Mold, method for manufacturing a mold, method for forming a film, apparatus for forming a film, and method for manufacturing an article.

Abstract

We provide new technologies related to molds. [Solution] A mold for use in imprint lithography is provided, comprising a substrate that is transparent to ultraviolet light, and a film formed on a structure provided on the side of the substrate opposite to the first surface to which the ultraviolet light is incident, wherein the film includes a portion having an electrical resistance lower than the electrical resistance of the outermost surface of the film.

Description

[Technical Field]

[0001] This disclosure relates to molds, methods for manufacturing molds, film formation methods, film formation apparatus, and methods for manufacturing articles. [Background technology]

[0002] With the increasing demand for miniaturization of semiconductor devices and MEMS (Micro Electro Mechanical Systems), imprint printing technology is attracting attention in addition to conventional photolithography technology. Imprint printing technology is a microfabrication technique that forms a predetermined shape (pattern) on a substrate by pressing a curable composition, which is placed (supplied) onto the substrate with a mold having a predetermined shape (pattern), and then curing the curable composition. This technology is called imprint printing technology, and it can form fine structures on the order of several nanometers on a substrate with a simpler process compared to conventional photolithography technology, which involves processes such as exposure and etching. Furthermore, imprint printing technology is also attracting attention as a processing technology that forms structures with a flat shape on a substrate by using a mold with a flat surface, so-called planarization technology.

[0003] In imprint technology, ultraviolet light is often used to cure the curable composition on the substrate. The curable composition onto which the mold pattern is transferred needs to be cured before the mold is separated from the curable composition. Therefore, a method is used in which the mold is made of a material that is transparent to the light used to cure the curable composition, and the curable composition between the mold and the substrate is cured by irradiating it with light from the side of the mold opposite to the side that comes into contact with the curable composition. Examples of materials that are transparent to the light used to cure the curable composition include quartz, glass, and resin.

[0004] On the other hand, the fine structures formed using imprint technology are expected to be on the order of several nanometers. Therefore, even if the particles are on the order of micrometers or nanometers, their adhesion to the mold can prevent the formation of fine structures on the substrate. Furthermore, even if the structure to be formed on the substrate has a flat shape, the adhesion of particles to the mold can impair the flatness of the structure formed on the substrate.

[0005] Insulating materials such as quartz, glass, and resin, which are commonly used as mold materials, tend to attract and deposit particles floating in the ambient air when they become electrically charged. Furthermore, discharges caused by the charging of the mold can potentially damage structures formed on the substrate or the mold itself.

[0006] Therefore, a technique has been proposed to form (coat) a conductive film, such as a metal, on the surface of the mold (see Patent Document 1). Patent Document 1 discloses the formation of a metal film (chromium film), such as chromium, on the surface of the mold. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Special Publication No. 2016-523449 [Overview of the project] [Problems that the invention aims to solve]

[0008] However, molds used in imprint technology are required to have various properties, one of which is release properties that allow the mold to be separated from the curable composition without damaging the structure of the curable composition formed on the substrate. In addition, the mold is required to have abrasion resistance to allow repeated imprinting on the curable composition on the substrate, and light transmittance to allow the curable composition to cure. However, while chromium films disclosed in the prior art have the effect of preventing static charge buildup in the mold, there is room for improvement in terms of abrasion resistance and light transmittance.

[0009] This disclosure is made in view of the problems of the prior art and aims to provide an exemplary new technology relating to molds. [Means for solving the problem]

[0010] To achieve the above objective, a mold as one aspect of the present disclosure is a mold used in imprint lithography, comprising a substrate that is transparent to ultraviolet light, and a film formed on a structure provided on a second surface of the substrate opposite to the first surface to which the ultraviolet light is incident, wherein the film includes a portion having an electrical resistance lower than the electrical resistance of the outermost surface of the film.

[0011] Further purposes or other aspects of this disclosure will be revealed by embodiments described below with reference to the accompanying drawings. [Effects of the Invention]

[0012] According to this disclosure, for example, it is possible to provide new technologies related to molds. [Brief explanation of the drawing]

[0013] [Figure 1] This is a schematic diagram showing the configuration of the mold as one aspect of this disclosure. [Figure 2] This is a diagram illustrating the structure of the membrane. [Figure 3] This is a diagram for explaining the structure of the film. [Figure 4] This is a schematic diagram showing the structure of the sputtering apparatus. [Figure 5] This is a schematic diagram showing the structure of the ADL apparatus. [Figure 6] This is a schematic diagram showing the structure of the imprint apparatus as one aspect of the present disclosure. [Figure 7] This is a diagram for explaining the manufacturing method of an article. [Figure 8] This is a diagram for explaining the case where the imprint apparatus shown in FIG. 6 is used as a planarization apparatus.

Mode for Carrying Out 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 scope of the claims. Although a plurality of features are described in the embodiments, not all of these plurality of features are necessary, and the plurality of features may be arbitrarily combined. Further, in the accompanying drawings, the same or similar configurations are denoted by the same reference numerals, and redundant descriptions are omitted. [[ID=​​​​​​​As shown in Figure 1, the mold 10 includes a structure 11, a back plate 13, a film 20, and a grounding portion 14. The structure 11 is provided on the second surface 13B of the back plate 13, opposite to the first surface 13A, and has a predetermined shape for molding a curable composition on a substrate. The back plate 13 is a substrate that supports the structure 11. The film 20 is formed on the surface of the structure 11. The film 20 may also be formed on the surface of the second surface 13B of the back plate 13 where the structure 11 is not provided. The grounding portion 14 is provided, for example, on the outer periphery of the second surface 13B of the back plate 13 and is connected to earth to release the charge accumulated on the surface of the film 20.

[0017] If the mold 10 is a hard mold, the structure 11 is constructed by processing a material that is transparent in the ultraviolet region, such as quartz or glass, into a predetermined shape using an electron beam or the like. If the mold 10 is a soft mold, the structure 11 is constructed by processing a curable composition that is transparent in the ultraviolet region into a predetermined shape. The predetermined shape of the structure 11 may be an uneven shape, specifically an uneven pattern, or a flat shape, specifically a flat surface. Transparent in the ultraviolet region means that it is transparent to ultraviolet light, and has a transmittance of 40% or more, preferably 60% or more, and more preferably 90% or more, for light with a wavelength of 350 nm to 400 nm. For example, quartz has a transmittance of 90% or more for light with a wavelength of 350 nm to 400 nm. In this embodiment, in addition to the structure 11, the back plate 13 and the film 20 are also transparent to ultraviolet light.

[0018] As shown in Figure 2, the film 20 consists of multiple layers. The film 20 includes a surface layer 201 including the outermost surface 201A, and one or more intermediate layers 202 between the structure 11 and the surface layer 201. In this embodiment, the conductivity required for the film 20 is, from the viewpoint of antistatic properties, a surface resistivity of 1 × 10⁻⁶. 9 The ratio will be less than or equal to Ω / □ (ohms per square). Figure 2 is a diagram illustrating the structure of film 20.

