Charge Transport in Trap-Sensitized Infrared PbS Quantum-Dot-Based Photoconductors: Pros and Cons

Control of quantum-dot (QD) surface chemistry offers a direct approach for the tuning of charge-carrier dynamics in photoconductors based on strongly coupled QD solids. We investigate the effects of altering the surface chemistry of PbS QDs in such QD solids via ligand exchange using 3-mercaptopropionic acid (MPA) and tetrabutylammonium iodide (TBAI). The roll-to-roll compatible doctor-blade technique was used for the fabrication of the QD solid films as the photoactive component in photoconductors and field-effect phototransistors. The ligand exchange of the QD solid film with MPA yields superior device performance with higher photosensitivity and detectivity, which is due to less dark current and lower noise level as compared to ligand exchange with TBAI. In both cases, the mechanism responsible for photoconductivity is related to trap sensitization of the QD solid, in which traps are responsible of high photoconductive gain values, but slow response times under very low incident optical power (100 pW), where traps are filled, both MPA- and TBAI-treated photodevices exhibit similar behavior, characterized by lower responsivity and faster response time, as limited by the mobility in the QD solid

Thin film growth and band lineup of In2O3 on the layered semiconductor InSe

Thin films of the transparent conducting oxide In2O3 have been prepared in ultrahigh vacuum by reactive evaporation of indium. X-ray diffraction, optical, and electrical measurements were used to characterize properties of films deposited on transparent insulating mica substrates under variation of the oxygen pressure. Photoelectron spectroscopy was used to investigate in situ the interface formation between In2O3 and the layered semiconductor InSe. For thick In2O3 films a work function of φ = 4.3 eV and a surface Fermi level position of EF−EV = 3.0 eV is determined, giving an ionization potential IP = 7.3 eV and an electron affinity χ = 3.7 eV. The interface exhibits a type I band alignment with ΔEV = 2.05 eV, ΔEC = 0.29 eV, and an interface dipole of δ = −0.55 [email protected]

Boosting Long-Term Stability of Pure Formamidinium Perovskite Solar Cells by Ambient Air Additive Assisted Fabrication

Due to the high industrial interest for perovskite-based photovoltaic devices, there is an urgent need to fabricate them under ambient atmosphere, not limited to low relative humidity (RH) conditions. The formamidinium lead iodide (FAPI) perovskite α-black phase is not stable at room temperature and is challenging to stabilize in an ambient environment. In this work, we show that pure FAPI perovskite solar cells (PSCs) have a dramatic increase of device long-term stability when prepared under ambient air compared to FAPI PSCs made under nitrogen, both fabricated with N-methylpyrrolidone (NMP). The T80 parameter, the time in which the efficiency drops to 80% of the initial value, increases from 21 (in N2) to 112 days (in ambient) to 145 days if PbS quantum dots (QDs) are introduced as additives in air-prepared FAPI PSCs. Furthermore, by adding methylammonium chloride (MACl) the power conversion efficiency (PCE) reaches 19.4% and devices maintain 100% of the original performance for at least 53 days. The presence of Pb–O bonds only in the FAPI films prepared in ambient conditions blocks the propagation of α- to δ-FAPI phase conversion. Thus, these results open the way to a new strategy for the stabilization in ambient air toward perovskite solar cells commercialization.Funding for open access charge: CRUE-Universitat Jaume

Tin perovskite solar cells with >1,300 h of operational stability in N2 through a synergistic chemical engineering approach

Despite the promising properties of tin-based halide perovskites, one clear limitation is the fast Sn+2 oxidation. Consequently, the preparation of long-lasting devices remains challenging. Here, we report a chemical engineering approach, based on adding Dipropylammonium iodide (DipI) together with a well-known reducing agent, sodium borohydride (NaBH4), aimed at preventing the premature degradation of Sn-HPs. This strategy allows for obtaining efficiencies (PCE) above 10% with enhanced stability. The initial PCE remained unchanged upon 5 h in air (60% RH) at maximum-power-point (MPP). Remarkably, 96% of the initial PCE was kept after 1,300 h at MPP in N2. To the best of our knowledge, these are the highest reported values for Sn-based solar cells. Our findings demonstrate a beneficial synergistic effect when additives are incorporated, highlight the important role of iodide in the performance upon light soaking, and, ultimately, unveil the relevance of controlling the halide chemistry for future improvement of Sn-based perovskite devices

In Situ Synthesis of Polythiophene and Silver Nanoparticles within a PMMA Matrix: A Nanocomposite Approach to Thermoelectrics

The processability of organic thermoelectric materials plays a crucial role due to their clear advantages of applicability in large-scale areas compared to traditional inorganic counterparts. A promising way to process thermoelectric materials based on conductive polymers is through in situ polymerization in an insulating polymer matrix. This work shows an interpenetrating polymeric network based on polythiophene, silver nanoparticles (Ag NPs), and poly(methyl methacrylate) (PMMA) produced by the oxidative polymerization of terthiophene by an oxidizing silver salt in a PMMA matrix. Ag NPs are in situ synthesized simultaneously as a byproduct. The reaction occurs very fast in the solid state, and after only 1 min, a homogeneous interpenetrating polymer network (IPN) film is obtained, reaching electrical conductivity values of 120 S cm–1. Ag NPs play a determining role in the conducting properties of the IPN. Moreover, the thermoelectric properties were evaluated as a function of the synthesis parameters, reaching a maximum power factor of 51 μW m–1 K–2. This study shows a promising method to enhance the processability of hybrid thermoelectric materials on the basis of conductive polymers and nanofillers

Solution-Processed Ni-Based Nanocomposite Electrocatalysts: An Approach to Highly Efficient Electrochemical Water Splitting

