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WO2006109408A1 - Sonde optique d’atténuation de réflexion totale et spectrophotomètre dans l’ultraviolet lointain - Google Patents

Sonde optique d’atténuation de réflexion totale et spectrophotomètre dans l’ultraviolet lointain Download PDF

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Publication number
WO2006109408A1
WO2006109408A1 PCT/JP2006/305262 JP2006305262W WO2006109408A1 WO 2006109408 A1 WO2006109408 A1 WO 2006109408A1 JP 2006305262 W JP2006305262 W JP 2006305262W WO 2006109408 A1 WO2006109408 A1 WO 2006109408A1
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WO
WIPO (PCT)
Prior art keywords
optical probe
optical
total reflection
refractive index
light
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2006/305262
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English (en)
Japanese (ja)
Inventor
Noboru Higashi
Yukihiro Ozaki
Akifumi Ikehata
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Kurashiki Spinning Co Ltd
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Kurashiki Spinning Co Ltd
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Application filed by Kurashiki Spinning Co Ltd filed Critical Kurashiki Spinning Co Ltd
Publication of WO2006109408A1 publication Critical patent/WO2006109408A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/55—Specular reflectivity
    • G01N21/552—Attenuated total reflection
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light

Definitions

  • the present invention relates to spectroscopic analysis in the far ultraviolet region.
  • spectroscopic analysis is widely used as a very effective means.
  • the spectroscopic analysis methods are roughly classified into ultraviolet-visible spectroscopy, near-infrared spectroscopy, and infrared spectroscopy depending on the measurement wavelength region.
  • the present invention focuses on the attenuated total reflection (Attenuated Total Reflectance) method as a method for measuring the absorption spectrum of a substance having very large absorption.
  • the total reflection attenuation method can measure the amount of light absorbed in the sample by the soaking of light of the wavelength order (evanescent wave) that is formed when light is totally reflected on the surface of the optical probe. Theoretically, an absorption spectrum similar to the transmission spectrum due to the cell length in the wavelength order can be obtained.
  • Japanese Patent Application Laid-Open No. 62-75230 proposes a method for measuring concentrated solutions by attenuated total reflection using an optical probe.
  • the optical system for optical analysis described in US Pat. No. 5,703,366 uses a probe that totally reflects incident light at the surface in contact with the sample substance in the infrared optical system.
  • the disadvantages of probes made of a single crystal member corrosion resistance, mechanical properties, high price, etc.
  • the probe is assembled from the first crystal member and the second crystal member in contact with the first crystal member.
  • the second crystal member has a surface that contacts the sample material.
  • the two crystal members have substantially the same refractive index.
  • the first crystal member is, for example, selenium zinc (ZnSe).
  • ZnSe selenium zinc
  • a diamond is used as an optical probe having a minute surface that causes total reflection of incident light and contacts the sample.
  • a ZnSe crystal is used as a condensing lens that guides light to the diamond crystal.
  • ZnSe is an optical material having substantially the same refractive index as diamond.
  • a second layer for example, zinc oxide, tin dioxide
  • a transparent first layer for example, silicon
  • the second layer is a layer in contact with the sample.
  • an optical material having a high refractive index is used as the first layer
  • an optical material having a low refractive index is used as the second layer.
  • the incident light on the first layer is totally reflected at the interface between the first layer and the second layer at the end face angle and the incident angle, and is opposite to the second layer. Do not enter the sample located on the side.
  • the idea of this invention is unknown.
  • an infrared transmitting optical device such as SiO 2 ZnSe is used.
  • a diamond thin film or a carbon (DLC) thin film containing a diamond structure (for example, a thickness of 600 nm) is formed on the surface of an optical element having a material strength in order to improve surface strength and moisture resistance.
  • an optical element is the multiple reflection prism of the total reflection attenuation absorption measurement accessory.
  • Patent Document 1 JP-A-62-75230
  • Patent Document 2 JP-A-7-12716
  • Patent Document 3 US Pat. No. 5,703,366
  • Patent Document 4 US Patent No. 6907390B1
  • Patent Document 5 JP 2001-91710 A
  • Patent Document 6 JP-A-64-56401
  • An object of the invention is to make it possible to easily perform spectroscopic measurement in the far ultraviolet region for a substance having a large absorption.
