JPH06222000A - Infrared spectrochemical analyzer - Google Patents

Abstract

PURPOSE:To obtain the analyzer having the excellent maintenability and economy by splitting the emitted light obtained by exciting a light emitting medium into contrast light and sample light, and measuring the sample light, which is made to act mutually, with a material under analysis as the contrast light. CONSTITUTION:For example, amplified naturally emitted luminous flux 9, which is emitted from a glass fiber 8 of light emitting base material containing Er that is excited with the laser light of a semiconductor laser exciting light source 3, is divided into two parts with a half mirror 10 and becomes a sample luminous flux 11 and a contrast luminous flux 12. The contrast luminous flux 12 reaches a selector 15 through reflecting mirrors 13 and 14. The sample luminous flux 11 and the contrast luminous flux 12 are alternately cast into a spectroscope 16 by the action of the selector 15. The material under analysis is contained into a cell, which sufficiently transmits the light and made to be a sensor part 41. The sensor part 41 is inserted between the half mirror 10 and the selector 15. The emitted light 17 from the spectroscope 16 is received with a photodetector 18 and converted into an electric signal 19. The signal is amplified with an electric amplifier 20 and the electric output is obtained. The spectrum data of the sample light and the contrast light are obtained and processed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an infrared spectroscopic analyzer for detecting the composition and concentration of a target substance by using light, which is an in-line analyzer in a plant such as petrochemical, food, steel and agriculture. The present invention relates to an infrared spectroscopic analysis device used as an analysis device for monitoring harmful substances emitted from devices and equipment in various industries.

[0002]

2. Description of the Related Art As a device for analyzing the components and concentrations of a target substance, there is a spectroscopic analyzer that utilizes the absorption of light by the target substance. Above all, an infrared spectroscopic analyzer that analyzes light from near infrared to far infrared is applied in various industrial fields. As such an analyzer, an incoherent light source spectroscopic analyzer using a thermal radiator light source such as a Grover / Nernst grower, or a coherent light source spectroscopic analysis using a semiconductor laser oscillating in a wavelength from near infrared to far infrared is used. There is a device. The advantage of the former is that the light source is from 3 μm to 1
Since it is a continuous light source that covers a wide spectral range of 00 μm, it has a wide analysis wavelength range. On the other hand, the advantage of the latter is that it is a coherent light source and it can be applied to remote sensing as a high-intensity, high-concentration light source.

[0003]

However, since the infrared spectroscopic analyzer using the thermal radiation source is an incoherent light source, the radiation source is 1000 ° C.
Since it has to be maintained at a high temperature of 000 ° C, it has the following drawbacks. (1) The brightness was low. (2) The light collecting property was low. (3) Electric / light energy conversion efficiency was low. (4) Water cooling was required. (5) Corrosion of electrical contacts such as the light source support and electrodes was premature. (Grover) (6) Preheating was required because it was an insulator up to 400 ° C.
(Nernst Grower) (7) The quality was poor and the life could not be predicted. (Nernst Grower) For this reason, it is not suitable for light sources for spectroscopic analysis that require brightness and light condensing properties such as remote sensing, and maintenance and
There was also a problem with economics.

On the other hand, the infrared spectroscopic analyzer using the semiconductor laser light source has the following drawbacks. (1) Since a semiconductor laser that oscillates in the near infrared to far infrared cannot oscillate at room temperature, it needs to be cooled with a cryogen such as liquid helium or liquid nitrogen. Especially, continuous operation such as in-line analysis and monitor analysis is required. In the case of continuous analysis in, a special heat-insulating container for storing a cryogen and a facility capable of automatically supplying were needed. (2) Since the semiconductor laser is a monochromatic light source that oscillates at a fixed wavelength, in order to obtain continuous light in a specific wavelength range, the temperature of the semiconductor laser is changed to adjust (tune) to the target oscillation wavelength, and It had to be swept, causing a time delay due to tuning and sweeping.

The object of the present invention was made in view of the above-mentioned drawbacks of the conventional infrared spectroscopic analyzer using a heat radiator or a semiconductor laser as a light source. Since it does not require a cryogen because it operates at the same time, and it generates continuous light in a specific wavelength range without tuning sweep, it uses a light emitting element that does not cause a time delay as a light source and can be applied to in-line monitor or remote sensing. An object of the present invention is to provide an infrared spectroscopic analyzer having excellent properties.

