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Feature Article

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Dynamics of Surface Plasmon Polaritons in Metal Nanowires

Paul Johns,† Gary Beane,† Kuai Yu,‡ and Gregory V. Hartland*,†
†
Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, United States
‡
College of Electronic Science and Technology, Shenzhen University, Shenzhen, 518060, P. R. China

ABSTRACT: Metal nanostructures have found extensive use in a variety of

applications in chemistry, including as substrates for molecular sensing and surface
enhanced spectroscopy and as nanoscale heaters for photothermal therapy. These
applications depend on the strong absorption and field enhancements associated
with localized surface plasmon resonance (LSPR). This has led to a number of
studies of how the LSPR line width, which measures energy losses for the coherent
electron motion, depends on the size and shape of different types of metal
nanoparticles, and the environment around the particle. Extended metal
nanostructures, such as nanowires and nanoplates, display propagating surface
plasmon modes, termed surface plasmon polaritons (SPPs), in addition to LSPRs.
These modes are important for applications where metal nanostructures are used as
waveguides. However, less is known about the damping of the propagating SPPs compared to the LSPRs. The energy losses for
the propagating SPP modes can be investigated by measuring propagation lengths. The goal of this Feature Article is to review
recent experiments that have provided quantitative information about the propagation lengths of SPPs in metal nanostructures,
and to provide a physical understanding of the important factors in SPP damping.

1. INTRODUCTION energy losses for the SPP mode,4,49,50,66−68 and is the

The interaction between metal nanostructures and light
generates surface plasmon polaritonswhich are mixtures of
photonic and plasmonic states.1−8 For nanoparticles, these
excitations are confined, and give rise to resonances that are
termed localized surface plasmon resonances (LSPRs).9−11 The
LSPRs of Ag and Au nanoparticles have been extensively
studied, primarily because of the applications of these materials
to surface enhanced spectroscopies,12−19 molecular sens-
ing,20−23 and imaging and photothermal therapy.24−31 For
most of these applications, it is desirable to have resonances
with high quality factors, that is, narrow line widths.32,33 The
line widths are hard to measure accurately in conventional
ensemble experiments, because of inhomogeneous broadening
effects from the different sizes and shapes present in the
samples.34 Thus, this field has benefitted tremendously from
the development of optical techniques that can record spectra
of single metal nanoparticles.35−43 There have been a number
of such studies in the past decade, so that the way the LSPR
line width depends on size, shape, and material is now
reasonably well understood.34,44−46
In extended metal nanostructures, such as metal nanowires,
the electron motions can have a well-defined momentum.47−52
These types of modes are termed propagating surface plasmon
polaritons (SPPs).4,6,53 The propagating SPPs have also found
applications in materials science and engineering. For example,
SPPs in metal nanowires provide a way of guiding electro-
magnetic fields with subdiffraction spatial resolution,54−60
which is useful for creating photonic devices with ultrasmall
mode volumes.2,61−65 In these applications, it is desirable to
have SPP modes that are strongly confined with long
propagation lengths. The propagation length depends on the
counterpart of the line width for the LSPRs.
Compared to the LSPRs of metal nanoparticles, there have
been fewer studies of the dephasing of SPPs. Primarily this is
because it is more difficult to couple photons to propagating
SPPs due to momentum matching restrictions.1,4,6,63 This
article will focus on calculations and experimental results for the
propagating SPP modes of metal nanowires,48,49,69,70 rather
than thin films2,65−67,71 and nanoplates.72,73 Finite element
simulations will be used to elucidate the different types of SPP
modes that are supported in the nanowires, and how the
propagation lengths depend on the dimensions of the nanowire
and the refractive index of the environment.74−77 Examples will
also be given of experimental measurements that provide
quantitative information about the complex wavevector of the
SPP modes.47,49,51,75,78−88 The focus will be on chemically
synthesized nanowires, as these have been the most studied
extended metal nanostructures to date. These materials are
crystalline with smooth surfaces and, thus, are expected to have
longer propagation lengths compared to the polycrystalline
nanowires made by electron-beam lithography or template
deposition.49,80,89 A major goal of the article will be to make a
connection between the line widths of LSPRs and the
propagation lengths of SPPs.
Received: December 19, 2016
Revised: January 23, 2017
Published: February 3, 2017

