Article

Cite This: J. Phys. Chem. C 2019, 123, 15761−15768 pubs.acs.org/JPCC

Controllable Single-Molecule Light Emission by Selective Charge

Injection in Scanning Tunneling Microscopy
Xiaoyan Wu,† Rulin Wang,‡,† Yu Zhang,§ Bowen Song,† and ChiYung Yam*,†,∥
†
Beijing Computational Science Research Center, Haidian District, Beijing 100193, China
‡
College of Physics, Qingdao University, No. 308 Ningxia Road, Qingdao 266071, China
§
Physics and Chemistry of Materials, Theoretical Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545,
United States
∥
Department of Chemistry, The University of Hong Kong, Pok Fu Lam, Hong Kong
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*
S Supporting Information

ABSTRACT: Tunneling electron-induced light emission in

scanning tunneling microscopy (STM) has recently been
explored as a novel light source with tunable properties. Here,
using first-principles-based atomistic simulations, we study the
STM-induced luminescence of a single free-base phthalocya-
nine (H2Pc) molecule and propose a way to control the
emission frequency of the STM molecular junction by precisely
controlling the charge injection at different molecular positions. The luminescence is found to be directly related to the spatial
distribution of the molecular states and thus depends sensitively on the tip position. Via careful refinement of the chemical
structures, devices with desirable frequencies at different parts of the emitting unit can be designed. Our proposal has profound
implications for applications in nanoscale optoelectronics and future hybrid electronic-photonic circuits.

■ INTRODUCTION
Advanced fabrication technologies for the semiconductor
electronics industry enable control over the charge transport
at the nanoscale. As the downsizing of electronic devices
continues, however, the operating frequencies of nano-
electronic circuits have a bandwidth limited to the GHz
range.1,2 To overcome this limit, hybrid electronic-photonic
devices have been proposed as future ultrafast devices. While
signals carried by photons offer the possibilities of extending
the working frequencies by several orders of magnitude,
because of the diffraction limit, optical components are too
large in size to compete with modern nanoelectronics.
Therefore, a key component of these hybrid devices is a
nanoscale transducer that allows the conversion of electrical
stimuli into optical signals. The atomic-scale resolution of
scanning tunneling microscopy (STM) provides the possibility
of extremely localized excitations. In addition to the imaging of
nanostructures at a subnanometer resolution, nanojunctions in
STM can also be used to induce light emission via the inelastic
scattering of tunneling electrons. In recent years, STM-induced
luminescence has attracted much attention.3,4 The interest is
motivated by its potential as a viable technology for obtaining
optical spectroscopic information using the subnanometer
spatial resolution of STM. Light emission induced by tunneling
electrons in STM has been reported in different systems,
including metal surfaces,5 semiconductor heterostructures,6
nanoparticles,7 quantum wells,8 and single molecules.9−14 In
the case of single molecules on a metallic surface, STM-
induced molecular luminescence has been observed when the
molecules are decoupled from STM substrates. In general, light
is emitted when an electron−hole pair recombines in the
molecules, which can be realized in STM when two molecular
states enter the bias voltage window. The injection of charges
into these states results in an excited state of the molecules,
which may decay radiatively via photon emission. In this
framework, single-molecule junctions can operate as light-
emitting devices and have recently been explored as novel
molecular light sources with tunable properties.15−17
Remarkably, luminescence is sensitive to the tip position on
the molecule, a phenomenon that can be attributed to the
spatial distribution of charges responsible for the photon
generation. The structural details of individual molecules can
thus be revealed through optical spectroscopy upon highly
localized charge injection at different molecular positions.13
This has proven to be an invaluable tool for understanding the
fundamental phenomena of single molecules and their
potential applications in nanoscale devices.15,16 Recently,
STM-induced luminescence was employed to visualize the
coherent coupling of intermolecular dipole−dipole interactions
between porphyrin molecules. The spatial distribution of the
coupling of the transition dipoles can be directly observed from
spectrally resolved photon images.18 Recently, Imada et al.
applied the technique to investigate energy transfer between
coupled molecular dimers,19 and Doppagne et al. used it to
Received: March 8, 2019
Revised: June 1, 2019
Published: June 3, 2019

