Nanocrystallization and optical properties of CsPbBr3−xIx perovskites in chalcogenide glasses

The confinement of CsPbX₃ (X = Cl, Br, and I) perovskite nanocrystals (NCs) in a stabilized inorganic glass matrix is a new strategy for improving their long-term stability and promoting their applications in the optoelectronic field. Here, in situ nanocrystallization strategy is developed to precipitate CsPbBr_3?xI_x NCs with arbitrary I/Br ratio among an elaborately designed GeS₂–Sb₂S₃-based chalcogenide glass matrix. Spherical CsPbBr_3?xI_x NCs are homogeneously distributed in the glass matrix after thermal treatment. The photoluminescence (PL) spectra show that the emission peaks of CsPbBr_3?xI_x NCs can be tuned from 570 nm to 722 nm with the replacement of Br by I. The fs transient absorption (TA) spectra reveal that there exists some structural defects in the NCs, leading to short PL decay life. This work would shed light on confining CsPbX₃ NCs into glassy matrices, facilitating their future applications in photoelectronic fields.     

Nonlinearity in regulating the metal to insulator transition of ReNiO3 towards low temperature range

Among the existing material family of the correlated oxides, the rare earth nickelates (ReNiO₃) exhibit broadly adjustable metal to insulator transition (MIT) properties that enables correlated electronic applications, such as thermistors, thermochromics, and logical devices. Nevertheless, how to accurately control the critical temperature (T_MIT) of ReNiO₃ via the co-occupation of the rare-earth elements is yet worthy to be further explored. Herein, we demonstrate the non-linearity in adjusting the T_MIT of ReNiO₃ towards lower temperatures via introducing Pr co-occupation within ReNiO₃ (e.g., Pr_xNd_1-xNiO₃ and Pr_xSm_1-xNiO₃) as synthesized by KCl molten-salt assisted high oxygen pressure reaction approach. Although the T_MIT is effectively reduced via Pr substitution, it does not strictly follow a linear relationship, in particular, when there is large difference in the ionic radius of the co-occupation rare-earth elements. Furthermore, the most significant deviation in T_MIT from the expected linear relationship appears at an equal co-occupation ratio of the two different rare-earth elements, while the abruption in the variation of resistivity across T_MIT is also reduced. The present work highlights the importance to use adjacent rare-earth elements with co-occupation ratio away from 1:1 for achieving more linear adjustment in designing the metal to insulator transition properties for ReNiO₃.     

A-site Ca2+ substitution induced polyvalent Cu cations and correlated polaron relaxations in colossal permittivity Li1-xCaxCuNb3O9

LiCuNb₃O₉ has been reported newly a colossal permittivity (CP) perovskite, in which the B-site NbO₆ octahedra play a bridging role in the polaron hopping. However, how the A-site modification affects the origin of the polarons and further the CP behaviours remains unexplored. To this end, A-site Ca²⁺ was incorporated to form Li_1-xCa_xCuNb₃O₉, and the local states, dielectric relaxations and conduction behaviours were comprehensively studied. The substitution induces the polyvalent Cu cations, i.e. Cu⁺/Cu²⁺/Cu³⁺. Bond valence sum calculations imply that Cu²⁺ and Cu³⁺ are underbonded, and Cu⁺ is overbonded, while B-site Nb⁵⁺ shows slightly different with theoretical pentavalence. All the compositions exhibit a similarly room-temperature CP response, but present two dielectric relaxations, i.e. T_R1:170–300 K and T_R2:260–400 K. Comprehensive investigations on universal dielectric response and bulk dc conductivity indicate that the T_R1 follows the variable-range-hopping where the electron hopping between the mixed Cu⁺/Cu²⁺, while T_R2 contributes from the Cu³⁺ nearest neighbor hopping.     

Structural and electrical studies of excessively Sm2O3 substituted soft PZT nanoceramics

The solid solution of Pb_1-x Sm_2x/3 (Zr_0.6 Ti_0.4) O₃ ceramics with x = 0.1, 0.2, 0.3, and 0.4 was prepared via the high-energy ball milling technique. Further, the effect of excessive Sm₂O₃ substitution at Pb-site on structural, dielectric, and dc-conductivity properties was studied. The X-ray diffraction (XRD) analysis confirmed that all samples were crystallized with perovskite and pyrochlore diphase form. Excess Sm³⁺ substitution in the PZT system increases the pyrochlore volume fraction from 5 to 20% and induces a structural phase transition from rhombohedral to a tetragonal structure. The microstructural study by TEM and SEM indicated that the particles were spherical with an average size of 43–55 nm. The frequency and temperature-dependent dielectric constant for all compositions was carried out and it is obtained that the dielectric constant decreases with Sm³⁺ content. The phase transition temperature first decreases up to x = 0.2 and then increases for the higher concentration of samarium. The dc-conductivity studies revealed that all samples showed an unusual mixed TCR effect (both positive and negative temperature coefficient of resistance). Such properties of the studied samples indicate that the material is suitable for potential applications in thermistors, and temperature sensors of the automotive, and petroleum industries.     

