Physical and chemical properties and degradation of MAPbBr3 films on transparent substrates.

To date, the potential exploitation of hybrid organic-inorganic perovskites (HOIPs) in photovoltaic technologies has been significantly hampered by their poor environmental stability. HOIP degradation can be triggered by conventional operational environments, with excessive heating and exposure to oxygen and moisture significantly reducing the performances of HOIP-based solar cells. An imperative need emerges for a thorough investigation on the impact of these factors on the HOIP stability. In this work, the degradation of methylammonium lead bromide (CH3NH3PbBr3) thin films, deposited via spin-coating on indium tin oxide (ITO) and strontium titanate (STO) substrates, was investigated by combining Raman and ultraviolet-visible (UV-Vis) absorption spectroscopy, as well as optical and fluorescence microscopy. We assessed the physical and chemical degradation of the films occurring under diverse preservation conditions, shedding light on the byproducts emerging from different degradation pathways and on the optimal HOIP preservation conditions.

Signatures of Polaron Dynamics in Photoexcited MAPbBr3 by Infrared Spectroscopy.

Hybrid organic-inorganic perovskites (HOIPs) have attracted considerable attention in the past years as photoactive materials for low-cost, high-performance photovoltaics. Polaron formation through electron-phonon coupling has been recognized as the leading mechanism governing charge carrier transport and recombination in HOIPs. In this work, two types of MAPbBr3 film samples deposited on different substrates (transparent insulating SrTiO3 and a heterostructure mimicking a functioning photovoltaic cell) were photoexcited with above-bandgap radiation at 450 nm, and the effects of illumination on the sample were analyzed in the infrared region. The infrared absorbance detected at different powers of the photoexciting laser allowed us to obtain an estimate of the characteristic decay time of photoexcited polaron population of the order of 100-1000 ns. When focusing on the absorption features of the MA molecular cation in the region of the NH stretching modes, we observed the influence of hydrogen bonding and the effect of the polaron dynamics on the cation reorientation.

EQCM Analysis of the Insertion Phenomena in a n-Doped Poly-Alkyl-Terthiophene With Regioregular Pattern of Substitution.

In the present work, we have undertaken the study of the n-doping process in poly-3,3″-didodecyl-2,2':5',2″-terthiophene (poly-33″-DDTT) employing the electrochemical quartz crystal microbalance (EQCM). The present study aims at understanding how cathodic charge in n-doped poly-33″-DDTT is compensated. For this purpose, the in situ analysis of the variations of the polymeric mass has been considered. Poly-33″-DDTT was obtained as a thin coating onto a metallic substrate via the anodic coupling of the corresponding monomer 3,3″-didodecyl-2,2':5',2″-terthiophene (33″-DDTT). When subjected to electrochemical n-doping in the polarization interval -2.5 ≤ E appl ≤ 0 V vs. Ag/Ag+, the films of poly-33″-DDTT varied their mass according to a mechanism of cations insertion during n-doping and cations extraction during polymer neutralization. In fact, the electrochemical doping of polythiophenes requires the accompanying exchange of charged species to maintain the electroneutrality within the structure of the polymer in all states of polarization. At the end of a full electrochemical cycle (consisting of the n-doping and the successive neutralization of poly-33″-DDTT), the polymer retains a fraction of the mass acquired during n-doping, thus manifesting the phenomena of mass trapping. The combined analysis of electrochemical and microgravimetric data suggests that poly-33″-DDTT in the n-doped state undergoes (or electrocatalyzes) uncontrolled electrochemical reactions that are not accompanied by mass variations.

Deep eutectic solvents (DES) as green extraction media for antioxidants electrochemical quantification in extra-virgin olive oils.

A new electroanalytical method has been developed for the determination of polar antioxidant compounds in extra virgin olive oils. This method is based on the extraction of polar antioxidant compounds from extra-virgin olive oils by means of a deep eutectic solvent and their determination by a modified screen-printed electrode platform. The platform sensitivity was increased by modifying the working electrode with MWCNT and TiO2 nanoparticles as modifiers and Nafion as a binder. The platform showed very good sensitivity in detecting polar antioxidant compounds in extra-virgin olive oils in a fairly wide range of concentrations. The measurements were performed by using square wave voltammetry. The extraction was performed without using organic solvents, making the method environmentally friendly. The proposed method has been compared with a common spectrophotometric one, the results appeared in good agreement. The method is sufficiently easy and quick to be used for screening analyses of polar antioxidant compounds in extra-virgin olive oils on the field.

