JP6177168B2 - Etching work material and etching method using the same - Google Patents

Description

  The present invention relates to an etching workpiece having at least a fine pattern mask on the surface and an etching method using the same.

  Conventionally, a photolithography technique has been often used as a fine pattern processing technique in LSI manufacturing. In the photolithography technique, there is 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. In the EB method, since a mask pattern is directly drawn by an electron beam, there is a problem that the drawing time increases as the number of drawing patterns increases, and the throughput until pattern formation decreases significantly. Further, 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, there is a problem that the apparatus cost increases.

  A nanoimprint technique is known as a fine pattern processing technique capable of solving these problems. In the nanoimprint technology, a mold with a fine pattern formed is pressed against a resist film formed on the surface of the workpiece, and the fine pattern formed on the mold is transferred to the resist film, using the resist film as a mask. This is a technique for forming a fine concavo-convex structure on a workpiece by dry etching the workpiece.

  In this nanoimprint method, the thickness of the resist film can be easily adjusted, so even if the pattern is fine, a fine pattern with a higher aspect ratio than when photolithography technology is used by increasing the thickness of the resist film. Thus, a fine pattern mask can be formed on the surface of the workpiece.

  A technique has been proposed in which a workpiece on which a fine concavo-convex structure is formed by such a method is used as a base material of a semiconductor light emitting device, and light extraction efficiency is increased by changing the light guiding direction (for example, patents) Reference 1).

JP 2003-318441 A

  However, even if a fine and high aspect ratio pattern mask can be formed by such a technique, the fine pattern mask cannot be formed due to the etching damage caused by the heat generated during dry etching of the workpiece because of the fine and high aspect ratio. The fine concavo-convex structure in the workpiece may not be a desired shape due to deformation.

  In addition, at the time of dry etching of a workpiece, in order to increase the throughput by processing a plurality of sheets at the same time, it is often necessary to use a sample stage such as a transfer tray industrially. Therefore, even if the dry etching apparatus has a cooling mechanism, the cooling effect is reduced because the sample stage exists between the cooling mechanism and the workpiece, and the heat generated during dry etching is sufficiently cooled. The fine concavo-convex structure in the workpiece cannot be formed into a desired shape.

  This invention is made | formed in view of this point, and it aims at providing the etching workpiece | work material which can form a desired fine uneven structure, and the etching method using the same.

  As a result of intensive studies in order to solve the above-mentioned problems, the inventor has developed an etching work material provided with a mask layer having a fine concavo-convex structure on a substrate, on a mounting member used during the etching process. It has been found that when the overall thermal resistance value when mounted satisfies a specific condition, etching damage due to heat generated during etching processing can be reduced, and a desired fine uneven structure can be formed on the substrate by etching. .

That is, the etching work material of the present invention is an etching work material provided with a mask layer having a pattern width of 2 μm or less and an aspect ratio of 0.1 to 5.0 on a base material. The overall thermal resistance value when the etching workpiece is placed on the placement member to be used is 6.79 × 10 ⁻³ (m ² · K / W) or less.
(The overall thermal resistance value refers to the thermal resistance value of the mounting member and the thermal resistance value of the base material in the mounting region of the etching workpiece in the mounting member, and When other members other than the etching workpiece are present, it is the sum of the thermal resistance values of the other members, and each thermal resistance value represents the thickness of each member and the heat of the material constituting each member. (The value is divided by the conductivity λ.)

  In the etching workpiece of the present invention, when the mounting member is composed of a plurality of materials, the smallest thermal resistance value among the thermal resistance values obtained for each material constituting the mounting member is It is preferable to use the thermal resistance value of the mounting member.

In the etching workpiece of the present invention, it is preferable that the overall thermal resistance value is 3.04 × 10 ⁻³ (m ² · K / W) or less.

In the etching workpiece of the present invention, it is preferable that the overall thermal resistance value is 1.21 × 10 ⁻³ (m ² · K / W) or less.

In the etching workpiece of the present invention, the mounting member includes silicon (Si), quartz (SiO ₂ ), aluminum (Al), silicon carbide (SiC), alumina (Al ₂ O ₃ ), aluminum nitride (AlN). ), Zirconia oxide (ZrO ₂ ), yttria oxide (Y ₂ O ₃ ), and one or more inorganic members coated with at least one of them, part or all of which are constituted. It is preferable.

In the etching workpiece of the present invention, the thickness calculated as the thermal resistance value of the mounting member is made of silicon (Si), aluminum (Al), or silicon (SiC). Alternatively, in the case of aluminum nitride (AlN), 0.001 m to 0.05 m, quartz (SiO ₂ ), alumina (Al ₂ O ₃ ), zirconia oxide (ZrO ₂ ), or yttria oxide (Y ₂ O _3). ), It is preferably 0.001 m or more and 0.02 m or less, and in the case of the inorganic member, it is preferably 0.001 m or more and 0.05 m or less.

The etching method of the present invention includes a step of forming a mask layer having a pattern width of 2 μm or less and a pattern having an aspect ratio of 0.1 to 5.0 on a substrate to obtain an etching workpiece, The step of etching the base material using the mask layer as a mask in a state where the etching workpiece is placed and the overall thermal resistance value is 6.79 × 10 ⁻³ (m ² · K / W) or less. It is characterized by comprising.
(The overall thermal resistance value refers to the thermal resistance value of the mounting member and the thermal resistance value of the base material in the mounting region of the etching workpiece in the mounting member, and When other members other than the etching workpiece are present, it is the sum of the thermal resistance values of the other members, and each thermal resistance value represents the thickness of each member and the heat of the material constituting each member. (The value is divided by the conductivity λ.)

  The semiconductor light emitting device of the present invention comprises a substrate having a fine concavo-convex structure obtained by etching the etching workpiece, and a semiconductor light emitting layer formed on the substrate.

  According to the present invention, it is possible to form a desired fine concavo-convex structure, that is, a uniform pattern shape (uniform pattern width and line shape).

It is a figure which shows an example of the etching workpiece material which concerns on embodiment of this invention. It is a figure which shows the other example of a mounting member. It is a figure which shows an example of the nanoimprint method. It is a figure which shows an example of the mold used for the nanoimprint method.

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

The etching work material of the present invention is an etching work material provided with a mask layer having a pattern width of 2 μm or less and an aspect ratio of 0.1 to 5.0 on a base material, and is used at the time of etching processing. The overall thermal resistance value when the etching workpiece is placed on the placement member is 6.79 × 10 ⁻³ (m ² · K / W) or less.
(The overall thermal resistance value refers to the thermal resistance value of the mounting member and the thermal resistance value of the base material in the mounting region of the etching workpiece in the mounting member, and When other members other than the etching workpiece are present, it is the sum of the thermal resistance values of the other members, and each thermal resistance value represents the thickness of each member and the heat of the material constituting each member. (The value is divided by the conductivity λ.)

  With this configuration, even when a mask layer having a fine concavo-convex pattern with a high aspect ratio is used as a mask, etching damage due to heat generated during etching processing is reduced, and a desired fine concavo-convex structure is formed on a substrate by etching. Can do. In addition, by using the mounting member, which is a component of the etching workpiece, as a conveying member, the throughput can be improved in the dry etching process.

FIG. 1 is a diagram illustrating a state in which an etching workpiece is placed on a placement member.
An etching workpiece 1 shown in FIG. 1 includes a base material 11 and a mask layer 12 formed on the base material 11. The pattern width (W) of the mask layer 12 is 2 μm or less, and the aspect ratio (H / W) of the mask layer 12 is 0.1 to 5.0. The pattern width (W) means the minimum length of a raised portion such as a convex portion in the pattern shape. For example, if the pattern shape is a circle in the cross section, the pattern width is the diameter of the circle in the cross section. Yes, if the pattern shape is elliptical in the cross section, it is the short axis of the ellipse in the cross section.If the pattern shape is rectangular in the cross section, it is the short side of the rectangle in the cross section. If so, it is the line width.

  In the etching workpiece 1 shown in FIG. 1, the mask layer 12 includes a first mask layer 12a and a second mask layer 12b. Note that the mask layer 12 is not limited to the configuration shown in FIG. 1, and may be composed of a single layer or may be composed of three or more layers.

  The etching workpiece 1 is placed on the placement region X of the placement member 2. That is, the etching workpiece 1 and the mounting member 2 are stacked on the mounting region X of the mounting member 2. FIG. 1A shows the case where the etching workpiece 1 is placed directly on the placement region X of the placement member 2, but in the present invention, as shown in FIG. The etching workpiece 1 may be placed on the placement region X via the heat transfer sheet 3. In the present invention, a member other than the heat transfer sheet 3 may be interposed between the mounting member 2 and the etching workpiece 1 as long as etching can be performed in the etching process. Two or more other members may be interposed between the mounting member 2 and the etching workpiece 1.

The overall thermal resistance value when the etching workpiece 1 is placed on the placing member 2 used during etching is 6.79 × 10 ⁻³ (m ² · K / W) or less. Here, the total thermal resistance value refers to the thermal resistance value of the mounting member 2 and the thermal resistance value of the etching workpiece 1 in the mounting region X of the etching workpiece 1 in the mounting member 2, the mounting When a member other than the etching workpiece 1 (for example, the heat transfer sheet 3 for bonding) exists on the member 2, the heat resistance value of the other member (for example, the heat transfer sheet 3 for bonding) It is sum.

Each thermal resistance value is a value obtained by dividing the thickness of each member by the thermal conductivity λ of the material constituting each member. That is, the thermal resistance value R (m ² · K / W) is a value calculated by the thickness d (m) of each member / the thermal conductivity λ (W / m · K) of each member. In the present invention, members and layers constituting the etching workpiece so that the overall thermal resistance value (sum of the thermal resistance values) is R ≦ 6.79 × 10 ⁻³ (m ² · K / W). The material and thickness, and the material and thickness constituting the mounting member are adjusted. The overall thermal resistance value (sum of the thermal resistance values) is more preferably R ≦ 3.04 × 10 ⁻³ (m ² · K / W) or less, and R ≦ 1.21 × 10 ⁻³ ( m ² · K / W) or less is more preferable. The lower limit of the overall thermal resistance value R is preferably 0 ≦ R.

  In the calculation of the thermal resistance value R, if the substrate 11 and the mounting member 2 are flat, the thickness of each plate is defined as the thickness d. Further, the mounting member 2 has a concave portion 2a as shown in FIG. 2A, or has a convex portion 2b as shown in FIG. 2B. When a material is placed, the thickness of the placement region X is set as the thickness d in the calculation of the thermal resistance value R.

In particular, there is no lower limit on the thickness d of the mounting member 2 from the viewpoint of the thermal resistance value. However, if the thickness d of the mounting member 2 is too small, the mounting member 2 may be damaged during transportation. Therefore, it is preferable to adopt a range having durability, for example, 0.001 m or more. Further, although there is an upper limit value for the thickness d considered from the viewpoint of the thermal resistance value, it is preferable that the thickness d of the mounting member 2 be within the following range at the same time from the viewpoint of workability during transportation and cost. . When the material constituting the mounting member 2 is silicon (Si), aluminum (Al), silicon (SiC), or aluminum nitride (AlN), 0.05 m or less, quartz (SiO ₂ ), alumina (Al ₂ In the case of O ₃ ), zirconia oxide (ZrO ₂ ) or yttria oxide (Y ₂ O ₃ ), 0.02 m or less, silicon (Si), quartz (SiO ₂ ), aluminum (Al), silicon carbide ( When the inorganic member is coated with one or more of SiC), alumina (Al ₂ O ₃ ), aluminum nitride (AlN), zirconia oxide (ZrO ₂ ), and yttria oxide (Y ₂ O ₃ ). Is preferably 0.05 m or less.

As described above, the overall thermal resistance value refers to the thermal resistance value of the mounting member 2 and the thermal resistance value of the etching workpiece 1 in the mounting region X of the etching workpiece 1 in the mounting member 2; When other members (for example, the heat transfer sheet 3) other than the etching workpiece 1 are present on the mounting member 2, this is the sum of the thermal resistance values of the other members (for example, the heat transfer sheet 3). For example, as shown in FIG. 1A, when the etching workpiece 1 is placed directly on the placement member 2, the overall thermal resistance value R = R _{base material} + R _{placement member} , and FIG. As shown, when the etching workpiece 1 is placed on the placement member 2 via the heat transfer sheet 3, the overall thermal resistance value R = R _{base material} + R _{placement member} + R _{heat transfer sheet.} It becomes.

  In the case where the mounting member 2 is composed of a plurality of materials, a plurality of calculation paths for the overall thermal resistance value can be considered. In this case, the smallest thermal resistance value among the thermal resistance values obtained for each material constituting the mounting member 2 is set as the thermal resistance value of the mounting member 2.

  The method for measuring the thermal conductivity λ of each material in the calculation of the overall thermal resistance value R is not particularly limited, and various measuring methods such as a laser flash method, a calorimeter method, a probe method, and a plate comparison method can be mentioned. . As the thermal conductivity of each material used for calculation of the thermal resistance value, the thermal conductivity measured in a state where each material exists alone is used. In this embodiment, the thermal conductivity measured by the laser flash method is used for the calculation.

  The material of the substrate 11 is not particularly limited as long as the overall thermal resistance value falls within the above range, and an inorganic material or an organic material can be used. Examples of the material of the base material 11 include sapphire, SiC, SiN, GaN, W-Cu, silicon, zinc oxide, magnesium oxide, manganese oxide, zirconium oxide, manganese zinc iron oxide, magnesium aluminum oxide, zirconium boride, and oxidation. Examples include gallium, indium oxide, lithium gallium oxide, lithium aluminum oxide, neodymium gallium oxide, lanthanum strontium aluminum tantalum, strontium titanium oxide, titanium oxide, hafnium, tungsten, molybdenum, GaP, and GaAs. Further, as the material of the base material 11, a material constituting the support substrate 5 described later or a material constituting the mold 4 may be selected.