© 2019 American Chemical Society 15761 DOI: 10.1021/acs.jpcc.9b02198

J. Phys. Chem. C 2019, 123, 15761−15768
The Journal of Physical Chemistry C
obtain vibronic signals at a submolecular resolution.20 On the
other hand, this tip-position dependence of light emission can
be exploited to control emission frequency at submolecular
levels. Here, we present state-of-the-art atomistic simulations
of the STM-induced luminescence of a single free-base
phthalocyanine (H2Pc) molecule on a gold substrate and
propose a way to control the emission frequency of molecular
light-emitting devices. This is achieved via selective charge
injection at different molecular positions. The precise control
of the tip position allows adjustable coupling to different
molecular orbitals where electron−hole recombinations are
involved. On the basis of the nonequilibrium Green’s function
(NEGF) method, interactions with the electromagnetic
vacuum environment are included21 to model the STM-
induced luminescence of realistic molecules. Taking into
account the atomistic details, our approach also provides the
possibility to simulate the spectrally resolved photon images
from first-principles-based simulations. This work permits a
greater understanding of fundamental phenomena and
facilitates the rational design of nanoscale optoelectronic
devices.
■
METHODS
Quantum Transport and Current-Induced Lumines-
cence. The Hamiltonian for the single-molecule STM
junction is given by
H = Hm + Hmt + Hms + Hep (1)
where Hm describes the Hamiltonian of an extended system
composed of the molecular junction with part of the tip and
substrate. Hmt and Hms stand for the coupling of the extended
system with the tip and substrate, respectively. Both the tip and
substrate are assumed to be in thermal equilibrium with a
density matrix that can be described by the Fermi−Dirac
distribution. Hep represents the electron−plasmon interaction
Hamiltonian, which describes the optical transition processes
in the system,
e a pUp(r)(be−iωpt + b†eiωpt )
Hep = ∑ ⟨μ|A p ·p|ν⟩dμ†dν
μν
m (2)
where d and d† are the annihilation and creation operators of
the electron, respectively.22 Ap is the time-dependent vector
potential for the plasmon mode, p is the electron momentum
operator, e is the elementary charge, and m is the electron
mass. The interaction effects of the last three terms in eq 1 can
be incorporated through self-energies.21,23,24 The lesser self-
energy represents the injection of charge carriers from the tip/
substrate, which is given by
Σ<t/s(E) = ift/s (E)Γt/s(E)
Σ>t/s(E) = −i[1 − ft/s (E)]Γt/s(E)
r
Γt/s(E) = i[Σt/s (E) − Σat/s(E)] (3)
where Γt/s is the coupling between the system and the tip and
substrate, respectively, which is related to the electron escape
rates from the molecule to the tip and substrate. f t/s gives the
Fermi−Dirac distribution. The lesser and greater self-energies
due to electron−plasmon interactions can be expressed as
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Σ<ep,>(E) = Mp[NG<, >(E ∓ ℏωp)
+ (N + 1)G<, >(E ± ℏωp)]Mp (4)
p
where M is the electron−plasmon coupling matrix for a
