Formamidinium Perovskite Deposition in Ambient Air Environment for Inverted p-i-n Solar Cells.

In order to move towards large-scale fabrication, perovskite solar cells need to detach themselves from strictly controlled environmental conditions and, to this end, fabrication in ambient air is highly desirable. Formamidinium iodide perovskite (FAPI) is one of the most promising perovskites but is also unstable at room temperature, which may make the ambient air deposition more difficult. Herein, we investigated different formulations of pure FAPI for the fabrication of perovskite solar cells (PSCs) in air. We found that formulations using a mixture of N,N-Dimethylformamide (DMF): N-methyl-2-pyrrolidone (NMP) and only dimethyl sulfoxide (DMSO) are suitable for the deposition in air. To fabricate inverted p-i-n solar cells, we tested different hole transporting layers (HTLs) and observed the effects on the wettability of the perovskite solution and on the performance. A self-assembly monolayer of 2PACz (2-(9H-Carbazol-9-yl)ethyl]phosphonic acid) was found to be the best option as a HTL, allowing us to achieve efficiencies >15% on both FTO and ITO.

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.

Tuning Film Stresses for Open-Air Processing of Stable Metal Halide Perovskites.

Challenges to upscaling metal halide perovskites (MHPs) include mechanical film stresses that accelerate degradation, dominate at the module scale, and can lead to delamination or fracture. In this work, we demonstrate open-air blade coating of single-step coated perovskite as a scalable method to control residual film stress after processing and introduce beneficial compression in the thin film with the use of polymer additives such as gellan gum and corn starch. The optoelectronic properties of MHP films with compression are improved with higher photoluminescence yields. MHP film stability is significantly improved under compression, under humidity, heat, and thermal cycling. By measuring the evolution of film stresses, we demonstrate for the first time that stress relaxation occurs in MHP films with tensile stress that correlates with film degradation. This discovery of a new mechanism underpinning MHP degradation shows that film stress can be used as a parameter to screen MHP devices and modules for quality control before deployment as a design for reliability criterion.

Advancements in tailoring PEDOT: PSS properties for bioelectronic applications: A comprehensive review.

In the field of bioelectronics, the demand for biocompatible, stable, and electroactive materials for functional biological interfaces, sensors, and stimulators, is drastically increasing. Conductive polymers (CPs) are synthetic materials, which are gaining increasing interest mainly due to their outstanding electrical, chemical, mechanical, and optical properties. Since its discovery in the late 1980s, the CP Poly(3,4-ethylenedioxythiophene):poly(styrene sulfonic acid) (PEDOT:PSS) has become extremely attractive, being considered as one of the most capable organic electrode materials for several bioelectronic applications in the field of tissue engineering and regenerative medicine. Main examples refer to thin, flexible films, electrodes, hydrogels, scaffolds, and biosensors. Within this context, the authors contend that PEDOT:PSS properties should be customized to encompass: i) biocompatibility, ii) conductivity, iii) stability in wet environment, iv) adhesion to the substrate, and, when necessary, v) (bio-)degradability. However, consolidating all these properties into a single functional solution is not always straightforward. Therefore, the objective of this review paper is to present various methods for acquiring and improving PEDOT:PSS properties, with the primary focus on ensuring its biocompatibility, and simultaneously addressing the other functional features. The last section highlights a collection of designated studies, with a particular emphasis on PEDOT:PSS/carbon filler composites due to their exceptional characteristics.

Pedot:PSS/Graphene Oxide (GO) Ternary Nanocomposites for Electrochemical Applications.

