Nanostructured semiconductors emit light from electronic states known as excitons. For organic materials, Hund's rules state that the lowest-energy exciton is a poorly emitting triplet state. For inorganic semiconductors, similar rules predict an analogue of this triplet state known as the 'dark exciton'. Because dark excitons release photons slowly, hindering emission from inorganic nanostructures, materials that disobey these rules have been sought. However, despite considerable experimental and theoretical efforts, no inorganic semiconductors have been identified in which the lowest exciton is bright. Here we show that the lowest exciton in caesium lead halide perovskites (CsPbX, with X = Cl, Br or I) involves a highly emissive triplet state. We first use an effective-mass model and group theory to demonstrate the possibility of such a state existing, which can occur when the strong spin-orbit coupling in the conduction band of a perovskite is combined with the Rashba effect. We then apply our model to CsPbX nanocrystals, and measure size- and composition-dependent fluorescence at the single-nanocrystal level. The bright triplet character of the lowest exciton explains the anomalous photon-emission rates of these materials, which emit about 20 and 1,000 times faster than any other semiconductor nanocrystal at room and cryogenic temperatures, respectively. The existence of this bright triplet exciton is further confirmed by analysis of the fine structure in low-temperature fluorescence spectra. For semiconductor nanocrystals, which are already used in lighting, lasers and displays, these excitons could lead to materials with brighter emission. More generally, our results provide criteria for identifying other semiconductors that exhibit bright excitons, with potential implications for optoelectronic devices.

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The hexagonal structure of graphene gives rise to the property of gas impermeability, motivating its investigation for a new application: protection of semiconductor photocathodes in electron accelerators. These materials are extremely susceptible to degradation in efficiency through multiple mechanisms related to contamination from the local imperfect vacuum environment of the host photoinjector. Few-layer graphene has been predicted to permit a modified photoemission response of protected photocathode surfaces, and recent experiments of single-layer graphene on copper have begun to confirm these predictions for single crystal metallic photocathodes. Unlike metallic photoemitters, the integration of an ultra-thin graphene barrier film with conventional semiconductor photocathode growth processes is not straightforward. A first step toward addressing this challenge is the growth and characterization of technologically relevant, high quantum efficiency bialkali photocathodes on ultra-thin freestanding graphene substrates. Photocathode growth on free-standing graphene provides the opportunity to integrate these two materials and study their interaction. Specifically, spectral response features and photoemission stability of cathodes grown on graphene substrates are compared to those deposited on established substrates. In addition, we observed an increase of work function for the graphene encapsulated bialkali photocathode surfaces, which is predicted by our calculations. The results provide a unique demonstration of bialkali photocathodes on free-standing substrates, and indicate promise towards our goal of fabricating high-performance graphene encapsulated photocathodes with enhanced lifetime for accelerator applications.

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