JP2014123684A - Laminate for fine pattern formation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily form a fine pattern with a thin residual film or without the residual film for forming the fine pattern having a high aspect ratio on an object to be processed.SOLUTION: A laminate (2) for fine pattern formation includes a first surface (2a) and a second surface (2b) which are substantially in parallel with each other, is used for forming a fine pattern on an object to be processed via a first mask layer (103) provided at a side of the first surface (2a), and comprises a protection layer (101), a plurality of nano particles (102) provided on the protection layer (101) to be functioned as a mask when processing the first mask layer (103) and the first mask layer (103) provided to cover the plurality of nano particles (102). The nano particles (102) are disposed in such a manner that the number of nano particles (102) crossing a virtual surface substantially parallel to a center surface (2c) decreases as it is separated away from the center surface (2c).

Description

  The present invention relates to a laminate for forming a fine pattern used for forming a fine pattern on an object to be processed.

  Conventionally, a photolithography technique has been often used as a fine pattern processing technique in LSI manufacturing. However, the photolithography technique has a problem that it is difficult to process a pattern having a size smaller than the wavelength of light used for exposure. Another fine pattern processing technique is a mask pattern drawing technique (EB method) using an electron beam drawing apparatus. However, in the EB method, since the mask pattern is directly drawn by the electron beam, there is a problem that the drawing time increases as the drawing pattern increases, and the throughput until the pattern formation is significantly reduced. In addition, these methods also have a problem that the apparatus cost increases due to high-precision control of the mask position in the exposure apparatus for photolithography and the enlargement of the electron beam drawing apparatus in the exposure apparatus for the EB method.

  Nanoimprint technology is known as a fine pattern processing technology that can eliminate these problems. In nanoimprint technology, a protective layer on which nano-scale fine patterns are formed is pressed against a resist film formed on the surface of the substrate to be transferred, so that the fine pattern formed on the protective layer is transferred to the surface of the substrate to be transferred. To do.

  1A and 1B are explanatory diagrams illustrating an example of a nanoimprint method. In FIG. 1A, in order to form a fine pattern on the surface of a desired base material (object to be processed) 1001, a nanoimprint method is applied to press the uneven structure formed on the mold 1002 against the object to be processed 1001.

  In the case where the fine pattern 1003 is used as a mask used for processing the object to be processed 1001, the fine pattern 1003 is made of a transfer material that serves as a mask when the object 1001 is processed. At the time of transfer, it is necessary to make the remaining film T thin. In order to reduce the remaining film T, it is necessary to reduce the coating film thickness of the transfer material and to press it with a large pressure for a long time. However, when the coating film thickness is reduced, not only is it easily affected by unevenness and particles existing on the surface of the object to be processed 1001, but the transfer material is poorly filled into the concavo-convex structure of the mold 1002 and air bubbles are mixed. Problems arise. Moreover, when it presses for a long time, throughput property will fall. Furthermore, in order to uniformly form a thin residual film, it is necessary to use a special device having a small pressure distribution. In particular, it is known that it is very difficult to form a uniform thin residual film with a large area. Since there are many problems in this way, it has not been able to take advantage of the advantages of the nanoimprint method, which is regarded as industrially superior, such as large area transfer, simplicity and throughput.

  On the other hand, when a fine pattern having a high aspect ratio is formed on the object 1001 to be processed, it is necessary to increase the aspect ratio of the concavo-convex structure formed on the surface of the mold 1002. However, when the aspect ratio of the concavo-convex structure formed on the surface of the mold 1002 is increased, filling defects are likely to occur, and when the mold 1002 is peeled off, mold release defects typified by destruction of the fine pattern 1003 are likely to occur. As shown in FIG. 1B, in order to form a fine pattern having a high aspect ratio on the object 1001, an organic layer 1004 is provided on the object 1001, and a fine pattern 1003 (mask layer) is formed on the organic layer 1004. And a method of processing the organic layer 1004 using the fine pattern 1003 as a mask has been proposed. However, when the fine pattern 1003 is used as a mask used for processing the organic layer 1004, the same problem as described above exists.

  Under such circumstances, a method of forming a fine mask pattern with a thin residual film T or no residual film T has been proposed (see Patent Document 1). In Patent Document 1, first, a film of a mask material is directly formed on a concavo-convex structure of a type having a concavo-convex structure on the surface. Subsequently, the residual film T is made thin or zero by applying etch back to the mask material film (the film thickness of the mask material film disposed on the uneven structure of the mold is made thin). Thereafter, a base material is bonded onto the mask material, and finally, the mold side is subjected to an ashing process, thereby eliminating a fine structure of the mold and obtaining a fine mask pattern having no residual film T.

JP 2011-66273 A

  However, the fine mask forming method described in Patent Document 1 is complicated because the total number of steps required to obtain a fine mask pattern with a thin residual film or no residual film is large. In addition, the surface area of the inorganic base material to be processed is not good in throughput until a mask layer having a thin residual film or no residual film is formed, and the entire mask material film needs to be etched back, resulting in a large area. It is not difficult to imagine that it is difficult to form a mask.

  The present invention has been made in view of the above points, and in order to form a fine pattern having a high aspect ratio on the object to be processed, a fine pattern that can easily form a fine pattern having a thin residual film or no residual film. It aims at providing the laminated body for formation.

  The laminate for forming a fine pattern of the present invention has a first surface and a second surface substantially parallel to each other, and the fine pattern is formed on the object to be processed through a first mask layer provided on the first surface side. And a plurality of nanoparticles functioning as a mask during processing of the first mask layer provided on the protective layer, and A first mask layer provided so as to cover the nanoparticles, wherein the nanoparticles have a maximum number of nanoparticles crossing a plane substantially parallel to the first surface and the second surface. When the virtual plane is a central plane, the number of nanoparticles crossing the virtual plane substantially parallel to the central plane is arranged so as to decrease as the distance from the central plane increases.

  According to this configuration, since the plurality of nanoparticles are dispersed and the number of the plurality of nanoparticles decreases as the distance from the central plane decreases, the nanoparticles are placed in the multilayer film for forming a fine pattern. It is not randomly distributed. Thereby, the nanoparticles transferred and applied to the object to be processed via the first mask layer are less likely to overlap with each other, so that the processing accuracy of the first mask layer is improved. That is, it is possible to omit a remaining film processing step of partially removing the nanoparticles in a later step. Thereby, it becomes possible to obtain a laminate composed of nanoparticles / first mask layer / object to be processed that do not overlap each other, and the processing accuracy of the first mask layer is improved. Therefore, a fine mask pattern having a high aspect ratio can be easily formed on the object to be processed.

In the laminate for forming a fine pattern of the present invention, the average pitch (Pav) in the central plane of the plurality of nanoparticles, the average end position (Spt) on the first surface side of the plurality of nanoparticles, and the The ratio (lor / Pav) to the distance (lor) between the first surface preferably satisfies the following formula (1).
Formula (1)
0.05 ≦ lor / Pav ≦ 10

  According to this configuration, the film thickness of the first mask layer is determined according to the density of the nanoparticles. When the thickness of the first mask layer satisfies the above formula (1), the bonding property of the first mask layer when the laminated body for forming a fine pattern is bonded to an object to be processed can be improved. . Furthermore, by satisfying the above-mentioned range, it is possible to suppress the disorder of the arrangement and shape of the nanoparticles that occur when the fine pattern-forming laminate is manufactured and transported, and the fine pattern-forming laminate is bonded to the object. Therefore, the nanoparticles can be transferred and applied to the object to be processed through the first mask layer with high shape and arrangement accuracy of the nanoparticles. In addition, the film thickness accuracy of the first mask layer can be improved. That is, it is possible to further increase the film thickness accuracy of the first mask layer transferred and applied to the object to be processed.

In the laminate for forming a fine pattern according to the present invention, the ratio (Vo1 / Vm1) between the etching rate (Vm1) of the nanoparticles by dry etching and the etching rate (Vo1) of the first mask layer is expressed by the following formula. It is preferable to satisfy (2).
Formula (2)
3 ≦ Vo1 / Vm1

  According to this configuration, since the first mask layer can be satisfactorily etched using the nanoparticles as a mask, the fine mask pattern composed of the nanoparticles and the first mask layer provided on the object to be processed is evenly distributed. Improves.

In the laminate for forming a fine pattern according to the present invention, the ratio (Vo2 / Vi2) between the etching rate (Vi2) of the object to be processed by dry etching and the etching rate (Vo2) of the first mask layer is as follows. It is preferable to satisfy Formula (3).
Formula (3)
Vo2 / Vi2 ≦ 3

  According to this configuration, since the processing accuracy of the object to be processed can be improved when the first mask layer is used as a processing mask, the alignment accuracy of a plurality of nanoparticles is reflected and the height accuracy is reflected. High fine pattern can be provided on the object to be processed.

  In the laminate for forming a fine pattern according to the present invention, the shape of the plurality of nanoparticles is asymmetrical with respect to a line segment in a direction parallel to the center plane in a cross-sectional view perpendicular to the center plane. It is preferably non-axisymmetric and symmetrical with respect to a line segment perpendicular to the center plane.

  According to this configuration, the array stability of the nanoparticles is improved. That is, it occurs when the first mask layer is formed, when the fine pattern forming laminate is transported, or when the first mask layer of the fine pattern forming laminate is bonded to the object to be processed. The disorder of the arrangement of nanoparticles can be suppressed.

  In the laminate for forming a fine pattern according to the present invention, it is preferable that the protective layer has a concavo-convex structure on a surface thereof, and the plurality of nanoparticles are disposed inside the concavo-convex structure of the concavo-convex structure.

  According to this configuration, the arrangement of the plurality of nanoparticles can be controlled by the uneven structure of the protective layer. In addition, the shape stability of the nanoparticles is improved. For this reason, it is possible to improve the alignment accuracy and processing accuracy of the fine mask pattern having a high aspect ratio provided on the object to be processed.

  In the laminate for forming a fine pattern according to the present invention, it is preferable to further provide an object to be processed on the first mask layer.

  In the laminate for forming a fine pattern of the present invention, it is preferable that the object to be processed is any one of sapphire, silicon, ITO, ZnO, SiC, a nitride semiconductor, or spinel.

  By employing these objects to be processed, it is possible to manufacture a semiconductor light emitting device having a high external quantum efficiency at a facility suitable for manufacturing the semiconductor light emitting device.

  ADVANTAGE OF THE INVENTION According to this invention, in order to form the fine pattern which has a high aspect ratio in a to-be-processed object, the laminated body for fine pattern formation which can form easily the fine pattern with a thin residual film or without a residual film is realizable.

It is explanatory drawing which shows an example of the nanoimprint method. It is process drawing for demonstrating the fine pattern formation method with respect to the to-be-processed object which concerns on this Embodiment. It is process drawing for demonstrating the fine pattern formation method with respect to the to-be-processed object which concerns on this Embodiment. It is a cross-sectional schematic diagram which shows an example of the laminated body for fine pattern formation which concerns on this Embodiment. It is a cross-sectional schematic diagram in the center plane in the laminated body for fine pattern formation which concerns on this Embodiment. It is a cross-sectional schematic diagram which shows an example of the shape of the nanoparticle in the laminated body for fine pattern formation which concerns on this Embodiment. It is explanatory drawing of the fine pattern formation method using the laminated body for fine pattern formation concerning this Embodiment. It is a cross-sectional schematic diagram which shows an example of the laminated body for fine pattern formation which concerns on this Embodiment. It is a figure which shows an example of the uneven structure in the protective layer of the laminated body for fine pattern formation which concerns on this Embodiment. It is a figure which shows an example of the arrangement | sequence of the uneven structure in the protective layer of the laminated body for fine pattern formation which concerns on this Embodiment. It is a cross-sectional schematic diagram which shows the dot-shaped uneven structure of the protective layer in the laminated body for fine pattern formation which concerns on this Embodiment. It is a plane schematic diagram which shows the hole-shaped uneven structure of the protective layer in the laminated body for fine pattern formation which concerns on this Embodiment. It is explanatory drawing of the aperture ratio of the uneven structure in the laminated body for fine pattern formation which concerns on this Embodiment. It is explanatory drawing of the aperture ratio of the uneven structure in the laminated body for fine pattern formation which concerns on this Embodiment. It is explanatory drawing of the manufacturing process of the reel-shaped protective layer in the manufacturing method of the laminated body for fine pattern formation which concerns on this Embodiment. It is explanatory drawing of the manufacturing process of the reel-shaped protective layer in the manufacturing method of the laminated body for fine pattern formation which concerns on this Embodiment. It is explanatory drawing of the manufacturing process of the reel-shaped protective layer in the manufacturing method of the laminated body for fine pattern formation which concerns on this Embodiment. It is explanatory drawing of the manufacturing process of the laminated body for fine pattern formation in the manufacturing method of the laminated body for fine pattern formation which concerns on this Embodiment. It is explanatory drawing of the manufacturing process of the laminated body for fine pattern formation in the manufacturing method of the laminated body for fine pattern formation which concerns on this Embodiment. It is explanatory drawing of the manufacturing process of the laminated body for fine pattern formation in the manufacturing method of the laminated body for fine pattern formation which concerns on this Embodiment. It is explanatory drawing which shows the relationship between the uneven structure and unit area of the laminated body for fine pattern formation concerning this Embodiment. It is explanatory drawing of the arrangement | sequence of the uneven structure of the laminated body for fine pattern formation which concerns on this Embodiment. It is explanatory drawing which shows the relationship between the fine pattern in the laminated body for fine pattern formation which concerns on this Embodiment, a unit area, and a recessed part volume. It is explanatory drawing which shows the relationship between the fine pattern in the laminated body for fine pattern formation which concerns on this Embodiment, a unit area, and a recessed part volume. It is a figure which shows the coating process conditions with respect to the uneven structure of the laminated body for fine pattern formation which concerns on this Embodiment. It is a figure which shows the coating process conditions with respect to the uneven structure of the laminated body for fine pattern formation which concerns on this Embodiment. It is a figure which shows the coating process conditions with respect to the uneven structure of the laminated body for fine pattern formation which concerns on this Embodiment. It is a cross-sectional schematic diagram of the semiconductor light-emitting device using the to-be-processed object created using the laminated body for fine pattern formation which concerns on this Embodiment.

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

  First, an outline of a method for forming a fine pattern of an object to be processed using the laminate for forming a fine pattern according to the present embodiment will be described. 2A to 2C and FIGS. 3A to 3F are process diagrams for explaining a method for forming a fine pattern of an object to be processed according to the present embodiment. As shown in FIG. 2A, the protective layer 10 preferably has a concavo-convex structure 11 formed on its main surface. The concavo-convex structure 11 includes a plurality of concave portions 11a and convex portions 11b. The protective layer 10 is, for example, a film-shaped or sheet-shaped resin protective layer. The protective layer 10 functions to protect the shape and arrangement of the nanoparticles 12.

  First, as shown in FIG. 2B, nanoparticles 12 for patterning a first mask layer to be described later are filled into the recesses 11 a of the concavo-convex structure 11 of the protective layer 10. The nanoparticles 12 are made of, for example, a sol-gel material, metal oxide particles, or metal particles. Here, the laminate including the protective layer 10 and the nanoparticles 12 is referred to as a first fine pattern forming laminate 1 or simply as a first laminate 1.

  Next, as shown in FIG. 2C, a first mask layer 13 is formed on the concavo-convex structure 11 including the nanoparticles 12 of the first laminate 1. The first mask layer 13 is used for patterning a target object 20 (see FIGS. 3A to 3F) described later. The first mask layer 13 is made of, for example, a photocurable resin, a thermosetting resin, or a thermoplastic resin.

  Furthermore, as shown in FIG. 2C, a cover film 14 can be provided on the upper side of the first mask layer 13. The cover film 14 protects the first mask layer 13 and is not essential. Here, the laminate composed of the protective layer 10, the nanoparticles 12, and the first mask layer 13 is referred to as the second fine pattern forming laminate 2 or simply as the second laminate 2. This 2nd laminated body 2 can be used for the patterning of the to-be-processed object 20 by bonding the 1st mask layer 13 to the to-be-processed object 20. FIG.

  Here, the plurality of nanoparticles 12 are disposed between the protective layer 10 and the first mask layer 13 so that the number of nanoparticles 12 decreases as the distance from the center plane decreases. There is no random dispersion in the second laminate 2. Thereby, the 1st mask layer 13 of the 2nd laminated body 2 is bonded to the to-be-processed object 20, and the nanoparticle 12 and the 1st mask layer 13 on the to-be-processed body 20 so that it may demonstrate below. Since the nanoparticles 12 do not overlap each other when transferred, the processing accuracy of the first mask layer 13 is greatly improved.

Further, the average pitch (Pav) in the center plane of the plurality of nanoparticles 12 and the distance (lor) between the average end position (Spt) on the first surface side of the plurality of nanoparticles 12 and the first surface When the ratio (lor / Pav) satisfies the following formula (1), the bonding property of the first mask layer 13 to the object to be processed 20 is improved, so that they overlap each other over the surface of the object to be processed 20. It is possible to transfer and impart the nanoparticles 12 without any problems.
Formula (1)
0.05 ≦ lor / Pav ≦ 10

  Next, a workpiece 20 as shown in FIG. 3A is prepared. The object 20 is, for example, a sapphire substrate, a Si (silicon) substrate, an ITO substrate, a ZnO substrate, a SiC (silicon carbide) substrate, a nitride semiconductor substrate, or a spinel substrate. First, as shown in FIG. 3B, the first mask layer 13 of the second laminate 2 after removing the cover film 14 protecting the first mask layer 13 on the main surface of the object 20 to be processed. Lamination (thermocompression bonding) is performed with the exposed surface facing the main surface of the object 20 to be processed.

  Next, as shown in FIG. 3C, the protective layer 10 that protects the shape and arrangement of the nanoparticles 12 is peeled from the first mask layer 13 and the nanoparticles 12. As a result, an intermediate body 21 including the object to be processed 20, the first mask layer 13, and the nanoparticles 12 is obtained.

  In addition, between the above-described lamination and peeling, the second laminate 2 may be irradiated with energy rays to cure or solidify at least one of the nanoparticles 12 and the first mask layer 13. In addition, at least one of the nanoparticles 12 and the first mask layer 13 may be cured or solidified by heat applied during lamination (thermocompression bonding). Furthermore, at least one of the nanoparticles 12 and the first mask layer 13 may be cured or solidified by energy beam irradiation or heat treatment after peeling.

  Next, using the nanoparticles 12 as a mask, the first mask layer 13 is patterned by oxygen ashing, for example, as shown in FIG. 3D. As a result, the fine pattern structure 16 provided with the fine mask pattern 16a having the high aspect ratio and composed of the first mask layer 13 and the nanoparticles 12 is obtained. That is, the nanoparticles 12 can be arranged on the top of the convex portion of the fine mask pattern 16a. Thus, since the nanoparticles 12 do not overlap each other, the fine mask pattern 16a can be favorably obtained. Using the patterned first mask layer 13 as a mask, for example, reactive ion etching is performed on the target object 20 to form a fine pattern 22 on the main surface of the target object 20 as shown in FIG. 3E. . Finally, as shown in FIG. 3F, the first mask layer 13 remaining on the main surface of the object to be processed 20 is removed to obtain the object to be processed 20 having the fine pattern 22.

  In the present embodiment, the process from obtaining the second stacked body 2 from the protective layer 10 shown in FIGS. 2A to 2C is performed in one line (hereinafter referred to as the first line). The subsequent steps from FIG. 3A to FIG. 3F are performed on another line (hereinafter referred to as a second line). In a more preferred embodiment, the first line and the second line are performed in separate facilities. For this reason, for example, when the protective layer 10 that protects the shape and arrangement of the nanoparticles 12 is in the form of a film and has flexibility, the second stacked body 2 is formed in a scroll shape ( Packed in a roll) and stored or transported. Moreover, when the protective layer 10 is a sheet form, the 2nd laminated body 2 stacks and packs the several 2nd laminated body 2, and is stored or conveyed.

  In a further preferred aspect of the present invention, the first line is a supplier line of the second laminate 2 and the second line is a user line of the second laminate 2. Thus, the following advantages are obtained by mass-producing the second laminate 2 in advance at the supplier and providing it to the user.

  (1) Since the protective layer 10 can maintain the alignment and shape accuracy of the nanoparticles 12 constituting the second laminate 2, the alignment accuracy and shape accuracy of the nanoparticles 12 are reflected, and the object 20 to be processed Fine processing can be performed. Furthermore, since the film thickness accuracy of the first mask layer 13 can be ensured in the second stacked body 2, the film thickness distribution accuracy of the first mask layer 13 transferred and formed on the object to be processed 20. Can be kept high. That is, by using the second stacked body 2, the nanoparticles 12 and the first mask layer 13 are formed in the surface of the object 20 to be processed with high film thickness distribution accuracy of the first mask layer 13 and the nanoparticles 12. It is possible to transfer and form with high transfer accuracy. For this reason, by finely processing the first mask layer 13 using the nanoparticles 12, the pattern accuracy (pattern alignment accuracy) of the nanoparticles 12 is reflected in the surface of the workpiece 20, and the film thickness distribution accuracy is reflected. It is possible to form the fine pattern structure 16 provided with the fine mask pattern 16 a having a high aspect ratio and composed of the nanoparticles 12 and the first mask layer 13. By using the fine pattern structure 16 with high accuracy, the object 20 can be processed with high accuracy, and the fine pattern 22 reflecting the alignment accuracy of the nanoparticles 12 in the surface of the object 20 is manufactured. can do.

  (2) Since the precision of the fine pattern can be ensured by the second laminate 2, the accuracy of the fine pattern can be secured in a facility suitable for processing the workpiece 20 without using a complicated process or apparatus. The processing body 20 can be finely processed. At the same time, since the periphery of the nanoparticles 12 is surrounded by the protective layer 10 and the first mask layer 13, scattering of the nanoparticles 12 can be suppressed.

  (3) Since the accuracy of the fine pattern 22 can be ensured by the second stacked body 2, the second pattern is used in a place optimal for manufacturing a device using the processed object 20 to be processed. The laminate 2 can be used. That is, a device having a stable function can be manufactured.

  As described above, the first line is the supplier line of the second laminated body 2 and the second line is the user line of the second laminated body 2, which is optimal for processing the workpiece 20. In addition, the second laminate 2 can be used in an optimum environment for manufacturing a device using the processed object 20 to be processed. For this reason, the throughput of the processing of the object 20 and the device assembly can be improved. Further, the second laminate 2 is a laminate composed of a protective layer 10 and functional layers (nanoparticles 12 and first mask layer 13) provided on the protective layer 10. That is, the arrangement accuracy of the first mask layer 13 and the nanoparticles 12 that govern the processing accuracy of the workpiece 20 is ensured by the accuracy of the concavo-convex structure 11 of the protective layer 10 of the second stacked body 2, and the first The film thickness accuracy of one mask layer 13 can be secured as the second stacked body 2. As described above, the processed object 20 is used by changing the first line to the supplier line of the second laminate 2 and the second line to the user line of the second laminate 2. In the optimum environment for manufacturing a device, the object 20 can be processed and used with high accuracy using the second laminate 2.

  By the way, when providing the fine mask pattern 16a with a high aspect ratio on the to-be-processed object 20, the remaining film at the time of producing the fine mask pattern 16a becomes a problem. In the fine pattern formation method described above, the ashing of the first mask layer 13 is performed when the nanoparticles 12 overlap each other, more specifically, when there are nanoparticles 12 overlapping in the thickness direction of the laminate for forming a fine pattern. Since it becomes difficult, it is necessary to provide a process of removing the overlapping nanoparticles 12 partially (hereinafter referred to as a residual film treatment process). By passing through such a process, the volume of the nanoparticles 12 originally intended to function as a mask is reduced and the volume distribution is increased. For this reason, there is a problem that the manufacturing process becomes complicated, the manufacturing efficiency of the object 20 having the fine pattern 22 decreases, and the processing accuracy of the object 20 decreases.

  The present inventors take the state in which the nanoparticles 12 are dispersed in a predetermined plane in the second fine pattern forming laminate 2, thereby ashing the first mask layer 13, that is, the remaining film processing step. It was found that the problem in the can be solved.

  That is, the laminate for forming a fine pattern according to the present invention has a first surface and a second surface that are substantially parallel to each other, and is disposed on the object to be processed via the first mask layer provided on the first surface side. A laminate for forming a fine pattern used for forming a fine pattern, a protective layer, and a plurality of nanoparticles functioning as a mask when processing the first mask layer provided on the protective layer, The first mask layer provided so as to cover the plurality of nanoparticles, wherein the plurality of nanoparticles cross the plane substantially parallel to the first surface and the second surface. When the virtual surface with the largest number is a central surface, the number of the nanoparticles crossing the virtual surface substantially parallel to the central surface is arranged so as to decrease with increasing distance from the central surface. Features.

  According to this fine pattern forming laminate, a plurality of nanoparticles are dispersed in the fine pattern forming laminate, and the number of the plurality of nanoparticles is arranged so as to decrease as the distance from the center plane increases. The nanoparticles are not randomly dispersed in the laminate film for forming a fine pattern. Thereby, the nanoparticles transferred and applied to the object to be processed via the first mask layer are less likely to overlap with each other, so that the processing accuracy of the first mask layer is improved. That is, it is possible to omit a remaining film processing step of partially removing the nanoparticles in a later step. Thereby, it becomes possible to obtain a laminate composed of nanoparticles / first mask layer / object to be processed that do not overlap each other, and the processing accuracy of the first mask layer is improved. Therefore, a fine mask pattern having a high aspect ratio can be easily formed on the object to be processed.

In the fine pattern-forming laminate of the present invention, the average pitch (Pav) of the plurality of nanoparticles in the central plane, and the average end position (Spt) of the plurality of nanoparticles on the first surface side, It is preferable that the ratio (lor / Pav) to the distance (lor) between the first surface satisfies the following formula (1).
Formula (1)
0.05 ≦ lor / Pav ≦ 10

  According to this configuration, the film thickness of the first mask layer is determined according to the density of the nanoparticles. When the thickness of the first mask layer satisfies the above formula (1), the bonding property of the first mask layer when the second laminate 2 is bonded to the object to be processed can be improved. . Furthermore, by satisfying the above range, the disorder and the disorder of the arrangement and shape of the nanoparticles that occur when the second laminate 2 is manufactured and transported and the second laminate 2 is bonded to the object to be processed are suppressed. Therefore, the nanoparticles can be transferred and applied to the object to be processed through the first mask layer with high shape and arrangement accuracy of the nanoparticles. In addition, the film thickness accuracy of the first mask layer can be improved. That is, it is possible to further increase the film thickness accuracy of the first mask layer transferred and applied to the object to be processed.

In the laminate for forming a fine pattern of the present invention, the ratio (Vo1 / Vm1) between the etching rate (Vm1) of the nanoparticles by dry etching and the etching rate (Vo1) of the first mask layer is expressed by the following formula ( 2) may be satisfied.
Formula (2)
3 ≦ Vo1 / Vm1

  According to this configuration, the first mask layer can be satisfactorily etched using the nanoparticles as a mask. Therefore, the fine mask pattern 16a composed of the nanoparticles and the first mask layer provided on the object to be processed can be obtained. Uniformity is improved.

In the fine pattern-forming laminate of the present invention, the ratio (Vo2 / Vi2) between the etching rate (Vi2) of the object to be processed by dry etching and the etching rate (Vo2) of the first mask layer is expressed by the following formula. (3) may be satisfied.
Formula (3)
Vo2 / Vi2 ≦ 3

  According to this configuration, since the processing accuracy of the object to be processed when using the first mask layer as a processing mask can be improved, the alignment accuracy of the nanoparticles of the second stacked body 2 is reflected, In addition, a fine pattern with high accuracy can be provided on the object to be processed.

  In the laminate for forming a fine pattern of the present invention, the shape of the plurality of nanoparticles is asymmetrical with respect to a line segment in a direction parallel to the center plane in a cross-sectional view perpendicular to the center plane. It is preferably non-axisymmetric and axisymmetric with respect to a line segment perpendicular to the center plane.

  According to this configuration, the array stability of the nanoparticles is improved. That is, when the first mask layer is formed on the first laminate 1 or when the second laminate 2 is transported, the first mask layer of the second laminate 2 is covered. It is possible to suppress the disorder of the arrangement of the nanoparticles that occurs when being bonded to the treatment body.

  In the laminate for forming a fine pattern according to the present invention, it is preferable that the protective layer has a concavo-convex structure on a surface thereof, and the plurality of nanoparticles are disposed inside the concave portion of the concavo-convex structure.

  According to this configuration, the arrangement of the plurality of nanoparticles can be controlled by the uneven structure of the protective layer. In addition, the shape stability of the nanoparticles is improved. For this reason, it is possible to improve the alignment accuracy and processing accuracy of the fine mask pattern having a high aspect ratio provided on the object to be processed.

  In the laminate for forming a fine pattern according to the present invention, an object to be processed can be further provided on the first mask layer.

  Furthermore, in the laminate for forming a fine pattern of the present invention, the object to be processed may be sapphire, silicon, ITO, ZnO, SiC, a nitride semiconductor, or spinel.

  By employing these objects to be processed, it is possible to manufacture a semiconductor light emitting device having a high external quantum efficiency at a facility suitable for manufacturing the semiconductor light emitting device.

  Hereinafter, the laminated body for fine pattern formation which concerns on embodiment of this invention is demonstrated in detail.

  FIG. 4 is a schematic cross-sectional view showing an example of a laminate for forming a fine pattern according to the present embodiment. As shown in FIG. 4, the second laminate 2 according to the present embodiment covers the protective layer 101, the plurality of nanoparticles 102 provided on the surface of the protective layer 101, and the plurality of nanoparticles 102. The first mask layer 103 is provided. The second stacked body 2 has a pair of main surfaces that are substantially parallel to each other, and one main surface is a surface (hereinafter referred to as a first surface) 2a of the first mask layer 103, and the other The main surface is a surface (hereinafter referred to as a second surface) 2b from which the protective layer 101 is exposed. Here, “substantially parallel” does not necessarily mean completely parallel, but allows a slight error within a range where the effects of the present invention can be achieved.

  This 2nd laminated body 2 has the layer 102a comprised including the some nanoparticle 102 between the 2nd surface 2b and the 1st surface 2a. The plurality of nanoparticles 102 are filled with at least the first mask layer 103 around the periphery. Further, the plurality of nanoparticles 102 have a predetermined spread in a plane substantially parallel to the second surface 2b and the first surface 2a in the above-described layer 102a, and are provided at predetermined intervals. It is arranged. The layer including the plurality of nanoparticles 102 includes a central surface 2c that is substantially parallel to the second surface 2b and the first surface 2a and has the largest number across the plurality of nanoparticles 102.

  That is, the second laminate 2 according to the present embodiment includes a plurality of nanoparticles 102 inside, and the nanoparticles 102 are in the central surface 2c substantially parallel to the second surface 2b and the first surface 2a. They are arranged so as to have a predetermined spread in the (front-rear direction and left-right direction). Further, the plurality of nanoparticles 102 crossing the center plane 2c are arranged at a predetermined interval in the center plane 2c.

  Next, the distribution of the nanoparticles 102 will be described. In the second stacked body 2 according to the present embodiment, the center plane 2 c is defined by the number of nanoparticles 102 that traverse the virtual plane in the second stacked body 2. Specifically, when a plurality of virtual surfaces substantially parallel to the second surface 2b and the first surface 2a are provided in the second stacked body 2, the nanoparticles 102 are included in the plurality of virtual surfaces. Is set as the center plane 2c.

  In the example illustrated in FIG. 4, five virtual planes A to F are provided between the second plane 2 b and the first plane 2 a of the second stacked body 2 from the second plane 2 b toward the first plane 2 a. E is provided. Among the virtual surfaces A to E, the number of nanoparticles 102 that cross the virtual surface C in the vicinity of the central portion in the film thickness direction of the second stacked body 2 is 12 and the maximum. Therefore, the virtual plane C becomes the center plane 2c. In the virtual surface B and the virtual surface A on the first surface 2a side with respect to the central surface 2c, as the distance from the central surface 2c toward the first surface 2a increases, the nanoparticles 102 that cross the virtual surface B and the virtual surface A The number decreases monotonously sequentially, such as 12, 9, and 0. In addition, in the virtual surface D and the virtual surface E on the second surface 2b side with respect to the central surface 2c, the number of nanoparticles 102 that cross the virtual surfaces D and E toward the second surface 2b as the distance from the central surface 2c increases. Gradually decreases monotonically, such as 12, 2, and 0.

  Thus, in the 2nd laminated body 2 which concerns on this Embodiment, the some nanoparticle 102 is nano between the virtual surface A-the virtual surface E substantially parallel to the 2nd surface 2b and the 1st surface 2a. The virtual plane C in which the number of particles 102 traverses the maximum is the central plane 2c, and the number of nanoparticles 102 that cross the virtual planes A, B, D, E decreases as the distance from the central plane 2c increases. . With this configuration, the plurality of nanoparticles 102 decrease as they move away from the central surface 2 c, so that the second stack of nanoparticles 102 is compared to the case where the nanoparticles 102 are randomly arranged in the second stack 2. The overlap with respect to the film thickness direction of the body 2 can be suppressed. Thus, the first surface 2a of the second stacked body 2, that is, the surface of the first mask layer 103 is composed of nanoparticles 102 / first mask layer 103 / object to be processed which can be bonded to the object to be processed. Since it is possible to omit the remaining film processing step of removing the overlapping nanoparticles 102 when the first mask layer 103 is etched from the nanoparticle 102 side, the processing accuracy of the first mask layer 103 is increased. Can be improved. Furthermore, since the plurality of nanoparticles 102 are provided in the vicinity of the center surface 2c, it is possible to suppress the influence of the nanoparticles 102 on the first surface 2a, and it is possible to keep the flatness of the first surface 2a favorable. It becomes. For this reason, since it is possible to suppress defects such as entrainment of air voids when the first mask layer 103 of the second laminate 2 is bonded to the object to be processed, the transferability within the surface of the object to be processed is improved. . It should be noted that the number of the plurality of nanoparticles 102 crossing the plurality of surfaces does not necessarily need to be completely monotonously reduced, and includes a mode in which the number of nanoparticles 102 is appropriately dispersed within a range in which the effect of the present invention is achieved.

