CN103765588B - 集成ir上转换器件和cmos图像传感器的红外成像器件 - Google Patents
集成ir上转换器件和cmos图像传感器的红外成像器件 Download PDFInfo
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Abstract
成像器件包括在CMOS图像传感器(CIS)上的IR上转换器件,其中所述上转换器件包括透明的多层堆叠体。所述多层堆叠体包括位于透明阳极与透明阴极之间的IR敏化层和发光层。在本发明的一些实施方案中,所述多层堆叠体在通过机械紧固件或粘合剂或者通过层叠耦接到CIS的透明支持件上形成。在本发明的另一个实施方案中,所述CIS起支持衬底的作用用于多层堆叠体的形成。
Description
相关申请的交叉引用
本申请要求于2011年6月6日提交的美国临时申请序列第61/493,691号的权益,其全部内容(包括任意数字、表格或图示)都通过引用并入本文。
背景技术
最近,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,所以它们吸引了极大的研究兴趣。早期的近红外(NIR)上转换器件主要基于其中光检测部件与发光部件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NIR-可见光上转换器件表现出的最大外部转换效率仅为0.048(4.8%)W/W。其中将InGaAs/InP光检测器耦接至有机发光二极管(OLED)的混合有机/无机上转换器件表现出的外部转换效率为0.7%W/W。
目前,无机上转换器件和混合上转换器件的制造昂贵,并且用于制造这些器件的工艺不适宜大面积应用。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际上转换器件的器件。对于一些应用(例如,夜视器件),非常期望的是具有宽吸收光谱的红外(IR)敏化层的上转换器件。另外,期望的是在无需月光或任意额外照明源的情况下放大信号。
发明内容
本发明的一些实施方案涉及成像器件,其包括具有多层堆叠结构的透明红外(IR)-可见光上转换器件和CMOS图像感应器(CIS)。所述堆叠层结构包括透明阳极、至少一个空穴阻挡层、IR敏化层、至少一个空穴传输层(HTL)、发光层(LED)、至少一个电子传输层(ETL)和透明阴极。另外,所述上转换器件可包括抗反射层和/或IR透过的可见光阻挡层。多层堆叠体可形成在衬底上。衬底可以是CIS。衬底可以是刚性的支撑层并且上转换器件与CIS通过机械紧固件或粘合剂耦接;或者支撑层可以是柔性的并且上转换器件被层叠至CIS以形成成像器件。
附图说明
图1是根据本发明一个实施方案的待与CMOS图像传感器(CIS)一起使用的红外-可见光上转换器件的截面示意图。
图2是图1的上转换器件的能带图。
图3示出可组合为根据本发明一个实施方案的成像器件的红外(IR)敏化层的多种直径的PBSeQD的吸收光谱复合图,其中插图示出50nm厚的单分散PbSe膜的吸收光谱和该膜的TEM图像。
图4示出如在本发明一个实施方案中可使用的近红外(NIR)照明下的插图所说明的,透明上转换器件对于不同偏压的转换效率的复合曲线图。
图5举例说明了根据本发明一个实施方案的成像器件的构造,其中刚性上转换器件与CIS耦接。
图6举例说明了根据本发明一个实施方案的成像器件的构造,其中柔性上转换器件被层叠至CIS。
图7举例说明了根据本发明一个实施方案的成像器件,其中上转换器件直接在CIS衬底上形成。
具体实施方式
本发明的一些实施方案涉及红外(IR)敏化层与可见光发光层耦接的上转换器件,所述上转换器件在CMOS图像传感器(CIS)上形成或与其耦接。图1是包括多层堆叠体的上转换器件的示意图,所述多层堆叠体包括夹在阴极与阳极之间的IR敏化层和产生可见光的有机发光层(LED)。图2示出根据本发明一个实施方案的上转换器件的能带图,其中空穴阻挡层***在IR敏化层与阳极之间以减少上转换器件中的暗电流。
在本发明的一个实施方案中,上转换器件使用多分散PbSe量子点(QD)的膜作为IR敏化层,其中多种尺寸的QD吸收如本文所用的IR或IR辐射,其多种吸收最大值在小于1μm至约2μm的波长范围内,以提供IR敏化层的广谱灵敏度。
图3示出的复合光谱中说明了不同尺寸的QD的不同吸收最大值。图3的插图示出在1.3μm处具有吸收峰的50nm厚的单分散PbSeQD膜的吸收光谱。然而,如图4所示,用图3的插图中示出的单分散QD构造的上转换器件的光子-光子转换效率对于NIR辐照没有实现多于数个百分比的效率,即使是在相对较高的20V的偏压下亦如此。因为转换效率在这个范围中小于10%,所以可通过放大IR输入信号或可见光输出信号来完成IR信号的合理探测。
在本发明的一些实施方案中,通过使上转换器件耦接至CIS来优化输出信号。上转换器件的电极是透明的,使得进入的IR辐射传输至IR敏化层,并且进入的光和产生的光可到达上转换器件的光出射表面处CIS的表面。CIS技术是成熟的并且广泛地在用于市售数码照相机中以用于捕获图像。这些CIS具有像素,具有至少一个放大器和光检测器。通过包括CIS与上转换器件,IR产生的图像信号的放大通过与CIS耦接来实现,使得成像器件能够用于夜视应用,即使是在IR辐照源的强度低时亦如此。
