Bandgap engineering by substitution of S by Se in nanostructured ZnS1−xSex thin films grown by soft chemical route for nontoxic optoelectronic device applications

Thin films of nanostructured ZnS_1−xSe_x with optimized growth parameters were prepared by soft chemical route on glass substrates. Ammonia free precursors were used at 80 °C constant bath temperature. The ratio of sulphur to selenium was changed continuously by changing the composition x (0-1), while atomic concentration of zinc was kept constant. Structure, composition and surface morphology of as-deposited films were characterized by X-ray diffraction (XRD), energy dispersive X-ray analysis (EDAX) and scanning electron microscopy (SEM), atomic force microscopy (AFM) respectively. XRD studies revealed that as-deposited films were nanostructured in nature with cubic zinc blended structure. It was further observed that the preferred orientations are along (1 1 1) plane and crystallite size decreased with increase in the value of x. SEM and AFM images revealed that films were uniform and pinhole free. The optical band gap (E_g) was calculated from the observed transmittance spectra by Urbach method. It was found that the band gap varied linearly from 3.71 to 2.70 eV, as composition x varies 0-1. The electrical properties’ study revealed that the decrease in resistivity and increase in photosensitivity, as composition x varied 0-1. The observed interesting properties of ZnS_1−xSe_x thin films justified their significance in optoelectronic device fabrication and applications, and as an environment friendly alternative to the commonly used toxic material such as CdS.     

Superconductors of SmFe1−xCoxAsO synthesized by mechanical alloying

The SmFe_1−xCo_xAsO (x = 0 − 0.25) superconductors were synthesized by mechanical alloying (MA) and rapid sintering method with Co atoms doped into FeAs layers to replace the Fe sites. The phase purity and superconducting properties of the samples were characterized by X-ray diffraction, electrical resistivity, magnetic susceptibility and Hall coefficient. All the samples belong to the tetragonal ZrCuSiAs structure type with the grain size in 1-3 μm. The superconducting critical temperature T_c of SmFe_0.9Co_0.1AsO was 12.5 K, and the structure/SDW transition was suppressed by Co doping. The negative Hall coefficient of SmFe_0.9Co_0.1AsO indicated the electron conduction in the sample. The charge carrier density is about 2 × 10²⁰ cm⁻³ at the temperature lower than 150 K, larger than that of SmFeAsO.     

Synthesis and thermoelectric properties of the PbSe1−xTex alloys

The PbSe_1−xTe_x alloys with x = 0.2, 0.3, 0.5, 0.85 and 1.0 were prepared by induction melting, ball milling and spark plasma sintering techniques. The thermoelectric properties of the samples were investigated. The XRD analysis indicated that all samples are NaCl-type structure solid solutions Pb(Se,Te) containing nanograins. Increasing Te content resulted in increasing the lattice parameter a. The thermoelectric measurements show that all samples are n-type semiconductors in temperature range from 300 K to 673 K. The electrical resistivity of the doped sample is much smaller than that of pure PbSe, but comparable to that of PbTe. The absolute Seebeck coefficients for the doped sample PbSe_1−xTe_x with x = 0.2, 0.3 and 0.5 range from 150 μV/K at 300 K to 250 μV/K at 673 K, which is much larger than that of pure PbSe (66-138 μV/K), but smaller than that of PbTe (230-310 μV/K) in the same experimental conditions. The thermal conductivity for the doped sample PbSe_1−xTe_x with x = 0.2, 0.3 and 0.5 range from 0.95 to 0.66 W/m K, which is much smaller than that of pure PbSe (2.1-1.3 W/m K) or PbTe (1.4-1.1 W/m K). As a result, the figure of merit for the doped sample can be enhanced. The maximum dimensionless figure of merit ZT of 1.15 was obtained in the sample PbTe_0.5Se_0.5 at 573 K, more than 50% higher than that of pure PbTe prepared in the same condition.     

