O3 Single Crystals Research Articles

Origin of giant dielectric constant in Ta+Gd co-doped TiO2 single crystals by optical traveling floating zone method

The co-doped TiO2 polycrystalline ceramics have dramatic dielectric behavior (>104), but its source is still not completely clarified. Compared to ceramic materials, single crystals can maintain most of the original properties of the material and eliminate the grain boundary and pore interferences, thus facilitating the exploration of the source of the dielectric properties. Here, we chose Gd3+ with a moderate ionic radius as the acceptor ion and Ta5+ as the donor, preparing (Gd0.5Ta0.5)0.01Ti0.99O2 single crystals by the optical traveling floating zone method to investigate giant dielectric properties. It was found that a dielectric constant (ε′ ∼1.5 × 104), and a dielectric loss (tanδ ∼ 0.07) were achieved simultaneously in (Gd0.5Ta0.5)0.01Ti0.99O2 single crystals at 105Hz. Electrochemical impedance spectroscopy and XPS analyses indicate that the high dielectric properties are mainly attributed to electrons pinning defective dipoles clusters. In addition, dielectric relaxation behavior under DC bias suggests that electrode effects also affect the dielectric constant. This study provides insights for the origin of the large dielectric constant and the growth of single crystals in TiO2-based materials.

Synthesis of Monodisperse and Discrete Ultra-High Nickel LiNi0.97Co0.02Mn0.01O2 Octahedral Single Crystals via Single Crystal Intermediates for Li-Ion Batteries.

Micrometer-sized single crystal cathodes have garnered significant interest as promising cathode materials for lithium-ion batteries due to their ability to reduce surface area exposure to electrolytes and suppress side reactions, thereby enhancing electrochemical performance. One of the challenging issues with single crystal cathode materials is synthesizing monodisperse and discrete single crystals rather than agglomerated quasi-single crystals. However, conventional solid-state synthesis of most single crystals results in severe agglomeration and cation mixing, as it requires high temperatures to promote particle growth to several micrometers. In this study, a novel morphology-conserving reaction strategy that employs octahedron single crystal intermediates is introduced to synthesize discrete, monodisperse LiNi0.97Co0.02Mn0.01O2 octahedron single crystals. This scalable and cost-effective approach involves using rock-salt Ni0.97Co0.02Mn0.01O1+x octahedrons as single crystal intermediates, which are transformed in unreactive unary lithium salt melts (LiCl and Li2SO4) from spherical Ni0.97Co0.02Mn0.01(OH)2 obtained via coprecipitation. These intermediates are then subjected to a stoichiometric amount of Li precursor in a conventional solid-state synthesis to produce layered LiNi0.97Co0.02Mn0.01O2. This process is a morphology-conserving lithiation reaction, leading to the formation of discrete and monodisperse LiNi0.97Co0.02Mn0.01O2 octahedron single crystals. The resultant LiNi0.97Co0.02Mn0.01O2 single crystals demonstrate superior electrochemical performance, including stable capacity retention over 150 cycles, which surpasses that of typical quasi-single crystals produced through conventional methods. This is attributed to negligible crack formation during cycling, in contrast to significant cracking observed in conventional quasi-single crystals. This implies that single-crystal forms are preferred over agglomerated quasi-single crystal forms for enhancing cycle performance. These findings provide valuable insights into the industrial synthesis of discrete and monodisperse ultrahigh-nickel oxide cathode materials.

Mn doping-induced twofold spin reorientation and multi-step spin switching in NdFeO3 single crystal

Magnetization reversal and magnetic state regulation are the basis of application for magnetic materials in information processing. Here, twofold spin reorientation transitions (SRT) and field-induced multi-step spin switching phenomena were observed in NdMn0.2Fe0.8O3 (NMFO) single crystals grown via the optical floating zone method. Magnetic anisotropy was systematically investigated in both Zero-Field-Cooled (ZFC) and Field-Cooled (FC) modes. The NMFO single crystal exhibited twofold SRTs: from Γ4 (Gx, Ay, Fz) to Γ1 (Ax, Gy, Cz) and from Γ1 (Ax, Gy, Cz) to Γ2 (Fx, Cy, Gz). Furthermore, a magnetic field-induced spin reorientation transition was identified along the c-axis. Additionally, closer proximity to the SRT temperature corresponded to a reduced magnetic field requirement for inducing the spin reorientation transition. These findings contribute to our comprehension of spin dynamics in NMFO, presenting possibilities for future device applications.

