Assessment of surface and electrical properties of the TiO2@zeolite hybrid materials.

Degradation of pollutants in aqueous medium is of high interest due to the impact on environment and human health, therefore, design and study of the physico-chemical properties of photocatalysts for water remediation are of major significance. Among properties of photocatalyst, those related to the surface and electrical mechanism are crucial to the photocatalyst´s performance. Here we report the chemical and morphological characteristics of TiO2@zeolite photocatalyst by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) respectively, and a coherent electrical conduction mechanism was proposed based on data obtained from assisted laser impedance spectroscopy (ALIS), in which the zeolite was synthesized from recycled coal fly ash. The results obtained by SEM and XPS verified the presence of spherical particles of TiO2 anatase with presence of Ti3+ state. ALIS results showed that impedance of the entire system increases when the amount of TiO2 increases and the samples with lower capacitive performance allowed a larger transfer of the charges between the solid-liquid interface. All results showed that higher photocatalytic performance of TiO2 growth over hydroxysodalite with 8.7 wt% and 25 wt% of TiO2 can be explained in terms of the morphology of TiO2 and the interactions between substrate-TiO2 mainly.

Exchange bias coupling and bipolar resistive switching at room temperature on GaSb/Mn multilayers for resistive memories applications.

This work present structural, morphological, magnetic, and electrical properties of GaSb/Mn multilayer deposited via DC magnetron sputtering at room temperature and at 423 K. The samples are characterized by forming layers of 3, 6 and 12 periods of the GaSb/Mn structure. Through XRD patterns, it was possible to stablish the formation of GaSb, Mn3Ga, and Mn2Sb2 phases. FTIR measurements present an optical interference associated with periodicity and the homogenous thickness of the layers. HR-SEM shows the multilayer architecture with columnar microstructure in the formation of layers with grain nucleation on the surface. A ferromagnetic-like behavior was observed in the multilayers at room temperature related to the domains and interlayers interaction. Additionally, the hysteresis curves present shifts attributed to the effect of exchange bias coupling. I-V curves show RESET-SET states of the multilayer system with bipolar resistive behavior, which can be modified by external magnetic fields. The resistive switching evidenced corresponds to the conductive mechanism based on the capacitive conductance and the formation of conductive filaments in multilayer structure.

The effect of Mn2Sb2 and Mn2Sb secondary phases on magnetism in (GaMn)Sb thin films.

In this work, a detailed study of structural, electrical and magnetic characterization of (GaMn)Sb diluted magnetic semiconductors (DMS) is presented. (GaMn)Sb thin films were grown by DC magnetron co-sputtering method as an innovative procedure to fabricate III-V DMS. The presence of unusual Mn2Sb2 and Mn2Sb secondary phases, induced by substrate temperature and deposition time, were revealed through XRD measurements. Magnetization measurements allow determining crossover between a paramagnetic-like to a ferromagnetic-like behavior controlled by secondary phases. It was found that both, the magnetic remanence and magnetic coercivity, increases with substrate temperature. Interestingly, the magnetic response is paramagnetic at lower deposition times and substrate temperatures, and XRD measurements suggest the absence of Mn2Sb and Mn2Sb2 in secondary phases. For longer deposition times or higher substrate temperature, XRD shows the presence of Mn2Sb2 and Mn2Sb phases and ferromagnetic-like behavior. The DC resistivity of our samples was characterized and the carrier density was determined by Hall measurements and, in contrast with the reported in other studies, found them to be a p-type semiconductor with carrier densities as big as one order of magnitude larger than reported values. From the ferromagnetic-like samples, evidence of an anomalous Hall-effect in the sample was found, with higher magnetic saturation and a anomalous Hall conductivity of 2380 S/cm. All the results point to a contribution of the secondary phases to the overall magnetic response of the samples used, and suggest the importance of studying the formation of secondary phases in the growth of DMS, especially, for the case of (GaMn)Sb where Mn ion can have multiple oxidation states.

