EP1915770A2 - Procede et dispositif pour la detection de composes par spectrometrie de masse - Google Patents

Procede et dispositif pour la detection de composes par spectrometrie de masse

Info

Publication number
EP1915770A2
EP1915770A2 EP06776639A EP06776639A EP1915770A2 EP 1915770 A2 EP1915770 A2 EP 1915770A2 EP 06776639 A EP06776639 A EP 06776639A EP 06776639 A EP06776639 A EP 06776639A EP 1915770 A2 EP1915770 A2 EP 1915770A2
Authority
EP
European Patent Office
Prior art keywords
pulses
photon
ionization
compounds
ions
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.)
Granted
Application number
EP06776639A
Other languages
German (de)
English (en)
Other versions
EP1915770B1 (fr
Inventor
Fabian Mühlberger
Ralf Zimmermann
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.)
Helmholtz Zentrum Muenchen Deutsches F
Original Assignee
Helmholtz Zentrum Muenchen Deutsches Forschungszentrum fuer Gesundheit und Umwelt 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 Helmholtz Zentrum Muenchen Deutsches Forschungszentrum fuer Gesundheit und Umwelt GmbH filed Critical Helmholtz Zentrum Muenchen Deutsches Forschungszentrum fuer Gesundheit und Umwelt GmbH
Publication of EP1915770A2 publication Critical patent/EP1915770A2/fr
Application granted granted Critical
Publication of EP1915770B1 publication Critical patent/EP1915770B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/10—Ion sources; Ion guns
    • H01J49/107—Arrangements for using several ion sources
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/10—Ion sources; Ion guns
    • H01J49/16—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission
    • H01J49/161—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission using photoionisation, e.g. by laser
    • H01J49/162—Direct photo-ionisation, e.g. single photon or multi-photon ionisation

