Mass spectrometer, use thereof, and method for the mass spectrometric examination of a gas mixture

Abstract

The disclosure relates to a mass spectrometer for mass spectrometric examination of gas mixtures, including: an ionization device and an ion trap for storage and mass spectrometric examination of the gas mixture. In one aspect of the disclosure, the ionization device is embodied for supplying ions and/or metastable particles of an ionization gas and/or for supplying electrons to the ion trap for ionizing the gas mixture to be examined and the mass spectrometer is embodied to determine the number of ions and/or metastable particles of the ionization gas present in the ion trap and/or the number of ions of a residual gas present in the ion trap prior to examining the gas mixture. The disclosure also relates to the use of such a mass spectrometer and a method for mass spectrometric examination of a gas mixture.

Claims

1. A mass spectrometer, comprising: an ionization device configured to provide an ionization component which comprises at least one member selected from the group consisting of: a) ions of an ionization gas; and b) metastable particles of the ionization gas; an ion trap configured to store and mass spectrometrically examine a gas mixture in the ion trap; and a controllable inlet configured to provide a pulsed supply of the gas mixture to the ion trap, wherein the mass spectrometer is configured so that, during use of the mass spectrometer: the ionization device provides the ionization component to the ion trap and the controllable inlet provides the pulsed gas supply to the ion trap so that the ionization component ionizes the gas mixture in the ion trap via a charge exchange process and/or impact ionization; determines a number of a substance which comprises at least one member selected from the group consisting of: a) ions of the ionization gas present in the ion trap; b) metastable particles of the ionization gas present in the ion trap; and c) ions of a residual gas present in the ion trap prior to examining the gas mixture; and reduces an influence of fluctuations of the ionization component by determining a particle number of ionized constituents of the gas mixture in the ion trap in a pulsed manner using a correction factor that takes into account the determined number of the substance.

2. The mass spectrometer of claim 1, wherein the mass spectrometer is configured to determine a particle number of an ionized constituent of the gas mixture in the ion trap with an inaccuracy of less than 5%.

3. The mass spectrometer of claim 1, wherein the ionization device is configured to supply metastable particles of an ionization gas in the form of a metastable noble gas.

4. The mass spectrometer of claim 3, wherein the mass spectrometer is configured to record at least 10 spectra per second with a mass bandwidth of 500 atomic mass units in each case.

5. The mass spectrometer of claim 1, further comprising a plasma source configured to produce the ionization component.

6. The mass spectrometer of claim 5, wherein the plasma source is configured to produce the ionization component at a temperature of less than 100 C.

7. The mass spectrometer of claim 1, wherein the mass spectrometer is configured so that, when a number of ionized constituents of the gas mixture present in the ion trap exceeds a threshold, the mass spectrometer removes at least some of the of ionized constituents from the ion trap.

8. The mass spectrometer of claim 1, wherein the mass spectrometer is configured to selectively detect ionized constituents of the gas mixture in predefined measurement ranges of mass-to-charge ratio.

9. The mass spectrometer of claim 1, wherein the mass spectrometer has a dynamic range of 10.sup.8 or more.

10. The mass spectrometer of claim 1, wherein the ion trap is configured to accumulate individual ionized gas constituents of the gas mixture, and the mass spectrometer has a detection limit of 10.sup.15 millibar or less.

11. The mass spectrometer of claim 1, further comprising a pressure reduction unit which comprises at least one modular pressure stages configured to be connected in series to reduce the gas pressure of the gas mixture.

12. The mass spectrometer of claim 1, wherein the mass spectrometer is configured to examine gas mixtures with a gas pressure of between 10.sup.5 millibar and 10.sup.15 millibar.

13. The mass spectrometer of claim 1, wherein the mass spectrometer is configured to: a) repeatedly excite ionized constituents of the gas mixture in the ion trap; and b) record a mass spectrum of the ionized constituents to be examined during a predetermined time duration of each excitation.

14. The mass spectrometer of claim 13, wherein the time duration for recording a mass spectrum is five milliseconds or less.

15. The mass spectrometer of claim 1, wherein the ion trap comprises a member selected from the group consisting of a Fourier transform ion trap, a Penning trap, a toroidal trap, a Paul trap, a linear trap, an orbitrap, an EBIT, and a nRF buncher.

16. The mass spectrometer of claim 1, wherein the mass spectrometer is configured to detect vibrations with a vibration frequency of between 1 Hz and 15 kHz.

17. The mass spectrometer of claim 1, wherein the mass spectrometer is configured to determine a number of ions present in the ion trap.

18. The mass spectrometer of claim 17, wherein the mass spectrometer is configured to determine a particle number of ionized constituents of the gas mixture in the ion trap, taking into account the determined number of ions present in the ion trap.

19. The mass spectrometer of claim 1, wherein: the ionization component comprises metastable particles of the ionization gas; and the mass spectrometer is configured to determine a number of the metastable particles of the ionization gas present in the ion trap.

20. The mass spectrometer of claim 19, wherein the mass spectrometer is configured to determine a particle number of ionized constituents of the gas mixture in the ion trap, taking into account the determined number of metastable particles of the ionization gas present in the ion trap.

21. The mass spectrometer of claim 1, wherein the mass spectrometer is configured so that, during use of the mass spectrometer: an increase in the determined particle number results in a decrease in the correction factor; and a decrease in the determined particle number results in an increase in the correction factor.

22. The mass spectrometer of claim 1, wherein the mass spectrometer is configured to: supply to the ion trap metastable particles of the ionization gas; determine the number of i) metastable particles of the ionization gas present in the ion trap; and ii) ions of a residual gas present in the ion trap prior to examining the gas mixture; and reduce the influence of fluctuations of the ions or metastable particles provided for the ionization by determining a particle number of ionized constituents of the gas mixture in the ion trap in a pulsed manner using a correction factor that takes into account the determined number of at least one member selected from the group consisting of: i) metastable particles of the ionization gas; and ii) ions of the residual gas.

