Removal method, removal apparatus, imprint apparatus, replica manufacturing apparatus, and article manufacturing method

Abstract

To make it possible to remove residue generated at least near the side surfaces of a convex portion of a mold.SOLUTION: A removal method is for removing residue adhering to a mold including a base having a main surface and a convex portion provided on the main surface, where the mold has an uneven pattern formed on the upper surface of the convex portion so as to be pressed against a curable composition. The method includes a first removal step of removing the residue, where a liquid-repellent layer formed on at least the side surface of the convex portion is dissolved with a specified solvent to remove the residue.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a removal method, a removal apparatus, an imprint apparatus, a replica manufacturing apparatus, and a method for manufacturing an article. [Background technology]

[0002] Photo-nanoimprinting technology has been attracting attention as a method for forming nano-sized (e.g., 1 nm or more and 1000 nm or less) fine patterns (relief structure). In photo-nanoimprinting technology, a mold (form, mask) for imprinting, on which a relief pattern is formed and which is transparent to exposure light, is brought into contact with a curable composition (resist, imprinting material) applied onto a base substrate. After the curable composition is cured to form a cured product, the mold is released from the cured product to form a cured product pattern on the base substrate. Then, the base substrate is processed using the cured product pattern as a mold, thereby forming a fine pattern on the base substrate. In the imprinting method, a process of forming a cured product pattern at a desired position on the substrate is repeated while moving the mold over the substrate.

[0003] Molds used in photo-nanoimprinting technology may be formed by processing materials such as quartz glass. The mold for imprinting forms a convex mesa, and forms a fine concave-convex pattern on the contact surface (imprint surface) with the curable composition, which is the upper surface of the mesa. This concave-convex pattern is pressed against the curable composition.

[0004] Here, when the concave-convex pattern formed on the upper surface of the mesa of the mold is pressed against the curable composition, the curable composition has fluidity, and therefore the curable composition may overflow from the contact surface (imprint surface) on the upper surface of the mesa and creep up onto the side wall of the mesa (hereinafter, this phenomenon is referred to as "seepage").

[0005] The mold is separated from the cured product on the substrate when the curable composition is cured, but the curable composition that has seeped out onto the sidewall of the mesa remains attached to the sidewall of the mesa. Therefore, when the process of pressing the mold against the curable composition is repeated, the amount of the curable composition adhering to the sidewall of the mesa gradually increases, and eventually this curable composition falls onto the substrate at an unintended timing, causing a problem of causing a major defect on the substrate.

[0006] Patent Document 1 discloses a technique for making only the mesa sidewalls liquid repellent to a curable composition by protecting the concave-convex pattern surface with a protective material in advance. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Patent No. 6441181 Summary of the Invention [Problem to be solved by the invention]

[0008] The method of protecting the uneven pattern surface described in Patent Document 1 includes a method of protecting the uneven pattern surface by bringing a shielding plate very close to the uneven pattern, or a method of protecting the uneven pattern surface by bringing a mold substrate into contact with the uneven pattern surface. However, even if the shielding plate is brought very close to the uneven pattern surface, it does not completely adhere, so the liquid-repellent component penetrates into the uneven pattern surface. In addition, in the method of protecting the uneven pattern surface by bringing the mold substrate into contact, since both the mold for imprinting and the mold substrate are hard solid materials, it is difficult to bring the plate material into contact with the entire area to be protected. Therefore, it is not possible to prevent the liquid-repellent component from penetrating into any place, and residues of the liquid-repellent material may remain on the uneven pattern surface. Therefore, the method described in Patent Document 1 may generate residues made of the liquid-repellent material, and the residues may remain on the mesa sidewalls. In other words, the method described in Patent Document 1 may not be able to remove the residues when they are generated.

[0009] Therefore, in order to solve the above problems, an object of the present invention is to provide a method for removing residues that occur at least near the side surfaces of the convex portion of the mold. [Means for solving the problem]

[0010] In order to achieve the above object, one aspect of the present invention provides a removal method for removing residue adhering to a mold having a base with a main surface and convex portions provided on the main surface, with a concave-convex pattern formed on the upper surfaces of the convex portions to be pressed against a curable composition, the removal method including a first removal step for removing the residue, wherein the first removal step is characterized in that the residue is removed by dissolving a liquid-repellent layer formed on at least the side surfaces of the convex portions with a predetermined solvent. Effect of the Invention

[0011] According to the present invention, it is possible to remove residues occurring at least near the side surfaces of the protruding portions of the mold. [Brief description of the drawings]

[0012] [Figure 1] FIG. 2 is a cross-sectional view of a mold according to an embodiment. [Diagram 2] FIG. 2 is a configuration diagram of a removal device according to an embodiment. [Diagram 3] FIG. 2 is a schematic diagram of a protective layer forming unit according to the embodiment. [Figure 4] FIG. 2 is a schematic diagram of a protective layer removal unit according to an embodiment. [Diagram 5] 4A to 4C are explanatory diagrams of each step of removing residue according to the embodiment. [Figure 6] 4 is a flowchart showing a residue removal process in the present embodiment. [Figure 7] 1A to 1C are diagrams illustrating an imprint method according to an embodiment. [Figure 8] FIG. 2 is a schematic diagram for explaining a method for manufacturing an article. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] Hereinafter, an embodiment of the present invention will be described in detail with reference to the drawings as appropriate. However, the present invention is not limited to the embodiment described below. In addition, in the present invention, modifications and improvements to the embodiment described below based on the ordinary knowledge of a person skilled in the art are also included in the scope of the present invention, as long as they do not deviate from the gist of the present invention.

[0014] <Embodiment 1> The mold (form, mask) used in nanoimprinting is formed so that the mold substrate other than the contact surface (imprint surface) does not come into contact with the substrate to be processed even if the parallelism between the mold and the substrate to be processed is not perfect. Specifically, the contact surface of the mold is formed so as to have a surrounding side wall surface and to have a protruding (projecting) shape from the mold base material. The convex portion where the contact surface is formed, that is, the plateau portion formed by the contact surface as the upper surface and the side wall surface, is called a mesa portion. With this configuration, a certain clearance can be obtained between the substrate to be processed and the surface other than the imprint surface of the mold during imprinting, and it is possible to prevent the two from coming into contact with each other.

[0015] Fig. 1 is a cross-sectional view of a mold 11 in this embodiment. Hereinafter, with reference to Fig. 1, the mold 11 of this embodiment on which a liquid-repellent layer has been formed and from which residues have been removed, and a method for removing residues attached to the mold in order to obtain the mold 11 (mold cleaning method) will be described.

[0016] As shown in Fig. 1, the mold 11 according to this embodiment has a mesa portion (a convex pattern forming portion) 11a, and a fine concave-convex pattern (pattern portion) 11b is formed on the lower surface (imprint surface) of the mesa portion 11a. By pressing this concave-convex pattern 11b against a curable composition 13 on a substrate 12, the concave-convex pattern 11b is transferred to the curable composition 13 to form a curable composition pattern 13a. That is, the mold 11 in this embodiment has a base having a main surface and a convex portion provided on the main surface, and a concave-convex pattern to be pressed against the curable composition is formed on the upper surface of the convex portion. The mold 11 is formed of, for example, quartz or the like.

[0017] When the concave-convex pattern 11b of the mold 11 is pressed against the curable composition 13, the curable composition 13 may protrude outside the imprint surface and creep up and adhere to the sidewall 11d of the mesa portion 11a. In order to prevent this, the mold 11 in this embodiment has a liquid-repellent layer 14 having a liquid-repellent surface formed on the sidewall 11d of the mesa portion 11a. The liquid-repellent layer 14 is formed to have a certain degree of thickness. The liquid-repellent layer 14 is a film (liquid-repellent layer) that has a higher contact angle with the curable composition 13 than the surface material of the mold 11 on which the liquid-repellent layer 14 is formed, such as quartz. The liquid-repellent layer is preferably formed by a wet method, in particular by applying a liquid material and drying it.

[0018] A method for forming the liquid-repellent layer 14 will be described later, but in this embodiment, the liquid-repellent layer 14 is formed at least on the side wall of the mold 11 (the side wall 11d of the mesa portion 11a). This makes it possible to prevent the curable composition 13, which is an organic material, from creeping up onto the side wall of the mold 11 when the mold 11 is pressed against the curable composition 13 on the substrate 12 as described above. The liquid-repellent layer 14 may also be formed on the upper surface 11e or the side wall 11f of the base portion 11c of the substrate supporting the mesa portion 11a, but is formed at least on the side wall 11d of the mesa portion 11a as described above.

[0019] Here, when forming the liquid-repellent layer 14 on the side wall 11d of the mesa portion 11a, it is necessary to prevent the liquid-repellent layer from being formed on the imprinted surface. If a liquid-repellent layer is formed on the imprinted surface, there is a risk of a defect of non-filling of the curable composition 13. In other words, it may happen that the concave-convex pattern 11b of the mold 11 is not sufficiently filled with the curable composition.

[0020] In the present embodiment, the liquid-repellent layer 14 is formed on the mold 11 by forming a protective layer on the imprint surface, forming the liquid-repellent layer 14 on the sidewall 11d of the mesa portion 11a, and then removing the protective layer formed on the imprint surface. When forming the liquid-repellent layer 14, the protective layer is formed on the imprint surface before the liquid-repellent layer 14 is formed, thereby preventing the liquid-repellent layer from being formed on the imprint surface. In addition, since a small amount of residue (residue made of the liquid-repellent material) made of the liquid-repellent layer 14 may be formed on the end of the imprint surface at that time, the liquid-repellent layer 14 (including the imprint surface of the mold 11) is finally washed with a predetermined solvent (solvent) that dissolves the residue made of the liquid-repellent component. In this way, by performing the processes in the order of forming the protective layer, forming the liquid-repellent layer 14, removing the protective layer, and washing the liquid-repellent layer 14 (removing the residue), the liquid-repellent layer 14 can be appropriately formed on the sidewall 11d of the mesa portion 11a of the mold 11 while removing the residue.

