JP2003028716A - Spectrometric instrument and method for spectrometric measurement - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a color center of a fatigue effect by irradiating a phosphor with an energy beam before and after measurement, to stabilize the measurement by negatively accelerated phosphorescence of an aftergrow, and to precisely measure a spectroscopic energy distribution and intensity. SOLUTION: This spectrometric instrument for measuring the spectroscopic energy distribution and the intensity of light has an integrating sphere 7 in the inside of which a phosphor film for converting the wavelength of the measured light is laid, and an energy beam emitting means 20 for emitting the energy beam 9 to the phosphor film before or after, or before and after the measurement to form the color center, and for negatively accelerating phosphorescence of the aftergrow.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a spectroscopic measurement device and a spectroscopic measurement method for measuring the spectral energy intensity and distribution of light, and particularly to the measurement and evaluation of light in the ultraviolet region. The present invention relates to an effective spectroscopic measurement device and a spectroscopic measurement method for improving measurement accuracy in the far ultraviolet region and vacuum ultraviolet region, which are low.

[0002]

2. Description of the Related Art Conventionally, the spectral energy of light is measured by measuring the spectral energy distribution, spectral transmittance, spectral reflectance, etc., and these measurements have been performed mainly in the visible region. The spectroscope used for spectroscopy also uses optical prisms, diffraction gratings, wavelength cut filters, interference filters, etc.
They are used properly depending on the precision and have come to the present day.

As a light source used for the measurement, since a relatively stable one such as a halogen lamp or a halogen lamp can be used, no problem has occurred. Also,
The integrating sphere that has been used to measure the spectral characteristics has been used by coating the inner surface with white powder such as barium sulfate.

[0004]

However, in contrast to the conventional spectroscopic measurement apparatus which has been mainly performed in the visible region,
In recent years, devices utilizing light rays in the ultraviolet region have come to be used in various fields. In particular, a g-line (λ = 435) of a mercury lamp is used for a light source such as a stepper used for manufacturing a semiconductor.
From 8Å) to i-line (λ = 3650Å), and more recently to the gas laser KrF (λ = 2486Å) laser. This means that the limit of semiconductor processing is from 0.35 μm line width to 0.16 μm and 0.12 μm further.
It indicates that the transition to the μm or less is going on.
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
34Å), F2 laser (λ = 1570Å) is promising.

The major problem here is the glass material and optical system used therein. As a glass material, Kr
Whether quartz used for F laser can be used,
This is because there are many problems such as how much fluorite can handle. Further, even a spectral spectrum measuring device used for measurement and evaluation does not support the vacuum ultraviolet region, and it is unlikely that accurate measurement and evaluation can be expected.

[0006] In the measurement of ultraviolet light, a method of converting ultraviolet light into light of long wavelength light energy for measurement is performed, and sodium salicylate is conventionally known for conversion of light energy into long wavelength. However, the conversion efficiency was low, no output was obtained even when used, and improvement in measurement accuracy could not be expected.

The present invention has been made in view of the problems of the prior art as described above, and in particular, a spectroscopic measuring device and a spectroscopic measurement having excellent measurement accuracy of light in the ultraviolet region, particularly light in the far ultraviolet region or vacuum ultraviolet region. It is intended to provide a method.

[0008]

That is, the first invention of the present invention is a spectroscopic measurement device for measuring the spectral energy intensity and distribution of light, which internally includes a phosphor film for wavelength-converting the light to be measured. The spectroscopic measurement device is characterized in that it has an integrating sphere installed in 1. and an energy ray irradiation means for irradiating the phosphor film with energy rays before, after, or before and after the measurement.

It is preferable that the energy ray irradiating means irradiates the energy ray from the surface of the phosphor film through the optical path of the light to be measured. It is preferable that the energy ray irradiation means irradiates the energy ray from the back surface of the phosphor film.

A second aspect of the present invention is a spectroscopic measurement method for measuring the spectral energy intensity and distribution of light using an integrating sphere, wherein a phosphor film for converting the wavelength of the measured light is installed inside. The spectroscopic measurement method is characterized in that the phosphor film of the integrating sphere is irradiated with energy rays before, after, or before and after the measurement.

The spectroscopic measurement method of the present invention comprises the steps of irradiating the phosphor film of the integrating sphere with energy rays by using an integrating sphere having a phosphor film for converting the wavelength of the light to be measured therein. The method comprises the steps of irradiating the phosphor film of the integrating sphere with light to emit fluorescent light, and diffusing and reflecting the emitted fluorescent light on the inner surface of the integrating sphere to measure the spectral energy intensity and distribution of the fluorescent light. Is preferred.

Further, the spectroscopic measurement method of the present invention uses an integrating sphere in which a phosphor film for wavelength-converting the light to be measured is installed, and the phosphor film of the integrating sphere is irradiated with light to cause fluorescence. A step of emitting a light beam, a step of diffusing and reflecting the emitted fluorescent light on the inner surface of an integrating sphere to measure the spectral energy intensity and distribution of the fluorescent light, and irradiating the phosphor film of the integrating sphere with an energy ray after the measurement. It is preferable to have a process.

Further, in the spectroscopic measurement method of the present invention, a step of irradiating the phosphor film of the integrating sphere with energy rays by using an integrating sphere having a phosphor film for converting the wavelength of the light to be measured therein. A step of irradiating the phosphor film of the integrating sphere with light to emit a fluorescent ray, a step of diffusely reflecting the emitted fluorescent ray on the inner surface of the integrating sphere, and measuring the spectral energy intensity and distribution of the fluorescent ray, It is preferable to have a step of irradiating the phosphor film of the integrating sphere with energy rays after the measurement.

Next, preferred embodiments of the spectroscopic measurement device and spectroscopic measurement method of the present invention will be shown below. It is preferable to irradiate the phosphor film with at least one energy ray selected from ultraviolet rays, visible rays, and infrared rays. It is preferable to stabilize the measurement by irradiating the energy beam with a fatigue effect on the phosphor film inside the integrating sphere and exhaustion of afterglow. It is preferable that the impartation of the fatigue effect is the formation of color centers.

