The excellent electro-mechanical properties of perovskite oxide ferroelectrics make these materials major piezoelectrics. Oxygen vacancies are believed to easily form, migrate, and strongly affect ferroelectric behavior and, consequently, the piezoelectric performance of these materials and devices based thereon. Mobile oxygen vacancies were proposed to explain high-temperature chemical reactions half a century ago. Today the chemistry-enabled concept of mobile oxygen vacancies has been extrapolated to arbitrary physical conditions and numerous effects and is widely accepted. Here, this popular concept is questioned. The concept is shown to conflict with our modern physical understanding of ferroelectrics. Basic electronic processes known from mature semiconductor physics are demonstrated to explain the key observations that are groundlessly ascribed to mobile oxygen vacancies. The concept of mobile oxygen vacancies is concluded to be misleading.

• Klíčová slova
• electronic, ferroelectric, oxygen vacancy, perovskite oxide, semiconductor,
• Publikační typ
• časopisecké články MeSH

Using solar energy to catalyse photo-driven processes to address the energy crisis and environmental pollution plays a role in the path to a sustainable society. Many oxide-based materials, especially perovskite oxides, have been widely investigated as catalysts for photocatalysis in energy and environment because of the low-cost and earth-abundant and good performance. At this stage, there is a need to present a scientific-based evaluation of the technologies developed so far and identify the most sustainable technologies and the existing limitations and opportunities for their commercialisation. This work comprehensively investigated the outcomes using various scientometric indices on perovskite oxide-based photo(electro)catalysts for water splitting, nitrogen fixation, carbon dioxide conversion, organic pollutant degradation, current trends and advances in the field. According to the results achieved, efforts in both energy and environment based on perovskite oxides have been initiated in the 1990s and accelerated since the 2010s. China and the United States were identified as the most contributing countries. Based on the results achieved in this study, the main milestones and current trends in the development of this field have been identified. The aim of this research is to provide useful guidelines for the further investigation of perovskite oxide-based catalysts for photoelectrocatalysis and photocatalysis both in energy and environment on the applications such as water splitting, nitrogen fixation, carbon dioxide conversion, and wastewater treatment.

• Klíčová slova
• Carbon dioxide conversion, Nitrogen fixation, Photocatalysis, Photoelectrocatalysis, Pollutant degradation, Water splitting,
• MeSH
• katalýza MeSH
• oxidy * MeSH
• sloučeniny vápníku * MeSH
• titan MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• oxidy * MeSH
• perovskite MeSH Prohlížeč
• sloučeniny vápníku * MeSH
• titan MeSH

Combining the unique properties of peptides as versatile tools for nano- and biotechnology with lead halide perovskite nanoparticles can bring exceptional opportunities for the development of optoelectronics, photonics, and bioelectronics. As a first step towards this challenge sub 10 nm methylammonium lead bromide perovskite colloidal nanoparticles have been synthetizes using commercial cyclic peptide Cyclo(RGDFK), containing 5 amino acids, as a surface stabilizer. Perovskite nanoparticles passivated with Cyclo(RGDFK) possess charge transfer from the perovskite core to the peptide shell, resulting in lower photoluminescence quantum yields, which however opens a path for the application where charge transfer is favorable.

• MeSH
• anorganické látky chemie   MeSH
• cyklické peptidy chemie   MeSH
• luminiscence * MeSH
• nanočástice chemie   MeSH
• olovo chemie   MeSH
• oxidy chemie   MeSH
• polovodiče * MeSH
• sloučeniny vápníku chemie   MeSH
• titan chemie   MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• anorganické látky MeSH
• cyklické peptidy MeSH
• olovo MeSH
• oxidy MeSH
• perovskite MeSH Prohlížeč
• sloučeniny vápníku MeSH
• titan MeSH

