Elucidating the real-time Ag nanoparticle growth on alpha-Ag2WO4 during electron beam irradiation: experimental evidence and theoretical insights

FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORWhy and how Ag is formed when electron beam irradiation takes place on alpha-Ag2WO4 in a vacuum transmission electron microscopy chamber? To find an answer, the atomic-scale mechanisms underlying the formation and growth of Ag on alpha-Ag2WO4 have been investigated by detailed in situ transmission electron microscopy (TEM) and field emission scanning electron microscopy (FE-SEM) studies, density functional theory based calculations and ab initio molecular dynamics simulations. The growth process at different times, chemical composition, size distribution and element distribution were analyzed in depth at the nanoscale level using FE-SEM, operated at different voltages (5, 10, 15, and 20 kV), and TEM with energy dispersive spectroscopy (EDS) characterization. The size of Ag nanoparticles covers a wide range of values. Most of the Ag particles are in the 20-40 nm range. The nucleation and formation of Ag on alpha-Ag2WO4 is a result of structural and electronic changes in the AgOx (x = 2,4, 6, and 7) clusters used as constituent building blocks of this material, consistent with metallic Ag formation. First principle calculations point out that Ag-3 and Ag-4-fold coordinated centers, located in the sub-surface of the (100) surface, are the most energetically favorable to undergo the diffusion process to form metallic Ag. Ab initio molecular dynamics simulations and the nudged elastic band (NEB) method were used to investigate the minimum energy pathways of these Ag atoms from positions in the first slab layer to outward sites on the (100) surface of alpha-Ag2WO4. The results point out that the injection of electrons decreases the activation barrier for this diffusion step and this unusual behavior results from the presence of a lower energy barrier process.Why and how Ag is formed when electron beam irradiation takes place on alpha-Ag2WO4 in a vacuum transmission electron microscopy chamber? To find an answer, the atomic-scale mechanisms underlying the formation and growth of Ag on alpha-Ag2WO4 have been investigated by detailed in situ transmission electron microscopy (TEM) and field emission scanning electron microscopy (FE-SEM) studies, density functional theory based calculations and ab initio molecular dynamics simulations. The growth process at different times, chemical composition, size distribution and element distribution were analyzed in depth at the nanoscale level using FE-SEM, operated at different voltages (5, 10, 15, and 20 kV), and TEM with energy dispersive spectroscopy (EDS) characterization. The size of Ag nanoparticles covers a wide range of values. Most of the Ag particles are in the 20-40 nm range. The nucleation and formation of Ag on alpha-Ag2WO4 is a result of structural and electronic changes in the AgOx (x = 2,4, 6, and 7) clusters used as constituent building blocks of this material, consistent with metallic Ag formation. First principle calculations point out that Ag-3 and Ag-4-fold coordinated centers, located in the sub-surface of the (100) surface, are the most energetically favorable to undergo the diffusion process to form metallic Ag. Ab initio molecular dynamics simulations and the nudged elastic band (NEB) method were used to investigate the minimum energy pathways of these Ag atoms from positions in the first slab layer to outward sites on the (100) surface of alpha-Ag2WO4. The results point out that the injection of electrons decreases the activation barrier for this diffusion step and this unusual behavior results from the presence of a lower energy barrier process.17753525359FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORFAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORFAPESP [2013/07296-2, 2012/14468-1, 2010/16970-0, 2013/02032-7]CNPq [573636/2008-7, 150753/2013-6]CAPES [088/2013]2010/16970-02012/14468-12013/02032-72013/07296-2573636/2008-7150753/2013-6088/2013The authors are grateful to Prometeo/2009/053 (GeneralitatValenciana), Ministerio de Economia y Competitividad (Spain), CTQ2012-36253-C03-02, Spanish Brazilian program (PHB2009-0065-PC), FAPESP (Project 2013/07296-2) (Project 2012/14468-1) (Project 2010/16970-0), grant (2013/02032-7), CAPES and CNPq (Project 573636/2008-7, Grant 150753/2013-6) and CAPES (Project 088/2013) for financially supporting this research. Most of the calculations were performed using IFGW-UNICAMP computer facilities and the National Center for High Performance Computing in São Paulo (CENAPAD-SP). We also acknowledge the Servei Informática, Universitat Jaume I, for the generous allotment of computer time

Faculty perceptions of extra-cognitive factors in virtual teaching during the pandemic

