Rare-earth Compounds Research Articles

Facile Synthesis of Ln-Doped Hydrogen-Bonded Organic Frameworks with Rare-Earth-Characteristic Long Persistent Luminescence.

Tunable luminescence-assisted information storage and encryption holds increasing significance in today's society. A promising approach to incorporating the benefits of both organic long persistent luminescent (LPL) materials and rare-earth (RE) luminescence lies in utilizing organic host materials to sensitize RE luminescence, as well as hydrogen-bonded organic framework (HOF) phosphorescence Förster resonance energy transfer to RE compound luminescence. This work introduces a one-pot, in situ pyrolytic condensation method, achieved through high-temperature melting calcination, to synthesize lanthanide ion-doped HOF materials. This method circumvents the drawback of molecular triplet energy annihilation, enabling the creation of organic LPL materials with RE characteristics. The HOF material serves as the host, exhibiting blue phosphorescence and cyan LPL. By fine-tuning the doping amount, the composite material U-Tb-100 achieves green LPL with a luminescent quantum yield of 56.4%, and an LPL duration of approximately 2-3 s, demonstrating tunable persistence. Single-crystal X-ray diffraction, spectral analysis, and theoretical calculation unveil that U-Tb-100 exhibits exceptional quantum yield and long-lived luminescence primarily due to the efficient sensitization of U monomer to RE ions and the PRET process between U and RE complexes. This ingenious strategy not only expands the repertoire of HOF materials but also facilitates the design of multifunctional LPL materials.

Machine-Learning Prediction of Curie Temperature from Chemical Compositions of Ferromagnetic Materials.

Room-temperature ferromagnets are high-value targets for discovery given the ease by which they could be embedded within magnetic devices. However, the multitude of potential interactions among magnetic ions and their surrounding environments renders the prediction of thermally stable magnetic properties challenging. Therefore, it is vital to explore methods that can effectively screen potential candidates to expedite the discovery of novel ferromagnetic materials within highly intricate feature spaces. To this end, we explore machine-learning (ML) methods as a means to predict the Curie temperature (Tc) of ferromagnetic materials by discerning patterns within materials databases. This study emphasizes the importance of feature analysis and selection in ML modeling and demonstrates the efficacy of our gradient-boosted statistical feature-selection workflow for training predictive models. The models are fine-tuned through Bayesian optimization, using features derived solely from the chemical compositions of the materials data, before the model predictions are evaluated against literature values. We have collated ca. 35,000 Tc values and the performance of our workflow is benchmarked against state-of-the-art algorithms, the results of which demonstrate that our methodology is superior to the majority of alternative methods. In a 10-fold cross-validation, our regression model realized an R2 of (0.92 ± 0.01), an MAE of (40.8 ± 1.9) K, and an RMSE of (80.0 ± 5.0) K. We demonstrate the utility of our ML model through case studies that forecast Tc values for rare-earth intermetallic compounds and generate magnetic phase diagrams for various chemical systems. These case studies highlight the importance of a systematic approach to feature analysis and selection in enhancing both the predictive capability and interpretability of ML models, while being devoid of potential human bias. They demonstrate the advantages of such an approach over a mere reliance on algorithmic complexity and a black-box treatment in ML-based modeling within the domain of computational materials science.

The Effect of the Rare Earth Element Cerium on the Electrocrystallization and Microstructure of Nickel Electrodeposits in Industrial Electrolytes

To meet the industrial production needs for high-quality and precisely controllable structured high-end nickel foils, rare Earth compounds are added as additives in complex industrial electrolytes to improve the quality of the nickel deposition layer. This study investigates the effects of adding rare Earth compounds to the existing industrial production electrolytes (which already contain various organic and inorganic additives in a mixed acid solution) on the surface microstructure, cerium content, grain size, and crystal orientation of the nickel deposition layer. Using direct current electrodeposition, different concentrations of rare Earth compounds were added to the industrial electrolyte, and the cerium content, grain size, and crystal orientation were characterized. The results show that adding 0.8 g·l−1 CeCl3 accelerates the nucleation rate and shortens the nucleation relaxation time. The addition of rare Earth elements promotes multi-directional preferential growth, resulting in uniform and fine grain size, improved grain structure of the deposition layer, and reduced surface roughness of the nickel plating layer. Therefore, rare Earth elements can be used to regulate the structure, microstructure, and grain refinement of the nickel deposition layer without affecting its composition.

