JP6301672B2 - Method for manufacturing inverted structure and substrate with concavo-convex structure using the same - Google Patents

Description

  The present invention relates to a method for manufacturing an inverted structure and a substrate manufactured using the same.

  In recent years, with increasing demands for higher density and higher integration in the fields of semiconductors, optical / magnetic recording, and the like, a technology for processing fine concavo-convex structures of about several hundreds to several tens of nanometers or less is essential. Therefore, in order to realize such fine concavo-convex structure processing, elemental technologies in each process such as a mask / stepper, exposure, resist material, etc. are actively studied.

  The fine concavo-convex structure is generally produced using a photoresist. This photoresist is roughly classified into a positive type resist and a negative type resist. When the positive resist is exposed, the solubility in the developer increases, and the exposed portion is removed to form an uneven structure. Development is mainly carried out with an alkaline solution. On the other hand, when the negative resist is exposed, the solubility in the developing solution decreases, and the exposed portion remains to form a concavo-convex structure. Development is mainly performed with an organic solvent. This negative resist is difficult to miniaturize because an organic solvent swells the resist during development. In addition, due to the large amount of organic solvent used, it has not been used much in recent years.

  However, there is a high demand for a pattern shape of a concavo-convex structure produced with a negative resist, such as a pattern shape of a fine concavo-convex structure that can be produced only with a negative resist, or a process using both a positive resist and a negative resist. In view of this, studies have been made on the production of an inverted structure in which the pattern shape of the concavo-convex structure produced using a positive resist is inverted. For example, a method of obtaining a second reverse pattern mask by embedding a resin in an opening of a first mask made of a photoresist and removing the first mask is disclosed (for example, see Patent Document 1). . Furthermore, a method of embedding an inorganic film instead of a resin in order to increase the dry etching resistance of the second inversion pattern has been disclosed (for example, see Patent Document 2). However, it has been difficult to embed a material uniformly in the opening of the first mask.

  On the other hand, as a method that does not pass through the embedding process, the thin film exposed to the opening of the first mask is subjected to surface treatment by dry etching using a reactive gas, and the first mask is removed, and the surface treated thin film portion. A method for obtaining a second mask by selectively etching a thin film using as a mask is disclosed (for example, see Patent Document 3).

Japanese Patent No. 5003279 JP 63-32935 A Japanese Unexamined Patent Publication No. Sho 63-113457

  However, in the method described in Patent Document 3, when the thin film exposed in the opening of the first mask is surface-treated, the first mask is simultaneously dry-etched, so that the first mask is completed before the second mask is completed. The mask 1 is gradually etched and its shape changes over time. Therefore, there is a problem that the pattern shape of the first mask cannot be faithfully reversed to the pattern shape of the second mask. In addition, since the first mask has disappeared at the time of forming the second mask, the entire surface is processed only by slightly increasing the surface treatment time, making it difficult to produce the second mask itself. There was a problem of becoming.

  The present invention has been made in view of such a point, and a second mask in which the pattern shape of the first mask is faithfully reversed is produced, and unevenness having an inverted structure by etching using the second mask. It is an object of the present invention to provide an inverted structure body and a substrate with a concavo-convex structure from which a substrate with structure can be obtained.

In the manufacturing method of the inversion structure according to the present invention, a plurality of convex portions made of resist are provided on a metal thin film provided on a substrate, and the metal thin film is exposed inside the convex portions. A step of forming a first mask having a concavo-convex structure composed of a plurality of concave portions and the first mask are used, and the metal thin film is not reactive to the resist. by the action of certain reactive gas, and forming a reforming target layer and facilities surface treatment in a partial region of the metal thin film exposed in the recess of the metal thin film having the to-be-reformed layer a partial area as a mask, other areas where the surface treatment is not applied selectively removing the metal thin film, the second is a part of a region of the metal thin film having the modified layer a mask, a front Symbol metal thin film wherein the substrate is exposed by removing regions, Configured, and obtaining an inverted structure corresponding to the concavo-convex structure, using said second mask, the substrate comprising the steps of etching, the resist is used in the course of the surface treatment A heat-reactive resist containing an inorganic material that has etching resistance to the reactive gas is used .

  According to this configuration, an inverted structure can be formed by faithfully inverting the pattern shape of the first mask, so that the surface treatment of the metal thin film is performed on the substrate by etching using the second mask as a second mask. An inversion structure can be formed.

  In the manufacturing method of the inversion structure of the present invention, it is preferable that the pitch of the uneven structure is 1 nm or more and 10 μm or less.

  In the method for producing an inverted structure according to the present invention, the resist is preferably a heat-reactive resist containing an inorganic material.

  In the inversion structure manufacturing method of the present invention, the mask includes a mold having an inversion structure corresponding to the concavo-convex structure, and the resist filled in the recess of the inversion structure of the mold. It is preferable to obtain the sheet for use by laminating the sheet on the substrate and peeling the mold.

  In the manufacturing method of the inversion structure of this invention, it is preferable to further comprise the process of removing the residual film of the said mask obtained by peeling the said mold.

  In the method for manufacturing an inverted structure according to the present invention, it is preferable to simultaneously perform the step of removing the residual film of the mask obtained by peeling the mold and the step of performing the surface treatment on the metal thin film.

  In the manufacturing method of the inversion structure of this invention, it is preferable that the said metal thin film is chromium, titanium, iron, cobalt, nickel, manganese, aluminum, or platinum.

  In the inversion structure manufacturing method of the present invention, the surface treatment is preferably performed using an oxygen-based gas.

  In the inversion structure manufacturing method of the present invention, the substrate is preferably made of quartz, sapphire, silicon, silicon nitride, or gallium nitride.

  The substrate with a concavo-convex structure according to the present invention is a reversal structure manufactured by the method for manufacturing a reversal structure, wherein the partial region where the surface treatment of the metal thin film constituting the reversal structure is performed is used as a mask. An uneven structure corresponding to the inverted structure is formed by etching the substrate.

  According to the present invention, since the inverted structure can be formed by faithfully reversing the pattern shape of the first mask, etching is performed on the substrate by etching using the surface-treated region of the metal thin film as the second mask. An inversion structure can be formed.

It is explanatory drawing of the manufacturing method of the inversion structure which concerns on this Embodiment, and a board | substrate with an uneven structure. It is a cross-sectional schematic diagram which shows the uneven structure which concerns on this Embodiment. It is a cross-sectional schematic diagram which shows the structure of the sheet | seat for mask transfer which concerns on this Embodiment.

