LETTERS
PUBLISHED ONLINE: 20 DECEMBER 2009 | DOI: 10.1038/NPHOTON.2009.257
Generation of molecular hot electroluminescence
by resonant nanocavity plasmons
Z. C. Dong*, X. L. Zhang, H. Y. Gao, Y. Luo, C. Zhang, L. G. Chen, R. Zhang, X. Tao, Y. Zhang,
J. L. Yang and J. G. Hou*
Control of the radiative properties of functional molecules
near metals is a key issue in nano-optics, and is particularly
important in the elds of energy transfer and light manipu-
lation at the nanoscale1,2 and the development of plasmonic
devices35. Despite the various vibronic transitions (S1(v0 ) !
S0(v)) available for frequency tuning of uorescence, the
molecular emissions near metals reported to date have been
subject to Kashas rule, with radiative decay from the lowest
excited state (S1(0)) (refs 610). Here, we show resonant hot
electroluminescence arising directly from higher vibronic
levels of the singlet excited state (S1(v0 > 0)) for porphyrin mol-
ecules conned inside a nanocavity in a scanning tunnelling
microscope, by spectrally tuning the frequency of plasmons.
We also demonstrate the generation of unexpected upconver-
sion electroluminescence. These observations suggest that
the local nanocavity plasmons behave like a strong coherent
optical source with tunable energy, and can be used to ac-
tively control the radiative channels of molecular emitters by
means of intense resonance enhancement of both excitation
and emission.
In principle, molecular uorescence can be controlled over a
wide energy range and with selected frequency by tuning the emis-
sion from various vibronic transitions (S1(v0 ) ! S0(v)) through res-
onance enhancement near plasmonic structures2. However, optical
excitation of polyatomic molecules with nanoantennas yields spec-
tral modications predominantly on normal uorescence (S1(0) !
S0(v  0)) (refs 610), and the observation of high-energy hot lumi-
nescence from highly excited vibronic states S1(v0 . 0) (ref. 11) is
inconclusive. Indeed, there are just a few reports suggesting a
slight increase in the intensity of scattered light near the incident
photon energy12,13. The challenging issue for the generation of hot
luminescence is whether one can create a situation in which the
radiative decay directly from S1(v0 . 0) can become comparable to
rapid internal relaxation in the excited state13.
One route to achieving such a situation is to use the strong near-
eld enhancement of resonant plasmons that are highly conned
inside a nanocavity13 dened by a metallic nanotip and substrate
in a scanning tunnelling microscope (STM)14. With the gap distance
controlled down to the sub-nanometre regime, intense radiation
enhancement of 425 orders of magnitude15 can be generated
and could lead to substantial plasmonexciton coupling when mol-
ecules are conned inside the small mode volume of the nanocav-
ity5. Electrical excitation by STM has the additional advantage
that it can tune, in situ, the spectral prole of nanocavity plasmons
(NCPs) by simply modifying the tip status, followed by direct
measurement of its resonance mode. Moreover, excitation by tun-
nelling electrons (a non-optical excitation) removes any complexity
that may occur due to disturbance of the incident light (for example,
Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026, China; These
authors contributed equally to this work. * e-mail: zcdong@ustc.edu.cn; jghou@ustc.edu.cn
50
2010 Macmillan Publishers Limited. All rights reserved.
through Rayleigh scattering), enabling clean detection of the
emitted photon signals, even for resonance uorescence.
In this work, we report an experimental study of electrically
driven molecular uorescence of porphyrins in a highly conned
nanocavity (,3 nm) in STM. By controlling the NCP resonance
mode, we can not only tune the colour of the molecular uo-
rescence, but can also generate hot electroluminescence from
highly excited vibronic states and upconversion electroluminescence
with the energy of emitted photons that is higher than that of exci-
tation electrons. These observations reveal new optoelectronic
effects that are useful for exploring the near-eld character of
NCPs and the associated eld enhancement, and provide a new
understanding of the coupling and interconversion of electrons,
excitons, plasmons and photons.
To generate molecule-specic electroluminescence near metals,
the electronic decoupling of molecular emitters by spacer layers is
crucial to avoid uorescence quenching1619. Here, we use a multi-
monolayer decoupling approach in which the top molecules act as
light emitters (Fig. 1). The widely studied tetraphenyl porphyrin
(TPP) molecules, with their characteristic double-peak Q-band
emission20, were used as both spacers and uorophores. The
growth of TPP molecules was monitored by high-resolution STM
imaging, which shows layer-by-layer growth with highly ordered
patterns. The asymmetric lobe distribution in the sub-molecular
resolved image (Fig. 1c) suggests a tilted molecular conguration
for the top molecules. Figure 1d shows STM induced luminescence
(STML) spectra for a well-decoupled sample of ve-monolayer
(ML) TPP on gold for excitation voltages larger than the optical
bandgap of the molecules (1.9 eV)20. The molecular origin of
the luminescence is clearly collaborated by the good agreement
with the photoluminescence spectrum of the same sample
through the molecule-specic double-peak emission of Qx(0,0) at
1.89 eV and Qx(0,1) at 1.73 eV (refs 17,20).
Surprisingly, even when the excitation voltages (for example,
Vb 1.8 V) are less than the optical bandgap, the luminescence
spectra for the molecular sample reveal the emission of energy-for-
bidden upconversion photons for which the energy hn exceeds the
energy of a tunnelling electron (eVb), as illustrated in the yellow-
shaded region of Fig. 2a. Two well-dened emission bands are
evident above 1.8 eV, one peaking at 1.89 eV and the other at
2.05 eV, with a peak spacing of 0.16 eV. Because light emission
from the pristine metal substrate is known to follow the quantum
cutoff hn  eVb , with the photon energy limited by the bias
voltage (Fig. 2b)21, these two emission bands are evidently
molecule-specic. The peak around 1.89 eV coincides with the
(0,0) radiative transition. However, the occurrence of the new
emission band around 2.05 eV is particularly interesting, not
only because this peak has never been reported in documented
NATURE PHOTONICS | VOL 4 | JANUARY 2010 | www.nature.com/naturephotonics
NATURE PHOTONICS DOI: 10.1038/NPHOTON.2009.257 LETTERS