  The first surface 2 a of the second laminate 2, that is, a surface substantially parallel to the surface of the first mask layer 103, and an average surface formed by the end portions of the plurality of nanoparticles 12 on the first surface 2 a side. Is defined as the average edge position (Spt). This average edge position (Spt) is the average value of the shortest distances between the edge of the plurality of nanoparticles 102 on the first surface 2a side and the first surface 2a in the film thickness direction M of the second laminate 2. Asking. The shortest distance between the end of the plurality of nanoparticles 102 on the first surface 2a side and the first surface 2a is a scanning electron microscope or transmission electron microscope observation, or a transmission electron microscope and energy dispersive X-ray spectroscopy. It can measure by using the method which used the method together. The average score for obtaining the average end position (Spt) is preferably 20 points or more.

Next, FIG. 5 is a schematic cross-sectional view in the center plane 2c of the second stacked body 2 shown in FIG. That is, FIG. 5 shows a top view when slicing the second laminate 2 along the center plane 2c shown in FIG. 4 and observing the second laminate 2 from the first surface 2a side. Yes. As shown in FIG. 5, since the center plane 2c crosses the plurality of nanoparticles 102, when observed from the first surface 2a side, the plurality of nanoparticles 102 are cleaved and arranged in the center plane within the center plane 2c. Has been. The distance (P) shown in FIG. 5 means the distance between adjacent centers of the nanoparticles 102. The distance _{P A1B1-1} ~ distance _{P A1B1-6} between the center of the nanoparticle B1-1~ nanoparticles B1-6 adjacent the center of a nanoparticle A1 to the nanoparticles A1, is defined as a pitch P. However, as shown in FIG. 5, when the pitch P differs depending on the adjacent nanoparticles 102, the average pitch (Pav) is determined according to the following procedure. (1) A plurality of arbitrary nanoparticles A1, A2... AN are selected. (2) The pitches P _{AMBM-1 to} P _AMBM-k between the nanoparticles AM and the nanoparticles (BM-1 to BM-k) adjacent to the nanoparticles AM (1 ≦ M ≦ N) are measured. (3) For the nanoparticles A1 to AN, the pitch P is measured as in (2). (4) The arithmetic average value of the pitches P _{A1B1-1 to} P _ANBN-k is defined as the average pitch (Pav). However, N is 5 or more and 10 or less, and k is 4 or more and 6 or less. Note that the pitch P can be obtained from cross-sectional image observation using a scanning electron microscope or a transmission electron microscope. When calculating | requiring the pitch P from a cross-sectional image, let the center of the nanoparticle mentioned above be a convex part top part center position.

  It is preferable that the pitch P of the nanoparticles 102 has a distribution of ± 35% or less because the transfer accuracy of the nanoparticles 102 and the processing accuracy of the first mask layer 103 can be improved. In particular, since the placement accuracy of the nanoparticles 102 is improved by being ± 20% or less, it is possible to suppress the number of nanoparticles overlapping in the film thickness direction M of the second laminate 2, and thus the first The processing accuracy of the mask layer 103 can be improved.

An average pitch (Pav) in the center plane of the nanoparticles 102, and a distance (lor) between the average end position (Spt) of the plurality of nanoparticles 102 on the first surface 2a side and the first surface 2a; It is preferable that the ratio (lor / Pav) satisfies the following formula (1). Satisfying the following formula (1) means that the film thickness of the first mask layer 103 is determined according to the density of the nanoparticles 102. When the thickness of the 1st mask layer 103 satisfy | fills Formula (1), the bonding property of the 1st mask layer 103 at the time of bonding the 2nd laminated body 2 to a to-be-processed object can be improved. it can. Furthermore, since the disorder | damage | failure of the arrangement | sequence and shape of the nanoparticle 102 which arise when manufacturing and conveyance of the 2nd laminated body 2 and bonding the 2nd laminated body 2 to a to-be-processed object can be suppressed, a nanoparticle The nanoparticles 102 can be transferred and applied to the object to be processed through the first mask layer 103 with high shape and arrangement accuracy of the 102. In addition, the film thickness accuracy of the first mask layer can be improved. That is, it is possible to further increase the film thickness accuracy of the first mask layer transferred and applied to the object to be processed.
Formula (1)
0.05 ≦ lor / Pav ≦ 10

  In particular, the ratio (lor / Pav) between the distance (lor) and the average pitch (Pav) is determined from the viewpoint of dry etching properties for the nanoparticles 102 and the first mask layer 103 transferred and formed on the object to be processed. / Pav ≦ 10 is preferable, and lor / Pav ≦ 5 is more preferable. From the viewpoint of suppressing the collapse of the pillar (fine mask pattern) composed of the nanoparticles 102 and the first mask layer 103 during dry etching, it is preferable that lor / Pav ≦ 2.5. On the other hand, it is preferable that lor / Pav ≧ 0.05 from the viewpoint of satisfactorily exerting the function of the first mask layer 103 as an adhesive layer and improving the bonding / transfer accuracy. The distance (lor) is preferably greater than 0 nm from the viewpoint of transfer accuracy, and is preferably 3000 nm or less from the viewpoint of dry etching accuracy. The unevenness of the distance (lor) depends on the average pitch (Pav) of the nanoparticles 102 from the viewpoint of the width variation of the first mask layer 103 on the object to be processed after the etching of the first mask layer 103. Generally, it is preferably ± 30% or less, more preferably ± 25% or less, and most preferably ± 10% or less.

  Furthermore, the ratio (Ra / lor) between the surface roughness Ra and the distance lor of the first mask layer 103 is preferably 1 or less. By satisfying this range, it becomes possible to suppress the entrainment of air voids when the first mask layer 103 is bonded to the object to be processed 20, thereby improving the transfer accuracy in the surface of the object to be processed. It becomes possible. From the same effect, the ratio (Ra / lor) is preferably 0.55 or less, more preferably 0.45 or less, and most preferably 0.40 or less. Furthermore, when the ratio (Ra / lor) is 0.2 or less, the first mask layer 103 can be made thin on the nanoscale, and the bonding accuracy can be greatly improved. From the same effect, it is preferably 0.15 or less, and more preferably 0.1 or less. The lower limit is not particularly limited, and the lower the ratio (Ra / lor), the better. However, it is 0.002 or more from the viewpoint of continuously producing a laminate for forming a fine pattern by a roll-to-roll method. Is preferable, 0.004 or more is more preferable, and 0.01 or more is most preferable.

The surface roughness Ra of the exposed surface (first surface 2a) of the first mask layer 103 is preferably 300 nm or less. By satisfying this range, the function of the first mask layer 103 as an adhesive layer can be favorably expressed. In particular, from the viewpoint of suppressing air voids when the first mask layer 102 of the second stacked body 2 is bonded to an object to be processed, the surface roughness Ra with respect to the exposed surface of the first mask layer 103 is 150 nm. Or less, preferably 100 nm or less, and most preferably 50 nm or less. Further, from the viewpoint of reducing the thickness of the first mask layer 103 and improving the transfer accuracy, the processing accuracy of the first mask layer 103, and the processing accuracy of the object to be processed, the exposure of the first mask layer 103 is performed. The surface roughness Ra with respect to the surface is preferably 35 nm or less, more preferably 25 nm or less, and most preferably 15 nm or less. The lower the surface roughness Ra, the better. The lower limit value is not particularly limited, but from the viewpoint of continuously producing the second laminate 2, it is preferably 2 nm or more, and preferably 5 nm or more. More preferred. The surface roughness Ra is defined as a value measured by scanning a measurement range of 150 μm × 150 μm or more using an atomic force microscope (Atomic Force Microscope) at a measurement frequency of 1.11 Hz or more. In addition, when the foreign matter is attached to the surface of the first mask layer 103 and the foreign matter is manipulated with the atomic force microscope, the surface roughness Ra is increased. For this reason, it is preferable that the environment to be measured by the scanning electron microscope is a clean room of class 1000 or less, and it is preferable to perform air blow cleaning in a static elimination environment with an ionizer or the like before the measurement. Further, when the surface of the first mask layer 103 (the first surface 2a) has a scratch represented by a scratch mark, and the entire surface of the scratch is operated with an atomic force microscope, the surface roughness Ra Becomes bigger. For this reason, when measuring with a scanning electron microscope, measurement shall be performed while avoiding scratches. The measurement can be performed, for example, with the following apparatus and conditions.
・ Nanoscale Hybrid Microscope VN-8000 manufactured by Keyence Corporation
・ Measurement range: 200μm (ratio 1: 1)
・ Sampling frequency: 1.11Hz

  The plurality of nanoparticles 102 traversing in the center plane 2c preferably have an average thickness in the direction perpendicular to the center plane 2c (film thickness direction) of the second laminate 2 of 5 nm or more and 1000 nm or less. When the average thickness of the nanoparticles 102 is 5 nm or more, the processing accuracy of the first mask layer 103 can be improved. On the other hand, when the average thickness of the nanoparticles 102 is 1000 nm or less, the physical stability of the nanoparticles 102 can be improved, and the roughness of the first surface 2a of the second laminate 2 can be reduced. Furthermore, the transfer accuracy of the nanoparticles 102 can be improved. From the viewpoint of further exerting this effect, the average thickness of the nanoparticles 102 is preferably 20 nm or more and 800 nm or less, more preferably 30 nm or more and 500 nm or less, and most preferably 50 nm or more and 300 nm or less.

  In addition, the nanoparticles 102 have a variation of ± 25% or less in the thickness (height) of the nanoparticles 102 in the film thickness direction of the second stacked body 2 from the viewpoint of improving the processing accuracy of the first mask layer 103. It is preferable to have. Here, the variation is a value calculated by measuring the thickness (height) in the film thickness direction of the second laminate 2 of each nanoparticle 102 with respect to 20 or more nanoparticles 102. In addition, with respect to 20 or more nanoparticles 102, the thickness (height) of each nanoparticle 102 in the film thickness direction M of the second laminate 2 is measured, and the average value of each measured nanoparticle 102 is This corresponds to the average thickness (Z) of the nanoparticles 102 in the film thickness direction.

  The average value of the diameter (D) of the fractured surface of the nanoparticles 102 cleaved by the center surface 2 c is taken as the average diameter of the nanoparticles 102. This average diameter is calculated as an average value of the diameters (D) by arbitrarily selecting a plurality of nanoparticles 102. The average score is preferably 20 points or more. Further, the center plane 2c when calculating the average diameter is a center plane set at the center between the average end position (Spt) on the first surface 2a side and the average end position on the second surface 2b side. . Here, the central plane is defined as follows. Let Z be the distance between the average edge position (Spt) on the first surface 2a side and the average edge position on the second surface 2b side. The center plane is a plane that has been lowered by Z / 2 in the second surface 2b direction from the average end position (Spt) on the first surface 2a side, that is, in the first surface 2a direction from the average end position on the second surface 2b side. It is the surface which raised Z / 2.

  The average diameter is preferably 1 nm or more and 1000 nm or less. When the average diameter is 1 nm or more, the processing accuracy of the first mask layer 103 can be improved. Moreover, the overlap with respect to the film thickness direction of the 2nd laminated body 2 of nanoparticles 102 can be suppressed because an average diameter is 1000 nm or less. From the viewpoint of further exerting this effect, the average diameter is preferably 10 nm to 800 nm, more preferably 50 nm to 500 nm, and most preferably 80 nm to 300 nm.

  The diameter of the nanoparticles 102 may have a distribution of ± 25% or less. Since the distribution of the diameters of the nanoparticles 102 is ± 25% or less, it is possible to suppress overlapping of the nanoparticles 102 with respect to the film thickness direction of the second stacked body 2, and thus the first mask layer 103. The machining accuracy can be improved. From the same effect, ± 15% or less is more preferable, and ± 10% or less is most preferable.

  Next, the shape of the nanoparticles 102 will be described in detail. There is no restriction | limiting in particular as a shape of the nanoparticle 102. FIG. Examples of the shape of the nanoparticle 102 include a triangular prism, a triangular pyramid, a quadrangular column, a quadrangular pyramid, a polygonal column, a polygonal pyramid, a cone, a cylinder, an elliptical cone, an elliptical column, and a shape in which these bottom surfaces are distorted, and their side surfaces. Or a spherical shape, a disk shape, a lens shape, a flat ellipsoidal shape (oblong shape), an ellipsoidal shape (oblong shape), or the like. Among these, in particular, a shape having a small angle at the bottom, such as a cone, a cylinder, an elliptical cone, and an elliptical column, is preferable. By adopting these shapes, the transfer accuracy of the nanoparticles 102 and the processing accuracy of the first mask layer 103 are improved. The ratio of the major axis radius to the minor axis radius (major axis radius / minor axis radius) when the bottom surface is an ellipse is preferably 1 or more. A circle with a ratio (major axis radius / minor axis radius) of 1 is a circle. From the viewpoint of improving the arrangement accuracy of the nanoparticles 102 and suppressing the overlapping of the nanoparticles 102 with respect to the film thickness direction of the second laminated body 2, the ratio (major axis radius / minor axis radius) is the case where the bottom surface is an ellipse nanoparticle. ) Is preferably 100 or less, more preferably 25 or less, and most preferably 5 or less.

  When the shape of the nanoparticles 102 includes a distribution equal to or less than the value described below, the arrangement accuracy of the nanoparticles 102 and the processing accuracy of the first mask layer 103 can be improved. Here, the distribution of the shape of the nanoparticles 102 is a distribution of variables expressing the shape of the nanoparticles 102. The shape of the nanoparticle 102 is the height (thickness) of the nanoparticle 102, the angle of the side surface, the number of inflection points on the side surface, the length of the side surface, the area (diameter) of the flat surface on the upper surface or the lower surface, Curvature, number of inflection points on upper or lower surface, roughness of upper or lower surface or side surface, aspect ratio (height / lower surface diameter or height / upper surface diameter), upper surface or lower surface and side surface Is defined by the curvature, etc. These are variables x representing the nanoparticles 102. The said effect can be expressed when the ratio (standard deviation / arithmetic mean) of the standard deviation with respect to the variable x and the arithmetic mean is 0.5 or less.

(Arithmetic mean)
The arithmetic mean value is defined by the following equation when N measured values of a certain element (variable) X are x1, x2,.

(standard deviation)
When N measured values of the element (variable) X are x1, x2,..., Xn, the arithmetic mean value defined above is used and is defined by the following equation.

  The number N of sample points when calculating the arithmetic mean is defined as 10 or more. The number of sample points when calculating the standard deviation is the same as the number N of sample points when calculating the arithmetic mean.

  The standard deviation / arithmetic mean is defined as a local value, not an in-plane value. That is, instead of measuring N points across the plane and calculating the standard deviation / arithmetic mean, local observation is performed and the standard deviation / arithmetic mean within the observation range is calculated. Here, the local range used for observation is defined as a range of about 5 to 50 times the average pitch Pav. For example, if the average pitch Pav is 500 nm, the observation is performed in the observation range of 2500 nm to 25000 nm.

  As described above, the shape of the nanoparticle 102 can be expressed by a variable, and if the standard deviation / arithmetic mean with respect to the variable is 0.5 or less, the film thickness direction of the second laminate 2 of the nanoparticle 102 And the processing accuracy of the first mask layer 103 can be improved. From the same viewpoint, the standard deviation / arithmetic average is preferably 0.35 or less, more preferably 0.25 or less, and most preferably 0.15 or less. In particular, it is preferable that the element x has a height (thickness), a diameter (area) of the upper surface or the lower surface, or an aspect because the transfer accuracy of nanoparticles in the above range (standard deviation / arithmetic mean) is improved. The arrangement of the nanoparticles 102 can be expressed by setting the pitch to a variable x. Also in this case, it is preferable that the above range is satisfied from the same effect.

  When the pitch P of the nanoparticles 102 is considered as an element constituting the nanoparticles 102, the above-described ratio (standard deviation / arithmetic mean) is preferably 0.4 or less. In this case, it is possible to suppress overlap of the second stacked body 2 of the nanoparticles 102 with respect to the film thickness direction. From the same viewpoint, it is preferably 0.35 or less, more preferably 0.25 or less, and most preferably 0.15 or less. On the other hand, the lower limit is not particularly limited. This is because as the ratio to the pitch P (standard deviation / arithmetic mean) is smaller, the arrangement regularity of the nanoparticles 102 is improved and the transfer accuracy of the nanoparticles 102 is improved. In particular, when the range of the ratio (lor / Pav) described above is satisfied, even if the ratio to the pitch P (standard deviation / arithmetic mean) is large within the range, the transfer accuracy of the nanoparticles 102 is improved. It becomes possible to keep.

  Furthermore, it is preferable that the apex diameter of the nanoparticles 102 on the first surface 2a side and the apex diameter of the nanoparticles 102 on the second surface 2b side are improved because the arrangement accuracy and transfer accuracy of the nanoparticles 102 are improved. That is, the side surface of the nanoparticle 102 preferably has a gradient from the thickness direction of the second stacked body 2. Since the nanoparticle 102 has a tilted structure, the shape of the nanoparticle 102 is stabilized and the transfer accuracy of the nanoparticle 102 is improved, so that the processing accuracy of the first mask layer 103 is improved. be able to. From the standpoint of more exerting this effect, the top diameter on the first surface 2a side of the nanoparticle 102 and the top diameter on the second surface 2b side of the nanoparticle 102 are preferably different by 2 times or more, and 5 times or more. More preferably, 10 times or more is most preferable. Most preferably, the top diameter of the nanoparticles 102 on the first surface 2a side or the top diameter of the nanoparticles 102 on the second surface 2b side is asymptotic to 0, in other words, flat on the upper surface or the lower surface of the nanoparticles 102. This is the case when there is no surface. In particular, when the apex diameter on the first surface 2a side is larger than the apex diameter on the second surface 2b side, the above-described effect can be further exerted.

  Further, (standard deviation) / (arithmetic mean) with respect to the height (thickness) of the nanoparticles 102 is preferably 0.40 or less from the viewpoint of the transfer accuracy of the nanoparticles 102. Further, it is preferably 0.35 or less because the processing accuracy of the first mask layer 103 can be improved. Especially, since it is the range of 0.25 or less, the stability of the shape of the nanoparticle 102 will improve, Therefore It becomes possible to process the 1st mask layer 103 more favorably. In particular, when the range of the ratio (lor / Pav) described above is satisfied, even if the ratio (standard deviation / arithmetic mean) to the height (thickness) is large within the above range, the transfer accuracy of the nanoparticles 102 is high. Can be kept good.

  6A to 6D are diagrams illustrating an example of the shape of the nanoparticle 102. 6A to 6D show vertical cross sections of the second stacked body 2 with respect to the first surface 2a and the second surface 2b, as in FIG.

  As shown in FIGS. 6A to 6D, the shape of the nanoparticle 102 is asymmetric with respect to a line segment X in a direction parallel to the center plane 2 c, and is centered. It is preferably substantially line symmetric with respect to the line segment Y in the direction perpendicular to the surface 2c. The term “substantially line symmetric” here does not mean only complete line symmetry, but also allows line symmetry whose symmetry is broken within a range where the effects of the present invention are exhibited. The shape of the nanoparticles 102 is such that the tip on the first surface 2a side protrudes toward the first surface 2a, and the tip on the second surface 2b side has a shape substantially parallel to the second surface 2b. The tip on the second surface 2b side protrudes toward the second surface 2b, and the tip on the first surface 2a side has a shape substantially parallel to the first surface 2a side. It may be present (see FIG. 6B). The nanoparticle 102 has a shape in which the tip on the first surface 2a side protrudes toward the first surface 2a and the tip on the second surface 2b side is recessed toward the first surface 2a. (See FIG. 6C), the tip on the second surface 2b side protrudes to the second surface 2b side, and the tip on the first surface 2a side is recessed toward the second surface 2b side. (See FIG. 6D). By using such nanoparticles 102, the array stability of the nanoparticles 102 is improved. That is, when the first mask layer 103 is formed on the first laminated body 1, when the second laminated body 2 is packaged, transported, and when the first laminated body 2 is transported, It is possible to suppress the disorder of the nanoparticle arrangement that occurs when the mask layer 103 is bonded to the object to be processed.

  The arrangement of the nanoparticles 102 is defined with respect to the center plane 2c. The arrangement of the nanoparticles 102 in the center plane 2c is not particularly limited because it can be selected depending on the use of a fine mask pattern having a high aspect ratio provided on the object to be processed. For example, a regular hexagonal arrangement, a quasi-hexagonal arrangement, A tetragonal array, a regular tetragonal array, a random array, an array obtained by combining these regularly or with low regularity, and the like can be employed. For example, an array that gradually changes from a hexagonal array to a tetragonal array and then returns to the hexagonal array can be employed. In particular, from the viewpoint of arrangement accuracy of the nanoparticles 102, a hexagonal array in which the distortion of the array in the regular hexagonal array is ± 25% or less is preferable.

  In the second stacked body 2 according to the present embodiment, an object to be processed may be provided on the surface (first surface 2a) of the first mask layer 103. In this case, an object to be processed is provided on the surface of the first mask layer 103, or a hard mask layer is provided on one main surface of the object to be processed, and the first mask layer 103 is provided on the hard mask layer. The surface (first surface 2a) is provided.

  The second laminated body 2 (hereinafter referred to as the third laminated body) in which the object to be processed is bonded to the surface (first surface 2a) side of the first mask layer 103 is manufactured, and the third laminated body is separated. Can be transported to other facilities. If the term already explained is used, it will be the state which manufactures to the 3rd laminated body in the 1st line, and uses the 3rd laminated body in the 2nd line. In this case, foreign matter can be prevented from entering the interface between the object to be processed and the first mask layer 103. Moreover, it becomes possible to ensure the bonding precision of the 1st mask layer 103 and a to-be-processed object with the installation and environment which manufacture a 3rd laminated body. For this reason, it is possible to perform processing at a facility that is optimal for processing the first mask layer 103 using the nanoparticles 102 as a mask. For this reason, since processing accuracy can be improved when processing the object to be processed and providing a fine pattern, the manufacturing stability of devices (particularly semiconductor light-emitting elements) manufactured using the object to be processed having the fine pattern is improved. Can be improved.

  By providing a hard mask layer on the object to be processed in advance, dry etching is performed on the first mask layer 103 and the nanoparticles 102 transferred and formed on the hard mask layer, so that the first mask layer 103 and the nanoparticles 102 are transferred. A fine mask pattern having a high aspect ratio can be formed on the hard mask layer. Using the fine mask pattern as a mask, the hard mask layer can be easily finely processed. By using the hard mask pattern obtained by finely processing the hard mask layer as a mask, the object to be processed can be easily etched. In particular, by applying the hard mask layer, when processing the object to be processed and obtaining a fine pattern on the object to be processed, applicability of wet etching is improved in addition to dry etching.

  The material of the hard mask layer is not particularly limited as long as it is determined by the selection ratio with the object to be processed (the etching rate of the object to be processed / the etching rate of the hard mask layer). The selection ratio is preferably 1 or more from the viewpoint of workability, and more preferably 3 or more. From the viewpoint of increasing the aspect ratio of the object to be processed, the selection ratio is preferably 5 or more, and more preferably 10 or more. Since the hard mask layer can be thinned, the selection ratio is more preferably 15 or more. Although the material of the hard mask layer is not limited, for example, silica, titania, spin-on-glass (SOG), spin-on-carbon (SOC), chromium, aluminum, tungsten, hafnium, an oxide thereof, or the like can be used. From the viewpoint of workability during etching, the thickness of the hard mask layer is preferably 5 nm to 500 nm, more preferably 5 nm to 300 nm, and most preferably 5 nm to 150 nm.

  The hard mask layer may have a multilayer structure. Here, the multilayer means the lamination of the hard mask layers in the film thickness direction. For example, the first hard mask layer (1) may be provided on the main surface of the object to be processed, and the second hard mask layer (2) may be provided on the first hard mask layer (1). . Similarly, an N + 1th hard mask layer (N + 1) may be provided on the Nth hard mask (N). The number of stacked hard mask layers is preferably 10 or less, more preferably 5 or less, and most preferably 3 or less from the viewpoints of workability of the hard mask layer and processing accuracy of the object to be processed. .

  When the hard mask layer has a multilayer structure, the thickness of each layer is preferably 5 nm or more and 150 nm or less, and the total film thickness of all layers is preferably 500 nm or less, including a single layer. . In particular, the total film thickness is preferably 300 nm or less, and more preferably 150 nm or less.

Examples of the configuration of the two hard mask layers include a configuration in which SiO ₂ is formed on the main surface of the object to be processed, and Cr is formed on the SiO ₂ . As the configuration of the 3-layer hard mask layer, for example, SiO ₂ is deposited on the main surface of the object, Cr is deposited on the SiO _2, SiO ₂ is deposited on the Cr On the main surface of the object to be processed, on the main surface of the object to be processed, SiO ₂ is formed on the main surface of the object to be processed, SOG is formed on SiO ₂ , and SOC is formed on the SOG. SiO ₂ is deposited, SOC is formed on SiO _2, configuration and the like SOG is deposited and the like on the SOC.

  Next, an outline of a fine pattern forming method using the second laminate 2 according to the present embodiment will be briefly described. As shown to FIG. 7A, the 1st mask layer 103 of the 2nd laminated body 2 and the to-be-processed object 200 are bonded.

  Next, as shown in FIG. 7C, the protective layer 101 is peeled off from the first mask layer 103 and the nanoparticles 102, whereby the stack composed of the nanoparticles 102 / first mask layer 103 / object 200 is formed. A body 201 can be obtained. Note that the peeling of the protective layer 101 can be replaced by not only a method of physically peeling the protective layer 101 but also swelling dissolution of the protective layer 101 and chemical dissolution of the protective layer 101. In FIG. 7A, the protective layer 101 is provided on the support substrate 100. The peeling of the protective layer 101 means peeling of the protective layer 101 and the support substrate 100. Here, when a curable substance is contained in at least one of the first mask layer 103 and the nanoparticles 102, the first mask layer 103 of the second laminate 2 and the target object 200 are bonded together. And / or it is preferable to promote hardening in the state of the laminated body 201. When the curing is photopolymerization, it is preferable to irradiate at least energy rays. In the case where a photopolymerizable substance is contained, in particular, as shown in FIG. 7B, after the first mask layer 103 of the second laminate 2 and the object to be processed 200 are bonded, the protective layer 101 or the object to be processed is bonded. It is preferable to irradiate energy rays from at least one of the treatment bodies 200. On the other hand, when the curing is thermal polymerization, it is preferable to perform at least heating. As described above, when the second laminated body 2 contains a curable substance, if the curing is promoted before the target object 200 is processed using the first mask layer 103 as a processing mask, the processing of the target object 200 is performed. Accuracy can be improved. In particular, when the glass transition temperature is present in the first mask layer 103, the glass transition temperature is increased by promoting the curing of the first mask layer 103, so that the processing accuracy of the workpiece 200 is improved. Can do.

  Next, as shown in FIG. 7D, the first mask layer 103 is etched using the nanoparticles 102 of the obtained stacked body 201 as a mask, so that a fine mask pattern 202a having a high aspect ratio is formed on the target object 200. As a result, a fine pattern structure 202 provided with is obtained. That is, a fine mask pattern 202a composed of the nano-particles 102 / the first mask layer 103 finely processed can be formed on the object 200. By etching the object to be processed 200 using the fine mask pattern 202a as a mask, even if the object to be processed 200 is a difficult-to-process substrate as shown in FIG. 7E, it can be easily processed. It becomes. Finally, as shown in FIG. 7F, by removing the residue (first mask layer 103) on the target object 200, the target object 200 on which the fine pattern 220 is formed can be obtained.

  In this manner, the laminate 201 composed of the nanoparticles 102 / the first mask layer 103 / the object to be processed 200 can be transferred and formed by laminating the second laminate 2 directly on the object to be processed 200. Thereby, know-how such as filling of the resist layer and uniform pressing in nanoimprint (transfer) can be eliminated, and transfer can be performed using a laminate which is a general method, and thus a laminate 201 can be obtained more easily. It becomes possible. Further, by using the second stacked body 2, it is possible to ensure the film thickness distribution of the first mask layer 103 with the coating accuracy of the first mask layer 103. That is, it becomes possible to further reduce the film thickness distribution of the first mask layer 103 by bonding and transfer to the object to be processed 200, and in the stacked body 201, the first mask layer in the surface of the object to be processed 200. The film thickness distribution accuracy of 103 can be improved, and the distribution accuracy of the fine mask pattern 202a formed by etching on the workpiece 200 can be improved. For this reason, by using the second stacked body 2, it is possible to improve the distribution accuracy of the fine mask pattern 202 a in the surface of the target object 200, and to reduce the in-plane distribution of the function to be expressed. . When processing the target object 200 using the fine mask pattern 202a as a mask, the fine pattern 220 of the processed target object 200 has high distribution accuracy in the surface of the target object 200.

  In the method of forming the fine pattern 220 on the surface of the object to be processed 200 using the second stacked body 2, the nanoparticle 102 is used as a mask from the viewpoint of forming the fine mask pattern 202 a on the object to be processed 200. The processing of one mask layer 103 is preferably dry etching. The ratio (Vo1 / Vm1) of the etching rate (Vm1) of the nanoparticles 102 by the dry etching and the etching rate (Vo1) of the first mask layer 103 is obtained by etching the first mask layer 103 using the nanoparticles 102 as a mask. It affects the processing accuracy when performing. Vo1 / Vm1> 1 means that the nanoparticles 102 are less likely to be etched than the first mask layer 103, and thus it is preferable that the ratio is larger. Further, from the viewpoint of the disposition property of the nanoparticles 102 to the protective layer 101, Vo1 / Vm1 ≦ 1000 is preferable, Vo1 / Vm1 ≦ 150 is more preferable, and Vo1 / Vm1 ≦ 100 is most preferable.

From the above viewpoint, it is preferable that the ratio (Vo1 / Vm1) of the etching rate (Vm1) of the nanoparticles 102 and the etching rate (Vo1) of the first mask layer 103 satisfies the following formula (2). Thereby, the etching resistance of the nanoparticles 102 is improved and the etching amount of the nanoparticles 102 is reduced, so that the fine pattern structure 202 can be formed.
Formula (2)
3 ≦ Vo1 / Vm1

  The ratio (Vo1 / Vm1) is more preferably 10 ≦ Vo1 / Vm1, and further preferably 15 ≦ Vo1 / Vm1. When the ratio (Vo1 / Vm1) satisfies the above range, even when the thick first mask layer 103 is used, the first mask layer 103 is formed by dry etching using the nanoparticles 102 as a mask. Microfabrication can be easily performed. Thereby, the finely processed fine mask pattern 202a can be formed on the workpiece 200. By using such a fine mask pattern 202a, the object to be processed 200 can be easily dry-etched, and functions such as super water repellency, super hydrophilicity, adhesiveness, and sensor can be provided on the object 200. be able to. For example, in the case of a sensor, the sensor can be produced by selecting a metal typified by gold or silver as the nanoparticle 102. When trace substances (molecules that measure the degree of progression or infection of a given disease) adhere to such metal surfaces, it is difficult to measure using surface plasmons (surface plasmon polaritons) on metal surfaces. Even a trace concentration such as ppb or ppb can be detected by doubling the sensitivity by the optical system.

On the other hand, the etching anisotropy in etching the first mask layer 103 (lateral etching rate _{(Vo //)} and vertical etching rate (Vo _⊥), the ratio of _{(Vo ⊥} / Vo _//) is , Vo _⊥ / Vo _// >> 1. It is more preferable that the _ratio is larger, where the vertical direction means the film thickness direction of the first mask layer 103, and the horizontal direction means the first mask. It means the in-plane direction of the layer 103. Further, the ratio ( _V0 / Vo _// ) depends on the use from the viewpoint of forming the fine mask pattern 202a on the workpiece 200, but generally _V0 / it is preferably Vo _// ≧ 2, more preferably from _{Vo ⊥} / Vo _// ≧ 3.5, the _{Vo ⊥} / Vo _// ≧ 10 and it is further preferred. the resulting fine mask pattern 202a Used, treated When processing the physical body 200, in a region where the pitch is submicron or less, a viewpoint of stably forming the first mask layer 103 having a high height, and a viewpoint of easily dry-etching the target object 200 Therefore, it is necessary to keep the width (diameter) of the first mask layer 103 large, and by satisfying the above range, the width (thickness of the trunk) of the first mask layer 103 after dry etching can be kept large. This is preferable because it is possible.

  The target object 200 is not particularly limited and can be appropriately selected depending on the use of the fine pattern structure 202 (water repellency, hydrophilicity, adhesiveness, sensor, mask for substrate processing, etc.). Therefore, as the object to be processed 200, a resin film, a resin plate, a resin lens, an inorganic base material, an inorganic film, an inorganic lens, or the like can be used.

  In particular, when the target object 200 is processed using the fine mask pattern 202a as a mask, examples of the target object 200 include quartz typified by synthetic quartz and fused silica, non-alkali glass, low alkali glass, Glass represented by soda lime glass, inorganic substrates such as silicon wafer, nickel plate, sapphire, diamond, SiC, mica, ZnO, semiconductor substrate (such as nitride semiconductor substrate), spinel substrate and ITO can be used. . Further, when the second laminated body 2 is flexible, an inorganic base material having a curved outer shape (for example, a lens shape, a cylindrical / columnar shape, a spherical shape, etc.) is selected as the object 200 to be processed. You can also. In particular, when the second laminate 2 is a film (reel), the shape of the second laminate 2 can be easily changed by cutting or punching. Thereby, the fine mask pattern 202a of a predetermined shape can be arbitrarily formed on the surface of the object 200. For this reason, for example, even when the object to be processed 200 has a cylindrical shape or a lens shape, the fine mask pattern 202a can be formed entirely or partially on the surface of the object to be processed.