plasmon mode with frequency ωp and N is the corresponding
plasmon mode occupation. G<,>(E) are the lesser and greater
electron Green’s functions. Equation 4 is a nonlinear equation
since Green’s function depends on the self-energies,
G<, >(E) = Gr(E)[Σ<t , >(E) + Σ<s , >(E) + Σ<ep,>(E)]Ga(E)
Gr(E) = [Ga(E)]* = G0r(E) + G0r(E)Σep
r
( E ) G r (E )
1
G0r(E) =
E − Hm − Σrt (E) − Σsr(E)
(5)
r a
where G (E) and G (E) are the retarded and advanced Green’s
functions, respectively. Gr0(E) is the retarded Green’s function
of the system without electron−plasmon interactions. In this
work, the electron Green’s function is calculated at the lowest
order with respect to the electron−plasmon coupling. Previous
works showed that the approximation is valid in the weak
coupling regime.25−27 In addition, it has been proved that the
lowest order expansion guarantees particle conservation and
therefore satisfies current continuity.28 Within the lowest order
approximation, the retarded Green’s function is given by
Gr(E) ≈ G0r(E) + G0r(E)Σep
r
(E)G0r(E) (6)
The plasmon is assumed to decay efficiently into far-field
photons and the system is therefore coupled to an empty
plasmon mode. The interaction self-energy can be simplified as
Σ<ep,>(E) = Mp[G0<, >(E ± ℏωp)]Mp (7)
Nanocavity Plasmons in STM. The vector potential for
the nanocavity plasmon used in this work is given by29,30
ji ℏ zyz
A p(r, t ) = jjjj zz
j 2ϵ0ωpVp zz
1/2
k {
(8)
where ϵ0 is the vacuum permittivity. ωp is the plasmon
frequency. ap defines the polarization direction of the plasmon
mode. Vp is the effective volume of the nanogap and Up(r)
gives the spatial distribution of the plasmon which depends on
the tip position. b and b† are the annihilation and creation
operators of plasmon mode. In principle, the characteristics of
the STM nanogap plasmon can be readily obtained numeri-
cally by either classical or quantum mechanical simula-
tions.31−33 Here, for simplicity, an analytical expression is
taken to describe the spatial distribution of the vector
potential.34,35
2
+ (rz − rz ,D)2 ] −β |rx − rx ,D|
Up(r) = e−α[(ry − ry ,D) e (9)
In this work, we chose the parameters based on a model tunnel
junction.34 rD is the position where the maximum field
enhancement is located and is set as 3 Å below the tip apex.
The parameters specifying the plasmon mode are summarized
in Table 1.
Substituting eq 8 into eq 2, we obtain the electron−plasmon
coupling matrix,
DOI: 10.1021/acs.jpcc.9b02198
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Table 1. Parameters Used for the Nanogap Plasmon molecule and calculated the emission spectrum for each
configuration using eq 13. The emission intensity for each peak
parameter value explanation
is then integrated to obtain each pixel in Figure 4d,e. Because
ωp 1.3 eV plasmon frequency the molecule has a D2h symmetry, only one-quarter of the
Γp 0.5 eV decay rate image is calculated. Overall, Figure 4d,e contains totally 19 ×
α 0.31 Å−2 spatial extent in y−z plane 19 simulation data. To increase the resolution, the figures are
β 0.15 Å−1 for rx < rx,D interpolated linearly to 37 × 37 pixels.

