TW201535044A - Patterning method and manufacturing method of patterning substrate - Google Patents

Abstract

The present invention provides a patterning method for reducing defects, lowering the cost and improving the yield. As a nanoimprint mold, an object which contains main patterning areas and non-main patterning areas is used. Concave-convex patterns to be transferred are formed on the surface of the object in the main patterning areas. The non-main patterning areas are adjacent to the main patterning areas and have dummy patterns or flat surfaces having a patterning density and an aspect ratio lower than those of the concave-convex patterns. As resists, a plurality of resists having different ingredients and demolding forces after hardening are prepared. In a coating step, a resist with a relatively low demolding force after hardening is disposed on regions of the surface of a nanoimprint substrate corresponding to the main areas. A resist with a relatively high demolding force after hardening is disposed on at least a part of regions of the surface of a nanoimprint substrate corresponding to the non-main areas.

Description

Pattern forming method and method of manufacturing patterned substrate

The present invention relates to a pattern forming method using an imprint method and a method of fabricating a patterned substrate.

The embossing method is a method in which a mold (mold) which has been patterned in a concave-convex shape in advance is pressed against a resist layer applied to a substrate (substrate to be processed) to be processed, and is rotated. The pattern corresponding to the pattern on the mold is formed on the substrate, and the formation and mass productivity of the fine pattern are in the field of miniaturization of a semiconductor element or a patterned medium such as a hard disk. The imprint method is attracting attention from the viewpoint of cost.

In the optical embossing method using a photocurable resist, a next-generation manufacturing technique for microfabrication is expected as the resist, and Patent Document 1 proposes the following method: In order to increase the critical dimension uniformity (CDU) and make it uniform in the plane, a plurality of resist materials having different etching speeds are used.

Further, in the nanoimprint method in which the pattern transfer of the nano-scale is particularly required, a fine pattern is required to be transferred with excellent precision and without defects.

In the nanoimprint used in semiconductor photolithography, in terms of improving the yield of the manufacturing process, it is extremely important to suppress defects in demolding when the mold is peeled off from the hardened resist. As is known from the experience, in the nanoimprint method, defects such as peeling and peeling frequently occur in the mold release process when the mold is peeled off from the resist.

As a method of suppressing defects occurring during mold release, an attempt is made to design a hard surface (mold, substrate) or a light source related to transfer such as a mold or a substrate (Patent Documents 2 to 4).

Patent Document 2 discloses a method of forming a dummy pattern having a high mold release force on a mold, and using a mold release terminal as a dummy pattern region, thereby suppressing generation of defects in the main pattern.

Patent Document 3 discloses a method of controlling the mold release force by adjusting the amount of exposure of the photocurable resin in accordance with the degree of exposure, and the mold release terminal having a high mold release force is easily used. The method of reducing the exposure amount of the part. Further, Patent Document 4 proposes to reduce the releasing force of the pattern transfer region by sharpening the shape of the four corners of the mesa structure.

Further, Patent Document 5 discloses a method in which two types of curable resin materials having different mold release forces are used as a resist, and a resist is locally applied separately in the transfer pattern, thereby reducing the release of the mold. The impact of the mold or resist layer at the time, thereby suppressing the occurrence of defects.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-61195

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2011-116032

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2012-212781

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2011-116032

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2012-114158

However, in the method described in Patent Document 2, the pattern density of the dummy pattern is made higher than that of the main pattern, and the mold release force of the dummy pattern is increased, whereby generation of defects in the main pattern can be suppressed, but peeling and peeling are likely to occur in the dummy pattern. The mold release defect occurs, and the transfer failure occurs due to the residue between the substrate and the mold. Further, a cleaning step or the like of a mold for preventing transfer failure is required, and the yield is lowered.

In order to adjust the exposure amount described in Patent Document 3, a special optical system or system is required. In the method described in Patent Document 4, it is necessary to form a special mesa shape, and in any case, it is high in cost.

As described in Patent Document 5, in the pattern to be transferred, even if the time of demolding differs depending on the portion, the peeling or peeling at the end of the mold release cannot be sufficiently suppressed. In particular, when a part of the pattern to be transferred is the most terminal end of the mold release, the mold cannot be used again, resulting in a problem of high cost and a low yield.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for suppressing generation of defects, low-cost, and excellent pattern formation, and a method for producing a patterned substrate using the same.

The concave-convex pattern forming method of the present invention comprises: a coating step of disposing a photo-curable resist liquid at a desired position on a substrate for nanoimprint; and a pressing step of extruding a mold having a fine concavo-convex pattern on the surface a surface on which the resist liquid is applied to the substrate for imprinting, a hardening step to cure the resist liquid to form a resist film, and a demolding step to release the mold from the resist film. In the mold, a surface having a main pattern region and a non-main pattern region in which a concave-convex pattern to be transferred is formed is provided, and the non-primary pattern region is adjacent to the main pattern region, and the pattern density or the aspect ratio is smaller than the concave-convex pattern. Faux pattern or flat surface, As the resist liquid, a plurality of resist liquids having different mold release forces different in composition and hardening are prepared, In the coating step, a resist liquid having a relatively low mold release force after hardening is disposed in a region corresponding to the main pattern region on the surface of the substrate for nanoimprint, on the surface of the substrate for nanoimprinting. At least a part of the region corresponding to the non-main pattern region is provided with a resist liquid having a relatively high releasing force after hardening.

As the resist liquid having a relatively high mold release force, a composition having a modulus of elasticity after hardening greater than a modulus of elasticity of the resist liquid after the mold release force is relatively low can be used.

As a method of making the modulus of elasticity after hardening greater than the modulus of elasticity of the resist liquid after the mold release force is relatively low, it is preferably a method of containing a relatively high release force in the resist liquid. The photopolymerization initiator has a higher sensitivity than the release force a method of sensitivity of a photopolymerization initiator contained in a lower resist liquid, or a content of a polyfunctional polymerizable compound in a resist liquid having a relatively high mold release force is larger than a mold release force A method of the content of a polyfunctional polymerizable compound in a resist liquid.

As the resist liquid having a relatively high mold releasing force, the free energy per unit area of the interface with the mold after curing can be used, and the hardened mold and the mold having a relatively low mold release force can be used. The composition of the free energy per unit area of the interface.

Preferably, the free energy per unit area of the interface with the mold after hardening is less than the free energy per unit area of the interface of the resist after hardening of the resist liquid having a relatively low mold release force, preferably The following method is used as a resist liquid having a relatively high mold releasing force, and a composition containing at least one photocurable resin component having an amine structure, a phosphate structure, and a sulfate structure And at least one or more of the polyalkylene oxide structures, as a resist liquid having a relatively low mold release force, a resist having a structure having a photocurable resin component is used, and a resist having a relatively high mold release force is used. A composition having a content of the photocurable resin component having the above structure in the liquid, or a resist having a relatively high releasing force, and a resist having a relatively lower releasing agent content than the releasing force. A composition of the release agent content in the liquid.

Further, as the uneven pattern forming method of the present invention, a plurality of resist liquids may be prepared by changing one or more components stepwise, and in the coating step, a plurality of anti-resistances may be changed in a stepwise manner. The etchant solution is configured to the nanoimprint base The surface of the panel spans from a region corresponding to the main pattern region to at least a portion of the region corresponding to the non-primary pattern region.

In the method for producing a patterned substrate of the present invention, a resist film having a concave-convex pattern transferred thereon can be formed on the surface of the substrate for nanoimprinting as a substrate to be processed by the concave-convex pattern forming method of the present invention, and the resist can be formed. The film is etched as a mask, and a concave-convex pattern corresponding to the uneven pattern transferred to the resist film is formed on the substrate to be processed.

