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Surface Optical Rectification from Layered MoS2 Crystal by THz Time-Domain

Surface Emission Spectroscopy

Article in ACS Applied Materials & Interfaces · January 2017

DOI: 10.1021/acsami.6b13961

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Surface Optical Rectification from Layered MoS2 Crystal by THz Time-

Domain Surface Emission Spectroscopy
Yuanyuan Huang, Lipeng Zhu, Qiyi Zhao, Yaohui Guo, Zhaoyu Ren, Jintao Bai, and Xinlong Xu*
Shaanxi Joint Lab of Graphene, State Key Lab Incubation Base of Photoelectric Technology and Functional Materials, International
Collaborative Center on Photoelectric Technology and Nano Functional Materials, Institute of Photonics and Photon-Technology,
Northwest University, Xi’an 710069, China
*
S Supporting Information

ABSTRACT: Surface optical rectification was observed from the layered semiconductor molybdenum disulfide (MoS2) crystal
via terahertz (THz) time-domain surface emission spectroscopy under linearly polarized femtosecond laser excitation. The
radiated THz amplitude of MoS2 has a linear dependence on ever-increasing pump fluence and thus quadratic with the pump
electric field, which discriminates from the surface Dember field induced THz radiation in InAs and the transient photocurrent-
induced THz generation in graphite. Theoretical analysis based on space symmetry of MoS2 crystal suggests that the underlying
mechanism of THz radiation is surface optical rectification under the reflection configuration. This is consistent with the
experimental results according to the radiated THz amplitude dependences on azimuthal and incident polarization angles. We
also demonstrated the damage threshold of MoS2 due to microscopic bond breaking under the femtosecond laser irradiation,
which can be monitored via THz time-domain emission spectroscopy and Raman spectroscopy.
KEYWORDS: molybdenum disulfide (MoS2), optical rectification, terahertz (THz) time-domain surface emission spectroscopy,
femtosecond laser, second-order susceptibility

1. INTRODUCTION to deduce the linear and nonlinear optical properties of

Terahertz (THz) technology as the cutting-edge technology1
shows great prospects for applications in imaging,2 medicine
biology,3 high-speed communication,4 and spectroscopy. It is
an interdiscipline between ultrafast nonlinear optics, condensed
matter physics, and optoelectronics. Recently, broadband THz
spectroscopy approaches have been used to study fundamental
physics in various materials such as the excitation of surface
plasmons in metallic grating,5 electrostatic coupling between
particles in GaAs,6 carrier drift and diffusion characteristics in
InAs,7 exciton-like trap states in TiO2 nanotubes,8 and dynamic
THz polarization in single-walled carbon nanotubes.9 Espe-
cially, among the spectroscopy approaches, THz time-domain
emission spectroscopy under femtosecond laser excitation
offers a contactless and sensitive method for the surface and
interface properties of the semiconductors.10
When the ultrafast femtosecond pulse laser impinges onto
the semiconductor surface, the polarity, amplitude, and phase
information on the generated THz pulses offer a powerful tool
semiconductors, such as the carrier mobility, doping concen-
tration, polarity of the static field,10 photo-Dember field,11
plasmon field enhancement,12 ultrafast carrier dynamics,13
optical rectification,14 and photon-drag current.15 Additionally,
THz time-domain emission spectroscopy can be steered
conveniently via external magnetic field, 16 temperature
control,17 angle-dependent incidence,18 and other experimental
configurations. Thus, the THz surface emission spectroscopy of
various semiconductors such as GaAs, GaSb, InAs, InSb, and
InP10 are systematically studied, and these spectroscopy
information in turn can be used for the rapid improvement
of THz sources, which once were the bottleneck for the THz
community.
Received: November 2, 2016
Accepted: January 13, 2017
Published: January 18, 2017

© 2017 American Chemical Society 4956 DOI: 10.1021/acsami.6b13961

ACS Appl. Mater. Interfaces 2017, 9, 4956−4965
ACS Applied Materials & Interfaces
Figure 1. Characterization of MoS2 crystal for (a) simplified energy band diagram, the blue and black arrows indicate the direct and indirect
transition from the valence band maximum to the conduction band minimum; (b) Raman spectrum under 514.5 nm excitation; (c) X-ray diffraction
spectrum.
