support 1.
- the ion source 2 is composed of a spiral grid 21 disposed above the center of the support 1 and a filament 22 disposed around the grid 21 and covering the surface of the Ir line with yttrium oxide. ing. Both free ends of the grid 21 and the filament 22 are respectively connected (directly attached) to the grid connection terminals 23a and 23b and the filament connection terminals 24a and 24b which are vertically provided through the support body 1. Yes.
- each electrode 31 is supported by a cylindrical holder 32 made of an insulating material so that the upper portion of each electrode 31 protrudes upward from the holder 32.
- two socket type connectors 34 respectively connected to the electrodes 31 through wirings 33 are provided. Then, the two connection terminals 35a and 35b erected on the support body 1 are fitted into the respective socket type connectors 34 of the holder 32 from above, so that the connection terminals 35a and 35b are eventually connected to the support body 1.
- the holder 32 is detachably supported and electrically connected. Thereby, the structure of the sensor part M1 is simplified.
- the method of supporting the holder 32 with the support 1 is not limited to the above, and a separate support member (not shown) is provided on the support 1 so that the holder 32 is supported on the support member. May be.
- An ion detection unit 4 is provided on the inner upper side of each electrode 31 of the quadrupole unit 3.
- the ion detection unit 4 is configured by a Faraday cup that collects gas molecules that are ionized by the ion source 2 and pass between the electrodes 31 of the quadrupole unit 3 and reach the upper side thereof.
- the wiring 41 from the ion detector 4 is also connected to a socket-type connector 42 provided on the lower surface of the holder 32 and is connected to a connection terminal 43 erected on the support 1 in the same manner as described above. Yes.
- the wirings 33 and 41 those in which a metal wire such as copper is covered with a ceramic cover are used.
- control unit C includes a control unit 51 including a computer, a memory, a sequencer, and the like.
- the control unit 51 is measured by operation of each power source described later, switching of switching elements in the power circuit, and an ammeter. Centrally controls the output of current values to a display (not shown).
- the control unit C also includes a filament power supply E1 and an ionization power supply E2 that ionizes the gas in the specimen TP.
- One output (positive) from the power supply E1 is connected to the filament connection terminal 24b, and one output (positive) from the power supply E2 is connected to one connection terminal 23a for the grid.
- the control unit C includes a power supply E3 for energization heating of the grid 21 and a switching element SW1.
- One (negative) output from the power supply E3 is connected to the connection terminal 23b, and the other output (positive) is connected to the other output from the power supply E2 via the switching element SW1.
- control unit C includes a DC + RF power source E4 that applies a DC voltage and a high-frequency voltage to each of the electrically coupled electrodes 31, and the output of the DC + RF power source E4 is applied to one of the opposing electrodes 31, respectively. Connected (only one is shown in FIG. 1).
- the control unit C includes a power source E5 for accelerating ions and a power source E6 for forming a central electric field in series, and one output from the power source E5 is connected to one (positive) output from the power source E2. The other output is grounded.
- the control unit C is provided with an ammeter 52 that measures an ion current value collected by the ion detector 4 and flowing to the ground.
- the quadrupole mass spectrometer MA1 can measure the total pressure in the test body. That is, a plate-like ion collector 61 is provided on the support 1 so as to be opposed to the ion detector 4 with the grid 21 interposed therebetween. The ion collector 61 is directly attached to a connection terminal 62 provided through the support 1 in the vertical direction. Further, the control unit C is provided with an ammeter 63 that measures an ion current value collected by the ion collector 61 and flowing to the ground.
- a tube P having flanges P1 and P2 at both ends is attached around the sensor unit M1. That is, the tubular body P is extrapolated from above the sensor portion M1, and the lower flange P2 of the tubular body P is brought into surface contact with the outer edge of the upper surface of the support 1, and fixed in this state by a clamp or the like. Thereby, the O-ring 11 is vacuum-sealed.
- the flange P1 on the upper side of the tube P is brought into surface contact with the flange TP2 of the test port TP1 of the test body TP via the O-ring 12, and fixed in this state by a clamp or the like to attach the sensor unit M1.
- the sensor unit M1 can be directly attached to the test port TP1 without using the tube P.
- the inside of the test body TP is evacuated by a vacuum pump, and when a predetermined vacuum pressure is reached, gas analysis is started.
