EP0889501A1 - Ionization cell for a mass spectrometer - Google Patents

Ionization cell for a mass spectrometer Download PDF

Info

Publication number
EP0889501A1
EP0889501A1 EP98401523A EP98401523A EP0889501A1 EP 0889501 A1 EP0889501 A1 EP 0889501A1 EP 98401523 A EP98401523 A EP 98401523A EP 98401523 A EP98401523 A EP 98401523A EP 0889501 A1 EP0889501 A1 EP 0889501A1
Authority
EP
European Patent Office
Prior art keywords
cathode
anode
ionization
mass spectrometer
electrons
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
EP98401523A
Other languages
German (de)
French (fr)
Other versions
EP0889501B1 (en
Inventor
Didier Pierrejean
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.)
Alcatel Lucent SAS
Original Assignee
Alcatel SA
Alcatel Alsthom Compagnie Generale dElectricite
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 Alcatel SA, Alcatel Alsthom Compagnie Generale dElectricite filed Critical Alcatel SA
Publication of EP0889501A1 publication Critical patent/EP0889501A1/en
Application granted granted Critical
Publication of EP0889501B1 publication Critical patent/EP0889501B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • H01J49/14—Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers
    • H01J49/147—Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers with electrons, e.g. electron impact ionisation, electron attachment

Definitions

  • the present invention relates to an ionization cell for mass spectrometer.
  • the invention applies to mass spectrometers in which the electron emitting heating electric filament is replaced by a cold microtip cathode.
  • the cold cathode at microdots degrades due to the too large number of ions formed between the cathode and anode, forming an ionization cage.
  • These ions, positive, formed between the cathode and the ionization cage indeed return to the cathode negative.
  • the present invention aims to overcome this drawback and has for object an ionization cell for mass spectrometer comprising a cold cathode with electron-emitting microtips, an anode, forming a cage ionization, in non-magnetic material, positively polarized with respect to said cathode and having an entry slot for the emitted electrons, being located opposite said cathode, characterized in that it further comprises an ion collecting electrode brought to a potential lower than that of said cathode and located outside the space going from the cathode to the anode, but placed laterally with respect to this space from the cathode to the anode, and in this that an axial magnetic field ⁇ is created in the cathode-anode direction.
  • Figure 1 is a schematic view showing an ionization cell according to the invention.
  • Figure 2 is an electrical diagram showing the electrical connections elements of figure 1.
  • an ionization cell comprises a ceramic substrate 1 serving as a support for a cold cathode to microtips 2, associated with a grid 3, an anode 4 in the form of a box parallelepiped in non-magnetic material forming a faraday cage and constituting an ionization cage and comprising an inlet slot 5 of electrons emitted by cold cathode 2 and an extraction slot 6 for ions ions formed in the ionization cage.
  • the extraction of ions through the extraction slot 6 as well as the selection of ions, is not part of the invention and is carried out, for example, from a classic way as in the analysis cells where the emission of electrons, for the production of ions, is carried out by a heating filament.
  • an ion collecting electrode 7 brought to a potential lower than that of the cold cathode 2.
  • This ion collecting electrode 7 makes it possible to capture all the ions formed between cathode 2 anode 4.
  • this electrode 7 is located outside of the space 8 going from cathode 2 to anode 4, but is placed laterally by relative to this space and covering the entire distance between cathode 2 of the anode 4.
  • the electrode 7 is bent behind the support substrate 1 and the assembly is fixed to a frame, not shown.
  • an axial magnetic field ⁇ is created directed as indicated by the arrow, in the cathode-anode direction. Indeed, without this field, because of the electrode 7, the electrons would be deflected by the field electrostatic created by this collecting electrode 7.
  • the magnetic field ⁇ is created by an electromagnetic coil or by magnets, not shown.
  • FIG. 2 shows the electrical connections of the different electrodes.

Abstract

The cell comprises a cold cathode (2) with micro-points, designed to emit electrons and mounted on a ceramic substrate (1), and an anode (4) of an magnetic material, forming an ionisation cage which is polarised positively relative to the cathode. The anode is positioned facing the cathode and has an entry slit (5) for the emitted electrons. The cell also has an ion collecting electrode (7) at a potential below that of the cathode (2) and situated to one side of a line between the cathode and anode. In addition, an axial magnetic field is created between the cathode and anode by means of a coil or magnets.

Description

La présente invention concerne une cellule d'ionisation pour spectromètre de masse.The present invention relates to an ionization cell for mass spectrometer.

