Challenges
Datasets
Workspaces
Papers
Discussions
Leaderboard
Log inSign up
Challenges
Datasets
Workspaces
Papers
Discussions
Leaderboard
Blog
Job Board
Q3AS

© 2026 Aqora Quantum S.A.S.

TermsPrivacyLegal Notice

Journal of Luminescence

Inhomogeneous broadening in solids: Progress towards a microscopic understanding

James L. Skinner, Brian B. Laird, Leslie J. Root

Published Jan 1, 1990• 16 citations
Publisher

Abstract

Abstract Inhomogeneous broadening is often considered a nuisance in solid state spectroscopy, and the usual treatment of it is phenomenological. In fact, the inhomogeneous broadening of absorption spectra, coupled with a microscopic theory, can provide one with interesting information about the nature of disorder in different systems. More sophisticated experiments can provide more detailed information about disorder by probing certain correlations between energy levels. For example, flourescence line narrowing spectra of isolated impurities involve correlations among three different vibronic levels. Pressure effects on hole burning spectra probe correlations of impurity transition energies before and after the pressure change. For interacting impurity systems, photon echo experiments involve transition energy correlations between different impurities. Efforts to understand these effects within a microscopic framework are discussed.

DOI
10.1016/0022-2313(90)90090-x

Related papers

Structure and Dynamics in Solids As Probed by Optical Spectroscopy

James L. Skinner, W. E. Moerner

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.

The Journal of Physical Chemistry•Jan 1, 1996•124 citations

Theory of photon echoes from interacting impurities in crystals with inhomogeneously broadened absorption spectra

Roger F. Loring, Hans C. Andersen, M. D. Fayer

We present a theory of photon echoes from impurity molecules in mixed crystals that takes into account electronic interactions among impurity molecules and inhomogeneous broadening of the electronic absorption spectrum. The system is modeled as a collection of randomly placed interacting two level systems with a distribution of transition energies. The observable of the echo experiment is expanded in powers of the density of two level systems, and the first two terms of this expansion are calculated. A scaling argument suggests that the density expansion is rapidly convergent for concentrations of experimental interest, and the density expansion is used to construct a Padé approximant. At times comparable to or less than the inverse of the width of the inhomogeneous distribution of resonance frequencies, the time dependence of the signal is determined primarily by the interactions between the impurities and is independent of the inhomogeneous width. At longer times the inhomogeneity becomes significant and the echo signal displays a much weaker time dependence. We examine the effect of different microscopic models of inhomogeneous broadening on the echo observable. We demonstrate that the photon echo experiment can provide a sensitive probe of interactions between impurities in mixed crystals.

The Journal of Chemical Physics•Dec 15, 1984•23 citations

Frequency-dependent optical dephasing and the nature of inhomogeneous broadening in crystals

Leslie J. Root, James L. Skinner

We present a theory of frequency-dependent optical dephasing as measured by narrow-band photon-echo experiments. We consider a substitutionally disordered crystal with inhomogeneous broadening (diagonal disorder) and electronic interactions between occupied sites. We include the possibility of site-energy correlations. We find that the frequency dependence of the dephasing rate 1/${T}_{2}$ is very sensitive to the ratio \ensuremath{\xi}/a, where \ensuremath{\xi} is the correlation length and a is the lattice spacing. When \ensuremath{\xi}/a\ensuremath{\rightarrow}\ensuremath{\infty}, and there are macroscopic domains of resonant ions, 1/${T}_{2}$ becomes frequency independent. In the other limit when \ensuremath{\xi}/a\ensuremath{\rightarrow}0, and the site energies are uncorrelated (microscopic broadening), 1/${T}_{2}$ is proportional to the inhomogeneous line shape. We have compared our results to experiments by Macfarlane and Shelby on ${\mathrm{Y}}_{2}$${\mathrm{O}}_{3}$:${\mathrm{Eu}}^{3+}$ (2 at. %) and ${\mathrm{EuP}}_{5}$${\mathrm{O}}_{14}$. We find reasonable agreement with experiment when \ensuremath{\xi} is less than a few lattice sites. Thus, for these systems the model of microscopic broadening is more appropriate than that of macroscopic broadening.

