JP2000321128A - Integrating sphere and spectroscopic measuring apparatus employing it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an integrating sphere exhibiting excellent measurement accuracy in far ultraviolet and vacuum ultraviolet regions by providing a phosphor coating containing a phosphor and a fluororesin coating containing fluororesin particles on the inner surface of a hollow sphere having a light incident window and a light receiving window. SOLUTION: A sample light 12 passes through the incident window 8 of an integrating sphere 7 and irradiates a light irradiating region 15, i.e., a phosphor coating 10 containing a phosphor, being irradiated directly with the sample light 12. A fluorescent light beam 22 emitted by irradiating the sample light 12 reaches a light reflecting/ diffusing region 16 on the inner surface of the integrating sphere 7 other than the light irradiating region 15, i.e., a detector 13 comprising a fluororesin coating 17 containing fluororesin particles and used for measurement. On the other hand, a reference light introduced from the reflector passes through another incident window from an angle shifted by 90 deg. from the incident window 8 and irradiates the phosphor coating 10 and eventually reaches the detector 13 while being diffuse reflected on the surface of the fluororesin coating 17 and used for measurement. A light having far ultraviolet or vacuum ultraviolet wavelength region of 300 nm or less is employed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an integrating sphere and a spectrometer for use in a spectrometer for measuring the spectral energy intensity and distribution of light. The present invention relates to an integrating sphere and a spectrometer that are effective for improving measurement accuracy in the deep ultraviolet region and the vacuum ultraviolet region, which are difficult and have low accuracy.

[0002]

2. Description of the Related Art Conventionally, light energy is measured by measuring spectral energy distribution, spectral transmittance, spectral reflectance, and the like, and these measurements are mainly performed in the visible region. The spectrometer measures the light emitted from the light source into monochromatic light by a spectroscope, splits the monochromatic light into reference light and sample light by a sector mirror, and the reference light is guided directly to an integrating sphere by a reflection mirror, The sample light is guided to the integrating sphere via the sample by the reflection mirror, and the energy of the light is measured by comparing the luminous flux of each light taken out from the integrating sphere.

As a spectroscope used for spectroscopy in a spectrometer, an optical prism, a diffraction grating, a wavelength cut filter, an interference filter, and the like are properly used depending on the application and accuracy.

[0004] Further, since a relatively stable light source such as a halogen lamp, mainly a tungsten light bulb, is used as a light source used for the measurement, no problem occurred.
Integrating spheres that have been used to measure spectral characteristics have been used with white powder such as barium sulfate applied to the inner surface.

[0005]

However, in contrast to the conventional spectrometer which mainly performs the visible region,
Recently, devices utilizing light rays in the ultraviolet region have been used in various fields. In particular, a light source such as a stepper used for manufacturing a semiconductor is a mercury lamp g-line (λ = 435).
8 °) to i-line (λ = 3650 °), and more recently to a gas laser KrF (λ = 2486 °) laser. This means that the limits of semiconductor processing are from line widths of 0.35 μm to 0.16 μm, and even 0.12 μm.
This indicates that it is about to shift to μm or less.
In the near future, it is inevitable that the light source used there will be a laser in the vacuum ultraviolet region, and ArF (λ = 19)
34 °), and F2 laser (λ = 1570 °) is promising.

The major problem here is the optical system used therein. This is because there are many problems, such as whether the quartz used for the KrF laser can be used as a glass material and how far fluorite can handle.
Further, even a spectroscopic spectrum measuring device or the like used for measurement evaluation does not correspond to the vacuum ultraviolet region, so that accurate measurement evaluation is unlikely to be expected.

For the measurement of the ultraviolet region, a white pigment such as barium sulfate is conventionally applied to the inner surface of the integrating sphere.
In the past, there was no problem because light mainly in the visible region was present, but in the ultraviolet region, particularly in the deep ultraviolet and vacuum ultraviolet regions, absorption was large and sufficient performance could not be exhibited.

The present invention has been made in view of such problems of the prior art, and more particularly, an integrating sphere having excellent measurement accuracy in light in the ultraviolet region, particularly in the deep ultraviolet and vacuum ultraviolet regions, and the use thereof. It is an object of the present invention to provide a spectrometer that has been used.

