US20150235829A1 - Method for mass spectrometric examination of gas mixtures and mass spectrometer therefor - Google Patents

Method for mass spectrometric examination of gas mixtures and mass spectrometer therefor Download PDF

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US20150235829A1
US20150235829A1 US14/658,577 US201514658577A US2015235829A1 US 20150235829 A1 US20150235829 A1 US 20150235829A1 US 201514658577 A US201514658577 A US 201514658577A US 2015235829 A1 US2015235829 A1 US 2015235829A1
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Prior art keywords
ionization
plasma
gas mixture
ionization device
detector
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Hin Yiu Anthony Chung
Michel Aliman
Gennady Fedosenko
Albrecht Ranck
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Carl Zeiss SMT GmbH
Carl Zeiss Microscopy GmbH
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Carl Zeiss SMT GmbH
Carl Zeiss Microscopy GmbH
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Assigned to CARL ZEISS SMT GMBH reassignment CARL ZEISS SMT GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: RANCK, ALBRECHT, FEDOSENKO, GENNADY, CHUNG, HIN YIU
Assigned to CARL ZEISS MICROSCOPY GMBH reassignment CARL ZEISS MICROSCOPY GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: Aliman, Michel
Publication of US20150235829A1 publication Critical patent/US20150235829A1/en
Priority to US15/244,720 priority patent/US10903060B2/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/0027—Methods for using particle spectrometers
    • H01J49/0031—Step by step routines describing the use of the apparatus
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
    • C23C16/4405—Cleaning of reactor or parts inside the reactor by using reactive gases
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/52—Controlling or regulating the coating process
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/32798—Further details of plasma apparatus not provided for in groups H01J37/3244 - H01J37/32788; special provisions for cleaning or maintenance of the apparatus
    • H01J37/32853—Hygiene
    • H01J37/32862—In situ cleaning of vessels and/or internal parts
    • 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
    • H01J49/009—Spectrometers having multiple channels, parallel analysis
    • 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
    • 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
    • H01J49/105—Ion sources; Ion guns using high-frequency excitation, e.g. microwave excitation, Inductively Coupled Plasma [ICP]
    • 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
    • H01J49/14—Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers
    • H01J49/145—Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers using chemical ionisation
    • 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
    • H01J49/42—Stability-of-path spectrometers, e.g. monopole, quadrupole, multipole, farvitrons
    • H01J49/4205—Device types
    • H01J49/424—Three-dimensional ion traps, i.e. comprising end-cap and ring electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
    • H01J2237/32—Processing objects by plasma generation
    • H01J2237/33—Processing objects by plasma generation characterised by the type of processing
    • H01J2237/335—Cleaning

Definitions

  • the invention relates to a method for mass spectrometric examination of a gas mixture.
  • the invention also relates to a mass spectrometer for mass spectrometric examination of gas mixtures comprising an ionization unit and a detector.
  • the mass or the mass-to-charge ratio of atoms or molecules is determined in order to obtain a chemical characterization of the gaseous substances.
  • the substances to be examined or the substance mixture to be examined is either already available in the gas phase or it is transformed into the gas phase in order to be ionized via an ionization unit.
  • the substances ionized in this manner are fed to an analyzer and typically routed through an electric and/or magnetic field, in which the ions describe characteristic trajectories due to different mass-to-charge ratios and are therefore able to be distinguished.
  • WO 02/00962 A1 has disclosed an in-situ cleaning system for removing deposits produced by process gases in a sample chamber of a process monitor in a wafer production apparatus.
  • a probe head of a gas analyzer is arranged in the sample chamber in order to analyze a gas sample ionized via a plasma.
  • Deposits setting in over the course of one or more analyses in the sample chamber or on the probe head can, when necessary, be removed via a cleaning gas.
  • the cleaning gas forms a gaseous cleaning product with the deposits, which cleaning product is discharged from the sample chamber.
  • a method for mass spectrometric examination of a gas mixture comprising the following method steps: parallel or serial ionization of the gas mixture to be examined by activating of at least two ionization devices operating using different is ionization procedures, and/or ionizing of the gas mixture, in particular by charge exchange ionization, in a detector, to which the gas mixture and ions and/or metastable particles of an ionization gas, which are produced by an ionization device, in particular a plasma ionization device, are fed, and detecting of the ionized gas mixture in the detector for the mass spectrometric examination thereof.
  • the different ionization procedures of the plurality of ionization devices can be freely selected depending on requirements (depending on the type of the gas mixture to be examined).
  • the ionization devices can be arranged in parallel or in series for ionizing the gas mixture and can be activated selectively.
  • a first part of the gas mixture to be examined is ionized via a first ionization device and a second part of the gas mixture to be examined is ionized via a second ionization device, wherein the first and the second is ionization device are arranged spatially separated next to one another.
  • the gas mixture to be examined can initially be ionized via a first ionization device and subsequently be ionized via a second ionization device, which is spatially separated from the first ionization device. If three or more ionization devices are present, there can also be a combination of serial and parallel ionization of the gas mixture.
