Inspection method, inspection device, imprint device, article manufacturing method, replica mold manufacturing method, and mold

Abstract

To provide a new technique advantageous for inspecting a mold.SOLUTION: An inspection method for a mold in which a liquid-repellent layer is formed on the side surface of a mesa portion protruding from a substrate includes a first step of acquiring information showing the relationship between the measurement results obtained by non-contact measurement of the liquid-repellent layer and the state of the liquid-repellent layer, a second step of non-contact measurement of the liquid-repellent layer formed on the side surface, and a third step of determining the state of the liquid-repellent layer formed on the side surface on the basis of the information acquired in the first step and the measurement results obtained in the second step.SELECTED DRAWING: Figure 3

Description

[Technical Field]

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

[0002] Imprinting technology has attracted attention as a technique for forming nano-sized fine patterns (relief structures) of 1 nm to 1000 nm. In imprinting technology, a pattern is formed on a light-transparent imprinting mold (die) and the mold is brought into contact with a curable composition (imprint material) placed on a substrate. After the curable composition on the substrate is cured to form a cured product, the mold is separated from the cured product (demolding), forming a pattern of the cured product on the substrate. The substrate is then processed using the pattern of the cured product as a mask, thereby forming a fine pattern on the substrate. This process (imprinting process) is repeated while changing the positional relationship between the mold and the substrate, thereby forming a pattern of the cured product at a desired position on the substrate.

[0003] Molds used in imprinting techniques are generally formed by processing silica glass. Specifically, a convex mesa is formed on the silica glass, and a fine pattern is formed on the upper surface of the mesa, i.e., the imprint surface, which is the surface that comes into contact with the curable composition. This pattern is pressed against the curable composition. However, since the curable composition is fluid at this stage, the curable composition may protrude from the imprint surface of the mesa and adhere to the sidewall of the mesa (mesa sidewall), a phenomenon known as seepage. The mold is removed when the curable composition on the substrate has cured, but the curable composition that has seeped onto the mesa sidewall remains attached to the mesa sidewall. Therefore, repeated imprinting processes gradually increase the amount of curable composition adhering to the mesa sidewall, causing the curable composition to fall onto the substrate at unintended times, resulting in significant defects on the substrate.

[0004] Therefore, a technique has been proposed for manufacturing a mold for imprinting that prevents the curable composition from adhering to the mesa sidewall (see Patent Document 1). Patent Document 1 discloses a technique in which the imprint surface of the mesa portion of the mold is protected with a protective material, and only the mesa sidewall is made liquid-repellent to the curable composition. Making the mesa sidewall liquid-repellent, that is, increasing the contact angle of the mesa sidewall with the curable composition, can prevent seepage. From the viewpoint of most effectively preventing seepage, the region of the mesa sidewall that should be made liquid-repellent is preferably made liquid-repellent up to the end of the mesa sidewall in the direction toward the imprint surface. Patent Document 1 discloses a technique for protecting the imprint surface by bringing a shielding plate close to the imprint surface, and a technique for protecting the imprint surface by bringing a masking material into contact with the imprint surface. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 6441181 Summary of the Invention [Problem to be solved by the invention]

[0006] However, with the technology disclosed in Patent Document 1, even if a shielding plate is brought close to the imprint surface of the mesa portion of the mold, the imprint surface and the shielding plate are not in complete contact, which may result in the liquid-repellent component penetrating the imprint surface. Furthermore, when a masking material is brought into contact with the imprint surface, it is difficult to bring the masking material into contact with the entire area of ​​the imprint surface to be protected because both the mold and the masking material are hard, solid materials. Therefore, the liquid-repellent component may penetrate into some part of the imprint surface, resulting in the liquid-repellent agent (residue) remaining on the imprint surface. Furthermore, Patent Document 1 also discloses a technology for protecting the imprint surface by pressing a mold against a resist (protective material) placed on a substrate. However, as described above, the resist seeps onto the mesa sidewall, making it difficult to make the mesa sidewall liquid-repellent without any defects.

[0007] As described above, in the conventional technology, there is a possibility that (residues of) the liquid-repellent agent may remain on the imprinted surface of the mesa portion of the mold, or that the liquid-repellent properties may be lost on the mesa sidewalls, so it is necessary to inspect whether only the mesa sidewalls have been made liquid-repellent with high precision. However, while the conventional technology inspects for the presence or absence of foreign matter of 0.2 μm or more on the imprinted surface, it does not disclose a technology for inspecting whether the desired area of ​​the mesa sidewall (for example, the entire surface of the mesa sidewall) has been made liquid-repellent.

[0008] To evaluate and inspect the liquid repellency, a test method is generally used in which a measurement liquid is placed (supplied) on the liquid-repellent portion (liquid-repellent layer) and the contact angle is measured. However, the liquid-repellent layer may come into contact with the measurement liquid and become contaminated, which may cause deterioration of the liquid-repellent layer, i.e., a decrease in its liquid-repellent function. Furthermore, since it is extremely difficult to place a measurement liquid on a minute area such as the sidewall of a mold mesa and measure the contact angle, it is not practical to apply such a test method to inspect the liquid repellency of the mesa sidewall (liquid-repellent layer).

[0009] The present invention has been made in view of the above problems of the conventional technology, and has as its exemplary object to provide a new technology that is advantageous for inspecting molds. [Means for solving the problem]

[0010] In order to achieve the above-mentioned object, one aspect of the present invention provides an inspection method for a mold having a liquid-repellent layer formed on the side surface of a mesa portion protruding from a substrate, characterized by comprising: a first step of acquiring information indicating the relationship between the measurement results obtained by non-contact measurement of the liquid-repellent layer and the state of the liquid-repellent layer; a second step of non-contact measurement of the liquid-repellent layer formed on the side surface; and a third step of determining the state of the liquid-repellent layer formed on the side surface based on the information acquired in the first step and the measurement results obtained in the second step.

[0011] Further objects and other aspects of the present invention will become apparent from the following description of the embodiments with reference to the accompanying drawings. [Effects of the Invention]

[0012] According to the present invention, for example, a new technique that is advantageous for inspecting a mold can be provided. [Brief explanation of the drawings]

[0013] [Figure 1] FIG. 1 is a cross-sectional view showing the configuration of a typical mold in the present invention. [Figure 2] 1 is a diagram showing a configuration of a system having an inspection unit according to one aspect of the present invention. [Figure 3] FIG. 2 is a schematic diagram showing an example of the configuration of an inspection unit. [Figure 4] FIG. 2 is a schematic diagram illustrating an example of the configuration of a protective layer forming unit. [Figure 5] FIG. 2 is a schematic diagram illustrating an example of the configuration of a protective layer removal unit. [Figure 6] FIG. 2 is a diagram for explaining an example of the operation of the system shown in FIG. [Figure 7] 2 is a flowchart illustrating an example of the operation of the system shown in FIG. 1. [Figure 8]FIG. 10 is a diagram showing an example of the arrangement relationship of an irradiation unit and a detection unit with respect to a mold. [Figure 9] 1 is a graph showing an example of the relationship between the reflectance of a liquid-repellent layer and the contact angle of a curable composition with respect to the liquid-repellent layer. [Figure 10] 1 is a graph showing an example of the relationship between the thickness of a liquid-repellent layer and the contact angle of a curable composition with respect to the liquid-repellent layer. [Figure 11] FIG. 1 is a schematic diagram illustrating an example of the configuration of an imprint apparatus. [Figure 12] 1A and 1B are diagrams for explaining an example of an imprint process performed by an imprint apparatus. [Figure 13] FIG. 10 is a diagram for explaining an example of a method for manufacturing an article. DETAILED DESCRIPTION OF THE INVENTION

[0014] Hereinafter, embodiments will be described in detail with reference to the accompanying drawings. Note that the following embodiments do not limit the invention according to the claims. Although multiple features are described in the embodiments, not all of these multiple features are necessarily essential to the invention, and multiple features may be combined arbitrarily. Furthermore, in the accompanying drawings, the same reference numerals are used to designate the same or similar components, and redundant explanations will be omitted.

[0015] Molds (forms) used in imprint lithography are configured so that portions of the mold other than the imprint surface do not contact the substrate, even if the parallelism between the mold and the substrate (workpiece) is not perfect. Specifically, the imprint surface of the mold is formed to have a shape that protrudes from the base material of the mold, i.e., to form a convex portion (plateau portion) with the imprint surface as the surface and sidewalls (side surfaces) surrounding it. Here, the imprint surface of the mold refers to the contact surface of the mold that comes into contact with the curable composition (imprint material) on the substrate. The convex portion of the mold that protrudes from the base material is also called a mesa portion. By forming a mesa portion in the mold in this way, a certain clearance is formed between the portion of the mesa portion of the mold other than the imprint surface and the substrate. Therefore, when the imprint surface is brought into contact with the curable composition on the substrate, it is possible to prevent contact between the portion other than the imprint surface and the substrate.

[0016] Fig. 1 is a cross-sectional view showing the configuration of a representative mold 11 in the present invention. With reference to Fig. 1, the mold 11 on which a liquid-repellent layer 14 has been formed and from which residues of the liquid-repellent layer 14 (the liquid-repellent agent constituting the liquid-repellent layer 14) have been removed will be described.

[0017] As shown in FIG. 1, the mold 11 includes a mesa portion 11a, and a pattern 11b consisting of fine projections and recesses is formed on an imprint surface 11g, which is the surface (lower surface) of the mesa portion 11a. By pressing the imprint surface 11g on which the pattern 11b is formed against a curable composition 13 arranged on a substrate 12, the pattern 11b is transferred to the curable composition 13, and a composition pattern 13a consisting of the curable composition 13 is formed. As described above, in this embodiment, the mold 11 includes a base material 11c that serves as a base, and a mesa portion 11a that protrudes from (the main surface of) the base material 11c. The pattern 11b to be transferred to the curable composition 13 on the substrate is formed on the imprint surface 11g of the mesa portion 11a. The mold 11 (base material 11c) is made of a material such as quartz, for example.

[0018] When the imprint surface 11g of the mesa portion 11a of the mold 11 is pressed against the curable composition 13 on the substrate, the curable composition 13 may protrude from the imprint surface 11g and adhere to the side surface 11d (mesa sidewall) of the mesa portion 11a, which is known as seepage. To prevent such seepage, a liquid-repellent layer 14 having liquid repellency is formed on the surface (surface layer) of the side surface 11d of the mesa portion 11a of the mold 11. The liquid-repellent layer 14 is formed to a certain thickness. The liquid-repellent layer 14 is a layer that has a larger contact angle with the curable composition 13 than the material of the mold 11 on which the liquid-repellent layer 14 is formed, such as quartz. In other words, the contact angle of the curable composition 13 with the liquid-repellent layer 14 is larger than the contact angle of the curable composition 13 with the mold 11. The contact angle of the curable composition 13 with the liquid-repellent layer 14 is preferably an angle that provides sufficient liquid repellency to suppress seepage, for example, 70 degrees or more. The liquid-repellent layer 14 is preferably formed using a wet method (liquid phase method) in which a liquid repellent agent is applied (supplied) to the side surface 11d of the mesa portion 11a and dried.

[0019] In this embodiment, the liquid-repellent layer 14 is formed at least on the side surface 11d of the mesa portion 11a of the mold 11. As described above, this prevents the curable composition 13, which is an organic material, from spilling out and adhering to the side surface 11d of the mesa portion 11a when the mold 11 (imprint surface 11g) is pressed against the curable composition 13 on the substrate. The liquid-repellent layer 14 may be formed on the upper surface 11e or the side surface 11f (sidewall) of the base material 11c that supports the mesa portion 11a, but is formed at least on the side surface 11d of the mesa portion 11a.

[0020] When forming the liquid-repellent layer 14 on the side surface 11d of the mesa portion 11a, it is necessary to prevent residues of the liquid-repellent layer 14 or the liquid-repellent agent from being formed on the imprint surface 11g. This is because if residues of the liquid-repellent layer 14 or the liquid-repellent agent are formed on the imprint surface 11g, there is a possibility that an unfilled defect of the curable composition 13 will occur when the mold 11 is pressed against the curable composition 13 on the substrate. The unfilled defect of the curable composition 13 is a phenomenon in which the pattern 11b formed on the imprint surface 11g is not sufficiently filled with the curable composition 13.

[0021] In this embodiment, first, a protective layer for protecting the imprint surface 11g is formed on the imprint surface 11g, and then the liquid-repellent layer 14 is formed on the side surface 11d of the mesa portion 11a. Thereafter, the protective layer is removed from the imprint surface 11g, and the liquid-repellent layer 14 is formed on the side surface 11d of the mesa portion 11a. By forming the protective layer on the imprint surface 11g before forming the liquid-repellent layer 14, it is possible to prevent the liquid-repellent layer 14 from being formed on the imprint surface 11g.

[0022] On the other hand, when forming the liquid-repellent layer 14, a small amount of the liquid repellent agent may overflow from the side surface 11d of the mesa portion 11a onto the protective layer formed on the imprint surface 11g. The liquid-repellent agent (or the liquid-repellent layer 14 formed therefrom) that has overflowed onto the protective layer may remain on the edge of the imprint surface 11g and become residue when the protective layer is removed from the imprint surface 11g. If residue of the liquid-repellent layer 14 is formed on the imprint surface 11g, it may cause poor contact or unfilled defects on the imprint surface 11g, and therefore must be removed from the imprint surface 11g.

[0023] In this embodiment, in order to remove the residue of the liquid-repellent layer 14 remaining on the imprint surface 11g, the imprint surface 11g is washed using a predetermined solvent (dissolving agent) that dissolves the residue of the liquid-repellent layer 14. In other words, a removal process (washing process) is performed in which the residue of the liquid-repellent layer 14 remaining on the imprint surface 11g is dissolved and removed with a solvent.

[0024] Specifically, it is preferable to dissolve and remove all of the unnecessary residue of the liquid-repellent layer 14 remaining on the imprint surface 11g using a volatile solvent that dissolves the liquid-repellent agent used to form the liquid-repellent layer 14. Therefore, it is preferable to select a volatile solvent that has a high solubility for the residue of the liquid-repellent layer 14 remaining on the imprint surface 11g (the liquid-repellent agent used to form the liquid-repellent layer 14) and that has little effect on the liquid-repellent layer 14.

