Core/Shell Quantum Dot Based Luminescent Solar Concentrators with Reduced Reabsorption and Enhanced Efficiency

CdSe/CdS core/shell quantum dots (QDs) have been optimized toward luminescent solar concentration (LSC) applications. Systematically increasing the shell thickness continuously reduced reabsorption up to a factor of 45 for the thickest QDs studied (with ca. 14 monolayers of CdS) compared to the initial CdSe cores. Moreover, an improved synthetic method was developed that retains a high-fluorescence quantum yield, even for particles with the thickest shell volume, for which a quantum yield of 86% was measured in solution. These high quantum yield thick shell quantum dots were embedded in a polymer matrix, yielding highly transparent composites to serve as prototype LSCs, which exhibited an optical efficiency as high as 48%. A Monte Carlo simulation was developed to model LSC performance and to identify the major loss channels for LSCs incorporating the materials developed. The results of the simulation are in excellent agreement with the experimental data

Improved Precursor Chemistry for the Synthesis of III–V Quantum Dots

The synthesis of III–V quantum dots has been long known to be more challenging than the synthesis of other types of inorganic quantum dots. This is attributed to highly reactive group-V precursors. We synthesized molecules that are suitable for use as group-V precursors and characterized their reactivity using multiple complementary techniques. We show that the size distribution of indium arsenide quantum dots indeed improves with decreased precursor reactivity

Media 1: Multispectral imaging via luminescent down-shifting with colloidal quantum dots

Originally published in Optical Materials Express on 01 August 2013 (ome-3-8-1167

Effect of Trace Water on the Growth of Indium Phosphide Quantum Dots

We report that trace amounts of water impurities in indium myristate precursors can negatively impact indium phosphide nanoparticle growth by limiting its size tunability. Without water, the growth can be effectively tuned by growth temperature and time with the first absorption peak reaching 620 nm; with water, the growth presents a “focused” behavior with the first absorption peak remaining around 550 nm. The results imply that water impurities, either from indium acetate derived indium precursors or generated in situ during nanoparticle growth, may be the cause of the currently observed inhibited growth behavior of indium phosphide quantum dots. We use multistage microfluidic reactors to show that this inhibiting effect occurs at the late stage of particle growth, following precursor depletion. We extend our study by showing that trace amounts of free hydroxide can also inhibit nanoparticle growth. We attribute the inhibited growth behavior to the hydroxylation effect of water or free hydroxide

The Dominant Role of Exciton Quenching in PbS Quantum-Dot-Based Photovoltaic Devices

We present a quantitative measurement of the number of trapped carriers combined with a measurement of exciton quenching to assess limiting mechanisms for current losses in PbS-quantum-dot-based photovoltaic devices. We use photocurrent intensity dependence and short-wave infrared transient photoluminescence and correlate these with device performance. We find that the effective density of trapped carriers ranges from 1 in 10 to 1 in 10 000 quantum dots, depending on ligand treatment, and that nonradiative exciton quenching, as opposed to recombination with trapped carriers, is likely the limiting mechanism in these devices

Imaging Schottky Barriers and Ohmic Contacts in PbS Quantum Dot Devices

We fabricated planar PbS quantum dot devices with ohmic and Schottky type electrodes and characterized them using scanning photocurrent and photovoltage microscopies. The microscopy techniques used in this investigation allow for interrogation of the lateral depletion width and related photovoltaic properties in the planar Schottky type contacts. Titanium/QD contacts exhibited depletion widths that varied over a wide range as a function of bias voltage, while the gold/QD contacts showed ohmic behavior over the same voltage range

Minority Carrier Transport in Lead Sulfide Quantum Dot Photovoltaics

Lead sulfide quantum dots (PbS QDs) are an attractive material system for the development of low-cost photovoltaics (PV) due to their ease of processing and stability in air, with certified power conversion efficiencies exceeding 11%. However, even the best PbS QD PV devices are limited by diffusive transport, as the optical absorption length exceeds the minority carrier diffusion length. Understanding minority carrier transport in these devices will therefore be critical for future efficiency improvement. We utilize cross-sectional electron beam-induced current (EBIC) microscopy and develop methodology to quantify minority carrier diffusion length in PbS QD PV devices. We show that holes are the minority carriers in tetrabutylammonium iodide (TBAI)-treated PbS QD films due to the formation of a p–n junction with an ethanedithiol (EDT)-treated QD layer, whereas a heterojunction with n-type ZnO forms a weaker n⁺–n junction. This indicates that modifying the standard device architecture to include a p-type window layer would further boost the performance of PbS QD PV devices. Furthermore, quantitative EBIC measurements yield a lower bound of 110 nm for the hole diffusion length in TBAI-treated PbS QD films, which informs design rules for planar and ordered bulk heterojunction PV devices. Finally, the low-energy EBIC approach developed in our work is generally applicable to other emerging thin-film PV absorber materials with nanoscale diffusion lengths

Measurement of Emission Lifetime Dynamics and Biexciton Emission Quantum Yield of Individual InAs Colloidal Nanocrystals

The understanding of the photophysics of visible-emitting colloidal nanocrystals (NCs) has long been aided by single-molecule studies of their emission. Until recently, no suitable detection technologies have existed for corresponding studies of shortwave-infrared (SWIR) emitters. Now, the use of superconducting nanowire single-photon detectors (SNSPDs) enables the detailed study of SWIR NC emission dynamics at the single-emitter level. Here, we report a detailed analysis of the emission dynamics of individual InAs/CdZnS NCs emitting in the SWIR region. We observe blinking akin to the type A and type B blinking previously observed in visible-emitting CdSe NCs. We determine the intrinsic radiative lifetime of several InAs/CdZnS NCs and find examples ranging from 50–200 ns, indicative of a quasi-type-II electronic structure. We also measure <i>g</i>₀⁽²⁾ for several of these NCs and find that their biexciton emission quantum yields vary from <1% up to 43%

Low-Temperature Solution-Processed Solar Cells Based on PbS Colloidal Quantum Dot/CdS Heterojunctions

PbS colloidal quantum dot heterojunction solar cells have shown significant improvements in performance, mostly based on devices that use high-temperature annealed transition metal oxides to create rectifying junctions with quantum dot thin films. Here, we demonstrate a solar cell based on the heterojunction formed between PbS colloidal quantum dot layers and CdS thin films that are deposited via a solution process at 80 °C. The resultant device, employing a 1,2-ethanedithiol ligand exchange scheme, exhibits an average power conversion efficiency of 3.5%. Through a combination of thickness-dependent current density–voltage characteristics, optical modeling, and capacitance measurements, the combined diffusion length and depletion width in the PbS quantum dot layer is found to be approximately 170 nm

Quantum-Dot Size and Thin-Film Dielectric Constant: Precision Measurement and Disparity with Simple Models

We study the dielectric constant of lead sulfide quantum dot (QD) films as a function of the volume fraction of QDs by varying the QD size and keeping the ligand constant. We create a reliable QD sizing curve using small-angle X-ray scattering (SAXS), thin-film SAXS to extract a pair-distribution function for QD spacing, and a stacked-capacitor geometry to measure the capacitance of the thin film. Our data support a reduced dielectric constant in nanoparticles