[0019] In this embodiment, the outermost layer 201 is made of a dielectric material and has a higher hardness (film hardness) than the intermediate layer 202. The outermost layer 201 is made of an oxide or nitride, which is a material with high hardness that provides wear resistance. Specifically, the outermost layer 201 (outermost surface 201A) is made of one of silicon oxide, tantalum oxide, titanium oxide, aluminum oxide, titanium nitride, aluminum nitride, and chromium nitride, or a mixture thereof. The outermost layer 201 preferably has a hardness equivalent to or greater than that of quartz or glass, which have a proven track record as conventional mold materials, specifically 8 GPa or higher.

[0020] In this embodiment, the intermediate layer 202 has an electrical resistance lower than that of the outermost layer 201. In other words, the intermediate layer 202 includes a portion having an electrical resistance lower than that of the outermost layer 201 (outermost surface 201A). The intermediate layer 202 is made of a conductive material such as a metal, oxide, or nitride that provides an antistatic effect.

[0021] Thus, in this embodiment, by assigning the necessary properties of the mold 10 to each layer of the film 20, multiple performance characteristics required for a mold used in imprint lithography can be achieved.

[0022] The film 20 can be formed on the structure 11 using methods such as physical vapor deposition, chemical vapor deposition, spin coating, and electroplating. When the structure 11 is on the order of nanometers in size, it is preferable to use physical vapor deposition or chemical vapor deposition, which allow for easy control of the film 20 thickness on the order of nanometers.

[0023] The backplate 13 is made of a material that is transparent to light incident from the first surface 13A, i.e., ultraviolet light used to cure the curable composition, such as quartz, glass, or resin. The backplate 13 and the structure 11 may be integrally constructed, i.e., made from the same substrate, or the structure 11 may be bonded to the second surface 13B of the backplate 13 via an adhesive.

[0024] The grounding portion 14 is formed as a metal film by covering a part of the outer periphery of the second surface 13B of the backplate 13 with a conductive material such as metal. The grounding portion 14 electrically connects the surface of the film 20 to the ground portion provided in the film forming apparatus using the mold 10, and is responsible for releasing the charge accumulated on the surface of the film 20 to the ground. The grounding portion 14 is made of a metal such as chromium or nickel and is formed using electroplating, physical vapor deposition, chemical vapor deposition, etc. Furthermore, it is preferable that the film 20 is formed on the side surface of the structure 11 in order to facilitate the release of the charge accumulated on the surface of the film 20 to the grounding portion 14.

[0025] In the mold 10, one factor that reduces the transmittance to ultraviolet light is the reflection of ultraviolet light when it is incident on the first surface 13A of the backplate 13. Therefore, it is preferable to form an anti-reflective film 22 on the first surface 13A of the backplate 13 (the surface opposite to the second surface 13B on which the structure 11 is provided), as shown in Figure 1, to suppress the reflection of ultraviolet light and improve the transmittance to ultraviolet light.

[0026] Furthermore, in the mold 10, a film 21 may be formed on the structure 11 instead of the film 20, as shown in Figure 3. Figure 3 is a diagram illustrating the structure of the film 21. The film 21 consists of one layer 211 and is a single layer that achieves conductivity, light transmittance, and abrasion resistance.

[0027] As one example of implementation, layer 211 is composed of a single composition and has conductivity and wear resistance. An example of such layer 211 (film 21) is tantalum oxidnitride.

[0028] Furthermore, as another implementation example, layer 211 is configured such that its composition is distributed in the thickness (film thickness) direction, and it has conductivity and wear resistance. However, layer 211 includes a portion within the layer (film) that has an electrical resistance lower than the electrical resistance of the outermost surface 211A of film 21. Examples of such layer 211 include titanium on the side of the structure 11 (initial lamination stage), and titanium oxide or titanium nitride on the side of the outermost surface 211A.

[0029] The following describes a manufacturing method for a mold 10 having a film 20 or a mold 10 having a film 21. The manufacturing method for the mold 10 includes the steps of preparing a back plate 13 which is a substrate that is transparent to ultraviolet light, and forming a film 20 or 21 on a structure 11 provided on the second surface 13B of the back plate 13.

[0030] In the process of forming a film 20 or 21 on the structure 11, a sputtering apparatus 40 is used, for example, as shown in Figure 4. Figure 4 is a schematic diagram showing the configuration of the sputtering apparatus 40. In the sputtering apparatus 40, for example, argon gas (introduction gas) for plasma discharge is introduced into the vacuum chamber 41, which is controlled under a predetermined reduced pressure by a vacuum pump (not shown), via a gas supply line 46. Also, by applying power to the sputtering target 42 using a power supply 44, a plasma discharge is formed between the sputtering target 42 (cathode) and the earth electrode 43 (anode). Ions in the plasma cause target atoms or molecules to be emitted from the sputtering target 42 toward the mold 10 which is provided opposite the sputtering target 42. A magnet 45 is placed on the back surface of the sputtering target 42. The magnetic field formed by the magnet 45 concentrates the plasma near the target, so that target atoms or molecules can be emitted from the sputtering target 42 more efficiently.

[0031] In the sputtering apparatus 40, by appropriately selecting the materials of the sputtering target 42 and the introduced gas, it is possible to make the material of the film 20 or 21 formed on the structure 11 a metal, oxide, nitride, or a mixture thereof. For example, by using titanium for the sputtering target 42 and argon and oxygen for the introduced gas, the titanium of the target reacts with the oxygen gas to form a titanium oxide (film) on the structure 11.

[0032] Furthermore, in the sputtering apparatus 40, the mold 10 is held by a rotatable holder 47. As shown in Figure 4, it is preferable to provide two sets of sputtering targets 42 and power supplies 44 for one holder 47. This makes it possible to form a film 20 or 21 by releasing target atoms or molecules from two directions onto the mold 10 (structure 11) which is rotating on the holder 47. Therefore, even if the structure 11 has an uneven pattern, a film 20 or 21 can be formed on the entire surface of the structure 11.

[0033] Furthermore, in terms of forming a film 20 or 21 over the entire surface of the uneven pattern of the structure 11, an ALD apparatus 50 using atomic layer deposition (ALD) may be used, as shown in Figure 5. Figure 5 is a schematic diagram showing the configuration of the ALD apparatus 50.

[0034] The ALD apparatus 50 has a vacuum chamber 51 that defines the interior, which is controlled under a predetermined reduced pressure by a vacuum pump (not shown). Inside the vacuum chamber 51, the mold 10 is held by a holder 55. A raw material gas is supplied to the inside of the vacuum chamber 51 via a gas supply line 52, and molecules of the raw material gas are adsorbed onto the surface of the mold 10, in particular, the structure 11. After the supply of the raw material gas is stopped, a reaction gas that reacts with the raw material gas molecules adsorbed on the surface of the structure 11 is supplied to the inside of the vacuum chamber 51 via the gas supply line 52. The reaction gas reacts with the raw material gas molecules to form layers of oxide, nitride, and metal molecules and atoms. By alternately introducing the raw material gas and the reaction gas into the inside of the vacuum chamber 51, a film 20 or 21 is formed (laminated) on the surface of the structure 11. In the ALD apparatus 50, since the film 20 or 21 is formed by adsorption of gas under reduced pressure, it is less affected by the shape of the structure 11 on which the film 20 or 21 is formed, and the film 20 or 21 can be formed over the entire surface of the uneven pattern of the structure 11.

[0035] In the ALD apparatus 50, an active reaction gas containing ions and radicals generated by the plasma from the plasma source 53 may be used as the reaction gas. The holder 55 may also include a heater (not shown) for heating the mold 10 (structure 11) to promote the reaction of the gas introduced into the vacuum chamber 51.