[0006]

In order to achieve this object, an infrared spectroscopic analyzer according to the first invention of the present application includes an optical waveguide structure including at least one luminescent medium that emits light when excited by light. A luminescent mother material glass provided or at least two kinds of luminescent mother material glasses having different luminescent mediums, and a luminescent mother having a structure for combining light emitted from each luminescent medium of the luminescent mother material glass A light emitting base material composed of a material glass group, a means for suppressing laser oscillation due to the emitted light of the light emitting medium in the light emitting base material, and the light emitting medium optically coupled to one of the optical waveguide termination surfaces of the light emitting base material. An excitation light source that emits light that excites light, a means that distributes the emitted light of the luminescent base material into sample light and reference light, a sensor unit that interacts the sample light with a substance to be analyzed, and the analysis by the sensor unit. Interaction with target substance And it has a configuration equipped with the sample beam and the means for extracting alternately the control light, and a measuring unit for measuring a sample light and the pair illumination obtained from means for retrieving. Also,
An infrared spectroscopic analyzer according to the second invention of the present application is a luminescent base glass having at least one kind of luminescent medium that emits light when excited by light, or a luminescent matrix glass having an optical waveguide structure, or at least two different types of the luminescent medium. A light emitting base material comprising a light emitting base material glass, and a light emitting base material glass group having a structure for multiplexing lights emitted from respective light emitting media of the light emitting base material glass; A means for suppressing laser oscillation due to the emitted light of the light emitting medium, an excitation light source for emitting light for exciting the light emitting medium by optically coupling with one of the optical waveguide termination surfaces of the light emitting base material, and the emitted light of the light emitting base material A sample portion that interacts with a substance to be analyzed as a sample light, a measuring portion that measures a signal light that is a sample light that has interacted with the subject to be analyzed by the sensor portion, and a light emitted from the luminescent base material to the sensor portion. To reach A sample optical system constituted by said signal signal light optical system to reach the measuring unit light from the sensor unit.

[0007]

The infrared spectroscopic analysis device of the present invention is an infrared spectroscopic analysis device for remote sensing having a light source of high brightness and high condensing property, and an infrared spectroscopic analysis device for in-line monitoring which does not require the supply of a cryogen. Furthermore, since the continuous light of a specific wavelength range is emitted, an infrared spectroscopic analyzer having excellent time response that does not cause a time delay due to tuning and sweeping can be realized.

[0008]

Example 1 The center wavelength of the glass light emitting element that is the light source
An example of a double-beam type infrared spectroscopic analyzer set to 2.7 μm will be described. As a glass light emitting element that is a light source, the shape of the light emitting base material glass is columnar, and a waveguiding structure is formed with a core to which one kind of light emitting medium is added and a clad not to be added, and a semiconductor laser is used as the excitation light source. Use a glass light emitting device that emits light at a wavelength of 2.7 μm. Its longitudinal section is shown in FIG.
Shown in. The shape of the light-emitting base material glass of the glass light-emitting element is a cylindrical fiber 8, a core 1 made of fluoride glass to which Er of rare earth element is added as a light-emitting medium, and a clad 2 made of fluoride glass having a lower refractive index than the core. To form a waveguide structure. When fluoride glass is used as the luminescent matrix glass, the luminescent medium may be excited with light having a wavelength of 790 nm in order to cause the luminescent medium Er to emit light with a central wavelength of 2.7 μm. Semiconductor laser with an oscillation wavelength of 790 nm, which is the excitation light source 3
Are arranged so as to be optically coupled to the terminal surface 4 of the light emitting base material glass. In this embodiment, they are directly coupled, but it goes without saying that they can be optically coupled via an optical component such as a lens or an optical fiber. A film 5 having a reflectance close to 0% with respect to the pumping light from the semiconductor laser 3 and an appropriate reflectance with respect to the amplified spontaneous emission light is provided on the end face 4, and the other end face 6 is provided with the film 5 from the semiconductor laser 3. 100 for excitation light of
%, And a film 7 having a reflectance close to 0% with respect to amplified spontaneous emission light is adhered to suppress the laser oscillation in the light emitting base material glass. As the film having such optical characteristics, a multi-layer film made of, for example, a dielectric material, which is manufactured by a general thin film manufacturing technique such as an electron beam evaporation method, can be used. When laser light with a wavelength of 790 nm emitted from the semiconductor laser 3 which is an excitation light source is coupled to the termination surface 4, the wavelength of 790 nm is generated in the core of the light emitting base material glass fiber.
The guided mode of the excitation light of is excited. E is a light emitting medium added to the core when the excitation light travels to the end surface 6.
The element r absorbs the excitation light and emits spontaneous emission light with a central wavelength of 2.7. The spontaneous emission light that is emitted in the direction of the terminal surface 6 and is guided in the core is amplified by the Er element that is in the excited state and absorbs the excitation light, and the amplified spontaneous emission light. Becomes Most of the excitation light that has not been absorbed at the time of reaching the end surface 6 is reflected by the action of the optical film 7 on the end surface according to the reflectance, and travels toward the other end surface 4, and during the same period. Then, the amplified spontaneous emission light is generated. The amplified spontaneous emission light generated in this way reaches the end surface 6 and most of the amplified spontaneous emission light is transmitted through the end surface 6 and emitted according to the reflectance by the action of the optical film 7 on the end surface. As a result, from the central wavelength of 2.7 μm to 2.65 μm
A glass light emitting device that emits amplified spontaneous emission light (amplified spontaneous emission light) having a continuous spectrum over the wavelength range of 2.77 μm can be used.

