Vol. 25, No.

25 | 11 Dec 2017 | OPTICS EXPRESS 31064

Third order nonlinear optics in Ag nanocubes:

local and nonlocal optical responses as a
function of excitation wavelength and particle
size
E. V. G ARCA R AMREZ , S. A. S ABINAS H ERNNDEZ , D. R AMREZ
M ARTNEZ , G. D AZ , AND J. A. R EYES E SQUEDA *
Instituto de Fsica, Universidad Nacional Autnoma de Mxico, Mxico City 04510, Mexico
* reyes@fisica.unam.mx

Abstract: Colloidal silver nanocubes in solution were analyzed by the Z-scan technique in
the resonant and non-resonant regimes. Three dierent systems with particle sizes of 56, 99
and 215 nm, and concentrations of 0.378, 0.831 and 0.715 mg/mL, respectively, were obtained
by the polyol method. Nonlinear excitation of the samples was performed with laser pulses
of 26 ps, at a repetition rate of 10 Hz, and using three dierent wavelenghts (355, 532 and
1064 nm), exciting only the electronic part of the optical nonlinearity, and avoiding induced
thermal loading of the samples. Whenever observable, samples showed saturable absorption
for all wavelengths, which was dependent, in general, on concentration and incident intensity.
For samples featuring sizes of 55 and 99 nm, saturable absorption could be observed for
wavelengths close to their dipolar surface plasmon resonances; while, for samples with sizes of
99 and 215 nm, saturable absorption and positive nonlinear optical refraction (only for size of
215 nm) could be observed at 1064 nm. Besides, for some samples, nonlinear optical response
followed the incident intensity profile at wavelengths close to resonance. On the contrary, for
wavelengths out of resonance, the nonlinear optical behavior showed to be nonlocal, ie, its
profile was narrower than the incident one.

c 2017 Optical Society of America
OCIS codes: (190.0190) Nonlinear optics; (190.4400) Nonlinear optics materials; (160.4236) Nanomaterials.

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1. Introduction
The synthesis and the nonlinear optical response of nanosized materials are being intensively
studied due to their possible applications in electronic and medical science. Noble metal
nanoparticles, in particular Au and Ag, possess interesting optical properties, which are
determined by their shape (any variation from spherical form leads to the origin of new
properties [1]), size and environment. These systems have a broad absorption band in the visible
region of the electromagnetic spectrum, called surface plasmon resonance (SPR). The SPR
is consequence of the electromagnetic field-induced collective oscillation of free conduction
electrons, appearing in dierent phenomena as optical response for materials at dierent
scales [2], for example, surface enhanced Raman spectroscopy (SERS) [3], longitudinal SPR
(LSPR) sensors [4], metal-enhanced fluorescence, catalysis, among others [58]. The strong
coupling between light and SPR in nanostructures leads to transport and storage of energy [9].
In the surface plasmon absorption region, materials show large nonlinear optical absorption
coecients and ultrafast response [10].
Metal nanoparticles have close lying bands where electrons move quite freely. Oscillations
of free electrons in the conduction band occupying the energy states near the Fermi level give
rise to the SPR, which depends on both size and chemical surrounding of metal nanoparticles
[11]. Ag nanoparticles exhibit SPR into the UV-VIS region with an energy far enough from
the interband transition energy. This situation helps to investigate separately nonlinear optical
eects arising from interband transitions and those due to SPR [12,13], which have been used in
biomedicine, antibacterial activity, imaging and nanophotonics. There exist dierent methods
for the synthesis of nanostructures [14, 15], with which is possible to get nanoparticles of a
strictly defined shape and size, by example spheres, bars, octahedrons, pyramids, cubes, etc
[1620]. Dierent methods have been demonstrated for the synthesis of Ag nanocubes, among
them it can be highlighted the polyol method to obtain colloidal systems [21].
In general, the reaction occurs in solution. The solvents used are polyols, for example,
diethylene glycol (DEG) [22], ethylene glycol [18], among others. These are able to dissolve
inorganic compounds (AgNO3 ) and polymers, like poly(vinyl pyrrolidone) (PVP), due to their
high dielectric constant. They also play the role of reducing agents. The process involves the
reduction of an inorganic salt (the precursor) by polyol at an elevated temperature between
130 C and 160 C [18, 2022]. To prevent agglomeration of the colloidal particles, PVP is
commonly added as stabilizer and capping agent for this method, and others [8, 17, 20, 22, 24
29].
Ag nanocubes have received particular interest due to the large possibilities that their sharp
corners bring on LSPR and SERS applications; they are used as seeds with well-defined facets
for directing overgrowth [28], and as a sacrificial template to generate gold, palladium, and
platinum nanoboxes or nanocages [29]. Several studies have been developed with the objective
of investigating the nonlinear optical properties of this kind of systems [3032]. However, in
the race to find a suitable material for all-optical switching is necessary to study more deeply its
third-order nonlinear optical properties. In this direction, it is also necessary including the study
of non-locality of this nonlinear optical response.
The nonlocality is a generic feature of a large number of nonlinear optical systems. In the
spatial context, this nonlocality means that the response of the medium at a particular point
 Vol. 25, No. 25 | 11 Dec 2017 | OPTICS EXPRESS 31067

