Generating and Detecting High Frequency Liquid-Based

3 days ago - We use metal nanostructures (nanoplasmonics) excited with dual frequency lasers to generate and detect high frequency ($>10$ GHz) sound ...
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Generating and Detecting High Frequency LiquidBased Sound Resonances with Nanoplasmonics Yanhong Wang, Jingzhi Wu, Shahram Moradi, and Reuven Gordon Nano Lett., Just Accepted Manuscript • DOI: 10.1021/acs.nanolett.9b02507 • Publication Date (Web): 04 Sep 2019 Downloaded from pubs.acs.org on September 4, 2019

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Nano Letters

Generating and Detecting High Frequency Liquid-Based Sound Resonances with Nanoplasmonics Yanhong Wang,† Jingzhi Wu,† Shahram Moradi,‡ and Reuven Gordon∗,‡ †Academy for Advanced Interdisciplinary Research, North University of China, No.3 Xueyuan Rd, Taiyuan, Shanxi, China, 030051 ‡Department of Electrical and Computer Engineering, University of Victoria, Victoria, BC, Canada, V8P5C2 E-mail: [email protected] Phone: +1 250 472 5179 . Fax: +1 250 721 6052

Abstract We use metal nanostructures (nanoplasmonics) excited with dual frequency lasers to generate and detect high frequency (> 10 GHz) sound wave resonances in water. The difference frequency between the two lasers causes beating in the intensity, which results in a drop in the transmission through the nanostructure when an acoustic resonance is excited. By observing the resonance frequency shifts with changing nanostructure size, the transition from slow to fast sound in water is inferred, which has been measured by inelastic scattering methods in the past. The observed behavior shows remarkable similarities to finite element simulations using a simple Debye model for sound velocity (without fitting parameters).

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Keywords nanoplasmonics, acoustic resonances, dynamics of water, sound velocity, extremely high frequency waves For nanostructures, acoustic resonances appear in the extremely high frequency range, typically greater than 10 GHz. (Note, extremely high frequency is the radio-frequency band term). Many works have explored the oscillation of nanostructures in this regime, as well as the impact of the surrounding medium, like water. Systematic studies have probed how solutions damp nanoparticle vibrations; 1 however, the dynamics of the liquid can be evasive. 2 Here we consider the use of nanostructured metals to generate and detect sound waves that travel through a liquid medium. The high frequency physical properties in water have been studied by several methods. Microwave studies show that the real electric permittivity drops by a factor of 45 3 in this range. Inelastic scattering experiments (particularly neutron and x-ray) have suggested that the speed of sound doubles 4,5 and the properties of water are similar to ice. 6 The sound velocity transition has been explored with computational methods. 7 Perhaps not coincidentally with these profound changes is that the vibrational modes of proteins are found in this regime. The oscillations in solution have been probed with the optical Kerr effect 8 and optical tweezers. 9 Inelastic scattering has also been applied to proteins to study their dynamics in this regime, 10 but there is a lack of methods that can access the dynamics in solution. 11 Here we use a double-nanohole (DNH) immersed in water as a means of exciting high frequency acoustic waves. The DNH is used also to detect resonances via changes in the optical transmission. We note variations in the acoustic resonances with geometry. Unlike our previous works on DNH structures, no trapping is used in this experiment. Rather, the intensity beating of two non-degenerate frequency lasers is used to excite sound waves with the source at the cusps between the DNHs where the field intensity is the greatest. This leads to a small variation in the transmission through the aperture when an acoustic resonance is encountered. The observed phenomenon has some relation to stimulated Brillouin and 2

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Raman scattering since two lasers are used to stimulate acoustic waves through photothermal heating (which may be viewed as a third order susceptibility effect). 12 Here the geometry of the structure is modified to probe the sound waves in the medium. Figure 1(a) shows the experimental setup. The lasers are an external cavity tunable laser and a distributed feedback tunable laser, both operating around 850 nm, with power at the aperture of approximately 6 mW (both lasers have the same intensity). The lasers had linewidths of 10 MHz and 200 kHz (DBR852P, Thorlabs, and TLB-6716-OI, New Focus). Therefore, their phase relationship is maintained for thousands of periods for the conditions of our experiment. Even though no locking is used, interference effects can be seen over this period. To ensure that there is minimal coupling between the lasers that would allow for locking of the different modes, 35 dB isolation was used. The optical isolators (labelled as ISO1 and ISO2 in Figure 1(a)) are used to stop the back reflection of laser light. The two lasers are coupled together and divided into two paths, one of which illuminates the nanostructures and the other to monitor the wavelength using an Optical Spectrum Analyzer (OSA). The laser polarization was controlled by a polarizer (PC) and half wave plate (λ/2). The laser beam after the beam expander (BE) was focused on the sample using an 100× oil immersion microscope objective (OI MO). The transmitted light was collected by a 10× MO and focused onto the avalanche photodiode (APD). The LED was used to find the double nanohole using the CCD camera (CAM). Two possible mechanisms are considered to allow for the sound generation in this DNH geometry: heating and electrostriction. While electrostriction is certainly present in water, it is typically probed with extremely high pulse intensities. 13 Since the present experiment uses much lower peak intensities, it is believed that thermal effects dominate here. The temperature differences found for CW measurements of a similar geometry and power was approximately one degree Kelvin per mW. 14,15 This creates a refractive index variation in the liquid and modifies the transmission. Furthermore, the small cusp separation (of the order of 10 nm) means that the thermal diffusion is fast when compared with the timescales of this

