Nanophotonics 2020; 9(10): 3089–3110

Review

Hyeongwoo Lee, Dong Yun Lee, Min Gu Kang, Yeonjeong Koo, Taehyun Kim and
Kyoung-Duck Park*

Tip-enhanced photoluminescence
nano-spectroscopy and nano-imaging
https://doi.org/10.1515/nanoph-2020-0079 1 Introduction
Received February 2, 2020; accepted April 9, 2020; published online
June 3, 2020
With fundamental understanding as well as engineering
studies for a range of organic and inorganic materials and
Abstract: Photoluminescence (PL), a photo-excited
hard and soft matter systems, we have achieved remark-
spontaneous emission process, provides a wealth of op-
able developments in modern device technologies. While
tical and electronic properties of materials, which enable
we mainly used bulk material systems for device applica-
microscopic and spectroscopic imaging, biomedical
tions in the past several decades [1], they have reached the
sensing and diagnosis, and a range of photonic device
limit in their electrical and optical properties, device per-
applications. However, conventional far-field PL mea-
formance, and application range. To overcome these lim-
surements have limitations in sensitivity and spatial res-
itations in bulk systems, on the one hand, a significant
olution, especially to investigate single nano-materials or
nano-scale dimension of them. In contrast, tip-enhanced effort is being made to discover unknown materials which
photoluminescence (TEPL) nano-spectroscopy provides show superior performance [2, 3]. On the other hand,
an extremely high sensitivity with <10 nm spatial resolu- dimensional reduction of conventional bulk systems gives
tion, which allows the desired nano-scale characteriza- rise to new physical phenomena, such as quantum
tions. With outstanding and unique optical properties, confinement effect [4] and dielectric screening effect [5],
low-dimensional quantum materials have recently which lead to significantly improved functions and prop-
attracted much attention, and TEPL characterizations, erties [6, 7]. Therefore, low-dimensional quantum mate-
i. e., probing and imaging, and even control at the nano- rials have emerged as appealing resources for the next
scale, have been extensively studied. In this review, we generation devices [8].
discuss the fundamental working mechanism of PL As the physical length scale of quantum materials is
enhancement by plasmonic tip, and then highlight recent reduced to the nano-scale, understanding physical proper-
advances in TEPL studies for low-dimensional quantum ties at their natural scale is desirable. To investigate struc-
materials. Finally, we discuss several remaining chal- tural properties of low-dimensional quantum materials,
lenges of TEPL nano-spectroscopy and nano-imaging, e. g., surface roughness, lattice structure, and structural
such as implementation in non-ambient media and in situ defects, scanning tunneling microscopy (STM) and trans-
environments, limitations in sample structure, and con- mission electron microscopy (TEM) are widely used [9–13].
trol of near-field polarization, with perspectives of the Specifically, STM is a unique local probe providing electrical
approach and its applications. properties [10, 11, 14] and spin information [15–17] with
Keywords: low-dimensional quantum materials; plasmonic atomic resolution. However, measurements are difficult in
tip; tip-enhanced photoluminescence (TEPL). ambient condition and careful sample preparation is needed
to obtain the desired information with high resolution [18].
In addition, optical properties associated with electronic
Hyeongwoo Lee and Dong Yun Lee are equally contributed. processes, such as absorption and photoluminescence (PL),
cannot be investigated with STM and TEM.
*Corresponding author: Kyoung-Duck Park, Department of Physics,
Ulsan National Institute of Science and Technology (UNIST), Ulsan, In contrast, confocal microscopy combined with PL
44919, South Korea, E-mail: [email protected]. https://orcid.org/ spectroscopy allows to investigate these optical re-
0000-0002-9302-9384 sponses in ambient condition, yet with diffraction limited
Hyeongwoo Lee, Dong Yun Lee, Min Gu Kang, Yeonjeong Koo
spatial resolution and low sensitivity [19]. To this end,
and Taehyun Kim: Department of Physics, Ulsan National Institute of
near-field PL measurement approach, i. e., tip-enhanced
Science and Technology (UNIST), Ulsan, 44919, South Korea

Open Access. © 2020 Hyeongwoo Lee et al., published by De Gruyter. This work is licensed under the Creative Commons Attribution 4.0
International License.
3090 H. Lee et al.: TEPL spectroscopy and imaging

PL (TEPL) nano-spectroscopy and -imaging [20], has The metal-coated optical fiber probe has a nano-aperture
emerged for multifunctional nano-characterizations of with a diameter of ∼50–100 nm, which determines a
low-dimensional quantum materials, since it provides spatial resolution of NSOM, to detect or to illuminate
high spatial resolution of ∼10 nm with high optical near-field signals on the surface of samples [27]. With a
sensitivity owing to the plasmonic nano-optical antenna high spatial resolution far beyond the diffraction limit,
effect [21, 22]. many groundbreaking works were allowed in physics [28,
In this review, we briefly describe technical limitations 29], chemistry [30, 31], biology [32, 33], and material
in far-field optical imaging and summarize near-field im- sciences [34–37].
aging methods from aperture fiber type approach to tip- However, against all expectations, the application
enhanced nano-spectroscopy and -imaging. Further, we range of NSOM had been highly limited due to the low
describe the principles and enhancement factor of TEPL. sensitivity, since the transmission intensity through the
We then discuss nano-scale field localization at the apex of NSOM probe is inversely proportional to the fourth power
plasmonic tip in various conditions, e. g., materials of a tip, of the aperture size [38, 39]. In addition, other problems of
substrates, and polarization, based on electromagnetic optical fibers, such as wavelength-selective optical loss,
simulation results. Next, we focus on highlighting recent polarization modification, and dispersion, also restricted
TEPL studies for low-dimensional materials, specifically the broad applications of NSOM. To overcome these con-
applications to 0-dimensional (0D), 1D, and 2D quantum straints of an optical fiber probe, an inverse approach using
systems. Lastly, we discuss several remaining challenges near-field scattering, so called apertureless NSOM
of TEPL nano-spectroscopy and nano-imaging, such as (ANSOM) or scattering-scanning near-field optical micro-
implementation in non-ambient media and in situ envi- scopy (s-SNOM), was proposed [29, 40–44]. In this method,
ronments, limitations in sample structure, and control of evanescent waves on the surface of a sample are scattered
near-field polarization, with perspectives of the approach by an apertureless tip and converted into propagating
and its further applications. waves, which provide a near-field image with a spatial
resolution of <10 nm in optimized conditions. This has been
a great step forward, but weak near-field scattering signal
2 Historical developments of near- was still a significant issue because image contrast and
field microscopies spatial resolution can be easily deteriorated due to the far-
field background.
In far-field spectroscopy and imaging, the Airy patterns At that time, plasmonic nano-materials (Au or Ag in
from two different objects are distinct and resolvable if the visible frequency) had gained great attention with
they are apart farther than the Rayleigh criterion [23]. To surface enhanced Raman scattering (SERS) studies, which
overcome this diffraction limit (λ/2NA, where λ is a showed single-molecule sensitivity [45, 46]. Similarly,
wavelength of light and NA is a numerical aperture of plasmonic tip has started to be used in s-SNOM to obtain
lens), near-field optical imaging techniques have the desired strong near-field signals. The first demonstra-
emerged. The original theoretical concept of high reso- tion was tip-enhanced Raman spectroscopy (TERS) [47–51]
lution near-field imaging was proposed by E. H. Synge in and this tip-enhanced nano-spectroscopy and -imaging
1928 [24]. He proposed to make a small aperture (diam- approach was extended widely to detect elastic [52, 53] and
eter of <10 nm) in thin metal film and use the transmitted other inelastic scattering [54, 55], as well as nonlinear op-
light through that aperture to illuminate a sample placed tical responses [56, 57]. Specifically, TEPL spectroscopy
near the nano-aperture. However, this innovative idea provides electronic properties of semiconducting materials
could not be practically implemented for a long time due at the nano-scale, such as quantum dots [58], quantum
to its several technological difficulties at that time, such wires [59], and transition metal dichalcogenides (TMDs)
as nano-fabrication, nano-precision positioning, and low [20]. Most studies showed highly enhanced PL signals, yet
sensitivity of an optical detector. Almost 60 years later, in the weak coupling regime. Recently, TEPL approach
this original idea of near-field imaging had been imple- further advanced to tip-enhanced strong coupling (TESC)
mented by the advent of a scanning probe microscopy spectroscopy using plasmonic tip-cavity at room tempera-
(SPM) technique [25, 26]. Near-field scanning optical mi- ture [60]. In brief, historical development in near-field mi-
croscopy (NSOM) is the first approach for measuring croscopy is summarized in Figure 1 and we focus on TEPL
near-field optical responses using an optical fiber probe. spectroscopy and its applications in this review.
 H. Lee et al.: TEPL spectroscopy and imaging 3091

Figure 1: (A) The brief experimental

schematics with spatial resolution for far-
field optical microscope, Synge’s
theoretical proposal, and near-field
scanning optical microscopy (NSOM). Δx
denotes spatial resolution. (B) Schematics
of scattering-type scanning near-field
optical microscopy (s-SNOM), tip-enhanced
nano-spectroscopy (TERS and TEPL), and
tip-enhanced strong coupling (TESC)
spectroscopy [37]. V/λ3 denotes mode
volume for an excitation wavelength.

3 TEPL mechanism and sample surface), an image dipole associated with the
localized surface charge is induced beneath the surface
enhancement factor at −d with the dielectric function of βsurf  (ϵsph [ω] − 1)/
(ϵsph [ω] + 1). Hence, the effective polarizability αef f and
Basically, field enhancement in plasmonic tips is attrib-
polarization pef f due to the dipole-dipole interaction can
uted to two phenomena as follows. First, electric charges
be expressed as
are highly concentrated in the vicinity of a plasmonic tip
due to the electrostatic lightning rod effect [61]. Second,
αsph 1 + βsurf 
when an external electromagnetic field, e. g., excitation αef f  , (2)
laser beam, is applied to the tip, optical fields are strongly 1 − αsph βsurf 16π(r + d)3 
localized at the apex due to the collective resonant oscil-
pef f  αef f ϵ0 Einc, z . (3)
lations of the electrons, i. e., localized surface plasmon
resonance (LSPR) effect [62]. The near-field localization at the apex of plasmonic tip
The LSPR of plasmonic tip can be understood with leads to much larger excitation rate for PL response of the
simple analytical models [37, 63, 58]. The tip is approxi- sample compared to that of conventional PL spectroscopy.
mated as a polarizable sphere with a radius r(≪λ) and In addition to the excitation rate, the spontaneous emission
frequency-dependent permittivity ϵsph [ω]. Based on the rate of the sample is also increased by the presence of
Clausius–Mossotti relation, the induced polarization of the plasmonic tip close to an emitter, known as the Purcell effect
sphere is defined by psph  αsph ϵ0 Einc , where Einc is the F p  (3/4π 2 )(λ/n)3 Q/V, where n is index of refraction of an
incident electric field. The polarizability αsph is given by optical cavity with the quality factor Q and mode volume V
ϵsph [ω] − 1 [65]. Even though a non-radiative energy transfer from the
αsph  4πr3
. (1) emitter to the plasmonic tip [66], i. e., PL quenching, occa-
ϵsph [ω] + 2
sionally occurs due to ohmic losses in the metal, PL signal is
Since the permittivity of Ag and Au nano-spheres generally enhanced by the plasmonic tip effect [67].
makes the denominator of Eq. (1) to be very small in the The enhancement factor EF of TEPL is estimated with
visible frequency, the polarizability, scattering cross-sec- contributions of the excitation rate and the spontaneous
tion (σscat ∝ α2sph ), and the induced polarization show emission rate [68]. In general, PL intensity is quantified by
resonance behaviors with nano-optical antenna effect. the product of the excitation rate Γex and the quantum effi-
When a plasmonic tip with Einc, z , approaches closely ciency η. The η can be expressed as η  k rad /(k rad + k nrad ),
to a sample or a substrate with a distance d, the polariz- where k rad is the radiative decay rate and k nrad is the non-
ability is understood with the coupled dipole model radiative decay rate. Accordingly, EF can be defined as the
[37, 63, 64]. If we assume the sphere as a point dipole with ratio between TEPL intensity and far-field PL intensity,
the dipole orientation in the z-axis (perpendicular to the given by
3092 H. Lee et al.: TEPL spectroscopy and imaging

