The effect of defects on electron-hole separation is not always clear and is sometimes contradictory. Herein, we initially built clear models of two-dimensional atomic layers with tunable defect concentrations, and hence directly disclose the defect type and distribution at atomic level. As a prototype, defective one-unit-cell ZnInS atomic layers are successfully synthesized for the first time. Aberration-corrected scanning transmission electron microscopy directly manifests their distinct zinc vacancy concentrations, confirmed by positron annihilation spectrometry and electron spin resonance analysis. Density-functional calculations reveal that the presence of zinc vacancies ensures higher charge density and efficient carrier transport, verified by ultrafast photogenerated electron transfer time of ∼15 ps from the conduction band of ZnInS to the trap states. Ultrafast transient absorption spectroscopy manifests the higher zinc vacancy concentration that allows for ∼1.7-fold increase in average recovery lifetime, confirmed by surface photovoltage spectroscopy and PL spectroscopy analysis, which ensures promoted carrier separation rates. As a result, the one-unit-cell ZnInS layers with rich zinc vacancies exhibit a carbon monoxide formation rate of 33.2 μmol g h, roughly 3.6 times higher than that of the one-unit-cell ZnInS layers with poor zinc vacancies, while the former's photocatalytic activity shows negligible loss after 24 h photocatalysis. This present work uncovers the role of defects in affecting electron-hole separation at atomic level, opening new opportunities for achieving highly efficient solar CO reduction performances.

The mechanisms of triplet energy transfer across the inorganic nanocrystal/organic molecule interface remain poorly understood. Many seemingly contradictory results have been reported, mainly because of the complicated trap states characteristic of inorganic semiconductors and the ill-defined relative energetics between semiconductors and molecules used in these studies. Here we clarify the transfer mechanisms by performing combined transient absorption and photoluminescence measurements, both with sub-picosecond time resolution, on model systems comprising lead halide perovskite nanocrystals with very low surface trap densities as the triplet donor and polyacenes which either favour or prohibit charge transfer as the triplet acceptors. Hole transfer from nanocrystals to tetracene is energetically favoured, and hence triplet transfer proceeds via a charge separated state. In contrast, charge transfer to naphthalene is energetically unfavourable and spectroscopy shows direct triplet transfer from nanocrystals to naphthalene; nonetheless, this "direct" process could also be mediated by a high-energy, virtual charge-transfer state.

Triplet energy transfer (TET) from semiconductor nanocrystals (NCs) has recently emerged as a new triplet sensitization paradigm. It remains unclear how trap states pervasive in NCs influence TET or whether trapped excitons can undergo efficient TET. Here we partially address this issue by studying TET from CuInS 2 NCs as a model system because their photogenerated excitons are known to be "self-trapped" due to hole localization to intragap Cu states. We found that, thanks to the long lifetime (209 ± 17 ns) of self-trapped excitons, they could be extracted with an efficiency of ∼92.3% by surface-anchored anthracene despite that the TET rate was relatively slow (57.1 ± 1.7 μs −1 ). We further leveraged this efficient sensitization to achieve triplet− triplet-annihilation photon upconversion (TTA-UC) with a quantum yield of 18.6 ± 0.3%. Thus, this study not only demonstrates trapped excitons can undergo efficient TET as well, but also presents the first TTA-UC system sensitized by nontoxic NCs which is important for the real-life application of this technique.