Two-step annealed CdS/CdSe co-sensitizers for quantum dot-sensitized solar cells

CdS/CdSe co-sensitizers on TiO₂ films were annealed using a two-step procedure; high temperature (300 °C) annealing of TiO₂/CdS quantum dots (QDs), followed by low temperature (150 °C) annealing after the deposition of CdSe QDs on the TiO₂/CdS. For comparison, two types of films were prepared; CdS/CdSe-assembled TiO₂ films conventionally annealed at a single temperature (150 or 300 °C) and non-annealed films. The 300 °C-annealed TiO₂/CdS/CdSe showed severe coalescence of CdSe QDs, leading to the blocked pores and hindered ion transport. The QD-sensitized solar cell (QD-SSC) with the 150 °C-annealed TiO₂/CdS/CdSe exhibited better overall energy conversion efficiency than that with the non-annealed TiO₂/CdS/CdSe because the CdSe QDs annealed at a suitable temperature (150 °C) provided better light absorption over long wavelengths without the hindered ion transport. The QD-SSC using the two-step annealed TiO₂/CdS/CdSe increased the cell efficiency further, compared to the QD-SSC with the 150 °C-annealed TiO₂/CdS/CdSe. This is because the 300 °C-annealed, highly crystalline CdS in the two-step annealed TiO₂/CdS/CdSe improved electron transport through CdS, leading to a significantly hindered recombination rate.     

Structural and optical properties of amorphous Sb2S3 thin films deposited by vacuum thermal evaporation method

Sb₂S₃ thin films have been deposited by vacuum thermal evaporation onto glass substrates at various substrate temperatures in the range of 30–240 °C. Crushed powder of the synthesized Sb₂S₃ was used as raw material for the vacuum thermal evaporation. The structural investigation performed by means of X-ray diffraction (XRD) showed that the all as-deposited films present an amorphous structure and all the films were highly resistive. The reflectance and transmittance of the films are measured in the incident wavelength range 300–1800 nm. The absorption coefficient spectral analysis revealed the existence of long and wide band tails of the localized states in the low absorption region. The band tails width is calculated and found to be varying between 0.024 and 0.032 eV. The analysis of the absorption coefficient in the high absorption region revealed two direct forbidden band gaps between 1.78–1.98 eV and 1.86–2.08 eV.     

Lattice Compatibility Theory LCT investigations on physical and optical constants of antimony processed antimonite nano-films

Antimonite (Sb₂S₃) thin films have been synthesized through an annealing process in sulfur vapors at 300 °C of Sb thermal evaporated films. Deposited films have been characterized by X-ray diffraction, scanning electron microscopy and UV–vis–NIR spectroscopy. X-ray diagrams of these films have confirms that they were well crystallized in orthorhombic structure and some parameters such as the lattice parameter, crystallite size, microstrain and degree of preferred orientation have been reported and correlated with the effect of crystallite size. Optical properties of Sb₂S₃ films have been characterized by solid-state UV–visible absorption spectroscopy, and the band gap E_g was between 1.75 and 2.23 eV. Moreover, additional opto-thermal investigation and analyses within the framework of the Lattice Compatibility Theory provided plausible explanation for thickness-dependent incorporation of sulfur element inside antimony elaborated matrices.     

Photovoltaic structures using AgSb(S x Se1−x )2 thin films as absorber

Photovoltaic structures were prepared using AgSb(S _x Se_1?x )₂ as absorber and CdS as window layer at various conditions via a hybrid technique of chemical bath deposition and thermal evaporation followed by heat treatments. Silver antimony sulfo selenide thin films [AgSb(S _x Se_1?x )₂] were prepared by heating multilayers of sequentially deposited Sb₂S₃/Ag dipped in Na₂SeSO₃ solution, glass/Sb₂S₃/Ag/Se. For this, Sb₂S₃ thin films were deposited from a chemical bath containing SbCl₃ and Na₂S₂O₃. Then, Ag thin films were thermally evaporated on glass/Sb₂S₃, followed by selenization by dipping in an acidic solution of Na₂SeSO₃. The duration of dipping was varied as 3, 4 and 5 h. Two different heat treatments, one at 350 °C for 20 min in vacuum followed by a post-heat treatment at 325 °C for 2 h in Ar, and the other at 350 °C for 1 h in Ar, were applied to the multilayers of different configurations. X-ray diffraction results showed the formation of AgSb(S _x Se_1?x )₂ thin films as the primary phase and AgSb(S,Se)₂ and Sb₂S₃ as secondary phases. Morphology and elemental detection were done by scanning electron microscopy and energy dispersive X-ray analysis. X-ray photoelectron spectroscopic studies showed the depthwise composition of the films. Optical properties were determined by UV–vis–IR transmittance and reflection spectral analysis. AgSb(S _x Se_1?x )₂ formed at different conditions was incorporated in PV structures glass/FTO/CdS/AgSb(S _x Se_1?x )₂/C/Ag. Chemically deposited post-annealed CdS thin films of various thicknesses were used as window layer. J–V characteristics of the cells were measured under dark and AM1.5 illumination. Analysis of the J–V characteristics resulted in the best solar cell parameters of V _oc = 520 mV, J _sc = 9.70 mA cm^?2, FF = 0.50 and η = 2.7 %.     