[0025] Examples of methods for supplying a volatile solvent to remove residue of the liquid-repellent layer 14 remaining on the imprint surface 11g include a spin method and an immersion method. In the spin method, the volatile solvent is supplied from a supply head to the imprint surface 11g while the mold 11 is rotated by a rotation mechanism, so that the unnecessary residue of the liquid-repellent layer 14 remaining on the imprint surface 11g can be dissolved in the volatile solvent and removed. In the immersion method, the mold 11 is repeatedly immersed in and pulled out of a container filled with the volatile solvent, so that the unnecessary residue of the liquid-repellent layer 14 remaining on the imprint surface 11g can be dissolved in the volatile solvent and removed.

[0026] Furthermore, when the residue of the liquid-repellent layer 14 remaining on the imprint surface 11g is dissolved in a volatile solvent and removed, the surface of the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a also dissolves slightly. The liquid-repellent performance of the liquid-repellent layer 14 depends on the liquid-repellent agent used to form the liquid-repellent layer 14, but a thickness of a few nanometers, for example, 3 nm or more, will ensure the minimum required liquid-repellent performance. The liquid-repellent layer 14 preferably has a thickness of 10 nm or more, and more preferably has a thickness of 15 nm or more to ensure sufficient liquid-repellent performance.

[0027] As described above, in this embodiment, the processes are performed in the following order: formation of a protective layer, formation of the liquid-repellent layer 14, removal of the protective layer, and removal of the liquid-repellent layer 14 and residues of the liquid-repellent layer 14 (cleaning of the imprint surface 11g). This makes it possible to remove residues of the liquid-repellent layer 14 formed on the imprint surface 11g and form the liquid-repellent layer 14 on the side surface 11d of the mesa portion 11a.

[0028] The protective layer is preferably formed by applying (supplying) the protective material that constitutes the protective layer to the imprint surface 11g. For example, the protective material can be applied to the imprint surface 11g using a dispenser or a printing method. The application area of ​​the imprint surface 11g to which the protective material is applied needs to include at least the outer periphery of the imprint surface 11g. For example, the protective material may be applied to the entire imprint surface 11g, or may be applied to the outer periphery of the imprint surface 11g and an area including its vicinity. The application area to which the protective material is applied may be selected (set) depending on the method for forming the liquid-repellent layer 14. Note that by limiting the application area to which the protective material is applied only to the outer periphery of the imprint surface 11g, the amount of protective material can be reduced and the application time for the protective material can be shortened.

[0029] Examples of the protective material constituting the protective layer include, but are not limited to, glycerin, diglycerin, an aqueous solution of polyacrylic acid, a mixture thereof, etc. It is preferable that the protective material and the liquid repellent agent have low compatibility, and more preferably no compatibility.

[0030] As described above, the liquid-repellent layer 14 is preferably formed using a wet method in which a liquid repellent agent is applied to the side surface 11d of the mesa portion 11a and then dried. However, it may also be formed using a dry method (gas phase method) such as sputtering or vapor deposition. When forming the liquid-repellent layer 14 using a dry method, it is preferable to form a protective layer over the entire imprint surface 11g. Furthermore, when using a wet method, it is possible to form the liquid-repellent layer 14 partially, so it is sufficient to form the protective layer in the outer peripheral region of the imprint surface 11g, but it is also possible to form the protective layer over the entire imprint surface 11g.

[0031] In a wet process, the liquid-repellent agent for forming the liquid-repellent layer 14 is preferably a liquid liquid-repellent agent, and examples thereof include a liquid-repellent agent containing a polymer having a fluorocarbon chain and a volatile solvent that dissolves the polymer. The polymer having a fluorocarbon chain has a large contact angle with the curable composition 13, allowing for the formation of an excellent liquid-repellent layer 14. Examples of the polymer having a fluorocarbon chain include a polymer having a perfluoropolyether group in its main chain and a (meth)acrylic polymer having a perfluoroalkyl group in its side chain. The perfluoropolyether group has 2 to 4 carbon atoms, and the perfluoroalkyl group has 4 to 8 carbon atoms. The polymer having a fluorocarbon chain may have a functional group depending on the application. Examples of such functional groups include a hydroxy group, a formyl group, a carboxyl group, a carbonyl group, an amino group, and an alkoxysilyl group. The volatile solvent contained in the liquid-repellent agent is not particularly limited as long as it dissolves the polymer having a fluorocarbon chain. When forming the liquid-repellent layer 14, it is necessary to evaporate the volatile solvent contained in the liquid-repellent agent. A volatile solvent with a low boiling point is preferable; however, if the boiling point is too low, the polymer having a fluorocarbon chain will solidify while the liquid-repellent agent is being applied, making it impossible to apply the liquid-repellent agent stably. Therefore, the boiling point of the volatile solvent is preferably 50°C to 140°C, and more preferably 60°C to 100°C. Specific examples of volatile solvents include, but are not limited to, Novec 7200 (manufactured by 3M), Novec 7300 (manufactured by 3M), and mixtures thereof.

[0032] Furthermore, in the dry method, the liquid-repellent agent for forming the liquid-repellent layer 14 is preferably a liquid-repellent agent containing at least a fluorocarbon chain and a monolayer-forming material that bonds to the side surface 11d of the mesa portion 11a upon vaporization. Examples include compounds that form an Si-O bond with the side surface 11d of the mesa portion 11a, such as alkoxysilanes having perfluoroalkyl groups, silazanes having perfluoroalkyl groups, and mixtures thereof. The perfluoroalkyl group has 4 to 8 carbon atoms. Such a liquid-repellent agent may be a solution further containing a volatile solvent. A liquid-repellent layer made of a liquid-repellent agent for the wet method and a liquid-repellent layer made of a liquid-repellent agent for the dry method may be formed by stacking them.

[0033] The protective layer formed on the imprint surface 11g is preferably removed by dissolving the protective material (protective component) that constitutes the protective layer using water or an organic solvent. A material that has high solubility in the protective material and does not affect the liquid-repellent layer 14 can be selected as the material for dissolving the protective material that constitutes the protective layer. Furthermore, while the protective layer is formed on the imprint surface 11g, contamination of the imprint surface 11g (adhesion of dust or organic matter) can be prevented. Therefore, the protective layer may be removed immediately after the liquid-repellent layer 14 is formed, or may be removed immediately before using the mold 11, i.e., immediately before performing the imprinting process.

[0034] The volatile solvent for removing the residue of the liquid-repellent layer 14 remaining on the imprint surface 11g after removing the protective layer is preferably a volatile solvent that dissolves a polymer having a fluorocarbon chain, which is a solvent contained in the liquid-repellent agent used to form the liquid-repellent layer 14. Furthermore, when the liquid-repellent layer 14 is formed using a dry method, the volatile solvent for removing the residue of the liquid-repellent layer 14 is preferably a volatile solvent that dissolves a monolayer-forming material that has a fluorocarbon chain and bonds to the side surface 11d of the mesa portion 11a upon vaporization.

[0035] It is preferable to inspect whether or not the liquid-repellent layer 14 is formed in the desired amount (thickness) and in the desired area (the entire area of ​​the side surface 11d) on the side surface 11d of the mesa portion 11a of the mold 11 on which the liquid-repellent layer 14 is formed. In this manner, by inspecting the state of the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11, it is possible to confirm, for example, whether or not it is possible to simultaneously suppress seepage and suppress defects in the composition pattern 13a.

[0036] Therefore, in this embodiment, an inspection unit ISU (inspection device) is provided that inspects a mold 11 in which a liquid-repellent layer 14 is formed on the side surface 11d of a mesa portion 11a protruding from a substrate 11c. In this embodiment, the inspection unit ISU constitutes part of a system 1 that performs processes in the following order: forming a protective layer, forming a liquid-repellent layer 14, removing the protective layer, removing residue of the liquid-repellent layer 14, and inspecting the mold 11, as shown in FIG. 2. In addition to the inspection unit ISU, the system 1 also includes a protective layer forming unit PLU, a liquid-repellent layer forming unit LLU, a protective layer removing unit PRU, a residue removing unit LRU, a transfer unit CVU, and a control unit 111. In the system 1, the transfer unit CVU includes a movable stage and a multi-axis robot, holds the mold 11, and transfers the mold 11 between each unit. The control unit 111 is configured as an information processing device (computer) including a CPU, memory, etc. The control unit 111 comprehensively controls each unit of the system 1 in accordance with a program stored in the storage unit to operate the system 1. Fig. 2 is a diagram showing the configuration of the system 1 having an inspection unit ISU according to one aspect of the present invention.

[0037] 2, the protective layer forming unit PLU, liquid-repellent layer forming unit LLU, protective layer removal unit PRU, residue removal unit LRU, and inspection unit ISU are each configured independently in the system 1. However, the functions of multiple units may be integrated into one unit. For example, the functions of the protective layer forming unit PLU and the liquid-repellent layer forming unit LLU may be integrated, and the formation of the protective layer and the formation of the liquid-repellent layer 14 may be performed in one unit.

[0038] The inspection unit ISU is a unit that has the function of inspecting the mold 11, and in particular, is a unit that inspects the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11. The inspection unit ISU measures the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a in a non-contact manner, and determines the state of the liquid-repellent layer 14 formed on the side surface 11d based on information (state information) that indicates the relationship between the measurement results obtained by the non-contact measurement of the liquid-repellent layer 14 and the state of the liquid-repellent layer 14.

[0039] 3 is a schematic diagram showing an example of the configuration of the inspection unit ISU. The inspection unit ISU has a measurement unit 20 including an irradiation unit 21 and a detection unit 22, a stage 102, a drive mechanism 104, a rotation mechanism 119, and a chamber 109. The inspection unit ISU may further have an alignment mechanism 106 and an imaging unit 110.

[0040] The measurement unit 20 includes an irradiation unit 21 that irradiates energy 23 and a detection unit 22 that detects energy 24, and has the function of non-contact measurement of the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11. However, the measurement unit 20 does not include the irradiation unit 21 and the detection unit 22 as separate units, but may include a unit having the functions of both the irradiation unit 21 and the detection unit 22, such as a laser displacement meter, a laser interferometer, a spectroscopic interference laser displacement meter, or an infrared thermograph. The measurement unit 20 is preferably configured as a non-contact measurement mechanism that measures the liquid-repellent layer 14 in a non-contact manner based on the difference between the properties of the liquid-repellent agent used to form the liquid-repellent layer 14 and the properties of the material constituting the mesa portion 11a. Furthermore, the irradiation unit 21 and the detection unit 22 are each configured to be drivable and rotatable.

[0041] The measuring unit 20 measures the liquid-repellent layer 14 in a non-contact manner by irradiating the side surface 11d on which the liquid-repellent layer 14 is formed with energy 23 from the irradiating unit 21 and detecting energy 24 incident on the detecting unit 22 from the side surface 11d in response to the irradiation by the irradiating unit 21. The energy 24 detected by the detecting unit 22 is energy acting on the side surface 11d of the mesa portion 11a and the liquid-repellent layer 14, specifically, energy affected by the side surface 11d and the liquid-repellent layer 14.

[0042] The irradiation unit 21 includes an energy source that emits energy 23, and an optical system such as a lens, beam splitter, slit, or pinhole for irradiating the energy 23 emitted by the energy source onto the side surface 11d of the mesa portion 11a of the mold 11. The irradiation unit 21 preferably irradiates the energy 23 onto the side surface 11d of the mesa portion 11a of the mold 11 within an area equal to or less than the height of the side surface 11d, and is configured to irradiate the energy 23 with a width or diameter equal to or less than the height of the side surface 11d. In this way, by irradiating the energy 23 only onto the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a and detecting the energy 24, the liquid-repellent layer 14 can be measured in a non-contact manner without being affected by the condition of the periphery of the side surface 11d of the mesa portion 11a.

[0043] The energy 23 emitted by the energy source is preferably at least one of infrared rays, visible light, ultraviolet rays, far ultraviolet rays, X-rays, charged particle rays, radioactive rays, electromagnetic waves, heat, microwaves, and ultrasonic waves. The energy 23 emitted by the energy source is selected appropriately depending on the liquid-repellent agent used to form the liquid-repellent layer 14 so that the liquid-repellent layer 14 is not altered by irradiation with the energy 23. This makes it possible to measure the liquid-repellent layer 14 in a non-contact manner without causing deterioration of the liquid-repellent layer 14 due to contamination of the liquid-repellent layer 14 (changes in the state of the liquid-repellent layer 14).

[0044] The detection unit 22 includes a detector that detects the energy 24 applied by the side surface 11d of the mesa portion 11a and the liquid-repellent layer 14, and an optical system such as a lens, beam splitter, slit, or pinhole for directing (guiding) the energy 24 to the detector. Examples of detectors that detect the energy 24 include photomultipliers, photodiodes, photoconductive elements, photovoltaic elements, and thermocouples. Other detectors that detect the energy 24 include MCDs (CCDs or photodiode arrays), SPADs (Single Photon Avalanche Diodes), and interferometers. If the detection unit 22 (detector) has a detection resolution smaller than the height of the side surface 11d of the mesa portion 11a of the mold 11, full-surface scanning (distribution, mapping) becomes possible.

[0045] The stage 102 holds the mold 11 on which the liquid-repellent layer 14 is formed, for example, by vacuum suction. The stage 102 is configured to be drivable in the X, Y, and Z directions while holding the mold 11, and is also configured to be rotatable within the XY plane (within the stage plane).

[0046] The driving mechanism 104 has a function of driving the stage 102 that holds the mold 11. The driving mechanism 104 is configured to drive the stage 102 at least in the X direction and the Y direction, which are directions (first directions) parallel to the imprint surface 11g (surface) of the mesa portion 11a of the mold 11 held by the stage 102. In this embodiment, the driving mechanism 104 includes an X driving system that drives the stage 102 in the X direction, a Y driving system that drives the stage 102 in the Y direction, and a Z driving system that drives the stage 102 in the Z direction, and each driving system is configured to operate independently. The driving mechanism 104 can be any of a variety of driving mechanisms, such as a linear motor driving mechanism, an air stage driving mechanism, or a feed screw driving mechanism.

[0047] The rotation mechanism 119 has a function of rotating the stage 102 that holds the mold 11. The rotation mechanism 119 is configured to rotate the stage 102 about an axis that is along the Z direction, which is a direction (second direction) perpendicular to the direction parallel to the imprint surface 11g of the mesa portion 11a of the mold 11 held by the stage 102. The rotation axis that rotates the stage 102 by the rotation mechanism 119, i.e., the rotation axis of the stage 102, is set to coincide with the center of the stage 102 (the axis that passes through the center and is along the Z direction).

