EP1658632B1 - Spectrometre de masse et source d'ions a metal liquide pour spectrometre de masse de ce type - Google Patents

Spectrometre de masse et source d'ions a metal liquide pour spectrometre de masse de ce type Download PDF

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Publication number
EP1658632B1
EP1658632B1 EP04740521A EP04740521A EP1658632B1 EP 1658632 B1 EP1658632 B1 EP 1658632B1 EP 04740521 A EP04740521 A EP 04740521A EP 04740521 A EP04740521 A EP 04740521A EP 1658632 B1 EP1658632 B1 EP 1658632B1
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EP
European Patent Office
Prior art keywords
bismuth
ion
ions
mass
mass spectrometer
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.)
Revoked
Application number
EP04740521A
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German (de)
English (en)
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EP1658632A2 (fr
Inventor
Felix Kollmer
Peter Hoerster
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ION-TOF TECHNOLOGIES GMBH
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ION-TOF Technologies GmbH
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Application filed by ION-TOF Technologies GmbH filed Critical ION-TOF Technologies GmbH
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    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J27/00—Ion beam tubes
    • H01J27/02—Ion sources; Ion guns
    • H01J27/26—Ion sources; Ion guns using surface ionisation, e.g. field effect ion sources, thermionic ion sources
    • 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

