TW201943529A - Template for nanoimprinting and method for producing thereof, as well as two-stage mesa blanks and method for producing therof - Google Patents

Abstract

Provided is a template for nanoimprinting characterized by comprising a base and a translucent substrate having a mesa structure arranged at a main surface of the base, wherein a concave and convex structured transfer pattern and a concave and convex structured pattern for marking are arranged at a main surface of the mesa structure, a high contrast film is arranged at a bottom surface of a concave part in the pattern for marking, and a tantalum oxide film is arranged at a surface of the high contrast film so as to cover the high contrast film.

Description

Nano-imprinting die and manufacturing method thereof, and two-stage mesa substrate and manufacturing method thereof

The invention relates to a nano-imprinting die and a manufacturing method thereof, and a two-stage mesa substrate and a manufacturing method thereof.

Nano-imprint lithography is a method for transferring a pattern to a transferee body by the following steps: a desired transfer pattern set on a nanoimprinting stencil is tightly adhered to the surface coated on the transferee body The hardening resin layer is transferred to the hardening resin layer by applying an external stimulus such as heat or light. Because nanoimprint lithography can be patterned by a simple method, it is expected as a next-generation lithography technology for the manufacture of LSI (Large Scale Integration, large scale integrated circuit). Furthermore, it is also expected as a technology for processing optical parts, light-emitting elements, photoelectric conversion elements, biosensors, decorations, beverage containers, food containers, and the like. Therefore, the development of nanoimprint stencils has been advanced.

In the nanoimprint lithography, when transferring the transfer pattern of the nanoimprint stencil to the transferee, the position of the nanoimprint stencil and the transferee must be aligned. In order to perform such alignment, an alignment mark may be set on a substrate through which light can be transmitted through the nanoimprinting die, and a corresponding alignment mark may also be set on the object to be transferred. In addition, a nano-imprinting die may be provided with an identification mark for identifying the type of the die itself.

The alignment mark or the identification mark includes, for example, a pattern of an uneven structure in a main surface of a base material of a nanoimprint die and a high-contrast film provided on the pattern. Such a high-contrast film may not be able to obtain a desired contrast because the film is reduced during the cleaning of the nanoimprint die. Therefore, various structures such as those that can reduce the film reduction of such a high-contrast film are used.

For example, Patent Document 1 describes a structure in which a high-contrast film is provided on a pattern of an uneven structure in a main surface of a base material of a die, and a protective high-contrast film is provided on the entire main surface of the base material. Of protective film. However, in such a structure, since a protective film is provided on the entire main surface, when the transfer pattern provided on the main surface is fine, the thickness of the protective film may cause the uniformity of the transferred pattern to be impaired. .

Further, Patent Document 2 describes a structure in which a high-contrast film is provided on a convex portion of a pattern of a concave-convex structure in a main surface of a base material of a die, and a region including a concave portion of a pattern of a concave-convex structure. A protective film is provided so as to cover the high-contrast film. However, in such a structure, in particular, a high-contrast film is provided on the convex portion, so that a cleaning solution or the like may penetrate into the high-contrast film depending on the film-forming state of the protective film in the end portion of the high-contrast film. Therefore, the film reduction of the high-contrast film cannot be sufficiently suppressed.

Furthermore, Patent Document 3 describes a structure in which a high-contrast film is provided in a recessed portion of a pattern of a concave-convex structure in a positional alignment region of a main surface of a base material of a mold, and the high-contrast film is provided on the high-contrast film. Protective film. However, in such a structure, the high-contrast film may not be sufficiently protected depending on the film-forming state of the protective film in the end portion of the high-contrast film.

Therefore, in the structure of the previous protective film, the reduction of the film of the high-contrast film cannot be sufficiently suppressed.
[Prior technical literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2009-200505
[Patent Document 2] Japanese Patent Laid-Open No. 2013-30522
[Patent Document 2] Japanese Patent Publication No. 2013-519236

[Problems to be solved by the invention]

The present invention has been made in view of the above-mentioned problems, and a main object thereof is to provide a nanoimprint die sheet capable of sufficiently suppressing a reduction in film of a high-contrast film and a method for manufacturing the same.
[Technical means to solve the problem]

In order to solve the above-mentioned problems, the present invention provides a nanoimprinting die, which is provided with a light-transmitting substrate having a base portion and a mesa structure provided on the main surface of the base portion, and is provided on the main surface of the mesa structure. A transfer pattern with a concave-convex structure and a marking pattern with a concave-convex structure are provided. A high-contrast film is provided on the bottom surface of the concave portion of the marking pattern. Tantalum oxide film.

According to the present invention, the reduction or disappearance of the film of the high-contrast film can be sufficiently suppressed.

In the above invention, the tantalum oxide film is preferably provided on a surface of the high-contrast film and an upper surface of a convex portion of the marking pattern. The reason is that the high-contrast film can be effectively covered without being exposed.

Moreover, in the said invention, it is preferable that a groove is provided in the main surface of the said mesa structure along the said tantalum oxide film. The reason is that the presence or absence of the tantalum oxide film can be easily determined.

In the above invention, it is preferable that the mesa structure includes a first step difference structure provided on the main surface of the base portion and a second step difference structure provided on the main surface of the first step difference structure, the transfer pattern and The marking pattern is provided on the main surface of the second step difference structure, a light shielding portion is provided in a region around the second step difference structure among the main surfaces of the first step difference structure, and the tantalum oxide film covers the The aspect of the main surface of the light shielding portion is provided on the main surface of the light shielding portion. The reason is that the light-shielding portion can be used to suppress exposure of light to unintended areas during photo-imprinting, and the tantalum oxide film can be used to suppress the reduction or disappearance of the film of the light-shielding portion.

In the above invention, it is preferable that the light-shielding portion has a multilayer structure in which a light-shielding film and the high-contrast film are laminated in this order. The reason is that it is possible to effectively suppress the exposure of exposed light to unintended areas during photoimprinting.

In the above invention, it is preferable that a recessed portion including the second step difference structure in plan view is provided on a surface of the base portion opposite to the main surface. This is because it is possible to suppress air from being trapped between the transfer pattern and the curable resin layer applied to the surface of the object to be transferred.

In addition, the present invention provides a method for manufacturing a nanoimprint die, which includes a preparation step for preparing a member for forming a die, the member for forming the die including a light-transmitting substrate and a high-contrast film. The translucent substrate has a base portion and a mesa structure provided on a main surface of the base portion, and a transfer pattern of a concave-convex structure and a marking pattern of the concave-convex structure are provided on the main surface of the mesa structure, and the high-contrast film is provided. The entire surface of the main surface side of the light-transmitting substrate; the first resin layer forming step is to use a marking pattern area provided with the marking pattern as a thin film, and a transfer pattern area provided with the transfer pattern. To form a thick film, a first resin layer is formed on the marking pattern and the transfer pattern. The first etching step is to etch the member for forming a mold sheet on which the first resin layer is formed. While leaving the high-contrast film on at least the bottom surface of the recessed portion of the marking pattern and the transfer pattern region, removing other parts of the high-contrast film; the tantalum oxide film shape A forming step of forming a tantalum oxide film on the entire surface of the main surface side of the die-forming member having undergone the first etching step; and a second resin layer forming step of forming a thick film with the pattern area for the marking, In addition, in a manner that the transfer pattern region is a thin film, a second resin layer is formed on the tantalum oxide film formed on the marking pattern region and the transfer pattern region; the second etching step is performed by forming the above The mold forming member of the second resin layer is etched to leave the tantalum oxide film formed on at least the surface of the high-contrast film, and to remove other parts of the tantalum oxide film; and a third etching step, which is By performing the etching using the remaining tantalum oxide film as a mask, the high-contrast film provided in the transfer pattern region is removed.

According to the present invention, it is possible to produce a nanoimprint die that can sufficiently suppress the reduction or disappearance of the film of the high-contrast film.

In the above invention, preferably, in the first etching step, in the marking pattern, the high-contrast film is left only on a bottom surface of the concave portion, and other parts of the high-contrast film are removed, and the first In the 2 etching step, the tantalum oxide film formed on the surface of the high-contrast film and the upper surface of the convex portion of the marking pattern is left. The reason for this is that the nanoimprint die sheet in which the tantalum oxide film is provided on the surface of the high-contrast film and the upper surface of the convex portion of the marking pattern can be manufactured.

In the above invention, it is preferable that in the second resin layer forming step, a region to be a thick film of the second resin layer is set to be inward from a region to be a film of the first resin layer in a plan view, and In the second etching step, a groove is formed along the region that becomes the thick film of the second resin layer on the main surface of the mesa structure by performing the etching. The reason for this is that the nanoimprint die sheet capable of judging the presence or absence of the tantalum oxide film by identifying the presence or absence of the groove can be manufactured.

In the above invention, it is preferable that, in the preparation step, the die-forming member is prepared. In the die-forming member, the mesa structure has a first step structure and an arrangement provided on a main surface of the base. A second step difference structure on the main surface of the first step difference structure, the transfer pattern and the mark pattern are provided on the main surface of the second step difference structure, and further, the second step difference structure is provided on the first step difference structure. In the main area of the light-shielding portion of the area around the second step structure, in the first resin layer forming step, the first resin layer is also formed on the light-shielding portion. In the first etching step, The light-shielding portion is left, and the tantalum oxide film is formed on the main surface of the light-shielding portion in the step of forming the tantalum oxide film. The second resin layer of the thick film is formed on the tantalum oxide film, and the tantalum oxide film formed on the main surface of the light shielding portion is left in the second etching step. The reason for this is that it is possible to manufacture the nano-light which can suppress the exposure of light to an unintended area during photo imprint by the light-shielding portion, and can suppress the reduction or disappearance of the film of the light-shielding portion by the tantalum oxide film. Rice embossing die.

In addition, in the present invention, a nanoimprint die is provided, which includes a light-transmitting substrate having a base portion and a mesa structure provided on the main surface of the base portion, and is provided on the main surface of the mesa structure. A transfer pattern with a concave-convex structure and a marking pattern with a concave-convex structure are provided. A high-contrast film is provided on the bottom surface of the concave portion of the marking pattern, and a continuous cover is provided so that the ends of the high-contrast film are not exposed. And a protective film including a surface of the high-contrast film and a side surface of the convex portion of the marking pattern and an upper surface of the convex portion of the marking pattern and including a material different from the high-contrast film, and the protective film The above-mentioned mark is provided on the upper surface of the convex portion of the pattern.

According to the present invention, a nanoimprint die sheet capable of sufficiently suppressing a reduction in film of a high-contrast film can be manufactured.

Further, in the above invention, it is preferable that the protective film includes an alignment mark region in which the concave portion and the convex portion of the marking pattern on which the high-contrast film is provided are arranged in a row in a plan view. This method is provided in an area larger than the above-mentioned alignment mark area. This is because the infiltration of the medicinal solution can be reliably suppressed by the protective film, and the reduction of the film of the high-contrast film can be suppressed.

In addition, according to the present invention, the protective film may be provided in a region larger than the plurality of alignment mark regions so as to include the plurality of alignment mark regions.

In addition, according to the present invention, the protective film is preferably provided in a rectangular shape in a plan view.

Moreover, according to this invention, it is preferable that the main surface of the said mesa structure is provided with a groove along the said protective film. The reason is that the presence or absence of the protective film can be easily determined.

According to the present invention, it is preferable that the protective film is a tantalum oxide film. The reason is that the tantalum oxide film is sufficiently resistant to sulfuric acid cleaning or alkaline cleaning to remove foreign matter such as resist used in nanoimprint lithography, and cannot be removed compared to such cleaning. Moreover, the resistance to plasma ashing using an oxygen-containing gas for the removal of residual foreign matter is also sufficiently high.

In addition, in the present invention, a two-stage mesa substrate is provided, which is used for manufacturing a nanoimprint die and has a light-transmitting two-stage mesa substrate forming member. The light-transmitting 2 The segment mesa base forming member has a base portion and a mesa structure provided on the main surface of the base portion. The mesa structure includes a first step structure provided on the main surface of the base portion and a main surface provided on the first step structure. The second step difference structure is provided with a light shielding portion at least in a region around the second step difference structure among the main surfaces of the first step difference structure, and is arranged on the light shielding portion so as to cover the main surface of the light shielding portion. The main surface is provided with a protective film.

With such a two-stage mesa substrate, the nanoimprint die sheet of the present invention described above can be easily obtained. Furthermore, the reason is that it is possible to manufacture the light-shielding portion that can suppress exposure of light to an unintended area during light imprinting, and that the protective film can suppress the reduction or disappearance of the film of the light-shielding portion. Nano-imprinting die.

Further, in the present invention, the light shielding portion may be provided from the main surface of the first step difference structure to the main surface of the base portion.

In addition, in the present invention, a method for manufacturing a two-stage mesa substrate is provided, which is characterized in that it is a method for manufacturing the two-stage mesa substrate, and a light-transmitting two-stage mesa substrate forming member is prepared, and the light-transmitting two-stage mesa substrate is prepared. The mesa base forming member has a base portion and a mesa structure provided on the main surface of the base portion. The mesa structure includes a first step structure provided on the main surface of the base portion and a first step structure provided on the main surface of the first step structure. A two-step difference structure in which a film for forming a light-shielding portion is formed on a main surface of the side of the light-transmitting two-stage mesa base formation member on which the first step difference structure and the second step difference structure are disposed,

A film for forming a protective film is formed on the film for forming a light-shielding portion, and a curable resin layer is formed on the main surface of the first step structure and the main surface of the second step structure. The film thickness of the curable resin layer formed on the main surface of the first step structure is thicker than the film thickness of the curable resin layer formed on the main surface of the second step structure. The light-shielding portion forming film and the protective film are etched so that only the main surface of the first step difference structure is left, thereby manufacturing the main member of the first step difference structure of the light-transmitting two-stage mesa substrate forming member. A two-stage mesa base in which a light shielding portion and a protective film are sequentially arranged in a region around the second step difference structure in the surface.

