Robust luminophores emitting light with broadly tunable colors are desirable in many applications such as light-emitting diode (LED)-based lighting, displays, integrated optoelectronics and biology. Nanocrystalline quantum dots with multicolor emission, from core- and shell-localized excitons, as well as solid layers of mixed quantum dots that emit different colors have been proposed. Here, we report on colloidal supraparticles that are composed of three types of Cd(Se,ZnS) core/(Cd,Zn)S shell nanocrystals with emission in the red, green, and blue. The emission of the supraparticles can be varied from pure to composite colors over the entire visible region and fine-tuned into variable shades of white light by mixing the nanocrystals in controlled proportions. Our approach results in supraparticles with sizes spanning the colloidal domain and beyond that combine versatility and processability with a broad, stable, and tunable emission, promising applications in lighting devices and biological research.Keywords: assembly; nanocrystal; quantum dot; supraparticles; tunable emission; white light;

Colloidal semiconductor nanocrystals become increasingly important in materials science and technology, due to their optoelectronic properties that are tunable by size. The measurement and understanding of their energy levels is key to scientific and technological progress. Here we review how the confined electronic orbitals and related energy levels of individual semiconductor quantum dots have been measured by means of scanning tunneling microscopy and spectroscopy. These techniques were originally developed for flat conducting surfaces, but they have been adapted to investigate the atomic and electronic structure of semiconductor quantum dots. We compare the results obtained on colloidal quantum dots with those on comparable solid-state ones. We also compare the results obtained with scanning tunneling spectroscopy with those of optical spectroscopy. The first three sections provide an introduction to colloidal quantum dots, and a theoretical basis to be able to understand tunneling spectroscopy on dots attached to a conducting surface. In sections 4 and 5, we review the work performed on lead-chalcogenide nanocrystals and on colloidal quantum dots and rods of II–VI compounds, respectively. In section 6, we deal with colloidal III–V nanocrystals and compare the results with their self-assembled counter parts. In section 7, we review the work on other types of semiconductor quantum dots, especially on Si and Ge nanocrystals.

The efficiency and stability of emission from semiconductor nanocrystal quantum dots (QDs) is negatively affected by “blinking” on the single-nanocrystal level, that is, random alternation of bright and dark periods. The time scales of these fluctuations can be as long as many seconds, orders of magnitude longer than typical lifetimes of exciton states in QDs. In this work, we investigate photoluminescence from QDs delayed over microseconds to milliseconds. Our results prove the existence of long-lived charge-separated states in QDs. We study the properties of delayed emission as a direct way to learn about charge carrier separation and recovery of the exciton state. A new microscopic model is developed to connect delayed emission to exciton recombination and blinking from which we conclude that bright periods in blinking are in fact not characterized by uninterrupted optical cycling as often assumed.

Semiconductor quantum wells are ubiquitous in high-performance optoelectronic devices such as solar cells and lasers. Understanding and controlling of the (hot) carrier dynamics is essential to optimize their performance. Here, we study hot electron cooling in colloidal CdSe quantum-well nanoplatelets using ultrafast two-photon photoemission spectroscopy at low excitation intensities, resulting typically in 1–5 hot electrons per platelet. We observe initial electron cooling in the femtosecond time domain that slows down with decreasing electron energy and is finished within 2 ps. The cooling is considerably faster at cryogenic temperatures than at room temperature, and at least for the systems that we studied, independent of the thickness of the platelets (here 3–5 CdSe units) and the presence of a CdS shell. The cooling rates that we observe are orders of magnitude faster than reported for similar CdSe platelets under strong excitation. Our results are understood by a classic cooling mechanism with emission of longitudinal optical phonons without a significant influence of the surface.

