Article

Cite This: ACS Photonics 2019, 6, 1002−1009 pubs.acs.org/journal/apchd5

Tailoring Photoluminescence from MoS2 Monolayers by Mie-

Resonant Metasurfaces
Tobias Bucher,*,†,‡ Aleksandr Vaskin,†,‡ Rajeshkumar Mupparapu,†,‡ Franz J. F. Löchner,†,‡
Antony George,‡,§ Katie E. Chong,∥ Stefan Fasold,†,‡ Christof Neumann,§ Duk-Yong Choi,⊥
Falk Eilenberger,†,‡,#,○ Frank Setzpfandt,†,‡ Yuri S. Kivshar,∥ Thomas Pertsch,†,‡,#,○
Andrey Turchanin,§,‡,□ and Isabelle Staude†,‡
†
Institute of Applied Physics, Friedrich Schiller University Jena, 07745 Jena, Germany
‡
Abbe Center of Photonics, Friedrich Schiller University Jena, 07745 Jena, Germany
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§
Institute of Physical Chemistry, Friedrich Schiller University Jena, 07743 Jena, Germany
∥
Nonlinear Physics Centre, Research School of Physics and Engineering, The Australian National University, Canberra, ACT 2601,
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Australia
⊥
Laser Physics Centre, Research School of Physics and Engineering, The Australian National University, Canberra, ACT 2601,
Australia
#
Fraunhofer-Institute for Applied Optics and Precision Engineering IOF, 07745 Jena, Germany
○
Max Planck School of Photonics
□
Jena Center for Soft Matter (JCSM), 07743 Jena, Germany
*
S Supporting Information

ABSTRACT: We experimentally investigate coupling of the photo-

luminescence (PL) from monolayers of MoS2 to Mie-resonant
metasurfaces consisting of silicon nanocylinders. By a systematic variation
of the nanocylinder diameter, we sweep the metasurface resonances over
the excitonic emission band of monolayer MoS2. We observe strong
enhancement, as well as spectral and directional reshaping of the
emission. By a comprehensive optical characterization, we unveil the
different physical factors, including electronic, photonic, and mechanical
influences, responsible for the observed PL changes. Importantly, we
show that by geometrical tuning of the nanocylinder resonances, the
emission can be tailored from occurring under very large angles to being directed out of the substrate plane. Our results
highlight the need and potential of controlling not only the photonic, but also electronic and mechanical environmental factors
for tailoring PL from TMD monolayers by integrating them in nanophotonic architectures.
KEYWORDS: light-emitting metasurfaces, Mie resonances, dielectric nanoantennas, transition metal dichalcogenides, 2D materials,
excitonic emission

V an der Waals stacked transition metal dichalcogenide

(TMD) crystals attracted massive research attention over
the past years due to their unique physical properties when
thinned down to few- or monolayer sheets.1−4 In the few-layer
regime, their mechanical, electronic, and optical properties not
only remarkably deviate from the properties of respective bulk
materials, but also strongly depend on the number of layers
forming the crystal stack. Importantly, it was shown
theoretically and experimentally that some TMDs (MX2,
where M = Mo, W and X = S, Se) transition from indirect to
direct band gap semiconductors when approaching the
monolayer phase,5,6 show strong excitonic effects7−9 as well
as large spin−orbit splitting,10 and exhibit circular dichroism at
the K/K′ valleys.11−14 These unique properties make TMDs
versatile emitters, which can be harnessed for light emitting
photonic applications by integrating them with resonant
photonic nanostructures.
The interaction of light with localized emitters such as
fluorescent molecules, nitrogen vacancy centers in diamond,
and semiconductor quantum dots placed in proximity to
photonic and plasmonic nanostructures has been widely
investigated.15−19 Similar studies have been extended to
TMD monolayers with plasmonic nanostructures for enhanc-
ing their interaction with light.20−25 Recently, plasmonic
nanostructures attracted further interest owing to their
capabilities of routing bichiral emission of TMD monolayers,
targeting valleytronics applications.26−28 However, plasmonic
Received: December 23, 2018
Published: March 5, 2019

© 2019 American Chemical Society 1002 DOI: 10.1021/acsphotonics.8b01771

ACS Photonics 2019, 6, 1002−1009
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Article

nanostructures may also induce strong local strain29,30 and can SAMPLE FABRICATION
mediate significant injection of hot carriers into TMD We fabricated hybrid structures of 1L-MoS2 supported by
monolayers, thus, quenching the emission31,32 and altering silicon nanocylinder metasurfaces using a poly(methyl
the crystalline phase.33 Therefore, alternative material plat- methacrylate) (PMMA) assisted wet-transfer process,41,42 as
forms for nanophotonic applications based on TMD depicted in Figure 2a. First, 1L-MoS2 flakes were synthesized
monolayers are highly desirable.
Resonant dielectric metasurfaces34,35 are promising candi-
dates in this respect. These metasurfaces consist of two-
dimensional arrays of dielectric nanoresonators with a size,
geometry, and spacing such that multipolar Mie-type
resonances are combined with little absorption in the visible
regime. Single dielectric nanoresonators provide only moderate
emission enhancement of emitters placed in their proximity as
compared to their plasmonic counterparts. However, their
dense arrangement in a resonant dielectric metasurface can
result in a strong collective response, which can be tailored to
simultaneously enhance the light−matter interaction and
efficiently manipulate emission directivity.36,37
Previous work has been done on integrating TMD
monolayers with resonant dielectric nanostructures. In
particular, Cihan et al.38 highlight the role of multipolar
electric and magnetic resonances of single silicon nanowires to
control the MoS2 emission directionality and spectrum,
whereas Chen et al.39 show enhanced directional emission
from WSe2 monolayers integrated with a multiresonant silicon
waveguide-grating structure. Furthermore, Zhang et al.40 have
considered Fano resonances in dielectric nanohole arrays to
simultaneously enhance the absorption and emission of MoS2
monolayers while achieving unidirectional emission.
In this work we explore the potential of resonant all-
dielectric metasurfaces to manipulate the light interaction with
molybdenum disulfide monolayers (1L-MoS2) by alteration of
their photonic and electric environment as well as their
surrounding topography. We realize a hybrid system
constituted of 1L-MoS2 placed on top of silicon nanocylinder
metasurfaces by means of a wet transfer process. Figure 1

