Enhancement of photosensitivity by annealing in Bi2S3 thin films grown using SILAR method

Bi₂S₃ thin films were grown by successive ionic layer adsorption and reaction method (SILAR) onto the glass substrates at room temperature. The as prepared thin film were annealed at 250 °C in air for 30 min. These films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM) and electrical measurement systems. The X-ray diffraction patterns reveal that Bi₂S₃ thin film have orthorhombic crystal structure. SEM images showed uniform deposition of the material over the entire glass substrate. The optical energy band gap observed to be decreased from 1.69 to 1.62 eV for as deposited and annealed films respectively. The I–V measurement under dark and illumination condition (100 W) show annealed Bi₂S₃ thin film gives good photoresponse as compared to as deposited thin film and Bi₂S₃ thin film exhibits photoconductivity phenomena suggesting its useful in sensors device. The thermo-emf measurements of Bi₂S₃ thin films revealed n-type electrical conductivity.     

Preparation and characterization of CdS–Bi2S3 nanocomposite thin film by successive ionic layer adsorption and reaction (SILAR) method

CdS, Bi₂S₃ and CdS–Bi₂S₃ nanocomposite thin films were grown by successive ionic layer adsorption and reaction method (SILAR) onto the glass substrates at room temperature. These films were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and electrical measurement systems. A comparative study was made between CdS, Bi₂S₃ and CdS–Bi₂S₃ nanocomposite thin films. The XRD patterns reveal that CdS, Bi₂S₃ and CdS–Bi₂S₃ nanocomposite thin film have hexagonal, orthorhombic and mixed phase of hexagonal CdS and orthorhombic Bi₂S₃ crystal structure, respectively. SEM images showed uniform deposition of the material over the entire glass substrate. The energy band gap for CdS, Bi₂S₃ and CdS–Bi₂S₃ thin films were revealed from the optical studies and were found to be 2.4, 1.6 and 1.69 eV, respectively. The thermoemf measurements of CdS–Bi₂S₃ nanocomposite thin film revealed n-type electrical conductivity, while the I–V measurement of CdS, Bi₂S₃ and CdS–Bi₂S₃ nanocomposite thin film under dark and illumination condition (100 mW/cm²) exhibited photoconductivity phenomena suggesting its applicability in photosensors devices.     

Microstructure and ferroelectric properties of dysprosium-doped bismuth titanate thin films

Bi₄Ti₃O₁₂ (BIT) ferroelectric thin films with Dy³⁺ substitution (Bi_4−xDy_xTi₃O₁₂, x = 0, 0.2, 0.4, 0.6, 0.8 and 1.0, respectively) were grown on Pt(111)/Ti/SiO₂/Si(100) substrates using sol–gel method. X-ray diffraction (XRD) and scanning electron microscopy (SEM) revealed that after annealing at 710 °C for 10 min, all Bi_4−xDy_xTi₃O₁₂ films became polycrystallites. Among all the deposited thin films, the Bi_3.4Dy_0.6Ti₃O₁₂ specimen exhibits improved ferroelectric properties with the largest average remanent polarization (2Pr) of 53.06 μC/cm² under applied field of 400 kV/cm and fatigue free characteristics (16% loss of 2Pr after 1.5 × 10¹⁰ switching cycles), indicating that it is suitable for non-volatile ferroelectric random access memories applications.     

Thickness and temperature effects on thermoelectric power and electrical resistivity of (Bi0.25Sb0.75)2Te3 thin films

Thin films (Bi_0.25Sb_0.75)₂Te₃ alloy of thickness in the range 400–2200 Å have been deposited on clean glass substrates by the flash evaporation technique in a vacuum of 1 × 10⁻⁵ Torr. Investigation by X-ray diffraction (XRD) and transmission electron microscopy (TEM) showed that all the films were polycrystalline and the grain size increased with increasing film thickness. Annealing treatment leads to grain growth. Electrical resistivity and thermoelectric power measurements were carried out for different thicknesses of the films in the temperature range 300–450 K. The dependences of resistivity and thermoelectric power on the temperature show that (Bi_0.25Sb_0.75)₂Te₃ films are semiconducting. Least square fit of electrical resistivity and thermoelectric power data with reciprocal thickness indicates that the results on (Bi_0.25Sb_0.75)₂Te₃ alloy films agree with the prediction of size effect theories. The effective mean free path model of size effect with perfect diffuse scattering is used for the analysis of the data. From the fit, the important physical parameters i.e., mean free path (l_g), bulk resistivity (ρ_g), bulk thermoelectric power (S_g) and energy dependent mean free path relation power index (U_g) have been evaluated.     

