JP2014202915A - Patterned substrate and production method of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a patterned substrate and a production method of the substrate that can exhibit sufficient adhesiveness to resins when a resin layer is disposed on a fine pattern of the substrate.SOLUTION: The patterned substrate includes a substrate (11) and a thermo-reactive resist layer (12) disposed on the substrate (11), which comprises a thermo-reactive resist material and has a pattern including projections (12b) and recesses (12c). The thermo-reactive resist layer (12) has a granular material (13) containing at least the above thermo-reactive resist material in the recesses (12c).

Description

  The present invention relates to a patterned substrate having a fine relief structure and a method for producing the same.

  In recent years, as the demand for higher density and higher integration in the fields of semiconductors, optical / magnetic recording, etc., fine pattern processing technology of several hundred nm to several tens of nm or less is indispensable. Therefore, in order to realize such fine pattern processing, elemental technologies of each process such as a mask / stepper, exposure, resist material and the like are actively studied.

  Although many studies have been made on resist materials, at present, the most common resist materials are photoreactive organic resists (hereinafter also referred to as photoresists) that react with exposure light sources such as ultraviolet light, electron beams, and X-rays. (See Patent Document 1 and Non-Patent Document 1).

In the laser beam used for exposure, the intensity of the laser beam focused by a lens usually shows a Gaussian distribution shape as shown in FIG. At this time, the spot diameter is defined as 1 / e ² . In general, a photoresist reaction is initiated by absorbing energy represented by E = hν (E: energy, h: Planck constant, ν: wavelength). Therefore, the reaction does not strongly depend on the intensity of light, but rather depends on the wavelength of the light, so that almost all reaction occurs in the portion irradiated with light (exposed portion). For this reason, when a photoresist is used, exposure is performed faithfully to the spot diameter.

  Although a method using a photoreactive organic resist is a very effective method for forming a fine pattern of about several hundreds of nanometers, a finer pattern is formed because a photoreactive photoresist is used. Therefore, it is necessary to perform exposure with a spot smaller than the pattern required in principle. Therefore, a KrF or ArF laser having a short wavelength must be used as the exposure light source. However, since these light source devices are very large and expensive, they are not suitable from the viewpoint of manufacturing cost reduction. Furthermore, when an exposure light source such as an electron beam or X-ray is used, the exposure atmosphere needs to be in a vacuum state, so a vacuum chamber is used, and there are considerable limitations from the viewpoints of cost and size.

  On the other hand, when an object is irradiated with laser light having a distribution as shown in FIG. 1, the temperature of the object also exhibits the same Gaussian distribution as the intensity distribution of the laser light. At this time, if a resist that reacts at a certain temperature or higher, that is, a heat-reactive resist is used, the reaction proceeds only at a portion that exceeds a predetermined temperature as shown in FIG. It becomes. That is, a pattern finer than the spot diameter can be formed without reducing the wavelength of the exposure light source. Therefore, the influence of the exposure light source wavelength can be reduced by using the heat-reactive resist.

  So far, techniques for forming a fine pattern by exposure using a semiconductor laser or the like and heat / photoreaction using a metal oxide as a heat-reactive resist have been reported (hereinafter, Patent Documents 2 to 4, Non-Patent Document 2). reference). Such metal oxides can change the degree of oxidation by heating due to exposure, and a fine pattern can be formed by developing a difference in solubility in a developing solution based on the difference in degree of oxidation.

JP 2007-144959 A Japanese Patent No. 4055543 Japanese Patent No. 4986137 Japanese Patent No. 4986138

Published by Information Organization Co., Ltd. “Latest Resist Materials” P.59-P.76 The 19th Symposium on Phase Change Optical Information Storage 2007 Proceedings P.77-P.80

  On the other hand, there is a technique for forming a fine pattern on a base material by forming a resist layer on the base material, patterning the resist layer, and then etching the base material using the resist layer remaining on the base material as a mask. The base material thus produced is used as a transfer base material for transferring the fine pattern to the resin layer by providing a resin layer on the surface on which the fine pattern is formed.

  Even if a fine pattern is formed on the substrate as described above using either a photoreactive resist or a heat-reactive resist, if this substrate is used as a substrate for transfer, sufficient for the resin layer There is a problem that the resin or the like is peeled off without obtaining an adhesive force.

  This invention is made | formed in view of this point, and when providing the resin layer in the fine pattern of a base material, providing the base material with a pattern which can exhibit sufficient adhesiveness with respect to resin, and its manufacturing method are provided. Objective.

  The patterned base material of the present invention comprises a base material, and a heat-reactive resist layer which is provided on the base material and is made of a heat-reactive resist material and has a pattern including a convex portion and a concave portion. The heat-reactive resist layer has a granular material containing at least the heat-reactive resist material in the recess.

  In the patterned substrate of the present invention, it is preferable that the granular material is obtained by changing the quality of the heat-reactive resist material when heat is applied to the heat-reactive resist layer.

  In the patterned substrate of the present invention, it is preferable that the average particle diameter of the granular material is 1 nm or more and 1000 nm or less.

