Selenium reduction pathways in the colloidal synthesis of CdSe nanoplatelets.

Several established procedures are now available to prepare zinc blende CdSe nanoplatelets. While these protocols allow for detailed control over both thickness and lateral dimensions, the chemistry behind their formation is yet to be unraveled. In this work, we discuss the influence of the solvent on the synthesis of nanoplatelets. We confirmed that the presence of double bonds, as is the case for 1-octadecene, plays a key role in the evolution of nanoplatelets, through the isomerization of the alkene, as confirmed by nuclear magnetic resonance spectroscopy and mass spectrometry. Consequently, 1-octadecene can be replaced as a solvent (or solvent mixture), however, only by one that also contains α protons to CC double bonds. We confirm this via synthesis of nanoplatelets in hexadecane spiked with a small amount of 1-octadecene, and in the aromatic solvent 1,2,3,4-tetrahydronaphthalene (tetralin). At the same time, the chemical reaction leading to the formation of nanoplatelets occurs to some extent in saturated solvents. A closer examination revealed that an alternative formation pathway is possible, through interaction of carboxylic acids, such as octanoic acid, with selenium. Next to shedding more light on the synthesis of CdSe nanoplatelets, fundamental understanding of the precursor chemistry paves the way to use optimized solvent admixtures as an additional handle to control the nanoplatelet synthesis, as well as to reduce potential self-polymerization hurdles observed with 1-octadecene.

Coherent Spin Dynamics of Electrons in CdSe Colloidal Nanoplatelets.

Coherent spin dynamics of electrons in CdSe colloidal nanoplatelets are investigated by time-resolved pump-probe Faraday rotation at room and cryogenic temperatures. We measure electron spin precession in a magnetic field and determine g-factors of 1.83 and 1.72 at low temperatures for nanoplatelets with a thickness of 3 and 4 monolayers, respectively. The dephasing time of spin precession T2* amounts to a few nanoseconds and has a weak dependence on temperature, while the longitudinal spin relaxation time T1 exceeds 10 ns even at room temperature. Observations of single and double electron spin-flips confirm that the nanoplatelets are negatively charged. The spin-flip Raman scattering technique reveals g-factor anisotropy by up to 10% in nanoplatelets with thicknesses of 3, 4, and 5 monolayers. In the ensemble with a random orientation of nanoplatelets, our theoretical analysis shows that the measured Larmor precession frequency corresponds to the in-plane electron g-factor. We conclude that the experimentally observed electron spin dephasing and its acceleration in the magnetic field are not provided by the electron g-factor anisotropy and can be related to the localization of the resident electrons and fluctuations of the localization potential.

Colloidal CdSe/CdS Core/Crown Nanoplatelets for Efficient Blue Light Emission and Optical Amplification.

The application of CdSe nanoplatelets (NPLs) in the ultraviolet/blue region remains an open challenge due to charge trapping typically leading to limited photoluminescence quantum efficiency (PL QE) and sub-bandgap emission in core-only NPLs. Here, we synthesized 3.5 monolayer core/crown CdSe/CdS NPLs with various crown dimensions, exhibiting saturated blue emission and PL QE up to 55%. Compared to core-only NPLs, the PL intensity decays monoexponentially over two decades due to suppressed deep trapping and delayed emission. In both core-only and core/crown NPLs we observe biexciton-mediated optical gain between 470 and 510 nm, with material gain coefficients up to 7900 cm-1 and consistently lower gain thresholds in crowned NPLs. Gain lifetimes are limited to 40 ps, due to residual ultrafast trapping and higher exciton densities at threshold. Our results provide guidelines for rational optimization of thin CdSe NPLs toward lighting and light-amplification applications.

Purifying single photon emission from giant shell CdSe/CdS quantum dots at room temperature.

Giant shell CdSe/CdS quantum dots are bright and flexible emitters, with near-unity quantum yield and suppressed blinking, but their single photon purity is reduced by efficient multiexcitonic emission. We report the observation, at the single dot level, of a large blueshift of the photoluminescence biexciton spectrum (24 ± 5 nm over a sample of 32 dots) for pure-phase wurtzite quantum dots. By spectral filtering, we demonstrate a 2.3 times reduction of the biexciton quantum yield relative to the exciton emission, while preserving as much as 60% of the exciton single photon emission, thus improving the purity from g2(0) = 0.07 ± 0.01 to g2(0) = 0.03 ± 0.01. At a larger pump fluency, spectral purification is even more effective with up to a 6.6 times reduction in g2(0), which is due to the suppression of higher order excitons and shell states experiencing even larger blueshifts. Our results indicate the potential for the synthesis of engineered giant shell quantum dots, with further increased biexciton blueshifts, for quantum optical applications requiring both high purity and brightness.

