Raman characterization of Cu2ZnSnS4 nanocrystals: phonon confinement effect and formation of Cu x S phases.

A Raman spectroscopic study of Cu2ZnSnS4 (CZTS) nanocrystals (NCs) produced by a "green" synthesis in aqueous solutions is reported. Size-selected CZTS NCs reveal phonon confinement that manifests itself in an upward shift of the main phonon peak by about 3-4 cm-1 by varying the NC diameter from 3 to 2 nm. A non-monotonous shift and narrowing of the main peak are attributed to the special shape of the phonon dispersion in this material. Moreover, the method of sample preparation, the nature of the supporting substrate and the photoexcitation regime are found to crucially influence the Raman spectra of the CZTS samples. Particularly, the possible oxidation and hydrolysis of CZTS NCs with the concomitant formation of a Cu-S phase are systematically investigated. The nature of the film support is found to strongly affect the amount of admixture copper sulfide phases with the Cu2-x S/CuS content being the highest for oxidized silicon and glass and notably lower for ITO and even less for gold supports. The effect is assumed to originate from the different hydrophilicity of the supporting surfaces, resulting in a different morphology and surface area of the NC film exposed to the atmosphere, as well as the degree of the NC oxidation/hydrolysis. The amount of copper sulfide increases with the laser power. This effect is interpreted as a result of photochemical/photocatalytic transformations of the CZTS NCs.

Immobilization of pH-sensitive CdTe Quantum Dots in a Poly(acrylate) Hydrogel for Microfluidic Applications.

Microfluidic devices present the basis of modern life sciences and chemical information processing. To control the flow and to allow optical readout, a reliable sensor material that can be easily utilized for microfluidic systems is in demand. Here, we present a new optical readout system for pH sensing based on pH sensitive, photoluminescent glutathione capped cadmium telluride quantum dots that are covalently immobilized in a poly(acrylate) hydrogel. For an applicable pH sensing the generated hybrid material is integrated in a microfluidic sensor chip setup. The hybrid material not only allows in situ readout, but also possesses valve properties due to the swelling behavior of the poly(acrylate) hydrogel. In this work, the swelling property of the hybrid material is utilized in a microfluidic valve seat, where a valve opening process is demonstrated by a fluid flow change and in situ monitored by photoluminescence quenching. This discrete photoluminescence detection (ON/OFF) of the fluid flow change (OFF/ON) enables upcoming chemical information processing.

Homogeneity and elemental distribution in self-assembled bimetallic Pd-Pt aerogels prepared by a spontaneous one-step gelation process.

Multi-metallic aerogels have recently emerged as a novel and promising class of unsupported electrocatalyst materials due to their high catalytic activity and improved durability for various electrochemical reactions. Aerogels can be prepared by a spontaneous one-step gelation process, where the chemical co-reduction of metal precursors and the prompt formation of nanochain-containing hydrogels, as a preliminary stage for the preparation of aerogels, take place. However, detailed knowledge about the homogeneity and chemical distribution of these three-dimensional Pd-Pt aerogels at the nano-scale as well as at the macro-scale is still unclear. Therefore, we used a combination of spectroscopic and microscopic techniques to obtain a better insight into the structure and elemental distribution of the various Pd-rich Pd-Pt aerogels prepared by the spontaneous one-step gelation process. Synchrotron-based extended X-ray absorption fine structure (EXAFS) spectroscopy and high-angle annular dark-field (HAADF) scanning transmission electron microscopy (STEM) in combination with energy-dispersive X-ray spectroscopy (EDX) were employed in this work to uncover the structural architecture and chemical composition of the various Pd-rich Pd-Pt aerogels over a broad length range. The Pd80Pt20, Pd60Pt40 and Pd50Pt50 aerogels showed heterogeneity in the chemical distribution of the Pt and Pd atoms inside the macroscopic nanochain-network. The features of mono-metallic clusters were not detected by EXAFS or STEM-EDX, indicating alloyed nanoparticles. However, the local chemical composition of the Pd-Pt alloys strongly varied along the nanochains and thus within a single aerogel. To determine the electrochemically active surface area (ECSA) of the Pd-Pt aerogels for application in electrocatalysis, we used the electrochemical CO stripping method. Due to their high porosity and extended network structure, the resulting values of the ECSA for the Pd-Pt aerogels were higher than that for a commercially available unsupported Pt black catalyst. We show that the Pd-Pt aerogels possess a high utilization of catalytically active centers for electrocatalytic applications based on the nanostructured bimetallic framework. Knowledge about the homogeneity and chemical distribution of the bimetallic aerogels can help to further optimize their preparation by the spontaneous one-step gelation process and to tune their electrocatalytic reactivity.

pH and concentration dependence of the optical properties of thiol-capped CdTe nanocrystals in water and D2O.

