Electronic Supplementary Material (ESI) for Nanoscale.

This journal is © The Royal Society of Chemistry 2020

Electronic Supplementary Information (ESI)

Gold nanowires growth through stacking fault mechanism by

oleylamine-mediated synthesis

Daniel A. Moraes,a# João B. Souza Junior,a# Fabio F. Ferreira,b Naga Vishnu V. Mogilic and Laudemir C.
Varanda*a

a
Colloidal Materials Group, Physical-Chemistry Department, Instituto de Química de São Carlos,
Universidade de São Paulo, São Carlos 13566-590, SP, Brazil. E-mail: [email protected].

b
Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, Santo André, 09210-580, SP,
Brazil.

C
Brazilian Nanotechnology National Laboratory (LNNano), Brazilian Center for Research in Energy and
Materials (CNPEM), Campinas, 13083-970, SP, Brazil.

#
These authors contributed equally to this work.

* Corresponding Author: Laudemir C. Varanda. E-mail: [email protected]

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Table of Contents

Additional experimental data about Au-TPNW samples with different reaction conditions, XRD code
simulation and results for stacking fault Au nanorods and crude data for the temperature dependence XRD,
and UV-Vis simulations for the LSPR spectrum with different dielectric mediums are included in this ESI.

Results and Discussion ____________________________________________________________ 3

Modifications in the gold tadpole-like nanowires synthesis _____________________________ 3

Table S1. Experimental parameters used in the syntheses of gold nanomaterials __________ 4

Fig. S1. Samples at different experimental conditions described in Table S1 _____________ 5

Figures and XRD Simulation Code ___________________________________________________ 6

Fig. S2. Face-centered cubic (fcc) unit cell observed for Au materials ____________________ 6

XRD simulation of stacking fault gold nanoparticles using DiFFaX _______________________ 7

DiFFax Code _________________________________________________________________ 7

Fig. S3. Close-packed planes and XRD simulations of the fcc and hcp structures____________ 8

Fig. S4. Temperature dependence of XRD data of gold nanowires_______________________ 9

HTEM images __________________________________________________________________ 10

Fig. S5. HRTEM images showing the stacking faulted tail growth from the [111]𝑓𝑐𝑐 _______ 10

Optical and Magnetic properties ___________________________________________________ 11

Fig. S6. Optical and magnetic characterizations ____________________________________ 11

Fig. S7. Simulated local electric field enhancement LSPR _____________________________ 14

Fig. S8. Simulated LSPR spectrum with a different aspect ratio (R) _____________________ 15

Fig. S9. Simulated scattering cross sections with different width and length _____________ 16

Fig. S10. Simulated scattering cross sections with different refractive index______________ 17

References ____________________________________________________________________ 17
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Results and Discussion

Modifications in the gold tadpole-like nanowires synthesis

Different parameters were used according to the experimental procedure to evaluate its influence on
the gold nanoparticles formation, and the main ones are described in Table S1. The influence of a solvent
mixture, and the synthesis parameters (Table S1) have been evaluated to advance in the knowledge of a
possible formation mechanism of gold tadpole-like nanowires (Au-TPNW). When pure OAm was used under
a gentle stirring and intermediate temperature (65 °C), a mixture consisting of nanowires (large amount) and
nanospheres were obtained, and the nanowires was easily separated by standard size-selective approach
(sample Au3, Fig. 1b and 1c) as described in the Methods section for Au-TPNW synthesis. This initial result is
in good agreement with the reported works showing that vigorous stirring and high temperature lead to
spherical nanoparticles growth. In small amounts of oleylamine and using the best conditions to synthesize
the Au-TPNW (sample Au2) did not was possible to observe the formation of the nanowires. Fig. S1d shows
that sample Au2 is composed majority for spherical nanoparticles and just a little portion of elongated
nanomaterials, inferring that the formation of the nanowires strongly depends on oleylamine presence,
besides more gently conditions of temperature and stirring.
The main synthesis procedure described in the Methods section using a mixture of 1-octadecene and
oleylamine as solvents, results in the monodisperse spherical gold nanoparticles (sample Au1, Fig. 1a and S1a)
with coefficient of variation (average diameter/standard deviation, 𝜎/𝜇) lower than 0.1, as observed in the
histogram presented in the Fig. S1b. The nucleation and growth processes control result in the spherical
nanoparticles as predicted by the theories already discussed in the literature for well-known spherical
nanoparticles formation.Low temperatures, slightly above room temperature, is enough to synthesize gold
nanoparticles since the gold has a positive reduction potential, meaning the reduction of Au3+ to metallic gold
is favorable at this condition. At temperatures around 70 °C, it is possible to visualize the reduction of Au3+ to
Au+ as the yellow gold solution becomes colorless while the reduction process takes place. The metallic gold
by the reduction of Au+ to Au and the formation of metallic nanoparticles can be readily observed by the
appearance of the red color related to the LSPR (Localized Surface Plasmon Resonance) absorption band
centered around 520 nm, Fig. S1c.
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Table S1. Experimental parameters used in the syntheses of gold nanomaterials.

