Improved Performance of Air-Processed Perovskite Solar Cells via the Combination of Chlorine Precursors and Potassium Thiocyanate.

Due to their low cost and high efficiency, hybrid perovskite solar cells (PSCs) have shown the most outstanding competitiveness among third-generation photovoltaic (PV) devices. However, several challenges remain unresolved, among which the limited stability is arguably the main. Chlorine (Cl) has been widely employed to yield PV performances, but the Cl-doping mechanism and its role in mixed-halide PSCs are not entirely understood. Here, we investigate the effect of Cl-doping using different precursors such as formamidinium chloride (FACl), cesium chloride (CsCl), and lead chloride (PbCl2), which lead to the incorporation of Cl at different sites of the perovskite crystal. We demonstrate that the stability and efficiency of air-processed PSCs are strongly affected by Cl bonding into the cationic chloride precursor. Furthermore, adding potassium thiocyanate (KSCN) leads to the maximum efficiency of 18.1%, improving the operational stability with only 18% PCE loss after 520 h, stored under ambient conditions. Incorporating CsCl and KSCN presents an effective approach to further boost the performance and thermal stability of PSCs by tailoring the composition of the perovskite's composition. Finally, we used the slot-die method to demonstrate that our strategy is scalable for large-area devices that have shown similar performance. Our results show that fully air-processed and stable PSCs with high efficiency for large production and commercialization are achievable.

High performance BiFeO3 ferroelectric nanostructured photocathodes.

Ferroelectric materials may be used as effective photoelectrocatalysts for water splitting due to enhanced charge carrier separation driven by their spontaneous polarization induced internal electric field. Compared to other ferroelectric materials, BiFeO3 exhibits a high catalytic efficiency due to its comparatively smaller bandgap, which enables light absorption from a large part of the solar spectrum and its higher bulk ferroelectric polarization. Here, we compare the photoelectrochemical properties of three different BiFeO3 morphologies, namely, nanofibers, nanowebs, and thin films synthesized via electrospinning, directly on fluorine-doped tin oxide (FTO) coated glass substrates. A significant photocathodic current in the range from -86.2 to -56.5 µA cm-2 at -0.4 V bias (vs Ag/AgCl) has been recorded for all three morphologies in 0.1M Na2SO4 aqueous solution (pH = 6.8). Among these morphologies, BiFeO3 nanofibers exhibit higher efficiency because of their larger surface area and improved charge separation resulting from rapid diffusion of photoinduced charge carriers along the axis of the nanofiber. In the case of BiFeO3 nanofibers, we obtained the highest photocurrent density of -86.2 µA/cm2 at -0.4 V bias (vs Ag/AgCl electrode) and an onset potential of 0.22 V. We also observed that the onset potential of the photocathodic current can be increased by applying a positive polarization voltage, which leads to favorable bending of band edges at the electrode/electrolyte interface resulting in increased charge carrier separation.

Halide Perovskite Nanocrystals for Next-Generation Optoelectronics.

Colloidal perovskite nanocrystals (PNCs) combine the outstanding optoelectronic properties of bulk perovskites with strong quantum confinement effects at the nanoscale. Their facile and low-cost synthesis, together with superior photoluminescence quantum yields and exceptional optical versatility, make PNCs promising candidates for next-generation optoelectronics. However, this field is still in its early infancy and not yet ready for commercialization due to several open challenges to be addressed, such as toxicity and stability. Here, the key synthesis strategies and the tunable optical properties of PNCs are discussed. The photophysical underpinnings of PNCs, in correlation with recent developments of PNC-based optoelectronic devices, are especially highlighted. The final goal is to outline a theoretical scaffold for the design of high-performance devices that can at the same time address the commercialization challenges of PNC-based technology.

Epitaxial Bi2FeCrO6 Multiferroic Thin-Film Photoanodes with Ultrathin p-Type NiO Layers for Improved Solar Water Oxidation.

