Quantum-Dot-Sensitized Solar Cells with Water-Soluble and Air-Stable PbS Quantum Dots

The sensitization of dispersed P25 TiO₂ nanoparticles (NPs) and macroporous TiO₂ films with water-soluble and air-stable PbS quantum dots (QDs) capped with l-glutathione (GSH) ligands was investigated. Optimum sensitization was achieved by careful adjustment of the surface charges of TiO₂ and PbS QDs by controlling the pH of the QD solution. Efficient electron transfer from photoexcited PbS QDs via the GSH ligands into the conduction band of TiO₂ was demonstrated by photoluminescence (PL) spectroscopy of PbS-sensitized P25 nanoparticles. The PbS QD-sensitized porous TiO₂ electrodes were used to prepare quantum-dot-sensitized solar cells (QDSSCs) utilizing a Cu_<i>x</i>S_<i>y</i> counter electrode and aqueous polysulfide electrolyte. Cells with up to 64% injection efficiency, 1.1% AM 1.5 conversion efficiency, and short circuit current density of 7.4 mA cm^–2 were obtained. The physical parameters of the cells were investigated using impedance spectroscopy

Epitaxial Halide Perovskite Lateral Double Heterostructure

Epitaxial III–V semiconductor heterostructures are key components in modern microelectronics, electro-optics, and optoelectronics. With superior semiconducting properties, halide perovskite materials are rising as promising candidates for coherent heterostructure devices. In this report, spinodal decomposition is proposed and experimentally implemented to produce epitaxial double heterostructures in halide perovskite system. Pristine epitaxial mixed halide perovskites rods and films were synthesized via van der Waals epitaxy by chemical vapor deposition method. At room temperature, photon was applied as a knob to regulate the kinetics of spinodal decomposition and classic coarsening. By this approach, halide perovskite double heterostructures were created carrying epitaxial interfaces and outstanding optical properties. Reduced Fröhlich electron–phonon coupling was discovered in coherent halide double heterostructure, which is hypothetically attributed to the classic phonon confinement effect widely existing in III–V double heterostructures. As a proof-of-concept, our results suggest that halide perovskite-based epitaxial heterostructures may be promising for high-performance and low-cost optoelectronics, electro-optics, and microelectronics. Thus, ultimately, for practical device applications, it may be worthy to pursue these heterostructures via conventional vapor phase epitaxy approaches widely practised in III–V field

Motional Narrowing Effects in the Excited State Spin Populations of Mn-Doped Hybrid Perovskites

Spin–orbit coupling in the electronic states of solution-processed hybrid metal halide perovskites forms complex spin-textures in the band structures and allows for optical manipulation of the excited state spin-polarizations. Here, we report that motional narrowing acts on the photoexcited spin-polarization in CH3NH3PbBr3 thin films, which are doped at percentage-level with Mn2+ ions. Using ultrafast circularly polarized broadband transient absorption spectroscopy at cryogenic temperatures, we investigate the spin population dynamics in these doped hybrid perovskites and find that spin relaxation lifetimes are increased by a factor of 3 compared to those of undoped materials. Using quantitative analysis of the photoexcitation cooling processes, we reveal increased carrier scattering rates in the doped perovskites as the fundamental mechanism driving spin-polarization-maintaining motional narrowing. Our work reports transition-metal doping as a concept to extend spin lifetimes of hybrid perovskites

Ultrafast Dynamics of Polariton Cooling and Renormalization in an Organic Single-Crystal Microcavity under Nonresonant Pumping

Microcavity systems with organic luminescent materials have a hot prospect for room-temperature cavity-polariton devices. The polariton dispersion relation of organic microcavities is significantly different from that of inorganic microcavities due to the strong localization of Frenkel excitons. Also photoexcited particles will undergo a different cooling mechanism until they reach the polariton ground state. In the characterization of efficient polariton condensates, therefore, the polariton cooling dynamics as well as the kinetics of the polariton eigenstate should be measured. Here we present experimental studies on ultrafast dynamics of cavity polaritons in an organic single-crystal microcavity under nonresonant pumping. In time-resolved photoluminescence measurements we observed, for the first time, an ultrafast dynamics of stimulated cooling of the organic cavity polariton. Transient transmission measurement enabled us to investigate the detailed renormalization dynamics of the polariton eigenstate. The results clearly demonstrated the prospect of organic microcavities for room-temperature polaritonic devices

Photon Transport in One-Dimensional Incommensurately Epitaxial CsPbX₃ Arrays

One-dimensional nanoscale epitaxial arrays serve as a great model in studying fundamental physics and for emerging applications. With an increasing focus laid on the Cs-based inorganic halide perovskite out of its outstanding material stability, we have applied vapor phase epitaxy to grow well aligned horizontal CsPbX₃ (X: Cl, Br, or I or their mixed) nanowire arrays in large scale on mica substrate. The as-grown nanowire features a triangular prism morphology with typical length ranging from a few tens of micrometers to a few millimeters. Structural analysis reveals that the wire arrays follow the symmetry of mica substrate through incommensurate epitaxy, paving a way for a universally applicable method to grow a broad family of halide perovskite materials. The unique photon transport in the one-dimensional structure has been studied in the all-inorganic Cs-based perovskite wires via temperature dependent and spatially resolved photoluminescence. Epitaxy of well oriented wire arrays in halide perovskite would be a promising direction for enabling the circuit-level applications of halide perovskite in high-performance electro-optics and optoelectronics

Preparation of Single-Phase Films of CH₃NH₃Pb(I_1–<i>x</i>Br_<i>x</i>)₃ with Sharp Optical Band Edges