  As a method of obtaining an inverted structure having a desired pattern as a result of intensive studies and experiments conducted to solve such problems, the present inventors have used a resist having an opening with a desired pattern as a first mask as a metal thin film. When the surface treatment is performed, the metal thin film can be surface-treated with the resist remaining by using a reactive gas having resist resistance to etching, so that the first mask shape can be faithfully inverted to the second mask shape. The headline and the present invention were completed.

Embodiments of the present invention will be specifically described below.
FIG. 1 is an explanatory diagram of a method for manufacturing an inversion structure according to the present embodiment. First, as shown in FIG. 1A, a metal thin film 12 formed on a substrate 11 is prepared.

  Next, as shown in FIG. 1B, a concavo-convex structure 13 having a pitch of 1 nm to 10 μm is formed. The concavo-convex structure 13 (also referred to as a first mask) is formed of a resist, and includes a plurality of convex portions 14 and a plurality of concave portions 15 provided between the convex portions 14. A part of the surface of the metal thin film 12 is exposed inside the recess 15.

  Here, the resist is characterized in that it has an etching resistance to a reactive gas used for the surface treatment of the metal thin film 12 to be described later and is not substantially etched in the course of the surface treatment. “Substantially not etched” means that the resist volume remains 50% or more before and after the surface treatment, preferably 70% or more, more preferably 90% or more, and still more preferably 95%. More preferably, it is 100% or more (a state where etching is not performed). By maintaining the resistance of the resist to the reactive gas within the above range, the shape of the first mask 13 can be faithfully inverted to the shape of the inversion structure 17 described later.

  Next, as shown in FIG. 1C, surface treatment is performed using the first mask 13 to modify a partial region on the surface of the metal thin film 12. Specifically, the surface treatment of the metal thin film 12 is reactive to the metal thin film 12, but not etched, using the convex portion 14 of the concavo-convex structure 13 as a first mask, and to the resist. Is performed by reacting a reactive gas which has no reactivity and the resist has etching resistance. As a result, the modification occurs as described in the partial region of the metal thin film 12 exposed in the recess 15 of the first mask 13, and the modified layer 16 is formed.

  In the present embodiment, the surface treatment of the metal thin film 12 can be performed by applying a general dry etching treatment method.

  Next, using the partial region of the metal thin film 12 having the modified layer 16 as a mask, the other region of the metal thin film 12 that has not been subjected to the surface treatment is selectively removed by etching. As a result, as shown in FIG. 1D, a part of the region 12 a having the layer to be modified 16 subjected to the surface treatment of the metal thin film 12, and a region 11 a where the metal thin film 12 is removed and the substrate 11 is exposed. The inversion structure 17 corresponding to the concavo-convex structure 13 is obtained. The substrate 11 having such an inversion structure 17 is referred to as an inversion structure 18. In addition, a partial region 12 a of the metal thin film 12 having the modified layer 16 constituting the inversion structure 17 is also referred to as a second mask.

  In the method for manufacturing the inversion structure 18 according to the present embodiment as described above, the reactive gas having resistance of the resist constituting the first mask 13 is used for the surface treatment of the metal thin film 12, so that the surface Since the first mask 13 remains substantially unremoved in the process, the pattern shape of the first mask 13 is faithfully inverted to the pattern shape of the layer to be modified 16, and the pattern of the layer to be modified 16 The shape is faithfully reflected in the inversion structure 17.

  The substrate with concavo-convex structure 20 can be manufactured using the inverted structure 18 obtained as described above. When the substrate 11 is etched using the second mask 12a as shown in FIG. 1E, a concavo-convex structure 19 is formed on the substrate 11 that faithfully reverses the pattern shape of the concavo-convex structure 13 as shown in FIG. 1F. . The substrate 11 having such a concavo-convex structure 19 is referred to as a concavo-convex structure-attached substrate 20. Note that the first mask 13 and the second mask 12a can be removed as necessary. The method for removing the mask can be selected from wet etching or dry etching. For example, when removing the first mask 13, it is only necessary to carry out an etching condition in which the first mask 13 is etched but the second mask 12 a is not etched. When removing the second mask 12 a The second mask 12a is etched but the substrate 11 is not etched.

  Hereinafter, the manufacturing method of the inversion structure 18 according to the present embodiment will be described in more detail.

  First, as shown in FIG. 1A, in the present embodiment, the metal thin film 12 is formed by forming a thin film made of a metal material on a substrate 11.

  As the substrate 11, a flat substrate, a cylindrical substrate (a sleeve substrate, a roll substrate, a drum substrate), a lens substrate, or the like can be used. Particularly in the case of a cylindrical substrate or a lens shape, it is suitable for a mold for nanoimprint.

  The material of the substrate 11 is not particularly limited, but it is possible to use a metal, glass, ceramics, or the like that is rich in workability. Specifically, aluminum, copper, titanium, SUS, glass, quartz, sapphire, silicon, silicon nitride, gallium nitride, or those plated with chrome may be mentioned. Quartz, sapphire, silicon, silicon nitride, More preferably, it is selected from any of gallium nitride. Quartz is suitable as the mold for nanoimprinting.

  Luminous efficiency of a nitride semiconductor element and an oxide semiconductor element used for a light-emitting device greatly depends on crystallinity, defects, and dislocations (amount and size) of the nitride film and the oxide film. Therefore, gallium nitride substrates, sapphire substrates, silicon nitride substrates, and inexpensive silicon substrates are often used to obtain higher quality nitride films and oxide films in the manufacturing process of nitride semiconductor elements and oxide semiconductor elements. It is used.

  In recent years, various studies have been made to minimize defects and dislocations resulting from a difference in lattice constant between a film crystal and a substrate. For example, it has been reported that a substrate having a concavo-convex structure on the surface is advantageous for epitaxial growth with few defects and dislocations. On such a substrate, the gallium nitride compound is epitaxially grown so as to fill the concave and convex grooves. Accordingly, a film including a region with a low dislocation density can be manufactured. According to a light emitting device manufactured using a crystal layer having a low dislocation density manufactured by this method, the amount of light generated in the light emitting layer can be increased, that is, the luminous efficiency can be increased by increasing the internal quantum efficiency. it can.

  Further, by producing a light emitting element using a laminate in which a film epitaxially grown on the concavo-convex structure on the surface of the substrate is formed, it is possible to increase the efficiency of extracting light emitted from the light emitting layer, so-called external quantum efficiency. it can. Thereby, the luminous efficiency of the light emitting element can be increased.

  The metal thin film 12 is not particularly limited as long as the metal thin film 12 can be surface-treated in the surface treatment step, and a general material can be used. The material used for the metal thin film 12 can be selected in consideration of the reactivity to the reactive gas used for the surface treatment and the resistance to etching of the metal thin film 12 using a part of the surface-treated region as a mask. .

