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•Achievements on 17 representative types of IR–NLO chalcogenides based on the chemical substitution strategy are overviewed.•The interrelationship of “chemical composition-NCS ...structure-NLO property” is studied and summarized systematically.•Several useful conclusions and future considerations have been provided.
Infrared nonlinear optical (IR–NLO) materials are crucial for obtaining the solid-state lasers in the spectral range of 2–20 μm, which have a broad range of applications, such as signal communication, microscopy, and data processing. Yet, the considerable challenge is how to obtain a strictly structural non-centrosymmetric (NCS) space group, which is the paramount precondition for the IR–NLO materials. Thus, over the past decades, continuous efforts have been made to obtain the crystals with NCS space groups by adopting various synthesis approaches, discovering numerous state-of-the-art IR–NLO materials, especially inorganic chalcogenides. Among them, the chemical substitution strategy has proven to be a general and effective method based on known structural prototypes, which can maintain or recombine the crystal structures by a simple element replacement. In this review, 17 representative types (including 6 crystal systems, 27 NCS space groups and about 600 inorganic chalcogenides) ranging from zero-dimensional (0D) molecular to the three-dimensional (3D) framework, and then to mixed-dimensional (MD) structures obtained by the chemical substitution strategy are selected and discussed. The interrelationship of “chemical composition-NCS structure-NLO property” for the 17 representative types is studied and summarized systematically. In addition, the two kinds of structural transformations based on the chemical substitution strategy, including centrosymmetric (CS) to NCS and NCS to NCS, are also described. Finally, we conclude and give the future prospects of this research area.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
The 0.94Bi0.5Na0.5TiO3–0.06BaTiO3(BNBT6) introduced by CaZrO3(CZ) lead-free ferroelectric ceramics are successfully fabricated by conventional solid state reaction. The influence of CZ substitution ...on the phase transition, microstructure, dielectric, ferroelectric, and energy storage properties of (1 − x)BNBT6-xCZ ceramics are systematically investigated. The energy-storage density 0.7 J/cm3 under the electric field 70 kV/cm is obtained in the 0.97BNBT6-0.03CZ. In addition, its energy-storage property exhibits thermal stability at the temperature range of 30–130 °C.
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•The CZ addition helps BNBT6 obtain the lower porosity and uniform surface.•The introduction of CZ lowers TF–R and enhances relaxor-ferroelectric of BNBT6.•The energy storage of BNBT6 is enhanced by CZ addition.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK, ZRSKP
We used the solid-state reaction (SSR) method to make samarium oxide-doped SrTiO3 perovskite ceramic. We then put the synthesized samples through PXRD analysis to look at their structural properties. ...It is observed that the Sm-doped SrTiO3 exhibited a cubic phase, with no secondary phase resulting from Sm-doping. For a higher doping concentration (at 5 %) of Sm2O3, we slightly increased the particle size (from 30 nm to 33 nm). HR-SEM is used to study the morphology and nature of each sample. We examined the component composition of Sr, Ti, O, and Sm using the EDAX spectra and matched it with the stoichiometry ratio. FT-IR spectroscopy was carried out to analyze the presence of functional groups and chemical bonding in the samples. We studied the magnetic properties of the synthesized samples at room temperature using the VSM technique. The coercivity, retentivity, and saturation magnetization of SrTiO3 considerably increased with a higher doping concentration of Sm. We used UV diffuse reflectance spectroscopy to record the reflectance spectra and calculate the optical energy values. An increase in Sm-doping concentration red-shifted the absorption peaks. The photoluminescence spectra revealed that the samples exhibited a wide spectrum of colours. The proposed combination of nanomaterials is suitable to become an appropriate candidate for white LED applications.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
A simple adduct from tin tetraiodide SnI4 and octasulfur S8, SnI4⋅(S8)2 (1), is obtained employing a facile reaction. The combination of Sn4+ ions with d10 electron configuration, acentric SnI4 ...tetrahedra, and lone‐pair effects of S8, makes 1 a phase‐matchable infrared NLO crystal with a moderate second‐harmonic generation (SHG) response and a very high laser‐induced damage threshold (LIDT), which is well confirmed by the DFT calculations.
The adduct SnI4⋅(S8)2, obtained by a solid‐state reaction, shows a moderate nonlinear optical (NLO) intensity and a large laser induced damage threshold (LIDT). Its phase‐matchable character and wide IR transparency make it a very promising IR NLO crystal, comparable to the benchmark system AgGaS2 (AGS).
