JP7060840B2 - Imprint mold and imprint method - Google Patents

Description

The present disclosure relates to an imprint mold and an imprint method using the imprint mold.

In recent years, in the manufacturing process of semiconductor devices (for example, semiconductor memory, etc.), a mold member (mold) having a fine concavo-convex structure formed on the surface of the substrate is used, and the fine concavo-convex structure is transferred to a workpiece such as a substrate. Nanoimprint technology, which is a pattern forming technology for transferring a fine concavo-convex structure at the same magnification, is used.

Nanoimprint molds and the like having such a fine uneven structure generally form a resist pattern corresponding to the fine uneven structure by exposing and developing a resist film provided on the surface of a quartz glass substrate or the like, and then forming a resist pattern. , The quartz glass substrate on which the resist pattern is formed is subjected to an etching process using the resist pattern as a mask.

Nanoimprint molds and the like having a fine concavo-convex structure have problems that the manufacturing cost is very high and the manufacturing takes a long time. Therefore, a resin mold having a fine pattern, which is produced by transferring a fine uneven structure to a resin by using such a nanoimprint mold as a master mold, is known.

However, since the resin mold is inferior in rigidity to the nanoimprint mold manufactured by using a quartz glass substrate or the like, there is a problem that defects or the like occur in the fine pattern while being used for the nanoimprint processing. .. Further, in order to improve the durability of the resin mold, it is considered to perform a mold release treatment. Further, in order to improve the rigidity of the resin mold, a base base material such as a silicon wafer or a glass wafer, a patterned polymer layer provided on the base base material, and a metal covering the polymer layer are conventionally provided. Alternatively, an imprint lithography template having an oxide layer has been proposed (see Patent Document 1).

Special Table 2016-514903 Gazette

In Patent Document 1, the metal or oxide layer covering the patterned polymer layer is a thin film having a thickness of about 2 to 50 nm, and only covers the polymer layer, so that the rigidity of the polymer pattern is not high. There is a problem that it is sufficient and the pattern collapses. Further, if a local force is applied to the metal or oxide layer during the imprinting process or the like, at least a part of the metal or oxide layer is peeled off, thereby reducing the releasability and durability. There is a problem that it will end up.

In view of the above problems, the present disclosure discloses an imprint mold having a fine pattern made of a resin having sufficient rigidity and an excellent pattern shape and capable of exhibiting stable releasability over time, and the imprint mold. One purpose is to provide the imprint method used.

In order to solve the above problems, as one embodiment of the present disclosure, a base material having a first surface and a second surface facing the first surface is provided on the first surface of the base material. Provided is an imprint mold comprising a fine pattern having a plurality of convex portions, wherein the base material and the fine pattern are composed of a reaction product of a resin material and an inorganic material.

The resin material preferably has a reactive functional group exhibiting reactivity with the inorganic material, and preferably further includes a release layer that covers the surface of the fine pattern, and the release layer contains fluorine. It is preferable to include the material.

It is preferable to further provide an inorganic oxide film between the surface of the fine pattern and the release layer, and the inorganic oxide film can be composed of silicon oxide or titanium oxide, and the first of the base materials. Further comprising a metal film covering the surface, the fine pattern may be provided on the metal film, further comprising an adhesion promoting layer covering the first surface of the substrate, said fine pattern. It may be provided so as to be in contact with the adhesion promoting layer.

The fine pattern and the base material may be integrally configured. Further comprising an alignment mark provided on the first surface of the substrate, the alignment mark may be composed of the reaction product and is part of a plurality of protrusions of the fine pattern. And the other part may be composed of a reaction product of the resin material and the inorganic material of different types from each other.

As one embodiment of the present disclosure, an imprint method using the imprint mold, in which a transfer substrate having a transfer surface and a back surface facing the transfer surface is prepared, and a transfer substrate. By the step of supplying the imprint resin onto the surface to be transferred and by bringing the fine pattern of the imprint mold into contact with the imprint resin, the first surface of the imprint mold and the substrate to be transferred are described. A step of developing the imprint resin between the imprinted surfaces and a step of curing the imprinted resin developed between the first surface of the imprint mold and the transferred surface of the transferred substrate. The resin material constituting the fine pattern, which comprises a step of pulling the imprint mold away from the cured imprint resin, is a material that can be softened by heating, and at least in the step of pulling the imprint mold away. An imprint method is provided in which a fine pattern is heated to separate the imprint mold from the imprint resin.

According to the present disclosure, an imprint mold having a fine pattern made of a resin having sufficient rigidity and an excellent pattern shape and capable of exhibiting stable releasability over time, and an imprint using the imprint mold. A method can be provided.

FIG. 1 is a cut end view showing a schematic configuration of an imprint mold according to an embodiment of the present disclosure. FIG. 2 is a cut end view showing a schematic configuration of another aspect of the imprint mold according to the embodiment of the present disclosure. FIG. 3 is a cut end view showing a schematic configuration of another aspect (No. 1) of the fine pattern of the imprint mold according to the embodiment of the present disclosure. FIG. 4 is a cut end view showing a schematic configuration of another aspect (No. 2) of the fine pattern of the imprint mold according to the embodiment of the present disclosure. FIG. 5 is a plan view showing a schematic configuration of one aspect of the alignment mark of the imprint mold according to the embodiment of the present disclosure. FIG. 6 is a plan view showing a schematic configuration of another aspect of the alignment mark of the imprint mold according to the embodiment of the present disclosure. FIG. 7 is a flowchart showing a gas exposure step in the method for manufacturing an imprint mold according to the embodiment of the present disclosure. FIG. 8 is a process flow chart showing the manufacturing method of the imprint mold according to the embodiment of the present disclosure on the cut end face. FIG. 9 is a process flow chart showing the imprint method according to the embodiment of the present disclosure on the cut end face. FIG. 10 is a block diagram schematically showing a resist pattern reforming apparatus according to an embodiment of the present disclosure. FIG. 11 is a block diagram showing a schematic configuration of a resist pattern reforming apparatus according to an embodiment of the present disclosure.

An embodiment of the present invention will be described with reference to the drawings.
In the drawings attached to the present specification, in order to facilitate understanding, the shape, scale, aspect ratio, etc. of each part may be changed or exaggerated from the actual product. The numerical range represented by using "-" in the present specification and the like means a range including each of the numerical values described before and after "-" as a lower limit value and an upper limit value. In the present specification and the like, terms such as "film", "sheet", and "board" are not distinguished from each other based on the difference in designation. For example, "board" is a concept that also includes members that may be commonly referred to as "sheets" or "films".

[Imprint mold]
The imprint mold 1 according to the present embodiment has a base material 2 having a first surface 2A and a second surface 2B facing the first surface 2A, a metal film 3 covering the first surface 2A of the base material 2, and a metal film 3 on the metal film 3. It is provided with a fine pattern 4 having a plurality of convex portions 41, which is provided in the above.