  The ratio (Vo2 / Vi2) between the etching rate (Vi2) of the target object 200 by dry etching and the etching rate (Vo2) of the first mask layer 103 is preferably as small as possible. If Vo2 / Vi2 <1, the etching rate of the first mask layer 103 is smaller than the etching rate of the workpiece 200, so that the workpiece 200 can be easily processed.

It is preferable that the etching rate ratio (Vo2 / Vi2) satisfies the following formula (3). Thereby, the coating property and etching accuracy of the first mask layer 103 are improved, so that the fine pattern structure 202 can be formed. Further, the etching rate ratio (Vo2 / Vi2) is more preferably Vo2 / Vi2 ≦ 2.5. From the viewpoint of making the first mask layer 103 thinner, it is more preferable that Vo2 / Vi2 ≦ 2. It is preferable that Vo2 / Vi2 ≦ 1 is satisfied. By satisfying Vo2 / Vi2 ≦ 1, the processing accuracy when processing the target object 200 is further improved using the fine mask pattern 202a formed on the target object 200 as a mask, and further on the target object 200. The shape controllability of the fine pattern 220 provided on the surface is improved. Furthermore, satisfying Vo2 / Vi2 ≦ 0.8 is preferable because the depth of the fine pattern 220 provided on the workpiece 200 can be increased. The lower limit is preferably 0.05 or more. By satisfying this range, even if the side surface of the first mask layer 103 or the nanoparticles 102 is rough, the smoothness of the uneven surface of the fine pattern 220 provided on the object 200 can be improved. . From the same viewpoint, it is preferable to satisfy Vo2 / Vi2 ≧ 0.1, more preferable to satisfy Vo2 / Vi2 ≧ 0.2, and most preferable to satisfy Vo2 / Vi2 ≧ 0.4.
Formula (3)
Vo2 / Vi2 ≦ 3

  Thus, in the second stacked body 2 according to the present embodiment, a plurality of nanoparticles 102 are arranged on the surface of the protective layer 101, and the first mask layer 103 is provided so as to cover the plurality of nanoparticles 102. Has a configuration. Accordingly, when the first mask layer 103 is bonded to the object to be processed 200, and the stacked body 201 including the first mask layer 103 and the nanoparticles 102 is formed on the object to be processed 200, the first mask layer 103 is formed. On the surface of the layer 103, there are almost no nanoparticles 102 overlapping in the thickness direction of the first mask layer 103. As a result, in the dry etching process when the fine mask pattern 202a is formed on the target object 200, the process of removing the overlapping nanoparticles 102 of the stacked body 201 corresponding to the remaining film can be omitted. Therefore, it is possible to improve the processing accuracy of the fine mask pattern 202a formed on the target object 200, and the accuracy of the fine pattern 220 provided on the target object 200 by further processing is improved.

  Furthermore, since the first mask layer 103 can be easily finely processed by satisfying the etching rate ratio between the first mask layer 103 and the nanoparticles 102 within a predetermined range, the fine mask pattern 202a is formed on the workpiece 200. It becomes possible to form stably on top.

The concentration of the solvent remaining in the first mask layer 103 and the nanoparticles 102 is preferably 2100 (g / ml) / m ³ or less when measured according to the following criteria. By satisfying this range, the bonding accuracy of the second laminate 2 to the target object 200, the processing accuracy of the first mask layer 103 by the nanoparticles 102, and the processing of the target object 200 by the first mask layer 103 are performed. Accuracy can be improved. From the viewpoint of more exerting the effect, it is preferably 1200 (g / ml) / m ³ or less, more preferably 600 (g / ml) / m ³ or less, 250 (g / ml) / m. Most preferably, it is ³ or less. Furthermore, from the viewpoint of improving the transfer accuracy of the nanoparticles 102 and the first mask layer 103 regardless of the surface state of the protective layer 101, it is preferably 170 (g / ml) / m ³ or less, and 150 (g / Ml) / m ³ or less, more preferably 130 (g / ml) / m ³ or less.
1. The 2nd laminated body 2 is cut into 20 mm x 20 mm, measured up with 10 mL acetone, and a solution is extract | collected.
2. The collected solution is analyzed by the SIM method using a GC / MS apparatus, and the amount of the solvent is obtained with a dimension of “g / ml”.
3. The average total thickness have [m] of the first mask layer 103 and the nanoparticles 102 of the second laminate 2 is obtained.
4.2. The value obtained by dividing the result by the volume of the first mask layer 103 and the nanoparticles 102 (0.02 m × 0.02 m × have) is the concentration of the solvent remaining in the first mask layer 103 and the nanoparticles 102. And

  Hereinafter, the material of each component will be described in detail.

[Protective layer]
The protective layer 101 is preferably in the form of a flat plate, a film, or a reel. In particular, when the protective layer 101 is in the form of a film or a reel, the ease of bonding the second laminate 2 to the object 200 and Accuracy is improved. Moreover, the protective layer 101 may be formed without using a support base material, and may be formed on the support base material.

  Examples of the protective layer 101 that does not include a supporting substrate include a film-like protective layer made of soft polydimethylsiloxane (PDMS), COP, polyimide, polyethylene, PET, polyolefin resin, fluororesin, or thermoplastic resin. It is done. Further, as the protective layer 101, a flat protective layer made of an inorganic material may be used. Examples of the inorganic material include quartz, glass, silicon, nickel, diamond-like carbon, fluorine-containing diamond-like carbon, SiC, diamond, chromium, and sapphire.

  By using the hard flat protective layer 101, the surface accuracy of the protective layer 101 can be kept high. Here, the surface accuracy means the parallelism between the end position of the nanoparticle 102 on the second surface 2b side and the surface of the protective layer 101 opposite to the nanoparticle 102 (second surface 2b). The surface accuracy (one main surface of the object 200 and the nanoparticles 102) of the stacked body 201 produced by using the second stacked body 2 using the protective layer 101 having such a high degree of parallelism (surface accuracy). The degree of parallelism with the surface formed by the tops of the two can be kept high. This improves the surface accuracy of the fine mask pattern 202a of the fine pattern laminate 201 produced by dry etching (the parallelism between the one main surface of the object 200 and the top of the nanoparticles 102). The surface accuracy of the fine pattern 220 of the workpiece 200 to be processed (the surface constituted by the top of the fine pattern 220 included in the workpiece 200 and the surface constituted by the bottom of the concave portion of the fine pattern 220) Parallelism) can be kept high.

  For example, in order to simultaneously improve the internal quantum efficiency and light extraction efficiency of LEDs, sapphire substrates, Si (silicon) substrates, ITO substrates, ZnO substrates, SiC (silicon carbide) substrates, nitride semiconductor substrates, or spinel substrates are processed. When microfabrication is performed as the body 200, the size and distribution of the fine pattern 220 produced on the substrate is important. The fact that the height accuracy of the fine pattern 220 on the substrate can be ensured by the surface accuracy of the protective layer 101 is directly linked to the accuracy of the thickness of the trunk of the fine mask pattern 202a formed by dry etching. The accuracy of the thickness of the trunk is directly related to the size accuracy of the fine pattern 220 formed on the substrate. Furthermore, transfer by a step-and-repeat method is possible, and productivity can be kept high.

  On the other hand, by using the soft protective layer 101, entrainment of large bubbles when the second laminate 2 is bonded to the object 200 can be suppressed. Furthermore, since unevenness and particles on the surface of the object 200 can be absorbed, transfer accuracy is improved. These effects improve the transfer formation accuracy of the laminate 201 and improve the processing accuracy when processing the target object 200 with the fine mask pattern 202a as a mask.

  As the protective layer 101 having a supporting base (100 in FIGS. 7A and 7B), a combination of a hard supporting base and a soft protective layer 101, a combination of a soft supporting base and a hard protective layer 101 Or the combination of a soft support base material and the soft protective layer 101 is mentioned. In particular, the combination of the soft support substrate 100 and the soft protective layer 101 is suitable for manufacturing the second laminate 2 continuously by a roll-to-roll process. Further, by using the obtained soft and reel-like (film-like) second laminate 2, the first mask layer 103 and the second mask 2 can be continuously and highly accurately transferred to the object 200. The nanoparticles 102 can be transferred and formed, that is, the laminate 201 can be obtained continuously and with high accuracy. In addition, by using the second laminated body 2 including the soft and reel-shaped (film-shaped) protective layer 101, the first mask layer 103 and the nanoparticles 102 can be formed on arbitrary portions of the object to be processed. It can be transferred and formed. The same applies to a curved surface.

  As a combination of a hard support base and a soft protective layer 101, a support base made of an inorganic material such as glass, quartz, silicon, SUS, and an aluminum plate, PDMS, polyimide, polyethylene, PET, COP, Examples thereof include a combination with a protective layer 101 composed of a fluororesin, a photocurable resin, or the like.

  Thus, by providing the soft protective layer 101 on a hard support base material, the surface physical property of the protective layer 101 can be easily changed in the state which ensured the surface precision of the hard support base material. Therefore, the film-forming property when forming the nanoparticles 102 on the protective layer 101, and hence the alignment property of the nanoparticles 102, and the coating property of the first mask layer 103 when manufacturing the second laminate 2. Will improve. In addition, the surface accuracy of the stacked body 201 formed by the transfer (parallelism between one main surface of the target object 200 and the top of the nanoparticles 102) can be kept high, and the nanostructure of the stacked body 201 can be maintained. It is possible to improve the height accuracy of the fine mask pattern 202a after etching from the particle 102. Accordingly, it is possible to ensure the processing accuracy when processing the workpiece 200 with the fine mask pattern 202a as a mask.

  As a combination of the soft support base and the hard protective layer 101, there are a support base made of a flexible elastic body typified by sponge or rubber (silicone rubber, etc.), silicon, quartz, nickel, chromium, sapphire. , SiC, diamond, diamond-like carbon, or a combination with a protective layer 101 made of an inorganic material such as fluorine-containing diamond-like carbon. When the supporting base material is a flexible elastic body, it is preferable that the Young's modulus (longitudinal elastic modulus) of the supporting base material is generally 1 Mpa or more and 100 Mpa or less because surface accuracy can be kept high. From the same effect, it is more preferable that it is 4 Mpa or more and 50 Mpa or less. In addition, from the viewpoint of transfer accuracy when forming the laminate 201 composed of the nanoparticles 102 / the first mask layer 103 / the workpiece 200, the thickness is preferably 0.5 mm or more and 20 cm or less, and preferably 1 mm or more and 10 cm. The following is more preferable, and most preferably 5 mm or more and 8 cm or less.

  With such a combination, when the second laminated body 2 is bonded and pressed to the object to be processed 200, the surface accuracy of the hard protective layer 101 is improved by the stress relaxation effect and the stress concentration absorption effect by the soft support base material. It can be further enhanced. As a result, the height accuracy of the fine pattern structure 202 can be improved. Accordingly, it is possible to ensure the processing accuracy when processing the target object 200 using the fine mask pattern 202a as a mask.

  The combination of the soft support base and the soft protective layer 101 is composed of a support base composed of a resin film such as a PET film, a TAC film, a COP film, a PE film, and a PP film, and a photocurable resin. And a combination with the protective layer 101 to be formed.

  By such a combination, the 2nd laminated body 2 can be continuously manufactured by the roll-to-roll method, and the bonding to the to-be-processed object 200 at the time of using the 2nd laminated body 2 is carried out. It becomes easy. By producing the second laminate 2 by the roll-to-roll method, the arrangement accuracy of the nanoparticles 102 on the protective layer 101 can be improved. Further, since the coating property of the first mask layer 103 is improved, the film thickness distribution accuracy of the first mask layer 103 can be improved. For this reason, the thickness distribution and pattern accuracy of the first mask layer 103 and the nanoparticles 102 transferred and formed on the target object 200 can be given high, reflecting the accuracy of the second stacked body 2. The accuracy of the laminate 201 is greatly improved. In particular, the second laminate 2 is bonded to the object 200 by using a cylindrical (columnar) bonding roll, and the support base material / protective layer 101 / nanoparticle 102 / first mask layer. It is possible to suppress defects such as air voids (macro bubbles) that are generated when a laminate composed of 103 / processed body 200, that is, a third laminate, and to improve the bonding speed. Furthermore, by applying the roll-to-roll method, the peeling stress acts as a line when peeling the supporting substrate and the protective layer 101 from the third laminate, so that the transfer accuracy is improved.

  In addition, by arranging the combination of the soft support base and the soft protective layer 101 on the hard support base, the same effect as the combination of the hard support base and the soft protective layer 101 described above is obtained. Can be obtained.

  There is no restriction | limiting in particular regarding the material of a support base material, It can use regardless of organic materials, such as inorganic materials, such as glass, a ceramic, a silicon wafer, and a metal, plastics, rubber | gum, sponge. Depending on the use of the laminate for forming a fine pattern, a plate, a sheet, a film, a reel, a thin film, a woven fabric, a non-woven fabric, and other arbitrary shapes and composites thereof can be used, but glass, quartz, silicon, SUS, etc. Only hard inorganic materials, rubber (silicone rubber, etc.) and soft elastic bodies such as sponge, or glass, quartz, silicon, SUS and other hard inorganic materials, rubber (silicone rubber, etc.) and sponge are laminated, PET film It is preferable to employ a resin film such as a TAC film, a COP film, a PE film, or a PP film as a supporting substrate.

  In order to improve the adhesion between the support base material and the protective layer 101, it is easy for chemical bonding with the protective layer 101 and physical bonding such as penetration on one main surface of the support base material on which the protective layer 101 is provided. Adhesive coating, primer treatment, corona treatment, plasma treatment, UV / ozone treatment, excimer treatment, high energy ray irradiation treatment, surface roughening treatment, porous treatment, and the like may be performed.

  The support base material (100 shown in FIGS. 7A and 7B) of the protective layer 101 may be transparent or colored. By being transparent, it is easy to apply a roll-to-roll method (photo nanoimprint method) when manufacturing the protective layer 101, and thus the accuracy and manufacturing performance of the protective layer 101 are improved. Furthermore, when irradiating the third laminated body composed of the supporting substrate / protective layer 101 / nanoparticle 102 / first mask layer 103 / object 200, energy is passed through the supporting substrate. It becomes possible to irradiate a line. On the other hand, when colored, the preservability of the second laminate 2 can be improved. In particular, when the second laminate 2 includes a photopolymerizable substance, the photopolymerization application wavelength of the photopolymerizable substance can be suppressed by coloring. Similarly, the protective layer 101 may be transparent or colored.

  Moreover, in the case of being transparent, it is preferable that the support base material has a transmittance of 50% or less for ultraviolet light (UV) because the storage stability of the second laminate 2 is improved. In particular, from the viewpoint of suppressing the photodegradation of the first mask layer 103, the transmittance of ultraviolet light to the support substrate is preferably 35% or less, more preferably 15% or less, and 5% or less. Most preferably it is. In the case of a support base material provided with an ultraviolet light absorbing material or a metal film, the transmittance of ultraviolet light can be reduced to almost 0%. In this case, the performance preservation | save property of the 2nd laminated body 2 can be improved more.

  On the other hand, when it is colored, the storage stability of the second laminate 2 is improved when the support substrate has a transmittance of 60% or less with respect to light of the photosensitive wavelength (λ) of the component contained in the second laminate 2. Therefore, it is preferable. In particular, from the viewpoint of suppressing the photodegradation of the first mask layer 103, the light transmittance of the photosensitive wavelength (λ) with respect to the support substrate is preferably 35% or less, and more preferably 15% or less. Preferably, it is most preferably 5% or less. In the case of a supporting base material provided with a metal film, the light transmittance of the photosensitive wavelength (λ) can be made almost 0%. In this case, the performance preservation | save property of the 2nd laminated body 2 can be improved more.

  As the support substrate of the protective layer 101, the above-mentioned support substrate can be adopted, but a support substrate considering the viewpoint of the resin layer containing the refractive index, haze, and fine particles described below should be used. As a result, the transfer accuracy of the first mask layer 103 and the nanoparticles 102 can be further improved.

  After using the second laminate 2 and forming a third laminate comprising the support substrate / protective layer 101 / nanoparticles 102 / first mask layer 103 / object 200, the support substrate surface side In the case of irradiating the energy beam from the substrate, the smaller the reflection of the energy beam at the interface between the support substrate and the protective layer 101, the better the transfer accuracy and the lower the power of the energy beam source to be used. For this reason, the difference (| n1-n2) | between the refractive index (n1) of the supporting substrate and the refractive index (n2) of the protective layer with respect to the main wavelength (λ) required for the reaction of the first mask layer 103 is 0. .3 or less, more preferably 0.2 or less, and most preferably 0.15 or less. Note that it is preferable that the difference in refractive index (| n1−n2) | is 0.1 or less because the energy beam does not substantially recognize the interface between the support substrate 100 and the protective layer 101.

  The haze of the supporting substrate is preferably 30% or less. By being 30% or less, the adhesion of the protective layer 101 can be ensured. In particular, from the viewpoint of transfer accuracy and adhesion of the protective layer 101, the haze is preferably 10% or less, more preferably 6% or less, and most preferably 1.5% or less. In addition, when the patterned energy beam is irradiated to the second stacked body 2 to form the stacked body 201 composed of the patterned nanoparticles 102 / first mask layer 103 / processed object 200, From the viewpoint of resolution, the haze is preferably 1.5% or less. The haze is a value representing turbidity, and is obtained from the total transmittance T of light irradiated by a light source and transmitted through the sample and the transmittance D of light diffused and scattered in the sample, and the haze value H = D / T × 100. These are defined by JIS K 7105. It can be easily measured with a commercially available turbidimeter (for example, NDH-1001DP manufactured by Nippon Denshoku Industries Co., Ltd.). Examples of the supporting substrate having a haze value of 1.5% or less include polyethylene terephthalate films such as Teijin's highly transparent film GS series, Diafoil Hoechst's M-310 series, and DuPont's Mylar D series. Etc.

  When a film-like support substrate is selected as the support substrate, a support substrate obtained by laminating a resin layer containing fine particles on one surface of a biaxially oriented polyester film may be employed. The workability when continuously manufacturing the protective layer 101 by a roll-to-roll process and the workability when continuously bonding the second laminate 2 to the workpiece 200 are improved. From the viewpoint of suppressing the occurrence of pattern defects and macro defects such as millimeter scale and centimeter scale, the average particle diameter of the fine particles is preferably 0.01 μm or more. Irradiation with a patterned energy beam is applied to the fine pattern forming laminate to improve the resolution in the case of forming the laminate 201 composed of the patterned nanoparticles 102 / first mask layer 103 / object 200. From the viewpoint, the average particle size of the fine particles is preferably 5.0 μm or less. From the viewpoint of further exerting this effect, the thickness is more preferably 0.02 μm to 4.0 μm, and particularly preferably 0.03 μm to 3.0 μm.

  The blending amount of the fine particles can be appropriately adjusted according to, for example, the base resin constituting the resin layer, the kind and average particle size of the fine particles, and desired physical properties. Examples of the fine particles include silica, kaolin, talc, alumina, calcium phosphate, titanium dioxide, calcium carbonate, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and other inorganic particles, crosslinked polymer particles, and calcium oxalate. And organic particles such as In particular, silica particles are preferable from the viewpoint of transparency. The fine particles include a filler. These fine particles may be used alone or in combination of two or more.

  Examples of the base resin constituting the resin layer containing fine particles include polyester resins, polyurethane resins, acrylic resins, mixtures thereof, and copolymers thereof. The workability when continuously producing the protective layer by a roll-to-roll process and the workability when continuously laminating the second laminate 2 to the workpiece 200 are improved. The thickness of the resin layer is preferably 0.01 μm or more from the viewpoint of suppressing the above defects and macro defects such as millimeter scale and centimeter scale. The second stacked body 2 is irradiated with patterned energy rays to improve the resolution when forming the stacked body 201 composed of the patterned nanoparticles 102 / first mask layer 103 / object 200. From the viewpoint, it is more preferably 0.05 μm to 3.0 μm, particularly preferably 0.1 to 2.0 μm, and very preferably 0.1 μm to 1.0 μm.

  There is no restriction | limiting in particular as a method of laminating | stacking a resin layer on one surface of a biaxially-oriented polyester film, For example, coating etc. are mentioned. Examples of the polyester resin constituting the biaxially oriented polyester film include, for example, aromatic linear polyesters and aliphatic dicarboxylics containing aromatic dicarboxylic acids and diols such as polyethylene terephthalate, polyethylene terephthalate, and polyethylene naphthalate. Examples thereof include aliphatic linear polyesters containing acids and diols as constituent components, and polyester resins mainly composed of polyesters such as copolymers thereof. These may be used alone or in combination of two or more. Furthermore, the biaxially oriented polyester film on which the resin layer is laminated may contain fine particles. Examples of these fine particles include the same fine particles as those contained in the resin layer. The content of the fine particles contained in the biaxially oriented polyester film is preferably 0 ppm to 80 ppm, more preferably 0 ppm to 60 ppm, and more preferably 0 ppm to 40 ppm from the viewpoint of maintaining the transparency of the support substrate. It is particularly preferred. The manufacturing method of the said biaxially-oriented polyester film is not specifically limited, For example, the biaxial stretching method etc. can be used. Moreover, after forming a resin layer on one surface of an unstretched film or a uniaxially stretched film, it is good also as a support base material by extending | stretching. The thickness of the biaxially oriented polyester film is preferably 1 μm to 100 μm, and more preferably 1 μm to 50 μm. Examples of these supporting films include A2100-16 and A4100-25 manufactured by Toyobo Co., Ltd. In addition, when using the support base material which laminates | stacks the resin layer containing microparticles | fine-particles on one surface of the said biaxially-oriented polyester film, when a protective layer is formed on the resin layer surface containing microparticles | fine-particles, adhesiveness And from the viewpoint of transfer durability.

  You may use it, arrange | positioning a support base material in the surface on the opposite side to the nanoparticle 102 in the flat protective layer 101 comprised with the material mentioned above. For example, an inorganic supporting group typified by glass or silicon wafer is provided on the surface opposite to the nanoparticle 102 surface of the protective layer 101 made of PDMS or thermoplastic resin (PI, PET, COP, PP, PE, etc.). A material, an elastic support substrate having rubber elasticity, or the like can be disposed. Further, for example, a support base material such as an elastic body having rubber elasticity may be disposed on the surface of the protective layer 101 made of silicon, diamond, nickel, sapphire, quartz, or the like on the side opposite to the surface of the nanoparticles 102. it can. Further, for example, a protective layer 101 made of a photocurable resin or a thermosetting resin is formed on a support base material such as an inorganic material such as glass or silicon wafer, or a support base material of an organic material such as a PET film, a COP film, or a TAC film. Can be formed. Further, for example, a protective layer 101 made of a photo-curing resin or a thermosetting resin is formed on a supporting substrate made of an inorganic material such as glass or silicon wafer, or a supporting substrate made of an organic material such as a PET film, a COP film, or a TAC film. In addition, a supporting substrate such as an elastic body can be further provided on the surface opposite to the supporting substrate.

  As the reel-shaped protective layer 101, a protective layer composed of only a thermoplastic resin without using a supporting substrate, a thermosetting resin, a photocurable resin or a sol-gel material formed on the supporting substrate, etc. Examples thereof include a protective layer 101 made of a cured product.

  Further, in the case where the cover film is not provided and the second laminate 2 is continuously manufactured by the roll-to-roll method, the surface (first surface) opposite to the protective layer 101 of the supporting substrate. Even if the surface roughness Ra of 2a) is large in the range equal to or larger than the surface roughness Ra of the surface (first surface 2a) of the first mask layer 103 described above, when rolling up, the surface roughness Ra By controlling the force, the surface accuracy of the first mask layer 103 can be maintained, and thus there is no particular limitation. However, from the viewpoint of stably manufacturing the second laminated body 2 and suppressing deterioration of the surface accuracy of the first mask layer 103 due to a force that is unexpectedly applied when the second laminated body 2 is conveyed. The surface roughness Ra of the back surface of the substrate 100 is preferably 1000 nm or less, more preferably 500 nm or less, and most preferably 100 nm or less. In particular, from the viewpoint of improving the production rate when the second laminate 2 is produced, it is preferably 60 nm or less, more preferably 45 nm or less, and most preferably 15 nm or less. The surface roughness Ra is the same as the definition of Ra for the first mask layer 103 described above.

In the second laminate 2 according to the present embodiment, a metal layer composed of metal, metal oxide, or metal and metal oxide may be provided on the surface of the protective layer 101 where the nanoparticles 102 are provided. . By providing the metal layer, the mechanical strength of the protective layer 101 is improved, so that damage to the surface of the protective layer 101 can be suppressed. Although the metal which comprises a metal layer is not specifically limited, Chromium, aluminum, tungsten, molybdenum, nickel, gold | metal | money, platinum, silicon, etc. are mentioned. As the metal oxide constituting the metal layer, other oxides of the _{metals, SiO 2, ZnO, Al 2} O 3, ZrO 2, CaO, SnO 2 and the like. Moreover, silicon carbide, diamond-like carbon, etc. can also be used as a material which comprises a metal layer. As diamond-like carbon, diamond-like carbon containing a fluorine element can be used. Furthermore, you may use these mixtures as a material which comprises a metal layer. The metal layer may be a single layer or a multilayer.

  A release layer may be formed on the surface of the protective layer 101 or the surface of the metal layer. By providing the release layer, the transfer accuracy of the nanoparticles 102 and the first mask layer 103 is improved. Further, by providing a release layer on the surface of the metal layer, the adhesion of the release treatment material (release layer) is improved, and the transfer accuracy and transfer durability of the nanoparticles 102 and the first mask layer 103 are improved. To do. The thickness of the release layer is preferably 30 nm or less from the viewpoint of transfer accuracy, and is preferably a monomolecular layer or more. From the viewpoint of releasability, the thickness of the release layer is more preferably 2 nm or more, and more preferably 20 nm or less from the viewpoint of transfer accuracy.

  The material constituting the release layer is not particularly limited as long as it exhibits the effect of reducing the surface free energy. For example, a material containing any of a methyl group, elemental fluorine, and silicone can be selected. The material constituting the release layer preferably has a contact angle with water of 90 ° or more.

  A cover film may be provided on the surface (first surface 2a) side of the first mask layer 103. In this case, the cover film is provided on the surface of the first mask layer 103, or the adhesive layer surface of the cover film having the adhesive layer on the surface is provided on the surface of the first mask layer 103. .

  By providing the cover film, it is possible to easily wind up the second laminated body 2 when it is continuously produced, and to protect the first mask layer 103 of the second laminated body 2. For this reason, the storage stability of the second laminate 2 is improved, and the adhesion of particles to the surface of the first mask layer 103 and the generation of scratches can be suppressed by transportation or the like. Will improve. By providing such a cover film, the function of the first mask layer 103 of the second laminated body 2 manufactured in the first line is preserved, and scratches on the surface of the first mask layer 103 are prevented. Particle adhesion can be suppressed. For this reason, in the 2nd line which is a user's line, by peeling a cover film, the 1st mask layer 103 of the 2nd layered product 2 is controlled with respect to to-be-processed object 200, defects, such as an air void. Can be pasted. As a result, defects such as micrometers and millimeters can be suppressed in the surface of the target object 200, and the first mask layer 103 and the nanoparticles 102 can be transferred and formed on the target object 200 with high accuracy. Even when the cover film is not provided on the first mask layer 103, when the second laminate 2 is rolled up and wound, or when the second laminate 2 is laminated, The first mask layer 103 is protected by the second surface 2b (the surface opposite to the nanoparticles 102 of the protective layer 101 or the surface opposite to the nanoparticles 102 of the supporting substrate) of the laminate 2 of 2 can do.

  The cover film is particularly suitable if the adhesive strength between the cover film and the first mask layer 103 is smaller than the adhesive strength between the first mask layer 103 and the nanoparticles 102 and the adhesive strength between the nanoparticles 102 and the protective layer 101. It is not limited.

  Even when the surface roughness Ra of the cover film is large in the range equal to or higher than the surface roughness Ra of the first mask layer 103 described above, the temperature and pressure when the cover film is bonded, or when the roll is rolled up Since the surface accuracy of the first mask layer 103 can be maintained by controlling the force for tightening, there is no particular limitation. However, from the viewpoint of stably manufacturing the second laminated body 2 and suppressing deterioration of the surface accuracy of the first mask layer 103 due to a force applied unexpectedly when the second laminated body 2 is transported, the cover The surface roughness Ra of the film is preferably 1000 nm or less, more preferably 500 nm or less, and most preferably 100 nm or less. In particular, from the viewpoint of improving the production rate when the second laminate 2 is produced, it is preferably 60 nm or less, more preferably 45 nm or less, and most preferably 15 nm or less. The surface roughness Ra is the same as the definition of Ra for the first mask layer 103 described above.

  Moreover, the cover film may be colored. The storage stability of the second laminate 2 can be improved. In particular, when the second laminate 2 includes a photopolymerizable substance, the photopolymerization application wavelength of the photopolymerizable substance can be suppressed by coloring.

  Further, when the cover film is transparent, it is preferable that the support base material has a transmittance of 50% or less for ultraviolet light (UV) because the storage stability of the second laminate 2 is improved. In particular, from the viewpoint of suppressing photodegradation of the first mask layer 103, the transmittance of ultraviolet light to the cover film is preferably 35% or less, more preferably 15% or less, and 5% or less. Most preferred. In the case of a cover film provided with an ultraviolet light absorbing material or a metal film, the transmittance of ultraviolet light can be made substantially 0%. In this case, the performance preservation | save property of the 2nd laminated body 2 can be improved more.

  On the other hand, when the cover film is colored, storage of the second laminated body 2 is a cover film having a transmittance of 60% or less of light of the photosensitive wavelength (λ) of the components contained in the second laminated body 2. This is preferable because of improved properties. In particular, from the viewpoint of suppressing the photodegradation of the first mask layer 103, the light transmittance of the photosensitive wavelength (λ) to the cover film is preferably 35% or less, and more preferably 15% or less. Most preferably, it is 5% or less. In the case of a cover film provided with a metal film, the light transmittance of the photosensitive wavelength (λ) can be made substantially 0%. In this case, the performance preservation | save property of the 2nd laminated body 2 can be improved more.

As described above, the cover film has an adhesive strength between the cover film and the first mask layer 103 based on an adhesive strength between the first mask layer 103 and the nanoparticles 102 and an adhesive strength between the nanoparticles 102 and the protective layer. If it is small, it will not specifically limit. For example, even when the number of fish eyes contained in the cover film is large (for example, a cover film containing 500 / m ² or more fish eyes having a diameter of 80 μm or more), and bubbles are generated when the cover film is bonded. Since the thickness of the first mask layer 103 is thin in a range satisfying the distance (lor) / pitch (Pav), it is considered that the deterioration of the first mask layer 103 can be suppressed using oxygen inhibition. When the thickness of the first mask layer 103 is thin in a range satisfying the distance (lor) / pitch (Pav), the first mask layer 103 is thicker than the thick first mask layer 103 such as several micrometers to several tens of micrometers. Since the Young's modulus of the layer 103 is large, the influence of the uneven transfer to the first mask layer 103 given by the fish eye of the cover film is small, and therefore the air void derived from the fish eye when bonded to the object 200 It becomes easy to suppress generation | occurrence | production. From the viewpoint of further suppressing air voids when using the second laminated body 2 provided with a cover film and bonding the first mask layer 103 of the second laminated body 2 to the target object 200. The number of fish eyes having a diameter of 80 μm or more contained in the film is preferably 5 / m ² or less. Here, the fish eye refers to a material in which undissolved and deteriorated materials are taken into the film when the material is melted by heat and the film is produced by the kneading, extrusion stretching method or casting method. Moreover, although the magnitude | size of the diameter of a fish eye changes with materials, it is about 10 micrometers-1 mm, and the height from the film surface is about 1 micrometer-50 micrometers. Here, the fish eye size can be measured by, for example, an optical microscope, a contact-type surface roughness meter, or a scanning electron microscope. Note that. The diameter of the fish eye means the maximum diameter.

  Such a cover film can be manufactured, for example, by changing the method for manufacturing the film, such as filtering the raw material resin after heat melting when manufacturing the film. The film thickness of the cover film is preferably 1 μm to 100 μm from the viewpoints of cover film bonding, roll-to-roll web handling, and environmental load reduction, and more preferably 5 μm to 50 μm. Most preferably, it is 15 micrometers-50 micrometers. As commercially available products, PP-type PT manufactured by Shin-Etsu Film Co., Ltd., Torayfan BO-2400, YR12 type manufactured by Toray Industries, Inc., Alfan MA-410, E-200C manufactured by Oji Paper Co., Ltd. Polyethylene terephthalate films such as polypropylene films, PS series such as Teijin's PS-25, and the like are exemplified, but the invention is not limited thereto. Moreover, it can be easily manufactured by sandblasting a commercially available film.

  As the thermoplastic resin constituting the protective layer 101, polypropylene, polyethylene, polyethylene terephthalate, polymethyl petaacrylate, cycloolefin polymer, cycloolefin copolymer, transparent fluororesin, polyethylene, polypropylene, polystyrene, acrylonitrile / styrene-based polymer, Acrylonitrile / butadiene / styrene polymer, polyvinyl chloride, polyvinylidene chloride, poly (meth) acrylate, polyarylate, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyimide, polyacetal, polycarbonate, polyphenylene ether, polyether ether ketone, polysulfone , Polyethersulfone, polyphenylene sulfide, polyvinylidene fluoride, tetrafluoro Ethylene / perfluoro (alkyl vinyl ether) copolymer, tetrafluoroethylene / ethylene copolymer, vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / propylene copolymer, polyfluoro (Meth) acrylate polymer, fluorine-containing polymer having a fluorine-containing aliphatic ring structure in the main chain, polyvinyl fluoride, polytetrafluoroethylene, polychlorotrifluoroethylene, chlorotrifluoroethylene / ethylene copolymer, Examples include chlorotrifluoroethylene / hydrocarbon alkenyl ether copolymers, tetrafluoroethylene / hexafluoropropylene copolymers, vinylidene fluoride / hexafluoropropylene copolymers, and the like.