is not determinated solely by the wave intensity at that point (as in local media), but it also
depends on the wave intensity in its vicinity [33]. The nonlocal nature is characteristic of several
nonlinear optical systems involving heat transfer [34], drifting or electric charges [35], etc. The
third-order nonlocal nonlinear optical response has been previously patterned, numerical and
analytically, with good agreement with respect to experimental results [3638].
In this paper, we show the third-order nonlinear optical response from colloidal Ag nanocubes
synthetized by the polyol method, using PVP as capping agent for the Ag (100) surface and HCl
as etching agent. Three dierent samples with edge length of 56, 99 and 215 nm, respectively,
were obtained by this method. The nonlinear optical absorption and refraction responses were
measured by using the Z-scan technique, in open (OA) and close aperture (CA) configurations,
respectively [39]. Nonlinear optical excitation of these samples was achieved through laser
pulses of 26 ps, featuring a repetition rate of 10 Hz, at wavelengths of 355, 532 and 1064
nm, using increasing irradiances. The Z-scan data corresponding to excitation with 355 and 532
nm were fitted by using the Sheik-Bahae analytic expressions [39], while the data for 1064 nm
were better fitted by using the nonlocal model proposed in [36]. A comparative study between
the nonlinear optical absorption coecients, , and nonlinear refraction indexes, , obtained
from Sheik-Bahae analytical expressions and those obtained when using the nonlocal model
was done, in cases where it was possible. Finally, Stegeman figures of merit W (one photon)
and T (two photon) were calculated too.

2. Experimental section
2.1. Synthesis of Ag nanocubes
The silver nanocubes studied in this work were synthesized through the polyol method, but with
a small modification reported elsewhere [8, 18, 20, 22] and [29]. In a typical synthesis, ethylene
glycol (35 mL, EG, Sigma-Aldrich 324558) was added to a 250 mL round bottom flask and
heated under magnetic stirring (400 rpm), for 1 hour, in an oil bath preset to 140 C-145 C in
air. After this step, an HCl solution (411 L, 24.35 mM, HCl, Sigma-Aldrich 320331, in EG)
was added to the heated solution. 5 min later, a PVP solution was added (10 mL, 0.225 M in
terms of the monomeric unit, PVP, molecular weight,. 55,000, Sigma-Aldrich 856568, in EG).
After other 10 min, AgNO3 (15 mL, 0.1 M, Aldrich 209139, in EG) was added into the mixture.
This mixture was then allowed to react for periods of 24, 32 and 38 hours, in order to obtain
nanocubes of dierent sizes. For these reaction times, nanocubes with edge sizes of 56, 99, 215
nm, respectively, were obtained. The dierent samples were then washed, first with acetone and
then with an ethanol-acetone mix (1:9) and water several times, to remove most of the EG and
PVP by centrifugation. A set of three colloidal deionized water Ag nanocubes samples labelled
as S1, S2 and S3, with silver concentration of 0.378, 0.831 and 0.715 mg/mL, respectively, were
obtained.
The morphology of the samples was studied using field emission scanning electron
microscopy (SEM), with a JEOL JSM-7200F microscope. Figures 1(a)-1(c) show the images for
each sample. The micrographs were analyzed with ImageJ software; the edge length histograms
obtained from statistical analysis of, at least, 150 particles are shown in Figs. 1(d)-1(f). Accord-
ing to them, the edge lengths are 56, 99, and 215 nm, approximately for S1, S2, and S3 samples,
respectively. A characteristic parameter obtained simultaneously to the size of particle was the
polydispersity index; this index provides information about size dispersion of the sample: values
close to 0 indicate a monodisperse sample, while samples with a variety of sizes are identified
by values close to the unit. Table 1 summarizes the main characteristics of the samples.
 Vol. 25, No. 25 | 11 Dec 2017 | OPTICS EXPRESS 31068

