CHIN. PHYS. LETT. Vol. 28, No.

11 (2011) 116101

Optical Limiting Properties of Ag-Cu Metal Alloy Nanoparticles Analysis by

using MATLAB *
WANG Yu-Hua()1** , LI Hui-Qing()2 , LU Jian-Duo()1 , WANG Ru-Wu()1
1

Key Laboratory for Ferrous Metallurgy and Resources Utilization of Ministry of Education, and Department of
Applied Physics, Wuhan University of Science and Technology, Wuhan 430081
2
Department of Endocrinology, Union Hospital, Tongji Medical College, Huazhong University of Science and
Technology, Wuhan 430022

(Received 6 June 2011)

Ag-Cu alloy nanoparticles were formed by sequential ion implantation (Ag and Cu) in silica using a metal vapor
vacuum arc (MEVVA) ion source. Third-order nonlinear optical properties of the nanoparticles were measured
at 1064 nm excitations using the Z-scan technique. Curve fitting analysis, based on the MATLAB features for
Ag-Cu alloy nanoparticle optical limiting experiments, is used. The results show that Ag-Cu alloy nanoparticles
display a refractive optical limiting effect at 1064 nm.

PACS: 61.46.+W, 61.72.Ww, 42.65.K

DOI:10.1088/0256-307X/28/11/116101

Recently, increasing attention has been focused

on the third-order nonlinear susceptibility and the
photorefractive effect of noble-metal clusters embedded in dielectric matrices.[13] Third-order nonlinearities of metal/dielectric composite materials are influenced not only by the type and size of the embedded metal clusters, but also by the dielectric constant,
thermal conductivity and heat capacity of the dielectric matrices.[46] Amongst the nanoparticles studied
earlier, high nonlinear absorption and nonlinear refraction coefficients were found in copper and copper
containing nanomaterials.[7,8] For silver, the nonlinear
refractive index changes from positive to negative
upon the growth of clusters.[9] Potential applications
of optical limiters in the protection of sensors from intense laser pulses have motivated great efforts to design new nonlinear optical systems.[10]
Ion implantation has been utilized to produce
high-density metal colloids in glass. The high precipitate volume fraction and the small size of nanoparticles in glass lead to a third-order susceptibility
greater than those for the corresponding metal-doped
solid. The third-order nonlinear optical responses of
the metal-nanoparticle-glass composites can be understood from the framework of dielectric and quantum confinement effects. The optical nonlinearities
and limiting effects of the nanocomposites with metal
nanoparticles can be significantly enhanced by increasing the number density and the size of metal
particles.[11] The application aspects of materials are
closely related to the change of optical properties versus the nanoparticle structure.
Currently, optical limiting results are obtained
through the analysis of experiments, including the

completion of specific research tasks. Engineers and

technicians drawings are usually analyzed using auxiliary tools, such as MicroCal Origin, Microsoft Excel,
and so on. Although these analysis tools supplement
various experimental results, all of them are in the
form of direct application software, which is not comprehensive enough to fit curves, and some limitations
therefore still remain in the analysis of experimental
data.
MATLAB incorporates science, engineering calculations and visual figure functions, and has a Windows interface design method. It has a stronger operating ability, powerful and intelligent mapping, and
higher programming efficiency; in particular, it can
be used for application development in this field. In
our previous work, the optical limiting properties of
Ag/Cu and Cu/Ag mixture nanoparticles have been
studied.[12,13] In this Letter, Ag-Cu alloy nanoparticles were prepared by Ag/Cu sequential ion implantation into silica using a MEVVA source implanter
according to the experimental protocol. We focus our
interest on studying the nonlinear optical properties
and optical limiting properties of this kind of metal
alloy nanoparticle.
Silica slides were sequentially implanted with 5
1016 Ag+ ions/cm2 and 5 1016 Cu+ ions/cm2 using a MEVVA source implanter at room temperature.
The acceleration voltages of 43 kV for Ag and 30 kV
for Cu, respectively, were chosen to reach the same
projected range for the implanted species. The flux
density was 2 mA/cm2 . Optical absorption spectra
were recorded at room temperature using a UV-VIS
dual-beam spectrophotometer with wavelengths from
900 nm to 200 nm. The measurements of the third-

* Supported

by the National Natural Science Foundation of China under grant(Nos 10805035 and No.11191240126).
author. Email: wyh61@163.com
Contributed equally to this work.
c 2011 Chinese Physical Society and IOP Publishing Ltd

** Corresponding

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CHIN. PHYS. LETT. Vol. 28, No. 11 (2011) 116101

order optical nonlinearities of the sample were carried

out using the standard Z-scan method. The excitation source is a mode-locked Nd:YAG laser (PY61-10,
Continuum) with a pulse duration of 38 ps and a repetition frequency of 10 Hz. The 1064 nm wavelength
is used for excitation in the experiment. The detector
is a dualchannel energy meter (EPM2000). It has a
converging lens of = 260 mm and the radius of the
Gaussian beam spot at focal waist 0 is 44.7 m. In
the Z-scan test, the sample was moved step by step
along the propagation direction of the Gaussian beam
under the control of a computer. Meanwhile, a detector was used to monitor the transmitted laser power
and the signals were sent back to the computer to
be recorded. Nonlinear refraction and nonlinear absorption were performed by both open- and closedaperture Z-scans of a series of the samples at room
temperature.
0.9
0.8

