CN111253084A - 一种薄膜器件 - Google Patents
一种薄膜器件 Download PDFInfo
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- CN111253084A CN111253084A CN202010215753.XA CN202010215753A CN111253084A CN 111253084 A CN111253084 A CN 111253084A CN 202010215753 A CN202010215753 A CN 202010215753A CN 111253084 A CN111253084 A CN 111253084A
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- 239000010409 thin film Substances 0.000 title claims abstract description 51
- 239000010408 film Substances 0.000 claims abstract description 383
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052709 silver Inorganic materials 0.000 claims abstract description 51
- 239000004332 silver Substances 0.000 claims abstract description 51
- 239000010410 layer Substances 0.000 claims description 339
- 230000000712 assembly Effects 0.000 claims description 19
- 238000000429 assembly Methods 0.000 claims description 19
- 229910001000 nickel titanium Inorganic materials 0.000 claims description 9
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910001120 nichrome Inorganic materials 0.000 claims description 6
- 229910003087 TiOx Inorganic materials 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 4
- 229910019923 CrOx Inorganic materials 0.000 claims description 3
- 229910015711 MoOx Inorganic materials 0.000 claims description 3
- 239000011229 interlayer Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 abstract description 37
- 238000010438 heat treatment Methods 0.000 abstract description 27
- 238000002834 transmittance Methods 0.000 abstract description 26
- 230000001681 protective effect Effects 0.000 abstract description 18
- 239000000126 substance Substances 0.000 abstract description 3
- 239000011521 glass Substances 0.000 description 55
- 238000012360 testing method Methods 0.000 description 23
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 22
- 238000001514 detection method Methods 0.000 description 20
- 238000002474 experimental method Methods 0.000 description 19
- 239000000463 material Substances 0.000 description 18
