JP2008100378A - Manufacturing method of pattern forming body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a pattern forming body, which prevents the leakage of a resin at the time of imprinting. <P>SOLUTION: The manufacturing method of the pattern forming body has: a resin layer-to-be-transferred forming process of using a substrate having a lyophilic layer and a liquid repelling layer formed on its surface and coating the lyophilic layer with a coating solution for forming a resin layer to be transferred to form the resin layer to be transferred; an adhesion laminate forming process for closely adhering a mold having an uneven pattern part to the resin layer to be transferred to form an adhesion laminate; and a curing process for curing the resin layer to be transferred of the adhesion laminate. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method of manufacturing a pattern forming body that can prevent resin leakage during imprinting.

  For example, when a semiconductor integrated circuit or a microlens is manufactured, a photolithography method is currently widely used. On the other hand, an imprint method is known as a method for forming a concavo-convex pattern at a lower cost than such photolithography. The imprint method is to form a concavo-convex pattern on the surface of a substrate to be transferred by using a mold having a desired concavo-convex pattern on the surface in close contact with the substrate to be transferred and applying an external stimulus such as heat or light. Is the method.

  However, the imprint method has the following problems. That is, as shown in FIG. 3 (a), in a general imprint method, shaping is performed by bringing the concave / convex pattern of the mold 5 into close contact with the transferred resin layer 4 formed on the substrate 3. However, there is a problem that the transferred resin layer may spread out of a predetermined range due to the pressure at the close contact (possibility of resin leakage), and a desired pattern may not be formed.

  In response to such problems, attempts have been made to prevent resin leakage by devising the shape of the mold. For example, Patent Document 1 discloses an imprint mold having a mesa structure. The mesa structure refers to a structure in which a level difference is formed on a portion where the concave / convex pattern is not formed (non-concave / convex pattern portion) on the surface where the mold is in contact with the transferred resin layer, and specifically, as shown in FIG. Further, by providing a step in the non-concave pattern portion 9 of the mold 5, contact with the transferred resin layer 4 is avoided, and the occurrence of resin leakage is suppressed.

  However, in order to produce an imprint mold having a mesa structure, a process for etching the non-recessed pattern portion is required as compared with the case of producing a normal mold, and there are problems such as poor throughput. It was. Furthermore, even when an imprint mold having a mesa structure is used, depending on the depth of the mesa structure part, there is a problem that resin flows into the mesa structure part and resin leakage occurs.

US Pat. No. 6,996,220

  This invention is made | formed in view of the said situation, and it aims at providing the manufacturing method of the pattern formation body which can prevent the resin leak at the time of imprint.

  In order to solve the above problems, in the present invention, a substrate having a lyophilic layer and a lyophobic layer formed on its surface is used, and a coating liquid for forming a resin layer to be transferred is applied onto the lyophilic layer. A transferred resin layer forming step for forming a transfer resin layer, a mold having a concavo-convex pattern portion in close contact with the transferred resin layer, and forming an adhesive laminate, and the adhesive laminate And a curing step of curing the transferred resin layer. A method for producing a pattern forming body is provided.

  According to the present invention, the resin leakage can be suppressed by providing the lyophilic layer and the liquid repellent layer on the substrate surface.

In the above invention, when the contact angle is measured using a test solution having a surface tension of 0.073 mN / m, the contact angle (θ _a ) in the lyophilic layer and the contact angle (θ in the lyophobic layer) and the difference between _{b) (θ b -θ a)} is 50 ° or more. This is because the occurrence of resin leakage can be effectively suppressed due to the large difference between the contact angle (θ _a ) and the contact angle (θ _b ).

  In the above invention, the lyophilic layer is formed of a silane coupling agent having a lyophilic functional group, and the lyophobic layer is formed of a silane coupling agent having a lyophobic functional group. It is preferable. This is because a lyophilic layer and a liquid repellent layer can be easily formed by separately coating two types of silane coupling agents.

  In the above invention, a wettability changing layer whose surface wettability is changed by the action of a photocatalyst is formed on the substrate, and the wettability changing layer and a photocatalyst containing layer containing a photocatalyst are formed on a substrate. The lyophilic layer and the liquid repellent layer are formed on the substrate by arranging the photocatalyst-containing layer side substrate at a predetermined interval and irradiating energy in a pattern from a predetermined direction. Is preferred. This is because the lyophilic layer and the liquid repellent layer can be easily formed only by the difference in the presence or absence of energy irradiation.