[0021] A method for forming the protective layer is preferably a method for applying a protective material to the imprint surface. For example, the protective material can be applied to the imprint surface by a dispenser or a printing method. The protective material may be applied to at least the outer periphery of the imprint surface. However, the protective material may be applied to the entire imprint surface, or may be applied to the outer periphery of the imprint surface and its vicinity, and may be selected according to the method for forming the liquid-repellent layer 14. When the outer periphery of the imprint surface is applied, the protective material can be reduced compared to application to the front surface, and the application time of the protective material can also be shortened.

[0022] Examples of materials for forming the protective layer (protective materials) include, but are not limited to, glycerin, diglycerin, and aqueous polyacrylic acid solutions. A mixture of a plurality of these materials may also be used.

[0023] The liquid-repellent layer 14 may be formed by a dry method such as a sputtering method or a vapor deposition method, or may be formed by a wet method in which a liquid material is applied and dried. The wet method is more preferable for forming the liquid-repellent layer 14. Here, when the liquid-repellent layer 14 is formed by a dry method, the protective layer may be formed on the entire imprint surface. Also, if the method is such that the liquid-repellent layer 14 can be formed partially, such as a wet method, the protective layer is formed on the outer periphery of the imprint surface. Here, the protective layer may be formed on the entire imprint surface in addition to the outer periphery.

[0024] In the present embodiment, the liquid-repellent material forming the liquid-repellent layer 14 is preferably a liquid liquid-repellent material in a wet method, and is particularly preferably a solution containing a polymer having a fluorocarbon chain and a volatile solvent that dissolves the polymer. The polymer having a fluorocarbon chain has a high contact angle with the cured composition, and can form a good liquid-repellent layer. The volatile solvent that dissolves the polymer is not particularly limited as long as it is a volatile solvent that dissolves the polymer having a fluorocarbon chain. For example, Novec7200 and Novec7300 manufactured by 3M can be mentioned, but is not particularly limited to these. A mixture of these materials may also be used.

[0025] A preferred method for removing the protective layer is to dissolve and remove the protective material forming the protective layer with water or an organic solvent. A material that has high solubility in the protective material and does not affect the liquid-repellent layer 14 may be selected as the material for dissolving the protective material. In addition, while the protective layer is being formed, contamination of the imprint surface, such as adhesion of dust or organic matter (adhesion of foreign matter), can be prevented, so the protective layer may be removed immediately after the liquid-repellent layer 14 is formed, or may be removed immediately before carrying out the imprint process.

[0026] When forming the liquid-repellent layer 14, a small amount of the liquid repellent material may overflow from the edge of the convex portion, and the overflowing liquid repellent material may rise slightly along the side wall of the convex portion. If this raised portion remains on the pattern surface as a residue, problems such as poor contact on the imprint surface may occur, so the residue must be removed. In this embodiment, in order to remove such residue, a removal process (cleaning process) is performed in which the residue of the liquid repellent material that occurs on the surface of the liquid repellent layer 14 and on the edge of the liquid repellent layer 14 is removed by dissolving it with a solvent.

[0027] A preferred method (cleaning method) for removing residues of the liquid-repellent material that forms the liquid-repellent layer 14 is to dissolve and remove all unnecessary residues while dissolving the surface of the liquid-repellent layer 14 with a volatile solvent that can dissolve the liquid-repellent material components in the liquid-repellent layer 14. For this reason, it is preferred to select a material that has high solubility in the liquid-repellent material, can remove the residues, and does not affect the liquid-repellent layer.

[0028] As a specific method for removing the residue, for example, a solvent for the liquid-repellent material is supplied from a supply head capable of supplying the liquid-repellent material to dissolve the protective material while rotating the mold 11 using a rotating mechanism. This allows unnecessary residue remaining around the liquid-repellent layer to be dissolved in the solvent for the liquid-repellent material and removed (spin method).

[0029] Also, for example, by using an immersion mechanism in which a container is filled with the solvent of the liquid-repellent material, the mold 11 can be repeatedly immersed in and pulled out of the solvent of the liquid-repellent material multiple times by the immersion mechanism, so that unnecessary residue remaining around the liquid-repellent layer 14 can be dissolved in the solvent of the liquid-repellent material and removed (immersion method).

[0030] Unwanted residues are quickly dissolved by contact with the solvent. In this case, the cleaning time is a few seconds, and the residues can be removed. It is possible to remove all of the unwanted residues with a minimum cleaning time of 5 seconds. In other words, by setting the cleaning time to 5 seconds, the residues can be reliably dissolved and removed.

[0031] Although the surface of the liquid-repellent layer 14 itself is slightly dissolved by this cleaning (dissolving the liquid-repellent layer 14 with a solvent to remove the residue), the minimum required liquid-repellent performance is maintained as long as a thickness of about several nm of the liquid-repellent layer remains. For example, the minimum required liquid-repellent performance is maintained as long as a thickness of about 3 nm or more remains. It is preferable that a thickness of 10 nm or more remains, and more preferable that a thickness of 15 nm or more remains, as this provides sufficient liquid-repellent performance.

[0032] The solvent for removing the residue of the liquid-repellent layer 14 contains at least one of hydrofluoroether, perfluorocarbon, and hydrofluorocarbon, and is liquid at room temperature (25° C.) having the following properties (a) to (d). (a) Boiling point is less than 100°C (b) Vapor pressure at 25°C is 5 to 30 KPa (c) Density at 25°C is 1050 kg / m3 or more (d) Surface tension at 25°C is 20 mN / m or less

[0033] The hydrofluoroether (HFE) used in this embodiment is not particularly limited, and is preferably one having the formula R1-O-R2 (wherein R1 is a C1 to C12 hydrocarbon alkyl group or a hydrofluorocarbon, and R2 is a C1 to C12, preferably a C3 to C12 perfluorocarbon or a hydrofluorocarbon).

[0034] Specific examples of hydrofluoroethers include 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, ethyl nonafluoroisobutyl ether, and ethyl nonafluorobutyl ether. Further examples include methyl perfluoroisobutyl ether, methyl perfluorobutyl ether, and HFE-347pc-f (CF3CH2OCF2CHF2). Further examples include HFC-52-13p (CF3CF2CF2CF2CF2CHF2), and HFC-569sf (CF3CF2CF2CF2CH2CH3). Specific examples of products include "Novec" manufactured by Sumitomo 3M, "Asahiclean" manufactured by Asahi Glass, Asahiclean AE-3000 (Asahi Glass), and Asahiclean AC-2000 (Asahi Glass). Further examples include Asahiklin AC-4000 (Asahi Glass), Novec HFE-7100 (Sumitomo 3M), Novec HFE-7200 (Sumitomo 3M), etc. The above hydrofluoroethers may be used alone or in combination of two or more kinds.

[0035] Specific examples of perfluorocarbons that can be used in this embodiment include perfluorobutane, perfluoropentane, and perfluorohexane. Further examples include perfluoroheptane, perfluorooctane, perfluorononane, and perfluorodecane. Specific commercial products include Fluorinert (Sumitomo 3M), Flutec (Rhoneplan), Galden (Ausimont), and Alfood (Asahi Glass). The above perfluorocarbons may be used alone or in combination of two or more types.

[0036] Specific examples of hydrofluorocarbons include HFC-43-10mee, 1,1,1,3,3 pentafluorobutane, 1,1,2,2,3,3,4-heptafluorocyclopentane, etc. In addition, octafluorocyclopentane, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-trifluoromethyl-pentane, 2,3-dihydrodecafluoropentane, etc. Specific commercial products include Zeorola manufactured by Zeon Corporation, Vertrel (Mitsui DuPont Fluorochemicals), Solkan 365mfc (Solvay), etc. The above hydrofluorocarbons may be used alone or in a mixture of two or more kinds.

[0037] The solvent for removing the residue of the liquid-repellent layer 14 is preferably a volatile solvent that dissolves the polymer having a fluorocarbon chain. When forming the liquid-repellent material, the volatile solvent is evaporated, so a low boiling point is desirable for rapid evaporation, but if the boiling point is too low, the polymer having a fluorocarbon chain solidifies at the tip of the supply head, making it impossible to apply stably. The boiling point is preferably 50 to 140°C, more preferably 60 to 100°C. Examples of the solvent include Novec7200 and Novec7300 manufactured by 3M, but are not limited to these. A mixture of these materials may also be used.

[0038] The above method allows the liquid-repellent layer 14 to be formed up to the end of the sidewall in the direction toward the pattern surface, which is the most effective in suppressing seepage, without leaving any residue of the liquid-repellent material on the outer peripheral edge of the mesa portion 11a, which is also the imprint surface. This makes it possible to effectively suppress seepage caused by the liquid-repellent layer.

[0039] 2 is a diagram showing an example of the configuration of a removal device (washing device, cleaning device) in this embodiment that removes (washes) residues from mold 11. The removal device in this embodiment functions as a device that forms liquid-repellent layer 14 on mold 11 after forming a protective layer, and then dissolves liquid-repellent layer 14 of mold 11 using a solvent to remove (wash, clean) residues of the liquid-repellent material.

[0040] 2 includes a protective layer forming unit (first forming section), a liquid repellent layer forming unit (second forming section), a protective layer removing unit (second removing section), a residue removing unit (first removing section), a transport section, and a control section 111. Each unit is connected to the transport section that transports the imprint mold. The control section also controls the operation content and operation timing of each unit and the transport section.