Recently, with the development of advanced materials
science, THz spectroscopy has also been used to understand
the photoelectric properties in some new applied materials such
as the effect of the surface states on topological insulator
Bi2Se3,19 built-in electric field along the aligned carbon
nanotubes,20 plasmon enhancement in monolayer graphene,21
and dynamical photon-drag effect in multilayer graphene.22
Among them, the emergence of two-dimensional (2D) layered
materials provides a new route for not only compact 2D THz
devices but also remarkable photoelectric properties under-
standing of layered materials. Recent experiments mainly focus
on the THz generation from graphite,23 plasmon-enhanced
single-layered graphene,21 and multilayered graphene.22 How-
ever, graphene and graphite are gapless semiconductors, which
limit the further optoelectronic applications in THz field.
Molybdenum disulfide (MoS2) as an emerging 2D layered
material possesses extraordinary physical, electrical, and optical
properties owing to its particular energy band structure.24 As an
indirect semiconductor with band gap energy Eg = 1.29 eV, the
bulk MoS2 can be transformed into direct semiconductor of
monolayer MoS2. Therefore, MoS2 is an attractive candidate for
various photonic and optoelectronic applications, such as
phototransistors,25 photodetectors,26 and heterojunction solar
cells.27 As the working frequency of devices improves gradually
from GHz to THz region, the unique advantages of MoS2 in
THz field are supposed to be accentuated. For the static optical
response of MoS2 in the THz region, the dielectric properties
have been studied, which suggest high absorption in THz
region with carrier densities as high as 1015 cm−3.28 As for the
dynamic optical response, the transient THz photoconductivity
of trilayer MoS2 can reach ultrafast picosecond (ps) scale.29
The momentum scattering time in multilayer MoS2 approaches
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1.46 ps at 30 K, with the corresponding carrier mobility of 4200
cm2 V−1 s−130 in THz spectroscopy. Virtually, although the
THz time-domain transmission/reflection spectroscopy has
been widely used to measure the linear THz properties of
MoS2, it is limited to achieve the surface research on the
optoelectronic semiconductors. However, THz time-domain
surface emission spectroscopy under reflection configuration
can make up for the limitation of the THz technology
effectively, as this technique focuses on the nonlinear properties
of MoS2 as a THz source.
In this report, we present investigations of THz pulse
radiation from layered MoS2 crystal under the linearly polarized
femtosecond laser excitation with the reflection configuration.
The linear dependence of radiated THz amplitude on incident
pump influence can confirm the second-order nonlinear
process. Interestingly, we can figure out the damage threshold
of MoS2 due to the microscopic chemical bond breaking under
the femtosecond laser irradiation by THz time-domain
emission spectroscopy and Raman spectroscopy. Moreover,
theoretical analysis based on azimuthal and incident polar-
ization angle-dependent THz radiation agrees well with the
experimental results, revealing the underlying radiation
mechanism is surface optical rectification. The investigation
can not only supplement the nonlinear property character-
ization of MoS2 but also deepen the understanding of the
surface optical rectification effect of these layered semi-
conductors.
2. EXPERIMENTAL SECTION
The free-standing MoS2 sample from SPI Supply is 90 μm in thickness,
and the size of the sample is approximately 8 × 8 mm. As an indirect
band gap semiconductor, the simplified energy band diagram of MoS2
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Figure 2. Schematic illustration of (a) experimental setup and (b) THz radiation in reflection configuration. XYZ and X′Y′Z′ represent the
laboratory and crystal coordinate, respectively. HWP: half-wave plate, wire-grid polarizer P1 and P2 are perpendicular and 45° aligned. The p-
polarized and s-polarized excitation are along the X-axis and Y-axis; (c) and (d): X- and Y-components of generated THz electric field under p-
polarized (red curves) and s-polarized (black curves) IR laser illumination.
