pubs.acs.

org/journal/apchd5 Article

Phase-Selective Four-Wave Mixing of Resonant Plasmonic

Nanoantennas
Veit Giegold, Karol Koła̧taj, Tim Liedl, and Achim Hartschuh*
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ABSTRACT: Metallic nanoantennas are key components of a

wide range of optical techniques that exploit their plasmonic
response for signal amplification and extremely sensitive detection.
For nonlinear techniques, the higher-order plasmonic response of a
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nanoantenna can be predicted by the product of the nanoantenna’s

linear susceptibilities, known as Miller’s rule, provided that the
spatial field distributions at the fundamental and the nonlinear
frequencies are the same. Here, we show that Miller’s rule also
holds for ultra-broadband excitation pulses and that it can be
utilized to predict the frequency dependence of the near-degenerate
four-wave mixing (ND-FWM) intensities generated by individual
resonant plasmonic nanoantennas. Importantly, this implies that
the nanoantenna’s nonlinear response can be deterministically
controlled and further optimized by varying the spectral phase of the laser pulse. We demonstrate this by measuring the chirp
dependence of the ND-FWM signal and observe an enhancement of up to 60% depending on the position of the plasmon resonance
with respect to the laser spectrum, in agreement with model predictions. Finally, we exploit this phase control for chirp-selective
confocal imaging of resonant nanoantennas. Our findings may help improve the sensitivity of nonlinear techniques such as plasmon-
enhanced coherent anti-Stokes Raman scattering.
KEYWORDS: plasmonics, four-wave mixing, nonlinear optics, pulse shaping, femtosecond, DNA origami

■ INTRODUCTION
Plasmonics evolved into a main pillar of nanophotonics and
profiles, phase shaping of the laser spectrum can be applied to
tune local plasmonic fields and the resulting optical response,
nano-optics by providing a means to manipulate optical fields which is fundamental for plasmonic coherent control
at sub-diffraction length scales. Its key elements are plasmonic schemes.8,9 To date, this approach has been used to control
nanoantennas which exploit localized surface plasmon second harmonic generation,10 photoelectron emission,11,12
resonances (LSPRs) and their unique property to convert two-photon photoluminescence of LSPR,13 and FWM of
propagating radiation into strongly confined and enhanced propagating surface plasmon polaritons.14 The intricate
optical fields.1,2 The efficiency of this process can be expressed interplay arising from multifrequency mixing of the plasmonic
in terms of the real-valued field enhancement factor f, which fields within the broadband laser pulse, however, complicates
denotes the ratio between the local and the incident electrical the prediction and optimization of the observed signal.
fields f = Elocal/Einc.. This field enhancement provides the basis Therefore, iterative or evolutionary optimization schemes
for extremely sensitive applications, such as surface-enhanced have often been employed to retrieve the phase dependence
of the nonlinear signal formation and to obtain optimized
fluorescence3 and surface-enhanced Raman scattering.2
phase profiles.7,10−13,15
Plasmonic field enhancement is particularly interesting for
Originally developed for transparent nonlinear crystals,
nonlinear spectroscopy because of the higher-order scaling of
Miller’s rule provides a simple way to predict the nonlinear
the signal enhancement ∝ f 2n, with n being the number of
susceptibility χ(n) of materials from the product of their linear
involved fields.4−6 As an example, coherent anti-Stokes Raman
scattering, a four-wave mixing (FWM) process involving a
phonon or vibrational resonance, is known to scale with f 8.5 Received: September 1, 2022
For ultrashort laser pulses, on the other hand, the response
of plasmonic systems has been shown to become sensitive to
the spectral phase profile of the excitation pulse.7 While
optimum efficiencies of nonlinear phenomena are usually
obtained for shortest input pulses and thus flat spectral phase
© XXXX The Authors. Published by
American Chemical Society https://doi.org/10.1021/acsphotonics.2c01362
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susceptibilities χ(1) at the fundamental frequencies.16,17 Miller’s
rule has been shown to be applicable also to plasmonic systems
in which the shape of the field distributions at the fundamental
and the nonlinear frequencies are unchanged. Otherwise, mode
matching at the different frequencies needs to be consid-
ered.17−19 To date, Miller’s rule has been mainly applied to
experiments with laser pulses with moderate spectral widths
and temporal durations typically larger than 100 fs.
Here, we first show that Miller’s rule holds also in the case of
ultra-broadband laser pulses, that is, pulses that are
substantially shorter than the dephasing time of the LSPR,
and hence, their linewidth substantially exceeds the LSPR
damping rate. More specifically, we show that the linear
susceptibility obtained from dark-field scattering (DFS) spectra
can be used to predict the dependence of the near-degenerate
FWM (ND-FWM) signal on the position of the nanoantenna’s
resonance energy with respect to the central energy of the laser
pulse. This allows us to deterministically control the ND-FWM
signal formation by chirping the pulse and to further enhance
the resulting intensity by up to 60% with respect to that
observed for the shortest input pulse. Finally, we exploit the
observed phase dependence for confocal phase contrast
imaging of individual nanoantennas.
