JP4601459B2 - Exposure mask and manufacturing method thereof - Google Patents

Description

  The present invention relates to an exposure mask that can be used for patterning utilizing the action of a photocatalyst accompanying energy irradiation, and a method for manufacturing the same.

  Conventionally, various methods have been proposed as a method for producing a pattern forming body for forming various patterns such as designs, images, characters, and circuits on a substrate. For example, lithographic printing, offset printing, and heat mode are proposed. A printing method for producing a lithographic printing original plate using a recording material is also used. In addition, for example, pattern exposure is performed on a photoresist layer coated on a substrate, and after exposure, the photoresist is developed and further etched, or the photoresist is exposed using a substance having functionality to the photoresist. There is also known a method of manufacturing a pattern forming body by photolithography, such as directly forming a target pattern by the above.

  However, when manufacturing a high-definition pattern forming body used for, for example, a color filter or the like, the printing method has a problem such as low positional accuracy, and is difficult to use. Further, in the photolithography method, there is a problem that a waste liquid needs to be processed because it is necessary to use a photoresist and to perform development or etching with a liquid developer after exposure. In addition, when a functional substance is used as a photoresist, there is a problem that it deteriorates due to an alkaline solution or the like used during development.

  Therefore, on the base material, a property changing layer whose properties are changed by the action of the photocatalyst accompanying energy irradiation is formed, arranged facing the photocatalyst-containing layer substrate containing the photocatalyst, and then exposed from a predetermined direction. The inventors have studied a method for producing a pattern forming body that forms a pattern in which the characteristics of the characteristic change layer have changed (Patent Document 1). According to this method, a pattern forming body capable of easily forming a functional part such as a colored layer by using the characteristics of the characteristic change layer by the action of a photocatalyst accompanying energy irradiation is manufactured with high definition. I can do it. In addition, there is an advantage that it is not necessary to use a developer or the like. The mechanism of action of such a photocatalyst is not necessarily clear, but carriers generated by irradiation of energy react directly with nearby compounds, or by active oxygen species generated in the presence of oxygen and water, It is thought to change the chemical structure of organic matter.

  Here, in the above-described method for producing a pattern formed body, the photocatalyst in the photocatalyst containing layer in the exposed region is excited to change the characteristics of the opposing characteristic change layer, resulting in a characteristic difference. It takes a predetermined time to make it happen. If this time can be shortened, further efficiency can be achieved.

Therefore, in the above invention, by forming a shielding part on the photocatalyst-containing layer containing the photocatalyst, the active oxygen species generated by the action of the photocatalyst accompanying the energy irradiation is reached without diffusing and reaching the surface of the characteristic change layer. The method of making it etc. is also proposed. However, since this shielding part is preferably not decomposed by the action of a photocatalyst accompanying energy irradiation, it is usually formed using a metal such as chromium. For this reason, carriers generated in the photocatalyst-containing layer due to energy irradiation may flow to the shielding part, and active oxygen species may not be generated efficiently.
JP 2000-249821 A

  Therefore, an exposure mask having a photocatalyst-containing layer, which is used when forming a pattern using the action of a photocatalyst accompanying energy irradiation, and can form a pattern with different characteristics efficiently and with high resolution. The provision of

  The present invention includes a substrate, a photocatalyst containing layer formed on the substrate and containing at least a photocatalyst, an inorganic oxide layer formed on the photocatalyst containing layer, and a pattern on the inorganic oxide layer An exposure mask characterized by having a shielding portion formed on the surface.

  According to the present invention, since the inorganic oxide layer is formed on the photocatalyst-containing layer, carriers generated in the photocatalyst-containing layer accompanying energy irradiation can be prevented from flowing to the shielding part. It is possible to efficiently generate active oxygen species and the like. Therefore, for example, a pattern having different characteristics can be obtained by disposing an exposure mask of the present invention opposite to a characteristic change layer whose characteristics change due to decomposition or modification of organic groups by active oxygen species and the like, and irradiating with energy. Can be formed efficiently. In addition, since the shielding part is formed on the inorganic oxide, the active oxygen species generated by the action of the photocatalyst accompanying the energy irradiation can reach the characteristic change layer and the like without diffusing. There is also an advantage that characteristics can be changed by resolution.

  The present invention also includes a photocatalyst-containing layer forming step for forming a photocatalyst-containing layer containing at least a photocatalyst on a substrate, and an inorganic oxide layer forming step for forming an inorganic oxide layer on the photocatalyst-containing layer. And a shielding part forming step of forming a shielding part on the inorganic oxide layer. A method for manufacturing an exposure mask is provided.

  According to the present invention, since the inorganic oxide layer forming step for forming the inorganic oxide layer is included, when energy is irradiated to the exposure mask manufactured according to the present invention, carriers generated from the photocatalyst are applied to the shielding portion. The active oxygen species and the like can be efficiently generated without flowing. Therefore, it is possible to manufacture an exposure mask that can efficiently form patterns having different characteristics with high resolution.

  At this time, the shielding part forming step is preferably a process of forming the shielding part by a lift-off method. When the shielding part is formed by a lift-off method, an inorganic substance can be left on the inorganic oxide layer, and an exposure mask capable of exhibiting a photocatalytic function more efficiently can be obtained. Because you can.

  The present invention also includes a photocatalyst-containing layer forming step of forming a photocatalyst-containing layer containing at least a photocatalyst on a substrate, and a shielding portion forming step of forming a shield portion on the photocatalyst-containing layer by a lift-off method. A method for manufacturing an exposure mask is provided.