■
0.22 Å−1 for rx > rx,D

e ij ℏ yzzz
Mp = jjjj
RESULTS
z
m j 2ϵ0ωpVp zz
1/2
Computational Approach. We model the experimental
k {
⟨μ|a pUp(r) ·p|ν⟩
(10)
setup of STM-induced luminescence as shown in Figure 1a.
For simplicity, the STM tip is modeled as a linear gold chain,
Previous experiments showed that photon density of states in while the bulk gold substrate is represented by four atomic
STM junctions can be enhanced due to cavity effect, and the layers with a (100) surface. An H2Pc molecule is placed in the
enhancement factor is found to be on the order of 104,36−39 nanogap between the tip apex and the substrate. It is known
compared to that in free space. Thus, we define the spectra that intrinsic emissions from molecules are quenched by
density of plasmon mode as electronic interactions with metal substrates. The luminescence
of single molecules, however, has been detected by introducing
ωp2 1 Γp a thin insulating layer to electronically decouple the systems
Jp (ω) = 104 × Vp 3 3 from the conducting substrates.9,10 To examine the intrinsic
(2π ) c 2π Γp 2
(ω − ωp)2 + ()2 (11) molecular emission, in our model, the H2Pc molecule is
separated from the substrate by 5 Å to avoid strong molecule−
where Γp is the decay rate of the plasmon mode. In this work, substrate interactions, while the distance is short enough to
the plasmon is coupled to free photons and is broadened by a allow electrons to tunnel through the junction and sustain a
Lorentzian function with width of 0.5 eV to account for the steady-state current. The simulations of electron transport and
plasmon decay.40−42 Taking into account the spectra density in luminescence are based on solving the NEGF equations for the
eq 11, the frequency-dependent self-energy for electron− nanojunction in the presence of electron−plasmon inter-
plasmon interaction is modified as actions, which has been applied to the study of various
nanoscale optoelectronic devices.21,23,24,43−45 The rate of
Σ<ep,>(E , ω) = Jp (ω)MpG0<(E ± ℏω)Mp (12) carrier exchange between the molecule and contacts, and
hence the steady-state current, are determined by self-energies
Finally, the luminescence intensity can be calculated by Σt and Σs for the tip and substrate, respectively. Electron−
substituting the interaction self-energy into the Meir-Wingreen plasmon interactions are included as perturbations via self-
formula21 energy Σep. To demonstrate our method, the electronic
structure of the model is described at the density functional
F(ω) =
2
ℏ
∫ 2dEπ Tr[Σ<ep(E , ω)G0>(E)] (13) tight-binding (DFTB) level46,47 using the augorg-1-1 param-
eter set, which was developed specifically for describing organic
Photon Image. To construct spatially resolved photon molecules in contact with gold systems.48 It has recently been
images, we systematically positioned the tip over the H2Pc shown that Coulomb interactions are important for accurate

Figure 1. (a) Atomistic model for the simulations. A single H2Pc molecule is placed at the nanogap between the tip and substrate of the STM.
Inset: Atomic structure of H2Pc molecule. Red crosses illustrate three different tip positions for acquiring luminescence spectra. PDOS of the (b)
gold substrate, (c) H2Pc molecule, and (d) tip.

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description of conductance and optical transitions in molecular