Experimental investigation of gamma-ray interaction parameters and buildup factors in lanthanide compounds: Insights into penetration depth

This experimental investigation focuses on the gamma-ray interaction parameters and the buildup factor in lanthanide compounds (CeO2, Ce(SO4)2, Dy2(SO4)3, C3O9Sm2, C3Gd2O9, Pr2O3). These compounds were exposed to weak radioactive gamma sources with energies of 356, 511, 662, 1173, 1275, and 1332 keV by adopting narrow and broad beam geometry experimental arrangements. The incident and transmitted radiation intensities were measured using a NaI (Tl) detector. Experimentally measured values of mass attenuation coefficient and effective atomic number of lanthanide compounds were found to be in precise agreement with theoretical values obtained from NIST XCOM and Direct-Zeff database respectively. Additionally, the experimentally determined buildup factor values were compared with energy absorption buildup factor (EABF) and exposure buildup factor (EBF) values obtained from Phy-X/PSD software, providing insights into the gamma-ray penetration depth in terms of mean free path (MFP). At 356 keV, the EABF analysis showed that most compounds had a penetration depth of around 8 mean free paths. In contrast, the EBF analysis indicated penetration depths exceeding 10 mean free paths for all compounds except Ce (SO4)2. This new approach holds immense potential for transformative advancements in medical diagnostics, therapy, and the development of innovative technologies in nuclear sciences.

Rare-Earth Metallocenes for Polymerization of Olefins and Conjugated Dienes: From Fundamental Studies to Olefin Block Copolymers.

The various steps in the mechanism of olefin polymerizations mediated by neutral rare-earth metallocene complexes are discussed. The complexes are either trivalent hydride and alkyl rare-earth compounds or divalent metallocenes that are activated by the monomer via an oxidation step. The stereospecific polymerizations of conjugated dienes based on the association of a cationic metallocene complex and an alkylaluminum and the polymerization mechanism based on monomer insertion into an aluminum-carbon bond are also discussed. The exploitation of metallocene complexes for the copolymerization of olefins with conjugated dienes is the subject of a third part of this review. The synthesis of new elastomers called ethylene butadiene rubber (EBR) is highlighted. Finally, the use of rare-earth metallocenes in macromolecular engineering is detailed. This includes the synthesis of functional polyolefins and block copolymers including thermoplastic elastomers.

Hidden Charge Order and Multiple Electronic Instabilities in EuTe4.

The rare-earth telluride compound EuTe4 exhibits a charge density wave (CDW) and an unconventional thermal hysteresis transition. Herein, we report a comprehensive study of the CDW states in EuTe4 by using low-temperature scanning tunneling microscopy. Two types of charge orders are observed at 4 K, including a newly discovered spindle-shaped pattern and a typical stripe-like pattern. As an exotic charge order, the spindle-shaped CDW is off-axis and barely visible at 77 K, indicating that it is a hidden order developed at low temperature. Based on our first-principles calculations, we reveal the origins of the observed electronic instabilities. The spindle-shaped charge order stems from a subsequent transition based on the stripe-like CDW phase. Our work demonstrates that the competition and cooperation between multiple charge orders can generate exotic quantum phases.

Overview of Functionalized Porous Materials for Rare-Earth Element Separation and Recovery.

