WO2011121922A1 - Plaque de verre comportant un film conducteur transparent et procédé pour fabriquer la plaque de verre - Google Patents
Plaque de verre comportant un film conducteur transparent et procédé pour fabriquer la plaque de verre Download PDFInfo
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- WO2011121922A1 WO2011121922A1 PCT/JP2011/001575 JP2011001575W WO2011121922A1 WO 2011121922 A1 WO2011121922 A1 WO 2011121922A1 JP 2011001575 W JP2011001575 W JP 2011001575W WO 2011121922 A1 WO2011121922 A1 WO 2011121922A1
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- WIPO (PCT)
- Prior art keywords
- transparent conductive
- conductive layer
- glass plate
- conductive film
- film
- Prior art date
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- 239000011521 glass Substances 0.000 title claims abstract description 104
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 238000000034 method Methods 0.000 title description 9
- 238000005530 etching Methods 0.000 claims description 28
- 239000011148 porous material Substances 0.000 claims description 22
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 18
- 230000003746 surface roughness Effects 0.000 claims description 18
- 239000007800 oxidant agent Substances 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- 229910001887 tin oxide Inorganic materials 0.000 claims description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 239000010408 film Substances 0.000 description 169
- 239000007789 gas Substances 0.000 description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 23
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 21
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 21
- 239000002585 base Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000010409 thin film Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000005229 chemical vapour deposition Methods 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000011800 void material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000994 depressogenic effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- PKKGKUDPKRTKLJ-UHFFFAOYSA-L dichloro(dimethyl)stannane Chemical compound C[Sn](C)(Cl)Cl PKKGKUDPKRTKLJ-UHFFFAOYSA-L 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 description 1
- YMLFYGFCXGNERH-UHFFFAOYSA-K butyltin trichloride Chemical compound CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
Images
Classifications
-
- 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
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO 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
- C03C2217/00—Coatings on glass
- C03C2217/90—Other aspects of coatings
- C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer 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
- C03C2218/32—After-treatment
- C03C2218/328—Partly or completely removing a coating
- C03C2218/33—Partly or completely removing a coating by etching
Definitions
- the present invention relates to a glass plate with a transparent conductive film used for a photoelectric conversion element and the like and a method for producing the same.
- Thin-film solar cell generally on a transparent substrate such as a glass plate, tin oxide (SnO 2) transparent conductive film (surface electrode) made of, of amorphous semiconductor such as amorphous silicon or amorphous silicon germanium A photoelectric conversion layer and a conductive film (back electrode) are sequentially stacked.
- a transparent substrate such as a glass plate
- tin oxide (SnO 2) transparent conductive film surface electrode
- amorphous semiconductor such as amorphous silicon or amorphous silicon germanium
- a photoelectric conversion layer and a conductive film (back electrode) are sequentially stacked.
- Patent Document 1 discloses a thin film solar cell in which a first underlayer having holes on a glass plate, a second underlayer, and a transparent conductive film are formed in this order. The second underlayer is depressed in the holes in the first underlayer, and the portion of the second underlayer that is depressed in the holes acts as a growth nucleus for efficiently forming the transparent conductive film.
- Patent Document 2 discloses a thin film solar cell in which irregularities are formed on the surface by etching the surface of a transparent conductive film formed of zinc oxide using hydrochloric acid.
- Patent Document 3 discloses a thin-film solar cell in which fine irregularities are provided on the irregularities on the surface of a transparent conductive film.
- the unevenness on the surface contributes to the light confinement of sunlight in the wavelength range of 600 nm to 800 nm, and the minute unevenness contributes to the light confinement of sunlight from 400 nm to 600 nm. Thereby, the photoelectric conversion efficiency with respect to the wide wavelength range of sunlight is improved.
- the light confinement effect is acquired by disperse
- Patent Document 4 When the technique disclosed in Patent Document 4 is used, the surface roughness of the surface of the transparent conductive film can be kept low even if the haze ratio is increased.
