JP4884730B2 - Nanoimprint method and nanoimprint apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nanoimprint method and a nanoimprint apparatus in which reproducibility of a pattern to be formed is improved. <P>SOLUTION: The nanoimprint method for forming a pattern on a substrate or a film provided on the substrate by using a mold includes steps of disposing a mold opposing to the substrate or the film provided on the substrate to leave a gap between the substrate or the film provided on the substrate and the mold, and applying a voltage between the mold and the substrate or the film provided on the substrate. The nanoimprint apparatus for forming a pattern on a substrate or a film provided on a substrate by using a mold includes a means of disposing the mold to oppose to the substrate or the film provided on the substrate to leave a gap between the substrate or the film provided on the substrate and the mold, and a means of applying a voltage between the mold and the substrate or the film provided on the substrate and the mold. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

The present invention relates to at least one of a nanoimprint method and a nanoimprint apparatus .

  In order to fabricate large-scale and high-performance devices such as LSIs, extremely fine patterns are required. Such a pattern is a resist pattern formed through exposure, development, and cleaning (rinsing), and an etching pattern formed through etching and cleaning (water washing). A resist is a polymer material that is sensitive to light, X-rays, electron beams, and the like, and a powder or a highly viscous liquid dissolved in an organic solvent is used. The exposure is performed by irradiating the resist with light or an electron beam through a mask having a pattern formed based on circuit design. However, an apparatus used for exposure is mainly an apparatus of several billion yen called a stepper. Therefore, there has been a demand for an apparatus that can form a fine pattern at low cost.

Therefore, in recent years, a technique called imprint lithography has been attracting attention (for example, Journal of Vacuum Science and Technology B Vol. 14, No. 6, pp. 4129-4133 (1996) ( Non-patent Document 1 ) and Japan Journal of ). Applied Physics, Vol. 43, No. 6B, pp. 4045-4049 (2004) ( see Non-Patent Document 2 ) .). This method is an application of the imprint method conventionally used in DVD production. In the imprint lithography, a mold (stamper) is pressed against a resist film on a thin film to be processed to transfer a pattern, and then etched to obtain a thin film pattern necessary for a semiconductor. FIG. 12 is a diagram illustrating a conventional imprint lithography process. That is, a mold 1001 such as silicon formed by a known exposure method shown in FIG. 12A is pressed against a resist film 1002 such as PMMA as shown in FIG. 12B, and as shown in FIG. Then, the pattern of the mold 1001 is transferred to the resist film 1002 to obtain a resist pattern as shown in FIG.

  Imprint lithography includes a batch transfer method and a step-and-repeat method. The batch transfer method is to form a mold having the same size as the substrate and press the substrate and the mold as they are. In the step-and-repeat method, the mold is set to a chip size and imprint lithography is performed for each chip. For example, a 20-mm square mold on which a pattern has been formed is pressed onto a 200 mm diameter silicon wafer by 5 pieces in the vertical direction and 5 pieces in the horizontal direction to transfer a 25-chip pattern. In general, the substrate and the mold are warped, and the degree of warpage increases as the size of the substrate increases. As a result, when the substrate becomes large, the depth to which the mold pattern is pressed may be different within the substrate surface. For this reason, a step-and-repeat method is desired for large-diameter substrates.

  A major problem with such imprint lithography is that when the mold 1001 is pressed against the substrate with the resist film 1002 as shown in FIG. 12D, the resist film 1002 is attached to the mold 1001 and becomes a defect. It is. In order to avoid this, a mold release agent such as a fluorine-based silane coupling agent is applied to the mold 1001, but the problem is not completely solved. In particular, since the mold 1001 is pushed against the resist film 1002 many times in the step-and-repeat method, the defect of the pattern due to the adhesion of the resist piece is a significant problem.

On the other hand, a pattern forming method that does not use a resist film in recent imprint lithography is a method in which a convex portion of a mold pattern and a substrate are brought into close contact with each other, a voltage is applied, and anodization is performed at the close contact portion (for example, Japan Journal of OF). Applied Physics, Vol. 42, Part 2, No. 2A, pp. L92-L94 (2003) ( Non-patent Document 3 ) , Journal of Vacuum Science and Technology B Vol.21, No. 6, pp. 2966-2966. 2003) ( Non-Patent Document 4 ) , and Japanese Journal of Applied Physics, Vol. 44, No. 2, pp. 1119-1122 (2005) ( Non-Patent Document 5 ) ). More specifically, only the portion of the substrate in close contact with the convex portion of the mold pattern is anodized. Thus, since the resist film is not used, the above-described defects are not generated.

However, this method has not yet achieved a pattern with good reproducibility. That is, the dimensional accuracy of the pattern formed by imprinting is poor, and in the worst case, there is a problem that the pattern cannot be formed.
Journal of Vacuum Science and Technology B Vol. 14, no. 6, pp. 4129-4133 (1996) Japan Journal of Applied Physics, Vol. 43, no. 6B, pp. 4045-4049 (2004) Japan Journal of Applied Physics, Vol. 42, Part 2, no. 2A, pp. L92-L94 (2003) Journal of Vacuum Science and Technology B Vol. 21, no. 6, pp. 2966-2969 (2003) Japan Journal of Applied Physics, Vol. 44, no. 2, pp. 1119-1122 (2005)

A first object of the present invention is to provide a burner Noin printing method.

A second object of the present invention is to provide a burner Noin printing device.

According to a first aspect of the present invention, there is provided a nanoimprint method for forming a pattern on a substrate or a film provided on the substrate using a mold, between the film provided on the substrate or the substrate and a convex portion of the mold. It is opposed to mold to the film provided to the substrate body or a substrate provided a gap, and, together with includes applying a voltage between the film and the mold provided on the base body or substrate, prior Symbol characterized in that it further comprises controlling the temperature of the mold dew point temperature below the temperature, which is nanoimprint method.

According to a second aspect of the present invention, in a nanoimprint apparatus that forms a pattern on a substrate or a film provided on the substrate using a mold, the substrate or the film provided on the substrate and a convex portion of the mold are provided. It means for facing the mold to film provided on the base body or substrate to provide a gap, and, together with includes means for applying a voltage between the membrane and the mold provided on the base body or substrate, prior to The nanoimprint apparatus further includes means for controlling the temperature of the recording mold to a temperature not higher than the dew point temperature.

According to a first aspect of the present invention, it is possible to provide a burner Noin printing method.

According to a second aspect of the present invention, it is possible to provide a burner Noin printing device.

  Next, embodiments of the present invention will be described with reference to the drawings.

  A first embodiment of the present invention is a nanoimprint method in which a pattern is formed on a substrate or a film provided on the substrate using a mold, and a gap is provided between the substrate or the film provided on the substrate and the mold. The method includes causing the mold to face the base or the film provided on the base so as to be provided, and applying a voltage between the base or the film provided on the base and the mold.

  A second embodiment of the present invention is a nanoimprint apparatus for forming a pattern on a substrate or a film provided on the substrate using a mold, and a gap is provided between the substrate or the film provided on the substrate and the mold. Means for making the substrate face the mold on the substrate or the film provided on the substrate, and means for applying a voltage between the film provided on the substrate or the substrate and the mold.

  The nanoimprinting method and the nanoimprinting apparatus are respectively a method and an apparatus for forming a pattern using a mold on a substrate or a film provided on the substrate. Preferably, the nanoimprinting method and the nanoimprinting device have a size of tens of nanometers to hundreds of nanometers. And a method and apparatus capable of forming a fine pattern on a substrate or a film provided on the substrate.

