2D Hybrid Perovskite Sensors for Environmental and Healthcare Monitoring.

Layered perovskites, a novel class of two-dimensional (2D) layered materials, exhibit versatile photophysical properties of great interest in photovoltaics and optoelectronics. However, their instability to environmental factors, particularly water, has limited their utility. In this study, we introduce an innovative solution to the problem by leveraging the unique properties of natural beeswax as a protective coating of 2D-fluorinated phenylethylammonium lead iodide perovskite. These photodetectors show outstanding figures of merit, such as a responsivity of >2200 A/W and a detectivity of 2.4 × 1018 Jones. The hydrophobic nature of beeswax endows the 2D perovskite sensors with an unprecedented resilience to prolonged immersion in contaminated water, and it increases the lifespan of devices to a period longer than one year. At the same time, the biocompatibility of the beeswax and its self-cleaning properties make it possible to use the very same turbidity sensors for healthcare in photoplethysmography and monitor the human heartbeat with clear systolic and diastolic signatures. Beeswax-enabled multipurpose optoelectronics paves the way to sustainable electronics by ultimately reducing the need for multiple components.

Room Temperature Polariton Condensation from Whispering Gallery Modes in CsPbBr3 Microplatelets.

Room temperature (RT) polariton condensate holds exceptional promise for revolutionizing various fields of science and technology, encompassing optoelectronics devices to quantum information processing. Using perovskite materials, like all-inorganic cesium lead bromide (CsPbBr3) single crystal, provides additional advantages, such as ease of synthesis, cost-effectiveness, and compatibility with existing semiconductor technologies. In this work, the formation of whispering gallery modes (WGM) in CsPbBr3 single crystals with controlled geometry is shown, synthesized using a low-cost and efficient capillary bridge method. Through the implementation of microplatelets geometry, enhanced optical properties and performance are achieved due to the presence of sharp edges and a uniform surface, effectively avoiding non-radiative scattering losses caused by defects. This allows not only to observe strong light matter coupling and formation of whispering gallery polaritons, but also to demonstrate the onset of polariton condensation at RT. This investigation not only contributes to the advancement of the knowledge concerning the exceptional optical properties of perovskite-based polariton systems, but also unveils prospects for the exploration of WGM polariton condensation within the framework of a 3D perovskite-based platform, working at RT. The unique characteristics of polariton condensate, including low excitation thresholds and ultrafast dynamics, open up unique opportunities for advancements in photonics and optoelectronics devices.

Thermochromic Printable and Multicolor Polymeric Composite Based on Hybrid Organic-Inorganic Perovskite.

Hybrid organic-inorganic perovskites (PVKs) are among the most promising materials for optoelectronic applications thanks to their outstanding photophysical properties and easy synthesis. Herein, a new PVK-based thermochromic composite is demonstrated. It can reversibly switch from a transparent state (transmittance > 80%) at room temperature to a colored state (transmittance < 10%) at high temperature, with very fast kinetics, taking only a few seconds to go from the bleached to the colored state (and vice versa). X-ray diffraction, Fourier-transform infrared spectroscopy, differential scanning calometry, rheological, and optical measurements carried out during heating/cooling cycles reveal that thermochromism in the material is based on a reversible process of PVK disassembly/assembly mediated by intercalating polymeric chains, through the formation and breaking of hydrogen bonds between polymer and perovskite. Therefore, differently from other thermochromic perovskites, that generally work with the adsorption/desorption of volatile molecules, the system is able to perform several heating/cooling cycles regardless of environmental conditions. The color and transition temperature (from 70 to 120 °C) can be tuned depending on the type of perovskite. Moreover, this thermochromic material is printable and can be deposited by cheap techniques, paving the way for a new class of smart coatings with an unprecedented range of colors.

Strongly enhanced light-matter coupling of monolayer WS2 from a bound state in the continuum.