© 2017 American Chemical Society 5445 DOI: 10.1021/acs.jpcc.6b12748

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Figure 1. (a) Extinction spectra σext for the LSPR of different sized Ag spheres in water. (b) Contributions from Landau damping Γh (nonradiative
relaxation) and radiation damping Γr to the line width for the spectra in panel a. (c) Extinction spectra σext for the transverse LSPR of different sized
Ag nanowires in water. (d) Contributions from Γh and Γr to the line width for the spectra in panel c. The spectra were calculated through COMSOL
Multiphysics, using the dielectric constant data from ref 96.
2. SIMULATIONS OF POWER DISSIPATION IN METAL
NANOSTRUCTURES
The starting point for our discussion is a classical description of
power losses in metal nanostructures, and how these are
calculated through finite element methods. Before discussing
propagating SPPs in nanowires, we first look at LSPRs of
particles. The width of the LSPR directly reports on energy
losses for the electron system. Traditionally, the LSPR line
width is divided into three contributions: nonradiative decay or
Landau damping (Γh decay of the coherent electron oscillation
into electron−hole pairs and, eventually, heat), radiation
damping (Γr energy loss by emission of photons), and
electron−surface scattering (Γsurf dephasing of the electron
oscillation due to collisions with the particle sur-
face).34,36,37,42,44,46,90−94 Electron−surface scattering will not
be discussed in this article, as the nanowires that have been
examined in experiments to date have lateral dimensions
greater than 20 nm, which is larger than the characteristic size
where electron−surface scattering effects are signifi-
cant.42,44,46,92,93 There have been several recent reviews of
electron−surface scattering effects in metal nanostructures, and
the interested reader is referred to these.34,44 Neglecting
electron−surface scattering means that the total line width is
simply given by Γ = Γh + Γr.
Figure 1a shows simulated extinction spectra for different
sized Ag nanospheres in water. The spectra were calculated
through finite element analysis, using the Wave Optics module
of COMSOL Multiphysics (v 5.2a). In these calculations, the
extinction cross section σext is obtained from the sum of the
absorption and scattering cross sections, σabs and σscat,
respectively.95 These cross sections were calculated from the
power losses for the incident electromagnetic field due to
absorption and scattering by the particle. Specifically, the
absorption cross section is calculated by integrating the power
dissipation Qrh over the volume of the sphere: σabs = ∭ Qrh dV/
P0, where P0 is the incident power of the electromagnetic field.
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In turn, the scattering cross section is obtained by integrating
the time-averaged power flow from the scattered field over a
spherical surface placed at some distance from the nanoparticle:
σscat = ∬ n̂·⇀
S dA/P0, where ⇀ S is the Poynting vector for the
scattered field and n̂ is a unit vector normal to the surface.95
More details on how n̂ and ⇀ S are specified in our COMSOL
simulations are given in the Appendix to this article. The
Johnson and Christy dielectric constant data was used for all of
the simulations presented below.96
The plasmon resonance for the spheres becomes more
intense and broader as size increases. The increase in the line
width arises from radiation damping: at large sizes, decay of the
plasmon oscillation into photons becomes a significant energy
loss mechanism.36,91,92,97,98 The radiative and nonradiative
contributions to the total line width can be determined by
analyzing the power dissipation from each process. Specifically,
by analogy with molecular quantum yields, Γh = (Ph/Ptot)Γ and
Γr = (Pr/Ptot)Γ, where Ptot = Ph + Pr is the total dissipated
power and Ph and Pr are the power dissipated by resistive
heating and radiation, respectively. Ph and Pr are given by Ph =
∭ Qrh dV and Pr = ∬ n̂·⇀ S dA as before. Figure 1b shows a plot
of Γh and Γr versus the size obtained from the spectra in Figure
1a. In this calculation, Ph and Pr were determined at the peak of
the LSPR, and Γ was obtained by fitting the spectra to a Fano
profile A(1 + (ω − ω0)/qw)2/(1 + ((ω − ω0)/w)2), where ω0
is the resonance frequency, A is the amplitude, w = Γ/2, and q
is the asymmetry factor.99,100 A Fano profile was used, rather
than the conventional Lorentzian profile,46,92 to provide a
consistent analysis with the LSPRs of the metal nanowires
presented below, which show asymmetrical lineshapes. This
profile has been extensively used to analyze the spectra of metal
nanostructures and, thus, is a natural choice for these
simulations.99−101 Figure 1b shows that, at sizes greater than
15−20 nm, light scattering becomes the dominant energy loss
mechanism for the LSPR of Ag spheres.34 Note that, because
the absorption and scattering cross sections are proportional to
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Figure 2. (a) Propagation length LSPP versus radius for Au nanowires with circular cross sections in air, water, and microscope immersion oil. (b)
LSPP versus width for Au nanowires with a square cross section in microscope immersion oil and supported on a glass surface. Panels c and d show
the corresponding propagation constants β/k0 for the nanowires in panels a and b, respectively. (e) Plots of the norm of the electric field for (from
left to right) nanowires with a circular cross section in microscope immersion oil, a square nanowire in oil, and the bound and leaky modes for a
square nanowire on a glass surface. The dimensions of the nanowires (diameter or width) were 500 nm.