Photonic effects in natural nanostructures on Morpho cypris and Greta oto butterfly wings.

Photonic crystals are some of the more spectacular realizations that periodic arrays can change the behavior of electromagnetic waves. In nature, so-called structural colors appear in insects and even plants. Some species create beautiful color patterns as part of biological behavior such as reproduction or defense mechanisms as a form of biomimetics. The interaction between light and matter occurs at the surface, producing diffraction, interference and reflectance, and light transmission is possible under suitable conditions. In particular, there are two Colombian butterflies, Morpho cypris and Greta oto, that exhibit iridescence phenomena on their wings, and in this work, we relate these phenomena to the photonic effect. The experimental and theoretical approaches of the optical response visible region were studied to understand the underlying mechanism behind the light-matter interaction on the wings of these Colombian butterflies. Our results can guide the design of novel devices that use iridescence as angular filters or even for cosmetic purposes.

Ferromagnetic-like behavior of Co doped TiO2 flexible thin films fabricated via co-sputtering for spintronic applications.

TiO2:Co thin films on ITO (Indium-tin-oxide)/PET (Poly Ethylene Terephthalate) flexible and glass substrates were fabricated via DC magnetron co-sputtering at room temperature. The samples deposited on glass substrates were subjected to annealing processes at 473 K for 2 h to improve the crystallization of the material. Both TiO2:Co/ITO/PET and TiO2:Co/glass thin films exhibited excellent optical properties with more than 80% transmission in the visible region. An increase on ITO/PET surface temperature was detected during the synthesis of the samples; this variation in the ITO substrate ( ∼ 2 K) was associated to impact energetic of ion or atoms bombarded during the deposition process. X-ray diffraction measurements evidenced local phases to growth on the flexible substrate; the random distributions of Cobalt crystals into the rutile and anatase phases were associated to a crystalline lattice embedded with magnetic ions. A configuration of small grains and absence of cluster formation on the surface of thin films was observed through SEM and AFM measurements. From this topographic study and MFM measurements evidenced that surface grains were not constituted magnetic domains formation in the thin films. The ferromagnetic-like behavior was observed in a magnetization as function of field measurement by PPMS. M vs H curves at room temperature for TiO2:Co/ITO/PET thin films, showed the hysteresis loop. The dipolar interaction between Cobalt ions without formation of domains were correlated to the magnetic behavior in the material, as the doping concentration is lower than 12%.

Optical Properties of Greta oto Butterfly Wings: Relation of Iridescence with Photonic Properties.

This work presents an experimental and theoretical study about the optical properties of the wings of butterfly Greta oto. UV-Vis spectroscopy was used to obtain the optical response of the sample as function of the incident light angle. It was possible to observe a shift in the maximum of the reflectance spectra towards lower values of lambda when the angle of incident light increases. The theoretical modeling allows us to relate photonic behavior with the optical properties of the wings of butterfly Greta oto. In particular, photonic behavior could be associated with the iridescent phenomenon on the butterfly wings.

Synthesis and characterization of porous silicon as hydroxyapatite host matrix of biomedical applications.

In this work, porous-silicon samples were prepared by electrochemical etching on p-type (B-doped) Silicon (Si) wafers. Hydrofluoric acid (HF)-ethanol (C2H5OH) [HF:Et] and Hydrofluoric acid (HF)-dimethylformamide (DMF-C3H7NO) [HF:DMF] solution concentrations were varied between [1:2]-[1:3] and [1:7]-[1:9], respectively. Effects of synthesis parameters, like current density, solution concentrations, reaction time, on morphological properties were studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM) measurements. Pore sizes varying from 20 nm to micrometers were obtained for long reaction times and [HF:Et] [1:2] concentrations; while pore sizes in the same order were observed for [HF:DMF] [1:7], but for shorter reaction time. Greater surface uniformity and pore distribution was obtained for a current density of around 8 mA/cm2 using solutions with DMF. A correlation between reflectance measurements and pore size is presented. The porous-silicon samples were used as substrate for hydroxyapatite growth by sol-gel method. X-ray diffraction (XRD) and SEM were used to characterize the layers grown. It was found that the layer topography obtained on PS samples was characterized by the evidence of Hydroxyapatite in the inter-pore regions and over the surface.