  In particular, a sapphire substrate can be used as the base material 11 in a case where the improvement of the internal quantum efficiency of the semiconductor light emitting device and the improvement of the light extraction efficiency are satisfied at the same time. In this case, the sapphire substrate is processed using the obtained mask layer having a fine concavo-convex structure with a high aspect ratio (a fine pattern composed of the first mask layer 12a and the second mask layer 12b) 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 mask layer having a fine concavo-convex structure with a high aspect ratio as a mask. A glass plate, a glass film, etc. can be selected if it is the objective of producing the non-reflective surface glass by a large area fine pattern. 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 in which carbon black is kneaded or coated on the surface can be employed.

  The shape of the base material 11 such as the thickness is not particularly limited as long as the overall thermal resistance value range is satisfied. A film can be used as the substrate 11.

[Mounting member]
The mounting member 2 is a member on which the etching work material 1 is placed, and can be used as a transport tray for fixing or transporting the etching work material 1. By using the mounting member 2, it is possible to reduce misalignment of the etching workpiece 1 when the etching workpiece 1 is transported to the vacuum reaction tank of the dry etching apparatus, and a plurality of etching workpieces Since 1 can be conveyed simultaneously, throughput is increased.

Examples of the material constituting the mounting member 2 include metal materials such as silicon (Si), aluminum (Al), and stainless steel, quartz (SiO ₂ ), silicon carbide (SiC), silicon nitride (SiN), and alumina (Al ₂ O ₃ ), aluminum nitride (AlN), zirconia oxide (ZrO ₂ ), yttria oxide (Y ₂ O ₃ ) and other ceramics, silicon and aluminum coated with alumite, silicon, aluminum and resin with ceramic sprayed on the surface Examples thereof include metal materials such as silicon and aluminum coated with the material. These materials are not particularly limited as long as the above-described overall thermal resistance value conditions are satisfied, but it is preferable to select materials that do not generate highly depositable reactants with respect to the dry etching gas. More preferable examples include silicon (Si), quartz (SiO ₂ ), and aluminum (Al), which have high availability and workability of the mounting member 2, silicon carbide (SiC), and alumina (Al ₂ O ₃ ). , Aluminum nitride (AlN), zirconia oxide (ZrO ₂ ), yttria oxide (Y ₂ O ₃ ), and inorganic members coated with one or more of these generate particularly highly depositable reactants It is preferable in terms of difficulty. In addition, the inorganic member used here is specifically a metal material having high workability such as silicon (Si) or aluminum. By coating such an inorganic member with a material such as silicon carbide (SiC) that does not generate a highly depositable reaction product, both ease of processing and compatibility with dry etching can be achieved. In this case, aluminum nitride (AlN) or the like is not 100% aluminum nitride (AlN) at the time of coating, and part of it is alumina (Al ₂ O ₃ ) and the coating layer is a mixture. There is. Therefore, the description of “coated with any one or more of these” means that there is a case where other materials are mixed when attempting to cover with a certain material. Yes.

  The shape of the mounting member 2 is not particularly limited as long as the overall thermal resistance value condition is satisfied, and examples thereof include a thin plate circular shape and a thin plate square shape. The surface of the mounting member 2 does not need to be flat, and as shown in FIG. 2A, a recess 2a for accommodating the etching workpiece 1 may be formed. Moreover, the mounting member 2 does not need to be comprised with the single material, and may be comprised with two or more types of materials. Furthermore, the mounting member 2 does not need to be formed as a single structure, and two or more types such as a lid for fixing the etching workpiece 1 by covering the base portion and a part of the etching workpiece 1. These structures may be combined.

[Formation of fine uneven mask layer]
Examples of a method for forming the mask layer 12 having a fine concavo-convex structure on the surface of the substrate 11 include generally known fine pattern formation techniques such as photolithography, thermal lithography, and nanoimprint. In the present embodiment, nanoimprint is used from the viewpoint that nano-sized pattern formation is inexpensive and easy, but the present invention is not limited to this.

FIG. 3 is an explanatory diagram showing an example of the nanoimprint method.
A first mask layer 12a and a second mask layer 12b constituting a mask layer are formed on the substrate 11 in that order to obtain a laminate. The mold 4 having a fine concavo-convex structure is pressed against the laminate so that the second mask layer 12b of the laminate and the fine concavo-convex structure surface are in contact with each other (FIG. 3A), and then the mold 4 is peeled from the laminate. Thereby, the fine concavo-convex structure is transferred to the first mask layer 12a and the second mask layer 12b (FIG. 3B).

  Next, the first mask layer 12a is dry-etched using the second mask layer 12b as a mask. Thereby, the etching workpiece 1 which has the mask layer 12 comprised by the 1st mask layer 12a and the 2nd mask layer 12b on the base material 11 is produced (FIG. 3C). By subjecting the etching workpiece 1 to dry etching using the mask layer 12 as a mask, a fine concavo-convex structure is formed on the substrate 11.

[mold]
The shape of the mold 4 is not particularly limited as long as a fine concavo-convex structure is formed on the surface, but is preferably a flat plate shape, a film shape or a reel shape, and particularly preferably a flat plate shape or a film shape. As shown in FIG. 4A, the mold 4 has a fine relief structure 4a on the surface. The mold 4 may be provided on a support substrate 5 as shown in FIG. 4B.

  Examples of the material of the mold 4 include inorganic materials such as silicon, quartz, nickel, chromium, sapphire, and SiC, and organic materials such as polydimethylsiloxane (PDMS), a thermoplastic resin, and a photocurable resin. The supporting substrate 5 includes a rigid substrate such as glass, quartz, silicon, and SUS, an elastic substrate made of an elastic material such as sponge and rubber (silicone rubber), and a resin film such as a PET film, a TAC film, and a COP film. Etc.

  As shown in FIG. 4A, as the mold 4 that does not include the support substrate 5, a hard flat plate mold made of an inorganic material such as silicon, quartz, nickel, chromium, sapphire, SiC, soft PDMS, COP, Examples thereof include a film mold made of polyimide, polyethylene, PET, fluororesin, or the like. By using the hard flat plate-shaped mold 4, the surface accuracy of the mold 4 can be kept high. Here, the surface accuracy means the parallelism between the top position of the fine concavo-convex structure 4a of the mold 4 and the surface opposite to the fine concavo-convex structure 4a. By using an etching work material to which a fine pattern is transferred using such a mold 4 having a high degree of parallelism (surface accuracy), the pattern formation accuracy of the transferred fine pattern (main target substrate 11) The parallelism between the surface and the surface constituted by the top of the mask layer 12 can be kept high, and when the mask layer 12 having a fine concavo-convex structure is etched (a fine pattern mask forming step), the aspect ratio A high fine concavo-convex structure can be formed with high accuracy. Thereby, it becomes possible to ensure the processing accuracy when processing the substrate of the etching workpiece having a fine concavo-convex structure with a high aspect ratio.

  On the other hand, by using the soft mold 4, large bubbles are entrained when the laminate for forming a fine pattern including the mold 4 is bonded to the substrate 11, and micro bubbles are formed inside the fine concavo-convex structure 4 a. Can be suppressed. Furthermore, since the irregularities on the surface of the substrate 11 can be absorbed, the transfer accuracy is improved. These effects improve the processing accuracy of the mask layer having a fine concavo-convex structure with a high aspect ratio produced on the base material 11 and also the base material 11 of the etching workpiece 1 having a fine concavo-convex structure with a high aspect ratio. The processing accuracy when processing is guaranteed.

[Second mask layer]
The material constituting the second mask layer 12b (second mask material) is not particularly limited as long as the etching selectivity described later is satisfied, and various known resins (organic substances) that can be diluted in a solvent, inorganic precursors, and inorganic condensations. Body, plating solution (chromium plating solution, etc.), metal oxide filler, metal oxide fine particles, HSQ, SOG (spin on glass) can be used.

  The second mask layer 12b is a photopolymerizable light from the viewpoint of transfer accuracy when a fine pattern having a high aspect ratio is transferred to the substrate 11 using a laminate for forming a fine pattern using the mold 4. It is particularly preferable that the polymerizable group and / or the polymerizable group capable of being thermally polymerized are included. The second mask layer 12b preferably contains a metal element from the viewpoint of dry etching resistance in the fine pattern mask forming step. Furthermore, the second mask layer 12b is preferable because it contains metal oxide fine particles, which makes it easier to perform dry etching on a substrate made of an inorganic material.

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, the concentration of the material constituting the second mask layer 12b diluted with the solvent is such that the solid content of the coating film applied on the unit area is the void (concave) of the fine concavo-convex structure in which the solid area exists on the unit area (down) The concentration is not particularly limited as long as the concentration is not more than the volume.

  Examples of the photopolymerizable group contained in the second mask layer 12b 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.

  The metal elements contained in the second mask layer 12b include titanium (Ti), zirconium (Zr), chromium (Cr), zinc (Zn), tin (Sn), boron (B), indium (In), It is preferably at least one selected from the group consisting of aluminum (Al) and silicon (Si). In particular, titanium (Ti), zirconium (Zr), chromium (Cr), and silicon (Si) are preferable.

  Examples of the known resin contained in the second mask layer 12b include both a photopolymerizable resin and a thermopolymerizable resin, or any one of the resins. For example, in addition to the resin constituting the mold 4 described above, a photosensitive resin used for photolithography, a photopolymerizable resin and a thermopolymerizable resin used for nanoimprint lithography, and the like can be given. In particular, for dry etching used in the fine pattern mask formation step, an etching selectivity (Vo1 /) calculated from an etching rate (Vm1) of the second mask layer 12b and an etching rate (Vo1) of the first mask layer 12a described later. Vm1) preferably contains a resin that satisfies 10 ≦ Vo1 / Vm1. When the etching selectivity (Vo1 / Vm1) between the second mask layer 12b and the first mask layer 12a satisfies Vo1 / Vm1> 1, this means that the second mask layer 12b is less likely to be etched than the first mask layer 12a. Means. In particular, by satisfying Vo1 / Vm1 ≧ 10, the thick first mask layer 12a can be easily processed by dry etching, and the dry etching micro-processed mask layer having a fine concavo-convex structure with a high aspect ratio (second mask) A fine pattern comprising the layer 12b and the first mask layer 12a) can be formed on the substrate 11, which is preferable.

  In addition, since the dry etching rate with respect to a fine pattern has large influence on a fine pattern, these etching selectivity is a value measured with respect to the flat film (solid film) of various materials.

The second mask material preferably includes a sol-gel material. By including the sol-gel material, the second mask layer 12b having good dry etching resistance can be easily filled into the fine concavo-convex structure of the mold 4, and in addition, when the first mask layer 12a is dry-etched. , a vertical dry etching rate (Vr _⊥), the ratio of the lateral dry etching rate _{(Vr //) (Vr ⊥ /} Vr //) can be increased. As the sol-gel material, only a metal alkoxide having a single metal species may be used, or metal alkoxides having different metal species may be used in combination. In particular, a metal alkoxide having a metal species M1 (where M1 is at least one metal element selected from the group consisting of Ti, Zr, Zn, Sn, B, In, and Al) and a metal having a metal species Si. It is preferable to contain at least two kinds of metal alkoxides together with alkoxides. Or the material which combined these sol-gel materials and well-known photopolymerizable resin can also be used as a 2nd mask material.

Further, from the viewpoint of dry etching resistance of the second mask layer 12b, the sol-gel material preferably contains at least two kinds 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 mask layer 12b preferably includes an inorganic segment and an organic segment (hybrid) from the viewpoint of transfer accuracy and dry etching resistance of the second mask layer 12b. Combinations include, for example, a combination of inorganic fine particles and a photopolymerizable (or thermally polymerizable) resin, a combination of an inorganic precursor and a photopolymerizable (or thermally polymerizable) resin, and an organic polymer and an inorganic segment covalently bonded. And combinations with molecules bound at. When a sol-gel material is used as the inorganic precursor, it is preferable to include a photopolymerizable resin in addition to the sol-gel material containing a silane coupling agent. In the case of a combination, 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 combination is not particularly limited as long as it can be photopolymerized, whether it is a radical polymerization system or a cationic polymerization system.

  If the diluted second mask material has poor wettability when applied directly onto the fine concavo-convex structure 4a of the mold 4, 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 second mask 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 second mask material and improving the transfer accuracy, when using a surfactant or a leveling material, the concentration of these additives is 20% by weight or less with respect to the second mask material. Preferably there is. Dispersibility is greatly improved when it is 20% by weight or less, and transfer accuracy is 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 second mask material in a state dissolved in a solvent.

  If the second mask material contains a material whose state changes in the solvent volatilization process after dilution coating, it is presumed that a driving force for reducing the area of the material itself also acts at the same time. This is preferable because the mask material is filled into the mold recess. 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 is polycondensed. As a result, the energy of the sol-gel material becomes unstable, so that a driving force that tries to move away from the solvent liquid surface (solvent-air interface) that decreases as the solvent is dried works, and as a result, the sol-gel material is well placed inside the mold recess. It is assumed that it will be filled.

  Next, examples of substances that may be used for the second mask layer 12b will be given, but it is not necessary to include all of them, and they can be selected according to the purpose.

