Emre Yassitepe

Homogeneously dispersed, multimetal oxygen-evolving catalysts

Modulating metal oxides The more difficult step in fuel cells and water electrolysis is the oxygen evolution reaction. The search for earth-abundant materials to replace noble metals for this reaction often turns to oxides of three-dimensional metals such as iron. Zhang et al. show that the applied voltages needed to drive this reaction are reduced for iron-cobalt oxides by the addition of tungsten. The addition of tungsten favorably modulates the electronic structure of the oxyhydroxide. A key development is to keep the metals well mixed and avoid the formation of separate phases. Science, this issue p. 333 The addition of tungsten to iron cobalt oxides lowers the overpotential required for the evolution of oxygen from water. Earth-abundant first-row (3d) transition metal–based catalysts have been developed for the oxygen-evolution reaction (OER); however, they operate at overpotentials substantially above thermodynamic requirements. Density functional theory suggested that non-3d high-valency metals such as tungsten can modulate 3d metal oxides, providing near-optimal adsorption energies for OER intermediates. We developed a room-temperature synthesis to produce gelled oxyhydroxides materials with an atomically homogeneous metal distribution. These gelled FeCoW oxyhydroxides exhibit the lowest overpotential (191 millivolts) reported at 10 milliamperes per square centimeter in alkaline electrolyte. The catalyst shows no evidence of degradation after more than 500 hours of operation. X-ray absorption and computational studies reveal a synergistic interplay between tungsten, iron, and cobalt in producing a favorable local coordination environment and electronic structure that enhance the energetics for OER.

QUANTUM-DOT-IN-PEROVSKITE SOLIDS

Heteroepitaxy—atomically aligned growth of a crystalline film atop a different crystalline substrate—is the basis of electrically driven lasers, multijunction solar cells, and blue-light-emitting diodes. Crystalline coherence is preserved even when atomic identity is modulated, a fact that is the critical enabler of quantum wells, wires, and dots. The interfacial quality achieved as a result of heteroepitaxial growth allows new combinations of materials with complementary properties, which enables the design and realization of functionalities that are not available in the single-phase constituents. Here we show that organohalide perovskites and preformed colloidal quantum dots, combined in the solution phase, produce epitaxially aligned ‘dots-in-a-matrix’ crystals. Using transmission electron microscopy and electron diffraction, we reveal heterocrystals as large as about 60 nanometres and containing at least 20 mutually aligned dots that inherit the crystalline orientation of the perovskite matrix. The heterocrystals exhibit remarkable optoelectronic properties that are traceable to their atom-scale crystalline coherence: photoelectrons and holes generated in the larger-bandgap perovskites are transferred with 80% efficiency to become excitons in the quantum dot nanocrystals, which exploit the excellent photocarrier diffusion of perovskites to produce bright-light emission from infrared-bandgap quantum-tuned materials. By combining the electrical transport properties of the perovskite matrix with the high radiative efficiency of the quantum dots, we engineer a new platform to advance solution-processed infrared optoelectronics.

Highly Efficient Perovskite-Quantum-Dot Light-Emitting Diodes by Surface Engineering

A two-step ligand-exchange strategy is developed, in which the long-carbon- chain ligands on all-inorganic perovskite (CsPbX3 , X = Br, Cl) quantum dots (QDs) are replaced with halide-ion-pair ligands. Green and blue light-emitting diodes made from the halide-ion-pair-capped quantum dots exhibit high external quantum efficiencies compared with the untreated QDs.

Colloidal Quantum Dot Photovoltaics Enhanced by Perovskite Shelling.

Solution-processed quantum dots are a promising material for large-scale, low-cost solar cell applications. New device architectures and improved passivation have been instrumental in increasing the performance of quantum dot photovoltaic devices. Here we report photovoltaic devices based on inks of quantum dot on which we grow thin perovskite shells in solid-state films. Passivation using the perovskite was achieved using a facile solution ligand exchange followed by postannealing. The resulting hybrid nanostructure created a more intrinsic CQD film, which, when incorporated into a photovoltaic device with graded bandstructure, achieved a record solar cell performance for single-step-deposited CQD films, exhibiting an AM1.5 solar power conversion efficiency of 8.95%.

Colloidal CdSe1–xSx Nanoplatelets with Narrow and Continuously-Tunable Electroluminescence

Colloidal nanoplatelets, quasi-two-dimensional quantum wells, have recently been introduced as colloidal semiconductor materials with the narrowest known photoluminescence line width (∼10 nm). Unfortunately, these materials have not been shown to have continuously tunable emission but rather emit at discrete wavelengths that depend strictly on atomic-layer thickness. Herein, we report a new synthesis approach that overcomes this issue: by alloying CdSe colloidal nanoplatelets with CdS, we finely tune the emission spectrum while still leveraging atomic-scale thickness control. We proceed to demonstrate light-emitting diodes with sub-bandgap turn-on voltages (2.1 V for a device emitting at 2.4 eV) and the narrowest electroluminescence spectrum (FWHM ∼12.5 nm) reported for colloidal semiconductor LEDs.