  The shape of the substrate or the film provided on the substrate is not particularly limited as long as the shape corresponding to at least a part of the shape of the mold can be transferred to the substrate or the film provided on the substrate. For example, it may be in the form of a plate, and the film provided on the substrate may be a so-called thin film. The thickness of the thin film is, for example, 10 nm to 20 nm. That is, the substrate may be a substrate, for example. The substrate alone is a substrate whose surface is oxidized. When a film is provided on the substrate, the substrate may be either a substrate whose surface is oxidized or a substrate whose surface is not oxidized. The provided film is a film to be oxidized. As the material of the substrate whose surface is oxidized and the material of the film to be oxidized, various semiconductor materials such as silicon (silicon), germanium, gallium arsenide (GaAs), indium phosphide (InP), and aluminum, zinc, Various metal materials such as titanium, chromium, iron, nickel, and lead are listed. Examples of the base material whose surface is not oxidized include oxides of various semiconductor materials such as silicon oxide, germanium oxide, GaAs oxide, and InP oxide, aluminum oxide, zinc oxide, titanium oxide, Examples thereof include oxides of various metal materials such as chromium oxide, iron oxide, nickel oxide and lead oxide, various organic polymer materials such as polycarbonate, and various glass materials. In the following, “substrate or film provided on the substrate” will be referred to as “substrate or the like”.

  The shape of the mold (mold) includes at least a shape corresponding to the shape to be transferred to the substrate or the like. The material of the mold may be silicon, but more preferably a metal such as iron, SUS, titanium, nickel, gold, carbon, or silicon carbide (SiC). This is because metals such as iron (electrolytic separation ratio 6 to 9) and nickel (electrolytic separation ratio 4 to 6) and carbon (electrolytic separation ratio 7 to 8) are electrodes with high electrolytic separation ratio of water. is there. In particular, the mold preferably comprises carbon and more preferably consists of carbon. A material obtained by processing a polymer block of carbon, such as glassy carbon, after forming a pattern and then firing the processed material is extremely strong, so it can be used as a mold can do. The mold material may be a material coated with the above metal, carbon, or silicon carbide. The mold material preferably includes a conductive material, but the entire mold need not be conductive, and at least a portion of the mold may be composed of an insulating material.

It is also convenient to coat the surface of the mold with a catalytic metal or compound. Examples of the metal having a catalytic action include Pt, Pd, Ag, and the like. Examples of the compound having a catalytic action include a photocatalyst such as titanium dioxide. In this case, active oxygen is generated from oxygen and water touching the coated surface of the mold, and the oxidation reaction on the surface of the substrate can be promoted by the oxidizing action of active oxygen. _{Also, V 2 O 5, MoO 3} , Cu 2 O, CoO, may be used an oxidation catalyst such as _MnO 2, WO _3.

  The means for making the mold face the base or the like so as to provide a gap between the base or the like and the mold is not particularly limited, and may be a means for providing a predetermined gap between the base or the like and the mold. The means for making the mold face each other is preferably a means capable of adjusting the relative positions of the base body and the mold. Means for making the mold face the base or the like is a spacer provided between the base or the like and the same size or different size, means for holding at least one of the base and the mold, and mechanically moving them relative to each other. Is mentioned. For example, an up / down (horizontal) moving jig for holding a pattern-formed mold and an XY stage for holding a substrate to be processed can be used.

The means for applying a voltage between the substrate and the mold is not particularly limited, but the substrate and the mold are electrically joined to each other, and the voltage between the substrate and the mold is controlled by a known voltage control system. May be. Here, the voltage is applied so that the substrate or the like has a positive potential with respect to the mold. That is, the substrate or the like becomes an anode, and the mold becomes a cathode. In this way, by applying a voltage between the base and the like and the mold, the surface of the base and the like can be anodized and an anodized film can be formed on the surface of the base and the like. For example, water such as moisture in the air exists in the gap provided between the substrate and the mold. Here, when a voltage is applied between the substrate or the like and the mold, the water present in the gap provided between the substrate or the like and the mold becomes the formula 2H ₂ O −4e ⁻ → O ₂ (or 2O ·) + 4H. ⁺
In accordance with electrolysis. As a result, oxygen or oxygen radicals generated by the electrolysis of water oxidize the surface of the substrate, which is the anode, and an anodic oxide film is formed on the surface of the substrate. In addition, when a voltage is applied between the substrate and the mold, a current may flow between the substrate and the mold.

  The size of the gap (gap) provided between the substrate and the mold is preferably 0.4 μm to 1.2 μm, and more preferably 0.5 μm to 0.8 μm. If the size of the gap provided between the substrate and the mold is less than 0.4 μm, particularly when the substrate and the mold are in close contact with each other, only a current flows between the substrate and the mold. Such a surface cannot be sufficiently anodized, and it may be difficult to form an anodized film on the surface of the substrate or the like. On the other hand, when the size of the gap provided between the substrate and the mold exceeds 1.2 μm, the voltage applied between the substrate and the mold is weak, and the surface of the substrate and the like is sufficiently anodized. In some cases, it may be difficult to form an anodized film on the surface of a substrate or the like. Therefore, in order to form an oxide film on the surface of the substrate or the like with good reproducibility, the size of the gap provided between the substrate and the mold is in the range of 0.4 μm to 1.2 μm. It is preferable. Further, by providing a gap between the substrate and the mold, water or moisture can be interposed between the substrate and the mold.

  As a result of performing an experiment using a mold and a silicon substrate having a pattern formed on the silicon surface, a load of 0.5 MPa was applied to the mold and the silicon substrate, and when the mold and the silicon substrate were completely adhered, the mold and silicon Even when a pulse voltage of 20 V was applied to the substrate, an anodic oxide film corresponding to the mold pattern was not formed on the surface of the silicon substrate. On the other hand, when the gap between the mold and the silicon substrate is formed, a pattern is formed on the surface of the silicon substrate. When the gap between the mold and the silicon substrate is further increased, this time, the silicon substrate is reversed. A pattern could not be formed on the surface.

  The thickness of the anodic oxide film formed on the substrate or the like is usually about 2 nm. Formation of the anodic oxide film can be confirmed by etching the surface of the substrate or the like with an aqueous potassium hydroxide solution. That is, if an anodic oxide film is present, the anodic oxide film cannot be etched at all, so that the formation of a pattern on the surface of the substrate or the like can be confirmed.

  In the nanoimprint method according to the first embodiment of the present invention, the size of the gap provided between the substrate and the mold may be varied. In other words, the size of the gap provided between the substrate or the like and the mold does not need to be a desired constant interval, and may be varied so as to include the desired interval. That is, when the size of the gap provided between the substrate or the like and the mold is about the same as the desired distance, the surface of the substrate or the like can be effectively anodized. In addition, the size of the gap provided between the substrate and the mold may be varied by means of applying a voltage between the substrate and the mold and simultaneously making the mold face the substrate and the like. Here, the variation in the size of the gap provided between the substrate and the mold includes an increase and / or decrease in the size of the gap provided between the substrate and the mold. For example, at the same time as applying a voltage between the base body and the mold, the upper mold may be lowered toward the lower base body, or the lower base body and the like may be raised toward the upper mold. Alternatively, increasing and decreasing the size of the gap between the substrate or the like and the mold may be repeated.

  When changing the size of the gap provided between the substrate and the mold and the mold, the means for changing the size of the gap provided between the substrate and the mold is at least one of the substrate and the mold. In addition to means for mechanically holding and moving relative to each other, means for having a stretchable spacer between the base and the mold and applying force to at least one of the base and the mold, at least the base and the mold Means for deforming one of them can be mentioned.