crystal (Figure 1a) is calculated from the software Quantum Espresso,
the in-plane lattice constants a = 3.166 Å and c = 18.41 Å. For
monolayer MoS2 with the band gap of approximate 1.9 eV, the second
conduction band minimum (CBM) lies at the symmetry point
between K and Γ,31 as shown in Figure 1a with a dash line. When the
valence band maximum (VBM) and CBM both locate at K point, the
direct transition indicated with a blue arrow occurs in monolayer
MoS2. However, the splitting caused by the interlayer interaction in
multilayer and bulk MoS2 forces the CBM to a lower-energy position
compared with the monolayer structure.32 Besides, the energy of
valence edge at Γ point increases and eventually becomes the VBM
instead of K point in the monolayer structure. Hence, the indirect
transitions of electrons occur from VBM at Γ point to the CBM in the
middle of K and Γ points, as shown by the black-arrow lines in Figure
1a. Additionally, the Raman spectrum (microscope model inVia from
Renishaw Company) of MoS2 crystal under 514.5 nm excitation
indicates that in-plane E2g1 and the out-of-plane A1g modes occur at
383.6 and 409.4 cm−1 (Figure 1b). The two characteristic peaks
manifest high purity of the MoS2 crystal. The typical polytypes of
layered MoS2 crystal are hexagonal 2H- and rhombohedral 3R-MoS2
differing from stacking orders,33 belong to D6h and C3v space groups,
respectively. Among them, the 2H polytype is centrosymmetric, while
the inversion symmetry of 3R polytype is broken. We take the X-ray
analysis (2θ-scanning) of MoS2 crystal via X-ray diffraction (XRD,
HaoYuan Instrument) to confirm which polytype the sample is. The
XRD primary peaks shown in Figure 1c suggest that the MoS2 crystal
is 2H polytype holding 6-fold screw axis of symmetry (JCPDS no. 03-
065-1951) with a good crystalline quality. However, similar to
graphite,34 as the surface breaking the bulk symmetry, the surface of
MoS2 crystal has one 3-fold axis of symmetry, which plays an essential
effect in our reflection configuration experiment.
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3. RESULTS AND DISCUSSION
THz radiation from layered MoS2 crystal is proceeded at room
temperature. Figure 2a illustrates the experimental setup and
key elements. The infrared (IR) wave emits from a mode-
locked Ti: sapphire regenerative amplifier (Spectra-Physics,
Spitfire) with 800 nm central wavelength, 35 fs pulse duration,
and 1 kHz repetition rate. The laser beam is divided into two
parts by a beam splitter. The pump wave with the primary
energy distribution illuminates the sample at 45° incident angle
(angle θ in Figure 2b) and 3 mm in diameter. THz radiation
from a sample is collected and collimated by an off-axis
parabolic mirror. Afterward, the THz radiation is focused onto
ZnTe crystal (110) via another parabolic mirror. The electro-
optical sampling35 via changing time delay between THz pulses
and probe beam is utilized to portray the THz waveforms. We
fixed the polarization of the probe beam at s-polarization with a
Glan-Taylor prism, and the power is fixed at 1.2 mW. The
polarization of THz radiation is fixed via a pair of wire-grid
polarizer (WGP), and the optimal crystalline direction of probe
ZnTe crystal has been optimized via rotating the crystal.36 A 10
mm-thick polyethylene plate and a 0.5 mm-thick silicon plate
are closely fixed in a holder and placed after the sample. The
polyethylene plate can not only attenuate the infrared wave but
also avoid the THz radiation from silicon after the residual
excitation laser.37 Then the silicon plate can totally block the
residual infrared wave across the polyethylene, while the THz
wave can pass through the plates. There are no multiple
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reflections from the plates, as we can distinguish the multiple
reflections from the time-domain windows. The polarization
states of the pump beam can be varied using a half-wave plate
(HWP).The EX component of the generated THz electric field
can be extracted with a perpendicularly aligned WGP (P1 in
Figure 2a), while the EY component can be obtained after
adding another 45° WGP (P2 in Figure 2a) in the optical path
and after simple mathematical operation without changing the
probe beam and ZnTe crystal.38 Then both THz components
defined in Figure 2b can be portrayed completely. We present
the THz waveforms of two components under p-polarized and
s-polarized excitation (Pin and Sin) in Figure 2c,d. The
absolute values of the THz electric field can be calculated
according to the current measurement from Lock-in amplifier
as following:36
ΔI ωn3E THzr41L
=
Iprobe c (1)
Here, the nonzero electro-optic coefficient (ZnTe) r41 = 3.9
pm/V, the refractive index of ZnTe in the infrared region n =
2.8.39 c and ω are the speed of light in vacuum and the circular
frequency, and the length of the crystal L = 2 mm. In the
experiment, Iprobe is 9.4 μA, and the peak amplitude of
measured ΔI/Iprobe = 1.3 × 10−4; therefore, we can calculate the
peak value of THz electric field ETHz = 96.72 V/m. According
to the previous demonstration of organic crystals DSTMS and
OH1, 40 this value could be enhanced after systematic
optimization such as adjusting the spot size on samples and
THz spot size on detectors. Strikingly, the EX (Figure 2c) and
EY (Figure 2d) components present giant amplitude differences,
suggesting the primary THz energy distributes along EX
component regardless of the incident polarization states. For
the EX component, the radiation amplitude from Sin excitation
are three times less than that from Pin, and the polarity of
generated pulses will reverse under different polarization (Pin
and Sin) excitations. Similarly, the THz polarity of EY
component under such two polarization excitations are also
reversed, but the amplitudes are approximately equal. The
polarization-induced polarity reversal is related to the THz
radiation mechanism. Generally, the THz radiation polarity are
hardly influenced by the incident polarization from the
photoconductivity mechanism either by intrinsic electric field
or by extrinsic electric field under linear process. For instance,
the THz polarity from the surface depletion field are decided by
the doping type not by the excitation polarization in
semiconductor, while the THz polarity from the photo-Dember
induced field are determined by the discrepant mobility
between electrons and holes instead of doping type.41 However,
the THz polarity of EX and EY components from MoS2 are
definitely influenced by the incident polarization states. Similar
to the previous demonstration of graphene,21 the resemblance
of polarity reversal under different excitation polarization stems
from the nonlinear process. Thus, we tentatively attribute the
THz radiation mechanism of MoS2 crystal to the nonlinear
process. The further quantitative investigation of THz radiation
on incident polarization states is proceeded to confirm which
nonlinear process occurs in MoS2 crystal in the following part.
