CN107408572A - 电子元件和显示器 - Google Patents
电子元件和显示器 Download PDFInfo
- Publication number
- CN107408572A CN107408572A CN201680008498.3A CN201680008498A CN107408572A CN 107408572 A CN107408572 A CN 107408572A CN 201680008498 A CN201680008498 A CN 201680008498A CN 107408572 A CN107408572 A CN 107408572A
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- China
- Prior art keywords
- color conversion
- electronic component
- color
- colour filter
- layer
- Prior art date
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Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/30—Devices specially adapted for multicolour light emission
- H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
- C09K11/881—Chalcogenides
- C09K11/883—Chalcogenides with zinc or cadmium
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/206—Filters comprising particles embedded in a solid matrix
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
- H10K59/12—Active-matrix OLED [AMOLED] displays
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/30—Devices specially adapted for multicolour light emission
- H10K59/35—Devices specially adapted for multicolour light emission comprising red-green-blue [RGB] subpixels
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/30—Devices specially adapted for multicolour light emission
- H10K59/35—Devices specially adapted for multicolour light emission comprising red-green-blue [RGB] subpixels
- H10K59/351—Devices specially adapted for multicolour light emission comprising red-green-blue [RGB] subpixels comprising more than three subpixels, e.g. red-green-blue-white [RGBW]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- G—PHYSICS
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- G02B2207/101—Nanooptics
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/015—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on semiconductor elements having potential barriers, e.g. having a PN or PIN junction