Figure 2. (a) Scheme of the PMMA-assisted wet-transfer process. (b)

True-color optical microscope image of 1L-MoS2 flakes as CVD-
grown on the sacrificial thermal-oxide capped silicon wafer. (c) Top-
view scanning electron micrograph of a silicon metasurface on glass
used as target substrate in the fishing step. (d) True-color optical
microscope image of a silicon metasurface after fishing and removal of
the PMMA transfer-layer. (e) Cross-sectional scanning electron
micrograph of the sample shown in (d) and for a region covered by
the monolayer molybdenum disulfide flake.

by chemical vapor deposition (CVD) from solid precursors

Figure 1. Sketch of a 1L-MoS2 flake (the crystal structure is shown in
the inset) placed on top of a silicon nanocylinder metasurface on a
glass substrate.
displays a conceptual sketch of the resulting structures.
Photoluminescence (PL) spectroscopy, microscopy, and
back-focal-plane imaging were performed to investigate the
interaction of the resonant dielectric nanostructures with the
1L-MoS2. Verification of the monolayer phase as well as further
characterization was done by means of Raman spectroscopy
and second-harmonic measurements. The multidimensional
analysis allows us to isolate different environmental factors that
may influence the emission characteristics of the 1L-MoS2.
1003
using silicon wafers capped with a 300 nm thermal-oxide layer
as substrates43 (see Methods for details on the growth
process). Our growth process results in densely spaced 1L-
MoS2 flakes with edge lengths typically reaching up to 60 μm
and is widely scalable for large area coverage. Figure 2b shows
an optical microscope image of as-grown 1L-MoS2 flakes that
are clearly visible as triangles (single crystal) or clusters. The
formation of clustered flakes can occur due to merging of
adjacent 1L-MoS2 flakes by either forming grain boundaries
(polycrystalline 1L-MoS2 flake) or an overlapping region
(bilayer MoS2). The latter case was excluded in our
experiments by observing the visual change in contrast in
optical microscope images for bilayer MoS2 as compared to
1L-MoS2. Note that the color impression of the 1L-MoS2
flakes in Figure 2b originates from thin film interferences in the
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Figure 3. (a) Spatial PL mappings of 1L-MoS2 on silicon nanocylinder metasurfaces shown for different samples of varying diameter D. The
metasurface areas are indicated by white dashed lines. (b) PL spectra of the same 1L-MoS2 flakes, as shown in (a), measured on top of the silicon
nanocylinder metasurface (red curves) and on bare substrate (blue curves), with each measurement position being indicated by a blue circle in (a),
respectively. The values for the bare substrate are multiplied by 3 for better visibility. For each metasurface, the relative emission enhancement
PLmetasurf/PLsubstr (green curves) as well as the transmittance spectrum (dotted black curves) are also plotted. The black dashed line denotes the
spectral position of the resonance with significant quadrupole contribution of the nanocylinders. Note that the enhancement curves were smoothed
by a three-pixel binning of the wavelength resolution of the spectrometer.

thermal-oxide capping of the growth substrate, where the blue
color is determined by the thickness of the layer. Next, silicon
nanocylinder metasurfaces were fabricated on standard micro-
scope coverslips (borosilicate glass) using an electron-beam
lithography based process (see Methods for details on the
fabrication process). Our samples consist of square arrays of
silicon nanocylinders with constant height H = 188 nm, lattice
constant Λ = 560 nm, and varying diameter D = 200−350 nm.
Note that in contrast to previous works employing nano-
cylinder arrays,44 the nanocylinders are designed such that they
support optical resonances throughout the visible and near-
infrared range including the emission band of 1L-MoS2 with a
center wavelength of 660 nm. In order to assess the multipolar
composition of the considered metasurface resonances, we
performed numerical simulations of the metasurface trans-
mittance, showing very good agreement with experimentally
measured spectra (see Supporting Information). Then, a
multipole decomposition of the local currents inside the
nanoresonators was performed,45 revealing that the resonances
overlapping with the emission band of 1L-MoS 2 are
characterized by electric dipolar as well as significant electric
and magnetic quadrupolar contributions (see Figure S4b).
Therefore, in the following we refer to them as resonances with
significant quadrupole contribution. A scanning electron
micrograph (SEM) of a typical fabricated sample is shown in
Figure 2c.
Finally, for transferring the 1L-MoS2 from the growth
sequently, the transfer layer can be fished from the surface by
catching it with the target substrate, that is, the fabricated
metasurface sample. In the final step, the PMMA layer was
removed in a critical point dryer using acetone as solvent and
liquid carbon dioxide as supercritical fluid.42,46 In Figure 2d, a
top-view optical microscope image of a fabricated silicon
metasurface (dark square) after the successful transfer of 1L-
MoS2 flakes (cyan triangles) is shown. Note that the structural
integrity of the 1L-MoS2 flakes is largely preserved during the
transfer. Further, we analyzed the placement of the 1L-MoS2
flakes on the silicon metasurface by taking an SEM of a cross-
section through the hybrid structure, milled using a focused
ion beam (see Figure 2e). To improve the quality of the cross-
sectional cut, we deposited platinum on top and below the
transferred 1L-MoS2 flake by means of electron-beam-induced
deposition (visible as grainy regions on top and in between the
silicon nanocylinders). The 1L-MoS2 flake is lying flat on top
of the metasurface providing physical contact of the 1L-MoS2
flakes with the nanocylinders, while it is freely suspended in the
region between adjacent nanocylinders. The suspended layer
appears thicker in the cross section image than expected from a
1L-MoS2 flake, which is likely due to organic residue and Si/
SiO2 debris accumulated during the focused ion beam milling
process. The monolayer phase of the transferred MoS2 flakes
was verified by Raman spectroscopy and second-harmonic
generation microscopy (see Supporting Information for
details). All measurements in this study were performed
under ambient conditions.