[0036] As one specific example, when forming a film 21 (see Figure 3) containing a layer 211 made of tantalum oxidiznitride, it can be formed in a sputtering apparatus 40 by using argon, oxygen, and nitrogen as the introduction gas. Alternatively, in an ALD apparatus 50, the film 21 containing the layer 211 made of tantalum oxidiznitride can be formed by using water vapor for the oxygen reaction and nitrogen or ammonia for the nitrogen reaction as the reaction gas.

[0037] As another specific example, consider the case where a film 21 (see Figure 3) is formed, which includes a layer 211 made of titanium on the side of the structure 11 and titanium oxide or titanium nitride on the side of the outermost surface 211A. In this case, in the sputtering apparatus 40, titanium should be used as the sputtering target 42, and argon and nitrogen should be used as the introduction gas. At the start, only argon should be used as the introduction gas, and then nitrogen should be introduced, and by gradually increasing the amount of nitrogen, a film 21 can be formed that includes a layer 211 whose composition is graded from metallic titanium to titanium nitride.

[0038] The film 20 or 21 formed on the structure 11 using the sputtering apparatus 40 or ALD apparatus 50 preferably has high transmittance to ultraviolet light in order to increase the intensity of ultraviolet light irradiated onto the curable composition. Metals and nitrides tend to reflect and absorb light more easily than oxides, and therefore tend to have lower transmittance to ultraviolet light. Therefore, when using a metal film such as chromium or titanium, or a nitride such as titanium nitride, as the film 20 or 21, it is preferable to make the thickness of the film 20 or 21 10 nm or less in order to achieve high transmittance to ultraviolet light. Furthermore, even with oxides, the transmittance can be improved by suppressing the reflectance to ultraviolet light by making the outermost surface 201A of the film 20 or the outermost surface 201A of the film 21 a layer with a low refractive index. Therefore, it is preferable that the outermost surface 201A of the film 20 or the outermost surface 201A of the film 21 have a refractive index lower than the refractive index of the internal part, i.e., the part that has an electrical resistance lower than the electrical resistance of the outermost surface 201A or 201A. From the viewpoint of hardness and durability, silicon oxide and aluminum oxide are preferred as materials with a low refractive index for ultraviolet light.

[0039] Furthermore, when the curable composition is imprinted onto the mold 10, some of the curable composition may adhere to and accumulate on the mold 10. In such cases, the curable composition adhering to and accumulated on the surface of the mold 10 is removed by cleaning the mold 10 with an acid or alkaline cleaning agent. Therefore, it is preferable that the outermost layer 201 be made of a material that is poorly soluble in acids or alkalis. Examples of materials that are poorly soluble in acids or alkalis include silicon oxide, silicon nitride, aluminum oxide, and aluminum nitride.

[0040] Furthermore, the hardness of film 201A can be estimated or predicted by forming the film on a smooth substrate such as a silicon wafer using the same process and measuring the hardness of the resulting film. Nanoindentation testing can be used as a method for measuring hardness. In nanoindentation testing, it is known that when the film being measured is several nanometers thick, the hardness of the underlying substrate affects the measured value. Therefore, it is preferable to form a film with a thickness of 100 nm or more and measure the hardness of such a film.

[0041] Furthermore, the surface resistivity of mold 10 can be estimated or predicted by forming a film on an insulating substrate such as quartz using the same process and film configuration, and then measuring the film. As a measuring instrument, for example, the Hiresta-UP MCP HT-450 surface resistance meter manufactured by Mitsubishi Chemical Corporation can be used, and conditions such as an applied voltage of 1000V can be used.

[0042] Furthermore, the transmittance (transmittance) of mold 10 to ultraviolet light can be estimated or predicted by forming a film on a substrate transparent to ultraviolet light, such as quartz, using the same process and film configuration, and then measuring the resulting film. As a measuring instrument, for example, a U4100 manufactured by Hitachi High-Tech Corporation can be used.

[0043] Furthermore, the composition ratio of the film can be measured using the QuanteraII XPS (X-ray Photoelectron Spectroscopy) system manufactured by ULVAC-PHI, Inc.

[0044] An example of the mold 10 in this embodiment is shown below, along with a comparative example.

[0045] (Example 1) In the mold 10 of Example 1, the backplate 13 is made of quartz with dimensions of 152 mm × 152 mm and a thickness of 6 mm, and has a structure 11 made of acrylic acid ester. The shape of the structure 11 is a 28 nm line-and-space relief pattern. On the surface of the structure 11, a film 20 is formed, which includes a silicon oxide film thickness of 7 nm as the outermost layer 201 and titanium film thickness of 3 nm as the intermediate layer 202.

[0046] When forming the film 20 on the structure 11, the outermost layer 201 was formed using the ALD apparatus 50, and the intermediate layer 202 was formed using the sputtering apparatus 40.

[0047] The hardness of the outermost layer 201 of film 20 was measured by nanoindentation testing and was 8 GPa. As mentioned above, in nanoindentation testing, it is known that the hardness of the underlying substrate affects the measured value when the film being measured is several nanometers thick. Therefore, the hardness of the outermost layer 201 was calculated by forming a 200 nm thick film on a silicon wafer using the same process and measuring its hardness.

[0048] The surface resistivity of mold 10 was measured using a Hiresta-UP MCP HT-450 surface resistivity meter manufactured by Mitsubishi Chemical Corporation, under the condition of an applied voltage of 1000V, resulting in 3 × 10⁻¹⁰ 5 The value was Ω / □. The surface resistivity of film 20 was calculated by forming a film on a glass substrate using the same process and film configuration, and measuring its surface resistivity.

[0049] The transmittance (transmittance) to ultraviolet light was measured using a Hitachi High-Tech Corporation U4100 and was 74.6% at a wavelength of 365 nm.

[0050] (Example 2) In the mold 10 of Example 2, the backplate 13 and the structure 11 are formed from the same substrate, and their shape is flat, with a diameter of 305 mm and a thickness of 1 mm, made of quartz. On the surface of the structure 11, a film 20 is formed, which includes titanium nitride with a thickness of 4 nm as the outermost layer 201 and titanium with a thickness of 2 nm as the intermediate layer 202.

[0051] An anti-reflective coating 22 is formed on the first surface 13A of the backplate 13 (the surface opposite to the second surface 13B on which the structure 11 is provided), consisting of two layers: tantalum oxide with a thickness of 60 nm and silicon oxide with a thickness of 40 nm.

[0052] Each layer of the film 20 was formed using a sputtering apparatus 40.

[0053] The hardness of the outermost layer 201 of film 20 was measured by nanoindentation testing and was 20 GPa.

[0054] The surface resistivity of mold 10 was measured using a Hiresta-UP MCP HT-450 surface resistivity meter manufactured by Mitsubishi Chemical Corporation, under the condition of an applied voltage of 1000V, resulting in 6 × 10⁻¹⁰ 5 It was Ω / □.

[0055] The transmittance (transmittance) to ultraviolet light was measured using a Hitachi High-Tech Corporation U4100 and was found to be 68.2%.