[0048] The alignment mechanism 106 is a mechanism for relatively aligning the mold 11 (the mesa portion 11a) and the stage 102 when the mold 11 is held on the stage 102. In this embodiment, the alignment mechanism 106 has a function of aligning the center of the mold 11 with the rotation axis of the stage 102. The alignment mechanism 106 aligns the mold 11 and the stage 102, for example, by using an alignment mark provided on the mold 11 or the mesa portion 11a.

[0049] The chamber 109 defines a processing space that houses the measurement unit 20, the stage 102, the drive mechanism 104, the rotation mechanism 119, etc. A filter unit 112, to which a filter for removing foreign matter contained in the gas (air) is attached, is provided on the upper surface of the chamber 109. An exhaust port 113 for discharging gas within the processing space (inside the chamber 109) to the outside is provided on the lower surface (bottom surface) of the chamber 109. Therefore, the processing space is kept clean by a downflow (vertical laminar flow) of gas flowing from the filter unit 112 toward the exhaust port 113. For example, a ULPA filter or a HEPA filter can be used as the filter.

[0050] The imaging unit 110 is provided on the top or side of the chamber 109 so as to be able to capture an image of the mold 11 held on the stage 102, particularly the mesa portion 11a and the vicinity of the mesa portion 11a. The image captured by the imaging unit 110 (for example, a planar image of the side surface 11d of the mesa portion 11a of the mold 11) is transmitted to the control unit 111, an external information processing device, or the like.

[0051] The control unit 111 comprehensively controls each part of the inspection unit ISU to operate the inspection unit ISU in accordance with a program stored in the storage unit. The control unit 111 may be configured integrally with the other parts of the inspection unit ISU (in a common housing), or may be configured separately from the other parts of the inspection unit ISU (in a different housing).

[0052] In this embodiment, the control unit 111 has a function for determining the state of the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11. To achieve this function, the control unit 111 functions as an acquisition unit that acquires state information indicating the relationship between the state of the liquid-repellent layer 14 and the measurement results obtained by non-contact measurement of the liquid-repellent layer 14. The control unit 111 acquires the state information in advance from, for example, an external information processing device that generates the state information and stores the state information in a storage unit such as a memory. However, the state information may also be generated inside the system 1. The control unit 111 also functions as a processing unit that determines the state of the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11 based on the state information and the measurement results obtained by the measurement unit 20 (measurement results obtained by non-contact measurement of the liquid-repellent layer 14).

[0053] In the state information, the measurement results obtained by measuring the liquid-repellent layer 14 include at least one of the material properties, optical properties, electromagnetic wave properties, radiation properties, and thermal properties of the liquid-repellent layer 14. Specifically, the measurement results obtained by measuring the liquid-repellent layer 14 include at least one of the transmittance, absorptance, reflectance, emissivity, vibration coefficient, and thickness of the liquid-repellent layer 14. The measurement results obtained by measuring the liquid-repellent layer 14 also include interference between the side surface 11d of the mesa portion 11a of the mold 11 and the liquid-repellent layer 14, a phase difference between the side surface 11d and the liquid-repellent layer 14, and the like.

[0054] In addition, in the state information, the state of the liquid-repellent layer 14 includes at least one of the liquid repellency and surface free energy of the liquid-repellent layer 14 with respect to the curable composition 13, the contact angle, sliding angle, and receding contact angle of the curable composition 13 with respect to the liquid-repellent layer 14.

[0055] In this embodiment, the status information is typically assumed to be the relationship between the reflectance of the liquid-repellent layer 14 and the contact angle of the curable composition 13 on the liquid-repellent layer 14, or the relationship between the transmittance of the liquid-repellent layer 14 and the contact angle of the curable composition 13 on the liquid-repellent layer 14, but is not limited thereto. The status information may also be the relationship between the thickness of the liquid-repellent layer 14 and the contact angle of the curable composition 13 on the liquid-repellent layer 14, or the relationship between the temperature of the liquid-repellent layer 14 and the contact angle of the curable composition 13 on the liquid-repellent layer 14. It is preferable to use a relationship based on the material properties and measurement conditions of the liquid-repellent layer 14 as the status information. In other words, if the material of the liquid-repellent layer 14 or the measurement conditions are changed, it is preferable to newly obtain these relationships. If the material of the liquid-repellent layer 14 and the measurement conditions are the same as those used in a previous measurement, the previously obtained relationship may be used.

[0056] The control unit 111 may also determine the difference between the measurement results (actual state of the liquid-repellent layer 14) obtained by the measurement unit 20 and a target state (set value) of the liquid-repellent layer 14 to be formed on the side surface 11d of the mesa portion 11a of the mold 11. This difference can be used for feedback as information for bringing the liquid-repellent layer 14 closer to the target state. For example, the control unit 111 determines formation conditions for forming the liquid-repellent layer 14 on the side surface 11d of the mesa portion 11a of the mold 11 based on the difference between the measurement results obtained by the measurement unit 20 and the target state of the liquid-repellent layer 14. The control unit 111 may also determine repair conditions for repairing the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11 based on the difference between the measurement results obtained by the measurement unit 20 and the target state of the liquid-repellent layer 14. The formation conditions and repair conditions include various conditions for bringing the liquid-repellent layer 14 into a target state, such as the amount (application amount) and position (application position) of the liquid-repellent agent to be applied to the side surface 11d of the mesa portion 11a of the mold 11.

[0057] The control unit 111 can also determine whether the mold 11 on which the liquid-repellent layer 14 is formed is usable, based on the difference between the measurement result obtained by the measurement unit 20 and the target state of the liquid-repellent layer 14. For example, the control unit 111 determines that the mold 11 is usable if the difference between the measurement result obtained by the measurement unit 20 and the target state of the liquid-repellent layer 14 is equal to or less than a threshold. On the other hand, the control unit 111 determines that the mold 11 is unusable if the difference between the measurement result obtained by the measurement unit 20 and the target state of the liquid-repellent layer 14 is greater than the threshold. Note that the mold 11 may be an unused mold that has not been used in the imprint process, or may be a used mold that has been used in the imprint process.

[0058] In this way, the inspection unit ISU measures the liquid-repellent layer 14 in a non-contact manner, thereby making it possible to inspect the state of the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11 without causing deterioration of the liquid-repellent layer 14 due to contamination of the liquid-repellent layer 14. Furthermore, as shown in FIG. 2, by providing the liquid-repellent layer forming unit LLU, which forms the liquid-repellent layer 14, and the inspection unit ISU in the same system, it is possible to suppress deterioration of the liquid-repellent layer 14. Therefore, according to this embodiment, it is possible to manufacture and inspect a mold 11 that suppresses both seepage and defects in the composition pattern 13a.

[0059] Furthermore, the inspection unit ISU can inspect not only the state of the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11, but also the state of the imprint surface 11g of the mesa portion 11a. In this case, the control unit 111 acquires in advance information (state information) indicating the relationship between the measurement results obtained by non-contact measurement of the imprint surface 11g and the state of the liquid-repellent layer 14, and stores the information in a storage unit such as a memory. The control unit 111 then determines the state of the imprint surface 11g based on the state information and the measurement results obtained by non-contact measurement of the imprint surface 11g by the measurement unit 20. In this case, the measurement unit 20 measures the imprint surface 11g in a non-contact manner by irradiating energy from the irradiation unit 21 onto the imprint surface 11g and detecting the energy incident on the detection unit 22 from the imprint surface 11g in response to the irradiation by the irradiation unit 21.

[0060] In this way, the inspection unit ISU measures the imprint surface 11g in a non-contact manner, thereby enabling inspection of the state of the imprint surface 11g without causing deterioration of the liquid-repellent layer 14 due to contamination of the liquid-repellent layer 14 or contamination of the imprint surface 11g. Here, inspecting the state of the imprint surface 11g means, for example, inspecting (confirming) whether or not unnecessary residue of the liquid-repellent layer 14 remains around the liquid-repellent layer 14, such as on the imprint surface 11g. Furthermore, as shown in FIG. 2, by providing the liquid-repellent layer forming unit LLU, which forms the liquid-repellent layer 14, and the inspection unit ISU in the same system, deterioration of the liquid-repellent layer 14 can be suppressed. Therefore, according to this embodiment, it is possible to manufacture and inspect a mold 11 that simultaneously suppresses seepage and suppresses defects in the composition pattern 13a.

[0061] The inspection unit ISU can also be combined with a transport mechanism, a loading unit, an unloading unit, and the like to be introduced into an apparatus other than the system 1, such as an imprinting apparatus, as an inspection apparatus for inspecting the mold 11. Imprinting apparatuses include imprinting apparatuses for device manufacturing, which manufacture devices such as semiconductor elements using the mold 11, and imprinting apparatuses for replica manufacturing, which manufacture the mold 11 from a blank substrate for the replica mold. In imprinting apparatuses for device manufacturing, the inspection unit ISU can inspect unused or used molds, as described above, to determine whether or not the molds are usable. In imprinting apparatuses for replica manufacturing, the inspection unit ISU can inspect manufactured replica molds, ensuring the manufacture of replica molds that simultaneously suppress leaching and defects in the composition pattern 13a.

[0062] 4 is a schematic diagram showing an example of the configuration of the protective layer forming unit PLU. The protective layer forming unit PLU is a unit that uses a liquid protective material to form a protective layer on the imprint surface 11g of the mesa portion 11a of the mold 11 to prevent the formation of a liquid-repellent layer 14 on the imprint surface 11g. The protective layer forming unit PLU forms a protective layer on at least the outer peripheral region of the imprint surface 11g of the mesa portion 11b of the mold 11. The protective layer forming unit PLU has a stage 102, a supply head 103, a drive mechanism 104A, a chamber 109, and an imaging unit 110.

[0063] The stage 102 holds the mold 11 for forming the protective layer by, for example, vacuum suction.

[0064] The supply head 103 includes, for example, a storage unit that stores a liquid protective material supplied from an external tank or the like, and a dispenser that dispenses the liquid protective material stored in the storage unit. Under the control of the control unit 111, the supply head 103 dispenses the liquid protective material from the dispenser at a predetermined timing onto the mold 11 held by the stage 102, thereby coating the mold 11 with the protective material and forming a protective layer.

[0065] The driving mechanism 104A holds the supply head 103 and drives the supply head 103 relative to the stage 102. The driving mechanism 104A is configured to drive the supply head 103 in the X, Y, and Z directions. In this embodiment, the driving mechanism 104A includes an X driving system that drives the supply head 103 in the X direction, a Y driving system that drives the supply head 103 in the Y direction, and a Z driving system that drives the supply head 103 in the Z direction, and each driving system is configured to operate independently. The driving mechanism 104A can be any of a variety of driving mechanisms, such as a linear motor driving mechanism, an air stage driving mechanism, or a feed screw driving mechanism.

[0066] The chamber 109 defines a processing space that houses the stage 102, the supply head 103, the drive mechanism 104A, the imaging unit 110, etc. A filter unit 112 is provided on the upper surface of the chamber 109, and an exhaust port 113 is provided on the lower surface of the chamber 109.

[0067] The imaging unit 110 is provided on the upper surface of the chamber 109 so as to be able to capture an image by imaging the mesa portion 11a of the mold 11 held on the stage 102 and the vicinity of the mesa portion 11a. The image captured by the imaging unit 110 (for example, a planar image of the mesa portion 11a (imprint surface 11g) of the mold 11) is transmitted to the control unit 111, an external information processing device, or the like.

[0068] The liquid-repellent layer forming unit LLU is a unit that forms a liquid-repellent layer at least on the side surface 11d of the mesa portion 11a of the mold 11. However, in this embodiment, when forming the liquid-repellent layer 14 on the side surface 11d of the mesa portion 11a, the liquid-repellent layer forming unit LLU also forms the liquid-repellent layer 14 on a partial region of the protective layer.

[0069] The configuration of the liquid-repellent layer forming unit LLU is not particularly limited, but differs between the dry method and the wet method. In the dry method, the liquid-repellent layer forming unit LLU has, for example, a chamber, a storage unit for storing a liquid-repellent agent, and a heating unit such as a heater. The liquid-repellent agent stored in the storage unit is heated by the heating unit to evaporate and gasify, thereby forming the liquid-repellent layer 14 on the mold 11. In the wet method, the liquid-repellent layer forming unit LLU has, for example, a configuration similar to that of the protective layer forming unit PLU shown in FIG. 4. In this case, the liquid-repellent agent is ejected from a supply head 103 onto the mold 11 held by a stage 102, and the liquid-repellent agent is applied to a predetermined region, including the side surface 11d of the mesa portion 11a of the mold 11, thereby forming the liquid-repellent layer 14.

[0070] 5 is a schematic diagram showing an example of the configuration of the protective layer removal unit PRU. The protective layer removal unit PRU is a unit that removes the protective layer formed on the imprint surface 11g of the mesa portion 11a of the mold 11 by dissolving the protective layer with a removal material that can dissolve the protective layer. By dissolving and removing the protective layer, the protective layer removal unit PRU can also remove the liquid-repellent layer 14 formed on a partial region of the protective layer. The protective layer removal unit PRU has a stage 102, a drive mechanism 104A, a chamber 109, a supply head 118, and a rotation mechanism 119.

[0071] The stage 102 holds the mold 11 on which the protective layer and the liquid-repellent layer 14 are formed, for example, by vacuum suction.

[0072] The driving mechanism 104A holds the supply head 118 and drives the supply head 118 relative to the stage 102. The driving mechanism 104A is configured to drive the supply head 118 in the X, Y, and Z directions. In this embodiment, the driving mechanism 104A includes an X driving system that drives the supply head 118 in the X direction, a Y driving system that drives the supply head 118 in the Y direction, and a Z driving system that drives the supply head 118 in the Z direction, and each driving system is configured to operate independently.

[0073] The chamber 109 defines a processing space that houses the stage 102, the supply head 118, the driving mechanism 104A, etc. A filter unit 112 is provided on the upper surface of the chamber 109, and an exhaust port 113 is provided on the lower surface of the chamber 109.

[0074] The supply head 118 includes, for example, a container that contains a liquid removal material that dissolves and removes the protective layer and is supplied from an external tank, and a dispenser that dispenses the liquid removal material contained in the container. Under the control of the control unit 111, the supply head 118 dispenses the liquid removal material from the dispenser at a predetermined timing onto the mold 11 held by the stage 102.

