ARTICLES

PUBLISHED ONLINE: 15 MAY 2011 | DOI: 10.1038/NMAT3029

Nanoantenna-enhanced gas sensing in a single

tailored nanofocus
Na Liu1 , Ming L. Tang1 , Mario Hentschel2 , Harald Giessen2 and A. Paul Alivisatos1 *
Metallic nanostructures possess plasmonic resonances that spatially confine light on the nanometre scale. In the ultimate limit
of a single nanostructure, the electromagnetic field can be strongly concentrated in a volume of only a few hundred nm3 or less.
This optical nanofocus is ideal for plasmonic sensing. Any object that is brought into this single spot will influence the optical
nanostructure resonance with its dielectric properties. Here, we demonstrate antenna-enhanced hydrogen sensing at the
single-particle level. We place a single palladium nanoparticle near the tip region of a gold nanoantenna and detect the changing
optical properties of the system on hydrogen exposure by dark-field microscopy. Our method avoids any inhomogeneous
broadening and statistical effects that would occur in sensors based on nanoparticle ensembles. Our concept paves the road
towards the observation of single catalytic processes in nanoreactors and biosensing on the single-molecule level.

anoscale field confinement by metallic nanostructures is one

of the key aspects of nanophotonics17 . Localized surface
plasmon resonances (LSPRs) of metallic nanostructures812 ,
which are associated with collective oscillations of free electrons, can
generate large field confinement in an extremely small volume13 .
This so-called nanofocusing offers remarkable opportunities to
improve fluorescence1416 , Raman scattering17,18 , single-molecule
detection1921 and nonlinear nanospectroscopy22 . Metallic nanostructures with sharp corners or edges are especially favourable
for these purposes. The local field strength in the vicinity of a
sharp gold tip can be enhanced by several orders of magnitude
compared with the incident light2,23 . Importantly, nanofocusing
has immediate implications for plasmon-mediated chemistry24
and sensing2529 . The strong enhancement of the local fields in
a small sensing volume can be used to monitor the response of
LSPRs to a change in the surrounding dielectric permittivity8 .
So far, plasmonic sensing has been widely applied in many
different research areas including label-free detection of molecular
binding30 as well as monitoring low concentrations of biochemical
agents31,32 and gases33,34 .
The detection of flammable gases such as hydrogen is a vital
safety issue concomitant with the fast development of fuel cell
technology. Concentrations of hydrogen exceeding 4% may ignite
explosively. Palladium, one of the most catalytically active transition
metals, can absorb a substantial quantity of hydrogen within
its crystal lattice and form palladium hydride in a reversible
manner35 . The electrical and dielectric properties of palladium
change on hydrogen exposure36 , which in turn form the backbone
of electrical37,38 and optical hydrogen sensing39 . When compared
with sensors requiring electrical measurements, optical detection of
hydrogen is much more desirable owing to its inherent safety, as
no sparking can occur.
Recently, palladium-based nanomaterials4043 have attracted
much attention in that they show faster reaction kinetics owing
to their shorter diffusion lengths44 . Nevertheless, the LSPRs of
palladium nanoparticles possess very broad spectral resonance
profiles45,46 resulting from interband transitions in the whole