[0056] (Example 3) In the mold 10 of Example 3, the same configuration as in Example 2 is used, except that the first surface 13A of the backplate 13 does not have an anti-reflective coating 22 formed on it, which consists of two layers: tantalum oxide with a thickness of 60 nm and silicon oxide with a thickness of 40 nm.

[0057] The transmittance (transmittance) to ultraviolet light was measured using a Hitachi High-Tech Corporation U4100 and was found to be 64.5%.

[0058] (Example 4) In the mold 10 of Example 4, the procedure is the same as in Example 3, but a film 20 with a thickness of 15 nm is formed on the surface of the structure 11, including a titanium nitride with a thickness of 10 nm as the outermost layer 201 and titanium with a thickness of 5 nm as the intermediate layer 202.

[0059] The surface resistivity of mold 10 was measured using a Hiresta-UP MCP HT-450 surface resistivity meter manufactured by Mitsubishi Chemical Corporation, under the condition of an applied voltage of 1000V, resulting in 1 × 10⁻⁶ 5 It was Ω / □.

[0060] The transmittance (transmittance) to ultraviolet light was measured using a Hitachi High-Tech Corporation U4100 and was found to be 41.4%.

[0061] (Example 5) In the mold 10 of Example 5, the structure is the same as in Example 2, but a film 20 is formed on the surface of the structure 11, which includes titanium oxide with a thickness of 2 nm as the outermost layer 201 and titanium nitride with a thickness of 3 nm as the intermediate layer 202.

[0062] The hardness of the outermost layer 201 of film 20 was measured by nanoindentation testing and was 8 GPa.

[0063] The surface resistivity of mold 10 was measured using a Hiresta-UP MCP HT-450 surface resistivity meter manufactured by Mitsubishi Chemical Corporation, under the condition of an applied voltage of 1000V, resulting in 3 × 10⁻¹⁰ 6 It was Ω / □.

[0064] The transmittance (transmittance) to ultraviolet light was measured using a Hitachi High-Tech Corporation U4100 and was found to be 73.4%.

[0065] (Example 6) In the mold 10 of Example 6, the structure is the same as in Example 2, but a film 20 is formed on the surface of the structure 11, which includes titanium nitride with a thickness of 4 nm as the outermost layer 201 and titanium nitride with a thickness of 2 nm as the intermediate layer 202.

[0066] The composition ratio of the intermediate layer 202 was measured using the Quantera II XPS (X-ray Photoelectron Spectroscopy) system manufactured by ULVAC-PHI, Inc. The ratio [N] / [Ti] of the atomic percentage of nitrogen [N] to the atomic percentage of titanium [Ti] in the film 20 of the titanium nitride intermediate layer 202 was 0.5, which is smaller than the usual stoichiometric ratio of 1. Therefore, in the nitride composition ratio, the ratio of nitrogen component to metal component is smaller than the stoichiometric value.

[0067] The hardness of the outermost layer 201 of film 20 was measured by nanoindentation testing and was 20 GPa.

[0068] The surface resistivity of mold 10 was measured using a Hiresta-UP MCP HT-450 surface resistivity meter manufactured by Mitsubishi Chemical Corporation, under the condition of an applied voltage of 1000V, resulting in 1 × 10⁻⁶ 6 It was Ω / □.

[0069] The transmittance (transmittance) to ultraviolet light was measured using a Hitachi High-Tech Corporation U4100 and was found to be 73.5%.

[0070] (Example 7) In the mold 10 of Example 7, the structure 11 is the same as in Example 1, but the structure 11 is made of quartz. On the surface of the structure 11, a film 20 is formed, which includes titanium oxide with a thickness of 5 nm as the outermost layer 201 and titanium with a thickness of 5 nm as the intermediate layer 202.

[0071] The composition ratio of the intermediate layer 202 was measured using XPS. The ratio [O] / [Ti] of the atomic percentage of oxygen [O] to the atomic percentage of titanium [Ti] in the film 20 of titanium oxide in the intermediate layer 202 was 1.7, which is smaller than the usual stoichiometric ratio of 2. Therefore, in the oxide composition ratio, the ratio of the oxygen component to the metal component is smaller than the stoichiometric value.

[0072] The hardness of the outermost layer 201 of film 20 was measured by nanoindentation testing and was 8 GPa.

[0073] The surface resistivity of mold 10 was measured using a Hiresta-UP MCP HT-450 surface resistivity meter manufactured by Mitsubishi Chemical Corporation, under the condition of an applied voltage of 1000V, resulting in 9 × 10⁻¹⁰ 8 It was Ω / □.

[0074] The transmittance (transmittance) to ultraviolet light was measured using a Hitachi High-Tech Corporation U4100 and was found to be 53.5%.

[0075] (Example 8) In the mold 10 of Example 8, the backplate 13 is made of quartz with dimensions of 152 mm × 152 mm and a thickness of 6 mm, and has a structure 11 made of quartz. The shape of the structure 11 is a 28 nm line-and-space relief pattern. A film 21 containing titanium nitride with a thickness of 5 nm is formed on the surface of the structure 11 as a layer 211, and the film 21 is made of a dielectric containing oxygen and nitrogen.

[0076] The composition ratio of layer 211 was measured using XPS. In the titanium nitride layer 211, the ratio of atomic percent of nitrogen [N] to atomic percent of oxygen [O] [O] in the film 21 was 10 in the 1 nm to 2 nm range of the outermost surface 211A, i.e., oxygen was approximately 10% of nitrogen. Therefore, the ratio of atomic percent of nitrogen [N] to atomic percent of oxygen [O] [O] [N] in the film 21 is larger on the outermost surface 211A side of the film 21.

[0077] The hardness of the outermost surface 211A of the film 21 was measured by a nanoindentation test and was 18 GPa.

[0078] The surface resistivity of the mold 10 was measured using Hiresta-UP MCP HT-450, a surface resistivity measuring instrument manufactured by Mitsubishi Chemical Corporation, under the condition of an applied voltage of 1000 V, and was 2×10 6 Ω / sq.

[0079] The transmittance (transmission rate) to ultraviolet light was measured using U4100 manufactured by Hitachi High-Tech Corporation and was 69.8%.

[0080] (Example 9) For the mold 10 of Example 9, it is the same as in Example 8, but the backplate 13 and the structure 11 are formed from the same base material, and its shape is a flat surface, which is quartz having a diameter of 305 mm and a thickness of 1 mm. On the surface of the structure 11, a film 21 containing tantalum oxynitride with a film thickness of 80 nm is formed as the layer 211.

[0081] The composition ratio of the layer 211 was measured using XPS. For the tantalum oxynitride of the layer 211, the ratio [N] / [O] of the atomic percentage of nitrogen [N] and the atomic percentage of oxygen [O] contained in the film 21 was 0.1.

[0082] The hardness of the outermost surface 211A of the film 21 was measured by a nanoindentation test and was 8 GPa.

[0083] The surface resistivity of the mold 10 was measured using Hiresta-UP MCP HT-450, a surface resistivity measuring instrument manufactured by Mitsubishi Chemical Corporation, under the condition of an applied voltage of 1000 V, and was 5×10 8 Ω / sq.

[0084] The transmittance (transmittance) to ultraviolet light was measured using a Hitachi High-Tech Corporation U4100 and was 92.8%.