Efecto Hall y estudio de fotovoltaje superficial transiente (SPV) en películas delgadas de Cu3BiS3 / Hall effect and transient surface photovoltage (SPV) study of Cu3BiS3 thin films / Efeito Hall e estudo de foto voltagem superficial transiente (SPV) em películas delgadas de Cu3BiS3

Se presentan las propiedades eléctricas del compuesto Cu3BiS3 depositado por co-evaporación. Este es un nuevo compuesto que puede tener propiedades adecuadas para ser utilizado como capa absorbente en celdas solares. Las muestras fueron caracterizadas a través de medidas de efecto Hall y fotovoltaje superficial transiente (SPV). A través de medidas de efecto Hall se encontró que la concentración de portadores de carga n es del orden de 10(16) cm-3 independiente de la relación de masas de Cu/Bi. También se encontró que la movilidad de este compuesto (μ del orden de 4 cm²V -1s-1) varía de acuerdo con los mecanismos de transporte que la gobiernan en dependencia con la temperatura. A partir de las medidas de SPV se encontró alta densidad de defectos superficiales, defectos que son pasivados al superponer una capa buffer sobre el compuesto Cu3BiS3.

Here, we present the electrical properties of the compound Cu3BiS3 deposited by co-evaporation. This new compound may have the properties necessary to be used as an absorbent layer in solar cells. The samples were characterized by Hall effect and transient surface photovoltage (SPV) measurements. Using Hall effect measurements, we found that the concentration of n charge carriers is in the order of 10(16) cm³ irrespective of the Cu/Bi mass ratio. We also found that the mobility of this compound (μ in the order of 4 cm² V-1s-1) varies according to the transport mechanisms that govern it and are dependent on temperature. Based on the SPV, we found a high density of surface defects, which can be passivated by superimposing a buffer layer over the Cu3BiS3 compound.

Apresentam-se as propriedades elétricas do composto Cu3BiS3 depositado por co-evaporação. É um composto novo que pode ter as propriedades adequadas para ser utilizado como capa absorvente em células solares. As amostras foram caracterizadas através de medidas do efeito Hall e foto voltagem superficial transiente (SPV). Através de medidas do efeito Hall se encontro que a concentração de portadores de carga n é da ordem de 10(16) cm³ independentemente da relação de massas de Cu/Bi. Também se encontrou que a mobilidade des composto (μ da ordem de 4 cm²V -1s-1) varia de acordo com os mecanismos de transporte que a governam em dependência com a temperatura. Partindo das medidas de SPV se encontrou uma alta densidade de defeitos superficiais, defeitos que são passivados a sobrepor uma capa buffer sobre o composto Cu3BiS3.

Procesos hopping a través del modelo difusional en materiales nanocristalinos usados para aplicaciones fotovoltaicas / Hopping processes in nanocrystalline materials used for photovoltaic applications using a diffusion model / Processos Hopping através do modelo de difusão em materiais nanocristalinos utilizados para aplicações fotovoltaicas

Se presentan los modelos de hopping de rango variable (variable range hopping; VRH), vecinos cercanos (nearest neighbor hopping; NNH) y barreras de potencial presentes en las fronteras de grano; como mecanismos de transporte eléctrico predominantes en los materiales semiconductores para aplicaciones fotovoltaicas. Las medidas de conductividad a oscuras en función de temperatura fueron realizadas para región de bajas temperaturas entre 120 y 400 K con Si y compuestos Cu3BiS2 y Cu2ZnSnSe4. Siguiendo la teoría de percolación, se obtuvieron parámetros hopping y la densidad de estados cerca del nivel de Fermi, N(E F), para todas las muestras. A partir de los planteamientos dados por Mott para VRH, se presentó el modelo difusional, que permitió establecer la relación entre la conductividad y la densidad de estados de defecto o estados localizados en el gap del material. El análisis comparativo entre modelos, evidenció, que es posible obtener mejora hasta de un orden de magnitud en valores para cada uno de los parámetros hopping que caracterizan el material.