Examples of the base material 2 include quartz glass, soda glass, fluorite, calcium fluoride substrate, magnesium fluoride substrate, glass substrate such as acrylic glass, polycarbonate substrate, polypropylene substrate, polyimide substrate, epoxy substrate, polyethylene substrate and the like. A resin substrate, a transparent substrate such as a laminated substrate formed by laminating two or more substrates arbitrarily selected from these; a metal substrate such as a nickel substrate, a titanium substrate, and an aluminum substrate; a semiconductor such as a silicon substrate and a gallium nitride substrate. A substrate or the like can be used.

The thickness of the base material 2 can be appropriately set in the range of, for example, about 300 μm to 10 mm in consideration of the strength of the substrate, handling suitability, and the like. In the present embodiment, "transparent" means that the transmittance of light rays having a wavelength of 300 nm to 450 nm is 85% or more, and is preferably 90% or more.

The fine pattern 4 (convex portion 41) is composed of a reaction product (complex) of a resin material and an inorganic material. Since the fine pattern 4 is composed of the reaction product (complex), sufficient rigidity can be achieved.

As will be described later, the fine pattern 4 is formed by exposing the resist pattern 4'(see FIG. 8D) made of the above resin material to a gas (first gas) containing an inorganic element-containing compound. To. Therefore, the resin material has a reactive functional group that exhibits reactivity with an inorganic element-containing compound. Examples of such a reactive functional group include a carbonyl group, a thiocarbonyl group, an acryloyl group, a hydroxyl group, a sulfanyl group, an epoxy group and the like. Examples of the resin material having such a reactive functional group include imprint resins (acrylic-based, methacrylic-based and other ultraviolet curable resins, etc.) generally used for imprint processing using an imprint mold, and electron beams. An electron beam-sensitive resin, an ultraviolet-sensitive resin, or the like generally used in a lithography process or a photolithography process can be preferably used. In particular, the imprint resin tends to contain a large amount of reactive functional groups as compared with the resin for electron beam lithography and the resin for photolithography, so that the reaction can proceed efficiently.

Further, it is preferable that the resin material can be softened by heating to the extent that the pattern shape of the fine pattern 4 does not collapse. When the fine pattern 4 in the present embodiment has sufficient rigidity, it may be difficult to separate the imprint mold 1 from the imprint resin cured in the imprint process using the imprint mold 1. However, since the resin material constituting the fine pattern 4 can be softened by heating, when the imprint mold 1 is heated when it is separated from the imprint resin, the fine pattern 4 is softened and the imprint mold is made from the imprint resin. The effect of making it easier to separate 1 is achieved.

The resin material constituting the plurality of convex portions 41 constituting the fine pattern 4 is not limited to one type. For example, one convex portion 41 and the other convex portion 41 may be made of a resin material having different types of reactive functional groups. Since the reactivity with the inorganic element-containing compound differs depending on the type of the reactive functional group of the resin material, the fine pattern 4 having different rigidity for each convex portion 41 can be obtained. For example, the pattern region on which the fine pattern 4 is formed on the first surface 2A of the base material 2 of the imprint mold 1 is divided into a plurality of regions, and the convex portions 41 formed in each region are of different types. It can be made of a resin material having a reactive functional group of. Thereby, for example, the mold release method can be controlled by utilizing the difference in the glass transition temperature and the elastic modulus of various resin materials constituting the convex portion 41 formed in each region. For example, the rigidity of the convex portion 41 (for example, the convex portion 41 located outside the pattern region) where the mold release is first started is delayed, and the convex portion 41 (for example, the pattern region) where the mold release is started later than that. By lowering the rigidity of the convex portion 41) located inside the mold, the stress at the start of mold release can be reduced. Further, by minimizing the rigidity of the convex portion 41 to be released at the end, the stress applied at the end of the mold release can be reduced.

The inorganic material constituting the reaction product (composite) may be any material that can be bonded to the reactive functional group of the resin material, and for example, aluminum (Al), titanium (Ti), silicon (Si) and the like may be used. Can be mentioned.

Regarding the abundance of the inorganic material inside the fine pattern 4, it is preferable that the abundance of the inorganic material is less than 90% by mass within the range from the side wall of the fine pattern 4 to 50 nm along the orthogonal direction of the side wall. Is 20% by mass to 50% by mass.

In the imprint mold 1 according to the present embodiment, the inorganic oxide film 42 covering the side wall and the top of the fine pattern 4 and the release layer 43 covering the inorganic oxide film 42 are provided (FIGS. 1 and 2). (See), the present invention is not limited to this embodiment, and the inorganic oxide film 42 may be provided without the release layer 43 (see FIG. 3), and the inorganic oxide film 42 and the release layer 43 may be provided. It may not be provided (see FIG. 4).

By providing the inorganic oxide film 42 that covers the side wall and the top of the fine pattern 4, the adhesion of the fine pattern 4 to the release layer 43 can be improved. The inorganic oxide film 42 is not particularly limited as long as it can improve the adhesion to the release layer 43, and examples thereof include a silicon oxide film, a titanium oxide film, aluminum oxide, and chromium oxide.

The film thickness of the inorganic oxide film 42 may be, for example, about 0.1 nm to 3 nm, preferably about 0.3 nm to 2 nm. If the thickness of the inorganic oxide film 42 is less than 0.3 nm, the inorganic oxide film 42 may not be able to completely cover the side wall and the top of the fine pattern 4, and the inorganic oxide film 42 may become non-uniform. If it exceeds 3 nm, the expansion rate of the inorganic oxide film 42 may be different from that of the resin material constituting the fine pattern 4, resulting in poor adhesion of the inorganic oxide film 42 to the fine pattern 4 or cracks in the inorganic oxide film 42. be.

By having the release layer 43, it is possible to easily separate the imprint mold 1 from the imprint resin. Examples of the material constituting the release layer 43 include a fluorine alkyl-containing silane coupling agent, a long-chain alkyl-containing silane coupling agent, and the like.

The film thickness of the release layer 43 may be, for example, about 0.1 nm to 3 nm, preferably about 0.3 nm to 2 nm. If the film thickness of the release layer 43 is less than 0.3 nm, the release layer 43 cannot completely cover the inorganic oxide film 42, and it may be difficult to obtain the effect of mold release property, which is 3 nm. If it exceeds, the filling property of the imprint resin in the imprint process may be affected.

In the imprint mold 1 according to the present embodiment, the first surface 2A of the base material 2 is coated with the metal film 3 (see FIGS. 1, 3, and 4). When the imprint resin and the base material 2 come into direct contact with each other, the base material 2 may be charged. However, since the first surface 2A of the base material 2 is covered with the metal film 3, the imprint mold 1 It is possible to prevent the base material 2 from being charged in the imprinting process using the above.