[0085] (Example 10) In the mold 10 of Example 10, the structure is the same as in Example 3, but a film 20 is formed on the surface of the structure 11, which includes a silicon oxide film with a thickness of 40 nm as the outermost layer 201 and a tantalum oxidiznitride film with a thickness of 60 nm as the intermediate layer 202.

[0086] The hardness of the outermost layer 201 of film 20 was measured by nanoindentation testing and was 8 GPa.

[0087] The surface resistivity of mold 10 was measured using a Hiresta-UP MCP HT-450 surface resistivity meter manufactured by Mitsubishi Chemical Corporation, under the condition of an applied voltage of 1000V, resulting in 9 × 10⁻¹⁰ 8 It was Ω / □.

[0088] The transmittance (transmittance) to ultraviolet light was measured using a Hitachi High-Tech Corporation U4100 and was found to be 94.7%.

[0089] (Example 11) In the mold 10 of Example 11, the procedure is the same as in Example 8, but a film 21 containing titanium nitride with a thickness of 5 nm is formed on the surface of the structure 11 as layer 211.

[0090] An anti-reflective coating 22 is formed on the first surface 13A of the backplate 13 (the surface opposite to the second surface 13B on which the structure 11 is provided), consisting of two layers: tantalum oxide with a thickness of 60 nm and silicon oxide with a thickness of 40 nm.

[0091] The composition ratio of layer 211 was measured using XPS. The ratio [N] / [Ti] of atomic percent nitrogen [Ti] to atomic percent nitrogen [N] in the film 21 of titanium nitride layer 211 was smallest on the side of structure 11, at 0.8, and on the side of the outermost surface 211A, it was 1.0.

[0092] The hardness of the outermost surface 211A of film 21 was measured by nanoindentation testing and was 20 GPa.

[0093] The surface resistivity of mold 10 was measured using a Hiresta-UP MCP HT-450 surface resistivity meter manufactured by Mitsubishi Chemical Corporation, under the condition of an applied voltage of 1000V, resulting in 7 × 10⁻⁶ values. 6 It was Ω / □.

[0094] The transmittance (transmittance) to ultraviolet light was measured using a Hitachi High-Tech Corporation U4100 and was found to be 73.5%.

[0095] (Example 12) In the mold 10 of Example 12, the procedure is the same as in Example 3. However, on the surface of the structure 11, a 3 nm thick film 20 is formed, consisting of a 1 nm thick aluminum oxide outer layer 201 and a 2 nm thick intermediate layer 202 containing aluminum, titanium, and nitrogen-containing aluminum titanium nitride.

[0096] The surface hardness of mold 10 is estimated to be 9 GPa, based on the outermost layer 201 formed on the measurement substrate.

[0097] The surface resistivity of mold 10 is 1 × 10⁻¹⁶ from the film 20 formed on the measurement substrate. 9 It is expected to be Ω / □.

[0098] The transmittance of mold 10 is expected to be 90.0% for light with a wavelength of 365 nm, based on the film 20 formed on the measurement substrate.

[0099] (Comparative Example 1) In the mold of Comparative Example 1, the backplate is made of quartz with dimensions of 152 mm x 152 mm and a thickness of 6 mm, and has a structure formed of quartz. The shape of the structure is a 28 nm line-and-space relief pattern. A chromium-containing film with a thickness of 10 nm is formed as a layer on the surface of the structure.

[0100] The film layer was formed using a sputtering apparatus 40.

[0101] The hardness of the outermost surface of the film was measured by nanoindentation testing and was found to be 6 GPa.

[0102] The surface resistivity of the mold was measured using a Hiresta-UP MCP HT-450 surface resistivity meter manufactured by Mitsubishi Chemical Corporation, under the condition of an applied voltage of 1000V, resulting in a value of 1 × 10⁻⁶. 4 It was Ω / □.

[0103] The transmittance (transmittance) to ultraviolet light was measured using a Hitachi High-Tech Corporation U4100 and was found to be 29.9%.

[0104] (Comparative Example 2) In the mold of Comparative Example 2, the backplate and the structure are formed from the same substrate, and their shape is flat, with a diameter of 305 mm and a thickness of 1 mm, made of quartz. A chromium-containing film with a thickness of 10 nm is formed as a layer on the surface of the structure.

[0105] The hardness of the outermost surface of the film was measured by nanoindentation testing and was found to be 6 GPa.

[0106] The surface resistivity of the mold was measured using a Hiresta-UP MCP HT-450 surface resistivity meter manufactured by Mitsubishi Chemical Corporation, under the condition of an applied voltage of 1000V, resulting in 2 × 10⁻⁶ values. 4 It was Ω / □.

[0107] The transmittance (transmittance) to ultraviolet light was measured using a Hitachi High-Tech Corporation U4100 and was found to be 29.9%.

[0108] (Comparative Example 3) In mold 10 of Comparative Example 3, the backplate is made of quartz with dimensions of 152 mm × 152 mm and a thickness of 6 mm, and has a structure made of acrylic acid ester. A layer containing aluminum oxide with a thickness of 10 nm is formed on the surface of the structure.

[0109] The film layer was formed using a sputtering apparatus 40.

[0110] The hardness of the outermost surface of the film was measured by nanoindentation testing and was found to be 8 GPa.

[0111] The surface resistivity of the mold was measured using a Hiresta-UP MCP HT-450 surface resistivity meter manufactured by Mitsubishi Chemical Corporation, under the condition of an applied voltage of 1000V, resulting in a value of 1 × 10⁻⁶. 14 It was Ω / □.

[0112] The transmittance (transmittance) to ultraviolet light was measured using a Hitachi High-Tech Corporation U4100 and was found to be 90.4%.

[0113] (Comparative Example 4) In the mold of Comparative Example 4, the conditions are the same as those of Comparative Example 2, but a chromium-containing film with a thickness of 10 nm is not formed as a layer.

[0114] The surface resistivity of the mold was measured using a Hiresta-UP MCP HT-450 surface resistivity meter manufactured by Mitsubishi Chemical Corporation, under the condition of an applied voltage of 1000V, resulting in 2 × 10⁻⁶ values. 4 It was Ω / □.

[0115] The transmittance (transmittance) to ultraviolet light was measured using a Hitachi High-Tech Corporation U4100 and was found to be 92.4%.

[0116] (Comparative Example 5) The mold of Comparative Example 5 is the same as that of Comparative Example 2, but the surface of the structure has a film formed thereon, consisting of a titanium film with a thickness of 7 nm as the outermost layer and a silicon oxide film with a thickness of 3 nm as the intermediate layer.

[0117] When forming the film on the structure, the outermost layer was formed using a sputtering apparatus 40, and the intermediate layer was formed using an ALD apparatus 50.

[0118] The hardness of the outermost layer of the film was measured by nanoindentation testing and was found to be 2 GPa.

[0119] The results of imprint tests conducted using molds 10 from Examples 1 to 12 and molds from Comparative Examples 1 to 5 are shown in Tables 1 and 2 below. In the imprint tests, 50 imprint processes were performed, and the surfaces of molds 10 from Examples 1 to 12 and molds from Comparative Examples 1 to 5 were observed. For structures with a line-and-space shape, the presence or absence of distortion of the uneven pattern was observed. For structures with a flat surface shape, the presence or absence of particle increase was observed to evaluate whether defects due to static charge or wear occurred.

