Perovskite Phase Research Articles

Sr doping effects on La(1-x)SrxMnO3-BaTiO3 nanocomposites: A comprehensive analysis of structural, optical, magnetic, and dielectric properties

Sol-gel synthesized La(1-x)SrxMnO3–BaTiO3 nanocomposites with varying strontium content were investigated to explore the influence of Sr doping on their properties. X-ray diffraction confirmed the perovskite phase purity. Sr doping resulted in a tunable bandgap, widening from 2.33 eV to 2.57 eV as Sr content increased, as revealed by Diffuse Reflectance Spectroscopy. Vibrating Sample Magnetometry measurements exhibited a Sr-dependent decrease in saturation magnetization (22 emu/g for x = 0.2 to 14 emu/g for x = 0.5). Dielectric analysis demonstrated an enhanced dielectric constant and the emergence of new relaxation behaviors with Sr doping. These findings unveil the tailorable optical, magnetic, and dielectric properties of LSMO-BTO nanocomposites due to Sr doping, suggesting their potential for diverse technological applications.

Synergetic Electrostatic and Steric Effects in α-FAPbI3 Single Crystals For X-Ray Detection and Imaging.

It is still challenging to stabilize α-FAPbI3 perovskite for high performance optoelectrical devices. Herein, a novel strategy is proposed utilizing the synergetic electrostatic and steric effect to stabilize the α-FAPbI3 phase and suppress the ion migration. Dimethylamine (DMA+) cations are chosen as the dopant to fabricate FA0.96DMA0.04PbI3 single crystals (SCs). DFT calculations reveal that DMA+ cations can improve the stability of α-FAPbI3 phase in both thermodynamics (lower Gibbs free energy) and kinetics (higher defect formation and migration energy). The resulting SCs exhibit an environmental stability over 100 days and an extraordinary low dark current drift of 3.7×10-7nAcm-1s-1V-1, comparable to 2D perovskite SCs. The X-ray detectors have also achieved the-state-of-the-art performance in X-ray detection and imaging. This work demonstrates the significance of electrostatic and steric effects in improving the phase and operational stability of perovskites.

Unraveling nano-scale effects of topotactic reduction in LaNiO2 crystals

Infinite-layer nickelates stand as a promising frontier in the exploration of unconventional superconductivity. Their synthesis through topotactic oxygen reduction from the parent perovskite phase remains a complex and elusive process. This study delves into the nano-scale effects of the topotactic lattice transformation within LaNiO2 crystals. Leveraging high-resolution scanning transmission electron microscopy and spectroscopy, our investigations uncover a panorama of structural alterations, including grain boundaries and coherent twin boundaries, triggered by reduction-induced transformations. In addition, our analyses unveil the formation of an oxygen-rich disordered transition phase encircling impurities and pervading crystalline domains and the internal strain is accommodated by grain boundary formation. By unraveling these nano-scale effects, our findings provide insights into the microscopic intricacies of the topotactic reduction process elucidating the transition from the perovskite to the infinite-layer phase within nickelate bulk crystals.

Spectroscopic, vibrational and structural insights into LaYbO3:Pr3+ and LaLuO3:Pr3+,Tb3+ perovskites at ambient and high-pressure conditions

The interlanthanide perovskites LaYbO3:Pr3+ and LaLuO3:Pr3+,Tb3+ were synthesized by a solid-state reaction and characterized at ambient conditions by means of X-ray diffraction (XRD), Raman spectroscopy and photoluminescence techniques. XRD measurements have shown that the synthesis method provided samples with pure perovskite phase (space group Pnma) for LaYbO3, while in the case of the LaLuO3 compound small traces of Lu2O3 could be found after several annealing. Up to 13 Raman active modes were observed in the Raman spectra of the studied perovskites and theoretical calculations performed for LaYbO3 allowed to assign their symmetry. Regarding their optical properties, the emission from Tb3+ ions at B sites of the ABO3 perovskite could be distinguished. Moreover, NIR emission from Pr3+ was observed in the LaLuO3 perovskite at ∼1000 nm and 1250–1600 nm. Emission in these spectral regions could be relevant for Si-based solar cell applications and fiber optic amplifiers, respectively. Moreover, the stability of both perovskites under high-pressure conditions has been studied spectroscopically, finding that LaYbO3 is stable up to 19 GPa and that LaLuO3 undergoes a possible pressure-induced phase transition at ∼21–24 GPa. This makes LaLuO3 the first interlanthanide perovskite showing phase transition under 40 GPa.

High thermoelectric performance of n–type SrTiO3 by Dy and Nb co–doping

The effects of Dy/Nb co–doping on the structural and thermoelectric properties of Sr1−xDyxTi1−yNbyO3−δ (0 ≤ x, y ≤ 0.10) are systematically investigated. Single–doped Sr0.95Dy0.05TiO3−δ and SrTi0.95Nb0.05O3−δ consist of tetragonal (I4/mcm space group) and cubic (Pm3¯m space group) perovskite phases. On the other hand, Dy/Nb co–doped SrTiO3, Sr1−xDyxTi1−yNbyO3−δ, has a tetragonal perovskite phase (I4/mcm space group) since the Dy/Nb co–doping induces a distortion of the TiO6 octahedra and lowers the crystal symmetry. The co–doping effectively increases the electrical conductivity and reduces the thermal conductivity, thus noticeably enhancing the dimensionless figure–of–merit (ZT). The highest ZT value (0.24) is achieved for Sr0.95Dy0.05Ti0.95Nb0.05O3−δ at 600 °C. This ZT value is 41 % and 50 % larger than those of single–doped Sr0.95Dy0.05TiO3−δ (0.17) and SrTi0.95Nb0.05O3−δ (0.16), respectively, at 600 °C.

Surface Reaction Induced Compressive Strain for Stable Inorganic Perovskite Solar Cells.

Cesium-based inorganic perovskites have emerged as promising light-harvesting materials for perovskite solar cells (PSCs) due to their promising thermal- and photo-stability. However, obstacles to commercialization remain regarding their phase instability. In this work, we report a facile and effective strategy to regulate the surface compressive strain via in-situ surface reaction to stabilize CsPbI3 perovskite. The use of a chelating ligand with a molecular configuration closely matching the integer multiples of the unit cell lattice parameters of CsPbI3 induces compressive strain at the surface of CsPbI3. The chemical bonding and strain modulation synergistically not only passivate film defects, but also inhibit perovskite phase degradation, thus significantly improving the intrinsic stability of inorganic perovskite. Consequently, enhanced power conversion efficiency (PCE) of 21.0% and 18.6% were respectively achieved in 0.16-cm2 lab-scale devices and 25.3-cm2 solar modules. Further, surface reaction enables PSCs with enhanced thermal and operational stability; these devices retain over 95% of their initial PCE after damp-heat tests (i.e., in 85 ℃ and 85% R.H. air) for 2000 h, and remain 99% of their initial PCE after operating for 2000 h, representing one of the most stable inorganic PSCs reported so far.

Ultralow thermal conductivity of 2D Dion-Jacobson (PDA)(FA)n - 1PbnI3n + 1 perovskite films.

Two-dimensional (2D) perovskites exhibit enhanced thermal stability compared to three-dimensional perovskites, especially the emerging 2D Dion-Jacobson (DJ) phase perovskite. However, the heat transfer mechanisms in DJ phase perovskites are rarely reported. Herein, we determine thermal conductivities of (PDA)(FA)n - 1PbnI3n + 1 films with n = 1-6 by time-domain thermoreflectance. The measured results indicate that the thermal conductivities of these films are extremely low, showing a trend from decline to rise with increasing n values, and reaching to the lowest when n = 2. We measure the propagation of acoustic phonons in films with n = 1-3 by time-domain Brillouin scattering and find phonon velocity plays a key role in the thermal conductivity, which can be explained by the mismatch of spring constants between the inorganic layer and the organic layer using the bead-spring model. The gradually increasing thermal conductivity for larger n values is attributed to the gradual transformation of the grain orientation from horizontal to vertical, which is demonstrated by the grazing-incidence wide-angle x ray scattering (GIWAXS) results. Our work deepens the understanding of the thermal transport process in 2D DJ phase perovskite films and provides insights into thermal management solutions for their devices.

Ionic radius effect on structural and electrical properties of barium strontium titanate thin films

The effect of ion radius on the structural and electrical properties of the perovskite oxide Ba1-x SrxTiO3 thin film is investigated in this work. X-ray diffraction analysis confirmed the formation of phase perovskite structures. Investigations of ceramic microstructures and mechanical properties showed their dependence on the value of ratio x. X-ray diffraction (XRD) and Field emission scanning electron microscopy (FESEM) are used to study the crystallographic aspects of the materials. The XRD pattern changed from tetragonal to cubic as x rose. FESEM images revealed the particle size varied with the values of x increased. The results show that as the ion radius varies, the crystal structure undergoes distortions, affecting the symmetry and stability of the BaSrTiO3 thin films. Electrical properties change depending on the change in particle size.

Enhanced Electrochemical Performance of Double Perovskites as Cathodes in Reversible Ceramic Electrochemical Cells through Nb Doping

Efficient and cost-effective generation of electricity and hydrogen holds promise through reversible protonic ceramic electrochemical cells (R-PCECs). However, the successful commercialization of R-PCECs depends on the advancement of air electrodes that are both highly active and durable. Here, we made an air electrode material with two phases of double perovskite and single perovskite by doping Nb into B-site of the traditional PrBaCo2O6 double perovskite. The coexistence of the mixed double perovskite and single perovskite phases demonstrates superior electrochemical performance and durability compared to pristine double perovskite and single perovskite materials when employed as cathode materials. X-ray photoelectron spectroscopy (XPS), synchrotron radiation X-ray absorption spectroscopy (XAS) and neutron diffraction analysis reveal that this enhancement is primarily attributed to the introduction of high-valence Nb5+, resulting in an increased number of oxygen vacancies and structural stability. The findings presented in this study contribute valuable insights into the design and development of advanced cathode materials for solid oxide fuel cells and electrolyzers, with the potential for applications in sustainable energy conversion and storage technologies.

Influence of CoFe2O4 content on the multifunctional properties of BiFeO3–CoFe2O4 core-shell nanocomposites

The utilization of magnetoelectric composites, particularly core-shell configurations, enhances their versatile applications in various sectors such as medicine and data storage. Among these composites, the perovskite-spinel combination is distinguished by its significant potential. A series of (1-x) BiFeO3-(x) CoFe2O4 (where x = 0.0, 0.2, 0.5, and 1.0) nano core-shell structures were synthesized using a sol-gel auto-combustion method to explore their multifunctional capabilities. Structural analyses identified peaks corresponding to both perovskite and spinel phases. Field Emission Scanning Electron Microscopy revealed a reduction in average particle size with an increase in CoFe2O4 content.The particle size in the BFO80-CFO20 sample has been reduced from 243 nm to 34 nm. Additionally, Transmission Electron Microscopy images of the BFO80-CFO20 sample highlighted the evolution of core-shell structures. Our findings indicate that higher CFO concentrations significantly affect the dielectric, ferroelectric, and optical properties. The bandgaps of the nanocomposites BFO80-CFO20 and BFO50-CFO50 were estimated to be 1.43 eV and 1.39 eV, respectively. Magnetic analysis showed increases in both saturation magnetization and remanent magnetization with increased CFO content, while the coercive field followed a different trend. The saturation magnetization values for the samples BFO, BFO80-CFO20, BFO50-CFO50, and CFO were calculated as 0.205, 14.612, 28.374, and 74.105 (emugr), respectively. The measured values for the same samples were 0.08, 5.07, 11.34, and 34.01 (emugr), respectively. Further, the electrochemical properties were thoroughly investigated using cyclic voltammetry, linear sweep voltammetry, and electrochemical impedance spectroscopy.

From Chalcogen Bonding to S-π Interactions in Hybrid Perovskite Photovoltaics.

The stability of hybrid organic-inorganic halide perovskite semiconductors remains a significant obstacle to their application in photovoltaics. To this end, the use of low-dimensional (LD) perovskites, which incorporate hydrophobic organic moieties, provides an effective strategy to improve their stability, yet often at the expense of their performance. To address this limitation, supramolecular engineering of noncovalent interactions between organic and inorganic components has shown potential by relying on hydrogen bonding and conventional van der Waals interactions. Here, the capacity to access novel LDperovskite structures that uniquely assemble through unorthodox S-mediated interactions is explored by incorporating benzothiadiazole-based moieties. The formation of S-mediated LD structures is demonstrated, including one-dimensional (1D) and layered two-dimensional (2D) perovskite phases assembled via chalcogen bonding and S-π interactions. This involved a combination of techniques, such as single crystal and thin film X-ray diffraction, as well as solid-state NMR spectroscopy, complemented by molecular dynamics simulations, density functional theory calculations, and optoelectronic characterization, revealing superior conductivities of S-mediated LD perovskites. The resulting materials are applied in n-i-p and p-i-n perovskite solar cells, demonstrating enhancements in performance and operational stability that reveal a versatile supramolecular strategy in photovoltaics.

Phase equilibria in the low-TiO2 part of the CaO–MgO–SiO2–Al2O3–TiO2 system at a fixed MgO/CaO mass ratio of 0.2 and Al2O3/SiO2 mass ratio of 0.4

Adding titanium oxide has become a common practice in modern blast furnace operating procedures. The blast furnace slag is based on the CaO–MgO–Al2O3–SiO2–TiO2 low titanium slag system rather than CaO–MgO–Al2O3–SiO2 system. Phase equilibria in the CaO–SiO2–Al2O3–MgO–TiO2 system in the low-TiO2 part have been experimentally determined by means of high temperature equilibration and quenching technique followed by electron probe X-ray microanalysis. Introducing a small quantity of titanium-bearing materials can lower the liquidus temperature. The TiO2 content in the slag should be controlled below 4.6 wt%, otherwise it will enter the perovskite phase region where the liquidus temperatures increases rapidly. The compositions of the solid solutions corresponding to the liquidus have been precisely measured and should be utilized for developing the thermodynamic database.

High-temperature relaxation and microwave dielectric response of (1-x)BaNd1.76Bi0.24Ti5O14-xBa0.6Sr0.4La4Ti4O15 compounds with adjustable medium-high dielectric constant

Dielectric ceramics in the microwave band are one of the crucial materials for mobile communication technology, and the studying of their phase evolution and defect behavior can help to understand and reduce dielectric loss. In this work, (1-x)BaNd1.76Bi0.24Ti5O14-xBa0.6Sr0.4La4Ti4O15 (x = 0.2, 0.4, 0.6 and 0.8, (1-x)BNT-xBSLT) ceramics were synthesized by solid-state reaction method. X-ray diffraction (XRD) and Raman spectra analysis reveal that tungsten bronze and hexagonal perovskite phases coexist in the ceramics, and BaNd2Ti3O10 is indexed as the main crystalline phase at x = 0.4, 0.6, leading to a deterioration of the microwave dielectric properties. The defect-related relaxation behavior and its effect on microwave dielectric properties were analyzed by dielectric temperature spectrum and thermally stimulated depolarization current (TSDC). The relationship between the dielectric constant and the electric field distribution was solved using the eigenmode of the high frequency structure simulator. In short, the (1-x)BNT-xBSLT ceramics at x = 0.8 exhibit excellent microwave dielectric properties: εr = 47.2, Q×f = 16,800 GHz, and τf = −4.6 ppm/°C. The microwave dielectric response of BNT-BSLT composite ceramics is closely related to the phase composition and defects, which is informative for the development of low dielectric loss ceramics.

Controlled solid‐state Phase Transition of Formamidinium Dominated Perovskite Layers Fabricated Through Magnetron Sputtering for Photovoltaics

AbstractPerovskite solar cells (PSCs) based on formamidinium lead iodide (FAPbI3) have demonstrated the highest power conversion efficiencies. Typically fabricated through solution‐processing, FAPbI3 films necessitate intricate crystallization control to avoid the formation of a more stable non‐perovskite phase. Magnetron sputtering, an effective solvent‐free technique, has gained attention for producing large‐area perovskite films. Here, a novel approach to create high‐quality FAPbI3‐based perovskite thin films by employing magnetron sputtering is presented. Specifically, a mechanosynthesized blend of (FA1‐xMAx)Pb(I1‐xBrx)3 (MA = methylammonium) is used as a single‐source target for sputtering, and a post‐annealing transforms various phases in the initial deposited film into coherent FAPbI3‐based films with an ultra‐long and controlled crystallization process. Despite minimal residual MABr after post‐annealing, its presence is crucial in the formation of perovskite film, as evidenced by a distinct solid‐state phase transformation process is presented. A comprehensive investigation of the films' structural, compositional, and optical properties, with respect to varying MABr doping ratios, reveals details of perovskite phase development and the pivotal influence of MABr. PSCs fabricated with the optimized films display a substantial increase in the power conversion efficiency, reaching 20.1%. These results underscore the potential of combining magnetron sputtering and post‐annealing in the scalable production of high‐efficiency PSCs.

Enhancing the Phase Crystallinity of Buried Layer Perovskites through Organic Salt Molecule‐Assisted Crystal Growth

The performance and stability of perovskite solar cells rely crucially on the purity of their active perovskite phase. While the two‐step method has emerged as a well‐known technique for fabricating high‐performance cells, it suffers from significant PbI2 phase impurities at the buried layer due to inefficient diffusion of cationic molecules into the preprepared PbI2 layer. Herein, a simple yet highly effective method is presented to boost phase purity within the buried layer by introducing formamidinium iodide (FAI) seed molecules into the underlying PbI2 layer. X‐Ray diffraction analysis result reveals that this process significantly reduces the PbI2 phase and enhances the purity of the perovskite's phase. It is also observed that this technique can produce perovskite layer with a remarkably smooth surface structure and large interconnected crystal grains, forming a continuous layer. These characteristics are subjected to further enhancement when hexamethylenetetramine molecules are concurrently introduced with FAI into the PbI2 layer. Solar cells fabricated using this method, with an active area of 0.1 cm2, achieve a remarkable power conversion efficiency of up to 24.52% with Voc as high as 1.18 V, representing a substantial improvement over cells produced using the standard two‐step method, which attains only 22.18% efficiency. With its simple yet impactful approach, the present method should find widespread adoption in the production of high‐performance perovskite solar cells.

Enhanced dielectric response and non-Ohmic properties of Cd-doped Na1/3Ca1/3Bi1/3Cu3Ti4O12 ceramics

In this study, Na1/3(Ca1−xCdx)1/3Bi1/3Cu3Ti4O12 (x = 0, 0.2, 0.4, 0.8, and 1.0) ceramics were prepared via solid-state method. Effects of substitution of Ca2+ with Cd2+ on the microstructure, dielectric response, and non-Ohmic properties of Na1/3Ca1/3Bi1/3Cu3Ti4O12 ceramics were studied systematically. Results showed that all samples possessed single perovskite phase, in which grain size increased with the increase in Cd2+ doping content. Energy band gaps and activation energy first increased and then decreased, achieving their maxima (4.22 and 0.642 eV, respectively) at x = 0.2. Besides, dielectric constant of doped samples increased with the decrease in dielectric loss in frequency range of 40–106 Hz. Moreover, improvement in non-Ohmic properties was also observed with Cd2+ doping. The optimal dielectric properties (dielectric constant of ∼12,500, dielectric loss of ∼0.032 at 10 kHz, nonlinear coefficient of ∼3.42, and breakdown strength of ∼2.7 kV·cm−1) were achieved at x = 0.2. Dielectric response mechanism of ceramics followed internal barrier layer capacitor model while nonlinear ohmic properties were derived from Schottky barrier structure. Dielectric relaxation peaks at high temperatures (120 °C–220 °C) were associated with grain boundaries. Therefore, partial substitution of Ca2+ with Cd2+ can improve simultaneously dielectric and non-Ohmic properties of Na1/3Ca1/3Bi1/3Cu3Ti4O12 ceramics, which is conducive to their application in high-energy-density storage capacitors and varistors.

Thermally and Mechanically Stable Perovskite Artificial Synapse as Tuned by Phase Engineering for Efferent Neuromuscular Control.