Semiconductors are indispensable as the active light-emitting element in many optoelectronic devices. However, even the purest bulk semiconductors suffer from considerable nonradiative recombination leading to low photoluminescence efficiencies. Zero-dimensional quantum dots show a much better carrier-to-photon conversion caused by confinement of the excitons but suffer from nonradiative recombination when assembled into a solid, due to exciton energy transfer. Here, we report on the shape-dependent optical properties of self-assembled supraparticles composed of CdSe/multishell nanocrystals. All supraparticles show stable and bright photoluminescence in ambient up to high excitation intensities. When the supraparticles are deposited on a silicon surface their spherical shape is deformed due to drying. In addition to single-exciton emission, we observe bright emission from multiexciton states at high excitation powers. In contrast, supraparticles that retain their perfectly spherical shape show a spectrum with sharp Mie whispering gallery modes, while multiexciton emission is absent.Keywords: assembly; Auger recombination; multiexciton emission; nanocrystal; quantum dot; quantum dot solid; whispering gallery mode;

Sufficiently large semiconductor nanocrystals are a useful model system to characterize bulk-like excitons, with the electron and hole bound predominantly by Coulomb interaction. We present optical characterization of excitons in individual giant CdTe nanocrystals with diameters up to 25.5 nm at 4.2 K under varying excitation power and magnetic field strength. We determine values for the biexciton binding energy, diamagnetic shift constant, and Landé g-factor, which approach the bulk values with increasing nanocrystal size.Keywords: exciton localization; multiexcitons; semiconductor quantum dots; weak quantum confinement;

Conventional colloidal quantum dots (QDs) suffer from rapid energy losses by nonradiative (Auger) processes, leading to sub-ns lifetimes in all excited states but the lowest-energy single exciton. Suppression of interband Auger decay, such as biexciton Auger recombination, has been achieved with the design of heterostructured core−shell QDs. Auger-like processes are also believed to be responsible for rapid intraband hot-electron cooling in QDs. However, the simultaneous effect of shell growth on interband Auger recombination and intraband hot-electron cooling has not been addressed. Here we investigate how the growth of a CdS shell affects these two relaxation processes in CdSe/CdS core–shell QDs. Using a combination of ultrafast pump–push–probe spectroscopy on the QD ensemble and analysis of the photon statistics from single QDs, we find that Auger losses in the biexciton state are suppressed with increasing shell thickness, while hot-electron cooling remains unaffected. Calculations conducted within an eight-band k·p model confirm the experimental dependence of the biexciton Auger decay on the shell thickness, and provide insights into the factors determining the cooling rate of hot carriers.Keywords: Auger processes; k·p theory; quantum dots; single quantum dot spectroscopy; transient absorption;

Currently, ultrathin colloidal CdSe semiconductor nanoplatelets (NPLs) with a uniform thickness that is controllable up to the atomic scale can be prepared. The optical properties of these 2D semiconductor systems are the subject of extensive research. Here, we reveal their natural morphology and atomic arrangement. Using cryo-TEM (cryo-transmission electron microscopy), we show that the shape of rectangular NPLs in solution resembles a helix. Fast incorporation of these NPLs in silica preserves and immobilizes their helical shape, which allowed us to perform an in-depth study by high angle annular dark field scanning transmission electron microscopy (HAADF-STEM). Electron tomography measurements confirm and detail the helical shape of these systems. Additionally, high-resolution HAADF-STEM shows the thickness of the NPLs on the atomic scale and furthermore that these are consistently folded along a ⟨110⟩ direction. The presence of a silica shell on both the top and bottom surfaces shows that Cd atoms must be accessible for silica precursor (and ligand) molecules on both sides.

In this work, we present a method for the incorporation of anisotropic colloidal nanocrystals of many different shapes in silica in a highly controlled way. This method yields a uniform silica shell, with thickness tunable from 3 to 17 nm. The silica shell perfectly adapts to the shape of the nanocrystals, preserving their anisotropy, a crucial requisite for shape-dependent applications. Our method is based on an adaptation of the reverse microemulsion method. High control over the nucleation and growth of the shell is obtained by slowing down the hydrolysis and condensation rates of the silica precursor by lowering the ammonia concentration. This is shown to be essential for the formation of a uniform silica shell in the case of CdSe/CdS core/shell nanorods. Additionally, the general applicability of this method is demonstrated by coating different anisotropic semiconductor nanocrystals such as nanostars and 2D nanoplatelets. These results thus represent a crucial step toward the fabrication of highly processable and functionalized anisotropic nanoparticles.

