JP5782673B2 - Transparent photo-oxidation layer thin film formation method - Google Patents

Description

In the present invention, since the silicone oil is bonded and coated by a photo-oxidation reaction in a short time, during the light irradiation, in order to promote the solidification of the applied silicone oil layer, the oxidant is not excessively contained in the silicone oil. In order to maintain the oxidant evaporation within the range that does not exceed the saturated vapor pressure and the solubility within the range that does not exceed the saturation solubility, cooling of the photoreaction atmosphere and irradiation light source, and the progress of the photooxidation reaction The present invention relates to a method for forming a transparent photo-oxidized layer thin film of silicone oil, which can monitor the process from the light emission amount of a fluorescent agent as a density distribution of a photo-oxidation reaction.

Conventionally, glass coating methods on the material surface include vacuum deposition, ion plating, sputtering, and CVD. However, these coating films are thin, the film quality is porous, and the water resistance is poor. On the other hand, there is an acrylic cyanol-based ultraviolet curable resin as a transparent adhesive, but there is no method other than the formation of a thin film by a silicone oil photo-oxidation bonding method that can be used in an ultraviolet region having a wavelength shorter than 250 nm.

As a glass film forming method, there is a method using water glass. However, since moisture is required for the glass curing reaction, foaming due to reaction heat remains a problem in transparency, adhesive strength, and formed film strength. On the other hand, silicone oil is irradiated with ultraviolet rays in an oxygen atmosphere to transmit ultraviolet rays at a high density, and further, a coating method and an adhesion method having high temperature resistance, high strength, high hardness, and water resistance are determined by the present inventor. Already reported [Patent Document 4, JP-A-2005-070243] and [Patent Document 5, JP-A-2005-070245].

Generally, since there is a lot of moisture inside the adhesive, it is necessary to raise the substrate temperature in order to form a hard film by means of vacuum deposition, ion plating, sputtering, or the like. However, this treatment changes the properties of the substrate and causes thermal strain in the film. For this reason, the substrate temperature is currently kept at 270 to 300 ° C., and a thin film and a hard film have not been put into practical use.

Furthermore, regarding film thickness coating of optical materials, Patent Document 1 “Optical Element Manufacturing Method” describes that a tetraisocyanate compound or a chlorosilane compound is dropped on a glass lens and then rotated at high speed to uniformly diffuse the solution. In addition, there is a method in which an infrared heater is heated from above the uniformly diffused solution to form a SiO ₂ film having a three-dimensional crosslinked structure by hydrolysis and then gradually cooled to room temperature. However, this film cannot be used at wavelengths shorter than 250 nm.

In addition, a method of laminating transparent SiO ₂ at room temperature by irradiating ArF laser or Xe excimer lamp light in the presence of a mixed gas of NF ₃ and O ₂ and a Si wafer is performed by the present inventors [Patent Document 2]. , Japanese Patent Laid-Open No. 05-102130], Patent Document 2, and [Patent Document 3, Japanese Patent Laid-Open No. 08-088222]. However, this method cannot produce a hard thin film that can be used at wavelengths shorter than 250 nm.

Regarding the formation of a hard thin film, a non-patent document 1 by the present inventors “ArF excimer in an oxygen atmosphere on a glass substrate coated with dimethylsiloxane silicone monomer (SiO (CH ₃ ) ₂ ) n (dimethylsiloxane silicone oil)”. Laser light is used to photodissociate methyl groups from siloxane bonds, and ground state oxygen atoms O (3P) generated by photoexcitation of oxygen are bonded to Si dangling bonds to form transparent SiO ₂ with a thickness of 2 μm. It is disclosed that a hard film is formed ”, but a uniform film thickness has not yet been formed. As disclosed in Non-Patent Document 2, when this silicone oil is irradiated with ultraviolet rays in an oxygen atmosphere, the organic silicone oil can be changed to SiO ₂ that is an inorganic material by photooxidation. Furthermore, in [Patent Document 4, Japanese Patent Application Laid-Open No. 2005-070243], in order to coat the surface of the optical material with glass, the surface of the sample to be processed is preliminarily subjected to plasma treatment or ultraviolet irradiation, and then each of ultraviolet rays and infrared rays is irradiated in an oxidizing agent atmosphere. While intermittently or continuously irradiating, silicone oil is dripped, spin rotation is started, rotation is stopped when it reaches a uniform film thickness, and then UV and infrared rays are irradiated to the interface to form a glass thin film. A method of forming is disclosed. Furthermore, it is disclosed that air, oxygen, ozone, hydrogen peroxide, water, and water vapor are effective as the oxidizing agent.

As for adhesion with silicone oil, in [Patent Document 5, Japanese Patent Application Laid-Open No. 2005-070245], both surfaces of the materials to be bonded are subjected to plasma treatment, silicone oil and an oxidizing agent are interposed, and these are overheated or left as they are. In this state, it is disclosed that both materials to be bonded are superposed and the interface thereof is irradiated with ultraviolet rays. Furthermore, in [Patent Document 6, Japanese Patent Application Laid-Open No. 2006-104046], as an optimum condition for bonding different kinds of glass materials, the molecular weight of silicone oil is 200 to 120,000, and the temperature is room temperature or 200 ° C. or less. The surfaces to be joined are overlapped, and the joining surfaces are at atmospheric pressure or inert by applying pressure in the range of 0 to 30 kg / cm ² or sucking the to-be-joined parts to a low pressure by mechanical pressurization or gas atmosphere pressurization It discloses that pressurization is performed while controlling the differential pressure between the two by an external pressure of gas, and ultraviolet rays are irradiated to the bonding interface. Further, carbon dioxide gas is also disclosed as an oxidant gas.

Japanese Patent Application No. 2-410824 (Japanese Patent Laid-Open No. 04-219349) Japanese Patent Application No. 3-260651 (Japanese Patent Laid-Open No. 05-102130) Japanese Patent Application No.6-222049 (Japanese Patent Laid-Open No. 08-088222) Japanese Patent Application 2003-298124 (Japanese Patent Laid-Open No. 2005-070243) Japanese Patent Application 2003-298158 (JP 2005-070245) Japanese Patent Application 2005-251257 (Japanese Patent Laid-Open No. 2006-104046) Japanese Patent Application No. 2007-192117 (Japanese Patent Laid-Open No. 2009-009075)

Masataka Murahara Plasticity and Processing (Journal of the Japan Society for Technology of Plasticity) Vol. 27, No. 30, 934-942 (1986) Murahara Masataka Room temperature adhesion and coating of quartz glass using excimer lamp, ceramics, 41 (6) 440-443 (2006)

Conventionally, there has been no report about supplying an oxidant mixed in silicone oil without excess or deficiency in a method of bonding or coating by irradiating vacuum ultraviolet light in an oxidant atmosphere with silicone oil. In general, quartz glass is made of silicon dioxide only, with a softening point of 1500 ° C or higher, an expansion coefficient of 5-6 × 10 ^-7 , withstanding rapid quenching, high corrosion resistance, UV transmission of 200 nm, good elastic performance, but melting Requires a high temperature of 1,800 ℃. Silicone oil, on the other hand, is a dimethyldichlorosilane polymer, which is generally a colorless and transparent liquid, and has a kinematic viscosity ranging from 0.65 to 1 million cS. These silicone oils have a small viscosity change with temperature, have a low freezing point, are chemically inert, have a low surface tension, and are excellent in water repellency, antifoaming properties, releasability, electrical insulation, etc. . Fortunately, looking at the chemical structural formula, both have a siloxane bond (—Si—O—) bond in the skeleton, and the Si atom has a methyl group (—CH ₃ ) or an ethyl group (—C ₂ H ₅ ). Those with etc. are silicone oil, and those with oxygen (= O) are quartz glass. The present inventor has the same siloxane bond in the skeleton in order to overcome the disadvantage of processing that the high temperature of 1,800 ° C. is required for melting while having the chemical stability and high resistance of quartz glass, In addition, we have been researching the transformation of quartz oil by irradiating liquid silicone oil with vacuum ultraviolet rays in an oxygen atmosphere, photo-cleaving methyl groups in Si side chains, and substituting oxygen atoms there. That is, the liquid was irradiated with ultraviolet rays in an oxidant atmosphere to form a solid.

As disclosed in 1986 [Non-patent Document 1], starting with the fact that a silica glass film was formed by irradiating a 193 nm ArF laser on the silicone oil layer in air, Patent Documents 2-7 and Non-Patent Document 2 As disclosed, in the process of irradiating silicone oil with vacuum ultraviolet rays in various oxidant atmospheres to photo-oxidize the silicone oil layers and transform those layers into amorphous quartz glass, the film formation method and adhesion method by coating are Has been disclosed.

However, in all of them, the reaction took 1 hour or more, and when the irradiation time was increased, the photocuring was completely completed and incomplete cases were various. In each case, trial and error was continued by changing the irradiation energy density of the vacuum ultraviolet lamp, the distance between the silicone oil layer and the light source, the atmosphere gas, etc., but the reproducibility was poor and the decisive condition for photooxidation was found. Did not come.

The following experiment showed a decisive phenomenon suggesting the lack of reproducibility. When a glass substrate coated with silicone oil was placed on a metal sample table with a hollow central part and light irradiation was attempted, the part where the sample table was in contact with the glass substrate was cured, but the hollow part in the center was not solidified. Instead, the liquid silicone oil layer was waved from the vicinity of the boundary so as to correspond to the shape of the sample stage.

When this portion was observed, an ultrathin film was formed in the portion of the silicone oil layer in contact with the atmosphere, and the silicone oil layer from the lower portion to the substrate was not photocured at all. At first, this phenomenon was thought to be due to the influence of the reflection of vacuum ultraviolet light between the sample stage and the glass substrate, and a large amount of light at the place where the sample and the sample stage were in close contact.

However, the reflection efficiency of ultraviolet rays was improved by making the boundary between the sample stage and the glass substrate a mirror surface, but there was no real change. Further, it was found that photocuring is inhibited when the boundary surface is painted black to improve heat absorption. In other words, the above-described metal sample stage with a hollow central portion serves as a heat diffusion plate, and the temperature increase is suppressed because heat diffuses in the portion in contact with the glass substrate, but the central hollow portion stores heat. As a result, the silicone oil was locally overheated, resulting in the conclusion that the oxidizer inside the silicone oil layer was dispersed. And it was found that the cause was lack of oxygen.

