Iwan Moreels

Size-Dependent Optical Properties of Colloidal PbS Quantum Dots

We quantitatively investigate the size-dependent optical properties of colloidal PbS nanocrystals or quantum dots (Qdots), by combining the Qdot absorbance spectra with detailed elemental analysis of the Qdot suspensions. At high energies, the molar extinction coefficient epsilon increases with the Qdot volume d(3) and agrees with theoretical calculations using the Maxwell-Garnett effective medium theory and bulk values for the Qdot dielectric function. This demonstrates that quantum confinement has no influence on epsilon in this spectral range, and it provides an accurate method to calculate the Qdot concentration. Around the band gap, epsilon only increases with d(1.3), and values are comparable to the epsilon of PbSe Qdots. The data are related to the oscillator strength f(if) of the band gap transition and results agree well with theoretical tight-binding calculations, predicting a linear dependence of f(if) on d. For both PbS and PbSe Qdots, the exciton lifetime tau is calculated from f(if). We find values ranging between 1 and 3 mus, in agreement with experimental literature data from time-resolved luminescence spectroscopy. Our results provide a thorough general framework to calculate and understand the optical properties of suspended colloidal quantum dots. Most importantly, it highlights the significance of the local field factor in these systems.

Size-Tunable, Bright, and Stable PbS Quantum Dots: A Surface Chemistry Study

PbS Qdots are synthesized using PbCl2 and elemental sulfur as precursors. The available size range is significantly expanded using tri-n-octylphosphine (TOP), enabling the synthesis of monodisperse suspensions of Qdots with a mean size varying between 3 and 10 nm. The ligand composition and dynamics are investigated with nuclear magnetic resonance (NMR) spectroscopy. We show that the Qdots are passivated solely by highly dynamic OlAm ligands, even when TOP is employed during synthesis. In this respect, TOP is a compound strongly modifying the Qdot synthesis, without affecting the final Qdot surface chemistry. Next, the OlAm ligands are exchanged for oleic acid (OlAc). NMR data show that the OlAc ligands are tightly bound to the Qdot surface, with a coverage of 3.0±0.4 nm(-2). In addition, we demonstrate that they are bound as oleate ions. Combining this with the inorganic Qdot composition, we observe that charge-neutral Qdots are obtained when taking into account the charge of the stoichiometric PbS Qdot core, the surface excess of Pb ions, the surface-adsorbed Cl ions and the oleate ligands. The Qdot suspensions are stable under atmospheric conditions, showing no changes in the NMR and absorbance spectra for several weeks. Finally, we determine the photoluminescence quantum yield (PL QY) for OlAc-capped PbS Qdots, synthesized either with or without TOP. In both cases, they are highly luminescent, with PL QY values varying between 20 and 90%, depending on the Qdot size.

Surface chemistry of colloidal PbSe nanocrystals

Solution nuclear magnetic resonance spectroscopy (NMR) is used to identify and quantify the organic capping of colloidal PbSe nanocrystals (Q-PbSe). We find that the capping consists primarily of tightly bound oleic acid ligands. Only a minor part of the ligand shell (0-5% with respect to the number of oleic acid ligands) is composed of tri- n-octylphosphine. As a result, tuning of the Q-PbSe size during synthesis is achieved by varying the oleic acid concentration. By combining the NMR results with inductively coupled plasma mass spectrometry, a complete Q-PbSe structural model of semiconductor core and organic ligands is constructed. The nanocrystals are nonstoichiometric, with a surface that is composed of lead atoms. The absence of surface selenium atoms is in accordance with an oleic acid ligand shell. NMR results on a Q-PbSe suspension, stored under ambient conditions, suggest that oxidation leads to the loss of oleic acid ligands and surface Pb atoms, forming dissolved lead oleate.

