Influence of ligand shape and steric hindrance on the composition of the nanocrystal ligand shell

Organic ligands play a key role in the synthesis of colloidal semiconductor nanocrystals or quantum dots. Generally they consist of a functional group and an aliphatic chain, with carboxylic acids, thiols and phosphonic acids as typical examples. The functional group ensures the binding to the nanocrystal surface, while the stability of the dispersion strongly depends on the interactions between the organic chains of the adjacent ligands. A number of studies already addressed the binding strength and the type of binding between the nanocrystal surface and the ligand yet none discuss the effect of the organic chain on the ligand exchange. By means of NMR spectroscopy, we examine the ligand shell composition of CdSe nanocrystals originally capped with oleic acid (OA), when exposed to a linear carboxylic acid. Regardless of chain length, we see a one-to-one exchange between the carboxylic acids. The composition of the ligand shell closely matches that of the ligand mixture in solution, indicating that the ligand shell can be seen as an ideal mixture of both ligands. As a consequence, a mixed ligand shell can easily be prepared by adding a ligand mixture with desired composition to the nanocrystal dispersion. On the other hand, when the CdSe nanocrystals are exposed to a branched carboxylic acid with two long aliphatic chains, like 2-hexyldecanoic acid, the ligand shell mainly consists of OA moieties. We interpret these results using an exchange process where the incoming ligand not only displaces oleic acid but also occupies additional space in the ligand shell to accommodate both aliphatic chains. Hence, given a one-for-one exchange reaction, steric hindrance in a fully packed ligand shell will prevent complete ligand exchange. These results can be very useful in view of producing nanocrystals with lower ligand densities by means of synthesis with these branched carboxylic acids

Identification of Free and Bound Exciton States and Their Phase-Dependent Trapping Behavior in Lead Halide Perovskites

In this work we probe the sub-gap energy states within polycrystalline and single crystal lead halide perovskites to better understand their intrinsic photophysics behaviors. Through combined temperature and intensity-dependent optical measurements, we reveal the existence of both free and bound exciton contributions within the sub-gap energy state manifold. The trapping and recombination dynamics of these excitons is shown to be strongly dependent on the structural phase of the perovskite. The orthorhombic phase exhibits ultrafast exciton trapping and distinct trap emission, while the tetragonal phase gives low monomolecular recombination velocity and capture cross-sections (~10-18 cm2). Within the multiphonon transition scenario, this suppression in charge trapping is caused by the increase in the charge capture activation energy due to the reduction in electron-lattice interactions, which can be the origin for the unexpected long carrier lifetime in these material systems.Comment: 5 figure

Lead-free Magnetic Double Perovskites for Photovoltaic and Photocatalysis Applications

The magnetic spin degrees of freedom in magnetic materials serve as additional capability to tune materials properties, thereby invoking magneto-optical response. Herein, we report the magneto-optoelectronic properties of a family of lead-free magnetic double perovskites Cs_{2}AgTX_{6} (T = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu; X=Cl, Br, I). This turns out to provide an extremely fertile series, giving rise to potential candidate materials for photovoltaic(PV) applications. In conjunction with high absorption coefficient and high simulated power conversion efficiency for PV applications, few compounds in this series exhibit novel magnetic character useful for spintronic applications. The interaction between magnetism and light can have far-reaching results on the photovoltaic properties as a consequence of the shift in the defect energy levels due to Zeeman effect. This subsequently affects the recombination rate of minority carriers, and hence the photoconversion efficiency. Moreover, the distinct ferromagnetic and anti-ferromagnetic ordering driven by hybridization and super-exchange mechanism can play a significant role to break the time-reversal and/or inversion symmetry. Such a coalescence of magnetism and efficient optoelectronic response has the potential to trigger magnetic/spin anomalous photovoltaic (non-linear Optical) effect in this Cs$_{2}$AgTX$_{6}$ family. These insights can thus channelize the advancement of lead-free double perovskites in magnetic/spin anomalous photovoltaic field as well.Comment: 9 pages, 5 figures, 1 tabl