To our best knowledge, the representative semiconductor
InAs is one of the most effective THz generators. According to
its basic physical properties, the comparison between MoS2 and
InAs42 is shown in Table 1 to further explore the radiation
mechanism. Different from the InAs with narrow direct band
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Table 1. Physical Properties of MoS2 and InAs
sample MoS2 InAs
band gap (eV) 1.29 0.36
electron mobility μe (cm2/(V·s)) 82544 30000
hole mobility μh (cm2/(V·s)) 155 240
electron mass me* 0.47 me 0.027 me
hole mass mh* 0.63 me 0.33 me
refractive index (at 800 nm) 4.8328 3.73
refractive index (at 1 THz) 2.95 3.78
penetration depth (at 800 nm) 5.33 μm43 142 nm
gap, the MoS2 crystal has a wide indirect band gap. As for the
carriers, the great differences of mobility and mass between
electrons and holes in InAs are essential elements to form
transient photo-Dember field,41 which further induce intense
THz radiation. However, the mobility and mass of electrons
and holes in MoS2 are in the same order of magnitude. In
addition, the penetration depth of MoS2 crystal can be
calculated from the absorption coefficient in reference43 at
1.55 eV (800 nm). The depth of MoS2 is much larger than that
of InAs. The differences between two crystals suggest that THz
radiation from MoS2 is not from the photo-Dember effect as it
is in InAs.
Similar to 2H-MoS2, another typical layered material graphite
is a centrosymmetric crystal possessing hexagonal symmetry23
as well. It also exhibits peculiar thermal, electrical, and optical
properties. In order to compare, we present the THz radiation
pulses from MoS2, graphite, and p-type InAs (100) (carrier
concentration: 1.5 × 1017cm−3) crystals. These samples are
mounted in the same holder and manipulated in the same
experimental condition. Notably, the penetration depth of
MoS2 is much larger than that of other two crystals, the
incident IR wave would transmit a penetration depth and cause
a transverse shift (Figure S2 in Supporting Information) on
MoS2. Thus, the combined effect of penetration depth and
rugged surface of MoS2 crystal would lead to the longer pulse
delay of THz radiation as shown in Figure 3a. Generally, the
single-cycle THz pulses generated from three samples have
similar waveforms. Among them, the maximum THz amplitude
of MoS2 and graphite are about 7.6% and 3.8% of the values
generated from InAs, respectively. Thus, the radiations from
MoS2 and graphite are expanded 15 times that of the original
values to guide the eyes in Figure 3a,b. For analogous
comparison in the frequency domain, the Fourier-transformed
spectra of three crystals are shown in Figure 3b. The central
frequency and bandwidth of the spectrum originating from
MoS2 are approximately 0.74 and 2.4 THz, which is similar to
the other two crystals.