Samples
Parameters
Au1[a] Au2 Au3[b]

HAuCl4/mmol 0.1 0.1 0.1

ODE/mL 8 11.5 0

OAm/mL 4 0.5 12

Time/h 2 72 72

Stirring Strong Gentle Gentle

Temperature/°C 80 65 65
[a] Spherical gold nanoparticles, and [b] tadpole-like gold nanowires both discussed in the main text.
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Fig. S1. Samples at different experimental conditions described in Table S1. Sample Au1: (a) TEM image of
the spherical gold nanoparticles synthesized using a mixture of HAuCl4.3H2O, octadecene and oleylamine at
80 °C and its (b) histogram concerning the particle size distribution. In (c), the UV-Vis spectrum shows the
LSPR band centered at 520 nm. The TEM image of the (d) Au2 sample synthesized at low OAm concentrations
in similar conditions for the Au-TPNW formation.
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Figures and XRD Simulation Code

Fig. S2. Face-centered cubic (fcc) unit cell observed for Au materials showing the three principal
crystallographic facets {111}, {110}, and {100}. The Truncated cuboctahedron shows the three different facets
within the unit cell.
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XRD simulation of stacking fault gold nanoparticles using DiFFaX

DiFFax Code

The code hereafter was used to generate the simulated XRD pattern (Fig. S3) for gold nanorods with a
length of 100 nm (425 layers of the close-packed planes (111)) and a diameter of 10 nm. The values of PFCC
(probability of fcc stacking) and PHCC (probability of hcp stacking) was changed accordingly keeping PFCC +
PHCC = 1.

{data file for gold with random hexagonal intergrowths}

{probability of cubic stacking was variable by changing layers transitions}
{cubic stacking sequence = 111111111.... or 222222222...}
{Hexagonal staking sequence = 1212121212121212....}

INSTRUMENTAL {Header for instrumental section}

X-RAY {Simulate X-ray diffraction}
1.5418 {X-ray wavelength}
Lorentzian 0.1 trim {Instrumental broadening (much faster)}

STRUCTURAL {Header for structural section}

2.8667 2.8667 2.3550 120.0 {unit cell coordinates, a, b, c, gamma}
6/MMM {hexagonal, c = cubic [111]}
2 {111 sheet, plus its mirror}
100 100 {Layers wide in the a-b plane Angstron, 10 nm}

LAYER 1
CENTROSYMMETRIC
Au 1 0.0 0.0 0.0 0.0 1.0 {Atom, Number id, x, y, z, B_iso - Debye-Waller, Occ}

LAYER 2 = 1

STACKING {Header for stacking description}

recursive {Statistical ensemble permutation all possibilities}
425 {425 layers near 100 nm, aspect ratio of 10}

TRANSITIONS {Header for stacking transition data}

{Transitions from layer 1}

PFCC 1/3 2/3 1.0 {layer 1 to layer 1, PFCC probabilities of FCC phase between 0-1}
PHCP 2/3 1/3 1.0 {layer 1 to layer 2, PHCP probabilities of HCO phase between 0-1}

