JP2002310798A - Integral sphere, spectral measuring device using the same, spectral measuring method and semiconductor manufacturing exposure printing device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a spectral measuring device superior in the measuring precision of light of a far ultraviolet, vacuum ultraviolet and soft X ray area. SOLUTION: In the spectral measuring device for measuring the intensity and distribution of the spectral energy of light in which the wavelength area of the light to be measured is 300 nm or less by using an integral sphere 7, a phosphor coat containing inorganic phosphor particles and fluorine resin particles in the whole or a part of the inner face of the integral sphere 7 is provided. The fluorine resin constituting the phosphor coat provided on the inner face of the integral sphere is tetrafluoroethylene resin, its derivative and their copolymer resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an integrating sphere, a spectroscopic measuring device, a spectroscopic measuring method, and an exposure printing apparatus for semiconductor manufacturing, which are used in a spectroscopic measuring device for measuring the spectral energy intensity and distribution of light. For light measurement and evaluation,
In particular, the present invention relates to an effective integrating sphere, a spectroscopic measuring device, and a spectroscopic measuring method for improving the measuring accuracy in the far ultraviolet region, the vacuum ultraviolet region, and the soft X-ray region (including EUV), which have been difficult to measure conventionally and have low accuracy. .

[0002]

2. Description of the Related Art Conventionally, the spectral energy of light 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 spectroscope used for spectroscopy is also used for optical prisms, diffraction gratings, wavelength cut filters, interference filters, etc.
It has been used today depending on the accuracy.

As a light source used for the measurement, a relatively stable light source such as a halogen lamp, mainly a tungsten light bulb, can be used, so that no problem occurred. Also,
As the integrating sphere used for measuring the spectral characteristics, a sphere coated with white powder such as barium sulfate on the inner surface has been used.

[0004]

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 °), an F2 laser (λ = 1570 °) is promising.

The major problems here are the glass materials and optical systems used therein. As glass material, Kr
Whether the quartz used for the F laser can be used,
This is because there are many problems such as 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.

[0006] In the measurement of the ultraviolet region, an integrating sphere having a white pigment such as barium sulfate coated on its inner surface has been used. In the past, there was no problem because light in the visible region was mainly used, but in the ultraviolet region, particularly in the deep ultraviolet and vacuum ultraviolet regions, absorption was large and sufficient performance could not be exhibited.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art. It is an object of the present invention to provide a spectrometer and a spectrometer using the same and an exposure printing apparatus for semiconductor production using the spectrometer.

[0008]

That is, the present invention relates to an integrating sphere used in a spectrometer for measuring the spectral energy intensity and distribution of light, wherein the inner surface contains inorganic phosphor particles and fluororesin particles. An integrating sphere characterized by having a phosphor film.

The present invention also provides a spectrometer for measuring the spectral energy intensity and distribution of light using an integrating sphere, wherein a phosphor film containing inorganic phosphor particles and fluororesin particles is provided on the inner surface of the integrating sphere. A spectrometer is provided.

Further, the present invention is an exposure printing apparatus for manufacturing a semiconductor using the above-mentioned spectrometer. Further, the present invention provides a spectroscopic measurement method for measuring the spectral energy intensity and distribution of light, wherein light is applied to an integrating sphere in which a phosphor film containing inorganic phosphor particles and fluororesin particles is provided on the inner surface. A spectrometric method comprising the steps of: emitting fluorescent light; and diffusely 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.

The wavelength range of the light to be measured is 300 nm.
It is preferred that: It is preferable that a phosphor film containing inorganic phosphor particles and fluororesin particles is provided on the entire inner surface of the integrating sphere. It is preferable that a phosphor film containing inorganic phosphor particles and fluororesin particles is provided on a part of the inner surface of the integrating sphere. It is preferable that the phosphor film containing the inorganic phosphor particles and the fluororesin particles provided on the entire surface or a part of the inner surface of the integrating sphere also serves as the light diffusion reflector.

