WO2018030703A1 - 나노돌기 표면 형성 방법 및 그 방법에 의해 형성된 나노돌기 표면을 갖는 모재 - Google Patents

나노돌기 표면 형성 방법 및 그 방법에 의해 형성된 나노돌기 표면을 갖는 모재 Download PDF

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WO2018030703A1
WO2018030703A1 PCT/KR2017/008349 KR2017008349W WO2018030703A1 WO 2018030703 A1 WO2018030703 A1 WO 2018030703A1 KR 2017008349 W KR2017008349 W KR 2017008349W WO 2018030703 A1 WO2018030703 A1 WO 2018030703A1
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forming
acid
acid solution
weight
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PCT/KR2017/008349
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English (en)
French (fr)
Korean (ko)
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이상로
김윤환
서재형
김기훈
이지영
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(주)에스이피
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Priority to JP2019507180A priority Critical patent/JP6698938B2/ja
Priority to US16/323,911 priority patent/US11618710B2/en
Priority to CN201780048666.6A priority patent/CN109564867B/zh
Publication of WO2018030703A1 publication Critical patent/WO2018030703A1/ko

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/30604—Chemical etching
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
    • G03F1/80—Etching
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2008—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the reflectors, diffusers, light or heat filtering means or anti-reflective means used
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02299—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment
    • H01L21/02307—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment treatment by exposure to a liquid
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
    • H01L21/0237—Materials
    • H01L21/0242—Crystalline insulating materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only

Definitions

  • the present invention relates to a method of forming nanoprotrusions on a base material (glass or a polymer film substrate having glass characteristics), and does not use a mask as a selective etching resistance means. Or it relates to a maskless wet nano patterning method for forming a projection having a width of several tens nm ⁇ um and a base material having a surface of the nano-protrusion formed by the method.
  • the etching process may be classified into wet etching and dry etching.
  • Wet etching is generally performed through chemical reaction between the etching solution having the property of corrosion dissolution and the base material to be etched.
  • Wet etching is isotropic etching with the same etching speed in the vertical and horizontal directions.
  • Dry etching is an etching process using a reaction by gas plasma or activated gas. Dry etching is anisotropic etching with different etching rates in the vertical and horizontal directions.
  • wet etching is easier to process and advantageous to mass production than dry etching, but the pattern formed through wet etching has an average width of 3 ⁇ m or more.
  • Nano patterning technology for realizing anti-reflection has been attracting attention, but the high-cost nano masks are difficult It is difficult to be used due to the difficulty in processing a curved surface or a large area.
  • One problem to be solved by the proposed invention is to form nanoprobes having a width of several nm to several tens nm or several tens of nm to several um through a wet etching process.
  • Another problem to be solved by the proposed invention is to produce a polymer film having glass or glass characteristics to prevent glare through a wet etching process.
  • Another problem to be solved by the proposed invention is to produce a polymer film having glass or glass properties to prevent reflection through a wet etching process.
  • Another problem to be solved by the proposed invention is to produce a polymer film having a glass or glass characteristics to prevent glare and reflection at the same time through a wet etching process.
  • the method of forming a protrusion according to the present invention includes forming a protrusion on a polymer film substrate having glass or glass characteristics by wet etching.
  • the forming of the protrusions may include forming an anti-glare layer including protrusions having a width of several tens of nm to several um by wet etching using an acid solution.
  • the acid solution is characterized in that it comprises a fluorine-based acid and nitric acid.
  • the acid solution also includes hydrogen fluoride and nitric acid, including ammonium fluoride, phosphoric acid, It further comprises at least one of hydrochloric acid.
  • the content of hydrogen fluoride in the acid solution is characterized in that less than 10% by weight.
  • the content of nitric acid in the acid solution is characterized in that more than 10% by weight and less than 25% by weight.
  • the content is characterized in that less than 5% by weight.
  • the content is characterized in that less than 5% by weight.
  • the content is characterized in that less than 10% by weight.