  According to this invention, since the said shielding part is formed by the lift-off method, it can prevent that an inorganic substance remains on the photocatalyst content layer of the area | region in which the shielding part is not formed. As a result, it is possible to provide an exposure mask that can efficiently form a pattern with different characteristics and with high resolution without the action of the photocatalyst being hindered by impurities.

  According to the present invention, active oxygen species and the like can be efficiently generated by energy irradiation, and there is an effect that patterns having different characteristics can be efficiently formed with high resolution.

  The present invention relates to an exposure mask that can be used for patterning utilizing the action of a photocatalyst accompanying energy irradiation, and a method for manufacturing the same. Each will be described separately below.

A. First, the exposure mask of the present invention will be described. The exposure mask of the present invention includes a base material, a photocatalyst-containing layer formed on the base material and containing at least a photocatalyst, an inorganic oxide layer formed on the photocatalyst-containing layer, and the inorganic oxide layer It has the shielding part formed in pattern shape on it, It is characterized by the above-mentioned.

  The exposure mask of the present invention includes, for example, as shown in FIG. 1, a base material 1, a photocatalyst containing layer 2 formed on the base material 1, and an inorganic oxide layer formed on the photocatalyst containing layer 2. 3 and a shielding part 4 formed in a pattern on the inorganic oxide layer 3. For example, as shown in FIG. 2, the exposure mask of the present invention comprises a characteristic change layer 11 and the like whose characteristics change as a result of decomposition or modification of organic groups on the surface by active oxygen species and the like, and the shielding portion 4 and the like. It is arranged and used so as to face each other (FIG. 2 (a)), and when the energy 5 is irradiated from a predetermined direction in this state, the characteristic changes into a pattern in which the shielding part 4 is not formed. The characteristic change pattern 12 in which the characteristic of the layer 11 is changed can be formed (FIG. 2B).

  According to the present invention, since the inorganic oxide layer is formed between the photocatalyst-containing layer and the shielding part, carriers generated from the photocatalyst excited by energy irradiation are, for example, a metallic shielding part or the like. It can stay in the field without contributing to the generation of active oxygen species. Therefore, when the exposure mask of the present invention is used for pattern formation as described above, the organic group can be efficiently decomposed or modified, and patterns having different characteristics can be efficiently formed. It is.

At this time, in the present invention, since the shielding part is formed on the inorganic oxide layer, in the region where the shielding part is formed, the active oxygen species generated when the photocatalyst is excited is shielded. It is possible to prevent the light from being exposed to the surface. Therefore, in this region, it is possible to form a pattern with changed characteristics at a high resolution without changing the characteristics of the opposing characteristic change layers and the like. In addition, for example, the shielding part can be used as a spacer between the exposure mask and the characteristic change layer. In this case, the characteristic change can be made without diffusing the active oxygen species generated in the region where the shielding part is not formed. Since it is possible to reach a layer or the like, it is possible to form a pattern having a changed characteristic with higher resolution.
Hereinafter, each configuration of the exposure mask of the present invention will be described in detail.

1. Inorganic oxide layer First, the inorganic oxide layer used in the exposure mask of the present invention will be described. The inorganic oxide layer used in the exposure mask of the present invention is a layer formed between a photocatalyst-containing layer and a shielding portion, which will be described later, and has an inorganic oxide, and this inorganic oxide layer has no conductivity. It is said. This is because when the inorganic oxide layer has conductivity, carriers generated from the photocatalyst containing layer by energy irradiation flow through the inorganic oxide layer, making it difficult to efficiently generate active oxygen species.

Here, the conductivity of the inorganic oxide layer used in the present invention is preferably in the range of 10 ⁻¹⁶ to 10 ⁻⁶ S, particularly in the range of 10 ⁻¹⁶ to 10 ⁻¹² S. This is because the carrier generated from the photocatalyst containing layer can be prevented from flowing.

  Moreover, in this invention, it is preferable that the said inorganic oxide layer permeate | transmits the active oxygen seed | species etc. which generate | occur | produced from the photocatalyst containing layer by energy irradiation efficiently. This is because when the inorganic oxide layer does not allow these active oxygen species to permeate, it is difficult to efficiently change the characteristics of the characteristic change layer and the like.

The material of the inorganic oxide layer used in the present invention is not limited as long as it is a layer having an inorganic oxide and is not decomposed by the action of a photocatalyst accompanying energy irradiation. Examples of the inorganic oxide contained include silica, alumina, zirconia, titania, itnia, selenia, and boronia. In the present invention, a layer containing silica is particularly preferable. In addition, the inorganic oxide layer used in the present invention may appropriately contain other materials in addition to the inorganic oxide as necessary. The inorganic oxide preferably has a conductivity in the range of 10 ⁻¹⁶ to 10 ⁻⁶ S, particularly in the range of 10 ⁻¹⁶ to 10 ⁻¹² S. This is because the conductivity of the inorganic oxide layer can be made as described above.

  At this time, the thickness of the inorganic oxide layer is preferably about 0.005 μm to 1 μm, more preferably 0.01 μm to 0.2 μm. If it is thicker than the above film thickness, it may be difficult to transmit active oxygen species generated from the photocatalyst-containing layer, and if it is thinner than the above film thickness, the inorganic oxide layer is non-conductive. This is because the effect as a protective layer cannot be exhibited, and carriers generated in the photocatalyst containing layer may flow to the shielding part or the like.

  Here, the method for forming the inorganic oxide layer is not particularly limited as long as it is a method capable of forming the layer as described above, and generally an inorganic oxide layer is formed. For example, a vacuum film-forming method such as a sputtering method, a CVD method or a vacuum deposition method, a chemical deposition method such as a sol-gel method or a liquid phase deposition method, or the like can be used.

