US20230174420A1 - Method of fabricating metal thin film supported by glass support - Google Patents
Method of fabricating metal thin film supported by glass support Download PDFInfo
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- US20230174420A1 US20230174420A1 US18/103,789 US202318103789A US2023174420A1 US 20230174420 A1 US20230174420 A1 US 20230174420A1 US 202318103789 A US202318103789 A US 202318103789A US 2023174420 A1 US2023174420 A1 US 2023174420A1
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- thin film
- metal thin
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- glass substrate
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- 239000011521 glass Substances 0.000 title claims abstract description 104
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 81
- 239000002184 metal Substances 0.000 title claims abstract description 81
- 239000010409 thin film Substances 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 60
- 239000010410 layer Substances 0.000 claims description 41
- 230000004888 barrier function Effects 0.000 claims description 16
- 239000011651 chromium Substances 0.000 claims description 9
- 239000002356 single layer Substances 0.000 claims description 6
- 239000010408 film Substances 0.000 claims description 5
- 230000001458 anti-acid effect Effects 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 229910001029 Hf alloy Inorganic materials 0.000 claims description 3
- 229910004353 Ti-Cu Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004809 Teflon Substances 0.000 claims description 2
- 229920006362 Teflon® Polymers 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- 238000010030 laminating Methods 0.000 claims description 2
- 239000005361 soda-lime glass Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 238000005530 etching Methods 0.000 abstract description 53
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 10
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 10
- 238000000034 method Methods 0.000 description 8
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- 241000282575 Gorilla Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3634—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer at least containing carbon, a carbide or oxycarbide
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3639—Multilayers containing at least two functional metal layers
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/06—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3649—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer made of metals other than silver
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/38—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal at least one coating being a coating of an organic material
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/25—Metals
- C03C2217/257—Refractory metals
- C03C2217/26—Cr, Mo, W
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/28—Other inorganic materials
- C03C2217/282—Carbides, silicides
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/32—After-treatment
- C03C2218/328—Partly or completely removing a coating
- C03C2218/33—Partly or completely removing a coating by etching
Definitions
- the present disclosure relates to a method of fabricating a metal thin film-on-glass structure. More particularly, the present disclosure relates to method of fabricating a metal thin film-on glass structure in which a local area of a glass substrate, on the top surface of which a layer including a metal thin film is formed, is removed by etching.
- metal thin films There are a range of technical fields in which metal thin films are required. Furthermore, a variety of technical fields need metal thin films having a thickness in the range of nanometers to micrometers.
- FIG. 1 schematically illustrates a conventional method of fabricating a metal thin film 21 supported by a glass support 10 b.
- the metal thin film 21 supported by the glass support 10 b is fabricated by welding the glass support 10 b, made by making a local hole in a glass substrate 10 , to the free-standing metal thin film 21 .
- fabrication costs may be inefficiently high, and may be difficult to handle the free-standing metal thin film.
- the method illustrated in FIG. 1 is not practical as a method of fabricating the metal thin film 21 supported by the glass substrate 10 b, and other methods that can overcome the above-mentioned limitations are required.
- Various aspects of the present disclosure provide a metal thin film supported by a glass support.
- a method of fabricating a metal thin film-on-glass structure may include: preparing a glass substrate, on a top surface of which a layer is formed; and etching a local area of the glass substrate from a bottom of the glass substrate to expose the layer downwardly, thereby forming an exposed area of the layer.
- the layer may be a metal thin film.
- the etching step may include: first-etching the glass substrate to a depth less than a thickness of the glass substrate using a first etching solution containing hydrofluoric acid and at least one of nitric acid and sulfuric acid, resulting in a first-etched portion of the glass substrate; and second-etching the first-etched portion of the glass substrate using an etching solution containing hydrofluoric acid without nitric acid or sulfuric acid, so that the layer is exposed downwardly, whereby the metal thin film is supported by a remaining portion of the glass substrate.
- a metal thin film having a thickness in the range of nanometers to micrometers and supported by a glass support can be fabricated.
- the thickness of a barrier layer can be minimized, and the thickness of the metal thin film can also be reduced.
