Synthesis and Shape Manipulation of Anisotropic Gold Nanoparticles by Laser Ablation in Solution

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C: Physical Processes in Nanomaterials and Nanostructures

Synthesis and Shape Manipulation of Anisotropic
Gold Nanoparticles by Laser Ablation in Solution
Valentina Piotto, Lucio Litti, and Moreno Meneghetti
J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.9b10793 • Publication Date (Web): 30 Jan 2020
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Page 1 of 29 The Journal of Physical Chemistry
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Synthesis and Shape Manipulation of Anisotropic
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Gold Nanoparticles by Laser Ablation in Solution
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17 Valentina Piotto, Lucio Litti*, Moreno Meneghetti*
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21 Department of Chemical Sciences, University of Padova, via Marzolo 1, Padova, Italy
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26 Abstract
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31 Anisotropic gold nanostructures are attracting attention due to the strong correlation
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35 between their shape and the localized surface plasmon resonances, that allows to tune
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38 their optical responses through morphological optimizations. Laser ablation synthesis in
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solution usually produces stable gold nanospheres colloids without any surfactant, which
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45 is important for their easy functionalization. Nevertheless, obtaining anisotropic
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nanoparticles with this technique is still a challenge, and few examples show that a post-
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52 synthesis approach is usually required. We show that a single pulse laser ablation allows
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the synthesis of anisotropic branched gold nanoparticles through a careful control of the
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60 ACS Paragon Plus Environment
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The Journal of Physical Chemistry Page 2 of 29
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4 number of laser pulses interacting with the generated nanoparticles. It is shown that the
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7 very first pulses considerably affect the morphology of the ablated nanomaterial.
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11 Moreover, also the fluence above the ablated target is found to have an important role in
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14 the final nanoparticle morphology. The study of the interaction between the
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18 nanostructures and the laser pulses is achieved using an inflow set up. The optical
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21 extinction behaviour of the produced anisotropic gold nanostructures was rationalized
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25 using Boundary Element Method (BEM) based calculations, by considering the
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28 contributions from several morphologies, which found good agreement with experimental
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32 observations.
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40 Introduction
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Anisotropic gold nanostructures are attracting wide interest for their optical properties,
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47 which can span the entire visible and near infrared (vis-NIR) spectral region. Interesting
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applications of these nanostructures exploit the near field enhancement of
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54 electromagnetic fields, due to localized surface plasmon excitation, like Surface
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4 Enhanced Raman Scattering (SERS). Nanostructures shapes can be studied for optimal
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7 excitation as in case of sensors for nanomedicine applications1,2 where exciting light has
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11 to be chosen in the near infrared biological window. Anisotropic nanostructures are
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14 interesting because they show, with respect to spherical ones, several hot spots, namely
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18 regions with high near field electromagnetic amplifications3 found also in nanostructures
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21 like nanoparticle aggregates,4 bypiramids5, rods6, cubes7, nanostars8,3 and nanoworms9.
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25 The control and manipulation of shape and anisotropy at the nanoscale is well established
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28 using wet chemistry approaches, such as in the synthesis of nanotriangles through
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32 intermediate seeds10, gold nanorods synthesis mediated by CTAB11 or also combined
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35 with Ag+ ions,12 or gold nanostars grown on seeds using HAuCl4 and PVP.13 All of these
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approaches are mostly based on selective growing of some crystal faces, using a wide
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42 variety of capping agent or, at least, stabilizing species to stop growing and avoiding
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coalescence and aggregation.
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49 Laser ablation synthesis in solvents (LASiS), is a clean top-down approach for colloids
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production that does not need any chemicals for stabilizing the synthesized
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56 nanostructures because of their native charge. This is an advantage for many
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4 applications, in particular when the nanostructures have to be functionalized, because
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7 any exchange reactions between stabilizing molecules and those of interest are not
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11 required, or when clean surfaces are important, like for larger SERS signals.14,15 Despite
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14 the clear advantages of this technique for the synthesis of nanoparticles, the control over
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18 their dimension and shape is poor. LASiS synthesis usually produces spherical shapes,
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21 which, as recalled above, show less interesting properties. Several studies have been
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25 presented exploring the role of solvent composition,16,17 laser wavelength,18 pulse
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28 duration,19,20 repetition rate21 or energy fluence.22 However, controlling the different
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32 stages of the nanoparticles synthesis, from the plasma plume formation to the collapse
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35 of the cavitation bubbles,23 is a challenging task because different steps hardly reach the
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thermodynamic equilibrium. Few studies report the possibility of obtaining anisotropic
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42 gold nanostructures due to post-production irradiation24,25,26,27. Here we present a one
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step synthesis of highly anisotropic nanostructures with the laser ablation process when
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49 the synthesis is obtained by controlling the number of laser pulses, which interact with the
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produced nanoparticles. This was possible using an in-flow system, which allows
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56 controlling the time in which the produced nanoparticles are resident within the irradiated
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4 region. Moreover, it will be shown how the morphology of the nanoparticles is influenced
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14 Experimental section
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19 Materials and Instruments
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23 Laser ablation was carried out with a Q-Smart 450 Nd:YAG laser (6 ns, 1064 nm).
