Implication of polymeric template agent on the formation process of hybrid halide perovskite films.

The use of polymeric additives supporting the growth of hybrid halide perovskites has proven to be a successful approach aiming at high quality active layers targeting optoelectronic exploitation. A detailed description of the complex process involving the self-assembly of the precursors into the perovskite crystallites in presence of the polymer is, however, still missing. Here we take starch:CH3NH3PbI3 (MAPbI3) as example of highly performing composite, both in solar cells and light emitting diodes, and study the film formation process through differential scanning calorimetry and in situ time-resolved grazing incidence wide-angle x-ray scattering, performed during spin coating. These measurements reveal that starch beneficially influences the nucleation and growth of the perovskite precursor phase, leading to improved structural properties of the resulting film which turns into higher stability towards environmental conditions.

Water-Stable DMASnBr3 Lead-Free Perovskite for Effective Solar-Driven Photocatalysis.

Water-stable metal halide perovskites could foster tremendous progresses in several research fields where their superior optical properties can make differences. In this work we report clear evidence of water stability in a lead-free metal halide perovskite, namely DMASnBr3 , obtained by means of diffraction, optical and X-ray photoelectron spectroscopy. Such unprecedented water-stability has been applied to promote photocatalysis in aqueous medium, in particular by devising a novel composite material by coupling DMASnBr3 to g-C3 N4 , taking advantage from the combination of their optimal photophysical properties. The prepared composites provide an impressive hydrogen evolution rate >1700 µmol g-1 h-1 generated by the synergistic activity of the two composite costituents. DFT calculations provide insight into this enhancement deriving it from the favorable alignment of interfacial energy levels of DMASnBr3 and g-C3 N4 . The demonstration of an efficient photocatalytic activity for a composite based on lead-free metal halide perovskite in water paves the way to a new class of light-driven catalysts working in aqueous environments.

Room-temperature processed films of colloidal carved rod-shaped nanocrystals of reduced tungsten oxide as interlayers for perovskite solar cells.

Thanks to their high stability, good optoelectronic and extraordinary electrochromic properties, tungsten oxides are among the most valuable yet underexploited materials for energy conversion applications. Herein, colloidal one-dimensional carved nanocrystals of reduced tungsten trioxide (WO3-x) are successfully integrated, for the first time, as a hole-transporting layer (HTL) into CH3NH3PbI3 perovskite solar cells with a planar inverted device architecture. Importantly, the use of such preformed nanocrystals guarantees the facile solution-cast-only deposition of a homogeneous WO3-x thin film at room temperature, allowing achievement of the highest power conversion efficiency ever reported for perovskite solar cells incorporating raw and un-doped tungsten oxide based HTL.

GO/PEDOT:PSS nanocomposites: effect of different dispersing agents on rheological, thermal, wettability and electrochemical properties.

In this work glucose (G), α-cyclodextrin (α-CD) and sodium salt of carboxymethyl cellulose (CMCNa) are used as dispersing agents for graphene oxide (GO), exploring the influence of both saccharide units and geometric/steric hindrance on the rheological, thermal, wettability and electrochemical properties of a GO/poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) nanocomposite. By acting on the saccharide-based additives, we can modulate the rheological, thermal, and wettability properties of the GO/PEDOT:PSS nanocomposite. Firstly, the influence of all the additives on the rheological behaviour of GO and PEDOT:PSS was investigated separately in order to understand the effect of the dispersing agent on both the components of the ternary nanocomposite, individually. Subsequently, steady shear and dynamic frequency tests were conducted on all the nanocomposite solutions, characterized by thermal, wettability and morphological analysis. Finally, the electrochemical properties of the GO/PEDOT composites with different dispersing agents for supercapacitors were investigated using cyclic voltammetry (CV). The CV results revealed that GO/PEDOT with glucose exhibited the highest specific capacitance among the systems investigated.

Stark effect in perovskite/TiO2 solar cells: evidence of local interfacial order.