In addition, in the present invention, a method for manufacturing a two-stage mesa substrate is provided, which is characterized in that it is a method for manufacturing the two-stage mesa substrate, and a light-transmitting two-stage mesa substrate forming member is prepared, and the light-transmitting two-stage mesa substrate is prepared. The mesa base forming member has a base portion and a mesa structure provided on the main surface of the base portion. The mesa structure includes a first step structure provided on the main surface of the base portion and a first step structure provided on the main surface of the first step structure. A two-level difference structure in which a light-shielding portion forming film is formed on the surface of the light-transmitting two-stage mesa substrate forming member, a protective film-forming film is formed on the light-shielding portion forming film, and the protective film-forming film is coated The resist composition is formed to form a resist layer. The resist layer is exposed and developed through a mask to remove the resist layer on the main surface of the second step structure, and the second layer is exposed. The light-shielding portion-forming film and the protective film-forming film formed on the main surface of the stepped structure are removed by etching, thereby manufacturing a laminated material obtained by laminating the light-shielding portion and the protective film in this order. Duantai Provided to the substrate 2 is formed a base section of the table of the main surface of the base portion with the first principal surface step difference of the configuration of the member.
[Effect of the invention]

In the present invention, the effect of sufficiently reducing or eliminating the film of the high-contrast film is exerted.

Hereinafter, the nanoimprint die sheet of the present invention and a manufacturing method thereof will be described in detail.

A. Nano Imprinting Die (First Embodiment)
The nanoimprinting die according to the first embodiment of the present invention is characterized by including a light-transmitting substrate having a base portion and a mesa structure provided on the main surface of the base portion, and provided on the main surface of the mesa structure. A transfer pattern with a concave-convex structure and a marking pattern with a concave-convex structure are provided with a high-contrast film on the bottom surface of the concave portion of the mark-forming pattern, and tantalum oxide is provided on the surface of the high-contrast film so as to cover the high-contrast film. membrane.

An example of the nanoimprint die sheet of the present invention will be described with reference to the drawings. FIG. 1 (a) is a schematic cross-sectional view showing an example of a nano-imprinting die of the present invention. FIG. 1 (b) is an enlarged view within a dotted frame shown in FIG. 1 (a). Fig. 1 (c) is a plan view of the mesa structure shown in Fig. 1 (b) from the main surface side.

As shown in FIGS. 1 (a) to 1 (c), the nanoimprint die 10 includes a light-transmitting substrate 20 having a base portion 21 and a mesa structure 22 provided on a main surface 21 a of the base portion 21. A transfer pattern 30 of a concave-convex structure and a marking pattern 40 of a concave-convex structure are provided on the main surface 22 a of the mesa structure 22. Further, a recessed portion 25 including a mesa structure 22 in plan view is provided on a surface of the base portion 21 opposite to the main surface 21 a. A high-contrast film 50 containing Cr is provided only on the bottom surface 42 a of the recessed portion 42 of the marking pattern 40. The high-contrast film 50 constitutes an alignment mark. The tantalum oxide film 60 containing tantalum oxide is provided continuously with the surface of the high contrast film 50 and the side surfaces 44 b and the upper surface 44 a of the convex portion 44 of the marking pattern 40 so as to cover the high contrast film 50 without exposure. Further, a groove 26 is provided on the upper surface 44 a of the convex portion 44 of the marking pattern 40 along the tantalum oxide film 60.

In recent years, in the case where the resist used for nanoimprint lithography, such as the cleaning with sulfuric acid cleaning or the alkaline cleaning, cannot be removed from the mold and remains, a plasma ash using an oxygen-containing gas is used. Turning away. On the other hand, in the protective film for protecting a high-contrast film described in the aforementioned patent document, Cr-based materials (Cr, CrN, etc.), Si-based materials (SiO ₂ , SiN _2, etc.), and Ta-based materials are used as constituent materials. However, there is a problem in that a protective film including these disappears together with the high-contrast film depending on the material when the plasma is ashed. In addition, regarding a protective film containing a Ta-based material, especially TaN, the high-contrast film and the etching gas constituting the alignment mark or the identification mark are, for example, a chlorine-based gas. It may disappear by dry etching. Therefore, it is difficult to provide the high-contrast film so as not to expose it.

On the other hand, the tantalum oxide film 60 containing tantalum oxide in the present invention has sufficiently high resistance to sulfuric acid cleaning or alkaline cleaning for removing foreign matters such as resist used in nanoimprint lithography, and is relatively The resistance to plasma ashing using an oxygen-containing gas for removing foreign matter that cannot be removed during such washing is also sufficiently high. Therefore, the tantalum oxide film 60 is not likely to disappear during sulfuric acid cleaning or alkaline cleaning and cleaning of the die sheet using plasma ashing.

Furthermore, since the tantalum oxide film 60 is different from a protective film containing TaN and is different from an etching gas of the high-contrast film 50, there is no possibility that the tantalum oxide film 60 will disappear by dry etching when the high-contrast film 50 is processed.

Therefore, according to the present invention, by covering the high-contrast film with the tantalum oxide film, the reduction or disappearance of the film of the high-contrast film can be sufficiently suppressed. Furthermore, in the method for manufacturing a nanoimprint die sheet of the present invention, since the tantalum oxide film may disappear when a high-contrast film is not processed, it is easier to install it so as to cover the high-contrast film.

1. Tantalum oxide film The tantalum oxide film is a film containing tantalum oxide which is provided on the surface of the high contrast film so as to cover the high contrast film.

Here, the above-described tantalum oxide, for example, refers to a TaO _2, Ta ₂ O ₅ and the like of the compound represented by TaOx.

It is preferable that x in the said TaOx exists in the range of 2-5.

As the above tantalum oxide, a small part of O may be replaced with N, but the ratio of N substituted with O is preferably 0.1 at% or less, and particularly preferably, O is not replaced with N. The reason is that if the ratio of N substituted with O increases, the tantalum oxide film may disappear by dry etching used when processing the high-contrast film. The reason is that it is difficult to process the tantalum oxide film by dry etching.

Here, FIG. 2 (a) is a schematic cross-sectional view showing another example of the nanoimprint die sheet of the present invention, and is a view showing a region corresponding to the region shown in FIG. 1 (b). Fig. 2 (b) is a plan view of the mesa structure shown in Fig. 2 (a) as viewed from the main surface side. The nano-imprinting die 10 shown in FIG. 2 is different from the nano-imprinting die 10 shown in FIG. 1 in that the bottom surface of a plurality of adjacent recesses 42 provided in the marking pattern 40 is provided. The tantalum oxide films 60 of 42a are separated from each other.

FIG. 3 (a) is a schematic cross-sectional view showing another example of the nanoimprinting die of the present invention, and is a view showing a region corresponding to the region shown in FIG. 1 (b). Fig. 3 (b) is a plan view of the mesa structure shown in Fig. 3 (a) from the main surface side. The difference between the nano-imprinting die 10 shown in FIG. 3 and the nano-imprinting die 10 shown in FIG. 1 is that the tantalum oxide film 60 is provided only on the bottom surface 42 a of the recess 42 of the marking pattern 40. The surface of the high-contrast film 50 provided above.

As the tantalum oxide film, as shown in FIGS. 1 to 3, it is not particularly limited as long as it is provided on the surface of the high-contrast film so as to cover the high-contrast film, but it is preferably as shown in FIGS. 1 and 2. Those shown on the surface of the high-contrast film and the upper surface of the convex portion of the marking pattern as shown are particularly preferably those provided on the surface of the high-contrast film and the side and upper surfaces of the convex portion of the marking pattern. Particularly preferred is a continuous setter. The reason is that the high-contrast film can be effectively covered without being exposed. Specifically, the reason is that, for example, as shown in FIG. 1 and FIG. 2, the tantalum oxide film is provided to be continuous with the surface of the high-contrast film and the side and upper surfaces of the convex portions of the marking pattern. In this case, even if the high-contrast film protrudes to the side surface of the convex portion of the marking pattern, the high-contrast film may be covered without being exposed.
In addition, the tantalum oxide film is formed over the entire surface of the nanoimprinting die by sputtering, for example, and is formed on the surface of the high-contrast film and the projection of the pattern for marking. In the case of the upper surface of the part, usually, it is also provided on the side of the convex part of the marking pattern.

As the tantalum oxide film, as shown in FIG. 2 and FIG. 3, the tantalum oxide film provided on the bottom surface of a plurality of adjacent recesses in the marking pattern is preferably separated from each other. Each of the high-contrast films provided on the bottom surface of the adjacent plurality of recesses may be covered with the tantalum oxide film separated from each other. The reason for this is that, since the light-transmitting substrate is exposed between the high-contrast films, the high-contrast film can be easily identified.

The thickness of the tantalum oxide film is not particularly limited as long as the reduction or disappearance of the high-contrast film can be sufficiently suppressed, but it is preferably in the range of 1 nm to 10 nm, and more preferably in the range of 3 nm to 6 nm. Inside. The reason is that if the tantalum oxide film is too thin, the reduction or disappearance of the film of the high-contrast film cannot be sufficiently suppressed, and if the tantalum oxide film is too thick, when it is provided on the upper surface of the convex portion of the marking pattern, It becomes an obstacle when transferring the said transfer pattern to a to-be-transferred body.

2. High-contrast film The high-contrast film is provided on the bottom surface of the recessed portion of the marking pattern. The high-contrast film constitutes a mark such as an alignment mark, a recognition mark, or the like.

The high-contrast film is not particularly limited as long as it is provided on the bottom surface of the recessed portion of the marking pattern, and may be provided on the bottom surface of the recessed portion of the marking pattern and on the side or on the convex portion of the marking pattern. On the surface, as shown in FIGS. 1 to 3, it is preferable to be provided only on the bottom surface of the recessed portion of the marking pattern. The reason is that if the high-contrast film is provided on the side surface or the upper surface of the convex portion of the marking pattern, it is difficult to cover the tantalum oxide film without being exposed, and it is difficult to suppress the reduction or disappearance of the high-contrast film. The reason is that the high-contrast film is thicker than the tantalum oxide film. Therefore, if the high-contrast film is provided on the upper surface of the convex portion of the marking pattern, the transfer pattern is transferred to the transferred substrate. It becomes an obstacle when printing.

The material of the high-contrast film is not particularly limited as long as it can constitute a mark that can be optically recognized. For example, a material having a refractive index different from that of the light-transmitting base material with respect to the light that recognizes the mark can be used. Examples of such a material include one or two or more of metals and their oxides, nitrides, and oxynitrides. Examples of the metal include Cr, Mo, Ta, W, Zr, and Ti. As such a material, Cr and a compound containing Cr (chromium nitride, chromium oxide, chromium carbide, chromium carbon nitride, etc.) are preferable. This is because the resistance to plasma ashing using an oxygen-containing gas is low, and the effect of suppressing the reduction or disappearance of the above-mentioned high-contrast film becomes apparent.

The thickness of the high-contrast film is not particularly limited as long as it can constitute a mark that can be optically recognized, but is preferably set so that the transmittance of light at a wavelength of 365 nm becomes 10% or less. For example, when chromium (Cr) is used as the material of the high-contrast film, in order to set the transmittance of light at a wavelength of 365 nm to 10% or less, the thickness of the high-contrast film may be 15 nm or more. .

3. Translucent base material The said translucent base material has a base part and a mesa structure provided in the main surface of the said base part.

(1) Mesa structure The mesa structure is a structure in which a transfer pattern of an uneven structure and a marking pattern of an uneven structure are provided on a main surface.

a. Pattern for marking The pattern for marking is a pattern having an uneven structure when the translucent substrate is viewed in cross section. The pattern for markings together with the high-contrast film constitute, for example, marks such as alignment marks, identification marks, and the like.

The shape of the marking pattern is not particularly limited, and examples thereof include a pattern of a concave-convex structure such as a line and a gap.

In the case where the pattern for marking is shown in FIG. 1 as a line and a gap, the depth of the concave portion of the uneven structure shown by D in FIG. 1 (b) is not particularly limited, for example, it is the same as that of the transfer pattern. The recesses have the same depth. The width of the concave portion and the width of the convex portion of the uneven structure are appropriately set in accordance with the use of the marking pattern.

b. Transfer pattern The transfer pattern is a pattern having an uneven structure when the translucent substrate is viewed in cross section. The above-mentioned transfer pattern is a pattern transferred from the above-mentioned nanoimprint stencil to the object to be transferred using a nanoimprint lithography.

The shape of the transfer pattern is not particularly limited, and examples include patterns of uneven structures such as lines and gaps, dots, holes, isolation spaces, isolation lines, columns, lenses, and steps.

