JP2015207698A - Method for manufacturing substrate with mask for lift-off process and method for manufacturing substrate with concavo-convex pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a substrate with a mask for a lift-off process, by which a concavo-convex structure is prevented from collapsing without decreasing convenience and high throughput property, burrs at an end are less likely produced, and a favorable concavo-convex pattern can be formed.SOLUTION: A substrate 10 with a mask for a lift-off process is obtained in the following way. A laminate 1 including a first resist layer 12 and a second resist layer 13 functioning as a mask, formed by a nano-imprinting process on a major surface 11a of a substrate 11 is treated with a developer that dissolves the first resist layer. The first resist layer is etched by using the second resist layer as a mask to form a mask layer 15 that is composed of the first resist layer and the second resist layer and constituting a concavo-convex structure 14 in which at least a part of the major surface is exposed. The structure is formed into a constricted shape in a cross-sectional view in a direction substantially perpendicular to the major surface of the first resist layer.

Description

  The present invention relates to a method for manufacturing a substrate with a lift-off mask and a method for manufacturing a substrate with an uneven pattern.

  Conventionally, a lift-off method is known as a method for forming a fine uneven pattern made of a metal film on the surface of a substrate. In the lift-off method, first, a resist pattern having a pattern obtained by inverting a fine concavo-convex pattern is formed on the surface of a substrate. Next, a metal film is deposited on the surface of the substrate including the resist pattern. Then, the fine uneven | corrugated pattern which consists of a metal film left on the surface of a base material is formed by removing the resist pattern which the metal film vapor-deposited on the surface.

  As a method for forming a fine resist pattern necessary for LSI production on the surface of a substrate, a photolithography technique or a mask pattern drawing technique (EB method) using an electron beam drawing apparatus is used. However, with a photolithography technique, it is difficult to process with a pattern of about the wavelength of light used for exposure. In the EB method, since the mask pattern is directly drawn by the electron beam, the drawing time increases as the drawing pattern increases, and there is a problem that the throughput until the pattern formation is significantly reduced. Furthermore, the exposure apparatus for photolithography requires high-precision control of the mask position, and the electron beam drawing apparatus is increased in size, which has the disadvantage that the apparatus cost increases.

  On the other hand, a nanoimprint technique is known as a fine pattern processing technique. Nanoimprint technology uses a mold with a fine concavo-convex pattern formed on the surface, presses the mold against a photocurable resin coated on the surface of the substrate, then cures the photocurable resin with light such as UV, This is a technique for transferring a fine concavo-convex pattern formed on a mold to a resin. In this nanoimprint technology, once a mold is manufactured, a fine structure can be easily and repeatedly formed, so that high throughput can be realized. Further, expensive apparatuses such as an exposure apparatus for photolithography and an electron beam drawing apparatus can be used. Since it is unnecessary, it is simple and economical, and its application to various fields is considered.

  It has been proposed to apply such nanoimprint technology to a lift-off method. Patent Document 1 discloses that a nanostructure can be easily produced by using a lift-off method in combination with a photo-curable resin that is capable of optical nanoimprinting at room temperature and whose cured product has excellent solvent solubility. Has been proposed.

  Further, Patent Document 1 discloses that when an inorganic compound or an organic compound is deposited on the surface of a substrate including a resin layer having a fine uneven pattern, the resin is dissolved because of the inorganic compound or the organic compound deposited on the side wall portion of the resin layer. It is described that a desired pattern shape may not be obtained due to remarkably hindering, particularly when the pattern shape formed of the resin layer is a trapezoid having a taper.

  In the nanoimprint described in Patent Document 1, a resin layer having a fine concavo-convex pattern is exposed and cured by pressing a mold having a fine concavo-convex pattern on a substrate coated with a photocurable composition and irradiating UV. Since the resin layer is formed, there is a problem that a fine uneven pattern having a high aspect ratio cannot be obtained.

  In Patent Document 2, an upper resist pattern composed of a second resist layer is formed by nanoimprinting on a first resist layer provided on a substrate surface, and then the first resist layer is dry-etched using the upper resist pattern as a mask. Then, forming a lower resist pattern is disclosed. According to this method, there is an advantage that a resist pattern having a high aspect ratio, which has been difficult with a normal nanoimprint method, can be obtained.

  Furthermore, in Patent Document 3, the number of steps can be reduced by using a nanoimprint mold integrated with the second resist layer in advance, and the first resist layer and the second resist layer are integrated in advance. A method for bonding bodies is disclosed. According to this method, high throughput can be realized.

  Patent Document 4 discloses forming a multilayer photoresist layer having an undercut shape that can be applied to a lift-off method. In this method, a second photoresist layer is formed on the first photoresist layer, and an undercut shape is formed by utilizing a difference in photosensitive speed between the first photoresist layer and the second photoresist layer.

JP 2011-181704 A International Publication No. 2007/142088 Pamphlet Japanese Patent No. 5243672 JP 2010-113356 A

  In the lift-off method using the nanoimprint method disclosed in Patent Document 1, in order to obtain a resist pattern having a high aspect ratio, the metal to be deposited is applied by applying the nanoimprint method disclosed in Patent Document 1 and Patent Document 2. The film thickness can be increased.

  However, it is desirable that the fine concavo-convex pattern desirable for the lift-off process not only has a high aspect ratio but also has a reverse tapered shape in cross-sectional shape. If the metal film is formed on the fine concavo-convex pattern when the cross-sectional shape of the fine concavo-convex pattern is a forward-tapered trapezoidal shape or a rectangular shape, the metal film remains on the side wall of the fine concavo-convex pattern. Things are easy to form. In such a state, since the upper part and the side wall of the fine concavo-convex pattern are continuous and easily integrated, when immersed in a resist stripping solution at the time of lift-off, the resist stripping solution does not easily penetrate into the resist layer, and lift-off is prevented. It becomes difficult to be done. Furthermore, the metal film residue formed on the sidewalls of the fine concavo-convex pattern remains at both ends of the metal film after lift-off, so that so-called burrs are likely to occur. This burr becomes a factor such as an electrical failure.

  However, in the nanoimprint method, since a process of peeling the mold from the cured resin layer is indispensable, in order to ensure releasability, the cross-sectional shape of the obtained fine uneven pattern must be trapezoidal or rectangular. .

  In addition, as described in Patent Document 2 and Patent Document 3, by adjusting the etching process conditions after nanoimprint, as reported in the existing two-layer resist method, the cross-sectional shape is an inverted trapezoidal fine unevenness It is also possible to form a pattern.

  However, in the nano-order fine concavo-convex pattern, there arises a new problem that the fine concavo-convex pattern tends to collapse when the inverted trapezoidal shape is used. This is because, when a nano-order fine concavo-convex pattern is formed, moisture in the air is condensed in the gaps between the concavo-convex patterns, and the concavo-convex patterns come into contact with each other due to surface tension. Although the details of the mechanism of this phenomenon are unknown, it is interpreted that the voids between the concavo-convex patterns act like pores and condense based on the Laplace law.

  Thus, the lift-off method using the nanoimprint technology has been difficult to realize.

  In addition, as described in Patent Document 4, in a method using a photolithographic technique without using a nanoimprint method, it is difficult to perform patterning at a nano-order with a pattern less than the wavelength of light used for exposure. There is a problem that the apparatus cost becomes excessive in the EB method.

  The present invention has been made in view of such points, and even when the nanoimprint method is applied for forming a mask layer used in the lift-off method, without impairing simplicity and high throughput, When manufacturing a substrate with a concavo-convex pattern by the lift-off method, it is possible to prevent the concavo-convex structure composed of the mask layer from falling down, and further, it is difficult to generate end burrs, and a substrate with a lift-off mask that forms a favorable concavo-convex pattern It aims at providing the manufacturing method and the manufacturing method of a base material with an uneven | corrugated pattern.

  The method for manufacturing a substrate with a lift-off mask according to the present invention includes a laminate in which a first resist layer and a second resist layer functioning as a mask are formed on a main surface of a substrate by a nanoimprint method. A developing step of treating with a developing solution that dissolves one resist layer; and etching the first resist layer using the second resist layer as a mask to form the first resist layer and the second resist layer; Forming a concavo-convex structure in which at least a part of the main surface of the material is exposed, and the first resist layer is constricted in a cross-sectional view in a direction substantially perpendicular to the main surface of the base material Forming a mask layer having a shape to obtain a substrate with a lift-off mask.

  With such a configuration, even when the nanoimprint method is applied to form the mask layer, the concavo-convex pattern is formed by the lift-off method without impairing the simplicity and high throughput characteristic of the nanoimprint method. In this case, it is possible to prevent the concavo-convex structure from collapsing, and it is possible to form an excellent concavo-convex pattern because the end burr hardly occurs.

  In the manufacturing method of a substrate with a lift-off mask according to the present invention, the concavo-convex structure is preferably nano-order.

