CdTe nanoclusters were prepared in aqueous solution by the reaction between Cd 2+ and NaHTe in the presence of thioglycolic acid. Under reflux, the clusters start to crystallize and show a narrow band emission. The photoluminescence efficiency of CdTe nanocrystals strongly depends on the pH value of the colloidal solution.The maximum quantum yield at room temperature is approximately 18% when the pH value of the CdTe solution is brought to 4.5 by using thioglycolic acid. The optical spectroscopy studies imply that the pHdependent behavior of the CdTe nanocrystals' fluorescence is caused by structural changes on the surface rather than the size of the nanocrystals. Systematic absorption and fluorescence studies on dialyzed samples suggest that in the acidic range a shell of cadmium thiol complexes is formed around the CdTe core. Thus, the fluorescence quantum yield is enhanced dramatically when the solution is made acidic. In contrast, such a shell can also be produced in the alkaline range, but only after the CdTe nanocrystal crude solution is purified by dialysis.

Light- and small-angle neutron scattering as well as cryo-transmission electron microscopy (cryo-TEM) studies were performed to probe the structure of J-aggregates formed by a series of achiral dye molecules of the 5,5‘,6,6‘-tetrachlorobenzimidacarbocyanine chromophore having 1,1‘-dialkyl substituents combined with 3,3‘-bis(4-sulfobutyl)-3,3‘-bis(4-carboxybutyl) or 3,3‘-bis(3-carboxypropyl) substituents. Assemblies that display a dependence on the substituents different complex supramolecular structures of nanometer-to-micrometer size have been directly visualized by cryo-TEM. The superstructures span from monomolecular layers formed by the 1,1‘-diethyl-3,3‘-bis(4-sulfobutyl) derivative and stacks of bilayer ribbons in the case of the 1,1‘-dioctyl-3,3‘-bis(4-carboxybutyl) derivative to twisted ropelike structures for the chiral aggregate of the 1,1‘-dioctyl-3,3‘-bis(3-carboxypropyl)-substituted chromophore.

Uniform exciton fluorescence from individual molecular nanotubes immobilized on solid substrates Eisele, Doerthe M.; Knoester, Jasper; Kirstein, Stefan; Rabe, Juergen P.; Vanden Bout, David A.; Rabe, Jürgen P. Take-down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim.Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons the number of authors shown on this cover page is limited to 10 maximum. Since the optical properties of the tubular J-aggregates strongly depend on their specific supramolecular structure, the absorption and emission spectra from the sample can be used to determine if the molecular structure of the aggregates has changed upon deposition onto the substrate. Because the tubules on the substrate are highly dilute, emission spectra rather than the very weak absorption spectra were used. Emission spectra were collected rather than excitation spectra because of the extremely small Stokes shift for the emission. Emission spectra of tubular J-aggregates in solution (red) and after preparation on a quartz surface (black)via spin-coating and slowly drying in air (c) Idem, but now the black line is the spectrum of aggregates prepared on quartz via the drop flow technique and drying by blowing with nitrogen.As shown in the manuscript, the sample prepared by the drop-flow technique and carefully dried in air in a black box had spectra that were nearly identical in both position and width to the solution, indicating no significant morphological and structural changes upon deposition.3

The simultaneous chemical linkage of cyanine dye chromophores with both hydrophobic and hydrophilic substituents leads to a new type of amphiphilic molecules with the ability of spontaneous self-organization into highly ordered aggregates of various structures and morphologies. These aggregates carry the outstanding optical properties of J-aggregates, namely, efficient exciton coupling and fast exciton energy migration, which are essential for the build up of artificial light harvesting systems. The morphology of the aggregates depends sensitively on the molecular structure of the chemical substituents of the dye chromophore. Accordingly, lamellar ribbon-like structures, vesicles , tubes, and bundles of tubes are found depending on the dyes and the structure can further be altered by addition of surfactants, alcohols, or other additives. Altogether the tubular structure is the most noticeable structural motif of these types of J-aggregates. The optical spectra are characterized in general by a complex exciton spectrum which is composed of several electronic transitions. The spectrum is red-shifted as a total with respect to the monomer absorption and exhibits resonance fluorescence from the lowest energy transition. For the tubular structures, the optical spectra can be related to a structural model. Although the molecules itself are strictly achiral, a pronounced circular dichroism (CD) is observed for the tubular aggregates and explained by unequal distribution of left- and right-handed helicity of the tubes. Photo-induced electron transfer (PET) reactions from the dye aggregates to electron acceptor molecules lead to superquenching which proves the delocalization of the excitation. This property is used to synthesize metal nanoparticles on the aggregate surface by photo-induced reduction of metal ions.

