TWI538797B - Nanoimprinting method, nanoimprinting apparatus for executing the nanoimprinting method, and method for producing patterned substrates - Google Patents

Description

Nano imprint method, nano imprint apparatus for performing the nano imprint method, and method of manufacturing patterned substrate

The present invention relates to a nanoimprinting method using a nanoimprinting mold having a fine concavo-convex pattern on the surface, a nanoimprinting apparatus for performing the nanoimprinting method, and a method of manufacturing a patterned substrate.

In the application of manufacturing magnetic recording media such as Discrete Track Media (DTM) and Bit Patterned Media (BPM) and semiconductor devices, the use of a nanoimprint method to transfer a pattern The use of pattern transfer techniques to resists applied to articles to be processed has high expectations.

Specifically, in nanoimprinting, a prototype (formerly referred to as a mold, a stamper or a stencil) on which a concavo-convex pattern is formed is pressed (embossed) on a curable resin applied to a substrate to be treated. Pressing the prototype onto the curable resin causes the curable resin to mechanically deform or flow to accurately transfer the fine pattern. Once the mold is produced, the nano-scale fine structure can be repeatedly formed in a simple manner. Thus, the nanoimprint method is a low cost transfer technique that produces very little hazardous waste and emissions. Thus, there is a high expectation regarding the application of the nanoimprint method in various fields.

Depending on the environment in which the mold is used (specifically, the atmospheric pressure and temperature of the mold), there is a case where the size of the concave-convex pattern of the mold is different from the predetermined design size. Under these conditions, a resist pattern having a design size is used for a mold having a pattern having a size deviating from a predetermined design size. A technique of forming a resist film on a substrate will become necessary.

An example of such a technique is disclosed in Patent Document 1. Patent Document 1 discloses a method of adjusting the size of a pattern of a mold 90 deviating from a predetermined design size by compressing the side wall of the mold 90 with the member 91 using a mechanical external force F (FIG. 18).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1]

Japanese Patent No. 4594305

The method disclosed in Patent Document 1 holds the side wall of the mold 90 and mechanically compresses the mold. Thus, the manner of shrinkage is not necessarily uniform, and as illustrated in Fig. 18, there is a problem that undulations 92 are generated in the mold 90. Although a system for pressurizing or decompressing the upper surface of the mold 90 to suppress such undulations is provided, since the pressure is applied to the entire upper surface, the occurrence of local undulations cannot be suppressed. In the case where a mold having such undulations is used to perform a nanoimprint operation, an imprint defect such as a thickness fluctuation of the residual resist film will occur.

Further, if the method disclosed in Patent Document 1 is applied to a thin mold having a thickness of about several hundred micrometers, there is a problem that the thin mold will be damaged.

The present invention has been developed in view of the foregoing circumstances. It is an object of the present invention to provide a nanoimprint method for achieving a resist pattern having a desired percentage of the size of a pattern of a mold under predetermined standard conditions. Another object of the present invention is to provide a nanoimprinting apparatus for performing the nanoimprinting method.

Furthermore, it is a further object of the present invention to provide a method of fabricating a patterned substrate using nanoimprint, which enables highly accurate processing.

The nanoimprint method of the present invention which achieves the above object is characterized in that a mold having a fine concavo-convex pattern having a predetermined standard size at a predetermined standard pressure and a predetermined standard temperature, and a substrate to be treated having a resist coated surface are used. The mold has a different Young's modulus and/or a different coefficient of thermal expansion from the substrate to be treated; and the concave and convex pattern is contacted with a resist coated on the resist coated surface to form a substrate An assembly of the mold, the resist, and the substrate to be treated; placing the assembly in a pressure vessel, and controlling the pressure P in the pressure vessel and the temperature T of the assembly While the following formula 1 is satisfied, the resist is cured, ΔD _all = (1/E _i -1/E _m ). (PP _st )+(α _m -α _i ). (TT _st ) (1)

Wherein the percentage of the difference between the size of the resist pattern and the standard size is expressed as ΔD _all , the standard pressure is expressed as P _st , the standard temperature is expressed as T _st , and the Young's modulus of the mold is expressed as E _m . The coefficient of thermal expansion of the mold is expressed as α _m , the Young's modulus of the substrate to be treated is expressed as E _i and the coefficient of thermal expansion of the substrate to be treated is expressed as α _i ; and thereafter the mold is separated from the resist .

In the present specification, the expression "standard size" means the size of the concave-convex pattern under standard conditions (standard pressure and standard temperature).

The expression "the percentage of the difference between the size of the resist pattern and the standard size" Ratio refers to the percentage of the difference between the resist pattern and the standard size under standard conditions.

In the nanoimprint method of the present invention, it is preferred to prioritize the control by the pressure in a state where the pressure P in the pressure vessel is in the range of 0 MPa to 5 MPa.

In the nanoimprint method of the present invention, it is preferred that the pressure in the pressure vessel is restored to atmospheric pressure after separating the mold from the resist.

In the nanoimprint method of the present invention, it is preferred that the temperature of the assembly is restored to the ambient temperature after separating the mold from the resist.

In the nanoimprint method of the present invention, it is preferable that the assembly is performed by supporting the assembly with a support member only at a portion other than a portion corresponding to the concave-convex pattern in the assembly. Place it. In this case, it is preferable that the support member has an annular shape or is composed of three or more protrusions.

In the present specification, "a portion corresponding to a pattern" refers to a predetermined portion of the assembly, the portion being a region in which the concave-convex pattern is formed and a portion projected in the plan view (from perpendicular to the coating) The direction of the surface of the resist is viewed).

The nanoimprinting apparatus of the present invention is a nanoimprinting apparatus for performing the nanoimprinting method of the present invention, characterized by comprising: a pressure vessel for accommodating an assembly, the assembly being set at a predetermined standard The pressure is formed by a mold having a predetermined concave-convex pattern of a predetermined standard size at a predetermined standard temperature, a substrate to be treated having a resist-coated surface, and a resist, which are always coated by applying the concave-convex pattern to the resist The agent is formed by coating the resist on the surface; and a control member for controlling the pressure P in the pressure vessel and/or the temperature T of the assembly to satisfy the following formula 2, ΔD _all = (1/E _i -1/E _m ). (PP _st )+(α _m -α _i ). (TT _st ) (2)

Wherein the percentage of the difference between the size of the resist pattern and the standard size is expressed as ΔD _all , the standard pressure is expressed as P _st , the standard temperature is expressed as T _st , and the Young's modulus of the mold is expressed as E _m . The coefficient of thermal expansion of the mold is expressed as α _m , the Young's modulus of the substrate to be treated is represented as E _i and the coefficient of thermal expansion of the substrate to be treated is expressed as α _i .

In the nanoimprinting apparatus of the present invention, it is preferable that the control member preferentially controls the pressure under the condition that the pressure P in the pressure vessel is in the range of 0 MPa to 5 MPa. Chemical.

Preferably, the nanoimprinting apparatus of the present invention further comprises: a support member for supporting the assembly, disposed in the pressure vessel; and: the assembly is only corresponding to the assembly A portion other than the portion of the concave-convex pattern is supported by the support member. In this case, it is preferable that the support member has an annular shape or is composed of three or more protrusions.

The method for manufacturing a patterned substrate of the present invention is characterized in that a substrate formed on a substrate to be transferred is formed by the nanoimprint method of the present invention. a resist film to which a concave-convex pattern is transferred; and etching is performed using the resist film as a mask to form a bump corresponding to a concave-convex pattern transferred to the resist film on a substrate to be processed pattern.

The nanoimprinting method and nanoimprinting apparatus of the present invention are characterized in that a mold having a fine concavo-convex pattern having a predetermined standard size at a predetermined standard pressure and a predetermined standard temperature is used, and a resist coated surface is to be used. Processing the substrate, the mold having a different Young's modulus and/or a different coefficient of thermal expansion from the substrate to be treated; and the pressure P in the pressure vessel and/or the temperature T of the assembly being controlled to satisfy the above formula The resist is cured at 1 o'clock, wherein the percentage of the difference between the size of the resist pattern and the standard size is expressed as ΔD _all , the standard pressure is expressed as P _st , and the standard temperature is expressed as T _st . The modulus is expressed as E _m , the coefficient of thermal expansion of the mold is expressed as α _m , the Young's modulus of the substrate to be treated is represented as E _i and the coefficient of thermal expansion of the substrate to be treated is expressed as α _i . With this configuration, the difference between the degree of change caused by the expansion and contraction of the mold and the degree of change caused by the expansion and contraction of the substrate to be treated can be utilized to control the size of the resist pattern. Therefore, it becomes possible to form a resist pattern which differs in size from the size of the pattern of the mold under a specific standard condition.

The method for producing a patterned substrate of the present invention is characterized in that a resist film on which a concave-convex pattern has been transferred is formed on a substrate to be transferred by the nanoimprint method of the present invention; and a resist film is formed The etching is performed as a mask to form a concavo-convex pattern corresponding to the concavo-convex pattern transferred to the resist film on the substrate to be processed. Because the resist pattern is imprinted by the nanoimprint of the present invention The method is formed such that the resist pattern is formed without any embossing defects. Therefore, highly accurate processing is made possible in the manufacture of patterned substrates using nanoimprinting.

Hereinafter, embodiments of the invention will be described with reference to the accompanying drawings. However, the invention is not limited to the embodiments described below. It should be noted that the dimensions and the like of the constituent elements in the drawings are different from the actual dimensions in order to facilitate visual understanding.

<First embodiment of nano imprint method and nano imprint apparatus>

1 is a cross-sectional view schematically showing a nanoimprinting apparatus 100 in accordance with a first embodiment of the present invention.

