Physical and Optical Study of Nd2O3 Doped Sodium Borosilicate

Glasses

V. Y. Ganvir a, * , H. V. Ganvir a , R. S. Gedam b

a
Department of Applied Physics, Yeshwantrao Chavan College of Engineering, Nagpur -
441110, (India)

b
Department of Physics, Visvesvaraya National Institute of Technology, Nagpur -
440010, (India)
*
Corresponding Author’s Email ID : vyganvir@gmail.com

Abstract :

In the present work, normal melt-quenching process was used to prepare Nd2O3
sodium borosilicate glasses. The synthesized glassy samples were investigated using various
characterization techniques like XRD analysis, FTIR spectroscopy, density analysis,
absorption and photoluminescence spectroscopy measurements. XRD spectra demonstrated
the amorphous existence in the studied glasses. The stretching and bending vibrations of
various borate groups were identified using FTIR analysis. The high molecular weight of
Nd2O3 and the broader ionic radius of Nd3+ ions resulted the rise in molar volume (Vm) and
density (ρ) with inclusion of Nd2O3. Optical band gap found to reduce as the concentration
of Nd3+ ions rises. The intensity of Nd3+ emission spectra increased from 0.5 mol per cent to
1.0 mol per cent with Nd2O3 material and the concentration of quenching was reported at
concentrations higher than 1.0 mol percent. The emission spectra of the synthesised glass
shows three notable peaks found at 902 nm (4F3/2→4I9/2), 1063 nm (4F3/2→4I11/2) and 1334 nm
4
F3/2→4I13/2 of Nd3+ ions transitions.

Keywords: Optical properties, Concentration quenching, Borosilicate Glasses, Band gap,

Density

1. Introduction

Recent studies have centered on rare earth oxide-doped glasses because of their
versatile applications in the field of laser, optical amplifiers, sensors, display devices, light
emitting diodes etc. [1-2]. Also the optical properties of REO doped glass materials play very
important role in the progress of glass lasers as well as in the production of variety of optical
fibers and filter glasses [3].

A comprehensive investigation on REO-doped glasses is necessary due to their variety

of applications in optical storage devices, immobilization of radioactive waste materials,
laser technology and optical communications [4-5]. Among different rare earth, neodymium
oxide is one of the most studied rare earth ion and is found to have huge applications in
photonic devices [3-4,6-8]. Neodymium doped glassy materials are continuously fascinating
to scientist and researchers due to their extensive applications as laser materials and
luminescent solar concentrators [9]. Moreover, a high transmission in the UV and low
exposure to defect formation entitle sodium borosilicate glasses as a very appropriate host
material for high performance optics [10].

Due to wide applications and advantages of neodymium doped glasses, it is quite

exciting to investigate the influence of Nd2O3 doping on sodium borosilicate glasses to
examine their potential use as a laser medium. So in present work, we discuss in-depth
analysis of various physical and optical properties of Nd 2O3 doped sodium borosilicate
glasses.

2. Experimental

The glass formulations used in the current work ‘30Na2O-(70-x) {1/7 SiO2 : 6/7 B2O3} – x
Nd2O3’ was prepared with normal melt quenching process where 'x' ranged from 0 to 2
in the stage of 0.5 mol percentage. High purity preliminary raw materials such as SiO 2,
Na2CO3, B2O3 and Nd2O3 ( Purity Quality greater than 99.9 per cent of make E-MERCK)
were used for sample preparations. These additives were thoroughly blended in acetone for
around 1 hour in adequate amounts and then this mixture was kept for 3 hours in a crucible
made of platinum in an electric furnace at 1223-1273 K. Then this hot melt was poured into
an aluminium moulding at normal temperature to obtain the desired form of the bulk glass
samples. Then immediately, these quenched bulk glasses were shifted to furnace at 590 K for
three hours. This facilitates in the dissipation of thermal stress caused by quenching and then
holding it for cooling till room temperature. The designation of samples along with their
composition variation is listed in table 1.

Table 1 : Compositions of the glass samples of prepared glasses

 Sample code Na2CO3 B2O3 SiO2 Nd2O3
0 BSNA 30 60 10 0
0.5 BSNAND 30 59.57 9.93 0.5
1.0 BSNAND 30 59.14 9.86 1
1.5 BSNAND 30 58.71 9.79 1.5
2.0 BSNAND 30 58.29 9.71 2

X-ray diffractograms of the synthesised glass specimens were recorded using X'pert pro-
PANalytical. The FTIR spectrum was reported by a Perkin Elmer spectrometer in the region
450-2000 cm-1. The SHIMADZU SMK-401 density measuring instruments (Archimedes
principle based) was employed to estimate the density of studied glass samples with toluene
as dipping solvent.
The glasses were crushed in the fine powder form for photoluminescence study. The
luminescence and excitation spectra of the glass samples were performed using a JASCO-FP-
8200 fluorescence spectrometer. The optical absorption spectrum was recorded at room
temperature using the JASCO V-670 Spectrometer..