  • the acid solution may also be hydrogen fluoride, ammonium fluoride, phosphoric acid, Including nitric acid, hydrochloric acid and water, the content of each component with respect to 100% by weight of the acid solution, the hydrogen fluoride 10% by weight or less, the ammonium fluoride 5% by weight or less, the nitric acid 10% by weight or more at 25% Up to percent, the phosphoric acid is up to 5 weight percent, the hydrochloric acid is up to 10 weight percent, and the remainder consists of the water.
  • the forming of the protrusions may include forming an anti-reflection layer including protrusions having a width of several nm to several tens of nm by wet etching using an acid solution.
  • the acid solution is characterized in that it contains a fluorine-based acid.
  • the acid solution also includes hydrogen fluoride, including ammonium fluoride, phosphoric acid, It further comprises at least one of nitric acid and hydrochloric acid.
  • the hydrogen fluoride content is greater than 0 weight percent and less than 10 weight percent with respect to 100 weight percent of the acid solution.
  • the content is characterized in that less than 5% by weight.
  • the content is characterized in that less than 5% by weight.
  • the content is characterized in that less than 5% by weight.
  • the content is characterized in that more than 10% by weight and less than 40% by weight.
  • the acid solution may also be hydrogen fluoride, ammonium fluoride, phosphoric acid, Including nitric acid, hydrochloric acid and water, the content of each component with respect to 100% by weight of the acid solution, the hydrogen fluoride 10% by weight or less, the ammonium fluoride 5% by weight or less, the nitric acid 5% by weight or less, the phosphoric acid Silver is less than 5% by weight, the hydrochloric acid is characterized in that more than 10% by weight to 40% by weight and the remainder is water.
  • the forming of the protrusions may include: forming an anti-glare layer including protrusions having a width of several tens of nm to several um by primary wet etching using an acid solution; And forming an anti-reflection layer including protrusions having a width of several nm to several tens nm on the anti-glare layer by secondary wet etching using an acid solution.
  • the base material having a nano-protrusion surface formed by the method is a base material with a plurality of protrusions formed on the surface, the protrusions are formed by wet etching, the wet etching is selective etching such as a mask before etching It is made without the process of forming the resistance means, and due to the absence of the selective etching resistance means such as the mask, the state in which the protrusions are formed is characterized in that it does not have any regularity in the position and size or shape of the protrusions.
  • the proposed invention can form nano protrusions having a width of several nm to several tens nm or several tens of nm to several um through a wet etching process.
  • the proposed invention can produce a polymer film having glass or glass characteristics to prevent glare through a wet etching process.
  • the proposed invention can produce a polymer film having glass or glass properties to prevent reflection through a wet etching process.
  • the proposed invention can produce a polymer film having glass or glass characteristics to prevent glare and reflection at the same time through the wet etching process.
  • FIG. 1 illustrates an overall flow of a method of forming a protrusion according to an embodiment.
  • FIG. 2 illustrates a cross-sectional view of a glass substrate having an antiglare layer according to one embodiment.
  • FIG. 3 is a scanning electron micrograph of a glass substrate having an anti-glare layer according to an embodiment
  • FIG. 4 is an enlarged scanning electron micrograph of FIG. 3.
  • FIG. 5 illustrates a cross-sectional view of a glass substrate on which an antireflective layer is formed, according to one embodiment.
  • FIG. 6 is a scanning electron micrograph of a glass substrate having an antireflective layer formed thereon
  • FIG. 7 is an enlarged scanning electron micrograph of FIG. 6.
  • FIG 8 illustrates a cross-sectional view of a glass substrate formed with an anti-glare layer and an anti-reflective layer according to one embodiment.
  • FIG. 9 is a scanning electron micrograph of a glass substrate formed with an anti-glare layer and an anti-reflection layer according to an embodiment.
  • FIG. 10 is a cross-sectional view of a glass substrate in which an anti-reflection layer is additionally formed in protrusions and grooves having a size of several um to several hundred um formed on the glass substrate by a conventional method rather than the present invention.
  • FIG. 11 is a scanning electron micrograph of a glass substrate in which antireflection protrusions of several nm to several tens of nm are additionally formed on an anti-glare protrusion of several um to several hundred um in size.
