Crystal Field Research Articles

Emerging Anomalous Hall Effect in (111)‐Oriented Artificial Iridate Honeycomb Lattices

AbstractComplex Ir oxides provide a promising platform for investigating cooperativity and competition between Mott physics and spin‐orbit coupling in condensed matter physics. These materials have the potential to reveal intriguing phases, such as topological phases and the Kitaev spin liquid state, an exactly solvable S = 1/2 spin model describing Ir4+ ions on a 2D honeycomb lattice. However, experimental confirmation of such phases in iridate films has been hindered by the difficulty of preparing (111)‐oriented samples of the perovskite phase. Herein, by constructing SrIrO3/SrTiO3 superlattices on SrTiO3 (111) substrates, (111)‐oriented perovskite phase SrIrO3 films are achieved with the unprecedentedly large thickness of 6 unit cells. Electrical and magnetic characterizations reveal that these films exhibit anomalous Hall insulating behavior, significant charge fluctuations, and long‐range antiferromagnetic order. Moreover, these properties can be tuned by varying the thickness of the SrIrO₃ layer. These emergent phenomena underscore the complex interactions among spin‐orbit coupling, electron–electron correlations, and crystal structure in (111)‐oriented artificial iridate honeycomb lattices. Further, spin fractionalization and topological quantum spin liquid may be achieved by tuning the spin–orbit coupling and crystal field intensity from interface engineering.

High‐Pressure Modulation of NIR Luminescence in Cr3+‐Doped Cs2AgInCl6 Double Perovskites: The Role of Ultrafast Energy Transfer

AbstractLead‐free halide double perovskites (DPs) have attracted much attention due to their potential applications in the field of near‐infrared (NIR) optoelectronics. However, regulating the NIR luminescence properties of such materials remains a challenge. In this study, it is found that Cs2AgInCl6:Cr3+ DPs exhibit a broad NIR emission under ultraviolet excitation, with a peak value of 980 nm. In the range of 9 GPa, the emission intensity increases significantly. As the pressure increases, a transition from broadband NIR emission to narrow‐line emission occurs, accompanied by a decrease in the full width at half maximum (FWHM) from 260 to 40 nm, attributed to increased local structural asymmetry and enhanced crystal field around Cr3+ ions. Ultrafast transient absorption experiments reveal the changes of energy transfer under pressure and the emergence of new radiation channels, demonstrating the dynamic evolution of emission characteristics under high pressure. The research results deepen the understanding of high pressure luminescence in Cr3⁺‐doped halide DPs, providing strategies for designing highly efficient NIR emitters in metal halide DPs.

Evolution of critical current density in CaKFe4As4 with La-doping

Abstract Single crystals of (Ca1-xLax)KFe4As4 (0 ≤ x ≤0.16) have been grown by using the self-flux method, and the evolution of physical properties including the critical current density (Jc) with La-doping has been investigated. Tc decreases monotonically with increasing x, while Jc at the same temperature and magnetic field increases initially and reach its maximum at x = 0.082. The increase in Jc is more obvious at low temperatures and high fields. At T = 5 K and H = 40 kOe, Jc reaches 0.34 MA/cm2, which is ~4 times larger than that for pure crystals. It is also found that anomalous temperature dependence of Jc in CaKFe4As4 is wiped away as the La content is increased. However, Jc shows non-monotonic field dependence (peak effect) at high fields in crystals with large x. In addition, we found that despite weak anisotropy of Hc2, there is extremely large anisotropy of Jc up to ~15, which is most likely caused by novel planar defects in the crystal, similar to CaKFe4As4. Jc characteristics in (Ca1-xLax)KFe4As4 with disorder outside FeAs planes is compared with that in CaK(Fe1-xCox)4As4 with disorder within FeAs planes.