[0120] The presence or absence of distortion in the surface texture was observed using a JEOL Ltd. SEM (Scanning Electron Microscope) JSM-IT. The presence or absence of particle increase was observed by shining light on the surface and observing the light scattering caused by the particles (convex). The size of the particles to be observed varied depending on the accuracy required for the imprinting process, but here, particles with a diameter of 0.19 μm to 5 μm were observed. Furthermore, considering the unavoidable particle adhesion due to mold handling, an increase in the number of particles of 30% or more was evaluated as NG, and an increase of less than 30% was evaluated as OK.

[0121] In the molds 10 of Examples 1 to 12, there was no collapse of the uneven pattern or an increase in particles. However, in the molds of Comparative Examples 1 to 5, collapse of the uneven pattern and an increase in particles were observed. This is thought to be due to discharge caused by static charge, the effects of film wear, and particle adhesion due to static charge.

[0122] Furthermore, as shown in Table 2 below, comparative examples 1 and 2 exhibit low transmittance to ultraviolet light, around 30%, while examples 1 to 12 show transmittance to ultraviolet light that is more than 10% higher than comparative examples 1 and 2.

[0123] [Table 1]

[0124] [Table 2]

[0125] Thus, according to this embodiment, it is possible to provide a mold that has antistatic properties, release properties for curable compositions, transmittance to light used to cure the curable composition, and abrasion resistance, which are required for imprint lithography.

[0126] <Second Embodiment> Figure 6 is a schematic diagram showing the configuration of an imprint apparatus 30 as one aspect of the present disclosure. The imprint apparatus 30 is a film forming apparatus that forms a film made of a cured product of a curable composition on a substrate using a mold 10. In this embodiment, the imprint apparatus 30 is employed in the lithography process, which is a manufacturing process for devices such as semiconductor elements, liquid crystal display elements, and magnetic storage media as articles, and is embodied as a lithography apparatus that forms a pattern on a substrate. The imprint apparatus 30 brings the curable composition placed (supplied or coated) on the substrate into contact with the mold 10 and applies curing energy to the curable composition, thereby forming a pattern (film) of cured material on which the uneven pattern of the mold 10 has been transferred.

[0127] As shown in Figure 6, the imprint apparatus 30 includes a stage 32 for holding and positioning a substrate 31 on which the curable composition is placed, and a head 33 (holding part) for holding the mold 10 and bringing the mold 10 into contact with the curable composition placed on the substrate 31. The imprint apparatus 30 also includes a base plate (not shown) for supporting the stage 32 and the head 33, a measuring unit (not shown) for measuring the position of the stage 32, and a dispenser (not shown) for placing the curable composition on the substrate. Furthermore, the imprint apparatus 30 includes an irradiation unit (not shown) for irradiating light 34 to cure the curable composition on the substrate, and a chamber (not shown) that encloses the various parts of the imprint apparatus 30 and stabilizes the process environment. The light 34 for curing the curable composition is selected according to the curable composition, but in this embodiment, it is ultraviolet light between 300 nm and 450 nm.

[0128] In the imprint apparatus 30, a curable composition is placed on the substrate using a dispenser. The dispenser includes, for example, a liquid spray head, and places the curable composition on the substrate in the form of droplets, or in the form of islands or films formed by multiple connected droplets.

[0129] A curable composition is a composition that hardens upon irradiation with light. A photocurable composition that hardens 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 needed. The non-polymerizable compound is at least one selected from the group consisting of sensitizers, hydrogen donors, internal release agents, surfactants, antioxidants, polymer components, etc. The viscosity of the curable composition (viscosity at 25°C) is, for example, 1 mPa·s or more and 100 mPa·s or less.

[0130] The substrate 31 may be made of glass, ceramics, metal, semiconductor, resin, etc., and if necessary, a component made of a different material from the substrate may be formed on its surface. Specifically, the substrate may include silicon wafers, compound semiconductor wafers, quartz glass, etc.

[0131] In the imprint apparatus 30 (film formation method), after placing the curable composition on the substrate 31, the substrate 31 is positioned relative to the mold 10 held by the head 33 via the stage 32. Next, the head 33 is lowered to bring the mold 10 held by the head 33 into contact with the curable composition on the substrate. Then, with the mold 10 and the curable composition on the substrate in contact, light 34 is irradiated onto the curable composition through the mold 10 to cure the curable composition. Finally, the head 33 is raised to separate the mold 10 from the cured curable composition on the substrate. As a result, a pattern of the curable composition with the uneven pattern of the mold 10 transferred onto it is formed on the substrate.

[0132] According to this embodiment, by using the mold 10, a pattern (uneven structure) of the curable composition can be formed more stably on the substrate.

[0133] <Third Embodiment> The pattern of the curable composition formed using the imprint apparatus 30 (film formation method) in this embodiment is used permanently on at least a part of various articles, or temporarily when manufacturing various articles. Articles include electrical circuit elements, optical elements, MEMS, recording elements, sensors, or molds. Examples of electrical circuit elements include volatile or non-volatile semiconductor memories such as DRAM, SRAM, flash memory, and MRAM, as well as semiconductor elements such as LSI, CCD, image sensors, and FPGAs. Examples of molds include molds for imprinting.

[0134] The pattern of the curable composition is used as is, or temporarily, as a component of at least some of the articles described above, or as a resist mask. After etching or ion implantation is performed during the substrate processing process, the resist mask is removed.

[0135] Next, we will explain the specific manufacturing method of the article. As shown in Figure 7(a), a substrate such as a silicon wafer with a workpiece material such as an insulator formed on its surface is prepared, and then a curable composition is applied to the surface of the workpiece by an inkjet method or the like. Here, we show how multiple droplet-shaped curable compositions are applied to the substrate.

[0136] As shown in Figure 7(b), the imprint mold is positioned with the side having the raised and recessed pattern facing the curable composition on the substrate. As shown in Figure 7(c), the substrate to which the curable composition has been applied and the mold are brought into contact, and pressure is applied. The curable composition is filled into the gap between the mold and the workpiece. In this state, when light is shone through the mold as curing energy, the curable composition hardens.

[0137] As shown in Figure 7(d), after curing the curable composition, when the mold and substrate are separated, a pattern of the cured material of the curable composition is formed on the substrate. In this pattern, the recesses of the mold correspond to the protrusions of the cured material, and the protrusions of the mold correspond to the recesses of the cured material. In other words, the uneven pattern of the mold is transferred to the curable composition.

[0138] As shown in Figure 7(e), when etching is performed using the cured material pattern as an etching-resistant mask, the parts of the workpiece surface where there is no cured material, or where a thin layer remains, are removed, forming grooves. As shown in Figure 7(f), when the cured material pattern is removed, an article with grooves formed on the surface of the workpiece can be obtained. Here, the cured material pattern was removed, but it may also be used without removal after processing, for example, as an interlayer insulating film included in semiconductor devices, i.e., as a component of the article.

[0139] <Fourth Embodiment> In the second and third embodiments, the mold 10 described was a mold for transferring a circuit pattern with an uneven pattern formed on it. However, as described above, the mold 10 may also be a mold (planar template) having a flat surface on which no uneven pattern is formed. The planar template is used in a planarization apparatus that performs a planarization process to shape the curable composition on the substrate so as to flatten it using the flat surface. The planarization process includes a step of curing the curable composition supplied to the substrate by irradiating it with light while the planar portion of the planar template is in contact with the curable composition.

