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Theory of photoluminescence excitation spectroscopy in

K Hannewald,1,2 S Glutsch,1 F Bechstedt1
Institut fr Festkrpertheorie und Theoretische Optik, Friedrich-SchillerUniversitt Jena, Max-Wien-Platz 1, 07743 Jena, Germany
Present address: Department of Applied Physics, Eindhoven University
of Technology, P.O.Box 513, 5600 MB Eindhoven, The Netherlands
Abstract. We develop a microscopic theory of photoluminescence
excitation spectroscopy (PLE) in semiconductors that is not restricted to
thermalized carrier distributions. The phenomenological assumption of
equivalence between PLE and absorption spectra is confirmed only for
thermal equilibrium. For nonequilibrium, i.e, small time intervals between
pulse excitation and luminescence detection, we observe significant
differences which can be attributed to incomplete relaxation and
bottleneck effects, and should be observable in experiment.

1. Introduction
Besides absorption and photoluminescence (PL) experiments, photoluminescence
excitation (PLE) measurements are a widely used spectroscopic tool for the
characterization of optical transitions in semiconductors. In contrast to the successful
development of microscopic theories for absorption [1-3] and PL [4,5] in recent years, an
analogous first-principles description of PLE experiments is still missing. Here, we
present the first microscopic theory of PLE spectroscopy in semiconductors.
A typical luminescence experiment in semiconductors can be divided into three
stages, as indicated in Fig. 1. First, the sample is excited out of the ground state which is
described by a completely filled valence band and an empty conduction band. Here, we
consider optical band-to-band excitation using a femtosecond laser pulse with a mean
photon energy of &pump. The laser pulse creates electron-hole pairs due to a transfer of
electrons from the valence into the conduction band (Fig. 1a). Second, the
nonequilibrium electron and hole distributions tend to relax back into the ground state.
The initial intraband relaxation is caused by energy transfer to the crystal lattice, i.e., a
step-by-step excitation of lattice vibrations (Fig. 1b), which are at low temperatures
primarily longitudinal optical (LO) phonons in polar semiconductors such as Gallium
Arsenide (GaAs). Finally, the electron-hole pairs recombine under emission of light
which is the photoluminescence process. Due to the attractive Coulomb interaction
between the charge carriers, the emission spectrum does not only contain contributions
from states at or above the fundamental energy gap Egap but also sharp discrete lines just

Figure 1. Sketch of the basic processes involved in a typical luminescence

experiment in optically excited semiconductors.
below Egap which originate from bound excitonic states. In PLE spectroscopy, the
spontaneous emission from the sample is detected at a fixed photon energy, typically at
the lowest excitonic resonance Eexc in high-purity materials (Fig. 1c). The intensity of
this signal is then recorded as a fuQFWL  WK SXP IUHTXHQF &pump. It is usually
assumed that the PLE spectrum obtained in this way is roughly equivalent to the linear
absorption spectrum. A qualitative phenomenological discussion of the relation between
PLE and absorption spectra can be found in several textbooks [6,7].
The supposed equivalence between PLE and absorption signals in semiconductors
strongly relies on the assumption that the recombination times are much larger than the
intraband relaxation times, i.e., if the laser-excited electrons and holes have enough time
to relax completely into quasi-equilibrium before radiative recombination. In this case,
the emission intensity at the lowest exciton becomes independent of the relaxation rate,
and the PLE spectrum can be argued phenomenologically to mimic the absorption signal
[6]. However, this assumption has never been justified by microscopic studies.
Furthermore, another intriguing question has remained completely unaddressed so far in
W between pulse excitation and PL detection is
kept shorter than the intraband thermalization times? Then, the one-to-one
correspondence between PLE and absorption signals should break down completely, and
no simple arguments can be given how the PLE signal looks like. In order to answer
these questions, we develop here the first nonequilibrium description of PLE

2. Theory and modelling

The PLE theory is developed by means of the following 3-step strategy which
incorporates the ultrafast nonequilibrium aspects (pulse excitation and intraband
relaxation) as well as Coulomb interaction (excitonic effects). First, we determine the
time evolution of the electron and hole distributions within the conduction and valence
band, respectively, during pulse excitation and relaxation. This is done by means of
electron-LO-phonon quantum-kinetic equations [8] which have previously been
employed to describe successfully ultrafast four-wave mixing [9,10] and absorption
signals [1-3] from coherently excited semiconductors. Details of the numerical
implementation are given in Ref. [3]. Second, the luminescence intensity at the exciton
energy Eexc is determined by converting the charge carrier distributions into spontaneous
emission spectra applying a recently developed Greens function approach to PL in
semiconductors [4]. This theory relates the PL spectrum to the semiconductor
polarization function which is then obtained from an explicit solution of the BetheSalpeter equation in ladder approximation. The key result can be expressed as an Elliottlike formula [11] for luminescence that, in contrast to previous results [12], allows to
treat arbitrary nonthermal situations. Moreover, compared to the alternative method of
photon-assisted density matrices [13,14], our approach overcomes several shortcomings
such as negative PL and overestimated excitonic signals, as demonstrated in Ref. [4].
Finally, in the third step, the PLE signals are obtained if the above procedure is repeated
&pump while keeping the other parameters (pump intensity,
pump pulse length, and lattice temperature) fixed.
For the explicit calculations, we use bulk GaAs parameters, Egap = 1.52 eV and &LO
= 36 meV. The exciton bindining energy is 4.7 meV and the homogeneous line
broadening is 0.94 meV. The lattice temperature is fixed at T = 0 K. The pump pulse is
assumed to be Gaussian shaped with a peak intensity of 0.1 MW/cm2, and the spectral
resolution of the luminescence signals is optimized by choosing the pump pulse length to
be 320 fs which is significantly larger than the LO phonon period of 115 fs in GaAs.
3. Results and discussion
In Fig. 2, we present the results for the time evolution of the PLE spectra. It follows that