  • the gas mixture can be ionized directly in the detector, i.e. in the measuring cell, which, for example, can be embodied as an ion trap or can contain an ion trap.
  • the gas mixture is typically led to the detector in a non-ionized state and the ionization only takes place directly in the detector.
  • all ions produced in the measuring cell or in the detector can be analyzed directly.
  • this ionization procedure can be carried out on its own, i.e. without the provision of other ionization procedures.
  • the ionization can be brought about by ions of the ionization gas and/or by metastable particles of the ionization gas.
  • Metastable particles are understood to mean atoms or molecules of the ionization gas, which are put into an excited electron state during the ionization.
  • the ionization in the detector can be implemented by e.g. a plasma ionization.
  • the plasma or the ions of an ionization gas are generated in this case in a plasma source outside of the detector and the ionization takes place in the detector by impact ionization or charge exchange ionization of the gas mixture.
  • a large number of gases or gas mixtures can serve as ionization gas, e.g. He, H 2 , Ar, N 2 , Xe, Kr, CH 4 etc.
  • the gas mixture to be examined is understood to mean mixtures of gaseous substances, in which, in particular, particles may also be contained.
  • the measurement chamber in which the detection of the ionized substance or substances takes place, may, in principle, be any chamber of a mass spectrometer, in particular a detector chamber (for example a detector chamber with an ion trap arranged therein), is which e.g. is provided in a lithography apparatus, a (chemical) production apparatus or the like.
  • the gas mixture comprises particles which have an atomic mass number of between 100 and 20 000 or of between 20 000 and 2 000 000.
  • Conventional gases generally have an atomic mass number of less than 100.
  • particles i.e. gaseous substances with a mass number >100
  • Particles with an atomic mass number (in atomic mass units; AMU) of more than 100 or an atomic mass number of between 1000 and 20 000 may have particle sizes of approximately 0.01-10 ⁇ m or more.
  • the energy provided for the ionization is set depending on the gas mixture to be ionized.
  • the option of (ideally continuously) setting or adapting the energy provided during the ionization to the gaseous substances or particles to be ionized (and to be detected), more precisely to the ionization energy thereof, was found to be advantageous since this supports both a (common) ionization of all types of gaseous substances and particles (broadband ionization) and a selective, narrowband ionization of selected substances without ionizing other surrounding substances (e.g. a carrier gas).
  • a carrier gas e.g. a carrier gas
  • the provided energy can be set in a targeted manner dependent on the gas mixtures to be ionized, but it is also possible to tune the energy continuously. Setting is the energy provided for the ionization dependent on the gas mixture to be ionized is advantageously possible, in particular in the case of the so-called charge exchange ionization (see below).
  • At least one of the ionization procedures is selected from the following group: charge exchange ionization, electron impact ionization, ionization via a filament, field ionization, ionization via a pulsed laser, photon ionization, in particular UV light ionization, VUV light ionization or EUV light ionization.
  • an electron of a neutral gaseous substance is typically transferred to an ionized gaseous substance.
  • the charge exchange can be excited by a plasma.
  • electron impact ionization electrons are released from an electrically heated filament and accelerated by an electric field to kinetic energies of generally between 5 eV and 200 eV (usually approximately 70 eV for stability reasons) and led through the gas mixture to be ionized.
  • kinetic energies generally between 5 eV and 200 eV (usually approximately 70 eV for stability reasons) and led through the gas mixture to be ionized.
  • the electrons impact on the molecules or atoms of the substance to be examined, these are ionized.
  • field ionization electrons are released from their bond by a sufficiently strong electric field.
  • the field ionization can be used in high vacuum and in ultra-high vacuum and, compared to ionization via a filament, does not lead to a possibly undesired temperature increase. Furthermore, molecules are not fragmented much during field ionization, as a result of which mixtures of a plurality of substances can also be examined well. Ionization with the aid of radiation, so-called photon ionization, is also possible.
  • use is typically made of radiation in the UV wavelength range, in the VUV wavelength range (with wavelengths less than 200 nm) and/or in the EUV wavelength range (with wavelengths between approximately 5 nm and approximately 20 nm), which radiation has sufficiently high energy so that a single photon of this radiation can overcome the ionization energy of the gaseous substance to be examined.
  • a variant of the method, wherein the gas mixture is ionized at least in part by the plasma of at least one ionization device embodied as a plasma ionization device, is also preferred.
  • the gas mixture can be ionized both directly in the detector (of the measuring cell/ion trap) by impact ionization or charge exchange ionization, but there can also be an ionization of the gas mixture in an external plasma source and the gas mixture or parts of the gas mixture is/are fed to the detector in the ionized state.
  • different substances with the same mass number or the same mass-to-charge ratio are advantageously ionized with a different frequency or to a different extent by the plasma due to their typically differing ionization energies, and so it is possible to distinguish between different substances with the same mass number by using analytical comparisons. It is also possible for the ionization optionally to take place by the generation of a gentle plasma, which does not break up the substances to be examined into a number of fragments, and so these substances remain (largely) unchanged in terms of their chemical structure during the ionization.