[0075] In this embodiment, the protective layer formed on the imprint surface 11g of the mesa portion 11a of the mold 11 is removed using a configuration that combines a supply head 118 and a rotation mechanism 119. Specifically, first, the mold 11 is held on the stage 102 so that the center of the stage 102 (the rotation axis of the stage 102) and the center of the mold 11 coincide. Next, the rotation mechanism 119 rotates the stage 102, thereby rotating the mold 11 held on the stage 102 in conjunction with the stage 102. At this time, it is preferable that the rotation mechanism 119 rotates the stage 102 at a low speed. Next, the drive mechanism 104A drives the supply head 118 above the center of the mold 11 while maintaining it at a predetermined height, and the supply head 118 discharges a removal material onto the mold 11. The removal material is supplied to the center of the mold 11 (imprint surface 11g) or near the center of the mold 11 and spreads outward due to the centrifugal force caused by the rotation of the stage 102. As a result, the protective layer formed on the imprint surface 11g is dissolved and removed by the removal material, and the removal material resulting from the dissolved protective layer can be flushed (discharged) out of the mold 11. Furthermore, by dissolving and removing the protective layer, the liquid-repellent layer 14 formed on a partial area of ​​the protective layer is also removed from the imprint surface 11g. By continuing to eject the removal material from the supply head 118, all of the protective layer formed on the imprint surface 11g is dissolved and removed. Then, once the protective layer (and the liquid-repellent layer 14 formed on the protective layer) has been removed from the imprint surface 11g, the ejection of the removal material from the supply head 118 and the rotation of the stage 102 by the rotation mechanism 119 are stopped, and the imprint surface 11g is dried.

[0076] In this embodiment, the protective layer removal unit PRU has been described as employing a spin method to remove the protective layer, in which a removal material is supplied to the imprint surface 11g of the mesa portion 11a of the mold 11 and the protective layer is removed by rotating the mold 11. However, the method for removing the protective layer is not limited to the spin method. For example, the protective layer removal unit PRU may employ an immersion method in which the protective layer formed on the imprint surface 11g is dissolved and removed by repeatedly immersing and pulling up the mold 11 into a container filled with a removal material.

[0077] The residue removal unit LRU is a unit that removes residue of the liquid-repellent layer 14 remaining on the imprint surface 11g of the mesa portion 11a of the mold 11 by dissolving it with a volatile solvent (solvent contained in the liquid-repellent agent) that can dissolve the liquid-repellent layer 14. The configuration of the residue removal unit LRU is not particularly limited. For example, the residue removal unit LRU has a configuration similar to that of the protective layer removal unit PRU shown in FIG. 5. In this case, the residue removal unit LRU rotates the mold 11 while supplying the volatile solvent to the imprint surface 11g of the mesa portion 11a of the mold 11, thereby dissolving and removing the residue of the liquid-repellent layer 14 remaining on the imprint surface 11g in the volatile solvent. Note that the volatile solvent in which the residue of the liquid-repellent layer 14 has been dissolved is washed out of the mold 11 (discharged) by the centrifugal force generated by the rotation of the stage 102. Furthermore, as described above, the protective layer removal unit PRU can also remove residue of the liquid-repellent layer 14 by repeatedly immersing and lifting the mold 11 into a container filled with a volatile solvent multiple times.

[0078] In the system 1, as described above, the protective layer forming unit PLU forms a protective layer on the imprint surface 11g of the mesa portion 11a of the mold 11, and then the liquid-repellent layer forming unit LLU forms the liquid-repellent layer 14 on the side surface 11d of the mesa portion 11a. The protective layer removing unit PRU removes the protective layer from the imprint surface 11g of the mesa portion 11a of the mold 11, and the residue removing unit LRU removes residue of the liquid-repellent layer 14 remaining on the imprint surface 11g. In this way, as shown in FIG. 1, a mold 11 is obtained in which the liquid-repellent layer 14 is formed on the side surface 11d of the mesa portion 11a and the residue of the liquid-repellent layer 14 has been removed from the imprint surface 11g of the mesa portion 11a. Then, in the inspection unit ISU, the state of the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11 and the state of the imprint surface 11g of the mesa portion 11a of the mold 11 are inspected.

[0079] The operation of the system 1 will be described in detail below with reference to Figures 6(a) to 6(f), 7(a), 7(b), 8(a) and 8(b). As described above, the system 1 operates by the control unit 111 comprehensively controlling each unit of the system 1.

[0080] In S101, as shown in Fig. 6(a), a protective layer 16 is formed. In this embodiment, in the protective layer forming unit PLU, a liquid protective material is applied from a supply head 103 to the imprint surface 11g of the mesa portion 11a of the mold 11, at least to the outer periphery of the imprint surface 11g, to form the protective layer 16. Note that by forming the protective layer 16 over the entire imprint surface 11g of the mesa portion 11a of the mold 11, the imprint surface 11g can be protected from dust adhesion and contamination, and therefore the protective layer 16 also functions as a contamination prevention layer when the mold 11 is transported.

[0081] Specifically, as shown in FIG. 6(b), the drive mechanism 104A drives the supply head 103 along a path including positions P1-1, P2-1, P3-1, P4-1, and P5-1 toward the mold 11, and the protective material is continuously discharged from the supply head 103. The path including positions P1-1 to P5-1 is spaced a predetermined distance L-1 (e.g., 0.2 mm) inward from the outer edge of the imprint surface 11g of the mold 11. Position P1-1 is the discharge start position where the supply head 103 starts discharging the protective material, and position P5-1 is the discharge stop position where the supply head 103 stops discharging the protective material. On the imprint surface 11g, the protective material supplied in a frame shape along the path including positions P1-1 to P5-1 spreads due to surface energy and reaches the outer edge 11h of the imprint surface 11g. As a result, the protective material is applied within a predetermined distance L-1 inward from the outer edge 11h of the imprint surface 11g, that is, only in the outer edge region of the imprint surface 11g, to form the protective layer 16.

[0082] In S102, as shown in Fig. 6(c), the liquid-repellent layer 14 is formed. In this embodiment, in the liquid-repellent layer forming unit LLU, the liquid-repellent layer 14 is formed by applying a liquid liquid-repellent agent from a supply head to the mesa portion 11a of the mold 11, at least to the side surface 11d of the mesa portion 11a.

[0083] Specifically, as shown in FIG. 6(d), the supply head is driven along a path including positions P1-2, P2-2, P3-2, P4-2, and P5-2 toward the mold 11, while continuously discharging the liquid-repellent agent from the supply head. The path including positions P1-2 to P5-2 is spaced a predetermined distance L-2 (e.g., 1 mm) outward from the outer edge 11h of the imprint surface 11g. Position P1-2 is the discharge start position where the supply head starts discharging the liquid-repellent agent, and position P5-2 is the discharge stop position where the supply head stops discharging the liquid-repellent agent. In the mold 11, the liquid-repellent agent supplied in a frame shape around the mesa portion 11a along the path including positions P1-2 to P5-2 spreads due to surface energy and reaches the side surface 11d of the mesa portion 11a. The liquid-repellent agent that has reached the side surface 11d of the mesa portion 11a of the mold 11 further spreads beyond the side surface 11d of the mesa portion 11a to the protective layer 16 formed on the outer peripheral region of the imprint surface 11g. As a result, when the volatile solvent contained in the liquid-repellent agent evaporates and dries, a liquid-repellent layer 14 is formed on the side surface 11d of the mesa portion 11a of the mold 11 and on a partial region of the protective layer 16. Note that the liquid-repellent agent does not reach the region of the imprint surface 11g where the protective layer 16 is not formed, and therefore the liquid-repellent layer 14 is not formed directly on the imprint surface 11g.

[0084] 6(b) and 6(d) are merely examples, and any path may be used as long as it is capable of supplying the protective material or liquid repellent agent in a frame shape around the imprint surface 11g or the mesa portion 11a. Furthermore, the ejection start and stop positions are not limited, and it is not essential that the protective material or liquid repellent agent be continuously ejected from the supply head.

[0085] In S103, the protective layer 16 is removed, as shown in FIG. 6( e). In this embodiment, in the protective layer removal unit PRU, a removal material capable of dissolving the protective layer 16 is supplied from the supply head 118 to the imprint surface 11g of the mesa portion 11a of the mold 11, thereby removing the protective layer 16 formed on the imprint surface 11g. As a result, the protective layer 16 is dissolved and removed by the removal material, and the liquid-repellent layer 14 formed on a partial region of the protective layer 16 is also removed from the imprint surface 11g. However, a portion of the liquid-repellent layer 14 may remain as residue 15 on the imprint surface 11g or in the peripheral region of the imprint surface 11g.

[0086] In S104, as shown in Fig. 6(f), residues 15 of the liquid-repellent layer 14 are removed. In this embodiment, in the residue removal unit LRU, a supply head supplies a volatile solvent capable of dissolving the liquid-repellent layer 14 to the imprint surface 11g of the mesa portion 11a of the mold 11, thereby removing unnecessary residues of the liquid-repellent layer 14 remaining on the imprint surface 11g. This results in a mold 11 in which the liquid-repellent layer 14 is formed only on the side surface 11d of the mesa portion 11a.

[0087] In this embodiment, after forming the protective layer 16 on the imprint surface 11g of the mesa portion 11a of the mold 11, the liquid-repellent layer 14 is formed on the side surface 11d of the mesa portion 11a. However, before forming the liquid-repellent layer 14 on the side surface 11d of the mesa portion 11a, a light-shielding layer that blocks light for curing the curable composition 13 on the substrate may be formed. Even when forming a light-shielding layer on the imprint surface 11g of the mesa portion 11a of the mold 11, forming the protective layer 16 on the imprint surface 11g in advance can prevent the light-shielding layer from being formed on the imprint surface 11g.

[0088] In S105, the mold 11 is inspected. In this embodiment, the inspection unit ISU performs non-contact measurement of the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11, and determines the state of the liquid-repellent layer 14 based on the state information. However, as described above, the inspection unit ISU can also perform non-contact measurement of the imprint surface 11g of the mesa portion 11a of the mold 11, and determine the state of the imprint surface 11g based on the state information. Note that, as described above, the state information indicating the relationship between the measurement results obtained by non-contact measurement of the liquid-repellent layer 14 and the state of the liquid-repellent layer 14 is acquired in advance and stored in a storage unit such as a memory of the control unit 111.

[0089] A specific method for non-contact measurement of the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11 will be described. First, the stage 102 holding the mold 11 is driven by the drive mechanism 104 or rotated by the rotation mechanism 119 to align each measurement point of the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a with the measurement unit 20. The measurement points of the liquid-repellent layer 14 are locations irradiated with energy 23 from the irradiation unit 21 and are set at any location on the side surface 11d of the mesa portion 11a of the mold 11. The measurement points of the liquid-repellent layer 14 are, for example, designated by the user and set at multiple locations on the side surface 11d so that the entire area of ​​the side surface 11d is scanned with the energy. Here, if the mesa portion 11a has a rectangular parallelepiped shape with dimensions of 26 mm wide x 33 mm long x 30 μm high, the number of side surfaces 11d of the mesa portion 11a will be four. In this case, energy 23 is irradiated from the irradiation unit 21 to a first measurement point (a1) on the liquid-repellent layer 14 formed on the first side surface 11d of the mesa portion 11a, and energy 24 incident from the first measurement point to the detection unit 22 in response to the irradiation by the irradiation unit 21 is detected. Then, while the mold 11 is driven in a direction parallel to the first side surface 11d of the mesa portion 11a, energy 23 is irradiated to each measurement point (a2,...a m) on that side, and energy 24 incident from each measurement point to the detection unit 22 in response to the irradiation by the irradiation unit 21 is detected. This allows non-contact measurement (scan measurement) of the entire first side surface 11d of the mesa portion 11a. Next, the mold 11 is rotated 90 degrees, and each measurement point on the liquid-repellent layer 14 formed on the second side surface 11d of the mesa portion 11a is aligned with the measurement unit 20. Energy 23 is irradiated from irradiation unit 21 to a first measurement point (b1) on liquid-repellent layer 14 formed on second side surface 11d of mesa portion 11a, and energy 24 incident on detection unit 22 from the first measurement point in response to the irradiation by irradiation unit 21 is detected. Then, while mold 11 is driven in a direction parallel to second side surface 11d of mesa portion 11a, energy 23 is irradiated to each measurement point (b2, ... bn) on that side, and energy 24 incident on detection unit 22 from each measurement point in response to the irradiation by irradiation unit 21 is detected. This allows the entire area of ​​second side surface 11d of mesa portion 11a to be measured (scan measurement) in a non-contact manner.By performing such scanning measurement on each of the third side surface 11d and the fourth side surface 11d of the mesa portion 11a, it is possible to measure the liquid-repellent layer 14 formed on each of the four side surfaces 11d of the mesa portion 11a in a non-contact manner.

[0090] 8(a) is a diagram showing an example of the positional relationship of the irradiation unit 21 and the detection unit 22 with respect to the mold 11 when measuring the side surface 11d of the mesa portion 11a of the mold 11 in a non-contact manner. In the irradiation unit 21, a light source capable of providing the optical output required to measure the liquid-repellent layer 14 is selected as the energy source, and is selected from, for example, a lamp, a laser diode, a laser such as a UV laser or a solid-state laser, an LED, etc. In this example, the energy source is a laser light source 21a that emits laser light with a wavelength of 550 nm.

[0091] Referring to FIG. 8(a), laser light 23a (energy 23) from laser light source 21a is irradiated via optical elements 28a and 28b to a measurement point on liquid-repellent layer 14 formed on side surface 11d of mesa portion 11a of mold 11. Optical element 28a is, for example, a slit or a pinhole, and optical element 28b is, for example, a lens, but is not limited thereto. Laser light 24a (energy 24) reflected by side surface 11d of mesa portion 11a of mold 11 and liquid-repellent layer 14 is detected by detector 22a via optical elements 28c and 28d. Optical element 28c is, for example, a lens, and optical element 28d is, for example, a slit or a pinhole, but is not limited thereto.

[0092] When a photomultiplier 22a is used as the detector 22a in the detection unit 22, the reflectance of the liquid-repellent layer 14 can be measured by detecting the laser light 24a incident on the detector 22a. Similarly, when a SPAD is used as the detector 22a, the reflectance of the liquid-repellent layer 14 can be measured by detecting the laser light 24a incident on the detector 22a.