Definitions

  • the invention relates to a method and an apparatus for mass spectrometric detection of compounds in a gas stream according to the first and eleventh claim.
  • a gas sample can consist of a large number of atoms, molecules and chemical compounds.
  • a ionization of a sample takes place via a photon and / or electron irradiation, wherein depending on the type and intensity of irradiation, a selective ionization of the various atoms, molecules or chemical compounds or a fragmentation of molecules and compounds.
  • the generated ions are deflected by means of an electric field and fed to mass spectrometric detection.
  • the resonance-enhanced multiphoton ionization technique (REMPI), the UY laser pulses (soft photoionization) for the selective ionization of e.g. Is used as a selective and soft ionization method for mass spectrometry.
  • the selectivity is u. a. determined by the soft UV spectroscopic properties and the position of the ionization potentials.
  • a disadvantage of the REK? I method is that it is limited to some substance classes and the ionization cross-section can sometimes be extremely different for similar compounds.
  • Single photon ionization (SPI) with VUV laser light also allows for a partially selective and soft ionization.
  • the selectivity is determined by the position of the ionization potentials.
  • a typical application is the detection of compounds that can not be detected by REMPI.
  • a disadvantage of the SPI method is that even here some substance classes can not be detected.
  • the selectivity is smaller than in the REMPI method, so that interference can occur with complex samples.
  • EI electron beam unselective but fragmenting electron impact ionization
  • mass spectrometry especially of volatile inorganic and organic compounds. It acts on all substances (ie, non-selective) and often results in many molecules very strong fragmentation. They are particularly suitable for detection of the compounds (such as O 2, N 2, CO 2, SO 2, CO, C 2 H 2), the aforementioned with a Photonenionsiation with UV and VUV-radiative (SPI, REMPI ) are difficult to detect.
  • ionization of a gas sample from a variety of compounds by the SPI method may cause several compounds to be ionized to the same mass and therefore unable to be resolved by mass spectrometry.
  • GC capillary gas chromatograph capillary
  • DE 100 14 847 A1 proposes a technology for the detection of compounds from a gas stream, which uses a combination of the aforementioned SPI and REMPI ionization.
  • a continuous gas stream with REMPI and SPI ionization pulses UV or VUV laser pulses
  • All laser pulses are using a structure with Solid state laser and a variety partly also variable optical elements generated.
  • the solid-state lasers used to produce a UV or VUV irradiation have only a very limited repetition rate in the range of 50 Hz.
  • changes in the gas stream composition typically with very short term concentration peaks, are to be expected, which requires increased temporal resolution and redundant measurements in rapid succession.
  • a repetition rate at the aforementioned level is no longer sufficient and leads to incorrect measurements.
  • the object of the invention is to propose a method and a device for the detection of compounds from a gas stream with an extended measuring range and a considerably improved temporal resolving power.
  • the object is achieved by a method according to the first and a device according to the eleventh claim for mass spectrometric detection of compounds in a gas stream.
  • the dependent claims described advantageous embodiments of the invention.
  • the method comprises ionizing volume units in a gas stream to form ions of the compounds, the ionization of beams crossing the gas stream alternating between electron and photon pulses or their pulse trains (ie electron pulses or electron pulse trains and photon pulses).
  • the volumetric units are self-contained gas flow sections which are defined by their volumetric expansion from the gas flow and the duration and penetration of the respective activated beams crossing the gas flow
  • the gas flow is continuous ie without flow interruption led from a supply line, preferably a capillary in the crossing region between the gas stream and beams.
  • Essential here is; a high Tdktfrequenz for the alternating change of electron and photon pulses or their pulse trains to over 50 Hz, preferably over 100 Hz (alternating frequency of the switching between photon and electron pulses). It is further preferred that, between the changes, the gas stream is irradiated with VUV light or electrons either continuously (as pulses) or at frequencies up to 150 kHz, preferably up to 100 kHz (as pulse sequences, repetition rate).
  • a generation of a photon pulse sequence with a laser such as an excimer laser, is possible only to a very limited extent, ie with significantly lower frequencies (laser repetition rates up to a maximum of approximately 4 kHz).
  • Lasers are indeed particularly suitable for the production of monochromatic photon radiation having a very high energy and good up in the UV range ( ⁇ > 193 nm) on ⁇ but not due to the poor transmission properties in glasses and crystals for the generation of photons in the VUV range ( ⁇ ⁇ 157 nm).
  • Another essential feature of the invention therefore comprises the means for generating the vacuum UV photon pulses (VUV) by a preferably electron beam pumped excimer lamp.
  • An electron-beam-pumped excimer lamp has a brilliant luminous spot, ie it produces a punctiform and therefore more focusable photon radiation and thus differs from discharge Exicimerlampen.
  • E-beam pumped excimer crystals also produce a more precise monochromatic
  • energetically excited noble gas atoms or molecules are formed by collisions with accelerated electrons (eg Ar% Kr + or NeH 2 ), the electrons depending on the gas full pressure with noble gas or halogen atoms to excimers ("excited di- mers ”) or exciplexes (" excited complexes ”) react.
  • accelerated electrons eg Ar% Kr + or NeH 2
  • excimer lamps generate VUV radiation continuously or as pulse sequences with a repetition rate, they have too low an intensity in the UV range for a resonance-enhanced multiphoton ionization (REMPI), which is a considerable limitation of the method (namely to an SPI-EI combination ) let expect.
  • REMPI resonance-enhanced multiphoton ionization
  • the apparatus comprising a switching device (trigger circuit), preferably nes on the basis of egg ⁇ fast process computer.
  • Essential in the continuous ionization between the changes is that the ion current is continuously passed through the ion exhaustion area of a mass spectrometer (time-of-flight mass spectrometer) and here high-frequency ion packets are extracted into the Mafe capsspek'trometer.
  • the ions are deflected by an electric field (ion extraction field) hm to form a mass spectrometric system for detecting the ions using a mass spectrometric method.
  • ionization takes place directly in an electric field.
  • the electric field in particular at the above-mentioned increased clock frequencies and the relatively low photon pulse intensity of the excimer lamp used, has a time offset to the photon and electron pulses 1 ' 1 Fit vor ⁇ ⁇ ri ? ⁇ n1 " Qir T ⁇ frequency clocked acti ⁇ iert vird.
  • Short pulses and a defined withdrawal of the ions from the jet advantageously produce a significantly improved mass resolution in the mass spectrometer (time-of-flight mass spectrometer).
  • the temporal measurement resolution can be improved.
  • averaging of individual data of several individual spectra and integration of individual measured values over time, i. an individual evaluation in a substantially extended form is pointed out.
  • the non-ionized by the aforementioned electron or photon pulses gas stream components behave in an electric field neutral and are not distracted. After removal of the ions in the electric field, they can again be charged and ionized with a second electron or photon pulse (second beam) of different energy density or wavelength, the ions then being generated in a second electric field (ion extraction field) towards a mass spectrometric system Detecting the ions are distracted with a mass spectrometric method.