CuIn1−xAlxS2 thin films prepared by sulfurization of metallic precursors

CuIn_1−xAl_xS₂ thin films (x = 0, 0.09, 0.27, 0.46, 0.64, 0.82 and 1) with thicknesses of approximately 1 μm were formed by the sulfurization of DC sputtered Cu-In-Al precursors. All samples were sulfurized in a graphite container for 90 min at 650 °C in a 150 kPa Ar + S atmosphere. Final films were studied via X-ray diffraction (XRD), scanning electron microscopy (SEM) and micro-Raman spectroscopy. It was found that all samples were polycrystalline in nature and their lattice parameters varied slightly nonlinearly from {a = 5.49 Å, c = 11.02 Å} for CuInS₂ to {a = 5.30 Å, c = 10.36 Å} for CuAlS₂. No unwanted phases such as Cu_2−xS or others were observed. Raman were recorded at a room temperature and the most intensive and dominant A₁ phonon frequency varied nonlinearly from 294 cm⁻¹ (CuInS₂) to 314 cm⁻¹ (CuAlS₂).     

Electrical properties of binder-free thick film BaYxBi1−xO3 NTC thermistors

The microstructure and electrical properties of BaY_xBi_1−xO₃ thick film negative temperature coefficient thermistors, fabricated by screen printing, were investigated. The sintered thick films were the single-phase solid solutions of the BaY_xBi_1−xO₃ compounds with a monoclinic structure. The added Y₂O₃ led to a significant decrease in the grain size of the thermistors. The resistivity and coefficient of temperature sensitivity for the BaY_xBi_1−xO₃ (0 ≤ x ≤ 0.15) thick film NTC thermistors decreased first with increasing x in the range of x < 0.04 and then increased with further increase in x.     

Effect of the sintering temperature on the properties of nanocrystalline Ca1−xSmxMnO3 (0 ≤ x ≤ 0.4) powders

Nanocrystalline Ca_1−xSm_xMnO₃ (0 ≤ x ≤ 0.4) manganites were prepared by a soft chemical method (Pechini method) followed by auto-combustion and sintering in air at 1073 or 1473 K. Single-phase powders with general composition Ca_1−xSm_xMnO₃ were obtained after 18 h annealing. The particle and grain sizes of the substituted Sm-manganites did not exhibit variation with samarium content, but increase with increasing the sintering temperature. All manganites show two active IR vibrational modes near 400 and 600 cm⁻¹ characteristic of the BO₆ octahedron vibrations.For the samples sintered at T_s = 1473 K, the partial substitution of calcium by samarium in the CaMnO₃ phase induces a marked decrease in the electrical resistivity, in the temperature range of 300-900 K, and at the same time a metal-to-insulator transition occurs; for T_s = 1073 K all the samples present semiconductor behaviour. With the increase of the annealing temperature the grain size increases and a metal-semiconductor transition appears. The results can be ascribed to the Mn⁴⁺/Mn³⁺ ratio and particle grain size. The effects of particle size on the electrical properties can be attributed to the domain status, changes in the Mn-O-Mn bond angle and Mn-O bond length.     

Fabrication and properties of Ba(Zr1−xCex)0.9Y0.1O2.95/NaCl composite electrolyte materials

Ba(Zr_1−xCe_x)_0.9Y_0.1O_2.95/NaCl (x = 0.1, 0.2 and 0.3) composite electrolyte materials were fabricated with ZnO as sintering aid. The effect of ZnO on the properties of Ba(Zr_1−xCe_x)_0.9Y_0.1O_2.95 matrix were investigated. The phase composition and microstructure of samples were characterized by XRD and SEM, respectively. The electrochemical performances were studied by three-probe conductivity measurement and AC impedance spectroscopy. XRD results showed that Ba(Zr_1−xCe_x)_0.9Y_0.1O_2.95 with 2 mol% of ZnO was perovskite structure. The relative density of this sample was above 95% when sintered at 1450 °C for 6 h. By adding 10 mol% of NaCl to Ba(Zr_1−xCe_x)_0.9Y_0.1O_2.95 with 2 mol% of ZnO that was sintered at 1400 °C for 6 h, the conductivity was increased. The electrical conductivity of 1.26 × 10⁻² S/cm and activation energy of 0.23 eV were obtained when tested at 800 °C in wet hydrogen.     

