Precursors’ order effect on the properties of sulfurized Cu2ZnSnS4 thin films

A dc magnetron sputtering-based method to grow high-quality Cu2ZnSnS4 (CZTS) thin films, to be used as an absorber layer in solar cells, is being developed. This method combines dc sputtering of metallic precursors with sulfurization in S vapour and with post-growth KCN treatment for removal of possible undesired Cu2−xS phases. In this work, we report the results of a study of the effects of changing the precursors’ deposition order on the final CZTS films’ morphological and structural properties. The effect of KCN treatment on the optical properties was also analysed through diffuse reflectance measurements. Morphological, compositional and structural analyses of the various stages of the growth have been performed using stylus profilometry, SEM/EDS analysis, XRD and Raman Spectroscopy. Diffuse reflectance studies have been done in order to estimate the band gap energy of the CZTS films. We tested two different deposition orders for the copper precursor, namely Mo/Zn/Cu/Sn and Mo/Zn/Sn/Cu. The stylus profilometry analysis shows high average surface roughness in the ranges 300–550 nm and 230–250 nm before and after KCN treatment, respectively. All XRD spectra show preferential growth orientation along (1 1 2) at 28.45◦. Raman spectroscopy shows main peaks at 338 cm−1 and 287 cm−1 which are attributed to Cu2ZnSnS4. These measurements also confirm the effectiveness of KCN treatment in removing Cu2−xS phases. From the analysis of the diffuse reflectance measurements the band gap energy for both precursors’ sequences is estimated to be close to 1.43 eV. The KCN-treated films show a better defined absorption edge; however, the band gap values are not significantly affected. Hot point probe measurements confirmed that CZTS had p-type semiconductor behaviour and C–V analysis was used to estimate the majority carrier density giving a value of 3.3 × 1018 cm−3.

Optical measurements of rat muscle samples under treatment with ethylene glycol and glucose

With the objective to study the variation of optical properties of rat muscle during optical clearing, we have performed a set of optical measurements from that kind of tissue. The measurements performed were total transmittance, collimated transmittance, specular reflectance and total reflectance. This set of measurements is sufficient to determine diffuse reflectance and absorbance of the sample, also necessary to estimate the optical properties. All the performed measurements and calculated quantities will be used later in inverse Monte Carlo (IMC) simulations to determine the evolution of the optical properties of muscle during treatments with ethylene glycol and glucose. The results obtained with the measurements already provide some information about the optical clearing treatments applied to the muscle and translate the mechanisms of turning the tissue more transparent and sequence of regimes of optical clearing.

Thermodynamic pathway for the formation of SnSe and SnSe2 polycrystalline thin films by selenization of metal precursors

In this work, tin selenide thin films (SnSex) were grown on soda lime glass substrates by selenization of dc magnetron sputtered Sn metallic precursors. Selenization was performed at maximum temperatures in the range 300 °C to 570 °C. The thickness and the composition of the films were analysed using step profilometry and energy dispersive spectroscopy, respectively. The films were structurally and optically investigated by X-ray diffraction, Raman spectroscopy and optical transmittance and reflectance measurements. X-Ray diffraction patterns suggest that for temperatures between 300 °C and 470 °C, the films are composed of the hexagonal-SnSe2 phase. By increasing the temperature, the films selenized at maximum temperatures of 530 °C and 570 °C show orthorhombic-SnSe as the dominant phase with a preferential crystal orientation along the (400) crystallographic plane. Raman scattering analysis allowed the assignment of peaks at 119 cm−1 and 185 cm−1 to the hexagonal-SnSe2 phase and those at 108 cm−1, 130 cm−1 and 150 cm−1 to the orthorhombic-SnSe phase. All samples presented traces of condensed amorphous Se with a characteristic Raman peak located at 255 cm−1. From optical measurements, the estimated band gap energies for hexagonal-SnSe2 were close to 0.9 eV and 1.7 eV for indirect forbidden and direct transitions, respectively. The samples with the dominant orthorhombic-SnSe phase presented estimated band gap energies of 0.95 eV and 1.15 eV for indirect allowed and direct allowed transitions, respectively.

