Performance of Spherical Quantum Well Down Converters in Solid State Lighting.

We report the color conversion performance of amber and red emitting quantum dots (QDs) on InGaN solid-state lighting (SSL) light emitting diode (LED) packages. Spherical quantum well (SQW) architectures (CdS/CdSe1-xSx/CdS) were prepared using a library of thio- and selenourea synthesis reagents and high throughput synthesis robotics. CdS/CdSe1-xSx QDs with narrow luminescence bands were coated with thick CdS shells (thickness = 1.6-7.5 nm) to achieve photoluminescence quantum yields (PLQY) up to 88% at amber and red emission wavelengths (λmax = 600-642 nm, FWHM < 45 nm). The photoluminescence from SQWs encapsulated in silicone and deposited on LED packages was monitored under accelerated aging conditions (oven temperature = 85 °C, relative humidity = 5-85%, blue optical power density = 3-45 W/cm2) by monitoring the red photon output over several hundred hours of continuous operation. The growth of a ZnS shell on the SQW surface increases the stability under long-term operation but also reduces the PLQY, especially of SQWs with thick CdS shells. The results illustrate that the outer ZnS shell layer is key to optimizing the PLQY and the long-term stability of QDs during operation on SSL packages.

Dynamic emission Stokes shift and liquid-like dielectric solvation of band edge carriers in lead-halide perovskites.

Lead-halide perovskites have emerged as promising materials for photovoltaic and optoelectronic applications. Their significantly anharmonic lattice motion, in contrast to conventional harmonic semiconductors, presents a conceptual challenge in understanding the genesis of their exceptional optoelectronic properties. Here we report a strongly temperature dependent luminescence Stokes shift in the electronic spectra of both hybrid and inorganic lead-bromide perovskite single crystals. This behavior stands in stark contrast to that exhibited by more conventional crystalline semiconductors. We correlate the electronic spectra with the anti-Stokes and Stokes Raman vibrational spectra. Dielectric solvation theories, originally developed for excited molecules dissolved in polar liquids, reproduce our experimental observations. Our approach, which invokes a classical Debye-like relaxation process, captures the dielectric response originating from the incipient anharmonicity of the LO phonon at about 20 meV (160 cm-1) in the lead-bromide framework. We reconcile this liquid-like model incorporating thermally-activated dielectric solvation with more standard solid-state theories of the emission Stokes shift in crystalline semiconductors.

Local Polar Fluctuations in Lead Halide Perovskite Crystals.

Hybrid lead-halide perovskites have emerged as an excellent class of photovoltaic materials. Recent reports suggest that the organic molecular cation is responsible for local polar fluctuations that inhibit carrier recombination. We combine low-frequency Raman scattering with first-principles molecular dynamics (MD) to study the fundamental nature of these local polar fluctuations. Our observations of a strong central peak in the cubic phase of both hybrid (CH_{3}NH_{3}PbBr_{3}) and all-inorganic (CsPbBr_{3}) lead-halide perovskites show that anharmonic, local polar fluctuations are intrinsic to the general lead-halide perovskite structure, and not unique to the dipolar organic cation. MD simulations indicate that head-to-head Cs motion coupled to Br face expansion, occurring on a few hundred femtosecond time scale, drives the local polar fluctuations in CsPbBr_{3}.

Unbalanced Hole and Electron Diffusion in Lead Bromide Perovskites.

We use scanning photocurrent microscopy and time-resolved microwave conductivity to measure the diffusion of holes and electrons in a series of lead bromide perovskite single crystals, APbBr3, with A = methylammonium (MA), formamidinium (FA), and Cs. We find that the diffusion length of holes (LDh+ ∼ 10-50 µm) is on average an order of magnitude longer than that of electrons (LDe- ∼ 1-5 µm), regardless of the A-type cation or applied bias. Furthermore, we observe a weak dependence of LD across the A-cation series MA > FA > Cs. When considering the role of the halide, we find that the diffusion of holes in MAPbBr3 is comparable to that in MAPbI3, but the electron diffusion length is up to five times shorter. This study shows that the disparity between hole and electron diffusion is a ubiquitous feature of lead halide perovskites. As with organic photovoltaics, this imbalance will likely become an important consideration in the optimization of lead halide perovskite solar cells.

Infrared Spectroscopic Study of Vibrational Modes in Methylammonium Lead Halide Perovskites.

The organic cation and its interplay with the inorganic lattice underlie the exceptional optoelectronic properties of organo-metallic halide perovskites. Herein we report high-quality infrared spectroscopic measurements of methylammonium lead halide perovskite (CH3NH3Pb(I/Br/Cl)3) films and single crystals at room temperature, from which the dielectric function in the investigated spectral range is derived. Comparison with electronic structure calculations in vacuum of the free methylammonium cation allows for a detailed peak assignment. We analyze the shifts of the vibrational peak positions between the different halides and infer the extent of interaction between organic moiety and the surrounding inorganic cage. The positions of the NH3(+) stretching vibrations point to significant hydrogen bonding between the methylammonium and the halides for all three perovskites.