To unveil the mechanisms controlling photovoltaic conversion in high-performing perovskite-based mesostructured solar cells, we focus on the key role played by the mesoporous oxide/perovskite interface. We employ several spectroscopic techniques to design a complete scenario and corroborate our results with first principle density functional theory calculations. In particular Stark spectroscopy, a powerful tool allowing interface-sensitive analysis is employed to prove the existence of oriented permanent dipoles, consistent with the hypothesis of an ordered perovskite layer, close to the oxide surface. The existence of a structural order, promoted by specific local interactions, could be one of the decisive reasons for highly efficient carriers transport within perovskite films.

Cyanobuta-1,3-dienes as novel electron acceptors for photoactive multicomponent systems.

The synthesis, electrochemical, and photophysical properties of five multicomponent systems featuring a Zn(II) porphyrin (ZnP) linked to one or two anilino donor-substituted pentacyano- (PCBD) or tetracyanobuta-1,3-dienes (TCBD), with and without an interchromophoric bridging spacer (S), are reported: ZnP-S-PCBD (1), ZnP-S-TCBD (2), ZnP-TCBD (3), ZnP-(S-PCBD)2 (4), and ZnP-(S-TCBD)2 (5). By means of steady-state and time-resolved absorption and luminescence spectroscopy (RT and 77 K), photoinduced intramolecular energy and electron transfer processes are evidenced, upon excitation of the porphyrin unit. In systems equipped with the strongest acceptor PCBD and the spacer (1, 4), no evidence of electron transfer is found in toluene, suggesting ZnP→PCBD energy transfer, followed by ultrafast (<10 ps) intrinsic deactivation of the PCBD moiety. In the analogous systems with the weaker acceptor TCBD (2, 5), photoinduced electron transfer occurs in benzonitrile, generating a charge-separated (CS) state lasting 2.3 µs. Such a long lifetime, in light of the high Gibbs free energy for charge recombination (ΔG(CR)=-1.39 eV), suggests a back-electron transfer process occurring in the so-called Marcus inverted region. Notably, in system 3 lacking the interchromophoric spacer, photoinduced charge separation followed by charge recombination occur within 20 ps. This is a consequence of the close vicinity of the donor-acceptor partners and of a virtually activationless electron transfer process. These results indicate that the strongly electron-accepting cyanobuta-1,3-dienes might become promising alternatives to quinone-, perylenediimide-, and fullerene-derived acceptors in multicomponent modules featuring photoinduced electron transfer.

Mimicking Natural Antioxidant Systems for Improved Photostability in Wide-Band-Gap Perovskite Solar Cells.

Fostered by the top power conversion efficiencies (PCEs) of lab-scale devices, industrialization of perovskite solar cells is underway. Nevertheless, the intrinsically poor stability of these materials still represents a major concern. Herein, inspired by Nature, the use of ß-carotene in perovskite solar cells is proposed to mimic its role as a protective pigment, as occurs in natural photosynthesis. Laser-mediated photostability (LMPS) assessment, Fourier-transform infrared spectra analysis acquired in attenuate total reflectance (ATR-FTIR), spectroscopy ellipsometry (SE), and time-resolved photoluminescence (TRPL) measurements under stress conditions prove that the inclusion of a thin ß-carotene interlayer promotes a high improvement in the photostability of the perovskite films against photooxidation. Importantly, this is accompanied by an improvement of the solar cell PCE that approaches 20% efficiency with no hysteresis, which is among the highest values reported for a mixed halide (I-Br) perovskite with a band gap of 1.74 eV, relevant for coupling with silicon in tandem cells.

Preparation of Heterojunctions Based on Cs3Bi2Br9 Nanocrystals and g-C3N4 Nanosheets for Photocatalytic Hydrogen Evolution.

Heterojunctions based on metal halide perovskites (MHPs) are promising systems for the photocatalytic hydrogen evolution reaction (HER). In this work, we coupled Cs3Bi2Br9 nanocrystals (NCs), obtained by wet ball milling synthesis, with g-C3N4 nanosheets (NSs), produced by thermal oxidation of bulk g-C3N4, in air. These methods are reproducible, inexpensive and easy to scale up. Heterojunctions with different loadings of Cs3Bi2Br9 NCs were fully characterised and tested for the HER. A relevant improvement of H2 production with respect to pristine carbon nitride was achieved at low NCs levels reaching values up to about 4600 µmol g-1 h-1. This work aims to provide insights into the synthesis of inexpensive and high-performing heterojunctions using MHP for photocatalytic applications.