■ RESULTS AND DISCUSSION
Well-defined plasmonic nanoantennas needed for the
quantitative study of the nonlinear signal enhancement were
fabricated using DNA origami as described in the Methods
section. This approach allowed us to precisely control the
dimer gap and the linear arrangement by the DNA framework
and provided gold nanorod dimers with a single longitudinal
plasmon resonance in the investigated spectral range and
reproducible field enhancement as we will show below. After
deposition on a cleaned glass slide, optical images were
captured for detecting the anti-Stokes ND-FWM signal (Figure
1a) and the DFS response (Figure 1b) on the scanning
confocal optical microscope as shown in Figure 1c. Both
images were recorded for the same sample area and exhibit
bright and well-separated spots. For each spot in the ND-FWM
image, a corresponding match can be seen in the DFS image.
This colocalization together with additional scanning electron
microscopy (SEM) measurements (example in Figure 2c)
proves individual nanorod dimers as the sources of the signals.
The smaller width of the ND-FWM spots results from the
nonlinear origin of the signal and the higher numerical
aperture used in this experiment (see the Methods section).
The ND-FWM signal formation process is shown in Figure 1d.
Intrapulse frequency mixing within the broadband laser
spectrum covering the spectral range from 1.355 to 1.734 eV
(gray area) strongly broadens the ωFWM signal (green dashed
line). The generated ND-FWM signal can be detected as either
Stokes or anti-Stokes radiation (green areas) using long- or
short-pass filters, respectively.
The ND-FWM signal intensities detected for individual
nanoantennas are a measure of the efficiency of the involved
nonlinear plasmonic process. We retrieved these values from
the confocal scans giving the initial ND-FWM intensities I0 for
a bandwidth-limited pulse. To quantitatively analyze the ND-
FWM intensities, we considered the orientation of the nanorod
dimers with respect to the excitation polarization. To this end,
ND-FWM radiation patterns for every nanoantenna were
recorded using back focal plane imaging, and an example is
shown in Figure 2a. The radiation patterns exhibit the
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Figure 1. (a,b) Scanning confocal images of gold nanorod dimer
nanoantennas on glass detecting ND-FWM (a) and DFS (b),
respectively. Inset: Detailed ND-FWM scan of a single nanoantenna.
(c) Schematic of the laser scanning confocal microscope setup
comprising a 4f pulse shaper to control the spectral phase profile of
broadband pulses from a Ti/Sa laser. (d) Scheme illustrating the ND-
FWM process: Three input photons taken from the laser spectrum
(gray area) ω1 (blue arrow), ω2 (yellow arrow), and ω3 (red arrow)
mix to create the ND-FWM photon ωFWM (green arrow). The total
generated ND-FWM spectrum is shown as dashed green line. The
detectable ND-FWM contributions on the Stokes and anti-Stokes side
of the laser spectrum are highlighted in green. The image in (a)
reflects anti-Stokes ND-FWM. The energies of the involved photons
represented by the arrows are given in the same color as the
corresponding lines in the spectrum.
characteristic point-dipole behavior consisting of two bright
lobes for angles exceeding the critical angle of the glass−air
interface (kx2/k 02 + k y2/k 02 1).17,20 The orientation of the
radiating dipole (dashed black line in Figure 2b) is
perpendicular to the lobes obtained by integration over high
numerical aperture (NA) values (NA>1, dashed blue line in
Figure 2b) and can be determined using a sin2 fit (solid red
line). SEM images taken for all dimers, an example is shown in
Figure 2c, confirm that the determined dipole orientation
matches the long axis of the nanorod dimers as expected since
our excitation spectrum coincides with the low-energy
longitudinal mode.21 The derived angle θ between each
nanoantenna and the excitation polarization allows scaling of
the ND-FWM intensities by cos6θ due to the cubic intensity
dependency of the ND-FWM process.22,23 As a result, the
scaled ND-FWM intensities I0 serve as orientation-independ-
ent values that allow us to compare the nonlinear plasmonic
response from different nanoantennas.
The prediction of the nonlinear ND-FWM signal using
Miller’s rule signal requires knowledge of the linear
susceptibility which we obtained from DFS spectra. For all
plasmonic nanoantennas, DFS spectra were measured,
exhibiting a single resonance in most cases due to the highly
reproducible linking of the nanorods achieved by DNA
origami. Three typical examples are reproduced in Figure 2d.
