Award Accounts

The Chemical Society of Japan Award for Creative Work for 2011
Nanooptical Studies on Physical and Chemical Characteristics
of Noble Metal Nanostructures
Hiromi Okamoto
1,2
1
Institute for Molecular Science, Myodaiji, Okazaki, Aichi 444-8585
2
The Graduate University for Advanced Studies, Myodaiji, Okazaki, Aichi 444-8585
Received October 2, 2012; E-mail: aho@ims.ac.jp
Studies on physical and chemical properties of noble metal nanostructures, mainly by near-eld optical microscopy
and spectroscopy, are described. Near-eld optical microscopy provides optical observation methodology with a spatial
resolution in nanometer regime beyond the diraction limit of light. We developed near-eld imaging systems equipped
with various light sources including ultrashort pulsed lasers, which enables advanced nonlinear and ultrafast near-eld
measurements as well as conventional near-eld imaging. In particular, near-eld two-photon excitation imaging was
shown to provide a convenient tool to visualize the enhanced optical elds in the vicinities of metal nanostructures. With
these methods we demonstrated that nanoscale optical eld structures in metal nanostructures can be directly visualized.
For single noble metal nanoparticles, such as gold nanorods as typical examples, plasmon standing wave functions were
visualized. Ultrafast imaging revealed that sub-picosecond relaxation was reected on the plasmon wave function images
through thermally induced dielectric function changes of the metal. In some cases optical eld distribution features arising
from the lightning rod eects were observed, depending on the resonance conditions of the incident wavelengths with the
plasmon modes. We also found anomalous near-eld transmission phenomenon for nanoapertures blocked by nanodisks
near the plasmon resonance wavelengths, which arise from the ecient near-eld to propagating-eld conversion ability
of the nanodisks. In assembled nanoparticles, enhanced optical elds at the gap sites between the particles were
visualized, which elucidates experimentally the mechanism of surface-enhanced Raman scattering. The characteristic eld
distributions in many particle assemblies were also observed and analyzed. Through these studies, we established a
valuable methodology to investigate optical and spectroscopic properties of metal nanostructures, and the information
obtained is available only by optical measurements with high spatial resolution.
1. Introduction
My research group started our project of the optical prop-
erties of noble metal nanoparticles rather by chance some years
ago. When I was given a chance to launch a research group at
the Institute for Molecular Science, I decided to carry out a
research plan that I had cherished for several years. That is,
I planned to develop new experimental methodologies based
on combination of near-eld optical microscopy
18
and laser
molecular spectroscopy,
9
and to apply it to materials that attract
interests from a physical chemistry point of view. I had some
research background of studies on excited-state molecules by
time-resolved spectroscopy and vibrational spectroscopy, and
hence had knowledge of advanced laser molecular spectros-
copy. However, I did not have any experience with treating
nanomaterials and probe microscopy. I had to launch a new
project in a research area that I was totally not familiar with.
I was not sure whether we could develop novel methods and
apparatuses that could provide suciently high-level research
achievements, and whether I would encounter any interesting
materials to study. For the rst few years we concentrated on
developing the near-eld apparatus. As a result, we succeeded
in constructing a suciently competent near-eld microspec-
troscopic imaging system,
1013
as described in Sections 2 and 7
of this account. I believe that the most successful achievements
of this project originate in the eorts toward the apparatus
development.
At the beginning, we conducted the research project not
bearing strongly metal nanoparticles in mind. In the discussion
of various possibilities of studies utilizing the uniqueness of
near-eld imaging, we considered that a new research area
might be expanded by combining near-eld microscopy with
the connement of optical elds by noble metal nanoparticles.
As a basis for that, we decided to perform near-eld imaging of
metal nanoparticles to reveal the basic nanooptical character-
istics. We began with the studies of near-eld characteristics
of spherical gold nanoparticles as the most basic case, and we
extended the study to rod-shaped particles (gold nanorods). The
rst observation of the steady-state wave functions of surface
plasmon resonance in gold nanorods
11,14,15
made me aware of
2013 The Chemical Society of Japan
Published on the web April 15, 2013; doi:10.1246/bcsj.20120268
Bull. Chem. Soc. Jpn. Vol. 86, No. 4, 397413 (2013) 397
possible development of a new research eld in nanoscience.
Then we applied the method to several other types of noble
metal nanoparticles
16,17
to promote the plasmon-mode imaging
and studies on nanooptical characteristics of them. In Sections
4 and 5 of this account I will describe mainly the research
achievements related to this topic.
The unique characters and functions of noble metal nano-
structures are not suciently claried only by studying iso-
lated single nanoparticles. Characteristics of assembled nano-
particles are sometimes essential to understand the functions. In
the last two decades studies on mechanism of surface-enhanced
Raman scattering have been greatly advanced,
1824
and it has
been revealed that assembled noble metal nanoparticles are
indispensable for ecient Raman enhancement. Optical char-
acteristics of noble metal nanoparticle assemblies attracted
much attention partly because of this reason. We applied near-
eld imaging to assembled gold nanoparticles and succeeded
in experimental visualization of localized enhanced optical
elds for the rst time.
25,26
I felt that this nding might also
stimulate a novel research area, as in the standing wave obser-
vation of a single nanoparticle mentioned above, and made
some eorts to develop the study. As a result we have derived
some guidelines for the structures of nanoparticle assemblies
to get ecient eld enhancement.
2730
Section 6 is devoted to
this topic.
My original purpose of this research project was to develop a
unique method of high spatial-resolution spectroscopic imaging
by combining dynamic/nonlinear spectroscopies with near-
eld microscopy, and to apply it to scientically interesting
nanostructured materials. To this end we constructed ultrafast/
nonlinear near-eld microscopy systems by introducing ultra-
short (tens of femtoseconds) pulsed laser sources.
1012,31
We
developed advanced devices to achieve very high time resolu-
tion under the near-eld microscope, and made measurements
of near-eld ultrafast imaging/spectroscopy for gold nano-
particles. Section 7 summarizes this topic. We have found by
using these systems that two-photon-induced photolumines-
cence from noble metal nanoparticles provides a valuable
detection method for near-eld imaging. We applied this
method in the near-eld imaging studies of plasmonic mate-
rials.
14,16,2529,32,33
Since then two-photon-induced emission
from gold has been utilized in many studies.
I wish to stress in this account the validity and the unique-
ness of nanooptical measurements in the studies of character-
istics of noble metal nanostructures.
2. Near-Field Optical Microscope Setup
In this section, the experimental methods of near-eld
optical microscopy are described, mainly on that equipped
with an apertured optical ber probe, which we have adopted
in this project. The methods of near-eld microscopy presently
utilized are roughly classied into two types, aperture
1,3,4,7,34
and nonaperture (or scattering) types.
2,8,3539
In the aperture
type, a tiny aperture with a diameter smaller than the wave-
length of light opened on an opaque thin lm (usually a
metallic lm) is installed. A nonpropagating radiation eld
localized in a space of approximately the aperture size (optical
near-eld) is generated when the aperture is irradiated by light.
The sample to be observed approaches the aperture, and is
illuminated by light through the aperture. Since the localized
light near the aperture does not propagate, the sample is never
photoexcited unless the aperture locates suciently close to it.
The sample interacts with light only when it enters into the
area of the near-eld radiation, to give absorption, scattering, or
emission of photons. By detecting the optical responses while
the aperture nears the surface of the sample and scanning the
position laterally relative to the sample, we can observe an
optical image of the sample with a spatial resolution deter-
mined approximately by the aperture size. This is the basic
principle of near-eld microscopy. In the scattering type near-
eld microscope, a sharpened metallic tip is installed and is
externally illuminated. A conned radiation eld is generated
in the region near the apex of the tip, approximately within its
radius of curvature from the apex, due to the electromagnetic
eect. By the use of the conned optical eld a high-resolution
optical image can be obtained with a method similar to the
aperture type method, which is the basic principle of the
scattering type near-eld optical microscopy.
In a practical experimental aperture-type near-eld micro-
scope, an aperture on an opaque metallic lm is fabricated at
a sharpened end of single-mode optical ber core.
1,4,7,34
Light
for the measurement is introduced from the other end of the
optical ber, and optical near-eld is generated at the aperture
probe tip. The height of the probe tip is maintained at several
nanometers to about 10 nm from the sample surface while the
lateral position relative to the sample is scanned and the optical
signal is recorded. In our apparatus we have adopted shear-
force feedback
1,3,4
to maintain the probe tip height. As other
methods for tip height control, the mechanism of an atomic
force microscope or that of a scanning electron microscope (for
conducting materials) can be also applied. To detect the optical
response, we can select one of the following three measurement
modes.
1,3
1) The sample is irradiated by light through the probe, and
transmitted, scattered, or emitted radiation is detected exter-
nally (this is called illumination mode).
2) The sample is irradiated by a far-eld excitation source,
and the optical near-eld induced by the excitation light is
picked up by the near-eld probe and detected (collection
mode).
3) The sample is irradiated by light through the probe, and
the optical response in the near-eld regime is also picked up
by the same probe (illuminationcollection mode).
The illuminationcollection mode is advantageous over the
other two because of its fundamental merit that irradiation
and detection are performed for an identical local area through
an identical probe, and in addition because of its practical
merit that it can be applied to opaque samples or samples on
opaque substrates. On the other hand, since the irradiation and
detection are done through a tiny low-throughput aperture, the
detection eciency is much lower than the other two modes.
In our studies on metal nanostructures, we adopted in most
cases illumination mode for the samples on transparent glass
substrates (Figure 1).
40,41
The radiation transmitted through
the probe and the sample is collected by an objective lens
with a high numerical aperture (NA) and detected by a
photodetector after passing through appropriate optical lters if
necessary. We use a polychromator equipped with a charge-
AWARD ACCOUNTS Bull. Chem. Soc. Jpn. Vol. 86, No. 4 (2013) 398
coupled device (CCD) multichannel detector when we need to
measure spectra.
The light for the measurement was coupled into the ber
from the other end of the near-eld probe tip. Continuous wave
(cw) lasers are frequently used as light sources for near-
eld measurements. In addition to them, we sometimes use
Xe discharge arc lamps for the transmission measurements.
Conventional light sources like discharge arc lamps are gener-
ally considered unsuitable for coupling into a single mode
ber because of their low focusability. However, for trans-
mission measurements, strong transmitted light is not neces-
sary. Coupling of only a small portion of the focused spot into
the ber core is actually sucient for the detection, and thus
the arc lamp is rather a convenient, easy-to-align light source
for this purpose. For nonlinear and ultrafast time-resolved
signal detection, we use mainly femtosecond mode-locked
Ti:sapphire lasers. When a femtosecond pulse propagates
through an optical ber, the pulse duration is broadened to
several picoseconds due to the group velocity dispersion of
the ber medium. This eect results in serious deterioration of
time resolution in time-resolved measurements, and in non-
linear optical measurements lowering of signal levels because
the rate of nonlinear processes becomes lower as the pulse
peak power decreases. To avoid that, we install dispersion
compensation devices for the optical beam before coupling into
the ber, which are precisely adjusted to get the shortest pulse
duration at the apertured probe tip. The details of the disper-
sion compensation are described in Section 7. The polariza-
tion of the incident light on the sample is in general elliptical
due to the retardation eects in the ber, even though the
light source provides perfectly linear polarization. We inserted
a half-wave plate and a quarter-wave plate to the optical beam
before the ber, which allows us to get approximately linear
polarization at the exit of the ber and to adjust the direction
of polarization.
3. Noble Metal Nanostructured Materials and Their
Fundamental Optical Characteristics
The noble metal nanoparticle samples for the near-eld
measurements were prepared either by dispersing chemically
synthesized particles on glass substrates or by electron beam
lithography. Spherical gold nanoparticles were commercially
perchased. Gold and silver nanorods and triangular nanoplates
were synthesized as described in previous reports.
4250
By
electron beam lithography,
51,52
we prepared particles that are
dicult to prepare by other synthetic methods, such as circular
nanoplates.
17
The samples of circular nanoapertures on metallic
thin lms (we call them voids in this article) were fabricated
by polymer bead lithography.
33,53
As an illustrative description of fundamental optical proper-
ties of the metal nanoparticles, typical extinction spectra of
aqueous colloidal solutions of spherical gold nanoparticles
and gold nanorods are shown in Figure 2. The solution of
spherical gold nanoparticles shows a strong extinction peak
at around 550 nm when the particle diameter is smaller than
ca. 100 nm, which is attributed to the collective oscillation of
conduction electrons in the particle, that is, surface plasmon
resonance (hereafter we call this simply plasmon or abbreviate
as SPR).
2,5457
The extinction spectrum of the spheric nano-
particle is reproduced nearly quantitatively by the analytical
formula of Mie scattering theory,
56,58,59
and the peak around
550 nm is assigned to the dipolar electric oscillation on the
particle. If the radius of the particle r is small enough compared
to the wavelength of light, which allows us to treat the system
with a dipolar approximation, the polarizability of a spherical
particle, , is given in general by the following formula:
2,56,57
= 4r
3
(
m
)=( 2
m
) (1)
where and
m
denote, respectively, (complex) dielectric con-
stants of the particle material and the medium. The polar-
fs Ti:sapphire
laser
780-920 nm
CW laser
Xe lamp
PZT
single channel
detector
polychro-
mator
CCD
PZT xyz stage
sample
for dithering
o
p
t
i
c
a
l

