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.

Cu2ZnSnS4 solar cells prepared with sulphurized dc-sputtered stacked metallic precursors

In the present work we report the details of the preparation and characterization results of Cu2ZnSnS4 (CZTS) based solar cells. The CZTS absorber was obtained by sulphurization of dc magnetron sputtered Zn/Sn/Cu precursor layers. The morphology, composition and structure of the absorber layer were studied by scanning electron microscopy, energy dispersive spectroscopy, X-ray diffraction and Raman scattering. The majority carrier type was identified via a hot point probe analysis. The hole density, space charge region width and band gap energy were estimated from the external quantum efficiency measurements. A MoS2 layer that formed during the sulphurization process was also identified and analyzed in this work. The solar cells had the following structure: soda lime glass/Mo/CZTS/CdS/i-ZnO/ZnO:Al/Al grid. The best solar cell showed an opencircuit voltage of 345 mV, a short-circuit current density of 4.42 mA/cm2, a fill factor of 44.29% and an efficiency of 0.68% under illumination in simulated standard test conditions: AM 1.5 and 100 mW/cm2.

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.

Short Assessment of Health Literacy for Portuguese-speaking Adults

OBJECTIVE: To develop and validate a short health literacy assessment tool for Portuguese-speaking adults. METHODS: The Short Assessment of Health Literacy for Portuguese-speaking Adults is an assessment tool which consists of 50 items that assess an individual's ability to correctly pronounce and understand common medical terms. We evaluated the instrument's psychometric properties in a convenience sample of 226 Brazilian older adults. Construct validity was assessed by correlating the tool scores with years of schooling, self-reported literacy, and global cognitive functioning. Discrimination validity was assessed by testing the tool's accuracy in detecting inadequate health literacy, defined as failure to fully understand standard medical prescriptions. RESULTS: Moderate to high correlations were found in the assessment of construct validity (Spearman's coefficients ranging from 0.63 to 0.76). The instrument showed adequate internal consistency (Cronbach's alpha=0.93) and adequate test-retest reliability (intraclass correlation coefficient=0.95). The area under the receiver operating characteristic curve for detection of inadequate health literacy was 0.82. A version consisting of 18 items was tested and showed similar psychometric properties. CONCLUSIONS: The instrument developed showed good validity and reliability in a sample of Brazilian older adults. It can be used in research and clinical settings for screening inadequate health literacy.

Self-mated tribological systems based on multilayer micro/nanocrystalline CVD diamond coatings

The tribological response of multilayer micro/nanocrystalline diamond coatings grown by the hot filament CVD technique is investigated. These multigrade systems were tailored to comprise a starting microcrystalline diamond (MCD) layer with high adhesion to a silicon nitride (Si3N4) ceramic substrate, and a top nanocrystalline diamond (NCD) layer with reduced surface roughness. Tribological tests were carried out with a reciprocating sliding configuration without lubrication. Such composite coatings exhibit a superior critical load before delamination (130–200 N), when compared to the mono- (60–100 N) and bilayer coatings (110 N), considering ∼10 µm thick films. Regarding the friction behaviour, a short-lived initial high friction coefficient was followed by low friction regimes (friction coefficients between 0.02 and 0.09) as a result of the polished surfaces tailored by the tribological solicitation. Very mild to mild wear regimes (wear coefficient values between 4.1×10−8 and 7.7×10−7 mm3 N−1 m−1) governed the wear performance of the self-mated multilayer coatings when subjected to high-load short-term tests (60–200 N; 2 h; 86 m) and medium-load endurance tests (60 N; 16 h; 691 m).

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.

Wind-CSP short-term coordination by MILP approach

This paper is on the maximization of total profit in a day-ahead market for a price-taker producer needing a short-term scheduling for wind power plants coordination with concentrated solar power plants, having thermal energy storage systems. The optimization approach proposed for the maximization of profit is a mixed-integer linear programming problem. The approach considers not only transmission grid constraints, but also technical operating constraints on both wind and concentrated solar power plants. Then, an improved short-term scheduling coordination is provided due to the more accurate modelling presented in this paper. Computer simulation results based on data for the Iberian wind and concentrated solar power plants illustrate the coordination benefits and show the effectiveness of the approach.