Crystal growth, structure and crystal field splitting and fitting of Yb:GdScO3

Crystal growth, structure and crystal field splitting and fitting of Yb:GdScO3

Crystal field and microscopic spin Hamiltonians approach for V3+ ions in α-ZnAl2S4 single crystals

Crystal field and microscopic spin Hamiltonians approach for V3+ ions in α-ZnAl2S4 single crystals

Manipulating photoluminescence properties of neodymium-doped fluorites through local structure regulation

The long upper level lifetimes are highly advantageous for laser diode pumped high energy laser systems. However, lifetimes of the rare earth neodymium ions, one of the most important active ions in 1 μm, are generally around 300 μs or less, which limits the development of laser diode pumped high energy lasers on neodymium gains. In this work, Nd:CaF2 and Nd:SrF2 were chosen and introduced with appropriate codopants to adjust the local structures, thereby modulating the coupling of active ions with the crystal fields. The transition rate was slowed down and a long lifetime nearly 600 μs was obtained. Neodymium-doped fluorites with broad emission bandwidths and high thermal conductivities are potential laser gains for generation of high repetition rate high power lasers.

Optimization of batch cooling crystallization systems considering crystal growth, nucleation and dissolution. Part I: Simulation

Optimal control of batch crystallization systems is still a focus and hot topic in the field of industrial crystallization, which seriously affects the consistency of batch product quality. In this paper, a new method with a new objective function and improved optimization algorithm was proposed for optimization of crystal size distribution (CSD) in case of fine crystals occurrence. The new objective function was developed with better margin metric and weighting technique to minimize fine crystal mass, meanwhile, a newly constructed sinusoidal weight function was introduced to improve the particle swarm optimization (PSO) algorithm. A precise control of CSD with suppressed numerical discrepancy caused by fine crystals removal was developed by combining seed recipe and temperature-swing. In addition, the effects of temperature curve segments on CSD during process optimization were systematically investigated to achieve optimal results. Two typical batch cooling crystallization systems were used to verify the effectiveness of the proposed method in controlling product CSD while minimizing fine crystal mass. Results demonstrated that the desired product CSD can be achieved with minor errors while the fine crystals could be shrunk to be negligible, i.e., the fine crystal mass and number can be reduced by over 90%. This work has an important guiding significance for the removal of fine crystals in industrial crystallization processes, especially when only operational optimization rather than equipment updating is considered.

Influence of crystal field inhomogeneities on the spontaneous and laser tuning emission of a Nd3+-doped Li2O-BaO-Al2O3-P2O5 glass

The present work focuses on the spectroscopic and laser properties of Nd3+ in a Li2O-BaO-Al2O3-P2O5 aluminophosphate glass which includes Judd-Ofelt calculation, stimulated emission cross-section of the 4F3/2→4I11/2 emission laser transition, lifetime of the 4F3/2 state and quantum efficiency. Site-selective laser spectroscopy and stimulated emission under selective excitation has been performed to determine the crystal field inhomogeneity at the Nd3+ site together with its broadening effect on the spontaneous and laser emissions. However, a much narrowed laser emission has been achieved by using an intracavity tilting plate which acts as a tunable optical filter to adjust the laser wavelength.

Customized Cyan Phosphors for Efficient Full-Spectrum Illumination and Fingerprint Detection.

Traditional lighting methods have environmental and efficiency drawbacks. These methods are gradually being overshadowed by light-emitting diodes (LEDs) because of their superior color rendering and energy efficiency. In this study, color-tunable NaBa2(Ba/Sr/Ca)Si2O7F:Eu2+ phosphors are successfully designed by modulating the local crystal field environment through homodominant-group cation substitution, thereby allowing for a spectral shift from blue to bright cyan. Detailed structural analysis of the samples demonstrated the synthesis of high-quality solid-solution materials. A comprehensive examination of the phosphor crystal structure, photoluminescence properties, and fluorescence lifetime reveal that the cyan phosphor possesses a remarkable internal quantum efficiency (IQE = 93%) and low thermal quenching characteristics (I423 K/I303 K = 84%). The results illustrate the critical role of Eu2+-activated cyan phosphors in reducing the spectral gap to attain a natural white-light spectrum, which is indispensable for achieving high color fidelity. The practical application of cyan phosphors in the fabrication of high-performance white LED (WLED) (Ra = 96.8) and fingerprint detection is validated, demonstrating their extensive utility in enhancing visual accuracy and identification.