f
i
b
e
r

c
o
r
e
m
e
t
a
l

c
o
a
t
aperture
50-100nm
near-field
probe tip
microscope
objective
s
i
n
g
l
e

m
o
d
e

f
i
b
e
r
Figure 1. Schematic diagram of a typical scanning near-eld optical microscope setup the authors group adopted. PZT:
piezoelectric transducer; CCD: charge-coupled device multichannel photodetector.
H. Okamoto Bull. Chem. Soc. Jpn. Vol. 86, No. 4 (2013) 399
izability shows a resonance peak at a wavelength giving
Re() = 2
m
, because the absolute value of the denominator
in the equation above is minimum at this wavelength. Since the
real part of is negative for metals, this resonance condi-
tion is realized in ordinary dielectric media. This resonance
corresponds to SPR. In nanorods, we nd a stronger extinction
peak at a longer wavelength, in addition to the peak of a similar
character to that of spheres.
6063
The peak shifts toward longer
wavelength when the aspect ratio (= length/diameter) increas-
es. These two peaks for the nanorods are assigned to the
oscillation of electrons in a direction perpendicular (transverse
mode) and parallel (longitudinal mode) to the long axis of
the rod, respectively, for the peak around 550 nm and that in
the longer wavelengths. For nanorods there is practically no
theoretical framework that allows us an analytical and quan-
titative treatment like Mie theory for spherical particles.
However, if the size of the nanorod is suciently small (which
permits the use of the dipolar approximation) and if the parti-
cle can be treated as an ellipsoid, the extended Gans theory
reproduces suciently well the observed features of the extinc-
tion spectra.
6063
4. Observation of Standing Wave Functions
of Plasmons in Noble Metal Nanorods
When we nished the initial construction of our near-eld
imaging apparatus, we decided to investigate the optical
characteristics of gold nanorods to utilize the localized elds,
and began near-eld transmission measurements for nanorods.
Before the experiment we expected to observe some shades
of the rod shapes with scattering from the ends. However, what
we actually obtained for some of the rods was optical extinc-
tion images consisting of bumpy structures, in contrast to the
expectation. After repeated conrmatory experiments, it be-
came clear that we can observe spatially oscillating features
in the near-eld transmission images of gold nanorods, with
sucient reproducibility.
11,15,40,6466
Typical examples are
shown in Figure 3.
11
The spatially oscillating features were
found when the image was recorded for the polarization
parallel to the long axis of the rod.
At rst we wondered what the physical origin of the features
were. After some time when I was thinking of a subject for
a grant application, I got an idea that the features might
correspond to the amplitudes of standing wave functions of
plasmon modes. The essential part of the idea is schematically
shown in Figure 4. The fundamental mode of the longitudinal
plasmon is the dipolar mode that gives the lowest resonance
frequencies (the mode of m = 1 in Figure 4 where m denotes
the mode index). In this mode, the collective oscillation of
electrons is essentially uniform in its phase throughout the rod.
The amplitude of the collective oscillation gives the standing
wave function of the plasmon mode. In addition to the dipolar
mode, there are higher order longitudinal modes (the modes
with m > 1 in Figure 4) where the phase (or direction) of the
collective electronic oscillation is not uniform and depends on
the position along the axis. The wave functions of the modes
have (m 1) nodes. The resonant frequency becomes higher
with increasing m. Radiationmatter interaction, which absorp-
tion and scattering of light originates in, is strong when the
electronic oscillation amplitude is large. Then, the rod gives
strong extinction at the loops of the plasmon standing wave
function. In other words, the optical image of the rod corre-
sponds to the square modulus of the standing wave function
of the plasmon mode resonant with the incident light. There is
a close analogy between this near-eld wave function imaging
and scanning tunneling microscopy imaging of electronic wave
functions.
6769
In scanning tunneling microscopy local den-
sity of states of electrons
70
is visualized, while in near-eld
microscopy electromagnetic (or photonic) local density of
states
7076
is imaged. Because of the dispersion characteristics
of SPR,
15,7784
the wavelength of the plasmon wave is shorter
than the wavelength of the resonant radiation (this is the
physical origin of photon connement by SPR), and thus the
wave functions cannot be imaged by conventional far-eld
optical microscopy since the spatial resolution is limited by the
wavelength. By the near-eld measurement, however, the wave
A
b
s
o
r
b
a
n
c
e