23. The mass spectrometer of claim 22, wherein the metastable particles of the ionization gas are electrically neutral.

24. A lithography apparatus, comprising the mass spectrometer of claim 1.

25. The lithography apparatus of claim 24, wherein the lithography apparatus is an EUV lithography apparatus.

26. The lithography apparatus of claim 25, wherein the EUV lithography apparatus comprises a projection system, and the mass spectrometer is connected to the projection system.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) Exemplary embodiments are depicted in the schematic drawing and will be explained in the following description. In detail:

(2) FIG. 1 shows a schematic illustration of a mass spectrometer for mass spectrometric examination of a gas mixture,

(3) FIG. 2 shows a schematic illustration of an exemplary embodiment of an ion trap of the mass spectrometer in FIG. 1,

(4) FIG. 3 shows a schematic illustration of the timing of a measurement process in the ion trap,

(5) FIG. 4 shows a measurement process for evaluating a mass spectrum, in which a measurement window is displaced for realizing a fast measurement, and

(6) FIGS. 5a,b show two mass spectra, which are evaluated by the SWIFT process or by a mass-selective time multiplex measurement,

(7) FIG. 6 shows a schematic illustration of an EUV lithography apparatus, which has a mass spectrometer, and

(8) FIG. 7 shows a schematic illustration of a device for atomic layer deposition on a substrate, having a mass spectrometer.

DETAILED DESCRIPTION

(9) In the following description of the drawings, identical reference signs are used for the same or functionally equivalent components.

(10) FIG. 1 schematically shows a mass spectrometer 1, which is connected to a chamber 8, or can be connected thereto, in which a gas mixture 2 to be examined is arranged. By way of example, the chamber 8, of which only a section is depicted in FIG. 1, can be a process chamber, which forms part of an industrial apparatus in which an industrial process is carried out. Alternatively, the chamber 8 can be e.g. a (vacuum) housing of a lithography apparatus or a different type of chamber, in which the gas mixture 2 to be examined is arranged. In the shown example, the gas mixture 2 has a substance 3a present in the gas phase (i.e. a gas) with an atomic mass number <100 and particles 3b, the mass number of which lies at 100 or more.

(11) The chamber has an outlet 4, which can be connected to the inlet 6 of a measurement chamber 7 via a controllable valve 5 belonging to the mass spectrometer 1. In the mass spectrometer 1 shown in FIG. 1, the gas mixture 2 is introduced directly, i.e. without a preceding ionization, into an ion trap 10 serving as measurement cell. An ionization device 12 serves for ionizing the gas mixture 2 directly in the ion trap 10, by virtue of ions 13a and/or metastable or excited particles 13b of an ionization gas 13 being supplied to the ion trap 10, which ions and/or particles ionize the gas mixture 2 by a charge exchange or impact ionization, typically in the ion trap 10. The ionization device 12 shown in FIG. 1 also has an electron beam source 20 in the form of an electron beam gun for producing electrons 20a with variable electron energies in the range between e.g. 1 eV and 100 eV, which electron beam source can be used in addition or as an alternative to the plasma source 18 and which is depicted by a dashed line in FIG. 1. The electrons 20a serve to ionize the gas mixture 2 directly in the ion trap 10 by electron impact ionization. In this way, the gas mixture 2 to be analyzed can be ionized, optionally accumulated and measured, directly in the measurement cell (ion trap 10), without transportation of the ionized gas mixture into the ion trap 10 being required. Alternatively, there can also be an ionization of the gas mixture 2 in the direct vicinity of the ion trap 10, wherein, in the latter case, there is a need for transportation of the ionized gas mixture to the ion trap 10.

(12) In order to produce the primary ions 13a or the excited particles 13b, the (neutral) ionization gas 13 is removed from a gas reservoir 17 by a metering valve 15 and a gas supply line 16 and supplied to a plasma source 18. The ionization gas 13 is ionized or excited in the plasma source 18 and the ions 13a and/or metastable/excited particles 13b produced hereby are supplied to the ion trap 10 in order to bring about the charge exchange ionization or impact ionization of the gas mixture 2. The plasma source 18 can be a radiofrequency plasma source, medium frequency plasma source, DC plasma source, dielectric barrier discharge plasma source, atmospheric pressure plasma source, corona discharge plasma source, etc.

(13) In the present example, the plasma source 18 is embodied to produce ions 13a and/or metastable particles 13b of the ionization gas 13 at a temperature of less than 100 C., i.e. the plasma discharge in the plasma source occurs at a low temperature (under 100 C.). By way of example, this can be achieved by applying an alternating radiofrequency field (with frequencies between 1 MHz and 30 MHz) since a corresponding RF discharge can advantageously occur at temperatures between 10 C. and 200 C. or it can be realized by the use of a DC plasma source specifically developed for this. It is understood that, in place of a plasma source 18, use can also be made of a different type of ionization device which is able to convert or ionize the (neutral) ionization gas 13 into an excited electron state in order to bring about an impact or charge exchange ionization of the gas mixture 2 in the ion trap 10.

(14) A plurality of gases and gas mixtures can be used as ionization gas 13, e.g. He, H.sub.2, Ar, N.sub.2, Xe, Kr, O.sub.2 etc. It was found to be particularly advantageous for a noble gas, in particular helium, to be used as ionization gas 13 which is converted into a metastable noble gas 13b, i.e. into noble gas particles (e.g. He*) which are in an excited electron state just before ionization, by the plasma source 18. A particularly sparing (cold) ionization with a small fragmentation of the analyte can be achieved, in particular, by a charge exchange between the analyte, i.e. a gas constituent 3a, 3b to be examined, and the metastable noble gas particle 13b.

(15) This also renders it possible to ionize particles 3b with an atomic mass number of between 100 and 20,000, in particular between 20,000 and 2,000,000, as linked macromolecular structures, since these are not fragmented further by the cold RF plasma of the metastable noble gas particles 13b. By way of example, the particles 3b can be macromolecular mixtures with a particle size of approximately 0.001-10 m or more. It is understood that, alternatively, the ionization gas, e.g. helium, can be present in a substantially completely ionized form (i.e. as He.sup.+) and that mixed forms are also possible, for example the use of an ionization gas with non-negligible proportions of both He.sup.+ and He*.

(16) For particle measurement and characterization of large particles 3b with mass numbers up to 2,000,000 amu in the ion trap 10, it is possible to make use of the fact that the mass-to-charge ratio m/z to be detected depends as follows on the storage amplitude V.sub.rf (trajectory diameter) and field frequency f.sub.rf in the ion trap 10:
m/zV.sub.rf/(f.sub.rf).sup.2.

