Luminescent solar concentrators doped with CdSe/CdS quantum dots provide a potentially low-cost and high-performance alternative to costly highband-gap III−V semiconductor materials to serve as a top junction in multijunction photovoltaic devices for efficient utilization of blue photons. In this study, a photonic mirror was coupled with such a luminescent waveguide to form an optical cavity where emitted luminescence was trapped omnidirectionally. By mitigating escape cone and scattering losses, 82% of luminesced photons travel the length of the waveguide, creating a concentration ratio of 30.3 for blue photons in a waveguide with a geometric gain of 61. Further, we study the photon transport inside the luminescent waveguide, showing unimpeded photon collection across the entire length of the waveguide. L uminescent solar concentrators 1−4 (LSCs) have been studied extensively for the last three decades as low-cost alternatives to single-and multijunction photovoltaic (PV) devices. As silicon prices have fallen, it has become increasingly clear that future solar panels will need to have both low cost and high efficiency. One promising strategy for achieving a higher efficiency is to use different parts of the solar spectrum in photovoltaic materials with varying band gaps to minimize losses associated with carrier thermalization and incomplete photon absorption. For these multijunction (MJ) PV devices, there is a strong need for developing low-cost, high-band-gap solar cells for efficient utilization of the high-energy part of the solar spectrum. A luminescent solar concentrator could provide exactly this function, serving as the top junction in a multijunction architecture by converting blue photons into guided luminescence. Due to the concentration effect, only small amounts of high-performing but expensive III−V photovoltaic materials are needed to collect the light from an inexpensive luminescent waveguide. Such a device requires high concentration factors to reduce the cost of the III−V photovoltaic material. High concentration also allows the Stokes shift of the lumophore to be recovered in the operating voltage of the photovoltaic cell.The concentration factor and collection efficiency achieved by LSCs to date have been limited due to parasitic losses such as nonunity quantum yields of the lumophores, imperfect light trapping within the waveguide, and reabsorption and scattering of propagating photons. 5 Previous studies have sought to solve each of these parasitic losses individually, resulting in modest performance improvements. 6−15 Here we achieve a luminescent concentration ratio greater than 30 with an optical efficiency of 82% for blue photons by simultaneously addressing the materials and optical challenges of the LSC system. These concentration ratios are achieved through the combination of designer quantum dot lumophores and photonic mirrors, and microscale silicon photovoltaic cells are used to detect the concentration of light in the waveguide. To the best of our knowledge, this is the highest ...

Quantum dot surfaces can have a substantial effect on their physical, chemical, and optoelectronic properties. When the chemistry that occurs at the surface of nanocrystals is studied, critical insights can be gained into the fundamental structural, thermodynamic, and optical properties of quantum dot materials providing a valuable guide for how to best adapt them for desired applications. Colloidal quantum dots are often terminated with organic ligands that consist of a long aliphatic chain and a head group that binds tightly to the nanocrystal surface. While extensive work has been done to understand how ligand head groups influence quantum dot properties, studies to unravel the influence of the organic ligand tail on ligands and surface reaction equilibria are incomplete. To further investigate the driving forces of quantum dot surface modification, a series of ligand exchange reactions with oleic acid were performed on indium phosphide quantum dots, initially terminated with straight-chain carboxylates of variable lengths. The reaction was monitored using isothermal titration calorimetry and 1H NMR to determine the extent of each reaction and its associated thermodynamics. From these measurements, interligand interactions were observed to be dependent on the length of the straight-chain ligand. A modified Ising model was used to investigate the enthalpic and entropic effects contributing to these ligand exchanges and reveal that interligand interactions play a much larger role than previously thought. Additional experimentation with phosphonic acid ligand exchange reveals complexity in the reaction mechanism but further illustrates the significant impact of ligand tail group length on thermodynamics, even in cases where there is a large difference in head group binding energy.

A phase transition within the ligand shell of core/shell quantum dots is studied in the prototypical system of colloidal CdSe/CdS quantum dots with a ligand shell composed of bound oleate (OA) and octadecylphosphonate (ODPA). The ligand shell composition is tuned using a ligand exchange procedure and quantified through proton NMR spectroscopy. Temperaturedependent photoluminescence spectroscopy reveals a signature of a phase transition within the organic ligand shell. Surprisingly, the ligand order to disorder phase transition triggers an abrupt increase in the photoluminescence quantum yield (PLQY) and full-width at half maximum (FWHM) with increasing temperature. The temperature and width of the phase transition shows a clear dependence on ligand shell composition, such that QDs with higher ODPA fractions have sharper phase transitions that occur at higher temperatures. In order to gain a molecular understanding of the changes in ligand ordering, fourier-transform infrared and vibrational sum frequency generation spectroscopies are performed. These measurements confirm that an order/disorder transition in the ligand shell tracks with the photoluminescence changes that accompany the order disorder ligand phase transition. The phase transition is simulated through a lattice model that suggests that the ligand shell is well-mixed, and does not 1 have completely segregated domains of OA and ODPA. Furthermore, we show that the unsaturated chains of OA seed disorder within the ligand shell.