Photoluminescence characteristics of ZnGa2O4 thin films prepared by chemical solution method

Zinc gallate (ZnGa₂O₄) thin film phosphors have been formed on ITO glass substrates by a chemical solution method with starting materials of zinc acetate dihydrate, gallium nitrate hydrate and 2-methoxiethanol as a solution. The thin films were firstly dried at 100 °C and fired at 500 °C for 30 min and then, annealed at 500 °C and 600 °C for 30 min under an annealing atmosphere of 3% H₂/Ar. XRD patterns of the thin film phosphors showed (311) and (220) peak indicating ZnGa₂O₄ crystalline phase in which all the (311) peaks of the film phosphors synthesized on ITO glass and soda-lime glass revealed high intensity with increasing annealing temperature from 500 °C to 600 °C. The ZnGa₂O₄ thin film phosphors represented marked change in AFM surface morphologies according to an annealing temperature under an annealing atmosphere (3% H2/Ar). The film phosphor, annealed at 600 °C, showed the embossed pattern with relatively regular spacing in AFM surface morphology. The ZnGa₂O₄ thin film phosphors formed on ITO glass, which were annealed at different temperatures and showed distinctive spectra with peak wavelengths of 434 nm and 436 nm in the blue emission region.     

Thermal stability and electronic structures of N-doped SiSb films for high temperature applications of phase-change memory

Undoped and N-doped Si_10.5Sb_89.5 films were deposited by magnetron sputtering. The X-ray diffraction spectra indicated that all of the films crystallized into crystalline Sb with a rhombohedral structure after annealing at 280°C for 3 min. X-ray photoelectron spectroscopy analysis indicated that the incorporated nitrogen combined with Si to form silicon nitride in the SiSb films. The changes in electrical resistance and thermal stability of the undoped and N-doped Si_10.5Sb_89.5 films were investigated. The crystallization temperature increased from ∼225°C to ∼250°C when 13 at.% nitrogen was added into the Si_10.5Sb_89.5 film and increased further with increasing nitrogen content. The thermal stability of the amorphous film was enhanced by nitrogen doping. The maximum temperature for 10-year retention of amorphous state of a pure Si_10.5Sb_89.5 film is ∼140°C and the temperature of N-doped Si_10.5Sb_89.5 films is even higher, which may be helpful to improve the data retention and performance of phase-change memory in high temperature applications.     

Improving the thermoelectric properties of thick Sb2Te3 film via Cu doping and annealing deposited by DC magnetron sputtering using a mosaic target

Thick Cu-doped Sb₂Te₃ films were deposited on flexible substrate by DC magnetron sputtering from a mosaic Cu–Sb₂Te₃ target. The Cu-doped Sb₂Te₃ films were vacuum annealed to improve their thermoelectric properties. Density functional theory was used to clarify the internal mechanism of the Cu doped into the Sb₂Te₃ system. The results showed that Cu substitution on a Sb site induced electronic states or impurity peaks of Sb₂Te₃ at a valence band maximum. The carrier concentration of the Cu-doped Sb₂Te₃ films increased as the Cu-doped concentration increased. However, the crystallite size and Seebeck coefficient of the Cu-doped Sb₂Te₃ films decreased as the Cu-doped concentration increased. Post-annealing treatment improved the microstructure and thermoelectric properties of the Cu-doped Sb₂Te₃ films. The maximum electrical conductivity and power factor values of 754.20 S/cm at 50 °C and 1.56 10⁻³ W/mK² at 100 °C were obtained in the annealed film with a Cu-doped concentration of 3 at%.     

