Prof Laura Herz FRS

Abstract:

Mixed‐halide perovskites are ideal mid‐ and wide‐gap absorbers for multijunction solar cells, but stable photovoltaic performance is severely hampered by halide segregation. This study reveals that crystalline film quality and halide segregation are critically affected by bromide fraction x in CH3NH3Pb(I1−xBr x )3 because of macrostrain and ordered‐phase formation. X‐ray diffractometry across stoichiometries spanning 22 bromide fractions demonstrates that central compositions near x = 0.5 form two macrostrained phases, which exhibit halide segregation under light at different rates. While the overall amplitude of phase segregation follows a broadly symmetric distribution in compositional space, maximized near x = 0.5, the potentially ordered compositions of CH3NH3PbIBr2 and CH3NH3PbI2Br diverge sharply, presenting particularly stable and unstable scenarios, respectively. Notably, halide segregation is shown to occur even below the widely quoted perceived threshold of x = 0.2. Such analysis highlights promising approaches to mitigate halide segregation, through engineering of macrostrained phases and local atomistic ordering. Together, these observations provide crucial benchmarks for proposed models of halide segregation and establish new routes toward segregation‐resistant materials for multijunction perovskite‐based photovoltaics.

Abstract:

Inorganic cesium‐based metal halide perovskite (MHP) semiconductors have great potential as active layers in optoelectronic devices, such as perovskite light‐emitting diodes (PeLEDs) and perovskite lasers. However, precise control of crystal type, quality, and thickness is required to create high‐performance and reproducible devices. Vapor‐phase vacuum deposition enables fabrication of MHP thin films and devices with excellent uniformity and control over layer thickness, although a full understanding of crystal growth mechanisms and products has proved elusive. Here, conditions of vapor co‐deposition of CsBr and PbBr are related with the optical performance and atomic microstructure of resulting CsPbBr3 thin films. It is found that the structure is predominantly photoactive γ‐CsPbBr3 over a wide range of conditions, but the presence of impurity phases and Ruddlesden–Popper (RP) planar defects both degrade optical performance as quantified through measured amplified spontaneous emission (ASE) thresholds. Furthermore, the atomic structure of the dominant impurity phases is resolved: CsPb2Br5 and Cs4PbBr6. It is revealed that a small nominal excess of CsBr‐precursor flux during co‐evaporation can significantly enhance the nucleation of thin films, resulting in well‐defined grains greater than 500 nm in size and the relative suppression of RP planar defects. Such films exhibit intensified photoluminescence (PL) emission and a reduced ASE threshold of 30.9 µJ cm−2.

Abstract:

Tin-halide perovskites currently offer the best photovoltaic performance of lead-free metal-halide semiconductors. However, their transport properties are mostly dominated by holes, owing to ubiquitous self-doping. Here we demonstrate a noncontact, optical spectroscopic method to determine the effective mass of the dominant hole species in FASnI3, by investigating a series of thin films with hole densities finely tuned through either SnF2 additive concentration or controlled exposure to air. We accurately determine the plasma frequency from mid-infrared reflectance spectra by modeling changes in the vibrational response of the FA cation as the plasma edge shifts through the molecular resonance. Our approach yields a hole effective mass of 0.28m e for FASnI3 and demonstrates parabolicity within ∼100 meV of the valence band edge. An absence of Fano contributions further highlights insignificant coupling between the hole plasma and FA cation. Overall, this approach enables noncontact screening of thin-film materials for optimized charge-carrier transport properties.

Abstract:

Fully conjugated 3D covalent organic frameworks (COFs) are a newly emerged class of materials that expands reticular chemistry to extended electron delocalization for optoelectronic applications. To overcome the limitations of sp3‐connected 3D frameworks, the pseudo‐tetrahedral motif cyclooctatetrathiophene (COTh) has gained attention for forming fully conjugated 3D COFs. We report on a novel COTh building block, featuring functional formyl groups directly attached to the core's conjugated thiophenes. The modulation synthesis approach with mono‐functionalized inhibitors enables the formation of COTh‐1P COF, which exhibited remarkable crystallinity and permanent porosity. By following this approach and by optimizing the synthesis conditions for the solvothermal growth of thin films, we fabricated the first preferentially oriented conjugated 3D COF films on various substrates without pre‐functionalization. With these thin films, optical pump terahertz probe studies allowed us, for the first time with 3D‐fully conjugated COFs, to provide insights into the excited state and charge‐carrier dynamics of these unique organic frameworks. Low effective masses are discovered for valence and conduction bands by density functional theory simulations. The ability to create crystalline and oriented films of fully π‐conjugated 3D COTh‐based COFs on non‐modified substrates is expected to open the way for integration of such frameworks into diverse optoelectronic applications.

Abstract:

The copper–silver–bismuth–iodide compound Cu2AgBiI6 has emerged as a promising lead-free and environmentally friendly alternative to wide-bandgap lead-halide perovskites for applications in multijunction solar cells. Despite its promising optoelectronic properties, the efficiency of Cu2AgBiI6 is still severely limited by poor charge collection. Here, we investigate the impact of commonly used charge transport layers (CTLs), including poly­[bis­(4-phenyl)­(2,4,6-trimethylphenyl)­amine] (PTAA), CuI, [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), and SnO2, on the structural and optoelectronic properties of coevaporated Cu2AgBiI6 thin films. We reveal that while organic transport layers, such as PTAA and PCBM, form a relatively benign interface, inorganic transport layers, such as CuI and SnO2, induce the formation of unintended impurity phases within the CuI–AgI–BiI3 solid solution space, significantly influencing structural and optoelectronic properties. We demonstrate that identification of these impurity phases requires careful cross-validation combining absorption, X-ray diffraction and THz photoconductivity spectroscopy because their structural and optoelectronic properties are very similar to those of Cu2AgBiI6. Our findings highlight the critical role of CTLs in determining the structural and optoelectronic properties of coevaporated copper–silver–bismuth–iodide thin films and underscore the need for advanced interface engineering to optimize device efficiency and reproducibility.