2. Photocatalyst containing layer Next, the photocatalyst containing layer used for the mask for exposure of this invention is demonstrated. The photocatalyst-containing layer used in the present invention is not particularly limited as long as it is formed on a substrate described later and contains at least a photocatalyst. Such a photocatalyst-containing layer may be composed of a photocatalyst and a binder, or may be formed of a photocatalyst alone. Further, the wettability of the surface may be particularly lyophilic or lyophobic. In the case of a photocatalyst-containing layer composed only of a photocatalyst, the efficiency of decomposing or modifying organic groups and the like is improved, which is advantageous in terms of cost such as shortening the processing time during pattern formation. On the other hand, in the case of a photocatalyst-containing layer comprising a photocatalyst and a binder, there is an advantage that the formation of the photocatalyst-containing layer is easy.

Examples of the photocatalyst contained in the photocatalyst-containing layer used in the present invention include titanium dioxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), and strontium titanate (SrTiO ₃ ), which are known as photo semiconductors. , Tungsten oxide (WO ₃ ), bismuth oxide (Bi ₂ O ₃ ), and iron oxide (Fe ₂ O ₃ ), and one or a mixture of two or more selected from these may be used. it can.

  In the present invention, titanium dioxide is particularly preferably used because it has a high band gap energy, is chemically stable, has no toxicity, and is easily available. Titanium dioxide includes an anatase type and a rutile type, and both can be used in the present invention, but anatase type titanium dioxide is preferred. Anatase type titanium dioxide has an excitation wavelength of 380 nm or less.

  Examples of such anatase type titanium dioxide include hydrochloric acid peptizer type anatase type titania sol (STS-02 manufactured by Ishihara Sangyo Co., Ltd. (average particle size 7 nm), ST-K01 manufactured by Ishihara Sangyo Co., Ltd.), nitric acid solution An anatase type titania sol (TA-15 manufactured by Nissan Chemical Co., Ltd. (average particle size 12 nm)) and the like can be mentioned.

  The smaller the particle size of the photocatalyst, the more effective the photocatalytic reaction occurs. The average particle size is preferably 50 nm or less, and it is particularly preferable to use a photocatalyst of 20 nm or less.

  Examples of the method for forming the photocatalyst-containing layer composed only of the photocatalyst as described above include a method using a vacuum film forming method such as a sputtering method, a CVD method, or a vacuum deposition method. By forming the photocatalyst-containing layer by a vacuum film forming method, it is possible to obtain a photocatalyst-containing layer that is a uniform film and contains only the photocatalyst. In addition, since the organic group can be uniformly decomposed and modified, and consists of only a photocatalyst, the organic group can be decomposed and modified more efficiently than when a binder is used. .

  Examples of a method for forming a photocatalyst-containing layer consisting of only a photocatalyst include a method in which amorphous titania is formed on a substrate and then phase-changed to crystalline titania by firing when the photocatalyst is titanium dioxide. . As the amorphous titania used here, for example, hydrolysis, dehydration condensation, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-propoxytitanium, tetrabutoxytitanium, titanium inorganic salts such as titanium tetrachloride and titanium sulfate, An organic titanium compound such as tetramethoxytitanium can be obtained by hydrolysis and dehydration condensation in the presence of an acid. Next, it can be modified to anatase titania by baking at 400 ° C. to 500 ° C. and modified to rutile type titania by baking at 600 ° C. to 700 ° C.

  On the other hand, when a binder is used for the photocatalyst-containing layer, one having a high binding energy such that the main skeleton of the binder is not decomposed by photoexcitation of the photocatalyst is preferable, and examples thereof include organopolysiloxane.

  When organopolysiloxane is used as a binder in this way, the photocatalyst-containing layer is prepared by dispersing the photocatalyst and the binder organopolysiloxane in a solvent together with other additives as necessary. The coating solution can be formed by coating on a substrate. As the solvent to be used, alcohol-based organic solvents such as ethanol and isopropanol are preferable. The application can be performed by a known application method such as spin coating, spray coating, dip coating, roll coating, or bead coating. When an ultraviolet curable component is contained as a binder, the photocatalyst-containing layer can be formed by irradiating with ultraviolet rays and performing a curing treatment.

An amorphous silica precursor can be used as the binder. This amorphous silica precursor is represented by the general formula SiX _4, X is a halogen, a methoxy group, an ethoxy group or a silicon compound an acetyl group or the like, and silanol or average molecular weight of 3,000 or less, their hydrolysates Polysiloxane is preferred.

  Specific examples include tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, tetrabutoxysilane, and tetramethoxysilane. In this case, the amorphous silica precursor and the photocatalyst particles are uniformly dispersed in a non-aqueous solvent, and hydrolyzed with moisture in the air on the substrate to form silanol, and then at room temperature. A photocatalyst-containing layer can be formed by dehydration-condensation polymerization. If dehydration condensation polymerization of silanol is carried out at 100 ° C. or higher, the degree of polymerization of silanol increases and the strength of the film surface can be improved. Moreover, these binders can be used individually or in mixture of 2 or more types.

  When the binder is used, the content of the photocatalyst in the photocatalyst containing layer can be set in the range of 5 to 80% by weight, preferably 20 to 70% by weight. The thickness of the photocatalyst containing layer is preferably in the range of 0.05 to 10 μm.