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27 99.999% pure gold was used for the target with the form of a disk of 5 mm diameter and
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30 2 mm thick. The M 045 (Techma gmp) peristaltic pump was used with 3.2 mm internal
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34 diameter Tygon tubes and operating at 0.125 mL/s. The ablation cells for the inflow
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37 system were made in Teflon with a linear geometry and channels of 5 mm width and 5
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mm (LV cell) height, as schematized in the Figure 5. In HV cell, the height was increased
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44 to 20mm. The upper surface of the cells was covered with a micro cover glass. DLS
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measurements were performed with a Malvern Instrument Zetasizer Nano operating with
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51 a 633 nm He-Ne laser. TEM images were collected at 100 kV with a FEI TECNAI G2
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electron microscope. Optical characterization was performed with an Agilent Cary 5000
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4 UV-Vis-NIR spectrometer using quartz cuvettes. All chemicals were purchased from
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7 Sigma Aldrich if not differently specified.
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12 Laser ablation synthesis in “standard condition”
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16 Standard gold nanoparticles synthesis was obtained by focusing the laser pulses on a
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20 gold target, fixed at the bottom of a cylindrical glass cell of 2 cm diameter. 10 µM NaCl
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23 aqueous solution was used as solvent over the target. The liquid level above the target
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27 was set to 2 cm and solvent flux or mechanical stirring were not present. The fluence was
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30 set at 2 J/cm2 on the target with a spot diameter of Ø=1 mm using a lens of 7.5 cm focal
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34 length, the repetition rate at 15 Hz and the ablation proceeded for 20 minutes.
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38 Laser ablation synthesis with the inflow system
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P1, P2 and P3 samples were obtained with an inflow system using a peristaltic pump
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46 and setting the liquid flow at 7.5 mL per minute. 10 µM NaCl aqueous solution was used
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as solvent. The laser repetition rate was changed from 5 Hz (P1 sample) to 10 Hz (P2
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53 sample) and to 15 Hz (P3 sample). Given the liquid flow and the different pulse
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4 frequencies, the liquid volume flowing above the target received one, two or three pulses
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7 before being completely flowed forward. The fluence was set at 2 J/cm2 on the target,
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11 which is not moved, as in most usual ablation setup, with respect of the laser beam.
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15 Looped laser ablation synthesis
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20 To reproduce, with the inflow system, the standard synthesis in which the nanoparticles
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23 receive multiple laser pulses, a closed circuit was used. The Tygon tubes were closed in
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27 a loop so that the peristaltic pump fluxed the same colloidal solution multiple times inside
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30 the ablation cell above the target. At each loop the solution enriched in particles and, at
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34 the same time, the previous synthesized particles were irradiated again. In the so called
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37 “low volume cell” (LV) the ablation chamber was 0.5 cm high, while in the “high volume
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cell” (HV) it was increased to 2 cm. The fluence was set at 2 J/cm2 on the target and the
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44 repetition rate at 15 Hz.
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53 Standard Irradiation of LV and HV samples
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4 LV and HV samples, obtained through looped laser ablation, were then irradiated in
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7 static condition. In this case the same cell of the static standard ablation was used and
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11 the laser beam was focused near the bottom of the cell, where the target is usually placed.
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14 For reproducing standard ablation conditions, the frequency of the laser and the fluence
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18 were set at 15 Hz and 2 J/cm2, and solution flux was not present. The irradiation was
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21 stopped after 180 minutes and UV-Vis spectra of the solution were collected at time 0,
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25 15, 30, 120 and 180 minutes to show the evolution of each sample.