It is preferable that the phosphor film provided on the inner surface of the integrating sphere contains a fluorine resin as a binder for suspending and supporting the inorganic phosphor particles. It is preferable that the content of the binder is 50% by weight or less based on 100 of the phosphor particles. It is preferable that the phosphor film containing the inorganic phosphor particles and the fluororesin particles provided on the inner surface of the integrating sphere is subjected to heat treatment.

The inorganic phosphor particles are made of BaMg ₂ Al ₁₆ O
_{27: Eu, (SrCaBa) 5} (PO 4) 3 Cl: E
u, BaSi ₂ O ₅ : Pb, YPO ₄ : Ce, Sr ₂ P ₂
O ₇ : Eu, ZnS: Cu, Al, CaWO ₄ , BaF
It is preferably at least one selected from Br: Eu, CaF ₂ : Eu, and BaSO ₄ : Pb.

It is preferable that the fluororesin constituting the phosphor film provided on the inner surface of the integrating sphere is an ethylene tetrafluoride resin, a derivative thereof and a copolymer resin thereof.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have studied the measurement of light energy in the ultraviolet region, in particular, the deep ultraviolet region, the vacuum ultraviolet region,
Improves and solves the problems that occur when using an integrating sphere with the above-mentioned conventional white pigment such as barium sulfate applied to the light in the soft X-ray range. In order to achieve this, we attempted to improve and improve the integrating sphere, which is the main point of measurement and evaluation of spectral energy.

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

Conventionally, as a characteristic required for an integrating sphere,
1. 1. high reflectance; 2. uniform diffusion (scattering); Uniform spectral characteristics. In addition, in order to measure light energy such as far ultraviolet light and vacuum ultraviolet light, it is necessary to set the light energy to 4. 4. Conversion of measuring instrument to sensitive wavelength range; Prevention of pollution by environment and atmosphere. However, the conversion of the light measuring instrument 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. As a result, direct measurement of deep ultraviolet and vacuum ultraviolet is difficult as a result.

Accordingly, the present invention uses a phosphor film containing a phosphor on the inner surface of an integrating sphere to convert light such as far ultraviolet light or vacuum ultraviolet light into a long-wavelength light having a fluorescent wavelength by wavelength conversion. It is characterized in that measurement is performed in the emission wavelength range that matches the characteristics of the device. In addition, we propose innovative measures to improve the conversion efficiency to long wavelengths such as far ultraviolet and vacuum ultraviolet, and to improve the reflectance and reflection characteristics of the integrating sphere, which are major problems here. These features include: 1. wavelength conversion of ultraviolet light to long wavelength by using a phosphor; 2. Improvement of conversion efficiency by adoption and installation of inorganic phosphor. Inorganic phosphors are further utilized and used as a reflection / diffusion material, thereby further improving conversion efficiency.

That is, the spectrometer of the present invention uses an integrating sphere having an inner surface provided with a phosphor film containing inorganic phosphor particles and fluororesin particles for spectroscopy of light such as far ultraviolet and vacuum ultraviolet. It is characterized by measuring energy intensity and distribution.

The spectral measurement method for measuring the spectral energy intensity and distribution of light is performed by irradiating light onto an integrating sphere having a phosphor film containing inorganic phosphor particles and fluororesin particles on its inner surface. A step of emitting a light beam; and a step of diffusing and reflecting the emitted fluorescent light beam on the inner surface of the integrating sphere to measure the spectral energy intensity and distribution of the fluorescent light beam.

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 reflected by the reflection mirror 6a.
Is guided to the integrating sphere 7 through the sample s.

FIGS. 2 and 3 are schematic views of an integrating sphere used in the spectrometer of the present invention. FIG. It is sectional drawing seen from the direction. On the inner surface of the integrating sphere 7, a phosphor film 10 containing inorganic phosphor particles and fluororesin particles is provided. 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 is irradiated to the light irradiation area 15 which is directly irradiated with the sample light. Phosphor film 1 containing a phosphor by irradiation with sample light 12
The fluorescent light 22 emits from 0, and the emitted fluorescent light 22
Further, the light is reflected and diffused on the surface of the light reflection / diffusion area 16 other than the light irradiation area 15 on the inner surface of the integrating sphere 7 and reaches the detector 13 composed of a photoelectric tube (photomultiplier) through the light receiving window 9 for measurement. You. On the other hand, the reference light 11 guided from the reflection mirror 6b of the spectrometer shown in FIG.
Irradiates the phosphor film 10 at the position of the inner surface of the integrating sphere 7 (below the paper surface) through another entrance window (not shown) from an angle (upper to the paper surface) shifted by 90 degrees from Similarly, the emitted fluorescent light is reflected by the light reflection / diffusion region 16 on the inner surface of the integrating sphere.
While reflecting and diffusing the surface of the photodetector, the light reaches the detector 13 composed of a phototube and used for measurement.