junctions.49,50 In this work, because of computational cost,
single-particle Hamiltonian is employed; however, the current
approach can be combined with more sophisticated electronic
structure methods to take into account electron−electron
interactions.51,52 The local density of states (LDOS) can be
obtained by projecting Green’s function on real space as
1
D(r, E) = − π ∑ij Im[Gijr(E)]ϕi*(r)ϕj(r). Here, the imaginary
part of the retarded Green’s function Gr describes the
electronic structure of the nanogap and ϕ(r) represents the
atomic basis function.
Electronic Properties of the Single-Molecule STM
Junction. We first examine the electronic structure of the Figure 2. (a) Emission spectra of the STM molecular junction (black
H2Pc molecule within the nanogap of the STM configuration. line) and a bare STM junction (red line). (b) Schematic diagram
Figure 1b−d shows respectively the projected density of states showing the processes of inelastic tunneling of hot carriers and the
(DOS) of the substrate, molecule, and tip under zero bias luminescence.
voltage condition. It is observed that both the tip and substrate
have a continuum of energy states. The DOS of the tip in significantly enhanced when the molecule is coupled to the
Figure 1d is consistent with that of an atomic gold wire plasmon because of the increased local density of photonic
calculated using density functional theory. Compared to states. In principle, luminescence can occur when excited
atomic gold tip employed in other studies,53 the atomic carriers are injected into the frontier orbitals of the molecule.
chain adopted in this study has similar electronic structure To understand why emission corresponding to HOMO−
where the energy band below Fermi level consists of mainly d- LUMO transition is not observed in the simulations, we varied
states. On the other hand, the H2Pc molecule shows discrete the tip position and investigated the emission properties of the
levels. As the molecule is well-separated from the substrate, the junction. Figure 3a shows the emission spectra calculated
molecular states only weakly hybridize with the orbitals of gold under a bias voltage of 2.0 V for three different tip positions as
atoms at the surface. At equilibrium, it is shown that the indicated in Figure 1. Interestingly, the spectra are completely
HOMO of H2Pc is approximately 0.35 eV below the Fermi different for the three tip positions. The results show that two
level. Because of the central hydrogen atoms, molecular different optical transitions occur when the tip is positioned at
symmetry is reduced from D4h to D2h, and the 2-fold different isoindole unit while no emission is observed when the
degeneracy of the LOMOs of phthalocyanine is split. tip is located over the H2Pc center. It is understood that charge
Consequently, the LUMO and LUMO+1 are 0.91 and 1.00
eV above the Fermi level, respectively.
STM Luminescence of H2Pc Molecule. The STM
junction is then driven into nonequilibrium by external voltage
and the electroluminescence spectrum is calculated. In STM
experiments, a nanocavity is formed between the tip and the
substrate, which supports localized plasmons. To simulate
photon emission from STM junctions, the interaction between
tunneling electrons and the plasmonic field is considered.
Because of its strongly confined nature, the spatial dependence
of the plasmonic field is taken into account explicitly.35,44 This
allows us to describe the inelastic tunneling and the associated
radiative recombinations of charge carriers in the nano-
junction. The tunneling-electron-induced light emission of
the STM molecular junction is shown in Figure 2a. The
emission spectrum is calculated with the tip positioned on top
of one of the isoindole units, and the applied voltage is 2.0 V. A
sharp emission peak centered at 1.35 eV is observed. For
comparison, the emission spectrum of a bare STM junction is
also presented in Figure 2a, and clearly, a broad featureless
emission is observed. Therefore, the sharp peak at 1.35 eV can
be attributed to molecular luminescence. The emission
frequency is consistent with the energy of the molecular
transition between HOMO and LUMO+1 whereas the
emission corresponds to HOMO−LUMO transition is
missing. The mechanism of the luminescence can be explained
Figure 3. (a) Emission spectra calculated at three tip positions over
by the process shown in Figure 2b. Here, electrons from the tip the H2Pc molecule, as indicated in Figure 1a. (b) LDOS of the system
tunnel through the molecule inelastically by losing energy to a along the tunneling current direction. The red dashed lines mark the
plasmon in the junction. The plasmon is then assumed to Fermi level for the tip and substrate. The black dashed lines separate
decay efficiently into far-field photons. Compared to the the system into tip, molecule, and substrate regions. All properties are
vacuum environment, the rate of spontaneous emission is calculated under a 2.0 V bias voltage and constant tip height.

