WO2014196539A1 - Feuille de verre ainsi que procédé de fabrication de celle-ci, et module luminescent - Google Patents

Feuille de verre ainsi que procédé de fabrication de celle-ci, et module luminescent Download PDF

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Publication number
WO2014196539A1
WO2014196539A1 PCT/JP2014/064766 JP2014064766W WO2014196539A1 WO 2014196539 A1 WO2014196539 A1 WO 2014196539A1 JP 2014064766 W JP2014064766 W JP 2014064766W WO 2014196539 A1 WO2014196539 A1 WO 2014196539A1
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Prior art keywords
glass
glass plate
fluorine
gas
light emitting
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PCT/JP2014/064766
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English (en)
Japanese (ja)
Inventor
信彰 井川
康宏 池田
亮祐 加藤
泰夫 林
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旭硝子株式会社
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Publication of WO2014196539A1 publication Critical patent/WO2014196539A1/fr

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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
    • 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
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic 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
    • C03C21/007—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in gaseous phase
    • 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
    • C03C2204/00—Glasses, glazes or enamels with special properties
    • C03C2204/08—Glass having a rough surface
    • 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
    • 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
    • C03C2218/345—Surface crystallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
    • H01L2933/0008—Processes
    • H01L2933/0033—Processes relating to semiconductor body packages
    • H01L2933/0058—Processes relating to semiconductor body packages relating to optical field-shaping elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
    • H01L2933/0083—Periodic patterns for optical field-shaping in or on the semiconductor body or semiconductor body package, e.g. photonic bandgap structures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
    • H01L2933/0091—Scattering means in or on the semiconductor body or semiconductor body package
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements

Definitions

  • the present invention relates to a glass plate, a light emitting module, and a glass plate manufacturing method.
  • light emitting modules having light emitting elements such as LEDs have been developed as light sources with long life and low power consumption.
  • a light emitting module includes a semiconductor light emitting element such as an LED, a wavelength conversion member, and a transparent member.
  • the wavelength conversion member has a phosphor and has a function of converting the wavelength of light emitted from the light emitting element to emit light of another wavelength.
  • the transparent member has a role as an emission surface that emits light to the outside.
  • light of the first wavelength is emitted from the light emitting element.
  • Light generated from the light emitting element is incident on the wavelength conversion member.
  • Part of the light having the first wavelength incident on the wavelength conversion member is wavelength-converted here, thereby generating light having the second wavelength.
  • the light having the first wavelength that has not been converted by the wavelength conversion member and the light having the second wavelength are combined to form light having a desired wavelength. By emitting this light from the transparent member side, it is possible to emit light having a desired wavelength to the outside of the light emitting module.
  • the light emitting module when the light emitted from the light emitting element and / or the wavelength conversion member is totally reflected (internal reflection) in the light emitting module, the amount of light emitted to the outside through the transparent member is reduced, and the luminance of the light emitting module is increased. It will decline. For this reason, in the light emitting module, it is an important subject to suppress the internal reflection of light and increase the light extraction efficiency.
  • Patent Document 1 discloses increasing the light extraction efficiency of a light emitting module by forming a plurality of protrusions on the surface of a transparent member.
  • Patent Document 1 describes that the light extraction efficiency of the light emitting module is increased by forming a plurality of protrusions on the surface of the transparent member.
  • Patent Document 1 describes that the light extraction efficiency of the light emitting module is increased by forming a plurality of protrusions on the surface of the transparent member.
  • An object of the present invention is to provide a glass plate, a light emitting module, and a glass plate manufacturing method capable of increasing light extraction efficiency when used in a light emitting module or the like.
  • the present invention provides the following aspects. (1) having a fluorine-containing layer with fluorine atoms on the surface, A glass plate, wherein a plurality of pillars are formed in the fluorine-containing layer. (2) The plurality of pillars are erected from the upper surface of the fluorine-containing layer, The glass plate according to (1), wherein a plurality of recesses are formed on the upper surface. (3) The plurality of pillars are erected from the upper surface of the fluorine-containing layer, The glass plate according to (1), wherein the upper surface is a flat surface. (4) The glass plate according to (2) or (3), wherein the pillar has a height from the top surface of 10 nm to 1000 nm.
  • a light emitting module comprising a light emitting element, a wavelength conversion member, and a transparent member, wherein light emitted from the light emitting element is emitted from the transparent member via the wavelength conversion member,
  • the transparent member is the glass plate according to any one of (1) to (8), A light emitting module, wherein the fluorine-containing layer is disposed on an emission side.
  • 10 In a temperature range of 715 ° C. or more and 1000 ° C.
  • the glass plate contains 4.5 ⁇ 10 ⁇ 5 mol / cm 2 or more of molecules having fluorine atoms in the structure in terms of hydrogen fluoride.
  • Spraying a gas or a liquid Etching the glass plate with an etching solution in which ammonia or an amino group and a molecule soluble in hydrofluoric acid, or both are dissolved in hydrofluoric acid, to form a plurality of pillars.
  • a glass plate manufacturing method (12) a molding step of floating a molten glass on a molten metal to form a glass ribbon; A slow cooling step of slowly cooling the glass ribbon, The glass sheet manufacturing method according to (10) or (11), wherein the forming step includes a step of spraying the gas or liquid.