visible region47 . This constitutes a fundamental obstacle for optical

hydrogen detection using palladium nanoparticles. Very recently,
indirect optical sensing for hydrogen was introduced48,49 , using an
ensemble of palladium nanoparticles which were separated from
underlying gold discs by a SiO2 dielectric spacer. However, owing
to the wide size distribution of the palladium particles and gold
discs, only inhomogeneously broadened average characteristics
were measured. Also, the presence of the SiO2 spacer leads to the
dielectric screening of the near-fields of the gold discs.
In contrast to studies on an ensemble, single-entity measurements offer a unique tool for probing individual behaviour and
processes, which cannot be distinguished on the ensemble level.
Importantly, this advantage is favourable for plasmonic gas sensing
and opens an avenue towards understanding the influence of
geometries and nano-sizing on hydrogen storage performance50 .
Here we demonstrate resonant antenna-enhanced single-particle
hydrogen sensing in the visible region. We present a fabrication approach to precisely position a single palladium nanoparticle in the nanofocus of a gold nanoantenna (see Fig. 1b). The
strongly enhanced gold-particle plasmon near-fields can sense
the change in the dielectric function of the proximal palladium
nanoparticle as it absorbs or releases hydrogen36 . Light scattered
by the system is collected by a dark-field microscope with attached spectrometer and the LSPR change is read out in real
time. We demonstrate how the antenna enhancement effect can
be quantitatively controlled by manipulating the distance between
sensing object and nanoantenna. Additionally, we lay out how
the nanoantenna shape plays a key role for optimum sensitivity.
Specifically, we show an unambiguous correlation between the
sensor response and the antenna geometry. In contrast, the single
palladium nanoparticle alone is barely visible in the microscope,
and no useful spectral information can be derived (see Fig. 1a).
Our work provides a general blueprint for amplifying sensing
signals at the single-particle level, eliminating the statistical and
average characteristics inherent to ensemble measurements48,49 . In
particular, the inclusion of catalytic species such as palladium can
also offer advantages to in situ monitoring of catalytic events51 ,

1 Department

of Chemistry, University of California, Berkeley, and Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California
94720, USA, 2 4. Physikalisches Institut and Research Center SCoPE, Universitt Stuttgart, D-70569 Stuttgart, Germany. These authors contributed
equally to this work. *e-mail: APAlivisatos@lbl.gov.
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NATURE MATERIALS DOI: 10.1038/NMAT3029

ARTICLES
a

10.9

Scattered intensity

0.4

(V m1)

Pd

2.2

0
0.4

Wavelength

Au

Scattered intensity

2.0
10.9

Pd
Wavelength

as well as opportunities to study enhancements in the efficiency

of chemical conversion processes in electrochemistry and surface
science52 . Our work will advance the field of catalytic-activity
studies, which largely rely on fluorescence techniques53 . Finding
appropriate fluorophores is still a hurdle for many experiments
associated with fluorescent detection of catalytic events. Our approach, however, offers a promising alternative by employing
the change of dielectric permittivity, that is, refractive index and
absorption, of targeted biochemical entities for catalytic-activity
detection and biosensing.
Figure 2 shows the simulated electric-field distributions of two
palladiumgold antennas at resonance. The plasmonic antennas
are a gold triangle and a gold rod, respectively (see Fig. 2). The
incident light is polarized parallel to the longer axis of the system.
It is evident that, when the gold antenna is resonantly excited,
collective dipolar-like particle plasmons lead to greatly enhanced
fields at the tips of the gold triangle or at the corners of the gold
rod. Specifically, owing to the sharp tip feature of the gold triangle,
the near-fields are spatially concentrated in a single spot right next
to the palladium particle.
The nanostructures with two materials on the same plane
were manufactured by high-resolution electron-beam lithography
using a dual-exposure method. Figure 3 shows the processing
scheme. The gold antenna and the palladium particle were
manufactured on a glass substrate in two separate nanofabrication
cycles, which are associated with electron-beam exposure, metal
evaporation and lift-off (see Methods). The relative positions of
the two metallic constituents were accurately aligned using gold
markers54 . Our fabrication approach offers a unique opportunity
to independently control the sizes, positions and materials of
different constituents.
The sample was placed in a stainless-steel chamber with optically
transparent windows at room temperature. The chamber was
connected to two gas channels (ultrahigh-purity hydrogen and
nitrogen). The concentration of hydrogen was adjusted by tuning
the proportion of the two gases through mass-flow controllers.
632

b
20.4
9.3
3.4

(V m1)