3. Results and Discussion

The X-ray diffraction (XRD) spectrum of as-prepared glasses is shown in Figure 1. This
X-ray spectra comprises the wide humps and there is lack of any prominent peaks related
to any of the constituent components. This confirms that the prepared glass materials are
amorphous.
Figure 1 : X-ray diffraction (XRD) spectra of sodium borosilicate glasses doped with
Nd2O3

The FTIR spectra of Nd2O3 doped sodium borosilicate glasses are shown in figure 2. The 460
cm-1 band refers to B-O-Si stretching and Si–O–Si and O–Si–O bending. The Si-O-Si
stretching vibration is assigned to the 701 cm-1 band. [4,11]. The band present about 819 cm-1
is associated with the vibration of the B-O bond in the BO4 unit. The band at 943 cm-1 is
assigned to the B-O bond stretching in the di borate functional unit [4,11]. The stretching
modes of tetrahedral boron are responsible for the weak band that emerged at 1121

cm-1.
The band at 819 cm-1 shifts little bit towards the lower wave number side, while the band at
1121 cm-1 switches slightly to the higher wave number side. This change in the bands
position affirms the structural changes and development of BO4 units [4,11]. Thus from this
spectra, the presence of tetrahedra is confirmed by observed bands for Nd2O3 doped
sodium borosilicate glasses [4,11].
 Figure 2 : FTIR spectra of Nd2O3 containing sodium borosilicate glasses

Figure 3 depicts the variation molar volume (Vm) and density (ρ) for Nd2O3 comprising

studied glasses. The molar volume (Vm) and density increases with increasing Nd2O3

material, as seen in this graph. The relatively high molecular weight of Nd2O3 than other

additives (Molecular weight of Nd2O3 is 336.48 gm/mol, Na2CO3=105.9888 g/mol , SiO2=

60.08 g/mol, B2O3= 69.63 g/mol ) and a larger Nd3+ ion radius are responsible for the rise in

molar volume and density This large radius of Nd3+ ion causes expansion of glassy

structures thereby increasing the molar volume. Also Nd3+ ions are fitted to the voids

connected with the units that open the glassy structure. These findings are reasonably

compatible with the published results, where molar volume and glass density increase with

REOs [12-13]. In addition to this, different physical parameters like neodymium ions

concentration (N), molar volume (Vm), polaron radius (rp), field strength (F) and inter nuclear

distance (ri) were determined using the density values. These physical parameters were

estimated using standard formulae [12-14]. The physical parameters perform a trivial role in
clarifying atomic arrangements in the glass network and provide useful knowledge

regarding glass structure [11-15].

Figure 3 : Variation of density and molar volume of Nd2O3 doped sodium

borosilicate glasses

Tables 2 represent the physical parameter values obtained for the studied glass system. It is
found that with rise in Nd3+ ions, polaron radius (rp) and inter-nuclear distance (ri) values
declines. Reduction in ri and rp values indicates an improvement in Nd-O bond power, which
increases overall field strength (F) around Nd3+ ions. These physical parameter values
reinforce the density findings and the compactness of glass construction with the rise of Nd 3+
ions.

Table 2 : Properties of sodium borosilicate glasses containing Nd2O3

X mol % Unit 0 0.5 1 1.5 2

ρ (g/cm3) 2.4086 2.4215 2.5131 2.5233 2.5394
Vm (cm3) 27.5569 27.719 27.8989 28.250 28.500
3 1 1
(N) ( × 1022 ) (ions/cm3) - 1.0769 2.1919 3.2383 4.2641
ri (Å) - 4.5283 3.5732 3.1373 2.8624
rp (Å) - 1.8246 1.4398 1.2641 1.1533
(F) ( × 1017) (cm-2) - 1.8023 2.8945 3.7547 4.5107
 Figure 4 illustrates the optical absorption spectra of studied glass system carried at
room temperature and its assignment of different absorption bands. This spectra indicates
that Nd3+-containing glasses display a variety of absorption bands in contrast to base glass. It
is also noted that the absorbance increases with the addition of Nd2O3. The various bands
found in the absorption spectra are 1) 350 nm (2I11/2) , 2) 356 nm (4D3/2) , 3) 430 nm (2P1/2) ,
4) 474 nm (2G9/2), 5) 511 nm (4G9/2) , 6) 524 nm (4G7/2 ) , 7) 583 nm (4G5/2), 8) 625 nm (2H11/2)
, 9) 680 nm (4F9/2) , 10) 746 nm (4S3/2 + 4F5/2) , 11) 803 nm (4F5/2) and 12) 873 nm (4F3/2) .
These bands were identified by contrasting their energy to that of Carnall et al.[16] and those
reported in the literature[17-19].