- FIG. 1 schematically illustrates a conventional method of fabricating a metal thin film supported by a glass support
- FIG. 2 schematically illustrates a method of fabricating a metal thin film supported by a glass support according to a first embodiment
- FIG. 3 schematically illustrates a metal thin film supported by a glass support according to a second embodiment
- FIG. 4 is an image illustrating a cross-section of a structure, including a glass substrate, a barrier layer, and a metal thin film, in the embodiment illustrated in FIG. 3 , the glass substrate having been first-etched before being second-etched;
- FIG. 5 is a bottom view illustrating the metal thin film supported by the glass support illustrated in FIG. 3 ;
- FIG. 6 schematically illustrates a metal thin film supported by a glass support according to a third embodiment.
- orientations such as “upper surface,” “lower surface,” “upward direction,” and “downward direction,” may be used herein for the ease of description of specific components with reference to the drawings. It should be understood, however, that these terms are not intended to indicate actual orientations.
- the terms “upper surface” and “lower surface” are only used to describe that an upper surface and a lower surface are opposite each other. In actual practice, the upper surface may be located at a lower location than the lower surface.
- Exemplary embodiments relate to a selective substrate etching process that can minimize damage to a metal thin film formed on a glass substrate to a thickness in the range of nanometers to micrometers.
- FIG. 2 schematically illustrates a method of fabricating a metal thin film 21 supported by a glass support 10 b according to a first embodiment
- FIG. 3 schematically illustrates a metal thin film 21 supported by a glass support 10 b according to a second embodiment
- FIG. 4 is an image illustrating a cross-section of a structure, including a glass substrate, a barrier layer, and a metal thin film, in the embodiment illustrated in FIG. 3 , the glass substrate having been first-etched before being second-etched
- FIG. 5 is a bottom view illustrating the metal thin film 21 supported by the glass support 10 b illustrated in FIG. 3 .
- a glass substrate 10 on the top surface of which a layer 20 is formed, is prepared (preparation step). Afterwards, a local area 10 a of the glass substrate 10 is etched from the bottom, so that the layer 20 is exposed downwardly (etching step).
- the layer 20 includes a metal thin film 21 .
- the layer 20 may be formed on the top surface of the glass substrate 10 by deposition.
- etching solution such as hydrofluoric acid (HF)
- HF hydrofluoric acid
- Si silicon
- etching solutions for glass substrates include a variety of materials, such as nitric acid (HNO 3 ) and sulfuric acid (H 2 SO 4 ), depending on the composition of glass, together with hydrofluoric acid, to increase the etching rate.
- a barrier layer 23 may be disposed between the metal thin film 21 and the glass substrate 10 to prevent the metal thin film 21 from being damaged by hydrofluoric acid when the glass substrate 10 is being etched.
- the barrier layer 23 may contain chromium (Cr) with or without hafnium (Hf).
- Cr may be a main component, and the weight of Hf may be less than 60% of the total weight of the barrier layer. In consideration of acid resistance against hydrofluoric acid, the amount of Hf may be less than that of Cr.
- the barrier layer 23 may be easily damaged by nitric acid and sulfuric acid, and consequently, the metal thin film 21 may be damaged or contaminated by the etching solution.
- the barrier layer 23 may be formed by i) laminating a SiC- or Teflon-based anti-acid film, ii) applying an anti-acid solution, or iii) deposition.
- the barrier layer 23 may have a thickness ranging from 0.001 ⁇ m to 5 ⁇ m. In some of such embodiments, the thickness of the barrier layer may range from 0.001 ⁇ m to 1 ⁇ m.
- the present disclosure suggests an etching process having two steps to achieve selective etching that can minimize damage to the metal thin film 21 formed on the glass substrate 10 .
- the glass substrate 10 is first-etched to a depth less than the thickness of the glass substrate 10 using a first etching solution.
- the etching depth may be obtained by multiplying the etching rate (i.e. etching depth per unit time) by elapsed time for etching.
- the first-etched portion is second-etched using a second etching solution, so that the layer 20 is exposed downwardly.
