Optical properties and electrical bistability of CdS nanoparticles synthesized in dodecanethiol

We reported the synthesis of CdS semiconductor nanoparticles using a simple one-pot reaction by thermolysis of cadmium acetylacetonate in dodecanethiol. Optical measurements of the as-obtained CdS nanoparticles revealed that their optical properties were closely related to surface effects. Based upon the cocktail of poly (N-vinylcarbazole) (PVK) and CdS nanoparticles, a bistable device was fabricated by a simple solution processing technique. Such a device exhibited a remarkable electrical bistability, which was attributed to the electric field-assisted charge transfer between PVK and the CdS nanoparticles capped by dodecaethiol. The conduction mechanism changed from an injection-controlled current to a bulk-controlled one during switching from OFF-state to ON-state.

Electroluminescence behavior of ZnO/Si heterojunctions: Energy band alignment and interfacial microstructure

n-ZnO/p-Si heterojunction light-emitting diodes (LEDs) show weak defect-related electroluminescence (EL). In order to analyze the origin of the weak EL, the energy band alignment and interfacial microstructure of ZnO/Si heterojunction are investigated by x-ray photoelectron spectroscopy. The valence band offset (VBO) is determined to be 3.15 +/- 0.15 eV and conduction band offset is -0.90 +/- 0.15 eV, showing a type-II band alignment. The higher VBO means a high potential barrier for holes injected from Si into ZnO, and hence, charge carrier recombination takes place mainly on the Si side rather than the ZnO layer. It is also found that a 2.1 nm thick SiOx interfacial layer is formed at the ZnO/Si interface. The unavoidable SiOx interfacial layer provides to a large number of nonradiative centers at the ZnO/Si interface and gives rise to poor crystallinity in the ZnO films. The weak EL from the n-ZnO/p-Si LEDs can be ascribed to the high ZnO/Si VBO and existence of the SiOx interfacial layer.

Broadband external cavity tunable quantum dot lasers with low injection current density

Broadband grating-coupled external cavity laser, based on InAs/GaAs quantum dots, is achieved. The device has a wavelength tuning range from 1141.6 nm to 1251.7 nm under a low continuous-wave injection current density (458 A/cm(2)). The tunable bandwidth covers consecutively the light emissions from both the ground state and the 1st excited state of quantum dots. The effects of cavity length and antireflection facet coating on device performance are studied. It is shown that antireflection facet coating expands the tuning bandwidth up to similar to 150 nm, accompanied by an evident increase in threshold current density, which is attributed to the reduced interaction between the light field and the quantum dots in the active region of the device.

One-pot synthesis and self-assembly of colloidal copper(I) sulfide nanocrystals

A simple one-pot method is developed to prepare size-and shape-controlled copper(I) sulfide (Cu2S) nanocrystals by thermolysis of a mixed solution of copper acetylacetonate, dodecanethiol and oleylamine at a relatively high temperature. The crystal structure, chemical composition and morphology of the as-obtained products are characterized by powder x-ray diffraction (PXRD), x-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The morphology and size of the Cu2S nanocrystals can be easily controlled by adjusting the reaction parameters. The Cu2S nanocrystals evolve from spherical to disk-like with increasing reaction temperature. The spherical Cu2S nanocrystals have a high tendency to self-assemble into close-packed superlattice structures. The shape of the Cu2S nanodisks changes from cylinder to hexagonal prism with prolonged reaction time, accompanied by the diameter and thickness increasing. More interestingly, the nanodisks are inclined to self-assemble into face-to-face stacking chains with different lengths and orientations. This one-pot approach may extend to synthesis of other metal sulfide nanocrystals with different shapes and sizes.