  According to the means for mechanically holding at least one of the base body and the mold and moving them relative to each other, at least one of the base body and the mold and the mold is simultaneously moved with respect to each other. Thus, the size of the gap provided between the base body and the mold can be varied.

  According to the means having a stretchable spacer between the base body and the mold and applying a force to at least one of the base body and the mold, a force is applied to at least one of the base body and the mold and between the base body and the mold. The size of the gap provided between the base body and the mold can be varied by expanding and contracting the stretchable spacer. The size of the gap provided between the substrate and the mold may be changed uniformly or may be changed non-uniformly. In the case where the size of the gap provided between the substrate or the like and the mold is uniformly changed, it is preferable to use a plurality of substantially the same stretchable spacers. Here, “substantially the same” means that they are the same to the extent that a uniform variation in the size of the gap provided between the substrate and the mold can be achieved. On the other hand, when the size of the gap provided between the substrate or the like and the mold is varied non-uniformly, it is preferable to use a plurality of different stretchable spacers, and at least one of the plurality of spacers is A non-stretchable spacer may be used. Here, the term “non-stretchable” means non-stretchable to such an extent that a nonuniform variation in the size of the gap provided between the base body and the mold can be achieved.

  According to the means for deforming at least one of the substrate and the mold, the size of the gap provided between the substrate and the mold can be varied by deforming at least one of the substrate and the mold. In this case, a substantially non-stretchable spacer may be provided between the substrate and the mold in order to deform at least one of the substrate and the mold. Here, substantially non-stretchable means that it is non-stretchable to such an extent that at least one of the base body and the mold can be deformed. In order to deform at least one of the base body and the mold, means for applying a force to at least one of the base body and the mold may be used. If necessary, the force applied to at least one of the substrate and the mold may be changed, and the force may be applied to at least one of the substrate and the mold multiple times. The position may be changed, and a force may be applied to at least one of the base body and the mold several times.

  According to the nanoimprint method which is the first embodiment of the present invention, it is possible to provide a nanoimprint method in which the reproducibility of the formed pattern is improved. According to the nanoimprint apparatus which is the second embodiment of the present invention, it is possible to provide a nanoimprint apparatus in which the reproducibility of the formed pattern is improved.

  The nanoimprint method according to the first embodiment of the present invention may be performed according to a step-and-repeat method. The nanoimprint method according to the first embodiment of the present invention may be carried out according to the batch transfer method, but it is more effective to carry out according to the step-and-repeat method. The step-and-repeat method makes it possible to form patterns with good uniformity even on large-diameter substrates. However, in the conventional imprint method, the resist pieces on the resist layer provided on the substrate adhere to the mold. In addition, a defect may occur in the pattern formed on the substrate or the like. However, since the nanoimprint method according to the first embodiment of the present invention does not use a resist, it realizes a step-and-repeat method in which a resist piece is attached to a mold and there is no pattern defect formed on a substrate or the like. Can be made.

  As described above, according to the nanoimprint method according to the first embodiment of the present invention, the imprint lithography method free from defects in the pattern formed on the substrate or the like due to the adhesion of the resist piece to the mold is used to remove defects. A small number of high resolution patterns can be formed. Therefore, a structure having a fine pattern can be easily formed at low cost, and a high-performance device can be manufactured at low cost and with high throughput.

  Preferably, the nanoimprint apparatus according to the second embodiment of the present invention further includes means for controlling the humidity of the atmosphere surrounding the substrate and the mold. The nanoimprint apparatus according to the second embodiment of the present invention may include means for controlling both the humidity of the atmosphere surrounding the substrate and the mold and the temperature of the substrate and the mold. Here, the humidity of the atmosphere surrounding the substrate and the mold is the relative humidity (%) of the atmosphere surrounding the substrate and the mold. As a means for controlling the humidity of the atmosphere surrounding the substrate and the mold (and both the temperature of the substrate and the mold), the humidity of the atmosphere surrounding the substrate and the mold (and both the temperature of the substrate and the mold) It may be a chamber for controlling. By using means for controlling the humidity of the atmosphere surrounding the substrate and the mold (and both the temperature of the substrate and the mold), an anodic oxide film can be more efficiently formed on the surface of the substrate and the like. The humidity of the atmosphere surrounding the substrate and the mold (and both the temperature of the substrate and the mold) can be controlled.

  Preferably, the nanoimprint method according to the first embodiment of the present invention further includes controlling the humidity of the atmosphere surrounding the substrate and the mold to 30% or more. In the nanoimprint method according to the first embodiment of the present invention, when the humidity of the atmosphere surrounding the substrate and the mold is less than 30%, anodization of the surface of the substrate or the like may not occur. For example, when a gap is provided between a mold having a pattern formed on the silicon surface and the silicon substrate, the mold and the silicon substrate are maintained at room temperature, and a pulse voltage of 20 V is applied between the mold and the silicon substrate, the substrate, etc. In addition, an anodic oxide film corresponding to the mold pattern was not formed on the surface of the silicon substrate unless the humidity surrounding the mold was 30% or more. Therefore, in order to more efficiently form the anodic oxide film on the surface of the substrate or the like, the humidity of the atmosphere surrounding the substrate and the mold is preferably 30% or more.

  Preferably, the nanoimprint apparatus according to the second embodiment of the present invention further includes means for attaching water to at least one of the substrate and the mold. Preferably, the nanoimprint method according to the first embodiment of the present invention further includes attaching water to at least one of the substrate and the mold. The attachment of water to at least one of the substrate and the mold or the mold is usually performed at the same time or before the voltage is applied between the substrate and the mold and the mold. The means for adhering water to at least one of the substrate and the mold is not particularly limited, and for example, a means for spraying water droplets on at least one of the substrate and the mold may be used. Note that at least one of the base body and the mold includes only the base body and the like, only the mold, and both the base body and the mold. Before applying a voltage between the substrate or the like and the mold, water is attached to at least one of the substrate or the mold and the substrate, in addition to the moisture in the air. Water attached to at least one of the molds can be electrolyzed to promote anodic oxidation on the surface of the substrate or the like. As a result, an anodized film can be more efficiently formed on the surface of the substrate or the like.

  Preferably, the nanoimprint apparatus according to the second embodiment of the present invention further includes means for controlling the temperature of at least one of the substrate and the mold. At least one of the base and the like and the mold includes only the base and the like, only the mold, and both the base and the like. The means for controlling the temperature of at least one of the substrate and the mold may be a means for circulating a temperature adjustment medium such as water and bringing the temperature adjustment medium into contact with at least one of the substrate and the mold, but preferably And means for controlling the temperature of at least one of the substrate and the mold using a Peltier element. Means using a Peltier element is preferable for space saving. By controlling the temperature of at least one of the substrate and the mold, it is possible to cause condensation on at least one of the substrate and the mold.

  Preferably, the nanoimprinting method according to the first embodiment of the present invention further includes controlling the temperature of at least one of the substrate and the mold to a temperature not higher than the dew point temperature. Further, when the temperature of at least one of the substrate and the mold is controlled to a temperature equal to or lower than the dew point temperature, dew condensation occurs spontaneously on the surface of at least one of the substrate and the mold. That is, a thin water layer can be easily formed on at least one surface of the substrate and the mold. In this way, by causing dew condensation on the surface of at least one of the substrate and the mold efficiently, in addition to moisture in the air between the substrate and the mold, the surface of at least one of the substrate and the mold The water in the thin water layer formed on the substrate can be electrolyzed to further promote the anodic oxidation of the surface of the substrate or the like. For example, the atmospheric humidity was 30%, and the mold temperature was lowered to a temperature of 10 ° C. or lower, so that water was adsorbed and a thin layer of water was formed on the mold surface. With this method, when water was adsorbed on the surface of the mold and a voltage was applied between the mold and the substrate, a good anodic oxide film pattern could be obtained. Note that if the humidity of the atmosphere surrounding the substrate and the mold is too high, the amount of condensed water on at least one surface of the substrate and the mold increases. Therefore, water is adsorbed so as to reduce the humidity of the atmosphere surrounding the substrate and the mold, reduce the temperature of at least one of the substrate and the mold, and form a thin layer on at least one surface of the substrate and the mold. It is preferable.