- the first etching solution is prepared by mixing an HF solution, a typical glass etching solution, with a chemical material, such as HNO 3 or H 2 SO 4 , at a predetermined mixture ratio to increase the etching rate of the glass substrate 10 .
- a chemical material such as HNO 3 or H 2 SO 4
- the chemical material may vary depending on the composition of glass.
- the addition of the chemical material can reduce the etching time by 50% or more compared to pure HF. Consequently, the glass substrate 10 can be etched at a fast rate to a depth close to the metal thin film 21 formed on the substrate 10 .
- the etching may be performed, for example, for several to tens of seconds. In some embodiments, the etching temperature typically does not exceed 80° C.
- the second etching solution may be prepared using pure HF alone. HF can selectively etch the glass substrate 10 while minimizing damage to the metal thin film 21 , due to low reactivity with Cr or Cr—Hf thereof.
- the first etching solution may include, by weight, hydrofluoric acid 50% to 100%, nitric acid 0% to 50%, and sulfuric acid 0% to 50%, while the second etching solution may include, by weight, hydrofluoric acid 50% to 100%.
- the etching may be wet etching.
- the glass substrate 10 may be etched by a variety of methods depending on the composition and thickness thereof and the shape and area thereof to be etched.
- the glass substrate 10 may be etched by spray etching, or a plurality of the glass substrate 10 may be etched in a batch.
- the first etching rate may not exceed 10 ⁇ m per minute, and the second etching rate may range from 0.1 to 10 ⁇ m per minute.
- the glass substrate 10 may include soda-lime glass.
- the glass substrate 10 may include glass which can be toughened by ion exchange (glass prior to being subjected to a chemical toughening process).
- the glass substrate 10 may be provided using Gorilla® Glass or EXG® Glass available from Corning Incorporated.
- the present disclosure is applicable to a case in which the diameter of the circumscribed circle of the exposed area 20 a of the layer 20 exposed after the etching may be 1 inch or greater. In some of such embodiments, the diameter of the circumscribed circle of the exposed area may be 3 inches or more. For example, as illustrated in FIG. 6 , when the local area 10 a (thus the exposed area 20 a ) is oblong, the diameter of the circumscribed circle of the exposed area is the length of a diagonal of the oblong figure.
- a seed layer facilitating the formation of the metal thin film 21 may be provided on the glass substrate 10 , and then, the metal thin film 21 may be provided on the seed layer.
- the seed layer may contain a conductive metal.
- the metal thin film 21 may be i) a Cr monolayer, ii) a Cr—Hf alloy monolayer, iii) a Cr—Ag multilayer or a Cr—Ti—Cu multilayer, or the like. In some embodiments, the metal thin film 21 may have a thickness in the range of nanometers to micrometers. In some embodiments, the metal thin film 21 may have a thickness not exceeding 10 ⁇ m. The metal thin film 21 , according to some embodiments, may have a thickness of 1 ⁇ m to 5 ⁇ m.
- the metal thin film 21 may be a metal thin film that is patterned prior to the etching step, or a step of pattering the metal thin film 21 after the etching step may be additionally provided.
- the metal thin film in which fine through-holes are patterned may be used as a fine-patterned mask for deposition, a water filter, or the like.
- the metal thin film may be coated with ceramic to be used as a battery separator.
- FIG. 6 schematically illustrates a metal thin film 21 supported by a glass support 10 b according to a third embodiment.
- a plurality of local areas l 0 a separated from each other may be provided.
- the plurality of local areas l 0 a may be arranged in a matrix (e.g. a 3 ⁇ 4 matrix in FIG. 6 ).
- a matrix e.g. a 3 ⁇ 4 matrix in FIG. 6 .
- the present disclosure is not limited thereto, but a variety of different arrangements are possible.
- the shape of a single local area 10 a (and thus the shape of an exposed area 20 a ) may have a variety of other forms instead of being limited to an oblong shape.