  In the said invention, it is preferable that the said to-be-transferred resin layer contains a thermosetting resin or a photocurable resin. This is because these curable resins are excellent in versatility and inexpensive.

  In the said invention, it is preferable that the said mold has an uneven | corrugated pattern part and a non-recessed pattern part on the surface, and the liquid repellency of the said uneven | corrugated pattern part is higher than the liquid repellency of the said uneven | corrugated pattern part. . This is because the occurrence of resin leakage can be further suppressed by increasing the liquid repellency of the non-concave pattern portion.

  Further, the present invention is characterized in that the surface has a concavo-convex pattern portion and a non-concave pattern portion, and the liquid repellency of the non-concave pattern portion is higher than the liquid repellency of the concavo-convex pattern portion. An imprint mold is provided.

  According to the present invention, the liquid repellency of the non-concave pattern portion is higher than the liquid repellency of the concavo-convex pattern portion. Occurrence can be suppressed.

In the above invention, when the contact angle is measured using a test solution having a surface tension of 0.073 mN / m, the contact angle (θ _c ) at the concavo-convex pattern portion and the contact angle (θ _c ) at the non-concave pattern portion ( the difference between _{θ d) (θ d -θ c} ) is preferably not more than 10 °. This is because the occurrence of resin leakage can be effectively suppressed due to the large difference between the contact angle (θ _c ) and the contact angle (θ _d ).

  In this invention, there exists an effect that generation | occurrence | production of a resin leak can be suppressed by using the board | substrate provided with the lyophilic layer and the liquid repellent layer.

  Hereafter, the manufacturing method of the pattern formation body of this invention and the mold for imprint are demonstrated in detail.

A. First, the manufacturing method of the pattern formation body of this invention is demonstrated. The method for producing a patterned product of the present invention uses a substrate having a lyophilic layer and a lyophobic layer formed on its surface, and applies a coating liquid for forming a transferred resin layer on the lyophilic layer, thereby transferring the transferred resin. A transfer resin layer forming step of forming a layer, a close-contact laminate forming step of closely attaching a mold having a concavo-convex pattern portion to the transfer resin layer to form a close-contact laminate, and a covering of the close-contact laminate. And a curing step for curing the transfer resin layer.

  According to the present invention, the resin leakage can be suppressed by providing the lyophilic layer and the liquid repellent layer on the substrate surface. Specifically, by applying a liquid repellent layer having poor affinity to the transfer resin layer forming coating liquid on the substrate, the transfer resin layer forming coating liquid is applied and When the transfer resin layer and the concavo-convex pattern portion of the mold are brought into close contact with each other, it is possible to suppress the transfer resin layer from spreading outside a predetermined range.

Next, the manufacturing method of the pattern formation body of this invention is demonstrated using drawing. FIG. 1 is a process diagram showing an example of a method for producing a pattern forming body of the present invention. 1 uses a substrate 3 having a lyophilic layer 1 and a lyophobic layer 2 formed on the surface thereof, and the lyophilic layer 1 is coated with a photocurable resin. A transferred resin layer forming step (FIG. 1A) for applying a liquid to form a transferred resin layer (photocurable resin layer) 4, and a mold having an uneven pattern portion with respect to the transferred resin layer 4 5 is in close contact with each other to form a close-contact laminate 6 (FIG. 1B), and a curing step in which the transferred resin layer 4 of the close-contact laminate 6 is cured by irradiation with light 7 (FIG. 1). (C)) and the peeling process (FIG.1 (d)) which peels the mold 5 from the contact | adherence laminated body 6 after a hardening process.
Hereinafter, the manufacturing method of the pattern formation body of this invention is demonstrated for every process.

1. Transferred resin layer forming step The transferred resin layer forming step in the present invention will be described. The transferred resin layer forming step in the present invention uses a substrate having a lyophilic layer and a lyophobic layer formed on the surface, and applies a transfer resin layer forming coating solution on the lyophilic layer, thereby transferring the transferred resin. It is a process of forming a layer. Usually, in the present invention, the transferred resin layer is formed only on the lyophilic layer having excellent affinity with the transferred resin layer forming coating solution.

