CN113412542A - 可调颜色led-oled混合引导照明设备 - Google Patents
可调颜色led-oled混合引导照明设备 Download PDFInfo
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- CN113412542A CN113412542A CN201980037844.4A CN201980037844A CN113412542A CN 113412542 A CN113412542 A CN 113412542A CN 201980037844 A CN201980037844 A CN 201980037844A CN 113412542 A CN113412542 A CN 113412542A
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L25/16—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof the devices being of types provided for in two or more different main groups of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. forming hybrid circuits
- H01L25/167—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof the devices being of types provided for in two or more different main groups of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. forming hybrid circuits comprising optoelectronic devices, e.g. LED, photodiodes
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- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/0001—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems
- G02B6/0011—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being planar or of plate-like form
- G02B6/0033—Means for improving the coupling-out of light from the light guide
- G02B6/0035—Means for improving the coupling-out of light from the light guide provided on the surface of the light guide or in the bulk of it
- G02B6/004—Scattering dots or dot-like elements, e.g. microbeads, scattering particles, nanoparticles
- G02B6/0041—Scattering dots or dot-like elements, e.g. microbeads, scattering particles, nanoparticles provided in the bulk of the light guide
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- C—CHEMISTRY; METALLURGY
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01L25/03—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes
- H01L25/04—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers
- H01L25/075—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers the devices being of a type provided for in group H01L33/00
- H01L25/0753—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers the devices being of a type provided for in group H01L33/00 the devices being arranged next to each other
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L25/16—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof the devices being of types provided for in two or more different main groups of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. forming hybrid circuits
