EP1082749B1 - Gaseinlass für eine ionenquelle - Google Patents

Gaseinlass für eine ionenquelle Download PDF

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Publication number
EP1082749B1
EP1082749B1 EP99925006A EP99925006A EP1082749B1 EP 1082749 B1 EP1082749 B1 EP 1082749B1 EP 99925006 A EP99925006 A EP 99925006A EP 99925006 A EP99925006 A EP 99925006A EP 1082749 B1 EP1082749 B1 EP 1082749B1
Authority
EP
European Patent Office
Prior art keywords
gas
ion source
guide tube
capillary
tube
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.)
Expired - Lifetime
Application number
EP99925006A
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German (de)
English (en)
French (fr)
Other versions
EP1082749A2 (de
Inventor
Egmont Rohwer
Ralf Zimmermann
Hans Jörg HEGER
Ralph Dorfner
Ulrich Boesl
Antonius Kettrup
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 Forschungszentrum fuer Gesundheit und Umwelt GmbH
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 EP1082749A2 publication Critical patent/EP1082749A2/de
Application granted granted Critical
Publication of EP1082749B1 publication Critical patent/EP1082749B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • H01J49/02—Details
    • H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
    • H01J49/0422—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components for gaseous samples
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
    • H01J49/0404—Capillaries used for transferring samples or ions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
    • H01J49/0468—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components with means for heating or cooling the sample

