X‐ray photoelectron spectroscopy analysis of Ge–Sb–Se pulsed laser deposited thin films

Pulsed laser deposition was used to prepare amorphous thin films from (GeSe₂)_100?x(Sb₂Se₃)_x system (x = 0, 5, 10, 20, 30, 40, 50, and 60). From a wide variety of chalcogenide glass‐forming systems, Ge–Sb–Se one, especially in thin films form, already proved to offer a great potential for photonic devices such as chemical sensors. This system has a large glass‐forming region which gives the possibility to adjust the chemical composition of the glasses according to required physical characteristics. The chemical composition of fabricated thin films was analyzed via X‐ray photoelectron spectroscopy (XPS) and compared to energy dispersive spectroscopy (EDS) data. The results of both techniques agree well: a small deficiency in chalcogen element and an excess of antimony was found. The structure of as‐deposited thin films has been investigated by XPS. The presence of the two main structural units, [GeSe₄] and [SbSe₃] proposed by Raman scattering spectroscopy data analysis, was confirmed by XPS. Moreover, XPS core level spectra analysis revealed the presence of M–M bonds (M = Ge, Sb) in (Ge,Sb)–Ge–(Se)₃ and (Ge,Sb)–Sb–(Se)₂ entities that could correspond to Ge‐based tetrahedra and Sb‐based pyramids where one of its Se atoms at corners is substituted by Ge or Sb ones. The content of depicted M–M bonds tends to increase with introduction of antimony in the amorphous network of as‐deposited thin films from x = 0 to x = 40 and then it decreases. XPS analysis of as‐deposited thin films shows also the presence of the (Ge,Sb)–Se–(Ge,Sb) and Se–Se–(Ge,Sb) entities.     

Effective ionic transport in AgI-based Ge(Ga)–Sb–S chalcogenide glasses

AgI-based Ge–Sb–S, Ga–Sb–S, and Ge–Ga–Sb–S chalcogenide glasses were designed and prepared by melt-quenching, thereafter their thermal properties and conductive performance were comparatively investigated on the basis of their composition-induced network structures. Glass transition in each sample was examined by DSC measurements. Results showed that the samples containing Ge had a higher thermal stability than the Ga–Sb–S–AgI sample, and the Ge–Sb–S–AgI sample obtained had the highest conductivity ion. Raman spectrum analysis was performed, and the results indicated that the [GeS_4-xI_x] structural units and [SbS_3−xI_x] pyramids in the matrix produced effective ion transport channel for dissolved conductive Ag⁺ ions. In the matrix containing Ga, the [Ga(Ge)S_4-xI_x] structure was consumed by part of [S₃Ga–GaS₃] ethane-like units, which had no contribution to the ion transition framework. The study provided the directions for composition and structure configuration control in effective conductive chalcogenide glasses.     

Structure and physical properties of Ge15Sb20Se65‐xSx glasses

We explored the structure and physical properties of Ge₁₅Sb₂₀Se_65‐xS_x (with x = 0, 16.25, 32.5, 48.75, and 65) glasses in order to screen the best compositions for the applications in photonics, since the laser damage thresholds in Se‐based glasses are too low although their optical nonlinearities are high. We found that, linear and nonlinear refractive index of the glasses decreased, but glass transition temperature T_g, optical bandgap E_g and the laser damage threshold increased with increasing S content. We further employed Raman scattering and high‐resolution X‐ray photoelectron spectra to probe the structure of the glasses. Through the analysis of the evolution of the different structural units in the glasses, it was concluded that, the heteropolar bonds (Ge–Se/S, Sb–Se/S) were dominated in these glasses. With the increase in chalcogen Se/S ratio, the number of the Se‐related chemical bonds (Ge–Se, Sb–Se and Se–Se) increased and that of S‐related chemical bond (Ge–S, Sb–S and S–S) decreased gradually, and Ge was prior to bond with S rather than Se. The elemental substitution thus had negligible effect on the glass structure. The change of the physical properties was mainly due to the difference of the strength of the chemical bonds between S–Ge(Sb) and Se–Ge(Sb).     