The nanoimprint method of this embodiment is performed using the nanoimprinting apparatus 100 illustrated in FIG. The nanoimprinting apparatus 100 of FIG. 1 is equipped with: a pressure vessel 110; a gas introduction section 120 for introducing a gas into the pressure vessel 110; and an exhaust section 130 for discharging gas from the inside of the pressure vessel 110; a mounting platform 145 equipped with a substrate supporting member 140 for supporting the substrate 7 to be processed; a mold supporting member 150 for supporting the mold 1; a lamp heater 155; a light receiving device 161 for positioning the concave-convex pattern; A light source 162 is used to expose the photocurable resin. It should be noted that FIG. 1 also shows a mold 1 having a fine concave-convex pattern 13 and a substrate 7 to be treated whose surface is coated with a photocurable resin 6. The assembly is formed by placing the mold 1 and the substrate 7 in contact such that the concave-convex pattern 13 and the photocurable resin 6 are in contact with each other.

(mold)

Si is an example of a material of a mold. For example, a Si mold is produced in the following manner. First, a Si substrate is coated with a photoresist liquid having polymethyl methacrylate (PMMA) or the like as a main component by a spin coating method or the like to form a photoresist layer. . Subsequently, when the Si substrate is scanned on the XY stage, an electron beam modulated corresponding to a predetermined line pattern is irradiated onto the Si substrate to have a square area of 10 mm on the surface of the photoresist layer The bump pattern is exposed. Thereafter, the photoresist layer is developed to remove the exposed portion. Finally, the photoresist layer after removing the exposed portion is used as a mask to perform etching up to a predetermined depth to obtain a Si mold having a predetermined pattern.

Alternatively, a quartz substrate can be used as the material of the mold 1. In the case where a fine pattern is to be formed on a quartz substrate, it is necessary to use a laminate structure composed of a metal layer and a photoresist layer as a mask when processing the substrate. An example of a method for processing a quartz substrate is as follows. The photoresist layer is used as a mask to perform dry etching to form a concavo-convex pattern corresponding to the concavo-convex pattern formed in the photoresist layer on the metal layer. Next, a metal layer is used as an etch stop layer to further dry-etch the quartz substrate to form a concavo-convex pattern on the quartz substrate. Thereby, a quartz mold having a predetermined pattern is obtained. Alternatively, an imprinted pattern transfer may be used instead of electron beam lithography as a method for forming the pattern.

It is also possible to use a mesa type mold. For example, the countertop mold is constructed in the manner of a mold 1 having a mesa structure as shown in FIGS. 2A and 2B. 2A is a perspective view schematically showing a table top mold 1; 2B is a cross-sectional view schematically showing a section of the mesa-type mold 1 taken along line A-A of FIG. 2A.

Specifically, the mold 1 illustrated in FIGS. 2A and 2B is provided with a planar support portion 11 and a mesa portion 12 which is disposed on the surface S1 (base surface) of the support portion 11 and from the base surface S1 There is a predetermined height D2. The patterned region R1 on which the fine concavo-convex pattern 13 is formed is disposed on the mesa portion 12.

In the case of using a mesa mold, there is an advantage that the range of flow of the curable resin can be limited when the mold is pressed against the curable resin coated on the substrate to be treated. The mesa mold can be produced by performing a mesa processing on the planar substrate (the process of removing the base material near the periphery of the mesa portion to allow the mesa portion to remain) and then forming a concavo-convex pattern on the surface of the mesa portion 1. In addition, a pattern other than the pattern to be transferred, such as an alignment mark, may be formed in the region R2 outside the patterned region of the mesa portion 12.

The mold 1 illustrated in Fig. 1 is a countertop mold.

Further, the mold 1 may be a mold that undergoes a release treatment to improve the separation property between the photocurable resin and the mold. This release treatment is carried out using an anthrone or a fluorodecane coupling agent. Examples of the silane coupling agent comprising silicon Daikin Industries, Ltd. (Daikin Industries KK) of Ou Putuo ^® (Optool ^®) DSX and Sumitomo 3M (Sumitomo 3M KK) of Nuowei Ke ^{® (Novec ®) EGC-1720} . Alternatively, other commercially available release agents can be advantageously used.

In the mold 1, the support portion 11 and the mesa portion 12 are integrally formed by the mesa processing by the planar substrate. As an alternative to the above quartz, the material of the mold 1 may be: metals such as ruthenium, nickel, aluminum, chromium, steel, ruthenium and tungsten; oxides, nitrides and carbides of such metals; and resins. Specific examples of materials of the mold 1 comprises a silicon oxide, alumina, quartz glass, Belle ^® (Pyrex ^®), glass and soda glass. The embodiment illustrated in FIG. 1 performs exposure via the mold 1. Thus, the mold 1 is formed of a light transmissive material. In the case where exposure is performed from the side of the substrate 7 to be processed, the material of the mold 1 does not have to be translucent.

The thickness D1 of the support portion 11 is in the range of 300 μm to 10 mm, more preferably in the range of 350 μm to 1 mm, and most preferably in the range of 400 μm to 500 μm. If the thickness D1 is less than 300 μm, there is a possibility that the mold will be damaged during the mold separation process, and if the thickness D1 is larger than 10 mm, the flexibility that enables the mold to withstand fluid pressure will be lost. The thickness D2 of the mesa portion 12 is in the range of from 100 nanometers to 10 millimeters, more preferably in the range of from 1 micrometer to 500 micrometers, and most preferably in the range of from 10 micrometers to 50 micrometers.

(substrate to be processed)

The substrate 7 to be treated is a substrate for imprinting coated with a resist. In the present invention, at least one of the Young's modulus and the thermal expansion coefficient of the material of the substrate 7 to be treated is different from the Young's modulus and the coefficient of thermal expansion of the material of the mold. Examples of the material of the substrate include nickel, aluminum, glass, and resin. These materials can be utilized individually or in combination. By adopting this configuration, the degree of change of the mold 1 accompanying the change in pressure and/or temperature during the embossing step will be different from the degree of change of the substrate 7 to be treated.

In the case where the mold 1 has a light transmitting property, the shape, structure, size and material of the substrate to be treated are not particularly limited, and may be selected depending on the intended use. The surface of the substrate 7 to be treated on which the pattern to be transferred is applied is a surface coated with a photocurable resin. For example, in the case where nanoimprinting is performed to manufacture a data recording medium, the substrate 7 to be processed is substantially in the shape of a disk. Regarding the structure of the substrate, a single layer substrate may be used or a laminate substrate may be used. The thickness of the substrate is not particularly limited and can be selected depending on the intended use.

On the other hand, in the case where the mold 1 is formed without using a light-transmitting material, a quartz substrate is used to achieve exposure of the photocurable resin.

(bump pattern)

The shape of the concavo-convex pattern 13 is not particularly limited and may be selected depending on the intended use of the nanoimprinting mold. An example of a typical pattern is the line and space pattern depicted in Figure 2B. The length of the line in the line and space pattern, the width of the line, the distance between the lines (the width of the space), and the height of the line at the bottom of the recess are set as appropriate. For example, the width of the line is in the range of 10 nm to 100 μm, more preferably in the range of 20 nm to 1 μm, and the distance between the lines is between 10 nm and 100 μm. In the range, more preferably in the range of 20 nm to 1 μm, and the height of the line (depth of the interval) is in the range of 10 nm to 500 nm, more preferably in the range of 30 nm to 100 nm. Within the scope.

(pressure vessel)

The pressure vessel 110 is composed of a container body 111 and a lid 112. The container body 111 is equipped with an introduction inlet through which gas is introduced from the gas The inlet section 120 is introduced; and an exhaust outlet through which the gas is exhausted by the gas exhaust section 130. The introduction inlet and the exhaust outlet are connected to the gas introduction section 120 and the exhaust section 130, respectively. The cover 112 is equipped with a glazing 113 that enables positioning and exposure to be performed with the cover 112 closed. However, in the case where positioning and exposure are performed in a state where the cover 112 is opened, the glazing 113 is not required.

(substrate placement platform and substrate support member)

The placement platform 145 is used to place the substrate 7 to be treated thereon. The mounting platform 145 is assembled to be in the x direction (horizontal direction in Figure 1), the y direction (perpendicular to the direction of the drawing in Figure 1), the z direction (vertical direction in Figure 1), and the θ direction (with z in The axis in the direction is moved as a rotation direction of the rotation center (including rotation in the present specification) in order to achieve positioning with respect to the concavo-convex pattern on the mold 1. Additionally, the placement platform 145 is equipped with a substrate support member 140 that is movable in the z-direction. The substrate support member 140 is utilized when the substrate 7 to be treated placed on the placement platform 145 is lifted off the placement platform 145, and also when the assembly is supported. The placement platform 145 can be equipped with a suction opening for sucking and holding the substrate 7 to be treated and a heater for heating the substrate 7 to be treated.

FIG. 3A is a plan view (a downward viewing angle in the z direction) of a first embodiment of a placement platform 145 for a substrate 7 to be treated. FIG. 3B is a plan view schematically showing a second embodiment of the placement platform 145 for the substrate 7 to be treated.

The mounting platform 145 illustrated in FIG. 3A is provided with a base support member 140 composed of a plurality of (four in this embodiment) dot-like protrusions and Suction opening 146. Preferably, the dot-like projections are assembled such that their contact surface with the assembly 8 is small to enable the assembly 8 to be supported within the pressure vessel 110 such that the fluid pressure of the environment substantially acts On the entire surface of the assembly 8. In particular, the tip of the dot-like protrusion may have a radius of curvature such that the contact surface is as close as possible to the point. This architecture is preferred because if the area of the contact surface becomes large, the fluid pressure will become difficult to apply to the assembly 8 in an isotropic manner. The number of the dot-like protrusions is not particularly limited. 8 are better, 6 are better, and 3 are best.