- H01L25/162—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof the devices being of types provided for in two or more different main groups of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. forming hybrid circuits the devices being mounted on two or more different substrates
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/85—Arrangements for extracting light from the devices
- H10K50/852—Arrangements for extracting light from the devices comprising a resonant cavity structure, e.g. Bragg reflector pair
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/85—Arrangements for extracting light from the devices
- H10K50/854—Arrangements for extracting light from the devices comprising scattering means
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/85—Arrangements for extracting light from the devices
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- 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
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Abstract
混合LED‑OLED照明设备包括波导层、于其光耦合的发光二极管(LED)阵列和有机发光二极管(OLED)阵列。LED阵列发出的光从波导层的边缘射入,OLED阵列发出的光从波导层的第一表面射入。从LED阵列发出的光和从OLED阵列发出的光穿过波导层第一表面对面的第二表面。照明设备发出的光包括LED阵列发出的光和OLED阵列发出的光。
Description
对相关应用程序的交叉引用
此申请声称受益于美国申请第62/680,474号,标题为"可调颜色 LED-OLED混合引导照明设备",于2018年6月4日提交的专利申请。
技术领域
本发明涉及具有高效率和稳定性的LED(无机发光二极管)-OLED (有机发光二极管)混合照明器件。
背景技术
高效稳定的发光二极管(LEDs)和有机发光二极管(OLEDs)有部分但不包括全部的颜色可供选择。虽然基于LED和OLED的照明设备已被开发出来,但室内照明还不具有可调颜色、均匀的平面发射、高效率、高稳定性的所有属性。
总述
在第一部分中,LED-OLED混合照明设备中包括有波导层、光耦合于波导层的发光二极管(LED)阵列以及有机发光二极管(OLED)阵列。 LED阵列发出的光从波导层的边缘射入,OLED阵列发出的光从波导层的第一表面射入。从LED阵列发出的光和从OLED阵列发出的光共同穿过与波导层的第一表面相对设置的波导层的第二表面,照明设备发出的光包括LED阵列发出的光和OLED阵列发出的光。
在第一部分实现过程中包括有以下一个或多个特征。
LED阵列发出的光位于可见光谱的蓝光范围内。OLED阵列发出的光位于可见光谱的黄色或橙黄色范围内。照明设备发出的光为白光(例如,暖白光或冷白光)。照明设备发出的光颜色是可调的。LED阵列的发光强度和OLED阵列的发光强度可独立控制。
波导层的边缘延伸到波导层的第一表面和第二表面之间。在某些情形下,波导层的边缘与波导层的第一表面大致垂直。照明装置可能包括有与波导层的第一表面直接接触的反射层。在某些情形下,照明设备包括有与波导层第二表面直接接触的扩散膜。在某些情形下,权利要求1所示的照明装置中包括有设置扩散膜和波导层第二表面之间的光学指标匹配粘合剂。
OLED阵列与波导层耦合(例如,光学耦合),并使其光射入波导层的第一表面。在某些实现过程中,OLED阵列的反光性金属电极设置于波导层和制造OLED阵列的基板之间。在某些实现过程中,波导层和 OLED阵列的透光性电极被承载OLED阵列的基板隔开。LED阵列通常是从波导层边缘射入,OLED阵列通常从波导层背面射入。
LED扩散光源包括有波导层,还可能包括有棱镜保护膜、伦兹薄膜、棱镜膜或它们之间的任意组合。OLED光源包括在OLED阵列内,可能还包括有内光提取层、外光提取层或两者兼有。在一个示例中,OLED光源包括有内光提取层、外光萃取层以及它们之间的基板。
OLED阵列中的每个OLED通常会选择一微腔长度,该微腔长度以优化黄光或橙黄光的共振条件为目的。在某些情形下,OLED阵列中的每个OLED都包含有一个由通用分子式Ⅰ表示的发光材料:
其中:
M表示二价铂或二价钯金属离子;
各R1,R3,R4和R5独立表示氢基、卤素基、羟基、硝基、氰基、硫醇基或可选替代的含有C1-C4烷基、烷氧基、氨基或芳香基;
每个n是独立的整数,在被允许的情况下;