  First, a metal alkoxide is mentioned. The metal alkoxide is a compound group in which an arbitrary metal species described in the element table and a functional group such as a hydroxy group, a methoxy group, an ethoxy group, a propyl group, or an isopropyl group are bonded. Examples of the metal alkoxide of the metal species (for example, Si) include dimethyldiethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, p-styryltriethoxysilane, and methylphenyldiethoxy. Examples include silane, 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. Even if one or more of the functional groups of the metal alkoxide is a photopolymerizable group such as acryloyl group, methacryloyl group, acryloxy group, methacryloxy group, acryl group, methacryl group, vinyl group, epoxy group, allyl group, oxetanyl group, etc. Good. For example, KBM-1003 (made by Shin-Etsu Silicone) which is vinyltrimethoxysilane, KBE-1003 (made by Shin-Etsu Silicone) which is vinyltriethoxysilane, SZ-6300 (made by Toray Dow Corning) which is vinyltrimethoxysilane SZ-6075 (made by Toray Dow Corning) which is vinyltriacetoxysilane, TSL8310 (made by GE Toshiba Silicone) which is vinyltrimethoxysilane, TSL8311 (made by GE Toshiba Silicone) which is vinyltriethoxysilane, 3- KMB-502 (made by Shin-Etsu Silicone) which is methacryloxypropylmethyldimethoxysilane, KMB-503 (made by Shin-Etsu Silicone) which is 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane KME-502 (manufactured by Shin-Etsu Silicone), KBM-503 (manufactured by Shin-Etsu Silicone) which is 3-methacryloxypropyltriethoxysilane, SZ-6030 (manufactured by GE Toshiba Silicone) which is γ-methacryloxypropyltrimethoxysilane ), TSL8370 (manufactured by GE Toshiba Silicone) which is γ-methacryloxypropyltrimethoxysilane, TSL8375 (manufactured by GE Toshiba Silicone) which is γ-methacryloxypropylmethyldimethoxysilane, and 3-acryloxypropyltrimethoxysilane. KBM-5103 (manufactured by Shin-Etsu Silicone), KBM-303 (manufactured by Shin-Etsu Silicone) which is 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, KBM-4 which is 3-glycidoxypropylmethyldimethoxysilane 2 (manufactured by Shin-Etsu Silicone), KBM-403 (manufactured by Shin-Etsu Silicone) which is 3-glycidoxypropyltrimethoxysilane, KBE-402 (manufactured by Shin-Etsu Silicone) which is 3-glycidoxypropylmethyldiethoxysilane And KBE-403 (manufactured by Shin-Etsu Silicone) which is 3-glycidoxypropyltriethoxysilane, KBM-1403 (manufactured by Shin-Etsu Silicone) which is p-styryltrimethoxysilane, and the like.

  Next, a metal chelate compound is mentioned. Examples of metal chelate compounds include titanium diisopropoxy bisacetylacetonate, titanium tetrakisacetylacetonate, titanium dibutoxybisoctylene glycolate, zirconium tetrakisacetylacetonate, zirconium dibutoxybisacetylacetonate, aluminum trisacetylacetonate, Examples include aluminum dibutoxy monoacetylacetonate, zinc bisacetylacetonate, indium trisacetylacetonate, and polytitanium acetylacetonate. 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.

  Next, halogenated silanes are mentioned, which is a group of compounds in which the metal species of the metal alkoxide is silicon and the functional group for hydrolysis polycondensation is replaced with a halogen atom.

  Next, liquid glass is mentioned, for example, the TGA series made from Apollo ring, etc. are mentioned. Other sol-gel compounds can be added in accordance with the desired physical properties.

Next, a silsesquioxane compound is mentioned. 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, but the polysiloxane having any structure such as a cage type, a ladder type, and a random type. It may be. Further, in the composition formula _{(RSiO 3/2) n,} R is a substituted or unsubstituted siloxy group, it may be any other substituent. n is preferably 8-12. 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 and the like, and an alkoxysilyl group. 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.

Next, a fluorine-containing silane coupling agent is mentioned. The fluorine-containing silane coupling agent is, for example, 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 straight-chain 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.

Next, polysilane is mentioned.
Next, a metal oxide particle is mentioned. This refers to particles, fillers, fibers, and the like made of metal oxides described in the periodic table. Examples of the metal oxide fine particles include silica, alumina, zirconia, titania, ITO (tin-doped indium oxide), tin oxide, zinc oxide, and antimony oxide.

  Next, silicone is mentioned. Examples of silicones include linear low-polymerization silicone oils that exhibit fluidity at room temperature, such as polydimethylsiloxane (PDMS), which is a polymer of dimethylchlorosilane, modified silicone oils thereof, Linear PDMS or three-dimensional network structure composed of silicone rubber that is moderately crosslinked by PDMS to exhibit rubbery elasticity, modified silicone rubber, resinous silicone, PDMS and tetrafunctional siloxane Silicone resin (or DQ resin) which is a resin having In some cases, an organic molecule is used as the cross-linking agent, or tetrafunctional siloxane (Q unit) is used. The silicone compound is preferably selected from the group consisting of PDMS, silicone oil, silicone resin, modified silicone oil and modified silicone resin. 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. The reactive silicone is preferably a silicone containing a hydroxyl group (—OH group), a silicone containing an alkoxy group, a silicone containing a trialkoxy group, or a silicone containing an epoxy group. 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. Specific examples of commercially available modified silicones include TSF4421 (manufactured by GE Toshiba Silicone), XF42-334 (manufactured by GE Toshiba Silicone), XF42-B3629 (manufactured by GE Toshiba Silicone), and XF42-A3161 (GE Toshiba Silicone). FZ-3720 (manufactured by Toray Dow Corning), BY 16-839 (manufactured by Toray Dow Corning), SF8411 (manufactured by Dow Corning Toray), FZ-3737 (manufactured by Dow Corning Toray) BY 16-876 (Toray Dow Corning), SF8421 (Toray Dow Corning), SF8416 (Toray Dow Corning), SH203 (Toray Dow Corning), SH230 (Toray Dow Corning) SH510 (Toray Dow Corning), SH550 (Tohoku) Les Dow Corning), SH710 (Toray Dow Corning), SF8419 (Toray Dow Corning), SF8422 (Toray Dow Corning), BY16 Series (Toray Dow Corning), FZ3785 (Toray Dow Corning), KF-410 (Shin-Etsu Chemical Co., Ltd.), KF-412 (Shin-Etsu Chemical Co., Ltd.), KF-413 (Shin-Etsu Chemical Co., Ltd.), KF-414 (Shin-Etsu Chemical Co., Ltd.) KF-415 (made by Shin-Etsu Chemical Co., Ltd.), KF-351A (made by Shin-Etsu Chemical Co., Ltd.), KF-4003 (made by Shin-Etsu Chemical Co., Ltd.), KF-4701 (made by Shin-Etsu Chemical Co., Ltd.), KF-4917 (Shin-Etsu Chemical Co., Ltd.), KF-7235B (Shin-Etsu Chemical Co., Ltd.), KR213 (Shin-Etsu Chemical Co., Ltd.), KR500 (Shin-Etsu Chemical Co., Ltd.), KF-970 (Shin-Etsu Chemical Co., Ltd.), X21-5841 (Shin-Etsu Chemical Co., Ltd.), X-22-2000 (Shin-Etsu Chemical Co., Ltd.), X-22-3710 (Shin-Etsu Chemical Co., Ltd.), X-22-7322 (Made by Shin-Etsu Chemical Co., Ltd.), X-22-1877 (made by Shin-Etsu Chemical Co., Ltd.), X-22-2516 (made by Shin-Etsu Chemical Co., Ltd.), PAM-E (made by Shin-Etsu Chemical Co., Ltd.) and the like. Examples of the reactive silicone include amino modification, epoxy modification, alicyclic epoxy modification, carboxyl modification, carbinol modification, methacryl modification, vinyl modification, mercapto modification, phenol modification, one-terminal reactivity, and heterofunctional modification. . Examples of the silicone compound containing a vinyl group include KR-2020 (manufactured by Shin-Etsu Silicone), X-40-2667 (manufactured by Shin-Etsu Silicone), CY52-162 (manufactured by Toray Dow Corning), CY52-190 (Toray). Dow Corning), CY52-276 (Toray Dow Corning), CY52-205 (Toray Dow Corning), SE1885 (Toray Dow Corning), SE1886 (Toray Dow Corning), SR-7010 Toray Dow Corning), XE5844 (GE Toshiba Silicone) and the like. Examples of the silicone compound containing a methacryl group include X-22-164 (manufactured by Shin-Etsu Silicone), X-22-164AS (manufactured by Shin-Etsu Silicone), X-22-164A (manufactured by Shin-Etsu Silicone), X- 22-164B (made by Shin-Etsu Silicone), X-22-164C (made by Shin-Etsu Silicone), X-22-164E (made by Shin-Etsu Silicone), etc. are mentioned.

  Examples of the silicone compound containing an amino group include PAM-E (manufactured by Shin-Etsu Silicone), KF-8010 (manufactured by Shin-Etsu Silicone), X-22-161A (manufactured by Shin-Etsu Silicone), X-22-161B ( Shin-Etsu Silicone), KF-8012 (Shin-Etsu Silicone), KF-8008 (Shin-Etsu Silicone), X-22-166B-3 (Shin-Etsu Silicone), TSF4700 (Momentive Performance Materials Japan) ), TSF4701 (made by Momentive Performance Materials Japan), TSF4702 (made by Momentive Performance Materials Japan), TSF4703 (made by Momentive Performance Materials Japan), TSF4704 (momentive Pa (Manufactured by Momentive Performance Materials Japan), TSF4705 (made by Momentive Performance Materials Japan), TSF4706 (made by Momentive Performance Materials Japan), TSF4707 (made by Momentive Performance Materials Japan) ), TSF4708 (made by Momentive Performance Materials Japan), TSF4709 (made by Momentive Performance Materials Japan), and the like.

  Examples of the silicone compound containing an epoxy group include X-22-163 (manufactured by Shin-Etsu Silicone), KF-105 (manufactured by Shin-Etsu Silicone), X-22-163A (manufactured by Shin-Etsu Silicone), X-22- 163B (manufactured by Shin-Etsu Silicone), X-22-163C (manufactured by Shin-Etsu Silicone), TSF-4730 (manufactured by Momentive Performance Materials Japan), YF3965 (manufactured by Momentive Performance Materials Japan), etc. Is mentioned. Examples of the silicone containing an alicyclic epoxy group include X-22-169AS (manufactured by Shin-Etsu Silicone), X-22-169B (manufactured by Shin-Etsu Silicone), and the like.

  Next, a polymerization initiator is mentioned. Examples of polymerization initiators include acetophenone, p-tert-butyltrichloroacetophenone, chloroacetophenone, 2,2-diethoxyacetophenone, hydroxyacetophenone, 2,2-dimethoxy-2′-phenylacetophenone, 2-aminoacetophenone, dialkyl In addition to aminoacetophenone, etc., benzoin 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-methylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyldimethyl ketal Benzophenone-based photopolymerization initiators: benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, hydroxypropylbenzophenone, acrylic benzophenone, 4,4'-bis (dimethyl) Amino) benzophenone, perfluorobenzophenone, etc., thioxanthone photopolymerization initiators: thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, diethylthioxanthone, dimethylthioxanthone, etc. Anthraquinone photopolymerization initiators: 2-methylanthraquinone, 2- Ketal photopolymerization such as ethyl anthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone Initiator: acetophenone dimethyl ketal, benzyl dimethyl ketal, and other photopolymerization initiators: α-acyl oxime ester, benzyl- (o-ethoxycarbonyl) -α-monooxime, acyl phosphine oxide, glyoxy ester, 3-ketocoumarin, 2-ethylanthraquinone, camphorquinone, tetramethylthiuram sulfide, azobisisobutyronitrile, benzoyl peroxide, dialkyl peroxide, tert-butyl peroxypivalate, etc., photopolymerization initiator having a fluorine atom: perfluoro tert-butyl peroxide, Known and conventional photopolymerization initiators such as perfluorobenzoyl peroxide can be used alone or in combination of two or more. Other examples of commercially available initiators include “Irgacure®” manufactured by BASF (for example, 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. As a combination in the case of using two types together, for example, “Irgacure” manufactured by BASF, or a combination of “Irgacure” and “Darocur” can be mentioned. For example, Darocur 1173 and Irgacure 819. This, IRGACURE 379 and Irgacure127, Irgacure819 and Irgacure127, Irgacure250 and Irgacure127, Irgacure184 and Irgacure 369, Irgacure184 and Irgacure379EG, Irgacure184 and Irgacure907, Irgacure127 and Irgacure379EG, Irgacure819 and Irgacure184, DarocurTPO and Irgacure184, and the like.

  Next, a photosensitizer is mentioned. As photosensitizers, n-butylamine, di-n-butylamine, tri-n-butylphosphine, allylthiourea, s-benzisoisouronium-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, triethanolamine, etc. It can be used in combination with one or more known and commonly used photosensitizers such as amines.

  Next, a photo-acid generator is mentioned. The photoacid generator may be a compound that generates an acid by receiving active energy such as ultraviolet rays, and examples thereof include aromatic onium salts such as sulfonium salts and iodonium salts. The cationic curable monomer is polymerized by the acid generated by the photoacid generator. Examples of the sulfonium salt include triphenylsulfonium, diphenyl-4-thiophenoxysulfonium, and the like. Examples of the iodonium salt include diphenyliodonium, bis (dodecylphenyl) iodonium, 4-isopropyl-4'-methyldiphenyliodonium, and the like. Sulfonium hexafluoroantimonate, benzyltriphenylphosphonium hexafluorophosphate, benzylpyridinium hexafluorophosphate, diphenyliodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, benzoin tosylate, adekatopomer sp-170 (manufactured by ADEKA), ADEKA Optomer sp-172 (made by ADEKA), WPAG-145 (made by Wako Pure Chemical Industries), WPAG-170 (made by Wako Pure Chemical Industries), WPAG-199 (made by Wako Pure Chemical Industries), WPAG-281 (Manufactured by Wako Pure Chemical Industries, Ltd.), WPAG-336 (manufactured by Wako Pure Chemical Industries, Ltd.), WPAG-367 (manufactured by Wako Pure Chemical Industries, Ltd.), CPI-100P (manufactured by San Apro), CPI-101A (manufactured by San Apro) , CPI-200K (manufactured by San Apro), CPI-210S (manufactured by San Apro), DTS-102 (manufactured by Midori Chemical), TPS-TF (manufactured by Toyo Gosei Co., Ltd.), DTBPI-PFBS (manufactured by Toyo Gosei Kogyo Co., Ltd.) Etc. As the photoacid generator, known and commonly used photoacid generators can be used alone or in combination of two or more. Examples of counter anions of the above aromatic onium salts include tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, hexafluoroarsenate, hexachloroantimonate, tetrakis (pentafluorophenyl) borate, perchlorate ion, Examples thereof include trifluoromethanesulfonate ion, bis (trifluoromethanesulfonyl) imidate ion, and bis (pentafluoroethylsulfonyl) imidate ion. Examples of the sensitizer include anthracene, 1,9-dibutoxyanthracene, 1,9-dipropoxyanthracene, carbazole, phenothiazine, perylene, xanthone, thioxanthone, benzophenone thioxanthone, 2,4-diethyl-9H-thioxanthene- 1-one is mentioned, and a well-known and usual sensitizer can be used individually or in combination of 2 or more types.

