LETTERS

PUBLISHED ONLINE: 2 DECEMBER 2012 | DOI: 10.1038/NMAT3505

Tightly bound trions in monolayer MoS2

Kin Fai Mak1 , Keliang He2 , Changgu Lee3 , Gwan Hyoung Lee4 , James Hone4 , Tony F. Heinz1
and Jie Shan2 *

Two-dimensional (2D) atomic crystals, such as graphene and photoluminescence spectroscopy. In our investigations we have
transition-metal dichalcogenides, have emerged as a new class made use of MoS2 monolayers prepared by mechanical exfoliation.
of materials with remarkable physical properties1 . In contrast Field-effect transistors (FETs) using MoS2 were fabricated on
to graphene, monolayer MoS2 is a non-centrosymmetric mate- SiO2 /Si substrates; the doping density in the MoS2 channel was
rial with a direct energy gap2–5 . Strong photoluminescence2,3 , a systematically varied by applying a voltage to the Si back gate. All
current on/off ratio exceeding 108 in field-effect transistors6 , measurements were performed at 10 K, if not otherwise specified.
and efficient valley and spin control by optical helicity7–9 have The typical variation of the drain–source current (Ids ) with the
recently been demonstrated in this material. Here we report the gate voltage (Vg ) is shown in the inset of Fig. 1d. The response
spectroscopic identification in a monolayer MoS2 field-effect is characteristic of a FET with an n-type channel. Spontaneous
transistor of tightly bound negative trions, a quasiparticle negative doping, presumably from defects within the MoS2 layer
composed of two electrons and a hole. These quasiparticles, and/or substrate interactions, has been commonly reported in
which can be optically created with valley and spin polarized mechanically exfoliated MoS2 (refs 6,19). Over the accessible range
holes, have no analogue in conventional semiconductors. They of the gate voltage (−100 to +80 V) our MoS2 FETs exhibit electron
also possess a large binding energy (∼20 meV), rendering doping. The low off-state current at high negative gate voltages is
them significant even at room temperature. Our results open understood to reflect electron localization in 2D (ref. 15) and/or a
up possibilities both for fundamental studies of many-body in- channel-contact barrier.
teractions and for optoelectronic and valleytronic applications The absorption spectrum of monolayer MoS2 at a gate voltage of
in 2D atomic crystals. −100 V (Fig. 1d) corresponds to that of a nearly undoped sample.
The trion binding energy that we observe in monolayer MoS2 is It shows pronounced absorption peaks from excitonic transitions,
nearly an order of magnitude larger than that found in conventional rather than the steps that would be expected for absorption
quasi-2D systems, such as semiconductor quantum wells10–13 . This arising from band-to-band transitions in 2D. The two features,
is a consequence of the greatly enhanced Coulomb interactions known as the A (∼1.92 eV) and B (∼2.08 eV) excitons2,3,20 , are
in monolayer MoS2 , arising from reduced dielectric screening associated with direct optical transitions from the highest spin-split
in gapped 2D crystals and the relatively heavy particle band valence bands to the lowest conduction bands. These transitions
masses associated with the Mo d-manifolds4,5,14 . For an electron are significantly modified by strong Coulomb interactions between
density as high as n = 1011 cm−2 , for instance, the dimensionless the photogenerated electron–hole pairs and the corresponding
interaction parameter rs is ∼60 in monolayer MoS2 (Supplementary formation of bound excitons.
Section S1). This value is significantly larger than that for carriers in In our investigation of the optical response of MoS2 in the
quantum wells even at very low doping levels15 . Monolayer MoS2 presence of a 2D electron gas (2DEG), we focus on the behaviour
is a strongly interacting system even in the presence of relatively of the low-energy (A) exciton over the spectral range of 1.8–2.0 eV.
high carrier densities; it thus presents an ideal laboratory for Figure 2a (red lines) shows representative absorption spectra of
exploring many-body phenomena, such as carrier multiplication a monolayer MoS2 FET under gate voltages from −100 to 80 V,
and Wigner crystallization16 . corresponding to approximate charge neutrality to a doping density
The atomic structure of MoS2 consists of hexagonal planes of S of ∼ 1013 cm−2 . We see an overall suppression of the optical
and Mo atoms in a trigonal prismatic structure (Fig. 1a; ref. 17). absorbance in this spectral region with increasing electron doping.
The two sublattices of the hexagonal MoS2 structure are occupied, The prominent A exciton peak evolves into two resonances,
respectively, by one Mo and two S atoms (Fig. 1b). Monolayer MoS2 with the emergence of a lower energy resonance (labelled as
is a direct gap semiconductor with energy gaps located at the K and A− ). For Vg > 0, the absorbance of feature A diminishes rapidly
K0 points of the Brillouin zone (Fig. 1c). Both the highest valence and disappears into the background. The A− feature, on the
bands and the lowest conduction bands are formed primarily from other hand, broadens gradually, while approximately preserving
the Mo d-orbitals4,17 . The large spin–orbit interaction splits the its spectral weight. Similarly, in the photoluminescence spectra
highest valence bands at the K (K0 ) point by ∼160 meV (refs 2,3,7). (Fig. 2a), both resonances can be identified for negative gate
The valley and spin degrees are coupled because of the lack of voltages. The photoluminescence intensity of the A exciton, like its
inversion symmetry in monolayer MoS2 (ref. 18). As has been absorbance, can be switched off by doping. In addition, redshifts
recently shown experimentally, this allows optical pumping of a in the photoluminescence peak energies from the corresponding
single valley (and spin) with circularly polarized light7–9 . absorption energies (Stokes shifts) are observed for both features;
Here we investigate the optical response of monolayer MoS2 the magnitude of Stokes shift is found to increase with doping level
as a function of carrier density by means of absorption and (Supplementary Fig. S1b).