[0009]

That is, the present invention relates to an integrating sphere for use in a spectrometer for measuring the spectral energy intensity and distribution of light, wherein the incident window receives light and the light receiving window receives light. And a fluorescent film containing a fluorescent material and a fluororesin film containing particles of a fluororesin are provided on the inner surface of a hollow sphere having at least one of the following.

The present invention is also a spectrometer for measuring the spectral energy intensity and distribution of light using the integrating sphere.

Preferably, the wavelength range of the light is 300 nm or less. It is preferable that the inner surface of the hollow sphere is made of a light-reflective substrate made of metal or a thin film of metal. Preferably, the phosphor is an inorganic phosphor or an organic phosphor. The inorganic phosphor is BaMg ₂ Al ₁₆ O ₂₇ : Eu;
(SrCaBa) ₅ (PO ₄ ) ₃ Cl: Eu, BaSi ₂
O ₅ : Pb, YPO ₄ : Ce, Sr ₂ P ₂ O ₇ : E
u, ZnS: preferably at least one selected from Cu and Al.

It is preferable that the phosphor coating contains the phosphor and a binder for suspending and supporting the phosphor in an amount of 0 to 10 parts by weight based on 100 parts by weight of the phosphor. Preferably, the binder comprises a water-soluble resin. It is preferable that the phosphor coating is provided in a light irradiation area of the inner surface of the hollow sphere which is directly irradiated with the incident light.

It is preferable that the fluororesin particles are particles of a tetrafluoroethylene resin, a derivative thereof, and a copolymer resin thereof. It is preferable that the fluororesin film contains 0 to 10 parts by weight of a binder for suspending and supporting the fluororesin particles and the fluororesin particles based on 100 parts by weight of the fluororesin particles. Preferably, the binder comprises a water-soluble resin. It is preferable that the fluororesin coating is provided in an area other than a light irradiation area on the inner surface of the hollow sphere where the incident light is directly irradiated.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION In the measurement of light energy, the present inventors applied the above-mentioned conventional white pigment such as barium sulfate on the inner surface to light in the ultraviolet region, particularly in the deep ultraviolet and vacuum ultraviolet regions. In order to improve and solve the problems that occur when using an integrating sphere, we attempted to improve and improve the integrating sphere, which is the main point of measurement and evaluation of spectral energy, in order to achieve highly accurate measurement evaluation and technological progress. As a result, the conventional integrating sphere is coated with a white pigment such as barium sulfate corresponding to the measurement of visible light, but a sufficient amount of reflected light cannot be obtained due to large absorption for light in the far ultraviolet region. It has been found that the measurement of low response causes poor accuracy.

Conventionally, as a characteristic required of an integrating sphere,
1. 1. high reflectance; 2. uniform diffusion (scattering); Uniform spectral characteristics. In addition, in order to measure the light energy of far ultraviolet light and vacuum ultraviolet light, it is necessary to use 4. 4. Conversion of measuring instrument to sensitive wavelength range; Prevention of pollution by environment and atmosphere. However, the conversion of the light measuring device used for measuring the visible light into the sensitive wavelength range is based on the fact that the photodetector such as a photoelectric tube for spectroscopic measurement corresponds to the far ultraviolet and vacuum ultraviolet regions including the window material. Not as a result, far ultraviolet,
Direct measurement of vacuum ultraviolet is difficult.

Accordingly, the present invention uses a phosphor coating containing a phosphor in a part of the inner surface of the hollow sphere of the integrating sphere, which is irradiated with the phosphor, to convert the ultraviolet light into a long-wavelength light having a fluorescence wavelength by wavelength conversion. It is characterized in that the measurement is performed in a long wavelength region of visible light that is converted and adapted to the characteristics of the light receiver. These features include: 1. Adoption of a phosphor that emits light at a long wavelength. 2. Place phosphor only in the direct light irradiation area; 3. Adoption of a binder resin for suspension support which does not absorb ultraviolet rays.
3. Eco-friendly (consideration) coating; For example, the phosphor is reused (recycled).

Further, the present invention solves the problems of a decrease in the reflectivity and reflection characteristics of the inner surface of the integrating sphere, which have been serious problems.
The measurement is performed using a white reflective diffuser made of a fluororesin film containing fluororesin particles in a region other than the light irradiation region.