As a result of these considerations, it has been found that the temperature of the oxidation reaction atmosphere is lowered to suppress the temperature rise. Furthermore, when the atmospheric temperature of the photo-oxidation reaction system cannot be lowered by developing this, a method has been found in which the reaction atmosphere is pressurized and the oxidant is not separated from the reaction system. That is, when the oxidizing agent is a liquid, the atmospheric pressure is increased and the saturated vapor pressure is maintained, or when the oxidizing agent is a gas, the atmospheric pressure is increased and the saturated solubility is maintained, thereby controlling the saturated vapor pressure and the saturated solubility. The idea of the present invention has been reached in which the oxidant is not dispersed from within the oil.

Furthermore, it is necessary to monitor the excess and deficiency of the oxidant and the photocuring in the photooxidation reaction in real time and feed back to the reaction control. However, there is no report of a method for monitoring the photooxidation reaction process of these silicone oils and measuring the timing of replenishing the oxidant and ending the light irradiation. There is no report of an irradiation apparatus that satisfies both cooling of the vacuum ultraviolet light source and increase in the amount of irradiation light.
Recently, it has been said that the efficiency of receiving light from astronomical objects has been reduced due to the blackening of mirrors and solar panels of Space Shuttle's Happle telescope.

Regarding this cause, the inventor of the present application received a low-molecular siloxane volatilized from a silicone rubber adhesive or a coating film for supporting a solar cell panel mounted on an artificial satellite in a vacuum irradiated with vacuum ultraviolet rays such as in space. The film is adsorbed on an optical surface such as a surface or an astronomical telescope mirror, and the surface of the light-receiving surface appears to be blackened or clouded, so that a film was formed in a vacuum vessel with RTV silicone rubber KE106 (manufactured by Shin-Etsu Chemical Co., Ltd.). The film was allowed to stand and irradiated with 172 nm Xe2 excimer lamp light for 100 hours. As a result, it was confirmed that the surface was blackened and carbon was liberated. However, there is no report which avoids these phenomena using a photo-oxidation technique.

Therefore, in the present invention, as means for solving the above-described problems, during photoexcitation, a method of keeping an appropriate amount of oxidizing agent in the low molecular weight siloxane and silicone oil and a proper amount of the oxidizing agent are constantly monitored, and this photooxidation reaction is constantly monitored. An object of the present invention is to provide a method for controlling an oxidation reaction and a vacuum ultraviolet light source for effectively performing a photo-oxidation reaction.

Therefore, the present invention provides a means for solving the above-mentioned problems, and it is possible to oxidize air, oxygen, carbon dioxide, ozone, moisture, etc. without excessively or insufficiently inside the silicone oil applied to the adherend sample surface for adhesion or coating. It is necessary to maintain the agent only in the middle of photoexcitation. For this reason, when the photo-oxidation reaction atmosphere is in the air, the oxidation reaction atmosphere is set to an organic solvent in order to avoid the oxidant gas and moisture from being dispersed outside the reaction system, that is, for the purpose of suppressing evaporation of the oxidant. Alternatively, it is necessary to maintain the reaction in the photooxidizing atmosphere within a range where the pressure of the liquid oxidant does not exceed the saturated vapor pressure and within a range where the solubility of the gaseous oxidant does not exceed the saturated solubility.

In general, the saturated vapor pressure is called the maximum vapor pressure, and its value varies depending on the substance and increases with increasing temperature. In general, silicone oil contains about 250 ppm of water, but the present inventor has found that this water is effective as an oxidant for the photo-oxidation reaction. For example, the saturated vapor pressure of water vapor is 760 mmHg at 100 ° C, 92.5 mmHg at 50 ° C, and 9.2 mmHg at 10 ° C. Further, hexane frequently used as a diluent solvent for silicone oil is 760 mmHg at 80.26 ° C., 200 mmHg at 31.61 ° C., and 60 mmHg at 5.36 ° C. Silicone oil also absorbs air and carbon dioxide very well. The inventors of this application have also found out that these gases are effective as an oxidant for the photooxidation reaction. For example, the saturation solubility is 20% by volume at 100 ° C. for oxygen gas, 30% by volume at 10 ° C., and 100% by volume at 10 ° C. for carbon dioxide. This saturation solubility is the concentration of the solute in the saturated solution and varies with temperature. The solubility of a gas in a liquid is also referred to as “solubility coefficient” or “Bunsen absorption coefficient”. Thus, control of temperature and pressure is indispensable for the photo-oxidation reaction of silicone oil.

[Claim 1 of Japanese Patent Application Laid-Open No. 2006-104046] discloses that the surfaces to be bonded are superposed in a room temperature or a temperature atmosphere of 200 ° C. or less as a photoreaction temperature. However, the oxidizing agent is scattered outside the temperature range in this description. In this case, no oxidation reaction occurs no matter how long the photoexcitation time is maintained. That is, in an atmosphere where the oxidizing agent is insufficient, the subsequent photooxidation reaction does not proceed even if the light intensity or irradiation time is increased. In order to prevent the scattering of the oxidant, the present invention cools the silicone oil layer and the sample to be processed or the atmosphere of the photo-oxidation reaction and the like, and does not exceed the saturated vapor pressure of the oxidant used in the oxidation reaction. And a control method for maintaining the solubility within a range that does not exceed the saturation solubility.

It is heat radiation from the vacuum ultraviolet lamp that raises the atmospheric temperature most in this photo-oxidation reaction. Furthermore, the oxidizing agent used in the photo-oxidation reaction oxidizes the electrodes and reflectors of the vacuum ultraviolet lamp, thereby reducing the reflectivity of the excitation light, which leads to electrode deterioration. For the purpose of preventing both the heat generation of the vacuum ultraviolet light source and the oxidation of the reflecting mirror or the electrode, there is also provided a method for cooling the inside of the reflecting mirror and the electrode.

Furthermore, when the photo-oxidation reaction of the silicone oil layer proceeds and the methyl group (—CH 3) in the silicone oil decreases and the methyl group and oxygen are replaced, the silicone oil layer gradually vitrifies and becomes a photo-oxidized layer. To form a vacuum ultraviolet ray. In order to monitor the process of photooxidation using this property, if a fluorescent agent layer that is sensitive to vacuum ultraviolet rays is placed on the back side of the photooxidation layer, the ratio of silicone oil to vitrification is monitored according to the emission intensity. It is possible to control the input of oxidant and the excitation light. This monitoring can also be done with a photosensor mounted on the back side of the fluorescent layer, but if only the emission spectrum of the phosphor is observed from the excitation light side with a TV camera through a bandpass filter, light emission occurs as the photooxidation reaction of silicone oil progresses. Since the intensity increases and the density distribution of the photooxidation reaction can be monitored as a distribution image of the light emission amount of the fluorescent layer, a highly efficient photooxidation reaction apparatus can be provided.

In the present invention, in order to photooxidize the silicone oil, it is necessary to supply an oxidizing agent that is not excessive or insufficient. Therefore, to suppress the saturated vapor pressure and saturation solubility of oxidizers and solvents, it is necessary to increase the atmospheric pressure when the atmospheric temperature of the photooxidation reaction is high, and even if the pressure is low when the temperature is low It ’s okay, but it should n’t be high. On the other hand, the temperature must be lowered when the atmospheric pressure of the photooxidation reaction is low, but the temperature may be raised when the pressure is high. Therefore, it is desirable to maintain the atmospheric temperature in the range of + 50 ° C. to −50 ° C. in order to cause the silicone oil itself to perform a photo-oxidation reaction. However, if the oxidant gas inside or at the boundary is lowered to the liquefaction temperature, excess oxygen At the same time, vacuum ultraviolet rays are not transmitted. Therefore, from the economical viewpoint, the photooxidation reaction is preferably in the range of 10 ° C. to 50 ° C. where the temperature of the cooling water can be maintained. On the other hand, when the atmosphere of the photo-oxidation reaction such as space is vacuum, vacuum ultraviolet light is irradiated with the oxidant gas adsorbed on the adsorption surface of the low-molecular siloxane, and the low-molecular siloxane adsorption layer performs photo-oxidation reaction. Since the methyl group contained in the low molecular weight siloxane is photodegraded in the presence of an oxidant, a transparent SiO ₂ layer is formed, thus avoiding obstruction of blackening of the surface of the light receiving surface due to generation of free carbon.

If the adhesion or coating sample is deliquescent, the solvent inside the silicone oil is volatile, or the photo-oxidation reaction atmosphere is hot, the oxidation reaction atmosphere should be kept in a reaction vessel that is isolated from the atmosphere. Need to be processed. This is because the oxidant such as air, oxygen, carbon dioxide, ozone or moisture dissolved in the silicone oil layer or adsorbed at the interface of the silicone oil layer, or benzene, toluene, xylene, cyclohexane dissolved in the silicone oil layer. In order to suppress evaporation of hydrocarbons such as ethyl ether or carbon chlorides such as carbon tetrachloride, chloroform, trichloroethylene, chlorobenzene, etc., pressurization is performed with an oxidizing gas or inert gas used in the oxidation reaction. As a result, the oxidant and solvent in the silicone oil can be prevented from leaving.

For general bonding, as disclosed in [Patent Document 6, JP-A-2006-104046], the higher the viscosity (viscosity) of silicone oil, the more effective, but in the case of coating, the lower the viscosity, Thinning with a spinner is easy. Therefore, after diluting with a solvent and applying to the sample, the spinner rotates faster to disperse excess silicone oil, but the solvent disperses ahead of the viscous silicone oil, resulting in a thin film It is impossible. Therefore, in the present invention, in a state where the inside of the reaction vessel is pressurized with an inert gas or an oxidant gas, silicone oil diluted with a solvent is applied to the surface of the sample to be treated, and after being thinned with a spinner, the pressure is gradually reduced. Then, after vaporizing the solvent, an oxidizing gas is introduced into the reaction vessel and irradiated with light from a vacuum ultraviolet lamp to form one photooxidized layer. By repeating this series of operations, a multilayer film or a mold is formed, and a method and apparatus for forming a constant film thickness or any desired film thickness or performing anastomosis can be provided.