(
n
o
r
m
a
l
i
z
e
d
)
1100 1000 900 800 700 600 500 400
Wavelength / nm
Figure 2. Extinction spectra of colloidal aqueous solutions
of spheric gold nanoparticles (diameter 1525 nm, dotted
curve) and gold nanorods with a low aspect ratio (solid
curve) and a high aspect ratio (dashed curve). Extinction
is normalized at ca. 520 nm (Reproduced with permis-
sion from Ref. 40. Copyright 2006, Royal Society of
Chemistry.).
A B
100 nm 100 nm
Figure 3. Near-eld transmission images of a golf nanorod
(diameter 30 nm, length 180 nm). (A) At 780 nm, polar-
ization parallel to the long axis of the rod, and (B) at 530
nm, polarization perpendicular to the rod axis (Reproduced
with permission from Ref. 11. Copyright 2004, American
Chemical Society.).
AWARD ACCOUNTS Bull. Chem. Soc. Jpn. Vol. 86, No. 4 (2013) 400
function was visualized thanks to the intrinsic high spatial
resolution of the method. The image in Figure 3 is interpreted
as coming from the plasmon mode of m = 2 that was visualized
with the polarization parallel to the rod axis.
As for the transverse modes where the electrons oscillate
along the direction perpendicular to the rod axis, they are also
indexed with m according to the number of loops, but the
resonant frequency does not strongly depend on m
56
and all of
them show an extinction peak around 550 nm. The image in
Figure 3 was observed with light polarized perpendicular to the
rod axis, at a wavelength of around 530 nm, and it looks like a
shade of the rod shape. This observed image is interpreted as
an overlap of many transverse modes with dierent ms.
Figure 5 shows near-eld transmission images of a gold
nanorod with a higher aspect ratio (diameter 20 nm, length
510 nm) observed with light polarized along the rod axis at
various wavelengths.
40,64
In these images further higher order
longitudinal modes are visualized. At 647 nm there are seven
dark spots aligned along the rod axis, which coorespond to the
loops of the plasmon wave function, while the number of the
dark spots decreases one by one as the observation wavelength
gets longer, and nally four spots are observable at 830 nm.
The wavenumber increases with increment of the resonant
frequency, reecting the dispersion relation of the longitu-
dinal plasmon in the rod.
40,41,62,65,66
This result also supports
the idea that the obtained near-eld images correspond to
optically visualized standing wave functions (square moduli)
of plasmons.
The high-resolution optical observation of plasmon standing
wave functions can be regarded as a special case of local
excitation of polarization waves in nanomaterials. We consider
here the nanorod as a symmetric one-dimensional system
and give a simple formalism of optical measurements of the
polarization waves to discuss the polarized excited state.
41,66
To discuss the spatial features of the excitation, the nanorod
is divided into N equivalent volume elements as shown in
Figure 6, and introduce local (elementary) polarization as a
function of the position. The total polarization on the rod is
Transverse modes
Longitudinal modes
m =1
m =2
m =3
m =1
m =2

Optical images
Figure 4. Schematic illustration for the plasmon modes of a nanorod (left) and expected optical images corresponding to them
(right). The dotted curves in the left represent the standing wave functions of plasmons.
625 nm 647 nm 679 nm
730 nm 830 nm
Figure 5. Near-eld transmission images of a gold nanorod
with a high aspect ratio (diameter 20 nm, length 510 nm), at
various wavelengths. The polarization of the observation
was parallel to the long axis of the rod.
H. Okamoto Bull. Chem. Soc. Jpn. Vol. 86, No. 4 (2013) 401
given by the summation of elementary polarizations p
i
on
volume elements i = 1, 2, +, N. The ground states of all the
volume elements are assumed to be described by a state vector
of symmetric character [0
i
) and unpolarized (0
i
[p
i
[0
i
) = 0).
The polarization on a volume element i is considered to be
induced by minimal hybridization of an excited state of
asymmetric character [1
i
) to the ground state [0
i
). The polarized
excited state of the volume element [x
i
) is then given as
[x
i
) = [0
i
)
i
[1
i
) (2)
where
i
has been introduced here as a coecient of the
asymmetric state (
i
1), while it gives the wave function of
the polarized excited state of the rod as will be claried later.
The expectation value for the excited state polarization of the
volume element i is given as
x
i
[p
i
[x
i
) 2Re(
i
0
i
[p
i
[1
i
)) =
i
Re(2p
01
) (3)
p
01
= 0
i
[p
i
[1
i
) corresponds to the transition moment for the
volume element i and we assume here that its value does not
depend on i. The ground state G] and the excited state X] of
the whole rod is given by the following equation.
[G] = [g
1
)[g
2
) [g
N
) =
i
[0
i
) (4)
[X] = [x
1
)[x
2
) [x
N
) =
i
[0
i
)

i

i
[1
i
)
j,=i
[0
j
) [G]
i

i
[1
i
] (5)
where
[1
i
] = [1
i
)
j,=i
[0
j
) (6)
corresponds to the locally excited state of the volume element i.
From this equation, we may understand that
i
gives a wave
function of the state X] as a function of the position i, with
{1
i
]} as a basis set. The polarization at a position i in the
ground and the polarized excited states, respectively, and the
total polarization P of the whole rod are given as
[G[p
i
[G] = 0
i
[p
i
[0
i
) = 0 (7)
[G[P[G] =
i
0
i
[p
i
[0
i
) = 0 (8)
[X[p
i
[X] = x
i
[p
i
[x
i
) - Re(2p
01
)
i
(9)
[X[P[X]
i
[X[p
i
[X] - Re(2p
01
)
i

i
(10)
From eq 9 we can understand that the wave function
i
is
directly related to the local polarization amplitude p
i
in the
excited state.
Now we discuss optical transition probabilities for this rod.
The probability of the optical transition from the ground state
to the polarized excited state is proportional to [GPEX]
2
where E denotes the incident electric eld. Electric eld E is in
general position dependent and thus can be expressed as E(i) =
E
0
e(i), where e(i) is a function that describes the position
dependence of the electric eld amplitude. For conven-
tional far-eld irradiation, the eld amplitude is assumed to
be uniform and independent of the position. In this case we
may set e(i) to be unity and the transition probability is
expressed as, based on the equation above,
[[G[PE[X][
2
= E
0
2
[
i
[G[p
i