If these characteristics are mentioned, 1. Improvement of the reflection efficiency of the fluorescent wave (ultraviolet light) by using a coating made of fluororesin particles. 2. Improvement of diffuse reflection characteristics by using a particulate control of fluororesin. Fluorescent wave (ultraviolet light) on integrating sphere substrate
3. Improvement of reflection characteristics using high reflection material. 3. Eco-friendly (consideration) coating; This includes reusing (recycling) fluorine resin particles.

FIG. 1 is an explanatory view showing an example of the spectrometer of the present invention. In FIG. 1, 1 is a light source, 2 is a light beam, 3 is a spectroscope, 4 is monochromatic light, 5 is a sector mirror, 1
1 is reference light, 12 is sample light, 6a and 6b are reflection mirrors,
7 is an integrating sphere, and s is a sample.

In the spectrometer for measuring the spectral energy intensity and distribution of light shown in FIG. 1, a light beam 2 emitted from a light source 1 is converted into a monochromatic light 4 by a spectroscope 3. The monochromatic light 4 is converted into a reference light 11 and a sample light 12 by a sector mirror 5.
Is divided into The reference light 11 is guided to the integrating sphere 7 by the reflection mirror 6b. On the other hand, the sample light 12 is
Is guided to the integrating sphere 7 through the sample s.

FIG. 2 is a schematic view of an integrating sphere used in the spectrometer of the present invention. FIG. 2 (a) is a sectional view seen from a direction perpendicular to the light irradiation direction, and FIG. It is sectional drawing seen from the irradiation direction of light. The sample light 12 guided through the sample s of the spectrometer shown in FIG. 1 passes through the entrance window 8 of the integrating sphere 7 and the light irradiation area 15 which is directly irradiated with the sample light.
Is applied to the phosphor coating 10 containing the phosphor. The fluorescent light 22 emitted by the irradiation of the sample light 12 is further reflected and diffused on the surface of the fluororesin coating 17 containing fluororesin particles, which is a light reflection and diffusion region 16 other than the light irradiation region 15 on the inner surface of the integrating sphere 7. While passing through the light receiving window 9, the light reaches the detector 13 composed of a photoelectric tube (photomultiplier) and is used for measurement. On the other hand, the reference light 11 guided from the reflection mirror 6b of the spectrometer shown in FIG.
From another angle (above the plane of the paper) through another entrance window (not shown) to the phosphor coating 10 at the position of the inner surface of the integrating sphere 7 (below the plane of the paper), Similarly, the emitted fluorescent light is reflected and diffused on the surface of the fluororesin film 17 of the highly reflective diffusion material on the inner surface of the integrating sphere, reaches the detector 13 composed of a phototube, and is subjected to measurement.

In the spectrometer of the present invention, it is desirable to use an integrating sphere for measuring the energy of light in a far ultraviolet or vacuum ultraviolet region having a wavelength region of light of 300 nm or less, preferably 120 to 250 nm.

As shown in FIG. 2, the integrating sphere of the present invention has a part of the inner surface of a hollow sphere 14 having at least one entrance window 8 for receiving light and at least one reception window 9 for receiving light at the detector. A phosphor coating 10 containing a phosphor is provided in a light irradiation area 15 which is directly irradiated with incident light, and a fluororesin particle is contained in a light reflection / diffusion area 16 which is an area other than the light irradiation area 15. It is characterized in that a fluorine resin film 17 is provided.

The integrating sphere is usually used in combination with a detector, and the size of a light receiving window 9 for receiving light to the detector and an entrance window 8 for allowing a light beam to enter the hollow sphere is 1/10 of the inner diameter of the sphere.
The degree is preferred.

The hollow sphere of the integrating sphere is not particularly limited and may be a commonly used hollow sphere. For example, as a base material, metals such as aluminum, duralumin, brass, ceramics, plastics and the like can be used. In order to obtain high reflection characteristics, a metal such as aluminum, silver, magnesium, and gallium is formed on the inner surface by a film forming method such as vacuum deposition and plating. It is also effective to apply a metal fluoride, such as magnesium fluoride, after further laminating it to improve the weather resistance.