The material constituting the metal film 3 may be a transparent material or an opaque material. If the material constituting the metal film 3 is a transparent material, the imprint mold 1 can be used for the optical imprint process via the imprint mold 1. On the other hand, even when the material constituting the metal film 3 is an opaque material, if the transferred substrate 101 is made of a transparent material, it can be used for the optical imprinting process via the transferred substrate 101. can. Examples of the material constituting such a metal film 3 include nickel, chromium, copper, titanium and the like.

In the imprint mold 1 according to the present embodiment, even if an adhesion promoting layer (not shown) having a function of improving the adhesion of the fine pattern 4 to the metal film 3 is provided on the metal film 3. good. The material constituting such an adhesion promoting layer may be, for example, a compound having a polymerizable functional group such as a vinyl group, an acryloyl group, a methacryloyl group, a vinyl ether group, an epoxy group, an oxetanyl group and an amino group. Specific examples thereof include a silane coupling agent. The thickness of the adhesion promoting layer provided on the metal film 3 is not particularly limited, but if the adhesion promoting layer is a monomolecular layer having a thickness of about several nm, the metal film 3 is provided. It is desirable because the antistatic effect is not hindered.

As shown in FIGS. 5 and 6, the alignment mark 5 may be provided on the first surface 2A of the base material 2. The alignment mark 5 is provided at a position away from the fine pattern 4 provided on the first surface 2A of the base material 2 and not affecting the transfer of the fine pattern 4.

The alignment mark 5 is made of the same material as the fine pattern 4. If the alignment mark 5 is made of only a resin material, it may be difficult to visually recognize the alignment mark when aligning with the transfer substrate 101. However, since the alignment mark 5 is composed of a reaction product (complex) of a resin material and an inorganic material, the visibility of the alignment mark 5 can be improved.

The alignment mark 5 may be composed of, for example, an aggregate of uneven patterns such as a line and space shape and a pillar shape (see FIG. 5), or may be composed of an uneven pattern such as a cross shape (FIG. 5). 6). The alignment mark 5 having such a shape can be formed at the same time as the fine pattern 4 provided on the first surface 2A of the base material 2, so that the alignment mark 5 with good visibility can be obtained.

[Manufacturing method of imprint mold]
An example of a method for manufacturing the imprint mold 1 according to the present embodiment having the above-described configuration will be described. FIG. 7 is a flowchart showing each process of the imprint mold manufacturing method according to the present embodiment, and FIGS. 8 and 9 show each step of the imprint mold manufacturing method according to the present embodiment as a cut end view. It is a process flow chart shown by.

<Resist pattern forming process>
A base material 2 having a first surface 2A and a second surface 2B facing the first surface 2A is prepared, and a pattern region on the first surface 2A of the base material 2 (a region where a fine pattern 4 in the imprint mold 1 is to be formed). A resist pattern 4'is formed therein (see S01 in FIG. 7 and FIGS. 8A to 8D). As the base material 2, the same base material 2 as that of the base material 2 of the imprint mold 1 can be used, and detailed description thereof will be omitted here.

As the resin material constituting the resist pattern 4', the same resin material as the resin material constituting the fine pattern 4 of the imprint mold 1 according to the present embodiment can be used. A detailed description of the resin material will be omitted here.

The method for forming the resist pattern 4'is not particularly limited, and is, for example, a photolithography method using a photomask having a predetermined opening and a light-shielding portion, and an electron beam lithography method using an electron beam drawing apparatus. , An imprint method using an imprint mold having a predetermined uneven pattern, and the like are particularly suitable from the viewpoint of mass productivity.

Here, a method of forming the resist pattern 4'by the imprint method will be described.
First, an imprint mold 10 having an uneven structure 11 corresponding to the resist pattern 4'is prepared, and an imprint resin film 40 is formed on the first surface 2A of the base material 2 (see FIG. 8A).

Next, the uneven structure 11 of the imprint mold 10 is pressed against the imprint resin film 40 to fill the uneven structure 11 with the imprint resin, and the imprint resin film 40 is cured in that state (FIG. 8 (FIG. 8). B) See). As a method for curing the imprint resin film 40, a method corresponding to the curing type of the resin material constituting the imprint resin film 40 may be adopted. For example, if the resin material is an ultraviolet curable resin, the in-print resin film 40 may be cured. A method of irradiating the imprint resin film 40 with ultraviolet rays via the print mold 10 or the like can be adopted. When the uneven structure 11 of the imprint mold 10 is pressed against the imprint resin film 40, it is preferably placed in a helium gas atmosphere or a cohesive gas atmosphere. A pattern defect (insufficient filling of the imprint resin) occurs in the resist pattern 4'due to the generation of air bubbles between the uneven structure 11 of the imprint mold 10 and the imprint resin filled in the uneven structure 11. However, in a helium atmosphere or a cohesive gas atmosphere, the helium gas and the cohesive gas constituting the bubbles can be dissolved in the imprint resin, and the pattern defects can be generated. Can be prevented.

The imprint mold 10 is separated from the cured imprint resin film 40 (see FIG. 8C). In this way, a resist pattern 4'having a plurality of convex portions 4a'and concave portions 4b' and a residual film portion 4c' located at the bottom of the concave portions 4b' can be formed by an imprint method.

When the resist pattern 4'is formed by an electron beam lithography method or a photolithography method, an electron beam sensitive resist material film or an ultraviolet sensitive resist material film is formed on the first surface 2A of the base material 2 to form an electron beam. The resist pattern 4'can be formed through a drawing process using a drawing device or the like, an exposure process using a photomask having a predetermined opening and a light-shielding portion, and a development process.

The shape of the resist pattern 4'is not particularly limited, and examples thereof include a line-and-space shape, a hole shape, a pillar shape, and the like, depending on the intended use. The size of the resist pattern 4'may be any size according to the intended use, but when it is 10 nm or more and less than 100 nm, particularly 10 nm or more and less than 20 nm (1X nm), the effect of the pattern forming method according to the present embodiment is remarkably exhibited. Therefore, it is preferable. The dimension means the width in the short side when the shape of the resist pattern 4'is line-and-space, and means the length or diameter of the short side when the shape is hole-shaped or pillar-shaped. It shall be. The aspect ratio of the resist pattern 4'is not particularly limited as long as it is the aspect ratio required for the imprint mold 1, and is, for example, about 0.5 to 10.

