Physics Letters A 372 (2008) 2920–2924

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Dynamic process of self-trapped polaron in photoexcited SrTiO3

Yu Qiu ∗ , Yong-Jin Jiang, Guo-Ping Tong, Jie-Fang Zhang
Department of Physics, Zhejiang Normal University, Jinhua, Zhejiang 321004, China
Received 13 November 2007; received in revised form 15 December 2007; accepted 2 January 2008
Available online 5 January 2008
Communicated by R. Wu

Abstract
Relaxation process of self-trapped polaron is investigated by a nonadiabatic molecular dynamic method. We show localized disorder due to
lattice fluctuations can give rise to a tightly-bound electronic state in ultraviolet illuminated SrTiO3 crystal. This bound state is actually a self-
trapped polaron in accordance with the experimentally observed large Stokes-shift. The formation of the self-trapped polaron is shown to be an
ultrafast process.
© 2008 Elsevier B.V. All rights reserved.

PACS: 78.20.Bh; 72.15.Lh; 71.38.-k

Keywords: Dynamics; Photoexcitation; Self-trapped polaron; Luminescence

1. Introduction nated SrTiO3 crystal to clarify the experimentally observed di-

The idea of self-trapping originally introduced by Landau
[1] describes an excess electron being trapped within a potential
well created by itself in a crystal. The electron together with the
locally distorted lattice around it can be considered as a quasi-
particle which is known as a polaron. In the past decades, many
studies have been investigated on polaron [2–7].
Polaron stability and polaron formation in the framework of
e–p coupling have been well discussed within the adiabatic
limit [7]. The occurrence of large polaron or small polaron
depends on whether long-range or short-range electron-lattice
interactions dominate. When interactions of both ranges are
sufficiently strong, only the small polaronic state can form [5].
In despite of the competition of large and small polarons, they
can coexist at the same time [8]. In contrast to researches on
narrow and sharp peaks in various spectra out of harmonic
effect, anharmonic features of lattice vibrations gained more at-
tentions [9–16]. Recently, the model of anharmonic phonons
coupling with electrons were studied for an ultraviolet illumi-
* Corresponding author. Tel.: +81 579 82298832.
E-mail address: yqiu@zjnu.cn (Y. Qiu).
0375-9601/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.physleta.2008.01.002
electric enhancement and photoconductivity in the crystal. The
large and small polarons were obtained unifiedly within a vari-
ational method [17]. As schematically shown in Fig. 1, they
are separated by an adiabatic barrier. It should be noted that
the anharmonic modes dominate the extended state and the har-
monic ones dominate the tightly bound state. The dynamics of
these two states are related to dielectric enhancement and large
Stokes-shift respectively in experiment [16,17].
As is known, an electron in an insulating crystal induces a
local lattice distortion around itself as it is excited by a photon.
A sudden change in charge distribution appears after optical ex-
citation, which induces a nonequilibrium state in the crystal lat-
tice. So the whole electron-lattice system will undergo certain
relaxation process to reach a new equilibrium state. The issue
of lattice relaxation process is concerned with the initial or-
der in transfer energy [18] as well as the hidden multi-stability
intrinsic to each solid [19]. The direction of lattice relaxation
is also affected by initial lattice configuration. Distinction in
initial conditions can lead to different relaxation routes as in-
dicated by the dash and dash-dot arrows in Fig. 1. For per-
ovskite SrTiO3 crystal, two metastable states can appear after
ultraviolet irradiations, superparaelectric large polaron and self-
trapped polaron [17]. Starting from the Frank–Condon state,
 Y. Qiu et al. / Physics Letters A 372 (2008) 2920–2924 2921

2. Model and method

We use the Hamiltonian (≡ H ) for SrTiO3 crystal employed

in the previous works [17,20]
  †   †
H = −T alσ al  σ + h.c. − Sb ωb Bl al,α al,α
{l,l  },σ l
1  
+ KB B2 + MB Ḃ2
2

