CN105189383B - 透明漫射性oled基材及制造此基材的方法 - Google Patents

透明漫射性oled基材及制造此基材的方法 Download PDF

Info

Publication number
CN105189383B
CN105189383B CN201480028425.1A CN201480028425A CN105189383B CN 105189383 B CN105189383 B CN 105189383B CN 201480028425 A CN201480028425 A CN 201480028425A CN 105189383 B CN105189383 B CN 105189383B
Authority
CN
China
Prior art keywords
refractive index
mineral
base material
layer
grain
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201480028425.1A
Other languages
English (en)
Other versions
CN105189383A (zh
Inventor
G.勒康
V.索维内
N.舍曼
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Saint Gobain Glass France SAS
Original Assignee
Saint Gobain Glass France SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Saint Gobain Glass France SAS filed Critical Saint Gobain Glass France SAS
Publication of CN105189383A publication Critical patent/CN105189383A/zh
Application granted granted Critical
Publication of CN105189383B publication Critical patent/CN105189383B/zh
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/062Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064Glass compositions containing silica with less than 40% silica by weight containing boron
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10Substrates, e.g. flexible substrates
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/001General methods for coating; Devices therefor
    • C03C17/002General methods for coating; Devices therefor for flat glass, e.g. float glass
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/007Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/008Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/008Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
    • C03C17/009Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/02Surface treatment of glass, not in the form of fibres or filaments, by coating with glass
    • C03C17/04Surface treatment of glass, not in the form of fibres or filaments, by coating with glass by fritting glass powder
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411Surface 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
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411Surface 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
    • C03C17/3417Surface 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
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C8/00Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02Frit compositions, i.e. in a powdered or comminuted form
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11Anti-reflection coatings
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/02Diffusing elements; Afocal elements
    • G02B5/0205Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/021Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
    • G02B5/0221Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures the surface having an irregular structure
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/02Diffusing elements; Afocal elements
    • G02B5/0205Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/021Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
    • G02B5/0226Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures having particles on the surface
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/02Diffusing elements; Afocal elements
    • G02B5/0205Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/0236Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element
    • G02B5/0242Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element by means of dispersed particles
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/80Constructional details
    • H10K50/85Arrangements for extracting light from the devices
    • H10K50/854Arrangements for extracting light from the devices comprising scattering means
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C2217/00Coatings on glass
    • C03C2217/40Coatings comprising at least one inhomogeneous layer
    • C03C2217/43Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/46Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C2217/00Coatings on glass
    • C03C2217/40Coatings comprising at least one inhomogeneous layer
    • C03C2217/43Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/46Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
    • C03C2217/47Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
    • C03C2217/475Inorganic materials
    • C03C2217/478Silica
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C2217/00Coatings on glass
    • C03C2217/70Properties of coatings
    • C03C2217/73Anti-reflective coatings with specific characteristics
    • C03C2217/734Anti-reflective coatings with specific characteristics comprising an alternation of high and low refractive indexes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/549Organic PV cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Glass (AREA)
  • Glass Compositions (AREA)
  • Optical Elements Other Than Lenses (AREA)

Abstract

本发明涉及透明漫射性OLED基材,其包含下列连续的层:(a)由具有介于1.45和1.65之间的折射率的矿物玻璃制成的透明平坦基材(1),(b)包含矿物颗粒的粗糙的低折射率层,所述矿物颗粒通过溶胶‑凝胶矿物粘合剂连接到所述基材的一侧,在所述矿物粘合剂的表面附近、所述矿物粘合剂的表面处或自所述矿物粘合剂的表面突出的矿物颗粒产生以介于0.15和3µm之间的算术平均偏差Ra为特征的表面粗糙度,所述矿物颗粒和矿物粘合剂两者都具有介于1.45和1.65之间的折射率;(c)由具有介于1.8和2.1之间的折射率的搪瓷制成的覆盖所述粗糙的低折射率层的高折射率层;并且涉及制造此漫射性OLED基材的方法。