(1) Lipophilic layer and liquid repellent layer First, the lyophilic layer and the liquid repellent layer used in the present invention will be described. The lyophilic layer used in the present invention is a layer that is formed on a substrate and holds a transferred resin layer described later. In the present invention, the lyophilic layer is not particularly limited as long as it has a higher affinity for the transferred resin layer forming coating solution than the liquid repellent layer. On the other hand, the liquid repellent layer used in the present invention is a layer formed on a substrate and having a function of mainly suppressing the occurrence of resin leakage. In the present invention, the liquid repellent layer is not particularly limited as long as the liquid repellent layer has a lower affinity for the transfer resin layer forming coating liquid than the liquid repellent layer.

In the present invention, when the contact angle is measured using a test solution having a surface tension of 0.073 mN / m, the contact angle (θ _a ) in the lyophilic layer and the contact angle (θ in the lyophobic layer) _b) the difference between (θ _b -θ _a) is 50 ° or more and preferably 60 ° or more, particularly preferably in the range of 70 ° to 120 °. This is because the occurrence of resin leakage can be effectively suppressed due to the large difference between the contact angle (θ _a ) and the contact angle (θ _b ). In addition, the said contact angle can be obtained by measuring using a contact angle measuring device (for example, Kyowa Interface Science Co., Ltd. CA-Z type) (after dropping a droplet from a microsyringe, 30 seconds later). . As the test solution having the surface tension, for example, pure water or the like can be used. Moreover, all the contact angles mentioned later can be measured by this method.

When the contact angle is measured using a test solution having a surface tension of 0.073 mN / m, the contact angle (θ _a ) in the lyophilic layer is formed by forming a desired transferred resin layer on the lyophilic layer. Although it is not particularly limited as long as it is possible, for example, it is preferably less than 60 °, more preferably less than 50 °, and particularly preferably in the range of 0 ° to 20 °. This is because the transfer resin layer-forming coating solution spreads well and a uniform transfer resin layer can be formed.

When the contact angle is measured using a test solution having a surface tension of 0.073 mN / m, the contact angle (θ _b ) in the liquid repellent layer is particularly limited as long as the occurrence of resin leakage can be suppressed. Although it is not a thing, it is preferable that it exists in the range of 110 degrees or more, especially 110 degrees or more, especially 110 degrees-120 degrees, for example. This is because the occurrence of resin leakage can be sufficiently suppressed by exhibiting high liquid repellency.

  Next, materials for the lyophilic layer and the liquid repellent layer will be described. The material of the lyophilic layer is not particularly limited as long as it can form a layer having a higher affinity for the coating liquid for forming the resin layer to be transferred compared to the liquid repellent layer. On the other hand, the material of the liquid repellent layer is not particularly limited as long as it can form a layer having a lower affinity for the coating liquid for forming the resin layer to be transferred compared to the lyophilic layer. Among these materials, it is preferable that these materials satisfy the above-described contact angle conditions.

  In particular, in the present invention, the lyophilic layer is preferably formed of a silane coupling agent having a lyophilic functional group. This is because a lyophilic layer excellent in lyophilicity can be easily formed. Specifically, as the lyophilic layer formed by the silane coupling agent having the lyophilic functional group, a monomolecular film formed by reacting the silane coupling agent with a functional group on the substrate, or The silane coupling agent can be reacted with a functional group on the substrate, and can also be hydrolyzed and polycondensed by a sol-gel reaction or the like. What formed the film | membrane is preferable. Examples of a method for forming a monomolecular film by reacting a silane coupling agent with a functional group on a substrate include the method described in JP-A-6-289627.

Specific examples of the lyophilic functional group possessed by the silane coupling agent include a hydroxyl group (—OH), a carboxyl group (—COOH), and a sulfone group (—SO ₃ H). Furthermore, as the silane coupling agent having the lyophilic functional group, specifically, C ₃ H ₆ NH ₂ Si (CH ₃ O) ₃ (for example, KBM903 manufactured by Shin-Etsu Silicone), C ₃ H ₆ NHC ₂ H ₄ NH ₂ Si (CH ₃ O) ₃ (for example, KBM603 manufactured by Shin-Etsu Silicone) can be used.

