EP4151776A1 - Galvanoplastik-master, verfahren zur herstellung des galvanoplastik-masters und verfahren zur herstellung eines galvanoplastik-materials - Google Patents

Galvanoplastik-master, verfahren zur herstellung des galvanoplastik-masters und verfahren zur herstellung eines galvanoplastik-materials Download PDF

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Publication number
EP4151776A1
EP4151776A1 EP22194324.4A EP22194324A EP4151776A1 EP 4151776 A1 EP4151776 A1 EP 4151776A1 EP 22194324 A EP22194324 A EP 22194324A EP 4151776 A1 EP4151776 A1 EP 4151776A1
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Prior art keywords
electroforming
master
oxide film
electroforming master
substrate
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EP22194324.4A
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English (en)
French (fr)
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Tomokazu Umezawa
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Fujifilm Corp
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Fujifilm Corp
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/20—Separation of the formed objects from the electrodes with no destruction of said electrodes
    • C25D1/22—Separating compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/20—Separation of the formed objects from the electrodes with no destruction of said electrodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/003—3D structures, e.g. superposed patterned layers

Definitions

  • the present disclosure relates to an electroforming master, a method for producing an electroforming master, and a method for producing an electroforming material.
  • An electroforming method is widely used as a method for producing parts having various shapes, dies, and the like.
  • a master having a pattern on a surface thereof is used, and nickel or the like is electroformed on the master to produce an electroforming material.
  • JP2005-256110A it is disclosed in JP2005-256110A to provide an electroforming mold including a plurality of mold structures consisting of silicon that is formed on a substrate consisting of silicon and that has side walls substantially perpendicular to a surface of the substrate, an insulator covering the side walls and an upper surface of each mold structure, and a support substrate that supports each mold structure through an insulating connection layer, in which the insulating connection layer connects a lower surface of each mold structure and an upper surface of the support substrate and includes a recessed portion that is formed such that at least a part of the insulating connection layer where each mold structure is not in contact is removed.
  • An oxide film is formed on a surface of the master over time, and the oxide film between an electroforming material during growth and the master exists to reduce the adhesive strength of the electroforming material to the master. As a result, there is a risk in which the electroforming material is peeled off on the way of production. Therefore, as described in JP2007-287216A , the oxide film is removed from the master using an acid such as hydrofluoric acid before the production of the electroforming material.
  • a pattern formed by an insulating film may be provided on a surface of a master.
  • the present inventor has found a knowledge that there is a difficulty in controlling the removal of an oxide film by using an acid, and a pattern may also be removed in a case where an oxide film is removed with respect to the master provided with the above-described pattern formed by the insulating film by using an acid.
  • the present inventor has also found that the adhesiveness of the electroforming material with respect to the electroforming master is improved by adjusting a thickness of the oxide film on a surface of a substrate provided in the electroforming master without removing the oxide film by an acid.
  • An object to be solved by an embodiment of the present disclosure is to provide an electroforming master that has excellent adhesiveness to an electroforming material and that is capable of suppressing an electroforming material during growth to be peeled off, a method for producing the above-described electroforming master, and a method for producing an electroforming material using the above-described electroforming master.
  • the electroforming master that has excellent adhesiveness to the electroforming material and that is capable of suppressing the electroforming material during growth to be peeled off, the method for producing the above-described electroforming master, and the method for producing an electroforming material using the above-described electroforming master.
  • the numerical ranges expressed using “to” include the numerical values before and after the “to” as each of the minimum value and the maximum value.
  • the upper limit value or the lower limit value described in one range of numerical values may be replaced with an upper limit value or a lower limit value of the range of numerical values described in other stages.
  • the upper limit value or the lower limit value of the range of numerical values may be replaced with values illustrated in the examples.
  • an "n-type semiconductor” refers to a semiconductor in which free electrons are used as carriers that carry charges.
  • a "thickness of an oxide film” is measured as follows.
  • the thickness of the oxide film is measured at 23°C ⁇ 2°C and 50%RH ⁇ 5%RH in an atmosphere by using an ellipsometer.
  • an ellipsometer an automatic ellipsometer DVA-36L manufactured by Mizojiri Optical Co., Ltd. or a similar device can be used.