AC poling of high Qm and low acoustic impedance Pb(Mg1/3Nb2/3)O3-Pb(Zr,Ti)O3 single crystals produced by a solid-state crystal growth

The AC poling cycle dependence of Mn-doped Pb(Mg1/3Nb2/3)O3-0.3Pb(Zr.Ti)O3 (PMN-0.3PZT) single crystals (SC) produced via the solid-state crystal growth (SSCG) method was investigated. The piezoelectric strain and charge constants, d 33 ＝ 1130 pC/N, g 33 = 42.7 × 10−3 Vm/N, and mechanical quality factor Q m = 800 were obtained under conditions of 1 Hz, bipolar sine wave, 7.5 kV cm−1 electric field, and 6000 cycles. In contrast to the conventional Bridgman process SC, the low-density and high Q m SSCG SC necessitates a substantial number of AC cycles due to the presence of pores within the SC. In addition, the ACP SC showed a 13 °C increase in the phase change temperature T rt compared to the DC-poled SC. This information on ACP SSCG SCs with improved thermal stability, low acoustic impedance, and enhanced receiving efficiency attributable to high g 33 offers new insight into high-frequency ultrasonic devices.

Low-frequency dynamics of 0.45PMN-0.55PSN solid solution

Lead magnoniobate-scandoniobate (PMN-PSN) solid solutions are important functional materials for transducer/actuator devices due to their extraordinary dielectric and electromechanical properties. These unique properties are related to the unusual low-frequency relaxation dynamics, which has not been sufficiently understood until now. In our paper the low-frequency relaxation dynamics of 0.45Pb(Mg1/3Nb2/3)O3–0.55Pb(Sc1/2Nb1/2)O3 single crystal is studied in frequency range 10 mHz–1 MHz at temperatures near the dielectric permittivity maximum. Four relaxation processes are identified. Low-frequency mode demonstrating the critical divergence around 306 K is revealed. However, the phase transition into ferroelectric phase at this temperature does not occur. Near 306 K, the appearance of M-type superstructure is found related to the combination of oxygen octahedral rotation and anti-parallel shifts of lead ions. The appearance of the additional order parameter suppresses the slowing down of the ferroelectric mode and the phase transition into the ferroelectric phase occurs only below 295 K. In addition, two relaxation processes, similar to reorientation and “breathing” polar nanoregion (PNR) modes reported for PMN, are found. The sharp softening of “reorientation mode” is observed on cooling from 315 to 295 K with Tf ∼288 K. The fourth relaxation process is the Debye process, and we assume that it is associated with defects relaxation. Below 295 K, all four relaxation processes still exist, but their parameters are practically temperature independent. The low-temperature phase is not exactly a “normal” ferroelectric phase, the PNRs persist in the FE phase.

Field-induced effects and ferroelectric critical endpoint in (K0.95Li0.05)(Nb1–x Ta x )O3 single crystals

Dielectric permittivities under dc biasing fields in the temperature range between –169 °C and 75 °C have been investigated in (K0.95Li0.05)(Nb1–x Ta x )O3 (KLNT–x, x = 71% and 74%). Field-induced ferroelectric phase transitions in KLNT–x have been clarified in the dc field applied along the [001] c direction (in the cubic coordinate). The ferroelectric critical endpoints in KLNT–71% and KLNT–74% have been determined to be 43.5 °C, 3.0 kV cm−1, and 30.3 °C, 2.0 kV cm−1, respectively. The tricritical point at which the first-order phase transition changes to the second-order phase transition has been estimated at 10.4 °C and x = 77.4% in the temperature–concentration phase diagram. The field-induced phase transitions and dielectric tunabilities have been discussed on the basis of the Landau-type free energy density.