  That is, the etching can be broadly classified into wet etching and dry etching, and the wet etching resistance varies depending on the etching solution used for etching. Therefore, the material of the metal thin film 12 can be selected with reference to the chemical handbook.

  On the other hand, the dry etching resistance varies depending on the etching gas used. For example, when a fluorine-based gas is used as the etching gas, as disclosed by the present inventors (International Publication No. 2010/044400 pamphlet), the main fluoride has a boiling point of 200 ° C. or higher in terms of a metal. When an oxygen-based gas is used as an etching gas, there is no particular limitation as long as the metal thin film 12 is other than a metal (Mo, In, P) that sublimes (vaporizes) by oxidation. The material used for the metal thin film 12 according to the present embodiment is preferably selected from Group III to Group XIV materials, more preferably from Group III, since Group I and Group II are very oxidized and difficult to handle. Examples include Group XIII materials.

  The material used for the metal thin film 12 according to the present embodiment is more preferably chromium, titanium, zirconium, hafnium, manganese, iron, cobalt, nickel, copper, from the viewpoint of dry etching resistance and sputtering film formation described later. Manganese, aluminum, or platinum is exemplified, and most preferably, chromium, titanium, iron, cobalt, nickel, manganese, aluminum, or platinum is exemplified.

  The metal thin film can be formed by using, for example, a sputtering method, a vapor deposition method, or a CVD method. Since fine pattern processing at a level of several tens of nanometers is performed, depending on the fine pattern size, the film thickness, film thickness distribution, and surface unevenness may be very greatly affected. Therefore, in order to reduce these effects as much as possible, the sputtering method, the evaporation method, the CVD method, etc. are used rather than the film forming method by the coating method or the spray method which is somewhat difficult to control the film thickness and the uniformity of the film thickness. It is preferable to form a film by a film forming method. Among these, the sputtering method is particularly preferable from the viewpoint of controlling the film thickness, film thickness uniformity, and surface roughness (unevenness).

  Next, as shown in FIG. 1B, a method for forming the uneven structure 13 in the present embodiment will be described in detail below.

  The pitch of the concavo-convex structure 13 of the present invention is preferably 1 nm or more and 10 μm or less. FIG. 2 is a schematic cross-sectional view showing the concavo-convex structure according to the present embodiment. In the concavo-convex structure 13 shown in FIG. 2, the concavo-convex structure 13 including a plurality of convex portions 14 and concave portions 15 is formed. In the present embodiment, the distance between adjacent convex portions 14 of the concavo-convex structure 13 is referred to as a pitch P. In FIG. 2, the distance between the illustrated right ends of the adjacent convex portions 14 is the pitch P. However, the distance between the illustrated left ends of the adjacent convex portions 14 may be the pitch P, and the upper surface of each adjacent convex portion 14. The distance between the centers in the width direction can be the pitch P. In the present invention, as shown in FIG. 2, the pitch P is not necessarily the pitch P between the adjacent convex portions 14 of the concavo-convex structure 13, and may be the pitch between the adjacent concave portions 15. In FIG. 2, the substrate 11 is flat and has a pitch P. However, when a roll-shaped substrate is used, the peripheral surface of the concavo-convex structure 13 is a curved surface, and the pitch P between the convex portions 14 at that time is shown. For example, a distance P ′ between the right end portions 13a (which may be the left end portion or the center of the width) linearly on the upper surface of adjacent convex portions 14 corresponds to the pitch. Since the diameter φ of the roll-shaped substrate is on the order of cm or more and the pitch P ′ is on the order of nm to μm, the pitch P ′ is not affected by the curvature, and the pitch P ′ is not affected by the height of the convex portion 14. It is possible to obtain a constant pitch P ′ (pitch error is about 0.1% or less between the upper surface side and the lower surface side) regardless of the measurement position.

  In the present embodiment, the pattern shape of the concavo-convex structure 13 is not particularly limited, and examples thereof include a line and space shape, a dot shape, a long hole shape, and a mixed shape thereof. Examples of the cross-sectional structure of the concavo-convex structure 13 include a rectangular shape, a triangular shape, a dome shape, and a lens shape.

  In the present embodiment, it is preferable to use a thermal reaction resist material containing an inorganic material.

The inorganic heat-reactive resist material is not particularly limited. For example, as disclosed by the present inventors (WO 2010/044400 pamphlet), the element whose boiling point of the main fluoride is 200 ° C. or higher is used. Inorganic heat-reactive resist materials containing at least one kind, WOx, MoOx, WMoOx, AgOx, PtOx, and the like can be used. Among them, CuO, CuO—SiO ₂ , CuO—Si, Mn ₂ O ₃ , Mn ₂ O ₃ —SiO ₂ , Mn ₂ O ₃ —Si, Co ₃ O ₄ —SiO ₂ , Co ₃ O ₄ —Si, GaSb, An inorganic thermal reaction type resist material containing at least one element having a boiling point of 200 ° C. or more represented by a main fluoride represented by CrOx and CrOx-SiO ₂ and being a decomposable oxide material or a phase-change composite metal material is preferable. When it is desired to satisfactorily form the fine concavo-convex structure 13, it is particularly preferable to include CuO—SiO ₂ , CuO—Si, and CrOx—SiO ₂ . When an element having a boiling point of 200 ° C. or higher is used, the main fluoride has resistance to dry etching using a fluorine-based gas, and thus can be suitably used for surface treatment of the metal thin film 12 with fluorine gas.

  Further, in the present embodiment, the concavo-convex structure 13 is a mask transfer sheet comprising a mold having a reversal structure corresponding to the concavo-convex structure 13 and a resist filled in a concave portion of the reversal structure of the mold. It is preferable to obtain by exfoliating and peeling the mold.

  The mask transfer sheet according to the present embodiment will be described with reference to FIG. FIG. 3 is a schematic cross-sectional view showing the structure of the mask transfer sheet according to the present embodiment. First, as shown in FIG. 3A, a mask transfer sheet 30 is prepared. The mask transfer sheet 30 includes a resin mold 31 and a first mask layer 32 and a second mask layer 33 filled in the recesses of the resin mold 31. Here, the 1st mask layer 32 is arrange | positioned in order to raise the tolerance with respect to the dry etching at the time of the surface treatment of the metal thin film 12, and the below-mentioned residual film removal. As a material of the first mask layer 32, for example, an inorganic material composed of a sol-gel material or the like is suitable. On the other hand, as a material of the resin mold 31 and the second mask layer 33, in terms of bonding properties (adhesiveness, flexibility, etc.), function imparting properties (etching resistance, surface energy control, etc.), ease of sheet production, and the like. For example, a UV curable resin is suitable.