As the phosphor used in the phosphor coating 10 of the present invention, a phosphor that emits light when stimulated by light in the ultraviolet region, particularly, light in the far ultraviolet or vacuum ultraviolet region to generate a fluorescent light is used. If the characteristics (spectral sensitivity) of the phototube and the spectral sensitivity of the phosphor are matched, high-sensitivity and high-performance measurement can be performed, and the type of the phosphor may be selected according to the type of the phototube. As the conditions required for the phosphor, those having good emission time, afterglow characteristics, stability, and weather resistance are preferable.

As the phosphor, an inorganic phosphor or an organic phosphor is used. Although there is no particular limitation on the type, examples of the inorganic phosphor include BaMg ₂ Al ₁₆ O ₂₇ : E
u, (SrCaBa) ₅ (PO ₄ ) ₃ Cl: Eu, Ba
Si ₂ O ₅ : Pb, YPO ₄ : Ce, Sr ₂ P ₂ O ₇ :
Eu, ZnS: Cu, Al, and the like. Examples of the organic phosphor include, for example, sodium salicylate, eosin, anthracene, a diaminostilbene derivative, terphenyl, lumogen, and coronene. Further, inorganic phosphors are preferable because they are superior in durability to organic phosphors.

In the present invention, the above-mentioned phosphor is applied to the light irradiation area on the inner surface of the hollow sphere of the integrating sphere to form a phosphor coating and used. The phosphor coating may be either a coating consisting of a single phosphor or a coating containing a phosphor and a binder for suspending and supporting the phosphor.

The phosphor coating consisting of the phosphor alone can be formed by dispersing the phosphor powder in a solvent such as alcohol, coating the inner surface of the hollow sphere of the integrating sphere, and drying.

The phosphor film containing the phosphor and a binder for suspending and supporting the phosphor is obtained by applying a solution containing a phosphor powder, a binder and a solvent to the inner surface of the hollow sphere of the integrating sphere and drying the solution. Can be formed.

The binder for suspending and supporting the phosphor is not particularly limited, but is preferably a water-soluble resin. Examples of the water-soluble resin include polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC),
Polyvinylpyrrolidone (PVP) and the like. The content of the binder in the phosphor coating is desirably 0 to 10 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the phosphor on a dry weight basis.

The thickness of the phosphor film is preferably in the range of about 0.5 to 2 mm. The above-mentioned phosphor coating has a reflectance of 90.
% Of the light reflecting / diffusing material. The method of forming the phosphor coating on the inner surface of the hollow sphere of the integrating sphere is not limited to the above-described coating method, and may be formed by depositing and depositing a phosphor.

On the other hand, in the light reflection / diffusion region 16 of the present invention,
The method is characterized by providing a fluororesin coating containing fluororesin particles. However, by granulating the fluororesin, the diffuse reflection performance can be improved.

As the fluororesin particles, ethylene tetrafluoride resin and its derivatives and copolymer resins can be used. Representative examples are ethylene tetrafluoride resin (PTFE), vinylidene fluoride resin (PVDF), vinyl fluoride resin (VDF), and ethylene trifluoride chloride (PC).
TFE), ethylene tetrafluoride-perfluoroalkyl vinyl ether copolymer resin (PFA), ethylene tetrafluoride-hexafluoropropylene copolymer resin (FEP), ethylene tetrafluoride
Particles such as ethylene copolymer resin (ETFE) and ethylene trifluoride-ethylene copolymer resin (ECTFE) are exemplified.

The average particle diameter of the fluororesin particles is 2 to 2.
Those having a range of 10 μm, preferably 5 to 7 μm are preferred. In addition, it is possible to increase the response at a specific wavelength by controlling the particle size and particle size distribution of the fluororesin particles.

In the present invention, the above-mentioned fluororesin particles are applied to the inner surface of the hollow sphere of the integrating sphere to form a fluororesin coating and used. The fluororesin coating may be either a coating consisting of fluororesin particles alone or a coating containing fluororesin particles and a binder for suspending and supporting the fluororesin particles.

The fluororesin coating consisting of the fluororesin particles alone can be formed by dispersing the fluororesin particles in a solvent such as alcohol, coating the inner surface of the hollow sphere of the integrating sphere, and drying.

Further, the fluororesin film containing the fluororesin particles and the binder for suspending and supporting the fluororesin particles is
It can be formed by applying a solution containing fluororesin particles, a binder and a solvent to the inner surface of the hollow sphere of the integrating sphere and drying.