Correlation Between Crystallization Behavior and Network Structure in GeS2–Ga2S3–CsI Chalcogenide Glasses

Diagram of the phase transformation behavior of GeS₂–Ga₂S₃–CsI glasses is realized in this article and the structure‐property dependence of the chalcogenide glasses is elucidated using differential scanning calorimetry and Raman spectroscopy. We observe the compositional threshold of crystallization behavior locates at x = 6–7 mol% in (100?x)(0.8GeS₂–0.2Ga₂S₃)–xCsI glasses, which is confirmed by the thermodynamic studies. Structural motifs are derived from the Raman result that [Ge(Ga)S₄], [S₂GeI₂], [S₃GaI], and [S₃Ga–GaS₃] were identified to exist in this glass network. Combined with the information of structural threshold, local arrangement of these structural motifs is proposed to explain all the experimental observations, which provides a new way to understand the correlation between crystallization behavior and network structure in chalcogenide glasses.     

Controllable Formation of the Crystalline Phases in Ge–Ga–S Chalcogenide Glass‐Ceramics

We prepared chemically stoichiometric, S‐poor and S‐rich Ge–Ga–S glasses and annealed them at a temperature that was 20°C higher than its respective glass transition temperature. We aimed at tuning the formation of the different crystals in chalcogenide glass‐ceramics. Through systematic characterization of the structure using X‐ray diffraction and Raman scattering spectra, we found that, GeS₂ and GeS crystals only can be created in S‐rich and S‐poor glass‐ceramics, respectively, while all GeS, Ga₂S₃, and GeS₂ crystals exist in chemically stoichiometric glass‐ceramics. Moreover, we demonstrated the homogeneous distribution of the crystals can be formed in the S‐rich glass‐ceramics from the surface to the interior via composition designing. The present approach blazes a new path to control the growth of the different crystals in chalcogenide glass‐ceramics.     

Compositional dependence of crystallization in Ge–Sb–Se glasses relevant to optical fiber making

For fiber‐optic mid‐infrared bio‐ and chemical‐sensing, Ge–Sb–Se glass optical fibers are more attractive than Ge–As–Se because of: (i) lowered toxicity and (ii) lower phonon energy and hence transmission to longer wavelengths, with potential to reach the spectral “fingerprint region” for molecular sensing. There is little previous work on Ge–Sb–Se fibers. Here, fibers are fabricated from two glass compositions in the Ge_xSb₁₀Se_90?x atomic (at.) % series. Both glass compositions are of similar mean‐coordination‐number, lying in the overconstrained region, yet of different chemical composition: stoichiometric Ge₂₅Sb₁₀Se₆₅ at. % and non‐stoichiometric Ge₂₀Sb₁₀Se₇₀ at. %. Thermal analysis on bulk glasses has previously shown that the former exhibited the maximum glass stability of the series. However, during fiber‐drawing of Ge₂₅Sb₁₀Se₆₅ at. %, the preform tip is found to undergo surface‐devitrification to monoclinic GeSe₂ alone, the primary phase, no matter if the preform is an annealed, as‐melted rod or annealed, extruded rod. The heating rate of the preform‐tip to the fiber‐drawing temperature is estimated to be up to ~100°C/min to ~490°C. Lower heating rates of 10°C/min using thermal analysis, in contrast, encourage crystallization of both Sb₂Se₃ and GeSe₂. The non‐stoichiometric: Ge₂₀Sb₁₀Se₇₀ at. % composition drew successfully to low optical loss fiber, no matter whether the preform was an annealed, as‐melted rod or annealed, extruded rod.     