According to the method for forming a concave-convex pattern of the present invention, in the step of applying the resist liquid to the substrate for nanoimprint, the hardened surface is disposed in a region corresponding to the main pattern region on the surface of the substrate for nanoimprinting. The resist liquid having a relatively low mold release force is disposed on at least a portion of the surface of the surface of the nanoimprint substrate corresponding to the non-primary pattern region, and the resist liquid having a relatively high mold release force after curing is disposed. Therefore, the most end of the demolding at the time of demolding can be used as the non-main pattern region, and the main surface region and the non-main pattern region on which the concave and convex patterns to be transferred are formed on the surface are used as the mold. The pattern region is adjacent to the main pattern region, and the pattern density or the aspect ratio is smaller than the dummy pattern or the flat surface of the concave-convex pattern, so that the non-main pattern region at the end of the mold release is a concave-convex pattern or a flat region having a small pattern density or an aspect ratio. Therefore, the occurrence of defects such as falling off and peeling can be suppressed during demolding.

Since the occurrence of defects at the time of demolding can be suppressed, the yield is improved and the cost can be reduced.

1, 21, 31, 41, 101, 111‧‧‧ mold

2, 22, 32, 42, 102, 112‧‧‧ main pattern area

3, 23, 33, 43, 103, 113‧‧‧ Non-main pattern areas

4‧‧‧ convex

4a‧‧‧ upper surface

4b‧‧‧ side

4c‧‧‧ bottom

5‧‧‧Part (corner)

10‧‧‧Nano imprint substrate

12‧‧‧1st resist liquid (resist liquid/resist film)

13‧‧‧Second resist liquid (resist liquid/resist film)

15‧‧‧Area

16, 17‧‧‧ central area

18‧‧‧ corner area

25, 48‧‧‧ corner

26, 37‧‧‧Mold Center

35, 45, 104, 114‧‧‧Dummy patterns

105, 115‧‧‧ part

H‧‧‧ Height of the convex part (depth of the recess)

P ₁ ‧‧‧pattern with small pattern density

P ₂ ‧‧‧pattern with high density

S1‧‧‧ the sum of the area

S2‧‧‧ area

W‧‧‧Width of the convex part

Fig. 1 is a plan view schematically showing a mold used in a method for forming a concave-convex pattern according to an embodiment of the present invention.

Fig. 2 is a cross-sectional view taken along line II-II of the mold shown in Fig. 1;

Fig. 3A is a schematic view showing an example of a concavo-convex pattern.

Fig. 3B is a schematic cross-sectional view for explaining an aspect ratio of a concavo-convex pattern.

4A is a perspective view for explaining definition of a pattern density of a concavo-convex pattern.

Fig. 4B is a perspective view for explaining the size of the density pattern.

FIG. 5 is a plan view schematically showing an example of an arrangement pattern in which a resist droplet is disposed on a substrate for nanoimprint.

Fig. 6 is a schematic view showing a procedure of a method of forming a concavo-convex pattern according to the first embodiment.

Fig. 7 is a plan view schematically showing a mold used in the method for forming a concave-convex pattern according to the second embodiment.

8 is a schematic view showing the procedure of a method of forming a concavo-convex pattern according to a second embodiment.

FIG. 9 is a plan view schematically showing an example of an arrangement pattern in which a resist droplet is placed on a substrate for nanoimprinting in the method for forming a concavo-convex pattern according to the third embodiment.

Fig. 10 is a schematic view showing the procedure of a method of forming a concavo-convex pattern according to a third embodiment.

Fig. 11 is a plan view schematically showing a mold used in the method for forming a concave-convex pattern according to the fourth embodiment.

Fig. 12 is a view schematically showing a method of forming a concave-convex pattern according to a fourth embodiment; A plan view showing an example of an arrangement pattern of resist droplets on a substrate for nanoimprint.

Fig. 13 is a schematic view showing the procedure of a method of forming a concavo-convex pattern in the fourth embodiment.

Fig. 14 is a plan view schematically showing a mold used in the method for forming a concave-convex pattern according to the fifth embodiment.

FIG. 15 is a plan view showing an example of an arrangement pattern in which a resist droplet is placed on a substrate for nanoimprinting in the method for forming a concavo-convex pattern according to the fifth embodiment.

Fig. 16 is a schematic view showing the procedure of a method of forming a concavo-convex pattern according to a fifth embodiment.

Fig. 17 is a plan view schematically showing a mold used in Examples and Comparative Examples.

18 is a schematic plan view of a mold used in a comparative example.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In addition, in order to make it easy to visually recognize, the scale of each component in the drawing and the like are appropriately different from the actual situation.

(Nylon imprinting mold)

First, the nanoimprint mold 1 used in the imprint method of the present embodiment will be described. 1 is a schematic view showing a plan view of a mold 1, and FIG. 2 is a cross-sectional view taken along line II-II of the mold 1 shown in FIG. 1.

As shown in FIGS. 1 and 2, the mold 1 includes a main pattern region 2 to be transferred to the surface, and a non-main pattern region 3 other than the same. Here, the main pattern region 2 is a region in which a concave-convex pattern (hereinafter sometimes referred to as a "main pattern") to be transferred to the substrate to be processed is formed. The non-main pattern region 3 is a region other than the main pattern region 2, and in this example, is a flat region having no concavo-convex pattern. In the non-main pattern region 3, for example, a dummy pattern for adjusting the remaining film of the resist in the nanoimprint lithography described later may be formed. The dummy pattern forming region of the non-main pattern region 3 is not particularly limited, and may be a part or a plurality of portions or the entire main pattern region.

In the mold 1 of the present invention, the dummy pattern is a concave-convex pattern that is more easily released from the uneven pattern (main pattern) to be transferred in the main pattern region 2. That is, the dummy pattern is a concavo-convex pattern in which the pattern density or the aspect ratio is smaller than the main pattern formed in the main pattern region 2. Here, the pattern density or the aspect ratio is smaller than the concave-convex pattern of the main pattern, and includes at least the following cases: 1) the pattern density is equal to the main pattern, and the aspect ratio is smaller than the main pattern, 2) the aspect ratio is equal to the main pattern, and the pattern density is smaller than The main pattern, 3) the aspect ratio and the pattern density are both smaller than the main pattern.

In the case where the dummy pattern is less likely to be released from the main pattern (for example, Patent Document 2), that is, in the case where the pattern density or the pattern aspect ratio of the dummy pattern is larger than the main pattern, the mold is peeled off from the resist film ( In the case of mold release, since the dummy pattern is less likely to cause peeling, the mold release terminal which is likely to cause defects is a dummy pattern. As a result, although the main pattern is protected without causing defects, defects are generated in the dummy pattern which becomes the mold release terminal, and since the resin defect adheres to the mold side, continuous imprinting cannot be performed. This is because if the imprinting is performed in a state in which the resin which is defective is adhered, the force which is supposed to be the dummy pattern peeling off of the mold release terminal is weakened, and as a result, the main pattern, not the dummy pattern, becomes the mold release terminal. Moreover, in order to avoid this, it is necessary to remove the mold due to the cleaning embossing or cleaning step at each embossing. The trapped resin residue is removed, so that each cleaning embossing or cleaning step results in a significant reduction in the amount of imprint lithography processed.

The concavo-convex pattern may be any pattern such as a line shape, a dot shape, or a combination of the above. 3A is a plan view showing an example of a concavo-convex pattern, and a portion indicated by oblique lines indicates a planar shape of the convex portion 4.

The longitudinal and lateral directions are, as shown in FIG. 3B, the ratio H/W of the width W of the convex portion 4 to the height (depth of the concave portion) H. As shown in FIGS. 3A(a) to 3A(c), when the planar shape of the convex portion 4 is elliptical or linear, the width of the convex portion 4 is the length in the short-side direction, as shown in FIG. 3A(d). In the case where the convex portion 10 is shown as a circular dot shape, the width of the convex portion 4 is the diameter thereof. In the case of the same pattern density, the larger the aspect ratio, the higher the mold release force (the more difficult it is to release the mold), and the smaller the aspect ratio, the lower the mold release force (the easier the mold release).

