WO2004001736A1

WO2004001736A1 - Process for producing stamper for production of optical recording medium and apparatus

Info

Publication number: WO2004001736A1
Application number: PCT/JP2003/006598
Authority: WO
Inventors: Hisaji Oyake; Akinori Nishizawa; Hideki Sunohara
Original assignee: Tdk Corporation
Priority date: 2002-06-25
Filing date: 2003-05-27
Publication date: 2003-12-31
Also published as: TW200402715A; AU2003241802A1

Abstract

A process for producing a stamper for production of optical recording medium wherein micro-flaws occurring at the formation of a metal thin film by electroless plating can be prevented with the use of a photoresist original plate having a light absorption layer; and an apparatus therefor. In particular, a process for producing a stamper for production of optical recording medium with the use of a photoresist original plate provided with a light absorption layer, characterized in that as a simulation, for example, a trial experiment prior to stamper production, over a light absorption layer original plate comprising a substrate for trial experiment overlaid with a light absorption layer, (a) multiple metal chloride solutions are sprayed, (b) a strong acid is sprayed so that only a metal capable of catalyzing electroless plating adheres to the surface of the light absorption layer, (c) a liquid is sprayed so as to effect cleaning, and (d) the resultant light absorption layer original plate is immersed in water, and that the spray time of each of these steps is determined so that in the step (d), the saturation amount of chloride ion extracted from the light absorption layer falls within the range of 0.0044 to 0.1990 μg/cm2 and electroless plating pretreatments are carried out as much as the spray times determined for the steps (a), (b) and (c) to thereby obtain a stamper; and an apparatus therefor.

Description

Specification

TECHNICAL FIELD The manufacturing method and apparatus of a stamper for manufacturing an optical recording medium

The present invention relates to a method and an apparatus for manufacturing a stamper used for manufacturing an optical recording medium having a concavo-convex pattern such as a group or a prepit. Background art

Currently, there are two types of optical recording medium disk substrates: optical disks that can be written on or rewritten, and read-only disks on which information is recorded in advance.

A group (guide groove) used for tracking or the like is formed on a disk substrate of the optical recording disk, and a recording layer containing a phase change material or an organic dye material is further laminated on the disk substrate. When the recording layer is irradiated with the laser beam, the recording layer undergoes a chemical or physical change to form a recording mark. "On the other hand, recording marks (information pits) are formed in advance on the disk substrate of a read-only disc as a part of an uneven pattern. These recording marks are irradiated with a reading laser beam. As a result, the amount of light reflection fluctuates, and it is possible to read (reproduce) information by detecting this fluctuation.

In order to manufacture a disk substrate having a concave / convex pattern such as a groove / information pit, a stamper in which a negative pattern of the concave / convex (also a kind of concave pattern) is formed in advance is used. For example, a method is generally used in which injection molding is performed using a mold in which a stamper having the negative pattern formed in a cavity is fixed, and the negative pattern is transferred to a filled resin to produce a disk substrate. .

A stamper having a concavo-convex pattern usually contains nickel (Ni) or the like. It is constituted by a metal plate. As a process of manufacturing the stamper, first, a photo resist master having a negative pattern of the concavo-convex pattern of the stamper is prepared in advance, and a metal thin film is formed on the photoresist master by electroless plating or the like. This converts the photoresist master into a conductor, and then forms a metal film by plating. Thereafter, the metal film is peeled off from the photoresist master, and a predetermined process such as surface cleaning is performed to obtain a stamper.

Specifically, a photoresist layer is formed on a glass substrate, and then the photoresist layer is exposed using a patterning beam such as a laser, and the latent image pattern is developed. As a result, a photoresist master having an uneven pattern formed on the photoresist layer can be obtained.

