CeF3 single crystals for UV-VIS-IR optical isolators

Optical isolators (OIs) are needed to protect laser sources from back-reflections. Driven by the fast-growing market of laser marking and machinery, and the increasing cost of rare-earth-based permanent magnets, single-crystalline Faraday rotators (FRs) with a large Verdet constant V are highly desired to reduce the cost and size of OIs. Furthermore, the need for finer laser procedures (marking, cutting, welding) is shifting the used laser emissions toward shorter wavelengths: into the visible (VIS), where standard Tb₃Ga₅O₁₂ (TGG) has a poor transmittance, and even into the ultraviolet (UV), where TGG possesses overlapping Tb 4f-4f absorption bands. In recent years CeF₃ has emerged as a new FR with a unique transmittance and an outstanding V in the UV wavelength region, and a superior figure-of-merit in the VIS range compared to TGG. Recently, its small thermal lensing and high damage threshold for high-power have been demonstrated, exhibiting optical isolation > 30 dB under 600 W @ 1070 nm. This review first summarizes the basic properties and crystal growth of CeF₃, then focuses on its Faraday magneto-optical performance. Last but not the least, the typical crystal defects encountered during the development of CeF₃ are discussed.     

Anisotropic domain structures of Pb(Mg1/3Nb2/3)O3–PbZrO3–PbTiO3 single crystals with high ferroelectric phase transition temperature

The anisotropic domain structures and local piezoresponse of rhombohedral Pb(Mg_1/3Nb_2/3)O₃–PbZrO₃–PbTiO₃ single crystals with high ferroelectric phase transition temperature (T_FE‐FE≥120°C) were systematically investigated by vector piezoresponse force microscopy. The typical size of labyrinthine domain pattern for [001]_C sample was in the range of 100‐200 nm, revealing its relaxor feature. While the [011]_C sample exhibited ordered ribbon‐shaped domain pattern with preferential alignment along <011> direction since the modulation effect of polar nanoregions. For [111]_C sample, it had messy and featureless domain patterns. For as‐grown crystal, the incorporation of Zr⁴⁺ cation in Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ system resulted in that the long‐range coulomb interactions of the charged ions in the short range order regions were weakened, leading to an increased relaxor feature. Concurrently, the incorporation of Zr⁴⁺ cation enhanced the Pb‐B repulsion intensity, resulting in an improved T_FE‐FE. Temperature‐dependent properties of as‐grown crystal exhibited good temperature stability from 30 to 120°C, indicating it is a promising material for actuator and ultrasonic transducer applications.     

Temperature-dependent phase transition in [001]C-oriented 0.72Pb(Mg1/3Nb2/3)O3-0.28PbTiO3 single crystals

Temperature-dependent dielectricity and polarization of [001]_C-oriented 0.72Pb(Mg_1/3Nb_2/3)O₃-0.28PbTiO₃ relaxor-based ferroelectric single crystals were studied by using a combined method of the X-ray diffraction, dielectric spectrum, polarization-electric (P-E) field hysteresis loops, and the Landau-phenomenological theory. Results show that the room-temperature rhombohedral phase experiences a rhombohedral-monoclinic-tetragonal coexisting state, then transforms to tetragonal phase, and finally to cubic phase during the zero-field-heating process. The six-order Landau-type thermal expansion parameters for the tetragonal phase were determined by using the typical characteristics at the cubic-tetragonal phase transition in the temperature range from 91 °C to 113 °C. The calculated dielectric curve, polarizations, and P-E loops fit well with the experimental results. The phase stability and piezoelectricity are further studied and compared with those of the PMN-0.36PT single crystal. The provided methods and obtained Landau parameters can be used for further studies on the relaxor-based ferroelectric single crystals.     

Hydrothermal method for the synthesis of Sb2Te3, and Bi0.5Sb1.5Te3 nanoplates and their thermoelectric properties

In this study, a modified hydrothermal method is reported for the preparation of Sb₂Te₃ and Bi_0.5Sb_1.5Te₃ nanoplates and their bulk samples was prepared by spark plasma sintering (SPS). The crystal structure, morphology, and thermoelectric properties were investigated. The microstructure results indicate that the bulk samples consisted nanograins after SPS. The presence of nanograins, high Seebeck coefficient (181 μV/K), high electrical conductivity (763 Ω^?1 cm^?1), and low thermal conductivity (1.15 W/mK) has been achieved in Sb₂Te₃ nanoplate bulk samples. As a result, the dimensionless thermoelectric figure of merit (ZT) of 0.55 at 400 K was achieved. Moreover, the peak ZT shifted to higher temperature compared with other reported results found in literature.     

