Physica B: Condensed Matter 558 (2019) 127–130

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Physica B: Condensed Matter

journal homepage: www.elsevier.com/locate/physb

Temperature dependent localization dynamics of excitons in Mg0.14Zn0.86O T

alloyed semiconductor
Md. Sherajul Islama,∗, Md. Soyaeb Hasana, E. Kobayashib, Takayuki Makinob
a
Department of Electrical and Electronic Engineering, Khulna University of Engineering & Technology, Khulna, 9203, Bangladesh
b
Department of Electrical and Electronic Engineering, University of Fukui, 3-9-1 Bunkyo, 910-8507, Fukui, Japan

A R T I C LE I N FO A B S T R A C T

Keywords: This paper explicates the temperature induced localization dynamics of exciton in Mg0.14Zn0.86O alloyed
Photoluminescence semiconductor. The photoluminescence (PL) spectroscopy measurement has been performed at the temperatures
Exciton localization ranging from 16 K to 180 K. The linewidths of the PL bands reveal the W-shaped behavior with temperature. We
Monte Carlo simulation also observe the temperature induced S-shaped characteristic of Stokes shift. These experimental findings are
MgZnO alloy
after that modeled using the Monte Carlo simulation of exciton hopping and relaxation. The simulation results
Stokes shift
quantitatively agree with both the Stokes shift and the PL linewidth for the whole temperature regime while
accounting for the band potential fluctuation, σ = 17 meV and the additional inhomogeneous broadening,
Γ = 8 meV. The band potential fluctuation is attributed here to the inhomogeneous distribution of Mg in
Mg0.14Zn0.86O alloyed semiconductor. These results may provide a meaningful reference to the development and
design of ZnO based optoelectronic devices.

1. Introduction knowledge of the electronic structures of the disorder-induced localized

states. The theoretical efforts have been mainly based on the effective
ZnO is a direct, wide band gap semiconductor material with nu- Hamiltonian approach, where the disorder potential is replaced with
merous potential applications in spintronics, sensors, transparent elec- the complex self-energy (the coherent-potential approximation). The
tronics, and especially in optoelectronic devices which operate in the density of states (DOS) of the localized state was obtained through its
violet and ultraviolet (UV) regime [1–6]. However, for competent op- numerical solution [6]. Quite recently, the first-principles-based ap-
toelectronics, the realization of suitable hetero-junction is the key re- proach is also adopted to take the electronic localization effect into
quirement in order to expedite the confinement of charge carriers and consideration [17].
photons. Ternary MgxZn1-xO alloys have been shown to be an appro- It is well known that the photocurrent spectroscopy enables us the
priate material as the band gap energy of this alloy can be made ad- quantitative evaluation of the line-shape of the localized states ex-
justable [5,7] by substituting Zn ions with Mg ions in the host lattice of perimentally using the Laplace transformation technique [18]. On the
ZnO. Thus, for the fabrication of hetero-structures with optimized op- other hand, Kazlauskas and coworkers deduced the line-shape of the
tical features, the detailed knowledge of the fundamental optical localized states by analyzing the temperature-dependent photo-
properties of MgxZn1-xO alloyed semiconductor is essential. Although, luminescence (PL) data with the technique of Monte Carlo simulation
the thin-film ZnO [3,4] along with its Quantum Wells (QWs) [8–11] [19]. This process has successfully clarified the experimentally ob-
have been subjected of many fundamental physics investigations, served anomalous ‘S-shaped’ and ‘W-shaped’ temperature dependence
however, it is only recently that MgZnO alloy commenced to be actively of the PL peak energy and line-width, respectively in InGaN/GaN QWs.
investigated both experimentally [5,7,12–15] and theoretically [16]. Using the similar technique, one of the authors of the present article
The above mentioned advantages renders urgent to increase our evaluated the characteristics of the line-shape of the localized states in
knowledge of the optical properties of these alloy materials. ZnO/MgZnO QWs [20]. Moreover, in case of Zn1-xCdxSe quantum is-
In general, semiconductor alloys suffer from the microscopic con- lands [21], the Monte Carlo technique has been employed to simulate
centration fluctuation which causes the generation of the localized the phonon-assisted redistribution processes of excitons which revealed
states, prevailing from the band edge. The full understanding of the the anomalous ‘S-shaped’ temperature behavior of PL peak energies.
optical properties of the alloyed semiconductors thus requires the Anomalous ‘Λ-shaped’ PL line-width is observed in the temperature

