CN103443935A - 带有增益（ec）的上转换器件和光检测器 - Google Patents

带有增益（ec）的上转换器件和光检测器 Download PDF

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CN103443935A
CN103443935A CN2012800105089A CN201280010508A CN103443935A CN 103443935 A CN103443935 A CN 103443935A CN 2012800105089 A CN2012800105089 A CN 2012800105089A CN 201280010508 A CN201280010508 A CN 201280010508A CN 103443935 A CN103443935 A CN 103443935A
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弗兰基·索
金渡泳
普拉丹·布哈本德拉
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Nanoholdings LLC
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Abstract

本发明的实施方案涉及带有增益的IR光检测器，其产生自将电荷倍增层（CML）置于光检测器的阴极和IR敏化层之间，其中在CML处累积的电荷降低了阴极和CML之间的能差以促进电子的注入，这导致了单载子电子元件的增益。本发明的其它实施方案涉及将带有增益的IR光检测器纳入可用在夜视和其它应用中的IR至可见光上转换器件中。

Description

带有增益(EC)的上转换器件和光检测器
相关申请的交叉引用
本申请要求2011年2月28日提交的美国临时申请序列号No.61/447,406的权益，其全部内容（包括任何插图、表格或附图）都通过引用并入本文中。
背景技术
现有的夜视镜是加强现有的光而不是依靠其自身光源的复杂光电器件。在典型的配置中，被称为物镜的常规镜头捕获环境光线和一些近红外光。然后将所收集的光送至图像增强管。图像增强管可利用光电阴极将光能的光子转换成电子。当电子穿过管时，可以有更多的电子从管内的原子释放，使初始的电子数乘以数千的因子，其通常利用微通道板（MCP）来实现。图像增强管可定位为使得级联电子（cascaded electrons）撞击管末端的涂覆有磷光体的屏，在管的末端电子保留它们所穿过的通道的位置。电子的能量导致磷光体达到激发态并释放光子以在屏上产生绿色图像，这赋予了夜视的特征。可通过目镜（图像在此处放大并聚焦）观察绿色磷光体图像。
近来，因为光上转换器件在夜视、测距和安全性以及半导体晶片检查中的潜在应用，它们引起了人们极大的研究兴趣。早期的近红外（NIR）上转换器件主要基于其中光检测部分与发光部分串联的无机半导体异质结结构。上转换器件主要通过光检测的方法来区别。器件的上转换效率通常非常低。例如，一种集成了发光二极管（LED）和基于半导体的光检测器的近红外-可见光上转换器件表现出仅有0.048(4.8%)W/W的最大外部转换效率。混杂型有机/无机上转换器件（其中InGaAs/InP光检测器与有机发光二极管（OLED）耦联）表现出0.7%W/W的外部转换效率。目前无机上转换器件和混合上转换器件的制造非常昂贵，并且用于制造这些器件的工艺不适宜大面积应用。人们正在努力实现具有更高转换效率的低成本上转换器件，然而尚未确认存在可能具有足够效率的用于实用上转换器件的器件。因此，仍然需要上转换器件实现更高的效率，所述上转换器件能够使用目前可用的红外光检测器和发光材料并且可以以具有成本效益的方式制造。
发明内容