We studied spontaneously self-assembled aggregates in a suspension of CdSe/CdS core/shell nanorods (NRs). The influence of the length and concentration of the NRs and the suspension temperature on the size of the aggregates was investigated using in situ small-angle X-ray scattering (SAXS) and linear dichroism (LD) measurements under high magnetic fields (up to 30 T). The SAXS patterns reveal the existence of crystalline 2-dimensional sheets of ordered NRs with an unusually large distance between the rods. The LD measurements show that the size of the sheets depends on the free-energy driving force for NR self-assembly. More precisely, the sheets are larger if the attraction between NRs is stronger, if the temperature is lower, or if the NR concentration is higher. We show that the formation of large NR sheets is a slow process that can take days. Our in situ results of the structures that spontaneously form in the bulk suspension could further our understanding of NR self-assembly into mono- or multilayer superlattices that occurs at the suspension/air interface upon evaporation of the solvent.Keywords: colloidal nanorod; magnetic linear dichroism; self-assembly; small-angle X-ray scattering; superlattice;

The self-assembly of different nanocrystals into a binary superlattice is of interest for both colloidal science and nanomaterials science. New properties may emerge from the interaction between the nanocrystal building blocks that are ordered in close contact in three dimensions. Identification of the superlattice structure including its defects is of key interest in understanding the electrical and optical properties of these systems. Transmission electron microscopy (TEM) has been very instrumental to reach this goal but fails for complex crystal structures and buried defects. Here, we use electron tomography to resolve the three-dimensional crystal structure of a binary superlattice that could not be resolved by TEM only. The structure with a [PbSe]6[CdSe]19 stoichiometry has no analogue in the atomic world. Moreover we will show how tomography can overcome the clouding effects of planar defects on structure identification by TEM.

Oriented attachment, the process in which nanometer-sized crystals fuse by atomic bonding of specific crystal facets, is expected to be more difficult to control than nanocrystal self-assembly that is driven by entropic factors or weak van der Waals attractions. Here, we present a study of oriented attachment of PbSe nanocrystals that counteract this tuition. The reaction was studied in a thin film of the suspension casted on an immiscible liquid at a given temperature. We report that attachment can be controlled such that it occurs with one type of facets exclusively. By control of the temperature and particle concentration we obtain one- or two-dimensional PbSe single crystals, the latter with a honeycomb or square superimposed periodicity in the nanometer range. We demonstrate the ability to convert these PbSe superstructures into other semiconductor compounds with the preservation of crystallinity and geometry.

Progress to reduce nonradiative Auger decay in colloidal nanocrystals has recently been made by growing thick shells. However, the physics of Auger suppression is not yet fully understood. Here, we examine the dynamics and spectral characteristics of single CdSe-dot-in-CdS-rod nanocrystals. These exhibit blinking due to charging/discharging, as well as trap-related blinking. We show that one-dimensional electron delocalization into the rod-shaped shell can be as effective as a thick spherical shell at reducing Auger recombination of the negative trion state.

CdSe(core)/CdS(shell) nanorods (NRs) have been extensively investigated for their unique optical properties, such as high photoluminescence (PL) quantum efficiency (QE) and polarized light emission. The incorporation of these NRs in silica (SiO2) is of high interest, since this renders them processable in polar solvents while increasing their photochemical stability, which would be beneficial for their application in LEDs and as biolabels. We report the synthesis of highly luminescent silica-coated CdSe/CdS NRs, by using the reverse micelle method. The mechanism for the encapsulation of the NRs in silica is unravelled and shown to be strongly influenced by the NR shape and its asymmetry. This is attributed to both the different morphology and the different crystallographic nature of the facets terminating the opposite tips of the NRs. These results lead to the formation of a novel class of NR architectures, whose symmetry can be controlled by tuning the degree of coverage of the silica shell. Interestingly, the encapsulation of the NRs in silica leads to a remarkable increase in their photostability, while preserving their optical properties.Keywords: nanocrystals; photoluminescence; reverse micelle method; silica shell;

