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Title:
HYDROGEN HALIDE DETECTION
Document Type and Number:
WIPO Patent Application WO/2019/175478
Kind Code:
A1
Abstract:
The disclosure of the embodiments concern a method of detecting hydrogen halides HX. Embodied method comprises sampling (301) a gas sample into a sample flow via a sampling port of the detection arrangement for detecting hydrogen halides HX, guiding (302) the sample flow to the ionization section volume of the detection arrangement, comprising an ionizer therein, producing (303) in the ionization section O2 ions into the flow passing through the volume of ionization section, in the detection arrangement, allowing (304) the formation of dioxygen-hydrogen halide adducts [HX*O2]- in said flow resulting from the produced ions, guiding the flow (305) with said dioxygen-hydrogen halide adducts [HX*O2]- to a detector. detecting (306) at least the adduct masses and/or adduct mobility with the detector. The disclosure concerns also monitoring method and arrangement to use the method.

Inventors:
HAKALA, Jani (Husbackankuja 8 A 24, Vantaa, 01610, FI)
MIKKILÄ, Jyri (Unioninkatu 39 B 25, Helsinki, 00170, FI)
KAUSIALA, Oskari (Malmin raitti 30 B 7, Helsinki, 00700, FI)
SHCHERBININ, Aleksei (Pariisinkatu 5 C 47, Helsinki, 00560, FI)
Application Number:
FI2019/050221
Publication Date:
September 19, 2019
Filing Date:
March 15, 2019
Export Citation:
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Assignee:
KARSA OY (A.I. Virtasen aukio 1 A 319, Helsinki, 00560, FI)
International Classes:
G01N1/22; G01N27/64; H01J49/04; H01J49/10; H01J49/14; H01J49/26
Domestic Patent References:
WO2009018305A12009-02-05
Foreign References:
JP4042885B22008-02-06
US20020048818A12002-04-25
US5095206A1992-03-10
JP2001351569A2001-12-21
US20130046485A12013-02-21
Attorney, Agent or Firm:
HEINONEN & CO, ATTORNEYS-AT-LAW, LTD (Fabianinkatu 29 B, Helsinki, 00100, FI)
Download PDF:
Claims:
Claim s

1. Method of detecting hydrogen halides HX comprising :

sampling (301) a gas sample into a sample flow via a sampling port of the detection arrangement for detecting hydrogen halides HX,

guiding (302) the sample flow to the ionization section volume of the detection arrangement, comprising an ionizer therein

producing (303) in the ionization section O2 ions into the flow passing through the volume of ionization section, in the detection arrangement, allowing (304) the formation of dioxygen-hydrogen halide adducts [HX*C>2] in said flow resulting from the produced ions,

guiding the flow (305) with said dioxygen-hydrogen halide adducts [HX*C>2] to a detector.

detecting (306) at least the adduct masses and/or adduct mobility with the detector.

2. The method of claim 1, further com prising to provide optionally (302b) additional make-up input of O2 to the sample flow, to provide material for ion production of O2 ions in the ionization section by the ionizer. 3. The method of claim 1 or 2, comprising to adjust the flow (305b) to correspond the residence time of said dioxygen-hydrogen halide adducts [HX*02]_ shorter than the decay time of said dioxygen-hydrogen halide adducts [HX*02]_ in the detection arrangement parts between the ionization section and the detecting parts of the detector.

4. The method of claim 1, 2 or 3, comprising producing (307) a signal when dioxygen-hydrogen halide adducts [HX*02] are detected in the sample flow.

5. The method of any previous claims, wherein the detecting (306) is made as based on the adduct mass observed by the detector.

6. The method of any of the previous claims, wherein there is a signal being produced (308) at a pre-determined threshold adduct [HX*C>2] concentration, the threshold being set by the control center for generation of a signal to be used as a response from the detected masses and/or mobility spectra of hydrogen halide adducts presence as an initiation to exceed or equal said threshold .