Fig. 1. Scanning electron microscope (SEM) images of Ag nanocubes (a) S1, (b) S2, (c)
S3; (d), (e), and (f) show the corresponding edge length histograms.

Table 1. Nanocubes characteristic parameters.

Sample Edge Concentration Particles/mL Volume Polydispersity
Length (mg/mL) 1 1010 Fraction Index
(nm) f (1 10 5 )
S1 56.28 0.75 0.378 20.52 3.6 0.186
S2 99.48 2.51 0.831 8.17 7.9 0.254
S3 214.59 0.23 0.715 0.69 6.8 0.086

2.2. Optical measurements

Linear optical absorption measurements were performed using a Cary 5000 spectrometer. Each
sample was deposited into a quartz cell with thickness of 1 mm. Nonlinear optical measure-
ments were performed using the well-known Z-scan technique, which consists in focusing a
laser beam through a thin sample, while this moves along the optical axis. The transmittance
is monitored in the far field as a function of the sample position Z, in the vicinity of the focal
position of the used lens. Two configurations are possible in this technique, one is called close-
aperture (CA), in which a small aperture is placed in front of a detector, where the amount of
energy transmitted through the aperture will depend on the sample location in the z-axis and
on the sign of the nonlinear refraction index [42]. The other is called open-aperture (OA),
where all the transmitted light is collected, being then insensitive to any beam distortion due
to nonlinear refraction [43]. In our case, Z-scan setup was implemented using as light source
a PL2143A laser system by EKSPLA, featuring laser pulses of 26 ps, at a repetition rate of
10 Hz, with fundamental emission in 1064 nm, and second and third harmonics at 532 and
 Vol. 25, No. 25 | 11 Dec 2017 | OPTICS EXPRESS 31069

355 nm, respectively. The laser beam was separated by a 50/50 beam splitter, one part was
used as a reference beam to monitor stability and incident energy, while the other part was
focused by a positive lens featuring a f = 400 mm focal distance. The beam waist for each
wavelength was determined by the knife-edge method [44]. For each wavelength, waist and its
corresponding Rayleigh length Z0 are shown in Table 2. For all the three wavelengths, the
thin medium condition is fulfilled since the same quartz cell of 1 mm thickness was used
in all the experiments. The reference and transmitted beams for CA and OA configurations
were registered using Thorlabs DET 10A fast photodiodes. An aperture of 25 mm in diameter
was used for CA setting. Since these photodiodes detect voltage, a 2 mV range around the
initial voltage detected was established for the reference detector, to allow the filtering of the
experimental data for values outside this range. Each point reported in Figs. 3-7 is the average
of 10 pulses within the selected voltage range.

Table 2. Beam parameters.

(nm) 0 (m) Z0 (cm)
355 25.31 0.78 0.550
532 35.20 0.97 0.732
1064 60.24 0.70 1.071

The Z-scan technique is generally used to study the third order nonlinear optical properties
of selected materials. This technique allows obtaining the nonlinear refraction index, , and
nonlinear absorption coecient, , which permits expressing the refraction index, n, and
coecient absorption, , as:

n = n0 + I (1)
= 0 + I , (2)

respectively, where I denotes the irradiance of the laser beam within the sample. The
characteristic CA and OA Z-scan curves are usually modeled by Sheik-Bahae et al model [39],
using the relationships (3) and (5) for CA and OA, respectively.
40 (z/Z0 )
T (z, 0 )  1 , (3)
[(z/Z0 ) 2 + 9][(z/Z0 ) 2 + 1]
where 0 is the change of phase induced by the sample, which is given by the following
equation
2
0 =I0 L e f f . (4)

