Spectroscopic properties of Er-Yb co-doped glass ceramics containing BaF2 nanocrystals

A Er³⁺ and Yb³⁺ co-doped transparent oxyfluoride glass ceramic containing BaF₂ nanocrystals has been prepared. The formation of BaF₂ nanocrystals in the glass ceramic was confirmed by X-ray diffraction. Intense upconversion luminescence in the Er³⁺ and Yb³⁺ co-doped glass ceramic could be observed. Stark splitting of the Er³⁺ upconversion luminescence peaks in the glass ceramic indicated that Er³⁺ and Yb³⁺ had been incorporated into the BaF₂ nanocrystals. Near infrared luminescence decay curves showed that the Er³⁺ and Yb³⁺ co-doped glass ceramic had higher luminescence efficiency than the precursor glass.     

A room temperature solution-phase process to synthesize pure phase single-crystalline hexagonal cobalt hydroxide nanoplates

A simple room temperature solution-phase method has been developed to synthesize pure phase single-crystalline hexagonal β-Co(OH)₂ nanoplates. The chemical composition and morphology of the as-prepared β-Co(OH)₂ nanoplates were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and selected area electron diffraction (SAED). The results indicated that the as-prepared β-Co(OH)₂ nanoplates were composed of pure brucite-like β-Co(OH)₂ phase with single-crystalline feature. The effect of polyethylene glycol (PEG), NH₄OH, and NaOH on the morphology and size of β-Co(OH)₂ nanocrystals were discussed in detail. The growth mechanism of the as-synthesized nanoplates was also discussed in detail based on the experimental results.     

Self-formation of dielectric layer containing CoSi2 nanocrystals by plasma-enhanced atomic layer deposition

Dielectric layer containing CoSi₂ nanocrystals was directly fabricated by plasma-enhanced atomic layer deposition using CoCp₂ and NH₃ plasma mixed with SiH₄ without annealing process. Synchrotron radiation X-ray diffraction and X-ray photoelectron spectroscopy results confirmed the formation of CoSi₂ nanocrystal. The gate stack composed of dielectric layer containing CoSi₂ nanocrystals with ALD HfO₂ capping layer together with Ru metal gate was analyzed by capacitance–voltage (C–V) measurement. Large hysteresis of C–V curves indicated charge trap effects of CoSi₂ nanocrystals. The current process provides simple route for the fabrication of nanocrystal memory compatible with the current Si device unit processes.     

Green synthesis of metal sulfide nanocrystals through a general composite-surfactants-aided-solvothermal process

In this paper, we developed a generalized and greener composite-surfactants-assisted-solvothermal process (CSSP) to produce colloidal nanoparticles of metal sulfides. X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectra (XPS) revealed that single-molecular-layer type of MoS₂ nanoparticles with diameter 6–10 nm were successfully synthesized. The molecular structure model of the capped MoS₂ nanoparticles was suggested through further examination by infrared spectra. Hexagonal CdS nanocrystals with spherical, triangle, and hollow sphere shapes were controllably synthesized by varying the experimental conditions. A possible in-situ reduction–sulfidation mechanism was proposed for the formation of Ag₂S nanocrystals, where the metal ions were reduced to metallic nanoparticles before the generation of sulfides. The obtained nanocrystals through this CSSP approach could provide the building blocks for the bottom-up approach to nanoscale fabrication in nanoscience and nanotechnology.     

Doped-metal oxide nanoparticles for use as photocatalysts

Nano-sized doped-metal oxides such as Fe-doped TiO₂, WO₃-doped ZnO and Fe-doped CeO₂ were synthesized by the modified sol-gel/impregnation, flame spray pyrolysis and homogeneous precipitation/impregnation methods respectively. The crystalline phase, particles size, and crystallinity of nano-sized powder were analyzed by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Specific surface area of the sample was examined by the Brunauer, Emmett and Teller (BET) adsorption–desorption of nitrogen gas. The photocatalytic activity of Fe-doped TiO₂, WO₃/ZnO, Fe-doped CeO₂ nanoparticles was examined by studying the mineralization of methanol, sucrose, glucose, oxalic acid and formic acid under UV and visible light irradiations in a pyrex spiral photoreactor. It was found that doped metal oxides could improve the photocatalytic activity of the pure metal oxides.     