■
substrate to the target metasurfaces, a silicon wafer with as-
grown 1L-MoS2 flakes was spin-coated with PMMA and
immersed into a weak potassium hydroxide (KOH) solution to PHOTOLUMINESCENCE ENHANCEMENT
separate the silicon oxide layer and the PMMA. Eventually, the To investigate the effect of the metasurfaces on the emission
wafer sinks down leaving the PMMA layer (plus superficially properties of 1L-MoS2 first, we compare the A-excitonic
embedded 1L-MoS2 flakes) floating on the surface. Sub- emission of single flakes of 1L-MoS2 situated on top of a
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Figure 4. (a) Relative spectral weights wX/T of exciton (red curves) and trion (blue curves) species in 1L-MoS2 situated on silicon nanocylinder
metasurfaces (solid lines) and glass substrate (dotted lines). (b) Enhancement factors of excitonic (red curve) and trionic (blue curve)
contributions. The lines were added as guides to the eye.
metasurface with that of flakes placed on the bare substrate. To
exclude possible variations of the emission properties between
different flakes, we consider only flakes which are partly
situated on top of the metasurface and partly on the substrate.
PL microscopy and spectroscopy measurements were
performed using a commercially available confocal laser-
scanning microscope setup (PicoQuant, MicroTime200). For
excitation, a 532 nm pulsed laser with a repetition rate of 80
MHz and pulse lengths of 100 ps was focused on the sample
using a 40x/0.65 NA objective resulting in an estimated spot
diameter of 2r = 2λ/(NA·π) ≈ 0.52 μm. The average laser
power in front of the objective was ≈5 μW. The same objective
was used to collect the PL in reflection configuration. In the
detection path the reflected laser light was blocked using a 550
nm long-pass filter. An additional 685 nm ± 35 nm bandpass
filter was used for acquiring spatial PL mappings. Measured PL
mappings of 1L-MoS2 flakes transferred onto four different
silicon nanocylinder metasurfaces with varying diameter (240,
260, 275, and 300 nm, as measured from SEMs) are shown in
Figure 3a. Each mapping shows a fairly uniformly enhanced PL
signal in the area of the silicon nanocylinder metasurfaces
(inside white dashed lines). Typical enhancement factors range
from 5 to 8.
Further, we measured PL spectra of the same four 1L-MoS2
flakes. Each measurement position is indicated by a blue circle
in the respective PL mapping in Figure 3a and was chosen to
exclude grain boundaries or damaged regions of the 1L-MoS2
flakes. The resulting spectra are presented in Figure 3b. When
situated on a bare substrate (blue curves), we observe emission
centered at around 668 nm ± 5 nm. In contrast to 1L-MoS2 on
bare substrate, 1L-MoS2 placed on top of the silicon
nanocylinder metasurfaces (red curves) shows not only
enhanced PL but also a spectral reshaping of the emission
band. We observe a spectral broadening and a shift of the
emission band maxima to shorter wavelengths around 655 nm
± 1 nm. The shift becomes eminent as a pronounced peak in
the relative PL enhancement spectra (green curve), defined as
the ratio PLmetasurf/PLsubstr. Additionally, the flat but non-
vanishing tails of the relative enhancement spectra are related
to a uniformly enhanced PL in the whole range of the emission
band. Note that the enhancement curves were smoothed using
a three-pixel binning of the wavelength resolution of the
spectrometer for better visibility in the plot.
Next, we aim to identify the physical origin of the
enhancement and spectral reshaping by considering photonic
influences from the resonant metasurfaces, strain modulations
from the nanostructured topography, and electronic influences
by unintentional doping from the substrate materials. We
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performed additional measurements and data analysis in order
to check for their individual contributions to the observed
changes in PL. First, we quantified the reshaping by employing
a multi-Lorentzian fitting scheme to the measured PL spectra
from 1L-MoS2 supported by bare substrate, as well as by
silicon nanocylinder metasurfaces of varying diameters. For all
samples, two dominant contributions can be identified, and
resulting fit parameters of a double-Lorentzian model show
peak positions at 655 nm ± 2 nm and 670 nm ± 3 nm and full-
widths at half-maximum (fwhm) of 17 nm ± 2 nm and 38 nm
± 7 nm, respectively. The well reproduced peak positions and
widths throughout all samples suggest a global reason common
to all samples leading to the observed reshaping. In agreement
with previously reported values,5 we attribute the peak at the
shorter wavelength to neutral A-excitonic (X) emission of 1L-
MoS2. Due to the red-shift of the center wavelength and the
broadening of the peak width, we attribute the second peak to
negatively charged A-trionic (T) emission induced by
unintentional n-doping mediated by the substrate material.47,48
Even though strain modulations can lead to similar changes