In addition to the photocatalyst and the binder, the photocatalyst containing layer can contain a surfactant. Specifically, hydrocarbons such as NIKKOL BL, BC, BO, BB series manufactured by Nikko Chemicals Co., Ltd., ZONYL FSN, FSO manufactured by DuPont, Surflon S-141, 145 manufactured by Asahi Glass Co., Ltd., Dainippon Megafac F-141, 144 manufactured by Ink Chemical Industry Co., Ltd., Footgent F-200, F251 manufactured by Neos Co., Ltd., Unidyne DS-401, 402 manufactured by Daikin Industries, Ltd., Fluorard FC-170 manufactured by 3M Co., Ltd. Fluorine-based or silicone-based nonionic surfactants such as 176, and cationic surfactants, anionic surfactants, and amphoteric surfactants can also be used.
Furthermore, in addition to the above surfactants, the photocatalyst containing layer includes polyvinyl alcohol, unsaturated polyester, acrylic resin, polyethylene, diallyl phthalate, ethylene propylene diene monomer, epoxy resin, phenol resin, polyurethane, melamine resin, polycarbonate, Polyvinyl chloride, polyamide, polyimide, styrene butadiene rubber, chloroprene rubber, polypropylene, polybutylene, polystyrene, polyvinyl acetate, polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, polyisoprene, oligomers, polymers, etc. It can be included.

3. Next, the shielding part used for the exposure mask of the present invention will be described. The shielding part used in the present invention is formed in a pattern on the inorganic oxide layer, as long as it can shield the active oxygen species generated from the photocatalyst containing layer by energy irradiation. The energy permeability and the like are not particularly limited. For example, it may be a transparent material that transmits energy, or may be a material that shields energy.

  In addition, the material of the shielding part used in the present invention is not particularly limited as long as it is not decomposed by the action of the photocatalyst of the photocatalyst-containing layer. It is appropriately selected and used depending on the etc.

  For example, the resin binder may be a layer in which shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments are included in a pattern. As the resin binder to be used, polyimide resin, acrylic resin, epoxy resin, polyacrylamide, polyvinyl alcohol, gelatin, casein, cellulose, or a mixture of one or more resins, photosensitive resin, or O / A W emulsion type resin composition, for example, an emulsion of a reactive silicone can be used. The thickness of such a resin shielding part can be set within a range of 0.5 to 10 μm. As a method for patterning the resin shielding part, a generally used method such as a photolithography method or a printing method can be used.

  Furthermore, the shielding part may be formed by a thermal transfer method. The thermal transfer method for forming a shielding part is usually a thermal transfer sheet provided with a light-to-heat conversion layer and a shielding part transfer layer on one side of a transparent film base material, and energy is applied to the area where the shielding part is formed. By irradiating, the shielding part transfer layer is transferred onto the substrate to form a shielding part. The film thickness of the shielding part formed by such a thermal transfer method can usually be about 0.5 μm to 10.0 μm, particularly about 0.8 μm to 5.0 μm.

  The shielding part transferred by the thermal transfer method is usually composed of a shielding material and a binder, and inorganic materials such as carbon black and titanium black can be used as the shielding material. The particle diameter of such a shielding material is preferably 0.01 μm to 1.0 μm, and more preferably 0.03 μm to 0.3 μm.

  Further, the binder is preferably a resin composition having thermoplasticity and thermosetting properties, has a thermosetting functional group, and has a softening point in the range of 50 ° C to 150 ° C, particularly 60 ° C. It is preferable to be comprised by the resin material which exists in the range of -120 degreeC, a hardening | curing agent, etc. Specific examples of such a material include a combination of an epoxy compound or epoxy resin having two or more epoxy groups in one molecule and a latent curing agent thereof. As a latent curing agent for epoxy resins, it does not have reactivity with epoxy groups up to a certain temperature, but when it reaches the activation temperature by heating, it changes to a molecular structure with reactivity with epoxy groups. A curing agent can be used. Specific examples include neutral salts and complexes of acidic or basic compounds having reactivity with epoxy resins, block compounds, high melting point bodies, and microcapsules. In addition to the above materials, the shielding part may contain a release agent, an adhesion assistant, an antioxidant, a dispersant, and the like.

  Here, in the present invention, the shielding part is preferably one that is not decomposed by the action of a photocatalyst accompanying energy irradiation, and is made of an inorganic substance such as a metal such as chromium, nickel, gold, silver, copper, or aluminum. Preferably there is. This is because the exposure mask of the present invention can be used repeatedly and the pattern can be stably formed. In the present invention, as a method for forming a shielding portion made of an inorganic material such as metal, it is particularly preferable that the shielding portion is formed by a lift-off method. Examples of a method for forming a shielding portion made of such a metal include a method of forming a metal thin film such as chromium having a thickness of about 1000 to 2000 mm by a sputtering method, a vacuum evaporation method, and the like, and patterning the thin film. In this case, it is difficult to completely remove the metal or the like in the region where the shielding portion is not formed during development, and the metal or the like is left as an impurity or the developer used for development contains metal or the like. In some cases, the metal or the like adheres to a region where the shielding portion is not formed. When such a metal adheres to a region other than the shielding part, it causes a decrease in the sensitivity of the photocatalyst, and it is difficult to remove because it cannot be decomposed by the action of the photocatalyst. is there.

