Journal of the Korean Physical Society, Vol. 65, No. 12, December 2014, pp.

2077∼2081

Photoluminescence Saturation and Exciton Decay Dynamics in Transition

Metal Dichalcogenide Monolayers

Min Ju Shin, Dong Hak Kim and D. Lim∗

Department of Applied Physics, College of Applied Science, Kyung Hee University, Yongin 449-701, Korea

(Received 17 September 2014, in final form 13 October 2014)

We report a photoluminescence (PL) and transient reflection spectroscopy study of the exci-
ton dynamics in monolayer transition-metal dichalcogenides (TMDs). PL saturation in monolayer
MoSe2 occurs at an excitation intensity more than two orders of magnitude lower than in monolayer
MoS2 . Transient reflection shows that nonlinear exciton-exciton annihilation is the dominant exci-
ton decay process in monolayer MoSe2 in contrast to the previously-reported linear exciton decay
in monolayer MoS2 . In addition, the exciton lifetime in MoSe2 , which is greater than 125 ps, is
more than an order of magnitude longer than the several-ps exciton lifetime in MoS2 . We find that
the dramatically different exciton decay mechanisms and PL saturation behaviors of the MoSe2 and
the MoS2 monolayers can be explained in terms of the difference in their exciton lifetimes.

PACS numbers: 73.21.Ac, 73.50.Gr, 78.47.+p, 78.55.HX

Keywords: Exciton dynamics, Photoluminescence, Transient reflection spectroscopy, MoS2 , MoSe2
DOI: 10.3938/jkps.65.2077

I. INTRODUCTION licity [13,14]. Based on the circular polarization of pho-

The transition-metal dichalcogenide (TMD) MX2 ,
such as MoS2 , MoSe2 , WS2 and WSe2 , has a layered
structure, where each layer is bonded by a weak van der
Waals interaction [1]. Although bulk MX2 is an indi-
rect bandgap semiconductor, it exhibits a crossover from
an indirect to a direct bandgap in the monolayer limit
[2–4]. Since the discovery of the direct bandgap struc-
ture in monolayer MoS2 , extensive research efforts have
been made on few-layer TMDs because of their excellent
optical and electrical properties [2,5–7]. In addition, elec-
trons in few-layer MX2 possess a valley degree of freedom
as in graphene [8–10]. Graphene has been the material
used in valleytronics research, but its drawbacks, such
as the inherent lack of inversion symmetry and bandgap
limit its applications [8,9]. In contrast, monolayer MX2
has an inherently broken inversion symmetry and direct
bandgap structure at degenerate valleys, K and K’, lo-
cated at the corners of the hexagonal Brillouin zone [10,
11]. Near the conduction and the valence band edges,
the electronic states are of a d-orbital character. There-
fore, the strong spin-orbit interaction in the d-orbital,
together with the broken inversion symmetry, spin-splits
the valence band significantly and couples the spin and
the valley degree of freedoms in the monolayer MX2 [12].
The first optical generation of valley polarization was
reported in 2012 for monolayer MoS2 by using optical he-
toluminescence (PL), the hole valley-spin lifetime greater
than 1 ns was proposed. Afterwards, the valley polariza-
tion, as well as the valley coherence, was reported for
other monolayer and bilayer TMDs, such as WS2 and
WSe2 [15, 16]. The exciton and the valley dynamics in
monolayer MoS2 have also been studied recently by us-
ing helicity-resolved transient absorption [17, 18], time-
resolved photoluminescence [19], and Kerr rotation [20].
The obtained exciton lifetimes of monolayer MoS2 are
typically several picoseconds [18,19], and the valley depo-
larization times range from sub-ps to several picoseconds
[17,20], in stark contrast with the greater than 1 ns valley
lifetime estimated based on circular polarization of the
PL [14]. On the other hand, a recent work on monolayer
MoSe2 showed a strongly density dependent exciton de-
cay and a relatively longer exciton lifetime [21]. Because
a long exciton lifetime is a prerequisite to valley-based
devices, a better understanding of the exciton dynam-
ics in atomically-thin TMDs is required for their future
applications.
In this paper, we report our work on the exciton de-
cay dynamics in monolayer MoSe2 and MoS2 studied by
using excitation intensity/fluence dependent photolumi-
nescence and transient reflection spectroscopy. We find
dramatically different PL saturation behaviors and exci-
ton decay mechanisms between MoSe2 and MoS2 mono-
layers. We find that the difference in the exciton lifetimes
can explain our results.