本发明的实施方案涉及带有增益的IR光检测器，其包含阴极、IR敏化材料层、电荷倍增层（CML）和阳极。CML将IR敏化材料层和阴极分隔开并在无IR辐射的情况下具有比阴极的费米能级高0.5eV以上的LUMO能级。或者，CML将IR敏化材料层与阳极分隔开并在无IR辐射的情况下具有比阳极费米能级低0.5eV以上的HOMO能级。在本发明的实施方案中，IR敏化材料层包含PCTDA、SnPc、SnPc:C60、AlPcCl、AlPcCl:C60、TiOPc、TiOPc:C60、PbSe QDs、PbS QDs、PbSe、PbS、InAs、InGaAs、Si、Ge或GaAs，且CML包含萘四羧酸酐（NTCDA）、2,9-二甲基-4,7-二苯基-1,10-菲咯啉（BCP）、对-双(三苯基甲硅烷基)苯（UGH2）、4,7-二苯基-1,10-菲咯啉（BPhen）、三-(8-羟基喹啉)铝（Alq3）、3,5’-N,N’-二咔唑-苯（mCP）、C60、三[3-(3-吡啶基)
Figure BDA00003719530600021
基]硼烷（3TPYMB）、ZnO或TiO2。在本发明的其它实施方案中，IR敏化材料层包含PbSe QDs和PbS QDs，且CML包含油酸、乙酰胺（actylamine）、乙硫醇、乙二硫醇（ethandithiol，EDT）、或苯二硫醇（bensenedithiol，BTD）。带有增益的IR光检测器可进一步包含将IR敏化材料层与阳极分隔开的空穴阻挡层。
本发明的其它实施方案涉及带有增益的上转换器件，其包含带有增益的IR光检测器和有机发光二极管（OLED）。OLED包含阴极、电子传输层（ETL）、发光层（LEL）、空穴传输层（HTL）和阳极。ETL包含三[3-(3-吡啶基)-
Figure BDA00003719530600022
基]硼烷（3TPYMB）、2,9-二甲基-4,7-二苯基-1,10-菲咯啉（BCP）、4,7-二苯基-1,10-菲咯啉（BPhen）、或三-(8-羟基喹啉)铝（Alq3）。发光层（LEL）包含三(2-苯基吡啶)合铱、Ir(ppy)3、聚[2-甲氧基,5-(2’-乙基-己氧基)亚苯基亚乙烯基]（MEH-PPV）、三-(8-羟基喹啉)铝（Alq3），或双-[(4,6-二氟苯基)-吡啶-N,C2’]吡啶甲酰合铱(III)（FIrpic）。HTL包括1,1-双[(二-4-甲苯基氨基)苯基]环己烷（TAPC）、N,N’-二苯基-N,N’-(2-萘基)-(1,1’-苯基)-4,4’-二胺（NPB）或N,N’-二苯基-N,N’-二(间甲苯基)联苯胺（TPD）。带有增益的上转换器件可进一步包含将带有增益的IR光检测器和OLED分开的互连层。互连层包含薄金属或堆叠互连层。
附图说明
图1示出了带有增益的IR光检测器的示意性能带图，根据本发明的实施方案，a)在IR敏化层和阳极之间没有空穴阻挡层，b)在IR敏化层和阳极之间有空穴阻挡层。
图2示出了根据本发明的实施方案的带有增益的IR光检测器的示意性能带图，a)在黑暗中，在施加的电压下，b)在施加的电压下在初始IR辐射下，和c)在施加的电压和IR辐射下，其中电荷倍增层（CML）中的空穴积聚降低了能级差，这降低或消除了其LUMO和阴极费米能级之间的能量差，从而促进了电子从阴极的注入。
图3示出了a)根据本发明的实施方案，具有有机IR敏化层的IR光检测器，以及光检测器的增益作为电压的函数的曲线图，和b)根据本发明的实施方案，具有无机IR敏化层的IR光检测器，以及在不同施加电压下光检测器的增益作为波长的函数的曲线图。
图4示出了根据本发明实施方案，带有增益的红外-可见光上转换器件的示意性能带图。
图5示出了根据本发明实施方案，带有增益的红外至可见光上转换器件的示意性能带图，a)在黑暗中，在施加电压下，b)在施加电压下在初始IR辐射下，和c)在施加的电压和IR辐射下，其中CML中的空穴积聚降低了能级差，这降低或消除了其LUMO和阴极费米能级之间的能量差，使得将阴极注入的电子和光检测器产生的电子提供至可见光发光层（LEL）。
具体实施方式