Meanwhile, the placement platform 145 illustrated in FIG. 3B is provided with a base support member 140 and a suction opening 146 formed by linear protrusions forming a ring. In FIG. 3B, the substrate support member 140 is in the form of a fracture ring shape. Alternatively, the substrate support member 140 can be in the form of a complete loop. Preferably, the linear projection is assembled such that the contact surface between it and the assembly 8 is small to enable the assembly 8 to be supported within the pressure vessel 110 such that the fluid pressure of the environment substantially acts upon Assembly 8 on the entire surface. Also in this case, the tip of the linear protrusion may have a radius of curvature such that the contact surface is close to a point. The number of linear protrusions only needs to be the number of formations that achieve a single annular shape.

Preferably, the protrusion is configured such that it only supports a portion of the assembly 8 other than its portion corresponding to the pattern. For example, in the case of using the substrate supporting member 140 illustrated in FIG. 3A, the substrate supporting member 140 composed of a plurality of protrusions is configured such that a plurality of protrusions are disposed uniformly disposed corresponding to the pattern The location around the part will be 8 Supported at a portion other than the portion corresponding to the pattern. In the case of using the substrate support member 140 illustrated in FIG. 3B, the annular base support member 140 is configured such that the assembly 8 is supported by a portion corresponding to the pattern corresponding to the inside of the annular shape. Outside the part of the pattern. These structures are employed such that the fluid pressure is applied isotropically to the portion corresponding to the pattern, and the expansion or contraction of the mold 1 corresponding to the pattern and the substrate 7 to be treated occurs in a uniform manner.

(mold support member)

The mold support member 150 supports the mold 1 in the pressure vessel 110 so as to face the substrate 7 to be treated placed on the placement platform 145. FIG. 3C is a plan view schematically showing the first embodiment of the mold supporting member 150. As shown in FIG. 3C, the mold support member 150 is composed of a ring portion 151 and a support post 152. The ring portion 151 may be in the shape of a discontinuous ring.

(gas introduction section, exhaust section and lamp heater)

For example, the gas introduction section 120 is composed of a gas introduction pipe 121; a valve 122; and a gas introduction source (not shown) connected to the other end of the gas introduction pipe 121. For example, the exhaust section 130 is composed of an exhaust duct 131, a valve 132, and an exhaust pump (not shown). Air and inert gas are examples of gases to be introduced. Examples of the inert gas include: N ₂ ; He; and Ar.

At the same time, the lamp heater 155 is a heat source for heating the assembly 8. The lamp heater 155 can be disposed within the pressure vessel 110 or external to the pressure vessel. Alternatively, the lamp heater 155 can be assembled to be movable and disposed directly above the mounting platform 145 to illuminate only the assembly 8 as necessary.

In the first embodiment, the gas introduction section 120, the exhaust section 130, the lamp heater 155, and a drive control section (not shown) for controlling the driving of these components serve as the control members of the present invention.

(light receiving device)

When the concave-convex pattern is positioned with respect to the substrate 7 to be processed in a state where the mold 1 is supported by the mold supporting member 150 and the resist-coated surface is coated with the photocurable resin 6 on the mounting platform 145, The light receiving device 161 is utilized. That is, when the cover 112 is opened or the concave-convex pattern 13 is observed by the light-receiving device 161 via the glazing 113, the placement platform 145 movable in the x, y, z, and θ directions is adjusted. The light receiving device 161 is also assembled to be movable in the x, y, z, and θ directions from the viewpoint of operability of the device. An optical microscope having a built-in CCD can be used as the light receiving device 161.

(exposure source)

The exposure light source 162 is utilized to expose the photocurable resin 6. From the standpoint of the operability of the device, the exposure source 162 is also assembled to move in the x, y, z, and θ directions. For example, a light source manufactured by Sen Lights Corporation that emits light having a wavelength in the range of 300 nm to 700 nm can be used as the exposure light source 162.

Hereinafter, a nano imprint method will be described. 4A and 4B are a set of cross-sectional views schematically illustrating steps of a nanoimprint method according to a first embodiment of the present invention. To aid in understanding the driver of the device, only the placement platform 145, the mold support member 150, and the nanoimprinting device 100 of FIG. 1 are illustrated in FIGS. 4A and 4B to explain the procedures for using such components. Other components needed. It should be noted in the following steps that it is assumed that the Young's modulus of the mold 1 and the coefficient of thermal expansion of the mold 1 are different from the Young's modulus of the substrate 7 to be treated and the coefficient of thermal expansion of the substrate 7 to be treated.

The nanoimprint method of the first embodiment is performed as follows. First, the user determines the percentage of the difference between the resist pattern to be formed and the standard size of the mold 1 under standard conditions. Next, the user sets a desired percentage in the drive control section of the control gas introduction section 120, the exhaust section 130, and the lamp heater 155 (the percentage of the difference between the size of the resist pattern and the standard size ΔD _all ) with other predetermined parameters. The drive control section obtains the target pressure P in the pressure vessel 110 and/or the target temperature of the assembly 8 from the predetermined relationship formula during the imprint based on the above parameters. Next, the cover 112 of the pressure vessel 110 is opened, the substrate 7 to be treated on which the resist coating surface is coated with the photocurable resin 6 is placed on the mounting platform 145, and the mold 1 is placed on the mold supporting member 150. The concave-convex pattern 13 is faced to the photocurable resin 6 (a of FIG. 4A). Next, the concave-convex pattern is positioned with respect to the substrate 7 to be processed using the light receiving device 161. Next, the lid 112 of the pressure vessel 110 is closed and the interior of the pressure vessel 110 is vented by the venting section 130. At this time, He is introduced into the pressure vessel 110 after the lid 112 is closed. Next, the placement stage 145 is moved upward in the z direction until the photocurable resin 6 comes into contact with the concave-convex pattern 13 to form an assembly 8 composed of the mold 1, the photocurable resin 6, and the substrate 7 to be processed (b of FIG. 4A). ). At this time, the concavo-convex pattern 13 is not completely filled with the photocurable resin 6, and a portion thereof has an unfilled position. Further, at this time, the assembly 8 is in a state in which only the mold 1, the photocurable resin 6, and the substrate 7 to be processed are assembled, and thus the entire surface thereof can be directly exposed to the environment. Thereafter, the substrate support member 140 is moved to further lift the assembly 8 upward in the z direction (c of FIG. 4A). Thereby, the mold 1 is separated from the mold supporting member 150, and the assembly 8 is in a state of being supported only by the substrate supporting member 140. The base supporting member 140 is composed of only four dot-like projections, and the contact surface between the projections and the assembly 8 is actively small. Thus, the assembly 8 is supported such that the fluid pressure of the environment acts substantially on its entire surface. When the assembly 8 is supported such that the fluid pressure of the environment acts substantially on its entire surface, the gas is introduced by the gas introduction section 120 under the control of the drive control section. Therefore, the mold 1 and the substrate 7 to be treated are pressed against each other by the fluid pressure applied by the gas, and the photocurable resin 6 completely fills the concave-convex pattern (d of FIG. 4B). Next, when the pressure P in the pressure vessel 110 and/or the temperature T in the pressure vessel 8 are maintained by the gas introduction section 120 and/or the lamp heater 155 under the control of the drive control section to the previously obtained target value, Ultraviolet light is irradiated onto the photocurable resin 6 in the assembly 8 to cure the photocurable resin 6. After the transfer and exposure of the photocurable resin 6 is completed, the substrate supporting member 140 is housed in the placement stage 145 (e of FIG. 4B). At this time, the assembly 8 is supported by the mold supporting member 150 and the seating platform 145. Next, the bottom surface of the substrate 7 to be treated (the surface opposite to the resist coating surface) is sucked and fixed to the placement stage 145. Finally, while the substrate 7 to be treated is sucked, the placement stage 145 is moved downward in the z direction to separate the mold 1 from the cured photocurable resin 6 (f of Fig. 4B).

(curable resin)

The photocurable resin 6 is not particularly limited. In the present embodiment, a photocurable resin prepared by adding a photopolymerization initiator (about 2% by mass) to a fluoromonomer (0.1 to 1% by mass) to the polymerizable compound can be used. An antioxidant (about 1% by mass) may be added as needed. The photocurable resin produced by the above procedure can be cured by ultraviolet light having a wavelength of 360 nm. Regarding the resin having poor solubility, it is preferred to add a small amount of acetone or acetate to dissolve the resin, and then remove the solvent. It should be noted that the present embodiment utilizes a photocurable material as a material of the curable resin film, but the present invention is not limited to such a configuration, and a heat curable material may be applied.

Examples of the polymerizable compound comprising: benzyl methacrylate (manufactured by Osaka Organic Chemical Industry Ltd. (Osaka Organic Chemical Industries, KK) of Wisk ^{® (Viscoat ®) # 160)} , ethyl carbitol acrylate (Osaka Organic Chemical Industry Ltd. (Osaka Organic Chemical Industries, KK) of Viscoat ^® # 190), polyethylene glycol diacrylate (manufactured by Toagosei Co., Ltd. (TOAGOSEI KK) of Onyx ^{® (Aronix ®) M-220} ) and trimethylolpropane PO modified triacrylate (Aronix ^® M-310 from TOAGOSEI KK). Further, the compound A represented by the following chemical formula (1) can also be used as the polymerizable compound.

[Chemical Formula 1]

Examples of the photopolymerization initiator include an alkylphenyl ketone type photopolymerization initiator such as 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-( 4-morpholinyl) phenyl] -1-butanone (Feng plastic Co. Tonghua (Toyotsu Chemiplas KK) of Irgacure ^® (IRGACURE ^®) 379.

Further, the compound B represented by the following chemical formula (2) can be used as a fluorine monomer.

In the case of an ink-jet method of coating a photocurable resin, is preferred, with fluorine Aronix ^® M-220 represented by the sum of the compound represented by the formula (1),, Irgacure ^® 379 by the chemical formula (2) The monomers were mixed at a ratio of 48:48:3:1 to form a photocurable resin. On the other hand, in the case where the photocurable resin is applied by a spin coating method, it is preferred to dilute to 1% by mass with Propylene Glycol Methyl Ether Acetate (PGMEA). The polymerizable compound is used as a photocurable resin.