Efficient Biexciton Interaction in Perovskite Quantum Dots Under Weak and Strong Confinement

Cesium lead halide perovskite quantum dots (PQDs) have emerged as a promising new platform for lighting applications. However, to date, light emitting diodes (LED) based on these materials exhibit limited efficiencies. One hypothesized limiting factor is fast nonradiative multiexciton Auger recombination. Using ultrafast spectroscopic techniques, we investigate multicarrier interaction and recombination mechanisms in cesium lead halide PQDs. By mapping the dependence of the biexciton Auger lifetime and the biexciton binding energy on nanomaterial size and composition, we find unusually strong Coulomb interactions among multiexcitons in PQDs. This results in weakly emissive biexcitons and trions, and accounts for low light emission efficiencies. We observe that, for strong confinement, the biexciton lifetime depends linearly on the PQD volume. This dependence becomes sublinear in the weak confinement regime as the PQD size increases beyond the Bohr radius. We demonstrate that Auger recombination is faster in PQDs compared to CdSe nanoparticles having the same volume, suggesting a stronger Coulombic interaction in the PQDs. We confirm this by demonstrating an increased biexciton binding energy, which reaches a maximum of about 100 meV, fully three times larger than in CdSe quantum dots. The biexciton shift can lead to low-threshold optical gain in these materials. These findings also suggest that materials engineering to reduce Coulombic interaction in cesium lead halide PQDs could improve prospects for high efficiency optoelectronic devices. Core-shell structures, in particular type-II nanostructures, which are known to reduce the bandedge Coulomb interaction in CdSe/CdS, could beneficially be applied to PQDs with the goal of increasing their potential in lighting applications.

Self-Assembled PbSe Nanowire:Perovskite Hybrids.

Inorganic semiconductor nanowires are of interest in nano- and microscale photonic and electronic applications. Here we report the formation of PbSe nanowires based on directional quantum dot alignment and fusion regulated by hybrid organic-inorganic perovskite surface ligands. All material synthesis is carried out at mild temperatures. Passivation of PbSe quantum dots was achieved via a new perovskite ligand exchange. Subsequent in situ ammonium/amine substitution by butylamine enables quantum dots to be capped by butylammonium lead iodide, and this further drives the formation of a PbSe nanowire superlattice in a two-dimensional (2D) perovskite matrix. The average spacing between two adjacent nanowires agrees well with the thickness of single atomic layer of 2D perovskite, consistent with the formation of a new self-assembled semiconductor nanowire:perovskite heterocrystal hybrid.

Nonlinear spectroscopy in perovskite quantum dots

Since the first reports of their successful synthesis in 2015, all-inorganic perovskite quantum dots (PQDs), emerged as promising material for lighting applications. Despite their unique optical properties, to date, PQDs based LEDs and lasing media operation is still far from ideal. One of the limiting factors is the strong Coulomb interaction, which contributes to nonradiative decay processes. Here, we discuss in detail the multiexciton interactions in PQDs based on their size dependence. We expand on their nonlinear optical properties, focusing on the two-photon absorption characteristics, showing results for two-photon pumped amplified stimulated emission, suggesting that these materials may be promising for two-photon pumped lasers.

Color tunable hybrid light-emitting diodes based on perovskite quantum dot/conjugated polymer

Inorganic organic metal halide perovskite materials have been investigated for several technological applications, such as photovoltaic cells, lasers, photodetectors and light emitting diodes (LEDs), either in the bulk form or as colloidal nanoparticles. Recently, all inorganic Cesium Lead Halide (CsPbX3, X=Cl,Br, I) perovskite quantum dots (PQDs) were reported with high photoluminescence quantum yield with narrow emission lines in the visible wavelengths. Here, green-emitting perovskite quantum dots (PQDs) prepared by a synthetic method based on a mixture of oleylamine and oleic acid as surfactants were applied in the electroluminescent layer of hybrid LEDs in combination with two different conjugated polymers: polyvinylcarbazole (PVK) or poly(9,9-di-n-octylfluorenyl-2,7-diyl) (PFO). The performance of the diodes and the emission color tuning upon dispersion of different concentrations of the PQDs in the polymer matrix is discussed. The presented approach aims at the combination of the optical properties of the PQDs and their interaction with wide bandgap conjugated polymers, associated with the solution processing ability of these materials.

Surface passivated colloidal CuIn(S,Se)2 quantum dots for quantum dot heterojunction solar cells (Presentation Recording)

Colloidal quantum dot heterojunction thin film solar cells (CQD-TFSC) utilize facile thin film deposition methods and promise high photon conversion efficiencies (PCE) to cost ratio which is highly desired for commercialization. So far, surface passivated PbS CQD-TFSCs show the highest PCE results, reaching 9.2% with good stability. Among other potential candidates, CuInSe2 CQDs stand out as a non-toxic material with high potential for performance, judging on bulk Cu(Ga,In)(S,Se)2 TFSCs reaching 20% PCE, with high stability. CuInSe2 CQDs has advantage over bulk films, mainly the much less expensive manufacturing cost of uniform deposition on large areas. Ga is known to cause phase separation in the bulk CIGS system. In a CQD form, CuInSe2 band gap can be tuned between 1 to 1.6 eV by quantum confinement without need for Ga and this eliminates the phase separation issue. Within our best knowledge, there are no reports on surface trap passivated CuInSe2 CQD-TFSCs. However Cu(In,Ga)(S,Se)2 colloidal particles were cast in thin film form and fused to form bulk-like crystals by various annealing conditions for solar cell devices. In this work, we investigated well-passivated CuInSe2 CQDs on n-type TiO2 and ZnO layers to form depleted heterojunction structure. We prepared luminescent CuInSe2 CQDs by synthetic wet chemistry methods and passivated the surface with 3-mercaptopropionic acid or tetrabutylammonium iodide using solid-state ligand exchange. X-ray photoelectron spectroscopy was used to confirm the ligand boding and surface coverage of the quantum dots. We will present the effect of synthesis and thin film preparation conditions on the solar cell device performance