7. The method of any of the previous claims, wherein the method comprises controlling (309) of the sampling from at least one selected sampling location to a selected sample port by a control of a control center (600) . 8. The method of any previous claims, wherein the detecting of the adduct masses and/or mobility spectra thereof, is based on such a detector as analyzer that is one of mass spectrometer of Time of Flight type, mass spectrometer of quadrupole type and ion mobility spectrometer. 9. The method of any of the previous claims, wherein the method comprises controlling (310) by a control center (600) the ion production of the ionizer by controlling at least one of the following : controlling ionization voltage of the corona discharge ionizer, controlling the voltage of soft X-ray ionizer part, controlling a shutter position of a particle source based alpha and/or beta- radiation source part of the ionizer, and controlling an X-ray filter position in the ray path to the ionization section.

10. The method of any of the previous claims, wherein the method comprises controlling by a control center (600) an additional make-up flow of O2 to the sample flow (311).

11. The method of any of the previous claims, wherein the method comprises controlling by a control center (600) to control the mass detector to detect the masses of the adducts (312), such as mass spectrometer (MS) .

12. A monitoring method of hydrogen halide concentration (400), comprising phase in which a response signal is formed (401) by a control center (600) to control a dioxygen-hydrogen halide adduct [HX*02] concentration associated event as an initiation in accordance of a method (300) according to any of the previous claims 1 to 11.

13. A non-transitory computer-readable medium (500) storing computer-executable instructions which when executed by one or more processors result in performing operations comprising at least one of: a software code for constituting control center (600) of any previous claims, to control means for controlling a mass spectrometer, ion source, flow-producing device, valves, an ensemble of ventilation devices, in accordance of use in any previous claims.

14. A detection arrangement to detect hydrogen halides HX comprising :

sampling means to sample a gas sample into a sample flow via a sampling port of the detection arrangement for detecting hydrogen halides HX, - guiding means to guide the sample flow to the ionization section volume of the detection arrangement, comprising an ionizer therein

ionizer to produce in an ionization section O2 ions into the flow passing through the volume of the ionization section, in the detection arrangement, reaction chamber allowing the formation of dioxygen-hydrogen halide adducts [HX*C>2] in said flow resulting from the produced ions,

guiding means to guide the flow with said dioxygen-hydrogen halide adducts [HX*02] to a detector,

detector arranged to detect at least the adduct masses and/or adduct mobility with the detector.

15. The detection arrangement of claim 14, arranged to implement the method according to any claim 1 to 12.

Description:
HYD ROGEN HALI D E D ETECTI ON

FIELD OF TECHNOLOGY

The invention concerns halide detection in a very general level, but more specifically method to detect hydrogen halides in very low-level concentrations. Even more specifically, by using Chemical ionization in the detection low concentrations of hydrogen halides

BACKGROU N D

Hydrogen halides as such are very reactive substances. The origin of these compounds, HX, where the X is considered as a member of Halogen group of elements, i.e. X€ {F, Cl, Br, I, At} it can be traced for example to certain etching process that are practiced in wafer manufacturing. However, the compounds have strong etchant properties, especially in high temperatures, but appearance to clean room environment even in small or ultralow level concentrations in normal conditions may destroy lithography of a wafer, for example, so that the made work has been ruined and consequently material losses occurred. Additionally the identification of the source may be not possible without proper devices that are sufficiently sensitive in low concentration levels. Even a single contamination event can cause significant capital damage through interference with production of silicon wafers, for example. The method can also embody other industrial process monitoring.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGs 1, 2 and 6 illustrate optional arrangements according to examples of embodiment,

FIG 3 illustrates a detection method according to examples of embodiment,

FIG 4 illustrates a monitoring method example that is using an embodied detection method,

FIG 5 illustrates a software product according to an embodiment,

FIG 7 illustrates an example of a control center according to an embodiment,

FIG 8 illustrate a system according to an embodiment

FIG 9a and 9b illustrate optional arrangement variants with use of calibration and/or reference standards, and Fig 10 illustrates optional embodiments in accordance of Fig 6.