<Remaining film removal process>
At the bottom of the recess 4b'of the resist pattern 4'formed by the imprint treatment, a residual film portion 4c'with a predetermined thickness (about 1 nm to 20 nm, preferably about 5 nm to 10 nm) is present (FIG. 8 (FIG. 8). See C). The residual film portion 4c'may remain in the imprint mold 1 according to the present embodiment, or may be removed. The presence of the residual film portion 4c'can improve the adhesion of the resist pattern 4'to the substrate 2 (first surface 2A). On the other hand, in the resist pattern 4'where the residual film portion 4c'exists, the rising portion from the concave portion 4b'to the convex portion 4a'is rounded, but the residual film portion 4c'is removed. The shape of the resist pattern 4'(the shape of the rising portion) can be sharpened. Further, since the metal film 3 is exposed from the residual film portion 4c'by removing the residual film portion 4c', the antistatic effect of the metal film 3 can be exhibited. Even when the adhesion promoting layer is formed on the metal film 3, if the thickness of the adhesion promoting layer is about several nm, the antistatic effect of the metal film 3 can be exhibited.

The method for removing the residual film portion 4c'is not particularly limited, and examples thereof include ashing treatment with oxygen plasma, UV ozone treatment with ultraviolet light, VUV treatment with vacuum ultraviolet light, and the like.

Even in the resist pattern formed by the electron beam lithography method or the photolithography method, a development residue may be present between the convex portions. Similarly, in this case, the development residue may be removed or may be left without being removed.

<Adsorption prevention layer forming process>
In the present embodiment, the resist pattern 4'(see FIG. 8D) obtained by removing the residual film portion 4c'as described above is exposed to the first gas and the second gas. Prior to this, an adsorption prevention layer is formed to cover the surface of the convex portion 4a'and the concave portion 4b'of the resist pattern 4'(the surface of the first surface 2A of the base material 2 exposed by removing the residual film portion 4c'). You may. Since the first gas to which the resist pattern 4'is exposed in the first gas exposure step (see S03 in FIG. 7) described later contains an inorganic element-containing compound, the surface of the resist pattern 4'is inorganic when exposed to the first gas. Element-containing compounds may be adsorbed. When the inorganic element-containing compound is adsorbed on the surface of the resist pattern 4', it becomes difficult for the inorganic element-containing compound to permeate into the inside of the resist pattern 4', and it becomes difficult to achieve the effect of improving the rigidity of the fine pattern 4. Further, the inorganic element-containing compound is deposited on the surface of the concave portion of the resist pattern 4'(the surface of the first surface 2A of the base material 2), or a part of the residual film portion 4c'cannot be completely removed and becomes the concave portion 4b'. If it remains, it becomes difficult to form the fine pattern 4 having excellent dimensional accuracy. Therefore, by forming an adsorption prevention layer on the surface of the resist pattern 4'before carrying out the first gas exposure step, it is difficult for the inorganic element-containing compound to be adsorbed on the surface of the resist pattern 4'and permeates into the inside. It can be facilitated, and as a result, it can be facilitated to form a fine pattern 4 having sufficient rigidity. Examples of the material constituting such an adsorption prevention layer include an alkylsilane coupling agent typified by a silane coupling agent (for example, hexyltrimethoxysilane, octadecyltriethoxysilane, etc.), a benzene ring, a silane having a benzophenone group, and the like. Coupling agent), hydrophobic polymer, carbon film such as graphene, etc., and the adsorption prevention layer is formed by, for example, a liquid phase method, a vapor phase method, a vapor deposition method such as CVD or ALD, a sputtering method, or the like. obtain. Before forming the resist pattern 4', the adsorption prevention layer may be formed in advance on the first surface 2A of the base material 2.

<First processing condition and second processing condition setting process>
Next, the base material 2 having the resist pattern 4'is exposed to the first gas and the second gas (S03 to S07 in FIG. 7), but the processing conditions (first) of the first gas exposure step (S03 in FIG. 7) are performed in advance. The treatment conditions (second treatment conditions) of the second gas exposure step (S06 in FIG. 7) are set (treatment conditions) (S02 in FIG. 7).

In the present embodiment, in consideration of the rigidity required for the fine pattern 4, the number of times the first gas exposure step (S03 in FIG. 7) is repeated, the treatment time of each first gas exposure step, and the like are the first treatments. Set as a condition. In setting the first treatment conditions, the resin material constituting the resist pattern 4'has been the target of the first gas exposure step in the past, and has the rigidity required for the fine pattern 4 and the like. If the corresponding first processing condition has already been optimized, the condition may be set. However, when the resin material constituting the resist pattern 4'has never been the target of the first gas exposure step, the relevance information indicating the relationship between the information on the resin material and the first treatment condition. If so, the first processing condition may be set based on the relevance information. Examples of the information regarding the resin material include information regarding the electron density of the resin material. In the first gas exposure step (S03 in FIG. 7), the resist pattern 4'is exposed to the first gas containing an inorganic element-containing compound exhibiting Lewis acidity, as will be described later. As a result, the inorganic element-containing compound permeates into the resist pattern 4'and reacts with the resin material constituting the resist pattern 4'. The progress of this reaction is considered to depend on, for example, the type of the inorganic element-containing compound (for example, whether it is a nucleophilic compound or an electrophilic compound), the electron density of the resin material, and the like. Therefore, the first treatment condition considered to be suitable by comparing the electron density of the resin material for which the first treatment condition has already been optimized with the electron density of the resin material to be the target of the first gas exposure step for the first time. Can be set. The first treatment conditions include the dimensions of the resist pattern 4', the type of resin material constituting the resist pattern 4', the type of the inorganic element-containing compound contained in the first gas, the rigidity required for the fine pattern 4, and the like. , The conditions may be set in consideration of various conditions and may be set as appropriate.

Further, as the second treatment condition of the second gas exposure step (S06 of FIG. 7) carried out after the first gas exposure step (S03 of FIG. 7), the treatment time of the second gas exposure step and the like are set. .. Similar to the first processing condition described above, this second processing condition can also be appropriately set by past experience, setting conditions in consideration of various conditions, and the like.

<First gas exposure process>
According to the first processing conditions set as described above, the first gas exposure step is performed on the resist pattern 4'(S03 in FIG. 7). Specifically, first, according to the first treatment condition, the atmosphere around the resist pattern 4'contains an inorganic element-containing compound showing Lewis acidity, and contains an inert gas such as nitrogen (N ₂ ) as a carrier gas. The resist pattern 4'is exposed to the first gas by creating an atmosphere of the first gas. By exposing the resist pattern 4'to the first gas according to the first treatment conditions, the reactive functional groups and the inorganic element-containing compounds in the chemical structure of the resin material constituting the resist pattern 4'are formed inside the resist pattern 4'. Can be reacted.