(Coating method of curable resin)

The coating of the photocurable resin 6 can be performed by a spin coating method, a dip coating method, an inkjet method, or the like.

(Control method of pressure in pressure vessel and/or temperature of assembly)

The control member controls the pressure P in the pressure vessel 110 and/or the temperature T of the assembly 8 based on the set predetermined parameters to satisfy the following formula 2.

The predetermined parameter is: a percentage of the difference between the size of the resist pattern and the standard size ΔD _all ; a standard pressure P _st ; a standard temperature T _st ; a Young's modulus E _m of the mold; a thermal expansion coefficient α _{m of the} mold; The Young's modulus E _{i of the} substrate to be treated; and the coefficient of thermal expansion α _{i of the} substrate to be treated. However, in the case where only the pressure P in the pressure vessel 110 is controlled (i.e., the temperature T is equal to the standard temperature T _st ), the coefficient of thermal expansion of the mold 1 and the substrate 7 to be treated is not required. Similarly, in the case where only the temperature T of the assembly 8 is controlled (i.e., the pressure P is equal to the standard pressure _Pst ), the Young's modulus of the mold 1 and the substrate 7 to be treated is not required.

△ D _all = (1/E _i -1/E _m ). (PP _st )+(α _m -α _i ). (TT _st ) (2)

In the present specification, the expression "standard size" means the size of the concave-convex pattern 13 of the mold 1 under standard conditions (standard pressure and standard temperature). There is no specific limit to the specific location of the measurement size. However, it is necessary to compare the size of the corresponding position of the concave-convex pattern 13 and the transferred resist pattern.

The standard condition is determined based on the required percentage of the difference of the size of the resist pattern to be formed with respect to the standard size of the mold 1 under standard conditions, that is, the standard condition is determined based on the size of the resist pattern to be formed. For example, in the case of forming a resist pattern having a desired percentage of a difference between the size and the concave-convex pattern 13 of the mold 1 under ambient conditions (atmospheric pressure and room temperature), the standard pressure is atmospheric pressure, the standard temperature is room temperature, and The standard size is the size of the concavo-convex pattern 13 under such conditions. Alternatively, considering the conditions at which the mold 1 is actually used, the standard conditions may be conditions of higher pressure and higher temperature than ambient conditions. In this case, the size of the concavo-convex pattern 13 under the conditions of the high pressure and the high temperature is a standard size.

The expression "percentage of the difference in size of the resist pattern from the standard size" means the percentage of the difference between the resist pattern and the standard size under standard conditions. Specifically, the percentage ΔD _all is represented by the following formula 3.

In the formula (3), D _st represents the size (standard size) of a predetermined region of the concavo-convex pattern 13 under standard conditions, and D _r represents the size of a region of the resist pattern corresponding to the predetermined pattern under standard conditions. . Accordingly, in the case of ΔD _all <0, the size of the resist pattern is smaller than the standard size D _st . Similarly, in the case of ΔD _all > 0, the size of the resist pattern is larger than the standard size D _st .

Equation 2 indicates that as long as at least one of (1/E _i -1/E _m ) and (α _m -α _i ) is not zero, that is, as long as the Young's modulus and thermal expansion coefficient of the mold 1 and the substrate 7 to be treated are At least one of the values is a different value, and the percentage _{ΔD lll of the} entire size difference depends on the pressure P in the pressure vessel and/or the temperature T of the assembly 8. This is because the percentage of expansion or the percentage of shrinkage of the mold 1 and the substrate 7 to be treated are each different. The present invention takes advantage of this fact to achieve a desired percentage of resist pattern that differs in size from the pattern of the mold under predetermined standard conditions.

Equation 2 is derived as follows.

First, Equation 4 is established from the definition of the entire percentage difference ΔD _all .

△D _all =△D _P +ΔD _T (4)

In Equation 4, ΔD _P is the percentage of the dimensional difference accompanying the change in the pressure P (the percentage of the dimensional difference accompanying the pressure change), and ΔD _T is a percentage of the dimensional difference accompanying the change in the temperature T (with temperature change) Percentage difference in size). More specifically, the percentage ΔD _P of the dimensional difference accompanying the pressure change and the percentage ΔD _T of the dimensional difference accompanying the temperature change are respectively defined by the following Equations 5 and 6.

That is, under the condition that the pressure P and/or the temperature T are controlled, the resist pattern is formed, and then only the pressure is changed to return the pressure to the standard pressure (ie, the temperature T=constant), the formula 5 will be accompanied by the pressure. The percentage of the dimensional difference of the change ΔD _{P is} expressed as a percentage of the dimensional difference with respect to the standard size D _st . In addition, under the condition that the pressure P and/or the temperature T are controlled, a resist pattern is formed, and then only the temperature is changed to restore the temperature to the standard temperature (ie, the pressure P=constant), the formula 6 will accompany the temperature. The percentage ΔD _{T of the} changed dimensional difference is expressed as a percentage of the dimensional difference with respect to the standard size D _st .

Next, after the photocurable resin 6 is cured, it is assumed that the photocurable resin 6 follows the expansion and contraction of the substrate 7 to be treated. In reality, this assumption is appropriate in view of the flexibility of the photocurable resin 6. In this case, the percentage ΔD _P of the dimensional difference accompanying the pressure change and the percentage ΔD _T of the dimensional difference accompanying the temperature change are obtained by the following Equations 7 and 8.

Δ D _P = ε _Pi - ε _Pm = Δ P / E _i - Δ P / E _m ⁼ (1/ E _i -1/ E _m ). ( P - P _st ) (7)

△ D _T = ε _Tm - ε _Ti = α _m . △ T -α _i . △ T = (α _m -α _i ). ( T - T _st ) (8)

In Formula 7, ε _Pi represents the amount of deformation when the substrate 7 to be treated is expanded in a state where only the pressure is changed after the resist pattern is formed to restore the pressure P to the standard pressure P _st (ie, the temperature T = constant). Percentage (ppm). ε _Pm represents a percentage (ppm) of the amount of deformation when the mold 1 is expanded in a state where only the pressure is changed after the resist pattern is formed to restore the pressure P to the standard pressure P _st (that is, the temperature T = constant).

In Formula 8, ε _Tm represents a percentage of the amount of deformation when the mold 1 is shrunk in a state where only the temperature is changed after the resist pattern is formed to return the temperature T to the standard temperature T _st (ie, the pressure P = constant) ( Ppm). ε _Ti represents a percentage (ppm) of the amount of deformation when the substrate 7 to be treated is contracted in a state where only the temperature is changed to return the temperature T to the standard temperature T _st (i.e., the pressure P = constant) after the resist pattern is formed.

Equation 2 is derived from Equation 4, Equation 7, and Equation 8.

In the present invention, it is preferable to prioritize the control by the pressure in a state where the pressure P in the pressure vessel 110 is in the range of 0 MPa to 5 MPa. The expression "prioritization of control by pressure" means first determining a target value for control by pressure during imprinting. For example, in the case where the pressure P is in the range of 0 MPa to 5 MPa and the above formula 2 can be satisfied using only the pressure, the assembly 8 is only expanded or contracted using pressure. In this case, ΔD _all = ΔD _P . Alternatively, the insufficient portion is compensated by controlling the temperature T in a situation where the required percentage ΔD _all of the entire dimensional difference cannot be achieved by merely controlling the pressure P in the range of 0 MPa to 5 MPa.

The reasons for adopting the above configuration are as follows. In order to achieve the required percentage ΔD _{all of the} entire dimensional difference according to Equation 2, two parameters of pressure P and temperature T are controlled. Here, the control of the pressure and the control of the temperature each have advantages and disadvantages. Specifically, the advantage of controlling the pressure is that the assembly 8 can be uniformly pressurized by the fluid pressure to achieve uniform dimensional adjustment. A disadvantage of controlling the pressure is that it is not possible to increase the gauge pressure to more than 5 MPa, and the range of size adjustment is limited compared to the case of controlling the temperature. The upper limit of the gauge pressure is set to 5 MPa, because if the pressure exceeds 5 MPa, there is a possibility that impurities between the intervening mold 1 and the substrate 7 to be treated will damage the mold 1 and the substrate 7 to be treated.

At the same time, the advantage of controlling the temperature is that the size adjustment range is greater than the control of the pressure. A disadvantage of controlling the temperature is that during heating, temperature fluctuations are generated in the assembly 8, resulting in difficulty in performing uniform dimensional adjustment; and reaching the target temperature is extremely time consuming. In the case where the material of the mold 1 or the substrate 7 to be treated is quartz, the disadvantage of controlling the temperature becomes particularly remarkable.

Accordingly, in the case where the pressure P in the pressure vessel 110 is in the range of 0 MPa to 5 MPa, the control by the pressure is prioritized to achieve uniform size adjustment.

5 is a cross-sectional view schematically showing the manner in which fluid pressures P1 and P2 act on the assembly 8 in the pressure vessel 110, which is filled with gas in the step illustrated in c of FIG. 4A. In Fig. 5, P1 indicates the fluid pressure applied to the surface of the mold 1, and P2 indicates the fluid pressure applied to the surface of the substrate 7 to be treated and the surface of the photocurable resin 6. As illustrated in Figure 5, the entire surface of the assembly 8 can be directly exposed to the environment in the steps depicted in c of Figure 4A. In addition, the base support member 140, which is constituted by the dot-like projections, supports the assembly 8 such that the fluid pressure of the environment substantially acts on the entire surface of the assembly 8. That is, to the surface of the assembly 8 (and in particular, the flange portion of the mold 1) 15) A uniform fluid pressure P1 is applied, and a uniform fluid pressure P2 is applied to a portion of the substrate 7 to be treated facing the flange portion 15. Thereby, uniform dimensional adjustment becomes possible. In addition, the substrate supporting member 140 supports the assembly 8 at a portion other than the portion 8a corresponding to the pattern. Thereby, an external force other than the fluid pressure P1 and the fluid pressure P2 is prevented from being applied to the portion 8a corresponding to the pattern.

