JP5537174B2 - Gas concentration measuring device - Google Patents

Description

  The present invention relates to a gas concentration measurement apparatus using Raman scattered light for measuring the concentration of a measurement target gas existing in a resonator, and for example, the gas concentration in the atmosphere is measured by opening the resonator. In addition, the present invention relates to an optical fiber coupled external resonator type gas concentration measuring device in which the concentration of the sucked gas is measured by making the resonator a closed system.

  Conventionally, gas detectors are widely used for measuring pollutants in the atmosphere and monitoring generation of flammable gas and toxic gas in plant facilities. An optical method, particularly a laser spectroscopic analysis technique has been actively studied as a trace gas detection method. Gas detection methods using laser light include laser absorption spectroscopy, laser-induced fluorescence, and Raman scattering spectroscopy.

  Here, Raman scattering is a phenomenon in which when the molecule is irradiated with monochromatic light, the frequency of the scattered light changes by the vibration frequency of the molecule, and the frequency shift amount of the scattered light is independent of the frequency of the emitted monochromatic light. This is the amount specific to the substance. Therefore, when laser light having a specific wavelength is irradiated onto a measurement target substance, Raman scattered light having a wavelength different from the wavelength of the laser light is generated from the substance hit with the laser light. Further, it is known that the intensity of the scattered light is proportional to the concentration of the substance.

  As a technique related to gas visualization or measurement using Raman scattering spectroscopy, the applicant proposed a first technique that scans a space to be monitored with laser light and has a transmission wavelength center at a wavelength obtained by Raman-shifting the wavelength of the laser light. Raman scattered light is collected by one optical bandpass filter, converted into an electric signal by one light receiving element, a first time waveform is measured, and transmitted light and wavelength of the first optical bandpass filter are measured. Light of a specific wavelength is collected by a second optical bandpass filter that transmits light having a different range, converted into an electrical signal by a single light receiving element, a time waveform is measured, and then the first time waveform and The difference from the second time waveform is taken, and a Raman scattered light signal image in which the corresponding position coordinates of the monitoring target space are colored based on the scanning position information of the laser beam is created. A hydrogen gas visualization method and system (see Patent Document 1) characterized in that hydrogen gas is visualized by being superimposed on a background image of a monitoring target space, and nitrogen gas is irradiated to the target space by laser light. The target light is irradiated with laser light in synchronism with the first process and the first process in which the scattered light from the light is collected by the light collecting mechanism and the Raman scattered light signal intensity is measured by the first light receiving mechanism. The second step of collecting the scattered light of the target by the light collecting mechanism and measuring the Raman scattered light signal intensity by the second light receiving mechanism, the target in the target space based on the intensity ratio of the Raman scattered light intensity of the nitrogen gas and the target gas There is a gas concentration remote measurement method and apparatus (see Patent Document 2) including a third step of calculating a gas concentration.

  Gas detectors that are small, can be measured in a short time, have few failures, and are extremely practical are, for example, semiconductor lasers and external lasers that increase the intensity of laser light output from semiconductor lasers. A resonator, a semi-cylindrical lens for collecting scattered light arranged in parallel with the external resonator, and a mirror for reflecting scattered light arranged on the opposite side of the semi-cylindrical lens across the optical axis of the external resonator And a gas detector including a filter that extracts Raman scattered light from the scattered light collected through the semi-cylindrical lens, and an optical sensor that detects the intensity of the Raman scattered light extracted by the filter (Patent Document 3). reference).

  In addition, hydrogen detection technology by Raman scattering analysis using an external cavity semiconductor laser (PLEC-DL) by optical feedback is known. In the technique described in this document, a rod lens is used as an optical system for condensing Raman scattered light, and the scattered light exiting on the opposite side is reflected back to the rod lens side by a cylindrical mirror and comes out in parallel. It has been reported that by condensing scattered light with a single biconvex lens, a condensing rate 2.58 times that of a conventional optical system was obtained (Non-patent Document 1).