  • the etching solution is a mixed solution in which hydrofluoric acid and ammonium fluoride are mixed at a predetermined ratio.
  • a fluorine-containing layer in which fluorine atoms are present is provided on the surface, and a plurality of pillars are formed in the fluorine-containing layer. Therefore, when used in a light emitting module or the like, the light extraction efficiency is improved. Can be increased.
  • (E)-(g) is a schematic diagram explaining the mechanism which a pillar produces
  • (A) is a figure which shows the photograph of the glass surface in which the fine recessed part before an etching was formed
  • (b) is a figure which shows the photograph of the glass surface in which the recessed part after an etching was formed
  • (c) is an etching. It is a figure which shows the photograph of the back cross section. It is sectional drawing which showed roughly one Embodiment of the light emitting module of this invention. It is sectional drawing which showed schematically other embodiment of the light emitting module of this invention.
  • 2 is a table showing conditions and results of hydrogen fluoride treatment in Examples 1 to 22.
  • FIG. 3 is a graph of photographs of the glass surface in Examples 1 to 22 based on the glass surface temperature and the amount of hydrogen fluoride gas sprayed (the amount of sprayed HF).
  • 34 is a table showing hydrogen fluoride treatment conditions and etching treatment conditions of Examples 23 to 34.
  • 34 is a table showing the results of hydrogen fluoride treatment and etching treatment of Examples 23 to 34.
  • FIG. 4 is a view showing photographs of glass surfaces obtained by hydrogen fluoride treatment and etching treatment in Examples 23 to 33.
  • FIG. 1 is a view schematically showing a cross section of an embodiment of the glass plate of the present invention.
  • the glass plate 110 of the present embodiment has a first surface 115 and a second surface 120, as shown in FIG.
  • a fluorine-containing layer 116 in which fluorine atoms (F) are present.
  • a plurality of pillars 117 are formed in the fluorine-containing layer 116.
  • the plurality of pillars 117 are erected from the upper surface 118 of the fluorine-containing layer 116.
  • a plurality of recesses 130 are formed on the upper surface 118.
  • the plurality of pillars 117 have a height H from the top surface 118 in the range of 10 nm to 1000 nm, preferably 50 nm to 900 nm.
  • standard of the height of the pillar 117 is the upper surface 118, and when the upper surface 118 has an unevenness
  • the area of the top surface 119 of the pillar 117 is in the range of 2 ⁇ 10 ⁇ 14 m 2 to 9 ⁇ 10 ⁇ 13 m 2 , preferably 3 ⁇ 10 ⁇ 14 m 2 to 8 ⁇ 10 ⁇ 13 m 2 .
  • the area ratio of the top surface 119 to the fluorine-containing layer 116 is 5% to 50%, preferably 10% to 35%. % Range.
  • the form of the top face 119 of the pillar 117 (the form when the pillar 117 is viewed from the top of the first surface 115) is not particularly limited, and the top face is substantially circular, substantially elliptical, or substantially rectangular. Also good.
  • One or more minute recesses 135 may be formed on the top surface 119 of the pillar 117. As will be described in detail later, the minute recess 135 typically has a circular shape with a diameter of about 20 nm and a depth of about 100 nm.
  • the plurality of recesses 130 formed on the upper surface 118 may be formed continuously as shown in FIG. 1, and a flat portion 140 may exist between adjacent recesses as shown in FIG. . Furthermore, the upper surface 118 may present a flat surface 150 on which the recess 130 is not formed as shown in FIG.
  • the cross-sectional shape of the glass plate 110 shown in FIGS. 1 to 3 is merely an example.
  • the cross-sectional shape of the recess 130 does not necessarily have to be “substantially hemispherical” as shown in FIGS. “Substantially hemispherical” refers to a form in which a sphere or an elliptical sphere is cut exactly in half.
  • the cross-sectional shape of the recess 130 includes a shape obtained by cutting a substantially sphere or a substantially oval sphere so as not to pass through the center in addition to a substantially hemispherical shape.
  • the form of the opening of the recessed part 130 (the form when the recessed part 130 is viewed from the top of the first surface 115) is not particularly limited, and the opening may be substantially circular, substantially elliptical, or substantially rectangular.
  • the maximum dimension R of the opening of the recess 130 is, for example, in the range of 20 nm to 2000 nm, and preferably in the range of 50 nm to 800 nm.
  • the average depth d of the recesses 130 is, for example, in the range of 20 nm to 1000 nm, and preferably in the range of 35 nm to 200 nm.
  • the glass plate 110 has a fluorine-containing layer 116 in which a plurality of pillars 117 are erected from the upper surface 118 on the first surface 115. Due to the presence of the upper surface 118 and the plurality of pillars 117, the light traveling inside the glass plate 110 is scattered in each direction on the first surface 115 of the glass plate 110. For this reason, the amount of light totally reflected inside the glass plate 110 is reduced.
  • the refractive index of fluorine atoms is about 1.3.
  • the glass plate 110 usually has a refractive index of about 1.5.
  • the light incident from the second surface 120 of the glass plate 110 is emitted from the glass plate 110 when the first surface 115 of the glass plate 110 is emitted.