For the OA configuration, the transmittance is expressed as


[q0 (z, 0)]n
T (z, S = 1) = , (5)
n=0
(n + 1) 3/2
 
I0 L e f f 
which is valid if the condition |q0 | =  1+(z/Z 2  < 1 is fulfilled, with L e f f =
1e L
and L the
0)
sample thickness.
In this work, values for and coecients were obtained mainly from data fitting using
Sheik-Bahae expressions (3) and (5), when it was possible. In the opposite case, fitting was
done using the numerical model reported by Garca Ramrez et al [36], for nonlinear refractive
media, and the extension of this model to include nonlinear absorption, reported by Martnez
 Vol. 25, No. 25 | 11 Dec 2017 | OPTICS EXPRESS 31070

Irivas et al [37]. This model considers a Gaussian beam crossing a thin nonlinear optical media
in such a way that the output field is expressed by equation (6) [37] :
 
Eout = E(r, z)exp(0 L/2) 1 + qm (i (0 /0 )1/2) (6)
with
m/2
qm = 0 G loc (7)

 
2r 2
exp 2
G loc = , (8)
1 + (z/Z0 ) 2
and 0 = kI0 L e f f , 0 = I0 L e f f , with L e f f = (1 exp(0 L))/0 and I0 the maximum
intensity on the beam axis at focus.
The parameter m is a positive number that represents the nonlocality of the sample. It is
considered as a factor that aects the width of the Gaussian function described in equation
(8), which should correspond to incident intensity profile in the local case. The equation
(6) represents the local case when m = 2, meaning that it reproduces numerically curves
corresponding to equations (3) and (5). The numerical Z-scan curves for this nonlocal model
can be obtained from the electric field calculated with eq. (6) only if this field is translated, by
means of Fourier transform, to the far field, as is required by the Z-scan technique. A comparison
between the results obtained with both models is showed in subsection 3.3.

3. Results and discussion

3.1. Linear optical absorption
In general, the number of SPRs shown by a nanostructure is related to the particles morphology
and size, for example, spherical particles exhibit one peak, whereas for cubic particles the
optical absorption shows a more abundant structure, which is linked to its cubic symmetry.
R. Fuch found nine resonances but only six of them had significant strength [40]. It has been
also demonstrated that the location of the SPR is sensitive to the dielectic environment, for
media with refractive index n > 1 the spectrum is red-shifted with respect to vacuum [41].
Regarding to nanocubes, it was also observed that the vertices play an important role in the
optical response, since their sharpeness may increase the number of resonances [2]. For our
samples, the absorption spectra of S1 and S2 show three SPRs, while for S3, it shows four, see
Fig. 2.

Fig. 2. (a) Absorption spectra for the studied samples; the inset shows the spectrum of S3
on large scale, (b) SPRs position.
 Vol. 25, No. 25 | 11 Dec 2017 | OPTICS EXPRESS 31071

The most intense and most red-shifted SPR corresponds usually to a dipolar charge distribu-
tion, while SPRs less intense and less red-shifted are generally related to quadropole, octupole,
etc charge distributions. The red-shifting increases with size, as can be seen in figure 2 (b).
This shifting has a linear behavior, being more evident for the dipolar resonance, for which, in
these experiments, can be expressed by ma x = 1.47l + 373.3 (R2 = 0.9974), where l and
ma x are the nanocubes edge length and their resonance position, respectively. By using the
equation absor bance = 0 L log10 (e), with L being the sample thickness; linear absorption
coecients, 0 , were calculated from experimental data for each sample. Three coecients per
sample were calculated, one for each laser line, 355, 532 and 1064 nm, used on the nonlinear
optical measurements. The values obtained are shown in Table 3.

Table 3. Linear absorption coecients.