Masked Divalent Reactivity of Heterobimetallic Lanthanide Isocarbonyl Complexes.

A new rare-earth reduction system is described in which trivalent yttrium and dysprosium react as though present in their unstable divalent oxidation state. This masked divalent reactivity is achieved using the isocarbonyl-bridged dimers [(Cpttt2M)(μ-Fp)]2 (M = Y, 1Y; M = Dy, 1Dy; Cpttt = 1,2,4-C5tBu3H2; Fp = CpFe(CO)2), where the reducing electrons originate from the bridging [Fp]- ligands. The reactivity of 1Y and 1Dy is showcased by reducing the N-heterocycles 2,2'-bipyridyl (bipy), phenazine (phnz) and hexaazatrinaphthylene (HAN) to give corresponding mono-, di- and tri-metallic rare-earth complexes, respectively, with the heterocyclic ligands present in their singly, doubly and triply reduced forms, respectively. The dynamic magnetic properties of the dysprosium compounds are described. Compound 1Dy is a single-molecule magnet (SMM) with an appreciable energy barrier of 449(17) cm-1, whereas [(Cpttt2Dy)2(m-phnz)] (3Dy) is not an SMM because of a strong, competing equatorial crystal field. Surprisingly, [(Cpttt2Dy)3(HAN)] (4Dy) is also not an SMM, the origins of which are traced to the impact of the tert-butyl substituents on the dysprosium centre and its interaction with the radical [HAN]3- ligand.

Masked Divalent Reactivity of Heterobimetallic Lanthanide Isocarbonyl Complexes

A new rare‐earth reduction system is described in which trivalent yttrium and dysprosium react as though present in their unstable divalent oxidation state. This masked divalent reactivity is achieved using the isocarbonyl‐bridged dimers [(Cpttt2M)(μ‐Fp)]2 (M = Y, 1Y; M = Dy, 1Dy; Cpttt = 1,2,4‐C5tBu3H2; Fp = CpFe(CO)2), where the reducing electrons originate from the bridging [Fp]– ligands. The reactivity of 1Y and 1Dy is showcased by reducing the N‐heterocycles 2,2'‐bipyridyl (bipy), phenazine (phnz) and hexaazatrinaphthylene (HAN) to give corresponding mono‐, di‐ and tri‐metallic rare‐earth complexes, respectively, with the heterocyclic ligands present in their singly, doubly and triply reduced forms, respectively. The dynamic magnetic properties of the dysprosium compounds are described. Compound 1Dy is a single‐molecule magnet (SMM) with an appreciable energy barrier of 449(17) cm–1, whereas [(Cpttt2Dy)2(m‐phnz)] (3Dy) is not an SMM because of a strong, competing equatorial crystal field. Surprisingly, [(Cpttt2Dy)3(HAN)] (4Dy) is also not an SMM, the origins of which are traced to the impact of the tert‐butyl substituents on the dysprosium centre and its interaction with the radical [HAN]3– ligand.

Structure-Photoluminescence Relationship in Ce3+-Doped K5Y(P2O7)2 and Its Sensitization to Dy3+ with Enhanced White Light Emission.

From a fundamental point of view, the structure-photoluminescence relationship is vitally important for developing efficient phosphors and rationally improving their performances. In this work, Rietveld refinements on high-resolution powder X-ray diffraction (XRD) data were conducted to verify the Ce3+ distribution in K5Y(P2O7)2 (KYPO). Ce3+ ions are located at both M1 and M2 sites, with occupation factors of 0.31(2) and 0.19(2), respectively. Importantly, the crystal field strength (CFS) is stronger at the former site due to the larger bond valence sum. Correspondingly, the Ce3+ emission can be deconvoluted into four Gaussian-type bands centered at ∼353, ∼383, ∼343, and ∼369 nm, where the former two belong to Ce3+ at the M1 site and the latter two are assigned to Ce3+ at the M2 site. Ce3+ in KYPO is a highly efficient activator, with optimal internal and external quantum efficiencies of 98.9 and 74.6%, respectively, and was thus utilized to sensitize the Dy3+ emission. Indeed, energy transfer from Ce3+ to Dy3+ was confirmed by fluorescent decay curves for Ce3+/Dy3+ codoped KYPO, and the mechanism was supposed to be dominated by dipole-dipole interactions. Indeed, it can be pumped by a 310 nm LED chip and emits a bright white light. Ce3+ photoluminescence exhibits high resistance to thermal quenching, and it can be further enhanced by codoping Dy3+, i.e. the emission intensity remains 96.3% at 423 K.

