红荧烯晶体薄膜的制备及应用研究进展

红荧烯具有导电性好、吸收系数高等优良的荧光特性和半导体特性,是目前报道的单晶迁移率最高的材料,在有机光电器件中有很好的发展前景,受到科研人员的广泛关注。目前国内外主要采用真空蒸镀方法和溶液加工方法制备红荧烯晶体薄膜,采用各种制备工艺来提高红荧烯薄膜质量。本文在系统介绍红荧烯晶体薄膜制备工艺研究进展的基础上,归纳总结了掺杂种类/聚合物浓度、后处理工艺/实验温度等对红荧烯晶体性能的影响,简要概述了红荧烯薄膜在有机光电子器件应用研究中所取得的研究成果,最后展望了基于红荧烯晶体薄膜的光电器件的发展趋势。     

High-performance self-powered photodetector based on organic/inorganic hybrid van der Waals heterojunction of rubrene/silicon

Organic/inorganic hybrid van der Waals heterostructure with an atomically abrupt interface has attracted great research interests within the field of multifunctional electronic and optoelectronic devices. The integration of organic rubrene films with inorganic Si semiconductors can avoid the atomic mutual-diffusion at the interface, and provide the possibility of forming two-dimensional van der Waals heterojunction accompanied with the type-II energy band alignment, due to the transfer behaviors of majority carriers at the interface. In this study, the high-quality rubrene/Si van der Waals heterostructure with an electronically abrupt junction was prepared, and a self-powered photodetector was then constructed based on this hybrid heterojunction. The photodetector demonstrated an excellent switching response to the 1064 nm monochromatic light with large on/off current ratio of 7.0×10~3, the maximum photocurrent of 14.62 m A, the maximum responsivity of 2.07 A/W, the maximum detectivity of 2.9×10~(11) Jones, and a fast response time of 13.0 μs. This study offers important guidance for preparing high-quality rubrene/Si hybrid van der Waals heterostructure with desirable band alignment, and the designed heterojunction photodetector has an important application prospect in the field of multifunctional optoelectronics.     

Grazing‐incidence X‐ray diffraction study of rubrene epitaxial thin films

The growth of organic semiconductors as thin films with good and controlled electrical performances is nowadays one of the main tasks in the field of organic semiconductor‐based electronic devices. In particular it is often required to grow highly crystalline and precisely oriented thin films. Here, thanks to grazing‐incidence X‐ray diffraction measurements carried out at the ELETTRA synchrotron facility, it is shown that rubrene thin films deposited by organic molecular beam epitaxy on the surface of tetracene single crystals have the structure of the known orthorhombic polymorph, with the (2 0 0) plane parallel to the substrate surface. Moreover, the exact epitaxial relationship between the film and the substrate crystalline structures is determined, demonstrating the presence of a unique in‐plane orientation of the overlayer.     

若干低维材料的拉曼光谱学研究--2004年度国家自然科学二等奖获奖项目介绍

文章扼要介绍了2004年国家自然科学二等奖获奖项目：《若干低维材料的拉曼光谱学研究》．用拉曼光谱研究低维纳米材料,必须对传统拉曼光谱学进行改造,创建新的“低维拉曼光谱学”．该项目通过若干低维材料的研究,为创建低维拉曼光谱学作出了系统的创新性贡献,如最先鉴认出典型低维材料的拉曼指纹谱,发现拉曼光谱的两个基本特征出现“反常”,但证明拉曼散射基本原理在低维体系中依然成立．通过低维拉曼光谱和光发射谱的应用研究,发现了材料的许多新奇物性,如发现超晶格和碳纳米管是类缺陷结构,和极性半导体纳米晶材料具有非晶特性,并提出了多孔硅的“量子限制电化学”形成和“多源量子阱”光发射模型,促进了低维材料和半导体器件的制备．     

Rubrene薄层的位置对器件发光性能的影响及器件内激子复合区域的分析

通过在主体材料上蒸镀一层荧光染料超薄层的方法,研究了有机小分子5,6,11,12-tetraphenyl-naphthacene(rubrene)薄层在器件中不同位置时,有机电致发光器件(OLED)的电致发光光谱及发光性能.实验发现当rubrene薄层位于NPB/AlQ界面处时,器件的发光几乎都来自rubrene的发光...     