[0041] 3 is a schematic diagram of a protective layer forming unit according to this embodiment. The protective layer forming unit is a unit that forms a protective layer on the mold 11 by using a liquid protective material to prevent a liquid-repellent layer 14 from being formed on the imprint surface. As will be described later, the protective layer forming unit forms a protective layer on at least the outer periphery of the concave-convex pattern 11b of the mold 11. The protective layer forming unit includes a stage (mold holding unit, moving mechanism) 102, a supply head 103, a moving mechanism 104, a processing chamber 109, and an imaging unit 110.

[0042] The stage 102 has the unprocessed mold 11 placed thereon, and functions as a mold holding section that can move the mold 11 in the X-axis, Y-axis, and Z-axis directions while holding the mold 11.

[0043] The supply head 103 is a dispenser that dispenses a liquid protective material. The supply head 103 is capable of storing therein the liquid protective material that is supplied from a tank or the like outside the processing chamber 109. The supply head 103 then dispenses the stored liquid protective material toward the unprocessed mold 11 on the stage 102 at a predetermined timing. The supply head 103 is electrically connected to a control unit 111, and its driving is controlled by the control unit 111.

[0044] The moving mechanism 104 holds the supply head 103 and moves it relative to the stage 102 while holding the supply head 103. The moving mechanism includes movable mechanisms that move in the X-axis, Y-axis, and Z-axis directions, each of which operates independently. As the moving mechanism 104, for example, a linear motor type moving mechanism, an air stage type moving mechanism, a feed screw type moving mechanism, or other moving mechanism can be used.

[0045] The processing chamber 109 is formed in a box shape so as to be able to accommodate the supply head 103, the stage 102, the imaging unit 110, the moving mechanism 104, and the like. A filter unit 112 having a filter attached thereto for removing foreign matter from the air is provided on the upper surface of the processing chamber, and an exhaust port 113 is provided on the lower surface (bottom surface) of the processing chamber 109. In the processing chamber 109, air flows from the filter in the filter unit to the exhaust port 113, and the inside of the processing chamber 109 is kept clean by a downflow (vertical laminar flow). For example, a ULPA filter or a HEPA filter can be used as the filter. The mold 11 is processed in the processing chamber 109.

[0046] The imaging unit 110 is an imaging device such as a camera capable of imaging the mold 11 on the stage 102. The imaging unit 110 is attached to the upper surface of the processing chamber 109 so as to be able to image, in particular, the convex portions of the mold 11 and their surroundings. The imaging unit 110 is electrically connected to the control unit 111, and transmits the captured image (for example, a planar image of the convex portions of the mold 11) to the control unit 111 or an external device such as an information processing device.

[0047] The liquid-repellent layer forming unit (second forming section) is a unit that forms liquid-repellent layer 14 at least on the mesa sidewall (side surface of the convex portion) of mold 11. In this embodiment, the liquid-repellent layer forming unit (second forming section) forms liquid-repellent layer 14 also on a portion of the protective layer when forming liquid-repellent layer 14 on sidewall 11d of mesa portion 11a of mold 11. The configuration of the liquid-repellent layer forming unit is not particularly limited, but the configuration differs between the dry method and the wet method.

[0048] Here, in the case of the dry method, for example, a chamber, a liquid-repellent material holding section, and a liquid-repellent material heating section such as a heater are provided, and the liquid-repellent material is heated in the liquid-repellent material heating section to evaporate and gasify the liquid-repellent material, thereby forming a liquid-repellent layer 14 on the mold 11.

[0049] In the case of a wet method, the configuration can be the same as that of the protective material application unit. That is, the configuration can be configured to include a stage, a supply head, a moving mechanism, a processing chamber, and an imaging unit. In this case, the liquid repellent material is supplied from the supply head, and the liquid repellent material is applied to a predetermined area including the mesa sidewall of the mold. The liquid repellent layer is also formed by applying the liquid repellent material onto the mold 11 in the same configuration as in FIG. 3.

[0050] 4 is a schematic diagram of the protective layer removal unit according to this embodiment. The protective layer removal unit (second removal section) is a unit that dissolves the protective layer with a protective layer removal material capable of dissolving the protective layer, and removes the protective layer formed on the mold 11. By dissolving the protective layer in the protective layer removal unit, the protective layer and the liquid repellent layer 14 formed on a part of the protective layer can also be removed. The protective layer removal unit (second removal section) includes a stage (mold holding section, moving mechanism) 102, a moving mechanism 104, a processing chamber 109, a supply head 118, and a rotating stage 119.

[0051] The mold 11, on which a protective layer and a liquid-repellent layer 14 are formed, is placed on the stage 102. The stage 102 also functions as a mold holding section that enables the stage 102 to move in the X-axis, Y-axis, and Z-axis directions while holding the mold 11.

[0052] The moving mechanism 104 holds the supply head 118 and moves it relative to the stage 102 while holding the supply head 118. The moving mechanism includes movable mechanisms that move in the X-axis, Y-axis, and Z-axis directions, each of which operates independently. As the moving mechanism 104, for example, a linear motor type moving mechanism, an air stage type moving mechanism, a feed screw type moving mechanism, or other moving mechanism can be used.

[0053] The processing chamber 109 is formed in a box shape so as to be able to accommodate the supply head 118, the stage 102, the moving mechanism 104, and the like. A filter unit 112 having a filter attached thereto for removing foreign matter from the air is provided on the upper surface of the processing chamber, and an exhaust port 113 is provided on the lower surface (bottom surface) of the processing chamber 109. In the processing chamber 109, air flows from the filter in the filter unit to the exhaust port 113, and the inside of the processing chamber 109 is kept clean by a downflow (vertical laminar flow). As the filter, for example, a ULPA filter or a HEPA filter can be used. The mold 11 is processed in the processing chamber 109.

[0054] The supply head 118 is a dispenser that dispenses the protective layer removal material. The supply head 118 is capable of storing a liquid removal material that is supplied from a tank or the like outside the processing chamber 109. The supply head 118 then dispenses the stored liquid protective material toward the mold 11 on the stage 102 at a predetermined timing. The supply head 118 is electrically connected to the control unit 111, and its driving is controlled by the control unit 111.

[0055] The rotation stage 119 is a rotation mechanism that rotates the mold 11 around the Z axis while holding the mold 11 by vacuum suction or the like.

[0056] In this embodiment, the protective layer is removed using a configuration that combines a supply head 118 and a rotating stage 119. Specifically, the mold 11 having the liquid-repellent layer formed thereon is placed on the rotating stage 119 so that the center of rotation is aligned with that of the rotating stage 119. At this time, the mold 11 is held on the rotating stage 119 by a method such as vacuum suction. After the mold 11 is held, the rotating stage 119 is rotated, whereby the mold 11 also rotates in conjunction with it. At this time, it is preferable to rotate the rotating stage 119 at a low speed.

[0057] Next, while maintaining the supply head 118 at a predetermined height, the movement mechanism 104 moves the supply head 118 to above the center of the imprint surface 11g, and then the supply head 118 discharges (applies, supplies) the protective layer removal material onto the mold 11. The protective layer removal material is discharged onto or near the center of the imprint surface 11g, and spreads toward the outer periphery due to the centrifugal force of the rotation. This allows the components of the protective layer to be dissolved, while the dissolved protective layer (protective material) flows out of the mold 11. Then, by dissolving and removing the protective layer, a part of the liquid-repellent layer 14 formed on the protective layer is also removed from the imprint surface 11g. By continuing to discharge the protective layer removal material, all of the components of the protective layer are dissolved into the protective layer removal material. Then, when the protective layer (including the liquid-repellent layer formed on the protective layer) is removed from the imprint surface 11g, the discharge of the protective layer removal material is stopped, and the surface of the mold 11 is dried. The rotation of the rotating stage 119 is also stopped.

[0058] In addition, when removing the protective layer, a so-called spin method may be used in which the protective layer removal material is supplied from the supply head 118 as described above, and the protective material is dissolved and removed while rotating the mold 11 on the rotating stage 119. However, the method of removing the protective layer is not limited to the spin method. For example, the protective layer removal unit may be equipped with an immersion mechanism that fills a container with the protective layer removal material. Then, a so-called immersion method may be used in which the mold 11 is repeatedly immersed in the immersion mechanism filled with the protective layer removal material and pulled up multiple times, thereby dissolving the protective material in the protective layer removal material and removing it.

[0059] The residue removal unit (first removal section) is a unit that removes residue from the mold 11 by dissolving the residue using a predetermined solvent (solvent of the liquid-repellent material) that can dissolve the residue made of the liquid-repellent layer. The configuration of the residue removal unit is not particularly limited. For example, the residue removal unit may include a supply head as shown in FIG. 3 or FIG. 4 that supplies the solvent of the liquid-repellent material, and a rotation mechanism that rotates the mold 11. By supplying the solvent of the liquid-repellent material from the supply head to dissolve the residue made of the liquid-repellent material while rotating the imprint mold with the rotation mechanism, the residue remaining around the liquid-repellent layer can be dissolved in the solvent of the liquid-repellent material and removed (spin method). The removal of the residue is also performed in the same manner as in the protective layer removal unit, by discharging a solvent onto the imprint surface on the mold 11, and dissolving the residue by the centrifugal force of the rotation and flowing it out of the mold.

[0060] Also, for example, an immersion mechanism may be provided in which a container is filled with a solvent for the liquid-repellent material. By repeatedly immersing and pulling up the mold 11 in the immersion mechanism filled with the solvent for the liquid-repellent material multiple times, the residue remaining around the liquid-repellent layer 14 can be dissolved in the solvent for the liquid-repellent material and removed (immersion method).

[0061] The transfer section transfers the mold 11 between each unit while holding the mold 11. As the transfer section, a movable stage or a multi-axis robot may be used.