  • the surface 115 / air interface that is, the refractive index 1.5 / 1.0 interface.
  • the width of change in the refractive index at this interface is relatively large. For this reason, when light enters this interface, reflection may occur in a part of the light.
  • the light incident from the second surface 120 of the glass plate 110 is emitted from the glass plate 110 when the fluorine atoms of the glass plate 110 are emitted.
  • Will pass through the first surface 115 / air interface ie, the refractive index 1.3 / 1.0 interface.
  • the refractive index 1.3 / 1.0 interface.
  • a rapid change in the refractive index is significantly suppressed as compared with the case where the first surface 115 does not contain a fluorine atom.
  • the fluorine atom concentration has a profile that gradually decreases from the first surface 115 of the glass plate 110 toward the inside of the glass plate 110, the effect of suppressing the variation in the refractive index is further increased. Enhanced.
  • the amount of light reflected at the interface of the first surface 115 / air can be significantly reduced, and more light can be emitted from the first surface 115.
  • the content of fluorine atoms on the first surface 115 may be, for example, in the range of 0.1 wt% to 0.4 wt%, or may be 0.2 wt% to 0.3 wt%.
  • the content of fluorine atoms on the surface can be measured by, for example, fluorescent X-ray analysis.
  • the mode of the fluorine atom is not particularly limited as long as it exists on the surface at a significant concentration.
  • the fluorine atom may be present in any manner in the depth direction.
  • FIG. 4 shows an example of a depth direction profile of the fluorine atom concentration on the first surface 115 of the glass plate 110. This graph is obtained by SIMS analysis on the first surface 115 of the glass plate 110. Note that the fluorine atom concentration on the first surface 115 is measured as the depth from the upper surface 118 by polishing and removing the pillar 117.
  • the fluorine atoms are distributed in a profile that gradually decreases from the upper surface 118 of the glass plate 110 to a depth of about 10 ⁇ m.
  • the fluorine atom content in the outermost surface of the upper surface 118 is about 0.2 wt%.
  • the depth direction profile of the fluorine atom concentration is not limited to such a mode, and fluorine atoms may exist at a constant concentration in a certain depth region, for example.
  • the glass plate 110 when the first surface 115 includes the fluorine-containing layer 116 in which the plurality of pillars 117 are formed, when the glass plate 110 is applied to, for example, a light emitting module, the glass plate 110 is thus, it is possible to significantly increase the extraction efficiency of light emitted from the light emitting module.
  • the glass plate 110 is made of transparent glass, its composition is not particularly limited.
  • “transparent” means a state in which the total light transmittance is 50% or more.
  • various glasses such as soda lime silicate glass, aluminosilicate glass, borate glass, lithium aluminosilicate glass, borosilicate glass, and alkali-free glass are used.
  • examples of the composition of the glass plate 110 include the following glass compositions (i) to (iv).
  • “contains 0 to 25% MgO” means that MgO is not essential but may contain up to 25%, and soda lime silicate glass is included in the glass of (i). .
  • the glass plate 110 may have a plate shape or a foil shape.
  • the thickness of the plate-like or foil-like glass plate 110 may be, for example, in the range of 0.1 mm to 2 mm.
  • the glass plate manufacturing method of this embodiment mainly has two steps. The first is hydrogen fluoride treatment and the second is etching treatment.
  • the hydrogen fluoride treatment is performed by spraying a gas or liquid containing a molecule having fluorine atoms in the structure in a predetermined amount or more in a temperature range of 620 ° C. to 1000 ° C. on the glass surface to form minute recesses on the glass surface. To form.
  • a suitable amount of the various raw materials that make up the glass described above is prepared, heated and melted, then homogenized by defoaming or stirring, and plate-shaped by a well-known float method, downdraw method (for example, fusion method) or press method, etc. It is possible to use glass that has been molded into a glass, and after slow cooling, cut into a desired size. Further, as will be described later, an on-line glass ribbon may be used during glass forming by a float method or a downdraw method (for example, a fusion method).
  • surface treatment is performed by blowing hydrogen fluoride gas on at least one surface of the glass.
  • hydrogen fluoride gas a gas or liquid containing a molecule having a fluorine atom in its structure may be used.
  • examples of the gas or liquid containing a molecule having a fluorine atom in its structure include chlorofluorocarbon (for example, chlorofluorocarbon, fluorocarbon, hydrochlorofluorocarbon, hydrofluorocarbon, and halon), hydrofluoric acid, and the like.
  • chlorofluorocarbon for example, chlorofluorocarbon, fluorocarbon, hydrochlorofluorocarbon, hydrofluorocarbon, and halon
  • hydrofluoric acid and the like.
  • a gas or liquid containing a molecule having a fluorine atom in its structure including hydrogen fluoride gas (hereinafter also referred to as hydrogen fluoride gas)
  • a liquid or gas other than those liquids or gases is used. It is preferably a liquid or gas that does not react with molecules having fluorine atoms at room temperature.
  • liquid or gas examples include, but are not limited to, N 2 , air, H 2 , O 2 , Ne, Xe, CO 2 , Ar, He, and Kr. Moreover, 2 or more types of these gases can also be mixed and used.
  • a carrier gas such as hydrogen fluoride gas
  • an inert gas such as N 2 or argon
  • the hydrogen fluoride gas or the like may further contain SO 2 .