Interpretation of mechanical properties gradient in laser-welded joints: Experiments and grain morphology-dependent crystal plasticity modeling

The grain size and morphology of laser welds show a gradient distribution, leading to variations in mechanical properties. This study proposes a microscopic crystal plasticity constitutive (CPC) model to examine the effect of ER4047 welding wire on the mechanical properties of laser-welded aluminum alloy joints. A finite element model updating strategy was used to fully invert the morphological mechanical parameters, marking a significant advancement. This study combines mesoscale electron backscatter diffraction (EBSD) observations with macroscopic uniaxial tensile tests to obtain crystal plasticity finite element analysis and strain field data from digital image correlation. The mechanical property gradient of the welded joints was systematically analyzed from a crystal perspective. The CPC parameters were inverted for different grain sizes and morphologies. The study found that using ER4047 welding wire significantly enhanced the mechanical properties of the welded joints, especially in the welding zone. As grain size increased, the yield strength of the material decreased, while the hardening modulus increased. Additionally, the cast characteristics of columnar crystal morphology reduced both yield strength and hardening modulus.

Ground state phase diagrams of mixed spin (S,σ,σ,S) infinite alternating double-layers system of a cubic lattice for S=5/2 and σ=2

The ground state phase diagrams of a cubic lattice of infinite mixed spin (S,σ,σ,S) double-layers have been studied at a temperature of T=0K with the Blume-Capel model spins S=5/2 and σ=2. The parameters used are the couplings describing the interactions between the first nearest neighbor spins, J1 for S‑S, J2 for σ‑σ and J3 for S‑σ; the crystal field Δ and the external magnetic field h. We have analyzed the phase diagrams obtained by exact calculations of our model. The obtained phases were listed in the planes between the parameters of our system and showed an abundance of ferromagnetic (FM), antiferromagnetic (AFM), nonmagnetic (NM), and ferrimagnetic (FiM) phases. The effect of the external magnetic field on the system configurations has been studied.

Structural comparison of [Ce(OtBu)Cl(THF)5](BPh4) to smaller rare earth analogues.

The introduction of the cerium(III) analogue (1-Ce, Ln = Ce) of (tert-butoxido)chloridopentakis(tetrahydrofuran)lanthanide(III) tetraphenylborate tetrahydrofuran disolvate, [Ln{OC(CH3)3}Cl(C4H8O)5][B(C6H5)4]·2C4H8O or [Ln(OtBu)Cl(THF)5](BPh4)·2THF (1-Ln) has been achieved with a structural comparison between the existing solid-state structures of other rare earth analogues and the title compound at 100 and 180 K. The cation in 1-Ce is targeted as the cerium(III) ion possesses the criteria to exhibit slow magnetic relaxation in axial point-charge crystal fields, akin to the dysprosium(III) ion in 1-Dy. AC magnetic susceptibility experiments reveal no such behaviour for 1-Ce, putting the viability of cerium-based SMMs into question.