  The mask transfer sheet 30 having such a configuration is bonded to the surface of the metal thin film 12 on the substrate 11 with the second mask layer 33 side facing, as shown in FIG. 3A.

Subsequently, as shown in FIG. 3B, after the resin mold 31 is peeled off, the remaining film at the bottom of the recess of the second mask layer 33 is removed by O ₂ ashing, and the metal thin film 12 is removed as shown in FIG. 3C. The surface of was partially exposed.

The O ₂ ashing condition is not particularly limited as long as it can introduce a chlorofluorocarbon gas in a vacuum, can form plasma, and can be etched. A commercially available dry etching apparatus, CCP (capacitive coupling type) An apparatus, an ICP (inductively coupled plasma type) apparatus, an ECR (electron cycloton resonance type) apparatus, or the like can be used. What is necessary is just to select suitably the time which performs dry etching process, electric power, the gas seed | species containing oxygen gas, etc. according to the material used for the 2nd mask layer 33, thickness, and an etching rate. It should be noted that the accuracy in removing the remaining film of the second mask layer 33 is increased using the first mask layer 32 as a mask, and the pattern shape of the first mask layer 32 is faithfully matched to the second mask 12a shown in FIG. 1E. For reversal, an ICP device or the like is preferable. For example, the pressure is 5 Pa or less, and 3 Pa or less is more preferable. The power is preferably selected according to the device size.

  Next, a method for bonding the mask transfer sheet 30 will be described. For example, while heating the board | substrate 11 and the metal thin film 12, what is necessary is just to pressure-bond the sheet | seat 30 for mask transfer, and according to the kind of 2nd mask layer 33, a general bonding method can be selected.

  As described above, it is possible to form the concavo-convex structure 13 according to the present embodiment by using the mask transfer sheet 30, and in particular, it is necessary to form a mask for each substrate by using the mask transfer sheet. There are also advantages such as mass production, cost reduction, and production time reduction.

  Next, as shown in FIG. 1C, a process of performing a surface treatment on a partial region of the metal thin film 12 will be described. In the present invention, the surface treatment of a part of the metal thin film 12 means that the metal thin film 12 in a region not covered with the first mask 13 is surface-modified with a reactive gas. Here, the surface modification refers to, for example, oxidation, sulfidation, fluorination, nitridation, hydrogenation, and chlorination, and the reactive gases used are oxygen-based gas, sulfur-based gas, fluorine-based gas, nitrogen, respectively. It can be implemented by using a system gas, a hydrogen-based gas, and a chlorine-based gas.

Examples of the gas that can be suitably used in the present invention include an oxygen-based gas, and oxygen or the like can be added as a main component and argon or the like can be added. As the sulfur-based gas, any one of H ₂ S and SF ₆ or a mixture thereof can be used as a main component, and argon or the like can be added thereto. The fluorine-based gas is CF ₄ , CHF ₃ , CH ₂ F ₂ , C ₂ F ₆ , C ₃ F ₈ , C ₄ F ₆ , C ₄ F ₈ , C ₄ F ₁₀ , C ₅ F ₁₀ , SF ₆ , CCl Argon or the like can be added to any one of ₂ F ₂ or a mixture of at least two of them as a main component. The nitrogen-based gas can contain nitrogen as a main component and argon or the like in addition. The hydrogen-based gas can contain hydrogen as a main component and argon or the like in addition. The chlorine-based gas can contain chlorine as a main component and argon or the like.

  In the surface treatment using a fluorine-based gas, depending on the treatment conditions, the fluorocarbon film is deposited (deposited) on the metal thin film 12, but this fluorocarbon film has poor adhesion to the metal thin film 12, and therefore serves as a mask. Hard to function. Therefore, it is preferable to exclude the deposition of fluorocarbon on the metal thin film 12 from the category of the surface treatment on the metal thin film 12 in the present invention.

  In the surface treatment of the metal thin film 12 according to the present embodiment, the first mask 13 having high etching resistance against the reactive gas is used, and therefore, the surface treatment is not particularly affected by the processing conditions. Fluorine-based gas or nitrogen-based gas is preferably used, more preferably oxygen-based gas or nitrogen-based gas is used, and most preferably oxygen-based gas is used.

  When the first mask 13 contains an inorganic material, it is not etched at all by the oxidation by the dry etching process using an oxygen-based gas. Therefore, the metal thin film 12 has a shape in which the concavo-convex structure of the first mask 13 is faithfully inverted. Can be formed.

In addition, when the mask transfer sheet 30 is used, O ₂ ashing is performed (see FIG. 3), which is preferable because O ₂ ashing and dry etching using an oxygen-based gas can be performed simultaneously. .

  A known dry etching apparatus can be used for the surface treatment of the metal thin film 12. The dry etching apparatus is not particularly limited as long as, for example, a fluorocarbon gas can be introduced in vacuum, plasma can be formed, and the metal thin film 12 can be subjected to surface treatment. A CCP (capacitive coupling type) device, an ICP (inductively coupled plasma type) device, an ECR (electron cycloton resonance type) device, or the like can be used. What is necessary is just to select suitably the time and electric power which perform a dry etching process according to the material to be used, thickness, and an etching rate. In order to faithfully reflect the pattern shape of the first mask 13 on the metal thin film 12, an ICP device or the like is suitable. For example, the pressure is 5P or less, and more preferably 3Pa or less. The power is preferably selected according to the device size.

  Next, as shown in FIG. 1D, a process of selectively removing other regions where the surface treatment of the metal thin film 12 has not been performed will be described. In the inversion structure 17 according to the present embodiment, the other region of the metal thin film 12 that has not been surface-treated is etched using a partial region of the metal thin film 12 that has been surface-treated and the layer 16 to be modified is formed as a mask. Can be obtained.

  Here, etching refers to either wet etching or dry etching, or a plurality of dry etchings after wet etching. Resist materials used for the metal thin film 12 and the first mask 13 It can select suitably according to surface treatment conditions. Dry etching has characteristics that can perform anisotropic etching such as ICP dry etching, and wet etching has features that equipment is inexpensive and etching speed is faster than dry etching. The etching method can be selected as appropriate.