(17) Consequently, it is possible to measure particles 3b with a very large mass by increasing the storage amplitude V.sub.rf and/or by reducing the field frequency f.sub.rf in the ion trap 10.

(18) A further advantage of the use of metastable noble gas particles 13b, i.e. of neutral particles in an excited electron state, for the ionization of the gas mixture 2 in the ion trap 10 consists of the fact that these have a particularly large cross section, resulting in a larger impact probability with the constituents of the gas mixture 2 to be examined in the ion trap 10. As a result, the ionized particles 3a, 3b to be examined are collected more quickly in the centre of the ion trap 10, without a higher pressure of a buffer gas being required for this purpose. Thus, by using metastable noble gas particles 13b for ionizing the gas mixture 2, it is possible to carry out a measurement in the ion trap 10 significantly more quickly than in already known solutions, and so the mass spectrometer 1 can be used to record at least 10 spectra/s with a mass bandwidth of in each case at least 500 amu or 1000 amu.

(19) As described further above, an electron beam source 20, which, in particular, can produce electrons 20a with variable electron energies in the range between e.g. 1 eV and 100 eV, can also be used in order to ionize constituents 3a, 3b of the gas mixture 2 with specific mass-to-charge ratios in a targeted manner. It is understood that, as an alternative to the example shown in FIG. 1, the ionization device 12 can have only a plasma source or only an electron beam source 20 in order to ionize the gas mixture 2 to be examined in the ion trap 10. The electrons 20a and/or the metastable particles 13b of the ionization gas 13 can also ionize residual gas 14 present in the ion trap 10, i.e. residual gas ions 14a are produced.

(20) It is likewise possible to identify in FIG. 1 that the mass spectrometer 1 has a pressure reduction unit 11, which is attached to the inlet 6 of the measurement chamber 7 and which connects the measurement chamber 7 with the outlet 4 of the chamber 8. In the shown example, the pressure reduction unit 11 has three modular pressure stages 11a-c, connected in series, for reducing the gas pressure p.sub.0 of the gas mixture 2 to be examined in the chamber 8. In the shown example, the mass spectrometer 1 is attached by flanges in the region of the outlet 4 of the chamber 8. The three pressure stages 11a-c each have two end-side flanges, via which they can be attached to the inlet 6 to the measurement chamber 7 or to one another.

(21) Depending on the application, i.e. depending on the gas pressure p.sub.0 of the gas mixture 2 in the chamber 8, it is possible to connect one, two or three or none of the pressure stages 11a-c in series in order to reduce the gas pressure so far that the gas mixture 2 can be supplied to the measurement chamber 7 for analysis purposes. The three pressure stages 11a-c are coordinated with one another. By way of example, the coordination can be realized by a pressure reduction by a factor of approximately 100-1000 mbar in each pressure stage 11a-c. It is possible to use all three pressure stages 11a-c in the case of a high gas pressure p.sub.0 of the gas mixture to be examined (100 bar-10.sup.2 mbar), it is possible to use two pressure stages 11a, 11b in the case of a medium pressure (10.sup.2 mbar-10.sup.5 mbar) of the gas mixture 2 in the chamber 8, and it is possible to use only one or no pressure stage 11a in the case of a low gas pressure (<10.sup.5 mbar) of the gas mixture 2 in the chamber 8, through which pressure stages the gas mixture 2 is transported.

(22) The pressure stages 11a-c can be connected in series by virtue of being attached to one another in a gas-tight manner, for example by virtue of these being screwed to one another on flanges. In this manner, it is possible to disassemble or reassemble the pressure stages 11a-c very quickly in order to serve a predefined pressure range of the gas pressure p.sub.0 of the gas mixture 2 to be detected and to ensure that the gas pressure p.sub.0 reduces to approximately 10.sup.5 mbar or to 10.sup.9 mbar in the direction of the ion trap 10 so that the ion trap 10 can be used for the gas analysis. By using one or more pressure stages 11a-c, it is possible to use the mass spectrometer 1 for examining gas mixtures 2 with a gas pressure p.sub.0 between 10.sup.5 mbar and 10.sup.15 mbar with an unchanging detection limit, wherein the mass spectrometer 1 can, in particular, be adapted to the desired pressure range in a particularly simple manner. Here, the (lower) detection limit can be defined as follows: it is possible to measure approximately 100 ions per second at a pressure of 10.sup.8 mbar in the measurement chamber 7.

(23) In the example shown in FIG. 1, the ion trap 10 is embodied as magnetic FT-ICR trap, which will be described in more detail below in conjunction with FIG. 2. In the magnetic FT-ICR trap 10, the ions 13a are trapped in a homogeneous magnetic field B, which extends along the Z-direction of an XYZ-coordinate system and forces the ions 13a trapped in the Z-direction in the FT-ICR trap 10 onto orbits with a mass-dependent orbital frequency. Furthermore, the FT-ICR trap 10 has an arrangement on which an alternating electric field is applied perpendicularly to the magnetic field B and therefore a cyclotron resonance is produced. In the shown example, the arrangement has six electrodes 21. If the frequency of the irradiated alternating field and the angular cyclotron frequency correspond, resonance occurs and the cyclotron radius of the relevant ion 13a increases by the take-up of energy from the alternating field. These changes lead to measurable signals on the electrodes 20 of the FT-ICR trap 10, which lead to a current flow I, which is supplied to an FFT (Fast Fourier Transform) spectrometer 23, likewise a component of the mass spectrometer 1, via an amplifier 22.

(24) The time-dependent current I, received in the FFT spectrometer 23, is subjected to a Fourier transform in order to obtain the frequency f dependent mass spectrum, which is illustrated bottom right in FIG. 2. Thus, the FT-ICR trap 10 enables direct detection or direct recording of a mass spectrum, and so a fast gas analysis is rendered possible. It is also possible to selectively remove individual ions or ions with specific mass numbers or mass-to-charge ratios m/z from the FT-ICR trap 10, for example by virtue of an alternating field being applied to the electrodes 21 in order to guide the selected ions to be removed from the trap 10 onto unstable trajectories.