- 10 glass substrate, 10 a: local area
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Abstract
A method of fabricating a metal thin film-on-glass structure. A glass substrate, on a top surface of which a layer is formed, is prepared. A local area of the glass substrate is etched from a bottom of the glass substrate to expose the layer downwardly, thereby forming an exposed area of the layer. The layer is a metal thin film. The etching includes first-etching the glass substrate to a depth less than a thickness of the glass substrate using a first etching solution containing hydrofluoric acid and at least one of nitric acid and sulfuric acid, resulting in a first-etched portion of the glass substrate; and second-etching the first-etched portion of the glass substrate using an etching solution containing hydrofluoric acid without nitric acid or sulfuric acid, so that the layer is exposed downwardly, whereby the metal thin film is supported by a remaining portion of the glass substrate.
Description
- This application is a divisional application of U.S. application Ser. No. 16/491,363 filed Sep. 5, 2019, which claims the benefit of priority under 35 U.S.C. § 371 of International Application Serial No. PCT/KR2018/002830, filed on Mar. 9, 2018, which claims the benefit of priority under 35 U.S.C. § 119 of Korean Patent Application Serial No.: 10-2018-0027639, filed on Mar. 8, 2018, which claims the benefit of priority under 35 U.S.C. § 119 of Korean Patent Application Serial No.: 10-2017-0030149, filed on Mar. 9, 2017, the content of which is relied upon and incorporated herein by reference in its entirety.
- The present disclosure relates to a method of fabricating a metal thin film-on-glass structure. More particularly, the present disclosure relates to method of fabricating a metal thin film-on glass structure in which a local area of a glass substrate, on the top surface of which a layer including a metal thin film is formed, is removed by etching.
- There are a range of technical fields in which metal thin films are required. Furthermore, a variety of technical fields need metal thin films having a thickness in the range of nanometers to micrometers.
-
FIG. 1 schematically illustrates a conventional method of fabricating a metalthin film 21 supported by aglass support 10 b. - As illustrated in
FIG. 1 , the metalthin film 21 supported by theglass support 10 b is fabricated by welding theglass support 10 b, made by making a local hole in aglass substrate 10, to the free-standing metalthin film 21. However, it may be difficult to fabricate a free-standing metal thin film having a thickness in the range of nanometers to micrometers. Even in the case that a free-standing metal thin film is fabricated, there may still be limitations, in that fabrication costs may be inefficiently high, and may be difficult to handle the free-standing metal thin film. - Accordingly, the method illustrated in
FIG. 1 is not practical as a method of fabricating the metalthin film 21 supported by theglass substrate 10 b, and other methods that can overcome the above-mentioned limitations are required. - Various aspects of the present disclosure provide a metal thin film supported by a glass support.
- According to an aspect, a method of fabricating a metal thin film-on-glass structure may include: preparing a glass substrate, on a top surface of which a layer is formed; and etching a local area of the glass substrate from a bottom of the glass substrate to expose the layer downwardly, thereby forming an exposed area of the layer. The layer may be a metal thin film. The etching step may include: first-etching the glass substrate to a depth less than a thickness of the glass substrate using a first etching solution containing hydrofluoric acid and at least one of nitric acid and sulfuric acid, resulting in a first-etched portion of the glass substrate; and second-etching the first-etched portion of the glass substrate using an etching solution containing hydrofluoric acid without nitric acid or sulfuric acid, so that the layer is exposed downwardly, whereby the metal thin film is supported by a remaining portion of the glass substrate.
- As set forth above, a metal thin film having a thickness in the range of nanometers to micrometers and supported by a glass support can be fabricated.
- In addition, it is possible to selectively etch a glass substrate while minimizing damage to the metal thin film.
- Furthermore, since damage to the metal thin film by the etching solution is minimized, the thickness of a barrier layer can be minimized, and the thickness of the metal thin film can also be reduced.
- In addition, relatively greater deviations in thickness of the glass substrate are possible, thereby reducing costs required for the manufacturing of a precision glass substrate allowing relatively low deviations only.
- The methods and apparatuses of the present disclosure have other features and advantages that will be apparent from or that are set forth in greater detail in the accompanying drawings which are incorporated herein, and in the following Detailed Description, which together serve to explain certain principles of the present disclosure.