- G02F1/017—Structures with periodic or quasi periodic potential variation, e.g. superlattices, quantum wells
- G02F1/01791—Quantum boxes or quantum dots
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/1336—Illuminating devices
- G02F1/133614—Illuminating devices using photoluminescence, e.g. phosphors illuminated by UV or blue light
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2202/00—Materials and properties
- G02F2202/10—Materials and properties semiconductor
- G02F2202/101—Ga×As and alloy
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Abstract
本发明尤其涉及包含纳米粒子的彩色显示器以及滤色体。
Description
本发明尤其涉及包含纳米粒子作为光致发光组分的彩色显示器。
大体上,有两种实现包含有机电致发光器件作为光源的全彩色显示器的图案化方法。
第一方法包括用于红色、绿色和蓝色(RGB发射)各者的有机电致发光层的独立沉积,但这样的显示器的制造是相当复杂的。
第二方法是其中红色、绿色和蓝色像素是横向排列在基板上的红/绿/蓝(RGB)图案,和使用包含产生白光的有机电致发光器件的垂直堆叠(stack),该垂直堆叠是与滤色体结合以产生RGB色彩。用于全彩色显示器的有机电致发光器件的最突出实例为有机发光二极管(OLED),但原则上也可使用其他有机电致发光器件,诸如有机发光电化学电池(OLEC)。发出白光的OLED也称为WOLED,且该第二方法称为WOLED方法。使用具有滤色体的WOLED特别有利于大型基板加工,且归因于无图案OLED沉积而提供优异的生产力。
常用的WOLED结构使用串联设计,其中多个发光单元是垂直堆叠的,这归因于额外方法步骤的要求而提高复杂度。再者,色彩性能通常逊于RGB发射法。使用具有窄带宽的滤色体允许改善色彩性能,然而也造成光效率降低。
因此,本发明的目的是去除现有技术的缺点。需要适于大的基板和大规模制造且展现经改良的色彩性能和高效率的彩色显示器。在改善上述特性的同时,应使有机电致发光器件的结构尽可能保持简单。
令人意外地,已发现通过在彩色显示器中使用纳米粒子和滤色体二者可解决该问题。
因此,本发明涉及一种包含下列的电子元件:
a)像素化有机电致发光器件100,其包含相同但独立电子控制的第一101、第二102、和第三103发光像素;
b)第一色彩转换体层201,其配置在该第一像素101的光输出路径151中,其中该色彩转换体层201包含至少一种发光半导体纳米粒子作为第一色彩转换体;
c)第一滤色体层301,其配置在包含第一滤色体的第一色彩转换体层201的光输出路径251中。
图1a)描绘了包含一种滤色体和一种色彩转换体层的电子元件。
在本发明一实施方案中,如果该第一色彩转换体层201只位于该第一像素101的光输出路径151中,即,该第一色彩转换体层201不在其他像素的光输出路径中,则其是优选的。
发光的强度可通过无源矩阵或有源矩阵技术电子地控制,优选地通过有源矩阵技术进行。
根据本发明的电子元件也可包含散射粒子。优选地,该电子元件不包含任何散射粒子。
该电子元件中所使用的光源为有机电致发光器件。任何已知的有机电致发光器件可用于本发明的目的。优选的有机电致发光器件选自由下列所组成的组:有机发光晶体管(OLET)、有机场猝熄器件(OFQD)、有机发光电化学电池(OLEC、LEC、LEEC)、有机激光二极管(O-激光)和有机发光二极管(OLED),非常优选OLEC和OLED,特别优选OLED。
优选如本文所公开的电子元件,其中该有机电致发光器件为有源矩阵器件。
术语“OLED”包括聚合物发光二极管(PLED)和包含非聚合型小分子的OLED二者。根据本发明的OLED也可包含非聚合型小分子和聚合物二者。
基于本发明目的,术语“蓝色”意指具有CIE(CIE 1931 RGB色空间)色坐标中CIE x在0.0至0.25的范围且CIE y在0.0至0.22的范围,或CIE x在0.0至0.2的范围且CIE y在0.22至0.35的范围的光。