- 229910007717 ZnSnO Inorganic materials 0.000 description 17
- 239000005340 laminated glass Substances 0.000 description 14
- 230000001070 adhesive effect Effects 0.000 description 11
- 239000011787 zinc oxide Substances 0.000 description 11
- 230000003287 optical effect Effects 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 9
- 238000010030 laminating Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 238000009863 impact test Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229910003437 indium oxide Inorganic materials 0.000 description 5
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 229910004205 SiNX Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910006854 SnOx Inorganic materials 0.000 description 2
- 229910007667 ZnOx Inorganic materials 0.000 description 2
- 229910003134 ZrOx Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000005329 float glass Substances 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 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
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000006063 cullet Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3618—Coatings of type glass/inorganic compound/other inorganic layers, at least one layer being metallic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3626—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer at least containing a nitride, oxynitride, boronitride or carbonitride
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3639—Multilayers containing at least two functional metal layers
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3644—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the metal being silver
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3647—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer in combination with other metals, silver being more than 50%
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
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- C—CHEMISTRY; METALLURGY
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3652—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the coating stack containing at least one sacrificial layer to protect the metal from oxidation
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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
- C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
- C03C27/06—Joining glass to glass by processes other than fusing
- C03C27/10—Joining glass to glass by processes other than fusing with the aid of adhesive specially adapted for that purpose
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
Abstract
本发明公开了一种薄膜器件,包括依次向上层叠的基板、底层电介质膜层、膜层组件和保护膜层,所述膜层组件包括沿基板向上依次层叠的银膜层、牺牲膜层和电介质膜层,或所述膜层组件包括沿基板向上依次层叠的牺牲膜层、银膜层和电介质膜层,所述膜层组件还包括AgLa膜层,所述AgLa膜层层叠在牺牲膜层与电介质膜层之间;或所述AgLa膜层层叠在银膜层下面;或所述AgLa膜层层叠在牺牲膜层与电介质膜层之间,同时所述AgLa膜层还层叠在银膜层下面;其中,所述AgLa膜层中La的含量≤50at%。本发明可以提高膜系在高温热处理的稳定性,又可提高该薄膜器件的化学稳定性和改善其机械性能,且具有高的可见光透过率、低的电阻。
Description
技术领域
本发明属于薄膜器件技术领域,具体地涉及一种可进行高温热处理的薄膜器件。
背景技术
普通的玻璃没有隔热功能,随着人们节能意识的增强,现在很多建筑物或汽车都已使用镀膜玻璃(薄膜器件),这些镀膜玻璃可以起到很好的隔热效果,使建筑物内部或车内的舒适度增加。
太阳能电池是用于通过阳光直接生成电流的光伏元件。由于对清洁能源的需求不断增加,最近几年太阳能电池的制造已经大幅扩大并且还在持续扩大。由于透明导电氧化物膜作为透明涂层和电极的多功能性,其在太阳能电池中得到广泛使用。在许多情况下,通过增加透明导电氧化物膜的掺杂物降低电阻导致不期望的透明度的降低,同时透明导电氧化物膜在进行高温热处理后,其一些性能会出现下降。还有为了进一步降低透明导电氧化物膜的电阻,则需要更厚的膜层,这会导致膜层的透过率降低、膜层的应力增大而导致膜层的不稳定性增加,也增加了膜层的制造成本。
在太阳能电池、建筑及汽车等应用领域所使用的薄膜器件,其在制备过程都需要经受高温热处理,因此要求该薄膜器件能够耐受高温热处理,同时具备高的可见光透过率、低的电阻、良好的抗机械性能及高的稳定性等,但现有的薄膜器件无法满足该要求,有必要对其进行改进。
发明内容
本发明的目的在于提供一种能够耐受高温热处理,同时具备高的可见光透过率、低的电阻、良好的抗机械性能及高的稳定性的薄膜器件用以解决上述存在的技术问题。
为实现上述目的,本发明采用的技术方案为:一种薄膜器件,包括依次向上层叠的基板、底层电介质膜层、膜层组件和保护膜层,所述膜层组件包括沿基板向上依次层叠的银膜层、牺牲膜层和电介质膜层,或所述膜层组件包括沿基板向上依次层叠的牺牲膜层、银膜层和电介质膜层,所述膜层组件还包括AgLa膜层,所述AgLa膜层层叠在牺牲膜层与电介质膜层之间;或所述AgLa膜层层叠在银膜层下面;或所述AgLa膜层层叠在牺牲膜层与电介质膜层之间,同时所述AgLa膜层还层叠在银膜层下面;其中,所述AgLa膜层中La的含量≤50at%。
进一步的,所述AgLa膜层的厚度为0.05-10nm,优选厚度为1-8nm。
进一步的,所述AgLa膜层中La的含量≤30at%。
更进一步的,所述AgLa膜层中La的含量≤20at%。
更进一步的,所述AgLa膜层中La的含量≤10at%。
进一步的,所述牺牲膜层的厚度为0.1-8nm,优选厚度为1-5nm。
进一步的,所述牺牲膜层的材料为NiCr、Ti、NiCrOx、Cr、NiCrMo、CrOx、MoOx、TiMo、TiMoOx、NiTi、TiOx和NiTiOx中的任意一种或它们的任一组合。
进一步的,所述电介质膜层、底层电介质膜层和保护膜层的材料为SnOx、TiOx、SiOx、SiNx、ZnOx、AlZnOx、ZnxSnyOn、ZrOx、ZnxTiyOn、NbOx、TixNbyOn、SiNOx、ITO、AZO、IWO、BZO、GZO、IZO、IMO、ICO、ITIO、IGZO、氧化锡基材料和金属硫化物中的任意一种或它们的任一组合。