-
FIG. 1 schematically illustrates a conventional method of fabricating a metal thin film supported by a glass support; -
FIG. 2 schematically illustrates a method of fabricating a metal thin film supported by a glass support according to a first embodiment; -
FIG. 3 schematically illustrates a metal thin film supported by a glass support according to a second embodiment; -
FIG. 4 is an image illustrating a cross-section of a structure, including a glass substrate, a barrier layer, and a metal thin film, in the embodiment illustrated inFIG. 3 , the glass substrate having been first-etched before being second-etched; -
FIG. 5 is a bottom view illustrating the metal thin film supported by the glass support illustrated inFIG. 3 ; and -
FIG. 6 schematically illustrates a metal thin film supported by a glass support according to a third embodiment. - Hereinafter, exemplary embodiments of the present disclosure will be described in detail with reference to the accompanying drawings.
- Terms relating to orientations, such as “upper surface,” “lower surface,” “upward direction,” and “downward direction,” may be used herein for the ease of description of specific components with reference to the drawings. It should be understood, however, that these terms are not intended to indicate actual orientations. For example, the terms “upper surface” and “lower surface” are only used to describe that an upper surface and a lower surface are opposite each other. In actual practice, the upper surface may be located at a lower location than the lower surface.
- Exemplary embodiments relate to a selective substrate etching process that can minimize damage to a metal thin film formed on a glass substrate to a thickness in the range of nanometers to micrometers.
-
FIG. 2 schematically illustrates a method of fabricating a metalthin film 21 supported by aglass support 10 b according to a first embodiment,FIG. 3 schematically illustrates a metalthin film 21 supported by aglass support 10 b according to a second embodiment,FIG. 4 is an image illustrating a cross-section of a structure, including a glass substrate, a barrier layer, and a metal thin film, in the embodiment illustrated inFIG. 3 , the glass substrate having been first-etched before being second-etched, andFIG. 5 is a bottom view illustrating the metalthin film 21 supported by theglass support 10 b illustrated inFIG. 3 . - According to the methods illustrated in
FIGS. 2 and 3 , first, aglass substrate 10, on the top surface of which alayer 20 is formed, is prepared (preparation step). Afterwards, alocal area 10 a of theglass substrate 10 is etched from the bottom, so that thelayer 20 is exposed downwardly (etching step). Thelayer 20 includes a metalthin film 21. In the preparation step, thelayer 20 may be formed on the top surface of theglass substrate 10 by deposition. - Conventional selective etching of a glass substrate is undertaken as follows. First, an acid resistant film is attached to the
glass substrate 10 and is then patterned. Afterwards, chemical etching is performed by bringing the glass substrate into physical contact with an etching solution using the patterned acid resistant film as a mask. - In general, an etching solution, such as hydrofluoric acid (HF), is used to etch a semiconductor substrate, such as a silicon (Si) substrate. However, when the etching solution for semiconductor substrates is used for etching a glass substrate, a relatively long etching time may cause damage to the acid resistant film, which is problematic. Thus, etching solutions for glass substrates include a variety of materials, such as nitric acid (HNO3) and sulfuric acid (H2SO4), depending on the composition of glass, together with hydrofluoric acid, to increase the etching rate.
