Localization Of Charge Carriers Research Articles

Peculiarities of magnetoresistance in GaAs whiskers at low temperatures

Magnetoresistance of GaAs whiskers with concentrations in the vicinity to metal-insulator transition (MIT) 1017–1018 cm−3 were studied at low temperatures and high magnetic fields (up to 14 T). The whiskers were doped with Te during the growth. The whisker diameter ranges from 10 to 40 μm. Temperature dependence of the whisker resistance have shown metallic and semiconductor character in the proximity to MIT from various sides of the transition. Depending on doping level the character of the whisker magnetoresistance changes from linear positive to quadratic negative. The magnetoresistance of metallic whiskers is explained in terms of weak antilocalization (WAL) model. The specimens with semiconductor character of conductance revealed negative magnetoresistance, magnitude of which rises due to moving away from MIT and reach 15% for the whiskers with concentration 1017 cm−3. The possible reasons of the negative magnetoresistance are discussed. The effect observed is attributed to weak localization (WL) of charge carriers in the region of hopping conductance for the whiskers in the vicinity to MIT. A high negative magnetoresistance (NMR) for the whiskers of low dopant concentration is connected with subsurface conductance in the disordered upper layers of the whiskers due to their core-shell structure.

Cocatalyst activity mapping for photocatalytic materials revealed by the pattern-illumination time-resolved phase microscopy.

Photocatalytic water-splitting represents a promising avenue for clean hydrogen production, necessitating an in-depth understanding of the photocatalytic reaction mechanism. The majority of the photocatalytic materials need cocatalysts to enhance the photo-oxidation or reduction reactions. However, the working mechanism, such as collecting charge carriers or reducing the reaction barrier, is not clear because they disperse inhomogeneously on a surface, and it is difficult to follow the local charge carrier behavior. This study employs the pattern-illumination time-resolved phase microscopy (PI-PM) method to unravel the spatial charge carrier behavior in photocatalytic systems, utilizing time-resolved microscopic image (refractive index change) sequences and their clustering analyses. This approach is robust for studying the change in local charge carrier behavior. We studied two major cocatalyst effects on photocatalysts: TiO2 with/without Pt and hematite with/without CoPi. The PI-PM method, supported by charge type clustering and the effects of scavengers, allowed for the analysis of local activity influenced by cocatalysts. This approach revealed that the introduction of cocatalysts alters the local distribution of charge carrier behavior and significantly impacts their decay rates. In TiO2 systems, the presence of Pt cocatalysts led to a local electron site on the micron scale, extending the lifetime to a few tens of microseconds from a few microseconds. Similarly, in hematite films with CoPi, we observed a notable accumulation of holes at cocatalyst sites, emphasizing the role of cocatalysts in enhancing photocatalytic efficiency. The study's findings highlight the complexity of charge carrier dynamics in photocatalytic processes and the significant influence of cocatalysts.

Coherent Carrier Spin Dynamics in FAPbBr3 Perovskite Crystals.

Coherent spin dynamics of electrons and holes are studied in hybrid organic-inorganic lead halide perovskite FAPbBr3 bulk single crystals using the time-resolved Kerr ellipticity technique at cryogenic temperatures. The Larmor spin precession of the carrier spins in a magnetic field is monitored to measure the Landé g-factors of electrons (+2.44) and holes (+0.41). These g-factors are highly isotropic. The measured spin dephasing times amount to a few nanoseconds, and the longitudinal hole spin relaxation time is 470 ns. The important role of the strong hyperfine interaction between carrier spins and nuclear spins is demonstrated via dynamic nuclear polarization. At low temperatures, electron and hole spin relaxation predominantly occurs via the hyperfine interaction, whose importance significantly decreases at temperatures above 12 K. We overview the spin dynamics in various lead halide perovskite crystals and polycrystalline films and conclude on their common features provided by charge carrier localization at cryogenic temperatures.