(25) It is likewise possible to identify from FIG. 2 that the amplitude of the envelope of the time-dependent image current I reduces with time after excitation, wherein the decrease in time or the transient of the current I depends directly on the mean free path length and hence on the pressure in the FT-ICR trap 10. If an exponential decrease of the amplitude of the current I is assumed, it is possible to determine the pressure in the FT-ICR trap 10 with great accuracy on the basis of e.g. the time constant , during which there is a reduction in the amplitude to a level of 1/e (i.e. approximately 37%) of the original value; this can be used, in particular, for determining the number of metastable particles (see below), since this number correlates with the pressure.

(26) Fast recording of a mass spectrum with the aid of Fourier spectrometry can occur not only in the above-described FT-ICR trap 10, but also in developments of the trap type shown in FIG. 2. By way of example, the FT-ICR ion trap 10 can be embodied as so-called electric FT-ICR trap, which includes 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. In the compact electric variant of an FT-ICR trap 10, ions are held trapped by a radiofrequency high voltage. If the ions experience an impulse excitation, they carry out characteristic vibrations in the high vacuum, depending on the mass/charge ratio (m/z), which vibrations are recorded by image charge detection at the cover electrodes. A low-distortion ion signal is obtained by forming the difference from the image charge signals at both cover electrodes. Via the low-noise amplifier 22 and the spectrometer 23 for fast Fourier analysis (FFT) of the ion output signal, the characteristic ion frequencies and the intensities thereof can be depicted. The frequency spectrum can subsequently be converted into a mass spectrum, in which the number of detected particles is depicted depending on the mass-to-charge ratio m/z.

(27) In order to obtain a quantitative analysis, which is as accurate as possible, of the gas mixture 2 to be examined or of the constituents 3a, 3b thereof, i.e. in order to determine as precisely as possible how many ions 13a are present in the ion trap 10 at a specific mass-to-charge ratio m/z, a continuous online in-situ calibration of the mass spectrometer 1 can be carried out. In the process, the number of primary ions, i.e. the ions 13a of the ionization gas 13 and the ions 14a of the residual gas, and the number 13b of the metastable particles of the ionization gas 13 which are available for the charge or impact ionization of the gas mixture 2 in the ion trap 10 are determined, as a result of which time fluctuations due to the variation or drift of the primary ions 13a, 14a or metastable particles 13b provided for the ionization can be practically completely eliminated.

(28) The above described result is possible due to a specific measurement procedure and a suitable control of the electronics of the mass spectrometer 1, which control is undertaken by a control device 19 (cf. FIG. 1). The timing of the measurement procedure is explained in more detail below on the basis of FIG. 3, wherein exemplary time durations t1 to t7 are specified for the individual steps of the measurement method.

(29) In a first step (time duration t1 approximately 1 ms) there is an accumulation of the primary ions 13a, 14a in the ion trap 10. For accumulation purposes, the control device 19 opens the metering valve 15 and lets ionization gas 13 flow into the plasma source 18, in which the gas is ionized and where it enters the ion trap 10 in the form of ions 13a. Additionally, a residual gas 14, present in the ion trap 10, can be (partly) ionized by the metastable particles 13b of the ionization gas 13 and/or by the electrons 20a supplied to the ion trap 10 so that residual gas ions 14a are formed.

(30) As soon as a sufficient number of primary ions 13a, 14a are accumulated in the ion trap 10, the primary ions 13a, 14a are excited in a second step (time duration t2 approximately 0.01 ms) by virtue of an excitation signal, likewise produced by the control device 19, being applied to the corresponding electrodes 21 of the ion trap 10. In a third step (time duration t3 approximately 0.1 ms) there is a measurement or detection of the number of primary ions 13a, 14a in the ion trap 10.

(31) Just before the end of the second step and during the third step, a fourth step (time duration t4<1 ms) occurs in parallel, to be precise the transportation of the (non-ionized) gas mixture 2, more precisely a gas pulse 2a of the gas mixture 2, from the inlet 6 of the measurement chamber 7 into the ion trap 10. In order to produce the gas pulse 2a, the valve 5 is briefly actuated by the control device 19 and opened, with the time duration in which the valve 5 is opened typically lying in a region of less than approximately 1 s or less than a few milliseconds. The control device 19 synchronizes the production of the gas pulse 2a of the gas mixture 2 with the step of measuring the number of primary ions 13a in such a way that the gas pulse reaches the ion trap 10 when the measurement of the number of primary ions 13a, 14a is complete. Optionally, the gas mixture 2 can also be ionized in the direct vicinity of the ion trap 10. In this case, the gas pulse reaches the ion trap 10 with a time offset, i.e. just after completion of the measurement of the number of primary ions. Since the gas pulse 2a moves toward the inlet of the ion trap 10, it is optionally possible to dispense with the provision of a transportation device for transporting the ionized gas mixture 2 into the ion trap 10.

(32) In order to facilitate the flow of the gas mixture 2 or of the gas pulse from the chamber 8 into the ion trap 10, a transportation device, e.g. in the type of a fan, can be provided in the region of the valve 5, in the region of the outlet 4 from the chamber 8, in the region of the inlet 6 into the measurement chamber 7 and/or in the region between the inlet 6 and the ion trap 10. For the purposes of transporting the gas mixture 2 or a gas pulse to the ion trap 10, the measurement chamber 7 can also be connected to a pumping device (not shown in FIG. 1).

(33) In a fifth step (time duration t5 approximately 0.1 ms) the gas mixture 2 transported in the gas pulse 2a is ionized in the ion trap 10 by impact ionization and/or by a charge exchange ionization via the primary ions 13a, 14a or via the metastable particles 13b. In the process, it was found to be advantageous if the flow of the ionization gas 13 or of the ions 13a and metastable particles 13b of the ionization gas 13 is directed counter to the flow direction of the gas pulse 2a such that the flow of the ionization gas 13 and the gas pulse 2a impact on one another in the interior of the ion trap 10. In order to achieve this, it is advantageous if, as shown in FIG. 1, the inlet 6 for supplying the gas pulse 2a and the inlet of the ionization device 12 for supplying the gas flow of the ionization gas 13 are arranged lying opposite one another. The same applies to the electron source 20 or the electron beam 20a, which should be likewise aligned with the gas pulse 2a or should be arranged lying opposite the inlet 6 for supplying the gas pulse 2a, as depicted in FIG. 1.

