WO2008101669A1 - Massenspektrometer - Google Patents
Massenspektrometer Download PDFInfo
- Publication number
- WO2008101669A1 WO2008101669A1 PCT/EP2008/001287 EP2008001287W WO2008101669A1 WO 2008101669 A1 WO2008101669 A1 WO 2008101669A1 EP 2008001287 W EP2008001287 W EP 2008001287W WO 2008101669 A1 WO2008101669 A1 WO 2008101669A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mass spectrometer
- ions
- electrodes
- spectrometer according
- mass
- Prior art date
Links
- 150000002500 ions Chemical class 0.000 claims abstract description 53
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 239000004065 semiconductor Substances 0.000 claims abstract description 25
- 238000005530 etching Methods 0.000 claims abstract description 13
- 238000000206 photolithography Methods 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- 230000001133 acceleration Effects 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 10
- 239000004020 conductor Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 230000001419 dependent effect Effects 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 230000005496 eutectics Effects 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000005388 borosilicate glass Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910052756 noble gas Inorganic materials 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 235000012431 wafers Nutrition 0.000 description 11
- 239000007789 gas Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 230000005684 electric field Effects 0.000 description 4
- 238000010884 ion-beam technique Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241001116459 Sequoia Species 0.000 description 1
- OFLYIWITHZJFLS-UHFFFAOYSA-N [Si].[Au] Chemical compound [Si].[Au] OFLYIWITHZJFLS-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
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
- the invention relates to a mass spectrometer, comprising:
- Electrodes for accelerating the ionizing electrons are Electrodes for accelerating the ionizing electrons
- 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 these purposes, in particular These mass spectrometers are small in size and 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.
- ISSN 0924-42457
- the substrate silicon which has an advantage of a wide variety of structuring possibilities, but has the disadvantage that large, the Substrate heating leakage currents flow.
- Another disadvantage is the high dielectric constant, which leads to signal distortions, even if an insulating intermediate layer of silicon dioxide is used.
- the previously known mass spectrometer is not completely built up; Separator and detector are separate elements as shown in FIG.
- a mass spectrometer of the type mentioned was 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 structure of the individual Components are separated 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 solution according to the invention consists in a mass spectrometer of the type mentioned in the introduction,
- the components are arranged on a flat non-conductive substrate
- the ionization chamber, the electrodes for accelerating the electrons and ions, the detector for the ions and the energy filter are produced by photolithography and etching a doped semiconductor wafer deposited on the substrate and the wiring and the aforementioned parts are covered by a second flat non-conductive substrate ,
- ctor is meant an arc section on which the ions move.
- the function of the mass spectrometer with the mass-dependent separation of the ions by acceleration / deceleration is based on the fact that accelerated by the fields of the electrodes different heavy 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 the ions in a channel (sector) are deflected between the electrodes between two electrodes with different, in particular opposite, potential.
- the particular advantage of the invention is that 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 nonconductive substrate on which first the metal connection wiring has been applied.
- the ionization chamber, the electrodes for accelerating the electrons and ions, the detector for the ions and the energy filter are produced by photolithography and etching of a semiconductor wafer applied to the substrate and the wiring, wherein in a photolithographic see and etching step all components are generated. 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 formed and arranged in an advantageous embodiment as a time-of-flight mass separator.
- 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 on a second gate electrode arrangement. Different transit times 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 section, which are subjected to alternating electrical voltages which "migrate" from one end to the other end with the ions.
- they At exactly the speed corresponding to the "rate of migration" of the electric fields, they always pass through electrodes to which no voltage is currently applied, and all other ions that are not in tact move between electrodes, to which just one electrical voltage is applied so that they are deflected to the side.
- the detector for the ions is advantageously designed as a Faraday detector.
- 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 can also be made of the semiconductor material, so that the previously known grating arrangement for accelerating the electrons of the prior art (DE 197 20 278 A), which is difficult to produce, 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.
- eutectic semiconductor metal contacts are on the wires or traces on the corresponding
- 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 metallic 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 semiconductor die corresponding to the wiring, so that the semiconductor material comes into contact only with the metal pads, but not with the wiring during bonding.
