JP5458975B2 - Manufacturing method of mold for nanoimprint - Google Patents

Description

  The present invention relates to a method for producing a nanoimprint mold for transferring and forming a desired line, pattern or the like (hereinafter also referred to as a pattern in the present invention) on a workpiece.

In recent years, attention has been focused on nanoimprint technology as a microfabrication technology. The nanoimprint technology is a pattern formation technology that uses a mold member having a fine concavo-convex structure formed on the surface of a substrate and transfers the concavo-convex structure to a workpiece to transfer the fine structure at the same magnification (Patent Document 1).
As one method of the nanoimprint technique, an optical imprint method is known. In this optical imprint method, for example, a photocurable resin layer is formed as a workpiece on the substrate surface, and a mold (mold member) having a desired uneven structure is pressed against the resin layer. In this state, the resin layer is irradiated with light from the mold side to cure the resin layer, and then the mold is separated from the resin layer. As a result, a concavo-convex structure (concave / convex pattern) in which the concavo-convex portion of the mold is inverted can be formed on the resin layer that is a workpiece (Patent Document 2). Such optical imprints are capable of forming nanometer-order fine patterns that are difficult to form with conventional photolithography techniques, and are promising as next-generation lithography techniques.

In this optical imprinting method, the resin surplus by pressing the mold protrudes outside the region where the mold and the resin are in contact and adheres to the side surface of the mold. The photocurable resin adhering to the side surface is cured simultaneously with the resin layer at a site where a concavo-convex structure (concave / convex pattern) is to be formed by light passing outside the mold during light irradiation. At this time, if curing is caused without controlling the light irradiation, there is a problem that when the mold is released, a non-uniform force acts on the resin layer and damages the mold and the workpiece.
Moreover, when forming the fine concavo-convex structure which a mold has in several places on a to-be-processed object, pattern formation may be performed by a step and repeat system. When a conventional mold is used, the resin layer outside the portion where the concavo-convex structure is to be formed is exposed by light passing outside the pattern region where the concavo-convex structure is formed, and the region that is cured by one pattern formation is It becomes larger than the pattern area of the mold. On the other hand, if the photocurable resin layer is exposed and cured, pattern formation cannot be performed at that location. For this reason, there has been a problem that the boundary width between regions where adjacent patterns are formed must be set large.

Further, when the mold is released from the resin layer, the resin layer adheres as a foreign matter, and there is a problem that a defect is generated in the next processing region.
In order to solve such a problem, a mold in which a light shielding member is provided in a portion (non-pattern region) that is not a pattern region has been proposed (Patent Document 3). In Patent Document 3, as one aspect of a mold, a mold having a so-called mesa structure having a convex structure having a third surface between a processed surface and a back surface having a fine concavo-convex structure, the third surface And a mold in which a light shielding member is disposed on a side surface that is a boundary between a processed surface and a third surface.

US Pat. No. 5,772,905 Special Table 2002-539604 JP 2008-168641 A

However, the production of a mold having the above mesa structure has the following problems. That is, when a light shielding member is provided after forming a processed surface having a fine concavo-convex structure, vacuum film formation, resist stripping, or polishing is required in the light shielding member forming process, and the fine concavo-convex structure on the processed surface is damaged. There was a problem that occurred. In addition, in order to provide the light shielding member on the third surface (the portion where the convex structure does not exist), a film forming process using a mask is required, and there is a problem that the process becomes complicated. On the other hand, when the light shielding member is formed on the other surface of the substrate having the mesa structure first, and then a fine uneven structure is formed on the processed surface, the light shielding member is damaged in the formation process of the uneven structure. There arises a problem that the light shielding by the light shielding member is incomplete.
The present invention has been made in view of the above circumstances, and provides a manufacturing method for easily manufacturing a nanoimprint mold capable of reliably suppressing exposure to an unintended portion of a workpiece. Objective.

  In order to achieve such an object, the present invention provides a base material having a base portion and a convex structure portion projecting from one surface of the base portion, and a surface on the side where the convex structure portion of the base material projects. In a method for producing a mold for nanoimprint, comprising: a resin layer that covers the resin layer; a concave portion that is located in the resin layer on the convex structure portion; and a light-shielding film that covers the resin layer located on the base portion. A base material having a convex structure portion projecting from one surface of the base portion is coated with a wettability changing resin material coating solution on the surface on which the convex structure portion projects, and then dried. A drying step of forming a resin layer having a surface water contact angle of 90 ° or more and a hardness of 400 or more, and irradiating the resin layer located on the base with light, to form a resin at the irradiated site A wettability changing step in which the water contact angle of the surface of the layer is 10 ° or less; A light shielding film forming step of forming a light shielding film on the resin layer located on the base by applying a composition liquid for forming a light shielding film on the resin layer, and drying and curing; A step of forming a recess in the resin layer by press-bonding the resin layer located at the center and the master mold and then separating the master mold.

  A base having a base and a convex structure protruding from one surface of the base; a resin layer covering the surface of the base on which the convex structure protrudes; and In the method for manufacturing a mold for nanoimprint, comprising: a concave portion located in the resin layer; and a light shielding film covering the resin layer located on the base portion, and a convex structure portion projecting from one surface of the base portion. A wettability changing resin material coating solution is applied and coated on a surface of the substrate having the protruding structure portion protruding thereon, and the wettability changing resin material layer and the master mold are located on the protruding structure portion. Are pressed, and then separated to form a recess in the wettability changing resin material layer, and the wettability changing resin material layer is subjected to a drying treatment so that the water contact angle on the surface is 90 °. Above, and the tree whose hardness is 400 or more A drying step for forming a layer, a wettability changing step for irradiating the resin layer located on the base with light so that a water contact angle on the surface of the resin layer at the irradiated portion is 10 ° or less, and the resin layer And a light-shielding film forming step of forming a light-shielding film on the resin layer located on the base by applying a composition for forming a light-shielding film thereon and drying and curing.

As another aspect of the present invention, the drying step is incorporated into the recess forming step, and the wettability changing resin material layer positioned on the convex structure portion and the master mold are pressure-bonded and dried to the wettability changing resin material layer. After the treatment, the master mold and the resin layer are separated from each other to form a resin layer having a recess, a surface water contact angle of 90 ° or more, and a hardness of 400 or more. .
As another aspect of the present invention, in the wettability changing step, the resin layer located on the side surface of the convex structure portion is irradiated with light together with the resin layer located on the base portion, and the resin at the irradiated portion is irradiated. The water contact angle on the surface of the layer is 10 ° or less, and in the light shielding film forming step, a light shielding film is formed on the resin layer located on the side surface of the convex structure portion as well as on the resin layer located on the base portion. It was set as the structure which forms.