  Preferably, in the nanoimprint apparatus according to the second embodiment of the present invention, the surface of at least one of the substrate and the mold is subjected to a hydrophilic treatment. Examples of the hydrophilic treatment include a hydrophilic treatment using corona discharge and a hydrophilic treatment using a surfactant.

  In the hydrophilization treatment by corona discharge, ozone, oxygen, nitrogen, moisture, etc. in the atmosphere surrounding the substrate and the mold are activated by corona discharge, and polar functional groups such as carbonyl group, carboxyl group, hydroxyl group, etc. And a process that is generated on at least one surface of the mold. The hydrophilic treatment by corona discharge improves the wettability of the surface of at least one of the substrate and the mold by hydrophilizing the surface of the substrate and the mold by corona discharge. As a result, water can be more easily adsorbed onto the surface of at least one of the substrate and the mold and the electrolysis of water between the substrate and the mold can be further promoted. As a result, anodization of the surface of the substrate or the like can be further promoted. For example, it has been confirmed that the reaction time required for pattern formation on the silicon substrate is shortened on average by 30% in the hydrophilization treatment of the silicon substrate by corona discharge.

In the hydrophilization treatment with the surfactant, the functional group of the surfactant is bonded to the moisture adsorbed on the surface of at least one of the substrate and the mold, and the water layer is adsorbed on at least the surface of the substrate and the mold. Is a process for forming the film more stably. Examples of the surfactant include fatty acid diethanolamide (C ₁₁ H ₂₃ CON (CH ₂ CH ₂ OH) ₂ ), polyoxyethylene alkyl ether (C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₈ H), poly nonionic surfactants such as polyoxyethylene alkyl phenyl ether _{(C 9 H 19 (C 6} H 4) O (CH 2 CH 2 O) 8 H), fatty acid salts _{(C 11} H 23 COONa), alpha sulfo fatty acid ester salts _{(C 10 H 21 CH (SO} 33 Na) COOCH 3), alkylbenzene sulfonate _{(C 12 H 25 (C 6} H 4) SO 3 Na), alkyl sulfate _{(C 12 H 25 OSO 3 Na} ), alkyl ether sulfate _{(C 12 H 25 O (CH} 2 CH 2 O) 3 SO 3 Na), alkyl sulfates Triethanolamine ^- anionic surface active agents such as ^{_{(C 12 H 25 OSO 3 ·}} + NH (CH 2 CH 2 OH) 3), alkyl trimethyl ammonium salts ^{_{(C 12 H 25 N + (}} CH 3) 3 · Cl ⁻ ), dialkyldimethylammonium chloride (C ₁₂ H ₂₅ N ⁺ (C ₈ H ₁₇ ) (CH ₃ ) ₂ · Cl ⁻ ), alkylpyridinium chloride (C ₁₂ H ₂₅ (N ⁺ C ₅ H ₅ ) · Cl) And a zwitterionic surfactant such as alkylcarboxybetaine (C ₁₂ H ₂₅ N ⁺ (CH ₃ ) ₂ .CH ₂ COO ⁻ ). The hydrophilic treatment with a surfactant improves the wettability of the surface of at least one of the substrate and the mold by hydrophilizing the surface of the substrate and the mold. As a result, water can be more stably adsorbed on the surface of at least one of the substrate and the mold, and the electrolysis of water between the substrate and the mold can be further promoted. For example, it has been confirmed that the reaction time required for pattern formation on a silicon substrate is reduced by 50% on average in the hydrophilic treatment of a silicon substrate with a surfactant.

  Next, examples of the nanoimprint method according to the first embodiment of the present invention and the nanoimprint apparatus according to the second embodiment of the present invention will be described with reference to the drawings.

1A to 1G are diagrams illustrating an example of a nanoimprint method and an example of a nanoimprint apparatus according to an embodiment of the present invention. FIG. 1 (a) shows the step of installing the mold and the substrate, FIG. 1 (b) shows the step of bringing the mold closer to the substrate, and FIG. 1 (c) shows the state of the substrate under the convex part of the mold. 1D shows a step of forming an oxide film on the surface, FIG. 1D shows a step of moving the mold away from the substrate, FIG. 1E shows a step of moving the mold relative to the surface of the substrate, and FIG. (F) shows the step of forming the oxide film by bringing the mold again to another place on the surface of the substrate, and FIG. 1 (g) shows the etching of the substrate using the oxide film formed on the surface of the substrate as a mask. The stage to do is shown.

  As shown in FIG. 1A, the nanoimprint apparatus has a mold 11, a voltage control system 12, and a temperature adjustment mechanism 13 in a humidity temperature control chamber (not shown) in which the internal temperature and humidity are controlled. . A substrate 14 to be processed is introduced into the nanoimprint apparatus 10. The mold 11 is made of, for example, a material such as silicon, carbon, SiC, or metal, and the mold 11 is patterned into a desired shape by a known method. In FIG. 1A, the mold 11 has a line-and-space pattern composed of concave and convex portions. The mold 11 is installed such that the uneven portion of the mold 11 faces the surface of the substrate 14 and is separated from the surface of the substrate 14. The substrate 14 is made of a material such as silicon or gallium / arsenic. The mold 11 and the substrate 14 are electrically connected to the voltage control system 12, respectively. Between the mold 11 and the substrate 14, the substrate 14 is an anode, and the mold 11 is a cathode. Thus, a voltage is applied. The mold 11 is further connected to a temperature adjustment mechanism 13 that uses a Peltier element or the like.

  Next, as shown in FIG. 1B, with a voltage applied between the mold 11 and the substrate 14, a gap is formed between the convex portion of the mold 11 and the surface of the substrate 14. The mold 11 is lowered toward the substrate 14 to bring the mold 11 closer to the substrate 14. Note that the size of the gap between the convex portion of the mold 11 and the surface of the substrate 14 may be varied within a range including the desired size of the gap. The mold 11 is cooled to a temperature not higher than the dew point by the temperature adjusting mechanism 13. At this time, condensation occurs on the surface of the mold 11, and water 15 derived from moisture in the air adheres to the surface of the mold 11.

  Next, as shown in FIG. 1C, moisture in the air between the convex portion of the mold 11 and the substrate 14 and water 15 attached to the surface of the convex portion of the mold 11 Is electrolyzed by the voltage applied during the period to generate oxygen or oxygen radicals. The generated oxygen anodizes the surface of the substrate 14 corresponding to the anode, and a fine pattern of the anodic oxide film 16 having a thickness of about 2 nm is formed on the surface portion of the substrate 14 corresponding to the convex portion of the mold 11. . In addition, since the height of the convex part of the mold 11 is usually 0.2 μm or more, the electric field between the concave part of the mold 11 and the surface of the substrate 14 is weak, and the height of the substrate 14 corresponding to the concave part of the mold 11 is low. The anodic oxide film 16 is not formed on the surface portion. Further, even when the convex portion of the mold 11 comes into contact with the surface of the substrate 14, a sufficient electric field is not applied between the concave portion of the mold 11 and the surface 14 of the substrate around the convex portion in contact with the mold 11. Similarly, the portion of the surface of the substrate 14 corresponding to the recess of the mold 11 is not oxidized. Therefore, only the surface portion of the substrate 14 corresponding to the convex portion of the mold 11 is oxidized to form the anodic oxide film 16, so that a fine pattern can be formed.