Sd ωd  2 † 1  
− Dl,i al,α al,α + 6
KD D,i + MD Ḋ,i
2
2 2
l,i ,i
1  1 
+ KBB B B + KDD 3
D,i D3 ,i  . (1)
2 
2  
{, } {, },i,i
Fig. 1. Variational result of the adiabatic surface for the single electron system.
Dash and dash-dot arrows schematically indicate distinct relaxation routes. Δ +
is the reciprocal localization length [20]. Parameters are: Sb = 7.1, Sd = 164.3.
Wherein, alσ (alσ ) is the creation (destruction) operator of an
electron at the lth lattice site with spin σ (= α, β) in a simple
cubic crystal, and T is the electronic transfer energy between
the neighboring two lattice sites. Sb (> 0) is the dimension-
less constant of the linear coupling between the electron and
the site localized breathing mode, whose energy is ωb and the
dimensionless coordinate is Bl . Sd (> 0) is the dimensionless
constant of the quadratic coupling between the electron and
the site localized T1u mode, whose energy is ωd and the di-
mensionless coordinate in the direction i(= x, y, z) is Dli . The
density of the excited electrons in a crystal is not strong under
ultraviolet illuminations. Thus, we do not consider many-body
effect. In consequence, in the Hamiltonian, we neglect the on-
site Coulomb repulsion term because it has no effect on the
single electron system. The summation index l (l  ) runs over the
e–p coupling region and the index  ( ) runs over the whole
Fig. 2. Schematic structure of the crystal lattice. Filled circles denote the e–p crystal. {· · · , · · ·} denotes the summation is over the nearest
coupling region. Vacant circles denote the reservoir. neighboring lattice sites. With the Plank constant h̄ being forced
to be a dimensionless constant, h̄ ≡ 0.6591, fs−1 is equivalent
the e–p coupling system relaxes into a ferroelectric domain to eV. In consequence, we have the elastic coefficients KB ∼ ωb
in picoseconds, which is a large polaron in the microscopic and KD ∼ ωd /3, and the effective masses MB ∼ h̄2 /ωb and
essence [20]. MD ∼ βm h̄2 /ωd . βm is an effective mass parameter [17]. The
To investigate the dynamic process of the e–p coupling sys- last two terms in the Hamiltonian reflect the coupling of the
tem in an illuminated crystal, the crystal can be divided into vibration degrees of freedom among the adjacent lattice sites.
two regions as shown in Fig. 2, the system (denoted by filled cir- With these terms, the system can exchange energy with the
cles) and the reservoir (denoted by vacant circles). In the system reservoir during the relaxation process. They serve to realize
region, the photoexcited electrons are assumed to couple with damping during real dynamical processes. The parameters in
the lattice. By contrast, in the region of reservoir, the lattice this tight-binding model take the same values as in the previous
vibrations are described by bare phonons. Lattice fluctuations, work [17]. Usually, the intersite elasticity KBB (KDD ) is much
in particular in the surface, are sensitive to environmental con- less than the intrasite elasticity KB (KD ), so practically we take
ditions. Even at low temperatures, lattice fluctuations can be KBB = KB /10 and KDD = KD /10.
aroused and readily give rise to localized disorders. In this Let- To employ the molecular dynamic method, it is convenient
ter, we numerically study the relaxation process of a dual e–p to divide the Hamiltonian into two parts, the electronic Hamil-
coupling system by using a nonadiabatic dynamic method. We tonian (≡ He ) and the lattice Hamiltonian (≡ HL ), as follows
will show that localized disorder due to lattice fluctuations can
H = He + HL , (2)
give rise to a stable tightly-bound electronic state in ultravio-   †   †
let illuminated SrTiO3 crystal, which explains the origin of the He ≡ − T alσ al  σ + h.c. − Sb ωb Bl al,α al,α
large Stokes-shift of the luminescence observed in this crystal {l,l  },σ l
[21]. The formation of the self-trapped polaron is an ultrafast Sd ω d  2 †
process. The relation of the self-trapped polaron and the dielec- − Dl,i al,α al,α ,
2
l,i
tric property of the crystal is also discussed.
2922 Y. Qiu et al. / Physics Letters A 372 (2008) 2920–2924

1   1  
HL ≡ KB B2 + MB Ḃ2 + 6
KD D,i + MD Ḋ,i
2
2 2
 ,i
1  1 
+ KBB B B + KDD 3
D,i D3 ,i  .
2 
2  
{, } {, },i,i

If the time interval of the dynamic process is small enough, the

dynamics of the electron and the lattice can be handled sepa-
rately. The electronic state evolves following the Schrödinger
equation,
∂|Ψ (t)  
i h̄ = He Ψ (t) . (3)
∂t
Meanwhile, the lattice evolves following the Newtonian equa-
tions
Ml Θ̈l (t) = flΘ (t) (Θ ≡ B, D), (4) Fig. 3. Energy evolution with respect to time for the crystal size of 15 × 15
and the system size of 5 × 5. Dot line and solid curve denote the energy evo-
flΘ (t) = − ∂Θ∂l (t) Ψ (t)|H |Ψ (t),
with Ml being the effective lutions of the crystal and the system respectively. Dash curve denotes system
Θ
mass for the lth lattice site and fl (t) the transient force on it. energy evolution with an introduction of factitious small damping. Parameters
As a result, the evolution of the e–p coupling system as well are: Sb = 7.1, Sd = 164.3.
as the reservoir can be obtained by numerically calculating the
coupled equations (3) and (4).
For the initial lattice configuration, we introduce a local
disorder in the center of the system, keeping other sites of
both the system and the reservoir in their equilibrium posi-
tions. The complete set of the electronic state (≡ ϕn (t)) satisfies
He ϕn (t) = n (t)ϕn (t) (n = 0, 1, 2, . . .), and the time dependent
electronic state |Ψ (t) can beexpanded with respect to the elec-
tronic eigenstates, |Ψ (t) = n Cn (t)ϕn (t). Initially, the elec-
tron is assumed to be at the bottom of the conduction band, thus
Cn (0) = δn0 and |Ψ (0) = |ϕ0 (0).