{Transitions from layer 2}

PHCP 1/3 2/3 1.0 {layer 2 to layer 1}
PFCC 2/3 1/3 1.0 {layer 2 to layer 2}
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Fig. S3. Close-packed planes and XRD simulations of the fcc and hcp structures. (a) Illustration of the stacking
sequence of the closed-packed planes that leads to hcp (ABABAB…) and fcc (ABCABC…) along with their in-
plane (𝑎𝑏-plane) dislocation vectors for axes 𝑎 and 𝑏 showing that transitions 1 to 2 or 2 to 1 leads to hcp
packing and transitions 1 to 1 or 2 to 2 leads to fcc packing. For each transition, a 2.35 Å dislocation that is
normal to the 𝑎𝑏-plane occurs (parallel to the 𝑐-axis and to the [111]𝑓𝑐𝑐 direction). (b) XRD simulations for
gold nanorods with an aspect ratio of 10 (width 10 nm and length 100 nm) using different amounts of stacking
sequences of the closed packed plane that leads to hcp (ABABAB…) or fcc (ABCABC…) phase performed using
DiFFaX software.
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Fig. S4. Temperature dependence of XRD data of gold nanowires showing (a) the typical Rietveld refinement
realized for sample at room temperature that was used to excluded the Pt peaks (XRD heating foil) and
background; different graphical plots to highlight (b) the diffraction halos vanishing and (c) 3D plot showing
the (111) peaks intensities.
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HTEM images

Fig. S5. HRTEM images showing the stacking faulted tail growth from the [111]𝑓𝑐𝑐 direction of the fcc head.
Insets correspond to the FFT images obtained from the fcc head regions.
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Optical and Magnetic properties