FIG. 2 shows a double-beam type infrared spectroscopic analyzer using the glass light emitting element of FIG. 1 as a light source. The amplified spontaneous emission light flux 9 emitted from the light emitting base material glass fiber 8 containing Er excited by the laser light of the semiconductor laser excitation light source 3 is divided into two by the action of the half mirror 10 and becomes a sample light flux 11 and a reference light flux 12. The reference luminous flux 12 reaches the selector 15 via the reflecting mirrors 13 and 14. Sample beam 11 and control beam 12
Are alternately incident on the spectroscope 16 by the action of the selector 15. The selector 15 can be realized by, for example, forming a semi-circular plane mirror and rotating it, but is not limited thereto. FIG. 2 shows a state in which the semi-circular plane mirror part of the selector 15 is located at the confluence position of both light beams. In this state, only the reference light beam is reflected by the action of the plane mirror of the selector 15 and enters the spectroscope 16. . The sample, that is, the substance to be analyzed is dispersed according to its ordinary infrared spectroscopy method, for example, with a suitable dispersant if it is a solid, or sufficiently transmitted to the light of the light source if it is a liquid or gas. Put it in a cell made of material to form the sensor part 14, and insert it between the half mirror 10 and the selector 15. Light 17 emitted from the spectroscope is received by the photodetector 18, converted into an electric signal 19, amplified by an electric amplifier 20, and converted into an electric output to obtain spectral information of the sample light and the control light. This is sent to the recorder as it is and used as the analysis result of the graph display, or it is converted to digital output and sent to the computer 21.
Performs qualitative analysis data processing and displays as graphs and numerical values. In this example, the wavelength range of the glass light emitting element used as the light source was 2.65 μm to 2.77 μm at the central wavelength of 2.7 μm.
Therefore, it is possible to provide a double-beam type infrared spectroscopic analyzer for analyzing a gaseous substance having an absorption in this wavelength range, for example, H ₂ O gas or CO ₂ gas.

[0010]

Example 2 The center wavelength of the glass light emitting element which is the light source
An example of the double-beam type infrared spectroscopy analyzer set to 2.3 μm, 2.7 μm, and 2.9 μm will be described. As a glass light emitting element that is a light source, the shape of the light emitting base material glass is cylindrical, and a waveguide structure is formed by a core to which three types of light emitting media are added at the same time and a clad not added, and the excitation light source is a semiconductor laser array. , An anti-reflection coating for the light emitted from the three types of light-emitting media is applied to all the optical waveguide termination surfaces, and the center wavelength is 2.3 μm,
A glass light emitting element that emits light at 2.7 μm and 2.9 μm is used.
The sectional view is shown in FIG. The shape of the light-emitting base material glass of the glass light-emitting element is a cylindrical fiber 29, and a core 22 made of fluoride glass to which Tm, Er, and Ho of rare earth elements are added as a light-emitting medium and a fluoride glass having a lower refractive index than the core are used. A waveguide structure is formed by a clad 23 composed of. When fluoride glass is used as the luminescent matrix glass, the luminescent medium T
In order to cause m, Er, and Ho to emit light with central wavelengths of 2.3 μm, 2.7 μm, and 2.9 μm, the luminescent medium has wavelengths of 790 nm, 790 nm, and 790 nm, respectively.
It can be excited by light of 640 nm. Therefore, the wavelength of the excitation light source may be two wavelengths of 640 nm and 790 nm. The pumping semiconductor laser array is constructed by placing two semiconductor laser chips with different oscillation wavelengths of 640 nm and 790 nm in close proximity or by monolithically integrating them within the range of ordinary semiconductor optical device fabrication technology. Can be made. A semiconductor laser array 24 having an oscillation wavelength of 640 nm and 790 nm, which is an excitation light source, is arranged so as to be optically coupled to the termination surface 25 of the light emitting base material glass.
In this embodiment, they are directly coupled, but it goes without saying that they can be optically coupled via an optical component such as a lens or an optical fiber. An optical film 2 having a reflectance close to 0% with respect to the excitation light from the semiconductor laser array 24 and having a suitable reflectance for the amplified spontaneous emission light is provided on the termination surface 25.
6 is attached to the other end face 27, and an optical film 28 having a reflectance close to 100% for the pump light from the semiconductor laser array and close to 0% for the amplified spontaneous emission light is attached, The structure is such that laser oscillation in the light emitting base material glass is suppressed. As the film having such optical characteristics, a multi-layer film made of, for example, a dielectric material, which is manufactured by a general thin film manufacturing technique such as an electron beam evaporation method, can be used. End face 2
Laser light with wavelengths of 640 nm and 790 nm emitted from the semiconductor laser array 24, which is the excitation light source, is coupled to the laser.
As a result, the central wavelength is
2.3 μm, 2.7 μm, 2.9 μm respectively 2.25 μm to 2.
50 μm, 2.65 μm to 2.77 μm, 2.83 μm to 2.95
It is possible to use a glass light emitting device that emits light in which three types of amplified spontaneous emission light having a continuous spectrum over a wavelength range of μm are emitted.