Before the measurement, it is preferable that the surface of the phosphor film is irradiated with an ultraviolet ray through the optical path of the light to be measured to exert a fatigue effect on the phosphor film. It is preferable that the irradiated ultraviolet ray is far ultraviolet ray or vacuum ultraviolet ray having a wavelength of 300 nm or less. Before and after the measurement, it is preferable to exhaust the afterglow of the phosphor film by irradiating the surface of the phosphor film with red and infrared rays through the optical path of the light to be measured.

Before the measurement, it is preferable that the back surface of the phosphor film is irradiated with ultraviolet rays to exert a fatigue effect on the phosphor film.
It is preferable that the irradiated ultraviolet ray is far ultraviolet ray or vacuum ultraviolet ray having a wavelength of 300 nm or less. Before and after the measurement, it is preferable to irradiate the back surface of the phosphor film with red and infrared rays to exhaust the afterglow of the phosphor film.

The ultraviolet rays, red rays and infrared rays to be applied are monochromatic rays of a spectrophotometer and rays obtained from lasers, diodes, and lamps such as tungsten, mercury, halogen and xenon using an external light source. Preferably. It is preferable that the irradiation of the energy rays and the measurement of the spectral energy intensity and distribution of light are performed in a non-oxygen atmosphere such as gas replacement with nitrogen or helium and reduced pressure or vacuum.

[0018]

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 to the inner surface of light in the ultraviolet region, particularly far ultraviolet and vacuum ultraviolet region. In order to improve and solve the problems that occur when an integrating sphere is used and to measure and evaluate with high accuracy and to advance the technology, we attempted to improve and improve the integrating sphere, which is the main point of spectral energy measurement and evaluation.

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 since it has a large absorption for light in the far ultraviolet region, it has a sufficient amount of reflected light. It has been found that a serious problem is that the low response output is a cause of poor measurement accuracy.

Conventionally, the characteristics required of the integrating sphere are:
1. High reflectance, 2. Uniform diffusion (scattering), 3. It has uniform spectral characteristics. In addition to this, in order to measure light energy such as far ultraviolet and vacuum ultraviolet, 4. 4. Use of highly reflective material for ultraviolet rays, An atmosphere that does not damage energy,
6. Examples include prevention of pollution. However, in the direct measurement of ultraviolet rays using the light measuring device used for conventional visible light measurement, the photodetector such as a spectrophotometer is used in the far ultraviolet and vacuum ultraviolet regions including the window material. As a result, direct measurement of far ultraviolet and vacuum ultraviolet is difficult.

Therefore, the present invention proposes to overcome this problem by converting the wavelength of ultraviolet rays by using a phosphor, thereby making it possible to perform measurement in a region matched to the characteristics of the light receiver. This is to solve the problem of the deterioration of the reflectance of the integrating sphere and the spectral reflectance characteristic, which is a big problem here, by measuring in the long wavelength region where the white diffuse reflection material absorbs little ultraviolet light. To raise its characteristics, l. Use of a phosphor that emits visible light, 2. 2. Place a phosphor in the measurement light irradiation area; 3. Adoption of a binder resin with low UV absorption for supporting suspension. Environmentally friendly (consideration) coating, 4. This is the reuse (recycling) of the phosphor.

A desirable characteristic of the emission wavelength distribution of the phosphor to be used is a wavelength region in which the white diffuse reflection material used conventionally has a small absorption, specifically, in the case of barium sulfate, a wavelength region longer than 300 nm. Is. The phosphors that meet this condition are listed below. BaMg ₂
Al ₁₆ O ₂₇ : Eu, (SrCaBa) ₅ (PO ₄ ) ₃ C
1: Eu, BaSi ₂ O ₅ : Pb, YPO ₄ : Ce, S
At least one selected from r ₂ P ₂ O ₇ : Eu and ZnS: Cu, Al can be mentioned.

These phosphors are in the form of fine particles. To use it in a stationary state, it can be dispersed in water, alcohol or the like and coated with a brush or a spray, but a binder resin for suspending and supporting is required to form a durable film. The binder resin for suspending and supporting the phosphor is not particularly limited, but a water-soluble resin can be applied. Typical examples include polyvinyl alcohol, carboxymethyl cellulose, polyvinyl pyrrolidone, and the like. As the white diffuse reflector, alumina, titanium oxide, zinc oxide, etc. have been conventionally used, typically barium sulfate. In the visible region, good absorption is obtained with little absorption. The same water-soluble binder resin as the phosphor can be applied to the coating on the integrating sphere.

When a phosphor film is installed inside the integrating sphere and high-precision measurement is performed using the phosphor, the problem is the fatigue effect of the phosphor on the center of color (color). The decrease in emission intensity is considered to be caused by the formation of (center) and the afterglow peculiar to the phosphor. No problem was observed in the spectroscopic measurement in which the wavelength of ultraviolet light with which the phosphor was irradiated was 250 nm or more, because the formation of color centers was relatively small.

However, the inventors of the present invention have further raised the problem by applying to the vacuum ultraviolet region. Color centers in the vacuum ultraviolet region (wavelength of 200 nm or less) are formed more as the wavelength of the irradiation ultraviolet light is shorter, which greatly affects the measurement. That is, the measurement accuracy is lowered. Then, as a result of the inventors' keen examination, the method proposed as a countermeasure thereof has a good reproducibility by preliminarily forming a color center by irradiating the phosphor with energy rays as a pre-process of the spectroscopic measurement. Enable measurement,
Also, the difference is large depending on the type of the phosphor, but the phosphor is irradiated with an energy ray to measure the exhaustion of the afterglow of the fluorescence. Infrared rays and visible rays can be used for exhaustion.

A diffraction grating is used as a spectroscopic element when converting an ultraviolet ray as an energy ray into a monochromatic light using a spectroscope (monochromator) and sending it to an integrating sphere. When the blaze wavelength is a problem, the diffraction grating is provided with two for ultraviolet and one for infrared and can be used by switching.

As a light source for energy rays, a phosphor for one-time irradiation can also be used for ultraviolet rays, for example, deuterium lamps, and tungsten lamps for infrared rays can be used while being switched or mixed. A xenon arc lamp can be used for simultaneous irradiation.

