JP2011111636A - Substrate for wet etching and its application - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a substrate which suppresses the peeling of a thermoplastic polymer and the permeation of a wet etching liquid and a plating liquid into a resist or into a boundary between a metal layer and the resist in a thermal nanoimprint process. <P>SOLUTION: The substrate includes: a substrate layer 1: a metal layer 2 having a metal oxide surface; a sensitive ultraviolet compound layer 3 exhibiting adhesive properties by ultraviolet irradiation which is shown by the following formula; and a thermoplastic polymer layer 4 in this order: R1 to R3: H, a 1-6C hydrocarbon group or the like; X: O, OCO, COO, NH or NHCO; m:1 to 20; R4: a 1C-3C hydrocarbon group; Y: a 1C-3C alkoxy group or a halogen atom; and n: 1 to 3. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a substrate for wet etching, a method for manufacturing a substrate having a metal pattern using the substrate, and a substrate having the metal pattern.

The wet etching technique is used for the production of metal patterns such as metal wirings and photomasks. Specifically, copper and gold metal patterns are used for printed circuit boards of household electrical appliances such as liquid crystal displays, silver metal patterns are used for collecting electrodes of solar cells, and chromium metal patterns are used for photomasks. ing. These metal patterns are required to be further miniaturized from the expectation for downsizing and multi-functioning of information equipment accompanying an increase in the amount of information in recent years.
The main metal pattern is produced by, for example, applying a positive resist or negative resist on the metal surface, forming a resist pattern by contact exposure or projection exposure photolithography, and using wet etching or electrolytic plating. The Since the resist for photolithography used here has a highly hydrophilic functional group in a photoacid generator, a photoactive substance, the resist resin itself, etc., the resist itself has high water absorption. Such high water absorption may cause the penetration of the chemical into the resist and the penetration into the resist-metal interface in wet etching and electroplating using aqueous chemicals, which may hinder the miniaturization of metal patterns. There is.

Therefore, Patent Document 1 discloses a method in which a hydrophobic resist pattern is formed by a thermal nanoimprint method that does not require a photoacid generator or a photoactive substance that increases water absorption, and a fine metal pattern is formed by wet etching. Proposed. This hydrophobic resist lowers the adhesion between the resist and the metal, and causes defects during thermal nanoimprinting. For this reason, in Patent Document 1, a compound having a benzophenone skeleton and a thiol skeleton is disposed between a resist and a metal, and adhesion is improved by a photocrosslinking reaction of benzophenone.
However, the metal species of the metal pattern that can be produced according to Patent Document 1 are limited to gold, silver, copper, and the like that can adsorb thiol groups. For this reason, the development of a technique for performing microfabrication of other industrially used metals is desired.

In general, in order to obtain adhesion between a resist and a metal, an anchor effect may be imparted by adding an adhesion improving component to the resist composition or roughening the metal surface. In changing the resist composition, there are methods such as adding an additive and making the resist itself hydrophilic. However, as described above, such a method may hinder miniaturization of the metal pattern. Further, surface roughening is not suitable because it causes defects when a resist pattern is formed by a thermal nanoimprint method.
As another method for obtaining adhesion between a polymer and a metal, a method using an analogous compound of a compound having a benzophenone skeleton and a thiol skeleton described in Patent Document 1 has been proposed. The method is a method in which adhesion is obtained by photocrosslinking reaction of a benzophenone group using a silane coupling group capable of binding to the surface of the metal oxide and a compound having a benzophenone skeleton as in Patent Document 1.

Specifically, for example, in Patent Document 2, a compound having a trimethoxysilane group as a silane coupling group is proposed, and the function and stabilization of the surface of the fine particle are achieved by bonding the compound to the surface of the metal oxide fine particle. The method of doing etc. is proposed. In Patent Document 3 and Non-Patent Document 1, a compound having a triethoxysilane group is proposed, and the compound is bonded onto a substrate, and further, a functional polymer is applied and then immobilized by a photocrosslinking reaction. A method for imparting a function derived from a functional polymer such as a DNA array on a substrate has been proposed.
Furthermore, Non-Patent Documents 2 to 4 report a compound having a dimethylchlorosilane group, and Non-Patent Document 5 reports a compound having a trichlorosilane group. In Non-Patent Documents 2 and 3, a functional polymer is immobilized on a substrate in the same manner as Non-Patent Document 1, and in Non-Patent Document 4, a functional molecule is immobilized on a silicon substrate using the compound. There has been reported a technique of dry-etching using as a thin film molecular resist. Non-Patent Document 5 reports a method for immobilizing a polymer having a fluorine group on a substrate in the same manner as Non-Patent Document 1.
Although there are reports as described above, there is no example of applying a compound having a benzophenone skeleton and a silane coupling group to a substrate for wet etching, and it is known to produce a fine metal pattern in combination with a thermal nanoimprint method. Not.

JP 2009-73809 A International Publication No. 2009/101016 US Pat. No. 7,176,297

Gianneli, Maria, et al., Soft Matter (2008), 4 (7), 1443-1447. Prucker, Oswald, et al., J. Am. Chem. Soc. (1999), 121 (38), 8766-8770. Loschonsky, S., et al. Biomacromolecules (2008), 9 (2), 543-552. Jarvholm, Jonas, et al., J. Am. Chem. Soc. (2009), 131 (2), 398 -399. Mock, Ulrike, et al ,. Journal of Physics: Condensed Matter (2005), 17 (9), S595-S605.

The subject of this invention is providing the board | substrate for wet etching which adhere | attached the metal and thermoplastic polymer of the board | substrate surface firmly using the ultraviolet sensitive compound which expresses adhesiveness by ultraviolet irradiation.
Another object of the present invention is to provide a method for producing a substrate having a fine metal pattern by a subtractive method or an additive method by producing a concavo-convex shape by a thermal nanoimprint method for the wet etching substrate of the present invention. There is to do.
Another object of the present invention is to provide a substrate having a fine metal pattern having a line width of 0.01 μm to 10 μm.

  As a result of diligent research to solve the above problems, the inventors of the present invention have developed a wet etching substrate in which a specific ultraviolet-sensitive compound is disposed between a metal layer having a metal oxide surface and a thermoplastic polymer layer. By using it, it discovered that the said subject could be solved and came to complete this invention.