Linking vertical bulk-heterojunction composition and transient photocurrent dynamics in organic solar cells with solution-processed MoOx contact layers

It is demonstrated that a combination of microsecond transient photocurrent measurements and fi lm morphology characterization can be used to identify a charge-carrier blocking layer within polymer:fullerene bulk-heterojunction solar cells. Solution-processed molybdenum oxide (s-MoO x ) interlayers are used to control the morphology of the bulk-heterojunction. By selecting either a low- or high-temperature annealing (70 C or 150 C) for the s-MoO x layer, a well-performing device is fabricated with an ideally interconnected, high-efficiency morphology, or a device is fabricated in which the fullerene phase segregates near the hole extracting contact preventing efficient charge extraction. By probing the photocurrent dynamics of these two contrasting model systems as a function of excitation voltage and light intensity, the optoelectronic responses of the solar cells are correlated with the vertical phase composition of the polymer:fullerene active layer, which is known from dynamic secondary-ion mass spectroscopy (DSIMS). Numerical simulations are used to verify and understand the experimental results. The result is a method to detect poor morphologies in operating organic solar cells

Sol-gel thin films for photonic application

For the fabrication of photonic devices the sol-gel technique is a potentially lucrative alternative to methods such as physical vapor or chemical vapor deposition because of its solution-processability, low cost and relative ease of production. In this work we harness this potential by developing based photonic devices which incorporate highly luminescent CdSe@ZnS core-shell semiconductor quantum dots (QDs) doped within inorganic (TiO2, ZrO2) or hybrid organic-inorganic sol-gel films. As a pre-requisite to the formation of such devices, luminescent waveguides emitting between green and red have been obtained and their optical properties have been characterized. The photochemical stability of these waveguides was found to highly dependent on the exact sol-gel material used. QDs:Titania based composites were found to be inherently photo-unstable due to photoelectron injection into the bulk matrix and subsequent nanocrystal oxidation. In comparison, zirconia composites were significantly more robust with high photoluminescence retained up to annealing temperatures of 300 \ub0C. Despite this difference in photo-chemical stability, both titania and zirconia composite waveguides exhibited amplified stimulated emission (ASE) with one-photon and two-photon optical pumping, however only zirconia based waveguides exhibited long term photostability. This Zirconia based films have been used for the realization of distributed feedback lasers and Bragg micro-cavities

Influence of ligand shape and steric hindrance on the composition of the nanocrystal ligand shell

Organic ligands play a key role in the synthesis of colloidal semiconductor nanocrystals or quantum dots. Generally they consist of a functional group and an aliphatic chain, with carboxylic acids, thiols and phosphonic acids as typical examples. The functional group ensures the binding to the nanocrystal surface, while the stability of the dispersion strongly depends on the interactions between the organic chains of the adjacent ligands. A number of studies already addressed the binding strength and the type of binding between the nanocrystal surface and the ligand yet none discuss the effect of the organic chain on the ligand exchange. By means of NMR spectroscopy, we examine the ligand shell composition of CdSe nanocrystals originally capped with oleic acid (OA), when exposed to a linear carboxylic acid. Regardless of chain length, we see a one-to-one exchange between the carboxylic acids. The composition of the ligand shell closely matches that of the ligand mixture in solution, indicating that the ligand shell can be seen as an ideal mixture of both ligands. As a consequence, a mixed ligand shell can easily be prepared by adding a ligand mixture with desired composition to the nanocrystal dispersion. On the other hand, when the CdSe nanocrystals are exposed to a branched carboxylic acid with two long aliphatic chains, like 2-hexyldecanoic acid, the ligand shell mainly consists of OA moieties. We interpret these results using an exchange process where the incoming ligand not only displaces oleic acid but also occupies additional space in the ligand shell to accommodate both aliphatic chains. Hence, given a one-for-one exchange reaction, steric hindrance in a fully packed ligand shell will prevent complete ligand exchange. These results can be very useful in view of producing nanocrystals with lower ligand densities by means of synthesis with these branched carboxylic acids