That is, the spectroscopic measurement device of the present invention is a spectroscopic measurement device for measuring the spectral energy intensity and distribution of light using an integrating sphere, and a phosphor film for wavelength conversion of the measured light is installed inside. And an energy beam irradiation means for irradiating the phosphor film with an energy beam before, after, or before and after the measurement.

FIG. 1 is an explanatory view showing an example of a spectroscopic measurement device according to the first embodiment 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, 6a and 6b are reflection mirrors, 7 is an integrating sphere, 8 is a mirror, 9 is an energy ray, and 10 is an energy ray. Is a light source of energy rays, 11 is reference light, 12 is sample light, and s is a sample. Two
Reference numeral 0 denotes an energy ray irradiation means, which comprises a mirror 8, an energy ray 9 and a light source 10 for the energy ray.

In the spectroscopic measuring apparatus 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 the reference light 11 and the sample light 12 by the sector mirror 5.
Is divided into The reference light 11 is guided to the integrating sphere 7 by the reflecting mirror 6b. On the other hand, the sample light 12 is reflected by the reflection mirror 6a.
Is guided to the integrating sphere 7 via the sample s.

2 and 3 are schematic views of an integrating sphere used in the spectroscopic measurement device according to the first embodiment of the present invention.
Is a cross-sectional view seen from a direction perpendicular to the light irradiation direction, FIG.
FIG. 4 is a cross-sectional view seen from the light irradiation direction. The sample light 12 guided through the sample s of the spectroscopic measurement device shown in FIG. 1 passes through the entrance window 14 of the integrating sphere 7 and is applied to the phosphor film 18 in the light irradiation region 15 which is directly irradiated with the sample light. To be done. Sample light 1
The fluorescent light beam 22 is emitted from the phosphor film 18 by the irradiation of 2, and the emitted fluorescent light beam 22 is further reflected on the surface of the light reflection diffusion region 16 made of the reflection diffusion material other than the light irradiation region 15 on the inner surface of the integrating sphere 7. While reflecting and diffusing, it passes through the light receiving window 19 and reaches the detector 13 composed of a photoelectric tube (photomul) for measurement.

On the other hand, the reference beam 11 guided from the reflection mirror 6b of the spectroscopic measurement device shown in FIG. 1 is shifted from the incident window 14 shown in FIG. A fluorescent light beam, which passes through (not shown) and is irradiated to the phosphor film 18 provided at the position of the inner surface of the integrating sphere 7 (downward with respect to the paper surface) and similarly emitted, is a light reflection / diffusion region 1 on the inner surface of the integrating sphere.
While reflecting and diffusing on the surface of 6, it reaches a detector 13 composed of a photoelectric tube (photomul) for measurement.

Here, the phosphor film 18 is coated and installed on the inner surface of the integrating sphere 7 at the irradiation position of the sample light 12 to be measured.
Here, the phosphor film 18 is irradiated by the energy beam irradiation means 20.
The energy beam 9 is irradiated before, after, or before and after the above measurement. An energy ray 9 composed of ultraviolet, visible and infrared rays is applied to the surface of the phosphor film 18 from the middle of the optical path through the mirror 8 and the same optical path as the sample light 12 of the measuring light. In this case, without setting the sample s, light irradiation of energy rays is given to the phosphor surface inside the integrating sphere, and the sample is set after the color center is sufficiently formed,
Measurement is performed by switching the mirror 8. After the measurement, the sample is removed, and the irradiation of energy rays is further continued to exhaust the fluorescence of the phosphor having a large amount of afterglow.

The first embodiment of the spectroscopic measurement method of the present invention is, as described above, a method for converting the wavelength of the light to be measured in the method of measuring the spectral energy intensity and distribution of light using an integrating sphere. Using an integrating sphere in which a phosphor film is installed, a step of irradiating the phosphor film of the integrating sphere with light to emit a fluorescent ray, and diffusing and reflecting the emitted fluorescent ray on the inner surface of the integrating sphere. The measuring method comprises a step of measuring the spectral energy intensity and distribution of the fluorescent light and a step of irradiating the phosphor film of the integrating sphere with an energy ray before, after, or before and after the measurement.

The energy rays applied to the phosphor film are
At least one selected from ultraviolet rays, visible rays or infrared rays is preferably used, and it is preferable to irradiate the surface of the phosphor film with energy rays through the optical path of the light to be measured.

When ultraviolet rays are used as the energy rays, it is preferable to irradiate the surface of the phosphor film with ultraviolet rays through the optical path of the light to be measured to exert a fatigue effect on the phosphor film before the measurement. , The wavelength of ultraviolet light emitted is 300n
Far-ultraviolet rays and vacuum ultraviolet rays of m or less are preferable. Further, it is preferable that one of the fatigue effects given by the irradiation of ultraviolet rays before the spectroscopic measurement is the formation of color centers.

When visible light or infrared light is used as the energy ray, before irradiation with the measurement light of the spectroscopic measurement,
It is preferable to exhaust the afterglow of the phosphor film by irradiating the surface of the phosphor film with red or infrared rays through the optical path of the light to be measured both before and after irradiation.

The above-mentioned ultraviolet rays, red rays and infrared rays to be irradiated are monochromatic rays of a spectrophotometer and rays obtained from lasers, diodes, and lamps such as tungsten, mercury, halogen, xenon using an external light source. Preferably.

Irradiation of the energy rays and measurement of the spectral energy intensity and distribution of light are preferably carried out in a non-oxygen atmosphere such as gas replacement with nitrogen or helium and reduced pressure or vacuum.

FIG. 4 is an explanatory view showing an example of the spectroscopic measurement device according to the second embodiment of the present invention. In FIG. 4, 20
Reference numeral a denotes an energy ray irradiation means, and the energy ray irradiation means 20a denotes an energy ray 9 and an energy ray light source 1
0, and the energy ray 9 irradiates the phosphor film with the energy ray 9 from the back surface of the integrating sphere 7 provided with the light-transmissive base material, that is, through the light-transmissive base material to perform stable and highly accurate spectroscopic measurement. The feature is that it is possible.