Tip h

e
NH N

N HN

5 ML
Spacer
+
Metal substrate

Wavelength (nm)
775 689 620 564 517

Qx(0,0)
W-tip/TPP/Au
Qx(0,1)

STML (a.u.) +3.0 V

+2.5 V

2.5 V

PL
1.6 1.8 2.0 2.2 2.4
Photon energy (eV)

Figure 1 | Electronic decoupling for molecular uorescence from local STM cavities. a, Molecular structure of TPP. b, Schematic junction geometry with
multi-monolayer stacking and localized electrical excitation from a nanotip. c, STM image showing highly ordered molecular stacking for 5-ML TPP molecules
on Au(111) (55  55 nm2, 2.5 V, 2 pA). The inset is a high-resolution image with each molecule resolved into one bright lobe and several other relatively
dark lobes (6  6 nm2, 2.5 V, 2 pA). d, Typical STML spectra for 5-ML TPP on gold excited at 200 pA using a tungsten tip. The zero-phonon Qx(0,0) peak
at 1.89 eV and the Qx(0,1) vibronic overtone at 1.73 eV (for simplicity, hereafter abbreviated as (0,0) and (0,1), respectively) have a peak spacing of
0.16 eV, both arising from the p*p transitions of porphyrins. Such molecule-specic uorescence occurs for both bias polarities and presents similar
spectral proles at different bias voltages. PL, photoluminescence.