Network Rearrangement in AgI‐Doped GeTe4 Glasses

The structure of (GeTe₄)_1?x(AgI)_x (x = 0.15 and 0.25) glasses has been investigated by X‐ray and neutron diffraction as well as extended X‐ray absorption spectroscopy (EXAFS) and Raman spectroscopy. Large‐scale structural models have been obtained by fitting simultaneously the experimental datasets in the framework of the reverse Monte Carlo simulation technique (RMC). Short‐range order parameters have been calculated and compared with that of GeTe₄. Doping with AgI affects the structure of the host GeTe₄ matrix in two ways. First, while Te is essentially twofold coordinated in GeTe_4, its coordination number is as high as ~2.9 ± 0.3 for x = 0.25. The change is mainly due to the increased fraction of Te–Te bonds. Second, Ge atoms remain fourfold coordinated but the tetrahedral symmetry is distorted due to the elongation of some Ge–Te bonds. The incorporation of AgI in the GeTe₄‐based host covalent matrix and the Te coordination increase explains the enhanced thermal stability of (GeTe₄)_1?x(AgI)_x in the supercooled liquid‐state hindering the crystallization of Te found in case of GeTe₄ glass.     

Phase Diagram of the Li4GeS4–Li3PS4 Quasi‐Binary System Containing the Superionic Conductor Li10GeP2S12

A phase diagram is constructed for the quasi‐binary Li₄GeS₄–Li₃PS₄ system containing the lithium superionic conductor Li₁₀GeP₂S₁₂ (LGPS), having an LGPS‐type structure, and the β‐Li₃PS₄‐type phase, having a thio‐LISICON structure. The LGPS and thio‐LISICON intermediate compounds are found to exhibit solid solution ranges and show incongruent melting at 650°C and 560°C, respectively. The end‐member Li₄GeS₄ has a compositional range of 0 < k < 0.3 in [(1?k) Li₄GeS₄ + k Li₃PS₄], while the other end‐member γ‐Li₃PS₄ has no solid solution range. The crystal structures appearing in the binary systems are the α‐, β‐, and γ‐type Li₃PS₄ structures and the LGPS‐type structure, and these are formed by PS₄ tetrahedra with different arrangements in each structure. The phase and structural relationships between the compounds appearing in the Li₄GeS₄–Li₃PS₄ system are thus clarified.     

Ultra‐Wide Temperature Stable Dielectrics Based on Bi0.5Na0.5TiO3–NaNbO3 System

The microstructure, phase structure, ferroelectric, and dielectric properties of (1?x)Bi_0.5Na_0.5TiO₃‐xNaNbO₃ [(1?x)BNT‐xNN] ceramics conventionally sintered in the temperature range of 1080°C–1120°C were investigated as a candidate for capacitor dielectrics with wide temperature stability. Perovskite phase with no secondary impurity was observed by XRD measurement. With increasing NN content, (1?x)BNT‐xNN was found to gradually transform from ferroelectric (x = 0–0.05) to relaxor (x = 0.10–0.20) and then to paraelectric state (x = 0.25–0.35) at room temperature, indicated by P–I–E loops analysis, associated with greatly enhanced dielectric temperature stability. For the samples with x = 0.25–0.35, the temperature coefficient of capacitance (TCC) was found <11% in an ultra‐wide temperature range of ?60°C–400°C with moderate dielectric constant and low dielectric loss, promising for temperature stable capacitor applications.     

Subsolidus Phase Relations of the BaO–Y2O3–MnO2 System in Air

The subsolidus phase relations of the BaO–Y₂O₃–MnO₂ system have been investigated in air. There are eight binary compounds, a new ternary compound and 11 three‐phase regions in this system. The ternary compound with the BaO:YO_1.5:MnO₂ molar ratio of 8:2:5 was indexed by a rhombohedral lattice with a = 5.7929 (6) and c = 28.586 (4) Å. The synthesized compounds were determined to be stoichiometric except for the Ba_1?xY_xMnO₃ phase (x ≤ 0.01).     