∗
Corresponding author.
E-mail address: sheraj_ruet@yahoo.com (Md. S. Islam).

https://doi.org/10.1016/j.physb.2019.01.049
Received 20 June 2018; Received in revised form 20 December 2018; Accepted 30 January 2019
Available online 30 January 2019
0921-4526/ © 2019 Elsevier B.V. All rights reserved.
Md. S. Islam et al. Physica B: Condensed Matter 558 (2019) 127–130

range of 0–200 K. Likewise, the evidence of localized exciton has also

been demonstrated in the ternary MgZnO alloyed semiconductor, re-
vealing the remarkable enhancement in emission spectra at certain 3.62 50
temperature and unusual behavior of PL line-width (increase-decrease-

PL Peak Energy (eV)

increase) with increasing temperature [13]. Moreover, Neumann et al.

FWHM (meV)
[22] reported the red-shifting behavior of the PL spectra with tem-
perature in this alloy. The signature of exciton motion and their con-
tribution to the inhomogeneous Stokes shift and the full width at half 3.61 40
maximum (FWHM) of PL bands have also been analyzed for different
Mg contents [22]. The unusual behavior of PL bands in MgZnO alloy
PL Peak Energy
can be elucidated adopting the above mentioned technique, which si-
PL FWHM
mulates the exciton hopping and relaxation. However, there is no prior
report on the quantitative interpretation of the exciton hopping to ex- 3.60 30
plain the anomalous PL properties in MgZnO alloyed semiconductor. 0 50 100 150 200
Thus, the theoretical authentication of the experimental results of the Temperature (K)
MgxZn1-xO alloy is more desirable.
Fig. 2. Temperature dependence of the experimental PL maximum and the
It should be noted that the above mentioned technique based on the
FWHM.
combination of the simulation and the PL spectroscopic measurement
allows us the acquisition of the information on the dynamical aspects,
in addition to the ‘static’ information. Accordingly, here in this work we positions show the shifting behavior with temperature. Up to the tem-
have investigated the PL spectroscopy of epitaxially grown perature of 60 K, a small shift in the PL peak energy is observed.
Mg0.14Zn0.86O alloyed semiconductor crystals in details. The dynamics However, a large shift is found till the temperature of 120 K even
of localized excitons in this alloy have been studied using the technique though the peak energy shifts again to a smaller value with further
of Monte Carlo simulation at the temperature range of 16–180 K. increase of the temperature. In addition, an anomalous characteristic of
Considering an additional inhomogeneous broadening with the band PL linewidth is visible with temperature. The PL linewidth remains
potential fluctuation, the phonon-assisted exciton hopping and relaxa- unchanged while T < 50 K, however, a sharp increase is observed up
tion has been quantified in the Mg0.14Zn0.86O alloy for the first time. to the temperature of 90 K. After remaining unchanged till T = 140 K, it
increases even more with the further increase of the temperature. The
anomalous behaviors of both the PL maximum and the linewidth have
2. Experimental details
been illustrated clearly in Fig. 2. It is found that the PL band peak
position exhibits a well-known S-shaped variation [23–25] with tem-
The sample measured in this study is 180-nm-thick Mg0.14Zn0.86O
perature. Moreover, the W-shaped behavior of PL line-width is seen
epilayer grown on ScAlMgO4 substrate fabricated by pulsed-laser de-
with the change of temperature. These anomalous behaviors of the PL
position. The PL were excited by a 325 nm continuous-wave He-Cd
spectra reveal the signature of exciton hopping over randomly dis-
laser, dispersed by a monochromator, and detected by a liquid-N2
persed localized states with a crossover from a non-thermalized to a
cooled charge coupled device (CCD). The PL measurements were per-
thermalized distribution function of the excitons [26] in Mg0.14Zn0.86O
formed at temperatures ranging from 16 K to 180 K.
ternary alloyed semiconductor.
The exciton hopping and relaxation over the localized states in the
3. Results and discussion Mg0.14Zn0.86O ternary alloy have been modeled here using the two
dimensional (2D) Monte Carlo simulation. The algorithm was given
Fig. 1 depicts the temperature dependent PL spectra of elsewhere in details [18], and we will only explain it briefly at this time.
Mg0.14Zn0.86O alloyed semiconductor. The dots indicate the PL peak The hopping transition rate of excitons from an occupied site i to an
energy positions for each temperature. It is found that the PL peak unoccupied site j is described by the Miller-Abrahams expression [27]:
2rij εj − εi + |εj − εi |
υij = υ0 exp(− − )
Mg0.14Zn0.86O α 2kT (1)