Y1a,Y1b,Y1c,Y1d,Y1e,Y1f,Y2a,Y2b,Y2c,Y2d,Y2e,Y2f,Y4a,Y4b, Y4c,Y4d,Y4e,Y5a,Y5b,Y5c,Y5d和Y5e独立表示碳、氮、硅、氧、硫;
X2表示NR,PR,CRR',SiRR',CRR',SiRR',O,S,S=O,O=S=O,
Se,Se=O,或O=Se=O,其中R和R'可以独立代表氢基、卤素基、羟基、硝基、氰基、硫醇基或含有C1-C4烷基、烷氧基、氨基或芳香基或杂芳香基;
每个L1和L3都可以独立存在或不存在,如果存在,则表示已取代或未取代的连结原子或连结官能团,其中已取代的连结原子可以与烷基、烷氧基、烷烃基、烷炔基、羟基、胺基、酰胺基、硫醇、芳香基、杂芳香基、环烷基或杂环烷基相结合;
Ar3和Ar4各独立代表一个六元环为基础的芳香环;
Ar1和Ar5各独立代表一个五元到十元的芳香环、杂芳香环、共轭芳香环或共轭杂芳香环。
在某些情形下,OLED阵列中的OLED都包含有一个由通用分子式Ⅱ- Ⅸ表示的发光材料:
其中:
M表示二价铂或二价钯金属离子;
R1,R2,R3,R4,R5和R6各独立表示氢基、卤素基、羟基、硝基、腈基、硫醇基或含有一个到四个碳原子的烷基、烷氧基、氨基或芳香基;
每个n是独立的整数,在被允许的情况下;
Y1a,Y1b,Y1c,Y1d,Y2a,Y2b,Y2c,Y3a,Y3b,Y3c,Y4a,Y4b,Y4c,Y5a, Y5b,Y5c,Y5d,Y6a,Y6b,Y6c,和Y6d各独立表示碳、氮和硅;
U1和U2各独立表示NR,O,S,其中R都独立代表氢基、卤素基、羟基、硝基、腈基、硫醇基或含有C1-C4烷基、烷氧基、氨基或芳香基;
U3和U4各独立表示氮,磷;
X表示O,S,NR,CRR',SiRR',PR,BR,S=O,O=S=O,Se,Se=O,或O=Se=O,其中R和R'都独立代表氢基、卤素基、羟基、硝基、腈基、硫醇基或含有C1-C4烷基、烷氧基、氨基或芳香基;
本申请的一个或多个实施例的细节在附图以及附图描述中有详细说明。主题的其他特征、方面和优点从描述、图纸和权利要求中显而易见。
附图简要说明
图1A和1B描述了可调颜色LED-OLED混合引导照明设备。
图2描述了边缘光照LED并光扩散器结构的示意图。
图3描述了OLED发光器结构的示意图。
图4描述了可调颜色LED-OLED混合引导照明设备产生的冷白色和暖白色发射光谱。
图5A-5D描述了OLED样品一的器件数据,包括工作电流密度与电压、使用寿命测试之前和之后电致(EL)发光光谱的对比、外部量子效率 (EQE)与发光亮度,以及电光能量转换效率与亮度。
图6A-6C描述了OLED样品二在不同配置情景下获得的外部量子效率与工作电流密度的器件数据。
图7A-7C描述了OLED样品三在不同配置情景下获得的外部量子效率与工作电流密度的器件数据。
图8A-8C描述了OLED样品四在针对OLED的各种驱动电流密度情景下,发射光谱为白色LED、蓝色LED以及多重电致发射光谱的混合 LED-OLED发光设备。
详细描述
介绍了可调颜色LED(发光二极管)-OLED(有机发光二极管)混合引导照明设备,用于发射高效率和稳定的冷白光或暖白光。通过独立控制LED和OLED的驱动电流,可以大范围调控混合LED-OLED照明设备的电致发光光谱,从LED发射的冷白光到占主导地位的OLED发射的暖白光。
图1A描述了可调颜色LED-OLED混合照明设备100。混合照明设备100包括有LED阵列102。LED阵列102包括有一个或多个LED104,这些LED 均位于光学器件106中。每个LED104可发出色温超过5000K的冷白光或波长范围约为440nm至500nm的蓝光。LED阵列102包括两种电极108、110。光学外壳106配置为将LED104的发光引导至混合照明设备100中的波导层112,LED阵列102和波导层112之间优选最小间距,以优化图2中描述的LED扩散光源的器件效率。波导层112是一种光波导,通常由玻璃、聚合物或半导体材料制成,具有用于引导可见光传播的平面形状、条状或光纤式配置。如所描述,LED阵列102是边缘照明的,因此LED阵列102的光被光学耦合到混合照明设备100中的波导层112。混合照明设备 100可包括有个或多个LED阵列102,其发光从混合照明设备100的两个或多个侧面被光学耦合到混合照明设备100中。
在某些实现过程中,波导层112可以作为OLED制造的基板。在某些实现过程中,混合照明设备100包括有与波导层112相触(例如,直接接触)的单独基板114,而OLED阵列116制造在基板114上。基板114通常由玻璃或塑料制成。OLED阵列116包括有一个或多个OLED面板118。每个OLED面板118通常发出黄色或橙黄色的光,具有从约480nm到约 700nm的宽波长范围的发射频谱。OLED阵列116是背面发光,包括不透明和反光的金属电极120和光透射电极122。在某些实现过程中,OLED 阵列116包括有一个或多个内光提取层和外光提取层。LED阵列102和 OLED阵列116可被独立控制。
在LED阵列102点亮期间,光从LED104射入波导层112,通过扩散膜 124从混合照明设备100发射出来。扩散膜124通常是半透明材料制成的薄膜,如地面玻璃、TEFLON、全息投影玻璃、蛋白石玻璃和灰玻璃,它们会以某种方式散射光,以发出柔和的光线。波导层112和基板114 之间的反射膜可以抑制LED阵列102的光线进入基板114。波导层112通常包括光学介质纳米颗粒126。在OLED阵列116点亮期间,光从OLED118 向基板114射入,通过波导层112,通过扩散膜124从混合照明设备100 发出。如图2所述,混合照明设备100可以包括一个或多个棱镜薄膜、伦茨薄膜、棱镜保护膜和扩散膜124。波导层112中的纳米颗粒126有助于产生散射的可见光128。当LED阵列102发出蓝光,OLED阵列116发出橙黄色或黄色光时,混合照明设备100发出可调的白色光。