- the technique of Patent Document 4 requires inorganic scattering fine particles (for example, alumina fine particles) separately from the binder matrix (for example, silica).
- the binder matrix for example, silica.
- the present invention improves the transparent conductive film itself, and even if the haze ratio of the transparent conductive film is increased, the glass plate with a transparent conductive film that can suppress the surface roughness of the surface can be suppressed.
- the purpose is to provide.
- the present invention comprises a glass plate and a transparent conductive film formed on the glass plate, the transparent conductive film having a transparent conductive layer A and a transparent conductive layer B, and the transparent conductive layer B is
- the transparent conductive layer A is formed on the transparent conductive layer A
- the transparent conductive film includes a plurality of holes, and each of the plurality of holes fills the concave portion on the surface of the transparent conductive layer A with the transparent conductive layer B
- a glass plate with a transparent conductive film is provided.
- this invention is a manufacturing method of the glass plate with a transparent conductive film provided with the glass plate and the transparent conductive film containing the several void
- the metal is formed on the transparent conductive layer A so as to close the plurality of recesses by supplying a film-forming gas containing an oxidizable component capable of generating oxidant and an oxidant capable of oxidizing the oxidizable component.
- this invention is a manufacturing method of the glass plate with a transparent conductive film provided with the glass plate and the transparent conductive film containing the several void
- supplying a mixed gas containing an oxidant capable of oxidizing the component a plurality of regions on the surface of the transparent conductive layer a are caused to recede in the film thickness direction by the etching component, and a plurality of regions are removed from the transparent conductive layer a.
- the transparent conductive layer A having recesses is formed, and the transparent holes are formed by forming the transparent conductive layer B containing the metal oxide on the transparent conductive layer A so as to close the plurality of recesses.
- the present invention it is possible to achieve a high haze ratio required for a thin film solar cell substrate while suppressing an increase in surface roughness of the surface of the transparent conductive film.
- FIG. 1A is a schematic cross-sectional view of an example of a glass plate with a transparent conductive film of the present invention.
- a glass plate 10 with a transparent conductive film includes a glass plate 11, a base film 12 formed on the surface of the glass plate 11, and a transparent conductive film formed on the surface of the base film 12. 15.
- the base film 12 includes a first base layer 12a and a second base layer 12b in this order from the glass plate 11 side.
- the transparent conductive film 15 includes a first transparent conductive layer (transparent conductive layer A) 13 and a second transparent conductive layer (transparent conductive layer B) 14 in order from the glass plate 11 side.
- the glass plate 10 with a transparent conductive film is preferably provided with a base film 12, and the transparent conductive film 15 is preferably formed on the glass plate 11 through the base film 12. Thereby, the alkali component of the glass plate 11 can be prevented from entering the transparent conductive film 15.
- the base film 12 may be composed of one layer, and in that case, it is preferable that silicon oxide, silicon oxycarbide, silicon nitride, aluminum oxide, silicon oxynitride, or tin-doped silicon oxide be a main component.
- the base film 12 may be composed of two layers, a first base layer 12a and a second base layer 12b.
- the first underlayer 12a is preferably composed mainly of silicon oxide, titanium oxide, zinc oxide, or silicon oxycarbide, and particularly preferably composed mainly of tin oxide.
- the second underlayer 12b is preferably composed mainly of silicon oxide or aluminum oxide, and particularly preferably composed mainly of silicon oxide.
- the “main component” refers to a component having a composition component content of 50% by mass or more according to common usage. Furthermore, if the film thickness and refractive index of these foundation layers 12a and 12b are appropriately adjusted, the reflectance and reflection interference color of the glass plate 10 with a transparent conductive film can be reduced.
- the film thickness of the first underlayer 12a is preferably 10 to 100 nm, particularly 20 to 70 nm.
- the refractive index of the first base layer 12a is preferably 1.8 to 2.4.
- the thickness of the second underlayer 12b is preferably 5 to 80 nm, particularly 10 to 40 nm.
- the refractive index of the second underlayer 12b is preferably 1.4 to 1.7.