（式中、Ｒ１〜Ｒ３は水素原子、炭素数１〜６の炭化水素基、酸素原子または窒素原子で連結された炭素数１〜６の炭化水素基を示す。ＸはＯ、ＯＣＯ、ＣＯＯ、ＮＨ、ＮＨＣＯ
を示し、ｍは１〜２０の整数を示す。Ｒ４は炭素数１〜３の炭化水素基を示し、Ｙは炭素数１〜３のアルコキシ基またはハロゲン原子を表し、ｎは１〜３の整数を表す。）
また本発明によれば、上記ウェットエッチング用基板に対して、少なくとも１部に紫外線照射を施したウェットエッチング用基板が提供される。 According to the present invention, there is provided a wet etching substrate having a substrate layer, a metal layer having a metal oxide surface, an ultraviolet-sensitive compound layer represented by formula (1), and a thermoplastic polymer layer in this order.

(In the formula, R1 to R3 represent a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a hydrocarbon group having 1 to 6 carbon atoms linked by an oxygen atom or a nitrogen atom. X represents O, OCO, COO, NH, NHCO
M represents an integer of 1-20. R4 represents a hydrocarbon group having 1 to 3 carbon atoms, Y represents an alkoxy group having 1 to 3 carbon atoms or a halogen atom, and n represents an integer of 1 to 3. )
According to the present invention, there is also provided a wet etching substrate in which at least a part of the wet etching substrate is irradiated with ultraviolet rays.

Furthermore, according to this invention, the manufacturing method of the board | substrate which has a metal pattern characterized by performing at least the following processes with respect to the board | substrate for wet etching which performed said ultraviolet irradiation.
(1a) a step of forming a concavo-convex shape by a thermal nanoimprint method,
(1b) removing the thermoplastic polymer layer remaining in the concave-convex shaped recess,
(1c) removing the metal layer under the recess by wet etching;
(1d) A step of peeling off the ultraviolet-sensitive compound layer and the thermoplastic polymer layer on the metal layer.
Furthermore, according to the present invention, there is provided a wet etching substrate in which at least a part of the wet etching substrate subjected to ultraviolet irradiation is irradiated with ultraviolet light.
(2a) a step of forming an uneven shape by a thermal nanoimprint method,
(2b) removing the thermoplastic polymer layer remaining in the concave-convex recess,
(2c) forming a metal pattern by electrolytic plating in the recesses,
(2d) a step of peeling off the UV-sensitive compound layer and the thermoplastic polymer layer on the metal layer,
(2e) A step of removing the metal film in the recess by wet etching.
Moreover, according to this invention, the board | substrate which has a metal pattern with a line width of 0.01-10 micrometers manufactured by one of the said manufacturing methods is provided.

In the substrate for wet etching according to the present invention, the metal layer having a metal oxide surface and the thermoplastic polymer layer are firmly bonded with an ultraviolet-sensitive compound that exhibits adhesiveness by ultraviolet irradiation, so that the thermoplastic polymer in the thermal nanoimprint method is used. Designed to suppress the peeling of the metal, the wet etching solution and the plating solution in wet etching and electroplating into the resist, and the penetration between the metal layer having the metal oxide surface and the resist. A substrate having the same fine metal pattern can be obtained.
The metal pattern production method of the present invention is excellent in mass productivity, and the metal pattern thus obtained is useful for semiconductors, wiring boards, electronic devices, optical devices, and the like.

It is a general | schematic process drawing for demonstrating the manufacturing method of the board | substrate which has a metal pattern of this invention using the wet etching board | substrate of this invention. It is a copy of the optical microscope image of the polystyrene pattern with which the line & space produced in Example 3-1 is 2 micrometers (left) and 1 micrometer (right). It is a copy of the optical microscope image of the copper pattern produced in Example 3-1 and having a line and space of 2 μm (left) and 1 μm (right). It is a copy of the optical microscope image of the polystyrene pattern produced in Comparative Example 3-1, with a line and space of 2 μm (left) and 1 μm (right). It is a copy of the optical microscope image of the copper pattern whose line & space produced in Comparative Example 3-1 is 2 micrometers (left) and 1 micrometer (right).

  DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the drawings as necessary. The following are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. And this invention can be deform | transformed suitably and implemented within the range of the summary. In addition, the dimensional ratio of drawing is not restricted to the ratio of illustration.

  In FIG. 1, (a) is an example of a substrate for wet etching according to the present invention, and includes a substrate layer 1, a metal layer 2 having a metal oxide surface (hereinafter sometimes abbreviated as metal layer 2), formula (1) ) And the thermoplastic polymer layer 4 in this order.

The material for forming the substrate layer 1 may be any material that has a glass transition temperature higher than the glass transition temperature of a thermoplastic polymer that is molded by a thermal nanoimprint method to be described later. For example, silicon, glass, quartz, alumina, titanic acid A material selected from the group consisting of inorganic or inorganic oxides such as barium, epoxy resin, phenol resin, polyimide resin, polyester resin, polyphenylene oxide resin, a laminate of two or more of these, and a composite of two or more of these Can be mentioned.
As the composite material, known materials can be used, and examples thereof include a material in which glass fibers are hardened with an epoxy resin and a composite material in which bakelite is laminated.

For example, when the metal layer 2 is made of copper and the finally obtained substrate is used as a wiring board for electronics, the substrate layer 1 is made of silicon, glass, quartz, etc. in terms of smoothness, low expansion coefficient, and insulation. A substrate made of a heat-resistant organic material such as an inorganic or inorganic oxide material or polyimide is preferable. When used for a flexible wiring substrate, a polyester resin, a polyphenylene oxide resin, or a composite material of glass fiber and an epoxy resin is preferable.
When the metal layer 2 is chromium, when the finally obtained substrate is used as a photomask, quartz is preferable from the viewpoint of ultraviolet transmittance.

The metal layer 2 has a metal oxide on the surface. The metal oxide only needs to be capable of binding the ultraviolet-sensitive compound represented by the formula (1). For example, silver oxide, copper oxide, chromium oxide, aluminum oxide, zinc oxide, tin oxide, platinum oxide, oxidation Examples include titanium, palladium oxide, and composites thereof.
The metal of the metal layer 2 may be the same or different from the metal oxide on the surface, for example, silver, copper, chromium, aluminum, zinc, tin, platinum, titanium, palladium, oxides of these metals, and These composites can be mentioned.