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injection from the tip to the molecule directly depends on the
spatial distribution of the molecular orbitals. Thus, the
luminescence should be sensitive to the tip position.
Examining the frontier molecular orbitals of an isolated H2Pc
obtained with DFTB (see Figure S1, Supporting Information),
it can be seen that the HOMO delocalizes along both
molecular axes, while LUMO and LUMO+1 each extend along
one of the molecular axes. These molecular states act as
channels for charge carriers to tunnel through the junction,
which can be seen in the transmission function (see Figure
S2). Hence, when the tip is located at P1, hot electrons are
injected from the tip into LUMO+1 and hot holes are injected
from substrate to HOMO. The emission peak at 1.35 eV can
therefore be attributed to the HOMO−LUMO+1 transition of
the molecule, whereas at P2 hot carriers are instead injected
into LUMO and the emission peak at 1.26 eV is assigned to
the HOMO−LUMO transition. On the other hand, no
emission is observed when the tip is positioned at the center
of H2Pc because of the absence of electronic state. The optical
transition mechanism is illustrated in the LDOS plotted in
Figure 3b. When the bias voltage is increased to 2.0 V, both
LUMO and LUMO+1 enter the external bias window. In
addition, HOMO is shifted upward toward the Fermi level
because of the change in electrostatic potential across the
junction. As a consequence, holes are injected from the
substrate into HOMO while electrons are injected from the tip
into the unoccupied molecular states. The latter depends
strongly on the tip position and the spatial distribution of the
corresponding electronic states. Radiative recombination of
these charge carriers then gives rise to light emission. It is
shown that light emission of the junction is also affected by the
molecular states even when there is no molecular lumines-
cence. As illustrated in Figure S4, at a low bias voltage of 1.2 V,
only LUMO is within the applied bias window and transitions
between the molecular state and electronic states in substrate
contribute to the light emission of the junction.
The subnanometer resolution of STM allows us to construct
photon images based on the emission intensities generated by
excitation at different molecular positions. To further illustrate
the above mechanism, we calculate the transition densities and
compare with the photon images of the involved optical
transitions. Figure 4a,b show respectively the corresponding
transition densities of HOMO−LUMO and HOMO−LUMO
+1 transitions. For the photon images, we systematically
calculated the emission spectra by moving the STM tip over
the molecule. The emission intensity is then integrated for
each tip position to construct the photon image. Figure 4c
presents the photon image which shows bright features over
the four isoindole units and a dark center. The result agrees
well with the experimental observations.13,18 Each pixel of the
photon image represents the excitation probability for the
radiative process when the tip is placed at that point. The
optical transitions can be further revealed spatially through the
spectrally resolved photon image. Energy-resolved photon
images are constructed by integrating separately for each
emission frequency. Figure 4d,e shows the STM-induced
luminescence images for the emission peaks at 1.26 and 1.35
eV, respectively. Each energy has an emission intensity
localized along one of the molecular axes. The emission
pattern for the lower energy peak closely resembles the
transition density associated with the HOMO−LUMO
transition in Figure 4a, and the pattern for the higher-energy
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Figure 4. Transition densities for the (a) HOMO−LUMO and (b)
HOMO−LUMO+1 transitions of the H2Pc molecule calculated with
DFTB. (c) Photon image obtained by integrating the whole emission
spectrum. Spectrally resolved photon images obtained by integrating
emission intensities for the (d) HOMO−LUMO and (e) HOMO−
LUMO+1 transitions. All photon images are calculated under a 2.0 V
bias voltage.
peak resembles that of the HOMO−LUMO+1 transition in
Figure 4b.
It has been reported that the molecular luminescence could
be suppressed by strong interactions with the metallic
substrate.9,10 This quenching effect is illustrated in Figure S3
which plots the electroluminescence spectrum when the
molecule is placed 3.36 Å (the sum of the van der Waals
radii) above the substrate. It can be seen that the emission
features associated with molecular transitions are missing, and
instead, a broad emission which resembles the spectrum of the
bare junction is resulted. The corresponding PDOS of the
substrate, molecule, and tip is plotted in Figure S3b−d. The
simulations reveal that the molecular orbitals strongly
hybridize with the electronic states of the substrate. This
results in charge and energy transfer between these states and
molecular luminescence is therefore quenched.
Controllable Light Emission in STM Junctions. The
position-dependent luminescence of STM junctions can be
exploited in optoelectronics as controllable single-molecule
emitters. Because of the D2h symmetry of H2Pc molecules, the
LUMOs lying along the two orthogonal molecular axes are
split. This gives rise to two possible optical transitions, which
can be excited locally by the tunneling electrons. As shown in