  Next, as shown in FIG. 1 (d), the mold 11 is raised to move the mold 11 away from the substrate 14. Next, if necessary, the mold 11 is moved to another location on the surface of the substrate 14 as shown in FIG. 1E, and the nanoimprint method is similarly performed as shown in FIG. Perform to form a fine pattern. In this manner, the nanoimprint method is performed according to the step-and-repeat method, and the pattern of the anodic oxide film 16 is formed on a necessary portion on the surface of the substrate 14.

  Finally, as shown in FIG. 1G, the substrate 14 with the pattern formed on the surface is taken out from the nanoimprint apparatus, and the anodic oxide film 16 formed on the surface of the substrate 14 using a known etching method. Using the pattern as a mask, the substrate 14 is etched to obtain a substrate pattern 17.

FIGS. 2A to 2D are diagrams for explaining an example of the structure of a pattern electrode as a mold used in the embodiment of the present invention.

As the structure of the pattern electrode used in the embodiment of the present invention , as shown in FIG. 2A, a pattern electrode having a concavo-convex structure on the surface of the conductive substrate 101, as shown in FIG. Further, a patterned electrode in which at least a part of the surface of the conductive substrate 102 is made into an insulator 103 by chemical reaction or physical embedding, is insulated from at least a part of the surface of the conductive substrate 104 as shown in FIG. A patterned electrode on which an object 105 is deposited, and a patterned electrode in which at least part of the concavo-convex structure on the surface of the conductive substrate 106 is formed as an insulator 107 by chemical reaction or physical embedding as shown in FIG. and so on. Here, the entire conductive substrate is not necessarily conductive, and a conductive substrate in which a conductive substance is deposited or applied on the surface of the insulating substrate can also be used.

Next, means and a method for changing the gap (gap) provided between the pattern electrode as the mold and the substrate as the base in the embodiment of the present invention will be described.

(Gap control example 1)
The gap control example 1 is based on the method shown in FIG.

  In FIG. 3, a conductive pattern electrode 201 is disposed on a processing target substrate 203 directly or via a spacer 202. In a state where a load 204 is applied on the pattern electrode 201, a voltage is applied between the processing target substrate 203 and the pattern electrode 201 using the power source 205. While monitoring with the ammeter 206, the load is increased and the load is fixed when the current value shows a predetermined value. Due to the current flowing at this time, an electrochemical reaction occurs on the processing target substrate 203 at a location corresponding to the convex portion of the pattern electrode 201 to form a reaction portion 207 and an unreacted portion 208, whereby a patterned substrate 309 is obtained. It is done.

As a pattern electrode, a surface of a stainless steel substrate having a 100 nm pitch line-and-space pattern formed by electron beam lithography and dry etching was used. A Si substrate was used as the substrate to be processed. As a spacer, a polyimide thin film having a film thickness of 50 nm was formed on the substrate, and a window was formed by photolithography so that a target location of the substrate to be processed was exposed. The pattern electrode was brought into contact with the substrate to be processed through a spacer. A pressure was applied to the entire pattern electrode while a voltage of 20 V was applied between the pattern electrode and the substrate to be processed. When the pressure was increased while monitoring the current value, the current value increased rapidly to 2A when the pressure reached 50 g / mm ² . The current continued to flow for 180 seconds. By SEM observation, it was confirmed that a SiO ₂ pattern corresponding to the pattern electrode conductive portion was formed. When a GaAs substrate is used as the substrate to be processed, a load is applied by bringing the pattern electrode into direct contact with the substrate to be processed, and when the pressure reaches 2 g / mm ² , the current value increases rapidly. It became. The current continued to flow for 180 seconds. By SEM observation, it was confirmed that a GaAs oxide pattern corresponding to the pattern electrode conductive portion was formed.

(Gap control example 2)
The gap control example 2 is based on the method shown in FIG.

  In FIG. 4, a conductive pattern electrode 301 is disposed on a processing target substrate 302. At this time, since the pattern electrode support stage 303 and the processing target support stage 304 are arranged non-parallel by the insulating spacers 310 and 311 having different heights, the pattern electrode 301 supported by each stage and the processing target The surface of the substrate 302 is in a non-parallel state. When the pattern electrode support stage 303 and the processing target support stage 304 are brought close to each other, a reaction optimum region 305 in which the distance between the pattern electrode 301 and the processing target substrate 302 is suitable for an electrochemical reaction is necessarily generated on the processing target substrate. In this state, a voltage is applied between the processing target substrate 302 and the pattern electrode 301 using the power source 306. Due to the current flowing at this time, an electrochemical reaction occurs at a location corresponding to the convex portion of the pattern electrode 301 in the reaction optimal region 305, forming a reaction portion 307 and an unreacted portion 308, and the patterned substrate 309 is formed. can get.

As a pattern electrode, a surface of a stainless steel substrate having a 100 nm pitch line-and-space pattern formed by electron beam lithography and dry etching was used. A Si substrate was used as the substrate to be processed. The pattern electrode was attached to the upper stage, the substrate to be processed was attached to the lower stage, and the spacer height was set so that the upper stage and the lower stage were inclined 0.05 from the parallel state. The upper stage and the lower stage were brought close to each other, and the pattern electrode was brought into contact with the spacer. With a voltage of 20 V applied between the pattern electrode and the substrate to be processed, a current was kept flowing for 180 seconds. By SEM observation, it was confirmed that a SiO ₂ pattern corresponding to the pattern electrode conductive portion was formed on a part of the substrate to be processed.

(Gap control example 3)
The gap control example 3 is based on the method shown in FIG.

  In FIG. 5, a conductive pattern electrode 401 is disposed on a processing target substrate 403 directly or via an insulating spacer 402. A load 404 is applied to a part of the pattern electrode 401. At this time, a load having a predetermined size or more according to the material and thickness of the substrate to be processed or the pattern electrode may be applied. There is no need to monitor the current or adjust the load, and the reaction optimal region where the distance between the pattern electrode and the substrate is suitable for the reaction in a part of the processing target substrate 403 due to the deflection of the processing target substrate or the pattern substrate. 405 occurs. In this state, a voltage is applied between the processing target substrate 403 and the pattern electrode 401 using the power source 406. Due to the current flowing at this time, an electrochemical reaction occurs at a location corresponding to the convex portion of the pattern electrode 401 in the reaction optimum region 405, thereby forming a reaction portion 407 and an unreacted portion 408, and a patterned substrate 409 is formed. can get.

