Assessment of the potential of tin sulphide thin films prepared by sulphurization of metallic precursors as cell absorbers

In this work, SnxSy thin films have been grown on soda-lime glass substrates by sulphurization of metallic precursors in a nitrogen plus sulphur vapour atmosphere. Different sulphurization temperatures were tested, ranging from 300 °C to 520 °C. The resulting phases were structurally investigated by X-Ray Diffraction and Raman spectroscopy. Composition was studied using Energy Dispersive Spectroscopy being then correlated with the sulphurization temperature. Optical measurements were performed to obtain transmittance and reflectance spectra, from which the energy band gaps, were estimated. The values obtained were 1.17 eV for the indirect transition and for the direct transition the values varied from 1.26 eV to 1.57 eV. Electrical characterization using Hot Point Probe showed that all samples were p-type semiconductors. Solar cells were built using the structure: SLG/Mo/SnxSy/CdS/ZnO:Ga and the best result for solar cell efficiency was 0.17%.

Detection of ZnS phases in CZTS thin-films by EXAFS

Copper zinc tin sulfide (CZTS) is a promising Earthabundant thin-film solar cell material; it has an appropriate band gap of ~1.45 eV and a high absorption coefficient. The most efficient CZTS cells tend to be slightly Zn-rich and Cu-poor. However, growing Zn-rich CZTS films can sometimes result in phase decomposition of CZTS into ZnS and Cu2SnS3, which is generally deleterious to solar cell performance. Cubic ZnS is difficult to detect by XRD, due to a similar diffraction pattern. We hypothesize that synchrotron-based extended X-ray absorption fine structure (EXAFS), which is sensitive to local chemical environment, may be able to determine the quantity of ZnS phase in CZTS films by detecting differences in the second-nearest neighbor shell of the Zn atoms. Films of varying stoichiometries, from Zn-rich to Cu-rich (Zn-poor) were examined using the EXAFS technique. Differences in the spectra as a function of Cu/Zn ratio are detected. Linear combination analysis suggests increasing ZnS signal as the CZTS films become more Zn-rich. We demonstrate that the sensitive technique of EXAFS could be used to quantify the amount of ZnS present and provide a guide to crystal growth of highly phase pure films.

Study of polycrystalline Cu2ZnSnS4 films by Raman scattering

Cu2ZnSnS4 (CZTS) is a p-type semiconductor that has been seen as a possible low-cost replacement for Cu(In,Ga)Se2 in thin film solar cells. So far compound has presented difficulties in its growth, mainly, because of the formation of secondary phases like ZnS, CuxSnSx+1, SnxSy, Cu2−xS and MoS2. X-ray diffraction analysis (XRD), which is mostly used for phase identification cannot resolve some of these phases from the kesterite/stannite CZTS and thus the use of a complementary technique is needed. Raman scattering analysis can help distinguishing these phases not only laterally but also in depth. Knowing the absorption coefficient and using different excitation wavelengths in Raman scattering analysis, one is capable of profiling the different phases present in multi-phase CZTS thin films. This work describes in a concise form the methods used to grow chalcogenide compounds, such as, CZTS, CuxSnSx+1, SnxSy and cubic ZnS based on the sulphurization of stacked metallic precursors. The results of the films’ characterization by XRD, electron backscatter diffraction and scanning electron microscopy/energy dispersive spectroscopy techniques are presented for the CZTS phase. The limitation of XRD to identify some of the possible phases that can remain after the sulphurization process are investigated. The results of the Raman analysis of the phases formed in this growth method and the advantage of using this technique in identifying them are presented. Using different excitation wavelengths it is also analysed the CZTS film in depth showing that this technique can be used as non destructive methods to detect secondary phases.