Ph and Pr, the nonradiative and radiative contributions to the
LSPR line width can equivalently be calculated by Γh = (σabs/
σext)Γ and Γr = (σscat/σext)Γ (this form is convenient for Mie
theory calculations, for example).
Extended metal nanostructures also display LSPRs. Figure 1c
shows calculated spectra for the transverse LSPR (electron
oscillation across the nanowire) for cylindrical silver nanowires
of different dimensions in water. These calculations were
performed in a two-dimensional simulation, which effectively
assumes infinitely long nanowires. The powers dissipated by
resistive heating and radiation were calculated in an analogous
way to what was done for the spheres, except now the volume
and surface integrals for Ph and Pr become area and line
integrals, respectively. Specifically, Ph = ∬ Qrh dA and Pr =
∫ n̂·⇀
S dl where the integral for Ph is over the area of the
nanowire and the integral for Pr is over a circle placed at a
distance from the nanowire. Note that the cross sections have
units of m2 per unit length, which we have expressed as nm in
Figure 1c. Figure 1d shows the contributions from radiative and
nonradiative damping determined using the analysis described
above, where the total line width was obtained from the spectra
in Figure 1c using the Fano profile. Similar to the spheres, the
radiation damping contribution increases as the lateral
dimensions of the nanowire increase, and dominates for radii
5447
greater than approximately 15 nm. The Γh contribution to the
line width is larger for the nanowires compared to that for the
spheres because the LSPRs of the nanowires are blue-shifted
and closer to the interband transitions of Ag.102 Note that the
spectra calculated through the finite element simulations are in
good agreement with spectra calculated using the full Mie
theory expressions for the extinction and scattering cross
sections of spheres,34 or the equivalent expressions for infinite
cylinders.95,103
For both the spheres and the cylinders, the contribution from
radiation damping to the line width increases with size. For the
spheres, Γr is simply proportional to volume.36,91,92 To
understand this scaling, we note that the damping constant
for the LSPR can be expressed as Γ = −(dW/dt)/W, where W
is the stored electromagnetic energy. The power dissipation
from emitting photons (−(dW/dt)r) is proportional to the
scattering cross section, which scales as the volume squared for
not too large particles (i.e., at sizes where retardation effects are
relatively small). In contrast, the stored energy W is simply
proportional to volume. Thus, for spheres, Γr increases with
volume. The size dependence for Γr is more complicated for
the cylinders, most likely because of retardation effects at large
sizes. Note that for both the spheres and the cylinders the
damping from nonradiative processes is roughly independent of
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Figure 3. (a) Plot of the relative amount of electromagnetic energy inside the nanowire Win/(Win + Wout) versus width for the different sized
nanowires in Figure 2. Note that Win/(Win + Wout) decreases as size increases. (b) Attenuation constant α versus Win/(Win + Wout). (c) Plots of the
normalized electric field for the bound mode of a square nanowire with different widths. (d) Plots of the normalized electric field for the different
nanowires in microscope immersion oil.
size. This is because the amount of energy dissipated by heating
is proportional to the volume of the nano-object, so that the
size dependent terms in −(dW/dt)/W cancel.
We now turn our attention to the propagating SPP modes of
the nanowires. We start with Au nanowires, as these have been
the most studied. The different SPP modes that are supported
by a nanowire can be determined in COMSOL by a two-
dimensional Mode Analysis calculation.74−77,84−88 This analysis
yields the complex wavevector of the SPP mode kSPP ̃ = β + iα,
where β and α are the propagation and attenuation constants,
respectively. The SPP propagation length is given by LSPP = 1/
2α.74−77,84−88 Parts a and b of Figure 2 show the propagation
lengths versus size for several different cases: cylindrical Au
nanowires in homogeneous environments (air, water, and
microscope immersion oil) (Figure 2a) and Au nanowires with
square cross sections on a glass surface and in microscope
immersion oil (Figure 2b). The corresponding propagation
constants (β/k0) are presented in Figure 2c and d. Note that
only the lowest order SPP modes are examined, as these are the
ones generally seen in experiments. Plots of the electric fields
associated with the different modes are shown in Figure 2e.
Square cross sections were investigated for the substrate
supported nanowires, because this shape roughly matches the
shape of the nanowires examined in our previous papers.84,86,87
For the square nanowire on glass, there are two supported
modesa bound mode where the field is localized at the
nanowire glass interface and a leaky mode where the field
appears on both the metal−air and metal−glass interfa-
ces.50,75,84,86 The propagation constant β for the leaky mode
is much smaller than that for the bound mode, and is small
enough that the leaky mode can couple to photons in the
substrate.75,76,85,88 In contrast, for the bound mode and for
nanowires in a homogeneous environment, β/k0 is always
greater than nmed, which means that SPPs cannot couple to free
space photons.50
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For all of the different cases in Figure 2, the propagation
length of the SPP modes increases (power losses decrease) with
increasing dimensions. For all of the modes except the leaky
mode, this has a fairly simple physical reason: for metal
nanostructures, the decay length of the field into the
environment increases as the diameter increases.52,66,67
However, the decay length for the field inside the nanostructure
is determined by the optical penetration depth in the metal,6,8
which does not depend on size. Thus, as the size of the
structure increases, the SPP modes are less confined in the
metal: proportionally more of the field is outside the nanowire.
Because the power losses arise from resistive heating inside the
metal, the propagation lengths increase as the dimensions
increase.
To illustrate this effect, Figure 3 shows plots of the
attenuation constant α and the relative amount of electro-
magnetic energy inside the nanowire Win/(Win + Wout) for the
nanowires in a homogeneous environment and for the bound
mode. For our two-dimensional calculations,
1
Wi = 2 ∬ (ϵiϵ0 |Ei|2 + |Bi |2 /(μi μ0 )) dA , where ϵi, Ei, μi, and
Bi are the dielectric constant, the electric field, the permittivity,
and the magnetic field in region “i”, respectively. In Figure 3a,
Win/(Win + Wout) is plotted versus dimensions for the
nanowires in a homogeneous environment and for the bound
mode of the substrate supported nanowires. The relative
amount of energy inside the nanowires decreases (the SPP
modes become less confined) as the dimensions increase.52,67
Figure 3b shows a plot of α versus Win/(Win + Wout). The
attenuation constant increases (LSPP decreases) as Win/(Win +
Wout) increases. This shows that as the SPP modes become
more confined they suffer greater attenuation.
Parts c and d of Figure 3 show plots of the normalized
electric field for the bound mode of a square nanowire and the
field for a square nanowire in microscope immersion oil. These
plots show that, as the dimensions of the nanowire increase, the
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Figure 4. (a) Attenuation constant α versus width for the leaky mode of Au nanowires with square cross sections. αh and αr are the contributions
from resistive heating and radiation damping, respectively. (b) Field plots for the leaky mode for several different sized square Au nanowires. (c)
Attenuation constants and (d) field plots for the leaky mode for pentagonal Ag nanowires.
field extends out further into the medium. However, the length
scale for the decay of the field inside the nanowire does not
change with size. Thus, the relative amount of electromagnetic
energy inside the nanowire Win/(Win + Wout) decreases as size
increases. This has an interesting consequence for the bound
mode: for large nanowires, the field inside is completely
damped, so that the field only appears at the glass−metal
interface. In contrast, for smaller nanowires, the field inside
does not decay completely, and some electric field appears at
the metal−air interface.
The leaky mode for the substrate-supported nanowires
shows a different behavior from the modes in Figure 3. Like the
other SPP modes, LSPP increases as the dimensions increase for
the leaky mode; however, the leaky mode becomes less
confined at small dimensions rather than at large dimensions
(see Figure 4). The analysis in Figure 3 cannot be used for the
leaky mode, because the leaky mode couples to propagating
fields in the substrate rather than evanescent fields. This means
that Win/(Win + Wout) changes with the size of the simulation
area. Thus, to understand the behavior of the leaky SPP mode,
we look at the power losses due to radiative and nonradiative
processes. Following the procedure for the LSPRs, we write the
total attenuation constant as α = αh + αr, where αh and αr are
the contributions from resistive heating and radiation,
respectively. The values of αh and αr can be calculated from
αh = (Ph/Ptot)α and αr = (Pr/Ptot)α, where the total attenuation
constant α is obtained from the Mode Analysis calculation in
COMSOL. The powers dissipated by resistive heating and
radiation were calculated in the same way as that for the LSPRs
in Figure 1.
Figure 4a shows a plot of αh and αr for the leaky mode of a
Au nanowire with a square cross section determined from this
analysis. The data shows that αr decreases rapidly as size
increases, and that it is the decrease in αr that causes the
increase in LSPP seen in Figure 2. This is in contrast to the other
(“regular”) SPP modes, where the increase in LSPP with size
arose from a decrease in αh due to the modes becoming less
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confined. This behavior is also very different from that for the
LSPRs of the spheres and cylinders in Figure 2, where radiation
damping becomes stronger as size increases. Figure 4b shows
plots of the norm of the electric field ( Ex 2 + Ey 2 + Ez 2 ,
where Ex, Ey, and Ez are the x-, y-, and z-components of the
electric field) for the leaky mode for square Au nanowires with
different widths (200−2000 nm). The calculations show very
clearly that the leaky mode is coupled to a propagating
(photonic) field in the substrate that radiates away from the
nanowire at an angle. The angle is a consequence of the
momentum matching conditions, and is discussed in more
detail below. The coupling to the photonic modes of the
substrate is clearly much stronger at small sizes.
The stronger coupling to photonic modes in the substrate at
small sizes is surprising given that there is very little change in
the propagation constant for the leaky mode with size (see
Figure 2d). However, we believe that this can be explained by a
simple geometric effect. Starting at the larger nanowires, we
note that the leaky mode is primarily localized at the top
metal−air interface; see Figure 4b.50,77,84−88 To couple to the
photonic modes in the substrate, the field at the top of the
metal nanostructure must overlap with the field in the substrate.
As the size of the metal nanostructure decreases, the two fields
become closer together, so the coupling between them
increases. Figure 4c and d shows an analogous analysis of αh
and αr and mode plots for Ag nanowires with pentagonal cross
sections (which is the common shape for chemically
synthesized Ag nanowires). The results are very similar to
those for the square Au nanowiresthe leaky mode is strongly
attenuated at small sizes due to increased coupling to photonic
modes in the substrate.
It is interesting to compare the damping for the LSPRs to
that for the propagating SPPs. To do this, we compare quality
factors. For the LSPR resonances, the quality factor is given by
Q = ωrW/(−dW/dt), where ωr is the resonance frequency, W
is the total stored energy in the oscillator, and dW/dt is the
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Figure 5. Quality factors versus size (radius) for the plasmon modes of Ag nanoparticles in water. (a) LSPR of a Ag sphere and transverse LSPR for a
cylindrical Ag nanowire; (b) propagating SPP mode for a cylindrical Ag nanowire.