  • the plasma ionization device can comprise a control device, which enables the aforementioned tuning by, for example, a variation in the amplitude or optionally in the frequency of an electric or electromagnetic field produced in the plasma ionization device.
  • a variant of the method wherein the plasma ionization device produces the plasma by a dielectric barrier discharge is preferred.
  • this particularly gentle ionization e.g. in the form of charge exchange
  • the ionization by a dielectric barrier discharge (DBD) can furthermore advantageously take place at comparatively low is temperatures of e.g. 10° C. to 200° C.
  • gas mixtures which, in addition to gaseous substances with a mass number of between 1 and 100, also comprise particles with an atomic mass number of between 100 and 200, an atomic mass number of between 200 and 20 000, or even an atomic mass number of between 20 000 and 2 000 000.
  • a thin dielectric which serves as dielectric barrier, is situated between two electrodes in order to produce a plasma in the form of a multiplicity of spark discharges and thus ionize a gas flow situated between the electrodes.
  • the use of a dielectric barrier discharge is possible using different excitation frequencies, such as e.g. direct current, medium frequency or high frequency.
  • the plasma of the plasma ionization device is a radiofrequency plasma (RF plasma) or a direct current plasma (DC plasma).
  • RF plasma radiofrequency plasma
  • DC plasma direct current plasma
  • the plasma of the plasma ionization device is a radiofrequency plasma (RF plasma) or a direct current plasma (DC plasma).
  • RF plasma radiofrequency plasma
  • DC plasma direct current plasma
  • the plasma of the plasma ionization device is a radiofrequency plasma (RF plasma) or a direct current plasma (DC plasma).
  • RF plasma radiofrequency plasma
  • DC plasma direct current plasma
  • a radiofrequency discharge can be ignited between e.g. two electrodes. It is understood that the production or excitation of an RF plasma can also be brought about in a manner different to that described above.
  • the RF plasma can also be a plasma produced in a pressure range that also lies in the region of atmospheric pressure or above the atmospheric pressure range.
  • a method variant wherein, in a method step preceding (and/or following) the ionization of the gas mixture, a plasma produced by the plasma ionization device is used to clean the detector, a measurement chamber, in which the detector is arranged, and/or to clean the further ionization devices is also preferred.
  • a plasma produced by the plasma ionization device for cleaning the detector, the measurement chamber and/or the further is ionization devices, self-cleaning is advantageously possible. This self-cleaning can be carried out via the plasma ionization device provided for ionizing the gas mixture, which is particularly simple and economical for the overall system.
  • the plasma ionization device can serve for cleaning a further ionization device embodied as a filament.
  • the cleaning comprises the following method steps: producing the plasma via a plasma gas for transforming contaminants deposited in the detector, in the measurement chamber and/or on the (further) ionization devices into the gas phase, and removing the contaminants (transformed into the gas phase) from the detector, the measurement chamber and/or the ionization devices.
  • the cleaning plasma reacts with the contaminants or the contaminations (e.g. particles deposited in the chamber), as a result of which volatile compounds are produced, which can be discharged from the measurement chamber (for example by ventilating or pumping away).
  • the contaminants are preferably removed via a pump device.
  • a pump device provided especially for this purpose, as a result of which there can be a particularly effective removal of the contaminants from the measurement chamber to be cleaned.
  • a pump device assigned to the mass spectrometer in any case, for example for evacuating available (measurement) chambers. In the latter case, is there is a more economical operation of the method.
  • Transforming contaminants into the gas phase can be brought about by a chemical reaction of the plasma gas or of the plasma with the contaminants to form volatile compounds.
  • contaminants can be hydrocarbon compounds or fluorides or Teflon.
  • the plasma gas is generally ignited in the measurement chamber in order to produce the plasma.
  • the plasma gas used during the production of the plasma for self-cleaning can be the gaseous substance (i.e. the gas or gas mixture) itself or a carrier gas for this gaseous substance, which is examined by mass spectroscopy.
  • use is typically made of a plasma gas provided especially for self-cleaning.
  • An inert gas for example helium and/or argon, which were found to be plasma gases with particularly good cleaning effect, can be used as plasma gas. It is understood that mixtures of these or optionally of other gases, such as e.g. hydrogen and/or oxygen, which perform a chemical reaction with the contaminants, can also be used as plasma gases.
  • the cleaning of the measurement chamber takes place at an operating pressure of between 1 bar and 1 ⁇ 10 ⁇ 10 mbar, in particular of between 10 mbar and 1 ⁇ 10 ⁇ 3 mbar.
  • the measurement chamber to be cleaned is filled with the plasma gas (gas for producing the plasma) up to an operating pressure of between 1 bar and 1 ⁇ 10 ⁇ 10 mbar, in particular in the plasma range between 10 mbar and 1 ⁇ 10 ⁇ 3 mbar.
  • normal operating pressure is built up again, which may, for example when using a filament as ionization device, lie in the high vacuum.
  • the corresponding pressures can be set by a vacuum producing device, which, for example, can be embodied as pump device.
  • a variant of the method is preferred, wherein, during the method step for cleaning the detector, the measurement chamber and/or for cleaning the ionization devices, at least one further ionization procedure is employed for transforming the is deposited contaminants into the gas phase in addition to producing the plasma.