1 Departments of Physics and Electrical Engineering, Columbia University, 538 West 120th Street, New York 10027, USA, 2 Department of Physics, Case
Western Reserve University, 10900 Euclid Avenue, Cleveland, Ohio 44106, USA, 3 SKKU Advanced Institute of Nanotechnology (SAINT) and Department
of Mechanical Engineering, Sungkyunkwan University, Suwon 440-746, Korea, 4 Department of Mechanical Engineering, Columbia University, New York
10027, USA. *e-mail: [email protected].

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LETTERS NATURE MATERIALS DOI: 10.1038/NMAT3505

a b d
A
S 0.08 400
Mo B
300

Current (nA)
S 0.06
200

Absorbance
c 100
0.04
mj = ¬3/2 +3/2 0
mj = ¬1/2 +1/2
¬80 ¬40 0 40 80
0.02 Gate voltage (V)
mj = ¬1/2 +1/2
mj = +1/2 ¬1/2

0.00
K K' 1.6 1.7 1.8 1.9 2.0 2.1 2.2
Photon energy (eV)

Figure 1 | Atomic structure, electronic band structure, and absorption spectrum of monolayer MoS2 . a, Representation of the trigonal prismatic structure
of monolayer MoS2 . b, Honeycomb lattice structure with each sublattice occupied by a Mo and two S atoms. c, The lowest-energy conduction bands and
the highest-energy valence bands labelled by the z-component of their total angular momentum near the K and K0 point of the Brillouin zone. The spin
degeneracy at the valence-band edges is lifted by spin–orbit interactions. The valley and spin degrees of freedom are coupled. Under left-circularly
polarized excitation, only the K-valley is populated, whereas under right-circularly polarized excitation, only the K0 -valley is populated. d, Absorption
spectrum of undoped monolayer MoS2 with two prominent resonances, known as the A and B excitons. The inset shows the drain–source current Ids ,
under a Vds = 40 mV bias voltage, as a function of back-gate voltage Vg . It is characteristic of an n-doped semiconductor that can be turned off at large
negative gate voltages.

a 0.08 A¬ b Gate voltage (V)

¬80 V
A 0.02 ¬100 ¬80 ¬60 ¬40 ¬20 0 20 40 60 80
0.04 1.96
ω A¬
0.00 ωA
0.08
¬60 V A
Resonance energy (eV)

0.02 1.94
0.04 A¬

0.00 1.92
0.08
Photoluminescence intensity (a.u.)