[0140] The underlying pattern on the substrate has an uneven profile resulting from the pattern formed in the previous process, and in particular, with the increasing multilayer structure of memory elements in recent years, the substrate (process wafer) may have steps of around 100 nm. Steps caused by the gentle undulation of the entire substrate can be corrected by the focus tracking function of the exposure equipment (scanner) used in the photolithography process. However, fine irregularities with a pitch that fit within the exposure slit area of ​​the exposure equipment consume the depth of focus (DOF) of the exposure equipment. Conventional techniques for planarizing the underlying pattern of the substrate include techniques for forming a planarization layer such as SOC (Spin On Carbon) and CMP (Chemical Mechanical Polishing). However, with conventional techniques, as shown in Figure 8(a), only a 40% to 70% reduction in unevenness can be obtained at the boundary between the isolated pattern region A and the repeating dense (dense line and space pattern) pattern region B, and sufficient planarization performance cannot be obtained. Furthermore, the difference in surface texture due to multi-layer construction is expected to increase even further in the future.

[0141] As a solution to this problem, U.S. Patent No. 9,415,418 proposes a technique for forming a continuous film by applying a resist, which will be the planarization layer, using an inkjet dispenser and imprinting it with a planar template. Furthermore, U.S. Patent No. 8,394,282 proposes a technique for reflecting the topographic measurement results on the substrate side into the density information for each position where the inkjet dispenser is used to instruct application. The imprint apparatus 30 can be applied in particular as a planarization apparatus that performs localized planarization on the substrate surface by pressing a planar template against a pre-applied, uncured resist.

[0142] Figure 8(a) shows the substrate before flattening. In isolated pattern region A, the area of ​​the pattern's raised portion is small. In repeating dense pattern region B, the area occupied by the pattern's raised portion and the area occupied by the pattern's recessed portion are in a 1:1 ratio. The average height of isolated pattern region A and repeating dense pattern region B will differ depending on the proportion of the pattern's raised portion.

[0143] Figure 8(b) shows the substrate after a resist has been applied to form a planarization layer. Figure 8(b) shows the resist being applied by an inkjet dispenser based on the technology proposed in U.S. Patent No. 9415418, but a spin coater may also be used for applying the resist. In other words, the imprint apparatus 30 is applicable as long as it includes a step of planarizing a pre-applied, uncured resist by pressing a planar template onto it.

[0144] As shown in Figure 8(c), the planar template is made of glass or quartz that transmits ultraviolet light, and the resist hardens when exposed to ultraviolet light from a light source. The planar template conforms to the profile of the substrate surface for smooth irregularities across the entire substrate. After the resist hardens, the planar template is separated from the resist, as shown in Figure 8(d).

[0145] Thus, according to this embodiment, by using the mold 10 (flat plate), a flat film (flat structure) of the curable composition can be formed more stably on the substrate.

[0146] The disclosures herein include the following molds, methods for manufacturing molds, methods for forming films, apparatus for forming films, and methods for manufacturing articles.

[0147] (Item 1) A mold used in imprint lithography, A substrate that is transparent to ultraviolet light, A film formed on a structure provided on the second surface of the substrate opposite to the first surface to which the ultraviolet light is incident, It has, The film includes a portion within the film having an electrical resistance lower than the electrical resistance of the outermost surface of the film. A mold characterized by the following features.

[0148] (Item 2) The film includes a top layer including the outermost surface, and an intermediate layer between the structure and the top layer. The intermediate layer includes the portion, The mold described in item 1, characterized by the features described above.

[0149] (Item 3) The mold according to item 2, characterized in that the hardness of the outermost layer is higher than the hardness of the intermediate layer.

[0150] (Item 4) The aforementioned outermost surface includes a dielectric, The aforementioned part includes metal, A mold as described in any one of items 1 to 3, characterized by the above.

[0151] (Item 5) The mold according to any one of items 1 to 4, characterized in that the outermost surface is made of one of silicon oxide, tantalum oxide, titanium oxide, aluminum oxide, titanium nitride, aluminum nitride, and chromium nitride, or a mixture thereof.

[0152] (Item 6) The mold according to any one of items 1 to 4, characterized in that the outermost surface has a refractive index lower than that of the portion with respect to ultraviolet light.

[0153] (Item 7) The mold according to item 6, characterized in that the outermost surface is made of one of silicon oxide and aluminum oxide, or a mixture thereof.

[0154] (Item 8) The aforementioned portion consists of an oxide or nitride, In the composition ratio of the oxide or nitride, the ratio of the oxygen component or nitrogen component to the metal component is smaller than the stoichiometric value. A mold as described in any one of items 1 to 7, characterized by the above.

[0155] (Item 9) The mold according to any one of items 1 to 8, characterized in that the aforementioned portion is a nitride containing titanium and aluminum, or a mixture thereof.

[0156] (Item 11) A mold used in imprint lithography, A substrate that is transparent to ultraviolet light, A film formed on a structure provided on the second surface of the substrate opposite to the first surface to which the ultraviolet light is incident, It has, The aforementioned film is made of a dielectric material containing oxygen and nitrogen. The ratio [O] / [N] of the atomic percentage of nitrogen [N] to the atomic percentage of oxygen [O] in the aforementioned film is higher towards the outermost surface of the film. A mold characterized by the following features.

[0157] (Item 11) The film includes a top layer including the outermost surface, and an intermediate layer between the structure and the top layer. The ratio [O] / [N] in the outermost layer is greater than the ratio [O] / [N] in the intermediate layer. The mold described in item 10, characterized by the features described above.

[0158] (Item 12) A mold used in imprint lithography, A substrate that is transparent to ultraviolet light, A film formed on a structure provided on the second surface of the substrate opposite to the first surface to which the ultraviolet light is incident, It has, The aforementioned film contains tantalum oxidnitridation, A mold characterized by the following features.

[0159] (Item 13) The ultraviolet light has a wavelength of 350 nm or more and 400 nm or less. The substrate, the structure, and the film have a transmittance of 40% or more to ultraviolet light. A mold as described in any one of items 1 to 12, characterized by the above.

[0160] (Item 14) The mold according to any one of items 1 to 13, characterized in that the film has a thickness of 10 nm or less.

[0161] (Item 15) The mold according to any one of items 1 to 14, further comprising an anti-reflective film formed on the first surface.

[0162] (Item 16) The mold according to any one of items 1 to 15, characterized in that the structure includes an uneven pattern.

[0163] (Item 17) The mold according to any one of items 1 to 15, characterized in that the structure includes a flat surface.