Fig. S6. UV-Vis spectroscopy for (a) experimental Au-TPNW sample in hexane and (b) simulated LSPR spectrum
for gold nanorods with a different aspect ratio (R) for the z-polarized band position (parallel to the rod
lengths). Nanorods simulation was achieved by keeping the width 10 nm and changing the length for the
different R values. The multiplication factor is shown to keep the maximum absorption aligned and give the
correct scattering cross-section. Magnetic characterization of the Au-TPNW: (c) the hysteresis loop measured
at 5 K shows the ferromagnetic behavior. The zoom (inset) highlighted the MREM and HC values assigned to
the ferromagnetic behavior; (d) field-cooled (FC) and zero field-cooled (ZFC) measured with a maximum
applied field of 100 Oe show a blocking temperature (TB) value of 301.15 K and inferring that ferromagnetic
behavior remains slightly above the room temperature.
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Fig. S6 shows the optical and magnetic properties of the Au-TPNW. The UV-Vis spectrum of Au-
TPNW sample featuring a broad absorption band from 800 nm to the near-IR region of the
electromagnetic spectrum. The sharp band about 500 nm was assigned to the presence of both the
LSPR from spherical gold nanoparticles and the y-polarized absorption of the gold nanowire. The two
LSPR modes for gold nanorods or nanowires, longitudinal and transverse plasmon bands, can be
visualized in Fig. S7. The simulated local electric field enhancement (|𝐸|2 /|𝐸0 |2 ) from the LSPR is
displayed in Fig. S7 showing both y-polarized (transverse) and z-polarized (longitudinal) plane-wave,
whereby the light propagates along the x-axis, and the nanorods are oriented with its long axis
oriented parallel to the z-axis. Whereas the y-polarized spectra for nanorods with a different aspect
ratio (length by width, 𝑅) keep their maximum absorption around 515 nm (Fig. S8) the z-polarized
absorption band is highly dependent upon 𝑅, Fig. S6b and Fig. S9. The longitudinal LSPR dependence
with 𝑅 arises from the depolarization field associated with the particle’s geometry, the depolarization
form factor. A red-shift of the longitudinal plasmon band is observed increasing 𝑅 and the longitudinal
absorption band ranges from ~600 nm (𝑅 = 3) to ~1700 nm (𝑅 = 20) when simulated using vacuum
permittivity constant (dielectric constant) as surrounding medium (Fig. S9) for water and hexane
medium. The broad plasmon band observed in Fig. S6a for the longitudinal mode, ranging from UV-
Vis to near-IR region, is originated by the presence of nanowires having a large size distribution in
lengths, i.e., it has a statistical contribution of nanorods having different 𝑅 values, as visualized by
simulated spectra in the Fig. S6b. The spectrum in Fig. S6a was limited at 1600 nm, but the
longitudinal band continues into the near-IR region, and it was not included due to the signal noise
originated by molecular absorptions. The longitudinal maximum band absorption position also
depends upon the surrounding media besides 𝑅 values (Fig. S10), and size-controlled nanorods can
also be used as in dielectric constant sensor devices.
Magnetic phenomena in gold nanoparticles have been reported in the literature. 1-7 The magnetic
behavior was initially observed in organic molecules-capped Au nanoparticles with just a few
nanometers in size. The ferromagnetic-like behavior was attributed to the covalent bonds between
the organic capping molecules and the nanoparticle surface gold atoms that, which induces
modifications in its electronic structure. Ligands covalent bonds induce the formation of a 5d hole,
and localized magnetic moments remain frozen due to the strong spin-orbit coupling, and
consequently, the magnetic behavior.1, 6, 7 After that, the magnetism has also been observed in other
Au materials such as gold clusters (small nanocrystals), films, and nanocrystalline films with or without
the organic molecules capping. Besides the presence of the covalent bond effects, the magnetic
behavior in bare Au nanocrystals was recently associated with the spin-glass-like behavior,1, 4 but the
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no is a complete comprehension concerning the magnetic phenomenon observed in gold
nanostructure until now. Here, the magnetic properties of the Au-TPNW were evaluated by the
typical magnetic hysteresis loop measured at 5 K (Fig. S6c) and also by the field-cooled (FC) and zero-
field cooled (ZFC) curves, as shown in Fig. S6d. The magnetic hysteresis curve of sample indicates an
unusual ferromagnetic behavior at 5 K exhibiting the typical profile corresponding to the
ferromagnetic behavior with remanent magnetization (MREM), saturation magnetization (MSAT), and
coercive field (HC) of 2.8 × 10−2 emu g-1, 9.1 × 10−2 emu g-1, and 230 Oe, respectively. The
temperature-dependence magnetization curves inferred that the Au tadpoles have ferromagnetic
behavior up to room temperature, with the blocking temperature (𝑇𝐵 ) value around 301 K (Fig. S6d).
The 𝑇𝐵 value, where the curves split, it corresponds to the onset of the change in the magnetic
behavior, since that the magnetic moments orientation is frozen below 𝑇𝐵 (ferromagnetic) and
becomes randomly oriented above this value (paramagnetic). The ferromagnetic behavior at room
temperature was previously reported in Au nanorods less than 80 nm in length, becomes
paramagnetic if the size of the nanorods increases above this limit. 8 Our results indicate that the
ferromagnetism holds on for tadpoles with size as large as 500 nm.
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Fig. S7. Simulated local electric field enhancement (|𝐸|2 /|𝐸0 |2) from the localized surface plasmon resonance
(LSPR) showing both y-polarized (transverse) and z-polarized (longitudinal) plane-wave excitations direction,
being light propagation direction (k) along the x-axis and the nanorods is oriented with its long axis parallel to
the z-axis. The z-polarized has the electric field E from the light aligned with the z-axis as shown on the bottom
of the figure and the y-polarized has the E vector aligned horizontally. The imagens were obtained for the
position’s maximums of their respective plasmon bans, being the wavelength 740 nm for the z-polarized and
520 nm for the y-polarized. The refractive index of the medium was vacuum ( of 1.0)
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Fig. S8. Simulated LSPR spectrum for gold nanowires with a different aspect ratio (R) for the y-polarized band
position as shown in Fig. S5. Nanorods simulation was achieved by keeping the width 10 nm and changing the
length for the different R values. The multiplication factor is shown to keep the maximum absorption aligned
and give the correct scattering cross-section. It is possible to observe that the maximum of the y-polarized
band is almost invariable with R, keeping the maximum scattering around 515 nm for the transverse plasmon
band. This value is close to the observed for spherical nanoparticles as shown in Fig. S1c.
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Fig. S9. Simulated scattering cross sections for gold nanowires with fixed aspect ratio (R) but different width
(W) and length (L) showing the small changing in peak position.
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Fig. S10. Simulated scattering cross sections for gold nanowires using the refractive index of the embedding
medium () for vacuum (0.0), water (1.33), and hexane (1.37).

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