DETAILED DESCRIPTION

Example embodiments described herein provide certain systems, methods, and devices for the hydrogen halide detection. The following description and the drawings sufficiently illustrate specific embodiments to enable those skilled in the art to practice them. Other embodiments may incorporate structural, logical, electrical, process, and other changes. Portions and features of some embodiments may be included in, or substituted for, those of other embodiments. Embodiments are combinable in suitable part.

As the sensitivity of the proposed method is below 0.1 ppt, this enables detection of ultralow concentrations of hydrogen halides in an air sample and this is highly beneficial for Airborne Molecular Contamination detection, for example in semi-conductor industry for monitoring clean rooms.

An embodied method is based on chemically ionizing hydrogen halides at atmospheric pressure with O2 chemistry. The method exploits short reaction time (~ 10 ms) to prevent the negative charge transfer from O2 to species with higher electron affinity, and prevent the decomposition of short lifetime O2 adducts (or intermediates). The embodied chemical ionization scheme relies on a formation of negatively charged hydrogen halide - dioxide adduct [HCΌ2] and its detection by a mass spectrometer or Ion Mobility Spectrometer.

[HCΌ2] rapidly decomposes forming a halide ion X-, but given short enough time between the adduct formation (reaction) and the means of detection, the adduct can be detected as noticed. Detecting a halide ion is not enough to confirm a presence of the hydrogen halide, because the halide ion can be formed from another source. A special care should also be taken about the conditions in the detector, which, in the embodiments, uses a mass spectrometer. The mass spectrometer tuning should be set to low fragmentation to increase the possibility of detecting the short-lived [HCΌ2] adduct.

The negative O2 reagent comes from ionized air, if the measurement is made in atmospheric conditions. If the gas matrix is something else (e.g. N2, Ar or He), a requirement of a make-up amount of O2 can be added to the sample. In embodiment variants, soft X-ray source is used to ionize air to generate the required O2 reagent ions by radiation, but also radioactive sources and electric discharges (e.g. corona discharge) can be used, in addition or optionally. A Method of detecting hydrogen halides HX according to an embodiment comprises: sampling a gas sample into a sample flow via a sampling port of the detection arrangement for detecting hydrogen halides HX,

guiding the sample flow to the ionization section volume of the detection arrangement, comprising an ionizer therein

producing in the ionization section O 2 ions into the flow passing through the volume of ionization section, in the detection arrangement,

allowing the formation of dioxygen-hydrogen halide adducts [HX*C> 2 ] in said flow resulting from the produced ions,

guiding the flow with said dioxygen-hydrogen halide adducts [HX*02] to a detector,

detecting the adduct masses with the detector (or ion mobility with ion mobility spectrometer).

An embodiment according to the method according to an embodiment is further comprising to provide optionally additional make-up input of O2 to the sample flow, when needed, to provide material for ion production of O 2 ions in the ionization section by the ionizer.

An embodiment according to the method according to an embodiment comprises for adjusting the flow to correspond the residence time of said dioxygen-hydrogen halide adducts [HX*C>2] shorter than the decay time of said dioxygen-hydrogen halide adducts [HX*02] in the detection arrangement parts between the ionization section and the detecting parts of the detector.

An embodiment according to the method according to an embodiment comprises producing a signal when dioxygen-hydrogen halide adducts [HX*C>2] are detected in the sample flow.

An embodiment according to the method according to an embodiment comprises detecting as made as based on the adduct mass observed by a mass spectrometer (or ion mobility by ion mobility spectrometer).

An embodiment according to the method according to an embodiment comprises producing a signal being produced at a pre-determined threshold adduct concentration. According to an embodiment, the threshold being set by the control center for the signal as a response from the detected masses and/or the concentrations based on the measurements of hydrogen halide adducts presence as an initiation to exceed or equal said threshold. An embodiment according to the method according to an embodiment comprises controlling of the sampling from at least one selected sampling location to a selected sample port by a control of a control center.