  On the other hand, in the present invention, the liquid repellent layer is preferably formed from a silane coupling agent having a liquid repellent functional group. This is because a liquid repellent layer having excellent liquid repellency can be easily formed. As the liquid repellent layer formed by the silane coupling agent having the liquid repellent functional group, specifically, a monomolecular film formed by reacting the silane coupling agent with a functional group on the substrate, or The silane coupling agent can be reacted with a functional group on the substrate, and can also be hydrolyzed and polycondensed by a sol-gel reaction or the like. What formed the film | membrane is preferable.

Specific examples of the liquid repellent functional group possessed by the silane coupling agent include a methyl group (—CH ₃ ), an ethyl group (—C ₂ H ₅ ), and a fluoromethyl group (—CF ₃ ). Can be mentioned. Furthermore, as the silane coupling agent having the liquid repellent functional group, specifically, CF ₃ Si (OCH ₂ CH ₃ ) ₃ (for example, 419982 manufactured by Aldrich), CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ (for example, T1770 manufactured by Tokyo Chemical Industry Co., Ltd.) and CH ₃ (CH ₂ ) ₅ Si (OCH ₃ ) ₃ (for example, H0879 manufactured by Tokyo Chemical Industry Co., Ltd.).

  In particular, in the present invention, the lyophilic layer is formed of a silane coupling agent having a lyophilic functional group, and the liquid repellent layer is formed of a silane coupling agent having a lyophobic functional group. It is preferable. This is because a lyophilic layer and a liquid repellent layer can be easily formed by separately coating two types of silane coupling agents.

  In the present invention, on the substrate, a wettability changing layer whose surface wettability is changed by the action of the photocatalyst is formed, and the wettability changing layer and the photocatalyst-containing layer containing the photocatalyst are formed on the substrate. The lyophilic layer and the liquid repellent layer are formed on the substrate by arranging the formed photocatalyst-containing layer side substrate at a predetermined interval and irradiating energy in a pattern from a predetermined direction. It is preferable to do. This is because the lyophilic layer and the liquid repellent layer can be easily formed only by the difference in the presence or absence of energy irradiation.

  Here, “the wettability changes by the action of the photocatalyst” specifically means that the wettability changes from lyophobic to lyophilic by the action of the photocatalyst accompanying energy irradiation. Therefore, for example, by forming a wettability changing layer on the entire surface of the substrate and irradiating energy only to the region to be a lyophilic layer, the portion that has been irradiated with energy functions as a lyophilic layer, and the portion that is not irradiated with energy It can function as a liquid repellent layer.

The material of the wettability changing layer (wetability changing material) is not particularly limited as long as it is a material whose wettability is changed by the action of the photocatalyst and is difficult to deteriorate or decompose by the action of the photocatalyst. Examples thereof include organopolysiloxanes obtained by hydrolyzing and polycondensing alkoxysilanes by sol-gel reaction or the like. Specifically, Y _n SiX _(4-n) (wherein Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group, or an epoxy group, and X represents an alkoxyl group, an acetyl group, or 1 represents a halogen, and n represents an integer of 0 to 3.) One or two or more hydrolyzed condensates or organopolysiloxanes which are hydrolyzed condensates. Here, the number of carbon atoms of the group represented by Y is preferably within the range of 1 to 20, and the alkoxyl group represented by X is a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. Is preferred.

  As another example of the wettability changing material, for example, polyethylene, polycarbonate, polypropylene, polystyrene, polyester, polyvinyl fluoride, acetal resin, nylon, ABS, PTFE, methacrylic resin, phenol resin, polyvinylidene fluoride, polyoxymethylene And polymer materials such as polyvinyl alcohol, polyvinyl chloride, polyethylene terephthalate, silicone, cellulose, rubber, polyvinyl alcohol, and nylon.

Examples of the photocatalyst contained in the photocatalyst-containing layer include titanium dioxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), strontium titanate (SrTiO ₃ ), tungsten oxide (WO ₃ ), and bismuth oxide. (Bi ₂ O ₃ ), iron oxide (Fe ₂ O ₃ ) and the like can be mentioned, and among these, titanium dioxide (TiO ₂ ) is preferable.