高性能聚合物白光电致发光器件研究

聚合物白光电致发光器件可以采用旋涂、喷墨打印等方法成膜，具有工艺简单、成本低等优点，在全色平板显示和照明光源等方面具有广阔的应用前景，吸引了广泛的关注。聚合物白光电致发光器件同小分子发光器件相比发光效率仍然很低，如何提高聚合物白光器件的效率是急需解决的问题。而另一个评价白光器件性能的重要参数就是显色指数(color rendering index , CRI)。目前所报道的有机白光器件的显色指数普遍低于80，如何提高聚合物白光器件的显色指数也是我们研究的重点。本论文在载流子的注入平衡控制、白光聚合物薄膜的聚集态调控改善其光电性能和设计新型器件结构提高白光器件效率等方面进行了系统、深入的研究，在提高聚合物白光电致发光器件的效率和色纯度方面取得了较大的研究进展，为发展高质量的聚合物白光电致发光器件提供了理论基础和实施途径。 1. 首次将醇溶性含磷酸脂基团的聚芴衍生物作为电子注入材料应用到聚合物电致发光器件中，并采用高功函数铝作为阴极获得了高效率的聚合物电致发光。醇溶性含磷酸酯聚芴界面材料不但实现了多层聚合物结构，而且磷酸酯与金属铝的特殊作用有利于高效率电子注入。我们成功地将其应用到红、绿、蓝三基色聚合物发光器件中，与传统的Ca/Al电极聚合物器件相比，这种新型界面材料的使用有效降低了器件的工作电压，发光效率提高了25 %以上。 2. 利用物理掺杂的方法通过选用白光聚合物(由蓝光和橙光组成)作为主体、高效率红光磷光染料作为客体实现了包含红、绿、蓝三基色的高显色指数白光聚合物电致发光，色坐标为 (0.34，0.35)，显色指数达到 92。通过在发光层中引入电子传输材料实现了载流子的传输平衡，提高了白光器件的发光效率，发光效率达到5.3 cd/A。 3. 采用含苯并噻二唑基元的聚芴衍生物作为白光发光层(由蓝光和橙光组成)，利用热退火及溶剂处理等方式控制白光聚合物薄膜聚集态结构，有效调控了白光聚合物薄膜的载流子传输平衡和白光的色纯度。利用热处理或溶剂处理提高了薄膜的空穴迁移率，平衡了载流子传输，使发光效率由原来的7.3 cd/A提高到10 cd/A以上。同过热处理及溶剂处理后的白光聚合物薄膜中出现了高发光效率的聚芴结晶相，提高了蓝光部分的发光效率和色纯度，进而提高了白光的色纯度。 4. 利用含苯并噻二唑基元的聚芴衍生物白光聚合物和含磷酸酯醇溶性蓝光聚芴构筑了高效率双发光层聚合物白光电致发光器件。通过控制白光聚合物薄膜的聚集态结构提高空穴迁移率和引入醇溶性蓝光聚芴界面层改善电子注入实现了载流子传输平衡，同时将激子复合区域限制在两个发光层之间，避免了由于电极造成的激子淬灭，器件的发光效率达到17 cd/A和11 lm/W，是目前国际上报道的非掺杂型聚合物白光电致发光的最高值。 5. 利用高色纯度的蓝光聚芴、绿光和红光磷光染料实现了包含红绿蓝三基色的高显色指数白光；通过器件结构的设计提高器件中三线态激子的利用效率和抑制磷光染料中三线态激子向聚芴低三线态能级的能量转移，实现了高效率、高显色指数聚合物白光电致发光。 其中红光和绿光发光层由高三线态能级的聚乙烯咔唑掺杂绿光和红光磷光染料组成，蓝光发光层采用含磷酸脂基团聚芴，在两个发光层间引入高三线态能级激子限制层，有效抑制了磷光染料三线态激子被低三线态能级聚芴的淬灭，实现了高发光效率的包含红、绿、蓝三基色的高显色指数聚合物电致白光。器件最高效率可达到10.4 cd/A， 色坐标为 (0.36, 0.39)，显色指数达到91。

