平面异质结有机-无机杂化钙钛矿太阳电池研究进展

高效低成本太阳电池的研发是太阳能光伏技术大规模推广应用的关键. 近年来兴起的有机- 无机杂化钙钛矿(以下简称钙钛矿)太阳电池因具有光电能量转换效率高、制备工艺简单等优点, 引起了学术界和产业界的广泛关注, 具有广阔的发展前景. 其中平面异质结钙钛矿太阳电池因具有结构简单, 可低温制备等诸多优点, 成为目前研究的一个重要方向. 平面异质结钙钛矿太阳电池分为n-i-p型和p-i-n型两种结构. 其中钙钛矿分别与电子传输层和空穴传输层形成两个界面, 在这两个界面上实现电子和空穴的快速分离. 电子传输层和空穴传输层分别为电子和空穴提供了独立的输运通道. 平面异质结结构有利于钙钛矿太阳电池中电子和空穴的分离、传输和收集. 此外, 该结构不需要高温烧结的多孔结构氧化物骨架, 扩大了电子和空穴传输材料的选择范围. 可以根据钙钛矿材料的能带分布及载流子传输特性, 来选择能级和载流子传输速率更为匹配的传输材料. 本文对钙钛矿的材料特性, 平面异质结结构的由来及发展进行了简要的概述. 其中重点介绍了平面异质结钙钛矿太阳电池的结构特征、工作机理、钙钛矿/电荷传输层的界面特性, 以及电池性能的优化, 包括钙钛矿薄膜制备、空穴和电子传输层的优化等. 最后对钙钛矿电池的发展前景及存在问题进行了阐述, 为今后高效、稳定钙钛矿太阳电池的研究提供参考.     

有机无机异质节中稀土配合物电致发光的研究

报道了有机无机异质节中稀土配合物的电致发光,器件结构为：ITO/PVK:Rare Earth Complex/无机材料/Al,其中无机材料可以选用ZnS,ZnSe,ZnO等。在这种结构的器件中,均获得了比较好的稀土离子的特征发射。以无机材料ZnS为例,讨论了异质节中稀土配合物的电致发光及优势。ZnS的电介质系数比PVK的电介质系数大3倍多,将有更大部分的电压降落在PVK层上,使PVK层内的电场强度增大,从而可以提高空穴在PVK层内的迁移速度,提高了空穴注入数目,有利于载流子的平衡。     

空穴传输层对有机电致发光器件性能的影响

制备了结构为ITO/MoO₃(40 nm)/空穴传输层/CBP:Ir(ppy)₂acac(8%)(30 nm)/BCP(10 nm)/Alq₃(40 nm)/LiF(1 nm)/Al(100 nm)的器件,其中Ir(ppy)₂acac为绿色磷光染料,空穴传输层分别为TAPC(50 nm)、TAPC(40 nm)/TCTA(10 nm)、NPB(50 nm)、NPB(40 nm)/TCTA(10 nm)。通过使用4种不同结构的空穴传输层,对器件的发光性能进行了研究。结果表明,空穴传输层对器件的发光性能有较大影响。在电压为6 V、电流密度为2 mA/cm²的条件下,4种结构的器件的电流效率分别为52.5,67.8,35.6,56.6 cd/A。其原因是TAPC/TCTA及NPB/TCTA能级结构更有利于空穴对发光层的注入而且TAPC拥有较高的空穴迁移率;另外,TAPC及TCTA拥有较高的LUMO和三线态能量,可以有效地将电子和三线态激子束缚在发光层内,增加绿光染料的复合发光几率。所制备的器件均表现出良好的色坐标稳定性。     

反向驱动的异质结有机薄膜电致发光

成功制备了结构为ITO／PDDOPV／PPQ／Al的异质结聚合物发光二极管。该器件在正反向偏压下均可发光。在正向偏压下的光发射主要来自PDDOPV，但在反向偏压下的光发射则包括来自PPQ的蓝光发射和PDDOPV的黄光发射。蓝光强度与黄光强度的比值随着反向偏压的增加而增加，当反向直流电压分别为22V、24V、26V、28V时，其电致发光光谱中PPQ与PDDOPV的峰高比IPPQ／IPDDOPV分别为1．092、1．329、1．605、2．046。换句话说，该器件的发光颜色是压控可调的，这对实现彩色显示是极为有利的。分析了在反向偏压下的发光机理以及IPPQ／IPDDOPV受电压控制的原因。     

