Hysteresis in hybrid perovskite indoor photovoltaics.

Halide perovskite indoor photovoltaics (PV) are a viable solution to autonomously power the billions of sensors in the huge technology field of the Internet of Things. However, there exists a knowledge gap in the hysteresis behaviour of these photovoltaic devices under indoor lighting conditions. The present work is the first experimental study dedicated to exploring the degree of hysteresis in halide perovskite indoor photovoltaic devices by carrying out both transient J-V scan and steady state maximum power point tracking (MPPT) measurements. Dependence of hysteresis on device architecture, selection of electron transporting layers and the composition of the perovskite photoactive layers were investigated. Under indoor illumination, the p-i-n MAPbI3-based devices show consistently high power conversion efficiency (PCE) (stabilized PCE) of greater than 30% and negligible hysteresis behaviour, whereas the n-i-p MAPbI3 devices show poor performance (stabilized PCE ∼ 15%) with pronounced hysteresis effect. Our study also reveals that the n-i-p triple cation perovskite devices are more promising (stabilized PCE ∼ 25%) for indoor PV compared to n-i-p MAPbI3 due to their suppressed ion migration effects. It was observed that the divergence of the PCE values estimated from the J-V scan measurements, and the maximum power point tracking method is higher under indoor illumination compared to 1 Sun, and hence for halide perovskite-based indoor PV, the PCE from the MPPT measurements should be prioritized over the J-V scan measurements. The results from our study suggest the following approaches for maximizing the steady state PCE from halide perovskite indoor PV: (i) select perovskite active layer composition with suppressed ion migration effects (such as Cs-containing triple cation perovskites) and (ii) for the perovskite composition such as MAPbI3, where the ion migration is very active, p-i-n architecture with organic charge transport layers is beneficial over the n-i-p architecture with conventional metal oxides (such as TiO2, SnO2) as charge transport layers. This article is part of the theme issue 'Developing resilient energy systems'.

Probing the structure-property-composition relationship in organic-inorganic tri-halide perovskites.

Here, we have synthesised a range of samples, with the formula (CH3NH3)1-2x(H3NC2H4NH3)xPbI3, with different levels of ethylenediammonium substitution to probe non-stoichiometry at the A-site of the perovskite. A single phase region was identified and is accompanied by a change in photophysical properties. The influence of aliovalent substitution with ethylenediammonium results in a decrease in HOMO level from -5.31 eV for x = 0 to -5.88 eV for x = 0.15.

Radio Frequency Coplanar ZnO Schottky Nanodiodes Processed from Solution on Plastic Substrates.

Coplanar radio frequency Schottky diodes based on solution-processed C60 and ZnO semiconductors are fabricated via adhesion-lithography. The development of a unique asymmetric nanogap electrode architecture results in devices with a high current rectification ratio (10(3) -10(6) ), low operating voltage (<3 V), and cut-off frequencies of >400 MHz. Device fabrication is scalable and can be performed at low temperatures even on plastic substrates with very high yield.

High-Efficiency Colloidal Quantum Dot Photovoltaics via Robust Self-Assembled Monolayers.

The optoelectronic tunability offered by colloidal quantum dots (CQDs) is attractive for photovoltaic applications but demands proper band alignment at electrodes for efficient charge extraction at minimal cost to voltage. With this goal in mind, self-assembled monolayers (SAMs) can be used to modify interface energy levels locally. However, to be effective SAMs must be made robust to treatment using the various solvents and ligands required for to fabricate high quality CQD solids. We report robust self-assembled monolayers (R-SAMs) that enable us to increase the efficiency of CQD photovoltaics. Only by developing a process for secure anchoring of aromatic SAMs, aided by deposition of the SAMs in a water-free deposition environment, were we able to provide an interface modification that was robust against the ensuing chemical treatments needed in the fabrication of CQD solids. The energy alignment at the rectifying interface was tailored by tuning the R-SAM for optimal alignment relative to the CQD quantum-confined electron energy levels. This resulted in a CQD PV record power conversion efficiency (PCE) of 10.7% with enhanced reproducibility relative to controls.

Manipulation of the Structure and Optoelectronic Properties through Bromine Inclusion in a Layered Lead Bromide Perovskite.

One of the great advantages of organic-inorganic metal halides is that their structures and properties are highly tuneable and this is important when optimizing materials for photovoltaics or other optoelectronic devices. One of the most common and effective ways of tuning the electronic structure is through anion substitution. Here, we report the inclusion of bromine into the layered perovskite [H3N(CH2)6NH3]PbBr4 to form [H3N(CH2)6NH3]PbBr4·Br2, which contains molecular bromine (Br2) intercalated between the layers of corner-sharing PbBr6 octahedra. Bromine intercalation in [H3N(CH2)6NH3]PbBr4·Br2 results in a decrease in the band gap of 0.85 eV and induces a structural transition from a Ruddlesden-Popper-like to Dion-Jacobson-like phase, while also changing the conformation of the amine. Electronic structure calculations show that Br2 intercalation is accompanied by the formation of a new band in the electronic structure and a significant decrease in the effective masses of around two orders of magnitude. This is backed up by our resistivity measurements that show that [H3N(CH2)6NH3]PbBr4·Br2 has a resistivity value of one order of magnitude lower than [H3N(CH2)6NH3]PbBr4, suggesting that bromine inclusion significantly increases the mobility and/or carrier concentration in the material. This work highlights the possibility of using molecular inclusion as an alternative tool to tune the electronic properties of layered organic-inorganic perovskites, while also being the first example of molecular bromine inclusion in a layered lead halide perovskite. By using a combination of crystallography and computation, we show that the key to this manipulation of the electronic structure is the formation of halogen bonds between the Br2 and Br in the [PbBr4]∞ layers, which is likely to have important effects in a range of organic-inorganic metal halides.