[0062] The control unit 111 includes a CPU, a memory (storage unit), and the like, and is configured as at least one computer, and is electrically connected to each component of the removal apparatus via a line. The control unit 111 also performs overall control of the operation adjustment of each component of the entire removal apparatus, such as the operation contents and operation timing of each unit and the transport unit, according to a program stored in the memory. The control unit 111 may also be configured integrally with other parts of the removal apparatus (in a common housing). Furthermore, the control unit 111 may also be configured separately from other parts of the removal apparatus (in a different housing), or may be installed in a different location from the removal apparatus and controlled remotely. The CPU may also be an MPU. The memory stores, for example, various operation contents and operation timings.

[0063] In this embodiment, as shown in Fig. 2, the protective layer forming unit, the liquid repellent layer forming unit, the protective layer removing unit, and the residue removing unit are each independently arranged in the processing apparatus. However, the mechanisms of multiple units may be integrated into one unit. For example, one unit may be provided with multiple material supply heads, and the formation of the protective layer and the liquid repellent layer may be performed in one unit.

[0064] FIG. 5 is an explanatory diagram of each processing stage of the removal process (washing process, cleaning process) for removing residues according to this embodiment. FIG. 6 is a flowchart showing the residue removal process in this embodiment. In FIG. 5, 15 indicates a protective layer (hereinafter, protective layer 15). Also, 14a indicates a liquid-repellent layer formed on the mesa sidewall and part of the protective layer 15 before the protective layer is removed (hereinafter, liquid-repellent layer 14a). Also, 14b indicates a liquid-repellent layer after the protective layer 15 is removed (hereinafter, liquid-repellent layer 14b). Also, 14c indicates a liquid-repellent layer after the residues are removed (hereinafter, liquid-repellent layer 14c). In FIG. 5, the protective layer and the liquid-repellent layer at each stage are given respective reference symbols for clarity of explanation.

[0065] In this embodiment, as described above, the protective layer 15 is formed on the outer periphery of the imprint surface of the mold 11, and the liquid-repellent layer 14a is formed on the mesa sidewall. Thereafter, the protective layer 15 is removed, and finally, unnecessary residues are removed by a residue removal method, thereby forming the liquid-repellent layer 14c as shown in FIG. 5. Hereinafter, a detailed description will be given with reference to FIG. 5 and FIG. 6. Each of the following processes is realized by the control unit 111 of the processing device executing a program stored in the memory. Also, each process (step) is represented by adding an S to the beginning, and the representation of the process (step) is omitted.

[0066] First, in S101, the control unit 111 controls the protective layer forming unit to apply a liquid protective material from the supply head 103 to the outer periphery of the imprint surface on the mold 11, thereby forming a protective layer 15 on the mold 11 as shown in Fig. 5 (first forming step). When forming the protective layer 15 that prevents the formation of a liquid-repellent layer, the protective layer 15 is formed on at least the outer periphery of the concave-convex pattern on the mold 11. Here, while maintaining a predetermined height, the supply head 103 is moved by the movement mechanism 104 along application paths P1-1 to P5-1 on the imprint surface 11g as shown in Fig. 5, and continuously supplies the protective material to the imprint surface 11g on the mold 11.

[0067] The application paths P1-1 to P5-1 are separated from the outer periphery of the imprint surface 11g by a predetermined distance L-1 (for example, 0.2 mm). P1-1 is the discharge start position and P5-1 is the discharge stop position. The protective material is applied only to the outer periphery of the imprint surface 11g by this application path. Furthermore, the liquid protective material applied on this application path spreads over the imprint surface due to wetting spread caused by surface energy, and reaches the outer periphery edge 11h of the imprint surface. In this way, by carrying out the first formation step, the protective layer 15 can be formed on the outer periphery of the mold 11.

[0068] Next, in S102, the control unit 111 controls the liquid-repellent layer forming unit to apply a liquid-repellent material from a supply head to the upper surface 11e of the mold 11, forming a liquid-repellent layer 14a as shown in FIG. 5 (second forming step). When forming the liquid-repellent layer 14a, it is formed on at least the side surface of the convex portion of the mold 11. The coating paths P1-2 to P5-2 move on the upper surface 11e along the outer periphery of the imprint surface 11g in the order of P1-2, P2-2, P3-2, P4-2, and P5-2. The coating paths are separated from the imprint surface 11g by a predetermined distance L-2 (for example, 1 mm). In this embodiment, P1-2 is the discharge start position, and P5-2 is the discharge stop position.

[0069] The area coated by this coating path has, for example, a frame shape surrounding the imprint surface 11g. The liquid repellent material coated by this coating path spreads due to its wettability, reaches the side wall 11d of the mesa portion 11a, and further passes over the side wall 11d of the mesa portion 11a to reach the protective layer 15 formed on the outer periphery of the imprint surface 11g. By coating in this manner, the liquid repellent material can be coated on the side wall 11d and the upper surface 11e around the side wall 11d.

[0070] Thereafter, when the volatile solvent contained in the liquid repellent material evaporates and dries, a liquid repellent layer 14a is formed on the side wall 11d of the mesa portion 11a and on a part of the protective layer 15. In this way, by performing the second forming step after the first forming step, the liquid repellent material does not reach the imprint surface on which the protective layer 15 is not formed. Therefore, it is possible to form a liquid repellent layer on at least the side surface of the convex portion of the mold 11 without forming the liquid repellent layer 14a on the imprint surface 11g.

[0071] Next, in S103, the control unit 111 controls the protective layer removal unit to supply a protective layer removal material capable of dissolving the protective layer 15 from the supply head 118 to the mold 11, and removes the protective layer 15 formed on the mold 11 (second removal step). When removing the protective layer 15, first, the mold 11 on which the liquid-repellent layer 14a has been formed is placed on the rotating stage 119 so that the center of rotation is aligned with the rotating stage 119. At this time, after the mold 11 is placed, the mold 11 is held on the rotating stage 119 by a method such as vacuum suction. After the mold 11 is held, the rotating stage 119 and the mold 11 are rotated at a low speed. After rotating the mold 11 at a low speed, the supply head 118 is moved to the upper part of the center on the imprint surface 11g by the moving mechanism 104 while maintaining the supply head 118 at a predetermined height, and then the protective layer removal material is discharged from the supply head 118 onto the mold 11.

[0072] The protective layer removal material is discharged onto the center of the imprint surface 11g, and spreads toward the outer periphery due to the centrifugal force of the rotation, dissolving the components of the protective layer 15 and flowing out of the mold 11. As the protective layer 15 is dissolved and removed, a part of the liquid-repellent layer 14a formed on the protective layer 15 is also removed. By continuing to discharge the protective layer removal material, when all the components of the protective layer 15 are dissolved in the protective layer removal material and removed from the imprint surface 11g, the discharge of the protective layer removal material is stopped and the surface of the mold 11 is dried. By performing the second removal step after the second formation step in this way, a liquid-repellent layer 14b as shown in FIG. 5 can be formed.

[0073] Finally, in S104, the control unit 111 controls the residue removal unit to remove residue from the mold 11 on which the liquid-repellent layer 14b, which is the liquid-repellent layer after the protective layer 15 has been removed, has been formed (first removal step). In removing the residue, the liquid-repellent layer 14b is dissolved with a predetermined solvent to remove the residue from the outer peripheral edge of the mesa portion 11a and the like. The residue is removed using a configuration that combines a supply head 118 and a rotating stage 119 shown in FIG. 4. The mold 11 on which the liquid-repellent layer 14b has been formed is placed on the rotating stage 119 so that the center of rotation is aligned with that of the rotating stage 119.

[0074] At this time, after the mold 11 is placed, the mold 11 is fixed to the rotating stage 119 by a method such as vacuum suction, and then the rotating stage and the mold are rotated at a low speed. While maintaining a predetermined height, the supply head 118 is moved to the upper part of the center of the imprint surface 11g by the moving mechanism 104, and then the solvent of the liquid repellent material is discharged from the supply head 118 onto the mold. The solvent of the liquid repellent material is discharged to the center of the imprint surface 11g, spreads toward the outer periphery due to the centrifugal force of the rotation, dissolves the residue, and flows out of the mold 11 and is removed. The solvent of the liquid repellent material is continuously discharged, and when all the unnecessary residue is dissolved in the solvent of the liquid repellent material and removed from the imprint surface 11g, the discharge of the solvent of the liquid repellent material is stopped. This makes it possible to form a liquid repellent layer 14c from which the unnecessary residue has been removed. Thereafter, the surface of the mold 11 is dried. In this manner, by carrying out the first removal step after the second removal step, it is possible to form a liquid-repellent layer 14c from which unnecessary residues have been removed, at least on the side wall 11d of the mesa portion 11a, as shown in FIG.

[0075] By using the above-described removal method, the protective material and unnecessary residues on the imprint surface are removed, and a mold can be obtained (a mold can be manufactured) in which a liquid-repellent layer 14c, which is a liquid-repellent layer with the residues removed only on the mesa side walls, is formed.

[0076] As described above, in the removal method using the removal device in the first embodiment, it is possible to form a liquid-repellent layer with high accuracy only on the mesa sidewalls without making the entire area of ​​the concave-convex pattern surface of the mold 11 liquid-repellent. Also, it is possible to remove residues generated at least on the side surfaces of the convex portions of the mold with high accuracy.

[0077] In this embodiment, the liquid repellent layer is formed after forming the protective layer on the pattern surface of the mold 11, but a light shielding layer for blocking exposure light may be formed on the side surface of the mesa portion 11a of the mold 11. The method of this embodiment in which a protective layer is formed in advance is also effective when forming a light shielding layer.

[0078] Furthermore, the protective layer formed over the entire imprint surface of the mold 11 can protect against debris and contamination other than the liquid-repellent material, and therefore functions not only for the mold 11 used for imprinting, but also as a contamination prevention layer for the mold 11 during transportation.

[0079] The removal device described above can be equipped with a transport mechanism, a loading section, an unloading section, etc. to make the mesa sidewall of the mold 11 liquid-repellent and to be used as a device for removing residues.