  • the additional use of further ionization procedures is advantageous if the contaminants to be removed cannot be converted into volatile compounds by the plasma ionization on its own. By way of example, this may be required in the case of particularly large (and/or compactly structured) contaminants. Accordingly, the further ionization procedures can be applied when necessary, in each case individually successively in time or together, in addition to the plasma ionization.
  • the further ionization procedure is preferably selected from the group: electron impact ionization, in particular ionization via a filament, field ionization and ionization via a pulsed laser. It is understood that these further ionization method(s) can be used in addition to the plasma ionization in order to ionize the substances to be examined. A variant of the method is also preferred, wherein, for detection purposes, more precisely for analysis and detection, the ionized gas mixture is led into a conventional detector, e.g.
  • a quadrupole detector or a quadrupole mass spectrometer
  • an ion trap which is selected from the group comprising: Fourier transform ion trap, in particular Fourier transform ion cyclotron resonance trap, Penning trap, toroidal trap, Paul trap, linear trap, orbitrap, EBIT and RF buncher.
  • a conventional quadrupole ion trap can also be used as ion trap. If the ionized gas mixtures are accumulated in an ion trap for detection purposes, an “in situ” particle measurement is thus advantageously possible.
  • the ion trap is preferably embodied for detecting the ions stored or accumulated in the trap.
  • the use of such an ion trap for example an FT ion trap, enables the implementation of quick measurements (with scan times in the second range or faster, e.g. in the millisecond range).
  • the induction current which is generated by the trapped ions on the measurement electrodes, is detected and amplified in a time-dependent manner. Subsequently, this time dependence is transformed into the frequency space by a frequency transform, such as e.g. a Fast Fourier Transform, and the mass dependence of the resonant frequencies of the ions is used to convert the frequency spectrum into a mass spectrum.
  • Mass spectrometry via a Fourier transform can be carried out to carry out fast measurements, in principle with different types of ion traps (e.g. with the above-described types), wherein the combination with the so-called ion cyclotron resonance trap is the most common.
  • the FT-ICR trap constitutes a development of the Penning trap, in which the ions are enclosed in alternating electric fields and a static magnetic field.
  • mass spectrometry can be performed via cyclotron resonance excitation.
  • the Penning trap can also be operated with an additional buffer gas, wherein a mass selection by spatial separation of the ions can be generated by the buffer gas in combination with a magnetron excitation via an electric dipole field and a cyclotron excitation via an electric quadrupole field, such that the Penning trap can also be used for separating the substance to be detected from other substances.
  • the buffer gas in this type of trap generally has a movement-damping and hence “cooling” effect on the enclosed ions, this type of trap is also referred to as “cooling trap”.
  • the so-called toroidal trap enables a more compact design compared to a conventional quadrupole trap, while substantially having is an identical ion storage capacity.
  • the linear trap is a development of the quadrupole trap or Paul trap, in which the ions are not held in a three-dimensional quadrupole field but rather in a two-dimensional quadrupole field via an additional edge field, in order to increase the storage capacity of the ion trap.
  • the so-called orbitrap has a central, spindle-like electrode, about which the ions are kept on orbitals as a result of the electric attraction, wherein an oscillation along the axis of the central electrode is produced by an off-center injection of the ions, which oscillation generates signals in the detector plates, which signals can be detected like in the case of the FT-ICR trap (by FT).
  • An EBIT electron beam ion trap
  • RF radiofrequency
  • RFQ quadrupole
  • the ionization unit comprises at least two ionization devices, arranged in parallel or in series, for ionizing the gas mixture via different ionization procedures, wherein the ionization devices alternatively can be activated individually or (at least two of the ionization devices can be activated) together.
  • the ionization unit can have an ionization device, in particular a plasma ionization device configured to feed ions and/or metastable particles of an ionization gas to the detector in order to ionize the gas mixture in the detector, to be precise typically by charge exchange ionization or impact ionization.
  • the impact ionization or charge exchange ionization directly in the measuring cell or in the detector can take place on its own, i.e. without the provision of additional ionization units in the mass spectrometer; however, it is also possible that the ionization device for charge exchange ionization or impact ionization of the gas mixture in the detector is is provided as one of several ionization devices in the mass spectrometer.
  • the mass spectrometer according to the invention results substantially in the same advantages as the method according to the invention.
  • the ionization devices being activated together should be understand to mean that, in the case where e.g. three ionization devices are provided, for example two or three of these ionization devices are activated together at a given time.
  • the ionization devices can be connected in parallel or in series, so that, in the case of their common activation, the ionization devices can be employed at the same time or in succession for ionizing the same gaseous substance or substance mixture.
  • two or more of the ionization devices can be connected to a common feed channel, in order to enable a feed of the substances to be examined to one, or optionally more ionization devices, for simultaneous ionization with the aid of several different ionization procedures.
  • the ionized substances to be examined can be fed to the measurement chamber or to the detector by a pipe connection or there can be impact ionization or charge exchange ionization of the gas mixture directly in the detector (in particular of an ion trap).