Figure 1 | Schematic representation of antenna-enhanced single-particle

hydrogen sensing. a, Hydrogen sensing with a single palladium
nanoparticle. Hydrogen molecules and adsorbed hydrogen atoms are
shown in red. The palladium nanoparticle scatters weakly, showing an
extremely damped and broad spectrum. The palladium particle alone
causes a barely detectable change on hydrogen exposure. b, Hydrogen
sensing using a resonant antenna-enhanced scheme. The same palladium
nanoparticle is placed at the nanofocus of a gold antenna, which scatters
much more strongly. Hydrogen absorption on the palladium particle
changes its complex dielectric function, which causes a resonance shift
(1) of the gold antenna that can be optically detected.

0
3.1
8.8

20.4
E

Figure 2 | Electromagnetic finite-difference time-domain simulation of

the local electric fields. The polarization is along the vertical direction. a, A
gold triangle antenna with a palladium nanoparticle. Near the tip of the gold
triangle antenna, the electromagnetic fields are highly localized and
strongly enhanced. Any change of the permittivity of the palladium particle
will significantly influence the plasmonic resonance of the gold antenna.
The side length of the equilateral gold triangle is 110 nm and the gold
thickness is 40 nm. The diameter of the palladium particle is 60 nm and the
palladium thickness is 40 nm. The gap distance between the gold antenna
and the palladium particle is 10 nm. b, A gold rod antenna with a palladium
nanoparticle. The field enhancement in a rod antenna is more concentrated
at the corners. The length and width of the gold rod are 130 nm and 80 nm,
respectively, and its thickness is 40 nm. The diameter and thickness of the
palladium particle are 60 nm and 40 nm, respectively. The gap distance
between the gold antenna and the palladium particle is 20 nm.

Figure 3b shows a dark-field image of the palladiumgold antennas.

The distance between neighbouring structures is 20 m, allowing
for isolated single-particle measurements. One representative
scanning electron microscopy (SEM) image of the palladiumgold
antennas is also shown in Fig. 3b, demonstrating the excellent
alignment of the palladium nanoparticle with respect to the
gold antenna. The side length of the equilateral gold triangle
is 110 nm and the gold thickness is 40 nm. The diameter of
the palladium particle is 60 nm and the palladium thickness is
40 nm. The grain-like features on the substrate result from a
thin metal film evaporated after all the optical measurements
were done for SEM imaging of the nanostructures on the
nonconductive glass substrate.
Figure 4 shows the scattering spectra of the gold triangle sensor
in response to hydrogen exposure. To investigate the influence
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NATURE MATERIALS DOI: 10.1038/NMAT3029

a

ARTICLES
Second exposure
Pd evaporation

First exposure
Au evaporation

Lift-off

Lift-off

20 m

100 nm
Dark-field image

SEM image

Figure 3 | Manufacturing process. a, The fabrication of a planar nanostructure with hybrid materials using double electron-beam lithography in
combination with a double lift-off procedure. The relative positions of the gold antenna and the palladium particle were accurately aligned using gold
markers, which are represented by the three small gold dots in the schematic diagram. b, Left: Dark-field image of the palladiumgold antennas. Right:
Representative SEM image of a single palladiumgold antenna.

Gap distance = 10 nm

Gap distance = 70 nm

0
636 640 644 648

Wavelength (nm)

0 torr

500 550 600 650 700

Wavelength (nm)

16
8

16 torr

0
620 624 628 632

Wavelength (nm)

500 550 600 650 700

Wavelength (nm)

16 torr

8 torr

0
616 620 624 628

Wavelength (nm)
0 torr

0 torr

d = 10 nm

Pressure (torr)

0 torr

8 torr

Cycle 2

Pressure (torr)

Cycle 2

16

16

Cycle 1

16 torr

16 torr

33

Scattered intensity (a.u.)

33 torr

Cycle 1

16

0 torr

Scattered intensity (a.u.)