Ferroelectric PbTiO3 Powders and Thin Films Derived from Sol-Gel Processing

Lead titanate powders and thin films were prepared by the sol-gel process of metal alkoxide solutions and solvents. From DSC measurements, phase transition temperature of crystallized PbTiO₃ powders was obtained at about 484 °C. From XRD investigation, it was confirmed that the tetragonal phase of polycrystalline PbTiO₃ thin films is formed by coating of concentrated solution on all of the substrates we used after heat treatment above 500 °C. It was found by SEM and ellipsometric analysis that the thin film coated with 0.25 M concentrated solutions once had an average thickness of about 720 Å. Surfaces of thin films were crack-free, uniform, and its average grain size investigated by SEM was 0.6–0.8 μm. Band gap energy of PbTiO₃ thin film coated on the Al₂O₃ (2243) substrate was 3.45 eV, which is assumed to be due to the direct band to band transition. Dielectric constant (ϵ) and dielectric loss (tan δ) of PbTiO₃ thin film amounted to 60–70 and 0.01–0.02 in the region of 10 kHz ∼ 1 MHz at room temperature, respectively, and transition temperature was 486 °C at 1 MHz. From the hysteresis loop of PbTiO₃ thin film, spontaneous polarization of 12 μC/cm² and coercive filed of 45 kV/cm were obtained.     

Optical and selected thermal properties of samarium-doped fluorochlorozirconate (FCZ) glass-ceramics: Formation and growth of BaCl2 nanocrystals in FCZ glass-ceramics

Photoluminescence (PL) and conventional and modulated temperature differential scanning calorimetry (DSC and MDSC) experiments have been carried out on a typical fluorochlorozirconate glass and glass-ceramics doped with Sm³⁺ and Sm²⁺ introduced by the addition of SmF₃ and a reducing agent, NaBH₄, into the initial mixture of constituents. The nominal FCZ composition was 53% ZrF₄, 20% NaF, 3% AlF₃, 3% LaF₃, 1% SmF₃, 1% BaF₂, 19% BaCl₂ (molar percentages). Prior to DSC and PL measurements, some of the glasses have been heat treated (annealed at an elevated temperature) under different conditions, which has resulted in glass-ceramics containing BaCl₂ nanocrystals with a hexagonal and/or orthorhombic crystal structure, depending on the heat treatment conditions. Hexagonal nanocrystals may be obtained by a simple one step annealing process while the formation of orthorhombic crystallites requires sequential multistep annealing treatments. Long duration, low temperature annealing, required for the formation of orthorhombic BaCl₂ nanocrystals, leads to the appearance of an endothermic enthalpy peak at around 250 °C on the conventional DSC thermogram. Temperature modulated DSC experiments identify a clear glass transformation in this regions; and the endothermic peak has been attributed to the structural relaxation enthalpy in the host glass which is usually obscured by the thermal effects associated with the formation of BaCl₂ nanocrystals. The observed thermodynamic effects correlate with the suppression of the broad PL band around 900 nm, which is most likely due to Sm²⁺ ions near or in the “shell-region” of the glass surrounding the nanocrystals.     