  In the method for manufacturing a substrate with a lift-off mask according to the present invention, the nanoimprint method includes a step of forming the first resist layer on the main surface of the substrate, and a recess of a mold having an uneven structure on the surface. Filling the second resist layer, pressing the surface of the mold against the surface of the first resist layer, peeling the mold from the substrate to obtain the laminate, It is preferable to comprise.

  In the method for manufacturing a substrate with a lift-off mask according to the present invention, the nanoimprinting method fills the concave portion of the mold having a concavo-convex structure on the surface with the second resist layer, and the concave portion on the surface of the mold. Forming the first resist layer so as to cover the surface, pressing the main surface of the substrate against the surface of the first resist layer, and peeling the mold to obtain the laminate It is preferable to comprise.

  In the method for manufacturing a substrate with a lift-off mask according to the present invention, it is preferable that the second resist layer is filled in a part of the recess of the mold.

In the method for manufacturing a substrate with a lift-off mask according to the present invention, the constricted shape includes a cross-sectional width W1 of the first resist layer on the interface side with the second resist, and the substrate of the first resist layer. It is preferable that the cross-sectional width W2 on the interface side and the minimum cross-sectional width Ws of the first resist layer satisfy the following formula (1).
Formula (1)
0.5 × W1 <Ws <W1 and 0.5 × W2 <Ws <W2

  The manufacturing method of the base material with a concavo-convex pattern according to the present invention includes a step of forming a patterning layer on the main surface of the base material including the mask layer of any one of the lift-off mask base materials, and the patterning layer. The lift-off mask substrate containing the first resist layer is treated with a stripping solution that dissolves the first resist layer, the mask layer containing the patterning layer formed on the surface is removed, and the main surface is filled with the And a step of obtaining a substrate with an uneven pattern on which an uneven pattern of a patterning layer is formed.

  According to the present invention, even when the nanoimprint method is applied to form a mask layer used in the lift-off method, a substrate with a concavo-convex pattern is manufactured by the lift-off method without impairing simplicity and high throughput. The method for producing a substrate with a lift-off mask and a substrate with a concavo-convex pattern that can prevent the concavo-convex structure composed of a mask layer from falling down and further prevent edge burrs from forming and form a good concavo-convex pattern. A manufacturing method can be provided.

It is a section schematic diagram showing each process of a manufacturing method of a substrate with a lift-off mask concerning an embodiment of the invention. It is a cross-sectional schematic diagram which shows each process of an example of the nanoimprint method in the manufacturing method of the base material with the mask for lift-offs concerning this Embodiment. It is a cross-sectional schematic diagram which shows each process of the other example of the nanoimprint method in the manufacturing method of the base material with the mask for lift-off which concerns on this Embodiment. It is a schematic diagram which shows the cross-sectional view shape of the 1st resist layer in the manufacturing method of the base material with the mask for lift-offs concerning this Embodiment. It is a schematic sectional drawing which shows the lift-off process in the manufacturing method of the base material with an uneven | corrugated pattern which concerns on this Embodiment. It is a schematic diagram which shows the observation result by the microscope picture of the surface of the base material with the mask for lift-off produced in the Example of this invention.

  Hereinafter, embodiments of the present invention will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

  FIG. 1 is a schematic cross-sectional view showing each step of a method for manufacturing a substrate with a lift-off mask according to an embodiment of the present invention.

(Production of laminate by nanoimprint method)
In the present embodiment, first, as shown in FIG. 1A, the first resist layer 12 and the second resist layer 13 functioning as a mask were formed on the main surface 11a of the substrate 11 by the nanoimprint method. A laminate 1 is prepared.

  As shown in FIG. 1A, a neck portion 12 a made of the first resist layer 12 is formed below the second resist layer 13.

(Nanoimprint method)
Hereinafter, the nanoimprint method performed in order to obtain the laminated body 1 is demonstrated.

  An example of the nanoimprint method (hereinafter referred to as “A method”) applied to the present embodiment includes a step of forming the first resist layer 12 on the main surface 11a of the substrate 11, and a concave portion of a mold having a concavo-convex structure on the surface. A step of filling the second resist layer 13 to the surface, a step of pressing the surface of the mold against the surface of the first resist layer 12, and a step of peeling the mold from the substrate 11 to obtain the laminate 1. To do.

  In addition, another example of the nanoimprint method (hereinafter referred to as “B method”) applied to the present embodiment includes a step of filling the second resist layer 13 in a concave portion of a mold having a concavo-convex structure on the surface, A step of forming the first resist layer 12 so as to cover the recess filled with the second resist layer 13, a step of pressing the main surface 11a of the substrate 11 against the surface of the first resist layer 12, Peeling the mold to obtain the laminate 1.

(Method A)
First, the method A will be described. FIG. 2 is a schematic cross-sectional view showing each step of an example of a nanoimprint method in the method for manufacturing a substrate with a lift-off mask according to the present embodiment. As shown in FIG. 2A, a first resist material is applied on the main surface 11a of the substrate 11 by spin coating or the like to form the first resist layer 12.

  The first resist layer 12 is formed by first applying the first resist material constituting the first resist layer 12 to the main surface 11a of the substrate 11 by spin coating, dispenser, intaglio printing, letterpress printing, and spray coating, for example. It can be performed by applying to. In this case, spin coating is preferable in that the first resist material can be applied to the entire surface of the substrate 11 with a uniform thickness.

  In addition, in order to improve the adhesiveness of the base material 11 and the 1st resist layer 12, on the main surface 11a of the base material 11 which provides the 1st resist layer 12, a chemical bond with the 1st resist layer 12, penetration, etc. An easy-adhesion coating for physical bonding, primer treatment, corona treatment, plasma treatment, UV / ozone treatment, high energy ray irradiation treatment, surface roughening treatment, porous treatment, and the like may be performed.

  Next, as shown in FIG. 2B, the second resist layer 13 is filled in the recesses 23 of the nanoimprint mold 22 having the uneven structure 21 on the surface.

2B, the nanoimprint mold 22 includes a distance (lcc) between the top position (S) of the convex portion 24 of the concavo-convex structure 21 and the surface position (Scc) where the second resist layer 13 is exposed in the concave portion 23, and the top portion. The height (depth) (h) of the concavo-convex structure 21 of the nanoimprint mold 22 expressed by the distance between the position (S) and the bottom of the recess 23, that is, the position of the surface of the nanoimprint mold 22, satisfies the following formula (1). It is preferable.
Formula (1)
0 <lcc <1.0h

  According to such a configuration, the second resist layer 13 is disposed so as to fill a part of the concave portion 23 of the concave-convex structure 21. Therefore, when the first resist layer 12 is etched using the second resist layer 13 as a mask to form the mask layer 15 in a later-described step (FIG. 2C), the mask layer 15 having no remaining film and having a high aspect ratio is formed. Can be obtained.

  The second resist layer 13 is transferred to the substrate 11 via the first resist layer 12 in a step (FIG. 2C) described later. Thereafter, the first resist layer 12 is etched using the second resist layer 13 as a mask. For this reason, the second resist layer 13 is required to have easy transfer and dry etching resistance. From the viewpoint of dry etching resistance and transfer ease, lcc ≦ 0.9 h is desirable. More preferably, lcc ≦ 0.7 h, and still more preferably lcc ≦ 0.6 h.

  Further, the lcc variation in the plane affects the variation of the mask layer 15 to be formed, leading to a variation in the uneven pattern formed on the desired substrate 11. From the viewpoint of reducing in-plane variation of lcc, lcc is preferably in a range satisfying 0 <lcc, and more preferably 0.02h ≦ lcc. More preferably, 0.05h ≦ lcc, and particularly preferably 0.1h ≦ lcc.

  Furthermore, lcc is the same as the length of the neck portion 12a in FIG. 1A. As described above, the neck portion 12a is preferably 0.9 h or less from the viewpoint of easy transfer and resistance to dry etching. More preferably, it is 0.7 h or less, and more preferably 10 0.6 h or less.

For the above reason, the distance (lcc) between the top position (S) of the convex portion 24 of the concavo-convex structure 21 and the surface position (Scc) where the second resist layer 13 is exposed in the concave portion 23 is expressed by the following formula (2). It is more preferable to satisfy.
Formula (2)
0.02h ≦ lcc ≦ 0.9h

  In addition, the second resist layer 13 formed on the top of the convex portion 24 of the nanoimprint mold 22 in FIG. 2B is unnecessary and needs to be removed in a subsequent dry etching step, and therefore it is preferable that the second resist layer 13 be small. It is preferable that there is substantially no influence on the pattern formation.

  In FIG. 2B, as a method of filling the concave portion 23 of the nanoimprint mold 22 with the second resist layer 13, for example, first, the second resist layer 13 is formed on the surface of a transfer member prepared separately from the nanoimprint mold 22. A second resist material is applied. Next, the surface of the transfer member coated with the second resist material (hereinafter also referred to as a transfer surface) is pressed in a state where the surface having the uneven structure 21 of the nanoimprint mold 22 is opposed.