In order to manufacture a stamper by plating using this photoresist master, first, a metal thin film containing Ni material etc. is formed on the surface of the uneven pattern by electroless plating, etc., and the photoresist master is made conductive. Give. In addition, as a pretreatment for electroless plating, a method of depositing a catalyst, which is a starting point of a metal deposition reaction, on the surface and depositing the catalyst using the catalyst as a nucleus is adopted. Thereafter, the metal thin film is used as a base. Then, a metal film containing Ni etc. is formed. If the metal thin film and the metal film are peeled off from the photoresist master, the concavo-convex pattern is transferred and a stamper can be obtained. '

In recent years, as the capacity of optical recording media has increased, concavo-convex patterns of groups and the like have become finer, and their shape errors have had a great effect on recording and reading accuracy. Therefore, it is required to form a sharp concavo-convex pattern on the disk substrate. For this purpose, it is necessary to form the concavo-convex pattern of the underlying resist layer with high precision (sharp).

However, if the photoresist layer is thin, the uneven pattern transferred to the stamper It is known that the turns become shallower, and the shape of the uneven pattern becomes rounded (this is called the “sag” of the pattern), resulting in insufficient sharpness. This is generally thought to be due to fluctuations in the thickness of the photoresist during exposure and development operations (this is referred to as “film loss”). It is considered that this film reduction is caused by the fact that the laser beam is reflected between the photoresist layer and the glass substrate, and the reflected light exposes the photoresist layer more than necessary. In order to prevent such reflection, Japanese Patent Laid-Open Publication No. Heisei 4'1-263100 proposes a glass master with an anti-reflection coat having an anti-reflection effect using light interference. I have. When a fine uneven pattern with a minimum width of about half of the exposure wavelength is formed, even if a non-reflective coating is provided, the effect of suppressing film loss is small and the shape of the uneven pattern is almost the same. Did not improve. Further, Japanese Patent No. 27279742 proposes providing a light absorbing layer containing graphite on the back surface of a glass substrate. Then, when ultraviolet light is incident on the glass substrate and the amount of light reflected from the front surface (light incident surface) and the back surface of the substrate is measured, the reflected light from the glass substrate surface is larger, and graphite is applied to the back surface of the glass substrate. The effect is small only by forming the light absorbing layer including the light absorbing layer.

In order to solve this problem, the present inventors have found that it is effective to form a light absorbing layer between a glass substrate and a photoresist layer. In this case, the light absorbing layer absorbs the laser beam reflected from the front and back surfaces of the glass substrate. Furthermore, the reflected light that is reflected on the back surface of the glass substrate and reaches the photoresist layer passes through the light absorption layer twice, and the intensity is extremely weak. As described above, light reflection can be suppressed, sag and film reduction can be suppressed, and a sharper uneven pattern can be obtained as compared with the conventional case.

However, the photoresist bed having a light absorbing layer had the following problems when forming a metal thin film by electroless plating. It is The photo resist is removed by the image, so that the photo resist master where the light absorption layer is partially exposed may have minute defects (fine irregularities) in the metal thin film after the electroless plating process. That is. Since these small defects can be considered as noise during reproduction, there is a problem in that even if an attempt is made to effectively use the light absorbing layer to increase the recording capacity, the noise degrades the recording and reproduction performance. Was. Disclosure of the invention

If this problem is solved, it is possible to manufacture a stamper having a sharp 囬 convexity by using a photoresist master using a light absorbing layer. An object of the present invention is to provide an effective means for that purpose.

The present inventor has studied the manufacturing method of the optical recording medium and the like, and as a result, the above object can be achieved by the invention described in the claims of the present application.

The present invention focuses on the fact that in the electroless plating process, microdefects are likely to be generated in the light absorbing layer that is partially exposed by development, and the metal chloride solution used in the pretreatment of the electroless plating is used. It was speculated that the coming chlorine ions would adhere to the surface of the light absorbing layer and cause micro defects in the metal thin film in the next electroless plating process. Specifically, since chlorine ions are easily deposited on the surface of the light absorbing layer, an uneven pattern is formed by development, and when the light absorbing layer is partially exposed, chlorine ions are deposited on the surface of the light absorbing layer. Chlorine ions not removed by the subsequent cleaning are heated during the electroless plating, and gasify and swell because the surface is covered with a metal thin film, resulting in minute defects on the metal thin film surface. It is thought that it is possible.