进一步的,所述电介质膜层、底层电介质膜层和保护膜层的膜层厚度为1-100nm。
进一步的,所述基板为玻璃基板、聚酰亚胺基板、或具有太阳能电池结构的基板。
进一步的,所述膜层组件的数量为两个,两个膜层组件依次层叠设置。
进一步的,所述膜层组件的数量为三个,三个膜层组件依次层叠设置。
进一步的,所述膜层组件的数量为四个,四个膜层组件依次层叠设置。
进一步的,该薄膜器件用于制作成夹层薄膜器件或中空薄膜器件。
本发明的有益技术效果:
本发明通过在牺牲膜层之上和/或银膜层之下形成AgLa膜层,AgLa膜层中La的含量≤50at%,可以使整个膜系的内应力减小,可很好的保护银膜层和牺牲膜层免受外界环境的破坏,该膜层在较高的温度环境下保持良好的膜层质量,从而可以提高膜系在高温热处理的稳定性,又可提高该薄膜器件的化学稳定性和改善其机械性能。此外,本发明还具有高的光透过率、低的电阻。
附图说明
为了更清楚地说明本发明实施例中的技术方案,下面将对实施例描述中所需要使用的附图作简要介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域的普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1为本发明的一种薄膜器件的结构示意图;
图2为本发明的另一种薄膜器件的结构示意图;
图3为本发明的第三种薄膜器件的结构示意图;
图4为本发明的第四种薄膜器件的结构示意图。
具体实施方式
为进一步说明各实施例,本发明提供有附图。这些附图为本发明揭露内容的一部分,其主要用以说明实施例,并可配合说明书的相关描述来解释实施例的运作原理。配合参考这些内容,本领域普通技术人员应能理解其他可能的实施方式以及本发明的优点。图中的组件并未按比例绘制,而类似的组件符号通常用来表示类似的组件。
现结合附图和具体实施方式对本发明进一步说明。
在此先说明,本发明中的氧化锡基材料为氧化锡掺杂氟的材料、氧化锡掺碘的材料、氧化锡掺杂锑的材料或它们的任一组合;本发明中的ITO是指氧化铟掺杂锡的材料、AZO是指氧化锌掺杂铝的材料、IWO是指氧化铟掺杂钨的材料、BZO是指氧化锌掺杂硼的材料、GZO是指氧化锌掺杂镓的材料、IZO是指氧化锌掺杂铟的材料、IMO是指氧化铟掺杂钼的材料、ICO是指氧化铟掺杂铈的材料、ITIO是指氧化铟掺杂钛的材料、IGZO是指氧化锌掺杂铟镓的材料。
如图1所示,一种薄膜器件,包括依次向上层叠的基板1、底层电介质膜层2、膜层组件和保护膜层7,所述膜层组件包括沿基板1向上依次层叠的银膜层3、牺牲膜层4和电介质膜层6,所述膜层组件还包括AgLa膜层5,所述AgLa膜层5层叠在牺牲膜层4与电介质膜层6之间,所述AgLa膜层5中La的含量≤50at%。
优选的,所述AgLa膜层5的厚度为0.05-10nm,优选厚度为1-8nm,若膜层太薄起不到应有的作用,若膜层太厚会降低膜层的光学性能,同时会使膜层间的粘接效果下降。
优选的,所述AgLa膜层5中La的含量≤30at%,使膜层可以耐受更高的温度。
更优选的,所述AgLa膜层5中La的含量≤20at%,在较高的温度下膜层仍然保持良好的界面状态,同时使膜层的光学性能更好。
更优选的,所述AgLa膜层5中La的含量≤10at%,膜层的功函数与牺牲层更加匹配,使膜系的电学性能更加优异。
优选的,所述底层电介质膜层2、电介质膜层6和保护膜层7的膜层厚度均为1-100nm,这些膜层太薄的话起不到应有的效果,太厚的话则会严重影响光的透过效果,同时会影响膜层之间的粘接效果,且会增加制造成本。
优选的,所述牺牲膜层4的厚度为0.1-8nm,优选厚度为1-5nm,若膜层太厚的话,会减弱整个膜系的粘接性能同时减弱其光学性能,若膜层太薄的话,其起不到应有的作用。
具体的,所述牺牲膜层4的材料可以为NiCr、Ti、NiCrOx、Cr、NiCrMo、CrOx、MoOx、TiMo、TiMoOx、NiTi、TiOx和NiTiOx中的任意一种或它们的任一组合。
所述底层电介质膜层2、电介质膜层6和保护膜层7的材料可以为SnOx、TiOx、SiOx、SiNx、ZnOx、AlZnOx、ZnxSnyOn、ZrOx、ZnxTiyOn、NbOx、TixNbyOn、SiNOx、ITO、AZO、IWO、BZO、GZO、IZO、IMO、ICO、ITIO、IGZO、氧化锡基材料和金属硫化物中的任意一种或它们的任一组合。
所述基板1为玻璃基板、聚酰亚胺基板、或具有太阳能电池结构的基板等。
当然,在一些实施例中,AgLa膜层也可以是设置在银膜层下面,或AgLa膜层设置在牺牲膜层与电介质膜层之间,同时还设置在银膜层下面。
当然,在一些实施例中,上述膜层组件中的牺牲膜层也可以是设置在银膜层下面,即膜层组件包括沿基板向外依次层叠的牺牲膜层、银膜层和电介质膜层。
此外,也可在沉积银膜层3之前先沉积一层牺牲膜层。
