JPH11288528A - Production of master disk for production of recording medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a recording medium capable of dealing with a higher recording density and higher recording capacity by using an exposure source which permits higher resolution and regulating process conditions of resist adaptive thereto. SOLUTION: This process has a resist coating application stage 2 for applying the resist on a glass substrate, a heat treatment stage 3 for heat treating the glass substrate coated with the resist, an exposure stage 4 for exposing the resist on the glass substrate subjected to the heat treatment by using any among a laser beam, electron rays, X-ray and ion rays, a developing stage 5 for forming patterns indicating information by developing the exposed resist by using a developer, a metallic film deposition stage for depositing a metallic film on the surface of the glass substrate formed with the patterns, a peeling stage 8 for peeling the metallic film from the glass substrate, a washing stage for washing the org. matter sticking to the peeled metallic film by a solvent and a UV irradiation stage 10 for decomposing and removing the org. matter remaining on the metallic film by irradiating the washed metallic film with UV rays.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method of manufacturing a master for manufacturing a recording medium.

[0002]

2. Description of the Related Art In a process of manufacturing a master for manufacturing a recording medium, which is a base of a disk-shaped recording medium such as an optical disk, first, a photoresist is coated on a polished glass substrate having a thickness of several mm.
Spin coating is performed uniformly to a thickness of 200 nm to 200 nm, and light from a laser is condensed by an objective lens while rotating the glass substrate to selectively expose the photoresist to a spot. Thereafter, a predetermined pattern, that is, pits or group-like fine irregularities are formed on the glass substrate by developing the photoresist with an alkaline solution, and a glass master is obtained.

Further, a master for recording medium production is manufactured by subjecting the glass master to a conductive process and electroforming plating. In this conductive treatment, a metal is deposited or deposited to a thickness of about 50 nm to 100 nm by electroless plating or sputtering to secure conduction. Furthermore, about 300 μm
A metal film is formed to a thickness of. Lastly, the metal film is polished on the back surface and the end surface is processed, and the metal film is peeled off from the glass master to complete a master for recording medium production as a replica of the glass master.

In recent years, with the rapid development of information communication and image processing technology, optical disks are required to have higher recording density and higher recording capacity. In particular,
It is required that one side of an optical disc having a diameter of 12 cm has an information capacity of 20 GB. The highest recording density among optical discs currently in practical use has been achieved, and DVD (trademark) having a capacity of 4.7 GB has been developed.
Track pitch 0.74μm, shortest pit length 0.4
Considering that the track pitch is 0.3 μm, a track pitch of 0.3
It is necessary to reduce the size to 5 μm and the minimum pit length to 0.2 μm.

[0005] Higher density optical discs have been realized by increasing the numerical aperture of the objective lens during exposure and shortening the exposure wavelength, as in the case of the photolithography technique using semiconductors. However, the numerical aperture of the objective lens used for the production of the glass master N.P. A. (Numerical Aparture) is already near the practical limit of 0.9. Therefore, in order to increase the recording density of the optical disk, it is necessary to shorten the exposure wavelength. The resolution R is determined by setting the exposure wavelength to λ
Is represented by the following equation. Here, k is a process factor value depending on the resist characteristics and the like, and is 0.8 to 0.9.
Take the value of

R = k × λ / N The resolution R corresponds to the shortest pit length that can be formed. For example, when short-wavelength ultraviolet laser light having a wavelength of about 250 nm is used, the shortest pit length is 0.23 μm. That is, in this case, the shortest pit length as described above is 0.2
In order to manufacture an optical disk having a size of 20 μm and a capacity of 20 μm, the resolution is still slightly insufficient.

Further, a novolak-based resist, which is an ultraviolet-sensitive resist generally used in the past, is exposed to a laser beam of 300 nm or less as described above to form a pattern such as fine pits. Is extremely difficult. In novolak-based resists, the light absorption of phenol novolak resin, a base resin, and naphthoquinonediazide, a photosensitizer, increases at 300 nm or less. Therefore, when exposed to light having a wavelength of 300 nm or less, the transmittance decreases due to absorption inside the resist. Resulting in. In addition, the absorbed energy becomes heat and the resist is deteriorated. Therefore, 30% for novolak-based resist
When a laser beam having a wavelength of 0 nm or less is used, the contrast value for determining the resolving power is remarkably deteriorated, and pits with poor edge cutting and poor bottom formation are formed.

For the reasons described above, a novolak-based resist having a quinonediazide-based compound, which has been used for g-line and i-line exposure, cannot obtain a high resolution because it has a large absorption for light of 300 nm or less. Was.

However, this problem can be solved by using a chemically amplified resist having a high transmittance in the far ultraviolet region, and a high resolution is obtained. The chemically amplified resist comprises a base resin, an acid generator, and a protective group, and contains a dissolution inhibitor, a bridge agent, and the like as necessary. The reaction mechanism of a typical chemically amplified resist is shown in chemical formulas (1) to (3).

First, as shown in chemical formula (1), when a chemically amplified resist is exposed, an acid is generated from an acid generator (sulfonium salt).

[0011]

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Then, as shown in chemical formula (2), the acid generated by the exposure acts as a protecting group for the resist.
It serves as a catalyst for a reaction for removing a tert-butoxycarbonyl (hereinafter referred to as t-BOC) group.

[0013]

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As shown in the chemical formula (3), this acid exists as an acid even after the reaction for removing the protecting group, and may cause the elimination reaction of many t-BOC groups. it can.

[0015]

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Since the polyhydroxystyrene from which the t-BOC group acting as a protecting group has been eliminated is dissolved in an aqueous alkali solution, a positive pattern can be obtained by alkali development.
That is, this reaction is called a chemical amplification reaction because one acid can contribute to many reactions. Therefore, the sensitivity can be increased, and the amount of the acid generator added can be suppressed, so that the light transmittance in the far ultraviolet region is excellent.

FIG. 14 shows an example of a process for forming a pattern using a chemically amplified resist. First, in a resist coating step 101, a resist is coated on a substrate by, for example, a spin coating method. Next, pre-bake step 1
In 02, a heat treatment is performed on the resist applied on the substrate in the resist application step. Next, in an exposure step 103, the resist is exposed to form a latent image having a pattern indicating information. Next, in a PEB (Post Exposure Bake) step 104, the exposed resist is further subjected to a heat treatment.
Finally, in a developing step 105, a pattern indicating information is formed in a groove or pit shape by developing the resist using a developing solution.

[0018]

However, such a chemically amplified resist has a problem that its characteristics are easily affected by various environmental conditions in each step, and as a result, the pattern shape is changed.