The optical properties of semiconductor nanocrystals (SC NCs) are largely controlled by their size and surface chemistry, i.e., the chemical composition and thickness of inorganic passivation shells and the chemical nature and number of surface ligands as well as the strength of their bonds to surface atoms. The latter is particularly important for CdTe NCs, which - together with alloyed CdxHg1-xTe - are the only SC NCs that can be prepared in water in high quality without the need for an additional inorganic passivation shell. Aiming at a better understanding of the role of stabilizing ligands for the control of the application-relevant fluorescence features of SC NCs, we assessed the influence of two of the most commonly used monodentate thiol ligands, thioglycolic acid (TGA) and mercaptopropionic acid (MPA), on the colloidal stability, photoluminescence (PL) quantum yield (QY), and PL decay behavior of a set of CdTe NC colloids. As an indirect measure for the strength of the coordinative bond of the ligands to SC NC surface atoms, the influence of the pH (pD) and the concentration on the PL properties of these colloids was examined in water and D2O and compared to the results from previous dilution studies with a set of thiol-capped Cd1-xHgxTe SC NCs in D2O. As a prerequisite for these studies, the number of surface ligands was determined photometrically at different steps of purification after SC NC synthesis with Ellman's test. Our results demonstrate ligand control of the pH-dependent PL of these SC NCs, with MPA-stabilized CdTe NCs being less prone to luminescence quenching than TGA-capped ones. For both types of CdTe colloids, ligand desorption is more pronounced in H2O compared to D2O, underlining also the role of hydrogen bonding and solvent molecules.

Flexible and fragmentable tandem photosensitive nanocrystal skins.

We proposed and demonstrated the first account of large-area, semi-transparent, tandem photosensitive nanocrystal skins (PNSs) constructed on flexible substrates operating on the principle of photogenerated potential buildup, which avoid the need for applying an external bias and circumvent the current-matching limitation between junctions. We successfully fabricated and operated the tandem PNSs composed of single monolayers of colloidal water-soluble CdTe and CdHgTe nanocrystals (NCs) in adjacent junctions on a Kapton polymer tape. Owing to the usage of a single NC layer in each junction, noise generation was significantly reduced while keeping the resulting PNS films considerably transparent. In each junction, photogenerated excitons are dissociated at the interface of the semi-transparent Al electrode and the NC layer, with holes migrating to the contact electrode and electrons trapped in the NCs. As a result, the tandem PNSs lead to an open-circuit photovoltage buildup equal to the sum of those of the two single junctions, exhibiting a total voltage buildup of 128.4 mV at an excitation intensity of 75.8 µW cm(-2) at 350 nm. Furthermore, we showed that these flexible PNSs could be bent over 3.5 mm radius of curvature and cut out in arbitrary shapes without damaging the operation of individual parts and without introducing any significant loss in the total sensitivity. These findings indicate that the NC skins are promising as building blocks to make low-cost, flexible, large-area UV/visible sensing platforms with highly efficient full-spectrum conversion.

Hyperbolic metamaterials based on quantum-dot plasmon-resonator nanocomposites.

We theoretically demonstrate that nanocomposites made of colloidal semiconductor quantum dot monolayers placed between metal nanoparticle monolayers can function as multilayer hyperbolic metamaterials. Depending on the thickness of the spacer between the quantum dot and nanoparticle layers, the effective permittivity tensor of the nanocomposite is shown to become indefinite, resulting in increased photonic density of states and strong enhancement of quantum dot luminescence. This explains the results of recent experiments [T. Ozel et al., ACS Nano 5, 1328 (2011)] and confirms that hyperbolic metamaterials are capable of increasing the radiative decay rate of emission centers inside them. The proposed theoretical framework can also be used to design quantum-dot/nanoplasmonic composites with optimized luminescence enhancement.

Resonance energy transfer in self-organized organic/inorganic dendrite structures.