Oxygen vacancy induced carrier localization in enhancing photocatalytic performance of ZnO

Within the realm of advancing photocatalysis, the investigation of material defects has perennially commanded paramount attention. However, a nuanced comprehension of the intricate interplay between these defects and the catalytic milieu necessitates deeper exploration. In the present study, oxygen vacancies (Vo) were adeptly harnessed to induce precise carrier localization, thereby effectuating a heightened augmentation of photocatalytic activity. This augmentation was deftly achieved through the deliberate modulation of external illumination parameters, resulting in the extension of carrier lifetimes. Specifically, the drastically enhanced carrier effective mass (m*) and the density of unoccupied state are directly uncovered by the density functional theory (DFT) calculation and Raman spectra. Through the utilization of wavelength dispersive in-situ fluorescence spectroscopy (WDIFS) experiments, it was observed that Vo-rich ZnO nanoparticles (NPs) displayed noteworthy photocatalytic activity around the central frequency of Vo (5.17 × 1014 Hz, 580 nm), owing to the highly efficient utilization of localized carriers. Moreover, based on Einstein rate equations, the charge carrier lifetime was found to be further prolonged with increased external illumination intensity and excitation wavelength. This work provides a methodology for optimizing the functionality of point defect on photocatalysis, where the photo-induced charge carrier localization is expected to be extensively used in further photocatalysis research.

Electrical Resistivity Behavior and Small Polaron Conduction Transport Mechanism in Semiconducting <I>R</I>MnO<sub>3</sub> Manganites

Rare earth manganites, denoted by the chemical formula <I>R</I>MnO<sub>3</sub>, where <I>R</I> signifies a rare earth element, have garnered significant interest in recent years. These perovskite oxides exhibit intriguing phenomena such as multiferroicity, ferroelectricity, and colossal magnetoresistance, primarily attributed to the role of polarons in conduction. The incorporation of rare earth ions imparts flexibility, making these compounds promising for applications in spintronics, sensors, and information storage devices. This study delves into the electrical resistivity behavior and Small Polaron Conduction (SPC) mechanisms of rare earth manganites, particularly <I>R</I>MnO<sub>3</sub>. In this manuscript, electrical resistivity of the pristine <I>R</I>MnO<sub>3</sub> (<I>R</I> = Sm, Eu, Gd) manganites are analyzed within the framework of adiabatic nearest-neighbor hopping of SPC. The high temperature state of <I>R</I>MnO<sub>3</sub> within the SPC mechanism is influenced by polaron concentration, hopping distance, and resistivity coefficient. The localized charge carriers in undoped manganites enable one to estimate the activation energy for the electrical conduction. The activation energy decreases with the decrease in ionic radii from Sm to Gd. Deduced polaron activation energy is low for GdMnO<sub>3</sub> as compared to SmMnO<sub>3</sub> and is attributed to reducing disorder state in GdMnO<sub>3</sub> as compared to SmMnO<sub>3</sub>. This work contributes to the fundamental understanding of condensed matter physics and the potential applications of rare earth manganites in emerging technologies. The interplay between electrical resistivity and Small Polaron Conduction offers insights for customizing these materials for specific technological needs.

Localized surface plasmon resonance-induced charge carrier localization at the silver nanoparticle/graphene quantum dot interface

We report a novel investigation into the effects of localized surface plasmon resonance (LSPR) on charge carrier localization and dynamics, utilizing a test structure where pentacene is layered over a graphene quantum dot (GQD) film. To induce LSPR, we strategically embedded silver nanoparticles (Ag NPs) between the pentacene and GQD films. This configuration led to a notable shift in the threshold voltage when the structure was illuminated at a resonance frequency of 450 nm. This shift is primarily attributed to the LSPR-induced charge transfer occurring at the interface between the Ag NPs and the GQD film. Remarkably, following the discontinuation of illumination, there was a noticeable and gradual release of electrons previously localized at the Ag NP/GQD interface. This phenomenon demonstrated effective retention of electrons at the interface, which subsequently led to an enhancement in the field-effect transistor (FET) mobility. This enhancement in the FET mobility is likely due to the diminished Coulombic interaction between the localized electrons and the mobile hole carriers within the pentacene channel.“

Toward Highly Efficient Low‐Carbon Footprint Solar Cells: Impact of High‐Temperature Processing on Epitaxially Grown p‐Type Silicon Wafers

Conventional silicon (Si) wafers are produced by energy‐intensive ingot crystallization which is responsible for a major share of a solar cell's carbon footprint. This work explores Si epitaxially grown silicon wafers (EpiWafers) that are produced by direct epitaxial deposition of trichlorosilane on a reusable substrate. This approach requires less energy and material and hence offers a potential for reduced cost and carbon footprint. Solar cells made from EpiWafers usually suffer from efficiency losses due to recombination at structural crystal defects associated with epitaxial growth. The nature of these defects is investigated and defects at the EpiWafer's back surface are critical. Most of these defects are highly recombination‐active, pairwise‐connected misfit dislocations in the <110> direction. They originate from a lattice mismatch between the highly doped substrate and the less‐doped epitaxially grown layer. In this contribution, the detrimental impact of these defects can be mitigated using typical manufacturing processes of high‐efficiency solar cells, such as KOH etching, gettering, and oxidation. Local minority charge carrier lifetimes as high as 2.2 ms after industrially feasible processes are reported. Simulations using efficiency‐limiting bulk recombination analysis implies that the material would allow conversion efficiencies of up to 25.6% considering tunnel oxide‐passivated contact acting as rear emitter solar cell design.

Trap suppression in ordered organic photovoltaic heterojunctions.

The high trap density (generally 1016-1018 cm-3) in organic solar cells (OSCs) brings about the localization of charge carriers and reduced charge carrier lifetime, mainly due to the weak intermolecular interactions of organic semiconductors resulting in their relatively poor crystallinity, which leads to low charge carrier mobilities and intense non-radiative recombination, thus impeding the further improvement of power conversion efficiencies (PCEs). Therefore, trap suppression is crucial to boost the performance of OSCs, and improving the crystallinity of donor/acceptor materials and enhancing the molecular order in devices can contribute to the trap suppression in OSCs. In this feature article, we summarize the recent advances of trap suppression in OSCs by material design and device engineering, and further outline possible development directions for trap suppression to enhance PCEs of OSCs.

Unveiling the role of linear alkyl organic cations in 2D layered tin halide perovskite field-effect transistors.

Two-dimensional (2D) tin halide perovskites are promising semiconductors for field-effect transistors (FETs) owing to their fascinating electronic properties. However, the correlation between the chemical nature of organic cations and charge carrier transport is still far from understanding. In this study, the influence of chain length of linear alkyl ammonium cations on film morphology, crystallinity, and charge transport in 2D tin halide perovskites is investigated. The carbon chain lengths of the organic spacers vary from propylammonium to heptanammonium. The increase of alkyl chain length leads to enhanced local charge carrier transport in the perovskite film with mobilities of up to 8 cm2 V-1 s-1, as confirmed by optical-pump terahertz spectroscopy. A similar improved macroscopic charge transport is also observed in FETs, only to the chain length of HA, due to the synergistic enhancement of film morphology and molecular organization. While the mobility increases with the temperature rise from 100 K to 200 K due to the thermally activated transport mechanism, the device performance decreases in the temperature range of 200 K to 295 K because of ion migration. These results provide guidelines on rational design principles of organic spacer cations for 2D tin halide perovskites and contribute to other optoelectronic applications.

Luminescence in Anion-Deficient Hafnia Nanotubes.

Hafnia-based nanostructures and other high-k dielectrics are promising wide-gap materials for developing new opto- and nanoelectronic devices. They possess a unique combination of physical and chemical properties, such as insensitivity to electrical and optical degradation, radiation damage stability, a high specific surface area, and an increased concentration of the appropriate active electron-hole centers. The present paper aims to investigate the structural, optical, and luminescent properties of anodized non-stoichiometric HfO2 nanotubes. As-grown amorphous hafnia nanotubes and nanotubes annealed at 700 °C with a monoclinic crystal lattice served as samples. It has been shown that the bandgap Eg for direct allowed transitions amounts to 5.65 ± 0.05 eV for amorphous and 5.51 ± 0.05 eV for monoclinic nanotubes. For the first time, we have studied the features of intrinsic cathodoluminescence and photoluminescence in the obtained nanotubular HfO2 structures with an atomic deficiency in the anion sublattice at temperatures of 10 and 300 K. A broad emission band with a maximum of 2.3-2.4 eV has been revealed. We have also conducted an analysis of the kinetic dependencies of the observed photoluminescence for synthesized HfO2 samples in the millisecond range at room temperature. It showed that there are several types of optically active capture and emission centers based on vacancy states in the O3f and O4f positions with different coordination numbers and a varied number of localized charge carriers (V0, V-, and V2-). The uncovered regularities can be used to optimize the functional characteristics of developed-surface luminescent media based on nanotubular and nanoporous modifications of hafnia.

Thermoelectric properties of La1.96Sr0.04CuO4 for energy harvesting and storage applications

AbstractThe polycrystalline pellet of La2‐xSrxCuO4 with x = 0.04, has been sintered using the solid‐state reaction process. X‐ray diffraction (XRD) and field emission scanning electron microscopy (FESEM) have been carried out for microstructural characterizations. The transport properties (electrical and thermal) of La2‐xSrxCuO4 for x = 0.04 have been investigated in the temperature range between 15 and 300 K with the aid of a closed‐cycle refrigerator (CCR). The DC four‐probe resistivity measurement confirms a decrease in resistivity with increasing temperature below 200 K. However, above 200 K, an increase in resistivity with temperature (metallic behaviour) has been noticed due to charge carrier localization. The Hall measurement conveys hole‐type conduction and phonon‐dominated mobility with carrier concentration ~1018/cm3, which lie somewhere between non‐degenerate and degenerate limit. The Seebeck coefficient also confirms hole type conduction and its temperature dependence can be explained in the light of the model applicable for mixed‐valence heavy fermions systems. The steady‐state method for thermal conductivity measurement has been employed. The plot of thermal conductivity (λ) as a function of temperature (T) shows a hump‐like structure at around 65 K, which may be attributed to an increase in the quasi‐particle mean free path. Further, the electronic and lattice (phononic) contributions to thermal conductivity have been separated using electrical conductivity data with the help of the Wiedemann‐Franz law. Our analysis confirms the phononic dominance in the thermal conductivity of the investigated sample. The figure of merit (ZT) estimated from the experimental data has a maximum value of 0.086 at 290 K and hence shows its inherent energy harvesting properties that can further be stored in a battery or capacitor.

Charge Carrier Localization in InAs Self-Organized Quantum Dots

Charge Carrier Localization in InAs Self-Organized Quantum Dots

The effect of 1 MeV electron irradiation on charge carrier localization in graphene quantum dot array of reduced graphene oxide

This paper presents a study of the effect of 1 MeV electron irradiation on the localization of charge carriers in graphene quantum dots (GQDs) located in a reduced graphene oxide (RGO). The electrical properties were analyzed in a wide temperature range of 4.2–340 K for fluences of 0–160 × 1015 cm−2. The localization length, dielectric permittivity, and density of localized states were estimated. It was found that the conductivity and charge localization parameters exhibit non-monotonic behavior depending on the electron fluences. It can change several times in the vicinity of a fluence of 10 × 1015 cm−2 compared to the higher or lower fluence. It is shown that electron irradiation affects the disordered surrounding matrix, which leads to an increase in the content of oxygen and functional groups. At the same time, the size of the sp2‑carbon domains does not depend on the fluence. It is assumed that electron irradiation indirectly affects the properties of GQDs. The transformation of the surrounding disordered matrix leads to a modification of the electronic properties of the GQDs array and the RGO as a whole. The non-monotonic behavior of the RGO conductivity upon irradiation is due to the features of the energy spectrum of the GQDs array, which is characterized by the presence of periodic peaks in the density of states. The irradiation-induced structural modification likely leads to a shift in the Fermi level and a change in the density of states. It is shown that the RGO behaves like a wide-band doped semiconductor. The difference is that the impurity level was formed by GQDs. At temperatures above 310 K, the RGO conductivity exhibits an Arrhenius behavior with an activation energy of about 60 meV due to charge carrier delocalization at thermal ejection into the extended band.

Novel nanocomposites based on Tetrazine liquid crystals for energy storage application

Polymethyl methacrylate (PMMA) /Tetrazine liquid crystal (LCTZ12) nanocomposites with different CNTs loadings have been prepared. The prepared nanocomposites were characterized using polarizing light microscope (POM), differential scanning calorimetry (DSC), Fourier transform Infrared Spectroscopy (FTIR) and broadband dielectric spectroscopy (BDS) in the range 10-1-106 Hz respectively. The most commonly observed texture of soft crystal phases was that of a mosaic pattern, as revealed by the POM technique. PMMA alone does not change the polarization states and appeared as isotropic material, but once LCTZ12 is added, crystal growth could be clearly noticed in the needle pattern inside the polymer matrix to compose an amazing structure of soft crystal G texture. The increase of LCTZ12 to about 20 wt% in the PMMA matrix led to more heterogeneous aggregation of liquid crystalline molecules. This ratio addition is enhancing of network connections inside the PMMA. Moreover, the dispersion of carbon nanotubes mounted on catalysts is found to accumulate in segregations in PMMA/ LCTZ12 nanocomposites. However, the location of CNTs is concentrated at bottom of polymer network due to the large difference in densities of LCs, PMMA, and CNTs. DSC is in agreement with the POM result of LCTZ12, which has multi soft crystals or highly self-assembled ordered liquid crystal phases near to room temperature. The FTIR proved that blend PMMA/ LCTZ12 (80/20) has a dramatic increase in the 1387 cm−1 peak of C = C as a response of the rise in the concentration or number of aromatic rings. Additionally, the vibrational scissoring peak located at 1477 cm−1 of methylene CH2 groups is increased significantly and C–H stretching in aliphatic regions at 2850 cm−1 and 2990 cm−1 as well. However, there is no significant change observed after CNTs addition to the PMMA/ 20 wt% LCTZ12 matrix. Regarding dielectric results, it was found that, the polymer dispersed liquid crystals PDLC system composed of (PMMA/20 wt% LCTZ12) possesses the most promising dielectric properties, that is; high dielectric permittivity with low losses compared to the other ratios. The addition of CNTs results in more localization of charge carriers along with mobile ions, causing higher ionic conductivity. The conductivity ranges altered from 3.2 × 10-10 S/cm in pure PDLC system to become 1.7 × 10-3 S/cm for PDLC doped with 10 wt% CNTs nanocomposite. The electrical energy density measurements for 3,6-bis(5-(Dodecyloxy) pyridin-2-yl)-1,2,4,5-tetrazine (LCTZ12) liquid crystals with 6 cationic centers in polymeric matrices proved to be suitable for flexible and efficient electrolytes for energy storage devices.

Disorder‐Controlled Efficient Doping of Conjugated Polymers for High‐Performance Organic Thermoelectrics

AbstractMolecular doping of conjugated polymers (CPs) is critical to improve their electrical properties in organic thermoelectric materials, which are promising candidates for low‐temperature energy harvesting and self‐powered sensors. Because excessive dopants are used in the doping process, securing highly crystalline CPs by suppressing dopant‐induced disorder is crucial. Recently, tris(pentafluorophenyl)borane (BCF) has attracted interest as a strong Brønsted acid dopant that enables efficient integer charge transfer by forming a complex with water. However, the crystalline ordering of BCF‐doped CPs has not been properly controlled; the resultant thermoelectric performance is therefore still lower than other p‐doped CPs prepared by conventional redox doping. Here, an efficient doping strategy is proposed with BCF to attain highly doped CPs with dramatically suppressed structural and energetic disorder. In a non‐polar aliphatic solvent, hexane, BCF can effectively diffuse into poly[2,5‐bis(3‐tetradecylthiophen‐2‐yl)thieno[3,2‐b]thiophene] (PBTTT) via sequential doping, leading to remarkable electrical conductivity and power factor of 230 S cm−1 and 140 µW m−1 K−2, respectively. In addition, sequentially doped films exhibit highly delocalized transport characteristics owing to the low degree of charge carrier localization within their high solid‐state ordering. The results provide an approach for disorder‐tolerant doping strategies with a systematic investigation of structure–property relationships in highly doped CPs.