  • the ionization devices are selected from the group comprising: charge exchange ionization device, plasma ionization device, electron impact ionization device, in particular filament ionization device, field ionization device, laser ionization device, photon ionization device, in particular UV light ionization device, VUV light ionization device and EUV light ionization device.
  • ICP inductively coupled plasma
  • dielectric barrier discharge, RF plasma, glow plasma, plasma at atmospheric pressure do not break up most of the substances to be examined into their elements as a result of is charge exchange, as a result of which the substance to be examined remains almost unchanged in terms of its structure and a simplified chemical characterization is possible.
  • different gases with the same mass number or the same mass-to-charge ratio are advantageously ionized by the plasma with different frequencies due to their typically differing ionization energies, and so it is possible to differentiate between different substances with the same mass number by analytical comparisons.
  • electron impact ionization electrons are generally released from an electrically heated filament and accelerated to high kinetic energies through an electric field in order to ionize the substance to be examined.
  • field ionization electrons are released from their bonds by a sufficiently strong electric field.
  • the field ionization can be used in high vacuum and in ultra-high vacuum and, compared to ionization via a filament, does not lead to a possibly undesired temperature increase. Furthermore, molecules are not fragmented much during field ionization, as a result of which gas mixtures can also be examined. It is understood that devices for chemical ionization, for electrospray ionization, for atmospheric pressure chemical ionization, for one photon ionization, for resonance-amplified multi-proton ionization, for matrix-supported laser desorption/ionization, for ionization via inductively coupled plasma or for ionization via glow plasma by charge exchange ionization can be provided as ionization devices.
  • the plasma ionization device is selected from the group comprising: high frequency plasma source, medium frequency plasma source, direct current plasma source, dielectric barrier discharge plasma source, atmospheric pressure plasma source and corona discharge plasma source.
  • the plasma can be excited by direct current, but it is also possible to use an (alternating) electromagnetic field for the excitation, e.g. a high frequency alternating field (with frequencies from 1 MHz to 30 MHz) or a medium frequency alternating field (with frequencies from 3 kHz to 1 MHz).
  • a high frequency alternating field with frequencies from 1 MHz to 30 MHz
  • a medium frequency alternating field with frequencies from 3 kHz to 1 MHz.
  • the ionization by an RF discharge can advantageously occur at temperatures from 10° C. to 200° C. In particular, it is possible to ionize particles with an atomic mass number of between 100 and 20 000 or of between 20 000 and 2 000 000.
  • the use of a dielectric barrier radiofrequency discharge is also possible.
  • ionization via an atmospheric pressure plasma source it is likewise possible to achieve particularly gentle ionization, via which entire linked macromolecular structures (particles) and not only individual molecules or molecule fragments are ionized.
  • the mass spectrometer comprises an ion trap for storing or accumulating the ionized gas mixture, which ion trap is selected from the group comprising: Fourier transform ion trap, in particular Fourier transform ion cyclotron resonance trap, Penning trap, toroidal trap, Paul trap, linear trap, orbitrap, EBIT and RF buncher.
  • the ion trap can be arranged in the measurement chamber, in which the detector is arranged. In particular, the ion trap can also be integrated in the detector.
  • the ion trap can form the detector itself, as is the case, for example, when using an ion trap in the form of an FT-ICR trap or orbitrap, in which it is also possible to detect the ions trapped in the ion trap in addition to storing these.
  • FIG. 1 shows a schematic representation of a mass spectrometer for mass spectrometric examination of gas mixtures
  • FIG. 2 shows a schematic representation of a mass spectrometer, in which self-cleaning of a measurement chamber is carried out
  • FIG. 3 shows a schematic representation of a mass spectrometer with an ionization unit, which comprises several ionization devices, and
  • FIG. 4 shows a schematic representation of a mass spectrometer with an ionization unit, which comprises an ionization device for carrying out a charge exchange ionization of the gas mixture directly in the detector.
  • FIG. 1 depicts a section of a chamber 1 , which is a process chamber in the current example, forming part of an industrial apparatus in which an industrial process is carried out.
  • the chamber 1 can alternatively be e.g. a (vacuum) housing of a lithography apparatus.
  • a gas atmosphere which contains at least one gas mixture 2 to be examined.
  • the gas mixture 2 has a substance 3 a present in the gas phase (i.e. a gas) with an atomic mass number ⁇ 100 and particles 3 b with mass numbers of 100 or more.
  • the gas mixture 2 is residual gas 3 a , in which a plurality of particles 3 b situated in the chamber 1 are held.
  • the chamber 1 has an outlet 4 , which is connected to the inlet 6 of a measurement chamber 7 , in particular directly connected to an inlet 8 of a plasma ionization device 9 arranged within the measurement chamber 7 , via a valve 5 .
  • a detector embodied as ion trap 10 is arranged in the interior of the measurement chamber 7 .
  • a conventional detector or a conventional spectrometer for example a conventional (quadrupole) spectrometer, which fulfills the functions of analysis and detection.