Description

透明漫射性OLED基材及制造此基材的方法
技术领域
本发明涉及制造用于有机发光二极管(OLED)的半透明光散射基材的新方法和由这样的方法可获得的基材。
背景技术
OLED是包含夹在两个电极之间的具有荧光或磷光染料的有机层堆的光电元件,至少一个电极是半透明的。当将电压施加到所述电极时,自阴极注入的电子和自阳极注入的空穴在有机层内重新结合,导致从所述荧光/磷光层发光。
众所周知,从常规的OLED的光提取性比较差,大部分光通过高折射率(highindex)有机层和透明导电层(TCL)中的全内反射被捕获。全内反射不仅发生在高折射率TCL与下层的玻璃基材(约1.5的折射率)之间的边界处,而且还发生在玻璃与空气之间的边界处。
据估计,在不包含任何另外的提取层的常规OLED中,自有机层发出的光的约60%的光被捕获在TCL/玻璃边界处,另外20%的份额被捕获在玻璃/空气表面处,并且仅约20 %离开OLED进入空气中。
已知借由TCL与玻璃基材之间的光散射层来减少这种光捕获(entrapment)。这样的光散射层具有接近于TCL折射率的高折射率且包含多个光漫射元件。
还已知通过使玻璃与OLED的高折射率层之间的界面形成纹理来增加光的出耦合(out-coupling)。
这些“内部”提取手段、通常也称为“内部提取层”(IEL)都包含在施加TCL和有机堆(organic stack)之前需要被平坦化的凹凸不平处。
WO2011/089343公开了包含至少一种用高折射率玻璃涂层平坦化的具有纹理的表面的OLED基材。所述基材被描述为通过酸蚀刻来形成纹理。使用强酸(特别是HF)的玻璃蚀刻是常用于使玻璃表面形成纹理的方法。然而,当在薄玻璃(厚度<1毫米)上进行时,这样的湿化学法是复杂的工艺。这种技术仅允许每个工艺步骤蚀刻两个面中的一面,因为玻璃板在蚀刻步骤期间必须保持在水平位置。此外,难以使粗糙度轮廓参数最优化,且尤其是HF的使用对环境和附近工作人员产生严重的安全问题。
本申请人最近已开发出用于使玻璃基材的一面或两面粗糙化的替代方法,所述方法包括机械粗糙化(研磨(lapping))。在2012年9月28日提交的欧洲申请12306179.8中描述的这种方法比化学蚀刻的危害性低得多,允许更好地控制粗糙度轮廓,且可以同时使所述基材的两面粗糙化,由此在单一工艺步骤中制造透明OLED玻璃基材的内部提取层和外部提取层(IEL和EEL)。
本发明涉及又一用于制造漫射性(diffusive)低折射率玻璃基材的方法,所述方法既不包括化学蚀刻步骤,也不包括机械磨损步骤。构成本发明基础的概念是通过低折射率矿物粘合剂将低折射率矿物颗粒粘合至低折射率玻璃基材,矿物粘合剂相对于矿物颗粒的量低至足以使所述矿物颗粒自所述粘合剂表面突出或至少在所述矿物粘合剂表面处产生显著的粗糙度。
然后对所得的漫射性低折射率基材施以众所周知的使用高折射率熔料(frit)的平坦化步骤,且随后可以用透明导电层(TCL)涂布所得到的平坦化漫射性基材,并将其用作OLED的光提取基材。
本发明的方法是容易实现的,只需要比较简单且公知的设备。一个超越EP12306179.8中所述的研磨方法的显著优点在于它可用于非常大的表面。由于它不会削弱所述基材的机械强度(对于大表面积蚀刻或研磨的玻璃基材可以观察到的不便之处),所有其是进一步有利的。
发明内容
本发明的第一主题是透明漫射性OLED基材,其包含下列连续的元件或层:
(a) 由具有介于1.45和1.65之间的折射率的矿物玻璃制成的透明平坦基材,