  • FIG. 12 is a photograph of a smartphone including a glass or polymer film having an anti-reflection layer formed by the method of forming a projection according to the present invention.
  • FIG. 1 shows an overall flow of a method of forming a protrusion according to an embodiment of the present invention.
  • the method of forming a protrusion may include cleaning a glass substrate (S610), forming a protrusion on the glass substrate through wet etching (S620), and neutralizing the glass substrate (S630).
  • the step of cleaning the glass substrate (S610) is to remove the organic material present in the glass substrate to form a protrusion on the glass substrate through the wet etching, which is a post-process acid (acid) in the acid solution in the step (S620)
  • the treatment is made uniform throughout the substrate.
  • IPA Isopropyl Alcohol
  • ethanol is used for cleaning a glass substrate.
  • the glass substrate is washed with water.
  • ultrasonic waves may be used or the glass substrate may be cleaned using a brush.
  • the forming of the protrusions on the glass substrate through wet etching according to an embodiment may be performed by dipping or dipping the glass substrate into an acid solution or spraying an acid solution onto the glass substrate. do. Forming the protrusions (S620) forms nano protrusions on the polymer film substrate having glass or glass characteristics through wet etching with an acid solution without a mask. Detailed description of the step (S620) of forming a protrusion on the glass substrate through wet etching will be described later.
  • neutralizing the glass substrate (S630) maintains the pH of the glass substrate surface having a low pH through the step (S620) of forming a protrusion on the glass substrate through wet etching.
  • the pH is neutralized by immersing the glass substrate having a low pH through the step (S620) of forming a protrusion on the glass substrate through wet etching in a water bath containing water.
  • FIG. 2 illustrates a cross-sectional view of a glass substrate having an antiglare layer according to one embodiment.
  • the forming of the protrusion may include forming an anti-glare layer including a protrusion having a width w1 of several tens of nm to several um through wet etching with an acid solution.
  • the protrusions include concave and convex surfaces as shown in FIG. 2.
  • the above-mentioned width W1 is the width of the iron surface. Projections having a width w1 of several tens nm to several um through wet etching with an acid solution have a height h1 of several tens of nm to several um.
  • the light irradiated onto the glass substrate is scattered by protrusions having a width w1 of several tens of nm to several um, and thus the glass substrate The reflectance of is lowered and glare is reduced.
  • the acid solution includes a fluorine-based acid and nitric acid.
  • Fluorine-based acids include, for example, hydrogen fluoride (HF) and ammonium fluoride (NH 4 F).
  • HF hydrogen fluoride
  • NH 4 F ammonium fluoride
  • the acid solution includes hydrogen fluoride (HF) and nitric acid (HNO 3 ), but ammonium fluoride (NH 4 F), phosphoric acid (H 3 PO 4 ), It further comprises at least one of hydrochloric acid (HCl), water (H 2 O).
  • the content of the hydrogen fluoride is characterized in that more than 0 weight percent and less than 10 weight percent with respect to 100 weight percent of the acid solution.
  • silicon dioxide reacts with hydrogen fluoride to etch the surface of the glass substrate, and as a result, protrusions having a width of several nm to several tens nm are formed on the glass substrate.
  • the content of nitric acid is characterized in that more than 10 weight percent and less than 25 weight percent with respect to 100 weight percent of the acid solution. At least 10% by weight and at most 25% by weight with respect to 100% by weight of the acid solution react with aluminum oxide to form a glass substrate comprising a protrusion having a width of several nm to several tens nm formed by the above-described process. Form a protrusion with a width.
  • nitric acid is introduced into the gap created by etching according to Chemical Formula 1, and reacts with aluminum oxide (Al 2 O 3 ). According to this reaction, protrusions having a width of several tens of nm to several um larger than those formed by hydrogen fluoride are formed on the glass substrate.
  • the acid solution includes ammonium fluoride, wherein the content of the ammonium fluoride is greater than 0 weight percent and less than 5 weight percent with respect to 100 weight percent of the acid solution.