  • a thickness of an inorganic insulating film or the like described later is also measured by the above-described method.
  • An electroforming master of the present disclosure includes an n-type semiconductor and a substrate provided with a pattern on a surface thereof, an oxide film is formed on the surface, and a thickness of the oxide film is 18 ⁇ or smaller.
  • the electroforming master of the present disclosure has excellent adhesiveness to an electroforming material and can suppress the electroforming material during growth to be peeled off.
  • the thickness of the oxide film formed on the surface of the substrate included in the electroforming master of the present disclosure is 18 ⁇ or smaller. It is presumed that since a decrease in electrostatic attraction between the substrate and the electroforming material to be grown on the oxide film is suppressed by setting the thickness of the oxide film to 18 ⁇ or smaller, the electroforming master of the present disclosure has excellent adhesiveness to the electroforming material, and the electroforming material during growth is suppressed to be peeled off.
  • the oxide film is not formed on the surface of the electroforming master, it is difficult that the produced electroforming material is peeled off from the electroforming master, and there is a possibility that cohesion failure and the like may occur on the electroforming material or the electroforming master. It is presumed that the presence of the oxide film improves the adhesive strength between the electroforming material and the electroforming master, and enables the peeling while suppressing the occurrence of cohesion failure and the like.
  • a pattern provided on a surface of the substrate is not particularly limited, and it is preferable to appropriately adjust the pattern according to the application of the produced electroforming material. The method of forming the pattern will be described later.
  • the thickness of the oxide film is preferably 17 ⁇ or smaller, more preferably 15 ⁇ or smaller, still more preferably 13 ⁇ or smaller, and particularly preferably 10 ⁇ or smaller.
  • the thickness of the oxide film is preferably 0.5 ⁇ or greater, more preferably 1 ⁇ or greater, still more preferably 2 ⁇ or greater, and particularly preferably 5 ⁇ or greater.
  • the thickness of the oxide film By setting the thickness of the oxide film to 0.5 ⁇ or greater, the adhesive strength between the electroforming material and the electroforming master is improved, and the peeling can be achieved while suppressing the occurrence of cohesion failure and the like.
  • the electroforming material on the oxide film it is possible to suppress inclusion of air bubbles between the oxide film and the electroforming material by setting the thickness of the oxide film to 0.5 ⁇ or greater, and it is possible to suppress the occurrence of defects due to an increase in surface roughness of the electroforming material, which is caused by the air bubbles included.
  • the thickness of the oxide film can be adjusted by adjusting an exposure time of the substrate to the atmosphere after dry etching described later.
  • the oxide film preferably contains a hydroxyl end-group (-OH).
  • the oxide film contains the hydroxyl end-group (-OH), the hydrophilicity on the surface of the oxide film can be improved, it is possible to suppress the inclusion of the above-described air bubbles, and it is possible to suppress the occurrence of defects due to an increase in surface roughness of the electroforming material, which is caused by the air bubbles included.
  • -OH hydroxyl end-group
  • Whether or not the oxide film contains a hydroxyl end-group is determined by X-ray photoelectron spectroscopy (XPS).
  • a hydroxyl group derived from a silanol group is detected on the surface of the oxide film is confirmed under the following measurement conditions using an X-ray photoelectron spectroscope device.
  • the X-ray source is monochromatic Al K ⁇ ray
  • the X-ray spot diameter is 100 ⁇ m
  • the photoelectron escape angle is 90° (inclination of a detector with respect to the surface of the oxide film).
  • the X-ray photoelectron spectroscope device is used for XPS, and for example, Axis-Ultra manufactured by Shimadzu Corporation or a similar device can be used.
  • a contact angle of the oxide film with water at 23°C is preferably 40° or smaller, more preferably 35° or smaller, still more preferably 30° or smaller, and particularly preferably 20°C or smaller.
  • the contact angle of the oxide film with water is set at 23°C to 40° or smaller, it is possible to suppress the inclusion of the above-described air bubbles, and it is possible to suppress the occurrence of defects due to an increase in surface roughness of the electroforming material, which is caused by the air bubbles included.
  • the "contact angle of the oxide film with water at 23°C" is measured by a method of dropping water in air with a water droplet volume of 1 ⁇ L using a contact angle meter.