∗ E-mail: dlim@khu.ac.kr
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-2078- Journal of the Korean Physical Society, Vol. 65, No. 12, December 2014
II. EXPERIMENTS
MoS2 and MoSe2 monolayer samples are obtained by
using mechanical exfoliation from bulk crystals on silicon
substrates with a 280 nm-thick thermal SiO2 or a 70-
nm thick pulsed-laser-deposited Al2 O3 overlayer. The
monolayer is first identified by using a optical microscope
and then the confirmed by raman and photoluminescence
measurements.
A Ti:sapphire femtosecond oscillator with a sub-100
fs pulse duration and an 82 MHz repetition rate was
used to excite the monolayer MoSe2 samples, both in
the photoluminescence and the transient reflection spec-
troscopy measurements. The 632-nm line from a He-
Ne laser was used for MoS2 excitation. A long-working-
distance 50X objective lens was used to focus the light
onto the monolayers with a spot diameter of ∼1.4 m.
The PL measurement of MoSe2 was performed by using
either a 760-nm CW or a mode-locked pulse laser beam.
After passing through the objective lens, the pulse from
the Ti:sapphire oscillator was broadened to ∼250 ps due
to group velocity dispersion. Band pass filters were used
to clean the laser beam before it was focused onto sam-
ples and edge pass filters were used to cut the laser line
from PL emission. Figure 1 shows a schematic diagram of
the transient reflection measurement setup. For the tran-
sient reflection measurement, mode-locked 780-nm pulses
from the oscillator were divided into pump and probe by
using a beam-splitter, and the pump-excitation-induced
reflection change in the probe at the chopper frequency
was measured as a function of the pump-probe delay by
using a lock-in amplifier. Here, a combination of a half-
wave plate and an analyzer was used to block the pump
before the detector.
III. RESULTS AND DISCUSSION
Figure 1 shows the PL intensity as a function of the
excitation laser intensity for monolayer MoSe2 and MoS2
samples. The PL responses are dramatically different for
the MoSe2 and the MoS2 monolayers. The PL from the
MoS2 monolayer on both SiO2 and Al2 O3 overlayers is
almost linear throughout the entire range of excitation
intensity (MoS2 monolayer on SiO2 displays a slightly
more nonlinear behavior, probably due to the low dielec-
tric constant of SiO2 ). The PL from MoSe2 , however, is
completely different, showing a highly nonlinear behav-
ior, even at very low excitation intensity. Because the
PL intensity is proportional to the exciton density, the
nonlinearity means that the steady-state exciton density
in monolayer MoSe2 is not proportional to the excitation
laser intensity (the nonlinearity is not from saturation of
the absorption, as will be shown later) and that the exci-
ton decay occurs via a strong exciton-exciton interaction.
The rate equation for exciton density N can be written
Fig. 1. (Color online) Schematic diagram of the transient
reflection measurement setup.
as:
dN N γ
=g− − N 2, (1)
dt τ 2
where g is the exciton generation rate, τ1 (τ ) is the linear
exciton decay rate (exciton lifetime), and γ is the nonlin-
ear exciton-exciton annihilation (EEA) coefficient. Be-
cause the steady-state exciton density N is constant for
CW excitation, it can be expressed
 as
a function of exci-
1 I
tation intensity I as N = τ r −1 + 1 + I0 . Here, I0
E
= 2τ 2pγa (Ep : excitation photon energy, a: absorbance
of the sample) is the excitation intensity at which the
dominant decay mechanism changes from linear exciton
decay to nonlinear EEA.
We fit the PL response from monolayer MoSe2 and plot
the result in Fig. 2(a) as a red line. In the low excitation
limit (I  I0 ), the nonlinear exciton-exciton interaction
is insignificant, and the PL intensity is proportional to
the excitation intensity. If the excitation intensity is high
(I  I0 ), EEA dominates the decay process, and the PL
intensity becomes a nonlinear function of the excitation
intensity. The contributions of the linear and the non-
linear decay terms to the total decay rate are calculated
and plotted in the inset of Fig. 2(a). The decay rate due
to EEA begins to exceed that due to linear exciton decay