Here, we present variable range hopping (VRH) models, nearest neighbor hopping (NNH) and potential barriers present at the grain boundaries, as well as mechanisms of electrical transport predominant in semiconductor materials for photovoltaic applications. We performed dark conductivity measures according to temperature for low temperature regions between 120 and 400 K in Si and Cu3BiS2 and Cu2ZnSnSe4 compounds. Using the percolation theory, we obtained hopping parameters and the density of states near the Fermi, N(E F) level for all samples. Using the approach by Mott for VRH, we obtained the diffusion model, which established the relationship between conductivity and density of defect states or localized gap states of the material. The comparative analysis between models evidenced that it is possible to obtain improvement of an order of magnitude in the values of each of the hopping parameters that characterize the material.

Apresentam-se os modelos de hopping de categoria variável (variable range hopping; VRH), vizinhos próximos (nearest neighbor hopping, NNH) e barreiras de potenciais presentes nas fronteiras de grãos; como mecanismo de transporte elétrico predominantes nos materiais semicondutores para aplicações fotovoltaicas. As medidas de condutividade no escuro em função da temperatura foram realizadas para região de baixas temperaturas entre 120 e 400 K com Si e compostos Cu3BiS2 e Cu2ZnSnSe4. Seguindo a teoria da percolação obtiveram-se parâmetros hopping e a densidade de estados próximos do nível Fermi[BO1] N(E F) para toda a amostra. A partir das abordagens seguidas por Mott para VRH, apresentou-se o modelo de difusão, que permitiu estabelecer a relação entre a condutividade e a densidade de estados de defeito ou estados localizados no gap do material. A análise comparativa dos modelos mostrou que é possível obter melhoria até de uma amplitude de magnitude em valores para cada um dos parâmetros hopping que caracterizam o material.

Estructura cristalina del compuesto Cu2ZnSnSe4 depositado por co-evaporación: análisis comparativo estannita-kesterita / Crystal structure of Cu2ZnSnSe4 deposited by co-evaporation: A Stannite-kesterite comparative analysis / Estructura cristalina do composto Cu2ZnSnSe4 depositado por co-evaporação: análise comparativa estannita-kesterita

Se fabricaron películas del compuesto cuaternario Cu2ZnSnSe4 por el método de co-evaporación de los precursores cobre, estaño y seleniuro de zinc en presencia de una atmosfera de selenio. Las muestras fueron depositadas sobre sustratos de vidrio tipo soda lime. A partir de las medidas de difracción de rayos X se estableció, que la fase que caracteriza el compuesto es sensible a cambios en los parámetros de síntesis afectando la estructura del material. Se detallaron propiedades estructurales como distancia interplanar, planos cristalinos, tamaños del cristalito y posiciones atómicas de los elementos del compuesto; a través de la comparación de las estructuras estannita y kesterita asociadas al crecimiento del Cu2ZnSnSe4. El análisis comparativo entre las estructuras, permitió determinar la tipo estannita como la que cristaliza el material. Usando el método Rietveld y programas de cómputo se logró simular la estructura estannita obtenida; evidenciando diferencias sutiles con la estructura kesterita.