En particulier, l'invention s'applique aux spectromètres de masse dans lesquels le filament électrique chauffant émetteur d'électrons est remplacé par une cathode froide à micropointes.In particular, the invention applies to mass spectrometers in which the electron emitting heating electric filament is replaced by a cold microtip cathode.

On connaít les avantages d'une telle cathode froide par rapport à un filament de tungstène chauffé à 1800°C :

  • le très bon rendement énergétique qui se situe pratiquement à 1, tout électron émis étant prélevé à la source émissive dans un rapport 1/1, contrairement au filament de tungstène qu'il est nécessaire de chauffer avec un courant important pour qu'il puisse émettre des électrons par effet thermoélectronique. Les ordres de grandeur des puissances mises en jeu sont : 10 W pour un filament chauffé, contre 0,2 W pour une source froide,
  • la rapidité de réaction du dispositif, aussi bien à l'allumage qu'à l'extinction : en cas d'entrée d'air brutale, le système peut être désactivé instantanément, contrairement au filament de tungstène qui va brûler à cause de son inertie thermique. Cette rapidité de réaction permet de plus d'envisager de couper l'alimentation du dispositif quand l'appareil n'est pas en mode mesure, et de le rallumer lorsqu'on veut effectuer une mesure,
  • la directivité du faisceau émis : les électrons sont émis : perpendiculairement à la surface du réseau de micropointes, contrairement à un filament pour lequel les électrons sont émis dans tout l'espace,
  • l'absence de dissipation thermique : le dispositif émettant des électrons par effet de champ ne dégage aucune chaleur, et par conséquent, ne perturbe pas les préamplificateurs de détection qui sont sensibles à la température.
We know the advantages of such a cold cathode compared to a tungsten filament heated to 1800 ° C:
  • the very good energy efficiency which is practically 1, all electron emitted being taken from the emissive source in a 1/1 ratio, unlike the tungsten filament which it is necessary to heat with a large current for it to emit electrons by thermoelectronic effect. The orders of magnitude of the powers involved are: 10 W for a heated filament, against 0.2 W for a cold source,
  • the speed of reaction of the device, both on switching on and off: in the event of sudden air entering, the system can be deactivated instantly, unlike the tungsten filament which will burn due to its inertia thermal. This speed of reaction also makes it possible to consider cutting the power supply to the device when the device is not in measurement mode, and turning it back on when a measurement is to be made,
  • the directivity of the emitted beam: the electrons are emitted: perpendicular to the surface of the microtip array, unlike a filament for which the electrons are emitted throughout the space,
  • the absence of heat dissipation: the device emitting electrons by field effect does not give off any heat, and therefore does not disturb the detection preamplifiers which are sensitive to temperature.

Cependant, la fiabilité et la capacité de fonctionnement à des pressions de l'ordre de 10-4 mbar ne sont pas assurées.However, reliability and ability to operate at pressures of the order of 10-4 mbar are not insured.

En effet, à partir de cette pression, et au-dessus, la cathode froide à micropointes se dégrade à cause du trop grand nombre d'ions formés entre la cathode et l'anode, formant une cage d'ionisation. Ces ions, positifs, formés entre la cathode et la cage d'ionisation reviennent en effet vers la cathode négative.Indeed, from this pressure, and above, the cold cathode at microdots degrades due to the too large number of ions formed between the cathode and anode, forming an ionization cage. These ions, positive, formed between the cathode and the ionization cage indeed return to the cathode negative.

La présente invention a pour but de pallier cet inconvénient et a pour objet une cellule d'ionisation pour spectromètre de masse comprenant une cathode froide à micropointes émettrice d'électrons, une anode, formant cage d'ionisation, en matériau amagnétique, polarisée positivement par rapport à ladite cathode et comportant une fente d'entrée pour les électrons émis, étant située en face de ladite cathode, caractérisée en ce qu'elle comporte en outre une électrode collectrice d'ions portée à un potentiel inférieur à celui de ladite cathode et située hors de l'espace allant de la cathode à l'anode, mais placée latéralement par rapport à cet espace depuis la cathode jusqu'à l'anode, et en ce qu'un champ magnétique axial β est créé dans le sens cathode-anode.The present invention aims to overcome this drawback and has for object an ionization cell for mass spectrometer comprising a cold cathode with electron-emitting microtips, an anode, forming a cage ionization, in non-magnetic material, positively polarized with respect to said cathode and having an entry slot for the emitted electrons, being located opposite said cathode, characterized in that it further comprises an ion collecting electrode brought to a potential lower than that of said cathode and located outside the space going from the cathode to the anode, but placed laterally with respect to this space from the cathode to the anode, and in this that an axial magnetic field β is created in the cathode-anode direction.