Organometallic lead-halide perovskite-based solar cells now approach 18% efficiency. Introducing a mixture of bromide and iodide in the halide composition allows tuning of the optical bandgap. We prepare mixed bromide–iodide lead perovskite films CH₃NH₃Pb­(I_1–<i>x</i>Br_<i>x</i>)₃ (0 ≤ <i>x</i> ≤ 1) by spin-coating from solution and obtain films with monotonically varying bandgaps across the full composition range. Photothermal deflection spectroscopy, photoluminescence, and X-ray diffraction show that following suitable fabrication protocols these mixed lead-halide perovskite films form a single phase. The optical absorption edge of the pure triiodide and tribromide perovskites is sharp with Urbach energies of 15 and 23 meV, respectively, and reaches a maximum of 90 meV for CH₃NH₃PbI_1.2Br_1.8. We demonstrate a bromide–iodide lead perovskite film (CH₃NH₃PbI_1.2Br_1.8) with an optical bandgap of 1.94 eV, which is optimal for tandem cells of these materials with crystalline silicon devices

Atmospheric Influence upon Crystallization and Electronic Disorder and Its Impact on the Photophysical Properties of Organic–Inorganic Perovskite Solar Cells

Recently, solution-processable organic–inorganic metal halide perovskites have come to the fore as a result of their high power-conversion efficiencies (PCE) in photovoltaics, exceeding 17%. To attain reproducibility in the performance, one of the critical factors is the processing conditions of the perovskite film, which directly influences the photophysical properties and hence the device performance. Here we study the effect of annealing parameters on the crystal structure of the perovskite films and correlate these changes with its photophysical properties. We find that the crystal formation is kinetically driven by the annealing atmosphere, time and temperature. Annealing in air produces an improved crystallinity and large grain domains as compared to nitrogen. Lower photoluminescence quantum efficiency (PLQE) and shorter photoluminescence (PL) lifetimes are observed for nitrogen annealed perovskite films as compared to the air-annealed counterparts. We note that the limiting nonradiative pathways (<i>i.e</i>., maximizing PLQE) is important for obtaining the highest device efficiency. This indicates a critical impact of the atmosphere upon crystallization and the ultimate device performance

Blue-Green Color Tunable Solution Processable Organolead Chloride–Bromide Mixed Halide Perovskites for Optoelectronic Applications

Solution-processed organo-lead halide perovskites are produced with sharp, color-pure electroluminescence that can be tuned from blue to green region of visible spectrum (425–570 nm). This was accomplished by controlling the halide composition of CH₃NH₃Pb­(Br_<i>x</i>Cl_1–<i>x</i>)₃ [0 ≤ <i>x</i> ≤ 1] perovskites. The bandgap and lattice parameters change monotonically with composition. The films possess remarkably sharp band edges and a clean bandgap, with a single optically active phase. These chloride–bromide perovskites can potentially be used in optoelectronic devices like solar cells and light emitting diodes (LEDs). Here we demonstrate high color-purity, tunable LEDs with narrow emission full width at half maxima (FWHM) and low turn on voltages using thin-films of these perovskite materials, including a blue CH₃NH₃PbCl₃ perovskite LED with a narrow emission FWHM of 5 nm

Photon Reabsorption in Mixed CsPbCl₃:CsPbI₃ Perovskite Nanocrystal Films for Light-Emitting Diodes

Cesium lead halide nanocrystals, CsPbX₃ (X = Cl, Br, I), exhibit photoluminescence quantum efficiencies approaching 100% without the core–shell structures usually used in conventional semiconductor nanocrystals. These high photoluminescence efficiencies make these crystals ideal candidates for light-emitting diodes (LEDs). However, because of the large surface area to volume ratio, halogen exchange between perovskite nanocrystals of different compositions occurs rapidly, which is one of the limiting factors for white-light applications requiring a mixture of different crystal compositions to achieve a broad emission spectrum. Here, we use mixtures of chloride and iodide CsPbX₃ (X = Cl, I) perovskite nanocrystals where anion exchange is significantly reduced. We investigate samples containing mixtures of perovskite nanocrystals with different compositions and study the resulting optical and electrical interactions. We report excitation transfer from CsPbCl₃ to CsPbI₃ in solution and within a poly­(methyl methacrylate) matrix via photon reabsorption, which also occurs in electrically excited crystals in bulk heterojunction LEDs

Enhanced Amplified Spontaneous Emission in Perovskites Using a Flexible Cholesteric Liquid Crystal Reflector

Organic–inorganic perovskites are highly promising solar cell materials with laboratory-based power conversion efficiencies already matching those of established thin film technologies. Their exceptional photovoltaic performance is in part attributed to the presence of efficient radiative recombination pathways, thereby opening up the possibility of efficient light-emitting devices. Here, we demonstrate optically pumped amplified spontaneous emission (ASE) at 780 nm from a 50 nm-thick film of CH₃NH₃PbI₃ perovskite that is sandwiched within a cavity composed of a thin-film (∼7 μm) cholesteric liquid crystal (CLC) reflector and a metal back-reflector. The threshold fluence for ASE in the perovskite film is reduced by at least two orders of magnitude in the presence of the CLC reflector, which results in a factor of two reduction in threshold fluence compared to previous reports. We consider this to be due to improved coupling of the oblique and out-of-plane modes that are reflected into the bulk in addition to any contributions from cavity modes. Furthermore, we also demonstrate enhanced ASE on flexible reflectors and discuss how improvements in the quality factor and reflectivity of the CLC layers could lead to single-mode lasing using CLC reflectors. Our work opens up the possibility of fabricating widely wavelength-tunable “mirror-less” single-mode lasers on flexible substrates, which could find use in applications such as flexible displays and friend or foe identification