JP 2007-232374 A WO 2009/101659 JP 2005-140558 A

Ken Yamauchi, Kouichi Sato, Kazuaki Tsuji, Shigeru Yamaguchi, Kenzo Nanzato, Tomoo Fujioka, “Study on Detection of Trace Combustible Gas Using Semiconductor Laser External Resonator”, Laser Society 358th Research Report (2007, 2)

Since the intensity of Raman scattered light is extremely weak, it is necessary to increase the length of the scattered light path in order to detect gas using Raman scattering. There is a problem that it cannot be decided freely.
In addition, when the environment where the measuring device is used is an explosion-proof area where flammable gas is handled, the gas concentration measuring device needs to have an explosion-proof structure, but the gas directly contacts the electrode like a contact-type gas sensor. There was no complete explosion-proof gas concentration measuring device.

By the way, in recent years, development of fuel cell vehicles, household fuel cell power generators, and the like has been performed, and accordingly, maintenance of hydrogen gas plants, hydrogen stations, and the like for supplying hydrogen gas is progressing. Since hydrogen gas undergoes a rapid combustion reaction in a range of 4% to 75% in air at normal temperature and pressure, a gas sensor that quickly measures gas concentrations from low to high is required. The contact-type hydrogen gas sensor has disadvantages such as a slow recovery time when contacted with a high-concentration gas and a shortened sensor life, and the development of a non-contact hydrogen gas sensor is desired.
As described above, hydrogen is a gas that explodes at a concentration of 4%, and the high-pressure gas safety method requires the ability to measure a concentration (1%) or less that is 1/4 of the lower explosion limit concentration as a gas sensor. Development of a hydrogen gas sensor that can quickly detect even a small amount of hydrogen gas is desired.
In addition, hydrogen gas sensors are required from those installed in infrastructure facilities to those installed in fuel cell vehicles, etc., and development of non-contact type sensors that require little maintenance is desired. ing.
Furthermore, it is desired to develop a small gas concentration measuring device that does not restrict the layout of the device while the sensor unit placed in the presence of hydrogen gas is a complete explosion-proof type in which no electric / electronic circuit exists.

  The present invention provides a gas concentration measuring apparatus that can solve the above-described problems.

In order to solve the above problems, it is possible to measure the concentration quickly regardless of the gas concentration, and to make it a non-contact type in order to achieve a long service life. In order to achieve this, it is assumed that no electrical or electronic device is mounted on the sensor unit and no complicated and inferior vibration resistance components are used.
In order to detect weak Raman scattered light, it is necessary to increase the intensity of the laser beam. On the other hand, it is not preferable to use a high-power laser device in order to achieve downsizing. Therefore, the present invention employs a configuration in which the size of the entire apparatus is suppressed using a semiconductor laser and the intensity of the laser beam is increased using an external resonator. Furthermore, in the present invention, a part of the light enhanced in the resonator is returned to the semiconductor laser oscillation unit via the polarization maintaining optical fiber, thereby confining the linearly polarized laser light in the resonator. Thereby, the incident laser beam is enhanced several thousand times in the resonator.
Furthermore, by using an optical fiber for the transmission of the laser light to the sensor unit and the transmission of the Raman scattered light from the sensor unit, there is no electrical / electronic component of the sensor unit, thereby achieving complete explosion protection.