  • SO 2 is used when continuously producing glass by the float method or the like, and has a function of preventing the transport roller from coming into contact with the glass in the slow cooling region and generating wrinkles on the glass.
  • disassembled at high temperature may be included.
  • the hydrogen fluoride gas or the like may contain water vapor or water.
  • Water vapor can be extracted by bubbling an inert gas such as nitrogen, helium, argon, carbon dioxide in heated water.
  • an inert gas such as nitrogen, helium, argon, carbon dioxide in heated water.
  • the treatment temperature for blowing hydrogen fluoride gas or the like is 620 ° C. to 1000 ° C. or less, preferably 625 ° C. to 900 ° C., more preferably 625 ° C. to 800 ° C.
  • the glass transition temperature of the glass is Tg
  • the glass surface temperature is preferably (Tg ⁇ 200) ° C. to (Tg + 300) ° C., and (Tg ⁇ 200) ° C. to (Tg + 250). More preferably, it is ° C.
  • the glass surface temperature is Tg or less
  • the glass surface temperature is (Tg + 200 ° C.). It is typically performed in the following temperature range.
  • the pressure of the glass surface when blowing hydrogen fluoride gas or the like is preferably an atmosphere in a pressure range of (atmospheric pressure ⁇ 100) Pascal to (atmospheric pressure + 100) Pascal, and (atmospheric pressure ⁇ 50) from Pascal.
  • An atmosphere in the pressure range of (atmospheric pressure + 50) Pascal is more preferable.
  • hydrogen fluoride toward the glass surface at a rate of 1.8 ⁇ 10 ⁇ 5 mol / cm 2 or more in terms of hydrogen fluoride.
  • hydrogen fluoride gas or the like is directed toward the glass surface at a rate of 4.5 ⁇ 10 -5 mol / cm 2 or more in terms of hydrogen fluoride. Need to be sprayed.
  • the gas or liquid containing a molecule having a fluorine atom in the structure is silicon tetrafluoride
  • 1 mol of silicon tetrafluoride is converted to 4 mol of hydrogen fluoride. (4 times the molecular substance amount (mol)).
  • the spraying amount of hydrogen fluoride gas or the like is set according to the pitch of the minute recesses formed on the glass surface.
  • the total gas flow rate is the same, the higher the concentration of hydrogen fluoride gas or the like, the higher the concentration of hydrogen fluoride gas or the like. The number of minute recesses increases.
  • a float method As a method of using an on-line glass ribbon during glass molding, for example, a float method can be mentioned.
  • a glass manufacturing apparatus having a melting furnace for melting glass raw materials, a float bath for floating glass on a molten metal (such as tin) to form a glass ribbon, and a slow cooling furnace for gradually cooling the glass ribbon Is used to produce glass.
  • the glass is conveyed with respect to the glass ribbon conveyed on the molten metal bath.
  • the glass ribbon is conveyed by a roller.
  • the surface of the glass ribbon may be treated by supplying hydrogen fluoride gas or the like to the glass ribbon. Good.
  • the slow cooling region includes not only the inside of the slow cooling furnace but also the portion from the time when the molten metal (tin) bath is carried out in the float bath to the time when it is carried into the slow cooling furnace.
  • hydrogen fluoride gas or the like may be supplied from the side not touching the molten metal (tin).
  • the surface of the glass ribbon may be treated by supplying hydrogen fluoride gas or the like to the glass ribbon in the heating step of heating the glass sheet offline with respect to the slowly cooled plate glass.
  • Examples of a method for supplying hydrogen fluoride gas or the like to the surface of the glass ribbon include a method using an injector and a method using an introduction tube.
  • FIGS. 5 is a schematic view of a double-flow type injector
  • FIG. 6 is a schematic view of a single-flow type injector.
  • the distance between the gas outlet of the injector and the glass is preferably 50 mm or less. By setting it to 50 mm or less, it is possible to suppress the gas from diffusing into the atmosphere, and to allow a sufficient amount of gas to reach the glass surface with respect to the desired gas amount. On the other hand, if the distance from the glass is too short, for example, when the glass ribbon produced by the float process is processed online, the glass ribbon and the injector may come into contact with each other due to the fluctuation of the glass ribbon.
  • the injector may be used in any manner such as double-flow or single-flow, and two or more injectors may be arranged in series in the glass flow direction to treat the glass surface.
  • the double-flow injector 10 ⁇ / b> A is an injector in which the gas flow 4 from the discharges 1 and 2 to the exhaust 5 is equally divided in the forward direction and the reverse direction with respect to the moving direction 21 of the glass 20.
  • the single-flow injector 10B is an injector in which the gas flow 4 from the discharges 1 and 2 to the exhaust 5 is fixed in either the forward direction or the reverse direction with respect to the moving direction 21 of the glass 20, as shown in FIG. is there.
  • the single-flow injector 10B it is preferable that the gas flow 4 on the glass and the glass moving direction 21 are the same in terms of airflow stability.
  • the glass surface may be treated by supplying the gas from the side touching the conveyor.
  • the glass when the glass is flowing on the roller, it may be supplied from the side not touching the roller, or may be supplied from between adjacent rollers on the side touching the roller.