基于本发明目的,术语“绿色”意指具有CIE(CIE 1931 RGB色空间)色坐标中CIE x在0.1至0.45的范围且CIE y在0.65至0.8的范围,或CIE x在0.24至0.45的范围且CIE y在0.45至0.65的范围的光。
基于本发明目的,术语“红色”意指具有CIE(CIE 1931 RGB色空间)色坐标中CIE x在0.55至0.75且CIE y在0.27至0.37的范围的光。
基于本发明目的,术语“蓝绿色”意指具有CIE(CIE 1931 RGB色空间)色坐标中CIEx在0.00至0.25且CIE y在0.36至0.55的范围的光。
基于本发明目的,术语“白色”意指具有以下CIE(CIE 1931 RGB色空间)色坐标的光:
CIE x在0.21至0.45的范围,且
CIE y在0.23至0.44的范围,
优选地CIE x在0.25至0.4的范围,且
CIE y在0.25至0.44的范围,
非常优选CIE x在0.3至0.4的范围,且
CIE y在0.3至0.44的范围,
特别优选
CIE x在0.3至0.35的范围,且
CIE y在0.3至0.35的范围,
非常特别优选CIE x在0.31至0.34的范围,且
CIE y在0.31至0.34的范围,
和甚至更优选CIE x在0.32至0.34的范围,且
CIE y在0.32至0.34的范围。
根据本发明,术语“层”包括“片”状结构。
根据本发明,术语“滤色体(color filter)”意指吸收光或辐射的材料,优选地该滤色体吸收可见光。本领域技术人员非常了解滤色体,且可从大量为人熟知的滤色体轻易地选择出最合适的滤色体。优选地,该滤色体为染料、颜料或其组合。
大体上,用于LCD滤色体的任何类型的众所周知的染料和颜料可以此方式使用。滤色体的优选实例为在“Technologies on LCD Color Filter and Chemicals”(CMCPublishing P.53(1998))中所公开的滤色体、偶氮螯合物颜料、稠合的偶氮颜料、喹吖啶酮颜料、异吲哚啉酮颜料、苝颜料、紫环酮(perinone)颜料、不可溶偶氮颜料、酞青颜料、二噁嗪颜料、蒽醌颜料、硫堇(thioin)颜料或任意这些的组合。
根据本发明,对该滤色体的主要要求之一是吸收由光源或色彩转换体(若存在)所发出的光,以改善由该电子元件最终发出的光的色彩纯度。
优选地,滤色体层的厚度是在500nm至5μm的范围,非常优选800nm至3μm,和特别优选1至2μm。
也优选地,若滤色体层的厚度在500nm至10μm的范围,非常优选750nm至7μm,和特别优选1至3μm。
根据本发明,术语“色彩转换体”意指将由有机电致发光器件100所发出的光或辐射转化成具有较长波长的光或辐射的材料。
根据本发明,术语“发光半导体纳米粒子”意指无机量子尺寸材料。优选地,该量子尺寸材料为量子点或量子棒或其组合。然而,纳米粒子也可具有无特别限制的形状,且可为四脚锥体(tetrapod)、圆碟形、棱柱形、球形、棒型、锥状或多臂形、或也可为纳米片类型。
根据本发明,术语“量子尺寸”涉及该材料本身的尺寸,其可显示量子尺寸效应,但无配体或另一表面改性。
通常,量子尺寸材料诸如量子点和/或量子棒可发出极其鲜艳(sharp vivid)的有色光。
该纳米粒子可为核/壳型或核/多壳型的经掺杂或渐变(graded)纳米粒子。
量子点和量子棒二者可容易地制造且相对于有机荧光或磷光化合物具有窄发射光谱(即,窄光谱线宽)。它们的尺寸可调整,该尺寸决定量子点或量子棒的发射最大值。以量子点和量子棒也可获得高光致发光效率。再者,其发射强度也可由其所使用浓度调整。此外,量子点和量子棒可溶于许多溶剂中或可轻易地制成可溶于常用有机溶剂中,使得能进行多样化处理方法,特别是印刷法,诸如丝网印刷、胶版印刷、和喷墨印刷。
优选地,该量子点选自II-VI族、III-V族、IV-VI族和IV族半导体,特别优选选自ZnO、ZnS、ZnSe、ZnTe、CdS、CdSe、CdTe、HgS、HgSe、HgTe、MgS、MgSe、GeS、GeSe、GeTe、SnS、SnSe、SnTe、PbO、PbS、PbSe、PbTe、GaN、GaP、GaAs、GaSb、InN、InP、InAs、InSb、AlN、AlP、AlAs、AlSb、GaN、GaP、GaAs、GaSb、及其组合。
优选地,该量子点为基于铅钙钛矿的量子点,非常优选选自如L.Protesecu等人(Nano Lett.,2015,15,3692-3696)中所公开的量子点。特别优选的基于铅的量子点选自CsPbl3、CsPbBr3、CsPbCl3、CsPb(I/Br)3和CsPb(Br/Cl)3。
作为量子点,视需要,优选可使用从例如Sigma-Aldrich可公开取得的量子点(下文称为“q-点”)。