(b) 包含矿物颗粒的粗糙的低折射率层,所述矿物颗粒通过溶胶-凝胶矿物粘合剂连接到所述基材的一侧,在所述矿物粘合剂的表面附近、所述矿物粘合剂的表面处或自所述矿物粘合剂的表面突出的矿物颗粒产生以介于0.15和3 µm之间的算术平均偏差Ra为特征的表面粗糙度,所述矿物颗粒和矿物粘合剂两者都具有介于1.45和1.65之间的折射率;
(c) 由具有介于1.8和2.1之间的折射率的搪瓷制成的覆盖所述粗糙的低折射率层(b)的高折射率层。
本发明还提供了用于制备如上定义的漫射性基材的方法。
所述术语“溶胶-凝胶矿物粘合剂”是指通过溶胶-凝胶法由小的前体(通常为金属烷氧化物)获得的矿物固体。此方法涉及将所述前体(例如金属四烷氧化物)转化为胶态溶液(溶胶),所述胶态溶液逐步形成整合的聚合物网络(凝胶),接着将其干燥并进一步通过烧制压实。
本发明的OLED基材的低折射率层由其折射率(1.45-1.65)及其表面粗糙度轮廓(即介于0.15和3 µm之间的算术平均偏差Ra(如在ISO 4287中所定义的那样))来限定。
所述粗糙度由所述矿物结合剂的表面附近、所述矿物结合剂的表面处或自所述矿物结合剂的表面突出的矿物颗粒造成。所述矿物颗粒不一定需要自所述矿物结合剂突出,但可以被嵌入到所述矿物结合剂层中,只要例如从截面SEM视图中明显看出,粗糙度或波纹度可以归因于下层的颗粒,表面轮廓密切地匹配所嵌入的矿物颗粒的存在/不存在。
本发明中使用的矿物颗粒可以是结晶的、非晶的或半结晶的颗粒。它们可以具有或多或少带有锐利边缘的任意形状,但优选没有锐利边缘的有点球状的颗粒。
在一个优选的实施方案中,所述矿物颗粒是固体珠粒。这样的珠粒相对于呈任意形状的带有锐利边缘的颗粒而言是优选的,原因是这样的珠粒容易地铺展在基材表面上,由此促进形成薄的单层珠粒,而不是大尺寸化的聚集体。没有锋利边缘的球状颗粒也比呈任意形状的颗粒更容易平坦化。要理解的是空心珠粒不包括在本发明的矿物颗粒的定义中,因为包含在其中的气体不具有介于1.45和1.65之间的折射率。
术语“矿物颗粒”(尤其是当用于描述本发明的方法时)包含采用有机表面基团(如三烷基甲硅烷基)官能化的颗粒。所述有机表面基团在溶胶-凝胶矿物粘合剂的烧制步骤过程中、或者在形成高折射率搪瓷层的过程中发生热分解。
本发明中使用的矿物颗粒(无论是否为球形)具有介于0.3 µm和10 µm之间、优选介于0.5 µm和8 µm之间、更优选介于0.8 µm和7 µm之间的平均等效球体直径(通过DLS测得),呈不规则形状的颗粒的等效球体直径定义为具有与该矿物颗粒相同的体积的球体的直径。
然而,平均等效球体直径不是唯一用于考虑选择在本发明中使用的矿物颗粒的尺寸参数。有利地,所述矿物颗粒基本不含大尺寸的颗粒,所述大尺寸的颗粒不仅从所述矿物粘合剂突出,还从所述高折射率搪瓷层突出,继而导致最终OLED中的电流泄漏。本发明中使用的矿物颗粒因此基本不含具有大于15 µm、优选大于12 µm的等效球体直径的颗粒。
如上文已经指出的,所述玻璃基材、所述矿物颗粒和所述矿物粘合剂全部都具有介于1.45和1.65之间、优选介于1.50和1.60之间的大致相同的折射率。
在本发明的一个优选实施方案中,所述矿物颗粒选自二氧化硅颗粒。
为了由全部都具有大致相同的折射率的成分获得漫射性基材,有必要产生和控制所述低折射率矿物层的表面粗糙度。如上所提及的,所述低折射率矿物层应具有介于0.15和3 µm之间、优选介于0.2和2 µm之间的算术平均偏差Ra
在ISO 4287中定义了算术平均偏差Ra。其可以通过样品的横截面的扫描电子显微法(SEM)、通过表面轮廓测量或通过3D激光显微法进行测量。