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experiment (considering a thermal diffusivity of approximately 10−7 m2 /s in water). Fast thermal relaxation has been considered in several other works at this time scale. 16–18 Thermal expansion of the metal in the gap region can also influence the transmission properties; however, the degree to which this plays a role requires further investigation. The DNH structures were fabricated by focused-ion beam milling; we have also observed resonances in DNH structures fabricated by colloidal methods. 19 Figure 1(b) shows repeated measurements of the transmission through the aperture when tuning the frequency difference (detuning) between the lasers from negative to positive frequencies (the data has been inverted for ease-of-viewing; raw data is shown in the Supporting Information). The acoustic resonances occur when the light transmitted through the aperture is at a minimum value. When on resonance, heating is greatest and the refractive index in the gap decreases on average resulting in less transmission. This is most clear for low frequency detuning (around 0 GHz). In this range, heating occurs when the lasers are in phase and the intensity is highest. This is also when the aperture transmits the least light because the refractive index is lowest, due to the same heating. When the lasers are out-of-phase, there is no heating, but there is also no light due to the destructive interference. As a result, the time-averaged transmission is reduced when averaging over the cycle, from in-phase to out-of-phase. For higher frequencies, resonances occur when the cavity resonances are excited so that the acoustic wave returns to the gap region in-phase. Considering a sound velocity of 1.5 km/s and a dimension of approximately 100 nm, we expect these resonances to occur around the 15 GHz. The exact frequency will differ from this value due to the geometry. We also note that the positive and negative beat frequency values display the same resonances, as would be expected by the symmetry of the experiment (it makes no difference if the lasers are interchanged). In Figure 1(b) we see that the resonance for a 164 nm diameter DNH (diameter of one of the holes) occurs at 12.7 GHz and also at -12.7 GHz. The symmetry and approximate value

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of this resonance are as expected from the above discussion. Also, there is a reduction in the transmission for low frequency beating (around 0 GHz) due to heating when the lasers are in-phase, as discussed above. We systematically repeated this experiment on different aperture sizes. One would expect an inverse size dependence with zero frequency for infinitely large apertures. Figure 2(a) shows this the observed resonances. It is clear that the linear fit to the inverse size does not go through the origin. This is because the observed resonances are shifted from the natural resonances, which is typical for a driven harmonic oscillator. Simple theoretical considerations show that the natural frequency f0 is related to the observed resonance frequency fr by the relation (see Supporting Information for details):

fr =

q f02 − γ 2 /(8π 2 )

(1)

where γ is the damping rate of the resonance. By forcing the data to go through the origin a damping time of 7.8 ps is found. The inset to this figure shows the scanning electron microscope images of the apertures used. Figure 2(a) also shows the finite element method (FEM) COMSOL calculated resonances frequencies, which agree well with the experimental data (see Supporting Information for more details). For the small gaps used in this work, there is no significant influence of the gap size on the resonances observed for the range of frequencies we measured (also see Supporting Information). To confirm the role of the liquid in these resonances, we added glycerol to the solution and noted that the resonance frequency increased. This is consistent with the increase in the sound velocity with the addition of glycerol. 20 Figure 2(b) shows a representative curve. Other concentrations were measured as well and showed the same trend; however, the detailed investigation of mixtures and other liquids is left for a later study. Figure 3(a) shows the resonances for two separate hole diameters of the DNH with resonances extending to higher frequencies. We selected maxima for one DNH structure and

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Figure 1: (a) Schematic of dual laser excitation setup of a DNH immersed in water. The intensity beating at the difference frequency between the lasers excites sound waves. Optical spectrum analyzer (OSA), isolators for the two lasers (IOS1 and IOS2), optical coupler (OC), beam splitter (BS), polarizer (PC), half-wave plate (λ/2), mirror (MR), beam expander (BE), dichroic reflector (DI), microscope objective (MO), avalanche photodiode (APD), CCD camera (CAM). (b) Repeated measurements of transmission (APD voltage) for the same 164 nm diameter DNH as a function of beat frequency between the two lasers. The maximum value measured is subtracted to emphasize the resonances which occur at the minima of the transmission.

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Figure 2: (a) Lowest frequency resonances measured for various aperture diameters, fr . Insets shows scanning electron microscope images of measured apertures. The natural acoustic resonance f0 is shifted from the measured resonance of the aperture fr since it is a driven damped oscillator. The shifted values are plotted as well as f0 . The FEM calculated resonance frequency values for the same structures are also shown. (b) Shift in resonance peaks when adding 10 % glycerol.