Area-Independence of the Biexciton Oscillator Strength in CdSe Colloidal Nanoplatelets.

Colloidal CdSe nanoplatelets (NPLs) are unique systems to study two-dimensional excitons and excitonic complexes. However, while absorption and emission of photons through exciton formation and recombination have been extensively quantified, few studies have addressed the exciton-biexciton transition. Here, we use cross-polarized pump-probe spectroscopy to measure the absorption coefficient spectrum of this transition and determine the biexciton oscillator strength (fBX). We show that fBX is independent of the NPL area and that the concomitant biexciton area (SBX) agrees with predictions of a short-range interaction model. Moreover, we show that fBX is comparable to the oscillator strength of forming localized excitons at room temperature while being unaffected itself by center-of-mass localization. These results confirm the relevance of biexcitons for light-matter interaction in NPLs. Moreover, the quantification of the exciton-biexciton transition introduced here will enable researchers to rank 2D materials by the strength of this transition and to compare experimental results with theoretical predictions.

Exciton Binding Energy in CdSe Nanoplatelets Measured by One- and Two-Photon Absorption.

Colloidal semiconductor nanoplatelets exhibit strong quantum confinement for electrons and holes as well as excitons in one dimension, while their in-plane motion is free. Because of the large dielectric contrast between the semiconductor and its ligand environment, the Coulomb interaction between electrons and holes is strongly enhanced. By means of one- and two-photon photoluminescence excitation spectroscopy, we measure the energies of the 1S and 1P exciton states in CdSe nanoplatelets with thicknesses varied from 3 up to 7 monolayers. By comparison with calculations, performed in the effective mass approximation with account of the dielectric enhancement, we evaluate exciton binding energies of 195-315 meV, which is about 20 times greater than that in bulk CdSe. Our calculations of the effective Coulomb potential for very thin nanoplatelets are close to the Rytova-Keldysh model, and the exciton binding energies are comparable with the values reported for monolayer-thick transition metal dichalcogenides.

Localization-limited exciton oscillator strength in colloidal CdSe nanoplatelets revealed by the optically induced stark effect.

2D materials are considered for applications that require strong light-matter interaction because of the apparently giant oscillator strength of the exciton transitions in the absorbance spectrum. Nevertheless, the effective oscillator strengths of these transitions have been scarcely reported, nor is there a consistent interpretation of the obtained values. Here, we analyse the transition dipole moment and the ensuing oscillator strength of the exciton transition in 2D CdSe nanoplatelets by means of the optically induced Stark effect (OSE). Intriguingly, we find that the exciton absorption line reacts to a high intensity optical field as a transition with an oscillator strength FStark that is 50 times smaller than expected based on the linear absorption coefficient. We propose that the pronounced exciton absorption line should be seen as the sum of multiple, low oscillator strength transitions, rather than a single high oscillator strength one, a feat we assign to strong exciton center-of-mass localization. Within the quantum mechanical description of excitons, this 50-fold difference between both oscillator strengths corresponds to the ratio between the coherence area of the exciton's center of mass and the total area, which yields a coherence area of a mere 6.1 nm2. Since we find that the coherence area increases with reducing temperature, we conclude that thermal effects, related to lattice vibrations, contribute to exciton localization. In further support of this localization model, we show that FStark is independent of the nanoplatelet area, correctly predicts the radiative lifetime, and lines up for strongly confined quantum dot systems.

Colloidal Synthesis of Laterally Confined Blue-Emitting 3.5 Monolayer CdSe Nanoplatelets.

