Homomeric chains of intermolecular bonds scaffold octahedral germanium perovskites.

Perovskites with low ionic radii metal centres (for example, Ge perovskites) experience both geometrical constraints and a gain in electronic energy through distortion; for these reasons, synthetic attempts do not lead to octahedral [GeI6] perovskites, but rather, these crystallize into polar non-perovskite structures1-6. Here, inspired by the principles of supramolecular synthons7,8, we report the assembly of an organic scaffold within perovskite structures with the goal of influencing the geometric arrangement and electronic configuration of the crystal, resulting in the suppression of the lone pair expression of Ge and templating the symmetric octahedra. We find that, to produce extended homomeric non-covalent bonding, the organic motif needs to possess self-complementary properties implemented using distinct donor and acceptor sites. Compared with the non-perovskite structure, the resulting [GeI6]4- octahedra exhibit a direct bandgap with significant redshift (more than 0.5 eV, measured experimentally), 10 times lower octahedral distortion (inferred from measured single-crystal X-ray diffraction data) and 10 times higher electron and hole mobility (estimated by density functional theory). We show that the principle of this design is not limited to two-dimensional Ge perovskites; we implement it in the case of copper perovskite (also a low-radius metal centre), and we extend it to quasi-two-dimensional systems. We report photodiodes with Ge perovskites that outperform their non-octahedral and lead analogues. The construction of secondary sublattices that interlock with an inorganic framework within a crystal offers a new synthetic tool for templating hybrid lattices with controlled distortion and orbital arrangement, overcoming limitations in conventional perovskites.

Strain data augmentation enables machine learning of inorganic crystal geometry optimization.

Machine-learning (ML) models offer the potential to rapidly evaluate the vast inorganic crystalline materials space to efficiently find materials with properties that meet the challenges of our time. Current ML models require optimized equilibrium structures to attain accurate predictions of formation energies. However, equilibrium structures are generally not known for new materials and must be obtained through computationally expensive optimization, bottlenecking ML-based material screening. A computationally efficient structure optimizer is therefore highly desirable. In this work, we present an ML model capable of predicting the crystal energy response to global strain by using available elasticity data to augment the dataset. The addition of global strains improves our model's understanding of local strains too, significantly improving the accuracy of energy predictions on distorted structures. This allows us to construct an ML-based geometry optimizer, which we used for improving the predictions of formation energy for structures with perturbed atomic positions.

Bipolar-shell resurfacing for blue LEDs based on strongly confined perovskite quantum dots.

Colloidal quantum dot (QD) solids are emerging semiconductors that have been actively explored in fundamental studies of charge transport1 and for applications in optoelectronics2. Forming high-quality QD solids-necessary for device fabrication-requires substitution of the long organic ligands used for synthesis with short ligands that provide increased QD coupling and improved charge transport3. However, in perovskite QDs, the polar solvents used to carry out the ligand exchange decompose the highly ionic perovskites4. Here we report perovskite QD resurfacing to achieve a bipolar shell consisting of an inner anion shell, and an outer shell comprised of cations and polar solvent molecules. The outer shell is electrostatically adsorbed to the negatively charged inner shell. This approach produces strongly confined perovskite QD solids that feature improved carrier mobility (≥0.01 cm2 V-1 s-1) and reduced trap density relative to previously reported low-dimensional perovskites. Blue-emitting QD films exhibit photoluminescence quantum yields exceeding 90%. By exploiting the improved mobility, we have been able to fabricate CsPbBr3 QD-based efficient blue and green light-emitting diodes. Blue devices with reduced trap density have an external quantum efficiency of 12.3%; the green devices achieve an external quantum efficiency of 22%.

Stabilizing Surface Passivation Enables Stable Operation of Colloidal Quantum Dot Photovoltaic Devices at Maximum Power Point in an Air Ambient.

Colloidal quantum dots (CQDs) are promising materials for photovoltaic (PV) applications owing to their size-tunable bandgap and solution processing. However, reports on CQD PV stability have been limited so far to storage in the dark; or operation illuminated, but under an inert atmosphere. CQD PV devices that are stable under continuous operation in air have yet to be demonstrated-a limitation that is shown here to arise due to rapid oxidation of both CQDs and surface passivation. Here, a stable CQD PV device under continuous operation in air is demonstrated by introducing additional potassium iodide (KI) on the CQD surface that acts as a shielding layer and thus stands in the way of oxidation of the CQD surface. The devices (unencapsulated) retain >80% of their initial efficiency following 300 h of continuous operation in air, whereas CQD PV devices without KI lose the amount of performance within just 21 h. KI shielding also provides improved surface passivation and, as a result, a higher power conversion efficiency (PCE) of 12.6% compared with 11.4% for control devices.