Impact of Sb and Na Doping on the Surface Electronic Landscape of Cu2ZnSnS4 Thin Films

Open-circuit voltage deficiency is the key limiting factor in Cu2ZnSnS4 (CZTS) thin-film solar cells, which is commonly associated with band tails and deep gap states arising from elemental disorder. The introduction of dopants such as Na and Sb has led to improvement in device performance, yet their effects on the optoelectronic properties of CZTS are yet to be fully elucidated. In this Letter, we unraveled the effect of Sb and Na:Sb co-doping on the surface energy landscape of solution-processed CZTS films employing energy-filtered photoelectron emission microscopy. In the absence of the additives, 150 nm resolution photoemission maps reveal oscillations in the local effective work function as well as areas of low photoemission energy threshold. The introduction of dopants substantially reshapes the photoemission maps, which we rationalize in terms of Cu:Zn and Sn disorder. Finally, we establish unprecedented correlations between the photoemission landscape of thin films and the performance of over 200 devices

Self-transformation and structural reconfiguration in coacervate-based protocells

We highlight a new approach for the design and construction of re-configurable soft colloidal scale objects (protocells) based on the pH-induced transition of dipeptide-containing coacervate micro-droplets into discrete aster-like micro-architectures.</p

Direct observation of electron emission from grain boundaries in CVD diamond by PeakForce-controlled tunnelling atomic force microscopy

AbstractA detailed investigation of electron emission from a set of chemical vapour deposited (CVD) diamond films is reported using high-resolution PeakForce-controlled tunnelling atomic force microscopy (PF-TUNA). Electron field emission originates preferentially from the grain boundaries in low-conductivity polycrystalline diamond samples, and not from the top of features or sharp edges. Samples with smaller grains and more grain boundaries, such as nanocrystalline diamond, produce a higher emission current over a more uniform area than diamond samples with larger grain size. Light doping with N, B or P increases the grain conductivity, with the result that the emitting grain-boundary sites become broader as the emission begins to creep up the grain sidewalls. For heavy B doping, where the grains are now more conducting than the grain boundaries, emission comes from both the grain boundaries and the grains almost equally. Lightly P-doped diamond samples show emission from step-edges on the (111) surfaces. Emission intensity was time dependent, with the measured current dropping to ∼10% of its initial value ∼30h after removal from the CVD chamber. This decrease is ascribed to the build-up of adsorbates on the surface along with an increase in the surface conductivity due to surface transfer doping

Directed assembly of defined oligomeric photosynthetic reaction centres through adaptation with programmable extra-membrane coiled-coil interfaces

A challenge associated with the utilisation of bioenergetic proteins in new, synthetic energy transducing systems is achieving efficient and predictable self-assembly of individual components, both natural and man-made, into a functioning macromolecular system. Despite progress with water-soluble proteins, the challenge of programming self-assembly of integral membrane proteins into non-native macromolecular architectures remains largely unexplored. In this work it is shown that the assembly of dimers, trimers or tetramers of the naturally monomeric purple bacterial reaction centre can be directed by augmentation with an α-helical peptide that self-associates into extra-membrane coiled-coil bundle. Despite this induced oligomerisation the assembled reaction centres displayed normal spectroscopic properties, implying preserved structural and functional integrity. Mixing of two reaction centres modified with mutually complementary α-helical peptides enabled the assembly of heterodimers in vitro, pointing to a generic strategy for assembling hetero-oligomeric complexes from diverse modified or synthetic components. Addition of two coiled-coil peptides per reaction centre monomer was also tolerated despite the challenge presented to the pigment-protein assembly machinery of introducing multiple self-associating sequences. These findings point to a generalised approach where oligomers or longer range assemblies of multiple light harvesting and/or redox proteins can be constructed in a manner that can be genetically-encoded, enabling the construction of new, designed bioenergetic systems in vivo or in vitro