If the pre-bake step is performed at a low temperature for a long time by the recirculation open used in the conventional production of a glass master, the properties of the resist often deteriorate. Also,
If the interval between processes is long, pattern formation may not be possible. This is because the acid is deactivated by impurities such as amines in the air and loses its ability as a catalyst. Conditions for pre-baking and PEB also vary depending on the composition of the chemically amplified resist. In an optical disc, since the pit shape and the steepness of the group greatly affect the jitter during reproduction, it is required to establish a condition with reproducibility.

In addition, the chemically amplified resist has a weak environmental resistance and is easily affected by working temperature, humidity, ammonia concentration and the like. In particular, an acetal-based chemically amplified resist having an acetal group as a protective group is sensitive to humidity, and the sensitivity is lowered at a low humidity of 20 ° C. and 20% or less, and deteriorates at a temperature of 20 ° C. and 70% or more. As a result, sensitivity decreases. In addition, there is also a problem in that the reaction is easily affected by a basic substance such as NH ₃ or NH ₄ ^+, and the acid H ⁺ contributing to the reaction in the resist is trapped by these and the reaction is stopped. For example, when the acid of the chemically amplified resist is inactivated by the basic substance, if the chemically amplified resist is a positive resist, the surface layer of the resist is not developed, so that the resist is called a T-top shape. An inverted tapered shape is formed. Therefore, it is necessary to control the atmosphere in the working environment.

Furthermore, it has been pointed out that the characteristics of the chemically amplified resist may be abnormal depending on the material and composition of the substrate used. Normally, soda lime glass used as a glass substrate for a glass master contains an alkali metal or an alkaline earth metal, so that the acid in the chemically amplified resist cannot react with these alkali metals or alkaline earth metals. This causes a problem that an exchange reaction occurs to stop the reaction.

Even when synthetic quartz glass containing no alkali metal or alkaline earth metal is used, the acid is easily deactivated when an acetal-based chemically amplified resist is used.
The sensitivity decreases. As a result of the decrease in the sensitivity of the resist, there is a problem that even if exposure or development is performed, the quality is changed by about 10 nm from the interface with the glass substrate, and the resist tends to remain.

When a metal film made of, for example, nickel or the like is formed on the glass master and the nickel film is peeled off to form a master for manufacturing a recording medium, the altered resist as described above becomes It adheres to the master. Therefore, it is necessary to remove organic substances such as a deteriorated resist adhered to the master for producing the recording medium.

Conventionally, organic substances adhering to a master for producing a recording medium are dissolved in a polar organic solvent such as acetone or ethanol, or an inorganic or organic alkaline solution, and further washed and removed with pure water. However, what can be washed and removed with an organic solvent or an alkaline solution as described above is limited to the case where a so-called novolak-based resist using a phenol novolak resin as a base resin and a naphthoquinonediazide as a photosensitive agent is used. Examples of the novolak-based resist include GX250ELS (manufactured by Nippon Synthetic Rubber) and OFPR77 (manufactured by Tokyo Ohka).

However, when a chemically amplified resist, on which an acid is generated by exposure and the acid acts as a catalyst, adheres to a master for producing a recording medium, the resist is removed with an organic solvent or an inorganic or organic alkaline solution as described above. A problem arises in that it cannot be performed.

Such a problem is caused by the following process. When a nickel film is formed by sputtering on a pattern formed by a chemically amplified resist, the chemically amplified resist at the interface that comes into contact with nickel is altered by electric discharge, and the chemically amplified resist itself takes a three-dimensional network structure. The reason for this is that the molecular weight increases and the compound does not dissolve in a polar solvent. The main component of such a chemically amplified resist is composed of polyhydroxystyrene, and among them, those containing an acetal in particular have a low glass transition point and tend to have poor heat resistance. One of them.

In the semiconductor process, a method of removing a photoresist by using oxygen plasma ashing is adopted. In this oxygen plasma ashing, oxygen (O ₂ ) is changed to ozone (O ₃ ) by plasma, and the ozone is further decomposed into excited oxygen atoms (O ^* ). Then, organic substances such as photoresist are converted to carbon dioxide (CO ₂ ) or water (H) by excited oxygen atoms having extremely strong oxidizing power.
It decomposes into volatile substances such as ₂ O) and volatilizes and removes them.

As described above, it is conceivable to volatilize and remove the chemically amplified resist adhering to the recording medium manufacturing master by oxygen plasma ashing.

However, since most of the oxygen is changed to ozone by the plasma, the decomposition and removal rates of the resist become extremely high. Further, the removal rate further increases due to the rise in the temperature of the substrate. It is difficult to control the removal rate of the resist. There is also a problem that the recording medium manufacturing master is damaged by the plasma. It is not appropriate to remove the resist by an oxygen plasma ashing method, which is difficult to finely control, because the roughness of the resist surface is directly reflected on the surface of the master and becomes one of the causes of jitter deterioration of the optical disk.

As described above, there is a need for a method of manufacturing a master for producing a recording medium using an exposure source that achieves high resolution.

Also, a chemically amplified resist in which an acid is generated by exposure and the acid acts as a catalyst, or an electron beam resist in which electrons incident on the resist cause the formation or collapse of constituent molecules of the resist. It is required to define various conditions for producing a master for recording medium production stably.

Further, there are problems in any of the method of removing the deteriorated resist on the master for producing the recording medium by wet treatment using an organic solvent, an inorganic or organic alkali solution, and the like, and the method of removing the resist by oxygen plasma ashing. There is a need for a method of removing the deteriorated resist attached to a recording medium manufacturing master without damaging the recording medium manufacturing master.

Accordingly, the present invention has been proposed in view of such a conventional situation, and uses an exposure source for realizing a high resolution, defines a resist process condition adapted to the exposure source, and defines an original master. Organic matter attached on top
An object of the present invention is to provide a method of manufacturing a master for manufacturing a recording medium capable of manufacturing a recording medium capable of coping with high recording density and high recording capacity by removing the master without damaging the master.

[0034]

According to the present invention, there is provided a method of manufacturing a master for a recording medium, comprising the steps of: applying a resist on a glass substrate; and applying the resist to the glass substrate coated with the resist in the resist applying step. A heat treatment step of performing a heat treatment, and exposing the resist on the glass substrate that has been subjected to the heat treatment in the heat treatment step, using an exposure beam including any of a laser beam, an electron beam, an X-ray, and an ion beam. An exposure step of forming a latent image of a pattern indicating information, a developing step of developing the resist exposed in the exposure step using a developer to form a pattern indicating information, and forming a pattern by the developing step A metal film forming step of forming a metal film on the surface of the glass substrate, a separating step of separating the metal film formed in the metal film forming step from the glass substrate, A cleaning step of cleaning an organic matter attached to the metal film which is peeled from the plate in a solvent, by irradiating ultraviolet light to the metal film that has been cleaned by the cleaning step,
An ultraviolet irradiation step of decomposing and removing organic substances remaining on the metal film.