0.98(K0.5Na0.5)NbO3–0.02(Bi0.5Na0.5)(Zr0.85Sn0.15)O3 Single Crystals Grown by the Seed-Free Solid-State Crystal Growth Method and Their Characterization

(K0.5Na0.5)NbO3-based single crystals are of interest as high-performance lead-free piezoelectric materials, but conventional crystal growth methods have some disadvantages such as the requirement for expensive Pt crucibles and difficulty in controlling the composition of the crystals. Recently, (K0.5Na0.5)NbO3-based single crystals have been grown by the seed-free solid-state crystal growth method, which can avoid these problems. In the present work, 0.98(K0.5Na0.5)NbO3–0.02(Bi0.5Na0.5)(Zr0.85Sn0.15)O3 single crystals were grown by the seed-free solid-state crystal growth method. Sintering aids of 0.15 mol% Li2CO3 and 0.15 mol% Bi2O3 were added to promote single crystal growth. Pellets were sintered at 1150 °C for 15–50 h. Single crystals started to appear from 20 h. The single crystals grown for 50 h were studied in detail. Single crystal microstructure was studied by scanning electron microscopy of the as-grown surface and cross-section of the sample and revealed porosity in the crystals. Electron probe microanalysis indicated a slight reduction in K and Na content of a single crystal as compared to the nominal composition. X-ray diffraction shows that the single crystals contain mixed orthorhombic and tetragonal phases at room temperature. Raman scattering and impedance spectroscopy at different temperatures observed rhombohedral–orthorhombic, orthorhombic–tetragonal and tetragonal–cubic phase transitions. Polarization–electric field (P–E) hysteresis loops show that the single crystal is a normal ferroelectric material with a remanent polarization (Pr) of 18.5 μC/cm2 and a coercive electrical field (Ec) of 10.7 kV/cm. A single crystal presents d33 = 362 pC/N as measured by a d33 meter. Such a single crystal with a large d33 and high Curie temperature (~370 °C) can be a promising candidate for piezoelectric devices.

Polar topological bubbles in (K,Na)NbO3-based single crystals via synergetic phase and defect engineering

The investigations of polar topological conformations have become one of the hotspots due to their multitudinous physical properties and potential applications in emerging electronic devices. However, constructing polar topologies in bulk form is exceedingly challenging. In this study, bubble domains with different polar topologies, including flux-closure and half-closure, are successfully achieved in Cu-doped (K,Na)(Nb,Ta)O3 single crystals by elaborately adjusting the phase structure and defect dipoles. The coexistence of orthorhombic and tetragonal phases results in a flattened free energy landscape, while the presence of a high concentration of defect dipoles in local regions leads to the generation of the strong internal electric field, further modifying the energy profile. The interplay of various types of energies gives rise to the smooth rotation of the polar vectors, facilitating the formation of topological structures. These findings provide a practical method for constructing topological bubble domains in bulk materials, thereby enriching the understanding of the physical properties arising from topological structures.

Impact of defect concentration on piezoelectricity in Mn/Fe-doped KTN crystals

Defect engineering via doping exhibits considerable potential for improving the performance of environment-friendly lead-free piezoelectric materials. Owing to the susceptibility to lattice vibrations and the micro-local chemical environment, the readily available Mn/Fe transition metal elements (TMEs) facilitate the construction of defect structures. However, the role of TMEs in shaping the domain structures and the corresponding promotional mechanism of piezoelectricity need to be further decoded. Herein, we propose the different influence mechanisms of Mn and Fe ions on the ferroelectric domain and piezoelectric properties. Different concentrations of (MnNb/Ta′-VO••)• and (FeNb/Ta″-VO••)× defect dipoles are obtained based on the synergy of Mn/Fe ions with oxygen vacancies. Diverse ferroelectric behaviors resulting from (MnNb/Ta′-VO••)• and (FeNb/Ta″-VO••)× defect dipoles are observed. Furthermore, the variation of the dielectric diffusiveness with the defect dipole concentration is investigated. Trace concentration of (MnNb/Ta′-VO••)• generates strong diffusiveness. With the characterization of the ferroelectric domain, this strong diffusiveness is attributed to the lattice-like domain structure. Thereafter, the mechanisms of Mn/Fe defect dipoles on the formation of domain structures are clarified. Macroscopically, the dielectric and piezoelectric properties are measured with Mn/Fe ion components. Trace Mn doping and the resulting lattice-like domain significantly enhance the piezoelectric coefficient, resulting in an increase of nearly 50% for K(Ta,Nb)O3 single crystals. This work highlights the tremendous potential of TME-induced defect dipoles for modifying the ferroelectric domain and provides a reference paradigm for improving piezoelectricity through defect engineering.