为了获得既具有合适的表面粗糙度又具有令人满意的机械抗性的矿物层,适当地选择相对于所述矿物颗粒的量的矿物粘合剂的量是重要的。若使用过高量的矿物粘合剂,则所述矿物颗粒将被完全嵌入所得的低折射率矿物粘合剂基质中且不会产生介于0.15和3µm之间的所需表面粗糙度(Ra)。另一方面,如果相对于矿物颗粒的矿物粘合剂的量太低,则矿物粘合剂的粘合强度太弱,且所得的矿物层在处理时将是过于易碎和容易损坏的。
本申请人发现介于0.2和4之间、优选介于0.4和3之间的矿物颗粒对所述溶胶的干物质的重量比产生合适的低折射率层的表面粗糙度和机械抗性。表述“溶胶的干物质”是指由所述溶胶获得的冷凝的三维矿物网络的干重。
最终的低折射率矿物层也可以以优选介于0.3和3之间、优选介于0.5和2之间、和更优选介于0.7和1.5之间的所述矿物颗粒对所述矿物结合剂的体积比为特征。
在所述低折射率矿物层(b)上的高折射率搪瓷(c)应该厚至足以完全覆盖和平坦化其粗糙度轮廓。
所述高折射率层的厚度有利地介于3 µm至20 µm之间,优选介于4 µm和15 µm之间,更优选介于5 µm和12 µm之间。所述高折射率层的厚度是所述低折射率层的粗糙度轮廓与所述高折射率层的粗糙度轮廓的中间线之间的平均距离(如在ISO 4287,3.1.8.1中所定义的那样)。
所述高折射率层的表面粗糙度应优选尽可能地低,且所述高折射率搪瓷有利地具有小于3 nm、更优选小于2 nm、和最优选小于1 nm的算术平均偏差Ra
所述高折射率层优选基本不含分散在其中的漫射性元件,尤其不含分散在其中的漫射性固体颗粒。事实上,这样的漫射性固体颗粒可能不期望地从所述高折射率层的表面突出,并导致最终OLED中的电流泄漏。
带有由所述高折射率玻璃熔料平坦化的低折射率矿物层(低折射率颗粒+溶胶-凝胶粘合剂)的所得平坦玻璃基材通常具有介于75和98%之间、优选85和97%之间、和更优选87和95%之间的雾度。雾度值可以通过诸如PE Lambda 950或Varian Carry 5000的光学分光光度计来测量,但也可以通过诸如BYK雾度计的更快和更便宜的专用设备来测量。
在一个优选的实施方案中,本发明的透明漫射性OLED基材还包含优选与所述高折射率搪瓷层(c)直接接触的透明导电层(d)。可用作OLED的阳极的这样的透明导电层是本领域中熟知的。最常用的材料是ITO(氧化铟锡)。透明导电层应当具有至少80%的透光率和介于1.8和2.2之间的折射率。其总厚度通常介于50和400 nm之间。
如上文所提到的,本发明还涉及用于制备本发明的OLED基材的方法。
所述方法包括以下连续的步骤:
(1) 提供由具有介于1.45和1.65之间的折射率的矿物玻璃制成的透明平坦基材;
(2) 将具有介于1.45和1.65之间的折射率的矿物颗粒分散在具有介于1.45和1.65之间的折射率的矿物粘合剂的至少一种前体的溶胶中;
(3) 将所得的分散体施加到所述基材的一侧上;
(4) 通过加热来干燥和烧制所得层,以获得包含矿物颗粒和矿物粘合剂的透明粗糙的低折射率层;
(5) 将具有介于1.8和2.1之间的折射率的高折射率玻璃熔料层施加到所述粗糙的低折射率层上;
(6) 干燥和熔化所述玻璃熔料,以获得覆盖所述粗糙的低折射率层的具有介于1.8和2.1之间的折射率的高折射率搪瓷层。
在步骤(1)提供的平坦玻璃基材通常具有介于0.1和5 mm之间、优选介于0.3和1.6mm之间的厚度。
在步骤(2),将之前所述的矿物颗粒分散在矿物粘合剂的至少一种前体的溶胶中。所述前体优选选自硅酸钠、硅酸钾、硅酸锂、四烷氧基硅烷、优选四乙氧基硅烷、烷氧化钛、烷氧化铝、烷氧化锆或其混合物。烷氧化锆和烷氧化钛以足够低以至不超过最终矿物粘合剂的最大折射率(1.65)的量用于与其它前体的混合物中。