As another aspect of the present invention, the wettability changing resin material coating solution is configured to contain at least an organopolysiloxane and a photocatalyst.
As another aspect of the present invention, the light shielding film forming composition liquid is configured to contain at least one of carbon, titanium oxide, copper oxide, and iron oxide as a light shielding material.
As another embodiment of the present invention, the composition for forming a light shielding film on the resin layer is applied by any one of a spin coating method, a spray coating method, and a dip coating method.

  According to the present invention, the water contact angle of the surface of the resin layer formed by subjecting the applied wettability changing resin material coating solution to a drying treatment is 90 ° or more, and then the resin layer at the site where the light shielding film is formed. Since the water contact angle is set to 10 ° or less by irradiating light, the light shielding film forming composition liquid has a water contact angle of 90 even if there is hydrophilic variation in the light shielding film forming composition liquid applied to the resin layer. Since the light-shielding film can be formed by applying only to the portion having a water contact angle of 10 ° or less without applying to the portion having an angle of ≧ °, the process is simple. Moreover, after forming the light shielding film, a recess is formed in the resin layer by pressure bonding using a master mold, or in the formation of the light shielding film after the depression is formed by pressure bonding using a master mold, an etching process or vacuum film formation is performed. Since there is no process, resist stripping process, or polishing process, damage to the light-shielding film and the fine concavo-convex structure of the convex structure portion can be prevented, and the hardness of the resin layer formed by drying is 400 or more. Therefore, a highly durable nanoimprint mold can be produced.

It is sectional drawing which shows an example of the mold for nanoimprint manufactured by the manufacturing method of the mold for nanoimprint of this invention. It is process drawing for demonstrating one Embodiment of the manufacturing method of the mold for nanoimprint of this invention. It is process drawing for demonstrating one Embodiment of the manufacturing method of the mold for nanoimprint of this invention. It is process drawing for demonstrating other embodiment of the manufacturing method of the mold for nanoimprint of this invention. It is process drawing for demonstrating other embodiment of the manufacturing method of the mold for nanoimprint of this invention. It is a figure for demonstrating an example of the pattern formation using the mold for nanoimprint manufactured by the manufacturing method of the mold for nanoimprint of this invention.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
First, an example of a nanoimprint mold produced by the method for producing a nanoimprint mold of the present invention will be described with reference to FIG.
A nanoimprint mold 11 shown in FIG. 1 is a mesa-structured nanoimprint mold, and is provided on a transparent substrate 12, a resin layer 15 that covers one surface 12 a of the substrate 12, and the resin layer 15. The recess 16 and the light shielding film 17 are provided. The base material 12 includes a base portion 13 and a convex structure portion 14 protruding from one surface of the base portion 13, and is defined by a pattern region X and a non-pattern region Y located around the pattern region X. ing. The concave portion 16 is provided in the resin layer 15 located on the convex structure portion 14 and is located in the pattern region X. Further, the light shielding film 17 is provided on the resin layer 15 located on the base portion 13 and the side surface 14a of the convex structure portion 14 in the resin layer 15 covering the one surface 12a of the base material 12, and is not It is located in the pattern area Y. The light shielding film 17 located in the non-pattern region Y shields the light irradiated to the non-pattern region Y from the back surface 12b of the base material 12 and suppresses exposure to an unintended part of the workpiece. It is a member.

Next, the manufacturing method of the nanoimprint mold of the present invention will be described.
2 and 3 are process diagrams for explaining an embodiment of the method for producing a nanoimprint mold of the present invention, and takes the above-described nanoimprint mold 11 as an example.
In the present invention, in the drying process, the wettability changing resin material coating liquid is applied to the surface 12a on the side where the convex structure portion 14 of the base member 12 having the convex structure portion 14 protruding from one surface of the base portion 13 protrudes. The resin layer 15 having a surface water contact angle of 90 ° or more, preferably 95 ° or more, and a hardness of 400 or more, preferably 600 or more is applied by coating and coating, followed by drying treatment. (FIG. 2A). The substrate 12 to be used is a substrate that can transmit irradiation light for curing the workpiece during nanoimprinting. As a material of such a base material 12, for example, quartz glass, silicate glass, calcium fluoride, magnesium fluoride, acrylic glass, or an arbitrary laminated material thereof can be used. Moreover, the thickness of the base material 12 can be set in consideration of the material of the workpiece, the height of the convex structure portion 14, the strength of the base material, the handling suitability, and the like. For example, the thickness is appropriately in the range of about 300 μm to 10 mm. Can be set.
The wettability changing resin material coating solution used in the present invention contains at least organopolysiloxane and a photocatalyst, and details will be described later.

The drying treatment for the applied wettability changing resin material coating liquid is not particularly limited as long as the solvent is removed from the coating liquid and the resin layer 15 having a hardness of 400 or more is obtained. For example, the temperature is 20 to 200 ° C. It can set suitably in the range. When the water contact angle of the surface of the resin layer 15 formed by performing such a drying process is less than 90 °, due to the hydrophilic variation of the light shielding film forming composition liquid used in the light shielding film forming process described later, It is not preferable because the light shielding film 17 may be formed on the resin layer 15 in the pattern region X where the light shielding film 17 is not required. Further, if the hardness of the resin layer 15 formed by the drying treatment is less than 400, the durability of the produced mold 11 may be insufficient, which is not preferable. In addition, the thickness of the resin layer 15 can be set in consideration of the depth, shape, and the like of the recess 16 formed in a later step, and can be set, for example, in the range of about 0.01 to 10 μm.
In the present invention, the water contact angle is measured using a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science Co., Ltd.) 30 seconds after dropping a water droplet from a microsyringe. The hardness is measured using a micro Vickers hardness tester (HMV-FA series, manufactured by Shimadzu Corporation).

