Tuning the Optical Absorption Edge of Vacancy-Ordered Double Perovskites through Metal Precursor and Solvent Selection.

Vacancy-ordered double perovskites with the formula (where is a +1 cation, is a +4 metal, and is a halide ion) offer improved ambient stability over other main-group halide perovskites and potentially reduced toxicity compared to those containing lead. These compounds are readily formed through a number of synthetic routes; however, the manner in which the synthetic route affects the resulting structure or optoelectronic properties has not been examined. Here, we investigate the role of distinct precursors and solvents in the formation of the indirect band gap vacancy-ordered double perovskite CsTeBr.

Molecular Origins of Near-Infrared Luminescence in Molybdenum and Tungsten Oxyhalide Perovskites.

Materials with near-infrared (near-IR) luminescence are desirable for applications in communications and sensing, as well as biomedical diagnostics and imaging. The most used inorganic near-IR emitters rely on precise doping of host crystal structures with select rare-earth or transition metal ions. Recently, another class of materials with intrinsic near-IR emission has been reported.

Hybrid Iodide Perovskites of Divalent Alkaline Earth and Lanthanide Elements.

Hybrid halide perovskites AMX (A = ammonium cation, M = divalent cation, X = Cl, Br, I) have been extensively studied but have only previously been reported for the divalent carbon group elements Ge, Sn, and Pb. While they have displayed an impressive range of optoelectronic properties, the instability of Ge and Sn and the toxicity of Pb have stimulated significant interest in finding alternatives to these carbon group-based perovskites. Here, we describe the low-temperature solid-state synthesis of five new hybrid iodide perovskites centered around divalent alkaline earth and lanthanide elements, with the general formula AMI (A = methylammonium, MA; M = Sr, Sm, Eu, and A = formamidinium, FA; M = Sr, Eu).

Time-resolved radioluminescence of the Cu(I) cluster CuI. Different responses to photo, X-ray, β-ray and α-particle excitation.

Time-resolved radioluminescence (TRRL) properties of the Cu(I) cluster CuI upon pulsed X-ray, β-ray or α-particle excitation are described. The longer (>2 μs) TRRL component displays exponential decay comparable to pulsed UV excitation; however, temporal behaviour at shorter times indicates that high local excited state density provides an alternative decay channel.

Photoswitchable Conjugated Oligoelectrolytes for a Light-Induced Change of Membrane Morphology.

The synthesis of a new conjugated oligoelectrolyte (COE), namely DSAzB, is described, which contains a conjugated core bearing a diazene moiety in the center of its electronically delocalized structure. Similar to structurally related phenylenevinylene-based COEs, DSAzB readily intercalates into model and natural lipid bilayer membranes. Photoinduced isomerization transforms the linear trans COE into a bent or C-shape form.

Widely Tunable Infrared Antennas Using Free Carrier Refraction.

We demonstrate tuning of infrared Mie resonances by varying the carrier concentration in doped semiconductor antennas. We fabricate spherical silicon and germanium particles of varying sizes and doping concentrations. Single-particle infrared spectra reveal electric and magnetic dipole, quadrupole, and hexapole resonances.

Data-driven discovery of energy materials: efficient BaM2Si3O10 : Eu2+ (M = Sc, Lu) phosphors for application in solid state white lighting.

In developing phosphors for application in solid state lighting, it is advantageous to target structures from databases with highly condensed polyhedral networks that produce rigid host compounds. Rigidity limits channels for non-radiative decay that will decrease the luminescence quantum yield. BaM(2)Si(3)O(10) (M = Sc, Lu) follows this design criterion and is studied here as an efficient Eu(2+)-based phosphor.

Mapping orientational order in a bulk heterojunction solar cell with polarization-dependent photoconductive atomic force microscopy.

New methods connecting molecular structure, self-organization, and optoelectronic performance are important for understanding the current generation of organic photovoltaic (OPV) materials. In high power conversion efficiency (PCE) OPVs, light-harvesting small-molecules or polymers are typically blended with fullerene derivatives and deposited in thin films, forming a bulk heterojunction (BHJ), a self-assembled three-dimensional nanostructure of electron donors and acceptors that separates and transports charges. Recent data suggest micrometer-scale orientational order of donor domains exists within this complex nanomorphology, but the link to the optoelectronic properties is yet unexplored.

Nitric oxide releasing materials triggered by near-infrared excitation through tissue filters.

Novel materials for the phototherapeutic release of the bioregulator nitric oxide (nitrogen monoxide) are described. Also reported is a method for scanning these materials with a focused NIR beam to induce photouncaging while minimizing damage from local heating. The new materials consist of poly(dimethylsiloxane) composites with near-infrared-to-visible upconverting nanoparticles (UCNPs) that are cast into a biocompatible polymer disk (PD).

Average and local structural origins of the optical properties of the nitride phosphor La(3-x)Ce(x)Si6N11 (0 < x ≤ 3).

Structural intricacies of the orange-red nitride phosphor system La(3-x)Ce(x)Si6N11 (0 < x ≤ 3) have been elucidated using a combination of state-of-the art tools, in order to understand the origins of the exceptional optical properties of this important solid-state lighting material. In addition, the optical properties of the end-member (x = 3) compound, Ce3Si6N11, are described for the first time. A combination of synchrotron powder X-ray diffraction and neutron scattering is employed to establish site preferences and the rigid nature of the structure, which is characterized by a high Debye temperature.