Among conductive polymers, poly(3,4 ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) has been widely used as an electrode material for supercapacitors, solar cells, sensors, etc. Although PEDOT:PSS-based thin films have acceptable properties such as good capacitive and electrical behaviour and biocompatibility, there are still several challenges to be overcome in their use as an electrode material for supercapacitors. For this reason, the aim of this work is to fabricate and characterise ternary nanocomposites based on PEDOT:PSS and graphene oxide (GO), blended with green additives (glucose (G) or ascorbic acid (AA)), which have the benefits of being environmentally friendly, economical, and easy to use. The GO reduction process was first accurately investigated and demonstrated by UV-Vis and XRD measurements. Three-component inks have been developed, and their morphological, rheological, and surface tension properties were evaluated, showing their printability by means of Aerosol Jet® Printing (AJ®P), an innovative direct writing technique belonging to the Additive Manufacturing (AM) for printed electronics applications. Thin films of the ternary nanocomposites were produced by drop casting and spin coating techniques, and their capacitive behaviour and chemical structures were evaluated through Cyclic Voltammetry (CV) tests and FT-IR analyses. CV tests show an increment in the specific capacitance of AAGO-PEDOT up to 31.4 F/g and excellent overtime stability compared with pristine PEDOT:PSS, suggesting that this ink can be used to fabricate supercapacitors in printed (bio)-electronics. The inks were finally printed by AJ®P as thin films (10 layers, 8 × 8 mm) and chemically analysed by FT-IR, demonstrating that all components of the formulation were successfully aerosolised and deposited on the substrate.

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.

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.

Development of an Innovative and Green Method to Obtain Nanoparticles in Aqueous Solution from Carbon-Based Waste Ashes.

In this study, an original and green procedure to produce water-based solutions containing nanometric recycled carbon particles is proposed. The nanometric particles are obtained starting from carbon waste ashes, produced by the wooden biomass pyro-gasification plant CMD (Costruzioni motori diesel) ECO20. The latter is an integrated system combining a downdraft gasifier, a spark-ignition internal combustion engine, an electric generator and syngas cleaning devices, and it can produce electric and thermal power up to 20 kWe and 40 kWth. The carbon-based ashes (CA) produced by the CMD ECO20 plant were, first, characterized by using differential scanning calorimetry (DSC) and microcomputed tomography (microCT). Afterward, they were reduced in powder by using a milling mortar and analyzed by scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) spectrometry, thermogravimetric analysis (TGA), X-ray diffraction (WAXD) and Fourier-transform infrared (FTIR) spectroscopy. The optimization of an original procedure to reduce the dimensions of the ashes in an aqueous solution was then developed by using ball milling and sonication techniques, and the nanometric dimensions of the particles dispersed in water were estimated by dynamic light scattering (DLS) measurements in the order of 300 nm. Finally, possible industrial applications for the nanomaterials obtained from the waste ashes are suggested, including, for example, inks for Aerosol Jet® Printing (AJ® P).

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.

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.

Optimizing the Interface between Hole Transporting Material and Nanocomposite for Highly Efficient Perovskite Solar Cells.

The performances of organometallic halide perovskite-based solar cells severely depend on the device architecture and the interface between each layer included in the device stack. In particular, the interface between the charge transporting layer and the perovskite film is crucial, since it represents both the substrate where the perovskite polycrystalline film grows, thus directly influencing the active layer morphology, and an important site for electrical charge extraction and/or recombination. Here, we focus on engineering the interface between a perovskite-polymer nanocomposite, recently developed by our group, and different commonly employed polymeric hole transporters, namely PEDOT: PSS [poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)], PEDOT, PTAA [poly(bis 4-phenyl}{2,4,6-trimethylphenyl}amine)], Poly-TPD [Poly(N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)-benzidine] Poly-TPD, in inverted planar perovskite solar cell architecture. The results show that when Poly-TPD is used as the hole transfer material, perovskite film morphology improved, suggesting an improvement in the interface between Poly-TPD and perovskite active layer. We additionally investigate the effect of the Molecular Weight (MW) of Poly-TPD on the performance of perovskite solar cells. By increasing the MW, the photovoltaic performances of the cells are enhanced, reaching power conversion efficiency as high as 16.3%.

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.

Catalytic Activity of Oxidized Carbon Waste Ashes for the Crosslinking of Epoxy Resins.