Next, in the wettability changing step, the resin layer 15 located on the base 13 and the side surface 14a of the convex structure 14 is irradiated with light to form a resin layer 15a having a surface water contact angle of 10 ° or less ( FIG. 2 (B)). The light irradiated here includes at least light within the excitation wavelength range of the photocatalyst contained in the resin layer 15, and for example, VUV (vacuum ultraviolet), ultraviolet, visible light, infrared, or the like can be used. . Further, the light irradiation only on the resin layer 15 located on the base 13 and on the side surface 14a of the convex structure portion 14 may be performed by, for example, irradiating through a mask having a light shielding portion corresponding to the convex structure portion 14, or by using a stepper blade. It can be performed by a method of adjusting and irradiating a desired part, an irradiation method using a spotlight, or the like.
When the water contact angle of the surface of the resin layer irradiated with light exceeds 10 °, the thickness of the light shielding film 17 to be formed is reduced due to the hydrophilic variation of the composition for forming the light shielding film used in the light shielding film forming process described later. This is not preferable because it may be insufficient or cause defects.
In this embodiment, the resin layer 15 located on the base 13 and the side surface 14a of the convex structure 14 is irradiated with light, but the present invention can irradiate the resin layer 15 located on the base 13 with light. It is essential and light irradiation to the resin layer 15 located on the side surface 14a of the convex structure portion 14 is arbitrary.

  Next, in the light shielding film forming step, a light shielding film forming composition liquid is applied on the resin layer 15 and the resin layer 15a. The applied composition liquid for forming a light shielding film is not applied to the resin layer 15 having a water contact angle of 90 ° or more, and the resin layer 15a has a water contact angle of 10 ° or less in the wettability changing step. Only applied on top. Then, the light shielding film 17 is formed on the resin layer 15a by drying and curing (FIG. 2C). The composition liquid for forming a light-shielding film used in the present invention is an aqueous dispersion containing at least one of carbon, titanium oxide, copper oxide and iron oxide and a binder as a light-shielding material. The content of the light shielding material in the composition for forming a light shielding film can be in the range of 5 to 50% by weight, preferably 25 to 45% by weight in the solid content. When the content of the light shielding material is less than 5% by weight, the light shielding film 17 has sufficient light shielding properties (for example, an optical density (OD) of 2 or more, preferably 3 or more with respect to ultraviolet rays having a wavelength of about 200 to 400 nm). If the amount exceeds 50% by weight, the durability of the light shielding film 17 may decrease, which is not preferable. Moreover, as a binder used for the light shielding film forming composition liquid, for example, poly (meth) acrylic acid resin, polyester resin, polyvinyl acetate resin, polyvinyl chloride resin, polyvinyl butyral resin, cellulose resin, Polystyrene / polybutadiene copolymer resin, polyurethane resin, alkyd resin, acrylic resin, unsaturated polyester resin, epoxy ester resin, epoxy resin, epoxy acrylate resin, urethane acrylate resin, polyester acrylate resin, polyether Examples thereof include acrylate resins, phenol resins, melamine resins, urea resins, diallyl phthalate resins, and the like. Moreover, application | coating of the light shielding film formation composition liquid on the resin layer 15 and the resin layer 15a can be performed by well-known coating methods, such as a spin coat method, a spray coat method, a dip coat method, for example. The thickness of the light shielding film 17 formed in this way can be set in consideration of light shielding properties, durability, and the like, and can be set, for example, in the range of about 0.5 to 50 μm.

  Thus, in the present invention, since the light shielding film forming composition liquid is applied and applied only on the resin layer having a water contact angle of 10 ° or less in the above-described wettability changing step, The light shielding film 17 can be easily formed on a surface having a different surface direction, such as the side surface 14a of the structure portion 14, and the process is simple. On the other hand, for example, in a film formation by a vacuum film formation method such as a sputtering method, it is difficult to form a film on a surface having a different surface direction, and the surface has a different surface direction, such as the side surface 14a of the base portion 13 and the convex structure portion 14. In the formation of the light shielding film, it is necessary to use a mask, control the direction of attachment of the light shielding material, etc., and the process becomes complicated.

  Next, in the concave portion forming step, the resin layer 15 and the master mold 21 positioned on the convex structure portion 14 are pressure-bonded (FIG. 3A), and then separated (FIG. 3B). A recess 16 is formed in 15. Thereby, the mold 11 for nanoimprinting is obtained. There is no restriction | limiting in particular in the master mold 21 to be used, The convex part 22 of the shape corresponding to the pattern shape formed by nanoimprint is provided. The material of the master mold 21 may be made of an inorganic material such as glass, quartz, or metal, or may be made of a resin material.

Here, the wettability changing resin material coating solution used in the present invention will be described.
As described above, the wettability changing resin material coating solution contains at least a photocatalyst and an organopolysiloxane.
The photocatalyst used in the wettability changing resin material coating solution changes the chemical structure of the surrounding organic matter when it absorbs the irradiated light. For example, titanium oxide known as an optical semiconductor ( TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), strontium titanate (SrTiO ₃ ), tungsten oxide (WO ₃ ), bismuth oxide (Bi ₂ O ₃ ), iron oxide (Fe ₂ O ₃ ), etc. The metal oxides can be used, and these can be used alone or in combination of two or more.
Among such photocatalysts, titanium oxide can be preferably used in the present invention because it has a high band gap energy, is chemically stable, has no toxicity, and is easily available. Titanium oxide includes anatase type and rutile type, and both can be used in the present invention, but anatase type titanium oxide is preferable. This anatase-type titanium oxide has an excitation wavelength of 380 nm or less, and preferably has a smaller particle size because the photocatalytic reaction occurs efficiently. For example, the average particle size is 50 nm or less, more preferably 20 nm or less. Those are preferred. Examples of such anatase type titanium oxide include hydrochloric acid peptizer type anatase type titania sol (STS-02 (average particle size: 7 nm) manufactured by Ishihara Sangyo Co., Ltd.), nitrate peptizer type anatase type titania sol (Nissan Chemical). TA-15 (average particle size: 12 nm)) manufactured by Co., Ltd.

The content of the photocatalyst in the solid content in the wettability changing resin material coating solution can be set in the range of 5 to 60% by weight, preferably 20 to 60% by weight. When the content of the photocatalyst is less than 5% by weight, the wettability change becomes insufficient, or the time required for the wettability change becomes long. When the content exceeds 60% by weight, the applied wettability change resin material coating solution is applied. The mechanical strength of the resin layer 15 formed by the drying treatment is not preferable because it is insufficient.
In addition, the organopolysiloxane used in the wettability-changing resin material coating liquid has a main chain whose wettability is changed by the photocatalyst and hardly deteriorated or decomposed by the action of the photocatalyst. For example, (1) Sol-gel reaction Examples include organopolysiloxanes that exhibit high strength by hydrolyzing and polycondensing chloro or alkoxysilanes, etc., and (2) organopolysiloxanes crosslinked with reactive silicones that are excellent in water and oil repellency. .