¬40 V
0.02
0.04
1.90
0.00
0.08
Absorbance

¬20 V 0.02
0.04

0.00 c 60
0.08
0V
0.02
0.04 50
ω A ¬ ω A¬ (meV)

0.00 EF
0.08 40
30 V e¬ e¬
Trion A¬
0.02
0.04 30 h+

0.00 20 EF
0.08 e¬
70 V Experiment Exciton A
0.02
0.04 10 Linear fit h+

0.00 0.00 0
1.8 1.9 2.0 1.9 2.0 0 10 20 30 40 50
Photon energy (eV) Fermi energy (meV)

Figure 2 | Doping dependence of the optical properties of a monolayer MoS2 FET. a, Absorption and photoluminescence spectra (red lines) in the range
of 1.8–2.0 eV for the indicated back-gate voltages. The exciton (A) and trion (A− ) resonances behave differently with gate voltage. Left: Absorption
spectra, with the dashed blue lines as a guide to the eye for the threshold energies of A and A− features. The green lines are power-law fits to the
experimental results, as described in the main text, with the A and A− components shown as the blue lines. Right: The photoluminescence spectra of the A
and A− features are fit to Lorentzians (green lines). The dashed blue line indicates the absorption peak of the A− resonance and the arrows show the
doping-dependent Stokes shift of the trion photoluminescence. b, Threshold energies of the trion ωA− (black symbols) and the neutral exciton ωA (red
symbols), determined from the absorption spectra, as a function of gate voltage (upper axis) and Fermi energy EF (lower axis). c, The difference in the
exciton and trion energies, ωA − ωA− (symbols), as a function of Fermi energy EF . The red line, a linear fit to the EF -dependence, has a slope of 1.2 and an
intercept of 18 meV. The latter determines the trion binding energy. Inset: representation of the dissociation of a trion into an exciton and an electron at the
Fermi level.

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NATURE MATERIALS DOI: 10.1038/NMAT3505 LETTERS
a
¬70 V
0.08 ¬40 V c 140
A exciton
¬10 V A¬ exciton
10 V Total 200
0.06 30 V
120 Ids ¬ Vg
Absorbance

50 V
80 V
0.04
100

Photoluminescence intensity (a.u.)

150
0.02
80

Current (nA)
0.00
1.7 1.8 1.9 2.0 2.1 2.2
Photon energy (eV) 60 100

b
1,400 A
Photoluminescence intensity (a.u.)

40
1,200

1,000 50

20
800

600
A¬ 0
400 0
200
–100 –80 –60 –40 –20 0 20 40 60 80 100
0 Gate voltage (V)
1.7 1.8 1.9 2.0 2.1 2.2
Photon energy (eV)

Figure 3 | Excitons and trions at room temperature in monolayer MoS2 . a,b, Absorption and photoluminescence spectra at different back-gate voltages.
Both the neutral exciton (A) and trion (A− ) features (with the corresponding resonance energies indicated by the dashed lines) can be identified, although
the resonances are significantly broadened. c, Dependence on gate voltage of the drain–source current (right) and the integrated photoluminescence
intensity of the A and A− features and their total contribution (left).