Γex η plasmonic tip owing to the lightning rod effect [71, 83–88].
EF  TE
⋅ TE , (4)
ΓFF ex ηFF Since free electrons of a metal tip resonantly oscillate with
excitation field perpendicular to the surface, optical near-
where subscripts TE and FF denote tip-enhancement and
fields of Ez and Ex components are distributed at the tip
far-field. Tip-enhanced excitation rate can also be
apex, as shown in Figure 2A and B. Figure 2C shows the
expressed as ΓexTE ≅ (E TE /E FF ) with tip-enhanced electric
2
simulated optical field distribution at the apex of tips
field intensity. Note that TEPL enhancement was reported
made with different materials, such as Au, W, Si, and
as high as ∼6 × 105 with Au tip-cavity for dark excitons in
glass [70]. Au tip shows the highest field enhancement
WSe2 monolayer [69].
due to the LSPR effect. On the other hand, tungsten (W) tip
shows low field enhancement, which is comparable to Si
4 Field enhancement in plasmonic and glass tips, due to the strong damping of the field
tips caused by absorptive loss in a poor conductor.
The geometry of a plasmonic tip, such as the apex size
Field enhancement in plasmonic tips leads to the large and the cone angle, influences the field enhancement and
excitation rate for strong TERS and TEPL responses, which plasmon resonance. Figure 2D shows the calculated field
provide high spatial resolution imaging. To quantify the enhancement of Au tip at a 630 nm excitation as a function
enhanced field distribution at the tip apex, there have been of the tip-radius and the cone angle [70]. The field
numerous theoretical studies [70–75]. In this section, we enhancement is gradually increased ranging from 10 to 103
discuss field distribution and enhancement in various times as the radius is decreased for different cone angles.
conditions, e. g., tip material, substrate, and excitation Decreasing cone angle also gives rise to stronger field
polarization, with electromagnetic simulation results per- enhancement. In contrast, an opposite simulation result
formed by finite difference time domain (FDTD) or finite was reported by Zhang et al. [72]. They modeled the ge-
element method (FEM). ometry of Ag tip with infinite length and the fixed tip-radius
Photo-induced electronic responses of plasmonic tip of 20 nm, and simulated the field enhancement of the tip
are described by the dielectric function [76]. When an with cone angles of 15°, 20°, and 25°. As can be seen in
external field is applied to a plasmonic tip, the real part of Figure 2E, tips with larger cone angle show higher field
the dielectric function describes the polarization strength enhancement in the visible and near infrared regions. This
as a function of the excitation frequency, i. e., it de- behavior is similar to the field enhancement of biconical
termines a spectral resonance of the LSPR. The imaginary antennas [89]. A more sophisticated simulation with
part describes the optical losses, which determine the respect to both the cone angle and the excitation wave-
plasmon bandwidth [77–79]. Silver and gold tips are length was performed by Goncharenko et al. [73]. Figure 2F
commonly used for TERS and TEPL spectroscopy due to shows the spectral and cone angle dependence of the field
their low losses in the visible and near infrared fre- enhancement for Ag tip. For the increasing cone angle, the
quencies [70, 80–82]. Under the side-illumination with plsamon resonance is blue-shifted with the increasing field
p-polarized light (E-field parallel with respect to the tip- enhancement. However, at the normal excitation wave-
axis), optical field is strongly localized at the apex of length of 550 ∼ 650 nm for TERS and TEPL, sharp tips give

Figure 2: (A–B) Simulated Ez and Ex field

distributions of Au tip illuminated by p-
polarized light [71]. Copyright 2004 Optical
Society of America. (C) Simulated electric
field distribution of free-standing tips made
with various materials, such as Au, W, Si,
and glass [70]. (D–F) Simulated field
enhancement of plasmonic tips with
respect to the tip-radius, cone angle, and
excitation wavelength [70, 72, 73].
Reprinted with permission from [70].
Copyright (2008) American Chemical
Society. Copyright 2009 John Wiley & Sons,
Ltd [72]. Reprinted from [73], with the
permission of AIP Publishing.
 H. Lee et al.: TEPL spectroscopy and imaging 3093

the higher field enhancement. These inconsistent simula-

tion results [70, 72, 73] of cone angle dependence are
mainly due to the complex interplay of competing mech-
anisms on the surface charge density. When the cone angle
is increased, on the one hand, the surface charge density
and field enhancement are increased due to the decreased
value of the imaginary part of the metal dielectric function.
On the other hand, larger cone angle leads to enlarging the
surface area, which reduces the charge density and field
enhancement [73].
As we described in section 3, a substrate plays an
important role for the field enhancement due to the dipole-
dipole interaction [70, 72, 74, 75, 90–92]. Figure 3A shows a
variation of the field enhancement for different distances
ranging from 2 to 40 nm between Au tip and Au substrate
[70]. In this simulation, the tip-radius is set to 10 nm and an
excitation wavelength of 630 nm is used. The Au surface is
fixed at z = 0 nm and the variable tip position is located at
z = d positions. The field enhancement is dramatically
increased when the tip-substrate distance is decreased to a
few nanometers because the effective polarizability is
inversely proportional to the third power of the distance d,
as can be seen in Eq. (2). Specifically, the near-field inter-
action becomes effective when the tip-substrate distance is Figure 3: (A) Simulated variation of the field enhancement for different
distances ranging from 2 to 40 nm between Au tip and Au substrate. (B)
shorter than twice the radius of tip. As for the spatial dis-
Simulated lateral cross-sections of the enhanced optical field near
tribution, the field localization is stronger near the tip apex the Au surface for different tip-substrate distances. Reprinted with
compared to the Au surface based on the tip geometry and permission from [70]. Copyright (2008) American Chemical Society.
the coupled dipole model. Figure 3B clearly demonstrates
the lateral spatial distribution of the localized field. The earlier. Based on this feature, the side-illumination geom-
curves show lateral cross-sections of the enhanced optical etry is generally used for TERS [93–96] and TEPL [20] ex-
field near the Au surface for different tip-substrate dis- periments. Some research groups use the bottom-
tances. This result indicates that the tip-substrate distance illumination geometry to measure transparent samples [53,
significantly influences the spatial resolution in near-field 97]. In this case, since the excitation direction is fixed along
imaging. Table 1 shows the simulated field enhancement in to the tip-axis, a linearly polarized excitation beam is not
the plasmonic gap between Ag tip and different substrates suitable for the large field enhancement, as can be seen in
[74]. As expected, good conductor substrates give stronger Figure 4A. Therefore, a radially polarized beam is used to
field enhancement due to the higher surface charge density. effectively excite plasmonic tip. Figure 4E and F shows the
In addition to the tip-material, geometry, and substrate field intensity distribution with a radially polarized light
effects, the field enhancement is also affected by the from the bottom. In this case, the enhancement factor is
propagation direction and polarization of the excitation much higher than the side-illumination case using a line-
field [75]. Figure 4 shows optical field intensity distribution arly polarized light because the excitation field is more
at the apex of Ag tip at an excitation wavelength of 532 nm effectively spatially localized near the tip, as also can be
for different polarization conditions. When the excitation seen in far-field studies [98–102]. Note that the field
polarization is perpendicular with respect to the tip-axis, enhancement factor can be additionally increased by using
the field enhancement on the tip shaft is more significant the tilted tip geometry [57].
compared to the tip apex as shown in Figure 4A. In
contrast, for the excitation polarization in parallel with the
tip-axis, optical near-fields are strongly localized at the 5 Applications to 0D materials
apex with ∼10 times larger field intensity (Figure 4C).
Figure 4B and D shows stronger field enhancement and Weak optical responses from 0D materials, such as single
localization due to the substrate effect, as we discussed molecules and nano-crystals, are generally hard to detect
3094 H. Lee et al.: TEPL spectroscopy and imaging

Table : Simulated field enhancement in the plasmonic gap between Ag tip and different substrates. FE: finite element, BCB: brilliant cresyl
blue []. Copyright  by John Wiley & Sons, Inc. Reprinted by permission of John Wiley & Sons, Inc.

Metal E (FDTD) E (FDTD) E (FE) TERS (BCB) TERS (PhS)

Au     
Cu . . . ± .
Ag . . . . ± . .
Al . .
Pd . .
Pt . .
Ni . . . ± . .
Cr . .
Ti . . . ± .
Mo . . . ± .
W . .
AlOname .
SiOnam . .
Tip only . .

Figure 4: Electric field intensity distribution

at the apex of Ag tip at an excitation
wavelength of 532 nm for different
polarization conditions. The bottom-
illumination with a linearly polarized light
without (A) and with Au substrate (B). The
side-illumination with a linearly polarized
light without (C) and with Au substrate (D).
The bottom-illumination with a radially
polarized light without (E) and with Au
substrate (F) [75]. Copyright (2013) Optical
Society of America.

with conventional optical microscopy [103, 104]. While a molecules were carefully selected for a photo-stability,
quantum dot, 0D semiconducting material which has and rapid spectral diffusions at room temperature were
smaller diameter than exciton Bohr radius, gives strong PL suppressed by coating the molecules with thin poly-
responses [105], characterizing intrinsic optical properties methylmethacrylate (PMMA) film. Although this experi-
of a single dot in interacting environments with diffraction ment provided many interesting optical properties of
limited spectroscopic methods remains challenging. single molecules, e. g., non-radiative energy transfer and
Therefore, tip-enhanced optical characterizations of 0D dipole orientation, luminescence signal through the
materials were highly desired in the early stage of near- nano-aperture was obviously too weak to extend its
field optics. In this section, we discuss tip-enhanced PL measurement range to broad applications. Therefore,
measurement of single molecules and quantum dots [103, NSOM measurement for single molecules could be per-
106–111]. In addition, we discuss recent observation of PL formed by only a few research groups [104, 113, 114], and
energy splitting of single quantum dots in the strong the necessity of higher sensitivity near-field microscopy,
coupling regime at room temperature [58, 60]. such as an ANSOM or a scattering-type NSOM, started
Since the first observation of single molecule signals blooming. Note that while the ANSOM was not proposed
from a solid crystal at cryogenic temperature by Moerner at that time, field-enhancement at the apex of illuminated
et al. [112], Betzig et al. demonstrated that a single-mole- tip was already studied even earlier than Betzig’s single-
cule detection is even allowed in ambient conditions us- molecule NSOM experiment [115].
ing illumination-mode NSOM [104]. In that experiment, Several years later, Azoulay et al. presented spectro-
an apertured fiber probe (diameter of <100 nm) and scopic measurements of single-molecule fluorescence us-
avalanche photodiode (APD) were used to measure PL ing Si AFM tip [103]. A home-built confocal microscope
from individual carboncyanine dye molecules. These setup was combined with an AFM to obtain enhanced
 H. Lee et al.: TEPL spectroscopy and imaging 3095

fluorescence from single molecules through localized aperture (TOA) NSOM [110]. This approach can improve
excitation field at the tip apex. Figure 5 shows measured optical sensitivity and spatial resolution in NSOM imaging
fluorescence spectra of Rh640 molecules in PVB thin film via field localization of the metallic tip. Furthermore, far-
when the tip is approached (A) to and retracted (B) from the field background noise, a general problem in apertureless
sample. Since they used a non-plasmonic tip for this NSOM, is highly suppressed by collecting near-field signals
experiment, the fluorescence enhancement factor was not through the fiber-type probe. With this TOA probe, Frey
very large. In addition, the excitation polarization and et al. investigated fluorescence properties of single Cy3
molecular orientation were not carefully controlled, as well molecules with a spatial resolution of 10 nm [110, 116].
as 30 nm thick PVB film gave unavoidable limitation in tip- Despite these advantages, TOA probe is not widely used
sample distance. Notwithstanding, it was the valuable first due to the complex fabrication process.
demonstration of spectral analysis for tip-enhanced single- While scattering signals in ANSOM are generally
molecule fluorescence. stronger than near-field signals through a nano-aperture,
As seen in these early stage works, both apertured and the detected scattering light is basically a mixture of near-
ANSOMs are capable of measuring single molecule fluo- field and far-field signals. The unwanted far-field signal is
rescence, yet with low optical sensitivity. To overcome a background noise which can reduce a spatial resolution
these technical limitations, a number of innovative ap- in near-field imaging, as aforementioned. To solve this
proaches were presented. For example, Frey et al. showed a problem, Ma et al. developed a novel phase filter to selec-
hybrid mode of apertured and ANSOM by fabricating tively detect near-field fluorescence [106]. In the ANSOM
metallic tip to an optical fiber probe, so-called tip-on- setup with a tapping mode AFM (∼80 kHz) and an inverted
microscope optics, they characterized the tip-oscillation
phase and fluorescence intensity from Cy3 molecules when
the distance between tip and sample is sinusoidally
changed. By analyzing correlation between the tip phase
and fluorescence intensity, they found a specific phase
which gives maximum fluorescence enhancement.
Through this phase filter, a signal-to-noise ratio (SNR) was
improved ∼6 times for Cy3 single molecules. In addition,
the measured near-field fluorescence image showed a
spatial resolution of 8.2 nm, which is even higher resolu-
tion than AFM topography, as shown in Figure 5B–E.
Based on these efforts for the advanced instrumenta-
tion, the application range of NSOM was extended to bio-
logical imaging in aqueous environments with single-
molecule sensitivity. The main difficulty of NSOM opera-
tion in liquid is low Q-factor of tuning fork or AFM canti-
lever. To achieve high Q-factor, Höppener and Novotny
used normal-mode AFM based on tuning fork and attached
a gold nano-sphere onto the apex of Si tip [108, 117]. This
approach enabled to resolve individual Ca2+ pumps and
PMCA4 proteins on the cell membrane in PBS solution with
50 nm spatial resolutions [108, 117]. The inverse approach
of near-field biological imaging in liquid was also
demonstrated [33]. This study showed a conventional
NSOM probe can be operated in liquid by increasing Q-
factor with a novel resonance control method. Further, the
single-molecule level sensitivity from membrane proteins
Figure 5: (A) Fluorescence spectra of Cy3 molecules when Si tip is could be achieved by labeling plasmonic gold nano-
approached (top) and retracted from sample (bottom). (B–C) Tip-
particles onto the target biomolecules.
induced fluorescence images of Cy3 molecules (pair) in different
positions. (D–E) Corresponding AFM images of fluorescence images
The another significant TEPL application for 0D mate-
(B) and (C). The scale bars in (B–E) are 50 nm. Reprinted [106] with rials is a quantum dot. The first experiment of fluorescence
permission from Copyright 2006 by the American Physical Society. enhancement at the Si tip apex was demonstrated by
3096 H. Lee et al.: TEPL spectroscopy and imaging