Definitions

  • the invention relates to a mass spectrometer for analyzing secondary ions and deionized neutral secondary particles with an ion source for generating a primary ion beam for irradiating a sample and generating secondary particles, which source has a heatable ion emitter, which is coated in the field-exposed area with a liquid metal layer, the contains ionizable metal that is emitted and ionized as a primary ion beam, the primary ion beam containing metal ions with different ionization levels and cluster states, as well as a spectrometer unit for mass analysis of the secondary particles.
  • the invention also relates to the ion source for such a mass spectrometer.
  • liquid metal ion sources in secondary ion mass spectrometry, which is especially operated as Time of Flight Secondary Ion Mass Spectroscopy (TOF-SIMS).
  • TOF-SIMS Time of Flight Secondary Ion Mass Spectroscopy
  • Applicant proposes a liquid metal gold cluster ion source for a spectrometer (see Prospectus "Liquid Metal Gold Cluster Ion Gun for Improved Molecular Spectroscopy and Imaging", no date, published 2002), which represents the state of the art according to the cited generic term.
  • bismuth is an anisotopic element with a melting point of 271.3 ° C.
  • bismuth alloys such as Bi + Pb, Bi + Sn and Bi + Zn are known which have a lower melting point (46 ° C - 140 ° C) than pure bismuth.
  • pure bismuth is preferred.
  • the document US 6,002,128 describes a secondary ion mass spectrometer in which the primary beam is generated by a gallium liquid metal ion source.
  • Other possible metal ions for the primary beam include cesium, indium, bismuth and gold.
  • a calibration alloy for a secondary ion mass spectrometer specified can be obtained with the mass spectra with high resolution.
  • the elements V, Ge, Cd, Os and Bi are mentioned as elements with high negative secondary ionization.
  • the isotope curves (patterns) with the aforementioned elements give characteristic, repeatable spectra.
  • this document does not speak of clustering or of a liquid metal ion source.
  • bismuth is particularly well suited for cluster production.
  • the invention thus has the task of developing an ion source with improved yield of cluster ions for the operation of secondary ion mass spectrometers in order to achieve a high efficiency of secondary ion formation with simultaneously high data rates and thus short analysis times.
  • the proposed improvement combines a high efficiency E of secondary ion formation from unchanged sample surfaces with high cluster currents and leads to a corresponding shortening of the analysis times.
  • a secondary ion mass spectrometer in which the liquid metal layer consists of pure metallic bismuth or a low melting bismuth alloy, wherein with the ion emitter under the influence of an electric field, a bismuth ion mixing beam is emitted one of several Bismutionenart, the mass of which is a multiple of the monatomic, singly or multiply charged bismuth Bi 1 p +, is filtered out using a filter device as a mass pure ion beam consisting exclusively of ions of a type Bi n pk , where n ⁇ 2 and p ⁇ 1 is and n and p are each a natural number.
  • the value of efficiency E corresponds to the number of secondary particles detected by the spectrometer, which can be detected per unit surface area of a fully consumed monolayer. From the efficiency it can be calculated, therefore, how many secondary ions are to be detected in a small-area chemical analysis under the selected bombardment conditions.
  • the filtered out for a mass-pure ion beam ions belong to one of the following type: Bi 2 +, Bi 3 +, Bi 3 2+, Bi 4 +, Bi 5 +, Bi 6 +, Bi 5 2+ or Bi 7 2+ . It should preferably be worked with an ionic species, which makes up a relatively high proportion of the total number of ions.
  • the mass spectrometer is operated as a time-of-flight secondary ion mass spectrometer (TOF-SIMS), since there is much experience for this type and the experimental operation has shown that the greatest user potential lies here.
  • TOF-SIMS time-of-flight secondary ion mass spectrometer
  • an ion emitter equipped with a nickel-chromium tip is, according to current knowledge, a favorable solution.
  • the average current in the operation of the secondary ion mass spectrometer is chosen for the emission current between 10 -8 and 5x10 -5 A.
  • a bismuth metallic alloy is chosen instead of pure bismuth, it is preferable to determine one having a low melting point with a high bismuth content.
  • bismuth alloys with one or more of the following metals as liquid metal coating in question Ni, Ag, Pb, Hg, Cu, Sn, Zn, wherein preferably an alloy is selected whose melting point is below the melting point of pure bismuth ,
  • a liquid metal ion source suitable for a TOF-SIMS is disclosed in U.S. Pat FIG. 1 shown.
  • Liquid metal ion sources are widely used for material processing and surface analysis. These ion sources have a very small virtual source size of about 10 nm and a high angle intensity. Due to these properties, liquid metal ion sources can focus very well, whereby up to 7 nm beam diameter can be achieved with relatively high beam currents.
  • FIG. 1 schematically the generation system for ions from a liquid metal ion source with an emitter unit 1 is shown.
  • the support unit 7 carries at its two ends depending on a rigid lead wire 6, wherein via the lead wires 6 a variable in its thickness heating current is supplied; Both supply wires 6 are connected to a reservoir 5 in which a supply of molten bismuth is present during operation of the emitter unit 1.
  • An emitter needle 1 protrudes centrally from the reservoir 5. The emitter needle 1 can thus be held at a temperature at which the bismuth remains molten and wets the needle.
  • the emitter needle 1 is made of a nickel-chromium alloy and is wetted to its tip with liquid bismuth 4.
  • the emitter needle has a wire diameter of about 200 microns and a radius of curvature at the top of 2 to 4 microns.
  • the emitter needle 1 is positioned centrally in front of an extraction panel 2 and surrounded by a suppression unit 3.
  • FIG. 2 shows the emission current components for bismuth and gold, normalized to the atomic, singly charged ions for AuGe and Bi emitters at an emission current of 1 ⁇ A.
  • the absolute emission currents of Au 1 + and Bi 1 + are approximately equal. While the atomic, singly charged beam components Au 1 + and Bi 1 + are comparable in size, the cluster yield shows a clear difference. For the singly charged ions, the advantage of Bi n + over Au n + increases steadily with the size of the clusters. Double-charged cluster ions are emitted only with bismuth with appreciable intensity.
  • the cluster components shown refer to a total emission current of 1 ⁇ A. Since the cluster components are emission current-dependent, the cluster current can still be increased depending on further parameters for bismuth.
  • the same liquid metal ion mass spectrometer was used to analyze the same organic surfaces with different kinds of primary ions (cf. Fig. 3 ).
  • the sample is a color filter array, which, for example, is switched in digital cameras in front of a photosensitive CCD surface to provide the color information.
  • This sample is very well suited as a comparison standard, since it is made very homogeneous and reproducible.
  • the differences achieved between the primary ion species are quite typical and can be qualitatively transferred to other molecular solid surfaces.
  • FIG. 3 Series of images shown show the lateral distribution of two dyes used with the masses 413u and 641u. Due to the increasing destruction of the surface as a result of the Primärionenbeschusses the signal intensity decreases continuously. Shown for all primary ion species of the designated type is the summed signal intensity with the same degree of surface damage (1 / e decrease in signal intensity). The signal intensity achieved is thus a measure of the efficiency of the analysis.
  • the primary ion currents over Au 3+ can be increased by a factor of 4 to fifth Due to the slightly increased yield, the increase in data rates is even higher.
  • the 1 / e decrease of the signal intensity is observed with Au 3 + primary ions after 750 s and with Bi 3 + primary ions already after a significantly reduced analysis time of 180s reached.
  • the reduction in the measuring time is essentially due to the increased Bi 3 + cluster currents.
  • An increase in efficiency can be achieved by using larger clusters, such as Bi 7 ++ , but these cluster currents are relatively small, so the analysis times are generally longer.
  • bismuth emitters have advantages over gold emitters in terms of emission stability at low emission currents and mass separation of the emitted ion species.
  • the advantages described therefore show that bismuth emitters have significant economic and analytical advantages which were not to be expected without further ado.