In the above-described method for manufacturing a master for producing a recording medium according to the present invention, since the resist applied to the glass substrate in the heat treatment step is subjected to the heat treatment, the sensitivity of the resist is improved. In the method for manufacturing a master for manufacturing a recording medium according to the present invention, in the exposure step, the resist is exposed using an exposure beam composed of any one of a laser beam, an electron beam, an X-ray, and an ion beam, and a pattern indicating information is exposed. Is formed, and the pattern is formed by developing with a developing solution in a developing step, so that a fine pattern is formed.
Then, a metal film is formed on the surface of the glass substrate on which the pattern has been formed in the metal film formation step, and the metal film is separated from the glass substrate in the separation step, whereby the pattern on the glass substrate is copied to the metal film. Can be Further, in the method for producing a master for recording medium production according to the present invention, the organic matter attached to the metal film is washed in a washing step, and further in the ultraviolet irradiation step,
Since the organic matter remaining on the metal film is decomposed and removed by irradiating the metal film with ultraviolet light, the organic matter remaining on the metal film is removed without damaging the metal film.

[0036]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, specific embodiments of the present invention will be described.

FIG. 1 shows a process chart of a method for producing a master for producing a recording medium according to the present invention. The method of manufacturing a recording medium manufacturing master includes a surface treatment step 1 and a resist coating step 2
Heat treatment step 3, exposure step 4, development step 5,
Conducting treatment step 6, plating step 7, peeling step 8,
A cleaning step 9 and an ultraviolet irradiation step 10 are provided.

Hereinafter, each step will be described with reference to FIGS.

In the surface treatment step 1, as shown in FIG.
First, a disk-shaped glass substrate 11 having a thickness of about several mm is prepared, and the surface of the glass substrate 11 is polished. And C
Using r, Ni, or hexamethyldisilazane, the surface of the glass substrate 11 is subjected to a surface treatment.

As the glass substrate 11, synthetic quartz glass or non-alkali glass is used. Synthetic quartz glass can be prepared by two methods: direct method and Vapor ph.
case Axial Deposition method (hereinafter, referred to as
It is called VAD method. ).

Glass substrate 11 manufactured by direct method
Has the advantage of low cost, but cannot control the concentration of hydroxyl groups, and has a hydroxyl group concentration of about 800 ppm to 1 ppm.
Present at 200 ppm. Also, there is an in-plane distribution of the hydroxyl group concentration, and the hydroxyl group concentration is high in the inner and outer peripheral portions. There is also about 100 ppm of chloride ions.

On the other hand, the glass produced by the VAD method has a hydroxyl group concentration of about 1 ppm to 400 ppm or less, and this value can be controlled to about ± 10%. Chloride ion is about 1 ppm or less, which is a very excellent synthetic quartz.

Table 1 shows the concentrations (ppm) of metal elements contained in the synthetic quartz glass produced by the VAD method and the direct method and in the fused quartz glass produced by the electric melting method.

[0044]

[Table 1]

The raw material of the synthetic quartz glass is silicon chloride such as SiCl ₄ or SiCl ₂ distilled and purified to a high purity, does not contain alkali metal ions having a large diffusion coefficient in the glass, and has no contamination in the production process. Therefore, the impurity metal ion content is 1 ppm or less. The concentration of hydroxyl groups incorporated into the glass in the vapor phase synthesis step is lower in the VAD method than in the direct method. This is because in the VAD method, densification is performed in an atmosphere containing no moisture. In the VAD method, the sintering condition is controlled to reduce the hydroxyl group concentration to one.
It can be adjusted to a wide range from less than 500 ppm to 500 ppm, and can be said to be an optimal substrate manufacturing method for a chemically amplified resist.

On the glass substrate 11, a chemically amplified resist is applied. This chemically amplified resist is sensitive to the environment and is very susceptible to the concentration of alkali metals and hydroxyl groups present on the surface of the glass substrate 11. Therefore, by performing a surface treatment on the glass substrate 11, the influence on the chemically amplified resist applied on the glass substrate 11 can be suppressed, and the adhesion between the glass substrate 11 and the chemically amplified resist can be increased. .

When a synthetic quartz glass substrate having a hydroxyl group concentration of 400 ppm or less produced by the VAD method is used as the glass substrate 11, Cr or Ni is formed on the surface of the glass substrate 11 or hexamethyldisilazane is used. Apply or heat steam treatment. Cr on the surface of the glass substrate 11
Alternatively, in the case of forming a film of Ni, a thin film is preferable because a large film thickness deteriorates surface properties. When using a synthetic quartz glass substrate having a hydroxyl group concentration of 400 ppm or less manufactured by the VAD method, the effect of hydroxyl groups can be suppressed even when the film thickness of Cr or Ni is small, so that the film thickness of Cr or Ni is 1 nm or less. It is preferable to set the degree.

Further, as the glass substrate 11, a non-alkali glass substrate or a hydroxyl group concentration of 40 produced by a direct method is used.
Similarly, when using a synthetic quartz glass substrate of 0 ppm or more, a film of Cr or Ni is formed on the surface of the glass substrate 11, or hexamethyldisilazane is applied or heated and steamed. However, the glass substrate 11 has a non-alkali glass or a hydroxyl concentration of 400 pp manufactured by a direct method.
When synthetic quartz glass having a thickness of at least m is used, the influence of an alkali metal or a hydroxyl group present on the surface of the glass substrate 11 is large.
The effect of alkali metals and hydroxyl groups on the surface cannot be suppressed. Therefore, when using a non-alkali glass substrate or a synthetic quartz glass substrate having a hydroxyl concentration of 400 ppm or more produced by a direct method, the film thickness is about 10 nm.
It is preferable to form Cr or Ni so as to form the above.

Next, in the resist coating step 2, as shown in FIG. 3, a chemically amplified resist 12 is coated on the glass substrate 11 which has been subjected to the surface treatment as described above.

The chemically amplified resist 12 generally comprises a polymer having polyhydroxystyrene as a main skeleton and a compound which generates an acid upon exposure. And
The polyhydroxystyrene has a phenolic hydroxyl group masked by an acid-decomposable protecting group. The protective group masks the phenolic hydroxyl group, thereby reducing the dissolution rate of the polyhydroxystyrene in the alkaline developer. Such a chemically amplified resist 12
Depends on the species used as a protecting group,
Butoxycarbonyloxystyrene, a chemically amplified resist of a high temperature bake type, and a chemically amplified resist of an acetal type or a ketal type are roughly classified into three types.