From the industrial use of the finally obtained metal pattern, the metal layer 2 is silver having a silver oxide surface when used for an electrode such as a touch panel or a solar cell, copper having a copper oxide surface when used for wiring, or Aluminum having an aluminum oxide surface and chromium having a chromium oxide surface are preferred when used for a photomask.
Although the thickness of the metal layer 2 changes with uses of the metal pattern finally obtained, 5 nm-20 micrometers are preferable. When the thickness is less than 5 nm, the smoothness of the substrate surface is insufficient, and when it is larger than 20 μm, the etching time in the subsequent process becomes long.

In the wet etching substrate of the present invention, the method for forming the metal layer 2 on the substrate layer 1 is not particularly limited, and a known method can be used. Examples thereof include dry plating methods such as sputtering and vacuum deposition, and wet plating methods such as electrolytic plating and electroless plating.
In the wet etching substrate of the present invention, in order to ensure adhesion between the substrate layer 1 and the metal layer 2, a metal such as chromium or titanium is previously subjected to a treatment such as sputtering to form the substrate layer 1 and the metal layer 2. It may be formed in between.

In Formula (1) which shows the compound which forms the ultraviolet-sensitive compound layer 3, R1-R3 are carbon atoms having 1 to 6 carbon atoms connected by hydrogen atoms, hydrocarbon groups having 1 to 6 carbon atoms, oxygen atoms or nitrogen atoms. Indicates a hydrogen group.
Specific examples of the hydrocarbon group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, isobutyl group, sec-butyl group, pentyl group, isopentyl group, A cyclopentyl group, a hexyl group, a cyclohexyl group, and a phenyl group;
Examples of the hydrocarbon group having 1 to 6 carbon atoms connected by an oxygen atom or a nitrogen atom include groups in which the above exemplified groups of the hydrocarbon group having 1 to 6 carbon atoms are connected by an oxygen atom or a nitrogen atom. It is done.
R1 to R3 are preferably a hydrogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group for the reason of photoreactivity due to steric hindrance.

In the formula (1), X represents O, OCO, COO, NH, NHCO, and m represents an integer of 1-20. From the viewpoint of ease of production, X is preferably O. When m exceeds 20, the flexibility of the molecular chain increases, the amount of adsorption of the compound decreases, and the adhesion function may be lowered.
In the formula (1), R4 represents a hydrocarbon group having 1 to 3 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, Y represents an alkoxy group having 1 to 3 carbon atoms or a halogen atom, n Represents an integer of 1 to 3.
In formula (1), examples of —Si (Y) _n (R4) _3-n include trimethoxysilane, dimethylmethoxysilane, triethoxysilane, dimethylethoxysilane, trichlorosilane, and dimethylchlorosilane. Trimethoxysilane, dimethylmethoxysilane, triethoxysilane, and dimethylethoxysilane are preferable from the reason for using for this.
Moreover, the 2nd-position, 6th-position, 2'-position, and 6'-position in the ultraviolet-sensitive compound of the formula (1) require a hydrogen atom for the reason of photoreactivity.

  As the UV-sensitive compound represented by the formula (1), for example, 4- (3-trimethyl) is preferable because of the availability of raw materials, ease of synthesis, photoreactivity with a thermoplastic polymer, and adhesion to a gold substrate. Methoxysilyl) propyloxybenzophenone, 4- (3-trimethoxysilyl) propyloxy-4'-methoxybenzophenone, 8- (3-trimethoxysilyl) octyloxybenzophenone, 8- (3-trimethoxysilyl) octyloxy- 4'-methoxybenzophenone, 4- (3-triethoxysilyl) propyloxybenzophenone, 4- (3-triethoxysilyl) propyloxy-4'-methoxybenzophenone, 8- (3-triethoxysilyl) octyloxybenzophenone, 8- (3-Triethoxysilyl) octyloxy-4′-methoxybenzo Enone, 4- (3-trichlorosilyl) propyloxybenzophenone, 4- (3-trichlorosilyl) propyloxy-4′-methoxybenzophenone, 8- (3-trichlorosilyl) octyloxybenzophenone, 8- (3-trichlorosilyl) ) Octyloxy-4′-methoxybenzophenone, 4- (3-dimethylchlorosilyl) propyloxybenzophenone, 4- (3-dimethylchlorosilyl) propyloxy-4′-methoxybenzophenone, 8- (3-dimethylchlorosilyl) Preferred examples include octyloxybenzophenone and 8- (3-dimethylchlorosilyl) octyloxy-4′-methoxybenzophenone. These ultraviolet-sensitive compounds can be produced by a known method.

In the wet etching substrate of the present invention, the method for forming the ultraviolet-sensitive compound layer 3 on the metal layer 2 may be a known method such as an immersion method or a vapor phase method.
In the dipping method, for example, first, UV / ozone treatment or the like is performed on the metal layer 2 to form a hydroxyl group on the surface of the metal layer. Next, a solution obtained by dissolving an ultraviolet-sensitive compound in a solvent is formed and reacted on a metal layer having a hydroxyl group by spin coating, dipping, spray coating, flow coating, roll coating, die coating, or the like. Then, the method of evaporating the component which is a solvent under ventilation, heating, and pressure reduction further is mentioned.

The solvent may be any solvent that dissolves the UV-sensitive compound and does not react with the UV-sensitive compound. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, propyl acetate, butyl acetate, methoxypropyl acetate, lactic acid Examples include ethyl, tetrahydrofuran, dioxane, chloroform, butyl chloride, toluene, xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, ethylene carbonate, and γ-butyrolactone, and toluene is preferred from the viewpoint of the working environment.
In solution-sensitive ultraviolet compound is dissolved in a solvent, the concentration of sensitive ultraviolet compound is usually in the range of 0.0001~1mol / dm ^3, preferably 0.0001~0.1mol / dm ^3. By setting the concentration to 0.0001 mol / dm ³ or more, the ultraviolet-sensitive compound layer can be formed uniformly. Further, when the concentration is 1 mol / dm ³ or less, a sufficient effect is obtained and it is economical.