[0093] Furthermore, the irradiation unit 21 and the detection unit 22 may be configured to measure the transmittance of the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11. For example, the transmittance of the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a can be obtained by measuring the difference between the transmittance of the side surface 11d of the mesa portion 11a before the liquid-repellent layer 14 is formed and the transmittance of the side surface 11d of the mesa portion 11a after the liquid-repellent layer 14 is formed.

[0094] Furthermore, by using a laser interferometer as the irradiation unit 21 and the detection unit 22, it is possible to measure the thickness of the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11. For example, the thickness of the liquid-repellent layer 14 can be obtained by measuring the interference between light reflected by the side surface 11d of the mesa portion 11a and light reflected by the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a.

[0095] Furthermore, the thickness of the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11 can also be measured by using a laser displacement meter as the irradiation unit 21 and the detection unit 22. For example, the thickness of the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a can be determined by measuring the difference between the distance to the side surface 11d of the mesa portion 11a before the liquid-repellent layer 14 is formed and the distance to the side surface 11d of the mesa portion 11a after the liquid-repellent layer 14 is formed. As the laser displacement meter, for example, a multicolor laser coaxial displacement meter CL-3000 series (minimum spot diameter: 3.5 μm) manufactured by Keyence Corporation can be used, but is not limited to this.

[0096] In addition to the measurement results obtained by non-contact measurement of the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11, various information associated with the measurement results may be acquired. Such various information includes at least one of information regarding the position of the side surface 11d of the mesa portion 11a of the mold 11, information regarding the coordinates of the side surface 11d, and information regarding the mold 11. Specific examples of mold-related information include, but are not limited to, mold identification information, mold measurement value information, and mold structure information. Examples of mold identification information include mold individual numbers, lot numbers, barcodes, and two-dimensional codes. Examples of mold measurement value information include measurements of the side surfaces before the liquid-repellent layer is formed. Examples of mold structure information include mold and mesa sizes, mesa position and coordinates, mesa sidewall position and coordinates, imprint surface pattern information, and alignment mark information. By acquiring the various information described above, the liquid-repellent layer at desired positions and coordinates can be measured non-contact.

[0097] When measuring the imprint surface 11g of the mesa portion 11a of the mold 11 in a non-contact manner, the irradiation unit 21 and the detection unit 22 may be arranged as shown in Fig. 8(b). Fig. 8(b) is a diagram showing an example of the arrangement of the irradiation unit 21 and the detection unit 22 with respect to the mold 11 when measuring the imprint surface 11g of the mesa portion 11a of the mold 11 in a non-contact manner.

[0098] Referring to FIG. 8(b), energy 23a from energy source 21b is irradiated onto a measurement point on imprint surface 11g of mesa portion 11a of mold 11 via optical elements 28e and 28f. Optical element 28e is, for example, a slit or a pinhole, and optical element 28f is, for example, a lens, but is not limited to these. Energy 24b acted upon by imprint surface 11g of mesa portion 11a of mold 11 and residue of liquid-repellent layer 14 is detected by detector 22b via optical elements 28g and 28h. Optical element 28g is, for example, a lens, and optical element 28h is, for example, a slit or a pinhole, but is not limited to these.

[0099] When, for example, an infrared thermograph is used as the irradiation unit 21 and the detection unit 22, the difference between the measurement result of the imprint surface 11g before the liquid-repellent layer 14 is formed and the measurement result of the imprint surface 11g after the liquid-repellent layer 14 is formed is measured. The presence or absence and location of residues of the liquid-repellent layer 14 remaining on the imprint surface 11g can be determined from the minute difference in temperature rise due to the difference in the amount of infrared light absorption between the imprint surface 11g and the residues of the liquid-repellent layer 14. As the infrared thermograph, for example, an infrared thermograph SC7000 series manufactured by FLIR Systems Inc. can be used, but is not limited to this.

[0100] In Figure 7(a), the operation of system 1 ends with the process of inspecting mold 11, but the operation of system 1 may also include a process of feeding back the inspection results of mold 11 in order to bring the liquid-repellent layer 14 closer to the target state, as shown in Figure 7(b).

[0101] Referring to FIG. 7(b), in S108, it is determined whether the liquid repellency of the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11 satisfies a standard. For example, the difference between the measurement result obtained by the measurement unit 20 in S105, i.e., the actual state of the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a, and the target state (set value) of the liquid-repellent layer 14 to be formed on the side surface 11d of the mesa portion 11a is calculated. Here, the target state of the liquid-repellent layer 14 is set within a range in which the liquid-repellent layer 14 exhibits appropriate liquid repellency with respect to the curable composition 13. If the difference between the measurement result obtained by the measurement unit 20 in S105 and the target state of the liquid-repellent layer 14 is equal to or less than a threshold, it is determined that the liquid repellency of the liquid-repellent layer 14 satisfies the standard, and the operation is terminated. On the other hand, if the difference between the measurement result obtained by the measurement unit 20 in S105 and the target state of the liquid-repellent layer 14 is greater than the threshold, the process proceeds to S109.

[0102] In S109, feedback information for bringing the liquid-repellent layer 14 closer to the target state is generated based on the difference between the actual state of the liquid-repellent layer 14 obtained in S108 and the target state. For example, based on the difference between the actual state of the liquid-repellent layer 14 and the target state, formation conditions for forming the liquid-repellent layer 14 on the side surface 11d of the mesa portion 11a of the mold 11 are determined, and formation information related to these formation conditions is generated as feedback information. The formation conditions generated in this manner are fed back to the step (S101) of forming the protective layer 16 on the side surface 11d of the mesa portion 11a of the new mold 11 or the step (S102) of forming the liquid-repellent layer 14 on the side surface 11d of the mesa portion 11a of the new mold 11. Furthermore, based on the difference between the actual state of the liquid-repellent layer 14 and the target state, repair conditions for repairing the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11 may be determined, and repair information related to these repair conditions may be generated as feedback information. The repair information thus generated is fed back to the process of repairing the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the current mold 11.

[0103] Hereinafter, the acquisition of state information indicating the relationship between the measurement results obtained by non-contact measurement of the liquid-repellent layer 14 and the state of the liquid-repellent layer 14 will be described with reference to specific examples.

[0104] Example 1 As described above, a liquid-repellent layer 14 was formed on the side surface 11d of the mesa portion 11a of the mold 11. Glycerin was used as the protective material constituting the protective layer 16, and pure water was used as the removal material for dissolving and removing the protective layer 16. The liquid-repellent agent used was a polymer having a perfluoroalkyl group with six carbon atoms in its side chain dissolved in a volatile solvent at a solids concentration of 0.06 wt%. Novec 7200 manufactured by 3M was used as the volatile solvent for dissolving and removing the residue of the liquid-repellent layer 14 remaining on the imprint surface 11g of the mesa portion 11a of the mold 11. The time required for removing the residue of the liquid-repellent layer 14 using the volatile solvent was 5 seconds.

[0105] The contact angle of the curable composition 13 with the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11 was measured using a technique well known in the art. One well-known technique is to apply a droplet of a measurement liquid, such as pure water or a curable composition, to the liquid-repellent layer 14 and, from a lateral image of the droplet applied to the liquid-repellent layer 14, determine the contact angle as the angle of the tangent of the droplet at its end point relative to the surface of the liquid-repellent layer 14. In particular, when determining the contact angle in a small region, such as the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11, it is preferable to apply a very small droplet on the order of pL. For example, an inkjet contact angle meter, DropMeasure-1000 manufactured by Microjet Corporation, can be used, but the method is not limited thereto. This contact angle meter can apply droplets with a minimum diameter of 20 μm to the liquid-repellent layer 14 in a non-contact manner, photograph the droplets from the side, and measure the contact angle in a small area, such as the liquid-repellent layer 14 formed on the side surface 11 d of the mesa portion 11 a. Furthermore, if the inspection unit ISU is incorporated into an imprinting apparatus, it is also possible to apply smaller droplets to the liquid-repellent layer 14 using a dispensing device (dispenser) that dispenses the curable composition included in the imprinting apparatus. Note that the presence of moisture (humidity), organic components, particles, etc. in the atmosphere in which the contact angle is measured can alter or deteriorate the liquid-repellent layer 14, making it difficult to accurately measure the contact angle. Therefore, it is preferable to perform contact angle measurement of the curable composition 13 on the liquid-repellent layer 14 and non-contact measurement of the liquid-repellent layer 14 in a low-humidity, clean atmosphere. For example, it is preferable to combine the liquid-repellent layer forming unit LLU and the inspection unit ISU into one unit, and to perform the formation of the liquid-repellent layer 14 and the inspection of the mold 11 (liquid-repellent layer 14) within this unit.

[0106] In this example, the curable composition 13 before curing was dropped onto the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11, and the contact angle of the curable composition 13 with respect to the liquid-repellent layer 14 was measured, and the contact angle was found to be 81.5 degrees.

[0107] When the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11 was measured in a non-contact manner using a laser beam with a wavelength of 550 nm as the energy 23, the reflectance of the liquid-repellent layer 14 was found to be 8.72%.

[0108] When the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11 was measured using a laser beam with a wavelength of 655 nm as the energy 23, the thickness of the liquid-repellent layer 14 was found to be 5.32 nm.

[0109] In addition, the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11 was measured non-contact, and then the mold 11 was observed to confirm that there was no peeling of the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a.

[0110] Example 2 As in Example 1, a liquid-repellent layer 14 was formed on the side surface 11d of the mesa portion 11a of the mold 11. However, the liquid-repellent agent used was a polymer having a perfluoroalkyl group with 6 carbon atoms in its side chain dissolved in a volatile solvent at a solids concentration of 0.03 wt%.

[0111] An uncured curable composition 13 was dropped onto the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11, and the contact angle of the curable composition 13 with respect to the liquid-repellent layer 14 was measured, and the contact angle was found to be 80.9 degrees.

[0112] When the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11 was measured in a non-contact manner using a laser beam with a wavelength of 550 nm as the energy 23, the reflectance of the liquid-repellent layer 14 was found to be 8.77%.

[0113] When the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11 was measured using a laser beam with a wavelength of 655 nm as the energy 23, the thickness of the liquid-repellent layer 14 was found to be 3.73 nm.

[0114] In addition, the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11 was measured non-contact, and then the mold 11 was observed to confirm that there was no peeling of the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a.

[0115] Example 3 As in Example 1, a liquid-repellent layer 14 was formed on the side surface 11d of the mesa portion 11a of the mold 11. However, the liquid-repellent agent used was a polymer having a perfluoroalkyl group with 6 carbon atoms in its side chain dissolved in a volatile solvent at a solids concentration of 0.015 wt%.

[0116] An uncured curable composition 13 was dropped onto the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11, and the contact angle of the curable composition 13 with respect to the liquid-repellent layer 14 was measured, and the contact angle was found to be 78.2 degrees.

[0117] When the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11 was measured in a non-contact manner using a laser beam with a wavelength of 550 nm as the energy 23, the reflectance of the liquid-repellent layer 14 was found to be 8.78%.

[0118] When the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11 was measured using a laser beam with a wavelength of 655 nm as the energy 23, the thickness of the liquid-repellent layer 14 was found to be 3.24 nm.

[0119] In addition, the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11 was measured non-contact, and then the mold 11 was observed to confirm that there was no peeling of the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a.

[0120] Example 4 As in Example 1, a liquid-repellent layer 14 was formed on the side surface 11d of the mesa portion 11a of the mold 11. However, the liquid-repellent agent used was a polymer having a perfluoroalkyl group with 6 carbon atoms in its side chain dissolved in a volatile solvent at a solids concentration of 0.0075 wt%.

[0121] An uncured curable composition 13 was dropped onto the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11, and the contact angle of the curable composition 13 with respect to the liquid-repellent layer 14 was measured, and the contact angle was found to be 76.9 degrees.

[0122] When the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11 was measured in a non-contact manner using a laser beam with a wavelength of 550 nm as the energy 23, the reflectance of the liquid-repellent layer 14 was found to be 8.79%.

[0123] When the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11 was measured using a laser beam with a wavelength of 655 nm as the energy 23, the thickness of the liquid-repellent layer 14 was found to be 3.00 nm.

[0124] In addition, the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11 was measured non-contact, and then the mold 11 was observed to confirm that there was no peeling of the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a.

[0125] Example 5 In Examples 1 to 4, the relationship between the reflectance of the liquid-repellent layer 14 and the contact angle of the curable composition 13 with the liquid-repellent layer 14 was determined as state information showing the relationship between the measurement results obtained by non-contact measurement of the liquid-repellent layer 14 and the state of the liquid-repellent layer 14, and the graph shown in Fig. 9 was obtained. Fig. 9 is a graph showing the relationship between the reflectance of the liquid-repellent layer 14 and the contact angle of the curable composition 13 with the liquid-repellent layer 14. In Fig. 9, the vertical axis represents the reflectance of the liquid-repellent layer 14, and the horizontal axis represents the contact angle of the curable composition 13 with the liquid-repellent layer 14.

[0126] Example 6 In Examples 1 to 4, the relationship between the thickness of the liquid-repellent layer 14 and the contact angle of the curable composition 13 with the liquid-repellent layer 14 was determined as state information showing the relationship between the measurement results obtained by non-contact measurement of the liquid-repellent layer 14 and the state of the liquid-repellent layer 14, and the graph shown in Fig. 10 was obtained. Fig. 10 is a graph showing the relationship between the thickness of the liquid-repellent layer 14 and the contact angle of the curable composition 13 with the liquid-repellent layer 14. In Fig. 10, the vertical axis represents the thickness of the liquid-repellent layer 14, and the horizontal axis represents the contact angle of the curable composition 13 with the liquid-repellent layer 14.

[0127] Example 7 As in Example 1, a liquid-repellent layer 14 was formed on the side surface 11d of the mesa portion 11a of the mold 11. However, the liquid-repellent agent used was the same as that used in Example 1, diluted slightly with a volatile solvent.

[0128] When the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11 was measured in a non-contact manner using a laser beam with a wavelength of 550 nm as the energy 23, the reflectance of the liquid-repellent layer 14 was found to be 8.740%.

[0129] From the state information obtained in Example 5 (FIG. 9), when the curable composition 13 before curing was dropped onto the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11, the contact angle was 81.4 degrees.

[0130] In addition, the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11 was measured non-contact, and then the mold 11 was observed to confirm that there was no peeling of the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a.