  Next, a chelating agent is mentioned. A chelating agent is a general term for substances in which a plurality of atoms in a ligand molecule are bonded to a metal ion to form a metal chelate complex. The chelating agent is not particularly limited as long as it can chelate a metal alkoxide and is cleaved by light irradiation, and examples thereof include β-diketone compounds and β-ketoester compounds. For example, β-diketones include β-diketones having 5 to 13 carbon atoms such as acetylacetone, benzoylacetone, dibenzoylmethane, 2,2,6,6-tetramethyl-3,5-heptanedione, vinylacetylacetone and the like. .

  In addition, the definition of the term used by the description so far is as follows. A (meth) acryl group means an acrylic group and a methacryl group. The (meth) acryloyl group means an acryloyl group and a methacryloyl group. The (meth) acryloxy group means an acryloxy group and a methacryloxy group.

[First mask layer]
The first mask layer 12a is not particularly limited as long as it satisfies the etching rate ratio (etching selection ratio) in the fine pattern mask forming step described above. As a material constituting the first mask layer 12a (first mask material), a photopolymerizable radical polymerization resin, a cationic polymerization resin, other known commercially available photopolymerizable or thermopolymerizable resins, dry A resin that is partially cross-linked and that can be thermocompression bonded, typified by a film resist, can be used.

  The second mask layer 12b and the first mask layer 12a are preferably chemically bonded from the viewpoint of transfer accuracy. Therefore, when the second mask layer 12b includes a photopolymerizable group, the first mask layer 12a also includes a photopolymerizable group, and when the second mask layer 12b includes a thermopolymerizable group, the first mask layer 12a. Also preferably contains a thermally polymerizable group. The first mask layer 12a may contain a sol-gel material in order to generate a chemical bond by condensation with the sol-gel material in the second mask layer 12b. As the photopolymerization method, there are a radical system and a cationic system, but from the viewpoint of curing speed and dry etching resistance, only a radical system or a combination of a radical system and a cationic system (hybrid) is preferable. In the case of the combination, it is preferable to mix the radical polymerization resin and the cationic polymerization resin in a weight ratio of 3: 7 to 7: 3, and it 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 12a during dry etching, the Tg (glass transition temperature) of the first mask layer 12a after curing is preferably 30 ° C. to 300 ° C., 600 More preferably, the temperature is from ℃ to 250 ℃.

  From the viewpoint of adhesion between the first mask layer 12a and the base material 11, and between the first mask layer 12a and the second mask layer 12b, the shrinkage rate of the first mask layer 12a by the specific gravity method is 5% or less. preferable.

  In addition, from the viewpoint of handling when using a structure in which the mold 4, the second mask layer 12 b, and the first mask layer 12 a are laminated, and bonding to the base material 11, the first mask layer 12 a is a dry film resist. It is preferable that the resin can be thermocompression-bonded represented by Here, the dry film resist is an organic material including at least a binder polymer, a reactive diluent, and a polymerization initiator, and means a resin capable of thermocompression bonding. In particular, the mold 4 and the laminate of the mold 4 and the support substrate 5 are preferably in the form of a film. In this case, the laminated body which consists of the mold 4, the 2nd mask layer 12b, and the 1st mask layer 12a is produced, a cover film can be match | combined, and it can wind up and collect | recover. This roll can be fed out and easily bonded to a desired substrate by thermocompression bonding. Such a usage method means that know-how such as filling and peeling of a transfer material for nanoimprint (transfer) can be eliminated by using the laminate for forming a fine pattern, and no special apparatus is required. . The resin that can be thermocompression bonded is preferably a resin that can be bonded at 200 ° C. or lower, and more preferably 150 ° C. or lower. For example, a known dry film resist is laminated on the mold 4 and the second mask layer 12b to form a laminate of the mold 4, the second mask layer 12b, and the first mask layer 12a. The dry film resist is more preferably a dry film resist containing a photosensitive resin from the viewpoint of adhesiveness with the second mask layer 12b.

  Next, examples of substances that may be used for the first mask layer 12a will be given, but it is not necessary to include all of them, and they can be selected according to the purpose.

  First, a resin having a polycyclic aromatic structure (molecular weight of 1000 or more) is exemplified. This includes a condensed polycyclic aromatic structure in which at least two ring structures are condensed. In addition, the “polycyclic aromatic” is not limited to those in which all condensed rings such as naphthalene are aromatic rings, but fused with aromatic and non-aromatic rings, for example, benzene and cyclohexane are fused. The 1,2,3,4-tetrahydronaphthalene structure and the like are also included. Further, from the viewpoint of suppressing depots, the polycyclic aromatic structure is preferably 2 to 4 condensed ring structures, more preferably 2 to 3 condensed ring structures, and two condensed ring structures. It is particularly preferred that Examples of the hydrocarbon-based polycyclic aromatic structure include naphthalene, anthracene, phenanthrene, pyrene, 1,2,3,4-tetrahydronaphthalene and the like. Examples of the heteropolycyclic aromatic structure include indole, carbazole, quinoline, benzoisoquinoline, and the like. In addition, examples of the cyclic structure of the present invention include a cyclic structure described in Chemical Formula Group A below.

In this specification, “*” represented in the chemical formula is bonded to another element via “*”, and “*” represents oxygen element (O), nitrogen element (N), sulfur element ( S) or carbon element (C). Further, the portion lacking a bond is bonded to a hydrogen element (H), a methyl group (CH ₃ ), or a hydroxyl group (OH).

  For example, examples of the cyclic structure exemplified in the chemical formula group A include polystyrene, poly p-hydroxystyrene, poly (9 vinyl carbazole), a polymer having a carbazole skeleton, and a polymer having a carbazole skeleton in a side chain. , Polymer having cresol novolac skeleton, polymer having phenol novolac skeleton, polymer having bisphenol A skeleton, polymer having fluorene skeleton, polymer having adamantane skeleton in side chain Or a polymer having an adamantyl skeleton in the side chain, a polymer having a norbornane skeleton in the side chain, or a polymer having a naphthalene skeleton in the side chain.

  Next, a photoinitiator is mentioned. The photopolymerization initiator causes a radical reaction or an ionic reaction by light, and a photopolymerization initiator that causes a radical reaction is preferable. Examples of the photopolymerization initiator include the following photopolymerization initiators.

  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. Photoinitiators having fluorine atoms: Known and commonly used photoinitiators such as perfluorotert-butyl peroxide and perfluorobenzoyl peroxide can be used alone or in combination of two or more.

  Examples of commercially available initiators include “Irgacure®” manufactured by BASF (for example, 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 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 part of the fine uneven structure 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. In addition, as a combination in the case of using two types together, for example, “Irgacure” manufactured by BASF Japan Co., Ltd., “Irgacure” and “Darocur”, Darocur 1173 and Irgacure 819, Irgacure 379 and Irgacure 127, Irgacure 819 and 1250 Irgacure 127, Irgacure 184 and Irgacure 369, Irgacure 184 and Irgacure 379EG, Irgacure 184 and Irgacure 907, Irgacure 127 and Irgacure 379EG, Irgacure 819 and Irgacure 819

  Next, a photosensitizer is mentioned. 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.

  Next, coloring substances, such as dye and a pigment, are mentioned. A coloring dye represented by a combination of a leuco dye or a fluoran dye and a halogen compound can also be used. Of these, combinations of tribromomethylphenyl sulfone and leuco dyes, combinations of triazine compounds and leuco dyes, and the like are useful. Examples of the coloring substance 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.), Examples thereof include Basic Blue 20 and Diamond Green (Eisen (registered trademark) DIAMOND GREENGH manufactured by Hodogaya Chemical Co., Ltd.). There are combinations of leuco dyes or fluoran dyes and halogen compounds.

  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.

  Next, a radical polymerization inhibitor is mentioned. Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2′-methylenebis. (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), diphenylnitrosamine and the like.

  Next, a plasticizer is mentioned. Examples of the plasticizer include phthalic acid esters such as diethyl phthalate, p-toluenesulfonamide, polypropylene glycol, polyethylene glycol monoalkyl ether, and the like.

  Next, an antioxidant is mentioned. The antioxidant here is preferably a light stabilizer. The light stabilizer can be classified into a radical chain initiation inhibitor, a radical scavenger, and a peroxide decomposer, and any of them can be adopted. Radical chain initiation inhibitors can be further classified into heavy metal deactivators and UV absorbers, heavy metal deactivators mainly include hydrazides and amides, and UV absorbers mainly include benzotriazoles, There are benzophenone series and triazine series. Among these, an ultraviolet absorber is more preferable. Since the resist composition can be optically stabilized by including an ultraviolet absorber, it can be used in a place suitable for use. Radical scavengers can be classified into hindered amine light stabilizers (HALS) and phenolic antioxidants. As these antioxidants, known general materials can be used.

  Next, a reaction aid thiol compound is mentioned. Although it does not specifically limit as a thiol compound, What has 2 or more thiol groups in 1 molecule is preferable, and what has 4 or more is the most preferable. As what has two thiol groups in 1 molecule as a polyfunctional thiol, Karenz MT PE1 is mentioned as what has four Karenz MT BD1 by Showa Denko KK, for example. In addition, alkoxysilylalkylthiol can be added and reacted with the polyfunctional (meth) acrylate in the resist composition.

  Next, a metal element is mentioned. Examples of the metal element include manganese (Mn), cobalt (Co), nickel (Ni), copper (Cu), rubidium (Rb), niobium (Nb), molybdenum (Mo), technetium (Tc), and ruthenium (Ru). ), Palladium (Pd), silver (Ag), cesium (Cs), osmium (Os), platinum (Pt), gold (Au), potassium (K), lithium (Li), sodium (Na), barium (Ba) ), Calcium (Ca), magnesium (Mg), lead (Pb), strontium (Sr), zinc (Zn), aluminum (Al), boron (B), bismuth (Bi), iron (Fe), gallium (Ga) ), Indium (In), lanthanum (La), antimony (Sb), vanadium (V), yttrium (Y), germanium (Ge), hafnium At least one selected from the group consisting of Hf), silicon (Si), tin (Sn), titanium (Ti), zirconium (Zr), niobium (Nb), tantalum (Ta), and tungsten (W). Preferably there is. Such a metal element can be introduced by adding metal oxide particles, metal particles, metal alkoxides, metal complexes, metal ions, or the like to the resist composition. Here, the particles include a filler.

  Next, a polymerizable monomer is mentioned. 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 a single monomer is used, 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.

  Specific examples of the (meth) 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-based (meth) acrylate [stearyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, allyl acrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol di Acrylate, trimethylolpropane triacrylate, pentaaerythritol triacrylate, dipentaerythritol hexaacrylate and the like. ], Hydrocarbon-based (meth) acrylates containing etheric oxygen atoms [ethoxyethyl acrylate, methoxyethyl acrylate, glycidyl acrylate, tetrahydrofurfryl acrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, polyoxyethylene glycol diacrylate , Tripropylene glycol diacrylate and the like. ], A hydrocarbon-based (meth) acrylate [2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl vinyl ether, N, N-diethylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate, N-vinyl pyrrolidone, dimethylaminoethyl methacrylate, etc. ], Silicone-based acrylates, and the like. 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 Acrylate, ethoxylated sphenol A diacrylate, propoxylated neopentyl glycol diacrylate, tricyclodecane dimethano And diacrylate. 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. Alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) Acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylonitrile, benzyl (meth) acrylate, methoxybenzyl (meth) acrylate, chlorobenzyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, Aryl (meth) acrylates such as phenoxyethyl (meth) acrylate, phenyl (meth) acrylate, cresyl (meth) acrylate, naphthyl (meth) acrylate, vinyl compounds having a phenyl group (for example, styrene), Le (meth) acrylate. Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, cyclohexyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate , 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, N-butoxymethyl acrylamide , Styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, (meth) acrylonitrile, glycidyl (meth) acrylate, and the like. Styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene and the like. Polyalkylene glycol dimethacrylate with 2 moles of propylene oxide and 6 moles of ethylene oxide added to both ends of bisphenol A, and polyethylene glycol with 5 moles of ethylene oxide added to both ends of bisphenol A, respectively. Dimethacrylate (NK ester BPE-500 made by Shin-Nakamura Chemical Co., Ltd.) and polyethylene glycol dimethacrylate (NK ester BPE-200 made by Shin-Nakamura Chemical Co., Ltd.) each having an average of 2 moles of ethylene oxide added to both ends of bisphenol A. . 1,6-hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2-di (p-hydroxyphenyl) propanedi (Meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyoxypropyltrimethylolpropane tri (meth) acrylate, polyoxyethyltrimethylolpropane triacrylate, pentaerythritol tetra (meth) acrylate, Dipentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, bisphenol A diglycidyl ester Terdi (meth) acrylate, β-hydroxypropyl-β ′-(acryloyloxy) propyl phthalate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyalkylene glycol (meth) acrylate, polypropylene glycol A mono (meth) acrylate etc. are mentioned.

  Examples of the urethane compound include a diisocyanate compound such as hexamethylene diisocyanate, tolylene diisocyanate, or 2,2,4-trimethylhexamethylene diisocyanate, and a compound having a hydroxyl group and a (meth) acryl group in one molecule (2- And urethane compounds obtained by reaction with hydroxypropyl acrylate, oligopropylene glycol monomethacrylate, etc.). Specifically, there is a reaction product of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (Nippon Yushi Co., Ltd., Bremma-PP1000).