  In the base material with a pattern of this invention, it is preferable that the height difference from the bottom part of the said recessed part in the said pattern to the top part of the said convex part is 5 nm or more and 10,000 nm or less.

  In the base material with a pattern of this invention, it is preferable that the said granular material contains a metal element at least.

  In the substrate with a pattern of the present invention, it is preferable that the pattern has a substantially lattice shape or a substantially dot shape in plan view.

  The transfer substrate of the present invention is characterized by etching the substrate using the pattern in the patterned substrate as a mask.

  The method for producing a patterned substrate of the present invention includes a step of forming a thermal reaction type resist layer composed of a thermal reaction type resist material on a substrate, and partially applying heat to the thermal reaction type resist layer. A pattern including a step of modifying the thermally reactive resist material, and removing at least a part of the modified thermal reactive resist layer to include a convex portion and a concave portion having a granular material including at least the thermal reactive resist material. And a step of forming.

  In the method for producing a patterned substrate of the present invention, it is preferable that the heat-reactive resist material is altered by partially applying heat to the heat-reactive resist layer by exposure using a laser.

  In the method for producing a patterned substrate of the present invention, the thermal reaction type resist material is silicon, aluminum, titanium, gallium, tantalum, cobalt, or an oxide thereof with respect to 100% by volume of the thermal reaction type resist material. Or it is preferable to contain a nitride by 80 volume% or less.

  The transfer substrate manufacturing method of the present invention is characterized in that the substrate is etched using the pattern in the patterned substrate obtained by the patterned substrate manufacturing method as a mask.

  According to the present invention, the surface area of the recesses increases due to the particulates present in the recesses of the pattern. Thereby, when providing the resin layer in the fine pattern of a base material, sufficient adhesiveness with respect to resin can be exhibited.

It is the figure which showed intensity distribution of the laser beam. It is the figure which showed the temperature distribution of the part irradiated with the laser beam. It is a figure which shows typically an example of the base material with a pattern of this invention. It is a figure which shows an example of the manufacturing method of the base material with a pattern of this invention.

  Hereinafter, an embodiment of the present invention (hereinafter abbreviated as “embodiment”) will be described in detail with reference to the accompanying drawings. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

FIG. 3A is a diagram schematically showing an example of a patterned substrate of the present invention.
As shown in FIG. 3A, the patterned substrate is mainly composed of a substrate 11 and a heat-reactive resist layer 12 provided on the substrate and made of a heat-reactive resist material. Yes. The heat-reactive resist layer 12 has a pattern including convex portions 12b and concave portions 12c. The heat-reactive resist layer 12 has a granular material 13 containing at least a heat-reactive resist material in the recess 12c.

  The material constituting the substrate 11 is preferably a material excellent in surface smoothness and workability, and examples thereof include glass, silicon, silicon dioxide, aluminum, titanium, copper, silver, and gold. Among these, Glass, silicon, silicon dioxide, aluminum, titanium and copper are particularly preferred.

  As the base material 11, a flat base material, a cylindrical base material (a sleeve base material, a roll base material, a drum base material), a lens-like base material, or the like can be used. By using these base materials, the shape of the base material can be used as it is as the shape of the mold. The shape of the substrate can be selected as appropriate according to the shape of the mold to be produced.

  The heat-reactive resist material constituting the heat-reactive resist layer 12 is molybdenum, tungsten, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, niobium, rhodium, silver, hafnium, tantalum, gold And oxides such as platinum, aluminum, zinc, gallium, indium, tin, antimony, lead, and bismuth. Among these, from the viewpoint of high selectivity during wet etching, oxides such as molybdenum, tungsten, titanium, vanadium, chromium, manganese, cobalt, nickel, copper, silver, tantalum, platinum, and lead are preferable. In terms of easy control of the crystal grain size, oxides such as molybdenum, tungsten, chromium, and copper are more preferable.

  In the pattern including the convex part 12b and the concave part 12c, the height difference (depth H) from the bottom part of the concave part 12c to the top part of the convex part 12b is preferably 5 nm or more and 10,000 nm or less. Further, the pattern may have a substantially lattice shape in plan view as shown in FIG. 3B, or may have a substantially dot shape as shown in FIG. 3C. In the substantially dot-shaped pattern, the recess 12c may be formed in a substantially dot shape.

  The recess 12c in the pattern may be in a state where the base material 11 is exposed through the thermal reaction type resist layer 12, or may be in a state where it does not penetrate through the thermal reaction type resist layer 12. Therefore, the bottom surface of the recess 12c may be made of a heat-reactive resist material, may be made of the material of the base material 11, or made of a heat-reactive resist material and the material of the base material 11. Also good. Therefore, the state in which the particulate matter 13 remains on the bottom surface of the recess 12c is a state in which the particulate matter 13 is present on the base material 11 and a state in which the particulate matter 13 is present on the thermal reaction type resist layer 12. And a state in which these states are mixed.

  The granular material 13 containing at least the heat-reactive resist material remains in the recesses 12 c of the pattern provided in the heat-reactive resist layer 12. The granular material 13 remains on the bottom surface and / or the side surface of the recess 12c. Here, the shape of the granular material 13 includes not only a true sphere shape but also a shape in which a true sphere is distorted such as a water droplet shape or a shape having a top portion such as a spine shape.