To further confirm the nonlinear process, we determined the
dependence between peak-to-peak amplitude of THz compo-
nents and the incident pump fluence. In the experiments, the
excitation laser beam is always p-polarized. Besides, the laser
focus point is behind the sample, which can prevent not only
damage from the intense focal laser beam on sample but also
the air ionization process. After measuring the beam diameter
on the samples (d = 3 mm) with a scale card, the pump fluence
can be calculated from the measured average optical power P
and the repetition rate f = 1 kHz of the laser system as I = P/(f
× S) (mJ/cm2). Where S is the beam area on the samples. The
dependences of EX and EY THz components with pump fluence
are depicted in Figure 3c,d. For E X component, the
experimental data can be divided into two parts. One can be
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Figure 3. Generated THz pulses in (a) time and (b) frequency domain from layered MoS2 (red solid curve), graphite (blue dash curve), and InAs
crystal (black dash curve). The THz radiations from MoS2 and graphite are expanded 15 times compared with the original values to the guide the
eyes. (c),(d) Dependences between peak-to-peak amplitude of EX and EY components of generated THz radiation from MoS2 and pump fluence.
The experimental and fitting results are depicted with dots and solid curves, respectively.

Figure 4. Raman spectra (514.5 nm excitation) of layered MoS2 crystal. (a) The spectra taken on one pristine spot (black curve) and two ablated
spots under low damage level (red curve) and high damage level (blue curves); (b) Optical image of MoS2 with dash circles depicting two ablated
spots; (c) Variation of prominent vibrational modes E2g1 and A1g of three measured spots. The green arrows are labeled to depict the intensity
variation.

fitted linearly up to 5.66 mJ/cm2, and the remaining data can be
fitted linearly with a different slope, as shown in Figure 3c.
Similarly, the fluence dependence of THz radiation for EY
component is consistent with that of EX component until the
critical point at 4.95 mJ/cm2. As the values are much lower than
that of EX component, the EY component could be easily
influenced by laser fluctuation and the ambient environment.
Moreover, this pump-fluence-increasing process is irreversible
once the fluence exceeds the critical point. Thus, we can rule
4960
out other effects such as free carrier absorption influencing the
variation of pump-fluence-dependent slopes. We can reasonably
infer that the decline of slopes are caused by the surface damage
of MoS2, and 4.95 mJ/cm2 ∼ 5.66 mJ/cm2 is the laser-damage
threshold for MoS2 crystal. This threshold is less than the
reported value ∼15 mJ/cm2 under 200 fs Ti: sapphire laser with
100 μm laser diameter on the sample.45 The divergence could
be attributed to the combined differences from samples, the
exposure time, and the ambient environment. The linear fitting
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Figure 5. THz radiation dependence on the azimuthal angle. (a) Diagram of the crystalline surface under p-polarized illumination (incoming arrow).
The THz radiation (outgoing arrow) generates in the reflective direction; (b) Microscopic illustration of MoS2 crystal with the crystalline azimuthal
angle φ; (c) THz electric field dependence on azimuthal angle φ under fixed p-polarized excitation. The experimental and fitting results are depicted
with dot and solid curves, respectively.
between pump fluence I and both THz components are
consistent with the second-order nonlinear effect (optical
rectification) for I ∝ |Eω|2, as this effect is quadratic with the
incident electric field: ETHz ∝ χ(2) · Eω · Eω. This suggests that
the strength of optical rectification (OR) effect is decided by
the interaction between incident electric field and the
susceptibility of nonlinear media. Comparing the bulk and
few layer MoS2, the different bandgap will lead to the different
absorption of the excitation infrared laser. Besides, it will also
lead to different nonlinear optical dispersion relations, which
result in different nonlinear dielectric polarization at the same
wavelength. From the solid-state physics point of view, the
monolayer MoS2 has D3h symmetry, and its inversion symmetry
is broken. However, the symmetry of the bulk structure is
related with stacking orders with different susceptibility. All
these distinctions could lead to the discrepancy in OR process
between the bulk and few-layer MoS2. Although the monolayer
MoS2 can also generate THz radiation under the average 200
mW infrared illumination in the same experimental config-
uration (Supporting Information), the primary THz radiation
mechanism would be essentially different from the bulk
structure.
Previously, there were still few experimental data on the
damage threshold and ablation for MoS2, to our best
knowledge. However, the optical damage threshold is very
important for the nonlinear optical responses under ultrafast
laser illumination, especially for the performance of nonlinear
photonic devices as well as the nonlinear THz devices.
Moreover, the THz emission mechanism by nonlinear optics
from the MoS2 is still unclear near the damage threshold.
Interestingly, we found the THz radiation can continue to
increase even after the ablation. This phenomenon is rarely
discussed in the nonlinear process. Our further investigation on
damage and ablation embodies the evolution of the surface and
structure during this laser heating process, which can be
effectively characterized via Raman spectroscopy. As shown in
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Figure 4a, the Raman spectra focus on one pristine spot and
two ablated spots. As the optical image shown in Figure 4b, we
can clearly observe the laser ablation (spot 1) on the surface
with eyes when the pump fluence increases to 7.07 mJ/cm2.