(release)

In the nanoimprint method of the present invention, it is preferred that the pressure P in the pressure vessel 110 is restored to atmospheric pressure after the mold 1 is released, and it is also preferable that the assembly is released after the mold 1 is demolded. The temperature T of 8 is restored to the ambient temperature. This is because uniform dimensional adjustment becomes possible by making the photocurable resin 6 only follow the expansion or contraction of the substrate 7 to be treated.

Preferably, the pressure vessel 110 is filled with gas such that the pressure in the pressure vessel is in the range of 0.1 MPa to 5 MPa, more preferably in the range of 0.5 MPa to 3 MPa, and the best In the range of 1 MPa to 2 MPa. The lower limit of the pressure is set to 0.1 MPa, because if the pressure is less than 0.1 MPa, since the residual gas is not driven out of the patterned region R1, the residual gas does not pass through the quartz substrate (in the case where the gas is He) or The residual gas is not dissolved in the photocurable resin 6 and an incomplete filling defect will occur. In addition, if the pressure is less than 0.1 MPa, the substrate 7 to be treated will not be mutated according to the fluid pressure, and fluctuations may occur in the residual film. On the other hand, the upper limit is set to 5 MPa, because if the pressure is more than 5 MPa, there is a possibility that the mold 1 and the substrate to be treated 7 will be damaged if impurities are interposed between the mold 1 and the substrate 7 to be treated. .

(Operational effect of the present invention)

Hereinafter, the operational effects of the present invention will be described. Figure 6 is a collection of cross-sectional views schematically illustrating the manner in which a mold having a different Young's modulus and/or coefficient of thermal expansion expands or contracts with a substrate to be treated.

If the pressure P in the pressure vessel 110 is increased in a state in which the assembly 8 composed of the substrate 7 to be treated, the photocurable resin 6 and the mold 1 is formed (a of Fig. 6), the assembly 8 is compressed by the fluid pressure. And shrink (b of Figure 6). At this time, the degree of shrinkage of the mold 1 and the substrate 7 to be treated will be different because the Young's modulus of the mold 1 is different from the Young's modulus of the substrate 7 to be treated. The photocurable resin 6 is cured in a state where the assembly 8 is compressed, and then the mold 1 is separated from the photocurable resin 6, whereby the uneven pattern 13 in the contracted state is transferred to the photocurable resin 6 (Fig. 6 c). At this time, the size of the concavo-convex pattern 13 is the same as the size of the resist pattern transferred to the photocurable resin 6. Thereafter, when the pressure P returns to the standard pressure, the mold 1 and the substrate 7 to be treated are restored to their original sizes. At this time, the photocurable resin 6 expands while following the expansion of the substrate 7 to be treated because the photocurable resin 6 is in close contact with the substrate 7 to be treated (d of FIG. 6). Accordingly, when the mold 1 and the substrate 7 to be processed by the compression dimension D _r D _st two patterns of the same due to different degrees of expansion deviates from the mold 1 corresponds to the substrate to be processed and a Young's modulus of the difference in the number of 7 Percentage.

As described above, the nanoimprint method and the nanoimprinting apparatus of the present invention utilize the difference in the degree of change due to the expansion and contraction of the mold and the substrate to be treated to control the size of the resist pattern. Therefore, it is possible to form a desired percentage of the size of the pattern of the mold under predetermined standard conditions. Resist pattern.

<Design Modification of First Embodiment>

In the first embodiment, a case where only the mold 1 has a mesa portion is described. The nanoimprinting method and nanoimprinting apparatus of the present invention can also be applied to a case where only the substrate 7 to be treated has a mesa portion or both the substrate 7 to be treated and the mold 1 have a mesa portion.

In the first embodiment, the case of using the mesa-type mold 1 is described. However, the invention is also applicable to nanoimprinting using a common planar mold.

Further, in the first embodiment, while the substrate 7 to be processed is moved by the placement stage 145, the mold 1 is placed in contact with the photocurable resin 6. Alternatively, as illustrated in FIGS. 7 and 8A, an arrangement may be employed at the central portion of the placement platform 145 for the insertion of the latch 147 of the central portion of the substrate 7 to be treated during contact. The mold 1 and the photocurable resin 6 are brought into contact with each other by pressing a central portion of the substrate on the mold 1 with a pin 147 while sucking the outer periphery of the substrate 7 to be treated. It should be noted that the plug 147 is retracted when the gas is introduced into the pressure vessel 110 to cause fluid pressure to act on the assembly 8. As shown in FIG. 8B, as another member for pressing the central portion of the substrate 7 to be processed on the mold 1 during the contact, the second gas introduction portion 148 may be disposed in the central portion of the placement platform 145. In this case, the gas introduced via the second gas introduction section 148 is blown onto the substrate 7 to be treated.

Further, in the first embodiment, the mold 1 and the substrate 7 to be treated are placed on the mold supporting member 150 and the placing platform 145, respectively. Alternatively, the mold 1 is placed in contact with the substrate 7 to be treated coated with the photocurable resin 6. At the touch, the assembly 8 is formed and then placed on the placement platform 145 in this state.

<Second Embodiment of Nano Imprinting Method and Nano Imprinting Apparatus>

A second embodiment of the nanoimprinting method and the nanoimprinting apparatus of the present invention will be described with reference to Figs. 9 to 10B. Figure 9 is a cross-sectional view schematically showing a nanoimprinting apparatus according to a second embodiment of the present invention. 10A and 10B are a set of cross-sectional views schematically illustrating steps of a nanoimprint method according to a second embodiment of the present invention. It should be noted that the structure of the placement platform for the substrate and the substrate supporting member of the second embodiment is different from that of the first embodiment, and a heating member such as a lamp heater is not provided. Accordingly, since the same elements as those of the first embodiment are not particularly necessary, a detailed description thereof will be omitted.

(nano imprinting device)

First, a nanoimprinting apparatus for performing a nanoimprinting method according to a second embodiment will be described. The nanoimprint method of the second embodiment is performed using the nanoimprinting apparatus 200 illustrated in FIG. The nanoimprinting apparatus 200 of FIG. 9 is equipped with: a pressure vessel 210; a gas introduction section 220 for introducing a gas into the pressure vessel 210; an exhaust section 230 for discharging gas from the inside of the pressure vessel 210; a support member 240 for supporting the substrate 7 to be processed; a substrate placement platform 245 on which the substrate 7 to be treated is placed; a mold support member 250 for supporting the mold 1; and a light receiving device 261 for positioning the concave and convex pattern And an exposure light source 262 for exposing the resist.

(mold and substrate to be treated)

In the second embodiment, the Young's modulus of the mold 1 is different from the Young's modulus of the substrate 7 to be treated. It should be noted that the thermal expansion coefficients of the mold 1 and the substrate 7 to be treated may be the same or different.

(base placement platform)

The placement platform 245 is used to place the substrate 7 to be treated thereon. The mounting platform 245 is assembled to be in the x direction (horizontal direction in FIG. 9), the y direction (perpendicular to the direction of the drawing in FIG. 9), the z direction (vertical direction in FIG. 9), and the θ direction (having The axis in the direction is moved as the direction of rotation of the center of rotation) in order to achieve positioning relative to the relief pattern on the mold 1. The placement platform 245 can be equipped with a suction opening for aspirating and holding the substrate 7 to be treated and a heater for heating the substrate 7 to be treated.

(base support member)

When the substrate 7 to be treated placed on the placement platform 245 is lifted off the placement platform 245, and also when the assembly 8 is supported, the substrate support member 240 is utilized. Similar to the placement platform 245, the substrate support member 240 is assembled to be movable at least in the z-direction. As shown in FIGS. 9 and 10A, similar to the mold support member 250, the base support member 240 of the second embodiment is constituted by the ring portion 241 and the support post 242. The ring portion 241 can be in the form of a broken ring shape.

(gas introduction section and exhaust section)

The gas introduction section 220 and the exhaust section 230 are the same as the corresponding sections of the first embodiment. The second embodiment is not provided with a heating member. Thus, the gas introduction section 220, the exhaust section 230, and a drive control section (not shown) for controlling the driving of such components serve as the control members of the present invention.

(nano imprint method)

To aid in understanding the driver of the device, only the placement platform 245, the substrate support member 240, the mold support member 250, and the components required to interpret the procedures for using such components are illustrated in Figures 10A and 10B. It should be noted that in the following description, ambient conditions (atmospheric pressure and room temperature) are expressed as standard conditions.