  The granular material 13 is obtained by changing the quality of the heat-reactive resist material when heat is applied to the heat-reactive resist layer 12. The heat-reactive resist material changes in quality when it is heated above a certain temperature, and the degree of oxidation changes. At this time, by heating at a temperature within a certain range, a part of the crystals become granular crystals. The part which became a granular crystal | crystallization reduces the solubility with respect to an etching liquid compared with the other quality-changed part from which the oxidation degree changed by heating. That is, it is possible to selectively dissolve and remove other altered portions while leaving only granular crystals. Thus, when the pattern which has the convex part 12b and the recessed part 12c is formed in the thermal reaction type resist layer 12, a granular material (granular protrusion) will remain in the side surface and / or bottom face of the recessed part 12c. This is the granular material 13. Therefore, the granular material 13 contains at least a metal element.

  The particle size of the granular material 13 can be any value as long as the uneven pattern shape is not significantly deformed, but is preferably 1 nm or more and 1000 nm or less. The particle size of the granular material 13 is preferably an average particle size of 1000 nm or less, more preferably 200 nm or less, still more preferably 100 nm or less, and most preferably 50 nm or less in consideration of the size of the uneven pattern shape formed of the heat-reactive resist material. preferable. In addition, the particle size of the granular material 13 is desirably a certain size or more in consideration of resist performance when the thermally-reactive resist layer 12 of the substrate with this pattern is used as a mask for dry etching. 1 nm or more is desirable, 5 nm or more is more desirable, and 10 nm or more is further desirable. These upper and lower limits of particle size can be arbitrarily combined. The particle size refers to the smallest true sphere diameter in which each granular material is included.

  In order to control the particle size of the granular material 13, it is effective to add an additive to the metal oxide. Examples of such additives include silicon, aluminum, titanium, gallium, tantalum, cobalt, and oxides and nitrides thereof. Among them, silicon and aluminum are preferable because of their high effects. When these additives are used, crystallization of the metal oxide that is a heat-reactive resist material can be suppressed, which is useful for controlling the crystal grain size. The amount of such an additive can be arbitrarily set depending on the degree to which crystallization is desired to be suppressed. However, in order to maintain the material performance as a heat-reactive resist, the main component is 100% by volume of metal oxide. On the other hand, it is preferably 80% by volume or less, more preferably 50% by volume or less, particularly preferably 20% by volume or less, and most preferably 10% by volume or less.

  Since the substrate with a pattern having such a configuration has an increased surface area due to the presence of the particulate matter as compared with the conventional substrate, the adhesion of the resins filled in the pattern can be improved.

  Further, such a patterned substrate can be used as a transfer substrate by etching the substrate using this pattern as a mask. As for the transfer substrate thus obtained, the pattern formed on the substrate is distorted by the particulate matter remaining in the heat-reactive resist pattern, the surface area of the pattern is increased, and the resins filled in the pattern It is possible to improve the adhesion.

  In the method for producing a patterned substrate of the present invention, a step (1) of forming a thermal reaction type resist layer composed of a thermal reaction type resist material on the substrate, and a part of the thermal reaction type resist layer are heated. (2) for altering the heat-reactive resist material by applying at least one part, and removing the heat-reactive resist layer that has been denatured at least partly, and having a convex part and a granular material containing at least the heat-reactive resist material And (3) forming a pattern including

  FIG. 4 is a diagram showing an example of a method for producing a patterned substrate of the present invention. In step (1) in the method for producing a patterned base material of the present invention, a heat-reactive resist layer made of a heat-reactive resist material is formed on the base material 11 shown in FIG. 4A (FIG. 4B). The heat-reactive resist layer 12 can be formed using a sputtering method, a vapor deposition method, or a CVD method. Since these layers can be processed with fine patterns on the order of several tens of nanometers, depending on the fine pattern size, the film thickness distribution of the heat-reactive resist during film formation and surface irregularities may have a significant effect. It is done. Therefore, in order to reduce these effects as much as possible, film formation methods such as sputtering, vapor deposition, and CVD are more difficult than film formation methods such as coating methods and spray methods that are somewhat difficult to control film thickness uniformity. It is preferable to form a heat-reactive resist layer. Among these, the sputtering method is particularly preferable from the viewpoints of composition adjustment, film thickness uniformity, film formation rate, and the like.

  In the step (2), the heat-reactive resist layer 12 is partially altered by applying heat to the heat-reactive resist layer 12. As a result, as shown in FIG. 4C, an altered portion 12a and an unaltered portion are generated. For example, heat is partially applied to the heat-reactive resist layer 12 by exposure using a laser to alter the heat-reactive resist material. As described above, when the heat-reactive resist layer 12 is exposed, an exposed portion (corresponding to the altered portion) and an unexposed portion are generated.

  In the step (2), when the heat-reactive resist material is denatured by heating, a part thereof becomes granular crystals and appears as a granular material 13 in the denatured portion 12a. The granular material 13 has a lower solubility in the etching solution than other altered portions (amorphous regions) whose degree of oxidation has changed by heating.