然后将所得的浆料以已知的方法施加到所述平坦基材的一面上,例如通过浸涂、辊涂、旋涂、狭缝涂布。
然后将溶胶相的溶剂蒸发且对经干燥的层施以烧制步骤。在步骤(4)中的干燥和烧制有利地通过在至少100℃、优选100℃至300℃、更优选110℃至200℃的温度下加热来进行。当所使用的矿物颗粒为带有有机表面基团(例如烷基甲硅烷基基团)的经有机改性的颗粒时,烘焙应在足够高以实现这些表面基团的热分解的温度下进行。
在步骤(5),然后将所述高折射率玻璃熔料通过任何合适的方法(例如玻璃颗粒的水性或有机悬浮液的丝网印刷、喷涂、棒涂、辊涂、狭缝涂布和旋涂)施加到所述烘焙的低折射率粗糙层上。合适的高折射率玻璃熔料和用于涂布和烧制所述熔料的方法的说明可见于例如EP 2 178 343中。
应选择所述玻璃熔料以具有介于450℃和570℃之间的熔点且应产生具有1.8-2.2的折射率的搪瓷。
优选的玻璃熔料具有下列组成:
Bi2O3:55-75 wt%
BaO:0-20 wt%
ZnO:0-20 wt%
Al2O3:1-7 wt%
SiO2:5-15 wt%
B2O3:5-20 wt%
Na2O:0.1-1 wt%
CeO2:0-0.1 wt%
在典型的实施方案中,将所述玻璃熔料颗粒(70-80 wt%)与20-30 wt%的有机载体(乙基纤维素和有机溶剂)混合。然后将所得的熔料糊状物通过丝网印刷或狭缝涂布施加到漫射性的经涂布的玻璃基材上。通过在120-200℃的温度下加热来干燥所得层。将所述有机粘合剂(乙基纤维素)在介于350-440℃之间的温度下烧尽,且产生最终搪瓷的烧制步骤在介于510°C和610℃之间、优选介于520℃和600℃之间的温度下进行。
当通过AFM在10 µm×10 µm的面积上测量时,所得搪瓷已经显示出具有小于3 nm的算术平均偏差Ra (ISO 4287)的表面粗糙度。
涂布在粗糙化的表面上的所述高折射率玻璃熔料的量通常介于20和200 g/m2之间、优选介于25和150 g/m2之间、更优选介于30和100 g/m2之间、和最优选介于35和70 g/m2之间。
在本发明中使用的高折射率玻璃熔料和由其生成的搪瓷优选基本不含固体散射颗粒(诸如结晶的SiO2或TiO2颗粒)。这样的颗粒通常用作高折射率散射层中的散射元件,但通常需要额外的平坦化层,从而增加所述高折射率涂层的总厚度。
采用高折射率搪瓷平坦化的漫射性基材作为底部发光型OLED的基材是特别有用的。在施加所述有机发光层堆之前,必须先将透明导电层施加到所述高折射率搪瓷的顶部上。
在一个优选的实施方案中,本发明的方法因此还包括采用透明导电层(优选透明导电氧化物)涂布由步骤(6)所生成的高折射率搪瓷的额外步骤。这样的TCL的形成可以按照诸如磁控溅射的常规方法进行。
实施例
将20 g的具有2.5 µm的平均直径的经有机改性的二氧化硅珠粒分散在150 g的2-甲氧基-丙醇中并通过超声分散。向该分散体中加入30 g的Xenios® Surface Perfection(Evonik GmbH)。然后将所得分散体通过浸涂施加到干净的玻璃基材上并在120℃下干燥约1分钟。然后将经干燥、涂布的基材以5℃/分钟的速率加热至500℃的温度并在此温度下烧制5分钟。
图1和图2示出了粗糙的低折射率层在烧制之后和采用高折射率熔料平坦化之前的SEM显微照片。可以看到球体颗粒以非常紧密堆积的单层形式铺设在所述玻璃基材上。
然后采用高折射率熔料(n=1.90)的浆料通过丝网印刷涂布所得的低折射率粗糙层。将所述涂层在150℃下干燥并在IR炉中于545℃下烧制10分钟。