First, poly-tert-butoxycarbonyloxystyrene (hereinafter, referred to as PBOCST) protects the hydroxyl group of polyhydroxystyrene with a tert-butoxycarbonyl group (t-BOC) as shown in chemical formula (4). This is a chemically amplified resist.

[0052]

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The high temperature bake type chemically amplified resist is a chemically amplified type resist in which the hydroxyl group of polyhydroxystyrene is protected by a tert-butyl ester type protecting group as shown in the chemical formula (5). .

[0054]

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Further, as shown in the chemical formula (6), an acetal-based or ketal-based chemically amplified resist is a chemically amplified resist obtained by protecting the hydroxyl group of polyhydroxystyrene with an acetal-based or ketal-based protecting group. It is.

[0056]

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Such a chemically amplified resist exhibits high transmittance even at a short wavelength, and has characteristics of high sensitivity and high resolution.

However, the chemically amplified resist is very easily influenced by the surrounding environment and affects the pattern shape. For example, when exposure and development are performed at a relative humidity of 80% or more, since many hydroxyl groups are attached to the glass substrate 11 before resist application, the acid serving as a catalyst reacts with the hydroxyl groups and is lost. I will live. Therefore, the sensitivity of the chemically amplified resist is reduced. As a result of the decrease in the sensitivity of the chemically amplified resist, the edge roughness of the pits to be formed increases, and the bottoming out becomes poor.

In addition to the hydroxyl group, a basic substance such as ammonia can be used as a substance for deactivating the acid. 2-Methylpropanolamine, which is used for controlling the humidity of a clean room, also causes acid deactivation. As described above, since the characteristics of the chemically amplified resist are extremely affected by the environment, it is necessary to pay attention to the surface condition of the glass substrate 11 and the surrounding environment.

Among the above three types of chemically amplified resists, a high temperature bake type chemically amplified resist represented by chemical formula (5), wherein the hydroxyl group of polyhydroxystyrene is protected by a tert-butyl ester type protecting group. Is a chemically amplified resist that is highly resistant to the effects of basic substances and is not easily affected by temperature, and is extremely excellent in environmental resistance.

In the resist coating step 2, such a chemically amplified resist 12 is uniformly coated on the glass substrate 11 by, for example, a spin coating method. At this time, the chemically amplified resist 12 may be diluted with a solvent. The thickness of the chemically amplified resist 12 is, for example, about 100 nm to
It is about 200 nm.

Next, in the heat treatment step 3, the glass substrate 11 coated with the chemically amplified resist 12 is subjected to heat treatment by a hot plate method, that is, pre-baking. By performing the pre-bake, the solvent contained as a diluent in the chemically amplified resist 12 is removed, and the sensitivity of the resist is increased.

The remaining amount of the solvent contained in the chemically amplified resist 12 varies depending on the prebaking temperature and time. If the remaining amount of the solvent is different, the diffusion coefficient of the acid is different, so that the sensitivity is changed and the dimension of the pattern is changed. Therefore, it is necessary to set conditions such as the prebaking temperature and time.

When a so-called high-temperature bake type chemically amplified resist containing polyhydroxystyrene as a skeleton and further containing a tert-butyl ester group as shown in the chemical formula (5) is used, the resist is used at 100 ° C. or more and 160 ° C. It is preferable to perform the heat treatment by a hot plate method at the following temperature for 5 minutes to 20 minutes.

Further, as shown in chemical formula (6), polyhydroxystyrene is used as a skeleton, and at least one of an acetal group and an alkoxy group is contained.
When a so-called acetal-based chemically amplified resist is used, it is preferable to heat-treat the resist by a hot plate method at a temperature of 80 ° C. or more and 120 ° C. or less for 5 minutes or more and 20 minutes or less.

If the prebaking temperature is too low or the time is too short, the solvent contained in the chemically amplified resist 12 cannot be sufficiently removed, and
Sensitivity cannot be increased. If the pre-baking temperature is too high or the time is too long, the resist is denatured by heat. By setting the pre-bake conditions as described above, the solvent contained in the chemically amplified resist 12 can be removed without denaturing the chemically amplified resist 12, and the sensitivity of the resist can be increased.

Next, in the exposure step 4, as shown in FIG. 4, a laser beam having a wavelength of 300 nm or less, an electron beam, an X-ray,
A latent image 12a having a pattern indicating information is formed by spot exposure of any one of the ion beams on the chemically amplified resist 12 on the glass substrate 11.

FIG. 10 is a diagram conceptually showing the configuration of a laser light exposure apparatus that performs exposure using laser light having a wavelength of 300 nm or less. The laser beam exposure apparatus 20 includes a light source 21, mirrors 22 and 23, a lens 24, an acousto-optic element 25, a lens 26, and a beam expander 27.
, A mirror 28, and an objective lens 29.

When exposing a resist using such a laser beam exposure apparatus 20, a laser beam 30 is first emitted from a light source 21. The laser beam 30 emitted from the light source 21 is incident on the acousto-optic element 25 via the lens 4 while its traveling direction is changed by the mirrors 22 and 23. The laser beam 30 incident on the acousto-optic device 25 is
The pulse is modulated by the digital signal by the acousto-optic element 25. Laser light 3 modulated by acousto-optic device 25
In the case of 0, the beam diameter is increased by the beam expander 27 via the lens 26. The laser beam 30 whose beam diameter has been increased by the beam expander 27 is changed in its traveling direction by a mirror 28 and is condensed by an objective lens 29 to be condensed by the glass substrate 1.
Irradiated on 1 The laser light 30 irradiated on the glass substrate 11 exposes the chemically amplified resist 12 applied on the glass substrate 11 to form a latent image 12 having a pattern indicating information.
a is formed.

At this time, the numerical aperture of the objective lens 29 is set to, for example, 0.9, and the spot diameter of the laser beam irradiated on the glass substrate 11 is set to 0.25 μm or less. Specifically, for example, Nd: YAG (Yt
trium aluminum garnet)
Its wavelength is 266 nm and the spot diameter is about 0.23.
μm.

FIG. 11 is a diagram conceptually showing the structure of an electron beam exposure apparatus for performing exposure using an electron beam. The electron beam exposure apparatus 40 is roughly divided into an electron beam emitting section 41, a mechanism section 42, and a control section (not shown).