0 (cm 1 )
S1 S2 S3
Concentration (mg/mL)
(nm) 0.378 0.831 0.715
355 14.23 0.15 20.28 0.11 7.57 0.12
532 31.20 0.10 45.25 0.08 10.70 0.15
1064 0.69 0.09 6.40 0.12 9.55 0.12

3.2. Local nonlinear optical response at 355 and 532 nm

Before studying the nonlinear optical response of the samples, in order to be sure that the
measurements provided information about the Ag nanocubes only, Z-scan measurements of
the empty quartz cell and the cell filled with deionized water were performed. A negligible
nonlinear optical response was found in both cases, in agreement with what has been found by
Chatzikyriakos et al [45] for deionized water, and Aloukos et al [46] for distilled water. These
authors reported, for pulses in the ps regime and a repetition rate between 1-10 Hz, nonlinear
optical refraction for distilled water, at 532 nm and irradiances higher than 66 GW/cm2 ;
and nonlinear refraction and negligible nonlinear absorption above 80 GW/cm2 , at 1064 nm,
respectively.
Figure 3 shows only the characteristic OA Z-scan curves for 355 and 532 nm, for all the
samples, since the nonlinear refraction response was negligible at these wavelengths. As can be
observed in Fig. 3 for both wavelengths, during the scanning of the z position, as the sample
approaches the focal point of the laser beam, that is, as the irradiance increases to a maximum
at that point, the transmission increases too, denoting a saturation of the samples absorption.
This behavior is usually referred as saturable absorption. For both wavelengths this behavior
was observed, as shown in Fig. 3(a) for 532 nm and Fig. 3(b) for 355 nm, respectively. This
saturable absorption is attributed to ground state plasmon bleaching, due to intraband electron
excitation at moderate input intensities [47]. This kind of response depends on the proximity
of the used wavelength to the plasmon resonance. That is why, for this irradiance at 532 nm,
S2 shows the most intense response and S3 shows no response at all. For S1, the obtained
response at this irradiance was the highest for all the set of irradiances used for this sample at
this wavelength. For 355 nm, the obtained results are similar for all the used irradiances, only
S2 shows saturable absorption for this wavelength. From Fig. 2, this wavelength is quite close to
the octupolar resonance of S1 and S2, but the linear absorption coecient for S1 is quite lower
than for S2; for S3, this octupolar resonance is far enough to show any appreciable response at
this wavelength.
 Vol. 25, No. 25 | 11 Dec 2017 | OPTICS EXPRESS 31072

Fig. 3. Z-scan curves for Ag nanocubes: Nonlinear optical absorption for (a) = 532 nm,
with I0 = 1.24 GW/cm2 ; and (b) = 355 nm, with I0 = 4.15 GW/cm2 .

The noisy signals observed in Fig. 3 can be attributed either to laser unstability or to the
presence of scattering, especially for 355 nm and sample S3, since the nanoparticle size is
comparable to the incident wavelength. SEM images presented in the paper are in fact images
taken after the nonlinear measurements, thus showing no structural modifications or damage.
Besides, it is worth mentioning that after these studies, these samples were diluted in order
to perform nonlinear optical measurements at dierent nanoparticle concentrations, in order to
understand the relationship between nonlocality and samples density. Again, SEM images after
optical measurements showed no damage to the nanocubes structure. The obtained results will
be submitted for publication separately.
The dependence of the measured saturable absorption on irradiance is shown in Fig. 4 for
S2 at both wavelengths. In both cases, the nonlinear optical response increases with the
irradiance, independently of the resonance excited, dipolar or octupolar, respectively. For these
wavelengths, the nonlinear absorption coecients were obtained by fitting the obtained data
using the expression (5). They are summarized in Table 4.

Fig. 4. SA curves for sample S2 at dierent irradiances: (a) 532 nm, (b) 355 nm.
 Vol. 25, No. 25 | 11 Dec 2017 | OPTICS EXPRESS 31073

Table 4. coecients.
10 9
(cm/W)
= 355 nm = 532 nm
I0 S1 S2 I0 S1 S2
(GW/cm2 ) (GW/cm2 )
2.52 0.12 -2.15 0.07 1.24 0.11 -0.12 0.04 -0.28 0.04
4.15 0.21 -4.12 0.13 1.74 0.20 -0.26 0.02
5.20 0.18 -4.45 0.11 2.40 0.09 -0.25 0.02