FIG. 5 is a schematic view of an integrating sphere used in the spectroscopic measurement device according to the second embodiment of the present invention, and FIG. 5 is a sectional view seen from a direction perpendicular to the light irradiation direction. Sample light 12 guided through the sample s of the spectroscopic measurement device shown in FIG.
Is irradiated through the entrance window 14 of the integrating sphere 7 onto the phosphor film 18 in the light irradiation region 15 which is directly irradiated with the sample light.
The fluorescent light beam 22 is emitted from the phosphor film 18 by irradiation of the sample light 12.
Is emitted, and the emitted fluorescent light beam 22 is further reflected and diffused on the surface of the light reflection / diffusion region 16 made of a reflection / diffusion material other than the light irradiation region 15 on the inner surface of the integrating sphere 7 while receiving the light.
After passing through, it reaches a detector 13 composed of a phototube and is used for measurement.

On the other hand, the reference beam 11 guided from the reflection mirror 6b of the spectroscopic measurement device shown in FIG. 4 is shifted from the incident window 14 shown in FIG. A fluorescent light beam, which passes through (not shown) and is irradiated to a phosphor film 18 provided at a position on the inner surface of the integrating sphere 7 (downward with respect to the paper surface) and similarly emitted, is a light reflection / diffusion region 16 on the inner surface of the integrating sphere. While being reflected and diffused on the surface of the device, it reaches the detector 13 composed of a photoelectric tube (photomul) for measurement. Here, the phosphor film 18 is coated and installed on the translucent base material 17 that constitutes the integrating sphere 7. Here, by the energy ray irradiation means 20a, the energy ray 9 is emitted before, after, or before and after the above measurement.
Is transmitted through the translucent base material 17 from the outside of the integrating sphere 7 and is irradiated from the back side of the phosphor film 18. The energy ray 9 composed of ultraviolet rays, visible rays and infrared rays is irradiated during spectroscopic measurement, that is, when the reference light 11 and the sample light 12 are not irradiated.

The second embodiment of the spectroscopic measurement method of the present invention is a method for measuring the spectral energy intensity and distribution of light using an integrating sphere, as described above, and a phosphor for wavelength conversion of ultraviolet rays. It is characterized in that the film is installed inside the integrating sphere, and means for irradiating energy rays such as ultraviolet rays, red rays and infrared rays from the back surface of the phosphor film is provided.

The translucent substrate may be made of a material that transmits energy rays, and for example, quartz, fluorite, Pyrex (registered trademark) or the like is used.

When an ultraviolet ray is used as the energy ray, it is preferable that irradiation of the ultraviolet ray to the phosphor film is performed before the spectroscopic measurement. Irradiation of the ultraviolet rays to the phosphor film is a means for imparting a fatigue effect to the phosphor in advance, and one of the fatigue effects imparted to the phosphor film in advance is the formation of a color center. preferable. It is preferable that the ultraviolet rays are far ultraviolet rays and vacuum ultraviolet rays having a wavelength of 300 nm or less. The means for irradiating the phosphor film with ultraviolet rays from the back side is preferably a light source such as an ultraviolet laser, a diode, and a lamp such as deuterium or mercury.

When ultraviolet rays are used as the energy rays, it is preferable that the phosphor film is irradiated with red and infrared rays before and after the spectroscopic measurement. Further, it is preferable that the substrate on which the phosphor film is placed is a glass material capable of transmitting ultraviolet rays, red rays and infrared rays. The irradiation of the red and infrared rays is a means for erasing the afterglow of the phosphor produced by the spectroscopic measurement, and the means for irradiating the phosphor film with the red and infrared rays from the back surface has a wavelength of 600 nm or more. It is preferable that the light source emits light, that is, a laser, a diode, tungsten, a halogen lamp, or the like.

[0047]

EXAMPLES The present invention will be specifically described below with reference to examples. In addition, "part" shows a relative amount (weight) standard.

Example 1 Measurement was carried out with the spectroscopic measurement device shown in FIGS. The integrating sphere used in this example had an inner surface processed by cutting and polishing an aluminum block. Further, the measurement light beam, that is, the inlet for introducing the sample light 12 and the reference light 11 and the hole-shaped inlet for the measuring aperture of the photoelectric tube (Photomul) were processed.

First, a coating solution for coating barium sulfate as a white light diffuse reflection material on the inner surface of the integrating sphere was prepared. 10 parts of barium sulfate, 3 parts of 2% PVA aqueous solution, and 10 parts of ethyl alcohol were prepared. After ethanol was added to the barium sulfate powder and mixed by stirring, the PVA solution was added and further mixed to prepare a barium silicate coating solution. Next, the inner surface of each hemisphere of the integrating sphere was coated with a brush and air-dried.

On the other hand, the phosphor was applied by coating on an uncoated area substrate left in a circular shape in advance. BaMg ₂ Al as a phosphor
₁₆ O ₂₇ : 10 parts of Eu, 10 parts of ethyl alcohol, 2
% Of PVA aqueous solution was prepared. After weighing the phosphor in a container, ethyl alcohol and a PVA aqueous solution were added and stirred. After the powder particles were sufficiently dispersed, the coating liquid was ready.

After setting the integrating sphere on the rotary plate of the rotary coating machine, the coating liquid was coated with a brush while rotating.
The coated surface had a white, matte and even finish. After drying, the integrating spheres were combined and set on a spectrophotometer. The measurement environment was such that the entire optical system was in a deoxygenated atmosphere by nitrogen gas replacement.

Next, the measurement results of the spectroscopic measurement device of the present invention will be described. FIG. 6 shows the measurement result of the spectral transmittance of the lens by the conventional measurement. The measurement was carried out in nitrogen gas to leave it in a deoxidized and dehydrated atmosphere, after leaving it overnight. Measurements were repeated 5 times for clarity. In the figure, 1 to 5 indicate the first to fifth times. In this case, the numerical value of the transmittance increases with each repetition. As a result, the measured value was stable from the fourth time.

Therefore, without setting the measurement sample before the measurement, as shown in FIG.
Was irradiated for 1 minute with stimulating light (xenon lamp). FIG. 7 shows the result of the actual measurement performed immediately after. Similarly, as a result of repeating the measurement 5 times, the measurement results of 5 times showed the same transmittance.