Physical properties of Bi2 (Te,Se)3 and Bi2Se1.2Te1.8 prepared using solid-state microwave synthesis

Bi₂(Te, Se)₃ and Bi₂Se_1.2Te_1.8 bulk products were synthesised using standard solid-state microwave synthesis. The Bi₂(Te, Se)₃ and Bi₂Se_1.2Te_1.8 were then deposited thermally onto glass substrates at a pressure of 10^? 6 Torr. The structure of the samples was analysed using X-ray diffraction (XRD), and the powders and thin films were observed to be polycrystalline and rhombohedral in structure. The surface morphology of the samples was determined using scanning electron microscopy (SEM). From the measurements of optical properties, the energy gap values for the Bi₂Te₃, Bi₂Se₃, and Bi₂Se_1.2Te_1.8 thin films were 0.43, 0.73, and 0.65 eV, respectively.     

Enhanced photoluminescence and electrical properties of 0-3 type ZnO/Bi3.6Eu0.4Ti3O12 nanocomposite thin films

0-3 type ZnO/Bi_3.6Eu_0.4Ti₃O₁₂ (BEuT) nanocomposite films with ZnO nanopowders in BEuT host were prepared by chemical solution deposition. The effects of ZnO content on the structure, photoluminescence, and electrical properties of the films were investigated. The ZnO/BEuT molar ratio strongly affected the grain size and growth orientation of BEuT, dielectric and ferroelectric properties, as well as emission intensity. The nanocomposite films showed strong red emission peaks due to ⁵D₀ → ⁷F₁ and ⁵D₀ → ⁷F₂ transitions of Eu³⁺ ions. Good electrical properties with high dielectric constant of 480 (at 1 kHz) and large remanent polarization (2P_r) of 32 μC/cm² were obtained for the nanocomposite films having a ZnO/BEuT molar ratio of 1:2. The mechanisms for enhanced photoluminescence and electric properties were discussed. The results suggest that the nanocomposite thin films are promising candidate materials for multifunctional optoelectronic devices.     

Cation distribution in the Bi4 − xRExTi3O12 (RE = La,Nd) solid solution and Curie temperature dependence

Bi_4 ? xRE_xTi₃O₁₂ (RE = La, Nd) ferroelectric powders were prepared by a co-precipitation route. Raman spectroscopy and X-ray diffraction were employed to determine the crystal site of La³⁺ and Nd³⁺ as well as the effect of their addition on the crystal structure. It was found that La atoms were not only placed preferentially in pseudo-perovskite A sites for concentrations x ≤ 1.2 but also substituted for Bi³⁺ in (Bi₂O₂)^2 + layers for greater concentrations. A similar behavior was observed with the limit value x = 0.8 in case of Nd³⁺. In solid solution La or Nd³⁺ ions diminish the distortions in the octahedron formed by oxygen atoms, so there is a tendency to undergo a transition in crystal symmetry from orthorhombic to tetragonal. Finally differential scanning calorimetry (DSC) shows a linear dependence of the Curie temperature (T_c) when the amount of La³⁺ or Nd³⁺ was increased.     