图1B描述了可调颜色LED-OLED混合照明设备130。混合照明设备 130包括LED阵列102。LED阵列102包括一个或多个LED104,这些LED均位于光学外壳106中。每个LED104可发出色温超过5000K的冷白光或波长范围约为440nm至500nm的蓝光。LED阵列102包括两种电极108、110。光学外壳106配置为将LED104的光线引导至混合照明设备130中的波导层112。如所描述,LED阵列102是边缘照明的,因此LED阵列102的光被光学耦合到混合照明设备130中的波导层112。混合照明设备130可包括两个或多个LED阵列102,其发光从混合照明设备130的两个或多个侧面被光学耦合到混合器件130。OLED阵列116位于波导层112和基板114之间,包括一个或多个OLED面板118。基板114通常由玻璃或塑料制成。每个OLED118通常发出黄色或橙黄色的光。OLED阵列116在波导层背面发光,包括不透明和反光的金属电极120和光透射电极122。如图3所示, OLED阵列116可以包括一个或多个内光提取层和外光提取层,以增强 OLED阵列116的发光效率。LED阵列102和OLED阵列116可被独立控制。
在LED阵列102点亮期间,光从LED104射入波导层112,通过扩散膜124从混合照明设备130发射出来。波导层112通常包括有光学介质纳米颗粒126。在OLED阵列116点亮期间,光从OLED118向波导层112射入,通过扩散膜124从混合照明设备130发出。因此,来自OLED阵列116的光从混合照明设备130发出时没有经受基板114相关的损耗。如图3所述, OLED阵列116可以包括一个或多个内光提取层和外光提取层,以增强 OLED阵列116的发光效率。波导层112中的纳米颗粒126有助于可见光 128扩散。当LED阵列102发出蓝光,OLED阵列116发出橙黄色或黄色光时,混合照明设备130发出可调的白色光。
提高LED器件发光效率的方法包括:选择高效LED光源,减少或最小化LED104和波导层112之间的气隙,减少或最小化光线在基板114中的损耗,减少或最小化基板114带来的光散射(例如,通过包含设置的内部提取层),匹配混合照明设备100和130之间使用的各种薄膜(例如波导层112和扩散膜124)的光学指标。不同薄膜之间光学指标的匹配可以通过在薄膜间加入直接接触的光学指标匹配胶或粘合剂来实现。合适的光学指标匹配粘合剂包括硅基高分子或其他适当的透明粘性聚合物,具有1.4到1.7之间的光折射率。合适的光学指标匹配粘合剂的示例包括有SYOPTEK国际有限公司的光学胶粘剂(匹配凝胶),诺兰的光学凝胶和康宁公司的光学指标匹配凝胶。
图2描绘了LED扩散发光器结构200,包括在光学外壳106中的LED 阵列102及耦合其发光的波导层112,是混合照明设备100、130的一部分。如图1A和1B所示,LED阵列102与波导层112进行光学耦合。反射膜 202可直接接触波导层112的第一表面。反射膜202的反射率可以调节,以实现LED102发光自波导层112侧面射入的内部反射量的最大化以及确保橙黄色OLED发射光进入波导层112的最大透光率,同时使来自LED 阵列102的光被禁止向OLED阵列射入。扩散膜124可与波导层112直接接触。混合照明设备100,130可包括一个或多个棱镜膜204,伦茨膜206,以及贴在扩散膜上的棱镜保护膜208。棱镜膜204通常是高分子薄膜(如聚酯),具有细棱镜结构,用于帮助凝结光源发光。棱镜保护膜208 通常是一个透明的薄膜,可以保护棱镜膜204免受物理性伤害。在实施例中,棱镜膜204在扩散膜124和伦茨膜206之间与其直接接触。棱镜保护膜208也可以是混合照明设备100和130的最外一层膜。
图3描述了OLED结构300,包括混合照明设备100和130的组成部分 OLED面板118。OLED面板118包括反射电极(金属阴极)120、光透射电极(阳极)122。反射电极120通常包括铝、银、金或它们组合的合金。反射电极120一般厚度在20纳米和300纳米之间。光透射电极122通常包括氧化铟锡(ITO)、氧化锌锡(ZTO)、氧化锡(SnOx)、氧化铟(InOx)、氧化钼(MoOx)、碳纳米管或它们之间的组合。光透射电极122的一般厚度在10纳米和100纳米之间。在反射电极120和光透射电极122之间, OLED118具有电致发光层302,通常包括在反射电极120和光透射电极 122之间的电子注入层304、电子传输层306、空穴阻断层308、发光材料层310、电子阻断层312、空穴传输层314、空穴注入层316。发光材料层310使用黄色或橙黄色的有机发光材料,包括双分子激发态电致磷光材料具有发射波长480-700nm的范围,或具有发射波长为480-700nm 范围的绿色和红色电致磷光材料混合物。发光材料层310可包括从芳香基取代胺、芳香基取代咔唑、芳香基取代恶二唑、芳香基取代三唑、芳香基取代菲咯啉和环氧喹啉金属络合物为主要官能团的主体材料,并包含至少一种分散在主体材料中的电致磷光材料,该电致磷光材料从包括环状金属络合物及其衍生物的磷光发光材料中挑选。平面化层 318可直接接触光透射电极122。平面化层318通常是由有机或无机材料制成的透明薄膜,有助于降低内光提取层320的表面粗糙度。内光提取层320可能与平面化层318直接接触。内光提取层320通常是薄膜,包括光学介质纳米粒子,可散射各种角度的入射光。一般而言,平面化层 318的总体表面粗糙度和内光提取层320通常小于约10纳米或小于约5 纳米。基板322可介于内光提取层320和外光提取层324之间并与其直接接触。外光提取层324为附着在基板322表面的高分子薄膜,它便于释放陷入基板322中的光子,并提高OLED面板的发光效率。