- A
barrier layer 23 may be disposed between the metalthin film 21 and theglass substrate 10 to prevent the metalthin film 21 from being damaged by hydrofluoric acid when theglass substrate 10 is being etched. Thebarrier layer 23 may contain chromium (Cr) with or without hafnium (Hf). According to some embodiments, Cr may be a main component, and the weight of Hf may be less than 60% of the total weight of the barrier layer. In consideration of acid resistance against hydrofluoric acid, the amount of Hf may be less than that of Cr. Thebarrier layer 23 may be easily damaged by nitric acid and sulfuric acid, and consequently, the metalthin film 21 may be damaged or contaminated by the etching solution. According to some embodiments, thebarrier layer 23 may be formed by i) laminating a SiC- or Teflon-based anti-acid film, ii) applying an anti-acid solution, or iii) deposition. According to some embodiments, thebarrier layer 23 may have a thickness ranging from 0.001 μm to 5 μm. In some of such embodiments, the thickness of the barrier layer may range from 0.001 μm to 1 μm. - To prevent damage by hydrofluoric acid, precise etching in the range of several nanometers is necessary. However, such a level of precision is impossible due to the characteristics of wet etching. In addition, when partial over-etching is caused due to deviations in the thickness of the
glass substrate 10, the metalthin film 21 is damaged. - To prevent the metal thin film from being damaged, the present disclosure suggests an etching process having two steps to achieve selective etching that can minimize damage to the metal
thin film 21 formed on theglass substrate 10. Specifically, in the first etching step, theglass substrate 10 is first-etched to a depth less than the thickness of theglass substrate 10 using a first etching solution. For example, the etching depth may be obtained by multiplying the etching rate (i.e. etching depth per unit time) by elapsed time for etching. In the second etching step, the first-etched portion is second-etched using a second etching solution, so that thelayer 20 is exposed downwardly. - The first etching solution is prepared by mixing an HF solution, a typical glass etching solution, with a chemical material, such as HNO3 or H2SO4, at a predetermined mixture ratio to increase the etching rate of the
glass substrate 10. For example, the mixture ratio of HF (20%), HNO3, and H2SO4 may be 1:1:1 by weight. The chemical material may vary depending on the composition of glass. The addition of the chemical material can reduce the etching time by 50% or more compared to pure HF. Consequently, theglass substrate 10 can be etched at a fast rate to a depth close to the metalthin film 21 formed on thesubstrate 10. The etching may be performed, for example, for several to tens of seconds. In some embodiments, the etching temperature typically does not exceed 80° C. - The second etching solution may be prepared using pure HF alone. HF can selectively etch the
glass substrate 10 while minimizing damage to the metalthin film 21, due to low reactivity with Cr or Cr—Hf thereof. - According to some embodiments, the first etching solution may include, by weight, hydrofluoric acid 50% to 100%, nitric acid 0% to 50%, and sulfuric acid 0% to 50%, while the second etching solution may include, by weight, hydrofluoric acid 50% to 100%.
- The etching may be wet etching. In each etching step, the
glass substrate 10 may be etched by a variety of methods depending on the composition and thickness thereof and the shape and area thereof to be etched. Theglass substrate 10 may be etched by spray etching, or a plurality of theglass substrate 10 may be etched in a batch. - According to some embodiments, in room temperature and normal pressure conditions, the first etching rate may not exceed 10 μm per minute, and the second etching rate may range from 0.1 to 10 μm per minute.
- The
glass substrate 10 may include soda-lime glass. Alternatively, theglass substrate 10 may include glass which can be toughened by ion exchange (glass prior to being subjected to a chemical toughening process). For example, theglass substrate 10 may be provided using Gorilla® Glass or EXG® Glass available from Corning Incorporated. - In some embodiments, the present disclosure is applicable to a case in which the diameter of the circumscribed circle of the exposed
area 20 a of thelayer 20 exposed after the etching may be 1 inch or greater. In some of such embodiments, the diameter of the circumscribed circle of the exposed area may be 3 inches or more. For example, as illustrated inFIG. 6 , when thelocal area 10 a (thus the exposedarea 20 a) is oblong, the diameter of the circumscribed circle of the exposed area is the length of a diagonal of the oblong figure. - According to some embodiments, prior to the formation of the metal
