Effect of A‐ or B‐site doping of perovskite calcium manganite on structure,resistivity, and thermoelectric properties

Bismuth‐, lanthanum‐, and molybdenum‐doped calcium manganite (CaMnO₃, abbreviated Mn113) are synthesized by solid‐state synthesis route from their respective oxide precursors at a same doping level (x=0.05). Depending on the ionic sizes, trivalent dopants (Bi³⁺ and La³⁺) replace Ca²⁺(A site), while penta/hexavalent dopant Mo⁵⁺/Mo⁶⁺ replaces Mn⁴⁺ (B site) in the Mn113 structure. XRD of all three doped samples confirm formation of single phase. In all three samples, doping causes unit cell volume to expand, while volume expansion is maximum for the Mo‐Mn113. The transport behavior of the doped samples follows small polaron hopping mechanism. Resistivity of the doped samples depends not only on the carrier concentration but also on the effective bandwidth determined by the structural distortion introduced by the dopant ions. Bi‐Mn113 has highest resistivity at the both temperature end, while La‐Mn113 has the lowest. Thermopower is determined by the carrier concentration only and does not depend on dopant type, having value ~260 μV/K at 1000 K. At high (>800 K), S reaches a saturation value and becomes independent of T. La‐Mn113 is having highest figure of merit (zT) 0.19 at 1000 K.     

Tuning of dielectric properties in Ti-Doped granular HfO2 nanoparticles for high-k applications

An array of titanium (Ti) doped HfO₂ [(Hf_1-xTi_xO₂) (x = 0.0–1.0)] nanoparticles (NPs) synthesis and the study of their structural, spectroscopic, and dielectric properties is reported. The Hf_1-xTi_xO₂ NPs were synthesized by a sol-gel type wet chemical process. The crystal structure of pure HfO₂ and TiO₂ NPs revealed by structural analysis is monoclinic (m) and tetragonal (t), respectively. The crystallinity of the doped samples was found to be dopant concentration-dependent. The microstructure of the obtained NPs was investigated along with their spectroscopic and dielectric characteristics. The tunable dielectric properties of Hf_1-xTi_xO₂ NPs make them ideal for high frequency, high-k applications.     

Li+ and Sm3+ co-doped AgNbO3-based antiferroelectric ceramics for high-power energy storage

Ag_1-x-3yLi_xSm_yNbO₃ (x≤0.05, y≤0.05) (ALSN) antiferroelectric ceramics were successfully prepared via conventional solid-state reaction and sinter routes in oxygen atmosphere for improving the energy storage characteristic of pure AgNbO₃. The results indicate that all of the studied compositions display a pure orthorhombic antiferroelectric (AFE) perovskite structure, while their key parameters of electric-field-induced antiferroelectric-ferroelectric transition can be affected by Li⁺ or/and Sm³⁺ doping contents. The Sm³⁺ doping can enhance the stability of antiferroelectric state, giving rise to higher antiferroelectric-ferroelectric transition electric-field (E_F and E_B), while Li⁺ doping can reduce E_F and E_B for Sm³⁺ doped AgNbO₃ with low Sm³⁺ content (y≤0.03). When co-doping the same amounts of Li⁺ and Sm³⁺ at x=y≤0.03, both E_F and E_B almost remain unchanged. At x=y=0.05, the diffuse phase transition (DPT) behavior of antiferroelectric-paraelectric (AFE-PE) phase transition occurred, resulting in a “slim-like” double-polarization hysteresis with significantly enhanced E_F. Due to these features, both W_rec and η are improved compared with pure AgNbO₃. The W_rec and η with composition at x=y=0.05 is 2.33 J/cm³ and 58% under applying electric field of 240 kV/cm, respectively. The results suggest that building DPT behavior of AFE-PE phase transition could be an alternative strategy to improve the energy storage characteristic of AgNbO₃.     