  The method of heating the heat-reactive resist material is arbitrary, but in the case of forming a submicron order fine pattern, a laser is generally used. The type of laser may be determined according to the desired pattern size or the like, but a semiconductor laser is preferable in view of the simplicity and cost of introducing the apparatus. When a finer pattern is formed, it is preferable to select a laser having a sharp heat distribution when the laser is irradiated.

  In order to control the density of the granular material 13 (the number of granular materials present), it is effective to control the temperature at which the heat-reactive resist material is heated. Specific temperature conditions are appropriately set depending on the type of metal oxide and substrate used. In general, most of the granular material is generated near the critical temperature at which the heat-reactive resist material changes in quality, and when the temperature exceeds the critical temperature, the generation of the granular material decreases. Therefore, it is preferable to appropriately set the heating temperature of the heat-reactive resist material so that the granular material 13 has a desired density. The critical temperature at which the heat-reactive resist material changes in quality can be estimated by the following method. When differential thermogravimetric analysis (TG-DTA) of a metal oxide used as a heat-reactive resist material is performed, a rapid decrease in weight is observed as decomposition proceeds at a specific temperature. This specific temperature is the critical temperature. For example, when the metal oxide is copper oxide, the critical temperature is 1100 ° C., and particulate matter is observed between this critical temperature and + 500 ° C.

  In the step (3), at least a part of the altered thermal reaction type resist layer 12 is removed to form a pattern including the convex part 12b and the concave part 12c having the granular material 13 containing at least the thermal reaction type resist material. As a method for forming the pattern (concave / convex pattern) including the convex portion 12b and the concave portion 12c having the granular material 13 containing at least the thermal reaction type resist material on the thermal reaction type resist layer 12, the following method may be considered. .

  As a first method, a heat-reactive resist layer 12 is provided in a known method, and a concavo-convex pattern is formed on the heat-reactive resist layer. There is a method of fixing the reactive resist layer 12 and the granular material 13 by dissolving / re-solidifying them. In this method, if the granular material 13 is unnecessary in the region other than the recess 12c depending on the application, the granular material may be removed by wiping the surface or air blowing after filling the granular material. In this method, the component constituting the heat-reactive resist layer 12 and the component constituting the granular material 13 may be greatly different. However, since the granular material 13 needs to be fixed, the process becomes complicated. This limits the materials that can be used.

  As a second method, there is a method in which a metal oxide that can be used as a positive-type heat-reactive resist material is used and a concavo-convex pattern is formed under the conditions that the granular material 13 is generated. In this method, since the granular material 13 is fixed to the heat-reactive resist layer 12 in advance, the process is simpler than that of the first method, and materials that can be used as much as dissolution / refixing is unnecessary are not limited. Therefore, it is more preferable.

  When removing the altered thermal reaction type resist layer, the altered thermal reaction type resist layer is dissolved using a wet etching solution (FIG. 4D). Thus, the recesses 12c of the thermal reaction type resist layer 12 have the granular material 13 containing at least the thermal reaction type resist material (bottom surface and side surface).

  The wet etching solution to be used is a heat-reactive resist in which the solubility of a portion other than the granular material 13 (a portion other than the granular material 13 in the altered portion 12a) of the heat-reactive resist altered by heat is not affected by heat. As long as it is higher than the (unmodified part) and the granular material 13, that is, as long as it can selectively dissolve the portion other than the granular material 13 in the heat-reactive resist modified by heat, use arbitrarily. Can do. Effective wet etching solution components, concentrations, and temperature conditions can be set as appropriate according to the materials used. In general, an acid, an alkali, or a chelating agent is used as the wet etching solution, and these may be used as a single component or may be used as a mixture. Moreover, you may add an electric potential regulator, surfactant, etc. to these as needed.

  Specific examples of the acid that can be used in the wet etching solution include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, phosphoric acid, trifluoromethanesulfonic acid, trifluoroacetic acid, and hydrofluoric acid. Examples of the alkali that can be used in the wet etching solution include sodium hydroxide, potassium hydroxide, ammonia, and tetramethylammonium hydroxide. Chelating agents that can be used in the wet etching solution include alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, ornithine, phenylalanine, serine, threonine, tryptophan. , Tyrosine, valine, proline, oxalic acid, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylethylenediaminediacetic acid, 1,3-propanediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,2-diamino Propanetetraacetic acid, ethylenediamine disuccinic acid, dihydroxyethyl ethylenediamine monosuccinic acid, 1,3-propanediamine disuccinic acid, triethyl Tetramine trisuccinic acid, 1,2-diaminopropane disuccinic acid, ethylenediaminetetrapropionic acid, hydroxyethylethylenediamine tripropionic acid, dihydroxyethylethylenediamine dipropionic acid, 1,3-propanediamine tetrapropionic acid, diethylenetriaminepentapropionic acid, triethylene Ethylenetetramine hexapropionic acid, 1,2-diaminopropanetetraacetic acid, citric acid, isocitric acid, fumaric acid, adipic acid, succinic acid, glutamic acid, malic acid, tartaric acid, bathocuproine sulfonic acid and lithium salts of these acids , Sodium salts, potassium salts, ammonium salts, calcium salts, magnesium salts, polyalkylammonium salts, and polyarylammonium salts. As a salt, when a plurality of carboxylic acids, sulfonic acids, etc. are contained in the molecule, all carboxylic acids, sulfonic acids, etc. may be in the form of a salt, and only some carboxylic acids, sulfonic acids, etc. are converted into the salt. It may be.