Revealing photoluminescence and nonlinear optical absorption characteristics of PbMo0.75W0.25O4 single crystal for optical limiting applications

Nonlinear absorption properties of PbMo0.75W0.25O4 single crystal fabricated by the Czochralski method were studied. The band gap energy of the crystal was determined as 3.12 eV. Urbach energy which represents the defect states inside the band gap was found to be 0.106 eV. PbMo0.75W0.25O4 single crystal has a broad photoluminescence emission band between 376 and 700 nm, with the highest emission intensity occurring at 486 nm and the lowest intensity peak at 547 nm, depending on the defect states. Femtosecond transient absorption measurements reveal that the lifetime of localized defect states is found to be higher than the 4 ns pulse duration. Open aperture (OA) Z-scan results demonstrate that the PbMo0.75W0.25O4 single crystal exhibits nonlinear absorption (NA) that includes two-photon absorption (TPA) as the dominant mechanism at the 532 nm excitations corresponding to 2.32 eV energy. NA coefficient (β eff ) increased from 7.24 × 10−10 m W−1 to 8.81 × 10−10 m W−1 with increasing pump intensity. At higher intensities β eff tends to decrease with intensity increase. This decrease is an indication that saturable absorption (SA) occurred along with the TPA, called saturation of TPA. The lifetime of the defect states was measured by femtosecond transient absorption spectroscopy. Saturable absorption behavior was observed due to the long lifetime of the localized defect states. Closed aperture (CA) Z-scan trace shows the sign of a nonlinear refractive index. The optical limiting threshold of PbMo0.75W0.25O4 single crystal at the lowest intensity was determined as 3.45 mJ/cm2. Results show that the PbMo0.75W0.25O4 single crystal can be a suitable semiconductor material for optical limiting applications in the visible region.

Growth and characterization of physical properties of photovoltaic (K,Ba)(Ni,Nb)O3 single crystals

The substitution of fossil energy for green-energy sources is a world demand. Photovoltaic devices are a well-known safety solution to convert solar energy into electricity. Ferroelectric materials are one of the most promising candidates for substituting Si-based compounds in solar-energy conversion devices due to their relatively low cost and bulk photovoltaic effect instead of the classical p-n junction. In this work, (K,Ba)(Nb,Ni)O3 single crystal was grown by vertical Bridgman-Stockbarger method, and structural, chemical, and optical properties of the as-grown material were characterized. Growth parameters were chosen based on the thermal properties of the precursor oxide and on theoretical models.

Self-poling and DC poling of Mn doped Pb(Mg1/3Nb2/3)O3-Pb(ZrTi)O3 single crystals grown by a solid state crystal growth process

Acceptor Mn-doped Pb(Mg1/3Nb2/3)O3-Pb(ZrTi)O3 (PMN-PZT) single crystals (SCs) grown by a solid state crystal growth (SSCG) process electrode with Ag at 650 °C showed a high piezoelectric coefficient (d 33) of 520 pC N−1 at 25 °C by self-poling, i.e. without any additional poling process. Upon heating above the Curie temperature (T c), the impedance characteristics’ oscillation peak due to piezoelectricity disappears. However, as the temperature falls below T c, these oscillation peaks reemerge around T c. And when the temperature is further lowered to around RT, the impedance characteristics return to almost the original state. The d 33 values of the non-poled SCs, initially 520 pC N−1, increased to 910 pC N−1 after DC poling (DCP) and to 1170 pC N−1 after field cooling (FC)-DCP. These values surpass those of commercially available high-Qm PZT ceramics. These high-Qm PMN-PZT single crystals developed using the SSCG method demonstrate huge potential for future transducer applications.