Co-doping effects of A-site Y3+ and B-site Al3+ on the microstructures and dielectric properties of CaCu3Ti4O12 ceramics

Different doping elements have been used to reduce the dielectric losses of CaCu₃Ti₄O₁₂ ceramics, but their dielectric constants usually are undesirably decreased. This work intends to reduce their dielectric losses and simultaneously enhance their dielectric constants by co-doping Y³⁺ as a donor at A site and Al³⁺ as an acceptor at B site for substituting Ca²⁺ and Ti⁴⁺, respectively. Samples with different doping concentrations x = 0, 0.01, 0.02, 0.03, 0.05 and 0.07 have been prepared. It has been shown that their dielectric losses are generally reduced and their dielectric constants are simultaneously enhanced across the frequency range up to 1 MHz. The doped sample with x = 0.05 exhibits the highest dielectric constant, which is well over 10⁴ for frequency up to 1 MHz and is about 20% higher than the undoped sample. Impedance spectra indicate that the doped samples have much higher grain boundary resistance than the undoped one.     

Structural,optical, electrical,dielectric, molecular vibrational and magnetic properties of La3+ doped Mg–Cd–Cu ferrites prepared by Co-precipitation technique

Ferrites are among the most frequently investigated materials mainly due to interesting and practically different properties. Therefore, easily and cost-effective lanthanum doped Mg_0.5Cd_0.25Cu_0.25Fe_2-xLa_xO₄ (x = 0.0, 0.0125, 0.025, 0.0375 and 0.05) ferrites were synthesized by a co-precipitation route, a comprehensive characterisation of their structural, optical, electric, dielectric, molecular vibrational, and magnetic properties were carried out. X-ray diffraction analysis confirmed the formation of a cubic spinel structure. Variations in frequency bands were also observed with amplification in optical band gap energy (2.95 – 3.38 eV) due to La³⁺ ions insertion. The electric resistivity had opposite trends at low and high temperatures with increasing La³⁺ content. The Curie temperature, activation energy, and drift mobility were also determined to have values consistent with the semiconducting behavior of the soft ferrites. The saturation magnetization (M_S) has a maximum value 49.385 emu/g with remanent magnetization (M_r) was 34.928 emu/g and coercivity 661.4 Oe for La³⁺ concentration x = 0.05. The minimum dielectric loss was observed for La³⁺ concentration x = 0.025. Moreover, the resistivity (ρ) has a maximum value of 7.95 × 10⁴ Ω cm for La³⁺ concentration x = 0.025. The calculated frequency range of La³⁺ doped Mg–Cd–Cu ferrites was detected in the microwave range (3.36 – 10.80 GHz), suggesting the potential application of the materials in longitudinal recording media and microwave absorbance.     

Intense broadband 3.1 μm emission in Er3+-doped fluoroaluminate-tellurite glass for mid-infrared laser application

Er³⁺ single doped fluoroaluminate-tellurite glasses were made by employing a conventional melt-quenching technique. A strong fluorescence around 3.1 μm was achieved from Er³⁺-doped fluoride glasses, under a 980 nm laser diode pump, which was assigned to the Er³⁺: ⁴S_3/2 → ⁴F_9/2 radiation transition process. The up-conversion and mid-infrared spectra of emission for fluoroaluminate-tellurite glasses with various concentrations of Er³⁺ ions dopant was researched. In addition, the calculated fluorescence lifetime value about 3.1 μm reaches 0.48 ms. The findings indicate that fluoroaluminate-tellurite glasses doped with Er³⁺ have prospects of being developed into 3.1 μm mid-infrared fiber and laser materials.     

Electrical properties of Y/Mg modified NiO simple oxides for negative temperature coefficient thermistors

The semiconductors based on simple oxide have unique features with controllable electrical property by element doping. Y³⁺ doped NiO (Ni_1−xY_xO, x ≤ 0.01) and Mg²⁺ substituted Ni_0.995Y_0.005O (Ni_0.995−yY_0.005Mg_yO, y ≤ 0.5) powders were synthesized by a wet chemical method. The related ceramics were obtained by conventional ceramic processing. Phase component, microstructure, electrical property and temperature sensitivity of the prepared ceramics were investigated. All ceramics have a rock-salt type crystalline structure. The room-temperature resistivity of the ceramics can be widely adjusted from 254 to 12 322 Ω·cm by changing the concentrations of Y³⁺ and Mg²⁺ ions. The samples show typical characteristics of negative temperature coefficient of resistivity and have high temperature sensitivity with material constants higher than 4745 K. The analysis of impedance spectra indicates that the electrical properties resulted from both grain effect and grain boundary effect. Both band conduction and small polaron hopping were proposed as possible conduction mechanisms in the studied ceramics.     