  On the other hand, in the lift-off method, for example, as shown in FIG. 3, a photosensitive resin layer 21 is applied on the entire surface of the inorganic oxide layer 3 (FIG. 3A) and exposed using a photomask 22 or the like. (FIG. 3B), the photosensitive resin layer 21 is formed only in the region where the shielding portion is not formed (FIG. 3C). Thereafter, a shielding layer 24 made of chromium or the like is formed on the inorganic oxide layer 3 in which the photosensitive resin layer 21 is formed in a pattern, for example, by vapor deposition (FIG. 3D). In this method, the shielding portion 4 is formed only in the target region by removing the layer 21 and the shielding layer 24 formed on the photosensitive resin layer 21 (FIG. 3E). According to this method, it is possible to prevent a metal such as chromium used as the shielding portion from contacting the inorganic oxide layer in the region where the shielding portion is not formed. In addition, it is not necessary to use a developer containing a metal for dissolving a metal used in a general photolithography method and the like, so that the metal does not adhere to the inorganic oxide layer. it can. Therefore, it is possible to provide an exposure mask that can perform pattern formation and the like efficiently without reducing the sensitivity of the photocatalyst.

  The photosensitive resin used in such a lift-off method may be any photosensitive resin used in a general photolithography method, but it is easier to remove the shielding layer on the photosensitive resin layer. A so-called negative photosensitive resin is preferable. Moreover, as a shielding part, it can be made to be the same as that of metal shielding parts, such as chromium, nickel, gold | metal | money, silver, copper, aluminum, generally formed by a vacuum evaporation method, a sputtering method, etc.

  The film thickness of the shielding part formed by the lift-off method can usually be about 0.01 μm to 10 μm, especially about 0.01 μm to 1 μm.

  Here, in the present invention, when the film thickness of the shielding portion as described above is exposed using the exposure mask of the present invention, the gap provided between the opposing property change layer or the like and the exposure mask. You may make it correspond with the width. This is because the shielding portion can be used as a spacer. In addition, by irradiating energy from the exposure mask side, for example, with the characteristic change layer and the exposure mask shielding part in close contact with each other without diffusing active oxygen species generated from the photocatalyst-containing layer. This is because it is possible to reach the characteristic change layer and the like, and it is possible to efficiently form a pattern whose characteristic has changed.

4). Next, the base material used for the exposure mask of the present invention will be described. The base material used for this invention is suitably selected by the irradiation direction of the energy irradiated when exposing using an exposure mask, whether the irradiation target has transparency, etc.

  The base material used in the present invention may be a flexible material such as a resin film, or may be a non-flexible material such as a glass substrate.

  In addition, in order to improve the adhesiveness of the base material surface and the said photocatalyst content layer, you may make it form an anchor layer on a base material. Examples of such an anchor layer include silane-based and titanium-based coupling agents.

5). Next, the exposure mask of the present invention will be described. The exposure mask of the present invention is not particularly limited as long as it has the above-described base material, photocatalyst-containing layer, inorganic oxide layer, and shielding part.

  As described above, the exposure mask of the present invention is used in opposition to a property change layer containing an organic group that is decomposed or modified by the action of a photocatalyst associated with energy irradiation. The exposure mask is arranged and used in a state where the action of the photocatalyst substantially reaches the surface of the property change layer or the like. In this case, in addition to the actual physical contact, it is preferably arranged at a predetermined interval, and when arranged with a gap, it is preferably 200 μm or less.

  In the present invention, such a gap has a very good pattern accuracy, a high photocatalyst sensitivity, and therefore a good characteristic change efficiency such as a characteristic change layer, so that it is particularly within the range of 0.2 μm to 10 μm. The thickness is preferably in the range of 1 μm to 5 μm. Such a range of the gap is particularly effective for a characteristic change layer having a small area that can control the gap with high accuracy.

  On the other hand, when processing is performed on a characteristic change layer having a large area of, for example, 300 mm × 300 mm or more, a fine gap as described above is formed between the exposure mask and the characteristic change layer without contact. It is extremely difficult to form. Therefore, when the characteristic change layer or the like has a relatively large area, the gap is preferably in the range of 10 to 100 μm, particularly in the range of 50 to 75 μm. By setting the gap within such a range, there is no problem of pattern accuracy deterioration such as blurring of the pattern or problems such as deterioration of photocatalyst sensitivity and deterioration of efficiency of characteristic change. This is because there is an effect that non-uniformity does not occur in the characteristic change on the layer.

  As described above, when the exposure mask of the present invention is used when exposing a characteristic change layer having a relatively large area, the gap in the positioning device between the exposure mask and the characteristic change layer in the energy irradiation apparatus is used. Is preferably set in the range of 10 μm to 200 μm, particularly in the range of 25 μm to 75 μm. By setting the set value within such a range, the pattern accuracy and the photocatalyst sensitivity will not be greatly deteriorated, and the exposure mask and the characteristic change layer will not be in contact with each other. This is because it becomes possible.

  Thus, by arranging the exposure mask and the surface of the characteristic change layer and the like at a predetermined interval, oxygen, water, and active oxygen species generated by photocatalysis can be easily desorbed. That is, when the distance between the exposure mask and the characteristic change layer is made narrower than the above range, it is difficult to desorb the active oxygen species, and as a result, the characteristic change rate may be slowed down. It is not preferable. In addition, it is not preferable that the active oxygen species generated are difficult to reach the characteristic change layer, and in this case as well, the speed of the characteristic change may be reduced.

  Such an arrangement state only needs to be maintained at least during the energy irradiation.

  Examples of a method for uniformly forming such an extremely narrow gap and arranging the exposure mask and the characteristic change layer include a method using a shielding portion as a spacer as described above.

B. Next, a method for manufacturing an exposure mask according to the present invention will be described. The exposure mask manufacturing method of the present invention has two embodiments. Hereinafter, each embodiment will be described in detail.