基于有机异质结的有机-无机复合单量子阱发光性质的研究

制备了包含有机异质结的有机-无机复合单量子阱器件ITO＼SiO₂(60 nm)＼MEH-PPV(40 nm)＼Alq₃(40 nm)＼SiO₂(60 nm)＼Al。通过对这种新结构器件光致发光和电致发光的研究,发现介电限域效应和量子尺寸效应对它的发光和电学性质有明显的影响。在交流电驱动下,OISQWOH(organic-inorganic quantum well with organic heterojunction)有三个发光峰：410,510和590 nm。其中410 nm的发光与MEH-PPV的扩展态相关,510和590 nm的发光分别来源于Alq₃和MEH-PPV的激子发光。     

有机/聚合物白光电致发光器件

将聚合物材料作为空穴传输材料,以有机小分子蓝光染料1,1,4,4－四苯基丁二烯,绿光染料8－羟基喹啉铝和黄光染料5,6,11,12－四苯基四苯并作为产生白光所需要的三种色源,制备了有机／聚合物白光电致发光器件。这种器件的设计使聚合物的热电稳定性好的优点与有机小分子材料荧光效率高的优点相结合,拓宽了材料的选择范围,更有利于选择能带匹配的材料体系。器件的开启电压为2.5V左右,发光效率在9V时达到最大1.24lm／W,该电压下的亮度达到1600cd/m^2,器件的最大亮度超过20000cd/m^2（18V）,器件最佳色度为（0.319,0.332),这在目前国际上有报道的有机／聚合物白光发光器件中居领先水平。     

PVK空穴传输层对有机电致发光器件性能的影响

以聚乙烯基咔唑poly(N-vinylcarbazole)(PVK)旋涂层为空穴传输层,着重研究了PVK层厚度对双层器件氧化铟锡(ITO)/PVK/tris-(8-hydroxyquinoline)aluminum(Alq₃)/Mg:Ag/Al器件性能的影响。测试结果表明,当Alq₃层厚度一定时(50nm),只有PVK层为适当厚度(18nm)时双层器件才有最优良的器件性能,即最低的起亮电压,最高的发光亮度和效率。同时对比了不同PVK层厚度的PVK/Alq₃双层器件之间以及PVK/Alq₃与N,N′-bis-(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine(NPB)/Alq₃双层器件寿命的差异。测试结果表明,尽管越厚的PVK层对应的PVK/Alq₃双层器件发光性能并不是越好,但器件寿命越长。原因是器件Alq₃层内形成的Alq³⁺越少,因此器件稳定性越好;而PVK/Alq₃与NPB/Alq₃双层器件寿命的差异来自不同空穴传输层的制备工艺和能级结构的不同。     

Rubrene作电子传输层的异质结有机太阳能电池

以Rubrene为电子传输层(ETL),制备了结构为ITO/MoO3(5nm)/Rubrene(50nm)/C60(45nm)/Rubrene(0,3,5.5,9.5nm)/Al(130nm)的有机太阳能电池.与没有ETL的器件相比,含5.5nmRubrene的电池的开路电压、填充因子、功率转换效率分别从0.68V,0.488,0.315%增加到0.86V,0.574,0.490%.实验结果分析表明:热的Al原子直接沉积在C60上,破坏了C60层,形成高功函数的C60/Al阴极,弱化内建电场,降低电池性能;当插入ETL后,C60层得到保护,热的Al原子沉积破坏了Rubrene层,形成了缺陷态能级,提高电池的内建电场,促进了电子的传输.进一步的单电子电池实验表明,缺陷态能级低于C60的最低未占据分子轨道.     

MEH-PPV/ZnO纳米晶无机有机复合电致发光器件的研究

以Ⅱ一Ⅵ族无机半导体ZnO纳米颗粒为电子传输层,MEH-PPV为空穴传输层兼发光层,得到的电致发光器件比单层MEH-PPV器件的发光亮度和效率都明显提高。器件结构为ITO／MEH-PPV／ZnO／Al的电致发光光谱同单层PPV器件的光谱出现了不同,在620nm处出现了一个小的发光峰,应该是ZnO的发光。另外,双层结构器件的启亮电压由单层器件的9V降到了4V左右。由I-V曲线及发光光谱可判断出发光区域应在MEH-PPV／ZnO界面处,并且复合区域可能随着电压的变化而变化。     

常压MOCVD制备ZnSe基pin二极管的蓝绿色电致发光

蓝色电致发光和激光器件的研究已有一段较长的历史.人们曾把GaN,SiC和ZnSe等半导体作为获得蓝色发光的主要材料.对于ZnSe,由于它是直接带隙且正好适于蓝区波段,因此,它是实现全彩色化显示、显像以及提高光存储合适的材料之一.     