The stamper (A) sprays a plurality of metal chloride solutions onto the photoresist master, and (B) sprays a strong acid to deposit only a metal that serves as a catalyst for electroless plating on the surface of the light absorbing layer. Process, (C) Cleaning by spraying liquid This is manufactured by performing electroless plating and then electrolytic plating.However, prior to the stamper manufacturing process, (A) (B) (C) ) By adjusting each injection time in the process, the saturation amount of chloride ions extracted from the light absorption layer, for example, the light absorption layer master when the light absorption layer is formed into the water et extracted 0.0 with saturated amount per area of the light absorbing layer master chlorine ions 044~0. 1 9 9 0 / ig / cm to determine the ² become conditions, by then making the static damper production However, we thought about suppressing minute defects in metal thin films. 'Specifically, the injection time is as follows.If the injection time in the step (A) is too long, a large amount of metal serving as a catalyst in electroless plating is deposited on the surface, but a large amount of chlorine ions is deposited, resulting in minute Defects are likely to occur. On the other hand, if the amount is too small, chlorine ions are reduced, but the amount of metal acting as a catalyst is reduced and the electroless plating makes it difficult to form a metal thin film. The injection time in the process (B) may be long enough to allow only the catalyst metal deposited in the process (A) to be deposited on the surface of the uneven pattern and to remove other metals. Only waste material. If the time is too short, other metals will remain, and the metal thin film will become uneven and cause noise. (C) If the injection time in the process is too long, not only chloride ions but also metals that serve as catalysts will be removed. On the other hand, if it is too short, chlorine ions cannot be sufficiently removed. Therefore, to verify during at each injection in preliminary experiments, most saturated amount of chlorine ions extracted into water from the light absorbing layer is such that 0. 0 044~0. 1 9 90 μ g / cm 2 Decide the matter. Thereafter, by manufacturing a stamper under these conditions, it is possible to suppress the occurrence of minute defects in the metal thin film.

As a result, by utilizing the advantages of the light absorbing layer, a stamper having no fine defects and having a sharper concavo-convex pattern than before can be obtained. As a result, the optical recording medium groups and information pits are sharply formed, so that the recording and reproducing characteristics can be improved. In the future Since it is possible to cope with the evolving miniaturization of concavo-convex patterns, it is also possible to increase the information storage (recording) capacity of optical recording media. '' Brief description of the drawings

FIG. 1 is a block diagram showing an apparatus used for manufacturing a stamper for an optical recording medium of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the method for manufacturing a stamper for an optical recording medium of the present invention will be described in detail.

The substrate for the preliminary experiment is not particularly limited, but preferably does not contain much chloride ions. A substrate different from the stamper manufacturing substrate may be used. The substrate for manufacturing the stamper is not particularly limited.

Before forming the light absorbing layer, a coupling agent layer may be provided on the substrate to facilitate adhesion of the light absorbing layer. The light absorbing layer preferably contains an organic compound having a light absorbing property (hereinafter, also referred to as a light absorbing agent). As the light absorber, it is preferable to use at least one compound selected from a photoinitiator, a photoinitiator and a dye. Generally, a photoinitiator is used together with a photocurable resin, and is an organic compound that absorbs light such as ultraviolet rays to generate radicals. In addition, when the photoinitiator is used in combination with a photoinitiator which is not activated by ultraviolet irradiation, the initiation reaction is accelerated by using the photoinitiator alone, and the curing reaction proceeds effectively. The photoinitiator generates radicals and decomposes. However, since the photoinitiator is stable, it is preferable to use the photoinitiator in the present invention. As the photoinitiating aid, an aliphatic or aromatic amine is mainly used. In the present invention, 4.4'-bis (dimethylamino) benzophenone, 4.4'-bis (getylamino) benzophenone, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, It is preferable to use at least one kind of 2-ethylhexyl 4-dimethylaminobenzoate, and it is particularly preferable to use a benzophenone compound.