FIG. 4 shows a double-beam type infrared spectroscopic analyzer using the glass light emitting element of FIG. 3 as a light source. The amplified spontaneous emission light flux 9 emitted from the light emitting base material glass fiber 29 containing Er excited by the laser light of the semiconductor laser excitation light source 24 is
It is divided into two by the action of the half mirror 10 and becomes a sample light beam 11 and a control light beam 12. The reference luminous flux 12 reaches the selector 15 via the reflecting mirrors 13 and 14. Sample beam 11 and control beam
12 is the spectrometer 16 alternately by the action of the selector 15.
Incident on. The selector 15 can be realized by, for example, forming a semi-circular plane mirror and rotating it, but is not limited thereto. FIG. 4 shows a state in which the semicircular plane mirror part of the selector 15 is located at the confluence position of both light fluxes 11 and 12. In this state, only the reference light flux is reflected by the action of the plane mirror of the selector to the spectroscope 16. Incident. Depending on the state of the sample, for example, if it is a solid, it is dispersed with a convenient dispersion material, and if it is a liquid, it is placed in a cell formed of a material that sufficiently transmits the light of the light source. , Insert between half mirror 10 and selector 15. Spectrometer 16
The emitted light 17 is received by a photodetector 18, converted into an electric signal 19, and amplified by an electric signal amplifier 20 to be an electric output. This is sent to the recorder as it is and used as the analysis result of the graph display, or it is converted to a digital output and sent to a computer for data processing of quantitative / qualitative analysis and displayed as a graph / numerical value. In this example, the wavelength range of the glass light-emitting element used for the light source is more, the central wavelength 2.3μm, 2.7μm, 2.9μ
From 2.25 μm to 2.50 μm and 2.65 μm respectively in m
2.77 μm, 2.83 μm to 2.95 μm, so gaseous substances that absorb in this wavelength range, such as H ₂ O, CO, CO ₂ , N
A double-beam type infrared spectroscopic analyzer for analyzing gases such as O, N ₂ O, and NH ₃ can be used.

[0012]

Example 3 The center wavelength of the glass light emitting element which is the light source
Another example of the double-beam type infrared spectroscopy analyzer set to 2.3 μm, 2.7 μm, and 2.9 μm will be described. The glass light-emitting element that is the light source is a group of light-emitting base glass composed of three types of light-emitting base glass, each light-emitting base glass has a cylindrical shape, and a core to which one type of light-emitting medium is added, A waveguide structure is formed with a cladding not added, each pumping light source is a semiconductor laser, and a structure for combining the light emitted from each light emitting medium of each light emitting base material glass is given. A glass light-emitting element that emits light with three types of center wavelengths of 2.3 μm, 2.7 μm, and 2.9 μm is used by coating an antireflection film against the light emitted from each light-emitting medium on all the end faces. As shown in FIG.
The shape of each light-emitting base material glass of the light-emitting base-material glass group of the glass light-emitting element is a cylindrical fiber 30, 31, 32. As shown in Example 1, the rare earth element Tm,
A waveguide structure is formed by a core made of fluoride glass to which Er and Ho are added as a light emitting medium and a clad made of fluoride glass having a refractive index lower than that of the core. When fluoride glass is used as the luminescent matrix glass, in order to make the luminescent media Tm, Er, and Ho emit light with central wavelengths of 2.3 μm, 2.7 μm, and 2.9 μm, the luminescent media have wavelengths of 790 nm, 790 nm, and 640 nm, respectively. You can excite with. Oscillation wavelength of excitation light source 790 nm, 790
The semiconductor lasers 33, 34 and 35 of nm and 640 nm are arranged so as to be optically coupled to the respective end faces of the light emitting base material glass fibers 30, 31 and 32 which include Tm, Er and Ho which constitute the light emitting base material glass group. To do. In this example, the connection is made directly,
It goes without saying that optical coupling can also be performed via an optical component such as a lens or an optical fiber. A film having a reflectance close to 0 for the pumping light from each semiconductor laser and a suitable reflectance for the amplified spontaneous emission light is provided on each end face, and each semiconductor laser is provided on each of the other end faces. A film with a reflectivity close to 100% for the excitation light from and a close to 0% for the amplified spontaneous emission light is attached to suppress the laser oscillation in the light emitting base material glass. . As the film having such optical characteristics, a multi-layer film made of, for example, a dielectric material, which is manufactured by a general thin film manufacturing technique such as an electron beam evaporation method, can be used. A pumping semiconductor laser 33,
Laser beams with wavelengths of 680 nm, 790 nm, and 640 nm emitted from 34 and 35 are coupled. As a result, according to the principle described in Example 1, the center wavelengths of 2.3 μm, 2.7 μm, and 2.9 μm are 2.25 μm to 2.50 μm and 2.65 μm to 2.77 μm, respectively.
m, 2.83 μm to 2.95 μm Wavelength of three types of amplified spontaneous emission light with continuous spectrum is generated, collected into output fiber 38 via fiber couplers 36 and 37, and emitted from the end surface as a glass light emitting element. be able to.