  • contact angle meter for example, DMo-701 manufactured by Kyowa Interface Science Co., Ltd. or a similar device can be used.
  • the n-type semiconductor contained in the substrate is not particularly limited, and known n-type semiconductors in the related art can be used.
  • the n-type semiconductor include silicon compounds (silicon-based semiconductors), fullerene compounds, electron-deficient phthalocyanine compounds, condensed ring polycyclic compounds (such as naphthalenetetracarbonyl compounds and perylenetetracarbonyl compounds), and tetracyanoquinodimethane compounds (such as TCNQ compounds), polythiophene compounds, benzidine compounds, carbazole compounds, phenanthroline compounds, and the like.
  • the n-type semiconductor is preferably a silicon-based semiconductor from the viewpoint of improving the adhesiveness to the electroforming material.
  • the silicon-based semiconductor include single crystal silicon, polycrystalline silicon, amorphous silicon, polysilicon, and the like.
  • a thickness of the substrate is preferably 50 ⁇ m to 1,500 ⁇ m, more preferably 300 ⁇ m to 1,000 ⁇ m, and still more preferably 500 ⁇ m to 750 ⁇ m.
  • the pattern provided on the surface of the substrate is preferably formed by an inorganic insulating film.
  • the pattern provided on the surface of the substrate is formed by the inorganic insulating film, electroforming of nickel or the like on the pattern can be suppressed, and an electroforming material having a desired shape can be formed.
  • the inorganic insulating film for forming the pattern is preferably a silicon-based oxide film.
  • the inorganic insulating film can be an inorganic insulating film formed of silane dioxide.
  • the inorganic insulating film is a silicon-based oxide film
  • electroforming of nickel or the like on the pattern can be further suppressed, and an electroforming material having a desired formation can be produced.
  • the inorganic insulating film is a silicon-based oxide film
  • the adhesiveness to the substrate can be improved.
  • the electroforming master including the substrate with the above pattern in a case where the formed electroforming material is peeled off from the electroforming master, it is possible to suppress that the pattern is also peeled off, so that regeneration of the pattern is not required. Therefore, the electroforming master including the substrate with the above pattern is suitable for continuous production of the electroforming material and is preferable.
  • silicon-based oxide film an oxide-containing film of the above-described silicon-based semiconductor can be used.
  • a thickness of the inorganic insulating film is preferably 0.1 ⁇ m or greater, more preferably 0.5 ⁇ m or greater, and still more preferably 1 ⁇ m or greater.
  • the upper limit of the thickness of the inorganic insulating film is not particularly limited, and may be, for example, 10 ⁇ m or smaller.
  • An electroforming master 10 of the present disclosure includes a substrate 12 in which an oxide film 11 is formed on a surface thereof.
  • the substrate 12 has a pattern 13 on the surface thereof.
  • the oxide film 11 is not formed on the surface of the pattern 13 in Fig. 1 , but the oxide film 11 may be formed on a part or the entire surface of the pattern 13.
  • a method for producing an electroforming master of the present disclosure includes a step of forming an oxide film having a thickness of 18 ⁇ or smaller by performing dry etching on a surface of a substrate that includes an n-type semiconductor and that is provided with a pattern on the surface, and exposing the substrate to an atmosphere.
  • an electroforming master of the present disclosure it is possible to produce an electroforming master that has excellent adhesiveness to an electroforming material and can suppress the electroforming material during growth to be peeled off.
  • the electroforming master produced by the method for producing an electroforming master of the present disclosure includes the substrate, and the oxide film having a thickness of 18 ⁇ or smaller is formed on the surface thereof. It is presumed that since a decrease in electrostatic attraction between the substrate and the electroforming material to be grown on the oxide film is suppressed by setting the thickness of the oxide film to 18 ⁇ or smaller, the above-described electroforming master has excellent adhesiveness to the electroforming material, and the electroforming material during growth is suppressed to be peeled off.
  • the electroforming master produced by the method for producing an electroforming master of the present disclosure in a case of forming the electroforming material on the oxide film, it is possible to suppress inclusion of air bubbles between the oxide film and the electroforming material, and it is possible to suppress the occurrence of defects due to an increase in surface roughness of the electroforming material, which is caused by the air bubbles included.
