Selective synthesis of Bi2Se3 nanostructures by solvothermal reaction

Bi₂Se₃ nanobelts, nanoflakes and sheets embedded nanotubes were prepared via solvothermal process with different solvents. The reaction conditions influencing the synthesis of Bi₂Se₃ nanostructures such as solvents, and reaction temperatures were studied and optimized. Results indicated that the mixed solvent composed of triethanolamine and ethanol (TEA-EtOH) or triethanolamine and distilled water (TEA-H₂O) can decrease the threshold temperature (TT) of Bi₂Se₃. With the solvents TEA-EtOH and TEA-H₂O, we originally accomplished the shape-controlled synthesis of Bi₂Se₃ nanocrystals by controlling reaction temperature. Based on the viewpoint of crystallography about Bi₂Se₃, the possible growth mechanisms of Bi₂Se₃ nanostructures were discussed.     

In situ fabrication of Bi2S3 nanocrystal film for photovoltaic devices

A facile wet-chemical method to prepare Bi₂S₃ thin films with flake nanostructures directly on ITO glass substrate is presented in this paper for the first time. The product was characterized by X-ray powder diffractometer (XRD), Raman spectrometer, scanning electron microscope (SEM), and atomic force microscope (AFM). The one-step solvothermal elements treatment on the ITO substrate spare time to form film by spin-coating process and the film could be tightly attached to the ITO electrode. A conjugated polymer, poly 3-hexylthiophene (P3HT), was then spin-coated on the as-prepared Bi₂S₃ film to form an inorganic-organic hybrid thin film. The photovoltaic performance of the resulting solar cell device was also investigated.     

Anisotropic grain growth of Bi4Ti3O12 in molten salt fluxes

Bismuth titanate (Bi₄Ti₃O₁₂) platelets were obtained by the molten salt synthesis method in NaCl-KCl and Na₂SO₄-K₂SO₄ fluxes, using an amorphous Bi₄Ti₃O₁₂ precursor and a mechanically mixed Bi₂O₃-TiO₂ mixture as the starting materials. It was found that the synthesizing temperature, salt species and starting materials could significantly affect the crystallization habit and morphology of Bi₄Ti₃O₁₂ platelets. Under the same processing conditions (i.e. in Na₂SO₄-K₂SO₄ flux at 1000 °C), the Bi₄Ti₃O₁₂ platelets synthesized from the Bi₂O₃-TiO₂ mixture generally showed a smaller particle size than those synthesized using the amorphous Bi₄Ti₃O₁₂ precursor. The Bi₄Ti₃O₁₂ platelets prepared in the chloride flux were faceted along either (0 0 1) or (1 1 2) planes, while those prepared in the sulfate flux were solely (0 0 1) faceted. The former system also had smaller particle size than the latter. Furthermore, the salt content and the addition of plate-like Bi₄Ti₃O₁₂ seeds in the amorphous Bi₄Ti₃O₁₂ precursor showed a strong influence on the particle size of the synthesized Bi₄Ti₃O₁₂ platelets. The particle size of Bi₄Ti₃O₁₂ platelets prepared in the sulfate flux decreased as the mole ratio of the sulfate salts to Bi₄Ti₃O₁₂ was increased from 7.9 to 23.7. And the addition of 10 wt.% plate-like Bi₄Ti₃O₁₂ seeds into the amorphous Bi₄Ti₃O₁₂ precursor led to a significant increase in the particle size of the resulting Bi₄Ti₃O₁₂ platelets.     

Microstructural features and deformation-induced lattice defects in hot-extruded Bi2Te3 thermoelectric compound

Bismuth telluride (Bi₂Te₃) bulk material was prepared by a powder hot-extrusion technique. The microstructure, texture evolution, and deformation-induced lattice defects, as well as the effect of heat treatment on its microstructure and thermoelectric properties were investigated. As-extruded Bi₂Te₃ compound was found to be characterized by a dynamically and statically recrystallized microstructure with fine-equiaxed grains and low dislocation density. The majority of boundaries in the extruded specimens were large-angle boundaries with average misorientation angles of more than 30°. There was no significant change in dislocation configuration, even after heat treatment at a temperature higher than the extrusion temperature. Moreover, the Seebeck coefficient and electrical resistivity of the extruded specimens could not be improved by annealing. Microstructural examinations indicated the existence of a deformation-induced stacking disorder with local atomic shift, which we term “phase disorder,” on the basal plane in the extruded Bi₂Te₃ compound. The presence of this structural defect may be one of the main reasons for the slightly lower values of thermoelectric properties for the hot-extruded Bi₂Te₃ compound, compared with a unidirectionally solidified specimen.     