Cation-Disorder Engineering Promotes Efficient Charge-Carrier Transport in AgBiS2 Nanocrystal Films.

Efficient charge-carrier transport is critical to the success of emergent semiconductors in photovoltaic applications. So far, disorder has been considered detrimental for charge-carrier transport, lowering mobilities, and causing fast recombination. This work demonstrates that, when properly engineered, cation disorder in a multinary chalcogenide semiconductor can considerably enhance the charge-carrier mobility and extend the charge-carrier lifetime. Here, the properties of AgBiS2 nanocrystals (NCs) are explored as a function of Ag and Bi cation-ordering, which can be modified via thermal-annealing. Local Ag-rich and Bi-rich domains formed during hot-injection synthesis are transformed to induce homogeneous disorder (random Ag-Bi distribution). Such cation-disorder engineering results in a sixfold increase in the charge-carrier mobility, reaching ≈2.7 cm2 V-1 s-1 in AgBiS2 NC thin films. It is further demonstrated that homogeneous cation disorder reduces charge-carrier localization, a hallmark of charge-carrier transport recently observed in silver-bismuth semiconductors. This work proposes that cation-disorder engineering flattens the disordered electronic landscape, removing tail states that would otherwise exacerbate Anderson localization of small polaronic states. Together, these findings unravel how cation-disorder engineering in multinary semiconductors can enhance the efficiency of renewable energy applications.

Evidence for nanosized magnetic clusters of Ce-ions in the archetypal heavy fermion metal CeB6

Fine details of crystal structure of archetypal CeB6 hexaboride with heavy fermions are studied at temperatures 85 and 500 K by precise X-ray diffraction technique. Small static Jahn-Teller distortions of a simple cubic lattice are observed at these temperatures, leading to emergence of (i) dynamic charge stripes along selected directions <110>, <100>, and <111> in the crystals in combination with (ii) vibrationally coupled pairs of Ce ions. Instead of a Currie-Weiss type behavior, the temperature dependence of magnetization M∼(T − TCrand)−0.8 with TCrand∼TQ∼3.3 K was deduced in a wide temperature range 5–800 K for various directions of external magnetic field, which indicates the Griffiths phase formation with nanosized clusters of magnetic ions in CeB6. Moreover, in contrast to the scenario of a single-ion Kondo lattice, when revealing the power-law behavior of the magnetic contribution ρm(T)∼T−0.4 to the resistivity in the range of 8–90 K, we conclude in favor of the regime of weak localization of charge carriers in CeB6. Fourier maps of electron density confirm the conclusion about the nanosized magnetic clusters of Ce ions in this archetypal strongly correlated electron system with unusual magnetic ground state.

Relative Local Electron Density Tuning in Metal‐Covalent Organic Frameworks for Boosting CO2 Photoreduction

