Photoluminescence Switching in Quantum Dots Connected with Carboxylic Acid and Thiocarboxylic Acid End-Group Diarylethene Molecules.

We contrast the switching of photoluminescence (PL) of PbS quantum dots (QDs) cross-linked with photochromic diarylethene molecules with different end groups, 4,4'-(1-cyclopentene-1,2-diyl)bis[5-methyl-2-thiophenecarboxylic acid] () and 4,4'-(1-cyclopentene-1,2-diyl)bis[5-methyl-2-thiophenethiocarboxylic acid] (). Our results show that the QDs cross-linked with the carboxylic acid end group molecules () exhibit a greater amount of switching in photoluminescence intensity compared to QDs cross-linked with the thiocarboxylic acid end group (). We also demonstrate that regardless of the molecule used, greater switching amounts are observed for smaller quantum dots.

Synthesis of Bis-Thioacid Derivatives of Diarylethene and Their Photochromic Properties.

Diarylethenes (DAEs) are an important class of photoswitchable compounds that typically undergo reversible photochemical conversions between the open and closed cyclized forms upon treatment with UV light or visible light. In this study, we introduced thioacid functional groups to several photochromic dithienylethene (DTE) derivatives and established a method that can be used to prepare these photoswitchable thioacids. Four thioacid-functionalized diarylethene derivatives were synthesized through the activation of carboxylic acids with -hydroxysuccinimide, followed by reactions with sodium hydrosulfide with yields over 90%.

Photoluminescence switching in quantum dots connected with fluorinated and hydrogenated photochromic molecules.

We investigate switching of photoluminescence (PL) from PbS quantum dots (QDs) crosslinked with two different types of photochromic diarylethene molecules, 4,4'-(1-cyclopentene-1,2-diyl)bis[5-methyl-2-thiophenecarboxylic acid] (1H) and 4,4'-(1-perfluorocyclopentene-1,2-diyl)bis[5-methyl-2-thiophenecarboxylic acid] (2F). Our results show that the QDs crosslinked with the hydrogenated molecule (1H) exhibit a greater amount of switching in photoluminescence intensity compared to QDs crosslinked with the fluorinated molecule (2F). With a combination of differential pulse voltammetry and density functional theory, we attribute the different amount of PL switching to the different energy levels between 1H and 2F molecules which result in different potential barrier heights across adjacent QDs.

Ytterbium-Doped Cesium Lead Chloride Perovskite as an X-ray Scintillator with High Light Yield.

Ytterbium-doped cesium lead halides are quantum cutting materials with exceptionally high photoluminescence quantum yields, making them promising materials as scintillators. In this work, we report ytterbium-doped cesium lead chloride (Yb:CsPbCl) with an X-ray scintillation light yield of 102,000 photons/MeV at room temperature, which is brighter than the current state-of-the-art commercial scintillators. The high light yield was achieved based on a novel method of synthesizing Yb:CsPbCl powders using water and low-temperature processing.

Organic molecular dynamics and charge-carrier lifetime in lead iodide perovskite MAPbI.

The long charge carrier lifetime of the hybrid organic-inorganic perovskites (HOIPs) is the key for their remarkable performance as a solar cell material. The microscopic mechanism for the long lifetime is still in debate. Here, by using a muon spin relaxation technique that probes the fluctuation of local magnetic fields, we show that the muon depolarization rate (Δ) of a prototype HOIP methylammonium lead iodide (MAPbI) shows a sharp decrease with increasing temperature in two steps above 120 K and 190 K across the structural transition from orthorhombic to tetragonal structure at 162 K.

Ultralow Thermal Conductivity of Two-Dimensional Metal Halide Perovskites.

We report on the thermal conductivities of two-dimensional metal halide perovskite films measured by time domain thermoreflectance. Depending on the molecular substructure of ammonium cations and owing to the weaker interactions in the layered structures, the thermal conductivities of our two-dimensional hybrid perovskites range from 0.10 to 0.

Crystal structures and rotational dynamics of a two-dimensional metal halide perovskite (OA)PbI.

The extended charge carrier lifetime in metal halide perovskites is responsible for their excellent optoelectronic properties. Recent studies indicate that the superb device performance in these materials is intimately related to the organic cation dynamics. Here, we focus on the investigation of the two-dimensional hybrid perovskite, (CHNH)PbI (henceforth, OA = CHNH ).

Crystallization of high aspect ratio HKUST-1 thin films in nanoconfined channels for selective small molecule uptake.

