From Chalcogen Bonding to S-π Interactions in Hybrid Perovskite Photovoltaics.

The stability of hybrid organic-inorganic halide perovskite semiconductors remains a significant obstacle to their application in photovoltaics. To this end, the use of low-dimensional (LD) perovskites, which incorporate hydrophobic organic moieties, provides an effective strategy to improve their stability, yet often at the expense of their performance. To address this limitation, supramolecular engineering of noncovalent interactions between organic and inorganic components has shown potential by relying on hydrogen bonding and conventional van der Waals interactions. Here, the capacity to access novel LD perovskite structures that uniquely assemble through unorthodox S-mediated interactions is explored by incorporating benzothiadiazole-based moieties. The formation of S-mediated LD structures is demonstrated, including one-dimensional (1D) and layered two-dimensional (2D) perovskite phases assembled via chalcogen bonding and S-π interactions, through a combination of techniques, such as single crystal and thin film X-ray diffraction, as well as solid-state NMR spectroscopy, complemented by molecular dynamics simulations, density functional theory calculations, and optoelectronic characterization, revealing superior conductivities of S-mediated LD perovskites. The resulting materials are applied in n-i-p and p-i-n perovskite solar cells, demonstrating enhancements in performance and operational stability that reveal a versatile supramolecular strategy in photovoltaics.

Buried-Interface Engineering Enables Efficient and 1960-Hour ISOS-L-2I Stable Inverted Perovskite Solar Cells.

High-performance perovskite solar cells (PSCs) typically require interfacial passivation, yet this is challenging for the buried interface, owing to the dissolution of passivation agents during the deposition of perovskites. Here, this limitation is overcome with in situ buried-interface passivation-achieved via directly adding a cyanoacrylic-acid-based molecular additive, namely BT-T, into the perovskite precursor solution. Classical and ab initio molecular dynamics simulations reveal that BT-T spontaneously may self-assemble at the buried interface during the formation of the perovskite layer on a nickel oxide hole-transporting layer. The preferential buried-interface passivation results in facilitated hole transfer and suppressed charge recombination. In addition, residual BT-T molecules in the perovskite layer enhance its stability and homogeneity. A power-conversion efficiency (PCE) of 23.48% for 1.0 cm2 inverted-structure PSCs is reported. The encapsulated PSC retains 95.4% of its initial PCE following 1960 h maximum-power-point tracking under continuous light illumination at 65 °C (i.e., ISOS-L-2I protocol). The demonstration of operating-stable PSCs under accelerated ageing conditions represents a step closer to the commercialization of this emerging technology.

Interplay of Kinetic and Thermodynamic Reaction Control Explains Incorporation of Dimethylammonium Iodide into CsPbI3.

CsPbI3 is a promising material for optoelectronics owing to its thermal robustness and favorable bandgap. However, its fabrication is challenging because its photoactive phase is thermodynamically unstable at room temperature. Adding dimethylammonium (DMA) alleviates this instability and is currently understood to result in the formation of DMA x Cs1-x PbI3 perovskite solid solutions. Here, we use NMR of the 133Cs and 13C local structural probes to show that these solid solutions are not thermodynamically stable, and their synthesis under thermodynamic control leads to a segregated mixture of yellow one-dimensional DMAPbI3 phase and δ-CsPbI3. We show that mixed-cation DMA x Cs1-x PbI3 perovskite phases only form when they are kinetically trapped by rapid antisolvent-induced crystallization. We explore the energetics of DMA incorporation into CsPbI3 using first-principles calculations and molecular dynamics simulations and find that this process is energetically unfavorable. Our results provide a complete atomic-level picture of the mechanism of DMA-induced stabilization of the black perovskite phase of CsPbI3 and shed new light on this deceptively simple material.

Reversible Pressure-Dependent Mechanochromism of Dion-Jacobson and Ruddlesden-Popper Layered Hybrid Perovskites.

Layered Dion-Jacobson (DJ) and Ruddlesden-Popper (RP) hybrid perovskites are promising materials for optoelectronic applications due to their modular structure. To fully exploit their functionality, mechanical stimuli can be used to control their properties without changing the composition. However, the responsiveness of these systems to pressure compatible with practical applications (<1 GPa) remains unexploited. Hydrostatic pressure is used to investigate the structure-property relationships in representative iodide and bromide DJ and RP 2D perovskites based on 1,4-phenylenedimethylammonium (PDMA) and benzylammonium (BzA) spacers in the 0-0.35 GPa pressure range. Pressure-dependent X-ray scattering measurements reveal that lattices of these compositions monotonically shrink and density functional theory calculations provide insights into the structural changes within the organic spacer layer. These structural changes affect the optical properties; the most significant shift in the optical absorption is observed in (BzA)2 PbBr4 under 0.35 GPa pressure, which is attributed to an isostructural phase transition. Surprisingly, the RP and DJ perovskites behave similarly under pressure, despite the different binding modes of the spacer molecules. This study provides important insights into how the manipulation of the crystal structure affects the optoelectronic properties of such materials, whereas the reversibility of their response expands the perspectives for future applications.

Nanoscale interfacial engineering enables highly stable and efficient perovskite photovoltaics.

We present a facile molecular-level interface engineering strategy to augment the long-term operational and thermal stability of perovskite solar cells (PSCs) by tailoring the interface between the perovskite and hole transporting layer (HTL) with a multifunctional ligand 2,5-thiophenedicarboxylic acid. The solar cells exhibited high operational stability (maximum powering point tracking at one sun illumination) with a stabilized T S80 (the time over which the device efficiency reduces to 80% after initial burn-in) of ≈5950 h at 40 °C and a stabilized power conversion efficiency (PCE) over 23%. The origin of high device stability and performance is correlated to the nano/sub-nanoscale molecular level interactions between ligand and perovskite layer, which is further corroborated by comprehensive multiscale characterization. These results provide insights into the modulation of the grain boundaries, local density of states, surface bandgap, and interfacial recombination. Chemical analysis of aged devices showed that molecular passivation suppresses interfacial ion diffusion and inhibits the photoinduced I2 release that irreversibly degrades the perovskite. The interfacial engineering strategies enabled by multifunctional ligands can expedite the path towards stable PSCs.

Structure-Based Theory of Fluctuation-Induced Energy Transfer in a Molecular Dyad.

We present a microscopic theory for the description of fluctuation-induced excitation energy transfer in chromophore dimers to explain experimental data on a perylene biscarboximide dyad with orthogonal transition dipole moments. Our non-Condon extension of Förster theory takes into account the fluctuations of excitonic couplings linear and quadratic in the normal coordinates, treated microscopically by quantum chemical/electrostatic calculations. The modulation of the optical transition energies of the chromophores is inferred from optical spectra of the isolated chromophores. The application of the theory to the considered dyad reveals a two to three order of magnitude increase in the rate constant by non-Condon effects. These effects are found to be dominated by fluctuations linear in the normal coordinates and provide a structure-based qualitative interpretation of the experimental time constant for energy transfer as well as its dependence on temperature.