0 torr

8 torr

Cycle 2

16

Cycle 1

16 torr

33

Pressure (torr)

Cycle 2

33 torr

Cycle 1

Scattered intensity (a.u.)

0 torr

Gap distance = 90 nm

Cycle 1

d = 70 nm

500 550 600 650 700

Wavelength (nm)

d = 90 nm

Figure 4 | Optical-scattering measurements of a single palladiumgold triangle antenna on hydrogen exposure in dependence on separation d between
the gold antenna and the palladium particle. a, d = 10 nm. b, d = 70 nm. c, d = 90 nm. In each part, the hydrogen partial pressure is raised from 0 torr to
higher pressures and driven back to 0 torr. Two cycles are shown. 33 torr corresponds approximately to a 4% hydrogen concentration. The vertical bars in
each figure are guides to the eye. The right diagram in each part shows the behaviour of the resonance peak on hydrogen cycles one and two. The lines
connecting the data points are guides to the eye. The arrow indicates the direction of measurements. Our error bar for the peak determination is estimated
to be 1 nm, as shown in a, in the case of pronounced scattering spectra with a gold nanoantenna present. The SEM image of the nanostructure is shown in
each part accordingly. The scale bar is 50 nm. At larger distances, the spectral shift substantially decreases. The spectral shift does not go back to its
original value owing to hysteresis effects of the hydrogen uptake.

of the local field enhancement on the sensor activity, the gap

distance d between the gold antenna and the palladium particle
is systematically increased. Figure 4a shows the optical scattering
measurements of the gold triangle sensor with d as small as 10 nm.
The spectral peak positions were extracted from the experimental
spectra. Smoothened curves are represented by black solid lines in
the same figure. To highlight the spectral shift in dependence on the
hydrogen concentration, the extracted spectral peak positions are
shown in the right column of Fig. 4a. When the hydrogen pressure is
0 torr, that is, pure nitrogen, a plasmonic resonance is visible around
638 nm, which is represented by the blue curve in Fig. 4a. This
resonance is associated with the resonant excitation of dipolar-like
particle plasmons in the gold triangle (see Fig. 2a). When the
hydrogen pressure is increased to 8 torr (1% concentration), a

clear resonance red-shift (5 nm) is observable and simultaneously

the resonance intensity is dramatically suppressed (see the green
curve in Fig. 4a). As a result, the hydrogen absorption event in
the palladium particle is indirectly detected by monitoring the
gold-antenna LSPR response. This relies on the fact that the
dielectric permittivity of the palladium is modified by Fermi-level
shifting owing to incorporation of free electrons from the adsorbed
hydrogen36,55 . A subsequent pressure increase of hydrogen (16 torr,
2%) leads to a further resonance red-shift (9 nm), as shown by
the red curve in Fig. 4a.
To probe the hydrogen desorption response, the hydrogen
pressure is driven back to 0 torr in the second cycle by purging
with nitrogen. As shown by the light-blue curve in Fig. 4a, the
resonance peak does not return to the original position at 0 torr in

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NATURE MATERIALS DOI: 10.1038/NMAT3029

ARTICLES
b

Gap distance = 20 nm

Gap distance = 50 nm

16 torr

676 680 684 688

Wavelength (nm)

0 torr
16 torr

8
0

652 656 660 664

Wavelength (nm)

16 torr

Pressure (torr)

0
16

16

Cycle 1

Cycle 2

Pressure (torr)

Cycle 2

16

8 torr

8 torr

8 torr
660 664 668 672

Wavelength (nm)
0 torr

0 torr

0 torr

550 600 650 700

Wavelength (nm)

16 torr

33

Scattered intensity (a.u.)

0 torr

33 torr

Cycle 1

16

0 torr

Scattered intensity (a.u.)

8
16 torr

Cycle 2

16

Cycle 1

Pressure (torr)

Cycle 2

33 torr

Cycle 1

Scattered intensity (a.u.)