The present invention for solving the above-described problems comprises the following technical means.
[1] A light source unit including a semiconductor laser device in which an antireflection treatment is performed on the laser emission window, a first reflection mirror disposed on the incident side, and a second reflection mirror facing the first reflection mirror are provided. And a sensor unit including a condensing system arranged in a direction orthogonal to the electric field of the laser beam in the resonator, and light detection for detecting Raman scattered light from the measurement target gas existing in the resonator And a detector including a controller that calculates the concentration of the gas to be measured, a polarization maintaining optical fiber that optically connects the light source and the sensor, and an optical fiber that optically connects the sensor and the detector. a gas concentration measuring apparatus comprising the sensor unit is provided with a scattered light reflecting curved mirror disposed on the opposite side of the light collecting system with respect to the laser beam axis of the resonator, the semiconductor laser device The laser light emitted from the laser beam is incident on the resonator via the polarization maintaining optical fiber, and a part of the light enhanced in the resonator is returned to the oscillation part of the semiconductor laser via the polarization maintaining optical fiber. A gas concentration measuring device which oscillates a narrow-band laser beam whose oscillation wavelength is locked by confining a linearly polarized laser beam with a laser beam.
[2] The gas concentration measuring device according to [1], further comprising a prism that shapes an elliptical beam irradiated from the semiconductor laser device into a circular shape .
[3] The control unit modulates the oscillation of the semiconductor laser at a specific frequency, synchronously amplifies the received light signal in synchronization with the frequency , and measures the signal intensity , and
The gas concentration measuring device according to [1] or [2], wherein the output intensity of the semiconductor laser light is kept constant based on the signal intensity of a photodiode incorporated in the semiconductor laser .
[4] Further, a correction light measuring device that measures laser light leaking from the second reflecting mirror is provided, and the control unit is configured to emit laser light that is irradiated into the resonator based on a change in the light amount in the correction light measuring device. When controlling the current of the semiconductor laser so that the intensity is constant and converting the concentration from the Raman scattered light intensity from the measurement target gas based on the calibration curve calculated in advance, the light intensity change in the correction light measuring instrument The gas concentration measuring device according to any one of [1] to [3], wherein the calibration curve is corrected based on the calibration curve .
[ 5 ] The gas concentration measurement device according to any one of [1] to [ 4 ], wherein the measurement target gas is hydrogen gas.

According to the present invention, since the light source unit, the detection unit, and the sensor unit are connected by an optical fiber, a complete explosion-proof structure in which the sensor unit in contact with the gas has no electric / electronic circuit can be realized.
Further, since the light source unit, the detection unit, and the sensor unit are connected by an optical fiber, there are few restrictions on the layout of each unit due to its structure.
Further, the present invention has a non-contact type sensor unit and can perform quick concentration measurement. In addition, even when the optical component is contaminated, the density value can be accurately calculated by automatically correcting the calibration curve.

It is a schematic block diagram of the whole apparatus of the gas concentration meter of this invention. It is a figure which shows the path | route to LD of the feedback light of the fundamental mode in a resonator, and the light reflected by the mirror back surface. It is a figure which shows the state in which the feedback light of the fundamental mode in a resonator, and the light reflected by the mirror back surface were returned to LD end surface. It is a graph which shows the relationship between hydrogen gas concentration and Raman scattered light signal intensity | strength.

In the present invention, light emitted from a semiconductor laser having an antireflection treatment applied to a laser emission window is incident on a resonator via a polarization-maintaining optical fiber having an antireflection coating applied to an end face, and is enhanced in the resonator. Part of the laser beam is returned to the semiconductor laser oscillation section via the polarization maintaining optical fiber, thereby confining the linearly polarized laser beam in the resonator and condensing the light in the direction orthogonal to the electric field of the linearly polarized laser beam in the resonator. An optical bandpass that collects the Raman scattered light from the molecules present in the resonator, transmits it to the receiver via an optical fiber, and transmits the Raman scattered light wavelength of the molecule to be measured installed in front of the receiver Optical fiber coupled external resonator that converts the intensity of the Raman scattered light wavelength of the target molecule selected by the filter into an electrical signal using the light receiving element, and measures the density of the target molecule from the intensity The present invention relates to gas concentration meter.
Preferably, a scattered light collecting curved mirror for reflecting the light from the resonator to the condensing system is disposed on the opposite side of the condensing system with respect to the laser optical axis.

When an electric field is applied to a molecule, the electron distribution of the molecule changes slightly. This phenomenon is called molecular polarization, and the present invention uses the Raman scattering phenomenon caused by this polarization to measure the concentration of the molecule.
When polarization occurs due to the electric field (electric field) of laser light, scattered light is strongly emitted in a direction perpendicular to the polarization. Therefore, a large signal can be obtained when the polarization of the laser beam is linearly polarized and the Raman scattered light is measured from a direction perpendicular to the electric field.
A general semiconductor laser has an elliptical beam pattern and oscillates with linearly polarized light having a polarization plane in the minor axis direction. Therefore, it is preferable to hold the polarization by connecting the polarization axis of the polarization maintaining optical fiber so as to match the polarization plane of the semiconductor laser light.
In addition, when the linearly polarized laser beam is guided to the resonator while the linearly polarized laser beam is confined in the resonator, the intensity of the laser beam confined in the resonator is increased. Therefore, a large signal can be obtained by observing the Raman scattered light emitted from the gas existing inside the resonator by laser light irradiation from a direction perpendicular to the laser polarization plane.
In the present invention, in order to use this phenomenon, linearly polarized laser light from a semiconductor laser is transmitted while maintaining polarization using a polarization maintaining optical fiber. Since it is sufficient to measure only the intensity of the Raman scattered light, the collected Raman scattered light can be transmitted by a normal optical fiber (single mode or multi mode).