Thermoelectric properties of layered oxyselenides with 3d transition metal ions

Layered oxychalcogenides have received extensive attention in the fields of magnetism, superconductivity, lithium battery, and luminescence due to their unique electronic, magnetic properties, and layered structure, among which layered oxyselenides have excellent and promising thermoelectric performance, such as BiCuSeO and Bi₂LnO₄Cu₂Se₂. Here, we successfully synthesized Sr₂MO₂Cu₂Se₂ (M = Co, Ni, Zn) and Sr₂FeO₃CuSe and investigated the thermoelectric properties at a wide temperature range (298–923 K). They have a relatively high Seebeck coefficient (>300 μV K⁻¹) in medium to high temperature range and possess a low thermal conductivity. The power factor and ZT reach 65 μW m⁻¹ K⁻¹ and 0.07 at 923 K for intrinsic Sr₂NiO₂Cu₂Se₂, and a higher performance is expected to be achieved by strategies like carrier concentration optimization and band structure engineering.     

Effects of Bi2Se3 Amount in Thermoelectric Performance of Bi2(TeSe)3 Materials Fabricated by High‐Energy Ball Milling

Amount of Bi₂Se₃ has significant role in controlling thermoelectric properties of n‐type Bi₂(TeSe)₃ material. In this study, effects of Se alloying amount in Bi₂(TeSe)₃ thermoelectric materials fabricated by high‐energy ball milling and spark plasma sintering were studied and compared with other fabrication methods. Amount of Bi₂Se₃ (5%, 10%, 15%, and 20%) did not have any significant effect over fabricated powder size, grains of consolidated bulks, and mechanical properties; however, electrical properties and thermoelectric efficiency were noticeably influenced. Both carrier concentration and carrier mobility decreased with increase in Se amount. In total, 20% Se alloying was effective in improving thermoelectric figure of merit ZT value by almost 40% compared with only 5% Se alloying.     

Thermoelectric properties and stability of glasses in the Cu‐As‐Te system

Chalcogenide glasses and more importantly their glass‐ceramics counterparts have been an interesting but very peculiar class of thermoelectric materials, with inherently low thermal conductivity (<0.3 W/m·K). In this study, we report on the fabrication of glasses in the ternary system Cu‐As‐Te (Cu_xAs_55?xTe₄₅ [5≤x≤20], Cu₁₅As_85?yTe_y [45≤y≤70], and Cu₂₀As_80?yTe_y [45≤y≤65]) by melt‐quenching and subsequent spark plasma sintering treatment. Their thermal and structural properties have been studied by differential scanning calorimetry and Raman spectroscopy, leading to give insights into the structural evolution of the glassy matrix. Coupling this information with the analysis of their electrical transport properties allowed us to deepen further our understanding of the compositional effect on their thermoelectric properties, and indirectly how the evolution of their electronic band structure is at play. Despite exhibiting low ZT values by themselves, Cu‐As‐Te glasses may still be interesting candidates for thermoelectricity through partial crystallization for which knowing the relationship between composition and properties remains essential.     

Electrical performance and ferroelectric phase transition characteristic in different oriented 0.73PMN-0.27PT single crystals

The electrical and optical properties of (001)- and (110)-oriented 0.73 Pb(Mg_1/3Nb_2/3)O₃-0.27PbTiO₃ single crystals are systematically investigated at various temperatures, both of which present a series of ferroelectric phase transition processes. Dielectric performance measurements reveal that the ferroelectric phase transition occurs over a temperature range, rather than at one temperature point. By testing the ferroelectric hysteresis P–E curves as well as bipolar and unipolar electric field-induced strain S–E curves, the values of remnant polarization, coercive field, maximum strain, and converse piezoelectric constant d₃₃^* change considerably near the phase transition temperatures. Simultaneously, the 0.73PMN-0.27PT single crystals with (001)- and (110)-orientations under a low electric field show ultrahigh d₃₃^* values of 3540 and 2817 pm/V, respectively, which can be attributed to the electric field-induced monoclinic and orthorhombic phases, respectively. The series of ferroelectric phase transitions upon heating, that is, from rhombohedral ferroelectric to monoclinic/orthorhombic, followed by from monoclinic/orthorhombic to tetragonal, and finally from tetragonal to cubic paraelectric, are further investigated via polarized light microscopy and Raman spectroscopy.     