The photoresist is not particularly limited.

When a thin metal film such as Ni is formed by electroless plating, palladium (Pd) is generally pre-deposited on the surface as a catalyst that serves as a starting point for a metal deposition reaction. Therefore, (a), (b) and (c) corresponding to the above-mentioned steps (A), (B) and (C) are performed as a pretreatment of the electroless plating. (A) The plurality of metal chloride solutions used in the process are generally a solution containing both tin (Sn) and Pd for adsorbing Pd nuclei, a so-called catalyst called primary palladium chloride (Pd C l ₂₎ and colloids solution containing stannous chloride (S n C l ₂₎ is used. In this solution, Pd is present in a state of being coated with the Sn ion colloid. In the subsequent step (b), the strong acid removes this colloid, and Pd adheres to the surface. Instead the P d C 1 ₂ and S n C 1 ₂ to including colloids solution, P d C 1 ₂ solution and S n C 1 ₂ solution may be used each independently, also using other metal It does not matter. The strong acid can be appropriately selected from hydrofluoric acid (HBF ₄ ), sulfuric acid, hydrochloric acid, and the like. (C) The liquid used in the step may be pure water, preferably ultrapure water. The flow rate is preferably at least 11 Zmin, more preferably at least 51 / min.

For the measurement of chloride ion saturation, the light absorption layer master plate that has been pretreated for electroless plating is put into pure water and the amount of chloride ion extracted is measured. Leave it in water until the chloride ion content is saturated, and use this saturated amount as the saturated amount of chlorine ion in the light absorption layer master. In consideration of the amount of chloride ions extracted from the substrate, a light-absorbing layer is formed on a glass substrate, and the amount of chloride ions that have passed through the process (d) without performing the processes (a), (b), and (c) Was measured, and this was defined as the saturation amount of chloride ions extracted from the substrate. Is the saturation amount of chloride ions in the light absorbing layer master The value obtained by subtracting the saturation amount of chloride ions extracted from the substrate from the above is taken as the saturation amount of chloride ions extracted from the light absorption layer.

A thin film of metal such as Ni is formed by electroless plating on the surface of the 囬 convex pattern on which Pd is adhered. At this time, the reducing agent in the plating solution is oxidized on the Pd surface having catalytic activity to release electrons, and the electrons reduce metal ions such as Ni in the solution to deposit a metal thin film. The metal thin film is not limited to Ni, and another metal may be used.

A metal film containing Ni or the like can be formed by applying a current by using a metal thin film of Ni or the like formed by electroless plating as a base. The metal is not limited to Ni, and other metals may be used.

In the example of the above-described embodiment, the saturation amount of chlorine ions and the injection time in each step when being injected into water are determined by using a substrate for preliminary experiments or a substrate for manufacturing a stamper. Alternatively, it may be determined by another simulation, for example, a simulation on a computer assuming underwater injection.

Next, an apparatus used for manufacturing the stamper for manufacturing an optical recording medium will be described with reference to FIG.

The manufacturing apparatus 10 is a pretreatment apparatus for substantially electroless plating, and includes a turntable 14 for rotatably supporting a photoresist master 12 in a horizontal plane, and the photoresist on the turntable 14. A solution ejector 16 capable of ejecting a plurality of metal chloride solutions from above, a strong acid solution ejector 18 capable of ejecting a strong acid solution, and a solution capable of ejecting a cleaning liquid from above. The body injection device 20, a control valve 17 1 19 21 for turning on and off the injection of each of these injection devices 16 18 20, and an on / off of these control valves 17 19 19 21 A controller 22 for controlling the injection time of the metal chloride solution, the injection time of the strong acid solution, and the injection time of the cleaning liquid, The control unit 22 includes an injection time memory unit 24 that stores the signal of each injection time and can output the signal.