  There may be a plurality of addition polymerizable unsaturated bonds in the molecule. Examples of compounds having only one addition polymerizable unsaturated bond in the molecule include alkylene glycol derivatives such as polyethylene glycol, polypropylene glycol monoacrylate and monomethacrylate, bisphenol A monoacrylate and monomethacrylate, and 1 mol to bisphenol A. After reacting more alkylene glycol, bisphenol A derivative esterified by reacting acrylic acid or methacrylic acid or the like at one OH terminal, after reacting 1 mol or more of alkylene glycol to phthalic acid, Phthalic acid derivatives obtained by reacting acrylic acid or methacrylic acid or the like with the OH terminal of the above, salicylic acid derivatives such as salicylic acid acrylate, phenoxyhydroxyalkyl (meth) acrylate, etc.The compound having only one addition polymerizable unsaturated bond in the molecule is preferably a phthalic acid derivative from the viewpoint of etching resistance, and more preferably β-hydroxypropyl-β ′-(acryloyloxy) propyl phthalate.

  Examples of compounds having a plurality of addition polymerizable unsaturated bonds in the molecule include trimethylolpropane derivatives such as trimethylolpropane dimethacrylate, tetramethylolpropane derivatives such as tetramethylolpropane tri (meth) acrylate, pentaerythritol trimethacrylate, etc. And isocyanuric acid derivatives such as isocyanic dimethacrylate. A case where β-hydroxypropyl-β '-(acryloyloxy) propyl phthalate and pentaerythritol triacrylate are simultaneously contained is mentioned. Urethaneization of polyvalent isocyanate compounds such as hexamethylene diisocyanate and toluylene diisocyanate with hydroxy acrylate compounds such as 2-hydroxypropyl (meth) acrylate, oligoethylene glycol mono (meth) acrylate and oligopropylene glycol mono (meth) acrylate A compound or the like can also be used.

  Phenoxytetraethylene glycol acrylate, 1,4-tetramethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, heptapropylene glycol di (meth) Acrylate, glycerol (meth) acrylate, glycerol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, diallyl phthalate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) Acrylate, 4-normal octyl phenoxypentapropylene glycol acrylate, 4-bis (triethylene glycol methacrylate) nonap Pyrene glycol, bis (tetraethylene glycol methacrylate) polypropylene glycol, bis (triethylene glycol methacrylate) polypropylene glycol, bis (diethylene glycol acrylate) polypropylene glycol, 4-normalnonylphenoxyoctaethylene glycol (meth) acrylate, 4-normalnonylphenoxyhepta Isocyanurate derivatives such as ethylene glycol dipropylene glycol (meth) acrylate, phenoxytetrapropylene glycol tetraethylene glycol (meth) acrylate, and tris (acryloxyethyl) isocyanurate can be used.

  Diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, nonaethylene glycol mono (meth) acrylate, tetradecaethylene glycol mono (meth) acrylate, trieicosaethylene glycol mono (Meth) acrylate, polyethylene glycol mono (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, methoxynonaethylene glycol (meth) acrylate, methoxytetradeca Ethylene glycol (meth) acrylate, methoxytrieicosaethylene glycol (meth) acrylate Rate, methoxypolyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxynonaethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) Monomers having polyoxyethylene units such as acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate; N-ethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (Meth) acrylamide, N-cyclopropyl (meth) acrylamide, N-methyl-N Ethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-methyl-N-isopropyl (meth) acrylamide, N-methyl-Nn-propyl (meth) Acrylamide, N- (meth) acryloylmorpholine, N- (meth) acryloylpyrrolidine, N- (meth) acryloylpiperidine, N-vinyl-2-pyrrolidone, N-methylenebisacrylamide, N-methoxypropyl (meth) acrylamide, N -Isopropoxypropyl (meth) acrylamide, N-ethoxypropyl (meth) acrylamide, N-1-methoxymethylpropyl (meth) acrylamide, N-methoxyethoxypropyl (meth) acrylamide, N-1-methyl-2-methoxyethyl (Meta ) Monomers having an amide bond such as acrylamide, N-methyl-Nn-propyl (meth) acrylamide, N- (1,3-dioxolan-2-yl) (meth) acrylamide; 2- (meth) acryloyloxyethyl Monomers having a carboxy group such as phthalic acid, 2- (meth) acryloyloxypropyl phthalic acid, 2- (meth) acryloyloxyethyl succinic acid; phosphate groups such as mono (2- (meth) acryloyloxyethyl) acid phosphate Monomers having an ammonium group such as (meth) acryloyloxyethyltrimethylammonium chloride and (meth) acryloyloxypropyltrimethylammonium chloride; 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-phenol Rupropanesulfonic acid, sodium (meth) acryloyloxyethylsulfonate, ammonium (meth) acryloyloxyethylsulfonate, bis (polyoxyethylene polycyclic phenyl ether) methacrylate sulfate, allylsulfonic acid, methallylsulfonic acid, vinyl Monomers having a sulfonic acid group such as sulfonic acid, styrene sulfonic acid, sodium sulfonic acid ethoxy methacrylate and the like.

  In particular, from the viewpoint of the density of the surface chemical structure group, nonylphenoxypolyethylene glycol (meth) acrylate, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, mono ( 2- (Meth) acryloyloxyethyl) acid phosphate, (meth) acryloyloxypropyltrimethylammonium chloride, sodium (meth) acryloyloxyethylsulfonate, and bis (polyoxyethylene polycyclic phenyl ether) methacrylate sulfate are preferred.

  The fluorine-containing (meth) acrylate has excellent adhesion to the support substrate 5 when it has a functional group. 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. The fluoro (meth) _{acrylate, CH 2 = CHCOO (CH 2} ) 2 (CF 2) 10 F, CH 2 = CHCOO (CH 2) 2 (CF 2) 8 F, CH 2 = CHCOO (CH 2) 2 ( CF ₂ ) ₆ F, CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₂ (CF ₂ ) ₁₀ F, CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₂ (CF ₂ ) ₈ F, CH _{2 = C (CH 3) COO (} CH 2) 2 (CF 2) 6 F, CH 2 = CHCOOCH 2 (CF 2) 6 F, CH 2 = C (CH 3) COOCH 2 (CF 2) 6 F, CH 2 = CHCOOCH ₂ (CF ₂ ) ₇ F, CH ₂ = C (CH ₃ ) COOCH ₂ (CF ₂ ) ₇ F, CH ₂ = CHCOOCH ₂ CF ₂ CF ₂ H, CH ₂ = CHCOOCH ₂ (CF _{2 CF 2) 2 H, CH 2} = CHCOOCH 2 (CF 2 CF 2) 4 H, CH 2 = C (CH 3) COOCH 2 (CF 2 CF 2) H, CH 2 = C (CH 3) COOCH 2 (CF _{2 CF 2) 2 H, CH} 2 = C (CH 3) COOCH 2 (CF 2 CF 2) 4 H, CH 2 = CHCOOCH 2 CF 2 OCF 2 CF 2 OCF 3, CH 2 = CHCOOCH 2 CF 2 O (CF _{2 CF 2 O) 3 CF 3} , CH 2 = C (CH 3) COOCH 2 CF 2 OCF 2 CF 2 OCF 3, CH 2 = C (CH 3) COOCH 2 CF 2 O (CF 2 CF 2 O) 3 CF _{3, CH 2 = CHCOOCH 2 CF} (CF 3) OCF 2 CF (CF 3) O (CF 2) 3 F, CH 2 = CHCOOCH 2 CF (CF 3) O _{CF 2 CF (CF 3) O} ) 2 (CF 2) 3 F, CH 2 = C (CH 3) COOCH 2 CF (CF 3) OCF 2 CF (CF 3) O (CF 2) 3 F, CH 2 = _{C (CH 3) COOCH 2 CF} (CF 3) O (CF 2 CF (CF 3) O) 2 (CF 2) 3 F, CH 2 = CFCOOCH 2 CH (OH) CH 2 (CF 2) 6 CF (CF _{3) 2, CH 2 = CFCOOCH} 2 CH (CH 2 OH) CH 2 (CF 2) 6 CF (CF 3) 2, CH 2 = CFCOOCH 2 CH (OH) CH 2 (CF 2) 10 F, CH 2 = _{CFCOOCH 2 CH (OH) CH 2} (CF 2) 10 F, CH 2 = CHCOOCH 2 CH 2 (CF 2 CF 2) 3 CH 2 CH 2 OCOCH = CH 2, CH 2 = C (CH 3 _{COOCH 2 CH 2 (CF 2 CF} 2) 3 CH 2 CH 2 OCOC (CH 3) = CH 2, CH 2 = CHCOOCH 2 CyFCH 2 OCOCH = CH 2, CH 2 = C (CH 3) COOCH 2 CyFCH 2 OCOC ( Fluoro (meth) acrylates such as CH ₃ ) ═CH ₂ are mentioned (where CyF represents perfluoro (1,4-cyclohexylene group). ).

The _{fluorodiene, CF 2 = CFCF 2 CF =} CF 2, CF 2 = CFOCF 2 CF = CF 2, CF 2 = CFOCF 2 CF 2 CF = CF 2, CF 2 = CFOCF (CF 3) CF 2 CF = CF ₂ , CF ₂ = CFOCF ₂ CF (CF ₃ ) CF = CF ₂ , CF ₂ = CFOCF ₂ OCF = CF ₂ , CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF = CF ₂ , CF ₂ = CFCF ₂ C _{(OH) (CF 3) CH} 2 CH = CH 2, CF 2 = CFCF 2 C (OH) (CF 3) CH = CH 2, CF 2 = CFCF 2 C (CF 3) (OCH 2 OCH 3) CH 2 Fluorodienes such as CH═CH ₂ , CF ₂ ═CFCH ₂ C (C (CF ₃ ) ₂ OH) (CF ₃ ) CH ₂ CH═CH _{2 and the} like can be mentioned.

Next, a fluororesin is mentioned. This includes fluorine-containing polyurethane, polytetrafluoroethylene (PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / ethylene copolymer. A polymer (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), a fluorine-containing acrylic resin, or the like can also be used. As ETFE, a molar ratio (TFE / E) of a repeating unit based on tetrafluoroethylene (hereinafter referred to as TFE) and a repeating unit based on ethylene (hereinafter referred to as E) is 70/30 to 30/70. The thing of 65/35-40/60 is more preferable. ETFE can also contain repeat units based on other comonomers. Other comonomers, for _example, CF 2 = fluoro ethylenes excluding the representative feel more alert TFE to _CFCl, hexafluoropropylene typified by CF 2 = CFCF ₃ or _{CF 2 = CHCF 3, CF 3} CF 2 CF 2 CF 2 fluoro ethylenes that CH = CH ₂ and _{CF 3 CF 2 CF 2 CF 2} CF = number of carbon atoms represented by CH ₂ has a 2-12 perfluoroalkyl _{group, Rf (OCFXCF 2) k OCF} = CF 2 ( provided that , Rf is a perfluoroalkyl group having 1 to 6 carbon atoms, X is a fluorine atom or a trifluoromethyl group, k is an integer of 0 to 5), and excluding E Olefins, C3 olefins typified by propylene, and C4 olefins typified by butylene and isobutylene. Emissions, and the like. Among these, CF ₃ CF ₂ CF ₂ CF ₂ CH═CH ₂ is particularly preferable. Further, the ratio of the repeating unit based on the other comonomer is preferably 30 mol% or less, more preferably 0.1 to 15 mol%, and more preferably 0.1 to 15 mol% of all repeating units (100 mol%) constituting ETFE. 10 mol% is particularly preferred. Moreover, a fluorine-containing cyclic polymer can be included. Here, the fluorinated cyclic polymer is a fluorinated polymer having a fluorinated aliphatic ring in the main chain, and at least one carbon atom constituting the fluorinated aliphatic ring is the main chain of the fluorinated polymer. It is defined as the carbon atom that constitutes the chain. The atoms constituting the fluorinated aliphatic ring may contain oxygen atoms, nitrogen atoms, etc. in addition to carbon atoms. The fluorine-containing aliphatic ring is preferably a fluorine-containing aliphatic ring having 1 to 2 oxygen atoms. The number of atoms constituting the fluorinated aliphatic ring is preferably 4 to 7. When the fluorinated cyclic polymer is a polymer obtained by polymerizing a cyclic monomer, the carbon atom constituting the main chain is a polymerizable double bond of the monomer constituting the fluorinated polymer. Derived from two carbon atoms. In the case of a polymer obtained by cyclopolymerizing a diene monomer, it is derived from 4 carbon atoms of 2 polymerizable double bonds. As the polymerizable double bond, a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group are preferable. Examples of the fluorinated cyclic polymer include homopolymers or copolymers of cyclic monomers, and homopolymers or copolymers obtained by cyclopolymerizing diene monomers. The cyclic monomer is a monomer having a fluorine-containing aliphatic ring and having a polymerizable double bond between carbon atoms constituting the fluorine-containing aliphatic ring, or a fluorine-containing aliphatic ring. And a monomer having a polymerizable double bond between a carbon atom constituting the fluorinated aliphatic ring and a carbon atom outside the fluorinated aliphatic ring. The diene monomer is a monomer having two polymerizable double bonds.