at a very low excitation intensity, ∼0.5 μW/μm2 . In con-
trast, the PL from monolayer MoS2 doesn’t show much
deviation from a linear response even at a more than
two orders of magnitude higher excitation intensity, ∼80
μW/μm2 .
We also perform PL measurements by using femtosec-
ond pulse excitation, and the resulting integrated PL
from monolayer MoSe2 is plotted in Fig. 2(b) as a func-
tion of the excitation pulse’s fluence. The integrated PL
saturates much faster than it does in CW excitation case
at the same laser power. Because the exciton density is
very high for pulse excitation case, especially just after
excitation, the excitons will decay mostly through EEA.
Photoluminescence Saturation and Exciton Decay Dynamics · · · – Min Ju Shin et al.
Fig. 2. (Color online) PL intensity vs. excitation inten-
sity graphs for monolayer MoS2 on 280-nm-thick SiO2 /Si (red
solid circles) and 70-nm-thick Al2 O3 /Si (open black circles),
and for monolayer MoSe2 on 280-nm-thick SiO2 /Si (blue solid
circles).
In this region, the integrated PL increases as ln(N0 ) as
the injected exciton density N0 is increased. If no ap-
preciable saturation of absorption is asuumed, the inte-
grated PL then has a functional form of ln(F) for a pulse
fluence F. We can see that the PL saturation in the high
fluence region can be fitted well by using this functional
form, supporting again the presence of a strong EEA
mechanism in monolayer MoSe2 .
To understand the physics underlying the dramatically
different PL saturation in monolayer TMDs, we per-
form degenerate transient reflection spectroscopy mea-
surements on monolayer MoSe2 and study its exciton
dynamics in the time domain. Figure 3 displays a typical
differential reflection (DR) signal for monolayer MoSe2
measured by using degenerate pump-probe spectroscopy
at a wavelength of 780 nm. During the overlap of the
pump and the probe pulses, a strong coherent artifact
signal shows up, making it hard to observe the build-up
process of excitons. Still, we can ignore the exciton de-
cay during the pump-probe overlap because the exciton
lifetime is much longer than the pulse duration. In the
inset of Fig. 3, the maximum DR signal is plotted as a
function of pump fluence. The plotted maximum DR is
not a linear function of the pump fluence. We should
point out that although the absorption may seem to be
saturated, it is not. The maximum DR signal of the
probe is less than 1%, so the change in the absorption
during the pump excitation should be small, too. There-
fore, the nonlinear dependence of the DR signal should
be related to other causes, such as bandgap renormal-
ization and/or a pump-heating induced A-exciton peak
shift. Irrespective of its origin, we can exclude saturation
of absorption and safely assume that the injected exciton
density is proportional to the pump fluence.
After pump excitation, the DR signal relaxes rapidly
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Fig. 3. (Color online) (a) PL intensity vs. excitation in-
tensity of monolayer MoSe2 . The red line is a fitting result.
(b) Integrated PL vs. excitation pulse fluence of monolayer
MoSe2 . The red line is a fitting result. The excitation is
made using a CW and a mode-locked 760-nm beam from a
Ti:sapphire oscillator.
at first and then slows down as the probe delay is in-
creased, as expected from the density-dependent EEA
rate. This is different from monolayer MoS2 , where
only a multi-exponential, linear exciton decay process
has been reported. If EEA dominates over linear exciton
decay, the linear exciton decay term in Eq. (1) can be
ignored, and the exciton density then evolves with time
as follows [21]:
N0
− 1 = γN0 t, (2)
N (t)
Equation (2) indicates that if EEA dominates over lin-
ear exciton decay, the slope of the NN(t)
0
− 1 graph should
be proportional to the injected exciton density and, thus,
to the pump fluence. In a linear exciton decay process,
however, the slope is given by the inverse of the life-
time time, τ −1 , which has no direct correlation with
the pump fluence. In Fig. 4(a), NN(t) 0
− 1 is plotted as
-2080- Journal of the Korean Physical Society, Vol. 65, No. 12, December 2014

