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Influence of secondary phases during annealing on re-crystallization of CuInSe_2 electrodeposited films

机译：退火过程中次生相对CuInSe_2电沉积膜再结晶的影响

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Electrodeposited CuInSe_2 thin films are of potential importance, as light absorber material, in the next generation of photovoltaic cells as long as we can optimize their annealing process to obtain dense and highly crystalline films. The intent of this study was to gain a basic understanding of the key experimental parameters governing the structural-textural-composition evolution of thin films as function of the annealing temperature via X-ray diffraction, scanning/transmission electron microscopy and thermal analysis measurements. The crystallization of the electrodeposited CuInSe_2 films, with the presence of Se and orthorhombic Cu_(2-x)Se (o-Cu_(2-x)Se) phases, occurs over two distinct temperature ranges, between 220 ℃ and 250 ℃ and beyond 520 ℃. Such domains of temperature are consistent with the melting of elemental Se and the binary CuSe phase, respectively. The CuSe phase forming during annealing results from the reaction between the two secondary species o-Cu_(2-x)Se and Se (o-Cu_(2-x)Se + Se→2 CuSe) but can be decomposed into the cubic β-Cu_(2-x)Se phase by slowing down the heating rate. Formation of liquid CuSe beyond 520℃ seems to govern both the grain size of the films and the porosity of the substrate-CuInSe_2 film interface. A simple model explaining the competitive interplay between the film crystalliniry and the interface porosity is proposed, aiming at an improved protocol based on temperature range, which will enable to enhance the film crystalline nature while limiting the interface porosity.
机译：只要我们可以优化其退火工艺以获得致密且高度结晶的薄膜，电沉积的CuInSe_2薄膜作为光吸收材料在下一代光伏电池中具有潜在的重要性。这项研究的目的是通过X射线衍射，扫描/透射电子显微镜和热分析测量，对作为退火温度函数的薄膜的结构-组织-组成演变的关键实验参数有基本的了解。在Se和正交晶体Cu_（2-x）Se（o-Cu_（2-x）Se）相的存在下，电沉积CuInSe_2薄膜的结晶发生在两个不同的温度范围内，介于220℃和250℃之间，甚至更高520℃。这种温度域分别与元素硒和二元CuSe相的熔化相一致。退火过程中形成的CuSe相是由两个次级物种o-Cu_（2-x）Se和Se（o-Cu_（2-x）Se + Se→2 CuSe）之间的反应引起的，但可以分解为立方β -Cu_（2-x）Se相通过降低加热速率来实现。超过520℃时，液态CuSe的形成似乎决定着膜的晶粒尺寸和基底-CuInSe_2膜界面的孔隙率。提出了一个简单的模型来解释薄膜结晶度和界面孔隙率之间的竞争相互作用，旨在基于温度范围的改进方案，这将能够在限制界面孔隙率的同时增强薄膜的晶体性质。

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