- the transparent conductive film 15 is composed of at least two transparent conductive layers 13 and 14.
- the transparent conductive layer A13 preferably contains zinc oxide as a main component.
- the material constituting the transparent conductive layer A13 is not particularly limited as long as it is conductive and can be etched by an etching component described later.
- the etching component may be selected as appropriate depending on the material to be etched, but hydrogen chloride, silicon chloride, or the like may be used.
- As an etching component of zinc oxide hydrogen chloride is suitable.
- the thickness of the transparent conductive layer A13 is preferably from 180 nm to 600 nm, more preferably from 200 nm to 600 nm, particularly preferably from 300 nm to 500 nm. If the transparent conductive layer A13 is too thin, the size of the pores 13a and 13b in the film thickness direction is the wavelength of sunlight that should cause scattering as described later (depending on the photoelectric conversion layer used, for example, a wavelength of about 800 nm) In comparison, it becomes too small. On the other hand, if the thickness of the transparent conductive layer A13 is excessively thick, there is a possibility that the visible light transmittance is reduced, or the stress in the film is increased to deteriorate the durability.
- Holes 13 a and 13 b are formed in the transparent conductive layer A 13, and the holes 13 a and 13 b scatter light that enters from below in FIG. 1 and reaches the photoelectric conversion layer formed above the transparent conductive film 15. Contribute to.
- the holes 13a and 13b are formed by the transparent conductive layer B14 closing the recess 13h, which is generated when a part of the surface 13s of the transparent conductive layer A13 recedes in the film thickness direction (specifically, downward in the drawing) from above. Is formed.
- the surface 13s of the transparent conductive layer A13 may recede over the entire thickness range (hole 13a) or may recede to a partial thickness range (hole 13b).
- the hole has a height equal to the film thickness of the transparent conductive film A13.
- FIG. 1B is an enlarged view of the region 13c in the transparent conductive film 15 of FIG.
- the hole 13a has a needle-like body 13d extending from the surrounding wall surface toward the inside of the hole 13a.
- the needle-like body 13d is typically formed so as to hang down from the bottom surface of the transparent conductive layer B14.
- the needle-like body 13d is assumed to have grown by the deposition of the material constituting the transparent conductive layer B14. However, depending on the film forming conditions of the transparent conductive film 15, the needle-like body 13d may not be formed. In some cases, the needle-like body grows not from above the hole 13a but from the side surface of the hole 13a. Needle-like bodies may be formed not only in the holes 13a but also in the holes 13b.
- the size of the holes 13a and 13b when the transparent conductive film 15 is observed along the film thickness direction is calculated by converting the average area into a circle (the diameter ( (Hereinafter referred to as “diameter A”), preferably 0.5 ⁇ m to 10 ⁇ m, and more preferably 1.0 ⁇ m to 5.0 ⁇ m. This diameter can be measured by a method using EPMA described later.
- the size of the holes 13a and 13b appearing in the cross section obtained by cutting the transparent conductive film 15 along the film thickness direction is expressed by a diameter (hereinafter referred to as “diameter B”) calculated by converting the average area into a circle. It is preferably 0.1 ⁇ m or more and 0.6 ⁇ m or less. This diameter can be measured by cross-sectional observation with an SEM. Further, the ratio of the total area of the holes 13a and 13b to the area of the transparent conductive layer A13 when observed along the film thickness direction is preferably 10% or more and 40% or less. When the size and area ratio of the holes 13a and 13b are in an appropriate range, the incident light can be efficiently scattered and the strength of the transparent conductive layer A13 can be maintained.
- the ratio of diameter A to diameter B (diameter A / diameter B) is preferably 3 or more and 10 or less. If the ratio of the diameter A to the diameter B is out of the above range, the incident light scattering effect may not be sufficiently obtained.
- the number of holes in a region of 100 ⁇ m ⁇ 100 ⁇ m is preferably 100 or more and 1000 or less. A larger number of pores is not preferable because it is difficult to maintain the mechanical strength of the film. On the other hand, if the number of holes is smaller than this, the effect of light scattering is lowered, which is not preferable.