An embodiment according to the method according to an embodiment comprises controlling by a control center the ion production of the ionizer by controlling at least one of the following : controlling ionization voltage of the corona discharge ionizer, controlling the voltage of soft X-ray ionizer part, controlling a shutter position of a particle source based alpha and/or beta-radiation source part of the ionizer, and controlling an X-ray filter position in the ray path to the ionization section.

An embodiment according to the method according to an embodiment comprises controlling by a control center an additional make-up flow of O2 to the sample flow.

An embodiment according to the method according to an embodiment comprises controlling by a control center the mass detector to detect the masses of the adducts (312), such as mass spectrometer.

A monitoring method of hydrogen halide concentration, comprises a phase in which a response signal is formed by a control center being arranged to control counter operations as response to a dioxygen-hydrogen halide adduct [HX*0 2 ] concentration being equaled and/or exceeded.

According to an embodiment the concentration level can be associated to an event as a response as said signal being latching a series of responses to an initiation in accordance of a method according to an embodiment to the threshold of said dioxygen-hydrogen halide adduct [HX*0 2 ] concentration. The number of the responses in the series is not limited as such.

According to an embodiment, the concentration exceed to latch an event can be a measurable concentration, but is one of an ensemble of threshold concentrations being monitored to be exceeded . The series of the events as a response may comprise in addition to the events of process guidance in detail, also such events as closing pre determined cells i.e. departments in a clean room or clean room area, for example, increasing ventilation, and/or making alarm, shutting down certain chemical lines, to mention few as non-limiting events for examples.

A non-transitory computer-readable medium according to an embodiment being arranged to store computer-executable instructions, which when executed by one or more processors result in performing operations comprising at least one of: a software code for constituting control center of any previous claims, to control means for controlling a mass spectrometer, ion source, flow-producing device, valves, an ensemble of ventilation devices, in accordance of an embodiment.

Fig 1 illustrates an arrangement 100 according to an embodiment of the invention. The arrangement 100 comprises the reaction chamber 101, which has an ionization section under the x-ray source 105 capable to radiate x-rays to the ionization section of the reaction chamber 101. The x-rays, according an embodiment soft x-rays, are illustrated by the symbol g.

Although the analyzer has been drawn outside the dashed line for the arrangement embodiments 100, 200, 300, according to an embodiment variant the analyzer is a part of the arrangement. According to an embodiment, an embodied arrangement can be embodied to form a device, i .e. the arrangement parts in same cover in suitable part.

According to an embodiment variant, the arrangement can have a pre-filter, which can be embodied in several ways, for example by a selective scrubber, as illustrated by the dashed line. According to a further embodiment, the pre-filter is arranged to be operative by an electric field E, being maintained by the HV source at the right for charging and/or collecting particulate matter out of the gas sample, that is about to be introduced via the sampling port 103 to the reaction chamber 101. However, as particles are not expected in clean room, the arrangement can be operated also without the pre filter.

The gas sample in a clean room monitoring, for example, can be an air sample, and consequently comprises O2. If there was not O2 in the sample to be taken, an additional make-up O2 can be provided, similar way as illustrated in Fig 6 for the optional geometry example of radiation and reaction chamber related embodiment of the arrangement 300. According to respective embodiment, the ionizer may also comprise at least one of a shutter and/or a filter, to be used for blocking the X-rays to enter to the reaction chamber, and/or to soften the X-rays, and/or to filtrate some components of the X-rays out of the X-ray spectrum . These can be embodied in a mechanical way as bringing a suitable purpose-specific blockage material between the X-ray source and the reaction chamber. The operation of the transducer for the task to open and/or close the shutter and/or the filter being operated in the control of the control center, in suitable part according to the user of the arrangement, and/or automatically. The control center can also control the shutter between the states of full radiation area exposed and shutting the area completely by its cover. The filter can be controlled also in similar way, so to provide different zones of radiation to the reaction chamber, if desired for the chemical ionization process. The word Vacuum is illustrative to a flow constituting means to provide the flow via the sampling port to the reaction chamber 101. The tube 102 is illustrative of the sampling port from the reaction chamber 101 to the analyzer, embodied in the FIGs as a mass spectrometer MS. The mass spectrometer can be used in the detection of the hydrogen halides said halides being as parts of the adducts [HX*02] .