where υ0 is the attempt-to-escape frequency, rij is the distance between

site i and j, α is the decay length of the exciton center-of-mass wave
PL Intensity (a.u)

function in the localized states, εi and εj are the energies of state i and j.
T=16K We considered the energy of the band tails, which follows a Gaussian
DOS as follows:
T=30K
T=50K N 1 ε2
g (ε ) = exp(− 2 )
T=60K σ 2π 2σ (2)

T=90K with σ as the scale of energy distribution. Here, N is the concentration

T=120K of the localized states. The reference energy is ε = 0 , which is the
T=150K middle of the distribution. All the energies in our simulation are below
this value which indicates that we have a “half” distribution of the DOS
T=180K [19]. For each generated exciton, the hopping process terminates by
recombination with the probability, τ0−1, here, τ0 is the radiative lifetime
3.55 3.6 3.65 of exciton. The energy of the localized state where the recombination
E (eV)
has taken place is scored to the emission spectrum. Combining the
Fig. 1. The PL spectra from Mg0.14Zn0.86O alloyed semiconductor measured at spatial fitting parameter Nα 2 and temporal fitting parameter τ0 υ0 with
different temperatures. The PL intensities are normalized with respect to the the scale of band potential fluctuation σ , the specific process is de-
highest intensity and shift vertically. Dots are the peak energies of each tem- termined.
perature. The calculated Stokes shift and the PL FWHM for Mg0.14Zn0.86O

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Md. S. Islam et al. Physica B: Condensed Matter 558 (2019) 127–130

-20 Table 1
2 3 Comparison of the potential profile fluctuations and additional inhomogeneous
(a) N =1, 0 0=10
broadening for different structures extracted by double-scaled potential profile
Stokes Shift (meV)

model.
-30 =16meV Materials σ (meV) Γ (meV) Ref.

=17meV In0.22Ga0.78N/GaN MQWs 31 29 [19]

In0.27Ga0.73N/GaN MQWs 38 47 [19]
Mg0.27Zn0.73O/ZnO QWs 20 12 [20]
-40 Mg0.12Zn0.88O/Cd0.04Zn0.96O QWs 20 29 [20]
Al0.35Ga0.65N/Al0.49Ga0.51N QWsa 46 29 [28]
=18meV Al0.26Ga0.74N epilayersa 19 20 [29]
Mg0.14Zn0.86O epilayers 17 8 Our sample

a
2 3 3D Monte-Carlo simulation results.
(b) N =1, 0 0=10
50 =18meV, =7meV
FWHM (meV)

