JP2000185950A - Stacked optical thin film and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a stacked optical thin film having reduced light scattering, high durability and higher performance by making a sublimable, crystalline organic compound exist as an amorphous compound, a microcrystalline one or solid solution. SOLUTION: When this stacked optical thin film is produced by putting the powder or film of a meltable organic compound between the substrate surface deposited with a sublimable organic compound and the second substrate, by melting the meltable organic compound under a vacuum and heated condition and then by subjecting two substrates to compression bonding, the sublimable organic compound is in at least one kind selected from following states: (1) an amorphous state; (2) a microcrystalline state where the diameter of a crystal grain doesn't exceed one fifth times the wavelength of light applied to the stacked optical thin film; (3) solid solution where the meltable organic compound is adopted as medium.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a laminated optical thin film and a method for producing the same. More specifically, the present invention is useful for optical technology such as wavelength selective transmission film, reflection film, optical nonlinear effect film, photoelectric conversion device, photochromic device, thermal lens effect device, and optoelectronic technology, and has high functionality and high durability. Regarding the laminated optical thin film,
Further, the present invention relates to a new manufacturing method capable of manufacturing a laminated optical thin film with high quality and high efficiency.

[0002]

2. Description of the Related Art Conventionally, optical thin films having various compositions have been used in various application fields, and those utilizing a wavelength selective transmission or reflection function utilizing light absorption or interference have been known for a long time. I have. In recent years, especially in the field of optoelectronics using laser light, in terms of applications, applications for multi-parallel high-speed processing of information using the multiplexing of light, and in terms of phenomena, applications of optical nonlinear effect or photoelectric effect. Therefore, development of an optical thin film having a high function different from the conventional one has been actively promoted.

An organic optical material has attracted attention as a material for forming such a new high-performance optical thin film and as a composition thereof. Various studies have been made on a method of manufacturing an organic optical thin film using the organic optical material, and the following methods are known, for example.

(1) Wet method using solution, dispersion liquid or developing solution Coating method such as coating method, blade coating method, roll coating method, spin coating method, dipping method, spraying method, planographic printing, letterpress printing, intaglio printing, Printing method such as stencil, screen, transfer, etc., electrodeposition method, electrolytic polymerization method, micellar electrolytic method
243298), a Langmuir-Blodgett method of transferring a monomolecular film formed on water, and the like.

(2) Method of utilizing polymerization or polycondensation reaction of raw material monomers When the monomer is a liquid, a casting method, a reaction injection molding method, a plasma polymerization method,
Photopolymerization method.

(3) Method using gas molecules (vaporization method by heating) Sublimation transfer method, evaporation method, vacuum evaporation method, ion beam method, sputtering method, plasma polymerization method, photopolymerization method and the like.

(4) Method utilizing melting or softening Hot press method (Japanese Patent Application Laid-Open No. 4-99609), solvent reprecipitation / heat melting method (Japanese Patent Application Laid-Open No. 6-263885), injection molding method, stretching method, Single crystallization method of molten thin film.

(5) A method of spraying a solution or a dispersion on a substrate placed in a vacuum. JP-A-6-306181 and JP-A-7-2526
The method described in No. 71. Generally, in order to practically use an organic optical thin film using an organic optical material, it is necessary to sufficiently control the following phenomena as basic requirements. [1] Light scattering in the wavelength band of light used. [2] Light absorption in the wavelength band of light used. [3] Evaporation / foaming of volatile components due to temperature rise due to light irradiation.

First, as the first basic requirement of an organic optical thin film using an organic optical material, scattering of light in a wavelength band of light to be used is extremely important. Light scattering of the light source of the liquid crystal display, such as a light diffusing film for homogenizing, except for the purpose of scattering light, the smaller the light scattering in the wavelength band of the light used, the better. . When the organic optical thin film contains an organic compound having high crystallinity, a method using a single crystal thin film of a crystalline organic compound, and a method using a crystal size of the crystalline organic compound are used to reduce light scattering. A method of making the wavelength significantly smaller than the wavelength of light in the light wavelength band (for example, 1/10 or less of the wavelength), and a method of allowing a crystalline organic compound to exist as an amorphous state alone or in combination with other components. And a method of dispersing molecules in a matrix material.