Structural,optical, and electrical properties of tin sulfide thin films grown with electron-beam evaporation

The effect of growth temperature on the phase evolution and morphology change of tin sulfide thin films by electron-beam evaporation was investigated. Orthorhombic tin monosulfide (SnS) was dominant at low growth temperature of 25 °C, whereas a sulfur-rich phase of Sn₂S₃ coalesced as the growth temperature increased over 200 °C. Thin film growth ceased at 280 °C due to re-evaporation of the tin sulfide. The dependence of growth temperature on the phase evolution of tin sulfide was confirmed by X-ray diffraction, scanning electron microscopy, and UV–Vis spectrophotometry. The lowest electrical resistivity of ∼51 Ω cm, with a majority hole concentration of ∼10¹⁷ cm⁻³, was obtained for the film grown at 100 °C, and the resistivity drastically increased with increasing growth temperature. This behavior was correlated with the emergence of resistive sulfur-rich Sn₂S₃ phase at high temperatures.     

Influence of vacuum annealing on the structural and photoelectrochemical properties of nanocrystalline MoBi2S5 thin films

In the present paper we report structural, optical, morphological and electrical properties of thin films of MoBi₂S₅ prepared by facile self organized arrested precipitation technique (APT) from aqueous alkaline bath. X-ray diffraction study on thin films suggests orthorhombic and rhombohedral mixed phase structure. The samples are further annealed under vacuum at 373 and 473 K. The EDS pattern shows minor loss of sulphur upto 473 K. The optical absorption in visible region shows direct allowed transition with band gap variation over 1.2–1.1 eV. Post-heat treated samples exhibit n-type electrical conductivity. SEM images show uniform distribution of spherical grains with diameter ∼200 nm for as-synthesized MoBi₂S₅ thin film. The grain size increases with annealing temperature and morphology becomes more compact due to crystallization of thin film. The surface roughness deduced from AFM, was in the range of 1.29–1.92 nm. The MoBi₂S₅ thin films are employed for the fabrication of photoelectrochemical solar cells as all the samples exhibit strong absorption in visible to near IR region. Due to vacuum annealing it gives a significant enhancement of power conversion efficiency (η) upto 0.14% as compared to as-synthesized MoBi₂S₅ thin film.     

Investigation of Sb-rich Si2Sb2+x Te6 material for phase change random access memory application

Sb-rich Si₂Sb_2+x Te₆ (x=0, 1.4, 10) thin films are proposed to present the feasibility for electronic phase change memory application. The crystallization behavior is improved by adding Sb into the material. The crystallization temperature is about 506, 502, and 450 K for Si₂Sb₂Te₆, Si₂Sb_3.4Te₆, and Si₂Sb₁₂Te₆ films, respectively, and the corresponding activation energy is in the range from 2.70 to 1.69 eV, which is expected for a low-power and high-speed SET operation. In addition, maximum temperature for a 10 year data lifetime is estimated to be 133, 127, and 98°C, respectively. The memory devices are successfully fabricated employing these films, promising that the stability of the low-resistance crystalline state is improved by adding Sb into the stoichiometric Si₂Sb₂Te₆ material, and the reversibility of the device is also realized for the Si₂Sb₁₂Te₆-based cell.     

Band gap tunable and improved microstructure characteristics of Cu2ZnSn(S1−x,Sex)4 thin films by annealing under atmosphere containing S and Se

Cu₂ZnSn(S_xS_1?x)₄ (CZTSSe) thin films were prepared by annealing a stacked precursor prepared on Mo coated glass substrates by the sputtering technique. The stacked precursor thin films were prepared from Cu, SnS₂, and ZnS targets at room temperature with stacking orders of Cu/SnS₂/ZnS. The stacked precursor thin films were annealed using a tubular two zone furnace system under a mixed N₂ (95%) + H₂S (5%) + Se vaporization atmosphere at 580 °C for 2 h. The effects of different Se vaporization temperature from 250 °C to 500 °C on the structural, morphological, chemical, and optical properties of the CZTSSe thin films were investigated. X-ray diffraction patterns, Raman spectroscopy, and X-ray photoelectron spectroscopy results showed that the annealed thin films had a single kesterite crystal structure without a secondary phase. The 2θ angle position for the peaks from the (112) plane in the annealed thin films decreased with increasing Se vaporization temperature. Energy dispersive X-ray results showed that the presence of Se in annealed thin films increased from 0 at% to 42.7 at% with increasing Se vaporization temperatures. UV–VIS spectroscopy results showed that the absorption coefficient of all the annealed thin films was over 10⁴ cm^?1 and that the optical band gap energy decreased from 1.5 eV to 1.05 eV with increasing Se vaporization temperature.     