Fig. 4. Differential reflection of monolayer MoSe2 . The

center wavelength of the pump and the probe is 780 nm and
the pump fluence is 53 μJ/cm2 . (Inset) Maximum DR as a
function of the excitation fluence.

a function of the probe delay for several pump fluencies.

Clearly, the slope of the graphs increases as the pump
fluence is increased, supporting a strong EEA in mono-
layer MoSe2 . A similar density-dependent decay rate has
been reported in a previous report [21]. The slope, how-
ever, is not exactly proportional to the injected exciton
density. This deviation may be explained by the resid-
ual linear decay term. Although the linear exciton decay
term is ignored in Eq. (2), it always contributes to the
total excition decay rate. This is increasingly so as the
pump fluence is decreased. It adds an additional slope
to Eq. (2) and causes the total slope to deviate from the
linear dependence, especially at low pump fluences.
When the exciton density is low, its linear decay can
dominate over the nonlinear EEA. This condition is met
at ‘low pump fluence’ and ‘long delay time’. We can thus
extract the exciton lifetime, or its lower limit because
EEA always co-exists, by fitting the long-delay part of
the DR data pumped at a low fluence. Figure 4(b) dis-
plays the DR signal measured at the lowest excitation
fluence, ∼5.3 J/cm2 , together with a single-exponential
fitting result as a red line (fitting region: delay > 50 ps).
The exciton lifetime obtained is around ∼125 ps. This is
more than an order of magnitude longer than the exciton
lifetime of monolayer MoS2 , which has been reported to
be several picoseconds [18, 19]. Why their exciton life-
times are so different is not clear. A 2D TMD mono-
layer has a more complicated structure than graphene
and, thus, has much more various point defects and dis-
location cores [22]. One possible reason may be that S-
related point defects such as vacancies are formed more
easily in MoS2 than Se-related defects in MoSe2 during
mechanical exfoliation.
Our work shows that the PL saturation behavior and
the exciton decay mechanism can change from one TMD
to another. Here, we will discuss the physics underly-
Fig. 5. (Color online) (a) Plot of NN(t)
0
− 1 vs. probe delay
for pump fluencies of 105, 53, 26 μJ/cm2 (from top to bot-
tom). The DR is assumed to be proportional to the exciton
density. The red lines are linear fits to the initial part (0 ∼ 40
ps delay) of the graphs. (b) Exponential fitting to the latter
part (50 − 300 ps) of DR at a pump fluence of ∼5.3 μJ/cm2 .
ing this dramatic change. The relative magnitude of the
nonlinear EEA compared to the linear exciton decay is
Nγτ /2. At a given exciton density, the longer the exci-
ton lifetime or the larger the EEA coefficient is, the more
significant the EEA becomes. As can be seen in the tran-
sient reflection for monolayer MoSe2 , the exciton-exciton
interaction is strong in 2-D TMDs. However, the EEA
coefficients of MoS2 and MoSe2 monolayers should be of
the same order, because the exciton binding energies and,
thus, the exciton radii are similar. Therefore, this does
not explain the difference in the decay mechanism. On
the other hand, the measured exciton lifetime of mono-
layer MoSe2 is more than an order of magnitude longer
than that of monolayer MoS2 . Therefore, the linear de-
cay rate is much smaller in monolayer MoSe2 than in
monolayer MoSe2 , leaving EEA as the dominant decay
mechanism.
The dramatically different PL saturation behaviors
can be explained also by the exciton lifetime. The
Photoluminescence Saturation and Exciton Decay Dynamics · · · – Min Ju Shin et al.
crossover excitation intensity from EEA to linear exci-
E J. Li, J. C. Grossman and J. Wu, Nano Lett. 12, 5576
ton decay scales as I0 = 2τ 2pa . The absorbance a is re-
ported to be around ∼0.05 for both MoS2 and MoSe2
monolayers [23]. Therefore, the main difference is the
exciton lifetime τ . Because I0 is proportional to τ −2 ,
the longer exciton lifetime in monolayer MoSe2 causes a
crossover from linear to nonlinear exciton decay to occur
at a more-than two orders of magnitude lower excitation
intensity than in monolayer MoS2 , as observed in our
experiment.
IV. CONCLUSION
We study the exciton decay dynamics in monolayer
TMDs. We observe a highly nonlinear PL response in
monolayer MoSe2 , in contrast to the almost linear one in
monolayer MoS2 . Transient differential reflection shows
that the exciton decay in monolayer MoSe2 is dominated
by exciton-exciton annihilation, in contrast to the linear
exciton decay in monolayer MoS2 . We find that the dif-
ferences in the exciton decay mechanism and the PL sat-
uration behavior in monolayer TMDs can be explained
in terms their different exciton lifetimes.
ACKNOWLEDGMENTS
This work was supported by grants from the Kyung
Hee University Research Fund (KHU- 20110464).
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