We present the ability to create unique morphologies of a prototypical metal organic framework (MOF), HKUST-1, by carrying out its crystallization within a set of nano-confined fluidic channels. These channels are fabricated on cyclic olefin copolymer by the high-fidelity hot embossing imprinting method. The picoliter volume synthesis in the nanochannels is hypothesized to bias the balance between nucleation and growth rates to obtain high aspect ratio large-crystalline domains of HKUST-1, which are grown in defined morphologies due to the patterned nanochannels.

Laser Annealing of TiO Electron-Transporting Layer in Perovskite Solar Cells.

Solution-processed TiO and other metal-oxide electron-transporting layers (ETLs) for perovskite solar cells commonly require high-temperature annealing (>450 °C), causing the underlying indium-tin oxide (ITO) to degrade and inhibiting the use of flexible plastic substrates, such as poly(ethylene naphthalate). Laser-based solar cell manufacturing is attracting increased interest and can enable rapid and low-temperature fabrication of perovskite solar cells. By using novel pulsed ultraviolet laser processing on the solution-processed TiO, we demonstrate a champion 17.

Impact of Crystallographic Orientation Disorders on Electronic Heterogeneities in Metal Halide Perovskite Thin Films.

Metal halide perovskite thin films have achieved remarkable performance in optoelectronic devices but suffer from spatial heterogeneity in their electronic properties. To achieve higher device performance and reliability needed for widespread commercial deployment, spatial heterogeneity of optoelectronic properties in the perovskite thin film needs to be understood and controlled. Clear identification of the causes underlying this heterogeneity, most importantly the spatial heterogeneity in charge trapping behavior, has remained elusive.

Origin of vertical orientation in two-dimensional metal halide perovskites and its effect on photovoltaic performance.

Thin films based on two-dimensional metal halide perovskites have achieved exceptional performance and stability in numerous optoelectronic device applications. Simple solution processing of the 2D perovskite provides opportunities for manufacturing devices at drastically lower cost compared to current commercial technologies. A key to high device performance is to align the 2D perovskite layers, during the solution processing, vertical to the electrodes to achieve efficient charge transport.

Origin of long lifetime of band-edge charge carriers in organic-inorganic lead iodide perovskites.

Long carrier lifetime is what makes hybrid organic-inorganic perovskites high-performance photovoltaic materials. Several microscopic mechanisms behind the unusually long carrier lifetime have been proposed, such as formation of large polarons, Rashba effect, ferroelectric domains, and photon recycling. Here, we show that the screening of band-edge charge carriers by rotation of organic cation molecules can be a major contribution to the prolonged carrier lifetime.

Room-Temperature Processing of TiO Electron Transporting Layer for Perovskite Solar Cells.

In order to realize high-throughput roll-to-roll manufacturing of flexible perovskite solar cells, low-temperature processing of all device components must be realized. However, the most commonly used electron transporting layer in high-performance perovskite solar cells is based on TiO thin films processed at high temperature (>450 °C). Here, we demonstrate room temperature solution processing of the TiO layer that performs as well as the high temperature TiO layer in perovskite solar cells, as evidenced by a champion solar cell efficiency of 16.

Entropy-driven structural transition and kinetic trapping in formamidinium lead iodide perovskite.

A challenge of hybrid perovskite solar cells is device instability, which calls for an understanding of the perovskite structural stability and phase transitions. Using neutron diffraction and first-principles calculations on formamidinium lead iodide (FAPbI), we show that the entropy contribution to the Gibbs free energy caused by isotropic rotations of the FA cation plays a crucial role in the cubic-to-hexagonal structural phase transition. Furthermore, we observe that the cubic-to-hexagonal phase transition exhibits a large thermal hysteresis.

Nature of the cubic to tetragonal phase transition in methylammonium lead iodide perovskite.

Hybrid organic-inorganic perovskites, as well as the perovskites in general, are known for their phase complexity evidenced by the stabilization of different polymorphs, and thus an understanding of their regions of stability and transitions can be important for their photovoltaic and optoelectronic technologies. Here we use a multiscale approach based on first-principles calculations with van der Waals corrections and classical force-field molecular dynamics to determine the finite-temperature properties of the tetragonal and cubic phases of CHNHPbI. Temperature effects are implicitly included using the quasi-harmonic approximation that can describe anharmonic behavior due to thermal expansion through the dependence of the harmonic frequencies on structural parameters.

Rotational dynamics of organic cations in the CH3NH3PbI3 perovskite.

