CdSe/ZnS Nanocrystals with Dye-Functionalized Polymer Ligands Containing Many Anchor Groups

Strong enhancement of the Breit-Wigner-Fano Raman line in carbon nanotube bundles caused by plasmon band formation

We investigate the origin of the Breit-Wigner-Fano line in the Raman spectra of individual single-walled carbon nanotubes and their bundles. Using confocal Raman microscopy and atomic-force microscopy we found that the Breit-Wigner-Fano line intensity increases strongly with the bundle thickness. We confirmed this result by Raman investigations of partially decomposed bundles, which were additionally investigated by transmission electron microscopy. Our random-phase approximation based theory, which identifies the Breit-Wigner-Fano line as an excited band of plasmon-phonon modes, is fully consistent with the experimental results.

Investigations of the emission properties of single CdS-nanocrystallites

Semiconductor nanocrystallites (NCs) with a radius in the range of the bulk exciton radius exhibit a strong quantum size effect. We investigated CdS-NCs, that were spin coated on a glass cover slip, with a low temperature confocal microscope. At low coverage we could image the fluorescence light from single NCs. The typical emission spectra of single NCs show four peaks. Besides the main peak related to near bandgap recombination, up to two LO-phonon satellites and one blue shifted peak were observed. It could be shown that the absorption can be polarization dependent. From the images as well as from the intensity autocorrelation function it could be concluded that the fluorescence emission…

Scanning near-field optical microscopy using semiconductor nanocrystals as a local fluorescence and fluorescence resonance energy transfer source

Local fluorescence probes based on CdSe semiconductor nanocrystals were prepared and tested by recording scanning near-field optical microscopy (SNOM) images of calibration samples and fluorescence resonance energy transfer SNOM (FRET SNOM) images of acceptor dye molecules inhomogeneously deposited onto a glass substrate. Thousands of nanocrystals contribute to the signal when this probe is used as a local fluorescence source while only tens of those (the most apical) are involved in imaging for the FRET SNOM operation mode. The dip-coating method used to make the probe enables diminishing the number of active fluorescent nanocrystals easily. Prospects to realize FRET SNOM based on a single…

Electrical Transport and Confocal Raman Studies of Electrochemically Modified Individual Carbon Nanotubes

Raman investigation of single oxidized carbon nanotubes

The oxidation process of single-walled carbon nanotubes via nitric acid treatment was followed by IR-, UV-Vis-NIR, and single bundle Raman spectroscopy. The introduction of functional, oxygen-containing groups is revealed by an additional absorption band at 1725 cm−1, characteristic of carbonyl stretch vibrations. No significant shift of the optical absorption bands could be detected after oxidation. The combination of atomic force microscopy and confocal scanning resonance-enhanced Raman microscopy was used to investigate thin bundles and, eventually, individual nanotubes in detail. These experiments enabled determination of the dependence of the Raman intensity of the G-line (around 1590 …

Buchbesprechung: Nanoscale Materials in Chemistry. Herausgegeben von Kenneth J. Klabunde

Carbon Nanotubes. By Stefanie Reich, Christian Thomsen and Janina Maultzsch.

Combination of Confocal Raman Spectroscopy and Electron Microscopy on the Same Individual Bundles of Single-Walled Carbon Nanotubes

We report a method to investigate the same individual single-walled carbon nanotube (SWNT) bundles with both transmission electron microscopy (TEM) and Raman spectroscopy. Free-standing individual bundles are obtained by depositing a solution of suspend SWNTs on a carbon film with a regular pattern of holes, which can be localized by TEM and also by confocal Raman microscopy. While most of the TEM images predict that the bundles consist of tubes with a similar diameter, we will show that occasionally a certain tube diameter can be associated with a particular radial breathing mode frequency of the Raman spectrum. Single-walled carbon nanotubes (SWNTs) are one-dimensional molecular structure…

Structure determination and homogeneous optical properties of CdS/HgS quantum dots

The structural and optical properties of heterogeneous semiconductor nanoparticles consisting of CdS and HgS are investigated by High Resolution Electron Microscopy (HRTEM) and selective spectroscopy like Hole Burning (HB) and Fluorescence Line Narrowing (FLN). The HRTEM study shows that epitaxy is possible in nanocrystals, provided the crystallites have well defined faceted shapes to begin with. From the HB- and FLN experiments homogeneous absorption and fluorescence spectra are calculated. It could be shown that the absorption is coupled to HgS-like phonons (250 cm -1 ) whereas the emission frequency is closer to the LO phonon frequency of CdS.

