JP2011247627A - Optical probe and spectrometry device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To quickly detect the breakage of an immersion type optical probe.SOLUTION: The optical probe 1 includes: a projecting optical fiber 3 for propagating light to irradiate a liquid sample with; a lens 5 facing the projecting optical fiber end face 3a and disposed at an interval from the projecting optical fiber end face 3a; a light reflecting material 7 arranged at an interval from the lens 5, for reflecting the light irradiated from the projecting optical fiber end face 3a and transmitted through the lens 5 and a liquid sample 25 to the lens 5; a light receiving optical fiber 9 arranged at an interval from the lens 5 on the same side as the projecting optical fiber 3 relative to the lens 5, for receiving the light reflected at the light reflecting material 7 and transmitted through the liquid sample 25 and the lens 5; a cylindrical member 13 and a sealing member 15 for isolating a space 23 between the optical fiber end faces 3a, 9a and the lens 5 from the liquid sample 25; and a liquid leakage detection sensor 11 for detecting the infiltration of the liquid sample 25 into the space 23.

Description

  The present invention relates to an optical probe and a spectroscopic measurement apparatus using the same, and more particularly to an immersion type optical probe and a spectroscopic measurement apparatus using the same.

There is an absorbance measurement method as a method of measuring the component concentration of a liquid sample. In the absorbance measurement method, the concentration of the measurement target substance can be quantitatively analyzed by irradiating the liquid sample with light and measuring the absorbance of the measurement target substance when the light passes through the liquid sample.
When continuously monitoring the component concentration of a liquid sample, an immersion type optical probe using an optical fiber may be used (see, for example, Patent Documents 1 and 2).

FIG. 10 is a cross-sectional view for explaining a conventional optical probe.
The optical probe 101 includes an irradiation optical fiber 103, a light receiving optical fiber 105, a capillary 107, a mirror 109, a lens 111, a reinforcing material 113, and a sample insertion cell 115.

JP 2006-23200 A JP 2009-250825 A

  Since the immersion type optical probe is generally a thin rod, the probe structure may be damaged if the tip of the optical probe comes into contact with another member. For example, in the optical probe 101 shown in FIG. 10, if the capillary 107 and the reinforcing material 113 are broken and broken, and the lens 111 and the optical fibers 103 and 105 are broken, light for measurement cannot pass and a failure state occurs. .

  Also, in the example of measuring the physical properties of the cleaning solution by immersing the optical probe in the semiconductor cleaning solution tank, the cleaning solution is very disliked of metal contamination, so that there is no metal contamination at the ppb (parts per billion) level and ppt (parts per trillion) level. Therefore, the optical probe is made of quartz. However, when quartz breakage occurs due to trouble or the like, the cleaning liquid may enter the optical probe, and the metal of the constituent members of the components in the optical probe may leak into the cleaning liquid, causing serious damage. For example, in the optical probe 101 shown in FIG. 10, when the capillary 107 and the reinforcing material 113 are damaged, the liquid sample comes into contact with the lens 111 and the optical fibers 103 and 105, and the metal contained in the lens 111 and the optical fibers 103 and 105 becomes the liquid sample. Melt in.

  An object of this invention is to provide the optical probe which can detect rapidly the failure | damage of an optical probe, and the spectroscopic measurement apparatus using the same.

An optical probe according to the present invention includes a light projecting optical fiber for propagating light applied to a liquid sample, a light receiving optical fiber for propagating light that has passed through the liquid sample, and a portion of the optical fiber. And a structure for forming a space that is isolated from the liquid sample, and a sensor for detecting the intrusion of the liquid into the space.
In the optical probe of the present invention, a space in which a liquid sample to be measured cannot enter the optical probe is formed. In the space, a part of the optical fiber for light projection, a part of the optical fiber for light reception, and a sensor for detecting the liquid are installed. When a liquid sample enters the space due to breakage of the optical probe, the breakage of the optical probe is detected by detecting the liquid sample entering the space by the sensor.