The COVID-19 pandemic obliged Argentina to adopt distance learning to continue university classes during 2020. In this article, a study is presented on the perceptions and perspectives of the faculty in the School of Education Sciences of the Universidad Nacional de Entre Ríos regarding this emergency educational virtualization. The methodology regards a case study. For the collection of information, a virtual survey was used that led to a qualitative and quantitative analysis of the responses. A statistical analysis of language patterns was implemented through the program Linguistic Inquiry and Word Count in order to examine affective, cognitive, and social processes linked to the use of technologies during the pandemic. The results indicate that, whereas the faculty had available technologies, abilities to use them, and an appropriate institutional environment, in that moment emerging difficulties manifested related to the conditions of livability and the possibilities of spatial-temporal organization for carrying out telework. It is concluded that extracognitive factors, such as domestic conditions and perceptions of virtuality in teaching, are two unavoidable aspects for moving towards modalities with a higher degree of mediatization during the post-pandemic period

Inversion charge study in TMO hole-selective contact-based solar cells

© 2023 IEEE. Personal use of this material is permitted. Permission from IEEE must be obtained for all other uses, in any current or future media, including reprinting/republishing this material for advertising or promotional purposes,creating new collective works, for resale or redistribution to servers or lists, or reuse of any copyrighted component of this work in other works.In this article, we study the effect of the inversion charge ( Q inv ) in a solar cell based on the hole-selective characteristic of substoichiometric molybdenum oxide (MoO x ) and vanadium oxide (VO x ) deposited directly on n-type silicon. We measure the capacitance–voltage ( C – V ) curves of the solar cells at different frequencies and explain the results taking into account the variation of the space charge and the existence of Q inv in the c-Si inverted region. The high-frequency capacitance measurements follow the Schottky metal–semiconductor theory, pointing to a low inversion charge influence in these measurements. However, for frequencies lower than 20 kHz, an increase in the capacitance is observed, which we relate to the contribution of the inversion charge. In addition, applying the metal–semiconductor theory to the high-frequency measurements, we have obtained the built-in voltage potential and show new evidence about the nature of the conduction process in this structure. This article provides a better understanding of the transition metal oxide/n-type crystalline silicon heterocontact.The authors would like to acknowledge the CAI de Técnicas Físicas of the Universidad Complutense de Madrid. The authors would also like to thank the Mexican grants program CONACyT for its financial collaboration.Peer ReviewedPostprint (author's final draft

Analysis of the immune system of multiple myeloma patients achieving long-term disease control by multidimensional flow cytometry

Spanish Myeloma Group (GEM) and Grupo Castellano-Leones de Gammapatias Monoclonales, cooperative study groups: et al.Multiple myeloma remains largely incurable. However, a few patients experience more than 10 years of relapsefree survival and can be considered as operationally cured. Interestingly, long-term disease control in multiple myeloma is not restricted to patients with a complete response, since some patients revert to having a profile of monoclonal gammopathy of undetermined significance. We compared the distribution of multiple compartments of lymphocytes and dendritic cells in the bone marrow and peripheral blood of multiple myeloma patients with long-term disease control (n=28), patients with newly diagnosed monoclonal gammopathy of undetermined significance (n=23), patients with symptomatic multiple myeloma (n=23), and age-matched healthy adults (n=10). Similarly to the patients with monoclonal gammopathy of undetermined significance and symptomatic multiple myeloma, patients with long-term disease control showed an expansion of cytotoxic CD8 + T cells and natural killer cells. However, the numbers of bone marrow T-regulatory cells were lower in patients with long-term disease control than in those with symptomatic multiple myeloma. It is noteworthy that B cells were depleted in patients with monoclonal gammopathy of undetermined significance and in those with symptomatic multiple myeloma, but recovered in both the bone marrow and peripheral blood of patients with long-term disease control, due to an increase in normal bone marrow B-cell precursors and plasma cells, as well as pre-germinal center peripheral blood B cells. The number of bone marrow dendritic cells and tissue macrophages differed significantly between patients with long-term disease control and those with symptomatic multiple myeloma, with a trend to cell count recovering in the former group of patients towards levels similar to those found in healthy adults. In summary, our results indicate that multiple myeloma patients with long-term disease control have a constellation of unique immune changes favoring both immune cytotoxicity and recovery of B-cell production and homing, suggesting improved immune surveillance.This work was supported by the Cooperative Research Thematic Network (RTICCs; RD06/0020/0006 and G03/136), Instituto de Salud Carlos III/ Subdirección General de Investigación Sanitaria (FIS: PI060339; 06/1354; 02/0905; 01/0089/01-02; PS09/01897/01370) and Consejeria de Educacion (GR37) and Consejería de Sanidad, Junta de Castilla y León, Valladolid, Spain (557/A/10). The authors also thank the Fundación Carolina-BBVA for supporting and promoting the exchange of medical researchers from Latin America to Spain.Peer Reviewe