In this study, we report an up-scalable and low-cost solution-processed method to in situ synthesize an earth-abundant non-stoichiometric NiOx-based electrocatalytic film for water oxidation. The catalytic activity was found to be inversely proportional to the baking temperature, which varied from 50 to 500 °C. We found the formation of a hybrid nanocomposite thin film of NiOx nanocrystals (<2 nm size) inside an acetate-based organic matrix at low temperatures (<200 °C). The defective and short-range structural order of the NiOx-based nanocomposite electrocatalysts, compatible with lattice stress, low electrical conductivity, and high density of catalytically active surface species, and higher Fe incorporation were responsible for the enhanced electrocatalytic activity. Our champion NiOx catalyst features a 358 mV overpotential at 10 mA cm–2 and more than 60 h of continuous operation without significant losses, which is a remarkable milestone for undoped NiOx electrocatalysts synthesized at nearly room temperature by a solution-processed up-scalable method.Funding for open access charge: CRUE-Universitat Jaume IThe authors acknowledge the financial support from the Ministerio de Ciencia, Innovación y Universidades of Spain through funded projects ENE2017-85087-C3-1-R, RYC-2015-18349, and TEC2017-86102-C2-1-R and Agencia Valenciana de la Innovacion (AVI) INNVAL10/18/032. The authors thank the Central Support Service for Experimental Research (SCSIE) (XRD and SEM facilities) and the Institute of Materials Science (TGA and DTA equipment) of the University of Valencia and the Central Service of Scientific Instrumentation (SCIC) at University Jaume I. The authors also thank Prof. Juan P. Martinez-Pastor for his constructive suggestions and scientific discussions

Revealing giant exciton fine-structure splitting in 2D perovskites using van der Waals passivation

The study of two-dimensional (2D) van der Waals materials has been an active field of research in the development of new optoelectronics and photonic applications over the last decade. Organic-inorganic layered perovskites are currently some of the most promising 2D van der Waals materials, due to their exceptional optical brightness and enhanced excitonic effects. However, low crystal quality and spectral diffusion usually broaden the exciton linewidth, obscuring the fine structure of the exciton in conventional photoluminescence experiments. Here, we propose a mechanical approach for reducing the effect of spectral diffusion by means of hBN-capping on layered perovskites with different thicknesses, revealing the exciton fine structure. We used a stochastic model to link the reduction of the spectral linewidth with the population of active charge fluctuation centres present in the organic spacer taking part in the dynamical Stark shift. Active fluctuation centres are reduced by a factor of 3.7 to 7.1 when we include hBN-capping according to our direct spectral measurements. This rate is in good agreement with the analysis of the overlap between the squared perovskite lattice and the hexagonal hBN lattice. Van der Waals forces between both lattices cause the partial clamping of the perovskite organic spacer molecules, and hence, the amplitude of the dynamical Stark shift characteristic of the spectral diffusion effect is reduced. Our work provides an easy and low-cost solution to the problem of accessing important fine-structure excitonic state information, along with an explanation of the important carrier dynamics present in the organic spacer that affect the quality of the optical emission

Architectural and intangible heritage in Andalusia: the impact of tourism after UNESCO’s inscriptions

Póster presentado en la muestra de la International Union of Architects (UIA), la UIA International Forum 2019, con sede en Bakú, bajo la temática ‘Turismo masivo en ciudades históricas'. El Consejo Superior de los Colegios de Arquitectos de España (CSCAE) seleccionó a partir de las propuestas de los Colegios de Arquitectos 6 paneles con los que participó en la exposición. Este panel ha sido desarrollado por miembros del grupo de investigación HUM700: Patrimonio y Desarrollo Urbano Territorial en Andalucía de la Universidad de Sevilla y coordinado por el catedrático y colegiado del COAS Eduardo Mosquera Adell.Poster presented at the exhibition of the International Union of Architects (UIA), the UIA International Forum 2019 in Baku, under the theme ‘Mass tourism in historical cities'. The Superior Council of the Colleges of Architects of Spain (CSCAE) selected 6 panels from the proposals of the Association of Architects. This panel has been developed by members of the Research Lab HUM700: Heritage and Urban Territorial Development in Andalusia at the University of Seville and coordinated by the professor and registered architect Eduardo Mosquera Adell.Colegio Oficial de Arquitectos de SevillaConsejo Andaluz de Colegios Oficiales de ArquitectosConsejo Superior de los Colegios de Arquitectos de Españ

High content and dispersion of Gd in bimodal porous silica: T2 contrast agents under ultra-high magnetic fields

Silica-based UVM-7-type bimodal mesoporous materials with high gadolinium content (∞ ≥ Si/Gd ≥ 13) have been synthesized through a one-pot surfactant-assisted procedure from hydroalcoholic solution using a cationic surfactant as template, and starting from atrane complexes of Gd and Si as inorganic precursors. The novel synthetic pathway developed in the study preserves the UVM-7-type architecture while optimizing the dispersion of the Gd-guest species at the nanoscale and even at atomic level. It has been determined that the number of Gd atoms forming clusters is always less than 10. The behaviour under exposure to ultra-high magnetic fields reveals a significant increase in the transversal relaxivity value when compared with related materials in the bibliography. Their activity as T2 instead of T1 contrast agents is discussed and explained considering the high Gd-dispersion and concentration, nature of the materials as well as due to the high magnetic fields used, typical of MRM studies. The absence of toxicity has been confirmed in preliminary cell cultures “in vitro” and the degradation of the solids studied under biological conditions. Results suggest that the atrane route could be a suitable synthesis approach for the preparation of Gd containing contrast agents