  An optical probe example according to the present invention includes a light projecting optical fiber for propagating light irradiated to a liquid sample, an irradiation lens for condensing or collimating light irradiated from the end surface of the light projecting optical fiber, A light receiving lens that collects or collimates light that has passed through the liquid sample by being irradiated from the irradiation lens, and a light receiving device for propagating the light irradiated from the light receiving lens to the optical fiber end surface for light reception A structure for separating the optical fiber from the liquid sample, for example, a cylindrical structure is provided. A space is formed in the structure, and the space is structured such that the liquid sample cannot enter without damage to the optical probe. In the space, a part of the light projecting optical fiber, a part of the light receiving optical fiber, and a sensor for detecting the intrusion of the liquid sample into the space are arranged in the space. When the optical probe is broken and a liquid sample enters the space, the sensor detects the liquid that has entered the space. Based on the detection of the liquid by the sensor, the user of the optical probe may cause a measurement abnormality of the related spectroscopic measurement device due to damage to the optical probe, metal contamination of the liquid in which the optical probe is immersed, or an optical probe component. Detect that contamination has occurred. For example, if the contaminated liquid is a semiconductor cleaning liquid, the user of the optical probe can minimize damage to the semiconductor manufacturing process abnormalities due to the contaminated liquid.

  In the optical probe of the present invention, the light projecting optical fiber and the light receiving optical fiber may be constituted by a single optical fiber. However, the light projecting optical fiber and the light receiving optical fiber may be constituted by separate optical fibers.

  In addition, one end face of the optical fiber may be disposed in the space, and the structure may include a lens through which the light is transmitted at a portion in contact with the liquid sample. For example, the structure includes a cylindrical member in which the lens is disposed inside a tip, a sealing member for filling a gap between the cylindrical member and the lens, and a part of the optical fiber disposed in the cylindrical member. An optical fiber support member. The space is formed in the cylindrical member. One end face of the optical fiber is disposed in the space.

In addition, one end face of the optical fiber is disposed in the space, and the structure includes a window plate through which the light is transmitted at a portion in contact with the liquid sample. You may make it provide the lens which the said light permeate | transmits between window plates. For example, the structure includes a cylindrical member in which the window plate is disposed inside a tip, a sealing member for filling a gap between the cylindrical member and the window plate, and a part of the optical fiber in the cylindrical member. The optical fiber support member for arrange | positioning, and the said lens are provided. The space is formed in the cylindrical member. One end face of the optical fiber is disposed in the space.
However, the structure of the structure is not limited to these, and may be any structure as long as the space in which a part of the optical fiber is arranged can be isolated from the liquid sample.

  The sensor may be any sensor as long as it can detect the intrusion of liquid into the space. For example, the sensor is generally called a liquid leakage detection sensor or a liquid level gauge.

  In the optical probe of the present invention, an independent sensor such as a liquid leakage detection sensor or a liquid level gauge may be installed as the sensor, but in the configuration in which one end surface of the optical fiber is disposed in the space. The sensor enters the space based on a change in the intensity of light irradiated from the end surface opposite to the one end surface of the light receiving optical fiber, which is caused by liquid entering the optical path in the space. Intrusion of liquid may be detected. When the optical probe is damaged, the liquid comes into contact with the end face of the optical fiber for projection, the end face of the optical fiber for light reception, the lens, the window plate, etc., so that the end face of the optical fiber for light reception (the end face arranged in the space) is opposite. The intensity of the light irradiated from the end face varies greatly as compared with a state where the optical probe is not damaged. By detecting the change in the light intensity, the intrusion of the liquid into the space can be detected. That is, one end surface of the light projecting optical fiber and / or one end surface of the light receiving optical fiber disposed in the optical probe can be used as the sensor. In addition, when the optical probe is broken, the liquid sample adheres not only to the end face of the optical fiber but also to the space side surface of the lens and window plate. Therefore, by detecting the intensity change of the light passing through these surfaces, Intrusion of liquid into the space can be detected.