the PLE spectrum significantly depends  WK WLP LQWHUYD  EHWZHH
and PL detection. For short intervals up to a few picoseconds, the PLE spectra are not
similar at all to the linear absorption but strongly dominated by the signal at the exciton
which is about three orders of magnitude larger than the PLE intensity above the band
gap. This is due to the fact that for high pump frequencies the excited electrons and holes
have not yet completely relaxed towards their band minima. As a consequence, the
emission is not solely from the exciton, but by definition only the excitonic emission
contributes to the PLE signal. Furthermore, there are pronounced satellite peaks in the
continuum region which are completely absent in the linear absorption spectrum. They
clearly reflect bottleneck effects that may occur in the charge-carrier relaxation process.
Once the electrons (or holes) have reached kinetic energies below the threshold for LOphonon emission, the intraband relaxation process drastically slows down. The strength
of this effect depends mainly on the ratio between &pump Egap and &LO, resulting
either in a weak or a strong bottleneck. This, in turn, gives rise to the peculiar satellite
features seen in the PLE signals at early times. It is worthwhile to note that for the more


0.7 ps


1.4 ps


2.8 ps

PLE intensity


5.6 ps


11.2 ps


19.6 ps


28.0 ps




energy (eV)
Figure 2. PLE intensity in bulk GaAs vs. pump energy &pump for times
t = 0.7, , 28.0 ps after pulse excitation (from top to bottom). The pump
intensity is 0.1 MW/cm2, the pump pulse length is 320 fs, and the lattice
temperature is T = 0 K.
polar II-VI semiconductors such as Zinc Selenide similar LO-phonon cascades have been
observed in stationary PLE experiments and were interpreted as hot-carrier effects
In the long-time limit, the picture changes dramatically and the PLE spectrum
resembles much more the absorption spectrum. Since the bottleneck effects are slowly
removed due to quantum-kinetic effects, the dips in the satellite structures become less
and less prRQRXQFHG D
out. Furthermore, the ratio between the PLE signal at the exciton and the continuum has
become almost the same as in the absorption signal because the PLE signal from the
from the exciton has decreased strongly by two orders of magnitude. While the first
effect can again be attributed to the removal of the bottleneck effect on long time scales,
the behavior for &pump Eexc is quite unexpected. An analysis of the time evolution of

the charge carrier distributions under these pump conditions (not shown) reveals the
important role played by quantum-kinetic effects such as scattering processes without
energy conservation. For &pump Eexc, the pump-induced electrons and holes occupy
initially only a very narrow region close to the band extrema. In the semiclassical limit,
these charge carriers would not experience any intraband relaxation at all at zero
temperature. However, this is no longer true in quantum mechanics where the timeenergy uncertainty principle renders a possibility for upward scattering even at T = 0 K.
As a consequence, the electrons and holes are gradually redistributed to higher kinetic
energies which, in turn, explains the significant decrease in the excitonic PLE signal seen
in Fig. 2.
The resemblance
between the absorption spectrum and the PLE signal in the long









assumed equivalence between PLE and absorption. Nevertheless, if both spectra are
plotted on a linear scale [17], we observe some slight deviations: the PLE spectrum
exhibits a broader exciton line and small but noticeable modulations in the continuum
signal. As explained above, the latter effect is related to bottleneck effects and we expect
it to vanish on nanosecond time scales, especially when the scattering with acoustic
phonons (not considered here) becomes important, too. The other effect, the line
broadening of the exciton in PLE, is mainly determined by the spectral width of the pump
pulse, in contrast to the excitonic linewidth in absorption which is only subject to
dephasing, i.e, homogeneous line broadening.
4. Summary
In conclusion, we have developed a novel description of photoluminescence excitation
spectroscopy in semiconductors. The theory is not restricted to thermal equilibrium but
also allows the treatment of highly nonequilibrium systems such as optically excited
electron-hole pairs created by ultrafast femtosecond laser pulses. The phenomenological
assumption of equivalence between PLE and absorption spectra is confirmed in the longtime limit, i.e., approaching thermal equilibrium. For small time intervals between
excitation and luminescence detection, we observe significant differences which can be
attributed to incomplete relaxation and bottleneck effects, and should be easily
observable in experiment since the setup can be customized to require only picosecond
time resolution. Thus, our findings offer a new possibility for time-resolved studies of
hot-carrier phenomena by means of emission spectroscopy.

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