Development of organic light‐emitting diodes for electro‐optical integrated devices

Organic light‐emitting diodes (OLEDs) are discussed for electro‐optical integrated devices that are used for optical signal transmission. Organic optical devices including polymeric optical fibers are used for optical communication applications to realize polymeric electro‐optical integrated devices. The OLEDs were fabricated by vacuum process, i.e. the organic molecular beam deposition (OMBD) technique or a solution process on a polymeric or a glass substrate, for comparison. Optical signals faster than 100 MHz have been created by applying pulsed voltage directly to the OLED utilizing rubrene doped in 8‐hydoxyquinolinum aluminum (Alq₃), as an emissive layer. OLEDs fabricated by solution process utilizing rubrene doped in carrier‐transporting materials have also discussed. OLEDs utilizing polymeric materials by solution process are also fabricated and discussed. Moving‐picture signals are transmitted utilizing both vacuum‐ and solution‐processed OLEDs, respectively.     

掺杂型红色有机电致发光显示器件

全色显示是有机电致发光显示(OLED)器件发展的目标,而高性能红色发光器件一直是制约全彩色OLED器件实用化的瓶颈,也是目前有机电致发光显示研究的热点。制作了掺杂DCJTB和不同浓度的rubrene两种荧光染料的红色有机电致发光显示器件,以NPB和Alq₃分别作为空穴传输层和电子传输层,发现器件性能与只掺杂DCJTB的器件相比有明显提高,发光效率提高到2～3倍。通过Frster理论和能带理论分析了器件的能量转移机理,研究发现Frster能量转移不是掺杂器件能量转移的主要形式,载流子俘获机制才是器件效率提高的主要原因;rubrene的引入使得能量能够更有效地从Alq₃转移到DCJTB,从而显著地提高了器件的发光效率和性能。     

Studies on stability of bi-functional P3HT:PCBM:rubrene optoelectronic devices

Investigations are carried out for stability in photovoltaic response of bifunctional electroluminescent and photovoltaic devices, based on ternary blend of poly(3-hexylthiophene) (P3HT), phenyl [6,6′]C₆₁ butyric acid methyl ester (PCBM), and 5,6,11,12-tetraphenylnaphthacene (rubrene). P3HT and PCBM are important and the most frequent materials used for photovoltaic applications, therefore, for relative comparison, photovoltaic cells were also prepared using a binary mixture of P3HT and PCBM. Devices based on the ternary blend exhibited better stability in all photovoltaic parameters and the lifetime was almost doubled, but their photovoltaic efficiency was lower than that of those based on the binary blend. Longer lifetime of ternary blend devices is because of a relatively better thermal, electrochemical, and morphological stabilities of the ternary blend system. However, the lower efficiencies are because of the reduced photo-current and low fill factor (FF) due to an increased recombination and introduction of defects/trapping sites by rubrene molecules.     

用于光通信的高速响应有机电致发光器件

采用直接光强调制的方法,建立了一种新型有机电致发光器件(OLED)的光电信号传输体系,研究了发光层掺杂、发光面积和预置电压对OLED响应速度的影响。结果发现:与发光层为单独的Alq3的器件相比较,掺杂rubrene的发光层的荧光寿命较短,响应较快;减小OLED的发光面积能提高OLED的响应速度,并在0.02 mm2的发光面积上实现了100 Mbit/s的信号传输速度;同时,预置直流电压也能改善OLED的响应速度。最后,提出将柔性OLED与聚合物波导及有机光电二极管结合,实现了一种全有机的柔性光电子体系。     

Enhanced blue photoluminescence and new crystallinity of Ag/organic rubrene core-shell nanoparticles through hydrothermal treatment