The size of the transfer pattern is not particularly limited. When the shape of the transfer pattern is a line and a gap as shown in FIG. 1, for example, the line width is about 30 nm and the height of the convex portion of the uneven structure. It is about 60 nm. When the shape of the transfer pattern is a column shape, for example, the diameter is about 50 nm, and the height of the convex portion of the uneven structure is about 60 nm.

c. Mesa structure Here, FIG. 4 (a) is a schematic cross-sectional view showing another example of the nanoimprinting die of the present invention, and is a view showing an area corresponding to the area shown in FIG. 1 (b). Fig. 4 (b) is a plan view of the mesa structure shown in Fig. 4 (a) as viewed from the main surface side. The nano-imprinting die 10 shown in FIG. 4 is different from the nano-imprinting die 10 shown in FIG. 1 in that the upper surface 44 a of the convex portion 44 of the marking pattern 40 does not follow the tantalum oxide film. 60 Trough 26 is provided.

The mesa structure may be a groove provided along the tantalum oxide film on the main surface of the mesa structure as shown in FIG. 1, or may be provided without the groove as shown in FIG. 4, but is preferably provided with The above slot. The reason is that because the tantalum oxide film is transparent, it is difficult to directly identify and judge the presence or absence of the tantalum oxide film. In contrast, the presence or absence of the tantalum oxide film can be judged by identifying the presence or absence of the groove, so it can be easily performed. The presence or absence of the above-mentioned tantalum oxide film is judged. Furthermore, the reason is that the existence of the groove indicates that the high-contrast film provided on the upper surface of the convex portion of the transfer pattern during the manufacture of the mold sheet has been reliably removed. Therefore, the existence of the groove makes it possible to It is determined that the high-contrast film does not become an obstacle when transferring the transfer pattern to a transfer target.

It should be noted that the above-mentioned grooves are as follows in "B. Manufacturing method of nanoimprinting die sheet 2. Manufacturing method of nanoimprinting die sheet (1) Manufacturing method of nanoimprinting die sheet" The item formed on the main surface of the mesa structure during etching in the second etching step in the manufacturing method described in the item "is not particularly limited, and is not limited to the concave-shaped removal portion shown in Fig. 1 It may also be a step-like removal portion.

Here, FIG. 5 (a) is a schematic cross-sectional view showing another example of the nanoimprint die sheet of the present invention. FIG. 5 (b) is an enlarged view within a dotted frame shown in FIG. 5 (a). Fig. 5 (c) is a plan view of the mesa structure shown in Fig. 5 (b) from the main surface side.

As shown in FIGS. 5 (a) and 5 (b), the nanoimprint die 10 includes a light-transmitting substrate 20 having a base portion 21 and a mesa structure 22 provided on a main surface 21 a of the base portion 21. The mesa structure 22 includes a first step difference structure 27 provided on the main surface 21 a of the base portion 21 and a second step difference structure 28 provided on the main surface 27 a of the first step difference structure 27. A transfer pattern 30 of a concave-convex structure and a marking pattern 40 of a concave-convex structure are provided on the main surface 28 a of the second step difference structure 28. In addition, a recessed portion 25 including a second step difference structure 28 and a first step difference structure 27 in plan view is provided on the surface of the base portion 21 opposite to the main surface 21a. The nanoimprint die 10 is provided with a high-contrast film 50 and a tantalum oxide film 60 similarly to the die shown in FIG. 1.

The above-mentioned mesa structure may have a single step structure as shown in FIG. 1, and the main surface of the single step structure is provided with the transfer pattern and the marking pattern, as shown in FIG. 5. The first step difference structure and the second step difference structure provided on the main surface of the first step difference structure are shown, and the transfer pattern and the marking pattern are provided on the main surface of the second step difference structure.

The shape of the mesa structure in plan view is not particularly limited, and for example, it may be rectangular as shown in FIG. 1 (c). The height of the mesa structure shown by M in FIG. 1 (b) varies depending on applications and the like, and is about 10 μm to 50 μm, for example. Furthermore, the vertical and horizontal lengths of the above-mentioned table structure having a rectangular shape in plan view are different depending on applications and the like, and are in a range of, for example, 20 mm to 35 mm.

Further, in the mesa structure including the first step difference structure and the second step difference structure, the shapes of the first step difference structure and the second step difference structure in plan view are not particularly limited, and for example, it may be As shown in Fig. 5 (c), it is rectangular. The height of the first step difference structure shown by M1 in FIG. 5 (b) varies depending on the application and the like. For example, the first step difference in a rectangular shape in a plan view ranges from 10 μm to 50 μm. The vertical and horizontal lengths of the structure are the same as the above-mentioned mesa structure. The height of the second step difference structure shown by M2 in FIG. 5 (b) varies depending on the application and the like, and is, for example, within a range of 1 μm to 5 μm. Furthermore, the vertical and horizontal lengths of the second stepped structure having a rectangular shape in a plan view are different depending on applications and the like, and are in a range of, for example, 18 mm to 33 mm.

Examples of the method for forming the mesa structure and the first step difference structure and the second step difference structure include wet etching using an etching mask and the like.

(2) Base portion The base portion is provided on the main surface with the mesa structure.

a. In the case where the mesa structure has the above-mentioned single step structure, as the base portion, a depression including the mesa structure in a plan view may be provided on the surface of the base portion opposite to the main surface as shown in FIG. 1. It is also possible that the above-mentioned recessed part is not provided, but it is preferable that the above-mentioned recessed part is provided. The reason is that when the transfer pattern of the nanoimprint stencil sheet is brought into close contact with the curable resin layer applied to the surface of the object to be transferred, the air pressure in the recessed portion is increased to increase the nanometer pressure. The printing die sheet is bent to prevent air from being trapped between the transfer pattern and the curable resin layer.

When the mesa structure includes the first step difference structure and the second step difference structure, the base portion may be provided with a plan view including a surface on the side of the base portion opposite to the main surface as shown in FIG. 5. The recessed portion of the second step structure may be a portion where the recessed portion is not provided, but it is preferable that the recessed portion is provided. This is because, similar to the above, it is possible to suppress air from being trapped between the transfer pattern and the curable resin layer. Furthermore, as the recessed portion, it is preferable to include the first step difference structure in a plan view as shown in FIG. 5. The reason is that when the air pressure in the recessed portion is increased and the nanoimprinting die is bent, the following problems such as peeling of the light-shielding portion and tantalum oxide film provided on the main surface of the first step structure described below can be suppressed. .

The shape of the recessed portion when viewed in plan is not particularly limited as long as the shape includes the second step structure in plan view, and may be, for example, circular. The depth of the recessed portion is, for example, in a range of 4 mm to 5.5 mm, and the diameter of the circular recessed portion is, for example, about 80 mm.

Examples of the method for forming the depressed portion include machining, and the like, as long as it is appropriately selected in accordance with the shape and size of the depressed portion and the material of the transparent substrate.

b. The shape of the base in plan view is not particularly limited, but is generally rectangular. In this case, the lengths of the above-mentioned bases in the vertical and horizontal directions are different depending on applications and the like, and are in the range of 142 mm to 162 mm, for example. The thickness of the base portion varies depending on materials, applications, and the like, and is, for example, within a range of 0.5 mm to 10 mm.

(3) Other examples of the material constituting the light-transmitting substrate include synthetic quartz, soda glass, fluorite, and calcium fluoride. Among them, synthetic quartz is preferably used because it has a high performance and stable quality in the substrate for forming a nanoimprint die, and can form a fine transfer pattern with high accuracy. As the light-transmitting property of the light-transmitting substrate, it is preferable that the transmittance of light in a wavelength range of 300 nm to 450 nm is 85% or more.

4. The above-mentioned mesa structure includes the first step difference structure and the second step difference structure, and the nano-imprinting die sheet is preferably as shown in FIG. 5, and is the main surface of the first step difference structure 27. The area around the second step difference structure 28 in 27a is provided with a light shielding portion 70, and a tantalum oxide film 60 is provided on the main surface 70a of the light shielding portion 70 so as to cover the main surface 70a of the light shielding portion 70 without being exposed. The reason is that the above-mentioned light-shielding portion can suppress exposure of exposed light to unintended areas during photo-imprinting, and can be used for sulfuric acid cleaning or alkaline cleaning and cleaning using plasma ashing. The tantalum oxide film sufficiently suppresses the reduction or disappearance of the light-shielding portion film.

Here, FIG. 6 is a schematic cross-sectional view showing another example of the nanoimprint die sheet of the present invention, and is a view showing a region corresponding to the region shown in FIG. 5 (a). In the nano-imprint die 10 shown in FIG. 6, the main surface 70 a and the side surface 70 b of the light shielding portion 70 are continuously provided so as to cover the main surface 70 a and the side surface 70 b of the light shielding portion 70 without being exposed.

The tantalum oxide film, which is provided on the main surface of the light-shielding portion, is preferably provided on the main surface and side surface of the light-shielding portion so as to cover the main surface and side surface of the light-shielding portion as shown in FIG. 6. The reason is that the light shielding portion can be restrained from being affected by sulfuric acid cleaning or alkali cleaning and plasma ashing from the side, so that the reduction or disappearance of the film of the light shielding portion can be effectively suppressed.

The light-shielding portion is not particularly limited as long as it can prevent the exposed light from being irradiated to the unintended area during photo-imprinting, and may have a single-layer structure including only a light-shielding film, but it is preferably as shown in FIG. As shown in FIG. 5 and FIG. 6, there is a multilayer structure in which a light-shielding film 80 and a high-contrast film 50 are laminated in this order. The reason is that the light-shielding property of the multilayer structure is higher than that of the single-layer structure, and therefore, it is possible to effectively suppress exposure of exposed light to unintended areas during light imprinting.

In addition, it is preferable that the light shielding portion is formed not only in a region around the second step difference structure among the main surfaces of the first step difference structure, but also on a side surface of the first step difference structure. Furthermore, in this case, a tantalum oxide film may be formed on a light shielding portion on the side surface of the first step structure.

Examples of the material of the light-shielding film include metals such as Al, Ni, Co, Cr, Ti, Ta, W, Mo, Sn, Zn, and the like. These oxides and nitrides may also be used. , Alloys, etc. As the light-shielding property of the light-shielding film, the transmittance of light in a wavelength range of 365 nm is preferably 1% or less, and particularly preferably 0.1% or less.

The thickness of the light-shielding film is not particularly limited as long as it can suppress exposure of exposed light to unintended areas during photoimprinting. For example, when Cr is used as the material of the light-shielding film, the thickness is 15 It suffices if it is in a range of nm or more. A particularly preferred range is from 35 nm to 1000 nm, and a particularly preferred range is from 55 nm to 1000 nm. The reason is that the thickness of the light-shielding film is greater than or equal to the lower limit of these ranges, and the transmittance of light in the wavelength range of 365 nm can be 1% or less and 0.1% or less, respectively.

Examples of the method for forming the light-shielding film include a PVD method (physical vapor deposition) such as a vacuum evaporation method, a sputtering method, and an ion plating method; a plasma CVD method; a thermal CVD method; And CVD (chemical vapor deposition), etc., as well as coatings, dyes, and pigments.

Since the high-contrast film in the multilayer structure is the same as the high-contrast film described in the item of "2. High-contrast film", the description here is omitted.

B. Method for manufacturing nano-imprinting die The method for producing nano-imprinting die of the present invention is characterized by including a preparation step for preparing a member for forming a die, and the member for forming the die is provided with a transparent member. An optical substrate and a high-contrast film, the light-transmitting substrate has a base portion and a mesa structure provided on a main surface of the base portion, and a bump pattern transfer pattern and a mark of the uneven structure are provided on the main surface of the mesa structure. The pattern is used to form the high-contrast film on the entire surface of the main surface side of the translucent substrate. In the first resin layer forming step, a marking pattern area provided with the marking pattern is formed into a thin film, and The first pattern of the transfer pattern region of the transfer pattern is a thick film, and a first resin layer is formed on the mark pattern and the transfer pattern. The first etching step is performed on the above-mentioned first resin layer. The die-forming member is etched, and the high-contrast film is left on at least the bottom surface of the recessed portion of the marking pattern and the transfer pattern region, and other parts of the high-contrast film are removed. A tantalum oxide film forming step of forming a tantalum oxide film on the entire surface of the main surface side of the die-forming member having undergone the first etching step; a second resin layer forming step of forming the pattern region with the mark A method of forming a thick film and forming the transfer pattern region into a thin film, forming a second resin layer on the tantalum oxide film formed on the marking pattern region and the transfer pattern region; the second etching step is performed by Etching the member for forming a die on which the second resin layer is formed, leaving the tantalum oxide film formed on at least the surface of the high-contrast film, and removing other parts of the tantalum oxide film; and a third etching In the step, the high-contrast film provided in the transfer pattern region is removed by performing etching using the remaining tantalum oxide film as a mask.

An example of a method for manufacturing the nanoimprint die sheet of the present invention will be described with reference to the drawings. 7 (a) to 9 (c) are schematic cross-sectional views showing an example of a method for manufacturing a nanoimprint die sheet according to the present invention.

First, as shown in FIG. 7 (a), a mold-forming member 1 is prepared. The mold-forming member 1 includes a light-transmitting substrate 20 having a base portion 21 and a table surface provided on the main surface 21 a of the base portion 21. Structure 22, and a transfer pattern 30 of a concave-convex structure and a marking pattern 40 of a concave-convex structure are provided on a main surface 22a of the mesa structure 22; and a high-contrast film 50 is provided on a bottom surface 42a and The upper surface 44 a of the convex portion 44 and the bottom surface 32 a of the concave portion 32 of the transfer pattern 30 and the upper surface 34 a of the convex portion 34.

