JP2016129263A - Nano-imprint method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nano-imprint method by which resin can be filled by faithfully mimicking a shape of a fine uneven pattern formed on a mold without requiring high pressing force or obstructing filling of resin.SOLUTION: With respect to filling of resin into a fine uneven pattern formed on a mold, capillary force can be efficiently used if relationship between surface free energy of the mold and surface free energy of the resin, magnitude of the surface free energy of the resin, relationship between adhesion energy between the mold and the resin, the surface free energy of the resin and its polar component, or the like satisfy specific conditions.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a nanoimprint method for transferring a fine concavo-convex pattern formed on a nanoimprint mold to a curable resin formed on a substrate to be transferred, and more specifically, filling a resin into the fine concavo-convex pattern of a mold. It is about technology.

  In recent years, especially for semiconductor devices, high speed operation and low power consumption operation are required due to further progress in miniaturization, and high technology such as integration of functions called system LSIs is required. Under such circumstances, the lithography technology that is necessary for producing the pattern of the semiconductor device has become very expensive as the exposure apparatus and the like as the pattern becomes finer, and the price of the mask used therefor also becomes expensive. Yes.

  On the other hand, the nanoimprint method (also called imprint method) proposed by Chou et al. In Princeton University in 1995 is a fine pattern formation technology having a high resolution of about 10 nm while the apparatus price and the materials used are low. (Patent Document 1).

  In the nanoimprint method, a mold (also referred to as a template, a stamper, or a mold) in which a nanometer-sized uneven pattern is formed on a surface in advance is pressed against a resin formed on the surface of a transfer substrate such as a semiconductor wafer, and the resin is In this technique, the concavo-convex pattern is transferred by being mechanically deformed, and the transferred substrate is processed using the resin having the pattern transferred as a resist mask. Once the mold is made, the nanostructure can be easily and repeatedly molded, resulting in high throughput and economics, and because it is a nano-processing technology with little harmful waste, not only semiconductor devices in recent years, Application to various fields is expected.

  As such a nanoimprint method, a thermal imprint method in which a concavo-convex pattern is transferred by heat using a thermoplastic resin, a photoimprint method in which a concavo-convex pattern is transferred by ultraviolet rays using a photocurable resin, and the like are known. (Patent Document 2).

  The above optical imprint method can transfer patterns at room temperature and does not require a heating / cooling cycle like the thermal imprint method and does not cause dimensional changes due to mold or resin heat. It is said that it is excellent in terms of sex.

  Here, when transferring the concavo-convex pattern to the transferred substrate using the nanoimprint method as described above, the resin before curing formed on the transferred substrate is filled faithfully to the shape of the concavo-convex pattern of the mold. After the resin is cured, it is necessary to release the cured resin so as not to cause pattern defects caused by adhesion and remaining of the cured resin without being released from the mold. In order to shorten the time required for resin filling before curing, there is a method of increasing the pressing force between the mold and the substrate to be transferred, and in order to improve the mold releasability between the mold and the resin after curing. There is a method of forming a release layer on the mold surface.

JP-T-2004-504718 JP 2002-93748 A

Toshio Kanehara "Basic physics, first volume" Hanakabo 1963 J. et al. N. Written by Israel Ativiri Yasuo Kondo / Hiroyuki Oshima "Intermolecular Force and Surface Force" Asakura Shoten 1963 2nd Edition 1996 D. K. Owens et al, J.A. Appl. Polym. Sci, 13, 1741-1747 (1969)

  However, when filling a resin having fluidity before curing into a minute uneven pattern of a mold with high pressure, the resin may spread to an undesired region of the substrate to be transferred. Further, there is a risk of inducing deformation of the mold, a risk that the spread of the resin becomes non-uniform, and a risk of damaging the mold or the transfer substrate.

  On the other hand, if a release layer with a small surface free energy is formed on the mold surface in order to improve the release property, the release force at the time of release becomes small, and thus the cured resin remains attached to the mold. Although effective in reducing pattern defects, there is a problem that the filling of the resin before curing is hindered.

  The present invention has been made in view of the above circumstances, and does not require high pressure, and does not hinder the filling of the resin, and faithfully follows the shape of the minute uneven pattern formed on the mold. An object of the present invention is to provide a nanoimprint method capable of filling a resin.