OLED118包括有一个光学微腔,并在基板322上定义了微腔的长度。 OLED118的微腔长度经过调整为发射黄色或橙黄色光提供共振条件。 OLED118光提取效率的提高可通过调整反射电极120和光透射电极122 之间的间距,通过调整透射电极122的厚度、电致发光层302的厚度或两者共同调整来确定。
图4描述了混合LED-OLED照明设备产生的冷白色和暖白色发射光谱,如图1A和1B所示。冷白色发射频谱400可通过提高LED驱动电流获得。暖白色发射频谱402可通过降低LED驱动电流获得。
适用于发光材料层310的黄色和橙黄色磷光材料(例如,发射光波长范围为480nm至700nm)的举例包括通用分子式Ⅰ表示的络合物。
通用分子式Ⅰ中:
M表示二价铂或二价钯金属离子;
各R1,R3,R4和R5独立表示氢基、卤素基、羟基、硝基、氰基、硫醇基或可选替代的含有C1-C4烷基、烷氧基、氨基或芳香基;
每个n是独立的整数,在被允许的情况下;
Y1a,Y1b,Y1c,Y1d,Y1e,Y1f,Y2a,Y2b,Y2c,Y2d,Y2e,Y2f,Y4a,Y4b, Y4c,Y4d,Y4e,Y5a,Y5b,Y5c,Y5d和Y5e独立表示碳、氮、硅、氧、硫;
X2表示NR,PR,CRR',SiRR',CRR',SiRR',O,S,S=O,O=S=O, Se,Se=O,或O=Se=O,其中R和R'可以独立代表氢基、卤素基、羟基、硝基、氰基、硫醇基或含有C1-C4烷基、烷氧基、氨基或芳香基或杂芳香基;
每个L1和L3都可以独立存在或不存在,如果存在,则表示已取代或未取代的连结原子或连结官能团,其中已取代的连结原子可以与烷基、烷氧基、烷烃基、烷炔基、羟基、胺基、酰胺基、硫醇、芳香基、杂芳香基、环烷基或杂环烷基相结合;
Ar3和Ar4各独立代表一个六元环为基础的芳香环;
Ar1和Ar5各独立代表一个五元到十元的芳香环、杂芳香环、共轭芳香环或共轭杂芳香环。
通用分子式Ⅰ代表的络合物示例如下所示。
合适的四配位铂系和钯系络合物还包括通用分子式Ⅱ-Ⅸ表示的络合物。
在通用分子式Ⅱ-Ⅸ中:
M表示二价铂或二价钯金属离子;
R1,R2,R3,R4,R5和R6各独立表示氢基、卤素基、羟基、硝基、腈基、硫醇基或含有一个到四个碳原子的烷基、烷氧基、氨基或芳香基;
每个n是独立的整数,在被允许的情况下;
Y1a,Y1b,Y1c,Y1d,Y2a,Y2b,Y2c,Y3a,Y3b,Y3c,Y4a,Y4b,Y4c,Y5a, Y5b,Y5c,Y5d,Y6a,Y6b,Y6c,和Y6d各独立表示碳、氮和硅;
U1和U2各独立表示NR,O,S,其中R都独立代表氢基、卤素基、羟基、硝基、腈基、硫醇基或含有C1-C4烷基、烷氧基、氨基或芳香基;
U3和U4各独立表示氮,磷;
X表示O,S,NR,CRR',SiRR',PR,BR,S=O,O=S=O,Se,Se=O,或O=Se=O,其中R和R'都独立代表氢基、卤素基、羟基、硝基、腈基、硫醇基或含有C1-C4烷基、烷氧基、氨基或芳香基;
通用分子式Ⅱ-Ⅸ的络合物示例如下所示:
如本文所述,"替代"一词考虑包括有机化合物的所有允许替代物。在广义上,允许的替代物包括非环化和环化、分枝和无分枝、碳环和杂环,以及有机化合物的芳香和非芳烃替代物。例如,说明性替代部分包括下文所述的替换内容。对于适当的有机化合物,允许的替代物可以是一种或多种,相同或不同的有机物。就本公开专利而言,杂原子,例如氮,可以为具有氢替代物和/或此处所述满足杂原子价的任何允许替代物。这种披露不应受到允许的有机化合物替代物的任何限制。此外,"替代"或"替代"一词包括隐含条件,即这种替换符合替代原子和替代物的允许价态,并且替代可以稳定的化合物,例如,不自发地进行转换的化合物,如重新排列、环化、消除等。此外,在某些方面,除非明确表明相反,否则可以进一步选择替代(例如:进一步取代或未取代)。
在定义各种术语时,"R1","R2",“R3",“R4"”等在此处用作通用符号,以表示各种特定的替代项。这些符号可以是任何替代的,并不限于本文中披露的符号,当它们被定义为一个实例中的某些替代项时,它们可以在另一个实例中定义为其他一些替代项。
此处使用的"C1-C4烷基"是一个分支或未分支的饱和烃组,由1至4 个碳原子组成,如甲基、乙基、n-丙基、异丙基、n-丁基、异丁基、 s-丁基和t-丁基。烷基组也可以取代或未取代。例如,烷基组可以替代一个或多个组,包括但不限于烷基、环碱、烷基、氨基、氨醚、卤化物、羟基、硝基或硫醇。
此处用的术语"烷氧"和"烷氧基"是指通过醚键连接的烷基或环烷基;也就是说,"烷基"组可以定义为—OA1,其中A1为烷基或环烷基。
此处使用的术语"芳烃基"是包含任何碳基芳烃组的组,包括但不限于苯、石脑油、苯、双苯、苯甲苯等。术语"芳烃基"还包括"杂芳基",它被定义为包含一个芳香基的基团,该基团在芳香基的环中至少包含一个杂原子。杂原子的示例包括但不限于氮、氧、硫和磷。同样," 非杂芳基"一词也包含在术语"芳烃基"中,它定义了一个包含不含杂原子的芳香基。芳烃基可以替换或未替换。芳烃基可以替换为一个或多个基团,包括但不限于,烷基,杂烷基,烷氧基,烯基,杂烯基,炔基,环炔基,芳基,杂芳基,醛,氨基酸,羧酸,酯,醚,卤素,羟基,酮,叠氮,硝基,硅基,磺胺,或硫醇等。
此处使用的术语"胺"或"亚胺"由公式—NA1A2表示,其中A1和A2可以独立地代表氢或烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基、杂芳基。
