Ishak Na

Sahar Mr

Sazali Es

Yusoff Nm

Zain Sk

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18RRJPAP | Volume 3 | Issue 3 | December, 2015
Research & Reviews: Journal of Pure and 
Applied Physics
Physical and Optical Analysis of Erbium Doped Magnesium Zinc 
Phosphate Glass
Sahar MR*, Zain SK, Ishak NA, Sazali ES and Yusoff NM
Faculty of Science, Department of Physics,  Advanced Optical Materials Research Group, University 
Technology, Malaysia
Research Article
INTRODUCTION
Recently, a lot of works are carried out into the study of phosphate glasses due to their good chemical and physical properties 
which is suitable for the application in the field of optical communication. Phosphate based glass has queried much attention due 
to their excellent properties such as high transparency, low melting point, high thermal stability, low dispersion and low refractive 
index [1]. Phosphate glass exhibits high solubility of rare earth ions which allowing high concentration of active ion without losing 
their peculiar properties [2-4]. 
The present of metal oxide in host material will improve the phosphate glass stability due to the P-O-M+ (M is the metal 
cation) which is generally more stable to the atmospheric hydrolysis [5]. The addition of zinc and magnesium will affect the 
properties of glass in different way. According to the previous work, the presence of Zn2+ and Mg2+ will improve the polarizable 
and chemical durability of glass, respectively [6].
Besides, rare earth doped phosphate glass gives such of excellent improvement in the development of many optical devices 
[7]. It gives higher emission efficiency with the enhancement in emission line from visible to the infrared spectral region under 
suitable excitation condition as reported elsewhere [8]. Among the rare earth ions, Er3+ ion has higher potential application in 
developing the optical and laser device. The presence of Er3+ ion in phosphate glass can generate 1.54 μm wavelengths which 
can be utilized for optical amplification and its visible upconversion emission can be used as a solid-state laser [9].  
ABSTRACT
Glasses with composition of (60-x)P2O5-10MgO-30ZnO-(x)Er2O3 
where x = 0, 0.5, 1.0 and 1.5 mol% have successfully been prepared by 
melt quenching technique. The amorphous nature of the glass has been 
determined by using X-ray Diffractometer (XRD). It is found that all glasses 
are amorphous in nature. The physical properties have been determined by 
mean of glass density and molar volume, while the optical properties have 
been characterized by UV-Vis Spectroscopy (UV-Vis). The glass density is 
found to be in range of (2.753-2.791) g cm-3 and is increasing as the Er2O3 
concentration is increased up to 0.5 mol%, but decreases as the Er2O3 
concentration is further increased up to 1.5 mol%. The molar volume of the 
glass exhibits an opposite trend with the density. UV-Vis spectra reveal seven 
absorption bands from the ground state 4I15/2 to to the excited states 
4F7/2, 
2H11/2, 
4S3/2, 
4F9/2, 
4I9/2, 
4I11/2 and 
4I13/2, centered at 486, 520, 550, 650, 792, 
974 and 1536 nm, respectively. The optical energy band gap of the glass 
decreases as the Er2O3 concentration is increased from 0.0 mol% to 0.5 
mol% but increases as the Er2O3 concentration is further increased up to 
1.5 mol%. Bonding characteristic of the glass is determined via calculation 
of Racah parameter. All the results are discussed with respect to the Er2O3 
concentration.
Received date: 23/10/2015
Accepted date: 01/12/2015
Published date: 12/03/2015
*For Correspondence
Sahar MR, Faculty of Science, Department of 
Physics,  Advanced Optical Materials Research 
Group, University Technology, 81310 UTM Skudai, 
Johor, Malaysia, Tel: +607-5566162 
E-mail: mrahim057@gmail.com
Keywords: Phosphate glasses, XRD, Optical energy, 
Band gap, Bonding characteristic, Racah parameter
19RRJPAP | Volume 3 | Issue 3 | December , 2015
 The purpose of this study is to prepare (60-x)P2O5-10MgO-30ZnO-(x)Er2O3 glass system by melt quenching technique and 
characterize their physical and optical properties. There are some advantages of melt quenching technique, which is easier 
than other method and can produce flexible glass geometry. The results are analysed, compared to the previous research and 
understood.