图2所示为本发明薄膜器件的另一种结构,其与图1所示的薄膜器件的区别为:膜层组件的数量为两个,两个膜层组件依次层叠,其具体结构为包括依次层叠的基板1、底层电介质膜层2、第一银膜层3、第一牺牲膜层4、第一AgLa膜层5、第一电介质膜层6、第二银膜层31、第二牺牲膜层41、第二AgLa膜层51、第二电介质膜层61和保护膜层7。图2的薄膜器件相对于图1的薄膜器件,方块电阻更低。
图3所示为本发明薄膜器件的另一种结构,其与图2所示的薄膜器件的区别为:膜层组件的数量为三个,三个膜层组件依次层叠,其具体结构为包括依次层叠的基板1、底层电介质膜层2、第一银膜层3、第一牺牲膜层4、第一AgLa膜层5、第一电介质膜层6、第二银膜层31、第二牺牲膜层41、第二AgLa膜层51、第二电介质膜层61、第三银膜层32、第三牺牲膜层42、第三AgLa膜层52、第三电介质膜层62和保护膜层7。图3的薄膜器件相对于图2的薄膜器件,方块电阻更低。
图4所示为本发明薄膜器件的另一种结构,其与图3所示的薄膜器件的区别为:膜层组件的数量为四个,四个膜层组件依次层叠,其具体结构为包括依次层叠的基板1、底层电介质膜层2、第一银膜层3、第一牺牲膜层4、第一AgLa膜层5、第一电介质膜层6、第二银膜层31、第二牺牲膜层41、第二AgLa膜层51、第二电介质膜层61、第三银膜层32、第三牺牲膜层42、第三AgLa膜层52、第三电介质膜层62、第四银膜层33、第四牺牲膜层43、第四AgLa膜层53、第四电介质膜层63和保护膜层7。图4的薄膜器件相对于图3的薄膜器件,方块电阻更低。
下面将通过几个具体实施例来说明本发明的薄膜器件。以下涉及的实施例及对比例,均是在干净的、厚度为2.0mm的透明浮法玻璃原片(标记为玻璃基板2.0C)的空气面上依次镀上各膜层。
单片玻璃基板镀膜高温热处理后,镀膜玻璃基板的最外镀膜层为最外保护膜层,最外保护膜层向外依次和厚度为0.76mm的PVB、另外一片没有镀膜的厚度为2.0mm的透明浮法玻璃基板层压在一起,形成镀膜夹层玻璃。而形成的镀膜夹层玻璃需要通过敲击实验——最重要的物理性能测试之一,该实验是衡量膜层与PVB、玻璃之间粘结性能的检测方法。Solutia Europe s.a.公司将夹层玻璃敲击标准分为9级。根据敲击后碎玻璃粘在PVB上的量从少到多,规定标准等级为第1级至第9级。满足国标GB9656-2003要求的夹层玻璃需要符合的敲击等级为:第3级≤敲击等级≤第6级。
敲击实验步骤为:
a.从整个镀膜夹层玻璃上切下两块100×300mm的试验片;b.将两试样放置在-18℃±2℃下保存至少2小时;c.将试样从上述低温处取出放置在常温下1-2分钟,便放在试样箱上用铁锤敲击;d.敲击后试样允许恢复到室温再与标准样片对照,但要等到冷凝水挥发后;e.将试样认真与标准样片比较,就可以判断出敲击实验的等级。
实施例1
在玻璃基板2.0C(基板1)上依次镀上厚度为32nm的ZnSnO2膜层;厚度为10nm的ZnO2膜层作为底层电介质膜层2;厚度为12nm的银膜层3;厚度为3nm的Ti膜层(牺牲膜层4);厚度为0.05nm的AgLa膜层5,其中La的含量为50at%;厚度为23nm的ZnSnO2膜层(电介质膜层6);厚度为17nm的Si3N4膜层作为保护膜层7,得到可热处理镀膜玻璃,即薄膜器件,结构如图1所示。
光学性能测试:
在热处理之前,单片镀膜玻璃的可见光透过率81.5%;580℃热处理10min后检测,单片镀膜玻璃的可见光透过率为83.8%,方块电阻为5.0Ω/□;然后洗涤、合片等工序后获得的镀膜夹层玻璃,经检测,其可见光透过率为77.6%。
物理性能:
按照GB9656-2003,冲击实验、耐辐照实验、湿热循环实验等均能满足要求。经检测,敲击实验等级为4级,说明膜层与玻璃和PVB的附着力都很好。
实施例2
在玻璃基板2.0C(基板1)上依次镀上厚度为28nm的ZnSnO2膜层;厚度为15nm的ZnO2膜层作为底层电介质膜层2;厚度为12nm的银膜层3;厚度为2nm的Ti膜层(牺牲膜层4);厚度为0.5nm的AgLa膜层5,其中La的含量为20at%;厚度为30nm的ZnSnO2膜层(电介质膜层6);厚度为12nm的Si3N4膜层作为保护膜层7,得到可热处理镀膜玻璃,即薄膜器件,结构如图1所示。
光学性能测试:
在热处理之前,单片镀膜玻璃的可见光透过率81.9%;580℃热处理10min后检测,单片镀膜玻璃的可见光透过率为84.1%,方块电阻为4.9Ω/□;然后洗涤、合片等工序后获得的镀膜夹层玻璃,经检测,其可见光透过率为77.9%。
物理性能:
按照GB9656-2003,冲击实验、耐辐照实验、湿热循环实验等均能满足要求。经检测,敲击实验等级为4级,说明膜层与玻璃和PVB的附着力都很好。
实施例3