Protasenko et al. in 2002 [109]. They prepared ZnS over

coated CdSe quantum dots on the prism surface, and excited
the sample with a 488 nm, vertically polarized laser to
effectively suppress the far-field background with the
evanescent illumination. The Si tip was approached to the
quantum dots with a tip-sample distance of 5–10 nm in non-
contact mode, and the tip-scattered fluorescence signal was
measured using a band-pass filter and an APD. The
enhancement factor of tip-induced fluorescence was as high
as 5-fold for a single isolated quantum dot, and the fluo-
rescence intensity difference for a tip-induced QD and
adjacent QD was obtained as high as 90-fold due to the
destructive interference between them. This effect also led to
high spatial resolution of 30–40 nm in near-field fluores-
cence imaging.
In addition, in this early stage study, they found that a
range of complex optical processes can occur in the tip-
sample gap including fluorescence enhancement and
quenching dependent on tip preparation condition, materials
of tip, and distance between tip and sample. Therefore, TEPL
experiment should be carried out carefully, and there are a lot
of optical processes to be investigated in the tip-emitter in-
teractions. Note that quenching effect or non-radiative charge
transfer to the tip was one significant issue in the early stage Figure 6: (A) Near-field fluorescence image of CdSe/ZnS quantum
dots using Si tip. (B) Distance dependent fluorescence intensity
of near-field fluorescence spectroscopy and imaging. Tradi-
between tip and different samples. The distance dependent curves
tionally, an intermittent contact mode with an optimized gap with solid circles, open squares, and open triangles are for a quantum
between tip and sample was used to minimize this effect with dot of 5 nm diameter, a nano-rod of 20 nm length, and a dye-doped
reasonably high fluorescence enhancement [118, 119]. latex sphere of 5 nm diameter, respectively. Reprinted [111] with
In addition to the quenching, another main difficulty of permission from Copyright 2004 by the American Physical Society.
TEPL approach is the far-field background. Since the detec-
ted signal is a mixture of far-field and near-field responses, sphere. This result shows that spatial confinement of near-
disrupting far-field signal reduces a spatial resolution when field fluorescence regarding tip-induced enhancement is
the enhancement factor is not high enough. To overcome this dependent on the size and shape of sample. The half-
limitation, Gerton et al. demonstrated a method to selectively maximum of distance dependent TEPL intensity was derived
collect near-field signal decoupled from the far-field back- as 1.7 nm for a quantum dot which is several times smaller
ground by making a large tapping amplitude in intermittent value than previous conventional tip-enhanced PL ap-
contact mode [111]. When the tip is intermittently contacted proaches [116, 120–123].
to the quantum dots, the near-field excitation rate is maxi- Quantum dots are widely used not only as bright op-
mized as well as near-field PL component. On the contrary, tical sources for modern display devices [124], but also as
the far-field component out of total detected PL signals is the solid-state single emitters for quantum information devices
highest rate when the distance between tip and sample is at [125]. Up to present, most TEPL studies of quantum dots
maximum. Therefore, by demodulating near-field PL signals were performed in the weak coupling regime, where
with tip oscillating frequency, far-field background can be coupling occurs between exciton and plasmon. Recently,
effectively suppressed. Using this approach, Gerton et al. the coupling strength between them was extended to
measured tip-enhanced fluorescence for single isolated strong coupling regime even at room temperature using
CdSe–ZnS core-shell quantum dot, and achieved sub-10 nm TEPL approach [58, 60], which provides new insight into
spatial resolution by effectively suppressing the far-field dynamic quantum photonic devices. As illustrated in
signal, as shown in Figure 6A [111]. Figure 6B shows fluo- Figure 7A and B, the experimental methods are roughly the
rescence intensity as a function of tip-sample distance for same as typical TEPL nano-spectroscopy. The key factor to
three different types of nano-crystals, such as a CdSe–ZnS reach the strong coupling regime is the small mode volume
quantum dot, a CdSe–ZnS nanorod, and a dye-doped latex V of the tip-cavity because the coupling strength g is
 H. Lee et al.: TEPL spectroscopy and imaging 3097

√
proportional to 1/ V . As seen in Figure 7A, Groß et al. retracted from a single quantum dot [60]. Prior to these
fabricated slit-like (<10 nm) plasmonic nano-resonator at a strong coupling works, most tip-enhanced microscopy
corner of a gold flake, which is mounted at the apex of a tip- studies tried to avoid perturbation of sample properties
less AFM cantilever. When single isolated colloidal induced by strong plasmon field. On the other hand, these
CdSeTe/ZnS quantum dots are positioned in the small works provide a new paradigm of tip-enhanced microscopy
mode volume of this nano-resonator, they could observe in the deliberate perturbative environments.
energy-split multiple-peaks in the measured TEPL spectra
with the coupling strength of up to 110 meV. They identified
that these results are attributed to collective coupling of a 6 Applications to 1D materials
band-edge multiplet of states [58]. A similar but reverse
approach was demonstrated by Park et al. using an elec- While 0D quantum materials are important building blocks
trochemically etched gold tip and gold substrate [60]. In as an appealing optical source for high performance op-
the experiment, drop-casted single isolated CdSe/ZnS toelectronic device applications [60], a separated wave-
quantum dots were used as the single emitter. To protect guide structure is needed to transport optical or electronic
quantum dots from photo-oxidation, gold substrate and information of them. In contrast, 1D quantum materials are
quantum dots were coated with a thin 0.5 nm Al2O3 the most ideal platforms because they not only have strong
capping layer. Using a scanning Au tip operated by a shear- quantum confinement effect in horizontal axis but also can
force AFM mode, they could find single quantum dots and transfer charges, photons, or other information along the
control cavity mode volume dynamically. In addition, the longitudinal axis [126]. Therefore, 1D materials have
tilted tip geometry was used to have maximum field attracted much attentions as a miniaturized photonic de-
enhancement, as seen in Figure 7B. vice in the new emerging field of integrated on-chip in-
Park et al. nicely demonstrated PL spectra of quantum formation technology [127]. To understand optical and
dot excitons, cavity plasmon, as well as TEPL spectra in the electronic properties of 1D materials, a range of PL char-
weak and strong coupling regime, as shown in Figure 8A. acterization studies have been performed, yet with
When the cavity loss is larger than the coupling strength, diffraction-limited far-field spectroscopy and imaging
TEPL spectrum is similar to far-field PL of a quantum dot. which cannot provide information on nano-scale hetero-
On the contrary, when the coupling strength exceeds the geneity [59]. In this section, we discuss TEPL applications
plasmonic cavity loss, two clear TEPL peak are observed on 1D quantum materials which show distinct nano-scale
due to the large PL enhancement and Rabi splitting (green). optical properties compared to far-field investigations.
The maximum mode splitting they observed was Single-walled carbon nanotubes (SWCNTs) are hollow
∼160 meV at room temperature. In addition, from cylinder shape 1D carbon materials with a diameter of
measured TEPL evolution of strongly coupled plexciton, typically smaller than 2 nm [59]. Semiconducting SWCNTs
they found that the typical blinking behavior of a quantum have low radiative recombination rate and short emission
dot is also observed in the strong coupling regime lifetime of photo-excited state due to their unique elec-
(Figure 8B). The main beauty of their works is tuning the tronic band structure and dimensional effect [59]. In
coupling strength by controlling the nano-cavity mode addition, PL energy of SWCNTs shows inverse proportional
volume through the dynamic tip-sample distance control behavior with respect to the nanotube diameter [59].
of AFM. Figure 8C shows the transition from strong Böhmler et al. demonstrated that these emission properties
coupling to weak coupling when Au tip is vertically can be locally controlled at the nano-scale by using a nano-

Figure 7: Tip-enhanced photoluminescence

spectroscopy experiments for single quantum
dots in the strong coupling regime
demonstrated by two different groups. (A)
Illustration of an experiment with fabricated
plasmonic nanoresonator (PNR) and measured
far-field and near-field PL spectra of CdSeTe/
ZnS quantum dots. Inset: SEM image of PNR.
The scale bar is 100 nm. (B) Illustration of an
experiment with a tilted Au tip geometry. From
[58, 60]. Reprinted with permission from
AAAS.
3098 H. Lee et al.: TEPL spectroscopy and imaging

Figure 8: (A) Far-field PL and TEPL spectra of a

single CdSe/ZnS quantum dot in the weak
and strong coupling regimes. Gap plasmon
response without a quantum dot is shown
with an orange curve. The dots and lines
indicate measured data and theoretical
model fit, respectively. (B) Time-series of
far-field PL spectra of quantum dot excitons
(top) and plexciton TEPL spectra for a single
quantum dot (bottom). (C) Distance
dependent TEPL spectra when the tip is
retracted from a single quantum dot from
0 to 4 nm. From [60]. Reprinted with
permission from AAAS.

optical antenna-tip [59]. Figure 9A shows a schematic di- PL radiation pattern, far-field PL radiation pattern shows
agram of the measurement setup equipped with an inver- linearly polarized behavior as shown in Figure 9F.
ted mode microscope and a tuning fork based shear force Figure 9G shows the same result as Figure 9F, but the
AFM. The SWCNTs are excited by radially polarized 594 nm intensity scale is changed for better comparison with
or 633 nm continuous wave HeNe laser, and the back- Figure 9E. From these results we know that when Au tip is
scattered far-field PL or TEPL signals are detected by an approached to the SWCNTs, the PL intensity is increased
APD and a charge coupled device (CCD). In the detection roughly 5 times, as well as emission polarization of single
beam path, a rotating linear polarizer is used to investigate dipole is changed to unpolarized radiation. The
radiation direction of PL (Figure 9B). Since 1D carbon enhanced PL intensity is attributed to the increased
nanotubes can be thought as a chain of point dipole excitation and radiative emission rates in the vicinity of
emitters, we expect linearly polarized dipolar emission Au tip. The observed circular radiation pattern is typical
from the sample. Figure 9C shows simulated radiation characteristic of a point dipole oriented vertically.
patterns for in-plane (θ = 90°, left) and out-of-plane (θ = 0°, Therefore, this result demonstrates that when the tip is
right) dipolar emitters. This expected dipolar radiation closed to the SWCNT, a new radiation channel is created
pattern was observed in polarization resolved far-field PL and the radiation energy is transferred to the tip. In this
measurement. case, the scattered PL emission with the ring-shape ra-
Through external control of excitation conditions diation pattern is detected [59]. This work demonstrates
with nano-optical antenna-tip, PL properties of 1D ma- that heterogeneous optical and electronic properties of
terial, e. g., radiative emission rate and angular distri- 1D materials can be resolved with TEPL imaging. Addi-
bution of radiation, can be modified. Figure 9D and E tionally, PL properties of 1D emitters are allowed to
show TEPL image of an SWCNT (inset shows a corre- control with improved performances at the nano-scale
sponding AFM topography) and near-field PL radiation through nano-optical antenna-tip.
pattern when Au tip is located in the arrow indicated in In addition to the modified dipolar emission of the
the near-field PL image (D). In contrast to the tip-induced SWCNTs in near-field [59], understanding their spatial

Figure 9: (A) Schematic diagram of near-field

PL measurement setup. (B) Modeling of the
detection beam path to analyze PL radiation
pattern. (C) Simulated radiation patterns for
the two different point dipole conditions,
i. e., horizontally oriented (θ = 90°) and
vertically oriented (θ = 0°) dipoles. (D) TEPL
image and topography of the SWCNT. The
scale bar is 100 nm. Tip-enhanced near-
field (E) and far-field (F, G) PL radiation
patterns at the point indicated by an arrow
in TEPL image (D). (G) is the same image as
(F), but the intensity scale is modified for
clearer comparison with (E) [59]. Copyright (2010) Optical Society of America.
 H. Lee et al.: TEPL spectroscopy and imaging 3099