  In this case, the transfer member is not particularly limited as long as it has a smooth surface. For example, it is represented by quartz, non-alkali glass, low alkali glass, soda lime glass, which is typified by synthetic molding or fused silica. Glass, silicon wafer, sapphire, diamond, SiC substrate, mica substrate and the like.

  Further, the method of applying the second resist material to the transfer member is not particularly limited as long as the thickness can be applied uniformly, and examples thereof include spin coating.

  The shape of the transfer member is such that the nanoimprint mold 22 is pressed against the transfer surface of the planar member coated with the second resist material, and the second resist layer 13 is evenly filled in the recesses 23 of the nanoimprint mold 22. The shape is not particularly limited, and examples thereof include a flat shape, a roll shape, and a curved surface shape.

  The mechanism by which the second resist material is filled only in the recesses 23 of the nanoimprint mold 22 is not clear, but it is considered that the recesses 23 are filled by capillary action because of the size of the nano order. Therefore, it is preferable to perform the surface treatment of the nanoimprint mold 22 in advance.

  Examples of the surface treatment method include primer treatment, corona treatment, plasma treatment, UV / ozone treatment, and high energy ray irradiation treatment. These surface treatments can be appropriately selected so that the filling of the second resist material into the recesses 23 satisfies the above-described formula (1) or formula (2).

  Next, as illustrated in FIG. 2C, the second resist layer 13 is filled in the concave portion 23 of the nanoimprint mold 22 with respect to the surface of the first resist layer 12 provided on the main surface 11 a of the base material 11. Press the surface.

In the step of FIG. 2C, the distance (ho) between the nanoimprint mold 22 disposed via the first resist layer 12 and the surface of the substrate 11 preferably satisfies the following formula (3).
Formula (3)
150 nm ≦ ho ≦ 1500 nm

  If it is less than 150 nm, the pressing force and pressing time when pressing the nanoimprint mold 22 become excessive, which is not preferable from the viewpoint of production efficiency. On the other hand, if it exceeds 1500 nm, it is not preferable because etching accuracy deteriorates when the first resist layer 12 is etched using the second resist layer 13 as a mask, and the etching time becomes long. Since it falls, it is not preferable.

  Next, the nanoimprint mold 22 is peeled from the substrate 11 to obtain the laminate 1 shown in FIG.

  Here, in order to chemically bond the first resist layer 12 and the second resist layer 13 before or after the nanoimprint mold 22 is peeled off, thermal energy and / or light energy may be irradiated. good.

  The thermal energy irradiation is not particularly limited as long as it causes a chemical bond with the first resist layer 12 and the second resist layer 13, and an infrared heating method, a microwave heating method, and a laser irradiation heating method. Etc. In addition, a method of generating chemical bonds by changing the surrounding gas atmosphere, such as an oxygen atmosphere, a nitrogen atmosphere, or an Ar atmosphere, even when the amount of heat is about room temperature.

  Similarly, the light energy irradiation is not particularly limited as long as it causes a chemical bond with the first resist layer 12 and the second resist layer 13, and is not limited to visible light irradiation, infrared irradiation, UV irradiation, A method of irradiating light having a wavelength that causes a specific chemical reaction, such as X-ray irradiation. A method of exciting by a photoradical reaction by a UV irradiation method is preferable from the viewpoint that the reaction other than the mold pressing point can be suppressed by oxygen inhibition.

  These thermal energy irradiation and light energy irradiation can be used alone, or both methods such as simultaneous irradiation or sequential irradiation can be used. It is preferable to use both methods because chemical bonding between the first resist layer 12 and the second resist layer 13 is promoted. For example, the first resist layer 12 and the second resist layer 13 are primarily reacted by light energy irradiation, and then heated to increase the reaction heat.

  In the method for manufacturing a substrate with a lift-off mask according to the present embodiment, as will be described later, the laminate 1 is processed with a developer that dissolves the first resist layer 12, and the first resist layer 12 is processed. A constricted shape forming step for forming a constricted shape is necessary. In thermal energy irradiation and / or light energy irradiation, when the first resist layer 12 is modified by thermal energy irradiation and / or light energy irradiation, In the subsequent development step, it is preferable to perform thermal energy irradiation and / or light energy irradiation under the condition that the first resist layer 12 is modified to such an extent that it dissolves.

(Method B)
Next, the method B will be described, but the same points as the method A will be omitted using the same reference numerals and symbols. FIG. 3 is a schematic cross-sectional view showing each step of another example of the nanoimprint method in the method for manufacturing a substrate with a lift-off mask according to the present embodiment. As shown in FIG. 3A, first, the second resist layer 13 is filled in the concave portion 23 of the nanoimprint mold 22 having the concavo-convex structure 21 on the surface.

  Next, as shown in FIG. 3B, the first resist layer 12 is formed on the surface of the nanoimprint mold 22 including the recess 23 filled with the second resist layer 13 so as to cover the recess 23.

  Next, as shown in FIG. 3C, the main surface 11 a of the substrate 11 is pressed against the surface of the first resist layer 12 opposite to the second resist layer 13.

  Next, the nanoimprint mold 22 is peeled from the substrate 11 to obtain the laminate 1 shown in FIG.

  When the laminate 1 is formed by the nanoimprint method as described above, the second resist layer 13 is filled in a part of the recess 23 of the nanoimprint mold 22, and the first resist is formed on the surface of the nanoimprint mold 22 including the recess 23. By pressing the layer 12 (Method A) or forming the first resist layer 12 (Method B), the first resist layer 12 is filled in the recesses 23 as shown in FIGS. 2C and 3C. At this time, in the nanoimprint mold, when lcc exceeds 0, that is, when the first resist layer 12 is filled in a part of the recess 23, when the nanoimprint mold 22 is peeled, as shown in FIG. A neck portion 12 a made of the first resist layer 12 is formed below the resist layer 13.

(Development process)
Next, the laminate 1 is treated with a developer that dissolves the first resist layer 12. In the development step, the second resist layer 13 does not dissolve, and the first resist layer 12 must be partially dissolved. As a result, as shown in FIG. 1B, the cross-sectional width of the neck portion 12 a of the first resist layer 12 is smaller than the cross-sectional width of the second resist layer 13. As described later, such a shape is necessary to make the first resist layer 12 have a constricted shape in a sectional view.

  The developing solution is not particularly limited as long as the second resist layer 13 is hardly dissolved and there is a solubility capable of dissolving a part of the first resist layer 12, and the developer is appropriately selected depending on the components constituting the resist layer. Although it can be selected, an organic solvent or an alkaline solution is preferred.

  Examples of the organic solvent include alcohol solvents, ether solvents, ketone organic solvents, amide solvents, ester organic solvents, hydrocarbon solvents, and the like.

  Examples of alcohol solvents include methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, and 2-methylbutanol. , Sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethyl Hexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, se - heptadecyl alcohol, furfuryl alcohol, phenol, cyclohexanol, methyl cyclohexanol, 3,3,5-trimethyl cyclohexanol, benzyl alcohol, mono-alcohol solvents such as diacetone alcohol;

  Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2 Polyhydric alcohol solvents such as ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol;

  Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, polyhydric alcohol partial ether solvents such as dipropylene glycol monopropyl ether.

  Examples of the ether solvent include anisole, diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane, diphenyl ether and the like.

  Examples of ketone solvents include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, methyl-n-amyl ketone, ethyl-n-butyl ketone, and methyl-n-. Examples include hexyl ketone, di-iso-butyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, and the like.

  Examples of the amide solvent include N, N′-dimethylimidazolidinone, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide. , N-methylpropionamide, N-methylpyrrolidone and the like.

  Examples of the ester solvent include diethyl carbonate, propylene carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, iso-propyl acetate, n-butyl acetate, iso-butyl acetate, and acetic acid. sec-butyl, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, aceto Methyl acetate, ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene acetate Recall mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, diacetic acid Glycol, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, iso-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate , Diethyl malonate, dimethyl phthalate, diethyl phthalate and the like.

  Examples of the hydrocarbon solvent include n-pentane, iso-pentane, n-hexane, iso-hexane, n-heptane, iso-heptane, 2,2,4-trimethylpentane, n-octane, iso-octane, Aliphatic hydrocarbon solvents such as cyclohexane and methylcyclohexane; benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, iso-propylbenzene, diethylbenzene, iso-butylbenzene, triethylbenzene, di And aromatic hydrocarbon solvents such as -iso-propyl benzene and n-amyl naphthalene.

  Of these, alcohol solvents, ketone solvents, and ester solvents are preferable, and propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, γ-butyrolactone, N-methylpyrrolidone, cyclohexanone, cyclopentanone, and the like are preferable. These solvents may be used alone or in combination of two or more.