  The spectroscopic measurement device according to the present invention includes an optical probe according to the present invention, a light source for irradiating light onto the second end face of the light projecting optical fiber opposite to the one end face of the light projecting optical fiber, and the light receiving optical fiber. A light detection unit for receiving light irradiated from the second optical fiber for receiving light on the side opposite to the one end surface, and a liquid sample component concentration according to a light intensity signal from the light detection unit A data processing unit, and a display unit for displaying a liquid leakage warning based on a liquid leakage detection signal from the liquid leakage detection sensor.

The optical probe of the present invention includes a sensor for detecting the intrusion of liquid into a space in which one end face of the projecting optical fiber and one end face of the receiving optical fiber are arranged and isolated from the liquid sample. I was prepared.
The spectroscopic measurement apparatus of the present invention includes the optical probe of the present invention and a display unit that displays a liquid leakage warning based on a liquid leakage detection signal from the liquid leakage detection sensor.
The optical probe and the spectroscopic measurement apparatus of the present invention can detect the intrusion of the liquid into the space due to the damage of the optical probe by the sensor, so that the damage of the optical probe can be detected quickly.
This urges the user of the optical probe to be alerted to prevent erroneous measurement due to liquid intrusion into the space between the end face of the optical fiber and the lens, contamination of the optical probe components into the liquid sample, and leakage of metal components. Minimizing the damage can prevent the spread of enormous damage.
In addition, when one end surface of the light projecting optical fiber or one end surface of the light receiving optical fiber in the optical probe is used as a sensor, the structure of the optical probe is simplified and the reliability of the apparatus is improved.

It is sectional drawing which expands and shows the lens periphery of Example 1 of an optical probe. 1 is a cross-sectional view illustrating an overall configuration of Example 1. FIG. It is a figure which shows roughly one Example of a spectrometer. It is sectional drawing which expands and shows the lens periphery of Example 2 of an optical probe. It is a figure which shows the signal change of a light receiving element when an optical probe is damaged and a liquid infiltrates into an optical probe. It is a figure which shows the signal change of the light receiving element when a tungsten lamp burns out. It is a figure which shows a signal change when an optical probe is taken out from the liquid sample in the air. It is sectional drawing which expands and shows the lens periphery of Example 3 of an optical probe. It is a figure which shows schematically the other Example of a spectrometer. It is sectional drawing for demonstrating the conventional optical probe.

Example 1
FIG. 1 is an enlarged sectional view showing the periphery of a lens according to an embodiment of the optical probe. FIG. 2 is a sectional view showing the entire structure of the embodiment.

  The optical probe 1 includes a light projecting optical fiber 3, a lens 5, a measurement light reflecting mirror (light reflecting material) 7, a light receiving optical fiber 9, a liquid level gauge (sensor) 11, a cylindrical member 13, a sealing member 15, and a lens positioning member. 17, an optical fiber and level gauge support member 19, and a mirror support member 21.

The lens 5 is disposed inside the tip of a cylindrical member 13 made of, for example, quartz. A gap between the lens 5 and the cylindrical member 13 is filled with an annular sealing member 15. The material of the sealing member 15 is, for example, fluororesin rubber. The lens 5 and the sealing member 15 are positioned by an annular lens positioning member 17 disposed in the cylindrical member 13. The material of the lens positioning member 17 is, for example, PTFE (Polytetrafluoroethylene).
The space 23 in the cylindrical member 13 is isolated from the atmosphere around the cylindrical member 13 by the lens 5 and the sealing member 15.

One end of the light projecting optical fiber 3, one end of the light receiving optical fiber 9, and the tip of the liquid level gauge 11 are disposed in the space 23 in the cylindrical member 13, and are made of PTFE disposed in the cylindrical member 13. It is supported by an optical fiber and a level gauge support member 19.
The light projecting optical fiber end surface 3 a and the light receiving optical fiber end surface 9 a face the lens 5 in the cylindrical member 13, and are disposed at positions spaced from the lens 5.
The tip of the liquid level gauge 11 is disposed at a position that does not intersect the optical path between the optical fiber end faces 3 a and 9 a and the lens 5. The tip of the liquid level gauge 11 is arranged on the lens 5 side by, for example, 3 mm (millimeter) from the optical fiber end faces 3a and 9a.