  • the same or different gas may be supplied from both sides of the glass.
  • the glass surface may be surface-treated by supplying gas from both the side not touching the roller and the side touching the roller.
  • the injector against the glass that is being continuously conveyed so that it faces the glass and the roller that does not touch the roller Gas may be supplied from both sides of the side touching.
  • the injector arranged on the side touching the roller and the injector arranged on the side not touching the roller may be arranged at different positions in the glass flow direction. In arranging at different positions, any of them may be arranged upstream or downstream with respect to the glass flow direction.
  • glass with a functional film is manufactured online by combining glass manufacturing technology using the float process and CVD technology.
  • the transparent conductive film and the underlying film are formed on the glass by supplying gas from the surface not touching tin or the surface not touching the roller. ing.
  • an injector may be disposed on the surface in contact with the roller, and the glass surface may be treated by supplying hydrogen fluoride gas or the like to the glass from the injector.
  • FIG. 7 is a view showing a photograph of the glass surface on which minute concave portions are formed by the hydrogen fluoride treatment.
  • FIG. 8 is a view showing a photograph of a cross section of a minute recess.
  • FIGS. 7A and 7B when the glass surface has a temperature range of 620 ° C. to 1000 ° C., a predetermined amount or more of hydrogen fluoride is sprayed on the glass surface, so that the glass surface has a diameter of about 20 nm. It can be seen that a plurality of circular minute concave portions having a depth of about 100 nm are formed. As shown in FIG.
  • the minute concave portion is reduced in diameter from the surface and then spreads in a substantially spherical bag shape, and foreign matter is present inside or traces of foreign matter are observed. It is done.
  • the diameter of such a micro recessed part represents the diameter of the constriction part between a reduced diameter part and a bag-like part, and the depth of a micro recessed part is from the glass surface to the deepest part of a bag-like part. Represents the depth of.
  • the size or diameter of the minute recess is typically 50 nm or less or 40 nm or less, and the depth is typically 250 nm or less or 200 nm or less.
  • FIG. 9 shows the result of analysis by an energy dispersive X-ray analyzer (EDX), where the dotted line shows the component analysis result of the minute recess, and the solid line shows the component analysis result around the minute recess.
  • EDX energy dispersive X-ray analyzer
  • etching process a glass plate on which minute recesses are formed by hydrogen fluoride treatment is etched with a predetermined etching solution to form a plurality of pillars on the glass surface.
  • the etching process is performed, for example, by immersing a glass plate in an etching solution.
  • the etching solution is a solution in which molecules having ammonia (NH 3 ) or amino groups (—NH 2 ) and soluble in hydrofluoric acid, or both, are dissolved in hydrofluoric acid.
  • Molecules having an amino group (—NH 2 ) and soluble in hydrofluoric acid include hydrazine (NH 2 —NH 2 ), triazane (NH 2 —NH—NH 2 ), and tetrazane (NH 2 —NH—NH—NH). 2 ) and the like.
  • ammonia and these molecules When ammonia and these molecules are dissolved in hydrofluoric acid and immersed in a glass plate with microrecesses formed by hydrogen fluoride treatment, it reacts with crystals inside the microrecesses to produce ammonium hexafluoroaluminate ( (NH 4 ) 3 AlF 6 ) is produced.
  • Ammonium hexafluoroaluminate is insoluble in hydrofluoric acid and functions as a mask. That is, when hydrofluoric acid melts the glass, ammonium hexafluoroaluminate prevents dissolution of the portion covered as a mask, and as a result, a plurality of pillars are formed on the glass surface.
  • the concentration of hydrofluoric acid is not limited to this, but is, for example, in the range of 50 wt% or less, and preferably in the range of 45 wt% or less.
  • the concentration of hydrofluoric acid contained in the etching solution affects the etching rate of the glass. The higher the concentration of hydrofluoric acid, the higher the etching rate.
  • the etching solution may further include a co-basic liquid such as LiOH, NaOH, KOH, RbOH, and CsOH.
  • the amount of the etching solution is not particularly limited, but it is preferable to use a sufficient amount of the etching solution for the glass plate.
  • a solution of 25 ml or more may be used per 50 cm 2 surface area of the glass plate.
  • Etching time that is, the immersion time of the glass plate in the etching solution varies depending on the size of the glass plate, but is, for example, about 1 second to 60 seconds.
  • the etching treatment time is preferably about 10 seconds to 5 minutes from the viewpoint of process efficiency.
  • ultrasonic vibration may be applied to the glass plate.
  • the glass plate may be etched while the etching solution is bubbled or stirred.
  • the etching temperature is, for example, about 10 ° C. to 50 ° C., and preferably in the range of 15 ° C. to 25 ° C.
  • the etching process may be performed at room temperature (25 ° C.).
  • the glass plate is taken out of the etching solution, and the mask and the etching solution are quickly removed by, for example, acid cleaning. Thereafter, the glass plate is dried.
  • the present inventors also considered the mechanism that the pillar generates. This mechanism will be described with reference to FIG.
  • hydrofluoric acid etching solution
  • ammonia or amino group-soluble molecules or both are dissolved
  • the crystals in the minute recesses of the part react with ammonia or an amino group to produce ammonium hexafluoroaluminate ((NH 4 ) 3 AlF 6 ) in the minute recesses (FIG. 11 (e)).