The electron beam emitting section 41 includes an electron gun 43,
A condenser lens 44, a blanking electrode 45, an aperture 46, a beam deflection electrode 47, a focus adjustment lens 48, and an objective lens 49 are housed in a lens barrel 50. The mechanism unit 52 includes a parallel movement mechanism 51 and a rotation movement mechanism 52, a stage on which the glass substrate 11 is mounted, and a machine (not shown) for loading the glass substrate 11 into an apparatus and moving the glass substrate 11 to an exposure position. The system is housed in the housing 53. The control unit includes a control circuit or a computer that generates a pattern while correcting a position error or the like in accordance with the pattern data. The electron beam emitting section 41 and the mechanism section 4
2 is provided on the vibration isolation table 54.

When exposing a resist using such an electron beam exposure apparatus 40, first, an electron beam 55 is emitted from the electron gun 43. The electron beam 55 emitted from the electron gun 43 is deflected by the blanking electrode 45 via the condenser lens 44. Among the electron beams 55 deflected by the blanking electrode 45, the electron beam 55 that has passed through the aperture 46 is wobbled by the beam deflection electrode 47. Then, the aperture of the electron beam 55 is adjusted by the focus adjustment lens 48, and the electron beam 55 is focused by the objective lens 49 and irradiated onto the glass substrate 11. The electron beam 55 irradiated on the glass substrate 11 exposes the chemically amplified resist applied on the glass substrate 11 to form a latent image having a pattern indicating information.

At this time, it is preferable that the inside of the lens barrel 50 and the housing 53 be kept at about 10 ⁻⁴ Pa or less by a vacuum exhaust device (not shown). If the pressure is higher than 10 ⁻⁴ Pa, electrons collide with particles in the air and are scattered.

As described above, since the exposure using the electron beam is performed in a high vacuum, the amount of the residual solvent in the chemically amplified resist varies depending on the vacuum holding time of the glass substrate 11.
As a result, the sensitivity differs depending on the time until the exposure is performed. Since the cutting time of a glass master having a capacity of 30 GB or more is several hours or more, a sensitivity difference occurs and a pattern dimension difference occurs. In order to avoid this, it is preferable to hold the glass substrate 11 in a vacuum for a certain period of time and wait until the amount of residual solvent in the resist becomes constant.

As described above, by performing exposure using an electron beam, the resolution can be improved to about 0.01 μm to 0.1 μm. When exposure is performed using a focused ion beam, the resolution can be increased to about 0.1 μm. When exposure is performed using X-rays,
It is possible to narrow the exposure size to 0.01 μm or less.

Next, in a developing step 5, as shown in FIG. 5, the exposed chemically amplified resist 12 is developed with an organic alkali developing solution to form a pit or group pattern 13 indicating information.

The chemically amplified resist 12 is a so-called acetal type chemical having a polyhydroxystyrene skeleton as shown in chemical formula (6) and further containing at least one of an acetal group and an alkoxy group. When an amplified resist is used, after exposure and before development, a temperature of 80 ° C. or more and 120 ° C. or less is used.
It is preferable to perform the heat treatment by a hot plate method under the conditions of not less than 20 minutes and not more than 20 minutes.

As the organic alkali developer, for example, an organic alkali developer containing tetramethylammonium hydride (hereinafter referred to as TMAH) is used. At this time, the concentration of TMAH ranges from 0.17 mol / l to 0.1.
Preferably it is 26 mol / l. When development is performed with an organic alkali developer having a TMAH concentration of 0.17 mol / l or less, a residue (scum) of the resist at the bottom of the exposed portion is generated. Moreover, the concentration of TMAH is 0.26mo.
When development is performed with an organic alkali developing solution of l / l or more, the edge of the resist film becomes severe, it is difficult to obtain contrast, and the surface of the resist is roughened, which is one of the causes of deterioration in jitter during reproduction of the optical disk. Therefore, by setting the concentration of TMAH to 0.17 mol / l to 0.26 mol / l, the remaining of the resist does not occur, and
The resist can be developed without roughening the resist surface.

In the above steps, as shown in FIG. 5, a pattern 13 indicating information is formed on the glass substrate 11 in the form of pits or grooves, and a glass master 14 is manufactured.

A series of steps of the above-described resist coating step 2, exposure step 4, and development step 5 and the step of storing the glass substrate 11 when moving from one step to the next step are performed at a temperature of 15 ° C. ~ 25 ° C, humidity 40% ~ 60%,
It is preferable to perform the reaction in an environment that satisfies the conditions that the ammonium ion concentration is 10 ppb or less and the 2-methylpropanolamine concentration is 5 ppb or less.

The chemically amplified resist is very sensitive to the environment. If the temperature is too low, the reaction speed of the resist during exposure and development is reduced. On the other hand, if the temperature is too high, the reaction speed of the resist during exposure and development becomes too high, so that control cannot be performed and the resist may be deteriorated. On the other hand, if the humidity is too high, the acid in the chemically amplified resist 12 becomes less than O in the water molecule.
It reacts with H and is inactivated. On the other hand, if the humidity is too low, the resist deteriorates, and the sensitivity also decreases.
The acid in the chemically amplified resist 12 is also deactivated by a basic substance such as ammonium ion or 2-methylpropanolamine.

Accordingly, by performing a series of steps for manufacturing the glass master 14 under the above-described conditions, the sensitivity of the resist can be increased and a finer pattern can be formed.

Next, a nickel film is formed on the glass master disk 14 and the nickel film is peeled off to produce a recording medium manufacturing master disk in which pits and grooves indicating information are formed in an inverted manner.

First, in the conductorization treatment step 6, as shown in FIG. 6, about 50 nm to 100 nm of nickel 15 is deposited or formed on the surface of the glass master 14 by nickel sputtering or electroless nickel plating.
The surface of is made conductive. However, when an acetal-based chemically amplified resist is used when producing the glass master 14, electroless plating cannot be performed because the amount of hydroxyl groups existing on the surface is small. Therefore, when the glass master 14 is manufactured using an acetal-based chemically amplified resist, the surface of the glass master 14 is made conductive by nickel sputtering.

Next, in the plating step 7, as shown in FIG. 7, the glass master 1
4 is electroplated with nickel and has a thickness of about 300μm
Is formed. Then, the nickel film 16 is subjected to predetermined processing such as back surface polishing and end face processing.

Then, in a peeling step 8, the nickel film 16 is peeled from the glass master 14 to obtain a recording medium manufacturing master 17 as a replica of the glass master 14 as shown in FIG.

Here, on the surface of the master 17 for recording medium peeled off from the glass master 14 that was in contact with the glass master 14, an organic material such as the chemically amplified resist used for manufacturing the glass master 14 was used. 18 are attached with a thickness of about 0.1 μm. Therefore, these deposits must be removed.