The nanoimprint method of the second embodiment is performed as follows. First, the user determines the percentage of the difference between the resist pattern to be formed and the standard size of the mold 1 under standard conditions. Next, the user sets the desired percentage and other predetermined parameters in the drive control section that controls the gas introduction section 220 and the exhaust section 230. The drive control section obtains the target pressure P within the pressure vessel 210 from the predetermined relationship formula during imprinting based on the above parameters. Next, the cover 212 of the pressure vessel 210 is opened, the substrate 7 to be treated whose surface is coated with the photocurable resin 6 is placed on the placement platform 245, and the mold 1 is placed on the mold support member 250 so that the concave-convex pattern faces Photocurable resin 6 (a of Fig. 10A). Next, the concave-convex pattern is positioned with respect to the substrate 7 to be processed using the light receiving device 261. Next, the lid 212 of the pressure vessel 210 is closed and the interior of the pressure vessel 210 is vented by the venting section 230. At this time, He may be introduced into the pressure vessel 210 after the lid 212 is closed. Next, the placement stage 245 is moved upward in the z direction until the photocurable resin 6 comes into contact with the concavo-convex pattern 13 of the mold 1 to form an assembly 8 composed of the mold 1, the photocurable resin 6, and the substrate 7 to be processed (Fig. b) of 10A. At this time, the concavo-convex pattern 13 is not completely filled with the photocurable resin 6, and a portion thereof has an unfilled position. In addition, the assembly 8 is at this time only The mold 1, the photocurable resin 6, and the substrate 7 to be treated are assembled together, and thus the entire surface thereof can be directly exposed to the environment. Thereafter, the substrate support member 240 is moved to further lift the assembly 8 upward in the z direction (c of FIG. 10A). Thereby, the mold 1 is separated from the mold supporting member 250, and the assembly 8 is in a state of being supported only by the substrate supporting member 240. The base support member 240 is constituted by the ring portion 241 and the support post 242, and at the outer periphery of the assembly 8, the contact area between the ring portion 241 and the assembly 8 is a very small area. Thus, the assembly 8 is supported such that the fluid pressure of the environment acts substantially on its entire surface. The gas is introduced from the gas introduction section 220 when the assembly 8 is supported such that the fluid pressure of the environment substantially acts on its entire surface. Therefore, the mold 1 and the substrate 7 to be treated are pressed against each other by the fluid pressure applied by the gas, and the photocurable resin 6 completely fills the concave-convex pattern (d of FIG. 10B). Next, when the gas introduction section 220 treats the pressure P in the pressure vessel 210 to the previously obtained target value under the control of the drive control section, ultraviolet light is irradiated onto the photocurable resin 6 in the assembly 8. To cure the photocurable resin 6. After the transfer and exposure of the photocurable resin 6 is completed, the substrate supporting member 240 is moved downward in the z direction and returned to its original position (e of Fig. 10B). At this time, the assembly 8 is supported by the mold supporting member 250 and the seating platform 245. Thereafter, the mold 1 and the cured photocurable resin 6 were separated in the same manner as in the first embodiment. Finally, the conditions of the assembly 8 are restored to standard conditions.

It should be noted that it is preferable to install a cold filter between the exposure light source 262 and the assembly 8 when exposing the photocurable resin 6 to The temperature of the assembly 8 is prevented from rising during exposure.

The second embodiment performs the resizing only using the control by the pressure. This is because the second embodiment employs ambient conditions as standard conditions, resulting in the temperature T of the assembly 8 not changing from the standard temperature (room temperature). Accordingly, the second term of Equation 2 can be ignored.

As described above, the nanoimprint method and the nanoimprinting apparatus of the second embodiment use a mold having a fine concavo-convex pattern of a predetermined standard size at a predetermined standard pressure and a predetermined standard temperature, and a resist-coated surface. The substrate to be treated has a different Young's modulus from the substrate to be treated; and the resist is cured when the pressure in the pressure vessel is controlled to satisfy a predetermined relationship formula using predetermined parameters. Accordingly, the same advantageous effects as those obtained by the nanoimprint method of the first embodiment can be obtained.

<Method of Forming Patterned Substrate>

Next, a method for manufacturing a patterned substrate according to an embodiment of the present invention will be described. In the present embodiment, the above-described nanoimprint method is used to fabricate a patterned substrate.

First, a resist film is formed on the surface of the substrate to be treated, and a pattern has been formed on the resist film by the above-described nanoimprint method. Next, the patterned resist film is used as a mask to etch the substrate to be processed to form a four-convex pattern corresponding to the concave-convex pattern of the resist film. Thereby, a patterned substrate (replica) having a predetermined pattern is obtained.

Forming on the surface of the substrate to be treated having the mask layer in a state where the substrate to be treated is a laminated structure and a mask layer is included on the surface thereof A resist film on which a pattern has been formed by the above-described nanoimprint method. Next, dry etching is performed using the resist as a mask to form a concavo-convex pattern corresponding to the concavo-convex pattern of the resist film in the mask layer. Thereafter, dry etching is further performed using the mask layer as an etch stop layer to form a concavo-convex pattern in the substrate. Thereby, a substrate having a predetermined pattern is obtained.

The dry etching method is not particularly limited as long as it can form a concavo-convex pattern in the substrate, and can be selected according to the intended use. Examples of the dry etching method that can be used include an ion milling method, a reactive ion etching (RIE) method, a sputtering etching method, and the like. Among these methods, the ion milling method and the RIE method are particularly preferred.

The ion milling method is also referred to as ion beam etching. In the ion milling method, an inert gas such as Ar is introduced into the ion source to generate ions. The generated ions are accelerated through the grid and collide with the sample substrate to perform etching. Examples of ion sources include: Kauffman type ion sources; high frequency ion sources; electron bombardment ion sources; duoplasma ion ion sources; Freeman ion sources (Freeman ion sources) And; Electron Cyclotron Resonance (ECR) ion source.

The Ar gas can be used as a processing gas during ion beam etching. A fluorine-based gas or a chlorine-based gas can be used as an etchant during RIE.

As described above, the method for manufacturing a patterned substrate of the present invention is carried out using a nanoimprint method of controlling the size of the resist pattern. Thus, in the manufacture of the patterned substrate, high precision processing becomes possible.

[Example]

An example of the nanoimprint method of the present invention will be described below.

<Example 1>

In Example 1, a quartz mold was used as a mold, and a Si substrate was used as a substrate to be treated. The Young's modulus E _m of the quartz mold is 72 gigapascals, and the thermal expansion coefficient α _m of the quartz mold is 5.5.10 ^-7 /°C. The Young's modulus E _i of the Si substrate was 185 gigapascals, and the thermal expansion coefficient α _i of the Si substrate was 2.6.10 ^-6 /-°C. Equation 9 is obtained by substituting this value into Equation 2.

△D _all =-8.48.10 ^-3 . Σ-2.05.10 ^-6 . △T (9)

It should be noted that in Formula 9, σ represents the gauge pressure and ΔT represents the temperature difference obtained by subtracting the room temperature from the temperature of the assembly.

A photocurable resist was coated on a Si substrate having a diameter of 4 Å to coat the Si substrate with a photocurable resist layer. The mold was fabricated based on a quartz substrate having a diameter of 6 inches and a thickness of 0.525 mm and having the pattern depicted in FIG. The quartz mold is subjected to mold release treatment.

In Example 1, imprinting is performed by adjusting only the gauge pressure in the pressure vessel during imprinting, so that the size of the resist pattern formed by imprinting will be larger than that on the quartz mold under ambient conditions. The size of the concave-convex pattern is 5 ppm. If ΔD _all = -5.10 ^-6 and ΔT = 0 are substituted into Equation 9, the calculated value σ is 0.59 MPa.

Next, imprinting was performed under ambient conditions (room temperature = 25 ° C) as follows. The quartz mold is brought into contact with the photocurable resist layer slightly to form an assembly. Connect Place the assembly in a pressure vessel. Further, air is introduced into the pressure vessel such that the pressure of the air becomes a gauge pressure of 0.59 MPa to pressurize the assembly. At this time, the temperature of the assembly was 25 °C. Thereafter, the photocurable resist layer is exposed. The temperature of the assembly during the exposure was 25 °C. Next, the pressure is reduced to atmospheric pressure, and then the quartz mold and the photocurable resist are separated. Details regarding each of the quartz mold, the photocurable resist, the resist pattern, the Si substrate, and the steps are as follows.

(quartz mold)

The pattern configuration of the quartz mold is as shown in FIG. Fig. 11 is a schematic view showing the configuration of a concavo-convex pattern of a mold viewed from the rear surface of the mold. Specifically, four alignment marks AM1 in the form of a cross-shaped pattern having a pattern depth of 100 nm, in which a line length of 55 μm and a line width of 10 μm were intersected (FIG. 12). In addition, grid patterns (W1, X1, Y1, and Z1) toward the outer peripheral side of each of the alignment marks AM1 are provided. A narrow pitch pattern G1 having a pattern depth of 100 nm and a wide pitch pattern G2 having a pattern depth of 100 nm parallel to each other are disposed in each of the grid patterns, wherein a distance of 1.9 μm in the narrow pitch pattern G1 is provided. A line having a width of 0.95 μm was arranged, and a line having a width of 1.0 μm was disposed in a wide pitch pattern G2 at a distance of 2.0 μm ( FIG. 11 ). The distance between the centers of the grid patterns W1 and Y1 and the distance between the centers of the grid patterns X1 and Z1 are both 60 mm (Fig. 11).

(Photocurable resist)

A mixture of a compound represented by the chemical formula (1), Aronix ^® M-220, Irgacure ^® 379, and a fluoromonomer represented by the chemical formula (2) at a ratio of 48:48:3:1 is used as a photocurable resist. .

(resist pattern)

In the case where the imprint using the above quartz mold is performed, a resist pattern such as the resist pattern illustrated in Fig. 13 is formed. Figure 13 is a schematic view showing the configuration of a resist viewed from the front surface of the resist. The resist pattern is a concavo-convex pattern transferred from a quartz mold. Specifically, four alignment marks AM1 in the form of a cross-shaped pattern having a pattern height of 100 nm were provided, in which lines having a length of 55 μm and a line width of 10 nm were crossed (Fig. 12). In addition, grid patterns (W2, X2, Y2, and Z2) toward the outer peripheral side of each of the alignment marks AM1 are provided. A narrow pitch pattern G1 having a pattern height of 100 nm parallel to each other and a wide pitch pattern G2 having a pattern depth of 100 nm are disposed in each of the grid patterns, wherein a distance of 1.9 μm in the narrow pitch pattern G1 is provided. A line having a width of 0.95 μm was disposed, and a line having a width of 1.0 μm was disposed in a wide pitch pattern G2 at a distance of 2.0 μm ( FIG. 13 ). The distance between the centers of the grid patterns W2 and Y2 and the distance between the centers of the grid patterns X2 and Z2 are both 60 mm (Fig. 13).