Comparative investigation on carbon dots and chloride fluxes modified ZnAl2O4:Cr3+ nanophosphors for temperature sensing, cutting-edge forensic, anti-counterfeiting and w-LEDs applications

A novel Cr3+ doped ZnAl2O4 is synthesized by grafting carbon dots (CDs) and chloride fluxes (NaCl, KCl, NH4Cl) through the solid-state reaction method. Upon excitation at 530 nm wavelength, the Cr3+ ions in the ZAO NPs emit red light due to the influence of a strong crystal field. This red emission arises from the electric dipole 2Eg→4A2g of the Cr3+ ions. Among the chloride fluxes examined, NH4Cl had a significant impact on the PL intensity. Notably, when CDs are incorporated into the ZAO:7Cr3+/NH4Cl NPs, a remarkable increase of 17.25-folds in photoluminescence (PL) intensity is observed. This enhancement is substantially higher than that of CDs alone (11.23-folds) and NH4Cl alone (3.82-folds). The increased PL intensity is attributed to the Förster resonance energy transfer (FRET) mechanism. Furthermore, the addition of CDs (5 wt.%) enhanced the colour purity (CP) of ZAO:7Cr3+/NH4Cl NCs to 99.8%, achieving a high Internal quantum efficiency (IQE) of 93.4 %. Notably, the CDs (5 wt.%)@ZAO:7Cr3+/NH4Cl NCs maintained 92.43 % of their emission intensity even at 420 K, demonstrating exceptional thermal stability compared to ZAO:7Cr3+ NPs. Moreover, the NPs holds promise for optical thermometry, boasting a high relative sensitivity (Sr) of 6.74 × 10–2 %K-1 across a temperature range spanning from 300 to 480 K. Moreover, the latent fingerprints (LFPs) developed using CDs(5 wt.%)@ZAO:7Cr3+/NH4Cl NCs demonstrate remarkable selectivity and high contrast. Under UV irradiation, the structural features of LFPs at levels I–III are clearly visible. In addition, the strong red fluorescence emitted by CDs(5 wt.%)@ZAO:7Cr3+/NH4Cl NCs makes them suitable for applications in AC. CDs(5 wt.%)@ZAO:7Cr3+ NCs exhibit significant potential for w-LED fabrication, achieving a correlated colour temperature (CCT) of 5517 K, a CIE coordinate of (0.332, 0.331), and a high colour rendering index (CRI) of Ra = 94, outperforming ZAO:7Cr3+/NH4Cl NPs. Overall results clearly demonstrates that, CDs(5 wt.%)@ZAO:7Cr3+/NH4Cl NCs are effective for applications in optical thermometry, dactyloscopy, w-LEDs, and AC.

Achieving Flat Ultra‐Broadband NIR Emission in Cr3+ Doped Garnet‐Type Phosphors Enabled by Structural Regulation Toward Multi‐Functional Spectroscopy Applications

AbstractCr3+‐activated near‐infrared (NIR) emitting phosphors are considered as one of the most potential light‐conversion materials for NIR phosphor converted light‐emitting diodes (NIR pc‐LEDs). However, it is still a challenge for a single Cr3+ ion to achieve a flat ultra‐broadband emission toward multi‐functional spectroscopy applications. Herein, a chemical unit co‐substituting strategy is utilized to regulate the crystallographic occupancy of Cr3+ ions, and a flat ultra‐broadband NIR emission is successfully realized with a record emission wavelength of 915 nm in garnet‐type phosphors Ca3Sc2‐xHfxAlxSi3‐xO12: yCr3+ (0 ≤ x ≤ 1, 0.02 ≤ y ≤ 0.06), together with a large full width at half maximum (FWHM) regulation from 130 to 250 nm. The relation between the site occupation of Cr3+ ions in disordered [CaO8], [(Sc, Hf)O6] and [(Si, Al)O4] polyhedrons and the corresponding NIR emission are clarified by carefully evaluating the structural evolution, Raman spectra, electron paramagnetic resonance and time‐resolved emission lifetime spectra of Cr3+ ions. The corresponding crystal field strength of Cr3+ ions is investigated to further clarify the multi‐sites induced flat broadband NIR emission. Finally, a blue light pumped NIR pc‐LED is fabricated with a total output power of 37.58 mW and photoelectric conversion efficiency (PCE) of 13.67%@100 mA, which realizes the multi‐functional applications in night vision imaging, non‐destructive detection and palmprint vein recognition for assistant medical treatment.