  • a first total reflection attenuation optical probe includes a first portion having a first optical material force having light transmission characteristics in a far ultraviolet region, an interface in contact with the first portion, and a sample substance. And a second portion that also has a second optical material power having a refractive index higher than that of the first portion.
  • the light that has passed through the first part enters the second part and can enter the plane of the second part that contacts the sample material at an angle of incidence greater than the critical angle. With a unique shape. If the refractive index of the sample material is smaller than that of the second optical material, total reflection occurs on the plane in contact with the sample material.
  • a plane of the second portion in contact with the sample material and an interface between the first portion and the second portion are parallel to each other.
  • the interface is semicircular.
  • the plane of the second portion and the interface are perpendicular to each other.
  • light transmission characteristics in the far ultraviolet region Preferably, further, light transmission characteristics in the far ultraviolet region.
  • a third portion that also has a third optical material force having a property, and the third portion is located on the opposite side of the second portion with respect to the second portion.
  • the first optical material is any one of magnesium fluoride, lithium fluoride, calcium fluoride, and barium fluoride,
  • the optical material is synthetic silica, quartz, sapphire, zinc selenide, and diamond!
  • the interface between the first part and the second part is such that light transmitted through the first part can enter the second part perpendicularly. Yes, and has a shape that allows the light that is totally reflected by the surface force to be incident vertically when entering the first portion.
  • the second total reflection attenuating optical probe according to the present invention is made of an optical material having light transmission characteristics in the far ultraviolet region, and the refractive index continuously changes at least partially.
  • This probe has a plane that totally reflects light having an incident angle greater than the critical angle on the side in contact with the sample substance, and the refractive index in the far ultraviolet region in the first portion including a part of the plane. Is higher than the rest.
  • the optical material is, for example, magnesium fluoride, and the portion where the refractive index continuously changes is formed by ion plating.
  • the first or second total reflection attenuating optical probe includes a coating layer (for example, a quartz or quartz thin film) having a thickness sufficiently thinner than a measurement wavelength on a surface in contact with water.
  • a coating layer for example, a quartz or quartz thin film
  • the far-ultraviolet spectroscopic measurement device includes a far-total ultraviolet light beam that is disposed in contact with water or an aqueous solution.
  • a light source for irradiating light a light receiving element for detecting the total reflection light of the total reflection attenuation type optical probe force, and a spectroscopic element for dispersing far ultraviolet light in the optical path from the light source to the light receiving element.
  • FIG.3 Diagram showing the configuration of a general reflection-absorption optical probe.
  • FIG.4 Diagram showing the configuration of a two-layer optical probe
  • FIG. 6 Diagram of a variation of the optical probe in Fig. 4.
  • FIG. 7 Diagram showing the configuration of an optical probe with a vertical three-layer structure
  • FIG. 8 is a diagram showing a configuration of a modification of the optical probe in FIG.
  • FIG. 9 is a diagram showing the configuration of another modification of the optical probe in FIG.
  • FIG. 11 is a graph showing the wavelength dependence of the refractive index of each optical material in the far ultraviolet region.
  • FIG. 16 is a graph showing the change in absorbance due to solute concentration with an optical probe whose surface is modified by ion plating.
  • the absorption spectrum of water that appears in the near-infrared region cannot measure the concentration of trace components that are inherently forbidden transitions and weakly absorbed. Therefore, the inventor conducted research focusing on the far ultraviolet spectrum, and pure water has a very large sharp absorption peak near 160 nm in the far ultraviolet region, and changes in the bottom of the sharp absorption. By measuring, it was found that the concentration of a very small amount of dissolved component hydrated in an aqueous solution can be measured. In other words, water itself shows a very steep decrease in absorption spectrum from the absorption peak near 160 nm to the absorption bottom near 200 nm, and the peak position and bandwidth of this absorption band are very small. It also changes with hydration of the minute.
  • Figure 1 shows the far-ultraviolet spectrum of an HC1 aqueous solution with 11 concentrations (1, 2, 3, 4, 5, 6, 8, 10, 12, 16, 20 ppm) in the range of 0-20 ppm.