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

Claims (10)

  1. Spectromètre de masse pour l'analyse d'ions secondaires et de particules secondaires neutres post-ionisées comprenant une source d'ions pour générer un faisceau d'ions primaires pour l'irradiation d'un échantillon et pour la production de particules secondaires, laquelle source d'ions présente un émetteur d'ions pouvant être chauffé, lequel est revêtu dans la zone exposée au champ d'une couche de métal liquide, qui contient un métal ionisable, lequel est émis sous forme de faisceau d'ions primaires et est ionisé, le faisceau d'ions primaires contenant des ions métalliques de bismuth avec différents niveaux d'ionisation et états de cluster, et comprenant une unité de spectromètre pour l'analyse de masse des ions secondaires et des particules secondaires, la couche de métal liquide étant à base de bismuth métallique pur ou d'un alliage à faible point de fusion et contenant du bismuth, un faisceau mixte d'ions de bismuth pouvant être émis avec l'émetteur d'ions sous l'influence d'un champ électrique, caractérisé en ce que ledit spectromètre de masse contient un dispositif de filtre qui permet de filtrer à partir du faisceau mixte d'ions de bismuth une sorte parmi plusieurs sortes d'ions de bismuth, dont la masse est un multiple de l'ion de bismuth Bin p+ monomère, chargé une ou plusieurs fois, sous forme de faisceau d'ions pur au niveau de la masse, qui contient exclusivement des ions d'un type Bin p+, avec lesquels n ≥ 2 et p ≥ 1 et n et p représentent chacun un nombre naturel.
  2. Spectromètre de masse selon la revendication 1, caractérisé en ce que les ions filtrés pour un faisceau d'ions pur au niveau de la masse appartiennent à l'un des types suivants : Bi2 +, Bi3 +, Bi3 2+, Bi4 +, Bi5 +, Bi6 +, Bi5 2+ ou Bi7 2+.
  3. Spectromètre de masse selon la revendication 1 ou 2, caractérisé en ce que le spectromètre de masse à ions secondaires peut être exploité sous forme d'un spectromètre de masse à ions secondaires à temps de vol.
  4. Spectromètre de masse selon l'une des revendications précédentes, caractérisé en ce que pendant le service, le flux d'émission du faisceau d'ions primaires se situe entre 10-8 et 5 x 10-5 A.
  5. Spectromètre de masse selon l'une des revendications précédentes, caractérisé en ce qu'un alliage métallique de bismuth avec un ou plusieurs des métaux suivants est choisi comme revêtement de métal liquide : Ni, Ag, Hg, Cu, Sn, Zn, sachant qu'on choisit de préférence un alliage dont le point de fusion se situe autour du point de fusion du bismuth pur.
  6. Procédé pour l'analyse d'échantillons ou surfaces, caractérisé en ce que l'échantillon ou la surface est irradiée avec un faisceau d'ions pur au niveau de la masse à base d'ions de bismuth d'un type Bin p+, avec lesquels n est ≥ 2 et p ≥ 1 et n et p sont chacun un nombre naturel, de sorte que des particules secondaires et/ou des ions secondaires sont formés, et la masse des particules secondaires et/ou des ions secondaires étant analysée.
  7. Procédé selon la revendication précédente, caractérisé en ce que le faisceau d'ions pur au niveau de la masse est généré en filtrant les ions de bismuth d'un type à partir d'un faisceau d'ions généré dans une source d'ions à métal liquide.
  8. Procédé selon l'une des revendications 6 et 7, caractérisé en ce que l'échantillon ou la surface présente des matériaux organiques.
  9. Utilisation d'un spectromètre de masse selon l'une des revendications 1 à 5 pour l'analyse d'échantillons et/ou de surfaces.
  10. Utilisation selon la revendication précédente, caractérisée en ce que les échantillons ou surfaces présentent des matériaux organiques.
EP04740521A 2003-08-25 2004-07-01 Spectrometre de masse et source d'ions a metal liquide pour spectrometre de masse de ce type Revoked EP1658632B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10339346A DE10339346B8 (de) 2003-08-25 2003-08-25 Massenspektrometer und Flüssigmetall-Ionenquelle für ein solches Massenspektrometer
PCT/EP2004/007154 WO2005029532A2 (fr) 2003-08-25 2004-07-01 Spectrometre de masse et source d'ions a metal liquide pour spectrometre de masse de ce type

