ARTICLE

Received 10 Oct 2012 | Accepted 15 Jan 2013 | Published 12 Feb 2013 DOI: 10.1038/ncomms2498

Electrical control of neutral and charged excitons

in a monolayer semiconductor
Jason S. Ross1,*, Sanfeng Wu2,*, Hongyi Yu3, Nirmal J. Ghimire4,5, Aaron M. Jones2, Grant Aivazian2,
Jiaqiang Yan5,6, David G. Mandrus4,5,6, Di Xiao7, Wang Yao3 & Xiaodong Xu1,2

Monolayer group-VI transition metal dichalcogenides have recently emerged as

semiconducting alternatives to graphene in which the true two-dimensionality is expected to
illuminate new semiconducting physics. Here we investigate excitons and trions (their singly
charged counterparts), which have thus far been challenging to generate and control in the
ultimate two-dimensional limit. Utilizing high-quality monolayer molybdenum diselenide, we
report the unambiguous observation and electrostatic tunability of charging effects in
positively charged (X þ ), neutral (Xo) and negatively charged (X  ) excitons in field-effect
transistors via photoluminescence. The trion charging energy is large (30 meV), enhanced by
strong confinement and heavy effective masses, whereas the linewidth is narrow (5 meV)
at temperatures o55 K. This is greater spectral contrast than in any known quasi-
two-dimensional system. We also find the charging energies for X þ and X  to be nearly
identical implying the same effective mass for electrons and holes.

1 Department of Material Science and Engineering, University of Washington, Seattle, Washington 98195, USA. 2 Department of Physics, University of
Washington, Seattle, Washington 98195, USA. 3 Department of Physics and Center of Theoretical and Computational Physics, University of Hong Kong,
Hong Kong, China. 4 Department of Physics and Astronomy, University of Tennessee, Knoxville, Tennessee 37996, USA. 5 Materials Science and Technology
Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA. 6 Department of Materials Science and Engineering, University of Tennessee,
Knoxville, Tennessee 37996, USA. 7 Department of Physics, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, USA. *These authors contributed
equally to this work. Correspondence and requests for materials should be addressed to X.X. (e-mail: [email protected]).

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ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms2498

valley polarization13–15 and electrical control of Berry phase

A
bove bandgap photo-excitation creates electrons and holes
in the conduction and valence bands, respectively. If the properties16.
screening is weak enough, the attractive Coulomb Using a back-gated field-effect transistor (FET) device,
interaction between one electron and one hole creates a bound we demonstrate the reversible electrostatic tunability of the
quasi-particle known as a neutral exciton (Xo), which has an exciton charging effects from positive (X þ ) to neutral (Xo) and to
energy structure similar to a neutral hydrogen atom. Excitons can negative (X  ). We observe a large trion-binding energy of
further become charged by binding an additional electron (X  ) 30 meV with a narrow emission linewidth of 5 meV. These
or hole (X þ ) to form charged three-body excitons analogous to narrow, well-separated features have temperature dependence of
H  or H2þ respectively1–3. These exciton species are elementary typical 2D excitons and exist at high temperature suggesting
quasi-particles describing the electronic response to optical remarkable stability. Interestingly, the binding energies of X þ
excitation in solids and are integral to many optoelectronic and X  are similar implying that low-energy electrons and holes
applications from solar cells and light-emitting diodes4 to optical in MoSe2 have the same effective mass. Our work demonstrates
interconnects5 and quantum logical devices6,7. that monolayer MoSe2 is a true 2D semiconductor opening the
The main arena for the exploration of excitonic physics has door for the investigation of phenomena such as exciton
been three-dimensional semiconductors and their heterostruc- condensation17–19 and the Fermi-edge singularity20,21, as
tures that form quasi-2D quantum wells where the carrier well as for a new generation of optoelectronic devices such as
wavefunction typically occupies a few tens to thousands of atomic light-emitting diodes and excitonic circuits5.
layers. Observation and control of excitons in truly 2D systems
has been a long pursued goal, largely motivated by the
enhancement in exciton- and trion-binding energies in the strict Results
2D limit8. In addition, unlike semiconductor heterostructures, the Crystal structure and spectral features of monolayer MoSe2. In
close proximity of external stimuli to the exciton wavefunction monolayer MoSe2, Mo and Se atoms form a 2D hexagonal lattice
can offer unprecedented tunability and diversifies the applications with trigonal prismatic coordination (Fig. 1a). First-principles
possible in devices made with 2D semiconductors. calculations show that it has a direct bandgap at the corners (K
Here we report the experimental observation and control of the points) of the first Brillouin zone (Fig. 1b). The curvature of the
fascinating excitonic physics in a 2D semiconductor by utilizing bands suggests comparable effective mass for low-energy elec-
high-quality monolayer molybdenum diselenide (MoSe2). MoSe2 trons and holes at K points (Fig. 1c)9. These band-edge electrons
belongs to the group-VI transition metal dichalcogenides, which and holes near K points are predominantly from the d-orbitals of
form in layers weakly bound to each other by Van der Mo atoms. Their wavefunctions are calculated to be strongly
Waals forces. The monolayers have received much attention confined in the Mo layer within a length scale of B0.2 nm in
recently as they make up a new class of 2D semiconductors with a the out-of-plane direction. Monolayer MoSe2 is thus an ideal
direct bandgap in the visible frequency range and are predicted nanomaterial for exploring excitonic physics in the ultimate
to exhibit coupled spin-valley physics9. Recent progresses focus 2D limit.
on MoS2, including the demonstration of having a direct We use mechanical exfoliation to obtain monolayer MoSe2 on
bandgap10,11, high mobility electronics12, optical generation of 300 nm SiO2 on nþ -doped Si and atomic force microscope to