EXPERIMENTAL
The raw material of P2O5, MgO, ZnO and Er2O3 are commercially provided in the powder forms. 20 gm batch from a proportion 
amount of P2O5 (purity 99.9%), MgO (purity 99.5%), ZnO (purity 99.1%) and Er2O3 (purity 99.9%) powder are weighed and mixed in 
an alumina crucible before being heated at 900oC for 30 minutes. After the required viscosity is obtained, the melts is quenched 
in a pre-heated metal plates. The glass is then annealed at 300oC for 3 hours before being allowed to cool down to room 
temperature. The composition for each sample of the glass is shown in Table 1.
Sample
Concentration (mol %)
P2O5 MgO ZnO Er2O3
S1 60.0 10.0 30.0 0.0
S2 59.5 10.0 30.0 0.5
S3 59.0 10.0 30.0 1.0
S4 58.5 10.0 30.0 1.5
Table 1. The Nominal Composition of Glass Samples.
X-ray Diffraction (XRD) analysis is performed by using Siemens Diffractometer D5000 using Cu-Kα radiations (λ≈1.54 Å) at 
40 kV and 100 mA, with scanning angle of 2θ ranges between 10-80°. The glass density (ρ in gcm-3) is determined by using the 
Archimedes method with toluene is used as an immersion liquid. The relation of Archimedes principle is written as [10],
aal
la
a
WW
W
ρρρρ +−
−
= )(                      (1)
where Wa and Wl are the weight of glass in air and in liquid, respectively. ρa is the air density (0.001 g cm
-3) and ρl is the 
density of toluene (0.8669 g cm-3). Meanwhile, the molar volume, Vm is calculated by using the relation 
[11]:
)(
ρ
MVm =                          (2)
where M is the molar mass of glass.
The absorption spectra have been performed in the range of 400-1600 nm by using the Shimadzu 3101 UV-Vis 
spectrophotometer. Optical absorption reflects to the density of states at the band edges which is used to calculate the glass 
absorption coefficient α(v) using Beer Lambert’s law as stated below [12],
d
A303.2)( =να                                                               (3)
where A is defined by log (Io/I).
The absorption coefficient, α is used to calculate the optical energy band gap (Eg) using Davis Mott equation 
[13]; 
𝛼(𝜔) ℏ𝜔= 𝐶 (ℏ𝜔−𝐸𝑔)𝑚                      (4) 
where ћω is the photon energy, C is a constant, α absorption coefficients, ω is a frequency dependent and m is the index value.
Racah parameter is useful to interpret the electrostatic repulsion in an atom when more than one electron exists. The total 
repulsion can be determined in terms of B and C Racah parameter [14]. The symbol of B and C represents a complex form from a 
transition metal in the free ion. The nephelauxetic ratio, h is used to elucidate the effect of reduction or enhancement electron-
electron repulsion between RE and ligand. The nephelauxetic ratio is a parameter used to explain the electron cloud expanding 
as early defined by Jorgensen [15]. All these parameters are calculated from absorption peak wavelength marked as (𝑣1, 𝑣2, 𝑣3 in 
𝑐𝑚−1), which finally provide the information of ionic or covalent between metal and ligand bond. The amorphous field strength (Dq) 
and the Racah Parameter B, C can be calculated from the following relations [16],
𝑣1 = 10𝐷𝑞		                                                                     (5)
𝐵 = 1 /3 (2𝑣1− 𝑣2)(𝑣2− 𝑣1) /9𝑣1−5𝑣2                                                    (6)
𝐶 = 𝑣3 −4𝐵 −10𝐷𝑞		/3                                                       (7)
The bonding formation can be predicted as:
ℎ = [(𝐵 𝑓𝑟𝑒𝑒−𝐵 )/𝐵 𝑓𝑟𝑒𝑒] 𝑘𝑖𝑜𝑛                                                            (8)
𝑘𝑖𝑜𝑛 = [𝑍 + 2 − 𝑆/5]2                                                          (9)
20RRJPAP | Volume 3 | Issue 3 | December , 2015
RESULTS AND DISCUSSION
Figure 1 shows the typical XRD pattern for all samples which shows the presence of broad hump in the range of 20-30 
degree. The broad peak confirmed the amorphous nature of the glass sample.