Then we keep on increasing the pump fluence until to 11.3 mJ/
cm2; subsequently, it can be observed that the ablated region
expands, and the ablation gets more severe (the spot 2). The
ablations are caused by local laser heating and may further
oxidize the surface. The previous transformation of MoS2 to
molybdenum trioxide (MoO3) does happen to the micro-
crystalline powder MoS2.46 However, the antisymmetric
stretching mode (Ag) of MoO3 at 817 cm−1 is absent in our
Raman measurement. This mode is a characteristic peak of
MoO3 with bonding aligning along the a-axis direction.47 It is
suggested that the laser-induced transformation from MoS2 to
crystalline MoO3 does not happen. Comparing the three
Raman spectra, a new peak appears at 284.9 cm−1 for ablated
spot 1, and another new peak at 201 cm−1 appears after
sequentially increasing pump fluence. These new Raman modes
correspond to the B2g modes due to the δO(1)MoO(1)
wagging mode and δO(2)MoO(2) scissor mode, respec-
tively,47 where O(1) and O(2) are nonequivalent types of O
atoms. These suggest that the new molecular Mo−O bonds
form on the surface because of the Mo−S bond dissociation
under intense pump fluence. The Mo−S bond breaking can
also be traced when we focus on the characteristic E2g1 and A1g
modes of the three spots. As shown in Figure 4c, the intensity
of E2g1 decreases monotonously from pristine to ablated spot 2,
while the intensity of A1g mode increases first and then
decreases (as labeled with green arrows in Figure 4c). E2g1 is an
in-plane vibrational mode related to both Mo and S atoms.48 It
is easily influenced by the decrease of the number of scattering
centers (Mo−S bonds) on the surface under the laser
irradiation.45 As for A1g mode, it is an out-of-plane molecular
vibrational mode and only relates to S atom. On one hand, we
speculate that the new constituent Mo−O bonds possibly
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protect the surface at the onset of laser irradiation. On the
other hand, under the protection of Mo−O bonds, Mo−S bond
breaking and atoms removal could enhance the A1g mode due
to its special vibrational feature. Afterward, the persistent laser
irradiation and subsequent surface damage lead to local lattice
sublimation,45 which may further weakens the intensity of A1g
mode. Although the laser irradiation can lead to surface bond
breaking, atom removal, new constituent Mo−O bonds, and
even the local lattice sublimation, the underneath lattice
structure does not change. Accordingly, the MoS2 structure
underneath the ablated top surface can still generate THz
radiation persistently. We believe that the corresponding
investigations can not only deepen the understanding of the
optical rectification process and the THz radiation mechanism
but also provide data for individuals who are interested in the
microscopic variation of MoS2, including bond breaking and
forming, atoms removal, and lattice sublimation.
4. THEORETICAL CALCULATIONS
For the quantitative analysis on crystalline orientation, we put
forward a prototypical model referring to the second-order
nonlinear harmonic generation.49 The model assumes that the
rectification process is confined to an interactive volume called
electric dipole sheet. This hypothetic region at Z = 0 above the
crystalline surface is shown in Figure 5a. The surface is
paralleled with X−Y plane in the laboratory coordinate. The
incident IR wave paralleled to X direction (p-polarized)
propagates along Z direction. The incident angle θ is fixed at
45°. Thus, the emitted THz radiation angle is also 45° and the
refraction angles can be given according to the Snell’s Law41 in
reflection configuration:
nair sin θ = sin 45◦ = nopt sin θopt = n THz sin θTHz (2)
Here, θopt is the refraction angle between normal direction of
the crystal’s surface and the infrared wave, θTHz is the refraction
angle of the generated THz wave in the interface between
sample and air. nopt and nTHz are refractive index when infrared
and THz waves propagate through the MoS2 sample in its
penetration depth. From the refractive index in Table 1, θopt
and θTHz are estimated to be 8.422° and 13.876°, respectively.