The binder for suspending and supporting the fluororesin particles is not particularly limited, but is preferably a water-soluble resin. Examples of the water-soluble resin include polyvinyl alcohol (PVA) and carboxymethyl cellulose (CM
C) and polyvinylpyrrolidone (PVP). The content of the binder in the fluororesin coating is desirably 0 to 10 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the fluororesin particles on a dry weight basis.

The thickness of the fluorine resin film is preferably in the range of about 0.5 to 2 mm. Further, it is preferable that the above-mentioned fluororesin coating is made of a light diffusion reflector having a reflectance of 90% or more. The method of forming a fluororesin coating on the inner surface of the hollow sphere of the integrating sphere is as follows:
It is not limited to the above-mentioned coating method, but can be formed by deposition.

As the diffuse reflection material conventionally used on the inner surface of the hollow sphere of the integrating sphere, a white pigment typified by barium sulfate for visible light can be used. These have good characteristics for visible light, but have large absorption in the far ultraviolet region. As described above, in the conventional method, an excessive load is required for the phototube receiving light at the time of measurement, and as a result, a measurement result with large noise and inaccuracy is obtained. In view of such a situation, the present invention has taken up a fluororesin having a good property with respect to ultraviolet rays as a material for coating the inner surface of the integrating sphere. The diffusion performance of the fluororesin is enhanced by granulation. The spectral characteristics are also very good, and it can sufficiently cope with the vacuum ultraviolet region of 200 nm or less. Furthermore, by using a material having high reflectivity for ultraviolet light for the base material of the integrating sphere to be coated, further improvement in diffuse reflection characteristics can be expected.

As shown in FIG. 2 (b), the light (sample light 12) irradiated through the entrance window and having a low wavelength of 300 nm or less in the deep ultraviolet or vacuum ultraviolet region (sample light 12) is emitted from the hollow sphere of the integrating sphere. Phosphor coating film 1 containing a phosphor provided on a part of the inner surface
Directly irradiating the light irradiation area 15 consisting of 0
A fluorescent light beam 22 having a high wavelength of 50 to 500 nm is emitted, and the fluorescent light beam 22 is further irradiated with a light irradiation area 15 on the inner surface of the integrating sphere 7.
Reflection and diffusion of the surface of the fluororesin film 17 containing the fluororesin particles in the light reflection / diffusion region 16 other than the light reflection / diffusion region 16, and the fluorescent light 22 repeats reflection and diffusion in the light reflection / diffusion region 16, passes through the light receiving window 9, and passes through the photoelectric tube. (Photomaru) detector 1
It reaches 3 and is used for measurement.

The wavelength of the fluorescent light 22 measured by the detector is usually 350 nm or more, preferably 400 to 500 n.
m.

The spectrometer of the present invention uses the above-mentioned integrating sphere to measure the energy such as the spectral energy intensity and distribution of light in the far ultraviolet and vacuum ultraviolet regions where the wavelength of light is 300 nm or less. Can be.

[0045]

EXAMPLES The present invention will be specifically described below with reference to examples.

Embodiment 1 The integrating sphere of this embodiment cuts an aluminum block,
A hollow sphere whose inner surface was processed into a mirror surface by polishing was used. First, a coating solution for coating the phosphor on the inner surface of the hollow sphere of the integrating sphere was prepared. BaMg ₂ Al as phosphor
₁₆ O ₂₇ : Eu powder (center particle size 6.2 μm, particle size 4.5 to 4.5)
10 parts by weight of 8.5 μm particles (85% or more), 5 parts by weight of a 2% aqueous solution of polyvinyl alcohol, and 10 parts by weight of ethyl alcohol.

After the phosphor was weighed in a container, ethyl alcohol was added and stirred. After the powder particles were sufficiently dispersed, a coating solution was prepared by adding an aqueous polyvinyl alcohol solution and further stirring.