In the case of (1) above, the general formula Y _n SiX _(4-n)
(Where Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, X represents an alkoxyl group, an acetyl group or a halogen. N is an integer from 0 to 3. is there.)
It is preferable that it is the organopolysiloxane which is a 1 type, or 2 or more types of hydrolysis condensate or cohydrolysis condensate of the silicon compound shown by these. In addition, it is preferable that carbon number of the group shown by Y exists in the range of 1-20, and it is preferable that the alkoxyl group shown by X is a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

  Specifically, methyltrichlorosilane, methyltribromosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-t-butoxysilane; ethyltrichlorosilane, ethyltribromosilane, ethyltrimethoxysilane, Ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-t-butoxysilane; n-propyltrichlorosilane, n-propyltribromosilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltriisopropoxy Silane, n-propyltri-t-butoxysilane; n-hexyltrichlorosilane, n-hexyltribromosilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hex Lutriisopropoxysilane, n-hexyltri-t-butoxysilane; n-decyltrichlorosilane, n-decyltribromosilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, n-decyltriisopropoxysilane, n- Decyltri-t-butoxysilane; n-octadecyltrichlorosilane, n-octadecyltribromosilane, n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, n-octadecyltriisopropoxysilane, n-octadecyltrit-butoxysilane; Phenyltrichlorosilane, phenyltribromosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltri-t-butoxysilane; tetrachlorosilane Tetrabromosilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane; dimethyldichlorosilane, dimethyldibromosilane, dimethyldimethoxysilane, dimethyldiethoxysilane; diphenyldichlorosilane, diphenyldibromosilane, Diphenyldimethoxysilane, diphenyldiethoxysilane; phenylmethyldichlorosilane, phenylmethyldibromosilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane; trichlorohydrosilane, tribromohydrosilane, trimethoxyhydrosilane, triethoxyhydrosilane, triisopropoxy Hydrosilane, tri-t-butoxyhydrosilane; vinyltrichlorosilane, vinyltribromosilane, vinyltri Methoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltrit-butoxysilane; trifluoropropyltrichlorosilane, trifluoropropyltribromosilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, trifluoropropyl Triisopropoxysilane, trifluoropropyltri-t-butoxysilane; γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxy Propyltriethoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropyltri-t-butoxysilane; γ-methacryloxypropylmethyldimeth Silane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltriisopropoxysilane, γ-methacryloxypropyl Tri-t-butoxysilane; γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ- Aminopropyltri-t-butoxysilane; γ-mercaptopropylmethyldimethoxylane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysila , Γ-mercaptopropyltriisopropoxysilane, γ-mercaptopropyltri-t-butoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxylane, β- (3,4-epoxycyclohexyl) ethyltriethoxylane And partial hydrolysates thereof; and mixtures thereof.

In particular, a polysiloxane containing a fluoroalkyl group can be preferably used, and specific examples thereof include one or two or more hydrolytic condensates and cohydrolytic condensates of the following fluoroalkylsilanes: In general, those known as fluorine-based silane coupling agents can be used.
_{CF 3 (CF 2) 3 CH} 2 CH 2 Si (OCH 3) 3;
_{CF 3 (CF 2) 5 CH} 2 CH 2 Si (OCH 3) 3;
_{CF 3 (CF 2) 7 CH} 2 CH 2 Si (OCH 3) 3;
_{CF 3 (CF 2) 9 CH} 2 CH 2 Si (OCH 3) 3;
(CF ₃ ) CF (CF ₂ ) ₄ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ;
(CF ₃ ) CF (CF ₂ ) ₆ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ;
(CF ₃ ) CF (CF ₂ ) ₈ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ;
_{CF 3 (C 6 H 4)} C 2 H 4 Si (OCH 3) 3;
_{CF 3 (CF 2) 3 (} C 6 H 4) C 2 H 4 Si (OCH 3) 3;
_{CF 3 (CF 2) 5 (} C 6 H 4) C 2 H 4 Si (OCH 3) 3;
_{CF 3 (CF 2) 7 (} C 6 H 4) C 2 H 4 Si (OCH 3) 3;
_{CF 3 (CF 2) 3 CH} 2 CH 2 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 5 CH} 2 CH 2 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 7 CH} 2 CH 2 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 9 CH} 2 CH 2 SiCH 3 (OCH 3) 2;
(CF ₃ ) CF (CF ₂ ) ₄ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ ;
(CF ₃ ) CF (CF ₂ ) ₆ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ ;
(CF ₃ ) CF (CF ₂ ) ₈ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ ;
_{CF 3 (C 6 H 4)} C 2 H 4 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 3 (} C 6 H 4) C 2 H 4 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 5 (} C 6 H 4) C 2 H 4 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 7 (} C 6 H 4) C 2 H 4 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 3 CH} 2 CH 2 Si (OCH 2 CH 3) 3;
_{CF 3 (CF 2) 5 CH} 2 CH 2 Si (OCH 2 CH 3) 3;
_{CF 3 (CF 2) 7 CH} 2 CH 2 Si (OCH 2 CH 3) 3;
_{CF 3 (CF 2) 9 CH} 2 CH 2 Si (OCH 2 CH 3) 3; and
_{CF 3 (CF 2) 7 SO} 2 N (C 2 H 5) C 2 H 4 CH 2 Si (OCH 3) 3.
In addition, examples of the reactive silicone (2) include compounds having a skeleton represented by the following general formula.

ただし、ｎは２以上の整数であり、Ｒ¹、Ｒ²はそれぞれ炭素数１〜１０の置換もしくは非置換のアルキル、アルケニル、アニールあるいはシアノアルキル基であり、モル比で全体の４０％以下がビニル、フェニル、ハロゲン化フェニルである。また、Ｒ¹、Ｒ²がメチル基のものが表面エネルギーが最も小さくなるので好ましく、モル比でメチル基が６０％以上であることが好ましい。また、鎖末端もしくは側鎖には、分子鎖中に少なくとも１個以上の水酸基等の反応性基を有することが好ましい。

However, n is an integer of 2 or more, and R ¹ and R ² are each a substituted or unsubstituted alkyl, alkenyl, anneal, or cyanoalkyl group having 1 to 10 carbon atoms, and the molar ratio is 40% or less. Vinyl, phenyl and phenyl halide. In addition, it is preferable that R ¹ and R ² are methyl groups because the surface energy is the smallest, and it is preferable that the methyl groups are 60% or more by molar ratio. Further, the chain end or side chain preferably has at least one reactive group such as a hydroxyl group in the molecular chain.