i
[1
i
][
2
= E
0
2
[p
01

i
[
2
(11)
The transition probability is thus determined by the summation
(integral) of the wave function (or the polarization wave) over
the whole rod, and gives a conventional selection rule of opti-
cal transitions. For example, antisymmetric modes of polar-
ization waves with respect to the rod center yield null integral
values of the wave functions, which results in null transition
probabilities (i.e., forbidden transition) from the ground state.
In contrast, under localized near-eld irradiation, e(i) is not
uniform and has nonzero values only at some specic posi-
tions. If a sample system is irradiated by light only at a posi-
tion k (here we assumed for the simplicity that the irradiated
area has a similar size to the volume element), then we may set
e(i) =
ik
, and in this case the transition probability is given as
[[G[PE[X][
2
= E
0
2
[
i
[G[p
i

ik

i
[1
i
][
2
= E
0
2
[p
01
[
2

k
2
(12)
This means that the transition probability is proportional to
the square modulus of the wave function at the position k.
This situation is totally dierent from the far-eld irradiation
case, and gives the basis for visualization of a polarization
wave (wave function) by near-eld measurements. It is worth
noting that, in the near-eld excitation, the transition proba-
bility is given not by the integral of the wave function but by
the local amplitude of the wave function, and hence the dipole
forbidden modes can be also excited by near-eld irradia-
tion.
85,86
In fact, in Figures 3 and 5, the dipole forbidden modes
with nodes at the center of the rod (giving null integral values
of wave functions) are visualized, indicating that these modes
were optically excited.
The model analysis described above can be extended to two-
dimensional systems, and may be also applicable to polarized
excited states of nanomaterials other than plasmons. That is,
visualization of excited-state wave functions may be possible
in general by the near-eld spectroscopic imaging under
appropriate conditions. Indeed, we succeeded in observation
of two-dimensional plasmon modes in metal nanoparticles,
16
and by another research group wave functions of excitons in
semiconductor quantum wells were visualized.
87,88
5. Spectral Characteristics of Near-Field
Transmission near the Plasmon Resonance
and Anomalous Transmission Phenomenon
Prior to near-eld imaging of metal nanorods, we inves-
tigated near-eld transmission characteristics of spheric gold
nanoparticles, to understand the basics of near-eld spectra of
nanoparticles. Near-eld transmission characteristics of gold
nanospheres were reported previously,
89
but we extended the
wavelength region of observation, and claried an important
fundamental feature of near-eld measurements of nanoparti-
cles. In some cases the feature provides unique information that
is available only with the near-eld measurement, but in some
other cases it may act as a drawback to make the interpretation
of experimental results dicult. Figure 7 shows a near-eld
transmission spectrum of a spherical gold nanoparticle (diam-
eter 100 nm).
13
The horizontal line at T = 0 means that the
transmission intensity detected through the near-eld probe and
i
p
i
1 N
Figure 6. Dividing a nanorod into N equivalent volume
elements (Reproduced with permission from Ref. 66.
Copyright 2008, The Japan Society of Applied Physics.).
AWARD ACCOUNTS Bull. Chem. Soc. Jpn. Vol. 86, No. 4 (2013) 402
the sample (particle + substrate) is identical to that on a bare
substrate with no particle. The plasmon resonance of the parti-
cle locates around 550 nm. The near-eld transmission spec-
trum shows a dierential type feature around this resonance
wavelength. In particular, it shows an interesting feature that
the transmission through the particle is even stronger than that
on a bare substrate at wavelengths longer than 700 nm.
We analyzed this feature based on Mie scattering theory.
With Mie scattering theory, we can estimate, in addition to
the extinction of propagating light (that includes contribu-
tions of absorption and scattering), the near-eld scattering
intensity for a spherical particle.
2,56,57
The near-eld scattering
is the conversion of propagating light irradiated on the particle
into the localized radiation eld in the vicinity of the particle
(near-eld radiation), and is of very dierent character from
the conventional sense of scattering in far-eld radiation. We
considered that Mies formulation of the near-eld scattering
also gives a description of the reverse process, i.e., conversion
of the near-eld radiation near the particle into the far-eld
propagating light. The near-eld transmission spectrum was
simulated based on this idea. The radiation from the apertured
probe is regarded as composed of the major component of
localized near-eld and the minor component of propagating
eld. Then the observed signal in the far-eld should be a
superposition of the extinction of the propagating wave (i.e.,
far-eld extinction) by the particle and the scattering from the
near-eld localized at the probe tip to the propagating wave.
The simulated near-eld transmission spectrum based on this
idea is shown in Figure 7. The simulated result reproduces
the observed spectrum well, at least qualitatively. The far-eld
extinction component is of course the same as the extinction
spectrum of the colloidal solution, which shows a resonance
peak around 550 nm, while the near-eld scattering component
has a resonance enhancement peak at a longer wavelength
than the far-eld extinction peak, based on Mie theory. The
superposition of these two contributions gives dierential
shape spectrum. It is worth noting, in particular, that the
enhancement of the transmitted light is observed at longer
wavelength than the plasmon resonance due to the near-eld
scattering.
This is expected to be observed not only for the spherical
gold nanoparticles but also plasmon resonances of metal
particles in general. In fact, we examined near-eld trans-
mission characteristics of circular nanodisks, and found further
interesting anomalous transmission phenomenon.
17
Circular
gold nanodisks (diameter 50200 nm, thickness 35 nm) were
fabricated by electron beam lithography, and near-eld trans-
mission spectra were measured using an aperture probe with
a diameter of 100 nm. The distance from the aperture to the
disk surface was 2030 nm or less, and hence the aperture was
blocked almost completely by the disk when the disk diameter
was 100 nm or larger. Under the conventional optics of far-eld
propagating radiation, the transmission light intensity must be
reduced signicantly when the aperture is blocked by the disk.
In Figure 8, observed near-eld spectra of the nanodisks are
shown. The 100% line corresponds to the transmittance for
the bare substrate without particles. In the region above this
line the transmitted light through the aperture is enhanced by
the existence of the nanodisk. What we observed in reality
was against the intuitive expectation from the conventional
optics mentioned above: the transmission was even enhanced
by blocking the whole area of the aperture with a nanodisk.
Further surprisingly, the maximum transmission increased as
the diameter of the blocking disk got larger. The transmission
spectra showed dierential shape features in a similar way to
the spherical particle case: the transmission enhancements were
found at the longer wavelength of the disk plasmon resonances.
Consequently, we consider that the feature originates again in
the superposition of far-eld extinction and near-eld scatter-
ing. In fact, simulation of the transmission spectra based on
an idea similar to the spherical particle case reproduced the
experimentally observed spectra qualitatively well. In this
simulation Gans theory (a dipolar approximation theory) for
spheroids
56,62,90
was used to calculate the far-eld extinction
and the near-eld scattering.
The observation of remarkably strong anomalous trans-
mission in nanodisks with large diameter indicates that noble
metal nanodisks yield highly ecient mutual conversion
between propagating elds (far-elds) and localized near-
elds, and this may provide valuable information in designing
enhanced optical elds. This example demonstrates that the
near-eld transmission spectra give some unique information
C
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-0.4
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B