Examples of the vapor phase method include a method in which a substrate having a metal layer in which a hydroxyl group is formed and an ultraviolet-sensitive compound are placed in the same container, sealed in a nitrogen atmosphere, and heated as in the immersion method.
The heating temperature is 140 to 250 ° C., preferably without any problem unless the UV-sensitive compound is volatilized and decomposes.

The material for forming the thermoplastic polymer layer 4 has a weight average molecular weight of 2,000 to 1,000,000, preferably 2,000 to 500,000, has a glass transition temperature of room temperature or higher, is soluble in a solvent, and is wet-etched. Preferred examples include thermoplastic polymers that are insoluble in the chemical solution used in electrolytic plating. Specific examples include polymethyl methacrylate, polystyrene, polyvinyl toluene, polybenzyl methacrylate, polycarbonate, polyethylene, polypropylene, polyvinyl chloride, and cyclic polyolefin.
From the viewpoint of use in a wet etching resist, it is preferable to use a thermoplastic polymer composed of a hydrocarbon group having low water absorption, and specifically, polystyrene, polyvinyl toluene, and cyclic polyolefin can be mentioned. When thermoplastic polymers composed of these hydrocarbon groups are used, it is difficult for the wet etching solution to enter the resist due to its low water absorption, so that the resist film thickness can be reduced. By shortening the molding time in nanoimprint molding, improving the stirring efficiency of the wet etching solution, and suppressing the progress of side etching, a metal pattern with good rectangularity can be produced.

In the wet etching substrate of the present invention, the method for forming the thermoplastic polymer layer 4 is, for example, a solution obtained by dissolving a thermoplastic polymer in a solvent, spin coating method, dipping method, spray coating method, flow coating method, Film formation can be performed by a roll coating method, a die coating method, or the like, and further by evaporating the solvent under blowing, heating, or reduced pressure.
The solvent only needs to dissolve the thermoplastic polymer used. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, propyl acetate, butyl acetate, methoxypropyl acetate, ethyl lactate, tetrahydrofuran, dioxane, chloroform, butyl chloride. , Toluene, xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, ethylene carbonate, and γ-butyrolactone.
In addition, a surfactant, a leveling agent or the like can be added to improve the coating properties on the substrate, or a fluorescent material for shape inspection can be added. Examples of these surfactants and leveling materials include ionic or nonionic surfactants, silicone derivatives, and fluorine derivatives. Examples of fluorescent materials include acridine fluorescent materials, anthracene fluorescent materials, rhodamine fluorescent materials, pyromethene fluorescent materials, and perylene fluorescent materials.

In a solution in which a thermoplastic polymer is dissolved in a solvent, the concentration of the thermoplastic polymer is usually in the range of 0.1 to 20% by mass. When the concentration is lower than 0.1% by mass, the film thickness of the thermoplastic polymer becomes too thin, and there is a possibility that it does not function as a resist. When the concentration is higher than 20% by mass, the film thickness may not be uniform.
The thickness of the thermoplastic polymer layer 4 is not particularly limited as long as it can be used in wet etching and electrolytic plating described later, and the protective ability of the metal layer 2 and the thermoplastic polymer layer 4 are not limited. From the viewpoint of ease of removal when removing, 0.2 to 10 μm is preferable, 0.2 to 5.0 μm is more preferable, and 0.2 to 2.0 μm is further preferable.
The thermoplastic polymer layer 4 may be two or more layers. For example, the thermoplastic polymer layer may be formed again after irradiating the wet etching substrate described later with ultraviolet rays.

Examples of the wet etching substrate of the present invention include those obtained by irradiating at least a part of the above-mentioned substrate with ultraviolet rays. FIG. 1B shows an ultraviolet irradiation step of irradiating the wet etching substrate with ultraviolet rays. FIG.
Ultraviolet irradiation can be usually performed by irradiating ultraviolet rays having a wavelength of 200 to 400 nm. By this ultraviolet irradiation, the carbonyl group of benzophenone in the ultraviolet sensitive compound is excited to generate a biradical. The radicals generated on the oxygen atoms of benzophenone quickly convert hydrogen into hydrocarbons by extracting hydrogen atoms from the hydrocarbons of the thermoplastic polymer. The radical generated on the carbon of one benzophenone forms a covalent bond by recombination with the radical generated on the hydrocarbon of the thermoplastic polymer. Based on this principle, the metal layer 2 and the thermoplastic polymer layer 4 are firmly bonded via the UV-sensitive compound layer 3 by the covalent bond of the silane coupling agent to the metal layer and the covalent bond of benzophenone to the thermoplastic polymer. The

As a light source for ultraviolet irradiation, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, an Hg-Xe lamp, or a halogen lamp can be used, and in consideration of the absorption band of the resin used for the thermoplastic polymer layer 4 A cut-off filter or the like can be used. A wavelength of 200 nm or more is preferable because the transmittance to the thermoplastic polymer layer 4 is high and the light source used is inexpensive. A wavelength of 400 nm or less is preferable because a photo-induced radical derived from a benzophenone structure can be efficiently formed.
The irradiation energy of ultraviolet rays is usually 10 to 250 J / cm ² at a detection wavelength of 365 nm, or usually 0.1 to 5 J / cm ² at a detection wavelength of 254 nm. In detection wavelength 365 nm 10J / cm ² or more, or, by a 0.1 J / cm ² or more at a detection wavelength 254 nm, it is possible to sufficiently proceed the photo-crosslinking reaction of the sensitive UV compounds, exhibit sufficient adhesive function it can. When the irradiation energy is 250 J / cm ² or less at a detection wavelength of 254 nm or 10 J / cm ² or less at a detection wavelength of 254 nm, film deterioration and surface cracks can be effectively prevented.

In the manufacturing method of the present invention, the step (1a) or the step (2a) of forming a concavo-convex shape by a thermal nanoimprint method is performed on the wet etching substrate of the present invention irradiated with the above-described ultraviolet rays (in FIG. C) Before thermal nanoimprint process, (d) After thermal nanoimprint process).
As the thermal nanoimprint method for forming the uneven shape, a known method can be used, and examples thereof include one-to-one transfer, step-and-repeat, roll-to-roll, and sheet-to-sheet.