本发明的实施方案涉及上转换器件，其包含带有增益的光检测器。通过增益的施加，可将来自IR光检测器的信号放大使得上转换器件的光发射器发射强度更高、对比度更大。本发明的实施方案涉及通过将光检测器与电荷倍增层（CML）耦合来实现增益。带有增益的光检测器示意图在图1a中示出，其中IR敏化层、光检测器通过CML与阴极分隔开，所述CML的特征在于相对于阴极功函数的深的最高占据分子轨道（HOMO）和最低未占据分子轨道（LUMO）的能级，这导致在没有IR辐射的情况下，注入势垒为至少0.5eV。任选地，如图1b所示，在本发明的实施方案中，空穴阻挡层（HBL）位于IR敏化层和阳极之间。
根据本发明的实施方案，带有增益的光检测器运行的方式在图2a中示意性地示出。如图2a所示，随着在黑暗中施加偏压，没有IR辐射照亮IR敏化层，由于CML的势垒≥0.5eV，所以很少或没有电子从阴极注入。如图2所示，该器件是作为单载子电子元件（electron only device）。尽管该器件和本公开大部分的器件都涉及单载子电子元件，本领域的技术人员应理解，作为单载子空穴元件（hole only device）的器件在没有IR辐射的情况下可以以类似的方式，通过施加反向电偏压和CML（其能级相对于阳极功函数促进电子的积聚而不是空穴的积聚）构造带有增益的器件。如图2b所示，IR辐射后，IR敏化层产生电子-空穴对，伴随着电子因施加的偏压流向阳极。如图2c所示，光生空穴的反向流动导致在CML处空穴的积聚，这将电子注入CML的势垒降低至小于0.5eV，并在施加的偏压下显著地增大了朝向阳极的电子电流。
在本发明的实施方案中，IR光检测层可以是无机的。在一个示例性的上转换器件中，可采用PbSe量子点（QDs）层作为IR光检测器，而可采用MEH-PPV作为场致发光OLED。除PbSe之外，其它可采用的QDs包括但不限于PbS。其它可用作IR光检测器的无机材料包括但不限于下列物质的连续薄膜：PbSe、PbS、InAs、InGaAs、Si、Ge或GaAs。在本发明的实施方案中，IR光检测器是含有机物的材料或含有机金属的材料，包括但不限于苝-3,4,9,10-四羧酸-3,4,9,10-二酐（PTCDA）、酞菁锡(II)（SnPc）、SnPc:C60、酞菁氯化铝（AlPcCl）、AlPcCl:C60、酞菁氧钛（TiOPc）和TiOPc:C60。
通过包含CML，IR光检测器显示增益使得上转换器件的效率提高。一个示例性的CML是萘四羧酸酐（NTCDA）。在本发明的实施方案中，其它可采用的CML包括但不限于2,9-二甲基-4,7-二苯基-1,10-菲咯啉（BCP）、对-双(三苯基甲硅烷基)苯（UGH2）、4,7-二苯基-1,10-菲咯啉（BPhen）、三-(8-羟基喹啉)铝（Alq3）、3,5’-N,N’-二咔唑-苯（mCP）、C60、三[3-(3-吡啶基)-
Figure BDA00003719530600041
基]硼烷（3TPYMB）、ZnO或TiO2。尽管IR光检测器是无机的，但是CML可以是有机配体，如对无机光敏材料进行封端的油酸。CML的包含显著地提高了光检测器的效率。例如，如图3a所示，利用PTCDA IR敏化层和NTCDA CML，当在电极之间施加-20V的电压时，观察到超过100的增益。使用PbSe QDs作为光检测器和油酸（有机配体），小的电势（-1.5V）足以在近红外产生高达6倍的增益，如图3b所示。
本发明的其它实施方案涉及具有光检测器的上转换器件，所述光检测器通过纳入CML而带有增益。在图4中示出了根据本发明的实施方案的上转换器件的示例性的示意性能带图。除IR光检测器和CML之外，上转换器件包含阳极、阴极、发光层、空穴传输层和电子传输层。阳极可以是但不限于铟锡氧化物（ITO）、铟锌氧化物（IZO）、铝锡氧化物（ATO）、铝锌氧化物（AZO）、碳纳米管和银纳米线。可用作发光层的材料包括但不限于三(2-苯基吡啶)合铱、Ir(ppy)3、聚[2-甲氧基，5-(2’-乙基-己氧基)亚苯基亚乙烯基]（MEH-PPV）、三-(8-羟基喹啉)铝（Alq3），和双-[(4,6-二氟苯基)-吡啶-N,C2’]吡啶甲酰合铱(III)（FIrpic）。阴极可以是LiF/Al或可以是任意具有适当功函数的导体，包括但不限于Ag、Ca、Mg、LiF/Al/ITO、Ag/ITO、CsCO3/ITO和Ba/Al。