EP1959476A1 - Spectromètre de masse - Google Patents

Spectromètre de masse Download PDF

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Publication number
EP1959476A1
EP1959476A1 EP07003392A EP07003392A EP1959476A1 EP 1959476 A1 EP1959476 A1 EP 1959476A1 EP 07003392 A EP07003392 A EP 07003392A EP 07003392 A EP07003392 A EP 07003392A EP 1959476 A1 EP1959476 A1 EP 1959476A1
Authority
EP
European Patent Office
Prior art keywords
electrodes
mass spectrometer
ions
spectrometer according
mass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07003392A
Other languages
German (de)
English (en)
Inventor
Jörg Dr.-Ing. Müller
Jan-Peter Dipl. Ing. Hauschild
Eric Dipl-Ing. Wapelhorst
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Ludwig Krohne GmbH and Co KG
Original Assignee
Technische Universitaet Hamburg TUHH
Tutech Innovation GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Technische Universitaet Hamburg TUHH, Tutech Innovation GmbH filed Critical Technische Universitaet Hamburg TUHH
Priority to EP07003392A priority Critical patent/EP1959476A1/fr
Priority to US12/526,163 priority patent/US8134120B2/en
Priority to CA002678460A priority patent/CA2678460A1/fr
Priority to JP2009549804A priority patent/JP2010519687A/ja
Priority to CN200880005532.7A priority patent/CN101636814B/zh
Priority to PCT/EP2008/001287 priority patent/WO2008101669A1/fr
Publication of EP1959476A1 publication Critical patent/EP1959476A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/0013—Miniaturised spectrometers, e.g. having smaller than usual scale, integrated conventional components
    • H01J49/0018—Microminiaturised spectrometers, e.g. chip-integrated devices, Micro-Electro-Mechanical Systems [MEMS]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/004—Combinations of spectrometers, tandem spectrometers, e.g. MS/MS, MSn
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/44—Energy spectrometers, e.g. alpha-, beta-spectrometers
    • H01J49/46—Static spectrometers
    • H01J49/48—Static spectrometers using electrostatic analysers, e.g. cylindrical sector, Wien filter
    • H01J49/482—Static spectrometers using electrostatic analysers, e.g. cylindrical sector, Wien filter with cylindrical mirrors