  As a result of various studies, the inventor of the present invention has studied the relationship between the surface free energy of the mold and the surface free energy of the resin, the magnitude of the surface free energy of the resin, and the filling of the resin into the minute uneven pattern formed in the mold. And, if the relationship between the adhesion energy between the mold and the resin, the surface free energy of the resin and its polar component, etc. satisfy a specific condition, the capillary force can be effectively used, thereby The present invention has been completed by finding that the problems can be solved.

That is, the invention according to claim 1 of the present invention is a nanoimprint method for transferring an uneven transfer pattern formed on a mold to a curable resin formed on a substrate to be transferred, wherein the curable resin is cured. The nanoimprint method is characterized in that the previous surface free energy is smaller than the surface free energy of the mold, and the surface free energy before curing of the curable resin is 10 mJ / m ² or more.

  The invention according to claim 2 of the present invention is the nanoimprint method according to claim 1, wherein a contact angle of the curable resin with respect to the mold is 40 degrees or less.

The invention according to claim 3 of the present invention is a nanoimprint method for transferring an uneven transfer pattern formed on a mold to a curable resin formed on a substrate to be transferred, the mold and the mold before curing. When the adhesion energy with the curable resin is W _{mold / resist} and the surface free energy before curing of the curable resin is γ _resist , the polar component of the surface free energy before curing of the curable resin (γ ^p _resist )
W _{mold / resist} / γ _resist -1> 0.996
The nanoimprint method is characterized in that the value satisfies the above range.

  According to the present invention, by utilizing the capillary force effectively, the resin before curing is filled in the minute uneven pattern formed on the mold faithfully following the shape without requiring high pressure. be able to.

It is explanatory drawing which shows the model of the capillary osmosis | permeation in the mold which has a hole-shaped concave pattern. It is a figure which shows the time dependency of the penetration height of resin in the mold which has a hole-shaped concave pattern. It is a figure which shows the relationship between the pattern size of the mold which has a hole-shaped concave pattern, and the penetration | attainment height of resin. It is a figure which shows the relationship between the surface free energy of resin, and the penetration penetration height of resin. It is a figure explaining the adhesion energy of a mold and resin. It is a schematic diagram explaining the force which acts on resin of the mold surface. It is an example of the figure which shows the relationship between the polar component of the surface free energy of resin, and a contact angle. It is another example of the figure which shows the relationship between the polar component of the surface free energy of resin, and a contact angle. It is a figure which shows the relationship between the surface free energy of a mold, and the maximum value of adhesion energy. It is an example of the figure which shows the relationship between the polar component of the surface free energy of resin, and adhesion energy. It is another example of the figure which shows the relationship between the polar component of the surface free energy of resin, and adhesion energy. It is explanatory drawing which shows the model of the theoretical formula of capillary penetration.

  First, the penetration penetration height in the concave pattern of the resin according to the present invention will be described.

  Formula (1) is a theoretical formula of the steady flow in the circular pipe (Hagen-Poiseule formula), and the flow rate Q of the steady flow of the circular pipe having the radius r and the length h is expressed as the pressure difference P between the length h ends. It is described by the viscosity coefficient η of the liquid (Non-Patent Document 1). FIG. 12 is an explanatory diagram showing the model.

次に、図１に、ホール状の凹パターン（円柱状の孔パターン）を有するモールド１における毛管浸透のモデルを示す。図１に示す凹パターンは円管の上部が閉じられた系に相当し、流体である硬化前の樹脂２がこの凹パターンに毛管浸透し、凹パターンの底部（閉じられた円管の上部に相当）に気体３が閉じ込められている。図１に示すモデルにおいては、樹脂２と接するモールド１の表面とホール状の凹パターン内に浸透した樹脂表面との圧力差Ｐは、数式（２）のように表される。ここで、第１項は、ラプラス圧力に起因する成分であり、ｒはホール状の凹パターンの半径、γは樹脂の表面自由エネルギー、θは樹脂の凹パターン内壁での接触角、ηは樹脂の粘性係数を表す。第２項は、重力に起因する成分であり、ρは樹脂の密度、ｇは重力加速度、ｈは樹脂の浸透高さを示す。第３項は、モールドの押圧力の成分である。第４項は、閉じ込められた気体の圧力の成分であり、ｈは浸透高さ、ｈ_mは凹パターンの深さ、ｐ_airは大気圧を示す。