3.3. Nonlocal nonlinear response at 1064 nm

In this section are shown the results corresponding to = 1064 nm. Only samples S2 and S3
exhibited any nonlinear response, since only these samples show a significant linear absorption
at this wavelength, being those for S3 the most relevant. Both samples exhibited saturable
absorption, as before, while only S3 showed positive nonlinear refraction. These nonlinear
optical responses were obtained using peak irradiances between 15 and 27 GW/cm2 . When
the nonlinear optical response presents a behavior where the measured curve is narrower than
the incident intensity profile, it is said that the induced nonlinear response in a given point
is nonlocal, that is, it depends on the incident intensity on a certain region around this point.
This behavior is illustrated in Fig. 5, where results corresponding to OA experiments, for S3 at
I0 = 23.33 GW/cm2 , are shown. When fitting the experimental data using equations (5) and (6)
under the same conditions, 0 = -0.35, with m = 2 for equation (6) (which corresponds to the
local case), it can be clearly seen that the experimental curve is much narrower than both fitting
curves. These fittings consider that the width of the incident intensity profile is the same as the
nonlinear response. Therefore, the only way to obtain an adequate fitting to the experimental
data is assuming a nonlocal response. Then, fitting again by using equation (6), with values of
m dierent from 2, as it is shown in Fig. 6, a better fitting was produced. A similar behavior was
obtained for CA measurements. E. V. Garca et al showed the analysis for CA experiments [36].

Fig. 5. Comparison between fittings obtained with equations (5) and (6) under same
conditions: 0 = -0.35, using m = 2, which corresponds to the local case. Experimental
results were obtained for sample S3 at I0 = 23.33 GW/cm2 (black dots).
 Vol. 25, No. 25 | 11 Dec 2017 | OPTICS EXPRESS 31074

Figure 6 (a) shows the experimental results mentioned above, but fitted by using the nonlocal
model for several values of m. It becomes clear how, by increasing the value of m, improves
data fitting since it leads to a narrowing of the calculated nonlinear response. Best fitting was
obtained for m = 5 and 0 = -0.35, which allows to obtain a nonlinear optical coecient with
a value of = 2.32 1010 cm/W. Figure 6 (b) shows CA results for S3, the best fitting
is also obtained using m = 5, as for OA measurements. In this case, the nonlinear phase shift
calculated is 0 = 0.81, which allows to obtain = 9.12 1013 cm2 /W. When increasing
the peak irradiance to 23.30 and 26.67 GW/cm2 , a similar behavior was observed. Figs. 6 (c)
and (d) show OA and CA results, respectively, at I0 = 26.67 GW/cm2 . It can be observed, again,
how the best fitting is obtained by using the nonlocal model. For this particular case, a value of
m = 5 was used too.

Fig. 6. Nonlinear optical response for S3 (black dots). (a) Saturable absorption, and (b)
positive nonlinear refraction, for I0 = 23.33 GW/cm2 . Fittings were obtained for dierent
values of m in equation (6). (c) Saturable absorption, and (d) positive nonlinear refraction,
for I0 = 26.67 GW/cm2 , with their corresponding nonlocal fittings.

Stegeman figures of merit for all-optical switching are defined as W = ||Is /0 and T =
| /|, where Is = 0 / is the saturation intensity. For a certain material to be used for this
purpose, it must satisfy both, W > 1 and T < 1. Although sample S3 does not satisfy these
conditions, it is important to mention that this sample presented a significant positive nonlinear
refraction, which is an atypical situation for colloidal systems, where thermal nonlinearities are
commonly observed. It is also relevant stressing that a value of m = 5 represents a decreasing
of approximately 43.8% for the width of the nonlinear response with respect of the incident
intensity profile. Therefore, the presence of nonlocal eects in this kind of systems can be
exploited for future applications. The nonlinear coecients , , and the Stegeman figures of
merit W (one photon), and T (two photon) for sample S3 are reported in Table 5.
 Vol. 25, No. 25 | 11 Dec 2017 | OPTICS EXPRESS 31075

Table 5. Nonlinear optical coecients and all-optical switching figures of merit for sample
S3 at 1064 nm.
I0 10 10 10 13 W T
GW/cm2 (cm/W) (cm2 /W)
20.36 0.17 -2.29 0.05 8.92 0.08 36.60 0.50 2.73 0.06
23.33 0.25 -2.32 0.09 9.12 0.09 36.88 0.47 2.71 0.10
26.67 0.42 -5.35 0.06 8.87 0.11 15.53 0.40 6.41 0.15

