A high luminescence efficiency is an important property of colloidal quantum dots (QDs), and quantum yields higher than 90% have been reported for coreÀshell QDs. 1 High efficiencies are especially important for application of QDs as luminescent biolabels, 2 in QD lasers, 3 in spectral converters for warm white LEDs, 4,5 electroluminescent devices, 6 and solar concentrators. 7 Luminescence efficiencies are strongly temperature-dependent. 8 Extensive temperature-dependent luminescence studies for colloidal QDs have been conducted at cryogenic temperatures (0.3À300 K). 9À15 In this temperature region, interesting effects were observed, including a prolonged lifetime below 20 K related to brightÀdark state splitting, 11,16 thermally activated quenching due to surface defect states, 9,10,17 and temperature antiquenching assigned to a phase transition in the capping layer. 14,15 However, the luminescence properties of QDs above room temperature (RT) are hardly investigated, and yet, for most applications in luminescent devices, the working temperature is higher than 300 K. An interesting example is the recent application of QDs as color converters in warm-white LEDs, 18 in which QDs serve as narrow band red emitters under excitation with blue light from a (In,Ga)N LED. The narrow emission bandwidth renders QDs superior to classical phosphors based on broad band emission from luminescent ions. 19 In high-power LEDs for general lighting applications, the heat generated in the pÀn junction and phosphor converter layer leads to temperatures as high as 150À200°C in the layer applied on top of the blue diode. 20 To avoid these high temperatures, the QD phosphor layer can be placed in a more remote configuration. Still, temperatures in such a configuration are expected to be well above 50°C due to heat dissipation of the QDs themselves (excess energy from converting the blue into red light). Clearly, the quenching of QD luminescence at elevated temperatures is relevant for application of QDs in luminescent devices, and a better insight in the quenching behavior is needed.Despite its importance, research on luminescence temperature quenching above RT is very limited for QDs. It is theoretically expected for a QD to have a very high luminescence quenching temperature (T q ). Three generally accepted mechanisms for thermal quenching involve thermally activated crossover from the excited state to the ground state, multiphonon relaxation, and thermally activated photoionization. The first mechanism is generally depicted in a simple configurational coordinate diagram. 8,21 The energy difference between the minimum * Address correspondence to a.meijerink@uu.nl.Received for review July 18, 2012 and accepted September 14, 2012. Published online 10.1021/nn303217qABSTRACT Thermal quenching of quantum dot (QD) luminescence is important for application in luminescent devices. Systematic studies of the quenching behavior above 300 K are, however, lacking. Here, high-temperature (300À500 K) luminescence studies are reported for highly ef...

Colloidal quantum dots (QDs) show great promises as LED phosphors due to their tuneable narrow-band emission and ability to produce high-quality white light.Currently, the most suitable QDs for lighting applications are based on cadmium, which presents a toxicity problem for consumer applications. The most promising cadmiumfree candidate QDs are based on InP, but their quality lags much behind that of cadmium based QDs. This is not only because the synthesis of InP QDs is more challenging than that of Cd-based QDs, but also because the large lattice parameter of InP makes it difficult to grow an epitaxial, defect free shell on top of such material. Here we propose an original approach to overcome this problem by alloying InP nanocrystals with Zn 2+ ions, which enables the synthesis of In x Zn y P alloy QDs having lattice constant that can be tuned from 5.93 Å (pure InP QDs) down to 5.39 Å by simply varying the concentration of the Zn precursor. This lattice engineering allows for subsequent strainfree, epitaxial growth of a ZnSe z S 1-z shell with lattice parameters matching that of the core. We demonstrate, for a wide range of core and shell compositions (i.e. varying x, y and z), that the photoluminescence quantum yield is maximal (up to 60%) when lattice mismatch is minimal.3

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.

ABSTRACT:We study the self-assembly of colloidal CdSe/CdS nanorods (NRs) at the liquid/air interface combining timeresolved 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. KEYWORDS: Nanocrystals, self-assembly, superlattice, grazing-incidence small-angle X-ray scattering T he ability to design the chemical and physical properties of colloidal nanocrystals (NCs) at the atomic level, combined with the possibilities of NC self-assembly is of great fundamental and applied interest. Self-assembly of NCs is a promising route toward the fabrication of new classes of materials in which collective properties may emerge as consequence of dipolar or quantum coupling between the NC building blocks.1,2 NC superlattices and NC "membranes" are increasingly exploited as tailored nanostructured materials in optoelectronic devices such as LEDs, 3−5 lasers 6 and solar cells.7−10 Direct formation of nanocrystal superlattices at the liquid/air interface is currently emerging as a promising method to fabricate functional ultrathin films. Previous works reported promising results on the formation of (mm 2 large) areas of thin films of binary and ternary superlattices composed of spherical NCs. These studies enhanced our understanding of the driving forces underlying NCs self-assembly. 11−17A new direction in this field is self-assembly of highly anisotropic nanocrystals, 18 such as nanorods (NRs). 19 The formation of vertically aligned and hexagonally packed superlattices was initially performed using an external electric field during the process of solvent evaporation.20,21 Subsequent efforts, however, have demonstrated that vertically aligned NR superlattices can be obtained by controlled solvent evaporation in the absence of any external forces.22−34 Self-assembly parameters like the aspect ratio of the NRs, evaporation temperature, and type of solvent were extensively explored. 35 However, only the final structures were studied. To our knowledge, no in situ investigation of the dynamics of the selfassembly process has been reported, yet.Here, we present a study of the mechanism of and the final structures formed by semiconductor NRs self-assembly. We observed that self-assembly occurs at the suspension/air interface and consists o...

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.

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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.

Light emission of semiconductor nanocrystals is a complex process, depending on many factors, among which are the quantum mechanical size confinement of excitons (coupled electron-hole pairs) and the influence of confined phonon modes and the nanocrystal surface. Despite years of research, the nature of nanocrystal emission at low temperatures is still under debate. Here we unravel the different optical recombination pathways of CdSe/CdS dot-in-rod systems that show an unprecedented number of narrow emission lines upon resonant laser excitation. By using self-assembled, vertically aligned rods and application of crystallographically oriented high magnetic fields, the origin of all these peaks is established. We observe a clear signature of an acoustic-phonon assisted transition, separated from the zero-phonon emission and optical-phonon replica, proving that nanocrystal light emission results from an intricate interplay between bright (optically allowed) and dark (optically forbidden) exciton states, coupled to both acoustic and optical phonon modes.