The exceptional photoelectromagnetic characteristics of rare-earth elements contribute significantly to their indispensable position in the high-tech industry. The exponential expansion of the demand for high-purity rare earth and related compounds can be attributed to the swift advancement of contemporary technology. Nevertheless, rare-earth elements are finite and limited resources, and their excessive mining unavoidably results in resource depletion and environmental degradation. Hence, it is crucial to establish a highly effective approach for the extraction and reclamation of rare-earth elements. Adsorption is regarded as a promising technique for the recovery of rare-earth elements owing to its simplicity, environmentally friendly nature, and cost-effectiveness. The efficacy of adsorption is contingent upon the performance characteristics of the adsorbent material. Presently, there is a prevalent utilization of porous adsorbent materials with substantial specific surface areas and plentiful surface functional groups in the realm of selectively separating and recovering rare-earth elements. This paper presents a thorough examination of porous inorganic carbon materials, porous inorganic silicon materials, porous organic polymers, and metal-organic framework materials. The adsorption performance and processes for rare-earth elements are the focal points of discussion about these materials. Furthermore, this work investigates the potential applications of porous materials in the domain of the adsorption of rare-earth elements.

The mechanism insight into the cooperative coordination of Aza-18-crown-6 ether with diglycolamide by p-benzyl as linkers enhancing the selectivity for heavy REEs(III)

The development of new ligands is crucial for the functional application of REEs(III), because the coordination compounds of rare-earth elements (REEs) have many important applications in pharmaceuticals and nuclear medicine. In this paper, a novel ligand (Cr6-Bz-DGA) with the aza-crown ether and diglycolamide (DGA) units was designed to coordinate with light, medium, and heavy REEs(III). It was found that M/L = 2:2 species (aza-crown ether-REEs(III)-DGA connection) was the thermodynamically stable complex. The stability constants of Nd(III), Eu(III), and Ho(III) complexes were determined by UV–Vis and fluorescence titration, respectively, which were logβNd = 7.49 ± 0.019, logβEu = 7.10 ± 0.013 and logβHo = 8.27 ± 0.032. The variation of fluorescence lifetime suggested that the Eu(III) ion was exclusively coordinated by the ligand with coordination number 9 in the inner sphere of the Eu(III) ion. The shifts of 1H NMR revealed that there are different coordination between the ligand and REEs(III). For larger ionic radii La(III), three O atoms of the DGA unit and five O and one N atoms of the aza-crown ether unit were supplied. While, for Y(III)/Lu(III) with smaller ion radii, the ligand supplied three O atoms from the DGA and one N atom and only two O atoms from the aza-crown ether. The displacement experiment of REEs(III) combined with ligand and the fitted stability constants prove that the smaller ionic radii REEs(III) more strongly bind with ligand than larger ionic radius REEs(III). These results may help understand the coordination behavior of REEs(III) and expand their potential applications.

Advances in Functional Ceramics for Water Splitting: A Comprehensive Review

The global demand for sustainable energy sources has led to extensive research regarding (green) hydrogen production technologies, with water splitting emerging as a promising avenue. In the near future the calculated hydrogen demand is expected to be 2.3 Gt per year. For green hydrogen production, 1.5 ppm of Earth’s freshwater, or 30 ppb of saltwater, is required each year, which is less than that currently consumed by fossil fuel-based energy. Functional ceramics, known for their stability and tunable properties, have garnered attention in the field of water splitting. This review provides an in-depth analysis of recent advancements in functional ceramics for water splitting, addressing key mechanisms, challenges, and prospects. Theoretical aspects, including electronic structure and crystallography, are explored to understand the catalytic behavior of these materials. Hematite photoanodes, vital for solar-driven water splitting, are discussed alongside strategies to enhance their performance, such as heterojunction structures and cocatalyst integration. Compositionally complex perovskite oxides and high-entropy alloys/ceramics are investigated for their potential for use in solar thermochemical water splitting, highlighting innovative approaches and challenges. Further exploration encompasses inorganic materials like metal oxides, molybdates, and rare earth compounds, revealing their catalytic activity and potential for water-splitting applications. Despite progress, challenges persist, indicating the need for continued research in the fields of material design and synthesis to advance sustainable hydrogen production.

