Materials Today: Proceedings xxx (xxxx) xxx

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Optical properties of the glasses from the system CaO-GeO2-Li2O-B2O3

doped by terbium
I. Koseva a,⇑, V. Nikolov a,c, M. Gancheva a, L. Aleksandrov a, P. Ivanov b, P. Petrova b, R. Iordanova a,
R. Tomova a
a
Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Acad. G. Bonchev Str., bl.11, 1113 Sofia, Bulgaria
b
Institute of Optical Materials and Technologies, Bulgarian Academy of Sciences, Acad. G. Bontchev Str., bl. 109, 1113 Sofia, Bulgaria
c
Institute of Mineralogy and Crystallography, Bulgarian Academy of Sciences, Acad. G. Bonchev Str., bl. 107, 1113 Sofia, Bulgaria

a r t i c l e i n f o a b s t r a c t

Article history: Terbium doped glasses with three different compositions from the system CaO-GeO2-Li2O-B2O3 and dif-
Available online xxxx ferent dopant concentrations were prepared. DTA analyses show weak influence of the rare earth ion on
the glass thermal properties. The FTIR spectra revealed variations between glass structures. Excitation
Keywords: and emission spectra of the doped glasses possess the characteristic transitions of Tb3+ ions. Peaks loca-
Germanate phosphor tions are not dependent on the rare earth ion concentration and the glass composition, but some splitting
Terbium doped glasses appears. Chromaticity coordinates of Tb3+ glasses are placed in a green and green-yellowish area of the
Photoluminescence
color space diagram.
Ó 2022 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the Third Workshop on
Size-Dependent Effect in Materials for Environmental Protection and Energy Application

1. Introduction
Glasses doped by rare earth ions are widely used as sensors,
solid state lasers, optical fibers in telecommunication and phos-
phors for monitors [1]. Borate glasses containing alkali oxides pos-
sess high electrical and chemical resistance, high hardness and low
melting temperature compared to silicate glasses [2]. Moreover,
borate glasses are of interests to researchers because of their coor-
dination geometry and high transparency [3]. The advantage of
germanate glasses are their good luminescent characteristics. Fur-
thermore, they are easier for preparing as opposite to silicate
glasses, which requires higher temperatures. Germanates possess
more appropriate conductivity, thus they are preferred in manu-
facturing of plasma and electroluminescent displays. Additionally,
germanates show low thermal quenching, as opposite to molyb-
dates and tungstates [4–6].
Tb3+ has a strong excitation band in the near UV region (around
380 nm) and emits green light (around 550 nm) because of the
5
D4?7F5 transition. This line is the strongest in almost all hosts.
The intensity depends on the Tb3+ concentration. When the con-
centration of the dopant is low, the emission from high excited
⇑ Corresponding author.
E-mail address: ikosseva@svr.igic.bas.bg (I. Koseva).
states can be observed in the blue part of the visible spectra. In
higher dopant concentrations, cross-relaxation quenching appears
because of the small distances between terbium ions in the host
lattice [7,8]. As the human vision is most sensitive to green light,
Tb3+ ion becomes more and more important [9]. Besides, Tb3+ ion
can be co-doped with Eu3+ ion for obtaining of white light emitting
medium [10].
Our previous investigations on the glass composition from the
oxide system CaO-GeO2-Li2O-B2O3 allow us to select the most
appropriate glasses for doping by rare earth activators [11].
The purpose of this study is to find out how the change of ter-
bium concentration affects the glass structure and glass spectral
characteristics. These studies are a part of a project, including pho-
toluminescence properties investigations on solid state synthe-
sized germanate samples, glasses, glass-ceramics and single
crystals doped by Eu3+, Tb3+ and Dy3+ ions.
2. Experimental part
CaCO3 (p.a., Valerus), Li2CO3 (p.a., Valerus), GeO2 (99.999%, Alfa
Aesar), H3BO3 (p.a., Valerus) and Tb4O7 (99.9%, Alfa Aesar) was
used as row materials. Glass synthesis were carried out in a resis-
tive furnace with Kantal heating wire permitted maximum work-

https://doi.org/10.1016/j.matpr.2021.12.118
2214-7853/Ó 2022 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the Third Workshop on Size-Dependent Effect in Materials for Environmental Protection and
Energy Application

Please cite this article as: I. Koseva, V. Nikolov, M. Gancheva et al., Optical properties of the glasses from the system CaO-GeO2-Li2O-B2O3 doped by terbium,
Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2021.12.118
I. Koseva, V. Nikolov, M. Gancheva et al. Materials Today: Proceedings xxx (xxxx) xxx

Table 1
Glass compositions from the oxide system CaO-GeO2-Li2O-B2O3 and concentrations of Tb3+ ion in the glasses.