[0080] In this embodiment, the protective layer is formed by the protective layer forming unit. Here, for example, after the concave-convex pattern 11b is protected by a light shielding plate having a predetermined shape, a liquid-repellent layer may be formed by the liquid-repellent layer forming unit, and the residue generated at the end of the mesa portion 11a may be removed by the residue removing unit. At this time, the shielding plate is disposed facing the concave-convex pattern 11b at a distance. Also, for example, a predetermined buffer material is brought into contact with the concave-convex pattern 11b, and a mold substrate is disposed on the buffer material to protect the concave-convex pattern 11b. Thereafter, the liquid-repellent layer 14 may be formed by the liquid-repellent layer forming unit, and the residue generated at the end of the mesa portion 11a may be removed by the residue removing unit. The buffer material may be, for example, a liquid such as water, alcohol, or thinner, or a gel-like material. Also, the mold substrate is formed of, for example, quartz. Also, for example, the liquid-repellent layer 14 may be formed by the liquid-repellent layer forming unit while the concave-convex pattern 11b is pressed against the curable composition 13, and the residues generated on the ends of the mesa portion 11a and the like may be removed by the residue removing unit. When such a removal method is used, the protective layer removing unit can be eliminated from the configuration of the removal apparatus. Eliminating the protective layer removing unit can reduce the overall size of the removal apparatus.

[0081] Furthermore, a mold 11 having a liquid-repellent layer 14 formed on the sidewall 11d of the mesa portion 11a may be prepared using an external device outside the removal device in this embodiment, and the residues generated on the ends of the mesa portion 11a may be removed using a residue removal unit. In such a case, the removal device may be configured with only the residue removal unit. That is, the protective layer formation unit, the liquid-repellent layer formation unit, and the protective layer removal unit may be eliminated from the configuration of the removal device, and the size of the entire removal device may be reduced. Also, the time required to remove the residues may be shortened.

[0082] Example 1 Hereinafter, an experimental example in which the side surface of the mold 11 (side wall 11d of mesa portion 11a) was made liquid repellent using the removal method of this embodiment will be described. As conditions for making the side surface of the mold 11 liquid repellent using the method of this embodiment, glycerin was used as the protective material, and water was used as the protective layer removal material. In addition, the liquid repellent material was a polymer having a perfluoropolyether group, which is a carbon chain 2, in its main chain, dissolved in a volatile solvent at a solid content concentration of 0.09 wt%, and Novec7200 manufactured by 3M was used as the cleaning solvent for the liquid repellent material. In addition, the cleaning time with the cleaning solvent was 5 seconds.

[0083] To evaluate the liquid repellency after the liquid repellent treatment, the presence or absence of residues of the liquid repellent material on the imprint surface was confirmed by an observation mechanism using an optical microscope. In addition, the formed liquid repellent layer was subjected to cross-sectional exposure processing using FIB-SEM and SEM observation to measure the film thickness. Furthermore, to evaluate the liquid repellency, the curable composition before curing was dropped on the side wall of the mold 11 after the liquid repellent layer was formed, and the contact angle was measured. The contact angle was judged as liquid repellency ◯ when it was 70-100°, liquid repellency △ when it was 65-69°, and liquid repellency × when it was 68° or less and 101° or more.

[0084] The film thickness measurement and evaluation results of the liquid-repellent layer in Example 1 showed that no residue remained, the film thickness was 35 nm, and the liquid repellency was ○ (circle). Therefore, under the conditions in Example 1, good results were obtained with respect to the removal of the residue and the film thickness after the removal of the residue.

[0085] Example 2 In Example 2, the side surface of the mold 11 was made liquid repellent by changing the cleaning time to 30 seconds using the same method as in Example 1. In Example 2, the conditions were the same as in Example 1 except that the cleaning time was changed to 30 seconds. Here, when the film thickness of the liquid repellent layer was measured and the liquid repellency was evaluated in the same manner as in Example 1, no residue remained, the film thickness was 30 nm, and the liquid repellency was ○ (circle). Therefore, under the conditions in Example 2, good results were obtained with respect to the removal of the residue and the film thickness after the residue was removed.

[0086] Example 3 In Example 3, the cleaning time was changed to 15 minutes using the same method as in Example 1 to make the side surface of the mold 11 liquid repellent. In Example 3, the conditions were the same as in Example 1 except that the cleaning time was changed to 15 minutes. Here, when the film thickness of the liquid repellent layer was measured and the liquid repellency was evaluated in the same manner as in Example 1, no residue remained, the film thickness was 21 nm, and the liquid repellency was ○ (circle). Therefore, under the conditions in Example 3, good results were obtained with respect to the removal of the residue and the film thickness after the residue was removed.

[0087] Example 4 In Example 4, the cleaning solvent was changed to Novec7300 manufactured by 3M in the same manner as in Example 1 to make the side surface of the mold 11 liquid repellent. In Example 4, the conditions were the same as in Example 1 except that the cleaning solvent was changed to Novec7300 manufactured by 3M. Here, when the film thickness of the liquid repellent layer was measured and the liquid repellency was evaluated in the same manner as in Example 1, no residue remained, the film thickness was 38 nm, and the liquid repellency was ○ (circle). Therefore, under the conditions in Example 4, good results were obtained with respect to the removal of the residue and the film thickness after the removal of the residue.

[0088] Example 5 In Example 5, the side surface of the mold 11 was made liquid repellent by changing the cleaning time to 30 seconds using the same method as in Example 4. In Example 5, the conditions were the same as in Example 4 except that the cleaning time was changed to 30 seconds. Here, when the film thickness of the liquid repellent layer was measured and the liquid repellency was evaluated in the same manner as in Example 1, no residue remained, the film thickness was 35 nm, and the liquid repellency was ○ (circle). Therefore, under the conditions in Example 5, good results were obtained with respect to the removal of the residue and the film thickness after the residue was removed.

[0089] Example 6 In Example 6, the cleaning solvent was changed to acetone in the same manner as in Example 1 to make the side surface of the mold 11 liquid repellent. In Example 6, the conditions were the same as in Example 1, except that the cleaning solvent was changed to acetone. Here, when the film thickness of the liquid repellent layer and the liquid repellency were evaluated in the same manner as in Example 1, no residue remained, the film thickness was 11 nm, and the liquid repellency was △. Therefore, as a result of Example 6, although the film thickness of the liquid repellent layer was less than in Examples 1 to 5, the necessary liquid repellency was maintained and the residue was also removed, so that no problem was obtained.

[0090] Comparative Example 1 In Comparative Example 1, the cleaning solvent was changed to water in the same manner as in Example 1 to make the side surface of the mold 11 liquid repellent. In Comparative Example 1, the conditions were the same as in Example 1 except that the cleaning solvent was changed to water. Here, when the film thickness of the liquid repellent layer was measured and the liquid repellency was evaluated in the same manner as in Example 1, residue remained on a part of the imprint surface. The film thickness was 80 nm, and the liquid repellency was rated as ○ (circle). Therefore, the result in Comparative Example 1 was that the film thickness of the liquid repellent layer was sufficiently thick, but the residue could not be removed.

[0091] Comparative Example 2 In Comparative Example 2, the cleaning solvent was changed to hexane to make the side surface of the mold 11 liquid repellent in the same manner as in Example 1. In Comparative Example 2, the conditions were the same as in Example 1 except that the cleaning solvent was changed to hexane. Here, when the film thickness of the liquid repellent layer was measured and the liquid repellency was evaluated in the same manner as in Example 1, residue remained on a part of the imprint surface. The film thickness was 71 nm, and the liquid repellency was ○ (circle). Therefore, the result in Comparative Example 1 was that the film thickness of the liquid repellent layer was sufficiently thick, but the residue could not be removed.

[0092] Comparative Example 3 In Comparative Example 3, the cleaning solvent was changed to ethanol in the same manner as in Example 1 to make the side surface of the mold 11 liquid-repellent. In Comparative Example 3, the conditions were the same as in Example 1 except that the cleaning solvent was changed to ethanol. Here, when the film thickness of the liquid-repellent layer was measured and the liquid-repellent performance was evaluated in the same manner as in Example 1, residue remained on a part of the imprint surface. The film thickness was 69 nm, and the liquid repellency was ○ (circle). Therefore, the result in Comparative Example 1 was that the film thickness of the liquid-repellent layer was sufficiently thick, but the residue could not be removed.

[0093] As described above, in comparison with the results in Examples 1 to 6, the liquid-repellent layer had a sufficient thickness, but the residue could not be removed in Comparative Examples 1 to 3. The cleaning conditions and evaluations in the above-mentioned Examples 1 to 6 and Comparative Examples 1 to 3 are shown in Table 1 below. [Table 1]

[0094] The processing apparatus in this embodiment described above can be mounted on an imprinting apparatus. The imprinting apparatus is an apparatus that forms a pattern made of a cured product of the imprinting material on a substrate by bringing an imprinting material arranged in a pattern formation region on the substrate into contact with a concave-convex pattern of a mold and curing the imprinting material. The imprinting apparatus forms patterns made of a cured product in a plurality of pattern formation regions, and is used, for example, in the manufacture of devices such as semiconductor devices. In this embodiment, the imprinting apparatus employs a photocuring method.

[0095] The imprint material used is a curable composition (sometimes called an uncured resin) that is cured by application of curing energy. The curing energy may be electromagnetic waves, heat, or the like. The electromagnetic waves may be, for example, light having a wavelength selected from the range of 10 nm or more and 1 mm or less, such as infrared rays, visible light, or ultraviolet rays. The curable composition may be a composition that is cured by irradiation with light or by heating.

