JP2014044245A - Production method of mold - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of a mold which can give a pattern with high resolution and improve stability of resolution or uniformity of resolution in a large area.SOLUTION: The production method of a mold includes a step of exposing a resist layer containing an incomplete oxide of a transition metal in an atmosphere having a relative humidity of 30% or lower. In the production method of a mold, the incomplete oxide of a transition metal is preferably an incomplete oxide of molybdenum (Mo) and/or tungsten (W).

Description

  The present invention relates to a method for manufacturing a mold, for example, a method for manufacturing a mold for fine processing.

  In recent years, fine processing with high resolution is required in the fields of semiconductors, optical devices, magnetic devices, and the like. In microfabrication of a semiconductor or the like, a photolithography technique for exposing through a mask is generally used. In this photolithography, since the focus cannot be reduced below the wavelength of the light to be exposed, a special radiation source such as ArF, an electron beam, and an X-ray, and a high-precision exposure apparatus are used to perform fine processing with high resolution. Was necessary. These special radiation sources and high-accuracy exposure apparatuses require excessive facilities in proportion to the processing accuracy, and are the main factors that push up the manufacturing cost of semiconductor manufacturing.

  Therefore, a thermal lithography technique capable of performing fine processing without using a special radiation source and a high-precision exposure apparatus has been proposed (for example, see Patent Documents 1 to 3). In this thermal lithography, fine processing is performed by utilizing the fact that the irradiation energy distribution becomes narrower than the optical irradiation distribution when the light irradiated to the heat-reactive resist and absorbed is changed into heat. That is, when a laser beam is irradiated to a resist whose chemical properties change due to thermal reaction when the temperature exceeds a predetermined temperature (hereinafter also referred to as “thermal reaction type resist”), the central portion of the exposure region of the thermal reaction type resist is predetermined. The outer edge of the exposure region becomes an unreacted region below a predetermined temperature. Thereby, since the chemical properties can be made different between the thermal reaction region and the unreacted region in the thermal reaction type resist, only the thermal reaction region or the unreacted region can be selectively processed. As a result, a range narrower than the optical irradiation region can be processed.

  By the way, the functions required for the heat-reactive resist include (1) absorbing irradiated light and converting it into heat energy, and (2) a large change rate of the resist material with respect to the heat energy, and a selection ratio during development. And (3) high resistance to dry etching after pattern formation. As one of the heat-reactive resists that satisfy the above requirements (1) to (3), an inorganic resist can be cited. As the inorganic resist, for example, an inorganic resist containing an incomplete oxide of a transition metal such as molybdenum (Mo) or tungsten (W) has been proposed (see, for example, Patent Document 1 and Patent Document 2). These inorganic resists substantially satisfy the above characteristics (1) to (3).

JP 2003-315988 A JP 2004-152465 A JP 2012-2967 A

  However, the inorganic resists described in Patent Document 1 and Patent Document 2 do not always have sufficient resolution when used for nano-order microfabrication by thermal lithography, and also have stable resolution and resolution in a large area. There was a problem of poor uniformity.

  The present invention has been made in view of such points, and an object of the present invention is to provide a mold manufacturing method capable of obtaining a high-resolution pattern and improving the stability of resolution and the uniformity of resolution over a large area. And

  The mold manufacturing method of the present invention includes a step of exposing a resist layer containing an incomplete oxide of a transition metal in an atmosphere having a relative humidity of 30% or less.

  According to this mold manufacturing method, the reactivity of the incomplete oxide of the transition metal at the time of exposure can be lowered, so that the oxidation reaction of the incomplete oxide of the transition metal can be suppressed even when the temperature becomes high at the time of exposure. . Thereby, since the function required as a heat-reactive resist of a resist layer can be maintained, a high resolution pattern can be obtained, and the stability of resolution and the uniformity of resolution in a large area can be improved.

  In the mold manufacturing method of the present invention, the incomplete oxide of the transition metal is preferably an incomplete oxide of molybdenum (Mo) and / or tungsten (W).

  In the mold manufacturing method of the present invention, the resist layer preferably contains an amorphous inorganic material containing an incomplete oxide of the transition metal.

  In the mold manufacturing method of the present invention, the resist layer preferably contains an element other than the transition metal.

  In the mold manufacturing method of the present invention, the element other than the transition metal is selected from the group consisting of aluminum (Al), carbon (C), boron (B), silicon (Si), and germanium (Ge). It is preferable that there is at least one.