  The measuring light reflecting mirror 7 is supported by a mirror support member 21 attached to the cylindrical member 13. The material of the mirror support member 21 is, for example, quartz. The measuring light reflecting mirror 7 is disposed opposite to the lens 5 and at a position spaced from the lens 5.

When the optical probe 1 is used, the tip portion of the optical probe 1 is immersed in the liquid sample 25. The tip portion of the optical probe 1 is immersed in the liquid sample 25 to a depth at least where the lens 5 contacts the liquid sample 25.
Measurement light is emitted from the optical fiber end surface 3a for light projection. The measurement light is converted into parallel light or condensed light by the lens 5 and applied to the measurement light reflecting mirror 7 through the liquid sample 25. The light reflected by the measurement light reflecting mirror 7 reaches the lens 5 through the liquid sample 25, is condensed again by the lens 5, and is condensed on the optical fiber end face 9a for light reception.

  When the optical probe 1 is broken and the liquid sample 25 enters the space 23, the intruded liquid sample comes into contact with the tip of the liquid level gauge 11 disposed in the space 23. The liquid level gauge 11 can detect breakage of the optical probe 1 by detecting the intrusion of the liquid sample into the space 23.

  Here, as the liquid level gauge 11, a photoelectric sensor HPF-D033 (a product of Yamatake Shokai Co., Ltd.) that detects the presence of liquid with light was used. However, the level gauge 11 may be a sensor that detects the electrical conduction state. In that case, two platinum wires are placed at a distance from each other, a voltage is applied between the platinum wires, current flows when immersed in liquid between the platinum wires, and the presence of the liquid is detected by detecting it. Can be detected. In addition, the liquid level meter which detects the height of the liquid level by ultrasonic waves may be used.

  The optical fiber and level gauge support member 19 includes a through hole for communicating the space 23 with the internal space of the cylindrical member 13 opposite to the space 23 with respect to the optical fiber and level gauge support member 19. You may be allowed to. When the optical probe 1 is damaged and the liquid sample 25 enters the internal space of the opposite cylindrical member 13, the infiltrated liquid sample passes through the optical fiber and the through hole provided in the level gauge support member 19. 23, it is possible to detect the breakage of the optical probe 1 even if the constituent parts of the optical probe 1 other than the constituent parts forming the space 23 are damaged.

FIG. 3 is a diagram schematically showing an embodiment of the spectroscopic measurement apparatus.
This spectroscopic measurement apparatus is substantially composed of an optical probe 1, a spectroscopic unit 27, a data processing unit 29, and a display unit 31.
First, a specific configuration of the spectroscopic unit 27 will be described.

  The spectroscopic unit 27 includes a tungsten lamp 33 serving as a light source, a convex lens 35, a rotating disk 39 including eight interference filters 37, a convex lens 41, a convex lens 43, and a light receiving element (light detection unit) 45. A drive motor 47 for rotating the rotary disk 39 is provided. The light emitted from the tungsten lamp 33 is collected by the convex lens 35 and passes through the interference filter 37. The interference filter is a band-pass filter that allows only light of a predetermined wavelength to pass. The interference filter 37 held by the rotating disk 39 separates the light into light of a predetermined wavelength within a range of 190 to 2600 nm.

  The light split by the interference filter 37 is collected by the convex lens 41 and irradiated on the incident end face (light projecting optical fiber second end face) 3b of the light projecting optical fiber 3. The projecting optical fiber 3 is connected to the optical probe 1. The structure and optical path of the optical probe 1 are as described with reference to FIGS.

  An emission end face (light receiving optical fiber second end face) 9 b of the light receiving optical fiber 9 of the optical probe 1 is disposed in the spectroscopic unit 27. The light incident on the light receiving optical fiber end surface 9 a by the optical probe 1 enters the convex lens 43 from the light receiving optical fiber end surface 9 b, is condensed, and enters the light receiving element 45. The light receiving element 45 converts the incident light into a current corresponding to the intensity.