FIG. 6 shows a double-beam type infrared spectroscopic analyzer using the glass light emitting element of FIG. 5 as a light source. Amplified spontaneous emission flux 9 synthesized into output fiber 38 by fiber couplers 36 and 37 emitted from Er-containing light emitting base material glass fibers 30, 31 and 32 excited by laser light from semiconductor laser excitation light sources 33, 34 and 35 Is halved by the action of the half mirror 10 to become a sample light beam 11 and a control light beam 12. The reference luminous flux 12 reaches the selector 15 via the reflecting mirrors 13 and 14. The sample light beam 11 and the control light beam are alternately incident on the spectroscope 16 by the action of the selector 15. Selector 15
Can be realized, for example, by forming it with a semicircular plane mirror and rotating it, but is not limited to this. Fig. 6 shows both luminous flux 1
This shows the state where the semi-circular plane mirror part of the selector 15 is located at the confluence position of 1 and 12, and in this state only the reference light beam is reflected by the action of the plane mirror of the selector 15 and the spectrometer
It is incident on 16. Depending on the state of the sample, for example, if it is a solid, it is dispersed with a convenient dispersion material, and if it is a liquid, it is placed in a cell formed of a material that sufficiently transmits the light of the light source. , Half mirror 10 and selector 1
Insert between 5. The light 17 emitted from the spectroscope 16 is detected by the photodetector.
The light is received by 18 and converted into an electrical signal 19 and the electrical signal amplifier 2
It is amplified at 0 and used as an electrical output. This is sent to the recorder as it is and used as the analysis result of the graph display, or it is converted to a digital output and sent to a computer for data processing of quantitative / qualitative analysis and displayed as a graph / numerical value. In this example, the wavelength range of the glass light-emitting device used as the light source was 2.25 μm at the central wavelengths of 2.3 μm, 2.7 μm, and 2.9 μm.
To 2.50 μm, 2.65 μm to 2.77 μm, 2.83 μm to 2.95 μm, so gaseous substances that absorb in this wavelength range, such as H ₂ O, CO, CO ₂ , NO, N ₂ O, NH ₃ etc. A double-beam type infrared spectroscopic analyzer that is an analysis target can be provided.

An embodiment of the remote infrared spectroscopy analyzer will be described. FIG. 7 shows a block diagram of a remote analyzer using an optical fiber for the sample light optical system and the signal light optical system in an example of the remote analyzer according to the present invention. Amplified spontaneous emission light emitted from the glass light emitting element 39 is used as the sample light and the sample optical waveguide fiber 4
It is coupled to 0 and guided to the sensor part 41 to interact with the substance to be analyzed. The light after the interaction, that is, the signal light is coupled to the signal light guide fiber 42 and guided to the measurement unit 43, where the target substance is analyzed. An example of a remote infrared spectroscopic analyzer using optical fibers for the sample light optical system and the signal light optical system will be described below.

[0015]

