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Molecular crystals and liquid crystals science technology. Section A, Molecular crystals and liquid crystals/Molecular crystals and liquid crystals science and technology. Section A, Molecular crystals and liquid crystals

Single Molecule Spectroscopy and Spectral Hole-Burning

Hermann Bach, Thomas Irngartinger, Alois Renn, Urs P. Wild

Published Dec 1, 1996• 4 citations
Publisher

Abstract

Spectral hole-burning in the Shpol'skii system terrylene in n-octane has been investigated on the single molecule level. Fluorescence microscopy provides a link between the two methods of spectral hole-burning and single molecule spectroscopy. Information about many different individual molecules can be obtained simultaneously under identical experimental conditions allowing the determination of statistical properties. From a single frequency scan after spectral hole-burning, the ground state population function and an average hole-width, as well as the single molecule linewidth distribution of 700 molecules have been determined.

DOI
10.1080/10587259608042735

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Optical Spectra of Single Impurity Molecules in a Polymer: Spectral Diffusion and Persistent Spectral Hole-Burning

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Recent advances in the optical detection and spectroscopy of single impurity centers in crystals has provided the possibility of obtaining information about defect-solid interactions on a truly local level. For the system composed of pentacene impurity molecules in the crystal p-terphenyl, single molecules have been studied using both absorption1 and fluorescence excitation2 techniques at liquid helium temperatures. The superior signal-to-noise of the latter technique has led to direct observations of the lifetime-limited Lorentzian homogeneous profile of a single pentacene impurity3 as well as the surprising observation of spontaneous spectral diffusion4. Spectral diffusion, or changes in the resonance frequency of an impurity molecule with time as a result of low-energy excitations (two-level system transitions (TLS)),5 is generally expected in amorphous hosts. Indeed, the presence of TLSs in amorphous solids is intimately connected with nonphotochemical mechanisms for persistent spectral hole-burning (PSHB) in amorphous materials6-8. Using perylene impurity molecules in poly(ethylene), we have observed the optical spectra of single molecules in a polymeric host for the first time. At 1.5K, individual perylene molecules show the expected spectral diffusion; moreover, we observe light-induced changes in resonance frequency, i.e., persistent spectral hole-burning, which allows one to envision optical storage on the single-molecule level.

Spectral Hole-Burning and Related Spectroscopies: Science and Applications•Jan 1, 1991•0 citations
Spectral hole-burning in the Shpol'skii system terrylene in n-octane has been investigated on the single molecule level. Fluorescence microscopy provides a link between the two methods of spectral hole-burning and single molecule spectroscopy. Information about many different individual molecules can be obtained simultaneously under identical experimental conditions allowing the determination of statistical properties. From a single frequency scan after spectral hole-burning, the ground state population function and an average hole-width, as well as the single molecule linewidth distribution of 700 molecules have been determined.
At very low temperatures, the spread in the different environments of matrix embedded dye molecules results in an inhomogeneously broadened S1 ← S0 band. Spectroscopic techniques based on the appearence of optical zero phonon lines, such as fluorescence line narrowing, spectral hole-burning, and single molecule spectroscopy provide an experimental resolution limited by the homogeneous linewidth. From the investigation of the homogeneous line width as a function of different parameters (time, temperature) information on the guest host interactions responsible for the observed linewidth is obtained. Spectrally narrow features are extremely sensitive probes for external perturbations, such as electric fields, magnetic fields, or hydrostatic pressure.
With high-efficiency fluorescence excitation techniques optical spectra of single impurity molecules of perylene in a polyethylene matrix can be obtained at 1.5 K. Analysis of such spectra shows a variety of spectral diffusion effects, including fast (<2 s) resonance frequency changes on the 1–100-MHz scale, which lead to a range of apparent linewidths, as well as discontinuous jumps in the resonance frequency of 10–1000 MHz on a longer time scale. In addition, light-induced changes in the resonance frequency of a single molecule (persistent spectral hole burning) have been conclusively observed by showing that the burning time decreases with increased laser power. Surprisingly, hole-burned single molecules often spontaneously return to the original frequency in 1–100 s. Measurements of the burning time for a large number of hole-burning events for the same single molecule yield an exponential burn-time distribution, which is the first direct measurement to our knowledge of the stochastic kinetics of a single molecule. Analysis of the signal-to-noise function appropriate to these experiments gives the conditions under which other systems may permit single-molecule detection: strong absorption, high fluorescence yield, weak bottlenecks in the optical pumping process, and low hole-burning quantum efficiency.
Fluorescence excitation spectra of single terrylene molecules in p-terphenyl crystals were investigated at low temperatures. The line shifts due to hydrostatic pressure and external electric fields were measured, with the electric field strength oriented either parallel or perpendicular to the k vector of the laser light. A linear Stark effect was found for most molecules, indicating local environments of low symmetry. In sites X1 and X3 (and XY, a photoproduct state), spectral hole burning was observed. Whereas the holes are stable in sites X1 and XY, they decay with a time constant of some minutes in X3. Pressure experiments were performed on the stable hole spectra in sites X1 and XY. In weakly doped samples, holes composed of very few molecular lines were generated with halfwidths distinctly narrower than twice the homogeneous linewidth.
As was recently demonstrated1 by using highly efficient fluorescence excitation spcctroscopy with N.A. = 0.98 collection optics, single impurity molecules in both crystals and polymers may now be detected with single-to-noiseratios (SNRs) as high as 30 in a 1 Hz bandwidth at low temperatures. In essence, the solid may be regarded as a trap for the single molecule, which effectively quenches rotation. Our measurements include precise determination of the lifetime limited linewidth and the temperature dependence of the optical dephasing, as well as spectral diffusion (wandering in frequency space due to perturbations by lattice degrees of freedom). For the polymeric host, light-induced changes in resonant frequency of a single molecule can be produced, a process that is normally termed spectral hole-burning when large ensembles of molecules are probed. In recent studies, nonclassical light emission from a single molecule (photon antibunching) has been observed in a fashion analogous to that reported earlier for a single atom in a trap.
Recent advances in the optical detection and spectroscopy of single impurity centers in crystals has provided the possibility of obtaining information about defect-solid interactions on a truly local level. For the system composed of pentacene impurity molecules in the crystal p-terphenyl, single molecules have been studied using both absorption1 and fluorescence excitation2 techniques at liquid helium temperatures. The superior signal-to-noise of the latter technique has led to direct observations of the lifetime-limited Lorentzian homogeneous profile of a single pentacene impurity3 as well as the surprising observation of spontaneous spectral diffusion4. Spectral diffusion, or changes in the resonance frequency of an impurity molecule with time as a result of low-energy excitations (two-level system transitions (TLS)),5 is generally expected in amorphous hosts. Indeed, the presence of TLSs in amorphous solids is intimately connected with nonphotochemical mechanisms for persistent spectral hole-burning (PSHB) in amorphous materials6-8. Using perylene impurity molecules in poly(ethylene), we have observed the optical spectra of single molecules in a polymeric host for the first time. At 1.5K, individual perylene molecules show the expected spectral diffusion; moreover, we observe light-induced changes in resonance frequency, i.e., persistent spectral hole-burning, which allows one to envision optical storage on the single-molecule level.