  In the mold manufacturing method of the present invention, the resist layer is provided on a substrate made of at least one selected from the group consisting of quartz, glass, plastic, silicon, alumina titanium carbide, and nickel. Is preferred.

  In the mold manufacturing method of the present invention, it is preferable that the resist layer is formed by sputtering or vapor deposition.

  ADVANTAGE OF THE INVENTION According to this invention, the high-resolution pattern is obtained and the manufacturing method of the mold which can improve the stability of resolution and the uniformity in a large area is realizable.

  In thermal lithography, a heat-reactive resist containing an incomplete oxide of a transition metal is used. The incomplete oxide of the transition metal contained in the heat-reactive resist is thermodynamically metastable and has a characteristic of easily changing to a transparent complete oxide by an oxidation reaction. This transparent transition metal perfect oxide has almost no light absorption, so when the oxidation reaction described above proceeds, it is a necessary characteristic for a heat-reactive resist. (1) It absorbs irradiated light and converts it into thermal energy. The characteristics to be lost.

  In thermal lithography, a heat-reactive resist is used by forming a thin film of several tens of nanometers. For this reason, the oxidation reaction of the incomplete oxide of the transition metal is likely to proceed due to the oxidizing atmosphere, and the characteristics of the thermal reaction resist may be deteriorated. In particular, this oxidation reaction is remarkable during exposure in which the heat-reactive resist is in a high temperature state, and oxidation from an incomplete oxide to a complete oxide is promoted during exposure. And if this oxidation reaction proceeds in the thermal energy irradiation area of the resist layer, there is no effect on pattern formation, but if it goes outside the thermal energy irradiation area, the characteristics as a thermal reaction resist deteriorate. This increases the area to be formed, making it difficult to form a high resolution pattern. In addition, since nano-order heat transfer control is difficult, there is a problem that it is difficult to ensure stability of resolution and uniformity of resolution in a large area.

  The inventor paid attention to the fact that the valence of the incomplete oxide of the transition metal contained in the resist layer is non-uniform in the resist layer and that it changes with time. It has been found that the change over time is affected by the atmospheric humidity and temperature after the formation of the resist layer, and that the influence of the atmospheric humidity becomes particularly significant during the exposure of thermal lithography. Then, the present inventor makes the incomplete oxidation state of the thermal reaction type resist including the incomplete oxide of the transition metal substantially constant by setting the atmospheric humidity to a predetermined range during the exposure of the thermal lithography, so The inventors have conceived of suppressing the change in the valence of the complete oxide, and have completed the present invention based on this idea.

  That is, the gist of the present invention is a mold manufacturing method including a step of exposing a resist layer containing an incomplete oxide of a transition metal in an atmosphere having a relative humidity of 30% or less. As a result, the reactivity of the incomplete oxide of the transition metal at the time of exposure can be lowered, so that the oxidation reaction of the incomplete oxide of the transition metal at the time of exposure can be suppressed, which is required as a thermally reactive resist for the resist layer. Function is not impaired. As a result, even in thermal lithography using a resist containing an incomplete oxide of a transition metal, a high resolution pattern can be obtained, and the stability of resolution and the uniformity of resolution in a large area can be improved.

Hereinafter, an embodiment of the present invention will be described in detail.
In the mold manufacturing method according to the present embodiment, a resist layer is obtained by providing a resist layer containing an incomplete oxide of a transition metal on a substrate, and the resist layer of the resist laminate is subjected to a relative humidity of 30. % An exposure step of exposing in an atmosphere of less than or equal to%, and a development step of developing a resist layer after exposure to obtain a mold. Hereinafter, each step will be described.

(Lamination process)
In the lamination step, a resist layer containing an incomplete oxide of a transition metal is formed on the substrate by an arbitrary method to produce a resist laminate. In the stacking step, the resist layer is preferably formed by sputtering or vapor deposition. Thereby, since the oxidation degree of the incomplete oxide of the transition metal forming the resist layer can be controlled, an incomplete oxide composition that is harder to oxidize can be obtained, and an unintended oxidation reaction after film formation can be suppressed.

  In the case of forming a resist layer by a sputtering method, for example, the resist layer is formed in an argon and oxygen atmosphere using a target made of a single transition metal. In this case, the degree of oxidation of the incomplete oxide of the transition metal can be controlled by changing the oxygen gas concentration in the vacuum atmosphere.

