Abstract
Although it has been exploited since the late 1900s to study hybrid perovskite materials, nuclear magnetic resonance (NMR) spectroscopy has only recently received extraordinary research attention in this field. This very powerful technique allows the study of the physico-chemical and structural properties of molecules by observing the quantum mechanical magnetic properties of an atomic nucleus, in solution as well as in solid state. Its versatility makes it a promising technique either for the atomic and molecular characterization of perovskite precursors in colloidal solution or for the study of the geometry and phase transitions of the obtained perovskite crystals, commonly used as a reference material compared with thin films prepared for applications in optoelectronic devices. This review will explore beyond the current focus on the stability of perovskites (3D in bulk and nanocrystals) investigated via NMR spectroscopy, in order to highlight the chemical flexibility of perovskites and the role of interactions for thermodynamic and moisture stabilization. The exceptional potential of the vast NMR tool set in perovskite structural characterization will be discussed, aimed at choosing the most stable material for optoelectronic applications. The concept of a double-sided characterization in solution and in solid state, in which the organic and inorganic structural components provide unique interactions with each other and with the external components (solvents, additives, etc.), for material solutions processed in thin films, denotes a significant contemporary target.
Highlights
Sustainable photovoltaic applications are evolving from silicon to perovskite materials, where a perovskite with 25.5% efficiency outperforms thin-film silicon solar cells (21.2%), and its efficiency is further increased to 29.5% in tandem devices of perovskite/c-Si [1]
The advantage of the perovskite structure (Scheme 1) is its versatility: it is obtained with different atoms and with different dimensionalities (nanocrystal 0D structure; layered perovskites of the general formula (RNH3 )2 An−1 Bn X3n+1 : n = 1, pure 2D layered; ABX3, 3D structure) [5], and it can be mixed with other components in solution [6]
Perwith the same[41], goodwith effects. This is due theinstability different solubility in the solvents commonly employed in perovskite preparation (i.e., dimethylformamide, ovskite, especially under operation conditions [42], as well as hysdimethylsulfoxide, N-methylpyrrolidone) [47], and the extent of the interaction, which teresis in the devices due to the ion vacancies acting as charge traps [43]
Summary
Sustainable photovoltaic applications are evolving from silicon to perovskite materials, where a perovskite with 25.5% efficiency outperforms thin-film silicon solar cells (21.2%), and its efficiency is further increased to 29.5% in tandem devices of perovskite/c-Si [1]. To investigate the perovskite properties at the atomic level, an array of structural, morphological and spectroscopic techniques is ordinarily used [16]; among them, in this review, we will focus on nuclear magnetic resonance (NMR) spectroscopy as a remarkable technique to entirely characterize the material and the whole system in which it is involved, such as solvents, additives and synthetic components [17,18] Both solution and solid-state (ss) NMR techniques provide useful information for the characterization of the material and for the elucidation of intermolecular interactions that affect the perovskite stability and the device’s final properties. Phase; NMR tools for perovskite characterization; perovskite nanocrystals with the inorganic core and organic coordinating ligands
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