Copper-containing Potassium-Alumina-Borate Glass
Structure and Nonlinear Optical Properties Correlation
Pavel Shirshnev
1
, Nikolaj Nikonorov
1
, Anastasija Babkina
1
, Alexander Kim
1
, Dmitrij Sobolev
1
,
Ivan Kislyakov
1,2
, Svjatoslav Povarov
1,2
, Inna Belousova
1,2
and Elena Kolobkova
1
1
Department of Optical Materials and Technology, ITMO University, Birzhevaya line 4, Saint-Petersburg, Russia
2
Laboratory of Laser Physics, Federal State Unitary Scientific and Industrial Corporation "Vavilov State Optical Institute",
Birzhevaya line 12, Saint-Petersburg, Russia
Keywords: Nanocrystalls, Nonlinear Optics, Glass Pottery.
Abstract: The paper describes the technology of obtaining potassium-alumina-borate glass with nanocrystalls of
copper chloride. Glass has transmission more than 75 % in visible range and nonlinear threshold less than
10
-5
Joules (at the wavelength of 532 nm). Such low threshold can be explained by special structure of
copper-containing nanophase in potassium-alumina-borate glass. In PAB glass low-melting temperatures of
nanophase induce nonlinear effects in optics. In phosphate glass copper ions and clusters are responsible for
optical nonlinearity.
1 INTRODUCTION
For the problems of photonics the special position
among transparent in visible range materials is taken
by crystal of copper chloride CuCl. CuCl is a wide
gap semiconductor, in which direct transitions of
electrons from the valence band to the conduction
band is allowed (Lucas, Cowley, McNally, 2008). It
has an extremely high exciton binding energy (190
meV), which allows to observe the exciton spectra at
room temperature and also at higher temperatures
(Efros, Onushchenko, Yekimov, 1985). The
excitonic absorption intensity in near-UV (384 nm)
is extremely high - more than 10
4
cm
-1
(Rivera,
Murray, Hoss, 1967; Cordona, 1963; Cowley, 2011).
Copper chloride has a high nonlinear optical
properties - due of two-photon absorption and of
radiation-induced changing of refractive index
(Yano, Goto, Itoh, 1996; Yasuaki, Makoto,
Hideyuki, 1988; Kondo et al, 2000; Ichimiya et al,
2009).
It's known that temperature of melting of a CuCl
is 426⁰C (Rivera, Murray, Hoss, 1967). CuCl has
one big disadvantage - it's hygroscopic (Lucas,
2008), that's why it's not easy to use it in practical
applications.
The solution of such problem is a formation of
nanocrystalls of copper chloride inside dielectric
matrix. The composite media based on dielectric
matrices with dispersed semiconductor nanoparticles
(glass pottery) have been extensively studied for
several decades. Copper chloride nanocrystalls was
grown in silicate glass host by metastable phase
separation (Dotsenko, Glebov, Tsekhomsky, 1998).
Usually such glasses are photochromic (Dotsenko,
Glebov, Tsekhomsky, 1998). Temperatures of
melting point of copper chloride nanocrystalls in this
glass are reached 380⁰C and of crystallization 200⁰C
(Onuschenko, Petrovskii, 1998; Valov, Leiman,
2009).
Potassium-alumina-borate glass host - is a
perspective host with high liquation ability (Imaoka,
Yamazaki, 1957; Kornilova, Petrovskii, Stepanov,
1980; Edelman et al, 2001). Copper chloride
nanocrystalls have been grown in potassium-
alumina-borate glass host (Nikonorov, Tsekhomsky,
Shirshnev, 2012) (PAB pottery). It was found, that
such glass pottery is non-photochromic (Nikonorov,
Tsekhomsky, Shirshnev, 2012). Also it was found,
that such glass pottery has optical nonlinear
properties (Kim et al, 2011). In (Golubkov et al,
2012) it was shown by small angle X-ray scatering
method (SAXS) that PAB pottery has a complicated
composition of nanophase which affects on melting
processes of nanocrystalls in glass. In (Babkina et al,
2014) it was shown, that copper clusters are formed
108
Shirshnev P., Nikonorov N., Babkina A., Kim A., Sobolev D., Kislyakov I., Povarov S., Belousova I. and Kolobkova E..
Copper-containing Potassium-Alumina-Borate Glass - Structure and Nonlinear Optical Properties Correlation.
DOI: 10.5220/0005339701080112
In Proceedings of the 3rd International Conference on Photonics, Optics and Laser Technology (PHOTOPTICS-2015), pages 108-112
ISBN: 978-989-758-092-5
Copyright
c
2015 SCITEPRESS (Science and Technology Publications, Lda.)
in PAB glass besides CuCl nanocrystalls which
affects in luminescence properties of glass pottery.