The cyclic monomer and the diene monomer are monomers having a fluorine atom, and the number of fluorine atoms bonded to the carbon atom relative to the total number of hydrogen atoms bonded to the carbon atom and fluorine atoms bonded to the carbon atom. A monomer having a ratio of 80% or more is preferable, and a perfluoromonomer (a monomer having the ratio of 100%) is more preferable. The cyclic monomer and the diene monomer are monomers in which a part of fluorine atoms (preferably 1 to 4) of the perfluoromonomer are substituted with chlorine atoms (hereinafter referred to as perhalopolyfluoromonomers). (Mer). The monomer to be copolymerized with the cyclic monomer and the diene monomer is also preferably a perfluoromonomer or a perhalopolyfluoromonomer. Examples of the monomer to be copolymerized with the cyclic monomer include CF ₂ = CF ₂ , CF ₂ = CFCl, CF ₂ = CFOCF _{3 and the} like. Further, as the diene _{monomer, CF 2 = CF-Q-} CF = CF 2 (Q is an etheric perfluoroalkylene group oxygen atom 1-3 carbon atoms which may have a .Q Is a perfluoroalkylene group having an etheric oxygen atom, the etheric oxygen atom in the perfluoroalkylene group may be present at one end of the group or at both ends of the group. And may be present between carbon atoms of the group, preferably from one end of the group from the viewpoint of cyclopolymerizability. As specific examples of the diene monomer, CF ₂ = CFOCF ₂ CF = CF ₂ , CF ₂ = CFOCF (CF ₃ ) CF = CF ₂ , CF ₂ = CFOCF ₂ CF ₂ CF = CF ₂ , CF ₂ = CFOCF _{2 CF (CF 3) CF =} CF 2, CF 2 = CFOCF (CF 3) CF 2 CF = CF 2, CF 2 = CFOCF 2 OCF = CF 2, CF 2 = CFOC (CF 3) 2 OCF = CF 2, _{CF 2 = CFCF 2 CF = CF} 2, CF 2 = CFCF 2 CF 2 CF = CF 2 , and the like. Noahsolve GS BP85 (manufactured by Green Noah Co., Ltd.), Zeorora (registered trademark) H (manufactured by ZEON CORPORATION), Zonyl (registered trademark) TC coat (manufactured by DuPont), "Cytop (registered trademark)" manufactured by Asahi Glass Co., Ltd. (For example, CTL-107M, CTL-107A), “Asahiklin (registered trademark)” (for example, AE-3000, AE-3100E, AK-225, AC-6000, AC-2000), Novec (registered trademark) EGC -1720 (manufactured by Sumitomo 3M), “OPTOOL (registered trademark)” (for example, DSX, DAC, AES), “Durasurf (registered trademark)” (for example, HD-2101Z, HD-2100, HD) manufactured by Daikin Industries, Ltd. -1101Z), "Eftone (registered trademark)" (for example, AT-100), "Zeffle (registered trademark)" (example) GH-701), “Unidyne (registered trademark)”, “Die Free (registered trademark)”, “Optoace (registered trademark)”, “Fuategent (registered trademark)” manufactured by Neos (for example, M series: Footgent (registered trademark) 251, Footent (registered trademark) 215M, Footent (registered trademark) 250, FTX-245M, FTX-290M; S series: FTX-207S, FTX-211S, FTX-220S, FTX-230S F series: FTX-209F, FTX-213F, Footgent® 222F, FTX-233F, Footgent® 245F; G series: Footent® 208G, FTX-218G, FTX-230G; , FTS-240G; Oligomer series: Footagent (Registered trademark) 730FM, phagegent (registered trademark) 730LM; phgentent (registered trademark) P series; phgentent (registered trademark) 710FL; FTX-710HL, etc.), DIC's "Megafuck (registered trademark)" (for example, F-114, F-410, F-493, F-494, F-443, F-444, F-445, F-470, F-471, F-474, F-475, F-477, F -479, F-480SF, F-482, F-483, F-489, F-172D, F-178K, F-178RM, MCF-350SF, etc.), "Fluorosurf (registered trademark)" manufactured by Fluoro Technology Can be used.

Next, a fluorine-containing silane coupling material is mentioned. The fluorine-containing silane coupling agent, for example, the 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 addition, the definition of the term used by the description so far is as follows. A (meth) acryl group means an acrylic group and a methacryl group. The (meth) acryloyl group means an acryloyl group and a methacryloyl group. The (meth) acryloxy group means an acryloxy group and a methacryloxy group.

[Fine pattern forming process]
The fine pattern forming step is a nanoimprint method in which a first mask layer 12a and a second mask layer 12b constituting a mask layer are formed in that order on the base material 11 to obtain a laminate, and has a fine concavo-convex structure. The mold 4 is pressed against the laminated body so that the second mask layer 12b of the laminated body and the fine concavo-convex structure surface are in contact with each other (FIG. 3A), and then the mold 4 is peeled from the laminated body. Is transferred to the first mask layer 12a and the second mask layer 12b (FIG. 3B). That is, this step includes a step of bonding the laminate for forming a fine pattern composed of the mold 4, the second mask layer 12b, and the first mask layer 12a and the base material 11, and a step of peeling the mold 4. Including at least.

  This laminates a laminate for forming a fine pattern composed of the mold 4, the second mask layer 12b, and the first mask layer 12a on the base material 11, and the composition of the bonding surface by heat or light (UV). After the product is cured, the mold 4 is peeled off. In addition, when bonding a fine pattern laminated body and the base material 11, in order to improve adhesiveness, 1 or more types of intermediate | middle layers may exist between a fine pattern laminated body and the base material 11. FIG. The intermediate layer is not particularly limited as long as it can be removed in the subsequent fine pattern mask forming process or the dry etching process of the substrate 11.

[Fine pattern mask forming process]
The fine pattern mask formation step is a process for etching the second mask layer shown in FIG. 3C by performing etching under the condition that only the first mask layer 12a is etched without using the second mask layer 12b as a mask. In this step, a mask layer (fine pattern mask) composed of 12b and the first mask layer 12a is formed on the surface of the substrate 11.

  As the etching in the fine pattern mask forming step, a generally known etching method such as wet etching or dry etching can be used. Various etching conditions can be designed depending on the material. For example, when dry etching is used, the following etching conditions can be used.

From the viewpoint of chemically etching the second mask layer 12b, O ₂ gas and H ₂ gas can be selected. Ar gas and Xe gas can be selected from the viewpoint of improving the etching rate in the vertical direction (vertical direction) by increasing the ion incident component. As a gas used for etching, a mixed gas containing at least one of O ₂ gas, H ₂ gas, and Ar gas is used. In particular, it is preferable to use only O ₂ .

  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.

Further, the mixed gas ratio of O ₂ gas or H ₂ gas and Ar gas or Xe gas is improved in anisotropy when the chemically reactive etching component and the ion incident component are in an appropriate amount. Therefore, when the gas layer flow rate is 100 sccm, 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. When the total flow rate of the gas changes, it becomes a mixed gas according to the above flow rate ratio.

As plasma etching, capacitively coupled RIE, inductively coupled RIE, inductively coupled RIE, or RIE using an ion attraction bias can be used. For example, using a gas in which only O ₂ gas or O ₂ gas and Ar gas are mixed at a gas flow ratio of 90 sccm: 10 sccm to 70 sccm: 30 sccm, the processing pressure is set to a range of 0.1 to 1 Pa, and Capacitive coupling RIE or RIE using an ion pull-in voltage is used. When the total flow rate of the mixed gas used for etching changes, the mixed gas conforms to the above flow rate ratio.

  Components having a low vapor pressure contained in the second mask layer 12b (for example, a sol-gel material having a metal element such as Ti, Zr, Ta, Zn, Si, or a metalloxane bonding site) etch the first mask layer 12a. At this time, it plays a role of protecting the side wall of the first mask layer 12a, and as a result, the thick first mask layer 12a can be easily etched.

  In this fine pattern mask forming step, it is not always necessary to use a mounting member, and it is not necessary to select the material and shape of each member so that the entire thermal resistance value is within the range.

In the etching method of the present invention, a mask layer having a pattern width of 2 μm or less and a pattern with an aspect ratio of 0.1 to 5.0 is formed on a substrate 11 to obtain an etching workpiece 1, and a mounting member 2. The substrate 1 is etched using the mask layer as a mask in a state where the etching workpiece 1 is placed thereon and the overall thermal resistance value is 6.79 × 10 ⁻³ (m ² · K / W) or less. . Here, the overall thermal resistance value refers to the thermal resistance value of the mounting member 2 and the thermal resistance value of the substrate 11 in the mounting region X of the etching workpiece 1 in the mounting member 2, and the mounting member 2. When other members other than the etching workpiece 1 are present, the sum of the thermal resistance values of the other members, and the respective thermal resistance values indicate the thickness of each member and the material constituting each member. It is a value divided by the thermal conductivity λ.

  For example, a semiconductor light emitting element can be obtained by forming a semiconductor light emitting layer on the substrate 11 having a fine concavo-convex structure obtained by etching in this way.

[Dry etching process of substrate]
The dry etching process of the base material 11 is based on the conditions under which the base material 11 is etched using the mask layer 12 (fine pattern mask) composed of the second mask layer 12b and the first mask layer 12a as shown in FIG. 3C as a mask. This is a step of forming a fine concavo-convex structure on the surface of the substrate 11 by performing dry etching.

From the viewpoint of etching the substrate 11, etching using a chlorine-based gas or a chlorofluorocarbon-based gas can be performed. O ₂ (oxygen) gas, Ar (argon) gas, or a mixed gas of O ₂ gas and Ar gas may be added to the chlorine-based gas. A mixed gas containing at least one kind of Freon-based gas (CxHzFy: x = 1 to 4, y = 1 to 8, z = 0 to 3 in the range) that is easy to reactively etch the substrate 11 Is used. Examples of the fluorocarbon gas include CF ₄ , CHF ₃ , C ₂ F ₆ , C ₃ F ₈ , C ₄ F ₆ , C ₄ F ₈ , CH ₂ F ₂ , and CH ₃ F. Furthermore, in order to improve the etching rate of the base material 11, a gas in which Ar gas, O ₂ gas, and Xe gas are mixed in a fluorocarbon gas to 50% or less of the total gas flow rate is used. Chlorine that can be reactively etched when etching the base material 11 that is difficult to be reactively etched with chlorofluorocarbon-based gas (base material that is difficult to etch) or the base material 11 that generates highly depositable reactants. A mixed gas containing at least one of the system gases is used. Examples of the chlorine-based gas include Cl ₂ , BCl ₃ , CCl ₄ , PCl ₃ , SiCl ₄ , HCl, CCl ₂ F ₂ , and CCl ₃ F. Further, in order to improve the etching rate of the difficult-to-etch base material, O ₂ gas, Ar gas, or a mixed gas of O ₂ gas and Ar gas may be added to the chlorine-based gas.

  The etching pressure is preferably 0.1 Pa to 20 Pa, more preferably 0.1 Pa to 10 Pa, because the ion incident energy contributing to the reactive etching increases and the etching rate of the substrate 11 is improved. preferable.

  Also, two kinds of CFCs (CxHzFy: x = 1 to 4, y = 1 to 8, z = 0 to 3) in which C and F ratios (y / x) are different are mixed. And the taper-shaped angle of the fine pattern produced in the base material 11 can be made separately by increasing / decreasing the deposition amount of the fluorocarbon film which protects the etching side wall of the base material 11. When the shape of the mask with respect to the base material 11 is controlled more precisely by dry etching, the ratio of the flow rate of the Freon gas with F / C ≧ 3 and the Freon gas with F / C <3 is 95 sccm: 5 sccm to 60 sccm: 40 sccm. It is preferably 70 sccm: 30 sccm to 60 sccm: 40 sccm, and more preferably. Even when the total gas flow rate changes, the ratio of the above flow rates does not change.

In addition, the mixed gas of chlorofluorocarbon and Ar gas, and O ₂ gas or Xe gas improves the etching rate of the substrate 11 when the reactive etching component and the ion incident component are in appropriate amounts. In view of the above, the gas flow rate ratio 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. In addition, the mixed gas of chlorine-based gas and Ar gas, and O ₂ gas or Xe gas improves the etching rate of the substrate 11 when the reactive etching component and the ion incident component are in appropriate amounts. In view of the above, 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 80 sccm: 20 sccm, and still more preferably 90 sccm: 10 sccm to 70 sccm: 30 sccm. Even when the total gas flow rate changes, the ratio of the above flow rates does not change.

Further, the etching of the substrate 11 using a chlorine-based gas only BCl ₃ gas, or it is preferable to use a BCl ₃ gas and a mixed gas of Cl ₂ gas and Ar gas or a mixed gas of Xe gas. These mixed gases preferably have a gas flow rate ratio of 99 sccm: 1 sccm to 50 sccm: 50 sccm from the viewpoint of improving the etching rate of the substrate 11 when the reactive etching component and the ion incident component are appropriate amounts, and 99 sccm: 1 sccm to 70 sccm: 30 sccm is more preferable, and 99 sccm: 1 sccm to 90 sccm: 10 sccm is more preferable. Even when the total gas flow rate changes, the ratio of the above flow rates does not change.

As plasma etching, capacitively coupled RIE, inductively coupled RIE, inductively coupled RIE, or RIE using an ion attraction voltage can be used. For example, using CHF ₃ gas alone or a gas in which CF ₄ and C ₄ F ₈ are mixed at a gas flow ratio of 90 sccm: 10 sccm to 60 sccm: 40 sccm, the processing pressure is set in the range of 0.1 to 5 Pa, In addition, capacitive coupling RIE or RIE using an ion pull-in voltage is used. Further, for example, when using a chlorine-based gas, treatment is performed using only BCl ₃ gas, or a gas in which BCl ₃ gas and Cl ₂ gas or Ar gas are mixed at a gas flow rate ratio of 95 sccm: 5 sccm to 85 sccm: 15 sccm. The pressure is set in the range of 0.1 to 10 Pa, and capacitive coupling RIE, inductive coupling RIE, or RIE using an ion pull-in voltage is used.

Further, for example, in the case of using a chlorine-based gas, treatment is performed using only BCl ₃ gas or a gas in which BCl ₃ gas and Cl ₂ gas or Ar gas are mixed at a gas flow rate ratio of 95 sccm: 5 sccm to 70 sccm: 30 sccm. The pressure is set in a range of 0.1 Pa to 10 Pa, and capacitive coupling type RIE, inductive coupling type RIE, or RIE using an ion attraction voltage is used. Even when the total gas flow rate of the mixed gas used for etching changes, the ratio of the above flow rates does not change.

  In the dry etching process of the base material 11, the base material 11 is etched in the state of the etching workpiece 1 within the range of the entire thermal resistance value. In this way, by dry etching the substrate 11, a fine pattern mask having a pattern width of 2 μm or less and an aspect ratio in the range of 0.1 to 5.0 is used as a mask while ensuring high throughput. Even in this case, it is possible to reduce the dry etching damage and form the fine uneven structure on the base material 11 as expected.

  The fine pattern mask forming process and the dry etching process of the substrate 11 may be continuously performed by the same apparatus. In this case, the mounting member 2 may be used also in the fine pattern mask forming step, and each material and shape may be selected so as to satisfy the range of the entire thermal resistance value.