Controlled synthesis and photoluminescence properties of BaXO4 (X = W, Mo) hierarchical nanostructures via a facile solution route

Shape-controlled synthesis of BaWO₄ hierarchical nanostructures has been achieved in a mixed solvent of water and ethanol at room temperature. By simply adjusting the volume ratio of C₂H₅OH and H₂O (R ratio), the size and shape of BaWO₄ nanostructures, such as shuttle-like and ellipsoid-like, are successfully controlled. This simple method has been extended to synthesize BaMoO₄ hierarchical nanostructures. Both BaWO₄ and BaMoO₄ hierarchical nanostructures exhibited new green emission peaks at 558 and 560 nm, respectively.     

Effect of complexing agent on growth process and properties of nanostructured Bi2S3 thin films deposited by chemical bath deposition method

Nanostructured Bi₂S₃ thin films have been prepared onto amorphous glass substrates by chemical bath deposition method at room temperature using bismuth nitrate and sodium thiosulphate as cationic and anionic precursors with EDTA as complexing agent in aqueous medium. The X-ray diffraction study reveals that the films deposited without the complexing agent are amorphous in nature and becomes nanocrystalline in the presence of EDTA. The resistivity for the films prepared from EDTA complexed bath is decreased due to the improvement in grain structure. The decrease in optical bandgap and activation energy is observed as the thickness of the film varies from 45 to 211 nm on account of the variation of the volume of complexing agent in reaction bath. Studies reveal that the growth mechanism of Bi₂S₃ gets affected in the presence of complexing agent EDTA and shows impact on structural, electrical and optical properties.     

Silver cofirable Bi1.5Zn0.92Nb1.5O6.92 microwave ceramics containing CuO-based dopants

Bi₂O₃–ZnO–Nb₂O₅ system has emerged as a good low sintering (1050 °C) microwave material because it exhibits high dielectric constant and low temperature coefficient of resonance frequency (τ_f). We have lowered the sintering temperature of Bi_1.5Zn_0.92Nb_1.5O_6.92 (BZN) below 900 °C by using 3 wt.% of CuO-based dopants, such as 0.21BaCO₃–0.79CuO (BC) and 0.81MoO₃–0.19CuO (MC). The doped BZN exhibits high microwave dielectric constant at 2.3 GHz (k  120). The interfacial behavior between BZN and silver was investigated by using X-ray diffractometer, scanning electronic microscope, and electronic probe microanalyzer. The extent of silver migration of MC and BC dopants is reduced at least by one order of magnitude as compared with V₂O₅ dopant when the samples was prepared at 900 °C for 4 h. Thus, CuO-based dopants can replace V₂O₅ to lower the sintering temperature of BZN and to be cofired with silver.     

Effect of chromium substitution on structure and magnetic properties of Bi2Fe4O9

Orthorhombic Bi₂Fe_4 − xCr_xO₉ (x = 0.0, 0.25, and 0.75) nanoplatelets were synthesized by a simple hydrothermal method. The structure, morphology, and magnetic properties of the obtained powders have been characterized. Calculation of the lattice parameters of Bi₂Fe_4 − xCr_xO₉, as well as bond lengths and angles, was carried out by X-ray diffraction Rietveld refinement. The volumes of the metal-oxygen tetrahedra and octahedra were calculated to be sequentially increasing as the Cr doping level increases. The samples undergo an antiferromagnetic transition at 250 ± 5 K. The magnetic moments of the samples increase with higher Cr doping level. The 3d electron spin state for Fe³⁺ in the as-prepared samples is different, which is possibly due to the distortion of Fe-O tetrahedra and octahedra in the crystal structure after chromium substitution.     

Investigations of Bi substitution in NdBa2Cu3Oy

Attempts to substitute Bi for Nd in orthorhombic NdBa₂Cu₃O _y , prepared in air or oxygen at about 950°C led instead to formation of Ba₂NdBiO₆, a new cubic compound witha=0.8703 nm. The possibility was then explored of preparing superconducting (Nd_1–x Bi _x )Ba₂Cu₃O _y , by first forming the tetragonal phase at 880–950°C in nitrogen or argon followed by reheating in oxygen or air at 250–500°C in order to insert the additional oxygen required to yield the orthorhombic form while avoiding oxidation of Bi³⁺ to Bi⁵⁺. X-ray diffraction studies, electrical conductivity measurements, and thermogravimetric analysis of products indicate that Bi does not enter the NdBa₂Cu₃O _y , lattice in either the tetragonal or the orthorhombic phase. Ba₂NdBiO₆ clearly forms on reheating in oxygen or air even at low temperatures, and evidence is presented that a poorly crystallized oxygen-deficient form of this compound is already present prior to the reheating.     