Structural determination, energy transfer and color-tunable photoluminescence of stable LiYSiO4: Ce/Tb/Sm Phosphors toward nUV pumped wLEDs application

Study on photon emission of Ce3+-doped phosphors is essential for advanced optoelectronic application. However, it remains quite difficult to design near-ultraviolet excitable Ce3+-activated silicate blue/cyan-emitting phosphors because of the combined influence of iconicity of Ce3+, crystal field strength, and nephelauxetic effect. Herein, Ce3+ incorporated into a proper host LiYSiO4 (LYS) phosphor is mechanistically investigated and shown efficient blue/cyan photoluminescence (PL) owing to Ce3+ 5d1 electronic state experiencing appropriate crystal field splitting. The comprehensive analysis based on structural refinement, dynamic/static spectra, and density functional theory calculations indicates that Ce3+ ions are energetically favored in octahedral Y site as compared with Li site in the host, resulting in attractive PL properties. According to the principle of color superposition and via cascading energy transfer (ET) from Ce3+ → Tb3+ → Sm3+, systematic PL tuning in a large color gamut is realized by further codoping with the green- and red-emissions of Tb3+ and Sm3+ in the phosphor LYS: Ce3+/Tb3+/Sm3+. The direct ET from Ce3+ → Sm3+ is difficult to occur due to the metal-metal charge transfer effect. Of note, the PL thermal-quenching of Ce3+ is mainly associated with multiphonon relaxation, while the quenching of Tb3+/ Sm3+ is primarily due to the cross relaxation (CR) process via dipole-dipole (d-d) interaction. The appropriate distance between the two nearest adjacent Y sites in the host together with the ET are conducive to weaken the CR process of Tb3+/Sm3+, leading to high PL efficiency. Finally, a prototype pc-wLED assembled via a remote ‘capping’ packaging strategy and by using only the stably composition-optimized white-emitting LYS: Ce3+/Tb3+/Sm3+ demonstrates that the phosphor is promising for high-quality of light.

Visualizing Ultrafast Photogenerated Electron and Hole Separation in Facet-Engineered Bismuth Vanadate Crystals.

Photogenerated charge separation is pivotal for effecting efficient photocatalytic reactions. Understanding this process with spatiotemporal resolution is vital for devising highly efficient photocatalysts. Here, we employed pump-probe transient reflection microscopy to directly observe the temporal and spatial evolution of photogenerated electrons and holes on the surface of facet-engineered bismuth vanadate (BiVO4) crystals. The findings suggest that the anisotropic built-in field of BiVO4 crystals propels the separation of photogenerated electrons and holes toward different facets through a two-step process across varying time scales. Photogenerated electrons and holes undergo ultrafast separation within ∼6 ps, with electrons transforming into localized small polarons toward the {010} facets of truncated BiVO4 octahedral crystals. However, the photogenerated holes prolong their separation up to ∼2000 ps in a drift-diffusion manner before ultimately accumulating on the {120} facets. This work provides a comprehensive visualization of spatiotemporal charge separation at the nano/microscale on semiconductor photocatalysts, which is beneficial for understanding the photocatalysis mechanism.

Improved Energy Transfer in the Sensitization of Americium Enables Observation of Circularly Polarized Luminescence

AbstractThe first example of circularly polarized luminescence (CPL) from a molecular americium (Am) complex is reported. Coordination of Am(III) by a combination of thenoyltrifluoroacetonate and a chiral diphosphine oxide ligand yielded a complex with strong sensitized metal‐centered luminescence. The energy transfer process for sensitization appears to occur via a unique resonant pathway, which results in the removal of the overlap between ligand phosphorescence and sensitized Am luminescence that has often been observed. Owing to this feature, and despite the limited amount of material that could be used due to the radioactivity of 241Am, CPL could be measured. The collected luminescence and CPL spectra provide insight into the crystal field splitting of the 5D1→7F1 transition. These results pave the way for future studies of Am(III) luminescence to investigate electronic structure effects in this and other 5 f elements.