High-resolution cathodoluminescence hyperspectral imaging of nitride nanostructures.

Hyperspectral cathodoluminescence imaging provides spectrally and spatially resolved information on luminescent materials within a single dataset. Pushing the technique toward its ultimate nanoscale spatial limit, while at the same time spectrally dispersing the collected light before detection, increases the challenge of generating low-noise images. This article describes aspects of the instrumentation, and in particular data treatment methods, which address this problem. The methods are demonstrated by applying them to the analysis of nanoscale defect features and fabricated nanostructures in III-nitride-based materials.

Wide-Bandgap Halide Perovskites for Indoor Photovoltaics.

Indoor photovoltaics (IPVs) are receiving great research attention recently due to their projected application in the huge technology field of Internet of Things (IoT). Among the various existing photovoltaic technologies such as silicon, Cadmium Telluride (CdTe), Copper Indium Gallium Selenide (CIGS), organic photovoltaics, and halide perovskites, the latter are identified as the most promising for indoor light harvesting. This suitability is mainly due to its composition tuning adaptability to engineer the bandgap to match the indoor light spectrum and exceptional optoelectronic properties. Here, in this review, we are summarizing the state-of-the-art research efforts on halide perovskite-based indoor photovoltaics, the effect of composition tuning, and the selection of various functional layer and device architecture onto their power conversion efficiency. We also highlight some of the challenges to be addressed before these halide perovskite IPVs are commercialized.

BODIPY derivatives with near infra-red absorption as small molecule donors for bulk heterojunction solar cells.

The study of small donor molecules as the active component of organic solar cells continues to attract considerable attention due to the range of advantages these molecules have over their polymeric counterparts. Here we report the synthesis and solar cell fabrication of three BODIPY small molecule donors. Two of the dyes feature triphenylamine and phenothiazine as donor units attached to the meso and α-positions of the BODIPY core (TPA-PTZ-DBP and PTZ-TPA-BDP). Additionally, we have synthesised a push-pull derivative featuring phenothiazine moieties in the α-positions and a nitrobenzene in the meso-position (N-TPA-BDP) in order to investigate what effect this type of functionalisation has on the photovoltaic properties compared to the other dyes. The optoelectronic properties were investigated and the dyes showed broad absorption in the near-infrared with high extinction coefficients. Electrochemical measurements indicated good reversibility for the dyes redox processes. In contrast with the all-donor functionalised systems, N-TPA-BDP demonstrated extensive HOMO-LUMO overlap by DFT. The dyes were investigated as donor molecules in bulk heterojunction solar cells along with PC71BM, and under optimal donor to acceptor ratio PTZ-TPA-BDP showed the highest PCE of 1.62%. N-PTZ-BDP:PC71BM was the only blend to further improve upon thermal annealing reaching the highest conversion efficiency among the dyes of 1.71%. A morphology comprised of finely mixed donor and acceptor components is observed for BHJ blends of each of the three donors at their optimum fullerene content. Upon thermal annealing, these morphological features remain mostly the same for PTZ-TPA-BDP:PC71BM and TPA-PTZ-DBP:PC71BM blends whereas for N-PTZ-BDP:PC71BM the domains show a larger size. These dyes show that phenothiazine functionalisation of BODIPY is useful for solar cells because it gives strong and broad absorption extending to the near infra-red and materials with reversible redox properties - both of which are desirable for organic solar cells.

Charge carrier localised in zero-dimensional (CH3NH3)3Bi2I9 clusters.

A metal-organic hybrid perovskite (CH3NH3PbI3) with three-dimensional framework of metal-halide octahedra has been reported as a low-cost, solution-processable absorber for a thin-film solar cell with a power-conversion efficiency over 20%. Low-dimensional layered perovskites with metal halide slabs separated by the insulating organic layers are reported to show higher stability, but the efficiencies of the solar cells are limited by the confinement of excitons. In order to explore the confinement and transport of excitons in zero-dimensional metal-organic hybrid materials, a highly orientated film of (CH3NH3)3Bi2I9 with nanometre-sized core clusters of Bi2I93- surrounded by insulating CH3NH3+ was prepared via solution processing. The (CH3NH3)3Bi2I9 film shows highly anisotropic photoluminescence emission and excitation due to the large proportion of localised excitons coupled with delocalised excitons from intercluster energy transfer. The abrupt increase in photoluminescence quantum yield at excitation energy above twice band gap could indicate a quantum cutting due to the low dimensionality.Understanding the confinement and transport of excitons in low dimensional systems will aid the development of next generation photovoltaics. Via photophysical studies Ni et al. observe 'quantum cutting' in 0D metal-organic hybrid materials based on methylammonium bismuth halide (CH3NH3)3Bi2I9.

Double-Sided Junctions Enable High-Performance Colloidal-Quantum-Dot Photovoltaics.

The latest advances in colloidal-quantum-dot material processing are combined with a double-sided junction architecture, which is done by efficiently incorporating indium ions in the ZnO eletrode. This platform allows the collection of all photogenerated carriers even at the maximum power point. The increased depletion width in the device facilitates full carrier collection, leading to a record 10.8% power conversion efficiency.