We fabricated quaternary compound, Cu2ZnSnSe4, films by co-evaporation of copper, tin and zinc selenide precursors in a selenium atmosphere and deposited the samples on soda-lime glass substrates. From the x-ray diffraction data, we established that the phase that characterizes the compound is sensitive to changes in the synthesis parameters and affects the structure of the material. Through a comparison of stannite and kesterite structures associated with Cu2ZnSnSe4 growth, we detailed structural properties such as interplanar distance, crystal planes, crystallite size and the atomic position of the elements of the compound. A comparative analysis of the structures revealed that the stannite is the crystallizing material. Using the Rietveld method and software we were able to simulate the stannite structure establishing subtle differences with the kesterite structure.

Fabricaram-se filmes do composto Cu2ZnSnSe4 pelo método de co-evaporação dos percursores cobre, estanho e seleneto de zinco na presença de uma atmosfera de selênio. As amostras foram depositadas sobre substratos de vidro tipo soda lime. A partir das medidas de difração de raios X se estabeleceu que a fase que caracteriza o composto é sensível a alterações nos parâmetros de síntese afetando a estrutura do material. Detalharam-se propriedades estruturais como distancia interplanar, planos cristalinos, tamanhos do cristalito e posições atómicas dos elementos do composto; através da comparação das estruturas estannita e kesterita associadas ao crescimento do Cu2ZnSnSe4. A análise comparativa entre as estruturas, permitiu determinar o tipo Estannita como a que cristaliza o material. Utilizando o método Rietveld e programas de computação conseguiu-se simular a estrutura estannita obtida; mostrando diferenças subtis com a estrutura kesterita.

Cálculo de constantes ópticas de películas delgadas de Cu3BiS3 a través del método de Wolfe / Calculation of the optical constants of Cu3BiS3 thin films using the Wolfe method / Calculou-se de constantes óticas de películas finas de Cu3BiS3 através do método de Wolfe

Se calculó la obtención de las constantes ópticas usando el método de Wolfe. Dichas contantes: coeficiente de absorción (α), índice de refracción (n) y espesor de una película delgada (d), son de importancia en el proceso de caracterización óptica del material. Se realizó una comparación del método del Wolfe con el método empleado por R. Swanepoel. Se desarrolló un modelo de programación no lineal con restricciones, de manera que fue posible estimar las constantes ópticas de películas delgadas semiconductoras, a partir únicamente, de datos de transmisión conocidos. Se presentó una solución al modelo de programación no lineal para programación cuadrática. Se demostró la confiabilidad del método propuesto, obteniendo valores de α = 10378.34 cm-1, n = 2.4595, d =989.71 nm y Eg = 1.39 Ev, a través de experimentos numéricos con datos de medidas de transmitancia espectral en películas delgadas de Cu3BiS3.

Using the Wolfe method, we calculated the procurement of optical constants. These constants, absorption coefficient (α), refraction index of (n) and thin film thickness (d ), are significant in the optical characterization of the material. We compared the Wolfe method with the method employed by R. Swanepoel. To estimate the optical constants of semiconductor thin films, we developed a constrained nonlinear programming model, based solely, on known transmission data. Ultimately, we presented a solution to this nonlinear programming model for quadratic programming. Through numerical experiments and transmittance spectral data of Cu3BiS3 thin films, we obtained values of a= 10378.34 cm-1, n = 2.4595, d =989.71 nm and Eg= 1.39 Ev, demonstrating the reliability of the proposed method.

Calculou-se a obtenção de constantes óticas utilizando o método de Wolfe. Estas constantes: coeficiente de absorção (α), índice de refração (n) e espessura de uma película fina (d), são importantes no processo de caracterização ótica do material. Realizou-se uma comparação do método de Wolfe com o método utilizado por R. Swanepoel. Desenvolveu-se um modelo de programação não linear com restrições, de modo que foi possível estimar as constantes óticas de películas finas semicondutores, a partir unicamente, de dados de transmissão conhecidos. Apresentou-se uma solução ao modelo de programação não linear para programação quadrática. Mostrou-se a confiabilidade do método proposto, obtendo valores de α = 10378.34 cm-1, n = 2.4595, d =989.71 nm y Eg = 1.39 Ev, através de experiências numéricas com dados de medidas de transmissão espectral em películas finas de Cu3BiS3.