As an example of forming the uneven shape by the thermal nanoimprint method, there is a method of transferring the uneven shape to the thermoplastic polymer layer 4 using the thermal nanoimprint mold 5 shown in FIG.
The mold 5 for thermal nanoimprinting has a concavo-convex shape for thermal nanoimprinting by processing the surface of a flat plate having a material such as silicon oxide, synthetic silica, fused silica, quartz, or nickel by a known semiconductor micromachining technique. It can be prepared by forming a pattern. For example, in the case of silicon oxide having a smooth surface, synthetic silica, fused silica, or quartz, a negative electron beam resist is applied, and electron beam drawing is performed on the electron beam resist by an electron beam drawing apparatus. Thereafter, when development is performed, the resist in the electron beam non-irradiated portion is removed, and the resist in the electron beam irradiated portion on the flat plate remains. By dry etching such as CHF ₃ / O ₂ plasma, SiO ₂ is etched using the negative image of the resist as an etching mask for dry etching. Then, a concave portion can be formed on the surface of the flat plate by immersing in a stripping solution to remove the negative image of the electron beam resist and washing. From the viewpoint of promoting the release property of the resist, a treatment with a release agent such as a fluorocarbon-containing silane coupling agent may be performed.

  The thermal nanoimprint mold 5 thus manufactured can be used as a mold as it is, but after a metal film such as nickel is formed on the surface of the mold, a metal film such as nickel is formed using an electroforming process technique. It is also possible to make a mold coated with a thicker layer. Further, after a metal film such as nickel is formed on the surface of the flat plate by a sputtering method, image formation may be performed using a photoresist or an electron beam resist. Further, by making the metal film thicker by electroforming process technology, and performing surface polishing and resist removal, a more inexpensive nickel mold can be obtained.

  As the thermal nanoimprint apparatus, a known apparatus can be used. For example, what is provided with a heating-cooling part, a pressurization part, and a pressure reduction part can be used. The heating / cooling unit includes a stage including a heater and a water cooling structure, and a substrate having a thermoplastic polymer layer is placed on the stage and heated to soften and cool the thermoplastic polymer layer. In the pressurizing unit, an uneven mold is pressed against the substrate having the resin layer. The uneven shape is transferred by pressurizing the fine uneven structure of the mold onto the softened substrate of the thermoplastic polymer. In the decompression unit, when the mold is pressed against the substrate, the decompression state is set. Thereby, a thermoplastic polymer can be made to follow the uneven | corrugated shape of a mold efficiently.

  As an example of a method for forming a concavo-convex shape by a thermal nanoimprint method, a wet etching substrate (see (b) in FIG. 1) irradiated with ultraviolet rays is placed on a heating and cooling stage of a thermal nanoimprint apparatus. The substrate for wet etching is heated at a temperature 10 to 50 ° C. higher than the glass transition temperature of the thermoplastic polymer forming the thermoplastic polymer layer 4 (heating step). By heating at a temperature higher than the glass transition temperature of the thermoplastic polymer by 10 ° C. or more, the thermoplastic polymer becomes a rubber state and is sufficiently softened, so that the edge portion of the transferred pattern can be prevented from being rounded. Heating at a temperature of 50 ° C. or less from the glass transition temperature of the thermoplastic polymer can prevent the resin from shrinking significantly during cooling after pattern transfer, thus preventing the line width of the formed pattern from thinning. it can.

Next, the mold 5 for thermal nanoimprint having a concavo-convex shape is pressed (pressurization step) and held for a certain time (holding step), whereby the concavo-convex shape of the mold is transferred to the thermoplastic polymer layer 4. Thereby, it becomes the thermoplastic polymer layer 4 which has an uneven | corrugated shape (refer (c) of FIG. 1, (d)).
The pressing pressure of the mold is not particularly limited, but is generally 1 to 100 MPa, preferably 5 to 20 MPa. The pressing time of the mold is generally 6 seconds to 10 minutes, preferably 15 to 120 seconds. It is preferable to maintain a reduced pressure between the mold and the wet etching substrate during pressing. Thereby, since the thermoplastic polymer layer 4 can be efficiently tracked to the fine concavo-convex shape of the mold, patterning with higher accuracy is possible.
Thereafter, the temperature is lowered below the glass transition temperature of the thermoplastic polymer forming the thermoplastic polymer layer 4 (cooling step), and the mold is released from the wet etching substrate (release step). Thereby, the thermoplastic polymer layer 4 to which the uneven shape of the mold is transferred can be obtained.

In the manufacturing method of this invention, the process (1b) or the process (2b) which removes the thermoplastic polymer layer which remains in the said uneven | corrugated shaped recessed part is performed (refer (d) of FIG. 1, (e)).
The method for removing the thermoplastic polymer layer 4 remaining in the concave and convex portions having the concave and convex shape formed by the thermal nanoimprint method is not particularly limited, and can be performed by a known method. For example, UV / ozone etching or oxygen reactive etching can be used. By such a method, since the metal layer 2 is exposed in the concave portion of the thermoplastic polymer layer 4, wet etching and electrolytic plating can be performed with high accuracy. Moreover, when removing the thermoplastic polymer layer 4 of this recessed part, you may remove the ultraviolet-sensitive compound layer 3 of a recessed part simultaneously.

In the production method of the present invention, after the step (1b) or the step (2b), a subtractive method (see (f) and (g) in FIG. 1) or a semi-additive method ((h) in FIG. A substrate having a metal pattern can be manufactured by (ii) and (nu)).
When the subtractive method is employed in the manufacturing method of the present invention, a step (1c) of removing the metal layer under the recess by wet etching is performed (see (f) of FIG. 1).
In the step (1c), the metal pattern 2 is formed by removing the portion of the metal layer 2 exposed in the step (1b) by wet etching.
The wet etching method is not particularly limited, and can be performed using a wet etching solution used in a conventional subtractive method. The type of wet etching solution can be selected according to the type of metal. For example, when the metal is copper, ferric chloride (FeCl ₃ ), cupric chloride (CuCl ₂ ), Cu (NH ₃ ) ₄ Cl ₂ In the case where the metal is chromium, an etching solution mainly containing nitric acid is preferably used.
Specifically, in the wet etching method, a wet etching solution is sprayed and sprayed on the substrate on which the metal layer 2 is exposed at a temperature of room temperature to 50 ° C., or the substrate is immersed in the wet etching solution to etch the metal.

