Proton conductivity of the protein-based velvet worm slime.

The properties of complex bodily fluids are linked to their biological functions through natural selection. Velvet worms capture their prey by ensnaring them with a proteinaceous fluid (slime). We examined the electrical conductivity of slime and found that dry slime is an insulator. However, its conductivity can increase by up to 106 times in its hydrated state, which can be further increased by an order in magnitude under acidic hydration (pH ≈ 2.3). The transient current measured using ion-blocking electrodes showed a continuous decay for up to 7 h, revealing slime's nature as a proton conducting material. Slime undergoes a spontaneous fibrilization process producing high aspect ratio ≈ 105 fibers that exhibit an average conductivity ≈2.4 ± 1.1 mS cm-1. These findings enhance our understanding of slime as a natural biopolymer and provide molecular-level guidelines to rationally design biomaterials that may be employed as hygroscopic conductors.

The importance of anchoring ligands of binuclear sensitizers on electron transfer processes and photovoltaic action in dye-sensitized solar cells.

The relatively low photon-to-current conversion efficiency of dye-sensitized solar cells is their major drawback limiting widespread application. Light harvesting, followed by a series of electron transfer processes, is the critical step in photocurrent generation. An in-depth understanding and fine optimization of those processes are crucial to enhance cell performance. In this work, we synthesize two new bi-ruthenium sensitizers with extended anchoring ligands to gain insight into underlying processes determining photovoltaic action mechanisms. The structure of the compounds has been confirmed, and their properties have been thoroughly examined by various techniques such as NMR, IR, elemental analysis UV-Vis, cyclic voltammetry, and electroabsorption. The experimental characterization has been supported and developed via extensive quantum-chemical calculations, giving a broad view of the presented molecules' properties. Finally, the DSSC devices have been assembled utilizing obtained dyes. The photovoltaic and EIS measurements, combined with performed calculations and fundamental dyes characterization, unraveled an intramolecular electron transfer as an initial step of the electron injection process at the dye/semiconductor interface. The overall photovoltaic action mechanism has been discussed. Our study demonstrates the significance of the anchoring group architecture in the molecular design of new sensitizers for DSSC applications.

Directional Emission from Electrically Injected Exciton-Polaritons in Perovskite Metasurfaces.

We present a new approach to achieving strong coupling between electrically injected excitons and photonic bound states in the continuum of a dielectric metasurface. Here a high-finesse metasurface cavity is monolithically patterned in the channel of a perovskite light-emitting transistor to induce a large Rabi splitting of ∼200 meV and more than 50-fold enhancement of the polaritonic emission compared to the intrinsic excitonic emission of the perovskite film. Moreover, the directionality of polaritonic electroluminescence can be dynamically tuned by varying the source-drain bias, which induces an asymmetric distribution of exciton population within the transistor channel. We argue that this approach provides a new platform to study strong light-matter interactions in dispersion engineered photonic cavities under electrical injection and paves the way to solution-processed electrically pumped polariton lasers.

Polarization-Tunable Perovskite Light-Emitting Metatransistor.

Emerging immersive visual communication technologies require light sources with complex functionality for dynamic control of polarization, directivity, wavefront, spectrum, and intensity of light. Currently, this is mostly achieved by free space bulk optic elements, limiting the adoption of these technologies. Flat optics based on artificially structured metasurfaces that operate at the sub-wavelength scale are a viable solution, however, their integration into electrically driven devices remains challenging. Here, a radically new approach to monolithic integration of a dielectric metasurface into a perovskite light-emitting transistor is demonstrated. It is shown that nanogratings directly structured on top of the transistor channel yield an 8-fold increase of electroluminescence intensity and dynamic tunability of polarization. This new light-emitting metatransistor device concept opens unlimited opportunities for light management strategies based on metasurface design and integration.

Phase-Change Perovskite Microlaser with Tunable Polarization Vortex.

Metasurfaces supporting optical bound states in the continuum (BICs) are emerging as simple and compact optical cavities to realize polarization-vortex lasers. The winding of the polarization around the singularity defines topological charges which are generally set by the cavity design and cannot be altered without changing geometrical parameters. Here, a subwavelength-thin phase-change halide perovskite BIC metasurface functioning as a tunable polarization vortex microlaser is demonstrated. Upon the perovskite structural phase transitions, both its refractive index and gain vary substantially, inducing reversible and bistable switching between distinct polarization vortexes underpinned by opposite topological charges. Dynamic tuning and switching of the resulting vector beams may find use in microscopy imaging, particle trapping and manipulation, and optical data storage.

Resonant Enhancement of Polymer-Cell Optostimulation by a Plasmonic Metasurface.

Organic semiconductors have shown great potential as efficient bioelectronic materials. Specifically, photovoltaic polymers such as the workhorse poly(thiophene) derivatives, when stimulated with visible light, can depolarize neurons and generate action potentials, an effect that has been also employed for rescuing vision in blind rats. In this context, however, the coupling of such materials with optically resonant structures to enhance those photodriven biological effects is still in its infancy. Here, we employ the optical coupling between a nanostructured metasurface and poly(3-hexylthiophene) (P3HT) to improve the bioelectronic effects occurring upon photostimulation at the abiotic-biotic interface. In particular, we designed a spectrally tuned aluminum metasurface that can resonate with P3HT, hence augmenting the effective field experienced by the polymer. In turn, this leads to an 8-fold increase in invoked inward current in cells. This enhanced activation strategy could be useful to increase the effectiveness of P3HT-based prosthetic implants for degenerative retinal disorders.