Electrochemically Deposited NiO Films as a Blocking Layer in p-Type Dye-Sensitized Solar Cells with an Impressive 45% Fill Factor.

The enhancement of photoelectrochemical conversion efficiency of p-type dye-sensitized solar cells (p-DSSCs) is necessary to build up effective tandem devices in which both anode and cathode are photoactive. The efficiency of a p-type device (2.5%) is roughly one order of magnitude lower than the n-type counterparts (13.1%), thus limiting the overall efficiency of the tandem cell, especially in terms of powered current density. This is mainly due to the recombination reaction that occurs especially at the photocathode (or Indium-doped Tin Oxide (ITO))/electrolyte interface. To minimize this phenomenon, a widely employed strategy is to deposit a compact film of NiO (acting as a blocking electrode) beneath the porous electrode. Here, we propose electrodeposition as a cheap, easy scalable and environmental-friendly approach to deposit nanometric films directly on ITO glass. The results are compared to a blocking layer made by means of sol-gel technique. Cells embodying a blocking layer substantially outperformed the reference device. Among them, BL_1.10V shows the best photoconversion efficiency (0.166%) and one of the highest values of fill factor (approaching 46%) ever reported. This is mainly due to an optimized surface roughness of the blocking layer assuring a good deposition of the porous layer. The effectiveness of the implementation of the blocking layer is further proved by means of Electrochemical Impedance Spectroscopy.

Progress, highlights and perspectives on NiO in perovskite photovoltaics.

The power conversion efficiency (PCE) of NiO based perovskite solar cells has recently hit a record 22.1% with a hybrid organic-inorganic perovskite composition and a PCE above 15% in a fully inorganic configuration was achieved. Moreover, NiO processing is a mature technology, with different industrially attractive processes demonstrated in the last few years. These considerations, along with the excellent stabilities reported, clearly point towards NiO as the most efficient inorganic hole selective layer for lead halide perovskite photovoltaics, which is the topic of this review. NiO optoelectronics is discussed by analysing the different doping mechanisms, with a focus on the case of alkaline and transition metal cation dopants. Doping allows tuning the conductivity and the energy levels of NiO, improving the overall performance and adapting the material to a variety of perovskite compositions. Furthermore, we summarise the main investigations on the NiO/perovskite interface stability. In fact, the surface of NiO is commonly oxidised and reactive with perovskite, also under the effect of light, thermal and electrical stress. Interface engineering strategies should be considered aiming at long term stability and the highest efficiency. Finally, we present the main achievements in flexible, fully printed and lead-free perovskite photovoltaics which employ NiO as a layer and provide our perspective to accelerate the improvement of these technologies. Overall, we show that adequately doped and passivated NiO might be an ideal hole selective layer in every possible application of perovskite solar cells.

Adsorption Dynamics of Redox Active Species onto Polarized Surfaces of Sensitized NiO.

Mesoporous NiO films were deposited by means of a screen printing technique onto fluorine-doped tin oxide transparent electrodes and consequently sensitized with Erythrosin B (EryB) dye. The obtained colored NiO material was used as a working electrode in a three-electrode cell to study the evolution of the triple semiconductor/dye/electrolyte interface upon electrochemical polarization in dark conditions. The electrolyte was a solution of I3 -/I- in acetonitrile, with the redox couple representing the typical redox shuttle of dye-sensitized solar cells (DSCs). The adopted electrochemical conditions were devised in order to simulate the actual electrical environment of the NiO/dye photocathode in a light-soaked DSC. The use of a benchmark sensitizer EryB and of the most widely used redox mediator I3 -/I- is particularly meaningful for the study of the adsorption dynamics and the determination of possible degradative phenomena on the basis of the behavior of numerous analogue systems. Therefore, for the first time, the evolution of the NiO/EryB/I3 -/I- multiple interface was investigated combining the electrochemical characterization with ex situ spectroscopic analysis by means of X-ray photoelectron spectroscopy. The resulting picture shows that EryB in the immobilized state promotes the redox processes based on the I3 -/I- couple. Moreover, the EryB sensitizer inhibits the phenomena of recombination between the metal oxide semiconductor and the redox couple.

Sodium Hydroxide Pretreatment as an Effective Approach to Reduce the Dye/Holes Recombination Reaction in P-Type DSCs.