The magnetic,thermal transport properties,magnetothermal effect and critical behavior of Co3Sn2S2 single crystal

Through the magnetic/thermal transport measurements combined with the analyses of magnetocaloric effect and critical behavior of Co₃Sn₂S₂ single crystal, the main results we obtained are as follows: in the case of the magnetic field H//c-axis, Co₃Sn₂S₂ exhibits the phase-separation state below T_c in the low-field region (H < 500 Oe). T_c increases slightly from 174 to 177 K with an increase in H from 100 to 10 kOe. The second-order magnetic phase transition near T_c and the itinerant ferromagnetism below T_c are identified. The magnetization below T_c matches well with the three-dimensional Ising model, instead of the mean-field model. In the case of H//ab, T_c changes between 175 and 178 K with varying H. Noticeably, M above T_c exhibits a small positive value, instead of the null M as commonly expected in the paramagnetic region. An extra phase transition below 166 K is observed. The magnetic transition near T_c seems not to be the second-order phase transition. All results show a significant characteristic of anisotropic magnetic phase transition for the Co₃Sn₂S₂ single crystal. They support mutually those in previous reports, moreover, some new phenomena are also observed. They also provide the experimental evidences for the deep insight into the magnetic phase–transition behavior of Co₃Sn₂S₂.     

Influence of Nb2O5 addition on dielectric properties and diffuse phase transition behavior of BaZr0.2Ti0.8O3 ceramics

Nb₂O₅ doped Ba(Zr_0.2Ti_0.8)O₃ (short as BZT20) ceramics were prepared by a mixed-oxide method using a high-energy planetary ball mill and the influence of Nb₂O₅ addition on microstructure, dielectric properties and diffuse phase transition behavior of BZT20 ceramics were investigated. It was demonstrated that Nb⁵⁺entered the B-site of BZT20 ceramic and substituted for Ti⁴⁺, which caused the expansion and distortion of crystal lattice. BZT20 ceramics doped with 0.2 mol% Nb₂O₅ showed excellent dielectric property and lower diffusivity with ε_m=37,823 and γ=1.49. We supposed that the increase of dielectric constant and decrease of diffuseness parameter with increasing Nb₂O₅ content were caused by lattice disorder and unbalancing of cations induced by the substitution of Ti⁴⁺ by Nb⁵⁺ in the B sites of BZT20 ceramics. The Curie temperature decreased with the increase of Nb₂O₅ content, which can be attributed to enlarged distortion energy of the Nb doped BZT20 structure. Besides, grain size effect on the dielectric property and diffuse phase transition behavior of Nb₂O₅ doped BZT20 ceramics was also investigated.     

Phase transition behavior of Pb(Hf,Sn, Ti,Nb)O3 ceramics at morphotropic phase boundary

The phase transition and dielectric properties of Pb_0.988(Hf_0.945Sn_xTi_0.03-xNb_0.025)O₃ ceramics (0 ≤ x ≤ 0.03, correspondingly abbreviated as H1, H2, H3, and H4) at the morphotropic phase boundary were systematically investigated. X-ray diffraction results and P-E hysteresis loops show that the dominate orthorhombic antiferroelectric phase and a small amount of the tetragonal FE phase coexist in Pb_0.988(Hf_0.945Sn_xTi_0.03-xNb_0.025)O₃ ceramics. As the Sn content increases, the antiferroelectricity is significantly enhanced, accompanied with an increased Curie temperature and sharply reduced peak dielectric constant. H1 and H2 experience an irreversible field-induced AFE-FE phase transition at the ambient temperature, and the transition from a metastable FE phase to the original AFE phase is observed in H2 when heated to 60°C. H3 and H4 experience an invertible AFE-FE phase transition, along with an enhanced forward phase switching field E_F. Moreover a decreased backward phase switching field E_A for H4 is detected as the electric field increases due to the AFE/FE coexistence. These results reveal the unique phase transition characteristics of AFE materials near the phase boundary, which is helpful for better understanding of AFE/FE materials.     

