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Heterogeneous Cationa??Lattice Interaction and Dynamics in Triple-Cation Perovskites Revealed by Infrared Vibrational Nanoscopy
摘要： Hybrid organic-inorganic perovskites exhibit extraordinary photovoltaic performance. This is believed to arise from almost liquid-like low-energy interactions among lattice ions and charge carriers. While spatial variations have recently been identified over multiple length scales in the optoelectronic responses, the relationship of the heterogeneity and the soft cation-lattice interactions has remained elusive. Here, we apply multivariate infrared vibrational nano-imaging to a formamidinium (FA)-methylammonium (MA)-cesium triple cation perovskite. By using the FA vibrational resonance as a probe of its local chemical environment, through spatial variation and correlation in composition, strength of cation-lattice coupling and its associated few-ps vibrational dynamics, we reveal how a varying local reaction field is correlated with the cation-lattice coupling. We attribute the associated heterogeneous lattice contraction to a non-uniform distribution of cesium cations. The observed varying elasticity of the lattice leads to disordered charge-phonon coupling and polaron formation, the control of which is central to improving perovskite photovoltaics.
关键词： charge-phonon coupling,infrared vibrational nano-imaging,Hybrid organic-inorganic perovskites,lattice contraction,photovoltaic performance,cation-lattice coupling,polaron formation,vibrational dynamics
更新于2025-09-19 17:13:59
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Impact of Molecular Order on Polaron Formation in Conjugated Polymers
摘要： The nature of polaron formation has profound implications on the transport of charge carriers in conjugated polymers, but still remains poorly understood. Here we develop in situ electrochemical resonant Raman spectroscopy, a powerful structural probe that allows direct observation of polaron formation. We report that polaron formation in ordered poly(3-hexyl)thiophene (P3HT) polymer domains (crystalline phase) results in less pronounced changes in molecular conformation, indicating smaller lattice relaxation, compared to polarons generated in disordered polymer domains (amorphous phase) for which we observe large molecular conformational changes. These conformational changes are directly related to the effective conjugation length of the polymer. Furthermore, we elucidate how blending the P3HT polymer with phenyl C-61 butyric acid methyl ester (PCBM) affects polaron formation in the polymer. We find that blending disturbs polymer crystallinity, reducing the density of polarons that can form upon charge injection at the same potential, whilst the lost capacity is partly restored during post-deposition thermal annealing. Our study provides direct spectroscopic evidence for a lower degree of lattice reorganisation in crystalline (and therefore more planarised) polymers than in conformationally disordered polymers. This observation is consistent with higher charge carrier mobility and better device performance commonly found in crystalline polymer materials.
关键词： electrochemical resonant Raman spectroscopy,conjugated polymers,polaron formation,molecular order,PCBM,charge transport,P3HT
更新于2025-09-09 09:28:46
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Geometry Distortion and Small Polaron Binding Energy Changes with Ionic Substitution in Halide Perovskites
摘要： Halide perovskites have demonstrated remarkable performance in optoelectronic applications. Despite extraordinary progress, questions remain about device stability. We report an in-depth computational study of small polaron formation, electronic structure, charge density, and reorganization energies of several experimentally relevant halide perovskites using isolated clusters. Local lattice symmetry, electronic structure, and electron-phonon coupling are interrelated in polaron formation in these materials. To illustrate this, first principles calculations are performed on (MA/Cs/FA)Pb(I/Br)3 and MASnI3. Across the materials studied, electron small polaron formation is manifested by Jahn-Teller like distortions in the central octahedron, with apical PbI bonds expanding significantly more than the equatorial bonds. In contrast, hole polarons cause the central octahedron to uniformly contract. This difference in manifestation of electron and hole polaron formation can be a tool to determine what is taking place in individual systems to systematically control performance. Other trends as the anion and cations are changed, are established for optimization in specific optoelectronic applications.
关键词： optoelectronic applications,reorganization energies,Jahn-Teller distortions,charge density,Halide perovskites,small polaron formation,electronic structure
更新于2025-09-09 09:28:46