In the production method of the present invention, when the subtractive method is adopted, a step (1d) of peeling the ultraviolet-sensitive compound layer and the thermoplastic polymer layer on the metal layer is performed (see (g) of FIG. 1). A metal pattern can be produced by the step (1d).
In the step (1d), peeling can be performed by, for example, solvent washing or dry etching treatment.
In the solvent washing, the solvent is not particularly limited as long as it can dissolve the ultraviolet-sensitive compound layer and the thermoplastic polymer layer. Specific examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, butyl acetate, ethoxypropyl acetate, ethyl lactate, tetrahydrofuran, chloroform, butyl chloride, benzene, toluene, xylene, dimethylformamide, dimethylacetamide. , Dimethyl sulfoxide, and N-methylpyrrolidone. In order to improve the peeling efficiency, it is preferable to perform ultrasonic cleaning.
Specific examples of the dry etching process include UV / ozone and oxygen reactive etching.

In the manufacturing method of the present invention, when the semi-additive method is employed, a step (2c) of forming a metal pattern by electrolytic plating in the concave portion is performed after the step (2b) (see (h) in FIG. 1).
In the step (2c), the metal pattern can be formed by performing electrolytic plating using the metal layer 2 as an electrode and depositing the plated metal 6.
As the plating metal 6, various plating metals can be used. For example, gold, silver, copper, nickel, aluminum, chromium, zinc, tin, platinum, titanium, and palladium can be mentioned, and silver, copper, nickel, and aluminum are particularly preferable. The plated metal 6 and the metal layer 2 may be the same or different metals.
When depositing the plating metal 6, the recess of the substrate may be protruded and deposited. The plating metal 6 deposited until the concave portion of the substrate protrudes is removed by polishing or etching until the thickness reaches a desired thickness, whereby the thickness of the plating metal 6 can be made uniform.

In the production method of the present invention, when the semi-additive method is employed, after the step (2c), a step (2d) for peeling the ultraviolet-sensitive compound layer and the thermoplastic polymer layer on the metal layer is performed ((( Refer to (i)).
The peeling in the step (2d) can be performed by solvent washing or dry etching treatment, and specific conditions thereof are the same as those in the above-described step (1d) described with reference to FIG. Include conditions.

In the manufacturing method of the present invention, when the semi-additive method is adopted, a step (2e) of removing the metal film in the concave portion by wet etching is performed after the step (2d) (see (N) in FIG. 1). A metal pattern can be produced by the step (2e).
The removal of the metal film in the step (2e) can be performed in the same manner as the above-described step (1c) described with reference to FIG.

  Since a substrate having a metal pattern manufactured by the manufacturing method of the present invention can be formed on a substrate layer with high accuracy even if the metal wiring has a fine shape, the substrate pattern has a predetermined area of 0.01 μm to 10 μm. A large number of metal patterns having fine line widths can be arranged, and as a result, the surface area of the metal wiring can be increased. A substrate having these metal patterns can contribute to the compactness of the device when used in a circuit configuration of the device or the like. Furthermore, it can be applied as a part such as a wiring, a photomask, and a polarizing plate according to the line and space (L / S) interval and shape.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these examples.
Preparation method of substrate layer and metal layer <Preparation of metal substrate a>
A metal substrate a having a copper oxide surface was prepared by subjecting a silicon wafer having a thickness of 0.35 mm to direct-current sputter deposition in the order of 20 nm-thick chromium and 200 nm-thick copper, and exposing to air conditions.

<Preparation of metal substrate b>
A metal substrate b having a copper oxide surface was prepared by electrolessly plating copper having a thickness of 3 μm on polyethylene naphthalate having a thickness of 0.1 mm and exposing it to air conditions.

<Production of metal substrate c>
A metal substrate c having a chromium oxide surface was obtained by sputtering a chromium substrate having a thickness of 80 nm, chromium having a thickness of 62 nm, and chromium oxide having a thickness of 30 nm on the glass substrate having a thickness of 1 mm.

Preparation method of UV-sensitive compound layer <Dipping method>
10.0 mg of 4- (3-trimethoxysilylpropyloxy) -benzophenone was dissolved in 100 mL of toluene to prepare a toluene solution of an ultraviolet-sensitive compound. Each metal substrate having a substrate layer and a metal layer was subjected to UV / ozone treatment for 15 minutes (PL16-116, manufactured by Sen Special Light Source Co., Ltd.) to produce a substrate having a hydroxyl group formed on the surface. Subsequently, the substrate was placed in a solution of an ultraviolet sensitive compound and heated at 100 ° C. for 1 hour. The substrate was taken out and washed with clean toluene to obtain a substrate having an ultraviolet-sensitive compound layer. The formation of the UV-sensitive compound layer was confirmed by a surface analysis by XPS measurement and a Si peak derived from a silane coupling group.

<Gas phase method>
Each substrate having a substrate layer and a metal layer was treated with UV / ozone for 15 minutes to form hydroxyl groups on the surface. Each metal substrate on which a hydroxyl group was formed and a sample tube containing 10.0 mg of 4- (3-trimethoxysilylpropyloxy) -benzophenone were placed in a Teflon (registered trademark) container and purged with nitrogen. After nitrogen substitution, the container was heated at 150 ° C. for 2 hours to modify the surface, and a substrate having an ultraviolet-sensitive compound layer was obtained. The formation of the UV-sensitive compound layer was confirmed by a surface analysis by XPS measurement and a Si peak derived from a silane coupling group.

Preparation method of thermoplastic polymer layer A toluene solution of 5% by mass of polystyrene (manufactured by Sigma-Aldrich, weight average molecular weight = 45000, glass transition temperature = 93 ° C.) or polyvinyl toluene (weight average molecular weight = 25000) is prepared. Spin coating was performed on the substrate at 3000 rpm for 30 seconds to form a 250 nm-thick thermoplastic polymer layer, and a wet etching substrate was produced.

Examples 1-1 to 1-4
Preparation of wet etching substrate (copper substrates 1 to 3 and chromium substrate 1) Under the conditions shown in Table 1, a substrate layer, a metal layer, an ultraviolet-sensitive compound layer, and a thermoplastic polymer layer were formed, and wet etching copper was formed. A substrate (copper substrates 1 to 3) and a chrome substrate for wet etching (chrome substrate 1) were produced.