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29 BEM simulation
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34 Boundary Element Method (BEM) simulation were carried out using the libraries from
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37 Hohenester et al,28,29 implemented in Matlab R2017b to arrange complex structures
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created with Blender 2.8. Extinction, scattering and absorption cross sections as well as
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44 the least squares linear regression of the experimental data with the simulated dataset,
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were calculated following the same approach reported in a previous study.4
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4 Result and Discussion
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8 Laser ablation of a target under solvents usually produces nanospheres because
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12 uncontrolled fusion and further ablation of the particles take place after the nanomaterials
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15 are first ablated from the target. The control of the interaction between laser pulses and
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19 the ablated particles is an important step in the synthesis and allows controlling fusion
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22 and further ablation processes. An inflow system, sketched in Figure 1a, was
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26 implemented within the laser ablation set up to control the number of laser pulses that
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29 interact with the solution volume flowing above the target. The inflow system consists of
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33 a low volume cell (LV cell, 5 mm height over the irradiated area) in which the µ-molar
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36 NaCl solution was flowed by a peristaltic pump. Setting the solution flow rate at 7.5 ml per
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minute and increasing the laser repetition frequency it is possible to control the number
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43 of pulses hitting the solution over the gold target before it is flowed away. Repetition rates
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of 5, 10 and 15 Hz were used for hitting the volume over the target with 1, 2 and 3 pulses
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29 Figure 1. (a) Set up scheme representing the inflow laser ablation system; (b) extinction
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spectra of sample P1, P2 and P3, normalized at 400 nm and compared to a solution of
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36 gold nanoparticles obtained in a static standard synthesis; (c, d and e) TEM images of
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respectively gold nanoparticles obtained in static standard ablation, branched
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43 nanoparticle (P1 sample) and reshaped branched nanoparticle (P3 sample).
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52 P1, P2 and P3 samples were characterized by TEM, DLS and vis-NIR spectra and
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55 compared with gold nanoparticles obtained in static standard conditions, in which the
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4 target, and the solution over it, receives thousands of pulses in 20 minutes. The
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7 nanoparticles obtained in a standard experiment are spherical (see Figure 1c), with a
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11 diameter distribution (by TEM) centred at 25 nm (Figure 2a) and a narrow plasmon peak
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14 at 522 nm (Figure 1b). The normalized spectra reported in Figure 1b show that P1 (i.e.
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18 the ablated particles that did not receive further pulses) is considerably different from that
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21 obtained in static standard conditions, with a broader plasmonic peak at about 520 nm,
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25 slightly shifted toward longer wavelengths, and a long, broad, tail in the NIR region. The
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28 spectra of P2 and P3 samples, in which the ablated nanoparticles received on average,
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32 after their formation, one or two more pulses, show a decrease of the extinction in the
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35 NIR and a narrowing of the resonance band at about 520 nm, a trend clearly moving
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toward the recovering of the static standard ablation extinction profile.
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29 Figure 2. TEM dimensional distribution of spherical nanoparticles (NP) and branched
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nanostructures (BR) for static standard ablated gold nanoparticles samples (a) and
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36 samples P1 (b), P2(c) and P3(d).
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In TEM images (see Figure S1) one can observe a consistent fraction of anisotropic
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44 nanoparticles (“branched”, BR, Figure 1d) in P1, P2 and P3 samples, which cannot be
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47 seen in the static standard synthesis (Figure 1c). About 30% of all analysed particles in
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51 P1, P2 or P3 samples can be described as BR nanostructures. Since gold laser ablated
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54 nanomaterials produced in diluted salt solution are stabilized by coulomb interactions due
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4 to surface charges,16 it can be deduced that the BR nanostructures are native structures,
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7 which are not formed after an aggregation and fusion process. Due to their anisotropic
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11 shape, equivalent diameters are defined in Figure 2 as that of a sphere having the same
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14 area of a BR nanoparticle observed in TEM images. The BR equivalent diameters were
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18 found within almost the same dimensional range of the spherical NP, for all samples. This
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21 suggests that the amount of material present in BR and spherical nanoparticles is almost
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25 the same, and, therefore, that the process generates nanoparticles with almost the same
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28 amount of material, although with different shapes. However, Dynamic Light Scattering
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32 (DLS) measurements, reported in Figure 3, being sensitive to the hydrodynamic diameter
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35 and so to the steric hindrance, show that P1, P2 and P3 samples have distribution centred
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at much larger dimensions than the relative equivalent diameters obtained by TEM
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42 images, and also larger than the diameters of the nanoparticles obtained in standard
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conditions. The comparison of the TEM and DLS data clearly show that, increasing the
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49 number of pulses, using the fluences for the ablation, the hydrodynamic size strongly
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reduces, with a trend toward standard gold nanoparticles usually obtained with a large
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56 number of pulses (Figure 3).