(red-shift and broadening) in the emission spectrum of 1L-
TMDs,49 we exclude macroscopic strain as dominant cause for
the occurrence of the second peak by Raman spectroscopy (see
Supporting Information). We quantified the intensity con-
tributions of the exciton species 0X and of the trion species 0T
by integrating the respective Lorentzian contributions within
their fwhm’s. Their relative spectral weight in the overall
observed emission is defined as wX/T = 0X/T/(0X + 0T). It
was measured for 1L-MoS2 on bare substrates as well as on top
of different silicon nanocylinder metasurfaces and is shown in
Figure 4a. For 1L-MoS2 on bare substrates, we observe a
dominant trion species, whereas for 1L-MoS2 supported by the
metasurfaces both exciton and trion species are of the same
order of brightness. Across all samples, the spectral weight of
the exciton species gets increased up to wX(metasurface) =
0.65 and a relative enhancement of the excitonic species up to
wX(metasurface)/wX(substrate) = 14 is observed, which can be
explained by the fact that the metasurfaces provide a regular
pattern of pillars supporting the 1L-MoS2 wherever they are
positioned directly above individual nanocylinders but
suspending the 1L-MoS2 in between nanocylinders of adjacent
unit cells. Hence, the freestanding 1L-MoS2 is not efficiently n-
doped and exhibits dominant neutral excitonic emission. From
purely geometric considerations, an even higher relative
enhancement of the excitonic species would be expected,
pointing toward residual doping of the freestanding 1L-MoS2
due to sample impurities. We further calculated the absolute
enhancement factors ηX/T = 0 metasurf
X/T /0 substr
X/T of the exciton
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Figure 5. Measured back-focal plane images of the photoluminescence emitted by 1L-MoS2 flakes on top of silicon nanocylinder metasurfaces with
diameters D = 240, 260, 275, and 300 nm collected with a 660 nm ± 5 nm bandpass filter.
(red curve) and trion (blue curve) populations mediated by
the silicon nanocylinder metasurfaces, as shown in Figure 4b. A
drastic enhancement of the absolute exciton emission up to a
factor of 170 is observed, strongly exceeding the aforemen-
tioned relative enhancement up to a factor of 14 due to the
repopulation of exciton and trion species. However, as shown
by Shin et al.,50 the surface roughness of amorphous substrates
can strongly influence the radiation efficiency of 1L-MoS2. By
random microscopic strain modulation on the amorphous
surface, the band structure of the supported 1L-MoS2 can
locally be modified resulting in a transition from a direct to an
indirect band gap material. Accordingly, freestanding 1L-MoS2
shows an up to 2 orders of magnitude higher radiation
efficiency, leading to the strong enhancement observed in our
experiments. For the trionic emission we observe an absolute
enhancement of up to 11 despite the relative depopulation of
the trion contribution in 1L-MoS2 situated on top of the
metasurfaces. Following the explanation above, this might
partly suggest a better surface quality of the nanostructured
silicon compared to the amorphous glass substrate which, as a
result of the etching process during the fabrication of the
silicon nanostructures, is expected to have a high surface
roughness. Further, we also need to consider the photonic
influence of the substrate itself which, due to its higher
refractive index, provides a higher density of photonic states
compared to air. Consequently, the emission efficiency can be
increased but, more importantly, the emitted radiation is
mainly directed into the substrate halfspace.51 This effect is
reduced for 1L-MoS2 situated some distance away when being
supported by the metasurfaces and, hence, leading to an
increased emission into the air halfspace, that is, the collection
side in our experiments. We also checked for a possible
photonic influence on the observed change of the PL spectra of
1L-MoS2 mediated by the resonant silicon metasurfaces.
However, from Figure 4b, no pronounced systematic depend-
ency of the observed enhancement factors on the nanocylinder
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diameter and supported resonances is apparent. We attribute
this to a combination of two factors. First, the radiative rate
enhancement is expected to be rather low for the considered
sample geometry.52 Second, slight differences in the 1L-MoS2
sample quality might be introduced during the wet transfer
process, making a comparison of the absolute enhancement
values across many flakes and samples difficult. Note that slight
changes in the weak photoluminescence signal emitted from
1L-MoS2 on bare substrate can lead to stronger variations in
the calculated enhancement factors as the emission from 1L-
MoS2 on bare substrate is used as reference.
■ DIRECTIONAL SHAPING OF EMISSION
While the resonant-photonic influence of the metasurface on
the emission spectra is weak, its influence on the 1L-MoS2
emission pattern remains to be investigated. We analyzed the