Example 1-5
Preparation of wet etching substrate (copper substrate 4) UV-sensitive compound by immersion method using 4- (10-trimethoxysilyldecyloxy) -benzophenone instead of 4- (3-trimethoxysilylpropyloxy) -benzophenone A copper substrate for wet etching (copper substrate 4) was obtained under the same conditions as in Example 1-1 except that the layer preparation operation was performed.

Example 1-6
Preparation of Wet Etching Substrate (Copper Substrate 5) Example 1 using a methyl ethyl ketone solution of 15% by mass of polymethyl methacrylate (manufactured by Sigma-Aldrich, weight average molecular weight = 20000) instead of 5% by mass of polystyrene in toluene -1 was performed to obtain a wet etching substrate (copper substrate 5) having a polymethyl methacrylate layer having a thickness of 1 μm on the thermoplastic polymer layer.

Comparative Example 1-1
Preparation of wet etching substrate without copper-sensitive compound layer (copper substrate 6) Wet etching without UV-sensitive compound layer under the same conditions as in Example 1-1, except that the UV-sensitive compound was not modified by the immersion method. A copper substrate for copper (copper substrate 6) was produced.

Comparative Example 1-2
Preparation of wet etching substrate (chrome substrate 2) using thiol group-containing benzophenone compound Using 4- (10-mercaptodecyloxy) -benzophenone instead of 4- (3-trimethoxysilylpropyloxy) -benzophenone A wet etching chrome substrate (chromium substrate 2) was obtained under the same conditions as in Example 1-4, except that the operation of producing the ultraviolet-sensitive compound layer by a vapor phase method was performed. Further, after the surface modification operation of the thiol group-containing benzophenone compound, surface analysis was performed by XPS measurement, and it was confirmed that the thiol group-containing benzophenone compound layer was not formed because the peak of the thiol group did not appear.

Comparative Example 1-3
Production of wet etching substrate without gold-sensitive compound layer (gold substrate 1) The same conditions as in Example 1-1 except that a gold substrate produced by sputtering gold instead of copper on a silicon wafer was used. Thus, a gold substrate for wet etching (gold substrate 1) was produced. Further, after the surface modification operation of the UV-sensitive compound, surface analysis was performed by XPS measurement, and it was confirmed that the UV-sensitive compound layer was not formed because there was no Si peak.

  Among the UV-sensitive compound layers in Tables 1 and 2, silane coupling agent type 1 is 4- (3-trimethoxysilylpropyloxy) -benzophenone, and silane coupling agent type 2 is 4- (10-trimethoxysilyldecyl). This shows that oxy) -benzophenone and thiol group type 4- (10-mercaptodecyloxy) -benzophenone were used. In the thermoplastic polymer layer, PS indicates that polystyrene is used, PVT indicates that polyvinyl toluene is used, and PMMA indicates that polymethyl methacrylate is used.

Examples 2-1 to 2-6
Production of each substrate (copper substrates 1A to 5A, chrome substrate 1A) subjected to ultraviolet irradiation Each substrate for wet etching (copper substrates 1 to 5, chrome substrate 1) was irradiated with ultraviolet rays. For the ultraviolet irradiation, Supercure 202S manufactured by Mitsunaga Electric Manufacturing Co., Ltd. was used, and the irradiation intensity was 13 W / cm ² at an observation wavelength of 254 nm. Exposure exposure amount 1 J / cm ² UV at 254nm only copper substrate 2, other substrates was 2J / cm ^2.
Each substrate subjected to ultraviolet irradiation is annealed at 180 ° C. for 1 minute to obtain a copper substrate 1A (Example 2-1), a copper substrate 2A (Example 2-2), and a copper substrate 3A (Example 2- 3) A chrome substrate 1A (Example 2-4), a copper substrate 4A (Example 2-5), and a copper substrate 5A (Example 2-6) were obtained.

Example 3-1
Production of Metal Pattern by Subtractive Method A thermal nanoimprint method was applied to the copper substrate 1A to produce an uneven shape.
The mold for thermal nanoimprinting has a pattern of 1 μm line & space (1: 1) and 2 μm line & space (1: 1) with a depth of 250 nm. A silicon mold surface-treated with a trade name “OPTOOL DSX”) was used.
As the thermal nanoimprint apparatus, NM-400 manufactured by Myeongchang Kiko was used.
Thermal nanoimprint is a heating process (pressing force 0N (0 MPa), mold temperature 160 ° C., time 60 seconds), mold pressing process (pressing force 3000 N (7.5 MPa), mold temperature 160 ° C., time 60 seconds). , Mold holding step (pressing force 3000 N (7.5 MPa), mold temperature 160 ° C., time 180 seconds), cooling step (pressing force 3000 N (7.5 MPa), mold temperature 35 ° C., time 60 seconds), mold The mold release step (pressing force 0 N (0 MPa), mold temperature 35 ° C., time 60 seconds) was performed under the conditions consisting of five stages.
The obtained uneven shape was observed and evaluated with an optical microscope. A copy of this optical microscope image is shown in FIG.
As can be seen from FIG. 2, 2 μm and 1 μm polystyrene irregularities are formed in the line & space 1: 1.

Subsequently, the substrate on which the concavo-convex shape was formed by the thermal nanoimprint method was subjected to UV / ozone treatment for 15 minutes, and the thermoplastic polymer layer in the concave portion was removed. Then, the metal layer which is not coat | covered with the thermoplastic polymer layer was removed using the wet etching liquid (ADEKA company make, brand name "Adeka super Kermica WAD-5001E"), and the metal pattern was formed. Furthermore, the thermoplastic polymer layer which coat | covered the metal pattern was removed using chloroform (made by Wako Pure Chemical Industries), and the metal pattern was obtained.
The metal pattern formed on the substrate was observed with an optical microscope to evaluate the pattern shape. A copy of this optical microscope image is shown in FIG.
From FIG. 3, it can be seen that 2 μm and 1 μm copper irregularities are formed in the line and space 1: 1.