Light-emitting organic semiconductors have attracted considerable attention for the nanoscale fabrication of organic-based displays and their potential application in optoelectronics, plasmonics, and photonics. In this study, core-shell hybrid nanostructures of organic rubrene coated on Ag nanoparticles (NPs) have been synthesized using a chemical reduction method. The thickness of the rubrene shell was 2.6–6.0 nm and the diameter of the Ag core was 30–70 nm. The optical and structural properties of the Ag/rubrene core-shell NPs were tuned by hydrothermal (HT) treatment at 190 °C. The Ag/rubrene core-shell NPs were characterized by high-resolution transmission electron microscopy and energy-dispersive X-ray (EDX) spectroscopy before and after the HT treatment, and their structural properties were confirmed through X-ray diffraction (XRD) analysis. XRD peaks related to an orthorhombic phase were observed along with the original triclinic crystal structure of the rubrene shell, and the triclinic crystal domain size increased from 28.2 nm to 30.8 nm owing to the HT treatment. Interestingly, the green light emission (λ_em = 550 nm) of the Ag/rubrene core-shell NPs changed to blue light emission (λ_em = 425 nm), increasing in intensity through the HT treatment. This is caused by the crystal change with H-type aggregation and enhanced energy transfer from a surface plasmon resonance.     

DPVBi的厚度和发光位置不同对有机电致发光器件性能的影响

通过调整发光层DPVBi的厚度和在器件中的位置,在同一实验条件下设计了不同的器件结构,制备了有机电致发光器件,在实验中可看到DPVBi的厚度不同,器件的色度发生了改变,并且发现DPVBi在器件的不同位置,器件的发光特性也是不同的。通过实验可以得知处于器件不同位置的DPVBi,其发光机理是不同的,这是由于DPVBi和Alq3的最高未占有轨道(HOMO)能级相差不多,而它们的最低占有轨道(LUMO)能级相差0.4eV,这样DPVBi的存在有利于电子的注入,同时由于rubrene和DPVBi的HOMO相差0.5eV,这样空穴和电子就在rubrene和DPVBi的界面处形成激子复合而发光。也就是说,在rubrene之后的DPVBi对空穴有了阻挡作用,使器件中的空穴和电子达到平衡。通过改变DPVBi的厚度,制备了白光器件,这组白光器件,在7～17V变化范围内器件的色坐标从(0.35,0.37)到(0.33,0.35)变化不大,接近白光等能点(0.33,0.33),是色度比较好的器件。     

Searching for better plasmonic materials

Plasmonics is a research area merging the fields of optics and nanoelectronics by confining light with relatively large free‐space wavelength to the nanometer scale ‐ thereby enabling a family of novel devices. Current plasmonic devices at telecommunication and optical frequencies face significant challenges due to losses encountered in the constituent plasmonic materials. These large losses seriously limit the practicality of these metals for many novel applications. This paper provides an overview of alternative plasmonic materials along with motivation for each material choice and important aspects of fabrication. A comparative study of various materials including metals, metal alloys and heavily doped semiconductors is presented. The performance of each material is evaluated based on quality factors defined for each class of plasmonic devices. Most importantly, this paper outlines an approach for realizing optimal plasmonic material properties for specific frequencies and applications, thereby providing a reference for those searching for better plasmonic materials.     

Organic materials in future integrated optoelectronic circuits

During the last two decades, lithium niobate has been extensively studied for applications in integrated optical circuits. However, it is difficult to integrate lithium niobate optical devices with semiconductor electronic devices because the materials are incompatible. In recent years, semiconductor materials have been emerging as the main contenders in applications; these materials have the advantage of allowing both optical and electronic devices to be integrated. Further, the semiconductor technology has advanced rapidly, allowing us to engineer device parameters very precisely. In semiconductor optoelectronic devices, that is, bulk and quantum well structures, electroabsorption has mainly been used for amplitude modulation of light. The electrorefraction effect is the most useful for devices employing phase-modulation techniques, but this effect cannot be effectively utilized in semiconductors since the strongest electrorefraction effect is near the absorption edge of the material. Recently, organic materials have been shown to have electro-optic coefficients equal to or larger than that of lithium niobate. There are major advantages of organic materials: (1) the organics can be deposited on semiconductor substrates, and therefore both electronic and optical circuits can be integrated; (2) in organic materials the electrorefraction can be effectively utilized to obtain both amplitude and phase modulation; (3) the organic material composition can be adjusted to satisfy some device requirements. In this paper, a comparison of these material systems are made in terms of device applications.     