Physical review. B, Condensed matter•Sep 15, 1985•25 citations

General properties of spectrally inhomogeneous media

С. В. Гапоненко

Because of inevitable size distribution, shape variations, different concentration of impurities and defects, and fluctuations of local environment and charge distribution, every ensemble of nanocrystals dispersed in some solid or liquid medium possesses inhomogeneously broadened absorption and emission spectra. Therefore, a number of properties inherent in molecular and atomic inhomogeneously broadened spectra can be a priori foreseen for nanocrystals. These include spectral hole-burning, fluorescence line narrowing under selective excitation, and decay time distribution. At the same time, spectrally selective techniques developed for inhomogeneously broadened molecular and atomic structures have been successfully applied to nanocrystals providing evaluation of individual parameters smeared as a result of inhomogeneous broadening. This chapter gives a brief overview of specific phenomena inherent in all spectrally inhomogeneous media and a survey of the relevant experimental techniques including nonlinear pump-and-probe spectroscopy, fluorescence excitation spectroscopy, and single molecule spectroscopy. Population-induced optical nonlinearity and spectral hole-burning Every real system consisting of particles with discrete energy levels exhibits absorption saturation under intense optical excitation. The only example of a nonsaturable system is an ensemble of ideal harmonic oscillators that possess an infinite number of equally spaced energy levels, optical transitions allowed only for a couple of neighboring levels, and the probability of optical transitions being proportional to the level number (Stepanov and Gribkovskii 1963).

Cambridge University Press eBooks•Oct 28, 1998•0 citations

Selective laser spectroscopy of molecules and ions in solids: a history, fundamentals and applications

M. N. Sapozhnikov

Abstract A history of the development of selective laser spectroscopy is presented, beginning with a pioneering work by Yu. V. Denisov and V. A. Kizel in 1967, who were the first to demonstrate the possibility of removing the inhomogeneous broadening of luminescence spectra of impurity ions in glasses upon monochromatic resonance excitation. Selective excitation of optical centers can be achieved due to existence of zero-phonon transitions corresponding to narrow homogeneous zero-phonon lines in the spectra of impurity centers in solids, which are hidden in broad inhomogeneous optical bands upon usual nonselective excitation. The fundamentals of zero-phonon transition spectroscopy are considered and the mechanism of removing the inhomogeneous broadening of optical spectra of ions and molecules in crystals and amorphous solids under selective laser excitation of luminescence and persistent hole burning in absorption spectra is presented in detail. Various applications of selective laser spectroscopy for fundamental and applied studies are discussed.

Physica Scripta•Jan 11, 2018•0 citations

Microwave-Induced Hole Burning of the 638 Nm Zero-Phonon Transition and Frequency-Dependent Dephasing of the N-V Center in Diamond

Max Glasbeek, Eric van Oort

In recent years the microscopic description of inhomogeneous broadening of electronic transitions of chromophores in crystals and glasses has attracted much interest [1–3]. In the phenomenological model proposed by Selzer [1], it is assumed that the energies of the initial and final states involved in the optical transition exhibit a one-to-one correlation. In an alternative approach by Lee et al [2], the two states are considered as completely uncorrelated. Very recently, a more general microscopic theory has been presented by Laird and Skinner [3]. In the latter theory the aforementioned models are obtained as limiting cases. So far relatively few experiments have been reported which focus on the origin of inhomogeneous broadening.