  The rotating disk 39 holds eight interference filters 37 at equal angular intervals in the circumferential direction, and is rotationally driven by a driving motor 47 at a predetermined rotational speed, for example, 1200 rpm (Revolutions Per Minute). Each interference filter 37 has predetermined transmission wavelengths different from each other in the range of 190 to 2600 nm depending on the measurement target. Here, when the rotating disk 39 rotates, the interference filters 37 are sequentially inserted into the optical axes of the convex lenses 35 and 41. Then, the light emitted from the tungsten lamp 33 is split by the interference filter 37 and then irradiated to the liquid sample 25 through the light projecting optical fiber 3 and the lens 5 of the optical probe 1. The light that has passed through the liquid sample 25 is reflected by the measurement light reflecting mirror 7, is again collected through the liquid sample 25 and the lens 5, enters the light receiving optical fiber 9, is collected through the convex lens 43, The light enters the light receiving element 45. Thereby, an electrical signal corresponding to the absorbance of light of each wavelength is output from the light receiving element 45.

The data processing unit 29 calculates the liquid sample component concentration according to the light intensity signal from the light receiving element 45.
The level gauge 11 of the optical probe 1 is electrically connected to the data processing unit 29. The data processing unit 29 displays a liquid leakage warning on the display unit 31 based on the liquid leakage detection signal from the liquid level gauge 11. The display unit 31 is, for example, a monitor screen or a warning display lamp. Here, the liquid leakage warning is displayed on the display unit 31 by the data processing unit 29, but a mechanism for displaying the liquid leakage warning on the display unit 31 based on the liquid leakage detection signal from the liquid level gauge 11 may be provided separately. Good.

(Example 2)
FIG. 4 is an enlarged cross-sectional view illustrating the periphery of a lens according to the second embodiment of the optical probe. Parts having the same functions as those in FIGS. 1 and 2 are denoted by the same reference numerals.

  The optical probe 49 includes a light projecting optical fiber 3, a light projecting lens 5a, a measuring light reflecting mirror 7, a light receiving lens 5b, a light receiving optical fiber 9, a cylindrical member 13, a mirror support member 21, a window plate 51, and a sealing member 53. A lens positioning member 55, an optical fiber support member 57, and a window plate pressing member 59.

  The window plate 51 is disposed inside the tip of the cylindrical member 13 made of, for example, quartz. The gap between the window plate 51 and the cylindrical member 13 is filled with a sealing member 53 made of, for example, a fluororesin O-ring. The window plate pressing member 59 positions the window plate 51 and presses the window plate 51 toward the sealing member 53 side.

  The light projecting lens 5a is disposed at a position facing the light projecting optical fiber end surface 3a. The light receiving lens 5b is disposed at a position facing the light receiving optical fiber end surface 9a. The lenses 5a and 5b are positioned by a lens positioning member 55 made of PTFE, for example. The optical fiber end faces 3 a and 9 a are disposed in a space 23 a surrounded by the lenses 5 a and 5 b, the cylindrical member 13, the lens positioning member 55, and the optical fiber support member 57.

  A space 23b surrounded by the lenses 5a and 5b, the cylindrical member 13, the window plate 51, and the lens positioning member 55 is formed. The lens positioning member 55 is provided with a through hole 55a for communicating the spaces 23a and 23b.

The optical fibers 3 and 9 are positioned by an optical fiber support member 57 made of PTFE, for example. The optical fiber support member 57 includes a through hole 57a for communicating the space 23a with a space 23c on the opposite side of the optical fiber support member 57 from the space 23a.
The measuring light reflecting mirror 7 is supported by a mirror support member 21 attached to the cylindrical member 13. The material of the mirror support member 21 is, for example, quartz.

  When the optical probe 49 is used, the optical fibers 3 and 9 of the optical probe 49 are the same as the optical fibers 3 and 9 of the optical probe 1 described with reference to FIGS. Connected to the measuring device. The tip portion of the optical probe 49 is immersed in the liquid sample 25. The tip portion of the optical probe 49 is immersed in the liquid sample 25 to a depth at least where the window plate 51 contacts the liquid sample 25.