  For example, when a chromium material is selected for the metal thin film 12 and surface treatment with oxygen gas is performed, the modified layer 16 becomes chromium oxide. In this case, the etching can be performed by wet etching, and an acidic solution such as hydrochloric acid can be used as an etching solution in which chromium is dissolved without dissolving chromium oxide. When a titanium material is selected for the metal thin film 12 and surface treatment with oxygen gas is performed, the modified layer 16 becomes titanium oxide. In this case, the etching can be performed by wet etching, and an acidic solution such as sulfuric acid, phosphoric acid, nitric acid and a mixture thereof can be used as an etching solution in which titanium oxide does not dissolve and titanium dissolves. When an iron material is selected for the metal thin film 12 and a surface treatment with oxygen gas is performed, the reformed layer 16 becomes iron oxide. In this case, the etching can be performed by wet etching, and an acidic solution such as nitric acid can be used as an etching solution in which iron oxide is dissolved without dissolving iron oxide. When a cobalt material is selected for the metal thin film 12 and surface treatment with oxygen gas is performed, the modified layer 16 becomes cobalt oxide. In this case, the etching can be performed by wet etching, and an acidic solution such as nitric acid can be used as an etching solution in which cobalt is dissolved without dissolving cobalt oxide. When a nickel material is selected for the metal thin film 12 and surface treatment with oxygen gas is performed, the reformed layer 16 becomes nickel oxide. In this case, the etching can be performed by wet etching, and an acidic solution such as nitric acid can be used as an etching solution in which nickel oxide does not dissolve and nickel is dissolved. When a manganese material is selected for the metal thin film 12 and surface treatment with oxygen gas is performed, the modified layer 16 becomes manganese oxide. In this case, the etching can be performed by wet etching, and an acidic solution such as sulfuric acid can be used as an etching solution in which manganese oxide is dissolved without dissolving manganese oxide. When an aluminum material is selected for the metal thin film 12 and surface treatment with oxygen gas is performed, the modified layer 16 becomes aluminum oxide. In this case, the etching can be performed by dry etching, and a chlorine-based gas can be used as a gas in which aluminum is not dry etched and aluminum is dry etched.

  In addition, when removing the other area | region of the metal thin film 12 by dry etching, in order to obtain the to-be-modified layer 16, it is preferable to implement other than the gas seed | species which surface-treated the metal thin film 12. FIG. When other regions of the metal thin film 12 are removed by dry etching with the same gas type as that used for the surface treatment of the metal thin film 12, the problem of the shape of the inversion structure 17 becoming unclear or the other regions of the metal thin film 12 are removed. Problems that can not be generated.

  As described above, as shown in FIG. 1D, the process of selectively removing another region where the surface treatment of the metal thin film 12 has not been performed has been described. However, the etching difference between the other region and the layer to be modified 16 has been described. Wet etching is more preferable from the viewpoint of easy release.

  As described above, the pattern shape of the first mask 13 can be faithfully reversed to the pattern shape of the second mask 12a by performing the method for manufacturing the reversal structure 18 according to the present embodiment. By etching the substrate 11 using the second mask 12a, the pattern shape of the second mask 12a can be reproduced on the substrate 11. That is, a pattern shape having a desired concavo-convex structure can be formed on the substrate 11 by producing a reverse pattern of the pattern shape having a desired concavo-convex structure using the first mask 13.

  The substrate with a concavo-convex structure 20 can be produced by etching the substrate 11 using a partial region 12a of the metal thin film 12 having the modified layer 16 constituting the inversion structure 17 of the inversion structure 18 as a mask. . Here, etching means either wet etching or dry etching, or a plurality of dry etchings after wet etching, and materials and surface treatment used for the metal thin film 12 constituting the inversion structure 17. It can select suitably according to the kind of gas used for. Dry etching has characteristics that can perform anisotropic etching such as ICP dry etching, and wet etching has features that equipment is inexpensive and etching speed is faster than dry etching. The etching method can be selected as appropriate.

  Hereinafter, the present invention will be described in detail with reference to examples carried out in order to clarify the effects of the present invention. In addition, this invention is not limited at all by the following examples.

Example 1
Chromium was selected as the material for the metal thin film, and CuO—SiO ₂ (10 at%) was selected as the thermal reaction resist material having dry etching resistance.

First, a chromium film having a thickness of 50 nm was formed on a 2 inΦ quartz substrate by a sputtering method, and then a thermal reaction type resist CuO—SiO ₂ (10 at%) was formed to a thickness of 20 nm. Film formation conditions were performed using a sputtering apparatus manufactured by Shibaura Mechatronics (CFS-8EP-350TH), a metal thin film using a φ3 inch Cr target, with a power of DC 80 W, and a thermal reaction resist of φ3 inch. _CuO-SiO 2 (10at%) using a target was performed at a power of RF100W.

The laminate formed as described above was exposed under the following conditions.
Semiconductor laser wavelength for exposure: 405 nm
Lens numerical aperture: 0.85
Exposure laser power: 1mW ~ 10mW
Feed pitch: 120 nm to 1000 nm

  Although various shapes and patterns can be produced by modulating the laser intensity during exposure, in this embodiment, an isolated circle was formed as a pattern in order to confirm the exposure accuracy. As a pattern shape to be formed, a continuous groove shape, an elliptical shape, or the like can be selected depending on a desired application. The present invention is not limited by the exposure shape.

  Subsequently, development of the heat-reactive resist was performed for 5 minutes using a 0.3 wt% glycine aqueous solution.

  Thereafter, using the thermal reaction resist pattern as a mask (first mask), surface treatment of the metal thin film made of chromium was performed with oxygen gas to form chromium oxide on a part of the metal thin film. At this time, a part of each sample was observed with a surface SEM (scanning electron microscope) to confirm the shape of the first mask.

  Next, 6N hydrochloric acid was used to dissolve the region of the metal thin film that was not surface-treated to obtain an inverted structure.

  When the surface inversion SEM observation of the obtained inversion structure and the first mask was performed, the inversion structure had a shape that faithfully inverted the concavo-convex structure of the first mask. Further, there was no change in the shape of the first mask before and after the surface treatment of the metal thin film with oxygen gas.

(Example 2)
Manganese was selected as the material for the metal thin film, and a mask transfer sheet containing an inorganic material having dry etching resistance was selected as the mask.

  First, a 30 nm-thick manganese film was formed on a 2 inΦ silicon substrate by sputtering. The film forming conditions were performed using a sputtering apparatus manufactured by Shibaura Mechatronics (CFS-8EP-350TH) and using a Mn target having a diameter of 3 inches for the metal thin film with a power of DC 200 W.

  Subsequently, a mask transfer sheet 30 having the pattern shown in FIG. 3A described above was prepared. In this example, a material A described later was used as the resin mold 31, a material B described later was used as the first mask layer 32, and a material C described later was used as the second mask layer 33. The pattern of the mask transfer sheet 30 was produced by selecting a pitch of 460 nm. In addition, although the pitch of the pattern this time was implemented with 460 nm, a pattern pitch can be changed as needed and this invention does not receive a restriction | limiting at all by a pattern shape.