Structure and luminescence properties of Eu3+ doped TiO2 nanocrystals and prolate nanospheroids synthesized by the hydrothermal processing

We report on a new approach to the synthesis of Eu³⁺ doped TiO₂ nanocrystals and prolate nanospheroids. They were synthesized by shape transformation of hydrothermally treated titania nanotubes at different pH and in the presence of Eu³⁺ ions. The use of nanotubes as a precursor to the synthesis of Eu³⁺ doped TiO₂ nanocrystals and prolate nanospheroids opens the possibility of overcoming the problems related to molecular precursors. The shapes and sizes of the nanotubes, Eu³⁺ doped TiO₂ nanocrystals and prolate nanospheroids were characterized by transmission electron microscopy (TEM) technique. Crystal structures of the resultant powders were investigated by X-ray diffraction (XRD) analysis. The percentage ratio of Eu³⁺ to Ti⁴⁺ ions in doped nanocrystals was determined using inductively coupled plasma atomic emission spectroscopy. The optical characterization was done by using fluorescence and ultraviolet-visible reflection spectroscopies. An average size of faceted Eu³⁺ doped TiO₂ nanocrystals was 13 nm. The lateral dimensions of Eu³⁺ doped TiO₂ prolate nanospheroids varied from 14 to 20 nm, while the length varied from 40 to 80 nm, depending on precursor concentrations. The XRD patterns revealed the homogeneous anatase crystal phase of Eu³⁺ doped TiO₂ nanocrystals and prolate nanospheroids independently of the amount of dopant. A postsynthetic treatment (filtration or dialysis) was applied on the dispersions of the doped nanoparticles in order to study the influence of the dopant position on photoluminescence (PL) spectra. In the red spectral region, room temperature PL signals associated with ⁵D₀ → ⁷F_J (J = 1–4) transitions of Eu³⁺ were observed in all samples. The increased contribution of dopants from the interior region of dialyzed nanocrystals to photoluminescence was confirmed by the increase of R value.     

Study on La2(Hf1-xTix)2O7 (x ≤ 0.20) pyrochlores for potential thermal/environmental barrier coating applications

Lanthanum hafnate (La₂Hf₂O₇) with a pyrochlore structure has excellent high temperature stability and low thermal conductivity, which is promising for thermal/environmental barrier coatings (T/EBCs) applications. To reduce its thermal expansion coefficient (TEC) so as to better match SiC_f/SiC composites, a smaller tetravalent dopant Ti⁴⁺ has been introduced in the Hf-sites to form La₂(Hf_1-xTi_x)₂O₇ (x ≤ 0.20). The phase composition and microstructure confirms that La₂(Hf_1-xTi_x)₂O₇ solid solutions possess a pure pyrochlore structure. With an increase of x, their TECs are decreasing consistently, whilst their thermal conductivities of La₂(Hf_1-xTi_x)₂O₇ are slightly increasing at high temperature but still much lower than those of meta-stable yttria partially stabilized zirconia, both of which are attributing to an increase of elastic modulus after Ti⁴⁺ doping on Hf-sites. The extremely excellent high temperature stability, relatively low thermal conductivities and low TECs suggest that La₂(Hf_1-xTi_x)₂O₇ is a prospective candidate material for T/EBC applications.     

Lead-free Ag1−3xLaxNbO3 antiferroelectric ceramics with high-energy storage density and efficiency

Environmentally benign lead-free bulk ceramics with high recoverable energy density (W_rec) are very attractive in advanced pulsed power capacitors. In this work, composition engineering was adopted by La³⁺ modification to improve the energy storage performance of Ag_1−3xLa_xNbO₃ ceramics. It was found that the antiferroelectric (AFE) phase was stabilized after La³⁺ substitution, as a result of the reduced tolerance factor t. Significant improvement of W_rec and energy storage efficiency (η) were achieved with value of 3.12 J/cm³ and 0.63 for x = 0.02 at an electric field of 230 kV/cm, more than 1.5 times the value of pure AgNbO₃ (W_rec = 1.9 J/cm³, η = 0.40). The excellent energy storage properties are resulted from the increased antiferroelectric-ferroelectric phase transition electric field (E_F), ferroelectric-antiferroelectric phase transition electric field (E_A), and breakdown electric field (E_b). The enhanced E_b was ascribed to the decreased grain size and increased electrical resistivity upon La³⁺ modification. The feature makes Ag_1−3xLa_xNbO₃ a potential candidate for energy storage applications.     