Ag

Optical density

0.7
0.6
0.5

Ag-Cu

0.4
0.3
0.2

Cu

0.1
0.0
300

400

500

600

700

800

Wavelength (nm)

Normalized transmittance

Fig. 1. Optical density vs wavelength for the Ag/Cu sequentially implanted sample with Ag 5 1016 and Cu
5 1016 ions/cm2 , Ag implanted sample with a dose of
1 1017 ions/cm2 and Cu implanted silica with a dose of
1 1017 ions/cm2 .

1.4
1.2
1.0
0.8
0.6
1.4

() =

(b)

(mm)

10

20

[0 ()]
,
(1 + 2 ) ( + 1)3/2
=0

40
() = 1 + 2
,
( + 9)(2 + 1)

Experiment
Theoritical fit

(a)

1.2
1.0
0.8
0.6 -30 -20 -10

Figure 1 shows the optical absorption spectra of

Ag/Cu sequentially implanted samples. For comparison, the optical absorption spectra of the Ag implanted sample with a dose of 1 1017 ions/cm2 at
an energy of 90 keV and Cu implanted sample with
a dose of 1 1017 ions/cm2 at energy of 60 keV are
also shown in the figure. The surface plasmon resonance (SPR) peak position is 442 nm for the sample
AgCu1:1, which lies between those of pure Ag and Cu
nanoparticles (about 400 and 570 nm, respectively).
Our previous work[14] has shown that intermetallic
Ag-Cu alloy nanoparticles can be formed instead of
two separated Ag and Cu nanoparticles.
The difference between the formed Ag-Cu alloy
nanoparticles and the Ag-Cu mixture nanoparticles
lies in different methods of ion implantation. In
this study, the implantation of Ag and Cu was carried out by using a MEVVA source ion implanter.
The MEVVA ion source is a high-current metal-ion
source. The ion flux densities for both elements are
2 mA/cm2 , which is much larger than those in the previous work.[12] In that work, the flux densities of Ag
and Cu ions were 1 A/cm2 and 1.5 A/cm2 , respectively. The alloy formation is related to the enhanced
diffusion of Cu in small Ag clusters, just like adding
Cu to Ag by the heat generated from the implantation
that gives rise to high local temperatures.[15]
The third-order nonlinear absorption and refraction are investigated by Z-scan techniques.[16] This
technique is simple and sensitive for studying nonlinear optical properties and determining the sign of the
nonlinear refractive and absorption indices. The openand closed-aperture Z-scan curves are theoretically fitted by[16]

30

Fig. 2. Normalized transmitance with closed-aperture

(a) and open-aperture (b) Z-scan experiment results at
1064 nm. Solid line: theoretical curve.

( 0)
(1)
(2)

where = /0 , is the normalized transmittance

and is the distance along the lens axis in the far
field. The nonlinear refractive index is calculated by
0 = (2/)0 eff . Here, 2/ is the wave vector
of the incident laser, 0 is the intensity of the laser
beam at the focus ( = 0), eff is the effective thickness of the sample, which can be calculated from the
real thickness and the linear absorption coefficient
0 , in the form of eff = [1 exp(0 )]/0 .
The third-order nonlinear optical property of the
sample was measured at 1064 nm. If the samples
possess nonlinear absorptive properties, the closedaperture transmittance should be affected by the nonlinear refraction and absorption. The determination
of is less straightforward from the closed-aperture
scans. It is necessary to separate the effect of nonlin-

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CHIN. PHYS. LETT. Vol. 28, No. 11 (2011) 116101

(3)

Re(3) = 220 0 ,

(4)

Thus, the obtained absolute value of (3) is

3.5107 esu for 1064 nm.
We perform curve-fitting analysis for the optical
limit experimental results using MATLAB. According to the experimental data obtained for the AgCu nanoparticles we apply the index regression curvefitting method to obtain the fitting procedure as follows:
x=[a:T:b];
y=[]; here [] is the output data of Z-scan
X=[ones(size(x)) exp(-x) x.*exp(-x)];
a=Xy;
Y=[ones(size(x)) exp(-x) x.*exp(-x)]*a;
plot(x,y,*,x,Y,-)
title(Alloy 1 index regression curve );
xlabel(Input laser intensity );
ylabel(Output laser intensity );
legend(Discrete points ,Index regression curve )
In this program, and are the initial value and
the final value, respectively, is the difference between the two values, (, ) are the data points of
the Z-scan. The valid data from the experiments are
shown in the program. The unit of laser intensity is
mJ/cm2 . The experimental data and the curve-fitting
result are shown in Fig. 3.
From Fig. 3, we can see that the fitting is not in
good agreement with the most experiment data, but
it reflects the trend of optical limiting properties of
the sample, implying that this kind of nanoparticle
possesses good limiting performance.
In order to obtain a fitting curve closer to the
experimental data, we apply the least square curve-