Plasmonic structures with more complex spectra were excluded
from the following study. The recorded spectral data are
divided by the ω4 dependence of the Rayleigh scattering
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Figure 2. (a) ND-FWM radiation pattern detected for the bottom
nanoantenna of (d) showing a characteristic single-dipole radiation
pattern. (b) Polar plot of the angular intensity distribution summed
over high NA values of the radiation pattern in (a) (dashed blue line)
and a sin2 fit (red line). The dashed black line perpendicular to the
observed radiation pattern indicates the dipole orientation along the
long axis of the nanorod dimer. (c) SEM image of the same nanorod
dimer confirming the dimer orientation obtained from the ND-FWM
radiation pattern. (d) Representative dark-field spectra measured on
three different gold nanorod dimer nanoantennas. The spectra were
fitted using a single Lorentzian function. (e) Scaled ND-FWM
intensities I0 of different nanoantennas (black triangles) plotted with
respect to their plasmon resonances retrieved from DFS spectra. The
obtained ND-FWM intensities are scaled for their in-plane
orientations with respect to the excitation polarization. The three
nanoantennas from (d) are highlighted using the corresponding
colors. The calculated curves without (solid blue line) and with the
field enhancement correction term (red dashed line) are shown as
lines.
probability to reflect the actual near-field amplitude present at
the nanoantenna.24 This allows us to connect the experimental
spectra to the theoretical model for a single resonant dipole
presented below. The scaled spectra are fitted with a single
Lorentzian function (black line), yielding resonance energies
ranging from 1.53 to 1.80 eV and a mean full-width at half-
maximum (FWHM) of 0.1 eV. The observed variations result
from small differences in the geometry and gap size of the
dimer25−27 and the length as well as the aspect ratio of the
monomers.21,27,28 In the present study, this distribution is
desired because it allows us to investigate the dependence of
the ND-FWM signal on the resonance energy with respect to
the laser spectrum.
In the following, we describe a quantitative model based on
Miller’s rule that uses the linear susceptibility of the resonant
fundamental plasmonic mode observed in the DFS measure-
ment to predict the nonlinear ND-FWM intensities. First, we
introduce the general equation used to calculate the total ND-
FWM signal intensity14,16,29
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max
(3)
IFWM( FWM ) ( FWM ; 1, 2, 3)
min
Einc( 1)Einc( *
2)Einc( 3)
2
( FWM 1 2 + 3)d 1d 2 d 3|
χ(3) is the third-order nonlinear susceptibility, E(ωn) is the
complex electric field at the given radial frequency ωn in the
used excitation spectrum, and E*(ωn) is its complex conjugate.
The two fields for ω1 and ω2 represent the two incoming fields,
whereas the complex conjugated electric field of ω3 and the
generated ωFWM field represent the two outgoing fields as
shown in Figure 1d. δ(···) ensures energy conservation in this
parametric process.29 The limits of the variables ωn in the triple
integral are given by the minimum ωmin and maximum ωmax
excitation laser frequencies. Following Miller’s rule,6,16 the
third-order susceptibility χ(3) can be approximated as the
product of the linear susceptibilities χ(1) of the involved
frequencies: χ(3)(ωFWM; ω1, ω2, ω3) ∝ χ(1)(ωFWM)χ(1)(ω1)-
χ(1)(ω2)χ(1)(ω3). In this approximation, the intrinsic non-
resonant third-order susceptibility of gold χ(3)
Au is considered to
be a frequency-independent constant and is hence neglected in
the following discussion.6,30,31 We express each complex linear
susceptibility χ(1)(ω) as the product of the plasmon resonance
term with resonance frequency ω0 and damping γ and the
linear bulk susceptibility of gold derived from Johnson et
al.:16,32 (1) ( ) (1)
. χ(1)(ω) can be understood as
0 i Au
being proportional to a complex field enhancement factor f(ω)
describing the local field at the plasmonic particle by Elocal(ω)
= f(ω)Einc(ω). Because the near-field distribution of nano-
antennas is strongly heterogeneous, f(ω) is a local quantity
such that the experimentally observed signal enhancement will
represent a spatial average corresponding to spatial integration
of the equation for the total ND-FWM intensity. In fact, the
given equation for the total ND-FWM intensity only holds in
the case of plasmon modes with similar spatial distributions at
the involved frequencies. Otherwise, spatial mode matching
would need to be considered.17−19 In our work, all involved
frequencies are located within the fundamental longitudinal
mode of the plasmonic structure and thus share the same
spatial distribution, enabling this approximation for broadband
excitation.