thin film 21 on theglass substrate 10, a seed layer facilitating the formation of the metalthin film 21 may be provided on theglass substrate 10, and then, the metalthin film 21 may be provided on the seed layer. The seed layer may contain a conductive metal. - In some embodiments, the metal
thin film 21 may be i) a Cr monolayer, ii) a Cr—Hf alloy monolayer, iii) a Cr—Ag multilayer or a Cr—Ti—Cu multilayer, or the like. In some embodiments, the metalthin film 21 may have a thickness in the range of nanometers to micrometers. In some embodiments, the metalthin film 21 may have a thickness not exceeding 10 μm. The metalthin film 21, according to some embodiments, may have a thickness of 1 μm to 5 μm. - The metal
thin film 21 may be a metal thin film that is patterned prior to the etching step, or a step of pattering the metalthin film 21 after the etching step may be additionally provided. The metal thin film in which fine through-holes are patterned may be used as a fine-patterned mask for deposition, a water filter, or the like. In addition, the metal thin film may be coated with ceramic to be used as a battery separator. -
FIG. 6 schematically illustrates a metalthin film 21 supported by aglass support 10 b according to a third embodiment. - As illustrated in
FIG. 6 , a plurality of local areas l0 a separated from each other may be provided. The plurality of local areas l0 a may be arranged in a matrix (e.g. a 3×4 matrix inFIG. 6 ). However, the present disclosure is not limited thereto, but a variety of different arrangements are possible. In addition, the shape of a singlelocal area 10 a (and thus the shape of an exposedarea 20 a) may have a variety of other forms instead of being limited to an oblong shape. - 10: glass substrate, 10 a: local area
- 10 b: glass support, 20: layer
- 20 a: exposed area, 21: metal thin film,
- 23: Barrier act
Claims (13)
1. The metal thin film-on-glass structure comprising:
a layer comprising a metal thin film;
a glass support, in which a local hole is foiled, provided on a bottom surface of the layer such that the layer is supported by the glass support and the local hole exposes the layer downwardly,
wherein the thickness of the metal thin film ranges from 1 micrometer to 5 micrometers.
2. The metal thin film-on-glass structure of claim 1 , wherein the metal thin film comprises at least one selected from the group consisting of a Cr monolayer, a Cr—Hf alloy monolayer, a Cr—Ag multilayer, and a Cr—Ti—Cu multilayer.
3. The metal thin film-on-glass structure of claim 1 , wherein the glass support comprises soda-lime glass.
4. The metal thin film-on-glass structure of claim 1 , wherein the glass support comprises non-alkali glass.
5. The metal thin film-on-glass structure of claim 1 , wherein the glass support comprises glass which can be toughened by ion exchange.
6. The metal thin film-on-glass structure of claim 1 , wherein the layer further comprises a barrier layer disposed between the metal thin film and the glass substrate.
7. The metal thin film-on-glass structure of claim 6 , wherein the barrier layer contains chromium with or without hafnium.
8. The metal thin film-on-glass structure of claim 6 , wherein the barrier layer is formed by i) laminating a SiC- or Teflon-based anti-acid film, ii) applying an anti-acid solution, or iii) deposition.
9. The metal thin film-on-glass structure of claim 6 , wherein the barrier layer has a thickness ranging from 0.001 μm to 5 μm.
10. The metal thin film-on-glass structure of claim 1 , wherein the metal thin film is a patterned metal thin film.
11. The metal thin film-on-glass structure comprising:
a layer comprising a metal thin film;
a glass support, in which a local hole is formed, provided on a bottom surface of the layer such that the layer is supported by the glass support and the local hole exposes the layer downwardly.
12. The metal thin film-on-glass structure of claim 11 , wherein the layer further comprises a barrier layer disposed between the metal thin film and the glass substrate.
13. The metal thin film-on-glass structure of claim 11 , wherein the metal thin film comprises at least one selected from the group consisting of a Cr monolayer, a Cr—Hf alloy monolayer, a Cr—Ag multilayer, and a Cr—Ti—Cu multilayer.
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KR1020180027639A KR102007428B1 (en) | 2017-03-09 | 2018-03-08 | Method of fabricating a metal thin film supported by a glass support |
KR10-2018-0027639 | 2018-03-08 | ||
PCT/KR2018/002830 WO2018164535A1 (en) | 2017-03-09 | 2018-03-09 | Method for manufacturing metal thin film supported by glass support |
US202016491363A | 2020-04-14 | 2020-04-14 | |
US18/103,789 US20230174420A1 (en) | 2017-03-09 | 2023-01-31 | Method of fabricating metal thin film supported by glass support |
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US16/491,363 Division US11584683B2 (en) | 2017-03-09 | 2018-03-09 | Method of fabricating a metal thin film supported by a glass support |
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US20200407272A1 (en) | 2020-12-31 |
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