Definitions

  • the invention relates to a gas inlet for an ion source.
  • the Gas supply is said to be the molecules (or atoms) to be ionized bring into the ion source in such a way that the best possible Ionization efficiency can be achieved (i.e. high Sensitivity can be achieved in the ionization step).
  • ion source of the mass spectrometer This leads a supply line (e.g. the end of a gas chromatographic capillary) into the ion source, which is a closed (e.g. many CI or EI ion sources for quadrupole or sector field mass spectrometers) or an open design (e.g. many ion sources for time-of-flight mass spectrometers [TOF mass spectrometers]) can.
  • ion sources with a closed design becomes an area of the ion source with the admitted gas "flooded", i.e. H.
  • the embedded atoms or molecules lead partial collisions with the ion source wall before it ionized and detected in the mass spectrometer.
  • the open one Design of many ion sources favored for TOF mass spectrometers the use of atomic or molecular beam techniques. This causes a relatively directed gas jet through the ion source led, which ideally has very little interaction with the same components.
  • Effective molecular beams are used for time-of-flight mass spectrometry [2], as well as skimmed [1] and unkimmed [3, 4] supersonic molecular beams for use (either pulsed or continuous (Cw)).
  • gas inlet systems can be used for effective molecular beams be constructed such that a metallic Needle that leads to the center of the ion source, the gas outlet is led directly into the ionization site [2].
  • This needle a certain electrical potential is applied to the Deduction fields in the ion source are not to be disturbed.
  • the needle must be heated to relatively high temperatures in order to condense out prevent less volatile analyte molecules in the needle. It should be noted that the coldest point is not at the Needle point should be.
  • the need to heat the needle is problematic because the needle is electrical compared to the rest of the construction must be insulated (e.g. by a transition piece made of ceramic). Electrical insulators are also generally thermal Insulators and allow only a very low heat flow from Z. B. the heated lead to the needle. A heater over electrical heating elements or IR emitters is also difficult because the needle is between the ion source trigger plates protrudes.
  • REMPI resonance ionization with lasers
  • EMB effusive molecular beam inlet system
  • jet Supersonic molecular beam inlet system
  • Both common, developed for spectroscopic experiments Supersonic gas nozzles represents the utilization of the sample amount (i.e. the achievable measuring sensitivity) is not a limiting factor
  • the existing systems are not on avoidance designed by memory effects.
  • valves are made of inert materials are built up to memory effects or chemical decomposition To avoid (catalysis) the sample molecules. Furthermore, should the inlet valves have no dead volumes. Besides, it is necessary to heat the valve to temperatures above 200 ° C to be able to use so also volatile compounds from the Mass range> 250 amu are accessible. In addition, the Jet arrangement as little sensitivity to the effective inlet technology are lost. Above all, this can through a more effective use of the embedded sample in the Compared to previous jet arrangements can be achieved.
  • Boesl and Zimmermann et al. For example, [5] a heatable jet valve for analytical applications e.g. B. for Gas chromatography-REMPI coupling with minimized dead volume in front. For applications in the field of ultra trace analysis or Online analysis with REMPI-TOFMS is however a further development in terms of sample utilization (sensitivity), inertness (e.g. avoidance of metal sample contact) and heatability (Avoiding memory effects) makes sense.
  • Pepich et al. featured a GC supersonic molecular beam coupling for laser-induced Fluorescence spectroscopy before, through the pulsed Inlet and others an increase in the duty cycle compared to the effective one Admission was reached [6].
  • the structure enables a repetitive, time-limited ( ⁇ 10 ⁇ s) compression of the sample, without affecting the GC flow.
  • the structure allows by Pepich et al. no cooling of the sample (this will only by inserting mixing elements such as B. glass wool, which the compression characteristics deteriorated or destroyed, reached).
  • the object of the invention is the gas inlet for an ion source To be designed so that the expansion location of the gas jet directly be guided into the ion source of a mass spectrometer can to achieve a high sensitivity and if possible low gas load of the vacuum as high as possible Sample concentrations at the ionization site of the ion source of the mass spectrometer to achieve.
  • the device has the following particular features over the prior art Benefits:
  • the supersonic molecular beam expansion can go directly into the ion source be placed. In principle, this is the highest possible Density of the gas jet in the ionization site. reached. Farther the device allows a compression of the analyte gas in the Jet gas pulse and thus an even higher sensitivity.
  • Particular advantages of the gas supply are that the sample is cooled adiabatically, the capillary down to its lower The end can be heated well, and the sample pulsed in can.
  • the device can be designed so that the sample molecules only come into contact with inert materials.
  • the inlet of the gas is said to be either pulsed or continuous can be done. Furthermore, the analyte gas pulses should be through a Shock gas pressure pulse are compressed to the detection sensitivity further increase.
  • suitable parameters can be a cooling of the gas through an adiabatic expansion into the vacuum of the mass spectrometer (Supersonic molecular beam or jet). Cooling the recessed Gases is there for many mass spectrometric questions advantageous.
  • the lower internal energy chilled Molecules often act by reducing the degree of fragmentation in the mass spectrum. The is particularly advantageous Cooling for the application of resonance ionization with lasers (REMPI).
  • the gas jet can with REMPI highly selective (sometimes even isomer selective) ionized become. Since the cooling takes place through the expansion, the Sample gas supply line, the valve and the expansion nozzle are heated without significantly deteriorating the cooling properties. This is important for analytical applications. Without Adequate heating could include sample components in the supply line or condense in the gas inlet. Important applications for the invention is the coupling of a chromatographic Eluents or a continuous sample gas flow from a online sampling (probe) into a supersonic molecular beam.
  • the inlet system described here allows the location of expansion in the ion source of the mass spectrometer. So that can the ions are generated directly under the expansion nozzle, which is very beneficial for the achievable detection sensitivity is.
  • FIG. 1 shows a schematic gas inlet
  • the figure 2 the gas inlet for the ion source of a mass spectrometer
  • FIG. 3 the compression effect.
  • FIG. 1 shows the diagram of an advantageous embodiment of the Gas inlets, the ion source is not shown.
  • the end of the tube 2 has a nozzle opening 5, which can be designed in different ways.
  • the nozzle 5 can be designed as a Laval nozzle.
  • the tube 2 tapers towards the nozzle opening 5.
  • This z. B. conical taper allows to minimize the influence of the tube 2 projecting into the ion source on the electrical extraction fields in the ion source.
  • the advantages of the gas inlet system come especially together with an advantageous embodiment of the fume hoods of the ion source z. B. a time-of-flight mass spectrometer to wear.
  • the outlet characteristic from the nozzle 5 in the supersonic molecular jet mode is approximately proportional to cos 2 ⁇ where ⁇ corresponds to the angular deviation from the straight gas jet [7]. In the case of an effective molecular beam, the directional characteristic is less pronounced.
  • the ion source should be set up as openly as possible.
  • FIG. 2 shows an advantageous embodiment of an ion source for z.
  • B a TOF mass spectrometer with positioning the top of the design of the gas inlet according to the invention shown.
  • the repeller 20 and trigger shield 21 of the ion source can be designed as a network 17 made of thin conductive wires.
  • the network 17 can, for. B. in a wire ring, a U-shaped or a rectangular bracket 18 made of thicker wire his.
  • the upper part of the repeller 20 and trigger plates 21 can be solid be designed.
  • the ions can either through the network or be withdrawn through a circular or slot-shaped opening 22.
  • an opening 22 is used in the network, it can be supported a thin, ring-shaped (or oval etc.) aperture Metal 19 around the opening in the net the ion-optical quality (e.g. important for the achievable mass resolution) improved become.
  • the configuration of the repeller 20 as a wire mesh 17 allows the easy use of an electron gun 23 behind the repeller 20 or in front of the hood 21 to generate a Electron beam for electron impact ionization (EI ionization).
  • the electron gun 23 can be in any position be installed behind the panels (when installing behind the repeller 20 in axis with the deduction direction or deviating from the axis, when installing in front of the panel 21 only different from the Axis).
  • the electron beam 24 passes through the network 17 of the respective Aperture 20 or 21 and hits the sample in the effusive molecular beam under the nozzle 5. It is advantageous that in this Arrangement in a time-of-flight mass spectrometer the electron impact ionization alternating with REMPI with a laser beam 25 can be done d. H. per second, according to the maximum Repetition rate of data acquisition and processing, several hundred to thousand EI ionization mass spectra recorded and in parallel, according to the maximum repetition rate of the ionization laser and the maximum repetition rate of data acquisition, a few to several tens of REMPI mass spectra are recorded.
  • the device described can be operated as follows, for example become:
  • valve 12 If the valve 12 is not operated, an effective molecular beam is formed under the nozzle 5 from the analyte gas stream 13 continuously fed through the capillary 1.
  • the capillary 1 can be withdrawn to such an extent that it just opens into the channel 10 in the holder 7.
  • the molecules to be analyzed can be directly under the nozzle 5 z.
  • REMPI laser
  • EI electron beam
  • the advantage of effusive operation over conventional effusive gas inlet techniques is e.g. B. the direct heatability of the part of the inlet system projecting into the ion source and the use of inert materials.
  • a pulse of impact gas 12 eg argon or air with a pulse length of eg 750 ⁇ s
  • a supersonic molecular beam is formed under the nozzle 5.
  • the gas pulse compresses the analyte gas that has accumulated in tube 2 into a spatially restricted band.
  • the analyte molecules are concentrated in the band (ie the number of analyte molecules per unit volume is increased).
  • the analyte gas band represents a region with an increased analyte concentration in the jet gas pulse. This “dynamic and transient” concentration allows an improvement in the sensitivity of detection.
  • FIG. 3 shows the compression effect, recorded with a Prototype of the described intake system. This was the delay time between the laser pulse and the trigger pulse of the valve 8 passed in small increments and the REMPI signal of benzene (benzene was added to sample gas 13). Although the length of the pulse from impact gas 12 is greater than Is 750 ⁇ s, the observed width of the analyte gas pulse is only 170 ⁇ s (FWHM). The sensitivity to the effusive inlet has increased significantly. The spectroscopically determined jet cooling is 15 K. This shows that. very good supersonic molecular beam Conditions are met.
  • the analyte gas does not come with internal ones Share z.
  • the compression takes place through a gas pulse.
  • good jet cooling can be achieved.
  • the structure described allows in other words, a sample guide as used for trace analysis applications is required (minimized memory effects, exclusion catalytic reactions).
  • the expansion takes place directly in the ion source of the mass spectrometer.
  • the ionization site can be placed as close to the nozzle 5 without that special ion-optical concepts [3] would have to be used or it is necessary for the ions to drift into the source.
  • In the Practice is to avoid z. B. ion-molecule reactions and a distance of 3 - 5 to achieve complete jet cooling mm makes sense [4].
  • the shock gas 12 sample gas or calibration gas be added directly.
  • a structure with two valves can also be implemented become.
  • the capillary 1 is through a capillary tube 15 (not shown in the figures) replaced in the side of a capillary to the sample feeder and into the from above further valve 16 (not shown in the figures) a compressed gas pulse can be given.
  • the valve 8 generates a supersonic molecular beam from the nozzle opening 5 of the tube 2.
  • Das in the capillary tube 15 sample gas is by a compressed further gas pulse from the valve 16, from the capillary tube 15 pushed and in the already trained Supersonic molecular beam of valve 8 injected.
  • This supersonic molecular beam of the valve 8 represents a so-called jacket gas flow ("sheath gas" pulse) for that from the capillary tube 15 coming sample gas pulse.
  • the sample gas is in this jacket gas embedded and expanded through the nozzle 5.
  • the "jacket gas principle" allows a further increase in detection sensitivity by locally focusing the sample molecules on the central axis of the supersonic mole