  Examples of the thermosetting resin constituting the protective layer 101 include polyimide, epoxy resin, and urethane resin.

  In the case where the protective layer 101 is made of a resin, if the adhesion between the nanoparticles 102 and the first mask layer 103 decreases due to the combination of the above-described resin, metal layer, or release layer, the protective layer 101 There are no particular restrictions on the material that constitutes. In particular, the protective layer 101 is preferably composed of a resin made of polydimethylsiloxane (PDMS) typified by silicone or a fluorine-containing resin from the viewpoint of transfer accuracy. However, when a release layer is provided on the protective layer 101, the material of the protective layer 101 is not particularly limited. On the other hand, when a release layer is not provided on the protective layer 101, it is preferably composed of a fluorine-containing resin, a polydimethylsiloxane resin represented by silicone, COP, polyimide, or the like, and in particular, a polydimethylsiloxane resin. Or a fluorine-containing resin. The fluorine-containing resin is not particularly limited as long as it contains elemental fluorine and has a contact angle with water larger than 90 degrees. From the viewpoint of transfer accuracy when the nanoparticles 102 are transferred to the object 200, the contact angle with water is more preferably 95 degrees or more, and still more preferably 100 degrees or more.

  In particular, the protective layer 101 is preferably composed of a cured product of a photocurable resin. It is preferable to select a photocurable resin as a material for forming the protective layer 101 because throughput and transfer accuracy when the protective layer 101 is manufactured are improved.

  Further, the fluorine concentration (Es) of the resin surface layer (near the interface between the nanoparticles 102 and the protective layer 101) in the protective layer 101 is made larger than the average fluorine concentration (Eb) in the resin layer constituting the protective layer 101. Thus, since the surface of the protective layer 101 has low free energy, the protective layer 101 having excellent releasability from the nanoparticles 102 and the first mask layer 103 can be obtained, and the free energy is kept high in the vicinity of the supporting substrate. As a result, the adhesiveness can be improved and the transferability can be repeated.

  Furthermore, the ratio of the average fluorine element concentration (Eb) in the resin layer constituting the protective layer 101 to the fluorine element concentration (Es) in the surface layer portion of the resin layer constituting the protective layer 101 is 1 <Es / Eb ≦ 30000. It is more preferable to satisfy the above condition because the above effect is more exhibited. In particular, it is preferable because the releasability is further improved as the range becomes 3 ≦ Es / Eb ≦ 1500 and 10 ≦ Es / Eb ≦ 100.

  In the widest range described above (1 <Es / Eb ≦ 30000) and in the range of 20 ≦ Es / Eb ≦ 200, the fluorine element concentration in the surface layer portion of the resin layer constituting the protective layer 101 ( Es) is sufficiently higher than the average fluorine concentration (Eb) in the resin layer, and the free energy on the surface of the protective layer 101 is effectively reduced, so that the releasability between the nanoparticles 102 and the first mask layer 103 is improved. improves. Further, the resin can be obtained by lowering the average fluorine element concentration (Eb) in the resin layer constituting the protective layer 101 relative to the fluorine element concentration (Es) of the resin layer surface portion constituting the protective layer 101. While the strength of itself is improved, the free energy can be kept high in the vicinity of the supporting base material in the protective layer 101, so that the adhesion with the supporting base material is improved. Thereby, it is particularly preferable since it is possible to obtain the protective layer 101 that has excellent adhesion to the support substrate, excellent releasability from the nanoparticles 102, and that can be repeatedly transferred. Further, the range of 26 ≦ Es / Eb ≦ 189 is preferable because the free energy on the surface of the resin layer constituting the protective layer 101 can be further reduced, and the repetitive transferability is improved. Furthermore, if it is in the range of 30 ≦ Es / Eb ≦ 160, the free energy on the surface of the resin layer constituting the protective layer 101 can be reduced, the strength of the resin can be maintained, and repeated transferability is further improved. Preferably, 31 ≦ Es / Eb ≦ 155 is more preferable. It is preferable that 46 ≦ Es / Eb ≦ 155 because the above effect can be further exhibited.

  The repetitive transfer property means that (1) another protective layer 101 can be easily copied from the protective layer 101, and (2) the once used protective layer 101 can be used again as the second laminate 2. To do. (1) The protective layer G1 having a surface state of “+” can be used as a template to transfer the protective layer G2 having a surface state of “−”, and the protective layer having a surface state of “+” can be formed using the protective layer G2 as a template. G3 can be transferred and formed. Similarly, the protective layer GN + 1 whose surface state is “−” can be transferred and formed using the protective layer GN whose surface state is “+” as a template. Further, it is possible to obtain a plurality of protective layers G2 using one protective layer G1 as a template, or to obtain a plurality of protective layers G3 using one protective layer G2 as a template. Similarly, a plurality of protective layers GM + 1 can be obtained using one protective layer GM as a template. Thus, environmental compatibility improves by using the protective layer 101 which satisfy | fills said Es / Eb.

  Here, the surface layer (nanoparticle 102 surface side region) of the resin layer constituting the protective layer 101 is, for example, from the nanoparticle 102 surface side of the resin layer constituting the protective layer 101 to the second surface 2b side. In other words, it means a portion that has penetrated approximately 1 to 10% in the thickness direction, or a portion that has penetrated 2 nm to 20 nm in the thickness direction. The fluorine element concentration (Es) in the region on the nanoparticle 102 surface side of the resin layer constituting the protective layer 101 can be quantified by X-ray photoelectron spectroscopy (XPS method). Since the penetration length of X-rays in the XPS method is as shallow as several nm, it is suitable for quantifying the Es value. As another analysis method, Es / Eb can be calculated using energy dispersive X-ray spectroscopy (TEM-EDX) using a transmission electron microscope. Further, the average fluorine concentration (Eb) in the resin constituting the resin layer constituting the protective layer 101 can be calculated from the charged amount. Alternatively, the average fluorine element concentration (Eb) in the resin can be identified by disassembling the section from which the resin layer constituting the protective layer 101 is physically peeled and then subjecting it to an ion chromatography analysis. can do

  Of the resins constituting the resin layer constituting the protective layer 101, the photopolymerizable radical polymerization resin is a mixture of non-fluorine-containing (meth) acrylate, fluorine-containing (meth) acrylate and photopolymerization initiator. A curable resin composition (1), a curable resin composition (2) that is a mixture of a non-fluorine-containing (meth) acrylate and a photopolymerization initiator, a non-fluorine-containing (meth) acrylate, silicone, and light It is preferable to use a curable resin composition (3) or the like that is a mixture of polymerization initiators. Moreover, the curable resin composition (4) containing the sol-gel material represented by the metal alkoxide can also be used. In particular, by using the curable resin composition (1), when the composition (1) is cured while the composition (1) is in contact with a hydrophobic interface having a low surface free energy, the protective layer The fluorine element concentration (Es) in the surface layer portion of the resin layer constituting 101 can be made larger than the average fluorine element concentration (Eb) in the resin constituting the resin layer constituting the protective layer 101, and further the average fluorine element in the resin The density (Eb) can be adjusted to be smaller.

(A) (Meth) acrylate The (meth) acrylate constituting the curable resin composition (1) is not limited as long as it is a polymerizable monomer other than (B) fluorine-containing (meth) acrylate described later, but acryloyl. A monomer having a group or a methacryloyl group, a monomer having a vinyl group, or a monomer having an allyl group is preferable, and a monomer having an acryloyl group or a methacryloyl group is more preferable. And it is preferable that they are non-fluorine containing monomers. In addition, (meth) acrylate means an acrylate or a methacrylate.

  The polymerizable monomer is preferably a polyfunctional monomer having a plurality of polymerizable groups, and the number of polymerizable groups is preferably an integer of 1 to 6 because of excellent polymerizability. Moreover, when mixing and using 2 or more types of polymeric monomers, 1.5-4 are preferable for the average number of polymeric groups. When using a single monomer, the number of polymerizable groups may be 3 or more in order to increase the crosslinking point after the polymerization reaction and to obtain physical stability (strength, heat resistance, etc.) of the cured product. preferable. In the case of a monomer having 1 or 2 polymerizable groups, it is preferably used in combination with monomers having different polymerizable numbers.

(B) Fluorine-containing (meth) acrylate As the fluorine-containing (meth) acrylate constituting the curable resin composition (1), a polyfluoroalkylene chain and / or a perfluoro (polyoxyalkylene) chain and a polymerizable group are used. It is preferable to have a linear perfluoroalkylene group, or a perfluorooxyalkylene group having an etheric oxygen atom inserted between carbon atoms and carbon atoms and having a trifluoromethyl group in the side chain. Further, a linear polyfluoroalkylene chain having a trifluoromethyl group at the molecular side chain or molecular structure terminal and / or a linear perfluoro (polyoxyalkylene) chain is particularly preferred.

  The polyfluoroalkylene chain is preferably a polyfluoroalkylene group having 2 to 24 carbon atoms. Moreover, the polyfluoroalkylene group may have a functional group.

The perfluoro (polyoxyalkylene) chain is a group consisting of (CF ₂ CF ₂ O) units, (CF ₂ CF (CF ₃ ) O) units, (CF ₂ CF ₂ CF ₂ O) units and (CF ₂ O) units. It is preferably composed of one or more perfluoro (oxyalkylene) units selected from: (CF ₂ CF ₂ O) units, (CF ₂ CF (CF ₃ ) O) units, or (CF ₂ CF ₂ CF ₂ O). ) Units. The perfluoro (polyoxyalkylene) chain is particularly preferably composed of (CF ₂ CF ₂ O) units because the physical properties (heat resistance, acid resistance, etc.) of the fluoropolymer are excellent. The number of perfluoro (oxyalkylene) units is preferably an integer of 2 to 200, more preferably an integer of 2 to 50, because the release property and hardness of the fluoropolymer are high.

The polymerizable group is represented by a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, an epoxy group, a diquitacene group, a cyano group, an isocyanate group, or a formula — (CH ₂ ) aSi (M1) _3-b (M2) _b. A hydrolyzable silyl group is preferable, and an acryloyl group or a methacryloyl group is more preferable. Here, M1 is a substituent which is converted into a hydroxyl group by a hydrolysis reaction. Examples of such a substituent include a halogen atom, an alkoxy group, and an acyloxy group. As the halogen atom, a chlorine atom is preferable. As an alkoxy group, a methoxy group or an ethoxy group is preferable, and a methoxy group is more preferable. As M1, an alkoxy group is preferable, and a methoxy group is more preferable. M2 is a monovalent hydrocarbon group. Examples of M2 include an alkyl group, an alkyl group substituted with one or more aryl groups, an alkenyl group, an alkynyl group, a cycloalkyl group, and an aryl group, and an alkyl group or an alkenyl group is preferable. When M2 is an alkyl group, an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable. When M2 is an alkenyl group, an alkenyl group having 2 to 4 carbon atoms is preferable, and a vinyl group or an allyl group is more preferable. a is an integer of 1 to 3, and 3 is preferable. b is 0 or an integer of 1 to 3, and 0 is preferable. Examples of the hydrolyzable silyl group include (CH ₃ O) ₃ SiCH ₂ —, (CH ₃ CH ₂ O) ₃ SiCH ₂ —, (CH ₃ O) ₃ Si (CH ₂ ) ₃ — or (CH ₃ CH ₂ O ) ₃ Si (CH ₂ ) ₃ — is preferred.

  The number of polymerizable groups is preferably an integer of 1 to 4 and more preferably an integer of 1 to 3 because of excellent polymerizability. When using 2 or more types of compounds, the average number of polymerizable groups is preferably 1 to 3.

  If the fluorine-containing (meth) acrylate has a functional group, the adhesiveness to the support substrate 100 is excellent. Examples of the functional group include a carboxyl group, a sulfonic acid group, a functional group having an ester bond, a functional group having an amide bond, a hydroxyl group, an amino group, a cyano group, a urethane group, an isocyanate group, and a functional group having an isocyanuric acid derivative. It is done. In particular, it preferably contains at least one functional group of a functional group having a carboxyl group, a urethane group, or an isocyanuric acid derivative. The isocyanuric acid derivatives include those having an isocyanuric acid skeleton and a structure in which at least one hydrogen atom bonded to the nitrogen atom is substituted with another group. As the fluorine-containing (meth) acrylate, fluoro (meth) acrylate, fluorodiene, or the like can be used. Specific examples of the fluorine-containing (meth) acrylate include the following compounds.

  From the viewpoint of adjusting the ratio (Es / Eb) between the fluorine element concentration (Es) and the average fluorine element concentration (Eb) of the surface layer, the fluorine-containing (meth) acrylate is represented by the following chemical formula (1). It is preferable to employ a fluorine-containing urethane (meth) acrylate. As such urethane (meth) acrylate, for example, “OPTOOL DAC” manufactured by Daikin Industries, Ltd. can be used.

(In the chemical formula (1), R1 represents the following chemical formula (2), and R2 represents the following chemical formula (3).)

(In chemical formula (2), n is an integer of 1 or more and 6 or less.)

(In the chemical formula (3), R is H or CH _3. )

  A fluorine-containing (meth) acrylate may be used individually by 1 type, and may use 2 or more types together. Further, it can be used in combination with surface modifiers such as abrasion resistance, scratch resistance, fingerprint adhesion prevention, antifouling property, leveling property and water / oil repellency.

  The fluorine-containing (meth) acrylate preferably has a molecular weight Mw of 50 to 50,000. From the viewpoint of compatibility, the molecular weight Mw is preferably 50 to 5,000, and the molecular weight Mw is more preferably 100 to 5,000. When using a high molecular weight material having low compatibility, a diluting solvent may be used. As a dilution solvent, the solvent whose boiling point of a single solvent is 40 to 180 degreeC is preferable, 60 to 180 degreeC is more preferable, and 60 to 140 degreeC is further more preferable. Two or more kinds of diluents may be used.

  The solvent content may be at least an amount capable of being dispersed in the curable resin composition (1), and is preferably more than 0 to 50 parts by weight with respect to 100 parts by weight of the curable resin composition (1). Considering removing the amount of residual solvent after drying as much as possible, more than 0 parts by weight to 10 parts by weight is more preferable.

  In particular, when a solvent is contained in order to improve leveling properties, the solvent content is preferably 0.1 parts by weight or more and 40 parts by weight or less with respect to 100 parts by weight of (meth) acrylate. If the solvent content is 0.5 part by weight or more and 20 parts by weight or less, the curability of the curable resin composition (1) can be maintained, more preferably 1 part by weight or more and 15 parts by weight or less. When the solvent is contained in order to reduce the film thickness of the curable resin composition (1), if the solvent content is 300 parts by weight or more and 10,000 parts by weight or less with respect to 100 parts by weight of (meth) acrylate, Since the solution stability in the drying process after a process can be maintained, it is preferable and it is more preferable if it is 300 to 1000 weight part.

(C) Photopolymerization initiator The photopolymerization initiator constituting the curable resin composition (1) causes a radical reaction or an ionic reaction by light, and a photopolymerization initiator that causes a radical reaction is preferable.

  The curable resin composition (1) may contain a photosensitizer.

  A photoinitiator may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types together, it is good to select from the viewpoint of the dispersibility of fluorine-containing (meth) acrylate, the surface layer on the nanoparticle surface side of the curable resin composition (1), and the internal curability. For example, the combined use of an α-hydroxyketone photopolymerization initiator and an α-aminoketone photopolymerization initiator can be mentioned.

  As the curable resin composition (2), one obtained by removing (B) fluorine-containing (meth) acrylate from the curable resin composition (1) described above can be used. In the case where the resin constituting the protective layer 101 is a cured product of the curable resin composition (2), it is possible to provide both or one of the metal layer and the release layer from the viewpoint of the transfer accuracy of the nanoparticles 102. preferable.

  As the curable resin composition (3), one obtained by adding silicone to the curable resin composition (1) described above or by adding silicone to the curable resin composition (2) can be used.

  By including silicone, the transfer accuracy of the nanoparticles 102 and the first mask layer 103 is improved by the release property and slipperiness unique to silicone. As the silicone used in the curable resin composition (3), for example, a linear low-polymerization silicone oil exhibiting fluidity at room temperature, typified by polydimethylsiloxane (PDMS) which is a polymer of dimethylchlorosilane. And their modified silicone oils, linear PDMS with a high degree of polymerization, or silicone rubbers that are moderately crosslinked to exhibit rubbery elasticity, their modified silicone rubbers, resinous silicones, and PDMS Examples thereof include a silicone resin (or DQ resin) which is a resin having a three-dimensional network structure composed of tetrafunctional siloxane. In some cases, an organic molecule is used as the cross-linking agent, or tetrafunctional siloxane (Q unit) is used.

  Modified silicone oils and modified silicone resins are those in which the side chain and / or terminal of polysiloxane is modified, and are classified into reactive silicones and non-reactive silicones. As the reactive silicone, a silicone containing an —OH group (hydroxyl group), a silicone containing an alkoxy group, a silicone containing a trialkoxy group, and a silicone containing an epoxy group are preferable. As the non-reactive silicone, a silicone containing a phenyl group, a silicone containing both a methyl group and a phenyl group, and the like are preferable. A single polysiloxane molecule having two or more modifications as described above may be used.

  Examples of the reactive silicone include amino modification, epoxy modification, carboxyl modification, carbinol modification, methacryl modification, vinyl modification, mercapto modification, phenol modification, one-terminal reactivity, and heterofunctional modification.

  In addition, since a silicone compound containing any one of a vinyl group, a methacryl group, an amino group, an epoxy group, or an alicyclic epoxy group can be contained, silicone can be incorporated into the protective layer 101 through a chemical bond. In addition, the transfer accuracy of the nanoparticles 102 and the first mask layer 103 is improved. In particular, the inclusion of a silicone compound containing any one of a vinyl group, a methacryl group, an epoxy group, and an alicyclic epoxy group is preferable because the above effects can be further exhibited. From the viewpoint of curability of the resin layer of the protective layer 101, it is preferable to contain a silicone compound containing either a vinyl group or a methacryl group. Moreover, it is preferable to contain the silicone compound containing either an epoxy group or an alicyclic epoxy group from a viewpoint of the adhesiveness to a support base material. As for the silicone compound containing any one of vinyl group, methacryl group, amino group, epoxy group and alicyclic epoxy group, only one kind may be used or a plurality may be used in combination. The silicone having a photopolymerizable group and the silicone having no photopolymerizable group may be used in combination or singly.

  The curable resin composition (4) is composed of the curable resin composition (1) to the curable resin composition (3) to which a sol-gel material described below is added or only a sol-gel material. Composition can be employed. By adding a sol-gel material to the curable resin composition (1) to the curable resin composition (3), the effect of improving the replication efficiency of the protective layer due to the shrinkage action specific to the sol-gel material, Since it becomes possible to exhibit properties as inorganic, the permeation suppression effect of the nanoparticles 102 and the first mask layer 103 to the protective layer 101 is improved, and the transfer accuracy of the nanoparticles 102 and the first mask layer 103 is improved. Do

  As the sol-gel material constituting the protective layer 101, metal alkoxide, metal alcoholate, metal chelate compound, halogenated silane, liquid glass, which is a group of compounds that are cured by hydrolysis and polycondensation by the action of heat and catalyst. , Spin-on-glass or any of these reactants is not particularly limited. These are collectively called metal alkoxides.

  A metal alkoxide is a combination of a metal species represented by Si, Ti, Zr, Zn, Sn, B, In, Al and a functional group such as a hydroxy group, a methoxy group, an ethoxy group, a propyl group, or an isopropyl group. It is a compound group. These functional groups cause hydrolysis and polycondensation reaction to proceed with water, an organic solvent, a hydrolysis catalyst, or the like, and a metalloxane bond (-Me1-O-Me2-bond. However, Me1 and Me2 are metal species, Which may be the same or different). For example, if the metal species is Si, a metalloxane bond (siloxane bond) such as -Si-O-Si- is generated. When the metal species (M1) and the metal alkoxide of the metal species (Si) are used, for example, a bond such as -M1-O-Si- can be generated.

  For example, as the metal alkoxide of the metal species (Si), dimethyldiethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, p-styryltriethoxysilane, methylphenyldiethoxysilane , Tetraethoxysilane, p-styryltriethoxysilane, and the like, and compounds in which the ethoxy group of these compound groups is replaced with a methoxy group, a propyl group, or an isopropyl group. In addition, a compound having a hydroxy group such as diphenylsilanediol and dimethylsilanediol can be selected.

  Further, one or more of the functional groups may be directly substituted with a phenyl group or the like from a metal species without an oxygen atom. For example, diphenylsilanediol, dimethylsilanediol, etc. are mentioned. By using these compound groups, the density after condensation is improved, the effect of suppressing the penetration of the nanoparticles 102 and the first mask layer 103 into the protective layer 101 is improved, and the nanoparticles 102 and the first mask layer 103 are improved. The transfer accuracy is improved.

  Halogenated silane is a group of compounds in which the metal species of the metal alkoxide is silicon and the functional group that undergoes hydrolytic polycondensation is replaced with a halogen atom.

  Examples of the liquid glass include TGA series manufactured by Apollo Ring. Other sol-gel compounds can be added in accordance with the desired physical properties.

A silsesquioxane compound can also be used as the metal alkoxide. Silsesquioxane is a compound in which one organic group and three oxygen atoms are bonded to one silicon atom. The silsesquioxane is not particularly limited as long as it is a polysiloxane represented by the composition formula (RSiO _3/2 ) _n. However, the polysiloxane having any structure such as a cage type, a ladder type, or a random structure. It may be. In the composition formula (RSiO _3/2 ) _n , R may be a substituted or unsubstituted siloxy group or any other substituent. n is preferably 8 to 12, more preferably 8 to 10 and further preferably n is 8 because the curability of the curable resin composition (4) is improved. The n Rs may be the same or different.

  Examples of the silsesquioxane compound include polyhydrogen silsesquioxane, polymethyl silsesquioxane, polyethyl silsesquioxane, polypropyl silsesquioxane, polyisopropyl silsesquioxane, polybutyl silsesquioxane, and polybutyl silsesquioxane. , Poly-sec-butylsilsesquioxane, poly-tert-butylsilsesquioxane, polyphenylsilsesquioxane, and the like. Moreover, you may substitute at least 1 among n R with respect to these silsesquioxane with the substituent illustrated next. Examples of the substituent include trifluoromethyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3 -Pentafluoropropyl, 2,2,2-trifluoro-1-trifluoromethylethyl, 2,2,3,4,4,4-hexafluorobutyl, 2,2,3,3,4,4,5 , 5-octafluoropentyl, 2,2,2-trifluoroethyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2,3,3 , 4,4,5,5-octafluoropentyl, 3,3,3-trifluoropropyl, nonafluoro-1,1,2,2-tetrahydrohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl , Heptade Fluoro-1,1,2,2-tetrahydrodecyl, perfluoro-1H, 1H, 2H, 2H-dodecyl, perfluoro-1H, 1H, 2H, 2H-tetradecyl, 3,3,4,4,5,5 , 6,6,6-nonafluorohexyl, alkoxysilyl groups and the like. Commercially available silsesquioxane can also be used. For example, various cage-type silsesquioxane derivatives manufactured by Hybrid Plastics, silsesquioxane derivatives manufactured by Aldrich, and the like can be mentioned.

  The metal alkoxide may be in a prepolymer state in which the polymerization reaction partially reacts and an unreacted functional group remains. When the metal alkoxide is partially condensed, a prepolymer in which metal species are connected via an oxygen element can be obtained. That is, a prepolymer having a large molecular weight can be produced by partial condensation. By partially condensing the metal alkoxide, flexibility is imparted to the protective layer 101. As a result, breakage of fine patterns and cracks when the protective layer 101 is produced by transfer using the metal alkoxide can be suppressed.

  The degree of partial condensation can be controlled by the reaction atmosphere, the combination of metal alkoxides, and the like, and the degree of partial condensation used in the prepolymer state can be appropriately selected depending on the application and method of use, and is not particularly limited. For example, when the viscosity of the partial condensate is 50 cP or more, transfer accuracy and stability to water vapor are further improved, and when the viscosity is 100 cP or more, these effects can be more exhibited, and still more preferable.

  Moreover, the prepolymer which promoted partial condensation can be obtained by polycondensation based on a dehydration reaction and / or polycondensation based on a dealcoholization reaction. For example, a prepolymer can be obtained by heating a solution composed of a metal alkoxide, water, and a solvent (alcohol, ketone, ether, etc.) in a range of 20 ° C. to 150 ° C., followed by hydrolysis and polycondensation. The degree of polycondensation can be controlled by temperature, reaction time, and pressure (decompression force), and can be selected as appropriate. Moreover, it is also possible to reduce the molecular weight distribution of the prepolymer by gradually performing hydrolysis and polycondensation using water (water vapor based on humidity) in the environmental atmosphere without adding water. Furthermore, in order to promote polycondensation, the method of irradiating energy rays is also mentioned. Here, the light source of the energy beam can be appropriately selected depending on the type of metal alkoxide, and is not particularly limited, but a UV-LED light source, a metal halide light source, a high-pressure mercury lamp light source, or the like can be employed. In particular, by adding a photoacid generator to the metal alkoxide and irradiating the composition with energy rays, photoacid is generated from the photoacid generator, and polycondensation of the metal alkoxide using the photoacid as a catalyst. And a prepolymer can be obtained. In addition, for the purpose of controlling the condensation degree and configuration of the prepolymer, the prepolymer can be obtained by performing the above-described operation in the state of chelating the metal alkoxide.

  The prepolymer is defined as a state in which at least four or more metal elements are connected via oxygen atoms. That is, a state in which a metal element is condensed to -O-M1-O-M2-O-M3-O-M4-O- or more is defined as a prepolymer. Here, M1, M2, M3, and M4 are metal elements, and may be the same metal element or different. For example, when a metal alkoxide having Ti as a metal species is pre-condensed to produce a metalloxane bond composed of —O—Ti—O—, a range of n ≧ 4 in the general formula [—O—Ti—] n And prepolymer. Similarly, for example, when a metal alkoxide having Ti as a metal species and a metal alkoxide having Si as a metal species are pre-condensed to form a metalloxane bond composed of —O—Ti—O—Si—O—, [ In the general formula of —O—Ti—O—Si—] n, a prepolymer is used in the range of n ≧ 2. However, in the case where a dissimilar metal element is included, the elements are not necessarily alternately arranged like -O-Ti-O-Si-. Therefore, in the general formula [-OM-] n (where M = Ti or Si), a prepolymer is used in the range of n ≧ 4.

  The metal alkoxide can include a fluorine-containing silane coupling agent. By including the fluorine-containing silane coupling agent, it is possible to reduce the energy of the fine pattern surface of the protective layer 101 made of the cured metal alkoxide, and the nano particles 102 can be formed without forming a release layer or the like. In addition, the transfer accuracy of the first mask layer 103 is improved. This means that the release layer is previously incorporated in the protective layer.

Examples of the fluorine-containing silane coupling agent include a general formula F ₃ C— (CF ₂ ) _n — (CH ₂ ) _m —Si (O—R) ₃ (where n is an integer of 1 to 11, m Is an integer of 1 to 4 and R is an alkyl group having 1 to 3 carbon atoms.), A polyfluoroalkylene chain and / or a perfluoro (polyoxyalkylene) chain. May be included. A linear perfluoroalkylene group, or a perfluorooxyalkylene group having an etheric oxygen atom inserted between carbon atoms and a carbon atom and having a trifluoromethyl group in the side chain is more preferred. Further, a linear polyfluoroalkylene chain having a trifluoromethyl group at the molecular side chain or molecular structure terminal and / or a linear perfluoro (polyoxyalkylene) chain is particularly preferred. The polyfluoroalkylene chain is preferably a polyfluoroalkylene group having 2 to 24 carbon atoms. The perfluoro (polyoxyalkylene) chain is composed of (CF ₂ CF ₂ O) units, (CF ₂ CF (CF ₃ ) O) units, (CF ₂ CF ₂ CF ₂ O) units, and (CF ₂ O) units. It is preferably composed of at least one perfluoro (oxyalkylene) unit selected from the group, and is a (CF ₂ CF ₂ O) unit, (CF ₂ CF (CF ₃ ) O) unit, or (CF ₂ CF ₂ More preferably, it is composed of (CF ₂ O) units. The perfluoro (polyoxyalkylene) chain is particularly preferably composed of (CF ₂ CF ₂ O) units from the viewpoint of excellent segregation on the surface.

  In the present invention, the metal alkoxide can contain polysilane. Polysilane is a compound in which a silicon element constitutes a main chain, and the main chain is composed of repeating -Si-Si-. By irradiating polysilane with energy rays (for example, UV), a —Si—Si— bond is cut and a siloxane bond is generated. For this reason, by containing polysilane, a siloxane bond can be effectively generated by UV irradiation, and the transfer accuracy when the protective layer is transferred and formed using metal alkoxide as a raw material is improved.

  Further, the protective layer 101 may be a hybrid including an inorganic segment and an organic segment. By being a hybrid, cracks and scratches on the protective layer when the second laminate 2 is continuously produced can be suppressed. Furthermore, although depending on the composition of the nanoparticles 102 and the first mask layer 103, the effect of suppressing the penetration of the nanoparticles 102 and the first mask layer 103 into the protective layer 101 is increased, and as a result, the transfer accuracy is improved. It becomes possible to improve. Examples of the hybrid include a resin that can be photopolymerized (or thermally polymerized) with an inorganic precursor, a molecule in which an organic polymer and an inorganic segment are bonded by a covalent bond, and the like. When the sol-gel material is used as the inorganic precursor, it means that a photopolymerizable resin is included in addition to the sol-gel material containing the silane coupling agent. In the case of a hybrid, for example, a metal alkoxide, a silane coupling material having a photopolymerizable group, a metal alkoxide, a silane coupling material having a photopolymerizable group, a radical polymerization resin, or the like can be mixed. . In order to further improve the transfer accuracy, silicone may be added thereto. The mixing ratio between the metal alkoxide containing the silane coupling agent and the photopolymerizable resin is preferably in the range of 3: 7 to 7: 3 by weight from the viewpoint of transfer accuracy.

[Nanoparticles]
The material of the nanoparticles 102 is not particularly limited as long as the selection ratio described later is satisfied, and an organic substance, an inorganic substance, or an organic-inorganic composite can be used. For example, various known resins (organic substances) that can be diluted in a solvent, inorganic precursors, inorganic condensates, plating solutions (such as chromium plating solutions), metal oxide fillers, metal oxide fine particles, metal fine particles, and HSQ are representative. Silsesquioxane, spin-on-glass, etc. can be used. From the viewpoint of transfer accuracy when the nanoparticle 102 uses the second laminate 2 to transfer and form the laminate 201, the nanoparticle 102 and the first mask layer 103 described later are chemically bonded. Or forming a hydrogen bond. In order to improve the transfer speed and accuracy, photopolymerization or thermal polymerization, and complex polymerization thereof are useful. Therefore, the nanoparticles can be used without containing a polymerizable functional group, but it is particularly preferable that the nanoparticles contain a photopolymerizable group capable of photopolymerization and / or a polymerizable group capable of thermal polymerization. The nanoparticles 102 preferably contain a metal element from the viewpoint of dry etching resistance. Furthermore, the nanoparticle 102 is preferable because it includes metal oxide fine particles, so that processing when the object to be processed 200 is dry-etched becomes easier.

  Examples of the metal elements contained in the nanoparticles 102 include titanium (Ti), zirconium (Zr), chromium (Cr), zinc (Zn), tin (Sn), boron (B), indium (In), and aluminum (Al). And at least one selected from the group consisting of silicon (Si), gold (Au), silver (Ag), molybdenum (Mo), tungsten (W), germanium (Ge), and hafnium (Hf). . In particular, titanium (Ti), zirconium (Zr), chromium (Cr), silicon (Si), or gold (Au) is preferable. In addition, the metal element contained in the nanoparticle 102 stably exists, satisfies the dry etching resistance described later, and the stacked body 201 composed of the nanoparticle 102 / the first mask layer 103 / the object to be processed 200, From the viewpoint of improving the processing accuracy when the first mask layer 103 is etched using the nanoparticles 102 as a mask, the nanoparticles 102 preferably contain a metalloxane bond (—O—Me 1 —O—Me 2 —O—). . Here, Me1 and Me2 are both metal elements and may be the same metal element or different. As Me1 or Me2, the above-described metal element can be employed. For example, in the case of a single metal element, —O—Ti—O—Ti—O—, —O—Zr—O—Zr—O—, —O—Si—O—Si—O—, and the like can be given. . In the case of a dissimilar metal element, —O—Ti—O—Si—O—, —O—Zr—O—Si—O—, —O—Zn—O—Si—O—, and the like can be given. In addition, three or more types of metal element species in the metalloxane bond may be included. In particular, when two or more types are included, it is preferable to include at least Si from the viewpoint of transfer accuracy of the mask layer.

If nanoparticles 102 includes a metalloxane bond, a Si element concentration _{(C pSi)} across nanoparticles 102, the total concentration of the metal elements other than Si _{(C pM1),} the ratio of _(C pM1 _/ C _pSi) is 0 0.02 or more and less than 24 is preferable because the processing accuracy is improved when the first mask layer 103 is etched using the nanoparticles 102 as a mask. In particular, it is more preferably 0.05 or more and 20 or less, and most preferably 0.1 or more and 15 or less.

  In addition, when metal nanoparticles or metal oxide nanoparticles are selected as the material of the nanoparticles 102, the primary mask diameter 103 is improved when the primary particle diameter is 500 nm or less because the array controllability of the nanoparticles 102 is improved. Machining accuracy is improved. From the same effect, the primary particle size is preferably 250 nm or less, more preferably 100 nm or less, and most preferably 50 nm or less. Furthermore, it is preferable that it is 30 nm or less because the controllability of the secondary particle diameter is improved.