Conducción hopping en películas nanocristalinas del compuesto CZTSe usado como capa absorbente en celdas solares / Hopping conduction in nanocrystalline composite films of CZTSe used as solar cell absorber layer / Condução hopping em películas nano-cristalinas do composto CZTSe utilizado como capa absorvente em painéis solares

Se presentan propiedades eléctricas y de transporte en películas nanocristalinas del compuesto cuaternario Cu2ZnSnSe4 (CZTSe) por método de co-evaporación física. Las muestras fueron crecidas sobre sustratos de vidrio soda-lime y variando en rango los parámetros de síntesis: masa de Cu y temperatura de sustrato. A partir de termopotencia a temperatura ambiente y de transmitancia espectral, se encontró que el material está caracterizado por conductividad tipo n y ancho de banda de energía prohibida de 1.7 eV, respectivamente. Las medias de conductividad eléctrica (región de bajas temperaturas; 90-200 K) mostraron que los procesos de conducción se realizan vía hopping de rango de variable entre estados extendidos. Los parámetros que caracterizaron éste mecanismo, energía de activación (Whopp) y rango hopping (Rhopp), fueron obtenidos mediante teoría de percolación y modelo difusional. Se obtuvo, que para las muestras CZTSe la densidad de estados de defecto cerca del nivel de Fermi del material, N(Ef), está alrededor de 3,403x10(18) cm-3 eV-1. Se presentó correlación entre parámetros de depósito y propiedades eléctricas. Se observó influencia de parámetros sobre formación de fases adicionales en el compuesto.

Here, we present electronic and transport properties of quaternary Cu2ZnSnSe4 (CZTSe) nanocrystalline films fabricated by physical co-evaporation. The samples were grown on soda-lime glass substrates and synthesis parameter ranges, Cu mass and substrate temperature were varied. Using thermopower at room temperature and spectral transmittance we found that the material is characterized by n-type conductivity and forbidden energy bandwidth of 1.7 eV, respectively. Electrical conductivity means (low temperature region; 90-200 K) showed that conductivity processes occur via variable range hopping between extended states. We obtained the parameters characterizing this mechanism, activation energy (Whopp), and range hopping (Rhopp), by employing the percolation theory and diffusion model. The density of defect states near the Fermi level of the material, N (Ef) of the CZTSe samples is about 3,403x10(18) cm-3 eV-1. We found a correlation between deposition parameters and electrical properties and observed a parameter influence on the formation of additional phases in the compound.

Apresentam-se propriedades elétricas e de transporte em películas nano-cristalinas do composto quaternário Cu2ZnSnSe4 (CZTSe) pelo método de co-evaporação física. As amostras foram crescidas sobre substratos de vidro soda-lime e variando a amplitude dos parâmetros de síntese: massa de Cu e temperatura do substrato. A partir de termo-potência a temperatura ambiente e de transmissão espectral, encontrou-se que o material está caracterizado pela condutividade tipo n e largura de banda de energia proibida de 1.7 eV, respetivamente. As medidas de condutividade elétrica (regiões de baixas temperaturas; 90-200 K) mostraram que os processos de condução se realizam via hopping de amplitude variável entre estados estendidos. Os parâmetros que caracterizaram este mecanismo, energia de ativação (Whopp) e amplitude hopping (Rhopp), foram obtidos mediante a teoria de percolação e o modelo de difusão. Obteve-se que, para as amostras CZTSe, a densidade de estados de defeito próximos do nível de Fermi do material, N(EF), está ao redor de, 3,403x10(18) cm-3 eV-1. Apresentou-se correlação entre parâmetros de depósito e propriedades elétricas. Observou-se influencia de parâmetros sobre a formação de fases no composto.