heterogeneity in optical and electronic properties is of

significance to material physicists. Qian et al. visualized
the nanoscale optical heterogeneity of semiconducting
carbon nanotubes wrapped by DNA with spectral analysis
[128]. The helical wrapping of a carbon nanotube by the
charged DNA backbone induces π–π stacking interactions
between them, as well as electrostatic interactions [129–
131]. These effects in the DNA-nanotube hybrid structure
make change in relative dielectric constant of the nano-
tube, which leads to modifications in electronic proper-
ties, such as exciton binding energy and band gap.
Additionally, it facilitates symmetry breaking in the
electronic band structure of carbon nanotubes which
gives rise to PL energy shifts. To characterize these
modified local optical responses, TEPL nano-imaging
study was performed [128]. As sample systems, DNA-
wrapped nanotubes were spin-coated on a thin mica
layer/cover slip. To adhere, the naturally negatively
Figure 10: AFM topography (A) and simultaneously measured near-
charged DNA onto the surface, the mica layer was made to field PL image (B) of a DNA-wrapped carbon nanotube on the mica
have positive charges with Mg2+ ions [129]. TEPL setup was substrate. (C, D) Position-dependent peak emission energies
based on an inverted optical microscope with confocal PL derived from the TEPL spectra along the 1D sample. To derive the
optics, and a distance between a sharp metallic tip and peak values at each position, the measured spectra were fitted with
the sample was regulated by a shear-force feedback a Lorentzian line function. (E) Position-dependent PL intensities for
emission peaks of 1.241 eV (DNA-wrapped segments) and 1.259 eV
mechanism. With the highly improved spatial resolution
(DNA-unwrapped segments). TEPL intensities with respect to the
of TEPL compared to confocal PL imaging, DNA-induced position of a carbon nanotube for the peaks of 1.259 eV (F) and
PL energy transition of carbon nanotube was visualized at 1.241 eV (G) [128]. Reprinted with permission from [128]. Copyright
the nano-scale [128]. Figure 10A and B show AFM topog- (2008) American Chemical Society.
raphy of a DNA-wrapped carbon nanotube and corre-
sponding TEPL image. To visualize the TEPL image, the In addition to the carbon nanotubes, CdSe nanowire is
integrated PL intensity between 970 and 1,030 nm, i. e., also one of the significant 1D material for integrated pho-
corresponding to emission range of the sample, was used. tonic devices, photo-voltaics, and sensing devices owing to
Figure 10C and D shows position-dependent peak emis- their strong photo-induced responses and controllability
sion energies along the 1D nanotube structure derived [132]. For example, CdSe nanowires have much higher
from the measured TEPL spectra. An obvious spectral absorption cross-section compared to CdSe quantum dots.
fluctuation between 1.241 and 1.259 eV was observed due In addition, the quantum confinement of CdSe nanowires
to the non-uniform DNA-wrapping around the nanotube. is highly increased when the diameter of nanowires is less
As can be seen in Figure 10D, the length scale in the than 11 nm because CdSe has an exciton Bohr radius of
transition of PL peak energy is sub-diffraction limit. 5.6 nm and the electronic band gap energy is inverse pro-
Therefore, the observed nano-scale heterogeneity could portional to the square of a diameter due to the changed
not be resolved with confocal PL imaging. As a matter of quantum confinement effect [126].
fact, the transition between PL energy levels of DNA- In 2011, Böhmler et al. demonstrated tip-enhanced PL
wrapped and unwrapped segments occurs on a smaller and Raman characterizations of CdSe quantum wires and
length scale than the spatial resolution of TEPL imaging revealed the diameter-dependent quantum confinement
(15 nm). Distance dependent intensity profiles effect [132]. Figure 11A shows a brief schematic diagram of
(Figure 10E) and individual TEPL intensity maps for the the experimental setup, which consists of a confocal mi-
1.259 eV (unwrapped) and 1.259 eV (wrapped) peaks in croscope and a shear-force AFM. CdSe nanowires
Figure 10F and G shows a clear anti-correlated behavior. (Figure 11B) were dispersed on a glass substrate and
Note that, from the tip-sample distance dependence of excited by a 632.8 nm radially polarized HeNe laser. An
TEPL measurement, they confirmed that the metallic tip electrochemically etched Au tip was used to scatter near-
does not perturb the PL emission energy of the sample field PL signal of the sample, and the signal was detected
[128]. either by an APD with spectral filtering or a CCD with a
3100 H. Lee et al.: TEPL spectroscopy and imaging

spectrometer. Strong field enhancement at the tip apex properties of bulk state are determined by free charge
leads to significant improvements in both spatial resolu- carriers [135, 136]. Therefore, TMD monolayers have
tion and PL intensity compared to confocal PL measure- attracted much attentions as 2D semiconductors and,
ment. Figure 11C shows a topography of CdSe quantum controlling these unique excitonic properties have poten-
wires measured with tip-enhanced near-field optical mi- tial applications for the next generation ultra-thin, -light,
croscopy and Figure 11D and E shows simultaneously and flexible optoelectronic devices [137]. For practical ap-
measured near-field PL and Raman images. With the plications of TMD-based optoelectronic device, character-
improved spatial resolution of 20 nm in near-field images, ization of optical and electronic properties should be
the diameter difference of two wire branches (I and II) and preceded. These properties on the microscopic scale can be
their tripod structure is clearly revealed. Additionally, easily understood from spectroscopic far-field PL mea-
spectral differences in PL between thin (II) and thick (I) surement [138, 139]. However, nano-scale optical and
nanowires were visualized which could not be resolved electronic properties at the defects of 2D TMD, such as
with the conventional far field PL imaging. The PL energy impurities, vacancies, grain boundaries, and edges cannot
shift between thin and thick wires was observed up to be understood with a conventional far-field PL spectros-
several tens of meV. Figure 11F shows near-field PL spectra copy due to the diffraction limit. Therefore, TEPL charac-
measured at branches I and II. The thicker wire (I) gives PL terization of these nano-scale defects and spatial
response at lower energy (red) compared to the thinner heterogeneity is highly desirable. In addition, tip-induced
wire (II, blue) due to the decreased band gap. As can be local control of TMD excitonic properties, e. g., PL
seen in Figure 11E, stronger Raman scattering signal was enhancement and bandgap modification, provides a new
obtained from the thinner quantum wire due to the reso- point of view for novel device platforms [140]. In this sec-
nance Raman effect [132]. tion, we discuss recent progress of TEPL applications to 2D
TMD materials.
Park et al. demonstrated TEPL nano-spectroscopy and
7 Applications to 2D materials -imaging for a WSe2 monolayer in 2016 [20]. This work was
the first TEPL approach for 2D TMDs with high sensitivity
Transition metal dichalcogenide monolayers are emerging and spatial resolution, even though a few apertured NSOM
2D semiconductors which have unique excitonic properties. works were performed prior to this work [141, 142]. The
Dimensional reduction of TMDs from bulk to monolayer experiment is basically based on a conventional confocal
gives rise to direct band-to-band transition of electric microscope setup which uses illumination from the top
charges, e. g., an exfoliated MoS2 monolayer shows direct with atomic force microscope (AFM) tip for performing
bandgap at ∼1.8 eV with strong PL emission even though its TERS and TEPL. Helium–Neon laser (632.8 nm, <0.5 mW) is
bulk state (multilayers) has an indirect bandgap at ∼1.3 eV focused through the objective lens (100×, NA = 0.8) and the
[133, 134]. In addition, stable neutral excitons, biexcitons, electrochemically etched gold tip with apex radius (<15 nm)
and trions are formed in 2D TMDs even at room temperature is fixed in the center of focal area. The tip is tilted with ∼40°
with large exciton binding energy due to the strong with respect to the vertical line of the sample surface [20].
Coulomb interaction, whereas optical and electronic Figure 12A shows confocal PL (top left) and TEPL images

Figure 11: (A) Schematic diagram of tip-

enhanced near-field optical microscopy
setup. (B) Transmission electron
microscopy (TEM) image of CdSe quantum
wires. (C) Topography of branched CdSe
nanowire measured with shear-force AFM.
(D–E) Corresponding near-field intensity
maps of PL and Raman responses. (F) Near-
field PL spectra at the positions I and II
indicated in (C) [132]. Copyright 2011 by
John Wiley Sons, Inc. Reprinted by
permission of John Wiley & Sons, Inc.
 H. Lee et al.: TEPL spectroscopy and imaging 3101

(bottom) of a chemical vapor deposition (CVD) grown WSe2 532 nm laser was focused on the sample surface using an
monolayer on SiO2 substrate with corresponding AFM inverted microscope. Ag- or Au-coated Si cantilevers were
topography. Compared to confocal PL image, TEPL images used for excitation field localization and PL enhancement.
show clear nano-scale defects, such as twin boundary, The distance regulation between tip and sample and
nucleation site, and edge, with highly enhanced PL intensity sample scanning were carried out using contact-mode
and spatial resolution <15 nm. In addition, an obvious commercial AFM. Figure 13A shows Raman and PL spectra
change in PL intensity with spectral peak shift is observed in of MoS2 monolayer with and without the Ag-coated tip.
the spectral TEPL analysis as shown in Figure 12B. Figure 12C When the tip is approached onto the sample, Raman and
shows TEPL spectra and deconvolution of exciton and trion PL intensities are enhanced overall, whereas PL in-
biexciton peaks obtained from the crystal edge, nucleation tensity of A0 exciton is decreased. The enhanced Raman
site, and crystal face. Compared to the PL response at the and trion PL signals are explained by the highly enhanced
crystal face, the decreased PL intensity with slight spectral excitation rate at the tip apex because absorption reso-
blue-shift at the edge is attributed to energy funneling from nance of the Ag-coated tip (2.4 eV) is close to the excitation
higher energy states to lower ones in the heterogeneous and beam energy (2.3 eV). On the other hand, the observed
disordered semiconducting system. This PL modification at decrease in A0 exciton PL is caused by the work function of
the edge is observed over ∼30–80 nm spatial extent, which is Ag (4.3 eV). Because the work function of Ag is lower than
a similar length scale to the edge roughness of TMD crystal the work function of monolayer of MoS2 (4.7 eV), electrons
[143]. The distinct blue-shift with largely decreased PL in- of Ag tip naturally move to the MoS2 crystal which causes n-
tensity at the nucleation site is possibly due to the imperfect type doping effect and PL decrease. As for the comparison
composite ratio of Se [144], as well as W residue on the with the Ag-coated tip, when the Au-coated tip is
surface of the crystal which can be a channel of non-radia- approached to the same sample, A0 exciton PL signal is
tive recombination [145]. Furthermore, through the high enhanced, yet Raman scattering intensity stays the same,
spatial resolution TEPL measurement and spectral analysis as shown in Figure 13B. This result shows that there is no
at twin boundaries, the exciton diffusion length of ∼25 nm at significant enhancement of the excitation field because the
room temperature is directly quantified. This work demon- plasmon resonance of Au-coated tip (1.9 eV) is quite far
strated that high resolution TEPL nano-spectroscopy and from excitation energy. Therefore, the enhanced PL of A0
-imaging allows to reveal heterogeneous optical and elec- exciton is mainly attributed to the charge transfer effect
tronic properties at the nanoscale defects of 2D TMD crystals. rather than the increased excitation rate. Figure 13C shows
Since understanding local excitonic processes was energy diagram of MoS2 and metallic tips which explains
desirable at the early stage of new emerging TMD mono- the flow of electrons and p- or n-doping effect of TMD
layers, similar TEPL work has done by Su et al. for MoS2 crystals depend on the material of tip. The unchanged PL
monolayer at about the same time [55]. They performed intensity of trions with the Au tip is also explained with this
direct nano-scale PL mapping of excitons and trions and p-doping effect. Figure 13D shows an overlay image of
found the difference in PL enhancement factor between TERS intensity for A1g mode and integrated TEPL intensity
them due to the influence of the metal-tip work function. for A-exciton band using the Ag-coated tip. Figure 13E and
For the experiment, an exfoliated MoS2 monolayer was F shows TEPL maps of A0-excitons and trions obtained
prepared on a glass coverslip, and a radially polarized from deconvolution of Figure 13D. For comparison, TEPL

Figure 12: (A) PL images of a WSe2 monolayer

measured with confocal microscopy (top)
and TEPL microscopy (bottom, the integrated
intensity of 770–805 nm and 725–760 nm)
with the corresponding AFM topography. (B)
TEPL spectra along the center axis of a WSe2
monolayer. (C) TEPL spectra with peak
energies of 1.610 eV at the edge, 1.630 eV at
the nuclear site (NS), and 1.606 eV at the
crystal face. Exciton (blue) and biexciton
(red) peaks are fitted with Voigt line function.
Reprinted with permission from [20].
Copyright (2016) American Chemical Society.
3102 H. Lee et al.: TEPL spectroscopy and imaging

Figure 13: (A–B) PL and Raman spectra of a

MoS2 monolayer when a metallic tip is
approached and retracted. Ag-coated tip (A)
and Au-coated tip (B) were used for these
measurements. Blue, purple, and red lines
represent the PL intensity of A0, A−, and B
excitons, respectively. (C) Energy diagram
exhibiting work functions of MoS2, Ag, and
Au with the flow of electric charges. (D)
Overlay near-field image of TERS (red) and
TEPL (green) signals of MoS2 monolayer.
TEPL images of A0 excitons (E) and trions (F),
and B-excitons (G) obtained by
deconvoluting the measured near-field PL
spectra. Reproduced from [55] with
permission from The Royal Society of
Chemistry.

map of B-excitons is shown in Figure 13G. In comparison decreased with no peak shift. The other sample was pre-
with the far-field measurement, PL intensity of trions and pared to have both single- and bi-layer flakes on the sub-
B-exciton are highly enhanced, yet PL quenching behavior strate. Figure 14B and D shows TEPL image and AFM
is shown for A0-exciton with TEPL. In addition, far-field PL topography measured simultaneously. As expected from
intensity is dominated by the emission of A0-exciton, but the difference in electronic band structure of single- and bi-
near-field PL intensity is mainly contributed by trion layer TMDs, strong PL emission was measured only from
emission. This study nicely demonstrated the local distri- monolayer flakes. Additionally, stronger TERS signal was
butions of excitonic components, such as excitons and observed from single layer flakes, as shown in Figure 14C.
trions, at the nano-scale with the tip-induced effects. In their experiment, bilayer structure was confirmed by the
Similar TEPL and TERS works for TMD monolayer were Raman peak shift of A1g mode as well as topographic line
carried out by Okuno et al. [146]. They also demonstrated profile (Figure 14E).
the nano-scale heterogeneity in optical properties for a Beyond the TEPL imaging of TMD crystals to under-
CVD grown MoS2. Furthermore, they showed that the local stand intrinsic optical and electronic properties, control of
variations PL properties are associated with the chemical these properties of TMDs through the nano-opto-mechan-
environments. Figure 14A shows TEPL image of short MoS2 ical tip force control was presented by Park et al. [20]. For
flake. The dark spot on the center is due to the presence of a the experiment, WSe2 monolayers grown on SiO2/Si sub-
nanoscale terrace, which was also confirmed with the AFM strate was used. The as-grown crystal is under a tensile
topography. Although the observed nano-scale terrace was strain of ∼1% through physical vapor deposition. To release
indeed confirmed as a multilayer structure, the MoS2 flake the initially applied tensile strain of the crystal, etched Au
is expected to be a monolayer because only PL intensity is tip was used. By carefully applying the tip contact force