- thermoelectron is drawn in by applying a positive voltage to the grid 21 with the power supply E2.
- positive ions are generated from gas atoms and molecules around the filament 22 colliding with the thermal electrons.
- ions of the ionized gas component are drawn into the quadrupole portion 3 from the grid 21 side.
- the switching element SW1 is held off (cut off).
- the value of the ionic current flowing through the ion collector 61 is measured by the ammeter 63, and the total pressure at that time can also be measured.
- a predetermined AC voltage is applied to the four electrodes 31 of the quadrupole unit 3 by a DC + RF power source E4, which is a DC voltage superimposed on the DC voltage that has risen from the ground potential by the center electric field voltage of the power source E6.
- a DC + RF power source E4 which is a DC voltage superimposed on the DC voltage that has risen from the ground potential by the center electric field voltage of the power source E6.
- a spectrum is obtained by linearly changing the AC voltage while keeping the ratio of the DC voltage and the AC voltage constant, and the gas component in the test body is analyzed from the ion current value. In this case, it is also possible to display an instruction value calculated from the ion current value for a specific gas component.
- the control unit 51 determines that the grid 21 is contaminated.
- the switching element SW1 is turned on (connected) by the control unit 51, and a current of about 2 A is supplied to the grid 21 by the power source E3, and energization heating is performed for a predetermined time. Thereby, molecules and atoms attached to the surface of the grid 21 are removed by evaporation.
- the ion source 2 is positioned on the support 1 side, and both free ends of the filament 22 and the grid 21 are on the support 1.
- the wiring to the ion detector 4 is longer than that of the conventional example, but only one wiring for detecting the ion current is sufficient. Therefore, the structure can be simplified and the assembly can be facilitated as compared with the conventional example, and the cost can be reduced.
- the wiring loss is eliminated, it is possible to realize a configuration in which the heating of the grid 21 is efficiently performed.
- the wiring for the ion source 2 can be made unnecessary and the effect of degassing from the wiring can be eliminated, and the contamination of the grid can be efficiently prevented by energization heating, and the sensitivity is high with high accuracy. It is possible to analyze the residual gas component.
- each electrode 31 of the quadrupole part 3 is held by the holder 32, and the ion detector 4 is detachably attached to the holder 32, and the socket type connector 34, If 42 is provided and is fitted to the connection terminals 35a, 35b, and 43 standing on the support plate 1, an assembly structure is adopted, so that the assembly and handling can be further facilitated.
- the total pressure of the test specimen can be measured with one quadrupole mass spectrometer MA1, and the ion collector 61 is provided on the support plate 1. Since it is directly attached to the connection terminal 62, an expensive wiring for ion current detection is not required, and a configuration for measuring the total pressure can be realized at a low cost.
- the quadrupole mass spectrometer MA1 of the first embodiment has been described above, but the present invention is not limited to the above.
- the sensor unit 3 and the control unit C are separated from each other.
- the sensor unit 3 and the control unit C may be integrally incorporated in the same housing.
- the ion detector 4 is located at a position farthest from the support 1 side, that is, a position in contact with the atmosphere in the test object to be analyzed. In such a case, even ions existing in the test body may be detected by the ion detection unit 4, and depending on the test body TP, the gas component may not be analyzed with high accuracy.
- the sensor unit M2 of the quadrupole mass spectrometer detects ions so as to shield the ion detection unit 4 from ions existing in the test body.
- a plate-shaped shielding member 7 that covers the upper portion of the portion 4 is further provided.
- the shape of the shielding member 7 is not limited to a plate-like shape, and a hemispherical shape can also be used.
- the sensor unit M2 of the modification includes a cylindrical ion collector 610 as shown in FIG.
- the sensor unit M ⁇ b> 2 further includes a Pirani gauge 8 so that pressure can be measured within a pressure range from atmospheric pressure to a pressure at which thermoelectrons can be emitted from the filament 22.
- the support 1 has been described as an example of a disk shape, but is not limited thereto.
- the support plate 10 includes a central base portion 10a formed of a flat plate, and the base portion 10a. It is comprised from the cylindrical wall part 10b standingly arranged by the outer periphery, and the flange 10c formed in the upper end of this cylindrical wall part 10b.