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Standard
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Diameter (nm)
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27 Figure 3. DLS measurement (number) of samples P1 (peak at 128 nm, 53 nm FWHM),
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30 P2 (67 nm, 27 nm FWHM) and P3 (46 nm, 20 nm FWHM) compared to a solution of
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34 standard gold nanoparticles (33 nm, 11 nm FWHM)
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43 A set of simulated nanospheres and branched nanostructures were designed to
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46 elucidate the relative trend of equivalent diameters, obtained by TEM, and hydrodynamic
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50 diameters, obtained by DLS. The virtual nanostructures take inspiration from the TEM
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4 maximum Feret diameter, namely the nanostructure’s maximum hindrance, was
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7 assumed as a fair approximation of the DLS hydrodynamic diameter. The equivalent
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11 diameters reported in Figure S2 is coherent with the definition used for TEM images,
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14 namely the diameter of a sphere having the same volume of the relative structure. In
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18 Figure S3 the equivalent diameters and the Feret diameters are plotted together and one
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21 can see, as expected, that the two align only in case of nanospheres, while the Feret
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25 diameters diverge consistently for anisotropic nanostructures. The extinction, scattering
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28 and absorption spectra of the same simulated geometries were then calculated using the
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32 Boundary Element Method (BEM), thanks to the libraries published by Hohenester at
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35 al.28,29, and are reported in Figure S4. While the red-shift of the ≈520 nm localized
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plasmon band is small through the series of nanospheres, the presence of new plasmon
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42 resonances in the NIR region becomes predominant as far as the nanostructure
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increases in both dimension (i.e. Feret diameter) and anisotropy. It should be noted that
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49 only the most branched nanostructures have consistent extinctions around 1064nm, i.e.
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the wavelength used for the ablation. This results also allows interpreting the trend
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56 observed in optical measurements of samples P1, P2 and P3 in Figure 1b, since the
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4 extinction in the NIR region progressively decreases through the series. The extinction
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7 profiles obtained by BEM simulations were used for deconvolving the experimental
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11 spectra in Figure 1b, following the same approach just reported for gold nanospheres
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14 aggregates.4 In Figure 4b-e are reported the normalized experimental spectra for the
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18 “Standard Ablation” sample and for P1, P2 and P3, together with the relative weighted
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21 simulated spectra. One first observes that the extinction contribution in the NIR region
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25 can derive almost exclusively from the BR nanostructures, since none of the spherical NP
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28 shows extinctions above 800 nm. Although the simulations are obtained with a limited
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32 library of structures, the vis-NIR spectral contribution of P1, P2 and P3 samples can be
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35 clearly deduced. The overall spherical nanoparticles contribution is maximum for the
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“Standard Ablation” sample and minimum for the P1 sample (see Figure S5) whereas the
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42 opposite is found for the simulated BR contributions. In accordance to what was just
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achieved observing the electron microscopy images, the trend observed with the TEM
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49 equivalent diameters and the DLS hydrodynamic diameters suggests that the pulse
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dosage has the effect to modulate the morphology of the ablated material toward more
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56 isotropic nanoparticles.
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33 Figure 4. Simulated nanostructures were inspired by TEM images (a) and used to
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calculate the relative extinction spectra of single spherical nanoparticles and BR particles.
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40 The simulated extinction spectra are used as a base set to interpret the extinction spectra
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of AuNPs in standard static ablation condition (b), P1 (c), P2 (d) and P3 (e) as a linear
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47 combination of several contributions.
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4 The conclusion that the number of pulses hitting the nanoparticles modifies in particular
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7 the roundness of the BR nanoparticles, suggested to perform in-flow ablation
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11 experiments, in which the solution circuit is closed in a loop (Figure 5a). This configuration
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14 was called ‘low volume’ (LV) cell because the solution over the target was only 0.5 cm
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18 high. Under this condition, the ablated material experienced multiple laser pulses. The
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21 extinction spectrum of a colloidal solution ablated for 20 minutes is compared, in Figure
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25 5b, to that of P3 and of the standard nanoparticles. One finds that increasing the number
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28 of pulses is not sufficient to reproduce the extinction spectrum of the standard colloidal
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32 solution. The reason can be found in the different setup used for a standard experiment
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35 and for the looped LV cell. In particular in a standard experiment the liquid height over
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the target is 2 cm, whereas it is 0.5 cm in the LV cell. Since reshaping is usually obtained
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42 at low fluence regimes,30 one deduces that reshaping is obtained in the liquid above the
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target, where the laser beam is not focused. It can be therefore predicted to be more
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49 efficient in the static, standard setup then in the looped LV cell.