power dissipation for the oscillator.104 dW/dt = −ΓW which

means that Q has the simple form of Q = ωr/Γ. For the
propagating SPPs, we use the expression for the quality factor
of a waveguide Q = ωτSPP, where τSPP is the lifetime of the SPP
mode and ω is the angular frequency.105−107 The lifetime τSPP is
related to the propagation length by τSPP = LSPP/vg, where vg is
the group velocity of the SPP mode.105−107
Figure 5a shows a plot of the quality factor versus size for the
LSPRs of Ag spheres and the transverse LSPR of cylindrical Ag
nanowires (both in water). The quality factor for the
propagating SPP mode of cylindrical Ag nanowires in water
is presented in Figure 5b. For the propagating SPP modes, the
group velocity was calculated by vg = (∂ω/∂k) ≈ Δω/Δk. The
quality factors for the LSPRs of both the Ag spheres and the
cylindrical Ag nanowires decrease with increasing size. This is
expected, as the LSPRs suffer increased radiation damping with
increasing size. Note that the LSPR quality factors for the
cylinders are lower than those for the spheres. This is because
Γh is larger for the cylinders, due to the blue shift in the
resonancesee Figure 1. Figure 5b shows that the quality
factor for the propagating SPPs of the nanowires increases as
size increasesopposite the trend that occurs for the LSPRs.
As discussed above, this is because the energy losses are smaller Figure 6. Scattered light images of Ag nanowires. Left: images of silver
at large sizes due to field confinement effects. Interestingly, the nanowires under white light illumination. Right: images recorded with
quality factors for the propagating SPPs for the larger a near-IR laser (880 nm) focused at one end of the wire. Parts a and b
nanowires are comparable to those for the LSPRs at small show a straight wire with no kinks or defects, and parts c and d show a
sizes. It is also important to note that in real systems electron− kinked wire. In the laser images, light emission can be seen from the
surface scattering effects would reduce the quality factors for distal end of the wire and at sharp bends in the wire. Reproduced with
permission from ref 108. Copyright © 2008 WILEY-VCH Verlag
the LSPRs at sizes less than 10 nm.34,44 GmbH & Co. KGaA, Weinheim.

3. VISUALIZING SURFACE PLASMON POLARITONS IN
METAL NANOWIRES
A variety of different optical techniques have been used to
image SPPs. In the following, we will discuss some of the more
common measurements. The example images are taken from
our work; however, this is not meant to imply that we are main
workers in this field. Figure 6 shows scattered light images of
silver nanowires recorded with a standard optical microscope in
reflection mode.108 The images on the left were obtained using
a lamp to illuminate the sample. The wires reflect strongly, and
appear bright on a dark background. This configuration does
not excite the propagating SPP modes because the momentum
of the photons is not matched to the SPP wavevector. The
panels on the right in Figure 6 show images where a near-IR
laser beam has been focused at one end of a nanowire.49,69,70,108
The break in symmetry at the end of the wire relaxes the
momentum matching conditions and allows excitation of the
SPP modes. This is the simplest way to interrogate SPPs in
5450
metal nanowires. For the wires in Figure 6, only bound modes
were detected: scattered photons were only observed at the end
of the wire or at kinks, not along the wire.49,69,70,108 This could
be because only bound modes were excited, or because the
propagation length for the leaky mode is very short so that this
mode does not appear in the images.
The scattered light images in Figure 6b and d clearly show
that SPPs are excited and that they travel down the wire. In
principle, the intensity of the light emitted at the distal end of
the nanowire provides a way of measuring the decay length for
the SPP modes.70 However, the details of the end structure will
also affect the scattered intensity, which means that analysis of
images such as those in Figure 6c and d does not provide
accurate information about the SPP propagation lengths. On
the other hand, scattered light measurements can provide
information about the propagation length for the leaky
modes.75,81,85,88 In the following, we will discuss light scattering
measurements for the leaky mode, before moving onto more
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Figure 7. (a) Scattered light image of the leaky mode for a Ag nanowire. (b) Fourier image of the nanowire in panel a. Panels c and d show line
profiles extracted for the images in panels a and b, respectively. Fitting the data in panel c to an exponential decay yields the propagation length for
the SPP mode (note that panel c is plotted on a natural log scale), and panel d yields the propagation constant β/k0. The inset of panel c shows a line
profile across the nanowire.

