Tailoring p-Type Behavior in ZnO Quantum Dots through Enhanced Sol-Gel Synthesis: Mechanistic Insights into Zinc Vacancies.

The synthesis and control of properties of p-type ZnO is crucial for a variety of optoelectronic and spintronic applications; however, it remains challenging due to the control of intrinsic midgap (defect) states. In this study, we demonstrate a synthetic route to yield colloidal ZnO quantum dots (QD) via an enhanced sol-gel process that effectively eliminates the residual intermediate reaction molecules, which would otherwise weaken the excitonic emission. This process supports the creation of ZnO with p-type properties or compensation of inherited n-type defects, primarily due to zinc vacancies under oxygen-rich conditions.

Early bird or night owl? Controlling the ultrafast photodynamics of triphenylamine substituted 2,2':6',2''-terpyridine.

Controlling the ultrafast photodynamics of metal-free organic molecules has great potential for technological applications. In this work, we use solvent polarity and viscosity as "external knobs" to govern the photodynamics of an electron-donating derivative of 2,2':6',2''-terpyridine (terpy), namely 4'-(4-(di(4--butylphenyl)amine)phenyl)-2,2':6',2''-terpyridine (tBuTPAterpy). We combine femtosecond fluorescence upconversion (FlUC), transient absorption (TA) and quantum mechanical calculations to provide a comprehensive description of the tBuTPAterpy's photodynamics.

Photogenerated charge transfer in Dion-Jacobson type layered perovskite based on naphthalene diimide.

Incorporating organic semiconducting spacer cations into layered lead halide perovskite structures provides a powerful approach to mitigate the typical strong dielectric and quantum confinement effects by inducing charge-transfer between the organic and inorganic layers. Herein we report the synthesis and characterization of thin films of novel DJ-phase organic-inorganic layered perovskite semiconductors using a naphthalene diimide (NDI) based divalent spacer cation, which is shown to accept photogenerated electrons from the inorganic layer. With alkyl chain lengths of 6 carbons, an NDI-based thin film exhibited electron mobility (based on space charge-limited current for quasi-layered 〈〉 = 5 material) was found to be as high as 0.

Perturbed free induction decay obscures early time dynamics in two-dimensional electronic spectroscopy: The case of semiconductor nanocrystals.

Two-dimensional electronic spectroscopy (2DES) has recently been gaining popularity as an alternative to the more common transient absorption spectroscopy due to the combination of high frequency and time resolution of 2DES. In order to advance the reliable analysis of population dynamics and to optimize the time resolution of the method, one has to understand the numerous field matter interactions that take place at an early and negative time. These interactions have historically been discussed in one-dimensional spectroscopy as coherent artifacts and have been assigned to both resonant and non-resonant system responses during or before the pulse overlap.

Push-Pull Effect of Terpyridine Substituted by Triphenylamine Motive-Impact of Viscosity, Polarity and Protonation on Molecular Optical Properties.

The introduction of an electron-donating triphenylamine motive into a 2,2',6',2''-terpyridine (terpy) moiety, a cornerstone molecular unit in coordination chemistry, opens new ways for a rational design of photophysical properties of organic and inorganic compounds. A push-pull compound, 4'-(4-(di(4-tert-butylphenyl)amine)phenyl)-2,2',6',2''-terpyridine (tBuTPAterpy), was thoroughly investigated with the use of steady-state and time-resolved spectroscopies and Density Functional Theory (DFT) calculations. Our results demonstrate that solvent parameters have an enormous influence on the optical properties of this molecule, acting as knobs for external control of its photophysics.

A molecular photosensitizer achieves a V of 1.24 V enabling highly efficient and stable dye-sensitized solar cells with copper(II/I)-based electrolyte.

To develop photosensitizers with high open-circuit photovoltage (V) is a crucial strategy to enhance the power conversion efficiency (PCE) of co-sensitized solar cells. Here, we show a judiciously tailored organic photosensitizer, coded MS5, featuring the bulky donor N-(2',4'-bis(dodecyloxy)-[1,1'-biphenyl]-4-yl)-2',4'-bis(dodecyloxy)-N-phenyl-[1,1'-biphenyl]-4-amine and the electron acceptor 4-(benzo[c][1,2,5]thiadiazol-4-yl)benzoic acid. Employing MS5 with a copper (II/I) electrolyte enables a dye-sensitized solar cell (DSC) to achieve a strikingly high V of 1.

Exciton and Carrier Dynamics in Two-Dimensional Perovskites.

Two-dimensional Ruddlesden-Popper hybrid lead halide perovskites have become a major topic in perovskite optoelectronics. Here, we aim to unravel the ultrafast dynamics governing the evolution of charge carriers and excitons in these materials. Using a combination of ultrabroadband time-resolved THz (TRTS) and fluorescence upconversion spectroscopies, we find that sequential carrier cooling and exciton formation best explain the observed dynamics, while exciton-exciton interactions play an important role in the form of Auger heating and biexciton formation.

Enhanced Intersystem Crossing and Transient Electron Spin Polarization in a Photoexcited Pentacene-Trityl Radical.

Identifying and characterizing systems that generate well-defined states with large electron spin polarization is of high interest for applications in molecular spintronics, high-energy physics, and magnetic resonance spectroscopy. The generation of electron spin polarization on free-radical substituents tethered to pentacene derivatives has recently gained a great deal of interest for its applications in molecular electronics. After photoexcitation of the chromophore, pentacene-radical derivatives can rapidly form spin-polarized triplet excited states through enhanced intersystem crossing.

Phenanthrene-Fused-Quinoxaline as a Key Building Block for Highly Efficient and Stable Sensitizers in Copper-Electrolyte-Based Dye-Sensitized Solar Cells.

Dye-sensitized solar cells (DSSCs) based on Cu bipyridyl or phenanthroline complexes as redox shuttles have achieved very high open-circuit voltages (V , more than 1 V). However, their short-circuit photocurrent density (J ) has remained modest. Increasing the J is expected to extend the spectral response of sensitizers to the red or NIR region while maintaining efficient electron injection in the mesoscopic TiO film and fast regeneration by the Cu complex.

Exciton, Biexciton, and Hot Exciton Dynamics in CsPbBr Colloidal Nanoplatelets.

Lead halide perovskites have emerged as promising materials for light-emitting devices. Here, we report the preparation of colloidal CsPbBr nanoplatelets (3 × 4 × 23 nm) experiencing a strong quasi-one-dimensional quantum confinement. Ultrafast transient absorption and broadband fluorescence up-conversion spectroscopies were employed to scrutinize the carrier and quasiparticle dynamics and to obtain a full description of the spectroscopic properties of the material.

Two-dimensional electronic spectroscopy reveals liquid-like lineshape dynamics in CsPbI perovskite nanocrystals.

Lead-halide perovskites have attracted tremendous attention, initially for their performance in thin film photovoltaics, and more recently for a variety of remarkable optical properties. Defect tolerance through polaron formation within the ionic lattice is a key aspect of these materials. Polaron formation arises from the dynamical coupling of atomic fluctuations to electronic states.