Enhanced in vitro immersion behavior and antibacterial activity of NiTi orthopedic biomaterial by HAp-Nb2O5 composite deposits.

NiTi is a class of metallic biomaterials, benefit from superelastic behavior, high biocompatibility, and favorable mechanical properties close to that of bone. However, the Ni ion leaching, poor bioactivity, and antibacterial activity limit its clinical applications. In this study, HAp-Nb2O5 composite layers were PC electrodeposited from aqueous electrolytes containing different concentrations of the Nb2O5 particles, i.e., 0-1 g/L, to evaluate the influence of the applied surface engineering strategy on in vitro immersion behavior, Ni2+ ion leaching level, and antibacterial activity of the bare NiTi. Surface characteristics of the electrodeposited layers were analyzed using SEM, TEM, XPS, and AFM. The immersion behavior of the samples was comprehensively investigated through SBF and long-term PBS soaking. Gram-negative Escherichia coli (E. coli) and Gram-positive Staphylococcus aureus (S. aureus) infective reference bacteria were employed to address the antibacterial activity of the samples. The results illustrated that the included particles led to more compact and smoother layers. Unlike bare NiTi, composite layers stimulated apatite formation upon immersion in both SBF and PBS media. The concentration of the released Ni2+ ion from the composite layer, containing 0.50 g/L Nb2O5 was ≈ 60% less than that of bare NiTi within 30 days of immersion in the corrosive PBS solution. The Nb2O5-reinforced layers exhibited high anti-adhesive activity against both types of pathogenic bacteria. The hybrid metallic-ceramic system comprising HAp-Nb2O5-coated NiTi offers the prospect of a potential solution for clinical challenges facing the orthopedic application of NiTi.

Air- and water-stable and photocatalytically active germanium-based 2D perovskites by organic spacer engineering.

There is increasing interest in the role of metal halide perovskites for heterogeneous catalysis. Here, we report a Ge-based 2D perovskite material that shows intrinsic water stability realized through organic cation engineering. Incorporating 4-phenylbenzilammonium (PhBz) we demonstrate, by means of extended experimental and computational results, that PhBz2GeBr4 and PhBz2GeI4 can achieve relevant air and water stability. The creation of composites embedding graphitic carbon nitride (g-C3N4) allows a proof of concept for light-induced hydrogen evolution in an aqueous environment by 2D Ge-based perovskites thanks to the effective charge transfer at the heterojunction between the two semiconductors.

Lead-Free Metal Halide Perovskites for Hydrogen Evolution from Aqueous Solutions.

Metal halide perovskites (MHPs) exploitation represents the next big frontier in photovoltaic technologies. However, the extraordinary optoelectronic properties of these materials also call for alternative utilizations, such as in solar-driven photocatalysis, to better address the big challenges ahead for eco-sustainable human activities. In this contest the recent reports on MHPs structures, especially those stable in aqueous solutions, suggest the exciting possibility for efficient solar-driven perovskite-based hydrogen (H2) production. In this minireview such works are critically analyzed and classified according to their mechanism and working conditions. We focus on lead-free materials, because of the environmental issue represented by lead containing material, especially if exploited in aqueous medium, thus it is important to avoid its presence from the technology take-off. Particular emphasis is dedicated to the materials composition/structure impacting on this catalytic process. The rationalization of the distinctive traits characterizing MHPs-based H2 production could assist the future expansion of the field, supporting the path towards a new class of light-driven catalysts working in aqueous environments.

Robust, High-Performing Maize-Perovskite-Based Solar Cells with Improved Stability.