  Measurement light is emitted from the optical fiber end surface 3a for light projection. The measurement light is converted into parallel light or condensed light by the light projection lens 5 a, passes through the window plate 51, and is applied to the measurement light reflection mirror 7 through the liquid sample 25. The light reflected by the measurement light reflecting mirror 7 passes through the window plate 51 through the liquid sample 25, then reaches the light receiving lens 5b, and is condensed on the light receiving optical fiber end surface 9a by the light receiving lens 5b.

  When the optical probe 49 is broken and the liquid sample 25 enters the space 23a, the space 23b, or the space 23c, the liquid sample that has entered enters the optical fiber end surface 3a for light projection, the optical fiber end surface 9a for light reception, and the light projection lens. 5a, the light receiving lens 5b, the surface of the window plate 51 on the space 23b side, and the like. Since the optical fiber support member 57 is provided with the through hole 57a, the liquid that has entered the space 23c reaches the space 23a. Since the lens positioning member 55 is provided with the through hole 55a, the liquid that has entered the space 23b also enters the space 23a and further enters the space 23c. Further, the liquid that has entered the space 23a enters the space 23b through the through hole 55a.

  The liquid in contact with the light projecting optical fiber end surface 3a, the light receiving optical fiber end surface 9a, the light projecting lens 5a, the light receiving lens 5b, the surface of the window plate 51 on the space 23b side, etc. is irradiated from the light projecting optical fiber end surface 3a. Thus, the optical path up to the incidence on the light receiving optical fiber end surface 9a is blocked. That is, the liquid enters the optical path in the spaces 23a and 23b.

  The state in which the liquid has entered the optical path in the spaces 23a and 23b is a change in the output of the light receiving element 45 of the spectroscopic measuring device described with reference to FIG. 3, that is, a change in the intensity of light irradiated from the optical fiber end face 9b for receiving light. It can be detected by analyzing.

  For example, the optical probe 49 is simulated for damage in advance, and the output change pattern of the light receiving element 45 is stored in a storage unit provided in the data processing unit 29. Simultaneously with the measurement of the concentration of the liquid sample 25 by the spectroscopic measurement device, the output change pattern accompanying the breakage of the optical probe 49 is collated, and the breakage of the optical probe 49 is constantly monitored.

  FIG. 5 is a diagram illustrating a signal change of the light receiving element 45 when the optical probe 49 is damaged and liquid enters the optical probe 49. FIG. 6 is a diagram showing a signal change of the light receiving element 45 when the tungsten lamp 33 is burned out. FIG. 7 is a diagram showing a signal change when the optical probe 49 is taken out from the liquid sample 25 into the air. FIG. 5 to FIG. 7 show eight wavelengths having different wavelengths. 5 to 7, the vertical axis represents light intensity (arbitrary unit), and the horizontal axis represents time.

  When the optical probe 49 is damaged and liquid enters the optical probe 49, as shown in FIG. 5, the intensity of each of the eight wavelengths decreases but does not become zero. Further, a sudden light intensity change 10 times or more than the light intensity change caused by the concentration change of the liquid sample 25 occurs.

On the other hand, when the tungsten lamp 33 is cut off, the intensities of the eight wavelengths are almost zero as shown in FIG.
Further, when the optical probe 49 is taken out from the liquid sample 25 into the air, the light absorption by the liquid sample 25 is lost as shown in FIG.

  Therefore, a change in the intensity of light irradiated from the optical fiber end face 9b for light reception is monitored to capture a specific change as shown in FIG. 5, for example, 10 changes from a change in light intensity caused by a change in the concentration of the liquid sample 25. By detecting a sudden change in light intensity that is twice or more, breakage of the optical probe 49 can be detected.

  Next, output change pattern examples are listed. Here, description will be made using the light intensities of eight wavelengths among the light irradiated from the optical fiber end face 9b for light reception. If at least two wavelengths are used, it is possible to detect breakage of the optical probe based on the light intensity change pattern.

(1) When the light intensities at the eight wavelengths all decrease and are not all zero and the decrease is greater than the light intensity change caused by the concentration change of the liquid sample, it is determined that the optical probe 49 is damaged. . The light intensity change caused by the change in the concentration of the liquid sample is stored in a storage unit provided in the data processing unit 29.