Admittance spectroscopy of Cu2ZnSnS4 based thin film solar cells

In this report, we propose an AC response equivalent circuit model to describe the admittance measurements of Cu2ZnSnS4 thin film solar cell grown by sulphurization of stacked metallic precursors. This circuit describes the contact resistances, the back contact, and the heterojunction with two trap levels. The study of the back contact resistance allowed the estimation of a back contact barrier of 246 meV. The analysis of the trap series with varying temperature revealed defect activation energies of 45 meV and 113 meV. The solar cell’s electrical parameters were obtained from the J-V curve: conversion efficiency, 1.21%; fill factor, 50%; open circuit voltage, 360 mV; and short circuit current density, 6.8 mA/cm2.

A study of ternary Cu2SnS3 and Cu3SnS4 thin films prepared by sulfurizing stacked metal precursors

Thin films of Cu2SnS3 and Cu3SnS4 were grown by sulfurization of dc magnetron sputtered Sn–Cu metallic precursors in a S2 atmosphere. Different maximum sulfurization temperatures were tested which allowed the study of the Cu2SnS3 phase changes. For a temperature of 350 ◦C the films were composed of tetragonal (I -42m) Cu2SnS3. The films sulfurized at a maximum temperature of 400 ◦C presented a cubic (F-43m) Cu2SnS3 phase. On increasing the temperature up to 520 ◦C, the Sn content of the layer decreased and orthorhombic (Pmn21) Cu3SnS4 was formed. The phase identification and structural analysis were performed using x-ray diffraction (XRD) and electron backscattered diffraction (EBSD) analysis. Raman scattering analysis was also performed and a comparison with XRD and EBSD data allowed the assignment of peaks at 336 and 351 cm−1 for tetragonal Cu2SnS3, 303 and 355 cm−1 for cubic Cu2SnS3, and 318, 348 and 295 cm−1 for the Cu3SnS4 phase. Compositional analysis was done using energy dispersive spectroscopy and induced coupled plasma analysis. Scanning electron microscopy was used to study the morphology of the layers. Transmittance and reflectance measurements permitted the estimation of absorbance and band gap. These ternary compounds present a high absorbance value close to 104 cm−1. The estimated band gap energy was 1.35 eV for tetragonal (I -42m) Cu2SnS3, 0.96 eV for cubic (F-43m) Cu2SnS3 and 1.60 eV for orthorhombic (Pmn21) Cu3SnS4. A hot point probe was used for the determination of semiconductor conductivity type. The results show that all the samples are p-type semiconductors. A four-point probe was used to obtain the resistivity of these samples. The resistivities for tetragonal Cu2SnS3, cubic Cu2SnS3 and orthorhombic (Pmn21) Cu3SnS4 are 4.59 × 10−2 cm, 1.26 × 10−2 cm, 7.40 × 10−4 cm, respectively.

CuxSnSx+1 (x = 2, 3) thin films grown by sulfurization of metallic precursors deposited by dc magnetron sputtering

We report the results of the growth of Cu-Sn-S ternary chalcogenide compounds by sulfurization of dc magnetron sputtered metallic precursors. Tetragonal Cu2SnS3 forms for a maximum sulfurization temperature of 350 ºC. Cubic Cu2SnS3 is obtained at sulfurization temperatures above 400 ºC. These results are supported by XRD analysis and Raman spectroscopy measurements. The latter analysis shows peaks at 336 cm-1, 351 cm-1 for tetragonal Cu2SnS3, and 303 cm-1, 355 cm-1 for cubic Cu2SnS3. Optical analysis shows that this phase change lowers the band gap from 1.35 eV to 0.98 eV. At higher sulfurization temperatures increased loss of Sn is expected in the sulphide form. As a consequence, higher Cu content ternary compounds like Cu3SnS4 grow. In these conditions, XRD and Raman analysis only detected orthorhombic (Pmn21) phase (petrukite). This compound has Raman peaks at 318 cm-1, 348 cm-1 and 295 cm-1. For a sulfurization temperature of 450 ºC the samples present a multi-phase structure mainly composed by cubic Cu2SnS3 and orthorhombic (Pmn21) Cu3SnS4. For higher temperatures, the samples are single phase and constituted by orthorhombic (Pmn21) Cu3SnS4. Transmittance and reflectance measurements were used to estimate a band gap of 1.60 eV. For comparison we also include the results for Cu2ZnSnS4 obtained using similar growth conditions.

