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Annual Review of Physical Chemistry

Hole-Burning Spectroscopy

Silvia Volker

Published Jan 1, 1989• 230 citations
Publisher

Abstract

The study of optical relaxation processes in solids at low temperature has progressed tremendously in the last 20 years due to the development of coherent optical techniques. The latter would not have been possible without the advent of narrow-band tunable lasers, on the one hand, and lasers with very short pulses (picoseconds, femtosecoods) on the other hand. Such coherent techniques are necessary because spectral line shapes of solids doped with guest molecules are seldom determined by dynamical interactions but principally by strain or structural disorder. This gives rise to inhomogeneous broadening, rlOh, which in crystalline hosts at low temperature varies between ' 0.1 and 10 cm -I, whereas in glasses it may amount to � 100-500 em-I. One of the techniques to achieve narrowing of spectral lines is site­ selection spectroscopy (1-3). A sub-ensemble of molecules within thc inhomogeneously broadened absorption band is selectively excited by mcans of a narrow-band laser, and the fluorescence or phosphoresccnce signal is detected with a high-resolution monochromator and/or a Fabry­ Perot interferometer. Fluorescence line-narrowing ( I) is a special case of this technique (for a review see 3). The intrinsic or homogeneous spectral linewidth, r hom, which yields information on the relaxation processes of the excited state, is given by the effective optical dephasing time, T2:

DOI
10.1146/annurev.pc.40.100189.002435

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The study of optical relaxation processes in solids at low temperature has progressed tremendously in the last 20 years due to the development of coherent optical techniques. The latter would not have been possible without the advent of narrow-band tunable lasers, on the one hand, and lasers with very short pulses (picoseconds, femtosecoods) on the other hand. Such coherent techniques are necessary because spectral line shapes of solids doped with guest molecules are seldom determined by dynamical interactions but principally by strain or structural disorder. This gives rise to inhomogeneous broadening, rlOh, which in crystalline hosts at low temperature varies between ' 0.1 and 10 cm -I, whereas in glasses it may amount to � 100-500 em-I. One of the techniques to achieve narrowing of spectral lines is site­ selection spectroscopy (1-3). A sub-ensemble of molecules within thc inhomogeneously broadened absorption band is selectively excited by mcans of a narrow-band laser, and the fluorescence or phosphoresccnce signal is detected with a high-resolution monochromator and/or a Fabry­ Perot interferometer. Fluorescence line-narrowing ( I) is a special case of this technique (for a review see 3). The intrinsic or homogeneous spectral linewidth, r hom, which yields information on the relaxation processes of the excited state, is given by the effective optical dephasing time, T2:
Optical spectroscopy provides a useful tool for probing the structure and dynamics of solids. Over the years, optical methods have evolved from absorption spectroscopy to more complex methods such as spectral hole burning, photon echoes, and luminescence line narrowing. The absorption spectrum provides information about inhomogeneous broadening, while the latter approaches provide information about the systematics of the homogeneous line shape information that is often obscured by inhomogeneous broadening. When external perturbations such as strain or electric fields are applied, details of the local site can be obtained. Recently, the ultimate limit of optical spectroscopy has been attained, in which the spectral properties of individual single impurity molecules in a solid can be measured, with all ensemble averaging removed. This novel regime has provided additional, previously unobtainable, information on a highly local scale, such as the direct observation of the spectral shifting of a single molecule produced by configurational transitions of the host. It is to be expected that further surprises await us in this new frontier of single-molecule spectroscopy in solids.
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.
Laser induced hole burning in optical absorption bands of low temperature solids has been investigated with emphasis on mechanisms for population hole burning, the interactions with the environment which limit the hole widths and the use of hole burning for ultra high resolution spectroscopy. Hole burning was observed in a wide range of solids including organic and organometallic molecules in crystals and rare earth ions in crystals and glasses. The mechanisms for hole burning also varied widely and a new mechanism involving optically induced nuclear spin flips of near neighbor nuclei was discovered. Examples of hole burning in new classes of materials are presented here for the first time, namely inorganic glasses (silicate glasses containing Nd(3+), Pr(3+) or Eu(3+)) and undoped stoichiometric compounds (e.g., EuP5O14). Hole recovery was used to determine nuclear spin lattice relaxation rates in praseodymium doped crystals. For allowed optical transitions (e.g., singlet states of zinc porphyrin, dibromoindigo and color centers in alkali halides) the hole widths at 2K are limited by population decay to approximately 50 MHz. For longer lived optical levels in crystalline materials, e.g., those containing rare earth ions, the hole widths are narrower (less than 10 MHz) and are limited by dynamical interactions with surrounding nuclei. In amorphous materials such as europium doped silicate glass, hole widths are much broader, being limited by low frequency tunneling motions. Hole burning measurements were complemented by time domain coherent transient (photon echo, and optical free decay) measurements of homogeneous linewidths which enabled us to measure optical resonances as narrow as 760 Hz in Eu(3+):Y2O3.
One very exciting application of laser spectroscopy would be to use the high-resolution capabilities of today’s lasers and the phenomenon of persistent spectral hole-burning to form a frequency domain optical storage system.1 In such a system, bits of information would be stored by locally modifying (in the frequency domain) the shape of an inhomogeneously broadened absorption line of an absorber in a solid at low temperatures. Because typical homogeneous widths are 1000X (or more) narrower than typical inhomogeneous widths, as many as 1000 bits could be written in one diffraction-limited 1-μm spot In a sample, yielding the impressive storage density of 1011 bits/cm2.
Each dye molecule embedded in an amorphous material such as a a polymer host experiences a specific molecular environment which strongly influences its electronic transition energies. At low temperatures the different microenvironments result in an inhomogeneously broadened absorption band. The invention of the laser brought new spectroscopic techniques based on energy selection, such as fluorescence line narrowing and spectral hole-burning [1]. These techniques enable convenient addressing of thousands of molecular subsets selected by their transition energy.
Until the advent of laser, optical spectroscopy was limited to absorption and emission. These linear techniques often provided incomplete information because of the presence of inhomogeneous broadening, which arises in gases from Doppler shifts and in solids from random crystal elds or structural disorder (Figure 10.1). Lasers provided the high intensity needed to implement nonlinear spectroscopic techniques, which can make measurements “below” the CONTENTS 10.1 Introduction 371 10.1.1 Physical Description of TFWM for a Two-Level System 373 10.1.2 Overview of Variants and Extensions of TFWM 375 10.1.3 Use of TFWM Spectroscopy in Solids, Semiconductors, and Complex Systems 376 10.2 Theory 377 10.2.1 TFWM Signal from an Inhomogeneously Broadened Ensemble of Two-Level Systems 378 10.2.2 Phenomenological Inclusion of Many-Body Effects 381 10.3 Experimental Details of TFWM 382 10.3.1 Basics of Excitation Pulse Generation, Alignment, and Signal Detection 382 10.3.2 Time-Integrated Two-Pulse TFWM 385 10.3.3 Time and Spectrally Resolved Two-Pulse TFWM 386 10.3.4 Three-Pulse TFWM 386 10.3.5 Co-Linear TFWM 387 10.4 Case Study: TFWM from Excitons in GaAs Quantum Wells 387 10.4.1 Dephasing 388 10.4.2 Many-Body Effects 389 10.4.3 Disorder 391 10.4.4 Quantum Beats 391 10.4.5 Polarization Dependence 392 10.5 Multidimensional Fourier Transform Spectroscopy 392 10.6 Summary 393 References 393 inhomogeneous line width and determine the underlying homogeneous line widths. Often the homogeneous width is more interesting because it reects dynamics such as scattering and/ or radiative decay.