Examples of the inorganic element-containing compound contained in the first gas include trimethylaluminum (Al (CH ₃ ) ₃ , TMA), methyltrichlorosilane, tris (dimethylamino) aluminum, tetrakis (diethylamino) titanium (IV), and titanium (IV). ) Isopropoxide, tetrachlorotitanium (IV), silicon tetrachloride, tris (t-pentoxy) silanol, bis (ethylmethylamino) silane can be exemplified. When the inorganic element-containing compound contained in the first gas is trimethylaluminum (TMA) and the reactive functional group is a carbonyl group, trimethylaluminum (TMA) and a carbonyl group are shown in the following reaction formula (1). Reacts with.

The first gas exposure step (S03 in FIG. 7) can be performed using, for example, a resist pattern reformer 50 (sequential gas phase chemical reaction apparatus, see FIGS. 10 and 11) described later. The first gas exposure step (S03 in FIG. 7) may be performed using an ALD (atomic layer deposition) device.

The first gas exposure step (S03 in FIG. 7) is carried out while monitoring the modified state of the resist pattern 4', that is, the progress of the reaction between the resin material constituting the resist pattern 4'and the inorganic element-containing compound. Is preferable. As the reaction between the resin material and the inorganic element-containing compound proceeds, for example, the optical properties of the resist pattern 4'change. Specifically, as the reaction between the resin material and the inorganic element-containing compound progresses, the reflectance, refractive index, IR characteristics, color tone, etc. for light rays having a predetermined wavelength change. Therefore, by monitoring the change in these optical characteristics, the progress of the reaction in the first gas exposure step can be confirmed and grasped, and the first gas exposure step may be controlled based on the result. Further, as the reaction between the resin material and the inorganic element-containing compound proceeds, for example, the weight of the resist pattern 4'changes. Therefore, by monitoring the weight change of the resist pattern 4', the progress of the reaction in the first gas exposure step can be confirmed and grasped, and the first gas exposure step may be controlled based on the result. ..

The time for exposing the resist pattern 4'to the first gas (treatment time of each first gas exposure step) may be in accordance with the first treatment conditions set as described above, and is, for example, 30 seconds to 10,000 seconds. Degree. When the exposure time of the first gas is less than 30 seconds, the inorganic element-containing compound contained in the first gas binds to the reactive functional group located on the outermost surface of the resist pattern 4'and is bonded to the outermost surface of the resist pattern 4'. There is a risk that a thin film of inorganic oxide (so-called ALD film) will be formed on the surface of the resist pattern 4'due to the action of the oxidizing agent contained in the second gas, which will be described later.

The temperature condition in the first gas exposure step (S03 in FIG. 7) may follow the first treatment condition set as described above, but is a temperature lower than the glass transition temperature of the resin material constituting the resist pattern 4'. Under the conditions, it is preferable to expose the resist pattern 4'to the first gas. By exposing the resist pattern 4'to the first gas while heating, the reaction between the reactive functional group and the inorganic element-containing compound contained in the first gas can be promoted inside the resist pattern 4', but each time. If the processing time of the first gas exposure step is relatively long, the resist pattern 4'may be deformed depending on the temperature conditions of the first gas exposure step. Therefore, by exposing the resist pattern 4'to the first gas under a temperature condition lower than the glass transition temperature of the resin material constituting the resist pattern 4', it is possible to prevent the resist pattern 4'from being deformed. can.

The processing pressure conditions in the first gas exposure step (S03 in FIG. 7) may be in accordance with the first processing conditions set as described above, and for example, 133.3 Pa to 1333.2 Pa (1.0 Torr to 10). It is preferably set to about 0.0 Torr), and more preferably set to about 400.0 Pa to 933.3 Pa (3.0 Torr to 7.0 Torr). When the treatment pressure condition is less than 133.3 Pa (1.0 Torr), the inorganic element-containing compound contained in the first gas is a resist, especially when the adsorption prevention layer is not formed on the surface of the resist pattern 4'. It binds to the reactive functional group located on the outermost surface of the pattern 4'and is chemically adsorbed on the outermost surface of the resist pattern 4', and is inorganic on the surface of the resist pattern 4'by the action of the oxidizing agent contained in the second gas described later. There is a risk that a thin film of oxide (so-called ALD film) will be formed.

The flow rate of the first gas is not particularly limited, and is, for example, 8.45 × 10 ^-4 Pa · m ³ / sec to 5.07 × 10 ⁻² Pa · m ³ / sec (5.0 sccm). ~ 300.0 sccm).

<First gas purging process>
Next, an inert gas such as nitrogen (N ₂ ) is supplied, and the surplus first gas is purged (exhausted) (S04 in FIG. 7). If the first gas is continuously exposed to the resist pattern 4', the reaction between the reactive functional group and the inorganic element-containing compound becomes difficult to proceed over time. Therefore, the excess first gas is purged (exhausted) and the first gas is again used. By performing the gas exposure step (S03 in FIG. 7), the reaction between the reactive functional group and the inorganic element-containing compound can be efficiently promoted. In addition, the inorganic element-containing compound can be effectively permeated into the resist pattern 4'. The first gas purging step can be carried out, for example, for about 10 seconds to 10000 seconds.

After the first gas purging step (S04 in FIG. 7) is completed, it is determined whether or not the number of repetitions of the series of steps of the first gas exposure step and the first gas purging step set as the first treatment condition has been reached ( In the case of S05 in FIG. 7), if the number of repetitions has not been reached (S05, No in FIG. 7), the first gas exposure step (S03 in FIG. 7) is performed again. On the other hand, when the number of repetitions has been reached (S05, Yes in FIG. 7), the next step (second gas exposure step, S06 in FIG. 7) is carried out.

<Second gas exposure process>
Subsequently, according to the second treatment condition, the resist pattern 4'is exposed to the second gas containing an oxidizing agent (second gas exposure step, S06 in FIG. 7). By exposing the resist pattern 4'that has been repeatedly exposed to the first gas over a plurality of cycles to the second gas, it is contained in the site of the inorganic element-containing compound bonded to the reactive functional group of the resin material constituting the resist pattern 4'. The remaining reactive active groups are hydrolyzed and replaced with hydroxyl groups. After that, a dehydration condensation reaction occurs, so that the rigidity of the resist pattern 4'can be improved. By repeating the series of steps of the first gas exposure step and the first gas purging step a plurality of times as in the present embodiment and then carrying out the second gas exposure step, the inorganic element-containing compound contained in the first gas is carried out. Can be effectively penetrated deep inside the resist pattern 4', and the chemical reaction can be efficiently performed inside the resist pattern 4'.

The oxidizing agent contained in the second gas may be any as long as it can replace the residual reactive active group contained in the moiety of the inorganic element-containing compound bonded to the reactive functional group with a hydroxyl group, for example, water ( H ₂ O), oxygen (O ₂ ), ozone, hydrogen peroxide and the like can be mentioned.