Exciton-polaritons derived from the strong light-matter interaction of an optical bound state in the continuum with an excitonic resonance can inherit an ultralong radiative lifetime and significant nonlinearities, but their realization in two-dimensional semiconductors remains challenging at room temperature. Here we show strong light-matter interaction enhancement and large exciton-polariton nonlinearities at room temperature by coupling monolayer tungsten disulfide excitons to a topologically protected bound state in the continuum moulded by a one-dimensional photonic crystal, and optimizing for the electric-field strength at the monolayer position through Bloch surface wave confinement. By a structured optimization approach, the coupling with the active material is maximized here in a fully open architecture, allowing to achieve a 100 meV photonic bandgap with the bound state in the continuum in a local energy minimum and a Rabi splitting of 70 meV, which results in very high cooperativity. Our architecture paves the way to a class of polariton devices based on topologically protected and highly interacting bound states in the continuum.

Rydberg polaritons in ReS2 crystals.

Rhenium disulfide belongs to group VII transition metal dichalcogenides (TMDs) with attractive properties such as exceptionally high refractive index and remarkable oscillator strength, large in-plane birefringence, and good chemical stability. Unlike most other TMDs, the peculiar optical properties of rhenium disulfide persist from bulk to the monolayer, making this material potentially suitable for applications in optical devices. In this work, we demonstrate with unprecedented clarity the strong coupling between cavity modes and excited states, which results in a strong polariton interaction, showing the interest of these materials as a solid-state counterpart of Rydberg atomic systems. Moreover, we definitively clarify the nature of important spectral features, shedding light on some controversial aspects or incomplete interpretations and demonstrating that their origin is due to the interesting combination of the very high refractive index and the large oscillator strength expressed by these TMDs.

Electrically tunable Berry curvature and strong light-matter coupling in liquid crystal microcavities with 2D perovskite.

The field of spinoptronics is underpinned by good control over photonic spin-orbit coupling in devices that have strong optical nonlinearities. Such devices might hold the key to a new era of optoelectronics where momentum and polarization degrees of freedom of light are interwoven and interfaced with electronics. However, manipulating photons through electrical means is a daunting task given their charge neutrality. In this work, we present electrically tunable microcavity exciton-polariton resonances in a Rashba-Dresselhaus spin-orbit coupling field. We show that different spin-orbit coupling fields and the reduced cavity symmetry lead to tunable formation of the Berry curvature, the hallmark of quantum geometrical effects. For this, we have implemented an architecture of a photonic structure with a two-dimensional perovskite layer incorporated into a microcavity filled with nematic liquid crystal. Our work interfaces spinoptronic devices with electronics by combining electrical control over both the strong light-matter coupling conditions and artificial gauge fields.

Tuning of the Berry curvature in 2D perovskite polaritons.

The engineering of the energy dispersion of polaritons in microcavities through nanofabrication or through the exploitation of intrinsic material and cavity anisotropies has demonstrated many intriguing effects related to topology and emergent gauge fields such as the anomalous quantum Hall and Rashba effects. Here we show how we can obtain different Berry curvature distributions of polariton bands in a strongly coupled organic-inorganic two-dimensional perovskite single-crystal microcavity. The spatial anisotropy of the perovskite crystal combined with photonic spin-orbit coupling produce two Hamilton diabolical points in the dispersion. An external magnetic field breaks time-reversal symmetry owing to the exciton Zeeman splitting and lifts the degeneracy of the diabolical points. As a result, the bands possess non-zero integral Berry curvatures, which we directly measure by state tomography. In addition to the determination of the different Berry curvatures of the multimode microcavity dispersions, we can also modify the Berry curvature distribution, the so-called band geometry, within each band by tuning external parameters, such as temperature, magnetic field and sample thickness.

Managing Growth and Dimensionality of Quasi 2D Perovskite Single-Crystalline Flakes for Tunable Excitons Orientation.

Hybrid perovskites are among the most promising materials for optoelectronic applications. Their 2D crystalline form is even more interesting since the alternating inorganic and organic layers naturally forge a multiple quantum-well structure, leading to the formation of stable excitonic resonances. Nevertheless, a controlled modulation of the quantum well width, which is defined by the number of inorganic layers (n) between two organic ones, is not trivial and represents the main synthetic challenge in the field. Here, a conceptually innovative approach to easily tune n in lead iodide perovskite single-crystalline flakes is presented. The judicious use of potassium iodide is found to modulate the supersaturation levels of the precursors solution without being part of the final products. This allows to obtain a fine tuning of the n value. The excellent optical quality of the as synthesized flakes guarantees an in-depth analysis by Fourier-space microscopy, revealing that the excitons orientation can be manipulated by modifying the number of inorganic layers. Excitonic out-of-plane component, indeed, is enhanced when "n" is increased. The combined advances in the synthesis and optical characterization fill in the picture of the exciton behavior in low-dimensional perovskite, paving the way to the design of materials with improved optoelectronic characteristics.