Figure 3a, the frequency of emitted photons can be controlled
by changing the tip position. When the tip is positioned at P2,
radiative recombination between charge carriers in HOMO
and LUMO occurs. On the other hand, when the tip is
positioned at P1, charge carriers in HOMO and LUMO+1
recombine. Via the selective injection of charge carriers into
the corresponding electronic state, excitation of the radiative
process with different frequencies can be chosen. It is therefore
possible to design single-molecule light-emitting devices with
controllable wavelengths. By careful refinement of the chemical
structures, devices with desirable frequencies at different parts
DOI: 10.1021/acs.jpcc.9b02198
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of the emitting unit can be designed. The proposal is therefore
versatile for applications in nanoscale optoelectronics and has
potential for use in future hybrid electronic−photonic circuits.
■
DISCUSSION
We have presented atomistic simulations of the STM-induced
luminescence of single-molecule junctions on the basis of our
recently developed NEGF quantum transport formalism.
Previous efforts have been made to successfully explain the
spectral features using simple models.54−56 In these theoretical
works, many-body effects like electron correlations, electron−
phonon interactions, can be readily included. Recently, it has
been demonstrated that Fano resonance appears in emission
spectrum because of the interaction between molecular
excitations and plasmons. In the current approach, the many-
body effects can be taken into account via interaction of self-
energies, which have to be solved self-consistently.57−60 In
addition, the effects of molecular excitations on plasmons can
also be included by this self-consistent calculation. Because of
the highly localized tunneling electrons originating from the
STM tip, the spatial distributions of the molecular states play
an important role in the transport and optical properties of
nanojunctions. The simulations in this work explicitly take into
account the nanoscale nature of the experiments, which is
crucial for obtaining the spatial variations of the molecular
electronic states and their transition probabilities for the
radiative process. Because of the highly localized tunneling
electrons originating from the STM tip, the spatial
distributions of the molecular states play an important role
in the transport and optical properties of nanojunctions. These
simulations also allow us to generate photon images, and the
results agree well with those of the experiments. This work
paves the way for understanding the complex interactions
between molecular excitations and plasmons in nanojunctions
and utilizing them in diverse applications in nanoscale
optoelectronics.
STM-induced luminescence is proposed as a new route
toward nanoscale tunable light sources. The emission
frequency of an STM molecular junction can be controlled
by precise positioning of the tip. This allows adjustable
coupling and charge injection to selected molecular electronic
states, where radiative decay occurs consequently. It is
therefore possible to realize controllable light emission by
the proper design of emitting units at the molecular
level.16,53,61 Recently, the atomically precise design of graphene
nanoribbon edges has been realized experimentally. This
allows the rational engineering of the topological electronic
structures for potential applications in spintronics and
quantum computing.62−64 Specifically designed graphene
nanoribbons achieved via edge functionalization can therefore
provide a platform for realizing the proposed nanoscale light-
emitting device. Our results demonstrate the possibility of
controlling light emission from single-molecule junctions. We
believe this finding may contribute to the fundamental
understanding and lead to the realization of applications in
nanoscale optoelectronics and high-resolution spectroscopy.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jpcc.9b02198.
15766
Article
Molecular orbitals of H2Pc molecule; transmission
spectra at a different bias voltage and the spatial
distribution of transmission within the molecular
plane; emission spectra of the STM junction when the
molecular orbitals strongly hybridize with the electronic
states of the substrate; formalism for calculating the
tunneling currents (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: yamcy@csrc.ac.cn (C.Y.Y.).
ORCID
Yu Zhang: 0000-0001-8938-1927
ChiYung Yam: 0000-0002-3860-2934
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The financial support from the National Natural Science
Foundation of China (21322306, 21673017, and U1530401),
Science Challenge Project (TZ2018004), and the National
Basic Research Program of China (2014CB921402) is
gratefully acknowledged. The computational support from
the Special Program for Applied Research on Super
Computation of the NSFC-Guangdong Joint Fund (the third
phase) (U1501501) and the Beijing Computational Science
Research Center (CSRC) is also acknowledged. Y.Z. acknowl-
edges the support from the Los Alamos National Laboratory
(LANL) Directed Research and Development Funds (LDRD,
LANL is operated by Triad National Security, LLC, for the
National Nuclear Security Administration of the U.S. Depart-
ment of Energy (Contract No. 89233218NCA000001).
■
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15768 DOI: 10.1021/acs.jpcc.9b02198

J. Phys. Chem. C 2019, 123, 15761−15768