  • the electroforming master it is not necessary to use an acid such as hydrofluoric acid, and the electroforming master can be produced by performing dry etching on the substrate and exposing the substrate to the atmosphere. Therefore, the surface of the oxide film tends to have excellent hydrophilicity.
  • the electroforming material it is possible to suppress inclusion of air bubbles between the oxide film and the electroforming material by the oxide film having excellent hydrophilicity, and it is possible to suppress the occurrence of defects due to an increase in surface roughness of the electroforming material, which is caused by the air bubbles included.
  • a method of performing dry etching on the surface of the substrate is not particularly limited, and the dry etching can be performed by using known etching gases in the related art.
  • the oxide film that is formed on the surface of the substrate in advance can be removed, and by exposing the substrate to the atmosphere, an oxide film having a thickness of 18 ⁇ or smaller can be formed on the surface of the substrate.
  • etching it is preferable to use one or more gases selected from the group consisting of a rare gas, a fluorine-based gas, and a chlorine-based gas.
  • gases selected from the group consisting of a rare gas, a fluorine-based gas, and a chlorine-based gas.
  • rare gas He gas, Ar gas, and the like can be used.
  • fluorine-based gas SF 6 gas, CF 4 gas, CHF 3 gas, C 2 F 6 gas, C 4 F 8 gas, and the like can be used.
  • chlorine-based gas Cl 2 gas, CHCl 3 gas, CH 2 Cl 2 gas, CCl 4 gas, BCl 3 gas, and the like can be used.
  • SF 6 gas or Ar gas is preferable from the viewpoint that the surface of the electroforming material can be a mirror surface.
  • an exposure time to the atmosphere is preferably 24 hours or shorter, more preferably 19 hours or shorter, still more preferably 5 hours or shorter, and particularly preferably 1 hour or shorter, and may be 10 minutes or shorter, under the conditions of 1 atm, 23°C ⁇ 2°C and a humidity of 50%RH ⁇ 5%RH
  • the lower limit of the exposure time to the atmosphere is not particularly limited, and may be, for example, one minute or longer.
  • the step of forming the oxide film may include performing one or more treatments selected from the group consisting of immersion in sulfuric acid-hydrogen peroxide, an ultraviolet (UV) ozone treatment, and an oxygen gas plasma treatment, on the substrate after the dry etching and before the exposure to the atmosphere.
  • one or more treatments selected from the group consisting of immersion in sulfuric acid-hydrogen peroxide, an ultraviolet (UV) ozone treatment, and an oxygen gas plasma treatment, on the substrate after the dry etching and before the exposure to the atmosphere.
  • the hydrophilicity on the surface of the oxide film can be improved, and it is possible to suppress inclusion of air bubbles between the oxide film and the electroforming material in a case of producing the electroforming material by using the electroforming master produced by the production method of the present disclosure, and it is possible to suppress the occurrence of defects due to an increase in surface roughness of the electroforming material, which is caused by the air bubbles included.
  • the substrate provided with a pattern on the surface of the electroforming master used for the production a commercially available substrate may be used, or a substrate produced by a known method in the related art may be used.
  • a substrate 20 containing a silicon-based semiconductor is prepared, and one surface of the substrate 20 is thermally oxidized to form an inorganic insulating film 21 as a silicon-based oxide film ( Fig. 2(A) ).
  • a resist is applied to the surface of the inorganic insulating film 21 to form a resist film 22 ( Fig. 2(B) ).
  • the resist is not particularly limited, and an ultraviolet curable resin or the like in the related art, which is used for photolithography, can be used.
  • the resist film 22 is exposed in a patterned manner ( Fig. 2(C) ).
  • the exposure of the resist film 22 can be performed in a patterned manner by using a known patterning mask 23 in the related art.
  • a known developer in the related art is used to remove an exposed portion of the resist film by washing to form a resist mask 24 ( Fig. 2(D) ).
  • the inorganic insulating film 21 formed in a portion where the resist mask 24 is not formed is removed by dry etching, and the resist mask 24 is then peeled off, thereby capable of obtaining a substrate 26 provided with a pattern 25 ( Fig. 2(E) ).