Next, FIG. 1 shows a model of capillary penetration in a mold 1 having a hole-like concave pattern (columnar hole pattern). The concave pattern shown in FIG. 1 corresponds to a system in which the upper part of the circular tube is closed, and the resin 2 before curing, which is a fluid, permeates the concave pattern into the capillary, and the bottom of the concave pattern (the upper part of the closed circular tube The gas 3 is confined in the equivalent). In the model shown in FIG. 1, the pressure difference P between the surface of the mold 1 in contact with the resin 2 and the resin surface that has permeated into the hole-shaped concave pattern is expressed as Equation (2). Here, the first term is a component caused by Laplace pressure, r is the radius of the hole-like concave pattern, γ is the surface free energy of the resin, θ is the contact angle at the inner wall of the concave pattern of the resin, and η is the resin Represents the viscosity coefficient. The second term is a component due to gravity, ρ is the density of the resin, g is the acceleration of gravity, and h is the penetration height of the resin. The third term is a component of the pressing force of the mold. Fourth term is a component of the pressure of the trapped gas, h is the penetration height, h _m is a concave pattern depth, p _air denotes the atmospheric pressure.

上記の数式（１）に、数式（２）を代入したものを数式（３）に示す。

Formula (3) is obtained by substituting Formula (2) into Formula (1) above.

ここで、流量Ｑは、体積速度であるため、数式（４）のようにも表される。なお、Ｖは流体の体積を、ｔは時間を示す。

Here, since the flow rate Q is a volume velocity, it is also expressed as Equation (4). V represents the volume of the fluid and t represents time.

それゆえ、数式（３）と数式（４）から、次の数式（５）が導き出される。

Therefore, the following equation (5) is derived from the equations (3) and (4).

図２は、Ｘ軸を時間（ｔ）、Ｙ軸を浸透高さ（ｈ）として上記数式（５）をプロットした図である。図２に示すように、浸透高さ（ｈ）は、時間（ｔ）の経過に伴って高くなるが、一定の時間を経過すると、変化の小さい安定した値となる。それゆえ、以降、この安定した値を浸透到達高さ（ｈ_C）とする。

FIG. 2 is a diagram in which the above equation (5) is plotted with the X axis as time (t) and the Y axis as penetration height (h). As shown in FIG. 2, the penetration height (h) increases with the passage of time (t), but after a certain amount of time has passed, it becomes a stable value with little change. Therefore, hereinafter, this stable value is referred to as the penetration penetration height (h _C ).

Next, the relationship between the opening size (diameter = 2 × r) of the concave pattern and the penetration penetration height (h _C ) in the capillary penetration model of the mold having the hole-shaped concave pattern shown in FIG. 1 will be described below. . The depth of the concave pattern (h _m) is described as 100 nm.

FIG. 3 shows the above formula (5) when the contact angle (θ) is changed, with the X axis as the opening size (diameter = 2 × r) of the concave pattern and the Y axis as the penetration penetration height (h _C ). FIG.

The surface free energy (γ) was 25 mJ / m ² and the pressure (p) was 3500 Pa. The value of this pressure (p) assumes a state in which the mold is left still on the resin without being pressed from the back side of the mold.

As shown in FIG. 3, when the opening size of the concave pattern is near 20 nm, the capillary force is strong, and if the contact angle (θ) is 40 degrees or less, the penetration penetration height (h _C ) is 95 nm or more, that is, the concave it reaches 95% of the depth of the pattern (h _m).

  However, in order to spread the resin on the transfer substrate over the entire transfer area of the mold without pressing the mold, the contact angle (θ) needs to be as small as possible. The size of the entire transfer area of the mold is, for example, about 40 mm square.

  Table 1 shows the measurement results of the contact angle between pure water and a curable resin (manufactured by Toyo Gosei Co., Ltd., PAK-01) in a quartz mold having various release layers on the transfer surface. The PAK-01 is a curable resin generally used for nanoimprint.