可用作电子传输层的材料包括但不限于三[3-(3-吡啶基)基]硼烷（3TPYMB）、2,9-二甲基-4,7-二苯基-1,10-菲咯啉（BCP）、4,7-二苯基-1,10-菲咯啉（BPhen）和三-(8-羟基喹啉)铝（Alq3）。可用作空穴传输层的材料包括但不限于1,1-双[(二-4-甲苯基氨基)苯基]环己烷（TAPC）、N,N’-二苯基-N,N’-(2-萘基)-(1,1’-苯基)-4,4’-二胺（NPB）和N,N’-二苯基-N,N’-二(间甲苯基)联苯胺（TPD）。本领域的技术人员可容易地通过阳极、阴极、IR光检测器、发光层、空穴传输层和电子传输层的相对功函数、HOMO和LUMO能级、层的相容性和在其制造过程中所用的任意所需的沉积方法的性质来确定阳极、阴极、IR光检测器、发光层、空穴传输层和电子传输层的适当组合。如图5中所示，还可包括互连层，其中互连层将上转换器件的IR光检测部分与器件的发光部分连接。当存在互连层时，所述互连层可以是薄金属（例如约0.5nm至3nm厚的Al、Ag或Au）或者包含n型掺杂有机层/薄金属互连层/p型掺杂有机层的堆叠互连层，其中：n型掺杂有机层可以是但不限于Cs2CO3掺杂的Bphen、Cs2CO3掺杂的BCP、Cs2CO3掺杂的ZnO、Li掺杂的Bphen、Li掺杂的BCP、LiF掺杂的Bphen、LiF掺杂的BCP；薄金属互连层可为约0.5nm至3nm厚的Al、Ag或Au；而p型掺杂有机层可以是但不限于MoO3掺杂的TAPC、MoO3掺杂的NPB、HAT CN掺杂的TAPC或HAT CN掺杂的NPB。
如图5中所示，上转换器件使得仅当IR敏化层产生空穴和电子时电子能够流向发光层（LEL），以便除了通过IR敏化层产生的电子流之外，CML还通过来自阴极的电子流促进增益。在图5中，电子传输层还作为相对于IR敏化层的空穴阻挡层。如图5中所示，互连层提供在如图5中所示的单载子电子元件中来自光检测器的电子传输。本领域的技术人员可理解的是，单载子空穴元件中互连层可提供空穴传输。
近来，包括部分本发明人的研究组已在2010年5月24日提交的美国临时申请No.61/347696（通过引用并入本文）中公开了具有改善效率的含有位于阳极和IR检测层之间的空穴阻挡层（HBL）的红外-绿光上转换器件。例如，可将HBL层放置在ITO阳极和SnPc:C60IR敏化层之间，以有效阻挡来自ITO阳极的空穴载流子，在施加足够高的电压和IR辐射之前抑制上转换器件的可见亮度。在包含HBL的本发明实施方案中，HBL可为有机化合物或无机化合物。有机HBL可包含例如在黑暗和IR辐射下的2,9-二甲基-4,7-二苯基-1,10-菲咯啉（BCP）或对-双(三苯基甲硅烷基)苯（UGH2）。这些HBL材料具有深HOMO能级。因为这些材料也具有小的LUMO能量，空穴阻挡层和IR敏化层之间的电荷产生可以忽略。除了BCP和UGH2，其它可用在本发明实施方案中的有机空穴阻挡层包括但不限于4,7-二苯基-1,10-菲咯啉（BPhen）、三-(8-羟基喹啉)铝（Alq3）、3,5’-N,N’-二咔唑-苯（mCP）、C60和三[3-(3-吡啶基)
Figure BDA00003719530600061
基]硼烷（3TPYMB）。在包括无机HBL的本发明实施方案中，无机化合物可为ZnO或TiO2。可用作电子传输层的材料包括但不限于三[3-(3-吡啶基)
Figure BDA00003719530600062
基]硼烷（3TPYMB）、2,9-二甲基-4,7-二苯基-1,10-菲咯啉（BCP）、4,7-二苯基-1,10-菲咯啉（BPhen）和三-(8-羟基喹啉)铝（Alq3）。
本发明的实施方案涉及用于检测红外（IR）辐射并提供可见光输出的方法和装置。由于它们与轻便坚固的柔性塑料基底的相容性，根据本发明实施方案中的上转换装置可在许多应用中用作组件，例如像素，所述应用包括但并不限于夜视、测距、安全性和半导体晶片检查。
方法和材料