[0164] (Item 18) A method for manufacturing molds used in imprint lithography, A step of preparing a substrate that is transparent to ultraviolet light, A step of forming a film on a structure provided on the second surface of the substrate opposite to the first surface to which the ultraviolet light is incident, It has, In the step of forming the film, the film is formed such that it includes a portion having an electrical resistance lower than the electrical resistance of the outermost surface of the film. A method for manufacturing a mold, characterized by the following:

[0165] (Item 19) A method for manufacturing molds used in imprint lithography, A step of preparing a substrate that is transparent to ultraviolet light, A step of forming a film on a structure provided on the second surface of the substrate opposite to the first surface to which the ultraviolet light is incident, It has, The aforementioned film is made of a dielectric material containing oxygen and nitrogen. In the step of forming the aforementioned film, the film is formed such that the ratio [O] / [N] of the atomic percentage of nitrogen [N] to the atomic percentage of oxygen [O] contained in the film is greater on the outermost surface side of the film. A method for manufacturing a mold, characterized by the following:

[0166] (Item 20) A method for manufacturing molds used in imprint lithography, A step of preparing a substrate that is transparent to ultraviolet light, A step of forming a film on a structure provided on the second surface of the substrate opposite to the first surface to which the ultraviolet light is incident, It has, In the step of forming the aforementioned film, the film is formed such that it contains tantalum oxidnitridation. A method for manufacturing a mold, characterized by the following:

[0167] (Item 21) A film forming method for forming a film on a substrate consisting of a cured product of a curable composition using a mold described in any one of items 1 to 17, A step of placing the curable composition on the substrate, A step of bringing the mold and the curable composition into contact, A step of curing the curable composition while it is in contact with the mold, A step of separating the mold from the cured curable composition on the substrate, Having, A film formation method characterized by the following:

[0168] (Item 22) A film forming apparatus for forming a film made of a cured product of a curable composition on a substrate, A retaining part for holding the mold described in any one of items 1 to 17, A film forming apparatus characterized by having the following features.

[0169] (Item 23) A step of forming a film of a curable composition on a substrate using the film formation method described in item 21, A step of processing the substrate on which the film is formed, A process for manufacturing an article from the processed substrate, A method for manufacturing an article, characterized by having the following:

[0170] The technical ideas derived from this disclosure are not limited to the exemplary embodiments disclosed, but are intended to encompass various modifications of the exemplary embodiments, or substitutions with equivalent structures or functions. The scope of the following claims should be interpreted in the broadest way to encompass all such modifications and equivalent structures and functions. [Explanation of Symbols]

[0171] 10: Mold 11: Structure 13: Backplate 13A: First surface 13B: Second surface 20: Film 201: Outermost layer 201A: Outermost surface 202: Intermediate layer

Claims

1. A mold used in imprint lithography, A substrate that is transparent to ultraviolet light, A film formed on a structure provided on the second surface of the substrate opposite to the first surface to which the ultraviolet light is incident, It has, The film includes a portion within the film having an electrical resistance lower than the electrical resistance of the outermost surface of the film. A mold characterized by the following features.

2. The film includes a top layer including the outermost surface, and an intermediate layer between the structure and the top layer. The intermediate layer includes the portion, The mold according to feature 1.

3. The mold according to claim 2, characterized in that the hardness of the outermost layer is higher than the hardness of the intermediate layer.

4. The aforementioned outermost surface includes a dielectric, The aforementioned part includes metal, The mold according to feature 1.

5. The mold according to claim 1, characterized in that the outermost surface is made of one of silicon oxide, tantalum oxide, titanium oxide, aluminum oxide, titanium nitride, aluminum nitride, and chromium nitride, or a mixture thereof.

6. The mold according to claim 1, characterized in that the outermost surface has a refractive index lower than that of the portion with respect to ultraviolet light.

7. The mold according to claim 6, characterized in that the outermost surface is made of one of silicon oxide and aluminum oxide, or a mixture thereof.

8. The aforementioned portion consists of an oxide or nitride, In the composition ratio of the oxide or nitride, the ratio of the oxygen component or nitrogen component to the metal component is smaller than the stoichiometric value. The mold according to feature 1.

9. The mold according to claim 1, characterized in that the aforementioned portion is a nitride containing titanium and aluminum, or a mixture thereof.

10. A mold used in imprint lithography, A substrate that is transparent to ultraviolet light, A film formed on a structure provided on the second surface of the substrate opposite to the first surface to which the ultraviolet light is incident, It has, The aforementioned film is made of a dielectric material containing oxygen and nitrogen. The ratio [O] / [N] of the atomic percentage of nitrogen [N] to the atomic percentage of oxygen [O] contained in the film is greater towards the outermost surface of the film. A mold characterized by the following features.

11. The film includes a top layer including the outermost surface, and an intermediate layer between the structure and the top layer. The ratio [O] / [N] in the outermost layer is greater than the ratio [O] / [N] in the intermediate layer. The mold according to feature 10.

12. A mold used in imprint lithography, A substrate that is transparent to ultraviolet light, A film formed on a structure provided on the second surface of the substrate opposite to the first surface to which the ultraviolet light is incident, It has, The aforementioned film contains tantalum oxidnitridation, A mold characterized by the following features.

13. The ultraviolet light has a wavelength of 350 nm or more and 400 nm or less. The substrate, the structure, and the film have a transmittance of 40% or more to ultraviolet light. A mold according to any one of claims 1, 10, and 12, characterized by the features described herein.

14. The mold according to any one of claims 1, 10, and 12, characterized in that the film has a thickness of 10 nm or less.

15. The mold according to any one of claims 1, 10, and 12, further comprising an anti-reflective coating formed on the first surface.

16. The mold according to any one of claims 1, 10, and 12, characterized in that the structure includes an uneven pattern.

17. The mold according to any one of claims 1, 10, and 12, characterized in that the structure includes a flat surface.

18. A method for manufacturing molds used in imprint lithography, A step of preparing a substrate that is transparent to ultraviolet light, A step of forming a film on a structure provided on the second surface of the substrate opposite to the first surface to which the ultraviolet light is incident, It has, In the step of forming the film, the film is formed such that it includes a portion having an electrical resistance lower than the electrical resistance of the outermost surface of the film. A method for manufacturing a mold, characterized by the following:

19. A method for manufacturing molds used in imprint lithography, A step of preparing a substrate that is transparent to ultraviolet light, A step of forming a film on a structure provided on the second surface of the substrate opposite to the first surface to which the ultraviolet light is incident, It has, The aforementioned film is made of a dielectric material containing oxygen and nitrogen. In the step of forming the aforementioned film, the film is formed such that the ratio [O] / [N] of the atomic percentage of nitrogen [N] to the atomic percentage of oxygen [O] contained in the film is greater on the outermost surface side of the film. A method for manufacturing a mold, characterized by the following:

20. A method for manufacturing molds used in imprint lithography, A step of preparing a substrate that is transparent to ultraviolet light, A step of forming a film on a structure provided on the second surface of the substrate opposite to the first surface to which the ultraviolet light is incident, It has, In the step of forming the aforementioned film, the film is formed such that it contains tantalum oxidnitridation. A method for manufacturing a mold, characterized by the following:

21. A film forming method for forming a film made of a cured product of a curable composition on a substrate using a mold according to any one of claims 1, 10, and 12, A step of placing the curable composition on the substrate, A step of bringing the mold and the curable composition into contact, A step of curing the curable composition while it is in contact with the mold, A step of separating the mold from the cured curable composition on the substrate, Having, A film formation method characterized by the following:

22. A film forming apparatus for forming a film made of a cured product of a curable composition on a substrate, A retaining part for holding a mold according to any one of claims 1, 10, and 12, A film forming apparatus characterized by having the following features.

23. A step of forming a film of a curable composition on a substrate using the film forming method described in claim 21, A step of processing the substrate on which the film is formed, A process for manufacturing an article from the processed substrate, A method for manufacturing an article, characterized by having the following:

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