  • This method step is also applicable more than twice in a row, is preferably secured via a corresponding delay control or 'Impulstrig- that the second steel m exclusively volume areas detects the aforementioned volume units.
  • a design of the capillary is advantageous as a GC capillary.
  • gravimetric splitting of lighter and heavier compounds takes place via a narrow gas flow diversion, for example. in the capillary with a subsequent gas flow branching into two partial gas flow streams (separating nozzle), wherein each partial gas stream can be analyzed separately with the abovementioned method.
  • the corresponding compound of the method and apparatus is in connection with a mass spectrometer (TOF) with orthogonal ion generation within the scope of the invention.
  • TOF mass spectrometer
  • ions are generated in the gas stream in the aforementioned manner with photon and electron pulses or their pulse sequences, but not directly in the pulsed ion extraction field but in the gas stream in front of the ion extraction field.
  • a prior ⁇ takes the ions are guided by electrostatic ion lens, wherein the ions are focused into the ion trigger field.
  • the advantage of this focusing is the high density and localization of the ions upon reaching the electric extraction field and thus causes a higher separation sharpness or mass resolution. This represents in particular an improvement when using a continuously lit excimer lamp.
  • Fig.l a basic structure of the embodiment (GC-EI-SPI device) and 2 shows the timing of the trigger signals dei: Umscha ⁇ tVorraum (trigger circuit) and the mass spectrometry detected signals.
  • the apparatus for detecting compounds from a gas stream comprises a supply line 1 for the gas stream 2 with a grounding 3 at the Gasaustritts- opening 4, the supply line 1, a gas chromatograph capillary (GC capillary 5) a gas inlet 6 and a gas outlet 7 comprises.
  • the gas stream flows into the ionization regions 8, which extends over the penetration volume of the gas stream 2 and the photon pulse beams 9 or the electron pulse beams 10, depending on the type of ionization. In these ionization areas, the respective ionization of volume units takes place.
  • Gas stream, photon pulse jets and electron pulse beams preferably intersect at a single point of intersection, so that the ionization regions for both aforementioned ionization types are congruent as far as technically possible.
  • the device also has an Ecimer lamp 11 and an electron gun 12 as means for generating photon or electron pulses or pulse trains (ion or electron beam source) for ionization of volume units in the gas stream for the formation of ions of the compounds Pulses or pulse sequences as described above as photon or electron pulse beams 9 and 10 cross the gas stream 2 in the ionization region 8.
  • an Ecimer lamp 11 and an electron gun 12 as means for generating photon or electron pulses or pulse trains (ion or electron beam source) for ionization of volume units in the gas stream for the formation of ions of the compounds Pulses or pulse sequences as described above as photon or electron pulse beams 9 and 10 cross the gas stream 2 in the ionization region 8.
  • the Ionsticians Society 8 is located in the active area 13 of a pulse-activatable and deactivatable electrical field between two acceleration electrons of the repeller 14 (positively charged) and the extraction electrode 15 (negatively charged) of a mass spectrometric system 16 for detecting ions which are called by the pre ⁇ electric field in the direction of the extraction electrode. accelerated by a centrally in the extraction, ktrode arranged extraction electrode opening 17 are deflected from the gas stream 2.
  • the mass spectrometric system preferably consists of a time-of-flight mass spectrometer for detecting the migration times of an activation pulse duration and duration for the electric field defined in the electric field accelerated ions to the ion detector 18.
  • the mass of detected ions is usually determined by the different flight times (small masses are accelerated faster) and typically range from 5 to 100 microseconds, which in this case allows repetition rates up to 20 KHz ,
  • a m Fig.l Umscnaltvorraum not shown f ⁇ r a "echsel- side alternately activating the photon and electron pulses or -Impuls Kunststoff with an alternating frequency large 50 Hz, preferably about 200 Hz.
  • the switching device preferably based on a process computer or a PC, which preferably also includes the aforementioned data evaluation unit, also serves to control the repetitive in the aforementioned pulse sequences preferably similar single pulses.
  • the Umschaltvorrich ⁇ tion is the activation of the electric field.
  • the activation begins with a certain time offset to the first pulse after a change of radiation (from photon to neutron radiation or vice versa) and ends before a period of the frequency of change after that pulse, ie starting with the first pulse of the photon or electron pulses or pulse trains.
  • the timing of the trigger signals of the switching device (trigger circuit) and the mass spectrometry detected signals is shown by way of example Fig.2.
  • the time axes 20 are divided by a plurality of successive sequences ⁇ 21 to 25, each sequence a high period length of the clock frequency for the alternating change of electron and photon pulses or pulse trains which (Alternating frequency).
  • the vertical axis reproduces the trigger pulse height 26, the time axes 21 representing the respective zero level of the qualitatively applied trigger signal high ("high" in the case of trigger pulses) or the detector signals to the ion detector for each of the trigger signal waveforms A to E shown.
  • the trigger waveform A represents the trigger pulses for the electron gun.
  • the sample gas In the "high" position, the sample gas is bombarded with one electron impulse or several electron impulse sequences, during which the sample gas is advantageously bombarded with several electron beam pulses during a sequence (21, 23, 25).
  • the trigger waveform B outputs the trigger pulses for the photon source, i. the VUV lamp (excimer lamp) again.
  • the sample gas is bombarded with a photon pulse (VUV) or preferably several photon pulse sequences (VUV)
  • VUV photon pulse
  • the sample gas is bombarded with several photon pulses.
  • the trigger signal curve C reproduces the trigger pulses for the electric field (ion withdrawal field).
  • a pulsed or continuous high voltage in the range of up to 1 kV, but preferably between 200 and 1000 V, is applied between the extraction electrode and the repeller and the ions are drawn off into the mass spectrometer (TOF) in the aforementioned manner a time offset, in the present case preferably but not necessarily activated only after completion of the photon or electron pulses or pulse trains.
  • the trigger signal waveform D represents the trigger pulses for the data acquisition.
  • a signal splitter conducts the detected detector signals (mass spectra according to signal curve E) to a data acquisition for the respective pulse types (eg EI or SPI) eg on two data acquisition memories and evaluation units (eg averaging, especially in the case of pulse fields).
  • the waveform reproduces the detector signals from individual pulses.
  • ionized compounds can optionally be carried out in each case a separate mass spectrometer, wherein the aforementioned switch circuit (waveform D) is used to control the electric field, the aforementioned extraction electrode and repeller as electrodes with a High voltage are acted upon with sequentially changing signs and both electrodes, each with an ion exhaust port (each acting as extraction electrode opening) are provided.
  • the deflection of the ions to one of the mass spectrometers takes place solely via the alignment of the electric field.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
  • Electron Tubes For Measurement (AREA)