Continuous-wave biexciton lasing at room temperature using solution-processed quantum wells

Solution-processed inorganic and organic materials have been pursued for more than a decade as low-threshold, high-gain lasing media, motivated in large part by their tunable optoelectronic properties and ease of synthesis and processing. Although both have demonstrated stimulated emission and lasing, they have not yet approached the continuous-wave pumping regime. Two-dimensional CdSe colloidal nanosheets combine the advantage of solution synthesis with the optoelectronic properties of epitaxial two-dimensional quantum wells. Here, we show that these colloidal quantum wells possess large exciton and biexciton binding energies of 132 meV and 30 meV, respectively, giving rise to stimulated emission from biexcitons at room temperature. Under femtosecond pulsed excitation, close-packed thin films yield an ultralow stimulated emission threshold of 6 μJ cm(-2), sufficient to achieve continuous-wave pumped stimulated emission, and lasing when these layers are embedded in surface-emitting microcavities.

Luminescence in Sulfides: A Rich History and a Bright Future

Sulfide-based luminescent materials have attracted a lot of attention for a wide range of photo-, cathodo- and electroluminescent applications. Upon doping with Ce3+ and Eu2+, the luminescence can be varied over the entire visible region by appropriately choosing the composition of the sulfide host. Main application areas are flat panel displays based on thin film electroluminescence, field emission displays and ZnS-based powder electroluminescence for backlights. For these applications, special attention is given to BaAl2S4:Eu, ZnS:Mn and ZnS:Cu. Recently, sulfide materials have regained interest due to their ability (in contrast to oxide materials) to provide a broad band, Eu2+-based red emission for use as a color conversion material in white-light emitting diodes (LEDs). The potential application of rare-earth doped binary alkaline-earth sulfides, like CaS and SrS, thiogallates, thioaluminates and thiosilicates as conversion phosphors is discussed. Finally, this review concludes with the size-dependent luminescence in intrinsic colloidal quantum dots like PbS and CdS, and with the luminescence in doped nanoparticles.

Short-chain alcohols strip X-type ligands and quench the luminescence of PbSe and CdSe quantum dots, acetonitrile does not.

The effect of short-chain alcohols and acetonitrile on the ligand shell composition and the photoluminescence quantum yield of purified PbSe and CdSe quantum dots is analyzed by solution NMR and photoluminescence spectroscopy. We find that short-chain alcohols induce the release of X-type carboxylate ligands with a concurrent reduction of the photoluminescence quantum yield, while acetonitrile does not. We interpret this difference in terms of the protic or aprotic character of both nonsolvents, where only the protic alcohols can provide the protons needed to desorb carboxylate ligands. We find similar differences between short-chain alcohols and acetonitrile when used as nonsolvents during the purification of crude synthesis products, a result stressing the importance of using aprotic nonsolvents for nanocrystal purification or processing.

In Situ Observation of Rapid Ligand Exchange in Colloidal Nanocrystal Suspensions Using Transfer NOE Nuclear Magnetic Resonance Spectroscopy

Recently, solution NMR-based approaches have been developed that represent useful new tools for the in situ characterization of the capping ligand in colloidal nanocrystal dispersions. So far, this development has focused mainly on tightly bound ligands (no exchange) or ligands in slow exchange with the nanocrystal surface. In such systems, the ligand can be identified and its amount and interaction quantified via 1D (1)H NMR, (1)H-(13)C HSQC, and DOSY spectra. Here, we explore the case where capping ligands are in fast exchange with the nanocrystal surface. Using dodecylamine-stabilized CdTe (Q-CdTe|DDA) and octylamine-stabilized ZnO (Q-ZnO|OctA) nanoparticles, we first show that the NMR methods developed so far fail to evidence the bound ligand when the effect of the latter on the exchange-averaged parameters is marginalized by an excess of free ligand. Next, transfer NOE spectroscopy, a well-established technique in biomolecular NMR, is introduced to demonstrate and characterize the interaction of a ligand with the nanocrystal surface. Using Q-PbSe nanocrystals capped with oleic acids as a reference system, we show that bound and free ligands have strongly different NOE spectra wherein only bound ligands develop strong and negative NOEs. For the Q-CdTe|DDA system, transfer NOE spectra show a similar rapid appearance of strong, negative NOEs, thereby unambiguously demonstrating that DDA molecules spend time at the nanocrystal surface. In the case of Q-ZnO|OctA, where a more complex mixture is analyzed, transfer NOE spectroscopy allows distinguishing capping from noncapping molecules, thereby demonstrating the screening potential offered by this technique for colloidal quantum dot dispersions.