  • the model correlation coefficient R and standard deviation ⁇ were 0.9987 and 0.18 ppm. It was possible to measure a very small amount of HC1 at least up to lOOppm with high accuracy.
  • the detection limit of HC1 in the aqueous solution in this measurement example was 0.5 ppm.
  • the measurement wavelength was limited to the bottom portion of the water absorption band at 180 to 210 nm.
  • the absorption cell with a peak near 160 nm of water has a very large extinction coefficient.
  • the measurement cell length must be reduced to several hundred nm. It is difficult to realize This is because of However, in order to carry out more sensitive component analysis, the change in spectrum absorption appears to be more significant 160 ⁇ ! It is necessary to measure the strong absorption slope of ⁇ 180nm.
  • ATR method total reflection attenuation absorption method
  • the spectral change force of the solvent, water is measured by the optical probe using the total reflection attenuation absorption method described below (hereinafter referred to as the total reflection attenuation optical probe) and the far ultraviolet spectrometer.
  • the measurement wavelength range is 160 ⁇ ! High sensitivity can be achieved by extending to ⁇ 180nm.
  • the refractive index is higher V
  • the medium 14 for example, synthetic quartz
  • the refractive index are lower
  • the medium sample material to be measured.
  • the medium 16 force with higher refractive index hits the interface between 18 (for example, water)
  • the ray 16 is totally reflected if the incident angle ⁇ is larger than the critical angle.
  • the light beam 16 enters a medium 18 having a lower refractive index into the wavelength order by a certain distance, travels toward the interface, and is then reflected.
  • the light rays that enter the medium 18 having a lower refractive index are called evanescent waves.
  • the electric field strength of the evanescent wave is maximum at the reflection point, and decays as soon as it is directed in the direction of the interface and the direction perpendicular to the interface.
  • the force evanescent wave electric field strength is shown schematically in the direction perpendicular to the interface of the evanescent wave above the surface 20 in Fig. 3. penetration depth).
  • the absorption of light with respect to the subduction (evanescent wave) of the wavelength order formed when the light is totally reflected can be measured from the reflected light. Since the penetration depth of this light corresponds to the optical path length of a normal transmission spectrum, an absorption spectrum similar to the transmission spectrum by the cell length of the wavelength order can be obtained theoretically.
  • optical probe total reflection attenuating optical probe
  • the refractive index of the material of the optical probe is larger than the refractive index of the sample substance.
  • optical transmittance of the optical probe material is sufficiently high (transparent) in the measurement wavelength region.
  • the optical probe and the spectroscopic measurement apparatus can also perform spectroscopic measurement using the attenuated total reflection method even for substances having large absorption in the far ultraviolet region other than water.
  • the total reflection attenuating optical probe has, for example, a combined force of the first part and the second part.
  • the first portion is made of a first optical material having light transmission characteristics in the far ultraviolet region.
  • the second part is a second optical material force having an interface in contact with the first part and a plane in contact with the sample substance, and having a refractive index higher than the refractive index of the sample in the far ultraviolet region.
  • the second optical material has a higher refractive index than the first optical material.
  • the second optical material generally cannot constitute an optical probe only with the second optical material having a lower transmittance than the first optical material.
  • the light ray enters the first part, passes through the first part, is refracted at the interface between the first part and the second part, enters the second part, and is totally reflected by the plane.
  • This interface has a shape that allows light rays to enter the plane at an incident angle greater than the critical angle. At this time, a part of the light beam is reflected as an evanescent wave after passing through the sample.
  • the two-layer structure optical probe of the first embodiment includes a holding material 10 and a high refractive index optical material layer 14 in close contact with the first surface 12 thereof.
  • the thickness of the high refractive index optical material layer 14 is preferably about several meters, which is sufficiently longer than the measurement wavelength. Also generally far ultraviolet Because the transmittance is low!
  • the high refractive index optical material layer 14 having a refractive index larger than that of the sample material is provided with a surface 20 in contact with the sample material 18, and the surface 20 enables total reflection.
  • the surface 20 is preferably substantially parallel to the interface 12, but it need not be parallel.
  • the holding material 10 also has an optical material force such as magnesium fluoride, lithium fluoride, and barium fluoride.