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EP1658632A2 EP1658632A2 (fr) 2006-05-24
EP1658632B1 true EP1658632B1 (fr) 2008-09-17

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US (4) US20060202130A1 (fr)
EP (1) EP1658632B1 (fr)
JP (3) JP5128814B2 (fr)
AT (1) ATE408891T1 (fr)
DE (1) DE10339346B8 (fr)
WO (1) WO2005029532A2 (fr)

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DE102005027937B3 (de) * 2005-06-16 2006-12-07 Ion-Tof Gmbh Verfahren zur Analyse einer Festkörperprobe
JP2009507212A (ja) * 2005-09-02 2009-02-19 オーストラリアン ヌークリア サイエンス アンド テクノロジー オーガニゼイション 同位体比質量分析計および同位体比の決定方法
WO2008031058A2 (fr) * 2006-09-07 2008-03-13 Michigan Technological University Nanopointes auto-régénérantes pour cathodes de propulsion électrique à faible puissance (ep)
US20080128608A1 (en) * 2006-11-06 2008-06-05 The Scripps Research Institute Nanostructure-initiator mass spectrometry
JP2008185547A (ja) * 2007-01-31 2008-08-14 Canon Inc 情報取得方法及び情報取得装置
JP4854590B2 (ja) * 2007-05-11 2012-01-18 キヤノン株式会社 飛行時間型２次イオン質量分析装置
US7723697B2 (en) * 2007-09-21 2010-05-25 Varian Semiconductor Equipment Associates, Inc. Techniques for optical ion beam metrology
EP2056333B1 (fr) * 2007-10-29 2016-08-24 ION-TOF Technologies GmbH Source ionique de métal liquide, spectromètre de masse ionique secondaire, procédé d'analyse à spectromètre de masse ionique secondaire, ainsi que leurs utilisations
WO2009061313A1 (fr) * 2007-11-06 2009-05-14 The Scripps Research Institute Spectrométrie de masse avec initiateur de nanostructures
JP2011527637A (ja) 2008-07-09 2011-11-04 エフ・イ−・アイ・カンパニー レーザ機械加工のための方法および装置
CN102226981B (zh) * 2011-05-10 2013-03-06 中国科学院地质与地球物理研究所 二次离子质谱仪的样品保护装置和保护方法
US9551079B2 (en) 2013-09-13 2017-01-24 Purdue Research Foundation Systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions
CN104616962B (zh) * 2015-02-16 2017-03-01 江苏天瑞仪器股份有限公司 用于液相色谱‑质谱仪的离子源组件
EP3290913B1 (fr) * 2016-09-02 2022-07-27 ION-TOF Technologies GmbH Procede spectroscopique de masse d'ions secondaire, système et ses utilisations
CN106920735B (zh) * 2017-03-20 2018-10-16 北京大学深圳研究生院 可检测活性中间体的方法、电喷雾离子源装置及质谱仪
GB2585327B (en) * 2018-12-12 2023-02-15 Thermo Fisher Scient Bremen Gmbh Cooling plate for ICP-MS
WO2020144321A1 (fr) * 2019-01-11 2020-07-16 HELMHOLTZ-ZENTRUM POTSDAM - Deutsches-Geoforschungszentrum GFZ Stiftung des Öffentlichen Rechts des Landes Brandenburg Source d'ions comprenant un échantillon structuré pour ionisation améliorée

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Publication number Publication date
US9378937B2 (en) 2016-06-28
JP5128814B2 (ja) 2013-01-23
US20060202130A1 (en) 2006-09-14
ATE408891T1 (de) 2008-10-15
JP2014006265A (ja) 2014-01-16
DE10339346B8 (de) 2006-04-13
WO2005029532A3 (fr) 2006-04-20
US20120104249A1 (en) 2012-05-03
JP5416178B2 (ja) 2014-02-12
WO2005029532A2 (fr) 2005-03-31
JP2007503685A (ja) 2007-02-22
DE10339346B4 (de) 2005-12-08
EP1658632A2 (fr) 2006-05-24
US20160254134A1 (en) 2016-09-01
DE10339346A1 (de) 2005-04-14
JP2011243591A (ja) 2011-12-01

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