Besides, the phase matching is negligible in our reflection
configuration due to the micrometer-order penetration depth of
MoS2. The incident electric field illuminating the sample is
labeled as E±(r), which is the summation of the upward (+)
and downward (−) propagation of the p- and s- polarized
waves34
E±(r ) = (s Ê ±s + p±̂ E±p)e±ikZZeikXX (3)
The spatial phase information on the electric field is divided
into Z component kzZ and X component kXX. p̂ and ŝ represent
the p- and s-polarized states. As a consequence, the
components EX, EY, and EZ of the incident electric field can
be deduced (Supporting Information). Notably, the Y
component (s-polarized component) is negligible in this
situation for the fixed p-polarized incidence. According to the
incident electric field components, the nonlinear optical
rectification process can be expressed via nonlinear dielectric
polarization, which can be given as
Pi(2)(0) = ∑ ε0χijk(2) (0, ω , −ω)Ej(ω)Ek*(ω)
j,k (4)
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Here, ε0 is the permittivity of the space and χ(2)
ijk is the second-
order susceptibility tensor of MoS2. According to the symmetry
on the surface of crystal, χ(2)
ijk must be invariant under the same
group of the symmetry operations49,50
χi(,ni)...′ i = ∑ Ti1, j Ti2 , j ...Tin+1, j χj(n, j) ...j
1 2 n+1 1 2 n+1 1 2 n+1
j1 , j2 ...jn + 1 (5)
Under the rotation operation R(φ) normal to the crystal, we
can obtain the transformed expression of susceptibility tensor
(Supporting Information). Herein, the single variable φ is the
azimuthal angle of MoS2 as shown in Figure 5b. In the optical
rectification process, the generated THz radiation ETHz has a
relationship with the nonlinear dielectric polarization as:
∂ 2P(0, t ) ∂ 2I(t )
E THz ∝ = χ (2) 2 . Thus, its amplitude is proportional
∂t 2 ∂t
to the nonlinear dielectric polarization and the p-polarized THz
radiation can be detected in reflection geometry41 as follows:
E THz ∝ −PX cos θTHz + PZ sin θTHz (6)
Here, the three components PX, PY, and PZ have been calculated
according to the operated susceptibility tensor (Supporting
Information), and then the THz radiation based on the
azimuthal angle can be written as
E THz ∝ 0.97[d 22 sin(3φ) − 2d15] + 0.24(d31 + d33) (7)
As for the experimental results, the dependence between the
maximum amplitude of THz radiation and azimuthal angle of
MoS2 is depicted in Figure 5c. The observed experimental
results agree well with the 3φ-dependence from the theoretical
calculation in eq 7. It is also confirmed that although the space
group of bulk 2H-MoS2 is D6h, the nonlinear effect on the
surface obeys the 3-fold rotational symmetry. Additonally, the
inversion symmetry on surface is broken, which is necessary in
the optical rectification process. Additionally, both curves in
Figure 5c obviously show that the polarity of the THz radiation
can reverse when φ is rotated approximately 90° and change
back again after rotating about 40°. The experimental results
deviate slightly from theoretical curve at some angles, which
mainly attribute to the imperfections such as stacking faults of
MoS2 crystal.51 We have tested another MoS2 sample in the
experiment and find that the THz electric field dependence on
azimuthal angle φ under fixed p-polarized excitation follows the
same tread as that in Figure 5c. However, the variations in the
amplitude are different, which suggest the existence of stacking
faults. This 3-fold azimuthal angle dependence of MoS2 is
definitely different from graphite and InAs crystals. The THz
radiation from the edge plane of graphite have one-fold
rotational symmetry on azimuthal angles, and the polarity is
reversed when graphite is rotated by approximately 180°. This
mainly stems from the accumulated carriers moving along a
preferential direction from stacking faults in graphite.23 While
for p-type InAs (100), the slight dependence of THz radiation
on the azimuthal angle is negligible, which is accordant with the
previous investigation.7 Thus, we emphasize that the THz
mechanism of MoS2 essentially is related to the crystalline
orientation in optical rectification process, differing from the
transient photocurrent induced THz generation in graphite and
photo-Dember filed induced THz radiation in InAs. According
to the former demonstration of classical semiconductor InP in
the optical rectification process,52 the proposed theoretical
model can explain most of the experimental observations and
emphasize the importance of the azimuthal dependence of
nonlinear signal. Thus, almost all the investigations of optical
DOI: 10.1021/acsami.6b13961
ACS Appl. Mater. Interfaces 2017, 9, 4956−4965
ACS Applied Materials & Interfaces
Figure 6. THz radiation dependence on incident polarization angle. (a) Diagram of the structural surface under variable pumping polarization
illumination (incoming arrow). The generated THz waves (outgoing arrow) propagate in the reflective direction; (b) THz electric field dependence
on the incident polarization angle with a fixed azimuthal angle. The experimental and fitting results are depicted with dot and solid curves,
respectively.
rectification process take the in-depth studies on the azimuthal
angles of materials. From the investigations, the (110) zinc-
blende crystals InP, GaAs, CdTe,14 and (111)-oriented InP10
also show 3φ-dependence on azimuthal angles due to their 3-
fold rotation symmetry.