Raman Imaging of Single Carbon Nanotubes

[19] The single crystals of the Bu4NBr0.6I1.4Cl salt, were obtained by addition of IBr to a solution of Bu4NCl in ethanol at a reagent ratio of 1:0.5. Stoichiometry of the anion has been found by EDX. Based on a Raman study the anion consists of the I2Br ‐ (band at 140 cm ‐1 ), IBr2 ‐ (band at 150‐ 176 cm ‐1 ), BrICl ‐ (band at 225 cm ‐1 ), and ICl2 ‐ (band at 250‐263 cm ‐1 ) trihalide anions. [20] The X-ray diffraction data from single crystals for both trihalide salts were measured using an Enraf Nonius CAD4 diffractometer with graphite monochromatic Mo Ka radiation (k = 0.71073 a) at room temperature. Unit cell parameters of the new a¢¢¢- crystal were determined from a leastsquares analy…

Ligand density on nanoparticles: A parameter with critical impact on nanomedicine

Nanoparticles modified with ligands for specific targeting towards receptors expressed on the surface of target cells are discussed in literature towards improved delivery strategies. In such concepts the ligand density on the surface of the nanoparticles plays an important role. How many ligands per nanoparticle are best for the most efficient delivery? Importantly, this number may be different for in vitro and in vivo scenarios. In this review first viruses as "biological" nanoparticles are analyzed towards their ligand density, which is then compared to the ligand density of engineered nanoparticles. Then, experiments are reviewed in which in vitro and in vivo nanoparticle delivery has b…

Raman imaging and spectroscopy of heterogeneous individual carbon nanotubes

Isolated single-walled carbon nanotubes (CNTs) were grown by chemical vapor deposition methods on Fe/Mo/Al2O3 catalysts, which were patterned by microcontact printing. The pattern allowed us to trace back and investigate the same isolated CNT by atomic-force (AFM) and confocal Raman microscopy with different excitation wavelengths. A change of the Raman intensity could be correlated with structural defects revealing that the molecular structure of the tubes is changing along the tube axis. By investigating the same tube segments with different excitation energies, we found that the D-line of isolated tubes shows a strong dispersive effect of 45−50 cm-1/eV. In contrast, the spectral position…

Quantum wells within quantum dots, a CdS/HgS nanoheterostructure with global and local confinement

Semiconductor nanocrystals prepared by methods of wet chemistry are similar to MBE grown quantum dots where the mobility of the charge carriers is reduced to zero dimensionality. In this paper we summarize the physics of a unique system in which the charge carriers are locally confined within a heterogeneous quantum dot. With high resolution electron microscopy we will show that epitaxial growth ot atomic layer precision is possible by methods of solution chemistry leading to CdS quantum dots with embedded HgS quantum wells (QDQWs). The photophysics of this system is investigated by time-correlated single photon counting, transient differential absorption and fluorescence line narrowing spe…

CdSe/ZnS-Nanokristalle mit farbstoffmarkierten Polymerliganden mit mehrfachen Ankergruppen

Semiconductor Nanocrystals with Multifunctional Polymer Ligands

In this letter, we describe the preparation of a versatile polymer ligand, which can be attached to CdSe/ZnS semiconductor nanocrystals via a phase transfer reaction. The ligand is based on a chain of reactive esters, which can, in principle, be substituted by any compound containing amino-functionalities. The polymer/nanocrystal complexes are characterized in terms of structure and photostability.

Oxygen-Induced Blinking of Single CdSe Nanocrystals

Synthesis and Characterization of Highly Luminescent CdSe—Core CdS/Zn0.5Cd0.5S/ZnS Multishell Nanocrystals.

We report on the preparation and structural characterization of CdSe nanocrystals, which are covered by a multishell structure from CdS and ZnS. By using the newly developed successive ion layer adhesion and reaction (SILAR) technique, we could gradually change the shell composition from CdS to ZnS in the radial direction. Because of the stepwise adjustment of the lattice parameters in the radial direction, the resulting nanocrystals show a high crystallinity and are almost perfectly spherical, as was investigated by X-ray diffraction and electron microscopy. Also, due to the radial increase of the respective valence- and conduction-band offsets, the nanocrystals are well electronically pas…

Book Review: Nanoscale Materials in Chemistry. Edited by Kenneth J. Klabunde

Fluorescence Decay Time of Single Semiconductor Nanocrystals

We present fluorescence decay measurements of single ZnS covered CdSe nanocrystals. It is shown that the fluorescence decay time is fluctuating during the investigation leading to a multiexponential decay even for a single nanocrystal. In combination with measurements of the fluorescence blinking behavior we find that a high fluorescence intensity is correlated with a long fluorescence decay time. This is consistent with a model of fluctuating nonradiative decay channels leading to variable dynamic quenching processes of the excited state.

Terrylene in p-terphenyl: single-molecule experiments at room temperature

Abstract This paper reports on fluorescence microscopy and spectroscopy of single terrylene molecules embedded in p -terphenyl at room temperature. The basic photophysical parameters of this crystalline host/guest system such as photostability, single-molecule emission rates and the properties of dispersed fluorescence spectra are reported. The stability of the single-molecule signals allowed the direct observation of singlet–triplet quantum jumps at room temperature, by means of which the underlying intersystem crossing rates can be investigated. The results of earlier investigations at liquid-helium temperatures are reviewed briefly where appropriate. The properties of terrylene in p -ter…

<title>Probing the interactions of single CdSe quantum dots with their local environment</title>

The fluorescence blinking of single CdSe/ZnS nanocrystals under different experimental conditions is investigated. We show that the blinking process is very sensitive to the particle environment even if the nanocrystals are covered with a few monolayers of ZnS. Especially the presence of oxygen leads to a shortening of the on-times but leaves the off-times almost unaffected. Therefore, oxygen which is adsorbed to the surface might act as a scavenger for photo generated electrons and leaves the particle in its (positively charged) dark state.