  • the acid solution comprises phosphoric acid
  • the content of the phosphoric acid is characterized in that more than 0 weight percent and less than 5 weight percent with respect to 100 weight percent of the acid solution.
  • the phosphoric acid reacts with aluminum oxide (Al 2 O 3 ) to smooth the surface of the projection having a rough surface.
  • Phosphoric acid has a higher viscosity than nitric acid, so that the surface of the protrusion formed by the chemical reaction of nitric acid can be smoothed.
  • the acid solution comprises hydrochloric acid
  • the hydrochloric acid content is characterized in that more than 0 weight percent and less than 10 weight percent with respect to 100 weight percent of the acid solution.
  • Hydrochloric acid according to Formula 5 reacts with silicon dioxide (SiO 2 ) to smooth the surface of the projection having a rough surface.
  • the acid solution is water, hydrogen fluoride, ammonium fluoride, phosphoric acid, Nitric acid and hydrochloric acid, wherein the hydrogen fluoride content is greater than 0 weight percent and less than 10 weight percent with respect to 100 weight percent of the acid solution, and the content of ammonium fluoride is greater than 0 weight percent with respect to 100 weight percent of the acid solution.
  • the content of nitric acid is greater than or equal to 10 weight percent and less than or equal to 25 weight percent of 100 weight percent of the acid solution
  • the content of phosphoric acid is greater than 0 weight percent of 100 weight percent of the acid solution and 5 It is less than a weight percent
  • the content of hydrochloric acid is greater than 0 weight percent and less than 10 weight percent with respect to 100 weight percent of the acid solution, the remainder is characterized in that the water.
  • the wet etching process using an acid solution containing nitric acid and hydrochloric acid forms protrusions having a width of several tens of nm to several um. Water dilutes the acid solution.
  • FIG. 3 is a scanning electron micrograph of a glass substrate having an anti-glare layer according to an embodiment.
  • the width of the protrusion formed on the glass substrate is several tens of nm to several um.
  • 4 is an enlarged scanning electron micrograph of FIG. 3.
  • FIG. 5 illustrates a cross-sectional view of a glass substrate on which an antireflective layer is formed, according to one embodiment.
  • the forming of the protrusions may include forming an anti-reflection layer including protrusions having a width w 2 of several nm to several tens nm through wet etching with an acid solution.
  • the protrusions include concave and convex surfaces as shown in FIG. 5.
  • the above-described width w2 is the width of the iron surface. If there are protrusions having a width w2 of several nm to several tens nm on the surface of the glass substrate, the transmittance of the light irradiated onto the glass substrate by these protrusions increases and the reflectance is lowered.
  • the acid solution contains a fluorine-based acid.
  • Fluorine-based acids include, for example, hydrogen fluoride (HF) and ammonium fluoride (NH 4 F).
  • HF hydrogen fluoride
  • NH 4 F ammonium fluoride
  • the acid solution including hydrogen fluoride, ammonium fluoride, phosphoric acid, It further comprises at least one of nitric acid and hydrochloric acid.
  • the content of the hydrogen fluoride is characterized in that more than 0 weight percent and less than 10 weight percent with respect to 100 weight percent of the acid solution.
  • silicon dioxide reacts with hydrogen fluoride to etch the surface of the glass substrate, and as a result, protrusions having a width of several nm to several tens nm are formed on the glass substrate.
  • the acid solution includes ammonium fluoride, wherein the content of the ammonium fluoride is greater than 0 weight percent and less than 5 weight percent with respect to 100 weight percent of the acid solution.
  • hydrogen fluoride is reduced according to the above formula (6), hydrogen fluoride is produced according to the formula (7). Accordingly, the weight ratio of hydrogen fluoride in the acid solution is kept constant. As the weight ratio of hydrogen fluoride is kept constant, a stable wet etching process may be achieved.
  • the acid solution, nitric acid, the content of nitric acid is characterized in that more than 0 weight percent and less than 5 weight percent with respect to 100 weight percent of the acid solution. More than 0 weight percent and less than 5 weight percent of nitric acid with respect to 100 weight percent of the acid solution serves to maintain the size of the protrusion formed by the hydrogen fluoride in the range of several nm to several tens of nm.