  As the wettability changing material, and the photocatalyst and binder used for the photocatalyst containing layer, for example, the same materials as those described in JP2003-295428A and JP2003-222626A can be used. . Further, as a method of irradiating energy to the wettability changing layer to form a lyophilic layer and a liquid repellent layer, specifically, a method similar to the method described in FIG. 1 of JP-A-2003-295428, etc. Can be mentioned. Furthermore, as the wettability changing material used in the present invention, for example, those disclosed in Japanese Patent Application Laid-Open Nos. 2001-074928 and 2003-209339 can be used.

  When the substrate used in the present invention is a highly lyophilic substrate, the substrate can be used as it is as a lyophilic layer. In this case, a substrate having a lyophilic / liquid repellent pattern can be obtained only by separately providing a liquid repellent layer by the above-described method. Similarly, when the substrate used in the present invention is a substrate having high liquid repellency, the substrate can be used as it is as a liquid repellent layer. In this case, a substrate having a lyophilic / repellent pattern can be obtained only by providing a separate lyophilic layer by the method described above.

The pattern of the lyophilic layer and the liquid repellent layer formed on the substrate is not particularly limited, and can be arbitrarily set according to the use of the pattern forming body.
The thickness of the lyophilic layer and the lyophobic layer varies depending on the material constituting the lyophilic layer and the lyophobic layer, but is usually in the range of 1 nm to 1 μm.

(2) Substrate Next, the substrate used in the present invention will be described. The substrate used in the present invention holds the lyophilic layer and the liquid repellent layer described above.

  The material of the substrate is different depending on the use of the pattern forming body, and for example, a semiconductor such as silicon (Si), gallium arsenide, (GaAs), aluminum gallium arsenide (AlGaAs), gallium nitride (GaN); Resins such as polyethylene, polystyrene, polypropylene, polycarbonate, vinyl chloride, and pet resin; metals such as titanium (Ti), copper (Cu), iron (Fe), nickel (Ni), aluminum (Al), and chromium (Cr); Examples thereof include glass such as quartz and soda lime glass; and alloys containing the above substances.

  The substrate may be transparent or opaque. For example, the transfer resin contained in the transfer resin layer is a photocurable resin, and light is irradiated from the substrate side. For this, the substrate is preferably transparent.

  The thickness of the substrate varies depending on the use of the pattern forming body and is not particularly limited, but is, for example, in the range of 10 μm to 1000 μm.

(3) Transferred resin layer forming coating solution Next, the transferred resin layer forming coating solution used in the present invention will be described. The coating liquid for forming a transferred resin layer used in the present invention usually contains a transferred resin and a solvent.

  The resin to be transferred is not particularly limited as long as it can be cured by a curing process described later, and examples thereof include a photocurable resin and a thermosetting resin. Specific examples of the photocurable resin include PAK-01 (manufactured by Toagosei), NIP-K (manufactured by Zen Photonics), and TSR-820 (manufactured by Teijin Seiki). On the other hand, specific examples of the thermosetting resin include polymethyl methacrylate (PMMA), polystyrene (PS), and polycarbonate (PC).

(4) Method for Forming Transferred Resin Layer Next, a method for forming the transferable resin layer used in the present invention will be described. In the present invention, the transfer resin layer is formed by applying the transfer resin layer forming coating solution on the lyophilic layer and removing the solvent.

  A general application method can be used as a method for applying the coating liquid for forming the transferred resin layer on the lyophilic layer, and is not particularly limited. Method, spraying method, spin coating method, etc., among which the dropping method is preferred. This is because it is possible to suppress the generation of air (air gap) between the substrate and the transferred resin layer.

  The thickness of the transferred resin layer varies depending on the use of the pattern forming body, but is usually in the range of 0.1 to 100 μm. In addition, since it is thought that possibility that resin leakage will arise when a to-be-transferred resin layer is too thick, according to the material of the to-be-transferred resin layer, etc., it is preferable to determine thickness suitably.

2. Adhesive Laminate Forming Step Next, the adhesive laminated body forming step in the present invention will be described. The adhesion laminated body formation process in this invention is a process of making the mold which has an uneven | corrugated pattern part closely_contact | adhere with respect to the to-be-transferred resin layer mentioned above, and forming an adhesion laminated body.

(1) Mold First, the mold used in the present invention will be described. The mold used in the present invention usually has a concavo-convex pattern portion and a non-recessed pattern portion on the surface. In particular, in the present invention, the uneven pattern portion is preferably a nano uneven pattern portion having nano-order unevenness. This is because it has nano-order irregularities and is useful for manufacturing semiconductor devices. Further, the non-recessed pattern portion refers to a region other than the uneven pattern portion, and is usually a region having a smooth surface.