Charge ordering analysis by electrical and dielectric measurements in Ca2−xPrxMnO4 (x = 0-0.2) compounds

Ca_2−xPr_xMnO₄ (0 ≤ x ≤ 0.2) polycrystalline ceramic powders were synthesized by sol-gel method. The X-ray diffraction (XRD) profiles were indexed with a tetragonal and orthorhombic structure for Ca₂MnO₄ and Pr-doped compounds, respectively. Electrical properties were investigated by dc and ac electrical measurements. The dc measurements have revealed an insulating state for all compounds in 80-350 K temperature range. Both dc and ac measurements have highlighted a charge ordering (CO) transition at T_CO = 233 and 245 K for x = 0.175 and 0.2, respectively. The CO state was found to be accompanied by a jump of the hopping activation energy and a rapid rise of both dielectric permittivity and imaginary part of ac electrical impedance.     

Synthesis and functional properties of the Ni1−xMnxFe2O4 ferrites

Nanocrystalline Ni_1−xMn_xFe₂O₄ (x = 0; 0.17; 0.34; 0.5) ferrite powders were successfully synthesized using the sol-gel combustion method, by using nitrates as cations source and citric acid (C₆H₈O₇) as combustion/chelating agent. The reaction advancement was observed by means of IR absorption spectroscopy, by monitoring two characteristic bands for the spinel compounds at about 600 cm⁻¹ and 400 cm⁻¹, respectively. The as-synthesized powders were characterized by IR spectroscopy, X-ray diffraction (XRD) and scanning electronic microscopy (SEM). The magnetic study shows that the saturation magnetization decreases with increasing the Mn addition, as result of the particle size reduction. The dielectric properties were measured as a function of frequency in the range of 10 Hz to 1 MHz. The real part of permittivity has values of ∼88 at 1 kHz and ∼7 at 1 Hz for x = 0. An increasing dielectric permittivity with increasing the amount of Mn is observed. For all the investigated compositions, both the real and imaginary parts of permittivity decrease with frequency.     

Influence of deposition conditions on mechanical and tribological properties of nanostructured TiN/CNx multilayer films

Nanostructured TiN/CN_x multilayer films were deposited onto Si (100) wafers and M42 high-speed-steel substrates using closed-filed unbalanced magnetron sputtering in which the deposition process was controlled by a closed loop optical emission monitor (OEM) to regulate the flow of N₂ gas. Multilayers with different carbon nitride (CN_x) layer thickness could be attained by varying the C target current (0.5 A to 2.0 A) during the deposition. It was found that the different bilayer thickness periods (i.e. the TiN layer thickness Λ_TiN was fixed at 3.0 nm while the CN_x layer thickness Λ_CNx was varied from 0.3 to 1.2 nm) significantly affected the mechanical and tribological properties of TiN/CN_x multilayer films. These multilayer films were characterized and analyzed by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), atomic force microscopy (AFM), Rockwell-C adhesion test, scratch test, pin-on-disc tribometer, and nanoindentation measurements. XPS analyses revealed that the chemical states, such as TiN, TiC, TiN_xO_y and TiO_2, existed in a TiN layer. Nanoindentation results showed that the hardness was highly dependent on the bilayer thickness. A maximum hardness of ~ 41.0 GPa was observed in a multilayer film at bilayer thickness Λ_TiN = 3.0 nm and Λ_CNx = 0.9 nm. All multilayer films exhibited extreme elasticity with elastic recoveries as high as 80% at 5 mN maximum load. The compressive stresses in the films (in a range of 1.5-3.0 GPa) were strongly related to their microstructure, which depended mainly on the incorporation of nitrogen in the films. By scratch and Rockwell-C adhesion tests, the multilayer films with smaller bilayer thicknesses (Λ_TiN = 3.0 nm, Λ_CNx = 0.3 and 0.6 nm) exhibited the best adhesion and cohesive strength. The critical load value obtained was as high as ~ 78 N for the films with Λ_TiN = 3.0 nm, Λ_CNx = 0.9 nm. The friction coefficient value for a multilayer at Λ_TiN = 3.0 nm and Λ_CNx = 0.9 nm was found to be low 0.11. These adhesive properties and wear performance are also discussed on the basis of microstructure, mechanical properties and tribochemical wear mechanisms.     