If the resist used for manufacturing the glass master is a novolak-based resist usually used for manufacturing an optical disk, an organic solvent such as acetone is dropped while the peeled recording medium manufacturing master is rotated. By washing, almost all organic substances adhering to the master for producing a recording medium can be removed. This is limited to the case where electroless plating is used for the conductive treatment in the process of preparing the master for producing the recording medium.
However, in the case where sputtering is used in the conductive process, the resist in contact with the interface with the nickel film is about 2 to 3 times.
nm, and cannot be completely removed by the above-mentioned organic solvent washing. However, the novolak-based resist thus modified can be removed by heating an organic solvent or an organic alkali solution and further performing ultrasonic cleaning.

Similarly, in the case where a chemically amplified resist is used for the production of the glass master 14, first, in the washing step 9, the recording medium manufacturing master 17 is prepared using an organic solvent or an alkaline solution.
Is washed to remove organic substances attached to the recording medium manufacturing master 17.

At this time, it is preferable that the organic solvent or the alkaline solution used for washing is kept at 20 ° C. or higher. If the temperature is lower than 20 ° C., the cleaning power is not sufficient. In addition, by heating the washing solvent, the washing and removal rates are improved. When an organic solvent such as acetone or hexane is used, the temperature of the solvent is up to about 60 ° C., and when an organic alkali solution such as monoethanolamine is used, the temperature of the solvent is up to about 130 ° C.

The organic solvent and the alkaline solution used as the washing solvent have high volatility, and must be carried out in a place equipped with an exhaust system. Further, it is preferable to perform ultrasonic cleaning on the master 17 for producing a recording medium. By performing ultrasonic cleaning, cleaning can be performed efficiently.

However, when a chemically amplified resist is used for producing the glass master 14, the altered resist thickness, that is, the negative resist thickness is different from the novolak-based resist. Of the altered resist having a thickness of 100 nm, the altered resist having a thickness of about 50 nm to 70 nm can be removed using an organic solvent such as acetone.
Degraded resist of a certain degree can hardly be removed with an organic solvent or an organic alkali solution even after ultrasonic cleaning or heating. There is the problem that the removal is very time-consuming and that there is also a risk of redeposition during cleaning.

The residual thickness of the acetal-based chemically amplified resist is about 30 nm to 50 nm. This is because the resist is three-dimensionally formed due to the plasma or temperature during nickel sputtering, the molecular weight is increased, and the remaining residue is generated. It seems to be because.

When the organic substance 18 on the recording medium manufacturing master 17 is removed, it is an essential condition that the recording medium manufacturing master 17 is not damaged. This is because if the surface is roughened by erosion of nickel, the jitter at the time of reproducing the disc is deteriorated. Therefore, the altered resist cannot be removed using an acid-based stripping solution.

Therefore, in order to remove the altered resist, in the ultraviolet irradiation step 10, a wavelength of 254 nm, 185 nm,
Irradiation with 22-nm or 172-nm far ultraviolet rays is performed, and an organic substance is removed by an ashing method in which CO ₂ and H ₂ O are converted.

First, ozone (O ₃ ) is generated by irradiating oxygen (O ₂ ) with far ultraviolet rays. Ozone is unstable and decomposes into oxygen (O ₂ ) and excited oxygen (O ^* ). This excited oxygen (O ^* ) has a very strong oxidizing power, and dissociates organic substances into C—C bonds and the like in the molecule, thereby generating volatile substances such as carbon dioxide (CO ₂ ) and water (H ₂ O). Volatile removal by decomposition.

Such a far-ultraviolet dry surface modification (cleaning)
As a light source of the apparatus, it is preferable to use at least one of a low-pressure mercury lamp having a wavelength of 254 nm and 185 nm, an excimer lamp having a wavelength of 172 nm, and an excimer lamp having a wavelength of 222 nm.

For example, a low-pressure mercury lamp of 254 nm, 1
The emission energy at 85 nm is 471 kJ / m.
ol, 647 kJ / mol. On the other hand, a typical chemical bond energy of an organic substance is that a C—C bond is 348 kJ /
mol, the C = C bond is 608 kJ / mol, the CH bond is 415 kJ / mol, and the C = O bond is 725 kJ / mol. Therefore, it can be seen that far-ultraviolet light is very effective in breaking typical chemical bonds of organic substances.

If the irradiation intensity of the light source is uneven, the removal speed of the resist differs on the recording medium manufacturing master 17. Where the removal rate is high, after the resist is removed, the recording medium manufacturing master 17 is also damaged, and the surface is oxidized and roughened. In order to avoid such a situation, it is preferable to use a light source that can irradiate far ultraviolet rays so that the in-plane distribution of the integrated light amount with respect to a master for manufacturing a recording medium having a diameter of 220 mm is within ± 15%.

As described above, in the method of removing the resist on the recording medium manufacturing master 17 by irradiating far ultraviolet rays, the rate of removing organic substances can be controlled by adjusting the supply amount of ozone, and damage to the master surface is small. FIG. 12 shows how the roughness of the surface of the master for recording medium production changes due to the irradiation of far ultraviolet rays. The vertical axis indicates the surface roughness of the master for producing a recording medium, and the horizontal axis indicates the irradiation time of far ultraviolet rays. At this time, the intensity of far ultraviolet light is 6 mW / cm ² at 254 nm. An initial master for manufacturing a recording medium is an original master on which no altered resist is deposited. Even if irradiation with far ultraviolet rays is continued for 15 minutes, the surface roughness of the master is increased only by about 10%, and the jitter during reproduction is not affected. The irradiation time margin is wide, the light illuminance unevenness of the far ultraviolet device is suppressed to about ± 7%, the far ultraviolet can be uniformly irradiated over the entire surface, and the master disk cleaning method by the far ultraviolet irradiation is very effective. You can see that.

Before the irradiation with the far ultraviolet rays, the thickness of the residual organic matter such as the resist on the recording medium manufacturing master 17 remaining by washing with an organic solvent or an alkaline solution is determined.
It is preferable to measure in advance by at least one of an ultraviolet-visible spectrophotometer, an ellipsometer, and a level difference measuring device, and adjust the irradiation amount of far ultraviolet rays. Master 17 for recording medium production
By measuring the thickness of the above-mentioned residual organic matter in advance and setting a standard for the irradiation amount of far ultraviolet rays, damage to the recording medium manufacturing master 17 caused by the irradiation of far ultraviolet rays can be minimized.

Through the above steps, a master 17 for recording medium production used for producing an optical disk as shown in FIG. 9 is completed.

In the above-described method for producing a master for producing a recording medium, a case where a chemically amplified resist in which an acid is generated by exposure and the acid acts as a catalyst is used as the photosensitive resist will be described as an example. However, the present invention is not limited to this, and can be applied to a case where an electron beam resist is used. Here, the electron beam resist means that the polymer constituting the resist receives energy by collision with electrons, and a part of the chain of the polymer is cut to reduce the molecular weight or to bond with another polymer. Polymerized into a high molecular weight polymer.

