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.

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.

InOx thin films deposited by plasma assisted evaporation: application in light shutters

An integration of undoped InOx and commercial ITO thin films into laboratory assembled light shutter devices is made. Accordingly, undoped transparent conductive InOx thin films, about 100 nm thick, are deposited by radiofrequency plasma enhanced reactive thermal evaporation (rf-PERTE) of indium teardrops with no intentional heating of the glass substrates. The process of deposition occurs at very low deposition rates (0.1-0.3 nm/s) to establish an optimized reaction between the oxygen plasma and the metal vapor. These films show the following main characteristics: transparency of 87% (wavelength, lambda = 632.8 nm) and sheet resistance of 52 Omega/sq; while on commercial ITO films the transparency was of 92% and sheet resistance of 83 Omega/sq. The InOx thin film surface characterized by AFM shows a uniform grain texture with a root mean square surface roughness of Rq similar to 2.276 nm. In contrast, commercial ITO topography is characterized by two regions: one smoother with Rq similar to 0.973 nm and one with big grains (Rq similar to 3.617 nm). For the shutters assembled using commercial ITO, the light transmission coefficient (Tr) reaches the highest value (Tr-max) of 89% and the lowest (Tr-min) of 1.3% [13], while for the InOx shutters these values are 80.1% and 3.2%, respectively. Regarding the electric field required to achieve 90% of the maximum transmission in the ON state (E-on), the one presented by the devices assembled with commercial ITO coated glasses is 2.41 V/mu m while the one presented by the devices assembled with InOx coated glasses is smaller, 1.77 V/mu m. These results corroborate the device quality that depends on the base materials and fabrication process used. (C) 2014 Elsevier Ltd. All rights reserved.

High-performance flexible hybrid field-effect transistors based on cellulose fiber paper

IEEE Electron Device Letters, VOL. 29, NO. 9,

PINPIN a-Si: H based structures for X-ray image detection using the laser scanning technique

Conventional film based X-ray imaging systems are being replaced by their digital equivalents. Different approaches are being followed by considering direct or indirect conversion, with the later technique dominating. The typical, indirect conversion, X-ray panel detector uses a phosphor for X-ray conversion coupled to a large area array of amorphous silicon based optical sensors and a couple of switching thin film transistors (TFT). The pixel information can then be readout by switching the correspondent line and column transistors, routing the signal to an external amplifier. In this work we follow an alternative approach, where the electrical switching performed by the TFT is replaced by optical scanning using a low power laser beam and a sensing/switching PINPIN structure, thus resulting in a simpler device. The optically active device is a PINPIN array, sharing both front and back electrical contacts, deposited over a glass substrate. During X-ray exposure, each sensing side photodiode collects photons generated by the scintillator screen (560 nm), charging its internal capacitance. Subsequently a laser beam (445 nm) scans the switching diodes (back side) retrieving the stored charge in a sequential way, reconstructing the image. In this paper we present recent work on the optoelectronic characterization of the PINPIN structure to be incorporated in the X-ray image sensor. The results from the optoelectronic characterization of the device and the dependence on scanning beam parameters are presented and discussed. Preliminary results of line scans are also presented. (C) 2014 Elsevier B.V. All rights reserved.

One-step preparation of optically transparent Ni-Fe oxide film electrocatalyst for oxygen evolution reaction

Optically transparent cocatalyst film materials is very desirable for improved photoelectrochemical (PEC)oxygen evolution reaction (OER) over light harvesting photoelectrodes which require the exciting light to irradiate through the cocatalyst side, i.e., front-side illumination. In view of the reaction overpotential at electrode/electrolyte interface, the OER electrocatalysts have been extensively used as cocatalysts for PEC water oxidation on photoanode. In this work, the feasibility of a one-step fabrication of the transparent thin film catalyst for efficient electrochemical OER is investigated. The Ni-Fe bimetal oxide films, 200 nm in thickness, are used for study. Using a reactive magnetron co-sputtering technique, transparent(> 50% in wavelength range 500-2000 nm) Ni-Fe oxide films with high electrocatalytic activities were successfully prepared at room temperature. Upon optimization, the as-prepared bimetal oxide film with atomic ratio of Fe/Ni = 3:7 demonstrates the lowest overpotential for the OER in aqueous KOH solution, as low as 329 mV at current density of 2 mA cm 2, which is 135 and 108 mV lower than that of as-sputtered FeOx and NiOx thin films, respectively. It appears that this fabrication strategy is very promising to deposit optically transparent cocatalyst films on photoabsorbers for efficient PEC water splitting.

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.