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23 Figure 5. (a) set up for the multi-pulse closed circuit ablation; (b) comparison between
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26 the extinction spectrum of standard gold nanoparticles, P3 sample and the solution
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30 obtained with the close circuit set up.
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39 This observation suggested that, in order to promote the nanoparticles reshaping, lower
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42 fluences are required. For this reason, a second in-flow ablation cell, in which the height
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46 of the liquid above the target was increased from 0.5 cm to 2 cm, was used for the
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49 ablation. This cell was called ‘high volume’ (HV) cell. The fluence on the gold target
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53 surface was maintained constant at 2 J/cm2, while, thanks to the new geometry of the HV
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4 cell, the fluence at the upper liquid surface reached a value of 0.4 J/cm2 whereas that
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7 obtained with the LV cell which was 1.4 J/cm2. Therefore, with the HV cell, the reshaping
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11 was expected to be more efficient along the light cone of the focused beam. The vis-NIR
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14 spectra (see Figure S6a) of the looped in-flow ablation, obtained with the HV cell,
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18 confirmed the expected results showing a further reduction of the NIR tail of the extinction
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21 spectra due to the BR nanostructures. As a final evidence of the reshaping mechanism
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25 of the BR nanostructures due to multiple pulses and a lower fluence regime, the
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28 nanoparticles of the LV experiment were irradiated in a static configuration, like that of a
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32 standard ablation setup. Figure 6a shows the variation of the extinction spectrum for the
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35 LV sample and one observes that the NIR spectral tail decreases with time, becoming
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more similar to that of the static standard ablated gold nanoparticles (black line). Some
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42 differences can be understood since in the standard synthesis a plasma plume, which
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can interact with the particles, is always present. Both DLS measurements (see Figure
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49 6b) and TEM images, (see Figure 6c) confirm that the static irradiation of the LV sample,
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produces more spherical nanoparticles. The same irradiation experiment was also
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56 conducted for the looped HV nanostructures showing that the recovering of the spectral
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4 shape of the standard nanoparticles is obtained faster (see Figure S6b), as also
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7 confirmed by DLS measurement (see Figure S6c).
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26 Figure 6. a) extinction spectra of LV cell sample during post-irradiation at time 0, 15,
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30 30, 120 and 180 minutes compared with a static standard solution of ablated gold
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33 nanoparticles; b) DLS measurement of LV sample before (peak at 39 nm, 19 nm of
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37 FWHM) and after irradiation (peak at 42 nm, 12 nm of FHWM); c) TEM images of the
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40 closed circuit ablation after 180 minutes of post-synthesis irradiation at 1064 nm. Scale
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44 bar refers to 100 nm.
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53 Conclusions
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4 Anisotropic gold nanostructures are obtained by pulsed laser ablation under solvent
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7 when a small number of pulses are used for the ablation. Extinction spectra, supported
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11 by TEM images and DLS measurements, were used to highlight the steps that lead, in a
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14 static standard experiment, to the synthesis of spherical nanoparticles. BEM simulations
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18 supported the interpretation of the extinction spectra of the colloidal solutions, underling
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21 the different contributions of the branched (BR) and spherical nanostructures for the
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25 different type of samples. As evidenced by the results, not only the number of pulses, but
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28 also the fluence profile optimization is crucial for controlling the nanostructure
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32 morphological evolution during the pulsed laser ablation process. The present study
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35 allows understanding the strategies for obtaining anisotropic nanoparticle with extinction
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spectra in the NIR spectral region using the laser ablation technique, which allows the
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42 synthesis of naked nanoparticles, useful for easy functionalization.
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51 ASSOCIATED CONTENT
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Supplementary data associated with this article can be found in the online version.
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4 AUTHOR INFORMATION
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8 Corresponding Author
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12 * lucio.litti@unipd.it, moreno.meneghetti@unipd.it
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Author Contributions
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20 The manuscript was written through contributions of all authors. All authors have given
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24 approval to the final version of the manuscript.
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28 Funding Sources
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32 This project was supported by P-DiSC project #04SID2016.
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36 ACKNOWLEDGMENT
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41 Authors would like to acknowledge F. Mancin for DLS and Z potential measurements.
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Synthesis and Shape Manipulation of Anisotropic Gold Nanoparticles by Laser Ablation in Solution

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