CaO GeO2 Li2O B2O3 Tb3+

[mass%] [mass%] [mass%] [mass%] [at%]
Glass
G1 45 38 5 12 1, 2, 3, 5, 6, 7
G2 40 43 5 12 3, 4, 5
G3 28 53 15 5 0.5, 1, 2, 3

ing temperature of 1200 °C and in a chamber furnace with MoSi2
heating elements. The temperature was controlled with Pt/Pt–
10 %Rh thermocouple and Eurotherm controller. Glasses were
melted in platinum crucibles in air. First the mixture was heated
at 700 °C for decomposition of the calcium carbonate, lithium car-
bonate and boric acid and then the melt was heated at 1250 or
1300 °C during 3 h for homogenization. As obtained melts were
cooled down to the room temperature by quick removing from
the furnace and quenched by pouring onto a steel plate and press-
ing with another steel plate.
Differential thermal analyses (DTA/TG) were done by the appa-
ratus SETARAM Labsys Evo 1600, France. The samples were heated
at a heating rate of 10 °C/min in air atmosphere with flow rate of
20 ml/min.
Fig. 1. XRD patterns of the glasses with composition G1, G2 and G3 doped by 7, 5
and 3 at% Tb3+ respectively.
The infrared spectra were recorded on a Nicolet iS5 Fourier
transform interferometer (resolution < 2 cm 1) at ambient temper-
atures using KBr discs as matrices. No ion exchange or other reac-
tions with KBr have been observed.
The emission and excitation spectra where measured on Horiba
Fluorolog 3–22 TCS spectrophotometer equipped with a 450 W
Xenon Lamp as the excitation source. All spectra were measured
at room temperature.
3. Results and discussion
The studied glass compositions from the oxide system CaO-
GeO2-Li2O-B2O3 and concentrations of Tb3+ ion in the glasses are
summarized in Table 1. The rare earth concentrations are chosen
based on our previous investigations [12,13].
Fig. 1 presents XRD patterns of the prepared glasses. As it is
seen, XRD shapes did not detect the presence of any sharp peaks,
which is a confirmation of the homogeneousness of the glasses.
The data from DTA analysis (Glass transition temperature Tg,
Crystallization onset Tx, Crystallization temperature Tc and Glass
stability parameter Tx-Tg) are presented in Table 2. The glasses
with composition G2 characterized with highest thermal stability
and glasses with composition G3 are most unstable. The influence
of the rare earth ion concentration on the glasses thermal proper-
ties is very weak.
IR spectra of pure and Tb3+ doped glasses are presented in Fig. 2.
The absorption bands above 1200 cm 1 in non-doped glasses is
attributed to the B-O stretching vibration of BO3 units. The bands
in the range 700–1200 cm 1 are attributed to vibration of B-O from
BO4 units [14–18]. High intensity band at 745 cm 1 and shoulder
at 570 cm 1 appear due to asymmetric stretching vibration of
the Ge-O-Ge and O-Ge-O deformation vibrations from GeO4 groups
[18–20]. The weak bands at 680 and 425 cm 1 are characteristic for
vibration of B-O-Ge bond, so the borate and germinate units are
not isolated in the glasses network [21,22]. In the range below
500 cm 1 are the bands of Li – O and Ca- O vibration from LiO4
and CaO units. The band at 470 cm 1 appears due to the Ca–O

Table 2
DTA data of the investigated glasses (Glass transition temperature Tg, Crystallization onset Tx, Crystallization temperature Tc and Glass stability parameter Tx-Tg).

Glass Dopant concentration Tg [°C] Tx [°C] Tc [°C] Tx-Tg [°C]

