Unravelling the Role of Stacking Disorder on the Optoelectronic Properties of Zn3P2
揭示堆叠无序对Zn3P2光电性质的作用
Francesco Salutari, Nico Kawashima, Aidas Urbonavicius, Helena Rabelo Freitas, Raphael Lemerle, Thomas Hagger, Kimberly A. Dick, Anna Fontcuberta i Morral, Simon Escobar Steinvall, Maria Chiara Spadaro, Silvana Botti, Jordi Arbiol
AI总结 通过透射电镜和第一性原理计算,发现Zn3P2中一种新型平面缺陷,其形成能极低且不引入带隙态,但可能通过吸引点缺陷间接影响器件性能。
Comments 33 pages
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磷化锌(Zn3P2)因其地球丰富的组成和有利的光电性质,是一种有前景的薄膜和柔性太阳能电池光伏吸收材料。尽管其晶格参数和热膨胀系数不匹配带来挑战,但外延技术的最新进展已能生长高质量Zn3P2薄膜。然而,Zn3P2仍然容易产生固有扩展缺陷,例如旋转畴,这些缺陷可能限制器件性能。在这里,使用(扫描)透射电子显微镜,我们识别出一类先前未报道的扩展缺陷,表现为由位于(001)平面的位移矢量描述的平面断层。在Zn3P2的伪立方描述中,我们建立了平面断层和旋转畴之间的直接对应关系,表明两者都源于Zn亚晶格中空位的灵活有序排列。第一性原理计算揭示平面缺陷的形成能极低,为2.5 mJ m-2,表明这些缺陷以几乎可忽略的能量成本形成,与实验观察到的高出现率非常一致。额外的密度泛函理论(DFT)计算表明,本征平面缺陷既不引入带隙中间电子态,也不显著扰动局部静电势,表明它们在电子上是良性的。相反,我们提出平面缺陷通过作为光学活性点缺陷的优先偏析位点,间接降低器件性能。
Zinc phosphide (Zn3P2) is a promising photovoltaic absorber for thin-film and flexible solar cells due to its earth-abundant composition and favourable optoelectronic properties. Recent advances in epitaxy have enabled the growth of high-quality Zn3P2 thin films despite the challenges posed by its incompatible lattice parameter and thermal expansion coefficient. However, Zn3P2 remains prone to intrinsic extended defects, such as rotated domains, that can limit device performance. Here, using (scanning) transmission electron microscopy, we identify a previously unreported class of extended defects that appear as planar faults described by displacement vectors lying in the (001) plane. Within a pseudo-cubic description of Zn3P2, we establish a direct correspondence between planar faults and rotated domains, showing that both arise from the flexible ordering of vacant sites in the Zn sublattice. First-principles calculations reveal an extremely low planar-defect formation energy of 2.5 mJ m-2, demonstrating that these defects form at essentially negligible energetic cost, in excellent agreement with their high experimentally observed occurrence. Additional density functional theory (DFT) calculations show that intrinsic planar defects neither introduce mid-gap electronic states nor significantly perturb the local electrostatic potential, indicating that they are electronically benign. Instead, we propose that planar defects indirectly degrade device performance by acting as preferential segregation sites for optically active point defects.