- the base 10a is provided with grid connection terminals 23a and 23b and filament connection terminals 24a and 24b. Further, the upper surface of the flange 10c is located above the grid 21 connected to the connection terminals 23a and 23b and the filament 22 connected to the connection terminals 24a and 24b. Thereby, if the quadrupole part 3 and the ion detection part 4 are detached, it is configured as a vacuum gauge (ionization vacuum gauge) for measuring the total pressure of the test body (see FIG. 3B).
- a vacuum gauge ionization vacuum gauge
- the control unit according to the modification is configured by connecting a main unit C1 that measures the total pressure and the like in the test body and a slave unit C2 that analyzes gas components in the test body. ing. That is, the main unit C1 has a first casing C11.
- the first casing C11 includes a power supply unit C12 that supplies power, a control unit C13 such as a CPU that controls the operation of the control unit, and an ion.
- An ion power supply unit C14 that supplies an electrode to the source 2 and a current detection circuit C15 that measures a current value of ions collected by the ion collectors 61 and 610 are provided.
- the slave unit C2 communicatively connected to the main unit C1 has a second casing C21.
- the second casing C21 has a DC voltage and a high-frequency voltage applied to the electrode 31 of the quadrupole portion 3.
- a current detection circuit C23 that measures the current value of ions collected by the ion detection unit 4.
- the sensor unit M4 includes a disk-shaped support body 100.
- the support 100 is made of metal such as aluminum or stainless steel, and an O-ring (seal means) 11 is provided on the outer peripheral edge of the upper surface.
- An ion source 2 is provided on the support 100.
- the ion source 2 oxidizes the spiral grid 21 arranged in parallel to the support 100 on one side in the radial direction of the support 100 and the surface of the Ir line arranged through the central space of the grid 21.
- a filament 22 covered with yttrium Both free ends of the grid 21 and the filament 22 are respectively connected (directly attached) to the grid connection terminals 23a and 23b and the filament connection terminals 24a and 24b which are vertically provided through the support body 100. Yes.
- An annular focus electrode FP is arranged on the inner side in the radial direction of the support body 100 adjacent to the ion source 2.
- the focus electrode FP is directly attached to a connection terminal FP1 for a grid that stands up and down through the support body 100, and the connection terminal FP1 is connected to a power source provided in the control unit C. Then, by applying a predetermined DC voltage to the focus electrode FP at the time of gas analysis, diffusion of ions incident on the quadrupole part 3 is suppressed.
- Each electrode 31 is held by a box-shaped holder 320 made of an insulating material and opened on the lower side, and this holder 320 is detachably attached to the support body 100.
- Two of the opposing electrodes 31 are electrically connected to the two connection terminals 35 a and 35 b erected on the support 100 by wiring W.
- An ion detector 4 is provided on the other radial side of the support 10 adjacent to the quadrupole 3.
- the ion detection part 4 is comprised from the Faraday cup which collects the gas molecule which passes between each electrode 31 of the quadrupole part 300, and reaches
- the ion detector 4 is also connected (directly attached) to a connection terminal 40 erected on the support 100.
- a plate-like ion collector 61 is provided so as to face the ion detector 4 with the grid 21 interposed therebetween.
- the ion collector 61 is directly attached to a connection terminal 62 provided through the support 1 in the vertical direction.
- a tube P having flanges P1 and P2 at both ends is attached around the sensor M4.
- the length of the tube body P can be shortened compared to that of the first embodiment, and as a result, the test body TP when mounted on the test body TP.
- the ion source 2 since the ion source 2, the quadrupole unit 300, and the ion detection unit 4 are arranged side by side on the support 100, no wiring is required, and the structure can be simplified. In addition to facilitating assembly, further cost reduction can be achieved.