Herein, we focus on improving the long-term chemical and thermomechanical stability of perovskite solar cells (PSCs), two major challenges currently limiting their commercial deployment. Our strategy incorporates a long-chain starch polymer into the perovskite precursor. The starch polymer confers multiple beneficial effects by forming hydrogen bonds with the methylammonium iodide precursor, templating perovskite growth that results in a compact and homogeneous film deposited in a simple one-step coating (antisolvent-free). The inclusion of starch in the methylammonium lead iodide films strongly improves their thermomechanical and environmental stability while maintaining a high photovoltaic performance. The fracture energy (G c) of the film is increased to above 5 J/m2 by creating a nanocomposite that provides intrinsic reinforcement at grain boundaries. Additionally, improved optoelectronic properties achieved with the starch polymer enable good photostability of the active layer and enhanced resistance to thermal cycling.

Inclusion of 2D Transition Metal Dichalcogenides in Perovskite Inks and Their Influence on Solar Cell Performance.

Organic-inorganic hybrid perovskite materials have raised great interest in recent years due to their excellent optoelectronic properties, which promise stunning improvements in photovoltaic technologies. Moreover, two-dimensional layered materials such as graphene, its derivatives, and transition metal dichalcogenides have been extensively investigated for a wide range of electronic and optoelectronic applications and have recently shown a synergistic effect in combination with hybrid perovskite materials. Here, we report on the inclusion of liquid-phase exfoliated molybdenum disulfide nanosheets into different perovskite precursor solutions, exploring their influence on final device performance. We compared the effect of such additives upon the growth of diverse perovskites, namely CH3NH3PbI3 (MAPbI3) and triple-cation with mixed halides Csx (MA0.17FA0.83)(1-x)Pb (I0.83Br0.17)3 perovskite. We show how for the referential MAPbI3 materials the addition of the MoS2 additive leads to the formation of larger, highly crystalline grains, which result in a remarkable 15% relative improvement in power conversion efficiency. On the other hand, for the mixed cation-halide perovskite no improvements were observed, confirming that the nucleation process for the two materials is differently influenced by the presence of MoS2.

Polymer-Assisted Single-Step Slot-Die Coating of Flexible Perovskite Solar Cells at Mild Temperature from Dimethyl Sulfoxide.

The industrialization of perovskite solar cells relies on solving intrinsic-to-material issues. To reach record efficiencies perovskite deposition needs to be finely adjusted by multi-step processes, in a humidity free glove-box environment and by means of hardly scalable techniques often associated with toxic solvents and anti-solvent dripping/bath. Herein, the use of polymeric material is proposed to deposit perovskite layers with easy processability. To the scope, a starch-polymer/perovskite composite is developed to suit slot-die coating technique requirement, allowing the deposition of hybrid halide perovskite material in a single straightforward step without the use of toxic solvents, and in uncontrolled humid environment (RH up to 70 %). The starch-polymer increases the viscosity of the perovskite precursor solutions and delays the perovskite crystallization that results in the formation of perovskite films at mild temperature (60 °C) with good morphology. These innovative inks enables the fabrication of flexible solar cells with p-i-n configuration featured by a power conversion efficiency higher than 3 %. . Overall, this approach can be exploited in the future to massively reduce perovskite manufacturing costs related to keeping the entire fabrication line at high-temperature and under nitrogen or dry conditions.

Biodegradable Carbon-based Ashes/Maize Starch Composite Films for Agricultural Applications.

The aim of this work is the development and characterization of biodegradable thermoplastic recycled carbon ashes/maize starch (TPAS) composite films for agricultural applications. A proper plasticizer, that is, glycerol, was added to a commercial maize starch in an amount of 35 wt.%. Carbon-based ashes were produced by the biomass pyro-gasification plant CMD ECO 20, starting from lignocellulosic wastes. The ashes were added to glycerol and maize native starch at different amounts ranging from 7 wt. % to 21 wt.%. The composite was mixed at 130 °C for 10 min and then molded. The effect of the different amounts of carbon based ashes on the thermal and physical-mechanical properties of the composite was assessed by using several techniques, such as rheology, wide- angle X-ray diffraction (WAXD), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), moisture absorption, degradation and mechanical tests. The presence of the carbon waste ashes allows to improve thermal and durability performances of the thermoplastic starch (TPS) films. It reduces the water absorption of starch matrix and strongly decreases the deterioration of starch, independently from fillers amount, enhancing the lifetime of the TPS films in outdoor conditions. In addition, the waste carbon ashes/maize starch films present an advantage in comparison to those of neat starch; it can biodegrade, releasing the plant nutrients contained in the ashes into the soil. In conclusion, this approach for recycling carbon waste ashes increases the efficiency of industrial waste management, along with a reduction of its impact on the environment.