  Potential adjustment agents added to these wet etching solutions as necessary include hydrogen peroxide, sodium permanganate, potassium permanganate, ammonium permanganate, calcium permanganate, magnesium permanganate, and permanganate. Silver, barium permanganate, lithium chlorate, sodium chlorate, potassium chlorate, ammonium chlorate, lithium bromate, sodium bromate, potassium bromate, ammonium bromate, lithium iodate, sodium iodate, potassium iodate , Ammonium iodate, perchloric acid, lithium perchlorate, sodium perchlorate, potassium perchlorate, ammonium perchlorate, calcium perchlorate, silver perchlorate, perbromate, lithium perbromate, perbromine Sodium phosphate, potassium perbromate, ammonium perbromate Calcium perbromate, silver perbromate, periodate, lithium periodate, sodium periodate, potassium periodate, ammonium periodate, calcium periodate, silver periodate, dichromate, dichrome Lithium acid, sodium dichromate, potassium dichromate, calcium dichromate, magnesium dichromate, osmium tetroxide, metachloroperbenzoic acid, lithium persulfate, sodium persulfate, potassium persulfate, ammonium persulfate, iron chloride, etc. Can be mentioned.

  In addition, surfactants to be added to these wet etching solutions as necessary include olefin sulfonic acid, alkyl sulfonic acid, benzene sulfonic acid, alkyl sulfate ester, alkyl ether sulfate ester, alkyl carboxylic acid, perfluoroalkyl sulfonic acid. , Monoalkyl phosphoric acid, poly (oxyethylene) alkyl ether, poly (oxyethylene) fatty acid ester, polyethylene glycol, polyoxyethylene polyoxypropylene ether, glycerin fatty acid ester, acetylene diol, acetylene glycol and the like.

  In addition, the said acid, an alkali, and a chelating agent may be used individually and may be used in combination of multiple. In addition, additives such as a potential adjusting agent and a surfactant may be used as a single component or a mixed component.

  The substrate with a pattern thus obtained can be used as a transfer substrate having a transfer pattern of convex portions 11a and concave portions 11b by etching the base material 11 using this pattern as a mask (FIG. 4E). ). Dry etching is used for etching the substrate 11.

The apparatus used for the dry etching process is not particularly limited as long as it can introduce a chlorofluorocarbon gas in vacuum, can form plasma, and can perform the etching process. For example, a commercially available dry etching apparatus or RIE apparatus may be used. An ICP device or the like can be used. The gas type, time, power, etc. for performing the dry etching process can be appropriately determined depending on the type of the heat-reactive resist, the type of the first heat conductive layer (etching layer), the thickness, the etching rate, and the like. In addition, as a gas used for dry etching of the base material, an etching gas used for general dry etching may be used. Examples of the etching gas include fluorine-based gases such as CF ₄ and SF ₆ , and these may be used alone or in combination with a plurality of gases. Further, a mixture in which the above-described fluorine-based gas and a gas such as O ₂ , H ₂ , Ar, N ₂ , CO, HBr, NF ₃ , HCl, HI, BBr ₃ , BCl ₃ , Cl ₂ , and SiCl ₄ are mixed. The gas is also within the range of fluorine-based gas.

  Hereinafter, examples carried out to clarify the effects of the present invention will be described, but the present invention is not limited to these examples.

Example 1
Copper oxide (II) to which Si was added was formed on a 50 mmφ glass substrate by sputtering to form a thermal reaction type resist layer having a thickness of 20 nm. The film formation was performed under the following conditions.
Target: Si-added copper oxide (3 inch φ, CuO: Si = 85 atomic%: 15 atomic%)
Power (W): RF100
Gas type: Mixed gas of argon and oxygen (ratio 90:10)
Pressure (Pa): 0.5

Next, the heat-reactive resist layer was exposed under the following conditions.
Semiconductor laser wavelength for exposure: 405 nm
Lens numerical aperture: 0.85
Exposure laser power: 7.7 mW
Feed pitch: 300nm
Although various shapes and patterns can be formed by modulating the laser intensity during exposure, in this embodiment, an isolated circular pattern is used as a pattern in order to make the state of the granular material easy to understand. The pattern shape to be formed may be an elliptical shape, a line shape, or the like depending on a desired application.

  Next, the thermally reactive resist layer was partially dissolved using a wet etching solution prepared with 9.0 g of glycine, 0.30 g of nonionic surfactant Adekatol SO-135 (trade name, manufactured by Adeka) and 300 g of water. (Wet etching (development processing)). The wet etching was performed by immersing the base material with a heat-reactive resist layer in a wet etching solution at 23 ° C. for 4 minutes. In this way, a patterned substrate of Example 1 was produced.