Figure 8. (a) Momentum matching conditions for coupling between SPPs of a metal nanowire and photonic modes in the substrate. (b) Plot of the
value of θ needed to achieve momentum matching for a given value of ϕ. (c) Polar plot of the projection of the wavevectors in panel a onto the (x,
y) plane. (d) Calculated real space image of the leaky mode. Note that the distances for the x- and y-axes are in μm.

complex optical measurements that can interrogate both the
bound and leaky modes.
Figure 7 shows scattered light images for the leaky mode of a
Ag nanowire. Two images are presented, a real space image
where the camera is placed at a primary focal plane of the
microscope, and the conjugate Fourier space image that is
obtained by projecting the back focal plane of the objective
onto the camera.75,81,85,88 In the real space image, emission can
be seen along the length of the nanowire. The double lobe
5451
shape is characteristic of the leaky mode and is a consequence
of momentum matching (see below). In the Fourier space
image, the leaky mode appears as a line that corresponds to the
wavevector for the mode.75,81,85,88
To understand the information content in these images,
Figure 8a shows a wavevector diagram for coupling between the
SPP modes of the nanowire and photons in the substrate
(adapted from refs 82 and 85). The wavevectors are matched
when the propagation constant for the SPP mode (β) equals
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nk0 sin(θ) cos(ϕ), where n is the refractive index of the
substrate, k0 = 2π/λ is the free space wavevector of the light,
and θ and ϕ are indicated in Figure 8a. Figure 8b shows a plot
of the value of θ = arcsin(β/(nk0 cos(ϕ))) that matches the
wavevectors for the SPP and light for a given ϕ. As ϕ increases,
the projection of the light wavevector onto the axis of the
nanowire (the y-axis in Figure 8) decreases, which means that θ
must increase to achieve momentum matching. The limiting
value of ϕ, beyond which momentum matching cannot be
achieved, occurs when β/(nk0 cos(ϕc)) = 1, or ϕc = arccos(β/
nk0). The value of ϕc is shown as the vertical dotted blue line in
Figure 8b. Note that in far-field optical microscopy measure-
ments the numerical aperture (NA) of the objective limits the
range of θ values and, thus, the values of ϕ. The maximum
value of θ assuming a NA = 1.4 (denoted as θNA) and the
corresponding maximum value of ϕ (denoted as ϕNA) are
shown as the dashed horizontal and vertical red lines in Figure
8b. Also shown in Figure 8b is the critical angle for total
internal reflection (θc dashed horizontal blue line).
Figure 8c shows a plot of the projection of the different
wavevectors in Figure 8a onto the (x, y) plane. The magnitude
of the wavevector of light parallel to the axis of the nanowire is
ky/k0 = β/k0, and the wavevetor for the perpendicular
component is kx/k0 = n sin(θ) sin(ϕ) = (β/k0) tan(ϕ). This
analysis shows that the SPP should appear as a line
perpendicular to the reciprocal space vector corresponding to
the long axis of the nanowire, which is exactly what is seen in
the Fourier space images in Figure 7. The outer circle in Figure
8c indicates the maximum wavevector allowed by the NA of the
objective, and the inner circle corresponds to the critical angle
for total internal reflection (which is not related to detecting
the SPPs but appears in the images).75,81,85,88
The Fourier space image in Figure 8c can be converted to a
real space image by performing a spatial Fourier transform.109
Specifically, the fields in the real space image f(x, y) and the
Fourier space image g(kx, ky) are related through the Fourier
∞
transform pair f (x , y) = ( 21π )∬−∞ g(kx , ky)ei(k x+k y) dkx dky
x y
∞
and g (kx , k y) = ( 21π )∬−∞ f (x , y)e−i(k x+k y) dx dy. We model
x y
the time-averaged fields in the Fourier space image as
g (kx , k y) = E0δ(k y − β)kx for |kx /k 0| ≤ NA2 − (β /k 0)2
=0 for |kx /k 0| > NA2 − (β /k 0)2
Fourier transforming g(kx, ky) yields f(x, y) = (iE0/π)eiβy(sin-
(kcx) − kcx cos(kcx))/x2 for the field in the real space image,
where kc = k 0 NA2 − (β /k 0)2 . The intensity pattern f(x, y)2
created by this field is plotted in Figure 8d. The calculated real
space image shows the characteristic two lobes, which are
separated by 570 nm for the choice of parameters in Figure 8d
(NA = 1.4 and β/k0 = 1.05). These lobes are a consequence of
the momentum matching conditions that introduce wave-
vectors for the light that are perpendicular to the SPP
wavevector. The spacing between the lobes depends on the
NA of the objective and, thus, does not carry any useful
physical information about the SPP. Note that the calculations
presented above assume an infinitely long nanowire with no
attenuation of the SPP mode. Damping can be included by
modeling g(kx, ky) as a Lorentzian in ky, rather than a delta
function. This introduces an exponential decay of the intensity
in the real space image.
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The images and analysis in Figures 7 and 8 show that light
scattering measurements can yield both the real and imaginary
components of the leaky mode wavevector kSPP ̃ = β + iα.
Specifically, the real space image provides information about
the propagation length LSPP = 1/2α, and the Fourier space
image yields β/k0.75,81,85,88 These types of measurements have
been used to study propagation lengths and constants in
nanowires with different sizes,81,88 and how the propagation
constant depends on the environment of the nanowire.85 They
have also demonstrated that pentagonal silver nanowires
(which is the characteristic shape for chemically synthesized
wires) support multiple leaky modes.88
The propagation constant and the damping for the leaky SPP
modes can also be measured by near-field scanning optical
microscopy (NSOM).47−49,51,110 In these experiments, the SPP
modes are launched at one end of the nanowire, and the tip of
the NSOM microscope is used to sample the SPP field near the
surface. However, NSOM measurements are very challenging,
and require highly specialized equipment. Thus, there have
been no systematic NSOM studies of how the SPP wavevector
depends on the size and shape of the nanowires, and their
environment.
The bound SPP modes are more difficult to quantitatively
study by far field optical microscopy because they only scatter
photons at defects in the nanowires or at the ends. The most
popular method for measuring the propagation lengths of these
modes is to coat the nanowires with emitters, such as inorganic
quantum dots or organic dyes.78−80,82,83,111,112 Similar to the
leakage microscopy measurements, SPPs are launched by
focusing a laser at one end of the nanowire. The electric field
from the SPPs couples to the transition dipole moment of dye
molecules near the surface of the nanowire, causing an
electronic transition. Recording an image of the dye emission
provides a map of the SPP field strength, which yields the
propagation length.78−80,82,83,111,112 Images have been pro-
duced using both single- and two-photon emission. Note that
both bound and leaky SPP modes are excited in these
measurements, and assigning the measured propagation lengths
to a specific SPP mode requires comparison to theory.78−80,83
An obvious issue with these experiments is the possibility of
bleaching the electronic transitions of the dye. To overcome
this problem, Link and co-workers developed a technique
termed bleach-imaged plasmon propagation (BlIPP),78,79,82,83
where confocal fluorescence images of dye-coated samples are
recorded before and after excitation of the SPPs in the
nanowire. Dye molecules near the surface of the nanowire are
bleached by the SPP, and the rate of bleaching depends on the
field strength. Subtracting the before and after images shows
the distribution of bleached molecules, which can be analyzed
to generate information about LSPP.78,79,82,83 A nice aspect of
these experiments is that prolonged excitation of the SPP
modes can bring out weak features, and allow modes to be
studied that are hidden in regular direct emission images.79,83
Recently, our laboratory has developed an alternative
approach for studying SPP propagation in nanostructures
based on transient absorption microscopy
(TAM).84,86,87,113−115 In these experiments, a near-IR pump
laser is used to excite the SPP modes of the nanowire. The
SPPs move down the wire, and as they move, they lose energy
via nonradiative and (for the leaky mode) radiative processes.
The nonradiative relaxation channel creates hot electrons that
cause a transient absorption signal in the nanowire, which is
monitored by a visible probe laser.84,86,87,114 The magnitude of
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Figure 9. (a) Scattered light image of a gold nanowire and (b) the corresponding AFM image. The dimensions determined from the AFM
measurements are 450 nm × 250 nm × 15 μm (width × height × length). (c and d) Transient absorption images with pump excitation parallel and
perpendicular to the long axis of the nanowire, respectively. The pump beam is fixed at the end indicated by the arrows. (e and f) Line profiles of the
signal extracted from the images in parts c and d. Note that the intensities are on a log scale. A fit to the linear portion (red lines) gives an estimate of
the SPP propagation length. Reproduced with permission from ref 84. Copyright 2014 American Chemical Society.