The present invention includes an external resonator that resonates laser light emitted from a semiconductor laser and feeds back part of the laser light to the semiconductor laser, and the oscillation wavelength (frequency) of the semiconductor laser is locked by the optical feedback. . As a result, laser light with a stable wavelength can be confined in the resonator. At this time, an antireflection treatment is applied to the laser emission window of the semiconductor laser device, so that self-oscillation can be suppressed and feedback can be favorably performed.
Further, it is preferable that the oscillation of the semiconductor laser is modulated at a specific frequency, and the received light signal is synchronously amplified in synchronization with this frequency.

When the electric field is weak (in the case of normal laser light), the molecular polarization is proportional to the electric field strength (laser light strength).
That is, the Raman scattered light signal intensity can be expressed by the formula of (laser light intensity) × (number of molecules) × (Raman scattering cross section) × (light receiving area) × (light receiving efficiency) × (light / electric conversion efficiency). it can.

Here, unless the components and arrangement of the light receiving system are changed, the change in the Raman scattered light signal intensity depends only on the change in the laser light intensity in the resonator. Most of the fluctuations in the intensity of the laser beam in the resonator are caused by a change in the intensity of the light source and a change in the reflectance of the resonator mirror. Therefore, as a method of keeping the laser light intensity inside the resonator constant, the laser light intensity leaking from the mirror in the direction opposite to the laser light incidence of the resonator is measured with a light receiver to monitor the laser intensity change inside the resonator. Then, by controlling the current of the semiconductor laser so that the laser light intensity becomes constant, the Raman scattered light signal intensity can be corrected to realize higher-accuracy measurement.
It is also possible to measure the exact molecular concentration by measuring the laser light leaking from the mirror of the resonator, obtaining the change in the amount of light due to contamination of the optical component, and correcting the calibration curve.

  Table 1 shows the Raman scattering light wavelength and the Raman scattering cross section of gas molecules when the center wavelength of the semiconductor laser is 637 nm.

In the present invention, it is preferable to use a semiconductor laser with an antireflection film (AR coating). A normal semiconductor laser has a coating on the laser emission surface, and emits laser light by itself. However, in the present invention, an antireflection film is deposited on the laser emission surface, emitted from the semiconductor laser into the resonator through the optical fiber, and a part of the light in the resonator is returned to the oscillation part of the semiconductor laser, Laser oscillation occurs at a wavelength and mode (laser intensity distribution) determined by the properties of the semiconductor laser and the resonator.
More specifically, when an antireflection film (AR coating) is applied to the output mirror of the semiconductor laser, the semiconductor laser self-oscillation is suppressed (the semiconductor laser has no resonator), and the emission wavelength of the semiconductor laser The width becomes the wavelength width of spontaneous emission of light, and light having a relatively wide wavelength is emitted. Therefore, when laser light is fed back to the semiconductor laser with the AR coating on the emission surface using an external mirror, a normal laser oscillation operation can be obtained. At this time, if the wavelength to be fed back is specified, it is possible to oscillate at that wavelength. In the resonator, the resonance condition (wavelength and mode) is determined by the interval between the resonators and the shape of the mirror (plane, concave, convex). Looking at the resonance wavelength, the energy is concentrated at the wavelength that matches the resonance condition (the oscillation wavelength width is extremely narrow, the energy that was emitted in a wide wavelength range is concentrated at that wavelength, and the specific wavelength determined by the resonator as a result. Peak intensity increases). By feeding back light having a wavelength determined by this resonator condition, the oscillation wavelength of the semiconductor laser is locked, and oscillation of a narrow band laser can be obtained.
If a powerful laser is used, neither the antireflection film nor the resonator is required. However, in this case, the feature of the present invention that the concentration measurement is performed by increasing the laser intensity in the resonator using a small-sized and low-power semiconductor laser is impaired.
In the present invention having the above configuration, an oscillation wavelength and mode determined by the properties of the resonator can be obtained by installing a resonator outside the laser light emitting section and feeding back the leaked light from the resonator to the semiconductor laser. can get.