Definitions

  • Mass spectrometers are widely used. While mass spectrometers were primarily used for scientific purposes, today there are more and more applications related to environmental protection, measurements of air quality for the detection of harmful gases, process monitoring and control, safety checks z. In airports, and the like. For this purpose, mass spectrometers are particularly suitable, which have small dimensions and are therefore easy to transport and use everywhere. Another requirement for large scale application is that these mass spectrometers are inexpensive to manufacture.
  • a magnetic field separator In another mass spectrometer, a magnetic field separator is used ( WO 96/16430 ). However, this requires a certain minimum size, since on the one hand for the magnetic field separator very high magnetic field strengths must be present, while elsewhere the magnetic field must be shielded in order not to influence the ionization or ion optics.
  • a mass spectrometer of the type mentioned at the outset has been developed for use in a microsystem which can be produced by the methods customary in microsystem technology ( DE 197 20 278 A1 ).
  • This mass spectrometer has very small dimensions.
  • the production is very complex, since it requires on the one hand self-supporting insulated grids for the acceleration of the ionization of the gas to be examined and on the other hand electrically contacted, galvanically grown structures of copper or nickel must be produced.
  • the construction of the individual components is carried out separately on a total of four substrates, which must be connected to a monolithic system with a suitable construction and connection technology.
  • the object of the invention is to provide a mass spectrometer of the type mentioned, which can be produced easily and inexpensively and is suitable for mass production.
  • the function of the mass spectrometer with the mass-dependent separation of the ions by acceleration / deceleration is based on the fact that the acceleration through the fields of the electrodes different ions reach a different speed and due to these differences in speed, the separation takes place.
  • the corresponding transmitted ion beam is not monochromatic, but also contains ions of greater or lesser mass, which had a greater or lesser start speed due to the thermal movement.
  • the energy filter is provided in which between two electrodes with different, in particular opposite potential, the ions are deflected by 90 ° in a channel between the electrodes.
  • the mass spectrometer is constructed completely planar and can be produced from wafers with the techniques of microelectronics.
  • the components are arranged on a flat, nonconducting substrate on which the metallic connection wiring has first been applied.
  • the ionization chamber, the electrodes for accelerating the electrons and ions, the detector for the ions and the energy filters are produced by photolithography and etching of a wafer applied to the substrate and the wiring, wherein all components are produced in a photolithographic and etching step. Subsequently, the components are then covered by a flat non-conductive substrate so as to obtain a closed unit.
  • the electron source is a thermal emitter.
  • the electron source comprises a plasma chamber having a rare gas feed passage and a microwave line for introducing and maintaining the plasma, the plasma chamber, the feed channel and the microwave line also being formed by etching the semiconductor die together with the others Parts are made.
  • the electrodes for mass-dependent separation of the ions by acceleration / deceleration are at an advantageous Embodiment designed as a time-of-flight mass separator and arranged.
  • a first gate electrode arrangement the ion beam is pulsed. Only short ion pulses reach the drift path, where the pulse diverges due to the different velocities of the ions.
  • the ion pulse is scanned. Different maturities corresponding to different masses. The energy filter then ensures that only ions with exactly one energy reach the detector and are registered there.
  • a larger number of electrodes are provided in the measuring path, which are subjected to alternating electrical voltages which "migrate" from one end to the other end with the ions. Only the ions at exactly the speed corresponding to the "rate of migration” of the electric fields always pass through electrodes to which no voltage is currently applied. All other ions that are out of sync move between electrodes that are being applied with an electrical voltage so that they are deflected to the side.
  • the detector for the ions is advantageously designed as a Faradaydetektor. In another advantageous embodiment, which has greater sensitivity, the detector for the ions is designed as an electron multiplier.
  • the electrodes for accelerating the electrons may be two apertured electrodes to which different electrical potentials can be applied. These Electrodes may also be made of the semiconductor material such that the prior art grating arrangement for accelerating electrons of the prior art (US Pat. DE 197 20 278 A ), which is difficult to manufacture, is avoided.
  • the mass spectrometer has a microcontroller, by which it is controlled.
  • the metallic conductors of the wiring and the electrodes are advantageously electrically connected by eutectic semiconductor metal contacts.
  • bumps of a suitable metal are arranged on the wires or printed conductors in the corresponding places, which form the eutectic semiconductor metal contacts during bonding with the semiconductor chip.
  • the semiconductor material is doped silicon.
  • a particularly advantageous metal for the eutectic contacts is gold.
  • the non-conductive substrates are advantageously made of borosilicate glass or quartz glass.
  • the invention is also characterized by a method for producing the mass spectrometer.
  • the metal wiring on which metal pads for connection to the semiconductor electrodes are disposed is applied to a flat non-conductive substrate. Cores are then etched into the die in order for the semiconductor resistor to contact only the metal pads but not the wiring during bonding.
  • the Semiconductor platelets are then applied to the substrate and arranged on the same a mask for photolithography. The alignment of the mask with respect to the wiring and gold pads can be done optically by using light of a wavelength for which the silicon wafer is transparent. For silicon, a wavelength above 1.2 ⁇ m is suitable.
  • the semiconductor die is then locally etched in one step to create the components of the mass spectrometer. Subsequently, the semiconductor wafer is covered with a second non-conductive substrate.
  • At the second non-conductive substrate can be applied in advance, a further wiring to z. B. electrodes of electrode pairs to each other.
  • the finished semiconductor chip is shown, which in this embodiment is made of doped silicon and in which the corresponding components are produced by etching.
  • the spectrometer has a supply channel a for the sample gas, which is passed into the ionization chamber b .
  • the electrons required for the ionization with an energy of typically 70 eV are extracted from a plasma chamber d and accelerated between two aperture openings c lying at different potentials.
  • the entire area between the apertures is evacuated to the sides of the system.
  • the noble gas is supplied via the channel e of the plasma chamber d . It is excited by the microwave waveguide f with microwaves to generate the plasma and thereby release the required electrons.
  • the pressure in the plasma chamber is controlled by the pre-pressure upstream of channel e or a connected capillary.
  • the ions from the ionization chamber b are extracted by an electric field between the chamber wall and ion optics g on a further aperture, accelerated with defined energy and focused.
  • the ion beam is pulsed at the first gate electronics array h .
  • the ion pulse is scanned.
  • the energy filter k ensures that ions only reach the detector 1 with exactly one energy and are registered there.
  • FIG. 3 and 4 show another embodiment, which in the area of the accelerating electrodes of the embodiment of the Fig. 1 and 2 different.
  • An alternating voltage is applied to the electrodes m of the traveling-field separator, so that ions which pass between electrodes which are currently subjected to a voltage are deflected to the side and removed from the beam. Only the ions at exactly the right speed, passing through the electrodes when there is no voltage across them, reach the energy filter k , whose two electrodes on both sides of the quarter-circle-shaped channel are at opposite potentials, so only ions with a well-defined one Let energy through. These ions then strike the detector 1 again .
  • FIGS. 5 and 6 is different from the one of Fig. 1 and 2 in that, instead of a noble gas plasma, a thermal emitter n is used to release the electrons required for the ionization.
  • FIGS. 7 and 8 the electrode area of the mass spectrometer according to the invention is shown.
  • the support for the system is the borosilicate glass 1, to which metallic conductor tracks 2 are applied in order to connect the electrodes electrically.
  • the structure of the electrodes is in Fig. 8 shown in section.
  • Fig. 9 the principle of manufacturing the mass spectrometer is shown.
  • etching in the silicon wafer recesses 8 are generated, which provide in the finished mass spectrometer for the required distance between the metallic interconnects 2 on the carrier substrate 1 and the silicon wafer 6 .
  • the depth of the etching pits 8 is designed so that the gold pads 3 come into contact with the bottom of the etching pit 8 when joining substrate 1 and silicon platelets 6 .
  • the arrangement thus produced according to I is then bonded in step II .
  • step III after applying a corresponding mask and exposure by etching, the desired structure is produced.
  • the upper substrate 7 shown in I, II and III is not actually present at these steps. It also carries a conductor and is then bonded to the device at IV , electrodes being connected by the conductor disposed on the upper substrate 7 .
  • the production of the mass spectrometer can take place in uniform steps in wafers.
  • the final mass spectrometer shown in the figures may have dimensions as small as 5x10 mm. Due to the small size and low demands on the pumping power of a vacuum pump are made.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
  • Electron Tubes For Measurement (AREA)
EP07003392A 2007-02-19 2007-02-19 Spectromètre de masse Withdrawn EP1959476A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP07003392A EP1959476A1 (fr) 2007-02-19 2007-02-19 Spectromètre de masse
US12/526,163 US8134120B2 (en) 2007-02-19 2008-02-19 Mass spectrometer
CA002678460A CA2678460A1 (fr) 2007-02-19 2008-02-19 Spectrometre de masse
JP2009549804A JP2010519687A (ja) 2007-02-19 2008-02-19 質量分析計
CN200880005532.7A CN101636814B (zh) 2007-02-19 2008-02-19 质谱仪
PCT/EP2008/001287 WO2008101669A1 (fr) 2007-02-19 2008-02-19 Spectromètre de masse