[Embodiment 4] FIG. 8 shows the center wavelength of a glass light emitting device as 2.7
An example of a single-beam type remote infrared spectroscopic analyzer set to μm for the purpose of analyzing a substance in a gas state is shown. As the glass light emitting element, the one described in Example 1 is used. In the drawing, only the light emitting base material glass fiber 8 containing the light emitting medium Er and the pumping semiconductor laser 3 are shown, but the details thereof are described in FIG. 1 and the first embodiment. The waveguide fibers 40 and 42 for the sample light and the signal light are composed of a core made of fluoride glass and a clad made of fluoride glass having a lower refractive index than that of the light emitting base material glass fiber 8. The composition of the fluoride glass of the core and the clad of the waveguide fibers 40 and 42 is preferably the same as the composition of the fluoride glass of the core and the clad of the light emitting glass fiber 8, but it is not limited thereto. Further, the composition of the fluoride glass of the core and the clad of the sample light guiding fiber 40 is not limited to the same as the composition of the fluoride glass of the core and the clad of the signal light guiding fiber 42. The light emitting base material glass fiber 8 and the sample optical waveguide fiber 40 are connected by a connecting portion 44 which is highly efficiently coupled by, for example, a fusion method. The sensor section 41 is composed of, for example, a pair of concave mirrors 45, and includes a sample optical waveguide fiber.
The sample light emitted from the end portion 46 of 40 is multiply reflected by a pair of concave mirrors. At the time of this multiple reflection, the gas to be analyzed is allowed to interact with the gas to be analyzed in the sensor section 41 so that the light having a specific wavelength of the sample light having a continuous spectrum is absorbed by the gas to be analyzed. The signal light after the interaction is coupled to the end 47 of the signal light guiding fiber 42 and guided to the entrance 48 of the spectroscope 16 in the measuring unit 43. The measuring unit 43 includes a spectroscope 16, a photodetector 18, an electric signal amplifier 20, and a computer 21. Spectroscope
The emitted light 17 of 16 is received by the photodetector 18, and the electrical signal 1
It is converted to 9 and amplified by an electric amplifier 20 and further converted to an electric digital signal and output as spectrum information. This is sent to the computer 21, the data processing of quantitative / qualitative analysis is performed, and it is displayed as a graph / numerical value. Alternatively, depending on the case, the analysis result can be sent to the recorder as it is without using a computer and used as the analysis result of the graph display. In this example, since the wavelength range of the glass light emitting element used as the light source is 2.65 μm to 2.77 μm at the central wavelength of 2.7 μm, a gaseous substance having absorption in this wavelength range, for example, H ₂ O gas or CO ₂ gas is used. It can be a remote infrared spectroscopic analysis device that is an analysis target.

[0016]

[Embodiment 5] FIG. 9 shows the center wavelength of a glass light emitting device with 2.3
An example of a remote infrared spectroscopic analyzer for gas substances set to μm, 2.7 μm, and 2.9 μm is shown. As the glass light emitting element, the one described in Example 2 is used. In the figure,
Only the light-emitting base material glass fiber containing three kinds of light-emitting mediums Tm, Er, and Ho at the same time and the pumping semiconductor laser array are shown, and the details thereof are described in FIG. 3 and the second embodiment. In this example, the wavelength range of the glass light emitting element used as the light source was 2.25 μm at the center wavelengths of 2.3 μm, 2.7 μm, and 2.9 μm, respectively.
To 2.50 μm, 2.65 μm to 2.77 μm, 2.83 μm
To 2.95 μm, so a remote infrared spectroscopic analyzer is used for the analysis of gaseous substances that have absorption in this wavelength range, such as gases such as H ₂ O, CO, CO ₂ , NO, N ₂ O and NH _3. be able to.

[0017]

Example 6 FIG. 10 shows the center wavelength of the glass light emitting device.
An example different from the example 5 of the remote infrared spectroscopic analyzer for the substances in the gas state, which are set to 2.3 μm, 2.7 μm, and 2.9 μm, will be shown. As the glass light emitting element, the one described in Example 3 is used. In the figure, the luminescent matrix glass group consisting of three luminescent matrix glass fibers 30, 31 and 32 each containing the luminescent medium Tm, Er, and Ho, and the three luminescent matrix glass fibers for exciting the three luminescent matrix glass fibers Only the semiconductor lasers 33, 34, 35 are shown, the details of which are given in FIG. 5 and in the third embodiment. In this example, the wavelength range of the glass light emitting element used as the light source is 2.25 μm to 2.50 μm, 2.65 μm to 2.77 μm at the center wavelengths of 2.3 μm, 2.7 μm, and 2.9 μm, respectively.
m, 2.83 μm to 2.95 μm, so gaseous substances that absorb in this wavelength range, such as H ₂ O, CO, CO ₂ , NO, N
It can be used as a remote infrared spectroscopic analyzer that analyzes gases such as ₂ O and NH ₃ .

In Examples 1 to 6 above, the luminescent medium Tm, E
The wavelengths of the pumping semiconductor lasers that pump r and Ho are respectively
Although described as 790 nm, 790 nm, and 640 nm, the central wavelengths of Tm, Er, and Ho, which are light emitting media, are 2.3 μm, 2.7 μm, and 2.9 μm.
It is not limited to this as long as it excites the light emission of.

Fluoride glass has been described as an example of the light emitting base material glass, but it is not limited to fluoride glass.
Any substance that has a high transmittance with respect to the emitted light of the effect medium and can be provided with a waveguide structure may be used.