We report the synthesis of a novel squaraine dye (VG21-C12) and investigate its behavior as p-type sensitizer for p-type Dye-Sensitized Solar Cells. The results are compared with O4-C12, a well-known sensitizer for p-DSC, and sodium hydroxide pretreatment is described as an effective approach to reduce the dye/holes recombination. Various variable investigation such as dipping time, dye loading, photocurrent, and resulting cell efficiency are also reported. Electrochemical impedance spectroscopy (EIS) was utilized for investigating charge transport properties of the different photoelectrodes and the recombination phenomena that occur at the (un)modified electrode/electrolyte interface.

Biologically friendly room temperature ionic liquids and nanomaterials for the development of innovative enzymatic biosensors: Part II.

A newly modified electrode based on glassy carbon (GC) has been prepared and characterized electrochemically for application in electroanalytical chemistry. In particular, a GC screen-printed electrode (SPE) has been modified with nanostructures, namely multi-walled carbon nanotubes (MWCNTs), and TiO2 nanoparticles, and combined with a new generation of eco-friendly room-temperature ionic liquids (RTILs). The green RTILs here used are suitable for the immobilization of enzymes on the electrode surface and, additionally, facilitate the kinetics of electron transfer due to their intrinsic electrical conductivity. Upon evaluation of these newly modified electrodes we found an improvement in terms of electrochemically active area (Aea) with respect to the electrodes we previously reported. The modified SPEs were then used as substrates for the construction of two enzymatic biosensors for analytical applications: the first is an enzymatic biosensor based on alcohol dehydrogenase (ADH) for the analysis of ethyl alcohol; the second biosensor is based on lipase enzyme and has been tested for the analysis and the classification of Extra Virgin Olive Oil (EVOO). The performances of the here projected sensors appear comparable with biosensors having similar finalities. It is here envisaged that such a kind of electrodes could represent the starting tool for the construction and the definition of new portable devices for screening and field analyses.

X-Ray structure and ionic conductivity studies of anhydrous and hydrated choline chloride and oxalic acid deep eutectic solvents.

In this study, we report the structural, thermodynamic and electrochemical properties of deep eutectic solvents (DESs) formed from choline chloride and oxalic acid in anhydrous and di-hydrated form in a 1 : 1 molar ratio. As far as we are aware, this is the first joint X-ray diffraction-molecular dynamics study focussed on analyzing the structural features of DESs.

Electrochemical and Photoelectrochemical Properties of Nickel Oxide (NiO) With Nanostructured Morphology for Photoconversion Applications.

The cost-effective production of chemicals in electrolytic cells and the conversion of the radiation energy into electrical energy in photoelectrochemical cells (PECs) require the use of electrodes with large surface area, which possess either electrocatalytic or photoelectrocatalytic properties. In this context nanostructured semiconductors are electrodic materials of great relevance because of the possibility of varying their photoelectrocatalytic properties in a controlled fashion via doping, dye-sensitization or modification of the conditions of deposition. Among semiconductors for electrolysers and PECs the class of the transition metal oxides (TMOs) with a particular focus on NiO interests for the chemical-physical inertness in ambient conditions and the intrinsic electroactivity in the solid state. The latter aspect implies the existence of capacitive properties in TMO and NiO electrodes which thus act as charge storage systems. After a comparative analysis of the (photo)electrochemical properties of nanostructured TMO electrodes in the configuration of thin film the use of NiO and analogs for the specific applications of water photoelectrolysis and, secondly, photoelectrochemical conversion of carbon dioxide will be discussed.

Intriguing transport dynamics of ethylammonium nitrate-acetonitrile binary mixtures arising from nano-inhomogeneity.

Binary mixtures of ethylammonium nitrate and acetonitrile show interesting properties that originate from the structural and dynamical nano-heterogeneity present in ionic liquids. These effects are most pronounced when the ionic liquid is the minority compound. In this study the transport properties of such mixtures are studied, including viscosity, self-diffusion and conductivity. The results strongly support the presence of structural inhomogeneity and show an interesting composition-dependent behaviour in the mixtures.

Nonlinear Optical Materials for the Smart Filtering of Optical Radiation.