Examples of the sputtering method include a method of forming a film in an argon (Ar) and oxygen (O ₂ ) atmosphere using a target containing molybdenum (Mo) and / or tungsten (W). In this case, oxygen (O ₂ ) is 5% to 20% with respect to the total flow rate of the introduced gas into the chamber. The gas pressure may be a normal sputtering gas pressure (1 Pa to 10 Pa). Alternatively, sputtering may be performed in an argon atmosphere using a target made of an incomplete oxide of a transition metal containing a desired amount of oxygen in advance.

  When forming a resist layer by a vapor deposition method, the method of vapor-depositing incomplete oxides of transition metals, such as molybdenum (Mo) and tungsten (W), is mentioned.

  The resist laminate is preferably stored in an atmosphere in which the incomplete oxidation state of the transition metal of the resist layer is unlikely to change before being processed in the next exposure step, and stored in an atmosphere with a relative humidity of 30% or less. Is more preferable. By storing in an atmosphere having a relative humidity of 30% or less until before the exposure step, the incomplete oxide of the transition metal contained in the resist layer is maintained at a substantially constant valence, and thus becomes a complete oxide with low absorbance. Can be prevented. As a result, it is possible to prevent the disappearance of the characteristic of absorbing the irradiated light and converting it into thermal energy, so that exposure can be performed satisfactorily.

(Exposure process)
In the exposure step, the resist layer of the resist laminate is exposed by an exposure device. By this exposure, a part of the exposed region in the resist layer becomes a heat reaction region in which the chemical properties are changed by heat reaction, and a heat reaction region and an unreacted region are formed in the resist layer. Since the thermal reaction region and the unreacted region have different etching rates with respect to alkali or acid, a so-called selective ratio is obtained.

  Here, in the mold manufacturing method according to the present embodiment, since the resist layer is exposed in an atmosphere having a relative humidity of 30% or less, the reactivity of the incomplete oxide of the transition metal at the time of exposure can be lowered. Therefore, even when the resist layer is in a high temperature state during exposure, the oxidation reaction of the incomplete oxide of the transition metal can be suppressed. Thereby, since it can expose without impairing the function requested | required as a heat-reactive resist of a resist layer, a high-resolution pattern can be formed.

  The relative humidity at the time of exposure is preferably 1% or more and 25% or less as the relative humidity at the time of exposure. If the relative humidity at the time of exposure is 1% or more, an excessive facility for obtaining a desired relative humidity is not required, and if the relative humidity is 25% or less, oxidation of incomplete oxides at a high temperature state at the time of exposure. Reaction can be suppressed and a higher definition pattern can be obtained.

  In the exposure process, for example, an exposure apparatus including a laser apparatus that irradiates ultraviolet light, visible light, or heat rays is used. In the mold manufacturing method according to the present embodiment, since a fine pattern can be formed without using a high-cost special light source and a high-precision exposure device, a light source device such as a small and inexpensive semiconductor laser is used. Can do.

  The pattern formed in the exposure step is a nano-order pattern, and the pitch is preferably 50 nm or more and 1 μm or less. The shape of the pattern is not particularly limited, and examples include line and space (hereinafter referred to as “L / S”), dots, and long holes. A plurality of these patterns may be provided in one base material, and patterns having different pitches may be mixed.

(Development process)
In the development step, the thermal reaction region of the resist layer is selectively dissolved and removed using a desired developer. As a result, a predetermined exposure pattern constituted by an unreacted region of the resist layer is formed on the substrate, and a resist master is obtained.

  In the development step, a wet process using an acid or alkali developer can be used. The wet process conditions can be appropriately selected according to the pattern selection ratio, the purpose of use of the mold, the application, the equipment and the like.

Examples of the alkali developer include inorganic alkali aqueous solutions such as tetramethylammonium hydroxide solution, KOH, NaOH, and Na ₂ CO ₃ . Examples of the acid developer include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, and hydrofluoric acid. These developers can be used alone or as a mixed solution.

  Further, as the developer, a developer to which a potential adjusting agent such as hydrogen peroxide or manganese peroxide is added may be used, or a developer having improved developability by adding a surfactant or the like may be used. . In addition, depending on the material used for the resist layer, first, development with an acid developer may be performed, followed by development with an alkali developer.

  Next, the structure of the resist laminated body used for the mold manufacturing method according to the above embodiment will be described in detail.

