【作者】 王宁；

【导师】 刘星元；

【作者基本信息】 中国科学院研究生院（长春光学精密机械与物理研究所） ， 凝聚态物理， 2010， 博士

【摘要】 透明导电氧化物(TCO)薄膜是一种重要的宽禁带光电薄膜,它是当代微电子学、光电子学、磁电子学、太阳能电池、传感器、电子物理器件等新兴交叉学科和技术的材料基础,并广泛地渗透到当代科技的各个领域。随着薄膜科学与技术的迅速发展,各种新型的光电子器件也不断出现,特别是以有机电致发光与有机光伏为代表的新型器件的出现,为开发新型功能薄膜和更优异的器件性能开辟了许多新的研究方向,并取得了令人瞩目的应用成果。本论文主要针对当前TCO的研究工作的热点问题,利用真空热蒸发和末端离子源辅助沉积的电子束蒸发方法,通过合理的理论设计,对当前氧化铟锡(ITO)在有机光电器件中的应用存在的问题进行了探索性研究,首次制备出一系列的二元及三元的新型TCO材料,获得了一些初步的结果。主要创新性结果如下:(1)首次报导了两种新的TCO材料,掺钒的氧化铟薄膜(IVO)及掺铋的氧化铟薄膜(IBO)。在薄膜未进行过退火处理的情况下,通过各种表征手段研究了薄膜的光电特性及钒与铋掺杂对氧化铟的电学及光学性质的影响。结果表明,IVO及IBO都有着与商业ITO可比拟的电学及光学特性。基于它们制备的有机电致发光器件(OLED)都获得了比基于ITO阳极器件更好的性能。(2)首次报导了两种新型的高功函数的三元体系TCO材料,掺钛酸镁的氧化铟薄膜(IMTO)及掺钛酸镨的氧化铟薄膜(IPTO)。我们详细地研究了这两种TCO材料的光电特性。IMTO与IPTO都有着较为平坦及光滑的表面,两者都有着较高的可见光透过率(~80%)和较大的禁带宽度(4.65 eV与4.26 eV)。IMTO与IPTO都有着可与金的功函数媲美的表面功函数(> 5.1 eV),而且两种薄膜的表面功函数有着非常高的均一性及大气稳定性。基于这两种薄膜的OLED器件表现出比基于ITO器件更好的性能。与传统的三元制备方法相比,我们的方法不仅对设备的要求不高而且成本较低,便于今后的大规模商业应用。(3)首次报导了一种新型的三元体系的TCO材料,掺杂钛酸镧的TCO薄膜(ILTO)。ILTO除了有着优异的光电特性外,在室温下该材料还具有近紫外(386 nm)的PL特性。我们期望该材料在金属氧化物体系,特别是多重氧化物体系中能够做为一种功能层去实现近紫外的光致发光(PL)及电致发光(EL)器件。ILTO具有高达5.2 eV的表面有效功函数,而且该薄膜功函数的热稳定性非常好。利用ILTO阳极制备的OLED比ITO阳极器件获得了更好的电致发光性能;基于ILTO阳极的有机太阳能电池(OSC)也取得了比基于ITO阳极的OSC更好的光电转换性能。ILTO作为新型TCO阳极,在有机光电子器件中表现出了优异的性能。更多还原

【Abstract】 Transparent conducting oxide （TCO） is an important wide band gap semiconductor and the basic material in the fields of microelectronics, optoelectronics, magnetoelectronics, solar cells, sensors and electrical physics devices. With quickly development of science and technology of thin films, many novel photoelectric devices are developed. Especially, the emergence of organic light-emitting diodes （OLEDs） and organic solar cells （OSCs） stimulates the deep investigation on novel functional thin films and device physics. In this thesis, we develop series of new binary and ternary TCO thin films by modified thermal evaporation deposition and double source reactive electron beam evaporation with End-Hall ion assisted deposited （EHIAD） technologies according to the investigation on the merit and shortcoming of indium tin oxide （ITO） in the application of OLED and OSC. The details are as follows:（1） Two new binary TCO thin films, vanadium and bismuth doped indium oxides （IVO and IBO）, are developed by a modified thermal evaporation deposition method. Under unannealed treatment for samples, we investigate the optical and electrical characteristics, and the effects of vanadium and bismuth incorporation on the optical and electrical properties of samples by using Hall measurements, spectrophotometer, Scanning Electron Microscope （SEM）, Energy-dispersive X-ray Spectroscopy （EDX） and so on. Our results show that the optical and electrical properties of IVO and IBO samples are comparable to that of commercial ITO. Furthermore, OLEDs based IVO and IBO anodes harvest better performance than the ITO control device.（2） EHIAD techonology is used to deposite two new high work-fucntion ternary TCO coatings, magnesium titanate （MgTiO₃） and praseodymium titanate （PrTiO3）-doped indium oxides （IMTO and IPTO, respectively）. Comparing with conventional preparation methods of ternary compound, our technique has a lower cost and the method is beneficial for future industrial manufacture. The surface root-mean-square （RMS） roughnesses of IMTO and IPTO samples have very low values of 0.704 and 1.943 nm, respectively. They are smoother than commercial sputter-derived ITO, which has a RMS roughness of 2.514 nm. All samples demonstrate a high surface work function beyond 5.1 eV, which is comparable to the work function of Au, and much higher than that of commercial ITO. Moreover, the stability of work function of samples is investigated in air. We apply samples as contact anodes to replace ITO in OLEDs, significant improvements in electroluminescence performance for the IMTO and IPTO-anode OLEDs are achieved.（3） A novel high work-function TCO, lanthanum titanate （LaTiO₃）-doped indium oxide （ILTO）, with notable electrical and optical features, synthesized by a double electron beam evaporation associated with EHIAD technology is introduced. Its room-temperature ultraviolet photoluminescence （PL） and thermally stable highly effective work function properties are determined. High performance OLEDs and OSCs based on ILTO anodes have been achieved and their effects are discussed in detail.更多还原