  • the method for producing an electroforming material of the present disclosure includes a step of forming, by using the electroforming master as a cathode, an electroforming material on the surface of the electroforming master on which the oxide film is formed, in an electroforming liquid, and a step of peeling the electroforming material from the electroforming master.
  • the method for producing an electroforming material of the present disclosure it is possible to suppress the electroforming material during growth to be peeled off from the electroforming master.
  • the electroforming master used in the method for producing an electroforming material of the present disclosure includes the substrate, and the oxide film having a thickness of 18 ⁇ or smaller is formed on the surface thereof. It is presumed that since a decrease in electrostatic attraction between the substrate and the electroforming material to be grown on the oxide film is suppressed by setting the thickness of the oxide film to 18 ⁇ or smaller, the above-described electroforming master has excellent adhesiveness to the electroforming material, and the electroforming material during growth is suppressed to be peeled off.
  • the electroforming material can be formed in the electroforming liquid by using the above-described electroforming master as a cathode through energization.
  • the electroforming liquid to be used is not particularly limited, and for example, nickel sulfamic acid electroforming liquid can be used.
  • a material that can be used as an anode is not particularly limited, and for example, a nickel plate can be used.
  • the current density and energization time in the energization are not particularly limited, and it is preferable to appropriately adjust the current density and energization time according to a desired size of the electroforming material to be formed.
  • the current density can be 5A/dm 2 to 10A/dm 2
  • the energization time can be 10 minutes to 2 hours.
  • the electroforming material may be formed only on the surface of the oxide film, but an electroforming material 32 grown on a surface of an oxide film 31 may be formed to ride on a pattern 33 formed by an inorganic insulating film (so-called overgrowth), as illustrated in Fig. 3 .
  • the substrate is denoted by the reference numeral 34.
  • a method for peeling the electroforming material from the electroforming master is not particularly limited, and a known method in the related art can be used.
  • a method for producing an electroforming material of the present disclosure can include a step of washing the electroforming master after the step of peeling the electroforming material from the electroforming master.
  • the method for producing an electroforming material of the present disclosure it is preferable to perform a cycle including the step of washing the electroforming master, the step of forming the electroforming material, and the step of peeling the electroforming material from the electroforming master a plurality of times.
  • a method for washing the electroforming master is not particularly limited, and the electroforming master can be washed by a known method in the related art, and for example, the electroforming master can be washed by using a washing solution containing Caro's acid.
  • the washing solution containing Caro's acid include SH303 manufactured by KANTO KAGAKU.
  • a substrate (thickness of 725 ⁇ m) containing a silicon-based semiconductor was prepared, and one surface of the substrate was thermally oxidized to form an inorganic insulating film having a thickness of 2 ⁇ m.
  • the inorganic insulating film was a silicon-based oxide film containing silane dioxide.
  • a resist (MICROPOSIT (registered trademark) S1818G, manufactured by ROHM AND HAAS ELECTRONIC MATERIALS K.K.) was applied to the surface of the inorganic insulating film by spin coating to form a resist film, and the resist film was exposed in a patterned manner. After the exposure, a developer was used to remove an exposed portion of the resist film by washing to form a resist mask on the inorganic insulating film.
  • the inorganic insulating film formed on a portion of the substrate where the resist mask was not formed was removed by a dry etching method using a mixed gas of CHF 3 and CF 4 .
  • the resist mask was peeled off to prepare a substrate provided with a pattern formed by the inorganic insulating film.
  • Conditions for dry etching included a CHF 3 gas flow rate of 24 ⁇ 10 -4 m 3 /hr, a CF 4 gas flow rate of 6 ⁇ 10 -4 m 3 /hr, a pressure of 0.6 Pa, an inductively coupled plasma (ICP) of 200 W, a bias of 30 W, a lower cooling temperature of 50°C, and a processing time of 80 minutes.
  • ICP inductively coupled plasma
  • the above-described substrate was left to stand in an environment of 23°C and a humidity of 50%RH for 168 hours.
  • the substrate After removing the oxide film, the substrate was exposed to an atmosphere for 5 minutes to form an oxide film on the above-described surface thereof, and an electroforming master was obtained.