Growth and characterization of Cu2ZnSn(S,Se)4 thin films for solar cells

Cu2ZnSnS4 (CZTS) and Cu2ZnSnSe4 (CZTSe) with their band gap energies around 1.45 eV and 1.0 eV, respectively, can be used as the absorber layer in thin film solar cells. By using a mixture of both compounds, Cu2ZnSn(S,Se)4 (CZTSSe), a band gap tuning may be possible. The latter material has already shown promising results such as solar cell efficiencies up to 10.1%. In this work, CZTSSe thin films were grown in order to study its structure and to establish the best growth precursors. SEM micrographs reveal an open columnar structure for most samples and EDS composition profiling of the cross sections show different selenium gradients. X-ray diffractograms show different shifts of the kesterite/stannite (1 1 2) peak, which indicate the presence of CZTSSe. From Raman scattering analysis, it was concluded that all samples had traces of CZTS and CZTSSe. The composition of the CZTSSe layer was estimated using X-ray diffraction and Raman scattering and both results were compared. It was concluded that Se diffused more easily in precursors with ternary Cu–Sn–S phases and metallic Zn than in precursors with ZnS and/or CZTS already formed. It was also showed that a combination of X-ray diffraction and Raman scattering can be used to estimate the ratio of S per Se in CZTSSe samples.

Properties of tantalum oxynitride thin films produced by magnetron sputtering: the influence of processing parameters

The main purpose of this work is to present and to interpret the change of structure and physical properties of tantalum oxynitride (TaNxOy) thin films, produced by dc reactive magnetron sputtering, by varying the processing parameters. A set of TaNxOy films was prepared by varying the reactive gases flow rate, using a N2/O2 gas mixture with a concentration ratio of 17:3. The different films, obtained by this process, exhibited significant differences. The obtained composition and the interpretation of X-ray diffraction results, shows that, depending on the partial pressure of the reactive gases, the films are: essentially dark grey metallic, when the atomic ratio (N + O)/Ta < 0.1, evidencing a tetragonal β-Ta structure; grey-brownish, when 0.1 < (N + O)/Ta < 1, exhibiting a face-centred cubic (fcc) TaN-like structure; and transparent oxide-type, when (N + O)/Ta > 1, evidencing the existence of Ta2O5, but with an amorphous structure. These transparent films exhibit refractive indexes, in the visible region, always higher than 2.0. The wear resistance of the films is relatively good. The best behaviour was obtained for the films with (N + O)/Ta ≈ 0.5 and (N + O)/Ta ≈ 1.3.

Mechanical and tribological characterization of TiB2 thin films

Titanium Diboride (TiB2) presents high mechanical and physical properties. Some wear studies were also carried out in order to evaluate its tribological properties. One of the most popular wear tests for thin films is the ball-cratering configuration. This work was focused on the study of the tribological properties of TiB2 thin films using micro-abrasion tests and following the BS EN 1071-6: 2007 standard. Due to high hardness usually patented by these films, diamond was selected as abrasive on micro-abrasion tests. Micro-abrasion wear tests were performed under five different durations, using the same normal load, speed rotation and ball. Films were deposited by unbalanced magnetron sputtering Physical Vapour Deposition (PVD) technique using TiB2 targets. TiB2 films were characterized using different methods as Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDS), Atomic Force Microscopy (AFM), X-ray Diffraction (XRD), Electron Probe Micro-Analyser (EPMA), Ultra Micro Hardness and Scratch-test Analysis, allowing to confirm that TiB2 presents adequate mechanical and physical properties. Ratio between hardness (coating and abrasive particles), wear resistance and wear coefficient were studied, showing that TiB2 films shows excellent properties for tribological applications.

Adhesion and wear behaviour of NCD coatings on Si3N4 by micro-abrasion tests

Nanocrystalline diamond (NCD) coatings offer an excellent alternative for tribological applications, preserving most of the intrinsic mechanical properties of polycrystalline CVD diamond and adding to it an extreme surface smoothness. Silicon nitride (Si3N4) ceramics are reported to guarantee high adhesion levels to CVD microcrystalline diamond coatings, but the NCD adhesion to Si3N4 is not yet well established. Micro-abrasion tests are appropriate for evaluating the abrasive wear resistance of a given surface, but they also provide information on thin film/substrate interfacial resistance, i.e., film adhesion. In this study, a comparison is made between the behaviour of NCD films deposited by hot-filament chemical vapour deposition (HFCVD) and microwave plasma assisted chemical vapour deposition (MPCVD) techniques. Silicon nitride (Si3N4) ceramic discs were selected as substrates. The NCD depositions by HFCVD and MPCVD were carried out using H2–CH4 and H2–CH4–N2 gas mixtures, respectively. An adequate set of growth parameters was chosen for each CVD technique, resulting in NCD films having a final thickness of 5 m. A micro-abrasion tribometer was used, with 3 m diamond grit as the abrasive slurry element. Experiments were carried out at a constant rotational speed (80 r.p.m.) and by varying the applied load in the range of 0.25–0.75 N. The wear rate for MPCVD NCD (3.7±0.8 × 10−5 m3N−1m−1) is compatible with those reported for microcrystalline CVD diamond. The HFCVD films displayed poorer adhesion to the Si3N4 ceramic substrates than the MPCVD ones. However, the HFCVD films show better wear resistance as a result of their higher crystallinity according to the UV Raman data, despite evidencing premature adhesion failure.