- MA1, MA2 quadrupole mass spectrometer, M1-M4: sensor unit, C: control unit, 1, 10, 100 ... support, 11: sealing means, 2 ... ion source, 21 ... grid, 22 ... filament 3 ... Quadrupole part, 31 ... Electrode, 32 ... Holder, 4 ... Ion detection part, 35a, 35b, 43 ... Connection terminal, E1 to E6 ... Power source, 61, 610 ... Ion collector (for total pressure measurement), 7 ... shielding member, 8 ... (Pirani) vacuum gauge
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Abstract
Description
Claims (10)
- 試験体内のガス成分を分析し得る四重極型質量分析計であって、
試験体に着脱自在に装着し得るセンサ部を備え、
この試験体に対するセンサ部の装着方向を上方として、センサ部は、下端に設けられた所定形状の支持体と、この支持体上に設けられた、フィラメント及びグリッドを有して上記ガスをイオン化するイオン源と、このイオン源上に設けられた、4本の柱状電極を周方向に所定間隔で配置してなる四重極部と、この四重極部上に設けられた、相対する電極間に直流電圧と交流電圧とを印加することで四重極部を通過した所定のイオンを捕集するイオン検出部と、を備えることを特徴とする四重極型質量分析計。 - 前記イオン検出部の上方に、このイオン検出部を遮蔽する遮蔽手段を更に備えることを特徴とする請求項1記載の四重極型質量分析計。
- 前記支持体は、イオン源を囲うようにして、イオン源の上方まで延びる筒状壁を備え、この筒状壁の上端に、試験体に固定可能なフランジが設けられていることを特徴とする請求項1または請求項2記載の四重極型質量分析計。
- 試験体内のガス成分を分析し得る四重極型質量分析計であって、
試験体に着脱自在に装着し得るセンサ部を備え、
この試験体に対するセンサ部の装着方向を上方として、このセンサ部は、下端に設けられた所定形状の支持体と、この支持体上に配置された、フィラメント及びグリッドを有して上記ガスをイオン化するイオン源と、支持体上でイオン源に隣接配置された、4本の円柱状電極を上下方向に対して直交する方向に平行にかつ周方向に所定間隔で配置してなる四重極部と、支持体上で四重極部に隣接配置された、相対する電極間に直流電圧と交流電圧とを印加することでこの四重極部を通過した所定のイオンを捕集するイオン検出部と、を備えることを特徴とする四重極型質量分析計。 - 前記イオン源のフィラメント及びグリッドの自由端は、前記支持体を上下方向に貫通して固定された接続端子に配線なしに接続されていることを特徴とする請求項1~請求項4のいずれか1項に記載の四重極型質量分析計。
- 前記四重極部の各電極は絶縁性のホルダで保持され、このホルダが前記支持体に着脱自在に取り付けられていることを特徴とする請求項1~請求項5のいずれか1項に記載の四重極型質量分析計。
- 前記イオン検出部は、前記ホルダまたは支持体に着脱自在に取り付けられていることを特徴とする請求項6記載の四重極型質量分析計。
- 前記支持体上に、イオン源のグリッドを挟んでイオン検出部に対向配置された板状のイオンコレクタを更に備え、試験体内の全圧を測定可能としたことを特徴とする請求項1~請求項7のいずれか1項に記載の四重極型質量分析計。
- 前記支持体上に、フィラメント及びグリッドを有するイオン源を囲繞するように配置された筒状のイオンコレクタを更に備え、試験体内の全圧を測定可能としたことを特徴とする請求項1~請求項7のいずれか1項に記載の四重極型質量分析計。
- 大気圧から、前記フィラメントから熱電子を放出し得るまでの圧力範囲内で圧力測定できる真空計を更に備えることを特徴とする請求項1~請求項9のいずれか1項に記載の四重極型質量分析計。
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US13/519,928 US8674298B2 (en) | 2010-02-17 | 2011-02-15 | Quadrupole mass spectrometer |
CN2011800086882A CN102763190A (zh) | 2010-02-17 | 2011-02-15 | 四极杆质谱仪 |
DE112011100568.7T DE112011100568B4 (de) | 2010-02-17 | 2011-02-15 | Vierpol-Massenspektrometer |
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WO2013069395A2 (ja) * | 2011-11-11 | 2013-05-16 | シャープ株式会社 | イオン発生ユニット及び電気機器 |
JP6335376B1 (ja) * | 2017-08-07 | 2018-05-30 | 株式会社アルバック | 四重極型質量分析計及びその感度低下の判定方法 |
WO2019155543A1 (ja) * | 2018-02-07 | 2019-08-15 | 株式会社島津製作所 | 質量分析装置 |
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Also Published As
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JP5669324B2 (ja) | 2015-02-12 |
US20120280122A1 (en) | 2012-11-08 |
DE112011100568T5 (de) | 2012-12-13 |
US8674298B2 (en) | 2014-03-18 |
DE112011100568B4 (de) | 2017-01-19 |
CN102763190A (zh) | 2012-10-31 |
JPWO2011102117A1 (ja) | 2013-06-17 |
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