4A is a perspective view for explaining the definition of the pattern density. The area where the concavo-convex pattern shown in FIG. 4A is formed, that is, the area where the convex portion 4 is formed (the projection surface area shown below) is S2, and the upper surface 4a and the side surface 4b of the convex portion 4 are When the sum of the areas of the bottom faces 4c of the concave portions between the convex portions is S1, the pattern density is defined as S1/S2. The area S1 is the total area of the portion in contact with the resist at the time of imprinting in the pattern. The larger the S1/S2, the larger the proportion of the portion in contact with the resist, and the greater the mold release force. Further, in the pattern region, the convex portion provided on the outermost periphery is defined as the end portion of the pattern region, and S1 and S2 are calculated.

4B is a pattern P1 showing a pattern P1 having a same aspect ratio and a small pattern density, and having a large pattern density. As shown in FIG. 4R, even if the pattern has the same aspect ratio, the larger the pattern density, the larger the area of the portion in contact with the resist, so the mold is released. The higher the force, the smaller the pattern density and the lower the release force.

Further, in the present invention, the size and structure of the mold that can be used are not particularly limited. For example, the size of the reticle used for semiconductor photolithography is 65 mm × 65 mm, 5 . The inch is 5 inches, 6 inches by 6 inches, or 9 inches by 9 inches in square shape, and the center of the back is given a counter boring. The shape of the hole expanding process is determined in consideration of the permeability of the gas and the deflection (bending rigidity) of the substrate at the portion which is thinned by the hole expanding process. For example, a substrate of 6 inches × 6 inches, a substrate thickness of 6.35 mm, a reaming diameter of 63 mm, and a reaming portion thickness of 1.1 mm can be used.

Preferably, the substrate has a stepped structure on the surface in such a manner that the pattern forming region can be defined within the range of the pedestal. This is because, due to the presence of the susceptor, when the template for the substrate processing is used in the component manufacturing step, the region in contact with the wafer using the template, that is, the wet diffusion region of the resin can be limited to the pedestal ( The mesa) surface thus avoids contact with structures present outside the pattern forming region of the substrate. The height of the susceptor is preferably from 1 μm to 1000 μm, more preferably from 10 μm to 500 μm, still more preferably from 20 μm to 100 μm. In addition, the shape of the substrate in Fig. 1 and the like only shows the base portion.

(manufacturing method of the mold)

The mold 1 can be manufactured in the following order, for example. First, a polyhydroxy styrene (PHS)-based chemical amplification resin, a novolac resin, a polymethyl methacrylate (PMMA), or the like is applied to a quartz substrate by spin coating or the like. a resin liquid containing a resin as a main component, A resin layer is formed. Then, the electron beam (or laser light) is irradiated on the quartz substrate while being modulated in accordance with the desired concavo-convex pattern, and the concave-convex pattern is exposed on the surface of the resin layer. Then, the resin layer is subjected to development treatment, the pattern of the removed resin layer is masked, and selective etching is performed by reactive ion etching (RIE) or the like to obtain a quartz mold having a predetermined uneven pattern.

Further, in the present embodiment, a case where a quartz mold is used will be described, but the mold 1 is not limited thereto, and a Si mold may be used. In this case, the Si mold can be produced by the same method as the quartz mold manufacturing method.

"Nano imprint method and method of manufacturing patterned substrate"

Next, an embodiment of the nanoimprint method will be described.

The nanoimprinting method of the present embodiment includes the steps of applying a resist on a substrate for imprinting a substrate (substrate to be processed) using the mold 1 of the embodiment; and extruding the mold 1 a pressing step of pressing the surface of the nanoimprint substrate coated with the resist liquid; a hardening step of hardening the resist liquid; and a demolding step of releasing the mold 1 from the hardened resist film .

(imprint substrate)

Here, the imprint substrate 10 is a substrate to be processed which transfers the concavo-convex pattern (main pattern) of the mold 1. The material and the like of the substrate 10 used in the present embodiment are not particularly limited and may be appropriately selected depending on the purpose. For example, 6-inch, 8-inch, 12-inch, 18-inch Si wafers can be used.

Moreover, the size and thickness of the mold and the substrate 10 for imprint can be adapted. When choosing a combination. However, at least any of the mold and the substrate for imprint needs to have light transmissivity.

Here, the light transmittance is sufficient as long as it has a transmittance capable of allowing 5% or more of light to enter, and the light is used to cure the photocurable resist material applied to the substrate for imprint.

(resist solution)

As described, the mold used in the present invention includes a main pattern area and a non-primary pattern area, the non-primary pattern area includes a dummy pattern having a flatness and/or a pattern density smaller than that of the main pattern area, and/or the non-main pattern area includes a flat pattern. And/or the aspect ratio is smaller than the dummy pattern of the main pattern area, so the mold release force is small in shape. Therefore, the main pattern region having a higher mold release force is likely to be a mold release terminal. Therefore, in order to make the mold release terminal a non-primary pattern region, a resist having a larger mold release force than the other regions is disposed in a predetermined region (predetermined region of the mold release terminal) in the non-main pattern region.

Although having the same mold release force, the region with a high pattern of vertical and horizontal and low adhesion is compared with a region with a low pattern of vertical and horizontal (including no pattern) and high adhesion, the latter is overwhelmingly less prone to defects (pattern shedding, Peeling, etc.). This is because, although having the same mold release force, the pattern existing in the high pattern density region or the high aspect pattern is more likely to cause damage due to local stress concentration at the root portion.

Therefore, in the present invention, a plurality of resist liquids having different mold release forces different from each other and having a different mold release force are prepared. At least two kinds of resist liquids are prepared: the first resist liquid having a relatively low mold release force after curing and the second resist liquid having a relatively high mold release force after curing. Here, the relatively low release force and relatively high pressure means that the first antibody is When the etchant liquid is compared with the second resist liquid, the mold release force after the first resist liquid is cured is lower than the mold release force after the second resist liquid is cured, and the second resist liquid is hardened. The subsequent mold release force is higher than the mold release force after the first resist liquid is hardened. Further, one or a plurality of resist liquids having a releasing force between the first resist liquid and the mold release force after curing of the second resist liquid are prepared, corresponding to the main pattern region. The region spans at least a portion of the region corresponding to the non-primary pattern region, and a plurality of resist liquids may be used to have the lowest mold release force in the region corresponding to the main pattern region, and the region corresponding to the non-primary pattern region The method in which at least a part of the releasing force is the highest is separately applied using a plurality of resist liquids whose compositions are changed stepwise.

The method of making the mold release force after the hardening of the resist liquid differs is a method of making the elastic modulus after hardening different, and the free energy per unit area of the interface between the cured resist film and the mold. (Method of (the adhesion between the resist film and the mold) is different.

As a method of adjusting the elastic modulus after curing of the resist liquid, there is a method of adjusting the sensitivity of the high-sensitivity photopolymerization initiator contained in the resist liquid or adjusting the content of the polyfunctional polymerizable compound. Moreover, as a method of adjusting the free energy of the interface between the cured resist film and the mold, a method of introducing a compound having an adsorption group into a composition constituting the resist liquid is mentioned, and the content of the release agent is adjusted. Methods. Further, the (surface) free energy at the interface between the resist film and the mold means a work required to peel the resist film from the mold, and the smaller the free energy, the easier the peeling is. That is, the smaller the free energy, the smaller the adhesion between the resist film and the mold. Hereinafter, each method of adjusting the releasing force will be described.

<Free energy adjustment: adsorption base>

First, as one of methods for adjusting the free energy of the interface with the mold after curing of the resist liquid, a method of introducing a compound having an adsorption group with a mold to the curable resin composition will be described. Examples of the adsorbing group include an amine structure, a phosphate structure, a nitrate structure, and a polyalkylene oxide structure. The polymerizable group may not be contained in the compound. Specific examples of the compound containing the adsorbing group include ethyl methacrylate (Osaka Organic Chemicals), N, N, N", N"-tetraisopropyldiethylenetriamine, N, N'. - Diisopropylethylenediamine (Tokyo Chemical Industry Co., Ltd.), 2-propenyloxyethyl acid phosphate (Kyoeisha Chemical Co., Ltd.), and the like. The amount of the compound having an adsorbing group is preferably 0.01% to 10%, more preferably 0.1% to 5%, based on the mass of the composition constituting the resist liquid. The compound having an adsorption group in the resist liquid may be one type or a plurality of types. The amount added is the total amount of the compound having the adsorbing group.