2 MATERIALS AND METHODS
In this paper three glass of different compositions
were synthesized. Glass with the content (mol %)
17,5K
2
O – 21Al
2
O
3
– 46B
2
O
3
– 8,9NaCl – 2,42Cu
2
O
– 0,23SnO
2
– 0,23Sb
2
O
3
-0,82Na
3
AlF
6
-2,9P
2
O
5
with
a glass transition temperature of about 380°C was
prepared as the basis for preparation of
halidecontaining glass crystalline materials. The
glass was synthesized in amounts of 100 g in a
corundum crucible with the use of a quartz stirrer at
a temperature of 1350°C for 2 h. To release
mechanical stresses, the annealing was conducted in
a stepwise regime, starting from 380°C (a fine
annealing according to the program for this glass). In
the following we denote it as glass 1.
In the second glass composition was (mol %):
20,12K
2
O – 24,14Al
2
O
3
– 52,89B
2
O
3
– 1,39Cu
2
O –
0,26 SnO
2
– 0,26Sb
2
O
3
-0,94Na
3
AlF
6
and 1 g of
C
12
H
22
O
11
. Conditions of synthesis were the same.
We denote it as glass 2.
Table 1: Properties of samples.
name of
sample
Glass host
Nanophase
type
details of
annealin
g
1 PAB CuCl
410°C
10 hours
2 PAB
copper-
containing
nanoclusters
Not
3 Phosphate CuCl Not
4 PAB No Not
The third one is (mol %) 20BaPO
3
- 5Na
3
AlF
6
-
70NaPO3 - 4CuCl - HCl. We denote it as glass 3. It
should be noted, that in this composition CuCl is in
“clear” form.
The glass transition temperatures were
determined on a differential scanning calorimeter
STA 6000 (Perkin Elmer) and were 380°C for all
samples.
The glass 1 sample were subjected to repeated
heat treatment at 410°C for 10 h.
The absorption spectra of glass were measured
by spectrophotometer Perkin Elmer Lambda 600.
Luminescence was measured by LS-11 Perkin Elmer
Spectrafluorimeter.
It should be noted, that measuring of absorption
spectra during heating - is a very effective method
for processes studying of melting and crystallization
in a copper chloride containing glass pottery
(Rivera, 1967). Scheme of experimental setup is in
figure 1. In this work avantes spectrometer Avaspec-
1028 UV-VIS and balanced halogen-deiterium lamp
was used. The measurement setup scheme is
vertically designed.
The scheme of experimental setup of nonlinear
optics characteristics studying is shown in figure 2.
The laser beam is divided on two beams. The first is
the reference beam, another one is directed to the
sample and after to the photodetector. An energy of
laser beam is varied by a system of filters from 10
-9
J
till 3х10
-2
J. This range is achieved by using two
casette filters with a total transmittance range from
10
-9
till 100%. The laser wavelength was 532,1 nm,
pulse length was 5x10
-9
seconds. All measurements
was made in focused beam.
Spectra and nonlinear properties were measured
on samples with thickness 2 mm, thermal
measurements were made on samples with thickness
0,1 mm.
Figure 1: An experimental setup for absorption
measurements: 1 – digital thermometer, 2,3 – heat
controller, 4,5 - fiber spectrometer, 6,7 - deuterium lamp,
8 – thermal sensor, 9 – sample, 10 – quartz glass plate, 11
– cooling of thermocell.
Figure 2: An experimental setup of nonlinear optical
characteristics studying: 1 - laser, 2,3 - lenses, 4, 9 -
photodetectors, 5,8 - blok of filters, 6 - sample, 7 -
diaphragms, 10 - half-transmittable mirror.
Copper-containingPotassium-Alumina-BorateGlass-StructureandNonlinearOpticalPropertiesCorrelation
109
3 RESULTS
3.1 Spectra of Optical Absorption
Spectra of absorption of glasses 1-3 are presented on
the figure 3. Figure 3 shows absorption band are at
365-384 nm in glass 1 and 3. This band was
identified as CuCl excitonic absorption (Dotsenko,
1998). There is no absorption at this wavelength
range for the glass 2, even after heat treatment.
3.2 Spectra of Photoluminescence
Spectra of luminescence was measured for glasses 1-
3 (figure 4). The excitation wavelength is 365 nm.
From the figure 4 one can see that the luminescence
of glasses 2-3 is identical. For the glass 1 the
luminescence is not observed.