(2) When the light intensity change values of each of the eight wavelengths are arranged according to the wavelength, if the light intensity decrease rate of the light having a short wavelength is higher than that of the light having a long wavelength, it is determined that the optical probe 49 is broken. To do. When a liquid adheres as a fine water droplet due to breakage of the optical probe 49 at a position where light passes through the optical fiber end faces 3a, 9a, the lenses 5a, 5b, and the window plate 51, the water droplet becomes a scatterer. Scattering follows Rayleigh scattering, and light having a shorter wavelength has a higher scattering rate than light having a longer wavelength. For this reason, light having a shorter wavelength has a higher rate of decrease in light intensity than light having a longer wavelength.

(3) Even if the light intensity is reduced at any one of the eight wavelengths, if the intensity of the other wavelengths is not changed, it is not determined that the optical probe 49 is damaged. The cause of the decrease in the light intensity of only a specific wavelength is assumed to be damage to the electrical system or the optical system related to the interference filter.

(4) When the light intensity of each of the eight wavelengths becomes almost zero, for example, the light intensity does not suddenly become zero in a time of less than 1 second, but gradually increases over a time of 1 second or more. When the voltage drops to, it is determined that the tungsten lamp 33 is not burned out and the optical probe 49 is broken. Such a light intensity change pattern appears when the optical probe 49 is severely damaged, and a large amount of liquid enters the optical path in the optical probe 49, so that no light reaches the optical fiber end surface 9b for receiving light.

  These light intensity change patterns are stored in a storage unit provided in the data processing unit 29, and the data processing unit 29 changes these light intensity change patterns and the intensity change of light emitted from the light receiving optical fiber end surface 9b. Damage to the optical probe 49 can be detected by comparing the pattern.

(Example 3)
FIG. 8 is an enlarged cross-sectional view showing the periphery of the lens of Example 3 of the optical probe. Parts having the same functions as those in FIG.

  The optical probe 61 includes one optical fiber 63 as a light projecting optical fiber and a light receiving optical fiber. A lens 5c that functions as a light projecting lens and a light receiving lens is positioned by a lens positioning member 55 so as to face the optical fiber end surface 63a.

FIG. 9 is a diagram schematically showing another embodiment of the spectrometer. The same parts as those in the spectroscopic measurement apparatus shown in FIG.
The spectroscopic measurement apparatus of this embodiment further includes a half mirror 65, convex lenses 67 and 69, and a mirror 69 in the spectroscopic unit 27, as compared with the spectroscopic apparatus shown in FIG.

  The half mirror 65 and the convex lens 67 are disposed in that order in the optical path between the convex lens 41 and the optical fiber end surface (optical fiber second end surface) 63b. The convex lens 67 and the mirror 69 are arranged in that order in the optical path between the half mirror 65 and the convex lens 43. Here, the convex lens 67 and the mirror 69 may be omitted, and the light reflected by the half mirror 65 may be condensed on the light receiving element 45 by the convex lens 43.

  The light emitted from the tungsten lamp 33 passes through the convex lens 35, the interference filter 37, the convex lens 41, the half mirror 65, and the convex lens 67, and is incident on the end surface 63b of the optical fiber 63, and the optical fiber end surface 63a, the lens 5c of the optical probe 63, The liquid sample 25 is irradiated through the window plate 51 (see also FIG. 8). The light that has passed through the liquid sample 25 is reflected by the measurement light reflecting mirror 7, is again collected through the liquid sample 25 and the lens 5 c, enters the optical fiber 63, is collected through the convex lens 67, and is collected by the half mirror. 65, reflected by the convex lens 69, reflected by the mirror 71, condensed by the convex lens 43, and incident on the light receiving element 45. Thereby, an electrical signal corresponding to the absorbance of light of each wavelength is output from the light receiving element 45.

  The signal intensity of the light receiving element 45, that is, the intensity change of the light irradiated from the optical fiber end face 63b of the optical probe 61 is monitored, and the light intensity change caused by the penetration of the liquid into the spaces 23a, 23b, 23c of the optical probe 61 is monitored. By detecting it, the breakage of the optical probe 61 can be detected.