the transient absorption signal is proportional to the number of
hot electrons, which depends on the intensity of the SPP
modes. Thus, scanning the probe over the nanowire generates
an image that directly reports on the SPP field strength.
Example TAM images for a gold nanowire are presented in
Figure 9, along with scattered light and atomic force
microscopy (AFM) images.84 Note that the TAM data is
plotted on a natural log scale. Fitting the line profiles to an
exponential yields the propagation length, which is 16.7 ± 0.8
μm for the nanowire in Figure 9 (for the pump laser polarized
parallel to the long axis of the nanowire).84 The nanowires
examined in ref 84 had relatively large lateral dimensions
(average heights of 550 ± 140 nm and widths 600 ± 220 nm)
and correspondingly long propagation lengths (between 10 and
20 μm). In contrast, the smaller 60 ± 10 nm diameter Au
nanowires examined in our initial report in ref 114 had much
shorter propagation lengths, on the order of 1−2 μm,
consistent with the results in Figure 2 above.
In order to maximize the signal, the wavelength of the probe
is chosen to be resonant to the transverse LSPR of the
nanowire, and the pump and probe are temporally overlapped.
A possible problem with these experiments is that the timing
between the pump and probe pulses could change when the
probe is scanned over the sample to form an image, due to
differences in the path length between the two beams.114
Transient absorption measurements for a long nanowire
recorded with the pump and probe separated by up to 25
μm show very little change in the form of the signal versus time
trace.84 This indicates that the path length differences created
by scanning the probe relative to the pump do not significantly
affect the signal in these experiments.
The TAM microscopy measurements provide similar
information to the fluorescence detection experiments
described above. Both bound and leaky modes are excited in
the experiments, and the measurements yield an effective
propagation length for the excited modes. For the fluorescence
detection experiments, the magnitude of the signal depends on
the SPP field outside the nanowire,78,83 whereas, for the TAM
5453
experiments (which detect electron heating), the magnitude of
the signal depends on the SPP field inside the nanowire.84,86,87
In principle, this could lead to different results for the two
measurements. Neither the TAM nor the fluorescence images
provide information about the propagation constant, which is a
disadvantage of these techniques compared to the Fourier
imaging measurements in Figure 7. TAM experiments are more
complex to implement than the fluorescence detection
experiments, but they have the advantage that they do not
require additional processing of the samples, and do not suffer
from bleaching. This means that repeated measurements can be
performed on the same nanowire. This is demonstrated in
Figure 9, where measurements with the pump laser polarized
parallel and perpendicular to the axis of the nanowire are
presented.84 The observation that the propagation lengths are
essentially the same in the two experiments implies that the
same SPP modes are excited by the two polarizations.
In general, the propagation lengths measured in these
experiments are in good agreement with the calculated values,
although it is important to note that the details of the shape of
the nanowire and effects such as rounding of the edges affect
the propagation length.84 The TAM images typically show a
single decay length (see Figure 9), and our interpretation of
this is that they report on the SPP mode with the longest
propagation length. Comparison between the experimental
results and the simulations shows that the leaky mode is
detected for large nanowires (dimensions greater than 500 nm)
and the bound mode is detected for smaller nanowires.84 The
measurements also show that the propagation lengths are
reduced when the refractive index of the environment is
increased, for example, by adding microscope immersion oil to
the samples,84 consistent with the results presented in Figure 2
above.
The relatively simple sample preparation and optical
alignment of the TAM experiments means that they can be
used on a variety of different systems. For example, we have
used these measurements to examine nanowires suspended
over trenches,86 and with cuts fabricated by focused ion-beam
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The Journal of Physical Chemistry C Feature Article