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
A series of Eu3+/Bi3+ single and co-doped La2MgSnO6 phosphors are synthesized by the solid-state method. The crystal structure, optical properties, energy transfer processes, and thermal stability of ...phosphors are investigated systematically. Under 331 nm excitation, both the orange-red emission of Eu3+ ions ranging from 500 to 750 nm and the blue emission band centered at 403 nm are observed in the La2MgSnO6:Eu3+, Bi3+ samples. With the doping concentration of Eu3+ changing, the emission of La2MgSnO6:Eu3+, Bi3+ phosphors can be adjusted from blue (0.219, 0.350) to orange-red light (0.644, 0.341) in chromaticity coordinate. Furthermore, the security ink prepared by phosphors can be effectively used for encryption writing and anti-counterfeit marking. Additionally, the latent fingerprint developed using La2MgSnO6: Eu3+, Bi3+ phosphor demonstrates excellent contrast and sensitivity.
•La2MgSnO6:Eu3+ phosphors were prepared by solid-state method, and the crystal optical properties were investigated.•A series of Eu3+/Bi3+ co-doped La2MgSnO6 phosphors was prepared, which exhibit adjustable emission properties.•The efficient energy transfer from Bi3+ to Eu3+ was discovered and studied.•The applications of security ink and latent fingerprint were explored.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK, ZRSKP
At room temperature, monoclinic In2W3O12 ceramics exhibits positive thermal expansion. However, it transforms into an orthorhombic phase above 253 ℃, and then stably exhibits negative thermal ...expansion (NTE). In this work, to improve the NTE performance and extend the NTE temperature range of In2W3O12, the KxMnxIn2-xW3O12(0≤x≤0.5) ceramics were synthesized via the solid-state reaction method. The effects of (KMn)3+ double cation co-doping on the composition, microstructure, and thermal expansion behaviors of In2W3O12 ceramics were studied using XRD, Raman, XPS, SEM, and TMA. The results show that (KMn)3+ cations can replace In3+ in In2W3O12 ceramics. As the (KMn)3+ doping amount increases, monoclinic In2W3O12 gradually changed into monoclinic KxMnxIn2-xW3O12. Meanwhile, the grains grow up and the density of KxMnxIn2-xW3O12 ceramics was increased. Pure monoclinic KxMnxIn2-xW3O12 ceramics were prepared when x rises to 0.25 and 0.4. Among them, the thermal expansion coefficient of K0.4Mn0.4In1.6W3O12 ceramics in 100–700 ℃ is as high as -17.83×10-6 ℃-1, which was significantly improved compared to In2W3O12 ceramics. In addition, the structural phase transition of In2W3O12 ceramics around 253 ℃ was gradually eliminated and the NTE temperature range was widened. Double cation (KMn)3+ co-doping effectively improves the NTE performance of In2W3O12.
•(KMn)3+ co-doped In2W3O12 ceramics were prepared by solid-state method.•(KMn)3+ co-doping induces a phase transition in In2W3O12 ceramics.•Monoclinic KxMnxIn2-xW3O12 ceramics show stronger NTE as x increases.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Inorganic-polymer composites have become promising materials to be processed by printing technologies because of their unique properties that allow the fabrication of flexible wearable electronics at ...reduced manufacturing costs. In the present work, a complete methodological process of assembling a flexible microthermoelectric generator based on inorganic-polymer materials is presented. The used microparticles were prepared by a top-down approach beginning with a previously prepared material by solid-state reaction and later scaled down through the use of ball milling. It was found that the necessity to proceed with a chemical treatment with HCl to reduce Bi
O
present on the surface of the microparticle leads to a power factor (PF) of 2.29 μW K
m
, which is two times higher than that of the untreated sample. On the fabrication of flexible inorganic-organic thermoelectric thick films based on Bi
Te
microparticles (<50 μm) and the poly(vinyl alcohol) (PVA) polymer with different thicknesses ranging from 11 to 265 μm and with different Bi
Te
weight percentages (wt %), we found that PVA allowed achieving a homogeneous dispersion of the parent inorganic thermoelectric materials, while still maintaining their high performance. The best produced ink was obtained with 25 wt % of PVA and 75 wt % of chemically treated Bi
Te
micropowder with a Seebeck coefficient of -166 μV K
and a PF of 0.04 μW K
m
. For this optimized concentration, a flexible thermoelectric device was fabricated using n-type thermoelectric inks, which constitutes a major advantage to be applied in printing techniques because of their low curing temperature. The device architecture was composed of 10 stripes with 0.2 × 2.5 cm
each in a one-leg configuration. This prototype yielded a power output up to ∼9 μW cm
with a 46 K temperature gradient (Δ T), and the results were combined with numerical simulations showing a good match between the experimental and the numerical results. The thermoelectric devices studied in this work offer easy fabrication, flexibility, and an attractive thermoelectric output for specific power requirements such as for environmental health monitoring.