1. First Embodiment First, the first embodiment of the exposure mask manufacturing method of the present invention will be described. The method for producing an exposure mask according to this embodiment includes a photocatalyst-containing layer forming step of forming a photocatalyst-containing layer containing at least a photocatalyst on a substrate, and an inorganic oxide layer forming an inorganic oxide layer on the photocatalyst-containing layer. It has an oxide layer formation process and the shielding part formation process which forms a shielding part on the said inorganic oxide layer, It is characterized by the above-mentioned.

  For example, as shown in FIG. 4, the exposure mask manufacturing method of the present embodiment includes a photocatalyst-containing layer forming step (FIG. 4A) for forming a photocatalyst-containing layer 2 on a substrate 1, and the photocatalyst-containing layer. Inorganic oxide layer forming step (FIG. 4B) for forming inorganic oxide layer 3 on 2 and shielding portion forming step for forming shielding portion 4 in a pattern on inorganic oxide layer 3 (FIG. 4). (C)).

  According to the present embodiment, since the inorganic oxide forming step of forming the inorganic oxide layer on the photocatalyst-containing layer is included, when performing exposure using the exposure mask manufactured according to the present embodiment, for example, Even if the shielding part is made of a metal or the like, carriers generated from the photocatalyst containing layer can be prevented from flowing to the shielding part. Therefore, the active oxygen species can be efficiently generated by this carrier.

Further, according to this embodiment, since the shielding portion is formed on the inorganic oxide layer, the active oxygen species generated by the excitation of the photocatalyst is shielded in the region where the shielding portion is formed. It is shielded by the part and cannot come out on the surface. Therefore, in this region, it is possible to form a pattern with changed characteristics at a high resolution without changing the characteristics of the characteristic change layers and the like arranged opposite to each other. At this time, it is also possible to use the shielding part as a spacer between the exposure mask and the characteristic change layer. In this case, the active oxygen species generated in the region where the shielding part is not formed does not diffuse, Since it is possible to reach the change layer or the like, it is possible to form a pattern whose characteristics are changed with higher resolution.
Hereinafter, each process of this embodiment will be described in detail.

(1) Photocatalyst containing layer formation process First, the photocatalyst content layer forming process in this embodiment is demonstrated. The photocatalyst containing layer forming step in this embodiment is a step of forming a photocatalyst containing layer containing at least a photocatalyst on the substrate. The photocatalyst-containing layer formed by this step may be composed of a photocatalyst and a binder, or may be formed from a photocatalyst alone.

  Examples of a method for forming a photocatalyst-containing layer composed only of a photocatalyst include a method using a vacuum film forming method such as a sputtering method, a CVD method, or a vacuum deposition method. Examples of a method for forming a photocatalyst-containing layer consisting of only a photocatalyst include a method in which amorphous titania is formed on a substrate and then phase-changed to crystalline titania by firing when the photocatalyst is titanium dioxide. .

  For example, when the photocatalyst-containing layer is composed of a photocatalyst and a binder, a photocatalyst and a binder are dispersed in a solvent to prepare a coating solution, and this coating solution is applied onto a substrate. Can be formed. The application can be performed by a known application method such as spin coating, spray coating, dip coating, roll coating, or bead coating. When an ultraviolet curable component is contained as a binder, the photocatalyst-containing layer can be formed by irradiating with ultraviolet rays and performing a curing treatment.

  Here, as the base material, photocatalyst, and various binder materials used in this step, the same materials as those described in the above-mentioned “A. Exposure mask” can be used. Detailed description is omitted.

(2) Inorganic oxide layer formation process Next, the inorganic oxide layer formation process in this embodiment is demonstrated. The inorganic oxide layer forming step in the present embodiment is a step of forming an inorganic oxide layer on the photocatalyst-containing layer, and any method that can form an inorganic oxide layer on the photocatalyst-containing layer. There is no particular limitation. At this time, it is preferable that the inorganic oxide layer to be formed does not have conductivity. This is because when the inorganic oxide has conductivity, carriers generated from the photocatalyst containing layer by energy irradiation flow through the inorganic oxide layer, making it difficult to efficiently generate active oxygen species. Moreover, in this embodiment, it is preferable that the said inorganic oxide layer is what permeate | transmits the carrier generate | occur | produced from the photocatalyst content layer by energy irradiation, an active oxygen species, etc. This is because when the inorganic oxide layer does not allow these active oxygen species to permeate, it is difficult to efficiently change the characteristics of the characteristic change layer and the like.

  As a method for forming such an inorganic oxide layer, for example, a vacuum film forming method such as a sputtering method, a CVD method, a vacuum deposition method, a sol-gel method, or the like can be used. Since it can be the same as that described in the section of the inorganic oxide layer, detailed description thereof is omitted here.

  At this time, the thickness of the inorganic oxide layer is preferably about 0.005 μm to 1 μm, more preferably about 0.01 μm to 0.2 μm. If it is thicker than the above film thickness, it may be difficult to transmit active oxygen species generated from the photocatalyst-containing layer, and if it is thinner than the above film thickness, the inorganic oxide layer is non-conductive. This is because the effect as a protective layer cannot be exhibited, and carriers generated in the photocatalyst containing layer may flow to the shielding part or the like.

(3) Shield part formation process Next, the shield part formation process in this embodiment is explained. This step is not particularly limited as long as it is a step of forming a shielding part on the inorganic oxide layer.

  As long as the shielding part formed in this step is not decomposed by the action of the photocatalyst of the photocatalyst containing layer, the type and formation method thereof are not particularly limited, and the characteristics of the formation surface of the shielding part and These are appropriately selected and used depending on the shielding properties against the required energy.