(34) In a subsequent sixth step (time duration t6 approximately 1 ms) the ions of the gas mixture 2 are excited. Prior to or during the excitation of the ions of the gas mixture 2, the primary ions 13a, 14a can be removed from or suppressed in the ion trap 10 by virtue of a suitable excitation signal being produced and applied to the electrodes 20. In a subsequent seventh step (time duration t7=up to 100 ms) there is a measurement or detection of the excited ions or ionized constituents 3a, 3b of the gas mixture 2, wherein the measured signal level Hf is directly proportional to the ion number of the respective ion population in the corresponding mass-to-charge ratio m/z.

(35) In order to minimize the influence of the time-dependent fluctuations in the number of primary ions 13a, 14a, provided for the ionization, or metastable particles 13b on the determination of the ion number Hf, the following procedure is adopted: the signal level Hf for each frequency for each mass-to-charge ratio m/z is determined by the following expression:
Hf(corrected)=K*Hf(uncorrected)*H1/Hf,(1),
where H1 denotes the signal level of all ions stably stored and excited in the ion trap, Hf(uncorrected) denotes the spectral level or signal level of the ion of interest or of the ionized constituent to be examined 3a, 3b, Hf denotes the sum of all signal levels of the spectral lines present in the measured spectrum and K denotes a correction factor independent of mass and frequency, which includes the determined number of primary ions 13a, 14b, provided for the ionization, or metastable particles 13b, to be precise, in such a way that a larger determined number brings about a smaller correction factor K and vice versa. It is understood that it is generally sufficient to determine the number of metastable particles 13b in the case of an ionization gas 13 present substantially in the form of metastable particles 13b (e.g. He*) and that it is generally sufficient to determine the number thereof for the calibration in the case of an ionization gas 13 present substantially in the form of primary ions 13a (e.g. He.sup.+).

(36) By detecting the level Hf of the induced signal on the measurement electrodes 21 multiplied by the degree of excitation or the number H1 of all ions 13a, 14a stably stored and excited in the ion trap and by taking into account the correction factor K, it is possible to determine the actual number of ionized constituents 3a, 3b of the gas mixture 2, situated in the ion trap 10, at a predefined mass-to-charge ratio with a high degree of precision, i.e. typically with an inaccuracy of less than 5%. The degree of excitation specifies the ratio of the radius of the rollercoaster movement to the core radius of the ion cell. The above-described calibration can be carried out at all times, in particular during the actual measurement, for any selected gas types.

(37) In principle, the procedure illustrated above can be repeated a number of times or any number of times. However, it may be advantageous if, after the ionization of the gas mixture 2, the ionized constituents 3a, 3b of the gas mixture 2 are excited repeatedly in the ion trap 10, without there being a re-ionization of the gas mixture 2 in the process, as is described below on the basis of FIG. 4.

(38) FIG. 4 shows an illustration of a measurement of ionized constituents 3a, 3b of the gas mixture 2 in the ion trap 10, in which there is an excitation (as desired, once to several tens of times) at a time to of the ionized constituents 3a, 3b of the gas mixture 2 with the aid of a pulsed excitation signal SA after the completion of the impact or charge exchange ionization, which is denoted by I in FIG. 4. A mass spectrum MS1 to MSx over an (in the present example) constant period of time Tm1 to Tmx (approximately 5 ms or less) is recorded during or after each excitation. In other words, a predefined measurement window (with the constant time duration) is repeatedly displaced in order to record respectively one mass spectrum MS1 to MSx during several successive excitations, without the need for a further ionization.

(39) This renders it possible to undertake a very fast mass spectrometric analysis of the gaseous constituents 3a, 3b situated in the ion trap 10, as a result of which a chemical process proceeding during the measurement can be observed in real time. In particular, it is possible to measure the analyte molecules before these react with one another and it is possible to detect intermediate products which are formed during a chemical reaction. A mass spectrometer 1, in which the above-described measurement principle is applied, is suitable, in particular, for use in chemical process analysis.

(40) In order to increase the dynamic range, i.e. the ratio between the maximum detectable signal strength and the minimal detectable signal strength, of the mass spectrometer 1, it is possible to evaluate a mass spectrum as described below on the basis of FIG. 5a and FIG. 5b.

(41) FIG. 5a shows a mass spectrum in which there is a so-called SWIFT excitation for increasing the dynamic response, in which relatively large ion populations, i.e. ion populations in which the particle number at a given mass-to-charge ratio m/z lies over a predefined threshold SW (cf. FIG. 5a), are removed from the ion trap 10 or suppressed during the measurement. In particular, the SWIFT excitation can be used to realize a comb filter, in which several subsets of ion populations, which each correspond to different measurement regions MB1 to MBx, i.e. to several intervals of mass-to-charge ratios, are measured simultaneously, as is indicated in FIG. 5a.

(42) The dynamic response can also be increased by switching a measurement region, as is depicted in FIG. 5b. There, the mass spectrum is split into measurement regions MB1 to MBx with in each case different mass-to-charge ratios, wherein each measurement region MB1 to MBx is evaluated at a different measurement time t1 to tx. It is likewise possible to increase the dynamic range by such a temporal switch between the measurement ranges MB1 to MBx or by the mass-selective time multiplex measurement realized in this manner.

(43) It is understood that the measurement modes described in conjunction with FIG. 5a and FIG. 5b can also be combined in order to increase the dynamic range. It is also possible to use more complicated types of measurement methods than the ones described here in order to further increase the dynamic range. Already when using one of the two measurement principles described in conjunction with FIG. 5a and FIG. 5b, it may optionally be possible to achieve a dynamic range of the mass spectrometer 1 of 10.sup.8:1 or more.