In the photo-oxidation film formation according to the present invention, when silicone oil is applied to a substrate or product by the same method as coating, and irradiation with vacuum ultraviolet rays in an oxidizing agent atmosphere is performed, a film that is transparent, hard, and excellent in electrical insulation is formed. Therefore, it can be used as an insulating base film or protective film for a large area solar cell panel or a large area liquid crystal display without using a glass plate. For this purpose, a film material as a sample to be processed or a metal plate having a shape such as a plane or curved surface, plastic, glass or ceramic as a base material, a wall building material panel, a roof material panel, an aircraft wing upper surface, an aircraft fuselage, Photo-oxidation layer as an electrical insulating substrate for forming photovoltaic power generation elements on the body surface or ship deck surface, or as a protective film such as transparency, moisture resistance, water resistance or salt resistance for photovoltaic power generation elements, or a liquid crystal display panel As a protective film with transparency, water resistance, moisture resistance on the entire surface of the mother glass and panel, or optical window surface, spectacle lens, optical lens, optical mirror, optical prism, nonlinear optical element, optical fiber end face, side face of laser medium It can be used as a protective film for optical surfaces. Alternatively, it can be used as an anti-icing film for windmill blades in polar regions and a salt-resistant film for offshore windmill blades. Semiconductor thermoelectric element modules such as Peltier elements and Seebeck elements used for temperature difference power generation are useful as protective films having water resistance, moisture resistance, salt resistance, heat resistance, and the like.

In order to form these photo-oxidation layers, spin coating, dip coating, dripping, roller, brush, spray, or touch the surface of the sample to be coated with the silicone oil momentarily and touch it immediately. A uniform silicone oil layer is formed by a coating means such as a touch and go coating method.

For this technique, that is, a technique for forming a thin film using photo-oxidation of silicone oil as a protective film, [Patent Document 4, JP 2005-070243], [Patent Document 5, JP 2005-070245], [Patent Document 6, JP-A-2006-104046] and [Patent Document 7, JP-A-2009-009075]. However, in the present invention, the vapor pressure of the oxidant is controlled in order to control the supply of the oxidant in the photooxidation reaction to shorten the film formation time and to reduce the abundance of unreacted silicone oil in the formed photooxidized film. It is also possible to provide a method and an apparatus for forming a photooxidized layer while maintaining an oxidizing agent without excess or deficiency during photoexcitation within the range where the vapor pressure does not exceed the saturated vapor pressure and the solubility does not exceed the saturated solubility.

Invention [Claim 1] described, relates steps of manufacturing an optical oxide film on a plate made of a single or a plurality to be photooxidation layer thin film formation, in the pretreatment step in board, the silicone oil light in forming a transparent photo-oxidation layer a thin film of SiO2 on a substrate by oxidation, an inert gas such as vacuum ultraviolet light or trace oxygen atmosphere or an argon gas or helium gas, such as Xe2 excimer lamp of 173nm the substrate surface beforehand in an oxygen gas atmosphere in mixed allowed the oxygen gas atmosphere by a Turkey be irradiated discharge plasma, the surface cleaning and oxygen gas or oxygen molecules are adsorbed to, Oite the coating step of the silicone oil of the substrate surface in addition, when the adhesive Apply a high-viscosity silicone oil with a viscosity of 500 to 50,000cs (molecular weight: 10,000 to 100,000) mixed with an oxidizing agent between the pair of pretreated substrates, and 1kg / c Pressure is applied at a pressure of m2 to 10 kg / cm2, and in the case of coating, silicone oil is applied with a viscosity of 0.65 to 50 cs. Silicone with lower viscosity after dilution with organic solvents such as hydrocarbon solvents such as benzene, toluene, xylene, cyclohexane ethyl ether or carbon chloride solvents such as carbon tetrachloride, chloroform, trichloroethylene, chlorobenzene, etc. Touch-and-go that immediately raises the oil on the pretreated substrate by spin coating, dip coating, dripping, roller, brush, spray, or touching the surface of the sample to be coated with the silicone oil. no rows uniform silicone oil layer formed by a coating method (Touch and go coating) such as by coating means, further at step of photoreaction an oxidizing agent and a silicone oil, liquid or gaseous in a silicone oil layer applied to the substrate Oxidation of In order to keep the agent without excess or deficiency, not only the oxidizing agent mixed in the silicone oil in advance, but also during the photooxidation reaction, there is no excess or deficiency on the surface or inside of the silicone oil layer, and air, oxygen, carbon dioxide, ozone or an oxidizing agent such as water is seen maintained in light excitation, and the emission intensity of the fluorescent agent layers sensitive to a vacuum ultraviolet course of vitrification by photooxidation of the silicone oil layer monitors photoreaction This is an invention in which the SiO2 transparent photo-oxidation thin film can be formed by a photo-oxidation reaction without excess or deficiency of the oxidizing agent by feeding back the emitted light intensity to a vacuum ultraviolet lamp .
A schematic overall process diagram relating to the invention of [Claim 1] is shown in FIG.

According to [claim 2] The invention described, oxidizing agent and a silicone oil for holding the silicone for oil layer applied to the adhesive surface of the sample just enough liquid or gaseous oxidizing agent for adhesion and coating The step of photoreacting is not excessive or insufficient during vacuum ultraviolet irradiation, and oxidants such as air, oxygen, carbon dioxide, ozone or moisture are continuously supplied, and these oxidant gases and moisture are dispersed outside the reaction system. It is necessary to avoid that. Generally, silicone oil left in the atmosphere contains about 250 ppm of water, and air contains 16 to 19% by volume. The atmosphere absorbs carbon dioxide very well. Therefore, it is convenient to mix an oxidant gas such as moisture, oxygen, hydrogen peroxide, ozone, carbon dioxide in the silicone oil. However, moisture, oxygen, oxygen peroxide, and ozone are strongly absorbed by the vacuum ultraviolet rays required for the photo-oxidation reaction. If the amount is too much, vacuum ultraviolet rays in the silicone oil layer (172 nm Xe2 excimer lamp light) Is absorbed by the light incident surface of the silicone oil layer, and only the ultrathin layer on the surface is cured and is not transmitted into the interior. For this reason, internal photooxidation does not proceed. In particular, the moisture increases in density when the ambient temperature is lowered, impeding the transmission of vacuum ultraviolet light. This is even more so when frozen. In particular, in the case of bonding, since the silicone oil mixed with the oxidizing agent is sandwiched between the two substrates, it is difficult to input the oxidizing gas during the light irradiation as compared with the coating. Furthermore, as the photo-oxidation reaction of silicone oil proceeds, transparent amorphous glass (SiO2) is formed. As a by-product of this reaction, the photo-decomposed methyl group (-CH3) reacts with the internal oxidizing agent to react with water and dioxide. Produces carbon. When the amount of the oxidizing agent is excessive, water and carbon dioxide remain inside the cured silicone oil layer of the generated water and carbon dioxide, causing internal distortion and cloudiness. On the other hand, when the oxidizing agent is insufficient, carbon (C) is liberated from the photodecomposed methyl group (—CH 3), which causes blackening. Fortunately, carbon dioxide and water produced as a by-product are photodegraded by re-vacuum ultraviolet irradiation and become a source of oxygen. Further, since the methyl group plays a role as an adhesive with the substrate, it is indispensable to mix an appropriate amount of an oxidizing agent. Carbon dioxide as an oxidizing agent transmits 172 nm vacuum ultraviolet light as compared with the other oxidizing agents described above. Therefore, it is suitable as an oxidizing agent. On the other hand, in the case of coating, since the light incident surface of the silicone oil layer is in contact with the oxidant gas, the silicone oil containing no oxidant may be applied to the substrate and then placed in the oxidant gas atmosphere. Of course, silicone oil in which an oxidizing agent is mixed in advance may be used. The silicone oil layer undergoes an oxidation reaction from the light incident surface side. That is, when the silicone oil is not reacted, it absorbs vacuum ultraviolet light strongly and is absorbed by the surface layer, and does not penetrate into the inside. However, since the oxide layer that has undergone the photo-oxidation reaction can transmit the vacuum ultraviolet light, the oxidation reaction sequentially proceeds to the inside, and finally the back layer is oxidized to reach the substrate and adhere to the substrate. Therefore, empirically, it is important to introduce an oxidant gas into the silicone oil layer until a very thin oxide film is formed on the surface of the silicone oil layer. As described above, it is desirable that the oxidant is added in the photoreaction of the silicone oil layer before the application of the silicone oil to the substrate before the light irradiation and until the photooxidation layer is formed on the surface of the silicone oil layer. In order not to scatter the oxidant mixed in the silicone oil layer from the silicone oil layer , the oxidant is liquid so long as it does not exceed the saturated vapor pressure of the oxidant. Irradiate with vacuum ultraviolet light in a state where the photoreaction atmosphere temperature is cooled to 10 to 50 ° C. within a range not exceeding the saturation solubility of the agent. Particularly in cases where the anti-reaction container device is in contact with the atmosphere, if the oxidant gas is photooxidation reaction temperature - it is preferably in the range of 50 ℃ ~ + 50 ℃. However, since water is often mixed in the silicone oil, the photo-oxidation reaction is economically performed in the range of 10 ° C. to 50 ° C. where the temperature of the cooling water can be maintained in order to avoid freezing of the water . Or if you can not cool the optical oxidizing ambient temperature range, the reaction vessel was shut off from the atmosphere, the oxidizing gas such as oxygen gas which is diluted by the inert gas such as argon gas or helium gas to the reaction vessel pressurized to above 1 atm, it is the child a transparent photo-oxidation thin film and vacuum ultraviolet irradiation in a state that lasted oxidation reaction by increasing the saturation solubility of the shea recone oil inside the oxidant gas.