When the inorganic element-containing compound contained in the first gas is trimethylaluminum and the reactive functional group is a carbonyl group, it is contained in dimethylaluminum bonded to the carbonyl group as shown in the following reaction formula (2). The remaining reactive active groups (two methyl groups) are hydrolyzed with water as an oxidizing agent and replaced with hydroxyl groups. Then, as shown in the following reaction formula (3), a dehydration condensation reaction of the dihydroxyaluminum moiety occurs.

The time for exposing the resist pattern 4'to the second gas (treatment time in the second gas exposure step) may be according to the second treatment condition, but is, for example, about 1 second to 3600 seconds, more preferably about 30 seconds to 1000 seconds. Is. When the treatment time of the second gas exposure step is less than 1 second, the hydrolysis reaction of the residual reaction active group contained in the site of the inorganic element-containing compound bonded to the reactive functional group inside the resist pattern 4'is sufficiently carried out. There is a risk that it will not be damaged.

In the second gas exposure step (S06 in FIG. 7), similarly to the first gas exposure step (S03 in FIG. 7), the temperature condition is equal to or lower than the melting point of the resin material constituting the resist pattern 4', preferably less than the glass transition temperature. Underneath, it is preferred to expose the resist pattern 4'to the second gas. This makes it possible to promote the hydrolysis reaction of the residual reactive active group contained in the site of the inorganic element-containing compound bonded to the reactive functional group while preventing the resist pattern 4'from being softened and deformed.

The treatment pressure condition in the second gas exposure step (S06 in FIG. 7) may be in accordance with the second treatment condition, but may be an atmospheric pressure condition or a vacuum condition. In the case of vacuum conditions, the processing pressure conditions are set to, for example, 133.3 Pa to 1333.2 Pa (1.0 Torr to 10.0 Torr), and 400.0 Pa to 933.3 Pa (3.0 Torr to 7. It is preferably set to about 0 Torr). If the second gas exposure step is carried out in a vacuum atmosphere, defects may occur in the resist pattern 4', but when the second gas exposure step is carried out under atmospheric pressure, the resist pattern 4'is defective. Can be prevented from occurring.

<Second gas purging process>
Next, an inert gas such as nitrogen (N ₂ ) is supplied, and the surplus second gas is purged (exhausted) (S07 in FIG. 7). The second gas purging step (S07 in FIG. 7) may be carried out, for example, for about 30 seconds to 10000 seconds. By the first gas exposure step and the second gas exposure step (S03 to S07 in FIG. 7), the fine pattern 4 having sufficient rigidity can be formed (see FIG. 8E).

In the above embodiment, an inorganic element-containing compound (trimethylaluminum, etc.) exhibiting Lewis acidity that can react with the resin material constituting the resist pattern 4'is used, but the inorganic compound that cannot or is difficult to react with the resin material. Element-containing compounds may be used. In this case, the resist pattern 4'is repeatedly exposed to the first gas containing an inorganic element-containing compound exhibiting Lewis acidity (for example, trimethylaluminum), if desired, and then exposed to the second gas. After that, the resist pattern 4'is repeatedly exposed to the gas containing the inorganic element-containing compound which cannot or is difficult to react with the resin material once or multiple times, and the resist pattern 4'is further exposed to the second gas. good. Thereby, the inorganic element-containing compound which cannot react or is difficult to react can be complexed with the resin material by sandwiching the reactive inorganic element-containing compound between the resin material and the resin material.

<Wet etching process>
By performing the first gas exposure step and the second gas exposure step (S03 to S07 in FIG. 7), a fine pattern 4 having sufficient rigidity can be obtained (see FIG. 8E), but the fine pattern 4 A thin film derived from an inorganic element-containing compound on the base material 2 exposed from between the convex portions 41 (when TMA is used as the inorganic element-containing compound, a thin film of Al ₂ O ₃ , film thickness: about 0.1 nm to 10 nm). Will be formed. When removing this thin film, the base material 2 on which the fine pattern 4 is formed may be subjected to a wet etching treatment.

The etching solution used in the wet etching step contains an acid capable of removing the thin film, and preferably an acid having a relatively strong oxidizing power for the material constituting the thin film (hypochlorous acid, chloric acid, etc.). It is a mixed acid solution containing a perchloric acid, nitric acid, sulfuric acid, peracetic acid, permanganic acid, dichromic acid, etc.) and a relatively weak acid (phosphate, acetic acid, phenol, etc.), and more preferably, the oxidizing power thereof is high. It is a mixed acid solution containing nitric acid as a relatively strong acid and phosphoric acid and acetic acid as relatively weak acids. The composition ratio (mass basis) of phosphoric acid, acetic acid and nitric acid in such a mixed acid solution is preferably 60 to 80: 1 to 20: 1 to 20, and preferably 65 to 75: 5 to 15: 1 to 5. Is particularly preferable. When the composition ratio of each acid in the mixed acid solution is within the above range, the thin film can be removed without damaging the fine pattern 4.

As a wet etching method, a method of immersing the base material 2 on which the fine pattern 4 is formed in an etching solution, and a method of injecting the etching solution onto the first surface 2A side of the base material 2 on which the fine pattern 4 is formed. Etc. can be exemplified, but the present invention is not limited to these.

In the wet etching step, an etching process using a low-concentration etching solution (mixed acid solution content: 1% by mass to 80% by mass) capable of removing the thin film formed between the convex portions of the fine pattern 4 and / Or, it is preferable to perform an etching treatment for a short time (about 1 second to 30 seconds) so that the thin film can be removed. As a result, the thin film can be removed without damaging the fine pattern 4.

<Inorganic oxide film forming process>
Next, the inorganic oxide film 42 that covers the top and side walls of the fine pattern 4 is formed. The inorganic oxide film 42 can be formed by sputtering or the like of a material (for example, silicon oxide, titanium oxide, etc.) constituting the inorganic oxide film 42.

<Release layer forming process>
After the inorganic oxide film 42 is formed, the release layer 43 that covers the inorganic oxide film 42 is formed. The release layer 43 can be formed by applying a fluorine alkyl-containing silane coupling agent, a long-chain alkyl-containing silane coupling agent, or the like. In this way, the imprint mold 1 having the fine pattern 4 is manufactured.

[Imprint method]
An imprint method using the imprint mold 1 according to the present embodiment will be described. FIG. 9 is a process flow chart showing each step of the imprint method in the present embodiment on the cut end face.

The imprint method in the present embodiment has an imprint mold 1, a first surface 102 and a second surface 103 facing the first surface 102, and if desired, metal chromium, chromium oxide, chromium nitride, and oxynitriding on the first surface 102. A step of preparing a transfer substrate 101 on which a hard mask layer made of chrome or the like is formed (see FIG. 9A), an imprint resin film on the first surface 102 (hard mask layer) of the transfer substrate 101. The process of forming 104 (a resin film made of an ultraviolet curable resin such as acrylic or methacrylic) and the fine pattern 4 of the imprint mold 1 are transferred to the imprint resin film 104, and the fine pattern 4 is inverted. The step of forming the uneven pattern 105 on the imprint resin film 104 is included.