Thermal-induced phase transition and assembly of hexagonal metastable In2O3 nanocrystals: A new approach to In2O3 functional materials

This paper reports on the thermal-induced performance of hexagonal metastable In₂O₃ nanocrystals involving in phase transition and assembly, with particular emphasis on the assembly for the preparation of functional materials. For In₂O₃ nanocrystals, the metastable phase was found to be thermally unstable and transform to cubic phase when temperature was higher than 600 °C, accompanied by assembly as well as evolution of optical properties, but the two polymorphs coexisted at the temperature ranging from 600 to 900 °C, during which the content of product phase and crystal size gradually increased upon increasing temperature. The assembly of In₂O₃ nanocrystals can be developed to fabricate In₂O₃ functional materials, such as various ceramic materials, or even desired nano- or micro-structures, by using metastable In₂O₃ nanocrystals as precursors or building blocks. The electrical resistivity of In₂O₃ conductive film fabricated by a hot-pressing route was as low as 3.72×10⁻³ Ω cm, close to that of In₂O₃ single crystal, which is important for In₂O₃ that is always used as conductive materials. The findings should be of importance for both the wide applications of In₂O₃ in optical and electronic devices and theoretical investigations on crystal structures.     

Thermal treatment-dependent chemical composition of ternary CdS1−xSex nanocrystals grown in borosilicate glass

Variation of the chemical composition of ternary CdS_1−xSe_x nanocrystals grown in borosilicate glass depending on the thermal treatment is studied by resonant Raman spectroscopy. It is shown that only for the nanocrystals with roughly equal content of substitutive S and Se chalcogen atoms (0.4<x<0.6) the nanocrystal composition is independent of the thermal treatment parameters. In other cases an increase of the thermal treatment temperature (625–700 °C) and duration (2–12 h) results in a considerable increase of the predominant chalcogen content in the nanocrystals.     

Dielectric properties of fine-grained PbTiO3 crystals precipitated in a glass

The spontaneous deformation of PbTiO₃ crystals precipitated in a PbOTiO₂Al₂O₃SiO₂ glass was found to decrease with decreasing grain size. This trend remains even after the glass matrix surrounding PbTiO₃ crystals is removed completely by HNO₃ acid immersion. Consequently, a linear electro-optic effect cannot be expected from transparent glass-ceramics which necessarily comprise very-fine-grained crystals. The dielectric constant of PbTiO₃ crystals surrounded by a glassy matrix shows two maxima at grain sizes 0.15 μm and 250 Å, but is still fairly high even at a grain size as small as 160 Å. This suggests that a material with a large quadratic electro-optic effect may be produced from a transparent glass-ceramic. The maxima of the dielectric constant at grain sizes 0.15 μm and 250 Å were interpreted in terms of the internal stress and internal electric field, respectively.     

Morphologies of calcium carbonate crystallites grown from aqueous solutions containing polyethylene glycol

Calcium Carbonate has been precipitated from aqueous solutions containing different concentrations and different molecular weight of Polyethylene Glycol (PEG). The precipitations were analyzed by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT‐IR) and X‐ray diffraction (XRD). The results demonstrated that PEG has profound influence on the nucleation and crystal growth of CaCO₃, under condition of low PEG6000 (refer to PEG M_W=6000) concentration, it favored the formation of calcite, while high PEG6000 concentration promoted vaterite formation. Additionally, low molecular weight PEG can stabilize vaterite phase. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Preparation of Sb2S3 nanomaterials with different morphologies via a refluxing approach

Single-crystalline antimony trisulfide (Sb₂S₃) nanomaterials with flower-like and rod-like morphologies were successfully synthesized under refluxing conditions by the reaction of antimony trichloride (SbCl₃) and thiourea with PEG400 and OP-10 as the surfactants. X-ray diffraction (XRD) indicates that the obtained sample is orthorhombic-phase Sb₂S₃ with calculated lattice parameters a=1.124 nm, b=1.134 nm and c=0.382 nm. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images show that the flower-like Sb₂S₃ is 9–10 μm in size, which is composed of thin leaves with thickness of 0.05–0.2 μm, width of 0.8–2.2 μm and length of 2.5–3 μm, and the rod-like Sb₂S₃ is 45–360 nm in diameter and 0.7–4 μm in length, respectively. UV–Vis analysis indicates that the band gap of Sb₂S₃ nanorods is 1.52 eV, suitable for photovoltaic conversion. A possible mechanism of formation was proposed. The effects of reaction time and surfactants on the growth of nanomaterials with different morphologies were also investigated.     