(Si substrate)

An Si substrate treated with a decane coupling agent having excellent adhesion to a photocurable resist is utilized. The surface is treated by diluting the decane coupling agent, coating the surface of the substrate with the diluted decane coupling agent using a spin coating method and then annealing the coated surface.

(Photocurable resist coating step)

DMP-2831 is used, which is a piezoelectric type inkjet printer of FUJIFILM Dimatix. A dedicated 10 picoliter head was used as the ink jet head.

(Mold contact step)

The quartz mold and the Si substrate are brought close to each other, and positioning is performed while observing the alignment mark from the surface of the quartz mold after using an optical microscope, so that the alignment mark is at a predetermined position.

(exposure step)

Exposure was performed at an irradiation dose of 300 mJ/cm 2 by ultraviolet light having a wavelength of 360 nm. A room temperature filter is installed between the exposure light source and the quartz mold/Si substrate to prevent the temperature of the quartz mold and the Si substrate from rising during exposure.

<Example 2>

A quartz mold was used as a mold in the same manner as in Example 1, and a Si substrate was used as a substrate to be treated.

A photocurable resist was coated on a Si substrate having a diameter of 4 Å to coat the Si substrate with a photocurable resist layer. The mold was fabricated based on a quartz substrate having a diameter of 6 inches and a thickness of 0.525 mm and having the pattern depicted in FIG. The quartz mold is subjected to mold release treatment.

In Example 2, imprinting is performed by adjusting the gauge pressure in the container pressure and the temperature of the assembly during imprinting so that the size of the resist pattern formed by imprinting will be greater than that under ambient conditions. The size of the concave-convex pattern on the quartz mold is 100 ppm. At this time, the gauge pressure was set to 5 MPa. In this case, the value of the first term in Equation 9 will be -42.4, which is less than the target value of 100ppm. Accordingly, ΔD _all = -100.10 ^-6 and σ = 5.0 were substituted into Formula 9, to calculate a ΔT value of 28.1 °C.

Next, imprinting was performed under ambient conditions (room temperature = 25 ° C) as follows. The quartz mold is brought into contact with the photocurable resist layer slightly to form an assembly. Next, the assembly is placed in a pressure vessel. Further, air was introduced into the pressure vessel so that the pressure of the air became a gauge pressure of 5.0 MPa to pressurize the assembly. At this time, the temperature of the assembly was 25 °C. Further, the assembly was heated using a lamp heater so that its temperature became 53.1 °C. Thereafter, the photocurable resist layer is exposed. The temperature of the assembly during the exposure was 53.1 °C. Next, the pressure is reduced to atmospheric pressure, the temperature of the assembly is returned to room temperature, and then the quartz mold and the photocurable resist are separated. Details regarding each of the quartz mold, the photocurable resist, the resist pattern, the Si substrate, and the steps are the same as those of Example 1.

<Example 3>

In Example 3, a quartz mold was used as a mold, and a Ni substrate was used as a substrate to be treated. The Young's modulus E _m of the quartz mold is 72 gigapascals, and the thermal expansion coefficient α _m of the quartz mold is 5.5.10 ^-7 /°C. The Young's modulus E _i of the Ni substrate is 200 gigapascals, and the thermal expansion coefficient α _i of the Ni substrate is 13.4.10 ^-6 /°C. Equation 10 is obtained by substituting this value into Equation 2.

△D _all =-8.89.10 ^-3 . Σ-12.9.10 ^-6 . △T (10)

The photocurable resist was coated on a Ni substrate having a diameter of 4 Å to coat the Ni substrate with a photocurable resist layer. Based on a diameter of 6 A quartz substrate having a thickness of 0.525 mm and having the pattern shown in Fig. 11 was formed to manufacture a mold. The quartz mold is subjected to mold release treatment.

In Example 3, imprinting is performed by adjusting only the gauge pressure in the pressure vessel during imprinting, so that the size of the resist pattern formed by imprinting will be larger than that on the quartz mold under ambient conditions. The size of the concave-convex pattern is 10 ppm smaller. If ΔD _all = -10.10 ^-6 and ΔT = 0 are substituted into Equation 10, the calculated value σ is 1.12 MPa.

Next, imprinting was performed under ambient conditions (room temperature = 25 ° C) as follows. The quartz mold is brought into contact with the photocurable resist layer slightly to form an assembly. Next, the assembly is placed in a pressure vessel. Further, air was introduced into the pressure vessel such that the pressure of the air became a gauge pressure of 1.12 MPa to pressurize the assembly. At this time, the temperature of the assembly was 25 °C. Thereafter, the photocurable resist layer is exposed. The temperature of the assembly during the exposure was 25 °C. Next, the pressure is reduced to atmospheric pressure, and then the quartz mold and the photocurable resist are separated. Details regarding each of the quartz mold, the photocurable resist, the resist pattern, the Ni substrate, and the steps are the same as those of Example 1.

<Comparative Example 1>

Embossing was performed in the same manner as in Example 1 except that a quartz substrate having a diameter of 4 Å was used as the substrate coated with the resist.

<Evaluation method for size adjustment>

The size of the resist pattern formed by the example and the comparative example with respect to the mold was performed by comparing the grid pattern formed on the quartz reference substrate having a diameter of 6 Å and the grid pattern in the resist pattern. Evaluation of the degree of reduction in the size of the pattern.

Specifically, the evaluation is performed as follows.

First, a reference substrate is prepared. Figure 14 is a schematic diagram showing the configuration of a pattern of reference substrates viewed from the back surface of the reference substrate. Specifically, four alignment marks AM2 having a pattern depth of 100 nm were disposed, in which four squares were arranged in the grid (Fig. 15). Each of the alignment marks AM2 has a size of 55 μm in both the vertical and horizontal directions, and an interval between the squares is 13 μm. In addition, grid patterns (W3, X3, Y3, and Z3) toward the outer peripheral side of each of the alignment marks AM2 are provided. A narrow pitch pattern G1 having a pattern depth of 100 nm and a wide pitch pattern G2 having a pattern depth of 100 nm parallel to each other are disposed in each of the grid patterns, wherein a distance of 1.9 μm in the narrow pitch pattern G1 is provided. A line having a width of 0.95 μm was disposed, and a line having a width of 1.0 μm was disposed in a wide pitch pattern G2 at a distance of 2.0 μm ( FIG. 14 ).

In the reference substrates used to evaluate Example 1 and Comparative Example 1, the distance between the centers of the grating patterns W3 and Y3 and the distance between the centers of the grating patterns X3 and Z3 are larger than those in the concave-convex pattern of the quartz mold. The grid pattern is 5 ppm smaller. That is, the distance between the centers of the grid patterns is from 60 mm to 300 nm (Fig. 14). In addition, the distance between the pair of opposite alignment marks AM2 (for example, alignment marks formed near the grid patterns W3 and Y3) is larger than the relative alignment mark AM1 formed in the quartz mold (for example, formed The distance between the grid pattern W1 and the alignment mark in the vicinity of Y1 is 5 ppm.

In the reference substrate used to evaluate Example 2, the distance between the centers of the grid patterns W3 and Y3 and the distance between the centers of the grid patterns X3 and Z3 It is 100 ppm smaller than the corresponding grating pattern in the concave-convex pattern of the quartz mold. That is, the distance between the centers of the grating patterns is 60 mm to 6 μm. In addition, the distance between the pairs of the opposite alignment marks AM2 is smaller than the distance between the relative alignment marks AM1 formed in the quartz mold by 100 ppm.

In the reference substrate used to evaluate Example 3, the distance between the centers of the grating patterns W3 and Y3 and the distance between the centers of the grating patterns X3 and Z3 are 10 ppm smaller than the corresponding grating pattern in the concave-convex pattern of the quartz mold. . That is, the distance between the centers of the grating patterns is from 60 mm to 600 nm. In addition, the distance between the pairs of the opposite alignment marks AM2 is 10 ppm smaller than the distance between the opposite alignment marks AM1 formed in the quartz mold.

Next, confirm the offset of the size. Confirmation was performed under ambient conditions (room temperature = 25 ° C). The reference substrate was brought close to the resist formed with the resist pattern until the distance between the resist and the reference substrate was 20 μm. Next, positional alignment is performed such that the alignment mark AM1 formed in the resist pattern is combined with the alignment mark AM2 formed in the reference substrate while observing the alignment mark after the surface is self-referenced using the optical microscope . At this time, the distance between the alignment mark AM1 and the protruding portion in the upper, lower, left, and right directions of the alignment mark AM2 was 1.5 μm (FIG. 16). Thereafter, the distance between the resist and the reference substrate is set to 10 μm or less.

After the above adjustment is completed, an image such as a map is observed at each of four regions in which the grating pattern is formed (i.e., regions in which the grating patterns W2 and W3, X2 and X3, Y2 and Y3, and Z2 and Z3 overlap). Moire fringe as depicted in 17.

Next, positional alignment is performed such that the position of the moire fringes observed at the region where W2 and W3 overlap becomes the same when the surface pattern is observed from the surface after the reference substrate. Next, when the grating pattern is observed on the surface after the reference substrate, the positional shift amount ΔY of the observed moire fringes measured in the region where Y2 and Y3 overlap is the same (FIG. 17). Thereafter, the relative offset amount Δy of the grating patterns G1 and G2 at the regions is calculated from the positional shift amount ΔY.

At the same time, the positional alignment is performed such that the position of the moire fringes observed at the region where X2 and X3 overlap becomes the same when the surface pattern is observed from the surface after the reference substrate. Next, when the grating pattern is observed on the surface after the reference substrate, the positional shift amount ΔX of the observed moire fringes measured in the region where Z2 and Z3 overlap is the same (FIG. 17). Thereafter, the amount Δx of the relative offset x of the grating patterns G1 and G2 at the regions is calculated from the positional shift amount ΔX.