  This step includes, for example, a step of forming a layer containing shielding fine particles in a resin binder in a pattern, a step of forming a shielding portion having a shielding material and a binder, for example, by a thermal transfer method, and the like. Also good.

  Here, in this embodiment, it is particularly preferable that the shielding portion is not decomposed by the action of the photocatalyst accompanying energy irradiation, and is preferably a layer made of an inorganic material such as a metal material. Thereby, the exposure mask manufactured according to the present invention can be repeatedly used, and the pattern can be stably formed.

  In this step, as a method for forming a layer made of such an inorganic material, for example, a method of forming a metal thin film such as chromium having a thickness of about 1000 to 2000 mm by sputtering, vacuum deposition or the like and patterning the thin film is used. However, it is preferable to use a method of forming a shielding portion made of metal or the like, particularly by a lift-off method. According to this method, it is possible to prevent a metal such as chromium used as the shielding portion from contacting the inorganic oxide layer in the region where the shielding portion is not formed. In addition, it is not necessary to use a developer containing a metal for dissolving a metal used in a general photolithography method and the like, so that the metal does not adhere to the inorganic oxide layer. it can. Therefore, it is possible to manufacture an exposure mask that can efficiently perform pattern formation and the like without reducing the sensitivity of the photocatalyst.

  The film thickness of the shielding part formed by the lift-off method can usually be about 0.01 μm to 10 μm, especially about 0.01 μm to 1 μm.

  The material used in this step, the method for forming various shielding portions, and the like can be the same as those described in the section of the shielding portion of “A. Exposure mask” described above. Detailed description is omitted.

2. Second Embodiment Next, a second embodiment of the method for manufacturing an exposure mask according to the present invention will be described. In the second embodiment of the method for producing an exposure mask of the present invention, a photocatalyst-containing layer forming step of forming a photocatalyst-containing layer containing at least a photocatalyst on a substrate, and a shield on the photocatalyst-containing layer by a lift-off method And a shielding part forming step for forming the part.

  For example, as shown in FIG. 5, the exposure mask manufacturing method of the present embodiment includes a photocatalyst-containing layer forming step (FIG. 5A) for forming a photocatalyst-containing layer 2 on a substrate 1, and the photocatalyst-containing layer. 2 and a shielding part forming step (FIG. 5B) for forming the shielding part 4 by a lift-off method.

  According to this embodiment, since the shielding part is formed by the lift-off method, the material for forming the shielding part cannot be in contact with the photocatalyst containing layer in the region where the shielding part is not formed. Moreover, since what does not contain a metal etc. can be used as a developing solution, a metal etc. cannot adhere on a photocatalyst content layer. Therefore, it is possible to manufacture an exposure mask capable of efficiently performing pattern formation without reducing the sensitivity of the photocatalyst due to impurities or the like adhering to the photocatalyst-containing layer.

  Hereafter, the shielding part formation process in this embodiment is demonstrated in detail. In addition, about the photocatalyst containing layer formation process in this embodiment, since it is the same as that of the 1st embodiment mentioned above, detailed description here is abbreviate | omitted.

(Shield part forming process)
The shielding part formation process in this embodiment is not particularly limited as long as it is a process of forming a shielding part on the photocatalyst-containing layer by a lift-off method. As a method for forming such a shielding portion, for example, a photosensitive resin layer is applied over the entire surface of the photocatalyst-containing layer, exposed using a photomask or the like, and photosensitive resin is applied only to a region where the shielding portion is not formed. Form a layer. Thereafter, a shielding layer made of chromium or the like is formed on the photocatalyst-containing layer in which the photosensitive resin layer is formed in a pattern, for example, by vapor deposition or the like, and is formed on the photosensitive resin layer and the photosensitive resin layer. By removing the shielding layer, the shielding part can be formed only in the target region.

  Here, the material for forming the shielding portion used in this step, the photosensitive resin, and the like can be the same as those in the above-described “A. Exposure mask”, and thus detailed description thereof is omitted here.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

  The following examples illustrate the present invention more specifically.

[Example 1]
<Production of exposure mask>
A titania sol (STS-01 manufactured by Ishihara Sangyo) is diluted with a mixed solution of water and isopropanol (weight ratio = 1: 1) so that the TiO ₂ concentration becomes 0.5 wt%, and a composition for forming a photocatalyst containing layer It was. The photocatalyst-containing layer forming composition was spin-coated on a quartz glass substrate and baked at 200 ° C. for 15 minutes to produce a photocatalyst-containing layer.
On the photocatalyst-containing layer, PMER-LA900 (manufactured by Tokyo Ohka Kogyo Co., Ltd.), which is a positive photosensitive resin, was spin-coated and baked at 100 ° C. for 5 minutes. This positive photosensitive resin is exposed to 300 mJ / cm ² with an ultrahigh pressure mercury lamp through a photomask having a black and black light-shielding layer with a line and space of 50 μm width and 100 μm pitch, and the developer is exposed for 3 minutes. A patterned photosensitive resin layer was produced by dipping.
Subsequently, after covering the photosensitive resin and the photocatalyst-containing layer with a Cr film having a thickness of 1000 mm by sputtering, the photosensitive resin layer and the Cr layer formed thereon were immersed in a resist stripping solution. Peeling was performed, and an exposure mask having a Cr shielding portion formed in a line-and-space shape with a width of 100 μm and a pitch of 50 μm was produced.