Regarding sample S2, it showed nonlinear optical absorption only for peak irradiances
smaller than 23 GW/cm2 , for higher irradiances the sample showed optical damage (no
nonlinear optical refraction was observed at all). Hence, this sample was studied at irradiances
of 15.56, 18.76 and 20.01 GW/cm2 . Figure 7 shows saturable absorption curves for the two first.
Fitting of the experimental data was performed by using again the nonlocal model, allowing to
obtain nonlinear coecients with values of = (2.69 0.1) 1010 , (3.24 0.09) 10 10 ,
and (3.44 0.12) 1010 cm/W, for 15.56 0.12, 18.76 0.15, and 20.01 0.18 GW/cm2 ,
respectively.

Fig. 7. Nonlinear optical response for S2 (black dots): Saturable absorption for (a) I0 =
15.56 GW/cm2 , and (b) I0 =18.76 GW/cm2 . Fittings were obtained using m = 5 in both
cases, with 0 = 0.31 for (a), and 0 = 0.45 for (b).

4. Conclusions
Three dierent colloidal systems containing Ag nanocubes with mean size of 56, 99 and 215
nm, with silver concentrations of 0.378, 0.831 and 0.610 mg/mL, respectively, were synthesized
using the polyol method. Their linear optical absorption clearly showed a very rich structure
featuring several maxima, corresponding to dierent multipolar contributions, as result of their
cubic shape and size increment. As size increased, a clear red-shift for the dipolar surface
plasmon resonance could be observed. Their nonlinear optical response was studied by using
the Z-scan technique for three dierent wavelengths at several peak irradiances. Samples with
sizes of 56 and 99 nm showed only saturable absorption at 355 and 532 nm, due to the closeness
of these wavelengths to their respective SPRs, in particular to the dipolar one for 532 nm. This
response increased with size and irradiance. For 1064 nm, only samples with size 99 and 215
nm showed a nonlinear optical response. Again, saturable absorption was observed for both
samples, but, for size of 215 nm, a positive nonlinear optical refraction could also be measured.
Although 1064 nm is quite far from the SPRs, for this last size, the linear optical absorption is
still very large. As for the other wavelengths, nonlinear optical response increased with size and
 Vol. 25, No. 25 | 11 Dec 2017 | OPTICS EXPRESS 31076

irradiance.
Experimental data for 355 and 532 could be fitted using Sheik-Bahae expression for
transmittance. This could not be done for 1064 nm, since a decreasing of the width of the
response was observed with respect to the incident intensity profile. For experimental curves
obtained with this wavelength, a nonlocal model had to be used, where its main parameter, m,
represents the spatial nonlocality of the nonlinear optical response. In general, the best fitting
was obtained using m = 5, meaning that the nonlinear phase shift after the sample, for the
nonlinear optical refraction, is narrower than the incident intensity distribution by a factor of
0.6. It can be noted that, when the incident wavelength is quite close to a SPR of the studied
system, no nonlinear optical refraction can be observed, and plasmonic eects can be associated
with local eects. On the other hand, for incident wavelengths far from resonance, nonlinear
refraction becomes measurable, as well as nonlocal eects.
From the calculated Stegeman figures of merit, these systems are not suitable candidates
for all-optical switching. However, their nonlocal behavior can be explored for possible
applications. Besides, the observation of a self-focusing eect, not associated to thermal eects
and opposite to the normal self-defocusing eect observed for colloidal systems, adds a very
interesting feature to this kind of systems.

Funding
Programa de Apoyo a Proyectos de Investigacin e Innovacin Tecnolgica (PAPIIT-
UNAM)(IN117116); Consejo Nacional de Ciencia y Tecnologa (CONACYT) (PhD. and
postdoctoral grants)

Acknowledgments
The authors thank Dr. Enrique Camarillo Garca for the use of Cary 5000, and Dr. Samuel
Tehuacanero Cuapa for his technical support in the acquisition of SEM micrographies within
Laboratorio Central de Microscopa facility at IF-UNAM.