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ABSTRACT
We have found that spherical gold nanoparticles immobilized on a gold substrate with a gap of a few nanometers, which
is supported by self-assembled monolayers, show large activity of second-harmonic generation (SHG). Spectroscopic
SHG measurements were performed with a Ti:Sa laser in order to investigate the origin of the intense SHG. It was
found that the SHG intensity increases with shorter wavelength region, indicating that the enhancement originates from
localized surface plasmon resonance in the system. We also fabricated microarrays of the surface immobilized gold
nanoparticles through photoregistration of the self-assembled monolayers used to support the nanogap. The
nanoparticle microarrays were characterized by SHG microscopy. The microarrays can be applied to multichannel
biological sensors using linear optical spectroscopy.
Keywords: surface plasmon resonance, nonlinear optics, second-harmonic generation, gold nanoparticles
1. INTRODUCTION
Localized surface plasmon in isolated spherical gold nanoparticles has a resonance frequency at around 520 nm. The
resonance is strongly modulated by boundary conditions such as an ambient refractive index and presence of adsobates
on the metallic surface. When the nanoparticles are located adjacent to the metallic surface, the mirror image effect
plays an important role to the resonance conditions. This has been already predicted both theoretically and
experimentally by a few groups1-5. When gold nanoparticles are located above a gold surface with a band gap of a few
nanometers, strong electromagnetic interactions occur between the nanoparticles and the metallic surface, and as a result,
enhanced optical electric fields are generated in the nanogap. A resonance red-shifted from that of isolated
nanoparticles is observed2,4,5. It is expected that the large electric field can be applied to various spectroscopic
techniques exemplified by Raman scattering6 and nonlinear optics. Our recent study showed that a gold surface
covered with gold nanoparticles show considerable activity of second-harmonic generation (SHG) by a few hundred
times much more that of a gold surface without any gold nanoparticles7.
In this report, we apply SHG spectroscopy to the gold surface covered with gold nanoparticles in order to
clarify the mechanism of the increase in the SHG intensity. The SHG intensity monotonically increases with decrease
of the wavelength of the fundamental light ranging from 720 nm to 850 nm. In this system, the resonance wavelength
of the localized surface plasmon lies at around 620 nm. Therefore, the increase can be attributed to the resonance
enhancement. We also fabricated gold-nanoparticle arrays of circular dots 125 µm in diameter on a gold surface. For
the preparation of the arrays, we examined two methods as schematically illustrated in Figure 1: (i) photopatterning of
an aminoalkanethiol self-assembled monolayer (SAM) film for making cross-linkage from the gold surface to the gold
nanoparticles followed by deposition of gold nanoparticles (method A). (ii) photopatterning of an octadecanethiol (ODT)
SAM film, followed by deposition of the aminoalkanethiol SAM films. Then gold nanoparticles are deposited by
immersion of the substrate in a solution of gold nanoparticles (method B). We characterized the arrays by SHG
microscopy, which is a powerful probe for the samples of this kind, and confirmed formation of the gold-nanoparticle
arrays. These localized surface plasmon resonance arrays can be applied to multichannel biological sensors using linear
optical spectroscopy.
------------------------------------------------
*Further author information: (Send correspondence to K. K.)
K. K.: E-mail: kajikawa@ep.titech.ac.jp, Telephone +81 (0) 45 924 5596
method B
UV irradiation immersion in the AUT or immersion in the
rinse with ethanol
merocyanine solution nanoparticle solution
grid
ODT SAM film
thin gold film
silica substrate
HS
ODT
NH2 AUT
HS
NH2 AHT
HS
NH2
HS AET
Figure 2. Chemical structure of the compounds used in the present study: octadecanethiol (ODT), aminoundecanethiol
(AUT), aminohexanethiol (AHT) and aminoethanethiol (AET).
half wave
plate
Glan-
×
cooled CCD
Taylor (1024 1024 pixels, {13 µm} 2)
prism
2ω-cut ×3
color filters for
( )
lens
×2.5
objective lens
f=200
100
color sample
filter for
ω-cut
Figure 3. Optical setup used in the present study.
2. EXPERIMENTS
The gold nanoparticles were prepared by reduction of NaAuCl4. An aqueous solution of 0.254 mM NaAuCl4 (100 mL)
was maintained at 95 C in a water bath, and an aqueous solution of 33.3 mM citrate (2.5 mL) was added, with stirring.
The color of the solution had turned ruby-red immediately. After further stirring for 10 min., the solution was cooled to
room temperature. The resulting gold nanoparticles were found to be spherical with a diameter of 40 nm according to
transmission electron microscopy.
Octadecanethiol (ODT) was used as a compound that covers the gold surface. The aminoundecanethiol
(AUT), aminohexanethiol (AHT) and aminoethanethiol (AET) were used for cross-linking between the gold
nanoparticles and the gold surface. The chemical structures of the compounds are illustrated in Figure 2. They were
dissolved in ethanol at a concentration of 1mM. The molecules are self-assembled by immersion of the gold substrate
in the ethanol solution for 2 hours. The UV-photopatterning8 was performed with a low-pressure mercury lamp (L937-
01: Hamamatsu Photonics K. K. , Japan). The intensity of the UV light was 25mW/cm2, and the irradiation time was
12 min for the AUT SAM film and 40 min for the ODT SAM film. Two kinds of masks were used. One was a cupper
grid for a transmission electron microscope having circular holes 125 µm in diameter ordered in a square lattice. This
mask was used in method B. The other mask was a homemade chromium mask, which was made by vacuum-
evaporation of a 100-nm thick thin chromium film on a fused quartz plate through the cupper grids. This mask was
used in method A. The outlines of the preparation process of method A and method B are illustrated in Figure 1.