此处使用的"烷胺基"一词由此处由公式—NH(—烷基)表示,其中烷基已在文中有所所述的。代表性的例子包括但不限于,甲基亚胺,乙酰亚胺,丙亚胺,异丙亚胺,丁亚胺,异丁亚胺,二级丁亚胺,叔丁亚胺,戊亚胺,异戊亚胺,叔戊亚胺,六丁亚胺等。
此处使用的"二烷胺基"一词由公式—N(—烷基)2表示,其中烷基已在文中有所所述的。代表性的例子包括但不限于,二甲基亚胺,二乙基亚胺,二丙基亚胺,二异丙基亚胺,二丁亚胺,二异丁基亚胺,二叔丁基亚胺,二戊丁基亚胺,二异戊基亚胺,二叔戊基亚胺,二己基亚胺,N-乙基-N-甲基亚胺,N-乙基-N-丙基亚胺等。
此处使用的"卤化物"一词包括氟化物、氯化物、溴化物和碘化物。
此处使用的"羟基"一词由公式-OH表示。
此处使用的术语"叠氮化合物"一词由公式-N3表示。
此处使用的术语"硝基"一词由公式-NO2表示。
此处使用的"氰化物"一词由公式-CN表示。
此处使用的"硫醇"一词由公式-SH表示。
"R1","R2","R3","Rn",其中n是一个整数,如本文所用,可以独立地拥有上面列出的一个或多个取代基。例如,如果R1是一个直链烷基组,则烷基组的氢原子可以选择用羟基、烷基、烷基、卤素等替代。根据所选取代基的不同,第一个取代基可以合并在第二个取代基中,或者,第一取代基可以吊坠(即附加)到第二个取代基中。例如,使用短语"包含氨基酸的烷基取代基",氨基酸可以合并在烷基取代基的骨干体内。所选取代基的性质将决定第一个取代基是嵌入还是附加到第二个取代基中。
此处描述的化合物可能含有"可选替代"的部分。一般说来,"替代 "一词,无论是否以"可选"一词为前,都意味着指定部分的一个或多个氢原子被适当的替代物所取代。除非另有说明,"可选替代"在每个可替换位置可有适当的替代,并且当任何给定结构中的多个职位可以由指定组选择的多个替代者替换时,则每个职位的替换可以是相同或不同的。本披露所设想的替代物的组合最好是导致形成稳定或化学上可行的化合物的组合。此外,在某些方面,除非明确表明相反,否则可以进一步选择替代(即进一步替代或未替代)。
在某些方面,化合物的结构可以由分子式表示:
被理解为等效于分子式:
其中n通常是一个整数。也就是说,Rn被理解为代表最多五个独立的非氢原子的替代官能团,Rn(a),Rn(b),Rn(c),Rn(d),Rn(e)。通过"独立替代",这意味着每个R替代项都可以独立定义。例如,如果在一个实例中Rn(a)是卤素,则Rn(b)在该实例中不一定是卤素。
其中对R,R1,R2,R3,R4,R5,R6,等进行了多次引用。对R,R1, R2,R3,R4,R5,R6等的任何描述分别适用于任何结构或引用R,R1,R2, R3,R4,R5,R6等。
实施例
实施例1
小面积OLED器件(OLEDA)具有以下结构:ITO(100nm)/HATCN (10nm)/NPD(70nm)/Tris-PCZ(10nm)/Pd3O8-P(20nm)/BAlq(10nm) /BPyTP(50nm)/Liq(2nm)/Al(100nm),其中ITO是氧化铟锡,HATCN 是1,4,5,8,9,12-六氮杂苯并菲-六氮杂苯甲腈,NPD是N,N'-苯基苯-N,N'-bis(1-基)-1,1'-联二苯-4,4'-二元胺,Tris-PCz是9,9',9”- 三苯基-9H,9'H,9”H-3,3':6',3”-三咔唑,Pd3O8-P是选定的基于钯系的磷光材料,其全名为钯(Ⅱ)7-(3-(吡啶-2-yl-κN)苯氧基-κ C)(苯并芘[4,5]咪唑并-κN)([1,2-f]菲啶-κC),BAlq是bis(8-氢氧基-2-甲基喹啉)-(4-甲基苯氧基)铝,和BPyTP是2,7-bis(2,2'-联吡啶 -5-yl)三亚苯2,7-di(2,2′-联吡啶-5yl)三亚苯,Liq是8-羟基喹啉, Al代表铝。器件大小为2×2毫米。电荷输送层的厚度(空穴输送层、电子输送层或两者都有)被调控以增强发射光波长在570-610纳米之间的出光效率。
图5A描述了OLED A的电流密度与电压之间的关系附图。图5B显示了OLED A的在寿命测试之前和之后的电致发光光谱对比。在20毫安/ 厘米2的恒定驱动电流下(约180小时后),初始的和约95%初始值的电致发光光谱基本相同,确认在寿命测试之前和之后的器件发光颜色没有显著变化,从而证明其出色的色彩稳定性。图5C显示了OLED A的外部量子效率(EQE)与器件亮度的相关画图。图5C下部(空心圆形符号) 显示OLED A的外部量子效率与亮度的关系附图。OLED A的外部量子效率峰值为34.8%,发光亮度在20毫安/厘米2电流下达到16650尼特/米2。在10000尼特/米2的亮度下,外部量子效率任然非常高接近30%。图5C上部(实心星形符号)显示了在OLED A基板和检测器之间加入光学指标匹配胶后的器件外部量子效率与亮度的关系附图。图5D显示了OLED A的电光能量转换效率(PE)与亮度的关系附图。由于使用Pd3O8-P发光材料而带来的低工作电压特性,图5D下部(空心圆形符号)显示了电光能量转换效率达到101流明/瓦(在1000尼特/米2时)和67流明/瓦, (在10000尼特/米2时)。在OLED A基板和检测器之间加入光学指标匹配胶后,图5D上部(实心星形符号)显示了电光能量转换效率达到188 流明/瓦(在1000尼特/米2时)和142流明/瓦,(在10000尼特/米2时),证明使用外光提取层的可进一步提高器件电光能量转换效率。这种拥有高效和低滚落的外部量子效率和高电光能量转换效率的橙黄色OLED 面板展示了满足照明行业对严格高亮度性能需求的能力。
实施例2