4
Mo Se
Energy (eV)

0 180 meV

–2
Γ K M Γ

2
Thickness (nm)

7Å
S D
0
SiO2
0 2 4 6 8 10 n+ Si Vg
Distance (μm)

Figure 1 | MoSe2 characteristics and devices. (a) Coordination structure and top view of monolayer MoSe2. (b) Density function theory calculated band
structure. (c) Band structure at K point shows 180 meV valence band splitting due to spin–orbit coupling. (d) Optical micrograph of exfoliated MoSe2 flake
on 300 nm SiO2. Scale bar, 5 mm. (e) atomic force microscope (AFM) image of area highlighted in (d). Scale bar, 1 mm. (f) AFM line scan along dashed line
in e. (g) Optical micrograph of MoSe2 device. Scale bar, 5 mm. (h) Schematic of back-gated MoSe2 device.

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NATURE COMMUNICATIONS | DOI: 10.1038/ncomms2498 ARTICLE

identify the layer thickness22. Figure 1d,e show the optical Energy (eV)
micrograph and the corresponding atomic force microscope 1.50 1.75 2.00 2.25
image of a representative sample, in which the monolayer 0.6
thickness of B0.7 nm is identified12 (Fig. 1f). Standard electron
beam lithography (EBL) is used to fabricate monolayer 0.4 B
FETs (Fig. 1g). With the contacts simply grounded, the nþ Si
functions as a back gate providing uniform electrostatic doping in

ΔR/R
0.2 A
the MoSe2 (Fig. 1h).
The excitonic features of MoSe2 are investigated by differential
reflectance and micro photoluminescence (PL) measurements 0.0
(Methods). Figure 2 shows the results from an unpatterned
MoSe2 sample, S1. At 20 K, we observe two main features –0.2
associated with the A and B excitons in the differential reflection
7.5
spectrum10,11,14,23–25 (Fig. 2a). The presence of A and B excitons 30 meV

PL (a.u.)
has been attributed to spin–orbit coupling-induced valence band 6.0
splitting in bulk24. The observed energy difference of B200 meV