  • the produced ammonium hexafluoroaluminate functions as a mask against hydrofluoric acid, and the glass exposed from the mask dissolves.
  • FIG. 12 (a) is a view showing a photograph of the glass surface on which a minute recess before etching is formed, (b) is a view showing a photograph of the glass surface on which a recess after etching is formed, and (c).
  • FIG. 3 is a view showing a photograph of a cross section after etching.
  • the hole diameter of the recess is expanded from about 20 nm to about 400 nm by etching.
  • the shape of a recessed part is also changing, and it turns out that a constriction lose
  • pillars are not formed because the etching solution does not include molecules having ammonia and amino groups and soluble in hydrofluoric acid.
  • etching solution When hydrofluoric acid in which ammonia or amino group-soluble molecules or both are dissolved is used as an etching solution, pillars are formed around the minute recesses where the mask is formed, and the mask is formed.
  • the minute recesses that did not exist are enlarged by etching to form recesses.
  • etching an upper surface including a flat portion between the concave portions as shown in FIG. 2 is obtained, and when the etching further proceeds, an upper surface consisting of continuous concave portions having almost no flat portion as shown in FIG. 1 is obtained.
  • the recess as shown in FIG. 3 disappears and a flat surface is obtained.
  • a glass plate having a fluorine-containing layer with a plurality of pillars formed on the surface as shown in FIGS. it can.
  • the glass plate manufacturing method by this invention demonstrated above is only an example, and a glass plate may be manufactured by another method.
  • chemical strengthening may be performed before or after the etching treatment, but is preferably performed after the etching treatment.
  • the chemical strengthening is performed, for example, by immersing the glass in a molten salt such as potassium nitrate (KNO 3 ) at 380 ° C. to 450 ° C. for 0.1 to 20 hours.
  • the temperature of the molten salt such as potassium nitrate (KNO 3 ) By changing the immersion time, the molten salt, etc., the way of chemical strengthening can be adjusted.
  • a compressive stress layer is formed on the glass surface, and a tensile stress layer is formed inside.
  • FIG. 13 schematically shows a configuration of a light emitting module used for, for example, a light source.
  • the light emitting module 300 includes a substrate 320 on which a semiconductor light emitting element 310 such as an LED is disposed, a sealing material 330, and a transparent member 340.
  • a side wall 325 is further installed on the side of the substrate 320 where the light emitting element 310 is installed.
  • the side wall 325 has a reflective member on the inner surface, or at least the inner surface is made of a reflective member.
  • the sealing material 330 is configured by dispersing a wavelength conversion member 335 such as a phosphor in a resin matrix.
  • the sealing material 330 fills the space formed by the substrate 320 and the side wall 325 so as to completely cover the light emitting element 310.
  • the transparent member 340 has a first surface 345 and a second surface 347.
  • the transparent member 340 is disposed on the top of the sealing material 330 such that the second surface 347 side is in contact with the sealing material 330.
  • the transparent member 340 side is the light extraction side.
  • the transparent member 340 is composed of the glass plate 110. More specifically, the first surface 345 of the transparent member 340 includes a fluorine-containing layer 116 on which a plurality of pillars 117 (not shown) are formed.
  • first light having a first wavelength is emitted from the light emitting element 310.
  • the first light is converted into second light having a second wavelength by the wavelength conversion member 335 included in the sealing material 330.
  • the first light and the second light generated inside the light emitting module 300 travel toward the transparent member 340 (upward in FIG. 13).
  • a reflective side wall 325 is disposed on the side surface of the light emitting module 300. For this reason, the 1st light and 2nd light which generate
  • the first light and the second light pass through the sealing material 330 / air interface and are emitted to the outside.
  • the refractive index changes from the refractive index (about 1.5) of the resin matrix constituting the sealing material 330 to the refractive index of air (1.0). Therefore, the first light and the second light passing through this interface undergo a relatively large refractive index variation. For this reason, internal reflection occurs in some of these lights, and there is a possibility that the first light and the second light cannot be sufficiently extracted.
  • the light emitting module 300 includes a transparent member 340, and the transparent member 340 is composed of the glass plate 110 having the above-described characteristics.
  • the first surface 345 containing fluorine atoms of the transparent member 340 / air interface that is, a refractive index of 1.3 / 1. .0 interface.
  • a rapid change in refractive index is significantly suppressed.
  • the amount of light reflected at the first surface 345 / air interface of the transparent member 340 can be significantly reduced, and more from the first surface 345 of the transparent member 340. Can be emitted.
  • a plurality of pillars 117 are formed on the first surface 345 of the transparent member 340, and the first and second lights are scattered in each direction on the first surface 345 of the transparent member 340. For this reason, the amount of light totally reflected inside the light emitting module 300 can be reduced. With such an effect, the light extraction module 300 can significantly increase the light extraction efficiency.
  • FIG. 14 schematically shows another configuration of the light emitting module.
  • the light emitting module 400 includes a substrate 420 on which a light emitting element 410 such as an LED is disposed, a wavelength conversion member 435, and a transparent member 440.
  • the transparent member 440 side is a light extraction surface.
  • the wavelength conversion member 435 includes a phosphor, and can convert the first light having the first wavelength emitted from the light emitting element 410 into the second light having the second wavelength.