Synthesis of nanostructured CuxS thin films by chemical route at room temperature and investigation of their size dependent physical properties

Nanostructured semiconductors show very interesting physical properties than bulk crystal due to size effects that arises because of quantum confinement of the electronic states. Using cupric acetate and sodium thiosulphate as cationic and anionic precursor, nanostructured Cu₂S thin films were successfully prepared at room temperature by chemical bath deposition technique. By varying the deposition time from 9 to 24 h, the Cu₂S films of thickness 70-233 nm were prepared. The different characterization methods such as X-ray diffraction (XRD), scanning electron microscopy (SEM), optical absorption and electrical resistivity measurement techniques were used to investigate size dependent properties of Cu₂S thin films. As thickness increases, the hexagonal covellite phase of CuS observed at thickness 70 nm gets converted to monoclinic chalcosite phase of Cu₂S. The resistivity and activation energy is found to be thickness dependent. The optical band-gap energy increases from 2.48 to 2.90 eV as thickness decreases from 233 to 70 nm. The influence of film thickness on carrier concentration, mobility and thermo-emf is reported.     

DC magnetization investigations in Ti1−xMnxO2 nanocrystalline powder

In the present paper, DC magnetization investigation on the insulating nanocrystalline powder samples of Ti_1−xMn_xO₂ (x = 0, 0.05, 0.10, and 0.15) prepared by simple chemical route is reported. Structural measurements revealed phase pure anatase structure of TiO₂ when x ≤ 0.05 and a mixture of anatase and rutile TiO₂ along with the signature of Mn₃O₄ phase for x > 0.05. Magnetic measurements exhibited the presence of ferromagnetic ordering at room temperature in samples having either small fraction of Mn or no Mn at all. This ferromagnetic signature is accompanied with paramagnetic contribution which is found to dominate with increase in Mn concentration. The Ti_1−xMn_xO₂ sample having highest Mn concentration of x = 0.15 showed nearly paramagnetic behavior. However, at low temperatures, additional ferrimagnetic ordering arising due to Mn₃O₄ (T_C = 42 K) is evidenced in the doped samples. Consistent with the XRD investigations, the isofield DC-magnetization measurements under field cooled and zero field cooled (FC-ZFC) histories corroborated the presence of Mn₃O₄ phase. Also, distinct thermomagnetic irreversibility has been observed above 42 K. These results are suggestive of presence of weak ferromagnetic ordering possibly due to defects related with oxygen vacancies.     

