Fundamental Investigations into Single Molecule Surface Enhanced Raman Spectroscopy

<p>After the first claim of single molecule (SM) detection by surface enhanced Raman spectroscopy (SERS) was published in 1997 and years of debate and maturing, SM-SERS can now be considered as an established subfield of SERS. Besides the obvious promising advances in analytical spectroscopy that SM-SERS enables, some more fundamental studies are now also accessible. The main focus of this thesis is to understand certain aspects and tackle some outstanding issues in SM-SERS, both in methods and applications. In the first part of this thesis, we focus on the application of SM-SERS to the study of the homogeneous broadening of molecular vibrations. We show that the homogeneous linewidth of the dye Nile blue as measured on single molecule SERS spectra is much smaller than the inhomogeneous broadening obtained from the average signal. Individual molecules having the central Raman frequency occurring at slightly different positions is therefore the main cause of the inhomogeneous broadening in this system. Furthermore, we show that the homogeneous broadening of the mode of single molecules exhibits a strong temperature dependence from 80K to 300 K. This is suggestive of the vibrational energy exchange model which explicitly relates the temperature dependence of the linewidth of a vibrational mode to its interaction with other modes of the molecule or its environment. The average signal does not show this temperature dependence, this property is indeed washed out by ensemble averaging and its unravelling is made possible by SM-SERS. This study is the first example of direct measurement and study of the homogeneous broadening of a Raman peak. In the second part of this work, we focus on a particular method to prove single molecule sensitivity and demonstrate the single molecule detection of the iconic C₆₀ by SM-SERS using its peculiar spectral properties regarding isotopic substitution. A change in one unit mass in one of the carbon atoms is readily observed as a detectable frequency shift in the Ag(2) mode on the Raman spectrum of one C₆₀. This remarkable result is a direct consequence of the high symmetry of the molecule and is only accessible experimentally by measuring individual molecules. We perform SM-SERS detection of a isotopically enriched C₆₀ and show how the distribution of frequencies for the Ag(2) mode reflects the isotopic spread of the sample. Density Functional Theory (DFT) calculations support the experimental results. This provides the first ever evidence of single molecule detection of C₆₀ via SERS. Finally, we focus on the photostability of dyes excited resonantly in SERS conditions. Photobleaching of the molecule is an issue when doing SERS (and SM-SERS) at resonance. Nile blue is deposited on a highly ordered gold nanolithographic substrate and the time dependence of the SERS signal is monitored. Using a simple two-level system model to describe the mechanisms of photobleaching and express the photobleaching rate, we analyse the SERS intensity decay at different powers. This study is the first to be dedicated to the photobleaching decay rates of molecules on metallic surfaces and to highlight that the decay dynamics contains rates spanning four orders of magnitude. This work can potentially reveal information on the distribution of SERS enhancement factors on the surface.</p>

Fundamental Investigations into Single Molecule Surface Enhanced Raman Spectroscopy

<p>After the first claim of single molecule (SM) detection by surface enhanced Raman spectroscopy (SERS) was published in 1997 and years of debate and maturing, SM-SERS can now be considered as an established subfield of SERS. Besides the obvious promising advances in analytical spectroscopy that SM-SERS enables, some more fundamental studies are now also accessible. The main focus of this thesis is to understand certain aspects and tackle some outstanding issues in SM-SERS, both in methods and applications. In the first part of this thesis, we focus on the application of SM-SERS to the study of the homogeneous broadening of molecular vibrations. We show that the homogeneous linewidth of the dye Nile blue as measured on single molecule SERS spectra is much smaller than the inhomogeneous broadening obtained from the average signal. Individual molecules having the central Raman frequency occurring at slightly different positions is therefore the main cause of the inhomogeneous broadening in this system. Furthermore, we show that the homogeneous broadening of the mode of single molecules exhibits a strong temperature dependence from 80K to 300 K. This is suggestive of the vibrational energy exchange model which explicitly relates the temperature dependence of the linewidth of a vibrational mode to its interaction with other modes of the molecule or its environment. The average signal does not show this temperature dependence, this property is indeed washed out by ensemble averaging and its unravelling is made possible by SM-SERS. This study is the first example of direct measurement and study of the homogeneous broadening of a Raman peak. In the second part of this work, we focus on a particular method to prove single molecule sensitivity and demonstrate the single molecule detection of the iconic C₆₀ by SM-SERS using its peculiar spectral properties regarding isotopic substitution. A change in one unit mass in one of the carbon atoms is readily observed as a detectable frequency shift in the Ag(2) mode on the Raman spectrum of one C₆₀. This remarkable result is a direct consequence of the high symmetry of the molecule and is only accessible experimentally by measuring individual molecules. We perform SM-SERS detection of a isotopically enriched C₆₀ and show how the distribution of frequencies for the Ag(2) mode reflects the isotopic spread of the sample. Density Functional Theory (DFT) calculations support the experimental results. This provides the first ever evidence of single molecule detection of C₆₀ via SERS. Finally, we focus on the photostability of dyes excited resonantly in SERS conditions. Photobleaching of the molecule is an issue when doing SERS (and SM-SERS) at resonance. Nile blue is deposited on a highly ordered gold nanolithographic substrate and the time dependence of the SERS signal is monitored. Using a simple two-level system model to describe the mechanisms of photobleaching and express the photobleaching rate, we analyse the SERS intensity decay at different powers. This study is the first to be dedicated to the photobleaching decay rates of molecules on metallic surfaces and to highlight that the decay dynamics contains rates spanning four orders of magnitude. This work can potentially reveal information on the distribution of SERS enhancement factors on the surface.</p>