(44) The option of accumulating individual ionized gas constituents of the gas mixture 2 in an ion trap 10 can be used in combination with the above-described measurement methods for increasing the dynamic range in order to reduce the detection limit of the mass spectrometer. What is used here is that ion trap mass spectrometers operate on a discontinuous basis and an analysis of the ion number only takes place after a predefined accumulation time (e.g. less than approximately 5 ms). By combining the above described processes for increasing the dynamic response (SWIFT or time multiplexing measurement, cf. FIG. 5a and FIG. 5b) with the accumulation ability of the ion trap 10, it is possible to accumulate individual ions until a sufficiently large measurement signal is present. In the case of a known (calibrated) measurement signal and a known accumulation time, the ion population to be examined can be determined quantitatively. In this manner, it is possible to lower the detection limit of the mass spectrometer to 10.sup.15 mbar or less.

(45) In addition to the types of ion traps described above, it is also possible to use other types of ion traps in the mass spectrometer 1, which ion traps enable three-dimensional storage or accumulation of ions and an evaluation via a Fourier transform, e.g. a Penning trap, toroidal trap, Paul trap, linear trap, orbitrap, EBIT and RF Buncher.

(46) The above-described mass spectrometer 1 can find use in various fields of application. In addition to the chemical process analysis, which was already described as possible application in conjunction with FIG. 4, the mass spectrometer 1 can, for example, be used in EUV lithography for analysing the residual gas situated in an EUV system, e.g. an EUV lithography apparatus, in order to determine the concentration or the amount of contaminating substances in the residual gas atmosphere present there.

(47) FIG. 6 schematically shows such an EUV lithography apparatus 101. The EUV lithography apparatus 101 includes a radiation generating system 102, an illumination system 103 and a projection system 104 which are accommodated in separate vacuum housings and arranged successively in a beam path of the EUV radiation 106 generated by the EUV light source 105, the beam path proceeding from an EUV light source 105 of the radiation generating system 102. By way of example, a plasma source or a synchrotron can serve as EUV light source 105. The radiation in the wavelength range of between approximately 5 nm and approximately 20 nm that emerges from the EUV light source 105 is firstly concentrated in a collimator 107. With the aid of a downstream monochromator 108, the desired operating wavelength .sub.B, which is approximately 13.5 nm in the present example, is filtered out by variation of the angle of incidence, as indicated by a double-headed arrow. The collimator 107 and the monochromator 108 are embodied as reflective optical elements.

(48) The EUV radiation treated with respect to wavelength and spatial distribution in the radiation generating system 102 is introduced into the illumination system 103, which has a first and second reflective optical element 109, 110 (mirror). The two reflective optical elements 109, 110 guide the radiation onto a photomask 111 as a further reflective optical element, which has a structure that is imaged with a reduced scale on a wafer 112 via the projection system 104. To this end, a third and fourth reflective optical element 113, 114 (mirror) are provided in the projection system 104.

(49) The reflective optical elements 109, 110, 111, 113, 114 each have an optical surface which is exposed to the EUV radiation 106 of the light source 105. The optical elements 109, 110, 111, 113, 115 are each operated under vacuum conditions in a residual gas atmosphere 102a of the radiation generation system 102, a residual gas atmosphere 103a of the illumination system 103 and a residual gas atmosphere 104a of the projection system 104, in which residual gas atmosphere there typically is a small proportion of air, hydrogen (H.sub.2) and/or helium (He) and optionally further residual gases. Since the interior of the EUV lithography apparatus 1 cannot be baked out, the presence of undesirable contaminating constituents in the respective residual gas atmosphere 102a, 103a, 104a cannot be completely avoided.

(50) During operation of the EUV lithography apparatus 1, a vacuum generation unit, which includes a vacuum pump 115, generates a residual gas atmosphere 104a with an overall pressure of typically more than 10.sup.5 mbar in the projection system 104. A vacuum or a residual gas atmosphere 103a, 102a can correspondingly also be generated in the illumination system 103 or in the radiation generating system 102.

(51) In order to determine the proportion of contaminating substances overall and/or individually for each contaminating substance in the residual gas atmosphere 104a of the projection system 104, in particular in the vicinity of the second mirror 114, a mass spectrometer 1 is connected by flanges to the projection system 104, which mass spectrometer 1 has a design as described further above, i.e. which has an inlet 6 in order to introduce the residual gas mixture situated in the projection system 104 directly, i.e. without a preceding ionization, into an ion trap 10, which serves as measurement cell and is arranged in a measurement chamber 7, in order to ionize the gas by e.g. a charge exchange or an impact ionization.

(52) The inlet 6 forms a vacuum connection between the residual gas atmosphere 104a of the projection system 104 and the mass spectrometer 1. The inlet 6, i.e. the vacuum connection (vacuum pipe), has a cross section A of less than 100 mm, preferably less than 5 mm, in particular less than 1 mm. As shown in FIG. 1, the mass spectrometer 1 can have one or more stops to ensure that the residual gas pressure reduces toward the ion trap 10 to <10.sup.5 mbar so that a conventional residual gas analyzer can be used for the residual gas analysis.

(53) It is likewise possible to identify in FIG. 6 that a distance D between the second mirror 114 and a connection position P.sub.S of the mass spectrometer 1, which is formed on the housing of the projection optical unit 104 in the middle of the vacuum connection or of the inlet 6, is less than 50 cm. This is advantageous for being able to detect as precisely as possible the portion or the partial pressure of contaminating substances which are present in the vicinity of the second mirror 114, more precisely in the vicinity of the optical surface thereof. During the mass spectrometric examination, it is possible, in particular, to measure or detect at least one of the following contaminating substances or the mixtures thereof: oxygen (O.sub.2), ozone (O.sub.3), water (H.sub.2O), C.sub.XH.sub.YO.sub.Z, typically up to 10 Mamu, and metal-C.sub.XH.sub.YO.sub.Z-compounds, typically up to 10 Mamu.

(54) Additionally, or alternatively, a further mass spectrometer or the mass spectrometer 1 can be provided at a connection position P.sub.B of the illumination system 103, which is arranged at a distance D of less than 50 cm from a mirror 109, 110, e.g. from the first mirror 109, arranged there.