Next, as shown in FIG. 7 (b), a thin film 91a of the first resin layer 91 is formed on the high-contrast film 50 provided on the bottom surface 42a of the concave portion 42 and the upper surface 44a of the convex portion 44 of the marking pattern 40, A thick film 91b of the first resin layer 91 which is thicker than the film 91a is formed on the high-contrast film 50 of the bottom surface 32a of the concave portion 32 and the upper surface 34a of the convex portion 34 of the transfer pattern 30.

In this case, first, the high-contrast film 50 provided on the bottom surface 42a of the recessed portion 42 and the upper surface 44a of the raised portion 44 of the marking pattern 40, and the bottom surface 32a and the raised portion provided on the concave portion 32 of the transfer pattern 30. A resin is dropped on the high-contrast film 50 on the upper surface 34 a of the portion 34. Next, the resin is cured in a state where it is pressed against the resin layer thickness specification die sheet 100, and then the resin layer thickness specification die sheet 100 is released. Thereby, the first resin layer 91 having the thickness H1 of the thin film 91a and the thickness H2 of the thick film 91b shown in FIG. 7 (b) is formed so as to satisfy H1> H2.

Next, as shown in FIG. 7 (c), the first resin layer 91 is partially removed by performing dry etching using an oxygen-based gas and using an etch-back method. In this case, as described above, the thickness H1 of the thin film 91a and the thickness H2 of the thick film 91b are specified so as to satisfy H1 <H2, whereby the high contrast of the bottom surface 42a provided on the recessed portion 42 of the marking pattern 40 can be achieved. The thick film 91b formed on the translucent substrate side of the thin film 91a formed on the film 50 and the high contrast film 50 provided on the bottom surface 32a of the concave portion 32 and the upper surface 34a of the convex portion 34 of the transfer pattern 30 The translucent base material side remains, and other parts of the first resin layer 91 are removed.

Next, as shown in FIG. 8 (a), the thin film 91a and the thick film 91b of the remaining first resin layer 91 are used as a mask, and dry etching using a chlorine-based gas is performed, thereby setting the pattern 40 for marking. The high-contrast film 50 of the bottom surface 42a of the concave portion 42 and the bottom surface 32a of the concave portion 32 of the transfer pattern 30 and the upper surface 34a of the convex portion 34 remain, and will be provided on the high surface 44a of the convex portion 44 of the marking pattern 40. The film 50 is removed.

Next, as shown in FIG. 8 (b), the remaining first resin layer 91 is removed by wet cleaning or dry etching using an oxygen-based gas, and then the remaining pattern 40 for marking is left uncovered. In the form of the high-contrast film 50 on the bottom surface 42a of the recessed portion 42, a tantalum oxide film 60 is continuously formed on the surface of the high-contrast film 50 and the side surface 44b and the upper surface 44a of the convex portion 44 of the marking pattern 40. A tantalum oxide film 60 is formed on the surface of the high-contrast film 50 remaining on the bottom surface 32a of the concave portion 32 and the upper surface 34a of the convex portion 34 of the transfer pattern 30.

Next, as shown in FIG. 8 (c), a tantalum oxide film is formed on the surface of the high-contrast film 50 remaining on the bottom surface 42a of the recessed portion 42 of the marking pattern 40 and the upper surface 44a of the protruding portion 44 of the marking pattern 40. A thick film 92a of the second resin layer 92 is formed on 60, and is formed on the tantalum oxide film 60 formed on the surface of the high-contrast film 50 remaining on the bottom surface 32a of the concave portion 32 and the upper surface 34a of the convex portion 34 of the transfer pattern 30 The thin film 92b of the second resin layer 92 which is thinner than the thick film 92a. At this time, the thick film 92a of the second resin layer 92 is formed in a region located inward of the formation region R of the thin film 91a of the first resin layer 91 shown in FIG. 7 (b) in a plan view.

In this case, first, a tantalum oxide film 60 formed on the surface of the high-contrast film 50 remaining on the bottom surface 42a of the recessed portion 42 of the marking pattern 40 and the upper surface 44a of the protruding portion 44 of the marking pattern 40, and A resin is dropped on the tantalum oxide film 60 formed on the surface of the high-contrast film 50 remaining on the bottom surface 32 a of the concave portion 32 and the upper surface 34 a of the convex portion 34 of the transfer pattern 30. Next, the resin is cured in a state where it is pressed against the resin layer thickness specification die sheet 100, and then the resin layer thickness specification die sheet 100 is released. Thereby, the second resin layer 92 having the thickness H3 of the thick film 92a and the thickness H4 of the thin film 92b shown in FIG. 8 (c) is formed so as to satisfy H3> H4.

Next, as shown in FIG. 9 (a), the second resin layer 92 is partially removed by performing dry etching using an oxygen-based gas and using an etch-back method. In this case, as described above, the thickness H3 of the thick film 92a and the thickness H4 of the thin film 92b are specified so as to satisfy H3> H4, whereby the high contrast of the bottom surface 42a of the recessed portion 42 remaining on the marking pattern 40 can be achieved. The surface of the film 50 and the thick film 92a formed on the tantalum oxide film 60 formed on the tantalum oxide film 60 formed on the upper surface 44a of the convex portion 44 of the marking pattern 40 remain on the transparent substrate side. Remove. At this time, as described above, the thick film 92a of the second resin layer 92 is formed in a region which is located inward of the formation region R of the thin film 91a of the first resin layer 91 in a plan view. The outer peripheral portion 61 of the tantalum oxide film 60 formed on the upper surface 44 a is exposed from the thick film 92 a of the second resin layer 92.

Next, as shown in FIG. 9 (b), the thick film 92a of the remaining second resin layer 92 is used as a mask, and dry etching using a fluorine-based gas is performed to thereby make the recessed portion remaining in the marking pattern 40 The surface of the high-contrast film 50 of the bottom surface 42a of 42 and the side surface 44b and the upper surface 44a of the convex portion 44 of the marking pattern 40 are continuously formed, and other portions of the tantalum oxide film 60 are removed. At this time, since the outer peripheral portion 61 of the tantalum oxide film 60 formed on the upper surface 44 a of the convex portion 44 of the marking pattern 40 is exposed from the thick film 92 a of the second resin layer 92, the outer peripheral portion 61 of the tantalum oxide film 60 is removed. In addition, a part of the upper surface 44 a side of the convex portion 44 of the marking pattern 40 is removed in the region of the outer peripheral portion 61. As a result, grooves 26 are formed on the upper surface 44 a of the convex portion 44 of the marking pattern 40 along the region that becomes the thick film 92 a of the second resin layer 92.

Next, as shown in FIG. 9 (c), the remaining thick film 92a of the second resin layer 92 is removed by wet cleaning or dry etching using an oxygen-based gas, and then the remaining tantalum oxide film 60 is removed. As a mask, dry etching using a chlorine-based gas is performed, thereby removing the high-contrast film 50 provided on the bottom surface 32 a of the concave portion 32 and the upper surface 34 a of the convex portion 34 of the transfer pattern 30. Thereby, the nanoimprint die 10 shown in FIG. 1 can be manufactured.

Therefore, according to the present invention, a nanoimprint die capable of sufficiently suppressing the reduction or disappearance of the film of the high-contrast film can be manufactured. Furthermore, since the tantalum oxide film may disappear when the high-contrast film is not processed, it is easy to install so as to cover the high-contrast film without exposing it.

1. Each step of the method for manufacturing a nanoimprinting die sheet Next, each step of a method for manufacturing a nanoimprinting die sheet will be described.

(1) Preparation step In the above preparation step, a member for forming a mold is prepared. The member for forming a mold includes a light-transmitting substrate having a base portion and a mesa structure provided on a main surface of the base portion. The main surface of the mesa structure is provided with a transfer pattern of a concave-convex structure and a pattern for marking a concave-convex structure; and a high-contrast film provided on the entire surface of the main surface side of the light-transmitting substrate.

The above-mentioned light-transmitting substrate is the same as the light-transmitting substrate described in the item "A. Nano-imprinting mold sheet 3. Light-transmitting substrate", and therefore description thereof is omitted.

The high-contrast film is the same as the "A. Nanometer" except that it is provided on the bottom surface of the concave portion and the upper surface of the convex portion of the marking pattern and the bottom surface of the concave portion and the upper surface of the convex portion of the transfer pattern. The high-contrast film described in the item "Imprinting mold 2. High-contrast film" is the same, so the description here is omitted.

(2) First resin layer forming step In the first resin layer forming step, a marking pattern area provided with the marking pattern is a thin film, and a transfer pattern area provided with the transfer pattern is a thick film. In a method, a first resin layer is formed on the marking pattern and the transfer pattern.

Here, the thickness of the film of the first resin layer refers to the thickness of the film of the first resin layer in the recessed portion of the marking pattern shown by H1 in FIG. 7 (b). The thickness of the thick film of the resin layer refers to the thickness of the thick film of the first resin layer in the concave portion of the transfer pattern shown by H2 in FIG. 7 (b).

The thickness of the thin film of the first resin layer and the thickness of the thick film of the first resin layer are appropriately set according to the etching conditions.

The material of the first resin layer is not particularly limited as long as it is a curable resin used in nanoimprint lithography, and examples thereof include a thermosetting resin and a photocurable resin. Particularly preferred is a photocurable resin, and particularly preferred is an ultraviolet curable resin.

(3) First etching step In the first etching step, at least the bottom surface of the recessed portion of the marking pattern and the transfer are performed by etching the member for forming a mold sheet on which the first resin layer is formed. The pattern region leaves the high-contrast film and removes other parts of the high-contrast film.

The above-mentioned first etching step is not particularly limited, and generally includes a first resin layer removing step and a high-contrast film removing step, as shown in FIGS. 7 (c) and 8 (a). This first resin layer removing step is provided by The light-transmitting substrate side of the thin film of the first resin layer formed on the high-contrast film on the bottom surface of the concave portion of the marking pattern, and provided on the bottom surface and convex portion of the concave portion of the transfer pattern The thick transparent film of the first resin layer formed on the surface of the high-contrast film remains on the translucent substrate side, and other parts of the first resin layer are removed. The high-contrast film removal step is performed by removing the remaining The first resin layer is used as a mask for etching, and the high-contrast film provided on the bottom surface of the concave portion of the marking pattern and the bottom surface of the concave portion of the transfer pattern and the upper surface of the convex portion is left, and the high-contrast film is left. The other parts of the contrast film are removed.

The method of removing the first resin layer is not particularly limited as long as the light-transmitting substrate side of the first resin layer can be left and other parts of the first resin layer can be removed, and an etch-back can be used. Dry etching etc. Examples of the gas used in the dry etching include an oxygen-based gas.

As a method for etching the high-contrast film, dry etching or wet etching may be used, but dry etching is preferred. Examples of the gas used in the dry etching include a chlorine-based gas.

(4) Tantalum oxide film formation step In the tantalum oxide film formation step, a tantalum oxide film is formed on the entire surface of the main surface side of the die-forming member having undergone the first etching step.

The tantalum oxide film is the same as the tantalum oxide film described in the item "A. Nano-imprinting die sheet 1. Tantalum oxide film", so the description here is omitted.

The method for forming the tantalum oxide film is not particularly limited, and examples thereof include a PVD method (physical vapor deposition) such as a vacuum evaporation method, a sputtering method, and an ion plating method; a plasma CVD method; a thermal CVD method; CVD methods (chemical vapor deposition), etc., and coatings, dyes, pigments, etc.

The step of forming the tantalum oxide film is performed after removing the remaining first resin layer.

(5) The second resin layer forming step In the second resin layer forming step, the marking pattern area and the transfer pattern area are formed into a thick film and the transfer pattern area are formed as a thin film in the marking pattern area and the transfer A second resin layer is formed on the tantalum oxide film formed in the pattern region.

Here, the thickness of the thick film of the second resin layer refers to the thickness of the thick film of the second resin layer in the recessed portion of the marking pattern as shown by H3 in FIG. 8 (c). The thickness of the film of the second resin layer refers to the thickness of the film of the second resin layer in the recessed portion of the transfer pattern shown by H4 in FIG. 8 (c).

The thickness of the thin film of the second resin layer and the thickness of the thick film of the second resin layer are appropriately set depending on the etching conditions.

Since the material of the second resin layer is the same as that of the first resin layer, the description here is omitted.

(6) Second etching step In the second etching step, the tantalum oxide formed on at least the surface of the high-contrast film is etched by etching the member for forming a mold on which the second resin layer is formed. The film remains, and other parts of the tantalum oxide film are removed.

The second etching step is not particularly limited. Usually, as shown in FIGS. 9 (a) and 9 (b), it includes a second resin layer removing step and a tantalum oxide film removing step. The second resin layer removing step is to leave the remaining The thick transparent film of the second resin layer formed on the tantalum oxide film formed on the surface of the high-contrast film on the bottom surface of the recessed portion of the marking pattern remains on the translucent substrate side of the thick resin, and the second resin The other part of the thick film of the layer and the thin film of the second resin layer are removed, and the tantalum oxide film removing step is performed by using the remaining thick film of the second resin layer as a mask to etch the remaining film on the mark The remaining tantalum oxide film formed on the surface of the high-contrast film on the bottom surface of the concave portion of the pattern is used to remove other parts of the tantalum oxide film.

As a method for removing the second resin layer, as long as the transparent substrate side of the thick film of the second resin layer can be left, and other parts of the thick film of the second resin layer and the second resin layer can be left. The thin film removal is not particularly limited, and examples thereof include dry etching using an etch-back method. Examples of the gas used in the dry etching include an oxygen-based gas.

