Karin Overgaag

Quantitative structural analysis of binary nanocrystal superlattices by electron tomography

Binary nanocrystal superlattices, that is, ordered structures of two sorts of nanocolloids, hold promise for a series of functional materials with novel collective properties. Here we show that based on electron tomography a comprehensive, quantitative, three-dimensional characterization of these systems down to the single nanocrystal level can be achieved, which is key in understanding the emerging materials properties. On four binary lattices composed of PbSe, CdSe, and Au nanocrystals, we illustrate that ambiguous interpretations based on two-dimensional transmission electron microscopy can be prevented, nanocrystal sizes and superlattice parameters accurately determined, individual crystallographic point and plane defects studied, and the order/disorder at the top and bottom surfaces imaged. Furthermore, our results suggest that superlattice nucleation and growth occurred at the suspension/air interface and that the unit cells of some lattices are anisotropically deformed upon drying.

Binary superlattices of PbSe and CdSe nanocrystals.

In this paper we show that self-organization of colloidal PbSe and CdSe semiconductor nanocrystals with a size ratio of 0.57 leads to binary structures with a AB2 or a cuboctahedral AB13 lattice. The type of superlattice formed can be regulated by the relative concentration of both nanocrystals in the suspension.

Scanning tunneling spectroscopy of individual PbSe quantum dots and molecular aggregates stabilized in an inert nanocrystal matrix

The electronic local density of states (LDOS) of single PbSe quantum dots (QDs) and QD molecules is explored using low-temperature scanning tunneling microscopy (STM) and spectroscopy (STS). Both individual PbSe QDs and molecular aggregates of PbSe QDs (dimers, trimers, etc.) are mechanically stabilized in a two-dimensional superlattice of wide band gap CdSe QDs acting as an inert matrix. The LDOS measured at individual QDs dispersed in the matrix is identical to that of single isolated QDs chemically linked to a substrate. We investigate the degree of quantum mechanical coupling between the PbSe QDs in molecular aggregates by comparing the LDOS measured at each site in the aggregates to that of an individual PbSe QD. We observe a variable broadening of the resonances indicating a spatially dependent degree of electron delocalization in the molecular aggregates.

Can scanning tunnelling spectroscopy measure the density of states of semiconductor quantum dots

Molecules, supramolecular structures and semiconductor nanocrystals are increasingly used as the active components in prototype opto-electrical devices with miniaturized dimensions and novel functions. Therefore, there is a strong need to measure the electronic structure of such single, individual nano-objects. Here, we explore the potential of scanning tunnelling spectroscopy to obtain quantitative information on the energy levels and Coulomb interactions of semiconductor quantum dots. We discuss the conditions under which shell-tunnelling, shell-filling and bipolar spectroscopy can be performed, and illustrate this with spectra acquired on individual CdSe and PbSe quantum dots. We conclude that quantitative information on the energy levels and Coulomb interactions can be obtained if the physics of the tip/quantum dot/substrate double-barrier tunnel junction is well understood.

Scanning tunnelling spectroscopy on arrays of CdSe quantum dots: response of wave functions to local electric fields

We use scanning tunnelling microscopy (STM) to controllably contact individual CdSe quantum dots (QDs) in a multilayer array to study electrical contacts to a model QD solid. The probability of electron injection into the QD array depends strongly on the symmetry of the QD wave functions and their response to the local electric field. Quantitative spectroscopy of the QD energy levels is possible if the potential distribution in the STM tip-QD array-substrate system is taken into account.

Electron-phonon coupling and intervalley splitting determine the linewidth of single-electron transport through PbSe nanocrystals

The linewidth of the resonances in the single-electron tunneling spectra has been investigated for PbSe semiconductor nanocrystals (NCs) with scanning tunneling spectroscopy at low temperature. The linewidth of the resonances corresponding to tunneling through the first conduction and valence levels is found to increase with decreasing size of the NCs. Based on theoretical calculations, this broadening is mainly induced by the coupling between the tunneling electrons and the longitudinal optical phonon mode of the NC, and by the splitting of the degenerate electronic levels between the different L-valleys in the Brillouin zone. For the smallest sizes, it is shown that the intervalley splitting is the major source of broadening.

Building Two and Three-dimensional Structures of Colloidal Particles on Surfaces using Optical Tweezers and Critical Point Drying

We describe a method for patterning substrates with colloidal particles in any designed twodimensional structure. By using optical tweezers particles are brought from a reservoir to a surface that carries a surface charge opposite to that of the particles. Using this technique large, two-dimensional patterns can be created, where the pattern can be manipulated on a single particle level. We show that these structures can be dried using critical point drying thus preventing distortions due to surface tension forces. After drying patterned surfaces can be used for further processing, which includes repeating the procedure of patterning. We show some first results of three-dimensional structures created using this layer-by-layer method. The method is generally applicable and has been demonstrated for a variety of (core-shell) colloidal particles including particles that are interesting for photonic applications like high-refractive index (ZnS)core – silica shell particles, metallodielectric (gold)-core – silica-shell particles, fluorescently labeled particles and small (several nanometers large) gold particles. Particle sizes used range from a few nanometers to several micrometers.