  Subsequently, the heat-reactive resist layer of the patterned substrate of Example 1 was measured by SEM (scanning electron microscope). As a result, it was confirmed that particles having an average particle diameter of 10 nm were present on the bottom and side surfaces of the recesses in the substantially circular main pattern.

  Next, a photocurable resin PAK-01 (trade name, manufactured by Toyo Gosei Co., Ltd.) is applied to the pattern surface side, and a polypropylene film is further applied thereon, followed by irradiation with a metal halide lamp. Cured. After curing was completed, one end of the polypropylene film was fixed only to the spring and the force required to peel the film from the substrate was 13N.

Next, the glass substrate was dry-etched under the following conditions using the heat-reactive resist layer of the patterned substrate of Example 1 as an etching mask.
Etching gas type: SF ₆
Etching power: 300W
Etching gas pressure: 1Pa
Etching gas flow rate: 50 sccm
Etching time: 15 minutes

  Thereafter, the heat-reactive resist layer was removed from the glass substrate with 1% sulfuric acid to prepare a transfer substrate. The SEM image of the cut surface of the obtained transfer substrate was measured from an angle of 45 °. As a result, it was found that a pattern having a zigzag side surface was obtained, and it was confirmed that the surface area was increased as compared with the smooth side surface.

  Next, a photocurable resin PAK-01 (trade name, manufactured by Toyo Gosei Co., Ltd.) is applied to the pattern surface side, and a polypropylene film is further applied thereon, followed by irradiation with a metal halide lamp. Cured. After the curing was completed, one end of the polypropylene film was fixed only to the spring, and the force required for peeling the film from the substrate was determined to be 23N.

(Example 2)
Chromium oxide was deposited on a 50 mmφ glass substrate by sputtering to form a 20 nm thick thermal reaction type resist layer. The film formation was performed under the following conditions.
Target: Chrome (3 inch φ)
Power (W): RF100
Gas type: Mixed gas of argon and oxygen (ratio 90:10)
Pressure (Pa): 0.5

Next, the heat-reactive resist layer was exposed under the following conditions.
Semiconductor laser wavelength for exposure: 405 nm
Lens numerical aperture: 0.85
Exposure laser power: 9.0mW
Feed pitch: 400nm
Although various shapes and patterns can be formed by modulating the laser intensity during exposure, in this embodiment, an isolated circular pattern is used as a pattern in order to make the state of the granular material easy to understand.

  Next, the heat-reactive resist layer was partially dissolved using a wet etching solution prepared with 45 g of diammonium cerium nitrate, 15 g of nitric acid, and 240 g of water (wet etching (development processing)). The wet etching was performed by immersing the substrate with a heat-reactive resist layer in a wet etching solution at 23 ° C. for 1 minute. In this way, a patterned substrate of Example 2 was produced.

  Subsequently, the heat-reactive resist layer of the patterned substrate of Example 2 was measured by SEM. As a result, it was confirmed that particles having an average particle diameter of 50 nm were present on the bottom and side surfaces of the recesses in the substantially circular main pattern.

  Next, a photocurable resin PAK-01 (trade name, manufactured by Toyo Gosei Co., Ltd.) is applied to the pattern surface side, and a polypropylene film is further applied thereon, followed by irradiation with a metal halide lamp. Cured. After curing was completed, one end of the polypropylene film was fixed only to the spring, and the force required for peeling the film from the substrate was 11N.

Next, the glass substrate was dry-etched under the following conditions using the heat-reactive resist layer of the patterned substrate of Example 2 as an etching mask.
Etching gas type: CF ₄
Etching power: 400W
Etching gas pressure: 5Pa
Etching gas flow rate: 50 sccm
Etching time: 15 minutes

  Thereafter, the heat-reactive resist layer was removed from the glass substrate with 5% nitric acid to prepare a transfer substrate. The SEM image of the cut surface of the obtained transfer substrate was measured from an angle of 45 °. As a result, it was found that a pattern having a zigzag side surface was obtained, and it was confirmed that the surface area was increased as compared with the smooth side surface.

  Next, a photocurable resin PAK-01 (trade name, manufactured by Toyo Gosei Co., Ltd.) is applied to the pattern surface side, and a polypropylene film is further applied thereon, followed by irradiation with a metal halide lamp. Cured. After the curing was completed, one end of the polypropylene film was fixed only to the spring, and the force required for peeling the film from the substrate was 19N.

Example 3
A tungsten oxide film was formed on a 50 mmφ glass substrate by sputtering to form a thermal reaction type resist layer having a thickness of 50 nm. The film formation was performed under the following conditions.
Target: Tungsten (3 inch φ)
Power (W): RF100
Gas type: Mixed gas of argon and oxygen (ratio 90:10)
Pressure (Pa): 0.5

Next, the heat-reactive resist layer was exposed under the following conditions.
Semiconductor laser wavelength for exposure: 405 nm
Lens numerical aperture: 0.85
Exposure laser power: 8.0mW
Feed pitch: 500nm
Although various shapes and patterns can be formed by modulating the laser intensity during exposure, in this embodiment, an isolated circular pattern is used as a pattern in order to make the state of the granular material easy to understand.