3. Results

We investigate a system with the size 5 × 5 and the whole

crystal of the size 15 × 15. A nonzero value (0.5) is assigned
to Bl of the central site to simulate the initial disorder in the
lattice of the system. The corresponding energy evolutions are
shown in Fig. 3. The dot line describes the evolution of the
total energy of the crystal. It well reflects energy conserva-
tion law. The dash curve indicates the evolution of the system
energy with the onset of an extra small damping. With this fac-
titious small damping, the transient force on the lth lattice site
reads
∂     Fig. 4. Schematic energy transmittal and energy dispersion processes in the
flΘ (t) = − Ψ (t)H Ψ (t) − MΘ αΘ Θ̇l . (5) crystal. Squares denote the effective regions of lattice vibration.
∂Θl (t)
As is shown by the dash curve, the system energy is gradu-
ally reduced before 2000 fs. After 2000 fs, the system energy electron is incipiently in the bottom of the conduction band.
rests on the value of about −1.20 eV. This appears to be a deep With time, the electron transmits energy first to the lattice of
and stable state in the gap. the system through e–p interactions as schematically shown by
The introduction of the factitious small damping is essen- (a)–(b) of Fig. 4. Rapidly the system energy is dispersed into
tially a mathematic management. It is employed simply to give the reservoir by inter-lattice interaction from inner to exterior
the significant tendency of the evolution of the system energy. as shown by (c)–(d) of Fig. 4. During this process, the reservoir
If the crystal is taken to be adiabatic from its environment, exchanges energy with the e–p coupling system periodically
the actual evolution process must be obtained without intro- as indicated by the fluctuations on the solid curve in Fig. 3.
duction of any factitious damping. The real process is given Gradually, the electron slips into a deep potential well formed
by the solid curve of Fig. 3. As the initial condition says, the by the lattice distortion and the system energy is released into
 Y. Qiu et al. / Physics Letters A 372 (2008) 2920–2924
(a)
(b)
Fig. 5. Electronic distributions within the e–p coupling region after 2000 fs
for different initial disorders in lattice vibration, (a) central site disorder and
(b) multi-site disorder.
the reservoir as guided by the dash curve. After 2000 fs, the
system attain a metastable state. The corresponding electronic
state is shown in Fig. 5(a). It is clear that this is a closely
bound state. It is just the self-trapped polaron as illustrated on
the adiabatic surface in Fig. 1. The relaxation process of the
self-trapped polaron is schematically indicated by the dash ar-
row.
SrTiO3 has a large energy gap of about 3.2 eV [21–23]. The
broad luminescence band (2.4 eV) [21] suggests a large Stokes-
shift (0.8 eV) for the crystal. With an assumption of identical
binding energy for electron and hole, the electronic binding
energy becomes 0.2 eV. Our numerical result comes to fit the
experiment well. Thus, the origin of the luminescence is as-
signed to a recombination of self-trapped polaron.
An alternative situation for initial disorder in lattice vibra-
tion is also considered. Besides the central disorder, we pre-
sume the nearest-neighbor-site disorders, i.e., Bl for the nearest
neighboring sites of the central site are assigned an identical
nonzero value (0.3). The energy evolution processes have quite
a similar tendency as those in Fig. 3. As the system energy
reaches its stable value of about −1.20 eV, the electronic state
appears to be shown by Fig. 5(b). It is clear that this is also
a closely self-trapped state. The formation of the self-trapped
polaron is also within several picoseconds. Beyond the above
discussed 2-dimension cases, we also calculate the energy evo-
lution processes for 3-dimension cases and obtain quite similar
consequences as is shown in Fig. 6. Thus, our numerical works
show that the formation of self-trapped polaron is insensitive
to dimensionality, which is in accordance with the perturbative
result [24].
2923
Fig. 6. Energy evolution with respect to time for the crystal size of 11 × 11 × 11
and the system size of 5 × 5 × 5. Dot line and solid curve denote the energy
evolutions of the crystal and the system respectively. Parameters are: Sb = 4.5,
Sd = 164.3. Initial lattice disorder is simulated by the central site displacement
of 0.5.
4. Discussion and conclusion
As is well known, temperatures tend to introduce disorders
in crystal lattices, which are ready to lead to self-trapped po-
larons in the crystal in terms of the above discussions. In that
work [17], it was shown that in the large polaron state, the di-
electric property of the crystal will be greatly enhanced. By
contrast, in the self-trapped polaron state, the crystal almost
shows no dielectric variance. In the immediate consequence,
temperatures tend to suppress polarization of the crystal. This
result can be extended to other crystals, and give a profile of
why most crystals show paraelectric phases at high tempera-
tures.
In conclusion, relaxation process of the self-trapped polaron
is investigated by a nonadiabatic molecular dynamic method
for ultraviolet illuminated SrTiO3 crystal. We show that local-
ized disorder due to lattice fluctuations can give rise to a tightly
bound electronic state in ultraviolet illuminated SrTiO3 crys-
tal. The formation of the self-trapped polaron is an ultrafast
process.
Acknowledgements
This work was supported by the Natural Science Founda-
tion of China and the Natural Science Foundation of Zhejiang
Province of China.
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