The above results show that in the spectral measurement in the far ultraviolet and vacuum ultraviolet regions, long wavelength light (450 n
m) and the spectral sensitivity of the phototube, the output was about 10 times that of conventional measurements that did not use phosphors, and the stimulating light irradiation before and after the measurement caused the color center to increase. It is shown that the formation is stable and the afterglow is exhausted, so that the measurement can be stably performed with high output and high accuracy.

Example 2 Measurement was carried out with the spectroscopic measurement device shown in FIGS. 4 and 5. A quartz substrate was fitted into the measuring light direct irradiation area of the integrating sphere. As in Example 1, a white diffuse reflector of barium sulfate was placed on the inner surface of the integrating sphere. This time ZnS: Cu, A as the phosphor
1 was used. The coating liquid is ZnS: Cu, Al 10 parts, P
A 1% aqueous solution of VA was mixed and adjusted with 4 parts and 6 parts of ethyl alcohol.

As a pre-measurement step of the spectroscopic measurement, a light beam was irradiated for 1 minute through a quartz substrate on the back surface of the phosphor using a xenon lamp. In this case, it is considered that the color center was formed and the afterglow of the fluorescence was exhausted at the same time by simultaneously irradiating the ultraviolet to infrared energy rays. As a result of repeating the measurement five times, the results were the same as those in FIG. 7. The results of five measurements showed the same transmittance.

The above results show that in spectroscopic measurement in the far-ultraviolet and vacuum-ultraviolet regions, long-wavelength light (5
(30 nm) and the spectral sensitivity of the phototube, the output was about 9 times that of conventional measurements that did not use phosphors, and the irradiation of visible and infrared rays before and after the measurement We were able to obtain stable measurement results with high output and high accuracy.

Example 3 In Example 1, this time, a similar firefly was used for the white diffuse reflection material.
Light body (SrCaBa) _Five (PO_Four )₃ Cl: Eu is used
did. The coating liquid is phosphor 10 parts, methyl alcohol 15
Department. Stir 2 parts of 1% aqueous solution of polyvinyl alcohol similarly
And dispersed evenly. Spray gun with adjusted coating liquid
In the same way, apply the hemispheres of the integrating sphere in the same way, dry and even
A coated white, non-selective integrating sphere was obtained.

After being sufficiently dried, both hemispheres were combined in the same manner, an integrating sphere was set, and the hemispheres were set in a spectrophotometer for spectroscopic measurement. For each measurement, a mercury lamp and a tungsten lamp were alternately used from the middle of the measurement optical path to irradiate the phosphor surface using a sector mirror.

As a result of comparison with the measurement result without using the conventional phosphor, the output became about 10 times, and the numerical values of repeated measurement coincided with each other, and a stable measurement result with very little noise was obtained.

Example 4 In Example 1, the phosphor was made of BaSi ₂ O ₅ : Pb10.
Part, carboxymethyl cellulose 2 as binder resin
% Aqueous solution and 15 parts of ethyl alcohol to prepare a coating solution. Through a similar process, a white non-selective integrating sphere and a fluorescent plate which were uniformly coated were obtained.

In this measurement, a wavelength scan was performed for 20 minutes without particularly applying an energy ray (stimulating ray) from the outside and setting the sample in advance before the measurement. The sample was continuously set and the spectroscopic measurement was performed.

The measurement was repeated 5 times. The result is Figure 7.
It was a stable result similar to. This means that the same color center formation and afterglow erasure can be achieved by performing measurements during continuous wavelength scanning.

Example 5 Measurement was carried out with the spectroscopic measurement device shown in FIGS. The integrating sphere used in this embodiment is made by cutting an aluminum block,
The inner surface is processed by polishing. In addition, an ultraviolet ray, that is, an inlet for introducing the sample light 12 and the reference light 11 and a hole-shaped inlet for the measuring port of the photoelectric tube (Photomul) were processed.

First, a coating solution for coating barium sulfate as a white light diffuse reflection material on the inner surface of the integrating sphere was prepared. Barium sulfate 10 parts, 2% PVA solution 5 parts, ethanol 1
0 parts were prepared. After adding ethanol to the barium sulfate powder and stirring and mixing, a PVA solution was added and further mixed to prepare a barium sulfate coating solution. Next, the inner surface of each of the integrating spheres was coated with a brush and air-dried.

On the other hand, the phosphor was applied by coating on an uncoated area substrate left in a circular shape in advance. BaMg ₂ Al as a phosphor
₁₆ O ₂₇ : 10 parts of Eu, 3 parts of a 2% aqueous solution of polyvinyl alcohol, and 10 parts of ethyl alcohol were prepared. After weighing the phosphor in a container, ethyl alcohol was added and stirred. After the powder particles were sufficiently dispersed, a polyvinyl alcohol aqueous solution was added and further stirred to prepare a coating liquid. After setting the integrating sphere on the turntable of the spin coater,
The coating liquid was applied using a brush while rotating. The coated surface had a white, non-selective and even finish.

After being sufficiently dried, the integrating spheres were combined and set in a spectrophotometer. The measurement environment was an oxygen-free atmosphere in which the entire optical system was replaced with nitrogen gas. In the spectroscopic measurement, a light beam in the vacuum ultraviolet region around a wavelength of 160 nm was scanned in the absence of a measurement sample in advance and irradiation was repeated 10 times.
Immediately after that, the lens having the antireflection film was set on the sample and the spectral transmittance was measured. 8 and 9
Is the measurement result of the spectral transmittance of the lens. Measurements were repeated 5 times for clarity. FIG. 8 shows the result of the conventional measurement. In this case, it is recognized that the numerical value of the transmittance is high in this case and decreases with each repetition. FIG. 9 shows the result of giving the fatigue effect immediately before the measurement of the present invention. Similarly, the measurement was repeated 5 times, and the measurement results of 5 times showed the same transmittance.