In this example, the following materials were used.
・ DACHP: OPTOOL DAC HP (manufactured by Daikin Industries)
M350: trimethylolpropane (EO-modified) triacrylate (M350, manufactured by Toagosei Co., Ltd.)
・ I. 184 ... Irgacure 184 (manufactured by BASF Japan)
・ I. 369 ... Irgacure 369 (manufactured by BASF Japan Ltd.)
・ TTB: Titanium tetrabutoxide ・ 3APTMS: KBM5103 (manufactured by Shin-Etsu Silicone)
SH710: Phenyl-modified silicone (Toray Dow Corning)
SR833: Tricyclodecane dimethanol diacrylate (SR833 (manufactured by SARTOMER))
SR368: Tris (2-hydroxyethyl) isocyanurate triacrylate (SR368 (manufactured by SARTOMER)
・ PGME: Propylene glycol monomethyl ether ・ MEK: Methyl ethyl ketone

The above-described mask transfer sheet 30 was bonded onto the metal thin film 12 by heating the silicon substrate to 80 ° C. and UV irradiation (500 mJ / cm ² ).

Subsequently, as shown in FIG. 3B, after the resin mold 31 is peeled off, the remaining film at the bottom of the concave portion of the second mask layer 33 is removed by O ₂ ashing, and as shown in FIG. Was partially exposed. Note that the O ₂ ashing conditions were a pressure of 1 Pa and an O ₂ gas. At this time, a surface SEM observation and a cross-sectional SEM observation of a part of the sample were performed, and the shape of the first mask composed of the first mask layer 32 and the second mask layer 33 was confirmed.

Next, using the first mask layer 32 and the second mask layer 33 as a first mask, a surface treatment with oxygen gas was performed on a part of the metal thin film 12. Note that the O ₂ ashing conditions were a pressure of 1 Pa and an O ₂ gas. In this example, O ₂ ashing and surface treatment with oxygen gas were performed continuously.

  Next, the area | region where the surface treatment of the metal thin film was not performed was melt | dissolved using 2N sulfuric acid, and the inversion structure was obtained.

  When the surface inversion SEM observation and the cross-sectional SEM observation of the obtained inversion structure and the first mask (the first mask layer 32 and the second mask layer 33) were performed, respectively, the inversion structure has the first mask layer 32 and the first mask. The pattern shape of the concavo-convex structure constituted by the two mask layers 33 was faithfully inverted. Further, there was no change in the shapes of the first mask layer 32 and the second mask layer 33 before and after the surface treatment with oxygen gas of the metal thin film.

  The mask transfer sheet 30 may be manufactured as a single sheet or a reel. In particular, the reel shape is preferable because it is suitable for mass production. Hereinafter, a process of manufacturing the reel-shaped mask transfer sheet 30 in this embodiment will be described.

  (1) A cylindrical master mold was prepared, and (2) a reel-shaped resin mold was prepared by applying an optical transfer method to the cylindrical master mold. (3) Thereafter, the reel-shaped resin mold was processed into a mask transfer sheet on the optical substrate.

(1) Production of cylindrical master mold An uneven structure was formed on the surface of cylindrical quartz glass by a direct drawing lithography method using a semiconductor laser. First, a resist layer was formed on the cylindrical quartz glass surface by sputtering. The sputtering method was performed using a sputtering apparatus manufactured by Shibaura Mechatronics (CFS-8EP-350TH) using φ3 inch CuO—Si (8 atm%) with an RF power of 100 W, and a 20 nm resist layer was formed. did. Subsequently, exposure was performed using a semiconductor laser having a wavelength of 405 nm while rotating the cylindrical quartz glass. Next, the resist layer after exposure was developed. The development of the resist layer was carried out for 5 minutes using a 0.3 wt% glycine aqueous solution. Next, using the developed resist layer as a mask, the etching layer (quartz glass) was etched by dry etching. Dry etching was performed using SF ₆ as an etching gas under conditions of a processing gas pressure of 5 Pa, a processing power of 300 W, and a processing time of 8 minutes. Finally, only the resist layer residue was peeled off from the cylindrical quartz glass having a concavo-convex structure on the surface using sulfuric acid having a pH of 1. The peeling time was 6 minutes.

  Durasurf HD-1101Z (produced by Daikin Chemical Industries), which is a fluorine-based mold release agent, is applied to the uneven structure of the obtained cylindrical quartz glass, heated at 60 ° C. for 1 hour, and then allowed to stand at room temperature for 24 hours. And fixed. Then, it wash | cleaned 3 times by Durasurf HD-ZV (made by Daikin Chemical Industries), and the cylindrical master mold was obtained.

(2) Production of reel-shaped resin mold Using the produced cylindrical master mold as a mold, the optical nanoimprint method was applied to continuously produce a reel-shaped resin mold G1. Subsequently, a reel-shaped resin mold G2 was continuously obtained by an optical nanoimprint method using the reel-shaped resin mold G1 as a template. By obtaining the resin mold G2, the same pattern shape as the cylindrical master mold was obtained. Hereinafter, a method for producing the resin molds G1 and G2 will be described in detail.

The material A shown below was applied to the easy-adhesion surface of PET film A-4100 (manufactured by Toyobo Co., Ltd .: width 300 mm, thickness 100 μm) by microgravure coating (manufactured by Yurai Seiki Co., Ltd.) so that the coating film thickness was 5 μm. . Next, the PET film coated with the material A is pressed against the cylindrical master mold with a nip roll so that the integrated exposure amount under the center of the lamp is 1500 mJ / cm ^{2 in} the atmosphere at a temperature of 25 ° C. and a humidity of 60%. The resin mold G1 in the form of a reel with a concavo-convex structure transferred to the surface by irradiating ultraviolet rays using a UV exposure apparatus (H bulb) manufactured by Fusion UV Systems Japan Co., Ltd. 200 m in width and 300 mm in width).

