【作者】 梁志强；

【导师】 B.B.阿布拉依莫夫（V. V. Abraimof）； 李春东；

【作者基本信息】 哈尔滨工业大学 ， 材料学， 2013， 博士

【摘要】 ZnO的优良光电性能以及可采用多种方法制备多种微纳结构的特点，使其在涂层颜料、太阳能电池、压敏和气敏原件、发光二极管和激光器、压电器件、紫外探测器和传感器等诸多领域得到广泛应用，具有广阔前景。此外，ZnO还具有优良的抗辐射能力，使其光电特性在空间辐射环境中具有良好稳定性，适合空间应用。近年来，ZnO的制备和应用研究取得不断进展，但为实现ZnO基光电器件的进一步发展和在实际上的广泛应用，仍需对ZnO微纳结构的可控合成、设计并制备性能优异且稳定可靠的光电器件等方面进行深入研究。本文致力于ZnO基微纳核壳结构颗粒和ZnO纳米薄膜的可控合成和性能研究，并基于不同微纳结构ZnO材料的性能特点，分别研究了ZnO基微纳核壳结构颗粒作为热控涂层颜料以及ZnO纳米薄膜作为倒置型聚合物太阳能电池（PSCs）阴极缓冲层和电子收集层的应用相关问题。主要研究内容如下：设计并采用固相反应法制备了具有微纳核壳结构的新型ZnO基复合颜料，研究了制备工艺参数对复合颜料结构和成分的影响，探讨了复合颜料的结构和成分与其光学性能和辐照光学稳定性之间的关系。研究发现ZnO基微纳核壳结构复合颜料不但具有优良的初始光学性能，并在模拟空间质子、电子单独及综合辐照作用下具有优于ZnO原料的辐照光学稳定性。X射线衍射谱、光谱反射率和太阳吸收比的测试和计算结果显示，当ZnO基微纳核壳结构复合颜料中Zn₂SiO₄壳层的相对含量约为67%时，复合颜料在质子辐照下太阳吸收比的变化（△αs）相比于ZnO原料降低了约36%，具有最佳的辐照光学稳定性。研究了ZnO基微纳核壳结构复合颗粒的表面Zn₂SiO₄壳层对复合颜料在模拟空间带电粒子辐照下光学稳定性的影响机制。研究发现Zn₂SiO₄壳层可有效吸收入射粒子的能量，降低带电粒子辐照对ZnO基体的辐照损伤，提高复合颜料的辐照光学稳定性。此外，Zn₂SiO₄壳层自身优良的辐照光学稳定性也在一定程度上有利于复合颜料辐照光学稳定性的提高。采用溶胶-凝胶法，通过调节溶胶浓度和热处理工艺制备了具有可控微观表面形貌、厚度和透光率的ZnO纳米薄膜。研究了以ZnO纳米薄膜作为阴极缓冲层的倒置型PSCs的制备和性能，系统研究了ZnO纳米薄膜的表面微观形貌、厚度和透光率对倒置型PSCs性能的影响规律和作用机理。研究发现，在一定厚度范围内，ZnO纳米薄膜的表面微观形貌可直接影响ZnO与P3HT:PCBM活性层的接触质量，是影响电池性能的关键因素，而ZnO纳米薄膜的厚度和透光率对电池性能影响较小。基于表面致密、光滑且无孔洞的ZnO纳米薄膜的倒置型PSCs的能量转换效率为³.3%，相比于以表面粗糙且有孔洞的ZnO纳米薄膜的倒置型PSCs的能量转换效率（2.5%）提高了约32%。基于化学溶液法设计了一种新的ZnO纳米墙薄膜制备工艺，在低温下制备了垂直于ITO基底的ZnO纳米墙薄膜。研究发现，通过适当提高反应溶液浓度、降低反应温度和溶液初始pH值可制备致密的ZnO棒薄膜。该致密ZnO棒薄膜可在KOH水溶液中发生沿ZnO棒c轴的选择性刻蚀，形成纳米墙结构。初步研究了基于ZnO纳米墙薄膜的倒置型PSCs的制备和性能，研究表明ZnO纳米墙薄膜可有效用作倒置型PSCs的电子收集层，具有进一步研究和发展的潜力。更多还原