T
Figure 7. (A) Near-eld transmission spectrum of a gold
spheric nanoparticle (diameter 100 nm). (B) Simulation of
the near-eld transmission spectrum based upon Mie
scattering theory. Long-dashed curve: far-eld extinction
component; short-dashed curve: near-eld scattering com-
ponent; solid curve: simulated curve considering both
components (Reproduced with permission from Ref. 13.
Copyright 2004, Elsevier.).
H. Okamoto Bull. Chem. Soc. Jpn. Vol. 86, No. 4 (2013) 403
on the localized optical near-elds in the vicinities of nano-
structures. On the other hand, for this feature the near-eld
transmission characteristics cannot be in general interpreted
simply in a similar way as the far-eld cases, and we have
to keep in mind that special care must be taken for correct
understanding of the near-eld experimental results.
6. Optical Field Enhancement in
Assembled Metal Nanoparticles
It has been known for a few decades that ecient surface-
enhanced Raman scattering is often observed in metal surfaces
with nanoscale roughness or in assembled metal nanoparti-
cles.
2024
At the end of the 1990s it was reported that surface-
enhanced Raman scattering with single molecule level sensi-
tivity is possible with gold and silver nanoparticle assem-
blies.
22,23
Since this nding, many experimental and theoretical
studies have been devoted to reveal this phenomenon and to
extend its relevant applications.
24,9197
Spherical particle dimers
are thoroughly studied theoretically as a prototypical assembly
of metal nanoparticles.
22,23,9193,95,97
As mentioned before, the
spheric gold nanoparticles show plasmon resonances around
550 nm if the diameter is 100 nm or smaller, and they show
coupled plasmon modes when they form dimers. For polar-
ization parallel to the the dimer axis (the line linking the centers
of the two particles), low-energy dipole-allowed mode (we
call it parallel mode here) and high-energy dipole-forbidden
mode (antiparallel mode) are generated. When the parallel
mode plasmon is excited on a dimer with a narrow interparticle
gap, it is anticipated that a highly enhanced electric eld is
induced in the gap. Based upon electromagnetic theoretical
calculations,
91,95,97
the highest enhancement of electric eld
at the gap relative to that of the incident eld in the free space
is predicted to be as high as a few thousands (i.e., 10
6
10
7
in
optical power), when two noble metal nanoparticles form a
dimer with a gap of a few nanometers. When molecules enter
this gap area, those molecules are irradiated with an optical
eld 10
6
10
7
times stronger than the normal situation. The
Raman scattered radiation from the molecule is also enhanced
by the plasmon resonance, and consequently 10
10
10
13
times
enhancement of the Raman intensity is possible as a whole.
This mechanism is believed to be the major origin of single-
molecular level sensitivity of surface-enhanced Raman scatter-
ing. The optical elds are also enhanced in the vicinities of
single metal nanoparticles, depending on the structures and
wavelengths, while the enhancements are generally not as high
as in the gaps of dimers.
The local enhancement of optical elds by metal nanostruc-
tures may provide potential applications not only in Raman
scattering but also in broad areas of spectroscopy, photo-
chemistry, photophysics, and so on. For this reason many
fundamental and applied studies have been devoted in the past
decade to the study of dimers of gold and silver spheric nano-
particles as well as various other assembled nanoparticles.
9197
To discuss possible applications of optical eld connement
in assembled nanoparticles, observation and analysis of spatial
features of the conned elds give indispensable fundamental
information. Direct observation of optical eld distribution
with a high-resolution optical method is straightforward and
eective to achieve that. While that is practically impossible
in conventional optical microscopy because of the diraction
limit of light, it becomes feasible by the use of near-eld
optical microscopy. We have indeed succeeded in the direct
observation of conned elds by applying near-eld two-
photon excitation imaging to assemblies of gold nanoparti-
cles
2530
(The details of the near-eld two-photon excitation
imaging is explained later in Section 9).
Figure 9 shows near-eld two-photon excitation images
for gold nanosphere dimers using a femtosecond Ti:sapphire
laser (wavelength 780 nm) as an excitation source.
25,26
In this
measurement the system is illuminated by the near-eld radia-
50-200 nm
Figure 8. (Top) Experimental conguration of anomalous
transmission for a nanoaperture blocked by a gold nano-
disk. (Middle) Observed near-eld transmission spectra of
gold nanodisks (thickness 35 nm) with various diameters.
(Bottom) Simulated near-eld transmission spectra based
upon Gans theory (Reproduced with permission from
Ref. 17. Copyright 2011, American Chemical Society.).
AWARD ACCOUNTS Bull. Chem. Soc. Jpn. Vol. 86, No. 4 (2013) 404
tion through the aperture probe, and hence may actually not
coincident with the eld distribution upon far-eld irradi-
ation. However, the near-eld images obtained in this way
can be regarded as essentially equivalent with the optical eld
distribution upon far-eld irradiation, based upon the consid-
eration of electromagnetic modes of the system mentioned later
in Section 9. By comparing the two-photon excitation images
of the sample with the topographic image, we found that the
dimer generates a strong localized optical eld in the gap site
between the particles when the incident polarization is parallel
to the dimer axis. The conned eld is not observed for isolated
nanoparticles, indicating that the local eld is not very much
enhanced at this excitation wavelength. Such features are very
consistent with the theoretical predictions in the past. The near-
eld two-photon excitation images obtained are thus attributed
to the optical eld distributions in the nanoparticle assemblies.
Similarly, we measured near-eld Raman excitation images
for the dimer samples very lightly doped with a Raman active
compound (dye molecules), by detecting Raman scattered
signals from the dye molecules while the sample is excited by
light through the near-eld aperture. The spatial distribution of
the Raman activity and its polarization dependence basically
coincided with those for the two-photon excitation images.
This result strongly supports the idea that the optical elds
conned in the interparticle gaps make major contributions to
the surface-enhanced Raman scattering.
This experimental method was also applied to the assemblies
of many spheric gold nanoparticles.
2730
From the application
viewpoint, high-sensitivity surface-enhanced Raman scattering
is of great use, and hence many studies have been reported to
date on bulk preparation of noble-metal nanoparticles-xed
substrates, to get highly ecient enhanced optical elds and
Raman scattering.
98102
We observed near-eld two-photon
excitation images for island-like
28
and band-like
29
assemblies
composed of spheric gold nanoparticles (diameter 100 nm)
at the excitation wavelength of 780 nm, to investigate optical
eld distribution. A typical example is shown in Figure 10.
In this Figure, the SEM image of the sample (in gray scale) is
superimposed on the near-eld two-photon excitation image (in
color scale). Although optical eld enhancements are found to
a certain degree in the inner part of the assembly compared to
the bare substrate, the enhancement factors are not very high.
Much higher enhancements are rather localized in the rim parts
of the island-like assembly. In the studies to develop highly
ecient Raman substrates with noble metal nanoparticles,
many researchers have been trying to prepare large-area particle
arrays as closely packed as possible.
99
However, the present
results show that this strategy is not eective to get highest
possible enhancement. We performed a model analysis and
electromagnetic calculations to get insight into the origin of the
characteristic spatial features of the optical elds.
30
The result
of model analysis suggested that the plasmons excited in the
inner parts of assemblies propagate to the outer rim through the
interactions between the particle plasmons, and that plasmons
form coupled modes localized in the boundary area, which
may be the basic origin of the characteristic spatial features of
the optical elds. Localized modes are sometimes found at
boundaries and defects also for electronic and atomic motions
in crystals.
103
The localized electromagnetic elds mentioned
above may be of a similar physical origin. We consider that
closely packed arrays of particles do not yield ecient
enhancements but fabrication of arrays with uctuations and
defects is essential to obtain ecient enhanced optical elds
(the situation might be dierent if the wavelength of excitation
is dierent, however, according to our model analysis
30
).
We investigated also the optical eld structures for assem-
blies of circular void apertures opened on thin metallic lms on
substrates, by applying near-eld two-photon excitation.
33
For
instance, we found for linear arrays of circular voids (diameter
ca. 400 nm) on a 25-nm thick gold lm that optical elds are
conned in gaps between the voids. This indicates that not
only assemblies of particles but also arrays of voids on thin
metallic lms can be utilized for spatial design of localized
optical elds.
7. Time-Resolved and Nonlinear Measurements
in Near-Field Microscopy
The original motivation of our near-eld research project
was to develop a new microspectroscopic method by com-
bining near-eld optical microscopy and laser spectroscopic
E
E
A B C
Figure 9. Near-eld observation of enhanced elds in gold
nanosphere dimers. (A) Topography of the sample. (B) and
(C) Near-eld two-photon excitation images of the sample.
The excitation wavelength was 785 nm. The arrows indi-
cate polarization of the excitation elds for respective
panels. The white circles indicate approximate positions of
the particles (Reproduced with permission from Ref. 66.
Copyright 2008, The Japan Society of Applied Physics.).
Figure 10. Near-eld two-photon excitation image of an
island-like gold nanosphere assembly. The scanning elec-
tron micrograph image of the sample (in gray scale) is
superimposed on the two-photon excitation image (in color
scale). The line prole of two-photon excitation proba-
bility along the dashed line in the image is indicated in
the left panel (Reproduced with permission from Ref. 28.
Copyright 2008, American Chemical Society.).