  In the present invention, a linearly polarized laser is incident on the resonator via the polarization maintaining optical fiber. Here, normally, the light emission pattern of the semiconductor laser is diffracted at the edge of the laser emission area and becomes an elliptical beam. Therefore, the configuration of the preferred embodiment of the anamorphic prism pair of the present invention is adopted. That is, the anamorphic prism pair is a prism that shapes an elliptical beam into a circular shape by enlarging / reducing one of the elliptical beam axes such as a semiconductor laser beam. Such shaping of the diode laser beam is effective for improving the coupling efficiency to the optical fiber and for mode matching with the external resonator.

[Structure of gas concentration meter]
An example of the structure of the optical fiber coupled external resonator type gas concentration meter of the present invention will be described with reference to FIG. The gas concentration meter of the present invention includes a light source part A, a sensor part B, and a detection part C, and these parts are optically connected by optical fibers.

[Light Source A]
In the light source section A, laser light is emitted from the AR-coated semiconductor laser 1, and the laser light is condensed by the AR-coated collimator lens 2 to form a thin laser beam, and the AR-coated anamorphic prism pair. 3 is converted into linearly polarized circular light, and then introduced from the AR-coated coupling lens 4 into the polarization-maintaining optical fiber 51 AR-coated on the end face. Thus, the linearly polarized laser light is introduced into the sensor unit B after passing through the polarization maintaining optical fiber. By applying the AR coating to the optical component, the reflected light (feedback light) to the semiconductor laser is reduced.

[Sensor part B]
The sensor unit B includes an external resonator 6 and a light collecting system. The resonator 6 includes a pair of resonance reflecting mirrors 61 and 62, and the laser light incident surface of the resonance reflecting mirror 61 is subjected to AR coating. The laser light introduced into the resonator 6 is repeatedly reflected inside the resonator to enhance the laser light intensity, and the Raman scattered light is laser-induced by the interaction between the laser light and the molecule to be measured in the resonator 6. It occurs in a direction perpendicular to the polarization direction of light. A condensing system comprising a lens group for condensing Raman scattered light emitted from molecules in the resonator 6 and a curved mirror 7 for reflecting scattered light are provided so as to face the optical axis of the resonator at right angles. Yes. The Raman scattered light is condensed by the cylindrical lens 8 and the collimating lens 32 and introduced into the optical fiber 52 through the coupling lens 24. The scattered light emitted to the opposite side of the resonator 6 from the cylindrical lens 8 is also reflected by the scattered light reflecting curved mirror (concave surface or cylindrical mirror) 7 and collected to the cylindrical lens 8 side to the optical fiber 52. be introduced. Since the transmission from the sensor unit B to the detection unit C is for measuring the intensity of light, the optical fiber 52 connecting the sensor unit B and the detection unit C does not necessarily have a polarization maintaining function.

[Detector C]
In the detection unit C, when measuring the intensity of the Raman scattered light transmitted by the optical fiber 52, the Raman scattered light having a wavelength emitted by the molecule to be measured by the bandpass filter 9 is selectively extracted to detect the photomultiplier tube and the semiconductor light. The intensity is measured by a photodetector 10 such as an element or an avalanche photodiode. The detected signal is synchronously amplified by the lock-in amplifier 201 and its intensity is measured. In the performance test, the signal intensity of the synchronous amplifier was observed with the oscilloscope 204. However, the output voltage of the synchronous amplifier can be converted into a digital signal by an AD converter and connected to a processing unit such as a personal computer to calculate the concentration.