High Na‐ion conducting Na1+x[SnxGe2−x(PO4)3] glass‐ceramic electrolytes: Structural and electrochemical impedance studies

Na‐ion conducting Na_1+x[Sn_xGe_2?x(PO₄)₃] (x = 0, 0.25, 0.5, and 0.75 mol%) glass samples with NASICON‐type phase were synthesized by the melt quenching method and glass‐ceramics were formed by heat treating the precursor glasses at their crystallization temperatures. XRD traces exhibit formation of most stable crystalline phase NaGe₂(PO₄)₃ (ICSD‐164019) with trigonal structure. Structural illustration of sodium germanium phosphate [NaGe₂(PO₄)₃] displays that each germanium is surrounded by 6 oxygen atom showing octahedral symmetry (GeO₆) and phosphorous with 4 oxygen atoms showing tetrahedral symmetry (PO₄). The highest bulk Na⁺ ion conductivities and lowest activation energy for conduction were achieved to be 8.39 × 10^?05 S/cm and 0.52 eV for the optimum substitution levels (x = 0.5 mol%, Na_1.5[Sn_0.5Ge_1.5(PO₄)₃]) of tetrahedral Ge⁴⁺ ions by Sn⁴⁺ on Na–Ge–P network. CV studies of the best conducting Na_1.5[Sn_0.5Ge_1.5(PO₄)₃] glass‐ceramic electrolyte possesses a wide electrochemical window of 6 V. The structural and EIS studies of these glass‐ceramic electrolyte samples were monitored in light of the substitution of Ge by its larger homologue Sn.     

Order–Disorder Phase Transition and Magneto‐Dielectric Properties of (1−x)LiFe5O8–xLi2ZnTi3O8 Spinel‐Structured Solid Solution Ceramics

In this study, the spinel solid solution ceramics (1?x)LiFe₅O₈–xLi₂ZnTi₃O₈ (0 ≤ x ≤ 1) were prepared via the solid‐state reaction method. The phase evolution, sintering behaviors, microstructures, magneto‐dielectric properties, and microwave dielectric properties were systematically investigated. The XRD and SEM analysis indicated that the LiFe₅O₈ phase and the Li₂ZnTi₃O₈ phase were almost fully soluble in each other at any proportion. Meanwhile, the evidence of ionic substitution has been directly observed at the atomic scale by means of scanning transmission electron microscopy, which is further confirmed by the Raman spectroscopy. Evidence shows that the magnetic and dielectric properties are quite sensitive to the compositions. The optimal results with remarkable magneto‐dielectric properties of μ′ = 38.2, tanδ_μ = 0.25, ε′ = 19.6, tanδ_ε = 8 × 10^?3 at 1 MHz, and ε′ = 19.1, Q × f = 10 400 GHz at about 7 GHz have been obtained in 0.25LiFe₅O₈–0.75Li₂ZnTi₃O₈ sample. The design of complex spinel solid solution can generate novel magneto‐dielectric single‐phase ceramics combining both high permeability and good dielectric properties, which provides a way in developing multifunctional materials for applications in electronic devices.     

Thermodynamic Assessment of the Pr–O System

The Calphad method was used to perform a thermodynamic assessment of the Pr–O system. Compound energy formalism representations were developed for the fluorite α‐PrO_2–x and bixbyite σ‐Pr₃O_{5 ± x} solid solutions while the two‐sublattice liquid model was used to describe the binary melt. The series of phases between Pr₂O₃ and PrO₂ were taken to be stoichiometric. Equilibrium oxygen pressure, phase equilibria, and enthalpy data were used to optimize the adjustable parameters of the models for a self‐consistent representation of the thermodynamic behavior of the Pr–O system from 298 K to melting.     

Reactive Hot Pressing of ZrC–SiC Ceramics at Low Temperature

Composites of ZrC–SiC with relative densities in excess of 98% were prepared by reactive hot pressing of ZrC and Si at temperature as low as 1600°C. The reaction between ZrC and Si resulted in the formation of ZrC_1?x, SiC, and ZrSi. Low‐temperature densification of ZrC?SiC ceramics is attributed to the formed nonstoichiometric ZrC_1?x and Zr–Si liquid phase. Adding 5 wt% Si to ZrC, the three‐point bending strength of formed ZrC_0.8–13.4 vol%SiC ceramics reached 819 ± 102 MPa with hardness and toughness being 20.5 GPa and 3.3 MPa·m^1/2, respectively.     