  As the contact angle measuring device, Drop Master manufactured by Kyowa Interface Science Co., Ltd. was used.

In Table 1, Optool (registered trademark) is a release layer (Optool-DSX, manufactured by Daikin Industries, Ltd.) mainly composed of a fluorine-based silane compound, and ODS is octadecyltrimethoxysilane (CH ₃ (CH ₃ ( HMDS is formed on the mold by exposing the mold to a release layer in which CH ₂ ) ₁₇ Si (OCH ₃ ) ₃ ) is formed on the mold by a vapor phase growth method and HMDS is in a hexamethyldisilazane (HMDS) atmosphere Each of the release layers made of HMDS is shown.

表１に示すように、離型層ＨＭＤＳと樹脂ＰＡＫ−０１の系において接触角（θ）が最も小さい結果となった。しかしながら、このＨＭＤＳとＰＡＫ−０１の系であっても、押圧しない状態では、樹脂はモールドの転写領域全体に広がりきらない場合がある。

As shown in Table 1, the contact angle (θ) was the smallest in the system of release layer HMDS and resin PAK-01. However, even in the HMDS and PAK-01 system, the resin may not be able to spread over the entire transfer area of the mold when not pressed.

  Therefore, the contact angle (θ) of the resin is preferably as small as possible, for example, 5 degrees or less.

Next, the relationship between the resin surface free energy (γ) and the penetration penetration height (h _C ) in the capillary penetration model of the mold having the hole-shaped concave pattern shown in FIG. 1 will be described below.

FIG. 4 shows a case where the opening size (diameter = 2 × r) of the concave pattern is changed with the X-axis being the surface free energy (γ) before curing of the resin and the Y-axis being the penetration penetration height (h _C ). It is the figure which plotted the said Numerical formula (5). The contact angle (theta) is 5 degrees, the depth of the concave pattern (h _m) is 100 nm, the pressure (p) is 3500Pa.

As shown in FIG. 4, when the surface free energy (γ) of the resin decreases, the penetration penetration height (h _C ) also decreases, and this change indicates that the surface free energy (γ) of the resin is less than 10 mJ / m ^2. When it becomes, it becomes remarkable. Therefore, the surface free energy (γ) of the resin is preferably 10 mJ / m ² or more.

Next, the relationship between the surface free energy (γ) of the resin and the adhesion energy (W _{mold / resist} ) of the _mold will be described below.

  FIG. 5 is a diagram illustrating the adhesion energy between the mold and the resin. The uneven pattern on the drawing is omitted. In FIG. 5, 21 indicates a mold and 22 indicates a resin.

Here, as shown in FIG. 5 (a), the unit areas of the mold 21 and the resin 22 that are in contact with each other are divided into the free energy required to separate them as shown in FIG. 5 (b). Adhesion energy indicating change is W _{mold / resist} as the adhesion energy for separating the mold from the resin surface, γ _mold as the surface free energy of the mold, γ _resist as the surface free energy of the resin, and γ _{mold as} the interface energy between the mold and resist. _{If it is / resist} , it is expressed by the following formula (6).

一方、樹脂とモールドの固体表面との間の現象は、簡単には樹脂の固体表面への濡れの程度で表される。本発明において、表面自由エネルギーを求めるのに用いる接触角は、固体表面上におかれた液滴の表面と固体表面との交点において、液滴に引いた接線と固体表面とのなす角度で、液滴を含む側の角度を示す。

On the other hand, the phenomenon between the resin and the solid surface of the mold is simply expressed by the degree of wetting of the resin on the solid surface. In the present invention, the contact angle used to determine the surface free energy is the angle formed between the tangent line drawn on the droplet and the solid surface at the intersection of the surface of the droplet placed on the solid surface and the solid surface. The angle on the side containing the droplet is shown.

FIG. 6 is a schematic diagram for explaining the force acting on the resin on the mold surface. As shown in FIG. 6, when the resin 32 is formed on the surface of the mold 31, the surface free energy of the mold is expressed as γ _mold with respect to the contact angle representing the degree of wettability, that is, hydrophilicity and hydrophobicity. When the interfacial energy is γ _{mold / resist} , the resin surface free energy is γ _resist , and the contact angle is θ, the force relationship indicated by the three arrows is balanced, and the Young-Dupre equation shown in Equation (7) (Non-Patent Document 2) holds.