- the transparent conductive layer B14 is made of a transparent and conductive material.
- the transparent conductive layer B14 preferably contains tin oxide as a main component and also contains fluorine. By adding fluorine, the conductivity of the transparent conductive layer B14 can be improved. In order to increase the conductivity of the transparent conductive layer B14, other trace components such as antimony may be added together with fluorine or instead of fluorine.
- the component to be oxidized (tin raw material) to be added to the film forming gas to produce tin oxide by chemical vapor deposition (CVD) include tin chloride, dimethyltin dichloride, and monobutyltin trichloride.
- the oxidizing agent to be added to the film forming gas in order to oxidize the tin raw material include oxygen and water vapor.
- the thickness of the transparent conductive layer B14 is preferably 200 nm to 1000 nm, more preferably 200 nm to 800 nm, and particularly preferably 250 nm to 700 nm. If the transparent conductive layer B14 is too thin, the conductivity of the transparent conductive film 15 may be too low. On the other hand, if the transparent conductive layer B14 is too thick, the light transmittance of the glass plate with the transparent conductive film is too low, the surface roughness of the surface of the transparent conductive film 15 is excessive, or the residual stress in the film is large. And durability may deteriorate.
- the surface of the transparent conductive film 15 is formed by the surface of the transparent conductive layer B14.
- the surface roughness Ra on the surface of the transparent conductive film 15 is preferably 40 nm or less, and more preferably 5 nm or more and 30 nm or less. When the surface roughness Ra on the surface of the transparent conductive film 15 exceeds 40 nm, the surface of the transparent conductive film 15 tends to cause defects in the photoelectric conversion layer, which is not preferable.
- the surface of the transparent conductive film 15 may be constituted by the surface of a transparent conductive layer (transparent conductive layer C) other than the transparent conductive layer B14 further laminated on the transparent conductive layer B14.
- the surface roughness of the transparent conductive film 15 is preferably in the above range.
- the transparent conductive layer C may be, for example, an ITO film or a zinc oxide film doped with aluminum.
- the haze ratio of the transparent conductive film 15 is preferably 10% or more, more preferably 15% or more, and particularly preferably 20% or more.
- the haze rate means a haze rate in the wavelength range of 400 nm to 800 nm.
- the sheet resistance Rs on the surface of the transparent conductive film 15 is preferably 30 ⁇ / ⁇ or less, more preferably 20 ⁇ / ⁇ or less, and particularly preferably 5 ⁇ / ⁇ or more and 15 ⁇ / ⁇ or less.
- FIG. 2A shows a preformed body 50 a in which only the base film 52 is formed on the glass plate 51.
- the base film 52 that is, the base layers 52a and 52b can be formed on the glass plate 51 by sputtering, CVD, or the like. However, it is not always necessary to form the base film 52.
- a transparent conductive layer (transparent conductive layer a) 57 is formed on the preform 50a to obtain a preform 50b shown in FIG.
- the transparent conductive layer 57 is preferably a zinc oxide film formed by a sputtering method, but may be formed by other methods such as a CVD method.
- a mixed gas containing an etching component for etching the transparent conductive layer 57 and an oxidizable component and an oxidizing component for forming an additional transparent conductive layer is sprayed on the transparent conductive layer 57 by a CVD method.
- a transparent conductive layer (transparent conductive layer A) 53 having a recess is obtained by retreating a part of the surface of the transparent conductive layer 57, and a transparent conductive layer (transparent conductive layer B) 54 is formed, and the transparent conductive layer having pores 53a.
- a glass plate 50 with a transparent conductive film provided with the film 55 is obtained (FIG. 2D).
- FIG. 2C In the middle of film formation using the mixed gas, as shown in FIG. 2C, a part of the surface of the transparent conductive layer 57 is retreated, and the transparent conductive layer B grows thereon, so that the preform 50c is formed. It is thought that is formed.