0 torr

33

Gap distance = 85 nm

Cycle 1

d = 20 nm

550 600 650 700

Wavelength (nm)

d = 50 nm

550 600 650 700

Wavelength (nm)

d = 85 nm

Figure 5 | Optical scattering measurements of a single palladiumgold rod antenna on hydrogen exposure in dependence on the separation d between
the gold antenna and the palladium particle. a, d = 20 nm. b, d = 50 nm. c, d = 85 nm. In each part, the hydrogen partial pressure is raised from 0 torr to
higher pressures and driven back to 0 torr. Two cycles are shown. The vertical bars in each part are guides to the eye. The right diagram in each part shows
the behaviour of the resonance peak on hydrogen cycles one and two. The lines connecting the data points are guides to the eye. The arrow indicates the
direction of measurements. The SEM image of the nanostructure is shown in each part accordingly. The scale bar is 50 nm. At larger distances, the spectral
shift substantially decreases. Hysteresis is also clearly observable.

the first cycle. It exhibits a net red-shift of around 4 nm, showing

hysteresis. In fact, at low pressures the incorporation of hydrogen
takes place at interstitial sites of the palladium lattice (-phase).
At high pressures46 , a palladium hydride phase (-phase) gradually
becomes stable. Hydrogen atoms progressively occupy lattice sites
and induce lattice expansion. The hysteresis is attributed to the
lattice strain resulting from hydrogen incorporation41,49,50,56 and/or
residual hydrogen that cannot be removed from the Pd nanoparticle
at room temperature57 . This is the first optical observation of
hysteresis effects in a single palladium nanoparticle.
When the hydrogen pressure is increased to 16 torr in the
second cycle, the resonance exhibits a red-shift (3 nm), yet
much smaller than the 9 nm red-shift in the first cycle at the
same pressure. This reveals that hysteresis causes a deterioration
of the sensor behaviour. This could be improved or avoided by
co-depositing nickel58 together with palladium for future practical
applications. When the hydrogen pressure is increased to 33 torr
(4%), the resonance shows a further red-shift. A subsequent
pressure decrease of hydrogen (0 torr) drives the resonance back,
yet again showing hysteresis effects. The net red-shift between the
last two measurements at 0 torr is around 3 nm.
To further corroborate the important role of nanofocusing
in single-particle hydrogen sensing, we successively enlarge the
distance between the gold triangle and the palladium particle.
Figure 4b presents the optical scattering spectra of the gold triangle
sensor in response to hydrogen exposure, in which d is increased to
70 nm. Just as in the case of d = 10 nm, the sensor follows an overall
similar trail on hydrogen absorption or desorption, but with much
smaller spectral shifts. This is due to the fact that plasmon-induced
electromagnetic fields decay exponentially away from the gold
antenna surface. As a result, the LSPR shows a substantially reduced
response to the dielectric change in a spot away from the nanofocus.
Further evidence is presented in Fig. 4c, in which the distance
between the gold triangle and the palladium particles is enlarged
to d = 90 nm. In this case, the antenna resonance shows no spectral
shift when the hydrogen pressure is 8 torr and exhibits a very small
red-shift at 16 torr. To effectively detect targeted events, the sensing
element should be placed as close as possible to the plasmonic
nanofocus, in which the near-fields have their largest strength.
The shape of the plasmonic antenna is another crucial
issue, which can significantly influence the hydrogen-sensor
634