The photoelectric properties of multiferroic double-perovskite Bi2FeCrO6 (BFCO), such as above-band gap photovoltages, switchable photocurrents, and bulk photovoltaic effects, have recently been explored for potential applications in solar technology. Here, we report the fabrication of photoelectrodes based on n-type ferroelectric (FE) semiconductor BFCO heterojunctions coated with p-type transparent conducting oxides (TCOs) by pulsed laser deposition and their application for photoelectrochemical (PEC) water oxidation. The photocatalytic properties of the bare BFCO photoanodes can be improved by controlling the FE polarization state. However, the charge recombination as well as the limited charge transfer kinetics in the photoanode/electrolyte cause major energy loss and thus hinder the PEC performance. We show that this problem may be addressed by the deposition of an ultrathin p-type NiO layer on the photoanode to enhance the charge transport kinetics and reduce charge recombination at surface-trapped states for increased surface band bending. A fourfold enhancement of photocurrent density, up to 0.4 mA cm-2 (at +1.23 V vs RHE), a best performance of stability over 4 h, and a high incident photon-to-current efficiency (∼3.7%) were achieved under 1 sun illumination in such p-NiO/n-BFCO heterojunction photoanodes. These studies reveal the optimization of PEC performance by polarization switching of BFCO and the successful achievement of p-TCOs/n-FE heterojunction photoanodes that are able to sustain water oxidation that is stable for many hours.

Highly Efficient and Ultrasensitive Large-Area Flexible Photodetector Based on Perovskite Nanowires.

Hybrid organic-inorganic perovskites have shown exceptional semiconducting properties and microstructural versatility for inexpensive, solution-processable photovoltaic and optoelectronic devices. In this work, an all-solution-based technique in ambient environment for highly sensitive and high-speed flexible photodetectors using high crystal quality perovskite nanowires grown on Kapton substrate is presented. At 10 V, the optimized photodetector exhibits a responsivity as high as 0.62 A W-1 , a maximum specific detectivity of 7.3 × 1012 cm Hz1/2 W-1 , and a rise time of 227.2 µs. It also shows remarkable photocurrent stability even beyond 5000 bending cycles. Moreover, a deposition of poly(methyl methacrylate) (PMMA) as a protective layer on the perovskite yields significantly better stability under ambient air operation: the PMMA-protected devices are stable for over 30 days. This work demonstrates a cost-effective fabrication technique for high-performance flexible photodetectors and opens opportunities for research advancements in broadband and large-scale flexible perovskite-based optoelectronic devices.

Epitaxial patterned Bi2FeCrO6 nanoisland arrays with room temperature multiferroic properties.

Epitaxial multiferroic Bi2FeCrO6 nanoisland arrays with a lateral size of ∼100 nm have been successfully fabricated by patterned SiO2 template-assisted pulsed laser deposition. The as-grown island structure exhibits promising multiferroic properties (i.e. ferroelectric and magnetic) even at nanometer dimensions at room temperature. This work demonstrates an effective strategy to fabricate high-density nonvolatile ferroelectric/multiferroic memory devices.

Hysteresis-Free 1D Network Mixed Halide-Perovskite Semitransparent Solar Cells.

The morphology of hybrid organic-inorganic perovskite films is known to strongly affect the performance of perovskite-based solar cells. CH3 NH3 PbI3-x Clx (MAPbI3-x Clx ) films have been previously fabricated with 100% surface coverage in glove boxes. In ambient air, fabrication generally relies on solvent engineering to obtain compact films. In contrast, this work explores the potential of altering the perovskites microstructure for solar cell engineering. This work starts with CH3 NH3 PbI3-x Clx , films with grain morphology carefully controlled by varying the deposition speed during the spin-coating process to fabricate efficient and partially transparent solar cells. Devices produced with a CH3 NH3 PbI3-x Clx film and a compact thick top gold electrode reach a maximum efficiency of 10.2% but display a large photocurrent hysteresis. As it is demonstrated, the introduction of different concentrations of bromide in the precursor solution addresses the hysteresis issues and turns the film morphology into a partially transparent interconnected network of 1D microstructures. This approach leads to semitransparent solar cells with negligible hysteresis and efficiencies up to 7.2%, while allowing average transmission of 17% across the visible spectrum. This work demonstrates that the optimization of the perovskites composition can mitigate the hysteresis effects commonly attributed to the charge trapping within the perovskite film.