photoluminescence data for TPP (ref. 20), but also because its
energy is even higher than that of the (0,0) transition, the highest
energy possible for relaxed uorescence. Judging from the peak
spacing of 0.16 eV being the same as the vibrational energy-level
spacing between (0,0) and (0,1), this new emission peak may be
attributed to the S1(v0 1) ! S0(v 0) transition in TPP molecules,
namely, the relaxationless (1,0) hot luminescence arising directly
from the higher vibrational level of the singlet excited state. The
observed strong (1,0) hot luminescence indicates a comparable
competition of this fast dynamic radiative process with the internal
relaxation13, which is quite remarkable for the large polyatomic TPP
molecule with its densely populated vibrational levels and near
metals. The underlying mechanism may be understood by applying
the model proposed by Le Ru and colleagues13. Furthermore, the
occurrence of unrelaxed hot electroluminescence at 2.05 eV
under an upconversion bias (for example, 1.8 V) is also remarkable
and implies the presence of some particular pumping and coupling
mechanism inside the STM nanocavity.
Another notable feature in Fig. 2a is the signicant modication
of the spectral proles from the conventional double-peak feature
in Fig. 1d to a very different three-peak structure. Such spectral
prole modications, together with the upconversion molecular
electroluminescence, appear quite universal for different combi-
nations of plasmonic tip and substrate materials (Fig. 2a).
Furthermore, depending on the tip status and resultant NCP
resonance mode22, the spectral prole modication can be even
more remarkable, with additional new emission bands extending
into both lower and higher energy regions. As shown in Fig. 3, as
the local plasmonic resonance mode of the nanocavity is spectrally
tuned by means of tip-status modications to match with the par-
ticular (v0 ,v) radiative transition of the TPP molecules, the selected
vibronic transition (lightly shaded peak in Fig. 3a) is greatly
enhanced owing to the strong resonant plasmonic pumping at
that frequency. Such a selected enhancement leads to a reversal of
the relative intensities for the double-peak structures from tip 2 to
tip 3 and the unprecedented occurrence of the low-energy (0,2)
sideband around 1.6 eV (tip 1) and the high-energy (2,0) hot lumi-
nescence band around 2.2 eV (tip 5), which gives a clear demon-
stration of colour-tuning over a considerably widened energy
range for molecular resonance electroluminescence. Resonance
here refers to the NCP mode rather than to the excitation voltage.
Owing to the broadband feature of the NCP resonance modes,
the conventional two Q-band emissions ((0,0) and (0,1)) of the
TPP molecules always show up in the molecular uorescence