According to the invention of [Claim 3 ], the step of monitoring the process of forming the photo-oxidation layer thin film, that is, the progress of the photo-oxidation reaction of the silicone oil layer and maintaining the photo-reaction is the oxidation supplied to the silicone oil layer. in order to monitor the excess and deficiency of agent has sensitivity to vacuum ultraviolet radiation to the back of the formed light oxide layer with a silicone oil, fluorescers layers sensitive to a vacuum ultraviolet light such as sodium salicylate having an emission peak around 450nm in emit light, to detect the proportion of photooxidation layer was silicone oil and glass of unreacted depending on the emission intensity of the fluorescent light adhesive layer, unreacted silicone oil and vitrified photooxidation according to the emission intensity of its Photocells with layer ratios on the back side of the fluorescent layer can also be used, but only the emission spectrum of the phosphor is observed from the excitation light side with a TV camera through a bandpass filter. If, the emission intensity as progress of photooxidation of the silicone oil is increased, the density distribution of the photo-oxidation reaction was monitored as a light emission amount of the distribution image of the fluorescent layer, the supply or vacuum ultraviolet light of the oxidizing agent of the liquid or gaseous can and this performing the irradiation intensity and the transparent photo-oxidation thin film formed is fed back to the irradiation time.

According to the invention described in [ 4 ], a low molecular weight siloxane is used as an adhesive and / or a coating agent used for a silicone oil layer for forming a transparent photo-oxidized thin film in the step of applying a silicone oil on the surface of the substrate. A gaseous low-molecular-weight siloxane adsorbing layer and / or a silicone oil layer having a bond is used. In particular, the surface tension of silicone oil is smaller than that of water or general synthetic oil. According to the measurement by the present inventors, the contact angle between the quartz glass substrate and water is 28 degrees, whereas the contact angle between the quartz glass substrate and silicone oil (KF-96: manufactured by Shin-Etsu Chemical Co., Ltd.) is as small as 6 degrees. The nature of this small contact angle indicates the ease of spreading on the substrate surface, and is a measure of the good adhesion of the adhesive layer and coating layer to the substrate. Furthermore, when the quartz glass substrate is subjected to plasma irradiation in a diluted oxygen atmosphere as a pretreatment for 2 minutes, the contact angle between the quartz glass and the silicone oil becomes 0 degree, and the adhesion between the substrate and the silicone oil layer becomes strong. Is heading. Silicone oil has a viscosity of 0.65 to 1 million cs, a high viscosity product is classified into 6,000 to 1 million cs, a medium viscosity product is classified into 10 to 5,000 cs, and a low viscosity product is classified into 0.65 to 9 cs. In the measurement by the present inventor, when used as an adhesive, a high viscosity silicone oil having a viscosity of 500 to 50,000 cs (molecular weight: 20,000 to 100,000) is suitable, preferably 10,000 cs (molecular weight 60,000). In the case of coating, silicone oil having a viscosity of 0.65 to 50 cs is preferable. According to the measurement by the present inventor, the viscosity of the silicone oil is 100 nm at 10 cs, 700 nm at 50 cs, and 4,000 nm at 100 cs. However, with a viscosity of 100 cs or more, it is difficult to apply a uniform film thickness of 4,000 nm or more when using a spinner, and uneven coating occurs. Therefore, when coating with high molecular weight silicone oil, that is, high viscosity silicone oil, hydrocarbons such as benzene, toluene, xylene, cyclohexane ethyl ether or carbon chlorides such as carbon tetrachloride, chloroform, trichloroethylene, chlorobenzene, etc. After diluting with an organic solvent such as a solvent, silicone oil having a low viscosity may be applied. However, in spinner coating in the silicone oil coating step on the substrate, it is necessary to pressurize with an oxidizing gas or inert gas used for the oxidation reaction in order to suppress evaporation of the organic solvent. A uniform film can be formed by thinly molding the polymer silicone oil layer and then returning the atmospheric pressure to atmospheric pressure, followed by vacuum ultraviolet irradiation in an oxidizing agent atmosphere.
During dimethylsiloxane as the main component of the silicone products, gaseous low-molecular-weight siloxane adsorbent layer having a low molecular Siloxane bonds are volatilized remaining in its production process, adhere to the contacts of the electronic components such as motors and relays or switches However, it has been reported that the decomposable organism, SiO ₂ , acts as an electrical insulator and causes contact failure. Recently, however, it has been reported that the light receiving surfaces of space-equipped solar panels and telescope mirrors in space are black. Generally, low molecular weight siloxane is cyclic polysiloxane, C ₈ H ₂₄ O ₄ Si ₄ , C ₁₀ H ₃₀ O ₅ Si ₅ , C ₁₂ H ₃₆ O ₆ Si ₆ , C ₁₄ H ₄₂ O ₇ Si ₇ , C ₁₆ H ₄₈ O ₈ Si ₈ , C ₁₈ H ₅₄ O ₉ Si ₉ , C ₂₀ H ₆₀ O ₁₀ Si ₁₀ MAS number 294, 370, 444, 518, 592, 666, 740 with low molecular weight gas Sure. In the present invention, it is considered that the low molecular weight siloxane volatilizes from silicone rubber, silicone adhesive, etc. in a vacuum atmosphere such as space and adheres to surrounding solid objects. In particular, solar cells and mirrors that receive light are serious problems because they affect the light receiving efficiency. The present inventor considers that the low molecular siloxane adsorbing layer adsorbed on the light receiving surface is irradiated with sunlight by vacuum ultraviolet rays and photodecomposed, and carbon in the components is liberated and blackened. Therefore, in the present invention, when vacuum ultraviolet light is irradiated with the oxidant gas adsorbed on the adsorption surface of the low molecular siloxane, the low molecular siloxane adsorption layer undergoes a photo-oxidation reaction and the methyl groups contained in the low molecular siloxane are oxidized. Since the photodecomposition is caused by the presence of the agent, a transparent SiO ₂ layer is formed, which is considered to be free from obstacles to blackening of the light receiving surface due to the generation of free carbon.

[Claim 5] According to the invention described in [5], after applying a silicone oil having a low viscosity to form one ultra-thin photo-oxidation layer, the series of steps described in [1] is repeated to form a film in order. The present invention relates to a method for forming a transparent photo-oxidized layer thin film. For co computing, viscosity to apply the silicone oil in 0.65～50Cs. For higher viscosity, dilute the silicone oil with organic solvents such as hydrocarbon solvents such as benzene, toluene, xylene, cyclohexane ethyl ether or carbon chloride solvents such as carbon tetrachloride, chloroform, trichloroethylene, chlorobenzene, etc. In order to lower the pressure and prevent them from exceeding the saturated vapor pressure, pressurization is performed with an inert gas such as nitrogen gas that transmits vacuum ultraviolet rays. In this pressurized state, after diluting the silicone oil, a uniform silicone oil layer is formed on the pretreated substrate by means of spin coating, and the solvent is evaporated by reducing the pressure. And after filling the oxidant gas and irradiating with vacuum ultraviolet light, forming a single layer of photo-oxidation layer, gradually reducing the pressure to vaporize the solvent, and then stopping the spinner rotation, carbon dioxide, etc. After the formation of a single layer of photo-oxidized layer by enclosing the oxidant gas and irradiating with vacuum ultraviolet light, the series of steps according to claim 1 is repeated to form a transparent photo-oxidized thick film. Can be formed.

According to the invention described in [Claim 6], a silicone rubber adhesive or an RTV silicone rubber as a protective film is used to adhere and fix the solar cell panel of an artificial satellite in outer space to the casing. However, C ₈ H ₂₄ O ₄ Si ₄ , C ₁₀ H ₃₀ O ₅ Si ₅ , C ₁₂ H ₃₆ O ₆ Si ₆ , C ₁₄ H ₄₂ are low molecular weight siloxanes from D4 to D10 remaining in the silicone rubber. It is considered that O ₇ Si ₇ , C ₁₆ H ₄₈ O ₈ Si ₈ , C ₁₈ H ₅₄ O ₉ Si ₉ , C ₂₀ H ₆₀ O ₁₀ Si _10, etc. are volatilized and adhere to surrounding solid substances. In particular, solar cells and mirrors that receive light are serious problems because they affect the light receiving efficiency. The present inventor considers that the low molecular siloxane adsorbing layer adsorbed on the light receiving surface is irradiated with sunlight by vacuum ultraviolet rays and photodecomposed, and carbon in the components is liberated and blackened. Therefore, in the present invention, a gas supply nozzle for injecting an oxidant gas such as oxygen gas, hydrogen peroxide, and moisture onto the low-molecular siloxane adsorption surface adsorbed on the light-receiving surface of a solar cell panel mounted on an artificial satellite, a telescope mirror, or the like. A metal oxide such as copper oxide, which is placed in a state where the oxidant is adsorbed on the optical surface constantly or intermittently, or scattered around the solar cell panel, telescope mirror, etc., is used as an oxygen supply source, and the light receiving surface is exposed to the sun. When irradiated with UV light of 200 nm or less, a low-molecular siloxane adsorption layer undergoes a photo-oxidation reaction to form a transparent SiO ₂ layer, which prevents blackening of the surface of the light-receiving surface due to the formation of free carbon. it can.

[7] The present invention relates to a method for producing a plate glass or a mother glass by etching only a substrate out of a thick film produced by photo-oxidizing a silicone oil layer on the substrate. According to the present invention, a transparent photo-oxidation layer thin film according to the above-mentioned [Claim 1], [Claim 2], [Claim 3], [Claim 4], [Claim 5] and [Claim 6] is formed. In order to form an insulating substrate constituting a solar cell panel, the method comprises forming the photo-oxidized layer thin film on the metal or plastic plate with the silicone oil layer, and further forming transparent light as described in [Claim 6 ]. A thick film insulating substrate formed by sequentially stacking films by repeating oxide layer thin film formation can be produced. In addition, in order to form the mother glass constituting the liquid crystal display panel, the photo-oxidation layer thin film is formed in advance on the metal, plastic, etc. by the silicone oil layer, and the transparent light as described in [Claim 6 ]. A thin glass obtained by etching and removing a thick film insulating substrate formed by sequentially stacking films by repeating oxide layer thin film formation with an acid or an organic solvent can be used as the mother glass. As this mother glass manufacturing method, there are many thin glass plates formed by etching a thick film formed by photo-oxidizing silicone oil on metal or plastic that is elastic and thin and has a mirror surface. Available in the field. In addition, a replica obtained by etching a silicone thick film on a metal or plastic surface formed by photo-oxidation of silicone oil on a mold with irregularities, patterns, or tops of the phase is an optical hologram. It can be used as a phase conversion plate, a pattern plate, or an eyelet lens. Furthermore, in order to form an electrically insulating transparent protective film on the front surface or the entire surface of an object to be coated such as a solar cell panel, a liquid crystal display panel or a thermoelectric conversion module, the transparent photo-oxidized layer thin film is formed by the silicone oil layer. You can also.

