Dynamics of excitons and carriers at the NPB/C60 interface by transient photocurrents

The transient photocurrent (TPC) technique was performed to explore the dynamics of excitons and carriers at organic active layer/buffer layer interfaces. A special device with ITO/PEIE/NPB/C₆₀/Al structure was designed to study the interfacial processes at the NPB/C₆₀ interface. An external electrical field was provided to neutralize the built-in electrical field of the device. Interestingly, a new phenomenon was observed, wherein the polarity of the TPC changed from negative to positive under an external electrical field. The initial negative signal was ascribed to exciton separation by the built-in field in C₆₀, and the subsequent positive signal can be attributed to the diffusion of electrons that accumulate at the NPB/C₆₀ interface. TPC measurements shown that further increasing the external electrical field causes polarity to change twice. Analyzing the two changes in polarity revealed that the NPB did not only extract holes from C₆₀ but also provided an effective interface for exciton dissociation.     

Excitonic processes at organic heterojunctions

Understanding excitonic processes at organic heterojunctions is crucial for development of organic semiconductor devices. This article reviews recent research on excitonic physics that involve intermolecular charge transfer (CT) excitons, and progress on understanding relationships between various interface energy levels and key parameters governing various competing interface excitonic processes. These interface excitonic processes include radiative exciplex emission, nonradiative recombination, Auger electron emission, and CT exciton dissociation. This article also reviews various device applications involving interface CT excitons, such as organic light-emitting diodes (OLEDs), organic photovoltaic cells, organic rectifying diodes, and ultralow-voltage Auger OLEDs.     

Transient photovoltage and photoluminescence study of exciton dissociation at indium tin oxide/pentacene interface

The exciton dissociation at ITO/pentacene interface is studied by means of transient photovoltage measurement.Opposite to ITO/NPB,ITO/CuPc or ITO/C60 interface where polarity change of transient photovoltage is observed,no interfacial dissociation is found at room temperature,which indicates a lack of Frenkel excitons in pentacene.Temperature-dependent photoluminescence (PL) is investigated.More like the behavior of inorganic semiconductors,the integrated PL intensity exhibits monotonic decrease with increa...     

NPB/Alq3 界面激子拆分研究

采用瞬态光电压技术研究了NPB和Alq₃界面激子拆分过程和拆分机理.对NPB和Alq₃组成双层结构的样品,在脉冲355nm激光照射下,测量样品的瞬态光电压信号,通过对不同结构的和有界面激子阻挡层的样品的瞬态光电压分析,并排除了ITO/有机外界面对激子拆分的影响,得出了NPB/ Alq₃界面激子拆分机理是向Alq₃ 注入电子,向NPB注入空穴. 关键词： 激子拆分 界面 瞬态光电压     

Wavelength dependence of transient photovoltage polarity

Using pulsed laser with different wavelengths, transient photovoltage (TPV) is investigated for the sandwich device of indium tin oxide (ITO)/poly (2-methoxy-5-(2′-ethylhexyloxy)-1, 4-phenylenevinylene) (MEH-PPV) (500 nm)/Al. At laser wavelength of 500 nm, a 0.1 millisecond negative TPV signal appears followed by a positive one lasting 40-80 milliseconds. With increasing laser wavelength, the negative signal becomes weak and disappears when wavelengths λ?560 nm. This work demonstrates the process of exciton dissociation at the interface between ITO and MEH-PPV. A new method measuring the relative dissociation rate at the interface between polymer and electrode is introduced. It is estimated that the dissociation rate at Al interface is 4-8 times of that at the ITO interface.     

Interfacial processes in small molecule organic solar cells

This paper presents an overview of the recent progress of small molecule organic solar cells mainly based on the previous worksof our group. We will mainly focus on the interfacial processes in the cells. The dissociation of excitons at electrode/organic andorganic/organic interfaces can be directly observed by transient photovoltage measurements. A simple model including dissociationof excitons at the interface and drift of free carriers in the built-in field is proposed to explain the observed signals of ...     