performance. We demonstrate this aspect in Fig. 5, where we use

a gold rod antenna. The length and width of the gold rod are
130 nm and 80 nm, respectively, and its thickness is 40 nm. The
diameter and thickness of the palladium particle is 60 nm and
40 nm, respectively. Its size is the same as that of the palladium
particle next to the gold triangle antenna. Figure 5a shows the
results for a distance of d = 20 nm between the gold rod and
the palladium particle. It is evident that in general the response
of the gold rod sensor on hydrogen absorption or desorption
resembles that of the gold triangle sensor in Fig. 4a. Nevertheless,
there are several dissimilarities that are noteworthy. First, the
resonance does not show a significant shape change on hydrogen
absorption at 8 torr compared with 0 torr. Second, the magnitudes
of red-shifts on hydrogen absorption and the hysteresis effects on
hydrogen desorption are much smaller. The above observations
can be attributed to the fact that for the gold rod antenna the
plasmon-induced near-fields are more located at the corners,
whereas the sharp tip of the gold triangle antenna facilitates an
excellent nanfocus at the palladium particle spot, giving rise to
a more sensitive detection response. When the distance between
the gold rod antenna and the palladium particle is enlarged to
d = 50 nm, the overall response to hydrogen is smaller with respect
to the case of d = 20 nm. Subsequently, when the distance is further
increased to d = 85 nm, the gold rod antenna can hardly sense the
optical changes of the palladium particle on hydrogen exposure.
In essence, the triangle antenna sensor shows stronger feedback to
hydrogen exposure than the rod antenna sensor as corroborated
by Figs 4a and 5a. The geometry of plasmonic antennas thus has
a substantial impact on determining the sensitivity of gas sensing at
the single-particle level.
As control experiments, we also measured the optical scattering
response of a single gold antenna and a single palladium nanoparticle on hydrogen exposure. As is evident from Fig. 6a, hydrogen does
not influence the spectral position of the gold-antenna resonance.
As Fig. 6b demonstrates, the palladium nanoparticles are nearly
indiscernible in a dark-field microscope owing to the extremely
damped plasmon excitations45 . The scattering response of a single
palladium nanoparticle shows unstructured and noisy spectra at
different hydrogen pressures (see Fig. 6b). In other words, a palladium nanoparticle alone cannot fulfil the role of single-particle
sensing in the visible range.
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NATURE MATERIALS DOI: 10.1038/NMAT3029

a

Methods

Gold antenna

Scattered intensity (a.u.)

Dark-field image

33 torr

10 m

0 torr

550 600 650 700

Wavelength (nm)

Pd nanoparticle
Dark-field image

Scattered intensity (a.u.)

ARTICLES

33 torr
10 m

0 torr

500 550 600 650

Wavelength (nm)

Structural fabrication. The antenna structures and alignment markers are first
defined in poly(methyl methacrylate) resist using electron-beam lithography on a
quartz substrate. The substrate is then covered with 2 nm chromium adhesion film
and 40 nm gold film using thermal evaporation followed by a lift-off procedure.
Next, the substrate is coated once more with poly(methyl methacrylate) resist.
Computer-controlled alignment at the sub-10-nm level using the gold alignment
markers is applied to ensure the accurate positioning of the single dot structure.
Subsequently, the palladium dot is generated by covering the substrate with 2 nm
chromium adhesion film and 40 nm palladium film using thermal evaporation
followed by a lift-off procedure.
Experimental set-up. Ultrahigh-purity hydrogen (UHP 5.0) and nitrogen (UHP
5.0) from Praxair were used with GFC 17 mass-flow controllers (Aalborg,
Orangeburg, NY) to control the partial pressure of hydrogen in a stainless-steel
cell. The total pressure was read by a NIST-certified diaphragm manometer gauge
(no. 902346, Vacuum Research Corp., Pittsburgh, PA). The dark-field optical
set-up consists of a 100 W tungsten lamp, a dark-field condenser and an objective.
The scattered light was analysed by a silicon CCD (charge-coupled device)
camera (1340 100 pixels) cooled by liquid nitrogen and attached to an imaging
spectrometer. The detection took place normal to the sample surface through
the objective optical axis (Zeiss dark-field objective, LC EC Epiplan Neofluar,
50, numerical aperture NA = 0.55), which is perpendicular to the illumination
polarization. The illumination took place through the dark-field condenser. The
measurements at different hydrogen concentrations were made after the system
was in equilibrium in hydrogennitrogen atmosphere for 1 h. Each spectrum
represents an average of 20 acquisitions that individually had an integration time
of 1 s at a single antenna structure. After a complete cycle, the system was purged
using nitrogen overnight. The black curves imposed on the experimental spectra in
Figs 46 were obtained using the SavitzkyGolay method by filtering the raw data
with a second-order polynomial and a frame size of 205.