Here, the unconverted sample light 12 is repeatedly reflected and diffused on the surface of the light reflection / diffusion region 16 inside the integrating sphere, whereby the wavelength conversion proceeds and the conversion efficiency is improved.

The spectrometer of the present invention can be applied to spectrometry and light quantity measurement in the deep ultraviolet, vacuum ultraviolet, and soft X-ray regions where the wavelength region of light is 300 nm or less, preferably 120 to 250 nm.

The inorganic phosphor particles used in the phosphor film provided on the inner surface of the integrating sphere of the present invention are phosphors that emit fluorescent light upon stimulation by light in the far ultraviolet, vacuum ultraviolet, and soft X-ray regions. use. Detector (phototube) characteristics (spectral sensitivity)
High sensitivity and high performance measurement can be expected if the emission wavelength of the phosphor is matched with that of the phosphor. However, the types of detectors (phototubes) are actually limited, and the inorganic phosphor It is preferred to select the type of particles. Other conditions required for the inorganic phosphor particles include emission time, remaining half characteristics, stability, and weather resistance.

In the present invention, the inorganic phosphor particles
It is not necessary to specifically limit the type of phosphor, but for example,
BaMg_Two Al₁₆O₂₇: Eu, (SrCaBa)_Five 
(PO _Four )_Three Cl: Eu, BaSi_TwoO_Five: Pb, YPO
_Four : Ce, Sr_Two P_Two O₇ : Eu, ZnS: Cu, A
1, CaWO_Four , BaFBr: Eu, CaF_Two : Eu,
BaSO_Four : At least one selected from Pb
It is.

These inorganic phosphor particles have an average particle diameter of 2
White particles of about 0 to 1 μm, preferably about 8 to 4 μm are desirable.

Typical examples of the fluororesin used for the phosphor film provided on the inner surface of the integrating sphere of the present invention include those generally referred to as ethylene tetrafluoride resin and its derivatives and copolymer resins thereof. And specifically,
Examples include ethylene tetrafluoride resin, vinylene fluoride resin, vinylidene fluoride resin, vinyl fluoride resin, ethylene tetrafluoride perfluoroalkyl vinyl ether copolymer resin, and trifluoroethylene chloride-ethylene copolymer resin.

These fluororesin particles have an average particle diameter of 20.
White particles of about 1 to 1 μm, preferably about 10 to 4 μm are desirable.

The mixing ratio of the inorganic phosphor particles and the fluororesin particles is 100 to 10 parts by weight, preferably 50 to 20 parts by weight, of the inorganic phosphor particles and 50 to 1 part by weight, preferably 50 to 1 part by weight. A range of 20 to 5 parts by weight is desirable.

Conventionally, a water-soluble resin has been used as a binder resin for suspending and supporting the phosphor, because of its easy handling. Representative examples include polyvinyl alcohol, carboxymethyl cellulose, polyvinylpyrrolidone, and the like. In the past, the problem did not appear on the surface because measurement was mainly in the visible region, but when entering the vacuum ultraviolet region, light absorption of oxygen, water, organic substances, etc. affected and became a problem .

According to the present invention, a non-aqueous phosphor film is provided on a phosphor film provided on the inner surface of an integrating sphere by using a fluorine resin as a binder resin for suspending and supporting the inorganic phosphor particles and the fluorine resin particles. Application of the substrate became possible.
As the fluorine resin, the above-mentioned ethylene tetrafluoride resin and its derivatives and their copolymer resins are used.