directionality of emission by back-focal plane (BFP) imaging of
the PL from the hybrid structures consisting of 1L-MoS2 on
silicon nanocylinder metasurfaces. BFP images were recorded
using a home-built setup with a 532 nm continuous wave
excitation laser and a 100×/0.73NA focusing objective. The
average laser power at the sample position was 0.8 mW. The
same objective was used for collecting the signal in reflection.
The signal was then coupled into a dedicated lens system for
imaging the back-focal plane of the objective onto a charge-
coupled device (CCD) camera. The collected light was filtered
using a 660 nm ± 5 nm bandpass filter. The experimental
results for the same four metasurfaces as presented above are
shown in Figure 5. For all measurements we observe a 4-fold
symmetric pattern in the measured BFP images of 1L-MoS2 on
top of silicon nanocylinder metasurfaces reflecting the
symmetry of the underlying nanostructures. However, strong
changes occur for the different nanocylinder diameters with
respect to the actual angular intensity distributions. To further
understand the measurement results, we analyzed the BFP
pattern regarding the influence of the resonators (nanocylinder
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diameter) and the lattice (square array arrangement). Starting
with the influence of the lattice, we analyzed the presence of
propagating lattice modes for different emission directions. For
a fixed wavelength (λ = 660 nm), as defined by the bandpass
filter used for the BFP measurements, we calculated the
number of propagating lattice modes for different emission
directions (θ,φ) and respective points in the back-focal plane
(kx,ky) = k0(sin(θ)cos(φ),sin(θ)sin(φ)). Regions of the back-
focal plane with a constant number of propagating lattice
modes accurately describe the underlying pattern in the
measured BFP images (see Supporting Information for
details). However, this simple analytical consideration cannot
make any predictions for the amount of light which is emitted
into the directions (θ,φ) due to the presence of the resonant
scatterers. To this end, the actual farfield pattern from each
unit cell needs to be considered, which will be dominated by
the scattering properties of the nanocylinders. As seen in the
measurements, for increasing nanocylinder diameter D, the PL
gets redirected more strongly toward the collection objective,
until the main lobe of the emission is directed normal to the
metasurface by sweeping the resonance with significant
quadrupole contribution of the nanocylinders into spectral
overlap with the 1L-MoS2 emission band maximum. Hence,
the radiation pattern directed into the air half space can be
tailored from emission under very large angles (off-resonant
case) to emission directed preferentially out of the substrate
plane (resonant case).
■ *
CONCLUSION
We have demonstrated experimentally the integration of CVD-
grown 1L-MoS2 with silicon nanocylinder metasurfaces and
have studied the influences of the electronic and photonic
environment on the spectral and directional properties of the
emitted photoluminescence. The observed spectral reshaping
and strong enhancement of the measured photoluminescence
spectra have been attributed to the charge transfer mediated
repopulation of excitons and trions as well as the freestanding
nature of 1L-MoS2 on silicon nanocylinder metasurfaces. Most
importantly, by tuning a metasurface resonance with significant
quadrupole contribution to spectrally overlap with the
emission band maximum of 1L-MoS2, a preferential emission
out of the metasurface plane could be achieved. By this, we
have demonstrated an efficient platform for accessing the
strong emission from freestanding TMD monolayers being
directed out of the substrate plane allowing for light collection
with simple low-NA optics, a crucial step for integrating TMD
monolayers in large-scale photonic applications.
■
METHODS
CVD Growth of Monolayer MoS2. 1L-MoS2 flakes were
grown by chemical vapor deposition on thermally oxidized
silicon substrates (Sil’tronix, oxide thickness 300 nm, rough-
ness < 0.2 nm RMS). After cleaning the growth substrates by
ultrasonication in acetone for 5 min followed by washing in
isopropanol, they were placed face down in a two-zone tube
furnace with a tube diameter of 55 mm. Two alumina boats,
one containing 200 mg of sulfur powder (99.98%, Sigma-
Aldrich), the other containing ∼1 μg MoO3 powder (99.97%,
Sigma-Aldrich), were placed in the first and second zone of the
tube furnace, respectively, such that the substrates were facing
the MoO3 precursors. Under atmospheric pressure and a
constant argon flow of 50 cm3 min−1, the second zone
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containing the MoO3 and the substrates was heated to the
growth temperature of 750 °C at a rate of 40 °C min−1 and
held at that temperature for 15 min. The heating of the first
zone containing the sulfur was controlled such that it reaches
200 °C at the same time when the second zone reaches 750