Figure 1. X-Ray Diffraction pattern of (60-x)P2O5-10MgO-30ZnO-(x)Er2O3 glass system.
The density and molar volume of the glasses are listed in Table 2. The relation of glass density and molar volume with 
the Er3+ concentration is shown in Figure 2. Glass density is found to be in the range of 2.754 - 2.915 g cm-3. The glass densiy 
increases with the concentration of Er3+ ions up to 1.0 mol%, but decreases as the Er3+ concentration is increased up to 1.5 
mol%. The addition of Er3+ into the glass network increases the number of non-bridging oxygen (NBO) and it also attributes to the 
replacement of atom with low density oxide (P2O5, 2.39 g cm
-3) with the atom of high density oxide (Er2O3, 8.64 g cm
-3) [4]. However, 
at the same range of Er3+ concentration, the molar volume shows an opposite behavior to the density where it decreases from 
41.257 to 40.594 cm3 mol-1 which presumably due to the decreases in the bond length or inter-atomic spacing between the atom. 
It is known that, the density and molar volume of material show an opposite behavior to each other [17].
Er2O3 concentration (mol%) Density, ρ (±0.001)(g cm
-3) Molar Volume, Vm (±0.001)(cm
3 mol-1)
0.0 2.754 41.257
0.5 2.802 40.594
1.0 2.915 40.792
1.5 2.788 40.896
Table 2. The Density and Molar Volume of (60-x)P2O5-10MgO-30ZnO-(x)Er2O3 Glasses.
Figure 2. The density and molar volume of (60-x)P2O5-10MgO-30ZnO-(x)Er2O3 glass system dependent concentration of Er2O3.
As the Er3+ is increases beyond 0.5 mol% it is presumed that the Er3+ ion will enter the network by breaking up the phosphate 
double bond. As a consequent, there will be a relatively increase in the amount of bridging oxygen (BO). This result shows the role 
of Er3+ in modifying the glass structure from PO3 to PO4. On the other hand, the increases of BO network will cause the increase in 
bond length or inter-atomic spacing between the atom and thus gives the increase in molar volume of the glass. 
Figure 3a shows the optical absorption spectra of the glass. Basically, the appearance peak in the spectra is due to the 
distribution of crystal field in the glass. From Figure 3a, it shows seven absorption peaks which correspond to the transition of 
Er3+ from ground state 4I15/2 to the excited states of 
4F7/2, 
2H11/2, 
4S3/2, 
4F9/2, 
4I9/2, 
4I11/2 and 
4I13/2 centered at 486, 520, 550, 650, 
792, 974 and 1536 nm, respectively.
From Figure 3a, a plot of (αhv)1/2 against photon energy(hv) can be made and the result is shown in Figure 3b. From Figure 
3b, the values of Eg can be estimated by extrapolating a linear part of (αhv)
1/2 against photon energy(hv). The meeting point of the 
straight line and x-axis is the value of the Eg of the sample. The value of Eg is summarized in Table 3. It can be seen that the value 
is in the range of (4.236 – 3.698) eV which is close to the result obtained in the previous work [18]. 
As can be seen that Eg decreases as the amount of Er
3+ concentration is increased up to 0.5 mol%, but slightly increases 
as further Er3+ is increased up to 1.5 mol%. The decrease of Eg is probably due to the increasing number of non-bridging oxygen 
21RRJPAP | Volume 3 | Issue 3 | December , 2015
(NBO) [19]. However further addition of the Er3+ ion shows an increasing of the Eg which indicates the increase in the formation of 
bridging oxygen (BO) in the glass. The larger magnitude of BO's, more energy is needed to excite the electrons to the upper state. 
This is due to the fact that the electrons are tightly bounded to the BO as compare to the electron connected to NBO. This changes 
is parallel to the results as observed in the variation of density.
Figure 3. (a) The optical absorption spectra (b) The (αhv)1/2 against photon energy (hv) of (60-x)P2O5-10MgO-30ZnO-(x)Er2O3 glasses.
Sample Er2O3 concentration (mol%) Eg  (±0.001 eV)
S1 0.0 4.236
S2 0.5 3.698
S3 1.0 3.800
S4 1.5 3.910
Table 3. The Optical Energy Band gap (Eg) for the Prepared Glasses.