Proton Detected Solid-State NMR of Membrane Proteins at 28 Tesla (1.2 GHz) and 100 kHz Magic-Angle Spinning

The available magnetic field strength for high resolution NMR in persistent superconducting magnets has recently improved from 23.5 to 28 Tesla, increasing the proton resonance frequency from 1 to 1.2 GHz. For magic-angle spinning (MAS) NMR, this is expected to improve resolution, provided the sample preparation results in homogeneous broadening. We compare two-dimensional (2D) proton detected MAS NMR spectra of four membrane proteins at 950 and 1200 MHz. We find a consistent improvement in resolution that scales superlinearly with the increase in magnetic field for three of the four examples. In 3D and 4D spectra, which are now routinely acquired, this improvement indicates the ability to resolve at least 2 and 2.5 times as many signals, respectively.

Stimulated Raman Scattering in Yttrium, Gadolinium, and Calcium Orthovanadate Crystals with Single and Combined Frequency Shifts under Synchronous Picosecond Pumping for Sub-Picosecond or Multi-Wavelength Generation around 1.2 µm

Comparative investigation of stimulated Raman scattering (SRS) characteristics in the YVO4, GdVO4, and Ca3(VO4)2 orthovanadate crystals at both low and high frequency anionic group vibrations is presented. It was found that GdVO4 is the most perspective for SRS generation on both the ν1 stretching and ν2 bending modes of internal anionic group vibrations with the strongest SRS pulse shortening under synchronous picosecond pumping. It is as a result of GdVO4‘s widest linewidth (17cm−1) of the homogeneously broadened scheelite-type component of the bending ν2 Raman line that led to the strongest SRS pulse shortening down to the dephasing time of the widest (scheelite-type) Raman mode at the secondary intracavity short-shifted SRS conversion. It allowed us to achieve SRS pulses with sub-picosecond duration under tens-of-picoseconds pumping due to the strongest 42-fold pulse shortening. Using the Ca3(VO4)2 crystal with essentially wider Raman lines (~50cm−1) did not allow us to generate SRS pulses shorter than 1 ps. It can be explained by inhomogeneous broadening of the Raman lines in Ca3(VO4)2 because of its structural disordering. Using the measured SRS pulse duration, the homogeneous broadening of the inhomogeneously broadened bending Raman line of Ca3(VO4)2 was estimated to be ~9cm−1. Among the orthovanadate crystals, the YVO4 crystal with the highest Raman gain and with homogeneously broadened Raman lines allowed us to realize the most efficient SRS lasing and SRS pulse shortening truly down to inverse half-width of the bending Raman line.

A Unified Pervasive Linebroadening Function for Quantum Wells in Light Emitting Diodes

The broadening functions for quantum wells in LEDs and laser diodes below the lasing threshold are examined. Inhomogeneous and homogeneous broadening mechanisms are included. Hydrogen-atom-like exciton and the electron-hole plasma recombination models are considered. Material disorder and the Urbach tail are reviewed as the main reasons for the inhomogeneous broadening. Charge carrier scattering and relaxation times in the conduction and valence bands are examined as the origin for the homogeneous lifetime broadening. Two homogeneous lineshapes are compared using the momentum relaxation times obtained from the electron and hole mobilities available for GaAs. In addition to crystal disorder, the mutual collision of charge carriers in the quantum wells is examined as the reason for the relaxation time shortening. The analogy to pressure broadening in gases is used to combine the proper homogeneous and inhomogeneous broadening functions to a unified quantum well lineshape.

Raman 2D Peak Line Shape in Epigraphene on SiC

We measured a 2D peak line shape of epitaxial graphene grown on SiC in high vacuum, argon and graphene prepared by hydrogen intercalation from the so called buffer layer on a silicon face of SiC. We fitted the 2D peaks by Lorentzian and Voigt line shapes. The detailed analysis revealed that the Voigt line shape describes the 2D peak line shape better. We have determined the contribution of the homogeneous and inhomogeneous broadening. The homogeneous broadening is attributed to the intrinsic lifetime. Although the inhomogeneous broadening can be attributed to the spatial variations of the charge density, strain and overgrown graphene ribbons on the sub-micrometer length scales, we found dominant contribution of the strain fluctuations. The quasi free-standing graphene grown by hydrogen intercalation is shown to have the narrowest linewidth due to both homogeneous and inhomogeneous broadening.