Colloidal quantum dot (CQD) films allow large-area solution processing and bandgap tuning through the quantum size effect. However, the high ratio of surface area to volume makes CQD films prone to high trap state densities if surfaces are imperfectly passivated, promoting recombination of charge carriers that is detrimental to device performance. Recent advances have replaced the long insulating ligands that enable colloidal stability following synthesis with shorter organic linkers or halide anions, leading to improved passivation and higher packing densities. Although this substitution has been performed using solid-state ligand exchange, a solution-based approach is preferable because it enables increased control over the balance of charges on the surface of the quantum dot, which is essential for eliminating midgap trap states. Furthermore, the solution-based approach leverages recent progress in metal:chalcogen chemistry in the liquid phase. Here, we quantify the density of midgap trap states in CQD solids and show that the performance of CQD-based photovoltaics is now limited by electron-hole recombination due to these states. Next, using density functional theory and optoelectronic device modelling, we show that to improve this performance it is essential to bind a suitable ligand to each potential trap site on the surface of the quantum dot. We then develop a robust hybrid passivation scheme that involves introducing halide anions during the end stages of the synthesis process, which can passivate trap sites that are inaccessible to much larger organic ligands. An organic crosslinking strategy is then used to form the film. Finally, we use our hybrid passivated CQD solid to fabricate a solar cell with a certified efficiency of 7.0%, which is a record for a CQD photovoltaic device.

Figure 7. Schematic representation of the system for spray-coating colloidal quantum dot films. Reprinted with permission from ref 117.

Colloidal quantum dots (CQDs) offer promise in flexible electronics, light sensing and energy conversion. These applications rely on rectifying junctions that require the creation of high-quality CQD solids that are controllably n-type (electron-rich) or p-type (hole-rich). Unfortunately, n-type semiconductors made using soft matter are notoriously prone to oxidation within minutes of air exposure. Here we report high-performance, air-stable n-type CQD solids. Using density functional theory we identify inorganic passivants that bind strongly to the CQD surface and repel oxidative attack. A materials processing strategy that wards off strong protic attack by polar solvents enabled the synthesis of an air-stable n-type PbS CQD solid. This material was used to build an air-processed inverted quantum junction device, which shows the highest current density from any CQD solar cell and a solar power conversion efficiency as high as 8%. We also feature the n-type CQD solid in the rapid, sensitive, and specific detection of atmospheric NO2. This work paves the way for new families of electronic devices that leverage air-stable quantum-tuned materials.

The absorbing layer in state-of-the-art colloidal quantum-dot solar cells is fabricated using a tedious layer-by-layer process repeated ten times. It is now shown that methanol, a common exchange solvent, is the main culprit, as extended exposure leaches off the surface halide passivant, creating carrier trap states. Use of a high-dipole-moment aprotic solvent eliminates this problem and is shown to produce state-of-the-art devices in far fewer steps.

A colloidal quantum dot solar cell is fabricated by spray-coating under ambient conditions. By developing a room-temperature spray-coating technique and implementing a fully automated process with near monolayer control-an approach termed as sprayLD-an electronic defect is eliminated resulting in solar cell performance and statistical distribution superior to prior batch-processed methods along with a hero performance of 8.1%.