As a pattern electrode, a surface of a stainless steel substrate having a 100 nm pitch line-and-space pattern formed by electron beam lithography and dry etching was used. A Si substrate was used as the substrate to be processed. A polyimide thin film having a film thickness of 50 nm was formed on the substrate as an insulating spacer, and a window was formed by photolithography so that the target location of the substrate to be processed was exposed. The polyimide film remaining around serves as a spacer. Due to the deflection of the pattern electrode or the substrate to be processed that occurs when the pattern electrode and the substrate to be processed are brought into contact with each other, there is always a place having the optimum reaction distance, and furthermore, the place can be controlled by the pressurizing position or the load. The thickness of the film does not require accuracy, and is about 0.5 μm. The pattern electrode was brought into contact with the substrate to be processed through a spacer. In a state where a voltage of 20 V was applied between the pattern electrode and the substrate to be processed, a part of the pattern electrode was pushed using a punch having a spherical tip, and pressure was applied so as to be 10 g / mm ² . In this state, the voltage was continuously applied for 180 seconds. It was confirmed by SEM observation that a SiO ₂ pattern corresponding to the pattern electrode conductive portion was formed on the substrate to be processed at a location as shown in FIG. 6A. In addition, when a part of the pattern electrode is pressed using a punch having a cylindrical tip and a voltage is applied, the pattern electrode is placed on the substrate to be processed at a position as shown in FIG. It was confirmed that a SiO ₂ pattern corresponding to the conductive portion was formed. In addition, when the pattern electrode is brought into direct contact with the processing target substrate without using an insulating spacer, the pattern substrate and the processing target are not in direct contact with each other, but are more suitable due to the deflection of the pattern substrate centering on the pressurizing part. The pattern was transferred to the place where the gap was generated. With a voltage of 20 V applied between the pattern electrode and the substrate to be processed, a part of the pattern electrode was pressed using a punch with a spherical tip, and pressure was applied to 50 g / mm ² . The reason why high pressure is required compared to the case where the pattern substrate and the object to be processed are in direct contact with each other through the spacer is that there is less space between the pattern substrate and the object to be processed, and the pattern substrate or the object to be processed is less likely to bend. Because. In this state, the voltage was continuously applied for 180 seconds. It was confirmed by SEM observation that a SiO ₂ pattern corresponding to the pattern electrode conductive portion was formed at a location similar to the above FIG. Further, even when a part of the pattern electrode is pressed using a punch having a cylindrical tip and a voltage is applied, the SiO 2 corresponding to the pattern electrode conductive portion is located at a position similar to the above-described FIG. It was confirmed that _two patterns were formed.

(Gap control example 4)
The gap control example 4 is based on the method shown in FIG.

  In FIG. 7, a conductive pattern electrode 501 is disposed on a processing target substrate 503 directly or via an insulating spacer 502. A load 504 is applied to a part of the pattern electrode 501. At this time, a load having a predetermined size or more according to the material and thickness of the substrate to be processed or the pattern electrode may be applied. There is no need to monitor the current, and due to the deflection of the substrate to be processed or the pattern substrate, a reaction optimum region A505 in which the distance between the pattern electrode and the substrate is suitable for the reaction occurs in a part of the substrate to be processed 503. . In this state, a voltage is applied between the processing target substrate 503 and the pattern electrode 501 using the power source 506. Due to the current flowing at this time, an electrochemical reaction occurs at a position corresponding to the convex portion of the pattern electrode 501 in the reaction optimum region A505, and a pattern A507 is formed. Next, when the load is changed, the deflection of the substrate to be processed or the pattern substrate changes, and the optimum reaction region in which the distance between the pattern electrode and the substrate is suitable for the reaction moves to the optimum reaction region B508. Accordingly, the pattern B509 is formed in the reaction optimum region B508. By continuously changing the load, it is possible to obtain the pattern forming substrate 510 on which the pattern is formed over the entire surface.

As a pattern electrode, a surface of a stainless steel substrate having a 100 nm pitch line-and-space pattern formed by electron beam lithography and dry etching was used. A Si substrate was used as the substrate to be processed. A polyimide thin film having a film thickness of 50 nm was formed on the substrate as an insulating spacer, and a window was formed by photolithography so that the target location of the substrate to be processed was exposed. The pattern electrode was brought into contact with the substrate to be processed through a spacer. In a state where a voltage of 20 V is applied between the pattern electrode and the substrate to be processed, a part of the pattern electrode is pressed using a punch having a spherical tip, and pressure is applied to 15 g / mm ² . While decreasing the pressure applied to the punch at a rate of 1 g / mm ² / sec, voltage application and pressurization were continued for 10 minutes. It was confirmed by SEM observation that the SiO ₂ pattern corresponding to the pattern electrode conductive portion was formed on the processing target substrate at the position shown in FIG. In addition, when a part of the pattern electrode is pressed using a punch with a cylindrical tip and a voltage is applied, the pattern electrode conductive portion corresponds to the portion shown in FIG. It was confirmed by SEM observation that the SiO ₂ pattern to be formed was formed. In addition, when the pattern electrode is brought into direct contact with the substrate to be processed, it is not at the place where the pattern substrate and the object to be processed are in direct contact but at the place where an appropriate gap is generated due to the deflection of the pattern substrate around the pressurizing part. The pattern was transferred. In a state where a voltage of 20 V is applied between the pattern electrode and the substrate to be processed, a part of the pattern electrode is pressed using a punch having a spherical tip, and pressure is applied to 50 g / mm ² , While decreasing the pressure applied to the punch at a rate of 1 g / mm ² / sec, voltage application and pressurization were continued for 10 minutes. The reason why high pressure is required compared to the case where the pattern substrate and the object to be processed are in direct contact with each other through the spacer is that there is less space between the pattern substrate and the object to be processed, and the pattern substrate or the object to be processed is less likely to bend. Because. In this state, voltage application and load change were continued for 10 minutes. It was confirmed by SEM observation that a SiO ₂ pattern corresponding to the pattern electrode conductive portion was formed at a location similar to FIG. Also, when a load is changed while a part of the pattern electrode is pressed using a punch whose tip is cylindrical and a voltage is applied, the pattern electrode is located at a position similar to that shown in FIG. It was confirmed by SEM observation that a SiO ₂ pattern corresponding to the conductive portion was formed.

(Gap control example 5)
The gap control example 5 is based on the method shown in FIG.

  In FIG. 9, a conductive pattern electrode 601 is disposed on a processing target substrate 603 directly or via an insulating spacer 602. A load 605 is applied to the pressurization position A604 of the pattern electrode 601. At this time, a load having a predetermined size or more according to the material and thickness of the substrate to be processed or the pattern electrode may be applied. There is no need to monitor the current, and due to the deflection of the substrate to be processed or the pattern substrate, a reaction optimum region A606 in which the distance between the pattern electrode and the substrate is suitable for the reaction occurs in a part of the substrate to be processed 603. . In this state, a voltage is applied between the processing target substrate 603 and the pattern electrode 601 using the power source 607. Due to the current flowing at this time, an electrochemical reaction occurs in a place corresponding to the convex portion of the pattern electrode 601 in the reaction optimum region A606, and a pattern A608 is formed. Next, when the pressure position is changed from the pressure position A604 to the pressure position B609, the deflection of the substrate to be processed or the pattern substrate changes, and the distance between the pattern electrode and the substrate is suitable for the reaction. The region moves to the reaction optimum region B610. Therefore, the pattern B611 is formed in the reaction optimum region B610. By continuously changing the pressure position, a pattern forming substrate 612 having a pattern formed on the entire surface can be obtained.