【Abstract】 ZnO shows excellent properties and a various of micro/nano-structured ZnOcan be readily achieved by many methods, which make it a promising material forwidespread application in pigments of coating, solar cells, pressure-sensitive andgas-sensitive elements, light-emitting diodes and lasering, piezoelectric device,ultraviolet detector and sensors and so on. In addition, ZnO holds high resistance toradiation damage making it suitable to space application.In recent year, although constant progresses have been achieved, controlledsynthesis of micro/nano-structured ZnO materials and the design and fabrication ofphoto-electric devices with excellent performance and high device stability are stillchallenging for further development and industrial application of ZnO materials. Inthis regard, this work is mainly focused on the controlled synthesis of the ZnObased micro/nano-partials with core-shell structure, ZnO nano-structured films withdesired optical properties and morphology. In addition, based on the differentproperties of the above-mentioned ZnO materials are explored to serve as thepigments of thermal control coating and the cathode buffer layer of invertedpolymer solar cells, respectively. The contents of this work are listed as following:ZnO based composited pigments with micro/nano and core-shell structure havebeen designed and fabricated. Fabrication and optical properties of the ZnO basedcomposited pigments are investigated, and the optical stability of the compositedpigments under the irradiation of space charge particles is also studied. It has beenfound that the ZnO-based composite pigments hold both high spectral reflectanceand good optical stability under the simulated space irradiation of protons andelectrons. Based on the analysis results of XRD patterns and spectral reflectance, ithas been found that the composite pigment contain67%Zn₂SiO₄shell layer exhibitsthe lowest change in solar absorptance, a37%decrease compared to that of theas-received ZnO pigments, the best optical stability under protons irradiation wasachieved.The mechanisms under the excellent optical stability of the composite pigmentirradiated by space charged particles are investigated. It has been demonstrated thatthe Zn₂SiO₄surface layer could effectively reduces the quantity of the irradiationinduced defects in ZnO substrate by absorbing part of the energy of the incidentparticles, and thus further improving the optical stability of the composite pigment.In addition, it has found that the optical stability of Zn₂SiO₄shell layer is better thanthat of as-received ZnO pigments to some extent, which partly enhanced the optical stability of the composite pigments.ZnO nano-films with controlled morphology, thickness and transmittance arefabricated by using an improved sol-gel method. The fabrication and devicesperformance of the inverted polymer solar cells with ZnO nano-films as a cathodebuffer layer are also investigated. The influence of the morphology, thickness andtransmittance of ZnO nano-films on the performance of inverted polymer solar cellsare systematically investigated. It has been demonstrated that, in a certain thicknessrange, the device performance is strongly dependent on the ZnO morphology ratherthan thickness and transmittance. The morphology of the ZnO nano-films plays adirect and important role in the contact quality between P3HT: PCBM active layerand ZnO, and thus impact on the fill factor and power conversion efficiency of theinverted devices. Inverted devices with a dense and homogenous ZnO buffer layerderived from0.1M sol exhibit an power conversion efficiency of3.3%which is a32%increase compared to devices with a rough ZnO buffer layer made from1Msol, which exhibited a power conversion efficiency of2.5%.A route based on the chemical solution deposition at low temperature isdesigned to fabricate the ZnO nanowall arrays. The films with super dense ZnOrods are prepared by increasing the precursor concentration and decreasing thegrowth temperature and initial temperature of solution. The nanowall formation isascribed to selective dissolution of （001） planes of chemical bath deposited denseZnO rods The ZnO nanowall arrays are firstly explored as an electrons collectinglayer in inverted polymer solar cells. The primary result shows that the aqueousgrowth ZnO NW networks with a potential to serve as a new electrode for thefurther development of inverted polymer solar cells.更多还原