On va maintenant donner la description d'un exemple de mise en oeuvre de l'invention en se référant au dessin annexé dans lequel :We will now give the description of an example of implementation of the invention with reference to the accompanying drawing in which:

La figure 1 est une vue schématique montrant une cellule d'ionisation selon l'invention.Figure 1 is a schematic view showing an ionization cell according to the invention.

La figure 2 est un schéma électrique montrant les connexions électriques des éléments de la figure 1.Figure 2 is an electrical diagram showing the electrical connections elements of figure 1.

En se référant à la figure 1, une cellule d'ionisation selon l'invention comprend un substrat en céramique 1 servant de support à une cathode froide à micropointes 2, associée à une grille 3, une anode 4 en forme de boíte parallélépipédique en matériau amagnétique formant cage de faraday et constituant une cage d'ionisation et comportant une fente d'entrée 5 des électrons émis par la cathode froide 2 et une fente d'extraction 6 des ions ⊕ formés dans la cage d'ionisation.Referring to Figure 1, an ionization cell according to the invention comprises a ceramic substrate 1 serving as a support for a cold cathode to microtips 2, associated with a grid 3, an anode 4 in the form of a box parallelepiped in non-magnetic material forming a faraday cage and constituting an ionization cage and comprising an inlet slot 5 of electrons emitted by cold cathode 2 and an extraction slot 6 for ions ions formed in the ionization cage.

L'extraction des ions par la fente d'extraction 6 ainsi que la sélection des ions, ne fait pas partie de l'invention et est effectuée, par exemple, d'une manière classique comme dans les cellules d'analyse où l'émission des électrons, pour la production des ions, est effectuée par un filament chauffant.The extraction of ions through the extraction slot 6 as well as the selection of ions, is not part of the invention and is carried out, for example, from a classic way as in the analysis cells where the emission of electrons, for the production of ions, is carried out by a heating filament.

Conformément à l'invention, afin d'éviter que les ions formés entre la cathode froide 2 et l'anode-cage d'ionisation 4 ne reviennent vers les pointes de la cathode et ne les dégradent, on dispose une électrode collectrice d'ions 7 portée à un potentiel inférieur à celui de la cathode froide 2.In accordance with the invention, in order to prevent the ions formed between the cold cathode 2 and the ionization cage anode 4 do not return towards the points of the cathode and do not degrade them, there is an ion collecting electrode 7 brought to a potential lower than that of the cold cathode 2.

Cette électrode collectrice d'ions 7 permet de capter tous les ions formés entre la cathode 2 l'anode 4.This ion collecting electrode 7 makes it possible to capture all the ions formed between cathode 2 anode 4.

Comme le montre la figure 1, cette électrode 7 est située en dehors de l'espace 8 allant de la cathode 2 à l'anode 4, mais est placée latéralement par rapport à cet espace et en couvrant toute la distance séparant la cathode 2 de l'anode 4. Pour des facilités mécaniques de liaison, l'électrode 7 est recourbée derrière le substrat support 1 et l'ensemble est fixé à un bâti non représenté. Afin que les électrons émis par la cathode 2 se dirigent néanmoins vers la fente d'entrée 5 de l'anode-cage d'ionisation 4, on crée un champ magnétique axial β dirigé comme l'indique la flèche, dans le sens cathode-anode. En effet, sans ce champ, à cause de l'électrode 7, les électrons seraient déviés par le champ électrostatique créé par cette électrode collectrice 7.As shown in FIG. 1, this electrode 7 is located outside of the space 8 going from cathode 2 to anode 4, but is placed laterally by relative to this space and covering the entire distance between cathode 2 of the anode 4. For mechanical connection facilities, the electrode 7 is bent behind the support substrate 1 and the assembly is fixed to a frame, not shown. To that the electrons emitted by cathode 2 nevertheless go to the slot input 5 of the ionization cage anode 4, an axial magnetic field β is created directed as indicated by the arrow, in the cathode-anode direction. Indeed, without this field, because of the electrode 7, the electrons would be deflected by the field electrostatic created by this collecting electrode 7.

Le champ magnétique β est créé par une bobine électromagnétique ou par des aimants, non représentés.The magnetic field β is created by an electromagnetic coil or by magnets, not shown.

Dans la figure 1, le signe ⊕ représente un ion positif, le signe O une molécule neutre et e- un électron.In Figure 1, the sign ⊕ represents a positive ion, the sign O a neutral molecule and e - an electron.

La figure 2 montre les connexions électriques des différentes électrodes.Figure 2 shows the electrical connections of the different electrodes.