Examples 3-2 to 3-5
Production of Metal Pattern by Subtractive Method A metal pattern was produced in the same manner as in Example 3-1, except that a metal pattern was produced under the conditions shown in Table 3. The results are shown in Table 3.
In Table 3, used substrate abbreviations represent the abbreviations of the above-mentioned wet etching substrates. The ones that were irradiated with ultraviolet rays were indicated by ◯, the ones that were not irradiated were indicated by ×. As in Example 3-1, from the image obtained by the above, a thermoplastic polymer layer concavo-convex pattern and a metal concavo-convex pattern corresponding to the mold for thermal nanoimprinting were obtained. A pattern having a defect as in the case of No. 1 was evaluated as x.

Example 3-6
Fabrication of metal pattern by subtractive method A copper substrate 5A is used instead of the copper substrate 1A, and a thermal nanoimprint mold having the same line and space of 1 μm depth is used instead of a thermal nanoimprint mold having a depth of 250 nm. Except that the holding step was changed from 180 seconds to 300 seconds, the same operation as in Example 3-1 was performed, and a metal pattern was produced and evaluated.
The results are shown in Table 3. As a result of observing and evaluating the concavo-convex pattern and metal pattern of the obtained thermoplastic polymer with an optical microscope, the concavo-convex shape corresponding to the mold for thermal nanoimprinting was formed as in Example 3-1.

Comparative Example 3-1
Production of Metal Pattern by Subtractive Method A metal pattern was produced in the same manner as in Example 3-1, except that a metal pattern was produced under the conditions shown in Table 4, and was similarly evaluated. The results are shown in Table 4. 4 and 5 show a copy of an optical microscope image of the polystyrene pattern after thermal nanoimprinting and the metal pattern after wet etching and removal of the thermoplastic polymer layer.
4 and 5, since the adhesion between the metal layer and the thermoplastic polymer layer was insufficient, defects were observed in the polystyrene pattern and the copper pattern after the thermal nanoimprint molding. Further, it was found that the metal pattern was also defective.

Comparative Examples 3-2 and 3-3
Production of Metal Pattern by Subtractive Method A metal pattern was produced in the same manner as in Example 3-1, except that a metal pattern was produced under the conditions shown in Table 4, and was similarly evaluated. The results are shown in Table 4.

Example 4-1
Preparation of metal pattern by semi-additive method In the same manner as in Example 3-1, formation of uneven shape by thermal nanoimprint method on copper substrate 1A and removal of the thermoplastic polymer layer of the recess by UV / ozone treatment went.
Next, electrolytic plating was performed using a copper substrate as a cathode electrode in a copper sulfate plating bath, and pattern plating with a copper plating thickness of 200 nm was performed. Subsequently, the polystyrene pattern was removed by washing with chloroform. Furthermore, the metal layer of the recessed part was etched using a wet etching solution (trade name “ADEKA SUPER KEMIKA WAD-5001E” manufactured by ADEKA) to form a metal pattern.
As a result of observing the obtained metal pattern with an optical microscope, it was found that metal patterns having a height of 200 nm, a line and space of 1: 1, and 2 μm and 1 μm were obtained.

Comparative Example 4-1
Production of metal pattern by semi-additive method A metal pattern was produced in the same manner as in Example 4-1, except that copper substrate 1 that was not irradiated with ultraviolet rays was used instead of copper substrate 1A.
As a result of observing the obtained metal pattern with an optical microscope, there was a defect in the polystyrene pattern after the thermal nanoimprint molding, so that a defect pattern in which metal was originally deposited in a portion without the metal pattern was obtained.

1: substrate layer 2: metal layer having a metal oxide surface 3: UV-sensitive compound layer 4 represented by formula (1) 4: thermoplastic polymer layer 5: mold for thermal nanoimprint 6: plated metal

Claims (8)

A substrate for wet etching having a substrate layer, a metal layer having a metal oxide surface, an ultraviolet-sensitive compound layer represented by formula (1), and a thermoplastic polymer layer in this order.

(In the formula, R1 to R3 represent a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a hydrocarbon group having 1 to 6 carbon atoms linked by an oxygen atom or a nitrogen atom. X represents O, OCO, COO, NH represents NHCO, m represents an integer of 1 to 20. R4 represents a hydrocarbon group having 1 to 3 carbon atoms, Y represents an alkoxy group having 1 to 3 carbon atoms or a halogen atom; Represents an integer of 3.)   The metal layer having the metal oxide surface is at least one selected from the group consisting of silver having a silver oxide surface, copper having a copper oxide surface, aluminum having an aluminum oxide surface, and chromium having a chromium oxide surface. The substrate for wet etching according to claim 1, comprising a metal layer having a metal oxide.   The substrate for wet etching according to claim 1 or 2, wherein the thermoplastic polymer of the thermoplastic polymer layer comprises at least one thermoplastic polymer selected from the group consisting of polystyrene, polyvinyl toluene, and cyclic polyolefin. .   The substrate layer is made of silicon, glass, quartz, alumina, barium titanate, epoxy resin, phenol resin, polyimide resin, polyester resin, polyphenylene oxide resin, a laminate of two or more of these, and a composite of two or more of these. The substrate for wet etching according to any one of claims 1 to 3, comprising a material selected from the group consisting of:   5. A substrate for wet etching, wherein at least a portion of the substrate for wet etching according to claim 1 is irradiated with ultraviolet rays. A method for producing a substrate having a metal pattern, wherein at least the following steps are performed on the substrate for wet etching according to claim 5.
(1a) a step of forming a concavo-convex shape by a thermal nanoimprint method,
(1b) removing the thermoplastic polymer layer remaining in the concave-convex shaped recess,
(1c) removing the metal layer under the recess by wet etching;
(1d) A step of peeling off the ultraviolet-sensitive compound layer and the thermoplastic polymer layer on the metal layer. A method for producing a substrate having a metal pattern, wherein at least the following steps are performed on the substrate for wet etching according to claim 5.
(2a) a step of forming an uneven shape by a thermal nanoimprint method,
(2b) removing the thermoplastic polymer layer remaining in the concave-convex recess,
(2c) forming a metal pattern by electrolytic plating in the recesses,
(2d) a step of peeling off the UV-sensitive compound layer and the thermoplastic polymer layer on the metal layer,
(2e) A step of removing the metal film in the recess by wet etching.   A substrate having a metal pattern having a line width of 0.01 to 10 μm, manufactured by the manufacturing method according to claim 6.

Images