Claims (15)

1.透明漫射性OLED基材,其包含下列连续的元件或层:
(a) 由具有介于1.45和1.65之间的折射率的矿物玻璃制成的透明平坦基材,
(b) 包含矿物颗粒的粗糙的低折射率层,所述矿物颗粒通过溶胶-凝胶矿物粘合剂连接到所述基材的一侧,在所述矿物粘合剂的表面附近、所述矿物粘合剂的表面处或自所述矿物粘合剂的表面突出的矿物颗粒产生以介于0.15和3 µm之间的算术平均偏差Ra为特征的表面粗糙度,所述矿物颗粒和矿物粘合剂两者都具有介于1.50和1.60之间的折射率;
(c) 由具有介于1.8和2.1之间的折射率的搪瓷制成的覆盖所述粗糙的低折射率层的高折射率层,其中所述高折射率层的厚度介于3 µm和20 µm之间。
2.根据权利要求1的基材,其中所述矿物颗粒具有介于0.3 µm和10 µm之间的平均等效球体直径。
3.根据权利要求1或2的基材,其中所述矿物颗粒是固体珠粒。
4.根据权利要求1的基材,其中所述矿物颗粒不含具有大于15 µm的等效球体直径的颗粒。
5.根据权利要求1的基材,其中所述基材、矿物粘合剂和矿物颗粒的折射率介于1.50和1.60之间。
6.根据权利要求1的基材,其中所述高折射率层的厚度介于4 µm和15 µm之间。
7.根据权利要求1的基材,其中所述高折射率层的表面粗糙度具有小于3 nm的算术平均偏差Ra
8.根据权利要求1的基材,其中所述高折射率层不含分散在其中的漫射性固体颗粒。
9.根据权利要求1的基材,其中所述矿物颗粒选自二氧化硅颗粒。
10.根据权利要求1的基材,其还包含所述高折射率层上的透明导电层。
11.根据权利要求1的基材,其中所述矿物颗粒对所述矿物粘合剂的体积比介于0.3和3之间。
12.用于制备根据前述权利要求任一项的透明漫射性基材的方法,所述方法包括以下连续步骤:
(1) 提供由具有介于1.45和1.65之间的折射率的矿物玻璃制成的透明平坦基材;
(2) 将具有介于1.50和1.60之间的折射率的矿物颗粒分散在具有介于1.50和1.60之间的折射率的矿物粘合剂的至少一种前体的溶胶中;
(3) 将所得的分散体施加到所述基材的一侧上;
(4) 通过加热来干燥和烧制所得层,以获得包含矿物颗粒和矿物粘合剂的透明粗糙的低折射率层;
(5) 将具有介于1.8和2.1之间折射率的高折射率玻璃熔料的层施加到所述粗糙的低折射率层上;
(6) 干燥和熔化所述高折射率玻璃熔料,以获得覆盖所述粗糙的低折射率层的具有介于1.8和2.1之间的折射率的高折射率层。
13.根据权利要求12的方法,其中所述矿物粘合剂的至少一种前体选自:硅酸钠、硅酸钾或硅酸锂、四烷氧基硅烷、烷氧化钛、烷氧化铝、烷氧化锆。
14.根据权利要求12的方法,其中在步骤(4)中的干燥和烧制通过在至少100℃的温度下加热来进行。
15.根据权利要求12的方法,其中所述矿物颗粒具有介于0.3 µm和10 µm之间的平均等效球体直径。
CN201480028425.1A 2013-05-17 2014-04-29 透明漫射性oled基材及制造此基材的方法 Expired - Fee Related CN105189383B (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP13168341.9 2013-05-17
EP13168341.9A EP2803644B1 (en) 2013-05-17 2013-05-17 Transparent diffusive oled substrate and method for producing such a substrate
PCT/EP2014/058738 WO2014183993A1 (en) 2013-05-17 2014-04-29 Transparent diffusive oled substrate and method for producing such a substrate