(55) Accordingly, the mass spectrometer 1 or a further mass spectrometer can be arranged at a first connection position P.sub.L1 in the radiation generating system 102, which is arranged at a distance of less than 1 m, preferably less than 50 cm, away from a passage opening 116 for the passage of the EUV radiation 106 into the illumination system 103. The mass spectrometer 1 can also be located at a second connection position P.sub.L2, which is arranged at a corresponding distance D of less than 100 cm, preferably less than 50 cm, from the collector 107 (typically in the form of a collector mirror), or at a third connection position P.sub.L3, which is arranged at a distance of less than 100 cm, preferably less than 50 cm, from the EUV light source 105. In the manner described above, it is possible to determine the contamination level in the vicinity of the respective optical elements 114, 109, 116, 107 or in the vicinity of the EUV light source 105 with high precision.

(56) FIG. 7 schematically shows a device 201 for atomic layer deposition on a substrate 202 (in this case: a silicon wafer), which is arranged on a mount 203 in an interior 204 of a process chamber 205 (reaction chamber). Both the mount 203 and the walls of the process chamber 205 can be heated to (optionally different) temperatures. The mount 203 can be connected to a motor to put the substrate 202 into a rotational movement during the coating. The device 201 also includes a container 206, in which a metal organic precursor material is contained, which, in the present example, is tetrakis(ethylmethylamino)hafnium (TEMAH) or another metal organic precursor. In order to move the precursor material from the container 206 to the process chamber 205, use is made of an inert carrier gas, e.g. argon or hydrogen, which can be supplied to the container 206 by a controllable valve 207. A further container 208 serves for the provision of ozone gas O.sub.3 or another doping gas as reactant in atomic layer deposition.

(57) The carrier gas with the precursor and the doping gas, for example the ozone gas, can in each case be introduced into the process chamber 205 by a controllable inlet in the form of a controllable valve 209a, 209b. A distributor manifold 210 is arranged in the chamber 205 in order to distribute the entering gas as homogeneous as possible in the direction on the substrate 202. Via the controllable valves 209a, 209b, it is also possible to supply a purge gas, e.g. argon, to the process chamber 205 in order to purge the process chamber 205 and the respective supply lines. A further controllable valve 211, which forms a gas outlet, is connected to a vacuum pump 212 in order to remove the gases from the process chamber 205. In order to monitor the residual gas atmosphere in the process chamber 205, a mass spectrometer 1 is arranged at an inclusion position E.sub.E in a vacuum line of a gas disposal system 213 formed downstream of the outlet valve 211, to be precise directly upstream of the vacuum pump 212. It is also possible to attach the mass spectrometer 1 to an inclusion position E.sub.G in an exhaust-gas line of the gas disposal system 213 downstream of the vacuum pump 212.

(58) Additionally, or alternatively, a mass spectrometer 1 can also be formed at an inclusion position E.sub.A, E.sub.B in a gas supply system 216 for supplying the reactants to the process chamber 205, for example in a respective supply line 216a, 216b. Additionally, or as an alternative thereto, a mass spectrometer 1 can also be integrated at an inclusion position E.sub.C of a gas mixing system 215, i.e. in a supply line formed downstream of the unification point of the two supply lines 216a, 216b. The latter is advantageous because the two supply lines 216a, 216b are not used simultaneously for supplying a gas to the process chamber 205 in the coating process described here. An inclusion position E.sub.D in the distributor manifold 210 is also possible, wherein the inclusion position E.sub.D in this case is preferably spaced at a distance D of less than 1 m, in particular of less than 50 cm, from the process chamber 205. Additionally, or as an alternative thereto, the mass spectrometer 1 or a further mass spectrometer and 1 can also be attached at an inclusion position E.sub.F on the housing of the process chamber 205, as described in conjunction with FIG. 6.

(59) The mass spectrometer 1 serves for the detection or determination of the amount of partial pressure of at least one gaseous constituent which is contained in the residual gas atmosphere of the chamber 205 (inclusion position E.sub.F) or which will be contained in the chamber 205 (inclusion positions E.sub.A, E.sub.B, E.sub.C, E.sub.D upstream of the process chamber 205) or which has been contained therein (inclusion positions E.sub.E, E.sub.G downstream of the process chamber 205). As shown on the basis of the mass spectrometer 1 arranged in the gas disposal system 213, the mass spectrometer has an ion trap 10, in which the gas or gas mixture to be examined can be ionized by e.g. a charge exchange or an impact ionization. In order to bring about a gas flow of the ionized gas constituents into the ion trap 10, the mass spectrometer 1 can be connected to a vacuum pump (not shown). The ions stored in the ion trap 10 can be detected directly in the ion trap 10.

(60) In order to apply a coating 214 of hafnium oxide (HfO.sub.2) onto the substrate 202, the following procedure is followed: initially, the carrier gas with the TEMAH-precursor is supplied to the process chamber 205 via the first valve 209a. Then, the first valve 209a is switched and the purge gas is supplied to the process chamber 205 by the first valve 209a (cf. arrow) and the latter is, together with the residues of the carrier gas or the precursor, suctioned away through the opened outlet valve 211 via the vacuum pump 212. After purging, the outlet valve 211 is closed and ozone or a doping gas is introduced into the chamber 205 via the second valve 209b, which ozone or doping gas undergoes chemical reaction with the precursor on the exposed surface of the substrate 202. Subsequently, there is a purging of the chamber 205 via the purge gas, which is supplied to the chamber via the second valve 209b (cf. arrow) and which is, together with the ozone or doping gas residues or possibly formed reaction products, suctioned away via the vacuum pump 212 when the outlet valve 211 is opened. In the procedure described above, a mono-layer made of hafnium oxide is deposited on the substrate 202. After closing the outlet valve 211, this procedure can be repeated a number of times, to be precise until the HfO.sub.2 coating 214 has reached a desired thickness d.

(61) The time duration for supplying the carrier gas with the precursor, the time duration for supplying the ozone or doping gas and the time duration of the purge procedure typically lie in the range of seconds. A control device 215 serves to actuate the valves 207, 209a, 209b, 211 so as to switch between the above-described steps of the deposition process. It is understood that the control device 215 can not only switch the valves 207, 209a, 209b, 211 between an opened position and a closed position, but that, optionally, the mass flow, which flows through the respective valves 207, 209a, 209b, 211, can also be controlled via the electronic control device 215.

(62) The overall pressure of the residual gas in the process chamber 205 typically lies between approximately 10.sup.3 mbar and 1000 mbar, wherein comparatively high overall pressures of more than 500 mbar or more than 900 mbar are also possible. The overall pressure in the chamber 205 can be monitored via a pressure sensor (not shown) and can optionally be modified via the control device 215 by a suitable control of the valves 207, 209a, 209b, 211.