  • the valve 5 between the process chamber 1 and the measurement chamber 7 is opened, and so a flow of the gas mixture 2 from the process chamber 1 into the plasma ionization device 9 sets in.
  • the gas mixture 2 which has thus reached the plasma ionization device 9 , is then ionized via a plasma produced by the plasma ionization device 9 but not depicted in FIG. 1 .
  • RF plasma radiofrequency plasma
  • gas mixtures 2 which have particles 3 b with an atomic mass number of between 100 and 20 000, in particular of between 20 000 and 2 000 000, can be ionized as linked macromolecular structure, which is not fragmented further by the RF plasma.
  • the particles 3 b can be macromolecular conglomerates with a particle size of approximately 0.01-10 ⁇ m or more.
  • the energy provided for the ionization by the plasma ionization device 9 can be set dependent on the gas mixture 2 to be ionized, in particular dependent on the type of particles 3 b to be ionized.
  • ionization of the gas mixture 2 broadband ionization
  • a selective, narrowband ionization of individual types of gaseous substances 3 a or of particles 3 b is also supported.
  • the plasma ionization device 9 can have a control device (not depicted here), which enables this adaptation, for example by virtue of the field strength (optionally the frequency) of an electric or electromagnetic field being selected appropriately.
  • a plasma ionization device 9 which produces an RF plasma
  • a plasma ionization device which produces the plasma by a dielectric barrier discharge.
  • a dielectric is situated between two electrodes (not depicted in FIG. 1 ), which dielectric serves as dielectric barrier in order to produce a plasma in the form of a multiplicity of spark discharges and thus ionize a gaseous substance 3 a situated between the electrodes or the particles 3 b .
  • the use of other types of plasma ionization devices 9 such as e.g. glow plasma or a plasma at atmospheric pressure (atmospheric pressure plasma) is also possible.
  • the gas mixture 2 ionized in the plasma ionization device 9 reaches the measurement chamber 7 through an outlet 11 of the plasma ionization device 9 .
  • the gas mixture 2 is subsequently detected by the detector, embodied as an ion trap 10 in FIG. 1 , in the form of an FT-ICR trap or by a conventional, continuously operated detector, e.g. a quadrupole detector or a quadrupole mass spectrometer.
  • a feed device (not shown), for example in the form of an ion optical unit, can serve to feed the gas mixture 2 from the plasma ionization device to the detector 10 .
  • the electric FT-ICR ion trap 10 comprises a ring electrode, to which a radiofrequency high voltage is applied, and two cover electrodes, which can serve both as image charge detectors and as excitation electrodes.
  • ions are held trapped by a radiofrequency high voltage.
  • the ions experience a pulse excitation, they carry out characteristic oscillations in the high vacuum, depending on the mass/charge rat (m/z), which oscillations are recorded by image charge detection at the cover electrodes.
  • a low-distortion ion signal is obtained by forming the difference from the is image charge signals at both cover electrodes.
  • a low-noise amplifier (not depicted here) and a fast Fourier analysis (FFT) (likewise not depicted here) of the ion output signal, the characteristic ion frequencies and the intensities thereof are described.
  • the frequency spectrum can subsequently be converted into a mass spectrum, which can be used for the chemical characterization of the substance mixture 2 .
  • the FT-ICR trap 10 therefore enables a direct detection or the direct recording of a mass spectrum without the use of an additional analyzer so that a fast examination of the ionized gas mixture 2 is made possible.
  • the provision of the ion trap 10 renders it possible to increase the detection sensitivity by multiple measurement of the same ion population.
  • the ionized molecules of the gas mixture 2 are available for measuring for a relatively long time, since it is only the image charges and not the ions themselves that are used for the mass analysis.
  • a transport device for example in the style of a fan, can be provided in the region of the valve 5 or in the region of the outlet 4 from the process chamber 1 , or in the region of the inlet 6 into the measurement chamber 7 or in the region of the inlet 8 into the plasma ionization device 9 .
  • the measurement chamber 7 can also be connected to a pump device (not shown in FIG. 1 ).
  • FIG. 2 shows a mass spectrometer 21 , which is embodied for carrying out self-cleaning of the measurement chamber 7 .
  • the plasma ionization device 9 is an ionization device which produces a plasma.
  • a radiofrequency discharge is ignited between two electrodes 13 , 14 .
  • the gas (with the gas mixture 2 to be examined) fed from the process chamber 1 can serve to produce the plasma, which gas is fed to a detector not shown in FIG. 2 .
  • the plasma ionization device 9 is connected by a further pipe-shaped connection 15 to a is storage container 16 for a plasma gas 17 that can be fed to the plasma ionization device 9 via a further valve 5 a .
  • a plasma gas 17 can be fed to the plasma ionization device 9 via a further valve 5 a .
  • hydrogen (H 2 ), helium (He), argon (Ar) or oxygen (O 2 ) can be provided as plasma gas 17 .
  • a pump device 18 for evacuating the measurement chamber 7 or for removing a (residual gas) atmosphere and possible contaminants 19 contained therein (see below) is furthermore arranged in the region of the measurement chamber 7 .