  • the shape of the holding member 10 is a triangular prism in this example, but is not limited thereto.
  • the light beam 16 incident on the holding material 10 passes through the holding material 10, is refracted at the interface 12, and enters the high refractive index material layer 14.
  • the light beam 16 transmitted through the high refractive index optical material layer 14 is incident on the surface 20 at an incident angle greater than the critical angle and is totally reflected.
  • the reflected light is refracted at the interface 12 and enters the holding material 10, passes through the holding material 10, and goes out.
  • the reflected light is measured, and the absorbance of the sample substance 18 is measured.
  • the two-layer structure optical probe according to the first embodiment will be further described.
  • the second optical material 14 in contact with water as the sample material needs to have a refractive index larger than the refractive index of water in the wavelength region reaching the far ultraviolet region near its refractive power of 60 nm.
  • materials that satisfy this requirement are quartz (or quartz) and sapphire.
  • the transmittance of quartz and sapphire in the far ultraviolet region near 160 nm is less than 50% at lmm thickness.
  • the second optical material has a sufficiently thin thickness of several hundreds of zm or less, the transmittance is 90% or more even near 160 nm, so that it can function as a total reflection attenuation probe.
  • optical materials such as magnesium fluoride (see Fig.
  • lithium fluoride, and barium fluoride have a refractive index lower than that of quartz up to the vacuum ultraviolet region and have a thickness of several millimeters or more.
  • the light transmittance is not impaired. Therefore, for example, in the ultraviolet region of 150 nm or more, these optical materials having a refractive index smaller than that of the second optical material and having sufficient transmission characteristics are used as the probe holding material 10, and the second optical material is totally reflected on the optical material.
  • a two-layer structure that forms a thin film 14 that is thicker than it can function as a probe (for example, 1 m or more for a wavelength range of 160 to 250 nm) is used.
  • the refractive index of each material is about 1 in the far ultraviolet region near 160 nm. 5, about 2.2 and about 1.6. This makes it possible to realize an optical probe that can measure the attenuated total reflection of water and aqueous solutions near 160 nm. Using this optical probe, measurement of trace component concentrations in aqueous solution Can be provided.
  • the optical probe having the two-layer structure described above has the first portion (holding) of the first optical material having light transmission characteristics in the far ultraviolet region to be measured (for example, the far ultraviolet wavelength region longer than 15 Onm).
  • the second optical material has a higher refractive index than the sample substance and the first optical material in the far ultraviolet region, and the second portion 14 has a thickness sufficiently longer than the measurement wavelength.
  • a surface 20 that totally reflects light having an incident angle greater than the critical angle is provided on the side in contact with the sample material 18.
  • the optical probe of the second embodiment as shown in FIG. 5, at least a part of the optical probe 14 ′ having an optical material (magnesium fluoride, etc.) having light transmission characteristics in the far ultraviolet region is also present.
  • the refractive index changes continuously.
  • the vicinity of the surface 20 in contact with the sample substance 18 is modified so that the refractive index is continuously increased as shown in the upper right of FIG.
  • the refractive index in the vicinity of the surface is higher than the refractive index in other portions, and finally higher in the plane 20 than the refractive index of the sample material 18.
  • the light reaches the surface in a circular arc or elliptical orbit.
  • ion plating is used for example.
  • metal ions such as aluminum, magnesium, argon, and sodium are distributed by ion plating on the surface of a vacuum ultraviolet transmission optical material such as magnesium fluoride, lithium fluoride, calcium fluoride, and barium fluoride with an energy of about 100 KWV. .
  • a vacuum ultraviolet transmission optical material such as magnesium fluoride, lithium fluoride, calcium fluoride, and barium fluoride with an energy of about 100 KWV. .
  • the embedded impurity concentration continuously changes and the refractive index continuously changes.
  • the refractive index of 180 nm to 150 nm can be increased intentionally.
  • an optical probe for total reflection attenuation absorption method can be formed.
  • the sample substance is When it is water, some of the optical material may ionize and elute into the water sample.