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%.

Protein–polyphenol interaction on silica beads for astringency tests based on eye, photography or reflectance detection modes

Astringency is an organoleptic property of beverages and food products resulting mainly from the interaction of salivary proteins with dietary polyphenols. It is of great importance to consumers, but the only effective way of measuring it involves trained sensorial panellists, providing subjective and expensive responses. Concurrent chemical evaluations try to screen food astringency, by means of polyphenol and protein precipitation procedures, but these are far from the real human astringency sensation where not all polyphenol–protein interactions lead to the occurrence of precipitate. Here, a novel chemical approach that tries to mimic protein–polyphenol interactions in the mouth is presented to evaluate astringency. A protein, acting as a salivary protein, is attached to a solid support to which the polyphenol binds (just as happens when drinking wine), with subsequent colour alteration that is fully independent from the occurrence of precipitate. Employing this simple concept, Bovine Serum Albumin (BSA) was selected as the model salivary protein and used to cover the surface of silica beads. Tannic Acid (TA), employed as the model polyphenol, was allowed to interact with the BSA on the silica support and its adsorption to the protein was detected by reaction with Fe(III) and subsequent colour development. Quantitative data of TA in the samples were extracted by colorimetric or reflectance studies over the solid materials. The analysis was done by taking a regular picture with a digital camera, opening the image file in common software and extracting the colour coordinates from HSL (Hue, Saturation, Lightness) and RGB (Red, Green, Blue) colour model systems; linear ranges were observed from 10.6 to 106.0 μmol L−1. The latter was based on the Kubelka–Munk response, showing a linear gain with concentrations from 0.3 to 10.5 μmol L−1. In either of these two approaches, semi-quantitative estimation of TA was enabled by direct eye comparison. The correlation between the levels of adsorbed TA and the astringency of beverages was tested by using the assay to check the astringency of wines and comparing these to the response of sensorial panellists. Results of the two methods correlated well. The proposed sensor has significant potential as a robust tool for the quantitative/semi-quantitative evaluation of astringency in wine.

Heparinized nanohydroxyapatite/collagen granules for controlled release of vancomycin

The purpose of this study was to develop a bone substitute material capable of preventing or treating osteomyelitis through a sustainable release of vancomycin and simultaneously inducing bone regeneration. Porous heparinized nanohydroxyapatite (nanoHA)/collagen granules were characterized using scanning electron microscopy, micro-computed tomography and attenuated total reflectance Fourier transform infrared spectroscopy. After vancomycin adsorption onto the granules, its releasing profile was studied by UV molecular absorption spectroscopy. The heparinized granules presented a more sustainable release over time, in comparison with nonheparinized nanoHA and nanoHA/collagen granules. Vancomycin was released for 360 h and proved to be bioactive until 216 h. Staphylococcus aureus adhesion was higher on granules containing collagen, guiding the bacteria to the material with antibiotic, improving their eradication. Moreover, cytotoxicity of the released vancomycin was assessed using osteoblast cultures, and after 14 days of culture in the presence of vancomycin, cells were able to remain viable, increasing their metabolic activity and colonizing the granules, as observed by scanning electron microscopy and confocal laser scanning microscopy. These findings suggest that heparinized nanoHA/collagen granules are a promising material to improve the treatment of osteomyelitis, as they are capable of releasing vancomycin, eliminating the bacteria, and presented morphological and chemical characteristics to induce bone regeneration.