  In the present invention, the concavo-convex pattern portion and the non-concave pattern portion preferably have appropriate liquid repellency. This is because the release property of the cured transferred resin is improved by having an appropriate liquid repellency. Furthermore, in the present invention, it is more preferable that the liquid repellency of the non-concave pattern portion is higher than the liquid repellency of the uneven pattern portion. This is because the occurrence of resin leakage can be further suppressed by increasing the liquid repellency of the non-concave pattern portion. As such a mold, for example, as shown in FIG. 2, the mold 5 has a concavo-convex pattern portion 8 and a non-recessed pattern portion 9, and the liquid repellency of the concavo-convex pattern portion 8 is that of the non-recessed pattern portion 9. Examples include those having higher liquid repellency.

In the present invention, when the contact angle is measured using a test solution having a surface tension of 0.073 mN / m, the contact angle (θ _c ) at the concavo-convex pattern portion and the contact angle (θ at the liquid repellent layer) are measured. _d) the difference between (θ _d -θ _c) is 10 ° or more and preferably 20 ° or more, particularly preferably in the range of 30 ° to 40 °. This is because the occurrence of resin leakage can be effectively suppressed due to the large difference between the contact angle (θ _c ) and the contact angle (θ _d ).

When the contact angle is measured using a test solution having a surface tension of 0.073 mN / m, the contact angle (θ _c ) at the concavo-convex pattern portion is not particularly limited. Among them, it is preferably 110 ° or more, particularly preferably within a range of 110 ° to 120 °.

When the contact angle is measured using a test solution having a surface tension of 0.073 mN / m, the contact angle (θ _d ) at the non-concave pattern portion is not particularly limited, but for example, 80 ° or more In particular, it is preferably 90 ° or more, particularly preferably in the range of 90 ° to 110 °.

  Examples of a method for imparting liquid repellency to the uneven pattern portion and the non-recessed pattern portion of the mold include, for example, the silane coupling agent and wettability change described in “(1) Lipophilic layer and liquid repellent layer”. A method using a material or the like can be given.

The material of the mold is not particularly limited as long as a desired uneven pattern can be formed. Examples thereof include silicon (Si), gallium nitride (GaN), and gallium arsenide (GaAs). Semiconductors; Glass such as quartz and soda lime glass; Metals such as nickel (Ni) and aluminum (Al); Ceramics such as silicon nitride (SiN), silicon oxide (SiO ₂ ) and silicon carbide (SiC); Diamond and diamond-like Examples thereof include carbon (DLC) and cubic boron nitride (CBN). Among these, silicon (Si) and quartz are preferable from the viewpoint that processing with finer dimensions is possible.

  The mold may be transparent or opaque. For example, the transfer resin contained in the transfer resin layer is a photocurable resin, and light is irradiated from the mold side. For this, it is preferable that the mold is transparent.

  Although it does not specifically limit as thickness of the said mold, For example, it exists in the range of 0.5 mm-20 mm. Further, the length and width of the mold and the method for forming the concave / convex pattern portion of the mold are the same as those of a mold used in a general imprint method, and thus the description thereof is omitted here.

(2) Method for Forming Adhesion Laminate Next, a method for forming an adhesion laminate in the present invention will be described. The close-contact laminate used in the present invention is usually formed by bringing the substrate and the mold into close contact with each other via the transferred resin layer at room temperature.

3. Curing Step Next, the curing step in the present invention will be described. The curing step in the present invention is a step of curing the transfer target resin layer of the above-described adhesion laminate. The method for curing the transferred resin layer differs depending on the type of transferred resin layer used.

When the transferred resin layer is a photocurable resin layer containing a photocurable resin, the transferred resin layer is cured by irradiating the contact laminate with light. The type of light varies depending on the type of the photo-curable resin, and examples thereof include ultraviolet rays, visible rays, infrared rays, and X-rays. Among these, ultraviolet rays are preferable. This is because the ultraviolet curable photocurable resin is excellent in versatility. Among the ultraviolet rays, a generally used wavelength band is specifically about 300 nm to 400 nm. The light irradiation amount is not particularly limited as long as the photocurable resin is sufficiently hardened, and is, for example, 100 mJ / cm ² or more.