优选地,该量子点的直径是在1至20nm的范围,非常优选在1与10nm的范围,和特别优选在2与7nm的范围。
在本发明优选实施方案中,该量子棒材料可选自由下列所组成的组:II-VI、III-V、或IV-VI半导体和这些中任意的组合。
更优选地,该量子棒材料可选自由下列所组成的组:Cds、CdSe、CdTe、ZnS、ZnSe、ZnTe、ZnO、GaAs、GaP、GaAs、GaSb、HgS、HgSe、HgSe、HgTe、InAs、InP、InSb、AlAs、AlP、AlSb、Cu2S、Cu2Se、CuInS2、CuInSe2、Cu2(ZnSn)S4、Cu2(InGa)S4、TiO2合金和这些中任意的组合。
例如,就发射红光用途而言,CdSe棒、在CdS棒中的CdSe点、在CdS棒中的ZnSe点、CdSe/ZnS棒、InP棒、CdSe/CdS棒、ZnSe/CdS棒或这些中任意的组合。就发射绿光用途而言,诸如CdSe棒、CdSe/ZnS棒、或这些中任意的组合,和就发射蓝光用途而言,诸如ZnSe、ZnS、ZnSe/ZnS核壳型棒、或这些中任意的组合。
量子棒材料的实例已描述于例如国际专利申请公开号WO2010/095140A中。
在本发明的优选实施方案中,该量子棒材料的整体结构长度为8nm至500nm。更优选地,为10nm至160nm。该量子棒材料的整体直径是在1nm至20nm的范围。更特别的是,其为1nm至10nm。
优选地,量子尺寸无机半导体材料,诸如量子棒和/或量子点包含表面配体。
量子棒和/或量子点材料的表面可外涂(over coat)有一种或多种类型的表面配体。
在不希望受理论束缚的情况下,据信该表面配体可导致量子尺寸无机半导体材料在溶剂中更易于分散。
常用表面配体包括膦和膦氧化物,诸如三辛基氧化膦(TOPO)、三辛基膦(TOP)和三丁基膦(TBP);膦酸,诸如十二烷基膦酸(DDPA)、十三烷基膦酸(TDPA)、十八烷基膦酸(ODPA)和己基膦酸(HPA);胺,诸如十二烷基胺(DDA)、十四烷基胺(TDA)、十六烷基胺(HDA)和十八烷基胺(ODA);硫醇,诸如十六烷硫醇和己烷硫醇;巯基羧酸,诸如巯基丙酸和巯基十一酸;和这些中任意的组合。
也可使用基于特定目的惯常制造的其他配体。
表面配体的实例已描述于例如国际专利申请公开号WO2012/059931A。
优选地,所转化的色彩埋在该色彩转换体层中的基质材料中。作为该基质材料,视需要,可使用任何类型的对于光学膜来说优选的众所周知的透明基质材料,但该基质材料应具有在色彩转换体层制造中的良好加工性和长期耐用性。
在本发明优选实施方案中,可使用聚合物,特别是光可固化聚合物,和/或光敏聚合物。例如,用于LCD滤色体中的丙烯酸酯树脂、任何光可固化聚硅氧烷、广泛用作光可固化的聚合物的聚肉桂酸乙烯酯或这些中任意的组合。
基于本发明目的,术语“散射粒子”意指一种材料,该材料具有的折射率不同于包括所述光散射粒子的层且可产生Mie散射效应的基质材料,该散射粒子优选地视需要使用。
根据本发明,作为光散射粒子,可使用任何类型的众所周知的光散射粒子。
例如,优选可使用以下的小的粒子:无机氧化物,诸如SiO2、SnO2、CuO、CoO、Al2O3、TiO2、Fe2O3、Y2O3、ZnO、MgO;有机粒子,诸如聚合的聚苯乙烯、聚合的PMMA;无机中空氧化物,诸如中空二氧化硅,硫酸盐,诸如BaSO4,或这些中任意的组合。
优选地,该光散射粒子的平均粒径可在350nm至5μm的范围。
在不希望受理论束缚的情况下,据信即使在光散射粒子与层基质之间的折射率差异小至0.1,大于350nm平均粒径也可导致较强前向散射,其由随后Mie散射导致。
另一方面,为了通过使用该光散射粒子获得更好的层形成性质,最大平均粒径优选为5μm或更小。更优选地,为500nm至2μm。
在优选实施方案中,该第一滤色体层301包含红色滤色体作为第一滤色体,且该第一色彩转换体层201包含发红光的半导体纳米粒子作为第一色彩转换体。
该电子元件也可包含含有第二滤色体的第二滤色体层302,其中该第二滤色体层配置在该第二像素102的光输出路径中,优选地该第二滤色体为绿色滤色体(图1b))。
该电子元件也可另外包含含有第三滤色体的第三滤色体层303,其中该第三滤色体层配置在该第三像素103的光输出路径中,优选地该第三滤色体为蓝色滤色体(图1b))。
各像素的滤色体和色彩转换体可在两个独立层或在单一层中。优选用于色彩转换体和彩色层为两个不同层。另外优选包含该色彩转换体和该滤色体二者的单一层。
因此,本发明还涉及本文所公开的电子元件,其中该第一滤色体和该第一色彩转换体位于相同层中而为第一合并层501(图2)。
非常优选地,包含该第一色彩转换体和该第一滤色体的该第一合并层在该色彩转换体的浓度方面展现与光输出路径平行的浓度梯度。