Abstract

L'invention concerne un procédé servant à la détection de composés dans un flux gazeux (2) par spectrométrie de masse. Le procédé selon l'invention comprend les étapes suivantes : ionisation d'unités de volume dans le flux gazeux (2) avec formation d'ions des composés, la ionisation se faisant par l'intermédiaire de rayons (9, 10) croisant le flux gazeux dans une zone d'ionisation qui est formée dans l'alternance d'impulsions ou de séquences d'impulsions d'électrons et d'impulsions ou de séquences d'impulsions de photons ; déviation des ions par un champ électrique (13) vers un procédé par spectrométrie de masse ; ainsi que détection des ions au moyen d'un procédé par spectrométrie de masse. L'invention vise à créer un procédé de ce type présentant une plage de mesure étendue et une résolution significativement améliorée. A cet effet, les impulsions ou séquences d'impulsions de photons sont générées par une lampe excimère (11) et l'alternance entre les impulsions ou séquences d'impulsions d'électrons et les impulsions ou séquences d'impulsions de photons se fait à une fréquence de transition supérieure à 50 Hz.
EP06776639.4A 2005-08-19 2006-08-05 Procede et dispositif pour la detection de composes par spectrometrie de masse Active EP1915770B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005039269A DE102005039269B4 (de) 2005-08-19 2005-08-19 Verfahren und Vorrichtung zum massenspektrometrischen Nachweis von Verbindungen
PCT/EP2006/007773 WO2007019982A2 (fr) 2005-08-19 2006-08-05 Procede et dispositif pour la detection de composes par spectrometrie de masse