Characterization of magnetic properties, including magnetocaloric effect, of RE5Pt2In4 (RE = Gd-Tm) compounds

The RE5Pt2In4 (RE = Gd-Tm) rare earth compounds have been investigated by means of X-ray diffraction (XRD) as well as by DC and AC magnetometric measurements. The compounds crystallize in an orthorhombic crystal structure of the Lu5Ni2In4-type (Pbam space group, No. 55). With decreasing temperature, the intermetallics undergo a transition from para- to ferro-/ferri- (RE = Gd, Tb, Ho, Er) or antiferromagnetic state (RE = Tm). In case of Dy5Pt2In4, the ferromagnetic state is reached through an intermediate antiferromagnetic order present in a limited temperature range. The critical temperatures of magnetic ordering range from 4.1 K (RE = Tm) up to 108 K (RE = Tb). For the majority of investigated compounds, a cascade of additional magnetic transitions is found below the respective critical temperatures of magnetic ordering. The magnetic moments are found solely on the rare earth atoms, while the moments of the remaining Pt and In atoms are absent or are too small to be detected while accompanied by the strong rare earth’s moments. The magnetocaloric (MCE) performance of RE5T2In4 (RE = Gd-Tm) is found quite good, especially while taking into account the compounds with RE = Ho and Er. Maximum magnetic entropy change (−ΔSMmax) reaches 11.8 (RE = Ho) or 11.4 J ⋅ kg−1 ⋅ K−1 (RE = Er) under magnetic flux density change of 0–9 T. Under the same conditions, the relative cooling power (RCP) and refrigerant capacity (RC) equal 607 and 495 J ⋅ kg−1 (RE = Ho) or 434 and 341 J ⋅ kg−1 (RE = Er).

Recovery of rare earth elements from rare earth molten salt electrolytic slag via fluorine fixation by MgCl2 roasting

Rare earth fluoride molten-salt electrolytic slag (REFES) is a precious rare earth element (REE) secondary resource, and considerable amounts of REEs exist in REFES as REF3; they are difficult to dissolve in acid or water and impede efficient REE extraction. In REFES recovery, the REF3 species in REFES are usually transformed into acid-soluble rare earth compounds by NaOH roasting or sulfating roasting and then extracted by acid leaching. Moreover, the fluorides in REFES are released as HF gas in the roasting process or enter the liquid phase during the water washing process; both of these processes cause fluorine pollution. Fixing the fluorine into the solid slag provides a way to avoid fluorine pollution. In this study, a novel method was proposed to extract REEs from REFES via MgCl2 roasting followed by HCl leaching. Thermodynamics calculations and thermogravimetry‒differential thermal analyses (TG-DTA) were conducted to investigate the reactions occurring in the roasting process. First, MgCl2 reacts with the REF3 and RE2O3 to form RECl3 and REOCl, respectively. Second, the RECl3 absorbs water and forms RE(OH)3. Third, MgCl2·6H2O is gradually dehydrated to MgCl2·2H2O and reacts with REF3 and RE(OH)3, and REOCl, MgF2 and MgO are formed. Through HCl leaching, the REOCl in the roasting products is leached by HCl acid, while fluoride remains in the solid slag as MgF2. The optimum experimental conditions are as follows: mass ratio of MgCl2 to REFES of 30%, roasting temperature of 700 °C, roasting time of 2 h, hydrochloride acid concentration of 4 mol/L, leaching time of 2 h, leaching temperature of 90 °C and leaching L/S ratio of 20:1. The efficiencies for total leaching of the REEs, La, Ce, Pr, and Nd are 99.13%, 99.20%, 98.42%, 99.38%, and 99.08%, respectively. Moreover, the concentration of fluoride in the leaching solution is 2.191 × 10−6 mol/L. This method has a short process flow with low reagent costs, and the problem of fluoride pollution from REFES recovery is solved; thus, our study has great industrial application potential.