Mesoporous SmMnO3/CuMnOx catalyst for photothermal synergistic degradation of gaseous toluene

Mesoporous SmMnO₃/CuMnO_x catalyst was prepared by a two-step method using flaky CuMnO_x with high specific surface and excellent catalytic ability as the carrier, which was further applied to photothermal synergistic degradation of gaseous toluene. Quantitative analysis of O₂-TPD and H₂-TPR showed that SmMnO₃/CuMnO_x exhibited abundant of the surface oxygen species and oxygen vacancies content, which enabled it to convert free oxygen to lattice oxygen more quickly during the reaction, and thus improving the reaction process. I-t and photoluminescence experiments demonstrated the improvement of photogenerated electron and hole separation ability of SmMnO₃/CuMnO_x catalyst. UV–Vis analysis manifested the full spectral range of absorption. XPS analysis verified the unequal positions of valence band of the two materials, which can facilitate the separation of photogenerated electrons from holes and improve the ability of better electron transfer. SmMnO₃/CuMnO_x catalyst has higher adsorbed oxygen content and light absorption capacity, which is beneficial to the catalytic oxidation. In situ DRIFTs proved that the oxidation reaction on the catalyst followed the Mars-van Krevelen redox cycle. The VOCs test found that SmMnO₃/CuMnOx composite catalyst is with lower onset reaction temperature (T₉₀ = 190 °C, T₉₀, corresponding to 90% conversion) and good mineralization (100% at 275 °C).     

Grain boundary engineered,multilayer graphene incorporated LaCoO3 composites with enhanced thermoelectric properties

Enhancement of thermoelectric properties by virtue of decreased electrical resistance through grain boundary engineering is realised in this study. A robust strategy of optimisation of the transport properties by tuning the energy filtering effects at the interfaces by decreasing the interfacial electrical resistance is achieved in LaCoO₃ (LCO). This is accomplished by the incorporation of multilayer graphene within the parent LCO matrix containing multi-scale nano/micro grains. The present work has attained a substantial increment in electrical conductivity from a value of 96 Scm^-1 for bare LCO to ～5300 Scm^-1 at 750 K by incorporating 0.08 wt% multilayer graphene in LCO. No significant change in thermal conductivity is observed due to the presence of multilayer graphene in LCO. A zT of 0.33 at 550 K for 0.08 wt% multi-layer graphene incorporated LCO composite is achieved which is the highest thermoelectric figure of merit value for undoped LCO reported until now.     

Comment on“Hole-pinned defect-dipoles induced colossal permittivity in Bi doped SrTiO3ceramics with Sr deficiency”

With this contribution,as a comment to the publication in Journal of Mate rials Science&Technology 44(2020)54,reporting giant dielectric response,structural characterization and numerical simulations in Sr_(1-1.5 x)Bi_xTiO₃ceramics,we show that the re ported results are rather contradicting and not well analysed,while the suggested mechanism for the giant permittivity response is not valid or doubtful and has to be reconsidered.Moreover,many details and data are missing making impossible not only to call the obtained results very suitable for practical application but even to reproduce them.     

Emergence of relaxor behavior along with enhancement in energy storage performance in light rare-earth doped Ba0.90Ca0.10Ti0.90Zr0.10O3 ceramics

Nano-sized light rare-earth (La, Pr, Nd, and Sm) doped Ba_0.90Ca_0.10Ti_0.90Zr_0.10O₃ ceramics were synthesized to enhance the energy storage performance. The Rietveld study of bare and doped samples has shown tetragonal crystal symmetry and a single-phase perovskite structure. The rare-earth addition in Ba_0.90Ca_0.10Ti_0.90Zr_0.10O₃ has resulted in a remarkable change in the microstructure of the doped samples. The addition of Nd in Ba_0.90Ca_0.10Ti_0.90Zr_0.10O₃ lattice has resulted in optimum grain size and density among the five compositions. As a result of improvement in morphological characteristics in the Nd-doped sample, the dielectric, ferroelectric and piezoelectric characteristics were significantly enhanced. The Nd-doped sample has shown a relaxor behavior with a maximum dielectric constant of 10788 combined with a high saturation polarization of 41.88 μC/cm². Further, the material has shown optimum electromechanical behavior with excellent aging characteristics. The obtained properties of Nd-doped Ba_0.90Ca_0.10Ti_0.90Zr_0.10O₃ sample justifies its potential application in multi-layer energy storage capacitors.     

CO2 sensing properties and mechanism of PrFeO3 and NdFeO3 thick film sensor

The CO_2 sensing of PrFeO_3 and NdFeO_3 sensors were investigated. Experimental results show that the resistances for PrFeO_3 and NdFeO_3 in CO_2 gas are larger than those in air and the responses for PrFeO_3and NdFeO_3 sensors increase with an increase in room-temperature relative humidity. When exposed to1000 ppm CO_2, the response of PrFeO_3 thick film based on nano-powders annealed at 700℃can reach8.44 at 160℃for the background of wet air with 58%of room-temperature relative humidity (RH),which is much larger than the corresponding value (3.03) in wet air with 25%RH. The sensing response S of NdFeO_3 thick-film sensor based on nano-powders annealed at 600℃to 3000 ppm CO_2 at the operating temperature 200℃can reach 2.36 for the background of wet air with 72%RH, which is larger than the corresponding value (1.83) in the air with 25%RH. Compared with other CO_2 sensing materials, the PrFeO_3 sensor has larger response at lower operating temperature for CO_2 gas and may be used as a new CO_2 sensing material.