[0096] Among these, the photocurable composition that is cured by irradiation with light contains at least a polymerizable compound and a photopolymerization initiator, and may further contain a non-polymerizable compound or a solvent as necessary. The non-polymerizable compound is at least one selected from the group consisting of a sensitizer, a hydrogen donor, an internal mold release agent, a surfactant, an antioxidant, a polymer component, etc. The imprint material can be arranged on the substrate in the form of droplets, or in the form of islands or a film formed by connecting a plurality of droplets.

[0097] The imprint apparatus may include a mold holding unit, a structure, an irradiation unit, a substrate driving mechanism, a base plate, a substrate holding unit (substrate stage), a dispenser (discharge device), a mold driving mechanism, an imaging unit, a control unit, and the like.

[0098] The mold holding unit has a drive mechanism (movement unit) that moves the mold while holding it. The mold holding unit can hold the mold by attracting the outer peripheral area of ​​the surface of the mold that is irradiated with the irradiation light by vacuum suction force or electrostatic force. The structure supports the mold drive mechanism.

[0099] The irradiation unit (curing unit) cures the imprint material on the substrate by irradiating the imprint material with irradiation light such as ultraviolet light through a prism. The irradiation unit may include an exposure light source, an optical element that adjusts the irradiation light irradiated from the exposure light source to light appropriate for imprinting, and a light shielding plate (masking blade) that limits the irradiation area (irradiation range) of the irradiation light irradiated from the exposure light source.

[0100] The substrate holding unit has a substrate driving mechanism (moving unit) that can move the substrate in each axial direction while holding the substrate. The base surface plate supports the substrate holding unit and the substrate driving mechanism. The substrate driving mechanism and the mold driving mechanism are configured as relative driving mechanisms that drive at least one of the substrate and the mold so that the relative positions of the substrate and the mold are adjusted. The adjustment of the relative positions by the relative driving mechanisms (substrate driving mechanism and mold driving mechanism) includes driving for contact between the imprint material on the substrate and the concave-convex pattern of the mold, and for separating the hardened imprint material from the mold.

[0101] The substrate driving mechanism may be configured to drive the substrate about multiple axes (e.g., three axes, namely, X-axis, Y-axis, and θZ-axis, and preferably six axes, namely, X-axis, Y-axis, Z-axis, θX-axis, θY-axis, and θZ-axis). The mold driving mechanism may be configured to drive the mold about multiple axes (e.g., three axes, namely, Z-axis, θX-axis, and θY-axis, and preferably six axes, namely, X-axis, Y-axis, Z-axis, θX-axis, θY-axis, and θZ-axis).

[0102] The dispenser (supply unit) places (supplies) the imprint material in a pattern formation region (imprint region) on the substrate. The dispenser can place the imprint material at a target position on the substrate, for example, by discharging the imprint material from the dispenser while scanning the substrate with a substrate driving mechanism.

[0103] The imaging unit is configured to include one or more imaging units, and measures the relative positions of the alignment marks in the pattern formation region of the substrate and the alignment marks of the mold by capturing an image formed by the alignment marks. The imaging unit may be configured to capture the above image via a prism.

[0104] The control unit includes a CPU, a memory (storage unit), and the like, and is configured by at least one computer, and is connected to each component of the imprint apparatus via a line. The control unit also performs overall control of the operation adjustment of each component of the entire imprint apparatus according to a program stored in the memory. That is, the control unit controls the irradiation unit, substrate driving mechanism, dispenser, mold driving mechanism, imaging unit, and the like. The control unit may be configured integrally with other parts of the imprint apparatus (within a common housing). Furthermore, the control unit may be configured separately from other parts of the imprint apparatus (in a different housing), or may be installed in a different location from the imprint apparatus and controlled remotely.

[0105] The control unit may be configured, for example, by a PLD (Programmable Logic Device) such as an FPGA (Field Programmable Gate Array), an ASIC (Application Specific Integrated Circuit), a general-purpose computer with a built-in program, or a combination of all or part of these.

[0106] The imprint process, which is a process for forming a pattern on a pattern formation region of a substrate by an imprint material, performed by the imprint apparatus of this embodiment, may include a lamination process, a contact process, a light irradiation process, and a release process. This imprint process is performed for one pattern formation region in the order of a lamination process, a contact process, a light irradiation process, and a release process. The imprint process may include an alignment process for aligning the substrate and the mold between the contact process and the light irradiation process. Each step of the imprint process according to this embodiment will be described below with reference to FIG. 7. FIG. 7 is a schematic cross-sectional view showing the imprint process performed by the imprint apparatus. FIG. 7(A) is a schematic cross-sectional view showing an example of the lamination process. FIG. 7(B) is a schematic cross-sectional view showing an example of the contact process. FIG. 7(C) is a schematic cross-sectional view showing an example of the light irradiation process. FIG. 7(D) is a schematic cross-sectional view showing an example of the release process.

[0107] The cured film of the curable composition obtained by the imprinting method according to this embodiment is preferably a film having a pattern with a size of 1 nm or more and 10 mm or less. Generally, a pattern formation technique for producing a film having a nano-sized (1 nm or more and 1000 nm or less) pattern (uneven structure) using light is called a photo-nanoimprinting method. The imprinting method according to this embodiment utilizes the photo-nanoimprinting method. Each step will be described below. Each process in the following steps is realized by the control unit of the imprinting device executing a program stored in the memory. Alternatively, the process may be realized by the control unit 111 of the processing device.

[0108] In one example of the lamination step illustrated in Fig. 7(A), droplets of the curable composition 202 are discretely dropped and disposed on the substrate 201 using a dispenser, as shown in Fig. 7. The inkjet method is particularly preferable as a disposing method. The droplets of the curable composition 202 are densely disposed on the substrate 201 facing an area on the mold 204 where recesses are densely present, and sparsely disposed on the substrate facing an area where recesses are sparsely present. This allows the residual film, which will be described later, to be controlled to a uniform thickness regardless of the density of the pattern on the mold 204.

[0109] The dropped droplet gradually spreads over the substrate surface over time. The arrow 203 in the figure indicates the direction in which the droplet spreads.

[0110] As another example of the lamination process, the curable composition 202 may be disposed on the substrate 201 by using a spin coating method. In this case, the curable composition 202 is disposed on the substrate 201 continuously.

[0111] The viscosity of the mixture of the components of the curable composition 202 according to this embodiment, excluding the solvent, at 25°C is preferably 1 mPa·s or more and less than 40 mPa·s. More preferably, it is 1 mPa·s or more and less than 20 mPa·s. If the viscosity of the curable composition 202 exceeds 40 mPa·s, it becomes impossible to apply the composition by an inkjet method, which can make the remaining film thickness uniform and form a high-precision pattern by disposing droplets discretely according to the coarseness and density of the desired pattern. If the viscosity is lower than 1 mPa·s, the composition may flow when applied (disposed), causing uneven application, or the composition may flow out from the edge of the mold 204 in the contact step described later, which is not preferable.

[0112] The surface tension of the curable composition 202 according to this embodiment, the surface tension of the composition of components excluding the solvent, at 23° C. is preferably 5 mN / m or more and 70 mN / m or less, more preferably 7 mN / m or more and 50 mN / m or less, and even more preferably 10 mN / m or more and 40 mN / m or less.

[0113] Here, the higher the surface tension, for example, 5 mN / m or more, the stronger the capillary force, and therefore filling (spreading and filling) is completed in a short time when the curable composition 202 is brought into contact with the mold 204. In addition, by setting the surface tension to 70 mN / m or less, the cured film obtained by curing the curable composition has a smooth surface.

[0114] The contact angle of the curable composition 202 according to this embodiment with respect to the imprint surface and the substrate surface is preferably 0° or more and 90° or less for a composition of components excluding the solvent. If the contact angle is greater than 90°, the capillary force acts in the negative direction (the direction that shrinks the contact interface between the mold and the curable composition) inside the concave-convex pattern of the mold 204 and in the gap between the substrate 201 and the mold 204, and filling does not occur. A contact angle of 0° or more and 30° or less is particularly preferable. The lower the contact angle, the stronger the capillary force acts, and the faster the filling speed.

[0115] The substrate 201 on which the curable composition 202 is placed is a substrate to be processed, and for example, a silicon substrate is used. A layer to be processed may be formed on the substrate 201. Another layer may be further formed between the substrate 201 and the layer to be processed. Furthermore, if a quartz substrate is used as the substrate 201, a replica (mold replica) of a quartz imprint mold can be produced.

[0116] However, the substrate 201 is not limited to a silicon substrate or a quartz substrate, and may be selected from among substrates known as substrates for semiconductor devices, such as aluminum, titanium-tungsten alloy, aluminum-silicon alloy, aluminum-copper-silicon alloy, silicon oxide, and silicon nitride.

[0117] The surface of the substrate 201 (substrate to be processed) or layer to be processed may be subjected to surface treatment such as silane coupling treatment, silazane treatment, or formation of an organic thin film to improve adhesion to the curable composition 202.

[0118] 7(B), in the contacting step, an imprinting mold 204 having a prototype pattern for transferring a pattern shape is brought into contact with the curable composition 202 formed in the previous step (lamination step). As a result, the curable composition 202 fills the recesses of the fine pattern on the surface of the mold 204, forming a liquid film that fills the fine pattern of the mold 204. Here again, the arrow 203 indicates the direction in which the droplets (curable composition) spread (fill the recesses).

[0119] As the mold 204, it is preferable to use a mold 204 made of a light-transmitting material in consideration of the next process (light irradiation process). Specifically, the material constituting the mold 204 is preferably a substrate such as glass, quartz, PMMA, light-transmitting resin such as polycarbonate resin, transparent metal deposition film, soft film such as polydimethylsiloxane, photocured film, metal film, etc. However, when a light-transmitting resin is used as the material constituting the mold 204, it is necessary to select a resin that is not dissolved in the components contained in the curable composition 202. Quartz is particularly preferable as the material constituting the mold 204 because of its small thermal expansion coefficient and small pattern distortion.

