Arthur Shapiro

Three-pulse femtosecond spectroscopy of PbSe nanocrystals: 1S bleach nonlinearity and sub-band-edge excited-state absorption assignment.

Above band-edge photoexcitation of PbSe nanocrystals induces strong below band gap absorption as well as a multiphased buildup of bleaching in the 1Se1Sh transition. The amplitudes and kinetics of these features deviate from expectations based on biexciton shifts and state filling, which are the mechanisms usually evoked to explain them. To clarify these discrepancies, the same transitions are investigated here by double-pump-probe spectroscopy. Re-exciting in the below band gap induced absorption characteristic of hot excitons is shown to produce additional excitons with high probability. In addition, pump-probe experiments on a sample saturated with single relaxed excitons prove that the resulting 1Se1Sh bleach is not linear with the number of excitons per nanocrystal. This finding holds for two samples differing significantly in size, demonstrating its generality. Analysis of the results suggests that below band edge induced absorption in hot exciton states is due to excited-state absorption and not to shifted absorption of cold carriers and that 1Se1Sh bleach signals are not an accurate counter of sample excitons when their distribution includes multiexciton states.

PbSe/CdSe Thin-Shell Colloidal Quantum Dots

Abstract The present work describes the structural and optical characterization of PbSe and PbSe/CdSe colloidal quantum dots (CQDs), the latter being produced by cation exchange of Pb2+ for Cd2+ ions. The cation exchange occurs on preferred crystallographic facets and results in either non-concentric CdSe shells or PbxCd1–xSe alloyed-shell layers. The obtained heterostuctures are referred to as PbSe/CdSe “thin shell” CQDs. The parent PbSe CQDs are limited to relatively small diameters of 3–4 nm, with absorption edge between 1.0 and 1.3 eV. The steady-state and time-resolved photoluminescence spectra recorded at various temperatures reveal the following properties of the PbSe/CdSe CQDs: (1) the photoluminescence intensity of air-free CQDs is maintained upon their exposure to oxygen; (2) the band-edge exciton lifetime is extended by about a factor of two relative to the parent PbSe CQDs. The experimental results and the effective mass-based calculations suggest the formation of alloyed shells and highlight a pronounced effect of core displacement from the CQD center on the heterostructure optical properties.

Cation Exchange Combined with Kirkendall Effect in the Preparation of SnTe/CdTe and CdTe/SnTe Core/Shell Nanocrystals

Controlling the synthesis of narrow band gap semiconductor nanocrystals (NCs) with a high-quality surface is of prime importance for scientific and technological interests. This Letter presents facile solution-phase syntheses of SnTe NCs and their corresponding core/shell heterostructures. Here, we synthesized monodisperse and highly crystalline SnTe NCs by employing an inexpensive, nontoxic precursor, SnCl2, the reactivity of which was enhanced by adding a reducing agent, 1,2-hexadecanediol. Moreover, we developed a synthesis procedure for the formation of SnTe-based core/shell NCs by combining the cation exchange and the Kirkendall effect. The cation exchange of Sn(2+) by Cd(2+) at the surface allowed primarily the formation of SnTe/CdTe core/shell NCs. Further continuation of the reaction promoted an intensive diffusion of the Cd(2+) ions, which via the Kirkendall effect led to the formation of the inverted CdTe/SnTe core/shell NCs.

Optical and electrical characterizations of a single step ion beam milling mesa devices of chloride passivated PbS colloidal quantum dots based film

Colloidal Quantum Dots (CQDs) are of increasing interest, thanks to their quantum size effect that gives rise to their usage in various applications, such as biological tagging, solar cells and as the sensitizing layer of night vision devices. Here, we analyze the optical absorbance of chloride passivated PbS CQDs as well as revealing a correlation between their photoluminescence and sizes distribution, using theoretical models and experimental results from the literature. Next, we calculate the CQDs resistivity as a film. Although resistivity can be calculated from sheet resistance measurement using four point probes, such measurement is usually carried-out on the layer’s surface that in most cases has dangling bonds and surface states, which might affect the charges flow and modify the resistivity. Therefore; our approach, which was applied in this work, is to extract the actual resistivity from measurements that are performed along the film’s thickness (z-direction). For this intent, we fabricated gold capped PbS mesas devices using a single step Ion Beam Milling (IBM) process where we milled the gold and the PbS film continually, and then measured the vertical resistance. Knowing the mesas’ dimensions, we calculate the resistivity. To the best of our knowledge, no previous work has extracted, vertically, the resistivity of chloride passivated PbS CQDs using the above method.

Towards Low-Toxic Colloidal Quantum Dots

Abstract Colloidal quantum dots (CQDs) are of enormous interest in the scientific and engineering fields. During the past few decades, significant efforts have been conducted in investigating Cd- and Pb-based CQDs, resulting in excellent photoluminescence (PL) properties and impressive performance in various applications. But the high toxicity of Cd and Pb elements pushed the scientific community to explore low-toxic CQDs excluding poisonous heavy metals. Several semiconductor materials with lower toxicity than Cd and Pb species have been proposed. This article presents a short overview of recent efforts involving low-toxic CQDs, focusing especially on IV–VI and III–V semiconductors which are active in the near- and short-wave-infrared (IR) regimes. Recent achievements pertinent to Sn- and In-based CQDs are highlighted as representative examples. Finally, limitations and future challenges are discussed in the review.

Fundamental Properties in Colloidal Quantum Dots

A multidisciplinary approach for the production and characterization of colloidal quantum dots, which show great promise for implementation in modern optoelectronic applications, is described. The approach includes the design and formation of unique core/shell structures with alloy-composed layers between the core and the shell. Such structures eliminate interfacial defects and suppress the Auger process, thus reducing the known fluorescence blinking and endowing the quantum dots with robust chemical and spectral stability. The unique design enables the generation and sustained existence of single and multiple excitons with a defined spin-polarized emission recombination. The studies described herein implement the use of single-dot magneto-optical measurements and optically detected magnetic resonance spectroscopy, for direct identification of interfacial defects and for resolving exciton fine structure. The results are of paramount importance for a fundamental understanding of optical transitions in colloidal quantum dots, with an impact on appropriate materials design for practical applications.

High performance infrared photodetectors up to 2.8 µm wavelength based on lead selenide colloidal quantum dots

The strong quantum confinement effect in lead selenide (PbSe) colloidal quantum dots (CQDs) allows to tune the bandgap of the material, covering a large spectral range from mid- to near infrared (NIR). Together with the advantages of low-cost solution processability, flexibility and easy scale-up production in comparison to conventional semiconductors especially in the mid- to near infrared range, PbSe CQDs have been a promising material for infrared optoelectronic applications. In this study, we synthesized monodisperse and high purity PbSe CQDs and then demonstrated the photodetectors working at different wavelengths up to 2.8 µm. Our high quality PbSe CQDs show clear multiple excitonic absorption peaks. PbSe CQD films of different thicknesses were deposited on interdigitated platinum electrodes by a simple drop casting technique to make the infrared photodetectors. At room temperature, the high performances of our PbSe CQD photodetectors were achieved with maximum responsivity, detectivity and external quantum efficiency of 0.96 A/W, 8.13 × 109 Jones and 78% at 5V bias. Furthermore, a series of infrared LEDs with a broad wavelength range from 1.5 μm to 3.4 μm was utilized to demonstrate the performance of our fabricated photodetectors with various PbSe CQD film thicknesses.