What is the origin of the A− resonance? Our observation cannot from the gate dependence of the photoluminescence Stokes shift21,25
be explained by a simple state-blocking effect. Although such Pauli (Supplementary Section S2).
blocking can account for the overall reduction in absorption with When the Fermi energy is varied from ∼0 to 30 meV, the exciton
doping21 , it cannot explain the appearance of two resonances with energy blue-shifts monotonically, whereas the trion energy remains
different doping dependences. Nor can the emergence of two largely unchanged, after a slight initial redshift (Fig. 2b). These
features be explained by an electric-field-induced band structure dependences arise from the combined effects of Pauli blocking and
modification. In the absence of magnetic fields, the valley and spin many-body interactions25,26 , and are consistent with the previous
degeneracy of the bands is protected and no available degeneracy theoretical results (Supplementary Section S3) and experimental
can be lifted to give rise to two distinct resonances. The observed studies on quantum wells (refs 10–13). The splitting between the
A− feature, however, can be understood as arising from trions. Such exciton and trion energy is predicted to be linearly dependent on
bound states of two electrons to a hole, that is, negatively charged the Fermi energy and obey11
excitons, are known to have finite binding energies10,11,22,23 . In our
experiment at low temperature, the optical response of monolayer
MoS2 is dominated by neutral excitons in undoped samples. Trions ωA − ωA− = EA− + EF (1)
emerge, accompanied by a reduction of exciton absorption and
photoluminescence, when excess electrons are introduced to bind where EA− is the trion binding energy. Because the exciton can be
to photoexcited electron–hole pairs. The exciton spectral weight is considered as an ionized trion, ωA − ωA− defines the minimum
transferred to the trion, as shown in our experiment. The detailed energy for the removal of one electron from the trion. In the
dependence on doping density of this phenomenon in the relatively limit of infinitesimal doping, it is just the trion binding energy
low doping regime is often governed by electron localization in EA− , the energy required to promote one of the electrons in a
inhomogeneous samples. trion to the conduction band edge. At finite doping densities,
We have analysed the absorption spectra to determine the an exciton is obtained by dissociation of a trion and placing
energies to create both neutral excitons (ωA ) and trions (ωA− ) as the extra electron at the Fermi level, all lower conduction band
a function of the doping level. The analysis is based on a fitting levels being occupied at zero temperature (inset of Fig. 2c). Our
procedure using the predicted power-law spectral dependence21,24 experimental result for ωA − ωA− agrees very well with equation (1)
of the features (see Methods for details)21,24 . We also convert the (Fig. 2c), further confirming the spectroscopic assignment of
gate voltage to the electron doping density (ne = CVg ) using the the exciton and trion features. We also determine the trion
back-gate capacitance of C = 1.2 × 10−8 F cm−2 and then to the binding energy from the linear fit to be 18.0 ± 1.5 meV. This
Fermi energy (EF = h̄2 πn/2me e 2 ) using an electron band mass of value is compatible with an estimated trion binding energy of
me = 0.35m0 (ref. 14), where m0 is the electron mass. Because of EA− ∼ 0.1EA (for isotropic 2D semiconductors with equal electron
intrinsic charging effects, we furthermore introduce an offset in the and hole masses23 ) and the calculated exciton binding energy of
gate voltage of −107 ± 6 V for EF = 0. This value was extrapolated EA ≈ 0.6 eV(refs 14,27).

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LETTERS NATURE MATERIALS DOI: 10.1038/NMAT3505

a on-resonance with the A exciton, by left-circularly polarized light

1,200 A¬ (σ− ). The trion emission is found to be nearly 100% of the same
Photoluminescence intensity (a.u.)

helicity as the pump light (Fig. 4b). Whereas the optical selection
1,000 rules dictate a single exciton state with hole spin up and electron
spin down in the K-valley on absorption of a σ− photon, multiple
800 trion states are allowed. Among them the lowest energy state
consists of hole spin up and two electrons spin down in the K-valley
A
600 when valley and spin exchange interactions are included. Our
photoluminescence result indicates that the optically excited hole
400 in the trion remains spin up, that is, in the K-valley (for a time
much longer than the trion lifetime), even in the presence of strong
200 exchange mediated spin relaxation. This suggests the robustness
of the hole valley index as a result of the coupled valley and spin
0 degree of freedom18,22 .
1.80 1.85 1.90 1.95 2.00 The existence of tightly bound trions with dynamically control-
Photon energy (eV) lable hole valley and spin in monolayer MoS2 opens up possibilities
of novel many-body phenomena. The large trion binding energy
b in 2D atomic crystals may also impact the development of new
1,600 σ¬ photonic and optoelectronic devices, such as optical detectors or
Photoluminescence intensity (a.u.)

σ+ photovoltaic cells. In contrast to neutral excitons, trions can be

guided by electric fields, suggesting schemes to overcome the losses
1,200
associated with the usual diffusive motion of neutral excitons.

800 Methods
Sample preparation. Monolayer MoS2 samples were mechanically exfoliated from
bulk MoS2 crystals (SPI) on silicon substrates covered by a 280 nm layer of thermal
400 oxide. Monolayer samples, typically of an area >50 µm2 , were identified by optical
microscopy. The sample thickness was confirmed independently by atomic-force
microscopy and photoluminescence measurements2,13 . Monolayer MoS2 FET
0 devices were fabricated by defining drain and source contacts either through
e-beam lithography or photolithography, followed by deposition of Cr/Au or Ni in
1.80 1.85 1.90 1.95 2.00 an e-beam evaporator. For the polarization resolved measurement, the exfoliated
Photon energy (eV) samples were transferred to hexagonal boron nitride substrates.