Hybrid materials formed by semiconductor quantum dots and J-aggregates of cyanine dyes provide a unique combination of enhanced absorption in inorganic constituents with large oscillator strength and extremely narrow exciton bands of the organic component. The optical properties of dendrite structures with fractal dimension 1.7-1.8, formed from J-aggregates integrated with CdTe quantum dots (QDs), have been investigated by photoluminescence spectroscopy and fluorescence lifetime imaging microscopy. Our results demonstrate that (i) J-aggregates are coupled to QDs by Förster-type resonant energy transfer and (ii) there are energy fluxes from the periphery to the centre of the structure, where the QD density is higher than in the periphery of the dendrite. Such an anisotropic energy transport can be only observed when dendrites are formed from QDs integrated with J-aggregates. These QD/J-aggregate hybrid systems can have applications in light harvesting systems and optical sensors with extended absorption spectra.

Saturated near-resonant refractive optical nonlinearity in CdTe quantum dots.

In this work, we report on an experimental investigation of the nonlinear optical properties near the first electronic resonance of thiol-capped CdTe quantum dots (QDs) being in the strong confinement regime. Using a cw laser excitation in a Z-scan experimental setup, we show the presence of saturated Kerr-type nonlinear optical properties of the QDs, at low intensity levels. The large optical nonlinearity and the control of the linear and nonlinear optical properties by the size of the QDs are of special interest for applications in integrated nanophotonic devices.

Switchable photoluminescence of CdTe nanocrystals by temperature-responsive microgels.

In the present study, we report a method for preparing a fluorescent thermosensitive hybrid material based on monodisperse, thermosensitive poly( N-isopropyl acrylamide) (PNIPAM) microgels covered with CdTe nanocrystals of 3.2 nm diameter. The CdTe nanocrystals were covalently immobilized on the surface of PNIPAM microgels. The chemical environment around the CdTe nanocrystals was modified by changing the temperature and inducing the microgel volume-phase transition. This change provoked a steep variation in the nanocrystal photoluminescence (PL) intensity in such a way that when the temperature was under the low critical solution temperature (LCST) of the polymer (36 degrees C) the PL of the nanocrystals was strongly quenched, whereas above the LCST the PL intensity was restored.

Red shift for CdTe nanoparticle thin films and suspensions during heating.

The work that we have conducted shows that temperature affects the wavelength of light emitted from CdTe nanoparticle clusters that are in a suspension or deposited into thin films via a layer-by-layer process. Compared with the stock suspension, the films show an initial photoluminescent shift, of circa 6-8 nm to the red, when the particles are deposited. A shift of circa 6-8 nm is also seen when the suspensions are first heated to 85 degrees C from room temperature (20 degrees C) having been stored in a fridge at 5 degrees C. This shift is non-recoverable. With continual cycling from room temperature to 85 degrees C the suspensions show a slight tendency for the emission to move increasingly to the red; whereas the films show no such tendency. In both cases, the range in emission is ca 10 nm from the room temperature state to 80 degrees C. The intensity of the emission from the film drops abruptly (ca 50% reduction) after one cycle of heating; in the suspension there is an initial increase (ca 3-5% increase) in intensity before it decays. We see that the shift towards the red has been attributed to energy transfer or a rearrangement of the packing of the particles in the thin films. After conducting analysis of the films using scanning probe microscopy we have determined that a change in the morphology is responsible for the permanent shift in emission wavelength associated with prolonged heating. The influence of traps has not been ruled out, but the morphological change in the samples is very large and is likely to be the dominating mechanism affecting change for the red shift at room temperature.

A photoluminescence study of film structure in CdTe nanoparticle thin films.

The layer-by-layer deposition of thin films of CdTe nanoparticles and three different polyelectrolytes has been investigated. Photoluminescence spectra were used to monitor the energy transfer properties within the films. As the number of bilayers in a thin film was increased a decrease in the energy of the light emitted was observed. The wavelength change is a two-stage process. Deposition of the first one to two bi-layers of a thin film produced a sharp energy change (626 nm to 637 nm with the addition of a single bi-layer) whereas deposition of subsequent bi-layers produced a more gradual energy change (642 nm-646 nm with the addition of 5 bi-layers). A space-filling mechanism is suggested to account for these changes; smaller nanoparticles penetrate the earlier levels of a thin film and increase the inter-particle energy transfer opportunities within the layers.

Emission stimulation in a directional band gap of a CdTe-loaded opal photonic crystal.

An anisotropic photonic crystal light source has been realized by impregnation of a thin film latex opal with brightly luminescent CdTe nanocrystals. Its photoluminescence along a given direction has been studied as a function of excitation power. An increase of the photoluminescence saturation threshold in the directional photonic band gap has been observed. This result is interpreted as a stimulation of emission coupled to specific eigenmodes of a directional band gap. A theoretical model exploiting the low group velocity eigenmodes has been elaborated to explain the resonance character of the emission with band gap frequencies.