The flow rate of the flow to the mass spectrometer MS is adjusted so that the ionization products and the hydrogen halides made combination adducts in the reaction chamber 101 are not yet decayed before the entry to the mass spectrometer.

The time scale is about to below 30 ms, preferably below 10 ms.

The reaction in the reaction chamber 101 as is expected is

HX + 0 2 - -> [HX*C>2]- which decays rapidly in 10 ms scale to release X-. The X€ {F, Cl, Br, I, At} i.e. it is considered as a halogen as the stable naturally abundant halogens. Although At deflects from the others as artificially produced, relatively short lived element (for the isotopes about 8h or even less), it is also behaving like iodine I, but is additionally poisonous because of its radioactive nature. According to an embodiment, At can be also detected and related warning as well as responsive events can be scheduled by the monitoring system, for a certain pre-determined threshold concentration in such labs where the process can produce At remarkably abundant, or it is directly handled as such. In this respect At can be considered as according to the other halogens, which are having more wide applicability in industrial processes, where to monitor.

According to an embodiment, the mass spectrometer is a TOF-type of mass spectrometer (Time Of Flight MS) . According to an embodiment, a quadrupole-type of mass spectrometer can be used in suitable part, where applicable.

Fig 2. illustrates optional arrangement 200 according to an embodiment of the invention for the hydrogen halide detection. According to the example embodied, the arrangement has a corona discharger in a needle electrode geometry to make ions to the sampled gas flow into the reaction chamber 101. The other markings follow the notation of Fig 1 in suitable part. The corona charger can be also implemented into different corona geometries, such as axial wire-tube, wire-plate and plate-to-plate geometries, according to the geometries used in the electrostatic precipitators.

Fig 6. illustrates even a further optional arrangement 300 according to an embodiment of the invention for the hydrogen halide detection. The notation of the reference numerals following those used in the Figs 1 and 2. The FIV1 is used for maintaining the electric field in such an optional variant of the embodiment in which there is a pre-filter used before the gas sample entry to the chamber. As the curved arrows illustrate, the arrangement 300 is using also radiation for the ion formation into the reaction chamber 101 at the ionization section at the radiation source 105. The radiation geometry can be tubular or optionally conical, or even further optionally a plate-to-plate type segment on the wall type of radiation source for the ion production. Optionally also alfa or beta radiation can be used in some embodiment variants.

Fig 3 illustrates a method (300M) of detecting hydrogen halides HX. The method comprises:

- sampling (301) a gas sample into a sample flow via a sampling port of the detection arrangement for detecting hydrogen halides HX,

- guiding (302) the sample flow to the ionization section volume of the detection arrangement, comprising an ionizer therein

- producing (303) in the ionization section O2 ions into the flow passing through the volume of ionization section, in the detection arrangement,

- allowing (304) the formation of dioxygen-hydrogen halide adducts [HX*C>2] in said flow resulting from the produced ions,

- guiding the flow (305) with said dioxygen-hydrogen halide adducts [HX*C>2] to a detector.

- detecting (306) the adduct masses with the detector.

According to an embodiment variant, the method is further comprising to provide optionally (302b) additional make-up input of 02 to the sample flow, to provide material for ion production of O2 ions in the ionization section by the ionizer.

According to a variant of the method it is comprising to adjust the flow (305b) to correspond the residence time of said dioxygen-hydrogen halide adducts [HX*C>2] shorter than the decay time of said dioxygen-hydrogen halide adducts [HX*02]- in the detection arrangement parts between the ionization section and the detecting parts of the detector.