[0010]

When an optical thin film containing an organic compound having a high crystallinity is to be formed so as to reduce light scattering by using the conventional film forming method as described above, the following problem arises. There are various issues.

In the case of a single crystal thin film of a crystalline organic compound, (1) Various methods for single crystallization of a molten thin film have been proposed, but this method can be applied only to compounds showing a melting point. (2) It is not easy to avoid thermal decomposition at the melting temperature. (3) Anisotropy in the film cannot be avoided corresponding to the orientation of the single crystal.

In the case of a crystal of a crystalline organic compound, (1) a case where microcrystals of the crystalline organic compound are dispersed in a medium or a liquid precursor of a matrix material (for example, a polymerizable oligomer or monomer) to form a film by a wet method; However, it is not easy to prevent crystal growth. In particular, it is necessary to add a crystal growth-inhibiting component or a surfactant in order to stably allow microcrystals of the crystalline organic compound to have a particle size of 1/10 or less of the wavelength of visible light, that is, 40 to 75 nm. , There are many restrictions.

(2) When a film is formed by the above-mentioned wet method or casting method, it is impossible to avoid that volatile components such as a medium or a precursor of a matrix material remain in the optical thin film. When the thickness of the thin film does not exceed 1 μm, it is possible to remove most of the volatile components by performing the heat treatment under high vacuum for a long time. However, when the film thickness exceeds, for example, 10 μm, even if the heat treatment is performed for a long time under a high vacuum, volatile components remain in the optical thin film, and the optical power durability of the optical thin film is significantly impaired. That is, when light with a high power density passes, the volatile components evaporate in the thin film to form bubbles, which damage the optical thin film.

When the crystalline organic compound is made amorphous: (1) When a plurality of similar structures of the crystalline organic compound are mixed and present, a non-equilibrium state is realized by kinetic control, Quality. However, it is in a metastable state to the last, and crystallization may proceed due to a rise in temperature due to light irradiation or the like. (2) When vacuum deposition is performed under non-equilibrium conditions by controlling the substrate temperature, even if a crystalline organic compound is used alone,
An amorphous deposited film can be obtained. However, it is in a kinetic frozen state, and crystallization may proceed due to a temperature rise due to light irradiation or the like.

Molecular dispersion (solid solution) in matrix material
In this case, (1) a matrix material is essential, and there is a limit to increasing the concentration of a solute component. (2) Only organic compounds having the property of solid solution in the matrix material can be used.

Next, as a second basic requirement required for an organic optical thin film using an organic optical material, absorption of light in a wavelength band of light to be used is extremely important. In a wavelength selective transmission film, a photoelectric conversion device, a thermal lens effect element, and the like, an organic optical material is used for light in its absorption band. There, a significant portion of the absorbed energy is converted to thermal energy. Here, when the organic optical thin film contains an organic compound having a high crystallinity, if the compound is present as a crystal, it takes time for the absorbed heat to radiate to the outside of the crystal, and as a result, the inside of the crystal becomes , Easily reach the thermal decomposition start temperature, and the optical power durability of the optical thin film is significantly reduced.

Third, it is necessary to thoroughly remove components that evaporate due to a temperature rise accompanying light irradiation from an organic optical thin film using an organic optical material. In particular, it is important in a usage form in which a high-power laser beam is converged and irradiated. As described above, not only when forming a film by a wet method such as the wet method or the casting method, but also when using a method utilizing melting or softening or a method of spraying a solution or dispersion liquid on a substrate placed under vacuum. Even in such a case, it is necessary to thoroughly degas the organic optical thin film using the organic optical material at any stage of the film forming material or the film forming process. Here, when the organic optical material contains an organic compound having a high sublimation property, during the deaeration treatment, the sublimable component is sublimated and lost, and the composition of the organic optical material deviates from a predetermined ratio. Problem.