Although the rare earth elements Tm, Er, and Ho are described as examples of the light emitting medium contained in the light emitting base material glass of the glass light emitting device, the rare earth elements other than these are not limited to Tm, Er, and Ho. Not only the element but also an element other than the rare earth element, as long as it has an emission characteristic, only the emission center wavelength and the emission wavelength range and the excitation wavelength of the excitation semiconductor laser are different, and the object of the present invention is achieved. A glass light emitting device and a remote analyzer can be implemented. Further, the condition of the light emitting medium is not limited to the elemental substance as long as it is a substance having a light emitting property. For example, Al _1-vw In _v Ga _w P
_{1-Xy As x Sb y (} 0 ≦ v, w, x, y ≦ 1, v + w ≦ 1, x + y ≦
1), or Pb _1-q Sn _q Se _1-r Te _r (0 ≦ q, r ≦ 1)
The compound semiconductor material represented by can also satisfy the conditions of the light emitting medium.

Although the shape of the light-emitting base material glass of the glass light-emitting element is limited to the cylindrical shape, the cylindrical shape is an example of the waveguide structure given to the light-emitting base material glass, and the shape is not limited to this.

Further, although the sensor section uses the multiple reflection by the concave mirror, it is not limited to this as long as it can effectively interact the analyte and the sample light.

As the spectroscope of the measuring unit, a normal spectroscope, for example, a dispersive spectroscope using a dispersive element such as a diffraction grating or a prism, or an interferometer using an interferometer typified by a Fourier transform interference spectrophotometer A spectroscope may be used.

In the first to third embodiments, the so-called multi-beam method is used in which the light from the glass light emitting element as the light source is made into two light beams, but the present invention is not limited to this, and a so-called single light beam is used. The luminous flux method may be used.

On the contrary, in the fourth to sixth embodiments, the so-called single-beam method in which the light from the glass light emitting element which is the light source is used as one light flux is described. However, the light flux is not limited to this and two light fluxes are used. A so-called multiple beam method may be used.

Further, in the fourth to sixth embodiments, the interaction between the substance to be analyzed and the sample light in the sensor part is described only by the intensity change due to the absorption of the sample light by the substance to be analyzed, but not limited to this, for example. It is possible to widely use physical-optical phenomena such as reflection, refraction, scattering, diffraction, phase change, polarization plane rotation, frequency change, etc. of sample light by the substance to be analyzed or fluorescence / phosphorescence of the substance to be analyzed by excitation of sample light.

[0027]

INDUSTRIAL APPLICABILITY The infrared spectroscopic analyzer according to the present invention is a glass light-emitting device that has a unique effect that it operates at room temperature, has high brightness, high condensing property, and generates continuous spectrum light without tuning and sweeping operation. Since it is used as a light source, it has a special effect that it does not require a cryogen and can perform spectroscopic analysis without time delay due to tuning and sweeping.

The remote infrared spectroscopic analyzer using a fiber as an optical system does not require a special heat insulating container for storing a cryogen and a facility capable of automatically supplying the cryogen, and does not cause a time delay due to sweeping. It has the effect of being able to perform continuous analysis in continuous operation, such as an in-line analyzer for chemical, food, steel and agricultural plants, and an analyzer for monitoring harmful substances emitted from devices and equipment in various industries.

In addition to this, the remote infrared spectroscopic analyzer using a fiber for the optical system can perform analysis even if the space in which the gas to be analyzed exists is extremely narrow as long as the sensor unit can be introduced. In addition, if the gas to be analyzed is a gas that is extremely dangerous to humans, such as an explosive gas or a toxic gas, and if the point where the gas to be analyzed is an environment that is extremely dangerous to humans, such dangerous gas or It can be analyzed at a location remote from the environment. Further, even when the point where the gas to be analyzed is present is an environment unsuitable for the infrared spectroscopic analyzer, for example, high temperature and high humidity, it is possible to perform analysis at a point distant therefrom.

Further, an infrared spectroscopic analyzer using a glass light emitting element having one kind of light emitting base material glass as the light source and two or more kinds of light emitting mediums as the light source can analyze in a wider wavelength range.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an example of a glass light emitting element which is composed of one light emitting base material glass fiber containing one kind of light emitting medium and is used for a light source in the present invention.

FIG. 2 is a system diagram showing a double-beam type infrared spectroscopic analyzer according to the present invention which uses the glass light emitting element of FIG. 1 as a light source.

FIG. 3 is a cross-sectional view showing an example of a glass light emitting element which is composed of a single glass fiber of a light emitting base material containing three types of light emitting media and which is used as a light source in the present invention.

FIG. 4 is a system diagram showing a double-beam type infrared spectroscopic analyzer according to the present invention which uses the glass light emitting element of FIG. 3 as a light source.

FIG. 5 is a schematic view showing an example of a glass light emitting element used for the light source in the present invention, which is composed of a group of light emitting base material glass fibers in which three light emitting base material glass fibers containing one kind of light emitting medium are assembled.

6 is a system diagram showing a double-beam infrared spectroscopic analyzer according to the present invention which uses the glass light emitting device of FIG. 5 as a light source.

FIG. 7 is a system diagram showing a configuration example of a remote analyzer using an optical fiber for a sample optical system and a signal optical system.