Next, the reel-shaped resin mold G1 was regarded as a template, and the optical nanoimprint method was applied to continuously produce the reel-shaped resin mold G2. The following material A was applied to an easy-adhesion surface of PET film A-4100 (manufactured by Toyobo Co., Ltd .: width 300 mm, thickness 100 μm) by microgravure coating (manufactured by Yurai Seiki Co., Ltd.) so as to have a coating film thickness of 3 μm. Next, the PET film coated with the material A is pressed against the concavo-convex structure surface of the reel-shaped resin mold G1 with a nip roll (0.1 MPa), and the temperature is 25 ° C., the humidity is 60%, and the bottom of the lamp center. The UV exposure apparatus (H bulb) manufactured by Fusion UV Systems Japan Co., Ltd. is used to irradiate ultraviolet rays so that the integrated exposure amount is 1200 mJ / cm ^2, and photocuring is continuously performed. A plurality of transferred reel-shaped resin molds G2 (length 200 m, width 300 mm) were obtained.
Material A ... DACHP: M350: I. 184: I.D. 369 = 17.5 g: 100 g: 5.5 g: 2.0 g

(3) Preparation of mask transfer sheet The diluted solution of the following material B was applied to the concavo-convex structure surface of the reel-shaped resin mold G2. Subsequently, a diluent for the following material C was applied on the concavo-convex structure surface of the reel-shaped resin mold G2 containing the material B inside the concavo-convex structure to obtain a mask transfer sheet.
Material B ... TTB: 3APTMS: SH710: I. 184: I.D. 369 = 65.2 g: 34.8 g: 5.0 g: 1.9 g: 0.7 g
Material C: Binding polymer: SR833: SR368: I.I. 184: I.D. 369 = 77.1 g: 11.5 g: 11.5 g: 1.47 g: 0.53 g
Binding polymer: Methyl ethyl ketone solution of binary copolymer of 80% by mass of benzyl methacrylate and 20% by mass of methacrylic acid (solid content 50%, weight average molecular weight 56000, acid equivalent 430, dispersity 2.7)

  Using the same apparatus as in the above-mentioned (2) production of the reel-shaped resin mold, the material B diluted with PGME was directly applied onto the concavo-convex structure surface of the reel-shaped resin mold G2 (resin mold 31). . Here, the dilution concentration is such that the solid content contained in the coating raw material per unit area (the material B diluted with PGME) is 20% or more smaller than the volume of the concavo-convex structure of the resin mold G2 per unit area. Was set to be. After coating, the material was passed through an air-drying oven at 80 ° C. for 5 minutes, and a reel-shaped resin mold G2 containing the material B inside the concavo-convex structure was wound and collected.

  Subsequently, the reel-shaped resin mold G2 enclosing the material B in the concavo-convex structure is unwound and diluted with PGME and MEK using the same apparatus as the above-described (2) production of the reel-shaped resin mold. Material C was directly coated on the concavo-convex structure surface. Here, the dilution concentration was set such that the distance between the interface between the material B and the coated material C arranged in the concavo-convex structure and the surface of the material C was 400 nm to 800 nm. After coating, the material was passed through an air-drying oven at 80 ° C. for 5 minutes, and a cover film made of polypropylene was put on the surface of the material C, and the material was wound and collected.

  In FIG. 3A, the resin mold 31 corresponds to the material A, the first mask layer 32 corresponds to the material B, and the second mask layer 33 corresponds to the material C.

(Comparative Example 1)
Chromium was selected as the material for the metal thin film, and UV photoresist was selected as the resist material.

  First, two sheets of a 2 inφ quartz substrate were prepared, and chromium was deposited to a thickness of 50 nm by sputtering. The film formation was carried out using a sputtering apparatus manufactured by Shibaura Mechatronics (CFS-8EP-350TH), and using a φ3 inch Cr target for the metal thin film with a power of DC 80 W. Subsequently, a UV photoresist (PAK-02; manufactured by Toyo Gosei) was formed by spin coating.

Next, the sapphire substrate on which the UV photoresist was formed was transferred to the UV photoresist using a nanoimprint mold. The remaining film of the UV photoresist was removed by dry etching using O ₂ gas to form a first mask. The dry etching conditions were a pressure of 1 Pa and 2 minutes. At this time, a surface SEM observation of a part of the sample was performed, and the shape of the first mask was confirmed.

Subsequently, of the two substrates on which the first mask was formed, the first substrate was subjected to surface treatment of a metal thin film made of chromium with oxygen gas. The second sheet was subjected to a surface treatment of a metal thin film made of chromium with CF ₄ gas.

  At this point, when the surface SEM observation of a part of the sample was performed, the shape of the first mask was significantly changed.

  Next, 6N hydrochloric acid was used to dissolve the region of the metal thin film that was not surface-treated to obtain an inverted structure.

  When the surface inversion SEM observation of the obtained inversion structure and the first mask was performed, the inversion structure did not have a shape that faithfully inverted the uneven structure of the first mask.

(Example 3)
Aluminum was selected as the material for the metal thin film, CuO-SiO ₂ (10 at%) was selected as the heat-reactive resist material having dry etching resistance, and quartz glass with a sleeve shape of φ80 mm × L50 mm was used as the substrate. .

First, an aluminum film having a thickness of 30 nm was formed on a quartz substrate by a sputtering method, and then a thermal reaction resist CuO—SiO ₂ (10 at%) was formed to a thickness of 20 nm. The film forming conditions were performed using a sputtering apparatus manufactured by Shibaura Mechatronics (CFS-8EP-350TH), a metal thin film using a φ3 inch Al target, with a power of DC 80 W, and a thermal reaction resist of φ3 inch. _CuO-SiO 2 (10at%) using a target was performed at a power of RF100W.

First, an aluminum film having a thickness of 30 nm was formed on a sleeve-shaped substrate by a sputtering method, and then a thermal reaction resist CuO—SiO ₂ (10 at%) was formed to a thickness of 20 nm.

Next, the laminated body formed on the sleeve-shaped substrate was exposed to form a thermal reaction region in the thermal reaction type resist layer. The exposure conditions are shown below.
Semiconductor laser wavelength for exposure: 405 nm
Lens numerical aperture: 0.85
Exposure laser power: 1mW to 25mW
Feed pitch: 120 nm to 350 nm
Rotation speed: 210rpm-1670rpm

  Next, the exposed heat-reactive resist layer was developed. Development was carried out for 5 minutes using a 0.3 wt% aqueous glycine solution. At this point, a surface SEM observation of a part of the sample was performed to confirm the first mask shape.

  Thereafter, the surface of the metal thin film made of aluminum was treated with oxygen gas using the thermal reaction type resist pattern as a mask (first mask) to form aluminum oxide on a part of the metal thin film.

  Next, the region where the metal thin film was not surface-treated was etched by dry etching using chlorine gas to obtain an inverted structure. The dry etching was carried out using SAMCO (RIE-230iP) under a pressure of 0.2 Pa, a processing power of ICP200W / Bias100W, and a processing time of 1 minute.

  When the surface inversion SEM observation of the obtained inversion structure and the first mask was performed, the inversion structure had a shape that faithfully inverted the concavo-convex structure of the first mask. Further, there was no change in the shape of the first mask before and after the surface treatment of the metal thin film with oxygen gas.