  • nitric acid is introduced into the gap created by etching according to Chemical Formula 6, and reacts with aluminum oxide (Al 2 O 3 ). According to the reaction described above, protrusions having a width of several nm to several tens nm formed on the glass substrate are formed.
  • nitric acid In the range of 10% by weight or more and 25% by weight or less with respect to 100% by weight of the acid solution, as described above, the higher the weight ratio of nitric acid can form projections having a larger width up to several um on the glass substrate.
  • nitric acid of more than 0 weight percent and 5 weight percent or less with respect to 100 weight percent of the acid solution keeps the width of the protrusion formed on the glass substrate in the range of several nm to several tens of nm.
  • the acid solution comprises phosphoric acid
  • the content of the phosphoric acid is characterized in that more than 0 weight percent and less than 5 weight percent with respect to 100 weight percent of the acid solution.
  • phosphoric acid reacts with aluminum oxide (Al 2 O 3 ) to smooth the surface of the projection having a rough surface.
  • Phosphoric acid has a higher viscosity than nitric acid, so that the surface of the protrusion formed by the chemical reaction of nitric acid can be smoothed.
  • the acid solution includes hydrochloric acid
  • the hydrochloric acid content is characterized in that more than 10% by weight and 40% by weight or less based on 100% by weight of the acid solution.
  • hydrochloric acid reacts with silicon dioxide (SiO 2 ) to smooth the surface of the projection having a rough surface.
  • the acid solution is water, hydrogen fluoride, ammonium fluoride, phosphoric acid, Nitric acid and hydrochloric acid, wherein the hydrogen fluoride content is greater than 0 weight percent and less than 10 weight percent with respect to 100 weight percent of the acid solution, and the content of ammonium fluoride is greater than 0 weight percent with respect to 100 weight percent of the acid solution.
  • the wet etching process using an acid solution containing nitric acid and hydrochloric acid forms protrusions having a width of several nm to several tens of nm on the glass substrate. Water dilutes the acid solution.
  • FIG. 6 is a scanning electron micrograph of a glass substrate on which an antireflective layer is formed, according to an embodiment.
  • the width of the protrusions formed on the glass substrate is several nm to several tens of nm
  • FIG. 7 is an enlarged scanning electron micrograph of FIG. 6.
  • FIG 8 illustrates a cross-sectional view of a glass substrate formed with an anti-glare layer and an anti-reflective layer according to one embodiment.
  • the forming of the protrusion may include forming an anti-glare layer including a protrusion having a width of several tens of nm to several um through primary wet etching with an acid solution; And forming an anti-reflection layer including protrusions having a width of several nm to several tens nm on the anti-glare layer through secondary wet etching with an acid solution.
  • the step of forming the anti-glare and anti-reflection layer first forms an anti-glare layer including protrusions having a width of several tens of nm to several um through primary wet etching with an acid solution.
  • the above-mentioned acid solution is water, hydrogen fluoride, ammonium fluoride, phosphoric acid, Nitric acid and hydrochloric acid, wherein the hydrogen fluoride content is greater than 0 weight percent and less than 10 weight percent with respect to 100 weight percent of the acid solution, and the content of ammonium fluoride is greater than 0 weight percent with respect to 100 weight percent of the acid solution.
  • the content of nitric acid is greater than or equal to 10 weight percent and less than or equal to 25 weight percent of 100 weight percent of the acid solution
  • the content of phosphoric acid is greater than 0 weight percent of 100 weight percent of the acid solution and 5 It is less than a weight percent
  • the content of hydrochloric acid is greater than 0 weight percent and less than 10 weight percent with respect to 100 weight percent of the acid solution, the remainder is characterized in that the water.
