Mo bilayer for thin film photovoltaics revisited

Thin film solar cells based on Cu(In,Ga)Se2 as an absorber layer use Mo as the back contact. This metal is widely used in research and in industry but despite this, there are only a few published studies on the properties of Mo. Properties such as low resistivity and good adhesion to soda lime glass are hard to obtain at the same time. These properties are dependent on the deposition conditions and are associated with the overall stress state of the film. In this report, a study of the deposition of a Mo bilayer is carried out by analysing first single and then bilayers. The best properties of the bilayer were achieved when the bottom layer was deposited at 10 × 10−3 mbar with a thickness of 500 nm and the top layer deposited at 1 × 10−3 mbar with a thickness of 300 nm. The films deposited under these conditions showed good adhesion and a sheet resistivity lower than 0.8 .

Study of optical and structural properties of Cu2ZnSnS4 thin films

Cu2ZnSnS4 is a promising semiconductor to be used as absorber in thin film solar cells. In this work, we investigated optical and structural properties of Cu2ZnSnS4 thin films grown by sulphurization of metallic precursors deposited on soda lime glass substrates. The crystalline phases were studied by X-ray diffraction measurements showing the presence of only the Cu2ZnSnS4 phase. The studied films were copper poor and zinc rich as shown by inductively coupled plasma mass spectroscopy. Scanning electron microscopy revealed a good crystallinity and compactness. An absorption coefficient varying between 3 and 4×104cm−1 was measured in the energy range between 1.75 and 3.5 eV. The band gap energy was estimated in 1.51 eV. Photoluminescence spectroscopy showed an asymmetric broad band emission. The dependence of this emission on the excitation power and temperature was investigated and compared to the predictions of the donor-acceptor-type transitions and radiative recombinations in the model of potential fluctuations. Experimental evidence was found to ascribe the observed emission to radiative transitions involving tail states created by potential fluctuations.

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.

Practices and trends of telework in the Portuguese industry: the results of surveys in the textile, metal and software sectors

The aim of the TeleRisk Project on labour relations and professional risks within the context of teleworking in Portugal – supported by IDICT – Institute for Development and Inspection of Working Conditions (Ministry of Labour), is to study the practices and forms of teleworking in the manufacturing sectors in Portugal. The project chose also the software industry as a reference sector, even though it does not intend to exclude from the study any other sector of activity or the so-called “hybrid” forms of work. However, the latter must have some of the characteristics of telework. The project thus takes into account the so-called “traditional” sectors of activity, namely textile and machinery and metal engineering (machinery and equipment), not usually associated to this type of work. However, telework could include, in the so-called “traditional” sectors, other variations that are not found in technologically based sectors. One of the evaluation methods for the dynamics associated to telework consisted in carrying out surveys by means of questionnaires, aimed at employers in the sectors analysed. This paper presents some of the results of those surveys. It is important to mention that, being a preliminary analysis, it means that it does not pretend to have exhausted all the issues in the survey, but has meant that it shows the bigger tendencies, in terms of teleworking practices, of the Portuguese industry.

In-situ X-ray diffraction studies during growth of Ni-Ti shape memory alloy films and their complementary ex-situ characterization

Shape Memory Alloy (SMA) Ni-Ti films have attracted much interest as functional and smart materials due to their unique properties. However, there are still important issues unresolved like formation of film texture and its control as well as substrate effects. Thus, the main challenge is not only the control of the microstructure, including stoichiometry and precipitates, but also the identification and control of the preferential orientation since it is a crucial factor in determining the shape memory behaviour. The aim of this PhD thesis is to study the optimisation of the deposition conditions of films of Ni-Ti in order to obtain the material fully crystallized at the end of the deposition, and to establish a clear relationship between the substrates and texture development. In order to achieve this objective, a two-magnetron sputter deposition chamber has been used allowing to heat and to apply a bias voltage to the substrate. It can be mounted into the six-circle diffractometer of the Rossendorf Beamline (ROBL) at the European Synchrotron Radiation Facility (ESRF), Grenoble, France, enabling an in-situ characterization by X-ray diffraction(XRD) of the films during their growth and annealing. The in-situ studies enable us to identify the different steps of the structural evolution during deposition with a set of parameters as well as to evaluate the effect of changing parameters on the structural characteristics of the deposited film. Besides the in-situ studies, other complementary ex-situ characterization techniques such as XRD at a laboratory source, Rutherford backscattering spectroscopy(RBS), Auger electron spectroscopy (AES), cross-sectional transmission electron microscopy (X-TEM), scanning electron microscopy (SEM), and electrical resistivity (ER) measurements during temperature cycling have been used for a fine structural characterization. In this study, mainly naturally and thermally oxidized Si(100) substrates, TiN buffer layers with different thicknesses (i.e. the TiN topmost layer crystallographic orientation is thickness dependent) and MgO(100) single crystals were used as substrates. The chosen experimental procedure led to a controlled composition and preferential orientation of the films. The type of substrate plays an important role for the texture of the sputtered Ni-Ti films and according to the ER results, the distinct crystallographic orientations of the Ni-Ti films influence their phase transformation characteristics.

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.

