Proceedings of International Conference on Perovskite Thin Film Photovoltaics and Perovskite Photonics and Optoelectronics (NIPHO25)
Publication date: 24th April 2025
Metal Halide Perovskites (MHPs), with the general formula ABX₃ (A = MA⁺, CH₃NH₃; B = Pb²⁺, Sn²⁺; X = I, Br, Cl), have emerged as very promising materials in optoelectronics due to their exceptional electronic, optical, and chemical properties. While 3D perovskite structures demonstrate high efficiency in applications such as solar cells and LEDs, they are prone to environmental degradation. In contrast, 2D perovskite structures, obtained by replacing methylammonium (MA⁺) with larger hydrophobic cations like phenyl-ethyl ammonium (PEA⁺), offer enhanced stability but lower efficiency compared to their 3D counterparts. Combining both 3D and 2D structures in a single device can harness their respective advantages, resulting in stable and high-performance systems.
Solid-State NMR (SSNMR) plays a crucial role in probing these materials at the atomic scale, enabling detailed analysis of surface composition and isotopic variations. In this work we developed a new method for single crystal deuteration to enhance surface regions for SSNMR analysis, providing deeper insights into interfacial properties.
Before deuteration, MAPbI₃ and MAPbBr₃ single crystal samples are prepared by inverse temperature crystallization. The resulting crystals are immersed in a solution of CD₃NH₃Cl in isopropanol, allowing for surface proton exchange between the CH₃ groups on the crystal and deuterium atoms from the CD₃ group in the solution, thus enabling surface deuteration.
Characterization of the samples includes X-ray diffraction (XRD) and both solution-state and solid-state nuclear magnetic resonance (NMR and SS-NMR) spectroscopy. XRD analysis confirms that the crystalline structure remains unaltered following deuteration treatment. NMR measurements validate successful deuteration, as evidenced by the absence of the CH₃ proton signal in the spectra.
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