The SHG measurements were performed with an optical set up depicted in Figure 3. A mode-locked Ti: Sa
laser (Tsunami, Spectra Physics Inc., USA) was used as a light source with a pulse width of 130 fs running at a
Figure 4 shows the reflection absorption spectra for the p-polarized light at an oblique incidence with an angle of 45
degrees from the surface normal. In addition to the first peak at around 520 nm, which is usually observed in isolated
spherical gold nanoparticles, another peak appears in the range from 650nm to 800nm. This peak is absent at normal
incidence or for s-polarized light, so that this band originates from the surface normal component of the electric field of
the p-polarized light. This is because the normal component of the electric field strongly produces quadra-polar
interaction between the nanoparticles and their mirror images in the gold substrate, whereas the in-plain component does
not. The position of the peak is blue-shifted with increasing the distance owing to the difference in the strength of the
interaction. These results support the previous theoretical1,2 and experimental5 studies.
0.8
reflection absorption
AET(n=2)
0.6
0.4 AHT
(n=6)
(n
AUT
0.2 (n=11)
400 500 600 700
wavelength/nm
Figure 4. The reflection absorption spectra for the p-polarized light at an oblique incidence with an
angle of 45 degrees from the surface normal.
3 3
2 2
1 1
0 0
700 750 800 850 700 750 800 850
wavelength /nm wavelength /nm
Figure 5. Spectroscopic SHG measurements (a) gold nanoparticles immobilized on a gold surface with an AET SAM film.
(b) gold nanoparticles immobilized on a gold surface with an AUT SAM film.
(a) (b)
200 µm 200 µm
Figure 6. (a) SHG images of the gold-nanoparticle array prepared by (a) method A and (b) method B.
200 µm 200 µm
Figure 7. The SH images before (a) and after (b) deposition of gold nanoparticles
The SHG spectra were measured at ranging from 730 nm to 850 nm. Figure 5(a) and 5(b) respectively show the spectra
from the sample with a gap of AET (n=2) and AUT (n=11). The intensity in the figure is normalized by the SHG
intensity form bare gold surface. The SHG spectra clearly show frequency dispersion: the SHG is larger with the
shorter wavelength excitation.
Since SHG is one of the second-order nonlinear optical phenomena, it is absent in a system with inversion center
under the electric dipole approximation. It is widely known that SHG occurs at a surface or an interface region, since
inversion center is essentially absent there. Therefore, SHG has been used as a powerful tool for surfaces and interfaces
so far. In the mean time, a bulk metal shows SHG activity. This originates from higher order contribution to the
second-order nonlinear polarization, such as quadruples and magnetic dipoles. While there are a few processes in the
higher order contribution, change in the electron density in the surface region gives the primary contribution to SHG.
Our recent study actually concluded that the SHG manly comes from the surface and interfaces even in case of metals9.
Hence the degree of asymmetry in the surface region will be an important factor in the effective surface susceptibility.
Since the presence of gold nanoparticles on a gold surface adds the degree of asymmetry in the surface region, it seems
that the gold nanoparticles immobilized above a gold surface will give a larger surface susceptibility than that of a gold
surface without any gold nanoparticles.
According to the knowledge previously studied described above, there are two possible reasons for the enhancement
of the SHG from the system of surface-immobilized gold nanoparticles on a gold surface with a nanogap. One is the
enhancement of electric field produced by localized surface plasmon resonance. This effect strongly depends on the
wavelength of the fundamental or SHG light. The other is addition of noncentrosymmetry due to the presence of gold
nanoparticles. This effect will hardly depends on the wavelength of light. The present results that the SHG intensity
clearly depends on the fundamental wavelength will support the former reason. Thus we conclude that the
enhancement originated from the localized surface plasmon resonance.
4. CONCLUSION
The spherical gold nanoparticles immobilized on a gold substrate with a gap of a few nanometers were
fabricated by SAM films. This system shows large SHG activity. The spectroscopic SHG measurements were
performed with a Ti: Sa laser. It was revealed that the intensity of SHG increases with short wavelength region,
indicating that the enhancement originates from localized surface plasmon resonance of this system. We also reported
the fabrication of the surface-immobilized gold nanoparticle microarrays on a gold surface obtained from UV-
photopatterned SAM films. Two kinds of methods to pattern the SAM films were examined: (i) patterning of
microdots of the AUT SAM films used as a spacer on the gold surface to form cross-linkage from the surface to the
nanoparticles. (ii) Patterning of inert SAM films having microholes in which a SAM film that make the cross-linkage are
formed. Both methods allow us to form the ordered microdots of gold nanoparticles. In the array formed through
method B, surface areas outside the microdots are inert by using a certain SAM film that resists the nonspecific binding
to proteins. The arrays of the microdots of gold nanoparticles were characterized by SHG microscopy, which delivers
the high contrast image due to enhancement of the electric field in the nanogap between the gold nanoparticles and the
surface. These localized surface plasmon resonance arrays can be applied to multichannel biological sensors using
linear optical spectroscopy.
ACKNOWLEDGEMENTS
This work was partly supported by Grants-in Aid from the Ministry of Education, Culture, Sports, Science and
Technology of Japan.
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