[Feedback from resonator]
The leakage light of the light confined in the resonator 6 is returned to the semiconductor laser 1, and a resonance state is caused between the semiconductor laser 1 and the resonator to lock the oscillation mode of the semiconductor laser 1. At this time, it is necessary to adjust so that the light reflected from the back surface of the mirror 61 or the light deviated from the laser optical axis in the resonator does not return to the light emitting portion of the semiconductor laser 1. This will be described with reference to FIGS.
As shown in FIG. 2, the feedback light 71 from the resonator 6 is fed back to the semiconductor laser 1 by the polarization maintaining optical fiber 51. At this time, the reflected light reflected by the back surface of the mirror 61 or the laser light in the resonator. Off-axis light 72 is also fed back. Here, as shown in FIG. 3, the feedback light from inside the resonator 6 is distributed near the center 71 of the optical axis 12, and the reflected light 72 is mainly distributed around the periphery 72. Therefore, by providing the LD active layer 11 of the semiconductor laser 1 in the central portion with the optical axis as the center, the LD active layer 11 is irradiated with only the feedback light 71 in the fundamental mode in the resonator. Can do.
Although schematically shown in FIG. 3, in fact, the return light receiving port is the end face of the polarization maintaining optical fiber 51 and is optically fed back to the semiconductor laser 1 through the optical fiber 51.

[Stabilization of irradiation laser light intensity]
In order to obtain an accurate measurement value, it is necessary to irradiate the resonator 6 with a laser beam having a stable intensity. As a specific means, the intensity of the laser beam leaking from the mirror 62 on the side opposite to the laser incident side of the resonator 6 is measured, and the current input to the semiconductor laser 1 is controlled so that the value becomes a constant value. Thus, the intensity of the laser beam may be held at a constant value. It is also possible to keep the semiconductor laser light output intensity constant by monitoring and adjusting the signal intensity of the photodiode incorporated in the semiconductor laser.

[Correction of calibration curve]
Since molecules to be measured enter and exit the resonator 6, it is inevitable that the measurement conditions change due to degradation of the performance of optical components such as contamination of the reflecting surfaces of the reflecting mirrors 61 and 62 for resonance. If the performance degradation of the optical component is slight, it is possible to obtain an accurate measurement value by storing a molecule having a known concentration in the resonator and checking and correcting the calibration curve. However, if the contamination of the optical system is not mild, correction of the calibration curve cannot deal with it. In this case, it is necessary to reassemble the optical system by cleaning the reflecting mirror and the lens and replacing parts.

  Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to the following examples.

The outline of the optical fiber coupled external resonator type gas concentration meter of the present embodiment is as shown in FIG. 1, and details of each element constituting the gas concentration meter are as follows.
[Light Source A]
The light source section A is configured by connecting an AR-coated semiconductor laser 1 (hereinafter referred to as “LD1”), a collimating lens 2, an anamorphic prism pair 3, and a coupling lens 4, and the LD 1 is operated by an LD power source 203. . The size of the light source unit A is 25 (W) × 25 (H) × 90 (L) mm (however, the LD power source 203 and the function generator 202 are not included).
The specifications of each part are as follows.
(LD1) Oscillation wavelength: 637nm, maximum output: 10mW
(Collimate lens 2) With antireflection film, focal length: 4.51 mm, aperture diameter: 4.95 mm, NA: 0.55, design center wavelength: 780 nm, applicable wavelength band: 600 to 1050 nm
(Anamorphic prism pair 3) with anti-reflection coating, anamorphic magnification: 3.8, design center wavelength: 670 nm
(Coupling lens 4) with antireflection film, focal length: 13.86 mm, aperture diameter: 5.10 mm, NA: 0.18, design center wavelength: 780 nm, applicable wavelength band: 600-1050 nm
(Function generator 202) Frequency: 100Hz
(LD power supply 203) DC voltage applied external modulation system

[Polarization-maintaining optical fiber 51]
The polarization maintaining optical fiber 51 is a member that connects the light source part A and the sensor part B and transmits linearly polarized laser light to the resonator 6. The specifications of the polarization maintaining optical fiber 51 are as follows.
Name: Panda fiber Fiber length: 1m
End face anti-reflective coating treatment: reflectance 0.27% (at 637nm)
Cladding diameter: 125μm
Mode field diameter: 4.5 ± 0.5μm
Operating wavelength range: 630-780nm
Transmission loss: <12dB / km (at 630nm)
Cut-off wavelength: 570 ± 50nm