According to an embodiment variant the method comprises producing (307) a signal when dioxygen-hydrogen halide adducts [HX*C>2] are detected in the sample flow. According to an embodiment variant the method comprises such detecting (306) that is made as based on the adduct mass observed by a mass spectrometer.

According to an embodiment variant the method can comprise producing a signal being produced (308) at a pre-determined threshold adduct concentration, the threshold being set by the control center for the signal as a response from the detected masses of hydrogen halide adducts presence as an initiation to exceed or equal said threshold .

According to an embodiment variant, the method comprises controlling (309) of the sampling from at least one selected sampling location to a selected sample port by a control of a control center.

According to an embodiment variant, the method can comprise controlling (310) by a control center the ion production of the ionizer by controlling at least one of the following : controlling ionization voltage of the corona discharge ionizer, controlling the voltage of soft X-ray ionizer part, controlling a shutter position of a particle source based alpha and/or beta-radiation source part of the ionizer, and controlling an X-ray filter position in the ray path to the ionization section.

According to an embodiment variant, the method can comprise controlling by a control center an additional make-up flow of O2 to the sample flow (311) .

According to an embodiment variant the method can method comprise controlling by a control center the mass detector to detect the masses of the adducts (312), such as mass spectrometer.

Fig 4 illustrates a monitoring method of hydrogen halide concentration (400), comprising phase in which a response signal is formed (401) by a control center to control a dioxygen-hydrogen halide adduct [HX*C>2] concentration associated event as an initiation in accordance of a method (300M) according to an embodied method of detecting hydrogen halides HX.

Fig 5 illustrates a non-transitory computer-readable medium (500) storing computer- executable instructions which when executed by one or more processors result in performing operations comprising at least one of: a software code for constituting control center (600) of any previous claims, to control means for controlling a mass spectrometer, ion source, flow-producing device, valves, an ensemble of ventilation devices, in accordance of any previous claims. The software can comprise also software means to implement the method of detecting hydrogen halides, and/or the monitoring method thereof.

Fig 7 illustrates a control center according to an embodiment. I/O illustrates input/output related operations to be controlled by control center 600, by software code in suitable part to control the related hardware parts of the I/O operations. Flow adj illustrates flow setting and/or maintaining means by corresponding software code in suitable part to control the related hardware parts of the flow setting, adjusting and maintaining operations. The Flow Adj can also embody software means to select and/or switch the flow routings according to the calibration and/or reference concentration measurement needs in embodiment variants. Ionizer Adj illustrates settings related to ion production, start, stop, filtering where applicable, and/or the ionizing action maintaining means, by corresponding software code in suitable part to control the related hardware parts of the ionizer operations. According to an embodiment variant, I/O operations comprise also the sampling related aspects so that the I/O module can co-operate with the other modules shown in the Fig 7. According to an embodiment, in software level in suitable part, but according to a variant embodiment, in suitable part in a hardware level, with hardware parts that a software module is controlling. About at least a state of the hardware part the software part is controlling by the control center, it is acknowledged, to have a holistic control of the arrangement, although information about the settings and/or sensor data can be also considered in the controlling center. According to an embodiment, the controlling center can be implemented as made in suitable part as a mediator structure, to control the communications between the modules, in a software level, but also to extend the control into a hardware level via suitable interfacing software.

Alg illustrates algorithms, to be stored in a volatile memory in suitable part in operation, and in permanent memory in suitable part when the arrangement is in switched off state. Algorithms can be also program parts, to be executed in a microprocessor in suitable parts. According to an embodiment, an algorithm can be distributed to different parts of a computer code, in suitable part.

MS cont illustrates such software means to control analyzer, particularly to control mass spectrometer or ion mobility spectrometer operations, that software means are controlling of the mass spectrometer operations by a suitable software code, in a suitable part, to control the related hardware parts responsible of the mass spectrometer operations. In embodiments that use as analyzer ion mobility spectrometer, the MS cont is arranged to control such analyzer.