  It is preferable to rinse the laminated body 1 after processing with a developing solution. The organic solvent used for rinsing preferably has a boiling point of 100 ° C. or lower, and is preferably an alcohol solvent or a ketone solvent, and examples thereof include methanol, ethanol, acetone, and methyl ethyl ketone. Further, water may be used as a rinsing liquid, and it is more preferable to develop or temporarily rinse with an organic solvent that dissolves in water before rinsing with water. By using water as the rinse liquid, there is an effect of tightening the swollen resist.

  Examples of the alkaline solution developer include solutions of alkaline compounds such as amine compounds and inorganic basic compounds.

  Examples of amine compounds include ethanolamine, diethanolamine, triethanolamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-butylamine, tri-n-butylamine, tetramethylammonium hydroxide, and tetraethylammonium. Hydroxide, tetra-n-propylammonium hydroxide, tetra-n-butylammonium hydroxide, tetramethylammonium fluoride, tetraethylammonium fluoride, tetra-n-propylammonium fluoride, tetra-n-butylammonium fluoride, tetramethylammonium chloride Tetraethylammonium chloride, tetra-n-propylammonium chloride, tetra-n-butylammonium chloride , Ammonia, and the like. In particular, tetramethylammonium hydroxide and tetraethylammonium hydroxide are preferable from the viewpoint of basicity.

  Examples of inorganic basic compounds include lithium hydroxide, potassium hydroxide, sodium hydroxide, calcium hydroxide, magnesium hydroxide, potassium carbonate, sodium carbonate, calcium carbonate, magnesium carbonate, potassium bicarbonate, sodium bicarbonate and the like. Can be mentioned.

  Although it will not specifically limit as a solvent used for an alkaline solution if an alkaline compound melt | dissolves, From a soluble viewpoint, water or an alcoholic solvent is preferable. These may be used alone or in combination of two or more.

(Mask layer forming process)
Next, using the second resist layer 13 as a mask, the first resist layer 12 is dry-etched. As shown in FIG. 1C, the second resist layer 13 of the first resist layer 12 is absent or very thin. (Residual film) of the first resist layer 12 is removed, and the mask is formed of the first resist layer 12 and the second resist layer 13 and constitutes the concavo-convex structure 14 exposing a part of the main surface 11a of the substrate 11. Layer 15 is formed.

The method of dry etching the first resist layer 12 using the second resist layer 13 as a mask is not particularly limited, but the mask layer 15 composed of the second resist layer 13 / the first resist layer 12 is formed. Therefore, the ratio (VV / VH) between the etching rate VH in the horizontal direction and the etching rate VV in the vertical direction is preferably large, and a plasma dry etching method is preferable. In particular, since the anisotropy can be increased, O ₂ gas can be selected as an etching gas, and a mixed gas in which H ₂ gas, Ar gas, Xe gas, and N ₂ gas are appropriately mixed is used. be able to.

  The pressure at the time of dry etching is preferably 0.1 Pa to 5 Pa, and is preferably in the range of 0.1 to 1 Pa, because the ion incident energy contributing to reactive etching can be increased and the etching anisotropy can be increased. In particular, it is preferable because anisotropy is enhanced.

  The plasma etching method is not particularly limited, and capacitively coupled RIE, inductively coupled RIE, or RIE using an ion pulling bias can be employed.

(Neck shape forming process)
Next, as shown in FIG. 1D, the shape of the first resist layer 12 in a cross-sectional view in a direction substantially perpendicular to the main surface 11a of the substrate 11 (hereinafter referred to as a cross-sectional view shape) is a constricted shape. Thus, the substrate 10 with a lift-off mask is obtained.

FIG. 4 is a schematic diagram showing a cross-sectional view of the first resist layer in the method for manufacturing a substrate with a lift-off mask according to the present embodiment. As shown in FIG. 4, the first resist layer 12 has a constricted shape in a cross-sectional view, at any location in the height direction of the first resist layer 12, an interface S1 with the second resist layer 13, And it is the shape which provided the location made smaller than cross-sectional width W1, W2 of the 1st resist layer 12 in interface S2 with the main surface 11a of the base material 11. FIG. More specifically, it means a state in which the smallest cross-sectional width (hereinafter referred to as the minimum cross-sectional width) Ws of the first resist layer 12 satisfies the relationship of the above-described cross-sectional widths W1 and W2 and the following formula (4).
Formula (4)
0.5 × W1 <Ws <W1 and 0.5 × W2 <Ws <W2

  As described above, since the minimum cross-sectional width Ws of the constricted shape is smaller than the cross-sectional width W1 on the interface S1 side, the lift-off process is performed using the substrate 10 with a lift-off mask as described later, and the patterning layer When forming the concave / convex pattern, the patterning layer (metal film) 13 is hardly formed on the side surface of the first resist layer 12 due to the shielding effect of the second resist layer 13, and therefore, end burr is less likely to occur. On the other hand, since the cross-sectional width W2 on the interface S2 side is larger than the minimum cross-sectional width Ws of the constricted shape, the cross-sectional shape of the first resist layer 12 is not a monotonous reverse taper structure, but the cross-sectional width in the vicinity of the base material 11 is widened. For this reason, the mechanical strength is increased and the concavo-convex structure 14 is unlikely to fall down. Therefore, as shown in FIG. 4, the portion of Ws is preferably near the center of the first resist layer 12.

  Furthermore, as described above, in nano-order fine concavo-convex patterns, condensation due to moisture in the air is likely to occur in the gaps between the concavo-convex patterns, and the concavo-convex patterns are stuck and fall down due to the surface tension of the generated water film. Is prone to occur. It is considered that by forming a cross-sectional structure as shown in FIG. 4, dew condensation in the gaps between the fine uneven patterns can be suppressed.

The constricted shape preferably satisfies the relationship of the following formula (5) from the viewpoint that an end burr is not easily generated and a good pattern can be formed.
Formula (5)
0.6 × W1 <Ws <0.95 × W1 and 0.6 × W2 <Ws <0.95 × W2

In particular, the constricted shape preferably satisfies the relationship of the following formula (6) from the viewpoint of making it difficult to cause collapse even when the concavo-convex structure 14 is nano-order.
Formula (6)
0.8 × W1 <Ws <0.90 × W1 and 0.8 × W2 <Ws <0.90 × W2

  Here, the shape of the concavo-convex structure 14 composed of the mask layer 15 composed of the first resist layer 12 and the second resist layer 13 may be such that the cross-sectional shape of the first resist layer 12 is constricted as described above. For example, there is no particular limitation. That is, the planar structure of the concavo-convex structure 14 may be a pillar shape with independent concavo-convex, such as a circle, a square, or a polygon, or a line and space. Here, the “pillar shape” is “a shape in which a plurality of columnar bodies as shown in FIG. 4 are arranged in a cross-sectional view”, and the line and space is a shape in a cross-sectional view in the in-plane direction of the base material surface Is a continuous shape.

Hereinafter, a method for forming a constricted shape will be described. In order to obtain a constricted shape, as shown in FIG. 1C, a reaction using a reactive gas having an etching rate of the first resist layer 12 higher than that of the second resist layer 13 using the second resist layer 13 as a mask. Dry etching is performed. Specifically, for example, a sol-gel material having Ti, Zr, Ta, or the like as a metal element is selected as the second resist layer 13, while an organic substance such as an acrylic resin is selected as the first resist layer 12, and O ₂ A constricted shape can be obtained by dry etching using a gas as a reactive gas (etching gas).

  Various dry etching conditions in the constricted shape forming step can be designed depending on the material. For example, the following etching method can be given.

From the viewpoint of chemically reacting the first resist layer 12, H ₂ gas can be selected in addition to O ₂ gas. Further, Ar gas and Xe gas can be selected from the viewpoint of improving the vertical etching rate by increasing the ion incident component. That is, as the gas used for etching, a mixed gas containing O ₂ gas and / or H ₂ gas and Ar gas and / or Xe gas can be used.

  The pressure at the time of etching is preferably 0.1 to 5 Pa, and preferably 0.1 to 1 Pa, because the ion incident energy contributing to reactive etching can be increased and the etching anisotropy can be further improved. More preferable.

The mixed gas ratio of O ₂ gas and / or H ₂ gas and Ar gas and / or Xe gas improves anisotropy when the chemically reactive etching component and the ion incident component are in appropriate amounts. Therefore, the ratio of the gas flow rate is preferably 99 sccm: 1 sccm to 50 sccm: 50 sccm, more preferably 95 sccm: 5 sccm to 60 sccm: 40 sccm, and still more preferably 90 sccm: 10 sccm to 70 sccm: 30 sccm.