  In addition, the direction of irradiating the light is not particularly limited as long as it is a direction in which the photocurable resin can be cured. Specifically, when irradiating from the substrate side of the close-contact laminated body, irradiation from the mold side of the close-contact laminated body can be mentioned. Note that the member positioned on the incident light side of the light needs to have sufficient light transmittance.

  On the other hand, when the transferred resin layer is a thermosetting resin layer containing a thermosetting resin, the transferred resin layer is cured by heating the adhesion laminate. The heating temperature is not particularly limited as long as the thermosetting resin is sufficiently cured, but is usually in the range of 50 ° C to 200 ° C. Moreover, as a heating method, the method of heating only a board | substrate, the method of heating only a mold, the method of heating a board | substrate and a mold, etc. can be mentioned, for example.

4). Other Steps The method for producing a pattern forming body of the present invention includes at least the transferred resin layer forming step, the adhesion laminate forming step, and the curing step described above. Furthermore, in this invention, the peeling process which peels a mold from a contact | adherence laminated body is normally performed after a hardening process. The method for peeling the mold from the adhesive laminate is not particularly limited, and can be performed by a method similar to the method used in general imprinting.

  In the present invention, the transferred resin layer is usually formed on the lyophilic layer formed on the substrate surface, and the transferred resin layer is not formed on the liquid repellent layer on the substrate surface. Therefore, if necessary, a liquid repellent layer removing step for removing the liquid repellent layer may be performed after the peeling step.

5. Next, the use of the pattern formed body obtained by the present invention will be described. The pattern formed body obtained by the present invention is a substrate and a transferred resin layer formed on the substrate and having a pattern corresponding to the concave / convex pattern of the mold (hereinafter sometimes referred to as “pattern forming layer”). And having. In the present invention, the pattern forming layer may be used as a resist for processing the substrate, or the pattern forming layer itself may be used as a functional layer.

  When the pattern forming layer is used as a resist, the pattern forming body can be used for lithography in the manufacture of semiconductor devices, microelectromechanical systems such as MEMS, NEMS, and the like. On the other hand, when the pattern forming layer is used as a functional layer, the pattern forming body includes, for example, an optical element such as a microlens array or a diffraction grating; a microelectromechanical system such as MEMS or NEMS; a recording of a patterned medium or the like It can be used for disc production.

B. Next, the imprint mold of the present invention will be described. The imprint mold of the present invention has an uneven pattern portion and a non-recessed pattern portion on the surface, and the liquid repellency of the non-recessed pattern portion is higher than the liquid repellency of the uneven pattern portion. It is what.

  According to the present invention, the liquid repellency of the non-concave pattern portion is higher than the liquid repellency of the concavo-convex pattern portion. Occurrence can be suppressed. Further, as described above, in order to produce an imprint mold having a mesa structure, there is a problem that a step of further etching the non-recessed pattern portion is required and throughput is poor. In contrast, the imprint mold of the present invention has an advantage that resin leakage can be prevented by an easy operation of making a liquid repellency difference between the uneven pattern portion and the non-recessed pattern portion. Have

In the present invention, when the contact angle is measured using a test solution having a surface tension of 0.073 mN / m, the contact angle (θ _c ) at the concavo-convex pattern portion and the contact angle at the non-concave pattern portion ( the difference between _{θ d) (θ d -θ c} ) is preferably not more than 10 °. This is because the occurrence of resin leakage can be effectively suppressed. In addition, about the suitable range of the said contact angle, the material of the mold for imprint of this invention, and other matters, what was described in the above-mentioned "A. Manufacturing method of a pattern formation body 2. Adhesion laminated body formation process". Since it is the same, description here is abbreviate | omitted.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the technical idea described in the claims of the present invention has substantially the same configuration and exhibits the same function and effect regardless of the case. It is included in the technical scope of the invention.