According to the present onset bright, thin film formation by photooxidation, a silicone oil was applied in the same way as coating to the substrate and product, after application, to control the temperature or atmospheric pressure, when the vacuum ultraviolet radiation in an oxidizing agent atmosphere, A thin film that is transparent, hard, and excellent in electrical insulation can be formed, so that it can be used as an insulating underlayer film or protective film for large-area solar cell panels and large-area liquid crystal displays that do not use a glass plate.
In the film formation by photo-oxidation of silicone oil, in order to store or replenish the oxidant in the oil without excess or deficiency, the present invention constantly monitors the photo-oxidation reaction during photo-excitation and controls the saturated vapor pressure of the oxidant. To solve this problem by providing a vacuum ultraviolet light source that effectively performs photo-oxidation reaction, and is short of a large-area thin film that is rich in electrical insulation, transparent in all wavelengths, and excellent in heat resistance and water resistance. Can be created on time.

Furthermore, a silicone oil diluted with a solvent is applied to a sample on a spinner placed in a reaction vessel that is shielded from the outside air, and an inert gas or an oxidizing agent is applied so that the atmosphere becomes a pressure higher than the saturated water vapor of the solvent. Viscosity of silicone oil at the time of application by thinning with a spinner while being pressurized with gas, vaporizing the solvent by degassing, and then irradiating with vacuum ultraviolet radiation with atmospheric pressure oxidant gas sealed Depending on the film thickness, a film having a thickness of 10 to 4,000 nm can be formed.
In addition, according to the present invention, by cooling the photo-oxidation reaction atmosphere, the vapor pressure of the oxidant in the silicone oil is suppressed to a saturation vapor pressure or less, and the oxidant can be maintained in the silicone oil without excess or deficiency. The conventional photoreaction time of 60 minutes or more can be shortened to 30 minutes or less, and if carbon dioxide is used as an oxidant, the reaction time can be shortened to 15 minutes or less, and there is an excess or shortage of oxidant. Since there is no film formation with high reproducibility.

Silicone oil formed on the back side of the photo-oxidation layer has a sensitivity to vacuum ultraviolet rays and a fluorescent agent layer such as sodium salicylate that has an emission peak near 450 nm. The ratio of the photo-oxidized layer can be monitored as the amount of light emitted from the fluorescent layer, and by monitoring this, it can be used as an effective index of oxidant input.

The vacuum ultraviolet lamp for forming the transparent photo-oxidation layer thin film of the present invention is as shown in [FIG. 1] to [FIG. 11].
Since the reflector and electrode are integrated into one body and the inside is cooled and the vacuum ultraviolet light source and the reflector mirror electrode are integrated by bonding silicone oil, deterioration due to oxidation of the electrode and reflector can be suppressed, can achievement of long life of the lamp is to further carry out the photooxidation with high efficiency.

According to the invention described in [Claim 4] and [Claim 6],
Silicone rubber adhesive is used to adhere and fix the solar panel of an artificial satellite in outer space to the housing, but the low-molecular siloxane from D4 to D10 remaining in the silicone rubber volatilizes and the surrounding material surface In particular, it is adsorbed on the solar cell light-receiving surface, telescope mirror, etc., and the optical surface becomes clouded or blackened, causing a decrease in the amount of incident light. This is because free carbon generated by photolysis of the adsorbed low-molecular siloxane in a vacuum free of oxygen with ultraviolet rays of 200 nm or less of sunlight remains on the optical surface. So, if the oxidant such as oxygen gas, hydrogen peroxide, water and metal oxides such as copper oxide is exposed to sunlight or intermittently adsorbed to the optical surface, the irradiated ultraviolet light will hit, It does not produce free carbon.

[Claim 5] and [Claim 7] inventions the case where is applied to a large-area solar cell panel and large area liquid crystal display or thermionic conversion module, the optical thin oxide formed and a transparent light oxidation layer film according to the invention Forming a thick film by repeating the formation and sequentially laminating the film is performed by applying silicone oil to the substrate or product in the same way as painting, and then applying the vacuum in an oxidant atmosphere with controlled temperature or atmospheric pressure. Irradiation with ultraviolet rays can form a film that is transparent, hard, and excellent in electrical insulation, so it can be used for insulation underlayers and protection such as large-area solar cell panels, large-area liquid crystal displays that do not use glass plates, and thermoelectric conversion modules. It can also be used as a membrane. Furthermore, it is a flexible metal film with a thin mirror surface, or a highly flexible and malleable metal foil such as stainless steel or phosphor bronze plate, or a plastic film such as acrylic resin, polyimide, or polysulfane. The thin glass obtained by etching and removing the photo-oxidized transparency formed in step 1 with an acid or an organic solvent can be used as the mother glass, protective glass, or semiconductor substrate. In addition, a thick film formed by photo-oxidizing silicone oil on a metal or plastic surface with a concavo-convex pattern is formed by etching and can be used as a mosaic or eyeglass lens.

Hereinafter, an effective embodiment of the present invention will be described in detail based on [FIGS. 1 to 12].

FIG. 1 is a schematic view showing a method and apparatus for forming a low-temperature photooxidized layer of silicone oil of the present invention. As shown in this figure, the feature of the present invention is that when a silicone oil is applied to the surface of a substrate 2 transparent to vacuum ultraviolet light in a reaction vessel 1 and photoexcited by a vacuum ultraviolet lamp 3, an adhesive layer, a coating layer, etc. The silicon oil photo-oxidation layer 4 is formed, and the sodium salicylate fluorescent agent layer 5 having sensitivity to vacuum ultraviolet rays and having an emission peak in the vicinity of 420 nm is placed on the back surface of the substrate 2 transparent to vacuum ultraviolet rays. The photooxidation reaction real time in which the ratio of the unreacted silicone oil and the vitrified photooxidized layer is the amount of light emitted from the fluorescent layer, and the image passing through the lens 6 and the bandpass filter 7 is constituted by the CCD camera 8. The observation monitor 9 can monitor the density distribution of the photo-oxidation reaction from the excitation light incident side, and can be used as an effective index of oxidant input.

Particularly noteworthy here is the provision of a vacuum ultraviolet light emitting lamp for solving both the rise in photoreaction atmosphere temperature and the stability of excitation light, which have the most adverse effects in the photooxidation reaction with silicone oil. is there. In particular, the reflecting surface that efficiently reflects vacuum ultraviolet rays is an aluminum mirror surface. However, this material oxidizes immediately when it is placed in the air, resulting in extremely low reflectivity. Therefore, if the mirror-polished aluminum reflecting mirror 10 is adhered by utilizing the photo-oxidation reaction of silicone oil so as to be in close contact with the outer periphery of the vacuum ultraviolet lamp (discharge tube) 3, deterioration due to oxidation of the mirror surface can be prevented permanently. . For example, if the electrode of the discharge tube is in contact with air or another gas body, a spark is generated, the electrode itself is deteriorated, and the electrode also becomes a heat radiation source. In order to solve all of these problems, an aluminum metal electrode 11 in which a mirror-polished aluminum reflecting mirror 10 and an electrode are integrated is provided, and discharge is performed between the mesh electrode 12. Furthermore, if the inside of the integrated aluminum metal electrode 11 is cooled by the cooling jacket 13 and a vacuum ultraviolet lamp as the main body is used for bonding, the solution can be solved by a series of lamp manufacturing processes. This is to suppress the deterioration due to the oxidation of the lamp and achieve a longer lamp life. More importantly, in order to lower the photoreaction atmosphere temperature, it is effective to cool the silicone oil photooxidized layer 4 with the sample stage 15 provided with the cooling jacket 14.

FIG. 2 is a system diagram for monitoring the real time observation of the photooxidation reaction from the back side of the fluorescent agent layer when the substrate is transparent to vacuum ultraviolet rays. A band having a central wavelength of 420 nm via the optical fiber 16 on the back surface side of the fluorescent agent layer 5 in which sodium salicylate having a sensitivity to vacuum ultraviolet rays as a fluorescent agent and having an emission peak in the vicinity of 420 nm is applied to the back surface of the transparent substrate 2. By detecting with a photocell (HAMAMATSU S2684-254) 17 with a pass filter, it can be used as an effective index of oxidant input. A spectroscope (Ocean Optics Inc. USB4000) can be attached to the optical fiber 16 to detect the emission spectrum and intensity.

FIG. 3 is a system diagram for monitoring real-time observation of the photooxidation reaction from the excitation light side when the substrate is opaque to vacuum ultraviolet rays. In the method of FIG. 1, only a substrate 2 transparent to vacuum ultraviolet rays can be used as a sample to be coated. Therefore, when the substrate is made of a material that is opaque to vacuum ultraviolet light such as metal, plastic, general glass, and ceramics, the emission of the fluorescent agent can be observed only from the excitation light incident side. Therefore, the silicone oil photooxidized layer 4 is formed on the surface of the opaque substrate 18, and the excitation light from the vacuum ultraviolet lamp 3 passes through the silicone oil photooxidized layer 4 and is reflected at the boundary with the substrate to return to the excitation light side. The photo-oxidation reaction real-time observation monitor 9 of FIG. 1 is detected by the sodium salicylate fluorescent agent layer 5 which is sensitive to vacuum ultraviolet rays and has a light emission peak at around 420 nm, and the relative change in the light emission intensity here is detected by the optical fiber 16. And a photocell (HAMAMATSU S2684-254) 17 with a bandpass filter having a central wavelength of 420 nm. The photo-oxidation reaction real-time observation monitor 9 detects the light reflected from the surface of the silicone oil photo-oxidation layer 4 and the light reflected from the surface of the substrate so that it passes through a band-pass filter having a center wavelength of 420 nm. The later light is amplified by an electronically cooled Si photocell (HAMAMATSU S2592-03), and the light traveling back and forth through the silicone oil photooxidized layer 4 is detected. In this case, if the aluminum vapor-deposited film 19 is applied only to the detection portion of the substrate surface, it can be used as a more effective index of oxidant input.