The above results show that, in the spectroscopic measurement in the far ultraviolet and vacuum ultraviolet regions, the conversion of far ultraviolet and vacuum ultraviolet light into long wavelength light (450 nm) using a phosphor and the spectral sensitivity of the photoelectric tube are combined. Shows that the output is about 10 times that of the conventional measurement without using a phosphor, and that the application of the fatigue effect of the phosphor has made it possible to obtain highly accurate and stable measurement results. There is.

Example 6 In Example 5, a phosphor (SrCaBa) ₅ (PO ₄ ) ₃ Cl: Eu was used as the white diffuse reflector this time. Similarly, the coating liquid was prepared. 10 parts of the phosphor, 20 parts of ethyl alcohol, and 4 parts of a 5% aqueous solution of polyvinyl alcohol were similarly stirred and uniformly dispersed. The adjusted coating liquid was similarly applied to each of the integrating sphere hemispheres using a spray gun and dried to obtain a uniformly coated white non-selective integrating sphere.

After being sufficiently dried, both hemispheres were similarly combined and set in a spectrophotometer for spectroscopic measurement. Immediately before the measurement, far ultraviolet light was irradiated for 5 minutes using a low pressure mercury lamp.
Far ultraviolet light was introduced into the front optical path of the rotating sector using a reflecting mirror for irradiation. Similarly, the measurement results were in good agreement with the measurement results of 5 repetitions. Along with the output being about 8 times that of the conventional one, stable measurement results with very little noise were obtained.

Example 7 In Example 6, the phosphor was made of BaSi ₂ O ₅ : Pbl0.
Part, carboxymethyl cellulose 1 as binder resin
% Aqueous solution 3 parts and ethyl alcohol 15 parts to prepare a coating liquid. Through a similar process, a uniformly coated white non-selective integrating sphere was obtained.

A deuterium lamp was used to give a fatigue effect to the phosphor. Similarly, ultraviolet rays were introduced from an optical path on the way and irradiation was performed immediately before the spectroscopic measurement. The spectroscopic measurement results were also good, and stable measurement results with less noise were obtained compared to the conventional method.

Example 8 In Example 6, a coating liquid was prepared by using ZnS: Cu, Al for the phosphor. After the barium sulfate white diffuse reflection material was applied to the inner surface of the integrating sphere, a coating solution containing 10 parts of the phosphor, 10 parts of ethyl alcohol, and 5 parts of a 2% aqueous solution of polyvinyl alcohol was prepared. Then, the coating was applied only to the area receiving the irradiation of the measuring light beam. Thus, a uniformly white unselected integrating sphere was obtained. After being sufficiently dried, both hemispheres were similarly combined and set in a spectrophotometer for spectroscopic measurement.

Immediately before the measurement, a red light combining a red filter and a tungsten lamp was irradiated for several seconds. A reflective mirror was installed in the optical path of the measurement light for irradiation.

Conventionally, there were large variations and lack of reliability, but the present measurement showed stable results. The output was about 8 times that of the conventional method that does not use a phosphor, and high-precision and stable measurement results were obtained.

Example 9 The entire optical system of Example 6 was subjected to spectroscopic measurement in an oxygen-free atmosphere by helium substitution. Even in the wavelength region around 160 nm, it was possible to perform highly accurate measurement with less noise compared to the conventional case.

Example 10 Measurement was carried out by the spectroscopic measurement device shown in FIGS. 4 and 5. The integrating sphere used in this embodiment has an inner surface processed by cutting and polishing an aluminum block. In addition, an inlet for passing the measurement light, that is, the sample light and the reference light, and a hole-shaped inlet for installing a translucent substrate for coating the phosphor were processed.

First, a coating solution for coating barium sulfate on the inner surface of the integrating sphere as a white light diffuse reflection material was prepared. Barium sulfate 10 parts, 2% PVA solution 5 parts, ethanol 10
I prepared a section. After adding ethanol to the barium sulfate powder and stirring and mixing, a PVA solution was added and further mixed to prepare a barium sulfate coating solution. Each hemisphere of the integrating sphere was coated on the inner surface with a brush and air-dried.

On the other hand, the phosphor was coated and set on a circular transparent substrate made of quartz. BaMg ₂ Al ₁₆ O ₂₇ : E as a phosphor
10 parts of u and 3% of a 2% aqueous solution of polyvinyl alcohol
And 10 parts of ethyl alcohol were prepared. The phosphor was weighed in a container, ethyl alcohol was added, and the mixture was stirred. After the powder particles were sufficiently dispersed, a coating solution could be prepared by adding an aqueous solution of polyvinyl alcohol and further stirring. The Pyrex (registered trademark) substrate was set on the rotary plate of a rotary coating machine, and then the coating liquid was applied using a brush while rotating. The coated surface had a white, non-selective and even finish.

After combining the integrating spheres, the phosphor substrate was set in the spectrophotometer. The measurement environment was an oxygen-free atmosphere in which the entire optical system was replaced with nitrogen gas. FIG. 10 shows the measurement results of the spectral transmittance of the lens provided with the antireflection film by the conventional measurement not using the present invention. 5 for clarity
The measurement was repeated repeatedly. In this case, the numerical value of the transmittance decreased with each repetition.

FIG. 11 shows the results obtained by irradiating the phosphor of the integrating sphere from the back surface with far ultraviolet rays using a low-pressure mercury lamp before irradiation of the measurement light, that is, before the start of the first measurement. In this case, since quartz was used for the substrate, light having a wavelength of 200 nm or less was also transmitted. Similarly, the measurement was repeated 5 times. The results of the 5 measurements agree very well.

The above results show that in the spectral measurement in the far ultraviolet and vacuum ultraviolet regions, long wavelength light (4
(50 nm) and the spectral sensitivity of the phototube, the output was about 10 times that of conventional measurements that did not use phosphors, and the high output due to the fatigue effect of irradiation with ultraviolet rays before measurement. It was possible to obtain highly accurate and stable measurement results.

Example 11 In Example 10, a phosphor (SrCaBa) ₅ (PO ₄ ) ₃ Cl: Eu was used as the white diffuse reflector this time. Similarly, the coating liquid was prepared. 10 parts of the phosphor, 20 parts of ethyl alcohol, and 4 parts of a 5% aqueous solution of polyvinyl alcohol were similarly stirred and uniformly dispersed. The adjusted coating liquid was similarly applied to each of the integrating sphere hemispheres using a spray gun and dried to obtain a uniformly coated white non-selective integrating sphere.