Phase Diagram and Enhanced Piezoelectric Response of Lead‐Free BaTiO3–CaTiO3–BaHfO3 System

Three composition groups in the BaTiO₃–CaTiO₃–BaHfO₃ ternary system, (1 ? x)Ba(Hf_yTi_1?y)O₃–x(Ba_1?zCa_z)TiO₃ (abbreviated as BH_yT–xBC_zT with x = 0–1.0, y = 0.16, z = 0.20; x = 0–1.0, y = 0.16, z = 0.30; x = 0–1.0, y = 0.20, z = 0.30, respectively), have been designed for investigating the variation of the intermediate O‐phase region and its effect on the electrical properties. The temperature‐composition phase diagram of each group has been proposed based on the X‐ray diffraction patterns and the temperature‐dependent dielectric behaviors. The enhanced piezoelectric properties are achieved in the O–T phase boundary compositions of the three groups, which are BH_0.16T–0.58BC_0.20T, BH_0.16T–0.48BC_0.30T and BH_0.20T–0.53BC_0.30T, respectively. Piezoelectric coefficient d₃₃ of 448 pC/N is obtained in BH_0.20T–0.53BC_0.30T, which is higher than those of the other two phase boundary compositions. The O‐phase zone in BH_0.20T–xBC_0.30T is narrower than those in the BH_0.16T–xBC_0.20T and BH_0.16T–xBC_0.30T. In spite of its small O‐phase volume occupancy, the O‐phase plays a key role in the properties of the system. Our work confirms that the enhancement in piezoelectric properties is not only related to the O–T phase boundary near room temperature (RT), but also related to the shift of T_R‐O toward RT. In addition, a quantitative relation between the phase boundary composition and atomic mole ratio of Hf to Ca (R_m) is proposed, which the R_m value corresponding to the phase boundary is about 0.58. The results clearly demonstrate that in this system high piezoelectric properties are achieved by tuning the specific R_m value. Such a work may provide new clues for designing lead‐free piezoelectric materials with enhanced piezoelectric property.     

Correlating Structure with Threshold Behavior of Chalcogenide Glasses Within Ge–Sn–Se Ternary System

A systematic investigation of the optical and structural properties of chalcogenide glasses in Ge–Sn–Se ternary system is presented. We have found a threshold behavior of optical property, namely, existence of transitional composition of the Ge–Sn–Se glasses, with progressive replacement of Se by Sn. Calculation of mean coordination number indicates that the transition‐like feature of optical property is associated with the evolution of chemical ordering of the Ge–Sn–Se network. Analysis of Raman spectra of the glasses explains that the interaction between Se–Se bonds, Sn(Se_1/2)₄ tetrahedra, and Sn–Sn homopolar bonds is the origination of such optical phenomenon.     

Energetic Effects of Substitution of La–Nd and Si–Ge Oxyapatite‐Type Materials

A series of lanthanide oxyapatites, neodymium silicates (Nd_9.33?xM_3x/2(SiO₄)₆O₂; x = 0.0 and 2.0 and M = Ca, Sr, and Ba), and lanthanum germanate (La₁₀(GeO₄)₆O₃) were prepared by a variety of heat treatments and characterized. High‐temperature oxide melt solution calorimetry in molten 2PbO–B₂O₃ solvent at 1078 K was performed to determine their enthalpies of formation from constituent oxides at room temperature. The energetics of these materials is discussed in terms of the effects of doping on two crystallographic sites, the lanthanide and tetrahedral sites. The enthalpy of formation from oxides becomes less exothermic by substituting La with Nd throughout the whole series, in both doped and undoped compositions, reflecting the smaller radius and lower basicity of Nd compared with La. Cation stoichiometric lanthanum germanate apatite (La₁₀(GeO₄)₆O₃) shows a more endothermic enthalpy of formation than the corresponding silicate, reflecting the larger radius and lower acidity of Ge than Si.     