Accordingly, the present invention solves the above-mentioned drawbacks of the prior art and reduces the light scattering by allowing a sublimable and crystalline organic compound to exist in an amorphous state, a fine crystalline state, or a solid solution. It is another object of the present invention to provide a highly durable laminated optical thin film having higher functionality.

According to the present invention, there is also provided an organic compound having a high sublimation property at a predetermined ratio, containing no volatile impurities, and furthermore, crystallization of amorphous or crystal growth of microcrystals by light irradiation. It is an object of the present invention to provide a method of manufacturing a multilayer optical thin film for efficiently manufacturing a higher-performance multilayer optical thin film that can withstand high-power-density light irradiation.

[0020]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention provides a method of forming a powder of a fusible organic compound between a deposition surface of a first substrate on which a sublimable organic compound is deposited and a second substrate. Sandwiching a film, heating under vacuum, a step of melting the fusible organic compound and a step of pressing the first and second substrates, a laminated optical thin film produced by the step of:
There is provided a laminated optical thin film wherein the sublimable organic compound is in at least one state selected from the group consisting of the following three states.

(A) an amorphous state, (b) a microcrystalline state having a crystal particle diameter not exceeding 1/5 of the wavelength of light irradiated to the laminated optical thin film, (c) the fusible organic material A solid solution using a compound as a medium.

According to the present invention, in order to solve the above-mentioned problems, the sublimable organic compound vapor-deposited surfaces of the two substrates on which the sublimable organic compound is vapor-deposited face each other, and the powder of the fusible organic compound or A laminated optical thin film produced by sandwiching a film, heating under vacuum to melt the fusible organic compound, and pressing two substrates together, wherein the sublimable organic compound comprises the following three components: There is provided a laminated optical thin film characterized by being in at least one state selected from states.

(A) an amorphous state, (b) a microcrystalline state in which the crystal particle diameter does not exceed 1/5 of the wavelength of light applied to the laminated optical thin film, (c) the fusible organic material A solid solution using a compound as a medium.

In order to solve the above-mentioned problems, the present invention provides a method of depositing an organic compound on at least one surface of a first substrate, and a step of depositing an organic compound on the first substrate on which the organic compound is deposited. Sandwiching a powder or a film of a fusible organic compound between the two substrates, heating under vacuum to melt the fusible organic compound, and further pressing the first and second substrates. A method for producing a laminated optical thin film is provided.

A step of depositing a sublimable organic compound on at least one surface of each of the two substrates; and a step of facing the surfaces of the two substrates on which the organic compound is deposited, and interposing a powder of the fusible organic compound therebetween. Alternatively, there is provided a method for producing a laminated optical thin film, comprising: a step of sandwiching the film, heating under vacuum to melt the fusible organic compound, and pressing two substrates together.

In any of the manufacturing methods, a step of purifying the substrate surface, for example, under a high vacuum may be performed prior to the above steps. Further, following the pressure bonding step, two sheets are used for the purpose of preventing water and oxygen from penetrating from the end face of the laminated film and adversely affecting the same, and for preventing the sublimable component from gradually sublimating and being lost from the end face. A step of molding the peripheral portion of the substrate may be added.

[0027]

DESCRIPTION OF THE PREFERRED EMBODIMENTS [Example of Sublimable and Crystalline Organic Compound] First, an organic low-molecular compound which forms a single crystal exhibiting a second-order nonlinear optical effect can be mentioned. Specific examples include urea and its derivatives, m-nitroaniline, 2-
Benzene derivatives such as methyl-4-nitro-aniline, 2- (N, N-dimethylamino) -5-nitroacetanilide, N, N'-bis (4-nitrophenyl) methanediamine, 4-methoxy-4'- Biphenyl derivatives such as nitrobiphenyl, stilbene derivatives such as 4-methoxy-4'-nitrostilbene, 4-nitro-3-picoline = N-oxide, (S)-(-)-N- (5-nitro-2- Examples thereof include pyridine derivatives such as (pyridyl) prolinol, chalcone derivatives such as 2 ′, 4,4′-trimethoxychalcone, and thienylchalcone derivatives.