In FIG. 1, reference numeral 16 A indicates a metal chloride solution tank, 18 A indicates a strong acid solution tank, and 20 A indicates a cleaning liquid tank. The nitrogen in the tank 16, 18 A, and 20 A is supplied with nitrogen gas from a nitrogen gas source (not shown), whereby the liquid in the tank is pushed out, and the control pulp 17, 19 , 21 through the photoresist master 12 on the turntable 14.

In addition, reference numeral 32 in FIG. 1 denotes a motor for rotating the photo resist master disk in the turntable 14, and reference numeral 34 denotes an input key for manually inputting to the control section 23 of the control device 22. Further, the control valves 17, 19, 21 and the motor 32 are configured to be controlled by a control unit 23.

In addition, a signal of each injection time is input to the control unit 23 from the injection time memory unit 24.

The injection time memory unit 24 stores the injection time signal determined in the above-described simulations, for example, the preliminary experiments in the steps (a), (b), and (c), and stores the signal for the photoresist master 12 in the chloride state. If the injection time of the metal solution injection time, the strong acid solution injection time, and the cleaning liquid injection time is input from the input key 34 through the control unit 23, the gold by electroless plating It is possible to obtain a stamper having a sharp ω convex pattern by suppressing the generation of minute defects at the time of forming a metal thin film. '

[Examples and Comparative Examples]

(Example 1)

After a coupling agent (hexamethyldisilazane (HMDS)) layer is formed on a polished glass substrate with a diameter of 12'cm, a 4.4-bis- (Jetylamino) benzophenone is used as a light absorbing agent on it. SWK contained as -T5D60 (Tokyo Ohka Kogyo Co., Ltd.) was spin-coated. Further, this coating film was baked at 200 ° C. for 15 minutes to cure and remove the residual solvent, thereby forming a light absorbing layer having a thickness of 140 nm.

Then, after forming the surfactant (alkyl ammonium Niu beam class i de) layer on the light absorbing layer surface, the light absorbing layer surface, and a plurality of metal chloride solution, P d C 1 ₂ and S n the colloids solution of C 1 ₂ to injection 1 2 sec. Then, a strong acid (HBF ₄ ) was sprayed for 7 seconds to remove Sn and precipitate Pd on the surface. Thereafter, the surface of the light absorption layer was washed with water by spraying pure water (water amount: 12 1 / min) for 10 minutes to obtain a light absorption layer master.

Put the light absorbing layer master and 100 m 1 of pure water into a beaker of 31 and leave it at room temperature (about 25 ° C). Then, use the ion chromatograph analyzer (DIONEX DX500, measurement conditions). (Column: AG15 / AS15, manufactured by DI ONEX, eluent: Lithium hydroxide (KOH) 38 mm o 1/1, 1.2 ml / min, Suppressor: AS, manufactured by DIONE X) RS—ULTRA (Recycle mode / 100 mA), thermostat temperature: 35 ° C, sample introduction amount: 25 μ1, detection: electric conductivity)) . Chloride ion levels were measured daily and continued until saturation. The saturated amount of chloride ions in the master disk of the light absorption layer was 5.25 g // g / 100 ml. The saturation amount of chloride ions extracted from the substrate was 4.5 ix g / 100 ml. Therefore, the saturated amount of chloride ion extracted from the light absorption layer was 5.0-4.5 = 0. This value was converted to the amount of chloride ions per area of the master (since the area was 11 cm, the area was 11.3 cm ² ), and was 0.044 g / cm ² .

Then, similarly after creating the light absorption layer master was subjected to pre-treatment of the electroless plated, the light absorbing layer master was dipped in a nickel chloride (N i C l ₂₎ bath, N i film by electroless main luck Was formed. Attach Ni thin film to light absorbing layer The whole surface was visually observed for ease. The easiness of attaching Ni was marked as 〇 for those with good attachment, and the X for those with very little Ni attachment. The easiness of attaching the Ni thin film was Δ.