Methylammonium lead iodide (CH3NH3PbI3) based solar cells have shown impressive power conversion efficiencies of above 20%. However, the microscopic mechanism of the high photovoltaic performance is yet to be fully understood. Particularly, the dynamics of CH3NH3(+) cations and their impact on relevant processes such as charge recombination and exciton dissociation are still poorly understood.

Heterojunction PbS nanocrystal solar cells with oxide charge-transport layers.

Oxides are commonly employed as electron-transport layers in optoelectronic devices based on semiconductor nanocrystals, but are relatively rare as hole-transport layers. We report studies of NiO hole-transport layers in PbS nanocrystal photovoltaic structures. Transient fluorescence experiments are used to verify the relevant energy levels for hole transfer.

Structure of methylammonium lead iodide within mesoporous titanium dioxide: active material in high-performance perovskite solar cells.

We report the structure of methylammonium lead(II) iodide perovskite in mesoporous TiO2, as used in high-performance solar cells. Pair distribution function analysis of X-ray scattering reveals a two component nanostructure: one component with medium range crystalline order (30 atom %) and another with only local structural coherence (70 atom %). The nanostructuring correlates with a blueshift of the absorption onset and increases the photoluminescence.

A hot electron-hole pair breaks the symmetry of a semiconductor quantum dot.

The best-understood property of semiconductor quantum dots (QDs) is the size-dependent optical transition energies due to the quantization of charge carriers near the band edges. In contrast, much less is known about the nature of hot electron-hole pairs resulting from optical excitation significantly above the bandgap. Here, we show a transient Stark effect imposed by a hot electron-hole pair on optical transitions in PbSe QDs.

Ligand exchange and the stoichiometry of metal chalcogenide nanocrystals: spectroscopic observation of facile metal-carboxylate displacement and binding.

We demonstrate that metal carboxylate complexes (L-M(O2CR)2, R = oleyl, tetradecyl, M = Cd, Pb) are readily displaced from carboxylate-terminated ME nanocrystals (ME = CdSe, CdS, PbSe, PbS) by various Lewis bases (L = tri-n-butylamine, tetrahydrofuran, tetradecanol, N,N-dimethyl-n-butylamine, tri-n-butylphosphine, N,N,N',N'-tetramethylbutylene-1,4-diamine, pyridine, N,N,N',N'-tetramethylethylene-1,2-diamine, n-octylamine). The relative displacement potency is measured by (1)H NMR spectroscopy and depends most strongly on geometric factors such as sterics and chelation, although also on the hard/soft match with the cadmium ion. The results suggest that ligands displace L-M(O2CR)2 by cooperatively complexing the displaced metal ion as well as the nanocrystal.

Interface-induced nucleation, orientational alignment and symmetry transformations in nanocube superlattices.

The self-assembly of colloidal nanocrystals into ordered superstructures depends critically on the shape of the nanocrystal building blocks. We investigated the self-assembly of cubic PbSe nanocrystals from colloidal suspensions in real-time using in situ synchrotron-based X-ray scattering. We combined small-angle and wide-angle scattering to investigate the translational ordering of nanocrystals and their orientational ordering in the lattice sites, respectively.

Bright infrared quantum-dot light-emitting diodes through inter-dot spacing control.

Infrared light-emitting diodes are currently fabricated from direct-gap semiconductors using epitaxy, which makes them expensive and difficult to integrate with other materials. Light-emitting diodes based on colloidal semiconductor quantum dots, on the other hand, can be solution-processed at low cost, and can be directly integrated with silicon. However, so far, exciton dissociation and recombination have not been well controlled in these devices, and this has limited their performance.

Predicting nanocrystal shape through consideration of surface-ligand interactions.

Density functional calculations for the binding energy of oleic acid-based ligands on Pb-rich {100} and {111} facets of PbSe nanocrystals determine the surface energies as a function of ligand coverage. Oleic acid is expected to bind to the nanocrystal surface in the form of lead oleate. The Wulff construction predicts the thermodynamic equilibrium shape of the PbSe nanocrystals.

Pulsed laser annealing of thin films of self-assembled nanocrystals.

We investigated how pulsed laser annealing can be applied to process thin films of colloidal nanocrystals (NCs) into interconnected nanostructures. We illustrate the relationship between incident laser fluence and changes in morphology of PbSe NC films relative to bulk-like PbSe films. We found that laser pulse fluences in the range of 30 to 200 mJ/cm(2) create a processing window of opportunity where the NC film morphology goes through interesting transformations without large-scale coalescence of the NCs.