- the transparent conductive layer 54 may be formed in two or more steps. In that case, it is preferable to spray a film-forming gas obtained by removing the etching component from the above-mentioned mixed gas at the time of forming the transparent conductive layer 54 for the second time and thereafter.
- a film-forming gas that does not include such an etching component is sprayed when the transparent conductive layer 54 is formed for the second time or later
- a mixed gas containing an etching component is sprayed when the transparent conductive layer 54 is formed for the second time or later.
- the film formation rate is increased, and the transparent conductive layer 54 is easily grown to a sufficient thickness.
- the surface characteristics such as the surface roughness Ra and the sheet resistance of the transparent conductive layer 54 can be improved.
- the electron mobility in the transparent conductive layer 54 can be improved.
- the transparent conductive film C may be formed by a CVD method, but formed by a physical vapor deposition method (PVD method) such as a sputtering method.
- PVD method physical vapor deposition method
- the transparent conductive layer 53 is preferably composed mainly of zinc oxide.
- mixed gas contains the tin raw material and oxidizing agent which are to-be-oxidized components, and also hydrogen chloride.
- the molar ratio of hydrogen chloride to the tin raw material in the mixed gas is preferably 0.24 or more and 0.72 or less. When the molar ratio of hydrogen chloride is smaller than this, vacancies are hardly formed and it is difficult to achieve a desired haze ratio.
- the molar ratio of hydrogen chloride is larger than this, by-products are generated excessively from the transparent conductive layer 57, the conductivity of the formed transparent conductive film 55 is lowered, or the pores 53a are too large. The mechanical strength of the transparent conductive film 55 may decrease.
- the temperature of the glass plate when supplying the mixed gas is preferably 400 ° C. or higher and 800 ° C. or lower, particularly preferably 600 ° C. or higher and 750 ° C. or lower.
- the transparent conductive layer 54 is formed using a mixed gas containing an etching component and a film forming component (oxidized component and oxidizing agent).
- a mixed gas containing an etching component and a film forming component oxidized component and oxidizing agent.
- an etching gas containing an etching component and a film forming gas containing a film forming component are used. May be sequentially supplied to form the transparent conductive layer 54.
- Example 1 A first underlayer (SnO 2 film: thickness 25 nm) and a second underlayer (SiO 2 film: thickness 25 nm) are formed on a glass plate (thickness 3.2 mm) made of soda lime silica glass by a CVD method. The layers were laminated in this order, and then a transparent conductive layer a (ZnO film: thickness 368 nm) was formed by a sputtering method to obtain a preform. This preform was put into a substrate transfer type atmospheric pressure CVD apparatus, and the glass plate was heated to 660 ° C., and dimethyltin dichloride (hereinafter referred to as “DMT”) (1.68 mol%), water vapor (water vapor relative to DMT).
- DMT dimethyltin dichloride
- Example 2 A glass plate with a transparent conductive film having pores in the transparent conductive film was obtained in the same manner as in Example 1 except that the concentration of hydrogen chloride in the mixed gas was changed so that the molar ratio to DMT was 0.48.
- Example 3 A glass plate with a transparent conductive film having pores in the transparent conductive film was obtained in the same manner as in Example 1 except that the concentration of hydrogen chloride in the mixed gas was changed so that the molar ratio to DMT was 0.96.
- Example 4 A glass plate with a transparent conductive film having pores in the transparent conductive film was obtained in the same manner as in Example 1 except that the concentration of hydrogen chloride in the mixed gas was changed so that the molar ratio to DMT was 1.20.
- Example 5 A glass plate with a transparent conductive film having pores in the transparent conductive film was obtained in the same manner as in Example 1 except that the thickness of the transparent conductive layer a was changed to 231 nm.
- Example 6 In the same manner as in Example 1, except that the thickness of the transparent conductive layer a was changed to 458 nm and the concentration of oxygen in the mixed gas was increased so that the molar ratio with respect to DMT was 24, pores were formed in the transparent conductive film. A glass plate with a transparent conductive film was obtained.