Figure 14: (A) Spectrally integrated TEPL

image MoS2 nano-flake. TEPL image (B) and
AFM topography (C) of single- and bi-
layered MoS2 nano-flakes. (D) TERS spectra
of MoS2 monolayer (blue) and bilayer
(green). (E) A topographic line profile of the
sample indicated in (C). Reproduced from
[146] with permission from The Royal
Society of Chemistry.
 H. Lee et al.: TEPL spectroscopy and imaging 3103

Figure 15B. Controlling optical and electronic properties of

semiconductors is essential for device applications. Con-
ventional methods, such as controlling impurities, defects,
and external dopants, are widely used, yet it is difficult to
control at the nano-scale region [148]. This work presented
a novel approach to dynamically control strain, band gap,
and PL energy of atomically thin semiconductor at the
nano-scale.
Recently, He et al. demonstrated the local control of
radiative emission of neutral excitons and trions in WS2
monolayer through precision gap control between Ag tip
and Au substrate [149]. Figure 16A shows a schematic
illustration of the experimental setup. They used Au-
coated Ag tip which was mounted on a cantilever. The
distance between the tip and substrate was regulated
with contact-mode AFM and precisely calibrated using
Figure 15: (A) Evolution of TEPL spectra of a WSe2 monolayer under
the force-distance analysis [55]. Figure 16B shows an
the tip-force regulation exhibiting irreversible PL energy shift (top).
Far-field PL spectra of as-grown and transferred WSe2 monolayer on illustration of the classical coupling regime of TEPL
the SiO2 substrate (bottom). (B) Evolution of TEPL spectra of a WSe2 spectroscopy. In this coupling regime, the tip-sample
monolayer under weaker tip interaction exhibiting reversible PL distance is ∼1 nm and PL responses for neutral exciton
energy shift. Reprinted with permission from [20]. Copyright (2016) (X0) and trions (X−) are observed, as shown in Figure 16C.
American Chemical Society.
In contrast, when the gap is decreased to ∼0.3 nm, direct
tunneling of electrons from Ag tip to WS2 is induced. In
onto the local spot and retracting the tip from the crystal, this regime, these tunneling charges facilitate the tran-
the tensile strain could be released at the nano-scale. They sition of neutral excitons to trions, as described in
could monitor the changed strain by measuring TEPL Figure 16D. Therefore, the measured TEPL spectra under
spectra simultaneously. Figure 15A shows an irreversible this regime show highly increased trion emission, as
strain shift with respect to the increased compressive force shown in Figure 16E. Further, as seen in Figure 16F,
by the tip regulation. The induced tensile strain on the when the tip-sample distance becomes smaller than
crystal was estimated from the peak shift of simultaneously 250 nm, PL intensity of trions increases in contrast to the
measured TEPL spectra. The maximum 48 meV of PL peak decreased PL intensity of neutral excions. This result
shift was observed through the nano-mechanical tip-force shows an obvious evidence of neutral exciton-trions
regulation. Note that PL quantum yield of TMD crystal is conversion with respect to the picometer gap between tip
decreased under strain due to the modified electronic band and sample. This work demonstrated the quantum
structure [147]. Furthermore, with the weaker tip-force plasmonic effects on WS2 monolayer in sub-1 nm gap of
control, tensile strain of the crystal and corresponding metallic cavity which opens new regimes of nano-scale
TEPL enegry could be reversibly controlled, as shown in control of TMD excitonic processes.

Figure 16: (A) Schematic illustration of tip-

enhanced quantum plasmonic (TEQPL)
imaging. Illustrations of the Au tip – Au
substrate cavity in the classical near-field
coupling regime (B) and quantum coupling
regime (D). Near-field PL spectra of neutral
excitons (blue) and trions (red) in the near-
field coupling (C) and quantum coupling (E)
regimes. (F) Distance dependent near-field PL
intensities for neutral excitons (top) and trions
(bottom) in the quantum coupling regime.
From [149]. Reprinted with permission from
AAAS.
3104 H. Lee et al.: TEPL spectroscopy and imaging

8 Conclusions and outlook interactions at the nano-scale. If we use highly conductive

metal substrates, the field enhancement and mode volume
Since Synge’s old proposal to overcome diffraction limit in of the tip-cavity are dramatically changed depending on
far-field optical imaging [24], near-field scanning micro- the tip-substrate gap. By precisely regulating tip-substrate
scopy has advanced considerably with the development of distance with atomic force feedback, we can control the
SPM technology in 1980s [150–152]. The initial approach to plasmon strength, which is easily coupled to other quasi-
implement near-field microscopy is NSOM using a metal- particles of materials, such as excitons. Recently, Park
coated optical fiber probe [25, 26]. NSOM is an innovative et al. demonstrated several studies on the tip-induced
nano-imaging technique with a spatial resolution of control of material properties, e. g., reversible control of PL
50 ∼ 100 nm, but several inevitable difficulties in using energy for TMD monolayers and single quantum dots in the
aperture-type probe, especially weak optical signals, have weak and strong coupling regimes [60]. As for the
restricted the popularization and broad applications. An perspective of instrumentation, currently most TEPL
inverse approach inducing near-field scattering by the tip, studies were performed in ambient conditions. For broader
e. g., s-SNOM, made improvements in near-field microscopy applications of TEPL approach as well as groundbreaking
by solving many problems of NSOM with an improved works, the advanced instrumentation studies must take
spatial resolution of <10 nm [29, 40–44]. However, obtaining precedence. For example, low-temperature TEPL setup will
high spatial resolution image is still challenging due to the allow to measure intrinsic excitonic properties with nar-
far-field background. To this end, tip-enhanced nano-im- rower PL linewidth and higher intensity by suppressing
aging approach has been developed using the LSPR effect of thermally activated processes, e. g., relaxation, quenching,
plasmonic tip [47–49]. With combined nano-spectroscopic and photoionization [153, 154]. This implementation en-
measurement of Raman and PL, i. e., TERS and TEPL, its ables to measure atomic defects of low-dimensional
application range is widely extended. Recently, TEPL quantum materials in great detail. In addition, cryogenic
approach further advanced to the strong coupling regime temperature will be more favorable for TESC experiment
using plasmonic tip-cavity, i. e., TESC spectroscopy [60]. because optical losses in plasmonic tip and substrates are
We focused on the principles and applications of TEPL decreased. For application to soft and living matters, such
in this review. Basically, the enhancement factor of TEPL as biological samples, a routine operation of TEPL setup in
signal is determined by the tip-induced excitation rate and liquid is desirable even though it has remained chal-
the spontaneous emission rate [69]. Since the spontaneous lenging. Furthermore, TEPL measurement for device sys-
emission rate is increased by the Purcell effect, we can tems with in situ control of electrical and electronic
achieve larger enhancement using metal substrates by properties will be a valuable advance. Because this multi-
making smaller mode volume, which also enables large functional measurement will allow to understand correla-
excitation rate based on the coupled dipole model [37, 63, tion information of structural, optical, electronic, and
64]. To demonstrate application studies, we discussed electrical properties. The other challenge is near-field po-
TEPL results on the low-dimensional quantum materials. larization control at the apex of plasmonic tip [57]. As we
For the sake of convenience, we classified the results by the discussed in section 4, the polarizability and the field in-
dimension, i. e., 0D, 1D, and 2D materials. In the 0D tensity are dominant in the axis perpendicular with respect
application section, we discussed TEPL studies of single to the sample surface. On the other hand, each of the ma-
molecules and single quantum dots from weak to strong terials has a different orientation of transition dipole
coupling regimes. We then discussed TEPL applications on moment, e. g., the electric dipole orientation of 1D and 2D
1D materials, such as single-walled carbon nanotubes and materials is preferably into in-plane direction [59, 20].
CdSe quantum wires. Lastly, we presented recent TEPL Therefore, controlling near-field polarization of in-plane
nano-spectroscopy and nano-imaging results on 2D TMDs. and out-of-plane components will be an innovative
In addition to the materials we have discussed in this approach for effective TEPL measurement as well as nano-
review, many kinds of new emerging low dimensional crystallography applications.
material systems are being studied today. Therefore, TEPL
will be a more important characterization method to un- Acknowledgment: This work was supported by the
derstand optical and electronic properties of new emerging National Research Foundation of Korea (NRF) grant funded
materials at the nano-scale. Beyond the high resolution by the Korea government (MEST) (No. 2019R1F1A1059892,
nano-spectroscopy, this tip-enhanced PL approach can be 2019K2A9A1A06099937, and 2020R1C1C1011301). This
used to dynamically control quantum light-matter work was supported by the Start-Up Research Fund
 H. Lee et al.: TEPL spectroscopy and imaging 3105

(1.180091.01) of UNIST (Ulsan National Institute of Science exfoliated graphene monolayers.,” Nano Lett., vol. 9, no. 12,
& Technology). pp. 4446–4451, 2009, https://doi.org/10.1021/nl902729p.
[15] S. Loth, M. Etzkorn, C. P. Lutz, D. M. Eigler, and A. J. Heinrich,
“Measurement of fast electron spin relaxation times with atomic
resolution.,” Science, vol. 329, no. 5999, pp. 1628–1630, 2010,
References https://doi.org/10.1126/science.1191688.
[16] S. Yoshida, Y. Aizawa, Z. Wang, et al., “Probing ultrafast spin
[1] L. J. A. Koster, E. C. P. Smits, V. D. Mihailetchi, and P. W. M. Blom, dynamics with optical pump–probe scanning tunnelling
“Device model for the operation of polymer/fullerene bulk microscopy.,” Nat. Nanotechnol., vol. 9, no. 8, pp. 588, 2014,
heterojunction solar cells.,” Phys. Rev. B, vol. 72, no. 8, 2005, Art https://doi.org/10.1038/nnano.2014.125.
no. 085205, https://doi.org/10.1103/physrevb.72.085205. [17] Z. H. Wang, C. H. Yoon, S. Yoshida, et al., “Surface-mediated
[2] G. K. Mercouri, Semiconductors and semimetals, Amsterdam, spin dynamics probed by optical-pump–probe scanning
Netherlands, Elsevier, 2001. tunneling microscopy.,” Phys. Chem. Chem. Phys., vol. 21, no.
[3] J. Li, A. Corma, and J. Yu, “Synthesis of new zeolite structures.,” 14, pp. 7256–7260, 2019, https://doi.org/10.1039/
Chem. Soc. Rev., vol. 44, no. 20, pp. 7112–7127, 2015, https:// c8cp07786j.
doi.org/10.1039/c5cs00023h. [18] A. M. Baro, R. Miranda, and J. L. Carrascosa, “Application to
[4] T. Takagahara and K. Takeda, “Theory of the quantum biology and technology of the scanning tunneling microscope
confinement effect on excitons in quantum dots of indirect-gap operated in air at ambient pressure.,” IBM J. Res. Dev., vol. 30,
materials.,” Phys. Rev. B, vol. 46, no. 23, p. 15578, 1992, https:// no. 4, pp. 380–386, 1986, https://doi.org/10.1147/rd.304.
doi.org/10.1103/physrevb.46.15578. 0380.
[5] S. Latini, T. Olsen, and K. S. Thygesen, “Excitons in Van der [19] D. R. T. Zahn, P. Tonndorf, R. Schmidt, et al.,
Waals heterostructures: The important role of dielectric “Photoluminescence emission and Raman response of
screening.,” Phys. Rev. B, vol. 92, no. 24, p. 245123, 2015, monolayer MoS2, MoSe2, and WSe2.,” Optic Express, vol. 21, no.
https://doi.org/10.1103/physrevb.92.245123. 4, pp. 4908–4916, 2013, https://doi.org/10.1364/oe.21.
[6] Z. B. Sheneve, M. H. Shawna, L. Cao, et al., “Progress, 004908.
challenges, and opportunities in two-dimensional materials [20] K. D. Park, O. Khatib, V. Kravtsov, G. Clark, X. Xu and M. B. Raschke,
beyond graphene.,” ACS Nano, vol. 7, no. 4, pp. 2898–2926, “Hybrid tip-enhanced nanospectroscopy and nanoimaging of
2013, https://doi.org/10.1021/nn400280c. monolayer WSe2 with local strain control.,” Nano Lett., vol. 16, no. 4,
[7] A. K. Geim, “Graphene: Status and prospects.,” Science, vol. pp. 2621–2627, 2016, https://doi.org/10.1021/acs.nanolett.
324, no. 5934, pp. 1530–1534, 2009, https://doi.org/10.1126/ 6b00238.
science.1158877. [21] A. Bouhelier, J. B. Renger, M. R. Beversluis, and L. Novotny,
[8] M. S. Dresselhaus, G. Chen, M. Y. Tang, et al., “New directions for “Plasmon-coupled tip-enhanced near-field optical
low-dimensional thermoelectric materials.,” Adv. Mater., vol. 19, microscopy.,” J. Microsc., vol. 210, no. 3, pp. 220–224, 2003,
no. 8, pp. 1043–1053, 2007, https://doi.org/10.1002/adma. https://doi.org/10.1046/j.1365-2818.2003.01108.x.
200600527. [22] V. G. Dmitry and V. K. Vasily, “Optical properties of a plasmonic
[9] A. C. Ferrari, J. C. Meyer, V. Scardaci, et al., “Raman spectrum of nano-antenna: an analytical approach.,” New J. Phys., vol. 13,
graphene and graphene layers.,” Phys. Rev. Lett., vol. 97, no. 18, no. 5, p. 053034, 2011, https://doi.org/10.1046/j.1365-2818.
p. 187401, 2006, https://doi.org/10.1103/physrevlett.97. 2003.01108.x.
187401. [23] M. Born and E. Wolf, Principles of optics: Electromagnetic theory
[10] T. W. Odom, J. L. Huang, P. Kim, and C. M. Lieber, “Atomic of propagation, interference and diffraction of light, 7th Edition,
structure and electronic properties of single-walled carbon Amsterdam, Netherlands, Elsevier, 1999.
nanotubes.,” Nature, vol. 391, no. 6662, pp. 62–64, 1998, [24] E. H. Synge, “XXXVIII. A suggested method for extending
https://doi.org/10.1038/34145. microscopic resolution into the ultra-microscopic region.,” Lond.
[11] R. Addou, L. Colombo, and R. M. Wallace, “Surface defects on Edinb. Dublin Phil. Mag. J. Sci., vol. 6, no. 35, pp. 356–362, 1928,
natural MoS2.,” ACS Appl. Mater. Interfaces, vol. 7, no. 22, https://doi.org/10.1080/14786440808564615.
pp. 11921–11929, 2015, https://doi.org/10.1021/acsami. [25] D. W. Pohl, W. Denk, and M. Lanz, “Optical stethoscopy: Image
5b01778. recording with resolution λ/20.,” Appl. Phys. Lett., vol. 44, no. 7,
[12] H. Kirmse, R. Schneider, M. Rabe, W. Neumann, and F. pp. 651–653, 1984, .
Henneberger, “Transmission electron microscopy investigation [26] A. Lewis, M. Isaacson, A. Harootunian, and A. Muray,
of structural properties of self-assembled CdSe/ZnSe quantum “Development of a 500 Å spatial resolution light microscope: I.
dots.,” Appl. Phys. Lett., vol. 72, no. 11, pp. 1329–1331, 1998, light is efficiently transmitted through λ/16 diameter
https://doi.org/10.1063/1.120984. apertures.,” Ultramicroscopy, vol. 13, no. 3, pp. 227–231, 1984,
[13] H. J. Liu, L. Jiao, L. Xie, et al., “Molecular-beam epitaxy of https://doi.org/10.1016/0304-3991(84)90201-8.
monolayer and bilayer WSe2: A scanning tunneling microscopy/ [27] E. Betzig, J. K. Trautman, T. D. Harris, J. S. Weiner, and R. L. Kostelak,
spectroscopy study and deduction of exciton binding energy.,” “Breaking the diffraction barrier: Optical microscopy on a nanometric
2D Mater., vol. 2, no. 3, p. 034004, 2015, https://doi.org/10. scale.,” Science, vol. 251, no. 5000, pp. 1468–1470, 1991, https://doi.
1088/2053-1583/2/3/034004. org/10.1126/science.251.5000.1468.
[14] K. Xu, P. Cao, and J. R. Heath, “Scanning tunneling microscopy [28] U. Ch. Fischer and D. W. Pohl, “Observation of single-particle
characterization of the electrical properties of wrinkles in plasmons by near-field optical microscopy.,” Phys. Rev. Lett.,
3106 H. Lee et al.: TEPL spectroscopy and imaging