Lightweight amorphous silicon photovoltaic modules on flexible plastic substrate

Solar cells on lightweight and flexible substrates have advantages over glass-or wafer-based photovoltaic devices in both terrestrial and space applications. Here, we report on development of amorphous silicon thin film photovoltaic modules fabricated at maximum deposition temperature of 150 degrees C on 100 mu m thick polyethylene-naphtalate plastic films. Each module of 10 cm x 10 cm area consists of 72 a-Si:H n-i-p rectangular structures with transparent conducting oxide top electrodes with Al fingers and metal back electrodes deposited through the shadow masks. Individual structures are connected in series forming eight rows with connection ports provided for external blocking diodes. The design optimization and device performance analysis are performed using a developed SPICE model.

The effect of metal transfer modes and shielding gas composition on the emission of ultraafine particles in MAG steel welding

The present study aims to characterize ultrafine particles emitted during gas metal arc welding of mild steel and stainless steel, using different shielding gas mixtures, and to evaluate the effect of metal transfer modes, controlled by both processing parameters and shielding gas composition, on the quantity and morphology of the ultrafine particles. It was found that the amount of emitted ultrafine particles (measured by particle number and alveolar deposited surface area) are clearly dependent from the main welding parameters, namely the current intensity and the heat input of the Welding process. The emission of airborne ultrafine particles increases with the current intensity as fume formation rate does. When comparing the shielding gas mixtures, higher emissions were observed for more oxidizing mixtures, that is, with higher CO2 content, which means that these mixtures originate higher concentrations of ultrafine particles (as measured by number of particles. by cubic centimeter of air) and higher values of alveolar deposited surface area of particles, thus resulting in a more hazardous condition regarding welders exposure.

Mono(Eta(5)-cyclopentadienyl)metal(II) complexes with thienyl acetylide chromophores: synthesis, electrochemical studies, and first hyperpolarizabilities

A series of mono(eta(5)-cyclopentadienyl)metal-(II) complexes with nitro-substituted thienyl acetylide ligands of general formula [M(eta(5)-C5H5)(L)(C C{C4H2S}(n)NO2)] (M = Fe, L = kappa(2)-DPPE, n = 1,2; M = Ru, L = kappa(2)-DPPE, 2 PPh3, n = 1, 2; M = Ni, L = PPh3, n = 1, 2) has been synthesized and fully characterized by NMR, FT-IR, and UV-Vis spectroscopy. The electrochemical behavior of the complexes was explored by cyclic voltammetry. Quadratic hyperpolarizabilities (beta) of the complexes have been determined by hyper-Rayleigh scattering (HRS) measurements at 1500 nm. The effect of donor abilities of different organometallic fragments on the quadratic hyperpolarizabilities was studied and correlated with spectroscopic and electrochemical data. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations were employed to get a better understanding of the second-order nonlinear optical properties in these complexes. In this series, the complexity of the push pull systems is revealed; even so, several trends in the second-order hyperpolarizability can still be recognized. In particular, the overall data seem to indicate that the existence of other electronic transitions in addition to the main MLCT clearly controls the effectiveness of the organometallic donor ability on the second-order NLO properties of these push pull systems.

The effect of metal transfer stability (spattering) on fume generation, morphology and composition in short-circuit MAG welding

The main objective of this work was to evaluate the hypothesis that the greater transfer stability leads also to less volume of fumes. Using an Ar + 25%CO2 blend as shielding gas and maintaining constant the average current, wire feed speed and welding speed, bead-on-plate welds were carried out with plain carbon steel solid wire. The welding voltage was scanned to progressively vary the transfer stability. Using two conditions of low stability and one with high stability, fume generation was evaluated by means of the AWS F1.2:2006 standard. The influence of these conditions on fume morphology and composition was also verified. A condition with greater transfer stability does not generate less fume quantity, despite the fact that this condition produces fewer spatters. Other factors such as short-circuit current, arcing time, droplet diameters and arc length are the likely governing factors, but in an interrelated way. Metal transfer stability does not influence either the composition or the size/morphology of fume particulates. (c) 2014 Elsevier B.V. All rights reserved.

Trits(Pyrazol-1-YL)methane metal complexes for catalytic mild oxidative functionalizations of alkanes, alkanes and ketones

This work concerns recent advances (since 2005) in the oxidative functionalization of alkanes, alkenes and ketones, under mild conditions, catalyzed by homoscorpionate tris(pyrazol-1-yl)methane metal complexes. The main types of such homogeneous or supported catalysts are classified, and the critical analysis of the most efficient catalytic systems in the different reactions is presented. These reactions include the mild oxidation of alkanes (typically cyclohexane as a model substrate) with hydrogen peroxide (into alkyl hydroperoxides, alcohols, and ketones), the hydrocarboxylation of gaseous alkanes (with carbon monoxide and potassium peroxodisulfate) into the corresponding Cn+1 carboxylic acids, as well as the epoxidation of alkenes and the Baeyer-Villiger oxidation of linear and cyclic ketones with hydrogen peroxide into the corresponding esters and lactones. Effects of various reaction parameters are highlighted and the preferable requirements for a prospective homogeneous or supported C-scorpionate-M-based catalyst in oxidative transformations of those substrates are identified. (C) 2014 Elsevier B.V. All rights reserved.