8 is a system diagram showing an example of a single-beam type remote infrared spectroscopic analyzer according to the present invention, which uses the glass light emitting element of FIG. 1 as a light source.

9 is a system diagram showing an example of a single-beam type remote infrared spectroscopic analyzer according to the present invention, which uses the glass light emitting element of FIG. 3 as a light source.

FIG. 10 is a system diagram showing an example of a single-beam type remote infrared spectroscopic analyzer according to the present invention which uses the glass light emitting element of FIG. 5 as a light source.

[Explanation of symbols]

1 Core made of fluoride glass to which Er of rare earth element is added as a light emitting medium 2 Cladding made of fluoride glass with a lower refractive index than the core 3 Semiconductor laser with an oscillation wavelength of 790 nm that is an excitation light source 4,6 Terminal surface 5 Optical film with reflectivity close to 0% for excitation light 7 Optical film with reflectivity close to 100% for excitation light and close to 0% for amplified spontaneous emission light 8 Luminescent matrix glass fiber containing luminescent medium 9 Amplified spontaneous emission light 10 Half mirror 11 Luminous flux for sample 12 Reference luminous flux 13,14 Reflective mirror 15 Selector 16 Spectroscope 17 Light emitted from spectroscope 18 Photodetector 19 Converted Electrical signal 20 Electrical signal amplifier 21 Computer 22 Core made of fluoride glass doped with rare earth elements Tm, Er, and Ho as light emitting medium 23 Cladding 24 Excitation semiconductor laser oscillating at two wavelengths of 640 nm and 790 nm The array 25,27 Emitting matrix glass fiber end 26 Film with reflectivity close to 0% for excitation light 28 Close to 100% for excitation light and close to 0% for amplified spontaneous emission light Film with reflectivity 29 Emitting matrix glass fiber containing Tm, Er, and Ho of rare earth elements as light emitting medium 30 Core made of fluoride glass with Tm of rare earth element added as light emitting medium 31 Er of rare earth element as light emitting medium A core made of fluoride glass added as a core 32 A core made of a fluoride glass doped with Ho of a rare earth element as a light emitting medium 33 A semiconductor laser having an oscillation wavelength of 790 nm as an excitation light source 34 A semiconductor laser having an oscillation wavelength of 790 nm as an excitation light source 35 Semiconductor laser with an oscillation wavelength of 640 nm as an excitation light source 36,37 Fiber coupler 38 Output fiber 39 Glass light emitting element 40 Sample optical waveguide fiber 41 Sensor section 42 Signal optical waveguide Fiber 43 Measurement part 44 Connection part between glass light emitting element fiber and sample optical waveguide fiber 45 Pair of concave mirrors 46 End of sample optical waveguide fiber 47 End of signal optical waveguide fiber 48 Entrance of spectroscope

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Osamu Shinbori 2-32 Nishishinjuku, Shinjuku-ku, Tokyo International Telegraph and Telephone Corporation

Claims (3)

[Claims] 1. A luminescent matrix comprising at least one luminescent medium that emits light when excited by light and having a light-guiding structure, or at least two types of luminescent matrix glass different in the luminescent medium. A light emitting base material composed of a light emitting base material glass group having a structure for combining respective lights emitted from respective light emitting media of the material glass, and laser oscillation by the emission light of the light emitting medium in the light emitting base material Suppressing means, an excitation light source that emits light that excites the luminescent medium by optically coupling to one of the optical waveguide termination surfaces of the luminescent base material, and the light emitted from the luminescent base material is divided into sample light and reference light. Means, a sensor part for interacting the sample light with the substance to be analyzed, a means for alternately extracting the sample light and the control light interacting with the substance to be analyzed by the sensor part, Sample light and the pair An infrared spectroscopic analyzer having a measuring unit for measuring illumination. 2. A luminescent matrix comprising at least one luminescent medium that emits light when excited by light and having an optical waveguide structure, or at least two types of luminescent matrix glass different in the luminescent medium. A light emitting base material composed of a light emitting base material glass group having a structure for combining respective lights emitted from respective light emitting media of the material glass, and laser oscillation by the emission light of the light emitting medium in the light emitting base material Means for suppressing, an excitation light source that emits light that optically couples to one of the optical waveguide termination surfaces of the luminescent base material and excites the luminescent medium, and the emitted light of the luminescent base material as sample light to interact with the substance to be analyzed. A sensor section to act, a measuring section to measure signal light that is sample light interacting with the analysis target in the sensor section, and a sample light optical system to make the emitted light of the luminescent base material reach the sensor section, The sensor An infrared spectroscopic analysis apparatus comprising a signal light optical system that allows the signal light from a unit to reach the measuring unit. 3. The infrared spectroscopic analyzer according to claim 2, wherein the sample light optical system and the signal light optical system have a cylindrical shape, and the core and the clad are formed into a waveguide structure. .