<Preparation of substrate for pattern formation>
Fluoroalkylsilane (TSL8233 GE manufactured by Toshiba Silicone) 1.5 g, tetramethoxysilane (TSL8114 GE manufactured by Toshiba Silicone) 5.0 g, and 0.01 N hydrochloric acid 2.5 g were stirred at room temperature for 24 hours to give a liquid repellent imparting agent. Produced. The liquid repellent imparting agent was diluted 20 times with isopropyl alcohol to prepare a composition for forming a characteristic change layer. A substrate for patterning formation was prepared by spin-coating the composition for forming a characteristic change layer on a glass substrate (NA-35 NH Techno Glass).

<Pattern formation>
The characteristic changing layer of the patterning substrate and the photocatalyst containing layer of the exposure mask are arranged at an interval of 50 μm, and the integrated exposure is 2.5 J / cm ² from the exposure mask side by an ultrahigh pressure mercury lamp. Exposure was performed by irradiating with light. As a result of applying black ink to the entire surface of the patterning substrate that has been exposed and visualizing the areas where wettability has changed due to the exposure described above, the width of the ink adhering, that is, the width of the area where wettability has changed due to exposure is It was 50 μm. As a result, it was confirmed that the wettability of the characteristic change layer was changed to the same pattern as the pattern of the opening of the exposure mask.

[Example 2]
<Formation of exposure mask>
The photocatalyst-containing layer forming composition produced in the same manner as in Example 1 was spin-coated on a quartz glass substrate and baked at 200 ° C. for 15 minutes to form a photocatalyst-containing layer.
Inorganic oxidation by stirring 1.5 g of decylmethoxysilane (LS-5280 manufactured by Shin-Etsu Chemical Co., Ltd.), 5.0 g of tetramethoxysilane (manufactured by TSL8114 GE Toshiba Silicone), and 2.5 g of 0.01N hydrochloric acid at room temperature for 24 hours. A material layer forming agent was prepared. The inorganic oxide layer forming agent was diluted 20 times with isopropyl alcohol to prepare an inorganic oxide layer forming composition. The inorganic oxide layer-forming composition was spin-coated on the photocatalyst-containing layer and baked at 200 ° C. for 15 minutes to form an inorganic oxide layer on the photocatalyst-containing layer.
Thereafter, a shielding part was formed in the same manner as in Example 1 to produce an exposure mask.

<Pattern formation>
As a result of exposure and visualization of the exposure pattern using the above exposure mask in the same manner as in Example 1, the width of the obtained black ink was 50 μm, and the same pattern as the pattern of the opening of the exposure mask It was confirmed that the wettability of the characteristic change layer was changed in the shape.

[Example 3]
Similar to Example 2, a photocatalyst-containing layer and an inorganic oxide layer were formed on a quartz glass substrate. Subsequently, 1000 nm of Cr was formed on the inorganic oxide layer by sputtering to form a shielding layer. A line-and-space pattern photosensitive resin layer having a width of 50 μm and a pitch of 100 μm was produced on the shielding layer in the same manner as in Example 1. Then, Cr of the area | region in which the photosensitive resin layer was not formed was removed by being immersed in Cr etching liquid. Thereafter, the photosensitive resin layer was peeled off by dipping in a resist stripping solution, and an exposure mask having a Cr shielding layer in a line-and-space pattern with a width of 50 μm and a pitch of 100 μm was prepared.
As in Example 1, when the characteristic change layer of the patterning substrate and the exposure mask are arranged to face each other, exposure is performed, and the exposure pattern is visualized, the integrated exposure amount is 2.5 J / cm ² . The width of the black ink was 20 μm, but when the integrated exposure was 6 J / cm ² , the ink width was 50 μm, and the wettability of the characteristic change layer changed to the same pattern as the pattern of the opening of the exposure mask. Was confirmed.

[Comparative Example 1]
An exposure mask was produced in the same manner as in Example 3 except that the inorganic oxide layer was not formed. Performing the same exposure as in Example 1 was subjected to a visualization of the exposure pattern, the integrated exposure amount can not pattern formation ink at 6J / cm ^2, the ink also increases the accumulated exposure to 18J / cm ² The width of the film was 10 μm, and the wettability of the characteristic change layer could only be changed to a pattern different from the pattern of the exposure mask.

It is a schematic sectional drawing which shows an example of the mask for exposure of this invention. It is explanatory drawing explaining the usage method of the mask for exposure of this invention. It is process drawing explaining the lift-off method used for this invention. It is process drawing which shows an example of the manufacturing method of the mask for exposure of this invention. It is process drawing which shows the other example of the manufacturing method of the mask for exposure of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... Photocatalyst content layer 3 ... Inorganic oxide layer 4 ... Shielding part

Claims (4)

  A substrate, a photocatalyst-containing layer formed on the substrate and containing at least a photocatalyst, an inorganic oxide layer formed on the photocatalyst-containing layer, and formed in a pattern on the inorganic oxide layer An exposure mask comprising a shielding portion. A photocatalyst-containing layer forming step of forming a photocatalyst-containing layer containing at least a photocatalyst on the substrate;
An inorganic oxide layer forming step of forming an inorganic oxide layer on the photocatalyst-containing layer;
And a shielding portion forming step of forming a shielding portion on the inorganic oxide layer.   3. The method of manufacturing an exposure mask according to claim 2, wherein the shielding portion forming step is a step of forming a shielding portion by a lift-off method. A photocatalyst-containing layer forming step of forming a photocatalyst-containing layer containing at least a photocatalyst on the substrate;
And a shielding portion forming step of forming a shielding portion on the photocatalyst-containing layer by a lift-off method.

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