[0120] The fine pattern on the surface of the mold 204 preferably has a pattern height of 4 nm or more and 200 nm or less. The lower the pattern height, the lower the force required to peel the mold from the photocured film of the curable composition in the demolding step, i.e., the demolding force, and the fewer demolding defects remaining on the mold 204 side due to the curable composition pattern being torn off during demolding. The elastic deformation of the curable composition pattern due to the impact when the mold is peeled off may cause adjacent curable composition patterns to come into contact with each other, resulting in adhesion or damage to the curable composition patterns. However, if the pattern height is about twice or less the pattern width (aspect ratio 2 or less), it is highly likely that these problems can be avoided. On the other hand, if the pattern height is too low, the processing accuracy of the substrate to be processed is low.

[0121] As described above, the present invention also includes the use of a mold having no fine pattern on the imprinted surface in order to obtain a flat surface of the curable composition. That is, the processing device of this embodiment can be mounted on a flattening device or the like that uses a mold having no fine pattern on the imprinted surface.

[0122] The mold 204 may be subjected to a surface treatment before the contact step between the curable composition 202 and the mold 204 in order to improve the releasability between the photocured curable composition 202 and the surface of the mold 204. An example of the surface treatment method is a method of applying a release agent to the surface of the mold 204 to form a release agent layer. Examples of the release agent applied to the surface of the mold 204 include a silicon-based release agent, a fluorine-based release agent, a hydrocarbon-based release agent, a polyethylene-based release agent, a polypropylene-based release agent, a paraffin-based release agent, a montan-based release agent, and a carnauba-based release agent. For example, a commercially available coating-type release agent such as Optool (registered trademark) DSX manufactured by Daikin Industries, Ltd. can also be suitably used. The release agent may be used alone or in combination of two or more types. Among these, fluorine-based and hydrocarbon-based release agents are particularly preferred.

[0123] 7(B), when the mold 204 and the curable composition 202 are brought into contact with each other, the pressure applied to the curable composition 202 is not particularly limited. The pressure may be 0 MPa or more and 100 MPa or less. The pressure is preferably 0 MPa or more and 50 MPa or less, more preferably 0 MPa or more and 30 MPa or less, and even more preferably 0 MPa or more and 20 MPa or less.

[0124] In the contact step, the time for contacting the mold with the curable composition 202 is not particularly limited, but may be, for example, 0.1 to 600 seconds. The time is preferably 0.1 to 3 seconds, and more preferably 0.1 to 1 second. If the time is shorter than 0.1 seconds, the spread and fill are insufficient, and defects called unfilled defects tend to occur frequently.

[0125] The contact step can be carried out under any of the conditions of air, reduced pressure, and inert gas. Here, it is preferable to use an inert gas atmosphere by using an inert gas as a reduced pressure atmosphere or atmosphere control gas, since it is possible to prevent the influence of oxygen and moisture on the curing reaction. Specific examples of the inert gas that can be used when the contact step is carried out under an inert gas atmosphere include nitrogen, carbon dioxide, helium, argon, various fluorocarbon gases, and the like, or a mixture of these gases. When the contact step is carried out under a specific gas atmosphere, including air, the preferred pressure is 0.0001 atm or more and 10 atm or less.

[0126] Next, in the light irradiation step, as illustrated in Fig. 7(C), the curable composition 202 is irradiated with light (irradiation light) 205 through a mold 204. More specifically, the curable composition 202 filled in the fine pattern of the mold 204 is irradiated with light 205 through the mold 204. As a result, the curable composition 202 filled in the fine pattern of the mold 204 is cured by the light 205 to become a cured film 206 having a pattern shape.

[0127] Here, the light 205 to be irradiated onto the curable composition 202 filled in the fine pattern of the mold 204 is selected according to the sensitivity wavelength of the curable composition 202. Specifically, it is preferable to appropriately select and use ultraviolet light having a wavelength of 150 nm or more and 400 nm or less, X-rays, electron beams, etc.

[0128] Among these, ultraviolet light is particularly preferred for the light 205. This is because many of the compounds commercially available as curing assistants (photopolymerization initiators) are sensitive to ultraviolet light. Examples of light sources that emit ultraviolet light include high-pressure mercury lamps, ultra-high-pressure mercury lamps, low-pressure mercury lamps, deep-UV lamps, carbon arc lamps, chemical lamps, metal halide lamps, and xenon lamps. In addition, KrF excimer lasers, ArF excimer lasers, and F2 excimer lasers are also included, with ultra-high-pressure mercury lamps being particularly preferred. The number of light sources used may be one or more. When light irradiation is performed, it may be performed on the entire surface of the curable composition 202 filled in the fine pattern of the mold 204, or only on a partial area.

[0129] The light irradiation process may be performed intermittently multiple times over the entire region on the substrate 201, or may be performed continuously over the entire region. Furthermore, the region A may be irradiated in the first irradiation process, and the region B different from the region A may be irradiated in the second irradiation process.

[0130] Next, in the demolding step, the cured film 206 having a pattern shape is separated from the mold 204, as exemplified in Fig. 7(D). As a result, the cured film 206 having a pattern shape that is a reverse pattern of the fine pattern formed on the mold 204 in the light irradiation step is obtained in a self-supporting state. Note that the cured film remains in the recesses of the concave-convex pattern of the cured film 206 having a pattern shape, and this film will be referred to as a residual film 207.

[0131] The method for separating the patterned cured film 206 and the mold 204 is not particularly limited as long as a part of the patterned cured film 206 is not physically damaged when they are separated, and various conditions are also not particularly limited. For example, the substrate 201 (substrate to be processed) may be fixed and the mold 204 may be moved away from the substrate 201 to separate them. Alternatively, the mold 204 may be fixed and the substrate 201 may be moved away from the mold 204 to separate them. Alternatively, both of them may be pulled in opposite directions to separate them.

[0132] By successively carrying out each of the above steps on multiple pattern formation regions (imprint regions), a cured film 206 having a desired concave-convex pattern shape (a pattern shape resulting from the concave-convex shape of the mold 204) at a desired position on the substrate 201 can be obtained.

[0133] The processing apparatus in this embodiment is not limited to an imprint apparatus, and can be installed in, for example, a mold cleaning apparatus or a replica manufacturing apparatus for manufacturing replicas of a mold. The replica manufacturing apparatus has the same configuration (including functional units and hardware configuration) as the imprint apparatus.

[0134] <Example of article manufacturing method> The method for manufacturing an article according to this embodiment is suitable for manufacturing an article such as a microdevice such as a semiconductor device or an element having a fine structure. The method for manufacturing an article according to this embodiment includes a step of forming a pattern on a composition applied to a substrate using the above-mentioned imprinting apparatus (a step of processing the substrate) and a step of processing the substrate on which the pattern has been formed in the above step. Furthermore, the manufacturing method includes other well-known steps (oxidation, film formation, deposition, doping, planarization, etching, composition peeling, dicing, bonding, packaging, etc.). The method for manufacturing an article according to this embodiment is advantageous in at least one of the performance, quality, productivity, and production cost of the article compared to conventional methods. In addition, in the method for manufacturing an article according to this embodiment, a removal step of removing residues of a mold (form, original plate) using the above-mentioned removal apparatus is performed before starting the imprinting process performed by the imprinting apparatus. That is, when performing the imprinting process, a mold from which residues have already been removed and on which a liquid-repellent layer has been formed on the mesa sidewall of the mold is used.

[0135] The pattern of the cured product formed using the imprinting apparatus is used permanently on at least a part of various articles, or temporarily when manufacturing various articles. The articles include electric circuit elements, optical elements, MEMS, recording elements, sensors, molds, etc. Examples of the electric circuit elements include volatile or non-volatile semiconductor memories such as DRAM, SRAM, flash memory, and MRAM, and semiconductor elements such as LSI, CCD, image sensors, and FPGAs. Examples of the molds include molds for substrate processing such as imprinting.

[0136] The pattern of the cured product may be used as it is as at least a part of a component of the article, or may be used temporarily as a composition mask, which is removed after etching or ion implantation is performed in a substrate processing step.

[0137] Next, a specific method for manufacturing an article will be described with reference to Fig. 8. As shown in Fig. 8(A), a substrate 1z such as a silicon substrate having a workpiece 2z such as an insulator formed on its surface is prepared, and then a composition 3z is applied to the surface of the workpiece 2z by an inkjet method or the like. Here, a state in which the composition 3z in the form of multiple droplets is applied onto the substrate 1z is shown.

[0138] As shown in FIG. 8(B), the mold 4z is placed so that the side on which the concave-convex pattern is formed faces the composition 3z on the substrate 1z. As shown in FIG. 8(C), the substrate 1z to which the composition 3z is applied is brought into contact with the mold 4z, and pressure is applied (contact step). The composition 3z fills the gap between the mold 4z and the workpiece 2z. When light is irradiated through the mold 4z in this state as energy for curing, the composition 3z is cured (curing step). At this time, in this embodiment, it is possible to irradiate the composition with light at an irradiation amount that results in an optimal degree of photopolymerization based on the spectral sensitivity characteristics acquired within the device.

[0139] As shown in Fig. 8(D), after the composition 3z is cured, the mold 4z and the substrate 1z are separated, and a pattern of the cured product of the composition 3z is formed on the substrate 1z (pattern formation step, molding step). In this cured product pattern, the concave portions of the mold 4z correspond to the convex portions of the cured product, and the convex portions of the mold 4z correspond to the concave portions of the cured product, that is, the concave-convex pattern of the mold 4z is transferred to the composition 3z.