  • the transparent member 440 is composed of the glass plate 110. More specifically, the first surface 445 of the transparent member 440 includes a fluorine-containing layer 116 on which a plurality of pillars 117 (not shown) are formed.
  • Glass composition In this example, glass having the following composition was used. In terms of mol%, SiO 2 is 64.3%, Al 2 O 3 is 8.0%, Na 2 O is 12.5%, K 2 O is 4.0%, MgO is 10.5%, and CaO is Glass containing 0.1%, 0.1% SrO, 0.1% BaO and 0.5% ZrO 2
  • ⁇ Hydrogen fluoride treatment> A double-flow injector used in the atmospheric pressure CVD method is placed in a float bath, and a gas containing hydrogen fluoride and nitrogen (N 2 ) is sprayed onto the surface of the glass as shown in the schematic diagram of FIG. did. After the surface treatment, it was washed in a container containing a sufficiently large amount of water or the glass area and dried by air blow. In the following description, “hole” represents a minute recess.
  • FIG. 15 also shows the results obtained (presence / absence of hole formation (indicated by “ ⁇ ” for formation, “ ⁇ ” for non-formation), hole diameter, hole depth, number of holes)). .
  • the amount of sprayed HF was calculated by multiplying the width of the injector by the linear velocity of hydrogen fluoride gas and the processing time.
  • the hole diameter was measured by observing the surface of the glass using a field emission scanning electron microscope (FE-SEM).
  • the hole depth was measured by observing a cross section of the glass using a field emission scanning electron microscope (FE-SEM).
  • a field emission scanning electron microscope (FE-SEM) was used to count the number of holes in the range of 2 ⁇ m ⁇ 2 ⁇ m on the surface of the glass, which was converted to 1 mm 2 and used as the number of holes.
  • FIG. 16 is a photograph of the glass surface obtained as a result, with the vertical axis representing the glass surface temperature (° C.) and the horizontal axis representing the amount of hydrogen fluoride gas sprayed (the amount of sprayed HF (mol / cm 2 )). It is on the graph.
  • “Y” indicates that a minute recess is formed, and “N” indicates that a minute recess is not formed.
  • the pitch of the minute recesses becomes smaller and more minute recesses are formed as the amount of hydrogen fluoride gas sprayed increases.
  • the lower the glass surface temperature the smaller the pitch of the minute recesses and the more minute recesses formed. That is, the pitch of the minute recesses becomes smaller as the glass surface temperature is lower and the amount of hydrogen fluoride gas sprayed is increased, and more minute recesses are formed. Therefore, it is considered that the density of the minute recesses can be adjusted by appropriately adjusting the glass surface temperature and the amount of hydrogen fluoride gas sprayed.
  • the observed minute recesses were not limited to the glass surface temperature and the amount of hydrogen fluoride gas sprayed, and the diameter was about 20 nm and the hole depth was about 100 nm.
  • the diameter of the minute recesses is not limited to the glass surface temperature and the amount of hydrogen fluoride gas sprayed, and the pitch of the minute recesses changes according to the glass surface temperature and the amount of hydrogen fluoride gas sprayed. This is consistent with the mechanism described in FIG. Examples 1 to 19 in which minute recesses are formed are intermediate products of the present invention, and Examples 20 to 22 in which minute recesses are not formed are comparative examples.
  • an etching solution (treatment) in which an aqueous solution containing 50 wt% hydrogen fluoride (HF) and an aqueous solution containing 40 wt% ammonium fluoride (NH 4 F) were mixed at a volume ratio of 1: 9.
  • HF hydrogen fluoride
  • NH 4 F aqueous solution containing 40 wt% ammonium fluoride
  • Examples 23 to 25 are obtained by further etching the sample of Example 10 described above, and Examples 26 to 29 are samples of Example 17 described above. Further, the samples were etched. Examples 30 to 33 were obtained by further etching the sample of Example 19 described above.
  • the sample of Example 10 has a pitch of minute recesses before etching of about 300 nm
  • the sample of Example 17 has a pitch of minute recesses of about 100 nm before etching
  • the sample of Example 19 has a pitch of minute recesses before etching.
  • Example 34 is a glass plate in which only the etching process was performed without performing the hydrogen fluoride process on the glass sheet manufactured by the float process.
  • FIG. 18 shows the results obtained (pillar height, area, occupation ratio, recess hole diameter, hole depth, average F concentration (wt%) at a depth of 0 to 1 ⁇ m, and average F at a depth of 50 to 70 ⁇ m. Concentration (wt%)) and light extraction efficiency).
  • the occupation ratio was calculated from the ratio of the top surface of the pillar on the treated surface of each glass plate. Specifically, the occupation ratio of the pillars was obtained by the following procedure. First, the number of pillars existing in an arbitrary 3 ⁇ m square region on the treated surface of the glass plate and the top surface dimensions of the pillars are measured by SEM.
  • Example 34 is a comparative example.
  • XRF method X-ray fluorescence analysis method
  • ZSX Primus II manufactured by Rigaku.