The typical synthesis protocol for blue-emitting CdSe nanoplatelets (NPLs) yields particles with extended lateral dimensions and large surface areas, resulting in NPLs with poor photoluminescence quantum efficiency. We have developed a synthesis protocol that achieves an improved control over the lateral size, by exploiting a series of long-chained carboxylate precursors that vary from cadmium octanoate (C8) to cadmium stearate (C18). The length of this metallic precursor is key to tune the width and aspect ratio of the final NPLs, and for the shorter chain lengths, the synthesis yield is improved. NPLs prepared with our procedure possess significantly enhanced photoluminescence quantum efficiencies, up to 30%. This is likely due to their reduced lateral dimensions, which also grant them good colloidal stability. As the NPL width can be tuned below the bulk exciton Bohr radius, the band edge blue-shifts, and we constructed a sizing curve relating the NPL absorption position and width. Further adjusting the synthesis protocol, we were able to obtain even thinner NPLs, emitting in the near-UV region, with a band-edge quantum efficiency of up to 11%. Results pave the way to stable and efficient light sources for applications such as blue and UV light-emitting devices and lasers.

The effect of sodium hydroxide on Al uptake by calcium silicate hydrates (CSH).

To reduce the CO2 emissions from cement production, Portland cement (PC) is partially replaced by supplementary cementitious materials (SCM). Reactions of SCM with PC during hydration leads to the formation of CSH with more silicon and aluminum than in PC, which affects the stability and durability of such concrete. Therefore, it is crucial to determine the role of aluminum on CSH properties to predict the formed hydrate phase assemblages and their effects on durability. Aluminum sorption isotherms including very low Al concentrations have been determined for CSH with Ca/Si ratios from 0.6 to 1.4. Elemental measurements were performed with ICP-MS and ICP-OES. The presence of secondary phases was investigated by using thermogravimetric analysis and XRD. Higher dissolved concentrations of Al were observed at increased alkali hydroxide concentrations and thus higher pH values. High alkali hydroxide led to an increased Al(OH)4- formation, which reduced the Al uptake in CSH. This comparable behavior of Al and Si towards changes in pH values, points toward the uptake of aluminum within the silica chain both at low and high Ca/Si ratios. A higher Al uptake in CSH was observed at higher Ca/Si ratios, which indicates a stabilizing effect of calcium in the interlayer on Al uptake.

Tracheal diverticula: A retrospective analysis of patients referred for thoracic CT.

To assess the prevalence of tracheal diverticula (TD) in patients referred for thoracic Computed Tomography (CT).1679 consecutive patients subjected to thoracic CT examination for different causes, from January to June 2017, were included in this cohort study. CT was performed with a 64 slice CT, using a standard protocol and Multiplanar Reformat Images (MPR). A TD was defined as a thin-walled air sac at the paratracheal wall with a communication with the tracheal lumen. Congenital or acquired nature of TD was determined by the anatomical location, being usually the congenital ones located 4 to 5 cm below the vocal cords or a few centimeters above the carina in the right paratracheal area, whereas acquired ones were located at the level of the thoracic inlet, in the posterolateral tracheal wall. Presence of TD was assessed and their number and size recorded based on 2 axial diameters and size of neck.One or more TD were found in 96 patients (5.7% of sample), with a slight preponderance (65%) in male gender. Globally, 124 TD were detected; they were solitary in 75% of cases, double in 20.8%, and in about 4.2% they were triple. Average size of the TD was 1.3×4.9 mm with a mean width of the neck of 1.9 mm. The peak of prevalence (9%) was in patients belonging to the fourth-decade group (see ). According to their anatomical location, the majority (97.6%) of TD were acquired in nature and devoided of specific symptoms (see below).(Table is included in full-text article.)Acquired TD were detected in about 1 out of 20 of thoracic CTs and were usually incidentally. Our findings show a slightly higher frequency than previously reported. The most frequent presentation was in male and as a single entity. Clinically, TD was not associated with specific symptoms, in particular with chronic cough or Chronic Obstructive Pulmonary Disease (COPD).

Update on the current recommendations and outcomes in pregnant women with antiphospholipid syndrome.

Pregnancy morbidity is part of the clinical spectrum of the antiphospholipid syndrome (APS), a chronic autoimmune condition serologically characterized by the persistent positivity of antiphospholipid antibodies (aPL). Antiplatelet and anticoagulant agents are the mainstay of the treatment of obstetric APS. However, there is an ongoing debate about the optimal management of women with most severe aPL-mediated obstetric complications, women not fulfilling APS criteria and those with refractory disease. Unfortunately, the literature cannot provide definite answers to these controversial issues, being flawed by many limitations. The evidence supporting the recommended therapeutic management of different aPL-related obstetrical clinical manifestations is presented, with a critical appraisal of each approach.