Next, as a specific example of a sublimable and crystalline organic compound (organic dye), which exhibits light absorption in a wavelength band from ultraviolet to visible light to near infrared, a porphyrin dye,
Examples include phthalocyanine dyes, naphthoquinone dyes, anthraquinone dyes, naphthalenetetracarboxylic diimide dyes, and perylenetetracarboxylic diimide dyes.

Further, a photochromic phenomenon occurs, and as a sublimable and crystalline organic compound, 6-bromo-
1 ′, 3′-dihydro-1 ′, 3 ′, 3′-trimethyl-8-nitrospiro [2H-1-benzopyran-2,
2 ′-(2H) -indole], 5-chloro-1,3-
Dihydro-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] naphtho [2,1-b]
[1,4] oxazine], 5-chloro-1,3-dihydro-1,3,3-trimethylspiro [2H-indole-2,3 ′-[3H] naphtho [9,10-b] [1,
4] oxazine], 6,8-dibromo-1 ′, 3′-dihydro-1 ′, 3 ′, 3′-trimethylspiro [2H-
1-benzopyran-2,2 '-(2H) -indole], 1', 3'-dihydro-1 ', 3', 3'-trimethyl-6-nitrospiro [2H-1-benzopyran-
2,2 ′-(2H) -indole], 1 ′, 3′-dihydro-5′-methoxy-1 ′, 3 ′, 3′-trimethyl-6-nitrospiro [2H-1-benzopyran-2,
2 ′-(2H) -indole], 1 ′, 3′-dihydro-8-methoxy-1 ′, 3 ′, 3′-trimethyl-6
Nitrospiro [2H-1-benzopyran-2,2'-
(2H) -indole], 1,3-dihydro-1,3,3
3-trimethylspiro [2H-indole-2,3'-
[3H] naphtho [2,1-b] [1,4] oxazine], 1,3-dihydro-1,3,3-trimethylspiro [2H-indole-2,3 ′-[3H] phenanthro [9, 10-b] [1,4] oxazine], 1,3-
Dihydro-1,3,3-trimethylspiro [2H-indole-2,3 ′-[3H] naphtho [2,1-b] pyran], 1,3-dihydro-5-methoxy-1,3,3-
Trimethylspiro [2H-indole-2,3 '-[3
Spiropyrans such as [H] naphtho [2,1-b] pyran], 2,5-dimethyl-3-furylethylidene succinic anhydride, Fulgides, 2,3-bis (2,4,5-trimethyl-3-thienyl) maleic anhydride, 2,3-bis (2,4,5-trimethyl-3-
Thienyl) maleimide, cis-1,2-dicyano-
Examples include diarylethenes such as 1,2-bis (2,4,5-trimethyl-3-thienyl) ethene.

[Evaporation method of organic compound] In addition to ordinary vacuum evaporation, evaporation under atmospheric pressure, evaporation in an inert gas such as nitrogen, argon, helium, and sputtering,
An evaporation method such as an ion beam method, a cluster ion beam method, or a molecular beam epitaxy method can be used.

[0031]

The present invention will be described below in more detail with reference to Examples.