vol. 62, no. 4, p. 458, 1989, https://doi.org/10.1103/ vol. 57, no. 2–3, pp. 263–269, 1995, https://doi.org/10.1016/
physrevlett.62.458. 0304-3991(94)00150-l.
[29] M. Specht, J. D. Pedarnig, W. M. Heckl, and T. W. Hänsch, [43] Y. C. Martin, H. F. Hamann, and H. K. Wickramasinghe, “Strength
“Scanning plasmon near-field microscope.,” Phys. Rev. Lett., of the electric field in aperture less near-field optical
vol. 68, no. 4, p. 476, 1992, https://doi.org/10.1103/ microscopy.,” J. Appl. Phys., vol. 89, no. 10, pp. 5774–5778,
physrevlett.68.476. 2001, https://doi.org/10.1063/1.1354655.
[30] A. G. T. Ruiter, J. A. Veerman, M. F. Garcia-Parajo, and N. F. Van [44] R. Hillenbrand and F. Keilmann, “Material-specific mapping of
Hulst, “Single molecule rotational and translational diffusion metal/semiconductor/dielectric nanosystems at 10 nm
observed by near-field scanning optical microscopy.,” J. Phys. resolution by backscattering near-field optical microscopy.,”
Chem. A, vol. 101, no. 40, pp. 7318–7323, 1997, https://doi.org/ Appl. Phys. Lett., vol. 80, no. 1, pp. 25–27, 2002, https://doi.org/
10.1021/jp971066s. 10.1063/1.1428767.
[31] D. A. Higgins, P. J. Reid, and P. F. Barbara, “Structure and [45] K. Kneipp, Y. Wang, H. Kneipp, et al., “Single molecule detection
exciton dynamics in J-aggregates studied by polarization- using surface-enhanced Raman scattering (SERS).,” Phys. Rev.
dependent near-field scanning optical microscopy.,” J. Phys. Lett., vol. 78, no. 9, pp. 1667, 1997, https://doi.org/10.1103/
Chem., vol. 100, no. 4, pp. 1174–1180, 1996, https://doi.org/ physrevlett.78.1667.
10.1021/jp9518217. [46] S. Nie and S. R. Emory, “Probing single molecules and single
[32] A. Lewis, A. Radko, N. B. Ami, D. Palanker, and K. Lieberman, nanoparticles by surface-enhanced Raman scattering.,”
“Near-field scanning optical microscopy in cell biology.,” Trends Science, vol. 275, no. 5303, pp. 1102–1106, 1997, https://doi.
Cell Biol., vol. 9, no. 2, pp. 70–73, 1999, https://doi.org/10. org/10.1126/science.275.5303.1102.
1016/s0962-8924(98)01437-8. [47] R. M. Stöckle, Y. D. Suh, V. Deckert, and R. Zenobi, “Nanoscale
[33] K. D. Park, M. B. Raschke, M. J. Jang, et al., “Near-field imaging of cell chemical analysis by tip-enhanced Raman spectroscopy.,”
membranes in liquid enabled by active scanning probe mechanical Chem. Phys. Lett., vol. 318, no. 1–3, pp. 131–136, 2000, https://
resonance control.,” J. Phys. Chem. C, vol. 120, no. 37, doi.org/10.1016/s0009-2614(99)01451-7.
pp. 21138–21144, 2016, https://doi.org/10.1021/acs.jpcc.6b06563. [48] M. S. Anderson, “Locally enhanced Raman spectroscopy with an
[34] H. D. Hallen, A. H. La Rosa, and C. L. Jahncke, “Near-field atomic force microscope.,” Appl. Phys. Lett., vol. 76, no. 21,
scanning optical microscopy and spectroscopy for pp. 3130–3132, 2000, https://doi.org/10.1063/1.126546.
semiconductor characterization.,” Phys. Status Solidi, vol. 152, [49] N. Hayazawa, Y. Inouye, Z. Sekkat, and S. Kawata, “Metallized tip
no. 1, pp. 257–268, 1995, https://doi.org/10.1002/pssa. amplification of near-field Raman scattering.,” Optic Commun.,
2211520126. vol. 183, no. 1–4, pp. 333–336, 2000, https://doi.org/10.1016/
[35] R. D. Grober, T. D. Harris, J. K. Trautman, et al., “Optical s0030-4018(00)00894-4.
spectroscopy of a GaAs/AlGaAs quantum wire structure using [50] Y. Fang, Z. Zhang, and M. Sun, “High vacuum tip-enhanced
near-field scanning optical microscopy.,” Appl. Phys. Lett., vol. 64, Raman spectroscope based on a scanning tunneling
no. 11, pp. 1421–1423, 1994, https://doi.org/10.1063/1.111903. microscope.,” Rev. Sci. Instrum., vol. 87, no. 3, p. 033104, 2016,
[36] M. S. Jeong, J. Y. Kim, Y. W. Kim, et al., “Spatially resolved https://doi.org/10.1063/1.4943291.
photoluminescence in InGaN/GaN quantum wells by near- [51] Z. Zhang, S. Sheng, R. Wang, and M. Sun, “Tip-enhanced Raman
field scanning optical microscopy.,” Appl. Phys. Lett., vol. 79, spectroscopy.,” Anal. Chem., vol. 88, no. 19, pp. 9328–9346,
no. 7, pp. 976–978, 2001, https://doi.org/10.1063/1. 2016, https://doi.org/10.1021/acs.analchem.6b02093.
1391227. [52] M. T. Wenzel, T. Härtling, P. Olk, et al., “Gold nanoparticle tips for
[37] J. M. Atkin, S. Berweger, A. C. Jones, and M. B. Raschke, “Nano- optical field confinement in infrared scattering near-field optical
optical imaging and spectroscopy of order, phases, and domains microscopy.,” Optic Express, vol. 16, no. 16, pp. 12302–12312,
in complex solids.,” Adv. Phys., vol. 61, no. 6, pp. 745–842, 2008, https://doi.org/10.1364/oe.16.012302.
2012, https://doi.org/10.1080/00018732.2012.737982. [53] K. D. Park, M. B. Raschke, J. M. Atkin, Y. H. Lee, and M. S. Jeong,
[38] H. A. Bethe, “Theory of diffraction by small holes.,” Phys. Rev., “Probing bilayer grain boundaries in large-area graphene with
vol. 66, no. 7–8, p. 163, 1944, https://doi.org/10.1103/physrev. tip-enhanced Raman spectroscopy.,” Adv. Mater., vol. 29, no. 7,
66.163. 2017, Art no. 1603601, https://doi.org/10.1002/adma.
[39] X. Shi, L. Hesselink, and R. L. Thornton, “Ultrahigh light 201603601.
transmission through a C-shaped nanoaperture.,” Optic Lett., [54] C. Zhang, B. Q. Chen, and Z. Y. Li, “Optical origin of
vol. 28, no. 15, pp. 1320–1322, 2003, https://doi.org/10.1364/ subnanometer resolution in tip-enhanced Raman mapping.,”
ol.28.001320. J. Phys. Chem. C, vol. 119, no. 21, pp. 11858–11871, 2015, https://
[40] Y. Inouye and S. Kawata, “Near-field scanning optical doi.org/10.1021/acs.jpcc.5b02653.
microscope with a metallic probe tip.,” Optic Lett., vol. 19, [55] W. Su, N. Kumar, S. Mignuzzi, J. Crain, and D. Roy, “Nanoscale
no. 3, pp. 159–161, 1994, https://doi.org/10.1364/ol.19. mapping of excitonic processes in single-layer MoS2 using tip-
000159. enhanced photoluminescence microscopy.,” Nanoscale, vol. 8,
[41] F. Zenhausern, M. P. O’ Boyle, and H. K. Wickramasinghe, no. 20, pp. 10564–10569, 2016, https://doi.org/10.1039/
“Apertureless near-field optical microscope.,” Appl. Phys. Lett., c5nr07378b.
vol. 65, no. 13, pp. 1623–1625, 1994, https://doi.org/10.1063/1. [56] J. T. Krug, E. J. Sánchez, and X. S. Xie, “Fluorescence quenching in
112931. tip-enhanced nonlinear optical microscopy.,” Appl. Phys. Lett.,
[42] R. B. G. De Hollander, N. F. Van Hulst, and R. P. H. Kooyman, vol. 86, no. 23, p. 233102, 2005, https://doi.org/10.1063/1.
“Near field plasmon and force microscopy.,” Ultramicroscopy, 1935769.
 H. Lee et al.: TEPL spectroscopy and imaging 3107