On the other hand, a coating liquid using fluororesin particles was prepared as a reflection / diffusion material for coating the inner surface of the hollow sphere of the integrating sphere. As a fluorine resin, tetrafluoroethylene resin (PT
FE) was used. Resin particle size is about 6μ average particle size
m (particle size as an aggregate of 0.2 μm particles having a peak in the range of 5 to 7 μm). 10 parts by weight of a fluorine resin, 5 parts by weight of a 5% aqueous solution of polyvinyl alcohol, and 10 parts by weight of ethyl alcohol were prepared. After weighing the fluororesin in the container, ethyl alcohol was added and stirred. After the particles were sufficiently dispersed, a coating solution was prepared by adding an aqueous polyvinyl alcohol solution and further stirring.

The coating is performed by setting a hemisphere of a hollow sphere, which has been previously maintained at a constant temperature (for example, 50 ° C.) in a thermostat, on a rotating plate, and then, while rotating, first coating a fluororesin as a reflection diffusion material. The solution was applied using a brush. Next, a phosphor coating solution was applied in a similar manner to an area directly irradiated with ultraviolet light, and dried. As a result, a uniform finish without unevenness was obtained.

The two hemispheres were combined (integrating sphere), and the spectrometer shown in FIG. 1 was set. The sample contains 20 mm thick Ca
With F _2, the transmittance was measured for each wavelength of light by using the ultraviolet light having a wavelength of 140～200Nm. The result is shown in FIG.

The ultraviolet light was converted into visible light at the center of 450 nm by the phosphor, and together with the spectral sensitivity of the phototube, a stable measurement result with a value close to the theoretical value and little noise was obtained.

Example 2 An integrating sphere having a hollow spherical body and an aluminum vapor-deposited film formed on the inner surface of a polycarbonate resin was used. In this embodiment, as a phosphor for coating the inner surface of the hollow sphere of the integrating _{sphere, (SrCaBa) 5 (PO 4} ) 3 Cl: Using Eu.

A coating solution was prepared in the same manner as in Example 1. 10 parts by weight of a phosphor, 10 parts by weight of ethyl alcohol, and 2 parts by weight of a 5% aqueous solution of polyvinyl alcohol were stirred and dispersed uniformly as in Example 1 to prepare a coating liquid.

On the other hand, as a fluororesin coating of a diffusion reflecting material for coating the inner surface of the hollow sphere of the integrating sphere, a tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP) is used as a material of the fluororesin particles. used. Particle size is about 8μ average particle size
m. For the preparation of the coating liquid, 10 parts by weight of a fluororesin, 20 parts by weight of ethyl alcohol, and 5 parts by weight of a 2% aqueous solution of polyvinyl alcohol were stirred and dispersed uniformly as in Example 1.

Using a brush, the adjusted coating solution is applied to each of the hollow sphere hemispheres in the same manner as in Example 1 in a predetermined area to be directly irradiated with ultraviolet light by a phosphor coating solution. A fluororesin coating liquid was applied to a non-direct irradiation area (light reflection / diffusion area) other than the area, and then dried. As a result, a white non-selective hemisphere whose inner surface was uniformly coated was obtained.

The two hemispheres were combined (integrating sphere), and the spectrometer shown in FIG. 1 was set. The sample contains 20 mm thick Ca
With F _2, the transmittance was measured for each wavelength of light by using the ultraviolet light having a wavelength of 140～200Nm. As a result, a stable measurement result with little noise and a transmittance similar to that of Example 1 was obtained.

Example 3 In Example 1, a coating liquid was prepared by using trifluorinated ethylene-ethylene copolymer resin (ECTFE) as a material for the particles of the fluororesin, and the non-direct coating was performed in the same manner as in Example 1. The irradiation area (light reflection diffusion area) was coated.

On the other hand, the phosphor is BaSi ₂ O ₅ : Pb1.
The coating liquid was prepared using 0 parts by weight, 3 parts by weight of a 1% aqueous solution of carboxymethyl cellulose as a binder resin, and 15 parts by weight of ethyl alcohol. Work was done.

The sample was set in a spectrometer and measured in the same manner as in Example 1. As a result of the measurement, as in the case of the first embodiment, a good measurement result having a high degree of accuracy with little noise was obtained.

Example 4 In Example 2, the coating liquid was adjusted using vinylidene fluoride resin (PVDF) as the fluorine resin, and the coating liquid was applied to the non-direct irradiation area (light reflection / diffusion area) as in Example 2. Work was done. On the other hand, in the same manner as in Example 2, a fluorescent coating solution was applied to the region directly irradiated with ultraviolet light.