The control of luminous radiation has extremely important implications for modern and future technologies as well as in medicine. In this Review, we detail chemical structures and their relevant photophysical features for various groups of materials, including organic dyes such as metalloporphyrins and metallophthalocyanines (and derivatives), other common organic materials, mixed metal complexes and clusters, fullerenes, dendrimeric nanocomposites, polymeric materials (organic and/or inorganic), inorganic semiconductors, and other nanoscopic materials, utilized or potentially useful for the realization of devices able to filter in a smart way an external radiation. The concept of smart is referred to the characteristic of those materials that are capable to filter the radiation in a dynamic way without the need of an ancillary system for the activation of the required transmission change. In particular, this Review gives emphasis to the nonlinear optical properties of photoactive materials for the function of optical power limiting. All known mechanisms of optical limiting have been analyzed and discussed for the different types of materials.

Adsorption Behavior of I3- and I- Ions at a Nanoporous NiO/Acetonitrile Interface Studied by X-ray Photoelectron Spectroscopy.

The adsorption of I- and I3- anions, i.e., the two species constituting the most common redox couple of dye-sensitized solar cells (DSCs), onto the surface of screen-printed nanoporous NiO was studied by means of X-ray photoelectron spectroscopy (XPS). Nanoporous NiO films were deposited on transparent metallic fluorine-doped tin oxide (FTO) and polarized as working electrodes in a three-electrode cell with differently concentrated I-/I3- electrolytes to simulate the different conditions experienced by the NiO cathodes during the lifecycle of a p-type DSC (p-DSC) at those atomic sites not passivated by the dye. Bare NiO films were tested also as photocathodes of nonsensitized p-DSCs. The ex situ XPS analysis of I 4d ionization region of both reference and electrochemically treated NiO films showed that the presence of native and electrochemically generated Ni3+ and Ni4+ centers induces fast adsorption/desorption of I- ions and catalyzes their oxidation to I3- ions. The adsorption phenomena generated by I- and I3- species on nanoporous NiO electrodes can also induce an effect of electrochemical passivation toward a fraction of charged Ni sites. Such an effect would render these sites inactive for the further realization of those photoelectrochemical processes at the basis of the operation of a p-DSC.

A comprehensive comparison of dye-sensitized NiO photocathodes for solar energy conversion.

We investigated a range of different mesoporous NiO electrodes prepared by different research groups and private firms in Europe to determine the parameters which influence good quality photoelectrochemical devices. This benchmarking study aims to solve some of the discrepancies in the literature regarding the performance of p-DSCs due to differences in the quality of the device fabrication. The information obtained will lay the foundation for future photocatalytic systems based on sensitized NiO so that new dyes and catalysts can be tested with a standardized material. The textural and electrochemical properties of the semiconducting material are key to the performance of photocathodes. We found that both commercial and non-commercial NiO gave promising solar cell and water-splitting devices. The NiO samples which had the two highest solar cell efficiency (0.145% and 0.089%) also gave the best overall theoretical H2 conversion.

Photoelectrochemical properties of mesoporous NiO x deposited on technical FTO via nanopowder sintering in conventional and plasma atmospheres.

Nanoporous nickel oxide (NiO x ) has been deposited with two different procedures of sintering (CS and RDS). Both samples display solid state oxidation at about 3.1 V vs Li+/Li. Upon sensitization of CS/RDS NiO x with erythrosine b (ERY), nickel oxide oxidation occurs at the same potential. Impedance spectroscopy revealed a higher charge transfer resistance for ERY-sensitized RDS NiO x with respect to sensitized CS NiO x . This was due to the chemisorption of a larger amount of ERY on RDS with respect to CS NiO x . Upon illumination the photoinduced charge transfer between ERY layer and NiO x could be observed only with oxidized CS. Photoelectrochemical effects of sensitized RDS NiO x were evidenced upon oxide reduction. With the addition of iodine RDS NiOx electrodes could give the reduction iodine â†’ iodide in addition to the reduction of RDS NiO x . p-type dye sensitized solar cells were assembled with RDS NiO x photocathodes sensitized either by ERY or Fast Green. Resulting overall efficiencies ranged between 0.02 and 0.04 % upon irradiation with solar spectrum simulator (I in: 0.1 W cm(-2)).

Probing the redox states at the surface of electroactive nanoporous NiO thin films.

