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 Not 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 E 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 mu s, 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

Impurity-enhanced solid-state amorphization : the Ni-Si thin film reaction altered by nitrogen

Solid-state amorphization, the growth of an amorphous phase during annealing, has been studied in a wide variety of thin film structures. Whereas research on the remarkable growth of such a metastable phase has mostly focused on strictly binary systems, far less is known about the influence of impurities on such reactions. In this paper, the influence of nitrogen, introduced via ion implantation, is studied on the solid-state amorphization reaction of thin (35 nm) Ni films with Si, using in situ x-ray diffraction (XRD), ex situ Rutherford backscattering spectrometry, XTEM, and synchrotron XRD. It is shown that due to small amounts of nitrogen (<2 at.%), an amorphous Ni-Si phase grows almost an order of magnitude thicker during annealing than for unimplanted samples. Nitrogen hinders the nucleation of the first crystalline phases, leading to a new reaction path: the formation of the metal-rich crystalline silicides is suppressed in favour of an amorphous Ni-Si alloy; during a brief temperature window between 330 and 350 degrees C, the entire film is converted to an amorphous phase. The first crystalline structure to grow is the orthorhombic NiSi phase. We demonstrate that this impurity-enchanced solid-state amorphization reaction occurs only under specific implantation conditions. In particular, the initial distribution of nitrogen upon implantation is crucial: sufficient nitrogen impurities must be present at the interface throughout the reaction. Introducing implantation damage without nitrogen impurities (e.g. by implanting a noble gas) does not cause the enhanced solid-state amorphization reaction. Moreover, we show that the stabilizing effect of nitrogen on amorphous Ni-Si films (with a composition ranging from 40% to 50% Si) is not restricted to thin film reactions, but is a general feature of the Ni-Si system

Independent tuning of size and coverage of supported Pt nanoparticles using atomic layer deposition

Synthetic methods that allow for the controlled design of well-defined Pt nanoparticles are highly desirable for fundamental catalysis research. In this work, we propose a strategy that allows precise and independent control of the Pt particle size and coverage. Our approach exploits the versatility of the atomic layer deposition (ALD) technique by combining two ALD processes for Pt using different reactants. The particle areal density is controlled by tailoring the number of ALD cycles using trimethyl(methylcyclopentadienyl) platinum and oxygen, while subsequent growth using the same Pt precursor in combination with nitrogen plasma allows for tuning of the particle size at the atomic level. The excellent control over the particle morphology is clearly demonstrated by means of in situ and ex situ X-ray fluorescence and grazing incidence small angle X-ray scattering experiments, providing information about the Pt loading, average particle dimensions, and mean center-to-center particle distance

Moessbauerstudie van epitaxiale Co-silicides

SIGLEKULeuven Campusbibliotheek Exacte Wetenschappen / UCL - Université Catholique de LouvainBEBelgiu

Lithium Diffusion in Copper

Copper is the conventional, broadly applied anode current collector in lithium-ion batteries, because Li does not form intermetallic alloys with Cu at room temperature. Fast diffusion and trapping of lithium in copper were, however, suggested in the past, and the involved diffusion mechanisms are still not clarified. By using three complementary methods, we determine grain boundary and lattice diffusion of lithium in copper. We show that indiffusion into copper is possible not only from metallic lithium deposits at the surface but also from a Li+-containing electrolyte. Lattice diffusion (D0 = 3.9 × 10-9 cm2/s; Ea = 0.68 eV) and grain boundary diffusion (D0 = 1.5 × 10-11 cm2/s; Ea = 0.36 eV) are found to be 13 orders of magnitude lower than previously published. Furthermore, for practical Li-ion battery considerations, lithium trapping in copper current collectors, which relies heavily on operating temperature and morphology, is discussed.status: publishe

Electrical and structural characterization of defects introduced in p-SiGe during low energy erbium implantation