Y3Al5O12–SiO2 Glasses: Structure and Polyamorphism

Aerodynamic levitation and CO₂ laser melting have been used to synthesize the yttrium aluminosilicate glasses zY₂O₃–yAl₂O₃–xSiO₂ with z/y = 3/5 corresponding to the YAG (Y₃Al₅O₁₂) composition and x between ~5 and ~45 mol%. The low‐ and high‐density (LDA inclusion and HDA matrix) polyamorphic phases in glasses with less than ~14 mol% SiO₂ were identified with backscattering electron imaging. Polarized and depolarized Raman spectra show the formation of various Qⁿ SiO₄ species whose relative populations change smoothly as the SiO₂ content is altered. The AlOs (s = 4–6) and YOz (z = 6–9) polyhedra formed in the YAG glass are preserved upon silica additions while the terminal oxygens of the Q²AlO₄ tetrahedra are gradually bridged to the Qⁿ‐SiO₄ species. The low‐frequency Boson Peak overlaps with the vibrational spectrum and its maximum is redshifted with increasing silica content. Micro‐Raman spectra measured for the LDA and HDA amorphous phases are found to be similar to the spectra of the bulk glass indicating common structural characteristics. The stability of the LDA phase against crystallization appears to be lower than that of the HDA phase. The crystallinity on certain inclusions consisted of YAG microcrystals and a new unidentified microcrystalline phase within Y₄Al_2(1?x)Si_2xO_(9+x) solid solution.     

Pyroelectric energy harvesting using low–TC (1–x)(Ba0.7Ca0.3)TiO3–xBa(Zr0.2Ti0.8)O3 bulk ceramics

Lead‐free ferroelectric ceramics (1–x)(Ba_0.7Ca_0.3)TiO₃–xBa(Zr_0.2Ti_0.8)O₃ (BCTZ100x) with x = 0.20, 0.30, 0.40, 0.50, 0.60, 0.70, and 0.80 were evaluated for their pyroelectric energy harvesting performance, using the Olsen cycle. As the composition ratio x increased, the crystal phase changed to tetragonal, orthorhombic, rhombohedral, and cubic; the phase boundaries crossed each other in the vicinity of BCTZ70. The crossover phase transition behavior between first‐order and diffuse phase transition changed to only the diffusion phase transition with increasing x. A pinching effect occurred because an increase in dielectric constant was also observed. Energy densities N_D of 229 mJ/cm³ and 256 mJ/cm³ for BCTZ50 and BCTZ80 were obtained, respectively, in temperature of 30°C‐100°C and an electric field of 0‐30 kV/cm. These N_D values are over two times higher than that of soft–Pb(Ti,Zr)O₃ (PZT), which exhibits piezoelectric performance equivalent to BCTZ50 at room temperature. Compared with soft–PZT, BCTZ50 and BCTZ80 exhibited larger N_D values owing to their lower Curie temperatures (T_C ~ 50°C‐110°C). We conclude that low–T_C ferroelectrics are useful for pyroelectric energy conversion based on the Olsen cycle even if they are unsuitable for piezoelectric applications at high temperatures.     

Structural,magnetic, electrical,and electrochemical properties of Sr–Co–Ru–O: A hybrid‐capacitor application

In this study, we report the synthesis of SrCo_1?xRu_xO_3?δ nominal compositions, where x = 0.0‐1.0, using solid‐state reaction technique. XRD analysis confirms the structure of x = 0 sample as hexagonal Sr₆Co₅O₁₅. As the Co ions are substituted by Ru, a two‐phase structure (hexagonal R32 and orthorhombic Pbnm) emerges up to x ≤ 0.5. As the Ru content is increased further, the hexagonal R32 phase disappears completely and an orthorhombic Pbnm phase becomes the main phase. SEM images show that grain size of the samples decreases with increasing Ru content. Temperature‐dependent electrical conductivity studies indicate upon Ru substitution in the nominal SrCo_1?xRu_xO_3?δ compounds, resistivity decreases due to appearance of metallic SrRuO₃ phase. The cyclic voltammogram (CV) of the samples show capacitive properties upon Ru substitution. The cycle measurements of the capacitors yield promising results for potential supercapacitor applications.