面积为0.04cm2的带增益有机光检测器在薄层电阻为每平方20Ω的图案化ITO基底上制造。ITO基底在超声清洗机中用丙酮和异丙醇清洗，用去离子水漂洗，用N2气体吹干，并用UV臭氧处理15分钟。PTCDA和NTCDA通过梯度升华（train sublimation）两次或三次而纯化。带有增益的有机光检测器具有ITO/NTCDA（50nm）/PTCDA（300nm）/NTCDA（50nm）/Au（100nm）结构，其中顶部三层PTCDA、NTCDA和Au分别是光敏化层、CML和顶部电极，并以
Figure BDA00003719530600063
的速率在1×10-6托的压力下真空沉积。所有的层都在1×10-6托的压力下真空沉积。
利用来自Lasermate Group，Inc.的532nm波长的绿色激光在黑暗中和在辐射下测量电流密度-电压（J-V）的特性。使用中性密度的过滤器和Newport Optical Power Meter 840-E来控制100μW/cm2的光强。增益按照通过光照而流经器件的电荷载流子数与被有机膜吸收的光子数的比率计算。Au电极接地并在ITO电极上施加电压偏压。在空气中没有封装的情况下进行器件的测量。
面积为0.04cm2的带增益有机光检测器在薄层电阻为每平方20Ω的图案化ITO基底上制造。将具有油酸封端基团的PbSe纳米晶体在氮手套箱中旋涂在经UV-臭氧处理的ITO涂覆玻璃基底上。在～10-6托的压力下通过有效面积为4mm2的遮光板热沉积100nm厚的Al阴极。最终的器件具有ITO/具有油酸封端配体的PbSe/Al的结构。
用Keithley 4200半导体参数分析仪测定器件的电流-电压（I-V）特性。器件用来自使用Oriel日光模拟器作为源的Newport单色器的单色光来辐射。使用两个经校准的Newport918D光电二极管来测量照明强度，一个用于光谱的可见部分，而另一个用于光谱的红外部分。入射辐射的强度通过使用一组中性密度过滤器来改变。为获得光检测器的光谱响应，来自单色器的光在400Hz斩波来调制光信号。作为偏置电压函数的光电流响应使用Stanford Research System SR810 DSP锁相放大器进行测量。
本文提及或引用的所有专利、专利申请、临时申请和出版物的全部内容（包括所有的图和表格）在它们不与本说明书的明确教导相矛盾的程度上，都通过引用并入本文。
应理解，本文所描述的实施例和实施方案仅用于说明目的，根据其向本领域技术人员建议了多种修改和变化，并且这些修改和变化包括在本申请的精神和范围内。

Claims (19)

1.一种带有增益的IR光检测器，其包含阴极、IR敏化材料层、电荷倍增层（CML）和阳极，其中所述CML使所述IR敏化材料层分隔于所述阴极并在无IR辐射的情况下具有比所述阴极的费米能级高0.5eV以上的LUMO能级，或者所述CML使所述IR敏化材料层分隔于所述阳极并在无IR辐射的情况下具有比所述阳极的费米能级低0.5eV以上的HOMO能级。
2.根据权利要求1所述的带有增益的IR光检测器，其中所述阴极包含Ag、Ca、Mg、铟锡氧化物（ITO）、铟锌氧化物（IZO）、铝锡氧化物（ATO）、铝锌氧化物（AZO）、LiF/Al/ITO、Ag/ITO、CsCO3/ITO、碳纳米管或银纳米线。
3.根据权利要求1所述的带有增益的IR光检测器，其中所述IR敏化材料层包含PCTDA、SnPc、SnPc:C60、AlPcCl、AlPcCl:C60、TiOPc、TiOPc:C60、PbSe QDs、PbS QDs、PbSe、PbS、InAs、InGaAs、Si、Ge或GaAs。
4.根据权利要求1所述的带有增益的IR光检测器，其中所述CML包含萘四羧酸酐（NTCDA）、2,9-二甲基-4,7-二苯基-1,10-菲咯啉（BCP）、对-双(三苯基甲硅烷基)苯（UGH2）、4,7-二苯基-1,10-菲咯啉（BPhen）、三-(8-羟基喹啉)铝（Alq3）、3,5’-N,N’-二咔唑-苯（mCP）、C60、三[3-(3-吡啶基)
Figure FDA00003719530500011
基]硼烷（3TPYMB）、ZnO或TiO2。