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

A phosphor film consisting of inorganic phosphor particles and fluororesin particles alone is prepared by dispersing powders of inorganic phosphor particles and fluororesin particles in a solvent such as alcohol and coating the inner surface of an integrating sphere hollow sphere. It can be formed by drying and heat treatment.

Further, the phosphor film containing the inorganic phosphor particles and the binder for suspending and supporting the fluororesin particles may be a solution containing the powder of the inorganic phosphor particles and the fluororesin particles, a binder and a solvent. Can be formed by applying the composition to the inner surface of the substrate, drying and heating.

The content of the binder in the phosphor film is 50% by weight or less, preferably 20 to 5% by weight, based on the inorganic phosphor 100 on a dry weight basis. The thickness of the phosphor film is preferably in the range of about 0.5 to 2 mm. Further, it is preferable that the above-mentioned phosphor film is made of a light reflection / diffusion material having a reflectance of 90% or more.

The method of forming the phosphor film on the inner surface of the hollow sphere of the integrating sphere is not limited to the above-mentioned coating method, but may be formed by vapor-depositing and depositing a phosphor.

The phosphor film containing the inorganic phosphor particles and the fluororesin particles may be provided on the entire inner surface of the integrating sphere, or may be provided on a part of the inner surface of the integrating sphere. Good. The phosphor film containing the inorganic phosphor particles and the fluororesin particles provided on the entire surface or a part of the inner surface of the integrating sphere can also serve as the light diffusion reflector.

When the above-mentioned phosphor film is provided in a part of the inner surface of the integrating sphere, an ultraviolet ray reflection film such as a fluororesin particle film is provided in another region. The integrating sphere is usually used in combination with a detector, and a light receiving window 9 for receiving light to the detector,
The size of the entrance window 8 through which the light beam enters the hollow sphere is preferably about 1/10 of the inner diameter of the sphere.

The hollow sphere of the integrating sphere is not particularly limited and may be a commonly used one. 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.

The spectrometer of the present invention uses the above-mentioned integrating sphere to obtain the spectral energy intensity and distribution of light in the deep ultraviolet, vacuum ultraviolet, and soft X-ray regions having a wavelength region of 300 nm or less. A measurement can be made. The exposure printing apparatus for manufacturing a semiconductor according to the present invention can be manufactured using the above-described spectrometer.

[0043]

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 : 10 parts by weight of Eu powder (average particle size: 6 μm)
4 parts by weight of ethylene tetrafluoride resin powder (average particle diameter 7 μm) and 20 parts by weight of ethyl alcohol were prepared.

After the phosphor was weighed in a container, ethyl alcohol was added and stirred. After the particles were sufficiently dispersed, the base liquid was prepared by adding tetrafluoroethylene resin powder and further mixing and stirring.

A constant temperature (for example, 5
After setting the hemisphere of the integrating sphere kept at 0 ° C.) on a rotating plate, the coating solution was applied using a brush while rotating. The inner surface of the completed integrating sphere had a white, matte, uniform finish with no unevenness. After the coated hemisphere was sufficiently dried, it was subjected to a heat treatment at 350 ° C. using a muffle furnace. The heat-treated film was sufficiently strengthened and became practical.

An integrating sphere was formed by combining the two hemispheres. The integrating sphere was set in the spectrometer shown in FIG. 1 and compared with a measurement result of a conventional integrating sphere using barium sulfate.
Visible light conversion was performed at the center of 50 nm, and the output was increased about 10 times as compared with the conventional one in combination with the spectral sensitivity of the phototube. Therefore, stable spectral measurement results with less noise were obtained.

Example 2 Using an integrating sphere substrate, brass was used, and an integrating sphere processed by cutting and polishing and silver-plated on the surface was used. This embodiment, as the phosphor _{(SrCaBa) 5 (PO 4)} 3 Cl: Using Eu (average particle size 8 [mu] m). A substrate liquid was prepared in the same manner as in Example 1. Phosphor 10 parts by weight, ethyl alcohol 15
3 parts by weight of vinylidene fluoride resin powder (average particle diameter: 10 μm) as a fluorine resin were uniformly stirred and mixed. The prepared substrate liquid was similarly applied to each hemisphere of the integrating sphere using a spray gun, and dried to obtain a uniformly coated white matte hemisphere. After the heat treatment at 320 ° C., the two hemispheres were combined to form an integrating sphere, and then set in the spectrometer shown in FIG.