Share GFS – Games, Films & Series: sistema de recomendação

Esta dissertação incide sobre o estudo e análise de uma solução para a criação de um sistema de recomendação para uma comunidade de consumidores de media e no consequente desenvolvimento da mesma cujo âmbito inicial engloba consumidores de jogos, filmes e/ou séries, com o intuito de lhes proporcionar a oportunidade de partilharem experiências, bem como manterem um registo das mesmas. Com a informação adquirida, o sistema reúne condições para proceder a sugestões direcionadas a cada membro da comunidade. O sistema atualiza a sua informação mediante as ações e os dados fornecidos pelos membros, bem como pelo seu feedback às sugestões. Esta aprendizagem ao longo do tempo permite que as sugestões do sistema evoluam juntamente com a mudança de preferência dos membros ou se autocorrijam. O sistema toma iniciativa de sugerir mediante determinadas ações, mas também pode ser invocada uma sugestão diretamente pelo utilizador, na medida em que este não precisa de esperar por sugestões, podendo pedir ao sistema que as forneça num determinado momento. Nos testes realizados foi possível apurar que o sistema de recomendação desenvolvido forneceu sugestões adequadas a cada utilizador específico, tomando em linha de conta as suas ações prévias. Para além deste facto, o sistema não forneceu qualquer sugestão quando o histórico destas tinha provado incomodar o utilizador.

Anomalous persistent photoconductivity in Cu2ZnSnS4 thin films and solar cells

A persistent photoconductivity effect (PPC) has been investigated in Cu2ZnSnS4 thin films and solar cells as a function of temperature. An anomalous increase of the PPC decay time with temperature was observed in all samples. The PPC decay time activation energy was found to increase when temperature rises above a crossover value, and also to grow with the increase of the sulfurization temperature and pressure. Both the anomalous behavior of the PPC decay time and the existence of two different activation energies are explained in terms of local potential fluctuations in the band edges of CZTS.

Effect of selenization conditions on the growth and properties of Cu2ZnSn(S,Se)4 thin films

The opto-electronic properties of copper zinc tin sulfide can be tuned to achieve better cell efficiencies by controlled incorporation of selenium. In this paper we report the growth of Cu2ZnSn(S,Se)4 (CZTSSe) using a hybrid process involving the sequential evaporation of Zn and sputtering of the sulfide precursors of Cu and Sn, followed by a selenization step. Two approaches for selenization were followed, one using a tubular furnace and the other using a rapid thermal processor. The effects of annealing conditions on the morphological and structural properties of the films were investigated. Scanning electron microscopy and energy dispersive spectroscopy were employed to investigate the morphology and composition of the films. Structural analyses were done using X-ray diffraction (XRD) and Raman spectroscopy. Structural analyses revealed the formation of CZTSSe. This study shows that regardless of the selenization method a temperature above 450 °C is required for conversion of precursors to a compact CZTSSe layer. XRD and Raman analysis suggests that the films selenized in the tubular furnace are selenium rich whereas the samples selenized in the rapid thermal processor have higher sulfur content.

Sistema de Recomendação: Share GFS Games, Films & Series

Esta dissertação incide sobre o estudo e análise de uma solução para a criação de um sistema de recomendação para uma comunidade de consumidores de media e no consequente desenvolvimento da mesma cujo âmbito inicial engloba consumidores de jogos, filmes e/ou séries, com o intuito de lhes proporcionar a oportunidade de partilharem experiências, bem como manterem um registo das mesmas. Com a informação adquirida, o sistema reúne condições para proceder a sugestões direccionadas a cada membro da comunidade. O sistema actualiza a sua informação mediante as acções e os dados fornecidos pelos membros, bem como pelo seu feedback às sugestões. Esta aprendizagem ao longo do tempo permite que as sugestões do sistema evoluam juntamente com a mudança de preferência dos membros ou se autocorrijam. O sistema toma iniciativa de sugerir mediante determinadas acções, mas também pode ser invocada uma sugestão directamente pelo utilizador, na medida em que este não precisa de esperar por sugestões, podendo pedir ao sistema que as forneça num determinado momento. Nos testes realizados foi possível apurar que o sistema de recomendação desenvolvido forneceu sugestões adequadas a cada utilizador específico, tomando em linha de conta as suas acções prévias. Para além deste facto, o sistema não forneceu qualquer sugestão quando o histórico destas tinha provado incomodar o utilizador.