[57] K. D. Park, and M. B. Raschke, “Polarization control with [72] W. Zhang, X. Cui, and O. J. F. Martin, “Local field enhancement of
plasmonic antenna tips: A universal approach to optical an infinite conical metal tip illuminated by a focused beam.,”
nanocrystallography and vector-field imaging.,” Nano Lett., vol. J. Raman Spectrosc., vol. 40, no. 10, pp. 1338–1342, 2009,
18, no. 5, pp. 2912–2917, 2018, https://doi.org/10.1021/acs. https://doi.org/10.1002/jrs.2439.
nanolett.8b00108. [73] A. V. Goncharenko, M. M. Dvoynenko, H. C. Chang, and J. K.
[58] H. Groß, J. M. Hamm, T. Tufarelli, O. Hess, and B. Hecht, “Near- Wang, “Electric field enhancement by a nanometer-scaled
field strong coupling of single quantum dots.,” Sci. Adv., vol. 4, conical metal tip in the context of scattering-type near-field
no. 3, p. eaar4906, 2018, https://doi.org/10.1126/sciadv. optical microscopy.,” Appl. Phys. Lett., vol. 88, no. 10, p. 104101,
aar4906. 2006, https://doi.org/10.1063/1.2183362.
[59] M. Böhmler, N. Hartmann, C. Georgi, et al., “Enhancing and [74] J. Stadler, B. Oswald, T. Schmid, and R. Zenobi, “Characterizing
redirecting carbon nanotube photoluminescence by an optical unusual metal substrates for gap-mode tip-enhanced Raman
antenna.,” Optic Express, vol. 18, no. 16, pp. 16443–16451, 2010, spectroscopy.,” J. Raman Spectrosc., vol. 44, no. 2, pp. 227–233,
https://doi.org/10.1364/oe.18.016443. 2013, https://doi.org/10.1002/jrs.4169.
[60] K. D. Park, M. A. May, H. Leng, et al., “Tip-enhanced strong [75] N. Kazemi-Zanjani, S. Vedraine, and F. Lagugné-Labarthet,
coupling spectroscopy, imaging, and control of a single quantum “Localized enhancement of electric field in tip-enhanced Raman
emitter.,” Sci. Adv., vol. 5, no. 7, p. eaav5931, 2019, https://doi. spectroscopy using radially and linearly polarized light.,” Optic
org/10.1126/sciadv.aav5931. Express, vol. 21, no. 21, pp. 25271–25276, 2013, https://doi.org/
[61] A. V. Ermushev, B. V. Mchedlishvili, V. A. Oleĭnikov, and A. V. 10.1364/oe.21.025271.
Petukhov, “Surface enhancement of local optical fields and the [76] R. L. Olmon, B. Slovick, T. W. Johnson, et al., “Optical dielectric
lightning-rod effect.,” Quant. Electron., vol. 23, no. 5, p. 435, function of gold.,” Phys. Rev. B, vol. 86, no. 23, p. 235147, 2012,
1993, https://doi.org/10.1070/qe1993v023n05abeh003090. https://doi.org/10.1103/physrevb.86.235147.
[62] V. M. Agranovich, Surface polaritons, Amsterdam, Netherlands, [77] F. Wang and Y. R. Shen, “General properties of local plasmons in
Elsevier, 2012. metal nanostructures.,” Phys. Rev. Lett., vol. 97, no. 20, p. 206806,
[63] F. Keilmann and R. Hillenbrand, “Near-field microscopy by 2006, https://doi.org/10.1103/physrevlett.97.206806.
elastic light scattering from a tip.,” Phil. Trans. Roy. Soc. Lond. [78] E. L. Ru and P. Etchegoin, Principles of surface-enhanced Raman
Ser. A Math. Phys. Eng. Sci., vol. 362, no. 1817, pp. 787–805, Spectroscopy: And related plasmonic effects, Amsterdam,
2004, https://doi.org/10.1098/rsta.2003.1347. Netherlands, Elsevier, 2008.
[64] M. B. Raschke and C. Lienau, “Apertureless near-field optical [79] X. Huang and M. A. El-Sayed, “Gold nanoparticles: Optical
microscopy: Tip–sample coupling in elastic light scattering.,” properties and implementations in cancer diagnosis and
Appl. Phys. Lett., vol. 83, no. 24, pp. 5089–5091, 2003, https:// photothermal therapy.,” J. Adv. Res., vol. 1, no. 1, pp. 13–28,
doi.org/10.1063/1.1632023. 2010, https://doi.org/10.1016/j.jare.2010.02.002.
[65] E. M Purcell, H. C. Torrey, and R. V. Pound, “Resonance [80] P. R. West, S. Ishii, G. V. Naik, N. K. Emani, V. M. Shalaev, and A.
absorption by nuclear magnetic moments in a solid.,” Phys. Rev., Boltasseva, “Searching for better plasmonic materials.,” Laser
vol. 69, no. 1–2, p. 37, 1946, https://doi.org/10.1103/physrev. Photon. Rev., vol. 4, no. 6, pp. 795–808, 2010, https://doi.org/
69.37. 10.1002/lpor.200900055.
[66] R. Carminati, J.-J. Greffet, C. Henkel, and J. M. Vigoureux, “Radiative [81] G. T. Boyd, Z. H. Yu, and Y. R. Shen, “Photoinduced luminescence
and non-radiative decay of a single molecule close to a metallic from the noble metals and its enhancement on roughened
nanoparticle.,” Optic Commun., vol. 261, no. 2, pp. 368–375, 2006, surfaces.,” Phys. Rev. B, vol. 33, no. 12, p. 7923, 1986, https://
https://doi.org/10.1016/j.optcom.2005.12.009. doi.org/10.1103/physrevb.33.7923.
[67] J. N. Farahani, D. W. Pohl, H. J. Eisler, and B. Hecht, “Single [82] L. Novotny and B. Hecht, Principles of nano-optics, Cambridge,
quantum dot coupled to a scanning optical antenna: A tunable United Kingdom, Cambridge University Press, 2012.
superemitter.,” Phys. Rev. Lett., vol. 95, no. 1, 2005, Art no. [83] R. M. Roth, N. C. Panoiu, M. M. Adams, R. M. Osgood, C. C.
017402, https://doi.org/10.1103/physrevlett.95.017402. Neacsu, and M. B. Raschke, “Resonant-plasmon field
[68] C. D. Geddes, Surface plasmon enhanced, coupled and enhancement from asymmetrically illuminated conical metallic-
controlled fluorescence, New Jersey, United States, John Wiley & probe tips.,” Optic Express, vol. 14, no. 7, pp. 2921–2931, 2006,
Sons, 2017. https://doi.org/10.1364/oe.14.002921.
[69] K. D. Park, T. Jiang, G. Clark, X. Xu, and M. B. Raschke, [84] A. Normatov, P. Ginzburg, N. Berkovitch, et al., “Efficient
“Radiative control of dark excitons at room temperature by coupling and field enhancement for the nano-scale: Plasmonic
nano-optical antenna-tip purcell effect.,” Nat. Nanotechnol., needle.,” Optic Express, vol. 18, no. 13, pp. 14079–14086, 2010,
vol. 13, no. 1, pp. 59–64, 2018, https://doi.org/10.1038/ https://doi.org/10.1364/oe.18.014079.
s41565-017-0003-0. [85] L. Novotny, R. X. Bian, and X. S. Xie, “Theory of nanometric
[70] N. Behr and M. B. Raschke, “Optical antenna properties of optical tweezers.,” Phys. Rev. Lett., vol. 79, no. 4, p. 645, 1997,
scanning probe tips: plasmonic light scattering, tip-sample https://doi.org/10.1103/physrevlett.79.645.
coupling, and near-field enhancement.,” J. Phys. Chem. C, vol. [86] R. G. Milner and D. Richards, “The role of tip plasmons in near-
112, no. 10, pp. 3766–3773, 2008, https://doi.org/10.1021/ field Raman microscopy.,” J. Microsc., vol. 202, no. 1, pp. 66–71,
jp7098009. 2001, https://doi.org/10.1046/j.1365-2818.2001.00864.x.
[71] D. S. Bulgarevich and M. Futamata, “Apertureless tip-enhanced [87] A. L. Demming, F. Festy, and D. Richards, “Plasmon resonances
Raman microscopy with confocal epi-illumination/collection on metal tips: Understanding tip-enhanced Raman scattering.,”
optics.,” Appl. Spectrosc., vol. 58, no. 7, pp. 757–761, 2004, J. Chem. Phys., vol. 122, no. 18, p. 184716, 2005, https://doi.org/
https://doi.org/10.1366/0003702041389292. 10.1063/1.1896356.
3108 H. Lee et al.: TEPL spectroscopy and imaging

[88] M. Micic, N. Klymyshyn, Y. D. Suh, and H. P. Lu, “Finite element [103] J. Azoulay, A. Débarre, A. Richard, and P. Tchénio, “Field
method simulation of the field distribution for AFM tip- enhancement and apertureless near-field optical spectroscopy
enhanced surface-enhanced Raman scanning microscopy.,” of single molecules.,” J. Microsc., vol. 194, no. 2–3,
J. Phys. Chem. B, vol. 107, no. 7, pp. 1574–1584, 2003, https:// pp. 486–490, 1999, https://doi.org/10.1046/j.1365-2818.
doi.org/10.1021/jp022060s. 1999.00558.x.
[89] C. A. Balanis, Antenna theory: analysis and design, New Jersey, [104] E. Betzig and R. J. Chichester, “Single molecules observed by
United States, John Wiley & Sons, 2016. near-field scanning optical microscopy.,” Science, vol. 262, no.
[90] M. Sun, Z. Zhang, L. Chen, S. Sheng, and H. Xu, “Plasmonic 5138, pp. 1422–1425, 1993, https://doi.org/10.1126/science.
gradient effects on high vacuum tip-enhanced Raman 262.5138.1422.
spectroscopy.,” Adv. Opt. Mat., vol. 2, no. 1, pp. 74–80, 2014, [105] T. Takagahara, “Enhanced excitonic optical nonlinearity and
https://doi.org/10.1002/adom.201300296. exciton dynamics in semiconductor microstructures.,” Surf.
[91] M. Sun, Z. Zhang, L. Chen, et al., “Plasmon-driven selective Sci., vol. 196, no. 1–3, pp. 590–595, 1988, https://doi.org/10.
reductions revealed by tip-enhanced Raman spectroscopy.,” 1016/0039-6028(88)90746-7.
Adv. Mater. Interface, vol. 1, no. 5, p. 1300125, 2014, https:// [106] Z. Ma, J. M. Gerton, L. A. Wade, and S. R. Quake, “Fluorescence
doi.org/10.1002/admi.201300125. near-field microscopy of DNA at sub-10 nm resolution.,” Phys.
[92] F. Lu, W. Zhang, L. Zhang, et al., “Nanofocusing of surface Rev. Lett., vol. 97, no. 26, 2006, https://doi.org/10.1103/
plasmon polaritons on metal-coated fiber tip under internal physrevlett.97.260801.
excitation of radial vector beam.,” Plasmonics, vol. 14, no. 6, [107] H. G. Frey, J. Paskarbeit, and D. Anselmetti, “Tip-enhanced
pp. 1593–1599, 2019, https://doi.org/10.1007/s11468-019- single molecule fluorescence near-field microscopy in aqueous
00951-8. environment.,” Appl. Phys. Lett., vol. 94, no. 24, 2009, https://
[93] N. Hayazawa, A. Tarun, Y. Inouye, and S. Kawata, “Near-field doi.org/10.1063/1.3155190.
enhanced Raman spectroscopy using side illumination [108] C. Höppener and L. Novotny, “Antenna-based optical imaging of
optics.,” J. Appl. Phys., vol. 92, no. 12, pp. 6983–6986, 2002, single Ca2+ transmembrane proteins in liquids.,” Nano Lett., vol.
https://doi.org/10.1063/1.1519945. 8, no. 2, pp. 642–646, 2008, https://doi.org/10.1021/
[94] D. Mehtani, N. Lee, R. D. Hartschuh, et al., “Nano-Raman nl073057t.
spectroscopy with side-illumination optics.,” J. Raman [109] V. V. Protasenko, M. Kuno, A. Gallagher, and D. J.
Spectrosc., vol. 36, no. 11, pp. 1068–1075, 2005, https://doi. Nesbitt, “Fluorescence of single ZnS overcoated CdSe
org/10.1002/jrs.1409. quantum dots studied by apertureless near-field scanning
[95] M. Sun, Y. Fang, Z. Zhang, and H. Xu, “Activated vibrational optical microscopy.,” Optic Commun., vol. 210, no. 1–2,
modes and Fermi resonance in tip-enhanced Raman pp. 11–23, 2002, https://doi.org/10.1016/s0030-
spectroscopy.,” Phys. Rev. E, vol. 87, no. 2, 2013, Art no. 4018(02)01759-5.
020401, https://doi.org/10.1103/physreve.87.020401. [110] H. G. Frey, S. Witt, K. Felderer, and R. Guckenberger, “High-
[96] M. Gao, M. Sun, and L. Meng, “Tip-enhanced spectroscopy of 2D resolution imaging of single fluorescent molecules with the
black phosphorus.,” J. Raman Spectrosc., vol. 50, no. 8, optical near-field of a metal tip.,” Phys. Rev. Lett., vol. 93, no.
pp. 1058–1064, 2019, https://doi.org/10.1002/jrs.5610. 20, 2004, Art no. 200801, https://doi.org/10.1103/physrevlett.
[97] D. Kurouski, S. Zaleski, F. Casadio, R. P. Van Duyne, and N. C. 93.200801.
Shah, “Tip-enhanced Raman spectroscopy (TERS) for in situ [111] J. M. Gerton, L. A. Wade, G. A. Lessard, Z. Ma, and S. R. Quake,
identification of indigo and iron gall ink on paper.,” J. Am. Chem. “Tip-enhanced fluorescence microscopy at 10 nanometer
Soc., vol. 136, no. 24, pp. 8677–8684, 2014, https://doi.org/ resolution.,” Phys. Rev. Lett., vol. 93, no. 18, 2004, Art no.
10.1021/ja5027612. 180801, https://doi.org/10.1103/physrevlett.93.180801.
[98] M. A. Lieb and A. J. Meixner, “A high numerical aperture [112] W. E. Moerner and L. Kador, “Optical detection and
parabolic mirror as imaging device for confocal microscopy.,” spectroscopy of single molecules in a solid.,” Phys. Rev. Lett.,
Optic Express, vol. 8, no. 7, pp. 458–474, 2001, https://doi.org/ vol. 62, no. 21, pp. 2535–2538, 1989, https://doi.org/10.1103/
10.1364/oe.8.000458. physrevlett.62.2535.
[99] C. J. R. Sheppard and A. Choudhury, “Annular pupils, radial [113] X. S. Xie and R. C. Dunn, “Probing single molecule dynamics.,”
polarization, and superresolution.,” Appl. Optic., vol. 43, no. Science, vol. 265, no. 5170, pp. 361–364, 1994, https://doi.org/
22, pp. 4322–4327, 2004, https://doi.org/10.1364/ao.43. 10.1126/science.265.5170.361.
004322. [114] W. P. Ambrose, P. M. Goodwin, J. C. Martin, and R. A. Keller,
[100] J. Kim, D.C. Kim, and S.H. Back, “Demonstration of high lateral “Single molecule detection and photochemistry on a surface
resolution in laser confocal microscopy using annular and using near-field optical excitation.,” Phys. Rev. Lett., vol. 72, no.
radially polarized light.,” Microsc. Res. Tech., vol. 72, no. 6, 1, pp. 160–163, 1994, https://doi.org/10.1103/physrevlett.72.
pp. 441–446, 2009, https://doi.org/10.1002/jemt.20689. 160.
[101] W. T. Tang, E. Y. S. Yew, and C. J. R. Sheppard, “Polarization [115] W. Denk and D. W Pohl, “Near-field optics: Microscopy with
conversion in confocal microscopy with radially polarized nanometer-size fields.,” J. Vac. Sci. Technol. B, vol. 9, no. 2,
illumination.,” Optic Lett., vol. 34, no. 14, pp. 2147–2149, 2009, pp. 510–513, 1991, https://doi.org/10.1116/1.585558.
https://doi.org/10.1364/ol.34.002147. [116] H. G. Frey, F. Keilmann, A. Kriele, and R. Guckenberger,
[102] Y. Kozawa, T. Hibi, A. Sato, et al., “Lateral resolution “Enhancing the resolution of scanning near-field optical
enhancement of laser scanning microscopy by a higher-order microscopy by a metal tip grown on an aperture probe.,” Appl.
radially polarized mode beam.,” Optic Express, vol. 19, no. 17, Phys. Lett., vol. 81, no. 26, pp. 5030–5032, 2002, https://doi.
pp. 15947–15954, 2011, https://doi.org/10.1364/oe.19.015947. org/10.1063/1.1530736.
 H. Lee et al.: TEPL spectroscopy and imaging 3109