In this study, two different fillers were prepared from carbon-based ashes, produced from the wooden biomass of a pyro-gasification plant, and starting from lignocellulosic waste. The first type was obtained by dry ball-milling (DBA), while the second one was prepared by oxidation in H2O2 of the dry ball-milled ashes (oDBA). The characterization of the fillers included wide-angle x-ray diffraction (WAXD), thermogravimetric, and Fourier-transform infrared spectroscopy (FTIR) analysis. The DBA and oDBA fillers were then tested as possible catalysts for the crosslinking reaction of a diglycidyl ether of bisphenol A (DGEBA) with a diamine. The cure reaction was studied by means of rheometry and differential scanning calorimetry (DSC). The oDBA filler exhibits both a higher catalytic activity on the epoxide-amine reaction than the DBA sample and improved mechanical properties and glass transition temperature. The results obtained indicate, hence, the potential improvement brought by the addition of carbon-based waste ashes, which allow both increasing the flexural properties and the glass transition temperature of the epoxy resin and reducing the curing time, acting as a catalyst for the crosslinking reaction of the epoxy resin.

Rheological Tunability of Perovskite Precursor Solutions: From Spin Coating to Inkjet Printing Process.

The high efficiencies (>22%) reached by perovskite-based optoelectronic devices in a very short period, demonstrates the great potential and tunability of this material. The current challenge lies in translating such efficiencies to commercially feasible forms produced through industrial fabrication methods. Herein, a novel first step towards the processability of starch-perovskite inks, developed in our previous work, is investigated, by using inkjet printing technology. The tunability of the viscosity of the starch-perovskite-based inks allows the selection of suitable concentrations to be used as printable inks. After exploration of several printing parameters, thick and opaque starch-perovskite nanocomposite films were obtained, showing interesting morphological and optical properties. The results obtained in this work underline the potential and versatility of our approach, opening the possibility to explore and optimize, in the future, further large-scale deposition methods towards fully printed and stable perovskite devices.

Ultra-Bright Near-Infrared Perovskite Light-Emitting Diodes with Reduced Efficiency Roll-off.

Herein, an insulating biopolymer is exploited to guide the controlled formation of micro/nano-structure and physical confinement of α-δ mixed phase crystalline grains of formamidinium lead iodide (FAPbI3) perovskite, functioning as charge carrier concentrators and ensuring improved radiative recombination and photoluminescence quantum yield (PLQY). This composite material is used to build highly efficient near-infrared (NIR) FAPbI3 Perovskite light-emitting diodes (PeLEDs) that exhibit a high radiance of 206.7 W/sr*m2, among the highest reported for NIR-PeLEDs, obtained at a very high current density of 1000 mA/cm2, while importantly avoiding the efficiency roll-off effect. In depth photophysical characterization allows to identify the possible role of the biopolymer in i) enhancing the radiative recombination coefficient, improving light extraction by reducing the refractive index, or ii) enhancing the effective optical absorption because of dielectric scattering at the polymer-perovskite interfaces. Our study reveals how the use of insulating matrixes for the growth of perovskites represents a step towards high power applications of PeLEDs.

Effect of inorganic and organic bioactive signals decoration on the biological performance of chitosan scaffolds for bone tissue engineering.

The present work is focused on the design of a bioactive chitosan-based scaffold functionalized with organic and inorganic signals to provide the biochemical cues for promoting stem cell osteogenic commitment. The first approach is based on the use of a sequence of 20 amino acids corresponding to a 68-87 sequence in knuckle epitope of BMP-2 that was coupled covalently to the carboxyl group of chitosan scaffold. Meanwhile, the second approach is based on the biomimetic treatment, which allows the formation of hydroxyapatite nuclei on the scaffold surface. Both scaffolds bioactivated with organic and inorganic signals induce higher expression of an early marker of osteogenic differentiation (ALP) than the neat scaffolds after 3 days of cell culture. However, scaffolds decorated with BMP-mimicking peptide show higher values of ALP than the biomineralized one. Nevertheless, the biomineralized scaffolds showed better cellular behaviour than neat scaffolds, demonstrating the good effect of hydroxyapatite deposits on hMSC osteogenic differentiation. At long incubation time no significant difference among the biomineralized and BMP-activated scaffolds was observed. Furthermore, the highest level of Osteocalcin expression (OCN) was observed for scaffold with BMP2 mimic-peptide at day 21. The overall results showed that the presence of bioactive signals on the scaffold surface allows an osteoinductive effect on hMSC in a basal medium, making the modified chitosan scaffolds a promising candidate for bone tissue regeneration.