大面积OLED面板(OLED B)具有以下结构:ITO(100nm)/HATCN (10nm)/NPD(70nm)/Tris-PCZ(10nm)/Pd3O8-P(20nm)/BAlq(10nm) /BPyTP(50nm)/Liq(2nm)/Al(100nm),其中面板实际大小为20x50 毫米。图6A下部(实心方形符号)显示了OLED B的的器件外部量子效率与电流密度的关系附图。图6A上部(空心方块符号)显示了具有外光提取层的OLED B的器件外部量子效率与电流密度的关系附图。图6A 的实心方块符号曲线在图6B中以同样方式显示出来。图6B实心三角形符号曲线显示了具有波导层的OLED B的器件外部量子效率与电流密度的关系附图。图6B空心三角形符号曲线显示了同时具有波导层和扩散膜的OLED B的器件外部量子效率与电流密度的关系附图。图6A和6B中的数据是在OLED B和检测器之间存在空气的情况下测量的。图6A的实心方块符号曲线在图6C中重现。图6C实心圆形符号曲线显示了具有使用光学指标匹配胶的波导层的OLED B的器件外部量子效率与电流密度的关系附图。图6C空心圆形符号曲线显示了同时具有使用光学指标匹配胶的波导层和扩散膜的OLED B的器件外部量子效率与电流密度的关系附图。光学指标匹配胶被用在OLED B基板和波导层之间和波导层和扩散器之间,用来增强基板与各薄膜间的光耦合效果。
OLED B(图6A)的器件效率略小于OLED A(图5C),效率差异的部分来自于OLED内部的电荷平衡差异,可能与大面积OLED B中使用的 ITO层的高电阻有关。通过在ITO和基板之间添加亚纳米网格Ag银金属层,可提高阳极层电导率来改进图6A所示的OLED器件的外部量子效率。外光提取层可将器件外部量子效率至少提高约50%。当波导层或波导层和扩散膜的组合简单地耦合到OLED基板的对面时,器件外部量子效率会降低,这是由于基板和波导层之间以及波导层与扩散膜之间的空隙存在。然而,如图6C所示,加入折射率在1.4和1.7之间光学指标匹配的粘合剂(例如聚硅烷或其他适当的透明粘性聚合物),通常消除这样的空气间隙,提高器件效率。图6A和图6C的数据比较表明,使用光学指标匹配胶的波导层和扩散膜的结合可以像商业化的外光提取层一样有效提高OLED器件外部量子效率。
实施例3
中等大小的OLED(OLED C)具有以下器件结构:ITO(100nm)/HATCN (10nm)/NPD(70nm)/Tris-PCZ(10nm)/Pd3O8-P(20nm)/BAlq(10nm) /BPyTP(50nm)/Liq(2nm)/Al(100nm),其中面板大小为10×20毫米。图7A实心方块符号曲线显示了具有内光提取层的OLED C的器件外部量子效率与电流密度的关系附图。图7A空心方块符号曲线显示了具有内光提取层和外光提取层的OLED C的器件外部量子效率与电流密度的关系附图。图7A实心方块符号曲线在图7B中重复显现。图7B实心三角形符号曲线显示了具有内光提取层和波导层的OLED C的器件外部量子效率与电流密度的关系附图。图7B空心三角形符号曲线显示了具有内光提取层和波导层/扩散膜叠层的OLED C的器件外部量子效率与电流密度的关系附图。图7A和7B中的数据是在OLED C和检测器之间存在空气的情况下测量的。图7A实心方块符号曲线在图7C中重复显现。图 7C实心圆形符号曲线显示了具有内光提取层和使用光学指标匹配胶的波导层的OLED C的器件外部量子效率与电流密度的关系附图。图7C空心圆形符号曲线显示了具有内光提取层和使用光学指标匹配胶的波导层和扩散膜的OLED C的器件外部量子效率与电流密度的关系附图。在 OLED C的基板和波导层之间和波导层与扩散膜之间加入了光学指标匹配胶。
如图7A所示,与只有内光提取层的OLED C相比,内光提取层和外光提取层的存在可使OLED C的外部量子效率增加约10-15%。图7A和7B 的比较表明,当波导层或波导层加扩散膜的组合简单地耦合到基板的对侧时,OLED C的外部量子效率会减少,这是由于基板和波导层之间以及波导层与扩散膜之间的空隙存在。但是,如图7C所示,加入光折射率在1.4和1.7之间光学指标匹配的粘合剂(例如聚硅烷或其他适当的透明粘性聚合物),通常消除这样的空气间隙,提高器件效率。图 7A和图7C的比较表明,使用光学指标匹配胶的波导层和扩散膜的结合可以像商业化的外光提取层一样有效提高OLED器件外部量子效率。
实施例4
图8A和图8B分别显示了白色LED和蓝色LED的电致发射光谱。图8C 显示了白色LED(空心方块符号)和混合LED/橙黄色OLED器件的电致发射光谱。OLED器件(OLED D)的结构如下:ITO(100nm)/HATCN(10nm) /NPD(70nm)/Tris-PCZ(10nm)/Pd3O8-P(20nm)/BAlq(10nm)/BPyTP (50nm)/Liq(2nm)/Al(100nm),其中器件大小为20×50毫米。混合器件具有波导层和扩散膜,并且在基板与波导层之间和波导层与扩散膜之间使用了光学指标匹配胶。OLED D器件的驱动电流密度为0.1 毫安/厘米2(实心圆形符号)、0.2毫安/厘米2(空心三角形符号)、 0.5毫安/厘米2(实心钻石符号)和0.7毫安/厘米2(实心方块符号)。如图8C所示,通过单独控制LED和橙黄色OLED的驱动电流,可以调控器件电致发射光谱从具有单独LED发射的冷白色(空心方块符号)改为橙黄色OLED发射占多数的暖白色(实心方块符号)。
虽然本文披露包含许多具体的实施案例细节,但这些细节不应解释为对主题事项的范围或可声称的范围的限制,而应解释为对可能特定于特定实施案例的特征的描述。在单独实施案例的上下文中描述的某些特征也可以在单个实施案例中组合实现。相反,在单个实施案例上下文中描述的各种特征也可以分别在多个实施案例或任何合适的子组合中实现。此外,虽然前面描述的功能可以描述为在某些组合中作用,甚至最初声称是这样的,但在某些情况下,声称组合中的一个或多个功能可以从组合中删去,并且所述组合可能指向子组合或子组合的变体。