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2010 Macmillan Publishers Limited. All rights reserved.
LETTERS
With molecules
(0,1) (0,0) (1,0) Vb = +1.8 V
Upconversion region
STML (a.u.) W-tip/TPP/Au
Pt-tip/TPP/Au
W-tip/TPP/Ag
1.6 1.8 2.0 2.2 2.4
Photon energy (eV)
Without molecules
Vb = +1.8 V
STML (a.u.)
Quantum cutoff: hv eVb
W-tip/Au
1.6 1.8 2.0 2.2 2.4
Photon energy (eV)
Figure 2 | Upconversion electroluminescence of molecules with unusual
hot luminescence. a, STML spectra acquired from a sample of 5-ML TPP
molecules on metal surfaces excited at 1.8 V and 400 pA for different
material combinations: tungsten-tip/TPP/gold (red curve), platinum-
tip/TPP/gold (pink curve) and tungsten-tip/TPP/silver (blue curve). The
photons of the two emission bands in the yellow-shaded region have an
energy higher than that of excitation electrons (1.8 eV), demonstrating the
occurrence of upconversion electroluminescence. The (1,0) band is
attributed to the relaxationless hot luminescence. b, Typical STML spectra
from the pristine metal surface (tungsten-tip/gold excited at 1.8 V and
400 pA), showing an NCP prole with the bias-limited energy cutoff for the
emitted photons.
spectra in Fig. 3a because of their relatively large FranckCondon
factors. However, the observed pronounced spectral modications
suggest that the molecular spectral prole F(v) under plasmonic
pumping no longer simply follows the FranckCondon distribution
of the emission process, Fem(v), but is closely related to the fre-
quency-dependent uorescence enhancement g(v) of NCP modes
via F(v) / g(v)Fex(v)Fem(v) (refs 6,9,13), where Fex(v) is the
NCP-modied excitation spectral prole of the molecules. The sub-
stantial plasmonexciton coupling at resonance thus plays a crucial
role in determining the spectral shape and generating new emission
bands. In other words, the spectral prole modications presented
here are not caused by a change of the energy levels of emitting mol-
ecules (which would usually occur due to molecular aggregation23,
absorption conguration variation24 or energy-level shift through
dipole interaction with nearby metals25), but is rather a result of
the strong resonant excitation by localized plasmonic elds, fol-
lowed by resonance uorescence from the non-equilibrium
excited states. To our knowledge, this is the rst rm observation
of molecular resonance uorescence with frequency tuning over a
wide spectral range.
How can such a resonance enhancement occur at low bias (for
example, 1.8 V) when the plasmon energy is lower than and off-res-
onance with the (0,0) or (1,0) electronic transitions (Fig. 2b)? To
establish the underlying mechanism for the occurrence of anoma-
lous upconversion molecular electroluminescence, we also investi-
gated the bias and current dependency of emission intensities.
52
2010 Macmillan Publishers Limited. All rights reserved.
NATURE PHOTONICS DOI: 10.1038/NPHOTON.2009.257
The quantum yield against bias indicates the presence of an onset
voltage around +1.6 V for molecular electroluminescence
(Fig. 4a). The onset voltage appears the same for different tip and
substrate materials, from tungsten-tip/TPP/gold to platinum-
tip/TPP/gold and tungsten-tip/TPP/silver, which implies that
the onset voltage does not depend on the electron injection
barrier between the Fermi level of the electrode and the lowest unoc-
cupied molecular orbital, but correlates with particular electronic
transitions inside the TPP molecule. On the other hand, unlike
the linear relation at bias larger than the optical bandgap
(for example, 2.5 V) that suggests essentially single-step excitation
events, the current dependency of photon intensities at 1.8 V
reveals a nonlinear behaviour with a power-law exponent of 1.6
(Fig. 4b), indicating the possibility of involvement of two-
or multi-step excitation processes for the upconversion
electroluminescence.
The observation of upconversion luminescence with an onset
voltage of 1.6 V at low currents (for example, 200 pA) and a
quantum efciency around 1  1025 photons/electron at 1.8 V
enables us to exclude the following four mechanisms (see
Supplementary Information): the stepwise accumulation of energy
via excited state absorption as in two-photon uorescence
spectroscopy26, the Auger-like27 and hot-electronhole cascade21
two-electron processes proposed for sodium quantum wells or
atomic contacts, and the triplettriplet annihilation mechanism in
CuPc on gold28.
The clear observations of both NCP-mode selective enhance-
ment and NCP-assisted generation of hot electroluminescence
strongly indicate not only the involvement of local NCPs in the
light excitation and emission process (a dominant excitation
channel), but also a considerable population rate of electrons
moving into higher vibrational states via plasmonic pumping.
Because there is little difference in the underlying physics of
light excitation processes between the normal bias (for example,
2.5 V) and upconversion bias (for exampe, 1.8 V) and, in fact,
the spectral shaping behaviour by resonant NCPs at a bias of
1.8 V appears similar to that at 2.5 V, one might expect a
similar pumping picture for upconversion electroluminescence.
In other words, the higher vibrational states could be populated
through a plasmon-assisted multi-step inelastic scattering
scheme (see Supplementary Information), in which the underlying
physics may resemble that invoked in surface-enhanced Raman
scattering29. The NCPs, excited by both tunnelling electrons and
plasmonexciton coupling, act as a near-eld light source,
pumping the molecule into higher vibrational excited states
S0(v . 1) through stepwise inelastic processes, and can eventually
reach the electronic excited state S1(0). The subsequent (0,0) u-
orescence triggers new plasmons that can be further amplied
through the substantial plasmonexciton coupling resonant at
(0,0). The intense near eld of the resonant plasmons behaves
like a strong coherent optical excitation source, leading to
increased population rates of excited states and new resonance-
enhanced uorescence of the molecules, although the exact
nature of this excitation process remains to be claried. The gen-
eration of (1,0) upconversion electroluminescence requires the res-
onant matching of NCP modes with the (1,0) vibronic transition,
which provides further evidence for the substantial involvement of
plasmons in the light amplication process. The molecules act not
only as an energy sink and active emitting medium, but also as
efcient local sensors to map out the NCP mode to the far eld.
The exquisite energy transfer and the coherent character of plas-
monic near elds demonstrated here shed new light on how energy
can be converted from electrons to photons by means of plasmon
exciton coupling in a nano-environment. The generation of higher-
energy plasmons and photons from low-energy electrons opens up
new opportunities to explore plasmonexciton coupling in
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NATURE PHOTONICS DOI: 10.1038/NPHOTON.2009.257 LETTERS
Wavelength (nm) Wavelength (nm)
775 689 620 564 775 689 620 564

W-tip W-tip (i) NL

+2.5 V, 200 pA
(0,2)
S1
TPP
Au Tip 1 h
(0,1) Au

(0,0) (0,2)
Tip 2
(0,1)
(0,0)
STML (a.u.)

E
Tip 3 S0 ~0.16 eV

(ii) HL
(1,0) S1

Tip 4

E h

(2,0)
(2,0)
Tip 5 (1,0)

1.4 1.6 1.8 2.0 2.2 2.4 1.4 1.6 1.8 2.0 2.2 2.4
S0
Photon energy (eV) Photon energy (eV)

Figure 3 | Shaping emission spectra of molecules by resonant NCP. a, Left: STML spectra from a pristine gold surface, showing NCP modes dened by the
tungsten-tip/gold cavity with different resonance maxima tuned to match the particular (v0 ,v) radiative transition (S1(v0 ) ! S0(v)) of the TPP molecules. Right:
Corresponding luminescence spectra acquired immediately afterwards from a molecular sample of 5-ML TPP on gold using the particularly dened tungsten-
tip status, showing great resonance enhancement of the particular emission peak (lightly shaded) and pronounced spectral prole modications. The peak
assignment was based on the equispacing feature of vibrational levels. b, Schematic of various vibronic transitions: (i) normal luminescence (NL) emitting
from S1(0) and (ii) hot luminescence (HL) from highly excited S1(1) or S1(2). All spectra were acquired at 2.5 V and 200 pA.