The double-perovskite material Cs2TiBr6 shows excellent photovoltaic potential, making it a promising alternative to lead-based materials. However, its high susceptibility to degradation in air has raised concerns about its practical application. This study introduces an interesting synthesis approach that significantly enhances the stability of Cs2TiBr6 powder. We implemented a gradual cation exchange process by substituting Ti4+ with Sn4+ in the efficient microwave-assisted synthesis method, developing a double perovskite Cs2SnxTi1-xBr6 type. A systematic study of increasing concentration of Sn4+ in Cs2TiBr6 perovskite has been performed to analyze the effect of Sn-doping degree on the chemical and thermal stability of the material and the optical features in both nitrogen and ambient atmospheres, significantly increasing the stability of the material in the air for over a week. Furthermore, introducing Sn4+ results in a more uniform polygonal crystal morphology of the powders and a slight band gap broadening. We show that microwave-assisted synthesis is highly efficient and cost-effective in producing more sustainable lead-free perovskite materials with enhanced stability and desirable electrical characteristics. This work suggests a promising method for synthesizing perovskite materials, opening new routes for scientific research and applications.

• Klíčová slova
• Cesium titanium tin bromide perovskite, Lead-free double perovskite, Microwave irradiation synthesis, Outdoor stability,
• Publikační typ
• časopisecké články MeSH

High defect concentrations at the interfaces are the basis of charge extraction losses and instability in perovskite solar cells. Surface engineering with organic cations is a common practice to solve this issue. However, the full implications of the counteranions of these cations for device functioning are often neglected. In this work, we used 4-fluorophenethylammonium cation with varying halide counteranions for the modification of both interfaces in methylammonium-free Pb-based n-i-p devices, observing significant differences among iodide, bromide, and chloride. The cation treatment of the buried and top interfaces resulted in improved surface quality of the perovskite films and largely improved carrier dynamics with reduced nonradiative recombination. Consequently, the optimal interface-modified methylammonium-free perovskite solar cells surpassed 20% efficiency and demonstrated remarkable operational stability. Our findings underscore the potential of comprehensive surface engineering strategies in advancing the perovskite film and device quality, thereby facilitating their broader and more successful applications.

• Klíčová slova
• 2D/3D perovskite, halide segregation, interface modification, perovskite solar cells, perovskite stability,
• Publikační typ
• časopisecké články MeSH

This study points out the importance of the templating effect in hybrid organic-inorganic perovskite semiconductors grown on graphene. By combining two achiral materials, we report the formation of a chiral composite heterostructure with electronic band splitting. The effect is observed through circularly polarized light emission and detection in a graphene/α-CH(NH2)2PbI3 perovskite composite, at ambient temperature and without a magnetic field. We exploit the spin-charge conversion by introducing an unbalanced spin population through polarized light that gives rise to a spin photoconductive effect rationalized by Rashba-type coupling. The prepared composite heterostructure exhibits a circularly polarized photoluminescence anisotropy gCPL of ∼0.35 at ∼2.54 × 103 W cm-2 confocal power density of 532 nm excitation. A carefully engineered interface between the graphene and the perovskite thin film enhances the Rashba field and generates the built-in electric field responsible for photocurrent, yielding a photoresponsivity of ∼105 A W-1 under ∼0.08 μW cm-2 fluence of visible light photons. The maximum photocurrent anisotropy factor gph is ∼0.51 under ∼0.16 μW cm-2 irradiance. The work sheds light on the photophysical properties of graphene/perovskite composite heterostructures, finding them to be a promising candidate for developing miniaturized spin-photonic devices.

• Klíčová slova
• Rashba splitting, chirality, graphene, optical helicity sensing, perovskite, photodetector,
• Publikační typ
• časopisecké články MeSH

Electrical characterisation of perovskite solar cells consisting of room-temperature atomic-layer-deposited aluminium oxide (RT-ALD-Al2 O3 ) film on top of a methyl ammonium lead triiodide (CH3 NH3 PbI3 ) absorber showed excellent stability of the power conversion efficiency (PCE) over a long time. Under the same environmental conditions (for 355 d), the average PCE of solar cells without the ALD layer decreased from 13.6 to 9.6 %, whereas that of solar cells containing 9 ALD cycles of depositing RT-ALD-Al2 O3 on top of CH3 NH3 PbI3 increased from 9.4 to 10.8 %. Spectromicroscopic investigations of the ALD/perovskite interface revealed that the maximum PCE with the ALD layer is obtained when the so-called perovskite cleaning process induced by ALD precursors is complete. The PCE enhancement over time is probably related to a self-healing process induced by the RT-ALD-Al2 O3 film. This work may provide a new direction for further improving the long-term stability and performance of perovskite solar cells.