  On the other hand, when the nanoparticle 102 does not include nanoparticles, the film formed on the protective layer 101 has an inertial radius of 5 nm or less when the nanoparticle material is dissolved in a solvent at a concentration of 3% by weight. This is preferable because the arrangement accuracy of the formed nanoparticles 102 is improved and the processing accuracy when the first mask layer 103 is etched using the nanoparticles 102 as a mask is also improved. The inertia radius is preferably 3 nm or less, more preferably 1.5 nm or less, and most preferably 1 nm or less. Here, the inertia radius is a radius calculated by applying a Gunier plot to a measurement result obtained by measurement by small-angle X-ray scattering using X-rays having a wavelength of 0.154 nm.

  Examples of a method for including such a metalloxane bond in the nanoparticles include a method of using metal oxide fine particles or a method of condensing an inorganic precursor. As a method for condensing the inorganic precursor, for example, the reaction by hydrolysis and polycondensation of the metal alkoxide described above can be used.

  The viscosity of the material of the nanoparticles 102 is preferably 10 cP or more at 25 ° C., because the processing accuracy when the first mask layer 103 is etched using the nanoparticles 102 as a mask is also improved. From the same effect, it is more preferably 50 cP or more, and most preferably 100 cP or more. From the viewpoint of suppressing overlapping of the nanoparticles 102 formed on the protective layer 101 in the film thickness direction of the second laminate 2, it is preferably 10000 cP or less, more preferably 8000 cP or less, and 5000 cP or less. Is most preferable. As will be described later, the nanoparticle raw material is diluted with a solvent and used.

  Examples of a method of including a metal element in the nanoparticle 102 include a method of including a metal oxide fine particle (filler), a sol-gel material typified by a metal fine particle or a metal alkoxide in the material of the nanoparticle 102. As the sol-gel material used for the nanoparticles 102, for example, a metal alkoxide constituting the protective layer 101 described above can be used.

Further, from the viewpoint of dry etching resistance as the nanoparticle 102, it is preferable to include a metal alkoxide having a metal element selected from the group consisting of Ti, Ta, Zr, Zn, and Si as a metal species. In particular, from the viewpoint of improving transfer accuracy and transfer speed, the sol-gel material preferably contains at least two types of metal alkoxides having different metal types. Examples of combinations of metal species of two types of metal alkoxides having different metal species include Si and Ti, Si and Zr, Si and Ta, and Si and Zn. From the viewpoint of dry etching resistance, the ratio C _M1 / C _Si of the molar concentration (C _Si ) of the metal alkoxide having Si as a metal species and the metal alkoxide (C _M1 ) having a metal species M1 other than _Si is 0. 2 to 15 is preferable. From the viewpoint of stability at the time of coating and drying when the nanoparticle material is applied on the surface of the protective layer 101 and the nanoparticles 102 are disposed, C _M1 / C _Si is preferably 0.5 to 15. From the viewpoint of physical strength, C _M1 / C _Si is more preferably 5 to 8.

Note that when C _M1 / C _Si is in the range of 0.2 to 10 in the widest range (0.2 to 15), the first mask layer 103 is etched using the nanoparticles 102 as a mask. This is preferable because the shape stability of the nanoparticles 102 is improved. In particular, the range of 0.2 to 5 is preferable because the physical stability of the nanoparticles 102 during etching is improved, and the range of 0.2 to 3.5 is more preferable. Moreover, it is preferable that it is 0.23 to 3.5 because the contour shape stability of the nanoparticles 102 is improved when the first mask layer 103 is etched using the nanoparticles 102 as a mask. From the same viewpoint, it is preferably 0.25 to 2.5.

  The nanoparticle 102 is preferably a hybrid including an inorganic segment and an organic segment from the viewpoint of the transfer accuracy and dry etching resistance of the nanoparticle 102. Hybrids include, for example, a combination of inorganic fine particles and a resin that can be photopolymerized (or thermally polymerized), a resin that can be photopolymerized (or thermally polymerized) with an inorganic precursor, or an organic polymer and an inorganic segment. And bonded molecules, inorganic precursors and inorganic precursors having a photopolymerizable group in the molecule. When the sol-gel material is used as the inorganic precursor, it means that a photopolymerizable resin is included in addition to the sol-gel material containing the silane coupling agent. In the case of a hybrid, for example, a metal alkoxide, a silane coupling material having a photopolymerizable group, a radical polymerization resin, and the like can be mixed. In order to further improve the transfer accuracy, silicone may be added thereto. In order to improve dry etching resistance, the sol-gel material portion may be pre-condensed in advance. The mixing ratio of the metal alkoxide containing the silane coupling agent and the photopolymerizable resin is preferably in the range of 3: 7 to 7: 3 from the viewpoint of dry etching resistance and transfer accuracy. More preferably, it is in the range of 3.5: 6.5 to 6.5: 3.5. The resin used for the hybrid is not particularly limited as long as it can be photopolymerized, whether it is a radical polymerization system or a cationic polymerization system.

  In addition, when an inorganic precursor having a photopolymerizable group in the molecule is used as a hybrid, a metal alkoxide having a metal element other than Si as a metal species is used as the inorganic precursor, and photopolymerizability is achieved. A silane coupling material having a photopolymerizable group can be employed as an inorganic precursor having a group in the molecule. These silicones can also be included.

  Furthermore, with respect to the laminate 201 composed of the nanoparticles 102 / first mask layer 103 / object 200 obtained using the second laminate 2, the first mask layer using the nanoparticles 102 as a mask. From the viewpoint of reducing the roughness of the side surface of the first mask layer 103 when etching 103, a molecule in which an organic polymer and an inorganic segment are bonded by a covalent bond, or an inorganic precursor and a photopolymerizable group are contained in the molecule. It is preferable to employ the inorganic precursor provided. As an inorganic precursor having an inorganic precursor and a photopolymerizable group in the molecule, for example, a metal alkoxide is selected as the inorganic precursor, and a photopolymerizable group is used as the inorganic precursor having the photopolymerizable group in the molecule. For example, selecting a silane coupling material to be provided. In particular, the metal species of the metal alkoxide used as the inorganic precursor is preferably Ti, Ta, Zr or Zn, and most preferably Ti, Zr or Zn.

  A method of diluting the nanoparticle material with a solvent when the nanoparticles 102 are disposed on the protective layer 101 and coating the diluted nanoparticle material on the protective layer 101 can be mentioned. Although it does not specifically limit as a dilution solvent, The solvent whose boiling point of a single solvent is 40 to 200 degreeC is preferable, 60 to 180 degreeC is more preferable, and 60 to 160 degreeC is more preferable. Two or more kinds of diluents may be used.

  In addition, when a solvent having a radius of inertia of 5 nm or less when a nanoparticle material is dissolved in a solvent at a concentration of 3% by weight, the placement accuracy on the protective layer 101 is improved and the nanoparticles 102 are formed. This is preferable because the processing accuracy when etching the first mask layer 103 as a mask is improved. The inertia radius is preferably 3 nm or less, more preferably 1.5 nm or less, and most preferably 1 nm or less. Here, the inertia radius is a radius calculated by applying a Gunier plot to a measurement result obtained by measurement by small-angle X-ray scattering using X-rays having a wavelength of 0.154 nm.

  Examples of the photopolymerizable group contained in the nanoparticles 102 include an acryloyl group, a methacryloyl group, an acryloxy group, a methacryloxy group, an acrylic group, a methacryl group, a vinyl group, an epoxy group, an allyl group, and an oxetanyl group.

  Examples of the known resin contained in the nanoparticle 102 include both photopolymerizable and thermal polymerizable resins, or any one of them. For example, in addition to the resin constituting the protective layer 101 described above, a photosensitive resin used in photolithography applications, a photopolymerizable resin and a thermopolymerizable resin used in nanoimprint lithography applications, and the like can be given. In particular, the ratio (Vo1 / Vm1) between the etching rate (Vm1) of the resin contained in the nanoparticles 102 and the etching rate (Vo1) of the first mask layer 103 by dry etching is 1 ≦ Vo1 / Vm1 ≦ 50. It is preferable to contain the resin which satisfy | fills.

The material forming the nanoparticles 102 preferably includes a sol-gel material. By including the sol-gel material, the dry etching rate (Vr _⊥ ) in the vertical direction and the dry etching rate in the horizontal direction when the first mask layer 103 of the nanoparticles 102 having good dry etching resistance is dry-etched. _{(Vr //)} ratio of _{(Vr ⊥} / Vr _//) can be increased. As the sol-gel material, only a metal alkoxide having a single metal species may be used, or a metal alkoxide having a different metal species may be used in combination, but the metal species M1 (where M1 is Ti, Zr, Zn, It is preferable to contain at least two types of metal alkoxides, ie, a metal alkoxide having at least one metal element selected from the group consisting of Sn, B, In, and Al) and a metal alkoxide having the metal type Si. Alternatively, a hybrid of these sol-gel materials and a known photopolymerizable resin can be used as the second mask material.

  From the viewpoint of suppressing physical destruction during dry etching, the second mask material preferably has a small phase separation after curing due to both condensation and photopolymerization. Here, the phase separation can be confirmed by the contrast of a transmission electron microscope (TEM). From the viewpoint of transferability of the nanoparticles 102, the phase separation size is preferably 20 nm or less from the contrast of TEM. From the viewpoint of physical durability and dry etching resistance, the phase separation size is preferably 15 nm or less, and more preferably 10 nm or less. From the viewpoint of suppressing phase separation, the sol-gel material preferably contains a silane coupling agent having a photopolymerizable group.

  As the photopolymerizable radical polymerization resin constituting the nanoparticles 102, a resin obtained by removing the fluorine-containing (meth) acrylate from the photopolymerizable radical polymerization resin constituting the protective layer 101 described above is used. It is preferable. Moreover, (C) photoinitiator used for the curable resin composition which is the material of the protective layer 101 demonstrated above can be used for the photoinitiator contained in nanoparticle material.

  The photopolymerizable cationic polymerization type resin constituting the nanoparticles 102 means a composition containing at least a cationic curable monomer and a photoacid generator. The cation curable monomer in the cation curable resin composition is a compound from which a cured product can be obtained by performing a curing treatment such as UV irradiation or heating in the presence of a cationic polymerization initiator. Examples of the cationic curable monomer include an epoxy compound, an oxetane compound, and a vinyl ether compound. Examples of the epoxy compound include an alicyclic epoxy compound and glycidyl ether. Among these, the alicyclic epoxy compound has an improved polymerization initiation rate, and the oxetane compound has an effect of improving the polymerization rate. Therefore, the alicyclic epoxy compound is preferably used, and glycidyl ether reduces the viscosity of the cationic curable resin composition It is preferable to use it because it is effective in coating properties. More preferably, the alicyclic epoxy compound and the oxetane compound are used in combination, and more preferably, the weight ratio of the alicyclic epoxy compound and the oxetane compound is used in a range of 99: 1 to 51:49. is there.

  The photoacid generator is not particularly limited as long as it generates a photoacid by light irradiation. Examples thereof include aromatic onium salts such as sulfonium salts and iodonium salts.

  By including such a photoacid generator in the nanoparticle material, even if the component other than the photoacid generator of the nanoparticle material is only a metal alkoxide, the metal alkoxide is generated by the photoacid generated by light irradiation. It is possible to improve the hydrolysis / polycondensation rate of the toner, and improve the transfer rate and accuracy. The solvent for dissolving the photoacid generator is not particularly limited as long as it can dissolve the photoacid generator to be used. Can be mentioned. The mixing ratio of propylene carbonate and solvent (A) is preferably a weight ratio of solvent (A) / propylene carbonate of 5 or more because of excellent compatibility.

  In the case where the wettability when the diluted solution 102S of the diluted nanoparticle material is directly applied on the protective layer 101 is poor, a surfactant or a leveling material may be added. Although these can use a well-known commercially available thing, it is preferable to have comprised the photopolymerizable group in the same molecule | numerator. The additive concentration is preferably 40 parts by weight or more and more preferably 60 parts by weight or more with respect to 100 parts by weight of the nanoparticle material from the viewpoint of coatability. On the other hand, from the viewpoint of resistance to dry etching, it is preferably 500 parts by weight or less, more preferably 300 parts by weight or less, and even more preferably 150 parts by weight or less.

  On the other hand, from the viewpoint of improving the dispersibility of the nanoparticle material and improving the transfer accuracy, when using a surfactant or a leveling material, the concentration of these additives should be 20% by weight or less based on the nanoparticle material. Is preferred. Dispersibility is greatly improved when it is 20% by weight or less, and transfer accuracy is also improved when it is 15% by weight or less, which is preferable. More preferably, it is 10% by weight or less. In particular, these surfactants and leveling materials preferably contain at least one functional group of a functional group having a carboxyl group, a urethane group, or an isocyanuric acid derivative from the viewpoint of compatibility. The isocyanuric acid derivatives include those having an isocyanuric acid skeleton and a structure in which at least one hydrogen atom bonded to the nitrogen atom is substituted with another group. As an example that satisfies these conditions, there is an OPTOOL DAC manufactured by Daikin Industries, Ltd. The additive is preferably mixed with the nanoparticle material in a state dissolved in a solvent.

  If the nanoparticle material constituting the nanoparticle 102 includes a material whose state changes in the solvent volatilization process after dilution coating, it is estimated that the driving force to reduce the area of the material itself also works, The nanoparticles 102 can be effectively arranged on the protective layer 101. Examples of the change in mode include an exothermic reaction and a change in viscosity. For example, when a sol-gel material is included, it reacts with water vapor in the air during the solvent volatilization process, and the sol-gel material undergoes polycondensation. As a result, the energy of the sol-gel material is destabilized, so that a driving force that moves away from the solvent liquid surface (solvent-air interface) that decreases as the solvent is dried works. The nanoparticles 102 can be generated and arranged.

  The concentration when the diluted solution of nanoparticles 102 is directly applied to the protective layer 101 is preferably 30% by weight or less. By satisfying this range, the overlap of the nanoparticles 102 in the film thickness direction of the second stacked body 2 can be reduced. Further, the concentration of the diluted solution of the nanoparticles 102 is preferably 15% by weight or less, more preferably 10% by weight or less, more preferably 7.5% by weight from the viewpoint of improving the shape uniformity of the nanoparticles 102. Most preferably: In particular, from the viewpoint of eliminating overlap as much as possible, the concentration of the diluted solution of the nanoparticles 102 is preferably 7% by weight or less, more preferably 5% by weight or less, and 3.5% by weight or less. Most preferred.

  Further, when the viscosity of directly applying the diluted solution of nanoparticles 102 to the protective layer 101 is 100 cP or less, the coating property of the diluted solution of nanoparticles 102 is improved and the alignment accuracy of the nanoparticles 102 is improved. To do. From the same effect, it is preferably 50 cP or less, more preferably 20 cP or less, and most preferably 10 cP or less. In addition, since die coating and micro gravure coating can be applied satisfactorily, it is preferably 8 cP or less, more preferably 5 cP or less, and most preferably 3.5 cP or less. The viscosity is measured at 25 ° C.

  Furthermore, the nanoparticles 102 may be transparent or colored. By being transparent, energy is applied to the third laminate composed of the supporting substrate (100 in FIGS. 7A and 7B) / protective layer 101 / nanoparticles 102 / first mask layer 103 / target object 200. When irradiating a line | wire, it becomes possible to irradiate an energy ray through a support base material. On the other hand, when colored, the transferability when the support substrate and the protective layer 101 are peeled from the third laminate can be easily confirmed by visual observation or optical inspection.

[First mask layer]
After the first mask layer 103 of the second stacked body 2 is bonded and bonded to the object 200, the protective layer 101 is peeled off so that the nanoparticles 102 can be easily passed through the first mask layer 103. It can be transferred onto the workpiece 200.

  The first mask layer 103 is not particularly limited as long as an etching rate ratio (selection ratio) described later is satisfied, and a photopolymerizable resin, a thermopolymerizable resin, a thermoplastic resin, or the like can be employed. In particular, by including the reactive diluent and the polymerization initiator, the adhesiveness when the first mask layer 103 is bonded to the target object 200 is improved, and the first mask layer 103 and the nanoparticles 102 are bonded. The interface adhesive strength is improved, and the adhesive strength between the first mask layer 103 and the nanoparticles 102 and between the first mask layer 103 and the object to be processed 200 can be fixed. As a result, the transfer accuracy of the nanoparticles 102 is improved.

  The nanoparticles 102 and the first mask layer 103 are preferably chemically bonded from the viewpoint of transfer accuracy. Therefore, when the nanoparticle 102 contains a photopolymerizable group, it is preferable that the 1st mask layer 103 also contains a photopolymerizable group. Moreover, when the nanoparticle 102 contains a thermopolymerizable group, it is preferable that the 1st mask layer 103 also contains a thermopolymerizable group.

  Further, the first mask layer 103 may contain a sol-gel material in order to generate a chemical bond by condensation with the sol-gel material in the nanoparticles 102. As the photopolymerization method, there are a radical system and a cation system. From the viewpoint of curing speed and dry etching resistance, only a radical system or a hybrid system of a radical system and a cation system is preferable. In the case of a hybrid, it is preferable to mix a radical polymerization resin and a cationic polymerization resin in a weight ratio of 3: 7 to 7: 3, which is 3.5: 6.5 to 6.5: 3.5. And more preferred.

  From the viewpoint of physical stability and handling of the first mask layer 103 during dry etching, the Tg (glass transition temperature) of the first mask layer 103 after curing is preferably 30 ° C. to 250 ° C. , 60 ° C to 200 ° C is more preferable.

  From the viewpoint of adhesion between the first mask layer 103 and the target object 200, or the first mask layer 103 and the nanoparticles 102, the shrinkage rate of the first mask layer 103 by the specific gravity method is 5% or less. Is preferred.

  The first mask layer 103 may include a binder resin. By including the binder resin, the physical stability of the first mask layer 103 is improved, and the bonding accuracy when the first mask layer 103 is bonded to the workpiece 200 is improved. Moreover, the 1st mask layer 103 can improve the precision stability of the 1st mask layer 103 in the 2nd laminated body 2 because binder resin, a reactive diluent, and a polymerization initiator are included. Therefore, the fine pattern arrangement accuracy of the nanoparticles 102 of the second stacked body 2 and the film thickness accuracy of the first mask layer 103 can be reflected and transferred to the object 200 to be processed.

  In addition, by including the binder resin, the first mask layer 103 can be dried. That is, the first mask layer 103 can be handled as a (semi) solid with extremely low tack. For this reason, while handling until the 2nd laminated body 2 is bonded on the to-be-processed object 200 improves, using thermocompression bonding (thermal bonding) for bonding to the to-be-processed body 200 and adhesion | attachment. This makes it possible to further improve the bonding / transfer accuracy.

  When the binder resin and the reactive diluent are included, the reaction mode of the binder resin and the reaction mode of the reactive diluent may be different. For example, when the binder resin is photopolymerizable and thermopolymerizable, and the binder resin is thermopolymerizable, the reactive diluent cross-links with the binder resin by photocuring and then crosslinks with the binder resin by subsequent heating. And can be further crosslinked. Similarly, when both the binder resin and the reactive diluent are thermally and photoreactive, it is possible to crosslink the binder resin and the reactive diluent by using both crosslinking by light and crosslinking by heat.

  When the binder resin is a reactive binder resin, the glass transition temperature of the first mask layer 103 can be improved. By increasing the glass transition temperature, the heat resistance when the workpiece 200 is etched is improved, so that the processing accuracy of the fine pattern 220 provided on the workpiece 200 can be improved. The reactive site of the reactive binder resin is preferably photoreactive when the reactive diluent is photoreactive, and is preferably thermally reactive when the reactive diluent is thermally reactive. Or the structure which has a photoreactive site | part and a heat-reactive part together may be sufficient. In this case, since the crosslinking by the photoreaction and the crosslinking by the thermal reaction can be used together, the increase degree of the glass transition temperature becomes large. Since the binder resin is a reactive binder resin, the adhesiveness between the first mask layer 103 and the object to be processed 200 and the adhesiveness between the first mask layer 103 and the nanoparticles 102 can be fixed. Since it is further improved, the transfer accuracy is improved.

  The binder resin can be appropriately selected depending on the use of the second laminate 2, but from the viewpoint of processing the object to be processed 200, the glass transition temperature of the backbone polymer of the binder resin is preferably 45 ° C. or higher. The temperature is more preferably 80 ° C. or higher, and most preferably 115 ° C. or higher.

  Furthermore, the binder resin may be an alkali-soluble resin. By being alkali-soluble, it is possible to easily remove the residue formed of the first mask layer 103 by applying alkali development after the fine pattern 220 is formed on the object to be processed 200. The processing margin of the body 200 increases. From the viewpoints of adhesion to the object 200 and alkali developability, the binder resin preferably contains a carboxyl group. The amount of the carboxyl group is preferably from 100 to 600, more preferably from 300 to 450, as an acid equivalent. An acid equivalent shows the mass of the linear polymer which has a 1 equivalent carboxyl group in it. The acid equivalent is measured by a potentiometric titration method using a Hiranuma automatic titration apparatus (COM-555) manufactured by Hiranuma Sangyo Co., Ltd., using a 0.1 mol / L sodium hydroxide aqueous solution.

  Moreover, it is preferable that the weight average molecular weight of binder resin is 5000-500000 from a viewpoint of pasting property and a transfer precision. In order to further improve the physical stability of the first mask layer 103 and to further improve the bonding accuracy when the first mask layer 103 is bonded to the object 200, a binder resin. The weight average molecular weight is more preferably 5,000 to 100,000, still more preferably 5,000 to 60,000.

  The degree of dispersion (sometimes referred to as molecular weight distribution) is represented by the ratio of the weight average molecular weight to the number average molecular weight ((dispersion degree) = (weight average molecular weight) / (number average molecular weight)). A dispersion degree of about 1 to 6 is used, preferably 1 to 4. The molecular weight was measured by Gel Permeation Chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko KK (KF-807, KF-806M, KF- 806M, KF-802.5) 4 in series, moving bed solvent: tetrahydrofuran, using a calibration curve based on polystyrene standard sample) to determine the weight average molecular weight (polystyrene conversion).

  Moreover, it is preferable to have the site | part shown by following Chemical formula (4) in the side chain of a binder resin, the inside of a principal chain, or a side chain and the inside of a principal chain from the viewpoint of the selection ratio mentioned later.

  Of the reactive diluents included in the first mask layer 103, the photopolymerizable diluent is not particularly limited. For example, the resin (photopolymerizable resin) described in the nanoparticle 102 may be used. it can. From the viewpoint of dry etching resistance, the average number of functional groups of the photopolymerizable diluent is preferably 1.5 or more. Further, from the viewpoint of film formation stability of the first mask layer 103, the average number of functional groups is preferably 4.5 or less. In the case where a chlorine-based gas is used when dry-etching the workpiece 200, it is preferable to include a reactive diluent containing in the molecule the site represented by the chemical formula (4) from the viewpoint of dry etching resistance. From the viewpoint of adhesion between the nanoparticles 102 and the first mask layer 103, it is preferable that the nanoparticles 102 and the first mask layer 103 contain at least one similar reactive diluent.

  The glass transition temperature of the reactive diluent contained in the first mask layer 103 is preferably 80 ° C. or higher because the processing accuracy of the workpiece 200 is improved. In particular, from the viewpoint of improving the glass transition temperature of the entire first mask layer 103, the glass transition temperature of the reactive diluent contained in the first mask layer 103 is preferably 120 ° C. or higher, and is 150 ° C. or higher. More preferably, it is most preferably 180 ° C. or higher.

  A compound having at least one OH group and at least one addition polymerizable unsaturated bond in one molecule may be employed as the reactive diluent. By adopting such a molecule as a reactive diluent, the adhesion between the nanoparticles 102 and the object to be processed 200 can be improved. There may be a plurality of OH groups in the molecule. The OH group may be alcoholic or phenolic, but alcoholic is preferable from the viewpoint of adhesion and etching resistance. There may be a plurality of addition polymerizable unsaturated bonds in the molecule.

  Among the polymerization initiators constituting the first mask layer 103, as the photopolymerization initiator, the photopolymerization initiator described for the nanoparticles 102 can be used.

  The ratio of the binder resin to the entire first mask layer 103 is in the range of 20% by mass to 90% by mass, preferably 30% by mass to 70% by mass, from the viewpoints of bonding properties and dry etching resistance.

  The content of the alkali-soluble binder resin is preferably in the range of 30% by mass to 75% by mass based on the total mass of the first mask layer 103. More preferably, it is 40 mass% or more and 65 mass% or less. From the viewpoint of developing alkali developability, it is preferably 30% by mass or more, and from the viewpoint of curability, transferability, and dry etching resistance, it is preferably 75% by mass or less.

The concentration of the solvent remaining in the first mask layer 103 is preferably 2000 (g / ml) / m ³ or less when measured according to the following criteria. By satisfying this range, the bonding accuracy of the second laminate 2 to the object to be processed, the processing accuracy of the first mask layer 103n by the nanoparticles 102, and the processing accuracy of the object 200 by the first mask layer 103 are increased. Can be improved. From the viewpoint of more exerting the effect, it is preferably 1000 (g / ml) / m ³ or less, more preferably 500 (g / ml) / m ³ or less, and 200 (g / ml) / m. Most preferably, it is ³ or less. Furthermore, from the viewpoint of improving the transfer accuracy of the nanoparticles 102 and the first mask layer 103 regardless of the arrangement and shape of the concavo-convex structure 101a of the protective layer 101, it is 150 (g / ml) / m ³ or less. Preferably, it is 130 (g / ml) / m ³ or less, and most preferably 120 (g / ml) / m ³ or less.
1. On the protective layer 101, only the first mask layer 103 is formed under the same conditions as in the case where the nanoparticles 102 are present, and the second stacked body 2 that does not include the nanoparticles 102 is obtained.
2. The 2nd laminated body 2 is cut into 20 mm x 20 mm, measured up with 10 mL acetone, and a solution is extract | collected.
3. The collected solution is analyzed by the SIM method using a GC / MS apparatus, and the amount of the solvent is obtained with a dimension of “g / ml”.
4.1. The average thickness have [m] of the first mask layer 103 of the laminated body manufactured in the above is obtained.
5.3. The value obtained by dividing the result by the volume of the first mask layer 103 (0.02 m × 0.02 m × have) is used as the concentration of the solvent remaining in the first mask layer 103.

  Further, the first mask layer 103 can contain coloring substances such as dyes and pigments. By containing the colored material, it is possible to visually determine whether or not the transfer is performed well when the laminate 201 is transferred and formed using the second laminate 2. Furthermore, absorption of a colored substance can be used for quality control of the first mask layer 103 formed on the protective layer 101.

  Examples of the coloring substance used include fuchsin, phthalocyanine green, auramine base, chalcoxide green S, paramadienta, crystal violet, methyl orange, Nile Blue 2B, Victoria Blue, Malachite Green (Eisen (registered trademark) MALACHITEGREEN manufactured by Hodogaya Chemical Co., Ltd.). ), Basic Blue 20, Diamond Green (Eisen (registered trademark) DIAMOND GREENGH manufactured by Hodogaya Chemical Co., Ltd.) and the like.

  From the same effect, the first mask layer 103 can contain a coloring dye that develops color when irradiated with light. Examples of the coloring dye used include a combination of a leuco dye or a fluorane dye and a halogen compound.

  Examples of the leuco dye include tris (4-dimethylamino-2-methylphenyl) methane [leuco crystal violet], tris (4-dimethylamino-2-methylphenyl) methane [leucomalachite green], and the like.

  Halogen compounds include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2,3 -Dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane, triazine compounds and the like. Examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine and 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine. Among such coloring dyes, a combination of tribromomethylphenylsulfone and a leuco dye or a combination of a triazine compound and a leuco dye is useful.

  Further, in order to improve the stability of the first mask layer 103, it is preferable to include a radical polymerization inhibitor in the first mask layer 103. Examples of such radical polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2 Examples include '-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), diphenylnitrosamine and the like.

  In addition, the first mask layer 103 may contain an additive such as a plasticizer as necessary. Examples of such additives include phthalic esters such as diethyl phthalate, p-toluenesulfonamide, polypropylene glycol, polyethylene glycol monoalkyl ether, and the like.

  Further, the first mask layer 103 may have a multilayer structure of n layers (n ≧ 2) or more. For example, two first mask layers 103-1 and 103-2 can be provided on the nanoparticles 102 of the first laminate 1. Similarly, the (N + 1) th first mask layer 103- (N + 1) can be provided over the Nth first mask layer 103-N. By adopting the first mask layer 103 having such an n-layer structure, the surface of the nanoparticle 102 is formed with respect to the laminate composed of the nanoparticle 102 / n-layer first mask layer 103 / object 200. When etching (dry etching) is performed from the side, controllability such as an inclination angle of the first mask layer 103 is improved. Therefore, the freedom degree of the process of the to-be-processed object 200 which continues is improved. From the viewpoint of exerting this effect, the multilayer degree n in the case of the multilayer first mask layer 103 is preferably 2 or more, 10 or less, more preferably 2 or more and 5 or less, and most preferably 2 or more and 4 or less. In the case of the multilayer first mask layer 103, when the volume of the nth layer is Vn, the total volume V of the first mask layer 103 is V1 + V2 +... Vn. At this time, it is preferable that the first mask layer 103 satisfying a selection ratio (dry etching rate ratio) range described later has a volume of 50% or more with respect to the volume V of the entire first mask layer 103. For example, in the case of the first mask layer 103 having a three-layer structure, the volume of the first mask layer 103 of the first layer is V1, the volume of the first mask layer 103 of the second layer is V2, and the first layer of the third layer is V2. The volume of one mask layer 103 is V3. Further, when the first mask layer 103 that satisfies the selection ratio is the second layer and the third layer, (V2 + V3) / (V1 + V2 + V3) is preferably 0.5 or more. Similarly, when only the third layer satisfies the selection ratio range, (V3) / (V1 + V2 + V3) is preferably 0.5 or more. In particular, from the viewpoint of the processing accuracy of the multilayer first mask layer 103 and the processing accuracy of the workpiece 200, the volume ratio is more preferably 0.65 (65%) or more, and 0.7 (70%) or more. Most preferred. In addition, since all the n layers satisfy the selection ratio range, the processing accuracy of the object to be processed 200 is greatly improved. Furthermore, in the case of the n-layer first mask layer 103, the composition on the outermost side (the layer farthest from the concavo-convex structure 101a) only needs to satisfy the composition described in the above [First mask layer], For the other layers, the composition of the nanoparticles 102 or the composition of the protective layer 101 described above can be adopted in addition to the composition described in the above [First mask layer]. Under such circumstances, from the viewpoint of stability as the first mask layer 103, it is preferable to adjust all the n layers within the composition range described in [First Mask Layer] described above.

[Selection ratio]
The ratio (Vo1 / Vm1) between the etching rate (Vm1) of the nanoparticles 102 by dry etching and the etching rate (Vo1) of the first mask layer 103 is determined by using the first mask layer 103 as a mask. This affects the processing accuracy when etching. Since Vo1 / Vm1> 1 means that the nanoparticles 102 are less likely to be etched than the first mask layer 103, (Vo1 / Vm1) is preferably as large as possible.

  (Vo1 / Vm1) preferably satisfies Vo1 / Vm1 ≦ 150, and more preferably satisfies Vo1 / Vm1 ≦ 100, from the viewpoint of the coating property of the nanoparticles 102. Further, (Vo1 / Vm1) preferably satisfies 3 ≦ Vo1 / Vm1 (formula (4)) from the viewpoint of etching resistance, more preferably satisfies 10 ≦ Vo1 / Vm1, and 15 ≦ Vo1 / Vm1. It is still more preferable to satisfy | fill.

  By satisfying the above range, the thick first mask layer 103 can be easily finely processed by dry etching using the nanoparticles 102 as a mask. As a result, a fine mask pattern 202a composed of the nanoparticles 102 and the first mask layer 103 finely processed by dry etching can be formed on the target object 200. By using such a fine pattern structure 202, the above-described functions can be obtained, and the object 200 can be easily dry-etched.

On the other hand, the etching anisotropy in etching the first mask layer 103 (lateral etching rate _{(Vo //),} the ratio of the vertical etching rate _{(Vo ⊥) (Vo ⊥ /} Vo //) is , _Vo⊥ / Vo _// > 1 is preferably satisfied and larger is more preferable, depending on the ratio of the etching rate of the first mask layer 103 to the etching rate of the object 200, but _Vo⊥ / it is preferable to satisfy the Vo _// ≧ 2, it is more preferable to satisfy the _{Vo ⊥} / Vo _// ≧ 3.5, it is further preferable to satisfy the _{Vo ⊥} / Vo _// ≧ 10.

  Note that the vertical direction means the film thickness direction of the first mask layer 103, and the horizontal direction means the surface direction of the first mask layer 103. In a region where the pitch is less than or equal to submicron, the first mask layer 103 is kept large in order to stably form the thick first mask layer 103 and easily dry-etch the workpiece 200. There is a need. By satisfying the above range, it is preferable because the width (the thickness of the trunk) of the first mask layer 103 after dry etching can be kept large.

  The ratio (Vo2 / Vi2) between the etching rate (Vi2) of the target object 200 and the etching rate (Vo2) of the first mask layer 103 by dry etching is preferably as small as possible. If Vo2 / Vi2 <1 is satisfied, the etching rate of the first mask layer 103 is smaller than the etching rate of the workpiece 200, so that the workpiece 200 can be easily processed. From the viewpoint of the coating property of the first mask layer 103 and the etching accuracy, (Vo2 / Vi2) preferably satisfies Vo2 / Vi2 ≦ 3, and more preferably satisfies Vo2 / Vi2 ≦ 2.5. (Vo2 / Vi2) is more preferable when Vo2 / Vi2 ≦ 2 is satisfied because the first mask layer 103 can be thinned. Most preferably, Vo2 / Vi2 <1.

  Ratio of etching rate of workpiece 200 and etching rate of hard mask layer The hard mask layer is preferably 1 or more and more preferably 3 or more from the viewpoint of workability. From the viewpoint of processing the workpiece 200 with a high aspect ratio, the selection ratio is preferably 5 or more, and more preferably 10 or more. From the viewpoint of reducing the thickness of the hard mask layer, the selection ratio is more preferably 15 or more.