[0131] Example 8 As in Example 2, a liquid-repellent layer 14 was formed on the side surface 11d of the mesa portion 11a of the mold 11. However, the liquid-repellent agent used was the same as that used in Example 2, diluted slightly with a volatile solvent.

[0132] When the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11 was measured in a non-contact manner using a laser beam with a wavelength of 550 nm as the energy 23, the reflectance of the liquid-repellent layer 14 was found to be 8.775%.

[0133] From the state information obtained in Example 5 (Figure 9), when the curable composition 13 before curing was dropped onto the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11, the contact angle was 80.5 degrees.

[0134] In addition, the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11 was measured non-contact, and then the mold 11 was observed to confirm that there was no peeling of the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a.

[0135] Example 9 As in Example 1, a liquid-repellent layer 14 was formed on the side surface 11d of the mesa portion 11a of the mold 11. However, the liquid-repellent agent used was the same as that used in Example 1, diluted slightly with a volatile solvent.

[0136] When the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11 was measured using a laser beam with a wavelength of 655 nm as the energy 23, the thickness of the liquid-repellent layer 14 was found to be 4.9 nm.

[0137] From the state information obtained in Example 6 (Figure 10), when the curable composition 13 before curing was dropped onto the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11, the contact angle was 81.4 degrees.

[0138] In addition, the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11 was measured non-contact, and then the mold 11 was observed to confirm that there was no peeling of the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a.

[0139] Example 10 As in Example 2, a liquid-repellent layer 14 was formed on the side surface 11d of the mesa portion 11a of the mold 11. However, the liquid-repellent agent used was the same as that used in Example 2, diluted slightly with a volatile solvent.

[0140] When the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11 was measured using a laser beam with a wavelength of 655 nm as the energy 23, the thickness of the liquid-repellent layer 14 was found to be 3.6 nm.

[0141] From the state information obtained in Example 6 (Figure 10), when the curable composition 13 before curing was dropped onto the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11, the contact angle was 80.5 degrees.

[0142] In addition, the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11 was measured non-contact, and then the mold 11 was observed to confirm that there was no peeling of the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a.

[0143] 9 and 10 has been described as being used to inspect the state of the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a of the mold 11, specifically, to inspect the contact angle of the curable composition 13 with the liquid-repellent layer 14. However, the state information shown in Figures 9 and 10 can also be used to inspect the state of the imprint surface 11g of the mesa portion 11a of the mold 11, specifically, to inspect whether or not any residue of the liquid-repellent layer 14 remains on the imprint surface 11g.

[0144] [Imprinting device] As described above, the system 1 in this embodiment, particularly the inspection unit ISU (inspection apparatus), can be incorporated into an imprint apparatus, and such an imprint apparatus also constitutes one aspect of the present invention. Furthermore, the system 1 and the inspection unit ISU can be incorporated into a mold cleaning apparatus, for example, without being limited to an imprint apparatus.

[0145] FIG. 11 is a schematic diagram showing the configuration of an imprint apparatus IMP incorporating an inspection unit ISU. The imprint apparatus IMP is employed in a lithography process, which is a manufacturing process for products such as semiconductor elements, liquid crystal display elements, and magnetic storage media. The imprint apparatus IMP is a lithography apparatus that forms a pattern on a substrate, specifically, that forms a pattern in a curable composition (imprint material) on the substrate using a mold. The imprint apparatus IMP brings the mold into contact with uncured curable composition placed (supplied) on the substrate, and applies energy for curing to the curable composition, thereby forming a pattern in a cured product to which the mold pattern has been transferred. In this embodiment, the imprint apparatus IMP employs a photocuring method as a method for curing the curable composition.

[0146] The curable composition is a material that cures when curing energy is applied. Examples of the curing energy include electromagnetic waves and heat. Examples of electromagnetic waves include light having a wavelength selected from the range of 10 nm to 1 mm, specifically infrared light, visible light, and ultraviolet light.

[0147] The curable composition is a composition that cures upon irradiation with light or heat. The photocurable composition that cures upon 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, and the like.

[0148] The curable composition may be applied to the substrate in the form of a film using a spin coater or a slit coater. Alternatively, the curable composition may be applied to the substrate in the form of droplets, or in the form of islands or a film formed by connecting multiple droplets using a liquid jet head. The viscosity of the imprint material (at 25°C) is, for example, 1 mPa·s or more and 100 mPa·s or less.

[0149] The substrate may be made of glass, ceramics, metal, semiconductor, resin, etc., and may have a member made of a material different from the substrate formed on its surface as needed. Specifically, the substrate may be made of a silicon wafer, a compound semiconductor wafer, quartz glass, etc.

[0150] In this specification and the accompanying drawings, directions are indicated in an XYZ coordinate system in which the direction parallel to the surface of the substrate is the XY plane. The directions parallel to the X-axis, Y-axis, and Z-axis in the XYZ coordinate system are the X-direction, Y-direction, and Z-direction, respectively, and rotation around the X-axis, Y-axis, and Z-axis are θX, θY, and θZ, respectively.

[0151] As shown in FIG. 11, the imprint apparatus IMP has a mold holding unit MHU, an irradiation unit IRU, a substrate holding unit SHU, an imaging unit ICU, a dispenser DPS, an inspection unit ISU, and a control unit 111.

[0152] The mold holding unit MHU includes a mold chuck that holds the mold 11 and a mold driver that drives the mold chuck. The mold holding unit MHU holds the mold 11 by attracting the outer peripheral region of the surface of the mold 11 that is irradiated with the irradiation light to the chuck by vacuum suction force or electrostatic force. The mold driver is configured to drive the mold 11 (or the mold chuck that holds it) about multiple axes (for example, three axes: Z-axis, θX-axis, and θY-axis, and preferably six axes: X-axis, Y-axis, Z-axis, θX-axis, θY-axis, and θZ-axis).

[0153] As described above, the mold 11 has the liquid-repellent layer 14 formed on the side surface 11d of the mesa portion 11a. Furthermore, when the inspection unit ISU measures the liquid-repellent layer 14 on the side surface 11d of the mesa portion 11a in a non-contact manner and determines the state of the liquid-repellent layer 14 based on the state information, it is guaranteed that the contact angle of the curable composition 13 with respect to the liquid-repellent layer 14 is 70 degrees or more. Furthermore, when the inspection unit ISU measures the liquid-repellent layer 14 on the imprint surface 11g of the mesa portion 11a in a non-contact manner and determines the state of the liquid-repellent layer 14 based on the state information, it is guaranteed that the contact angle of the curable composition 13 with respect to the liquid-repellent layer 14 is 30 degrees or less.

[0154] The irradiation unit IRU irradiates the curable composition 13 arranged on the substrate 12 with irradiation light such as ultraviolet light, thereby curing the curable composition 13. The irradiation unit IRU includes, for example, a light source that emits the irradiation light, an optical element that adjusts the irradiation light from the light source to a state appropriate for the imprint process, and a light shielding plate (masking blade) that limits the irradiation area (irradiation range) of the irradiation light.

[0155] The substrate holding unit SHU includes a substrate chuck that holds the substrate 12, and a substrate driving unit that drives the substrate chuck. The substrate driving unit is configured to drive the substrate 12 (or the substrate chuck that holds the substrate 12) about multiple axes (e.g., three axes: X-axis, Y-axis, and θZ-axis, and preferably six axes: X-axis, Y-axis, Z-axis, θX-axis, θY-axis, and θZ-axis).

[0156] The mold driving unit and the substrate driving unit are configured as relative driving mechanisms that drive at least one of the mold 11 and the substrate 12 so as to adjust the relative positions of the mold 11 and the substrate 12. The adjustment of the relative positions by the relative driving mechanisms (mold driving unit and substrate driving unit) includes driving for contact between the curable composition 13 on the substrate and the mold 11 (imprint surface 11a) and for separating the cured curable composition 13 on the substrate from the mold 11.

[0157] The dispenser DPS places (supplies) the curable composition 13 on (the imprint area of) the substrate. For example, the curable composition 13 can be placed at a target position on the substrate by discharging the curable composition 13 from the dispenser DPS while scanning the substrate 12.

[0158] The imaging unit ICU is configured to be one or more, and measures the relative positions of the alignment marks of the substrate 12 and the mold 11 by capturing an image formed by these alignment marks.

[0159] The inspection unit ISU and the control unit 111 have the configurations and functions described above, and therefore detailed description thereof will be omitted here. However, the control unit 111 also has the function of comprehensively controlling each unit of the imprint apparatus IMP in accordance with a program stored in a storage unit, etc. The control unit 111 controls the operation of each unit of the imprint apparatus IMP, thereby performing an imprint process in which the curable composition 13 on the substrate is shaped by the mold 11 to form a pattern of the curable composition 13.

[0160] 12(a) to 12(d), the imprint process performed by the imprint apparatus IMP will be described. The imprint process includes a placement step, a contact step, an irradiation step, and a release step. Note that the imprint process may include an alignment step of aligning the mold 11 and the substrate 12 between the contact step and the irradiation step.

[0161] The cured product of the curable composition 13 obtained by the imprinting process in this embodiment is preferably a film having a pattern with a size of 1 nm to 10 mm. Generally, the technology for forming a film having a nano-sized (1 nm to 1000 nm) pattern (relief structure) using light is also called a photo-nanoimprinting method.

[0162] In the disposing step, as shown schematically in FIG. 12(a), droplets of the curable composition 13 are discretely disposed on the substrate 12. An inkjet method is particularly preferred as a disposing method for disposing the droplets of the curable composition 13 on the substrate. The droplets of the curable composition 13 are preferably densely disposed on the region of the substrate 12 facing the region where the recesses constituting the pattern 11b of the mold 11 are densely located, and sparsely disposed on the region of the substrate 12 facing the region where the recesses constituting the pattern 11b are sparsely located. This allows the film (residual film) of the curable composition (described later) formed on the substrate 12 to be controlled to a uniform thickness regardless of the density of the pattern 11b of the mold 11. The droplets of the curable composition 13 disposed on the substrate 12 gradually spread over time in the direction indicated by the arrow 203.

[0163] In the disposing step, the curable composition 13 may be disposed on the substrate 12 by spin coating. In this case, the curable composition 13 is disposed on the substrate 12 continuously.

[0164] In this embodiment, the viscosity at 25° C. of the mixture of the components of the curable composition 13 excluding the solvent is preferably 1 mPa·s or more and less than 40 mPa·s, and more preferably 1 mPa·s or more and less than 20 mPa·s. If the viscosity of the curable composition 13 exceeds 40 mPa·s, it becomes impossible to use an inkjet method as a disposition method for disposing droplets of the curable composition 13 on a substrate. If the viscosity of the curable composition 13 is lower than 1 mPa·s, the curable composition 13 may flow and cause uneven application in the disposition step, or the curable composition 13 may flow out of the imprint surface 11g of the mesa portion 11a of the mold 11 in the contact step.

[0165] In this embodiment, the surface tension of the curable composition 13, excluding the solvent, is preferably 5 mN / m or more and 70 mN / m or less at 23°C. Furthermore, the surface tension of the curable composition 13, excluding the solvent, is 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 at 23°C. The higher the surface tension, for example, 5 mN / m or more, the stronger the capillary force, and therefore the faster the filling (spreading and filling) when the curable composition 13 is brought into contact with the mold 11. Furthermore, by setting the surface tension to 70 mN / m or less, the cured film obtained by curing the curable composition 13 has a smooth surface.

[0166] In this embodiment, the contact angle of the curable composition 13, for the composition of components excluding the solvent, is preferably 0 to 90 degrees, particularly preferably 0 to 30 degrees, with respect to both the surface of the substrate 12 and the imprint surface 11g of the mold 11. If the contact angle is greater than 90 degrees, capillary force acts in the negative direction (a direction that shrinks the contact interface between the mold 11 and the curable composition 13) inside the pattern 11b of the mold 11 and in the gap between the substrate 12 and the mold 11, and filling may not occur. The smaller the contact angle, the stronger the capillary force, and the faster the filling speed.

[0167] The substrate 12, onto which the curable composition 13 is to be applied, is a workpiece substrate, typically a silicon wafer. The substrate 12 may have a workpiece layer on its surface. The substrate 12 may also have another layer formed below the workpiece layer. Furthermore, by using a quartz substrate (a blank substrate for a replica mold) as the substrate 12, a replica (replica mold) of the mold 11 used in imprinting technology can be manufactured. However, the substrate 12 is not limited to a silicon wafer or a quartz substrate. The substrate 12 can be selected from any known substrate for semiconductor devices, such as aluminum, titanium-tungsten alloy, aluminum-silicon alloy, aluminum-copper-silicon alloy, silicon oxide, or silicon nitride. The surface of the substrate 12 or the workpiece layer may be subjected to surface treatment, such as silane coupling treatment, silazane treatment, or organic thin film formation, to improve adhesion to the curable composition 13.

[0168] In the contacting step, as shown schematically in FIG. 12(b), the curable composition 13 arranged on the substrate in the disposing step is brought into contact with the mold 11. The contacting step includes a step of changing the state in which the curable composition 13 and the mold 11 are not in contact with each other to a state in which they are in contact with each other, and a step of maintaining the state in which they are in contact with each other. As a result, the curable composition 13 fills the recesses in the pattern 11b of the mold 11, forming a liquid film that fills the pattern 11b of the mold 11. Note that arrow 203 indicates the direction in which the droplets of the curable composition 13 spread.

[0169] When the curing step includes a step of irradiating light (light irradiation step), a mold made of a light-transmitting material is used as the mold 11 in consideration of this. Specific examples of materials constituting the mold 11 include glass, quartz, light-transmitting resins such as PMMA and polycarbonate resin, transparent metal vapor deposition films, flexible films such as polydimethylsiloxane, light-cured films, and metal films. However, when a light-transmitting resin is used as the material constituting the mold 11, a resin that is insoluble in the components contained in the curable composition 13 is selected. Quartz is suitable as a material constituting the mold 11 because it has a small thermal expansion coefficient and small pattern distortion.

[0170] The pattern 11b formed on the imprint surface 11g of the mold 11 has a height of, for example, 4 nm or more and 200 nm or less. The lower the height of the pattern 11b of the mold 11, the smaller the force required to separate the mold 11 from the cured film of the curable composition during the demolding process, i.e., the demolding force. This reduces the number of demolding defects remaining on the mold 11 due to the curable composition pattern being torn off. Furthermore, the impact of separating the mold 11 can elastically deform the curable composition pattern, causing adjacent pattern elements to come into contact with each other, resulting in adhesion or breakage. However, to avoid these problems, it is advantageous for the height of the pattern elements to be approximately twice or less the width of the pattern elements (aspect ratio of 2 or less). On the other hand, if the height of the pattern elements is too low, the processing accuracy of the substrate 12 decreases.