  • a third layer is formed of a material (for example, synthetic stone or quartz) on the surface 20 in contact with the sample substance, and does not elute into the sample substance. Since the refractive index of the optical material is larger than that of quartz (quartz), the incident light is totally reflected at the interface 20 between the optical material and the quartz (quartz) coating layer 22. At this time, if the coating layer 22 is sufficiently thinner than the measurement wavelength and has a thickness (about several tens of nm), the penetrating light (evanescent wave) reaches the sample, so that the absorbance of the sample can be measured.
  • the positional relationship between the holding material and the high refractive index optical material layer is made different in order to reduce the incident angle.
  • the surface where the high refractive index optical material layer is in contact with the sample substance and the interface where the high refractive index optical material layer is in contact with the holding material are positioned perpendicular to each other, for example.
  • FIG. 7 shows an optical probe having a vertical three-layer structure according to the fourth embodiment.
  • This optical probe includes a rectangular high refractive index optical material layer 40 and a first holding material 42 and a second holding material 44 which are in contact with both sides thereof.
  • the sample material 46 is in contact with the end face 48 in the longitudinal direction of the high refractive index optical material layer 40 having a higher refractive index than the sample material 46.
  • the thickness of the high-refractive index optical material layer 40 is preferably several hundred ⁇ m or less, but can be barely practical up to about lmm.
  • the light beam 50 incident on the first holding material 42 enters the interface 52 between the first holding material 42 and the high refractive index optical material layer 40 and is refracted. Incident and totally reflected.
  • the reflected light beam is refracted at the second interface 54 between the high refractive index optical material layer 40 and the second holding material 44 and exits from the second holding material 44.
  • the absorbance of the sample substance 46 is measured.
  • the outer shape of the first holding member 42 is preferably designed so that the light beam 50 is incident substantially perpendicularly from the outside.
  • the optical material for the high refractive index optical material layer 40 and the holding materials 42 and 44 the same materials as those in the first embodiment are used.
  • FIG. 8 shows a modification of the optical probe of the fourth embodiment.
  • the second holding material is omitted.
  • the light beam 50 reflected by the end surface 48 of the high refractive index optical material layer 40 is emitted into the air at the interface 54.
  • FIG. 9 shows another modification of the optical probe of the fourth embodiment.
  • the outer shapes 56 and 58 of the first holding material 42 'and the second holding material 44' are semicircular. Therefore, the light beam 50 can be incident substantially perpendicular to the holding material 42 'even if the incident direction is changed.
  • FIG. 10 shows an optical probe according to the fifth embodiment.
  • the high refractive index optical material layer 60 includes an end face 64 in contact with the sample material 62.
  • the side of the high refractive index optical material layer 60 that does not contact the sample material 62 is in contact with the holding material 66 through the interface 68.
  • Both the interface 68 and the outer shape 70 of the retaining material 66 are semicircular. Therefore, the light beam 50 can enter the holding member 66 and the interface 68 almost perpendicularly even if the incident direction changes.
  • FIG. 11 shows various materials, that is, sapphire, synthetic quartz, quartz (SiO 2), glass, and the like.
  • FIG. 12 shows the calculation data of the incident angle dependence of the absorbance of pure water measured by the vertical three-layer structure optical probe according to the fourth embodiment.
  • quartz quartz
  • the absorbance peak decreases as the incident angle ⁇ force 1 ⁇ 28 ° force increases. If the high refractive index optical material layer is also quartz (quartz), the same result is obtained in the first embodiment.
  • FIG. 13 shows quartz (quartz) as a high refractive index optical material in the two-layer structure optical probe according to the first embodiment or the vertical three-layer structure optical probe according to the fourth embodiment.
  • the wavelength dependence of the penetration depth when using is shown.
  • Incident angle ⁇ force 1 ⁇ 28 ° force
  • the depth of penetration decreases as the force increases.
  • the penetration depth is 50 to lOOnm at a wavelength near 160 nm. This corresponds to the optical path length in a normal optical cell.
  • FIG. 14 shows the absorbance of aqueous solutions having different solute concentrations when quartz (quartz) is used as the optical material of the high refractive index optical material layer in the vertical three-layer structure optical probe according to the fourth embodiment.
  • quartz quartz
  • the incident angle ⁇ was 70 °.