In the following experimental examples, masters for manufacturing optical disks were manufactured by changing the conditions for manufacturing masters for manufacturing recording media.

<Experimental Example 1> Cr was deposited to a thickness of about 1 nm by sputtering on a synthetic quartz glass having a hydroxyl group concentration of 400 ppm or less produced by the VAD method, and a chemically amplified resist was applied. Next, the chemically amplified resist was exposed to laser light having a wavelength of 266 nm,
Paddle development was performed for 15 seconds using an organic alkali developer having an AH concentration of 0.22 mol / l.

As a result, there was no remaining resist left in the exposed area, and good results were obtained for the bottoming out. This also improved the reproduction signal jitter from 11% to 9.5% on a 12 GB density optical disc.

<Experimental Example 2> Hexamethyldisilazane was applied to the surface of a glass substrate made of a synthetic quartz glass manufactured by a direct method and treated, and an acetal-based chemically amplified resist was applied. The substrate was exposed to light and subjected to paddle development for 15 seconds using an organic alkali solution having a TMAH concentration of 0.22 mol / l. The result obtained was that no remaining resist was observed in the exposed area.

<Experimental Example 3> When a glass master was produced using an acetal-based chemically amplified resist, edge roughness was improved by introducing an alkoxy group into the resist, and jitter of a 12 GB density optical disc reproduction signal was reduced. Could be improved.

<Experimental Example 4> A glass master was formed using an acetal-based chemically amplified resist. At this time, a series of steps were performed when the ammonium ion concentration was 10 ppb or less.
The test was performed in an environment that satisfies the conditions of a methylpropanolamine concentration of 5 ppb or less, a temperature of 15 ° C to 25 ° C, and a humidity of 40% to 60%.

At this time, before the development, PEB is applied to the glass substrate 11 on which the pattern latent image has been formed in the exposure step.
However, even if the pattern was left for 3 hours as an interval between the exposure step and the PEB step, there was no difference in pattern shape, and a pattern could be formed with good reproducibility.

<Experimental Example 5> An altered resist having a thickness of 0.1 μm was adhered to a master for recording medium peeling from a glass master. The master was washed with acetone, and the thickness of the altered resist that could not be removed by washing with an organic solvent was measured using an ellipsometer to be about 0.03 μm.

Then, a deep ultraviolet ray dry type surface modification (cleaning) device (UVOcleane, manufactured by technovision)
Using r), the recording medium production master was irradiated with far ultraviolet rays having wavelengths of 254 nm and 185 nm. The irradiation intensity of far ultraviolet rays having a wavelength of 254 nm was 6 mW / cm ² . FIG. 1 shows the relationship between the deep ultraviolet irradiation time and the altered resist thickness at this time.
3 is shown. By irradiating far ultraviolet rays for 10 minutes,
Deposits of 0.03 μm could be removed.

Further, TDUR-P is used for the chemically amplified resist.
When 009 (manufactured by Tokyo Ohka) is used, the removal rate is about 3 n
m / min. By using this method, the altered resist could be completely removed without damaging the base, and a master for recording medium production could be manufactured.

Further, the master for producing a recording medium to which the chemically amplified resist of 0.1 μm was adhered was first washed with acetone and irradiated with far ultraviolet rays for further 8 minutes. Finally, the master for the production of the recording medium was
% Of an aqueous solution, heated to 100 ° C., and sonicated to remove organic substances attached to the master for producing a recording medium.

<Experimental Example 6> Dry UV-based surface modification (cleaning) device for unevenness in light intensity of ± 7% using a low-pressure mercury lamp on a master for producing a recording medium having a diameter of 220 nm (technique)
By irradiating far ultraviolet rays with UVO Cleaner (manufactured by Novision), it was possible to uniformly produce a master for producing a recording medium with very little surface roughness over the entire surface.

[0117]

According to the method for producing a master for producing a recording medium of the present invention, since the surface treatment is performed on the glass substrate, the resist applied on the glass substrate can be stably held without lowering the sensitivity. And a pattern having no change in shape can be formed stably.

In the method of manufacturing a master for manufacturing a recording medium according to the present invention, since the resist applied on the glass substrate is subjected to the heat treatment, the sensitivity of the resist is improved and a pattern having no edge roughness is formed. be able to.

In the method of manufacturing a master for manufacturing a recording medium according to the present invention, since at least one of a laser beam, an electron beam, an X-ray and an ion beam is used as an exposure source, a fine pattern can be formed. Can be.

Further, in the method for manufacturing a master for recording medium production according to the present invention, the organic substance adhering to the master for recording medium production is
Since it is decomposed and removed by irradiating far ultraviolet rays, it is possible to stably provide a recording medium manufacturing master having excellent surface properties without damaging the master.

Therefore, according to the method of manufacturing a master for producing a recording medium of the present invention, a fine pattern can be formed stably, and a master for producing a recording medium compatible with high recording density can be realized.

[Brief description of the drawings]

FIG. 1 is a process chart showing a method for producing a master for producing a recording medium according to the present invention.

FIG. 2 is a diagram illustrating a method of manufacturing a master for manufacturing a recording medium, and is a cross-sectional view illustrating a state where a glass substrate is prepared.

FIG. 3 is a view for explaining a method of manufacturing a master for manufacturing a recording medium, and is a cross-sectional view showing a state where a chemically amplified resist is applied on a glass substrate.

FIG. 4 is a diagram for explaining a method of manufacturing a master for manufacturing a recording medium, and is a cross-sectional view showing a state where a chemically amplified resist is exposed to form a pattern latent image.

FIG. 5 is a cross-sectional view for explaining a method of manufacturing a master for producing a recording medium, and showing a state in which a pattern is formed by developing a chemically amplified resist.

FIG. 6 is a cross-sectional view illustrating a method for manufacturing a recording medium manufacturing master, and showing a state where the surface of the glass master is made conductive.

FIG. 7 is a cross-sectional view illustrating a method for manufacturing a master for producing a recording medium, which is a state in which a nickel film is formed on a glass master.

FIG. 8 is a cross-sectional view illustrating a method of manufacturing a master for recording medium manufacture, showing a state where a nickel film is peeled off from a glass master.

FIG. 9 is a cross-sectional view illustrating a method for manufacturing a recording medium manufacturing master, and showing a state where organic substances attached to the recording medium manufacturing master are removed.

FIG. 10 is a conceptual diagram illustrating an example of a laser light exposure apparatus.

FIG. 11 is a conceptual diagram illustrating an example of an electron beam exposure apparatus.