After this Ni thin film is formed, the surface of the Ni thin film (the side opposite to the glass substrate) is visually observed over the entire surface and at least 20 places are observed with an optical microscope (magnification: 200 times), and minute defects existing on the surface are observed. Was evaluated. The microdefects that did not occur were marked with 〇, and those that were very small were marked with X. Small defects were not observed.

(Example 2)

A sample was prepared in the same manner as in Example 1 except that the injection time of pure water was 0.5 minute.

(Example 3)

Except that the P d C 1 ₂ and injection time of the S n 1 ₂ of colloids solution with 1 5 seconds to create a sample in the same manner as Example 1.

(Example 4)

P d C 1 and ₂ and S n C 1 ₂ of the injection time of the colloids solution 3 0 seconds, except that the injection time of HBF ₄ solution and 1 0 seconds to create a sample in the same manner as Example 1.

(Example 5)

P d C ₂ and S n C 1 ₂ of the injection time of the colloids solution with 3 0 seconds, HB F ₄ solution injection time was 1 0 seconds, except that the injection time of the pure water was 1 minute Example 1 A sample was prepared in the same manner as described above. .

(Example 6)

P d C 1 and ₂ and S n C 1 ₂ of the injection time of the colloids solution 3 0 seconds, HB F ₄ solution injection time was 1 0 seconds, except that the injection time of the pure water was 30 minutes Examples A sample was prepared as in 1.

(Comparative Example 1) P d. A C l ₂ and S n C l injection time of a colloidal solution of ₂ for 3 seconds, and 3 seconds injection time of HBF ₄ solution, the samples in the same manner as Example 1 except that no jetting pure water Created.

(Comparative Example 2)

A sample was prepared in the same manner as in Example 1 except that the injection time of pure water was set to 30 minutes.

(Comparative Example 3)

A sample was prepared in the same manner as in Example 1 except that pure water was not injected. (Comparative Example 4)

P d C l and ₂ and S n C l injection time of colloids solution ₂ 3 0 seconds, and 1 0 seconds injection time of HBF ₄ solution, except that the injection time of the pure water was 40 minutes Example 1 A sample was prepared in the same manner as described above.

(Comparative Example 5)

P d C l and ₂ and S n C l injection time of colloids solution ₂ 3 0 seconds, and 1 0 seconds injection time of HBF ₄ solution, similarly to Example 1 except that no injection of pure water A sample was created.

The evaluation results of each of these tests are shown in Table 1 below. Occurrence of minute defects when saturating amounts of chloride ions exceeds 0. 1 9 90 μ gZ cm ² is increased, 0. 0044 / g Bruno _C m and less than ² N i thin film is hardly made can be seen attached. According to the above experiment, the saturation amount of chloride ion is small (the number of micro defects is small) and the Ni thin film is easily attached to the light absorption layer. (1. Determine the 1 ₂ and 3 11. injection time of 1 _second roller Id solution, and HB F ₄ solution injection time, the condition of the cleaning time due to the injection of pure water.

【table 1】

HBF ₄ solution Pure water ίππ Micro defect Ni thin film

SnGI ₂

Injection time Injection time Generation of ion amount Ease of adhesion Colloidal solution

Injection time

(Seconds) (minutes) (g / cm ² )

(Seconds)

iHll 1 1 I 71 1 Π J iHll 0 19 7 U.0 υ υ.1 I Q y Ω yΠ υ

W 110 7/1 υ Π U .01111 ϋ ^

Example 4 30 10 10 0.0575 O 例 Example 5 30 10 1 0.1990 o ο Example 6 30 10 30 0.0044 o ο Comparative example 1 3 3 0 0.0035 o X Comparative example 2 12 7 30 0.0018 o X Comparative example 3 12 7 0 0.2078 X Ο Comparative Example 4 30 10 40 0.0027 o X Comparative Example 5 30 10 0 0.2176 X Ο