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then found the corresponding maxima for a different DNH by similarity in the shape of the curve. The corresponding resonances are shifted and labelled in that figure; the smaller aperture has higher frequency versions of the larger aperture. We can consider the relative changes in the frequency to estimate the change of the sound velocity of water as a function of frequency. The resonance frequency, f is expected to depend on the sound velocity in the liquid, v(f ), as well as the diameter of the aperture d and a geometric parameter for the given resonant mode index m, αm , that depends on the shape of the aperture:

f = αm v(f )/d.

(2)

We can remove the geometric parameter by dividing the frequency of the larger aperture’s resonances, f by the frequency of the smaller aperture’s resonances, denoted as f 0 , and scaling by the size: v(f ) fd = . 0 0 fd v(f 0 )

(3)

We can see that if the velocity of sound in the liquid is a constant, this ratio should be independent of the frequency, yet Figure 3(b) shows a dip in the ratio in the intermediate frequency regime. We attempt to use the Debye model that has been applied to model the frequency dependence of the permittivity of water in this regime. 3 The model has a single parameter for the frequency dependence, the scattering time τ , which is temperature dependent. We take the scattering time to be the same as from microwave measurements of 8 ps. 3 We consider that the Debye model captures the transition from the low frequency response (speed of sound) to the high frequency response in a manner analogous to the real part of the permittivity:

v(f ) = v∞ +

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v0 − v∞ 1 + 4π 2 f 2 τ 2

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(4)

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Figure 3: (a) Resonances of two separate apertures up to higher frequencies. (b) Ratio of the resonance frequencies shown in part (a) scaled by diameter for 3 separate diameters.

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where v∞ is the high frequency limit of the sound velocity and v0 is the low frequency limit. The values for these two limits can be taken from past experiments to be 3200 m/s and 1500 m/s. 4 Figure 4 (a) shows the resonances in the pressure calculated with FEM using the velocity model above for two separate diameters. Figure 4(b) shows the dip in the ratio of resonance frequencies (scaled by geometry), which is similar to the observation of Figure 3(b).

Figure 4: (a) Simulated resonances of pressure for two separate apertures at higher frequencies using a Debye model for velocity. (b) Simulation of ratio of the resonance frequencies scaled by diameter (as shown in part (a)) showing a dip due to varying velocity. In summary, here we directly measure acoustic resonances of the DNH structure in water in the extremely high frequency regime. This measurement was enabled by nanoplasmonic 10

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excitation driven from the gap between the cusps of a DNH aperture in a gold film. The ability to directly excite and measure acoustic waves in water and other liquids in this regime has remarkable implications for studying the physics of liquids and their interactions with nanoparticles. In particular, it may offer understanding of how protein dynamics are influenced by the aqueous medium in this frequency range. 21,22

Acknowledgement The authors thank Cuifeng Ying for providing samples when our local FIB was non-operational. The authors thank Amirhossein Alizadehkhaledi for assistance with aligning the setup. The authors acknowledge support from the NSERC Discovery Grants program and the Chinese Scholarship Council grant 201708140170.

Supporting Information Available Supporting information contains driven damped harmonic oscillator shift of resonance frequency, raw data for measurements on 4 different DNH sizes, polarization dependence of measurements and finite difference time domain simulations of polarization dependence, finite element simulations of acoustic resonances with different cusp separations and diameters. This material is available free of charge via the Internet at http://pubs.acs.org/.

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(17) Juv´e, V.; Crut, A.; Maioli, P.; Pellarin, M.; Broyer, M.; Del Fatti, N.; Vall´ee, F. Nano Letters 2010, 10, 1853–1858. (18) Su, M.-N.; Dongare, P. D.; Chakraborty, D.; Zhang, Y.; Yi, C.; Wen, F.; Chang, W.-S.; Nordlander, P.; Sader, J. E.; Halas, N. J.; Link, S. Nano Letters 2017, 17, 2575–2583. (19) Ravindranath, A. L.; Shariatdoust, M. S.; Mathew, S.; Gordon, R. Optics Express 2019, 27, 16184–16194. (20) Fergusson, F.; Guptill, E.; MacDonald, A. The Journal of the Acoustical Society of America 1954, 26, 67–69. (21) Tarek, M.; Tobias, D. Physical Review Letters 2002, 89, 275501. (22) Kitao, A.; Hirata, F.; G¯o, N. Chemical Physics 1991, 158, 447–472.

Figure 5: TOC figure. Schematic showing oscillations and observed resonances.

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Graphical TOC Entry Acoustic resonances in water generated and detected by a nanoplasmonic gap in double-nanohole structure in a gold film. Resonance shifts from different structures used to infer changes in water sound velocity.

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TOC figure: Acoustic resonances in water generated and detected by a nanoplasmonic gap in doublenanohole structure in a gold film. Resonance shifts from different structures used to infer changes in water sound velocity. 82x44mm (300 x 300 DPI)

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