FIG. 12 is a diagram showing a relationship between irradiation time of far ultraviolet rays and roughness of a surface of a master for producing a recording medium.

FIG. 13 is a diagram showing a relationship between irradiation time of far ultraviolet rays and thickness of a deteriorated resist.

FIG. 14 is a process chart showing a conventional method for forming a pattern on a glass master.

[Explanation of symbols]

11 glass substrate, 12 chemically amplified resist, 1
4 glass master, 16 nickel film, 17 master for recording media production

Claims (28)

[Claims] A resist application step of applying a resist on the glass substrate; a heat treatment step of performing a heat treatment on the glass substrate coated with the resist in the resist application step; and a heat treatment in the heat treatment step. Exposing the resist on the applied glass substrate using an exposure beam composed of any one of a laser beam, an electron beam, an X-ray, and an ion beam to form a latent image having a pattern indicating information; A developing step of developing the resist exposed in the step using a developing solution to form a pattern indicating information, and a metal film forming step of forming a metal film on the surface of the glass substrate on which the pattern is formed in the developing step And a peeling step of peeling the metal film formed in the metal film forming step from the glass substrate; and washing a solvent with an organic substance attached to the metal film peeled from the glass substrate in the peeling step. A recording step, comprising irradiating the metal film cleaned in the cleaning step with ultraviolet rays to decompose and remove organic substances remaining on the metal film. A method for producing a master for medium production. 2. A method for applying a resist to the glass substrate in the resist applying step,
2. The method according to claim 1, wherein the surface treatment is performed using any one of Cr, Ni, and hexamethyldisilazane. 3. The method according to claim 1, wherein the glass substrate has a hydroxyl group concentration of 4%.
2. The method for manufacturing a master for manufacturing a recording medium according to claim 1, wherein a synthetic quartz glass substrate having a content of not more than 00 ppm is used. 4. The method according to claim 1, wherein said synthetic quartz glass substrate is Vap.
er phase Axial Deposition
4. The method according to claim 3, wherein a synthetic quartz glass substrate produced by a method is used. 5. The method according to claim 1, wherein before applying the resist on the glass substrate in the resist applying step, 1n is applied on the glass substrate.
4. The method according to claim 3, wherein Cr or Ni is deposited to a thickness of not more than m. 6. The method according to claim 1, wherein an alkali-free glass substrate or a synthetic quartz glass substrate having a hydroxyl group concentration of 400 ppm or more is used as the glass substrate. 7. The method according to claim 1, wherein the glass substrate has a hydroxyl group concentration of 4%.
7. The method for producing a master for recording medium production according to claim 6, wherein a synthetic quartz glass substrate of at least 00 ppm is used, and a synthetic quartz glass substrate produced by a direct method is used as the synthetic quartz glass substrate. 8. The method according to claim 6, wherein Cr or Ni is deposited to a thickness of 10 nm or more on the synthetic quartz glass substrate before applying the resist on the glass substrate in the resist applying step. Of producing a master for producing a recording medium. 9. The method according to claim 1, wherein the resist is a chemically amplified resist. 10. The master according to claim 9, wherein the chemically amplified resist has a polyhydroxystyrene skeleton and further contains at least one of an acetal group and an alkoxy group. Manufacturing method. 11. The recording medium according to claim 10, wherein in the heat treatment step, the temperature of the heat treatment is 80 ° C. or more and 120 ° C. or less, and the time is 5 minutes or more and 20 minutes or less. Master disc manufacturing method. 12. The method according to claim 9, wherein the chemically amplified resist has polyhydroxystyrene as a skeleton and further contains a tert-butyl ester group. 13. In the heat treatment step, the temperature is set to 100.
13. The method for producing a master for producing a recording medium according to claim 12, wherein the temperature is set to not lower than 160 ° C. and the time is not shorter than 5 minutes and not longer than 20 minutes. 14. After the exposing step and before the developing step, exposure is performed in the exposing step at a temperature of 100 ° C. or more and 160 ° C. or less and a time of 5 minutes or more and 20 minutes or less. 13. The method according to claim 12, wherein a second heat treatment is performed on the resist. 15. The method according to claim 1, wherein the resist is an electron beam resist. 16. The method according to claim 1, wherein the heat treatment is performed by a hot plate method. 17. The method according to claim 1, wherein in the exposing step, a beam having a wavelength of 300 nm or less is used as the exposure beam. 18. The method according to claim 1, wherein in the developing step, a developing solution containing tetramethylammonium hydride is used as the developing solution. 19. The developer according to claim 1, wherein the concentration of tetramethylammonium hydride is 0.17 mol / l to 0.1 mol / l.
The method for producing a master for producing a recording medium according to claim 18, wherein the amount is 26 mol / l. 20. The method according to claim 19, wherein the resist coating step, the exposing step and the developing step are performed at a temperature of 15 ° C. to 25 ° C.
2. The method according to claim 1, wherein the method is performed in an environment satisfying the conditions of 0% to 60%, an ammonium ion concentration of 10 ppb or less, and a 2-methylpropanolamine concentration of 5 ppb or less. 21. The metal film forming step includes: a step of applying a metal to the surface of the pattern formed in the developing step to convert the surface of the pattern into a conductor; 2. A method for producing a master for producing a recording medium according to claim 1, further comprising a plating step of forming a metal film by electroforming plating. 22. The method according to claim 21, wherein in the metal film forming step, nickel is used as a material of the metal film. 23. The method according to claim 21, wherein a metal is applied to the surface of the pattern by sputtering or electroless plating in the conductor-forming step. 24. The method according to claim 1, wherein in the cleaning step, a solvent used for cleaning the metal film is maintained at a temperature of 20 ° C. or more and 130 ° C. or less. 25. The method according to claim 1, wherein the cleaning step is performed by ultrasonic cleaning. 26. Before performing an ultraviolet irradiation step on the metal film on which the cleaning step has been performed, the thickness of an organic substance remaining on the metal film is measured by using an ultraviolet-visible spectrophotometer, an ellipsometer,
The method for producing a master for producing a recording medium according to claim 1, wherein the measurement is performed using any one of a step measuring device. 27. In the ultraviolet irradiation step, at least one of a low-pressure mercury lamp having a wavelength of 254 nm and 185 nm, an excimer lamp having a wavelength of 172 nm, and an excimer lamp having a wavelength of 222 nm is used as an ultraviolet light source. The method for producing a master for producing a recording medium according to claim 1, wherein: 28. In the ultraviolet irradiation step, the in-plane distribution of the integrated amount of ultraviolet light applied to the metal film is ± 1.
2. The method according to claim 1, wherein the ultraviolet rays are irradiated so as to be within 5%.