As compared with the measurement result of the integrating sphere using the conventional barium sulfate, the output was 450
Since the wavelength was increased about 8 times in combination with the converted wavelength at the center of nm, a stable measurement result with little noise was obtained.

Example 3 In Example 1, the coating liquid was applied only to the area which was directly irradiated with ultraviolet rays. BaSi ₂ O ₅ : Pb as phosphor
10 parts by weight (average particle diameter: 7 μm), 4 parts by weight of ethylene tetrafluoroethylene perfluoroalkyl vinyl ether copolymer resin (average particle diameter: 10 μm), and 12 parts by weight of ethyl alcohol were prepared. The substrate liquid was adjusted by mixing and stirring in the same manner as in Example 1, and after coating, a heat treatment at 320 ° C. was performed.

Thereafter, PVA (5% aqueous solution) of tetrafluoroethylene resin particles and ethyl alcohol dispersion (mixing ratio, fluorine resin: PVA solution: alcohol = 10:
2:15) was applied using a brush. The result was a white, matte, uniform finish as a whole. After combining the two hemispheres to form an integrating sphere, it was set in the spectrometer shown in FIG.

As compared with the measurement result of the integrating sphere using barium sulfate in the same manner as in Example 1, it was found that the ultraviolet light was 35%.
The light was converted to near-ultraviolet light having a center of 0 nm, and a stable spectral measurement result with a noise of about eight times the output and less noise was obtained in combination with the spectral sensitivity of the phototube.

Example 4 In Examples 1 to 3, YPO ₄ : Ce, Sr was used as the phosphor.
₂ P ₂ O ₇ : Eu, ZnS: Cu, Al, etc., and an integrating sphere is made by the same method using vinyl tetrafluoride resin, ethylene trifluoride chloride-ethylene copolymer resin, etc. as a fluorine resin. did. In each case, the integrating spheres produced provided stable measurement results with little noise in combination with the spectral sensitivity of the phototube.

Example 5 In the same manner as in Example 1, the entire optical system of the spectrometer shown in FIG. 1 was subjected to spectrometry in an oxygen-free atmosphere by purging with nitrogen. In the wavelength region of 200 nm or less, high-precision measurement with much less noise than before can be performed.
FIG. 4 shows data obtained by measuring the spectral transmittance of the calcium fluoride glass material in the vacuum ultraviolet region, and a high-precision measurement according to the theoretical value was possible.

Example 6 An integrating sphere having an inner spherical surface with a diameter of 20 mm was prepared. The substrate was made by cutting aluminum blocks into hemispheres. Through the same steps as in Example 1, a phosphor BaMg ₂ Al ₁₆ O ₂₇ : Eu using ethylene tetrafluoride as a binder is formed on the inner surface of the integrating sphere.
Was formed.

FIG. 5 is a schematic view showing an apparatus for measuring the exposure illuminance of an exposure printing apparatus for manufacturing semiconductors. The integrating sphere was set on the exposure stage 21 for measuring the exposure illuminance of the exposure printing apparatus for semiconductor production. Part of the irradiation light projected by the projection optical system 24 is introduced into the integrating sphere 25 through a pinhole 23 provided on the stage 21 for measurement. The introduced measurement light is converted into long-wavelength light by the phosphor film 26 on the inner surface, sent to the detector 27, and used for measurement. By applying this method, the illuminance and illuminance non-uniformity of vacuum ultraviolet rays, soft X-rays, etc., which were impossible to measure conventionally
Measurements can be made with high accuracy, and as a result, the productivity can be improved.