上記の数式（６）、（７）より、付着エネルギー（Ｗ_mold/resist）は、次の数式（８）で表される。したがって、樹脂の表面自由エネルギー（γ_resist）と接触角（θ）がわかれば、樹脂表面からモールドを引き離す付着エネルギー（Ｗ_mold/resist）を求めることができる。なお、樹脂の表面自由エネルギー（γ_resist）と接触角（θ）は計測により求めることができる。

From the above formulas (6) and (7), the adhesion energy (W _{mold / resist} ) is expressed by the following formula (8). Therefore, if the surface free energy (γ _resist ) and the contact angle (θ) of the resin are known, the adhesion energy (W _{mold / resist} ) for separating the mold from the resin surface can be obtained. The surface free energy (γ _resist ) and the contact angle (θ) of the resin can be obtained by measurement.

それゆえ、数式（８）から、次の数式（９）が導き出される。

Therefore, the following equation (9) is derived from the equation (8).

そして、数式（９）から、次の数式（１０）に示す範囲において５度以下の接触角（θ）が得られることになる。

From the formula (9), a contact angle (θ) of 5 degrees or less is obtained in the range shown in the following formula (10).

一方、数式（１１）に示すように、表面自由エネルギーγを分散相互作用による表面自由エネルギーγ^dと極性相互作用による表面自由エネルギーγ^pとの和とすると、オーエンス（Ｏｗｅｎｓ）の式（非特許文献３）から、下記の数式（１２）、（１３）が成り立つ。なお、γ^d _resistおよびγ^p _resistは、それぞれレジストの表面自由エネルギーの分散成分と極性成分であり、γ^d _moldおよびγ^p _moldは、それぞれモールド（モールド表面に離型層が設けられている場合は、その離型層）の表面自由エネルギーの分散成分と極性成分である。

On the other hand, as shown in Equation (11), when the surface free energy γ is the sum of the surface free energy γ ^d due to the dispersion interaction and the surface free energy γ ^p due to the polar interaction, the Owens equation (non-patent) From the literature 3), the following formulas (12) and (13) hold. Γ ^d _resist and γ ^p _resist are the dispersion component and polar component of the resist surface free energy, respectively. Γ ^d _mold and γ ^p _mold are molds (when a mold release layer is provided on the mold surface), respectively. Are the dispersion component and the polar component of the surface free energy of the release layer).

数式（１３）が示す通り、付着エネルギー（Ｗ_mold/resist）は、樹脂とモールドの表面自由エネルギーの分散成分（γ^d _resistおよびγ^d _mold）と極性成分（γ^p _resistおよびγ^p _mold）で決まるが、付着エネルギーの最大値（Ｗ_mold/resistｍａｘ）は、数式（１１）の関係から、分散成分と極性成分に依存せずに、数式（１４）のように表される。

As shown in Equation (13), the adhesion energy (W _{mold / resist} ) is the dispersion component (γ ^d _resist and γ ^d _mold ) and polar component (γ ^p _resist and γ ^p _mold ) of the surface free energy of the resin and the mold. Although it is determined, the maximum value (W _{mold / resist} max) of the adhesion energy is expressed by the equation (14) without depending on the dispersion component and the polar component from the relationship of the equation (11).

図７は、Ｘ軸を樹脂の表面自由エネルギーの極性成分（γ^p _resist）、Ｙ軸を接触角（θ）として、上記数式（１１）、（１３）に基づき、上記数式（９）をプロットした図である。接触角は、液体と固体の表面自由エネルギーの分散成分、極性成分によって変わるため、極性成分の関数として示してある。なお、図７においては、樹脂の表面自由エネルギー（γ_resist）を２５ｍＪ／ｍ²、モールドの表面自由エネルギーの極性成分（γ^p _mold）をモールドの表面自由エネルギー（γ_mold）の１／２としている。

FIG. 7 plots the above equation (9) based on the above equations (11) and (13), where the X axis is the polar component (γ ^p _resist ) of the surface free energy of the resin and the Y axis is the contact angle (θ). FIG. The contact angle is shown as a function of the polar component because it varies depending on the dispersion component and polar component of the surface free energy of the liquid and solid. In FIG. 7, the surface free energy (γ _resist ) of the resin is 25 mJ / m ² , and the polar component (γ ^p _mold ) of the mold surface free energy is ½ of the _mold surface free energy (γ _mold ). Yes.