EXAMPLE 1 Two ultraviolet lamps having a center wavelength of 185 nm and an output of 5 W and ultraviolet rays having a center wavelength of 254 nm and an output of 5 W were provided inside a vacuum vessel for cleaning a substrate connected to a vacuum deposition apparatus via a gate valve. Two lamps are mounted in such a manner that ultraviolet light is irradiated on the substrate surface, and a glass plate (24 mm × 30 mm × 0.15 mm) is used as the substrate.
After loading one or more sheets into the vacuum container,
Fill with clean nitrogen gas that has passed through a gas filter that collects 100% of fine particles with a diameter of 0.05 μm, and purify the atmosphere until no suspended dust (0.1 μm or more in diameter) and contaminant gas are detected inside. 0.0
Oxygen gas that has passed through a gas filter that collects 100% of 5 μm fine particles is introduced, the oxygen concentration is increased to 60% or more, and then an ultraviolet lamp is turned on. Processing was performed. After the above purification process is completed, the inside of the substrate cleaning vacuum vessel is evacuated,
After a high vacuum of 10 ⁻⁴ Pa or less,
^The substrate was transferred into a vacuum evaporation apparatus under a high vacuum of ⁻⁴ Pa or less. The spiropyran compound 1,3-dihydro-1,3,3-trimethylspiro (2H-indole-2,3 ′-[3H] naphtho [2,
1-b] [1,4] oxazine) (manufactured by Aldrich)
Was heated to 150 ° C. by a resistance wire and vacuum-deposited on the substrate. The control of the substrate temperature was not particularly performed. Monitor the progress of the deposition with a quartz crystal film thickness meter,
When the film thickness reached 0.5 μm, the shutter of the evaporation source was closed, and the evaporation was terminated. At this stage, the spiropyran compound exists as microcrystals in the deposited film on the glass substrate, causing significant light scattering, and the film is opaque.

On the other hand, a solution obtained by dissolving 0.1 g of poly (benzyl methacrylate) (manufactured by Aldrich) in 19 g of acetone was poured into 300 ml of n-hexane with stirring.
The precipitated resin lumps were filtered, washed with 30 ml of n-hexane, and the solvent was removed in clean air.
It was pulverized to a fine powder of less than μm. This poly (benzyl methacrylate) fine powder was gradually heated in a high vacuum container of 10 ⁻⁴ Pa or less and degassed in a temperature range of 40 ° C. to 50 ° C. for 48 hours.

In a clean atmosphere, fine resin powder subjected to high vacuum degassing was sprayed on the spiropyran vapor-deposited film on the glass substrate previously prepared, and another glass substrate (with no vapor-deposited film) was spread thereon. ) Are placed on a heating stage placed in a high vacuum container, and the pressure plate is evacuated to 10 ⁻⁴ Pa or less and heated to 95 to 100 ° C., while the pressure plate heated to 95 to 100 ° C. Pressing, 5kgf /
Vacuum hot pressing was performed at a pressure of cm ² .

By the above procedure, a transparent laminated optical thin film having a structure of glass / poly (benzyl methacrylate) in which the spiropyran compound was solid-solution / glass was prepared. This optical thin film was observed with a combination of a transmission optical microscope and a polarizing plate placed in a crossed Nicols arrangement, and it was confirmed that the spiropyran compound was not present as microcrystals.

When the transmission spectrum of the laminated optical thin film was measured, no influence of light scattering was observed.
The transmittance was 90% or more in the range of 0 nm to 900 nm (less than 500 nm, and absorption of the spiropyran compound exists in the ultraviolet region).

The thickness of the poly (benzyl methacrylate) layer in which the spiropyran compound was solubilized in the laminated optical thin film of the present embodiment was determined by the amount of the poly (benzyl methacrylate) fine powder sprayed and the heating temperature (60 ° C.). The temperature can be adjusted in the range of several μm to several hundred μm by adjusting the pressure treatment time (several minutes to several tens of hours) and, if necessary, by using a spacer in combination. .

In order to examine the laser proof strength of the laminated optical thin film of this embodiment, the wavelength of the Nd: YAG laser was 532 nm.
The output of the laser light obtained by converting the higher harmonic wave into 625 nm by a dye laser is adjusted to oscillate pulse light having a pulse light oscillation period of 10 Hz, a pulse width of 10 ns, and an average power of 20 mW. Focus on a beam cross section of 1.8 × 10 ⁻⁴ cm ² , 1.13 GW / c
Irradiation was performed at a peak power density of m ^{2 on} the laminated optical thin film of the present example [100 μm in thickness of the poly (benzyl methacrylate) layer in which the spiropyran compound was dissolved), but no optical damage occurred.