优选地,在该包含色彩转换体与滤色体二者的层中的色彩转换体的浓度为相对于于该层整体质量在10mg/m2至1g/m2的范围,优选地在20mg/m2至500mg/m2的范围,非常优选在50mg/m2至300mg/m2的范围,和特别优选在100mg/m2至200mg/m2的范围。
在本发明另一优选实施方案中,该电子元件包含第四像素104(图1、2和6)。
在本发明非常优选的实施方案中,该有机电致发光器件100发出白光。这可以不同方式实现,且本领域技术人员将毫无问题地建造适当发白光的有机电致发光器件(例如S.Reineke等人,Reviews of Modern Physics,85,No.3(2013年7月),1245-1293)。
另外优选位于该第二像素102与该第二滤色体层302之间的第二像素102的光输出路径152中的第二色彩转换体层202(图3)。非常优选第二色彩转换体为发光半导体纳米粒子,特别优选该第二色彩转换体发出绿光。
该第一色彩转换体层201和该第二色彩转换体层202也可以由配置在该第一101与该第二102像素的光输出路径中的单一色彩转换体层212表示,其中该公共色彩转换体层212包含该第一色彩转换体和该第二色彩转换体的组合(图4)。
在另一优选实施方案中,该电子元件的有机电致发光器件发出蓝光。
再者,该第二和第三滤色体可位于位于该第二152和第三153像素的光输出路径中的组合滤色体层523中,其中该公共滤色体层523包含该第二滤色体和该第三滤色体的组合。
在仍另一优选实施方案中,该电子元件的有机电致发光器件发出蓝绿光。
优选地,该第一色彩转换体层、第二色彩转换体层或第三色彩转换体层中的发光半导体纳米粒子的浓度在10mg/m2与1g/m2之间,非常优选在20mg/m2与500mg/m2之间,特别优选地在50mg/m2与300mg/m2之间,和非常优选在100mg/m2与200mg/m2之间。
优选地,该电子元件在该像素化有机电致发光器件100与一个或多个色彩转换体层之间另外包含平坦化层150,或如果不存在色彩转换体层,则该电子元件在该像素化有机电致发光器件100与一个或多个滤色体层之间另外包含平坦化层150。平坦化层为本领域技术人员熟知。因平坦化层常用于显示器技术,本领域技术人员可轻易地选择最适当的平坦化层。
图6的电子元件表示本发明的特别优选的实施方案。该元件包含4个像素、第一色彩转换体层、第一、第二和第三滤色体层。优选地,该有机电致发光器件100发出白光。
该电元件可用于例如移动设备、笔记本电脑、电视的屏幕中的彩色显示器。因此,本发明还涉及包含根据本发明的电子元件中的至少一者的彩色显示器。
优选地,该彩色显示器也包含TFT底板600。
使用本文所公开的发红光的色彩转换体具有数个有益效果。发红光的半导体纳米粒子与彩色显示器中的红色滤色体结合使用造成出人意料的经改善的红光发射,其具有有益的色域和高功率效率。
本发明还涉及包含至少一种发红光的半导体纳米粒子和至少一种红色滤色体的组合。该组合可另外包含至少一种散射粒子。
本发明还涉及包含至少一种发光半导体纳米粒子,优选地至少一种发红光的半导体纳米粒子,和至少一种红色滤色体的层。
可通过特别制备包含量子棒或核壳型量子棒作为色彩转换体可进一步改善性能数据。因此,本发明还涉及一种制备根据本发明的包含量子棒或核壳型量子棒或其组合的电子元件的方法,其特征在于包括该量子棒或核壳型量子棒的色彩转换体层是至少部分定向,该定向优选是通过定向沉积或通过在其沉积至该像素化有机电致发光器件之前拉伸而进行。可使用任何方法以定向该色彩转换体层。本领域技术人员可毫无困难地选择最适当方法。色彩转换体层的定向特别有利于光的极化、光的外耦合(out coupling)、和光的亮度。
该定向可例如经由拉伸(例如WO 2012/059931)或使用通过预结构化成具有凹口的基板而发生。
可使用本领域中熟知的其他技术以极化该发出的光或改善外耦合。实现其的优选方法为WO 2015/151092 A1和WO 2015/198327 A1中所公开的方法。
所得的器件具有取决于该色彩转换体层的结构化程度的特殊结构。
因此,本发明还涉及通过上述方法所获得的电子元件。
根据本发明的彩色显示器的特征在于下列相对于现有技术的令人惊奇的优点:
1.根据本发明的器件显示比根据现有技术器件更高的色彩纯度;
2.根据本发明的器件显示经改良的效率;
3.根据本发明的器件可以以低制造成本容易地制备;
4.根据本发明的器件特别适于大量制造;
5.根据本发明的器件具有与根据现有技术的器件相比更长的使用寿命。
应了解,可对本发明的前述实施方式作出修改,而仍处于本发明的范围内。除非另有说明,否则起到相同、等效或类似目的的替代特征可代替本说明书中所公开的每一特征。因此,除非另有说明,否则每一所公开特征仅是一系列等效或类似特征中的一个实例。