Oxygen Diffusion in Li(Nb,Ta)O3 Single Crystals

Oxygen tracer self‐diffusion in LiNbO3, LiTaO3, and LiNb0.15Ta0.85O3 single crystals between 880 and 1050 °C is investigated. 18O2 isotope‐exchanged samples are analyzed by secondary ion mass spectrometry. The diffusivities of each of the three different materials can be described by the Arrhenius law with an activation enthalpy of diffusion of about 3.2–3.5 eV. The diffusivities are highest for LiNbO3 and are lower by about one order of magnitude for LiNb0.15Ta0.85O3 and LiTaO3. The change of the pre‐exponential factor is identified as the reason for the difference in diffusivities. The experimental results are compared to defect formation energy calculations as given in literature and to energy barrier calculations for the diffusion of a single O vacancy as determined by nudged elastic band calculations based on density‐functional theory. An oxygen vacancy mechanism is suggested to govern diffusion. The difference in diffusivities is tentatively attributed to a different number of freely migrating vacancies, probably due to defect complex formation.

Experiments on Hydrogen Uptake and Diffusion in LiNb<sub>0.15</sub>Ta<sub>0.85</sub>O<sub>3</sub> Single Crystals by Infra-Red Spectroscopy

Hydrogen is an impurity that is often present in LiXO3 (X= Nb, Ta) single crystals and related materials. In this context, the diffusion of hydrogen is an important process because it may influence the overall conductivity of the material. We investigated the diffusional hydrogen uptake in LiNb0.15Ta0.85O3 single crystals at 600 °C. For the experiments, O2 is bubbled through liquid deuterated water (D2O), which leads to a saturation of the gas atmosphere with D2O that is incorporated into the crystal during isothermal annealing. The diffusivities of deuterium during uptake were determined by infra-red spectroscopy. We identified a fast process that can be associated with tracer diffusion and a second slower process with an almost three times lower diffusivity.

Imaging Voids and Defects Inside Li-Ion Cathode LiNi0.6Mn0.2Co0.2O2 Single Crystals.

Li-ion battery cathode active materials obtained from different sources or preparation methods often exhibit broadly divergent performance and stability despite no obvious differences in morphology, purity, and crystallinity. We show how state-of-the-art, commercial, nominally single crystalline LiNi0.6Mn0.2Co0.2O2 (NMC-622) particles possess extensive internal nanostructure even in the pristine state. Scanning X-ray diffraction microscopy reveals the presence of interlayer strain gradients, and crystal bending is attributed to oxygen vacancies. Phase contrast X-ray nano-tomography reveals two different kinds of particles, welded/aggregated, and single crystal like, and emphasizes the intra- and interparticle heterogeneities from the nano- to the microscale. It also detects within the imaging resolution (100 nm) substantial quantities of nanovoids hidden inside the bulk of two-thirds of the overall studied particles (around 3000), with an average value of 12.5%v per particle and a mean size of 148 nm. The powerful combination of both techniques helps prescreening and quantifying the defective nature of cathode material and thus anticipating their performance in electrode assembly/battery testing.

Enhanced piezoelectricity of Cu-doped K(Ta,Nb)O3 single crystals

As a class of solid solution material, K(Ta,Nb)O3 (KTN) single crystals have attracted significant interest due to their excellent piezoelectric and electro-optic performance. In this study, the piezoelectric properties of KTN were improved through Cu doping. Utilizing the advantages of composition-regulating phase transition, a large, high-quality Cu:KTN crystal measuring 30 mm × 25 mm × 20 mm in size was grown using the improved top seeded solution growth method. Cu-doped KTN exhibited better piezoelectric properties than pure KTN, and the full matrix parameters were investigated. Excellent dielectric, piezoelectric, and electromechanical coupling responses (ε11T∼ 2,136, d33∼303 pC/N, kt∼0.515, and k33∼0.672) were successfully obtained. To realize the optimized orientation of the piezoelectric properties, the orientation dependence of the single domain properties was investigated, and the mechanism of Cu doping to improve piezoelectric properties was explored. We found that 0.36% (in mass) Cu doped crystal consisted of A-site substitution, following ferroelectric and domain analysis. The small ferroelectric domain sizes led to a large domain wall mobility rate and high domain wall density, which contributed to high piezoelectric properties. This work revealed the effect of A-position doping on piezoelectric properties and provided a theoretical and experimental foundation for the performance optimization of KTN-based materials.