The plasma etching is performed using capacitively coupled RIE, inductively coupled RIE, or RIE using an ion pulling bias. For example, only O ₂ gas or a gas in which O ₂ gas and Ar gas are mixed at 90 sccm: 10 sccm to 70 sccm: 30 sccm, the processing pressure is set in the range of 0.1 to 1 Pa, and capacitively coupled RIE Alternatively, an etching method using RIE using an ion pull-in voltage or the like can be given.

  In the etching process for forming the constricted shape as described above, the sol-gel material, which is a component having a low vapor pressure of the compound with the etching component, contained in the second resist layer 13 is applied to the side wall of the first resist layer 12. It is presumed that the thick first resist layer 12 can be easily etched because it plays a protective role.

  Furthermore, in the development process, the laminate 1 is treated with a developer, and a part of the first resist layer 12 is eluted with a developer at a very thin portion where the second resist layer 13 is not present, or the elution is performed. The range extends almost isotropically into the first resist layer 12, and the dry etching resistance of the first resist layer 12 at the eluted portion decreases. In such a state, the following phenomenon occurs by performing dry etching having anisotropy in the vertical direction in the constricted shape forming step. At this time, if the neck portion 12a in FIG. 1A is excessively larger than the second resist layer 13, the minimum cross-sectional width Ws is too thin in the constricted shape, which is not preferable. Therefore, the neck portion 12a in FIG. 1A is preferably 0.9 h or less in relation to the height (depth) (h) of the uneven structure 21 of the nanoimprint mold 22 illustrated in FIG. 2B. More preferably, it is 0.7 h or less, and further preferably 0.6 h or less.

  (1) In the mask formation step, etching at a location where the second resist layer 13 is not present or very thin proceeds in a direction substantially perpendicular to the main surface 11a by anisotropic dry etching. To do. Furthermore, as described above, the component having a low vapor pressure contained in the second resist layer 13 serves to protect the sidewall of the first resist layer 12, and as a result, etching with a high aspect ratio proceeds.

  (2) Etching of the first resist layer 12 immediately below the second resist layer 13 does not proceed because the second resist layer 13 serves as a mask.

  (3) Since a portion where the first resist layer 12 is eluted in the development process has low etching resistance, the etching proceeds slightly even at the lower portion of the second resist layer 13. It becomes narrower than the cross-sectional width of the resist layer 13. However, if the etching of the first resist layer 12 progresses and the etching depth becomes deeper, the effect of the development process is reduced, so that the cross-sectional width of the second resist layer 13 is again about the same. From this state, the constriction shape is obtained by moving to the constriction portion forming step and further proceeding with dry etching.

  The constricted shape forming step may be carried out continuously from the above-described mask layer forming step, or may be a step subjected to sequential processing. It is preferable to perform the mask layer forming step and the constricted portion forming step successively because collapse due to dew condensation in the gaps between the concave and convex patterns can be prevented in a break to the air atmosphere during the dry etching step.

  In the above description, the mask layer forming process and the constricted shape forming process are described as independent processes. However, the two processes can be simultaneously performed in one process by appropriately selecting the dry etching conditions. .

(Lift-off process)
Next, the case where a base material with a concavo-convex pattern is manufactured by the lift-off method using the base material 10 with a lift-off mask manufactured as described above will be described.

  FIG. 5 is a schematic cross-sectional view showing a lift-off process in the method for manufacturing a substrate with an uneven pattern according to the present embodiment. As shown to FIG. 5A, the patterning layer 51 is formed with respect to the main surface 11a of the base material 11 containing the mask layer 15 of the base material 10 with a mask for lift-off. The patterning layer 51 is a metal film, for example, and is formed by vapor deposition or the like.

  Next, the substrate 10 with a lift-off mask including the patterning layer 51 is treated with a stripping solution that dissolves the first resist layer 12 to include the patterning layer 51 formed on the surface as shown in FIG. 5B. The mask layer 15 is removed to obtain a substrate 50 with an uneven pattern in which the uneven pattern 52 of the patterning layer 51 is formed on the main surface 11a.

  At this time, if the patterning layer 51 is formed on the concavo-convex structure 14 when the cross-sectional shape of the first resist layer 12 of the mask layer 15 is a constricted shape, due to the shielding effect of the second resist layer 13, It is difficult for the residue of the patterning layer 51 to be formed on the side wall. For this reason, since the upper part and the side wall of the concave / convex pattern 52 are continuous and difficult to be integrated, when immersed in the resist stripping solution at the time of lift-off, the resist stripping solution easily penetrates into the first resist layer 12 and lift-off is not performed. It becomes easy. Furthermore, since burrs are unlikely to occur at both ends of the patterning layer 51 after lift-off, it is possible to prevent electrical failures from occurring.

  As described above, according to the method for manufacturing the substrate 50 with the uneven pattern using the substrate 10 with the lift-off mask according to the present embodiment, when the nanoimprint method is applied for forming the mask layer 15. Even so, the concavo-convex structure 14 can be prevented from falling when the concavo-convex pattern 52 is formed by the lift-off method without impairing the simplicity and high throughput characteristic of the nanoimprint method. It is difficult to generate burrs, and a good uneven pattern 52 can be formed. Such an effect is remarkable when the size of the concavo-convex structure 14 or the concavo-convex pattern 52 is nano-order.

  In the present embodiment, the concavo-convex structure 14 of the substrate 10 with the lift-off mask and the concavo-convex pattern 52 of the substrate 50 with the concavo-convex pattern are nano-orders means that the average pitch of the concavo-convex structure 14 and the concavo-convex pattern 52 is 1 nm to 1500 nm. Indicates the following.

  Hereinafter, the manufacturing method of the substrate with the lift-off mask according to the present embodiment will be described in more detail.

(Base material)
The base material 11 may be selected according to its use and is not particularly limited. For example, quartz typified by synthetic quartz or fused silica, non-alkali glass, low alkali glass, glass typified by soda lime glass, silicon wafer, nickel plate, sapphire, diamond, SiC substrate, mica substrate, semiconductor substrate ( Nitride semiconductor substrate) and ITO.

(First resist layer)
In the manufacturing method of the substrate 10 with a lift-off mask according to the embodiment of the present invention, it can be used as an application for manufacturing the substrate 50 with an uneven pattern by the lift-off method using the fine uneven pattern as a mask. Therefore, the first resist layer 12 in the present invention is not particularly limited as long as it satisfies the heat resistance generated in the patterning process.

  For example, a photopolymerizable radical polymerizable resin, a photopolymerizable cationic polymerizable resin, other known commercially available photopolymerizable or thermopolymerizable resins, and dry film resists. A resin that can be cross-linked and thermocompression bonded can be used. These are configured by adding at least a polymerization initiator.

  As the photopolymerizable radical polymerizable resin, a monomer having an acryloyl group or a methacryloyl group, a monomer having a vinyl group, and a monomer having an allyl group are preferable, and a monomer having an acryloyl group or a methacryloyl group is preferable.

  As a resin that can be partially crosslinked and thermocompression bonded as a dry film resist, a polyfunctional monomer having a plurality of polymerizable groups is also preferable in addition to the above-described monomers. The number is preferably an integer of 1 to 4 because of excellent polymerizability. In addition, when two or more kinds of polymerizable monomers are used, the number of polymerizable groups is 3 or more in order to increase the crosslinking point after the polymerization reaction and obtain the physical stability (strength, heat resistance, etc.) of the cured product. It is preferable that it is a monomer. In the case of a monomer having 1 or 2 polymerizable groups, it is preferably used in combination with a monomer having a different polymerization property.

  Specific examples of the acrylate monomer include the following compounds. Examples of the monomer having an acryloyl group or a methacryloyl group include (meth) acrylic acid, aromatic (meth) acrylate [phenoxyethyl acrylate, benzyl acrylate and the like. ],

  Hydrocarbon (meth) acrylate [stearyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, allyl acrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, Trimethylolpropane triacrylate, pentaaerythritol triacrylate, dipentaerythritol hexaacrylate and the like. ],

  Hydrocarbon (meth) acrylates containing etheric oxygen atoms [ethoxyethyl acrylate, methoxyethyl acrylate, glycidyl acrylate, tetrahydrofurfryl acrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, polyoxyethylene glycol diacrylate, trioxy Propylene glycol diacrylate and the like. ],

  Hydrocarbon (meth) acrylates containing functional groups [2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl vinyl ether, N, N-diethylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate, N- Vinylpyrrolidone, dimethylaminoethyl methacrylate, etc. ], Silicone acrylate, etc.