As mentioned above, although the Example of this invention was described, material, a shape, arrangement | positioning, a dimension, etc. are examples, This invention is not limited to these, In the range of this invention described in the claim Various changes can be made.
For example, in the above embodiment, the structure for forming the spaces 23, 23a, 23b, and 23c in which a part of the optical fiber is disposed is not limited to the configuration of the above embodiment, and a part of the optical fiber is disposed. Any configuration may be used as long as the space can be isolated from the liquid sample.

  The optical probe 49 shown in FIG. 4 and the optical probe 61 shown in FIG. 8 do not include a physical sensor such as a liquid leakage detection sensor, a liquid level gauge, or a platinum electrode, but the spaces 23a, 23b, and 23c. You may make it provide the physical sensor for detecting the penetration | invasion of the liquid to the inside. In this case, a physical sensor is arranged in at least one of the spaces 23a, 23b, and 23c.

  Moreover, based on the intensity change of the light irradiated from the optical fiber end surface 9b for light reception resulting from the liquid entering the optical path in the space 23 using the optical probe 1 shown in FIGS. The breakage of the optical probe 1 may be detected by detecting liquid intrusion into the space 23. In this case, the level gauge 11 of the optical probe 1 is not necessary.

Further, in the optical probe 49 shown in FIG. 4 and the optical probe 61 shown in FIG. 8, instead of the lenses 5 a and 5 b, similar to the optical probe 1 shown in FIG. 1 and FIG. One lens may be provided.
In addition, the optical probe 1 shown in FIGS. 1 and 2 may be provided with a light projecting lens and a light receiving lens in place of the lens 5 in the same manner as the optical probe 49 in FIG.

1, 49, 61 Optical probe 3 Optical fiber 3a for projecting Optical fiber end surface 3b for projecting Optical fiber second end surface 5, 5a, 5b, 5c Lens 9 for receiving light Optical fiber end surface 9a for receiving light Optical fiber second end surface for receiving light 11 Level gauge (sensor)
23, 23a, 23b, 23c Space 25 Liquid sample 29 Data processing unit 31 Display unit 33 Light source 45 Light receiving element (light detection unit)
51 Window plate 63 Optical fiber 63a for projecting and receiving light Optical fiber end surface 63b Optical fiber second end surface

Claims (8)

A light projecting optical fiber for propagating the light irradiated to the liquid sample;
A light-receiving optical fiber for propagating light that has passed through the liquid sample;
A structure for forming a space in which a part of the optical fiber is disposed and isolated from the liquid sample;
An optical probe comprising: a sensor for detecting intrusion of liquid into the space.   The optical probe according to claim 1, wherein the light projecting optical fiber and the light receiving optical fiber are configured by a single optical fiber. One end face of the optical fiber is disposed in the space,
The optical probe according to claim 1, wherein the structure includes a lens through which the light is transmitted at a portion that contacts the liquid sample. One end face of the optical fiber is disposed in the space,
The structure includes a window plate through which the light is transmitted at a portion in contact with the liquid sample.
The optical probe according to any one of claims 1 to 3, further comprising a lens through which the light passes between the end face of the optical fiber and the window plate in the space.   The optical probe according to any one of claims 1 to 4, wherein the sensor is a liquid leakage detection sensor disposed in the space.   The optical probe according to any one of claims 1 to 4, wherein the sensor is a liquid level gauge disposed in the space.   The sensor enters the space based on a change in intensity of light emitted from the end face of the light receiving optical fiber opposite to the end face of the light receiving optical fiber caused by liquid entering the optical path in the space. The optical probe according to claim 3, wherein the intrusion of the liquid is detected. An optical probe according to any one of claims 1 to 7,
A light source for irradiating light to the second optical fiber for projecting optical fiber opposite to the optical fiber end surface for projecting light;
A light detection unit for receiving light irradiated from the second optical fiber for receiving light on the side opposite to the end surface of the optical fiber for receiving light;
A data processing unit for calculating a liquid sample component concentration according to a light intensity signal from the light detection unit;
And a display unit that displays a liquid leakage warning based on a liquid leakage detection signal from the sensor.

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