H. Okamoto Bull. Chem. Soc. Jpn. Vol. 86, No. 4 (2013) 405
techniques and to apply it to the studies of nanomaterials.
In particular I intended to perform ultrafast time-resolved and
nonlinear optical measurements in the near-eld regime. We
thus set up a near-eld imaging system by introducing a
mode-locked Ti:sapphire laser to a near-eld optical micro-
scope.
1012,31,104
Figure 11 shows the experimental arrangement
for time-resolved measurements. There are two possible modes
of measurements: the collection-mode arrangement where the
ultrashort pulses illuminate the sample as propagating far-eld
radiation and the system response is collected by the near-eld
probe;
105
and the illumination-mode setup where the pulses are
illuminated through the near-eld aperture.
106110
We adopted
the illumination-mode setup because we preferred to specify
the location of photoexcitation by the position of the near-
eld probe, although the system arrangement is more compli-
cated than that for the collection-mode measurement. As the
ultrashort optical pulses transmit through the ber for quite a
long distance in the illumination-mode measurements with an
apertured ber probe, the pulse width suers from serious
broadening due to the dispersion eect of the ber material.
The pulse broadening results in lowering of time resolution
in the time-resolved measurements, and lowering of signal
eciency in the nonlinear optical measurements. To avoid
that, the pulse is passed through a dispersion compensation
device before coupling into the ber to give a negative dis-
persion.
10,106,107
The dispersion compensation device is adjust-
ed to yield the shortest possible pulse width at the exit of the
aperture probe tip. A grating pair device is adopted typically as
a dispersion compensation device. We achieved ca. 100 fs time
resolution in the near-eld ultrafast imaging by introducing a
grating pair device that nearly recovers the original pulse width
of the laser output (ca. 80 fs) after ca. 1-m optical ber.
10,11
The principle of the near-eld ultrafast measurement is
basically the same as that of transient absorption correlation
method
10,106,110
in the far-eld experiment that is often used in
ultrafast spectroscopy, except that the dispersion compensation
is indispensable.
10,106,110
The optical beam from the pulsed laser
source was divided into pump and probe beams with approx-
imately the same intensity, and the two beams passed through
respective optical delay lines to give a variable delay time
between the pump and probe pulses. The two beams were
collinearly combined again into one beam, which was coupled
into the ber after the dispersion compensation device men-
tioned above. Here, the pump and probe pulses have essentially
the same characteristics (equal pulse correlation method),
111
and there is no discrimination between them except for the
dierence in the pulse timing. We can also perform two-color
experiments if necessary by converting the probe pulse wave-
length using a photonic crystal ber or other nonlinear media,
but in this case the time resolution usually becomes worse
than the equal pulse correlation method.
12,104
The pump and
probe beams were modulated by a mechanical chopper, and the
light intensity after transmission through the aperture probe
and the sample was lock-in detected to extract the signal of
pump-induced transmission change for the probe beam. With
this setup, near-eld measurements with transient absorption
changes were feasible.
We have performed also near-eld nonlinear optical imaging
measurements with a similar setup. For the two-photon excita-
tion probability imaging
14,16,2529,32,33,112,113
that has been used
as the major technique to visualize enhanced optical elds, no
pumpprobe delay is necessary, and thus the optical delay lines
were removed from the setup. The signal detected was the two-
photon-induced luminescence from gold nanostructures (wave-
length around 500 to 700 nm). We can also perform near-eld
nonlinear optical imaging by detecting second-harmonic gen-
eration signal with a one-color experimental setup, that of sum-
or dierence-frequency generation or coherent Raman scatter-
ing signal with a two-color experimental setup, and so forth, by
minor modications of the apparatus.
Ti:sapphire laser
grating
chopper
optical delay line
detector
sample
near-field probe
optical fiber
coupler
microscope objective
grating pair
device
(A)
(B)
Figure 11. Schematics of ultrafast near-eld measurement
setups. (A) A setup for measurements with ca. 100-fs time
resolution. (B) A setup for measurements with <20-fs time
resolution, equipped with a pulse-shaping system (Repro-
duced with permission from Ref. 31. Copyright 2012, The
Japan Society of Applied Physics.).
AWARD ACCOUNTS Bull. Chem. Soc. Jpn. Vol. 86, No. 4 (2013) 406
Figure 12 demonstrates the time-resolved measurement of
energy relaxation in a gold nanorod after photoexcitation, as
a typical example of near-eld ultrafast time-resolved imag-
ing.
11
Since the plasmon has already dissipated in a very fast
dephasing time (less than ca. 20 fs for gold nanorods), the
dynamics observed here are electronelectron scattering,
electronlattice scattering, and cooling processes, which follow
after the dissipation of the plasmon.
114120
A characteristic
spatial feature is observed at several hundred femtoseconds
after photoexcitation, where the sign of the transient absorption
in the center of the nanorod is opposite from that at both sides
of the nanorod. We analyzed the origin of this with the aid
of electromagnetic theoretical simulations, and found that this
reects the transient change of the plasmon modes (plasmon
waves) due to the electronic temperature rise induced by the
pump pulse.
121
This nding suggests potential for develop-
ment of a new way to control the plasmon waves in metal
nanostructures.
As mentioned above, we can observe dynamic behavior
of the metal nanostructured materials after the dissipation of
plasmon resonance, when the time resolution of the measure-
ment is of the order of 100 fs. However, this time resolution
is still not sucient to investigate the essential function of
plasmons from a dynamic point of view, and time resolution
even higher than the plasmon dephasing is necessary. For this
purpose, near-eld ultrafast measurements with time resolu-
tion higher than 20 fs is required, since the dephasing times of
plasmons in gold nanostructures are in the range between a
few femtoseconds to ca. 20 fs.
122
Very recently scattering type
ultrafast near-eld measurements with <20 fs optical pulses
have been reported,
123,124
but we chose to develop aperture-
type ultrafast measurements considering the dierence in
polarization characteristics of these methods. It is dicult to
achieve that in a ber-probe-based near-eld microscope by the
simple use of passive dispersion compensation devices like
grating pairs and prism pairs, because of higher order group
velocity dispersion eects. To overcome that, we developed an
ultrafast near-eld optical measurement setup (Figure 11) by
introducing dispersion compensation with a spatial phase modu-
lator.
31
In this setup, among various order dispersion eects
arising from the optical ber and other elements, the major parts
of the low order dispersion are compensated with prism and
grating pairs, and the higher order dispersion is adaptively com-
pensated with a spatial phase modulator. With this arrangement
we succeeded in delivering 17-fs optical pulses to the aperture
probe tip. Time-domain observation of plasmon dephasing with
a time constant of ca. 8 fs was also successful. Further extension
of the methodology may give us the chance to reveal optical
functions of metal nanostructures before dissipation of plas-
mons, and to control plasmon waves in time domain.
8. Two-Photon-Induced Photoluminescence
from Noble Metal Nanoparticles
Generally speaking, two-photon excitation of molecules and
materials, which is a nonlinear optical process, is more dicult
than one-photon excitation. The nonlinear optical process
becomes prominent as the pulse duration of the incident light
gets shorter, if the average power of the light is kept constant.
The recent progress of femtosecond light sources makes
nonlinear optical experiments much easier than before. In far-
eld optical imaging, the spatial resolution is improved by
the use of nonlinear processes because the nonlinear process
takes place locally near the focal spot when the incident beam
is focused. This has strengthened application of two-photon
microscopy to bioimaging studies greatly. It is speculated that
the nonlinear optical process may occur relatively easily if
the optical transition involved is accompanied with a large
oscillator strength. Since plasmons are collective oscillations
of many conduction electrons in metals and thus have huge
oscillator strengths, the nonlinear optical transitions for the
plasmon resonances may be easily observable (In fact, we
found a nonlinear phenomenon in optical trapping of gold
nanoparticles, which was interpreted as being caused by the
strong nonlinearity due to the plasmon resonance.
125
We do not
discuss the details here.).
It has been known from a few decades ago that noble metals
(in particular gold) show faint photoluminescence, and its
mechanism has been discussed.
126128
Owing to the develop-
ments in fabrication methods of metal nanostructures and
in femtosecond light sources, investigation of two-photon-
induced luminescence from gold nanostructures has become
feasible. It has been found recently that isolated gold nano-
particles (nanorods, triangle nanoplates, etc.) and assemblies
of them show quite strong two-photon-induced luminescence
when excited with ultrashort pulses.
14,32,129131
Application of
two-photon-induced luminescence to bioimaging studies has
been also reported.
132134
The intensity of the two-photon-
induced luminescence from gold is much higher than what is
expected from low-eciency one-photon luminescence, which
suggests the highly ecient two-photon transition for the gold
nanostructures. This ecient two-photon process may be rele-
vant to the huge oscillator strength of the plasmon resonances
as mentioned above. In this section, studies on characteristics
of the two-photon-induced photoluminescence from noble
metals (mainly gold) are summarized.
Figure 13 shows a typical two-photon-induced photolumi-
nescence spectrum from a gold nanorod, measured by the near-
T
r
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c
h
a
n
g
e