Figure 4 | Valley and spin control of trions in monolayer MoS2 . Optical measurements. Monolayer MoS2 FETs were first characterized at 10 K
and at room temperature when the back gate was varied systematically from
a, Photoluminescence spectrum of a monolayer MoS2 sample on a h-BN −100 to 80 V. No significant hysteresis was observed. The drain–source current
substrate at 10 K with fully resolved exciton (A) and trion (A− ) emission. Ids was measured in the linear response regime under a drain–source bias
b, The left-circularly polarized (σ− ) and right-circularly polarized (σ+ ) voltage Vds = 40 mV across a channel length of 10 µm. For optical absorption
component of the trion emission for excitation by σ− light at 1.96 eV, nearly measurements, the broadband radiation from a quartz tungsten halogen source
on-resonance with the A exciton. was focused onto monolayer MoS2 by a 40× objective. The reflected radiation
was collected and analysed with a grating spectrometer equipped with a liquid
nitrogen cooled CCD.
The large trion binding energy observed in monolayer MoS2 The reflectance contrast was measured by normalizing the radiation reflected
suggests the importance of trions even at elevated temperatures. from the sample on substrate to that from the bare substrate. The sample
Indeed, both the exciton and trion features can be identified in the absorbance was obtained from the reflectance by using a Kramers–Kronig
constrained variational analysis28 (Supplementary Section S4). Photoluminescence
optical response of doped monolayer MoS2 at room temperature
measurements were performed using the same set-up with a single-mode
(Fig. 3a,b), although the resonances are significantly broadened. solid-state laser centred at 532 nm. The laser intensity on the sample was kept
The absorption and especially photoluminescence are highly de- below 500 W cm−2 , which corresponds to a steady-state photoexcitation density
pendent on doping (Fig. 3c). Whereas the trion photoluminescence of ∼ 1010 cm−2 in monolayer MoS2 (refs 2,29). This is ∼2–3 orders of magnitude
is largely gate independent, the exciton photoluminescence varies lower than the electron doping density induced by the silicon back gate. For the
polarization resolved measurements, a Babinet–Soleil compensator was used to
by nearly two orders of magnitude, which is also correlated with produce circularly polarized 632.8 nm light from a HeNe laser. Emission from the
the Ids − Vg dependence12 . This dependence arises primarily from sample passed through a combination of a quarter-wave Fresnel rhomb and an
a spectral weight reduction of the exciton resonance with doping, analyser for selection of the left- and right-circularly polarized components.
which is consistent with the low-temperature data (although less
noticeable at low doping levels owing to the finite temperature Analysis of the absorption spectra. We used the predicted single-sided
power-law spectral dependence of the exciton and trion absorbance in doped 2D
effects). The tuning range of the exciton photoluminescence could semiconductors, A(ω) = 6X =A,A−1 aX (ω − ωX )−αX (for ω > ωX ) (refs 21,24). This
be further increased with better quality samples. Such strong tun- expression corresponds to a shake-up process, a non-instantaneous evolution
ability of the exciton photoluminescence was not observed at 10 K, of the 2DEG to a new equilibrium configuration on creation of a hole21,24 . Here
where emission originates from hot photoluminescence before aX , ωX and αX are, respectively, the amplitude, threshold energy and critical
exciton–trion equilibrium is reached, whereas at room temperature, exponent of resonance X (= A and A− ). In the limit of relatively low doping
densities, as in our experiment, aX (X = A,A− ) depend weakly on doping24 and
exciton photoluminescence originates primarily from populations were kept as constants. To compare with experiment, the power-law dependence
thermally excited from the trion state. was convoluted with a Gaussian to account for sample inhomogeneity and the
Finally, we demonstrate the unique spin and valley properties of onset of indirect optical transitions in doped semiconductors21 . In addition, a
trions in monolayer MoS2 . Figure 4a shows the photoluminescence smooth background describing the low-energy tail of higher energy transitions
spectrum for a monolayer MoS2 sample on a hexagonal boron was subtracted from experimental spectra. (See Supplementary Sections S3
and S4 for details.) The fits (green lines, Fig. 2a), with individual contributions
nitride (h-BN) substrate at 10 K, where the trion and exciton from excitons and trions (blue lines), are in good agreement with experiment
features are fully resolved because of the high homogeneity of (red lines). At positive gate voltages the exciton absorption is very weak and is
the sample. We optically pump the sample at 1.96 eV, nearly omitted from the fitting.

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NATURE MATERIALS DOI: 10.1038/NMAT3505 LETTERS
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