Grain size tailoring and enhanced energy storage properties of two-step sintered Nd3+-doped AgNbO3

AgNbO₃ as a lead-free antiferroelectric material, has received widespread attention in recent years due to its promising application in the aspects of energy storage devices. However, the high remnant polarization and low breakdown strength limits its energy storage properties. In this work, Nd³⁺-doped AgNbO₃ (Ag_1−3xNd_xNbO₃, x=0−0.015) ceramics were prepared and a two-step sintering method was employed. The introduction of Nd³⁺ leads to the enhanced stability of the antiferroelectric phase, refined grain size and increased resistivity. Furthermore, by adjusting the pre-heating temperature in the two-step sintering, the homogeneity of microstructure is improved and the resistance of pre-heated samples increases by one order of magnitude compared with normally sintered samples, leading to the enhanced breakdown strength. Ag_0.97Nd_0.01NbO₃ pre-heated at 1100 °C for 2 h exhibits promising energy storage properties, with a recoverable energy storage density of 3.2 J/cm³ and energy efficiency of 52 % under an applied electric field of 210 kV/cm.     

Luminescent Er3+ doped transparent alumina ceramics

We report on successful preparation of Er³⁺ doped transparent alumina (0.1–0.17 at.%) exhibiting visible light photoluminescence using wet shaping method and hot isostatic pressing. The effects of dopant amount, type of doping powder and powder pre-treatment on final microstructure, real in-line transmittance and photoluminescence characteristics were studied.The real in-line transmittance ranged between 28 and 56%, depending on processing parameters. The transparency decreased with increased amount of dopant. The decrease is dependent on the type of doping powder and its pre-treatment.The photoluminescence spectra measured in both visible and NIR region showed typical emission bands due to the presence of Er³⁺ ions. The decay profiles of the ⁴S_3/2 → ⁴I_15/2 transition were fitted with a 2-exponential function, with faster component in the range of 360–700 ns and slower component around 1.6-2.4 μs. The intensity of emissions and lifetime of the ⁴S_3/2 level decrease significantly with increasing concentration of Er³⁺ ions.     

Mechanical and thermal properties of δ-RE4Hf3O12 (RE = Yb,Lu)

Rare-earth (RE) hafnates are promising thermal and environmental barrier coating (TEBC) materials for SiC_f/SiC ceramic matrix composites. In this study, pure-phase and dense δ-RE₄Hf₃O₁₂ (RE = Yb, Lu) bulk ceramics have been fabricated via a hot-pressing method. The crystal structure, microstructure, mechanical, and thermal properties of δ-RE₄Hf₃O₁₂ were systematically investigated in order to probe their potential application as TEBCs. The high-temperature elastic moduli of δ-Yb₄Hf₃O₁₂ and δ-Lu₄Hf₃O₁₂ are measured to be 185 and 188 GPa at 1673 K, respectively, which are over 85% values of room temperature. The coefficients of thermal expansion are 7.64 × 10⁻⁶ and 7.46 × 10⁻⁶ K⁻¹ for δ-Yb₄Hf₃O₁₂ and δ-Lu₄Hf₃O₁₂, respectively. The relatively low coefficient of thermal expansion and thermal conductivity as well as their excellent high-temperature stability endow these hafnates as potential TEBC candidates.     

Fabrication and characterization of In doped Li13.9Sr0.1Zn(GeO4+δ)4 electrolytes for proton-conducting solid oxide fuel cells