Electronic structure of interfaces with conjugated organic materials

The function and efficiency of most organic electronic and opto‐electronic devices greatly depend on the electronic structure of the interfaces therein. Charge injection from electrical contacts into the organic semiconductor, charge extraction, or exciton dissociation at organic semiconductor heterojunctions are crucial processes that must be optimized for high device efficiency. Consequently, the energy levels at these interfaces must be matched to allow for optimal performance. The key mechanisms that determine the energy level alignment at organic/electrode and organic/organic interfaces are reviewed, and methods to adjust the levels at such interfaces are presented. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Exciton dissociation in organic light emitting diodes at the donor-acceptor interface

Experimental in situ photoluminescence and transient photovoltage results show that the interface formed by N, N{'}-Bis(naphthalene-1-yl)-N, N{'}-bis(phenyl) benzidine (NPB) and tris(8-hydroxyquinoline) aluminum (Alq{3}) acts as an exciton dissociation site. Because of this dissociation effect, excitons formed in NPB at or within a diffusion length of the interface tend to dissociate before they radiatively decay to generate blue light. This suggests that the action of the "hole-blocking layer" used in indium tin oxide\NPB\hole-blocking layer\Alq{3}\aluminium to promote blue light emission from the NPB is more "exciton dissociation inhibition" than "hole blocking."     

有机高分子链内的场致激子解离

基于SSH(Su-Schrieffer-Heeger)模型,采用静态及动力学自洽算法模拟了有机高分子链内激子在光激发及外电场作用下的形成与解离过程。结果表明,受光激发后,有机高分子链内激子的生成与解离密切依赖于施加外电场的时机,当外电场与光激发同时发生时,激子能否生成完全取决于电场强度的大小;而当外电场在光激发后的一段时间(通常为皮秒量级)之后被引入,则在有机高分子链内能够形成稳定的激子,且该激子只有在强外电场(超过1MV/cm)的作用下,才会发生解离,临界场强量级与实验结果相符合。     

High current density in light-emitting transistors of organic single crystals

We measured the external electroluminescence quantum efficiency (eta(ext)) in light-emitting field-effect transistors (LETs) made of organic single crystals and found that, in the ambipolar transport region, eta(ext) is not degraded up to several hundreds A/cm(2) current-density range, which is 2 orders of magnitude larger than that achieved in conventional organic light-emitting diodes. The present result indicates the single-crystal organic LET is a promising device structure that is free from various kinds of nonradiative losses such as exciton dissociation near electrodes and exciton annihilations.     

基于混合空穴注入层的湿法制备高效蓝光热激活延迟有机发光二极管

在溶液法制备有机电致发光器件(OLEDs)的研究中, PEDOT∶PSS由于具有较好的成膜性与高透光性而常被用作器件的空穴注入层。但相关研究表明, PEDOT∶PSS本身稳定性较差以及功函数较低,这使得溶液法制备OLEDs的性能差且不稳定。蓝色作为全彩色的三基色之一,制备高效的蓝光器件对于实现高质量显示器件和固态照明装置必不可少。而目前溶液法制备蓝光OLEDs的器件效率普遍较差,针对此问题,本文利用传统的蓝光热激活延迟荧光发光(TADF)材料DMAC-DPS作为发光层,用溶液法制备了蓝光TADF OLEDs,通过在PEDOT∶PSS中掺杂PSS-Na制备混合空穴注入层(mix-HIL)来提高空穴注入层的功函数,研究其对于蓝光TADF OLEDs器件性能的影响。首先在PEDOT∶PSS水溶液中掺入不同体积的PSS-Na溶液,在相同条件下旋涂制膜,进行器件制备。通过观测各个实验组器件的电致发光(EL)光谱,发现掺入PSS-Na后器件EL谱存在光谱蓝移的现象,这是由于掺入PSS-Na水溶液后, mix-HIL层的厚度有所降低,使得在微腔效应作用下, EL光谱发生蓝移。通过对比各组器件的电流密度-电压-亮度(J-V-L)曲线及其计算所得器件的电流效率,结果显示随着PSS-Na的掺入,器件的亮度和电流都有所增大,器件的电流效率也得到了提升,当掺杂比例为0.5∶0.5(PEDOT∶PSS/PSS-Na)时提升幅度最大(亮度提升86.7%,电流效率提升34.3%)。通过在瞬态电致发光测试过程中施加或撤去驱动电压观测了器件EL强度的变化,分析了在混合空穴注入层/发光层(mix-HIL/EML)界面处的电荷积累情况。实验证明,通过在PEDOT∶PSS中掺杂PSS-Na制备mix-HIL获得了蓝光TADF OLEDs器件性能的提升,这是一个获得高效率溶液法制备OLEDs的可行方法。     