Structural and optical characterization of Sb-doped CuInS2 thin films grown by vacuum evaporation method

Structural, electrical and optical properties of Sb-doped CuInS₂ thin films grown by single source thermal evaporation method were studied. The films were annealed from 100 to 500 °C in air after the evaporation. The X-ray diffraction spectra indicated that polycrystalline CuInS₂ films were successfully obtained by annealing above 200 °C. This temperature was lower than that of non-doped CuInS₂ films. Furthermore, We found that the Sb-doped CuInS₂ thin films became close to stoichiometry in comparison with non-doped CuInS₂ thin films. The Sb-doped samples annealed above 200 °C has bandgap energy of 1.43–1.50 eV.     

Impact of growth temperature on the properties of SnS film prepared by thermal evaporation and its photovoltaic performance

Tin(II) sulfide (SnS) films are one of the most promising absorber materials for high efficiency solar cells without using rare metals. In this work, SnS films were deposited by the thermal evaporation on glass substrates under the variation of growth temperatures of 100–250 °C. It was revealed that the SnS thin film prepared under the temperature of 100 °C had relatively small crystal grains. On the other hand, the denser and larger crystal grains of the SnS films were obtained with the constant compositions, when the growth temperature increased to 225 °C. With the temperature of higher than 225 °C, the SnS began to be re-evaporated from the films. The highest Hall mobility of the films was obtained under the temperature of 200 °C. Ultimately, the results suggested that the optimized growth temperature of SnS by the evaporation is 200 °C, giving rise to compact and large crystal grains and the highest Hall mobility, thereby contributing to the 2.53%-efficient SnS thin-film solar cell.     

Optical properties of PMN–PT thin films prepared using pulsed laser deposition

(1 ? x)Pb(Mg_1/3Nb_2/3)O₃–xPbTiO₃ (PMN–PT) thin films have been deposited on quartz substrates using pulsed laser deposition (PLD). Crystalline microstructure of the deposited PMN–PT thin films has been investigated with X-ray diffraction (XRD). Optical transmission spectroscopy and Raman spectroscopy are used to characterize optical properties of the deposited PMN–PT thin films. The results show that the PMN–PT thin films of perovskite structure have been formed, and the crystalline and optical properties of the PMN–PT thin films can be improved as increasing the annealing temperature to 750 °C, but further increasing the annealing temperature to 950 °C may lead to a degradation of the crystallinity and the optical properties of the PMN–PT thin films. In addition, a weak second harmonic intensity (SHG) has been observed for the PMN–PT thin film formed at the optimum annealing temperature of 750 °C according to Maker fringe method. All these suggest that the annealing temperature has significant effect on the structural and optical properties of the PMN–PT thin films.     

Growth of AlN nanostructures by a rapid thermal process

Aluminum nitride nanorods were grown during rapid thermal annealing of multi-layered Al₂S₃ /BaS thin films. Depending on the thickness ratio between the BaS and Al₂S₃ layers, nanowires or straight nanorods were obtained. Typical dimensions for the nanorods were a diameter in the range of 50-100 nm and a length of 2-5 μm. The nanostructures are formed upon annealing at a relatively low temperature of 900 ^°C when aluminum evaporates from the thin film, but remains trapped between the thin film surface and the Si wafer, which is used as a support during the annealing. The nitrogen is provided by N₂ gas flushed through the annealing chamber. High-resolution transmission electron microscopy showed crystalline, wurtzite-structured AlN nanorods. The growth mechanism in terms of thin film composition, annealing parameters and the role of catalysts is discussed.     

Crystallization mechanism in Sb:Te thin films

The aim of this work is to study the mechanism of crystallization in Sb:Te thin films using differential scanning calorimetry (DSC), four-probe resistivity and X-ray diffraction (XRD) measurements.The DSC showed that the Sb_70+xTe_30−x films with x in the range of −3⩽x⩽3 show one exothermic reaction at 110 °C, whereas the films with x in the range of 3⩽x⩽13 present an additional one at about 70 °C. XRD measurements and Rietveld analysis have shown that the first exothermal peak can be associated to the formation of crystalline Sb and the second to the process of transformation of the Sb and the remaining material into a more stable Sb_2nTe₃ crystalline phase. Appearance of additional Sb phase decreases the crystallization temperature of Sb_70+xTe_30−x films.These structural transformations are also observed in the four-probe resistivity measurements: a one-step crystallization process in the Sb_70+xTe_30−x films with x in the range of −3⩽x⩽3and a two-steps crystallization process in films with x in the range of 3⩽x⩽13.The results of this investigation have shown that the amorphous-to-crystalline phase transformation in eutectic Sb:Te depended on the films composition.     