Using these equations, the ND-FWM intensity can be
calculated as a function of the plasmon resonance energy and
an applied spectral phase profile. The present model requires
the measured laser spectrum, the plasmon resonance energy,
and the damping as the only input parameters. For the latter
two, the experimentally observed values with plasmon
resonance energies ranging from 1.3 to 1.9 eV and a damping
of 50 meV were used. The damping was derived from the
FWHM of the plasmon resonance obtained from the
Lorentzian fits in the DFS spectra γ = FWHM/2.16
In Figure 2e, the results obtained from the calculation are
plotted as the blue line against the plasmon resonance energy
of the respective nanoantenna together with the scaled
plasmon-enhanced ND-FWM intensities I0 obtained from the
experiments (black triangles). The three example dimers from
Figure 2d are highlighted in the plot using the same colors as
in the corresponding DFS spectra.
The calculated curve matches the experimental data points
very well, both peaking at ∼1.6 eV. The peak energy is shifted
by 60 meV toward higher plasmon resonance energies with
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respect to the central laser energy. This results from the
plasmon enhancement of the emitted FWM photon detected
on the anti-Stokes side of the laser spectrum. For detecting the
Stokes ND-FWM signal, on the other hand, the maximum of I0
is observed for a red-shifted resonance energy (see Figure S6 of
the Supporting Information). For larger plasmon resonance
energies, the predicted ND-FWM intensities are higher than
those observed in the experiment. This deviation is attributed
to small variations in the monomer and dimer geo-
metries21,25−28 affecting the magnitude of the field enhance-
ment for smaller nanoantennas and larger gap sizes. Therefore,
we introduced a correction factor derived from the observed
DFS intensities (see Figure S7 of the Supporting Information).
The resulting curve, shown as a red dashed line in Figure 2e,
shows a significantly improved match with the experimental
data. A larger data set including a second measurement without
associated SEM images confirms this observation (see Figure
S8 of the Supporting Information). The good agreement
between the parameter-free model calculations and the
experimental intensities verifies the applicability of Miller’s
rule to predict higher-order plasmonic responses such as ND-
FWM by their linear susceptibility for broadband laser pulses.
Having established the resonance energy dependence of the
plasmon-enhanced ND-FWM intensity, we can now focus on
the influence of the spectral phase in the presence of a spectral
resonance. To this end, we systematically varied the group
delay dispersion (GDD) of the excitation pulses while
recording the ND-FWM signal for each dimer nanoantenna.
These GDD or “chirp” scans turn out to be simple and fast
phase-sensitive measurements that are very well suited for
reflecting the main contributions to the plasmonic phase
response. The phase ϕGDD induced by a certain GDD value is
2
GDD
( ) = GDD ·( laser0) /2 and is imprinted onto the
compressed laser pulse for every frequency component ω with
respect to the central excitation laser frequency laser0 using the
4f pulse shaper.33 Adding phase ϕGDD increases the pulse
duration and therefore decreases the peak electric field in the
focal spot while keeping the time integrated intensity constant.
For every nanorod dimer, the GDD value was scanned, and
typical measurements are shown in Figure 3a normalized to
their respective peak intensities for comparison. We used
single-layer graphene as a reference material as it provides a
strong ND-FWM signal.23,34 As a side note, the ND-FWM
intensities of resonant dimer nanoantennas were found to be
about 3 orders of magnitude higher than those of graphene
under the same experimental conditions. This indicates their
potential for nonlinear applications especially in the context of
local sensing. The GDD scan for single-layer graphene (black
dashed line) exhibits a symmetric bell-shaped peak centered
around 0, as expected for a bandwidth-limited pulse.23 The
GDD scans of the nanoantennas shown in Figure 2d feature
similar shaped curves containing the previously reported initial
ND-FWM intensity I0 for the unchirped pulse (GDD = 0). For
most nanoantennas, however, the maximum of the GDD scans
does not coincide with I0 but is shifted along the x-axis. These
shifts reach values below −30 fs2, as seen for the purple curve,
and can yield significantly increased ND-FWM intensities Imax.
This means that the highest ND-FWM intensities are not
observed for the shortest input pulse in these cases. For
comparison, adding a GDD of −30 fs2 corresponds to
propagating the pulse through ∼0.7 mm of N-BK7 glass.35
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Figure 3. (a) Normalized ND-FWM GDD scans of the three
nanoantennas from Figure 2d shown as solid-colored lines. The
dashed black line is the reference measurement of ND-FWM detected
from graphene. I0 is the ND-FWM intensity for the unchirped
excitation pulse and Imax is the maximum intensity observed at the
respective GDDImax for each nanoantenna. (b) Obtained GDDImax for
all nanoantennas plotted with respect to their plasmon resonance
energy. (c) Enhancement in Imax/I0 observed in the chirp scan
measurements as a function of plasmon resonance energy. The three
nanoantennas shown in Figure 2d are highlighted in (b,c) with the
same colors as before. The solid blue lines in (b,c) are the numerical
curves obtained from our quantitative model.