  • Conditions for dry etching included a SF 6 gas flow rate of 6 ⁇ 10 -4 m 3 /hr, a pressure of 0.6 Pa, an inductively coupled plasma (ICP) of 500 W, a bias of 15 W, and a processing time of one minute.
  • ICP inductively coupled plasma
  • Conditions of the exposed atmosphere included 1 atm, 23°C, a humidity of 50%RH, and an exposure time of 5 minutes.
  • a thickness of the oxide film formed on the surface of the electroforming master was 8 ⁇ in the atmosphere at 23°C and 50%RH, which was measured with an ellipsometer (automatic ellipsometer DVA-36L manufactured by Mizojiri Optical Co., Ltd.).
  • Electroforming masters were produced in the same manner as in Example 1, except that the exposure time to the atmosphere was changed to times illustrated in Table 1. Thicknesses of oxide films were measured in the same manner as in Example 1, and the results are illustrated in Table 1.
  • An electroforming master was produced in the same manner as in Example 1, except that dry etching was performed with SF 6 gas and CHF 3 gas on a surface of a substrate on which a pattern was formed.
  • Conditions for dry etching included a SF 6 gas flow rate of 6 ⁇ 10 -4 m 3 /hr, a CHF 3 gas flow rate of 24 ⁇ 10 -4 m 3 /hr, a pressure of 0.6 Pa, an inductively coupled plasma of 500W, and a bias of 15W.
  • Thicknesses of oxide films were measured in the same manner as in Example 1, and the results are illustrated in Table 1.
  • An electroforming master was produced in the same manner as in Example 1, except that dry etching was performed with Ar gas on a surface of a substrate on which a pattern was formed.
  • Conditions for dry etching included an Ar gas flow rate of 6 ⁇ 10 -3 m 3 /hr, a pressure of 3 Pa, an inductively coupled plasma of 300 W, a bias of 120 W, and a processing time of one minute.
  • Thicknesses of oxide films were measured in the same manner as in Example 1, and the results are illustrated in Table 1.
  • An electroforming master was produced in the same manner as in Example 1, except that an oxygen gas plasma treatment was performed after dry etching using SF 6 gas was performed on a surface of a substrate on which a pattern is formed and before exposure to the atmosphere.
  • Conditions for oxygen gas plasma treatment included an O 2 gas flow rate of 18 ⁇ 10 -3 m 3 /hr, a pressure of 10 Pa, an inductively coupled plasma of 800 W, a bias of 100 W, and a processing time of one minute.
  • Thicknesses of oxide films were measured in the same manner as in Example 1, and the results are illustrated in Table 1.
  • An electroforming master was produced in the same manner as in Example 1, except that immersion in sulfuric acid-hydrogen peroxide was performed after dry etching using SF 6 gas was performed on a surface of a substrate on which a pattern is formed and before exposure to the atmosphere.
  • the immersion in sulfuric acid-hydrogen peroxide was performed with SH303 manufactured by KANTO KAGAKU. under conditions of an immersion time of 20 minutes and a washing time of 5 minutes.
  • Thicknesses of oxide films were measured in the same manner as in Example 1, and the results are illustrated in Table 1.
  • An electroforming master was produced in the same manner as in Example 1, except that an UV ozone treatment was performed after dry etching using SF 6 gas was performed on a surface of a substrate on which a pattern is formed and before exposure to the atmosphere.
  • the UV ozone treatment was performed by using an UV ozone washing device manufactured by SEN LIGHTS Co., Ltd. and irradiation with ultraviolet rays of a low-pressure mercury lamp (wavelength of 185 nm) for 5 minutes.
  • Thicknesses of oxide films were measured in the same manner as in Example 1, and the results are illustrated in Table 1.
  • An electroforming master was obtained in the same manner as in Example 1, except that no dry etching using SF 6 gas was performed on a surface of a substrate on which a pattern is formed, and no exposure to the atmosphere was performed. Since no dry etching and no exposure to the atmosphere were performed, the surface treatment method and the exposure time to the atmosphere are described as "-" in Table 1.
  • Thicknesses of oxide films were measured in the same manner as in Example 1, and the results are illustrated in Table 1.