Perovskite metasurfaces with large superstructural chirality.

Recent attempts to synthesize hybrid perovskites with large chirality have been hampered by large size mismatch and weak interaction between their structure and the wavelength of light. Here we adopt a planar nanostructure design to overcome these limitations and realize all-dielectric perovskite metasurfaces with giant superstructural chirality. We identify a direct spectral correspondence between the near- and the far- field chirality, and tune the electric and magnetic multipole moments of the resonant chiral metamolecules to obtain large anisotropy factor of 0.49 and circular dichroism of 6350 mdeg. Simulations show that larger area metasurfaces could yield even higher optical activity, approaching the theoretical limits. Our results clearly demonstrate the advantages of nanostructrure engineering for the implementation of perovskite chiral photonic, optoelectronic, and spintronic devices.

Reversible Photochromism in ⟨110⟩ Oriented Layered Halide Perovskite.

Extending halide perovskites' optoelectronic properties to stimuli-responsive chromism enables switchable optoelectronics, information display, and smart window applications. Here, we demonstrate a band gap tunability (chromism) via crystal structure transformation from three-dimensional FAPbBr3 to a ⟨110⟩ oriented FAn+2PbnBr3n+2 structure using a mono-halide/cation composition (FA/Pb) tuning. Furthermore, we illustrate reversible photochromism in halide perovskite by modulating the intermediate n phase in the FAn+2PbnBr3n+2 structure, enabling greater control of the optical band gap and luminescence of a ⟨110⟩ oriented mono-halide/cation perovskite. Proton transfer reaction-mass spectroscopy carried out to precisely quantify the decomposition product reveals that the organic solvent in the film is a key contributor to the structural transformation and, therefore, the chromism in the ⟨110⟩ structure. These intermediate n phases (2 ≤ n ≤ ∞) stabilize in metastable states in the FAn+2PbnBr3n+2 system, which is accessible via strain or optical or thermal input. The structure reversibility in the ⟨110⟩ perovskite allowed us to demonstrate a class of photochromic sensors capable of self-adaptation to lighting.

Optical Rashba Effect in a Light-Emitting Perovskite Metasurface.

The Rashba effect, i.e., the splitting of electronic spin-polarized bands in the momentum space of a crystal with broken inversion symmetry, has enabled the realization of spin-orbitronic devices, in which spins are manipulated by spin-orbit coupling. In optics, where the helicity of light polarization represents the spin degree of freedom for spin-momentum coupling, the optical Rashba effect is manifested by the splitting of optical states with opposite chirality in the momentum space. Previous realizations of the optical Rashba effect relied on passive devices determining the surface plasmon or light propagation inside nanostructures, or the directional emission of chiral luminescence when hybridized with light-emitting media. An active device underpinned by the optical Rashba effect is demonstrated here, in which a monolithic halide perovskite metasurface emits highly directional chiral photoluminescence. An all-dielectric metasurface design with broken in-plane inversion symmetry is directly embossed into the high-refractive-index, light-emitting perovskite film, yielding a degree of circular polarization of photoluminescence of 60% at room temperature.

Room temperature synthesis of low-dimensional rubidium copper halide colloidal nanocrystals with near unity photoluminescence quantum yield.

Metal lead halide perovskite nanocrystals have emerged as promising candidates for optoelectronic applications. However, the inclusion of toxic lead is a major concern for the commercial viability of these materials. Herein, we introduce a new family of non-toxic reduced dimension Rb2CuX3 (X = Br, Cl) colloidal nanocrystals with one-dimensional crystal structure consisting [CuX4]3- ribbons isolated by Rb+ cations. These nanocrystals were synthesised using a room-temperature method under ambient conditions, which makes them cost effective and scalable. Phase purity quantification was confirmed by Rietveld refinement of powder X-ray diffraction and corroborated by 87Rb MAS NMR technique. Both samples also exhibited high thermal stability up to 500 °C, which is essential for optoelectronic applications. Rb2CuBr3 and Rb2CuCl3 display PL emission peaks at 387 nm and 400 nm with high PLQYs of ∼100% and ∼49%, respectively. Lastly, the first colloidal synthesis of quantum-confined rubidium copper halide-based nanocrystals opens up a new avenue to exploit their optical properties in lighting technology as well as water sterilisation and air purification.

Activated Carbon Produced by Pyrolysis of Waste Wood and Straw for Potential Wastewater Adsorption.

Pyrolysis of straw pellets and wood strips was performed in a fixed bed reactor. The chars, solid products of thermal degradation, were used as potential materials for activated carbon production. Chemical and physical activation processes were used to compare properties of the products. The chemical activation agent KOH was chosen and the physical activation was conducted with steam and carbon dioxide as oxidising gases. The effect of the activation process on the surface area, pore volume, structure and composition of the biochar was examined. The samples with the highest surface area (1349.6 and 1194.4 m2/g for straw and wood activated carbons, respectively) were obtained when the chemical activation with KOH solution was applied. The sample with the highest surface area was used as an adsorbent for model wastewater contamination removal.