On the other hand, fluorite was used for the transparent substrate. The phosphor coating solution was applied in the same manner. After being sufficiently dried, both hemispheres were combined in the same manner to set a phosphor, and the phosphor was set in a spectrophotometer for spectroscopic measurement. This time, just before the measurement, a deep-ultraviolet ray was sufficiently irradiated from the back surface using a deuterium lamp. Then, the spectroscopic measurement was continuously performed. The values of repeated measurement were in good agreement and stable measurement results with less noise were obtained. The output was about 8 times as compared with the measurement result without using the conventional phosphor.

Example 12 In Example 11, the phosphor was made of BaSi ₂ O ₅ : Pbl.
A coating solution was prepared by using 0 part, 3 parts of a 1% aqueous solution of carboxymethyl cellulose as a binder resin, and 15 parts of ethyl alcohol. Through a similar process, a uniformly coated white non-luminous integrating sphere and phosphor were obtained. An ArF laser was used for the light beam irradiated from the back surface of the phosphor immediately before the measurement. The measurement results were good, and stable measurement results with less noise were obtained compared to the conventional method.

Example 13 In Example 11, the phosphor was YPO ₄ : Ce, Sr ₂
A coating solution was prepared using P ₂ O ₇ : Eu, ZnS: Cu, Al and the like, and the same coating was performed. A mercury lamp or the like was used to irradiate the phosphor from the back surface. Similarly, when the measurement was carried out by setting it in a spectroscopic measurement device, it was possible to perform highly stable and highly accurate measurement with much less noise than in the past.

Example 14 In Example 10, barium sulfate was used as the white diffuse reflection material, and ZnS: CuAl was selected as the phosphor. Similarly, the coating liquid was prepared. Barium sulfate 10 parts, ethyl alcohol 20 parts, and polyvinyl alcohol 5% aqueous solution 4 parts were similarly stirred and uniformly dispersed. The adjusted coating liquid was similarly applied to each of the integrating sphere hemispheres using a spray gun and dried to obtain a uniformly coated white non-selective integrating sphere.

On the other hand, 10 parts of phosphor ZnS: CuAl, 10 parts of ethyl alcohol, and 5 parts of a 2% solution of polyvinyl alcohol were similarly stirred and mixed to prepare a coating solution. Pyrex (registered trademark) was used for the transparent substrate. The phosphor coating solution was applied onto a translucent substrate using a spin coater and a brush. After being sufficiently dried, both hemispheres were combined in the same manner, a phosphor was attached, and the hemisphere was incorporated into a spectroscopic measurement device for spectroscopic measurement.

This time, immediately before the measurement, the He-Ne laser beam was irradiated from the back surface of the Pyrex (registered trademark) substrate. After that, after each measurement, the H
It was irradiated with an e-Ne laser beam. The obtained numerical values were stable with little variation.

Example 15 The entire optical system of Example 10 was subjected to spectroscopic measurement in an oxygen-free atmosphere by substituting nitrogen and helium. In the measurement of the present example, even in the wavelength region around 160 nm, high-precision measurement with less noise than the conventional case was possible.

[0091]

As described above, according to the present invention, particularly in the ultraviolet region, particularly in the far ultraviolet region and the vacuum ultraviolet region,
The irradiation of energy rays before and after the measurement formed a fluorescent color center in the phosphor, and afterglow was exhausted, the measurement was stable and the spectral energy distribution and intensity could be measured accurately. A spectroscopic measurement device and a spectroscopic measurement method that can be performed can be provided.

[Brief description of drawings]

FIG. 1 is an explanatory diagram showing an example of a spectroscopic measurement device of the present invention.

FIG. 2 is a schematic view showing an integrating sphere used in the present invention.

FIG. 3 is a schematic view showing an integrating sphere used in the present invention.

FIG. 4 is an explanatory diagram showing another example of the spectroscopic measurement device of the present invention.

FIG. 5 is a schematic view showing an integrating sphere used in the present invention.

FIG. 6 is a diagram showing a measurement result of a spectral transmittance of a lens by a conventional measurement.

FIG. 7 is a diagram showing a measurement result of a spectral transmittance of a lens by the measurement of Example 1.

FIG. 8 is a diagram showing a measurement result of a spectral transmittance of a lens by a conventional measurement.

FIG. 9 is a diagram showing a measurement result of a spectral transmittance of a lens obtained by measurement in Example 5;

FIG. 10 is a diagram showing a measurement result of a spectral transmittance of a lens by a conventional measurement.

FIG. 11 is a diagram showing a measurement result of a spectral transmittance of a lens obtained by measurement in Example 10;

[Explanation of symbols]

1 light source Two rays 3 spectroscope 4 monochromatic light 5 sector mirror 6a and 6b are reflection mirrors 7 integrating sphere 8 mirror 9 energy rays 10 Energy ray light source 11 Reference light 12 Sample light 13 detectors 14 incident window 15 Light irradiation area 16 Light reflection diffusion area 17 Translucent base material 18 Phosphor film 19 Light receiving window 20, 20a Energy ray irradiation means 22 Fluorescent light s sample

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 2G020 AA04 AA05 BA02 BA20 CB05                       CB25 CB26 CB27 CB32 CB33                       CB34 CB43 CB44 CC02 CC26                       CC47 CD13 CD14 CD23                 2G059 BB08 EE01 EE12 FF09 GG01                       GG02 GG10 HH03 HH04 JJ01                       JJ13 JJ16 KK02                 2G065 AA04 AB04 AB05 AB09 AB11                       AB23 AB27 AB28 BA18 BA29                       BB14 BB15 BB26 BB42 DA05                 2G086 FF06

Claims (29)