In the case where the first resist liquid having a relatively high mold release force after the hardening is prepared and the second resist liquid having a relatively high mold release force after curing, the second resist liquid is used in the second resist liquid. The amount of the compound having the adsorption group added may be larger than the amount of the first resist liquid added.

<Elastic Modulus Adjustment: Photopolymerization Starter>

As a method of changing the elastic modulus of the resist liquid after curing, a method of changing the sensitivity of the photopolymerization initiator contained in the resist liquid will be described.

As long as it is a photopolymerization initiator containing a photopolymerization initiator in a curable resist liquid having a sensitivity ratio as a standard, it can exhibit a higher modulus of elasticity after hardening.

For example, when the curable resist liquid which is the standard contains Irgacure (registered trademark) 754 as a photopolymerization initiator, it is a photopolymerization initiator which is higher in sensitivity than Irgacure (registered trademark) 754. For example, Irgacure (registered trademark) 379, Irgacure (registered trademark) 369, Irgacure (registered trademark) OXE01, Irgacure (registered trademark) OXE02, Irgacure (registered trademark) 907, and the like can be cited.

In the case where the first resist liquid having a relatively high mold release force after hardening and the second resist liquid having a relatively high mold release force after curing are prepared, the second resist liquid is contained in the second resist liquid. The photopolymerization initiator may be used as long as the sensitivity of the photopolymerization initiator contained in the resist liquid having a relatively lower sensitivity than the mold release force is used.

<Elastic modulus adjustment: polyfunctional polymerizable compound>

One of the methods for changing the elastic modulus of the resist liquid after curing is a method of changing the amount of the polyfunctional polymerizable compound contained in the resist liquid.

When a resist liquid containing a composition which exhibits a higher modulus of elasticity after curing, the polyfunctional polymerizable compound contained in the composition is more polyfunctionally polymerized than the reference curable resist liquid. The amount of the compound is large.

Examples of the polyfunctional polymerizable compound include 1,6-hexanediol diacrylate (Kyoeisha Scientific Co., Ltd.), neopentyl glycol diacrylate (Japanese chemical), and pentaerythritol triacrylate (East Asia) Synthesis), trimethylolpropane triacrylate (East Asia Synthetic), and the like.

The first resist liquid having a relatively low mold releasing force after preparation for hardening, and hard In the case of the second resist liquid having a relatively high mold release force, the content of the polyfunctional polymerizable compound contained in the second resist liquid is higher than the resist liquid having a relatively low mold release force. The content contained in it can be large.

<Free energy adjustment: release agent>

As another method of adjusting the free energy of the interface with the mold after curing of the resist liquid, there is a method of changing the content of the release agent in the resist liquid.

A fluorine-type surfactant is mentioned as a mold release agent.

In the case where the first resist liquid having a relatively high mold release force after the hardening is prepared and the second resist liquid having a relatively high mold release force after curing, the second resist liquid is used in the second resist liquid. The content of the release agent may be smaller than the content of the first resist liquid.

(resist solution coating)

As a method of applying the resist liquid, a method in which a predetermined amount of liquid droplets can be placed on a predetermined position on a substrate or a mold by an inkjet method is used. When the resist droplets are disposed on the substrate, the ink jet printer or dispenser can be used separately depending on the amount of droplets required. For example, there is a method in which an ink jet printer is used in the case where the droplet amount is less than 100 nl (nanoliter), and a dispenser or the like is used in the case of 100 nl or more.

Examples of the ink jet head that ejects the resist droplets from the nozzle include a piezoelectric method, a thermal method, and an electrostatic method. Among these, a piezoelectric method in which an appropriate amount of liquid (the amount of each droplet to be disposed) or a discharge speed can be adjusted is preferable. The droplet amount or the ejection speed is set and adjusted in advance before the resist droplets are placed on the substrate. For example, it is preferable to adjust the amount of liquid in the following manner, and the position on the substrate corresponding to the region where the spatial volume of the concave-convex pattern of the mold is large is increased, or in the mold The area of the concave-convex pattern having a small volume is correspondingly reduced in position on the substrate. The adjustment can be appropriately controlled in accordance with the amount of droplet discharge (the amount of each droplet ejected). Specifically, when the amount of droplets is set to 5 pl (picoliter), the amount of droplets is controlled so that the same portion is ejected five times using an inkjet head having a droplet discharge amount of 1 pl. The amount of liquid droplets is determined by, for example, measuring a three-dimensional shape of droplets ejected onto the substrate under the same conditions by a confocal microscope or the like in advance, and calculating a volume based on the shape.

After the amount of liquid droplets is adjusted as described above, droplets are placed on the substrate in accordance with a predetermined droplet arrangement pattern. The droplet arrangement pattern includes 2-dimensional coordinate information (refer to FIG. 5 and the like), and the 2-dimensional coordinate information includes a lattice point group corresponding to the droplet arrangement on the substrate.

FIG. 5 is a plan view schematically showing an example of an arrangement pattern in which a resist droplet is placed on the substrate 10 for imprint. For example, in the case where a part (the corner portion in FIG. 1) 5 of the non-main pattern region 3 of the mold 1 is used as the predetermined portion of the mold release terminal using the mold 1 shown in FIG. 1, as shown in FIG. The region 15 on the substrate 10 for nanoimprinting corresponding to a portion 5 of the predetermined portion of the mold release terminal (opposite when pressed) is provided with a resist liquid having a relatively high mold release force after curing, and includes a main pattern In the other areas including the region 2, a resist liquid having a relatively low releasing force after hardening is disposed.

The ink jet method has a mechanism that can coat a plurality of different resist liquids. It is appropriately controlled so that two or more kinds of resist liquids can be disposed at any position.

(imprint method)

Contacting the mold 1 with the resist liquid applied to the substrate for nanoimprinting Preferably, the residual gas is reduced by setting the environment of the mold 1 and the substrate for nanoimprint to a reduced pressure or a vacuum environment. However, it is difficult to maintain a uniform film thickness by volatilizing the resist liquid before hardening in a high vacuum environment. Therefore, it is preferable to reduce the residual gas by making the environment between the mold 1 and the substrate a He environment or a reduced pressure He environment. Since He passes through the quartz substrate, the residual gas (He) entering is gradually reduced. Since the passage of He takes time, it is more preferable to set it as a decompression He environment. The reduced pressure environment is preferably from 1 kPa to 90 kPa, and more preferably from 1 kPa to 10 kPa.

The mold 1 and the substrate coated with the resist liquid are brought into contact after being aligned in a predetermined relative positional relationship. It is preferred to use an alignment mark in the positional alignment.

The pressing of the mold 1 is performed in a range of a pressure of 100 kPa or more and 10 MPa or less. The larger the pressure, the more the flow of the resist liquid is promoted, and the more the compression of the residual gas, the dissolution of the residual gas in the resist liquid, and the transmission of He in the quartz substrate, thereby improving the removal rate of the residual gas. However, if the pressing force is too strong, there is a possibility that the mold 1 and the substrate are broken when the foreign matter is caught by the contact of the mold. Therefore, the pressing pressure of the mold 1 is preferably 100 kPa or more, 10 MPa or less, more preferably 100 kPa or more, 5 MPa or less, still more preferably 100 kPa or more and 1 MPa or less. The reason why it is 100 kPa or more is that when the liquid is filled between the mold 1 and the substrate when imprinting in the atmosphere, the mold 1 and the substrate are pressurized at atmospheric pressure (about 101 kPa).