Spectral Hole-Burning and Related Spectroscopies: Science and Applications•Jan 1, 1991•0 citations
Abstract Inhomogeneous broadening is often considered a nuisance in solid state spectroscopy, and the usual treatment of it is phenomenological. In fact, the inhomogeneous broadening of absorption spectra, coupled with a microscopic theory, can provide one with interesting information about the nature of disorder in different systems. More sophisticated experiments can provide more detailed information about disorder by probing certain correlations between energy levels. For example, flourescence line narrowing spectra of isolated impurities involve correlations among three different vibronic levels. Pressure effects on hole burning spectra probe correlations of impurity transition energies before and after the pressure change. For interacting impurity systems, photon echo experiments involve transition energy correlations between different impurities. Efforts to understand these effects within a microscopic framework are discussed.
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.
We present a theory of photon echoes from impurity molecules in mixed crystals that takes into account electronic interactions among impurity molecules and inhomogeneous broadening of the electronic absorption spectrum. The system is modeled as a collection of randomly placed interacting two level systems with a distribution of transition energies. The observable of the echo experiment is expanded in powers of the density of two level systems, and the first two terms of this expansion are calculated. A scaling argument suggests that the density expansion is rapidly convergent for concentrations of experimental interest, and the density expansion is used to construct a Padé approximant. At times comparable to or less than the inverse of the width of the inhomogeneous distribution of resonance frequencies, the time dependence of the signal is determined primarily by the interactions between the impurities and is independent of the inhomogeneous width. At longer times the inhomogeneity becomes significant and the echo signal displays a much weaker time dependence. We examine the effect of different microscopic models of inhomogeneous broadening on the echo observable. We demonstrate that the photon echo experiment can provide a sensitive probe of interactions between impurities in mixed crystals.
We present a theory of frequency-dependent optical dephasing as measured by narrow-band photon-echo experiments. We consider a substitutionally disordered crystal with inhomogeneous broadening (diagonal disorder) and electronic interactions between occupied sites. We include the possibility of site-energy correlations. We find that the frequency dependence of the dephasing rate 1/T2{T}_{2}T2​ is very sensitive to the ratio \ensuremath{\xi}/a, where \ensuremath{\xi} is the correlation length and a is the lattice spacing. When \ensuremath{\xi}/a\ensuremath{\rightarrow}\ensuremath{\infty}, and there are macroscopic domains of resonant ions, 1/T2{T}_{2}T2​ becomes frequency independent. In the other limit when \ensuremath{\xi}/a\ensuremath{\rightarrow}0, and the site energies are uncorrelated (microscopic broadening), 1/T2{T}_{2}T2​ is proportional to the inhomogeneous line shape. We have compared our results to experiments by Macfarlane and Shelby on Y2{\mathrm{Y}}_{2}Y2​O3{\mathrm{O}}_{3}O3​:Eu3+{\mathrm{Eu}}^{3+}Eu3+ (2 at. %) and EuP5{\mathrm{EuP}}_{5}EuP5​O14{\mathrm{O}}_{14}O14​. We find reasonable agreement with experiment when \ensuremath{\xi} is less than a few lattice sites. Thus, for these systems the model of microscopic broadening is more appropriate than that of macroscopic broadening.
Because of inevitable size distribution, shape variations, different concentration of impurities and defects, and fluctuations of local environment and charge distribution, every ensemble of nanocrystals dispersed in some solid or liquid medium possesses inhomogeneously broadened absorption and emission spectra. Therefore, a number of properties inherent in molecular and atomic inhomogeneously broadened spectra can be a priori foreseen for nanocrystals. These include spectral hole-burning, fluorescence line narrowing under selective excitation, and decay time distribution. At the same time, spectrally selective techniques developed for inhomogeneously broadened molecular and atomic structures have been successfully applied to nanocrystals providing evaluation of individual parameters smeared as a result of inhomogeneous broadening. This chapter gives a brief overview of specific phenomena inherent in all spectrally inhomogeneous media and a survey of the relevant experimental techniques including nonlinear pump-and-probe spectroscopy, fluorescence excitation spectroscopy, and single molecule spectroscopy. Population-induced optical nonlinearity and spectral hole-burning Every real system consisting of particles with discrete energy levels exhibits absorption saturation under intense optical excitation. The only example of a nonsaturable system is an ensemble of ideal harmonic oscillators that possess an infinite number of equally spaced energy levels, optical transitions allowed only for a couple of neighboring levels, and the probability of optical transitions being proportional to the level number (Stepanov and Gribkovskii 1963).
Abstract A history of the development of selective laser spectroscopy is presented, beginning with a pioneering work by Yu. V. Denisov and V. A. Kizel in 1967, who were the first to demonstrate the possibility of removing the inhomogeneous broadening of luminescence spectra of impurity ions in glasses upon monochromatic resonance excitation. Selective excitation of optical centers can be achieved due to existence of zero-phonon transitions corresponding to narrow homogeneous zero-phonon lines in the spectra of impurity centers in solids, which are hidden in broad inhomogeneous optical bands upon usual nonselective excitation. The fundamentals of zero-phonon transition spectroscopy are considered and the mechanism of removing the inhomogeneous broadening of optical spectra of ions and molecules in crystals and amorphous solids under selective laser excitation of luminescence and persistent hole burning in absorption spectra is presented in detail. Various applications of selective laser spectroscopy for fundamental and applied studies are discussed.
In recent years the microscopic description of inhomogeneous broadening of electronic transitions of chromophores in crystals and glasses has attracted much interest [1–3]. In the phenomenological model proposed by Selzer [1], it is assumed that the energies of the initial and final states involved in the optical transition exhibit a one-to-one correlation. In an alternative approach by Lee et al [2], the two states are considered as completely uncorrelated. Very recently, a more general microscopic theory has been presented by Laird and Skinner [3]. In the latter theory the aforementioned models are obtained as limiting cases. So far relatively few experiments have been reported which focus on the origin of inhomogeneous broadening.