Demonstration of Self-Starting Nonlinear Mode Locking in Random Lasers.

In ultrafast multimode lasers, mode locking is implemented by means of saturable absorbers or modulators, allowing for very short pulses. This occurs because of nonlinear interactions of modes with well equispaced frequencies. Though theory predicts that, in the absence of any device, mode locking would occur in random lasers, this has never been demonstrated so far. Through the analysis of multimode correlations we provide clear evidence for nonlinear mode coupling in random lasers. The behavior of multiresonance intensity correlations is tested against the nonlinear frequency matching condition equivalent to the one underlying phase locking in ordered ultrafast lasers. Nontrivially large correlations are clearly observed for spatially overlapping resonances that sensitively depend on the frequency matching condition to be satisfied, eventually demonstrating the occurrence of nonlinear mode-locked mode coupling. This is the first example, to our knowledge, of an experimental realization of self-starting mode locking in random lasers, allowing for many new developments in the design and use of nanostructured devices.

Improved Photostability in Fluorinated 2D Perovskite Single Crystals.

Hybrid organic-inorganic perovskites are very promising semiconductors for many optoelectronic applications, although their extensive use is limited by their poor stability under environmental conditions. In this work, we synthesize two-dimensional perovskite single crystals and investigate their optical and structural evolution under continuous light irradiation. We found that the hydrophobic nature of the fluorinated component, together with the absence of grain boundary defects, lead to improved material stability thanks to the creation of a robust barrier that preserve the crystalline structure, hindering photo-degradation processes usually promoted by oxygen and moisture.

Pseudocapacitive behaviour in sol-gel derived electrochromic titania nanostructures.

Nanostructured thin films are widely investigated for application in multifunctional devices thanks to their peculiar optoelectronic properties. In this work anatase TiO2 nanoparticles (average diameter 10 nm) synthesised by a green aqueous sol-gel route are exploited to fabricate optically active electrodes for pseudocapacitive-electrochromic devices. In our approach, highly transparent and homogeneous thin films having a good electronic coupling between nanoparticles are prepared. These electrodes present a spongy-like nanostructure in which the dimension of native nanoparticles is preserved, resulting in a huge surface area. Cyclic voltammetry studies reveal that there are significant contributions to the total stored charge from both intercalation capacitance and pseudocapacitance, with a remarkable 50% of the total charge deriving from this second effect. Fast and reversible colouration occurs, with an optical modulation of ∼60% in the range of 315-1660 nm, and a colouration efficiency of 25.1 cm2 C-1 at 550 nm. This combination of pseudocapacitance and electrochromism makes the sol-gel derived titania thin films promising candidates for multifunctional 'smart windows'.

Quantum Nature of Light in Nonstoichiometric Bulk Perovskites.

Sources of single photons are a fundamental brick in the development of quantum information technologies. Great efforts have been made so far in the realization of reliable, highly efficient, and on demand quantum sources that could show an easy integration with quantum devices. This has recently culminated in the use of solid state quantum dots as promising candidates for future sources of quantum technologies. However, some challenges, like their complex fabrication, random distribution, and difficult integrability with silicon technology, could hinder their broad application, making necessary the study of alternative systems. In this work, we clearly demonstrate single photon emission from quantum dots formed in nonstoichiometric bulk perovskites. Their simple growing procedures, exceptional stability under constant illumination, easy control of their optical properties, as well as ease of integrability make these materials very interesting candidates for the development of quantum light sources in the near-infrared.

Role of direct and inverted undoped spiro-OMeTAD-perovskite architectures in determining solar cells performances: an investigation via electrical impedance spectroscopy.