As shown in FIG. 7, when the surface free energy (γ _resist ) of the resin is smaller than the surface free energy (γ _mold ) of the _mold , a region where the contact angle (θ) is 5 degrees or less appears.

Specifically, in FIG. 7, when the surface free energy of the _mold (γ _mold ) is 20 mJ / m ² , the contact component can be obtained _regardless of the polar component (γ ^p _resist ) of the surface free energy of the resin. The angle (θ) is 30 degrees or more, but when the mold surface free energy (γ _mold ) is 25 mJ / m ² , the polar component (γ ^p _resist ) of the resin surface free energy is approximately 11 to 14 mJ / In the range of m ² , the contact angle (θ) is 5 degrees or less, and when the mold surface free energy (γ _mold ) is 30 mJ / m ² , the polar component of the resin surface free energy (γ ^p _In the range of 4 to 21 mJ / m ² , the contact angle (θ) is 5 degrees or less.

FIG. 8 is an example in which the polar component (γ ^p _mold ) of the surface free energy of the _mold in FIG. 7 is set to 1/5 of the surface free energy (γ _mold ) of the _mold as in FIG.

As shown in FIG. 8, when the polar component (γ ^p _mold ) of the surface free energy of the _mold changes, the range of the polar component (γ ^p _resist ) of the surface free energy of the resin that the contact angle (θ) becomes 5 degrees or less. Also changes.

Specifically, in FIG. 7, when the mold surface free energy (γ _mold ) is 25 mJ / m ² , the polar component (γ ^p _resist ) of the resin surface free energy is approximately 11 to 14 mJ / m ² . In the range, the contact angle (θ) was 5 degrees or less, but in FIG. 8, the polar component (γ ^p _resist ) of the surface free energy of the resin is in the range of approximately 4 to 6 mJ / m ^2. (Θ) is 5 degrees or less.

On the other hand, in FIG. 9, the X-axis is the mold surface free energy (γ _mold ), the Y-axis is the maximum adhesion energy (W _{mold / resist} max), and the resin surface free energy (γ _resist ) is the parameter. The expression (14) is plotted. As shown in FIG. 9, the smaller the surface free energy (γ _mold ) of the _mold and / or the smaller the surface free energy (γ _resist ) of the resin, the smaller the maximum value (W _{mold / resist} max) of the adhesion energy. Become. Therefore, considering the mold releasability between the mold and the resin, it is desirable to reduce each surface free energy.

Furthermore, focusing on the polar component and the dispersion component of the surface free energy, the increase and decrease of the adhesion energy will be shown. FIG. 10 is a diagram in which the above equation (13) is plotted with the X axis as the polar component (γ ^p _resist ) of the surface free energy of the resin and the Y axis as the adhesion energy (W _{mold / resist} ). In FIG. 10, as in FIG. 7, the resin surface free energy (γ _resist ) is 25 mJ / m ² , and the mold surface free energy polar component (γ ^p _mold ) is the mold surface free energy (γ _mold). ).

As shown in FIG. 7 and FIG. 10, in the polar component (γ ^p _resist ) of the surface free energy of the resin where the contact angle (θ) is minimum (or the center of the region where the contact angle is 5 degrees or less), The adhesion energy (W _{mold / resist} ) is maximized.

Specifically, when the surface free energy of the _mold (γ _mold ) is 25 mJ / m ² , the contact angle (γ ^p _resist ) is approximately 12 mJ / m ^{2 in} the vicinity of the polar component (γ ^p _resist ) of the resin surface free energy. θ) is minimized (FIG. 7), and the adhesion energy (W _{mold / resist} ) is maximized (FIG. 10).