基于空穴注入层摩擦定向的偏振蓝光聚合物电致发光器件

研究了利用摩擦空穴注入层3,4-乙撑二氧噻吩:聚苯乙烯磺酸(PEDOT:PSS)作为定向层实现聚芴(PFO)薄膜的偏振电致发光,蓝光的色坐标为(0.20,0.21).从聚合物薄膜的紫外可见吸收和光致发光偏振特性,研究了不同定向层摩擦强度、退火温度以及退火时间下PFO薄膜的二向色性,并证明退火温度是决定器件偏振性能的关键因素.当摩擦强度为25 mm退火温度和时间分别为200℃和30 min时,得到较好的偏振性能,器件的电致发光偏振率约为3. 关键词： 偏振发光 摩擦定向 聚合物电致发光 空穴注入层     

新型TPBI/Ag阴极结构的红色有机发光二极管

采用可溶液加工的小分子红光材料2为发光层（EML）,制备了不同阴极结构的系列电致发光器件.结果表明,空穴阻挡层（HBL）TPBI的引入能有效降低高功函数（Al, Ag, Au）金属阴极的电子注入势垒,显著改善器件发光效率,与传统阴极结构（Ba/Al）比较,采用TPBI/Ag阴极结构的器件外量子效率提高了57%,主要原因是TPBI/Ag阴极界面形成较低的电子注入势垒,有利于电子注入,使器件发光效率明显提高. 关键词： 电致发光 电子注入 阻挡层 高功函数金属阴极     

Performance improvement of blue InGaN light-emitting diodes with a specially designed n-AlGaN hole blocking layer

Blue InGaN light-emitting diodes (LEDs) with a conventional electron blocking layer (EBL), a common n-AlGaN hole blocking layer (HBL), and an n-AlGaN HBL with gradual Al composition are investigated numerically, which involves analyses of the carrier concentration in the active region, energy band diagram, electrostatic field, and internal quantum efficiency (IQE). The results indicate that LEDs with an n-AlGaN HBL with gradual Al composition exhibit better hole injection efficiency, lower electron leakage, and a smaller electrostatic field in the active region than LEDs with a conventional p-AlGaN EBL or a common n-AlGaN HBL. Meanwhile, the efficiency droop is alleviated when an n-AlGaN HBL with gradual Al composition is used.     

Influence of thermal stress on the relative permittivity of the AlGaN barrier layer in an AlGaN/GaN heterostructure Schottky contacts

Ni Schottky contacts on AlGaN/GaN heterostructures were fabricated. Some samples were thermally treated in a furnace with N₂ ambience at 600 °C for different times (0.5 h, 4.5 h, 10.5 h, 18 h, 33 h, 48 h, and 72 h), the others were thermally treated for 0.5 h at different temperatures (500 °C, 600 °C, 700 °C, and 800 °C). With the measured current—voltage (I—V) and capacitance—voltage (C—V) curves and by self-consistently solving Schrodinger's and Poisson's equations, we found that the relative permittivity of the AlGaN barrier layer was related to the piezoelectric and the spontaneous polarization of the AlGaN barrier layer. The relative permittivity was in proportion to the strain of the AlGaN barrier layer. The relative permittivity and the strain reduced with the increased thermal stress time until the AlGaN barrier totally relaxed (after 18 h at 600 °C in the current study), and then the relative permittivity was almost a constant with the increased thermal stress time. When the sample was treated at 800 °C for 0.5 h, the relative permittivity was less than the constant due to the huge diffusion of the contact metal atoms. Considering the relation between the relative permittivity of the AlGaN barrier layer and the converse piezoelectric effect, the conclusion can be made that a moderate thermal stress can restrain the converse piezoelectric effect and can improve the stability of AlGaN/GaN heterostructure devices.     

卟啉铜接枝SiO2有机-无机复合材料及强的非线性折射率

通过卟啉配合物Meso-四(4-羧基苯基)卟啉铜(简称Cu(Ⅱ)-TCPP)中的羧基与γ-氨基丙基三乙氧基硅烷(NH₂(CH₂)₃Si(OC₂H₅)₃,KH550)中的氨基的相互化学作用,成功地把卟啉配合物接枝到KH550中,随着KH550中乙氧基的水解与聚合反应的进行,卟啉铜连接到固体介质中,从而大幅度提高了卟啉在无机固体介质中的掺杂浓度. 将反应产物与γ-(2,3-环氧丙氧基)丙基三甲氧基硅烷(CH₂CHCH₂O(CH₂)₃Si(OCH₃)₃,KH560) 相杂化,形成物化性能良好、连接卟啉的有机-无机复合材料. 用红外光谱表征了Cu(Ⅱ)-TCPP与KH550的化学反应产物,用紫外—可见吸收光谱研究Cu(Ⅱ)-TCPP的分子状态. 应用Z扫描技术研究不同Cu(Ⅱ)-TCPP掺杂浓度的复合材料的非线性光学性质,其三介非线性折射率n₂达-1.1161×10^-16 m²/W. 关键词： 非线性折射率 有机-无机复合材料 接枝 Meso-四(4-羧基苯基)卟啉铜     