FIG. 4 is a system diagram in which a photo-oxidation layer is formed after applying a fluorescent agent in advance to a substrate surface opaque to vacuum ultraviolet rays. It is a system diagram which monitors from the back surface side of a fluorescent agent layer. On the surface of the opaque substrate 18, a sodium salicylate fluorescent agent layer 5 having a sensitivity to vacuum ultraviolet rays and having an emission peak near 420 nm is applied partially or entirely, and a silicone oil photooxidized layer 4 is formed thereon, The actual time of photooxidation reaction comprising the ratio of unreacted silicone oil and vitrified photooxidized layer according to the luminescence intensity, the amount of light emitted from the fluorescent layer as the lens 6, and the image passing through the bandpass filter 7 as the CCD camera 8. The observation monitor 9 can monitor the density distribution of the photooxidation reaction from the excitation light incident side. In this method, if the fluorescent agent layer is partially formed on the substrate surface, the overall photooxidation degree can be estimated from the light emission intensity at that portion.

FIG. 5 is a structural view of a cooling water circulation type vacuum ultraviolet Xe2 excimer lamp for photooxidation reaction excitation. (a) is a mesh electrode (positive electrode), (b) is a rod electrode (positive electrode). Cylindrical Xe2 excimer lamp that constitutes the Xe2 excimer lamp in order to prevent a decrease in reflectivity of the electrode-concave secondary curved reflector 11 in close contact with the Xe2 excimer lamp discharge tube 21 and to suppress the secular change of the vacuum ultraviolet light quantity. A cooling jacket 13 that circulates cooling water is provided in the electrode-concave secondary curved reflector 11 that is in close contact with the discharge tube 21. Here, silicone oil is applied along the concave surface of the electrode / concave secondary curved reflector 11, the Xe2 excimer lamp discharge tube 21 is brought into close contact with the applied surface, and the electrode / concave secondary curved reflector is opposed to the electrode / concave secondary curved reflector. The electrode / concave secondary curved surface 11 is made to emit vacuum ultraviolet light from the Xe2 excimer lamp discharge tube 21 while the electrode / concave secondary curved reflector 11 is cooled with the mesh electrode 12 placed in pressure contact. The method of photoadhering the reflecting mirror 11 and the Xe2 excimer lamp discharge tube 21 is (a), and the electrode / concave secondary curved reflecting mirror 11 is cooled in a state where the two rod electrodes 20 are pressed and adhered. However, (b) is a method in which vacuum ultraviolet light is emitted from the Xe2 excimer lamp discharge tube 21 and the electrode-concave secondary curved reflector 11 and the Xe2 excimer lamp discharge tube 21 are photobonded. This is a low-temperature vacuum ultraviolet light source in which contact between the reflecting mirror surface of the electrode / concave secondary curved reflecting mirror and the atmosphere is cut off. The temperature of the vacuum ultraviolet light source is preferably 10 to 50 ° C.

FIG. 6 is a structural diagram of a vacuum ultraviolet Xe2 excimer lamp in which cooling water circulation jackets and electrodes for photooxidation reaction excitation are alternately arranged. (a) The cooling jacket is a square pipe type, and (b) is a round pipe type cooling jacket. The electrode / concave secondary curved reflector 11 closely attached to the Xe2 excimer lamp discharge tube 21 and the cooling water circulation type (−) electrode / concave secondary curved reflector 22 are alternately arranged, and the reflection of each electrode / reflector is reflected. In order to prevent a decrease in the rate and suppress the secular change in the amount of vacuum ultraviolet light, the electrode-concave secondary curved reflector 11 closely attached to the cylindrical Xe2 excimer lamp discharge tube 21 constituting the Xe2 excimer lamp and the cooling water circulation type (- ) A cooling jacket 13 for circulating cooling water is provided in the electrode / concave secondary curved reflecting mirror 22. Here, a silicone oil is applied along the concave surface of each electrode / concave secondary curved reflector, the Xe2 excimer lamp discharge tube 21 is adhered along the applied surface, and the electrode / concave secondary curved reflector 11 is applied. Xe2 excimer lamp discharge while cooling each electrode / concave secondary curved reflector with the cooling water circulation type (-) electrode / concave secondary curved reflector 22 placed in pressure contact with each other Vacuum ultraviolet light is emitted from the tube 21, and the electrode / concave secondary curved reflector 11, the cooling water circulation type (−) electrode / concave secondary curved reflector 22 and the Xe 2 excimer lamp discharge tube 21 are optically bonded. Here, (a) is a square pipe type cooling jacket, and (b) is a round pipe type cooling jacket. In the low-temperature vacuum ultraviolet light source, the contact between the reflecting mirror surface of the electrode / concave secondary curved reflecting mirror and the atmosphere is blocked.

FIG. 7 is a structural diagram of a cooling water circulation type multistage vacuum ultraviolet Xe2 excimer lamp for photooxidation reaction excitation. (a) is a mesh electrode type and (b) a bar electrode type. A plurality of Xe2 excimer lamp discharge tubes 21 are arranged coaxially around the cooling water circulation pipe as a central axis, and each Xe2 excimer lamp discharge tube 21 is in close contact with the electrode-and-concave concave curved surface reflecting mirror 11, and each A cooling jacket 13 that circulates cooling water is provided in order to prevent a decrease in reflectivity of the electrode / reflector and suppress the secular change of the amount of vacuum ultraviolet light. Here, silicone oil is applied along the concave surface of each electrode / concave secondary curved reflector 11, the Xe2 excimer lamp discharge tube 21 is brought into close contact with the applied surface, and this electrode / concave secondary curved reflector 11 is applied. In a state where the mesh electrode 12 or the rod-shaped electrode 20 placed opposite to each other is pressed and adhered to each other, vacuum ultraviolet light is emitted from the Xe2 excimer lamp discharge tube 21 while cooling the electrode-concave secondary curved reflector. The electrode / concave secondary curved reflector 11 and the Xe2 excimer lamp discharge tube 21 are optically bonded. Here, (a) is a mesh electrode type and (b) a bar electrode type. In the low-temperature vacuum ultraviolet light source, the contact between the reflecting mirror surface of the electrode / concave secondary curved reflecting mirror and the atmosphere is blocked.

FIG. 8 is a schematic view of a touch and go silicone oil application device. The sample stage 15 is used for coating an optical crystal or an optical window. Here, the sample 23 to be coated is sucked by the suction clamp 24 and fixed to the sample table 15, and the sample is cooled by the Peltier cooling element 25 and the cooling jacket 13. First, the sample is fixed by facing the bag containing the silicone oil 26 below, and then instantaneously moves downward, touches the silicone oil surface 26, and then immediately rises by the spring 27. This operation is a touch-and-go method. Here, the sample to which the silicone oil is attached is rotated 180 degrees smoothly by the bearing 28 and turned upward, and then irradiated with light. In particular, the silicone oil drips into a uniform surface while the sample coated with silicone oil slowly rotates 180 degrees and the sample stage faces upward.

FIG. 9 is a schematic view of a reaction vessel equipped with a pressure jig for photobonding. The reaction vessel is composed of a photoreaction vessel pressurizing chamber 29 and a photoreaction chamber 30, and each chamber is provided with a right thread 31 and a left thread 32 so as to pressurize each other in parallel. When the screw thread is rotated in one direction by the photoreaction chamber pressurizing screw 33, both chambers approach each other. A piezo pressurizing element 34 is provided in the photoreaction vessel pressurizing chamber 29, and a sample stage 15 having a cooling jacket 14 is placed between the two chambers, and an adherend sample 37 transparent to vacuum ultraviolet light is placed thereon. 38 is sandwiched between silicone oils 26, and a photocell 17 with a band-pass filter is placed on the back surface of the adherend sample 38 with an optical fiber 16 via a sodium salicylate fluorescent agent layer 5 for the purpose of monitoring the photo-oxidation reaction process. Install.
A synthetic quartz window 36 is placed on the adherend sample 37 that is transparent to vacuum ultraviolet light, and the outside air is blocked by the O-ring 35 between the sample stage 15 and the synthetic quartz window 36 as a photoreaction chamber 30, and the reaction gas is introduced. A high-efficiency photobonding can be performed by supplying an oxidant gas from the exhaust port 39, applying a voltage to the piezo pressurizing element 34, and photoexciting with vacuum ultraviolet light 40 in a temperature atmosphere below room temperature.

FIG. 10 is a schematic view of a spinner thin film device. The photoreaction chamber 30 is shielded from the outside air by the synthetic quartz plate 6 and the photoreaction chamber lid 41 through the O-ring 35, and the reaction gas and the pressure in the container can be adjusted by the reaction gas inlet / exhaust port 39. Silicone oil (silicone) provided on a substrate 2 transparent to vacuum ultraviolet fiber by a rotational force transmitted by a motor 43 outside the photoreaction chamber, provided with a spinner sample stage 42 in the photoreaction chamber 30 (reaction vessel). The oil photooxidized layer 4) is thinned by high speed rotation. Thinning a silicone oil with relatively strong viscosity with a spinner is a difficult task. Therefore, dilute the silicone oil with a hydrocarbon solvent such as benzene, xylene or cyclohexaneethyl ether or a carbon chloride solvent such as carbon tetrachloride or chlorobenzene to make the viscosity extremely low so that they do not exceed the saturated vapor pressure. In order to achieve this, pressurization is performed with an inert gas such as nitrogen gas that transmits vacuum ultraviolet rays. In this pressurized state, the low-viscosity silicone oil applied on the substrate 2 placed on the spinner sample stage 42 by the motor 43 is thinned with a spinner, and then gradually reduced in pressure to vaporize the solvent. The rotation of the spinner is stopped, and an oxidant gas such as carbon dioxide is sealed by the reaction gas inlet / exhaust port 39. Next, the photo-oxidation layer is formed by irradiating light from a Xe2 excimer lamp (vacuum ultraviolet lamp 3). By repeating this series of operations, a thick film can be formed .