  • the valve 5 is closed and the measurement chamber 7 is separated from the process chamber 1 in a first method step. Subsequently, the plasma gas 17 from the storage container 16 is fed to the plasma ionization device 9 , until a pressure of between approximately 1 bar and 1 ⁇ 10 10 mbar, preferably of between 10 mbar and 1 ⁇ 10 ⁇ 3 mbar sets in the measurement chamber. As a result of this, the cleaning effect of the self-cleaning method is particularly effective.
  • a plasma 20 is produced between the electrodes 13 , 14 in the plasma ionization device 9 .
  • the plasma ionization device 9 is aligned within the measurement chamber 7 in such a way that the plasma 20 reaches the region of contaminants 19 , which, for example, have been deposited on an inner structure 27 of the measurement chamber 7 .
  • the inner structure 27 can be a further ionization device, e.g. in the form of a filament, on which contaminants, e.g. in the form of hydrocarbons, have been deposited.
  • the contaminants 19 may also have been deposited on a detector (not depicted in FIG. 2 ) situated in the measurement chamber 7 . It is understood that, unlike as depicted in FIG. 2 , the plasma ionization device 9 may optionally be embodied in such a way that a plasma is produced in (almost) the entire measurement chamber 7 .
  • the contaminants 19 e.g. particles deposited on a filament
  • the produced plasma 20 an RF plasma in the present case
  • a conversion or decomposition of the contaminants 19 sets in, which converts the contaminants 19 into volatile compounds, wherein the decomposition or conversion can be brought about by a chemical reaction with the plasma gas 17 or optionally merely by splitting the is contaminants 19 up into a plurality of highly volatile fragments.
  • the contaminants 19 transformed into the gas phase are removed from the measurement chamber 7 wherein the pump device 18 is activated and the contaminants 19 are sucked away.
  • the further valve 5 a is closed and the operating pressure is reestablished in the measurement chamber 7 .
  • the mass spectrometer 21 can again be used for carrying out a mass spectrometric examination of a gas mixture present in the process chamber 1 .
  • the structure 27 (structured component) of the measurement chamber 7 depicted in FIG. 2 shows a location of a possible deposition of the contaminants 19 in merely an exemplary manner, and that the structure 27 can vary in terms of its form. If the structure 27 is a filament, the latter can be switched off during the cleaning, but it is optionally also possible for the filament to be activated additionally for transforming the contaminants 19 into the gas phase.
  • the structure 27 can also be a further ionization device, which is not embodied as a filament, but, for example, is embodied as a field ionization device or which structure serves for ionization via a pulsed laser. It is likewise understood that the embodiment of the plasma ionization device 9 can deviate from the configuration shown in FIG. 2 in order to bring the plasma 20 into the region of the contaminants 19 deposited on the inner structure 27 .
  • FIG. 3 depicts a mass spectrometer 21 with an ionization unit 22 , which comprises a first, second and third ionization device 9 a , 9 b , 9 c and also a selection device 23 .
  • the mass spectrometer 21 serves for mass spectrometric examination of the gas mixture 2 , which comprises gaseous substances 3 a and particles 3 b contained in a residual gas.
  • the gas mixture 2 is ionized by the ionization unit 22 , more precisely by the first to third ionization devices 9 a to 9 c , and detected or evaluated via a detector embodied as ion trap or as quadrupole 10 .
  • the mass spectrometer 21 is connected to a process chamber 1 in FIG. 3 , in which process chamber the gas mixture 2 to be examined can initially be stored.
  • the process chamber 1 is connected to the selection device 23 via an outlet 4 and a valve 5 .
  • the selection device 23 is or can be connected respectively to one of the first to third ionization devices 9 a to 9 c by pipes 24 . Proceeding from the individual ionization devices 9 a to 9 c , further pipe connections 25 are provided, which open into a measurement chamber 7 , in which the ion trap or a conventional (quadrupole) detector 10 (with analyzer) is arranged for detecting the ionized gas mixtures 2 .
  • the first ionization device 9 a is embodied as a plasma ionization device
  • the second ionization device 9 b is embodied as e.g. a filament ionization device
  • the third ionization device 9 c is embodied as a field ionization device, wherein the individual ionization devices 9 a , 9 b , 9 c are arranged or connected parallel to one another.
  • the gas mixture 2 introduced into the first to third ionization devices 9 a to 9 c can be ionized in each case via different ionization procedures.
  • the ionization devices 9 a , 9 b , 9 c can also be arranged in series or spatially in succession such that the gas mixture 2 to be examined passes through all ionization devices 9 a , 9 b , 9 c prior to reaching the measurement chamber 7 . It is understood that mixed forms between serial and parallel arrangement of the three ionization devices 9 a , 9 b , 9 c are also possible.
  • the individual ionization devices 9 a , 9 b , 9 c can alternatively be activated individually or together by the selection device 23 (e.g. in the form of a switchable valve) of the ionization unit 22 .
  • a common activation of ionization devices 9 a to 9 c should also be understood to mean the case where only two of the ionization devices 9 a to 9 c are activated at a given time. It is understood that the selection device 23 , via which the feed of substances 2 to be detected to the ionization devices 9 a to 9 c is controlled or regulated, can also individually activate or switch off the ionization devices 9 a to 9 c themselves.