A titre d'exemple, on peut avoir les valeurs suivantes pour les tensions entre les différentes électrodes :

  • Vci : 80 V
  • VGK : 50 à 100 V
  • VAG : 80 V.
    • As an example, we can have the following values for the voltages between the different electrodes:
  • V ci : 80 V
  • V GK : 50 to 100 V
  • V AG : 80 V.

    • Claims (1)

    Cellule d'ionisation pour spectromètre de masse comprenant une cathode froide à micropointes(2) émettrice d'électrons, une anode (4) formant cage d'ionisation, en matériau amagnétique, polarisée positivement par rapport à ladite cathode et comportant une fente d'entrée (5) pour les électrons émis, étant située en face de ladite cathode (2), caractérisée en ce qu'elle comporte en outre une électrode collectrice d'ions (7) portée à un potentiel inférieur à celui de ladite cathode (2) et située hors de l'espace (8) allant de la cathode (2) à l'anode (4), mais placée latéralement par rapport à cet espace, depuis la cathode jusqu'à l'anode, et en ce qu'un champ magnétique axial β est créé, dans le sens cathode-anode.Ionization cell for mass spectrometer comprising a cold electron-emitting microtip cathode (2), an anode (4) forming an ionization cage, made of non-magnetic material, positively polarized with respect to said cathode and comprising a slit input (5) for the emitted electrons, being located opposite said cathode (2), characterized in that it further comprises an ion collecting electrode (7) brought to a potential lower than that of said cathode (2 ) and located outside the space (8) going from the cathode (2) to the anode (4), but placed laterally with respect to this space, from the cathode to the anode, and in that an axial magnetic field β is created, in the cathode-anode direction.
    EP98401523A 1997-07-03 1998-06-22 Ionization cell for a mass spectrometer Expired - Lifetime EP0889501B1 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    FR9708440A FR2765728B1 (en) 1997-07-03 1997-07-03 IONIZATION CELL FOR MASS SPECTROMETER
    FR9708440 1997-07-03

    Publications (2)

    Publication Number Publication Date
    EP0889501A1 true EP0889501A1 (en) 1999-01-07
    EP0889501B1 EP0889501B1 (en) 2003-09-10

    Family

    ID=9508822

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP98401523A Expired - Lifetime EP0889501B1 (en) 1997-07-03 1998-06-22 Ionization cell for a mass spectrometer

    Country Status (5)

    Country Link
    US (1) US6111252A (en)
    EP (1) EP0889501B1 (en)
    JP (1) JP4071362B2 (en)
    DE (1) DE69817929T2 (en)
    FR (1) FR2765728B1 (en)

    Families Citing this family (1)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    CN100445421C (en) * 2005-07-08 2008-12-24 清华大学 Sputter ion pump

    Citations (4)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US3852595A (en) * 1972-09-21 1974-12-03 Stanford Research Inst Multipoint field ionization source
    DE4137527A1 (en) * 1991-11-14 1993-05-19 Siemens Ag Ionisation gas pressure gauge for low pressure measurement - has electron emitting cathode with numerous field emitter elements, and applies positive voltage to extraction grating
    JPH05190148A (en) * 1992-01-14 1993-07-30 Matsushita Electric Works Ltd Luminous element
    US5541408A (en) * 1993-11-01 1996-07-30 Rosemount Analytical Inc. Micromachined mass spectrometer

    Family Cites Families (1)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE2810736A1 (en) * 1978-03-13 1979-09-27 Max Planck Gesellschaft FIELD EMISSION CATHODE AND MANUFACTURING METHOD AND USE FOR IT

    Patent Citations (4)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US3852595A (en) * 1972-09-21 1974-12-03 Stanford Research Inst Multipoint field ionization source
    DE4137527A1 (en) * 1991-11-14 1993-05-19 Siemens Ag Ionisation gas pressure gauge for low pressure measurement - has electron emitting cathode with numerous field emitter elements, and applies positive voltage to extraction grating
    JPH05190148A (en) * 1992-01-14 1993-07-30 Matsushita Electric Works Ltd Luminous element
    US5541408A (en) * 1993-11-01 1996-07-30 Rosemount Analytical Inc. Micromachined mass spectrometer

    Non-Patent Citations (1)

    * Cited by examiner, † Cited by third party
    Title
    PATENT ABSTRACTS OF JAPAN vol. 017, no. 608 (E - 1457) 9 November 1993 (1993-11-09) *