Water soluble thiol capped CdTe nanocrystals are assembled into ultrathin films in combination with poly(diallyldimethylammonium chloride) (PDDA) by the self-assembly method of layer-by-layer adsorption of oppositely charged polyelectrolytes. Electroluminescent devices, which produce different color emissions, are fabricated by sandwiching CdTe/PDDA films between indium–tin–oxide (ITO) and aluminum electrodes using CdTe nanocrystals of different sizes. It is shown that the electroluminescence (EL) spectra of the CdTe/polymer films are nearly identical to the photoluminescence spectra of the corresponding CdTe nanocrystals in aqueous solutions. The devices produce room-light visible light output with an external quantum efficiency up to 0.1%. Light emission is observed at current densities of 10 mA/cm2 and at low onset voltages of 2.5–3.5 V, which depends on the thickness of the film indicating field-dependent current injection. A variation of the EL efficiency with the size of the CdTe particles is observed and explained by the size dependent shift of the CdTe energy levels with respect to the work function of the electron injecting Al electrode. This is confirmed by the behavior of two-layer devices prepared from two differently sized CdTe particles being spatially separated, i.e., one size CdTe near ITO and the other size CdTe near Al by using the self-assembly method.

The amphiphilic dye 3,3'-bis(2-sulfopropyl)-5,5',6,6'-tetrachloro-1,1'-dioctylbenzimidacarbocyanine (C8S3) self-aggregates in aqueous solution to form tubular J-aggregates with a diameter of 17.0 +/- 0.5 nm, a wall thickness of approximately 4 nm, and a length exceeding several hundred nanometers. The absorption spectrum shows the typical features expected for tubular J-aggregates with several sharp and red-shifted absorption bands. Morphological investigations using cryo-transmission electron microscopy (cryo-TEM) and spectroscopic investigations reveal a high stability of the tubular morphology but a tendency of the aggregates to assemble into ropelike bundles after several weeks of storage. It is found that aggregation in solutions containing additives such as alcohols or surfactants results in the formation of new types of aggregates. A second type of tubular aggregate with a diameter of 13.0 +/- 0.5 nm is observed when the solutions contain more than 10 wt % MeOH. On the time scale of days these tubular aggregates transform into ribbonlike structures characterized by a new absorption spectrum, and they convert after several weeks into giant tubes with diameters of up to 500 nm.

Electrooptical and structural studies on self-assembled films composed of CdSe nanoparticles, poly(p-phenylene vinylene) (PPV), and different nonconjugated polyelectrolytes are reported. It is demonstrated by optical spectroscopy and X-ray reflectivity measurements that CdSe nanoparticles and PPV can successfully be incorporated into homogeneous ultrathin films by the self-assembly method. The surface roughness obtained from the X-ray measurements is 2.7 and 1.3 nm respectively for CdSe/PAH (PAH, poly(allylamine) hydrochloride) and PSS/PPV (PSS, poly(styrenesulfonic acid)) multilayer films. This allows us to stack a (PSS/PPV)*n film on top of a (CdSe/PAH)*n film to build up well-defined two-layer composite film devices. Electroluminescence studies show that pure (PSS/PPV)*n film devices exhibit green light emission but with a very short lifetime (several seconds) if operated in ambient air. During operation, the PPV emission shifts toward the blue, which indicates that the mean conjugation length of PPV is shortened due to oxidation. Oxidation of CdSe particles is also observed in (CdSe/PAH)*n devices during operation. However, the stability of CdSe particles is enhanced if they are combined alternately with PPV, and a (CdSe/PPV)*n device gives a broad, nearly white emission. The turn-on voltage of it is much smaller and better defined than that for a (CdSe/PAH)*20 device. This proves that PPV works like a charge-transportation layer rather than an emitting layer in the (CdSe/PPV)*n film device. In an ITO//PEI(CdSe/PAH)*10/(PSS/PPV)*10//Al two-layer composite film device the lifetime of PPV electroluminescence can be prolonged for at least 1 order of magnitude only after the device is first operated under backward bias (positive pole on Al electrode). This suggests that the oxygen within the film is removed by this operation due to oxidation of the particles. Afterward, this two-layer composite film device presents emission from PPV and CdSe, respectively, when the sign of the external voltage is changed.

We demonstrate trench channeling of mono- and multilayer graphenes with silver nanoparticles with high speed in ambient environment and at elevated temperatures. A silver nanoparticle located at a graphene edge catalyzes oxidation of neighboring carbon atoms, thereby burning a trench into the graphene layer. High-resolution scanning tunneling microscopy imaging reveals that the trench edges are very smooth with a peak-to-peak roughness below 2 nm. We discuss the channeling mechanism and demonstrate that channeling speeds of up to 250 nm/s and the smoothness of the resulting trenches indicate the prospect of a "catalytic pen" for high-precision lithography on graphenes.