垂直结构金属基极有机晶体管及其在有机发光驱动中的应用

近几十年来，有机半导体材料作为新一代的信息功能材料正以其光电性能优异、生产成本低廉、加工工艺简单、选材范围宽广、机械性能柔软等显著的优点，吸引了世界范围内的目光，成为越来越多研究机构竞相研究和开发的对象，被广泛应用于发光二极管、薄膜晶体管、太阳能电池、存储器等光电子器件中。这些有机半导体器件的应用前景十分广阔，其巨大的商业价值极大地推动了有机半导体器件的发展。 本论文主要制备了N型金属基极有机晶体管，并对其性能进行了研究和分析，并在此基础上，研究了其在有机发光驱动中的应用。 (1) 用N型有机半导体材料Alq3、F16CuPc和BAlq3作发射极层，Au作为基极，N型硅作为收集极层，Al作为发射极接触电极成功地制备出了一系列N型无机/有机杂化金属基极晶体管，这些器件都表现出了良好的共基极增益特性，最大共基极增益达到了0.991，接近理想值1。在此基础上，通过在发射极层和发射极电极之间引入V2O5界面修饰层，还实现了具有良好共发射极特性的N型无机/有机杂化金属基极晶体管。研究发现，V2O5界面修饰层的引入明显地减小了共基极漏电流，使器件的共基极特性得到了进一步的改善，同时也使器件表现了共发射极特性，实现了电流的放大，我们已经把共基极特性的改善和共发射极特性的实现归功于界面修饰层的引入提高了电子注入的结果。 (2) 根据金属与半导体的接触理论,设计制备出了带有Au/Al双层金属基极的N型无机/有机杂化金属基极晶体管。由于Al和Alq3之间好的接触特性和有效的从Al到Alq3的空穴阻挡特性以及Au和Si之间良好的肖特基接触特性，大大降低了器件的漏电流，使器件在低的电压下表现了优异的共基极和共发射极特性，共基极增益达到了近似理想值1，最大共发射机增益达到了4000，克服了单层金属基极晶体管难实现共发射极特性的问题，为实现高性能金属基极晶体管提供了新的思路。 (3) 利用异质结的概念，设计制备出了带有BAlq3/Alq3异质结结构的N型无机/有机杂化金属基极晶体管，该器件同样表现了优异的共基极和共发射极特性。研究发现，同Alq3单发射极层结构的金属基极晶体管相比，BAlq3/Alq3异质结发射极层的使用进一步降低了器件的漏电流，使器件在相同的电压下表现了更高的输出电流和更高的共发射极增益，为进一步实现高性能金属基极晶体管提供了新的方法。 (4) 用有机半导体材料取代无机高掺杂硅作为收集极层，制备出了带有Al单层金属基极和Au/Al双层金属基极的N型垂直结构全有机金属基极晶体管，该器件表现出了良好的共基极特性和共发射极特性。研究表明，全有机金属基极晶体管表现了和无机/有机混合型金属基极晶体管相似的特性，其从本质上说也是一种渗透型金属基极晶体管。 (5) 实现了金属基极有机晶体管驱动有机发光二极管的集成器件。利用金属基极有机晶体管的共发射极电流放大特性，在基极输入电流IB量级比较低（uA）的情况下，得到了较大量级（mA）的输出电流IC，从而实现了对白光有机发光二极管的驱动，在基极输入电流IB为1×10-5A时有机发光二极管的亮度达到了1279 cd/m2。

稀土配合物光致发光和电致发光性能的研究

有机电致发光器件(organic light-emitting diodes, OLEDs)由于具有全色、低压直流驱动、视角广、高效率和易于制备大屏幕等优点，在平板显示领域具有广阔的应用前景，已引起世界范围内科技界和企业界的广泛重视。稀土配合物作为发光及载流子传输层材料，具有窄带发射和发射波长分布范围广的特点，有利于实现高的色纯度。然而，有机电致发光的机理还未完全弄清楚，稀土配合物电致发光器件距离实际应用还比较远，需要进一步进行研究。本论文研究了Tb~(3+)、Eu~(3+), Sm~(3+)配合物的光致发光和电致发光性质，制备了绿色、红色和橙色电致发光器件，并对稀土配合物的电致发光机理进行了探讨。对于试配合物，以acac为第一配体，研究了第二配体AAP和bath对配合物和器件发光性能的影响并对器件的优化进行了讨论；以Tb(acac)_3bath为发光中心，发现电致发光中~5D_4→~7F_5跃迁相对~5D_4→~7F_5跃迁的增强现象；以Tfacac为第一配体，首次讨论了F取代H对于配体的三重态能级的降低和对配合物以及电致发光器件发光强度的增强作用，对于提高稀土配合物电致发光的性能提供了参考依据。对于铺配合物，以Tfacac为第一配体，以phen和bipy为第二配体，制备了红色电致发光器件并进一步验证了F取代H对于配体的三重态能级的降低作用；以HTH为第一配体，国际上首次报道了室温下Eu~(3+)离子的~5D_1→~7F_J的跃迁，并且其强度依赖于驱动电压的强度，光致发光和电致发光的不同表明二者的发光机理有所不同，并对铺配合物电致发光机理进行了讨论；以HTH为第一配体，国际上首次报道了衫配合物的电致发光现象，并且最大得到了21 cd/m~2的发光强度；为了改善稀土β-二酮配合物光稳定性和热稳定性差的缺点，引入了稀土芳香梭酸配合物，并对配体进行了引入长链的化学修饰，提高了配合物在一般有机溶剂中的溶解度，用旋涂法制备的器件的最大发光亮度达到了174 cd/m~2.