To systematically investigate the influence of the spectral
phase, the optimum GDD GDDI max and the maximum ND-
FWM intensity Imax are extracted from the GDD scans of all
nanoantennas. In Figure 3b, the obtained GDDI max values are
plotted with respect to the corresponding plasmon resonance
energies together with the calculation results from our
quantitative model for the corresponding input fields. The
experimental data and the theoretical curve match very well,
both showing a minimum at 1.65 eV. The calculated curve
predicts an additional maximum at ∼1.44 eV outside the range
of the plasmon resonances observed in the present experi-
ments. The ratio of Imax versus I0 is used to quantify the
additional enhancements achieved in the GDD scans (Figure
3c) and is seen to reach up to 60% for nanoantennas resonant
at 1.65 eV.
The achievable ND-FWM enhancement together with its
spectral and GDD dependence can be understood from the
equation for the total ND-FWM intensity. In principle, by
applying an appropriate spectral phase to the excitation pulse
field Einc(ω), the phase of the plasmonic response χ(1) (ω) can
be compensated, leading to local pulse compression and
maximized field enhancement.9 For the single resonant
nanoantennas studied here, the spectral phase resembles a π-
(
step at the resonance energy arc tan ( 0
)). A quadratic
GDD phase ϕGDD can partially compensate for this plasmonic
phase, thereby restoring constructive interference depending,
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however, on the position of the plasmonic resonance (see also
Figure S9 of the Supporting Information). For resonances on
opposite sides of the central laser energy, the phase can be
compensated for by GDD with an opposite sign, leading to the
two peaks found in Figure 3c and the sign reversal in Figure
3b. When the plasmon resonance energy coincides with the
central laser frequency, however, no additional enhancement
can be achieved. A perfect phase compensation and local pulse
compression could, in principle, be achieved using the inverted
plasmon resonance phase, leading to the cancellation of all
phase contributions in the integral. Surprisingly, this is
predicted to yield only a minor improvement of about 6% as
compared to that of a simple quadratic profile (see Figure S10
of the Supporting Information). At the same time, the
experimental realization would require a pulse shaper and
the optimization of two parameters (ω0 and γ) versus the
single chirped value which can be achieved by simply varying
the amount of glass in the optical beam path.
Finally, we show that the observed chirp dependence can be
exploited for phase-selective confocal imaging. Phase-contrast
images are obtained by recording confocal scans for different
ϕGDD phases and taking their difference (see the Supporting
Information for details). Figure 4 shows a phase-contrast image
Figure 4. Confocal phase-contrast image showing the phase
dependency of the ND-FWM signal from two Au-nanorod dimers
with different plasmon resonance energies. The inset shows the ND-
FWM signal intensities for the two dimers obtained from confocal
images recorded with different ϕGDD phases.
derived by switching from an applied GDD of −12 fs2 to 8 fs.2
While the ND-FWM intensity of dimer 1 increases by 4%, the
signal intensity seen for dimer 2 drops by about 19%. The
phase-contrast images not only illustrate the induced changes
in the achieved near-field intensity at the nanoantenna but also
allow retrieving of traces similar to those of the GDD scans
shown in Figure 3a. This is achieved by summation of the
signal for each dimer spot and each confocal image for a given
GDD value, shown as inset in Figure 4. The obtained chirp-
dependent traces would enable the retrieval of the plasmon
resonance energy for all antennas included in the confocal
scans.
In conclusion, we investigated the nonlinear response of
nanorod dimer antennas to ultrafast broadband laser pulses.
First, we established the correlation between the ND-FWM
intensity and the plasmon resonance energy of the nanorod
dimer antennas. In the next step, we determined the phase
dependence of the ND-FWM intensity. Applying a quadratic
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Article
phase profile enhances the ND-FWM signal by up to 60%
depending on the resonance energy of the nanoantenna. All
experimental data are in good agreement with model
predictions based on Miller’s rule, which only requires the
linear susceptibility of the nanoantennas and the laser
spectrum as input parameters. This model accurately predicts
the chirp dependence as well as the magnitude of the
achievable enhancement of the ND-FWM intensity. In
addition, we show that the explicit phase dependence of the
ND-FWM process enables phase contrast imaging providing, a
fast method to gain information on the properties of the
plasmonic nanoantennas. The presented model description is
very general and not limited to plasmonic resonances and
could thus be utilized to enhance the nonlinear response of
other resonant systems.