Publications (2)

Publication Number Publication Date
CN105189383A CN105189383A (zh) 2015-12-23
CN105189383B true CN105189383B (zh) 2018-08-10

Family

ID=48482931

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201480028425.1A Expired - Fee Related CN105189383B (zh) 2013-05-17 2014-04-29 透明漫射性oled基材及制造此基材的方法

Country Status (10)

Country Link
US (1) US10147894B2 (zh)
EP (2) EP2803644B1 (zh)
JP (1) JP6495894B2 (zh)
KR (1) KR102142437B1 (zh)
CN (1) CN105189383B (zh)
ES (1) ES2695052T3 (zh)
MY (1) MY175975A (zh)
RU (1) RU2656264C2 (zh)
TW (1) TWI622562B (zh)
WO (1) WO2014183993A1 (zh)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2814078B1 (en) 2013-06-14 2016-02-10 Saint-Gobain Glass France Transparent diffusive oled substrate and method for producing such a substrate
CN107533190A (zh) * 2015-03-31 2018-01-02 康宁公司 包含光散射表面的波导以及包含所述波导的显示装置
EP3353583A1 (en) * 2015-09-23 2018-08-01 Corning Incorporated Oled light extraction using nanostructured coatings
US11327205B2 (en) 2019-07-29 2022-05-10 Viavi Solutions Inc. Encapsulated diffuser

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002075373A1 (fr) * 2001-03-21 2002-09-26 Fuji Photo Film Co., Ltd. Couche mince antireflet et dispositif d'affichage d'images
CN1759637A (zh) * 2003-03-12 2006-04-12 三菱化学株式会社 电致发光元件
CN103098223A (zh) * 2010-08-31 2013-05-08 康宁股份有限公司 散射覆材的颗粒掺杂方法