Publications (2)

Publication Number Publication Date
EP1915770A2 true EP1915770A2 (fr) 2008-04-30
EP1915770B1 EP1915770B1 (fr) 2017-12-06

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Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Status (5)

Country Link
US (1) US7910883B2 (fr)
EP (1) EP1915770B1 (fr)
JP (1) JP5542334B2 (fr)
DE (1) DE102005039269B4 (fr)
WO (1) WO2007019982A2 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4958258B2 (ja) * 2006-03-17 2012-06-20 株式会社リガク ガス分析装置
JP4825028B2 (ja) * 2006-03-17 2011-11-30 浜松ホトニクス株式会社 イオン化装置
EP2428796B1 (fr) * 2010-09-09 2015-03-18 Airsense Analytics GmbH Dispositif et procédé d'ionisation et d'identification de gaz moyennant rayonnement à UV et électrons
CN102479661B (zh) 2010-11-30 2014-01-29 中国科学院大连化学物理研究所 用于质谱分析的真空紫外光电离和化学电离的复合电离源
GB2518122B (en) 2013-02-19 2018-08-08 Markes International Ltd An electron ionisation apparatus
DE202013005959U1 (de) * 2013-07-03 2014-10-06 Manfred Gohl Bestimmungsvorrichtung für Kohlenwasserstoff-Emissionen von Motoren
DE102016113771B4 (de) * 2016-07-26 2019-11-07 Bundesrepublik Deutschland, Vertreten Durch Den Bundesminister Für Wirtschaft Und Energie, Dieser Vertreten Durch Den Präsidenten Der Bundesanstalt Für Materialforschung Und -Prüfung (Bam) Analysevorrichtung für gasförmige Proben und Verfahren zum Nachweis von Analyten in einem Gas
JP7451344B2 (ja) * 2020-08-06 2024-03-18 日本製鉄株式会社 真空紫外１光子イオン化質量分析装置

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US5206594A (en) * 1990-05-11 1993-04-27 Mine Safety Appliances Company Apparatus and process for improved photoionization and detection
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US5397895A (en) * 1992-09-24 1995-03-14 The United States Of America As Represented By The Secretary Of Commerce Photoionization mass spectroscopy flux monitor
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JP3707348B2 (ja) * 1999-04-15 2005-10-19 株式会社日立製作所 質量分析装置及び質量分析方法
DE10014847A1 (de) * 2000-03-24 2001-10-04 Gsf Forschungszentrum Umwelt Verfahren und Vorrichtung zum Nachweis von Verbindungen in einem Gasstrom
US20020104962A1 (en) * 2000-06-14 2002-08-08 Minoru Danno Device for detecting chemical substance and method for measuring concentration of chemical substance
DE10044655A1 (de) * 2000-09-09 2002-04-04 Gsf Forschungszentrum Umwelt Ionenquelle bei der UV-VUV-Licht zur Ionisation verwendet wird
JP3626940B2 (ja) * 2002-03-22 2005-03-09 三菱重工業株式会社 化学物質の検出方法及び検出装置
JP2005093152A (ja) * 2003-09-16 2005-04-07 Hitachi High-Technologies Corp 質量分析装置

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Also Published As

Publication number Publication date
WO2007019982A3 (fr) 2007-11-29
US7910883B2 (en) 2011-03-22
DE102005039269A1 (de) 2007-03-15
JP2009505082A (ja) 2009-02-05
WO2007019982A2 (fr) 2007-02-22
DE102005039269B4 (de) 2011-04-14
JP5542334B2 (ja) 2014-07-09
US20090218482A1 (en) 2009-09-03
EP1915770B1 (fr) 2017-12-06

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