As the method for etching the tantalum oxide film, dry etching or wet etching may be used, but dry etching is preferred. Examples of the gas used in the dry etching include a fluorine-based gas.

(7) Third etching step In the third etching step, the high-contrast film provided in the transfer pattern region is removed by performing etching using the remaining tantalum oxide film as a mask.

Since the method of etching the high-contrast film is the same as the first etching step, the description here is omitted.

The second step of removing the high-contrast film may be performed after removing the remaining second resin layer or may be performed before removing them, but it is usually performed after removing these.

2. Manufacturing Method of Nanoimprinting Die The method of manufacturing the nanoimprinting die of the present invention will be described below.

(1) Manufacturing method of nanoimprinting die sheet A preferred aspect of the above-mentioned method of manufacturing a nanoimprinting die sheet will be described.

As the method for manufacturing the nanoimprint die, the manufacturing method is preferably as shown in FIGS. 7 (c) and 8 (a) and FIGS. 9 (a) and 9 (b). In the first etching step, the contrast film is left only on the bottom surface of the recessed portion in the marking pattern, and other parts of the contrast film are removed. In the second etching step, the surface of the high-contrast film is left. And the tantalum oxide film formed on the upper surface of the convex portion of the marking pattern remains. The reason is that the nano imprint die can be manufactured as shown in FIG. 1 and FIG. 2. In the marking pattern, the contrast film is provided only on the bottom surface of the concave portion, and the high The tantalum oxide film is provided on the surface of the contrast film and the upper surface of the convex portion of the marking pattern.

Furthermore, as a method for manufacturing such a nanoimprint die, a manufacturing method is particularly preferred, as shown in FIGS. 8 (c) to 9 (b), in the above-mentioned second resin layer forming step, The area that becomes the thick film of the second resin layer is set to be inward than the area that becomes the thin film of the first resin layer in a plan view. In the second etching step, the etching is performed on the mesa structure. The main surface has grooves formed along a region that becomes a thick film of the second resin layer. The reason for this is that the nanoimprint die sheet capable of judging the presence or absence of the tantalum oxide film by identifying the presence or absence of the groove can be manufactured.

(2) Manufacturing method of nano-imprint die sheet including mesa structure including first step difference structure and second step difference structure As the above-mentioned method for manufacturing nano-imprint die, the following manufacturing method is preferred: In the preparation step, the die-forming member is prepared. In the die-forming member, the mesa structure has a first step structure provided on the main surface of the base portion and a main surface provided on the first step structure. The second step difference structure is provided with the transfer pattern and the marking pattern on the main surface of the second step difference structure, and further has the second step difference provided on the main surface of the first step difference structure. In the light-shielding portion of the surrounding area of the structure, in the first resin layer forming step, the first resin layer is also formed on the light-shielding portion, and in the first etching step, the light-shielding portion is left and the tantalum oxide is left. In the film forming step, the tantalum oxide film is formed on the main surface of the light-shielding portion. In the second resin layer forming step, the first tantalum oxide film is also formed on the tantalum oxide film formed on the main surface of the light-shielding portion. 2 resin layers, In the second etching step, the tantalum oxide film formed on the main surface of the light shielding portion is left. Hereinafter, this manufacturing method will be described with reference to the drawings.

10 (a) to 12 (c) are cross-sectional views schematically showing steps in another example of a method for manufacturing a nanoimprint die sheet according to the present invention.

First, as shown in FIG. 10 (a), a mold-forming member 1 is prepared. In the mold-forming member 1, the mesa structure 22 includes a first step structure 27 provided on a main surface 21 a of the base 21 and a first step structure 27 provided on the main surface 21 a. The second step difference structure 28 of the main surface 27a of the first step difference structure 27 is provided with the transfer pattern 30 of the uneven structure and the mark pattern 40 of the uneven structure on the main surface 28a of the second step difference structure 28. The light-shielding portion 70 having a region around the second-step difference structure 28 in the main surface 27a of the first-step difference structure 27 has a member for forming a mold similar to that shown in FIG. 7 (a) in addition to the above. 1 the same structure. The light-shielding portion 70 has a multilayer structure in which a light-shielding film 80 and a high-contrast film 50 are laminated in this order.

Next, as shown in FIG. 10 (b), the thin film 91a and the thick film 91b of the first resin layer 91 are formed in the same manner as in the step shown in FIG. 7 (b), and the first resin layer 91 is formed on the light shielding portion 70. The light shielding film 91c.

In this case, first, resin is dripped in the area | region of the marking pattern 40 and the transfer pattern 30 similarly to the process shown in FIG.7 (b), and resin is dripped in the main surface 70a of the light-shielding part 70. Next, as shown in FIG. 10 (b), the resin is cured in a state where it is pressed against the resin layer thickness specification die sheet 100, and then the resin layer thickness specification die sheet 100 is released. Thereby, the thin film 91a, the thick film 91b, and the light-shielding part film 91c of the first resin layer 91 are formed.

Next, as shown in FIG. 10 (c), the first resin layer 91 is partially removed by performing dry etching using an oxygen-based gas and using an etch-back method. In this case, the light-transmitting substrate side of the thin film 91a and the thick film 91b of the first resin layer 91 can be left in the same manner as shown in FIG. 7 (c), and the light-shielding portion of the first resin layer 91 can be left. The other part of the resin layer was removed by leaving the transparent substrate side of the film 91c.

Next, as shown in FIG. 11 (a), the thin film 91a, the thick film 91b, and the light-shielding portion film 91c of the remaining first resin layer 91 are used as a mask, and dry etching using a chlorine-based gas is performed. The high-contrast film 50 is left in the same manner as in the step shown in FIG. 8 (a), and the high-contrast film 50 in the light-shielding portion 70 is left, and other parts of the high-contrast film 50 are removed.

Next, as shown in FIG. 11 (b), after the remaining first resin layer 91 is removed, a tantalum oxide film 60 is formed in the same manner as that shown in FIG. 8 (b), and the light shielding portion 70 is covered without being exposed. In the form of the main surface 70a and the side surface 70b, a tantalum oxide film 60 is formed continuously with the main surface 70a and the side surface 70b of the light shielding portion 70.

Next, as shown in FIG. 11 (c), the thick film 92a and the thin film 92b of the second resin layer 92 are formed in the same manner as in the step shown in FIG. 8 (c), and are oxidized on the main surface 70a formed on the light-shielding portion 70. On the tantalum film 60, a thick film 92c for a light-shielding portion of the second resin layer 92 which is thicker than the thin film 92b is formed.

In this case, first, resin is added dropwise to the areas of the marking pattern 40 and the transfer pattern 30 in the same manner as shown in FIG. 8 (c), and a tantalum oxide film is formed on the main surface 70a of the light shielding portion 70. Add 60 drops of resin. Next, the resin is cured in a state where it is pressed against the resin layer thickness specification die sheet 100, and then the resin layer thickness specification die sheet 100 is released. Thereby, the thickness H3 of the thick film 92a, the thickness H4 of the thin film 92b, and the thickness H6 of the thick film 92c for the light-shielding portion shown in FIG. 11 (c) are formed to satisfy the second requirement of H3> H4 and H6> H4. Resin layer 92.

Next, as shown in FIG. 12 (a), the second resin layer 92 is partially removed by performing dry etching using an oxygen-based gas and using an etch-back method. In this case, as described above, the thickness of each resin layer is specified so as to satisfy H3> H4 and H6> H4, whereby the thick film 92a can be made to transmit light in the same manner as the step shown in FIG. 9 (a). The base material side remains, and the light-transmitting base material side of the thick film 92c for the light-shielding portion remains, and the other parts of the resin layer are removed.

Next, as shown in FIG. 12 (b), the thick film 92a of the remaining second resin layer 92 and the thick film 92c for the light-shielding portion are used as a mask, and dry etching using a fluorine-based gas is performed. In the step shown in (b), the tantalum oxide film 60 is similarly left, and the tantalum oxide film 60 formed on the main surface 70a of the light shielding portion 70 is left, and the other parts of the tantalum oxide film 60 are removed.

Next, as shown in FIG. 12 (c), after removing the remaining thick film 92a of the second resin layer 92 and the light-shielding portion of the second resin layer 92 with the thick film 92c, the procedure is the same as that shown in FIG. 9 (b). The high-contrast film 50 is removed. Thereby, the nanoimprint die 10 shown in FIG. 5 is manufactured. The removal of the high-contrast film 50 may be performed after removing the thick film 92a of the remaining thick film 92a of the second resin layer 92 with the thick film 92c, but it is usually performed after removing these.

Therefore, as the method for manufacturing the nanoimprint stencil, the method for manufacturing a nanoimprint stencil having the mesa structure including the first step difference structure and the second step difference structure is preferable. The reason for this is that it is possible to manufacture the nano-light which can suppress the exposure of light to an unintended area during photo imprint by the light-shielding portion, and can suppress the reduction or disappearance of the film of the light-shielding portion by the tantalum oxide film. Rice embossing die.

Hereinafter, each step of the method for manufacturing a nanoimprint die sheet including the first step difference structure and the second step difference structure will be described.

a. Preparation step In the above preparation step, the die-forming member is prepared. In the die-forming member, the mesa structure has a first step structure provided on the main surface of the base portion and is provided on the first step. The second step difference structure of the main surface of the difference structure is provided with the transfer pattern and the marking pattern on the main surface of the second step difference structure, and further includes a second step structure provided on the main surface of the first step difference structure. The light-shielding portion in the area around the second step difference structure.

The mesa structure having the first step difference structure and the second step difference structure is the same as the above-mentioned "A. Nano-imprinting mold 3. Light-transmitting substrate (1) mesa structure c. Mesa structure" The table structure described in the items is the same, so the description here is omitted.

The above-mentioned light-shielding portion is the same as the light-shielding portion described in the item "A. Nanoimprinting mold sheet 4. Others", and therefore description thereof is omitted here.

b. First resin layer forming step In the first resin layer forming step, the first resin layer is also formed on the light shielding portion.

As the thickness of the first resin layer formed on the light-shielding portion as indicated by H5 in FIG. 10 (b), as long as it is formed in the first resin layer removal step in the first etching step described below, The residue on the light-transmitting substrate side of the first resin layer on the light-shielding portion is not particularly limited, and is appropriately set depending on the etching conditions.

c. First etching step In the first etching step, the light shielding portion is left.

The first etching step is not particularly limited, but as shown in FIG. 10 (c) and FIG. 11 (a), in the first resin layer removing step, the first resin layer formed on the light-shielding portion is usually formed. The light-transmitting substrate is left, and other parts of the first resin layer are removed. In the high-contrast film removing step, the remaining first resin layer is used as the mask for the etching, and The light-shielding portion is left.

d. tantalum oxide film forming step In the tantalum oxide film forming step, the tantalum oxide film is formed on a main surface of the light shielding portion.

In the step of forming the tantalum oxide film, it is preferable to continuously form the tantalum oxide film on the main surface and side surfaces of the light shielding portion so as to cover the main surface and side surfaces of the light shielding portion as shown in FIG. 11 (b). . The reason is that the following nanoimprinting die sheet can be manufactured, and since the light-shielding portion can be restrained from being affected by sulfuric acid cleaning or alkali cleaning and plasma ashing from the side, the light-shielding portion can be effectively suppressed. The film is reduced or disappeared.

e. Second resin layer forming step In the second resin layer forming step, the second resin layer of the thick film is also formed on the tantalum oxide film formed on the main surface of the light shielding portion.

Here, the thickness of the thick film formed on the tantalum oxide film formed on the main surface of the light-shielding portion refers to the second resin in the light-shielding portion shown by H6 in FIG. 11 (c). The thickness of the thick film of the layer is, for example, in the same range as the thickness of the thick film of the second resin layer in the recessed portion of the marking pattern shown by H3 in FIG. 8 (c).

f. Second etching step In the second etching step, the tantalum oxide film formed on the main surface of the light shielding portion is left.

The second etching step is not particularly limited, but as shown in FIG. 12 (a) and FIG. 12 (b), in the second resin layer removing step, the tantalum oxide formed on the main surface of the light-shielding portion is usually made. The second resin layer of the thick film formed on the film remains on the light-transmitting substrate side, and other parts of the thick film of the second resin layer are removed. In the step of removing the tantalum oxide film, the remaining The second resin layer of the thick film formed on the tantalum oxide film formed on the main surface of the light shielding portion is used as the mask for the etching, and the tantalum oxide film formed on the main surface of the light shielding portion remains. .

C. Nano-imprinting die (second embodiment)
In addition, in the present invention, as a second embodiment, a nanoimprinting die is provided, comprising a light-transmitting substrate having a base portion and a mesa structure provided on the main surface of the base portion, and The main surface of the mesa structure is provided with a transfer pattern with a concave-convex structure and a marking pattern with a concave-convex structure. A high-contrast film is provided on the bottom surface of the concave portion of the marking pattern, and the ends of the high-contrast film are not exposed. Preferably, a protective film that continuously covers the surface of the high-contrast film and the side surface of the convex portion of the marking pattern and the upper surface of the convex portion of the marking pattern and includes a material different from the high-contrast film is provided. A protective film is provided so that an edge part may be located on the upper surface of the convex part of the said marking pattern.