Electron spin resonance and resistivity studies of charge-ordered Bi(1−x)SrxMnO3

In this paper we report the temperature dependent electron spin resonance (ESR) and electrical resistivity studies of Bi_(1−x)Sr_xMnO₃ (x = 0.3, 0.4, 0.45, and 0.5). The double integrated (DI) intensity of the ESR signal vs temperature (T) and ln DI vs 1000/T plots have been used to get information about magnetic interactions in the sample. A sharp change in the slope of this plot indicates the onset of long range antiferromagnetic (AFM) order. The Neel temperatures (T_N) of the sample increases with increase in Sr content. In the temperature range T > T_N, domains of ferromagnetic (FM) and AFM correlations co-exist. The contributions of AFM correlations increase with the increase in Sr content. The observation of weak ESR signal in the temperature range below T_N indicates the freezing of FM microdomains/inhomogeneities in the AFM long range ordered state. The resistivity (ρ) data are analyzed in view of polaron model and variable range hopping (VRH) models given by Mott and Efros-Shklovskii (ES). As per Motts VRH model, ln ρ varies linearly with T^−1/4 with a change in slope at T_N. The estimated values of hopping distance and localization length are reasonable. It is also found that ln ρ varies linearly with T^−1/2 in accordance with the ES VRH model. However, the estimated values of the model parameters are unrealistic. The ESR and resistivity data are also analyzed in view of phase separation (PS) model.     

A study of structural, optical and magnetic properties of Zn0.97−xCuxCr0.03O diluted magnetic semiconductors

A set of Zn_0.97−xCu_xCr_0.03O (0 ≤ x ≤ 0.03) samples has been synthesized by the sol-gel method. The structural, optical and magnetic properties of the samples were investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL) and vibrating sample magnetometer (VSM). With Cu doping concentration increasing up to 2 at%, the XRD results showed that all diffraction peaks corresponded to wurtzite structure of ZnO, but for Zn_0.94Cu_0.03Cr_0.03O, the secondary phase of Cu emerged. PL measurements showed that Zn_0.97−xCu_xCr_0.03O powders and pure ZnO with the Cu concentration varied from 0.00 to 0.02 exhibited obvious blue shift; the green emission peak could be effectively enhanced with the increase of the Cu concentration. Magnetic measurements indicated that room-temperature ferromagnetism of Zn_0.97−xCu_xCr_0.03O was an intrinsic property when Cu concentration was less than 0.02. The saturation magnetization of Zn_0.97−xCu_xCr_0.03O (x = 0, 0.01, 0.02) increased with the increase of the Cu concentration.     

Structural, magnetic and electrical properties of Bi1.4La0.6Sr2CaCu2−xMnxOy compounds

The Mn-doped compounds Bi_1.4La_0.6Sr₂CaCu₂O_y were prepared by sol-gel method. The structural variation was characterized systematically by X-ray diffraction (XRD), infrared (IR) spectra and Raman scattering spectra, respectively. The electrical and magnetic properties of the compounds were investigated by the temperature dependence of resistivity (R-T) and magnetic hysteresis loop (M (H)) measurements. Results indicate that the subtle change of lattice parameters has taken place in the compounds, which is attributed to CuO₂ planes canting and Mn valence alternation. In the condition of preserving Bi-2212 structure, Bi_1.4La_0.6Sr₂CaCu_2−xMn_xO_y compound has optimal resistivity and magnetism at x = 2%, which could provide a candidate as new barrier in Josephson junction in future.     

Dielectric properties of Cu substituted Ni0.5−xZn0.3Mg0.2Fe2O4 ferrites

Dielectric properties of Cu substituted Ni-Zn-Mg ferrite samples having the general formula Ni_0.5−xCu_xZn_0.3Mg_0.2Fe₂O₄ (where x = 0.0, 0.1, 0.2, 0.3, 0.4, and 0.5) synthesized by Pramanik method are reported. The single phase formation of the ferrites was confirmed by XRD technique. The lattice parameter is found to increase with increase in Cu content. Average grain size, obtained from SEM micrographs, is found to increase with increase in Cu content. Dielectric parameters were measured as a function of frequency at room temperature as well as at higher temperatures. The variation in dielectric constant (?′) with temperature at four different fixed frequencies viz. 1 kHz, 10 kHz, 100 kHz, and 1 MHz was also studied. The room temperature dielectric constant (?′) and dielectric loss (tan δ) are found to decrease with increase in frequency. The ac conductivity (σ_ac) is found to increase with increase in the frequency.     