[0140] As shown in FIG. 8(E), when etching is performed using the pattern of the cured material as an etching-resistant mask, the portion of the surface of the workpiece 2z where there is no cured material or where only a thin portion remains is removed, forming a groove 5z. As shown in FIG. 8(F), when the pattern of the cured material is removed, an article having grooves 5z formed on the surface of the workpiece 2z can be obtained. Here, the pattern of the cured material is removed, but it may be used as an interlayer insulating film included in a semiconductor element or the like, that is, a component of an article, without being removed after processing. Note that, although an example of using a mold for transferring a circuit pattern provided with a concave-convex pattern as the mold 4z has been described, a flat template having a flat portion without a concave-convex pattern may also be used.

[0141] Although the preferred embodiments of the present invention have been described above, the present invention is not limited to these embodiments, and various modifications and changes are possible within the scope of the present invention. In addition, the above-described embodiments may be combined to carry out the present invention.

[0142] The disclosure of this embodiment includes the following configuration.

[0143] (Configuration 1) A method for removing residues adhered to a mold having a base having a main surface and a convex portion provided on the main surface, the mold having an uneven pattern formed on an upper surface of the convex portion to be pressed against a curable composition, the method comprising the steps of: A first removal step of removing the residue, The method for removing the residue, wherein in the first removing step, the liquid-repellent layer formed on at least the side surface of the convex portion is dissolved with a predetermined solvent to remove the residue.

[0144] (Configuration 2) 2. The method according to claim 1, wherein the liquid repellent layer contains a polymer having a fluorocarbon chain.

[0145] (Configuration 3) 3. The method according to claim 1, wherein in the first removal step, the liquid-repellent layer is dissolved so that the film thickness of the liquid-repellent layer becomes 3 nm or more.

[0146] (Configuration 4) 4. The method for removing a polymer according to any one of claims 1 to 3, wherein the predetermined solvent is a volatile solvent that dissolves a polymer having a fluorocarbon chain.

[0147] (Configuration 5) 5. The method according to any one of claims 1 to 4, wherein the predetermined solvent includes at least one of hydrofluoroether, perfluorocarbon, and hydrofluorocarbon.

[0148] (Configuration 6) The removal method according to any one of configurations 1 to 5, further comprising a first forming step of forming a protective layer that prevents the liquid-repellent layer from being formed at least on the outer periphery of the concave-convex pattern in the mold.

[0149] (Configuration 7) a second forming step of forming the liquid-repellent layer on at least the side surface of the protrusion of the mold, 7. The method according to claim 6, wherein the second forming step is carried out after the first forming step.

[0150] (Configuration 8) a second removal step of removing the protective layer and the liquid-repellent layer formed on a part of the protective layer, 8. The method according to claim 7, wherein the second removing step is performed after the second forming step.

[0151] (Configuration 9) 9. The method according to claim 8, wherein the first removing step is carried out after the second removing step.

[0152] (Configuration 10) A removal device for removing residues attached to a mold, the mold having a base having a main surface and a convex portion provided on the main surface, the convex portion having an upper surface on which a concave-convex pattern to be pressed against a curable composition is formed, the device comprising: a stage that is movable while holding the mold; and a first removal unit that removes the residue by dissolving the liquid-repellent layer formed on at least the side surface of the convex portion with a predetermined solvent. A removal device characterized by:

[0153] (Configuration 11) 11. The removal device according to claim 10, wherein the liquid repellent layer contains a polymer having a fluorocarbon chain.

[0154] (Configuration 12) 12. The removal apparatus according to claim 10 or 11, wherein the thickness of the liquid repellent layer after removing the residue is 3 nm or more.

[0155] (Configuration 13) 13. The removal apparatus according to any one of configurations 10 to 12, wherein the predetermined solvent is a volatile solvent that dissolves a polymer having a fluorocarbon chain.

[0156] (Configuration 14) 14. The removal apparatus of any one of configurations 10 to 13, wherein the predetermined solvent includes at least one of a hydrofluoroether, a perfluorocarbon, and a hydrofluorocarbon.

[0157] (Configuration 15) 15. The removal device according to any one of configurations 10 to 14, further comprising a first forming section that forms a protective layer that prevents the liquid-repellent layer from being formed on at least the outer periphery of the concave-convex pattern in the mold.

[0158] (Configuration 16) 16. The removal device according to any one of configurations 10 to 15, further comprising a second forming section for forming the liquid-repellent layer on at least a side surface of the protrusion of the mold.

[0159] (Configuration 17) 16. The removal device according to configuration 15, further comprising a second removal section that removes the protective layer and the liquid-repellent layer formed on a part of the protective layer.

[0160] (Configuration 18) An imprinting apparatus for forming a pattern of a curable composition in a plurality of pattern formation regions on a substrate using a mold having a concave-convex pattern, comprising: a discharge device that discharges the curable composition onto the substrate; a substrate stage that is movable while holding the substrate; and a removal device according to any one of configurations 10 to 17. 1. An imprint apparatus comprising:

[0161] (Configuration 19) A replica manufacturing apparatus for manufacturing a replica of a mold having a concave-convex pattern, comprising: A discharge device that discharges the curable composition onto a substrate; a substrate stage that is movable while holding the substrate; and a removal device according to any one of configurations 10 to 17. A replica manufacturing apparatus.

[0162] (Configuration 20) A pattern forming step of forming the concave-convex pattern on the substrate using the imprint apparatus according to configuration 18; a processing step of processing the substrate on which the pattern has been formed in the pattern forming step; manufacturing an article from the substrate processed in the processing step; A method for producing an article, comprising:

[0163] Furthermore, a computer program for implementing all or part of the control in each of the above-described embodiments may be supplied to a removal apparatus, an imprint apparatus, a replica manufacturing apparatus, or the like via a network or various storage media. Then, a computer (or a CPU, MPU, or the like) in each of the apparatuses may read and execute the program. In this case, the program and the storage medium storing the program constitute the present invention. [Explanation of symbols]

[0164] 11 Mold 11a Mesa section 11b Concave and convex pattern 11c Base 11d side wall 12 Substrate 13 Curable composition 14 Liquid repellent layer

Claims

1. A removal method for removing residue adhering to a mold having a base having a main surface and a protrusion provided on the main surface, wherein a textured pattern for pressing a curable composition is formed on the upper surface of the protrusion, The process includes a first removal step for removing the aforementioned residue, The removal method is characterized in that, in the first removal step, the residue is removed by dissolving at least the liquid-repellent layer formed on the side surface of the protrusion with a predetermined solvent.

2. The removal method according to claim 1, characterized in that the liquid-repellent layer contains a polymer having a fluorinated carbon chain.

3. The removal method according to claim 1, characterized in that the first removal step involves dissolving the liquid-repellent layer such that the thickness of the liquid-repellent layer is 3 nm or more.

4. The removal method according to claim 1, characterized in that the predetermined solvent is a volatile solvent that dissolves polymers having fluorinated carbon chains.

5. The removal method according to claim 1, characterized in that the predetermined solvent includes at least one of hydrofluoroether, perfluorocarbon, and hydrofluorocarbon.

6. The removal method according to claim 1, further comprising a first forming step of forming a protective layer that prevents the formation of the liquid-repellent layer on at least the outer periphery of the uneven pattern in the mold.

7. The process includes a second forming step of forming the liquid-repellent layer on at least the side surface of the protrusion of the mold, The removal method according to claim 6, characterized in that the second forming step is performed after the first forming step.

8. The process includes a second removal step of removing the protective layer and the liquid-repellent layer formed on a part of the protective layer, The removal method according to claim 7, characterized in that the second removal step is performed after the second forming step.

9. The removal method according to claim 8, characterized in that the first removal step is performed after the second removal step.

10. A removal device for removing residue adhering to a mold, comprising a base having a main surface and a protrusion provided on the main surface, wherein a textured pattern for pressing a curable composition is formed on the upper surface of the protrusion, A stage that can move while holding the aforementioned mold, It has a first removal unit that removes the residue by dissolving the liquid-repellent layer formed at least on the side surface of the protrusion with a predetermined solvent, A removal device characterized by the following features.

11. The removal device according to claim 10, characterized in that the liquid-repellent layer contains a polymer having a fluorinated carbon chain.

12. The removal apparatus according to claim 10, characterized in that the thickness of the liquid-repellent layer after the removal of the residue is 3 nm or more.

13. The removal apparatus according to claim 10, characterized in that the predetermined solvent is a volatile solvent that dissolves polymers having fluorinated carbon chains.

14. The removal apparatus according to claim 10, characterized in that the predetermined solvent includes at least one of hydrofluoroether, perfluorocarbon, and hydrofluorocarbon.

15. The removal device according to claim 10, characterized in that it has a first forming portion that forms a protective layer that prevents the formation of the liquid-repellent layer on at least the outer periphery of the uneven pattern in the mold.

16. The removal device according to claim 10, further comprising a second forming portion that forms the liquid-repellent layer on at least the side surface of the protrusion of the mold.

17. The removal device according to claim 15, further comprising a second removal unit for removing the protective layer and the liquid-repellent layer formed on a part of the protective layer.

18. An imprint apparatus for forming patterns of a curable composition in multiple pattern formation regions on a substrate using a mold having an uneven pattern, An extrusion device for extruding the curable composition onto the substrate, A substrate stage that can move while holding the substrate, A removal device according to any one of claims 10 to 17, An imprinting device characterized by the following features.

19. A replica manufacturing apparatus for manufacturing a replica of a mold having an uneven pattern, An extrusion device for extruding a curable composition onto a substrate, A substrate stage that can move while holding the substrate, A removal device according to any one of claims 10 to 17, A replica manufacturing apparatus characterized by the following features.

20. A pattern forming step of forming the uneven pattern on the substrate using the imprint apparatus described in claim 18, A processing step for processing the substrate on which the pattern has been formed in the pattern formation step, A process for manufacturing an article from the substrate processed in the above processing step, A method for manufacturing an article, characterized by including the following:

Images