Comparação dos Perfis Lipídicos de Plasma de uma População da Região Norte

Os ácidos gordos desempenham um papel fisiológico importante como componentes indispensáveis na estrutura celular, bem como fontes de energia. Nas últimas décadas, tem havido um aumento notável do interesse público nos ácidos gordos polinsaturados ómegas 3 e 6 e no seu impacto sobre a saúde humana, especialmente em doenças metabólicas e cardiovasculares. Estes ácidos gordos específicos podem prevenir e/ou tratar várias patologias metabólicas, atuando nomeadamente como compostos anti-inflamatórios. A menopausa é um fator de risco para doença cardiovascular, a diminuição de estrogénio, que ocorre neste estado fisiológico, provoca disfunção endotelial e stresse oxidativo. Consequentemente há uma redução dos níveis de ácidos gordos polinsaturados ómegas 3, o que contribui para o aparecimento de aterosclerose e doença cardiovascular. Neste contexto, o objetivo deste estudo foi avaliar e caracterizar o perfil lipídico de ácidos gordos de uma amostra de mulheres pós-menopausa e com este, estudar as associações entre o perfil lipídico determinado e parâmetros metabólicos de risco (parâmetros clínicos e bioquímicos). Inicialmente, os ácidos gordos foram extraídos da matriz plasmática através da derivatização destes e a sua composição percentual no plasma foi determinada com recurso a cromatografia gasosa com deteção de ionização de chama. De seguida, através do software IBM SPSS Statistics 21, foram estabelecidas associações entre os parâmetros clínicos e bioquímicos e o perfil lipídico determinado. A população em estudo foi divida em dois grupos consoante o período de entrada na menopausa (há menos de 7 anos e há 7 anos ou mais). Não há conhecimento de estudos semelhantes ao apresentado, que relacionem todo o perfil de ácidos gordos com parâmetros metabólicos de risco considerando o estado menopausal. Os resultados obtidos mostram que o perfil lipídico influencia vários marcadores metabólicos / endócrinos com relevância clínica que devem ser explorados em futuros ensaios clínicos. Para as mulheres na menopausa há menos de 7 anos foram estabelecidas as seguintes relações: i) entre os ácidos gordos saturados e insaturados cis e os níveis de ALP; ii) entre os ácidos gordos mono e polinsaturados cis e os níveis de GGT, IL10 e estradiol; iii) entre os ácidos gordos polinsaturados trans e o IMC e os níveis de IL6; iv) entre os ómegas 3 e os níveis de IL10 e ácido úrico; v) entre os ómegas 6 e os níveis de estradiol, ALP e GGT; vi) entre os ómegas 9 e os níveis de estradiol e GGT; vi) entre os ácidos gordos de curta cadeia e os níveis de colesterol total, LDL, triglicerídeos e IL10; vii) entre os ácidos gordos saturados de cadeia longa e o ΣÁcido láurico, mirístico, palmítico e esteárico e os níveis de triglicerídeos, ALP e GGT; viii) os níveis de IL10 podem ser simultaneamente associados com os ácidos gordos de curta cadeia e os ómegas 3. Para as mulheres na menopausa há 7 anos ou mais foram estabelecidas relações: i) entre os ómegas 3 e o IMC e os níveis de triglicerídeos; ii) entre os ácidos gordos monoinsaturados cis e os ómegas 9 com os níveis de ALT. Relações independentes do estado menopausal também foram estabelecidas, nomeadamente: i) entre os ácidos gordos polinsaturados cis e ómegas 6 e os níveis de ALT, triglicerídeos e AST; ii) entre os níveis de ácidos gordos monoinsaturados cis e ómegas 9 e os níveis de AST e triglicerídeos. O perfil lipídico de ácidos gordos pode ser considerado um biomarcador para a condição de saúde da mulher na menopausa.