Growth and optical properties of (Na0.5Bi0.5)(Mo1−xWx)O4 (x = 0.25) single crystal: a potential candidate for optoelectronic devices

Growth and optical properties of (Na0.5Bi0.5)(Mo1−xWx)O4 (x = 0.25) single crystal: a potential candidate for optoelectronic devices

Defects and nanostrain gradients control phase transition mechanisms in single crystal high-voltage lithium spinel.

Lithiation dynamics and phase transition mechanisms in most battery cathode materials remain poorly understood, because of the challenge in differentiating inter- and intra-particle heterogeneity. In this work, the structural evolution inside Li1-xMn1.5Ni0.5O4 single crystals during electrochemical delithiation is directly resolved with operando X-ray nanodiffraction microscopy. Metastable domains of solid-solution intermediates do not appear associated with the reaction front between the lithiated and delithiated phases, as predicted by current phase transition theory. Instead, unusually persistent strain gradients inside the single crystals suggest that the shape and size of solid solution domains are instead templated by lattice defects, which guide the entire delithiation process. Morphology, strain distributions, and tilt boundaries reveal that the (Ni2+/Ni3+) and (Ni3+/Ni4+) phase transitions proceed through different mechanisms, offering solutions for reducing structural degradation in high voltage spinel active materials towards commercially useful durability. Dynamic lattice domain reorientation during cycling are found to be the cause for formation of permanent tilt boundaries with their angular deviation increasing during continuous cycling.

Bright Transparent Scintillators with High Fraction BaCl2 : Eu2+ Nanocrystals Precipitation: An Ionic-Covalent Hybrid Network Strategy toward Superior X-Ray Imaging Glass-Ceramics.

Metal halide crystals are bright but hygroscopic scintillator materials that are widely used in X-ray imaging and detectors. Precipitating them in situ in glass to form glass ceramics (GCs) scintillator offers an efficient avenue for large-scale preparation, high spatial resolution, and excellent stability. However, precipitating a high fraction of metal halide nanocrystals in glass to maintain high light yield remains a challenge. Herein, an ionic-covalent hybrid network strategy for constructing GCs scintillator with high crystallinity (up to ≈37%) of BaCl2 : Eu2+ nanocrystals is presented. Experimental data and simulations of glass structure reveal that the Ba2+ -Cl- clustering promotes the high crystallization of BaCl2 nanocrystals. The ultralow phonon energy (≈200 cm-1 ) of BaCl2 nanocrystals and good Eu reduction effect enable high photoluminescence inter quantum efficiency (≈80.41%) in GC. GCs with varied crystallinity of BaCl2 : Eu2+ nanocrystals demonstrate efficient radioluminescence and tunable scintillator performance. They either outperform Bi4 Ge3 O14 single crystal by over 132% steady-state light yield or provide impressive X-ray imaging resolutions of 20 lp mm-1 . These findings provide a new design strategy for developing bright transparent GCs scintillators with a high fraction of metal halide nanocrystals for X-ray high-resolution imaging applications.

Investigation of ferroelectric Ba1−xCaxZryTi1−yO3 single crystal by in situ temperature-dependent x-ray diffraction and first-principles calculations

In situ temperature-dependent crystal structure of lead-free ferroelectric perovskite Ba0.798Ca0.202Zr0.006Ti0.994O3 single crystal was characterized using x-ray diffraction from 170 to 380 K. Three phases were identified at different temperatures of 170, 220, and 298 K, revealing rhombohedral (R3m), orthorhombic (Pmm2), and tetragonal (P4mm) crystal structures, respectively. The change in the bond length and its distortion are reported for both AO12 and BO6 polyhedrons, allowing for the estimation of the spontaneous polarization. The Debye–Waller factor is reported as a function of temperature for A and B-sites. Density-functional theory calculations on the tetragonal phase were performed to obtain information on the distribution of the Ca ions, the local atomic displacements, and the ideal value of the spontaneous polarization of a defect-free crystal at 0 K. We find that Ca prefers to arrange in columnar 2D plates oriented along the tetragonal axis. The Ca ions avoid being next neighbors of Zr; however, the specific arrangement of Ca has only a minor impact on the spontaneous polarization.