30

Output (mJ/cm2)

= 0.406(1 )0.25 |0 |,

fitting method to determine a value for the shape factor and the procedure is as follows:
Program Ag-Cu.m
x=[a:T:b];
y= []; here [] is the output data of Z-scan
x1=a:b;
p=polyfit(x,y,n);
y1=polyval(p,x1);
plot (x,y,,x1,y1,-r);
title(Alloy 1 polynomial fitting curve );
xlabel(Input laser intensity );
ylabel(Output laser intensity );
legend(Discrete points ,n fitting curve);
grid on;
In this program, refers to the order of the polynomial. The valid data from the experiments are shown
in the program. Now, we choose = 3, 5, 8, 12,
respectively, running the program, as shown Fig. 4

25
20
15
10
5

Discrete points
Index regession curve

0
-5
5

10

15

20

25

30

Input (mJ/cm2)
Fig. 3.
curve.

Ag-Cu alloy nanoparticless index regression

30
25

Output (mJ/cm2)

ear absorption by closed/open-aperture. The experimental results of the Z-scan for Ag-Cu alloy nanoparticles are shown in Fig. 2. The open-aperture Z-scan
(b) shows no nonlinear signal, which indicates that
the sample has no nonlinear absorption at 1064 nm.
The peak-valley configuration in Fig. 2(a) indicates
the negative sign of the nonlinear refractive index
(<
2 0). A self-defocusing refraction is verified from
the peak-valley curve of the closed-aperture data. It
is considered to come from the optical Kerr effect. The
nonlinear property of the bare silica substrate was also
measured and it shows no detectable change of the
transmitted intensity under the same Z-scan conditions.
In our experiments, eff (nm) for the sample is
60 nm. The peak intensity of 0.38 GW/cm2 is selected
for the sample. Fitting the Z-scan data of the closedaperture with Eq. (2), we obtain 0.34 cm2 /GW
for 1064 nm. The absolute value of third-order nonlinear susceptibility (3) for the sample is calculated
using the equations[16,17]

20
15
10

Discrete points
Third-order fitting curve
Fifth-order fitting curve
Eighth-order fitting curve
Twelfth-order fitting curve

5
0

10

15

20

25

30

Input (mJ/cm2)
Fig. 4. Ag-Cu alloy nanoparticless least square curvefitting method analysis.

In Fig. 4, we can see that = 3 or = 5 is not a

good fit, especially in the first half of the data. Compared with = 3 or 5, = 8 or 12 largely identical but with minor differences, all basically reflect
optical limiting characteristic of the sample. In fact,
we know the polynomial fitting is based on the least
square method. If the data does not have binomial
characteristics, we will find that the curve can produce
a big backlash, despite this method being very attractive. This phenomenon is called the polynomial swing.

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CHIN. PHYS. LETT. Vol. 28, No. 11 (2011) 116101

It is more likely to happen in high order polynomial

cases. For this reason, we rarely used more than a 6order polynomial, unless the polynomial we used was
real polynomial. Generally, we choose = 3 or = 5.
Here, because the amount of data is not very large,
the regularity is good. Considering the computer running time, the curve fitting accuracy, smoothness and
so on, we choose = 8. We can see that the fitting
sample image output values increase with the increase
of . However, the rate of increase of the output value
is gradually reduced to zero and there is a drop in the
curve tail section. The fitting curve aligns well with
the optical limiting characteristics of the curve, indicating that Ag-Cu alloy nanoparticles play a part in
the optical limiting effect.
In summary, Ag-Cu alloy nanoparticles exhibit interesting nonlinear optical properties and optical limiting properties. The analysis methods from MATLAB we choose in this study are different from the
previous work.[12] Here we apply the index regression
curve-fitting method to obtain the fitting procedure,
which reflects the trend of optical limiting properties
of the sample. Then, we apply the least square curvefitting method to determine the values for the shape
factor. Comparing the different orders of the polynomial, we find that = 8 can fit well with the experimental results. As far as the samples optical limiting
character and its physical origin, we think that the
optical limiting character of the sample comes from
the optical Kerr effect. Because there is no nonlinear absorption at 1064 nm, the nonlinear refraction
plays the whole role on the optical limiting character
of these kinds of samples.
In this study, metal alloy nanoparticles in silica
have been synthesized by sequential ion implantation
of Ag and Cu ions using MEVVA. We report the experimental observations of the nonlinear optical responses of Ag-Cu alloy nanoparticles using picosecond
laser pulses. For 1064 nm excitation, the sample has
no nonlinear absorption and the nonlinear susceptibil-

ity (3) is 3.5 107 esu, which arises from the nonlinear refraction contribution. Moreover, the optical limiting effect at 1064 nm is also observed. We apply the
index regression analysis and the least square curvefitting method analysis by using MATLAB software.
Basically, the curve-fitting reflects that the sample has
an optical limiting property at the near-infra-red field.
MATLAB is effective for the study of optical limits of
materials and further studies are in progress.

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