After the mold layer 1 is pressed to form a resist liquid layer (resist film), exposure is performed with light having a wavelength corresponding to the polymerization initiator contained in the resist liquid. The resist hardens. As a method of peeling (releasing) the mold 1 from the cured resist film, a method of holding the back surface or the outer edge portion of one of the mold 1 or the substrate 10 and holding the other side In a state where the back surface or the outer edge portion is held, the holding portion of the outer edge or the holding portion of the back surface is relatively moved in a direction opposite to the pressing. Alternatively, a method may be employed in which the entire surface of both the mold 1 and the substrate 10 is sucked by a vacuum chuck or the like, and the mold 1 and the substrate 10 are relatively moved in opposite directions, whereby the mold 1 is peeled off.

(Concave-convex pattern forming method of the first embodiment)

A first embodiment of a concave-convex pattern forming method using an imprint method will be described. In the first embodiment, the mold 1 shown in Fig. 1 and the substrate 10 for nanoimprint shown in Fig. 5 are used. Here, the resist liquid (first resist liquid) 12 having a relatively low mold release force after curing and the resist liquid having a relatively high mold release force after curing (second resist) The case where the liquid 13 is used as a resist liquid will be described.

First, as shown in FIG. 5, in the coating step, the second resist liquid 13 is placed in the region 15 of the substrate 10 for imprint, and the first resist liquid 12 is placed in a region other than the second resist liquid.

Then, as a pressing step, as shown in a of FIG. 6, the mold 1 is brought close to at least the main pattern region 2 and the region where the first resist liquid 12 is applied, and is pressed to the substrate 10 (Fig. 6 b).

Then, as the hardening step, light is irradiated from the back side (upper side of the paper surface) of the mold 1 in the state of b of FIG. 6, and the resist liquid 12 and the resist liquid 13 are hardened.

Then, the resist film 12 and the resist film formed by hardening the mold 1 are formed. Stripping in 13 At this time, the resist film 12 having a large mold release force is first released from the mold, and the region 15 of the resist film 13 having a large mold release force is the terminal end of the mold release (see c of FIG. 6). The region 15 and the portion 5 of the mold 1 are the most terminal ends of the mold release. However, since the region of the mold 1 which is the terminal for demolding is a flat portion, peeling, peeling, and the like hardly occur (see d of Fig. 6).

(Concave-convex pattern forming method of the second embodiment)

A second embodiment of the concave-convex pattern forming method using the imprint method will be described. In the second embodiment, the mold 21 shown in Fig. 7 in which the formation region of the main pattern region is different from that of the mold 1 of the first embodiment is used. FIG. 7 is a schematic view showing a plan view of the mold 21.

In the mold 21 shown in FIG. 7, the concavo-convex pattern of the main pattern to be transferred is divided into four regions 22. The non-main pattern area 23 is formed outside the main pattern area 22, and the non-main pattern area 23 in the transfer area is formed flat.

In the present embodiment, a resist liquid (first resist liquid) 12 having a relatively low mold release force after curing and a resist liquid having a relatively high mold release force after curing (second resistance) are also used. The etchant liquid 13 is used as a resist liquid. Further, in the present embodiment, the mold releasing end of the mold 21 is the corner portion 25.

First, as shown in FIG. 5, as shown in FIG. 5, in the coating step, the second resist liquid 13 is placed in the region 15 of the substrate 10 for imprint, and the first resist is placed in the other region. Corrosion solution 12.

Then, as a pressing step, as shown in a of FIG. 8, the mold 21 is made to have at least the main pattern region 22 and the region to which the first resist liquid 12 is applied. The pattern is approximated and extruded to the substrate 10 (b of Fig. 8).

Then, as the hardening step, light is irradiated from the back surface side (above the paper surface) of the mold 21 in the state of b of FIG. 8 to cure the resist liquid 12 and the resist liquid 13.

Further, the mold 21 is released from the resist film 12 and the resist film 13 which are formed by curing. At this time, the resist film 12 having a large mold release force is first released from the mold, and the region 15 of the resist film 13 having a large mold release force is the terminal end of the mold release (see c of FIG. 8). The corner portion 25 of the region 15 and the corresponding mold 21 serves as the final end of the mold release. However, since the corner portion 25 of the mold 21 is a flat portion, peeling, peeling, and the like hardly occur (see d of Fig. 8).

(Concave-convex pattern forming method of the third embodiment)

A third embodiment of the concave-convex pattern forming method using the imprint method will be described. In the third embodiment, the same mold 21 as in the second embodiment is used, and the resist liquid (first resist liquid) 12 having a relatively low mold release force after curing and the mold release force after curing are used. A higher resist liquid (second resist liquid) 13 is used as the resist liquid. On the other hand, in the present embodiment, the mold release end of the mold 21 is set to the mold center portion 26 in the non-main pattern region 23.

First, as shown in FIG. 9 , as shown in FIG. 9 , the second resist liquid 13 is placed in the center region 16 of the nanoimprint substrate 10 as the coating step, and the first region is disposed in the other region. Resist solution 12. The central region 16 is a region corresponding to the central portion 26 of the non-primary pattern region 23 of the mold 21.

Then, as a pressing step, as shown in a of FIG. 10, the mold 21 is made The mold center portion 26 is close to the center region 16 on which the second resist liquid is applied on the substrate, and is pressed to the substrate 10 (b of FIG. 10).

Then, as the hardening step, light is irradiated from the back side (upper side of the paper surface) of the mold 21 in the state of b of FIG. 10, and the resist liquid 12 and the resist liquid 13 are hardened.

Then, the mold 21 is released from the resist film 12 and the resist film 13 which are formed by hardening. At this time, the resist film 12 having a large mold release force is first released from the mold, and the region 16 of the resist film 13 having a large mold release force is the terminal end of the mold release (see c of FIG. 10). The region 16 and the center portion 26 of the corresponding mold 21 are the most terminal ends of the mold release. However, since the center portion 26 of the mold 21 is a flat portion, peeling, peeling, and the like hardly occur (see d of Fig. 10).

(Concave-convex pattern forming method of the fourth embodiment)

A fourth embodiment of the concave-convex pattern forming method using the imprint method will be described. In the fourth embodiment, the mold 31 shown in Fig. 11 having a configuration different from the mold 21 of the above embodiment is used. FIG. 11 is a schematic view showing a plan view of the mold 31.

In the mold 31 shown in Fig. 11, the concave-convex pattern of the main pattern to be transferred is divided into four regions 32. The main pattern area 32 is a non-main pattern area 33, and the mold center portion 37 in the non-main pattern area 33 is formed with a dummy pattern 35, and other areas of the non-main pattern area 33 are formed flat. As described above, here, the dummy pattern includes a concavo-convex pattern (a convex portion of the concavo-convex pattern) in which the pattern density and the aspect ratio are smaller than the concavo-convex pattern (the convex portion of the concavo-convex pattern) of the main pattern.

In the present embodiment, a resist liquid (first resist liquid) 12 having a relatively low mold release force after curing and a resist liquid having a relatively high mold release force after curing (second resistance) are also used. The etchant liquid 13 is used as a resist liquid. Further, in the present embodiment, the mold release end of the mold 31 is the mold center portion 37 in which the dummy pattern 35 is formed in the non-main pattern region 33.

First, as shown in FIG. 12, as shown in FIG. 12, the second resist liquid 13 is placed in the center region 17 of the nanoimprint substrate 10, and the first region is disposed in the other region. Resist solution 12.

Then, as a pressing step, as shown in a of FIG. 13, the mold 31 is formed such that at least the main pattern region 32 faces the region where the first resist liquid 12 is applied, and the mold center portion 37 in which the dummy pattern 35 is formed is formed. It is close to the surface in which the center region 17 of the second resist liquid 13 is applied, and is pressed to the substrate 10 (b of Fig. 13).