5.根据权利要求1所述的带有增益的IR光检测器，其中所述阳极包含Ag、Ca、Mg、铟锡氧化物（ITO）、铟锌氧化物（IZO）、铝锡氧化物（ATO）、铝锌氧化物（AZO）、LiF/Al/ITO、Ag/ITO、CsCO3/ITO、碳纳米管或银纳米线。
6.根据权利要求1所述的带有增益的IR光检测器，其中所述IR敏化材料层包含PbSe QDs或PbS QDs，所述CML包含油酸、乙酰胺、乙硫醇、乙二硫醇（EDT）、或苯二硫醇（BTD）。
7.根据权利要求1所述的带有增益的IR光检测器，还包含使所述IR敏化材料层分隔于所述阳极的空穴阻挡层。
8.根据权利要求7所述的带有增益的IR光检测器，其中所述空穴阻挡层包含2,9-二甲基-4,7-二苯基-1,10-菲咯啉（BCP）、对-双(三苯基甲硅烷基)苯（UGH2）、4,7-二苯基-1,10-菲咯啉（BPhen）、三-(8-羟基喹啉)铝（Alq3）、3,5’-N,N’-二咔唑-苯（mCP）、C60、三[3-(3-吡啶基)
Figure FDA00003719530500021
基]硼烷（3TPYMB）、ZnO或TiO2。
9.带有增益的上转换器件，包含权利要求1所述的带有增益的IR光检测器和有机发光二极管（OLED）。
10.根据权利要求9所述的带有增益的上转换器件，其中所述OLED包含所述阴极、电子传输层（ETL）、发光层（LEL）、空穴传输层（HTL）和所述阳极。
11.根据权利要求10所述的带有增益的上转换器件，其中所述阴极包含Ag、Ca、Mg、铟锡氧化物（ITO）、铟锌氧化物（IZO）、铝锡氧化物（ATO）、铝锌氧化物（AZO）、LiF/Al/ITO、Ag/ITO、CsCO3/ITO、碳纳米管或银纳米线。
12.根据权利要求10所述的带有增益的上转换器件，其中所述ETL包含三[3-(3-吡啶基)
Figure FDA00003719530500022
基]硼烷（3TPYMB）、2,9-二甲基-4,7-二苯基-1,10-菲咯啉（BCP）、4,7-二苯基-1,10-菲咯啉（BPhen）或三-(8-羟基喹啉)铝（Alq3）。
13.根据权利要求10所述的带有增益的上转换器件，其中所述发光层（LEL）包含三(2-苯基吡啶)合铱Ir(ppy)3、聚[2-甲氧基,5-(2’-乙基-己氧基)亚苯基亚乙烯基]（MEH-PPV）、三-(8-羟基喹啉)铝（Alq3）或双-[(4,6-二氟苯基)-吡啶-N,C2’]吡啶甲酰合铱(III)（FIrpic）。
14.根据权利要求10所述的带有增益的上转换器件，其中所述HTL包含1,1-双[(二-4-甲苯基氨基)苯基]环己烷（TAPC）、N,N’-二苯基-N,N’-(2-萘基)-(1,1’-苯基)-4,4’-二胺（NPB）或N,N’-二苯基-N,N’-二(间甲苯基)联苯胺（TPD）。
15.根据权利要求10所述的带有增益的上转换器件，其中所述阳极包含铟锡氧化物（ITO）、铟锌氧化物（IZO）、铝锡氧化物（ATO）、铝锌氧化物（AZO）、碳纳米管或银纳米线。
16.根据权利要求9所述的带有增益的上转换器件，还包含将根据权利要求1所述的带有增益的IR光检测器分隔于所述OLED的互连层。
17.根据权利要求16所述的带有增益的上转换器件，其中所述互连层包含薄金属或堆叠互连层。
18.根据权利要求17所述的带有增益的上转换器件，其中所述薄金属包含Al、Ag和Au并且具有0.1nm至3nm的厚度。
19.根据权利要求17所述的带有增益的上转换器件，其中所述堆叠互连层包含n型掺杂有机层、薄金属层和p型掺杂有机层，其中：所述n型掺杂有机层包含Cs2CO3掺杂的Bphen、Cs2CO3掺杂的BCP、Cs2CO3掺杂的ZnO、Li掺杂的Bphen、Li掺杂的BCP、LiF掺杂的Bphen或LiF掺杂的BCP；所述薄金属包含Al、Ag或Au的0.1nm至3nm厚的层；所述p型掺杂有机层包含MoO3掺杂的TAPC、MoO3掺杂的NPB、HATCN掺杂的TAPC或HAT CN掺杂的NPB。
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