Moreover, you may mix the stable organosilicone compound which does not produce a crosslinking reaction like dimethylpolysiloxane with said organopolysiloxane.
The wettability changing resin material coating liquid may further contain a surfactant. Specifically, hydrocarbons such as NIKKOL BL, BC, BO, BB series manufactured by Nikko Chemicals Co., Ltd., ZONYL FSN, FSO manufactured by DuPont, Surflon S-141, 145 manufactured by Asahi Glass Co., Ltd., Dainippon Megafac F-141, 144 manufactured by Ink Chemical Industry Co., Ltd., Fientent F-200, F-251 manufactured by Neos Co., Ltd. Yunidyne DS-401, 402 manufactured by Daikin Industries, Ltd., manufactured by 3M Co., Ltd. Fluorine-based or silicone-based nonionic surfactants such as Fluorard FC-170 and 176 can be mentioned, and cationic surfactants, anionic surfactants and amphoteric surfactants can also be used.

  In addition to the above-mentioned surfactant, the wettability changing resin material coating solution includes polyvinyl alcohol, unsaturated polyester, acrylic resin, polyethylene, diallyl phthalate, ethylene propylene diene monomer, epoxy resin, phenol resin, polyurethane, Melamine resin, polycarbonate, polyvinyl chloride, polyamide, polyimide, styrene butadiene rubber, chloroprene rubber, polypropylene, polybutylene, polystyrene, polyvinyl acetate, polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, polyisoprene, etc. An oligomer, a polymer, etc. can be contained.

Such a wettability changing resin material coating liquid can be prepared by dispersing the above-described components in a solvent together with other additives as required. As the solvent to be used, alcohol-based organic solvents such as ethanol and isopropanol are preferable. The coating can be performed by a known coating method such as spin coating, spray coating, or dip coating.
Next, another embodiment of the method for producing a nanoimprint mold of the present invention will be described with reference to FIGS. 4 and 5, taking as an example a nanoimprint mold 31 having the same structure as the nanoimprint mold 11 described above.
In the present invention, in the recess forming step, the wettability changing resin material coating liquid is applied to the surface 32a of the base 32 having the protruding structure 34 protruding from one surface of the base 33, on the side where the protruding structure 34 protrudes. Is applied to form a wettability changing resin material layer 35 '(FIG. 4A). The base material 32 to be used can be the same as the base material 12 described in the above embodiment. Further, the wettability changing resin material coating liquid described in the above embodiment can also be used as the wettability changing resin material coating liquid, and the thickness of the wettability changing resin material layer 35 ′ is the depth of the recess 36 to be formed. It can be set in consideration of the shape and the like, and can be set, for example, in the range of about 0.01 to 10 μm. Next, the wettability changing resin material layer 35 ′ located on the convex structure 34 and the master mold 41 are pressure-bonded (FIG. 4B), and then separated from each other to form a recess in the wettability changing resin material layer 35 ′. 36 is formed. The master mold 41 to be used can be the same as the master mold 21 described in the above embodiment.

Next, in the drying step, the wettability-changing resin material layer 35 ′ having the recesses 36 is subjected to a drying treatment so that the water contact angle on the surface is 90 ° or more, preferably 95 ° or more, and the hardness is A resin layer 35 of 400 or more, preferably 600 or more is formed (FIG. 4C). The drying treatment is not particularly limited as long as the solvent is removed from the wettability changing resin material layer 35 ′ and the resin layer 35 having a hardness of 400 or more can be obtained. For example, the temperature is in the range of 20 to 200 ° C. It can be set appropriately. When the water contact angle of the surface of the resin layer 35 formed by performing such a drying treatment is less than 90 °, due to the hydrophilic variation of the light shielding film forming composition liquid to be used in the light shielding film forming step described later, Since the light shielding film 37 is also formed on the resin layer 35 in the pattern area X where the light shielding film 37 is not required, it is not preferable. Further, if the hardness of the resin layer 35 formed by performing the drying process is less than 400, the durability of the produced mold 31 may be insufficient, which is not preferable.
In the present invention, the drying process may be incorporated into the recess forming process. That is, as shown in FIG. 4B, the wettability changing resin material layer 35 ′ and the master mold 41 are bonded to each other in a state where the wettability changing resin material layer 35 ′ and the master mold 41 are pressed. May be applied to form the resin layer 35, and then the master mold 41 and the resin layer 35 may be separated.

Next, in the wettability changing step, the resin layer 35 located on the base 33 and the side surface 34a of the convex structure 34 is irradiated with light to form a resin layer 35a having a water contact angle of 10 ° or less on the surface ( FIG. 5 (A)). The light irradiated here includes at least light within the excitation wavelength range of the photocatalyst contained in the resin layer 35. For example, VUV (vacuum ultraviolet light) and ultraviolet light can be used. Moreover, visible light, infrared rays, etc. may be included. Light irradiation only on the resin layer 35 located on the base 33 and on the side surface 34a of the convex structure 34 is light only on the resin layer 15 located on the base 13 and on the side 14a of the convex structure 14 in the above-described embodiment. It can be similar to irradiation.
When the water contact angle of the surface of the resin layer irradiated with light exceeds 10 °, the thickness of the light shielding film 37 to be formed is reduced due to the hydrophilic variation of the light shielding film forming composition liquid used in the light shielding film forming process described later. This is not preferable because it may be insufficient or cause defects.
In this embodiment, the resin layer 35 positioned on the base 33 and the side surface 34a of the convex structure 34 is irradiated with light. However, in the present invention, the resin layer 35 positioned on the base 33 may be irradiated with light. Light irradiation to the resin layer 35 located on the side surface 34a of the convex structure 34 is optional.

  Next, in the light shielding film forming step, a light shielding film forming composition liquid is applied onto the resin layer 35 and the resin layer 35a. The applied composition liquid for forming a light shielding film is not applied to the resin layer 35 having a water contact angle of 90 ° or more, and the resin layer 35a has a water contact angle of 10 ° or less in the wettability changing step. Only applied on top. Then, the light shielding film 37 is formed on the resin layer 35a by drying and curing (FIG. 5B). Thereby, the mold 31 for nanoimprint is obtained. The light shielding film forming composition liquid and the light shielding film forming composition liquid used can be applied in the same manner as in the above-described embodiment. Here, for example, in film formation by a vacuum film formation method such as sputtering, film formation on surfaces having different surface directions is difficult, and the surface directions are different as in the side surface 34a of the base portion 33 and the convex structure portion 34. The formation of the light shielding film on the surface requires the use of a mask, control of the adhesion direction of the light shielding material, and the like, and the process becomes complicated. On the other hand, in the present invention, the composition liquid for forming a light shielding film is applied and applied only on the resin layer having a water contact angle of 10 ° or less in the wettability changing step. The light shielding film 37 can be easily formed on a surface having a different surface direction, such as the side surface 34a of the convex structure 34, and the process is simple.