Growth and characterization of chemical bath deposited Cd1−xZnxS thin films

Cd_1−xZn_xS (0 ≤ x ≤ 1) thin films have been deposited by chemical bath deposition method on glass substrates from aqueous solution containing cadmium acetate, zinc acetate and thiourea at 80 ± 5 °C and after annealed at 350 °C. The structural, morphological, compositional and optical properties of the deposited Cd_1−xZn_xS thin films have been studied by X-ray diffractometer, scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), photoluminescence (PL) and UV-vis spectrophotometer, respectively. X-ray diffraction analysis shows that for x < 0.8, the crystal structure of Cd_1−xZn_xS thin films was hexagonal structure. For x > 0.6, however, the Cd_1−xZn_xS films were grown with cubic structure. Annealing the samples at 350 °C in air for 45 min resulted in increase in intensity as well as a shift towards lower scattering angles. The parameters such as crystallite size, strain, dislocation density and texture coefficient are calculated from X-ray diffraction studies. SEM studies reveal the formation of Cd_1−xZn_xS films with uniformly distributed grains over the entire surface of the substrate. The EDX analysis shows the content of atomic percentage. Optical method was used to determine the band gap of the films. The photoluminescence spectra of films have been studied and the results are discussed.     

Hydrothermal synthesis of superconductors Ba1−xKxBiO3 and double perovskites Ba1−xKxBi1−yNayO3

Superconductors Ba_1−xK_xBiO₃ and body-centered double perovskites Ba_1−xK_xBi_1−yNa_yO₃ have been selectively synthesized by a facile hydrothermal route. The appropriate ratio and adding sequence of initial reagents, alkalinity, reaction temperature and time are the critical factors that influence the crystal growth of the compounds. The purity and homogeneity of the crystals were detected by the ICP, SEM, EDX and TEM studies. Magnetic measurements show that the superconducting transition temperatures T_C of Ba_1−xK_xBiO₃ decrease from 22 K (for x = 0.35) to 8 K (for x = 0.55) with increasing the K doping level.     

Fabrication and properties of p-type K doped Zn1−xMgxO thin film

A series of K doped Zn_1−xMg_xO thin films have been prepared by pulsed laser deposition (PLD). Hall-effect measurements indicate that the films exhibit stable p-type behavior with duration of at least six months. The band gap of the K doped Zn_1−xMg_xO films undergoes a blueshift due to the Mg incorporation. However, photoluminescence (PL) results reveal that the crystallinity decreased with the increasing of Mg content. The fabricated K doped p-type Zn_0.95Mg_0.05O thin film exhibits good electrical properties, with resistivity of 15.21 Ω cm and hole concentration of 5.54 × 10¹⁸ cm⁻³. Furthermore, a simple ZnO-based p-n heterojunction was prepared by deposition of a K-doped p-type Zn_0.95Mg_0.05O layer on Ga-doped n-type ZnO thin film with low resistivity. The p-n diode heterostructure exhibits typical rectification behavior of p-n junctions.     

Structural, optical and transport properties of Al doped BiFeO3 nanopowder synthesized by solution combustion method

Aluminum doped Bismuth ferrite (BFO) nanopowders (grain size 13-20 nm) having composition Bi_1−xAl_2xFe_1−xO₃ (x = 0.00, 0.025, 0.05, 0.10, 0.15, 0.20, 0.25 and 0.30) were successfully synthesized by solution combustion method using citric acid as fuel at a temperature as low as 200 °C. As-prepared samples were examined by powder XRD for phase identification and crystallite size determination. The d.c. resistivity as a function of temperature was measured by standard two probe setup which exhibits clear metal to insulator transition for all samples. FTIR analysis was carried out to identify the chemical bonds present in the system. The optical band gap was calculated from the UV-vis absorbance spectra using classical Tauc relation which was found to vary from 2.78 eV to 2.93 eV for different Al³⁺ concentrations. The activation energies calculated from the slopes of ln(ρ) versus 10³/T plots are in the range 0.54-0.73 eV.