Solvent-Antisolvent Ambient Processed Large Grain Size Perovskite Thin Films for High-Performance Solar Cells.

In recent years, hybrid organic-inorganic halide perovskites have been widely studied for the low-cost fabrication of a wide range of optoelectronic devices, including impressive perovskite-based solar cells. Amongst the key factors influencing the performance of these devices, recent efforts have focused on tailoring the granularity and microstructure of the perovskite films. Albeit, a cost-effective technique allowing to carefully control their microstructure in ambient environmental conditions has not been realized. We report on a solvent-antisolvent ambient processed CH3NH3PbI3-xClx based thin films using a simple and robust solvent engineering technique to achieve large grains (>5 µm) having excellent crystalline quality and surface coverage with very low pinhole density. Using optimized treatment (75% chlorobenzene and 25% ethanol), we achieve highly-compact perovskite films with 99.97% surface coverage to produce solar cells with power conversion efficiencies (PCEs) up-to 14.0%. In these planar solar cells, we find that the density and size of the pinholes are the dominant factors that affect their overall performances. This work provides a promising solvent treatment technique in ambient conditions and paves the way for further optimization of large area thin films and high performance perovskite solar cells.

An ultra-broadband perovskite-PbS quantum dot sensitized carbon nanotube photodetector.

Organic-inorganic perovskites have been hailed as promising candidates for optoelectronic and photovoltaic devices, but their operation remains limited to the visible spectrum. Here, we combine single-wall carbon nanotubes, PbS quantum dots and a perovskite to synthesize hybrid devices suitable for operation in both the visible and near-infrared. The photodetectors thus fabricated show responsivities as high as 0.5 A W-1 and 0.35 A W-1 at 500 nm and at 1300 nm, respectively, with an applied bias of 1 V. Moreover, the incorporation of nanotubes within the perovskite matrix facilitates the carrier extraction, resulting in response time under 250 µs, a gain-bandwidth product of 0.1 MHz and detectivities of 1.4 × 1011 Jones and 0.9 × 1011 Jones at 500 nm and at 1300 nm, respectively. This unique approach opens new pathways for the development of low-cost, high-speed and broadband perovskite-based optoelectronic devices for large-scale manufacturing.

Highly Sensitive Switchable Heterojunction Photodiode Based on Epitaxial Bi2FeCrO6 Multiferroic Thin Films.

Perovskite multiferroic oxides are promising materials for the realization of sensitive and switchable photodiodes because of their favorable band gap (<3.0 eV), high absorption coefficient, and tunable internal ferroelectric (FE) polarization. A high-speed switchable photodiode based on multiferroic Bi2FeCrO6 (BFCO)/SrRuO3 (SRO)-layered heterojunction was fabricated by pulsed laser deposition. The heterojunction photodiode exhibits a large ideality factor ( n = ∼5.0) and a response time as fast as 68 ms, thanks to the effective charge carrier transport and collection at the BFCO/SRO interface. The diode can switch direction when the electric polarization is reversed by an external voltage pulse. The time-resolved photoluminescence decay of the device measured at ∼500 nm demonstrates an ultrafast charge transfer (lifetime = ∼6.4 ns) in BFCO/SRO heteroepitaxial structures. The estimated responsivity value at 500 nm and zero bias is 0.38 mA W-1, which is so far the highest reported for any FE thin film photodiode. Our work highlights the huge potential for using multiferroic oxides to fabricate highly sensitive and switchable photodiodes.

Highly Efficient Thermoelectric Microgenerators Using Nearly Room Temperature Pulsed Laser Deposition.