Lanthanide-Containing Polyoxometalate Crystallized with Bolaamphiphile Surfactants as Inorganic–Organic Hybrid Phosphors

Lanthanide elements such as europium exhibit distinctive emissions due to the transitions of inner-shell 4f electrons. Inorganic materials containing lanthanide elements have been widely used as phosphors in conventional displays. The hybridization of lanthanide ions with organic components enables to control of the material’s shapes and properties and broadens the possibility of lanthanide compounds as inorganic–organic materials. Lanthanide ion-containing polyoxometalate anions (Ln-POM) are a promising category as an inorganic component to design and synthesize inorganic–organic hybrids. Several inorganic–organic Ln-POM systems have been reported by hybridizing with cationic surfactants as luminescent materials. However, single-crystalline ordering has not been achieved in most cases. Here, we report syntheses and structures of inorganic–organic hybrid crystals of lanthanide-based POM and bolaamphiphile surfactants with two hydrophilic heads in one molecule. An emissive decatungstoeuropate ([EuW10O36]9−, EuW10) anion was employed as a lanthanide source. The bolaamphiphile counterparts are 1,8-octamethylenediammonium ([H3N(CH2)8NH3]2+, C8N2) and 1,10-decamethylenediammonium ([H3N(CH2)10NH3]2+, C10N2). Both hybrid crystals of C8N2-EuW10 and C10N2-EuW10 were successfully obtained as single crystals, and their crystal structures were unambiguously determined using X-ray diffraction measurements. The photoluminescence properties of C8N2-EuW10 and C10N2-EuW10 were investigated by means of steady-state and time-resolved spectroscopy. The characteristic emission derived from the EuW10 anion was retained after the hybridization process.

Polyoxometalate Ligands Reveal Different Coordination Chemistries Among Lanthanides and Heavy Actinides.

Experimental studies involving actinide compounds are inherently limited in scope due to the radioactive nature of these elements and the scarcity and cost of their research isotopes. Now, ∼80 years after the introduction of the actinide concept by Glenn Seaborg, we still only have a limited understanding of the coordination chemistry of f-block metals when compared to more common elements such as the s-, p-, and d-blocks. This is particularly true for transplutonium actinides (Am, Cm, Bk, etc.) whose chemistry is often considered similar to trivalent lanthanides-mainly because of the lack of experimental data. We here report a metal-ligand system for which lanthanide and heavy actinide coordination compounds can be synthesized efficiently (i.e., requiring only a few micrograms) under identical conditions. Seventeen single crystal XRD structures of trivalent f-elements complexed to the polyoxometalate (POM) PW11O39 7- were obtained, including the full lanthanide series (Cs11Ln(PW11O39)2·nH2O, Ln = La to Lu, except Pm), the equivalent yttrium compound, a curium-POM compound (α2-Cs11Cm(PW11O39)2·33H2O), and the first two Am3+-POM compounds structurally characterized (α1-Cs11Am(PW11O39)2·6H2O and α2-Cs11Am(PW11O39)2·21H2O). Importantly, this represents a unique series of compounds built on the same 1:2 metal:ligand unit and where all the f-elements are 8-coordinated and squared antiprismatic, thus providing a consistent platform for intra- and inter-series comparison. Despite a similar first coordination sphere environment, significant crystallographic and spectroscopic differences were observed among early and late lanthanides, as well as lanthanides and actinides, and even between americium and curium. These results show that even within the same coordination chemistry framework, 4f and 5f elements exhibit fundamental chemical differences that cannot be explained by simple size-match arguments. This study offers a versatile coordination platform to magnify differences within the f-block that have remained difficult to observe with traditional ligand systems.