The film thickness dependent thermal stability of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>:Ag thin films as high-temperature solar selective absorbers

The monolayer Al₂O₃:Ag thin films were prepared by magnetron sputtering. The microstructure and optical properties of thin film after annealing at 700 °C in air were characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and spectrophotometer. It revealed that the particle shape, size, and distribution across the film were greatly changed before and after annealing. The surface plasmon resonance absorption and thermal stability of the film were found to be strongly dependent on the film thickness, which was believed to be associated with the evolution process of particle diffusion, agglomeration, and evaporation during annealing at high temperature. When the film thickness was smaller than 90 nm, the film SPR absorption can be attenuated until extinct with increasing annealing time due to the evaporation of Ag particles. While the film thickness was larger than 120 nm, the absorption can keep constant even after annealing for 64 h due to the agglomeration of Ag particles. On the base of film thickness results, the multilayer Al₂O₃:Ag solar selective thin films were prepared and the thermal stability test illustrated that the solar selectivity of multilayer films with absorbing layer thickness larger than 120 nm did not degrade after annealing at 500 °C for 70 h in air. It can be concluded that film thickness is an important factor to control the thermal stability of Al₂O₃:Ag thin films as high-temperature solar selective absorbers.     

Structural and magnetic properties of thin epitaxial Fe films on (1 1 0) GaAs prepared by metalorganic chemical vapor deposition

Iron films have been grown on (1 1 0) GaAs substrates by atmospheric pressure metalorganic chemical vapor deposition at substrate temperatures (T_s) between 135°C and 400°C. X-ray diffraction (XRD) analysis showed that the Fe films grown at T_s between 200°C and 330°C were single crystals. Amorphous films were observed at T_s below 200°C and it was not possible to deposit films at T_s above 330°C. The full-width at half-maximum of the rocking curves showed that crystalline qualities were improved at T_s above 270°C. Single crystalline Fe films grown at different substrate temperature showed different structural behaviors in XRD measurements. Iron films grown at T_s between 200°C and 300°C showed bulk α-Fe like behavior regardless of film thickness (100–6400 Å). Meanwhile, Fe films grown at 330°C (144 and 300 Å) showed a biaxially compressed strain between substrate and epilayer, resulting in an expanded inter-planar spacing along the growth direction. Magnetization measurements showed that Fe films (>200 Å) grown at 280°C and 330°C were ferromagnetic with the in-plane easy axis along the [1 1 0] direction. For the thinner Fe films (⩽200 Å) regardless of growth temperature, square loops along the [1 0 0] easy axis were very weak and broad.     

Simple solar cells of 3.5% efficiency with antimony sulfide‐selenide thin films

Thin films of antimony sulfide‐selenide solid solutions (Sb₂S_x Se_3–x) were prepared by chemical bath deposition and thermal evaporation to constitute solar cells of a transparent conductive oxide (FTO)/CdS/Sb₂S_x Se_3–x/C–Ag. The cell parameters vary depending on the sulfide‐selenide composition in the films. The best solar cell efficiency of 3.6% was obtained with a solid solution Sb₂S_1.5Se_1.5 prepared by thermal evaporation of the precipitate for which the open circuit voltage is 0.52 V and short circuit current density, 15.7 mA/cm²under AM 1.5G (1000 W/m²) solar radiation. For all‐chemically deposited solar cells of Sb₂S_1.1Se_1.9 absorber, these values are: 2.7%, 0.44 V, and 15.8 mA/cm², and for Sb₂S_0.8Se_2.2, they are: 2.5%, 0.38 V and 18 mA/cm². (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Effect of post annealing on the characteristics of In2S3 buffer layer grown by chemical bath deposition on a CIGS substrate

In₂S₃ as an alternative Cd-free buffer in Cu(In,Ga)Se₂ (CIGS) solar cells was deposited on CIGS substrate by a chemical bath deposition and characterized after post annealing to optimize film properties for CIGS solar cells. A uniform and pinhole-free In₂S₃ film was deposited on a CIGS substrate by H₂O₂ treatment prior to chemical bath deposition. The In₂S₃ layer was an amorphous state due to the co-existence of In–S, In–O, and In–OH bonds. Annealing at 200 °C induced copper diffusion from CIGS into In₂S₃ layer and lowered the band gap from 3.3 to 1.9 eV, leading to phase change from amorphous state to crystalline state. The conduction band alignment at the In₂S₃/CIGS interface can be controlled by the post annealing. The shunt current through In₂S₃ film was prevented down to the thickness of 30 nm and a 1.15 eV shallow defect was eliminated by the annealing. The results indicated that post annealing in air is a critical to fabricate CIGS solar cells with a sub-30 nm CBD-In₂S₃ buffer layer.