本说明书中所公开的全部特征可以任何组合形式来组合,但其中这样的特征和/或步骤中的至少一些互斥的组合除外。特别地,本发明的优选特征适用于本发明的全部方面且可以任何组合形式使用。同样,以非必需组合形式描述的特征可分别地(不以组合形式)使用。
应了解,上述多个特征(特别是实施方案的特征)以它们自身是发明性的,而不仅仅作为本发明实施方式的一部分。除目前所要求保护的任何发明以外或作为目前所要求保护的任何发明的替代发明,可寻求这些特征的独立保护。
此处所公开的教导可被摘要以及与所公开的其他实施例合并。
本发明的其他特征在附图和下文示例性实施方案的描述过程中将变明白,给出其提供说明本发明且无意限制本发明。
在下文操作实施例中,参考附图将更详细描述一些上述实施方案。
附图简述
图1在a)及b)中描绘了根据本发明电子器件的不同配置。该电子器件包含含有第一像素101、第二像素102、第二像素103及任选的第四像素104的有机电致发光器件100。该像素发出相同的光,但电子地独立控制。该器件在第一像素的光输出路径151中包括包含第一发光半导体纳米粒子的色彩转换体层201。在该第一色彩转换体层201的光输出路径251中,该电子器件另外包含第一滤色体层301。该第一滤色体层301最终发出光351。第二102、第三103及第四104像素的光输出路径分别以152、153及154表示。通过像素直接或通过滤色体层发射至该电子器件外部的光是以351、352、353及354表示。在b)中,第二滤色体层302及第三滤色体层303分别配置在该第二像素102和该第三像素103的光输出路径中。
图2显示根据本发明的电子器件,其中该第一色彩转换发光半导体纳米粒子和该第一滤色体作为组合用于单一层501中。
图3显示另一根据本发明的电子器件,其中第二色彩转换体层202配置在该第二像素102的光输出路径152中。该第二滤色体层302配置在该色彩转换体层202的光输出路径252中。
图4显示根据本发明的像素化器件,其具有第一像素及第二像素的公共色彩转换体层212。
图5显示根据本发明的另一电子器件,其中公共滤色体层523配置在该第二像素102及第三像素103的光输出路径152及153中。
图6描绘包含像素化串联OLED作为发白光有机电致发光器件100的全彩色显示器的实例,其中编号具有下列意义:201-包含至少一种发红光的半导体纳米粒子的第一色彩转换体层;301-第一滤色体(其为红色滤色体);302-第二滤色体(其为绿色滤色体);303-第三滤色体(其为蓝色滤色体);10-第一、第二、第三及(任选的)第四像素的阴极层;20-第一、第二、第三及第四像素的电子传输层(ETL);30-第一、第二、第三及第四像素的红/绿或黄光发射层;40-第一、第二、第三及第四像素的空穴传输层(HTL);50-第一、第二、第三及第四像素的电荷产生层;60-第一、第二、第三及第四像素的蓝光发射层;70-第一、第二、第三及第四像素的空穴传输层(HTL);90-第一、第二、第三及第四像素的阳极(例如ITO);150-平坦化层;600-TFT底板:氧化物、LTPS(低温多晶硅);700-玻璃。
图7显示实施例3中所使用的白色OLED的电致发光光谱。
图8显示实施例3中所使用的红色滤色体的透射光谱。
工作实施例
实施例1
制备发光半导体纳米粒子
制备发红光的纳米棒的CdSe核:
在150℃将含有0.06g的氧化镉、0.28g的十八基膦酸(ODPA)及3g的三辛基氧化膦(TOPO)的3颈烧瓶除气一个半小时。在手套箱中通过将58mg的单质Se溶解于20mL小瓶中的0.36g的三正辛基膦(TOP)而制备硒前体。将1.5g的TOP置于第二个小瓶中。在除气之后,用氩冲洗该烧瓶,并加热至约300℃(当达到光学清洗度时)。此时,将1.5g的TOP缓慢注入该烧瓶中。将该烧瓶进一步加热至350℃,于此时,将TOP:Se快速注入该烧瓶中。反应时间取决于所希望的核尺寸。该反应是通过移除加热源而停止。通过1:1甲苯:甲醇混合物将该核溶解并且沉淀。在该第一步骤中,合成直径为3.4nm的CdSe核。
制备CdSe/CdS发红光的纳米棒:
在150℃将含有0.12g的氧化镉、0.16g的六膦酸(hexaphosphonic acid,HPA)、0.56g的十八基膦酸(ODPA)及3g的三辛基氧化膦(TOPO)的3颈烧瓶除气一个半小时。硫前体是通过将0.12g的单质硫溶解于20mL小瓶中的1.5g的三正辛基膦(TOP)而制备。将1.5g的TOP置于第二个小瓶中。所希望的核的量取决于所希望的纳米棒长度。就23nm长的棒而言,需要2.3*10-7摩尔的CdSe。在将该硫溶解之后,将TOP:S倒至该经纯化的核上并混合直到该核达到完全溶解。在除气之后,用氩冲洗该烧瓶并加热至约300℃(当达到光学澄清度时)。此时,将1.5g的TOP缓慢注入该烧瓶中。将该烧瓶进一步加热至360℃,于此时,将TOP:S:CdSe快速注入该烧瓶中。使该反应静置8分钟。该反应是通过移除加热源而停止。使用上述直径为3.4nm的CdSe核所合成的所得纳米棒在甲苯溶液中测量时具有23x7nm的尺寸,其发射最大值在628nm,且半高宽(FWHM)为24nm。
实施例2
色彩转换膜的制备及表示
未拉伸的膜是依照与WO 2011/092646(LIGHTING DEVICES WITH PRESCRIBEDCOLOUR EMISSION)中所公开程序相似的程序制备。制备两种不同的膜,一种为散射膜(称为QFilm2)及一种为非散射膜(称为QFilm1)。用于制备该膜的纳米棒的制备是如上文所述。
制备非散射膜(QFilm1):
制备纳米棒溶液。为此,将特定量的纳米棒添加至4ml甲苯中。选择用量以使得当该溶液稀释50倍时,在450nm获得10mm路径的石英比色皿(cuvette)的光学密度为0.27。接着,将例如可得自Sigma-Aldrich的1.1g的聚(乙烯基丁醛-共-乙烯醇-共-乙酸乙烯酯)(PVB)溶解于15ml甲苯中。在搅拌下将25%的该PVB溶液添加至该纳米棒溶液。将所得的纳米棒及PVB的溶液放于6cm×6cm玻璃板上,将其插入干燥器并抽真空15小时,之后该混合物为固态,且可从该玻璃板移除所得的膜。
制备散射膜(QFilm2):
该散射膜(QFilm2)是以相同方式制备,除了将额外的55mg的BaSO4添加至该PVB溶液。该膜的量子产率是以Hamamatsu Quantaurus QY C11347-11测量,且获得该非散射膜的值为63%,而散射膜的值为66%。该非散射膜的光学密度是使用Shimadzu UV-1800分光光度计测量,且获得1.28的值。
经拉伸膜(称为QFilm3)是依照WO 2012/059931(POLARIZING LIGHTING SYSTEMS,实施例1)中所述的程序,以拉伸比为4来制备。在拉伸之前的膜是依照与上述非散射膜的相同程序制备。极化比是通过将平行于拉伸轴极化的发射的强度除以与垂直于拉伸轴的发射而获得。该实施例的经拉伸膜展现2.7的极化比。该膜的量子产率是以HamamatsuQuantaurus QY C11347-11测量,且获得64%的值。该膜的光学密度是使用Shimadzu UV-1800分光光度计测量,且获得0.75的值。
实施例3
器件制造及表示
性能数据的测定:
由亮度及电流密度计算电流效率(以cd/A计)。亮度是以经校准的光电二极管沿前向方向测量。记录亮度为1000cd/m2的电致发光光谱。计算这些光谱的CIE 1931 x及y色坐标。外部量子效率(EQE,以%测量)是在朗伯发射(lambertian emission)的假设下,由电流效率、电压及电致发光光谱(对于1000cd/m2)的测量来计算。
对于下列实施例,使用发白光的OLED。该电致发光光谱示于图7中。该OLED具有的EQE为29.3%。
作为根据现有技术的对比实施例,将红色滤色体(Lee Filter 106,"原色红(Primary red)")置于该OLED上。该滤色体的透射光谱示于图8中。使用C14H12O2作为介于该OLED与该滤色体之间的浸油。所得的器件显示红光发射,CIE 1931色坐标x=0.67,y=0.32,且EQE为4.7%。
作为本发明实施例,将含有纳米棒的膜(QFilm)置于该滤色体与该OLED之间。应用C14H12O2作为介于该OLED与该QFilm之间以及介于该QFilm与该红色滤色体之间的浸油。
若使用非散射QFilm1,该EQE提高至7.1%,其相当于相对于现有技术的50%改善。此器件的色坐标为x=0.68,y=0.32,且因此与来自该对比实施例的器件的色坐标实质上相同。
若使用散射QFilm2,该EQE提高至8.0%,其相当于70%改善。此器件的色坐标为x=0.68,y=0.32,且因此与来自该对比实施例的器件的色坐标几乎相同。
若使用经拉伸的非散射QFilm3,该EQE提高至5.8%,其相当于约20%的改善。此器件的色坐标为x=0.68,y=0.32,且因此与来自该对比实施例的器件的色坐标几乎相同。
若使用两个QFilm3代替一个QFilm3,且在该两个膜之间应用浸油,该EQE提高至6.3%,其对应于35%的改善。此器件的色坐标为x=0.68,y=0.32,且因此与来自该对比实施例的器件的色坐标实质上相同。
Claims (23)
1.电子元件,其包含