  Next, the heat-reactive resist layer was partially dissolved using a wet etching solution prepared with 300 g of a 2.4% tetramethylammonium hydroxide aqueous solution (wet etching (development processing)). The wet etching was performed by immersing the base material with a heat-reactive resist layer in a wet etching solution at 23 ° C. for 2 minutes. In this way, a patterned substrate of Example 3 was produced.

  Subsequently, the heat-reactive resist layer of the patterned substrate of Example 3 was measured by SEM. As a result, it was confirmed that particles having an average particle diameter of 40 nm were present on the bottom and side surfaces of the recesses in the substantially circular main pattern.

  Next, a photocurable resin PAK-01 (trade name, manufactured by Toyo Gosei Co., Ltd.) is applied to the pattern surface side, and a polypropylene film is further applied thereon, followed by irradiation with a metal halide lamp. Cured. After curing was completed, one end of the polypropylene film was fixed only to the spring, and the force required for peeling the film from the substrate was 11N.

Subsequently, the glass substrate was dry-etched under the following conditions using the heat-reactive resist layer of the patterned substrate of Example 3 as an etching mask.
Etching gas type: CF ₄
Etching power: 400W
Etching gas pressure: 5Pa
Etching gas flow rate: 50 sccm
Etching time: 15 minutes

  Thereafter, the heat-reactive resist layer was removed from the glass substrate with 1% sulfuric acid to prepare a transfer substrate. The SEM image of the cut surface of the obtained transfer substrate was measured from an angle of 45 °. As a result, it was found that a pattern having a zigzag side surface was obtained, and it was confirmed that the surface area was increased as compared with the smooth side surface.

  Next, a photocurable resin PAK-01 (trade name, manufactured by Toyo Gosei Co., Ltd.) is applied to the pattern surface side, and a polypropylene film is further applied thereon, followed by irradiation with a metal halide lamp. Cured. After curing was completed, one end of the polypropylene film was fixed only to the spring and the force required for peeling the film from the substrate was 20 N.

Example 4
A tin oxide film was formed on a 50 mmφ glass substrate by sputtering to form a heat-reactive resist layer having a thickness of 25 nm. The film formation was performed under the following conditions.
Target: Tin (3 inches φ)
Power (W): RF100
Gas type: Mixed gas of argon and oxygen (ratio 85:15)
Pressure (Pa): 0.5

Next, the heat-reactive resist layer was exposed under the following conditions.
Semiconductor laser wavelength for exposure: 405 nm
Lens numerical aperture: 0.85
Exposure laser power: 6.0mW
Feed pitch: 500nm
Although various shapes and patterns can be formed by modulating the laser intensity during exposure, in this embodiment, an isolated circular pattern is used as a pattern in order to make the state of the granular material easy to understand.

  Next, the heat-reactive resist layer was partially dissolved using a wet etching solution prepared with 300 g of a 1% nitric acid aqueous solution (wet etching (development process)). The wet etching was performed by immersing the base material with a heat-reactive resist layer in a wet etching solution at 23 ° C. for 2 minutes. In this way, a patterned substrate of Example 4 was produced.

  Subsequently, the heat-reactive resist layer of the patterned substrate of Example 4 was measured by SEM. As a result, it was confirmed that particles having an average particle diameter of 150 nm were present on the bottom and side surfaces of the recesses in the substantially circular main pattern.

  Next, a photocurable resin PAK-01 (trade name, manufactured by Toyo Gosei Co., Ltd.) is applied to the pattern surface side, and a polypropylene film is further applied thereon, followed by irradiation with a metal halide lamp. Cured. After curing was completed, one end of the polypropylene film was fixed only to the spring and the force required for peeling the film from the substrate was 14N.

Next, the glass substrate was dry-etched under the following conditions using the heat-reactive resist layer of the patterned substrate of Example 4 as an etching mask.
Etching gas type: CF ₄
Etching power: 400W
Etching gas pressure: 5Pa
Etching gas flow rate: 50 sccm
Etching time: 15 minutes

  Thereafter, the heat-reactive resist layer was removed from the glass substrate with 1% sulfuric acid to prepare a transfer substrate. The SEM image of the cut surface of the obtained transfer substrate was measured from an angle of 45 °. As a result, it was found that a pattern having a zigzag side surface was obtained, and it was confirmed that the surface area was increased as compared with the smooth side surface.

  Next, a photocurable resin PAK-01 (trade name, manufactured by Toyo Gosei Co., Ltd.) is applied to the pattern surface side, and a polypropylene film is further applied thereon, followed by irradiation with a metal halide lamp. Cured. When curing was completed, one end of the polypropylene film was fixed only to the spring, and the force required to peel the film from the substrate was 25 N.

(Comparative Example 1)
A heat-reactive resist layer of tungsten oxide was formed on a 50 mmφ glass substrate under the same conditions as in Example 3.

Next, the heat-reactive resist layer was exposed under the following conditions.
Semiconductor laser wavelength for exposure: 405 nm
Lens numerical aperture: 0.85
Exposure laser power: 9.2mW
Feed pitch: 500nm
Various shapes and patterns can be formed by modulating the intensity of the laser during exposure, but in this comparative example, an isolated circular pattern was used as a pattern in order to make the state of the granular material easier to understand.