[Sensor part B]
The sensor unit B includes a collimating lens 22, a resonator 6, a scattered light reflecting curved mirror 7, and a condensing system. The resonator 6 includes resonance reflecting mirrors 61 and 62. By repeating the reflection of linearly polarized laser light between the resonance reflecting mirrors 61 and 62, the laser light is enhanced and Raman scattered light is generated in the molecule to be measured. Let The Raman scattered light from the resonator 6 is condensed by the cylindrical lens 8 and the collimating lens 32 and introduced into the optical fiber 52 from the coupling lens 24. The curved mirror 7 for reflecting scattered light is a cylindrical mirror disposed on the opposite side of the light collecting system of the resonator 6. The size of the sensor B is 100 (W) × 40 (H) × 90 (L) mm, and the size of the resonator 6 is 30 (W) × 30 (H) × 90 (L) mm. .
Moreover, the specification of each component which comprises the sensor part B is as follows.
(Collimate lens 22) with antireflection film, focal length: 5.0mm, aperture diameter: 1.5mm, NA: 0.15, design center wavelength: 780nm, applicable wavelength band: 600-1050nm
(Resonator 6) Resonator length: 80 mm, design wavelength: 633 nm
(Incoming mirror 61) Laser light incident surface with antireflection film, reflectance: 99.97%, radius of curvature: -100mm
(Reflection mirror 62) Reflectivity: 99.999%, curvature radius: -100mm
(Curved mirror 7 for scattered light reflection) Reflective surface: gold coat, radius of curvature: -10 mm
(Cylindrical lens 8) Focal length: 20.4mm, Dimensions: 20x40mm
(Collimate lens 32) Focal length: 42.1mm, aperture diameter: 40mm
(Coupling lens 24) with antireflection film, focal length: 15.29mm, aperture diameter: 5mm, NA: 0.16, design center wavelength: 780nm, applicable wavelength band: 600-1050nm

[Optical fiber 52]
The optical fiber 52 is a member for transmitting Raman scattered light from the sensor unit B to the detection unit C. The specifications of the optical fiber 52 are as follows.
Fiber length: 1.5m
Core diameter: 1mm
Applicable wavelength band: 340-2500nm

[Detector C]
The detection unit C detects the Raman scattered light having a wavelength emitted from the measurement target gas selected by the bandpass filter 9 from the Raman scattered light transmitted by the optical fiber 52 by using the photodetector 10 formed of an avalanche photodiode. To 204. The size of the detection unit C is 50 (W) × 25 (H) × 100 (L) mm (however, the lock-in amplifier 201 and the oscilloscope 204 are not included).
Moreover, the specification of each component which comprises the detection part C is as follows.
(Band pass filter 9) Center wavelength: 872.98 nm, full width at half maximum: 9.82 nm
(Photodetector 10) Light-receiving surface: 3.0 mmφ, sensitivity: 0.5 A / W (at 800 nm magnification 1), response frequency band: DC to 100 kHz, measurement wavelength band: 400 to 1000 nm
(Lock-in amplifier 201) Synchronization frequency: 100 Hz, integration time: 3 seconds (oscilloscope 204) coupling: DC coupling

[Calibration curve]
FIG. 4 is a graph showing a calibration curve for measuring the hydrogen concentration with the gas concentration meter of this example. In FIG. 4, the correlation coefficient R ² = 0.9906 between the hydrogen gas concentration and the Raman scattered light.
Needless to say, for other types of gases, the concentration of gases other than hydrogen can be measured by accommodating other gases in the resonator 6 and irradiating them with laser light to create a calibration curve.