Subsequently, the pattern was transferred to the quartz substrate using the inverted structure. The transfer was performed by dry etching with a fluorine-based gas. As dry etching conditions, CF ₄ gas was used as the fluorine-based gas, and the processing gas pressure was 5 Pa, the processing power was 300 W, and the processing time was 8 minutes.

  After transfer, the surface shape was transferred to a film using a UV curable resin. When the surface shape of the obtained film and the inverted structure was observed with a surface SEM, an inverted pattern was observed, and the inverted structure had a shape that faithfully inverted the concavo-convex structure of the first mask. Was confirmed.

Example 4
The second mask layer 33 and the first mask layer were all used under the same conditions as in Example 2 except that a 2inΦ sapphire substrate was selected as the substrate, two sheets were prepared, and iron and platinum were selected as the metal thin film materials. Up to 32 manufacturing steps were performed. The film formation conditions are as follows: a sputtering device manufactured by Shibaura Mechatronics (CFS-8EP-350TH) is used. In the case of iron as the metal thin film, a φ3 inch Fe target is used, and the power is DC 200 W. In the case of platinum as the metal thin film. Using a Pt target with a diameter of 3 inches, it was performed with a power of DC 200 W. At this time, the surface SEM observation of a part of the sample was performed, and the shapes of the second mask layer 33 and the first mask layer 32 were confirmed.

Next, using the second mask layer 33 and the first mask layer 32 as a mask, a part of the metal thin film 12 made of iron and a part of the metal thin film 12 made of platinum were subjected to surface treatment with oxygen gas, respectively. . The O ₂ ashing condition was performed under a pressure of 1 Pa and O ₂ gas. In this embodiment, O ₂ ashing and surface treatment with oxygen gas were performed continuously.

  Next, the area | region where the surface treatment of the metal thin film was not performed was melt | dissolved using 2N sulfuric acid, and the inversion structure was obtained.

  When the surface SEM observation and the cross-sectional SEM observation of the two types of obtained inverted structures and the first mask (the first mask layer 32 and the second mask layer 33) were performed, the inverted structure was found to be the first mask layer. The pattern shape of the concavo-convex structure composed of 32 and the second mask layer 33 was faithfully inverted. Further, there was no change in the shapes of the first mask layer 32 and the second mask layer 33 before and after the surface treatment with oxygen gas of the metal thin film.

Subsequently, the pattern was transferred to the sapphire substrate using the inverted structure. The transfer using the inverted structure produced from the metal thin film 12 made of iron was performed by dry etching using chlorine gas. The dry etching conditions were SAMCO (RIE-230iP), Cl ₂ gas as chlorine gas, pressure 0.2 Pa, processing power 300 W, and processing time 3 minutes. On the other hand, the transfer using the inverted structure produced from the metal thin film 12 made of platinum was performed by wet etching. Wet etching conditions were carried out for 3 minutes by heating a solution in which phosphoric acid and sulfuric acid were mixed at 1: 1 vol% to 230 ° C.

  When the surface shape of each of the obtained substrates and the inversion structure was observed with a surface SEM, it was observed that the patterns of the substrate and the inversion structure were the same, and the inversion structure had the first mask layer 32 and the second inversion structure. It was confirmed that the pattern shape of the concavo-convex structure constituted by the mask layer 33 was faithfully inverted. In addition, the shapes of the second mask layer 33 and the first mask layer 32 before and after the surface treatment with the oxygen gas of the metal thin film were not changed.

  In addition, this invention is not limited to the said embodiment, It can implement variously. In the above-described embodiment, the size, shape, and the like illustrated in the accompanying drawings are not limited thereto, and can be appropriately changed within a range in which the effect of the present invention is exhibited. In addition, various modifications can be made without departing from the scope of the object of the present invention.

  In the fine pattern processing required in the fields of semiconductors, optical / magnetic recording, etc., it becomes possible to reverse the shape of the fine concavo-convex structure of the resist.

11 Substrate 12 Metal thin film 12a Second mask 13 Uneven structure (first mask)
14 Convex part 15 Concave part 16 Modified layer 17 Inverted structure 18 Inverted structure 20 Substrate with concave-convex structure 30 Mask transfer sheet 31 Mold 32 First mask layer 33 Second mask layer

Claims (9)

A concavo-convex structure composed of a plurality of convex portions made of resist on a metal thin film provided on a substrate and a plurality of concave portions provided between the convex portions and exposing the metal thin film to the inside thereof. Forming a first mask having:
Using the first mask, a reactive gas that is not reactive to the resist but reactive to the metal thin film is allowed to act on a part of the metal thin film exposed in the recess. forming a reforming target layer provide Reinforced surface treatment,
As a mask some of the regions of the metal thin film having the to-be-reformed layer, the metal in which the other region in which the surface treatment is not applied in a thin metal film is selectively removed, with the object to be modified layer a second mask is a part of the area of the thin film, a step of the substrate before Symbol metal thin film is removed to obtain the exposed area, in which is constituted, the inverted structure corresponding to the concavo-convex structure,
Etching the substrate using the second mask , and
The method for manufacturing an inverted structure , wherein the resist is a heat-reactive resist containing an inorganic material that has etching resistance to the reactive gas used in the surface treatment .   2. The method for manufacturing an inverted structure according to claim 1, wherein the pitch of the concavo-convex structure is 1 nm or more and 10 μm or less.   The mask is a mask transfer sheet comprising a mold having a reversal structure corresponding to the concavo-convex structure and the resist filled in a concave portion of the reversal structure of the mold, and is bonded onto the substrate. The method for producing an inverted structure according to claim 1, wherein the method is obtained by peeling the mold. The method for manufacturing an inverted structure according to claim 3 , further comprising a step of removing a residual film of the mask obtained by peeling the mold. 4. The manufacturing of the inverted structure according to claim 3 , wherein a step of removing a residual film of the mask obtained by peeling off the mold and a step of performing the surface treatment on the metal thin film are simultaneously performed. Method. The method for manufacturing an inverted structure according to any one of claims 1 to 5 , wherein the metal thin film is chromium, titanium, iron, cobalt, nickel, manganese, aluminum, or platinum. Method for manufacturing a reversed structure as claimed in any one of claims 6, characterized in that performing the surface treatment, using an oxygen-based gas. The method for manufacturing an inverted structure according to any one of claims 1 to 7 , wherein the substrate is made of quartz, sapphire, silicon, silicon nitride, or gallium nitride. In inverted structures manufactured by the manufacturing method of the inverted structure according to any one of claims 1 to 8, the region of the portion of the surface-treated in the metal thin film constituting the inverted structure A substrate with a concavo-convex structure, wherein the concavo-convex structure corresponding to the inversion structure is formed by etching the substrate using a mask as a mask.

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