  In the case of satisfying the overall thermal resistance value in the present invention, the expected shape of the fine concavo-convex structure formed on the substrate 11 is the pattern width of the fine concavo-convex structure formed on the substrate 11 after the dry etching step This means that the center point is not deviated from the center point in the pattern width of the fine pattern mask before the dry etching process. When the overall thermal resistance value is not satisfied, the center point in the pattern width of the fine concavo-convex structure formed on the substrate 11 after the dry etching step is from the center point in the pattern width of the fine pattern mask before the dry etching step. It will be out of shape as expected.

  The effect when the overall thermal resistance value defined in the present invention is satisfied is particularly preferably exhibited when the dry etching rate of the substrate 11 is higher than the dry etching rates of the first mask layer 12a and the second mask layer 12b. Is not fast enough. In such a case, the first mask layer 12a and the second mask layer 12b are not only subjected to dry etching damage, but the first mask layer 12a and the second mask layer 12b simultaneously with the base material 11 have a large volume by dry etching. Therefore, there is a high possibility that the pattern will be shifted from the center point in the pattern width of the fine pattern mask before processing due to these two effects, and the substrate 11 may not be formed with the expected fine uneven shape. In particular, when the first mask layer 12a and the second mask layer 12b have a fine pattern width as in the present invention, the width of the first mask layer 12a and the second mask layer 12b during etching is small because the width is fine. Although the influence of the reduction is great, it is necessary to strongly reduce the etching damage. However, when the entire thermal resistance value defined in the present invention is satisfied, this dry etching damage can be particularly reduced. Can be formed.

  Here, the case where the dry etching rate of the base material 11 at which the effect of the present invention is expressed particularly preferably is not sufficiently fast with respect to the dry etching rates of the first mask layer 12a and the second mask layer 12b is a selectivity ratio ( (The dry etching rate of the substrate 11 / the dry etching rate of the first mask layer 12a) is 50 or less, more preferably 25 or less, and particularly preferably 10 or less.

  In addition, since the dry etching rate with respect to a fine pattern has a large influence on the fine pattern, these etching selection ratios are such that the base material 11 is only the base material 11 and the first mask layer 12a is a flat film (solid film) of various materials. It is a value measured against.

  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)

  In the following examination, in order to form a fine concavo-convex structure on the surface of a substrate, first, (1) a cylindrical master mold is produced, and (2) a light transfer method is applied to the cylindrical master mold, and the reel A resin mold was prepared. (3) Thereafter, the reel-shaped resin mold, the second mask layer, and the first mask layer were processed to produce a laminate for forming a fine pattern. Subsequently, (4) a fine pattern forming step of transferring the second mask layer and the first mask layer onto the substrate by nanoimprinting is performed, and (5) a predetermined pattern is formed by dry etching the first mask layer. After performing the fine pattern mask forming step, (6) fixing the etching work material on which the fine pattern mask is formed to the mounting member with a heat transfer sheet, and performing dry etching on the etching work material. After forming a concavo-convex structure on the material surface and peeling the base material from the mounting member, the concavo-convex structure shape of the base material was evaluated.

(1) Production of cylindrical master mold A texture 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. Sputtering was performed with a power of RF 100 W using φ3 inch CuO (containing 8 atm% Si) as a target (resist layer). In this way, a 20 nm resist layer was formed on the cylindrical quartz glass. Thereafter, the entire surface of the cylindrical quartz glass was exposed once. Subsequently, exposure was performed using a semiconductor laser having a wavelength of 405 nm while rotating the cylindrical quartz glass. Next, the resist layer after exposure was developed. The development of the resist layer was performed by processing for 240 seconds using a 0.03 wt% glycine aqueous solution. Next, quartz glass was etched by dry etching using the developed resist layer as a mask. Dry etching was performed using SF ₆ gas as an etching gas under 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 textured surface using hydrochloric acid having a pH of 1. The peeling time was 6 minutes.

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

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

The material 1 shown below was apply | coated to the easily bonding surface of PET film A-4100 (Toyobo Co., Ltd .: width 300mm, thickness 100micrometer) by micro gravure coating (manufactured by Yurai Seiki Co., Ltd.) so that it might become a coating film thickness of 5 micrometers. . 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 photo-curing was performed. , Width 300 mm).

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

Material 1 was applied to an easily adhesive surface of PET film A-4100 (manufactured by Toyobo Co., Ltd .: width 300 mm, thickness 100 μm) by microgravure coating (manufactured by Yurai Seiki Co., Ltd.) so as to have a coating film thickness of 3 μm. Next, the PET film coated with the material 1 is pressed against the textured surface of the reel-shaped resin mold G1 with a nip roll (0.1 MPa), and integrated exposure under the center of the lamp at 25 ° C. and 60% humidity in the air. Ultraviolet rays were irradiated using a UV exposure apparatus (H bulb) manufactured by Fusion UV Systems Japan Co., Ltd. so that the amount was 1200 mJ / cm ^2, and photocuring was continuously performed, and the texture was transferred to the surface. A plurality of reel-shaped resin molds 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

(3) Production of Laminate for Fine Pattern Formation A diluted solution of the following material 2 (second mask layer material) was applied to the textured surface of the reel-shaped resin mold G2. Subsequently, a diluted liquid of the following material 3 (first mask layer material) was applied on the texture surface of the reel-shaped resin mold G2 containing the material 2 inside the texture to obtain a laminate for forming a fine pattern. .
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)

  Using the same apparatus as that for the production of the reel-shaped resin mold (2), the material 2 diluted with PGME was directly coated on the textured surface of the reel-shaped resin mold 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 20% or more smaller than the texture volume per unit area. After coating, the material was passed through an air-drying oven at 80 ° C. for 5 minutes, and the reel-shaped resin mold G2 containing the material 2 inside the texture was wound up and collected.

  Subsequently, while unwinding the reel-shaped resin mold G2 containing the material 2 inside the texture, the material 3 diluted with PGME and MEK was used using the same device as the production of the above-mentioned (2) reel-shaped resin mold. Direct coating on the textured surface. Here, the dilution concentration was set such that the distance between the interface between the material 2 disposed inside the texture and the coated material 3 and the surface of the material 3 was 400 nm to 800 nm. After coating, the material was passed through an air-drying oven at 80 ° C. for 5 minutes, and a cover film made of polypropylene was put on the surface of the material 3 and wound up and collected.

(4) Fine pattern formation process The produced | generated laminated body for fine pattern formation (fine pattern laminated body) was used, and the 2nd mask layer and the 1st mask layer were transcribe | transferred on the base material by the nanoimprint method. A sapphire substrate was used as the substrate. The sapphire substrate was subjected to UV-O ₃ treatment for 5 minutes to remove surface particles and to make it hydrophilic. Subsequently, the surface of the first mask layer of the fine pattern laminate was bonded to the sapphire substrate. At this time, the sapphire substrate was bonded in a state heated to 80 ° C. Subsequently, using a high-pressure mercury lamp light source, light was irradiated through the reel-shaped resin mold G2 so that the integrated light amount was 1200 mJ / cm ² . Thereafter, the reel-shaped resin mold G2 was peeled off.

(5) by etching using O ₂ gas from the second mask layer side of the mask layer and etching a workpiece made of sapphire substrate having a fine pattern mask formation process obtained fine pattern, a second mask layer as a mask The first mask layer was nano-processed to partially expose the sapphire substrate surface to form a mask layer having a fine pattern. Oxygen etching was performed under conditions of a pressure of 1 Pa and a power of 300 W.

(6) Dry etching of base material An etching work material comprising a mask layer having a fine pattern and a sapphire substrate is placed on a placement member so as to have a thermal resistance value as in each of the following examples. Reactive ion etching using BCl ₃ gas was performed from the sapphire substrate side of the processed material to form a fine concavo-convex structure on the sapphire substrate. Etching using BCl ₃ gas was performed under two types of conditions, and both fine concavo-convex structures were evaluated. In addition, the stage part of the dry etching apparatus in which an etching workpiece and a mounting member are mounted is temperature-controlled by He gas of each set temperature.
Condition 1: BCl ₃ gas only, ICP: 150 W, BIAS: 50 W, pressure 0.2 Pa, temperature controlled He gas temperature 50 ° C. (gas pressure 2.0 kPa), reactive ion etching apparatus (RIE-101iPH, manufactured by Samco Corporation) )use.
Condition 2: Mixing of BCl ₃ and Cl ₂ gas (BCl ₃ : Cl ₂ = 6: 4), ICP: 150 W, BIAS: 50 W, pressure 0.2 Pa, temperature-controlled He gas temperature 20 ° C. (gas pressure 2.0 kPa) Using a reactive ion etching apparatus (RIE-230iP, manufactured by Samco Corporation).

  After dry etching, the sapphire substrate is peeled off from the etching workpiece, the sapphire substrate is washed with a solution in which sulfuric acid and hydrogen peroxide are mixed at a weight ratio of 2: 1, and a sapphire substrate having a fine concavo-convex structure on the surface is obtained. Obtained.

  This fine concavo-convex structure shape of the base material is processed until the first mask layer is completely dry-etched in the dry etching process of the base material, and the tip of the fine concavo-convex structure of the base material after processing is a fine pattern mask. The degree of deviation from the center of the pattern width was evaluated by observation with a scanning microscope (SEM). In both of the above conditions 1 and 2 of dry etching, the case where the deviation amount is 10% or less with respect to the fine pattern mask width is the expected shape and the case is evaluated as “good”, and the deviation amount is 5% or less. Evaluate as “better”, and if the deviation amount is 3% or less, evaluate as “particularly good”, and if the deviation amount is greater than 10% in either of the above conditions 1 or 2, the shape is not as expected. Evaluated as “bad”.

  In addition, for the conditions in which the amount of deviation with respect to the pattern mask width is “good”, “better” or “particularly good”, the following comparative example 1, comparative example 2 or comparative example having the same pattern mask width The improvement rate with respect to the shift amount in Example 3 was evaluated. The improvement rate here is represented by {1- (deviation amount in each embodiment / deviation amount in each comparative example)}. An improvement rate of 50% or more was evaluated as “good”, an improvement rate of 65% or more was evaluated as “better”, and an improvement rate of 80% or more was evaluated as “particularly good”.

(Measurement of thermal conductivity)
The measurement of the thermal conductivity λ of each material in this example was calculated from specific heat × thermal diffusivity × density.
Specific heat and thermal diffusivity were measured using a laser flash method, and density was measured by a weight / dimension measurement method. The sample shape at the time of measurement was about φ10 × t2 (mm), the measurement temperature was 23 ° C., the measurement atmosphere was in the air, and TC-7000 manufactured by ULVAC-RIKO was used as the measurement apparatus.

  In Table 1 and Table 2 below, for the examples and comparative examples, the pattern shape of the fine pattern mask, the material of the base material, the thermal conductivity and the thermal resistance value, the material of the mounting member, the thermal conductivity and the thermal resistance value, etc. The material, thermal resistivity and thermal resistance value of the used member, the thermal resistance value of the entire process, the evaluation result of the fine unevenness of the substrate, and the improvement rate are described.

Example 1
The base material is a sapphire substrate, an etching work material having a mask layer with a pattern width of 300 nm and an aspect ratio of 5.0 is produced, and the etching work material is placed on a quartz mounting member with a heat transfer sheet interposed therebetween. Then, dry etching was performed on the condition 1 and condition 2 described above. The overall thermal resistance at this time was 6.26 × 10 ⁻³ (m ² · K / W). As a result of the evaluation, the amount of deviation of the tip portion of the fine concavo-convex structure was 10% or less, which was good. Further, the improvement rate when compared with Comparative Example 3 was 80% or more, which was particularly good.

(Example 2)
The base material is a sapphire substrate, an etching work material having a mask layer with a pattern width of 300 nm and an aspect ratio of 5.0 is produced, and this etching work material is placed on a quartz placing member by a heat transfer sheet. Then, this was dry-etched under the above conditions 1 and 2. The overall thermal resistance at this time was 6.79 × 10 ⁻³ (m ² · K / W). As a result of the evaluation, the deviation amount of the tip portion of the fine concavo-convex structure was 10% or less, which was good. Further, the improvement rate when compared with Comparative Example 3 was 80% or more, which was particularly good.

(Example 3)
The base material is a sapphire substrate, an etching work material having a mask layer with a pattern width of 300 nm and an aspect ratio of 1.0 is produced, and the etching work material is placed on a quartz placing member by a heat transfer sheet. Then, this was dry-etched under the above conditions 1 and 2. The overall thermal resistance at this time was 6.79 × 10 ⁻³ (m ² · K / W). As a result of the evaluation, the amount of deviation of the tip portion of the fine concavo-convex structure was 10% or less, which was good. Further, the improvement rate when compared with Comparative Example 3 was 80% or more, which was particularly good.

Example 4
The base material is a sapphire substrate, an etching work material having a mask layer with a pattern width of 300 nm and an aspect ratio of 0.5 is manufactured, and this etching work material is placed on a quartz placing member by a heat transfer sheet. Then, this was dry-etched under the above conditions 1 and 2. The overall thermal resistance at this time was 6.79 × 10 ⁻³ (m ² · K / W). As a result of the evaluation, the deviation amount of the tip portion of the fine concavo-convex structure was 5% or less, which was better. Further, the improvement rate when compared with Comparative Example 3 was 80% or more, which was particularly good.

(Example 5)
The base material is a sapphire substrate, an etching work material having a mask layer with a pattern width of 700 nm and an aspect ratio of 5.0 is produced, and this etching work material is placed on a quartz placing member by a heat transfer sheet. Then, this was dry-etched under the above conditions 1 and 2. The overall thermal resistance at this time was 6.79 × 10 ⁻³ (m ² · K / W). As a result of the evaluation, the amount of deviation of the tip portion of the fine concavo-convex structure was 10% or less, which was good. Moreover, the improvement rate when compared with Comparative Example 2 was 65% or more, which was better.

