| Summary: | Recently, layered hybrid perovskites have been attracting huge interest due to a wide range of possible chemical compositions and the resulting tunability of the materials’ properties. In this study, we investigate the effect of the chain length of the organic ligands on the optical properties of stacks of two-dimensional perovskite layers consisting of alkylammonium lead iodide (CnH2n+1NH3)2PbI4 with n = 4, …, 18. Photoluminescence and absorption spectroscopy reveal a blueshift with increasing chain length n including a jump of 110 meV between the n = 10 and n = 12 ligands due to a change in octahedral tilting. Using X-ray diffraction, we determine the crystal structure and find the octahedral tilting to be the main cause of this blueshift. However, for very short chain lengths, additional effects further reduce the transition energy. Results of effective mass approximation model calculations show good agreement between the expected reduction of transition energy and measured photoluminescence emission wavelength for these samples. This highlights how octahedral tilting plays a major role in determining the optical bandgap and suggests that miniband formation plays only a minor role in this material.
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