Then, as the hardening step, light is irradiated from the back surface side (above the paper surface) of the mold 31 in the state of b of FIG. 13, and the resist liquid 12 and the resist liquid 13 are hardened.

Further, the mold 31 is released from the resist film 12 and the resist film 13 which are formed by hardening. At this time, the resist film 12 having a large mold release force is first released from the mold, and the center region 17 of the resist film 13 having a large mold release force is formed as the mold release terminal (see c of FIG. 13). The central region 17 of the resist film and the dummy pattern 35 (the mold center portion 37) of the corresponding mold 31 serve as the mold release terminal. The pattern density and the aspect ratio of the dummy pattern 35 are lower than the concavo-convex pattern of the main pattern region 32 of the mold 31, and the shape is easily released, so that generation of peeling, peeling, and the like can be suppressed (see d of FIG. 13).

(Concave-convex pattern forming method of the fifth embodiment)

A fifth embodiment of the concave-convex pattern forming method using the imprint method will be described. In the fifth embodiment, the mold 41 shown in Fig. 14 having a configuration different from that of the mold 21 of the above embodiment is used. FIG. 14 is a schematic view showing a plan view of the mold 41.

In the mold 41 shown in FIG. 14, the concave-convex pattern of the main pattern to be transferred is divided into four regions 42 and formed. The main pattern area 42 is a non-main pattern area 43, and the mold corner portion 48 in the non-main pattern area 43 is formed with a dummy pattern 45, and other areas of the non-main pattern area 43 are formed flat. Here, the dummy pattern includes a concavo-convex pattern (a convex portion of the concavo-convex pattern) in which the pattern density and the aspect ratio are smaller than the concavo-convex pattern (the convex portion of the concavo-convex pattern) of the main pattern.

In the present embodiment, a resist liquid (first resist liquid) 12 having a relatively low mold release force after curing and a resist liquid having a relatively high mold release force after curing (second resistance) are also used. The etchant liquid 13 is used as a resist liquid. Further, in the present embodiment, the mold release terminal in the mold 41 is a corner portion 48 in which the dummy pattern 45 is formed in the non-main pattern region 43.

First, as shown in FIG. 15 , as shown in FIG. 15 , the second resist liquid 13 is placed in the corner region 18 of the nanoimprint substrate 10 as a coating step, and the other regions are disposed in the other regions. 1 resist liquid 12.

Then, as a pressing step, as shown in a of FIG. 16, the mold 41 is faced with at least the main pattern region 42 and the region where the first resist liquid 12 is applied, and the dummy pattern 45 and the second coating are applied. The manner in which the corner region 18 of the etchant liquid 13 faces It is approached and pressed to the substrate 10 (b of Fig. 16).

Then, as the hardening step, light is irradiated from the back side (upper side of the paper surface) of the mold 41 in the state of b of FIG. 16 to cure the resist liquid 12 and the resist liquid 13.

Further, as a mold release step, the mold 41 is released from the resist film 12 and the resist film 13 which are formed by hardening. At this time, the resist film 12 having a large mold release force is first released, and the corner region 18 of the resist film 13 having a large mold release force is formed as the mold release terminal (see c of FIG. 16). The corner region 18 of the resist film and the dummy pattern 45 of the corresponding mold 41 become the most terminal ends of the mold release. Since the aspect ratio of the dummy pattern 45 is lower than the uneven pattern of the main pattern region 42 of the mold 41, the shape is easily released, so that generation of peeling, peeling, and the like can be suppressed (see d of FIG. 16).

(Method of Manufacturing Patterned Substrate)

Next, an embodiment of a method of manufacturing a patterned substrate (mold replica) will be described. In the present embodiment, a replica of the mold 1 is produced by using the quartz mold as a master and using the nanoimprint method.

First, a resist film to which a pattern is transferred is formed on one side of a substrate by the nanoimprint method. Then, the resist film to which the pattern has been transferred is used as a mask, dry etching is performed, and a concave-convex pattern corresponding to the uneven pattern formed on the resist film is formed on the substrate to obtain a substrate having a predetermined pattern.

The dry etching is not particularly limited as long as it can form a concavo-convex pattern on the substrate, and can be appropriately selected according to the purpose, and examples thereof include an ion polishing method, reactive ion etching (RIE), and sputtering etching. Among these, especially the ion milling method, RIE.

As described above, according to the method of manufacturing a patterned substrate of the present invention, the region which is the terminal end when demolding is the substrate flat portion or the pattern density is smaller than the main pattern, and/or the dummy pattern portion having an aspect ratio lower than that of the main pattern is used. According to the method, a plurality of resist liquids are separately applied and controlled, whereby the occurrence of defects at the time of mold release can be effectively suppressed, and the patterned substrate can be manufactured with good yield.

[Examples]

Hereinafter, examples and comparative examples of the uneven pattern forming method using the imprint method of the present invention will be described.

First, the steps and evaluation methods of the mold used in the examples and the comparative examples, the substrate for nanoimprint, and the method for forming a concavo-convex pattern common to each example will be described.

<mold>

A synthetic quartz substrate having a shape of 6 inches long, 6 inches wide, and 0.25 inches thick was used as a substrate for a mold.

The substrate has a stepped structure on the surface in such a manner that the pattern forming region can be defined in the range of the susceptor. The susceptor has a height (step difference) of 20 μm and a length × width of 33 mm × 26 mm. The back surface of the substrate was subjected to a reaming process, the diameter of the reaming was 63 mm, and the thickness of the reaming portion was 1.1 mm.

On the surface of the base of the synthetic quartz substrate, an electron beam resist was applied to a thickness of 60 nm, subjected to electron beam drawing and development, and then dry-etched to form a mold having a concavo-convex pattern.

17 and 18 are schematic diagrams showing the present embodiment and/or comparative example. A plan view of the base portion of the mold 101 and the mold 111 used.

First, the first mold 101 shown in Fig. 17 will be described. The surface (surface of the base portion) of the first mold 101 includes a main pattern region 102 in which a concave-convex pattern to be transferred is formed, and a non-main pattern region 103 other than the non-main pattern region 103 in the center portion of the mold. The dummy pattern 104 for adjusting the mold release force is provided, and the non-main pattern region 103 is a blank region (flat region) having no pattern other than the portion 105 in which the dummy pattern 104 is formed.

The main pattern area 102 is provided in four in the transfer area, and one mold has a pattern of four wafers. A line and space pattern having a width of 30 nm, a pitch of 60 nm, and a height of 60 nm is provided as a main pattern in one wafer (one main pattern region 102), and main pattern regions 102 at the center portion in the transfer region are mutually A line and gap pattern having a width of 50 nm, a pitch of 100 nm, and a height of 60 nm is provided as the dummy pattern 104 in the non-main pattern region 103. At this time, the aspect ratio (height/width) of the convex portion (line) of the main pattern is 60/30, and the aspect ratio (height/width) of the convex portion (line) of the dummy pattern is 60/50, and the aspect ratio of the dummy pattern is 60/50. Less than the aspect ratio of the main pattern.

Next, the second mold 111 shown in Fig. 18 will be described. The surface (base surface) of the second mold 111 includes a main pattern region 112 in which a concave-convex pattern to be transferred is formed, and a non-main pattern region 113 other than the non-main pattern region 113 in the center portion of the mold. A dummy pattern different from the concavo-convex pattern to be transferred is provided, and the non-main pattern region 113 is a non-patterned blank region (flat region) except for a portion 115 in which the dummy pattern 114 is formed.

The main pattern area 112 is provided in the transfer area by four, and one mold has 4 pattern of wafer size. A line and gap pattern having a width of 30 nm, a pitch of 60 nm, and a height of 60 nm is provided in the first wafer (one main pattern region 112) as a main concavo-convex pattern, and a non-primary pattern between the main pattern regions 112 at the center portion in the transfer region In the region 113, a dot pattern having a diameter of 20 nm, a pitch of 40 nm, and a height of 60 nm was provided as the dummy pattern 114.