Photocatalytic degradation of an azo dye using Bi3.25M0.75Ti3O12 nanowires (M = La,Sm, Nd,and Eu)

Bi_3.25M_0.75Ti₃O₁₂ (BMT, M = La, Sm, Nd, and Eu) nanowires were synthesized through simple hydrothermal route and their structural and photocatalytic properties were investigated. XRD results indicated that these compounds are of layered perovskites structure. In addition, the band gaps of Bi_3.25La_0.75Ti₃O₁₂ (BLT), Bi_3.25Sm_0.75Ti₃O₁₂ (BST), Bi_3.25Nd_0.75Ti₃O₁₂ (BNT), and Bi_3.25Eu_0.75Ti₃O₁₂ (BET) were estimated to be about 2.403, 2.594, 2.525, and 2.335 eV, respectively. Their photocatalytic activities were evaluated by photocatalytic degradation of methyl orange (MO) under visible light irradiation (λ > 420 nm). Bi_3.25M_0.75Ti₃O₁₂ (M = La, Sm, Nd, and Eu) showed markedly higher catalytic activity compared to traditional N doped TiO₂ (N-TiO₂) and pure bismuth titanate (Bi₄Ti₃O₁₂, BIT) for MO photocatalytic degradation under visible light irradiation. The high photocatalytic performance of Bi_3.25M_0.75Ti₃O₁₂ photocatalysts could be attributed to the strong visible light absorption and the recombination restraint of the e^?/h⁺ pairs resulting from doping of rare earth metal ions. Furthermore, BET nanowires exhibited the highest photocatalytic activity.     

Effect of processing parameters on structural,morphological and optical Y2O3:Yb3+/Ho3+ powders characteristics

Rod-like and flake-like up-converting Y₂O₃:Yb³⁺/Ho³⁺ particles which are composed of nanoparticles with size less than 100 nm, are prepared by a simple hydrothermal processing at 473 K (3 h) followed by additional thermal treatment at 1373 K (3 and 12 h). The effect of precursor pH value on the formation of Y₂O₃:Yb³⁺/Ho³⁺ is followed through X-ray powder diffractometry (XRPD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). Structural refinement confirms formation of the cubic bixbyte structure (S.G. Ia-3) with the non-uniform accommodation of dopants at C₂ and S₆ cationic sites. Under 978 nm laser excitation, strong green (530–570 nm) up-conversion is observed in all samples. The emission shows a decrease in intensity with an increase in external temperature, indicating FIR (fluorescence intensity ratio) based temperature sensing behavior of 0.52% for the ⁵F₄ → ⁵I₈/⁵S₂ → ⁵I₈ transitions.     

Fabrication and electrical properties of Si-based La10−xBix(SiO4)6O3 apatite ionic conductor

In this paper we report an investigation about the relationship between Bi content and conductivity for the La_10?xBi_x(SiO₄)₆O₃ (x = 0.5–2) specimens. Increasing Bi content in apatite-type La_10?xBi_x(SiO₄)₆O₃ specimen leads to increasing the average grain size and sinterability because some Bi ion deposited at grain boundaries which promotes grain growth. The relative sintered density of the La₈Bi₂(SiO₄)₆O₃ specimen is 98%. There is a small shift in diffraction angle of XRD peaks, complicated lattice distortion was observed in the X-ray pattern with increasing content of Bi. Electrical conductivity of La_10?xBi_x(SiO₄)₆O₃ specimen increased with increasing Bi contents and the value of the La₈Bi₂(SiO₄)₆O₃ specimen is 2.4 × 10^?4 S cm^?1 at 700 °C.     

Second-order optical nonlinearities of metastable BiBO3 phases in crystallized glasses

Metastable BiBO₃ and rare-earth (RE)-doped RE_xBi_1−xBO₃ crystals were prepared through the crystallization of 50Bi₂O₃ · 50B₂O₃ and xRE₂O₃ · (50−x)Bi₂O₃ · 50B₂O₃ glasses (RE = Y, La, Gd, Yb), and their second harmonic (SH) intensities were examined using the Kurtz powder method. It was confirmed that BiBO₃ has two different crystalline forms, i.e., BiBO₃(I) and BiBO₃(II), and that BiBO₃(I) transforms into BiBO₃(II) at temperatures around 500 °C. Both phases were found to be nonlinear optical crystals with a phase matchable character, and the SH intensity of BiBO₃(II) powders was approximately 110 times as large as α-quartz powders. The incorporation of RE³⁺ into BiBO₃(II) was confirmed from X-ray diffraction analysis, and in particular, Gd_xBi_1−xBO₃(II) showed an enhanced SH intensity of approximately 145 times as large as α-quartz.     