unchanged. The FWHM increases again after T > 120 K, which is re-
lated to the influence of phonon coupling. To get a quantitative
agreement with the experimental linewidth, an additional in-
40 homogeneous broadening, Γ is incorporated based on the double-scaled
potential profile model proposed by K. Kazluskas et al. [26]. We have
=17meV, =8meV presented the data regarding the relevant values of potential profile
30 fluctuation scales σ and Γ in Table 1. These parameters were used to
=16meV, =8.5meV
perform the double-scaled potential profile model in several samples,
including epitaxial layer and QW structure. The additional in-
0 50 100 150 200 homogeneous broadening, Γ in the ternary alloy is significantly smaller
Temperature (K) than that in the QWs. It is suggested that the excitonic localization ef-
fect can be more simply interpreted in the alloy system because the Γ is
Fig. 3. Temperature dependence of the Stokes shift and PL linewidth. Circles related to the effect that cannot be taken into account with the present
indicate the experimental results. Solid line represents the best fitting with the model. This is somehow unexpected if we consider about the well-width
fitting parameters σ = 17 meV , Nα 2 = 1, υ0 τ0 = 1 × 103 , Γ = 8 meV, respec-
dependence of the quantized energy. Thus, the comparative study
tively. Dashed line and dash dot line are the calculated results with different
sets of σ and Γ .
suggested that the Γ can be a descriptive parameter for universally
understanding the contributions from the well-width and microscopic
concentration fluctuations against the (localization) mechanism of the
ternary alloy have been compared with the experimental results in material-informative perspectives.
Fig. 3(a) and Fig. 3(b), respectively. The solid line in Fig. 3(a) illustrates It is evident that each sample possesses a certain degree of in-
the simulated Stokes shift with most relevant set of fitting parameters homogeneity due to their constituent elements and structural differ-
(σ = 17 meV , Nα 2 = 1 and τ0 υ0 = 1 × 103 ). It shows a good quantitative ences. The QWs structures where both wells and barrier consist of al-
agreement with the experimental Stokes shift except in the temperature loyed semiconductor materials possess more roughness than the usual
range of 30 K–50 K. In this regime, the calculated Stokes shift is slightly QWs. The inhomogeneity in epilayer turned out to be much smaller
smaller than the experimental observation. The smaller Stokes shift than multiple QWs and QWs structures. Moreover, to increase the
may be attributed to the reduced value of PL peak position. The si- content of the dopant material leads to the more potential fluctuation.
mulated PL peak position shifts to the smaller value owing to adopting For Mg0.14Zn0.86O epilayer, the repeated simulation shows that the
the constant lifetime of exciton in the whole temperature regime. realistic fitting of the PL linewidth with the experimental results is
However, the temperature dependence of the lifetime of excitons is not obtained while considering the additional inhomogeneity parameter, Γ
monotonous, it first increases at low temperatures and decreases con- in the calculation. Thus, the actual density of localized states with en-
tinuously with increasing temperatures. Moreover, the increase of ergy incorporating the additional inhomogeneous broadening becomes:
lifetime of excitons at low temperature in Mg0.14Zn0.86O epilayer is
higher than that of other materials. (E − E0)2
D (E ) ∝ exp[− ]
The temperature behavior of the Stokes shift is deduced from the 2(σ 2 + Γ 2) (3)
peak position of the simulated PL spectra. The PL peak position shows
the redshift behavior at low temperature due to the increased mobility We have successfully reproduced the PL spectra and estimated the
of the excitons. With the increase of temperatures, the excitons become optimized linewidth by varying the additional inhomogeneous broad-
competent to move long distances to reach deeper localized states. ening parameter, Γ although this result shows some discrepancies with
During this process, the excitons can be trapped by lower energy states the experiment. The calculated FWHM is narrower than the experi-
up to T > 60 K. Thus, the lower energy states become populated gra- mental results in the low temperature regime which is mainly due to the
dually and the PL peak energy shows the blue shift behavior. After assumption that all the excitons have a same lifetime.
120 K, the redshifts of the PL peak energy is mainly caused by the band The calculated results show that for any temperature the estimated
gap shrinkage. band potential fluctuation, σ of the Mg0.14Zn0.86O epilayer is about
Fig. 3(b) depicts the W-shaped temperature behavior of the PL 17 meV. The energy of the potential fluctuation, σ is estimated from the
linewidth. The anomalous broadening of the PL linewidth is also at- kink of the temperature dependence of experimental linewidth using
tributed to the increased mobility of the localized excitons. At low the expression, σ = 2KBTkink. The characteristic kink of the PL linewidth
temperature regime, only the weakly localized states are occupied and of this alloy is observed at T = 90 K, which indicates a crossover from
the PL linewidth is narrow. By raising the temperature, the weakly non-thermalized to thermalized energy distribution of excitons. The
localized excitons become more mobile and recombine in a broader additional inhomogeneous broadening, Γ is found to be 8 meV.
energy distribution of the localized states. In the range of 90 K–120 K, However, at high temperature, the simulated PL FWHM is narrower
the excitons achieve thermal equilibrium and the PL linewidth remains than that of the experimental FWHM. The discrepancy of the calculated
and experimental linewidth at higher temperature may be originated by

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