在玻璃基板2.0C(基板)上依次镀上厚度为30nm的ZnSnO2膜层;厚度为13nm的ZnO2膜层作为底层电介质膜层;厚度为1.5nm的AgLa膜层,其中La的含量为10at%;厚度为11nm的银膜层;厚度为3nm的Ti膜层(牺牲膜层);厚度为28nm的ZnSnO2膜层(电介质膜层);厚度为15nm的Si3N4膜层作为保护膜层,得到可热处理镀膜玻璃,即薄膜器件。
光学性能测试:
在热处理之前,单片镀膜玻璃的可见光透过率82.1%;580℃热处理10min后检测,单片镀膜玻璃的可见光透过率为84.5%,方块电阻为5.1Ω/□;然后洗涤、合片等工序后获得的镀膜夹层玻璃,经检测,其可见光透过率为78.1%。
物理性能:
按照GB9656-2003,冲击实验、耐辐照实验、湿热循环实验等均能满足要求。经检测,敲击实验等级为4级,说明膜层与玻璃和PVB的附着力都很好。
实施例4
在玻璃基板2.0C(基板)上依次镀上厚度为35nm的ZnSnO1.8膜层(底层电介质膜层);厚度为1nm的AgLa膜层,其中La的含量为10at%;厚度为8nm的银膜层;厚度为0.1nm的NiTi膜层(牺牲膜层);厚度为10nm的AgLa膜层,其中La的含量为10at%;厚度为77nm的ZnSnO1.8膜层(电介质膜层);厚度为11nm的银膜层;厚度为3nm的NiTi膜层(牺牲膜层);厚度为2nm的AgLa膜层,其中La的含量为30at%;厚度为28nm的ZnSnO1.8膜层(电介质膜层);厚度为8nm的TiO2膜层作为保护膜层,得到可热处理镀膜玻璃,即薄膜器件。
光学性能测试:
在热处理之前,单片镀膜玻璃的可见光透过率79.2%;585℃热处理10min后检测,单片镀膜玻璃可见光透过率为81.3%,方块电阻为3.2Ω/□;然后洗涤、合片等工序后获得的镀膜夹层玻璃,经检测,其可见光透过率为75.9%。
物理性能:
按照GB9656-2003,冲击实验、耐辐照实验、湿热循环实验等均能满足要求。经检测,敲击实验等级为4级,说明膜层与玻璃和PVB的附着力都很好。
实施例5
在玻璃基板2.0C(基板1)上依次镀上厚度为15nm的Si3N4膜层;厚度为18nm的ZnSnO2.3膜层作为底层电介质膜层2;厚度为12nm的银膜层(第一银膜层3);厚度为2nm的TiMo膜层(第一牺牲膜层4);厚度为1nm的AgLa膜层(第一AgLa膜层5),其中La的含量为20at%;厚度为73nm的ZnSnO2.3膜层(第一电介质膜层6);厚度为10nm的银膜层(第二银膜层31);厚度为1nm的NiCr膜层(第二牺牲膜层41);厚度为1nm的AgLa膜层(第二AgLa膜层51),其中La的含量为20at%;厚度为68nm的ZnSnO2.3膜层(第二电介质膜层61);厚度为9nm的银膜层(第三银膜层32);厚度为8nm的NiTi膜层(第三牺牲膜层42);厚度为0.05nm的AgLa膜层(第三AgLa膜层52),其中La的含量为50at%;厚度为20nm的AlZnO2膜层(第三电介质膜层62);厚度为15nm的ZrO2膜层作为保护膜层7,得到可热处理镀膜玻璃,即薄膜器件,结构如图3所示。
光学性能测试:
在热处理之前,单片镀膜玻璃的可见光透过率77.7%;590℃热处理10min后检测,单片镀膜玻璃可见光透过率为79.7%,方块电阻为2.3Ω/□;然后洗涤、合片等工序后获得的镀膜夹层玻璃,经检测,其可见光透过率为71.5%。
物理性能:
按照GB9656-2003,冲击实验、耐辐照实验、湿热循环实验等均能满足要求。经检测,敲击实验等级为3级,说明膜层与玻璃和PVB的附着力都很好。
实施例6
在玻璃基板2.0C(基板1)上依次镀上厚度为10nm的CdS膜层;厚度为15nm的Si3N4膜层;厚度为8nm的ZnO膜层作为底层电介质膜层2;厚度为12nm的银膜层(第一银膜层3);厚度为2nm的TiMo膜层(第一牺牲膜层4);厚度为2nm的AgLa膜层(第一AgLa膜层5),其中La的含量为10at%;厚度为65nm的ZnSnO2.3膜层;厚度为8nm的ZnO膜层作为第一电介质膜层6;厚度为10nm的银膜层(第二银膜层31);厚度为2nm的NiCr膜层(第二牺牲膜层41);厚度为1nm的AgLa膜层(第二AgLa膜层51),其中La的含量为20at%;厚度为68nm的ZnSnO2.3膜层(第二电介质膜层61);厚度为8nm的银膜层(第三银膜层32);厚度为3nm的NiTi膜层(第三牺牲膜层42);厚度为0.1nm的AgLa膜层(第三AgLa膜层52),其中La的含量为20at%;厚度为70nm的AlZnO2膜层;厚度为8nm的ZnO膜层作为第三电介质膜层62;厚度为6nm的银膜层(第四银膜层33);厚度为2nm的NiCr膜层(第四牺牲膜层43);厚度为2nm的AgLa膜层(第四AgLa膜层53),其中La的含量为50at%;厚度为25nm的AlZnO2膜层(第四电介质膜层63);厚度为15nm的ZrO2膜层作为保护膜层7,得到可热处理镀膜玻璃,即薄膜器件,结构如图4所示。
光学性能测试:
在热处理之前,单片镀膜玻璃的可见光透过率74.3%;590℃热处理10min后检测,单片镀膜玻璃可见光透过率为75.4%,方块电阻为1.0Ω/□;然后洗涤、合片等工序后获得的镀膜夹层玻璃,经检测,其可见光透过率为68.3%。
物理性能:
按照GB9656-2003,冲击实验、耐辐照实验、湿热循环实验等均能满足要求。经检测,敲击实验等级为3级,说明膜层与玻璃和PVB的附着力都很好。
实施例7
在玻璃基板2.0C上依次镀上厚度为35nm的ZnSnO1.8膜层;厚度为8nm的银膜层;厚度为0.1nm的NiTi膜层;厚度为77nm的ZnSnO1.8膜层;厚度为11nm的银膜层;厚度为3nm的NiTi膜层;厚度为28nm的ZnSnO1.8膜层;厚度为8nm的TiO2膜层作为保护膜层,得到可热处理镀膜玻璃,即薄膜器件。
光学性能测试:
在热处理之前,单片镀膜玻璃的可见光透过率77.9%;585℃热处理10min后检测,单片镀膜玻璃的可见光透过率为79.8%,方块电阻为4.6Ω/□;然后洗涤、合片等工序后获得的镀膜夹层玻璃,经检测,其可见光透过率为73.3%。
物理性能:
按照GB9656-2003,冲击实验、耐辐照实验、湿热循环实验等均能满足要求。经检测,敲击实验等级为3级,说明膜层与玻璃和PVB的附着力都很好。
实施例8
将实施例4制得的镀膜玻璃进行高温热处理,使其在620℃的加热炉内停留14min,然后测试单片镀膜玻璃的方块电阻为5.8Ω/□。
将该单片膜玻璃通过合片等工序后获得的镀膜夹层玻璃按照GB9656-2003,冲击实验、耐辐照实验、湿热循环实验等均能满足要求。经检测,敲击实验等级为3级,说明膜层与玻璃和PVB的附着力都很好。
实施例9
将实施例7制得的镀膜玻璃进行高温热处理,使其在620℃的加热炉内停留14min,然后测试单片镀膜玻璃的方块电阻为22.1Ω/□。
将该单片镀膜玻璃通过合片等工序后获得的镀膜夹层玻璃按照GB9656-2003,冲击实验、耐辐照实验、湿热循环实验等均不能满足要求。经检测,敲击实验等级为2级,说明膜层与玻璃和PVB的附着力变差。
实施例8与实施例9的比较可以看出:实施例8的方块电阻与实施例4的方块电阻相差不大,而实施例9的方块电阻比实施例7的方块电阻增大了很多,说明经过实施例9的高温热处理后其银膜层受到一定程度的破坏;从另一方面讲,采用在所述牺牲层之上形成AgLa膜层,所述AgLa膜层中La的含量≤50at%;或在所述银膜层之下形成AgLa膜层,所述AgLa膜层中La的含量≤50at%;或在所述牺牲层之上形成AgLa膜层,同时在所述银膜层之下形成AgLa膜层,所述AgLa膜层中La的含量≤50at%;可以提高整个膜系结构的耐高温性能、耐机械性能和化学稳定性。
本发明的薄膜器件可以用于制作成夹层薄膜器件或中空薄膜器件。
尽管结合优选实施方案具体展示和介绍了本发明,但所属领域的技术人员应该明白,在不脱离所附权利要求书所限定的本发明的精神和范围内,在形式上和细节上可以对本发明做出各种变化,均为本发明的保护范围。
Claims (10)
1.一种薄膜器件,包括依次向上层叠的基板、底层电介质膜层、膜层组件和保护膜层,所述膜层组件包括沿基板向上依次层叠的银膜层、牺牲膜层和电介质膜层,或所述膜层组件包括沿基板向上依次层叠的牺牲膜层、银膜层和电介质膜层,其特征在于:所述膜层组件还包括AgLa膜层,所述AgLa膜层层叠在牺牲膜层与电介质膜层之间;或所述AgLa膜层层叠在银膜层下面;或所述AgLa膜层层叠在牺牲膜层与电介质膜层之间,同时所述AgLa膜层还层叠在银膜层下面;其中,所述AgLa膜层中La的含量≤50at%。
2.根据权利要求1所述的薄膜器件,其特征在于:所述AgLa膜层的厚度为0.05-10nm。
3.根据权利要求1所述的薄膜器件,其特征在于:所述AgLa膜层中La的含量≤30at%。
4.根据权利要求3所述的薄膜器件,其特征在于:所述AgLa膜层中La的含量≤20at%。
5.根据权利要求1所述的薄膜器件,其特征在于:所述牺牲膜层的材料为NiCr、Ti、NiCrOx、Cr、NiCrMo、CrOx、MoOx、TiMo、TiMoOx、NiTi、TiOx和NiTiOx中的任意一种或它们的任一组合。
6.根据权利要求1所述的薄膜器件,其特征在于:所述牺牲膜层的厚度为0.1-8nm。
7.根据权利要求1-6任意一项所述的薄膜器件,其特征在于:所述膜层组件的数量为两个,两个膜层组件依次层叠设置。
8.根据权利要求1-6任意一项所述的薄膜器件,其特征在于:所述膜层组件的数量为三个,三个膜层组件依次层叠设置。
9.根据权利要求1-6任意一项所述的薄膜器件,其特征在于:所述膜层组件的数量为四个,四个膜层组件依次层叠设置。
10.根据权利要求1-6任意一项所述的薄膜器件,其特征在于:该薄膜器件用于制作成夹层薄膜器件或中空薄膜器件。
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