Li_13.9Sr_0.1Zn(GeO_4+δ)₄ (LSZG) materials can exhibit proton conduction by Li⁺/H⁺ ion exchange in hydrogen atmosphere. It can be used in solid oxide fuel cells (SOFCs) as an electrolyte. In this study, In³⁺ doped LSZG powders are synthesized by sol-gel method. X-ray diffraction, scanning electron microscopy, thermal gravimetric analyzer, and electrochemical impedance spectroscopy are used to investigate the effects of In doping on LSZG. All Li_13.9-xIn_xSr_0.1Zn(GeO_4+δ)₄ (LISZG, 0 ≤ x ≤ 0.3) ceramics exhibit the same phase with LSZG. The dopant of In promotes the sintering activity and Li⁺/H⁺ ion exchange rate of LSZG. The optimum doping of In is x = 0.2. At 600 °C, Li_13.7In_0.2Sr_0.1Zn(GeO_4+δ)₄ (0.2LISZG) shows a proton conductivity of 0.094 S/cm under 0.9 V direct current bias voltage. In addition, the single cell based on 0.2LISZG electrolyte is prepared, and it has been demonstrated that the practical utilization of 0.2LISZG in IT-SOFCs is feasible.     

Ionic conductivity of tetragonal ZrO2 polycrystal doped with TiO2 and GeO2

The effects of the co-doping and the resultant co-segregation of 2 mol% TiO₂ and 2 mol% GeO₂ on the ionic conductivity and on the chemical bonding state in a tetragonal ZrO₂ polycrystal were investigated. The conductivity data and grain boundary microstructure showed that the doped Ti⁴⁺ and Ge⁴⁺ cations segregate along the grain boundary, and this segregation causes a reduction in the conductivity of both the grain interior and grain boundary and an increase in the activation energy of the grain boundary conductivity. Overall, the data indicate that the segregation retards the diffusion of oxygen anions. A first-principle molecular orbital calculation explains the retarded diffusion of the oxygen anion from a change in the covalent bonds around the dopant cations; an increase in the strength of the covalent bond between the oxygen and doped cation should work to suppress the diffusion of the oxygen anion.     

Optimization of Opto-Electrical and Photocatalytic Properties of SnO<Subscript>2</Subscript> Thin Films Using Zn<Superscript>2+</Superscript> and W<Superscript>6+</Superscript> Dopant Ions

Abstract  

A series of Zn²⁺ and W⁶⁺ doped tin oxide (SnO₂) thin films with various dopant concentrations were prepared by spray pyrolysis deposition, and were characterized by X-ray diffraction, atomic force microscopy, contact angle, absorbance, current density–voltage (J–V) and photocurrent measurements. The results showed that W⁶⁺ doping can prevent the growth of nanosized SnO₂ crystallites. When Zn²⁺ ions were used, the crystallite sizes were proved to be similar with the undoped sample due to the similar ionic radius between Zn²⁺ and Sn⁴⁺. Regardless of the dopant ions’ type or concentration, the surface energy has a predominant dispersive component. By using Zn²⁺ dopant ions it is possible to decrease the band gap value (3.35 eV) and to increase the electrical conductivity. Photocatalytic experiments with methylene blue demonstrated that with zinc doped SnO₂ films photodegradation efficiencies close to 30% can be reached.     

Design of Efficient Ce<Subscript>x</Subscript>M<Subscript>1−x</Subscript>O<Subscript>2−δ</Subscript> (M = Zr,Hf, Tb and Pr) Nanosized Model Solid Solutions for CO Oxidation

Abstract  

Nanosized Ce_xM_1−xO_2−δ (M = Zr, Hf, Tb and Pr) solid solutions were prepared by a modified coprecipitation method and thermally treated at different temperatures from 773 to 1073 K in order to ascertain the thermal behavior. The structural and textural properties of the synthesized samples were investigated by means of X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), BET surface area, X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy (RS) techniques. The catalytic efficiency has been performed towards oxygen storage/release capacity (OSC) and CO oxidation activity. The characterization results indicated that the obtained solid solutions exhibit defective cubic fluorite structure. The solid solutions of ceria–hafnia, ceria–terbia and ceria–praseodymium exhibited good thermal stability up to 1073 K. A new Ce_0.6Zr_0.4O₂ phase along with Ce_0.75Zr_0.25O₂ was observed in the case of ceria–zirconia solid solution due to more Zr⁴⁺ incorporation in the ceria lattice at higher calcination temperatures. The reducibility of ceria has been increased upon doping with Zr⁴⁺, Hf⁴⁺, Tb^3+/4+ and Pr^3+/4+ cations. This enhancement is more in case of Hf⁴⁺ doped ceria. Among various solid solutions investigated, the ceria–hafnia combination exhibited better OSC and CO oxidation activity. The high efficiency of Ce–Hf solid solution was correlated with its superior bulk oxygen mobility and other physicochemical characteristics.     