A description will be given of the nanoimprint die for this aspect with reference to the drawings. FIG. 13 (a) is a schematic cross-sectional view showing an example of the nanoimprint die in this aspect. FIG. 13 (b) is an enlarged view within a dotted frame shown in FIG. 13 (a). FIG. 13 (c) is a diagram illustrating a region where the protective film is formed.

As shown in FIGS. 13 (a) to 13 (c), the nanoimprint die 10 includes a light-transmitting substrate 20 having a base portion 21 and a mesa structure 22 provided on a main surface 21 a of the base portion 21. A transfer pattern 30 of a concave-convex structure and a marking pattern 40 of a concave-convex structure are provided on the main surface 22 a of the mesa structure 22. Further, a recessed portion 25 including a mesa structure 22 in plan view is provided on a surface of the base portion 21 opposite to the main surface 21 a. A high-contrast film 50 containing Cr is provided only on the bottom surface 42 a of the recessed portion 42 of the marking pattern 40. The high-contrast film 50 constitutes an alignment mark. The protective film 600 including a material different from the high-contrast film is formed so as to continuously cover the surface of the high-contrast film 50 and the side surface 44b of the convex portion 44 of the marking pattern 40 so that the ends of the high-contrast film 50 are not exposed. And the convex upper surface 44a of the marking pattern. Furthermore, the protective film 600 is provided so that an edge part may be located on the upper surface 44a of the convex part 44 of the marking pattern.

In this way, the protective film including a material different from the high-contrast film is formed so as to continuously cover the surface of the high-contrast film and the side of the convex portion of the marking pattern and the marking pattern so that the ends of the high-contrast film are not exposed. The upper surface of the convex portion is provided so that the end portion is located on the upper surface of the convex portion of the marking pattern. As a result, the end portion of the high-contrast film is sealed by the above-mentioned protective film, so that high contrast can be reliably suppressed. The infiltration of the drug solution in contact with the film can suppress the reduction of the film of the high-contrast film. Moreover, even if the said high-contrast film protrudes to the side surface of the convex part of the said marking pattern, it can cover the said high-contrast film without being exposed.

1. Protective film As a constituent material of the protective film, it is not particularly limited as long as it is a material different from the high-contrast film. Examples include tantalum oxide, silicon (amorphous; a-Si), silicon oxide (SiO), and nitrogen. Silicon silicide (SiN), silicon oxynitride (SiON), silicon carbide (SiC), molybdenum silicide (MoSi), tantalum silicide (TaSi), tungsten silicide (WSi), etc.
It is particularly preferred that the protective film is a tantalum oxide film containing tantalum oxide. The tantalum oxide film is sufficiently resistant to sulfuric acid or alkaline cleaning to remove foreign materials such as resist used in nanoimprint lithography, and it is more resistant to foreign materials that cannot be removed during such cleaning. The removed plasma ashing resistance using oxygen-containing gas is also sufficiently high. Therefore, the tantalum oxide film does not disappear when washing with sulfuric acid or alkali, and washing of a die sheet using plasma ashing.

Furthermore, since the tantalum oxide film is different from the etching gas of the high-contrast film, there is no fear that the tantalum oxide film will disappear by dry etching during processing of the high-contrast film.

The protective film of the present invention is characterized by being formed so as to continuously cover the surface of the high-contrast film, the side surface of the convex portion of the marking pattern, and the upper surface of the convex portion of the marking pattern so that the ends of the high-contrast film are not exposed. As a method for forming the protective film in this manner, for example, a PVD method (physical vapor deposition) such as a vacuum evaporation method, a sputtering method, and an ion plating method, a plasma CVD method, a thermal CVD method, and a photo CVD method may be mentioned. CVD method (chemical vapor deposition).

In the present invention, it is particularly preferable to use a method in which the marking pattern surface and the target serving as a material of the protective film are formed in a sputtering method so as to be surely formed on the side surface of the convex portion of the marking pattern. The position of the surface is set at a position that is not horizontal but has an angle of 1 ° to 30 °. A protective film can also be formed on the side of the convex portion, and the substrate can be formed uniformly by rotating the substrate.

Further, as shown in FIG. 13 (c), it is preferable that the protective film 600 includes, in a plan view, a plurality of alignment mark regions 40A in which a concave portion and a convex portion of a marking pattern provided with a high-contrast film are arranged in series. In the method, the area is larger than the alignment mark area 40A.

In this case, generally, it is preferable that the alignment mark area 40A is rectangular, and the end of the protective film 600 is located at a distance of 50 nm or more from each side of the alignment mark area 40A. That is, as shown in FIG. 13 (b), only when the bottom surface 42a of the concave portion 42 of the marking pattern 40 is provided with a high-contrast film 50 containing Cr, the protective film 600 is preferably one of the upper surfaces of the convex portions. The width (w3 and w4 in FIG. 13 (c)) is 50 nm or more.

Further, as shown in FIG. 14 (a), a plurality of the alignment mark regions may be provided on the main surface of the mesa structure. In this case, for example, the concave-convex patterns in the respective alignment mark regions may also be directions orthogonal to each other.
In the case where a plurality of alignment mark regions are provided on the main surface of the mesa structure as described above, it is preferable that the protective film 600 is provided on a plurality of alignment mark regions as shown in FIG. 14 (b). Align the large area of the mark area.

In this case, it is also preferable that the end portion of the protective film is located at a distance of 50 nm or more from each side of the alignment mark region 40A.

As the width from the upper surface of the convex portion of the protective film to the end of the protective film (w3 and w4 in FIG. 13 (c)), as described above, it is preferably 50 nm or more, and particularly preferably 100 nm or more. It is particularly preferable to set it to 500 nm or more. The reason is that the sealing performance with respect to the high-contrast film by the protective film is made more reliable. In addition, generally, the upper limit may be a range that does not affect the pattern surface for marking.

The thickness of the protective film 600 is usually 1 nm to 20 nm, and preferably 1 nm to 10 nm. The reason is that if the protective film formed on the upper surface of the convex portion is too thin, the reduction or disappearance of the film of the high-contrast film cannot be sufficiently suppressed, and if the protective film is too thick, the convex portion of the pattern for marking is provided. In the case of the upper surface, it becomes an obstacle when the transfer pattern is transferred to a transfer target.

Furthermore, the thickness of the protective film in the side surface of the convex portion is preferably in a range of 0.5 nm to 10 nm, and more preferably in a range of 0.5 nm to 5 nm. The reason is that it is difficult to sufficiently protect the high-contrast film when the thickness is thinner than the above range, and it is difficult to form the film thicker than the above range, and it takes time, which is disadvantageous in terms of cost. Furthermore, the thickness of the protective film on the side surface of the convex portion may be uneven. Generally, the upper surface side of the convex portion is thicker, and the opposite side (bottom surface side of the concave portion) becomes thin. Therefore, the value of the thickness of the said film thickness is an average value.

In addition, the nano-imprinting die sheet in this aspect can also separate the protective films provided on the bottom surfaces of the adjacent recesses in the marking pattern.

2. High-contrast film The high-contrast film in this aspect is provided on the bottom surface of the concave portion of the marking pattern. As shown in FIG. 13 (b), the high-contrast film is preferably provided only on the bottom surface 42a of the recessed portion 42 of the marking pattern.
In addition, the high-contrast film is the same as the high-contrast film described in the item "A. Nano-imprinting die sheet 2. High-contrast film", and therefore description thereof is omitted here.

3. Translucent substrate The translucent substrate in this aspect is a person having a base portion and a mesa structure provided on the main surface of the base portion. The light-transmitting base material is the same as the light-transmitting base material described in the item "A. Nano-imprinting mold sheet 3. Light-transmitting base material" described above, and therefore description thereof is omitted here. Furthermore, in this aspect, as in the first embodiment, it is preferable to provide a groove along the protective film on the main surface of the mesa structure. In addition, as in the first embodiment, the mesa structure may be a structure having a single step structure and having the transfer pattern and the marking pattern on the main surface of the single step structure. The first step difference structure and the second step difference structure provided on the main surface of the first step difference structure, and the transfer pattern and the marking pattern are provided on the main surface of the second step difference structure.

D. Two-stage mesa substrate In the present invention, a two-stage mesa substrate is provided, which is characterized in that it is a member for forming a nano-imprint die and has a light-transmitting two-stage mesa substrate forming member. The light-transmitting two-stage mesa base forming member has a base portion and a mesa structure provided on the main surface of the base portion, and the mesa structure includes a first step difference structure provided on the main surface of the base portion and a first step difference structure provided on the main portion. The second-order difference structure of the main surface of the first-order difference structure is provided with a light-shielding portion at least in a region around the second-order difference structure of the main-surface of the first-order difference structure, and covers the main surface of the light-shielding portion on the main surface. A protective film is provided on the main surface of the light shielding portion.

An example of the two-stage mesa substrate of the present invention will be described with reference to the drawings. Fig. 15 is a schematic cross-sectional view showing an example of a two-stage mesa substrate of the present invention. As shown in FIG. 15, the two-stage mesa substrate 200 of the present invention has a light-transmitting two-stage mesa substrate forming member 201, and the light-transmitting two-stage mesa substrate forming member 201 has a base 210 and a mesa provided on the main surface of the base. Construct 220. The mesa structure 220 includes a first step difference structure 270 provided on the main surface of the base 210 and a second step difference structure 280 provided on the main surface of the first step difference structure. In addition, a recessed portion 250 including the second step difference structure in plan view is provided on a surface of the base portion 210 opposite to the main surface 210a. A light shielding portion 70 is provided in a region around the second step difference structure among the main surfaces of the first step difference structure, and a protective film 600 is provided on the main surface of the light shielding portion so as to cover the main face of the light blocking portion 70.

With such a two-stage mesa substrate, it is possible to manufacture a nanoimprinting die that can suppress the exposure of light to an unintended area during light imprinting by the light-shielding portion, and that The protective layer suppresses a reduction or disappearance of a film of the light shielding portion.

1. Translucent 2-stage mesa base formation member The aforementioned translucent 2-stage mesa base formation member is a mesa structure having a base portion and a main surface provided on the base portion.
(1) Mesa structure The light-transmitting two-stage mesa base forming member according to the present invention is the same as the above-mentioned light-transmitting substrate, except that the uneven structure is not formed on the main surface of the mesa structure. That is, the pattern and the transfer pattern are not formed. The mesa structure includes a first-order difference structure provided on the main surface of the base and a second-order difference structure provided on the main surface of the first-order difference structure. The shape of the first-order difference structure and the second-order difference structure when viewed from above, or the heights of the first-order difference structure and the second-order difference structure when viewed from above, and the vertical and horizontal directions of the first-order difference structure and the second-order difference structure when viewed from the top. The length is the same as that described in the item "A. Nano-imprinting mold sheet 3. Light-transmitting substrate (1) mesa structure", so the description here is omitted.

Examples of the method for forming the mesa structure and the first step difference structure and the second step difference structure include wet etching using an etching mask and the like.

(2) Base The above-mentioned base is the same as that described in the item "A. Nano-imprinting mold sheet 3. Translucent base material (2) Base", so the description here is omitted.

2. Light-shielding portion The light-shielding portion is provided in a region around the second-order difference structure among the main surfaces of the first-order difference structure. The light-shielding portion is not particularly limited as long as the light-shielding portion can suppress exposure of exposed light to unintended areas during photo-imprinting. The light-shielding portion may have a single-layer structure including only a light-shielding film, A multilayer structure in which a high-contrast film is laminated in this order. The reason is that the light-shielding property of the multilayer structure is higher than that of the single-layer structure, and therefore, it is possible to effectively suppress exposure of exposed light to unintended areas during light imprinting.

The material, light-shielding property, thickness, transmittance, forming method, and high-contrast film of the light-shielding film are the same as those described in the item "A. Nanoimprinting Die 4. Other", so The description here is omitted.

In addition, the light-shielding portion may be provided only in a region around the second-order difference structure in the main surface of the first-order difference structure as shown in FIG. 15, or may be provided from the main member of the first-order difference structure 270 as shown in FIG. 16. The surface is provided to the main surface of the base 210.

3. Protective film The protective film in the two-stage mesa substrate of the present invention is provided on the main surface of the light-shielding portion so as to cover the main surface of the light-shielding portion without being exposed. With the above-mentioned protective film, the reduction or disappearance of the film of the light shielding portion can be sufficiently suppressed. As shown in FIG. 16, when the light shielding portion 70 is provided from the main surface of the first step difference structure 270 to the main surface of the base portion 210, the protective film 600 is provided at least from the main surface of the first step difference structure 270 to the main portion of the base 210. surface.

The material and film thickness of the protective film are the same as those described in the item "C. Nano Imprinting Die (Second Embodiment) 1. Protective Film", so the description here is omitted. .

E. Method for manufacturing a two-segment mesa substrate In the present invention, a method for manufacturing a two-segment mesa substrate is provided, which is characterized in that it is a method for manufacturing the two-segment mesa substrate, and a light-transmitting two-segment mesa substrate is formed. The light-transmitting two-stage mesa base forming member has a base portion and a mesa structure provided on the main surface of the base portion, and the mesa structure includes a first step difference structure provided on the main surface of the base portion and a first step structure provided on the first step. The second step difference structure of the main surface of the difference structure is for forming a light-shielding portion on the main surface of the side where the first step difference structure and the second step difference structure are arranged on the light-transmitting two-stage mesa base forming member. A film for forming a protective film forming film on the film for forming a light-shielding portion, forming a curable resin layer on the main surface of the first step structure and the main surface of the second step structure, and for the curable resin layer The embossing is performed such that the film thickness of the curable resin layer formed on the main surface of the first step structure is thicker than the film thickness of the curable resin layer formed on the main surface of the second step structure. In the shape of a shade Etching is performed with a film and a protective film remaining only on the main surface of the first step difference structure, thereby manufacturing the main surface of the first step difference structure of the transparent two-stage mesa substrate forming member. A two-stage mesa substrate in which a light shielding portion and a protective film are sequentially arranged in a region around the second step difference structure.