Nanoporous NiO thin film electrodes were obtained via plasma-assisted microwave sintering and characterized by means of a combination of electrochemical techniques and X-ray photoelectron spectroscopy (XPS). The aim of this study is the elucidation of the nature of the surface changes introduced by the redox processes of this nanostructured material. NiO undergoes two distinct electrochemical processes of oxidation in aqueous electrolyte with the progress of NiO anodic polarization. These findings are consistent with the sequential formation of oxyhydroxide species at the surface, the chemical nature of which was assessed by XPS. Electronic relaxation effects in the Ni 2p spectra clearly indicated that the superficial oxyhydroxide species resulted to be ß-NiOOH and γ-NiOOH. We also show for the first time spectral evidence of an electrochemically generated Ni(IV) species. This study has direct relevance for those applications in which NiO electrodes are utilized in aqueous electrolyte, namely catalytic water splitting or electrochromism, and may constitute a starting point for the comprehension of electronic phenomena at the NiO/organic electrolyte interface of cathodic dye-sensitized solar cells (p-DSCs).

Recent progress in the development of bimetallic photocatalysts for hydrogen generation.

In this contribution recent developments in the design and application of bimetallic photocatalysts for the generation of hydrogen via intramolecular processes are assessed. The basic concepts of such assemblies are discussed together with an overview of the factors and molecular issues that affect their potential as photocatalysts. Issues that so far have limited progress are discussed and suggestions for future directions are made.

Dye sensitised solar cells with nickel oxide photocathodes prepared via scalable microwave sintering.

Photoactive NiO electrodes for cathodic dye-sensitised solar cells (p-DSCs) have been prepared with thicknesses ranging between 0.4 and 3.0 µm by spray-depositing pre-formed NiO nanoparticles on fluorine-doped tin oxide (FTO) coated glass substrates. The larger thicknesses were obtained in sequential sintering steps using a conventional furnace (CS) and a newly developed rapid discharge sintering (RDS) method. The latter procedure is employed for the first time for the preparation of p-DSCs. In particular, RDS represents a scalable procedure that is based on microwave-assisted plasma formation that allows the production in series of mesoporous NiO electrodes with large surface areas for p-type cell photocathodes. RDS possesses the unique feature of transmitting heat from the bulk of the system towards its outer interfaces with controlled confinement of the heating zone. The use of RDS results in a drastic reduction of processing times with respect to other deposition methods that involve heating/calcination steps with associated reduced costs in terms of energy. P1-dye sensitized NiO electrodes obtained via the RDS procedure have been tested in DSC devices and their performances have been analysed and compared with those of cathodic DSCs derived from CS-deposited samples. The largest conversion efficiencies (0.12%) and incident photon-to-current conversion efficiencies, IPCEs (50%), were obtained with sintered NiO electrodes having thicknesses of ~1.5-2.0 µm. In all the devices, the photogenerated holes in NiO live significantly longer (τ(h) ~ 1 s) than have previously been reported for P1-sensitized NiO photocathodes. In addition, P1-sensitised sintered electrodes give rise to relatively high photovoltages (up to 135 mV) when the triiodide-iodide redox couple is used.

Dendritic cells in blood and urine samples from bladder cancer patients undergoing BCG immunotherapy.

OBJECTIVES: Immunotherapy with BCG (Bacille Calmette-Guérin) after transurethral resection of the bladder tumor represents a highly effective primary treatment for intermediate and high-risk superficial bladder cancer. The effectiveness of this therapy has been documented, but its mechanism of action is not clear yet. In the present study, we investigated the changes of dendritic cells (DC) numbers in peripheral blood and urine of patients with superficial bladder cancer undergoing BCG intravescical therapy. MATERIAL AND METHOD: We have enumerated plasmacytoid and myeloid DCs in the peripheral blood and in the urine of patients with bladder cancer in order to clarify the role of these cells in the evolution of the disease and the effect of therapy. DCs in blood and urine samples were assessed using the single-platform TruCOUNT assay with monoclonal antibodies. The study population included 37 healthy donors and 13 patients with diagnosis of primitive superficial bladder cancer. RESULTS: At the time of diagnosis a reduction of blood DCs was found in patients as opposed to healthy donors, while DCs were not found in the urine in the same way as in healthy subjects. Six of these patients were followed before and after weekly and monthly instillations of BCG. In the peripheral blood, we observed an immunological recovery of DCs from the third weekly instillation up to the sixth. In the urine of patients, we didn't find mDCs or pDCs at T0, but we found a statistically significant change from the third instillation up to the sixth. On the contrary, we didn't find mDCs in urine during monthly instillation. CONCLUSIONS: DC Count could be used in the monitoring of patients undergoing BCG therapy. Immunological restoration of mDC numbers in peripheral blood and the efflux in urine could be important for confirming the effectiveness of BCG instillation.