Evolution of the surface plasmon resonance of Au:TiO2 nanocomposite thin films with annealing temperature

This paper reports on the changes in the structural and morphological features occurring in a particular type of nanocomposite thin-film system, composed of Au nanoparticles (NPs) dispersed in a host TiO2 dielectric matrix. The structural and morphological changes, promoted by in-vacuum annealing experiments of the as-deposited thin films at different temperatures (ranging from 200 to 800 C), resulted in a well-known localized surface plasmon resonance (LSPR) phenomenon, which gave rise to a set of different optical responses that can be tailored for a wide number of applications, including those for optical-based sensors. The results show that the annealing experiments enabled a gradual increase of the mean grain size of the Au NPs (from 2 to 23 nm), and changes in their distributions and separations within the dielectric matrix. For higher annealing temperatures of the as-deposited films, a broad size distribution of Au NPs was found (sizes up to 100 nm). The structural conditions necessary to produce LSPR activity were found to occur for annealing experiments above 300 C, which corresponded to the crystallization of the gold NPs, with an average size strongly dependent on the annealing temperature itself. The main factor for the promotion of LSPR was the growth of gold NPs and their redistribution throughout the host matrix. On the other hand, the host matrix started to crystallize at an annealing temperature of about 500 C, which is an important parameter to explain the shift of the LSPR peak position to longer wavelengths, i.e. a red-shift.

Surface plasmon resonance-coupled photoluminescence and resistive switching behavior of pulsed laser-deposited Ag:SiC nanocermet thin films

In this study, Ag:SiC nanocermets were prepared via rapid thermal annealing (RTA) of pulsed laser-deposited SiC/Ag/SiC trilayers grown on Si substrate. Atomic force microscope images show that silver nanoparticles (Ag NPs) are formed after RTA, and the size of NPs increases with increasing Ag deposition time (t Ag). Sharp dip observed in the reflectance spectra confirmed the existence of Ag surface plasmons (SPs). The infrared transmission spectra showed an intense and broad absorption band around 780–800 cm−1 that can be assigned to Si-C stretching vibration mode. Influence of t Ag on the spectral characteristics of SP-enhanced photoluminescence (PL) and electrical properties of silicon carbide (SiC) films has been investigated. The maximum PL enhancement by 5.5 times for Ag:SiC nanocermets is achieved when t Ag ≈ 50 s. This enhancement is due to the strong resonant coupling between SiC and the SP oscillations of the Ag NPs. Presence of Ag NPs in SiC also induces a forming-free resistive switching with switching ratio of 2 × 10−2. The analysis of I–V curves demonstrates that the trap-controlled space-charge-limited conduction with filamentary model is the governing mechanism for the resistive switching in nanocerment thin films.

The influence of nitrogen and oxygen additions on the thermal characteristics of aluminium-based thin films

The ternary aluminium oxynitride (AlNxOy) system offers the possibility to obtain a wide range of properties by tailoring the ratio between pure Al, AlNx and AlOy and therefore opening a significant number of possible applications. In this work the thermal behaviour of AlNxOy thin films was analysed by modulated infrared radiometry (MIRR), taking as reference the binary AlOy and AlNx systems. MIRR is a non-contact and non-destructive thermal wave measurement technique based on the excitation, propagation and detection of temperature oscillations of very small amplitudes. The intended change of the partial pressure of the reactive gas (N2 and/or O2) influenced the target condition and hence the deposition characteristics which, altogether, affected the composition and microstructure of the films. Based on the MIRR measurements and their qualitative and quantitative interpretation, some correlations between the thermal transport properties of the films and their chemical/physical properties have been found. Furthermore, the potential of such technique applied in this oxynitride system, which present a wide range of different physical responses, is also discussed. The experimental results obtained are consistent with those reported in previous works and show a high potential to fulfil the demands needed for the possible applications of the systems studied. They are clearly indicative of an adequate thermal response if this particular thin film system is aimed to be applied in small sensor devices or in electrodes for biosignal acquisition, such as those for electroencephalography or electromyography as it is the case of the main research area that is being developed in the group.

Evolution of the functional properties of titanium–silver thin films for biomedical applications: Influence of in-vacuum annealing