有机半导体光伏打电池--共轭聚合物及其与C60的复合体系

近年来，有机半导体太阳能电池引起科学工作者的极大兴趣，共轭聚合物/60复合体系在光伏打电池中的应用更是成为其中一个新的研究热点，文中介绍了有机半导体太阳能电池研究的背景，进展情况及存在的问题，并式材料合成，器件研究，机理探讨，薄膜制备等几个方面总结了文章作者在这一领域的研究工作进展。     

高效率和色稳定性的双超薄发光层的黄光有机电致发光器件

主要对rubrene黄光发光材料制作0.1nm厚度的超薄发光层的有机电致发光器件作了研究,并配合BCP空穴阻挡层探讨了对器件效率和色坐标稳定性的影响。双超薄rubrene发光层配合BCP空穴阻挡层的有机电致发光器件的性能得到了很好的改善,外加电压6V时,器件电流效率为6.35cd.A-1;外加电压10V时,器件发光亮度达到了7068cd.m-2。另外,在较大的外加电压驱动范围内,器件的色坐标一直保持在(0.49,0.49)。增加的发光效率和良好的色坐标稳定性主要是取决于空穴与电子的注入与输运平衡以及激子在超薄rubrene发光层中稳定性的复合平衡。     

与半导体相容的半金属铁磁体

文章在自旋电子学与新型计算机元件的背景下介绍了与半导体相容的半金属铁磁体，及其实验和理论研究进展情况．指出其中半稳能量低并且稳定性好的理论预测材料有可能不久通过外延方式在合适的基底上生长出来，并且得到实际应用．     

Organic field-effect transistors

The paper reviews the recent year publications concerning organic field-effect transistors (OFETs). A lot of works have been performed to help understanding the structural and electrical properties of materials used to construct OFETs. It has been established that in partially ordered systems, the charge transport mechanism is thermally activated and field-assisted hopping transport and the hopping transport between disorder-induced localized states dominate over intrinsic polaronic hopping transport seen in organic single crystals. Many research attempts have been carried out on the design of air-stable organic semiconductors with a solution process which is capable of producing OFETs with excellent properties and good stability when subjected to multiple testing cycles and under continuous electrical bias. Recent experiments have demonstrated ambipolar channel conduction and light emission in conjugated polymer FETs. These achievements are the basis for construction of OLED based displays driven by active matrix consisting of OFETs.     

High-efficiency Simple Structure White Organic Light-emitting Devices Based on Rubrene Ultrathin Layer

White organic light-emitting devices (WOLEDs) were fabricated with an ultrathin layer of rubrene inserted between NPB and TPBI. With a simple three-layer structure of ITO/NPB(50 nm)/rubrene(0.1 nm)/TPBI(50 nm)/LiF/Al, a white light with CIE coordinates of (0.31, 0.30) were generated. The device gave a maximum luminance efficiency of 2.04 lm/W at 5 V. Furthermore, with a multilayer structure of ITO/m-MTDATA(30 nm)/NPB(20 nm)/rubrene(0.1 nm)/TPBI(40 nm)/Alq₃(10 nm)/LiF/Al, the device reached a maximum luminance efficiency of 4.29 lm/W at 4 V and the luminance could exceed 10 000 cd/m² at 10 V.     

过渡金属掺杂的扶手椅型氮化硼纳米带的磁电子学特性及力-磁耦合效应

基于密度泛函理论的第一性原理计算方法,研究了多种过渡金属(TM)掺杂扶手椅型氮化硼纳米带(ABNNR-TM)的结构特点、磁电子特性及力-磁耦合效应.计算的结合能及分子动力学模拟表明ABNNRTM的几何结构是较稳定的,同时发现对于不同的TM掺杂,ABNNRs能表现出丰富的磁电子学特性,可以是双极化磁性半导体、一般磁性半导体、无磁半导体或无磁金属.双极化磁性半导体是一种重要的稀磁半导体材料,它在巨磁阻器件和自旋整流器件上有重要的应用.此外,力-磁偶合效应研究表明:ABNNR-TM的磁电子学特性对应力作用十分敏感,能实现无磁金属、无磁半导体、磁金属、磁半导体、双极化磁性半导体、半金属等之间的相变.特别是呈现的宽带隙半金属对于发展自旋电子器件有重要意义.这些结果表明:可以通过力学方法来调控ABNNR-TM的磁电子学特性.