新型高效聚合物/富勒烯有机光伏电池研究进展

有机聚合物/富勒烯本体异质结光伏电池以其不断提高的能量转换效率受到了研究人员的广泛关注, 近年来成为光伏电池研究领域的热点之一. 本文主要通过对聚合物/富勒烯太阳能电池的内部机理,包括光吸收、激子扩散和解离以及自由载流子输运和提取等关键科学问题, 从器件材料和结构优化、形貌控制和界面修饰等不同侧面介绍了提高聚合物/富勒烯太阳能电池性能的方法, 讨论了各种器件的结构和能量转换效率, 对于进一步开展这方面的研究工作指明了方向, 最后对其未来的发展前景做出了展望.     

Charge‐transfer‐induced doping at an electron donor (α‐sexithiophene)/acceptor (C60) interface and mobility improvement

We studied various aspects relating to surface charge‐transfer‐induced doping at an organic/organic interface using in situ electrical measurements with a field‐effect transistor (FET) during the formation of the electron donor/acceptor interface. Adsorption of the electron‐accepting molecules (C₆₀) on top of the electron donating molecules (α‐6T) led to an increase in the FET hole mobility in an α‐6T film. Under illumination, the FET hole mobility in the α‐6T film with C₆₀ deposition was significantly increased in comparison with that in the dark due to exciton dissociation at the C₆₀/α‐6T interface, resulting in a large threshold voltage shift. The origin of the mobility increase is explained by the multiple trapping and release (MTR) model in which the mobility is determined by the carrier density. Various phenomena relevant to charge transfer and charge transport at the organic/organic interface are reported and their origins are discussed. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

激子复合区厚度对有机磁效应的影响

在常规型有机发光二极管的基础上, 通过改变发光层tri-(8-hydroxyquinoline) aluminum (III) (Alq₃)厚度, 研究了激子复合区厚度对有机发光二极管磁效应的影响.测量了器件在不同温度及偏压下电致发光及注入电流在外加磁场作用下的变化, 着重研究了低温下的有机磁电导效应和有机磁电致发光效应.实验发现, 低温(50 K)高磁场 (500 mT)下, 器件表现出随Alq₃厚度的减薄, 磁电导值由正到负再到正的非单调变化.利用磁场调控的超精细相互作用、 磁场抑制的三重态激子-电荷反应以及激子在界面的淬灭效应, 对有机磁电导在低温下表现出的现象进行了定性的解释.实验结果表明, 通过改变激子复合区的厚度, 可以实现对激子浓度的有效调节, 进而实现对有机磁电导和磁电致发光效应的调节. 该研究进一步丰富了有机磁效应的实验现象, 同时提供了一种调控有机磁效应的手段. 关键词： 激子复合区 激子浓度 有机磁电导 有机磁电致发光     

Electrically Driven InAs Quantum-Dot Single-Photon Sources

Electrically driven single photon source based on single InAs quantum dot （QDs） is demonstrated. The device contains InAs QDs within a planar cavity formed between a bottom AlCaAs/CaAs distributed Bragg reflector （DBR） and a surface CaAs-air interface. The device is characterized by I-V curve and electroluminescence, and a single sharp exciton emission line at 966nm is observed. Hanbury Brown and Twiss （HBT） correlation measurements demonstrate single photon emission with suppression of multiphoton emission to below 45% at 80 K     

Direct measurement of the triplet exciton diffusion length in organic semiconductors