  In addition, since the dry etching rate with respect to a fine pattern receives the influence of a fine pattern deeply, these selection ratios are the values measured with respect to the flat film (solid film) of various materials.

  For example, the etching rate for the first mask layer 103 is dry etching or wet etching on a flat film obtained by forming the first mask layer 103 on a substrate such as Si or quartz. It is calculated by. When the first mask layer 103 is reactive, it is cured to obtain a flat film.

  The etching rate for the nanoparticles 102 is calculated by performing dry etching on a flat film obtained by forming the nanoparticles 102 on a substrate such as Si or quartz. When the nanoparticles 102 are reactive, they are cured to obtain a flat film.

  The etching rate for the hard mask layer is calculated by forming a hard mask layer on a substrate such as Si or quartz and performing dry etching or wet etching.

  The etching rate for the object 200 is calculated by performing dry etching or wet etching on the object 200.

  Moreover, when calculating | requiring the said etching rate ratio, it calculates as a ratio of the etching rate which applied the same etching conditions. For example, Vo1 / Vm1 is calculated as the ratio of the respective etching rates (Vo1 and Vm1) obtained by performing the same dry etching process on the flat film of the first mask layer 103 and the flat film of the nanoparticles 102. doing.

  Similarly, Vo2 / Vi2 is the ratio of the respective etching rates (Vo2 and Vi2) obtained by performing the same dry etching or wet etching process on the flat film of the first mask layer 103 and the target object 200. It is calculated as

  Similarly, the etching rate of the object to be processed 200 / the etching rate of the hard mask layer is obtained by performing the same dry etching or wet etching process on the object to be processed 200 and the hard mask layer. The ratio of the etching rate of the body 200 and the etching rate of the hard mask layer is calculated.

[To-be-processed object]
The target object 200 to be processed using the fine mask pattern 202a manufactured using the second stacked body 2 as a mask is not particularly limited as long as it is appropriately selected depending on the application. From inorganic substrates to organic substrates and films can be used. For example, the material which comprises the support base material 100 and the protective layer 101 which were demonstrated above can be selected. In addition, in the case of an application that satisfies the improvement of the internal quantum efficiency of the LED and the improvement of the light extraction efficiency at the same time, examples of the object 200 include a sapphire substrate, a spinel substrate, a Si substrate, a SiC substrate, or a nitride semiconductor substrate. be able to. In this case, the substrate is processed using the obtained fine mask pattern 202a as a mask. On the other hand, a GaN substrate can be selected for the purpose of improving light extraction. In this case, the GaN substrate is processed using the obtained fine mask pattern 202a as a mask. In addition, a base material made of GaAsP, GaP, AlGaAs, InGaN, GaN, AlGaN, ZnSe, AlHaInP, ZnO, ITO, or the like can also be used. For the purpose of producing a non-reflective surface glass with a large area fine pattern, a glass plate, a glass film, or the like can be selected. In order to improve light absorption efficiency, conversion efficiency, etc. for solar cell applications, a Si substrate can also be employed. Moreover, when producing a super water-repellent film and a super hydrophilic film, a film base material can be used. For the purpose of a complete black body, a substrate or the like in which carbon black is kneaded or coated on the surface can be employed. In addition, when a metal is used for the nanoparticle 102, the mask layer itself transferred and formed on the surface of the object 200 exhibits a function and can be applied as a sensor (optical sensor). In this case, the base material may be appropriately selected from the viewpoint of the usage environment of the sensor.

  Subsequently, a case where an uneven structure is formed on the surface of the protective layer 101 will be described. When the surface of the protective layer 101 has a concavo-convex structure, the nanoparticles 102 are disposed inside the concavo-convex structure. For this reason, the arrangement and shape of the nanoparticles 102 can be protected by the uneven structure of the protective layer 101. Even when the protective layer 101 has a concavo-convex structure, preferable requirements for the second laminate 2 satisfy the above-described range.

  As shown in FIG. 8, nanoparticles 102 are provided inside the recesses 101c of the uneven structure 101a of the protective layer 101, and a first mask layer 103 is provided so as to cover the nanoparticles 102 and the uneven structure 101a. Here, the nanoparticle 102 is disposed in the concave portion 101c of the concavo-convex structure 101a and does not protrude outward from the top of the convex portion of the concavo-convex structure 101a. This is preferable because the processing accuracy of one mask layer 103 is improved.

  In this way, the nanoparticles 102 are arranged so as to fill the concave portion 101c of the concave-convex structure 101a. As a result, the first mask layer 103 is bonded to the object to be processed 200, and dry etching is further performed. As shown in FIG. 7C, the first mask layer 103 and the nanoparticles 102 are formed on the object to be processed 200. When the laminated body 201 to be manufactured is manufactured, the nanoparticles 102 arranged in the recesses of the first mask layer 103 can be removed. As a result, in the dry etching process when the fine mask pattern 202a is formed on the target object 200, the nanoparticles 102 disposed on the bottom of the concave portion of the first mask layer 103 of the stacked body 201 corresponding to the remaining film are removed. The process to perform can be omitted. Therefore, it is possible to improve the processing accuracy of the fine mask pattern 202a formed on the target object 200, and the accuracy of the fine pattern 220 provided on the target object 200 by further processing is improved.

[Uneven structure]
The shape of the concavo-convex structure 101a of the protective layer 101 in the second stacked body 2 is not particularly limited. For example, a line and space structure in which a plurality of fence-like bodies are arranged, a lattice structure in which a plurality of fence-like bodies intersect, Examples include a dot structure in which a plurality of dot (convex portion, protrusion) -like structures are arranged, a hole structure in which a plurality of hole (concave) -like structures are arranged, and the like. Examples of the dot structure and the hole structure include a cone, a cylinder, a quadrangular pyramid, a quadrangular prism, a double ring shape, and a multiple ring shape. These shapes include a shape in which the outer diameter of the bottom surface is distorted and a shape in which the side surface is curved.

  When the concavo-convex structure 101a has a dot shape, a continuous gap between dots can be used for application of the diluted solution of the nanoparticle material, and the arrangement accuracy and shape accuracy of the nanoparticles 102 are improved. On the other hand, regarding the use of the second laminate 2, when the transferred nanoparticles 102 function as a mask, the shape of the concavo-convex structure 101 a is preferably a hole shape. Furthermore, since the shape of the concavo-convex structure 101a is a hole shape, the durability of the concavo-convex structure (resistance to physical destruction) when a diluted solution of the nanoparticle material is directly applied to the concavo-convex structure 101a is improved.

  In the case where the concavo-convex structure 101a has a dot shape, it is preferable that adjacent dots are connected through a smooth concave portion because the above-described effect is more exhibited. Moreover, when the uneven | corrugated structure 101a is a hole shape, since the said effect is exhibited more when the adjacent hole is connected through the smooth convex part, it is preferable.

  Here, the “dot shape” is “a shape in which a plurality of columnar bodies (conical bodies) are arranged”, and the “hole shape” is a “shape in which a plurality of columnar (conical) holes are formed”. It is. That is, as shown in FIG. 9A, the dot shape is a shape in which a plurality of convex portions 101b (columnar bodies (conical bodies)) are arranged, and the concave portions 101c between the convex portions 101b are in a continuous state. is there. On the other hand, the hole shape is a shape in which a plurality of concave portions 101c (columnar (conical) holes) are arranged as shown in FIG. 9B, and adjacent concave portions 101c are separated from each other by the convex portions 101b. It is.

  In the concavo-convex structure 101a, the center-to-center distance between the protrusions 101b in the dot shape or the center-to-center distance between the recesses 101c in the hole shape is 50 nm or more and 5000 nm or less, and the height of the protrusion 101b or the depth of the recess 101c is 10 nm or more. It is preferable that it is 2000 nm or less. In particular, the center-to-center distance between the protrusions 101b in the dot shape or the center-to-center distance between the recesses 101c in the hole shape is 100 nm to 1000 nm, and the height of the protrusion 101b or the depth of the recess 101c is 50 nm to 1000 nm. Preferably there is. By satisfying these ranges, the controllability of the shape of the nanoparticles 102 provided in the recesses 101c of the concavo-convex structure 101a can be improved. Here, the convex portion 101b refers to a portion higher than the average height of the concavo-convex structure 101a, and the concave portion 101c refers to a portion lower than the average height of the concavo-convex structure 101a.

  As the arrangement of the concavo-convex structure 101a, a regular hexagonal arrangement, a quasi-hexagonal arrangement, a quasi-tetragonal arrangement, a regular tetragonal arrangement, a random arrangement, an arrangement obtained by combining these regularly or with low regularity, and the like can be adopted. For example, an array that gradually changes from a hexagonal array to a tetragonal array and then returns to the hexagonal array can be employed. In particular, from the viewpoint of the arrangement accuracy of the nanoparticles 102, a hexagonal array in which the distortion of the array in the regular hexagonal array is ± 15% or less is preferable. Here, even if the distortion of the arrangement is irregularly generated on the unit cell scale, or even when the distortion of the unit cell scale changes continuously over a long period, a plurality of unit cells are combined into one set. The distortion provided in each set may be provided irregularly or may be provided regularly.

  The shape of the concavo-convex structure 101a can be described by variables such as the concave depth, the width of the concave bottom, the width of the convex top, the angle of the concave side, and the number of inflection points on the concave side. On the other hand, the arrangement can be described by using the pitch as a variable. Here, when the variable is x, the ratio of the standard deviation to the arithmetic average with respect to x and the arithmetic average (standard deviation / arithmetic average) is 0.025 or more, so that the nanoparticles 102 can be disturbed. . For this reason, disturbance can be applied to the first mask layer 103 etched using the nanoparticles 102 as a mask and the fine pattern 220 of the processed object 200 further processed. By including such a disturbance, when the target object 200 having the fine pattern 220 is used for an optical application, for example, an LED or an OLED, scattering can be strongly added.

  As described above, if the standard deviation / arithmetic mean is 0.025 or more, it is possible to strongly add scattering. From the viewpoint of enhancing the scattering property and improving the performance as an optical element, the standard deviation / arithmetic average is preferably 0.03 or more. On the other hand, the upper limit value is preferably 0.5 or less from the viewpoint of the arrangement accuracy of the nanoparticles 102. Further, from the viewpoint of improving the processing accuracy of the first mask layer 103, it is preferably 0.35 or less, more preferably 0.25 or less, and most preferably 0.15 or less.

  10A and 10B, the concavo-convex structure 101a of the protective layer 101 has convex portions 101b (or concave portions 101c) at a pitch P in the first direction with respect to the first direction and the second direction orthogonal to each other in the plane. , The same applies hereinafter) and the protrusions 101b are arranged at a pitch S in the second direction, the deviation (shift amount (α)) of the protrusions 101b forming a row in the second direction with respect to the first direction. It may be an array with high regularity (see FIG. 10A) or an array with low regularity of the shift amount (α) (see FIG. 10B). The shift amount (α) refers to the distance between line segments parallel to the second direction passing through the center of the closest convex portion 101b in adjacent rows parallel to the first direction. For example, as shown in FIG. 10A, the line segment parallel to the second direction passing through the center of the arbitrary convex portion 101b in the (N) th row parallel to the first direction and the closest distance from the convex portion 101b. The distance from the line segment parallel to the second direction passing through the center of the convex portion 101b in the (N + 1) th row is defined as the shift amount (α). The array shown in FIG. 10A can be said to be an array having periodicity because the shift amount (α) is almost constant regardless of which column is the (N) th column. On the other hand, the array shown in FIG. 10B can be said to be an array having aperiodicity because the value of the shift amount (α) varies depending on which column is the (N) th column.

  The pitch P and the pitch S can be appropriately designed according to the intended use. For example, the pitch P and the pitch S may be equal. In FIGS. 10A and 10B, the convex portions 101b are depicted in an independent state without overlapping, but the convex portions 101b arranged in both the first direction and the second direction overlap. It may be.

  For example, when processing the surface of the sapphire substrate (object 200) of the LED, in order to improve the internal quantum efficiency of the LED, the concavo-convex structure 101a of the protective layer 101 has a pitch P, S of 200 nm to 800 nm, high Is preferably 50 nm to 800 nm. The sequence is preferably a regular sequence. In particular, in order to improve the internal quantum efficiency and improve the light extraction efficiency, the arrangement having the non-periodicity described above is preferable. In addition, in order to improve the internal quantum efficiency and the light extraction efficiency at the same time, the uneven structure 101a of the protective layer 101 has a pitch P, S having a regular arrangement on the nanoscale and a large periodicity on the microscale. It is more preferable to have a hole shape in which modulation having a microscale period is added.

  When manufacturing the 2nd laminated body 2, it is preferable to use the structure and nanoparticle material which are shown next from a viewpoint which arrange | positions the nanoparticle 102 inside the recessed part of the uneven structure 101a.

  11A and 11B are schematic cross-sectional views showing the dot-shaped concavo-convex structure 101 a of the protective layer 101 in the second stacked body 2. When the concavo-convex structure 101a of the protective layer 101 has a dot shape, the length of the longest line segment (lx) on the surface on which one convex portion top 101b-1 is formed is submicron scale. The particulate material is preferable because it is efficiently filled into the recess 101c so as to reduce the energy of the system. In particular, the length of the longest line segment is preferably 500 nm or less because the above effect can be further exhibited, more preferably 300 nm or less, and most preferably 150 nm or less. In addition, the surface which forms one convex part top part 101b-1 means the surface where the surface which passes through the top part position of each convex part 101b, and one convex part top part 101b-1.

  As shown in FIG. 11A, the convex part 101b has a structure in which the area of the convex part bottom part 101b-2 is larger than the area of the convex part top part 101b-1, that is, the convex part 101b has a slope. This is preferable because the effect can be further exhibited. Furthermore, as shown in FIG. 11B, when the convex part top part 101b-1 and the inclined part 101b-3 are continuously connected smoothly, the solid-liquid interface at the time of diluting and coating the nanoparticles 102 is applied. This is preferable because the pinning effect in (a pinning effect by TPCL) can be suppressed and the above effect can be further exhibited.

  FIG. 12 is a schematic plan view showing the hole-shaped concavo-convex structure 101 a of the protective layer 101 in the second stacked body 2. When the concavo-convex structure 101a of the protective layer 101 has a hole shape, in one hole (A) and the hole (B) closest to the hole (A), the opening flange of the hole (A) and the opening of the hole (B) When the length of the shortest line segment (ly) connecting the ridges is submicron scale, the diluted nanoparticle material is efficiently filled into the recess 101c so as to reduce the energy of the system. As a result, the nanoparticles 102 with little overlap in the film thickness direction of the second laminate 2 can be obtained. In particular, it is preferable that the length of the shortest line segment is 500 nm or less because the above effect can be further exhibited, more preferably 400 nm or less, and most preferably 300 nm or less. Among these, the length of the shortest line segment is preferably 150 nm or less, more preferably 100 nm or less, and most preferably 0 nm. In addition, the length of the shortest line segment of 0 nm means a state in which part of the opening flange portion of the hole (A) and the hole (B) overlaps.

  Moreover, it is preferable that the area of the hole opening is larger than the area of the hole bottom because the above-described effect can be further exhibited. In addition, if the opening wrinkles and the side surfaces of the recesses are connected continuously and smoothly, the pinning effect at the solid-liquid interface (pinning effect by TPCL) when diluting and applying the nanoparticle material can be suppressed. It is preferable because the above effect can be further exhibited.

  Furthermore, in the second laminate 2, the pitch P and pitch S of the concavo-convex structure 101a of the protective layer 101 are both preferably 1500 nm or less in order to further exhibit the above effects, and more preferably 1000 nm or less. In particular, from the viewpoint of reducing the number of nanoparticles 102 overlapping each other and improving the processing accuracy of the first mask layer 103, it is preferably 800 nm or less, more preferably 500 nm or less, and most preferably 350 nm or less. . Moreover, it is preferable that a pitch is 50 nm or more from a viewpoint of the filling arrangement | positioning precision of the nanoparticle 102, and transcription | transfer property. When the nanoparticle material is applied onto the concavo-convex structure of the protective layer 101 and the nanoparticles 102 are filled into the recesses, the pitch P and S are within the range of 50 nm to 1000 nm when the aperture ratio is 45% or more. In this case, the nanoparticle 102 can recognize the concavo-convex structure 101a and wets into the pattern so as to maximize the radius of curvature of the virtual droplet of the nanoparticle 102 formed inside the concavo-convex structure 101a. Since it spreads, it is preferable. The virtual droplet means a droplet of a nanoparticle material that is assumed to exist inside the recess of the uneven structure 101a of the protective layer 101. In particular, it is preferably 50% or more, and more preferably 55% or more. Furthermore, when the aperture ratio is 65% or more, in addition to the above effect, the potential from the convex portion of the concavo-convex structure 101a of the protective layer 101 toward the concave portion works, and after the droplet is filled into the concave portion, It is more preferable because the nanoparticle material can be prevented from re-moving to the surface. Moreover, in order to exhibit the said effect much more, 70% or more of aperture ratio is desirable. More preferably, the aperture ratio is 75% or more, and further preferably 80% or more.

  In addition, when the concavo-convex structure 101a of the protective layer 101 has a hole shape, as shown in FIG. 13A, it is included below the unit area (Sc) on the concavo-convex structure 101a in a plane parallel to the main surface of the concavo-convex structure 101a. The ratio of the area (Sh) of the recess 101c is the aperture ratio. FIG. 13C is a schematic diagram in which the concavo-convex structure 101a included under the unit area (Sc) illustrated in FIG. 13A is extracted. In the example shown in FIG. 13C, 12 fine holes (recesses 101c) are included in the unit area (Sc). The sum of the opening area (Sh1 to Sh12) of the twelve fine holes (recesses 101c) is given as Sh, and the opening ratio Ar is given by (Sh / Sc). On the other hand, when the concavo-convex structure 101a is dot-shaped, as shown in FIG. 13B, the concave portion 101c included under the unit area (Sc) on the concavo-convex structure 101a in a plane parallel to the main surface of the concavo-convex structure 101a. The area ratio (Sc-Sh) is the aperture ratio. FIG. 13C is a schematic diagram in which the concavo-convex structure 101a included under the unit area (Sc) illustrated in FIG. 13B is extracted. In the example shown in FIG. 13C, twelve fine dots (convex portions 101b) are included in the unit area (Sc). The sum of the top areas (Sh1 to Sh12) of the twelve fine dots (projections 101b) is given as Sh, and the aperture ratio Ar is given by ((Sc-Sh) / Sc). If the aperture ratio Ar is multiplied by 100, it can be expressed as a percentage.

  For example, in the case of the concavo-convex structure 101a as shown in FIG. 14, in which concave portions having an opening diameter (φ) of 430 nm, a pitch Px in the x-axis direction of 398 nm, and a pitch Py in the y-axis direction of 460 nm are arranged in a hexagonal close-packed array. Sh / Sc is 0.79 (aperture ratio 79%).

  Similarly, for example, for a concavo-convex structure in which concave portions having an opening diameter (φ) of 180 nm, a pitch Px in the x-axis direction of 173 nm, and a pitch Py in the y-axis direction of 200 nm are arranged in a hexagonal close-packed arrangement, Sc) is 0.73 (aperture ratio 73%).

  Similarly, for example, for a concavo-convex structure in which recesses having an aperture diameter (φ) of 680 nm, a pitch Px in the x-axis direction of 606 nm, and a pitch Py in the y-axis direction of 700 nm are arranged in a hexagonal close-packed arrangement, / Sc) is 0.86 (aperture ratio 86%).

  For example, as shown in FIG. 14, a concavo-convex structure in which convex portions having a convex top diameter (φ) of 80 nm, a pitch Px in the x-axis direction of 398 nm, and a pitch Py in the y-axis direction of 460 nm are arranged in a hexagonal close-packed arrangement. In the case of 101a, (Sc-Sh) / Sc is 0.97 (opening ratio 97%).

  Similarly, for example, for a concavo-convex structure in which convex portions having a convex portion top diameter (φ) of 30 nm, a pitch Px in the x-axis direction of 173 nm, and a pitch Py in the y-axis direction of 200 nm are arranged in a hexagonal close-packed arrangement, ((Sc-Sh) / Sc) is 0.98 (aperture ratio 98%).

  Similarly, for example, for a concavo-convex structure in which convex portions having a convex top diameter (φ) of 100 nm, a pitch Px in the x-axis direction of 606 nm, and a pitch Py in the y-axis direction of 700 nm are arranged in a hexagonal close-packed arrangement , ((Sc-Sh) / Sc) is 0.98 (aperture ratio 98%).

  Further, the uneven structure 101a of the protective layer 101 may include a coating improving structure. The coating improvement structure is arranged so as to sandwich the region (basic structure) in which the nanoparticles 102 are filled and arranged in the uneven structure 101a of the protective layer 101, and the pitch of the coating improvement structure is larger than the basic structure Is preferred. In particular, it is preferable that the pitch in the coating improving structure gradually increases from the basic structure side to the film edge. For example, in the case of a hole shape, it is preferable to set the aperture ratio of the coating improvement structure portion to be smaller than the aperture ratio of the basic structure portion.

Next, the manufacturing method of the 2nd laminated body 2 which concerns on this Embodiment is demonstrated in detail.
[Production method]
Since the 2nd laminated body 2 expresses an effect by satisfy | filling the requirements demonstrated above, the manufacturing method is not specifically limited. For example, a dispersion liquid in which nanoparticles 102 are dispersed is applied to the surface of the protective layer, the nanoparticles 102 are arranged by removing the solvent, and then the first mask layer material is coated so as to cover all the nanoparticles. A method for forming a film can be mentioned. Although the second laminate 2 according to the present embodiment can also be manufactured by such self-alignment using the energy stabilization of the nanoparticles 102 as a driving force, the array in the predetermined plane of the nanoparticles 102 is controlled, In order to suppress the overlapping of the nanoparticles 102 and improve the processing accuracy of the first mask layer 103, it is preferable to employ the following manufacturing method. The manufacturing method described below uses a guide for arranging the nanoparticles 102.

  Regardless of its outer shape such as a reel shape or a flat plate shape, it includes a step of applying a diluted solution of a nanoparticle material on the surface of the concavo-convex structure 101a of the protective layer 101 and a step of removing excess solvent at least in this order. The 1st laminated body 1 is manufactured. Subsequently, a step of applying a diluted solution of the first mask layer material and a step of removing excess solvent on the surface of the concavo-convex structure 101a of the first laminated body 1 at least in this order is included. The body 2 is manufactured.

[Laminate for forming reel-like fine pattern]
The reel-shaped second laminate 2 is (1) thermoplastic by transfer of a photopolymerizable resin using a reel-shaped support substrate 100 or by transfer of a thermopolymerizable resin, or without using the support substrate 100. A reel-shaped protective layer 101 is manufactured by transferring to a resin (reel-shaped protective layer manufacturing step), and then (2) a metal layer is formed if necessary (metal layer manufacturing step). (3) If necessary, a release layer is formed (release layer forming step), (4) the nanoparticle material is introduced into the concavo-convex structure 101a (nanoparticle filling step), and finally (5) The first mask layer 103 can be formed (first mask layer forming step). The laminate obtained up to the nanoparticle filling step is the first laminate 1.

(1) Reel-shaped protective layer production step 1-1: With a supporting base material Reel-shaped protective layer 101 (with a supporting base material 100) is produced by sequentially performing the following steps (1) to (4). Can do. 15A to 15C are explanatory views of a manufacturing process of the reel-shaped protective layer 101. The following steps are preferably produced by a roll-to-roll continuous transfer process.
Process (1): The process of apply | coating the curable resin composition 111 on the support base material 100 (process of apply | coating resin, refer FIG. 15A).
Step (2): A step of pressing the applied curable resin composition 111 against the master mold 110 that has been subjected to a release treatment (step of pressing a resin against a mold, see FIG. 15B).
Step (3): a step of curing the curable resin composition 111 to obtain a cured product (step of curing the resin).
Step (4): A step of peeling the cured product from the master mold 110 to obtain a protective layer 101 having a reverse shape of the pattern shape of the master mold 110 (a step of peeling the cured product from the mold, a step of obtaining the resin protective layer A) FIG. 15C).

  In the step (2), when producing a resin protective layer excellent in surface releasability satisfying the Es / Eb value described above, a release agent component internally added to the curable resin composition 111 is used for the resin protective layer A. When segregating to the uneven structure 101a surface side (the fine pattern surface side of the master mold 110), the master mold 110 which has been subjected to a release treatment is used. On the other hand, when the subsequent step (2) metal layer preparation step and / or (3) release layer formation step is performed, the release treatment to the master mold 110 may not be performed.

When a photopolymerizable resin composition is used as the curable resin composition 111, particularly when a roll-to-roll process is used, a continuous high transfer is achieved when a cylindrical master mold is used as the master mold 110. The protective layer 101 can be manufactured with accuracy. In the step (3), curing is performed by irradiating light from the supporting base material 100 side. Here, the light source for light irradiation can be appropriately selected depending on the composition of the photopolymerizable resin composition, and is not particularly limited, but a UV-LED light source, a metal halide light source, a high-pressure mercury lamp light source, or the like can be employed. Further, the integrated light quantity of until after irradiated from the start of irradiation with ^light, when a range of ^{500mJ / cm 2 ~5000mJ / cm 2} , preferably for improving the transfer accuracy. More ^{preferably 800mJ / cm 2 ~2500mJ / cm 2} . Further, the light irradiation may be performed by a plurality of light sources. Moreover, when using a thermopolymerizable resin composition as the curable resin composition 111, in the step (3), both or one of the support substrate 100 side and the master mold 110 side, or the support substrate 100 is used. A system capable of heating the entire master mold 110 and the entire curable resin composition 111 is prepared and cured. In particular, from the viewpoint of obtaining the resin protective layer A continuously with high productivity and high transfer accuracy, the curable resin composition 111 is preferably a photopolymerizable resin composition.

  In addition, although the master mold 110 is described in a flat plate shape in the drawing, it is preferably a cylindrical master mold. By using a roll having a fine pattern on the surface of the cylinder as the master mold 110, the protective layer 101 can be manufactured by a continuous process.

A resin protective layer B is produced as shown in FIGS. 16A to 16D using the resin protective layer A obtained in step (4) as a mold, and this resin protective layer B is used as a reel-shaped protective layer 101. May be. In addition, it is preferable that the curable resin composition 111 used when producing the resin protective layer B from the resin protective layer A is a photopolymerizable resin composition, and more preferably a fluorine-containing photocurable resin composition. A composition satisfying the above Es / Eb is most preferable from the viewpoint of transfer accuracy.
Process (4-1): The process of apply | coating the curable resin composition 111 on the support base material 100 (process of apply | coating resin, refer FIG. 16A).
Step (4-2): A step of pressing the applied curable resin composition 111 against the resin protective layer A (step of pressing a resin against a mold, see FIG. 16B).
Step (4-3): Light irradiation is performed from either or both of the support base material 100 side of the resin protective layer A and the support base material 100 side of the resin protective layer B, and the curable resin composition 111 is photoradical. A step of obtaining a cured product by polymerization (a step of photocuring a resin, see FIG. 16C).
Step (4-4): A step of peeling the cured product from the resin protective layer A to obtain a protective layer 101 having a shape similar to the fine pattern shape of the master mold 110 (step of peeling the mold from the cured product, resin protection Step of obtaining layer B, see FIG. 16D).

  As the coating method in the steps (1) and (4-1), a roller coating method, a bar coating method, a die coating method, a spray coating method, an air knife coating method, a gravure coating method, a micro gravure coating method, a flow coating method, a curtain Examples thereof include a coating method and an ink jet method.

  After steps (4) and (4-4), a cover film may be put (matched) and wound up. In addition, as a cover film, the cover film mentioned above is employable, for example.

1-2: No supporting base material The reel-shaped protective layer 101 (without the supporting base material 100) can be produced by sequentially performing the following steps (11) to (12). 17A to 17C are explanatory views of a manufacturing process of the reel-shaped protective layer 101. The following steps are preferably produced by a roll-to-roll continuous transfer process.

Step (11): A step of pressing the master mold 110 obtained by subjecting the thermoplastic resin composition 121 to the mold release treatment in a heating environment at a temperature equal to or higher than the Tg of the thermoplastic resin composition 121 (pressing the mold onto the resin). Step, see FIGS. 17A and 17B).
Step (12): Step of peeling master mold 110 from thermoplastic resin composition 121 at a temperature lower than Tg of thermoplastic resin composition 121 (step of peeling from mold, step of obtaining resin protective layer A, see FIG. 17C ).

  After the step (12), a step of covering (matching) and winding the cover film may be added. In addition, as a cover film, the cover film mentioned above is employable, for example.

  In addition, although the master mold 110 is described in a flat plate shape in the drawing, it is preferably a cylindrical master mold. By using a roll having a fine pattern on the surface of the cylinder as the master mold 110, the protective layer 101 can be manufactured by a continuous process.

(2) Metal layer formation step If necessary, a metal layer composed of metal, metal oxide, or metal and metal oxide on the surface of the concavo-convex structure 101a of the reel-shaped protective layer 101 obtained in (1). Form. The formation method of the metal layer can be classified into a wet process and a dry process.

  In the case of a wet process, the reel-shaped protective layer 101 is immersed in a metal layer precursor solution typified by a metal alkoxide or a plating solution, and then the precursor is partially reacted at a temperature of 25 ° C. to 200 ° C. Alternatively, a metal layer precursor solution typified by metal alkoxide or plating solution is applied to the surface of the concavo-convex structure 101a of the reel-shaped protective layer 101, and then the precursor is partially reacted at a temperature of 25 ° C to 200 ° C. Let Subsequently, the metal layer can be formed by washing the excess precursor. Before immersing in the precursor solution, the surface of the concavo-convex structure 101a of the reel-shaped protective layer 101 may be activated with UV-O3, excimer, or the like.

  In the case of the dry process, the metal layer can be formed by passing the reel-shaped resin protective layer through the vapor of the metal layer precursor represented by metal alkoxide. Before the exposure to the precursor vapor, the surface of the concavo-convex structure 101a of the reel-shaped resin protective layer may be activated with UV-O3, excimer, or the like. On the other hand, a metal layer can also be formed by sputtering or vapor deposition. From the viewpoint of the homogeneity of the metal layer, it is preferably formed by sputtering.

(3) Release layer forming step The reel-like protective layer 101 obtained in (1) or the reel-like protective layer 101 on which the metal layer obtained in (2) is formed are separated if necessary. A mold layer is formed. Hereinafter, the protective layer 101 in which the metal layer is formed and the protective layer 101 in which the metal layer is not formed are simply referred to as a reel-like protective layer 101. The release layer forming method can be classified into a wet process and a dry process.

  In the case of a wet process, the reel-shaped protective layer 101 is submerged in the release material solution, or the release material solution is applied. Subsequently, a dry atmosphere at 25 ° C. to 200 ° C. is passed, and finally the excess release material is washed and dried. Before the immersion in the release agent solution, the surface of the concavo-convex structure 101a of the reel-shaped protective layer 101 may be activated with UV-O3 or excimer.

  On the other hand, in the case of the dry process, the release layer can be formed by passing the reel-shaped protective layer 101 through the release material vapor. Prior to exposure to the release vapor, the surface of the concavo-convex structure 101a of the reel-shaped resin protective layer may be activated with UV-O3, excimer, or the like. Further, the pressure may be reduced during heating.

(4) Nanoparticle filling process The 1st laminated body 1 can be produced by filling the nanoparticle 102 inside the uneven structure 101a of the reel-shaped protective layer 101 obtained in (1) to (3). FIG. 18A to FIG. 18C and FIG. 19A to FIG. 19C are explanatory views of a manufacturing process of the first stacked body 1. Hereinafter, the reel-shaped protective layer 101 obtained in (1), the reel-shaped protective layer 101 obtained by forming the metal layer obtained in (2), or the release layer obtained in (3) is formed. The formed reel-shaped protective layer is also simply referred to as a reel-shaped protective layer 101.
Step (5): A step of applying a diluted solution 102S of nanoparticle material onto the concavo-convex structure 101a of the reel-shaped protective layer 101 (see FIGS. 18A and 19A) (see FIGS. 18B and 19B).
Step (6): A step of removing excess solvent by drying to obtain nanoparticles 102 (see FIGS. 18C and 19C).

  As a coating method in the step (5), a roller coating method, a bar coating method, a die coating method, a reverse coating method, a spray coating method, a gravure coating method, a micro gravure coating method, an ink jet method, an air knife coating method, and a flow coating method. The curtain coating method can be applied. In particular, the micro gravure method, the reverse coating method, and the die coating method are preferable because the coating accuracy of the nanoparticles 102 can be improved. The nanoparticle material is preferably used after being diluted, and the concentration is not particularly limited as long as the solid content of the nanoparticle material per unit volume is smaller than the volume of the concavo-convex structure existing under the unit area. The coating method relating to the filling of the nanoparticles 102 will be described in detail later.

  When the sol-gel material is included in the nanoparticles 102, the step (6) serves not only for solvent drying but also for condensation of the sol-gel material. Moreover, when the sol-gel material is included in the nanoparticles 102, a step of curing after winding may be added. Curing is preferably performed between room temperature and 120 ° C. In particular, the temperature is preferably room temperature to 105 ° C.

(5) 1st mask layer film-forming process 2nd by forming the 1st mask layer 103 on the uneven | corrugated structure 101a surface of the 1st laminated body 1 obtained by (1)-(4). The laminate 2 can be manufactured. 20A to 20C are explanatory diagrams of a manufacturing process of the second stacked body 2. Hereinafter, the reel-shaped protective layer 101 obtained in (1), the reel-shaped protective layer 101 obtained by forming the metal layer obtained in (2), or the release layer obtained in (3). Any of the reel-like protective layers on which the film is formed is denoted as the first laminate 1.
Step (7): A step of applying a diluted solution 103S of the first mask layer material (see FIG. 20B) on the concavo-convex structure 101a of the first laminate 1 (see FIG. 20A).
Step (8): A step of removing excess solvent by drying to obtain a first mask layer 103 (see FIG. 20C).