HV cont illustrates such software means to control high voltage operations, that are controlling of the high voltage operations by a suitable software code, in suitable part, to control the related hardware parts responsible of the high voltage operations. In some embodiment variants, the X-ray production related high voltage can be controlled, as well as in an other embodiment variant corona discharge related ionization producing high voltage to maintain the electric field for the corona discharge. Also in x-ray applications shutters and/or filters can be controlled by the HV cont, so that the mechanical position of the shutter/filter can be adjusted according to a control signal, although the shutter/filter related control signal were only in a level of voltage of industrial control signals of a stepper motor or similar used in manipulators to move a body from a position to another positon, to reveal and/or cover an area in the radiation section of the reaction chamber. According to an embodiment variant, shutter as controlled can be used also in ionization location selection in such embodiments that can use make-up O2 ionization. The flow adj can be used in combination to select at least one of the selection variant routings between the ionization section of the ionizer (105) of the reaction chamber 101, and such variants that can use the make up O2 ionization (FiglO) . According to an embodiment, the ionizer can comprise a corona discharge charger optionally or in addition to soft x-ray source.

Settings module is illustrative of the operational settings of the arrangement according to which the arrangement is operational at a moment. The settings content can be embodied to have mode-type settings to generalize the operation in a certain mode as defined by permanent type settings, but settings that can also comprise measurement data bound guiding values for the arrangement parts.

Drivers, Interfaces module illustrates the drivers and interfaces that the control center 600 can use in the controlling of the operations of the arrangement parts, in software level and/or in hardware level.

Sampling site select illustrates such an embodiment, that a control center can actually control several arrangements, which may be not necessarily identically embodied. According to an embodiment, the control center can select also the sampling site as illustrated in Fig 8.

Fig 8 is illustrative of a system that uses embodiments 100, 200, 300, under control of a control center, to control at least one arrangement to take sample via selection. The selection can be made so that the Cell 1, Cell2, Cell 3, Cell 4, Cell 5, Cell 6 and/or Cell 7 can be parts of a clean room for example, from which samples can be taken according to the selection under the control of the control center 600, at least one of the cells to be monitored. The clean room parts just mentioned need not to be necessarily parts of the same clean room or clean room area. The cells Cell 1 to Cell7 are arranged to a star- like topology, to keep the sampling lines short and the losses to piping walls low. The control center can also make an alarm and/or disintegrate a part of a clean room from the conformity of the other parts as based on the monitoring result. If a cell, for example a clean room part Cell 3 were found to have a contamination, the control center can produce a control signal to be addressed to such a transducer that is responsible in a hardware level about the make the mechanical isolation from the other parts of the clean room . The transducer can make the operation according to the control signal from the control center, the signal being a dedicated control signal as an example of dedicated control signals for a special purpose.

According to an embodiment there can be such similar dedicated control signals to control/communicate with the modules of the control center 600 (in hardware level and/or software level in suitable part). Such to mention few examples, for the pre-filter operation, high voltage switch on/offs, shutter/filter positions, flow settings, etc. A suitable control signal can be used in communication with the mass spectrometer and/or the resulting data communications.

According to an embodiment, the use of short-lived adduct produced by chemical ionization being detected during its presence can distinguish the adduct from the other masses in the mass spectrometer spectrum from the other masses, and the detection limit can be thus low.

Fig 9a and Fig 9b illustrate examples on optional arrangements that use at least one of the calibration standard Stdr (FIX) adapted to an arrangement specific set up, as depicted by the symbols CALI, CAL2, CAL3 referring to the respective arrangements 100, 200, and 300 in Figl, Fig 2 and Fig 6, but also to Fig 10 as an option to Fig 6 radiation arrangements. According to an embodiment these symbols refer to a specific chambers via which the standard HX has being measured .