The self-assembly of tetranuclear [Gd4] cluster: Magnetic refrigeration and efficient CO2 chemical fixation

In this paper, the self-assembly of Gd3+ ions and ligand 5-chlorine-8-hydroxylquinoline (HL) successfully generated one tetranuclear lanthanide compound [Gd4(µ3-OH)2(L)6(acac)4] (1) (L = 5-chlorine-8-hydroxylquinoline; Hacac = acetylacetone), in which four Gd3+ ions are connected into a [Gd4O2] cluster. Magnetic studies revealed that anti-ferromagnetic interactions between neighbouring Gd3+ ions were observed in 1. In addition, 1 also shows magnetocaloric effect and the −ΔSm value reaches 28.05 J kg−1 K−1 at T = 2.0 K and ΔH = 7 T. Catalytic experiments indicated that 1 and tetra-n-butylammonium bromide (TBAB) could synergistically catalyze the cycloaddition reaction of CO2 and epoxides at relatively mild condition.

Atomic layer molecular beam epitaxy of kagome magnet RMn6Sn6 (R = Er, Tb) thin films

Kagome lattices have garnered substantial interest because their band structure consists of topological flat bands and Dirac cones. The RMn6Sn6 (R = rare earth) compounds are particularly interesting because of the existence of the large intrinsic anomalous Hall effect (AHE), which originates from the gapped Dirac cones near the Fermi level. This makes RMn6Sn6 an outstanding candidate for realizing the high-temperature quantum AHE. The growth of RMn6Sn6 thin films is beneficial for both fundamental research and potential applications. However, most of the studies on RMn6Sn6 have focused on bulk crystals, and the synthesis of RMn6Sn6 thin films has not been reported so far. Here, we report the atomic layer molecular beam epitaxy growth, structural and magnetic characterizations, and transport properties of ErMn6Sn6 and TbMn6Sn6 thin films. It is especially noteworthy that TbMn6Sn6 thin films have out-of-plane magnetic anisotropy, which is important for realizing the quantum AHE. Our work paves the avenue toward the control of the AHE using devices patterned from RMn6Sn6 thin films.

New hematite method: efficient and enhanced separation of rare earth and iron by alkaline regulation of pH in rare earth chloride solutions

Iron in RECl3 solutions is a detrimental impurity, adversely impacting both the purification efficiency of RECl3 and purity of rare earth compounds. RECl3 solutions employs the neutralization precipitation method for iron removal, leading to iron slag rich in valuable rare earth elements and radioactive thorium. This practice not only results in rare earth resource wastage but also poses significant ecological challenges. This study introduces an innovative hematite method for efficient and enhanced separation of rare earth and iron from RECl3 solutions. This method involves adjusting the solution's pH using alkali in a high-pressure reactor. Results indicate optimal conditions: a OH− to Fe3+ ratio of 1.5:1, temperature at 180°C, duration of 3 hours, and a Fe3+ (as Fe2O3) to Fe2O3 crystal seed molar ratio of 1:1. Under these conditions, the iron slag contains 1.3% REO and 63.69% TFe, with a rare earth loss rate of 0.35% and a TFe removal rate of 90.36%. Thermodynamic analysis reveals that at 25°C, ammonia water adjusts the pH of RECl3 solutions to 2-3, with the presence of Fe(OH)2+ and Fe(OH)2+ in the solution. The potential pH diagram of Ce-Fe-H2O at 180°C indicates that a pH range of -1.87 to 2.99 is crucial for Fe2O3 and Ce3+ formation. SEM analysis shows that the iron slag phase is a densely packed elliptical hematite sphere of approximately 1 micron and contains 0.36% thorium. This new hematite method using alkali-regulated high-temperature and high-pressure conditions for iron removal from RECl3 solutions not only minimizes rare earth loss but also mitigates iron slag's environmental impact. Furthermore, it offers a novel iron removal technique for the smelting industry.

Enhanced anomalous Hall effect in kagome magnet YbMn6Sn6 with intermediate-valence ytterbium

We report on the magnetization and anomalous Hall effect (AHE) in the high-quality single crystals of the kagome magnet YbMn6Sn6, where the spins of the Mn atoms in the kagome lattice order ferromagnetically and the intermediate-valence Yb atoms are nonmagnetic. The intrinsic mechanism plays a crucial role in the AHE, leading to an enhanced anomalous Hall conductivity (AHC) compared with the other rare-earth RMn6Sn6 compounds. Our band structure calculation reveals a strong hybridization between the 4f electrons of Yb and conduction electrons.