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP07003392A EP1959476A1 (fr) 2007-02-19 2007-02-19 Spectromètre de masse

Publications (1)

Publication Number Publication Date
EP1959476A1 true EP1959476A1 (fr) 2008-08-20

Family

ID=38235375

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07003392A Withdrawn EP1959476A1 (fr) 2007-02-19 2007-02-19 Spectromètre de masse

Country Status (6)

Country Link
US (1) US8134120B2 (fr)
EP (1) EP1959476A1 (fr)
JP (1) JP2010519687A (fr)
CN (1) CN101636814B (fr)
CA (1) CA2678460A1 (fr)
WO (1) WO2008101669A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015132005A1 (fr) * 2014-03-06 2015-09-11 Gregor Quiring Dispositif pour la séparation d'ions par accélération sélective

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010018830A1 (de) 2010-04-29 2011-11-03 Bayer Technology Services Gmbh Flüssigkeitsverdampfer
CN101963596B (zh) * 2010-09-01 2012-09-05 中国科学院广州地球化学研究所 基于四极杆质谱的稀有气体测定系统
DE102011015595B8 (de) * 2011-03-30 2015-01-29 Krohne Messtechnik Gmbh Verfahren zur Ansteuerung eines synchronous ion shield Massenseparators
JP5813536B2 (ja) * 2012-03-02 2015-11-17 株式会社東芝 イオン源
US9418827B2 (en) * 2013-07-23 2016-08-16 Hamilton Sundstrand Corporation Methods of ion source fabrication
JP6624482B2 (ja) * 2014-07-29 2019-12-25 俊 保坂 超小型加速器および超小型質量分析装置
JP7018090B2 (ja) * 2020-04-08 2022-02-09 俊 保坂 超小型加速器および超小型質量分析装置およびイオン注入装置