[Effect of Example 1]
As a result of performing a function verification test using the gas concentration meter of this example, the laser irradiation intensity from the polarization maintaining optical fiber when the LD is operated at an output of 3 mW is 1 mW, and the laser intensity inside the resonator is 3 W. It was confirmed that a hydrogen concentration of 100 ppm could be measured.
The gas concentration meter of the present embodiment is a small apparatus using a small and low-power semiconductor laser, but uses an external resonator to increase the intensity of the laser light and confine linearly polarized laser light within the resonator. This makes it possible to measure a trace amount of 100 ppm in about 3 seconds.
In addition, since laser light and Raman scattered light are transmitted by optical fiber, the sensor part in contact with the gas is completely explosion-proof because there is no electric / electronic circuit.

  The present invention enables a sensor unit to be installed at an arbitrary position by connecting a light source, a sensor unit and a detection unit with an optical fiber, and is useful for measuring the concentration of an arbitrary gas. Is particularly useful for measuring concentrations of flammable, explosive or toxic gases.

  By selecting the Raman scattering wavelength to be measured for the target gas species, it is possible to measure concentrations of a plurality of gases, for example, nitrogen, oxygen, hydrogen, carbon monoxide, nitrogen dioxide, hydrogen sulfide and the like. The gas concentration meter of the present invention capable of measuring such various gas concentrations with explosion proof and high sensitivity can be used from a fuel cell vehicle, a household fuel cell power generator, etc., to a hydrogen station, various gases. It can be widely used for leak detection in manufacturing plants.

1: Semiconductor laser (LD)
2, 22, 32: Collimating lens 3: Anamorphic prism pair 4, 24: Coupling lens 6: Resonator 7: Curved mirror for reflecting scattered light 8: Cylindrical lens 9: Band pass filter 10: Photo detector 11: LD active layer 12: optical axis 13: LD end face 51: polarization-maintaining optical fiber 52: optical fiber 61, 62: reflection mirror 71 for resonance: feedback light 72 in resonator basic mode 72: reflected light 201: lock-in amplifier 202: function Generator 203: LD power supply 204: Oscilloscope A: Light source unit B: Sensor unit C: Detection unit

Claims (5)

A light source unit including a semiconductor laser device in which an antireflection treatment is applied to the laser emission window;
A resonator comprising a first reflecting mirror and a second reflecting mirror facing the first reflecting mirror disposed on the incident side, and disposed in a direction perpendicular to the electric field of the laser light in the resonator A sensor unit including a condensing system;
A detector including a photodetector for detecting Raman scattered light from the measurement target gas existing in the resonator and a control unit for calculating the concentration of the measurement target gas;
A polarization maintaining optical fiber that optically connects the light source unit and the sensor unit;
An optical fiber for optically connecting the sensor unit and the detection unit, and a gas concentration measuring device comprising:
The sensor unit includes a curved mirror for reflecting scattered light disposed on the opposite side of the light condensing system with respect to the laser optical axis of the resonator,
The laser light emitted from the semiconductor laser device is incident on the resonator via the polarization maintaining optical fiber, and a part of the light enhanced in the resonator is returned to the semiconductor laser oscillation part via the polarization maintaining optical fiber. A gas concentration measuring device that oscillates a narrow-band laser beam whose oscillation wavelength is locked by confining linearly polarized laser beam in a resonator. The gas concentration measuring apparatus according to claim 1, further comprising a prism that shapes the elliptical beam irradiated from the semiconductor laser device into a circular shape . The control unit modulates the oscillation of the semiconductor laser at a specific frequency, synchronously amplifies the received light signal in synchronization with the frequency , and measures the signal intensity ; and
3. The gas concentration measuring apparatus according to claim 1, wherein the output intensity of the semiconductor laser light is kept constant based on the signal intensity of the photodiode incorporated in the semiconductor laser . And a correction light measuring device for measuring laser light leaking from the second reflecting mirror,
The control unit controls the current of the semiconductor laser based on the change in the light amount in the correction light measuring device so that the intensity of the laser light irradiated in the resonator becomes constant , and based on a calibration curve calculated in advance. 4. The gas concentration according to claim 1 , wherein, when the concentration is converted from the Raman scattered light intensity from the measurement target gas, the calibration curve is corrected based on a change in the amount of light in the correction light measuring device. measuring device. Gas concentration measuring apparatus according to any one of 4 to the measurement target gas claims 1 is hydrogen gas.