Received 17 January 2011; accepted 18 April 2011; published online

15 May 2011

Figure 6 | Control experiments. a, Optical scattering measurements of a

single gold antenna. Upper right: Dark-field image of the gold antennas.
Lower right: SEM image of a single gold antenna; scale bar 50 nm. The
plasmonic resonance of the gold antenna does not show any spectral shift
on hydrogen exposure. b, Optical scattering measurements of a single
palladium nanoparticle. Upper right: Dark-field image of the palladium
nanoparticles. Lower right: SEM image of a single palladium particle; scale
bar 50 nm. The palladium nanoparticle alone shows an unstructured and
noisy spectrum. No useful information can be extracted on
hydrogen exposure.

Resonant antenna-enhanced single-particle sensing pushes the

sensitivity of plasmonic gas sensors to an ultimate limit and opens
up myriad possibilities for detecting optically inactive (that is, not
luminescent, with low oscillator strength or largely damped) species
in a controlled fashion. The single-particle sensing strategy will have
profound significance for the optical observation of chemical reactions and catalytic activities on a single platform in nanoreactors,
and has the potential to be extended to biochemical systems in
the future. Moreover, antenna-enhanced sensing comprises a noninvasive and generalizable scheme that is applicable to a variety of
physical and biochemical materials. For example, it can be directly
applied to detect gases such as CO and NOx using platinum48 ,
palladium or other inorganic catalysts, to detect CO2 adsorption
in metalorganic frameworks34 and to detect other gases using
appropriate analytes in the nanofocus. The device presented here is
biocompatible and can operate in aqueous environments. Our work
could pave the way towards the observation of catalytic reactions
such as hydrogenation of carbohydrates59 on individual palladium
nanoparticles. The extension of indirect plasmonic sensing to the
observation of single chemical or biological events is challenging,
but worth further investigation. Our sensing concept will also
stimulate the synthesis of advanced hybrid particles for plasmonic
sensing. For example, it is possible to use appropriate biochemical
linkers to connect a gold particle with a Pd particle and to carry out
hydrogen sensing at the single-particle level. We believe that this will
bridge two important fields: plasmonics and biochemistry.

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Acknowledgements
We would like to thank X. Meng for help with the metal deposition at the Microlab
Facility of the Electrical Engineering and Computer Science Department, University of
California, Berkeley. The SEM studies were supported by the Molecular Foundry at the
National Center for Electron Microscopy at Lawrence Berkeley National Laboratory. The
experimental set-up was funded by the grant A Synergistic Approach to the Development
of New Classes of Hydrogen Storage Materials from the US Department of Energy,
DE-AC03-76SF00098. We acknowledge S. Hein for his material visualizations. We thank
Th. Schumacher and M. Lippitz for discussions and comments. We thank A. Tittl and
N. Strohfeldt for help with the measurements and data analysis. N.L., M.L.T. and A.P.A.
acknowledge financial support through the Plasmonic-Enhanced Catalysis Project of
the Air Force Office of Science Research, award number FA9550-10-1-0504. M.H. and
H.G. were financially supported by Deutsche Forschungsgemeinschaft (SPP1391 and
FOR557), by BMBF (13N9048 and 13N10146) and by Landesstiftung BW.

Author contributions
All authors contributed extensively to the work presented in this paper.

Additional information
The authors declare no competing financial interests. Reprints and permissions
information is available online at http://www.nature.com/reprints. Correspondence and
requests for materials should be addressed to A.P.A.

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