  According to the present invention, the water contact angle of the surface of the resin layers 15 and 35 formed by drying the applied wettability changing resin material coating solution is 90 ° or more, and then the light shielding films 17 and 37. Since the resin layers 15 and 35 at the surface are irradiated with light to form the resin layers 15a and 35a having a water contact angle of 10 ° or less on the surface, the hydrophilicity of the light shielding film forming composition liquid applied to the resin layer Even if there is a variation in properties, the composition for forming a light-shielding film is not applied to a portion (resin layers 15 and 35) having a water contact angle of 90 ° or more, and a portion having a water contact angle of 10 ° or less (resin Since the light-shielding film can be formed only on the layers 15a and 35a), the process becomes simple. Further, since the recess 16 is formed in the resin layer 15 by pressure bonding using the master mold 21 after the light shielding film 17 is formed, the recess 36 is formed in the wettability changing resin material layer 35 ′ by pressure bonding using the master mold 41. In the formation of the light shielding film 37 after the formation, there is no etching process, vacuum film forming process, resist stripping process, or polishing process, so that the recesses 16 and 36 and the light shielding films 17 and 37 can be prevented from being damaged. Since the resin layer formed by the drying treatment has a hardness of 400 or more, a highly durable mold for nanoimprinting can be produced.

Here, an example of pattern formation in nanoimprinting by an imprinting apparatus using the nanoimprinting mold 11 manufactured by the method for manufacturing a nanoimprinting mold of the present invention will be described with reference to FIG.
As shown in FIG. 6, the convex structure portion 14 (pattern region X) of the nanoimprint mold 11 is pushed into a resin layer 53 disposed as a workpiece on the surface of the substrate 52 to a predetermined depth. In this state, the back surface 12b of the substrate 12 of the nanoimprint mold 11 is irradiated with ultraviolet rays from an illumination optical system (not shown), and the resin layer 53 is cured by the ultraviolet rays that have passed through the nanoimprint mold 11. At this time, the ultraviolet rays irradiated to the non-pattern region Y are shielded by the light shielding film 17, and thereby, exposure to an unintended portion of the resin layer 53 is reliably suppressed. Further, in the nanoimprint mold 11, the resin layer 15 formed by performing a drying process has a hardness of 400 or more, while the resin layer 53 that is a workpiece is more fragile than the resin layer 15. Therefore, the nanoimprint mold 11 has good durability.

Thereafter, the nanoimprint mold 11 is released from the resin layer 53, whereby a concavo-convex structure in which the concave portions 16 of the nanoimprint mold 11 are inverted is transferred and formed on the resin layer 53 that is a workpiece.
The above-described embodiment is an exemplification, and the present invention is not limited to this.

Next, the present invention will be described in more detail by showing more specific examples.
[Example 1]
Quartz glass (65 mm square) with a thickness of 6.35 mm was prepared as a base material for a mold for nanoimprinting.

<Drying process>
First, a commercially available resist is applied to one surface of the base material, exposed and developed through a desired mask, and an etching resist is applied to a 35 mm square region (pattern region) located at the center of the base material. Formed. Next, the base material was half-etched using this etching resist as a mask to form a base portion having a thickness of 6.335 mm and a convex structure portion having a height of 15 μm protruding from the base portion. Thereafter, the etching resist was removed to obtain a mesa base material.

Next, a wettability changing resin material coating liquid having the following composition is applied and coated on the surface of the base material on which the convex structure portion protrudes by spin coating, followed by drying treatment (150 ° C., 10 ° C. Minutes) to form a resin layer (thickness 1 μm).
(Composition of wettability changing resin material coating solution)
・ Amorphous silica: 50 parts by weight
(Glaska HPC7002 manufactured by JSR Corporation)
・ Wettability changing component: 10 parts by weight
(Glaska HPC402H manufactured by JSR Corporation)
・ Photocatalyst: 20 parts by weight
(TA-15 manufactured by Nissan Chemical Industries, Ltd. (average particle size 12 nm))
-Solvent component (toluene) 20 parts by weight The water contact angle of the surface of the resin layer thus formed was 90 °, and the hardness of the resin layer was 610. In addition, the water contact angle was measured using a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science Co., Ltd.) 30 seconds after dropping water droplets from the microsyringe. Further, the hardness was measured using a micro Vickers hardness tester (HMV-FA series, manufactured by Shimadzu Corporation). The same applies to the following examples and comparative examples.

<Wettability change process>
Next, light was irradiated to the resin layer located on the base part of a base material and the side surface of a convex structure part among the resin layers formed as mentioned above. This light irradiation was performed by irradiating 200 mJ / cm ^{2 of} parallel light (vacuum ultraviolet light having a wavelength of 172 nm) through a mask having a light shielding portion (35 mm square) corresponding to the convex structure portion. As a result, the water contact angle on the surface of the irradiated region was 10 °.

<Light shielding film forming step>
Next, by applying a light-shielding film-forming composition liquid having the following composition on the resin layer by spin coating, drying and curing (230 ° C., 30 minutes), the surface water contact angle in the wettability changing step described above A light-shielding film (thickness 1 μm) was formed on the resin layer having an angle of 10 °.
(Composition of composition liquid for light shielding film formation)
Carbon black: 61 parts by weight Photopolymer composition: 39 parts by weight Methoxybutyl acetate: 300 parts by weight

Said photosensitive resin composition has the following composition.
(Composition of photosensitive resin composition)
• Acrylic resin: 32 parts by weight • Dipentaerythritol hexaacrylate: 42 parts by weight • Epicoat 180S70 (manufactured by Mitsubishi Yuka Shell Co., Ltd.): 18 parts by weight • Irg. 907 (manufactured by Ciba Specialty Chemicals)
... 8 parts by weight

<Recess formation process>
A quartz mold is processed to produce a master mold in which cylindrical convex portions having a diameter of 100 nm are arranged in a 30 mm square region at a pitch of 200 nm, and this master mold is pressure-bonded to a resin layer located on the convex structure portion. Then, it was separated and a recess (depth 200 nm, diameter 100 nm) was formed in the resin layer. Thereby, a mold for nanoimprinting was obtained.