We present a new method to measure the triplet exciton diffusion length in organic semiconductors. N,N'-di-[(1-naphthyl)-N,N'-diphenyl]-1,1'-biphenyl)-4,4'-diamine (NPD) has been used as a model system. Triplet excitons are injected into a thin film of NPD by a phosphorescent thin film, which is optically excited and forms a sharp interface with the NPD layer. The penetration profile of the triplet excitons density is recorded by measuring the emission intensity of another phosphorescent material (detector), which is doped into the NPD film at variable distances from the injecting interface. From the obtained triplet penetration profile we extracted a triplet exciton diffusion length of 87±2.7 nm. For excitation power densities >1 mW/mm(2) triplet-triplet annihilation processes can significantly limit the triplet penetration depth into organic semiconductor. The proposed sample structure can be further used to study excitonic spin degree of freedom.     

Strain-confined wires and dots at a GaAs/AlxGa1-xAs interface

We have observed lateral exciton confinement at the GaAs/Al_xGa_1-xAs interface. The confinement is achieved in both the growth and lateral directions by the strain potential under an amorphous carbon stressor. The potential welt varies from 15 meV to 40 meV for different stressor sizes. We have also made transient measurements on this structure, which show efficient exciton transfer from the bulk GaAs to the confined region.     

Interactions at tetraphenyl-porphyrin/InP interfaces observed by surface photovoltage spectroscopy

Illumination induced charge separation processes at tetraphenyl-porphyrin (H₂TPP)/InP interfaces are characterized. The results indicate that upon illumination an electronic transition takes place between the organic highest occupied molecular orbital (HOMO) and the InP conduction band. A 70 meV blue shift in the characteristic modulated surface photovoltage spectrum of a 50 nm H₂TPP film was observed when n-InP substrate was used. Such blue shift was not observed when Au, SnO₂:F or p-InP substrates were used. The shift may suggest a presence of an ordered interfacial sub-layer in an almost lying orientation, due to chemical or physical interactions at the interface. The results indicate that the Fermi level is unpinned at the interface. An exciton diffusion barrier in close proximity to the H₂TPP/n-InP interface has been demonstrated.     

共轭聚合物作为有机光电池电子受体的特性研究

以聚3-已基噻吩(P3HT)和聚对苯亚乙烯衍生物(MDMO-PPV)作为电子给体,聚 (TQ1)作为电子受体,制备并研究了聚合物给体/聚合物受体有机光伏电池性能。当给体P3HT、受体TQ1共混质量比为1∶1时,器件性能最佳。热处理会改变薄膜形貌,导致激子扩散到达界面的距离增加和激子分离界面数量下降,进而引起器件性能下降。溶剂效应对器件性能影响不明显。研究了相似能带结构给体聚合物对MDMD-PPV光电池性能的影响,发现结晶程度较低的给体材料会进一步导致器件性能降低。     

Transport and recombination in organic light-emitting diodes studied by electrically detected magnetic resonance

We have used electrically detected magnetic resonance (EDMR) to study a series of multilayer organic devices based on aluminum (III) 8-hydroxyquinoline (Alq₃). These devices were designed to identify the microscopic origin of different spin-dependent processes, i.e. hopping and exciton formation. The EDMR signal in organic light-emitting diodes (OLEDs) based on Alq₃ is only observed when the device is electroluminescent and is assigned to spin-dependent exciton formation. It can be decomposed in at least two Gaussians: one with peak-to-peak line ( ΔH_PP) of 1.6 mT and another with ΔH_PP of 2.0 to 3.4 mT, depending on bias and temperature. The g-factors of the two components are barely distinguishable and close to 2.003. The broad line is attributed to the resonance in Alq₃ anions, while the other line is attributed to cationic states. These attributions are supported by line shape and its electrical-field dependence of unipolar Alq₃-based diodes, where hopping process related to dication and dianion formation is observed. In these unipolar devices, it is shown that the signal coming from spin-dependent hopping occurs close to organic semiconductor/metal interfaces. The sign of the magnetic-resonance-induced conductivity change is dominated by charge injection rather than charge mobility. Our results indicate that the probability of singlet exciton formation in our OLEDs is smaller than 25%.