(Example 1 1)

Next, the stamper manufacturing process is actually started. After forming a coupling agent (hexamethyldisilazane (HMDS)) layer on a polished glass substrate, it contains 4.4'-bis (getylamino) benzophenone as a light absorber on it. SWK—T5D60 (Tokyo Ohka Kogyo Co., Ltd.) was spin-coated. Further, the coating film was baked at 200 ° C. for 15 minutes to cure and remove the residual solvent, thereby forming a light absorbing layer having a thickness of 140 nm. Next, a photo resist (DVR100, manufactured by Zeon Corporation) is spin-coated on the light absorbing layer, and the remaining solvent is evaporated by baking to form a 25-nm thick photo resist layer. did.

Then, using a cutting machine manufactured by Sony Corporation, a Kr laser (wavelength = 351 nm) was used to form a groove pattern with a track pitch of 320 nm and a groove width of 150 nm. Photoresist layer The substrate was exposed to light and developed to form a concavo-convex pattern, thereby obtaining a photoresist master.

Then, the follower Torejisu coat layer surface after activation with a surfactant (alkyl en monitor Umukurai de), similar to the conditions of Example 1, the colloids solution of P d C l ₂ and S n C l ₂ 1 Injected for 2 seconds. Then, injected HBF ₄ solution 7 seconds and then pure water (water; 1 2 1 / min) to wash the uneven pattern surface by a 1 0 minute injection (Example 1 conditions), prior to electroless plating key A processed photoresist master was obtained.

This photoresist master was dipped in N i C 1 ₂ bath, I. Ri to form an N i thin film in an electroless plated. The easiness of attaching the Ni thin film was Δ.

Electric plating was performed using the Ni thin film as a base to form Ni. The Ni thin film and the laminate composed of the Ni film were peeled from the master, and the back surface was polished and the front surface was cleaned to form a stamper. No micro defects on the surface of the Ni thin film of this stamper were observed.

(Example 1 2)

A sample was prepared in the same manner as in Example 11 except that the injection time of pure water was 0.5 minute (the condition of Example 2).

(Example 13)

Except that P d C 1 ₂ and S n C 1 ₂ of the injection time of the colloids solution 1 5 seconds (the conditions of Example 3) was prepared in the same manner as in Sample in Example 1 1.

(Comparative Example 1 1)

A sample was prepared in the same manner as in Example 11 except that the injection time of pure water was 30 minutes (the conditions of Comparative Example 2).

(Comparative Example 1 2)

A sample was prepared in the same manner as in Example 11 except that pure water was not injected (the conditions of Comparative Example 3).

Table 2 below shows the evaluation results of each of these tests. Chlorine in preliminary experiment Under such conditions that the saturation amount of oxygen is from 0.0044 to 0.190 μg / cm ² , there is no generation of minute defects and no peeling of the Ni thin film. Further, minute defects occur in conditions of saturated amount of chlorine ions in the preliminary experiments exceeds 0. 1 9 9 0 / ig / cm 2, in 0. 0 044 / i gZ cm ² less than the condition, N i It can be seen that it is difficult to form a thin film. From the above experiments, (a), (b), and (c) each injection time was determined by preliminary experiments, and then the stamper was manufactured. A stamper could be formed. , [Table 2]

Industrial applicability

In the present invention, first, as a preliminary experiment, the saturation amount of chloride ions extracted from the light absorbing layer by a simulation such as using a master disk of the light absorbing layer is set to 0.04 to 0.190 / ig / cm ^2. (A) (b) (c) Determine each injection time. By subsequently manufacturing a stamper, the generation of minute defects during the formation of a metal thin film by electroless plating can be suppressed, and the stamper with a sharper uneven pattern than before can be obtained by taking advantage of the light absorbing layer. It became possible.