[117] C. Höppener and L. Novotny, “Imaging of membrane proteins [131] S. Manohar, T. Tang, and A. Jagota, “Structure of
using antenna-based optical microscopy.,” Nanotechnology, homopolymer DNA-CNT hybrids.,” J. Phys. Chem. C, vol. 111,
vol. 19, no. 38, p. 384012, 2008, https://doi.org/10.1088/ no. 48, pp. 17835–17845, 2007, https://doi.org/10.1021/
0957-4484/19/38/384012. jp071316x.
[118] J. Azoulay, A. Débarre, A. Richard, and P. Tchénio, [132] M. Böhmler, Z. Wang, A. Myalitsin, A. Mews, and A. Hartschuh,
“Quenching and enhancement of single-molecule “Optical imaging of CdSe nanowires with nanoscale
fluorescence under metallic and dielectric tips.,” Europhys. resolution.,” Angew. Chem. Int. Ed., vol. 50, no. 48,
Lett., vol. 51, no. 4, p. 374, 2000, https://doi.org/10.1209/ pp. 11536–11538, 2011, https://doi.org/10.1002/anie.
epl/i2000-00504-y. 201105217.
[119] V. V. Protasenko, A. Gallagher, and D. J. Nesbitt, “Factors that [133] K. F. Mak, C. Lee, J. Hone, J. Shan, and T. F. Heinz, “Atomically
influence confocal apertureless near-field scanning optical thin MoS2: A new direct-gap semiconductor.,” Phys. Rev. Lett.,
microscopy.,” Optic Commun., vol. 233, no. 1–3, pp. 45–56, vol. 105, no. 13, 2010, Art no. 136805, https://doi.org/10.1103/
2004, https://doi.org/10.1016/j.optcom.2004.01.004. physrevlett.105.136805.
[120] A. Hartschuh, E. J. Sánchez, X. S. Xie, and L. Novotny, “High- [134] Q. H. Wang, K. Kalantar-Zadeh, A. Kis, J. N. Coleman, and M.
resolution near-field Raman microscopy of single-walled S. Strano, “Electronics and optoelectronics of two-
carbon nanotubes.,” Phys. Rev. Lett., vol. 90, no. 9, 2003, dimensional transition metal dichalcogenides.,” Nat.
Art no. 095503, https://doi.org/10.1103/physrevlett.90. Nanotechnol., vol. 7, no. 11, p. 699, 2012, https://doi.org/
095503. 10.1038/nnano.2012.193.
[121] E. J. Sánchez, L. Novotny, and X. S. Xie, “Near-field fluorescence [135] A. Chernikov, T. C. Berkelbach, H. M. Hill, et al., “Exciton binding
microscopy based on two-photon excitation with metal tips.,” energy and nonhydrogenic Rydberg series in monolayer WS2.,”
Phys. Rev. Lett., 82, no. 20, pp. 4014–4017, 1999, https://doi. Phys. Rev. Lett., vol. 113, no. 7, 2014, Art no. 076802, https://
org/10.1103/physrevlett.82.4014. doi.org/10.1103/physrevlett.113.076802.
[122] H. F. Hamann, M. Kuno, A. Gallagher, and D. J. Nesbitt, [136] A. Boulesbaa, B. Huang, K. Wang, et al., “Observation of two
“Molecular fluorescence in the vicinity of a nanoscopic probe.,” distinct negative trions in tungsten disulfide monolayers.,”
J. Chem. Phys., vol. 114, no. 19, pp. 8596–8609, 2001, https:// Phys. Rev. B, vol. 92, no. 11, 2015, Art no. 115443, https://doi.
doi.org/10.1063/1.1365931. org/10.1103/physrevb.92.115443.
[123] A. Kramer, W. Trabesinger, B. Hecht, and U. P. Wild, “Optical [137] K. F. Mak and J. Shan, “Photonics and optoelectronics of 2D
near-field enhancement at a metal tip probed by a single semiconductor transition metal dichalcogenides.,” Nat.
fluorophore.,” Appl. Phys. Lett., vol. 80, no. 9, pp. 1652–1654, Photon., vol. 10, no. 4, p. 216, 2016, https://doi.org/10.1038/
2002, https://doi.org/10.1063/1.1453479. nphoton.2015.282.
[124] X. Dai, Z. Zhang, Y. Jin, et al., “Solution-processed, high- [138] P. K. Chow, R. B. Jacobs-Gedrim, J. Gao, et al., “Defect-induced
performance light-emitting diodes based on quantum dots.,” photoluminescence in monolayer semiconducting transition
Nature, vol. 515, no. 7525, pp. 96–99, 2014, https://doi.org/10. metal dichalcogenides.,” ACS Nano, vol. 9, no. 2,
1038/nature13829. pp. 1520–1527, 2015, https://doi.org/10.1021/nn5073495.
[125] P. Michler, “A quantum dot single-photon turnstile device.,” [139] Z. Wu, W. Zhao, J. Jiang, et al., “Defect activated
Science, vol. 290, no. 5500, pp. 2282–2285, 2000, https://doi. photoluminescence in WSe2 monolayer.,” J. Phys. Chem. C, vol.
org/10.1126/science.290.5500.2282. 121, no. 22, pp. 12294–12299, 2017, https://doi.org/10.1021/
[126] J. J. Glennon, R. Tang, W. E. Buhro, and R. A. Loomis, acs.jpcc.7b03585.
“Synchronous photoluminescence intermittency (blinking) [140] L. Meng and M. Sun, “Tip-enhanced photoluminescence
along whole semiconductor quantum wires.,” Nano Lett., vol. 7, spectroscopy of monolayer MoSe2.,” Photon. Res., vol. 5, no. 6,
no. 11, pp. 3290–3295, 2007, https://doi.org/10.1021/ pp. 745–749, 2017, https://doi.org/10.1364/prj.5.000745.
nl0714583. [141] Y. Lee, S. Park, H. Kim, G. H. Han, Y. H. Lee, and J. Kim,
[127] Y. Yan, C. Zhang, J. Yao, and Y. S. Zhao, “Recent advances in “Characterization of the structural defects in CVD-grown
organic one-dimensional composite materials: Design, monolayered MoS2 using near-field photoluminescence
construction, and photonic elements for information imaging.,” Nanoscale, vol. 7, no. 28, pp. 11909–11914, 2015,
processing.,” Adv. Mater., vol. 25, no. 27, pp. 3627–3638, 2013, https://doi.org/10.1039/c5nr02897c.
https://doi.org/10.1002/adma.201300325. [142] W. Bao, N. J. Borys, C. Ko, et al., “Visualizing nanoscale
[128] H. Qian, P. T. Araujo, C. Georgi, et al., “Visualizing the local excitonic relaxation properties of disordered edges and grain
optical response of semiconducting carbon nanotubes to DNA- boundaries in monolayer molybdenum disulfide.,” Nat.
wrapping.,” Nano Lett., vol. 8, no. 9, pp. 2706–2711, 2008, Commun., vol. 6, no. 1, pp. 1–7, 2015, https://doi.org/10.1038/
https://doi.org/10.1021/nl801038t. ncomms8993.
[129] H. Jin, E. S. Jeng, D. A. Heller, et al., “Divalent ion and [143] A. M. Van Der Zande, P. Y. Huang, D. A. Chenet, et al., “Grains
thermally induced DNA conformational polymorphism on and grain boundaries in highly crystalline monolayer
single-walled carbon nanotubes.,” Macromolecules, vol. 40, molybdenum disulphide.,” Nat. Mater., vol. 12, no. 6,
no. 18, pp. 6731–6739, 2007, https://doi.org/10.1021/ pp. 554–561, 2013, https://doi.org/10.1038/nmat3633.
ma070608t. [144] B. Liu, M. Fathi, L. Chen, A. Abbas, Y. Ma, and C. Zhou,
[130] R. R. Johnson, A. T. C. Johnson, and M. L. Klein, “Probing the “Chemical vapor deposition growth of monolayer WSe2 with
structure of DNA-carbon nanotube hybrids with molecular tunable device characteristics and growth mechanism study.,”
dynamics.,” Nano Lett., vol. 8, no. 1, pp. 69–75, 2008, https:// ACS Nano, vol. 9, no. 6, pp. 6119–6127, 2015, https://doi.org/
doi.org/10.1021/nl071909j. 10.1021/acsnano.5b01301.
3110 H. Lee et al.: TEPL spectroscopy and imaging

[145] C. Cong, J. Shang, X. Wu, et al., “Synthesis and optical [150] G. Binnig and H. Rohrer, “Scanning tunneling microscopy.,”
properties of large-area single-crystalline 2D semiconductor Surf. Sci., 126, no. 1–3, pp. 236–244, 1983, https://doi.org/10.
WS2 monolayer from chemical vapor deposition.,” Adv. Opt. 1016/0039-6028(83)90716-1.
Mater., vol. 2, no. 2, pp. 131–136, 2014, https://doi.org/10. [151] J. Tersoff and D. R. Hamann, “Theory and application for the
1002/adom.201300428. scanning tunneling microscope.,” Phys. Rev. Lett., vol. 50, no.
[146] Y. Okuno, O. Lancry, A. Tempez, et al., “Probing the nanoscale 25, p. 1998, 1983, https://doi.org/10.1103/physrevlett.50.
light emission properties of a CVD-grown MoS2 monolayer by 1998.
tip-enhanced photoluminescence.,” Nanoscale, vol. 10, [152] G. Binnig, C. F. Quate, and Ch. Gerber, “Atomic force
no. 29, pp. 14055–14059, 2018, https://doi.org/10.1039/ microscope.,” Phys. Rev. Lett., vol. 56, no. 9, p. 930, 1986,
c8nr02421a. https://doi.org/10.1103/physrevlett.56.930.
[147] S. Deng, A. V. Sumant, and V. Berry, “Strain engineering in two- [153] Y. Zhao, C. Riemersma, F. Pietra, R. Koole, C. de Mello
dimensional nanomaterials beyond graphene.,” Nano Today, vol. Donegá, and A. Meijerink, “High-temperature luminescence
22, pp. 14–35, 2018, https://doi.org/10.1016/j.nantod.2018.07.001. quenching of colloidal quantum dots.,” ACS Nano, vol. 6, no.
[148] S. T. Pantelides, “The electronic structure of impurities and other 10, pp. 9058–9067, 2012, https://doi.org/10.1021/
point defects in semiconductors.,” Rev. Mod. Phys., vol. 50, no. 4, nn303217q.
p. 797, 1978, https://doi.org/10.1103/revmodphys.50.797. [154] M. Y. Shen, M. Oda, and T. Goto, “Direct evidence for
[149] Z. He, Z. Han, J. Yuan, et al., “Quantum plasmonic control of trions photoionization in CdTe nanocrystals embedded in
in a picocavity with monolayer WSe2.,” Sci. Adv., vol. 5, no. 10, trioctylphosphine oxide.,” Phys. Rev. Lett., vol. 82, no. 19,
p. eaau8763, 2019, https://doi.org/10.1126/sciadv.aau8763. p. 3915, 1999, https://doi.org/10.1103/physrevlett.82.3915.