The present study involved an investigation on the reasoning behind the dependence of the perovskite solar cells photovoltaic efficiencies on the relative position of the undoped spiro-OMeTAD hole-transport material with respect to the perovskite in the device. We adopted impedance spectroscopy to investigate the modification of the carrier transport mechanisms across the spiro-OMeTAD/perovskite interface constituting the active part where the main device processes occur. We investigated two interface structures, referred to as the direct (or regular, n-i-p) and the inverted (p-i-n) configuration. This work also intended to further stress the possible adoption of alternative device structures working with undoped hole-transport materials.

Rational Design of Molecular Hole-Transporting Materials for Perovskite Solar Cells: Direct versus Inverted Device Configurations.

Due to a still limited understanding of the reasons making 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene (Spiro-OMeTAD) the state-of-the-art hole-transporting material (HTM) for emerging photovoltaic applications, the molecular tailoring of organic components for perovskite solar cells (PSCs) lacks in solid design criteria. Charge delocalization in radical cationic states can undoubtedly be considered as one of the essential prerequisites for an HTM, but this aspect has been investigated to a relatively minor extent. In marked contrast with the 3-D structure of Spiro-OMeTAD, truxene-based HTMs Trux1 and Trux2 have been employed for the first time in PSCs fabricated with a direct (n-i-p) or inverted (p-i-n) architecture, exhibiting a peculiar behavior with respect to the referential HTM. Notwithstanding the efficient hole extraction from the perovskite layer exhibited by Trux1 and Trux2 in direct configuration devices, their photovoltaic performances were detrimentally affected by their poor hole transport. Conversely, an outstanding improvement of the photovoltaic performances in dopant-free inverted configuration devices compared to Spiro-OMeTAD was recorded, ascribable to the use of thinner HTM layers. The rationalization of the photovoltaic performances exhibited by different configuration devices discussed in this paper can provide new and unexpected prospects for engineering the interface between the active layer of perovskite-based solar cells and the hole transporters.

Multi-Scale-Porosity TiO2 scaffolds grown by innovative sputtering methods for high throughput hybrid photovoltaics.

We propose an up-scalable, reliable, contamination-free, rod-like TiO2 material grown by a new method based on sputtering deposition concepts which offers a multi-scale porosity, namely: an intra-rods nano-porosity (1-5 nm) arising from the Thornton's conditions and an extra-rods meso-porosity (10-50 nm) originating from the spatial separation of the Titanium and Oxygen sources combined with a grazing Ti flux. The procedure is simple, since it does not require any template layer to trigger the nano-structuring, and versatile, since porosity and layer thickness can be easily tuned; it is empowered by the lack of contaminations/solvents and by the structural stability of the material (at least) up to 500 °C. Our material gains porosity, stability and infiltration capability superior if compared to conventionally sputtered TiO2 layers. Its competition level with chemically synthesized reference counterparts is doubly demonstrated: in Dye Sensitized Solar Cells, by the infiltration and chemisorption of N-719 dye (∼1 × 1020 molecules/cm3); and in Perovskite Solar Cells, by the capillary infiltration of solution processed CH3NH3PbI3 which allowed reaching efficiency of 11.7%. Based on the demonstrated attitude of the material to be functionalized, its surface activity could be differently tailored on other molecules or gas species or liquids to enlarge the range of application in different fields.

[1]Benzothieno[3,2-b]benzothiophene-Based Organic Dyes for Dye-Sensitized Solar Cells.

Three new metal-free organic dyes with the [1]benzothieno[3,2-b]benzothiophene (BTBT) π-bridge, having the structure donor-π-acceptor (D-π-A) and labeled as 19, 20 and 21, have been designed and synthesized for application in dye-sensitized solar cells (DSSC). Once the design of the π-acceptor block was fixed, containing the BTBT as the π-bridge and the cyanoacrylic group as the electron acceptor and anchoring unit, we selected three donor units with different electron-donor capacity, in order to assemble new chromophores with high molar extinction coefficients (ε), whose absorption features well reflect the good performance of the final DSSC devices. Starting with the 19 dye, which shows a molar extinction coefficient ε of over 14,000 M(-1) cm(-1) and takes into account the absorption maximun at the longer wavelength, the substitution of the BFT donor unit with the BFA yields a great enhancement of absorptivity (molar extinction coefficient ε > 42,000 M(-1) cm(-1)), until reaching the higher value (ε > 69,000 M(-1) cm(-1)) with the BFPhz donor unit. The good general photovoltaic performances obtained with the three dyes highlight the suitable properties of electron-transport of the BTBT as the π-bridge in organic chromophore for DSSC, making this very cheap and easy to synthesize molecule particularly attractive for efficient and low-cost photovoltaic devices.