  Others include EO-modified glycerol tri (meth) acrylate, ECH-modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meth) acrylate, pentaerythritol triacrylate, EO-modified phosphate triacrylate, trimethylolpropane tri (meth) Acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, EO-modified trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meta) ) Acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate Alkyl modified dipentaerythritol penta (meth) acrylate, dipentaerythritol poly (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, alkyl modified dipentaerythritol tri (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, penta Erythritol tetra (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, di (meth) acrylated isocyanurate, 1,3-butylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, EO-modified 1,6-hexanediol di (meth) acrylate, ECH-modified 1,6-hexanediol di (Meth) acrylate, allyloxypolyethylene glycol acrylate, 1,9-nonanediol di (meth) acrylate, EO modified bisphenol A di (meth) acrylate, PO modified bisphenol A di (meth) acrylate, modified bisphenol A di (meth) acrylate , EO-modified bisphenol F di (meth) acrylate, ECH-modified hexahydrophthalic acid diacrylate, neopentyl glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, EO-modified neopentyl glycol diacrylate, PO Modified neopentyl glycol diacrylate, caprolactone modified hydroxypivalate ester neopentyl glycol, stearic acid modified pentaerythritol di (meth) Acrylate, ECH-modified propylene glycol di (meth) acrylate, ECH-modified phthalic acid di (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) di (meth) acrylate, poly (propylene glycol-tetramethylene glycol) di (meth) Acrylate, polypropylene glycol di (meth) acrylate, silicone di (meth) acrylate, tetraethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyester (di) acrylate, polyethylene glycol di (meth) acrylate, di Methylol tricyclodecane di (meth) acrylate, neopentyl glycol modified trimethylol propane di (meth) acrylate, dipropylene glycol di (Meth) acrylate, tripropylene glycol di (meth) acrylate, triglycerol di (meth) acrylate, EO-modified tripropylene glycol di (meth) acrylate, divinylethyleneurea, divinylpropyleneurea, 2-ethyl-2-butylpropanediol acrylate 2-ethylhexyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-methoxyethyl (Meth) acrylate, 3-methoxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, acrylic acid dimer, benzyl (meth) acrylate, butanedio Rumono (meth) acrylate, butoxyethyl (meth) acrylate, butyl (meth) acrylate, cetyl (meth) acrylate, EO-modified cresol (meth) acrylate, ethoxylated phenyl (meth) acrylate, ethyl (meth) acrylate, dipropylene glycol (Meth) acrylate, isoamyl (meth) acrylate, isobutyl (meth) acrylate, isooctyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyloxyethyl (Meth) acrylate, isomyristyl (meth) acrylate, lauryl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxypolyethylene Lenglycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methyl (meth) acrylate, methoxytripropylene glycol (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonyl Phenoxy polypropylene glycol (meth) acrylate, octyl (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, ECH modified phenoxy acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxytetraethylene glycol ( (Meth) acrylate, phenoxyethyl (meth) acryl , Polyethylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, stearyl (meth) acrylate, EO-modified succinic acid (meth) acrylate, tert-butyl (meth) acrylate, Tribromophenyl (meth) acrylate, EO-modified tribromophenyl (meth) acrylate, tridodecyl (meth) acrylate, isocyanuric acid EO-modified di- and triacrylate, ε-caprolactone-modified tris (acryloxyethyl) isocyanurate, ditrimethylolpropane tetra An acrylate etc. are mentioned.

  Examples of the monomer having an allyl group include p-isopropenylphenol, and examples of the monomer having a vinyl group include styrene, α-methylstyrene, acrylonitrile, and vinylcarbazole. Here, EO modification means ethylene oxide modification, ECH modification means epichlorohydrin modification, and PO modification means propylene oxide modification.

  In addition, it is preferable to add an alkali-soluble compound to the first resist layer 12 from the viewpoint of easy peeling of the first resist layer 12 at the time of lift-off. Examples of the alkali-soluble compound include compounds in which functional groups such as a hydroxy group, a phenol group, a carboxy group, a sulfone group, a phosphone group, and a silanol group are bonded.

  Alkali-soluble polymers / oligomers include (meth) acrylic acid polymers, copolymers of (meth) acrylic acid with the above acrylate monomers, polymers of hydroxystyrene, copolymers of hydroxystyrene with the above acrylate monomers and styrene derivatives, and epoxy group-containing Examples include polymer / oligomer acid anhydride adducts and phenol resins.

  Examples of the alkali-soluble acrylate monomer include compounds having a carboxyl group and a (meth) acrylate group in one molecule. Specific examples include (meth) acrylic acid, (meth) acrylic acid, carboxyethyl (meth) acrylate, Carboxypentyl (meth) acrylate, 2- (meth) acryloxyethyl succinic acid, 2- (meth) acryloxyethyl hexahydrophthalic acid, 2- (meth) acryloxyethyl phthalic acid, fumaric acid, cinnamic acid, croton Examples include acids, itaconic acid, and maleic acid half esters.

  Examples of the alkali-soluble low molecular weight compound include carboxylic acid compounds. Specifically, sorbic acid, lauric acid, myristic acid, oleic acid, 2-methyl-4-pentenoic acid, 4-methyl-2-pentenoic acid, 2-methyl-2-pentenoic acid, 2-methyl-n- Valeric acid, 3-methyl-n-valeric acid, 4-methyl-n-valeric acid, 2-ethylbutyric acid, heptanoic acid, octanoic acid, n-nonanoic acid, isononanoic acid, decanoic acid, DL-leucine acid, N- Acetyl-DL-methionine, 2-heptenoic acid, 2-octenoic acid, 2-nonenoic acid, 2-decenoic acid, 9-decenoic acid, 2-dodecenoic acid, 10-undecenoic acid, 3-cyclohexene-1-carboxylic acid, 1-cyclohexene-3-carboxylic acid, cyclohexanecarboxylic acid, cyclopentylacetic acid, cyclohexylacetic acid, cyclohexylpropionic acid, 4-cyclohexanebutyric acid, 5-norbornene-2 Carboxylic acid, m-anisic acid, m-toluic acid, m-tolylacetic acid, o-anisic acid, o-toluic acid, o-tolylacetic acid, p-anisic acid, p-toluic acid, p-tolylacetic acid, benzoic acid Etc.

  Further, the first resist layer 12 may be a positive resist. For example, the resin composition containing alkali-soluble resin and the compound which generate | occur | produces an acid by light is mentioned.

Examples of alkali-soluble resins include polymers of (meth) acrylic acid, copolymers of (meth) acrylic acid and the above acrylate monomers, polymers of hydroxystyrene, copolymers of hydroxystyrene and the above acrylate monomers and styrene derivatives, and epoxy group containing Examples include polymer / oligomer acid anhydride adducts and phenol resins. As the phenol resin, a condensation reaction product of a phenol compound and formaldehyde or an aldehyde compound is preferable. Examples of phenolic compounds include phenol, cresol, xylenol, trimethylphenol, the following compound (1), and the like. These may be used alone or in combination of two or more. In the compound (1), R is represented by the following compound (2). In the compound (2), R ² is a C1 to C12 hydrocarbon, which may be branched or may be bonded to an atom or functional group other than hydrogen.

  As the compound that generates an acid by light, any compound may be used as long as it generates an acid by an activation energy ray (for example, ultraviolet rays). For example, a photo-acid generator, a quinonediazide sulfonic acid compound, etc. are mentioned. A naphthoquinonediazide compound is preferred because it can suppress the solubility of the unexposed area.

  Examples of the photoacid generator include aromatic onium salts such as sulfonium salts and iodonium salts. Examples of the photoacid generator include sulfonium hexafluoroantimonate, benzyltriphenylphosphonium hexafluorophosphate, benzylpyridinium hexafluorophosphate, diphenyliodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, benzoin tosylate, adekatopomer ( (Registered trademark) sp-170, sp-172 (manufactured by ADEKA), WPAG-145, WPAG-170, WPAG-199, WPAG-281, WPAG-336, WPAG-367 (manufactured by Wako Pure Chemical Industries, Ltd.), CPI- 100P, CPI-101A, CPI-200K, CPI-210S, DTS-102 (Midori Chemical Co., Ltd.), TPS-TF, DTBPI-PFBS (Toyo Gosei Co., Ltd.) It is below.

  Examples of the quinonediazidesulfonic acid compound include 1,2-benzoquinonediazide-4-sulfonic acid, 1,2-naphthoquinonediazide-4-sulfonic acid, 1,2-benzoquinonediazide-5-sulfonic acid, and 1,2- Examples include o-quinonediazidesulfonic acid compounds such as naphthoquinonediazide-5-sulfonic acid, and other quinonediazidesulfonic acid derivatives. These sulfonic acid chlorides and sulfonic acid esters may be used, and sulfonic acid chlorides and sulfonic acid esters are preferable.

  The photopolymerization initiator causes a radical reaction or an ionic reaction by light, and a photopolymerization initiator that causes a radical reaction is preferable. As the photopolymerization initiator, the following known and commonly used photopolymerization initiators can be used alone or in combination of two or more.