This apparatus is provided with a Peltier cooling element 25 with a water cooling jacket for lowering the reaction atmosphere temperature after the spinner is stopped. Further, a sodium salicylate fluorescent agent layer 5 is placed on the back surface of the substrate, and can be used as an effective index of oxidizing agent by detecting with a photocell 17 with a bandpass filter via an optical fiber 16. In this reactor, even with a silicone oil having a relatively high viscosity, spin coating was performed in a state of being heated by the Peltier cooling element 25 with a water cooling jacket, and after thinning, the rotation was stopped and the reverse voltage of the Peltier cooling element 25 was applied to cool. In this state, after oxidizing gas such as carbon dioxide is sealed from the reaction gas inlet / exhaust port 39, light from the Xe2 excimer lamp (vacuum ultraviolet lamp 3) is irradiated to form a photo-oxidized layer.

[FIG. 11] is a large area insulating film forming apparatus using a creeping discharge excimer lamp. The discharge method of the excitation light source of this apparatus is to discharge between a series of gas layers (Xe gas and atmosphere) made of different gases by means of the electrode 11 and the electrode 44, and the electrode 44 and the glass outer wall 45 of the excimer lamp (vacuum ultraviolet lamp 3). Between the silicone oil layer 4 and the outer wall of the excimer lamp glass, and the ultraviolet light from the vacuum ultraviolet lamp 3 is placed between the silicon oil layer 4 and the outer wall of the excimer lamp glass. Both perform a photo-oxidation reaction with high efficiency, and both metal electrodes 11 and 44 are water-cooled to prevent the oxidant contained in the silicone oil from exceeding the saturated vapor pressure and scattering out of the system. Further, the sodium salicylate fluorescent agent layer 5 is applied to the main point of the large-area long substrate 45 and is detected by a photocell (HAMAMATSU S2684-254) 17 with a bandpass filter having a central wavelength of 420 nm through the optical fiber 16. By doing so, it can be used as an index of effective oxidant input.

[FIG. 12] is a schematic entire process diagram relating to the invention of [Claim 1].

[Fig. 2] Using the low-temperature photo-oxidation apparatus of FIG. 2, using a reaction vessel, a plate-like sodium salicylate fluorescent agent layer 5 is inserted on the back surface of the quartz glass substrate 2, and silicone oil (Shin-Etsu Chemical Co., Ltd. Apply KF96-500cs), open the reaction gas inlet / exhaust port 39 attached to the reaction vessel 1, and after 30 minutes in an air atmosphere mixed with air and moisture, the silicone oil photo-oxidation layer 4 Photoexcitation was started with a distance of 15 mm between the network electrode 12 of the vacuum ultraviolet lamp discharge tube 3 (Xe2 excimer lamp, oscillation wavelength 157 nm).

The photoreaction here was detected by a photocell 17 with a band-pass filter via an optical fiber 16 attached to the back surface of the sodium salicylate phosphor layer 5. However, it was found that in the air, the film did not harden when the distance between the silicone oil photooxidized layer 4 and the mesh electrode 12 was 15 mm or more, and it took 120 minutes for the photooxidized film to form when the distance was 8 mm or less. When the interval was further reduced to 1 mm, the signal of the photocell 17 gradually increased from the start of irradiation and reached a peak in 5 minutes, and thereafter, there was no change. Moreover, the coating film at that time was only the surface layer cured, and the interface with the substrate remained silicone oil.

Then, the silicone oil 4 is applied again on the substrate 2, the reaction gas inlet / exhaust port 39 is opened, and after 30 minutes, when cooling water of 25 ° C. is circulated through the cooling jacket 14 of the sample table 15, the photocell 17. The signal increased to 15 minutes, but became dull after that. Therefore, the substrate was cooled using a Peltier cooling element having a 2Φ hole in the center between the sodium salicylate fluorescent agent layer 5 and the sample stage 15. Here, the substrate temperature is preferably 50 ° C. to 10 ° C. so that the vapor pressure of the oxidant mixed in the silicone oil is less than or equal to the saturated vapor pressure, but when it is 10 ° C. or less, frost is formed on the silicone oil photooxidized layer 4. It adheres and the signal of the photocell 17 becomes extremely weak. It was concluded that water vapor in the atmosphere dewed and hindered UV transmission, and at the same time the oxidant, which was water, was overconcentrated and the oxidation reaction would not proceed.

Therefore, in the case of the reaction in the atmosphere, the temperature at which the vapor pressure of the oxidizer does not exceed the saturated vapor pressure is determined to be between 15 and 30 ° C., and the cooling of the sample stage 15 is only cooling water, In order to prevent this, the vacuum ultraviolet lamp 3 (Xe2 excimer lamp) is circulated through the cooling water in the cooling jacket 13, so that all the heat sources at ambient temperature are suppressed only by water cooling, and the vapor pressure of the oxidant is saturated. The pressure was not exceeded.

As a result, the vapor pressure of the oxidizer inside or at the interface of the silicone oil is kept below the saturated vapor pressure without any atmospheric temperature control, and the Xe2 excimer lamp (20 mW) is irradiated for 60 minutes as in Example 4 of Patent Document 4. The film formed in this way had a transmittance of 90.6% at 193 nm, but achieved 91% with half the irradiation for 30 minutes. Furthermore, when the gas incident from the reaction gas inlet / exhaust port 39 was changed from air to carbon dioxide, the reaction time was further reduced to 15 minutes. Furthermore, even if the distance between the silicone oil photooxidation layer 4 and the mesh electrode 12 is increased to 20 cm, the light of the vacuum ultraviolet lamp 3 (Xe2 excimer lamp) reaches the silicone oil photooxidation layer 4 with little ultraviolet absorption in the optical path, and It has been clarified that carbon dioxide is photodegraded to form active oxygen, which acts as an oxidant and promotes photooxidation.

Therefore, from this experimental result, according to the present invention, by cooling the photo-oxidation reaction atmosphere, the vapor pressure of the oxidant in the silicone oil is suppressed within a range that does not exceed the saturated vapor pressure. Since the oxidizing agent can be maintained without a shortage, the conventional photoreaction time of 60 minutes or more can be reduced to 30 minutes or less, and if carbon dioxide is used as the oxidizing agent, the reaction time can be further reduced to 15 minutes or less. I knew it was possible. Here, a silicone oil containing oxygen, carbon dioxide, or water vapor mixed in advance under atmospheric pressure is used as a silicone oil containing an oxidizing agent, and if this is applied, the silicone oil is sandwiched between two samples and compressed. In the adhesion using vacuum ultraviolet irradiation, the oxidizing agent can be used for photooxidation without excess or deficiency. It should be noted here that when the oxidant is exhausted, the silicone oil is formulated so that the light irradiation is terminated, and the vapor pressure of the oxidant is controlled within a range not exceeding the saturated vapor pressure. Is to do.

[FIG. 9] Using a reaction vessel with a pressure bonding jig for photobonding, insert a silicone oil having a molecular weight of 60,000 (KF96-10000 manufactured by Shin-Etsu Chemical Co., Ltd.) into the gap between the synthetic quartz glass substrates 37 and 38, and the substrate. The Xe ₂ excimer lamp having a light emission wavelength of 172 nm is covered with a synthetic quartz window plate 36 and filled with an oxidant gas from the reaction gas inlet / exhaust port 39 and pressurized with the piezo pressurizing element 34 from below. Light 40 was irradiated for 10 to 60 minutes. Here, the photoreaction measures the effect of carbon dioxide gas, the effect of adhesion pressure, and the substrate temperature effect on a photocell 17 with a bandpass filter via an optical fiber 16 attached to the back surface of the sodium salicylate phosphor layer 5. % Of carbon dioxide gas mixed with nitrogen gas at 1 atm, adhesion pressure of 15 kg / cm ² , substrate temperature of 20 ° C., irradiated with 172 nm Xe ₂ excimer lamp for 15 minutes, tensile shear strength 180 kg / cm ² It can be seen that the adhesive strength is high. This value is 1/6, 15 minutes, compared with the light irradiation time of 90 minutes in Patent Document 6.

Using the spinner light thin film apparatus of FIG. 10, the film formation in a state where the viscosity of the silicone oil coating with a high viscosity silicone oil was diluted with a solvent was compared with that of the silicone oil diluted with a solvent. First, in a photoreaction chamber 30 that is blocked from outside air, a silicone oil silicone oil (KF96-50cs manufactured by Shin-Etsu Chemical Co., Ltd.) is applied with a solvent such as xylene and chlorobenzene coated on the substrate 2 that is transparent to the vacuum ultraviolet fiber. In order to dilute to extremely reduce the viscosity and not to exceed the saturated vapor pressure, pressurize with nitrogen gas that transmits vacuum ultraviolet light. In this pressurized state, the low-viscosity silicone oil applied on the substrate 2 placed on the spinner sample stage 42 by the motor 43 is thinned with a spinner, and then gradually reduced in pressure to vaporize the solvent. After the rotation of the spinner was stopped, the temperature of the reaction chamber was changed from 5 to 50 ° C. with the Peltier cooling element 25, and carbon dioxide was sealed with the reaction gas inlet / exhaust port 39. The state of the oxidation reaction at this time is detected by a photocell 17 with a band-pass filter through the optical fiber 16, and irradiated with light from a Xe2 excimer lamp (vacuum ultraviolet lamp 3) for 20 minutes, and the film thickness is reduced to 100 nm. We were able to.

Next, the silicone oil 4 that is not diluted with a solvent is spin-coated with the Peltier cooling element 25 heated to 80 ° C., and after thinning, the rotation is stopped, the reverse voltage of the Peltier cooling element 25 is applied, and the liquid is cooled. After oxidizing gas such as carbon dioxide was sealed from the reaction gas inlet / exhaust port 39, Xe2 excimer lamp (vacuum ultraviolet lamp 3) was irradiated to form a photo-oxidized layer. Obtained.