(103 counts)
PL intensity
X– Xo
agrees well with the calculated splitting (180 meV) in monolayers 4.5
(Fig. 1c).
With the same sample and temperature under 2.33 eV laser 3.0
excitation, the PL spectrum does not show a measurable feature 1.60 1.64 1.68
that can be attributed to the B exciton, likely because it is not the 1.5 Energy (eV)
lowest energy transition. Instead, we observe two pronounced
peaks at 1.659 and 1.627 eV in the vicinity of the A exciton 0.0
1.50 1.75 2.00 2.25
(Fig. 2b). Note that the PL spectrum lacks the broad low-energy
peak observed in MoS2, which has been attributed to defect- Energy (eV)
related, trapped exciton states10,11,14,25. Figure 2 | Differential reflectance and PL spectra of monolayer MoSe2 at
The striking spectral features demonstrate the high quality of 20 K. (a) Differential reflectance shows A and B excitons. (b) PL excited
our MoSe2 samples (Methods) and provide strong evidence for by 2.33 eV laser shows neutral exciton (Xo) and the lower-energy charged
monolayer MoSe2 being a direct bandgap semiconductor exciton (X  ). PL from the B exciton has not been observed. Inset, PL of the
(Supplementary Fig. S1) where the two distinct transitions are exciton peaks. The X  shows a binding energy of about 30 meV.
excitons. The higher-energy emission at 1.659 eV is the neutral
exciton, Xo, and the lower-energy peak is a trion3. In unpatterned
samples, we assume the trion to be X  because all measured is within 1.5 meV over the whole applied Vg range. Because the
devices show n-doped characteristics (Supplementary Fig. S2). All binding energy of a trion is dependent on its effective mass, this
measured unpatterned samples show a binding energy, which is observation implies that the electron and hole have approximately
the energy difference between trion and Xo, of B30 meV (Fig. 2b, the same effective mass.
inset). This is more than twice the typical numbers reported The gate-dependent measurements unambiguously demon-
in GaAs quantum wells3,26,27 and similar to a recent mention strate the electrical control of exciton species in a truly 2D
in MoS214. semiconductor, as illustrated in Fig. 3b. The conversion from Xo
to trion can be represented as e(h) þ Xo-X  (X þ ), where e and
h represent an electron or a hole, respectively. By setting Vg to be
Gate dependence of MoSe2 PL. To confirm the above assignment negative, the sample is p-doped, favouring excitons to form
and control the exciton charging effects, we performed gate- lower-energy-bound complexes with free holes. As Vg decreases,
dependent PL measurements using monolayer MoSe2 FETs. more holes are injected into the sample, and all Xo turn into X þ
Here the excitation laser is at 1.73 eV for better resonance with to form a positively charged hole-trion gas. With positive Vg, a
the luminescent states. Figure 3a shows a colour map of the PL similar situation occurs with free electrons to form an electron-
spectrum of device D1 at 30 K as a function of back-gate voltage, trion gas. In the following, we show that a standard mass action
Vg, in which we clearly observe four spectral features whose model can be used to describe the conversion dynamics.
intensities strongly depend on Vg. Near zero Vg, the spectrum Figure 3c shows the extracted Xo (black) and trion (red) peak
shows a broad low-energy feature around 1.57 eV and a narrow intensity as a function of Vg where we have adjusted the negative
high-energy peak at 1.647 eV. With large Vg of either sign, Vg data due to background signal. The plot shows that the
these peaks disappear and a single-emission peak dominates the maximum Xo intensity is about equal to the saturated trion PL
spectrum. Both peaks (at negative or positive Vg) have similar when Xo vanishes. This observation indicates conservation of the
energies and intensities with the latter increasing with the total number of Xo and trion in the applied voltage range and
magnitude of Vg. similar radiative decay rates for both quasi-particles. Thus, the PL
This observed gate dependence confirms the assignment of intensity represents the amount of the corresponding exciton
states as labelled in Fig. 3a. Because the broad low-energy peak species. Because the dynamic equilibrium of free electrons, holes
does not show up in unpatterned samples before FET fabrication, and excitons are governed by the rate equation and law of mass
we attribute it to exciton states trapped to impurities action27, we calculate the gate-dependent Xo and trion abundance
(XI)10,11,14,25, which are likely introduced during EBL processing (Supplementary Fig. S3), shown by the solid lines in Fig. 3c,
and are not the focus of this paper. The sharp peak at 1.647 eV is which agrees with the data.
the Xo, slightly red-shifted compared with unpatterned samples. In the simulation, we first fit the Xo curve to obtain our two
From the gate dependence, we identify the peaks near 1.627 eV as free parameters: the maximum background electron
the X  and X þ trions when Vg is largely positive and negative, concentration nmaxB ¼ 3:610 cm
10 2
when the trion intensity
respectively. Remarkably, these two distinct quasi-particles (X þ saturates and the photo-excited electron concentration
and X  ) exhibit a nearly identical binding energy. The difference np ¼ 1.5  1010cm  2. We then fit the trion gate dependence

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ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms2498

Vg
1.67 Xo 200 p n
150 h e
e e
100
h h e h X+ Xo X–

Energy (eV)
50 150

PL intensity (counts)
X+ X– 0
1.6
100
XI

X+ Xo X– 50

1.53 0
–60 –30 0 30 60 –60 –30 0 30 60
Vg (V) Vg (V)

Figure 3 | Electrostatic control of exciton charge. (a) MoSe2 PL (colour scale in counts) is plotted as a function of back-gate voltage. Near zero doping, we
observe mostly neutral and impurity-trapped excitons. With large electron (hole) doping, negatively (positively) charged excitons dominate the spectrum.
(b) Illustration of the gate-dependent trion and exciton quasi-particles and transitions. (c) Trion and exciton peak intensity versus gate voltage at dashed
arrows in (a). Solid lines are fits based on the mass action model.

T(K):

Peak position (eV)

295 1.64
270 10,000
PL (counts)

250
230
210 1.60
190 5,000
170
150
130 1.56
Normalized PL (a.u.)