- Example 7 In the same manner as in Example 1, except that the thickness of the transparent conductive layer a was changed to 540 nm and the concentration of water vapor in the mixed gas was increased so that the molar ratio with respect to DMT was 15. A glass plate with a transparent conductive film was obtained.
- Example 8 The first film formation was performed in the same manner as in Example 1 except that the thickness of the transparent conductive layer a was changed to 458 nm and the concentration of hydrogen fluoride in the mixed gas was changed so that the molar ratio to DMT was 0.10. Went. Subsequently, hydrogen chloride is removed from the mixed gas used in the first film formation (that is, using a film forming gas obtained by removing hydrogen chloride from the mixed gas), and the second transparent film is formed in the same manner as in the first time. Conductive layer B was formed to obtain a glass plate with a transparent conductive film having pores in the transparent conductive film.
- Example 1 A glass plate with a transparent conductive film was obtained in the same manner as in Example 1 except that hydrogen chloride was removed from the mixed gas (that is, a film forming gas from which hydrogen chloride was removed from the mixed gas was used).
- Example 2 A glass plate with a transparent conductive film was obtained in the same manner as in Example 2 except that the transparent conductive layer a was not formed.
- Example 3 A glass plate with a transparent conductive film was obtained in the same manner as in Example 7 except that hydrogen chloride was removed from the mixed gas (that is, a film forming gas from which hydrogen chloride was removed from the mixed gas was used).
- the thickness of the transparent conductive layer B, the haze ratio, the shape of the pores, the surface roughness Ra, the sheet resistance, and the light beam are as follows.
- the transmittance and durability were examined.
- the cross section of the glass plate with a transparent conductive film was image
- the thickness of the transparent conductive layer B was measured by observing the cross section along the film thickness direction of the transparent conductive layer B using SEM. Note that the thickness of the transparent conductive layer a (which becomes the transparent conductive layer A after the supply of the mixed gas) does not change even after the transparent conductive layer B is formed using the mixed gas. Has been confirmed.
- hole with respect to the area of the transparent conductive layer A whole was computed.
- the cross section along the film thickness direction of the glass plate with the transparent conductive film was observed by SEM, the area of the voids in the transparent conductive layer A that appeared in the range of 4 mm in the cross section direction was measured, and this average area was true.
- the diameter (diameter B) when considered as a circle was calculated. However, in the calculation of the diameter A and the area ratio, only the part where the area of the part where zinc does not exist is 1 ⁇ m 2 or more was regarded as a hole.
- the thickness of the transparent conductive layer B, the haze ratio, the shape and distribution of the holes, the surface roughness Ra, the sheet resistance as described above Table 1 shows the results of measurement of light transmittance and durability.
- the composition of the second transparent conductive layer B is formed. Only the measurement results after the film are described.
- Voids were formed in any of the transparent conductive films of the glass plates with the transparent conductive film of Examples 1 to 8. On the other hand, no pores were formed in the glass plates with transparent conductive films of Comparative Examples 1 to 3.
- the transparent conductive layer A does not exist in the glass plate with a transparent conductive film of Comparative Example 2, no pores are formed.
- the surface roughness Ra increases as the haze ratio increases because the surface irregularities are the main factor determining the haze ratio.
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Abstract
L'invention porte sur une plaque de verre comportant un film conducteur transparent, dans laquelle une augmentation de la rugosité de la surface peut être supprimée, même si le taux de voile du film conducteur transparent est accru. La plaque de verre comportant le film conducteur transparent comporte la plaque de verre et le film conducteur transparent formé sur la plaque de verre. Le film conducteur transparent comporte une couche conductrice transparente (couche conductrice transparente (A)), et une couche conductrice transparente (couche conductrice transparente (B)), la couche conductrice transparente (B) étant formée sur la couche conductrice transparente (A), le film conducteur transparent comprend une pluralité de trous, et chacun des trous est formé par le fait que la couche conductrice transparente (B) couvre une section en creux dans la surface de la couche conductrice transparente (A).