Next, FIG. 11 is an example in which the polar component (γ ^p _mold ) of the mold surface free energy in FIG. 10 is set to 1/5 of the _mold surface free energy (γ _mold ) and plotted in the same manner as FIG. is there.

As shown in FIG. 11, when the polar component (γ ^p _mold ) of the surface free energy of the _mold changes, the polarity component (γ ^p _resist ) of the surface free energy of the resin that maximizes the adhesion energy (W _{mold / resist} ). The value also changes.

Similarly to the relationship between FIG. 7 and FIG. 10 described above, the polar component (γ ^p of the surface free energy of the resin having the minimum contact angle (θ) (or the center of the region where the contact angle is 5 degrees or less). _{In resist} ), the adhesion energy (W _{mold / resist} ) is maximized.

Specifically, when the surface free energy of the _mold (γ _mold ) is 25 mJ / m ² , the contact angle (γ ^p _resist ) is approximately 5 mJ / m ^{2 in} the vicinity of the polar component (γ ^p _resist ) of the resin. θ) is minimized (FIG. 8), and the adhesion energy (W _{mold / resist} ) is maximized (FIG. 11).

  Here, considering the mold releasability between the mold and the resin, the region where the adhesion energy is maximized should be avoided. Therefore, the value of the polar component of the surface free energy of the resin in a state before curing is a value far from the value of the polar component of the surface free energy of the resin that maximizes the adhesion energy between the resin after curing and the mold. A resin may be desirable.

  As described above, regarding the filling of the resin into the minute uneven pattern formed in the mold, the relationship between the surface free energy of the mold and the surface free energy of the resin, the magnitude of the surface free energy of the resin, and the mold If the relationship between the adhesion energy between the resin and the resin, the surface free energy of the resin and its polar component, etc. satisfy the range specified in the present invention, the resin spreads over the entire transfer area, and the capillary force is effective. Therefore, the resin can be filled by faithfully following the minute uneven pattern shape formed in the mold without requiring high pressure.

1, 21, 31 ... Mold 2, 22, 32 ... Resin 3 ... Gas 42 ... Liquid

That is, the invention according to claim 1 of the present invention is a nanoimprint method for transferring an uneven transfer pattern formed on a mold to a curable resin formed on a substrate to be transferred, wherein the curable resin is cured. prior to surface free energy, the a value smaller than the surface free energy of the mold, the surface free energy before curing of said curable resin is state, and are 1 3 mJ / m ² or more, the curable to said mold contact angle of the resin is nanoimprint method comprising der Rukoto 40 degrees or less.

The invention according to claim 2 of the present invention is the transfer pattern, a nanoimprint method according to claim 1 aperture size characterized that you have included the following concave pattern 100 nm. The invention according to claim 3 of the present invention is the nanoimprint method according to claim 2, wherein the concave pattern is a hole-shaped concave pattern.

Further, the invention according to claim 4 of the present invention is a nanoimprint method for transferring an uneven transfer pattern formed on a mold to a curable resin formed on a substrate to be transferred, the mold and the mold before being cured. When the adhesion energy with the curable resin is W _{mold / resist} and the surface free energy before curing of the curable resin is γ _resist , the polar component of the surface free energy before curing of the curable resin (γ ^p _resist )
W _{mold / resist} / γ _resist −1> 0.766
The nanoimprint method is characterized in that the value satisfies the above range.

Claims (3)

A nanoimprint method for transferring an uneven transfer pattern formed on a mold to a curable resin formed on a transfer substrate,
The surface free energy before curing of the curable resin is a value smaller than the surface free energy of the mold,
The nanoimprint method, wherein the surface free energy before curing of the curable resin is 10 mJ / m ² or more.   The nanoimprint method according to claim 1, wherein a contact angle of the curable resin with respect to the mold is 40 degrees or less. A nanoimprint method for transferring an uneven transfer pattern formed on a mold to a curable resin formed on a transfer substrate,
When the adhesive energy between the mold and the curable resin before curing is W _{mold / resist,} and the surface free energy before the curable resin is cured is γ _resist , the surface _freeness before the curable resin is cured. The value of the polar component of energy (γ ^p _resist ) is
W _{mold / resist} / γ _resist -1> 0.996
A nanoimprint method characterized in that the value satisfies the above range.

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