Carbon nanotubes functionalized with dye molecules and metal nanoparticles

Single-walled carbon nanotubes are highly interesting quasi one-dimensional nanostructures. They possess a multitude of fascinating optical, mechanical and electrical properties, which can be even further expanded through appropriate functionalization strategies. This thesis covers a number of functionalization strategies and their effects on the nanotube's optical and electrical properties. The first part deals with the functionalization of carbon nanotubes with dye molecules and the characterization of the functionalized system. Both covalent and noncovalent approaches were investigated with the goal of modifying the nanotubes' photoelectrical properties. Upon excitation with light of the appropriate wavelength, a clear electrical response could be observed on some functionalized individual nanotubes. Depending on the attached dye molecule, the conductivity change is either induced by a light-induced conformational change or by a charge transfer between the nanotube and the excited dye molecule. The perspectives of constructing an optoelectronic nanoswitch based on these effects are discussed. The second part of the thesis addresses carbon nanotubes functionalized by a low density of electrodeposited gold nanoparticles with sizes in the range between 10 and 100nm. In this case, the functionalization is targeted on amplifying the nanotube's Raman response (SERS effect). The novel sample preparation technique developed in this thesis allowed for an investigation of SERS on the level of individual molecule / nanoparticle hybrids. The optical emission spectra of the nanotube-nanoparticle hybrid structure disclosed Raman peaks associated with the nanotubes, which are superimposed on a broad luminescence background originating from the metal particles. Wavelength dependent experiments revealed maximum Raman intensity when both the nanotube and the metal particle are in optical resonance. In well-prepared samples the Raman signals collected over isolated particles exhibited an intensity enhancement by at least one order of magnitude, as compared to bare sections on the same tube, without appreciably interfering with polarization dependent Raman measurements.

Surface enhanced Raman scattering of carbon nanotubes decorated by individual fluorescent gold particles

Tilman Assmus, Kannan Balasubramanian, Marko Burghard, Klaus Kern

Confocal optical microscopy was employed to study the effect of surface-enhanced Raman scattering on individual single-walled carbon nanotubes covered with isolated gold particles. The gold particles with diameters between 10 and 120 nm were deposited in low densities on the tubes' sidewalls by an electrochemical method. In the spectra, Raman peaks associated with the nanotubes were found to be superimposed on a broad luminescence background originating from the metal particles. With increasing particle size, both the luminescence intensity as well as the Raman enhancement increased at ion er wavelengths. This finding is consistent with a size-dependent broadening of the gold plasmon frequency and a corresponding extension of the energetic range for local field enhancement on the particle surface. In addition, wavelength-dependent experiments revealed a maximum Raman intensity when both nanotube and metal particle were in optical resonance.

2008

Non-invasive continuous monitoring of pro-oxidant effects of engineered nanoparticles on aquatic microorganisms

Paul Bowen, Volodymyr Koman, Olivier Martin, Christian Santschi, Nadia Rachel Von Moos

Engineered nanomaterials (ENMs) are key drivers for the development of highly sophisticated new technologies. As all new attainments, the rapidly increasing used of ENMs raise concerns about their safety for the environment and humans. There is growing evidence showing that if engineered nanomaterials are released into the environment, there is a possibility that they could cause harm to aquatic microorganisms. Among the divers effects triggering their toxicity the ability of ENMs to generate reactive oxygen species (ROS) capable of oxidizing biomolecules is currently considered a central mechanism of toxicity. Therefore, development of sensitive tools for quantification of the ROS generation and oxidative stress are highly sought. After briefly introducing ENMs-induced ROS generation and oxidative stress in the aquatic microorganisms (AMOs), this overview paper focuses on a new optical biosensor allowing sensitive and dynamic measurements of H2O2 in real-time using multiscattering enhanced absorption spectroscopy. Its principle is based on sensitive absorption measurements of the heme protein cytochrome c whose absorption spectrum alters with the oxidation state of constituent ferrous Fe-II and ferric Fe-III. For biological applications cytochrome c was embedded in porous random media resulting in an extended optical path length through multiple scattering of light, which lowers the limit of detection to a few nM of H2O2. The sensor was also integrated in a microfluidic system containing micro-valves and sieves enabling more complex experimental conditions. To demonstrate its performance, abiotic absorption measurements of low concentrations of dye molecules and 10 nm gold particles were carried out achieving limits of detection in the low nM range. Other biologically relevant reactive oxygen species can be measured at sub-mu M concentrations, which was shown for glucose and lactate through enzymatic reactions producing H2O2. In ecotoxicological investigations H2O2 excreted by aquatic microorganisms exposed to various stressors were measured. Pro-oxidant effects of nano-TiO2 and nano-CuO towards green alga Chlamydomonas reinhardtii were explored in various exposure media and under different light illuminations. Dynamics of Cd2+ induced effects on photosynthetic activity, sensitisation and recovery of cells of C. reinhardtii was also studied.