At this time, the aspect ratio (height/width) of the convex portion (line) of the main pattern is 60/30, and the aspect ratio (height/width (diameter)) of the convex portion (dot) of the dummy pattern is 60/20, and the dummy pattern is The aspect ratio is greater than the aspect ratio of the main pattern.

<Nano imprint substrate (substrate to be processed)>

As a substrate for nanoimprint, a 12-inch Si wafer was used.

<resist liquid>

In the resist liquid used in each of the examples and the comparative examples, the raw materials described in Tables 1 to 6 which will be described later for each of the examples and the comparative examples are used. In Tables 1 to 6, each of the resists dropped to the substrate region (denoted as "dummy") corresponding to the dummy pattern region of each example and the region corresponding to the region other than the region (denoted as "main") are shown. The raw material of the liquid.

<Coating of resist liquid>

Coating of the resist liquid (disposition of resist droplets) was performed using an inkjet device level jet manufactured by Tritek. Two or more inkjet heads and a resist liquid tank are mounted so that two or more types of resist liquid lipids can be preliminarily disposed. With an alignment mechanism using an optical microscope, it is possible to arrange desired droplets on a desired position on the wafer with reference to an arbitrary position on the wafer (here, a substrate for nanoimprint).

<Nano imprint>

After the resist liquid is applied onto the substrate for nanoimprinting, the mold is pressed to the resist liquid application surface of the substrate for nanoimprinting under a reduced pressure of He, and the resist liquid is sufficiently filled. After passing between the mold and the substrate, UV light having a peak wavelength of about 370 nm and an irradiation intensity of 2.5 W/cm ² was irradiated for 20 seconds to cure the resist liquid. Then, while holding the outer edge portion of the mold and holding the back surface of the substrate for nanoimprint by the vacuum chuck, the holding portion of the outer edge of the mold and the holding portion of the back surface of the substrate are oriented. The opposite direction of the press is relatively moved to peel the mold.

<Determination of the position of the demolding terminal>

The terminal position of the demolding is observed from the peeling surface of the mold by a charge coupled device (CCD) camera, and it is determined whether the demolding terminal is a dummy pattern or a main pattern.

<Determination of the presence or absence of the mold release defect>

The vicinity of the position of the mold release terminal was evaluated by an optical microscope and a scanning electron microscope (SEM) on the cured resin pattern after peeling. In the case where there is a region where the pattern formation is defective, it is determined that there is a defect, and in the case where there is no region where the pattern is not formed, it is determined that there is no defect.

<Comprehensive evaluation>

A comprehensive evaluation is performed based on the determination result.

When the position of the mold release terminal is a dummy pattern and there is no mold release defect near the mold release terminal, it is evaluated as good (A), and when the mold release end position is a dummy pattern and there is a mold release defect near the mold release terminal, the evaluation is performed. Poor (B), at the position of the demolding terminal When the main pattern had a mold release defect near the mold release terminal, it was evaluated as defective (C).

Each of the examples and the comparative examples was embossed in the stated order, and judged and evaluated.

(Example 1-1, Example 1-2, Example 1-3, and Example 1-4)

The first mold 101 described above is used in the region corresponding to the dummy pattern region on the substrate for nanoimprint (described as "dummy" in Table 1 and the same in Tables 2 to 6). The substrate region is referred to as "dummy" and other regions (described as "main" in Table 1, and the same in Tables 2 to 6 are also referred to as "main"). Each of the resist liquids of the resist raw materials described in Table 1 was used. Table 1 is a resist raw material to be applied in a dummy region and a main region for Example 1-1, Example 1-2, Example 1-3, and Example 1-4 (the unit in the table is mass) %), the location of the demolding terminal, the defects of the demolding terminal, and the comprehensive evaluation are combined. In the embodiment, the resist liquid for the dummy region is used to have a higher mold release force than the resist liquid for the main region. The resist liquid applied to the dummy region contains a compound having a predetermined adsorption group, and the resist liquid used in the main region does not contain a compound having a predetermined adsorption group. In Examples 1-1 to 1-4, a resist liquid each containing a compound having a different adsorption group was applied to a dummy region.

As shown in Table 1, the positions of the demolding terminals of Examples 1-1 to 1-4 were all dummy pattern regions, and the mold release terminal did not cause defects.

(Comparative Example 1-1)

In the same manner as in the first embodiment, the first mold 101 described above is used, and in the substrate for nanoimprinting, the resist containing the resist material shown in Table 2 is placed in the dummy region and the region other than the dummy region. Liquid. As shown in Table 2, in the comparative example, the same composition of the resist liquid was used in the dummy region and the main region.

(Comparative Example 1-2, Comparative Example 1-3, Comparative Example 1-4, Comparative Example 1-5, Comparative Example 1-6)

In the second imprinted substrate, the respective resist liquids using the resist raw materials described in Table 2 were placed in the dummy region and the main region in the nanoimprint substrate. As shown in Table 2 As shown in Comparative Example 1-2, in the same manner as in Comparative Example 1-1, the resist liquid of the same component as the main region of the dummy region was used, and Comparative Examples 1-3 to 1-6 contained different adsorptions. A resist liquid of the base compound is applied to the dummy region, and a resist liquid containing no compound having an adsorption group is applied to the main region.

Table 2 is a comparison of Comparative Example 1-1 to Comparative Example 1-6, in which a resist material applied to a dummy region and a main region, a position of a mold release terminal, a defect of a mold release terminal, and a comprehensive evaluation are combined.

As shown in Table 2, when the same resist liquid was applied to the dummy region and the main region as in Comparative Example 1-1, the mold release terminal position was the main pattern region, and The demolding terminal produces defects. Further, as in Comparative Example 1-2 to Comparative Example 1-6, a concave-convex pattern including an aspect ratio higher than that of the main concave-convex pattern is used. The mold 111 as the dummy pattern is not separately coated with the resist liquid in the dummy region (Comparative Example 1-2) or separately (Comparative Example 1-3~) In Comparative Example 1-6), although the position of the demolding terminal was a dummy area, defects were generated in the demolding terminal.

(Example 2-1, Example 2-2, Comparative Example 2-1)

In the nanoimprint substrate, the composition of the resist liquid disposed in each of the dummy region and the main region was the same as that of Example 1-1 except that the components of Table 3 were described.

In these embodiments, the resist liquid used in the dummy region is used to have a higher mold release force after curing than the resist liquid used in the main region. As the resist liquid applied to the dummy region, the content of the multi-induction compound is larger than that of the resist liquid applied to the main region.

(Comparative Example 2-2, Comparative Example 2-3, Comparative Example 2-4)

The same as Example 2-1 except that the second mold 111 was used and the components of the resist liquid disposed in each of the dummy region and the main region were as described in Table 3.

Table 3 shows the resist materials applied to the dummy region and the main region and the elastic modulus after curing for Example 2-1, Example 2-2, Comparative Example 2-1 to Comparative Example 2-4 ( The standardized elastic modulus), the position of the demolding terminal, the defects of the demolding terminal, and the comprehensive evaluation are collected. The elastic modulus is measured by a nano Indentation method using an atomic force microscope (AFM). The elastic modulus is expressed by dividing the highest elastic modulus, specifically, by the resist disposed in the dummy region of Example 3-3 (= the dummy region of Comparative Example 3-5) in all the examples and the comparative examples. The standardized modulus of elasticity of the agent's modulus of elasticity (standardized).

As shown in Table 3, the positions of the release terminals of Example 2-1 and Example 2-2 were all dummy pattern regions, and the mold release terminal did not generate defects.

As shown in Table 3, when the same resist liquid was applied to the dummy region and the main region as in Comparative Example 2-1, the mold release terminal position was the main pattern region, and The demolding terminal produces defects. Further, as in the case of Comparative Example 2-2 to Comparative Example 2-4, the mold 111 including the concave-convex pattern having an aspect ratio higher than that of the main concavo-convex pattern as the dummy pattern is used, and is not separately coated in the dummy region from the main region. In the case of the cloth resist liquid (Comparative Example 2-2), or in the case of separate application (Comparative Example 2-3, Comparative Example 2-4), although the position of the mold release terminal was a dummy area, the mold release terminal All have defects.