In this work, the thermal stability of TiAgx thin films, deposited by magnetron sputtering, was evaluated, envisaging their application in biomedical devices, namely as electrodes for biosignal acquisition. Based on the composition and microstructural characterization, a set of four representative TiAgx thin films was selected in order to infer whether they are thermally stable in terms of functional properties. In order to achieve this purpose, the structural and morphological evolution of the films with annealing temperature was correlated with their electrical, mechanical and thermal properties. Two distinct zones were identified and two samples from each zone were extensively analysed. In the first zone (zone I), Ti was the main component (Ti-rich zone) while in the second, zone II, the Ag content was more significant. The selected samples were annealed in vacuum at four different temperatures up to 500 oC. For the samples produced within zone I, small microstructural changes were observed due to the recrystallization of the Ti structure and grain size increment. Also, no significant changes were observed with annealing temperature regarding the f l ’ functional properties, being thermally stable up to 500 oC. For higher Ag contents (zone II) the energy supplied by thermal treatments was sufficient to activate the crystallization of Ti-Ag intermetallic phases. A strong increase of the grain size of these phases was also reported. The structural and morphological organization proved to be determinant for the physical responses of the TiAgx system. The hardness and Y g’s modulus were significantly improved with the formation of the intermetallic phases. The silver addition and annealing treatments also played an important role in the electrical conductivity of the films, which was once again improved by the formation of Ti-Ag phases. The thermal diffusivity of the films was practically unchanged with the heat-treatment. This set of results shows that this intermetallic-like thin film system has good thermal stability up to high temperatures (as high as 500 oC), which in case of the highest Ag content zone is particularly evident for electrical and mechanical properties, showing an important improvement. Hardness increases about three times, while resistivity values become half of those from the lowest Ag contents zone. These set of characteristics are consistent with the targeted applications, namely in terms of biomedical sensing devices.

Morphology and oxygen incorporation effect on antimicrobial activity of silver thin films

Ag and AgxO thin films were deposited by non-reactive and reactive pulsed DC magnetron sputtering, respectively, with the final propose of functionalizing the SS316L substrate with antibacterial properties. The coatings were characterized chemically, physically and structurally. The coatings nanostructure was assessed by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), while the coatings morphology was determined by scanning electron microscopy (SEM). The XRD and XPS analyses suggested that Ag thin film is composed by metallic Ag, which crystallizes in fcc-Ag phase, while the AgxO thin film showed both metallic Ag and Ag-O bonds, which crystalize in fcc-Ag and silver oxide phases. The SEM results revealed that Ag thin film formed a continuous layer, while AgxO layer was composed of islands with hundreds of nanometers surrounded by small nanoparticles with tens of nanometers. The surface wettability and surface tension parameters were determined by contact angle measurements, being found that Ag and AgxO surfaces showed very similar behavior, with all the surfaces showing a hydrophobic character. In order to verify the antibacterial behavior of the coatings, halo inhibition zone tests were realized for Staphylococcus epidermidis and Staphylococcus aureus. Ag coatings did not show antibacterial behavior, contrarily to AgxO coating, which presented antibacterial properties against the studied bacteria. The presence of silver oxide phase along with the development of different morphology were pointed as the main factors in the origin of the antibacterial effect found in AgxO thin film. The present study demonstrated that AgxO coating presented antibacterial behavior and its application in cardiovascular stents is promising.

Magnetic hardening mechanisms in Nd-Fe-B nanocrystalline material

Microstructural and magnetic measurements of the evolution by heat treatment of initially amorphous Nd16Fe76B8 alloys prepared by melt spinning are presented. Evidence of magnetic hardening above a threshold temperature induced by magnetic isolation of the Nd2Fe14B grains is provided. A thermodynamic and kinetic explanation of local melting of the intergranular nanostructured Nd¿rich eutectic phase at temperatures below 900 K based on capillary effects is presented. A subsequent Ostwald ripening process moves Nd to wet intimately the hard magnetic grains, becoming, on cooling, a real paramagnetic isolating thin film (~2.5 nm). By using a simple analogy, it is shown that the switching magnetization field in a single¿domain crystal can be drastically affected through the exchange coupling to neighboring grains with different orientation of the easy axis. This effect should be important enough to reinforce the coercive field of polycrystalline hard magnetic materials and explains the observed enhancement from 0.9 to 1.9 T.

Dynamics of driven three-dimensional thin films: from hdrophilic to superhydrophobic substrates

We study the forced displacement of a thin film of fluid in contact with vertical and inclined substrates of different wetting properties, that range from hydrophilic to hydrophobic, using the lattice-Boltzmann method. We study the stability and pattern formation of the contact line in the hydrophilic and superhydrophobic regimes, which correspond to wedge-shaped and nose-shaped fronts, respectively. We find that contact lines are considerably more stable for hydrophilic substrates and small inclination angles. The qualitative behavior of the front in the linear regime remains independent of the wetting properties of the substrate as a single dispersion relation describes the stability of both wedges and noses. Nonlinear patterns show a clear dependence on wetting properties and substrate inclination angle. The effect is quantified in terms of the pattern growth rate, which vanishes for the sawtooth pattern and is finite for the finger pattern. Sawtooth shaped patterns are observed for hydrophilic substrates and low inclination angles, while finger-shaped patterns arise for hydrophobic substrates and large inclination angles. Finger dynamics show a transient in which neighboring fingers interact, followed by a steady state where each finger grows independently.