  • Absorbance peaks decrease with increasing solute concentration.
  • the high refractive index optical material layer is also made of quartz ( Crystal), the same result is obtained in the first embodiment.
  • FIG. 15 shows the absorbance spectra of aqueous solutions having different solute concentrations when sapphire is used as the optical material of the high refractive index optical material layer in the vertical three-layer structure optical probe according to the fourth embodiment.
  • the incident angle ⁇ was 60 °.
  • the absorbance peak decreases as the solute concentration increases. If the high refractive index optical material layer is also a sapphire, the same result is obtained in the first embodiment.
  • the absorbance peak decreases as the solute concentration increases.
  • FIG. 17 is a spectrum in the far ultraviolet region when pure water is measured using the quartz-coated optical probe according to the third embodiment.
  • Sapphire was used as the second optical material.
  • the absorbance of water having a huge absorption peak at 160 nm is assumed (in the case of lmm transmission measurement), and the thickness of the quartz coating film is 0, 10, 20, 30, 40 , The spectrum was obtained at 50 nm. (Note that the spectrum was obtained based on the ratio of the reflectance of the sample material to water.) As a result, even if a quartz thin film is present, the evanescent wave reaches the sample water layer. I was divided.
  • FIG. 18 is a spectrum in the far ultraviolet region when aqueous solutions having different solute concentrations are measured using the quartz-coated optical probe according to the third embodiment.
  • Sapphire was used as the second optical material.
  • quartz quartz (quartz) coating film (thickness 20 nm).
  • the far ultraviolet spectrum is calculated.
  • the incident angles are both 60 °.
  • changes in the far-ultraviolet spectrum appear as the solute concentration increases. It can be seen that the concentration can be quantified. This result is exactly the same as in the fourth embodiment even when the quartz coating is applied to the surface in contact with the sample.
  • FIG. 19 shows the configuration and refractive index profile of the optical probe of the 78th embodiment. Similar to the optical probe of the first embodiment, this optical probe is a first optical material (magnesium fluoride, lithium fluoride, barium fluoride, etc.) having light transmission characteristics in the far ultraviolet wavelength region. It consists of a first part 10 'and a second part 14' of a second optical material (synthetic stone, sapphire, etc.) placed in contact with the first part 10 '. The second optical material has a higher refractive index than water in the far ultraviolet region. The difference from the optical probe of the first embodiment is that the interfaces 12 ′ and 12 ′′ between the first portion 10 ′ and the second portion 14 ′ allow the vertical incidence of incident light and reflected light.
  • first optical material magnesium fluoride, lithium fluoride, barium fluoride, etc.
  • the second portion 14 ' is to totally reflect light having an incident angle greater than the critical angle at the interface 20 with the sample substance 18.
  • the thickness of the second portion 14' has sufficient transmission characteristics. The normal incidence described above is to reduce the reflection loss when entering the second portion 14 ', and an anti-reflection coating is applied to the interfaces 22 and 22' having a large refractive index gap. If sapphire is used for the second part 14 ', it is desirable to apply non-reflective coating to the interfaces 12' and 12 ". Further, the surfaces 22 and 22 'of the first portion 10' are also provided with a shape that makes normal incidence. Total reflection occurs at the surface where the second portion 14 ′ contacts the sample material 18.
  • the evanescent wave travels in the direction of the interface between the second portion 14 ′ and the sample material 18. This reflected wave is measured to measure the absorption of the sample material. Therefore, the reflected wave is affected by transmission to the sample material (water or aqueous solution) 18. Also, as in the second embodiment, when using a surface modification portion by Mg F ion plating, the light beam is bent in the traveling direction.
  • the refractive index profile shows the refractive index change along ray 16 when magnesium fluoride is used as the first optical material and quartz and sapphire are used as the second optical material. It also shows the change in refractive index when a surface modification part is provided by ion plating of an optical material of magnesium fluoride.
  • FIG. 20 shows the configuration of a deep ultraviolet spectroscopic trace component concentration meter (measurement wavelength: 160 to 210 nm) using any of the optical probes described above (total reflection attenuation optical probe).