  Acetophenone-based photopolymerization initiators: acetophenone, p-tert-butyltrichloroacetophenone, chloroacetophenone, 2,2-diethoxyacetophenone, hydroxyacetophenone, 2,2-dimethoxy-2′-phenylacetophenone, 2-aminoacetophenone, dialkyl Aminoacetophenone and the like.

  Benzoin-based photopolymerization initiators: benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-2-methyl Propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyldimethyl ketal and the like.

  Benzophenone-based photopolymerization initiators: benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, hydroxypropylbenzophenone, acrylic benzophenone, 4,4'-bis (dimethylamino) ) Benzophenone, perfluorobenzophenone, etc.

  Thioxanthone photopolymerization initiators: thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, diethylthioxanthone, dimethylthioxanthone, and the like.

  Anthraquinone photopolymerization initiators: 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone.

  Ketal photopolymerization initiators: acetophenone dimethyl ketal and benzyl dimethyl ketal.

  Other photopolymerization initiators: α-acyloxime ester, benzyl- (o-ethoxycarbonyl) -α-monooxime, acylphosphine oxide, glyoxyester, 3-ketocoumarin, 2-ethylanthraquinone, camphorquinone, tetramethylthiuram Sulfide, azobisisobutyronitrile, benzoyl peroxide, dialkyl peroxide, tert-butyl peroxypivalate and the like.

  Photopolymerization initiator having a fluorine atom: perfluoro tert-butyl peroxide, perfluorobenzoyl peroxide or the like.

  The photopolymerizable mixture may contain a photosensitizer. Specific examples of the photosensitizer include n-butylamine, di-n-butylamine, tri-n-butylphosphine, allylthiourea, s-benzisothiuronium-p-toluenesulfinate, triethylamine, diethylaminoethyl methacrylate. , Triethylenetetramine, 4,4′-bis (dialkylamino) benzophenone, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, tri It can be used in combination with one or more known and commonly used photosensitizers such as amines such as ethanolamine.

  Examples of commercially available initiators include “Irgacure®” manufactured by BASF (eg, Irgacure 651, 184, 500, 2959, 127, 754, 907, 369, 379, 379EG, 819, 1800, 784). , OXE01, OXE02), “Darocur (registered trademark)” (for example, Darocur 1173, MBF, TPO, 4265) and the like.

  A photoinitiator may be used individually by 1 type, or may use 2 or more types together. When two or more types are used in combination, it may be selected from the viewpoint of the dispersibility of the acrylate to be used, the surface portion of the fine concavo-convex structure of the photopolymerizable mixture, and the internal curability. For example, the combined use of an α-hydroxyketone photopolymerization initiator and an α-aminoketone photopolymerization initiator can be mentioned.

  In addition, as a combination of two types, for example, “Irgacure” to each other, “Irgacure” to “Darocur”, Darocur 1173 and Irgacure 819, Irgacure 379 and Irgacure 127, Irgacure 819 and Irgacure 127, Irgacure 819 Examples include Irgacure 184 and Irgacure 379EG, Irgacure 184 and Irgacure 907, Irgacure 127 and Irgacure 379EG, Irgacure 819 and Irgacure 184, Darocur TPO and Irgacure 184, and the like.

(Second resist layer)
The composition of the second resist material constituting the second resist layer 13 is not particularly limited, and various known resins (organic substances) that can be diluted in a solvent, inorganic precursors, inorganic condensates, plating solutions (chromium plating solutions, etc.) ) Can be used. The second resist layer 13 is chemically bonded to the first resist layer 12, and the first resist layer 12 is dry-etched using the second resist layer 13 as a mask to form the substrate 10 with a lift-off mask. From the viewpoint of the transfer accuracy in carrying out, it is particularly preferred to include either or both of a photopolymerizable group capable of photopolymerization and a polymerizable group capable of thermal polymerization. The second resist material preferably contains a metal element from the viewpoint of dry etching resistance.

  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.

  The concentration of the solvent-diluted second resist material is such that the solid content of the coating film filled on the unit area is equal to or less than the volume of the voids (concaves) of the fine concavo-convex structure existing on the unit area (bottom). If it is, it will not be specifically limited.

  Examples of the photopolymerizable group contained in the second resist material include acryloyl group, methacryloyl group, acryloxy group, methacryloxy group, methacryl group, vinyl group, epoxy group, allyl group, and oxetanyl group.

  The metal elements contained in the second resist material include titanium (Ti), zirconium (Zr), chromium (Cr), zinc (Zn), tin (Sn), boron (B), indium (In), and aluminum. It is preferably at least one selected from the group consisting of (Al) and silicon (Si). In particular, titanium (Ti), zirconium (Zr), chromium (Cr), or silicon (Si) is preferable.

  The second resist material preferably contains a sol-gel material. By including the sol-gel material, the second resist layer 13 having good dry etching resistance can be easily filled into the concave portion 23 of the nanoimprint mold 22. 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 species Si. Moreover, the 2nd resist material can also use the hybrid of these sol-gel materials and well-known photopolymerizable resin.

  From the viewpoint of suppressing physical destruction during dry etching, the second resist material preferably has 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 second resist layer 13, 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.

From the viewpoint of dry etching resistance as the second resist layer 13, 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, and Si and Ta. 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 during coating drying, 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.

  The second resist material is preferably a hybrid including an inorganic segment and an organic segment from the viewpoint of transfer accuracy of the second resist layer 13 and dry etching resistance. 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 by covalent bonding. A bound molecule, 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 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.

  As the photopolymerizable radical polymerization resin constituting the second resist layer 13, the photopolymerizable radical polymerization resin constituting the first resist layer 12 is preferably used.

  The photopolymerizable cationic polymerization resin constituting the second resist layer 13 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 the nanoimprint mold 22 because it is effective in filling the recess 23 of the nanoimprint mold 22. 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.

  Specific examples of the cationic curable monomer include the following. Examples of the alicyclic epoxy compound include 3 ′, 4′-epoxycyclohexanecarboxylic acid-3,4-epoxycyclohexylmethyl, 3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylic acid-3,4-epoxy. Examples include -6'-cyclohexylmethyl, vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

  Examples of the glycidyl ether include bisphenol A glycidyl ether, bisphenol F glycidyl ether, hydrogenated bisphenol A glycidyl ether, hydrogenated bisphenol F glycidyl ether, 1,4-butanediol glycidyl ether, 1,6-hexanediol glycidyl ether, Examples include methylolpropane triglycidyl ether, glycidyl methacrylate, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylethyldiethoxysilane, and 3-glycidyloxypropyltriethoxysilane.

  Examples of the oxetane compound include 3-ethyl-3- (phenoxymethyl) oxetane, di [1-ethyl (3-oxetanyl)] methyl ether, 3-ethyl-3allyloxymethyloxetane, 3-ethyl-3- ( 2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-{[3- (triethoxysilyl) propoxy] methyl} oxetane, and the like.

  Examples of the vinyl ether include 2-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, 2-hydroxybutyl vinyl ether, 4-hydroxybutyl vinyl ether, triethylene glycol divinyl ether, cyclohexane dimethanol divinyl ether, 1,4-butanediol divinyl ether, and the like. .

  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. Examples of the photoacid generator include sulfonium hexafluoroantimonate, benzyltriphenylphosphonium hexafluorophosphate, benzylpyridinium hexafluorophosphate, diphenyliodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, benzoin tosylate, adekatopomer sp -170, sp-172 (manufactured by ADEKA), WPAG-145, WPAG-170, WPAG-199, WPAG-281, WPAG-336, WPAG-367 (manufactured by Wako Pure Chemical Industries, Ltd.), CPI-100P, CPI- 101A, CPI-200K, CPI-210S (manufactured by San Apro), DTS-102 (manufactured by Midori Chemical), TPS-TF, DTBPI-PFBS (Toyo Gosei Co., Ltd.) ), And the like.

  In the case where the filling property when filling the second resist layer 13 into the concave portion 23 of the nanoimprint mold 22 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. From the viewpoint of filling, the additive concentration is preferably 40 parts by weight or more, more preferably 60 parts by weight or more with respect to 100 parts by weight of the mask material. 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. In particular, it is preferable from the viewpoint of compatibility that at least one functional group of a functional group having a carboxyl group, a urethane group, or an isocyanuric acid derivative is included. 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 second resist material in a state dissolved in a solvent.

(Nanoimprint mold)
The material of the nanoimprint mold 22 is not particularly limited as long as the concave-convex structure 21 can be formed and the second resist layer 13 filled in the concave portion 23 can be transferred to the first resist layer 12. Transparent material such as quartz, glass, and alumina can be used. A metal oxide, a metal such as Ni, Cr, Al, or Si, or an organic material such as a resin can be used as appropriate.

  The shape of the concavo-convex structure 21 of the nanoimprint mold 22 is not particularly limited, and various shapes are selected according to the concavo-convex pattern 52 formed by lift-off. For example, a pillar shape including a plurality of convex portions having a conical shape, a pyramid shape, or an elliptical cone shape, a line and space structure, a circuit structure, and the like can be given.