120 0
110
100 1.62 1.64 1.66 0 50 100 150 200 250 300
90
80
70
65 12,000
60 2
55
Area ratio (X–/Xo)
50
PL (counts)

45 8,000
40
35 1
30
25 4,000
20
15
0
0
1.52 1.56 1.60 1.64 1.68 1.72 1.62 1.65 1.68 0 50 100 150
Energy (eV) Energy (eV) Temperature (K)

Figure 4 | Temperature dependence of PL spectrum. (a) Normalized PL of monolayer MoSe2 versus temperature. (b) Line shape fitting at 15 K. Black is
data. Red and blue curves are fits with and without considering the electron-recoil effect, respectively. (c) Data and fit at 70 K using two symmetric peaks.
(d) Neutral exciton (black) and trion (red) peak position versus temperature with fits (solid lines). (e) Integrated area ratio of trion:exciton versus
temperature with mass action model fitting (red).

with these parameters held fixed (Supplementary Note 1). The energy of 30 meV. As the temperature rises, we see the X  signal
deviation in the trion experimental data from the calculated curve drop significantly at about 55 K, which we attribute to electrons
near zero Vg is artificial due to the mutual background from Xo escaping their bound trion state due to thermal fluctuations
and XI. We note that this inferred electron concentration is much (Supplementary Note 1).
smaller than the product of the gate capacitance and Vg. This Figure 4b is the zoom-in plot at 15 K where we observe slightly
discrepancy can be attributed to the large contact resistance different line shapes for X  and Xo. The Xo peak is symmetric
(Supplementary Fig. S4) of the sample, which prevents the carrier showing homogenous thermal broadening effects and is well fit
concentration from reaching equilibrium on the experimental by a hyperbolic secant function that yields a full-width half-
time scale at 30 K. We expect that future improved contact maximum of 5 meV27,28. However, the X  peak shows a slightly
technologies will eliminate this effect. asymmetric profile with a long low-energy tail consistent
with electron-recoil effects27. The recombination of a X  with
momentum k will emit a photon and leave a free electron with the
Temperature dependence of MoSe2 PL. The observed exciton same momentum k due to momentum conservation. From
states also show fine features consistent with 2D excitons, such as energy conservation, the emitted photon has an energy
hk2 MXo
temperature-dependent line shape, peak energy and relative ho ¼ 
 hoo  2m hoo is the energy of trions with
2 M  , where 
X
weight of Xo and trion, which further supports the excitonic k ¼ 0, and MXo and MX  are the Xo and X  effective masses,
e

nature of this monolayer system (Fig. 4). Figure 4a shows the respectively. The line shape of trion PL will thus be the
evolution of X  and Xo (normalized PL) as a function of tem- convolution of a symmetric peak function (hyperbolic secant)
perature in an unpatterned sample, S2, under 1.96 eV laser and an exponential low-energy tail function (Supplementary Fig.
excitation. At low temperatures, we again observe a binding S5 and Supplementary Note 2). When the temperature is 470 K,

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NATURE COMMUNICATIONS | DOI: 10.1038/ncomms2498 ARTICLE

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measurements, an Ocean Optics tungsten halogen white light source is reflected
into a  40 ultra-long working distance objective using a neutral density,
achromatic beam splitter and then focused on the sample (B2 mm spot size). The Acknowledgements
reflected signal from the sample is collected by the objective and sent back through We thank David Cobden and Ming Gong for their helpful discussions. This work is
the beam splitter into the spectrometer. For PL measurements, a similar setup is mainly supported by the US DoE, BES, Materials Sciences and Engineering Division
used, except the neutral density beam splitter is replaced by a dichroic beam splitter (DE-SC0008145). H.Y. and W.Y. were supported by Research Grant Council of
appropriate for the laser wavelength and a laser line notch filter is inserted before Hong Kong (HKU706412P). N.J.G., J.Y., D.G.M. and D.X. were supported by the US
the spectrometer. DoE, BES, Materials Sciences and Engineering Division. Device fabrication was

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performed at the University of Washington Microfabrication Facility and NSF-funded Additional information
Nanotech User Facility. Supplementary Information accompanies this paper at http://www.nature.com/
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Author contribution Competing financial interests: The authors declare no competing financial interests.
X.X. conceived the experiments. J.S.R. fabricated the devices and performed the Reprints and permission information is available online at http://npg.nature.com/
measurements, assisted by S.W., A.M.J. and G.A. S.W., J.S.R. and X.X. performed data reprintsandpermissions/
analysis. H.Y., W.Y. and D.X. contributed to the theoretical explanation. N.G., J.Y. and
D.G.M. synthesized and performed bulk characterization measurements on the How to cite this article: Ross, J.S. et al. Electrical control of neutral and charged excitons
MoSe2 crystals. All authors discussed the results and contributed to writing the manuscript. in a monolayer semiconductor. Nat. Commun. 4:1474 doi: 10.1038/ncomms2498 (2013).

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