composition
G1 Non-doped 0 526 584 671 58

3+
Tb 2 527 581 677 54
7 522 610 625 88
G2 Non-doped 0 517 634 657 117

Tb3+ 4 512 638 652 126

5 518 653 673 135
G3 Non-doped 0 437 457 482 20

Tb3+ 1 432 463 494 31

3 438 482 489 44

2
I. Koseva, V. Nikolov, M. Gancheva et al.
Fig. 2. IR spectra of pure and Tb3+ doped glasses with compositions G1, G2 and G3.
bending vibrations [23] and Li-O stretching vibrations [24] and the
band close to 400 cm 1 is due to the Li-O vibration from LiO4 units.
The presences of Tb3+ ion in the glasses influence the glass
structure. In the non-doped IR spectra of glass with composition
G1 bands for BO3, BO4, GeO4 units and B-O-Ge linkages are
observed. In the Tb3+ doped glasses change in the glass network
is observed when the dopant concentration is higher than 2 at%.
The weak bands characteristic of BO4 units are transformed into
shoulders with increasing of the terbium content. On the other
hand, the band at 680 cm 1 disappears, so the presence of the
Tb3+ ion in the glass leads to partially transformation of BO4 to
BO3 units and to breaking the B-O-Ge linkages.
In the glass with composition G2 the typical bands for BO3, BO4
and GeO4 groups are observed. Bands at 570 and 470 cm 1 are
more pronounced, which indicate district presence of GeO4 units
and CaO units. The BO3, BO4 and GeO4 structural units are isolated
in the non-doped glass and glass doped by 4 at% Tb3+ because the
absorption band at 680 cm 1 is not detected. When the dopant
concentration reaches 5 at%, a new band at 700 cm 1 appears
and the band at 570 cm 1 transforms in shoulder. The band at
700 cm 1 is due to bending vibration of B-O-B bond from connec-
tion between BO3 and BO4 units, so in higher dopant concentra-
tions the linkages between borate structural groups is formed [25].
The main structural units in the glass with composition G3 are
BO3, BO4 and GeO4 units again. Band at 680 cm-1exists, so boron
and the germanium groups are connected. The band at about
425 cm 1, which is connected with LiO4 units, is more clearly pre-
sented compared with another two glasses. No significant changes
are observed in the IR spectra up to 2 at% Tb3+ concentration. In
3
Materials Today: Proceedings xxx (xxxx) xxx
higher dopant concentrations the Ge-O-B bonds brake and BO4
groups transform to BO3 groups.
Figs. 3, 4 and 5 present excitation and emission spectra of Tb3+
doped glasses with compositions G1, G2 and G3 and the influence
of the dopant concentration on the luminescence intensity of
5
D3?7F5 transition in the emission spectra.
Tb3+ doped excitation spectra of the glasses with composition
G1, G2 and G3 in the range 300–500 nm, monitored at 545 nm,
consist of the characteristic peaks of Tb3+ ion in this range and
do not show significant differences. The highest peak is located
at 377 nm corresponding to the 7F6?5D3 transition. Other peaks
are located at 303 nm (7F6?5H5), 317 nm (7F6?5H7), 351 nm
(7F6?5D2), 358 nm (7F6?5L10) and 483 nm (7F6?5D4) [26]. For
glasses with composition G1 highest intensity is seen in the 5 at
% Tb3+ doped glass spectrum. For glasses with composition G2
highest intensity is seen in the 4 at% Tb3+ doped glass spectrum
and for glasses with composition G3 highest intensity is seen in
the 2 at% Tb3+ doped glass spectrum.
Emission spectra of the studied glasses in the range 400–
720 nm, monitored at 377 nm excitation also consist of the Tb3+
ion characteristic peaks. Some differences are observed in the spec-
tra depending on the glass composition and Tb3+ ion concentration.
As can be seen, peaks in the all emission spectra are wide. It is
expected, as the glasses are not with a clear structure in opposite
to the crystalline spices. Peaks locations are not dependent on
the Tb3+ ion concentration, as well as the glass composition, but
some splitting appears. Splitting of different transitions is pre-
sented in Fig. 6.
I. Koseva, V. Nikolov, M. Gancheva et al.
Fig. 3. Excitation (a) and emission (b) spectra of Tb3+ doped glasses with
composition G1 and (c) influence of the dopant concentration on the luminescence
intensity of the 5D4?7F5 transition in the emission spectra.
According to Aspinall [27] and Ligner [28], 5D4 ?7F6 transition
and 5D4 ?7F4 transition in the terbium emission spectrum are sen-
sitive to the close active ion surrounding. It was mentioned above,
that glasses with composition G1 consist of BO3, BO4, GeO4 units
and B-O-Ge linkages; glasses with composition G2 consist of BO3,
BO4, GeO4 and CaO units; glasses with composition G3 consist of
BO3, BO4, GeO4, LiO4 units and Ge-O-B bonds.
As can be seen, 5D4 ?7F6 transition splitting depends both on
the glass composition and Tb3+ concentration. In the glass spectra
with composition G1 a weak shoulder appears at 496 nm in the
peak at 488 nm when the concentration of active ion reaches 3
at%. In the IR spectra transformation of BO4 groups to BO3 ones is
indicates. In the spectra of the glass composition G2 four-fold split
presents. The shoulder at 483 nm disappears when the dopant con-
centration reaches 4 at%. In the IR spectra band for BO4-BO3 con-
nection appears. In the spectra of the glass composition G3 six-
fold splitting appears. Shoulder at 495 nm disappears when the
active ion concentration reaches 2 at%. In the IR spectra transfor-
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Materials Today: Proceedings xxx (xxxx) xxx
Fig. 4. Excitation (a) and emission (b) spectra of Tb3+ doped glasses with
composition G2 and (c) influence of the dopant concentration on the luminescence
intensity of the 5D4?7F5 transition in the emission spectra.
mation of BO4 to BO3 groups and braking of the Ge-O-B bonds
are detected.
Examination of the 5D4 ?7F4 transition show changes in the
glasses spectra at the same concentrations of the active ion. In
the glass spectra with composition G1 a new splitting appears at
584 nm when the dopant concentration reaches 3 at%. In the spec-
tra of the glass with composition G2 a weak shoulder appears at
589 nm above 4 at% Tb3+ concentration. In the same time a small
peak at 590 nm disappears. In the spectra of the glass with compo-
sition G3 a weak shoulder appears at 584 nm when the active ion
concentration reaches 2 at%.
For glasses with composition G1 concentration quenching is
observed above 3 at% Tb3+. For glasses with composition G2 and
G3 concentration quenching appear above 4 and 2 at% Tb3+
respectively.
The Commission International de I’Eclairage (CIE) 1931 chro-
maticity coordinates (x, y) of the invested glasses are presented
in Fig. 7 and Table 3. As it is seen, they are placed in a green and
I. Koseva, V. Nikolov, M. Gancheva et al.
Fig. 5. Excitation (a) and emission (b) spectra of Tb3+ doped glasses with
composition G3 and (c) influence of the dopant concentration on the luminescence
intensity of the 5D4?7F5 transition in the emission spectra.
5
Materials Today: Proceedings xxx (xxxx) xxx
green-yellowish area. Coordinates of the glasses with composition
G3 are located in wider chromaticity range.
4. Conclusion
Terbium doped glasses with three different compositions and
different dopant concentrations were prepared from the oxide sys-
tem CaO-GeO2-Li2O-B2O3. DTA analyses show that the influence of
the rare earth ion and its concentration on the glasses thermal
properties is very weak. On the other hand the thermal stability
depends on the glass composition. The glasses with composition
G2 are more thermally stable compared to the other two groups
of glasses (G1 and G3). The IR spectra display some variations
between glass structures depending on the glass composition
and terbium concentration. The presence of the Tb3+ ion in the
glasses with composition G1 leads to breaking the B-O-Ge linkages
and to partially transformation of BO4 to BO3 units. The same struc-
tural changes are observed in the glasses with composition G3. In
glasses with composition G2 the linkages between borate struc-
tural groups is formed when the dopant concentration reaches 5
at%. When BO4 groups transform to BO3 ones and B-O-Ge linkages
are broken, 5D4 ?7F6 and 5D4 ?7F4 transition are more split in the
emission spectra. For glasses with composition G1 concentration
quenching appears when the Tb3+ concentration reaches 5 at%.
For glasses with compositions G2 and G3 this concentration is 4
and 2 at% respectively. Chromaticity coordinates of Tb3+ doped
samples are placed in a green and green-yellowish area in the color
space diagram. The as prepared glasses could be used for producing
of green phosphors or for including in the tricolor for white light
emitting diodes.
CRediT authorship contribution statement
I. Koseva: Conceptualization, Visualization. V. Nikolov:
Conceptualization. M. Gancheva: Data curation, Writing – review
& editing. L. Aleksandrov: Data curation, Writing – review &
editing. P. Ivanov: Formal analysis. P. Petrova: Formal analysis.
R. Iordanova: Formal analysis, Writing – review & editing. R.
Tomova: Formal analysis, Writing – review & editing.
I. Koseva, V. Nikolov, M. Gancheva et al. Materials Today: Proceedings xxx (xxxx) xxx