- the semiconductor wafer is then applied to the substrate and disposed thereon 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 wafer 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.
- FIG. 1 shows the basic arrangement of the essential parts of an advantageous embodiment of the mass spectrometer without wiring and non-conductive substrates.
- Fig. 2 is a section along the line A-A of Fig. 1, wherein the non-conductive substrates are shown.
- FIG. 4 in a similar representation as Fig. 2 a
- FIG. 6 to Figures 1 and 2 or 3 and 4 are corresponding views of a third embodiment, •
- Fig. 8 is a section along the line A-A of Fig. 7;
- FIG. 9 shows the principle of production of the mass spectrometer of the invention.
- the finished semiconductor chip is shown, which consists in this embodiment of doped silicon and in which the corresponding components are prepared 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 edible gas is supplied via the channel e to 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 the ion optics g to a further aperture, accelerated and focused with a defined energy.
- 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.
- FIGS. 3 and 4 show another embodiment which is different in the area of the accelerating electrode of the exporting ⁇ approximate shape of FIGS. 1 and 2.
- the electrodes m of the traveling field separator are subjected to an alternating voltage, so that ions which move 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, which pass through the electrodes when no voltage is applied to them, reach the energy filter k, whose two electrodes on both sides of the quarter-circle-shaped channel are at opposite potential, so that only ions with one to pass exactly defined energy. These ions then strike the detector 1 again.
- FIGS. 5 and 6 differs from that of FIGS. 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 show the electrode region of the mass spectrometer according to the invention.
- 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 shown in Fig. 8 in section.
- Fig. 9 the principle of manufacturing the mass spectrometer is shown.
- recesses 8 are produced, which in the finished masonry senspektrometer provide for the required distance between the metallic interconnects 2 on the carrier substrate 1 and the silicon wafer 6. This is necessary so that the substrate 1 and the silicon wafer 6 can be bonded in a planar manner.
- 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.
- step II 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 finished 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.
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Electron Tubes For Measurement (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002678460A CA2678460A1 (en) | 2007-02-19 | 2008-02-19 | Mass spectrometer |
JP2009549804A JP2010519687A (ja) | 2007-02-19 | 2008-02-19 | 質量分析計 |
US12/526,163 US8134120B2 (en) | 2007-02-19 | 2008-02-19 | Mass spectrometer |
CN200880005532.7A CN101636814B (zh) | 2007-02-19 | 2008-02-19 | 质谱仪 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP07003392.3 | 2007-02-19 | ||
EP07003392A EP1959476A1 (de) | 2007-02-19 | 2007-02-19 | Massenspektrometer |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2008101669A1 true WO2008101669A1 (de) | 2008-08-28 |
WO2008101669A8 WO2008101669A8 (de) | 2008-12-24 |
Family
ID=38235375
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2008/001287 WO2008101669A1 (de) | 2007-02-19 | 2008-02-19 | Massenspektrometer |
Country Status (6)
Country | Link |
---|---|
US (1) | US8134120B2 (de) |
EP (1) | EP1959476A1 (de) |
JP (1) | JP2010519687A (de) |
CN (1) | CN101636814B (de) |
CA (1) | CA2678460A1 (de) |
WO (1) | WO2008101669A1 (de) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011134968A1 (de) | 2010-04-29 | 2011-11-03 | Bayer Technology Services Gmbh | Flüssigkeitsverdampfer |