Examples of the transferred substrate 101 include quartz glass, soda glass, fluorite, calcium fluoride substrate, magnesium fluoride substrate, glass substrate such as acrylic glass, polycarbonate substrate, polypropylene substrate, resin substrate such as polyethylene substrate, and the like. Transparent substrates such as laminated substrates made by laminating two or more substrates arbitrarily selected from among them; metal substrates such as nickel substrates, titanium substrates and aluminum substrates; semiconductor substrates such as silicon substrates and gallium nitride substrates are used. obtain.

In the step of forming the uneven pattern 105 on the imprint resin film 104, first, the fine pattern 4 of the imprint mold 1 is pressed against the imprint resin film 104 on the first surface 102 of the substrate 101 to be transferred (FIG. 9 (B). )reference). In that state, the imprint resin film 104 is irradiated with ultraviolet rays UV or the like to cure the imprint resin film 104 (see FIG. 9C). Then, the imprint mold 1 is separated from the cured imprint resin film 104 (see FIG. 9D). When the imprint mold 1 is pulled away from the imprint resin film 104, the imprint resin film 104 is provided to such an extent that the imprint resin film 104 is slightly softened (to the extent that the pattern shape of the uneven pattern 105 to be transferred does not collapse). It can also be heated. The stress when pulling the imprint mold 1 away from the cured imprint resin film 104 can be reduced by heating the imprint resin film 104. As a result, the fine pattern 4 of the imprint mold 1 can be transferred to the imprint resin film 104 with high accuracy.

[Resist pattern reformer]
Subsequently, an example of a resist pattern reforming apparatus capable of carrying out the first gas exposure step and the second gas exposure step (S03 to S07 in FIG. 7) in the method for manufacturing an imprint mold according to the present embodiment will be described. FIG. 10 is a schematic configuration diagram schematically showing the configuration of the resist pattern reforming apparatus in the present embodiment, and FIG. 11 is a block diagram showing the schematic configuration of the resist pattern reforming apparatus in the present embodiment.

As shown in FIG. 10, the resist pattern reforming apparatus 50 in the present embodiment has a chamber 51, a gas inlet 52 and a gas exhaust port 53, and is an object to be treated (in the pattern forming method according to the present embodiment). A stage 54 on which the substrate 2 on which the resist pattern 4'is formed (see FIG. 8D)) can be placed, and a heater capable of heating the object to be processed placed on the stage 54 (not shown). And a detection unit 55 located above the stage 54 and detecting the modified state of the resist pattern 4'.

When the detection unit 55 is exposing the first gas to the resist pattern 4'formed on the first surface 2A of the base material 2 as the object to be treated, the optical characteristics of the resist pattern 4'(for example, the detection unit 55). It may be composed of an optical sensor, a weight sensor, or the like that can monitor changes in reflectance, refractive index, IR characteristics, color tone, etc.) and weight over time. When the detection unit 55 is composed of a weight sensor, the detection unit 55 may be built in the stage 54.

In the resist pattern reforming apparatus 50, when the first gas is supplied into the chamber 51 from the gas inlet 52, the first gas flows toward the gas exhaust port 53, and the object to be processed located between them ( The surroundings of the resist pattern 4') can be made into a first gas atmosphere. As a result, the inorganic element-containing compound contained in the first gas can be infiltrated into the resist pattern 4', and the reactive functional group of the resin material can be reacted with the inorganic element-containing compound.

As shown in FIG. 11, the resist pattern reforming device 50 in the present embodiment is a communication unit 63 for transmitting and receiving data and the like between the control unit 61, the storage unit 62, and the resist pattern reforming device 50. Further includes a control device 60 having the above. The control unit 61 is based on various information stored in the storage unit 62, information input from the user, and the like, and data related to the first processing condition (for example, the number of times the first gas exposure step is repeated, each time). Data on the processing time of the first gas exposure process, etc.) and data on the second processing conditions (for example, data on the processing time, etc. of the second gas exposure process) can be generated, and the registration pattern can be modified based on those data. Arithmetic processing for controlling the first gas exposure step (S03 in FIG. 7), the second gas exposure step (S06 in FIG. 7), and the like in the quality apparatus 50 is performed.

The storage unit 62 temporarily stores information input from the user, a program for the control unit 61 to perform various arithmetic processes, data related to the first processing condition generated by the control unit 61, and a second. Data on processing conditions, monitoring information obtained by monitoring by the detection unit 55 (for example, information on changes in optical properties and weight of resist pattern 4'), information on various resin materials that can constitute resist pattern 4'. (For example, information on the type of resin material, the electron density of the resin material, etc.) is stored.

The data regarding the first processing condition and the data regarding the second processing condition stored in the storage unit 62 are the data when the first gas exposure step and the second gas exposure step were performed in the past by the resist pattern reformer 50. The data regarding the first processing condition and the second processing condition are associated with the information regarding the resin material constituting the resist pattern 4'at that time. Further, the data regarding the first treatment condition and the second treatment condition are obtained by being monitored by the detection unit 55 when the first gas exposure step and the second gas exposure step have been performed in the past by the resist pattern reformer 50. It may be updated based on the monitoring information provided.

When the resist pattern reforming apparatus 50 in the present embodiment performs the resist pattern reforming process, the control unit 61 generates data related to the first processing condition and data related to the second processing condition according to the information input from the user and the like. do. For example, when information regarding the type of the resin material constituting the resist pattern 4'is input, the data regarding the first processing condition and the data regarding the second processing condition associated with the resin material are stored in the storage unit 62. If so, the data related to the first processing condition and the data related to the second processing condition are read out. On the other hand, when the data regarding the first processing condition and the data regarding the second processing condition associated with the resin material are not stored in the storage unit 62, the first is based on the information on the electron density of the resin material. Generate data related to the processing condition and data related to the second processing condition. For example, the electron density of the new resin material is obtained from the information regarding the type of the resin material input by the user. Then, in comparison with the electron density of the resin material associated with the data regarding the first treatment condition and the data regarding the second treatment condition, the data regarding the first treatment condition and the second treatment condition associated with the resin material having the closest electron density are obtained. Based on the data regarding the processing conditions, the data regarding the first processing conditions and the data regarding the second processing conditions for the resist pattern 4'composed of the new resin material are generated.