We have used electrical measurements Deep level transient spectroscopy (DLTS) complemented by high-resolution X-ray diffraction (HRXRD) and Rutherford backscattering spectroscopy (RBS) measurements for assessment of the defects introduced in p-Si1-xGex during 160keV erbium ion implantation. From deep-level transient spectroscopy, it was observed that two prominent defects with discrete energy levels above the valence band, were introduced during Er ion implantation. The observed defects have similar signatures as those introduced during alpha-particle irradiation and electron beam metal deposition, indicating that these defects are more likely not related to Er but only to implantation induced damage such as primary defects. The generated defects expand the Si1-xGex lattice in the implanted region, which results in the presence of the tail in the high-resolution X-ray diffraction spectra. After rapid thermal annealing (RTA) at 850degreesC for 30 s in nitrogen ambient, a reduction in defect density as well as a relaxation of the Si1-xGex lattice is observed for all x values. A dominant Er-related sharp emission in the 1.541 mum region was observed at room temperature and neither the intensity of the Er emission nor the emission peak position were influenced by the Ge content or the strain relaxation in the epilayers

Acid-base mediated ligand exchange on near-infrared absorbing, indium-based III-V colloidal quantum dots

Colloidal quantum dots (QDs) made from In-based III-V semiconductors are emerging as a printable infrared material. However, the formulation of infrared inks and the formation of electrically conductive QD coatings is hampered by a limited understanding of the surface chemistry of In-based QDs. In this work, we present a case study on the surface termination of IR active III-V QDs absorbing at 1220 nm that were synthesized by reducing a mixture of indium halides and an aminoarsine by an aminophosphine in oleylamine. We find that this recently established synthesis method yields In(As,P) QDs with minor phosphorus admixing and a surface terminated by a mixture of oleylamine and chloride. Exposing these QDs to protic surface-active compounds RXH, such as fatty acids or alkanethiols, initiates a ligand exchange reaction involving the binding of the conjugate base RX- and the desorption of 1 equiv of alkylammonium chloride. Using density functional theory simulations, we confirm that the formation of the alkylammonium chloride salt can provide the energy needed to drive such acid/base mediated ligand exchange reactions, even for weak organic acids such as alkanethiols. We conclude that the unique surface termination of In(As,P) QDs, consisting of a mixture of L-type and X- type ligands and acid/base mediated ligand exchange, can form a general model for In-based III-V QDs synthesized using indium halides and aminopnictogens

A case study of ALD encapsulation of quantum dots: embedding supported CdSe/CdS/ZnS quantum dots in a ZnO matrix

We study the encapsulation of monolayers of CdSe/CdS/ZnS core/shell/shell quantum dots (QDs) in a ZnO matrix by atomic layer deposition (ALD) in order to gain insight in the interaction between quantum dots and ALD precursors and the resulting metal oxide coating. Using in situ XRF and GISAXS, we show the inhibition of ZnO growth on as-deposited QDs. Growth can, however, be triggered by exposing the QDs to a single pulse of trimethylaluminum (TMA) vapor. Such a TMA pretreatment results in the substitution of 35-40% of the surface Zn by Al. Whereas this drops by half the photoluminescence quantum yield of the QDs, we argue that this replacement primes the QD monolayer for ZnO growth by ALD. Finally, the evolution of the GISAXS pattern during subsequent ALD growth attests the preservation of the ordering of the QDs in the monolayer. These results illustrate the important interplay between highly reactive ALD precursors and the QD surface

Light Absorption Coefficient of CsPbBr3 Perovskite Nanocrystals

Inductively coupled plasma mass spectrometry (ICP-MS) was combined with UV-vis absorption spectroscopy and transmission electron microscopy to determine the size, composition, and intrinsic absorption coefficient μi of 4 to 11 nm sized colloidal CsPbBr3 nanocrystals (NCs). The ICP-MS measurements demonstrate the nonstoichiometric nature of the NCs, with a systematic excess of lead for all samples studied. Rutherford backscattering measurements indicate that this enrichment in lead concurs with a relative increase in the bromide content. At high photon energies, μi is independent of the nanocrystal size. This allows the nanocrystal concentration in CsPbBr3 nanocolloids to be readily obtained by a combination of absorption spectroscopy and the CsPbBr3 sizing curve.status: publishe

Magnetic characterization of oblique angle deposited Co/CoO on gold nanoparticles

© 2019 Elsevier B.V. The influence of a patterned substrate on obliquely deposited, exchange biased Co/CoO films was studied. It was found that substrates decorated with nanoparticle patterns provide the option to manipulate the orientation of the magnetic easy axis in obliquely deposited thin films. The complementary methods of SQUID magnetometry and polarized neutron reflectometry were used to disentangle the different contributions to the magnetic hysteresis of such complex magnetic systems.status: publishe