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

Glimse项目的目标是深入了解金属-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性质。我们将在化学和物理之间的跨学科框架内，利用紧密交织的实验和理论方法来解决这些研究问题。该项目分为三个方面，以确定分子金属卤化物络合物的结构、光谱和在薄膜形成过程中的演化。在实验上，将结合最先进的X射线光谱技术(EXAFS，XANES)和X射线衍射(XRD)研究卤化铅配合物的配位化学、几何结构和结构，并与理论密度泛函理论(DFT)计算进行比较。根据密度泛函理论确定的卤化物和溶剂与金属的结合强度将与由吸收数据的贝内西-希尔德布兰德分析确定的化学平衡常数进行比较。我们将通过光学光谱和基于多体微扰理论(MBPT)的第一性原理计算来识别和合理化溶液中金属-卤化物-溶剂络合物的光谱指纹。用原位光学监测和相关的X射线技术相结合的方法，研究了代表三维金属卤化物钙钛矿半导体零维构建块的溶液络合物通过低维一维和二维晶体中间体的演化。这些研究将得到晶体中间体的DFT和MBPT计算的补充，使人们能够以最先进的精度获得电子、光学和核心水平的激发。该项目的成果将对金属-卤化物溶液络合物(积木)的结构如何决定金属-卤化物钙钛矿薄膜的形貌和光电子质量、电荷载流子动力学、缺陷、缺陷容限和内在降解机制提供前所未有的深入了解。

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.