■ METHODS
Phase Shaping Microscope. The ND-FWN measure-
ments were performed on the scanning confocal optical
microscope shown in Figure 1c. A fs-pulsed Ti/Sa laser
(Venteon Pulse One; 80 MHz repetition rate) with a
bandwidth restricted from 1.355 to 1.734 eV (from 915 nm
to 715 nm) and a central laser frequency of 1.54 eV (805 nm)
was used for excitation. Phase control of the excitation pulses
was provided using a home-built 4f pulse shaper unit including
a liquid-crystal modulator (JENOPTIK SLM-S640D). Bandwidth-
limited pulses were achieved by local pulse compression using
iterative multiphoton intrapulse interference phase scans
detecting the second harmonic generation of iron(III) iodate
nanoparticles,36 followed by signal optimization of the ND-
FWM intensity of graphene with the help of a generic
algorithm.23 The laser was focused onto the sample using the
NA adjustable microscope objective set to the maximum NA of
1.3. The sample response was detected using the same
objective (epi-configuration), and short-pass filters in the
detection beam path were used to limit the recorded signal to
anti-Stokes ND-FWM (ωdet < 1.77 eV). Confocal images were
recorded using a single-photon avalanche photodiode (Laser
Components Count 100C) while scanning the sample.
Radiation patterns (BFP images) were measured using a
charge-coupled device (CCD) camera (Andor iDus 401 BR-
DD) placed in a conjugate plane of the back focal plane of the
microscope objective. Spectra were measured using a
spectrometer (Acton SpectraPro 2500i) equipped with a
CCD camera (Andor iDus 401 BR-DD). The detection
sensitivity of the overall setup was determined by recording the
emission of a calibrated thermal light source and was used to
correct all spectral data.
Sample Preparation. The synthesis and dimer formation
were achieved by DNA origami. Au-nanorods (AuNR) with a
size of 63.5 nm × 24.0 nm (see Figure S1 in the Supporting
Information) were synthesized using a modified wet chemical
procedure based on the study of Ming et al.37 The detailed
procedure is given in the Supporting Information. In the next
step, caDNAno software38,39 was used to design a DNA
origami structure based on a long 14 helix bundle framework
providing two binding sites for AuNRs in a tip-to-tip fashion as
shown in Figure S2a in the Supporting Information.
Assembling both structures and subsequent purification
yielded well-defined AuNR dimers as seen in the transmission
electron microscopy images shown in Figure S2d with an
average gap size of 9.2 ± 2.0 nm (Figure S2e in the Supporting
Information). This approach allows precise control of the
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dimer gap while maintaining the predetermined linear
arrangement of the DNA origami. This provides dimers with
a single longitudinal plasmonic resonance and reproducible
field enhancement in the gap.
Before deposition, the surface of microscope coverslips with
a size of 24 mm × 60 mm and a thickness of 170 μm (Carl
Roth GmbH, Germany) was thoroughly cleaned. In the first
step, glass slides were sonicated in Hellmanex III (Sigma-
Aldrich), acetone, isopropanol, and Milli-Q water for 15 min
each. Afterward, glass slides were exposed for oxygen plasma (5
min) to ensure hydrophilicity of the surface. The deposition
was carried out by dropping 50 μL of Au-dimers on the surface
and letting them to bind for 1 min. Finally, the surface was
rinsed two times with distilled water and blow-dried with
nitrogen.
■ ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsphotonics.2c01362.
Experimental details with sample preparation, electron
microscopy and DFS measurements, optical reference
measurements, ND-FWM spectra, Stokes ND-FWM
numerical calculations, field-enhancement correction
term, extended dataset, phase compensation by the
GDD phase, π-step calculation, and details of the phase-
sensitive imaging (PDF)
■ AUTHOR INFORMATION
Corresponding Author
Achim Hartschuh − Department of Chemistry, LMU Munich,
81377 Munich, Germany; Center for Nanoscience (CeNS),
LMU Munich, 80799 Munich, Germany; orcid.org/
0000-0002-0518-6559; Email: achim.hartschuh@lmu.de
Authors
Veit Giegold − Department of Chemistry, LMU Munich,
81377 Munich, Germany; Center for Nanoscience (CeNS),
LMU Munich, 80799 Munich, Germany
Karol Koła̧taj − Department of Physics, LMU Munich, 80539
Munich, Germany; Center for Nanoscience (CeNS), LMU
Munich, 80799 Munich, Germany; Present
Address: Département de Physique - Photonic
Nanosystems, Université de Fribourg - Faculté des
Sciences et Médicine, Chemin de Musée 3, CH-1700
Fribourg, Switzerland
Tim Liedl − Department of Physics, LMU Munich, 80539
Munich, Germany; Center for Nanoscience (CeNS), LMU
Munich, 80799 Munich, Germany; orcid.org/0000-0002-
0040-0173
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsphotonics.2c01362
Funding
We acknowledge financial support from the Deutsche
Forschungsgemeinschaft (DFG) through the Excellence
Cluster e-conversion (EXC 2089/1-390776260) and
HA4405/8 and from Horizon 2020. K.K. received funding
from the European Union’s Horizon 2020 research and
innovation program under the Marie Skłodowska-Curie grant
agreement no. 765703. T.L. received funding through the ERC
Consolidator Grant 818635 DNA Funs.