COMPARATIVE EXAMPLE 1 An ultraviolet curable resin (Dainichi Seiki) was placed between a glass substrate on which the spiropyran compound used in Example 1 was vapor-deposited in the same manner as in Example 1 and another glass substrate (no vapor-deposited film). "Seika Beam VDAL-3"
92 "), and cured by irradiating ultraviolet rays to prepare a laminated optical thin film having a structure of glass / ultraviolet curable resin layer containing the spiropyran compound / glass. Although the spiropyran compound deposited on the glass plate partially dissolves in the ultraviolet curing resin before curing, most of the spiropyran compound exists as microcrystals, causing light scattering, and transmitting through the obtained laminated optical thin film. The percentage was less than 50%.

A peak power density of 1.13 G was applied to the laminated optical thin film (the thickness of the ultraviolet curable resin layer containing the spiropyran compound was 100 μm) in the same manner as in Example 1.
When laser light of W / cm ² was irradiated, remarkable optical damage occurred only by irradiation of one pulse.

Comparative Example 2 An acetone solution containing 1 part by weight of the spiropyran compound used in Example 1 and 99 parts by weight of poly (benzyl methacrylate) was dissolved according to the method described in JP-A-10-202153. 0.1% by weight)
^Is sprayed onto a substrate placed in a high vacuum container of 10 ⁻⁴ Pa or less. At this time, the surface temperature of the substrate is set to a temperature (100) higher than the melting start temperature of poly (benzyl methacrylate).
C). Both the spiropyran compound and poly (benzyl methacrylate) do not decompose at 100 ° C. As a result, although a smooth film of poly (benzyl methacrylate) was deposited on the substrate, the concentration of the spiropyran compound in the film was measured under a microscope by an ultraviolet spectral absorption spectroscopy. However, it was found that the average density was significantly lower than that produced by the ordinary coating method. It is presumed that the spiropyran compound was deposited and sublimated from the heated substrate surface and lost at the same time as it was deposited in the film forming step under vacuum.

Comparative Example 3 1 part by weight of the spiropyran compound used in Example 1 and poly (benzyl methacrylate) 99
Acetone solution in which parts by weight are dissolved (solid content 10% by weight)
Was coated on a slide glass using an applicator. The film thickness after drying was adjusted to 20 μm. This coating film is ^{placed in} a vacuum vessel capable of reaching 10 ⁻⁴ Pa or less,
Heating was performed at 60 ° C. for 48 hours. Spectroscopic analysis confirmed that the spiropyran concentration decrease in the film before and after the treatment was very small.

When the laser proof strength of this coating film was measured in the same manner as in Example 1, foaming occurred at the irradiation point only by irradiation with one pulse of laser light having a peak power density of 1.13 GW / cm ² , Continued irradiation caused significant photodamage. The cause of the optical damage is presumed to be the solvent (acetone) remaining in the coating film. Therefore, Japanese Patent Application Laid-Open
The coating film was analyzed by the test method for organic optical materials described in -202179, and the presence of acetone was confirmed.

Example 2 Platinum phthalocyanine was used on the surface of a clean glass substrate in the same manner as in Example 1 except that platinum phthalocyanine was used in place of the above spiropyran compound and the temperature of the evaporation source was changed to 600 ° C. Evaporated. The progress of vapor deposition was monitored by a quartz crystal film thickness meter, and when the film thickness reached 0.2 μm, the shutter of the vapor deposition source was closed to terminate vapor deposition.

When the surface of the deposited film formed on the substrate was observed with a scanning electron microscope, platinum phthalocyanine vacuum-deposited under the above conditions had an outer diameter of 30 to 5 mm.
It turned out that it exists in the particle state of 0 nm. This particle size is one of the wavelengths of visible light (400 to 800 nm).
/ 5, which is a size that does not cause light scattering.