[0057]

As described above, according to the present invention, it is possible to accurately measure the spectral energy distribution and intensity in the ultraviolet region, particularly in the deep ultraviolet, vacuum ultraviolet, and soft X-ray regions. , A spectrometer and a spectrometer using the same. Also, there is provided an exposure printing apparatus for semiconductor manufacturing using a spectrometer capable of accurately measuring the spectral energy intensity and distribution of light in the ultraviolet region, particularly in the deep ultraviolet, vacuum ultraviolet region, and soft X-ray region. can do.

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

FIG. 4 is a view showing data obtained by measuring a spectral transmittance of a calcium fluoride glass material in a vacuum ultraviolet region in Example 5.

FIG. 5 is a schematic view showing an apparatus for measuring exposure illuminance of an exposure printing apparatus for manufacturing a semiconductor.

[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 reception window 10 phosphor film 11 reference light 12 sample light 13 detector 14 hollow sphere 15 light irradiation area 16 light Reflection / diffusion area 22 fluorescent light s sample 21 exposure stage 23 pinhole 24 projection optical system 25 integrating sphere 26 phosphor film 27 detector 28 wafer

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2G020 AA05 BA20 CA01 CB23 CB43 CB44 CB55 CD23 2H097 CA13 LA10 5F046 DB01 DB11 GA14

Claims (14)

[Claims] 1. An integrating sphere used in a spectrometer for measuring the spectral energy intensity and distribution of light, wherein an inner surface is provided with a phosphor film containing inorganic phosphor particles and fluororesin particles. Integrating sphere to feature. 2. The wavelength range of the measured light is 300 n.
2. The integrating sphere according to claim 1, wherein m is equal to or less than m. 3. The integrating sphere according to claim 1, wherein a phosphor film containing inorganic phosphor particles and fluororesin particles is provided on the entire inner surface of said integrating sphere. 4. The integrating sphere according to claim 1, wherein a phosphor coating containing inorganic phosphor particles and fluororesin particles is provided on a part of the inner surface of said integrating sphere. 5. The integrating sphere according to claim 3, wherein the phosphor film containing the inorganic phosphor particles and the fluororesin particles provided on the entire surface or a part of the inner surface of the integrating sphere also functions as a light diffusion reflector. 6. The integration according to claim 1, wherein the phosphor coating provided on the inner surface of the integrating sphere contains a fluororesin as a binder for suspending and supporting the inorganic phosphor particles. ball. 7. The integrating sphere according to claim 6, wherein the content of the fluorine resin as the binder is 50% by weight or less based on 100 of the inorganic phosphor particles. 8. The integrating sphere according to claim 1, wherein the phosphor film containing the inorganic phosphor particles and the fluororesin particles provided on the inner surface of the integrating sphere is subjected to a heat treatment. 9. The method according to claim 9, wherein the inorganic phosphor particles are BaMg ₂ Al ₁₆
O ₂₇ : Eu, (SrCaBa) ₅ (PO ₄ ) ₃ Cl: E
u, BaSi ₂ O ₅ : Pb, YPO ₄ : Ce, Sr ₂ P ₂
O ₇ : Eu, ZnS: Cu, Al, CaWO ₄ , BaF
_{Br: Eu, CaF 2: Eu} , BaSO 4: integrating sphere according to any one of claims 1 to 8 is at least one selected from Pb. 10. The fluororesin constituting the phosphor film provided on the inner surface of the integrating sphere is an ethylene tetrafluoride resin, a derivative thereof, and a copolymer resin thereof.
The integrating sphere according to any one of the above items. 11. A spectrometer for measuring the spectral energy intensity and distribution of light using an integrating sphere.
A spectrometer using the integrating sphere according to any one of claims 1 to 10. 12. An exposure printing apparatus for manufacturing a semiconductor using the spectrometer according to claim 11. 13. A spectrophotometric method for measuring the spectral energy intensity and distribution of light, comprising: irradiating light onto an integrating sphere having a phosphor film containing inorganic phosphor particles and fluororesin particles on an inner surface thereof to emit light. A method of emitting a light beam, and a step of measuring the spectral energy intensity and distribution of the emitted fluorescent light by diffusely reflecting the emitted fluorescent light on an inner surface of an integrating sphere. 14. The wavelength range of the measured light is 300.
The spectrometry method according to claim 13, which is not more than nm.