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IJS, KILJ, NUK, PNG, UL, UM
(1-x)NBT-xBSN (0.1 ≤ x ≤ 0.35) ceramics were prepared by solid state methods and their energy storage properties and high-temperature capacitor applications were systematically investigated. All ...samples showed a perovskite structure and the structure transformed to lower symmetry orthorhombic phase (x ≥ 0.1) from rhombohedral phase (x < 0.1) to with the addition of BSN. The more addition content of BSN significantly decreases phase transition temperature Tm of NBT ceramics. The x = 0.25 sample exhibits a stable relative permittivity of 1605 ± 15% in a broad temperature range of 38 °C to 319 °C. With increasing BSN concentration, the slope of the P-E loops and the energy loss gradually decreases. When x = 0.25, a high breakdown strength of 190 kV/cm and the maximum discharge energy density of 1.91 J/cm3 were obtained, of which the energy efficiency was as high as 86.4%. Thus, it was believed that our work could provide a significant guidance for designing the new system for energy storage.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK, ZRSKP
•GLNSYMnO3 has a single-phase orthorhombic perovskite structure sintered at 1250 °C.•The high configurational entropy drives the structural stability of GLNSYMnO3 even at temperatures below ...TC.•GLNSYMnO3 has good magnetism due to the lattice distortion and double-exchange.•GLNSYMnO3 is a second-order magnetic phase transition material with potential applications in magnetic storage.
Rare-earth transition element high-entropy perovskite ceramics (HEPCs) (Gd0.2La0.2Nd0.2Sm0.2Y0.2)MnO3 (GLNSYMnO3) were prepared by using a solid-state reaction method, and the structure, morphology and magnetic properties of the GLNSYMnO3 were studied. The crystalline structure of GLNSYMnO3 is a smooth surface and similar to “cashews” tubular particles, and a single-phase orthorhombic (Pbnm Space group) perovskite without impurities is confirmed when the sintered temperature reaches or exceeds 1250 °C by the analysis of phase composition and microstructures. Magnetic measurements indicate that GLNSYMnO3 HEPCs have low Curie temperature (TC = 61 K), but they exhibit a good magnetism by comparison with other high-entropy ceramics, which is caused by the lattice distortion and exchange interactions between high concentrations of Mn3+ (92.4 %) and non-magnetic oxygen ions, promoting the movement of circulating electrons. GLNSYMnO3 HEPCs did not undergo a phase transition below TC due to high configurational entropy driving structural stability. In addition, GLNSYMnO3 HEPCs undergo a second-order magnetic phase transition from isothermal magnetization curves and Arrot curves, which have potential applications in magnetic storage.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Facile fabrication of advanced catalysts toward oxygen reduction reaction with improving activity and stability is significant for proton‐exchange membrane fuel cells. Based on a generic solid‐state ...reaction, this study reports a modified hydrogen‐assisted, gas‐phase synthesis for facile, scalable production of surfactant‐free, thin, platinum‐based nanowire‐network electrocatalysts. The free‐standing platinum and platinum–nickel alloy nanowires show improvements of up to 5.1 times and 10.9 times for mass activity with a minimum 2.6% loss after an accelerated durability test for 10k cycles; 8.5 times and 13.8 times for specific activity, respectively, compared to commercial Pt/C catalyst. In addition, combined with a wet impregnation method, different substrate‐materials‐supported platinum‐based nanowires are obtained, which paves the way to practical application as a next‐generation supported catalyst to replace Pt/C. The growth stages and formation mechanism are investigated by an in situ transmission electron microscopy study. It reveals that the free‐standing platinum nanowires form in the solid state via metal‐surface‐diffusion‐assisted oriented attachment of individual nanoparticles, and the interaction with gas molecules plays a critical role, which may represent a gas‐molecular‐adsorbate‐modified growth in catalyst preparation.
Free‐standing platinum and platinum–nickel alloy nanowires are synthesized by a modified facile hydrogen‐assisted gas‐phase method. In situ transmission electron microscopy observation reveals that the formation of nanowires is attributed to surface‐diffusion‐assisted, solid‐state oriented attachment. The Pt and Pt1.3Ni‐alloy nanowires exhibit promising catalytic activity and excellent stability compared with commercial Pt/C toward oxygen reduction reaction.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
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