  • An electroforming master was produced in the same manner as in Example 1, except that the exposure time to the atmosphere was changed for 116 hours illustrated in Table 1.
  • Thicknesses of oxide films were measured in the same manner as in Example 1, and the results are illustrated in Table 1.
  • An electroforming master was obtained in the same manner as in Example 1, except that no exposure to the atmosphere was performed. Since no exposure to the atmosphere was performed, the exposure time to the atmosphere is described as "-" in Table 1.
  • the contact angle with water was measured by a method of dropping water in air using DMo-701 manufactured by Kyowa Interface Science Co., Ltd. in an environment of 23°C.
  • the water droplet volume used for the measurement was 1 ⁇ L.
  • the electroforming master was immersed in trifluoroacetic anhydride.
  • the end-groups on the surfaces of the oxide films were identified by detecting the presence of a trifluoromethyl group by XPS, all of the end-groups on the surfaces of the oxide films included in the electroforming masters produced in Examples and Comparative Examples were hydroxyl groups.
  • the X-ray source is monochromatic Al K ⁇ ray
  • the X-ray spot diameter is 100 ⁇ m
  • the photoelectron escape angle is 90° (inclination of a detector with respect to the surface of the oxide film).
  • the X-ray photoelectron spectroscope device (Axis-Ultra manufactured by Shimadzu Corporation) was used as XPS.
  • the electroforming master produced in each of Examples and Comparative Examples was used as a cathode and immersed in a nickel electroforming liquid, and energization was performed at a current density of 6.2 A/dm 2 for 50 minutes to electroform nickel on the surface of the electroforming master on which the oxide film was formed, thereby producing an electroforming material having a thickness of 50 ⁇ m.
  • a nickel plate was used as an anode.
  • the current density was changed to 6.2 A/dm 2 , and the energization time was changed to 10 minutes, thereby producing an electroforming material having a thickness of 10 ⁇ m in the same manner as described above.
  • the produced electroforming material was visually observed and evaluated based on the following evaluation standard.
  • the evaluation results are illustrated in Table 1.
  • Comparative Example 3 Although no peeling of either the electroforming material having a thickness of 50 ⁇ m or the electroforming material having a thickness of 10 ⁇ m from the electroforming master was confirmed, cohesion failure of the electroforming material or the electroforming master occurred in a case where these electroforming materials were peeled off from the electroforming masters.
  • the produced electroforming material was peeled off from the electroforming master, and a surface roughness Ra of a peeled surface of the electroforming material was measured by using a non-contact 3D surface roughness/shape measuring machine (New View 7300 manufactured by Zygo Corporation), and the measurement results are illustrated in Table 1.
  • the surface roughness Ra of the electroforming material having a thickness of 50 ⁇ m was measured in each of Examples and Comparative Examples evaluated as A in the adhesiveness evaluation, and the surface roughness Ra of the electroforming material having a thickness of 10 ⁇ m was measured in each of Examples and Comparative Examples evaluated as B in the adhesiveness evaluation.
  • Example 1 Surface treatment method for surface of substrate on which pattern is formed Exposure time to atmosphere Thickness of oxide film [ ⁇ ] Contact angle with water [°] End-group Evaluation of adhesiveness Surface roughness Ra [nm]
  • Example 1 Etching with SF 6 gas 5 minutes 8 28 -OH A 3.0
  • Example 2 Etching with SF 6 gas One hour 15 29 -OH A 3.3
  • Example 3 Etching with SF 6 gas 2.5 hours 16 31 -OH A 8.6
  • Example 4 Etching with SF 6 gas 4.5 hours 17 31 -OH A 8.7
  • Example 5 Etching with SF 6 gas 20 hours 18 27 -OH B 8.7
  • Example 6 Etching with SF 6 gas and etching with CHF 3 gas 5 minutes 9 26 -OH A 5.0
  • Example 7 Etching with Ar gas 5 minutes 7 11 -OH A 2.1
  • Example 8 Etching with SF 6 gas and oxygen gas plasma treatment 5 minutes 14 24 -OH A 9.0
  • Example 9 Etching with SF 6 gas and immersion in sulfuric acid-hydrogen peroxide
  • the electroforming master including the oxide film having a thickness of 18 ⁇ or smaller in each of Examples has excellent adhesive strength to the electroforming material, and peeling of the electroforming material during growth can be effectively suppressed.