We study the self-assembly of colloidal CdSe/CdS nanorods (NRs) at the liquid/air interface combining time-resolved in situ grazing-incidence small angle X-ray scattering (GISAXS) and ex situ transmission electron microscopy (TEM). Our study shows that NR superstructure formation occurs at the liquid/air interface. Short NRs self-assemble into micrometers long tracks of NRs lying side by side flat on the surface. In contrast, longer NRs align vertically into ordered superstructures. Systematic variation of the NR length and initial concentration of the NR dispersion allowed us to tune the orientation of the NRs in the final superstructure. With GISAXS, we were able to follow the dynamics of the self-assembly. We propose a model of hierarchical self-organization that provides a basis for the understanding of the length-dependent self-organization of NRs at the liquid/air interface. This opens the way to new materials based on NR membranes and anisotropic thin films.

We present a study of Cd2+-for-Pb2+ exchange in PbSe nanocrystals (NCs) with cube, star, and rod shapes. Prolonged temperature-activated cation exchange results in PbSe/CdSe heterostructured nanocrystals (HNCs) that preserve their specific overall shape, whereas the PbSe core is strongly faceted with dominance of {111} facets. Hence, cation exchange proceeds while the Se anion lattice is preserved, and well-defined {111}/{111} PbSe/CdSe interfaces develop. Interestingly, by quenching the reaction at different stages of the cation exchange new structures have been isolated, such as core–shell nanorods, CdSe rods that contain one or two separated PbSe dots and fully zinc blende CdSe nanorods. The crystallographically anisotropic cation exchange has been characterized by a combined HRTEM/HAADF-STEM study of heterointerface evolution over reaction time and temperature. Strikingly, Pb and Cd are only intermixed at the PbSe/CdSe interface. We propose a plausible model for the cation exchange based on a layer-by-layer replacement of Pb2+ by Cd2+ enabled by a vacancy-assisted cation migration mechanism.Keywords: cation exchange; core/shell nanocrystals; HAADF-STEM; near-infrared-active nanocrystals; PbSe/CdSe;

Atomic force microscopy (AFM) images of graphene and graphite show contrast with atomic periodicity. However, the contrast patterns vary depending on the atomic termination of the AFM tip apex and the tip–sample distance, hampering the identification of the atomic positions. Here, we report quantitative AFM imaging of epitaxial graphene using inert (carbon-monoxide-terminated) and reactive (iridium-terminated) tips. The atomic image contrast is markedly different with these tip terminations. With a reactive tip, we observe an inversion from attractive to repulsive atomic contrast with decreasing tip–sample distance, while a nonreactive tip only yields repulsive atomic contrast. We are able to identify the atoms with both tips at any tip–sample distance. This is a prerequisite for future structural and chemical analysis of adatoms, defects, and the edges of graphene nanostructures, crucial for understanding nanoscale graphene devices.Keywords: AFM; atomic contrast; atomic force microscopy; graphene; graphene edge; Ir(111)

The pathway towards the realization of optical solid-state lasers was gradual and slow. After Einstein's paper on absorption and stimulated emission of light in 1917 it took until 1960 for the first solid state laser device to see the light. Not much later, the first semiconductor laser was demonstrated and lasing in the near UV spectral range from ZnO was reported as early as 1966. The research on the optical properties of ZnO showed a remarkable revival since 1995 with the demonstration of room temperature lasing, which was further enhanced by the first report of lasing by a single nanowire in 2001. Since then, the research focussed increasingly on one-dimensional nanowires of ZnO. We start this review with a brief description of the opto-electronic properties of ZnO that are related to the wurtzite crystal structure. How these properties are modified by the nanowire geometry is discussed in the subsequent sections, in which we present the confined photon and/or polariton modes and how these can be investigated experimentally. Next, we review experimental studies of laser emission from single ZnO nanowires under different experimental conditions. We emphasize the special features resulting from the sub-wavelength dimensions by presenting our results on single ZnO nanowires lying on a substrate. At present, the mechanism of lasing in ZnO (nanowires) is the subject of a strong debate that is considered at the end of this review.