<Evaluation>
As a result of observing the recesses and the light-shielding film with a microscope for 100 nanoimprint molds thus produced, no damage occurred. Moreover, as a result of measuring the optical density (OD) of the light shielding film under the following conditions, it was confirmed that it was 2 or more.
(Measurement of optical density)
Measurement is performed with an optical system based on the reflection optical density measurement of JIS B9622: 2000 (ISO 13656: 2000). Using a 2405 type microdensitometer manufactured by Sakata Inx Engineering Co., Ltd., 10 light absorption parts were measured, and the average value was taken as the optical density.

In addition, a photocurable resin (PAK-01 manufactured by Toyo Gosei Co., Ltd.) is applied onto a 625 μm thick quartz wafer to form a workpiece, and placed on the substrate stage of the imprint apparatus so that the quartz wafer comes into contact therewith. did. Next, the mold was pushed into the photocurable resin layer, and in this state, parallel light (ultraviolet light having a peak wavelength of 365 nm) was irradiated from the illumination optical system of the imprint apparatus at 100 mJ / cm ² . Thereby, the photocurable resin layer was cured, and then the pattern was formed by separating the mold. About the pattern formed in this way, the defect rate was measured as follows. As a result, the defect rate was 0.02, and it was confirmed that good imprint transfer was performed.
(Defect rate measurement)
The inside of the pattern region was observed with an optical microscope at five locations, and the ratio of the area where the peeling of the resin layer and the pattern defect could be confirmed was measured within one observation location (1.0 mm × 1.0 mm). Therefore, it means that there are many defects, so that this defect rate is large, and in this invention, it determines with a defect rate being less than 0.1 as a practical use level.

[Example 2]
Quartz glass (65 mm square) with a thickness of 6.35 mm was prepared as a base material for a mold for nanoimprinting.
<Recess formation process>
First, the above-mentioned base material was used and a base material having a mesa structure was obtained in the same manner as in Example 1.
Next, a wettability changing resin material coating solution having the same composition as that of Example 1 is applied and coated on the surface of the base material from which the convex structure portion projects, and then heat treatment ( (40 ° C., 2 minutes) to remove the solvent to form a wettability changing resin material layer.
Next, the same master mold as used in Example 1 is pressure-bonded to the wettability changing resin material layer located on the convex structure portion, and then separated from the wettability changing resin material layer to form a recess (depth). 200 nm, diameter 100 nm).

<Drying process>
The wettability changing resin material layer in which the recesses were formed as described above was subjected to a drying treatment (150 ° C., 10 minutes) to form a resin layer (thickness 1 μm).
The water contact angle on the surface of the resin layer thus formed was 95 °, and the hardness of the resin layer was 610.

<Wettability change process>
Next, in the resin layer formed as described above, the resin layer located on the base portion of the base material and the side surface of the convex structure portion is irradiated with a dose of 150 mJ / cm ² , and the same as in Example 1. Then, light irradiation was performed. As a result, the water contact angle on the surface of the irradiated region was 8 °.

<Light shielding film forming step>
Next, a light-shielding film forming composition liquid having the same composition as in Example 1 is applied onto the resin layer by spin coating, and dried and cured (230 ° C., 30 minutes). A light-shielding film (thickness 1 μm) was formed on the resin layer having a water contact angle of 8 °. Thereby, a mold for nanoimprinting was obtained.

<Evaluation>
As a result of observing the recesses and the light-shielding film with a microscope for 100 nanoimprint molds thus produced, no damage occurred. Moreover, as a result of measuring the optical density (OD) of the light shielding film in the same manner as in Example 1, it was confirmed that it was 2 or more.
Further, pattern formation was performed in the same manner as in Example 1, and the defect rate was measured. As a result, it was 0.03, and it was confirmed that good imprint transfer was performed.

[Example 3]
Quartz glass (65 mm square) with a thickness of 6.35 mm was prepared as a base material for a mold for nanoimprinting.
<Recess formation process / drying process>
First, the above-mentioned base material was used and a base material having a mesa structure was obtained in the same manner as in Example 1.
Next, a wettability changing resin material coating solution having the same composition as that of Example 1 is applied and coated on the surface of the base material from which the convex structure portion projects, and then heat treatment ( (40 ° C., 2 minutes) to remove the solvent to form a wettability changing resin material layer.
Next, the same master mold as used in Example 1 was pressure-bonded to the wettability changing resin material layer located on the convex structure portion, and in that state, the wettability changing resin material layer was dried (150 ° C., For 10 minutes) to form a resin layer. Thereafter, the master mold and the resin layer were separated from each other, and a recess (depth 200 nm, diameter 100 nm) was formed in the resin layer.
The water contact angle on the surface of the resin layer (thickness 1 μm) thus formed was 90 °, and the hardness of the resin layer was 610.

<Wettability change process>
Next, among the resin layers formed as described above, light irradiation was performed on the resin layers located on the base portion of the base material and on the side surfaces of the convex structure portion in the same manner as in Example 1. As a result, the water contact angle on the surface of the irradiated region was 10 °.

<Light shielding film forming step>
Next, a light-shielding film forming composition liquid having the same composition as in Example 1 is applied onto the resin layer by spin coating, and dried and cured (230 ° C., 30 minutes). A light-shielding film (thickness 1 μm) was formed on the resin layer having a water contact angle of 10 °. Thereby, a mold for nanoimprinting was obtained.

<Evaluation>
As a result of observing the recesses and the light-shielding film with a microscope for 100 nanoimprint molds thus produced, no damage occurred. Moreover, as a result of measuring the optical density (OD) of the light shielding film in the same manner as in Example 1, it was confirmed that it was 2 or more.
Further, pattern formation was performed in the same manner as in Example 1, and the defect rate was measured. As a result, it was 0.02, and it was confirmed that good imprint transfer was performed.

[Comparative Example 1]
In the <Drying Step> of Example 1, the conditions for the drying treatment were 100 ° C. for 1 minute, the water contact angle on the surface of the resin layer was 70 °, and the hardness was 220. A mold for nanoimprinting was produced.
<Evaluation>
As a result of observing the recesses and the light-shielding film with a microscope with respect to 100 nanoimprint molds thus produced, the light-shielding film was also traced in the resin layer region (pattern region) where the recesses were formed using the master mold. It was formed and could not be put to practical use.