[0171] When the objective is to obtain a flat film of the curable composition 13, the fine pattern 11b is not formed on the imprint surface 11g of the mold 11, and the imprint surface 11g is configured with a flat surface for flattening the curable composition 13. In other words, the imprint apparatus IMP can also be realized as a flattening apparatus that performs a flattening process.

[0172] The mold 11 may be subjected to a surface treatment before the contact step in order to improve the releasability of the mold 11 from the curable composition 13. Examples of surface treatments include applying a release agent to the imprint surface 11g of the mold 11 to form a release agent layer. Examples of release agents that can be applied to the imprint surface 11g of the mold 11 include silicone-based release agents, fluorine-based release agents, hydrocarbon-based release agents, polyethylene-based release agents, polypropylene-based release agents, paraffin-based release agents, montan-based release agents, and carnauba-based release agents. For example, commercially available coating-type release agents such as Optool (registered trademark) DSX manufactured by Daikin Industries, Ltd. can also be suitably used. One type of release agent may be used alone, or two or more types may be used in combination. Of the above-mentioned release agents, fluorine-based and hydrocarbon-based release agents are particularly preferred.

[0173] In the contacting step, when the mold 11 is brought into contact with the curable composition 13, the pressure applied to the curable composition 13 is not particularly limited and is, for example, 0 MPa or more and 100 MPa or less. The pressure applied to the curable composition 13 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.

[0174] In the contacting step, the time for which the mold 11 and the curable composition 13 are in contact is not particularly limited. The time for which the mold 11 and the curable composition 13 are in contact is, for example, preferably from 0.1 to 600 seconds, more preferably from 0.1 to 3 seconds, and particularly preferably from 0.1 to 1 second. If the time for which the mold 11 and the curable composition 13 are in contact is shorter than 0.1 seconds, the curable composition 13 tends to be insufficiently filled or spread, resulting in frequent defects known as unfilled defects.

[0175] The contacting step can be carried out under any of the conditions of air, reduced pressure, and inert gas atmosphere, but a reduced pressure or inert gas atmosphere is preferred because it can prevent the influence of oxygen and moisture on the curing reaction. Specific examples of the inert gas used when the contacting step is carried out under an inert gas atmosphere include nitrogen, carbon dioxide, helium, argon, various chlorofluorocarbon gases, and mixtures of these. When the contacting step is carried out under a specific gas atmosphere, including air, the preferred pressure is 0.0001 atmospheres or more and 10 atmospheres or less.

[0176] 12(c), the curing step involves irradiating the curable composition 13 with irradiation light 205 as curing energy, thereby curing the curable composition 13 and forming a cured film. In the curing step, for example, the curable composition 13 is irradiated with irradiation light 205 through the mold 11. More specifically, the curable composition 13 filled in the pattern 11b of the mold 11 is irradiated with irradiation light 205 through the mold 11. As a result, the curable composition 13 filled in the pattern 11b of the mold 11 is cured to form a cured film 206 having the pattern.

[0177] The irradiation light 205 is selected according to the wavelength to which the curable composition 13 is sensitive. Specifically, the irradiation light 205 is appropriately selected from ultraviolet light, X-rays, electron beams, or the like having a wavelength of 150 nm or more and 400 nm or less. It is particularly preferable that the irradiation light 205 be ultraviolet light. This is because many commercially available curing aids (photopolymerization initiators) are compounds that 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, xenon lamps, KrF excimer lasers, ArF excimer lasers, and F2 lasers. However, ultra-high-pressure mercury lamps are particularly preferable as light sources that emit ultraviolet light. The number of light sources may be one or more. Furthermore, the entire area of ​​the curable composition 13 filled in the pattern 11b of the mold 11 may be irradiated with light, or only a partial area (a limited area) may be irradiated with light. The light irradiation may be performed intermittently multiple times over the entire area of ​​the substrate, or may be performed continuously over the entire area of ​​the substrate. Furthermore, light may be irradiated over a first area of ​​the substrate in a first irradiation process, and light may be irradiated over a second area of ​​the substrate different from the first area in a second irradiation process.

[0178] In the demolding step, as shown schematically in FIG. 12(d), the mold 11 is separated from the cured film 206. By separating the patterned cured film 206 from the mold 11, a free-standing cured film 206 having a pattern that is an inverse of the pattern 11b of the mold 11 is obtained. Here, the cured film remains in the recesses of the patterned cured film 206. This film is called a residual film 207.

[0179] The method for separating the mold 11 from the cured film 206 having the pattern is not particularly limited as long as a portion of the cured film 206 having the pattern is not physically damaged during the separation, and various conditions are not particularly limited. For example, the substrate 12 may be fixed, and the mold 11 may be driven so as to move away from the substrate 12. Alternatively, the mold 11 may be fixed, and the substrate 12 may be driven so as to move away from the mold 11. The mold 11 may be separated from the cured film 206 having the pattern by driving both the mold 11 and the substrate 12 in opposite directions.

[0180] A series of steps (manufacturing process) including the above-mentioned placement step to demolding step in this order can produce a cured film having the desired concave-convex pattern shape (a pattern shape that follows the concave-convex shape of the mold 11) in the desired position.

[0181] [Production method] The pattern of the cured product formed using the imprinting apparatus IMP can be used permanently on at least a portion of various articles, or temporarily when manufacturing various articles. Examples of articles include electrical circuit elements, optical elements, MEMS, recording elements, sensors, and molds. Examples of electrical circuit elements include volatile or non-volatile semiconductor memories such as DRAM, SRAM, flash memory, and MRAM, and semiconductor elements such as LSIs, CCDs, image sensors, and FPGAs. Examples of molds include imprinting molds. Examples of optical elements include quantum dot structures, subwavelength antireflection structures, light extraction structures for LEDs and the like, photonic crystals, ultraviolet wire-grid polarizers, structural birefringence wave plates, diffraction gratings, and metalenses.

[0182] The pattern of the cured product may be used as it is as at least a part of a component of the above-mentioned article, or may be used temporarily as a resist mask, which is removed after etching or ion implantation is performed in a substrate processing step.

[0183] [Production method] A specific method for manufacturing the article will now be described. As shown in Figure 13(a), a substrate such as a silicon wafer is prepared, on the surface of which a workpiece such as an insulator is formed. Then, a curable composition is applied to the surface of the workpiece by an inkjet method or the like. Here, the state in which multiple droplets of the curable composition are applied to the substrate is shown.

[0184] As shown in Figure 13(b), the mold is placed so that the side on which the concave-convex pattern is formed faces the curable composition on the substrate. As shown in Figure 13(c), the substrate on which the curable composition has been applied is brought into contact with the mold, and pressure is applied. The curable composition fills the gap between the mold and the workpiece. In this state, when light is irradiated through the mold as curing energy, the curable composition cures.

[0185] 13(d), when the mold and substrate are separated after the curable composition is cured, a pattern of the curable composition is formed on the substrate. In this cured product pattern, the recesses of the transfer pattern of the mold correspond to the protrusions of the cured product, and the protrusions of the transfer pattern of the mold correspond to the recesses of the cured product, i.e., the transfer pattern of the mold is transferred to the curable composition.

[0186] As shown in Figure 13(e), when etching is performed using the cured material pattern as an etching-resistant mask, the portions of the surface of the workpiece where no cured material or only a thin layer remains are removed, forming grooves. As shown in Figure 13(f), when the cured material pattern is removed, an article with grooves formed in the surface of the workpiece is obtained. Here, the cured material pattern is removed, but it may also be used as an interlayer insulating film included in semiconductor devices, i.e., a component of an article, without being removed after processing.

[0187] In this embodiment, a manufacturing method for manufacturing various devices has been described, but it is also possible to manufacture a replica mold by using a blank substrate for a replica mold instead of a substrate for a device.

[0188] The disclosure of this specification includes the following inspection method, inspection apparatus, imprint apparatus, article manufacturing method, replica mold manufacturing method, and mold.

[0189] (Item 1) A method for inspecting a mold in which a liquid-repellent layer is formed on a side surface of a mesa portion protruding from a substrate, comprising: a first step of acquiring information indicating a relationship between a measurement result obtained by non-contact measurement of the liquid-repellent layer and a state of the liquid-repellent layer; a second step of measuring the liquid-repellent layer formed on the side surface in a non-contact manner; a third step of determining the state of the liquid-repellent layer formed on the side surface based on the information acquired in the first step and the measurement results obtained in the second step; An inspection method comprising:

[0190] (Item 2) The second step comprises: an irradiation step of irradiating the side surface on which the liquid-repellent layer is formed with energy from an irradiation unit; a detection step of detecting energy incident on a detection unit from the side surface in response to the irradiation step; 2. The inspection method according to item 1, comprising:

[0191] (Item 3) 3. The inspection method according to item 2, wherein in the irradiation step, energy is irradiated onto the side surface within a range equal to or less than the height of the side surface.

[0192] (Item 4) In the irradiation step, energy is irradiated from the irradiation unit to each of a plurality of locations on the side surface, In the detecting step, energy incident on the detecting unit from each of the plurality of points on the side surface is detected. 4. The inspection method according to item 2 or 3,

[0193] (Item 5) the mesa portion includes a plurality of side surfaces on which the liquid-repellent layer is formed, In the irradiation step, energy is irradiated from the irradiation unit onto each of the plurality of side surfaces, In the detecting step, energy incident on the detecting unit from each of the plurality of side surfaces is detected. 5. The inspection method according to any one of items 2 to 4,

[0194] (Item 6) 6. The inspection method according to item 2 or 5, wherein in the irradiating step, energy is irradiated from the irradiating unit to a location on the side surface designated by a user.

[0195] (Item 7) 6. The inspection method according to item 2 or 5, wherein in the irradiation step, the side surface is irradiated with energy from the irradiation unit so that the entire area of ​​the side surface is scanned with energy.

[0196] (Item 8) 8. The inspection method according to any one of items 1 to 7, wherein in the second step, the liquid-repellent layer is measured in a non-contact manner based on a difference between the characteristics of a liquid-repellent agent used to form the liquid-repellent layer and the characteristics of a material constituting the mesa portion.

[0197] (Item 9) 9. The inspection method according to any one of items 1 to 8, wherein in the second step, together with the measurement results obtained by non-contact measurement of the liquid-repellent layer, at least one of information regarding the position of the side surface, information regarding the coordinates of the side surface, and information regarding the mold from which the measurement results were obtained is obtained.

[0198] (Item 10) 3. The inspection method according to item 2, wherein the energy includes at least one of infrared rays, visible light, ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, radiation, electromagnetic waves, heat, microwaves, and ultrasound.

[0199] (Item 11) 11. The inspection method according to any one of items 1 to 10, wherein the measurement results include at least one of material properties, optical properties, electromagnetic wave properties, radiation properties, and thermal properties related to the liquid-repellent layer.

[0200] (Item 12) 11. The inspection method according to any one of items 1 to 10, wherein the measurement results include at least one of the transmittance of the liquid-repellent layer, the absorbance of the liquid-repellent layer, the reflectance of the liquid-repellent layer, the emissivity of the liquid-repellent layer, the vibration rate of the liquid-repellent layer, the thickness of the liquid-repellent layer, the interference between the side surface and the liquid-repellent layer, and the phase difference between the side surface and the liquid-repellent layer.

[0201] (Item 13) 13. The inspection method according to any one of items 1 to 12, wherein the state of the liquid-repellent layer includes at least one of the liquid repellency of the liquid-repellent layer with respect to a curable composition, the contact angle of the curable composition with respect to the liquid-repellent layer, the sliding angle of the curable composition with respect to the liquid-repellent layer, the receding contact angle of the curable composition with respect to the liquid-repellent layer, and the surface free energy of the liquid-repellent layer with respect to the curable composition.

[0202] (Item 14) 11. The inspection method according to any one of items 1 to 10, wherein the information includes at least one of a relationship between the reflectance of the liquid-repellent layer and the contact angle of the curable composition on the liquid-repellent layer, a relationship between the thickness of the liquid-repellent layer and the contact angle of the curable composition on the liquid-repellent layer, a relationship between the transmittance of the liquid-repellent layer and the contact angle of the curable composition on the liquid-repellent layer, and a relationship between the temperature of the liquid-repellent layer and the contact angle of the curable composition on the liquid-repellent layer.

[0203] (Item 15) 15. The inspection method described in any one of items 1 to 14, further comprising a fourth step of determining the difference between the state of the liquid-repellent layer determined in the third step and the target state of the liquid-repellent layer to be formed on the side surface.

[0204] (Item 16) Item 16. The inspection method according to item 15, further comprising a fifth step of determining, based on the difference determined in the fourth step, at least one of formation conditions for forming a liquid-repellent layer on the side surface of a mesa portion protruding from a base material of a new mold different from the mold, and repair conditions for repairing the liquid-repellent layer formed on the side surface.

[0205] (Item 17) Item 16. The inspection method according to item 15, further comprising a sixth step of determining whether the mold is usable or not based on the difference obtained in the fourth step.

[0206] (Item 18) 18. The inspection method according to any one of items 1 to 17, wherein the second step is performed after the liquid-repellent layer is formed on the side surface.

[0207] (Item 19) 19. The inspection method according to any one of items 1 to 18, wherein the liquid-repellent layer is formed from at least one of a liquid-repellent agent containing a polymer having a fluorocarbon chain and a volatile solvent that dissolves the polymer, and a liquid-repellent agent containing a monolayer-forming material that has a fluorocarbon chain and bonds to the side surface by vaporization.

[0208] (Item 20) 20. The inspection method according to any one of items 1 to 19, wherein the contact angle of the curable composition with respect to the liquid-repellent layer is larger than the contact angle of the curable composition with respect to the mold.