As a pattern electrode, a surface of a stainless steel substrate having a 100 nm pitch line-and-space pattern formed by electron beam lithography and dry etching was used. A Si substrate was used as the substrate to be processed. A polyimide thin film having a film thickness of 50 nm was formed on the substrate as an insulating spacer, and a window was formed by photolithography so that the target location of the substrate to be processed was exposed. The pattern electrode was brought into contact with the substrate to be processed through a spacer. In a state where a voltage of 20 V is applied between the pattern electrode and the substrate to be processed, a part of the pattern electrode is pressed using a punch having a spherical tip, and pressure is applied to 10 g / mm ² . The punch was moved in a fixed direction at a speed of 5 μm / second. In this state, voltage application and punch movement were continued for 10 minutes. It was confirmed by SBM observation that the SiO ₂ pattern corresponding to the pattern electrode conductive portion was formed on the processing target substrate at the position shown in FIG. In addition, when a part of the pattern electrode is pressed using a punch having a cylindrical tip and a voltage is applied, the pattern electrode conductive portion corresponds to the portion shown in FIG. It was confirmed by SEM observation that the SiO ₂ pattern to be formed was formed. In addition, when the pattern electrode is brought into direct contact with the substrate to be processed, it is not at the place where the pattern substrate and the object to be processed are in direct contact but at the place where an appropriate gap is generated due to the deflection of the pattern substrate around the pressurizing part. The pattern was transferred. With a voltage of 20 V applied between the pattern electrode and the substrate to be processed, a part of the pattern electrode was pressed using a punch with a spherical tip, and pressure was applied to 50 g / mm ² . The reason why high pressure is required compared to the case where the pattern substrate and the object to be processed are in direct contact with each other through the spacer is that there is less space between the pattern substrate and the object to be processed, and the pattern substrate or the object to be processed is less likely to bend. Because. Further, the punch was moved in a fixed direction at a speed of 5 μm / second. In this state, voltage application and punch movement were continued for 10 minutes. It was confirmed by SEM observation that a SiO ₂ pattern corresponding to the pattern electrode conductive portion was formed at a location similar to FIG. In addition, when a punch is moved while pressing a part of the pattern electrode using a punch having a cylindrical tip and applying a voltage, a pattern is formed at a location similar to that shown in FIG. It was confirmed by SEM observation that a SiO ₂ pattern corresponding to the electrode conductive portion was formed.

  A resist pattern having a width of 50 to 300 nm was formed on a silicon substrate by using a known electron beam lithography method. After etching the silicon layer with chlorine plasma to a depth of 200 nm, the resist was removed with oxygen plasma to form a silicon mold.

  A silicon substrate whose surface was washed with a hydrofluoric acid aqueous solution was introduced into a chamber whose humidity was controlled to 20% together with the mold formed as described above. While the mold temperature was 10 ° C., a voltage of 20 V was applied between the mold and the silicon substrate. After checking the parallelism between the mold and the substrate, the distance between the mold and the substrate was decreased from 1 mm to 0.1 mm / min, and the mold was lowered toward the substrate. While applying a load with a pressing pressure of 0.5 MPa, the convex portion of the mold was completely adhered to the substrate. This was repeated twice. While raising the mold, the mold was moved to the next chip position, and the mold was lowered similarly. An ultrathin oxide film was formed on the part where the mold was lowered.

  FIG. 11 is a diagram showing the relationship between the size of the gap between the substrate and the convex portion of the mold and the number of patterns transferred to the substrate. The horizontal axis in FIG. 11 is the size [μm] of the gap between the substrate and the convex portion of the mold, and the vertical axis in FIG. 11 is the number of patterns transferred to the substrate. As shown in FIG. 11, in order to transfer the pattern to the substrate, it was confirmed that there was a suitable range for the gap (gap) provided between the substrate and the convex portion of the mold. Specifically, the size of the gap provided between the substrate and the convex portion of the mold is preferably 0.4 μm to 1.2 μm, and more preferably 0.5 μm to 0.8 μm. .

  After forming the required number of oxide films at desired positions, the substrate is taken out of the chamber and etched using electron cyclotron resonance plasma of chlorine gas to obtain a substrate pattern corresponding to the mold pattern. It was. As a result, a pattern having a width of 50 to 300 nm could be formed on the substrate without any defects.

  A silicon-containing resist pattern having a width of 50 to 300 nm was formed on an organic polymer substrate of polymethylmethacrylate by using a known electron beam lithography method. An organic polymer substrate was etched to a depth of 200 nm with oxygen plasma and then baked at 400 ° C. to form a carbon mold.

  A gallium arsenide substrate was introduced into a chamber whose humidity was controlled to 20% together with the mold formed as described above. While the mold temperature was 10 ° C., a voltage of 10 V was applied between the mold and the gallium arsenide substrate. After checking the parallelism between the mold and the substrate, the distance between the mold and the substrate was decreased from 1 mm to 0.1 mm / min, and the mold was lowered toward the substrate. While applying a load with a pressing pressure of 0.5 MPa, the convex portion of the mold was completely adhered to the substrate. While raising the mold, the mold was moved to the next chip position, and the mold was lowered similarly. An ultrathin oxide film was formed on the part where the mold was lowered.

  After forming the required number of oxide films at desired positions, the substrate is taken out of the chamber and etched using electron cyclotron resonance plasma of chlorine gas to obtain a substrate pattern corresponding to the mold pattern. It was. As a result, a pattern having a width of 50 to 300 nm could be formed on the substrate without any defects.

  A silicon-containing resist pattern having a width of 50 to 300 nm was formed on an organic polymer substrate of polymethylmethacrylate by using a known electron beam lithography method. An organic polymer substrate was etched to a depth of 200 nm with oxygen plasma and then baked at 400 ° C. to form a carbon mold.

  A silicon substrate whose surface was cleaned with a hydrofluoric acid aqueous solution was introduced into the chamber together with the mold formed as described above. The humidity was controlled to 50%, the mold temperature was 20 ° C., and a voltage of 5 V was applied between the mold and the silicon substrate. After checking the parallelism between the mold and the substrate, the distance between the mold and the substrate was decreased from 1 mm to 0.1 mm / min, and the mold was lowered toward the substrate. While applying a load with a pressing pressure of 0.5 MPa, the convex portion of the mold was completely adhered to the substrate. While raising the mold, the mold was moved to the next chip position, and the mold was lowered similarly. An ultrathin oxide film was formed on the part where the mold was lowered.

  After the required number of oxide films were formed at desired positions, the substrate was taken out of the chamber and etched using chlorine gas plasma to obtain a substrate pattern corresponding to the mold pattern. As a result, a pattern having a width of 50 to 300 nm could be formed on the substrate without any defects.

  Although the embodiments and examples of the present invention have been specifically described above, the present invention is not limited to these embodiments and examples, and these embodiments and examples of the present invention are not limited thereto. Can be changed or modified without departing from the spirit and scope of the present invention.

[Appendix]
Embodiments described herein relate generally to a nanoimprint method and a nanoimprint apparatus.

One object of an embodiment of the present invention is to provide a nanoimprint method in which the reproducibility of a pattern to be formed is improved.

Another object of an embodiment of the present invention is to provide a nanoimprint apparatus in which the reproducibility of a pattern to be formed is improved.

Embodiment (1): In a nanoimprint method for forming a pattern on a substrate or a film provided on the substrate using a mold, the gap is provided between the substrate or the film provided on the substrate and the mold. A nanoimprinting method comprising: causing a mold to face a substrate or a film provided on the substrate; and applying a voltage between the mold or the film provided on the substrate or the substrate.

Embodiment (2): The nanoimprint method according to Embodiment (1), further comprising attaching water to at least one of the substrate or the film provided on the substrate and the mold.

Embodiment (3): The embodiment (1) or (3), further comprising controlling the temperature of at least one of the substrate or the film provided on the substrate and the mold to a temperature not higher than a dew point temperature. The nanoimprint method according to 2).

Embodiment (4): The embodiment (1) to (3), further comprising controlling the humidity of the atmosphere surrounding the substrate or the film provided on the substrate and the mold to 30% or more. The nanoprinting method according to any one of the above.

Embodiment (5): The nanoimprint method according to any one of Embodiments (1) to (4), wherein the mold includes carbon.

Embodiment (6): In a nanoimprint apparatus for forming a pattern on a substrate or a film provided on the substrate using a mold, the gap is provided between the substrate or the film provided on the substrate and the mold. A nanoimprint apparatus comprising: a substrate or a film provided on the substrate; and a means for applying a voltage between the substrate or the film provided on the substrate and the mold.