All-conjugated triblock polyelectrolytes.

All-conjugated triblock polyfluorenes with well-defined molecular weights and low polydispersities are synthesized via chain-growth Suzuki-Miyaura polymerization. Ionization of pendant alkylbromide chains by pyridine affords amphiphilic triblock polyelectrolytes with neutral/charged/neutral or charged/neutral/charged segments. The immiscible blocks lead to aggregation in polar and nonpolar solvents, and to complex surface morphologies depending on the polarity of the substrate.

Quantum dot photoluminescence quenching by Cr(III) complexes. Photosensitized reactions and evidence for a FRET mechanism.

Reported are quantitative studies of the energy transfer from water-soluble CdSe/ZnS and CdSeS/ZnS core/shell quantum dots (QDs) to the Cr(III) complexes trans-Cr(N(4))(X)(2)(+) (N(4) is a tetraazamacrocycle ligand, X(-) is CN(-), Cl(-), or ONO(-)) in aqueous solution. Variation of N(4), of X(-), and of the QD size and composition allows one to probe the relationship between the emission/absorption overlap integral parameter and the efficiency of the quenching of the QD photoluminescence (PL) by the chromium(III) complexes. Steady-state studies of the QD PL in the presence of different concentrations of trans-Cr(N(4))(X)(2)(+) indicate a clear correlation between quenching efficiency and the overlap integral largely consistent with the predicted behavior of a Förster resonance energy transfer (FRET)-type mechanism.

Towards enhanced ligand-centred photoluminescence in inorganic-organic frameworks for solid state lighting.

Three novel inorganic-organic framework compounds containing the organic chromophore ligand 9-fluorenone-2,7-dicarboxylic acid (abbreviated H(2)FDC) and barium (BaFDC), cadmium (CdFDC) and manganese (MnFDC), respectively, have been synthesized and evaluated for their use as phosphor materials for solid state lighting and other applications. The results are compared with two earlier reported structures containing the same ligand with calcium (CaFDC) and strontium (SrFDC). The barium- and cadmium-containing compounds both show blue excited, yellow photoluminescence, while the manganese structure does not.

One- and two-photon induced polymerization of methylmethacrylate using colloidal CdS semiconductor quantum dots.

The development of one- and two-photon induced polymerization using CdS semiconductor quantum dots (QDs) and amine co-initiators to promote radical generation and subsequent polymerization is presented. Two-photon absorption (TPA) cross-section measurements, linear absorption, and transmission electron microscopy are used to characterize the QDs. The effectiveness of the co-initiators in increasing the efficiency of photopolymerization (polymer chains formed per excitation) is examined.

Quantum dot fluorescence quenching pathways with Cr(III) complexes. photosensitized NO production from trans-Cr(cyclam)(ONO)2+.

Described is the photoluminescence (PL) of water-soluble CdSe/ZnS core/shell quantum dots (QDs) as perturbed by salts of the chromium(III) complexes trans-Cr(cyclam)Cl2+ (1), trans-Cr(cyclam)(ONO)2+ (2), and trans-Cr(cyclam)(CN)2+ (3) (cyclam = 1,4,8,11-tetraazacyclo-tetradecane). The purpose is to probe the characteristics of such QDs as antennae for photosensitized release of bioactive agents (in the present case, the bioregulatory molecule NO) from transition metal centers. Addition of 1 or 2 to a QD solution results in concentration-dependent quenching of the band edge emission, but 3 has a minimal effect.

Broadband near-field interference spectroscopy of metal nanoparticles using a femtosecond white-light continuum.

We demonstrate a new nanoscale spectroscopic technique that combines subwavelength near-field imaging with broadband interference spectroscopy. We apply this technique to study phase spectra of surface plasmons in individual gold nanoparticles and nanoparticle dimers. Collective plasmon oscillations in selected nanostructures are excited by a femtosecond white-light continuum transmitted through a subwavelength aperture.

Optical gain and stimulated emission in nanocrystal quantum dots.

The development of optical gain in chemically synthesized semiconductor nanoparticles (nanocrystal quantum dots) has been intensely studied as the first step toward nanocrystal quantum dot lasers. We examined the competing dynamical processes involved in optical amplification and lasing in nanocrystal quantum dots and found that, despite a highly efficient intrinsic nonradiative Auger recombination, large optical gain can be developed at the wavelength of the emitting transition for close-packed solids of these dots. Narrowband stimulated emission with a pronounced gain threshold at wavelengths tunable with the size of the nanocrystal was observed, as expected from quantum confinement effects.

Quantization of multiparticle auger rates in semiconductor quantum dots.

We have resolved single-exponential relaxation dynamics of the 2-, 3-, and 4-electron-hole pair states in nearly monodisperse cadmium selenide quantum dots with radii ranging from 1 to 4 nanometers. Comparison of the discrete relaxation constants measured for different multiple-pair states indicates that the carrier decay rate is cubic in carrier concentration, which is characteristic of an Auger process. We observe that in the quantum-confined regime, the Auger constant is strongly size-dependent and decreases with decreasing the quantum dot size as the radius cubed.