NiO/MAPbI(3-x)Clx/PCBM: a model case for an improved understanding of inverted mesoscopic solar cells.

A spectroscopic investigation focusing on the charge generation and transport in inverted p-type perovskite-based mesoscopic (Ms) solar cells is provided in this report. Nanocrystalline nickel oxide and PCBM are employed respectively as hole transporting scaffold and hole blocking layer to sandwich a perovskite light harvester. An efficient hole transfer process from perovskite to nickel oxide is assessed, through time-resolved photoluminescence and photoinduced absorption analyses, for both the employed absorbing species, namely MAPbI3-xClx and MAPbI3. A striking relevant difference between p-type and n-type perovskite-based solar cells emerges from the study.

Influence of porphyrinic structure on electron transfer processes at the electrolyte/dye/TiO2 interface in PSSCs: a comparison between meso push-pull and ß-pyrrolic architectures.

Time-resolved photophysical and photoelectrochemical investigations have been carried out to compare the electron transfer dynamics of a 2-ß-substituted tetraarylporphyrinic dye (ZnB) and a 5,15-meso-disubstituted diarylporphyrinic one (ZnM) at the electrolyte/dye/TiO2 interface in PSSCs. Although the meso push-pull structural arrangement has shown, up to now, to have the best performing architecture for solar cell applications, we have obtained superior energy conversion efficiencies for ZnB (6.1%) rather than for ZnM (3.9%), by using the I(-)/I3(-)-based electrolyte. To gain deeper insights about these unexpected results, we have investigated whether the intrinsic structural features of the two different porphyrinic dyes can play a key role on electron transfer processes occurring at the dye-sensitized TiO2 interface. We have found that charge injection yields into TiO2 are quite similar for both dyes and that the regeneration efficiencies by I(-), are also comparable and in the range of 75-85%. Moreover, besides injection quantum yields above 80%, identical dye loading, for both ZnB and ZnM, has been evidenced by spectrophotometric measurements on transparent thin TiO2 layers after the same adsorption period. Conversely, major differences have emerged by DC and AC (electrochemical impedance spectroscopy) photoelectrochemical investigations, pointing out a slower charge recombination rate when ZnB is adsorbed on TiO2. This may result from its more sterically hindered macrocyclic core which, besides guaranteeing a decrease of π-staking aggregation of the dye, promotes a superior shielding of the TiO2 surface against charge recombination involving oxidized species of the electrolyte.

Enhancing dye-sensitized solar cell performances by molecular engineering: highly efficient π-extended organic sensitizers.

This study deals with the synthesis and characterization of two π-extended organic sensitizers (G1 and G2) for applications in dye-sensitized solar cells. The materials are designed with a D-A-π-A structure constituted by i) a triarylamine group as the donor part, ii) a dithienyl-benzothiadiazole chromophore followed by iii) a further ethynylene-thiophene (G1) or ethynylene-benzene (G2) π-spacer and iv) a cyano-acrylic moiety as acceptor and anchoring part. An unusual structural extension of the π-bridge characterizes these structures. The so-configured sensitizers exhibit a broad absorption profile, the origin of which is supported by density functional theory. The absence of hypsochromic shifts as a consequence of deprotonation as well as notable optical and electrochemical stabilities are also observed. Concerning the performances in devices, electrochemical impedance spectroscopy indicates that the structural modification of the π-spacer mainly increases the electron lifetime of G2 with respect to G1. In devices, this feature translates into a superior power conversion efficiency of G2, reaching 8.1%. These results are comparable to those recorded for N719 and are higher with respect to literature congeners, supporting further structural engineering of the π-bridge extension in the search for better performing π-extended organic sensitizers.