  • the filament of the filament ionization device 9 b can optionally be heated or the heating of the filament can be deactivated, dependent on whether or not the gas mixture 2 to be examined is fed to the filament ionization device 9 b .
  • the selection is device 23 can be operated manually by an operator or optionally with the aid of a control device (not shown here).
  • the selection device 23 can also be switched, e.g. via a control unit, depending on the result of the detection of the gas mixture 2 , e.g. if the amount of a detected ionized substance per time unit is too low.
  • the gas mixture 2 to be examined is initially introduced into the process chamber 1 or the gas mixture 2 has already accumulated in the process chamber.
  • the gas mixture 2 to be examined is fed to the selection device 23 , which optionally can be supported by a pump device (not shown here) or a feed device in the form of a fan or the like.
  • the selection device 23 can make the fed gas mixture 2 available to either only one of the three plasma ionization devices 9 a to 9 c (e.g. only the first ionization device 9 a embodied as plasma ionization device) or to several ionization devices 9 a to 9 c (in this case two or three). It is possible in an advantageous fashion to examine by mass spectroscopy a gas mixture 2 which is still unknown in terms of its chemical structure as a result of the option of individually activating the ionization devices 9 a to 9 c or adding these during the examination.
  • the ion trap 10 arranged in the measurement chamber 7 can be an ion trap 10 described in conjunction with FIGS. 1 and 2 , preferably an electric FT-ICR trap.
  • transport devices 26 which can be e.g. ion optical units, in the pipe connections 25 between the individual ionization devices 9 a to 9 c and the measurement chamber 7 .
  • the self-cleaning illustrated above in conjunction with FIG. 2 can also take place in the mass spectrometer 21 depicted in FIG. 3 , to be precise by virtue of the plasma ionization device 9 a being employed for generating a plasma which is fed to the measurement chamber 7 for cleaning purposes.
  • the plasma produced in the plasma ionization device 9 a can be fed to the other two ionization devices 9 b , 9 c in order to clean these.
  • a plasma gas from a storage container can be fed to the plasma ionization device 9 a (cf. FIG. 2 ).
  • the plasma gas can be an inert gas, e.g. argon or helium, or else a reactive gas, e.g. hydrogen or oxygen.
  • the contaminants transformed into the gas phase can reach the measurement chamber 7 via the pipe connections 25 and can be discharged from there.
  • FIG. 4 shows a mass spectrometer 21 , which has a similar configuration to the mass spectrometer 21 shown in FIG. 1 .
  • the mass spectrometer 21 serves for mass spectrometric examination of the gas mixture 2 , which comprises gaseous substances 3 a and particles 3 b contained in a residual gas.
  • the mass spectrometer 21 has an ionization unit 22 with a plasma ionization device 9 , which enables charge exchange ionization directly in the detector 10 .
  • the detector 10 is embodied as ion trap, in particular as FT-ICR trap or as orbitrap.
  • a conventional measuring cell or a conventional mass spectrometer can also serve as detector 10 ; the conventional mass spectrometer having a photomultiplier, a secondary electron multiplier or the like for detection purposes and typically additionally house an analyzer for mass selection, i.e. the detector 10 corresponds to a conventional (quadrupole) mass spectrometer in which both analysis and detection are performed.
  • the gas mixture 2 is introduced directly, i.e. without prior ionization, into the detector 10 (i.e. into the measuring cell/ion trap).
  • Ions and/or metastable or excited particles 29 produced by the plasma ionization device 9 , are fed to the detector 10 in order to enable a charge exchange with the gas mixture 2 or an impact ionization.
  • a (neutral) ionization gas 30 is taken from a gas reservoir 33 via a metering valve 31 and a gas feed 32 and fed to the plasma ionization device 9 .
  • the ionization gas 30 is ionized or excited in the plasma ionization device 9 and the ions or metastable/excited particles 29 produced herein are fed to the detector 10 , in which the charge exchange ionization or impact ionization of the gas mixture 2 takes place.
  • the gas mixture 2 to be analyzed can be ionized, accumulated and measured directly in the measuring cell (detector 10 ), without transport of the ionized gas mixture into the detector 10 being required.
  • a large number of gasses and gas mixtures can be used as ionization gas 30 , e.g. He, H 2 , Ar, N 2 , Xe, Kr, CH 4 etc.
  • a plasma source which may be configured as high frequency plasma source, medium frequency plasma source, direct current plasma source, dielectric barrier discharge plasma source, atmospheric pressure plasma source, corona discharge plasma source or the like, can serve as plasma ionization device 9 . It is understood that another ionization device, which can produce an impact or charge exchange ionization of the gas mixture 2 in the detector 10 , can also be used in place of a plasma source.
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US20160372310A1 (en) 2016-12-22
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DE102013201499A1 (de) 2014-07-31
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US10903060B2 (en) 2021-01-26
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JP2018032641A (ja) 2018-03-01
KR101868215B1 (ko) 2018-06-15

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