Figure 10. (a) SEM image of a nanobar with three cuts created by FIB milling. The widths of the gaps from left to right are 20, 30, and 25 nm,
respectively. (b) Scattered light image where the pump-laser was focused on the right end of the nanobar. (c) Transient absorption image of the
nanobar plotted on a natural log scale. (d) Line profile taken from the image in panel c. The percentage drop in the signal for each gap is given in the
figure. The lines represent exponential fits to the SPP signal in the different segments of the nanobar. (e) Simulated power dissipation as a function
of gap width for the bound (solid line) and leaky (dashed line) modes of a supported nanobar. The experimental measurements are shown as the
symbols. (f) Data for a nanobar in microscope immersion oil. The excitation wavelength was 800 nm. Reproduced with permission from ref 87.
Copyright 2016 American Chemical Society.

(FIB) milling.87 Both of these systems would be difficult to
study by either the light scattering, NSOM, or fluorescence
detection methods. The experiments on the nanowires
suspended over trenches showed an unexpected effect: for
approximately half the nanowires, the propagation lengths were
different on the two sides of the trench. The pump laser excites
both the bound and leaky modes; however, finite element
simulations show that the bound mode (which is localized at
the metal−glass interface) is strongly attenuated by the trench,
so that only the leaky mode is detected on the far side of the
trench. Thus, different propagation lengths can be measured in
these experiments when the bound mode dominates the signal
on the near side of the trench.86
Figure 10 shows results for a system with a different type of
discontinuity: Au nanowires with gaps that have been fabricated
by FIB milling.87 Figure 10a shows a scanning electron
microscopy image of the nanowire, and a scattered light
image recorded by focusing a near-IR laser at one end of the
nanowire is presented in Figure 10b. The scattered light image
shows that the leaky mode is definitely excited, although the
bound mode could also be excited, and that the leaky mode
couples across the gaps created by the FIB. Although it is not
evident from the figure, the signal-to-noise in the scattered light
image is not good enough to accurately measure the probability
for transmission across the gaps. Figure 10c shows a TAM
image of the nanowire where the near-IR pump laser is focused
at one end of the nanowire, and the probe laser is scanned
across the sample to form an image. There is a clear drop in the
signal at each cut, and analysis of the image (Figure 10d) yields
5454
the relative loss in the SPP intensity (which is related to the
transmission probability) at each gap.
The results show that the SPP modes are attenuated by 60−
80% for cut widths ranging from 20 to 100 nm. Interestingly,
on average, larger losses are observed at smaller gap widths
see Figure 10e and f. Intuitively, one would expect the
oppositelarger losses should be observed at larger gap sizes
because the coupling between the SPPs on either side of the
gap should be reduced.87 Finite element simulations show that
the increased losses at small gap sizes arise from coupling
between the SPP modes of the nanowire and localized surface
plasmon resonances associated with the gap.87 These
resonances cause additional losses through energy dissipation
and scattering. In the finite element simulations, the power
dissipation in the vicinity of the gap was calculated versus
wavelength for a given gap size and versus gap size for a given
wavelength. Both data sets show resonances. The dissipated
powers as a function of gap size for 800 nm excitation for the
bound and leaky modes and for the nanowires in microscope
immersion oil are presented in Figure 10e and f.87 The
increased losses at approximately 50 nm gap size for the bound
and leaky modes are consistent with the experimental results.87
Coupling between propagating SPP modes and localized gap
plasmon modes has not been previously observed in experi-
ments, and represents a fundamental energy loss mechanism for
the SPP modes that must be considered in designing plasmonic
devices.
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The Journal of Physical Chemistry C Feature Article