  As the coating method in the step (7), roller coating method, bar coating method, die coating method, spray coating method, gravure coating method, micro gravure coating method, ink jet method, air knife coating method, flow coating method, curtain coating method Etc. are applicable. In particular, the die coating method is preferable because the coating accuracy of the first mask layer 103 can be improved. A coating method relating to the formation of the first mask layer 103 will be described in detail later.

[Laminate for forming flat fine pattern]
Next, the flat second laminate 2 will be described. The flat plate-like second laminate 2 is manufactured by (1) producing a flat protective layer 101 (a flat protective layer producing step), and subsequently (2) forming a metal layer if necessary (metal Layer preparation step), then (3) forming a release layer if necessary (release layer formation step), (4) introducing nanoparticles 102 into the fine pattern (nanoparticle filling step), Finally, (5) the first mask layer 103 can be formed (first mask layer forming step). The laminate obtained up to the nanoparticle filling step is the first laminate 1.

(1) Flat protective layer preparation step 1-1: With support base The flat protective layer 101 cuts out the reel-shaped protective layer 101 obtained above (A) and pastes it to the flat support base 100. Or (B) a method of forming a transfer structure of the curable resin composition on the flat support substrate 100 using the reel-shaped protective layer 101 obtained as a template, or (C) A method of forming a transfer structure of a curable resin composition on a flat support substrate 100 using a flat master as a template, or a concavo-convex structure of a flat protective layer without a support substrate described in 1-2 below It can be produced by disposing the support base material 100 on the opposite surface.

1-2: No support base material The flat protective layer 101 can be produced by performing fine pattern processing directly on the flat base material. Examples of the processing method include a laser cutting method, an electron beam drawing method, a photolithography method, a direct drawing lithography method using a semiconductor laser, an interference exposure method, an electroforming method, an anodic oxidation method, and a thermal lithography method. Among these, as a processing method, a photolithography method, a direct drawing lithography method using a semiconductor laser, an interference exposure method, an electroforming method, and an anodizing method are preferable, and a direct drawing lithography method using a semiconductor laser, an interference exposure method. An anodic oxidation method is more preferable. Further, the flat protective layer 101 can also be produced by transferring the concavo-convex structure of the flat protective layer 101 produced by the direct processing to a thermosetting resin typified by a thermoplastic resin or PDMS. . Moreover, the flat protective layer 101 made of Ni can be obtained by electroforming these flat protective layers 101 typified by Ni. The above-described reel-shaped protective layer can be obtained by processing the flat protective layer 101 in a cylindrical shape and using the obtained cylindrical master as a template.

(2) Metal layer forming step If necessary, a metal layer is formed on the concavo-convex structure 101a surface of the flat protective layer 101 obtained in (1). The formation method of the metal layer can be classified into a wet process and a dry process.

  In the case of a wet process, the flat protective layer 101 is submerged in a metal layer precursor solution typified by a metal alkoxide or a plating solution, and then the precursor is partially reacted at a temperature of 25 ° C. to 200 ° C. Subsequently, the metal layer can be formed by washing the excess precursor. Before dipping in the precursor solution, the surface of the concavo-convex structure 101a of the flat protective layer 101 may be treated with UV-O3, excimer, or the like. Further, a method of casting a precursor solution on the surface of the concavo-convex structure 101a of the flat protective layer 101, or a spin coating method can be employed. Moreover, it is preferable to add a precursor partial reaction step and a washing step.

  In the case of the dry process, the metal layer can be formed by allowing the flat protective layer 101 to stand in the vapor of the metal layer precursor represented by the metal alkoxide. Before the exposure to the precursor vapor, the fine pattern surface side of the flat protective layer 101 may be treated with UV-O3, excimer or the like. On the other hand, a metal layer can also be formed by sputtering or vapor deposition. Sputtering is preferable from the viewpoint of the homogeneity of the metal layer.

(3) Release layer forming step The flat protective layer 101 obtained in (1) or the flat protective layer 101 on which the metal layer obtained in (2) is formed may be separated if necessary. A mold layer is formed. Hereinafter, the protective layer 101 having a metal layer formed thereon and the protective layer 101 having no metal layer formed thereon are simply referred to as a flat protective layer 101. The release layer forming method can be classified into a wet process and a dry process.

  In the case of the wet process, the flat protective layer 101 is submerged in the release material solution. Subsequently, a dry atmosphere at 25 ° C. to 200 ° C. is passed, and finally the excess release material is washed and dried. Before dipping in the release agent solution, the surface of the concavo-convex structure 101a of the flat protective layer 101 may be treated with UV-O3, excimer, or the like. Moreover, the method of casting a mold release material solution on the fine pattern surface of the flat protective layer 101, or a spin coating method can also be employed. Moreover, it is preferable to add the process of allowing a dry atmosphere to pass through, and the washing process.

  On the other hand, in the case of a dry process, the release layer can be formed by passing the flat protective layer 101 through the release material vapor. Prior to exposure to the release vapor, the surface of the concavo-convex structure 101a of the flat protective layer 101 may be treated with UV-O3, excimer, or the like. Further, the pressure may be reduced during heating.

(4) Nanoparticle filling process The 1st laminated body 1 can be produced by filling the nanoparticle 102 inside the uneven structure 101a of the flat protective layer 101 obtained in (1) to (3). FIG. 18A to FIG. 18C and FIG. 19A to FIG. 19C are explanatory views for explaining a manufacturing process of the first stacked body 1. Hereinafter, the flat protective layer 101 obtained in (1), the flat protective layer 101 obtained by forming the metal layer obtained in (2), or the release layer obtained in (3). The flat protective layer 101 on which the film is formed is also simply referred to as a flat protective layer 101.
Step (5): A step of applying a diluted solution 102S of the nanoparticle material on the concavo-convex structure 101a of the flat protective layer 101 (see FIGS. 18A and 19A) (see FIGS. 18B and 19B).
Step (6): A step of removing excess solvent by drying to obtain nanoparticles 102 (see FIGS. 18C and 19C).

  Examples of the coating method in the step (5) include a spin coating method. In addition, a method of performing a spin coating method after a slit coating method, a casting method, a die coating method, a dipping method, or the like can be given. In the case of the spin coating method, it is desirable to form a diluted solution 102S of nanoparticles 102 as a liquid film on the uneven structure 101a of the flat protective layer 101, and then spin coat. When the sol-gel material is included in the nanoparticles 102, the step (6) serves not only for solvent drying but also for condensation of the sol-gel material. The coating method related to the filling of the nanoparticles 102 will be described later.

(5) 1st mask layer film-forming process 2nd by forming the 1st mask layer 103 on the uneven | corrugated structure 101a surface of the 1st laminated body 1 obtained by (1)-(4). The laminate 2 can be manufactured. 20A to 20C are explanatory diagrams for explaining a manufacturing process of the second stacked body 2. Hereinafter, the flat protective layer 101 obtained in (1), the flat protective layer 101 obtained by forming the metal layer obtained in (2), or the release layer obtained in (3). Even when any of the flat protective layers on which the film is formed is used, it is referred to as the first laminate 1.
Step (7): A step of applying a diluted solution 103S of the first mask layer material (see FIG. 20B) on the concavo-convex structure 101a of the first laminate 1 (see FIG. 20A).
Step (8): A step of removing the excess solvent by drying to obtain the first mask layer 103 (see FIG. 20C).

  Examples of the coating method in the step (7) include a spin coating method. In addition, a method of performing a spin coating method after a slit coating method, a casting method, a die coating method, a dipping method, or the like can be given. In the case of the spin coating method, it is desirable to form a diluted first mask layer 103 as a liquid film on the concavo-convex structure 101a of the first laminate 1, and then spin coat. A coating method related to the formation of the first mask layer 103 will be described later.

  Next, a method for coating a nanoparticle material on the surface of the concavo-convex structure 101a of the protective layer 101 and a method for forming the first mask layer 103 will be described in more detail.

  As described above, the first laminate 1 includes a coating step (see FIGS. 18B and 19B) for applying the diluted solution 102S of the nanoparticle material on the surface of the uneven structure 101a of the protective layer 101, and an extra solution. And a solvent removing step (see FIGS. 18C and 19C) for forming nanoparticles 102.

(Coating process)
In the coating process, Sc is a unit area in a plane parallel to one main surface of the protective layer 101 in the coating region of the coating process, and the coating film thickness (wet film) of the diluted solution 102S in the coating process is used. (Thickness) is hc, the volume concentration of the diluted solution 102S of the nanoparticle material is C, and the concave volume of the concave-convex structure 101a existing under the unit area Sc is Vc, The dilute solution 102S of the nanoparticle material is applied on the concavo-convex structure 101a so as to fill. By satisfy | filling following formula (4), it becomes possible to fill a nanoparticle material uniformly into the inside of the recessed part 101c of the uneven structure 101a. In addition, the coating method will not be specifically limited if the following formula is satisfy | filled, The system mentioned above is employable.
Formula (4)
Sc · hc · C <Vc

(Unit area Sc)
The unit area (Sc) in a plane parallel to one main surface of the protective layer 101 is arranged on the top of the concavo-convex structure 101a of the protective layer 101 as shown in FIGS. 21A and 21B. (100)) indicates the area of a plane parallel to one principal surface. 21A and 21B are diagrams showing the relationship between the concavo-convex structure 101a and the unit area (Sc). 21A is a schematic top view of the concavo-convex structure 101a, and FIG. 21B is a schematic cross-sectional view. As shown in FIG. 21B, the unit area (Sc) is an area on a plane parallel to one main surface of the protective layer 101 (support base material (100)), which is disposed on the concavo-convex structure 101a. The size of the unit area (Sc) is defined as the unit cell area (Ac) or more. The unit cell area Ac is defined as follows.

1. In the case where the concavo-convex structure 101a has a dot shape or a hole shape and has a regular arrangement.
FIG. 22A shows a state in which the concavo-convex structure 101a has a dot shape or a hole shape and is arranged with regularity. From the concavo-convex structure 101a, the concavo-convex structure 101a group (n) forming N rows and the concavo-convex structure 101a group (n + 1) forming N + 1 rows are selected. Subsequently, two adjacent structures m and m + 1 are selected from the uneven structure 101a group (n). Subsequently, the concavo-convex structures 101al and l + 1 that are closest to the structures m and m + 1 are selected from the concavo-convex structure 101a group (n + 1). A region connecting the centers of these structures m, m + 1, l, and l + 1 is defined as a unit cell, and the area of the unit cell is defined as Ac.

2. The concavo-convex structure 101a has a dot shape or a hole shape, and has a regular arrangement or a random arrangement.
FIG. 22B shows a state in which the concavo-convex structure 101a has a dot shape or a hole shape and is arranged in a weak regularity or randomly. In this case, when the average pitch Pav of the concavo-convex structure 101a is smaller than 500 nm, a square of 1 μm × 1 μm is taken in the region having the concavo-convex structure 101a, and this is used as a unit cell. When the average pitch Pav of the concavo-convex structure 101a is 500 nm or more and 1000 nm or less, the square is 2 μm × 2 μm, and when the average pitch Pav of the fine pattern is more than 1000 nm and 1500 nm or less, the square is 3 μm × 3 μm.

3. The uneven structure 101a is a line and space structure.
In FIG. 22C, the concavo-convex structure 101a shows a line and space structure. Each line may be arranged at equal intervals, or the intervals may vary. From these concavo-convex structures 101a, the Nth line and the (N + 1) th line are selected. Subsequently, a line segment of 1 μm is drawn on each of these lines. A square or rectangle formed by connecting the end points of these line segments is defined as a unit cell.

  Note that the arrangement and shape of the uneven structure 101a in FIGS. 21A and 21B do not affect the definition of the unit area (Sc), and the above-described shape can be adopted as the arrangement and shape of the uneven structure 101a.

(Recess volume Vc)
The recess volume (Vc) is defined as the recess volume of the concavo-convex structure 101a existing under the unit area (Sc) as shown in FIGS. 23A and 23B. FIG. 23A and FIG. 23B are diagrams showing the relationship among the concavo-convex structure 101a, the unit area (Sc), and the concave volume (Vc). FIG. 23A is a schematic top view of the concavo-convex structure 101a, and FIG. 23B is a schematic cross-sectional view. As shown in FIG. 23B, when the unit area (Sc) is lowered perpendicularly to the main surface direction of the protective layer 101 (supporting base material (100)), the unit area (Sc) becomes the top of the concavo-convex structure 101a. The volume of the void (concave portion 101c) of the concavo-convex structure 101a that has passed from the intersection to the end of the intersection is the concave portion volume (Vc). Although FIG. 23A and FIG. 23B describe the case where the concavo-convex structure 101a has a hole shape as a representative, the concave volume Vc is defined similarly in the case of a dot shape or a line and space shape. Note that the arrangement and shape of the concavo-convex structure in FIGS. 23A and 23B do not affect the definition of the concave volume (Vc), and the above-described shape can be adopted as the arrangement and shape of the concavo-convex structure.

(Coating thickness hc)
The coating film thickness (hc) is defined as the coating film thickness (wet film thickness) of the dilute solution 102S, but it is difficult to measure the coating film thickness in a state where it is applied to the concavo-convex structure 101a. The film thickness on the flat film surface produced with the material substantially equivalent to the uneven | corrugated structure 101a is defined as a coating film thickness (hc). That is, the film thickness of a film applied on a flat film made of a material substantially the same as or equivalent to the material constituting the concavo-convex structure 101a under the same conditions as the film formation conditions on the concavo-convex structure 101a is defined as the coating film thickness ( hc). The range of the coating film thickness (hc) is not particularly limited because it can be appropriately set so as to satisfy the above formula (4), but from the viewpoint of coating accuracy, it is preferably 0.1 μm or more and 20 μm or less.

(Volume concentration C)
The volume concentration (C) is defined as the volume concentration of the diluted solution 102S of nanoparticle material. When the relationship between the unit area (Sc), the coating film thickness (hc), the volume concentration (C), and the recess volume (Vc) satisfies the above formula (4), the nanoparticles 102 are formed inside the recesses 101c of the uneven structure 101a. Can be placed. From the viewpoint of arrangement accuracy to be arranged inside the concave portion 101c of the concavo-convex structure 101a, Sc · hc · C ≦ 0.9Vc is more preferable, and Sc · hc · C ≦ 0.8Vc is more preferable.

  Hereinafter, although it demonstrates using the specific value of the structure of the uneven structure 101a, coating film thickness (hc), and volume concentration (C), the manufacturing method of this invention is not limited to this.

  24A and 24B show a rounded circle at the tip of the concavo-convex structure 101a having an opening diameter (φ) of 430 nm, a pitch in the x-axis direction of 398 nm, a pitch in the y-axis direction of 460 nm, and a depth (height) of 460 nm. It shows a structure in which columnar recesses are arranged in a hexagonal close-packed arrangement. In this case, the relationship satisfying the above equation (4) can be considered as follows.

  As shown in FIG. 24A, when the unit area (Sc) is set as a hexagonal unit cell, the values of the unit area (Sc) and the recess volume (Vc) are determined and calculated as hc · C <Vc / Sc = 364. Is done. In addition, the volume of the cylindrical recessed part with one rounded tip was defined as 80% of the volume of one cylindrical recessed part. When the coating film thickness (hc) is considered between 1000 nm and 5000 nm, the relationship between the coating film thickness (hc) and the volume concentration (C) can be arranged as shown in FIG. FIG. 25 is a diagram showing the relationship between the coating film thickness (hc) and the volume concentration (C) satisfying hc · C <Vc / Sc = 364, that is, the coating process conditions for the concavo-convex structure 101a shown in FIGS. 24A and 24B. It is. The horizontal axis in FIG. 25 is an axis in which the coating film thickness (hc) is expressed in the dimension nm, and the vertical axis is the volume concentration (C) (vol./vol.). The plot shown in FIG. 25 is a plot that satisfies hc · C = Vc / Sc = 364, and the lower side of the plot (gray portion in FIG. 25) is a condition that can be applied.

  Similarly, for example, a cylindrical recess with a rounded tip with an opening diameter (φ) of 180 nm, a pitch in the x-axis direction of 173 nm, a pitch in the y-axis direction of 200 nm, and a depth (height) of 200 nm is hexagonally close packed. For the concavo-convex structure 101a arranged in an array, the conditions shown in FIG. The horizontal axis in FIG. 26 is an axis in which the coating film thickness (hc) is expressed in the dimension nm, and the vertical axis is the volume concentration (C) (vol./vol.). The plot shown in FIG. 26 is a plot that satisfies hc · C = Vc / Sc = 147, and the lower side of the plot (the gray portion in FIG. 26) is a condition that can be applied.

  Similarly, for example, a cylindrical recess having a rounded tip with an opening diameter (φ) of 680 nm, a pitch in the x-axis direction of 606 nm, a pitch in the y-axis direction of 700 nm, and a depth (height) of 700 nm is hexagonally close packed. For the uneven structure 101a arranged in an array, the conditions shown in FIG. 27 are the coating process of the present invention. The horizontal axis in FIG. 27 is an axis in which the coating film thickness (hc) is expressed in the dimension nm, and the vertical axis is the volume concentration (C) (vol./vol.). The plot shown in FIG. 27 is a plot that satisfies hc · C = Vc / Sc = 599, and the lower side of the plot (gray portion in FIG. 27) is a condition that can be applied.

(Coating pressure)
The pressure related to coating is preferably 1 kPa or more because coating properties including the inside of the concavo-convex structure 101a of the diluted solution 102S of the nanoparticle material are improved. In particular, from the viewpoint of improving the accuracy of filling and arranging the nanoparticles 102 in the concave portion 101c of the concavo-convex structure 101a, the pressure applied to the coating is preferably 10 kPa or higher, preferably 20 kPa or higher, and 100 kPa or higher. Most preferably it is.

(Solvent removal process)
After applying the diluted solution 102S of the nanoparticle material on the concavo-convex structure 101a so as to satisfy the above formula (4) (see FIG. 19B), a nanoparticle inside the concavo-convex 101c of the concavo-convex structure 101a is obtained through a solvent removal step. The particles 102 can be filled, and the first laminate 1 can be manufactured (see FIG. 19C).

  The temperature and time in the solvent removal step are not particularly limited because they can be set as appropriate depending on the vapor pressure and boiling point of the solvent used when preparing the diluted solution 102S of the nanoparticle material, and the coating film thickness (hc). In general, a temperature range of 20 ° C. to 120 ° C. and a time range of 10 seconds to 1 hour is preferable because the arrangement accuracy of the nanoparticles 102 increases. Further, when the boiling point of the solvent used is Ts, it is preferable that the temperature (T) of the solvent removal step includes a solvent removal step (1) that satisfies T <Ts, because the placement accuracy of the nanoparticles 102 is further improved. It is more preferable to satisfy <Ts / 2. Furthermore, it is preferable to include a solvent removal step (2) satisfying T≈Ts after the solvent removal step (1) because the storage stability of the first laminate 1 and the transfer accuracy during use are improved. Note that T≈Ts is approximately T = Ts ± 20%.

  In addition, in the manufacturing process of the 1st laminated body 1, the pre-processing process of the uneven structure 101a may be added before a coating process, and an energy-beam irradiation process may be added after a solvent removal process. That is, in the manufacturing process of the first laminate 1, the pretreatment process, the coating process, and the solvent removal process may be performed in this order, or the coating process, the solvent removal process, and the energy ray irradiation process may be performed in this order. In addition, the pretreatment process, the coating process, the solvent removal process, and the energy beam irradiation process may be performed in this order.

(Pretreatment process)
By passing through the pretreatment process on the surface of the concavo-convex structure 101a of the protective layer 101, the coating property of the diluted solution 102S of the nanoparticle material is kept good. As a result, the arrangement accuracy of the nanoparticles 102 is improved and the first lamination is performed. The transfer accuracy of the nanoparticles 102 when using the body 1 can be improved, which is preferable.

As the pretreatment (1) for obtaining the effect of improving the positional accuracy of the nanoparticles 102, the metal layer described above can be formed. Furthermore, oxygen ashing treatment, plasma treatment, ethishima treatment, UV-O ₃ treatment, alkaline solution treatment, etc. can be performed on the metal layer surface. As a means for forming a metal layer, the above-described method for forming a metal layer can be employed. More specifically, for example, surface coating with a metal alkoxide represented by tetraethoxysilane, silane coupling having an olefin moiety. Surface treatment with a material, dry coating of a metal layer typified by Cr (for example, sputtering), dry coating of a metal oxide layer typified by SiO ₂ (for example, sputtering), or a combination of these Can be mentioned. On the other hand, as the pretreatment (2) for obtaining the effect of improving the transfer accuracy of the nanoparticles 102, the film formation of the release layer described above can be cited. In the pretreatment step, the pretreatment (1) may be followed by a pretreatment (2) step.

(Energy beam irradiation process)
After the solvent removal step, the nanoparticle material is subjected to a step of irradiating energy rays from at least one of the concavo-convex structure 101a surface side (nanoparticle 102 surface side) or the support substrate 100 surface side (second surface 2b side). Is improved, and the transfer accuracy of the nanoparticles 102 is improved when the first laminate 1 is used. Examples of energy rays include X-rays, UV, and IR.

  Furthermore, in the manufacturing process of the 1st laminated body 1, you may add a cover film bonding process. Here, as the cover film, a cover film provided on the surface of the first mask layer 103 in the second laminate 2 can be used. By going through the cover film bonding step, the uneven structure 101a and the nanoparticles 102 can be protected.

  In the manufacturing process of the 1st laminated body 1, a coating process and a solvent with respect to an unwinding process, a pre-processing process, a coating process, a solvent removal process, an energy ray irradiation process, a cover film bonding process, and a winding process. It is possible to include the removal steps in this order and go through two to seven steps from these seven steps in this order.

(Uneven structure and contact angle of protective layer)
The physical properties of the concavo-convex structure 101a used for manufacturing the first laminate 1 are not particularly limited. However, when the contact angle of the water droplet on the surface of the concavo-convex structure 101a is smaller than 90 degrees, the arrangement accuracy of the nanoparticles 102 is improved. Preferably, 70 degrees or less is preferable because this effect can be further exhibited. On the other hand, when the contact angle of water droplets on the surface of the concavo-convex structure 101a is larger than 90 degrees, it is preferable because the transfer accuracy of the nanoparticles 102 when using the manufactured first laminate 1 is improved. It is preferable to have this effect even more.

  It is preferable that the contact angle of water on the surface of the concavo-convex structure 101a is 90 degrees or more because the overlap of the nanoparticles 102 in the film thickness direction of the second stacked body 2 can be reduced. In particular, the contact angle of water on the surface of the concavo-convex structure 101a is 90 degrees or more, an aperture ratio range described below, and an aqueous solvent selected as a solvent for diluting the nanoparticle material, and a coating satisfying the above (2) It is preferable because the overlap between the nanoparticles 102 can be reduced as much as possible.

(Nanoparticle material and diluted solution)
From the viewpoint of the arrangement accuracy of the nanoparticles 102 inside the recesses of the concavo-convex structure 101a, the contact angle of the diluted solution 102S of the nanoparticle material onto the concavo-convex structure 101a is preferably 110 degrees or less, and 90 degrees or less. More preferred. Since it is possible to further exert a capillary force inside the concave portion of the concavo-convex structure 101a, the contact angle of the diluted solution 102S on the concavo-convex structure 101a is preferably 85 degrees or less, and more preferably 80 degrees or less. Preferably, it is most preferably 70 degrees or less.

  Examples of the solvent satisfying such a contact angle range include aqueous solvents. An aqueous solvent means a solvent having a high affinity for water, and examples thereof include alcohols, ethers, and ketones.

  Although it does not specifically limit as the diluted solution 102S, The solvent whose boiling point of a single solvent is 40 to 200 degreeC is preferable, 60 to 180 degreeC is more preferable, and 60 to 160 degreeC is further more preferable. Two or more kinds of diluents may be used. In particular, when two types of solvents are used in combination, the difference in the boiling points of the respective solvents is preferably 10 ° C. or more, more preferably 20 ° C. or more, from the viewpoint of leveling properties of the diluted solution of the nanoparticle material. Further, the selection method considering the influence on the radius of inertia given by the nanoparticles 102 and the solvent is preferable as the selection method of the diluted solution 102S. The contents described above can be adopted as the shape and arrangement of the concavo-convex structure 101a.

  Among them, while satisfying the following aperture ratio, the contact angle of water on the surface of the concavo-convex structure 101a is 75 ° or more, preferably 85 ° or more, most preferably 90 ° or more, and an aqueous solvent for diluting the nanoparticle material. It is preferable to select a solvent and perform coating satisfying the above (2) because the overlap between the nanoparticles 102 can be easily reduced or reduced to zero. Furthermore, when the uneven structure 101a that satisfies the contact angle of water of 90 degrees or more on the surface of the uneven structure 101a is a protective layer that satisfies the above-mentioned range of Es / Eb, the second laminate 2 is continuously accurate. It is preferable because it can be made high and the transferability during use is improved.

When the diluted solution 102S of the nanoparticle material is applied onto the concavo-convex structure 101a and the nanoparticle 102 is filled into the concave portion 101c, the aperture ratio Ar described above (when the concavo-convex structure 101a is dot-like: (( Sc-Sh) / Sc, when the concavo-convex structure 101a has a hole shape; Sh / Sc) preferably satisfies the following formula (5).
Formula (5)
Ar ≧ 0.45

When the aperture ratio Ar satisfies the above formula (5) and the pitch is in the range of 150 nm to 800 nm, the diluted solution 102S of the nanoparticle material can recognize the concavo-convex structure 101a. For this reason, the diluted solution 102S of the nanoparticle material is preferable because it wets and spreads into the concavo-convex structure 101a so as to maximize the radius of curvature of the virtual droplet. The virtual droplet means a droplet of the diluted solution 102S of the nanoparticle material that is assumed to exist inside the concave portion of the concavo-convex structure 101a. In particular, the aperture ratio Ar is preferably 0.50 or more, and more preferably 0.55 or more. Furthermore, the aperture ratio Ar preferably satisfies the following formula (6).
Formula (6)
Ar ≧ 0.65

  When Ar satisfies the above formula (6), in addition to the above effect, a potential from the top of the convex portion 101b of the concave-convex structure 101a to the inside of the concave portion 101c works, and the inside of the concave portion 101c is filled with droplets. It is more preferable because it is possible to prevent the diluted solution 102S of the nanoparticle material from moving again onto the convex portion 101b later. In order to further exhibit the above effect, the aperture ratio Ar is preferably 0.7 or more. More preferably, Ar is 0.75 or more, and more preferably 0.8 or more.

  In particular, the first mask layer 103 is processed from the nanoparticle 102 surface side of the laminate 201 composed of the nanoparticles 102 / first mask layer 103 / object 200, and the object to be processed is provided with the fine mask pattern 202a. From the viewpoint of obtaining 200, the fine pattern of the protective layer 101 is preferably concave.

  Furthermore, if the area of the hole opening is larger than the area of the bottom of the hole, the pinning effect (pinning effect by TPCL) at the solid-liquid interface at the hole end can be easily suppressed, and the above effect can be exerted more. preferable. Furthermore, it is preferable that the opening rod and the side surface of the recess are continuously and smoothly connected, because the above effect can be further exhibited.

  The second laminated body 2 is a second coating step (FIG. 24B) in which a dilute solution 103S of the first mask layer material is coated on the concavo-convex structure 101a including the nanoparticles 102 in the first laminated body 1. And a second solvent removal step (see FIG. 24C) for removing the excess solution to form the first mask layer 103.

(Second coating process)
The coating property of the first mask layer material with the diluted solution 103S is such that the coating film thickness (wet film thickness) of the diluted solution 103S in the coating process is ho and the volume concentration of the diluted solution 103S of the first mask layer material is In the case of Co, there is no particular limitation as long as the following formula (7) is satisfied.
Formula (7)
Sc · ho · Co ≧ Vc

  Here, the coating film thickness (ho) is defined as the coating film thickness of the diluted solution 103S of the first mask layer material. However, the coating film thickness (ho) is a state in which the coating film is applied onto the concavo-convex structure 101a including the nanoparticles 102. Since it is difficult to measure the coating film thickness, the film thickness on a flat film surface made of a material substantially equivalent to the uneven structure 101a is defined as ho. That is, a film of a film that is applied to a flat film made of a material that is substantially the same as or equivalent to the material constituting the concavo-convex structure 101a under the same conditions as the film formation conditions on the concavo-convex structure 101a of the first laminate 1. The thickness is adopted as the coating film thickness (ho).

  The range of the coating film thickness (ho) can be appropriately set so as to satisfy the above formula (7), and is not particularly limited. However, from the viewpoint of coating accuracy, it is preferably 0.1 μm or more and 20 μm or less. .2 um to 10 um is more preferred, most preferably 0.3 um to 2 um. In particular, from the viewpoint of the film formability of the first mask layer 103 on the second laminated body 2 and the bonding property at the time of use, Sc · ho · Co ≧ 1.5Vc is preferable, and Sc · ho -Co ≧ 2Vc is more preferable. A coating method will not be specifically limited if the said Formula (7) is satisfy | filled, The coating method mentioned above is employable.

(Second solvent removal step)
After applying the diluted solution 103S of the first mask layer material on the concavo-convex structure 101a containing the nanoparticles 102 so as to satisfy the above formula (7) (see FIG. 20B), the second solvent removal step is performed. Thus, the first mask layer 103 can be formed over the uneven structure 101a including the nanoparticles 102 (see FIG. 20C).

  The second laminated body 2 includes a second coating step in which the diluted solution 103S of the first mask layer material is coated on the concavo-convex structure 101a including the nanoparticles 102 in the first laminated body 1, and an extra step. It is manufactured by including a second solvent removal step of removing the solution to form the first mask layer 103 at least in this order.

  That is, the second laminate 2 has an unwinding step, a pretreatment step, a coating step, a solvent removal step, an energy ray irradiation step, a cover film bonding step, and a winding step, a coating step and a solvent removal step. And the cover film laminating step and the winding step of the first laminate 1 manufactured through two or more steps from these seven steps in this order, the unwinding step and After passing through the cover film peeling step in this order, the second patterning step and the second solvent removing step are manufactured at least in this order on the fine pattern surface. On the other hand, when there is a cover film bonding step and there is no winding process, after passing through the cover film peeling step, the second coating step and the second solvent removal step are performed on the surface of the concavo-convex structure 101a. It is manufactured through at least this order. Moreover, when there is no cover film bonding process and there is a winding process, the second coating process and the second solvent removal process are performed at least in this order on the fine pattern surface after the unwinding process. It is manufactured after. Furthermore, when there is no cover film bonding process and a winding-up process, it manufactures by passing through a 2nd coating process and a 2nd solvent removal process at least in this order with respect to the uneven structure 101a surface.

  Furthermore, a cover film laminating step for laminating a cover film on the exposed surface of the first mask layer 103 of the second laminate 2 manufactured by any one of the above manufacturing methods is a second solvent removing step. It may be added after. In addition, the cover film mentioned above can be employ | adopted for a cover film. Moreover, you may wind up and collect | recover, after bonding a cover film. The cover film can be taken up without being provided.

[Use of laminate for forming reel-like fine pattern]
Then, the usage method of the 2nd laminated body 2 is demonstrated.
FIG. 7A to FIG. 7F are explanatory views showing the processing steps of the object 200 using the second laminate 2. By performing the following steps (2-1) to (2-5) in order, the second laminated body 2 is used and dry etching is performed, so that the nanoparticles 102 / the first mask layer 103 / the object to be processed. A third laminate composed of 200 can be obtained. By processing the first mask layer 103 from the nanoparticle 102 surface side of the obtained laminate 201, the fine pattern structure 202 provided with the fine mask pattern 202a on the object 200 can be transferred. By using the fine mask pattern 202a of the fine pattern structure 202 as a mask, the workpiece 200 can be processed. FIG. 7A to FIG. 7F are explanatory views showing the processing steps of the object 200 using the second laminate 2.
Process (2-1): The process of bonding the to-be-processed object 200 and the 1st mask layer 103 by thermocompression bonding (refer FIG. 7A).
Step (2-2): A step of irradiating energy rays from at least one of the protective layer 101 surface side or the target object 20 surface side. (See FIG. 7B).
Process (2-3): The process of peeling the protective layer 101 and obtaining the laminated body 201 (refer FIG. 7C).
Step (2-4): Step of forming the fine pattern structure 202 having the fine mask pattern 202a composed of the nanoparticles 102 and the first mask layer 103 by performing etching from the nanoparticle 102 surface side of the laminate 201. (See FIG. 7D).
Step (2-5): A step of etching the workpiece 200 using the fine mask pattern 202a obtained in the step (2-4) as a mask (see FIG. 7E).

  In addition, before a process (2-1), a hard mask layer may be formed on the to-be-processed object 200, and a process (2-1)-a process (2-4) may be performed sequentially after that. In this case, after the step (2-4), the hard mask layer can be etched using the fine mask pattern 202a composed of the nanoparticles 102 and the first mask layer 103 as a mask. By treating the fine mask pattern 202a composed of the nanoparticles 102 and the first mask layer 103 and the etched hard mask layer (hard mask pattern) as a mask, the object 200 can be processed. Alternatively, after the etching of the hard mask layer, the fine pattern composed of the remaining nanoparticles 102 and the first mask layer 103 is removed, and only the etched hard mask layer is regarded as a mask, and the object 200 is processed. be able to. Either dry etching or wet etching can be employed as an etching method for the object to be processed 200.

  The thermocompression bonding temperature in the step (2-1) is preferably 40 ° C. or higher and 300 ° C. or lower, more preferably 50 ° C. or higher and 200 ° C. or lower, and most preferably 80 ° C. or higher and 150 ° C. or lower. In particular, it is preferable that the temperature of the surface on which the first mask layer of the object to be processed satisfies the above range because the bonding property and the transfer property are improved. The thermocompression bonding may be performed by heating only the target object 200 or by heating the entire system surrounding the target object 200 and the second laminate 2. In particular, from the viewpoint of transfer accuracy, it is preferable to heat the workpiece 200 and perform thermocompression bonding.