(Patterning layer)
As a material of the patterning layer 51 formed by the lift-off method, for example, a metal, a metal oxide, a metal compound, or the like that can be formed by a normal vapor deposition method can be used. For example, aluminum, molybdenum, chromium, copper, platinum, gold, silver or ITO, or a mixture thereof can be used.

  Hereinafter, the present invention will be described in more detail based on examples carried out to clarify the effects of the present invention. Note that the materials, composition of use, processing steps, and the like in the following embodiments are illustrative and can be implemented with appropriate changes. Other modifications can be made without departing from the scope of the present invention. Therefore, the present invention is not limited at all by the following examples.

As the nanoimprint mold used in the examples, a resin mold having a dot pattern composed of the following concave portions on the surface thereof was used.
Concave diameter: 650 nm
Concave depth: 800 nm
Pitch Px in the X axis direction: 700 nm
Y-axis direction pitch Py: 700 nm

  The resin mold is formed through a transfer process from a mold for producing a resin mold having a fine dot pattern by a direct drawing lithography method using a semiconductor pulse laser.

  The photosensitive resin materials (A) and (B) prepared as described below were prepared. The photosensitive resin material (A) is applied onto a resin mold using an automatic bar coater (bar coater No. 4), dried in an oven at 105 ° C. for 10 minutes, and a photosensitive resin composition is formed on a part of the concave portion of the resin mold. Sheet I filled with product (A) was obtained. The filling depth of the photosensitive resin composition (A) into the resin mold recess was 630 nm.

  Further, the photosensitive resin material (B) is applied to the obtained sheet I using an automatic bar coater (bar coater No. 4), dried in an oven at 105 ° C. for 15 minutes, and photosensitive so as to cover the recess. A sheet II coated with the resin material (B) was obtained.

  Thereafter, the obtained sheet II was bonded to a quartz base material that had been heated to 85 ° C. and on which ITO was formed on the surface, to obtain a laminate A-1.

  Photosensitive resin material (A) (second resist material): 2.73 parts by mass of tetra-n-butoxytitanium (manufactured by Tokyo Chemical Industry Co., Ltd.), 3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 1.45 Parts by mass, SH710 (trimethyl-terminated phenylmethylsiloxane, manufactured by Toray Dow Corning) 0.21 parts by mass, Irgacure 369 (BASF) 0.029 parts by mass, Irgacure 184 (BASF) 0.083 parts by mass, propylene glycol monomethyl ether 5 .12 parts by mass and 20.4 parts by mass of acetone mixed

  Photosensitive resin material (B) (first resist material): CNEA-100 (Novolak acrylate, manufactured by KSM, solid content 50%) 7.53 parts by mass, EA-HG001 (main component 9, 9′-bis (4 -(Acryloxyethoxy) phenyl) fluorene, manufactured by Osaka Gas Chemical Co., Ltd.) 1.00 parts by mass, Irgacure 369 (BASF) 0.040 parts by mass, Irgacure 184 (BASF) 0.11 parts by mass, propylene glycol monomethyl ether 15. 6 parts by mass and 10.4 parts by mass of acetone mixed

A patterning mask was placed on the upper side of the laminate A-1 on the resin mold side, and contact exposure was performed using a parallel light exposure machine. At the time of exposure, two colored glass filters (UV-D36C) manufactured by Asahi Techno Glass Co., Ltd. were placed on the patterning mask. The illuminance at that time was 2.2 mW / cm ² . The exposure amount was 100 mJ / cm ² . In addition, PLA-501F (made by Canon Inc.) was used for the exposure machine. After the exposure, post-exposure baking was performed at 120 ° C. for 30 seconds. Subsequently, the resin mold was peeled off, developed by immersion for 15 seconds with PGME, then rinsed with ethanol for 10 seconds and dried under pressure to produce a laminate A-2.

Next, the obtained laminate A-2 was dry-etched. Etching with O ₂ gas was performed from the photosensitive resin material surface side, and the photosensitive resin material (B) was finely structured using the photosensitive resin material (A) as a mask to obtain a substrate with a lift-off mask.

Etching with O ₂ gas was performed in the following two steps.
First step:
O ₂ 40 sccm / Ar 10 sccm
Pressure 1Pa
Power 300W
Time 10min
Second step O ₂ 50 sccm
Pressure 1Pa
Power 300W
Time 5min

  When the substrate with the lift-off mask in this state was observed with a scanning electron microscope (SEM), an uneven structure as shown in FIG. 6 was observed. FIG. 6 is a schematic view showing an observation result by a micrograph of the surface of the substrate with a lift-off mask produced in the example of the present invention.

In the base material with a lift-off mask, the cross-sectional shape of the photosensitive resin material (B) was a constricted shape as follows.
Section diameter φ1: 525 nm at the interface between the photosensitive resin material (A) and the photosensitive resin material (B)
Section diameter φ2 of the interface between the photosensitive resin material (B) and the quartz substrate: 500 nm
Minimum cross-sectional diameter φs of photosensitive resin material (B): 425 nm

  From the above results, it was confirmed that a constricted shape can be formed in the first resist layer in the substrate with a lift-off mask.

Next, an aluminum film having a thickness of 50 nm was formed on the quartz substrate with a lift-off mask obtained by the above operation using an electron beam vacuum deposition method (EB deposition method). Deposition was performed at a vacuum degree of 2.5 × 10 ⁻³ Pa, a deposition rate of 20 nm / s, and a substrate temperature of room temperature.

After vapor deposition, the mask layer was peeled off to obtain a quartz substrate on which an uneven pattern was formed. The obtained concavo-convex pattern was a pattern in which holes with a diameter of 525 nm were opened at the following pitch, and no end burr was generated at the concavo-convex edge.
Pitch Px in the X axis direction: 700 nm
Y-axis direction pitch Py: 700 nm

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

  The present invention can be suitably used, for example, for manufacturing a semiconductor device that requires a fine uneven pattern processing technique.

DESCRIPTION OF SYMBOLS 1 Laminated body 10 Base material with mask for lift-off 11 Base material 12 1st resist layer 13 2nd resist layer 14, 21 Uneven structure 15 Mask layer 22 Nanoimprint mold 50 Substrate with uneven pattern 51 Patterning layer 52 Uneven pattern

Claims (7)

A development process in which a laminate in which a first resist layer and a second resist layer functioning as a mask are formed on a main surface of a substrate by a nanoimprint method is processed with a developer that dissolves the first resist layer;
The first resist layer is etched using the second resist layer as a mask to form a concavo-convex structure composed of the first resist layer and the second resist layer and exposing at least a part of the main surface of the substrate. Forming a mask layer having a constricted shape in a cross-sectional view in a direction substantially perpendicular to the main surface of the base material of the first resist layer. Obtaining a material;
The manufacturing method of the base material with a mask for lift-off characterized by comprising.   The method for producing a substrate with a lift-off mask according to claim 1, wherein the uneven structure is nano-order. The nanoimprint method includes:
Forming the first resist layer on the main surface of the substrate;
Filling the second resist layer into the concave portion of the mold having a concavo-convex structure on the surface;
Pressing the surface of the mold against the surface of the first resist layer;
Peeling the mold from the substrate to obtain the laminate;
The manufacturing method of the base material with the mask for lift-offs of Claim 1 or Claim 2 characterized by the above-mentioned. The nanoimprint method includes:
Filling the second resist layer into the concave portion of the mold having a concavo-convex structure on the surface;
Forming the first resist layer on the surface of the mold so as to cover the recess;
Pressing the main surface of the substrate against the surface of the first resist layer;
Peeling the mold to obtain the laminate;
The manufacturing method of the base material with the mask for lift-offs of Claim 1 or Claim 2 characterized by the above-mentioned.   5. The method of manufacturing a lift-off mask substrate according to claim 3, wherein the second resist layer is filled in a part of the concave portion of the mold. The constriction shape includes a cross-sectional width W1 of the first resist layer on the interface side with the second resist, a cross-sectional width W2 of the first resist layer on the interface side with the base material, and the first resist layer 6. The method for manufacturing a lift-off mask substrate according to claim 1, wherein the minimum cross-sectional width Ws satisfies the following formula (1).
Formula (1)
0.5 × W1 <Ws <W1 and 0.5 × W2 <Ws <W2 Forming a patterning layer on the main surface of the base material including the mask layer of the lift-off mask base material according to any one of claims 1 to 6;
The lift-off mask substrate including the patterning layer is treated with a stripping solution that dissolves the first resist layer, the mask layer including the patterning layer formed on the surface is removed, and the main surface is removed. Obtaining a substrate with a concavo-convex pattern in which the concavo-convex pattern of the patterning layer is formed;
The manufacturing method of the base material with an uneven | corrugated pattern characterized by comprising.

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