An example of a manufacturing method of the two-stage mesa substrate of the present invention will be described with reference to the drawings. 17 (a) to 17 (c) are schematic cross-sectional views showing an example of a method for manufacturing a two-stage mesa substrate according to the present invention.

First, as shown in FIG. 17 (a), a light-transmitting two-stage mesa base forming member 201 is prepared. The light-transmitting two-stage mesa base forming member 201 has a base 210 and a mesa structure 220 provided on the main surface of the base. The mesa structure 220 has a first step difference structure 270 provided on the main surface 210 a of the base 210 and a second step difference structure 280 provided on the main surface 270 a of the first step difference structure 270.

Next, as shown in FIG. 17 (b), a light-shielding portion forming film 70 is formed on the surface of the two-stage mesa base forming member 201. Next, as shown in FIG. 17 (c), a protective film-forming film 610 is formed on the light-shielding portion-forming film 70.

Next, as shown in FIGS. 17 (d) and (e), the curable resin layer 17 is formed into a thick film on the main surface of the first step structure and a thin film on the main surface of the second step structure. After being cured in a state of being pressed against the resin layer thickness specification die sheet 101, the resin layer thickness specification die sheet 101 is demolded, thereby performing embossing. The material of the curable resin layer is not particularly limited as long as it is a curable resin used in nanoimprint lithography, and examples thereof include a thermosetting resin and a photocurable resin. Particularly preferred is a photocurable resin, and particularly preferred is an ultraviolet curable resin.

Next, as shown in FIG. 17 (f), the main surface of the first step structure in which the curable resin layer is formed as a thick film is left, and the protective film and the film for forming a light-shielding portion are removed by etching. As a result, a two-stage mesa substrate can be manufactured in which a light-shielding portion 70 is provided in a region around the second-stage difference structure among the main surfaces of the first-stage difference structure of the light-transmitting two-stage mesa substrate forming member. A protective film 600 is provided on the main surface of the light shielding portion 70 so as to cover the main surface of the light shielding portion 70.

In addition, in the present invention, a method for manufacturing a two-stage mesa substrate is provided, which is characterized in that it is a method for manufacturing the two-stage mesa substrate, and a light-transmitting two-stage mesa substrate forming member is prepared, and the light-transmitting two-stage mesa substrate is prepared. The mesa base forming member has a base portion and a mesa structure provided on the main surface of the base portion. The mesa structure includes a first step structure provided on the main surface of the base portion and a first step structure provided on the main surface of the first step structure. A two-level difference structure in which a light-shielding portion forming film is formed on the surface of the light-transmitting two-stage mesa substrate forming member, a protective film-forming film is formed on the light-shielding portion forming film, and the protective film-forming film is coated The resist composition is applied to form a resist layer. The resist layer is exposed and developed through a mask to remove the resist layer on the main surface of the second step structure and expose the second step. The light-shielding portion-forming film and the protective film-forming film formed on the main surface of the poor structure are removed by etching, thereby producing a laminated material obtained by laminating the light-shielding portion and the protective film in this order. mesa Forming the first substrate 1 provided with the step difference structure of the principal surface of the member to the main surface of the base section 2 of the substrate table.

Another example of the manufacturing method of the two-stage mesa substrate of the present invention described above will be described with reference to the drawings. 18 (a) to 19 (c) are schematic cross-sectional views showing an example of a method for manufacturing a two-stage mesa substrate according to the present invention.

First, as shown in FIG. 18 (a), a light-transmitting two-stage mesa base forming member 201 is prepared. The light-transmitting two-stage mesa base forming member 201 has a base 210 and a mesa structure 220 provided on the main surface of the base. The mesa structure 220 has a first step difference structure 270 provided on the main surface 210 a of the base 210 and a second step difference structure 280 provided on the main surface 270 a of the first step difference structure 270.

Next, as shown in FIG. 18 (b), a light-shielding portion forming film 70 is formed on the surface of the light-transmitting two-stage mesa base forming member. Next, as shown in FIG. 18 (c), a protective film-forming film 610 is formed on the light-shielding portion-forming film.

Next, as shown in FIG. 18 (d), a resist composition is applied on the protective film to form a resist layer 18. Next, as shown in FIGS. 18 (e) and 19 (a), the resist on the main surface of the second step structure is removed by exposure and development through a mask. Next, as shown in FIG. 19 (b), the light-shielding portion forming film and the protective film formed on the main surface of the second step structure are removed by etching. Next, as shown in FIG. 19 (c), by removing the resist, the light-shielding portion 70 and the protective film 600 are manufactured from the main surface of the first step structure of the translucent two-stage mesa substrate to the base portion. Two-section mesa base on the main surface.

In the above-mentioned two-stage mesa substrate manufacturing method, when the resist layer 18 shown in FIG. 18 (e) is exposed, the main surface of the base 210 is also exposed and developed, as shown in FIG. 15. Shown in the mesa base.
The present invention is not limited to the embodiments described above. The above-mentioned embodiment exemplifies that any one having a configuration substantially the same as the technical idea of the patent application scope of the present invention and exhibiting the same function and effect is included in the technical scope of the present invention.
[Example]

Hereinafter, the present invention will be described more specifically using examples.

[Example 1]
A nanoimprint die having the same configuration as that of the nanoimprint die 10 shown in FIG. 1 was produced by the production method shown in FIGS. 7 (a) to 9 (c). At this time, the material of the light-transmitting substrate is quartz glass, and the material of the high-contrast film is Cr. The tantalum oxide film was formed by a sputtering method, and the thickness of the tantalum oxide film was set to 4 nm. Hereinafter, a film including the tantalum oxide film in Example 1 and provided so as to cover the high-contrast film without being exposed is referred to as a protective film.

[Example 2]
A nano-imprint die was manufactured in the same manner as in Example 1 except that a chromium oxynitride film having the same thickness as the tantalum oxide film of Example 1 and containing chromium oxynitride was formed as a protective film.

[Example 3]
A nano-imprint die was produced in the same manner as in Example 1 except that a silicon oxide film having the same thickness as the tantalum oxide film of Example 1 and containing SiO ₂ was formed as a protective film.

[Example 4]
A nano-imprint die was produced in the same manner as in Example 1 except that a tantalum nitride film having the same thickness as that of the tantalum oxide film of Example 1 and containing TaN was formed as a protective film.

[Comparative Example 1]
A nano-imprint mold was manufactured in the same manner as in Example 1 except that a protective film was not formed on the surface of the high-contrast film.

[Evaluation]
About Examples 1 to 4 and Comparative Example 1, the film-forming properties, processability, contrast, acid resistance, alkali resistance, and oxygen ash resistance were evaluated as follows.

I. Film Formability The ease of film formation when various protective films are formed on the surface of a high-contrast film is evaluated. The evaluation conditions and evaluation criteria are as follows.
(Evaluation conditions)
Various protective films are formed by sputtering.
(Evaluation criteria)
○: Film formation is easy.
×: Film formation is difficult.

2. Processability The ease of processing the protective film during the manufacture of the nanoimprint die was evaluated. The evaluation conditions and evaluation criteria are as follows.
(Evaluation conditions)
Various protective films are processed by dry etching using an etching gas suitable for processing of various protective films.
(Evaluation criteria)
○: Processing is easy.
×: Processing is difficult.

3. Contrast The contrast (reflectivity) of the high-contrast film in the nanoimprint stencil was evaluated. The evaluation conditions and evaluation criteria are as follows.
(Evaluation conditions)
In the imprint apparatus, an alignment mark including a high-contrast film is used to align the position of the nanoimprint die with the object to be transferred.
(Evaluation criteria)
○: A contrast sufficient for positional alignment is obtained.
×: A contrast sufficient for positional alignment cannot be obtained.

4. Acid resistance The resistance of a protective film (compared to Comparative Example 1 as a high-contrast film) when the nanoimprinting die was washed using SPM (a mixed solution of sulfuric acid and hydrogen peroxide water) was evaluated. The evaluation conditions and evaluation criteria are as follows.
(Evaluation conditions)
The nano-imprint die was immersed in SPM of H ₂ SO ₄ : H ₂ O ₂ = 3: 1, 100 ° C for 40 minutes. Then, AFM (Atomic Force Microscopy) was used to measure the height of the protective film (comparative example 1 is a high-contrast film) before and after immersion, and the height of the protective film after immersion to the height of the protective film before immersion was determined. The reduced amount is the disappearance of the protective film.
(Evaluation criteria)
：: The protective film (high-contrast film in Comparative Example 1) did not disappear at all.
Δ: The protective film (high-contrast film in Comparative Example 1) disappeared, and the disappearance amount did not reach 30%.
×: The protective film (high-contrast film in Comparative Example 1) disappeared, and the disappearance amount was 30% or more.

5. Alkali resistance The resistance of the protective film (about Comparative Example 1 to a high-contrast film) when the nanoimprint stencil was cleaned by SC1 (washing treatment using ammonia water and hydrogen peroxide water) was evaluated. The evaluation conditions and evaluation criteria are as follows.
(Evaluation conditions)
・ SC1
The nanoimprint die was immersed in NH ₄ OH: H ₂ O ₂ : H ₂ O = 1: 1: 5 and 30 ° C. ammonia water and hydrogen peroxide water for 40 minutes. Then, the height of the protective film before and after the immersion (comparative example 1 is a high-contrast film) was measured by AFM, and the decrease in the height of the protective film after the immersion relative to the height of the protective film before the immersion was determined as the disappearance of the protective film .
(Evaluation criteria)
：: The protective film (high-contrast film in Comparative Example 1) did not disappear at all.
Δ: The protective film (high-contrast film in Comparative Example 1) disappeared, and the disappearance amount was 30% or less.
×: The protective film (high-contrast film in Comparative Example 1) disappeared, and the disappearance amount was 30% or more.

6. Oxygen ash resistance The resistance of the protective film (comparative example 1 is a high-contrast film) at the time of cleaning by plasma ashing using an oxygen-containing gas was evaluated. The evaluation conditions and evaluation criteria are as follows.
(Evaluation conditions)
Using a parallel-plate type plasma ashing device, the nanoimprinting die was ashed in an oxygen atmosphere for 10 minutes. Then, the height of the protective film (comparative example 1 is a high-contrast film) before and after ashing was measured by AFM, and the reduction amount of the height of the protective film after ashing relative to the height of the protective film before ashing was determined as the protective film. Its disappearance.
(Evaluation criteria)
：: The protective film (high-contrast film in Comparative Example 1) did not disappear at all.
Δ: The protective film (high-contrast film in Comparative Example 1) disappeared, and the disappearance amount did not reach 30%.
×: The protective film (high-contrast film in Comparative Example 1) disappeared, and the disappearance amount was 30% or more.

The evaluation results are shown in Table 1 below.

[Table 1]

As shown in the above Table 1, the tantalum oxide film of Example 1 had good film-forming properties, processability, contrast, acid resistance, alkali resistance, and oxygen ash resistance. Therefore, the reduction or disappearance of the film of the high-contrast film can be sufficiently suppressed.

On the other hand, as shown in Table 1 above, the chromium oxynitride film of Example 2 had good acid resistance and alkali resistance, but had poor oxygen ash resistance. The silicon oxide film of Example 3 had good acid resistance and alkali resistance, but had poor processability. Specifically, when processing is performed by etching, it may not be possible to stop the etching at the boundary between the silicon oxide film and the light-transmitting substrate, and the processing may be difficult. In addition, the silicon oxide film of Example 3 was insufficient in oxygen ashing resistance, but had good acid resistance and alkali resistance enough to suppress a decrease in high contrast films.

The tantalum nitride film of Example 4 had good acid resistance and alkali resistance, but had poor film-forming properties and processability. Specifically, a tantalum nitride film is easily oxidized by contact with oxygen during film formation, and therefore, it may be difficult to form a film. In addition, there is a case where the tantalum nitride film is oxidized when the tantalum nitride film is processed by dry etching to generate a tantalum oxide film. Since tantalum nitride film and tantalum oxide film-based etching gas are different from chlorine-based gas and fluorine-based gas, the processing of the film may be difficult when the tantalum nitride film is processed by dry etching.

Furthermore, from the results of Comparative Example 1 without a protective film shown in Table 1 above, it can be seen that the high-contrast film has poor acid resistance and oxygen ash resistance.