Probing the wave function delocalization in CdSe/CdS dot-in-rod nanocrystals by time- and temperature-resolved spectroscopy.

Colloidal semiconductor quantum structures allow controlling the strong confinement of charge carriers through material composition and geometry. Besides being a unique platform to study fundamental effects, these materials attracted considerable interest due to their potential in opto-electronic and quantum communication applications. Heteronanostructures like CdSe/CdS offer new prospects to tailor their optical properties as they take advantage of a small conduction band offset allowing tunability of the electron delocalization from type-I toward quasi-type-II. Here, we report on a detailed study of the exciton recombination dynamics in CdSe/CdS heterorods. We observed a clear size-dependent radiative lifetime, which can be linked to the different degree of electron wave function (de)localization. Moreover, by increasing the temperature from 70 to 300 K, we observed a considerable increase of the radiative lifetime, clearly demonstrating a reduction of the conduction band offset at higher temperatures. Understanding and controlling electron delocalization in such heterostructures will be pivotal for realizing efficient and low-cost photonic devices.

From Binary Cu2S to ternary Cu-In-S and quaternary Cu-In-Zn-S nanocrystals with tunable composition via partial cation exchange.

We present an approach for the synthesis of ternary copper indium sulfide (CIS) and quaternary copper indium zinc sulfide (CIZS) nanocrystals (NCs) by means of partial cation exchange with In(3+) and Zn(2+). The approach consists of a sequential three-step synthesis: first, binary Cu2S NCs were synthesized, followed by the homogeneous incorporation of In(3+) by an in situ partial cation-exchange reaction, leading to CIS NCs. In the last step, a second partial exchange was performed where Zn(2+) partially replaced the Cu(+) and In(3+) cations at the surface, creating a ZnS-rich shell with the preservation of the size and shape. By careful tuning reaction parameters (growth and exchange times as well as the initial Cu(+):In(3+):Zn(2+) ratios), control over both the size and composition was achieved. This led to a broad tuning of photoluminescence of the final CIZS NCs, ranging from 880 to 1030 nm without altering the NCs size. Cytotoxicity tests confirmed the biocompatibility of the synthesized CIZS NCs, which opens up opportunities for their application as near-infrared fluorescent markers in the biomedical field.

Synthesis of Uniform Disk-Shaped Copper Telluride Nanocrystals and Cation Exchange to Cadmium Telluride Quantum Disks with Stable Red Emission

We present the synthesis of novel disk-shaped hexagonal Cu2Te nanocrystals with a well-defined stoichiometric composition and tunable diameter and thickness. Subsequent cation exchange of Cu to Cd at high temperature (180 °C) results in highly fluorescent CdTe nanocrystals, with less than 1 mol % of residual Cu remaining in the lattice. The procedure preserves the overall disk shape, but is accompanied by a substantial reconstruction of the anion sublattice, resulting in a reorientation of the c-axis from the surface normal in Cu2Te into the disk plane in CdTe nanodisks. The synthesized CdTe nanodisks show a continuously tunable photoluminescence (PL) peak position, scaling with the thickness of the disks. The PL lifetime further confirms that the CdTe PL arises from band-edge exciton recombination; that is, no Cu-related emission is observed. On average, the recombination rate is about 25-45% faster with respect to their spherical quantum dots counterparts, opening up the possibility to enhance the emission rate at a given wavelength by controlling the nanocrystal shape. Finally, with a PL quantum efficiency of up to 36% and an enhanced PL stability under ambient conditions due to a monolayer of CdS formed on the nanocrystal surface during cation exchange, these flat quantum disks form an interesting enrichment to the current family of highly fluorescent, shape-controlled nanocrystals.