(
a
r
b
.

u
n
i
t
)
0.0
1.0
1.0
Figure 12. Near-eld transient transmission change images
for a gold nanorod (diameter 30 nm, length 300 nm)
(Reproduced with permission from Ref. 11. Copyright
2004, American Chemical Society.).
H. Okamoto Bull. Chem. Soc. Jpn. Vol. 86, No. 4 (2013) 407
eld nonlinear optical measurement setup described before,
with the near-eld illumination mode. The excitation wave-
length was 785 nm. The spectral features depend on the geo-
metries of the gold nanostructures measured, but in most cases
two peaks (or shoulders in some cases) appear around 550 and
650 nm regardless of the geometries.
14,32,112
According to the
band theory calculation of gold, these emission wavelengths
correspond well with that of recombination of an electron in the
sp band and a hole in the d band near L (for the peak around
550 nm) symmetry points of the rst Brillouin zone and that
near X point (650 nm), respectively.
127,135
The polarization
measurement of the emission show that the emission around
650 nm (we call it hereafter X emission) is strongly polarized
along the rod axis, while that around 550 nm (L emission) is
only weakly polarized along the axis.
32,112
These observed
polarization characteristics are consistent with the assignment
of the emission to the electronhole recombination near X and
L points. Based on the polarization characteristics of the
luminescence and analysis of the X- and L-emission intensity
ratios for various nanorods, we presently believe that the
luminescence is attributable to the spd electronhole recom-
bination emission resonantly enhanced with the plasmons.
112
Each nanoparticle shows its own characteristic X and L
intensity ratio, probably because the plasmon resonance
condition strongly depends on the geometry of the particle.
Dulkeith et al. reported, on the other hand, that the lumines-
cence from gold is attributed to radiative decay of a plasmon
that is excited by the electronhole recombination, from the
analysis of diameter dependence of the emission quantum yield
for spherical gold nanoparticles.
128
This interpretation of the
emission mechanism looks similar to that mentioned above, but
is dierent in its basic physical picture. Further investigation
is necessary to clarify the luminescence mechanism of gold
nanoparticles. In either case, appearance of strong plasmon
resonances in the wavelength region longer than ca. 600 nm
(corresponding to the X emission region) may be the major
factor for the strong luminescence from gold nanostructures.
This luminescent property suggests a potential utility of gold
nanoparticles as probe materials for two-photon imaging, and
some researchers indeed attempted application of gold nano-
particles to bioscience.
132,133
Our group found that triangular
plate nanoparticles of gold, among various single gold nano-
particles, show particularly strong two-photon-induced lumi-
nescence,
16
and proposed that this material may be applied to
bioimaging.
134
Silver nanoparticles also show two-photon-induced lumi-
nescence in the visible to near-infrared region when excited
with ultrashort near-infrared pulses. However, each particle
shows a dierent luminescence spectrum with dierent peak
wavelengths, unlike gold nanoparticles.
113
Interband transi-
tions are not expected in this wavelength region from the band
structure of silver. Meanwhile, the surfaces of silver nanostruc-
tures are easily oxidized compared with that of gold, and thus
the surface is thought to be covered with silver oxide under
ambient conditions, which gives rise to photoluminescence.
It is therefore likely that the two-photon excitation energy
imposed on silver is transferred to silver oxide on the surface,
and the luminescence from the silver oxide is resonantly
enhanced by the plasmon modes of the nanoparticle. This is the
most probable origin of the two-photon-induced luminescence
from silver nanoparticles.
113
For both gold and silver nanostructures the two-photon-
induced photoluminescence shows suciently strong intensity
that we can record near-eld two-photon excitation images by
detecting the luminescence as a signal, as mentioned in the
previous sections. Figure 14 shows two typical near-eld two-
photon excitation images of gold nanorods.
14
The sample was
irradiated by femtosecond near-infrared (wavelength 780 nm)
pulses through an apertured optical ber probe, and the inten-
sity of the emission from gold was detected while raster-
scanning the sample, to construct the image. The dimensions of
the respective rods were 40 nm