(63) The detection of the gaseous constituents, more precisely determining the amount or the partial pressure of a respectively detected gaseous constituent, can be used for controlling or regulating the deposition process. By way of example, on the basis of the concentration of the metal organic precursor or of process relevant reactants such as ozone, doping gas or optionally metal organics and/or H.sub.2O in the residual gas atmosphere, it is possible to identify when the purging step can be completed (e.g. as soon as the respective partial pressure falls under a predefined threshold). The control unit 215, which has a signal connection to the process gas analyzer 213a, can then open or close the respective inlet valve 209a, 209b or the outlet valve 211 at suitable times and thus optimize the time duration used for the purging step. It is understood that, analogously, an optimization of the time duration of the two above-described supply steps is also possible.

(64) With the aid of the mass spectrometer 1, it is not only possible to optimize a process during the atomic layer deposition, but rather there can also be an optimization in other coating processes, for example when carrying out a (optionally plasma assisted) CVD process, a metal organic CVD process, in the case of metal organic chemical vapour phase epitaxy or in the case of molecular beam epitaxy, which can typically likewise be carried out in the (optionally slightly modified) device 1 from FIG. 1. The same applies to coating processes based on physical vapour deposition. In all of these cases, it is possible to adapt or optimize the process parameters (temperature, pressure, etc) in a suitable manner on the basis of the detected gas constituents in the residual gas atmosphere.

(65) When the mass spectrometer 1 is used in a coating apparatus, in particular, at least one of the following substances, the mixtures and/or reaction products, clusters and/or compounds thereof can be measured or detected during the mass spectrometric examination: H.sub.2, He, N.sub.2, O.sub.2, PH.sub.3, AsH.sub.3, B, P, As, CH.sub.4, CO, CO.sub.2, Ar, SCl.sub.4, SiHCl.sub.3, SiH.sub.2Cl.sub.2, H.sub.2O, C.sub.xH.sub.y, trimethylgallium, triethylgallium, trimethylaluminium, triethylaluminium, trimethylindium, triethylindium, Cp.sub.2Mg, SiH.sub.4, Si.sub.2H.sub.6, tetrabutylammonium, tetrabutylsilane, Xe isotropes, Kr isotropes, hexamethyldisiloxane, tert-butylarsine, trimethylarsine, diethyl-tert-butylarsine, diethyl-tert-butylphosphine, di-tert-butylphosphine, tert-butylhydrazine, dimethylhydrazine, indium, aluminium, gallium, boron, silicon, gold, antimony, bismuth.

(66) The at least one substance, the mixture, the reaction product, the cluster and/or the compound can, in particular, be measured or detected at a temperature in the process chamber 205 of between 15 C. and 5000 C., preferably between 100 C. and 2000 C., and at a pressure in the process chamber 205 of between 10.sup.10 mbar and 5 bar, preferably between 10.sup.8 mbar and 1 bar.

(67) In particular, when using the mass spectrometer 1 for examining a (process) gas mixture during a coating process, it can be advantageous if the mass spectrometer 1 has a self-cleaning function in order to remove constituents of the process gas which are deposited in the measurement chamber 7 or in the ion trap 10. An option for realizing such an in-situ self-cleaning is described in WO 02/00962 A1, in which a cleaning gas is used for removing deposits produced by process gases. In the mass spectrometer 1 from FIG. 1, the cleaning gas can be converted into a plasma in the plasma source 18 by virtue of the cleaning gas being supplied by a gas supply (not depicted here) in place of the ionization gas 13. The ionized or excited cleaning gas enters the ion trap 10 on the same path as the ionization gas 13. Optionally, the cleaning gas can also enter the measurement chamber 7 via a further gas supply (not depicted here) and, there, form a gaseous cleaning product with the deposits, which cleaning product can be removed from the ion trap 10 or from the measurement chamber 7.

(68) In particular, if the ion trap 10 is embodied as an electric FT-ICR trap, which uses a small installation space, the mass spectrometer 1 can also be used in applications in which the installation space plays an important role, e.g. in MOCVD processes or the like.

(69) It is understood that, due to the properties thereof described above, the mass spectrometer 1 can also be used in other fields, for example in other coating or etching or implanting processes, in gas analysis, in doping tests, in forensic examinations, etc.

(70) In addition to the use of the above-described mass spectrometer for mass spectrometric examination of gases, it is also possible to use the mass spectrometer in the field of vibration detection or vibration analysis of, typically, mechanical vibrations. In particular, the vibrations can be natural vibrations of a setup or a device, into which the mass spectrometer is installed, i.e. the vibrations are detected at the point of use of the mass spectrometer and the mass spectrometer is used as vibration sensor. For this purpose, the mass spectrometer is used to record a spectrum within a frequency range in which the vibration frequencies to be analyzed lie. By way of example, this frequency spectrum can lie between approximately 1 Hz and approximately 15 kHz. A plurality of parasitic frequencies typically lie within this frequency range, which parasitic frequencies are produced by mechanical vibrations and which can be detected and analyzed by the measurement electrodes of e.g. an FT ion trap, in particular an FT-ICR trap. By way of example, in order to analyze the vibrations, a frequency spectrum can be recorded as soon as the mass spectrometer is installed into the device. If the device was in good working order at the time of the installation, this frequency spectrum can serve as reference spectrum. Measuring the frequency spectrum can be repeated at a later time or at several later times, and the measured frequency spectrum can be compared to the reference spectrum. If one or more additional lines or peaks are detected in the measured frequency spectrum, this is an indication that undesired vibrations are occurring somewhere in the device, which e.g. can be traced back to mechanical problems. By way of example, the vibrations can be undesired natural vibrations of sliding bearings or ball bearings, which are arranged in the vicinity of the mass spectrometer, or vibrations caused by a power supply unit (mains hum). By way of example, in the coating apparatus 201 depicted in FIG. 7, the natural frequencies f of the vacuum pump 212 arranged in the vicinity of the mass spectrometer 1, in particular the sliding bearings or ball bearings of the pump, can be analyzed or detected.