Structural,electrical and magnetic properties of Co0.5Zn0.5AlxFe2−xO4 (x = 0, 0.2, 0.4, 0.6, 0.8 and 1.0) prepared via sol–gel route

Nanoparticles of Co_0.5Zn_0.5Al_xFe_2?xO₄ (x = 0, 0.2, 0.4, 0.6, 0.8 and 1.0) were synthesized by sol–gel method and the influence of Al³⁺ doping on the properties of Co_0.5Zn_0.5Fe₂O₄ was studied. X-ray diffraction studies revealed the formation of single phase spinel type cubical structure having space group Fd-3m. A decreasing trend of the lattice parameter was observed with increasing Al³⁺ concentration due to the smaller ionic radii of Al³⁺ ion as compared to Fe³⁺ ion. TEM was used to characterize the microstructure of the samples and particle size determination, which exhibited the formation of spherical nanoparticles. The particle size was found to be increases up to ～45 nm after annealing the sample at 1000 °C. Electrical resistivity was found to increase with Al³⁺ doping, attributed to the decrease in the number of Fe²⁺–Fe³⁺ hopping. The activation energy decreased with increasing Al³⁺ ion concentration, indicating the blocking of conduction mechanism between Fe³⁺–Fe²⁺ ions. The value of saturation magnetization decreased, when Fe³⁺ ions were doped with Al³⁺ ions in Co_0.5Zn_0.5Fe₂O₄; however, the coercivity values increased with increasing Al³⁺ ion content.     

Enhanced energy storage performance in samarium and hafnium co-doped silver niobate ceramics

Improving energy storage density and efficiency of antiferroelectric materials could promote their use within energy storage field, particularly in the context of pulsed power sources. In this study, Sm and Hf co-doped silver niobate (AgNbO₃; AN) ceramics were prepared using traditional solid-state method. Comprehensive analysis of crystal structure, microstructure, defects, absorbance, and energy storage performance of the material was conducted. Results reveal that co-doping increased the concentration of cation vacancies and band gap, decreased the M₁–M₂ and M₂–M₃ phase transition temperatures, and enhanced the antiferroelectric phase stability and energy storage performance. The (Ag_0.955Sm_0.015)(Nb_0.95Hf_0.05)O₃ ceramic exhibited energy storage density of 5.35 J/cm³ and energy storage efficiency of 73% at electric field (E) of 295 kV/cm, demonstrating significant improvement. The (Ag_0.955Sm_0.015)(Nb_0.95Hf_0.05)O₃ ceramic exhibited excellent thermal stability (<5% in the range of 25 °C-125 °C) and frequency stability (<3% in the range of 1–100 Hz under E = 290 kV/cm). Additionally, the (Ag_0.955Sm_0.015)(Nb_0.95Hf_0.05)O₃ ceramic exhibited ultrahigh discharge speed (∼18 μs) and high discharge energy density (4.9 J/cm³). These advantages make these ceramics promising materials for energy storage applications.     

On the way to understand the keys for the stabilization of the conductive phase in doped- NASICON-type materials

A family of doped-NASICON-type structures according to the chemical compositions: Li_1.2 Zr_1.9M_0.1(PO₄)₃ [with M = Ca²⁺, Mg²⁺, Zn²⁺]; Li_1.1 Zr_1.9Y_0.1(PO₄)₃ and Li_1.0 Zr_1.9Ce_0.1(PO₄)₃ have been synthesized by solid state reaction. The modification on the thermal treatment proposed in this work makes possible to obtain a high purity phase confirmed by XRD, SEM, microRaman-confocal and FTIR. Rietveld refinement evidences how the LZP lattice parameters are affected by each of those five different dopant cations incorporated into the pristine structure. Impedance spectroscopy proves how the relationship radius - charge of each dopant-ion affects the ionic conductivity. Unravelling that the partial replacement of Zr⁴⁺ in the LZP by a dopant improves the conductivity behavior. When the dopant cation has a lower charge and a larger size than the Zr⁴⁺ the developed structure favours the lithium-ion mobility at room temperature and the lithium conductivity increases.