°C. After the growth, the two zones were allowed to cool down
slowly by turning off the furnace until the second zone reached
a temperature of 350 °C, followed by a rapid cool down to
room temperature by opening the tube furnace.
Fabrication of Silicon Metasurfaces. For fabrication of
the silicon metasurfaces, we first deposited thin films of
hydrogenated amorphous silicon (a-Si:H) with a thickness of
188 nm on standard microscope coverslips (borosilicate glass)
using plasma-enhanced chemical vapor deposition at a
temperature of 250 °C. Afterward, the substrates were spin-
coated with the negative-tone electron-beam resist maN-2403.
The nanocylinders were then defined by electron-beam
lithography in combination with inductively coupled plasma
etching of the silicon thin film using the developed electron-
beam resist as an etch mask. As etch gases, we used sulfur
hexafluoride (SF6, 1.8 sccm) and fluoroform (CHF3, 50 sccm).
Etching was performed at 20 °C with 10 mTorr at 500 W
induction power and 15 W bias power. Finally, residual resist
and organic solvent residue left on the sample were removed
using an oxygen plasma.
■ ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsphoto-
nics.8b01771.
Raman (Figure S1) and second-harmonic (Figure S2)
analysis of transferred 1L-MoS2 flakes. Discussion of the
lattice influence on measured back-focal plane images
(Figure S3). Numerically calculated metasurface trans-
mittance and corresponding multipole decomposition
(Figure S4) (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: tobias.bucher@uni-jena.de.
ORCID
Tobias Bucher: 0000-0003-1335-0432
Aleksandr Vaskin: 0000-0002-3014-1002
Franz J. F. Löchner: 0000-0002-8003-7916
Stefan Fasold: 0000-0001-5330-2465
Yuri S. Kivshar: 0000-0002-3410-812X
Isabelle Staude: 0000-0001-8021-572X
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
Financial support by the Thuringian State Government within
its ProExcellence initiative (ACP2020) and by the German
Research Foundation (STA 1426/2-1) is gratefully acknowl-
edged. This research was partly funded by the German
Ministry of Education and Research (BMBF) under the project
identifier 13N14147; responsibility for the content of this work
resides with the authors. Furthermore, the authors acknowl-
edge their participation in the Erasmus Mundus NANOPHI
project, Contract Number 2013 5659/002-001. Y.S.K.
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acknowledges support from the Humboldt Foundation. F.J.F.L.
has been funded by the German Research Foundation (DFG)
through the International Research Training Group (IRTG)
2101. This research is supported by an Australian Government
Research Training Program (RTP) Scholarship. This work was
performed in part at the ACT node of the Australian National
Fabrication Facility, a company established under the National
Collaborative Research Infrastructure Strategy to provide
nano- and microfabrication facilities for Australian researchers.
This project has also received funding from the joint European
Unions Horizon 2020 and DFG research and innovation
programme FLAG-ERA under a Grant TU149/9-1. We thank
Stephanie Höppener and Ulrich S. Schubert for enabling our
Raman spectroscopy and microscopy studies at the JCSM.
■
REFERENCES
(1) Zeng, H.; Cui, X. An optical spectroscopic study on two-
dimensional group-VI transition metal dichalcogenides. Chem. Soc.
Rev. 2015, 44, 2629−2642.
(2) Mak, K. F.; Shan, J. Photonics and optoelectronics of 2D
semiconductor transition metal dichalcogenides. Nat. Photonics 2016,
10, 216.
(3) Schaibley, J. R.; Yu, H.; Clark, G.; Rivera, P.; Ross, J. S.; Seyler,
K. L.; Yao, W.; Xu, X. Valleytronics in 2D materials. Nat. Rev. Mater.
2016, 1, 16055.
(4) Manzeli, S.; Ovchinnikov, D.; Pasquier, D.; Yazyev, O. V.; Kis, A.
2D transition metal dichalcogenides. Nat. Rev. Mater. 2017, 2, 17033.
(5) Mak, K. F.; Lee, C.; Hone, J.; Shan, J.; Heinz, T. F. Atomically
Thin MoS2: A New Direct-Gap Semiconductor. Phys. Rev. Lett. 2010,
105, 136805.
(6) Splendiani, A.; Sun, L.; Zhang, Y.; Li, T.; Kim, J.; Chim, C.-Y.;
Galli, G.; Wang, F. Emerging Photoluminescence in Monolayer MoS2.
Nano Lett. 2010, 10, 1271−1275.
(7) Mak, K. F.; He, K.; Lee, C.; Lee, G. H.; Hone, J.; Heinz, T. F.;
Shan, J. Tightly bound trions in monolayer MoS2. Nat. Mater. 2013,
12, 207.
(8) Shi, H.; Yan, R.; Bertolazzi, S.; Brivio, J.; Gao, B.; Kis, A.; Jena,
D.; Xing, H. G.; Huang, L. Exciton Dynamics in Suspended
Monolayer and Few-Layer MoS2 2D Crystals. ACS Nano 2013, 7,
1072−1080.
(9) Ugeda, M. M.; Bradley, A. J.; Shi, S.-F.; da Jornada, F. H.; Zhang,
Y.; Qiu, D. Y.; Ruan, W.; Mo, S.-K.; Hussain, Z.; Shen, Z.-X.; Wang,
F.; Louie, S. G.; Crommie, M. F. Giant bandgap renormalization and
excitonic effects in a monolayer transition metal dichalcogenide
semiconductor. Nat. Mater. 2014, 13, 1091.
(10) Molina-Sánchez, A.; Sangalli, D.; Hummer, K.; Marini, A.;
Wirtz, L. Effect of spin-orbit interaction on the optical spectra of
single-layer, double-layer, and bulk MoS2. Phys. Rev. B: Condens.
Matter Mater. Phys. 2013, 88, 045412.