Effect of mixed solvent on the morphologies of nanostructured Bi2S3 prepared by solvothermal synthesis

Different morphologies of nanostructured bismuth sulfide (Bi₂S₃) including nanotubes and nanorods have been prepared by solvothermal synthesis at a low temperature of 120 °C for 12 h using various mixed solvents as the reaction medium and urea as the mineralizer. X-ray diffraction analysis showed that all the as-prepared Bi₂S₃ samples are orthorhombic phase. Transmission electron microscopy analysis showed that the morphologies of the nanostructures are mainly related to the viscosity and surface tension of the mixed solvent used in the solvothermal synthesis.     

Effects of Bi2O3 and Cr2Ti3O9 Co-doping on dielectric properties in BaTiO3-based ceramics

A microwave ceramic with general composition (1-x-y) BaTiO₃ + x Cr₂Ti₃O₉ + y Bi₂O₃ has been prepared by solid state synthesis at 1300-1400 °C. The phase composition, perovskite structural parameters and dielectric properties have been obtained by X-ray diffraction and dielectric measurements as a function of chemical composition and temperature. At low doping levels the formation of BaTiO₃-based solid solution has been found. The precipitation of BaCrO₃ has been detected at x = y = 2.0 mol%. A model of the incorporation of Cr³⁺ and Bi³⁺ ions into BaTiO₃-based crystal lattice has been proposed. Diffused phase transition in the temperature range 100-140 °C have been revealed by dielectric measurements for different ceramic composition. As high dielectric constant as 7311 and as low dielectric loss as 0.02 have been found for the composition of 0.98BaTiO₃-0.01Cr₂Ti₃O₉-0.01Bi₂O₃.     

Observation of broadband infrared luminescence in a novel Bi-doped P2O5-B2O3-Al2O3 glass

A novel Bi-doped P₂O₅-B₂O₃-Al₂O₃ glass was investigated, and strong broadband NIR (near infrared) luminescence was observed when the sample was excited by 445 nm, 532 nm, 808 nm and 980 nm lasers, respectively. The max FWHM with 312 nm, the lifetime with 580 μs and the σ_emτ product with 5.3 × 10^− 24 cm² s were obtained which indicates that this glass is a promising material for broadband optical amplifier and tunable laser. The effect of the introduction of B₂O₃ on the glass structure and Bi-ions illuminant mechanism were discussed and analyzed. It is suggested that the introduction of B₂O₃ makes the glass structure closer, and the broadband NIR emission derives from Bi⁰:²D_3/2 → ⁴S_3/2 and Bi⁺:³P₁ → ³P₀ transitions.     

All-chemically deposited Bi2S3/PbS solar cells

We report on solar cells with a cross-sectional layout: TCO/window/Bi₂S₃/PbS, in which a commercial SnO₂ transparent conductive oxide (TCO-PPG Sungate 500); chemically deposited window layers of CdS, ZnS or their oxides; n-type Bi₂S₃ (100 nm) and p-type PbS (360-550 nm) absorber films constitute the cell structures. The crystalline structure, optical, and electrical properties of the constituent films are presented. The open circuit voltage (V_oc) and short-circuit current density (J_sc), for 1000 W/m² solar radiation, of these solar cells depend on the window layers, and vary in the range, 130-310 mV and 0.5-5 mA/cm², respectively. The typical fill factors (FF) of these cells are 0.25-0.42, and conversion efficiency, 0.1-0.4%.     

Growth and structure characterization of epitaxial Bi2Sr2Co2Oy thermoelectric thin films on LaAlO3 (001)

Epitaxial Bi₂Sr₂Co₂O_y thin films with excellent c-axis and ab-plane alignments have been grown on (001) LaAlO₃ substrates by chemical solution deposition using metal acetates as starting materials. Microstructure studies show that the resulting Bi₂Sr₂Co₂O_y films have a well-ordered layer structure with a flat and clear interface with the substrate. Scanning electron microscopy of the films reveals a step-terrace surface structure without any microcracks and pores. At room temperature, the epitaxial Bi₂Sr₂Co₂O_y films exhibit a resistivity of about 2 mΩ cm and a seebeck coefficient of about 115 μV/K comparable to those of single crystals.     