Design and fabrication of ultra broadband infrared antireflection hard coatings on ZnSe in the range from 2 to 16 μm

In conventional infrared multilayer antireflection coatings (MLAR) materials of fluoride and chalcogenide types are used, which are disadvantaged due to their low mechanical strength and poor stability against humidity and environmental impacts. In this paper, we show that high performance ultra broadband and hard infrared multilayer antireflection coatings on ZnSe substrates in the wavelength range from 2 to 16 μm can be designed and fabricated. Diamond-like carbon (DLC) hard coating as a mechanical and environmental protection layer was proposed and deposited onto MLAR surfaces (MLAR + DLC) using a pulsed vacuum arc ion deposition technique. The thickness of the high optical quality DLC can be optimized in the design simulation to achieve a practically best antireflection and surface protection performance. We show that a germanium thin film (15 nm) between the MLAR and DLC surfaces can be used as a transition layer for optical and material match. The average transmission of the fabricated MLAR+DLC surfaces was 93.1% in the wavelength range between 2 and 16 μm. The peak transmission was about 97.6%, close to the simulated values. The durability and stability against mechanical impacts and environmental tests was improved significantly compared with the conventional infrared windows.     

Improved performances in top-emitting organic light-emitting diodes based on a semiconductor zinc oxide buffer layer

Electroluminescence performances are improved by inserting a semiconductor zinc oxide (ZnO) buffer layer into the emissive tris-(8-hydroxyquinoline)aluminum (Alq₃) layer and the semitransparent Al/Ag cathode in top-emitting organic light-emitting diodes (TEOLEDs) with structures of Si/SiO₂/Ag/Ag₂O/4,4′, 4″-tris(3- methylphenylphenylamino)triphenylamine/ 4,4′-bis[N-(1-naphthyl-1-)-N-phenyl- amino]-biphenyl/Alq₃/ZnO/Al/Ag. The thermal deposition of ZnO layer onto Alq₃ results in Alq₃ anion formation, which is beneficial to electron injection by generating some new energy levels in the forbidden band of Alq₃. In addition, a large hole-injection barrier of 2 eV at the interface of Alq₃/ZnO effectively blocks hole injection into Al/Ag cathode, leading to more carrier recombination in the emissive region.     

Improving the color purity and efficiency of blue organic light-emitting diodes (BOLED) by adding hole-blocking layer

This work demonstrates the fabrication of a bright blue organic light-emitting diode (BOLED) with good color purity using 4,4′-bis(2,2-diphenylvinyl)-1,1′-biphenyl (DPVBi) and bathocuproine (BCP) as the emitting layer (EML) and the hole-blocking layer (HBL), respectively. Devices were prepared by vacuum deposition on indium tin oxide (ITO)-glass substrates. The thickness of DPVBi used in the OLED has an important effect on color and efficiency. The blue luminescence is maximal at 7670 cd/m² when 13 V is applied and the BCP thickness is 2 nm. The CIE coordinate at a luminance of 7670 cd/m² is (0.165, 0.173). Furthermore, the current efficiency is maximum at 4.25 cd/A when 9 V is applied.     

Comparison of electrical characteristic between AlN/GaN and AlGaN/GaN heterostructure Schottky diodes

Ni/Au Schottky contacts on AlN/GaN and AlGaN/GaN heterostructures are fabricated.Based on the measured current–voltage and capacitance–voltage curves,the electrical characteristics of AlN/GaN Schottky diode,such as Schottky barrier height,turn-on voltage,reverse breakdown voltage,ideal factor,and the current-transport mechanism,are analyzed and then compared with those of an AlGaN/GaN diode by self-consistently solving Schrdinger’s and Poisson’s equations.It is found that the dislocation-governed tunneling is dominant for both AlN/GaN and AlGaN/GaN Schottky diodes.However,more dislocation defects and a thinner barrier layer for AlN/GaN heterostructure results in a larger tunneling probability,and causes a larger leakage current and lower reverse breakdown voltage,even though the Schottky barrier height of AlN/GaN Schottky diode is calculated to be higher that of an AlGaN/GaN diode.