Microwave Dielectric Properties of Low-Fired ZnNb2O6 Ceramics with BiVO4 Addition

The BiVO₄ additive was found effective for low-temperature firing of ZnNb₂O₆ polycrystalline ceramics below 950°C in air without a serious degradation in their microwave dielectric properties. Dense BiVO₄-doped ZnNb₂O₆ samples of a relative sintered density over 95% could be prepared even at 925°C. An optimally processed specimen exhibited excellent microwave dielectric properties of Q · f = 55000 GHz, ɛ_r= 26, and τ_f=−57 ppm/°C. With increasing BiVO₄ addition up to 20 mol% relative to ZnNb₂O₆, while the quality factor Q · f was gradually decreased, the relative dielectric constant, ɛ_r, was linearly increased and the temperature coefficient of resonant frequency, τ_f, was slightly increased. The variations in Q · f and ɛ_r are surely attributable to the residual BiVO₄ in the ZnNb₂O₆ matrix. An unexpected slight increase in τ_f is probably due to the formation of the Bi(V,Nb)O₄-type solid solution.     

Ca3Co4O9基氧化物热电材料研究进展

详细综述了提高Ca3Co4O9基氧化物热电性能的主要途径,包括制备工艺的改进、掺杂改性研究、热电性能的结构调控等,着重从Ca位掺杂和Co位掺杂两个方面介绍了Ca3Co4O9在掺杂改性方面的研究进展,并提出了该材料存在的问题和今后的发展方向。     

Effect of Mn-doping on optical properties of lead-free (K0.4Na0.6)NbO3 ferroelectric single crystals

Optical properties of <001>-oriented pure (K_0.4Na_0.6)NbO₃ (KNN) and 0.5 wt% Mn-doped KNN (Mn-KNN) single crystals were studied. The refractive indices (n) of both crystals exhibited a normal dispersion behavior in the wavelength range of 300−1100 nm. The modified Sellmeier dispersion equations for n were obtained by least-squares fit. In addition, Sellmeier coefficients were determined by single-oscillator dispersion relation, which related to energy band structures of crystals. Compared with KNN, a decrease about 10 % in transmittance (over 350 nm) was observed in Mn-KNN due to the losses resulting from the increase of domain wall density. Furthermore, a 20 nm blue-shift in the absorption edge was observed for Mn-KNN. Based on Tauc equation, the band gap energies of 3.26 and 3.42 eV were obtained for KNN and Mn-KNN, respectively. The increase of band gap energy in Mn-KNN was attributed to the distortion of BO₆ octahedron building block caused by Mn²⁺ occupying the B-site.     

Tuning oxygen vacancy in LiNbO3 single crystals for prominent memristive and dielectric behaviors

Understanding and manipulating the behavior of oxygen vacancy in oxide materials are of vital importance for rejuvenating materials with novel functionalities. We herein report a exciting phenomenon of oxygen vacancies changing from an isolated state to a clustered state in LiNbO₃ single crystals. The clustering of the oxygen vacancies induces a relaxor-like dielectric anomaly and a first-order phase transition. The relaxor-like dielectric anomaly was argued to be a pseudo-relaxor behavior resulting from the combined contributions of a dipolar relaxation and a Maxwell-Wagner relaxation. The first-order phase transition was ascribed to be an electric-ferroelectric phase transition. Interestingly, a well-defined melting point of the oxygen-vacancy clusters was observed. At temperatures near the point, a small dc field can lead to resistance switching from a high resistance state to a low resistance state, yielding a prominent memristive effect with the OFF/ON ratio of 10². Our results underscore that controlling the oxygen vacancy state is a promising strategy to tailor the properties of oxides for novel device applications.     

Pulsed electrodeposition of (Bi1-xSbx)2Te3 thermoelectric thin films

(Bi_1-xSb_x)₂Te₃ thermoelectric thin films were deposited on stainless steel discs in 1 M perchloric acid and 0.1 M tartaric acid by pulse electrodeposition in order to optimize the grain growth. The influence of the electrolyte composition, the cathodic current density and the cathodic pulse time on film stoichiometry were studied. The results show that it is necessary to increase the Sb content in the electrolyte to obtain the (Bi_0.25Sb_0.75)₂Te₃ film stoichiometry. Pulse plating reduced the grain size and the roughness, compared with continuous plating. Thermoelectric and electrical properties were also studied and it was found that the Seebeck coefficient and electrical resistivity were related to two parameters: the cathodic pulse current density and the films thickness.     