Preparation,crystal structure and characterization of α-NaSbP2S6 and β-NaSbP2S6 phases

The new phases α-NaSbP₂S₆ and β-NaSbP₂S₆ were synthesized by ceramic and reactive flux methods at 773 K. The structures of α-NaSbP₂S₆ and β-NaSbP₂S₆ were determined by the single-crystal X-ray diffraction technique. α-NaSbP₂S₆ crystallizes in the monoclinic space group P2₁/c with a = 11.231(2) Å, b = 7.2807(15) Å, c = 11.640(2) Å, β = 108.99(3)°, V = 900.0(3) Å³ and z = 4. β-NaSbP₂S₆ crystallizes in the monoclinic space group P2₁ with a = 6.6167(13) Å, b = 7.3993(15) Å, c = 9.895(2) Å, β = 92.12(3) °, V = 484.10(17) Å³ and z = 2.The α- and β-phases of NaSbP₂S₆ are closely related, the main difference lies in the stacking of the [Sb[P₂S₆]]_nⁿ⁻ layers. The structure of α-NaSbP₂S₆ consists of two condensed layers (MPS₃ type) to give an ABAB… sequence with Na⁺ cations located in the interlayer space. The packing of β-NaSbP₂S₆ is formed by monolayers of [Sb[P₂S₆]]_nⁿ⁻ stacked in an AA… fashion separated by a layer of Na⁺ cations. Both phases are derivates of the M¹⁺M³⁺P₂Q₆ family.The optical band gaps of α-NaSbP₂S₆ and β-NaSbP₂S₆ were determined by UV–vis diffuse reflectance measurements to be 2.17 and 2.25 eV, respectively.     

Synthesis and characterization of Bi2S3 nanorods by solvothermal method in polyol media

Bi₂S₃ nanorods were synthesized via a simple solvothermal process in polyol media through the reaction between Bi(NO₃)₃·5H₂O, urea and CS₂ at 150 °C for 15 h using diethylene glycol as solvent. The nanorods were characterized by XRD, TEM and SAED. The results showed that the products were well-crystallized orthorhombic phase with lattice parameters a = 11.15 Å, b = 11.3 Å and c = 3.984 Å, which are consistent with the value in standard JCPDS card No. 17-0320. DEG served as an excellent solvent and structure director. Besides, compared to water and EG as solvents, the DEG system can provide a mild and homogenous condition, which is favorable to anisotropic growth and increases the yield of high quality Bi₂S₃ nanorods. Based on the experimental results, the growth mechanism was discussed.     

Facile preparation of heterostructured Bi2O3/Bi2MoO6 hollow microspheres with enhanced visible-light-driven photocatalytic and antimicrobial activity

Hierarchical β-Bi₂O₃/Bi₂MoO₆ heterostructured flower-like microspheres assembled from nanoplates with different β-Bi₂O₃ loadings (0–26.5 mol%) were synthesized through a one-step template-free solvothermal route. Under visible-light illumination (λ > 420 nm), over 99% of rhodamine B was degraded within 90 min on the 21.9 mol% of β-Bi₂O₃ loading Bi₂O₃/Bi₂MoO₆ microspheres. The remarkable enhancement of photocatalytic activity of the hierarchical Bi₂O₃/Bi₂MoO₆ micro/nanostructures can be attributed to the effective separation of the photoinduced charge carriers at the interfaces and in the semiconductors. The electrons (e⁻) are the main active species in aqueous solution under visible-light irradiation. The Bi₂O₃/Bi₂MoO₆ also displays visible-light photocatalytic activity for the destruction of E. coli. In addition, the β-Bi₂O₃ in the hierarchical Bi₂O₃/Bi₂MoO₆ microspheres is very stable and the composite can be easily recycled by a simple filtration step, thus the second pollution can be effectively avoided. A possible photocatalytic mechanism was proposed based on the experimental results.     