3 100
W-tip/TPP/Au
W-tip/TPP/Au
+1.6 V Iph It
Photon intensity, Iph (kcps)

+1.5 V
STML (a.u.)
Quantum yield (105)

2 +2.5 V
10

1.5 2.0 2.5

1 Photon energy (eV) 1.6
Iph It

1.6 V turn on 1
+1.8 V
0
3 2 1 0 1 2 3 100 200 300 400 500
Bias (V) Current, It (pA)

Figure 4 | Bias and current dependence of molecular junction electroluminescence. a, Quantum yield versus bias voltage, showing a +1.6 V onset voltage
that was also conrmed by the uorescence spectrum (inset), It 200 pA. b, Double-logarithmic plot of photon intensity versus current, showing a linear
relation at 2.5 V and a power-law nonlinear variation at 1.8 V with an exponent of 1.6.

molecular nanoplasmonics. Our ndings may pave the way for the layer by layer and conrmed by STM imaging (Supplementary Fig. S2). Tungsten
development of electrically driven nanoscale light sources2,6, ultra- tips were prepared by electrochemical etching and cleaned by electron
bombardment and argon-ion sputtering, followed by voltage pulses on clean metal
high-resolution spectroscopy and sensing3,4 and ultrafast dynamic surfaces until a stable tip condition with the desired NCP modes was achieved. STM
techniques8,30. images were taken in a constant-current topographic mode with the sample biased.
Photons emitted from the tunnel junction were collected by a double-lens system.
Luminescent spectra were acquired at 80 K over a typical period of 10 min, at a
Methods spectral resolution of 4 nm over 330900 nm, using a liquid-nitrogen-cooled
All experiments were performed with a custom-designed system of an ultrahigh- charge-coupled device spectrometer (Princeton Instruments). The thermal drift at
vacuum, low-temperature STM (Unisoku) combined with optical detectors 80 K was 50 pm min21. The luminescent spectra from molecules were acquired in
(Supplementary Fig. S1). TPP molecules were evaporated in ultrahigh vacuum by the tunnelling regime at small currents, typically 200 pA (unless specied explicitly).
sublimation from a Knudsen cell at 250 8C onto atomically clean Au(111). The During acquisition, the tip was positioned statically above the sample with a stable
deposition rate, 0.12 ML min21, was monitored by a quartz microbalance and tunnel resistance to avoid modication of the tip and surface conditions, as
calibrated by STM images. The growth of TPP molecules on gold was carried out conrmed by subsequent STM imaging with intact ordered structures. Light

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2010 Macmillan Publishers Limited. All rights reserved.
LETTERS
intensities were measured by a cooled microchannel plate photomultiplier tube
(Hamamatsu) over 1852870 nm and calibrated using the photon collection
efciency and detection efciency.
Received 28 July 2009; accepted 18 November 2009;
published online 20 December 2009
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Acknowledgements
The authors acknowledge discussions with B. Wang and X.P. Wang, and support from the
National Basic Research Program of China (grant nos 2006CB922003 and 2010CB923300),
the Chinese Academy of Sciences (grant no. KJCX2.YW.H06) and the Natural Science
Foundation of China (grant nos 10574117 and 10974186).
Author contributions
X.L.Z. and H.Y.G. contributed equally to this work. Z.C.D., Y.L. and J.G.H. supervised the
project, designed experiments, analysed the data and wrote the paper. X.L.Z. and H.Y.G.
performed experiments and analysed data. C.Z., L.G.C. and R.Z. performed experiments.
X.T. and Y.Z. performed simulations and data analysis. J.L.Y. analysed data and edited
the paper.
Additional information
The authors declare no competing nancial interests. Supplementary information
accompanies this paper at www.nature.com/naturephotonics. Reprints and permission
information is available online at http://npg.nature.com/reprintsandpermissions/.
Correspondence and requests for materials should be addressed to Z.C.D. and J.G.H.
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