Thermoelectric Bi2Te3 and Sb2Te3 thin films with high power factor were successfully obtained by pulsed laser deposition (PLD). Here, we demonstrate a well-controlled deposition of Bi2Te3/Sb2Te3 structures on glass substrates, through a shadow mask with micrometer-scale features. We establish an optimal growth temperature of 45 °C to attain compounds with suitable stoichiometric composition, as well as structural and electrical properties, to achieve high thermoelectric power factor. These films are produced without additional postannealing treatment or added gases. Indeed, crystalline films with Seebeck coefficients of 624 and -78 µV K-1 are obtained for Sb2Te3 and Bi2Te3, respectively. Microgenerators consisting of four pairs of n-type Bi2Te3 and p-type Sb2Te3 legs connected in series generate a maximum voltage of 50 mV and a power density of around 120 µW cm-2 for a temperature difference of 30 K across the hot and cold ends of the device. This low-temperature and simple PLD-deposited device represents an important step toward practical thermoelectric materials as well as efficient and compact microgenerators for low-temperature energy-harvesting applications.

Epitaxial magnetite nanorods with enhanced room temperature magnetic anisotropy.

Nanostructured magnetic materials with well-defined magnetic anisotropy are very promising as building blocks in spintronic devices that operate at room temperature. Here we demonstrate the epitaxial growth of highly oriented Fe3O4 nanorods on a SrTiO3 substrate by hydrothermal synthesis without the use of a seed layer. The epitaxial nanorods showed biaxial magnetic anisotropy with an order of magnitude difference between the anisotropy field values of the easy and hard axes. Using a combination of conventional magnetometry, transverse susceptibility, magnetic force microscopy (MFM) and magneto-optic Kerr effect (MOKE) measurements, we investigate magnetic behavior such as temperature dependent magnetization and anisotropy, along with room temperature magnetic domain formation and its switching. The interplay of epitaxy and enhanced magnetic anisotropy at room temperature, with respect to randomly oriented powder Fe3O4 nanorods, is discussed. The results obtained identify epitaxial nanorods as useful materials for magnetic data storage and spintronic devices that necessitate tunable anisotropic properties with sharp magnetic switching phenomena.

High-performance nanotube-enhanced perovskite photodetectors.

Organic-inorganic perovskites have already shown a tremendous potential for low-cost light-harvesting devices. Yet, the relatively low carrier mobilities in bulk perovskites still prevent large-area devices with performances competing with state-of-the-art technologies. Here, we tackle this fundamental challenge by incorporating single-wall carbon nanotubes within a perovskite matrix by means of a simple two-step method in ambient air. Using this nano-engineered hybrid film, we demonstrate large-area photodetectors with responsivities up-to 13.8 A.W-1 and a broad spectral response from 300 to 800 nm, indicating that photocurrent generation arises from the charge transfer from the perovskite matrix to the embedded nanotube network. As the nanotubes facilitate the carrier extraction, these photodetectors also show a fast response time of 10 ms. This is significantly faster than most of previous reports on perovskite-based photodetectors, including devices with much smaller photosensitive areas. This approach is also well-suited for large-scale production of other perovskite-based light-harvesting devices.

Enhanced photovoltaic properties in bilayer BiFeO3/Bi-Mn-O thin films.

We report an external solar power conversion efficiency of ∼1.43% in BiFeO3(BFO)/BiMnO3(BMO) bilayer thin films. Both films are epitaxially grown on (111) oriented niobium doped SrTiO3 (NSTO) single crystal substrates by pulsed laser deposition. By illuminating the BFO/BMO films under 1 Sun (AM 1.5 G), we found a remarkably high fill factor of ∼0.72, much higher than values reported for devices based on BFO or BMO alone. In addition, we demonstrate that the photocurrent density and photovoltage are tunable by changing the polarization direction in the BFO/BMO bilayer, as confirmed by the macroscopic polarization-voltage (P-V) hysteresis loop. This effect is described in terms of a more favorable energy band alignment of the electrode/bilayer/NSTO heterostructure junction, which controls photocarrier separation.

Epitaxial Bi2 FeCrO6 Multiferroic Thin Film as a New Visible Light Absorbing Photocathode Material.