  Further, in the step (2-1), the first mask layer 103 and the target object 200 are bonded together while peeling the cover film of the second laminate 2, or after the cover film is peeled off. It is preferable that the first mask layer 103 of the second stacked body 2 and the object to be processed 200 be bonded by a laminate roll provided on the upper portion of the second stacked body 2 in a manner of bonding.

  The temperature of the laminating roll is preferably 50 to 150 ° C., and the laminating speed is preferably 0.1 [m / min] to 6 [m / min]. The pressure is preferably 0.01 [Mpa / cm] to 1 [Mpa / cm], preferably 0.1 [Mpa / cm] to 1 [Mpa / cm] as the pressure per unit length of the laminate roll. .2 [Mpa / cm] to 0.5 [Mpa / cm] is more preferable.

  As a laminator, a single-stage laminator that uses one set of laminate rolls on the upper part of the second laminate 2, a multi-stage laminator that uses two or more sets of laminate rolls, and the part to be laminated is sealed in a container and then depressurized with a vacuum pump Alternatively, a vacuum laminator for making a vacuum is used. A vacuum laminator is preferable in order to suppress air mixing during lamination.

  The energy source of the step (2-2) can be appropriately selected depending on the nanoparticle material and the first mask layer material. For example, when the interface between the nanoparticle 102 and the first mask layer 103 forms a chemical bond by thermal polymerization, the step (2-2) can be performed by applying thermal energy. Application of thermal energy can be performed by heating infrared rays from both the second laminate 2 surface side and the to-be-processed object 200 surface side, even when the entire second laminate 2 bonded to the object 200 is heated. You may irradiate from either one. When the 2nd laminated body 2 does not contain a polymeric substance, a process (2-2) does not need to be performed. Moreover, even if it is a case where the 2nd laminated body 2 contains a polymeric substance, a process (2-2) can be skipped. When at least one of the first mask layer 103 and the nanoparticles 102 contains a curable substance, the first mask layer 103 of the second laminate 2 and the target object 200 are bonded together and / or It is preferable to promote curing in the state of the laminate 201. When the curing is photopolymerization, it is preferable to irradiate at least energy rays. When a photopolymerizable substance is contained, in particular, after the first mask layer 103 of the second laminate 2 and the object to be processed 200 are bonded together as in the step (2-2), the protective layer It is preferable to irradiate energy rays from at least one of 101 or 200. On the other hand, when the curing is thermal polymerization, it is preferable to perform at least heating. As described above, when the second laminated body 2 contains a curable substance, if the curing is promoted before the target object 200 is processed using the first mask layer 103 as a processing mask, the processing of the target object 200 is performed. Accuracy can be improved. In particular, when the glass transition temperature is present in the first mask layer 103, the glass transition temperature is increased by promoting the curing of the first mask layer 103, so that the processing accuracy of the workpiece 200 is improved. Can do.

In addition, the step (2-2) can be simultaneously performed by adjusting the temperature of the step (2-1) and the bonding (crimping) speed. For example, when the interface between the nanoparticle 102 and the first mask layer 103 is in photopolymerization and forms a chemical bond, the step (2-2) can be performed by applying light energy. The light energy can be appropriately selected from a light source including a wavelength suitable for the photopolymerization initiator contained in the nanoparticles 102 and the first mask layer 103. Light energy typified by UV light can be irradiated from both or one of the second laminate 2 surface side and the object 200 surface side. In addition, when either one of the 2nd laminated body 2 or the to-be-processed object 200 is optical energy impermeable, it is preferable to irradiate from the optical energy transparent body side. Here, the light source for light irradiation can be appropriately selected depending on the composition of the nanoparticles 102 and the first mask layer 103, and is not particularly limited. However, a UV-LED light source, a metal halide light source, a high-pressure mercury lamp light source, or the like can be employed. Further, the integrated light quantity of until after irradiated from the start of irradiation with ^light, when a range of ^{500mJ / cm 2 ~5000mJ / cm 2} , preferably for improving the transfer accuracy. More ^{preferably 800mJ / cm 2 ~2500mJ / cm 2} . Further, the light irradiation may be performed by a plurality of light sources.

  In addition, you may add a heating process and a cooling process between a process (2-2) and a process (2-3). By adding a heating step, the stability of the nanoparticles 102 and the first mask layer 103 can be improved, and the peelability of the protective layer 101, which is good for adding a cooling step, is improved. The heating temperature is preferably 30 ° C to 200 ° C. Cooling is preferably performed so that at least the temperature of the object to be processed 200 is 120 ° C. or lower because the peelability can be improved. In particular, 5 ° C. or more and 60 ° C. or less are preferable, and 18 ° C. or more and 30 ° C. or less are more preferable.

  The method of the step (2-3) is not particularly limited, but it is preferable to fix the target object 200 and peel the protective layer 101 from the viewpoint of transfer accuracy and reproducibility. Such peeling in a state where the object to be processed 200 is fixed can reduce stress concentration on the nanoparticles 102 to which the shape of the fine pattern is transferred.

  In addition, you may add both or both of a light energy irradiation and a heating process between a process (2-3) and a process (2-4). Depending on the composition of the nanoparticles 102, the reaction may still be able to proceed after the fine pattern is peeled off. In this case, the nanoparticles can be irradiated by irradiating light energy typified by UV light from either the nanoparticle 102 surface side and / or the target object 200 surface side, or by heating or irradiating infrared rays. The reaction of 102 can be promoted, and the shape of the fine pattern after the step (2-4) is stabilized.

Here, the light source for light irradiation can be appropriately selected depending on the composition of the nanoparticles 102 and the first mask layer 103, and is not particularly limited. However, a UV-LED light source, a metal halide light source, a high-pressure mercury lamp light source, or the like can be employed. Further, the integrated light quantity of until after irradiated from the start of irradiation with ^light, when a range of ^{500mJ / cm 2 ~5000mJ / cm 2} , preferably for improving the transfer accuracy. More ^{preferably 800mJ / cm 2 ~2500mJ / cm 2} . Further, the light irradiation may be performed by a plurality of light sources.

  The etching in the step (2-4) may be dry etching or wet etching. However, dry etching is preferable because the first mask layer 103 is preferably etched anisotropically.

  In the step (2-5), etching is performed until the first mask layer 103 disappears or the first mask layer 103 is left, depending on the shape of the fine pattern 220 to be formed on the object 200. You can choose to end. In particular, when it is desired to design the tip of the fine pattern 220 formed on the object 200 to be acute, it is preferable to perform etching until the first mask layer 103 is eliminated. When it is desired to design the cross-sectional shape of the pattern 220 to be trapezoidal, the etching is preferably finished with the first mask layer 103 left.

  In the latter case, it is preferable to add a peeling step after the step (2-5). In the peeling process, conditions and methods can be appropriately selected depending on the composition of the first mask layer 103, but by designing the first mask layer 103 to a composition that can be developed with an alkali, peeling with an alkaline solution can be easily performed. . In the former case, it is preferable to add a washing step after the step (2-5). By the etching in the step (2-5), the gas component used for the etching may be doped into the region of the surface layer of several nm to several tens of nm of the workpiece 200. In order to peel off these layers, it is preferable to wash with an alkali or acid solution.

<Semiconductor light emitting device>
Next, with reference to FIG. 28, a semiconductor light emitting element using the target object 200 manufactured using the above-described second stacked body 2 will be described. FIG. 28 is a schematic cross-sectional view of a semiconductor light emitting element 40 using a target object 200 manufactured using the second stacked body 2. FIG. 28 shows an example in which a fine pattern 41 a is provided on the sapphire substrate 41 as the object to be processed 200 using the second stacked body 2. Here, an LED element will be described as a semiconductor light emitting element. In addition, the to-be-processed object 200 produced using the 2nd laminated body 2 mentioned above is not limited to an LED element, It can apply to various semiconductor light-emitting elements.

  As the sapphire substrate 41, for example, a 2 inch φ sapphire substrate, a 4 inch φ sapphire substrate, a 6 inch φ sapphire substrate, an 8 inch φ sapphire substrate, or the like can be used. In the case of a sapphire substrate having a size of 8 inches φ or more, since the warpage after the semiconductor crystal layer is formed becomes large, a Si wafer can be used. In this case, the Si wafer is finally removed.

  As shown in FIG. 28, the semiconductor light emitting device 40 includes an n-type semiconductor layer 42, a light-emitting semiconductor layer 43, and a p-type semiconductor layer sequentially stacked on a fine pattern 41a provided on one main surface of the sapphire base 41. 44, an anode electrode 45 formed on the p-type semiconductor layer 44, and a cathode electrode 46 formed on the n-type semiconductor layer 42. As shown in FIG. 28, the semiconductor light emitting device 40 has a double hetero structure, but the stacked structure of the light emitting semiconductor layer 43 is not particularly limited. In addition, a buffer layer (not shown) can be provided between the sapphire substrate 41 and the n-type semiconductor layer 42.

  By using the sapphire substrate 41 having such a fine pattern 41a on the surface and manufacturing a semiconductor light emitting device, the external quantum efficiency can be improved according to the fine pattern 41a, and the efficiency of the semiconductor light emitting device is improved. To do. In particular, when the pitch of the fine pattern is 100 nm to 500 nm and the height of the fine pattern is about 50 nm to 500 nm, the crystallinity of the semiconductor light emitting layer can be improved, more specifically, the number of dislocations can be greatly reduced. Efficiency can be improved. Further, it is estimated that the light extraction efficiency can be improved at the same time by making the arrangement into a structure with disordered periodicity. Thereby, the external quantum efficiency is greatly improved. Furthermore, by forming a dot shape that has a regular arrangement at the nanoscale and has a large microscale periodicity, and a modulation having a microscale period added to the pitch, the above-described effect is further enhanced and the efficiency is increased. It is considered that a semiconductor light emitting device can be manufactured.

  Examples performed to confirm the effects of the present invention will be described below.

The symbols used in the following description have the following meanings.
・ DACHP: Fluorine-containing urethane (meth) acrylate (OPTOOL DAC HP (manufactured by Daikin Industries))
M350: trimethylolpropane (EO-modified) triacrylate (M350, manufactured by Toagosei Co., Ltd.)
・ I. 184 ... 1-hydroxycyclohexyl phenyl ketone (Irgacure (registered trademark) 184, manufactured by BASF)
・ I. 369 ... 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Irgacure (registered trademark) 369, manufactured by BASF)
-TTB: Titanium (IV) tetrabutoxide monomer (Wako Pure Chemical Industries, Ltd.)
SH710: Phenyl-modified silicone (Toray Dow Corning)
・ 3APTMS ... 3-acryloxypropyltrimethoxysilane (KBM5103 (manufactured by Shin-Etsu Silicone))
DIBK: diisobutyl ketone MEK: methyl ethyl ketone MIBK: methyl isobutyl ketone DR833: tricyclodecane dimethanol diacrylate (SR833 (manufactured by SARTOMER))
SR368 ... Tris (2-hydroxyethyl) isocyanurate triacrylate (SR833 (manufactured by SARTOMER)

(Examples 1-5)
In the following examination, first, (1) a cylindrical master mold was prepared, and (2) a light transfer method was applied to the cylindrical master mold to prepare a reel-shaped resin protective layer. (3) Thereafter, a nanoparticle and a first mask layer were formed on the reel-shaped resin protective layer, respectively, to produce a fine pattern-forming laminate (second laminate). Subsequently, (4) using the second laminate, forming a mask on the optical substrate, and performing dry etching through the obtained mask, an optical substrate having a concavo-convex structure on the surface Produced. Finally, (5) using the obtained optical base material provided with the fine pattern, a semiconductor light emitting device was produced.

(1) Production of cylindrical master mold An uneven structure was formed on the surface of cylindrical quartz glass by a direct drawing lithography method using a semiconductor laser. First, a resist layer was formed on the surface of the cylindrical quartz glass by a sputtering method. The sputtering method was carried out using φ3 inch CuO (containing 8 atm% Si) as a target (resist layer) with a power of RF 100 W to form a 20 nm resist layer. Subsequently, the surface of the resist layer was exposed once using a semiconductor laser having a wavelength of 405 nm while rotating the cylindrical quartz glass. Subsequently, a laser beam having a wavelength of 405 nm was pulse-irradiated to the resist layer once exposed. Next, the resist layer after exposure was developed. The development of the resist layer was performed for 240 seconds using a 0.03 wt% glycine aqueous solution. Next, using the developed resist layer as a mask, the etching layer (quartz glass) was etched by dry etching. Dry etching was performed using SF ₆ as an etching gas under the conditions of a processing gas pressure of 1 Pa, a processing power of 300 W, and a processing time of 5 minutes. Finally, only the resist layer residue was peeled off from the cylindrical quartz glass having a concavo-convex structure on its surface using hydrochloric acid having a pH of 1. The peeling time was 6 minutes.

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

(2) Production of reel-shaped resin protective layer Using the produced cylindrical master mold as a mold, the optical nanoimprint method was applied to continuously produce a reel-shaped resin protective layer G1. Subsequently, a reel-shaped resin protective layer G2 was continuously obtained by an optical nanoimprint method using the reel-shaped resin protective layer G1 as a template.

The material 1 shown below was applied to the easy-adhesion surface of PET film A-4100 (manufactured by Toyobo Co., Ltd .: width 300 mm, thickness 100 μm) by microgravure coating (manufactured by Yurai Seiki Co., Ltd.) to a coating film thickness of 2 μm. . Next, the PET film coated with the material 1 is pressed against the cylindrical master mold with a nip roll so that the integrated exposure amount under the center of the lamp is 1500 mJ / cm ^{2 at} 25 ° C. and 60% humidity in the air. In addition, a UV-irradiated UV exposure apparatus (H bulb) manufactured by Fusion UV Systems Japan Co., Ltd. was used to irradiate ultraviolet rays, and continuous photocuring was performed. 200 m in width and 300 mm in width).

  Next, the reel-shaped resin protective layer G1 was regarded as a template, and the optical nanoimprint method was applied to continuously produce the reel-shaped resin protective layer G2.

Material 1 was applied to an easy-adhesion surface of PET film A-4100 (manufactured by Toyobo Co., Ltd .: width 300 mm, thickness 100 μm) by microgravure coating (manufactured by Yurai Seiki Co., Ltd.) so as to have a coating film thickness of 2 μm. Next, the PET film coated with the material 1 is pressed against the concavo-convex structure surface of the reel-shaped resin protective layer G1 with a nip roll (0.1 MPa), and the atmosphere is at a temperature of 25 ° C. and a humidity of 60% under the center of the lamp. The UV exposure apparatus (H bulb) manufactured by Fusion UV Systems Japan Co., Ltd. is used to irradiate ultraviolet rays so that the integrated exposure amount is 1200 mJ / cm ^2, and photocuring is continuously performed. A plurality of transferred reel-shaped resin protective layers G2 (length 200 m, width 300 mm) were obtained.
Material 1 ... DACHP: M350: I. 184: I.D. 369 = 17.5 g: 100 g: 5.5 g: 2.0 g

  The reel-shaped resin protective layer G2 was cut out and observed with a scanning electron microscope. The uneven structure of the reel-shaped resin protective layer G2 was a hole-shaped structure in which a plurality of recesses were provided at the intersections of the triangular lattice. The average pitch was 300 nm, the average aperture diameter was 280 nm, the average aperture ratio was 79%, and the average recess depth was 300 nm. Moreover, the opening diameter of the recessed part was larger than the diameter of the recessed part bottom part, and the recessed part side surface had the inclination. Furthermore, the convex part top part and the concave part side part were the structures connected smoothly smoothly.

(3) Production of Fine Pattern Formation Laminate (Second Laminate) A diluted liquid of the following material 2 is applied to the concavo-convex structure surface of the reel-shaped resin protective layer G2 to produce a first laminate. did. Subsequently, a dilution liquid of the following material 3 was applied on the concavo-convex structure surface of the reel-shaped resin protective layer G2 enclosing the material 2 in the concavo-convex structure to obtain a second laminate.
Material 2 ... TTB: 3APTMS: SH710: I. 184: I.D. 369 = 65.2 g: 34.8 g: 5.0 g: 1.9 g: 0.7 g
Material 3 ... Binding polymer: SR833: SR368: I.I. 184: I.D. 369 = 77.1 g: 11.5 g: 11.5 g: 1.47 g: 0.53 g
Binding polymer: Methyl ethyl ketone solution of binary copolymer of 80% by mass of benzyl methacrylate and 20% by mass of methacrylic acid (solid content 50%, weight average molecular weight 56000, acid equivalent 430, dispersity 2.7)

  (2) Using a device similar to the production of the reel-shaped resin protective layer, the material 2 diluted with PGME was directly coated on the concavo-convex structure surface of the reel-shaped resin protective layer G2. Here, the dilution concentration was set such that the solid content contained in the coating raw material per unit area (material 2 diluted with PGME) was smaller than the volume of the concavo-convex structure per unit area. The concentration of the diluted solution was changed in the range of 1% by weight to 7% by weight with the apparatus driving conditions for coating being constant. After the coating, it was passed through a 95 ° C. blast drying oven for 5 minutes, and the first laminated body containing the material 2 inside the concavo-convex structure was wound and collected.

  When the first laminate was cut out and cross-sectional observation was performed using a scanning electron microscope, the recess 2 of the reel-shaped resin protective layer G2 was filled with the material 2, that is, the inside of the recess of the reel-shaped resin protective layer G2. It was observed that nanoparticles were formed. Moreover, it was confirmed that no nanoparticles were formed on the top of the convex portion of the reel-shaped resin protective layer G2 by using a transmission electron microscope and energy dispersive X-ray spectroscopy in combination. The size of the nanoparticles changed depending on the dilution concentration of the material 2. From Example 1 to Example 5, the average height of the nanoparticles was 30 nm, 50 nm, 100 nm, 150 nm, and 250 nm. Moreover, the nanoparticles did not overlap each other in the film thickness direction of the first laminate. Further, the shape of each nanoparticle was such that the top diameter on the reel-shaped resin protective layer G2 side was smaller than the diameter on the surface side where the nanoparticle was exposed.

  Subsequently, the first laminate was unwound and the material 3 diluted with PGME and MEK was directly applied onto the concavo-convex structure surface using a die coater. The dilution concentration was 3% by weight. After coating, the film was passed through an air-drying oven at 85 ° C. for 5 minutes, and the cover film was aligned with the surface of the material 3 and wound up and collected. In the case of Example 1, Example 3, and Example 4, the cover film was not used and was wound up and collected. On the other hand, in Example 2 and Example 5, the surface roughness of the 1st mask layer surface of a 2nd laminated body is controlled by controlling the pressure and temperature at the time of bonding the kind of cover film, and a cover film. Three types of samples with different Ra were prepared.

  The 2nd laminated body was cut | disconnected and cross-sectional observation was performed using the transmission electron microscope. The arrangement of the nanoparticles with respect to the reel-shaped resin protective layer G2 was the same as in the case of the first laminate. The distance (lor) between the top position (Spt) on the first surface side of the nanoparticles and the surface of the first mask layer is 370 nm, 350 nm, 300 nm, 250 nm, and 150 nm from Example 1 to Example 5. Thus, it was confirmed that lor / Pav (average pitch) was 1.23, 1.17, 1.00, 0.83, and 0.5. The average position on the surface of the first mask layer was arbitrarily selected from 15 points from the cross-sectional observation image, and was used as the average position.

  For the samples of Example 2 and Example 5, atomic force microscope analysis was performed on the surface of the first mask layer, and the surface roughness Ra was calculated.

(Comparative Example 1)
Titanium oxide fine particles having an average primary particle size of 25 nm were added to isopropyl alcohol, and the mixture was dispersed by applying ultrasonic waves for 30 minutes while being heated to 60 ° C. The obtained liquid was used as a nanoparticle diluent, and the coating film thickness was 2 μm by microgravure coating (manufactured by Yasui Seiki Co., Ltd.) on the PET surface of PET film A-4100 (Toyobo Co., Ltd .: width 300 mm, thickness 100 μm). It applied so that it might become. Subsequently, the inside of a 85 degreeC drying furnace was passed over 5 minutes, and the PET reel which comprises a nanoparticle was obtained.

  Next, the material 3 diluted with PGME and MEK was directly applied to the nanoparticle surface side of the PET reel including the nanoparticles using a die coater. The dilution concentration was 3% by weight. After coating, the film was passed through an air-drying oven at 85 ° C. for 5 minutes, and the cover film was aligned with the surface of the material 3 and wound up and collected.

(Comparative Example 2)
Titanium oxide fine particles having an average primary particle size of 25 nm were added to material 3 and ultrasonic waves were applied for 30 minutes at a temperature of 60 ° C. to disperse the fine particles. The obtained liquid was applied on the PET surface of PET film A-4100 (manufactured by Toyobo Co., Ltd .: width 300 mm, thickness 100 μm) by microgravure coating (manufactured by Yurai Seiki Co., Ltd.) so as to have a coating film thickness of 2 μm. Next, it was passed through a drying furnace at 85 ° C. for 5 minutes and wound up and collected.

  The details of the samples prepared in Examples 1 to 5 and Comparative Examples 1 and 2 described above are summarized in Tables 1 to 9.

  Table 1 shows the average height of the nanoparticles, the distance (lor) between the average edge position (Spt) on the first surface side of the nanoparticles and the first surface, and the average pitch (Pav) in the central surface of the nanoparticles. The ratio (lor / Pav) is summarized in a table. These values were obtained from cross-sectional observation images using a scanning electron microscope.

  Tables 2 to 8 show changes in the number of nanoparticles (described as “number” in the table) according to the distance from the center plane (described as “distance” in the table). In Table 2, the case of counting in the second surface direction (protective layer direction) with reference to “center surface” is described in “column to the left of center surface” in the table. The moving distance from the center plane was “minus Xnm”. On the other hand, the case of counting in the first surface direction (first mask layer direction) with reference to the “center surface” is described in “column to the right of the center surface” in the table. The moving distance from the center plane was “plus Xnm”.

  Table 9 relates to the second laminated body of Example 2 and Example 5, the surface roughness Ra of the first mask layer, the surface roughness Ra, and the average edge position on the first surface side of the nanoparticles It is the table | surface which showed ratio (Ra / lor) of the distance (lor) of (Spt) and the 1st surface.

  No. in Table 9 2a and no. The sample of 5a is a case where the second laminate 2 is manufactured without using a cover film. That is, this is a case where the surface opposite to the concave-convex structure of the PET film, which is the support substrate, functions as a protective layer for the first mask layer. No. 2b and no. The sample of 5b is a case where a COP film is used as a cover film. No. Samples 2c and 5c are obtained when an LDPE (low density polyethylene) film is selected as the cover film. No. 2a is a case where the temperature at the time of winding up the 2nd laminated body 2 is 24 degreeC. No. 2b and no. 2c is a case where the temperature at the time of matching a cover film with a 2nd laminated body is 24 degreeC. No. 5a is a case where the temperature at the time of winding a 2nd laminated body is 45 degreeC. No. 5b and no. 5c is a case where the temperature at the time of matching a cover film with a 2nd laminated body is 45 degreeC.

(4) Test 1: Workability Using the samples prepared in Examples 1 to 5 and Comparative Examples 1 and 2, workability was confirmed.

A sapphire substrate was selected as the workpiece. The sapphire substrate was subjected to UV-O3 treatment for 5 minutes to remove surface particles and to make it hydrophilic. Then, the 1st surface (surface on the opposite side to a protective layer) of the 2nd laminated body was bonded with respect to the sapphire base material. At this time, the sapphire substrate was bonded in a state heated to 105 ° C. Subsequently, using a high-pressure mercury lamp light source, light was irradiated through the sapphire substrate so that the integrated light amount was 1200 mJ / cm ² . Thereafter, the reel-shaped resin protective layer G2 was peeled off.

  Etching using oxygen gas was performed on the obtained laminate. Oxygen etching was performed under conditions of pressure 1 Pa and power 300 W.

The sapphire substrate after oxygen ashing was analyzed using an optical microscope and an atomic force microscope. The analysis results are summarized in Table 10. In addition, the definition of the symbol of Table 10 is as follows.
“◎”: A pattern similar to the average pitch of the nanoparticles of the second laminate is formed on the sapphire substrate after ashing, and when the 100 patterns are arbitrarily selected, the defect rate is When it was 5% or less.
“◯”: On the sapphire substrate after ashing, a pattern similar to the average pitch of the nanoparticles of the second laminate is formed, and when 100 patterns are arbitrarily selected, the defect rate is When it is more than 5% and 10% or less.
“Δ”: A pattern similar to the average pitch of the nanoparticles of the second laminate is formed on the sapphire substrate after ashing, and the defect rate is determined when 100 patterns are arbitrarily selected. When it is more than 10% and 20% or less.
“×”: A pattern similar to the average pitch of the nanoparticles of the second laminated body is formed on the sapphire substrate after ashing, and the defect rate is determined when 100 patterns are arbitrarily selected. When it is more than 20%, or when a pattern different from the average pitch of the nanoparticles of the second laminate by 10% or more is formed on the sapphire substrate after ashing.

  First, in Examples 1 to 5, it was confirmed that the first mask layer could be etched using nanoparticles as a mask in all samples. This is because, as can be seen from Tables 2 to 5, in the second laminates of Examples 1 to 5, there are no nanoparticles overlapping each other in the film thickness direction of the second laminate. More specifically, when the nanoparticles overlap each other, the etching of the first mask layer is started after the overlapping nanoparticles are removed. That is, the non-overlapping part of the nanoparticles is etched in advance. Moreover, it was confirmed that the reason why the accuracy of Example 1 is slightly inferior to the accuracy of Examples 2 to 4 is due to the uneven shape of the nanoparticles arranged inside the concavo-convex structure of the protective layer. The spot in this case is a state in which, when one nanoparticle is observed, a depressed portion or a through-hole is partially in the nanoparticle. On the other hand, the reason why the accuracy of Example 5 is slightly inferior to the accuracy of Examples 2 to 4 is that the nanoparticles arranged inside the concavo-convex structure of the protective layer are disturbed in the shape of the ridges on the first surface side. confirmed. That is, when the protective layer is viewed from the center, the nanoparticles are partially deposited on the side surface of the concave portion of the concave-convex structure of the protective layer.

  Next, in Comparative Example 1, it was confirmed that the first mask layer was hardly processed. As can be seen from Table 7, in Comparative Example 1, the nanoparticles are overlapped in the film thickness direction of the second laminate. That is, since the time for removing the overlapping nanoparticles and the time for etching the first mask layer existing between the nanoparticles are greatly different, the first mask layer is etched even when the first mask layer is etched. The trunk of one mask layer becomes extremely thin and falls down.

  In Comparative Example 2, when the wording is unified in the second laminate, the nanoparticles are dispersed in the first mask layer. For this reason, lor / Pav in Table 1 is 0, and as can be seen from Table 8, the nanoparticles overlap in the film thickness direction of the second laminate. In particular, the difference from Comparative Example 1 is that nanoparticles are dispersed throughout the first mask layer. Therefore, when attention is paid to a certain nanoparticle, removal of the nanoparticle, etching of the first mask layer by oxygen ashing, Removal of nanoparticles and etching of the first mask layer are repeated.

  From the above, it can be seen that the first mask layer can be processed with high processing accuracy by providing the nanoparticles so as to decrease in the film thickness direction of the second laminate from the center surface. Further, in this embodiment, high processing accuracy of the first mask layer is expressed when lor / Pav is in the range of 0.50 to 1.23, and the processing accuracy is more preferably 0.83 to 1.17. It was confirmed to improve.

(5) Test 2: Transferability In order to investigate the influence of the surface roughness Ra of the first mask layer using the samples shown in Table 9, transferability was confirmed.

A safa eye base material was selected as the object to be treated. The sapphire substrate was subjected to UV-O3 treatment for 5 minutes to remove surface particles and to make it hydrophilic. Then, the 1st surface (surface on the opposite side to a protective layer) of the 2nd laminated body was bonded with respect to the sapphire base material. At this time, the sapphire substrate was bonded in a state heated to 105 ° C. Subsequently, using a high-pressure mercury lamp light source, light was irradiated through the sapphire substrate so that the integrated light amount was 1200 mJ / cm ² . Thereafter, the reel-shaped resin protective layer G2 was peeled off. The results are summarized in Table 11. In addition, the symbol of Table 11 has the following meaning.
A: When the nanoparticles and the first mask layer are transferred and applied at a ratio of 90% or more in the sapphire substrate surface.
O: When the nanoparticles and the first mask layer are transferred and applied at a ratio of 70% or more and less than 90% in the sapphire substrate surface.
Δ: When the nanoparticles and the first mask layer are transferred and applied at a ratio of 45% or more and less than 70% within the surface of the sapphire substrate.
X: When the transfer ratio of the nanoparticles and the first mask layer in the sapphire substrate surface is 20% or less.

  From the above, it can be seen that as Ra / lor is smaller, the transfer accuracy is improved. This is probably because Ra / lor is small because the fluidity at the time of bonding of the first mask layer is improved and the air environment escapes at the time of bonding. In particular, when the surface roughness Ra of the first mask layer is 40 nm or less, the transferability is further improved, and when it is 20 nm or less, the nanoparticles and the first mask layer are transferred onto almost the entire surface of the sapphire substrate. It was confirmed that it was possible.

(6) Processing of sapphire Finally, it was confirmed whether the sapphire substrate could be nano-processed. The 2nd laminated body used is Example 1, 2a, 3, 4, 5a. All the usage methods were the same. First, (4) Test 1: Similar to workability, ashing was performed, and a fine mask pattern having a high aspect ratio composed of nanoparticles and the first mask layer was formed on the object to be processed.

  Subsequently, reactive ion etching using BCl 3 gas was performed from the material 2 (nanoparticle) surface side to nano-process sapphire. Etching was performed at ICP: 150 W, BIAS: 50 W, and pressure 0.2 Pa, and a reactive ion etching apparatus (RIE-101iPH, manufactured by Samco Corporation) was used.

  Finally, it was washed with a solution in which sulfuric acid and hydrogen peroxide solution were mixed at a weight ratio of 2: 1 to obtain a sapphire substrate having a concavo-convex structure on the surface.

  It was observed that a plurality of substantially conical convex portions were arranged apart from each other on the sapphire substrate. It was also confirmed that a flat surface was formed at the bottom of the recess. Moreover, it was confirmed that the contour shape is not a perfect circle but slightly distorted. Furthermore, the inclination angle of the convex side surface of the substantially conical convex portion changed in two stages.

  In particular, it was confirmed that the diameter of the convex bottom portion of the fine pattern on the sapphire substrate was increased in the order of Examples 1, 2a, 3, 4, 5a. This is because the diameter of the nanoparticles of the second laminate on the first mask layer side increases in the order of Examples 1, 2, 3, 4, and 5a. This means that the processing accuracy of the mask layer 1 and the processing accuracy of the object to be processed are high.

  The present invention has the effect of realizing a laminate for forming a fine pattern that can easily form a fine pattern with a thin residual film or no residual film in order to form a fine pattern with a high aspect ratio on a desired object. In particular, it can be suitably applied as an optical member for a semiconductor light emitting device and a method for producing the same. Moreover, the obtained fine pattern can be used as a water-repellent film, a hydrophilic film, and an adhesive tape.

1 1st laminated body (1st laminated body for fine pattern formation)
2 2nd laminated body (2nd laminated body for fine pattern formation)
DESCRIPTION OF SYMBOLS 10,101 Protective layer 11,101a Uneven structure 12,102 Nanoparticle 13,103 1st mask layer 20,200 To-be-processed object 22,220 Fine pattern 100 Support base material

Claims (8)

For forming a fine pattern, which has a first surface and a second surface that are substantially parallel to each other, and is used to form a fine pattern on an object to be processed via a first mask layer provided on the first surface side. A laminate,
A protective layer; a plurality of nanoparticles functioning as a mask during processing of the first mask layer provided on the protective layer; and the first mask layer provided to cover the plurality of nanoparticles; , And
The nanoparticle has a virtual plane substantially parallel to the central plane when the virtual plane having the maximum number of nanoparticles crossing the plane substantially parallel to the first plane and the second plane is a central plane. A laminate for forming a fine pattern, wherein the number of the nanoparticles traversing is arranged so as to decrease with increasing distance from the center plane. The average pitch (Pav) in the central plane of the plurality of nanoparticles, and the distance (lor) between the average end position (Spt) on the first surface side of the plurality of nanoparticles and the first surface And the ratio (lor / Pav) satisfies the following formula (1): The laminate for forming a fine pattern according to claim 1.
Formula (1)
0.05 ≦ lor / Pav ≦ 10 The ratio (Vo1 / Vm1) between the etching rate (Vm1) of the nanoparticles by dry etching and the etching rate (Vo1) of the first mask layer satisfies the following formula (2): A laminate for forming a fine pattern as described.
Formula (2)
3 ≦ Vo1 / Vm1 The ratio (Vo2 / Vi2) between the etching rate (Vi2) of the object to be processed by dry etching and the etching rate (Vo2) of the first mask layer satisfies the following formula (3): 3. A laminate for forming a fine pattern according to 3.
Formula (3)
Vo2 / Vi2 ≦ 3   The shapes of the plurality of nanoparticles are asymmetric with respect to the center plane, and are non-axisymmetric with respect to a line segment in a direction parallel to the center plane in a cross-sectional view perpendicular to the center plane. The laminate for forming a fine pattern according to any one of claims 1 to 4, wherein the laminate is line symmetric with respect to a line segment in a vertical direction.   The laminate for forming a fine pattern according to claim 5, wherein the protective layer has a concavo-convex structure on a surface thereof, and the plurality of nanoparticles are disposed inside the concave portion of the concavo-convex structure.   The laminate for forming a fine pattern according to any one of claims 1 to 6, wherein an object to be processed is further provided on the first mask layer.   The laminate for forming a fine pattern according to any one of claims 1 to 7, wherein the object to be processed is any one of sapphire, silicon, ITO, ZnO, SiC, a nitride semiconductor, or spinel. .