Embodiment (7): The nanoimprint apparatus according to Embodiment (6), further comprising means for attaching water to at least one of the substrate or the film provided on the substrate and the mold.

Embodiment (8): The nanoimprint apparatus according to Embodiment (6) or (7), further comprising means for controlling the temperature of at least one of the substrate or the film provided on the substrate and the mold .

Embodiment (9): Any one of Embodiments (6) to (8), further comprising means for controlling the humidity of an atmosphere surrounding the substrate or the film provided on the substrate and the mold. The nanoimprint apparatus described in 1.

Embodiment (10): The nanoimprint apparatus according to any one of Embodiments (6) to (9), wherein the mold includes carbon.

According to at least one of the embodiments of the present invention, it is possible to provide a nanoimprint method in which the reproducibility of a pattern to be formed is improved.

According to at least one of the embodiments of the present invention, it is possible to provide a nanoimprint apparatus in which the reproducibility of a formed pattern is improved.

1A to 1G are diagrams illustrating an example of a nanoimprint method and an example of a nanoimprint apparatus according to an embodiment of the present invention. FIG. 2 is a diagram for explaining an example of the structure of a patterned electrode as a mold used in the embodiment of the present invention. FIG. 3 is a diagram for explaining a gap control example 1 in the embodiment of the present invention. FIG. 4 is a diagram for explaining a gap control example 2 in the embodiment of the present invention. FIG. 5 is a diagram for explaining a gap control example 3 in the embodiment of the present invention. FIGS. 6A and 6B are diagrams illustrating patterns formed according to the gap control example 3 in the embodiment of the present invention. FIG. 7 is a diagram for explaining a gap control example 4 in the embodiment of the present invention. FIGS. 8A and 8B are diagrams illustrating patterns formed according to the gap control example 3 in the embodiment of the present invention. FIG. 9 is a diagram illustrating a gap control example 5 according to the embodiment of the present invention. FIGS. 10A and 10B are diagrams illustrating patterns formed according to the gap control example 5 in the embodiment of the present invention. FIG. 11 is a diagram showing the relationship between the size of the gap between the substrate and the convex portion of the mold and the number of patterns transferred to the substrate. FIG. 12 is a diagram illustrating a conventional imprint lithography process.

DESCRIPTION OF SYMBOLS 11 Mold 12 Voltage control system 13 Temperature control mechanism 14 Substrate 15 Water 16 Anodized film 17 Substrate pattern 101,102,104,106 Conductive substrate 103,105,107 Insulator 201,301,401,501,601 Pattern electrode 202, 402, 502, 602 Spacers 203, 302, 403, 503, 603 Substrate 204, 404, 504, 605 Load 205, 306, 406, 506, 607 Power supply 206 Ammeter 207, 307, 407 Reaction unit 208, 308,408 Unreacted part 209,409 Pattern forming substrate 1
303 Pattern electrode support device 304 Work target support stage 305,405 Reaction optimum region 309,510,612 Pattern forming substrate 505,606 Reaction optimum region A
507,608 Pattern A
508,610 Reaction optimum region B
509,611 Pattern B
604 Pressurizing position A
609 Pressurizing position B
1001 Mold 1002 Resist film

Claims (12)

In the nanoimprint method of forming a pattern on a substrate or a film provided on the substrate using a mold,
The mold is opposed to the base or the film provided on the base so that a gap is provided between the base or the film provided on the base and the convex portion of the mold, and provided on the base or the base. together it includes applying a voltage between the film and the mold,
Characterized in that it further comprises controlling before Symbol Temperature Temperature dew point temperature below the nanoimprint method. The nanoimprint method according to claim 1,
By expanding and contracting the elastic spacer provided between the mold and the film provided on the substrate or substrate with addition of at least one force of the membrane and the type provided in the base or substrate, wherein The nanoimprint method further comprising changing the size of the gap while applying a voltage between the substrate or a film provided on the substrate and the mold . The nanoimprint method according to claim 1,
By deforming at least one of the obtained film and the type provided on the substrate or substrate with addition of at least one force of the membrane and the type provided in the substrate or substrate layer provided on the substrate or substrate The method of claim 1, further comprising changing the size of the gap while applying a voltage between the mold and the mold . The nanoimprint method according to claim 3, wherein
Varying the size of the gap while applying a voltage between the substrate or the film provided on the substrate and the mold is applied to at least one of the substrate or the film provided on the substrate and the mold A nanoimprinting method comprising changing the magnitude of the force. The nanoimprint method according to claim 3, wherein
Varying the size of the gap while applying a voltage between the base or the film provided on the base and the mold may be performed by the at least one of the base or the film provided on the base and the mold. A nanoimprint method comprising changing a position to apply force. In the nanoimprint method according to any one of claims 1 to 5,
A pattern electrode having a concavo-convex structure on the surface of the conductive substrate, a pattern electrode having an concavo-convex structure on the surface of the conductive substrate and having an insulator provided in the concave portion of the concavo-convex structure up to the height of the convex portion of the concavo-convex structure, conductive Pattern electrode provided with an insulator having a concavo-convex structure on the surface of the substrate, or an insulator in a concave portion of the concavo-convex structure having a concavo-convex structure on the surface of the conductive substrate and a height smaller than the height of the convex portion of the concavo-convex structure A nanoimprint method, wherein a pattern electrode provided with is used as the mold. In a nanoimprint apparatus that forms a pattern on a substrate or a film provided on the substrate using a mold,
Means for making the mold face the base or the film provided on the base so as to provide a gap between the base or the film provided on the base and the convex portion of the mold; and provided on the base or the base Means for applying a voltage between the membrane and the mold ,
Characterized in that it comprises further means for controlling the temperature of the pre-Symbol type dew point below the temperature, nanoimprint apparatus. The nanoimprint apparatus according to claim 7 , wherein
A stretchable spacer provided between the base or the film provided on the base and the mold, and a force applied to at least one of the base or the film provided on the base and the mold, and the stretchable spacer The nanoimprint apparatus , further comprising means for changing a size of the gap while applying a voltage between the base or the film provided on the base and the mold, and having means for expanding and contracting. The nanoimprint apparatus according to claim 7 , wherein
Having means for deforming at least one of film and the type provided in the base body or substrate with addition of at least one force of the membrane and the type provided in the base or substrate, provided on the substrate or substrate The nanoimprint apparatus further comprising means for changing a size of the gap while applying a voltage between the film and the mold . The nanoimprint apparatus according to claim 9 , wherein
Means for changing the size of the gap while applying a voltage between the base or the film provided on the base and the mold is applied to at least one of the base or the film provided on the base and the mold A nanoimprint apparatus comprising means for changing the magnitude of the force. The nanoimprint apparatus according to claim 9 , wherein
The means for changing the size of the gap while applying a voltage between the base or the film provided on the base and the mold is the means for at least one of the base or the film provided on the base and the mold. A nanoimprint apparatus comprising means for changing a position to apply a force. In the nanoimprint apparatus according to any one of claims 7 to 11,
The pattern includes a pattern electrode having a concavo-convex structure on the surface of a conductive substrate, a pattern having a concavo-convex structure on the surface of the conductive substrate, and an insulator provided in the concave portion of the concavo-convex structure up to the height of the convex portion of the concavo-convex structure. An electrode, a patterned electrode provided with an insulator having a concavo-convex structure on the surface of the conductive substrate, or a surface of the conductive substrate having a concavo-convex structure and a height smaller than the height of the convex portion of the concavo-convex structure. A nanoimprint apparatus, which is a patterned electrode in which an insulator is provided in a recess.

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