Lead-free electrostrictive bismuth perovskite ceramics with thermally stable field-induced strains

Electric field-induced strain (EFIS) properties of Bi_1/2(Na_0.82K_0.18)_1/2TiO₃ (BNKT) ceramics modified with Sr(K_1/4Nb_3/4)O₃ (SKN) have been investigated as functions of composition and temperature. BNKT ceramics near a phase boundary revealed the coexistence of ferroelectric rhombohedral and tetragonal phases, resulting in a typical ferroelectric butterfly-shaped bipolar S–E loop at room temperature, whose normalized strain (S_max/E_max) showed a significant temperature coefficient of 0.38 pm/V/K. However, 5 mol% SKN-modified BNKT ceramics revealed a typical electrostrictive behaviour with a thermally stable electrostrictive coefficient, Q₃₃ = 0.021 m⁴/C², which is almost comparable to that of Pb(Mg_1/3Nb_2/3)O₃ (PMN) ceramics that have been dominantly used as Pb-based electrostrictive materials over the last decades.     

Fluorescence properties and relaxation processes of Tb3+ ions in ZnCl2-based glasses

60ZnCl₂–20KCl–20BaCl₂–xTbCl₃ glasses (x = 0.10, 0.25, 0.50, 0.75, 1.00, and 1.25) were prepared by melt-quenching method, and Tb³⁺ fluorescence properties were investigated under 355 nm excitation. Regardless of x values, the electrons that were relaxed from the ⁵D₃ to ⁵D₄ level of Tb³⁺ ions by the multiphonon relaxation, were repressed to 28% of all the excited electrons because the ZnCl₂-based glass had much lower phonon energy than oxide glasses. For 0 < x ≤ 0.34, the cross relaxation, (⁵D₃ → ⁵D₄) → (⁷F₀ ← ⁷F₆), was repressed, and consequently 72% and 28% of all the excited electrons were radiatively relaxed by the ⁵D₃ → ⁷F_J (J = 6, 5, 4, 3, and 2) and ⁵D₄ → ⁷F_J (J = 6, 5, 4, and 3) transitions, respectively. The lifetimes of the ⁵D₃ and ⁵D₄ initial levels were obtained to be 1.1 and 2.1 ms, respectively.     

Lithium solubility limit in ZnGa2O4:Bi0.0013+,Li+ phosphor

The lithium solubility limit, photoluminescence (PL) and photoluminescence excitation (PLE) properties of lithium ion co-activated ZnGa₂O₄:Bi³⁺,Li⁺ phosphor have been investigated. A LiGaO₂ second phase began to appear from 3 mol% Li⁺ ion co-activated ZnGa₂O₄:Bi³⁺,Li⁺ phosphor. The enhanced brightness of blue (λ_ex = 254 nm) and white (λ_ex = 315 nm) colors of bismuth ions doped ZnGa₂O₄:Bi³⁺,Li⁺ phosphor was assigned to the formation of LiGaO₂. Bi³⁺ activated lithium zinc gallate phosphor showed a more enhanced PLE peak around 315 nm than that of lithium zinc gallate phosphor when λ_em = 520 nm. Thus, we observed that the PL intensity of ZnGa₂O₄:Bi³⁺,Li⁺ phosphor with λ_em = 520 nm was much greater than that of ZnGa₂O₄:Li⁺ phosphor. Also, ZnGa₂O₄:Bi³⁺,Li⁺ phosphor exhibited a shorter decay time than that of ZnGa₂O₄:Li⁺ phosphor by about a factor of about 2.     

Spectroscopic properties of B2O3–PbO–Bi2O3–GeO2 glass doped with Sm3+ and gold nanoparticles

Heavy metal oxide B₂O₃–PbO–Bi₂O₃–GeO₂ transparent glass doped with Sm³⁺ was synthesized and implanted with Au⁺ using energy of 300 keV and fluence of 1 × 10¹⁶ cm⁻². The annealing of the implanted glass at moderate temperature below the glass transition temperature induced the nucleation of gold nanoparticles, confirmed by the characteristic absorption band in the visible range and by transmission electron microscopy. Using Miés and Doylés theories for the surface plasmon resonance, the average size of the gold nanoparticles was about 4.6 nm, similar to the values observed by transmission electron microscopy. It was also observed the crystallization of a thin layer of the glass at the implanted surface after annealing, detected by X-ray diffraction and scanning electron microscope. Visible and near-infrared emission of Sm³⁺ was enhanced after annealing of the glass implanted with gold. Judd–Ofelt parameters and radiative parameters were calculated for the glass doped with Sm³⁺ with and without gold nanoparticles.     