4. SUMMARY AND PERSPECTIVES complicated and involves separating the Poynting vector into
A number of far-field optical techniques have been developed its x-, y-, and z-components:
to study the properties of propagating SPP modes in extended
metal nanostructures. These techniques provide information n̂ ·⇀
S = ewfd.relPoavx*onx + ewfd.relPoavy*ony
about the propagation lengths LSPP of the SPPs, and in some + ewfd.relPoavz*onz (A1)
cases can also determine the propagation constant β. The
different techniques have different strengths and weaknesses. The functions ewfd.relPoavx, ewfd.relPoavy, and ewfd.relPoavz
For example, light scattering measurements are easy to call for the x-, y-, and z-components of the relative Poynting
implement and provide information about β as well as vector. onx, ony, and onz are defined as
LSPP,47−51,75,76,81,85,88 but they can only be used to study (A2a)
onx = nx*ofact
leaky modes. The propagation lengths for both the bound and
leaky SPP modes can be interrogated by observing emission
from dye molecules or quantum dots coated on the ony = ny*ofact (A2b)
sample.78−80,82,83,111,112 These experiments provide high
signal-to-noise images but suffer from photobleaching. Our onz = nz*ofact (A2c)
group has used TAM to measure SPP propagation.84,86,87,114 where nx, ny, and nz are the normal vectors in each direction.
This technique allows repeated measurements on the same The value of ofact takes into account the quadrant of the
sample but is more complex than light scattering or simulation and takes the value of ±1 according to
fluorescence imaging and requires specialized laser sources.
The results from experiments on Au nanowires show that if (nx*x + ny*y + nz*z) ≥ 0, 1, −1 (A3)
LSPP increases as the lateral dimensions of the nanowire
increase, which means that the SPPs suffer reduced losses at For the two-dimensional case (i.e., the infinite nanowire), the z-
large sizes.84,114 This is opposite to what occurs for the LSPRs component of all of the above equations was omitted. For the
of particles, where the energy losses increase at large sizes due two-dimensional calculations, it was not necessary to break the
to increased radiation damping.36,46,91,92 Finite element Poynting vector into its components to calculate the value of
simulations show that for the bound modes this effect arises n̂·⇀
S . This was simply called by ewfd.nPoav.
because the coupling between the field is outside the nanowire,
Stored Electromagnetic Energy
which means that resistive heating effects are reduced. For the 1
leaky SPP modes, the increased propagation lengths at large The value Wi = 2 ∬ (ϵiϵ0 |Ei|2 + |Bi |2 /(μi μ0 )) dA is called in
sizes are due to reduced radiative damping. This is counter- COMSOL as ewfd.Wav.

■
intuitive given that radiation damping strongly increases with
size for the LSPRs of nanoparticles. We believe that this effect AUTHOR INFORMATION
arises because the coupling between the field at the surface of
the nanowire and photonic modes in the substrate decreases as Corresponding Author
size increases. It is also interesting to note that the quality *E-mail: ghartlan@nd.edu. Phone: +1 (574) 631-9320.
factors for the propagating SPP modes for large nanowires are ORCID
comparable to those for the LSPRs of small particles. Gary Beane: 0000-0001-5312-0477
We have also used TAM to study how the SPP modes couple Gregory V. Hartland: 0000-0002-8650-6891
between nanostructures.87 TAM is well suited for these types of
measurements, as it does not require special sample preparation Notes
and multiple measurements can be performed in different The authors declare no competing financial interest.
environments. The results from the experiments on cut Biographies
nanowires show increased losses at small gap sizes. This is
attributed to excitation of LSPRs associated with the gaps in the
structure.

■ APPENDIX
In this section, we give details of the COMSOL commands
used to calculate the extinction cross sections, dissipated
powers, attenuation constants, and stored electromagnetic
energy for the different nanostructures.
Extinction Cross Sections, Power Dissipation, and
Attenuation Constants
When calculating the absorbance cross section, σabs =
∭ Qrh dV/P0, the value of P0 is defined as
(1 V / m)2
P0 = ( 2Z 0 )n med , where Z0 is the characteristic impedance
Paul Johns is a Ph.D. Candidate in Physical Chemistry at the
of vacuum and nmed is the refractive index of the surrounding University of Notre Dame and a Graduate Assistance for Areas of
medium. The value Qrh is called by ewfd.Qrh, and the integral is National Need (GAANN) Teaching Fellow. He received his B.S. in
over the volume of the nanostructure (this becomes an integral Chemistry from Saint Francis University in Loretto, PA. His research
over area for the two-dimensional calculations). Calculating the focuses on finite element calculations of surface plasmon polaritons in
scattering cross section, σscat = ∬ n̂ ·⇀ S dA/P0, is more different types of metal nanostructures.

5455 DOI: 10.1021/acs.jpcc.6b12748

J. Phys. Chem. C 2017, 121, 5445−5459
The Journal of Physical Chemistry C
Gary Beane received his Ph.D. in chemistry with Prof. Paul Mulvaney
at The University of Melbourne in 2014. From 2014 to 2016, he
worked with Professor David F. Kelley at the University of California,
Merced, as a postdoctoral scholar in the Department of Natural
Sciences on Auger recombination in graded semiconducting nano-
crystals. He is currently a postdoctoral scholar with Prof. Gregory
Hartland in the Department of Chemistry and Biochemistry at the
University of Notre Dame, where he studies single metal
nanostructures.
Kuai Yu obtained his Ph.D. degree from the National University of
Singapore in 2013. He was then a postdoctoral researcher in Professor
Hartland’s group. In 2016, He started working at Shenzhen University,
China, where he is currently an Associate Professor. His research
interests are applying nonlinear spectroscopy for nanomaterials and
cell biology.
Gregory V. Hartland is a Professor in the Department of Chemistry
and Biochemistry at the University of Notre Dame. He obtained a
Ph.D. from UCLA in 1991 and was a postdoctoral researcher at the
University of Pennsylvania. His current research interests are in
5456
Feature Article
applying novel spectroscopy techniques to study single nanostructures,
with the goal to understand energy relaxation processes in nanoma-
terials, and how these materials interact with their environment. Prof.
Hartland is a Fellow of the AAAS, the ACS, and the RSC.
■ ACKNOWLEDGMENTS
This work has been supported by the US National Science
Foundation, most recently through CHE-1502848. K.Y.
acknowledges financial support from the National Natural
Science Foundation of China (NSFC) (Grant Nos. 11274247,
11574218). The authors would also like to thank their co-
workers who have been involved in these projects, most notably
Mary Sajini Devadas, Libai Huang, Shun-Shang Lo, and
Hristina Musto.
■
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J. Phys. Chem. C 2017, 121, 5445−5459