  The substrate is not particularly limited as long as a resist layer can be provided on the substrate and the resist layer can be exposed. Among these, the substrate is preferably at least one selected from the group consisting of quartz, glass, plastic, silicon, alumina, titanium carbide, and nickel from the viewpoint of obtaining high exposure sensitivity. As quartz, synthetic quartz, fused quartz, or the like can be used, and as glass, alkali-free glass, low alkali glass, soda lime glass, or the like can be used.

  As a base material, a thing with small heat conductivity is preferable from a viewpoint of obtaining high exposure sensitivity. As the thermal conductivity of the base material decreases, the temperature rise during exposure increases, and the chemical properties of the resist materials that make up the resist layer on the base material change greatly, facilitating the thermal reaction of the resist layer. can do.

  The shape of the substrate is not particularly limited as long as a fine pattern can be continuously formed on the resist layer at the time of exposure, and a substrate such as a wafer shape, a square shape such as a square shape, or a cylindrical shape can be used. . In particular, a cylindrical base material is preferable from the viewpoint of reducing the area limit of the pattern formed on the resist layer.

  The resist layer is not particularly limited as long as it contains an incomplete oxide of a transition metal element. The film thickness of the resist layer can be arbitrarily set, and can be, for example, in the range of 10 nm to 80 nm.

  The incomplete oxide of transition metal is preferably an incomplete oxide of molybdenum (Mo) and / or tungsten (W). Thereby, since light absorptivity is obtained from the ultraviolet region to the visible light to infrared region, developability is improved.

  Note that in this specification, an incomplete oxide of molybdenum (Mo) and / or tungsten (W) means that the oxygen content in the incomplete oxide is that of molybdenum (Mo) and / or tungsten (W). The compound is smaller than the oxygen content of the stoichiometric composition according to the possible valence.

As an example of an oxide of molybdenum (Mo) and / or tungsten (W), molybdenum oxide represented by the chemical formula MoO ₃ will be described in detail. When the oxidation state of molybdenum oxide (chemical formula MoO ₃ ) is converted to the composition ratio Mo _1-x O _x , the case of x = 0.75 is a complete oxide, whereas 0 <x <0.75. It can be said that it is an incomplete oxide whose oxygen content is less than the stoichiometric composition.

In addition, some transition metals such as molybdenum (Mo) and tungsten (W) can form oxides having different valences in one element. In this case, depending on the valence that the transition metal can take. When the actual oxygen content is less than the stoichiometric composition, the incomplete oxide is included. For example, for the molybdenum (Mo), the trivalent oxide (MoO ₃ ) described above is most stable, but there is also a monovalent oxide (MoO). In this case, in terms of the composition ratio Mo _1-x O _x , it can be said that the incomplete oxide has an oxygen content that is less than the stoichiometric composition when in the range of 0 <x <0.5.

  The oxidation degree (valence) of transition metal oxides such as molybdenum (Mo) and tungsten (W) can be analyzed with a commercially available analyzer. For example, it can be analyzed by an analyzer such as EDX (energy dispersive X-ray detector), XRF (fluorescent X-ray analyzer), or X-ray photoelectron spectrometer.

  Such incomplete oxides of transition metals such as molybdenum (Mo) and tungsten (W) are used for light from a laser device mounted on a conventional exposure apparatus, that is, ultraviolet light, visible light, or heat rays. It shows absorption, and its chemical properties change when irradiated. As a result, although it is an inorganic resist, a difference occurs in the etching rate between the thermally reacted region and the unreacted region in the development process, and so-called selectivity is obtained. In addition, the resist material made of incomplete oxides of transition metals such as molybdenum (Mo) and tungsten (W) has a small film particle size, so the boundary pattern between the thermal reaction region and the unreacted region is clear. Therefore, the resolution can be increased.

  The resist layer preferably contains an amorphous inorganic material containing an incomplete oxide of a transition metal. As the amorphous inorganic material, for example, a material made of an incomplete oxide of molybdenum (Mo) and / or tungsten (W) is preferable. Thereby, since the size of the crystal grains constituting the resist layer is reduced, the pattern of the boundary portion between the thermal reaction region and the unreacted region becomes clear, and the resolution can be improved.

  Moreover, the small crystal grain size constituting the resist layer means that the resist layer is easily affected by the oxidizing atmosphere and the incomplete oxidation state of the transition metal is likely to change. However, even if the size of the crystal particles constituting the resist is small, unnecessary oxidation of the resist layer can be achieved by applying the mold manufacturing method according to the present embodiment and exposing in an atmosphere with a relative humidity of 30% or less. Can be suppressed.