a)像素化有机电致发光器件100,其包含相同但独立电子控制的第一101、第二102、第三103发光像素;
b)第一色彩转换体层201,其配置在该第一像素101的光输出路径151中,其中该色彩转换体层201包含至少一种发光半导体纳米粒子作为第一色彩转换体;
c)第一滤色体层301,其配置在包含第一滤色体的第一色彩转换体层201的光输出路径251中。
2.根据权利要求1的电子元件,其特征在于该第一滤色体层301包含红色滤色体作为第一滤色体,和该第一色彩转换体层201包含发红光的半导体纳米粒子作为第一色彩转换体。
3.根据权利要求1或2的电子元件,其特征在于包含第二滤色体的第二滤色体层302配置在该第二像素102的光输出路径中,优选地该第二滤色体为绿色滤色体。
4.根据权利要求1至3中一项或多项的电子元件,其特征在于包含第三滤色体的第三滤色体层303配置在该第三像素103的光输出路径中,优选地该第三滤色体为蓝色滤色体。
5.根据权利要求1至4中一项或多项的电子元件,其特征在于该第一滤色体和该第一色彩转换体位于相同层中作为第一合并层501。
6.根据权利要求1至5中一项或多项的电子元件,其特征在于该显示器包含第四像素104。
7.根据权利要求1至6中一项或多项的电子元件,其特征在于该像素化有机电致发光器件的像素发出白光。
8.根据权利要求1至7中一项或多项的电子元件,其特征在于该器件在该第二像素102与该第二滤色体层302之间的第二像素102的光输出路径152中包括包含第二色彩转换体的第二色彩转换体层202,优选地该第二色彩转换体为发光半导体纳米粒子,非常优选该第二色彩转换体发出绿光。
9.根据权利要求8的电子元件,其特征在于该第一色彩转换体层201和该第二色彩转换体层202以配置在该第一101与该第二102像素的光输出路径中的单一公共色彩转换体层212表示,其中该公共色彩转换体层212包含该第一色彩转换体和该第二色彩转换体的组合。
10.根据权利要求1至6、8或9中一项或多项的电子元件,其特征在于该有机电致发光器件发出蓝光。
11.根据权利要求1至10中一项或多项的电子元件,其特征在于该器件包含在该第二152和第三153像素的光输出路径中的公共滤色体层523,其中该公共滤色体层包含该第二滤色体和该第三滤色体的组合。
12.根据权利要求1至11中一项或多项的电子元件,其特征在于该有机电致发光器件发出蓝绿色光。
13.根据权利要求1至12中一项或多项的电子元件,其特征在于该第一色彩转换体层、第二色彩转换体层或第三色彩转换体层中的发光半导体纳米粒子的浓度是在10mg/m2至1g/m2,优选地在20mg/m2至500mg/m2,非常优选地在50mg/m2至300mg/m2,和特别优选地在100mg/m2至200mg/m2的范围。
14.根据权利要求1至13中一项或多项的电子元件,其特征在于该发光半导体纳米粒子选自量子点、核壳型量子点、量子棒、核壳型量子棒及其组合。
15.根据权利要求1至14中一项或多项的电子元件,其特征在于该发光半导体纳米粒子选自InGaP、CdSe、CdS、CdTe、ZnO、ZnSe、ZnS、ZnTe、HgSe、HgTe、CdZnSe、InP、InN、GaN、InSb、InAsP、InGaAs、GaAs、GaP、GaSb、AlP、AlN、AlAs、AlSb、CdSeTe、ZnCdSe、PbSe、PbTe、PbS、PbSnTe、和Tl2SnTe5及其组合。
16.根据权利要求1至15中一项或多项的电子元件,其特征在于该滤色体选自染料和颜料。
17.根据权利要求1至16中一项或多项的电子元件,其特征在于该器件在该像素化有机电致发光器件100与一个或多个色彩转换体层之间另外包含平坦化层150,或如果不存在色彩转换体层,则该器件在该像素化有机电致发光器件100与一个或多个滤色体层之间另外包含平坦化层150。
18.彩色显示器,其包含根据权利要求1至17中一项或多项的电子元件中的至少一者。
19.根据权利要求18的彩色显示器,其特征在于该彩色显示器包含TFT底板600。
20.在彩色显示器中发红光的半导体纳米粒子与红色滤色体结合以产生红光发射的用途,这导致有益的色域和高功率效率,该彩色显示器包含有机电致发光器件,优选包含有机发光二极管(OLED)。
21.层,其包含至少一种发红光的半导体纳米粒子和至少一种红色滤色体。
22.制备根据权利要求1至17中一项或多项的电子元件的方法,其特征在于包含量子棒、核壳型量子棒或其组合的色彩转换体层是至少部分定向的,该定向优选是通过定向沉积或通过在其沉积至像素化有机电致发光器件之前拉伸而进行。
23.电子元件,其可根据根据权利要求22的方法获得。
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