All-Inorganic CsPbBr3 Perovskite Films Prepared by Single Source Thermal Ablation.

Hybrid organo-lead halide perovskites are becoming the benchmark material for next generation photovoltaics and a very important player for other applications such as photodetectors and light emitting diodes. Nevertheless, the most important issue hindering the large-scale application of these materials remains their intrinsic instability due to the organic cation. Although the substitution with inorganic cesium (Cs) enhances stability, in most cases solution deposition methods of fully inorganic perovskites result in high surface roughness and poor surface coverage. This work reports on the evaporation of the CsPbBr3 precursor by Single Source Thermal Ablation, showing that just after deposition films consist of a mixture of CsPbBr3, CsPb2Br5, and Cs4PbBr6 due to a vertical composition gradient. We point out that mild post deposition treatments lead to the conversion of CsPb2Br5 and Cs4PbBr6 into CsPbBr3 due to its higher thermodynamic stability. Conversion results into smooth and pinhole-free CsPbBr3 films with good light absorption and emission properties. We demonstrate the suitability of obtained films for planar devices by preparing perovskite-based pure-green light emitting diodes, thus promoting Single Source Thermal Ablation as a promising alternative deposition technique for all-inorganic perovskite-based devices.

Simple Processing Additive-Driven 20% Efficiency for Inverted Planar Heterojunction Perovskite Solar Cells.

Compositional engineering has been a strong tool to improve the quality of the perovskite materials and, in turn, the reproducibility of the solar cells. However, the control over the active layer uniformity, one of the most important requirements for the obtainment of efficient devices, is still a weak point of perovskite solar cells (PSCs) manufacturing. Here, we develop an approach to grow a uniform mixed cation perovskite layer, foreseeing its implementation in inverted solar cells endowing organic transporting layers, through the addition of a stoiochiometric amount of tropolone as chelating agent for the lead. Thanks to low melting and boiling temperatures, tropolone is present in the system only during the colloidal liquid phase, leaving the film during its formation; this unique characteristic promotes the obtainment of ideal perovskite surface morphologies and an increased short circuit current of photovoltaic devices. A maximum power conversion efficiency of 20% was obtained, with a 25% increase with respect to the reference.

Engineering of supramolecular H-bonded nanopolygons via self-assembly of programmed molecular modules.

Discrete and multicomponent nanoscale noncovalent assemblies on surfaces featuring polygonal porous domains are presented. The molecular engineering concept involves multivalent molecular modules that are preprogrammed to undergo heteromolecular recognition by exploiting complementary multiple H bonds. Two types of molecular modules have been engineered: (i) a linear unit of twofold symmetry exposing two 2,6-di(acylamino)pyridyl [donor-acceptor-donor (DAD)] recognition sites at its extremities with a 180 degree orientation relative to each other and (ii) an angular unit constituted by a 1,3,6,8-tetraethynylpyrene core peripherally functionalized with four uracil groups [acceptor-donor-acceptor (ADA)] positioned at 60 degrees and 120 degrees relative to each other. These molecular modules self-assemble through H-bonds between the complementary recognition sites, forming supramolecular architectures. Their symmetry depends upon the type of each individual subunit and the stoichiometry as well as on the combination and distribution of the main symmetry axes. These so-formed two-dimensional (2D) supramolecular oligomers have been studied in solution by optical spectroscopy and on highly ordered pyrolitic graphite (HOPG) substrates by scanning tunneling microscopy (STM) at the solid-liquid interface. Steady-state UV/vis absorption and emission titration measurements suggest the reversible formation of multiple oligomeric species with slightly modulated fluorescence spectra. This likely reflects the presence of various aggregates between the two polytopic receptors, which exhibit somewhat different electronic delocalization as a function of the aggregate size. The presence of multiple species is further confirmed by time-resolved luminescence measurements: lifetime values are fitted as double/multiple exponentials and are always shorter than 6.5 ns. The formation of several oligomeric species is further supported by in situ STM measurements at the solid-liquid interface that provided evidence, with submolecular resolution, for the formation of multicomponent and discrete 2D polygon-like assemblies. We highlight the role of accurate control of the concentration required to image on the surface the 2D oligomeric species formed in solution, which allows us to bypass the determinant role of the substrate-molecule interactions in forming the thermodynamically stable monocomponent architectures at the solid-liquid interface.