Topological aspects of multi-k antiferromagnetism in cubic rare-earth compounds

We advertise rare-earth intermetallics with high-symmetry crystal structures and competing interactions as a possible materials platform hosting spin structures with non-trivial topological properties. Focusing on the series of cubic RCu compounds, where R = Ho, Er, Tm, the bulk properties of these systems display exceptionally rich magnetic phase diagrams hosting an abundance of different phase pockets characteristic of antiferromagnetic order in the presence of delicately balanced interactions. The electrical transport properties exhibit large anomalous contributions suggestive of topologically non-trivial winding in the electronic and magnetic structures. Neutron diffraction identifies spontaneous long-range magnetic order in terms of commensurate and incommensurate variations of (ππ0) antiferromagnetism with the possibility for various multi- k configurations. Motivated by general trends in these materials, we discuss the possible existence of topologically non-trivial winding in real and reciprocal space in the class of RCu compounds including antiferromagnetic skyrmion lattices. Putatively bringing together different limits of non-trivial topological winding in the same material, the combination of properties in RCu systems promises access to advanced functionalities.

Ultrastrong Electron-Phonon Coupling in Uranium-Organic Frameworks Leading to Inverse Luminescence Temperature Dependence.

Electron-phonon interactions, crucial in condensed matter, are rarely seen in Metal-Organic Frameworks (MOFs). Detecting these interactions typically involves analyzing luminescence in lanthanide- or actinide-based compounds. Prior studies on Ln- and Ac-based MOFs at high temperatures revealed additional peaks, but these were too faint for thorough analysis. In our research, we fabricated a high-quality, crystalline uranium-based MOF (KIT-U-1) thin film using a layer-by-layer method. Under UV light, this film showed two distinct "hot bands," indicating a strong electron-phonon interaction. At 77 K, these bands were absent, but at 300 K, a new emission band appeared with half the intensity of the main luminescence. Surprisingly, a second hot band emerged above 320 K, deviating from previous findings in rare-earth compounds. We conducted a detailed ab-initio analysis employing time-dependent density functional theory to understand this unusual behaviour and to identify the lattice vibration responsible for the strong electron-phonon coupling. The KIT-U-1 film's hot-band emission was then utilized to create a highly sensitive, single-compound optical thermometer. This underscores the potential of high-quality MOF thin films in exploiting the unique luminescence of lanthanides and actinides for advanced applications.

Thermoelectric performance optimization of GeMnSbTe compounds through increasing the Mn solid solubility: Effects of the co-doping of rare earth elements

GeTe is a p-type thermoelectric (TE) material that exhibits a high ZT value and holds promise for a wide range of applications. In this study, a series of Ge0.86Mn0.1Sb0.04Te + 1 mol.% RE (Rare Earth elements = Er, Tm, Yb, Lu) compounds are synthesized through the melt-quenching method followed by fast-hot-pressing. Findings indicate that the TE properties are improved by simultaneously increasing the Seebeck coefficient and reducing the thermal conductivity, making the peak ZT value experiences an enhancement of 73%, while the average ZT value through 450–800 K shows an improvement of 70%. The solid solubility of Mn is significantly increased by the addition of the REs, that promotes the regulating effect of Mn on the energy band. A diverse range of microstructures including ordered atomic staggered arrays, van der Waals interstitials, dislocation enrichment, dislocation networks, nano precipitation phases with cavity structures, interstitial clusters, and vacancy clusters are introduced by REs, significantly contributing to the reduction of the κL. Thus, this study offers valuable insights and mechanism analysis into enhancing the properties of GeMnSbTe materials by incorporating REs, and proves that Tm has better thermoelectric performance optimization effect in this.