Effect of ferric ions on the morphology and size of magnetite nanocrystals synthesized by ultrasonic irradiation

Two‐dimensional plate‐like Fe₃O₄ nanocrystals and nanoparticles could be synthesized by a simple one‐step sonochemical method through ultrasonic irradiation in reverse co‐precipitation solution at low temperature. This technique provided a facile and rapid way to prepare Fe₃O₄nanocrystals with different morphology and size. Magnetite nanoplates were synthesized with only ferrous salt adding into alkali solution, and adding ferric ions with low molar ratio in the metal salts solution would lead to the formation of very small magnetite nanoparticles (∼10 nm). The size of as‐prepared magnetite nanoparticles increased with increasing reaction temperature and showed narrow size distribution, the standard deviation less than 2 nm. This investigation indicated that ferric ions had significant influence on the morphology of Fe₃O₄ nanocrystals. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and characterization of magnetite nanocrystals

Nanocrystals of magnetite (Fe₃O₄) were prepared by sol‐gel technique. The prepared nanocrystals were characterized for phase by powder X‐ray diffraction (XRD) of the samples annealed at successively higher temperature. The magnetite phase was formed during the annealing of the synthesized powder at 400 °C for a few hours. The Fourier transform infrared spectroscopy (FTIR) was performed to analyze the functional groups in the material. The energy dispersive X‐ray diffraction (EDAX) was performed for chemical composition analysis. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) techniques were used to analyze the morphology of nanocrystals and for estimating their average size. The results confirm the formation of Fe₃O₄nanocrystals of the sizes ∼20–50 nm. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Erbium doped fluoride glass-ceramics waveguides fabricated by PVD

Transparent amorphous and glass-ceramics waveguides in the system ZrF₄-LaF₃-ErF₃-AlF₃ (ZELA) have been fabricated by physical vapor deposition (PVD). The ceramming process was studied by means of X-ray diffraction and transmission electron microscopy for different deposition temperatures. With increasing deposition temperature, formation of La_xEr_1−xF₃ nanocrystals with x ∼ 0.3 was observed. The decay curves of the ⁴I_13/2 level in the glass-ceramics with 14.5 mol% Er³⁺ gave evidence of the presence of erbium both in the amorphous matrix (τ = 8.6 ms) and in the crystal phase (τ = 2.2 ms). The decrease of lifetime was due to clustering of erbium incorporated in LaF₃ crystal lattice. No significant increase of attenuation loss was detected after waveguide cerammization (1.3 dB/cm at 1304 nm).     

The properties of xPbTiO- (0.9 — x) PbZrO- 0.1 PbW0.5Cd0.5O3 solutions in the region of coexistence of tetragonal and rhombohedral phases

The changes of the dielectric permittivity η, dielectric loss tg δ, piezoelectric coefficient d₃₃, pyroelectric coefficient p, remanent polarization P_r and reorientation processes of polarization in dependence on percent content of PbTiO₃ in the xPbTiO₃−(0.9 — x) PbZrO₃− 0.1 PbW_0.5Cd_0.5O₃ solid solutions in the phase coexistence region (PCR) wree investigated. It was pointed out that the characteristics of mentioned parameters possess singularities in this region. The values of average Curie temperature obtained from structural, dielectric and pyroelectric measurements were compared. Presented results let us connect dielectric properties of studied solid solutions with their structure.     

