FTu4E.2.

pdf CLEO 2018 © OSA 2018

Nonlinear and Quantum-Light Scattering from Gold

Nanorods
Theodore B. Norrisa, Benjamin Girodiasa, Miao-Bin Liena, Ji-Young Kimb, Zhen Xua, Heather Georgea, You-
Chia Changa, Myung-Geun Hanc, Yimei Zhuc, John C. Schotlandd, Nicholas A. Kotovb, Mackillo Kiraa
a
Department of Electrical Engineering, University of Michigan, Ann Arbor, MI 48109, USA
b
Department of Materials Science and Engineering, University of Michigan, Ann Arbor, MI 48109, USA
c
Condensed Matter Physics and Materials Sciences Department, Brookhaven National Laboratory, Upton, NY 11973, USA
d
Department of Mathematics, University of Michigan, Ann Arbor, Ann Arbor, MI 48109, USA

Abstract: We study the spectral dependence of the scattered light from Au nanorods illuminated
by 50-fs pulses resonant with the longitudinal plasmon, and determine the origin of the scattering
in terms of the plasmon modes. We project the expected spectrum under illumination from a
squeezed optical pump. ©2018TheAut hor(
s)

OCIS codes: (190.4720, 290.5850, 270.6570)

1. Introduction
Metallic nanoparticles exhibiting plasmonic resonances have been widely investigated for many applications such as
biosensing, as well as for their fundamental interest in light–matter interactions. Asymmetric structures such as
chemically synthesized or self-organized Au nanorods (AuNRs) exhibit two resonances, corresponding to
longitudinal and transverse plasmon modes. Interestingly, nanoscale imaging of the plasmon modes has shown the
mode amplitudes to generally be asymmetric, despite the essentially perfect structural uniformity and symmetry of
crystalline AuNRs [1]. It has generally been assumed that the optical and electronic properties reflect the same
symmetry. We have recently applied a suite of experimental techniques, most notably state-of-the-art electron
holography in a TEM, for a detailed characterization of AuNRs. Our results show that AuNRs with perfect structural
symmetry nevertheless almost always are electrically asymmetric, producing a static dipole moment [2]. This
discovery has highly significant consequences for the optical response; by removing the inversion symmetry, the
second order optical response becomes dominant in the nonlinear scattering of light. In this paper, we discuss how
the charge asymmetry quantitatively explains all the features of the scattering of ultrashort pulses from AuNRs,
resolving several previously unanswered questions regarding the origin of nonlinear “photoluminescence” from
metallic nanostructures [3]. Based on the results employing excitation by classical light fields, we then utilize
recently developed theoretical techniques in quantum spectroscopy to project the expected behavior of scattering
under excitation by a quantum light source [4,5,6].
2. Nonlinear light scattering.
We have performed a detailed and comprehensive study of the nonlinear light scattering from AuNRs designed so
that the excitation wavelength is resonant with the longitudinal surface plasmon mode at 800 nm. 50-fs pulses from
a Ti:sapphire laser are incident on a dilute solution of AuNRs in water, and the scattered light spectrum (Fig. 1)

Fig. 1: Spectrum of scattered light from dilute AuNR
solution under 800-nm, 50-fs excitation.
Fig. 2: Data points are the experimentally measured
intensity scaling of the nonlinear signal vs wavelength.
The line is the scaling predicted from a fluctuation-
dissipation model of scattering from second-order
plasmon modes including hot electron effects.
 FTu4E.2.pdf CLEO 2018 © OSA 2018

is measured at 90 degrees direction from the incident beam. Both second and third harmonic hyper-Rayleigh
scattering signals are measured, as well as a broad-band component that has been attributed in the literature to
multiphoton luminescence involving d-band holes.
The observed scaling of the second and third harmonic signals with excitation power is found to not follow the
expected quadratic and cubic behavior, but exhibits unexpected scaling that can be quantitatively understood in a
Fermi liquid model as plasmon damping via hot electrons. Through detailed studies of the spectral dependence of
the scaling across the broadband feature (Fig. 2), we show that multiphoton “luminescence” in fact arises from
second order light scattering from the free electrons enabled by the broken symmetry, and is not in fact
luminescence dependent on the band structure. The spectra and the spectral dependence of the intensity scaling of
both the “luminescence” and the 2w and 3w signals are self-consistently and quantitatively understood though a
Fermi liquid model.
3. Quantum spectroscopy theory of light scattering
Quantum spectroscopy [4,5,6] enhances many-body interactions by using quantum light sources with distinct photon
correlations that directly excite correlated clusters in a many-body system. As demonstrated by the discovery of
dropletons [6], quantum spectroscopy reveals futher insights into a nonlinear system that may have been obscured in
coherent laser spectroscopy. We apply a robust scheme [5] to numerically project measurements in Fig. 1 to desired
quantum responses.
Fig. 3 shows the projected differential counts between 2-photon correlated Schrödinger cat state and a classical
pump. We observe that the quantum differentials shift the broad peak toward the second harmonic peak (Fig. 3). As
the pump intensity is increased, the narrow peak becomes reduced unlike the broad peak, which identifies the
different physical origin of the narrow and broad peak. This trend is particularly clear in the relative counts shown in
Fig. 4. Thus, we conclude from quantum spectroscopy that these two processes must be separate due to their
different sensitivity to 2-photon correlations.

Fig. 3: The differential response for a Schrödinger Cat Fig. 4: Relative differential shows that the nonlinear
state with squeexed fluctuations in the displacement scattering has many-body correlations that are strongest
direction. close to, but not at the second harmonic peak.
[1] M. Ngom, S. Li, G. Schatz, R. Ernie, A. Agarwal, N. Kotov, and T.B. Norris, “Electron beam mapping of plasmon resonances in
electromagnetically interacting gold nanorods,” Phys. Rev. B 80, 113411 (2009).

[2] Ji-Young Kim, Miao-Bin Lien, Myung-Geun Han, Sergei Magonov, Yimei Zhu, Heather Ferguson, Theodore Norris, Nicholas A. Kotov,
“Hidden Asymmetry of Gold Nanorods,” accepted for publication in Science Advances.

[3] Miao-Bin Lien, Ji-Young Kim, Heather Ferguson, You-Chia Chang, Myung-Geun Han, Yimei Zhu, John C. Schotland, Nicholas A. Kotov,
Theodore B. Norris, “Optical Asymmetry and Nonlinear Light Scattering from Colloidal Gold Nanorods,” ACS Nano 11, 5925-5932 (2017).

[4] M. Kira and S. W. Koch, “Quantum-optical spectroscopy of semiconductors,” Phys. Rev. A 73, 013813 (2006).

[5] M. Kira, S. W. Koch, R. P. Smith, A. E. Hunter and S. T. Cundiff, “ Quantum spectroscopy with Schodinger-cat states,” Nat. Phys. 7, 799
(2011).

[6] A. E. Almand-Hunter, H. Li, S. T. Cundiff, M. Mootz, M. Kira, and S. W. Koch, “Quantum droplets of electrons and holes,” Nature 506, 471
(2014).