Biomedical subjects
Publications and source records attributed to Achim Hartschuh.
We report on chemically specific, subsurface imaging with high spatial resolution. Using tip-enhanced Raman spectroscopy, we probe carbon nanotubes buried beneath a host dielectric media. We demonstrate our ability to map and resolve specific vibrational modes with 30 nm spatial resolution for dielectric layers with different thicknesses.
The dynamics of excitons in individual semiconducting single-walled carbon nanotubes was studied using time-resolved photoluminescence (PL) spectroscopy. The PL decay from tubes of the same (n,m) type was found to be monoexponential, however, with lifetimes varying between less than 20 and 200 ps from tube to tube. Competition of nonradiative decay of excitons is facilitated by a thermally activated process, most likely a transition to a low-lying optically inactive trap state that is promoted by a low-frequency phonon mode.
We present for the first time cavity-controlled fluorescence spectra and decay curves of single dipole emitters interacting at room temperature with the first longitudinal mode of a Fabry-Perot microcavity offering a lambda/2-spacing between its silver mirrors. The spontaneous emission rate of individual dye molecules was found to be enhanced by the Purcell effect by up to three times compared to the rate in free space, in agreement with theoretical predictions. Moreover, our new microcavity design was found to provide long-term stability and single-molecule sensitivity under ambient conditions for several months without noticeable reduction of the cavity-Q value. We consider this as a significant advance for single-photon sources operating at room temperature.
Fluorescence imaging is used to visualize directly the transfer of two inner hydrogen atoms in single porphycene molecules. This reaction leads to a chemically equivalent but differently oriented structure and hence results in a rotation of the transition dipole moments. By probing single immobilized molecules with an azimuthally polarized laser beam in the focal spot of a confocal microscope we observe ring-like emission patterns, possible only for a chromophore with two nearly orthogonal transition dipole moments. Numerical simulations of the observed emission patterns yield a value of 72 degrees for the angle between the S0-S1 transition moments in the two tautomeric forms.
We use near-field Raman imaging and spectroscopy to study localized vibrational modes along individual, single-walled carbon nanotubes (SWNTs) with a spatial resolution of 10-20 nm. Our approach relies on the enhanced field near a laser-irradiated gold tip which acts as the Raman excitation source. We find that for arc-discharge SWNTs, both the radial breathing mode (RBM) and intermediate frequency mode (IFM) are highly localized. We attribute such localization to local changes in the tube structure (n, m). In comparison, we observe no such localization of the Raman active modes in SWNTs grown by chemical vapor deposition (CVD). The direct comparison between arc-discharge and CVD-grown tubes allows us to rule out any artifacts induced by the supporting substrate.
This Minireview discusses novel insights into the electronic structure of carbon nanotubes obtained using single-molecule fluorescence spectroscopy. Fluorescence spectra from single nanotubes are well described by a single, Lorentzian lineshape. Nanotubes with identical structures fluoresce with different energies due to local electronic perturbations. Carbon nanotube fluorescence unexpectedly does not-show any intensity or spectral fluctuations at 300 K The lack of intensity blinking or bleaching demonstrates that carbon nanotubes have the potential to provide a stable, single-molecule infrared photon source, allowing for the exciting possibility of applications in quantum optics and biophotonics.
We present simultaneous near-field photoluminescence (PL) and Raman imaging of single-walled carbon nanotubes (SWNTs) with a spatial resolution better than 15 nm. Highly localized excitation is used to visualize the spatial extent of the contributing excited states. For SWNTs on glass, we typically observe highly confined PL from short segments of about 20 nm in length. The PL from micelle-encapsulated SWNTs on mica is extended along the tube up to several hundreds of nanometers. We find that near-field enhancement is much stronger for photoluminescence than for Raman scattering, an observation that is explained by the low intrinsic quantum yield of SWNTs.
Spectroscopic methods with high spatial resolution are essential for understanding the physical and chemical properties of nanoscale materials including biological proteins, quantum structures and nanocomposite materials. In this paper, we describe microscopic techniques which rely on the enhanced electric field near a sharp, laser-irradiated metal tip. This confined light-source can be used for the excitation of various optical interactions such as two-photon excited fluorescence or Raman scattering. We study the properties of the enhanced fields and demonstrate fluorescence and Raman imaging with sub-20 nm resolution.
Single-molecule fluorescence spectroscopy was used to determine the electronic properties of individual single-walled carbon nanotubes. Carbon nanotube structure was determined simultaneously from Raman spectroscopy. Fluorescence spectra from individual nanotubes with identical structures have different emission energies and linewidths that likely arise from defects or the local environment. Unlike most other molecules studied to date, the fluorescence intensity or spectrum from a single nanotube unexpectedly did not fluctuate.
We present near-field Raman spectroscopy and imaging of single isolated single-walled carbon nanotubes with a spatial resolution of approximately 25 nm. The near-field origin of the image contrast is confirmed by the measured dependence of the Raman scattering signal on tip-sample distance and the unique polarization properties. The method is used to study local variations in the Raman spectrum along a single single-walled carbon nanotube.