On the other hand, a solution prepared by dissolving 1 g of polycarbonate resin (Panlite L1250 manufactured by Teijin Chemicals Co., Ltd.) in 19 g of dichloromethane was poured into 300 ml of n-hexane while stirring, and the precipitated resin small lump was filtered.
The powder was washed with water, the solvent was removed in clean air, and pulverized to a fine powder having a particle outer diameter of less than 50 μm. This polycarbonate resin fine powder was gradually heated in a high vacuum container of 10 ⁻⁴ Pa or less and degassed in a temperature range of 100 ° C. to 120 ° C. for 48 hours.

In a clean atmosphere, a high vacuum degassed resin fine powder is sprayed on the platinum phthalocyanine vapor-deposited film on the glass substrate previously formed, and platinum phthalocyanine on another glass substrate is further spread thereon. The deposited films are placed one on top of the other, placed on a heating stage placed in a high vacuum vessel, evacuated to 10 ⁻⁴ Pa or less,
C., while a pressure plate heated to 240 to 260 ° C. was pressed, and vacuum hot pressing was performed at a pressure of 5 kgf / cm ² .

By the above procedure, glass / platinum phthalocyanine vapor-deposited film (thickness 0.2 μm) / polycarbonate resin layer / platinum phthalocyanine vapor-deposited film (thickness 0.
A laminated optical thin film having a structure of 2 μm) / glass was prepared.

The thickness of the polycarbonate resin layer is adjusted to 10 μm to 200 μm by adjusting the application amount of the resin powder, the heating temperature, and the pressure treatment time (from several minutes to several hours).
m were created.

The thickness of the polycarbonate resin layer is 100 μm
FIG. 1 shows the transmission spectrum of the laminated optical thin film of this embodiment in the case of (1). From this spectrum, it can be seen that a high transmittance was obtained except for the absorption band of platinum phthalocyanine.

A helium-neon laser (wavelength 632.6 nm, continuous oscillation power 20 mW, helium-neon laser) was applied to this laminated optical thin film (thickness of the polycarbonate resin layer 100 μm).
The expanded beam diameter was 8 mm and the energy distribution of the beam cross section was Gaussian distribution), and the beam was irradiated with a microscope objective lens having an effective aperture radius of 4 mm and a numerical aperture of 0.65 to a beam waist radius of 0.45 μm. The beam waist position was adjusted to match the platinum phthalocyanine vapor deposition film on the beam incident side. At this position, the continuous irradiation laser power density is 3 MW / cm ² . As a result, it was confirmed that even after the continuous irradiation for 8 hours, no light damage occurred at the irradiation point.

In the laminated optical thin film of this embodiment, the oxidizing decomposition reaction is suppressed because the irradiation point is shielded from the air, and the heat generated at the irradiation point is transmitted not only to the glass substrate but also to the resin layer. It is presumed that light damage can be prevented by smooth diffusion by propagation of light.

COMPARATIVE EXAMPLE 4 The same procedure as in Example 2 was carried out, except that the resin layer was not laminated on the platinum phthalocyanine vapor-deposited film on the glass substrate prepared in Example 2 but the wavelength was 632. .8 nm, laser power density 3M
When a laser beam of W / cm ² was irradiated from the glass substrate side, light scattering from the irradiation point increased within several minutes. The irradiation time was set to 1 second, 10 seconds, 100 seconds, and 10 minutes, and the irradiation point was moved to perform an irradiation experiment. When each irradiation point was observed with a microscope, discoloration started at 10 seconds and irradiation at 100 seconds. A hole was opened at the center of the sample, and after 10 minutes of irradiation, the hole was widened and the periphery was carbonized. It is presumed that the temperature rise due to light absorption is concentrated at the irradiation point because the glass substrate is only on one side, and that the glass substrate is exposed to the atmosphere, which results in a change in crystal form and dissipation due to sublimation, and further oxidative decomposition reaction has progressed. You.