Studies of Er doped germanate-oxyfluoride and tellurium-germanate-oxyfluoride transparent glass-ceramics

An erbium doped germanate-oxyfluoride glass 60GeO₂ · 20PbO · 10PbF₂ · 10CdF₂ (GPOF) and a tellurium-germanate-oxyfluoride glass 30TeO₂ · 30GeO₂ · 20PbO · 10PbF₂ · 10CdF₂ (TGPOF) were prepared in the bulk form. By appropriate heat treatment of the as-prepared glasses above, transparent glass-ceramics were obtained with the formation of β-PbF₂ nanocrystals in the glass matrix confirmed by X-ray diffraction. Optical absorption and photoluminescence measurements were performed on as-prepared glass and glass-ceramics. The luminescence of Er³⁺ ions in transparent glass-ceramics revealed sub-band splitting generally seen in a crystal host. The intensity of red and near infrared luminescence significantly increased in transparent glass-ceramic compared to that in as-prepared glass. Two luminescence bands at 758 nm from ⁴F_7/2 → ⁴I_13/2 and at 817 nm from ²H_11/2 → ⁴I_13/2 transitions were observed from transparent glass-ceramic but cannot be seen from the corresponding as-prepared glass. These results are attributed to the change of ligand field of Er³⁺ ions and the decrease of effective phonon energy when Er³⁺ ions were incorporated into the precipitated β-PbF₂ nanocrystals.     

The morphotropy phase transition in PZT-Pb(WCd)O3- ceramics

The changes of the crystal lattice parameters of the solid solution formed on the basis of PbTiO₃ and PbZrO₃ with the constant addition of 10 mol percent PbW_0.5Cd_0.5O₃ has been investigated. In samples containing 37.5 to 45.5 mol percent of PbTiO₃ the coexistence of two phases was observed. In this concentration region the change of lattice constant and homogeneous parameter of deformation appeared.     

An effective growth method to improve the homogeneity of relaxor ferroelectric single crystal Pb(In1/2Nb1/2)O3‐ Pb(Mg1/3Nb2/3)O3‐PbTiO3

Compositional segregation usually has negative effects on the growth of solid solution ferroelectric single crystals of Pb(In_1/2Nb_1/2)O₃‐Pb(Mg_1/3Nb_2/3)O₃‐PbTiO₃ (abbr. PIN‐PMN‐PT or PIMNT). A modified Bridgman method was adopted in this work to control the segregation and improve the compositional homogeneity significantly. The characteristic of this work is to use multiround growths and gradient composition raw materials in order to keep the PbTiO₃ concentration constant during the crystal growth. As an example, the two‐round growth of ternary PIN‐PMN‐PT single crystal is conducted in the same Pt crucible with gradient raw materials, where the first‐round boule was used as the seed crystal for the second‐round growth. Our results show that the as‐grown (Ф80 mm × 270 mm) PIN‐PMN‐PT crystals exhibit higher phase transition temperatures (T_c∼180 °C, T_r/t∼110 °C) and larger coercive field (E_c∼5–5.5 kV/cm), which are much better than the performances of Pb(Mg_1/3Nb_2/3)O₃‐PbTiO₃ crystals, and similar dielectric and piezoelectric performances (ε∼5000, tanδ∼1.25%, d₃₃∼1500 pC/N, k_t∼60%). And about 85 percent of the crystal boule grown by the two‐round growth technique could maintain its compositions around the morphotropic phase boundary.     

Gain cross-section of 1.06 μm emission in Nd-doped SiO2-LaF3 glass-ceramics prepared by sol-gel method

The room temperature near-infrared emission at 1.06 μm corresponding to the ⁴F_3/2 → ⁴I_11/2 laser transition in Nd³⁺-doped SiO₂-LaF₃ transparent glass-ceramics prepared by sol-gel method has been characterized in terms of the product of emission cross-section and fluorescence lifetime. Stimulated emission cross-sections have been calculated from experimental emission spectra using the Füchtbauer-Ladenburg equation. The precipitation of LaF₃ nanocrystals after heat-treatment, confirmed by X-ray diffraction, induces a significant increment of the 1.06 μm near-infrared emission compared with the as made sample. An enhancement of emission cross-section of about 10% has been achieved with increasing temperature of heat-treatment of the nano-ceramming process from 800 to 1000 °C, which is related to the growth of LaF₃ nanocrystals.