  Moreover, it is preferable that the resist layer which comprises a resist laminated body contains elements other than a transition metal other than the incomplete oxide of a transition metal. Thereby, since the crystal grains of the incomplete oxide of the transition metal are reduced, the boundary between the thermal reaction region and the unreacted region becomes clearer, the resolution is improved, and the exposure sensitivity is also improved. .

  Also in this case, since the size of the crystal grains constituting the resist layer is reduced, the resist layer is easily affected by the oxidizing atmosphere, and the incomplete oxidation state of the transition metal is likely to change. However, even if the size of the crystal particles constituting the resist is small, unnecessary oxidation of the resist layer can be achieved by applying the mold manufacturing method according to the present embodiment and exposing in an atmosphere with a relative humidity of 30% or less. Can be suppressed.

  The element other than the transition metal is preferably at least one selected from the group consisting of aluminum (Al), carbon (C), boron (B), silicon (Si), and germanium (Ge). The element other than the transition metal can be appropriately selected according to the characteristics required for the resist. For example, when using light in the vicinity of infrared light for exposure, silicon (Si) or germanium (Ge), which has a large absorption in the wavelength range, may be added. In the ultraviolet range, aluminum (Al) is used. What is necessary is just to add.

  As described above, according to the mold manufacturing method of the present embodiment, it is possible to use a conventional inexpensive exposure apparatus and perform high-precision microfabrication without using molybdenum (Mo) and / or tungsten (W). Since the incomplete oxidation state of the thermal reaction resist containing a complete oxide can be kept substantially constant, and unnecessary oxidation reaction during exposure can be suppressed, high resolution and stability of resolution, as well as large area uniformity can be achieved. It becomes possible to improve.

  Hereinafter, the present invention will be described more specifically based on examples carried out in order to clarify the effects of the present invention. In addition, this invention is not limited at all by the following examples.

<Example 1>
As the substrate, a glass substrate having a diameter of 2 inches was used. On this glass substrate, a resist layer made of an incomplete oxide of tungsten (W) was formed by sputtering to form a resist laminate. The sputtering method was performed in a mixed atmosphere of argon and oxygen using a sputtering target made of a single element of tungsten (W). The degree of oxidation of the incomplete oxide of tungsten (W) was controlled by changing the oxygen gas concentration.

When the deposited resist layer was analyzed by an energy dispersive X-ray detector, x = 0.62 when expressed by the composition ratio W _1-x O _x . Moreover, the film thickness of the resist layer was 40 nm. The obtained resist laminate was stored in a constant temperature and humidity chamber at a temperature of 25 ° C. and a relative humidity of 30% until the exposure process.

Next, an L / S pattern was exposed on the resist laminate under the following conditions in an atmosphere of a temperature of 25 ° C. and a relative humidity of 30%.
Semiconductor laser wavelength for exposure: 405 nm
Lens numerical aperture: 0.85
Exposure laser power: 8mW
Feed pitch: 300nm

  Next, the exposed resist laminate was developed with an alkali developer. A tetramethylammonium hydroxide solution was used as the alkaline developer. The development time was 30 minutes. After completion of development, the film was thoroughly washed with pure water and isopropyl alcohol and dried by air blow or the like.

  The obtained pattern was an L / S pattern having a pitch (P) of 300 nm and a pattern width (W) of 100 nm. The results are shown in Table 1 below together with the standard deviation of the pattern width.

<Example 2>
A resist laminate was formed in the same manner as in Example 1 except that a resist layer made of a trivalent incomplete oxide of molybdenum (Mo) was formed as the resist layer.

When the deposited resist layer was analyzed by an energy dispersive X-ray detector, x = 0.60 when expressed by the composition ratio Mo _1-x O _x . The thickness of the resist layer was 40 nm. The obtained resist laminate was stored in a constant temperature and humidity chamber at a temperature of 25 ° C. and a humidity of 30% until the exposure process.

Next, an L / S pattern was exposed on the resist laminate under the following conditions in an atmosphere of a temperature of 25 ° C. and a relative humidity of 30%.
Semiconductor laser wavelength for exposure: 405 nm
Lens numerical aperture: 0.85
Exposure laser power: 8mW
Feed pitch: 500nm

  Next, the exposed resist laminate was developed with an alkali developer. A tetramethylammonium hydroxide solution was used as the alkaline developer. The development time was 30 minutes. After the development, the film was thoroughly washed with pure water and isopropyl alcohol and dried by air blow or the like.