[Comparative Example 2]
In the <Wettability changing step> of Example 1, the irradiation amount was 110 mJ / cm ² irradiation, and the water contact angle on the surface of the resin layer at the light irradiation site was 20 °, as in Example 1, A mold for nanoimprinting was produced.
<Evaluation>
As a result of observing the recesses and the light-shielding film with a microscope for 100 nanoimprint molds thus produced, no damage occurred. However, as a result of measuring the optical density (OD) of the light-shielding film in the same manner as in Example 1, there were locations less than 2 and there was variation in the thickness of the light-shielding film.

[Comparative Example 3]
Quartz glass (65 mm square) with a thickness of 6.35 mm was prepared as a base material for a mold for nanoimprinting.
A chromium thin film (thickness: 50 nm) was formed on one surface of the substrate by sputtering, and then a commercially available resist was applied on the chromium thin film.
Next, the base material was placed on a stage in a commercially available electron beam drawing apparatus so that the back surface of the base material faces the stage, and the resist was irradiated with an electron beam to form a desired pattern latent image.
Next, the resist is developed to form a resist layer, and the resist layer is used as a mask to form openings (patterns in which circular openings with a diameter of 100 nm are arranged in a grid with a pitch of 200 nm) in a chromium thin film by dry etching. An etching mask was obtained. Next, a recess was formed in the base material by anisotropic etching through this light-shielding etching mask. The formed recess had a depth of 200 nm and a diameter of 100 nm. The pattern area in which the recess was formed was a 30 mm square area located in the center of the substrate.

Next, the light-shielding etching mask was removed by etching using ceric ammonium nitrate as an etchant.
Next, a commercially available resist was applied to the surface of the base material on which the recesses were formed, exposed through a desired mask, and developed to form an etching resist in the 35 mm square pattern region. Next, the base material was etched using the etching resist as a mask to form a base portion having a thickness of 6.335 mm and a convex structure portion having a height of 15 μm protruding from the base portion.
Next, a silicon thin film (thickness: 50 nm) was formed on the substrate by vacuum deposition so as to cover the etching resist, thereby forming a light shielding film. Thereafter, the etching resist was stripped using a resist stripping solution, and the light shielding film on the etching resist was also removed. Thereby, the light shielding film remained only on the side surface and the base portion of the convex structure portion, and a mesa structure mold for nanoimprinting as shown in FIG. 1 was obtained.

<Evaluation>
As a result of observing the recesses and the light-shielding film using a microscope for 100 nanoimprint molds thus produced, damage to the recesses occurred in 30 molds, and in particular, there was a lot of damage at the edges of the pattern area of 35 mm square. It has occurred.

  It can be used for microfabrication using nanoimprint technology.

DESCRIPTION OF SYMBOLS 11, 31 ... Mold for nanoimprint 12, 32 ... Base material 13, 33 ... Base part 14, 44 ... Convex structure part 14a, 34a ... Side surface of convex structure part 15, 35 ... Resin layer 15a, 35a ... The wettability was changed Resin layer 35 '... wettability changing resin material layer 16, 36 ... concave portion 17, 37 ... light shielding film 21, 41 ... master mold

Claims (7)

A base having a base and a convex structure protruding from one surface of the base; a resin layer covering a surface of the base from which the convex structure protrudes; and the base on the convex structure In a method for producing a mold for nanoimprint, comprising: a recess located in a resin layer; and a light-shielding film covering a resin layer located on the base.
A base material having a base and a convex structure protruding from one surface of the base is coated with a wettability-changing resin material coating solution on the surface of the base on which the convex structure protrudes, and then dried. Applying a treatment to form a resin layer having a surface water contact angle of 90 ° or more and a hardness of 400 or more;
A wettability changing step of irradiating the resin layer located on the base with light so that the water contact angle of the surface of the resin layer at the irradiated site is 10 ° or less;
A light-shielding film forming step of forming a light-shielding film on the resin layer located on the base by applying a composition liquid for forming a light-shielding film on the resin layer, and drying and curing;
A recess forming step of forming a recess in the resin layer by pressure-bonding the resin layer located on the projecting structure and the master mold, and then separating the master mold, and a mold for nanoimprint, Production method. A base having a base and a convex structure protruding from one surface of the base; a resin layer covering a surface of the base from which the convex structure protrudes; and the base on the convex structure In a method for producing a mold for nanoimprint, comprising: a recess located in a resin layer; and a light-shielding film covering a resin layer located on the base.
A base material having a base and a convex structure projecting from one surface of the base is coated with a wettability-changing resin material coating solution on the surface of the base on which the convex structure projects. A recess forming step of forming a recess in the wettability changing resin material layer by pressing the wettability changing resin material layer and the master mold located on the part, and then separating the master mold;
A drying process in which the wettability changing resin material layer is subjected to a drying treatment to form a resin layer having a surface water contact angle of 90 ° or more and a hardness of 400 or more;
A wettability changing step of irradiating the resin layer located on the base with light so that the water contact angle of the surface of the resin layer at the irradiated site is 10 ° or less;
A light-shielding film forming step of forming a light-shielding film on the resin layer located on the base by applying a composition liquid for forming a light-shielding film on the resin layer, and drying and curing. The manufacturing method of the mold for nanoimprint made.   Incorporating the drying step into the recess forming step, subjecting the wettability changing resin material layer positioned on the convex structure portion and the master mold to pressure bonding, subjecting the wettability changing resin material layer to a drying treatment, and then master mold 3. The nanoimprint for nanoimprint according to claim 2, wherein the resin layer is separated from the resin layer to form a resin layer having a recess, a surface water contact angle of 90 ° or more, and a hardness of 400 or more. Mold manufacturing method.   In the wettability changing step, light is also applied to the resin layer located on the side surface of the convex structure portion together with the resin layer located on the base portion, and the water contact angle on the surface of the resin layer at the irradiated portion is set. The light-shielding film is formed on the resin layer located on the side surface of the convex structure portion as well as on the resin layer located on the base portion in the light-shielding film forming step. The manufacturing method of the mold for nanoimprints in any one of Claims 1 thru | or 3.   The method for producing a nanoimprint mold according to any one of claims 1 to 4, wherein the wettability changing resin material coating solution contains at least an organopolysiloxane and a photocatalyst.   The nanoimprint mold according to any one of claims 1 to 5, wherein the light shielding film forming composition liquid contains at least one of carbon, titanium oxide, copper oxide, and iron oxide as a light shielding material. Manufacturing method.   The application of the light-shielding film forming composition liquid onto the resin layer is performed by any one of a spin coating method, a spray coating method, and a dip coating method. The manufacturing method of the mold for nanoimprint of description.

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