图2是根据本发明一个实施方案的具有IR敏化层的上转换器件的示意性能带图,所述IR敏化层可以是包括多分散QD的宽吸收敏化层。HBL可以是有机HBL,包括例如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或三[3-(3-吡啶基)-基]硼烷(3TPYMB)。空穴阻挡层(HBL)可以是无机HBL,包括例如ZnO或TiO2。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)或碳纳米管。
可用作空穴传输层(HTL)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)。可采用的电致发光的发光(LED)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)。可用作电子传输层(ETL)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)。
阴极可以是铟锡氧化物(ITO)、铟锌氧化物(IZO)、铝锡氧化物(ATO)、铝锌氧化物(AZO)、碳纳米管、银纳米线或Mg:Al层。在本发明的一个实施方案中,将厚度小于20nm的堆叠的10:1Mg:Ag层用作透明电极。在本发明的一个实施方案中,抗反射层位于透明阴极的外表面上。例如,当Alq3层的厚度小于约100nm时,所述Alq3层可以是允许良好透明度的抗反射层。或者,抗反射层可以是厚度约50nm或更小的金属氧化物,例如MoO3。在本发明的一个实施方案中,可见光出射面包括约10nm的10:1Mg:Al阴极层并且50nm的Alq3层位于该阴极之上。
通过阳极、阴极、LED材料、空穴传输层、HBL和电子传输层相对的功函数、HOMO和LUMO能级、层的相容性、以及在其制造过程中所用的任意期望的沉积方法性质,得益于本公开内容的本领域技术人员可以容易地确定阳极、阴极、LED材料、空穴传输层、HBL与电子传输层的适当的组合。在本发明的一些实施方案中,阳极和阴极是透明的,并且多层堆叠体可以在刚性的(例如,玻璃)或柔性的(例如,有机聚合物)透明支持件上形成。
在本发明的一个实施方案中,上转换器件包括位于衬底与阳极之间的IR透过的可见光阻挡层。用在上转换器件中的IR透过的可见光阻挡层可采用多电介质堆叠层。IR透过的可见光阻挡层包括电介质膜的堆叠体,所述电介质膜的堆叠体有具有不同折射率的交替的膜,一层膜具有高折射率而另一层膜具有显著较低的折射率。示例性的IR透过的可见光阻挡层由厚度为10nm至100nm的2至80个Ta2O5(RI=2.1)和SiO2(RI=1.45)交替层的复合物构造成。
可通过多种方式实现CIS至上转换器件的耦接以形成成像器件。在图5和图6中,上转换器件独立于CIS构造,并且两个器件通过将两个器件堆叠而耦接,使得由发光层发射的可见光激活所述CIS像素的光检测器并且所得电信号通过像素中的放大器放大。图5的上转换器件包括一对玻璃衬底,并且置于CIS上。两个刚性器件可以例如通过机械紧固件或粘合剂耦接。在图6中,上转换器件被构造成透明的柔性膜,其随后被层叠至CIS。
在本发明的一些实施方案中,CIS是图像传感器,并提供放大而无需用于特定辐射频率范围的滤光器或将光导向像素的光检测器的微透镜(micro lens)。
在本发明的另一个实施方案中,如图7所举例说明的,CIS用作衬底,上转换器件的层构造在其上,得到了包括成像器件的上转换器件和CIS的单一模块。
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,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,本文所述的实施例和实施方案仅为了说明性目的,本领域技术人员将从其想到多种修改或变化,并且这些修改或变化包括在本申请的精神和范围内。
Claims (18)
1.一种成像器件,其包括透明IR上转换器件和CMOS图像传感器(CIS),其中所述透明IR上转换器件是多层堆叠体,所述多层堆叠体包括:阳极层、空穴阻挡层、IR敏化层、空穴传输层、发光层、电子传输层和阴极。
2.根据权利要求1所述的成像器件,其中所述阳极包括铟锡氧化物(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。
3.根据权利要求1所述的成像器件,其中所述空穴阻挡层包括TiO2、ZnO、BCP、Bphen、3TPYMB或UGH2。
4.根据权利要求1所述的成像器件,其中所述IR敏化层包括PbSeQD、PbS QD、PbSe膜、PbS膜、InAs膜、InGaAs膜、Si膜、Ge膜、GaAs膜、苝-3,4,9,10-四羧酸-3,4,9,10-二酸酐(PTCDA)、酞菁锡(II)(SnPc)、SnPc:C60、酞菁氯化铝(AlPcCl)、AlPcCl:C60、酞菁氧钛(TiOPc)或TiOPc:C60。