  Next, the heat-reactive resist layer was partially dissolved using a wet etching solution prepared with 300 g of a 2.4% tetramethylammonium hydroxide aqueous solution (wet etching (development processing)). The wet etching was performed by immersing the base material with a heat-reactive resist layer in a wet etching solution at 23 ° C. for 2 minutes. In this way, a patterned substrate of Comparative Example 1 was produced.

  Subsequently, the heat-reactive resist layer of the patterned substrate of Comparative Example 1 was measured by SEM. As a result, no particulate matter was observed on the bottom surface or the side surface of the recess in the substantially circular main pattern.

  Next, a photocurable resin PAK-01 (trade name, manufactured by Toyo Gosei Co., Ltd.) is applied to the pattern surface side, and a polypropylene film is further applied thereon, followed by irradiation with a metal halide lamp. Cured. After the curing was completed, one end of the polypropylene film was fixed only to the spring, and the force required to peel the film from the substrate was 6 N. It was peeled off with about half the force of the patterned substrate of Example 3. I have.

Subsequently, the glass substrate was dry-etched under the following conditions using the heat-reactive resist layer of the patterned substrate of Comparative Example 1 as an etching mask.
Etching gas type: CF ₄
Etching power: 400W
Etching gas pressure: 5Pa
Etching gas flow rate: 50 sccm
Etching time: 15 minutes

  Thereafter, the heat-reactive resist layer was removed from the glass substrate with 1% sulfuric acid to prepare a transfer substrate. The SEM image of the cut surface of the obtained transfer substrate was measured from an angle of 45 °. As a result, it was confirmed that a smooth pattern without zigzags was obtained on the side surface.

  Next, a photocurable resin PAK-01 (trade name, manufactured by Toyo Gosei Co., Ltd.) is applied to the pattern surface side, and a polypropylene film is further applied thereon, followed by irradiation with a metal halide lamp. Cured. After the curing was completed, one end of the polypropylene film was fixed only to the spring, and the force required to peel the film from the substrate was 6 N. It was peeled off with about half the force of the patterned substrate of Example 3. I have. As described above, in the main pattern having a substantially circular shape, the adhesion is reduced when there is no granular material on the bottom surface or the side surface of the recess.

  The present invention is not limited to the embodiment described above, and can be implemented with various modifications. For example, the material, arrangement, shape, and the like of the members in the above embodiment are illustrative, and can be implemented with appropriate changes. In addition, various modifications can be made without departing from the scope of the present invention.

  The substrate with a pattern according to the present invention may be used as it is as a pattern having an increased surface area, and can also be used as an etching mask pattern. In any case, it can be used for applications requiring high adhesion and the like. Is possible.

DESCRIPTION OF SYMBOLS 11 Base material 11a, 12b Convex part 11b, 12c Concave part 12 Thermal reaction type resist layer 12a Altered part 13 Granules

Claims (11)

  A heat-reactive resist layer provided on the base material and made of a heat-reactive resist material and having a pattern including convex portions and concave portions, and the heat-reactive resist layer is A substrate with a pattern, characterized in that the recess includes a granular material containing at least the heat-reactive resist material.   2. The patterned substrate according to claim 1, wherein the granular material is obtained by altering the heat-reactive resist material when heat is applied to the heat-reactive resist layer.   The patterned substrate according to claim 1 or 2, wherein an average particle diameter of the granular material is 1 nm or more and 1000 nm or less.   The substrate with a pattern according to any one of claims 1 to 3, wherein a difference in height from the bottom of the concave portion to the top of the convex portion in the pattern is 5 nm or more and 10,000 nm or less.   The substrate with a pattern according to any one of claims 1 to 4, wherein the granular material contains at least a metal element.   The substrate with a pattern according to any one of claims 1 to 5, wherein the pattern has a substantially lattice shape or a substantially dot shape in plan view.   A substrate for transfer, wherein the substrate is etched using the pattern in the substrate with a pattern according to any one of claims 1 to 6 as a mask.   Forming a heat-reactive resist layer composed of a heat-reactive resist material on a base material; and applying heat to the heat-reactive resist layer partially to alter the heat-reactive resist material; Removing the altered heat-reactive resist layer to form a pattern including a convex part and a concave part having a granular material containing at least the heat-reactive resist material. A method for producing a patterned substrate.   The method for producing a patterned substrate according to claim 8, wherein the heat-reactive resist material is altered by partially applying heat to the heat-reactive resist layer by exposure using a laser.   The heat-reactive resist material contains 80% by volume or less of silicon, aluminum, titanium, gallium, tantalum, cobalt, or an oxide or nitride thereof with respect to 100% by volume of the heat-reactive resist material. The manufacturing method of the base material with a pattern of Claim 8 or Claim 9. A substrate for transfer, wherein the substrate is etched using the pattern in the substrate with a pattern obtained by the method for producing a substrate with a pattern according to any one of claims 8 to 10 as a mask. Production method.

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