(Example 6)
A base material is a sapphire substrate, an etching work material having a mask layer with a pattern width of 700 nm and an aspect ratio of 1.0 is manufactured, and the etching work material is placed on a quartz placing member by a heat transfer sheet. Then, this was dry-etched under the above conditions 1 and 2. The overall thermal resistance at this time was 6.79 × 10 ⁻³ (m ² · K / W). As a result of the evaluation, the amount of deviation of the tip portion of the fine concavo-convex structure was 10% or less, which was good. Moreover, the improvement rate when compared with Comparative Example 2 was 65% or more, which was better.

(Example 7)
A base material is a sapphire substrate, an etching work material having a mask layer with a pattern width of 2 μm and an aspect ratio of 5.0 is manufactured, and this etching work material is placed on a quartz placing member by a heat transfer sheet. Then, this was dry-etched under the above conditions 1 and 2. The overall thermal resistance at this time was 6.79 × 10 ⁻³ (m ² · K / W). As a result of the evaluation, the amount of deviation of the tip portion of the fine concavo-convex structure was 10% or less, which was good. Moreover, the improvement rate when compared with Comparative Example 1 was 50% or more, which was good.

(Example 8)
A base material is a sapphire substrate, an etching work material having a mask layer with a pattern width of 2 μm and an aspect ratio of 1.0 is manufactured, and this etching work material is placed on a quartz placing member by a heat transfer sheet. Then, this was dry-etched under the above conditions 1 and 2. The overall thermal resistance at this time was 6.79 × 10 ⁻³ (m ² · K / W). As a result of the evaluation, the deviation amount of the tip portion of the fine concavo-convex structure was 5% or less, which was better. Moreover, the improvement rate when compared with Comparative Example 1 was 50% or more, which was good.

Example 9
The base material is a sapphire substrate, an etching work material having a mask layer with a pattern width of 300 nm and an aspect ratio of 5.0 is produced, and this etching work material is placed on a quartz placing member by a heat transfer sheet. Then, this was dry-etched under the above conditions 1 and 2. The overall thermal resistance at this time was 3.04 × 10 ⁻³ (m ² · K / W). As a result of the evaluation, the deviation amount of the tip portion of the fine concavo-convex structure was 5% or less, which was better. Further, the improvement rate when compared with Comparative Example 3 was 80% or more, which was particularly good.

(Example 10)
A base material is a sapphire substrate, an etching work material having a mask layer with a pattern width of 2 μm and an aspect ratio of 5.0 is manufactured, and this etching work material is placed on a quartz placing member by a heat transfer sheet. Then, this was dry-etched under the above conditions 1 and 2. The overall thermal resistance at this time was 3.04 × 10 ⁻³ (m ² · K / W). As a result of the evaluation, the deviation amount of the tip portion of the fine concavo-convex structure was 5% or less, which was better. Moreover, the improvement rate when compared with Comparative Example 1 was 50% or more, which was good.

(Example 11)
The base material is a sapphire substrate, an etching work material having a mask layer with a pattern width of 300 nm and an aspect ratio of 5.0 is manufactured, and the etching work material is placed on an alumina mounting member by a heat transfer sheet. Then, this was dry-etched under the above conditions 1 and 2. The overall thermal resistance at this time was 1.21 × 10 ⁻³ (m ² · K / W). The evaluation result was particularly good with the amount of deviation of the tip of the fine concavo-convex structure being 3% or less. Further, the improvement rate when compared with Comparative Example 3 was 80% or more, which was particularly good.

(Example 12)
The base material is a sapphire substrate, an etching work material having a mask layer with a pattern width of 700 nm and an aspect ratio of 5.0 is manufactured, and this etching work material is placed on an alumina mounting member by a heat transfer sheet. Then, this was dry-etched under the above conditions 1 and 2. The overall thermal resistance at this time was 1.21 × 10 ⁻³ (m ² · K / W). The evaluation result was particularly good with the amount of deviation of the tip of the fine concavo-convex structure being 3% or less. Moreover, the improvement rate when compared with Comparative Example 2 was 65% or more, which was better.

(Example 13)
The base material is a sapphire substrate, an etching work material having a mask layer with a pattern width of 2 μm and an aspect ratio of 5.0 is produced, and this etching work material is placed on an alumina mounting member by a heat transfer sheet. Then, this was dry-etched under the above conditions 1 and 2. The overall thermal resistance at this time was 1.21 × 10 ⁻³ (m ² · K / W). The evaluation result was particularly good with the amount of deviation of the tip of the fine concavo-convex structure being 3% or less. Moreover, the improvement rate when compared with Comparative Example 1 was 50% or more, which was good.

(Example 14)
The base material is a sapphire substrate, an etching work material having a mask layer with a pattern width of 300 nm and an aspect ratio of 5.0 is manufactured, and the etching work material is placed on a Si placement member by a heat transfer sheet. Then, this was dry-etched under the above conditions 1 and 2. The overall thermal resistance at this time was 6.03 × 10 ⁻⁴ (m ² · K / W). The evaluation result was particularly good with the amount of deviation of the tip of the fine concavo-convex structure being 3% or less. Further, the improvement rate when compared with Comparative Example 3 was 80% or more, which was particularly good.

(Example 15)
The base material is a sapphire substrate, an etching work material having a mask layer with a pattern width of 300 nm and an aspect ratio of 5.0 is manufactured, and the etching work material is placed on a SiC mounting member by a heat transfer sheet. Then, this was dry-etched under the above conditions 1 and 2. The overall thermal resistance at this time was 5.81 × 10 ⁻⁴ (m ² · K / W). The evaluation result was particularly good with the amount of deviation of the tip of the fine concavo-convex structure being 3% or less. Further, the improvement rate when compared with Comparative Example 3 was 80% or more, which was particularly good.

(Example 16)
The base material is a sapphire substrate, an etching work material having a mask layer with a pattern width of 300 nm and an aspect ratio of 5.0 is manufactured, and the etching work material is placed on a Si placement member by a heat transfer sheet. Then, the Si mounting member was attached to another SiC mounting member with a heat transfer sheet to form a two-stage mounting member, and dry etching was performed under the above conditions 1 and 2. The overall thermal resistance at this time was 1.17 × 10 ⁻³ (m ² · K / W). The evaluation result was particularly good with the amount of deviation of the tip of the fine concavo-convex structure being 3% or less. Further, the improvement rate when compared with Comparative Example 3 was 80% or more, which was particularly good.

(Example 17)
An etching workpiece having a mask layer with a substrate width of 300 nm and an aspect ratio of 5.0 is manufactured, and the etching workpiece is placed on a quartz placement member by a heat transfer sheet. Then, this was dry-etched under the above conditions 1 and 2. The overall thermal resistance at this time was 6.79 × 10 ⁻³ (m ² · K / W). As a result of the evaluation, the deviation amount of the tip portion of the fine concavo-convex structure was 10% or less, which was good. Further, the improvement rate when compared with Comparative Example 3 was 80% or more, which was particularly good.

(Example 18)
The base material is a Si substrate, an etching work material having a mask layer with a pattern width of 700 nm and an aspect ratio of 5.0 is manufactured, and the etching work material is placed on a quartz placing member by a heat transfer sheet. Then, this was dry-etched under the above conditions 1 and 2. The overall thermal resistance at this time was 6.79 × 10 ⁻³ (m ² · K / W). As a result of the evaluation, the deviation amount of the tip portion of the fine concavo-convex structure was 10% or less, which was good. Moreover, the improvement rate when compared with Comparative Example 2 was 65% or more, which was better.

(Comparative Example 1)
A base material is a sapphire substrate, an etching work material having a mask layer with a pattern width of 2 μm and an aspect ratio of 5.0 is manufactured, and this etching work material is placed on a quartz placing member by a heat transfer sheet. Then, the quartz mounting member was attached to another quartz mounting member with a heat transfer sheet to form a two-stage mounting member, and dry etching was performed under the above conditions 1 and 2. The overall thermal resistance at this time was 9.83 × 10 ⁻³ (m ² · K / W). As a result of the evaluation, the amount of deviation of the tip portion of the fine concavo-convex structure was 10% or more, which was poor.

(Comparative Example 2)
The base material is a sapphire substrate, an etching work material having a mask layer with a pattern width of 700 nm and an aspect ratio of 5.0 is produced, and this etching work material is placed on a quartz placing member by a heat transfer sheet. Then, the quartz mounting member was attached to another quartz mounting member with a heat transfer sheet to form a two-stage mounting member, and dry etching was performed under the above conditions 1 and 2. The overall thermal resistance at this time was 9.83 × 10 ⁻³ (m ² · K / W). As a result of the evaluation, the amount of deviation of the tip portion of the fine concavo-convex structure was 10% or more, which was poor.

(Comparative Example 3)
The base material is a sapphire substrate, an etching work material having a mask layer with a pattern width of 300 nm and an aspect ratio of 5.0 is produced, and this etching work material is placed on a quartz placing member by a heat transfer sheet. Then, the quartz mounting member was attached to another quartz mounting member with a heat transfer sheet to form a two-stage mounting member, and dry etching was performed under the above conditions 1 and 2. The overall thermal resistance at this time was 9.83 × 10 ⁻³ (m ² · K / W). As a result of the evaluation, the amount of deviation of the tip portion of the fine concavo-convex structure was 10% or more, which was poor.

(Comparative Example 4)
A base material is a sapphire substrate, an etching work material having a mask layer with a pattern width of 2 μm and an aspect ratio of 5.0 is manufactured, and this etching work material is placed on a quartz placing member by a heat transfer sheet. And the two-stage mounting member was comprised by affixing the quartz mounting member on another alumina mounting member with a heat-transfer sheet | seat, and the dry etching was performed on the said conditions 1 and 2 conditions. The overall thermal resistance at this time was 7.99 × 10 ⁻³ (m ² · K / W). As a result of the evaluation, the amount of deviation of the tip portion of the fine concavo-convex structure was 10% or more, which was poor.

(Comparative Example 5)
The base material is a sapphire substrate, an etching work material having a mask layer with a pattern width of 300 nm and an aspect ratio of 5.0 is produced, and this etching work material is placed on a quartz placing member by a heat transfer sheet. And the two-stage mounting member was comprised by affixing the quartz mounting member on another alumina mounting member with a heat-transfer sheet | seat, and the dry etching was performed on the said conditions 1 and 2 conditions. The overall thermal resistance at this time was 7.99 × 10 ⁻³ (m ² · K / W). As a result of the evaluation, the amount of deviation of the tip portion of the fine concavo-convex structure was 10% or more, which was poor.

  The present invention is not limited to the embodiment described above, and can be implemented with various modifications. For example, the material, arrangement, shape, and the like of the members in the above embodiment are illustrative, and can be appropriately changed and implemented within a range in which the effect of the present invention is exhibited. In addition, various modifications can be made without departing from the scope of the present invention.

  INDUSTRIAL APPLICATION This invention can be utilized suitably for the use which forms a fine uneven structure in a base material.

DESCRIPTION OF SYMBOLS 1 Etching workpiece 2 Mounting member 3 Heat transfer sheet 4 Mold 5 Support substrate 11 Base material 12 Mask layer 12a First mask layer 12b Second mask layer

Claims (8)

An etching workpiece comprising a mask layer having a pattern with a pattern width of 2 μm or less and an aspect ratio of 0.1 to 5.0 on a substrate, the etching workpiece on a mounting member used during etching An etching workpiece having an overall thermal resistance value of 6.79 × 10 ⁻³ (m ² · K / W) or less when the material is placed.
(The overall thermal resistance value refers to the thermal resistance value of the mounting member and the thermal resistance value of the base material in the mounting region of the etching workpiece in the mounting member, and When there is another member other than the workpiece to be etched, it is the sum of the thermal resistance values of the other members, and each thermal resistance value represents the thickness of each member and the heat conduction of the material constituting each member. (The value divided by the rate λ.)   When the mounting member is composed of a plurality of materials, the smallest thermal resistance value among the thermal resistance values obtained for each material constituting the mounting member is the thermal resistance value of the mounting member. The etching workpiece according to claim 1. The etching work material according to claim 1, wherein the overall thermal resistance value is 3.04 × 10 ⁻³ (m ² · K / W) or less. The etching work material according to claim 1, wherein the overall thermal resistance value is 1.21 × 10 ⁻³ (m ² · K / W) or less. The mounting member includes silicon (Si), quartz (SiO ₂ ), aluminum (Al), silicon carbide (SiC), alumina (Al ₂ O ₃ ), aluminum nitride (AlN), zirconia oxide (ZrO ₂ ) and yttria oxide (Y 2 _{O 3)} as well as according to claim 1, wherein a part or all is composed of one or more selected from among the coated inorganic member in any one or more of these Etching work material. The thickness calculated as the thermal resistance value of the mounting member is determined when the material constituting the mounting member is silicon (Si), aluminum (Al), silicon (SiC), or aluminum nitride (AlN). Is 0.001 m or more and 0.05 m or less, and 0.001 m or more when quartz (SiO ₂ ), alumina (Al ₂ O ₃ ), zirconia oxide (ZrO ₂ ), or yttria oxide (Y ₂ O ₃ ) is used. The etching workpiece according to claim 5, wherein the etching workpiece is 0.02 m or less and, in the case of the inorganic member, 0.001 m or more and 0.05 m or less. Forming a mask layer having a pattern width of 2 μm or less and a pattern having an aspect ratio of 0.1 to 5.0 on a substrate to obtain an etching workpiece; and placing the etching workpiece on a mounting member And the step of etching the base material using the mask layer as a mask in a state where the overall thermal resistance value is 6.79 × 10 ⁻³ (m ² · K / W) or less. Etching method characterized.
(The overall thermal resistance value refers to the thermal resistance value of the mounting member and the thermal resistance value of the base material in the mounting region of the etching workpiece in the mounting member, and When other members other than the etching workpiece are present, it is the sum of the thermal resistance values of the other members, and each thermal resistance value represents the thickness of each member and the heat of the material constituting each member. (The value is divided by the conductivity λ.)   A substrate having a fine concavo-convex structure obtained by etching the etching workpiece according to any one of claims 1 to 6, and a semiconductor light emitting layer formed on the substrate. A semiconductor light emitting device.

Images