OLED中空穴传输层NPB薄膜的结晶化行为研究

近年来，虽然有机电致发光材料和有机电致发光器件得到了广泛的研究，然而贯穿整个有机电致发光研究主线的稳定性问题仍是一个重要的议题。作为发光器件的主要组成部分，有机小分子薄膜的性能不仅由组成分子结构决定，而且还受到自身形态结构的制约。要解决有机材料的热稳定性问题，材料薄膜的形态结构是一个重要的影响因素。弄清有机小分子薄膜的形态结构和性能间的相互关系对于进一步提高器件性能（效率和寿命）是十分必要的。有机分子的热不稳定性表现在形态结构上主要是由非晶态到结晶态的转变，从而引起器件性能的不稳定。所以本文详细研究了一种典型的半晶性有机分子薄膜（同时也是最经常使用的有机小分子空穴传输材料之一）-NPB薄膜的结晶化相转变，分别从均相成核结晶化相转变和异相成核结晶化相转变两个角度来阐述。本文通过AFM、PLM、X射线衍射、DSC等实验方法和研究手段表征了NPB薄膜由非晶态到结晶态的相态转化，并从热力学上进行了分析。同时结合了实际OLED器件中的应用。本论文研究表明NPB分子是一种典型的半晶性小分子，非晶与结晶两种状态的并存导致热力学上的不稳定。本论文详细研究了NPB薄膜的均相成核结晶化相转变和异相成核结晶化相转变，并指出半晶性的NPB分子薄膜的均相成核结晶化存在一个临界结晶厚度，当薄膜厚度超过临界结晶厚度时才能发生结晶。并且临界结晶厚度的大小与基底温度有关。而NPB薄膜的异相成核结晶化转变则由于异核的引入结晶能的降低相对来说容易许多。本论文首次从理论角度归纳提出了均相成核结晶老化机制和异相成核结晶老化机制两种关系到OLED器件稳定性（老化问题）的机制。是为数不多的从薄膜形态角度来研究器件稳定性的一篇文章，对从材料化学角度深入理解OLED器件稳定性有着重要的意义。

LIQUID-PHASE EPITAXY GROWTH AND PROPERTIES OF GAINASSB/ALGAASSB/GASB HETEROSTRUCTURES

The GaInAsSb/AlGaAsSb/GaSb heterostructures were grown by the liquid phase epitaxy (LPE) technique. The materials were characterized by means of optical microscopy, electroprobe microanalysis (EPMA), double-crystal X-ray diffraction, capacitance-voltage (C-V) and Van der Pauw measurments, infrared absorption spectra, photoluminescence and laser Raman scattering. The results show that the materials have fine surface morphology, low lattice mismatch and good homogeneity. Room-temperature light-emitting diodes with an emission wavelength of 2.2-mu-m were obtained by using the GaInAsSb/AlGaAsSb DH structures.

Some properties of gallium nitride films grown on (0001) oriented sapphire substrates by gas source molecular beam epitaxy

The Raman and photoreflectivity spectra of gallium nitride (GaN) films grown on (0001) oriented sapphire substrates by gas source molecular beam epitaxy (GSMBE) have been investigated. The Raman spectra showed the presence of the E-2(high) mode and a shift in the wavenumber of this mode with respect to the GaN epilayer thickness. The Raman scattering results suggest the presence of stress due to lattice and thermal expansion misfit in the films, and also indicate that the buffer layer play an important role in the deposition of high quality GaN layers. The residual stress changes from tensile to compressive as the epilayer thickness increases. Samples subjected to anneal cycles showed an increase in the mobility due probably to stress relaxation as suggested by an observed shift in the E-2(high) mode in the Raman spectra after annealing.