Fig. 6. Splitting of 5D4 ?7F6 transition and 5D4 ?7F4 transition in the Tb3+ doped glasses with compositions G1, G2 and G3.

6
I. Koseva, V. Nikolov, M. Gancheva et al. Materials Today: Proceedings xxx (xxxx) xxx

Fig. 7. CIE coordinates of Tb3+ doped glasses from the system CaO-GeO2-Li2O-B2O3.

Table 3 Declaration of Competing Interest

CIE coordinates of Tb3+ doped glasses from the system CaO-GeO2-Li2O-B2O3.

Glass composition Tb3+ concentration x y The authors declare that they have no known competing finan-
[at.%] cial interests or personal relationships that could have appeared
G1 1 0.340 0.565 to influence the work reported in this paper.
2 0.341 0.575
3 0.344 0.574
4 0.344 0.582
6 0.344 0.581 Acknowledgements
G2 3 0.345 0.576
4 0.366 0.559
5 0.347 0.578
The research is financial supported by the National Science
G3 0.5 0.319 0.501 Fund of Bulgaria (Contract No. KP-06-H29/10). Research equip-
1 0.331 0.546 ment of distributed research infrastructure INFRAMAT supported
2 0.327 0.538 by Bulgarian Ministry of Education and Science under contract
3 0.334 0.555
D01-284/17.12.2019 was used.

7
I. Koseva, V. Nikolov, M. Gancheva et al. Materials Today: Proceedings xxx (xxxx) xxx

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