The measurement was carried out in the same manner as in Example 1 by setting in a spectrometer. As a result of the measurement, as in the case of the first embodiment, a good measurement result having a high degree of accuracy with little noise was obtained.

Example 5 The entire optical system of Example 1 was subjected to spectrometry in an oxygen-free atmosphere by purging with nitrogen. The measurement results were as good as in Example 1, and high-precision measurement with little noise was possible even in the wavelength region of 200 nm or less.

[0063]

As described above, according to the present invention, the measurement accuracy such as the spectral energy distribution, the spectral transmittance, and the spectral reflectance is excellent particularly in the ultraviolet region, particularly in the deep ultraviolet region and the vacuum ultraviolet region. An integrating sphere was obtained. Further, the spectral energy intensity and distribution of light in the ultraviolet region, particularly, light in the far ultraviolet and vacuum ultraviolet regions can be accurately measured by the spectrometer using the integrating sphere of the present invention.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram illustrating an example of a spectrometer according to the present invention.

FIG. 2 is a schematic diagram showing an integrating sphere of the present invention.

FIG. 3 shows a wavelength of 140 to 200 using the integrating sphere of Example 1.
It is a figure showing the result of having measured transmittance using ultraviolet light of nm.

[Explanation of symbols]

 Reference Signs List 1 light source 2 light beam 3 spectroscope 4 monochromatic light 5 sector mirrors 6a and 6b are reflection mirrors 7 integrating sphere 8 entrance window 9 light receiving window 10 phosphor coating 11 reference light 12 sample light 13 detector 14 hollow sphere 15 light irradiation area 16 light Reflection / diffusion area 17 Fluororesin coating 22 Fluorescent light s Sample

Continued on the front page F term (reference) 2G020 AA05 CA02 CB43 CB44 CD23 CD28 2G065 AA04 AB05 BA18 BA29 BB37 BB42

Claims (13)

[Claims] 1. An inner surface of an integrating sphere used in a spectrometer for measuring the spectral energy intensity and distribution of light, the hollow sphere having at least one entrance window for receiving light and one receiving window for receiving light. A phosphor coating containing a phosphor and a fluororesin coating containing fluororesin particles. 2. The integrating sphere according to claim 1, wherein the wavelength range of the light is 300 nm or less. 3. The integrating sphere according to claim 1, wherein the inner surface of the hollow sphere is made of a light-reflective substrate made of metal or a thin film of metal. 4. The integrating sphere according to claim 1, wherein the phosphor is an inorganic phosphor or an organic phosphor. 5. The method according to claim 1, wherein the inorganic phosphor is BaMg ₂ Al.
₁₆ O ₂₇ : Eu, (SrCaBa) ₅ (PO ₄ ) ₃ Cl:
Eu, BaSi ₂ O ₅ : Pb, YPO ₄ : Ce, Sr _{2
P 2 O 7: Eu, ZnS} : Cu, claim 4 integrating sphere, wherein the at least one selected from Al. 6. The phosphor coating according to claim 1, wherein the phosphor coating contains the phosphor and a binder for suspending and supporting the phosphor in an amount of 0 to 10 parts by weight based on 100 parts by weight of the phosphor. Integrating sphere. 7. The integrating sphere according to claim 6, wherein said binder comprises a water-soluble resin. 8. The integrating sphere according to claim 1, wherein the phosphor coating is provided in a light irradiation area of the hollow sphere that is directly irradiated with light incident thereon. 9. The integrating sphere according to claim 1, wherein said fluororesin particles are particles of a tetrafluoroethylene resin, a derivative thereof, and a copolymer resin thereof. 10. The fluororesin coating comprises from 0 to 10 parts by weight of a binder of the fluororesin particles and a binder for suspending and supporting the fluororesin particles, based on 100 parts by weight of the fluororesin particles. 2. The integrating sphere according to 1. 11. The integrating sphere according to claim 10, wherein said binder comprises a water-soluble resin. 12. The integral according to claim 1, wherein the fluororesin coating is provided in a region other than a light irradiation region where the inner surface of the hollow sphere is directly irradiated with light incident thereon. ball. 13. A spectrometer for measuring the spectral energy intensity and distribution of light using the integrating sphere according to claim 1. Description: