Search Results (259)

Recently, we have described SrMo_1-xMg_xO_3-δ perovskites (x = 0.1, 0.2) as excellent anode materials for solid oxide fuel cells (SOFCs), with mixed ionic and electronic conduction (MIEC) properties. After depositing on the solid electrolyte, they were annealed for sintering at high temperatures (typically 1000 °C), giving rise to oxidized scheelite-type phases, with SrMo_1-xMg_xO_4-δ (x = 0.1, 0.2) stoichiometry. To obtain the active perovskite phases, they were reduced again in the working anode conditions, under H₂ atmosphere. Therefore, there must be an excellent reversibility between the oxidized Sr(Mo, Mg)O_4-δ scheelite and the reduced Sr(Mo, Mg)O_3-δ perovskite phases. This work describes the topotactical oxidation, by annealing at 400 °C in air, of the SrMo_0.9Mg_0.1O_3-δ perovskite oxide. The characterization by X-ray diffraction (XRD) and neutron powder diffraction (NPD) was carried out in order to determine the crystal structure features. The scheelite oxides are tetragonal, space group I4₁/a (No. 88), whereas the perovskites are cubic, s.g. Pm-3m (No. 221). The Rietveld refinement of the scheelite phase from NPD data after annealing the perovskite at 400 °C and cooling it down slowly to RT evidences the absence of intermediate phases between perovskite and scheelite oxides, as well as the presence of oxygen vacancies in both oxidized and reduced phases, essential for their performance as MIEC oxides. The topotactical relationship between both crystal structures is discussed. Full article

Poly[bis(4-phenyl) (2,5,6-trimethylphenyl) amine (PTAA), as a hole transfer material, has been widely used in perovskite solar cells (PSCs). However, the optimal solvent for preparing the PTAA solution and coating the PTAA layer is still uncertain. In this work, we investigated three types of organic solvents (toluene, chlorobenzene and dichlorobenzene) for processing PTAA layers as the hole transport layer in PSCs. Based on the experimental verification and molecular dynamics simulation results, all the evidence indicated that toluene performs best among the three candidates. This is attributed to the significant polarity difference between toluene and PTAA, which leads to the formation of a uniform surface morphology characterized by granular protuberances after spin coating. The contact area of the hole transfer layer with the surface aggregation is increased in reference to the rough surface, and the hydrophilicity of the PTAA layer is also increased. The improvement of these two aspects are conducive to the effective interfacial charge transfer. This leads to the generation of more photocurrent. The PSCs employing toluene-processed PTAA exhibit an average power conversion efficiency (PCE) of 19.1%, which is higher than that of PSCs using chlorobenzene- and dichlorobenzene-processed PTAA (17.3–17.9%). This work provides a direct optimization strategy for researchers aiming to fabricate PSCs based on PTAA as a hole transport layer and lays a solid foundation for the development of high-efficiency inverted PSCs. Full article

Two−dimensional halide perovskites have emerged as promising optoelectronic materials, yet the uncontrolled defect formation during synthesis remains a critical challenge for their practical applications. In this work, we systematically investigate the structural, electronic, and optical properties of monolayer CsPb₂Br₅ in two representative configurations: ds−CsPb₂Br₅ and ss−CsPb₂Br₅. By introducing four types of vacancy defects—V_Br−c, V_Br−b, V_Cs, and V_Pb, we analyze their structural distortions, formation energies, and their impact on band structure and optical response using first−principles calculations. Our results reveal that Br−related vacancies are energetically most favorable and induce shallow defect levels and absorption edge redshifts in the ds−CsPb₂Br₅ structure, while in the ss−CsPb₂Br₅ configuration, only V_Br−b forms a defect state. V_Pb and V_Cs lead to significant sub−bandgap absorption enhancement and dielectric response due to band−edge reorganization, despite not introducing in−gap states. Notably, V_Br−c exhibits distinct infrared absorption in the ss−CsPb₂Br₅ model without electronic trap formation. These findings underscore the critical influence of defect type and slab asymmetry on the optoelectronic behavior of CsPb₂Br₅, providing guidance for defect engineering in perovskite−based optoelectronic applications. Full article

In this study, we report the synthesis and characterization of hybrid heterostructures composed of red carbon, an organic semiconductor polymer, and the perovskite (NH₄)₃ZnCl₅. Red carbon was synthesized via the polymerization of carbon suboxide (C₃O₂), exhibiting strong light absorption and distinctive optical properties. The hybrid material was obtained by crystallizing (NH₄)₃ZnCl₅ in the presence of red carbon, leading to significant modifications in the optical characteristics of the perovskite. Comprehensive analyses, including X-ray diffraction, FTIR spectroscopy, UV-vis spectroscopy, and cyclic voltammetry, confirmed the formation of a type I heterostructure with enhanced luminescence and potential for advanced optical applications. The energy band alignment suggests that red carbon can function effectively as both a hole and electron transport medium. This work underscores the potential of (NH₄)₃ZnCl₅@red carbon hybrid heterostructures in the development of next-generation optoelectronic devices, including sensors and LEDs. Full article

Single-phase white-light-emitting materials, particularly 2D hybrid organic–inorganic halide perovskites, have garnered significant attention due to their strong electron–phonon interactions, which lead to broad luminescence and a notable Stokes shift resulting from self-trapped exciton recombination. However, 2D lead iodide perovskites typically display these characteristics poorly, restricting their efficiency as white-light emitters. This study presents a 2D lead iodide perovskite that incorporates a fluorinated π-conjugated aggregation-induced enhanced emission luminophore, FPCSA, as a bulky organic cation to create a quasi-2D perovskite. The FPCSA cation establishes a Type II energy level alignment with the lead iodide layer in the 2D perovskite, and a significant energy offset effectively suppresses charge transfer, enabling independent emission from both the organic and inorganic layers while facilitating self-trapped exciton formation. Under 315 nm UV excitation, this material demonstrates warm white-light emission with RGB triple-band photoluminescence stemming from the electronically decoupled FPCSA and perovskite layers. These findings provide a promising new method for designing efficient single-phase white-light-emitting materials for optoelectronic applications. Full article

Various types of strain, as well as chemical pressure induced by dopants, can effectively tailor the performance of perovskite thin films, including their optical, electrical or photoelectrochemical properties. The control of these functional properties through such engineering techniques is key to fulfilling the application-specific requirements of ferroelectric devices in various fields. Numerous models and experimental data have been published on this subject, especially on ferrite-based ferroelectric materials. Within this paper, the mechanisms of tuning ferroelectric intrinsic properties, such as polarization and ferroelectric domain configurations, through epitaxial strain and doping, as well as the role of these techniques in influencing functional properties such as dielectric and photoelectrochemical ones, are presented. This review examines the significant improvements in dielectric properties and photoelectrochemical efficiency achieved by the strategical control of key functionalities including dielectric losses, domain structures, charge separation and surface reactions in strained/doped ferroelectric thin films, highlighting the advancements and research progress made in this field in recent years. Full article

This study focuses on enhancing the photoelectrocatalytic (PEC) performance of LaFeO₃ photocathodes by incorporating Ag nanocrystals. LaFeO₃, a perovskite-type metal oxide semiconductor, has potential in PEC water splitting but suffers from fast charge carrier recombination. Ag nanoparticles are introduced due to their surface plasmon resonance (SPR) property and ability to form Schottky junctions with LaFeO₃. A series of Ag/LaFeO₃ materials are prepared using the molten salt method for LaFeO₃ synthesis and the direct reduction method for Ag loading. The results show that Ag nanoparticles are uniformly dispersed on LaFeO₃. The 3 mol% Ag/LaFeO₃ photocathode demonstrates a remarkable ninefold increase in photocurrent density (15 mA·cm⁻² at −0.2 V vs. RHE) compared to pure LaFeO₃ (1.7 mA·cm⁻²). The band gap of LaFeO₃ is reduced from 2.07 eV to 1.92 eV with 3 mol% Ag loading, and the charge transfer impedance is reduced by 77%, while the carrier concentration increases by 2.3 times. The novelty of this work lies in the comprehensive investigation of the interaction mechanisms between Ag nanoparticles and LaFeO₃, which lead to enhanced light absorption, improved charge separation, and increased electrochemical activity. The optimized Ag loading not only improves the photocatalytic efficiency but also enhances the stability of the photocathode. This work provides valuable insights into the interaction between Ag and LaFeO₃, and offers experimental and theoretical support for developing efficient photocatalytic materials for PEC water splitting. Full article

In this work, we report the synthesis of perovskite-type Ba-doped LaFeO₃ (La_1−xBa_xFeO₃, x = 0.00, 0.02, 0.04, and 0.06) nanofibers (NFs) using the electrospinning method. The synthesized La_1−xBa_xFeO₃ materials have a fibrous structure with an average fiber diameter of 250 nm. The fibers, in turn, consist of smaller crystalline particles of 20–50 nm in size. The sensor properties of La_1−xBa_xFeO₃ nanofibers were studied when detecting 20 ppm CO, CH₄, methanol, and acetone in dry air in the temperature range of 50–350 °C. Doping with barium leads to a significant increase in sensor response and a decrease in operating temperature when detecting volatile organic compounds (VOCs). The process of acetone oxidation on the surface of the most sensitive La_0.98Ba_0.02FeO₃ material was studied using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temperature-programmed desorption in combination with mass spectrometry (TPD-MS). A mechanism for the sensor signal formation is proposed. Full article

Among hole transport materials (HTMs), 2,2′,7,7′-Tetrakis(N,N-di-p-methoxyphenylamino)-9,9′-spirobifluorene (spiro-OMeTAD) is the most frequently adopted, due to its suitable energy band level in conventional-type perovskite solar cells (PSCs). However, the high price of spiro-OMeTAD is an obstacle faced in its research and commercialization. In our previous work, we introduced a low-cost HTM, (E,E,E,E)-4,4′,4″,4‴-[Benzene-1,2,4,5-tetrayltetrakis(ethene-2,1-diyl)]tetrakis[N,N-bis(4-methoxyphenyl)aniline] (α2); however, it was immiscible in the conventional solvent chlorobenzene, leading to the adoption of dichloromethane (DCM) as an alternative. Nevertheless, its high vapor pressure led to poor reproducibility, limiting its practical applicability. To address this issue, we investigated alternative solvents to DCM to facilitate the application of α2 to dichloride alkane materials, from 1,2-dichloroethane (DCE) to 1,4-dichlorobutane. In these materials, DCE exhibits the most superior properties in terms of layer formation control, due to its vapor pressure in spin-coating. Accordingly, a PSC containing α2-DCE HTL showed high performance, with 1.15V of open-circuit voltage and a 22.7% power conversion efficiency. Full article

As one of the representative transparent conducting oxides, perovskite-typed La-doped BaSnO₃ (LBSO) films could be integrated with other perovskite materials to create all-perovskite oxide devices exhibiting exotic physical properties. To overcome the intricate trade-off between conductivity and transmittance in LBSO-based devices, understanding the structural modulating mechanisms of transmittance is definitely crucial. In this paper, the influences of the prevailing Ruddlesden–Popper faults (RP faults) on the transmittance of LBSO films were systematically illuminated, whose density were regulated by the oxygen partial pressures during film growth. High-angle annular dark field (HAADF) STEM and X-ray diffraction (XRD) were employed to characterize the microstructures of the films growing under various oxygen partial pressures and annealing under different oxygen partial pressures. A decrease in RP fault density was observed in the films grown and annealed at high oxygen partial pressures, which displayed improved visible light transmittance. Atomic-scale energy-dispersive spectroscopy (EDS) and electron energy-loss spectroscopy (EELS) analyses revealed the different electronic structure at RP faults compared with the bulk material, including the double concentration of La and increased M5/M4 white line ratio, which is modulative by the oxygen deficiency in LBSO film. It is revealed that the RP defaults in LBSO films annealed at low oxygen pressures displayed larger changes in electronic structure compared with the counterparts with low oxygen deficiency. This work suggests that the oxygen deficiency in LSBO films plays a crucial role in changing the density of RP faults and their electronic structures, thereby regulating the transmittance of LBSO films, which would provide guidance for fabricating high-performance LBSO films. Full article

Hybrid organic–inorganic perovskites have emerged as promising materials for next-generation optoelectronic devices owing to their tunable properties and low-cost fabrication. We report the synthesis of 3D hybrid perovskites with monoethanolammonium cations. Specifically, we investigated the optoelectronic properties and morphological characteristics of polycrystalline films of hybrid perovskites MA_xMEA_1−xPbI₃, which contain methylammonium (MA) and monoethanolammonium (MEA) cations. MA_xMEA_1−xPbI₃ crystallizes in a tetragonal perovskite structure. The substitution of methylammonium cations with monoethanolammonium ions led to an increase in the lattice parameters and the bandgap energy. Energy level diagrams of the synthesized samples were also constructed. The bandgap of MA_0.5MEA_0.5PbI₃ makes it a promising material for use in tandem solar cells. These polycrystalline films, namely MA_0.5MEA_0.5PbI₃ and MA_0.25MEA_0.75PbI₃ were fabricated using a one-step spin-coating method without an antisolvent. These films exhibit a uniform surface morphology under the specified deposition parameters. Within the scope of this study, no evidence of dendritic structures or pinhole-type defects were observed. All synthesized samples demonstrated photocurrent generation under visible light illumination. Moreover, using monoethanolammonium cations reduced the hysteresis of the I–V characteristics, indicating improved device stability. Full article

Perovskite-type materials containing Bi³⁺ cations at A sites are interesting from the viewpoints of applications and fundamental science as the lone pair of Bi³⁺ cations often stabilizes polar, ferroelectric structures. This can be illustrated by a lot of discoveries of different new functionalities in bulk and thin films of BiFeO₃ and its derivatives. In this work, we investigated solid solutions of BiCr_1−xFe_xO₃ with 0.1 ≤ x ≤ 0.4 prepared by a high-pressure (HP) method and post-synthesis annealing at ambient pressure (AP). HP-BiCr_1−xFe_xO₃ modifications with 0.1 ≤ x ≤ 0.3 were mixtures of two phases with space groups C2/c and Pbam, and the amount of the C2/c phase decreased with increasing x. The amount of the C2/c phase was also significantly decreased in AP-BiCr_1−xFe_xO₃ modifications, and the C2/c phase almost disappeared in AP-BiCr_1−xFe_xO₃ with 0.2 ≤ x ≤ 0.3. Fundamental, strong reflections of HP-BiCr_1−xFe_xO₃ and AP-BiCr_1−xFe_xO₃ were almost unchanged; on the other hand, weak superstructure reflections were different and showed clear signs of strong anisotropic broadening and incommensurate positions. These structural features prevented us from determining their room-temperature structures. On the other hand, HP-BiCr_1−xFe_xO₃ and AP-BiCr_1−xFe_xO₃ showed high-temperature structural phase transitions to the GdFeO₃-type Pnma modification at T_srt = 450 K (x = 0.1), T_srt = 480 K (x = 0.2), T_srt = 510 K (x = 0.3), and T_srt = 546 K (x = 0.4). Crystal structures of the GdFeO₃-type Pnma modifications of all the samples were investigated by synchrotron powder X-ray diffraction. Magnetic properties of HP-BiCr_1−xFe_xO₃ and AP-BiCr_1−xFe_xO₃ were quite close to each other (HP vs. AP), and the x = 0.2 samples demonstrated negative magnetization phenomena without signs of the exchange bias effect. Full article