From Figure 4a, it can be seen that parameter B is increasing as Er2O3 is increased up to 1.0 mol% Er2O3.
 The increasing 
of parameter B shows that Er–O bond is ionic. However, as the Er2O3 is further increased, the 𝐵  parameter decreases which 
reflects to the increase in covalent bond between 𝐸𝑟3+ ion and ligand. It indicates that more electrons delocalized in the d-shell 
as reported elsewhere [20]. From Figure 4b, it can be seen that parameter 𝐶 shows a similar trend as parameter 𝐵  but keep 
increasing beyond 1.0 mol%. This increment is presumably due to the mix between ionic with covalence bond of Er-O. Figure 5a 
shows the ratio of crystal field 𝐷𝑞		 to parameter B against the Er2O3 concentration.
(a)       (b) 
Figure 4. (a) Parameter 𝐵  (b) Parameter 𝐶 versus Er2O3 concentration in mol%.
From Figure 5a, it can be seen that the ratio of Dq/B decreases as increasing of Er2O3 concentration. The reduction of Dq/B 
from 16.830 to 13.300 reflected that the bond of Er-O has smaller crystal field strength. Meanwhile, the nephelauxetic function 
is decreasing from 0.061 to 0.059 with the addition of Er2O3 concentration up to 1.0 mol% as shown in Figure 5b. This is once 
again shows that the Er-O bonds are ionic because of the less overlapping of d-orbital of Er3+ and ligand orbital. Beyond 1.0 mol%, 
the Nephelauxetic function increases with Er2O3 concentration. This is due to the increasing of overlapping in Er-O orbital 
[21,22].
(a)       (b) 
Figure 5. (a) 𝐷𝑞		/𝐵  (b) Nephelauxetic Function, h versus Er2O3 concentration in mol%.
22RRJPAP | Volume 3 | Issue 3 | December , 2015
CONCLUSION
A series of glass with composition of (60-x)P2O5-10MgO-30ZnO-(x)Er2O3 where x = 0, 0.5, 1.0, and 1.5 mol% have successfully 
been prepared by melt quenching technique. All glasses are found amorphous in nature. The glass density is found in the range 
of (2.754 - 2.915) g cm-3, increases with the increasing of Er3+ concentration up to 1.0 mol%, but decreases as the concentration 
of Er3+ is added up to 1.5 mol%. The molar volume of the glass is found to be in the range of (41.257 - 40.594) cm3 mol-1. The 
variation of density and molar volume of the glass is due to the rearrangement of the lattice cause by the increasing number 
of non-bridging oxygen (NBO) and bridging oxygen (BO). The UV-Vis spectra reveal seven absorption bands centered at 486, 
520, 550, 650, 792, 974 and 1536 nm which correspond to the transition of Er3+ from ground state to excited state 4I15/2 to the 
excited states of 4F7/2, 
2H11/2, 
4S3/2, 
4F9/2, 
4I9/2, 
4I11/2 and 
4I13/2 respectively. The optical energy band gap (Eg) is found to decrease 
as the Er3+ concentration is increased from 0.0 mol% to 0.5 mol%, but increases as the Er3+ concentration is further increased 
up to 1.5 mol%. Racah parameter B and C are found to be in the range of (114.262-120.667) cm-1 and (812.025-893.890) cm-
1, respectively. Meanwhile the Dq/B and h are (16.830-13.300) and (0.061-0.059), respectively. The bonding parameters are 
depending on the composition of Er2O3. It is found that the Er-O bond becomes more covalence as Er2O3 is increased.
ACKNOWLEDGEMENTS
The authors gratefully acknowledge the financial support from Ministry of Education, Malaysia and Universiti Teknologi 
Malaysia via grants of Vot: 05H45, 05H36, 4F424, 4F319, 4F083, and 07J80.
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Research &amp; Reviews: Journal of Pure and Applied Physics Physical and Optical Analysis of Erbium Doped Magnesium Zinc Phosphate Glass

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Research & Reviews: Journal of Pure and Applied Physics Physical and Optical Analysis of Erbium Doped Magnesium Zinc Phosphate Glass