  • the electroforming master including the oxide film having a thickness of 18 ⁇ or greater in each of Comparative Examples had a lower adhesive strength to the electroforming master than the electroforming master in each of Examples, and the electroforming material during growth was peeled off.
  • the electroforming material produced for the evaluation of the adhesiveness between the electroforming master and the electroforming material was peeled off from the electroforming master in each of Examples 1 to 10, and the electroforming master was washed with SH303 manufactured by KANTO KAGAKU.
  • nickel was electroformed on the electroforming master by the above-described method to produce an electroforming material.
  • the production of the electroforming material, the peeling of the electroforming material, and the washing of the electroforming master were set as one cycle, and this cycle was repeated 5 times.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacture Or Reproduction Of Printing Formes (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
EP22194324.4A 2021-09-17 2022-09-07 Galvanoplastik-master, verfahren zur herstellung des galvanoplastik-masters und verfahren zur herstellung eines galvanoplastik-materials Pending EP4151776A1 (de)

Applications Claiming Priority (1)

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JP2021152119A JP2023044211A (ja) 2021-09-17 2021-09-17 電鋳用原盤、電鋳用原盤の製造方法及び電鋳物の製造方法

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1510599A2 (de) * 2003-09-01 2005-03-02 Matsushita Electric Industrial Co., Ltd. Herstellungsverfahren einer Matrize, Matrize und optische Aufzeichnungsträger
JP2005256110A (ja) 2004-03-12 2005-09-22 Seiko Instruments Inc 電鋳用型の構造と製造方法およびその電鋳用型を用いた電鋳方法
US7088116B1 (en) * 2005-02-09 2006-08-08 Haian Lin Optoelectronic probe
JP2007287216A (ja) 2006-04-14 2007-11-01 Shin Etsu Chem Co Ltd 磁気記録媒体用基板およびその製造方法ならびに磁気記録媒体
US20090008703A1 (en) * 2007-07-06 2009-01-08 Macronix International Co., Ltd. Non-volatile memory cell and fabricating method thereof
US20100116676A1 (en) * 2008-11-12 2010-05-13 Samsung Electro-Mechanics Co., Ltd. Method of fabricating probe pin for probe card
WO2013084429A1 (ja) * 2011-12-09 2013-06-13 コニカミノルタ株式会社 金属格子の製造方法、金属格子およびｘ線撮像装置
EP2781626A1 (de) * 2011-11-15 2014-09-24 Leap Co. Ltd. Herstellungsverfahren für eine pressspritzform, in diesem verfahren hergestellte pressspritzform sowie unter verwendung dieser pressspritzform hergestellte komponente

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1510599A2 (de) * 2003-09-01 2005-03-02 Matsushita Electric Industrial Co., Ltd. Herstellungsverfahren einer Matrize, Matrize und optische Aufzeichnungsträger
JP2005256110A (ja) 2004-03-12 2005-09-22 Seiko Instruments Inc 電鋳用型の構造と製造方法およびその電鋳用型を用いた電鋳方法
US7088116B1 (en) * 2005-02-09 2006-08-08 Haian Lin Optoelectronic probe
JP2007287216A (ja) 2006-04-14 2007-11-01 Shin Etsu Chem Co Ltd 磁気記録媒体用基板およびその製造方法ならびに磁気記録媒体
US20090008703A1 (en) * 2007-07-06 2009-01-08 Macronix International Co., Ltd. Non-volatile memory cell and fabricating method thereof
US20100116676A1 (en) * 2008-11-12 2010-05-13 Samsung Electro-Mechanics Co., Ltd. Method of fabricating probe pin for probe card
EP2781626A1 (de) * 2011-11-15 2014-09-24 Leap Co. Ltd. Herstellungsverfahren für eine pressspritzform, in diesem verfahren hergestellte pressspritzform sowie unter verwendung dieser pressspritzform hergestellte komponente
WO2013084429A1 (ja) * 2011-12-09 2013-06-13 コニカミノルタ株式会社 金属格子の製造方法、金属格子およびｘ線撮像装置

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