Synthesis and photoluminescence study of La1.8Eu0.2O3 coating on nanometric α-Al2O3

In this work the La_1.8Eu_0.2O₃ coating on nanometric alpha-alumina, α-Al₂O₃@La_1.8Eu_0.2O₃, was prepared for the first time by a soft chemical method. The powder was heat-treated at 100, 400, 800 and 1200 °C for 2 h. X-ray powder diffraction patterns (XRD), transmission electronic microscopy (TEM), emission and excitation spectra, as well as Eu³⁺ lifetime were used to characterize the material and to follow the changes in structure as the heating temperature increases. The Eu³⁺ luminescence data revealed the characteristic transitions ⁵D₀ → ⁷F_J (J = 0, 1 and 3) of Eu³⁺ at around 580, 591 and 613 nm, respectively, when the powders were excited by 393 nm. The red color of the samples changed to yellow when the powder was annealed at 1200 °C. The decrease in the (⁵D₀ → ⁷F₂)/(⁵D₀ → ⁷F₁) ratio from around 5.0 for samples heated at lower temperatures to 3.1 for samples annealed at 1200 °C is consistent with a higher symmetry of the Eu³⁺ at higher temperature. The excitation spectra of the samples also confirms this change by the presence of a more intense and broad band at around 317 nm, instead of the presence of the characteristic peak at 393 nm, which corresponds to the ⁷F₀ → ⁵L₆ transition of the Eu³⁺. The lifetimes of the ⁵D₀ → ⁷F₂ transition of Eu³⁺ for the samples heat-treated at 100, 400, 800 and 1200 °C was evaluated as 0.57, 0.72, 0.43 and 0.31 ms, respectively.     

Formation and spectral probing of transparent oxyfluoride glass-ceramics containing (Eu2+, Eu3+:BaGdF5) nano-crystals

In the present study, we report the formation of transparent glass-ceramics containing BaGdF₅ nanocrystals under optimum ceramization of SiO₂–BaF₂–K₂O–Sb₂O₃–GdF₃–Eu₂O₃ based oxyfluoride glass and the energy transfer mechanisms in Eu²⁺ → Eu³⁺ and Gd³⁺ → Eu³⁺ has been interpreted through luminescence study. The modification of local environment surrounding dopant ion in glass and glass ceramics has been studied using Eu³⁺ ion as spectral probe. The optimum ceramization temperature was determined from the differential scanning calorimetry (DSC) thermogram which revealed that the glass transition temperature (T_g), the crystallization onset temperature (T_x), and crystallization peak temperature (T_p) are 563 °C, 607 °C and 641 °C, respectively. X-ray diffraction pattern of the glass-ceramics sample displayed the presence of cubic BaGdF₅ phase (JCPDS code: 24-0098). Transmission electron microscopy image of the glass-ceramics samples revealed homogeneous distribution of spherical fluoride nanocrystals ranging 5–15 nm in size. The emission transitions from the higher excited sates (⁵D_J, J = 1, 2, and 3) as well as lowered asymmetry ratio of the ⁵D₀ → ⁷F₂ transition (forced electric dipole transition) to that of the ⁵D₀ → ⁷F₁ transition (magnetic dipole) of Eu³⁺ in the glass-ceramics when compared to glass sample demonstrated the incorporation of dopant Eu³⁺ ions into the cubic BaGdF₅ nanocrystals with higher local symmetry with enhanced ionic nature. The presence of absorption bands of Eu²⁺ ions and Gd³⁺ ions present in the glass matrix or fluoride nanocrystals in the excitation spectra of Eu³⁺ by monitoring emission at 614 nm indicated energy transfer from (Eu²⁺ → Eu³⁺) and (Gd³⁺ → Eu³⁺) in both glass and glass-ceramics samples.