已对主题的具体实施案例进行说明。所述实施案例的其他实施案例、变更和排列属于以下权利要求的范围,对本领域技术人员来说,这是显而易见的。虽然操作按特定顺序在图纸或权利要求中描述,但不应理解为要求按显示的特定顺序或顺序执行此类操作,或执行所有图示操作(某些操作可视为可选操作),以实现理想的结果。
因此,前面描述的示例实施案例不定义或约束此披露。其他更改、替换和变更也可能发生,且不会偏离本发明披露的精神和范围。
Claims (23)
1.可调颜色LED-OLED混合引导照明设备,其特征在于,包括:
波导层;
发光二极管(LED)阵列与波导层光耦合;以及有机发光二极管(OLED)阵列,
其中:从LED阵列发出的光从波导层的边缘射入,从OLED阵列发出的光从波导层的第一表面射入,从LED阵列发出的光和从OLED阵列发出的光穿过波导层第一表面对面的第二表面,照明设备发出的光包括LED阵列发出的光和OLED阵列发出的光。
2.如权利要求1所述的照明设备,其特征在于,其中LED阵列发出的光在可见光谱的蓝色范围内。
3.如权利要求1所述的照明设备,其特征在于,其中OLED阵列发出的光在可见光谱的黄色或橙黄色范围内。
4.如权利要求1所述的照明设备,其特征在于,其中照明设备发出的光为白光。
5.如权利要求4所述的照明设备,其特征在于,其中白光为暖白光或冷白光。
6.如权利要求1所述的照明设备,其特征在于,其中照明设备发出的光是可调的。
7.如权利要求1所述的照明设备,其特征在于,其中LED阵列和OLED阵列的发光强度可独立控制。
8.如权利要求1所述的照明设备,其特征在于,进一步包括有直接接触波导层第一表面的反射层。
9.如权利要求1所述的照明设备,其特征在于,进一步包括有直接接触波导层第二表面的扩散膜。
10.如权利要求1所述的照明设备,其特征在于,进一步包括在扩散膜和波导层第二表面之间使用的光学指标匹配粘合剂。
11.如权利要求1所述的照明设备,其特征在于,其中OLED阵列的反射金属电极位于波导层和制造OLED阵列的基板之间。
12.如权利要求1所述的照明设备,其特征在于,其中波导层和OLED阵列的光透射电极被制造OLED阵列的基板隔开。
13.如权利要求1所述的照明设备,其特征在于,其中LED阵列发出的光从波导层的边缘射入。
14.如权利要求1所述的照明设备,其特征在于,其中OLED阵列发出的光从波导层的背面射入。
15.如权利要求1所述的照明设备,其特征在于,其中包括波导层的LED扩散发光器结构中还包括有棱镜保护膜、伦兹膜、棱镜膜或它们的任何组合。
16.如权利要求1所述的照明设备,其特征在于,其中OLED阵列进一步包括有内光提取层、外光提取层或两者都有。
17.如权利要求16所述的照明设备,其特征在于,其中OLED结构包括内光提取层、外光提取层和内光提取层与外光提取层之间的基板。
18.如权利要求1所述的照明设备,其特征在于,其中OLED阵列中每个OLED都选择一个特定微腔长度,用于为黄色或橙黄色光的发射提供共振条件。
19.如权利要求1所述的照明设备,其特征在于,其中波导层的边缘与波导层的第一表面大致垂直。
20.如权利要求1所述的照明设备,其特征在于,其中波导层的边缘保持与第一表面和第二表面同样长度。
21.如权利要求1所述的照明设备,其特征在于,其中OLED阵列是在波导层上制成的。
22.如权利要求1所述的照明设备,其特征在于,其中OLED阵列中的每个OLED都包含有一个由通用分子式Ⅰ表示的发光材料:
其中:
M表示二价铂或二价钯金属离子;
各R1,R3,R4和R5独立表示氢基、卤素基、羟基、硝基、氰基、硫醇基或可选替代的含有C1-C4烷基、烷氧基、氨基或芳香基;
每个n是独立的整数,在被允许的情况下;
Y1a,Y1b,Y1c,Y1d,Y1e,Y1f,Y2a,Y2b,Y2c,Y2d,Y2e,Y2f,Y4a,Y4b,Y4c,Y4d,Y4e,Y5a,Y5b,Y5c,Y5d和Y5e独立表示碳、氮、硅、氧、硫;
X2表示NR,PR,CRR',SiRR',CRR',SiRR',O,S,S=O,O=S=O,Se,Se=O,或O=Se=O,其中R和R'可以独立代表氢基、卤素基、羟基、硝基、氰基、硫醇基或含有C1-C4烷基、烷氧基、氨基或芳香基或杂芳香基;
每个L1和L3都可以独立存在或不存在,如果存在,则表示已取代或未取代的连结原子或连结官能团,其中已取代的连结原子可以与烷基、烷氧基、烷烃基、烷炔基、羟基、胺基、酰胺基、硫醇、芳香基、杂芳香基、环烷基或杂环烷基相结合;
Ar3和Ar4各独立代表一个六元环为基础的芳香环;
Ar1和Ar5各独立代表一个五元到十元的芳香环、杂芳香环、共轭芳香环或共轭杂芳香环。
23.如权利要求1所述的照明设备,其特征在于,其中OLED阵列中的OLED都包含有一个由通用分子式Ⅱ-Ⅸ表示的发光材料:
其中:
M表示二价铂或二价钯金属离子;
R1,R2,R3,R4,R5和R6各独立表示氢基、卤素基、羟基、硝基、腈基、硫醇基或含有一个到四个碳原子的烷基、烷氧基、氨基或芳香基;
每个n是独立的整数,在被允许的情况下;
Y1a,Y1b,Y1c,Y1d,Y2a,Y2b,Y2c,Y3a,Y3b,Y3c,Y4a,Y4b,Y4c,Y5a,Y5b,Y5c,Y5d,Y6a,Y6b,Y6c,和Y6d各独立表示碳、氮和硅;
U1和U2各独立表示NR,O,S,其中R都独立代表氢基、卤素基、羟基、硝基、腈基、硫醇基或含有C1-C4烷基、烷氧基、氨基或芳香基;
U3和U4各独立表示氮,磷;
X表示O,S,NR,CRR',SiRR',PR,BR,S=O,O=S=O,Se,Se=O,或O=Se=O,其中R和R'都独立代表氢基、卤素基、羟基、硝基、腈基、硫醇基或含有C1-C4烷基、烷氧基、氨基或芳香基。
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