2017

Challenges and Applications to Operando and In Situ TEM Imaging and Spectroscopic Capabilities in a Cryogenic Temperature Range

Martial Duchamp, Reinis Ignatans, Vasiliki Tileli

In this Account, we describe the challenges and promising applications of transmission electron microscopy (TEM) imaging and spectroscopy at cryogenic temperatures. Our work focuses on two areas of application: the delay of electron-beam-induced degradation and following low-temperature phenomena in a continuous and variable temperature range. For the former, we present a study of LiMn1.5Ni0.5O4 lithium ion battery cathode material that undergoes electron beam-induced degradation when studied at room temperature by TEM. Cryogenic imaging reveals the true structure of LiMn1.5Ni0.5O4 nanoparticles in their discharged state. Improved stability under electron beam irradiation was confirmed by following the evolution of the O K-edge fine structure by electron energy-loss spectroscopy. Our results demonstrate that the effect of radiation damage on discharged LiMn1.5Ni0.5O4 was previously underestimated and that atomic-resolution imaging at cryogenic temperature has a potential to be generalized to most of the Li-based materials and beyond. For the latter, we present two studies in the imaging of low-temperature phenomena on the local scale, namely, the evolution of ferroelectric and ferromagnetic domains walls, in BaTiO3 and Y3Fe5O12 systems, respectively, in a continuous and variable temperature range. Continuous imaging of the phase transition in BaTiO3, a prototypical ferroelectric system, from the low-temperature orthorhombic phase continuously up to the centrosymmetric high-temperature phase is shown to be possible inside a TEM. Similarly, the propagation of domain walls in Y3Fe5O12, a magnetic insulator, is studied from similar to 120 to similar to 400 K and combined with the application of a magnetic field and electrical current pulses to mimic the operando conditions as in domain wall memory and logic devices for information technology. Such studies are promising for studying the pinning of the ferroelectric and magnetic domains versus temperature, spin-polarized current, and externally applied magnetic field to better manipulate the domain walls. The capability of combining operando TEM stimuli such as current, voltage, and/or magnetic field with in situ TEM imaging in a continuous cryogenic temperature range will allow the uncovering of fundamental phenomena on the nanometer scale These studies were made possible using a MEMS-based TEM holder that allowed an electron-transparent sample to be transferred and electrically contacted on a MEMS chip. The six-contact double-tilt holder allows the alignment of the specimen into its zone axis while simultaneously using four electrical contacts to regulate the temperature and two contacts to apply the electrical stimuli, i.e., operando TEM imaging. This Account leads to the demonstration of (i) the high-resolution imaging and spectroscopy of nanoparticles oriented in the desired [110] zone-axis direction at cryogenic temperatures to mitigate the electron beam degradation, (ii) imaging of low-temperature transitions with accurate and continuous control of the temperature that allowed single-frame observation of the presence of both the orthorhombic and tetragonal phases in the BaTiO3 system, and (iii) magnetic domain wall propagation as a function of temperature, magnetic field, and current pulses (100 ns with a 100 kHz repetition rate) in the Y3Fe5O12 system.