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5674625A (en) * 1993-11-10 1997-10-07 Central Glass Company, Limited Multilayered water-repellent film and method of forming same on glass substrate
US6777871B2 (en) * 2000-03-31 2004-08-17 General Electric Company Organic electroluminescent devices with enhanced light extraction
JP5066814B2 (ja) 2005-03-11 2012-11-07 三菱化学株式会社 エレクトロルミネッセンス素子及び照明装置
EP1860919B1 (en) 2005-03-11 2012-02-15 Mitsubishi Chemical Corporation Electroluminescence element and lighting apparatus
JP5023737B2 (ja) * 2007-02-27 2012-09-12 凸版印刷株式会社 有機エレクトロルミネセンスデバイス
JP5195755B2 (ja) 2007-07-27 2013-05-15 旭硝子株式会社 透光性基板、その製造方法、有機led素子及びその製造方法
KR20100063729A (ko) 2007-08-27 2010-06-11 파나소닉 전공 주식회사 유기 이엘 소자
FR2924274B1 (fr) * 2007-11-22 2012-11-30 Saint Gobain Substrat porteur d'une electrode, dispositif electroluminescent organique l'incorporant, et sa fabrication
EP2278852A4 (en) 2008-03-18 2011-08-03 Asahi Glass Co Ltd ELECTRONIC DEVICE SUBSTRATE, LAYERED BODY FOR ORGANIC ELECTROLUMINESCENT DIODE ELEMENT, MANUFACTURING METHOD THEREOF, ORGANIC ELECTROLUMINESCENT DIODE ELEMENT, AND MANUFACTURING METHOD THEREOF
DE102009036134A1 (de) * 2009-08-05 2011-02-10 Schott Ag Substratglas für Lumineszenzdioden mit einer Streupartikel enthaltenden Schicht und Verfahren zu dessen Herstellung
CA2777649A1 (en) 2009-10-15 2011-04-21 Asahi Glass Company, Limited Organic led element, glass frit for diffusion layer for use in organic led element, and method for production of diffusion layer for use in organic led element
FR2955575B1 (fr) 2010-01-22 2012-02-24 Saint Gobain Substrat verrier revetu d'une couche haut indice sous un revetement electrode et dispositif electroluminescent organique comportant un tel substrat.
KR20130143547A (ko) * 2010-07-16 2013-12-31 에이쥐씨 글래스 유럽 유기발광소자용 반투명 전도성 기재
FR2963705B1 (fr) * 2010-08-06 2012-08-17 Saint Gobain Support a couche diffusante pour dispositif a diode electroluminescente organique, dispositif electroluminescent organique comportant un tel support
US9224983B2 (en) * 2010-12-20 2015-12-29 Samsung Electronics Co., Ltd. Substrate for surface light emitting device and method of manufacturing the substrate, surface light emitting device, lighting apparatus, and backlight including the same
EP2693839A4 (en) * 2011-03-31 2014-11-26 Asahi Glass Co Ltd ORGANIC LED ELEMENT, TRANSLUCENT SUBSTRATE AND METHOD FOR PRODUCING THE LIGHT TRACEABLE SUBSTRATE
JP5956673B2 (ja) * 2012-03-30 2016-07-27 エルジー ディスプレイ カンパニー リミテッド 有機電子素子用基板、有機電子装置、基板の製造方法及び照明
KR101715112B1 (ko) * 2012-06-14 2017-03-10 쌩-고벵 글래스 프랑스 Oled 소자용 적층체, 그 제조방법 및 이를 구비한 oled 소자
EP2712851B1 (en) 2012-09-28 2015-09-09 Saint-Gobain Glass France Method of producing a transparent diffusive oled substrate
EP2803645B1 (en) * 2013-05-17 2018-08-01 Saint-Gobain Glass France Transparent diffusive oled substrate and method for producing such a substrate
EP2814078B1 (en) * 2013-06-14 2016-02-10 Saint-Gobain Glass France Transparent diffusive oled substrate and method for producing such a substrate
KR101642120B1 (ko) * 2014-12-24 2016-07-22 코닝정밀소재 주식회사 유기발광소자용 광추출 기판 제조방법, 유기발광소자용 광추출 기판 및 이를 포함하는 유기발광소자
US10401539B2 (en) * 2016-04-21 2019-09-03 Corning Incorporated Coated articles with light-altering features and methods for the production thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002075373A1 (fr) * 2001-03-21 2002-09-26 Fuji Photo Film Co., Ltd. Couche mince antireflet et dispositif d'affichage d'images
CN1759637A (zh) * 2003-03-12 2006-04-12 三菱化学株式会社 电致发光元件
CN103098223A (zh) * 2010-08-31 2013-05-08 康宁股份有限公司 散射覆材的颗粒掺杂方法

Also Published As

Publication number Publication date
EP2803644B1 (en) 2018-08-08
TW201505988A (zh) 2015-02-16
US10147894B2 (en) 2018-12-04
RU2656264C2 (ru) 2018-06-04
KR20160009029A (ko) 2016-01-25
US20160072083A1 (en) 2016-03-10
JP6495894B2 (ja) 2019-04-03
KR102142437B1 (ko) 2020-08-07
TWI622562B (zh) 2018-05-01
CN105189383A (zh) 2015-12-23
JP2016524788A (ja) 2016-08-18
EP2803644A1 (en) 2014-11-19
RU2015153822A3 (zh) 2018-04-02
ES2695052T3 (es) 2018-12-28
EP2996995A1 (en) 2016-03-23
WO2014183993A1 (en) 2014-11-20
MY175975A (en) 2020-07-19
RU2015153822A (ru) 2017-06-22

Similar Documents

Publication Publication Date Title
CN105189383B (zh) 透明漫射性oled基材及制造此基材的方法
JP6117995B2 (ja) 透明散乱性oled基材及び当該基材の作製方法
CN105189384B (zh) 透明漫射性oled基材及制造这样的基材的方法
CN106488893B (zh) 透明扩散性oled基板和制造这样的基板的方法
TW201630844A (zh) 透明擴散oled基板及製造此基板之方法

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20180810

Termination date: 20210429

CF01 Termination of patent right due to non-payment of annual fee