F https://doi.org/10.1021/acsphotonics.2c01362
Article
Notes
The authors declare no competing financial interest.
■ REFERENCES
(1) Maier, S. A.Plasmonics: Fundamentals and Applications; Springer:
New York, 2007.
(2) Radziuk, D.; Moehwald, H. Prospects for plasmonic hot spots in
single molecule SERS towards the chemical imaging of live cells. Phys.
Chem. Chem. Phys. 2015, 17, 21072−21093.
(3) Sultangaziyev, A.; Bukasov, R. Review: Applications of surface-
enhanced fluorescence (SEF) spectroscopy in bio-detection and
biosensing. Sens. Bio-Sens. Res. 2020, 30, 100382.
(4) Li, S.; Li, Y.; Yi, R.; Liu, L.; Qu, J. Coherent anti-Stokes Raman
scattering microscopy and its applications. Front. Phys. 2020, 8,
598420.
(5) Fast, A.; Potma, E. O. Coherent Raman scattering with
plasmonic antennas. Nanophotonics 2019, 8, 991−1021.
(6) Obermeier, J.; Schumacher, T.; Lippitz, M. Nonlinear spectros-
copy of plasmonic nanoparticles. Adv. Phys.: X 2018, 3, 1454341.
(7) Accanto, N.; Piatkowski, L.; Renger, J.; van Hulst, N. F.
Capturing the optical phase response of nanoantennas by coherent
second-harmonic microscopy. Nano Lett. 2014, 14, 4078−4082.
(8) Piatkowski, L.; Accanto, N.; van Hulst, N. F. Ultrafast Meets
Ultrasmall: Controlling Nanoantennas and Molecules. ACS Photonics
2016, 3, 1401−1414.
(9) Brixner, T.; García de Abajo, F. G.; Spindler, J.; Pfeiffer, C.;
Pfeiffer, W. Ultrafast adaptive optical near-field control. Phys. Rev. B
2006, 73, 125437.
(10) Accanto, N.; Nieder, J. B.; Piatkowski, L.; Castro-Lopez, M.;
Pastorelli, F.; Brinks, D.; van Hulst, N. F. Phase control of
femtosecond pulses on the nanoscale using second harmonic
nanoparticles. Light Sci. Appl. 2014, 3, No. e143.
(11) Aeschlimann, M.; Bauer, M.; Bayer, D.; Brixner, T.; Cunovic,
S.; Fischer, A.; Melchior, P.; Pfeiffer, W.; Rohmer, M.; Schneider, C.;
Strüber, C.; Tuchscherer, P.; Voronine, D. V. Optimal open-loop
near-field control of plasmonic nanostructures. New J. Phys. 2012, 14,
033030.
(12) Aeschlimann, M.; Brixner, T.; Fischer, A.; Hensen, M.; Huber,
B.; Kilbane, D.; Kramer, C.; Pfeiffer, W.; Piecuch, M.; Thielen, P.
Determination of local optical response functions of nanostructures
with increasing complexity by using single and coupled Lorentzian
oscillator models. Appl. Phys. B 2016, 122, 119.
(13) Brinks, D.; Castro-Lopez, M.; Hildner, R.; van Hulst, N. F.
Plasmonic antennas as design elements for coherent ultrafast
nanophotonics. Proc. Natl. Acad. Sci. U.S.A. 2013, 110, 18386−18390.
(14) Kravtsov, V.; Ulbricht, R.; Atkin, J. M.; Raschke, M. B.
Plasmonic nanofocused four-wave mixing for femtosecond near-field
imaging. Nat. Nanotechnol. 2016, 11, 459−464.
(15) Comin, A.; Hartschuh, A. Efficient optimization of SHG
hotspot switching in plasmonic nanoantennas using phase-shaped
laser pulses controlled by neural networks. Opt. Express 2018, 26,
33678.
(16) Boyd, R. W.Nonlinear Optics, 3rd ed.; Elsevier: Amsterdam,
2008.
(17) Wolf, D.; Schumacher, T.; Lippitz, M. Shaping the nonlinear
near field. Nat. Commun. 2016, 7, 10361.
(18) O’Brien, K.; Suchowski, H.; Rho, J.; Salandrino, A.; Kante, B.;
Yin, X.; Zhang, X. Predicting nonlinear properties of metamaterials
from the linear response. Nat. Mater. 2015, 14, 379−383.
(19) Metzger, B.; Schumacher, T.; Hentschel, M.; Lippitz, M.;
Giessen, H. Third Harmonic Mechanism in Complex Plasmonic Fano
Structures. ACS Photonics 2014, 1, 471−476.
(20) Lieb, M. A.; Zavislan, J. M.; Novotny, L. Single-molecule
orientations determined by direct emission pattern imaging. J. Opt.
Soc. Am. B 2004, 21, 1210.