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.

Catalytic Activity of Oxidized Carbon Black and Graphene Oxide for the Crosslinking of Epoxy Resins.

This article compares the catalytic activities of oxidized carbon black (oCB) and graphene oxide (eGO) samples on the kinetics of a reaction of diglycidyl ether of bisphenol A (DGEBA) with a diamine, leading to crosslinked insoluble networks. The study is mainly conducted by rheometry and Differential Scanning Calorimetry (DSC). Following the same oxidation procedure, CB samples are more efficiently oxidized than graphite samples. For instance, CB and graphite samples with high specific surface areas (151 and 308 m²/g), as oxidized by the Hummers' method, exhibit O/C wt/wt ratios of 0.91 and 0.62, respectively. Due to the higher oxidation levels, these oCB samples exhibit a higher catalytic activity toward the curing of epoxy resins than fully exfoliated graphene oxide.

Microwave-induced porosity and bioactivation of chitosan-PEGDA scaffolds: morphology, mechanical properties and osteogenic differentiation.

In this study, a new foaming method, based on physical foaming combined with microwave-induced curing, is proposed in combination with a surface bioactivation to develop scaffold for bone tissue regeneration. In the first step of the process, a stable physical foaming was induced using a surfactant (Pluronic) as blowing agent of a homogeneous blend of Chitosan and polyethylene glycol diacrylate (PEGDA700) solutions. In the second step, the porous structure of the foaming was chemically stabilized by radical polymerization induced by homogeneous heating of the sample in a microwave reactor. In this step, 2,2-azobis[2-(2-imidazolin-2yl)propane]dihydrochloride was used as thermoinitiator (TI). Chitosan and PEGDA were mixed in different blends to investigate the influence of the composition on the final properties of the material. The chemical properties of each sample were evaluated by infrared attenuated total reflectance analysis, before and after curing in order to maximize reaction yield and optimize kinetic parameters (i.e. time curing, microwave power). Absorption capacity, elastic modulus, porosity and morphology of the porous structure were measured for each sample. The stability of materials was evaluated in vitro by degradation test in phosphate-buffered saline. To improve the bioactivity and biological properties of chitosan scaffold, a biomineralization process was used. Biological characterization was carried out with the aim to prove the effect of biomineralization scaffold on human mesenchymal stem cells behaviour. Copyright © 2016 John Wiley & Sons, Ltd.

Cellulose-based porous scaffold for bone tissue engineering applications: Assessment of hMSC proliferation and differentiation.

Physical foaming combined with microwave-induced curing was used in this study to develop an innovative device for bone tissue regeneration. In the first step of the process, a stable physical foaming was induced using a surfactant (i.e. pluronic) as blowing agent of a homogeneous blend of Sodium salt of carboxymethylcellulose (CMCNa) and polyethylene glycol diacrylate (PEGDA700) solution. In the second step, the porous structure of the scaffold was chemically stabilized by radical polymerization induced by a homogeneous rapid heating of the sample in a microwave reactor. In this step 2,2-Azobis[2-(2-imidazolin-2 yl)propane]Dihydrochloride was used as thermoinitiator (TI). CMCNa and PEGDA were mixed with different blends to correlate the properties of final product with the composition. The chemical properties of each sample were evaluated by spectroscopy analysis ATR-IR (before and after curing) in order to maximize reaction yield, and optimize kinetic parameters (i.e. time curing, microwave power). The stability of the materials was evaluated in vitro by degradation test in Phosphate Buffered Saline. Biological analyses were performed to evaluate the effect of scaffold materials on cellular behavior in terms of proliferation and early osteogenic differentiation of human Mesenchymal Stem Cells. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 726-733, 2016.