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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)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP99925006A 1998-05-20 1999-05-18 Gaseinlass für eine ionenquelle Expired - Lifetime EP1082749B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19822674 1998-05-20
DE19822674A DE19822674A1 (de) 1998-05-20 1998-05-20 Gaseinlaß für eine Ionenquelle
PCT/EP1999/003420 WO1999060603A2 (de) 1998-05-20 1999-05-18 Gaseinlass für eine ionenquelle

Publications (2)

Publication Number Publication Date
EP1082749A2 EP1082749A2 (de) 2001-03-14
EP1082749B1 true EP1082749B1 (de) 2002-04-10

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EP99925006A Expired - Lifetime EP1082749B1 (de) 1998-05-20 1999-05-18 Gaseinlass für eine ionenquelle

Country Status (7)

Country Link
US (1) US6646253B1 (ja)
EP (1) EP1082749B1 (ja)
JP (1) JP2002516460A (ja)
AT (1) ATE216130T1 (ja)
DE (2) DE19822674A1 (ja)
DK (1) DK1082749T3 (ja)
WO (1) WO1999060603A2 (ja)

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Publication number Publication date
ATE216130T1 (de) 2002-04-15
WO1999060603A3 (de) 2000-01-27
DK1082749T3 (da) 2002-07-22
WO1999060603A2 (de) 1999-11-25
DE59901196D1 (de) 2002-05-16
JP2002516460A (ja) 2002-06-04
US6646253B1 (en) 2003-11-11
DE19822674A1 (de) 1999-12-09
EP1082749A2 (de) 2001-03-14

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