High temperature‐insensitive ferro‐/piezoelectric properties and nanodomain structures of Pb(In1/2Nb1/2)O3–PbZrO3–Pb(Mg1/3Nb2/3)O3–PbTiO3 relaxor single crystals

For rhombohedral (R) Pb(In_1/2Nb_1/2)O₃–PbZrO₃–Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ (PIN–PZ–PMN–PT) relaxor single crystal, high temperature‐insensitive behaviors under different external stimuli were observed (remnant polarization P_r from 30°C to 180°C and piezoelectric strain d₃₃* from 30°C to 116°C). When electric field E ≥ 50 kV/cm in the case of an activation field E_a = 40‐50 kV/cm was applied, it was found that the domain switching was accompanied by a phase transition. The high relaxor nature of the R phase PIN–PZ–PMN–PT was speculated to account for the large E_a and high piezoelectric response. The short‐range correlation lengths extracted from the out‐of‐plane (OP) and in‐plane (IP) nanodomain images, were 64 nm and 89 nm, respectively, which proved the high relaxor nature due to In³⁺ and Zr⁴⁺ ions entering the B‐site in the ABO₃‐lattice and enhancing the disorder of B‐site cations in the R phase PIN–PZ–PMN–PT. The switching process of R nanodomain variants under the step‐increased tip DC voltage was visually revealed. Moreover, the time‐dependent domain evolution confirmed the high relaxor nature of the R phase PIN–PZ–PMN–PT single crystal.     

Thermoelectric properties of the textured Bi1.9Gd0.1Te3 compounds spark-plasma-sintered at various temperatures

Elemental composition, crystal and grain structures, specific electrical resistivity, Seebeck coefficient, thermal conductivity, and thermoelectric figure-of-merit of n-type grained Bi_1.9Gd_0.1Te₃ compounds, spark-plasma-sintered at T_S = 690, 720, 750, 780 and 810 K, have been studied. All the samples are highly textured along the 001 direction parallel to the pressing direction. The average grain size measured along the pressing direction is much less as compared to the average grain size measured in the perpendicular direction. A strong anisotropy in the transport properties measured along directions parallel and perpendicular to the pressing direction was found within the 290 ÷ 630 K interval. Electrical resistivity decreases and thermal conductivity increases for parallel orientation as compared to these properties for perpendicular orientation. The T_S - effect on thermoelectric figure-of-merit of textured Bi_1.9Gd_0.1Te₃ compounds has been found and analyzed. Highest thermoelectric figure-of-merit (∼0.75) was observed for sample with T_S = 750 K at perpendicular orientation.     

Concentration threshold effect on properties of zinc‐doped lithium niobate crystals

Results of LiNbO₃:Zn researches often diverge because sharp changes in physicochemical characteristics of the system melt‐crystal that occur at doping are usually not taken into consideration. When a series of doped crystals is grown Zn is usually added to the melt with step 1.5‐2 mol%. This obstructs detection of exact threshold concentration. We have grown LiNbO₃:Zn crystals doped by 4.0÷9.0 mol% ZnO with step ~1 mol%. Around the dopant, threshold concentration step was narrowed to ~0.1 mol%. We have researched physicochemical properties of the system melt‐crystal and structure evolution by Raman spectroscopy and full‐profile analysis of XRD. We have detected exact threshold concentration for LiNbO₃:Zn and concluded that crystals doped by prethreshold concentrations of ZnO are the best for most applications because of the higher optical homogeneity.     

Antiferroelectric‐ferroelectric phase transition in lead‐free AgNbO3 ceramics for energy storage applications

The high‐energy storage density reported in lead‐free AgNbO₃ ceramics makes it a fascinating material for energy storage applications. The phase transition process of AgNbO₃ ceramics plays an important role in its properties and dominates the temperature and electric field dependent behavior. In this work, the phase transition behavior of AgNbO₃ ceramics was investigated by polarization hysteresis and dielectric tunability measurements. It is revealed that the ferrielectric (FIE) phase at room temperature possesses both ferroelectric (FE)‐like and antiferroelectric (AFE)‐like dielectric responses prior to the critical AFE‐FE transition point. A recoverable energy storage density of 2 J/cm³ was achieved at 150 kV/cm due to the AFE‐FE transition. Based on a modified Laudau phenomenological theory, the stabilities among the AFE, FE and FIE phases are discussed, laying a foundation for further optimization of the dielectric properties of AgNbO₃.