[0054]

As described above in detail, according to the present invention, a sublimable and crystalline organic compound is present in an amorphous state, a microcrystalline state, or a solid solution to reduce light scattering and to have high durability. Thus, it is possible to provide a laminated optical thin film having a higher function.

The present invention also provides an organic compound having a high sublimation property at a predetermined ratio, does not contain volatile impurities, and further has an amorphous crystallization or crystal growth of microcrystals by light irradiation. Thus, it is possible to provide a method of manufacturing a laminated optical thin film for efficiently producing a more sophisticated laminated optical thin film that can withstand high power density light irradiation.

[Brief description of the drawings]

FIG. 1 is a diagram showing a transmission absorption spectrum of a laminated optical thin film of Example 2.

 ──────────────────────────────────────────────────続 き Continuing on the front page (74) The above two agents 100075258 Attorney Kenji Yoshida (two outsiders) (72) Inventor Takashi Hiraga 1-4-1 Umezono, Tsukuba, Ibaraki Pref. Within the research institute (72) Kuniei Chen 1-1-4 Umezono, Tsukuba, Ibaraki Pref.Industrial Technology Research Institute (72) Inventor Tetsuro Moriya 1-1-4 Umezono, Tsukuba, Ibaraki Pref. Inside the Electrotechnical Laboratory (72) Norio Tanaka, Inventor 1-7-6 Nibashi Bakurocho, Chuo-ku, Tokyo Inside Dainichi Seika Kogyo Co., Ltd. (72) Hiromitsu Yanagimoto 1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo (72) Inventor Ichiro Ueno 3-12-12 Moriyacho, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture Inside of Victor Company of Japan (72) Akira Shaji Kouji Tsujida 3-12 Moriyacho, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture F-term (reference) 2J048 DA04 GA05 GA09 GA12 GA60 4F100 AG00A AG00C AH00B AH02 AH07 AT00A AT00B AT00C BA03 BA10A BA10C DE01B EC66E66 EJ20 EJ42 EJ59 GB41 GB48 GB56 JM02 JN30 4G061 AA20 AA22 BA03 BA07 CA02 CB03 CB04 CB16 CD02 CD12 DA23 DA24 DA29 DA30 DA42

Claims (4)

[Claims] 1. A fusible organic compound powder or film is sandwiched between a deposition surface of a first substrate on which a sublimable organic compound is deposited and a second substrate, and the fusible organic compound is heated by heating under vacuum. A laminated optical thin film manufactured by a step of melting and a step of compressing the first and second substrates, wherein the sublimable organic compound is at least one selected from the group consisting of the following three states: A laminated optical thin film characterized in one of two states. (A) Amorphous state (b) Microcrystalline state in which the crystal particle diameter does not exceed 1/5 of the wavelength of light applied to the laminated optical thin film (c) The fusible organic compound as a medium Solid solution 2. The two substrates on which a sublimable organic compound is vapor-deposited face the sublimable organic compound vapor-deposited surfaces to each other, and a powder or film of a fusible organic compound is interposed therebetween, and heated under vacuum to melt the sublimable organic compound. Melt the organic compound
A laminated optical thin film manufactured by pressing a plurality of substrates, wherein the sublimable organic compound is in at least one state selected from the following three states. Thin film. (A) Amorphous state (b) Microcrystalline state in which the crystal particle diameter does not exceed 1/5 of the wavelength of light applied to the laminated optical thin film (c) The fusible organic compound as a medium Solid solution 3. a step of depositing an organic compound on at least one surface of the first substrate; and a powder of a fusible organic compound between the deposition surface of the first substrate on which the organic compound is deposited and the second substrate. Or a step of sandwiching the film, heating under vacuum to melt the fusible organic compound, and further pressing the first and second substrates under pressure. 4. A step of depositing a sublimable organic compound on at least one surface of each of at least two substrates; and opposing the surfaces of the two substrates on which the organic compound has been deposited. A step of sandwiching the powder or film of the above, heating under vacuum to melt the fusible organic compound, and further pressing two substrates under pressure.