Fullerene derivatives functionalized with diethylamino-substituted conjugated oligomers: synthesis and photoinduced electron transfer.

Diethylamino-substituted oligophenylenevinylene (OPV) building blocks have been prepared and used for the synthesis of two [60]fullerene-OPV dyads, F-D1 and F-D2, which exhibit different conjugation length of the OPV fragments. The electrochemical properties of these acceptor-donor dyads have been studied by cyclic voltammetry. The first reduction is always assigned to the fullerene moiety and the first oxidation centered on the diethylaniline groups of the OPV rods, thus making these systems suitable candidates for photoinduced electron transfer. Both the OPV and the fullerene-centered fluorescence bands are quenched in toluene and benzonitrile, which suggests the occurrence of photoinduced electron transfer from the amino-substituted OPVs to the carbon sphere in the dyads in both solvents. By means of bimolecular quenching experiments, transient absorption spectral fingerprints of the radical cationic species are detected in the visible (670 nm) and near-IR (1300-1500 nm) regions, along with the much weaker fullerene anion band at lambda(max)=1030 nm. Definitive evidence for photoinduced electron transfer in F-D1 and F-D2 comes from transient absorption measurements. A charge-separated state is formed within 100 ps and decays in less than 5 ns.

Tunable photophysical properties of phenyleneethynylene based bipyridine ligands.

A bipyridine-based system with phenyleneethynylene at the 4,4' positions (1) and its p-methyl (2) and p-methoxy (3) substituted derivatives were synthesized via Sonogashira coupling reactions. The photophysical properties of 1-3 and their related H+ and Zn2+ adducts (1:H+-3:H+ and 1:Zn2+-3:Zn2+) were investigated, as a function of solvent polarity, by using steady-state and time-resolved spectroscopic techniques. Molecular systems 1-3 exhibit trans conformation, whereas adducts with H+ and Zn2+ are conformationally locked cis species. The unsubstituted compound 1 emits at 360 nm with low fluorescence quantum yield (phi(fl) = 0.2%) regardless of the solvent polarity. Fluorescence spectra of 2 and 3 are bathochromically shifted in polar solvents, and the p-methoxy (3) derivative possesses phi(fl) as high as 12%. Complexation of 1-3 with H+ or Zn2+ in acetonitrile causes red-shift of the lowest energy absorption bands, whereas dramatic changes of the emission properties are found as a function of the electron donating ability of the substituents on the phenyleneethynylene moiety (-CH3 or -OCH3), suggesting a charge-transfer character of the lowest electronic transition of 1-3. 1:H+, 1:Zn2+, 2:H+ and 2:Zn2+ exhibit intense fluorescence with phi(fl) up to 33% (1:Zn2+) whilst 3:H+ and 3:Zn2+ are found to be weakly emissive. The singlet radiative and non-radiative rate constants of compounds and complexes were determined, along with triplet parameters, via phosphorescence and transient absorption spectroscopy. More conclusive evidence regarding the protonation of bipyridine nitrogen atoms of compounds 1-3 were obtained through 1H NMR titration studies. These studies indicate that the conjugate molecular systems based on 2,2'-bipyridine and phenyleneethenylenes possess tunable optical properties which can be further utilized for preparing organic and inorganic luminophores with potential application in optoelectronic systems.