(11) Cao, T.; Wang, G.; Han, W.; Ye, H.; Zhu, C.; Shi, J.; Niu, Q.;
Tan, P.; Wang, E.; Liu, B.; Feng, J. Valley-selective circular dichroism
of monolayer molybdenum disulphide. Nat. Commun. 2012, 3, 887.
(12) Zeng, H.; Dai, J.; Yao, W.; Xiao, D.; Cui, X. Valley polarization
in MoS2 monolayers by optical pumping. Nat. Nanotechnol. 2012, 7,
490.
(13) Mai, C.; Barrette, A.; Yu, Y.; Semenov, Y. G.; Kim, K. W.; Cao,
L.; Gundogdu, K. Many-Body Effects in Valleytronics: Direct
Measurement of Valley Lifetimes in Single-Layer MoS2. Nano Lett.
2014, 14, 202−206.
(14) Xiao, J.; Ye, Z.; Wang, Y.; Zhu, H.; Wang, Y.; Zhang, X.
Nonlinear optical selection rule based on valley-exciton locking in
monolayer WS2. Light: Sci. Appl. 2015, 4, No. e366.
(15) Bharadwaj, P.; Deutsch, B.; Novotny, L. Optical Antennas. Adv.
Opt. Photonics 2009, 1, 438−483.
(16) Barth, M.; Schietinger, S.; Schrüder, T.; Aichele, T.; Benson, O.
Controlled coupling of NV defect centers to plasmonic and photonic
nanostructures. J. Lumin. 2010, 130, 1628−1634.
1008
Article
(17) Beams, R.; Smith, D.; Johnson, T. W.; Oh, S.-H.; Novotny, L.;
Vamivakas, A. N. Nanoscale Fluorescence Lifetime Imaging of an
Optical Antenna with a Single Diamond NV Center. Nano Lett. 2013,
13, 3807−3811.
(18) Bauch, M.; Toma, K.; Toma, M.; Zhang, Q.; Dostalek, J.
Plasmon-Enhanced Fluorescence Biosensors: a Review. Plasmonics
2014, 9, 781−799.
(19) Krasnok, A.; Caldarola, M.; Bonod, N.; Alú, A. Spectroscopy
and Biosensing with Optically Resonant Dielectric Nanostructures.
Adv. Opt. Mater. 2018, 6, 1701094.
(20) Najmaei, S.; Mlayah, A.; Arbouet, A.; Girard, C.; Léotin, J.;
Lou, J. Plasmonic Pumping of Excitonic Photoluminescence in
Hybrid MoS2-Au Nanostructures. ACS Nano 2014, 8, 12682−12689.
(21) Goodfellow, K. M.; Beams, R.; Chakraborty, C.; Novotny, L.;
Vamivakas, A. N. Integrated nanophotonics based on nanowire
plasmons and atomically thin material. Optica 2014, 1, 149−152.
(22) Butun, S.; Tongay, S.; Aydin, K. Enhanced Light Emission from
Large-Area Monolayer MoS2 Using Plasmonic Nanodisc Arrays. Nano
Lett. 2015, 15, 2700−2704.
(23) Kern, J.; Trügler, A.; Niehues, I.; Ewering, J.; Schmidt, R.;
Schneider, R.; Najmaei, S.; George, A.; Zhang, J.; Lou, J.; Hohenester,
U.; Michaelis de Vasconcellos, S.; Bratschitsch, R. Nanoantenna-
Enhanced LightMatter Interaction in Atomically Thin WS2. ACS
Photonics 2015, 2, 1260−1265.
(24) Lee, B.; Park, J.; Han, G. H.; Ee, H.-S.; Naylor, C. H.; Liu, W.;
Johnson, A. C.; Agarwal, R. Fano Resonance and Spectrally Modified
Photoluminescence Enhancement in Monolayer MoS2 Integrated
with Plasmonic Nanoantenna Array. Nano Lett. 2015, 15, 3646−3653.
(25) Chen, H.; Yang, J.; Rusak, E.; Straubel, J.; Guo, R.; Myint, Y.
W.; Pei, J.; Decker, M.; Staude, I.; Rockstuhl, C.; Lu, Y.; Kivshar, Y. S.;
Neshev, D. Manipulation of photoluminescence of two-dimensional
MoSe2 by gold nanoantennas. Sci. Rep. 2016, 6, 22296.
(26) Chen, H.; Liu, M.; Xu, L.; Neshev, D. N. Valley-selective
directional emission from a transition-metal dichalcogenide mono-
layer mediated by a plasmonic nanoantenna. Beilstein J. Nanotechnol.
2018, 9, 780−788.
(27) Gong, S.-H.; Alpeggiani, F.; Sciacca, B.; Garnett, E. C.; Kuipers,
L. Nanoscale chiral valley-photon interface through optical spin-orbit
coupling. Science 2018, 359, 443−447.
(28) Sun, L.; Wang, C.-Y.; Krasnok, A.; Choi, J.; Shi, J.; Gomez-Diaz,
J. S.; Zepeda, A.; Gwo, S.; Shih, C.-K.; Alù, A.; Li, X. Separation of
valley excitons in a MoS2 monolayer using a subwavelength
asymmetric groove array. Nat. Photonics 2019, 13, 180−184.
(29) Sun, Y.; Liu, K.; Hong, X.; Chen, M.; Kim, J.; Shi, S.; Wu, J.;
Zettl, A.; Wang, F. Probing Local Strain at MX2-Metal Boundaries
with Surface Plasmon-Enhanced Raman Scattering. Nano Lett. 2014,
14, 5329−5334.
(30) Hwang, D. Y.; Suh, D. H. Evolution of a high local strain in
rolling up MoS2 sheets decorated with Ag and Au nanoparticles for
surface-enhanced Raman scattering. Nanotechnology 2017, 28,
025603.
(31) Bhanu, U.; Islam, M. R.; Tetard, L.; Khondaker, S. I.
Photoluminescence quenching in gold - MoS2 hybrid nanoflakes.
Sci. Rep. 2015, 4, 5575.
(32) Li, J.; Ji, Q.; Chu, S.; Zhang, Y.; Li, Y.; Gong, Q.; Liu, K.; Shi, K.
Tuning the photo-response in monolayer MoS2 by plasmonic nano-
antenna. Sci. Rep. 2016, 6, 23626.
(33) Kang, Y.; Najmaei, S.; Liu, Z.; Bao, Y.; Wang, Y.; Zhu, X.;
Halas, N. J.; Nordlander, P.; Ajayan, P. M.; Lou, J.; Fang, Z.
Plasmonic Hot Electron Induced Structural Phase Transition in a
MoS2 Monolayer. Adv. Mater. 2014, 26, 6467−6471.
(34) Decker, M.; Staude, I. Resonant dielectric nanostructures: a
low-loss platform for functional nanophotonics. J. Opt. 2016, 18,
103001.
(35) Kruk, S.; Kivshar, Y. Functional Meta-Optics and Nano-
photonics Governed by Mie Resonances. ACS Photonics 2017, 4,
2638−2649.
(36) Vaskin, A.; Bohn, J.; Chong, K. E.; Bucher, T.; Zilk, M.; Choi,
D.-Y.; Neshev, D. N.; Kivshar, Y. S.; Pertsch, T.; Staude, I. Directional
DOI: 10.1021/acsphotonics.8b01771
ACS Photonics 2019, 6, 1002−1009
ACS Photonics Article