  • the above-mentioned acid solution is water, hydrogen fluoride, ammonium fluoride, phosphoric acid, Nitric acid and hydrochloric acid, wherein the hydrogen fluoride content is greater than 0 weight percent and less than 10 weight percent with respect to 100 weight percent of the acid solution, and the content of ammonium fluoride is greater than 0 weight percent with respect to 100 weight percent of the acid solution.
  • protrusions having a width w1 of several tens of nm to several um As protrusions having a width w1 of several tens of nm to several um are formed, transmittance and reflectance of light of the glass substrate decrease. Subsequently, as protrusions having a width w2 of several nm to several tens of nm are additionally formed on protrusions having a width w1 of several tens of nm to several um, the transmittance is relatively increased and the reflectance is further lowered. This results in a glass substrate that prevents glare and reflections.
  • FIG. 9 is a scanning electron micrograph of a glass substrate formed with an anti-glare layer and an anti-reflection layer according to an embodiment.
  • the picture at the bottom of FIG. 9 is a further enlarged picture of the rectangular area of the picture shown at the top of FIG. 9.
  • FIG. 10 is a cross-sectional view of a glass substrate in which an anti-reflection layer is additionally formed in protrusions and grooves having a size of several um to several hundred um formed on the glass substrate by a conventional method rather than the present invention.
  • the conventional method other than the present invention on the anti-glare layer comprising a projection of the size of several um ⁇ several hundred um formed on the glass substrate through the wet etching by acid solution additionally has a width of several nm ⁇ several tens nm.
  • the method may further include forming an antireflection layer including protrusions.
  • FIG. 11 is a scanning electron micrograph of a glass substrate on which an anti-reflection layer having a size of several nm to several tens nm is additionally formed on an anti-glare layer including protrusions having a size of several um to several hundred um formed by a conventional method.
  • the above-mentioned acid solution is water, hydrogen fluoride, ammonium fluoride, phosphoric acid, Nitric acid and hydrochloric acid, wherein the hydrogen fluoride content is greater than 0 weight percent and less than 10 weight percent with respect to 100 weight percent of the acid solution, and the content of ammonium fluoride is greater than 0 weight percent with respect to 100 weight percent of the acid solution.
  • 11 is a scanning electron microscope photograph of the anti-reflection layer by enlarging a rectangular portion of the upper portion.
  • the base material surface formed by the nanoprotrusion surface forming method of the present invention is formed by wet etching of protrusions on the surface, and the wet etching is performed by using a mask before etching.
  • the state in which the protrusions are formed does not have any regularity in the position of the protrusions and the size or shape of the protrusions.
  • the irregularity of the surface protrusions as described above can be said to be an inherent feature obtained by maskless wet etching.
  • FIG. 12 is a photograph of a smartphone including a glass or polymer film having an anti-reflection layer formed by the method of forming a projection according to the present invention.
  • the anti-reflection layer is formed on the left side of the glass included in the smartphone on the basis of the dotted line by the protrusion forming method according to the present invention.
  • the anti-reflection layer is not formed on the right side of the glass included in the smartphone by the projection forming method according to the present invention. It can be seen that the fingerprint formed on the left glass is not dark compared to the right side.

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  • General Chemical & Material Sciences (AREA)
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  • Crystallography & Structural Chemistry (AREA)
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  • Surface Treatment Of Glass (AREA)
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  • Surface Treatment Of Optical Elements (AREA)
PCT/KR2017/008349 2016-08-08 2017-08-02 나노돌기 표면 형성 방법 및 그 방법에 의해 형성된 나노돌기 표면을 갖는 모재 WO2018030703A1 (ko)

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JP2019507180A JP6698938B2 (ja) 2016-08-08 2017-08-02 ナノ突起表面の形成方法
US16/323,911 US11618710B2 (en) 2016-08-08 2017-08-02 Nano protrusion surface forming method and base material having nano protrusion surface formed by method
CN201780048666.6A CN109564867B (zh) 2016-08-08 2017-08-02 纳米突起表面形成方法及具有通过该方法形成的纳米突起表面的母材

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JP2019526520A (ja) 2019-09-19
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CN109564867B (zh) 2023-06-16
KR20180016887A (ko) 2018-02-20

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