AbstractThe high local electron density and efficient charge carrier separation are two important factors to affect photocatalytic activity, especially for the CO2 photoreduction reaction. However, the systematic studies on the structure‐functional relationship regarding the above two factors based on precisely structure model are rarely reported. Herein, as a proof‐of‐concept, we developed a new strategy on the evaluation of local electron density by controlling the relative electron‐deficient (ED) and electron‐rich (ER) intensity of monomer at a molecular level based on three rational‐designed vinylene‐linked sp2 carbon‐covalent organic frameworks (COFs). As expected, the as‐prepared vinylene‐linked sp2 carbon‐conjugated metal‐covalent organic framework (MCOFs) (VL‐MCOF‐1) with molecular junction exhibited excellent activities for CO2‐to‐HCOOH conversion (283.41 μmol g−1 h−1) and high selectivity of 97.1 %, much higher than the VL‐MCOF‐2 and g‐C34N6‐COF, which is due to the synergistic effect of the multi‐electronic metal clusters (Cu3(PyCA)3) (PyCA=pyrazolate‐4‐carboxaldehyde) as strong ER roles and cyanopyridine units as ED roles and active sites, as well as the boosted photo‐induced charge separation efficiency of vinyl connection and increased light utilization ability. These results not only provide a strategy for regulating the electron‐density distribution of photocatalysts at the molecular level but also offers profound insights for metal clusters‐based COFs to effective CO2 conversion.

Revival of Ferromagnetic-Metallic Phase and Emergence of Griffiths Phase via Ni and Cr Substitution in Charged-Ordered Pr0.75Na0.25MnO3 Manganite

Polycrystalline samples of Pr0.75Na0.25Mn1-xAxO3 (A = Ni, Cr; x = 0, 0.03) were prepared using conventional solid-state method and their structural and magnetic properties were investigated. Monovalent-doped Pr0.75Na0.25MnO3 exhibits insulating behavior which is related to the strong localization of charge carriers due to the presence of charge ordering (CO). The substitution of different types of magnetic ions, A, which are Ni2+ and Cr3+, at a concentration of x = 0.03 at the Mn site in the CO Pr0.75Na0.25Mn1-xAxO3 manganite, has been found to dramatically modify its structural and magnetic properties. X-ray diffraction patterns showed that all samples were present in single phase and crystallized in orthorhombic structure with Pnma space group. The Rietveld refinement analysis showed that the unit cell volume increased due to Ni2+ substitution, while it decreased due to Cr3+ substitution, which may be attributed to the different ionic radii of both ions. The suppression of the CO state and the induction of the ferromagnetic-metallic state in the Ni-substituted and Cr-substituted samples are suggested to be due to the induction of double-exchange interaction involving Ni2+–O–Mn4+ and Mn3+–O–Cr3+, respectively. The variation in magnetic properties between the Ni-substituted and Cr-substituted samples is suggested to be due to the existence of different strengths of ferromagnetic interaction between Ni2+–O–Mn4+ and Mn3+–O–Cr3+. In addition, the deviation of the temperature dependence of the inverse magnetic susceptibility curves from the Curie-Weiss law suggests the existence of Griffith’s phase-like behaviour for both substitution samples. The Ni-substituted sample induced a greater GP effect than the Cr-substituted sample due to the larger difference of TC and TG value (TC-TG).

Bright Green-Emitting All-Inorganic Terbium Halide Double Perovskite Nanocrystals for Low-Dose X-ray Imaging.

Inorganic halide double perovskite (DP) nanocrystals (NCs) have attracted great attention because of their nontoxicity, mild reaction conditions, good stability, and excellent optical and optoelectronic properties. Herein, we prepare the inorganic terbium halide DP Cs2BTbCl6 (B = Na or Ag) NCs with bright green photoluminescence (PL) emission. The Na-Tb-based DP NCs exhibit better PL properties compared with the Ag-Tb-based DP NCs, which is due to Cs2NaTbCl6 NCs having a more localized charge carrier distribution on the [TbCl6]3- octahedron. The incorporation of Sb3+ dopant in Cs2NaTbCl6 NCs can construct a more efficient energy transfer process, resulting in a doubling of PL efficiency. Furthermore, Cs2NaTbCl6: Sb3+ NCs possess excellent X-ray scintillating performance with a low-dose detection limit of 140 nGyair/s, which is nearly 5 times more sensitive than the undoped NCs. The optimized NCs show great application prospects in X-ray imaging. This work helps deepen the understanding of the luminescence mechanism, excited state dynamics, and scintillation property in Tb-based DP NCs.