[0209] (Item 21) A method for inspecting a mold in which a liquid-repellent layer is formed on a side surface of a mesa portion protruding from a substrate, comprising: a first step of acquiring information indicating a relationship between a measurement result obtained by non-contact measurement of a contact surface of the mesa portion that is to be brought into contact with the curable composition and a state of the liquid-repellent layer; a second step of measuring the contact surface of the mesa portion in a non-contact manner; a third step of determining the state of the contact surface of the mesa portion based on the information acquired in the first step and the measurement results obtained in the second step; An inspection method comprising:

[0210] (Item 22) An inspection device for a mold in which a liquid-repellent layer is formed on a side surface of a mesa portion protruding from a substrate, a stage for holding the mold; a measurement unit that measures, in a non-contact manner, the liquid-repellent layer formed on the side surface of the mesa portion of the mold held by the stage; a processing unit that determines the state of the liquid-repellent layer formed on the side surface based on information indicating a relationship between a measurement result obtained by non-contact measurement of the liquid-repellent layer and a state of the liquid-repellent layer, and based on the measurement result obtained by the measurement unit; An inspection device comprising:

[0211] (Item 23) The measurement unit an irradiation unit and a detection unit, the side surface on which the liquid-repellent layer is formed is irradiated with energy from the irradiation unit, and the liquid-repellent layer formed on the side surface is measured in a non-contact manner by detecting the energy incident on the detection unit from the side surface in response to the irradiation by the irradiation unit. 23. The inspection device according to item 22,

[0212] (Item 24) a driving mechanism that drives the stage along a first direction parallel to a surface of the mesa portion; a rotation mechanism that rotates the stage about an axis that is along a second direction perpendicular to the first direction; 24. The inspection device according to item 23, further comprising:

[0213] (Item 25) Item 25. The inspection device described in item 24, characterized in that, while the stage is driven by the driving mechanism, the measurement unit irradiates energy from the irradiation unit to each of a plurality of locations on the side surface, and detects energy incident on the detection unit from each of the plurality of locations on the side surface in response to irradiation by the irradiation unit, thereby measuring the liquid-repellent layer formed on the side surface in a non-contact manner.

[0214] (Item 26) the mesa portion includes a plurality of side surfaces on which the liquid-repellent layer is formed, 26. The inspection device according to item 24 or 25, wherein the measurement unit irradiates energy from the irradiation unit onto each of the plurality of side surfaces while rotating the stage using the rotation mechanism, and detects energy incident on the detection unit from each of the plurality of side surfaces in response to the irradiation by the irradiation unit, thereby measuring the liquid-repellent layer formed on the side surfaces in a non-contact manner.

[0215] (Item 27) 26. The inspection device according to any one of items 24 to 25, further comprising an alignment mechanism for aligning the center of the mold with the rotation axis.

[0216] (Item 28) 28. The inspection device described in any one of items 22 to 27, further comprising an acquisition unit that acquires information indicating the relationship between the measurement results obtained by non-contact measurement of the liquid-repellent layer and the state of the liquid-repellent layer.

[0217] (Item 29) 1. An imprinting apparatus for forming a pattern in a curable composition on a substrate using a mold having a liquid-repellent layer formed on a side surface of a mesa portion protruding from a base material, 29. The mold inspection device according to any one of items 22 to 28, An imprinting apparatus comprising:

[0218] (Item 30) Forming a pattern on a substrate using the imprinting apparatus according to Item 29; processing the substrate on which the pattern has been formed in the process; manufacturing an article from the processed substrate; A method for manufacturing an article, comprising:

[0219] (Item 31) Item 29. A process of forming a pattern on a blank substrate for a replica mold using the imprinting apparatus according to Item 29; a step of manufacturing a replica mold by processing the blank substrate on which the pattern has been formed in the step; A method for manufacturing a replica mold, comprising:

[0220] (Item 32) 1. A mold for use in imprint lithography, comprising: A substrate; a mesa portion protruding from the substrate; a liquid-repellent layer formed on a side surface of the mesa portion; and the liquid-repellent layer formed on the side surface is measured in a non-contact manner, and the state of the liquid-repellent layer formed on the side surface is determined based on information indicating a relationship between the measurement result obtained by the non-contact measurement of the liquid-repellent layer and the state of the liquid-repellent layer, and the contact angle of the curable composition with the liquid-repellent layer formed on the side surface is 70 degrees or more. A mold characterized by:

[0221] (Item 33) Item 33. The mold according to item 32, wherein the liquid-repellent layer formed on the surface of the mesa portion is measured in a non-contact manner, and the state of the liquid-repellent layer formed on the surface is determined based on information showing the relationship between the measurement results obtained by the non-contact measurement of the liquid-repellent layer and the state of the liquid-repellent layer, and the contact angle of the curable composition with the liquid-repellent layer formed on the surface is 30 degrees or less.

[0222] The invention is not limited to the above-described embodiments, and various changes and modifications can be made without departing from the spirit and scope of the invention. Accordingly, the following claims are appended to apprise the public of the scope of the invention. [Explanation of symbols]

[0223] 11: Mold 11a: Mesa portion 11b: Pattern 11c: Base material 11d: Side surface 12: Substrate 13: Curable composition 14: Liquid-repellent layer

Claims

1. A method for inspecting a mold in which a liquid-repellent layer is formed on a side surface of a mesa portion protruding from a substrate, comprising: a first step of acquiring information indicating a relationship between a measurement result obtained by non-contact measurement of the liquid-repellent layer and a state of the liquid-repellent layer; a second step of measuring the liquid-repellent layer formed on the side surface in a non-contact manner; a third step of determining the state of the liquid-repellent layer formed on the side surface based on the information acquired in the first step and the measurement results obtained in the second step; An inspection method comprising:

2. The second step comprises: an irradiation step of irradiating the side surface on which the liquid-repellent layer is formed with energy from an irradiation unit; a detection step of detecting energy incident on a detection unit from the side surface in response to the irradiation step; 2. The inspection method according to claim 1, further comprising:

3. 3. The inspection method according to claim 2, wherein in the irradiation step, energy is irradiated onto the side surface within a range equal to or less than the height of the side surface.

4. In the irradiation step, energy is irradiated from the irradiation unit to each of a plurality of locations on the side surface, In the detecting step, energy incident on the detecting unit from each of the plurality of points on the side surface is detected.

3. The inspection method according to claim 2.

5. the mesa portion includes a plurality of side surfaces on which the liquid-repellent layer is formed, In the irradiation step, energy is irradiated from the irradiation unit onto each of the plurality of side surfaces, In the detecting step, energy incident on the detecting unit from each of the plurality of side surfaces is detected.

3. The inspection method according to claim 2.

6. 6. The inspection method according to claim 2, wherein in the irradiating step, the irradiating unit irradiates energy onto a location on the side surface designated by a user.

7. 6. The inspection method according to claim 2, wherein in the irradiating step, the side surface is irradiated with energy from the irradiating unit so that the entire area of ​​the side surface is scanned with the energy.

8. 2. The inspection method according to claim 1, wherein the second step measures the liquid-repellent layer in a non-contact manner based on a difference between characteristics of a liquid-repellent agent used to form the liquid-repellent layer and characteristics of a material constituting the mesa portion.

9. 2. The inspection method according to claim 1, wherein in the second step, together with the measurement results obtained by non-contact measurement of the liquid-repellent layer, at least one of information regarding the position of the side surface, information regarding the coordinates of the side surface, and information regarding the mold on which the measurement results were obtained is obtained is obtained.

10. 3. The inspection method according to claim 2, wherein the energy includes at least one of infrared light, visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams, radioactive rays, electromagnetic waves, heat, microwaves, and ultrasound.

11. 2. The inspection method according to claim 1, wherein the measurement results include at least one of material properties, optical properties, electromagnetic wave properties, radiation properties, and thermal properties related to the liquid-repellent layer.

12. 2. The inspection method according to claim 1, wherein the measurement results include at least one of a transmittance of the liquid-repellent layer, an absorptance of the liquid-repellent layer, a reflectance of the liquid-repellent layer, an emissivity of the liquid-repellent layer, a vibration rate of the liquid-repellent layer, a thickness of the liquid-repellent layer, an interference between the side surface and the liquid-repellent layer, and a phase difference between the side surface and the liquid-repellent layer.

13. 2. The inspection method according to claim 1, wherein the state of the liquid-repellent layer includes at least one of the liquid repellency of the liquid-repellent layer with respect to the curable composition, the contact angle of the curable composition with respect to the liquid-repellent layer, the sliding angle of the curable composition with respect to the liquid-repellent layer, the receding contact angle of the curable composition with respect to the liquid-repellent layer, and the surface free energy of the liquid-repellent layer with respect to the curable composition.

14. 2. The inspection method according to claim 1, wherein the information includes at least one of a relationship between the reflectance of the liquid-repellent layer and the contact angle of the curable composition with respect to the liquid-repellent layer, a relationship between the thickness of the liquid-repellent layer and the contact angle of the curable composition with respect to the liquid-repellent layer, a relationship between the transmittance of the liquid-repellent layer and the contact angle of the curable composition with respect to the liquid-repellent layer, and a relationship between the temperature of the liquid-repellent layer and the contact angle of the curable composition with respect to the liquid-repellent layer.

15. 2. The inspection method according to claim 1, further comprising a fourth step of determining a difference between the state of the liquid-repellent layer determined in the third step and a target state of the liquid-repellent layer to be formed on the side surface.

16. 16. The inspection method according to claim 15, further comprising a fifth step of determining, based on the difference determined in the fourth step, at least one of formation conditions for forming a liquid-repellent layer on the side surface of a mesa portion protruding from a base material of a new mold different from the mold, and repair conditions for repairing the liquid-repellent layer formed on the side surface.

17. 16. The inspection method according to claim 15, further comprising a sixth step of determining whether the mold is usable or not based on the difference obtained in the fourth step.

18. 2. The inspection method according to claim 1, wherein the second step is performed after the liquid-repellent layer is formed on the side surface.

19. 2. The inspection method according to claim 1, wherein the liquid-repellent layer is formed from at least one of a liquid-repellent agent containing a polymer having a fluorocarbon chain and a volatile solvent that dissolves the polymer, and a liquid-repellent agent containing a monolayer-forming material that has a fluorocarbon chain and bonds to the side surface by evaporation.

20. 2. The inspection method according to claim 1, wherein a contact angle of the curable composition with respect to the liquid-repellent layer is larger than a contact angle of the curable composition with respect to the mold.

21. A method for inspecting a mold in which a liquid-repellent layer is formed on a side surface of a mesa portion protruding from a substrate, comprising: a first step of acquiring information indicating a relationship between a measurement result obtained by non-contact measurement of a contact surface of the mesa portion that is to be brought into contact with the curable composition and a state of the liquid-repellent layer; a second step of measuring the contact surface of the mesa portion in a non-contact manner; a third step of determining a state of the contact surface of the mesa portion based on the information acquired in the first step and the measurement results obtained in the second step; An inspection method comprising:

22. An inspection device for a mold in which a liquid-repellent layer is formed on a side surface of a mesa portion protruding from a substrate, a stage for holding the mold; a measurement unit that measures, in a non-contact manner, the liquid-repellent layer formed on the side surface of the mesa portion of the mold held by the stage; a processing unit that determines the state of the liquid-repellent layer formed on the side surface based on information indicating a relationship between a measurement result obtained by non-contact measurement of the liquid-repellent layer and a state of the liquid-repellent layer, and based on the measurement result obtained by the measurement unit; An inspection device comprising:

23. The measurement unit an irradiation unit and a detection unit, the side surface on which the liquid-repellent layer is formed is irradiated with energy from the irradiation unit, and the liquid-repellent layer formed on the side surface is measured in a non-contact manner by detecting the energy incident on the detection unit from the side surface in response to the irradiation by the irradiation unit.

23. The inspection device according to claim 22.

24. a driving mechanism that drives the stage along a first direction parallel to a surface of the mesa portion; a rotation mechanism that rotates the stage about an axis that is along a second direction perpendicular to the first direction; 24. The inspection device of claim 23, further comprising:

25. 25. The inspection device according to claim 24, wherein, while the stage is being driven by the driving mechanism, the measurement unit irradiates energy from the irradiation unit onto each of a plurality of locations on the side surface, and detects energy incident on the detection unit from each of the plurality of locations on the side surface in response to irradiation by the irradiation unit, thereby measuring the liquid-repellent layer formed on the side surface in a non-contact manner.

26. the mesa portion includes a plurality of side surfaces on which the liquid-repellent layer is formed, 26. The inspection device according to claim 24, wherein the measurement unit measures the liquid-repellent layer formed on the side surfaces in a non-contact manner by irradiating energy from the irradiation unit onto each of the plurality of side surfaces while rotating the stage using the rotation mechanism and detecting energy incident on the detection unit from each of the plurality of side surfaces in response to irradiation by the irradiation unit.

27. 25. The inspection device according to claim 24, further comprising an alignment mechanism for aligning the center of the mold with the rotation axis.

28. 23. The inspection device according to claim 22, further comprising an acquisition unit that acquires information indicating a relationship between a measurement result obtained by non-contact measurement of the liquid-repellent layer and a state of the liquid-repellent layer.

29. 1. An imprinting apparatus for forming a pattern in a curable composition on a substrate using a mold having a liquid-repellent layer formed on a side surface of a mesa portion protruding from a base material, 23. The inspection apparatus of claim 22 for inspecting the mold. An imprinting apparatus comprising:

30. forming a pattern on a substrate using the imprint apparatus according to claim 29; processing the substrate on which the pattern has been formed in the process; manufacturing an article from the processed substrate; A method for manufacturing an article, comprising:

31. forming a pattern on a blank substrate for a replica mold using the imprint apparatus according to claim 29; a step of manufacturing a replica mold by processing the blank substrate on which the pattern has been formed in the step; A method for manufacturing a replica mold, comprising:

32. 1. A mold for use in imprint lithography, comprising: A substrate; a mesa portion protruding from the substrate; a liquid-repellent layer formed on a side surface of the mesa portion; and the liquid-repellent layer formed on the side surface is measured in a non-contact manner, and the state of the liquid-repellent layer formed on the side surface is determined based on information indicating a relationship between the measurement result obtained by the non-contact measurement of the liquid-repellent layer and the state of the liquid-repellent layer, and the contact angle of the curable composition with the liquid-repellent layer formed on the side surface is 70 degrees or more. A mold characterized by:

33. 33. The mold according to claim 32, wherein when the liquid-repellent layer formed on the surface of the mesa portion is measured in a non-contact manner and the state of the liquid-repellent layer formed on the surface is determined based on information indicating a relationship between the measurement results obtained by the non-contact measurement of the liquid-repellent layer and the state of the liquid-repellent layer, a contact angle of the curable composition with the liquid-repellent layer formed on the surface is 30 degrees or less.

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