Ferroelectric materials have been studied increasingly for solar energy conversion technologies due to the efficient charge separation driven by the polarization induced internal electric field. However, their insufficient conversion efficiency is still a major challenge. Here, a photocathode material of epitaxial double perovskite Bi(2) FeCrO(6) multiferroic thin film is reported with a suitable conduction band position and small bandgap (1.9-2.1 eV), for visible-light-driven reduction of water to hydrogen. Photoelectrochemical measurements show that the highest photocurrent density up to -1.02 mA cm(-2) at a potential of -0.97 V versus reversible hydrogen electrode is obtained in p-type Bi(2) FeCrO(6) thin film photocathode grown on SrTiO(3) substrate under AM 1.5G simulated sunlight. In addition, a twofold enhancement of photocurrent density is obtained after negatively poling the Bi(2) FeCrO(6) thin film, as a result of modulation of the band structure by suitable control of the internal electric field gradient originating from the ferroelectric polarization in the Bi(2) FeCrO(6) films. The findings validate the use of multiferroic Bi(2) FeCrO(6) thin films as photocathode materials, and also prove that the manipulation of internal fields through polarization in ferroelectric materials is a promising strategy for the design of improved photoelectrodes and smart devices for solar energy conversion.

Remarkably enhanced photocatalytic activity of laser ablated Au nanoparticle decorated BiFeO3 nanowires under visible-light.

Hybrid photocatalysts consisting of single crystalline BiFeO3 nanowires and laser ablated Au nanoparticles were synthesized by a functionalization-step-free solution process. The 1.0 wt% Au nanoparticle decorated BiFeO3 nanowires exhibit ~30 times higher photocatalytic activity for water oxidation than that exhibited by the parent wires during the first 4 h.

Bifunctional catalytic/magnetic Ni@Ru core-shell nanoparticles.

Core-shell structured Ni@Ru bimetallic nanoparticles are demonstrated as a bifunctional nanoplatform system for the hydrolysis reaction of ammonia-borane and also for magnetic separation.

Imaging, core-loss, and low-loss electron-energy-loss spectroscopy mapping in aberration-corrected STEM.

High-angle annular dark-field and annular bright-field imaging experiments were carried out on an aberration-corrected transmission electron microscope. These techniques have been demonstrated on thin films of complex oxides Ba3.25La0.75Ti3O12 and on LaB6. The results show good agreement between theory and experiments, and for the case of LaB6 they demonstrate the detection of contrast from the B atoms in the annular bright-field images. Elemental mapping with electron-energy-loss spectroscopy has been used to deduce the distribution of Cr and Fe in a thin film of the complex oxide Bi2(Fe1/2Cr3/2)O6 at the unit cell level and the changes in the near-edge structure within the inequivalent regions in the crystalline unit cell. Energy-filtered images in the low-loss region of the energy-loss spectrum show contrast and resolution consistent with the modulation of the signals from elastic scattering. High-resolution contrast, mediated by phonon scattering, is observed for interband transitions. The limitations in terms of detection and signal are discussed.

Growth, structure, and properties of BiFeO3/-BiCrO3 films obtained by dual cross beam PLD.

The properties of epitaxial Bi(2)FeCrO(6) thin films, recently synthesized by pulsed laser deposition, have partially confirmed the theoretical predictions (i.e., a magnetic moment of 2 micro(B) per formula unit and a polarization of approximately 80 microC/cm(2) at 0 K). The existence of magnetic ordering at room temperature for this material is an unexpected, but very promising, result that needs to be further investigated. Because magnetism is assumed to arise from the exchange interaction between the Fe and Cr cations, the magnetic behavior is strongly dependent on both their ordering and the distance between them. We present here the successful synthesis of epitaxial Bi(2)Fe(x)CryO(6) (BFCO x/y) films grown on SrTiO3 substrates using dual crossed-beam, pulsed-laser deposition. The crystal structure of the films has different types of (111)-oriented superstructures, depending on the deposition conditions. The multiferroic character of BFCO (x/y) films is proven by the presence of both ferroelectric and magnetic hysteresis at room temperature. The oxidation state of Fe and Cr ions in the films is shown to be 3+ only, and the difference in macroscopic magnetization with Fe/Cr ratio composition could only be due to ordering of the Cr(3+) and Fe(3+) cations to the modification of the exchange interaction between them.