230 nm
l
and 35 nm

440
nm
l
. These two images look very dierent. Obviously the image
in Figure 14B corresponds to the square modulus of the wave
function of the plasmon mode resonant with the incident
light, as we discussed in Section 4. In contrast, in Figure 14A
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(A)
(B)
Figure 13. Typical two-photon-induced luminescence spec-
tra for a gold nanorod. Excitation wavelength was 780 nm.
Black curve (A): polarization of the luminescence perpen-
dicular to the rod axis; red curve (B): polarization parallel
to the axis of the rod (Reproduced with permission from
Ref. 112. Copyright 2009, American Chemical Society.).
A B
Figure 14. Near-eld two-photon excitation images of gold
nanorods (A: diameter 40 nm, length 230 nm; B: diameter
35 nm, length 440 nm). Incident wavelength was 780 nm,
and the polarizations of excitation were approximately
parallel to the long axes of the rods. Scale bars: 200 nm
(Reproduced with permission from Ref. 14. Copyright
2004, American Chemical Society.).
AWARD ACCOUNTS Bull. Chem. Soc. Jpn. Vol. 86, No. 4 (2013) 408
the excitation probability is conned near both ends of the
rod. Such an observed image corresponds well with the eld
distribution associated with the lightning rod eect, where the
electric elds are conned near sharpened edges and apexes of
metal structures.
93,136139
We introduced in Section 4 an inter-
pretation of the plasmon modes as polarization standing waves.
Since the longitudinal polarization wave is accompanied by
an electric eld along the rod axis, the wave observed in
Figure 14B corresponds to the optical eld distribution arising
from the standing wave of the plasmon mode. In Figure 14B,
the plasmon mode was resonant with the incident light and
thus the image was reected by the optical eld distribution
arising from the mode. The image in Figure 14A, in contrast, is
interpreted as the optical eld due to the lightning rod eect
being visualized because the incident light is not resonant with
any standing wave modes of plasmons. The lightning rod eect
occurs not only under oscillating electric eld but also under
direct current (DC) eld, and shows only weak frequency
dependence. This eect is hence observable at frequencies not
in resonance with any standing wave plasmon mode.
9. Correlation between the Near-Field Excitation Image
and the Localized Field Distribution
As illustrated in the previous section, the near-eld two-
photon excitation imaging method provides a valuable tool to
visualize the localized optical elds in nanostructures and we
utilized this method in our studies of assembled nanoparticles
as described in Section 6. To rationalize this way of observing
eld distributions, it is necessary to ensure that the near-eld
excitation probability corresponds to the eld intensity upon
far-eld irradiation of light to the system. We discuss here
qualitatively the correlation between the near-eld excitation
images and the optical eld distributions.
What is obtained directly by the two-photon excitation
image is basically the distribution of excitation probability and
not that of eld enhancement in the system. The optical eld
distribution is a map of the eld intensity when the whole area
of the system is irradiated by light. These two (the excitation
probability distribution and the eld distribution) are related
to dierent physics and are not necessarily equivalent to each
other. However, we believe that a kind of reciprocity relation
holds roughly among these two as mentioned in the following,
and in that case the excitation probability image gives the
optical eld distribution.
140
As a model system to discuss the physical picture, we con-
sider oscillation of a string. An oscillating local eld is applied
to the string, which excites a wave on the string (Figure 15). If
the excitation is at the fundamental oscillation frequency of the
string
1
, the string may be excited at any position on the string
but particularly eciently at the center. On the other hand, if
the excitation is at the rst overtone frequency
2
, the overtone
mode cannot be excited at the center where the oscillation
amplitude is null. Instead, strong excitation is possible at both
sides of the center of the string. Based on this consideration, we
may expect that a plot of oscillation amplitude against the
excitation position gives the spatial structure of the oscillating
wave on the string (i.e., mode) that is in resonance with the
excitation frequency. In this model, the local excitation source
corresponds to the localized irradiation of light with an aperture
probe in near-eld optical microscopy. The oscillating string
corresponds to the electromagnetic eld of the system. This
qualitatively explains the physical picture that the observation
of excitation probability distribution gives the spatial structure
of the electromagnetic modes of the system, and as a con-
sequence localized optical elds are visualized. In other words,
the near-eld excitation probability gives the local density of
electromagnetic modes, and a strong electromagnetic eld exist
if the density of modes is high at the position.
10. Summary
In this account, I described near-eld microscopic studies
on noble metal nanoparticles and related topics. On noble
VU
filter
strong
speaker
resonantly excited
moderate
VU
weak
VU
VU
strong
near-field (localized) excitation far-field excitation
fundamental overtone
fundamental
frequency
Figure 15. Excitation of mechanical oscillation waves in strings as analogies to near-eld and far-eld excitation of optical modes
of materials. See the text for the details.
H. Okamoto Bull. Chem. Soc. Jpn. Vol. 86, No. 4 (2013) 409
metal nanoparticles and assemblies, we showed that plasmon
waves and enhanced optical eld structures can be visualized
by near-eld optical microscopy. Development of near-eld
ultrafast and nonlinear optical measurement methods, which
played essential roles in visualization of plasmon elds,
was also described. Through these studies, we established
a valuable methodology to investigate optical properties of
metal nanostructures, and succeeded in obtaining informa-
tion that is available only by optical measurements with high
spatial resolution beyond the diraction limit of light. I hope
that the methodology we developed and the information
we got provide foundations for basic and applied studies of
plasmon resonances in the future. We may expect not only to
deepen understanding of fundamental physical and chemical
properties of plasmons in metal nanostructures, but also to
contribute to broad research areas, which include, for example,
ultrasensitive analytical methods on the basis of enhanced
spectroscopy, luminescence properties of metal nanoparticles
and application of that to bioimaging materials, application
of enhanced optical elds to energy and chemical conversion
systems and photolithography, design of novel nanooptical
devices based upon the characteristics of plasmon modes, and
so forth.
We are now planning (or partly executing) the following
projects as the next step of this study. One is to perform
near-eld measurements of enhanced eld distributions in a
wide wavelength range for metal nanostructures (nanoparticle
assemblies in particular), to verify the validity of the inter-
particle coupling model we proposed in Section 6. This may
provide valuable designing guidelines of enhanced optical
elds. Next is application of the near-eld ultrafast method
to various systems and development of space-time manipula-
tion methodology for plasmon elds. By the pulse shaping
technique for the excitation light combined with proper design
of metal nanostructures, potential utilities of dynamic charac-
teristics of metal nanostructures may be increased. Another one
is to pursue potentials of polarization dependent near-eld
measurements, in particular circular dichroism measurements.
This methodology provides novel and valuable techniques for
the study of chirality of nanomaterials, and may develop a new
research area in photo- and materials sciences.
For further progress in application of near-eld optical
methods, development in theoretical and calculation methods
to interpret the observed images is essential, in addition to that
in experimental methods. The far-eld optics theory has a su-
cient accuracy to interpret images obtained by conventional
optical microscopes,
58
while the near-eld theory is much more
complex and not so accurate as the far-eld theory at least
at present.
4,7176,141143
One of the reasons is that the probe is
almost in contact with the sample in the near-eld measure-
ments and hence the perturbation of the probe to the sample is
sometimes not negligible. Another diculty in the theoretical
treatment of near-eld imaging is that the wide range of the
spatial scale (nano to macro) must be involved in the system,
since the material system treated is of subwavelength spatial
scale while the photodetection is usually done in the far-eld
macroscopic regime. If these diculties can be overcome and
the theoretical framework is established to interpret near-eld
images of various samples from a unied viewpoint, it will
be highly useful for the studies of nanooptical properties of
materials.
In recent years, various other experimental methods to study
excited-states of materials in spatial resolutions beyond the
diraction limit of light have been highly advanced.
144146
Typical examples are electron/X-ray diraction
147150
and
electron microscopy
144,145,151
combined with ultrashort pulsed
light sources. Nanooptical methods are expected to provide
valuable information complementary to that by the advanced
methods mentioned above, and further developments are highly
desired to advance nano-photosciences.
I am very much grateful to collaborators who contributed
to this research project, in particular Prof. K. Imura (now
at Waseda University), who was the rst member of my
laboratory at the Institute for Molecular Science and made
major contributions to most of this research project, and many
other members (present and former) of my laboratory as
well: Dr. T. Nagahara (Kyoto Institute of Technology), Prof.
J. K. Lim (Chosun University), Dr. N. N. Horimoto (Tohoku
University), Dr. Hui Jun Wu, Prof. Y. Jiang (South China
Normal University), Dr. T. Narushima, Dr. Y. Harada (The
University of Tokyo), Dr. S. I. Kim (Samsung), and Dr. Y.
Nishiyama. I also thank many collaborators from other insti-
tutions: Dr. M. K. Hossain (King Fahd University of Petroleum
and Minerals), Dr. T. Shimada (Hirosaki University), Prof.
M. Kitajima (National Defense Academy), Prof. K. Ueno
(Hokkaido University), Prof. H. Misawa (Hokkaido Univer-
sity), Ms. Y. C. Kim (Seoul National University), Mr. S. Kim
(Seoul National University), Minwoo Lee (Seoul National
University), Prof. D. H. Jeong (Seoul National University),
Prof. K. Sawada (Shinshu University), Prof. H. Nakamura
(National Institute for Fusion Science), Prof. T. Saiki (Keio
University), Dr. K. Matsui (National Institute for Physio-
logical Sciences), Prof. R. Shigemoto (National Institute for
Physiological Sciences), and Prof. S. Kim (KAIST). The
author is also indebted to the Equipment Development Center
and the Laser Research Center for Molecular Science of
Institute for Molecular Science. This research was supported
by the Grants from Ministry of Education, Culture, Sports,
Science and Technology (Nos. 17034062 and 19049015), from
Japan Society for the Promotion of Science (Nos. 16350015,
17655011, 18205004, 21655008, and 22225002), and from
Kurata Science Foundation. The project was also supported in
part by the Extreme Photonics Project and by the Consortium
for Photon Science and Technology.
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Hiromi Okamoto received B.S. (1983) and M.S. (1985) degrees from Department of Chemistry,
Faculty of Science, The University of Tokyo. He received a Doctor degree in 1991 from The
University of Tokyo. He was appointed as a Research Associate at Institute for Molecular Science
in 1985, where he developed femtosecond coherent Raman spectroscopic methods and studied
vibrational dephasing in liquids. He then moved to The University of Tokyo in 1990, and was
promoted to Associate Professor in 1993, where he studied vibrational relaxation phenomena
using picosecond Raman spectroscopy, and also excited-state molecular structures/dynamics by
using picosecond infrared spectroscopy in the ngerprint region. Since 2000, he has been serving
as a Professor at Institute for Molecular Science. His present major research interests are near-eld
optical and spectroscopic studies of nanomaterials, especially excited-state dynamics.
H. Okamoto Bull. Chem. Soc. Jpn. Vol. 86, No. 4 (2013) 413