Molecular design strategies such as noncovalent conformational locks, self-assembly, and D-A molecular skeletons have been extensively used to devise efficient and stable hole transport materials. Nevertheless, most of the existing excellent examples involve only single or dual strategies, and triple strategies remain scarcely reported. Herein, we attempt to develop two quinoxaline-based hole transport materials (DQC-T and DQ-T-QD) through a triple strategy encompassing an S···N noncovalent conformational lock, D-A molecular skeletons, and self-assembly or conjugate engineering. The S···N noncovalent conformational lock formed by thiophene sulfur atoms and quinoxaline nitrogen atoms improves molecular planarity, further inducing the formation of high-quality perovskite films and enhancing hole transport ability; the asymmetric D-A molecular backbone endows the material with a larger dipole moment (μ = 5.80 D) to promote intramolecular charge transfer; and the carboxyl group, methoxy, and sulfur atom establish strong interactions between the NiO_x and perovskite layers, including self-assembly and defect passivation, which mitigates the occurrence of detrimental interfacial charge recombination and reactions. Thus, the 2-thiophenecarboxylic acid derivative DQC-T, featuring an asymmetric D-A molecular backbone, exhibits superiority in terms of good interface contact, hole extraction, and transport compared to DQ-T-QD with a D-A-π-A-D type structure. Naturally, the optimal power conversion efficiency of NiO_x/DQC-T-based p-i-n flexible perovskite solar cells is 18.12%, surpassing that of NiO_x/DQ-T-QD-based devices (16.67%) and NiO_x-based devices with or without DQC (a benzoic acid derivative without a noncovalent conformational lock) as co-HTMs (16.75% or 15.52%). Our results reflect the structure–performance relationship well, and provide a referable triple strategy for the design of new hole transport materials. Full article

The chemical looping reforming of methane using an SrFeO₃ oxygen carrier to produce synthesis gas from solar energy was experimentally investigated and validated. High-temperature solar heat was used to provide the reaction enthalpy, and therefore the methane feedstock was entirely dedicated to producing syngas. The two-step isothermal process encompassed partial perovskite reduction with methane (partial oxidation of CH₄) and exothermic oxidation of SrFeO_3-δ with CO₂ or H₂O splitting under the same operating temperature. The oxygen carrier material was shaped in the form of a reticulated porous foam structure for enhancing heat and mass transfer, and it was cycled in a solar-heated tubular reactor under different operating parameters (temperature: 950–1050 °C, methane mole fraction: 5–30%, and type of oxidant gas: H₂O vs. CO₂). This study aimed to assess the fuel production capacity of the two-step process and to demonstrate the potential of using strontium ferrite perovskite during solar cycling for the first time. The maximum H₂ and CO production rates during CH₄-induced reduction were 70 and 25 mL/min at 1000 °C and 15% CH₄ mole fraction. The increase in both the cycle temperature and the methane mole fraction promoted the reduction step, thereby enhancing syngas yields up to 569 mL/g during reduction at 1000 °C under 30% CH₄ (778 mL/g including both cycle steps), and thus outperforming the performance of the benchmark ceria material. In contrast, the oxidation step was not significantly affected by the experimental conditions and the material’s redox performance was weakly dependent on the nature of the oxidizing gas. The syngas yield remained above 200 mL/g during the oxidation step either with H₂O or CO₂. Twelve successive redox cycles with stable patterns in the syngas production yields validated material stability. Combining concentrated solar energy and chemical looping reforming was shown to be a promising and sustainable pathway toward carbon-neutral solar fuels. Full article

The most commonly used optical oxygen sensing materials are phosphorescent molecules and functionalized nanocrystals. Many exploration studies on oxygen sensing have been carried out using the fluorescence or phosphorescence of semiconductor nanomaterials. Lead halide perovskite nanocrystals, a new type of ionic semiconductor, have excellent optical properties, making them suitable for use in optoelectronic devices. They also show promising applications in analytical sensing and biological imaging, especially manganese-doped perovskite nanocrystals for optical oxygen sensing. As a class of materials with diverse sources, copper iodide cluster semiconductors have rich structural and excellent luminescent properties, and have attracted attention in recent years. These materials have adjustable optical properties and sensitive stimulus response properties, showing great potential for optical sensing applications. This review paper provides a brief introduction to traditional oxygen sensing using organic molecules and introduces research on oxygen sensing using novel luminescent semiconductor materials, perovskite metal halides and copper iodide hybrid materials in recent years. It focuses on the mechanism and application of these materials for oxygen sensing and evaluates the future development direction of these materials for oxygen sensing. Full article