The properties of hetero-nanocrystals (HNCs) depend strongly on the mutual arrangement of the nanoscale components. In this work we have investigated the structural and morphological evolution of colloidal PbSe/CdSe core/shell quantum dots upon annealing under vacuum. Prior to annealing the PbSe core has an approximately octahedral morphology with eight {111} facets, and the CdSe shell has zinc-blende crystal structure. Thermal annealing under vacuum at temperatures between 150 °C and 200 °C induces a structural and morphological reconstruction of the HNCs whereby the PbSe core and the CdSe shell are reorganized into two hemispheres joined by a common {111} Se plane. This thermally induced reconstruction leads to considerable changes in the optical properties of the colloidal PbSe/CdSe HNCs.

Colloidal crystallisation is the only way to obtain three-dimensional ordered materials in which semiconductor, metallic, and magnetic nanocrystals are in close contact. It is expected that the quantum mechanical and dipolar interactions between the nanocrystal units can lead to unseen physical phenomena and materials. Here we review the development of this new and exciting field. We first compare nanocrystal superlattices with regular atomic solids regarding their mechanical strength and opto-electronic properties. We describe how nanocrystal superlattices have been obtained from colloid suspensions in several ways. The thermodynamic driving force for colloidal crystallisation is discussed in terms of inter-particle interactions in a good solvent and entropy. We compare the binary superlattices that have been obtained by solvent evaporation with the predictions of the hard-sphere model and show that semiconductor nanocrystals in a good solvent can behave as hard spheres. Finally, we discuss the quantum mechanical and dipolar interactions in nanocrystal superlattices and review recent studies of the opto-electronic and magnetic properties of novel superlattice materials.Graphical abstractHighlights► We review the differences between a nanocrystal superlattice and a regular atomic solid. ► We review the methods used to characterise the structure of nanocrystal superlattices. ► We review the methods to prepare nanocrystal superlattices and discuss the thermodynamic driving forces. ► We review collective electronic and magnetic properties of nanocrystals superlattices. ► We discuss the emerging applications of nanocrystal superlattices.

Here we advocate the use of single-dot electrical and optical spectroscopy, or combinations of both, to study subtle energetic and dynamic features of colloidal core (shell) nanocrystalline quantum dots. In ensemble experiments, these features are hidden because of inhomogeneous broadening. The remarked physics of confined electrons and excitons as revealed by single-dot spectroscopy often reflects a coupling – enhanced by confinement in the nanocrystal – with other excitations such as lattice phonons and other carriers. We philosophize on a comprehensive single-dot experiment on semiconductor quantum dots that would combine optical and electrical spectroscopy with complete atomic imaging of the investigated structure.

One of the main reasons for the current interest in colloidal nanocrystals is their propensity to form superlattices, systems in which (different) nanocrystals are in close contact in a well-ordered three-dimensional (3D) geometry resulting in novel material properties. However, the principles underlying the formation of binary nanocrystal superlattices are not well understood. Here, we present a study of the driving forces for the formation of binary nanocrystal superlattices by comparing the formed structures with full free energy calculations. The nature (metallic or semiconducting) and the size-ratio of the two nanocrystals are varied systematically. With semiconductor nanocrystals, self-organization at high temperature leads to superlattices (AlB2, NaZn13, MgZn2) in accordance with the phase diagrams for binary hard-sphere mixtures; hence entropy increase is the dominant driving force. A slight change of the conditions results in structures that are energetically stabilized. This study provides rules for the rational design of 3D nanostructured binary semiconductors, materials with promises in thermoelectrics and photovoltaics and which cannot be reached by any other technology.

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.

The properties of hetero-nanocrystals (HNCs) depend strongly on the mutual arrangement of the nanoscale components. In this work we have investigated the structural and morphological evolution of colloidal PbSe/CdSe core/shell quantum dots upon annealing under vacuum. Prior to annealing the PbSe core has an approximately octahedral morphology with eight {111} facets, and the CdSe shell has zinc-blende crystal structure. Thermal annealing under vacuum at temperatures between 150 °C and 200 °C induces a structural and morphological reconstruction of the HNCs whereby the PbSe core and the CdSe shell are reorganized into two hemispheres joined by a common {111} Se plane. This thermally induced reconstruction leads to considerable changes in the optical properties of the colloidal PbSe/CdSe HNCs.