  • the analysis conditions of the XRF method were as follows. Quantification was performed by a calibration curve method using a standard sample of F. Measuring device: ZSX100 manufactured by Rigaku Corporation Output: Rh 50kV-72mA Filter: OUT attenuator: 1/1 Slit: Std. Spectroscopic crystal: RX25 Detector: PC Peak angle (2 ⁇ / deg.): 47.05 Peak measurement time (seconds): 40 B. G. 1 (2 ⁇ / deg.): 43.00 B. G. 1 measurement time (seconds): 20 B. G. 2 (2 ⁇ / deg.): 50.00 B. G. 2 measurement time (seconds): 20 PHA: 110-450
  • the produced light emitting module has the configuration shown in FIG.
  • a commercially available blue LED chip package (Platinum Dragon Blue; manufactured by OSRAM) was used in the light emitting module other than the transparent member.
  • This package includes a light emitting element (blue LED element) attached to an opaque ceramic substrate, a ceramic side wall having a reflective film on the inner surface, and a resin layer covering the light emitting element, filled in a space surrounded by the side wall and the substrate.
  • the glass plate according to Examples 23 to 34 was used as the transparent member.
  • the glass plate was arrange
  • the wavelength conversion element is not contained in the resin layer in the produced light emitting module. Therefore, in this light emitting module, the light extraction efficiency was measured using blue light as a measurement target.
  • the light emitting modules manufactured using the glass plates according to Examples 23 to 34 will be referred to as light emitting modules according to Examples 23 to 34, respectively.
  • a light emitting module using the glass plate according to Example 34 as a transparent member was used as a reference module.
  • an LED total luminous flux measurement device (Spectra Corp.) equipped with a 6-inch integrating sphere was used. With this device, in a state where a current of 350 mA is applied between the two terminals of the light emitting elements of each light emitting module, the amount of light emitted from the transparent member side is measured, and with respect to the amount of light emitted from the blue LED, The improvement rate of the amount of light increased by passing through the transparent member was defined as the light extraction efficiency.
  • each light emitting module is standardized based on the value of the light extraction efficiency obtained in the reference module as a base (1.0).
  • Examples 23 to 33 are examples of the present invention. In any of the examples, fluorine was not detected at a depth of 50 to 70 ⁇ m.
  • FIG. 19 is a view showing SEM photographs of the treated surfaces of Examples 23 to 33.
  • group 33 a plurality of minute recesses were observed on the top surface of the pillar. This is considered that the mask was formed over a plurality of minute recesses.
  • the groups of Examples 23 to 25 and Examples 26 to 29 of other pitches (300, 100 nm) of the other minute recesses one minute recess was typically observed on the top surface.
  • the pillars of the groups of Examples 30 to 33 formed across a plurality of minute recesses have a large top surface area and a large occupation ratio. This suggests that not only the density of the minute recesses but also the top surface area and the occupation ratio of the pillars can be adjusted by appropriately adjusting the glass surface temperature and the amount of hydrogen fluoride gas sprayed in the hydrogen fluoride treatment. .
  • the shape of the upper surface changes as the processing time of the etching process becomes longer.
  • the processing time is 10 seconds (sec) and 30 seconds (sec)
  • there is a flat portion between adjacent concave portions as shown in FIG. 2 and when the processing time is 60 seconds (sec), there is a concave portion as shown in FIG. Are formed continuously, and in 90 seconds (sec), a concave surface 130 is not formed.
  • the height of a pillar is also high according to processing time.
  • the treatment plate does not have a plurality of pillars and does not contain fluorine atoms. It was confirmed that the light extraction efficiency was significantly improved as compared with the glass plate.
  • the present invention can be used for, for example, a light emitting module having a glass plate.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)
  • Led Device Packages (AREA)

Abstract

L'invention fournit une feuille de verre ainsi qu'un procédé de fabrication de celle-ci, et un module luminescent. La feuille de verre de l'invention permet d'augmenter l'efficacité d'extraction lumineuse lors de sa mise en œuvre dans un module luminescent, ou similaire. La feuille de verre possède à sa surface une couche fluorée dans laquelle des atomes de fluor sont présents. Dans cette couche fluorée, est formée une pluralité de piliers.
PCT/JP2014/064766 2013-06-07 2014-06-03 Feuille de verre ainsi que procédé de fabrication de celle-ci, et module luminescent WO2014196539A1 (fr)

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JP6814986B2 (ja) * 2017-02-28 2021-01-20 パナソニックＩｐマネジメント株式会社 ガラスパネルユニット、ガラス窓、およびガラスパネルユニットの製造方法

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Publication number Priority date Publication date Assignee Title
WO2011004844A1 (fr) * 2009-07-08 2011-01-13 日本電気硝子株式会社 Plaque de verre
WO2012141311A1 (fr) * 2011-04-15 2012-10-18 旭硝子株式会社 Substrat de verre antireflet
WO2014123089A1 (fr) * 2013-02-07 2014-08-14 旭硝子株式会社 Procédé de fabrication de verre

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011004844A1 (fr) * 2009-07-08 2011-01-13 日本電気硝子株式会社 Plaque de verre
WO2012141311A1 (fr) * 2011-04-15 2012-10-18 旭硝子株式会社 Substrat de verre antireflet
WO2014123089A1 (fr) * 2013-02-07 2014-08-14 旭硝子株式会社 Procédé de fabrication de verre

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