• Klíčová slova
• aluminum oxide, perovskite, photoelectron spectroscopy, solar cells, thin films,
• Publikační typ
• časopisecké články MeSH

A novel all-inorganic CsCu2I3 single-crystalline perovskite as a nonhygroscopic and efficient X-ray and γ-ray scintillator is described herein. It is featured by a one-dimensional (1D) perovskite structure with an orthorhombic system and a space group of Cmcm. The CsCu2I3 crystal emits yellow light peaking at 570 nm originated from strongly localized 1D exciton emission. It appears self-absorption free because of the large Stokes shift of 1.54 eV. The photophysics process of the self-trapped exciton was studied using temperature dependent photoluminescene spectra and decay kinetics measurements. The CsCu2I3 crystal exhibits an extremely low afterglow level of 0.008% at 10 ms under X-ray excitation. Under 137Cs γ-ray irradiation, its light yield is 16 000 photons/MeV with an energy resolution of 7.8% at 662 keV.

• Klíčová slova
• Bridgman method, cesium copper iodide, perovskite, radiation detection, scintillator, single crystal,
• Publikační typ
• časopisecké články MeSH

Dual-functional devices that can simultaneously detect light and emit light have a tremendous appeal for multiple applications, including displays, sensors, defense, and high-speed optical communication. Despite the tremendous efforts of scientists, the progress of integration of a phototransistor, where the built-in electric field separates the photogenerated excitons, and a light-emitting diode, where the radiative recombination can be enhanced by band offset, into a single device remains a challenge. Combining the superior properties of perovskite quantum dots (PQDs) and graphene, here we report a light-emissive, ultrasensitive, ultrafast, and broadband vertical phototransistor that can simultaneously act as an efficient photodetector and light emitter within a single device. The estimated value of the external quantum efficiency of the vertical phototransistor is ∼1.2 × 1010% with a photoresponsivity of >109 A W-1 and a response time of <50 μs, which exceed all the presently reported vertical phototransistor devices. We also demonstrate that the modulation of the Dirac point of graphene efficiently tunes both amplitude and polarity of the photocurrent. The device exhibits a green emission having a quantum efficiency of 5.6%. The moisture-insensitive and environmentally stable, light-emissive, ultrafast, and ultrasensitive broadband phototransistor creates a useful route for dual-functional optoelectronic devices.

• Klíčová slova
• LED, broadband photoresponse, graphene, perovskite quantum dots, vertical phototransistor,
• Publikační typ
• časopisecké články MeSH

Thin films made of formamidinium lead iodide (FAPbI3) perovskites prepared by a two-step sequential deposition method using various solvents for formamidinium iodide (FAI) - isopropanol, n-butanol and tert-butanol, were studied with the aim of finding a correlation between morphology and solvent properties to improve film quality. They were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) and their photophysical properties were studied by means of absorption and photoluminescence (PL) spectroscopies. XRD patterns, absorption and PL spectra proved α-phase formation for all selected solvents. An excessive amount of PbI2 found in perovskite films prepared with n-butanol indicates incomplete conversion. Thin film morphology, such as grain and crystallite size, depended on the solvent. Using tert-butanol, thin films with a very large grain size of up to several micrometers and with preferred crystallite orientation were fabricated. The grain size increased as follows: 0.2-0.5, 0.2-1 and 2-5 µm for isopropanol, n-butanol and tert-butanol, respectively. A correlation between the grain size and viscosity, electric permittivity and polarizability of the solvent could be considered. Our results, including fabrication of perovskite films with large grains and fewer grain boundaries, are important and of interest for many optoelectronic applications.

• Klíčová slova
• SEM, XRD, formamidinium lead iodide, morphology, perovskite, photophysics,
• Publikační typ
• časopisecké články MeSH