  The obtained pattern was an L / S pattern having a pitch (P) of 500 nm and a pattern width (W) of 150 nm. The results are also shown in Table 1 below together with the standard deviation of the pattern width.

<Comparative Example 1>
Similarly to Example 1, a resist layer made of an incomplete oxide of tungsten (W) represented by W _1-x O _x was formed on glass. When the deposited resist layer was analyzed by an energy dispersive X-ray detector, x = 0.62 when expressed by the composition ratio W _1-x O _x . The obtained resist laminate was stored in a constant temperature and humidity chamber at a temperature of 25 ° C. and a humidity of 30% until the exposure step.

  Next, the resist laminate was exposed and developed under the same conditions as in Example 1 except that the atmosphere was a temperature of 25 ° C. and a relative humidity of 50%.

  The obtained pattern was an L / S pattern having a pitch (P) of 300 nm and a pattern width (W) of 150 nm.

<Comparative example 2>
A resist laminate was prepared in the same manner as in Example 1, and stored in a constant temperature and humidity chamber at a temperature of 25 ° C. and a humidity of 30% until the exposure process.

  Next, the resist laminate was exposed and developed under the same conditions as in Example 1 except that the atmosphere was a temperature of 25 ° C. and a relative humidity of 80%.

  A clear pattern was not observed in the obtained glass. The results are also shown in Table 1 below.

<Comparative Example 3>
In the same manner as in Example 2, a resist layer represented by x = 0.60 when represented by Mo _1-x O _x was formed on glass.

  The obtained resist laminate was stored in a constant temperature and humidity chamber at a temperature of 25 ° C. and a humidity of 30% until the exposure step.

  Next, the resist laminate was exposed and developed under the same conditions as in Example 1 except that the atmosphere was a temperature of 25 ° C. and a relative humidity of 50%.

  The obtained pattern was an L / S pattern having a pitch (P) of 300 nm and a pattern width (W) of 200 nm. The results are also shown in Table 1 below.

  As can be seen from Table 1, when the exposure is performed at a relative humidity of 30% or less, the pitch (P) and the pattern width (W) are in an appropriate range, and a high-resolution pattern can be obtained (Example) 1 and Example 2). On the other hand, when the relative humidity is 50%, the width becomes wider with respect to the pattern pitch and the variation amount of the pattern width becomes larger, so that it can be seen that the resolution is lower than that of the first embodiment (comparative example). 1: Resolution 33% reduction, Comparative Example 3: Resolution 25% reduction). Further, it can be seen that the pattern cannot be formed when the relative humidity is 80% (Comparative Example 2). These results are thought to be due to the progress of the oxidation reaction of the resist layer during exposure.

  In addition, this invention is not limited to the said embodiment, It can implement variously. In the above-described embodiment, the size, shape, and the like illustrated in the accompanying drawings are not limited thereto, and can be appropriately changed within a range in which the effect of the present invention is exhibited. In addition, various modifications can be made without departing from the scope of the object of the present invention.

  INDUSTRIAL APPLICABILITY The present invention has an effect of realizing a mold manufacturing method capable of obtaining a high-resolution pattern and improving the stability of resolution and the uniformity of resolution with a large area, and in particular, an optical device such as an optical disk and a wire. It can be suitably used for the production of molds used in the production of various devices and materials such as optical materials such as grid polarizers, display devices, and magnetic devices.

Claims (7)

  A method for producing a mold, comprising a step of exposing a resist layer containing an incomplete oxide of a transition metal in an atmosphere having a relative humidity of 30% or less.   2. The mold manufacturing method according to claim 1, wherein the incomplete oxide of the transition metal is an incomplete oxide of molybdenum (Mo) and / or tungsten (W).   The method for producing a mold according to claim 1, wherein the resist layer contains an amorphous inorganic material containing an incomplete oxide of the transition metal.   The said resist layer contains elements other than a transition metal, The manufacturing method of the mold in any one of Claims 1-3 characterized by the above-mentioned.   The element other than the transition metal is at least one selected from the group consisting of aluminum (Al), carbon (C), boron (B), silicon (Si), and germanium (Ge). The method for producing a mold according to claim 4.   The said resist layer is provided on the base material which consists of at least 1 sort (s) selected from the group which consists of quartz, glass, a plastics, a silicon | silicone, an alumina titanium carbide, and nickel, The Claim 1 characterized by the above-mentioned. 6. The method for producing a mold according to any one of 5 above.   The method for producing a mold according to claim 1, wherein the resist layer is formed by sputtering or vapor deposition.