After calculating the relative offsets Δx and Δy, the relative offset is satisfied to the inequality - 30 nm △x 30 nm and -30 nm △y The condition of 30 nm is evaluated as the size adjustment performed. Other conditions are evaluated as not performing dimensional adjustments. The above measurement method using moiré fringes is described in detail in Japanese Unexamined Patent Publication No. 2010-267682.

<evaluation result>

Table 1 summarizes the evaluation results for the examples and comparative examples. For the item "Size", the evaluation to "Yes" indicates that the resizing is performed, and the evaluation to "No" indicates that the resizing is not performed. It can be understood from Table 1 that the implementation of the present invention enables the formation of dimensions of the pattern of the mold under standard and standard conditions. The required percentage of the resist pattern is poor.

[Field of industrial availability]

The nanoimprint method and nanoimprinting apparatus of the present invention can be used to fabricate a patterned medium or a semiconductor device to be a next-generation hard disk.

1, 90‧‧‧ mold

6‧‧‧Photocurable resin

7‧‧‧Substrate to be treated

8‧‧‧assembly

Section 8a‧‧‧

11‧‧‧Support section

12‧‧‧ countertop section

13‧‧‧ concave pattern

15‧‧‧Flange section

91‧‧‧ Parts

92‧‧‧ undulation

100,200‧‧‧ nano imprinting device

110, 210‧‧‧ Pressure vessel

111, 211‧‧‧ container body

112, 212‧‧ ‧ cover

113, 213‧‧ ‧ glass windows

120, 220‧‧‧ gas introduction section

121, 221‧‧‧ gas introduction pipeline

122, 132, 222, 232‧ ‧ valves

130, 230‧‧‧Exhaust section

131, 231‧‧‧ exhaust duct

140, 240‧‧‧Base support parts

145, 245‧‧‧ Resettlement platform

146‧‧‧ suction opening

147‧‧‧ latch

148‧‧‧Second gas introduction section

150, 250‧‧‧Mold support parts

151, 241, 251‧‧ ‧ ring section

152, 242, 252‧‧‧ support columns

155‧‧‧Light heater

161, ‧‧‧‧ light receiving equipment

162, 262‧‧‧ exposure light source

AM1, AM2‧‧‧ alignment mark

D1, D2‧‧‧ thickness

D _st , D _r ‧‧‧ size

F‧‧‧External force

G1‧‧‧ narrow pitch pattern

G2‧‧‧ wide spacing pattern

P1, P2‧‧‧ fluid pressure

R1‧‧‧ patterned area

R2‧‧‧ area

S1‧‧‧ base

W1, W2, W3, X1, X2, X3, Y1, Y2, Y3, Z1, Z2, Z3‧‧‧ grille pattern

△X, △Y‧‧‧ position offset

1 is a cross-sectional view schematically showing a nano imprint apparatus according to a first embodiment of the present invention.

2A is a perspective view schematically showing an example of a mesa type mold.

2B is a cross-sectional view schematically showing a section of the mesa-type mold taken along line A-A of FIG. 2A.

3A is a plan view schematically showing a first embodiment of a placement platform for a substrate to be processed of the nanoimprinting apparatus of the present invention.

3B is a plan view schematically showing a second embodiment of a placement platform for a substrate to be processed of the nanoimprinting apparatus of the present invention.

Figure 3C is a plan view schematically showing a first embodiment of a support member for a mold of the nanoimprinting apparatus of the present invention.

4A is a set of cross-sectional views schematically illustrating steps of a nanoimprint method according to a first embodiment of the present invention.

4B is a set of cross-sectional views schematically illustrating steps of a nanoimprint method according to a first embodiment of the present invention.

Figure 5 is a cross-sectional view schematically showing the manner in which fluid pressure acts on the assembly in the present invention.

Figure 6 is a collection of cross-sectional views schematically illustrating the manner in which a mold having a different Young's modulus and/or coefficient of thermal expansion expands or contracts with a substrate to be treated.

Figure 7 is a plan view schematically showing a third embodiment of a substrate mounting platform for a nanoimprinting apparatus of the present invention.

Fig. 8A is a cross-sectional view schematically showing a manner in which a mold and a substrate coated with a curable resin are placed in contact with each other using a placement platform equipped with the first embodiment of the contact mechanism.

Fig. 8B is a cross-sectional view schematically showing a manner in which a mold and a substrate coated with a curable resin are placed in contact with each other using a placement platform equipped with a second embodiment of the contact mechanism.

Figure 9 is a cross-sectional view schematically showing a nanoimprinting apparatus according to a second embodiment of the present invention.

Figure 10A is a collection of cross-sectional views schematically illustrating the steps of a nanoimprint method in accordance with a second embodiment of the present invention.

FIG. 10B is a schematic view of a second embodiment of the present invention A collection of cross-sectional views of the steps of the nanoimprint method.

Fig. 11 is a schematic view showing the configuration of a concavo-convex pattern of a mold viewed from the rear surface of the mold.

Figure 12 is a diagram schematically showing the configuration of an alignment mark formed on a mold and a resist.

Figure 13 is a schematic view showing the configuration of a resist pattern viewed from the front surface of the resist pattern.

Figure 14 is a schematic diagram showing the configuration of a pattern of reference substrates viewed from the back surface of the reference substrate.

Figure 15 is a diagram schematically showing the configuration of alignment marks formed on a reference substrate viewed from the back surface of the reference substrate.

Figure 16 is a diagram schematically showing a state in which two alignment marks are positioned relative to each other.

Figure 17 is a diagram schematically showing the manner in which the moir patterns overlap.

Figure 18 is a diagram schematically showing a conventional adjustment method for matching the pattern size of a mold that deviates from a predetermined design size to the design size.

1‧‧‧Mold

7‧‧‧Substrate to be treated

6‧‧‧Photocurable resin

8‧‧‧assembly

13‧‧‧ concave pattern

D _st , D _r ‧‧‧ size

Claims (14)

A nanoimprinting method comprising: using a mold having a fine concavo-convex pattern of a predetermined standard size at a predetermined standard pressure and a predetermined standard temperature, and a substrate to be treated having a resist coated surface, the mold and the mold The substrate to be treated has different Young's modulus and/or different coefficients of thermal expansion; the mold is formed by contacting the concave and convex pattern with a resist coated on the resist coated surface a resist and an assembly of the substrate to be treated; placing the assembly in a pressure vessel, the pressure P in the pressure vessel is between 0.1 MPa and 5 MPa, and at the pressure The pressure P in the container and/or the temperature T of the assembly is controlled to satisfy the following formula 1 to cure the resist, ΔD _all = (1/E _i -1/E _m ). (PP _st )+(α _m -α _i ). (TT _st ) (1) wherein a percentage of a difference in size of the resist pattern with respect to the standard size is expressed as ΔD _all , the standard pressure is expressed as P _st , and the standard temperature is expressed as T _st , The Young's modulus of the mold is expressed as E _m , the thermal expansion coefficient of the mold is expressed as α _m , the Young's modulus of the substrate to be treated is represented as E _i and the thermal expansion coefficient of the substrate to be treated is expressed as α _i ; And thereafter separating the mold from the resist. The nanoimprint method as described in claim 1, wherein The control by the pressure P in the pressure vessel is prioritized. The nanoimprint method according to claim 1, wherein the pressure P in the pressure vessel is restored to atmospheric pressure after the mold is separated from the resist. The nanoimprint method of claim 1, wherein the temperature T of the assembly is restored to an ambient temperature after the mold is separated from the resist. The nanoimprint method of claim 3, wherein the temperature T of the assembly is restored to an ambient temperature after the mold is separated from the resist. The nanoimprint method according to claim 1, wherein the assembly is supported by the support member only at a portion other than the portion corresponding to the concave-convex pattern in the assembly To perform the placement of the assembly. The nanoimprint method of claim 6, wherein the support member has a ring shape. The nanoimprint method of claim 6, wherein the support member is composed of three or more protrusions. A nanoimprinting apparatus for performing the nanoimprinting method according to any one of claims 1 to 8, the apparatus comprising: a pressure vessel for use at 0.1 a plenum to 5 MPa pressure P under the assembly, the assembly being processed by a mold having a fine concave-convex pattern of a predetermined standard size at a predetermined standard pressure and a predetermined standard temperature, having a resist coated surface to be processed a substrate and a resist formed by contacting the concave-convex pattern with the resist applied on the resist coated surface; and a control member for controlling the The pressure P in the pressure vessel and/or the temperature T of the assembly satisfy the following formula 2, ΔD _all = (1/E _i -1/E _m ). (PP _st )+(α _m -α _i ). (TT _st ) (2) wherein a percentage of a difference in size of the resist pattern with respect to the standard size is expressed as ΔD _all , the standard pressure is expressed as P _st , and the standard temperature is expressed as T _st , The Young's modulus of the mold is expressed as E _m , the thermal expansion coefficient of the mold is expressed as α _m , the Young's modulus of the substrate to be treated is represented as E _i and the thermal expansion coefficient of the substrate to be treated is expressed as α _i . The nanoimprinting apparatus according to claim 9, wherein the control member prioritizes the control by the pressure P in the pressure vessel. The nanoimprinting device as claimed in claim 9 further includes: a support member for supporting the assembly, disposed in the pressure vessel, and wherein the assembly is only in a portion of the assembly other than a portion corresponding to the concave-convex pattern Support member support. The nanoimprinting device according to claim 11, wherein the support member has a ring shape. The nanoimprinting apparatus according to claim 11, wherein the support member is composed of three or more protrusions. A method of manufacturing a patterned substrate, comprising: forming a resist having a transferred concave-convex pattern on a substrate to be processed by the nanoimprint method according to any one of claims 1 to 8. a film of the agent; and etching is performed using the resist film as a mask to form a concavo-convex pattern corresponding to the concavo-convex pattern transferred to the resist film on the substrate to be processed.