DE102014003356A1 (de) | 2014-03-06 | 2015-09-10 | Gregor Quiring | Vorrichtung zur Ionentrennung durch selektive Beschleunigung |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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*** |
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 (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0427532A2 (de) * | 1989-11-08 | 1991-05-15 | Schultz, J. Albert | Hochauflösende Rücklaufionen-Massenspektrometrie zur Isotopen- und Elementenspuren-Analyse |
US5486697A (en) * | 1994-11-14 | 1996-01-23 | California Institute Of Technology | Array of micro-machined mass energy micro-filters for charged particles |
WO1996011492A1 (en) * | 1994-10-07 | 1996-04-18 | Northrop Grumman Corporation | Miniaturized mass filter |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
US5492867A (en) * | 1993-09-22 | 1996-02-20 | Westinghouse Elect. Corp. | Method for manufacturing a miniaturized solid state mass spectrograph |
US5386115A (en) * | 1993-09-22 | 1995-01-31 | Westinghouse Electric Corporation | Solid state micro-machined mass spectrograph universal gas detection sensor |
US5481110A (en) * | 1993-09-22 | 1996-01-02 | Westinghouse Electric Corp | Thin film preconcentrator array |
US5466932A (en) * | 1993-09-22 | 1995-11-14 | Westinghouse Electric Corp. | Micro-miniature piezoelectric diaphragm pump for the low pressure pumping of gases |
EP0745268B1 (de) * | 1994-11-22 | 1998-10-21 | Northrop Grumman Corporation | Mikrostruktarierter festkörpermassenspektrograph für verwendung als sensor für einen gasdetektor |
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 |
GB2391694B (en) * | 2002-08-01 | 2006-03-01 | Microsaic Systems Ltd | Monolithic micro-engineered mass spectrometer |
CA2605871A1 (en) * | 2004-05-07 | 2005-11-24 | Stillwater Scientific Instruments | Microfabricated miniature grids |
EP1779409A2 (de) * | 2004-08-02 | 2007-05-02 | Owlstone Ltd | Ionenmobilitätsspektrometer |
EP1746631B1 (de) * | 2005-07-20 | 2013-06-19 | Microsaic Systems PLC | Mikromechanisches Nano-Elektrodensystem |
-
2007
- 2007-02-19 EP EP07003392A patent/EP1959476A1/de not_active Withdrawn
-
2008
- 2008-02-19 US US12/526,163 patent/US8134120B2/en not_active Expired - Fee Related
- 2008-02-19 JP JP2009549804A patent/JP2010519687A/ja active Pending
- 2008-02-19 CA CA002678460A patent/CA2678460A1/en not_active Abandoned
- 2008-02-19 WO PCT/EP2008/001287 patent/WO2008101669A1/de active Application Filing
- 2008-02-19 CN CN200880005532.7A patent/CN101636814B/zh not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0427532A2 (de) * | 1989-11-08 | 1991-05-15 | Schultz, J. Albert | Hochauflösende Rücklaufionen-Massenspektrometrie zur Isotopen- und Elementenspuren-Analyse |
WO1996011492A1 (en) * | 1994-10-07 | 1996-04-18 | Northrop Grumman Corporation | Miniaturized mass filter |
US5486697A (en) * | 1994-11-14 | 1996-01-23 | California Institute Of Technology | Array of micro-machined mass energy micro-filters for charged particles |
Non-Patent Citations (1)
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 (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011134968A1 (de) | 2010-04-29 | 2011-11-03 | Bayer Technology Services Gmbh | Flüssigkeitsverdampfer |
DE102010018830A1 (de) | 2010-04-29 | 2011-11-03 | Bayer Technology Services Gmbh | Flüssigkeitsverdampfer |
DE102014003356A1 (de) | 2014-03-06 | 2015-09-10 | Gregor Quiring | Vorrichtung zur Ionentrennung durch selektive Beschleunigung |
WO2015132005A1 (de) | 2014-03-06 | 2015-09-11 | Gregor Quiring | Vorrichtung zur ionentrennung durch selektive beschleunigung |
Also Published As
Publication number | Publication date |
---|---|
EP1959476A1 (de) | 2008-08-20 |
CA2678460A1 (en) | 2008-08-28 |
US8134120B2 (en) | 2012-03-13 |
CN101636814A (zh) | 2010-01-27 |
CN101636814B (zh) | 2013-01-23 |
WO2008101669A8 (de) | 2008-12-24 |
JP2010519687A (ja) | 2010-06-03 |
US20100090103A1 (en) | 2010-04-15 |
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