[Claims] 1. In a spectroscopic measurement device for measuring the spectral energy intensity and distribution of light, an integrating sphere in which a phosphor film for converting the wavelength of the light to be measured is installed, and the phosphor film before measurement. A spectroscopic measurement device having an energy ray irradiation means for irradiating the energy ray after or before and after. 2. The spectroscopic measurement device according to claim 1, wherein the phosphor film is irradiated with at least one energy ray selected from ultraviolet rays, visible rays, and infrared rays. 3. The spectroscopic measurement device according to claim 1, wherein the energy ray irradiating means irradiates the surface of the phosphor film with energy rays through an optical path of the light to be measured. 4. The spectroscopic measurement apparatus according to claim 1, wherein the energy ray irradiating means radiates energy rays from the back surface of the phosphor film. 5. The measurement according to claim 1, wherein irradiation with the energy beam imparts a fatigue effect to the phosphor film inside the integrating sphere and exhausts the afterglow to stabilize the measurement. Spectrometer. 6. The spectroscopic measurement device according to claim 5, wherein the application of the fatigue effect is the formation of color centers. 7. The method according to claim 1, wherein before the measurement, the surface of the phosphor film is irradiated with an ultraviolet ray through the optical path of the light to be measured to exert a fatigue effect on the phosphor film. The spectroscopic measurement device described. 8. The ultraviolet ray for irradiation has a wavelength of 300 n.
The spectroscopic measurement device according to claim 7, which is far ultraviolet ray or vacuum ultraviolet ray of m or less. 9. The method according to claim 1, wherein before and after the measurement, the surface of the phosphor film is irradiated with red and infrared rays through the optical path of the light to be measured to exhaust the afterglow of the phosphor film. The spectroscopic measurement device described in that item. 10. The spectroscopic measurement device according to claim 1, wherein before the measurement, the back surface of the phosphor film is irradiated with ultraviolet rays to exert a fatigue effect on the phosphor film. 11. The ultraviolet ray for irradiation has a wavelength of 300.
The spectroscopic measurement device according to claim 10, which is far ultraviolet rays or vacuum ultraviolet rays having a wavelength of nm or less. 12. The spectrum according to claim 1, wherein before and after the measurement, the back surface of the phosphor film is irradiated with red and infrared rays to exhaust the afterglow of the phosphor film. measuring device. 13. The irradiating ultraviolet rays, red rays and infrared rays are obtained from monochromatic rays of a spectrophotometer and lasers, diodes, and lamps of tungsten, mercury, halogen and xenon using an external light source. The spectroscopic measurement device according to any one of claims 7 to 11. 14. In a spectroscopic measurement method for measuring the spectral energy intensity and distribution of light, a phosphor film of an integrating sphere in which a phosphor film for converting the wavelength of the light to be measured is installed, before measurement, A spectroscopic measurement method characterized by irradiating energy rays behind or before and after. 15. A step of irradiating an energy ray to the phosphor film of the integrating sphere by using an integrating sphere having a phosphor film for converting the wavelength of the light to be measured therein, the phosphor film of the integrating sphere. 15. The spectroscopic measurement according to claim 14, further comprising the steps of irradiating light on the surface to emit fluorescent light and measuring the spectral energy intensity and distribution of the fluorescent light by diffusing and reflecting the emitted fluorescent light on the inner surface of the integrating sphere. Method. 16. A step of irradiating the phosphor film of the integrating sphere with light to emit a fluorescent ray by using an integrating sphere having a phosphor film for converting the wavelength of the light to be measured therein, 15. The method according to claim 14, further comprising the steps of: diffusing and reflecting the fluorescent light on the inner surface of the integrating sphere to measure the spectral energy intensity and distribution of the fluorescent light; Spectroscopic measurement method. 17. A step of irradiating the phosphor film of the integrating sphere with energy rays by using an integrating sphere having a phosphor film for converting the wavelength of the light to be measured therein, the phosphor film of the integrating sphere. A step of irradiating a fluorescent light to emit light, a step of measuring the spectral energy intensity and distribution of the fluorescent light by diffusively reflecting the emitted fluorescent light on the inner surface of the integrating sphere, and a phosphor of the integrating sphere after measurement. The spectroscopic measurement method according to claim 14, further comprising the step of irradiating the film with energy rays. 18. The spectroscopic measurement method according to claim 14, wherein the phosphor film is irradiated with at least one energy ray selected from ultraviolet rays, visible rays, and infrared rays. 19. The spectroscopic measurement method according to claim 14, wherein the energy beam is irradiated from the surface of the phosphor film through the optical path of the light to be measured. 20. The spectroscopic measurement method according to claim 14, wherein the energy beam is irradiated from the back surface of the phosphor film. 21. The measurement is stabilized by applying a fatigue effect to the phosphor film inside the integrating sphere and exhausting afterglow by irradiating with the energy beam. Spectroscopic measurement method. 22. The spectroscopic measurement method according to claim 21, wherein the imparting of the fatigue effect is the formation of color centers. 23. Before the measurement, the surface of the phosphor film is irradiated with an ultraviolet ray through the optical path of the light to be measured to exert a fatigue effect on the phosphor film. The spectroscopic measurement method described. 24. The ultraviolet ray for irradiation has a wavelength of 300.
24. The spectroscopic measurement method according to claim 23, which is far ultraviolet rays or vacuum ultraviolet rays having a wavelength of nm or less. 25. Before and after the measurement, the surface of the phosphor film is irradiated with red and infrared rays through an optical path of the light to be measured to exhaust the afterglow of the phosphor film. The spectroscopic measurement method described in that section. 26. Before the measurement, the back surface of the phosphor film is irradiated with ultraviolet rays to exert a fatigue effect on the phosphor film.
25. The spectroscopic measurement method according to any one of items 24 to 24. 27. The ultraviolet ray for irradiation has a wavelength of 300.
27. The method for spectroscopic measurement according to claim 26, which is far ultraviolet rays or vacuum ultraviolet rays having a wavelength of nm or less. 28. The spectrum according to claim 14, wherein before and after the measurement, the back surface of the phosphor film is irradiated with red and infrared rays to exhaust the afterglow of the phosphor film. measuring device. 29. The method according to any one of claims 14 to 28, wherein the irradiation of the energy rays and the measurement of the spectral energy intensity and distribution of light are performed in a non-oxygen atmosphere such as gas replacement with nitrogen or helium and reduced pressure or vacuum. The spectroscopic measurement method described.