1‧‧‧Mold for forming a mold

10‧‧‧Nano imprinting die

17‧‧‧curable resin layer

18‧‧‧ resist

20‧‧‧ Transparent substrate

21‧‧‧ base

21a‧‧‧Main face of base 21

22‧‧‧ Countertop Structure

22a‧‧‧The main surface of the mesa structure 22

25‧‧‧ Depression

26‧‧‧slot

27‧‧‧ 1st order difference structure

27a‧‧‧ the first face of the first-order difference structure 27

28‧‧‧ 2nd order difference structure

28a‧‧‧ 2nd order difference structure 28

30‧‧‧ transfer pattern

32‧‧‧ recess

32a‧‧‧ the bottom surface of the recess 32

34‧‧‧ convex

34a‧‧‧ convex surface 34 upper surface

40‧‧‧Marking pattern

40A‧‧‧Alignment mark area

42‧‧‧ Recess

42a‧‧‧underside

44‧‧‧ convex

44a‧‧‧upper surface

44b‧‧‧ side

50‧‧‧high contrast film

60‧‧‧Tantalum oxide film

61‧‧‧ Peripheral Department

70‧‧‧Shading Department

70a‧‧‧ The main surface of the shading section 70

70b‧‧‧side

80‧‧‧Light-shielding film

91‧‧‧1st resin layer

91a‧‧‧The first resin layer 91 film

91b‧‧‧Thick film of the first resin layer 91

91c‧‧‧film for light-shielding part

92‧‧‧Second resin layer

92a‧‧‧thick film of the second resin layer 92

92b‧‧‧ film of the second resin layer 92

92c‧‧‧Thick film for light shielding part

100‧‧‧ Mould for specifying resin layer thickness

101‧‧‧ Mould for specifying resin layer thickness

200‧‧‧2 section base

201‧‧‧ Translucent 2-stage mesa base formation member

210‧‧‧ base

210a‧‧‧Main face of base 210

220‧‧‧ Countertop structure

250‧‧‧ Depression

270‧‧‧First order difference structure

270a‧‧‧The first surface of the first order difference structure 270

280‧‧‧ 2nd order difference structure

600‧‧‧ protective film

610‧‧‧film for protective film formation

D‧‧‧ Depth of Concave and Concave Structure

H ₁ ‧‧‧thickness of film 91a

H ₂ ‧‧‧Thickness of Thick Film 91b

H ₃ ‧‧‧Thickness of Thick Film 92a

H ₄ ‧‧‧Thickness of film 92b

H ₅ ‧‧‧thickness

H ₆ ‧‧‧Thick film 92c thickness

M‧‧‧ height of countertop structure

M1‧‧‧ height of first order difference structure

M2‧‧‧ height of second-order difference structure

Formation area of the thin film 91a of the R‧‧‧ first resin layer 91

w3‧‧‧Width

w4‧‧‧ width

Figs. 1 (a) to (c) are schematic views showing an example of a nanoimprint die sheet according to the present invention.

2 (a) and 2 (b) are schematic views showing another example of the nanoimprint die sheet of the present invention.

3 (a) and 3 (b) are schematic views showing another example of the nanoimprint die sheet of the present invention.

4 (a) and 4 (b) are schematic views showing another example of the nanoimprint die sheet of the present invention.

5 (a) to (c) are schematic views showing another example of the nanoimprint die sheet of the present invention.

Fig. 6 is a schematic cross-sectional view showing another example of the nanoimprint die sheet of the present invention.

7 (a) to 7 (c) are schematic cross-sectional views showing an example of a method for manufacturing a nanoimprint die sheet according to the present invention.

8 (a) to 8 (c) are cross-sectional views schematically showing an example of a method for manufacturing a nanoimprint die sheet according to the present invention.

9 (a) to 9 (c) are cross-sectional views schematically showing an example of a method for manufacturing a nanoimprint die sheet according to the present invention.

Figs. 10 (a) to (c) are cross-sectional views schematically showing the steps of another example of the method for manufacturing a nanoimprint die sheet according to the present invention.

11 (a) to (c) are cross-sectional views schematically showing the steps of another example of the method for manufacturing a nanoimprint die sheet according to the present invention.

Figs. 12 (a) to (c) are cross-sectional views schematically showing the steps of another example of the method for manufacturing a nanoimprint die sheet according to the present invention.

13 (a) to (c) are schematic views showing another example of the nanoimprint die sheet of the present invention.

14 (a) and 14 (b) are plan views showing a plurality of alignment mark regions and a protective film formation region formed on the main surface of the mesa structure of the nanoimprint die sheet of the present invention.

Fig. 15 is a schematic cross-sectional view showing an example of a two-stage mesa substrate of the present invention.

Fig. 16 is a schematic cross-sectional view showing another example of the two-stage mesa substrate of the present invention.

Figs. 17 (a) to (f) are cross-sectional views schematically showing steps in a method for manufacturing a two-stage mesa substrate according to the present invention.

18 (a) to 18 (e) are cross-sectional views schematically showing the steps of another example of the method for manufacturing the two-stage mesa substrate of the present invention.

19 (a)-(c) are cross-sectional views schematically showing the steps of another example of the method for manufacturing the two-stage mesa substrate of the present invention.

Claims (20)

A die for nanoimprinting, comprising a light-transmitting substrate having a base portion and a mesa structure provided on a main surface of the base portion, and On the main surface of the above-mentioned mesa structure, a transfer pattern with a concave-convex structure and a marking pattern with a concave-convex structure are provided. A high-contrast film is provided on the bottom surface of the concave portion of the marking pattern, and A tantalum oxide film is provided on the surface of the high-contrast film so as to cover the high-contrast film. For example, the nanoimprint die for claim 1, wherein the tantalum oxide film is provided on the surface of the high-contrast film and the upper surface of the convex portion of the marking pattern. For example, the nanoimprint die for claim 2, wherein a groove is provided on the main surface of the mesa structure along the tantalum oxide film. The nano-imprinting die according to any one of claims 1 to 3, wherein the mesa structure includes a first step structure provided on the main surface of the base portion and a first step structure provided on the main surface of the first step structure. 2nd order difference structure, The transfer pattern and the marking pattern are provided on a main surface of the second step structure, A light shielding portion is provided in a region around the second step difference structure among the main surfaces of the first step difference structure, and The tantalum oxide film is provided on the main surface of the light shielding portion so as to cover the main surface of the light shielding portion. In the nanoimprinting die of claim 4, wherein the light-shielding portion has a multilayer structure in which a light-shielding film and the high-contrast film are laminated in this order. For example, the nanoimprinting die of claim 4, wherein a recessed portion including the second step difference structure in plan view is provided on a surface of the base portion opposite to the main surface. A method for manufacturing a nano-imprinting die, which is characterized by: The preparation step is to prepare a member for forming a mold having a light-transmitting substrate and a high-contrast film, the light-transmitting substrate having a base portion and a mesa structure provided on a main surface of the base portion, and A transfer pattern of a concave-convex structure and a marking pattern of a concave-convex structure are provided on the main surface of the mesa structure, and the high-contrast film is provided on the entire surface of the main surface side of the transparent substrate; The first resin layer forming step is such that the marking pattern area provided with the above-mentioned marking pattern becomes a thin film, and the transfer pattern area provided with the above-mentioned transfer pattern becomes a thick film. Forming a first resin layer on the printed pattern; In the first etching step, the high-contrast film is left on at least the bottom surface of the recessed portion of the marking pattern and the transfer pattern region by etching the member for forming the mold sheet on which the first resin layer is formed. To remove other parts of the above-mentioned high-contrast film; The tantalum oxide film forming step is to form a tantalum oxide film on the entire surface of the main surface side of the die-forming member having undergone the first etching step; The second resin layer forming step is performed on the tantalum oxide film formed on the marking pattern area and the transfer pattern area such that the marking pattern area becomes a thick film and the transfer pattern area becomes a thin film. Forming a second resin layer; In the second etching step, the tantalum oxide film formed on at least the surface of the high-contrast film is left by etching the member for forming a mold on which the second resin layer is formed, and the tantalum oxide film is formed. Other parts removed; and The third etching step is to remove the high-contrast film provided in the transfer pattern region by performing etching using the remaining tantalum oxide film as a mask. For example, in the method for manufacturing a nanoimprint die sheet according to claim 7, in the first etching step, the high-contrast film is left only on the bottom surface of the recess in the marking pattern, and the high-contrast film Other parts are removed, and In the second etching step, the tantalum oxide film formed on a surface of the high-contrast film and an upper surface of a convex portion of the marking pattern is left. For example, the method for manufacturing a nanoimprint die sheet according to claim 8, wherein in the above-mentioned second resin layer forming step, a region to be a thick film of the second resin layer is set to be the first resin layer in a plan view. The area of the film is on the inside, and In the second etching step, a groove is formed along the region that becomes the thick film of the second resin layer on the main surface of the mesa structure by performing the etching. The method for manufacturing a nanoimprint die sheet according to any one of claims 7 to 9, wherein in the above preparation step, the die sheet forming member is prepared, and among the die sheet forming member, the mesa structure has a setting The first step difference structure on the main surface of the base portion and the second step difference structure provided on the main surface of the first step difference structure, the transfer pattern and the mark are provided on the main surface of the second step difference structure. Using a pattern, and further having a light-shielding portion provided in a region around the second step difference structure in the main surface of the first step difference structure, In the first resin layer forming step, the first resin layer is also formed on the light shielding portion, In the first etching step, the light shielding portion is left, In the step of forming the tantalum oxide film, the tantalum oxide film is formed on a main surface of the light shielding portion. In the second resin layer forming step, the second resin layer of the thick film is also formed on the tantalum oxide film formed on the main surface of the light-shielding portion, and In the second etching step, the tantalum oxide film formed on the main surface of the light shielding portion is left. A die for nanoimprinting, comprising a light-transmitting substrate having a base portion and a mesa structure provided on a main surface of the base portion, and On the main surface of the above-mentioned mesa structure, a transfer pattern with a concave-convex structure and a marking pattern with a concave-convex structure are provided. A high-contrast film is provided on the bottom surface of the concave portion of the marking pattern. The surface of the high-contrast film and the side surface of the convex portion of the marking pattern and the upper surface of the convex portion of the marking pattern are provided so that the ends of the high-contrast film are not exposed. Protective film of different materials with high contrast film, and The said protective film is provided so that an edge part may be located on the upper surface of the convex part of the said marking pattern. For example, the nanoimprinting die of claim 11, wherein the protective film is an alignment mark formed by continuously arranging a plurality of concave portions and convex portions of the marking pattern provided with the high-contrast film in a plan view. The method of including the area on the inner side is provided in an area larger than the above-mentioned alignment mark area. For example, the nanoimprinting die of claim 11, wherein the protective film is provided in a region larger than the plurality of the alignment mark regions in a manner of including the plurality of the alignment mark regions in a plan view. For example, the nanoimprinting die sheet of claim 11, wherein the protective film is provided in a rectangular shape in a plan view. In the nanoimprinting die of claim 11, a groove is provided along the protective film on the main surface of the mesa structure. The nanoimprinting die according to any one of claims 11 to 15, wherein the protective film is a tantalum oxide film. A two-stage mesa substrate, characterized in that it is used for manufacturing a nanoimprinting die, and The light-transmitting two-stage mesa base formation member has a base portion and a mesa structure provided on the main surface of the base portion, and the mesa structure includes a first portion provided on the main surface of the base portion. First-order difference structure and second-order difference structure provided on the main surface of the first-order difference structure, A light shielding portion is provided at least in a region around the second step difference structure among the main surfaces of the first step difference structure, and A protective film is provided on the main surface of the light-shielding portion so as to cover the main surface of the light-shielding portion. For example, the second stage mesa substrate of claim 17, wherein the light-shielding portion is provided from the main surface of the first step difference structure around the second step difference structure to the main surface of the base portion around the first step difference structure, And The protective layer is provided on the main surface of the light shielding portion so as to cover the main surface of the light shielding portion. A method for manufacturing a two-stage mesa substrate, which is characterized in that it is the method for manufacturing a two-stage mesa substrate according to claim 17, and A light-transmitting two-stage mesa base forming member is prepared. The light-transmitting two-stage mesa base forming member has a base portion and a mesa structure provided on the main surface of the base. The mesa structure includes a first First-order difference structure and second-order difference structure provided on the main surface of the first-order difference structure, Forming a film for forming a light-shielding portion on the main surface of the light-transmitting two-stage mesa base formation member on the side where the first step structure and the second step structure are arranged, Forming a film for forming a protective film on the film for forming a light-shielding portion, A hardening resin layer is formed on the main surface of the first step structure and the main surface of the second step structure. The hardening resin layer is formed on the main surface of the first step structure. The film thickness of the layer is embossed so that the film thickness of the curable resin layer formed on the main surface of the second step structure is a thick film. Etching is performed such that the film for forming the light-shielding portion and the protective film remain only on the main surface of the first step difference structure. A two-stage mesa substrate in which a light shielding portion and a protective film are sequentially provided in a region around the second-stage difference structure among the main surfaces of the first-stage difference structure of the light-transmitting two-stage mesa substrate forming member. A method for manufacturing a two-stage mesa substrate, which is characterized in that it is the method for manufacturing a two-stage mesa substrate according to claim 18, and A light-transmitting two-stage mesa base forming member is prepared. The light-transmitting two-stage mesa base forming member has a base portion and a mesa structure provided on the main surface of the base. The mesa structure includes a first First-order difference structure and second-order difference structure provided on the main surface of the first-order difference structure, Forming a film for forming a light-shielding portion on the surface of the light-transmitting two-stage mesa base forming member, Forming a film for forming a protective film on the film for forming a light-shielding portion, Applying a resist composition on the film for forming a protective film to form a resist layer, By exposing and developing the resist layer through a mask, the resist layer on the main surface of the second step difference structure is removed. The light-shielding portion-forming film and the protective film-forming film formed on the exposed main surface of the second step structure are removed by etching. The laminated material produced by laminating the light-shielding portion and the protective film in this order is provided from the main surface of the first step structure of the transparent two-stage mesa substrate forming member to the two-stage mesa substrate of the main surface of the base portion. .