The incident polarization states can definitely influence the
THz radiation in the optical rectification process. For
transmission configuration, the wave vector of incident beam
is perpendicular to the interface of sample, hence the variation
of incident polarization can be realized via changing azimuthal
angle of sample.53 However, the rotational symmetries of
azimuthal and incident polarization angles are different in the
reflection configuration. Thus, we rotate the incident polar-
ization angle α (see Figure 6a) from 0° to 360° (0° and 90°
correspond to p-polarized and s-polarized, respectively) via a
HWP instead of rotating sample. The incident angle θ is still
45°. After the investigation of azimuthal angle dependence, the
azimuthal angle φ is fixed at the optimal angle with the
strongest radiation efficiency (negative maximum value in
Figure 5c). Similar to the above analysis, the nonlinear
dielectric polarization can be given on the basis of the
interactions between susceptibility tensor and incident electric
field. After the coordinate transformation (Supporting In-
formation) based on the polarization angle, the generated THz
radiation has the dependence on α as
E THz ∝ A cos α + B sin α + C cos(2α) + D sin(2α) + E
(8)
A, B, C, D, and E are fitting constants related with nonzero
susceptibility terms and have been calculated (Supporting
Information). The experimental results along with the fitting
results from eq 8 are shown in Figure 6b. The experimental
results fit well with the calculated results, which further confirm
the validity of the theoretical analysis. From α = 0° at p-
polarization, the THz amplitude decreases monotonously until
α reaches to 90° at s-polarization. Then the amplitude increases
to maximum again after α reaches to 180° at p-polarization
once more. Consequently, the THz amplitudes exhibit 2-fold
rotational symmetry with the changing polarization angle in the
whole process. In addition, the polarity of THz radiation also
shows the 2-fold symmetry. It reverses sign when α is in the
range of 60° ∼ 120° and 240° ∼ 300°, which are adjacent to
the s-polarization. The reversed polarities of THz radiations are
4963
Research Article
related to the dielectric polarization components PX, PY, and PZ.
The amplitudes of these three components can be changed by
the variable incident polarization angle α according to the
mathematical expressions (Supporting Information). Thus, the
amplitudes as well as polarities of detected THz radiations are
further influenced. It is determined from these results that the
THz radiation mechanism of MoS2 in reflection configuration is
surface optical rectification in reflection configuration.
5. CONCLUSIONS
In summary, we observe that 2H-MoS2 crystal can generate
THz radiation efficiently ranging from 0.1−3.5 THz under
linearly polarized femtosecond laser excitation. The linear
dependence of THz amplitude on incident pump fluence
indicates the second-order nonlinear process. We take the
theoretical analysis of optical rectification mechanism based on
the space symmetry. The calculated results fit well with the
results from experiments with respect to the dependences on
azimuthal and incident polarization angles. These consistent
dependences of two angles verify the THz radiation of MoS2 by
surface optical rectification. Furthermore, the bond breaking of
MoS2 can be monitored by combining THz emission and
Raman spectra after the laser-damage threshold 5.66 mJ/cm2.
The investigations on layered MoS2 crystal can not only deepen
the understanding of nonlinear optical rectification process but
also potentially provide a sensitive and noninvasive method to
characterize the surface and interface properties of MoS2 by
THz surface emission spectroscopy.
■ ASSOCIATED CONTENT
* Supporting Information
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsami.6b13961.
Dependence of THz radiation on azimuthal angle, the
dependence of THz radiation on incident polarization
angle, THz radiation from monolayer MoS2, and THz
surface emission considering the penetration depth
(PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: xlxuphy@nwu.edu.cn. Fax: +86 29 88303336.
DOI: 10.1021/acsami.6b13961
ACS Appl. Mater. Interfaces 2017, 9, 4956−4965
ACS Applied Materials & Interfaces
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by National Natural Science
Foundation of China (No. 11374240), Ph.D. Programs
Foundation of Ministry of Education of China (No.
20136101110007), National Key Basic Research Program
(2014CB339800), and Postgraduate Innovative Talent Train-
ing Program of Northwest University (YZZ15031).
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