Short-term Value for the Water Stored in Headsensitivity Power System Reservoirs

As it is well known, competitive electricity markets require new computing tools for generation companies to enhance the management of its resources. The economic value of the water stored in a power system reservoir is crucial information for enhancing the management of the reservoirs. This paper proposes a practical deterministic approach for computing the short-term economic value of the water stored in a power system reservoir, emphasizing the need to considerer water stored as a scarce resource with a short-term economic value. The paper addresses a problem concerning reservoirs with small storage capacities, i.e., the reservoirs considered as head-sensitivity. More precisely, the respective hydro plant is head-dependent and a pure linear approach is unable to capture such consideration. The paper presents a case study supported by the proposed practical deterministic approach and applied on a real multi-reservoir power system with three cascaded reservoirs, considering as input data forecasts for the electric energy price and for the natural inflow into the reservoirs over the schedule time horizon. The paper presents various water schedules due to different final stored water volume conditions on the reservoirs. Also, it presents the respective economic value of the water for the reservoirs at different stored water volume conditions.

Metaheuristic approach to the Holt-Winters optimal short term load forecast

Electricity short-term load forecast is very important for the operation of power systems. In this work a classical exponential smoothing model, the Holt-Winters with double seasonality was used to test for accurate predictions applied to the Portuguese demand time series. Some metaheuristic algorithms for the optimal selection of the smoothing parameters of the Holt-Winters forecast function were used and the results after testing in the time series showed little differences among methods, so the use of the simple local search algorithms is recommended as they are easier to implement.

Metaheuristhic approach to the Holt-Winters optimal short term load forecast

Electricity short-term load forecast is very important for the operation of power systems. In this work a classical exponential smoothing model, the Holt-Winters with double seasonality was used to test for accurate predictions applied to the Portuguese demand time series. Some metaheuristic algorithms for the optimal selection of the smoothing parameters of the Holt-Winters forecast function were used and the results after testing in the time series showed little differences among methods, so the use of the simple local search algorithms is recommended as they are easier to implement.

O auteur a ver-se a si mesmo ao espelho: as alegorias do enunciador em Jean Cocteau

ABSTRACT - Jean Cocteau, French cinema auteur avant la lettre, has consecrated his uniqueness to the defense of the “poet” and the promotion of its artistic ideals, before the French Nouvelle Vague inspired the break away from the filmic tradition and ahead of the eulogistic tendency to consider the director the undisputed creative entity of the filmmaking process. The Orphic trilogy expresses Cocteau’s cinematic philosophy in action. In other words, it reveals the way by which the creative entity affirms itself as the major filmic enunciator, through an allegorical relationship with vision. Therefore, Cocteau’s self-reflexive metacinema conjoins, in a fertile attunement, the starting point and the ultimate goal, the creation and the reception. Without being exactly a cinema about the cinema, this artistic practice is, nonetheless, very much with the cinema, feeding as it does on its essence. The films Le Sang d’un poète (“The Blood of a Poet”, 1932), Orphée (“Orpheus”, 1950) and Le Testament d’Orphée, ou ne me demandez pas pourquoi! (“Testament of Orpheus”, 1960) recreate, in allegorical form, the double creative function: the look of the directing entity reflects the gaze of the observer, just as this one always restores the presence of the creator. In short: Cocteau’s films, more than anyone else’s, deliberately reflect its auteur as enunciator.

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.

Proposal of a short-form version of the Brazilian Food Insecurity Scale

OBJECTIVE To propose a short version of the Brazilian Food Insecurity Scale. METHODS Two samples were used to test the results obtained in the analyses in two distinct scenarios. One of the studies was composed of 230 low income families from Pelotas, RS, Southern Brazil, and the other was composed of 15,575 women, whose data were obtained from the 2006 National Survey on Demography and Health. Two models were tested, the first containing seven questions, and the second, the five questions that were considered the most relevant ones in the concordance analysis. The models were compared to the Brazilian Food Insecurity Scale, and the sensitivity, specificity and accuracy parameters were calculated, as well as the kappa agreement test. RESULTS Comparing the prevalence of food insecurity between the Brazilian Food Insecurity Scale and the two models, the differences were around 2 percentage points. In the sensitivity analysis, the short version of seven questions obtained 97.8% and 99.5% in the Pelotas sample and in the National Survey on Demography and Health sample, respectively, while specificity was 100% in both studies. The five-question model showed similar results (sensitivity of 95.7% and 99.5% in the Pelotas sample and in the National Survey on Demography and Health sample, respectively). In the Pelotas sample, the kappa test of the seven-question version totaled 97.0% and that of the five-question version, 95.0%. In the National Survey on Demography and Health sample, the two models presented a 99.0% kappa. CONCLUSIONS We suggest that the model with five questions should be used as the short version of the Brazilian Food Insecurity Scale, as its results were similar to the original scale with a lower number of questions. This version needs to be administered to other populations in Brazil in order to allow for the adequate assessment of the validity parameters.