5.根据权利要求1所述的成像器件,其中所述空穴传输层包括1,1-双[(二-4-甲苯氨基)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)。
6.根据权利要求1所述的成像器件,其中所述发光层包括三-(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)。
7.根据权利要求1所述的成像器件,其中所述电子传输层包括三[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)或三-(8-羟基喹啉)铝(Alq3)。
8.根据权利要求1所述的成像器件,其中所述阴极包括铟锡氧化物(ITO)、铟锌氧化物(IZO)、铝锡氧化物(ATO)、铝锌氧化物(AZO)、碳纳米管、银纳米线或Mg:Al。
9.根据权利要求1所述的成像器件,其中所述阴极包括厚度小于30nm的10:1Mg:Ag层。
10.根据权利要求1所述的成像器件,其中所述多层堆叠体还包括在所述阴极上的抗反射层。
11.根据权利要求10所述的成像器件,其中所述抗反射层包括厚度小于200nm的Alq3层。
12.根据权利要求1所述的成像器件,其中所述多层堆叠体还包括位于所述阳极上的IR透过的可见光阻挡层。
13.根据权利要求12所述的成像器件,其中所述IR透过的可见光阻挡层包括多个具有不同折射率的材料的交替层。
14.根据权利要求13所述的成像器件,其中所述交替层包括厚度为10至100nm的Ta2O5层和SiO2层,并且所述IR透过的可见光阻挡层包括2至80个层。
15.根据权利要求1所述的成像器件,其中所述CIS是用于所述多层堆叠体的衬底。
16.根据权利要求1所述的成像器件,其中所述多层堆叠体还包括支撑层。
17.根据权利要求16所述的成像器件,其中所述支撑层是刚性的,并且所述上转换器件通过机械紧固件或粘合剂耦接至所述CIS。
18.根据权利要求16所述的成像器件,其中所述支撑层是柔性的,并且所述上转换器件被层叠至所述CIS。
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- 2012-06-06 WO PCT/US2012/040980 patent/WO2012170456A2/en active Application Filing
- 2012-06-06 AU AU2012268322A patent/AU2012268322A1/en not_active Abandoned
- 2012-06-06 JP JP2014514568A patent/JP6309449B2/ja not_active Expired - Fee Related
- 2012-06-06 KR KR1020147000227A patent/KR102031996B1/ko active IP Right Grant
- 2012-06-06 CA CA2837739A patent/CA2837739A1/en not_active Abandoned
- 2012-06-06 SG SG2013083548A patent/SG194906A1/en unknown
Also Published As
Publication number | Publication date |
---|---|
KR102031996B1 (ko) | 2019-10-14 |
EP2718974A2 (en) | 2014-04-16 |
WO2012170456A3 (en) | 2013-04-25 |
WO2012170456A2 (en) | 2012-12-13 |
RU2013158842A (ru) | 2015-07-20 |
AU2012268322A1 (en) | 2014-01-16 |
EP2718974A4 (en) | 2015-05-20 |
JP6309449B2 (ja) | 2018-04-11 |
JP2014522578A (ja) | 2014-09-04 |
SG194906A1 (en) | 2013-12-30 |
CA2837739A1 (en) | 2012-12-13 |
CN103765588A (zh) | 2014-04-30 |
BR112013031013A2 (pt) | 2016-11-29 |
US20140111652A1 (en) | 2014-04-24 |
EP2718974B1 (en) | 2019-10-09 |
KR20140053943A (ko) | 2014-05-08 |
MX2013014311A (es) | 2014-01-23 |
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