Investigation of Cu(In,Ga)Se2/In2S3 diffuse interface by Raman scattering

The CIGSe/In₂S₃ interface is known to be highly diffuse because of the migration of Cu from the CIGSe into the In₂S₃. Most of the analytical techniques allowing the determination of composition profiles throughout this interface involve ion etching either during the samples preparation or during data acquisitions. In the present work, we have explored the potential of the Raman scattering for the characterization of such interfaces. This technique is non destructive and provides information on both the composition and the structure of the materials that are probed. Three CIGSe/In₂S₃ structures have been investigated; the parameter varying being the substrate temperature during the In₂S₃ deposition. For the first time we could demonstrate that at high temperature, the CuInS₂ Cu-Au phase is formed at the CIGSe/In₂S₃ interface. Furthermore, the thickness of the ordered defect compound at the CIGSe surface increases with the deposition temperature. All of the new knowledge collected during this work shows the relevance of using the Raman scattering technique for the characterization of the CIGSe/In₂S₃ interface.     

One-pot synthesis of intestine-like SnO2/TiO2 hollow nanostructures

In the present study the intestine-like binary SnO₂/TiO₂ hollow nanostructures are one-pot synthesized in aqueous phase at room temperature via a colloid seeded deposition process in which the intestine-like hollow SnO₂ spheres and Ti(SO₄)₂ are used as colloid seeds and Ti-source, respectively. The novel core (SnO₂ hollow sphere)-shell (TiO₂) nanostructures possess a large surface area of 122 m²/g (calcined at 350 °C) and a high exposure of TiO₂ surface. The structural change of TiO₂ shell at different temperatures was investigated by means of X-ray diffraction and Raman spectroscopy. It was observed that the rutile TiO₂ could form even at room temperature due to the presence of SnO₂ core and the unique core-shell interaction.     

The low temperature synthesis and characterization of Bi3.25La0.75Ti3O12 powder by hydroxide coprecipitation in aqueous medium

The fine powders of Bi_3.25La_0.75Ti₃O₁₂ (BLT) were prepared by coprecipitaton method in aqueous medium at low temperature. The differential thermal analysis (DTA), thermo-gravimetric analysis (TG) and X-ray diffraction (XRD) were employed to evaluate the phase formation of BLT and TEM was used to characterize and observe the particle size and morphology of BLT powder obtained. The results show that the bismuth layer perovskite phase of BLT can begin to form at as low as 500 °C by the coprecipitation method. When the precipitates obtained were calcined at 600 °C for 2 h, the mono-phase and perfect BLT powder was synthesized. The BLT powder obtained consists of irregular or plate-like particles which are less than about 100 nm and is nearly aggregate free.     

Nest-like structures of Sr doped Bi2WO6: Synthesis and enhanced photocatalytic properties

A series of Sr-doped Bi₂WO₆ with three-dimensional (3D) nest-like structures were synthesized through simple hydrothermal route and characterized by XRD, FESEM, TEM, XPS, UV-vis DRS, etc. Morphology observation revealed that the as-synthesized Bi₂WO₆ were self-assembled three-dimensional (3D) nest-like structures, which were constructed from nanoplates. UV-vis diffuse reflectance spectra indicated that the samples had absorption in both UV and visible light areas. Their photocatalytic activities were evaluated by photodegradation of rhodamine B (RhB) under UV and visible light irradiation (λ > 420 nm). The photocatalytic properties were enhanced after Sr doping. Samples subsequently thermal treated at 500 °C showed higher photocatalytic activities. The reasons for the differences in the photocatalytic activities of these nest-like Bi₂WO₆ microstructures were further investigated.     

Spectroscopic properties of red Bi4Ge3O12 by vertical Bridgman method

Red Bi₄Ge₃O₁₂ (BGO) single crystals had been grown by vertical Bridgman (VB) method. The structure of this crystal was determined by XRD. The absorption and emission spectra of the red BGO in visible and near infrared region (NIR) were measured at room temperature. The emission intensity of the red BGO is weaker than that of ordinary BGO at about 500 nm. Interestingly, the red BGO shows a significant emission band centered at about 1495 nm. The red BGO faded and its properties recovered after ultraviolet (UV) irradiation or annealing.     

Hydrothermal synthesis of single-crystalline Bi2Te3 nanoplates

Novel Bi₂Te₃ nanoplates with about 0.2-1 μm in diagonal and 100 nm in thickness have been facilely synthesized via hydrothermal routes in the presence of polyvinylpyrrolidone (PVP). Various techniques such as X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), and Fourier transform infrared spectrometry (FT-IR) have been used to characterize the obtained products. The results show that the existence of PVP is vital to the formation of the plate-like morphology. Other factors, such as the reaction temperature and the different surfactants also have influence on the morphology of the final products to some extent.