The control unit 61 controls the processing in the resist pattern reforming apparatus 50 based on the data regarding the first processing condition and the data regarding the second processing condition generated as described above, and the resist pattern reforming apparatus 50 controls the processing. A series of steps of the first gas exposure step and the first gas purging step are repeated a plurality of times. At this time, the detection unit 55 monitors changes in the optical characteristics and weight of the resist pattern 4'over time, and the monitoring information output from the detection unit 55 is stored in the storage unit 62. After the series of steps of the first gas exposure step and the first gas purge step is completed, the series of steps of the second gas exposure step and the second gas purge step are carried out, and the reforming process for the resist pattern 4'is completed.

After the series of steps of the first gas exposure step and the first gas purge step is completed, the control unit 61 has a series of steps of the second gas exposure step and the second gas purge step based on the monitoring information output from the detection unit 55. You may decide whether or not to carry out. For example, the first gas exposure step of the number of repetitions in the data regarding the first treatment condition generated at the start of the treatment in the resist pattern reformer 50 is completed, but the resin material and the inorganic material constituting the resist pattern 4'are based on the monitoring information. If it is determined that the reaction with the element-containing compound is insufficient, the first gas exposure step may be carried out again without shifting to the second gas exposure step. By performing such control, the optimum modification treatment of the resist pattern 4'can be performed.

Further, the control unit 61 feeds back the monitoring information output from the detection unit 55 to the data related to the first processing condition first generated, and the number of repetitions of a series of steps of the first gas exposure step and the first gas purge step. Etc. may be changed during the processing in the resist pattern reformer 50. By providing such a feedback function, the resist pattern 4'can be modified under the optimum processing conditions.

The embodiments described above are described for facilitating the understanding of the present invention, and are not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents belonging to the technical scope of the present invention.

In the method for manufacturing an imprint mold of the above embodiment, before the first gas exposure step (S03 in FIG. 7) is carried out, active energy rays are applied to the resist pattern 4'formed on the first surface 2A of the base material 2. The exposure step of irradiating with the above may be carried out. When the resist pattern 4'is irradiated with active energy rays, the reactive functional groups (particularly, highly nucleophilic functional groups that easily emit electrons) of the resin material constituting the resist pattern 4'are eliminated or modified. Occurs. The degree of desorption or denaturation of the reactive functional group varies depending on the irradiation amount of this active energy ray. When the reactive functional group is desorbed or modified, the number of reaction points (reactive functional groups) of the inorganic element-containing compound contained in the first gas decreases, so that the rigidity of the fine pattern 4 can be easily adjusted. ..

The active energy ray irradiated to the resist pattern 4'may be any one having an energy amount capable of desorbing or modifying the reactive functional group of the resin material constituting the resist pattern 4', for example, ultraviolet rays and electrons. Examples include lines and X-rays.

In the above embodiment, a mode in which a series of steps of the first gas exposure step and the first gas purge step are repeatedly carried out a plurality of times and then the second gas exposure step and the second gas purge step are carried out has been described as an example. , Not limited to this aspect. For example, a series of gas exposure steps of a first gas exposure step, a first gas purge step, a second gas exposure step, and a second gas purge step may be repeated a plurality of times.

In the above embodiment, the base material 2 of the imprint mold 1 may be composed of a reaction product of a resin material and an inorganic material, similarly to the fine pattern 4. In this case, the base material 2 and the fine pattern 4 may be configured separately or as an integral body. For example, a base substrate made of a resin material having a predetermined reactive functional group is prepared, a resist pattern 4'is formed on the base substrate, and the resist pattern 4'and the base substrate are exposed to the first gas. A step, a first gas purging step, a second gas exposure step, and a second gas purging step (S03 to 07 in FIG. 7) can be performed. Thereby, the base material 2 can be composed of the reaction product together with the fine pattern 4.

In the above embodiment, the imprint mold 1 having the metal film 3 covering the first surface 2A of the base material 2 has been described as an example, but the present invention is not limited to this embodiment, and the first surface of the base material 2 is not limited to this. The fine pattern 4 may be formed on the 2A, and the metal film 3 may not be formed. In this case, an adhesion promoting layer may be provided to cover the first surface 2A of the base material 2, and the fine pattern 4 may be formed on the adhesion promoting layer.

The present disclosure is useful in the technical field of imprint molds used for forming fine concavo-convex structures in the manufacturing process of semiconductor devices and the like.

1 ... Imprint mold 2 ... Base material 2A ... 1st surface 2B ... 2nd surface 3 ... Metal film 4 ... Fine pattern 41 ... Convex part 42 ... Inorganic oxide film 43 ... Release layer 5 ... Alignment mark

Claims (12)

A base material having a first surface and a second surface facing the first surface,
It is provided with a fine pattern having a plurality of convex portions provided on the first surface of the base material.
The base material and the fine pattern are imprint molds composed of reaction products of a resin material and an inorganic material. The imprint mold according to claim 1, wherein the resin material has a reactive functional group exhibiting reactivity with the inorganic material. The imprint mold according to claim 1 or 2, further comprising a release layer that covers the surface of the fine pattern. The imprint mold according to claim 3, wherein the release layer contains a fluorine-containing material. The imprint mold according to claim 3 or 4, further comprising an inorganic oxide film between the surface of the fine pattern and the release layer. The imprint mold according to claim 5, wherein the inorganic oxide film is a silicon oxide film or a titanium oxide film. Further provided with a metal film covering the first surface of the substrate,
The imprint mold according to any one of claims 1 to 6, wherein the fine pattern is provided on the metal film. Further provided with an adhesion promoting layer covering the first surface of the substrate,
The imprint mold according to any one of claims 1 to 7, wherein the fine pattern is provided so as to be in contact with the adhesion promoting layer. The imprint mold according to any one of claims 1 to 6, wherein the fine pattern and the base material are integrally formed. Further provided with an alignment mark provided on the first surface of the substrate,
The imprint mold according to any one of claims 1 to 9 , wherein the alignment mark is composed of the reaction product. The imprint mold according to any one of claims 1 to 10 , wherein a part of the plurality of convex portions of the fine pattern and the other portion are composed of the reaction products of different types from each other. The imprint method using the imprint mold according to any one of claims 1 to 11 .
A step of preparing a transferred substrate having a surface to be transferred and a back surface facing the surface to be transferred, and a step of preparing the substrate to be transferred.
The step of supplying the imprint resin onto the transfer surface of the transfer substrate,
A step of developing the imprint resin between the first surface of the imprint mold and the transfer surface of the transfer substrate by bringing the fine pattern of the imprint mold into contact with the imprint resin.
A step of curing the imprint resin developed between the first surface of the imprint mold and the transfer surface of the transfer substrate.
Including the step of pulling the imprint mold away from the cured imprint resin.
The resin material constituting the fine pattern is a material that can be softened by heating.
An imprint method in which at least the fine pattern is heated to separate the imprint mold from the imprint resin in the step of separating the imprint mold.

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