In general, when a resist is applied to a semiconductor substrate, the viscosity of the spinner resist is extremely low. However, silicone oil is viscous, and even if it is spun at high speed, there is a limit to thinning the film. When rotation is stopped, it returns to its original state due to the surface tension of the remaining oil itself, and a thin film with a uniform thickness is formed. There wasn't.

Therefore, according to the present invention, silicone oil diluted with a solvent is applied to a sample on a spinner placed in a reaction vessel that is blocked from outside air, and the atmosphere is set to a pressure equal to or higher than the saturated water vapor of the solvent. Rotate the spinner at a high speed in a state pressurized with an inert gas or an oxidant gas, thin the film, and then irradiate it with vacuum ultraviolet radiation in a state where an oxidant gas of 1 atm or less is sealed while vaporizing the solvent by deaeration. As a result, a thin film of 100 nanometers or less could be formed.

A solar cell coated with RTV silicone rubber and a solar cell attached to an aluminum substrate and a quartz glass substrate are fixed in a vacuum container, sucked up to 10 ^-4 Torr, then the container cock is closed, and 6 hours / day. The Xe2 excimer lamp of 172nm was irradiated simultaneously with the heater heating for 1 month. One month later, using a mass spectrometer (QMAS), C ₈ H ₂₄ O ₄ Si ₄ , C ₁₀ H ₃₀ O ₅ Si ₅ , C ₁₂ H ₃₆ O ₆ Si ₆ , C ₁₄ H ₄₂ O ₇ Si ₇ , C ₁₆ H ₄₈ O ₈ Si ₈ , C ₁₈ H ₅₄ O ₉ Si ₉ , C ₂₀ H ₆₀ O ₁₀ Si ₁₀ MAS numbers 294, 370, 444, 518, 592, 666, 740 The quartz substrate became slightly black. Therefore, when the trace amount of oxygen peroxide was continuously adsorbed to the substrate under the same conditions, no clouding or blackening of the substrate was observed.

The first feature of the present invention is to mass-produce large-area solar cell panels and large-area liquid crystal displays that do not use a conventional thick and heavy plate glass. Photo-oxidation film formation involves applying silicone oil to a substrate or product in the same way as painting, and monitoring the progress of the photoreaction using the luminescence of the fluorescent agent while irradiating with vacuum ultraviolet rays. By controlling the vapor pressure of the liquid to below the saturated vapor pressure and supplying the oxidizer without excess or deficiency to the silicone oil, a film that is transparent, hard, and excellent in electrical insulation can be formed. It can be used as an insulating base film or protective film for liquid crystal displays and the like.

The second feature of the present invention is that it is possible to form a photo-oxidized thin film rich in weather resistance. It can be applied when taking observation photographs of the ground from the windows.

Furthermore, it can also be used as an insulating base film or protective film for a thermoelectric conversion module or the like. Further, the transparent photo-oxidized layer thin film formed on the substrate can be etched with an acid or an organic solvent to form a film-like thin glass. This thin glass can be used in many fields as a semiconductor substrate or as an optical glass in addition to a mother glass of a liquid crystal panel.

It is the schematic which shows the low-temperature photo-oxidation layer forming method and apparatus of silicone oil. It is a system diagram which monitors photooxidation reaction real-time observation from the back side of a fluorescent agent layer when the substrate is transparent to vacuum ultraviolet rays. It is a system diagram which monitors the photo-oxidation reaction real-time observation when a board | substrate is opaque to a vacuum ultraviolet ray from the excitation light side. It is a system diagram in which a photo-oxidation layer is formed after applying a fluorescent agent in advance to a substrate surface opaque to vacuum ultraviolet rays. FIG. 3 is a structural diagram of a vacuum ultraviolet Xe2 excimer lamp for photooxidation reaction excitation. (a) The positive electrode is a mesh electrode, (b) is the positive electrode and a plurality of rod electrodes FIG. 3 is a structural diagram of a vacuum ultraviolet Xe2 excimer lamp in which cooling water circulation jackets and electrodes for photoacid reaction excitation are alternately arranged. (a) The cooling jacket is a square pipe type, and (b) is a round pipe type cooling jacket. FIG. 4 is a structural diagram of a cooling water circulation type multi-stage vacuum ultraviolet Xe2 excimer lamp for photooxidation reaction excitation. (a) is a mesh electrode type and (b) a bar electrode type. 1 is a schematic diagram of a touch-and-go type silicone oil application device. FIG. It is a reaction container schematic with a pressure jig for photobonding. It is a spinner optical thin film apparatus schematic. This is a large area insulating film forming apparatus using a creeping discharge excimer lamp. FIG. 3 is a schematic entire process diagram related to the invention of [Claim 1].

1 Reaction vessel 2 Substrate transparent to vacuum ultraviolet rays
3 Vacuum ultraviolet lamp (discharge tube)
4 Silicone oil photo-oxidation layer 5 Sodium salicylate phosphor layer 6 Lens 7 Bandpass filter 8 CCD camera 9 Photo-oxidation reaction real-time observation monitor 10 Mirror-polished aluminum reflector 11 Aluminum metal electrode (negative electrode)
12 Mesh electrode (positive electrode)
13 Cooling jacket 14 Cooling jacket (for sample stage)
15 Sample stage 16 Optical fiber 17 Photocell 18 with bandpass filter Opaque substrate 19 Aluminum vapor deposition film 20 Bar electrode (positive electrode)
21 Xe2 excimer lamp discharge tube 22 Cooling water circulation type (-) electrode and concave secondary curved reflector 23 Sample to be coated 24 Suction clamp 25 Peltier cooling element 26 Silicone oil 27 Spring 28 Bearing 29 Photoreaction vessel pressurization chamber 30 Photoreaction chamber 31 Right Thread 32 Left Thread 33 Photoreaction Chamber Pressure Screw 34 Piezo Pressure Element 35 O-ring 36 Synthetic Quartz Window Plate 37 Bonded Sample 1 (Transparent to Vacuum Ultraviolet)
38 Adhered sample 2 (Transparent to vacuum ultraviolet)
39 Reaction gas inlet / outlet 40 Vacuum ultraviolet light (excitation light)
41 Photoreactor lid 42 Spinner sample stage 43 Motor 44 Pipe-shaped slide electrode 45 Excimer lamp glass outer wall
46 Large area long substrate

Claims (7)

When forming a transparent photo-oxidized layer thin film of SiO2 on a substrate by photooxidation of silicone oil, a pretreatment step of the substrate,
A coating step of the silicone for oil to the substrate table surface,
A step for photoreaction an oxidizing agent and silicone oil because the liquid or gaseous oxidizing agent is just enough held in a silicone oil layer applied to the substrate,
And step for sustaining a light reaction by monitoring the emission intensity of the fluorescent agent layers sensitive to a vacuum ultraviolet course of vitrification by photooxidation of the silicone oil layer,
A method for forming a transparent photo-oxidized thin film, comprising feeding back the emitted light intensity to a vacuum ultraviolet lamp and forming a SiO2 thin film by a photo-oxidation reaction without excess or deficiency of an oxidizing agent. Steps to photoreaction an oxidizing agent and silicone oil because just enough to hold the liquid or gaseous oxidizing agent in the silicone oil layer is, when the oxidizing agent is a liquid exceeds the saturation vapor pressure of the oxidizing agent If the oxidizing agent is a gas in a range, the ultraviolet light is irradiated with the photoreactive atmosphere temperature cooled to 10 to 50 ° C. within the range not exceeding the saturation solubility of the oxidizing agent, or the photooxidizing atmosphere. If it cannot be cooled to the temperature range, the reaction vessel is shut off from the atmosphere, and vacuum ultraviolet irradiation is performed with an oxidant that has been pressurized with an oxidant gas diluted with an inert gas to 1 atmosphere or more in the reaction vessel. 2. The method for forming a transparent photo-oxidized thin film according to claim 1, wherein To sustain the photoreaction to monitor the course of photooxidation of the silicone oil layer
Step is, the excess and deficiency of the oxidizing agent supplied to the silicone oil layer, light is emitted by the fluorescent agent layers sensitive to a vacuum ultraviolet light that has passed through the silicone oil layer, depending on the emission intensity of the fluorescent light adhesive layer Not The ratio of the reaction silicone oil and the vitrified photo-oxidized layer is detected, and the transparent photo-oxidized layer is formed by feeding back to the liquid or gaseous oxidant supply or the irradiation intensity and irradiation time of vacuum ultraviolet light. The method for forming a transparent photo-oxidized thin film according to claim 1 or 2. In coating fabrics step of the silicone oil on the surface of the substrate, and wherein the silicone oil layer for forming a transparent photo-oxidation thin film is a gaseous low-molecular siloxanes adsorbed layer or a silicone oil layer having a siloxane bond of the low molecular 2. The method for forming a transparent photo-oxidized layer thin film according to claim 1. In forming a transparent photo-oxidation layer thin film thick film substrate, coated fabrics step of shea Rikon'oi Le of the front surface of the substrate is, after the viscosity was applied silicone oil in the range of 0.65~50cs on the substrate, or After applying a silicone oil diluted with an organic solvent at a higher viscosity, vaporize the solvent by reducing the pressure, and enclose the oxidant gas and irradiate vacuum ultraviolet light to form one photooxidized layer. a transparent photo-oxidation thin film forming method according to claim 1 Symbol mounting, characterized in that claim 1 by repeating a series of steps sequentially laminating a film according to the formation of a thick film. As a means for preventing fogging and blackening of the light-receiving surface by the low-molecular siloxane adsorbing layer scattered from the silicone-based material employed in an artificial satellite-mounted solar panel and a telescope mirror in outer space, the light-receiving surface Means for adsorbing an oxidant gas such as oxygen gas, hydrogen peroxide, moisture and / or a metal oxide capable of supplying oxygen to the light receiving surface material, and the light receiving surface material by vacuum ultraviolet rays of sunlight. The method of forming a transparent photo-oxidized layer thin film according to claim 1, wherein the transparent photo-oxidized layer is formed to inhibit formation of free carbon. A substrate having a planar or uneven surface shape, and after forming a thick film on the substrate by the method according to claim 5, only the substrate is etched to form a thin plate glass or a patterned plate glass. The method for forming a transparent photo-oxidized layer thin film according to claim 1 or 5.

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