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JP2010-083847 | 2010-03-31 | ||
JP2010083847A JP2011212988A (ja) | 2010-03-31 | 2010-03-31 | 透明導電膜付きガラス板およびその製造方法 |
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PCT/JP2011/001575 WO2011121922A1 (fr) | 2010-03-31 | 2011-03-17 | Plaque de verre comportant un film conducteur transparent et procédé pour fabriquer la plaque de verre |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014137967A1 (fr) * | 2013-03-08 | 2014-09-12 | Corning Incorporated | Films minces d'oxyde conducteurs transparents en couches |
CN104718581A (zh) * | 2012-10-17 | 2015-06-17 | 旭硝子株式会社 | 带导电性薄膜的玻璃基板、薄膜太阳能电池、低辐射玻璃基板、带导电性薄膜的玻璃基板的制造方法 |
EP3100986A4 (fr) * | 2014-01-31 | 2017-09-20 | Nippon Sheet Glass Company, Limited | Procédé de production de plaque de verre et plaque de verre |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019139008A1 (fr) * | 2018-01-11 | 2019-07-18 | 日本板硝子株式会社 | Substrat avec film mince, et procédé de fabrication de celui-ci |
JP7306502B2 (ja) * | 2019-07-12 | 2023-07-11 | Agc株式会社 | 膜付きガラス基板及びその製造方法 |
Citations (3)
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JP2001053307A (ja) * | 1999-05-28 | 2001-02-23 | Nippon Sheet Glass Co Ltd | 光電変換装置用基板とその製造方法、およびこれを用いた光電変換装置 |
JP2004323321A (ja) * | 2003-04-25 | 2004-11-18 | Nippon Sheet Glass Co Ltd | 透明導電膜付き基板の製造方法 |
JP2007530311A (ja) * | 2004-02-23 | 2007-11-01 | シン アン エスエヌピー タイワン カンパニー リミテッド | 電気光学ディスプレイにおける透明電極用の改善されたエッチング特性を有する2層型透明導体スキーム |
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2010
- 2010-03-31 JP JP2010083847A patent/JP2011212988A/ja active Pending
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2011
- 2011-03-17 WO PCT/JP2011/001575 patent/WO2011121922A1/fr active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2001053307A (ja) * | 1999-05-28 | 2001-02-23 | Nippon Sheet Glass Co Ltd | 光電変換装置用基板とその製造方法、およびこれを用いた光電変換装置 |
JP2004323321A (ja) * | 2003-04-25 | 2004-11-18 | Nippon Sheet Glass Co Ltd | 透明導電膜付き基板の製造方法 |
JP2007530311A (ja) * | 2004-02-23 | 2007-11-01 | シン アン エスエヌピー タイワン カンパニー リミテッド | 電気光学ディスプレイにおける透明電極用の改善されたエッチング特性を有する2層型透明導体スキーム |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104718581A (zh) * | 2012-10-17 | 2015-06-17 | 旭硝子株式会社 | 带导电性薄膜的玻璃基板、薄膜太阳能电池、低辐射玻璃基板、带导电性薄膜的玻璃基板的制造方法 |
CN104718581B (zh) * | 2012-10-17 | 2018-04-13 | 旭硝子株式会社 | 带导电性薄膜的玻璃基板、薄膜太阳能电池、低辐射玻璃基板、带导电性薄膜的玻璃基板的制造方法 |
WO2014137967A1 (fr) * | 2013-03-08 | 2014-09-12 | Corning Incorporated | Films minces d'oxyde conducteurs transparents en couches |
US9688570B2 (en) | 2013-03-08 | 2017-06-27 | Corning Incorporated | Layered transparent conductive oxide thin films |
EP3100986A4 (fr) * | 2014-01-31 | 2017-09-20 | Nippon Sheet Glass Company, Limited | Procédé de production de plaque de verre et plaque de verre |
US10358381B2 (en) | 2014-01-31 | 2019-07-23 | Nippon Sheet Glass Company, Limited | Method for producing glass sheet, and glass sheet |
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