Illuminating building block evolution of metal-halide perovskite semiconductors from solutions to thin films (GLIMPSE)

GLIMPSE项目的目标是从根本上了解金属卤化物溶液络合物如何决定3D固态金属卤化物钙钛矿半导体的光电特性。我们将在化学和物理之间的边界，利用强烈交织的实验和理论方法的跨学科框架解决这些研究问题。该项目分为三个方面，以确定薄膜形成过程中分子金属卤化物配合物的结构、光谱和演变。实验上，卤代铅酸盐配合物的配位化学，几何形状和结构将与最先进的X射线光谱技术（EXAFS，XANES）以及X射线衍射（XRD）相结合，并与理论密度泛函理论（DFT）计算进行比较。将从DFT确定的卤化物和溶剂与金属的结合强度与从吸收数据的Benesi-Hildebrand分析确定的化学平衡常数进行比较。我们将确定和合理化的光谱指纹的金属卤化物溶剂络合物在溶液中的光谱补充的第一性原理计算的基础上多体微扰理论（MBPT）的装置。代表3D金属卤化物钙钛矿半导体的0 D结构单元的溶液络合物通过低维1D和2D晶体中间体的演变将通过原位光学监测和相关的基于X射线的技术相结合来研究。这些研究将通过对结晶中间体的DFT和MBPT计算来补充，以最先进的精度获得电子，光学和核心水平的激发。该项目的成果将为金属卤化物溶液复合物（构建块）的结构如何决定金属卤化物钙钛矿薄膜的形态和光电质量、电荷载体动力学、缺陷、缺陷容限和内在降解机制提供前所未有的见解。

The goal of the GLIMPSE project is gaining fundamental insight into how metal-halide solution complexes determine the opto-electronic properties of 3D solid state metal-halide perovskite semiconductors. We will tackle these research questions in an interdisciplinary framework at the boundary between chemistry and physics utilizing strongly intertwined experimental and theoretical methods. The project is divided into the three aspects to identify structure, spectra and evolution of molecular metal-halide complexes during thin film formation. Experimentally, the coordination chemistry, geometry and structure of halido-plumbate complexes will be investigated with a combination of state-of-the-art X-ray spectroscopy techniques (EXAFS, XANES) as well as X-ray diffraction (XRD) and compared to theoretical density-functional theory (DFT) calculations. The binding strength of halide and solvents to the metal determined from DFT will be compared to chemical equilibrium constants determined from Benesi-Hildebrand analysis of absorption data. We will identify and rationalize the spectral fingerprints of metal-halide-solvent complexes in solution by means of optical spectroscopy complemented by first-principles calculations based on many-body perturbation theory (MBPT). The evolution of solution complexes representing 0D building blocks of 3D metal-halide perovskite semiconductors via low-dimensional 1D and 2D crystalline intermediates will be investigated by a combination of in-situ optical monitoring and correlative X-ray based techniques. These studies will be complemented by DFT and MBPT calculations on the crystalline intermediates, giving access to electronic, optical, and core-level excitations with state-of-the-art accuracy. The outcomes of this project will provide unprecedented insight into how the structure of metal-halide solution complexes (building blocks) determine morphology and opto-electronic quality, charge carrier dynamics, defects, defect tolerance and intrinsic degradation mechanisms of metal-halide perovskite thin films.