Claims

The scope of the claims

1. forming a light absorbing layer and a photo resist layer in this order on a stamper manufacturing substrate;

Irradiating the photoresist layer with light to form a latent image; developing the latent image to form a concave / convex pattern to produce a photoresist master;

(A) a step of spraying a plurality of metal chloride solutions onto the surface of the 囬 convex pattern, (B) a step of spraying a strong acid to deposit only a metal serving as a catalyst for electroless plating on the surface of the light absorbing layer, ( C) a step of injecting and cleaning a liquid; and

Forming a metal thin film on the uneven pattern by electroless plating;

Further comprising, after forming a metal film on the metal thin film by electroplating, separating the metal thin film and the metal film from the photoresist master.

Each of the injection times in the steps (A), (B), and (C) is based on the assumption that the photo-resist master after the step (C) is put into water. A method for producing a stamper for producing an optical recording medium, wherein the condition is such that the saturation amount of chlorine ions is 0.0044 to 0.190 μg / cm ² .

2. In claim 1,

As a preliminary experiment before manufacturing the stamper, a light absorption layer master with a light absorption layer formed on a substrate for the preliminary experiment was

(a) injecting a plurality of metal chloride solutions,

(b) By injecting a strong acid, only the metal that serves as a catalyst for electroless plating Attaching to the light absorbing layer surface,

(c) a step of spraying and cleaning the liquid,

(d) charging the light absorbing layer master into water,

After the step (d), the condition that the saturation amount of chloride ions extracted from the light absorbing layer in the step (d) is 0.0044 to 1.900 / ig / cm ² , that is, the condition (a) (b) (c) determining each injection time of the step, and using these as the respective injection times of the steps (A), (B), and (C), manufacturing a stamper for manufacturing an optical recording medium. Method.

3. A latent image is formed by irradiating light on the photoresist layer of the stamper manufacturing substrate having a light absorbing layer and a photoresist layer formed on the surface in this order, and the latent image is developed. A turntable that rotatably supports a photoresist master having a concave pattern formed by being formed in a horizontal plane, and a plurality of metal chloride solutions can be sprayed on the photoresist master on the turntable. A liquid ejecting apparatus capable of ejecting a strong acid solution, a strong acid solution ejecting apparatus capable of ejecting a strong acid solution, and a liquid ejecting apparatus capable of ejecting a cleaning liquid.

A control valve for turning on and off each of these injection devices; and a control device for controlling the injection time of the metal chloride solution, the injection time of the strong acid solution, and the injection time of the cleaning liquid by turning on and off these control valves. A part of an injection time memory included in the control device, which stores the signal of each injection time, and which can output the signal;

Having.

In part of this injection time memory,

(C) a step of spraying a plurality of metal chloride solutions onto the surface of the uneven pattern; (C) a step of spraying a strong acid to deposit only a metal serving as a catalyst for electroless plating on the surface of the light absorbing layer; ) When it is assumed that the photoresist master having undergone the step of spraying and washing the liquid is put into water, Light saturation amount of chlorine ions extracted from Osamuso is, 0. 0 0 4 4~0. 1 9 9 0 ig Bruno cm ² become such conditions injection time signal is equal to or stored Manufacturing equipment for stampers for manufacturing recording media.

4. In claim 3,

As a preliminary experiment before manufacturing the stamper, a light absorption layer master with a light absorption layer formed on a substrate for the preliminary experiment

(a) injecting a small number of metal chloride solutions;

(b) a step of applying only a metal serving as a catalyst for electroless plating by injecting a strong acid onto the surface of the light absorbing layer,

(c) a step of spraying and cleaning the liquid,

(d) a step of putting the light absorbing layer master into water,

After passing through (d) is a saturating amount of chlorine ions extracted from the light absorbing layer in the step, 0. 0 0 4 4~0. 1 9 9 0 / ig Bruno cm ² become such conditions i.e., above) (b) (c) An apparatus for manufacturing a stamper for manufacturing an optical recording medium, wherein each injection time in the step is determined and used as an injection time signal stored in the injection time memory section.