and Spectral Shaping of Light Emission with Mie-Resonant Silicon

Nanoantenna Arrays. ACS Photonics 2018, 5, 1359−1364.
(37) Liu, S.; et al. Light-Emitting Metasurfaces: Simultaneous
Control of Spontaneous Emission and Far-Field Radiation. Nano Lett.
2018, 18, 6906−6914.
(38) Cihan, A. F.; Curto, A. G.; Raza, S.; Kik, P. G.; Brongersma, M.
L. Silicon Mie resonators for highly directional light emission from
monolayer MoS2. Nat. Photonics 2018, 12, 284−290.
(39) Chen, H.; Nanz, S.; Abass, A.; Yan, J.; Gao, T.; Choi, D.-Y.;
Kivshar, Y. S.; Rockstuhl, C.; Neshev, D. N. Enhanced Directional
Emission from Monolayer WSe2 Integrated onto a Multiresonant
Silicon-Based Photonic Structure. ACS Photonics 2017, 4, 3031−3038.
(40) Zhang, X.; Choi, S.; Wang, D.; Naylor, C. H.; Johnson, A. T.
C.; Cubukcu, E. Unidirectional Doubly Enhanced MoS2 Emission via
Photonic Fano Resonances. Nano Lett. 2017, 17, 6715−6720.
(41) Turchanin, A.; Beyer, A.; Nottbohm, C. T.; Zhang, X.; Stosch,
R.; Sologubenko, A.; Mayer, J.; Hinze, P.; Weimann, T.; Gölzhäuser,
A. One Nanometer Thin Carbon Nanosheets with Tunable
Conductivity and Stiffness. Adv. Mater. 2009, 21, 1233−1237.
(42) Winter, A.; George, A.; Neumann, C.; Tang, Z.; Mohn, M. J.;
Biskupek, J.; Masurkar, N.; Reddy, A. L. M.; Weimann, T.; Hübner,
U.; Kaiser, U.; Turchanin, A. Lateral heterostructures of two-
dimensional materials by electron-beam induced stitching. Carbon
2018, 128, 106−116.
(43) George, A.; Neumann, C.; Kaiser, D.; Mupparapu, R.; Lehnert,
T.; Hübner, U.; Tang, Z.; Winter, A.; Kaiser, U.; Staude, I.;
Turchanin, A. Controlled growth of transition metal dichalcogenide
monolayers using Knudsen-type effusion cells for the precursors. J.
Phys. Mater. 2019, 2, 016001.
(44) Chaste, J.; Missaoui, A.; Huang, S.; Henck, H.; Ben Aziza, Z.;
Ferlazzo, L.; Naylor, C.; Balan, A.; Johnson, A. T. C.; Braive, R.;
Ouerghi, A. Intrinsic Properties of Suspended MoS2 on SiO2/Si Pillar
Arrays for Nanomechanics and Optics. ACS Nano 2018, 12, 3235−
3242.
(45) Grahn, P.; Shevchenko, A.; Kaivola, M. Electromagnetic
multipole theory for optical nanomaterials. New J. Phys. 2012, 14,
093033.
(46) Angelova, P.; et al. A Universal Scheme to Convert Aromatic
Molecular Monolayers into Functional Carbon Nanomembranes.
ACS Nano 2013, 7, 6489−6497.
(47) Ross, J. S.; Wu, S.; Yu, H.; Ghimire, N. J.; Jones, A. M.;
Aivazian, G.; Yan, J.; Mandrus, D. G.; Xiao, D.; Yao, W.; Xu, X.
Electrical control of neutral and charged excitons in a monolayer
semiconductor. Nat. Commun. 2013, 4, 1474.
(48) Scheuschner, N.; Ochedowski, O.; Kaulitz, A.-M.; Gillen, R.;
Schleberger, M.; Maultzsch, J. Photoluminescence of freestanding
single- and few-layer MoS2. Phys. Rev. B: Condens. Matter Mater. Phys.
2014, 89, 125406.
(49) Schmidt, R.; Niehues, I.; Schneider, R.; Drüppel, M.; Deilmann,
T.; Rohlfing, M.; de Vasconcellos, S. M.; Castellanos-Gomez, A.;
Bratschitsch, R. Reversible uniaxial strain tuning in atomically thin
WSe2. 2D Mater. 2016, 3, 021011.
(50) Shin, B. G.; Han, G. H.; Yun, S. J.; Oh, H. M.; Bae, J. J.; Song,
Y. J.; Park, C.-Y.; Lee, Y. H. Indirect Bandgap Puddles in Monolayer
MoS2 by Substrate-Induced Local Strain. Adv. Mater. 2016, 28, 9378−
9384.
(51) Novotny, L.; Hecht, B. Principles of Nano-Optics; Cambridge
University Press, 2012.
(52) Bouchet, D.; Mivelle, M.; Proust, J.; Gallas, B.; Ozerov, I.;
Garcia-Parajo, M. F.; Gulinatti, A.; Rech, I.; De Wilde, Y.; Bonod, N.;
Krachmalnicoff, V.; Bidault, S. Enhancement and Inhibition of
Spontaneous Photon Emission by Resonant Silicon Nanoantennas.
Phys. Rev. Appl. 2016, 6, 064016.

1009 DOI: 10.1021/acsphotonics.8b01771

ACS Photonics 2019, 6, 1002−1009