Hereinafter, the present invention will be described more specifically with reference to examples.
[Example]
A chromium film is formed to a thickness of 100 nm on a quartz substrate, a resist (IP) is applied by a spin coating method, exposed by an I-line stepper, developed, and etched to form a chromium pattern on a smooth quartz substrate. did.
The patterned substrate was cleaned by removing organic substances on the surface by O ₂ plasma ashing. Next, as a silane coupling agent exhibiting a liquid repellent functional group, CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ solution (solvent: 1,3-bistrifluorobenzene) for 5 minutes at room temperature And heated at 55 degrees for 30 minutes. Next, the chromium pattern of the substrate was peeled off with a chromium etchant to obtain a patterned liquid repellent layer.
Next, as a silane coupling agent showing a lyophilic functional group, a C ₃ H ₆ NH ₂ Si (CH ₃ O) ₃ solution (solvent: water) was used, and the substrate on which the pattern-like liquid repellent layer was formed was used. A spin coat method was applied thereon and heated at 70 ° C. for 15 minutes to obtain a patterned lyophilic layer. In this way, a substrate patterned with two types of silane coupling agents was obtained.
Next, when the contact angle of the obtained substrate was measured using a test solution (pure water) having a surface tension of 0.073 mN / m, the contact angle of the lyophilic layer was 60 °, and the liquid repellent layer was The contact angle was 113 °. Moreover, when the obtained board | substrate was observed with AFM (Atomic Force Microscope), it confirmed that the lyophilic layer and liquid repellent layer of the monomolecular coat were able to be produced on the board | substrate. As a result of imprinting using this substrate, it was confirmed by an optical microscope that the imprint resin spread only in the lyophilic layer and that the imprint resin did not flow into the liquid repellent layer.

It is process drawing which shows an example of the manufacturing method of the pattern formation body of this invention. It is a schematic sectional drawing which shows an example of the mold used for this invention. It is explanatory drawing explaining resin leakage.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Lipophilic layer 2 ... Liquid repellent layer 3 ... Board | substrate 4 ... Transferred resin layer 5 ... Mold 6 ... Adhesion laminated body 7 ... Light 8 ... Concave / convex pattern part 9 ... Non-concavity / convex pattern part

Claims (8)

A transferred resin layer forming step of forming a transferred resin layer by applying a transfer resin layer forming coating liquid on the lyophilic layer using a substrate having a lyophilic layer and a liquid repellent layer formed on the surface; ,
Adhering laminate forming step of closely adhering a mold having an uneven pattern portion to the transferred resin layer to form an adhering laminate,
A curing step of curing the transferred resin layer of the adhesive laminate;
A method for producing a pattern-formed body, comprising: When the contact angle was measured using a test solution having a surface tension of 0.073 mN / m, the difference between the contact angle (θ _a ) in the lyophilic layer and the contact angle (θ _b ) in the lyophobic layer The method for producing a pattern forming body according to claim 1, wherein (θ _b −θ _a ) is 50 ° or more.   The lyophilic layer is formed of a silane coupling agent having a lyophilic functional group, and the lyophobic layer is formed of a silane coupling agent having a lyophobic functional group. The manufacturing method of the pattern formation body of Claim 1 or Claim 2.   A photocatalyst-containing layer is formed by forming a wettability changing layer whose surface wettability is changed by the action of a photocatalyst on the substrate, and the wettability changing layer and a photocatalyst-containing layer containing a photocatalyst are formed on a substrate. The lyophilic layer and the lyophobic layer are formed on the substrate by arranging a side substrate at a predetermined interval and irradiating energy in a pattern from a predetermined direction. The manufacturing method of the pattern formation body of Claim 1 or Claim 2.   The method for producing a pattern forming body according to any one of claims 1 to 4, wherein the transferred resin layer contains a thermosetting resin or a photocurable resin.   The mold has a concavo-convex pattern portion and a non-concave pattern portion on the surface, and the liquid repellency of the non-concave pattern portion is higher than the liquid repellency of the concavo-convex pattern portion. The manufacturing method of the pattern formation body in any one of Claim 5 to Claim 5.   An imprint mold characterized in that it has a concavo-convex pattern portion and a non-recessed pattern portion on the surface, and the liquid repellency of the non-recessed pattern portion is higher than the liquid repellency of the uneven pattern portion. When the contact angle was measured using a test solution having a surface tension of 0.073 mN / m, the contact angle (θ _c ) at the uneven pattern portion and the contact angle (θ _d ) at the non-recessed pattern portion The imprint mold according to claim 7, wherein the difference (θ _d −θ _c ) is 10 ° or more.

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