Fig 9a and Fig 9b illustrate also optional arrangements that use at least one of the reference standards adapted to the arrangement specific set up, as depicted by the symbols REF1, REF2, REF3 referring to the respective arrangements 100, 200, and 300 in Fig l, Fig 2 and Fig 6, but also to Fig 10 as an option to Fig 6 radiation arrangements. According to an embodiment, the reference standard can be a clean, zero, standard . According to an embodiment, these symbols refer to specific chambers via which the clean reference has being measured .

The dashed-line boxes in Figs 9a and 9b illustrate various embodiment options to couple to the same arrangement at least one of arrangement specific calibration standards and/or arrangement specific reference standards, in the arrangement option 100, 200, 300, specific way. According to an embodiment variant the reference standard is a clean reference. Although mass spectrometer MS is used as an example of the detector, according to an embodiment also suitable ion mobility spectrometer can be used as the analyzer, in suitable part.

The box Select is illustrating operational state of the arrangement so that when line leading to CALI, CAL2, CAL3 is selected, corresponding arrangement 100, 200, 300 is being calibrated with the calibration standard Stdr HX, where X is a halogen. Correspondingly, when the selection of the line leading to REF1, REF2, REF3 is selected, corresponding arrangement 100, 200, 300 is being used with the analyzer to measure the clean reference.

The line between the box CALI, CAL2, CAL3 and the box 101 is illustrative that the reaction chamber 101 in an arrangement 100, 200, 300 is being used in the calibration against the standard . Then the select is selecting the analyzer sampling via the reaction chamber in the calibration. However, according to an embodiment the select can also select an omitting line (not shown as such), so that the analyzer as such can be calibrated, even without the reaction chamber 101 in the calibration line. This way, the influence of the reaction chamber to the detected mass can be estimated. The box 901c is illustrative with the dashed line leading to the Select box controlling of the flow routing related to the calibration under the control of the control unit 600.

The line between the box REF1, REF2, REF3 and the box 101 is illustrative that the reaction chamber 101 in an arrangement 100, 200, 300 is being used in a clean reference measurement against a clean reference. The Select can select the analyzer sampling via the reaction chamber in such measurement. However, according to an embodiment the Select can also select an omitting line (not shown as such), so that the analyzer as such can be evaluated in respect of the clean concentration of the reference, even without the reaction chamber in the reference measurement line. This way, the influence of the reaction chamber to the detected mass can be estimated. The box 901R is illustrative with the dashed line leading to the Select box controlling of the flow routing related to the reference measurement under the control of the control unit 600.

The dashed lined boxes are indicative of embodiment variants that comprise at least one of reaction chamber, calibration line and a reference chamber for clean reference.

Fig 10 illustrate such embodiments that use radiation geometry in which the make up oxygen O2 is exposed to radiation and then the oxygen ions Ch are lead to the reaction chamber 101NR, that is comprised by an arrangement 100NR, 200NR, 300NR variant. The letters NR in the reference numerals in Fig 10 are used to indicate embodiments where ionization of O2 is produced via the make up O2 input line, via such ionization section, so that the reaction chamber 101NR does not necessarily have further ionization in operation, although the chamber 101 were otherwise similar to 101NR. According to a further variant, the chamber 101 that has the shutter to be used as controlled in to the closed mode to prevent further radiation by the radiation source 105 to radiate in such a reaction chamber 101 that has shutter embodied, the chamber 101 with a shutter in closed mode can operate as chamber 101NR, to be used with the make up O2 input with embodied additional ionization source in option. A skilled person in the art knows from the embodiments of Fig 6 and Fig 10 how to bring the make up 02 in the arrangements in Figs 1 and 2 to the reaction chamber.

According to an embodiment a reference chambers embodied via the REF1, REF2, REF3 can be used in an online concentration measurements (FIX) by reaction chamber 101, 101NR, and can be compared continuously to the reference chamber readings, in control of the control unit 600.