  • An optical probe 102 is provided in contact with the sample material 18 in the sample passage 100. Ensure that sample material is introduced into the cell and that the optical probe faces the sample material in the cell. Alternatively, without using a cell, for example, a wall surface of a pipe for introducing a spraying path may be used as a probe.
  • Light generated from an ultraviolet light source (for example, a deuterium lamp) 104 passes through a grating mirror 106, which is a monochromator, is reflected by the mirror 108, and enters the optical probe 102.
  • an ultraviolet light source for example, a deuterium lamp
  • the incident angle to the optical probe 102 is set appropriately.
  • the reflected light from the optical probe 102 is reflected by the mirror 110 and then enters the ultraviolet light sensor 112.
  • nitrogen gas is introduced into the above-mentioned optical system.
  • the air is replaced with argon gas or the air itself is evacuated to vacuum, a method can be used.
  • the spectrum detected by the ultraviolet light sensor 112 is processed by the signal processing unit 114, and the absorbance is calculated based on the measurement data.
  • a calibration curve can be created by a known multivariate analysis for absorbance at multiple wavelengths. To measure the water spectrum at 160 nm, the cell length needs to be about lOOnm.
  • the above-mentioned optical probe measures various liquids, gases, and solid samples that have large absorption in the far ultraviolet region in addition to water using the attenuated total reflection method. It can. For example, liquids such as isopropyl alcohol and gases such as oxygen can be measured.

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Abstract

L’invention concerne une sonde optique d’atténuation de réflexion totale pour une utilisation dans la spectrophotométrie dans la région ultraviolette lointaine d’un échantillon comme une trace de composant soluté dissout dans l’eau. La sonde optique comprend une première portion d’un premier matériau optique présentant une caractéristique de transmission de lumière dans la région ultraviolette lointaine et une seconde portion d’un second matériau optique au contact de celle-ci. Par exemple, le second matériau optique présente un indice de réfraction plus élevé dans la région ultraviolette lointaine que dans la première portion. La seconde portion est disposée sur le côté au contact d’un échantillon, avec une surface qui reflète totalement la lumière ayant un angle incident supérieur ou égal à l’angle critique. En variante, la sonde optique se compose d’un matériau optique présentant une caractéristique de transmission de lumière dans la région ultraviolette lointaine et pourvu, sur le côté au contact d’un échantillon, d’une surface qui reflète totalement la lumière ayant un angle incident supérieur ou égal à l’angle critique. L’indice de réfraction au voisinage de la surface est plus élevé dans la région ultraviolette lointaine que dans l’autre partie.
PCT/JP2006/305262 2005-04-11 2006-03-16 Sonde optique d’atténuation de réflexion totale et spectrophotomètre dans l’ultraviolet lointain Ceased WO2006109408A1 (fr)

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EP1970695A1 (fr) * 2007-03-08 2008-09-17 Kurashiki Boseki Kabushiki Kaisha Sonde de réflexion totale atténuée et spectromètre la comportant
WO2009110463A1 (fr) * 2008-03-04 2009-09-11 倉敷紡績株式会社 Spectroscopie d'un ultraviolet lointain de type à atténuation de réflexion totale et dispositif de mesure de concentration utilisant la spectroscopie
EP1998163A4 (fr) * 2006-03-16 2010-12-15 Kurashiki Boseki Kk Sonde optique a attenuation de reflexion totale et dispositif spectrometrique pour solution aqueuse
CN105071216A (zh) * 2015-09-10 2015-11-18 中国科学院理化技术研究所 一种提高短波深紫外激光输出效率的倍频晶体耦合器
CN115903108A (zh) * 2022-12-07 2023-04-04 光子集成(温州)创新研究院 一种atr晶体及附件

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EP1998163A4 (fr) * 2006-03-16 2010-12-15 Kurashiki Boseki Kk Sonde optique a attenuation de reflexion totale et dispositif spectrometrique pour solution aqueuse
US7978331B2 (en) 2006-03-16 2011-07-12 Kurashiki Boseki Kabushiki Kaisha Attenuated total reflection optical probe and apparatus therewith for spectroscopic measurement of aqueous solution
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CN115903108A (zh) * 2022-12-07 2023-04-04 光子集成(温州)创新研究院 一种atr晶体及附件

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