(Example 3-1, Example 3-2, Example 3-3)

The composition of the resist liquid and the composition of the resist liquid disposed in each of the dummy region and the main region are the same as those described in Table 4, and are the same as those in the embodiment 1-1.

In these embodiments, the resist liquid used in the dummy region is used to have a higher mold release force after curing than the resist liquid used in the main region. The resist liquid applied to the dummy region contains a polymerization initiator which is sensitive to the resist liquid applied to the main region.

Table 4 shows the resist materials applied to the dummy region and the main region, and the elastic modulus (normalized elastic modulus) after curing in Example 3-1, Example 3-2, and Example 3-3. The position of the demolding terminal, the defect of the demolding terminal, and the comprehensive evaluation are collected.

As shown in Table 4, the positions of the demolding terminals of Examples 3-1 to 3-3 were all dummy pattern regions, and the mold release terminal did not cause defects.

(Comparative Example 3-1)

Except for the dummy pattern, and the dummy area and the resist liquid respectively disposed in the main area The components are the same as those described in Table 5, and are the same as in Example 3-1.

(Comparative Example 3-2, Comparative Example 3-3, Comparative Example 3-4)

The same as Example 3-1 except that the second mold 111 was used and the components of the resist liquid disposed in each of the dummy region and the main region were as described in Table 5.

Table 5 shows the resist materials applied to the dummy region and the main region, the elastic modulus after curing (normalized elastic modulus), the position of the mold release terminal, and the comparative examples 3-1 to 3-4. Model terminal defects and comprehensive evaluation are brought together.

As shown in Table 5, when the same mold 101 was used as in Comparative Example 3-1, when the dummy region and the main region were applied to the same resist liquid, the demolding end position was the main pattern region, and The demolding terminal generates defects. Further, as in Comparative Example 3-2 to Comparative Example 3-6, the mold 111 including the concave-convex pattern having an aspect ratio higher than that of the main concave-convex pattern as the dummy pattern is used, and is not divided into the dummy region and the main region. When the resist liquid was applied (Comparative Example 3-2), or when it was applied separately (Comparative Example 3-3 to Comparative Example 3-5), although the position of the mold release terminal was a dummy region, The die terminals all have defects.

(Example 4, Comparative Example 4-1)

The composition of the resist liquid disposed in each of the dummy region and the main region was the same as that of Example 1-1 except that the components described in Table 6 were used.

In the fourth embodiment, the resist liquid used in the dummy region is such that the mold release force after curing is higher than that of the resist liquid used in the main region. As the resist liquid applied to the main region, a mold containing a mold release agent (fluorine surfactant) is used as the resist liquid applied to the dummy region, and a mold release agent is not used.

On the other hand, as Comparative Example 4-1, the dummy region and the resist liquid used in the main region were the same composition, and both contained a release agent.

(Comparative Example 4-2, Comparative Example 4-3)

The same applies to Example 4 except that the second mold 111 is used and the components of the resist liquid disposed in each of the dummy region and the main region are as described in Table 6.

Table 6 shows the resist materials applied to the dummy region and the main region, the elastic modulus after curing (normalized elastic modulus), and demolding in Example 4 and Comparative Example 4-1 to Comparative Example 4-3. The terminal location, the defect of the demolding terminal and the comprehensive evaluation are brought together.

As shown in Table 6, the position of the demolding terminal of Example 4 was a dummy pattern area, and the mold release terminal did not generate a defect.

As shown in Table 6, when the same resist liquid was applied to the dummy region and the main region as in Comparative Example 4-1, the demolding terminal position was the main pattern region, and The demolding terminal produces defects. Further, as in Comparative Example 4-2 and Comparative Example 4-3, the mold 111 including the concave-convex pattern having an aspect ratio higher than that of the main concave-convex pattern as the dummy pattern is used, and is not separately coated in the dummy region from the main region. In the case of the cloth resist liquid (Comparative Example 4-2), or in the case of separate application (Comparative Example 4-3), although the position of the mold release terminal was a dummy area, the mold release terminals all had defects.

1‧‧‧Mold

2‧‧‧Main pattern area

3‧‧‧Non-main pattern area

5‧‧‧Part of the non-primary pattern area (corner)

Claims (9)

A concave-convex pattern forming method comprising: a coating step of disposing a photo-curable resist liquid at a desired position on a substrate for nanoimprint; and a pressing step of extruding a mold having a fine concavo-convex pattern on the surface to a surface of the nanoimprint substrate coated with the resist liquid; a hardening step of curing the resist liquid to form a resist film; and a demolding step of removing the mold from the substrate In the resist film, the main mold region and the non-main pattern region in which the concave and convex patterns to be transferred are formed on the surface are used as the mold, and the non-main pattern region and the main pattern are used. The region is adjacent to each other and is a dummy pattern or a flat surface having a pattern density or an aspect ratio smaller than the concave-convex pattern of the uneven pattern, and as the resist liquid, a plurality of anti-separation forces having different compositions and different mold release forces are prepared. In the coating step, in the region corresponding to the main pattern region on the surface of the substrate for nanoimprinting, a resist liquid having a relatively low releasing force after hardening is disposed. In the nanoimprint At least a portion of the relatively high release force is disposed after curing the resist solution to the non-patterned region corresponding to the main area of the surface of the plate. The method for forming a concave-convex pattern according to claim 1, wherein the resist liquid having a relatively high mold release force uses a resist having a modulus of elasticity after hardening that is larger than a relatively low mold release force. The composition of the elastic modulus of the solution after hardening. a method for forming a concave-convex pattern according to claim 2, wherein The sensitivity of the photopolymerization initiator contained in the resist liquid having a relatively high mold release force is higher than the sensitivity of the photopolymerization initiator contained in the resist liquid having a relatively low mold release force. The uneven pattern forming method according to claim 2, wherein the content of the polyfunctional polymerizable compound in the resist liquid having a relatively high releasing force is larger than the resist having a relatively low releasing force The content of the polyfunctional polymerizable compound in the solution liquid. The concave-convex pattern forming method according to claim 1, wherein the resist liquid having a relatively high mold release force uses a free energy per unit area of the interface with the mold after hardening, which is smaller than The composition of the free energy per unit area of the interface with the mold after the hardening of the resist liquid is relatively low. The method for forming a concave-convex pattern according to the second or fifth aspect of the invention, wherein a composition containing at least one of the photocurable resin components is used as the resist liquid having a relatively high releasing force. The photocurable resin component has at least one of an amine structure, a phosphate structure, a sulfate structure, and a polyalkylene oxide structure, and is used as a resist liquid having a relatively low mold release force. The content of the photocurable resin component of the above-described structure is smaller than the composition of the photocurable resin component having the above-described structure in the resist liquid having a relatively high releasing force. The concave-convex pattern forming method according to claim 2, wherein the resist liquid having a relatively high mold release force has a mold release agent content of which the mold release agent is relatively lower than the mold release force. A composition of the release agent content in the resist liquid. The concave-convex pattern forming method according to claim 1, wherein the plurality of resist liquids are prepared by changing one or more components in stages, and in the coating step, the composition is stepwise a manner of varying the arrangement of the plurality of resist liquids to the surface of the substrate for nanoimprinting from a region corresponding to the main pattern region to correspond to the non-primary pattern region At least part of the area. A method for producing a patterned substrate, which is formed on the surface of the substrate for nanoimprint as a substrate to be processed, by the concave-convex pattern forming method according to any one of claims 1 to 8. a resist film to which a concave-convex pattern is transferred, and the resist film is used as a mask to etch the substrate to be processed, and the unevenness corresponding to the uneven pattern transferred to the resist film is formed A pattern is formed on the substrate to be processed.