The doping of perovskites with mixed cations and mixed halides is an effective strategy to optimize phase stability. In this study, we introduce a cubic black phase perovskite CsyFA(1-y)Pb(BrxI(1-x))3 artificial synapse, using phase engineering by adjusting the cesium-bromide content. Low-bromine mixed perovskites are suitable to improve the electric pulse excitation sensitivity and stability of the device. Specifically, the low-bromine and low-cesium mixed perovskite (x = 0.15, y = 0.22) annealed at 373 K allows the device to maintain logic response even after 1000 mechanical flex/flat cycles. The device also shows good thermal stability up to temperatures of 333 K. We have demonstrated reflex-arc behavior with MCMHP synaptic units, capable of making sensory warnings at high frequency. This compositionally engineered, dual-mixed perovskite synaptic device provides significant potential for perceptual soft neurorobotic systems and prostheses.

Synthesized Cs-rich Cs0.7FA0.3PbI2Br perovskite film by two-dimensional to three-dimensional phase transition

Stability of perovskite is the main limitation of the commercialization of perovskite solar cells. Recent studies have shown that FA-Cs perovskites are expected to achieve ideal crystal structures with outstanding stability when FA content is 30 %. And its bandgap can be adjusted to 1.8 eV, making it suitable for a top battery in the tandem cell. However, when the content of Cs ions in the component exceeds 30 %, phase separation occurs. In this study, a Cs-rich Cs0.7FA0.3PbI2Br perovskite film was synthesized by using a 2D to 3D phase transition method. Through the high orientation of the 2D CsPbI3-FAI alloy-like phase and the anisotropic volatilization of FA, a well-oriented α-Cs0.7FA0.3PbI2Br perovskite phase is obtained. The α-Cs0.7FA0.3PbI2Br shows excellent thermal and UV stability and improved humidity stability. Meanwhile, the fabricated Cs0.7FA0.3PbI2Br perovskite solar cell achieved a competitive power conversion efficiency of 14.87 % successfully breaking the world record for this perovskite system. This further advances the research progress of Cs-rich perovskites in highly efficient and stable solar cells.

High-n Phase Suppression for Efficient and Stable Blue Perovskite Light-Emitting Diodes.

Quasi-2D perovskites light-emitting diodes (PeLEDs) have achieved significant progress due to their superior optical and electronic properties. However, the blue PeLEDs still exist inefficient energy transfer and electroluminescence performance caused by mixed multidimensional phase distribution. In this work, transition metal salt (zinc bromide, ZnBr2) is introduced to modulate phase distributions by suppressing the nucleation of high n phase perovskites, which effectively shortens the energy transfer path for blue emission. Moreover, ZnBr2 also facilitates energy level matching and reduces non-radiative recombination, thus improving electroluminescence (EL) efficiency. Benefiting from these combined improvements, an efficient blue PeLEDs is obtained with a maximum external quantum efficiency (EQE) of 16.2% peaking located at 486nm. This work provides a promising approach to tune phase distribution of quasi-2D perovskites and achieving highly efficient blue PeLEDs.

Lanthanum‐Nickel‐Based Mixed‐Oxide‐Coated Nickel Electrodes for the OER Electrocatalysis

ABSTRACTThe anodic oxygen evolution reaction (OER) remains a bottleneck for electrocatalytic water splitting due to its sluggish kinetics and, thus, high overpotentials. This limits water electrolysis as a key technology for the generation of hydrogen as a sustainable alternative to fossil fuels. For alkaline water splitting, perovskite phases (ABO3) with earth‐abundant first‐row transition‐metals have emerged as a promising material class for OER electrocatalysts. Among these, LaNiO3 has been found to exhibit high intrinsic OER activity. To increase catalyst utilization, a high surface area of the catalyst is desirable and can be achieved by impregnation of porous templates. In this work, La–Ni‐based oxides were prepared via impregnation of activated carbon and subsequent heating, combining precursor calcination and template removal into one step. The phase structure of the samples is analyzed via powder X‐ray diffractometry, and the morphology is determined by scanning electron microscopy. The synergistic effect of B‐site mixing iron as well as A‐site mixing strontium into LaNiO3 is studied and found to increase its OER activity, confirming the activity‐enhancing effect of Fe in Ni‐based OER electrocatalysts. To allow for facile technical application of the catalysts, the electrodes are prepared by coating a perovskite ink onto Ni‐metal as industrially relevant substrates, followed by calcination.