Growth of GaN layers on GaAs and GaP (111) and (001) substrates by molecular beam epitaxy

Films of GaN have been grown using a modified MBE technique in which the active nitrogen is supplied from an RF plasma source. Wurtzite films grown on (001) oriented GaAs substrates show highly defective, ordered polycrystalline growth with a columnar structure, the (0001) planes of the layers being parallel to the (001) planes of the GaAs substrate. Films grown using a coincident As flux, however, have a single crystal zinc-blende growth mode. They have better structural and optical properties. To improve the properties of the wurtzite films we have studied the growth of such films on (111) oriented GaAs and GaP substrates. The improved structural properties of such films, assessed using X-ray and TEM method, correlate with better low-temperature FL.

Optical properties of AIInGaN quaternary alloys

Carrier recombination dynamics in AlInGaN alloy has been studied by photoluminescence (PL) and time-resolved photoluminescence (TRPL). The fast redshift of PL peak energy is observed and well fitted by a physical model considering the thermal activation and transfer processes. This result provides evidence for the exciton localization in the quantum dot (QD)-like potentials in our AlInGaN alloy. The TRPL signals are found to be described by a stretched exponential function of exp[(-t/tau)(beta)], indicating the presence of a significant disorder in the material. The disorder is attributed to a randomly distributed quantum dots or clusters caused by indium fluctuations. By studying the dependence of the dispersive exponent 8 on the temperature and emission energy, we suggest that the exciton hopping dominate the diffusion of carriers localized in the disordered quantum dots. Furthermore, the localized states are found to have OD density of states up to 250 K, since the radiative lifetime remains almost unchanged with increasing temperature.

The growth and characterization of GaN grown on a gamma-Al2O3/(001) Si substrate by metalorganic vapor phase epitaxy

Wurtzite single crystal GaN films have been grown onto a gamma-Al2O3/Si(001) substrate in a horizontal-type low pressure MOVPE system. A thin gamma-Al2O3 layer is an intermediate layer for the growth of single crystal GaN on Si although it is only an oriented polycrystal film as shown by reflection high electron diffraction. Moreover, the oxide is not yet converted to a fully single crystal film, even at the stage of high temperature for the GaN layer as studied by transmission electron microscopy. Double crystal x-ray linewidth of (0002) peak of the 1.3 mu m sample is 54 arcmin and the films have heavy mosaic structures. A near band edge peaking at 3.4 eV at room temperature is observed by photoluminescence spectroscopy. Raman scattering does not detect any cubic phase coexistence.

Growth and characterization of GaN on LiGaO2 and LiAlO2

The nearly lattice-matched LiGaO2 and LiAlO2 substrates have been used for the growth of GaN by LP-MOVPE. GaN epilayers have been grown on the two substrates at very low input partial pressure of hydrogen and relatively low growth temperature. The difference in the growth rate, crystal and optical qualities of hexagonal GaN epilayers grown on LiAlO2 and LiGaO2 substrate with two polar domains are investigated. LiAlO2 and LiGaO2 single crystal with a single domain structure and an adequate surface plane are promising substrates for the growth of high quality of hexagonal GaN thin films.

Yellow luminescence mechanism and persistent photoconductivity in n-GaN single crystal films grown on alpha-Al2O3(0001) substrates by LP-MOCVD

Unintentionally doped and Si-doped single crystal n-GaN films have been grown on alpha-Al2O3 (0001) substrates by LP-MOCVD. Room temperature photoluminescence measurement showed that besides the bandedges, the spectrum of an undoped sample was a broad deep-level emission band peaking from 2.19 to 2.30eV, whereas the spectrum for a Si-doped sample was composed of a dominant peak of 2.19eV and a shoulder of 2.32eV. At different temperatures, photoconductance buildup and its decay were also observed for both samples.. The likely origins of persistent photoconductivity and yellow luminescence, which might be associated with deep defects inclusive of either Ga vacancy(V-Ga)/Ga vacancy complex induced by impurities or N antisite (N-Ga), will be proposed.