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0427532A2 (fr) * 1989-11-08 1991-05-15 Schultz, J. Albert Spectrométrie de masse d'ions de recul à haute résolution pour l'analyse d'isotopes et de traces d'éléments
US5486697A (en) * 1994-11-14 1996-01-23 California Institute Of Technology Array of micro-machined mass energy micro-filters for charged particles
WO1996011492A1 (fr) * 1994-10-07 1996-04-18 Northrop Grumman Corporation Filtre de masse miniaturise
GB2391694A (en) * 2002-08-01 2004-02-11 Microsaic Systems Ltd A monolithic micro-engineered quadrupole mass spectrometer
US20050258514A1 (en) * 2004-05-07 2005-11-24 Stillwater Scientific Microfabricated miniature grids

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JP2765890B2 (ja) * 1988-12-09 1998-06-18 株式会社日立製作所 プラズマイオン源微量元素質量分析装置
JP2774878B2 (ja) * 1991-04-25 1998-07-09 株式会社日立製作所 多層膜絶縁物試料の二次イオン質量分析方法
US5386115A (en) 1993-09-22 1995-01-31 Westinghouse Electric Corporation Solid state micro-machined mass spectrograph universal gas detection sensor
US5466932A (en) * 1993-09-22 1995-11-14 Westinghouse Electric Corp. Micro-miniature piezoelectric diaphragm pump for the low pressure pumping of gases
US5492867A (en) * 1993-09-22 1996-02-20 Westinghouse Elect. Corp. Method for manufacturing a miniaturized solid state mass spectrograph
US5481110A (en) * 1993-09-22 1996-01-02 Westinghouse Electric Corp Thin film preconcentrator array
JPH09511614A (ja) * 1994-11-22 1997-11-18 ノースロップ グルマン コーポレーション ソリッドステート型の質量分析器汎用ガス検出センサ
DE19720278B4 (de) 1997-05-13 2007-08-02 Sls Micro Technology Gmbh Miniaturisiertes Massenspektrometer
JPH11250854A (ja) * 1998-03-02 1999-09-17 Ulvac Corp エッチングプラズマにおける基板入射イオンの分析法及び装置
US6815668B2 (en) * 1999-07-21 2004-11-09 The Charles Stark Draper Laboratory, Inc. Method and apparatus for chromatography-high field asymmetric waveform ion mobility spectrometry
US6396057B1 (en) * 2000-04-18 2002-05-28 Waters Investments Limited Electrospray and other LC/MS interfaces
MX2007001434A (es) * 2004-08-02 2008-03-07 Owlstone Ltd Espectrometro de movilidad ionica.
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Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0427532A2 (fr) * 1989-11-08 1991-05-15 Schultz, J. Albert Spectrométrie de masse d'ions de recul à haute résolution pour l'analyse d'isotopes et de traces d'éléments
WO1996011492A1 (fr) * 1994-10-07 1996-04-18 Northrop Grumman Corporation Filtre de masse miniaturise
US5486697A (en) * 1994-11-14 1996-01-23 California Institute Of Technology Array of micro-machined mass energy micro-filters for charged particles
GB2391694A (en) * 2002-08-01 2004-02-11 Microsaic Systems Ltd A monolithic micro-engineered quadrupole mass spectrometer
US20050258514A1 (en) * 2004-05-07 2005-11-24 Stillwater Scientific Microfabricated miniature grids

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YOON H J ET AL: "Fabrication of a novel micro time-of-flight mass spectrometer", SENSORS AND ACTUATORS A, ELSEVIER SEQUOIA S.A., LAUSANNE, CH, vol. 97-98, 1 April 2002 (2002-04-01), pages 441 - 447, XP004361634, ISSN: 0924-4247 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015132005A1 (fr) * 2014-03-06 2015-09-11 Gregor Quiring Dispositif pour la séparation d'ions par accélération sélective

Also Published As

Publication number Publication date
WO2008101669A8 (fr) 2008-12-24
JP2010519687A (ja) 2010-06-03
US20100090103A1 (en) 2010-04-15
CA2678460A1 (fr) 2008-08-28
WO2008101669A1 (fr) 2008-08-28
CN101636814B (zh) 2013-01-23
CN101636814A (zh) 2010-01-27
US8134120B2 (en) 2012-03-13

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