(21) Shao, L.; Woo, K. C.; Chen, H.; Jin, Z.; Wang, J.; Lin, H.-Q.
Angle- and energy-resolved plasmon coupling in gold nanorod dimers.
ACS Nano 2010, 4, 3053−3062.
ACS Photonics XXXX, XXX, XXX−XXX
ACS Photonics pubs.acs.org/journal/apchd5 Article

(22) Kumar, J.; Wei, X.; Barrow, S.; Funston, A. M.; Thomas, K. G.;
Mulvaney, P. Surface plasmon coupling in end-to-end linked gold
nanorod dimers and trimers. Phys. Chem. Chem. Phys. 2013, 15,
4258−4264.
(23) Ciesielski, R.; Comin, A.; Handloser, M.; Donkers, K.; Piredda,
G.; Lombardo, A.; Ferrari, A. C.; Hartschuh, A. Graphene Near-
Degenerate Four-Wave Mixing for Phase Characterization of
Broadband Pulses in Ultrafast Microscopy. Nano Lett. 2015, 15,
4968−4972.
(24) Menzel, C.; Hebestreit, E.; Mühlig, S.; Rockstuhl, C.; Burger,
S.; Lederer, F.; Pertsch, T. The spectral shift between near- and far-
field resonances of optical nano-antennas. Opt. Express 2014, 22,
9971−9982.
(25) Jain, P. K.; Eustis, S.; El-Sayed, M. A. Plasmon coupling in
nanorod assemblies: optical absorption, discrete dipole approximation
simulation, and exciton-coupling model. J. Phys. Chem. B 2006, 110,
18243−18253.
(26) Danckwerts, M.; Novotny, L. Optical frequency mixing at
coupled gold nanoparticles. Phys. Rev. Lett. 2007, 98, 026104.
(27) Funston, A. M.; Novo, C.; Davis, T. J.; Mulvaney, P. Plasmon
coupling of gold nanorods at short distances and in different
geometries. Nano Lett. 2009, 9, 1651−1658.
(28) Tsung, C.-K.; Kou, X.; Shi, Q.; Zhang, J.; Yeung, M. H.; Wang,
J.; Stucky, G. D. Selective shortening of single-crystalline gold
nanorods by mild oxidation. J. Am. Chem. Soc. 2006, 128, 5352−5353.
(29) Min, W.; Lu, S.; Rueckel, M.; Holtom, G. R.; Xie, X. S. Near-
degenerate four-wave-mixing microscopy. Nano Lett. 2009, 9, 2423−
2426.
(30) Boyd, R. W.; Shi, Z.; De Leon, I. The third-order nonlinear
optical susceptibility of gold. Opt. Commun. 2014, 326, 74−79.
(31) Knittel, V.; Fischer, M. P.; Vennekel, M.; Rybka, T.;
Leitenstorfer, A.; Brida, D. Dispersion of the nonlinear susceptibility
in gold nanoantennas. Phys. Rev. B 2017, 96, 125428.
(32) Johnson, P. B.; Christy, R. W. Optical Constants of the Noble
Metals. Phys. Rev. B 1972, 6, 4370−4379.
(33) Monmayrant, A.; Weber, S.; Chatel, B. A newcomer’s guide to
ultrashort pulse shaping and characterization. J. Phys., B 2010, 43,
103001.
(34) Hendry, E.; Hale, P. J.; Moger, J.; Savchenko, A. K.; Mikhailov,
S. A. Coherent nonlinear optical response of graphene. Phys. Rev. Lett.
2010, 105, 097401.
(35) SCHOTT AG, Datasheet N-BK7. https://www.schott.com/
shop/advanced-optics/de/Optisches-Glas/SCHOTT-N-BK7/c/
glass-SCHOTT%20N-BK7%C2%AE, (accessed on Feb 15, 2022).
(36) Lozovoy, V. V.; Pastirk, I.; Dantus, M. Multiphoton intrapulse
interference IV Ultrashort laser pulse spectral phase characterization
and compensation. Opt. Lett. 2004, 29, 775−777.
(37) Ming, T.; Feng, W.; Tang, Q.; Wang, F.; Sun, L.; Wang, J.; Yan,
C. Growth of tetrahexahedral gold nanocrystals with high-index facets.
J. Am. Chem. Soc. 2009, 131, 16350−16351.
(38) Hong, F.; Zhang, F.; Liu, Y.; Yan, H. DNA Origami: Scaffolds
for Creating Higher Order Structures. Chem. Rev. 2017, 117, 12584−
12640.
(39) Douglas, S. M.; Marblestone, A. H.; Teerapittayanon, S.;
Vazquez, A.; Church, G. M.; Shih, W. M. Rapid prototyping of 3D
DNA-origami shapes with caDNAno. Nucleic Acids Res. 2009, 37,
5001−5006.

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