Figure 3: Spectra of optical absorption of glasses 1-3
(digits in figure the same as number of glasses).
Figure 4: Spectra of photoluminescence for glass 1-3
(digits are the same as numbers of glasses).
3.3 Thermal Excitonic Spectroscopy
The dependence of excitonic absorption on
temperature (glasses 1,3) is given in the figure 5 (the
thickness of samples 0,1 mm). As it can be seen, the
temperature of excitone destruction for glasses 1 and
3 is really different (the difference is more than
200
ο
C).
3.4 Nonlinear Properties Results
The dependence of optical transmission on energy of
pulse for glasses 1-3 is shown in figure 6. It can be
seen, that for the blank glass 1 there is no nonlinear
effects. Nonlinear absorption characteristics of
glasses 2 and 3 are the same, and the strongest effect
is obtained on glass 1 (copper chloride containing
PAB glass).
Figure 5: Excitonic absorption intensity of glass 1,3 at
different temperatures.
Figure 6: Nonlinear optical limiting on different samples
(thickness of glass 2 mm): 1 – glass 1, 2 – glass 2, 3 –
glass 3, 4 – blank (without CuCl) glass 1. Arrow shows
the starting point of optical limiting process.
4 DISCUSSION
Let’s discuss figure 5. As mentioned above, first
glass had the lowest threshold of nonlinear limitting,
first glass without nanocrystalls had the highest one.
PHOTOPTICS2015-InternationalConferenceonPhotonics,OpticsandLaserTechnology
110
As we can see from absorption spectra of glass 3
(figure 3) nanocrystalls of copper chloride were
formed in glass. The relative concentration of CuCl
in glass 1 and 3 can be estimated by absorption
spectra intensity. So, for the glass 3 it’s two times
more than for the glass1. So, we can say that the
concentration of CuCl in sample 3 it’s two times
more than for the sample 1, but the strongest
nonlinear optical limitting effect is in glass 1. Why?
Let’s discuss the figure 5. The temperature of full
disappearing of excitone in glass 1 is less than
150
ο
C, for glass 3 it’s 420
ο
C. It was shown in
(Golubkov et al, 2012), that there are two
characteristic temperatures of nanophase melting in
PAB glass. One of that melting points is near 150
ο
C
another one is at 270
ο
C. So, if we compare processes
of nanophase melting in PAB glass with similar
phenomena in silicate glasses with CuCl nanophase
(Dotsenko, Glebov, Tsekhomsky, 1998), we can say,
that temperature of excitone absorption disappearing
at 150
ο
C is the point of CuCl nanocrystalls melting
in glass 1. Point of CuCl melting in glass 3 is 361
ο
C.
It is known (Dotsenko, Glebov, Tsekhomsky, 1998;
Golubkov et al, 2012) that CuCl containing
nanophase can include another crystal components
which can affects on value of melting point of
nanophase. For CuCl-KCl eutectics such
temperatures can be 150⁰C. So, in glass 3 CuCl
nanophase can be “clear” and in glass 1 – nanophase
can contain mixed eutectic crystals of CuCl and
K
2
CuCl
3
.
The phase transition in such heterogeneous
material as a PAB glass with CuCl nanocrystalls can
induce the optical limiting effect because of
difference of refraction index of liquid CuCl-KCl
solution and glass host. Also, the melting of
nanophase can induce the growth of scattering and
growth of optical absorption in visible range
(including 532 nm).
In figure 5 the curves for glass 3 and 2 are
identical. That could be mean, that the mechanisms
of nonlinear limiting are the same in this glasses. As
it shown in figure 4, the luminescence bands in glass
2 and 3 are the same. We suggested that glass 2 and
3 has Cu
+
ions and (maybe) Cu
0
n
clusters after
comparing luminescence spectra with spectral
luminescence data at (Babkina et al, 2014). In the
article (Qiaohong et al, 2009) authors has shown that
metal clusters in glass can induce nonlinear optical
effects.
5 CONCLUSIONS
The new material with low-limit optical threshold
was synthesized – a PAB glass with copper chloride
nanocrystalls. Numerical value of threshold was
5x10
-6
Joules. This threshold is due of special
structure of nanophase of such glass, which contains
CuCl and K
2
CuCl
3
nanocrystalls. Such complicated
structure of nanophase gives low points of melting
of nanophase. That’s why during laser irradiation of
PAB-glass phase is melting and that’s induces the
appearance of additional color centers in glass.
It was shown that copper clusters also induce
nonlinear effects.
ACKNOWLEDGEMENTS
This work was financially supported by Russian
Scientific Foundation (Agreement # 14-23-00136).
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