Figure 4: Room Temperature optical absorption spectra of studied glasses

It is obvious from this figure that the absorption edge is not precisely and sharply established
for all glasses due to its amorphous existence. The optical edges provide valuable knowledge
pertaining to optical band gap and optically stimulated transitions in glassy materials. The
linear part of the plot is extended to determine the values of band gap energies of all glass
samples, as shown in table 3. The table shows that optical energy band gap ( ) decreases

as the content of Nd2O3 increases. This decrease in the energy band gap ( ) with the
inclusion of Nd2O3 could be attributed to structural modifications [20-22] which are
apparent from the FTIR findings. Theses structural modifications increases the degree of
localizations, resulting in the amount of the donor centres in the glass network [20-22]. The
growth in donor centres with the inclusion of Nd2O3 contributes to a reduction in the optical
band gap.

Table 3 : Optical energy band gap for Nd2O3 doped sodium borosilicate glasses

Mol % Nd2O3 Band gap (eV)

0 3.4734
0.5 3.3333
1 3.2208
1.5 3.1714
2 3.1313

Figure 5 displays the 0.5 mol% excitation spectra of Nd2O3 doped sodium
borosilicate glass sample monitoring emission at 1063 nm. The excitation spectra reveals
seven prominent peaks owing to quantum transition from ground energy state to excited
state. These peaks corresponds to 432 nm ( 4I9/2→2P1/2 ), 474 nm ( 4I9/2→2G9/2), 513 nm
(4I9/2→4G9/2), 527 nm (4I9/2→4G7/2), 588 nm (4I9/2→4G5/2), 682 nm (4I9/2→4F9/2) and 744 nm
(4I9/2→4F7/2 ). It is found that the peak at 588 nm is more prominent among all which is used
as an excitation wavelength for measurement of emission spectra.
 Figure 5 : Excitation spectra of 0.5 mol % Nd2O3 doped sodium borosilicate glasses
(λem =1063 nm)

Figure 6 illustrates the emission spectra (excited at 588 nm) of Nd3+ containing
sodium borosilicate glass samples. This spectrum has three prominent bands at 902 nm
(4F3/2→4I9/2), 1063 nm (4F3/2→4I11/2) and 1334 nm (4F3/2→4I13/2) attributable to Nd3+ ions
transitions. Emission spectra shows that the emission intensity rises till 1 mol% Nd2O3 and
emission intensity declines with the further increase in Nd2O3. This phenomenon is known as
luminescence quenching. The intensity of emission spectra depends on number of active
centers. The active centers are Nd3+ ions in the present glassy matrix. The density of Nd3+ ions
rises with the doping of Nd2O3 at the expense of B2O3 and SiO2. As a result of which,
emission rate rises up to 1 mol% Nd2O3. With a rise in the concentration of Nd3+ ions, the
intermolecular gap decreases and above 1 mol percent of Nd2O3, the Nd3+ ions are very closed
resulting significant interaction between Nd3+ ions. Thus, there is an effective energy transfer
between Nd3+ and Nd3+ ions resulting in luminescence quenching as displayed in figure 6.
These findings are reasonably consistent with previously published results [18-22].

Figure 6: Emission spectra for Nd2O3 containing sodium borosilicate glass samples
Conclusion:

Neodymium oxide-doped sodium borosilicate glasses were prepared using a typical melt-
quenching method. Prepared glass samples revealed to be amorphous by XRD study. The
FTIR analysis verified the different functional groups. The various functional groups were
confirmed by FTIR study. The density of prepared glass samples found to rise with the
inclusion of Neodymium oxide. This is due to the Nd2O3 molecule being larger in molecular
weight than other elements of glass samples. The estimated values for different physical
parameters such as neodymium ion concentrations (N), polaron radius (rp), mean spacing
between RE ions (ri), and field intensity (F) of Nd-O bonds appear to support variation in
glass density and molar volume. Optical absorption study shows increase in absorbance with
the additions of neodymium oxide. The optical energy band gap ( ) of studied glasses
found to decrease with the inclusion of neodymium oxide due to structural changes. The
emission spectra of Nd2O3 comprising sodium borosilicate glasses emits infrared emissions at

902 nm, 1062 nm and 1334 nm attributable to ‘4F3/2 4

I9/2, 11/2, 13/2’ Nd3+ ions transitions. The

luminescence quenching anomaly is observed above 1 mol percent. This is effectively

interpreted by means of neodymium ion concentration and ‘Nd3+ - Nd3+’ interaction in the

glassy matrix. A significantly greater 4F3/2 4

I11/2 transitions intensity indicates the glass can

be suitable for 1.06 micrometer IR laser applications. The Excellent correlation between
physical and optical properties is observed in studied glass system.

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