    Also Published As

    Publication number Publication date
    FR2765728A1 (en) 1999-01-08
    DE69817929D1 (en) 2003-10-16
    EP0889501B1 (en) 2003-09-10
    JPH1173909A (en) 1999-03-16
    US6111252A (en) 2000-08-29
    DE69817929T2 (en) 2004-07-22
    JP4071362B2 (en) 2008-04-02
    FR2765728B1 (en) 1999-09-24

    Similar Documents

    Publication Publication Date Title
    JP2010192454A (en) Cathode assembly used for indirectly heated cathode ion source
    WO2009085165A2 (en) Ionization gauge having electron multiplier cold emmission source
    US5463277A (en) Micro vacuum device
    EP0480518B1 (en) Electron source providing a particle retention device
    US6236156B1 (en) Micro vacuum pump for maintaining high degree of vacuum and apparatus including the same
    US5543625A (en) Filament assembly for mass spectrometer ion sources
    EP0889501B1 (en) Ionization cell for a mass spectrometer
    EP0132180B1 (en) X-ray tube having a rotary anode and a device for carrying off the anode current
    EP0077738A1 (en) Ion source having a gas ionization chamber with oscillations of electrons
    EP0295743B1 (en) Ion source with four electrodes
    EP1162648A1 (en) Hollow-cathode lamp
    US6060839A (en) Thin diamond electron beam amplifier
    WO2002089168A2 (en) Silicon-based dielectric tunneling emitter
    JP2001505355A (en) Display screen with microchip electron source observable through microchip support and method of manufacturing microchip electron source
    JPH10223162A (en) Electron tube
    EP0300932B1 (en) Electron source
    FR2792770A1 (en) Increased vacuum residual pressure micropoint electron emission generator having cathode and interspersed electrons with rear heating element maintaining temperature above ambient.
    US3527937A (en) Electron bombardment type ion source for a mass spectrometer
    WO1994014153A1 (en) Flat screen having individually dipole-protected microdots
    FR2645676A1 (en) CATHODE HAVING IMPROVED SECONDARY TRANSMISSION SURFACE AND CROSS-FIELD AMPLIFIER CONTAINING SUCH A CATHODE
    JP2000243354A (en) Hollow cathode lamp
    TW202221760A (en) Ion source assembly with multiple ionization volumes for use in a mass spectrometer
    TW202131366A (en) Light modulated electron source
    JP2001523388A (en) Electron tube with cesium source
    SREENIVASAN Parameters Influencing the Energy Spread in a Duoplasmatron Source

    Legal Events

    Date Code Title Description
    PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

    Free format text: ORIGINAL CODE: 0009012

    AK Designated contracting states

    Kind code of ref document: A1

    Designated state(s): CH DE GB IT LI

    AX Request for extension of the european patent

    Free format text: AL;LT;LV;MK;RO;SI

    RAP3 Party data changed (applicant data changed or rights of an application transferred)

    Owner name: ALCATEL

    RAP3 Party data changed (applicant data changed or rights of an application transferred)

    Owner name: ALCATEL

    17P Request for examination filed

    Effective date: 19990707

    AKX Designation fees paid

    Free format text: CH DE GB IT LI

    17Q First examination report despatched

    Effective date: 20020927

    GRAH Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOS IGRA

    GRAA (expected) grant

    Free format text: ORIGINAL CODE: 0009210

    GRAS Grant fee paid

    Free format text: ORIGINAL CODE: EPIDOSNIGR3

    AK Designated contracting states

    Kind code of ref document: B1

    Designated state(s): CH DE GB IT LI

    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: FG4D

    Free format text: NOT ENGLISH

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: EP

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: NV

    Representative=s name: CRONIN INTELLECTUAL PROPERTY

    REF Corresponds to:

    Ref document number: 69817929

    Country of ref document: DE

    Date of ref document: 20031016

    Kind code of ref document: P

    GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

    Effective date: 20031029

    PLBE No opposition filed within time limit

    Free format text: ORIGINAL CODE: 0009261

    STAA Information on the status of an ep patent application or granted ep patent

    Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

    26N No opposition filed

    Effective date: 20040614

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: IT

    Payment date: 20060630

    Year of fee payment: 9

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: DE

    Payment date: 20070622

    Year of fee payment: 10

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: GB

    Payment date: 20070621

    Year of fee payment: 10

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: CH

    Payment date: 20080613

    Year of fee payment: 11

    GBPC Gb: european patent ceased through non-payment of renewal fee

    Effective date: 20080622

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: DE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20090101

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: GB

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20080622

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: IT

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20070622

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: PL

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: LI

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20090630

    Ref country code: CH

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20090630