Materials Today: Proceedings xxx (xxxx) xxx

Contents lists available at ScienceDirect

Materials Today: Proceedings

journal homepage: www.elsevier.com/locate/matpr

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 states can be observed in the blue part of the visible spectra. In
higher dopant concentrations, cross-relaxation quenching appears
Glasses doped by rare earth ions are widely used as sensors, because of the small distances between terbium ions in the host
solid state lasers, optical fibers in telecommunication and phos- lattice [7,8]. As the human vision is most sensitive to green light,
phors for monitors [1]. Borate glasses containing alkali oxides pos- Tb3+ ion becomes more and more important [9]. Besides, Tb3+ ion
sess high electrical and chemical resistance, high hardness and low can be co-doped with Eu3+ ion for obtaining of white light emitting
melting temperature compared to silicate glasses [2]. Moreover, medium [10].
borate glasses are of interests to researchers because of their coor- Our previous investigations on the glass composition from the
dination geometry and high transparency [3]. The advantage of oxide system CaO-GeO2-Li2O-B2O3 allow us to select the most
germanate glasses are their good luminescent characteristics. Fur- appropriate glasses for doping by rare earth activators [11].
thermore, they are easier for preparing as opposite to silicate The purpose of this study is to find out how the change of ter-
glasses, which requires higher temperatures. Germanates possess bium concentration affects the glass structure and glass spectral
more appropriate conductivity, thus they are preferred in manu- characteristics. These studies are a part of a project, including pho-
facturing of plasma and electroluminescent displays. Additionally, toluminescence properties investigations on solid state synthe-
germanates show low thermal quenching, as opposite to molyb- sized germanate samples, glasses, glass-ceramics and single
dates and tungstates [4–6]. crystals doped by Eu3+, Tb3+ and Dy3+ ions.
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. 2. Experimental part
The intensity depends on the Tb3+ concentration. When the con-
centration of the dopant is low, the emission from high excited CaCO3 (p.a., Valerus), Li2CO3 (p.a., Valerus), GeO2 (99.999%, Alfa
Aesar), H3BO3 (p.a., Valerus) and Tb4O7 (99.9%, Alfa Aesar) was
⇑ Corresponding author. used as row materials. Glass synthesis were carried out in a resis-
E-mail address: [email protected] (I. Koseva). 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 The infrared spectra were recorded on a Nicolet iS5 Fourier
heating elements. The temperature was controlled with Pt/Pt– transform interferometer (resolution < 2 cm 1) at ambient temper-
10 %Rh thermocouple and Eurotherm controller. Glasses were atures using KBr discs as matrices. No ion exchange or other reac-
melted in platinum crucibles in air. First the mixture was heated tions with KBr have been observed.
at 700 °C for decomposition of the calcium carbonate, lithium car- The emission and excitation spectra where measured on Horiba
bonate and boric acid and then the melt was heated at 1250 or Fluorolog 3–22 TCS spectrophotometer equipped with a 450 W
1300 °C during 3 h for homogenization. As obtained melts were Xenon Lamp as the excitation source. All spectra were measured
cooled down to the room temperature by quick removing from at room temperature.
the furnace and quenched by pouring onto a steel plate and press-
ing with another steel plate. 3. Results and discussion
Differential thermal analyses (DTA/TG) were done by the appa-
ratus SETARAM Labsys Evo 1600, France. The samples were heated The studied glass compositions from the oxide system CaO-
at a heating rate of 10 °C/min in air atmosphere with flow rate of GeO2-Li2O-B2O3 and concentrations of Tb3+ ion in the glasses are
20 ml/min. 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
Fig. 1. XRD patterns of the glasses with composition G1, G2 and G3 doped by 7, 5 500 cm 1 are the bands of Li – O and Ca- O vibration from LiO4
and 3 at% Tb3+ respectively.
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. Materials Today: Proceedings xxx (xxxx) xxx

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 higher dopant concentrations the Ge-O-B bonds brake and BO4
band close to 400 cm 1 is due to the Li-O vibration from LiO4 units. groups transform to BO3 groups.
The presences of Tb3+ ion in the glasses influence the glass Figs. 3, 4 and 5 present excitation and emission spectra of Tb3+
structure. In the non-doped IR spectra of glass with composition doped glasses with compositions G1, G2 and G3 and the influence
G1 bands for BO3, BO4, GeO4 units and B-O-Ge linkages are of the dopant concentration on the luminescence intensity of
observed. In the Tb3+ doped glasses change in the glass network 5
D3?7F5 transition in the emission spectra.
is observed when the dopant concentration is higher than 2 at%. Tb3+ doped excitation spectra of the glasses with composition
The weak bands characteristic of BO4 units are transformed into G1, G2 and G3 in the range 300–500 nm, monitored at 545 nm,
shoulders with increasing of the terbium content. On the other consist of the characteristic peaks of Tb3+ ion in this range and
hand, the band at 680 cm 1 disappears, so the presence of the do not show significant differences. The highest peak is located
Tb3+ ion in the glass leads to partially transformation of BO4 to at 377 nm corresponding to the 7F6?5D3 transition. Other peaks
BO3 units and to breaking the B-O-Ge linkages. are located at 303 nm (7F6?5H5), 317 nm (7F6?5H7), 351 nm
In the glass with composition G2 the typical bands for BO3, BO4 (7F6?5D2), 358 nm (7F6?5L10) and 483 nm (7F6?5D4) [26]. For
and GeO4 groups are observed. Bands at 570 and 470 cm 1 are glasses with composition G1 highest intensity is seen in the 5 at
more pronounced, which indicate district presence of GeO4 units % Tb3+ doped glass spectrum. For glasses with composition G2
and CaO units. The BO3, BO4 and GeO4 structural units are isolated highest intensity is seen in the 4 at% Tb3+ doped glass spectrum
in the non-doped glass and glass doped by 4 at% Tb3+ because the and for glasses with composition G3 highest intensity is seen in
absorption band at 680 cm 1 is not detected. When the dopant the 2 at% Tb3+ doped glass spectrum.
concentration reaches 5 at%, a new band at 700 cm 1 appears Emission spectra of the studied glasses in the range 400–
and the band at 570 cm 1 transforms in shoulder. The band at 720 nm, monitored at 377 nm excitation also consist of the Tb3+
700 cm 1 is due to bending vibration of B-O-B bond from connec- ion characteristic peaks. Some differences are observed in the spec-
tion between BO3 and BO4 units, so in higher dopant concentra- tra depending on the glass composition and Tb3+ ion concentration.
tions the linkages between borate structural groups is formed [25]. As can be seen, peaks in the all emission spectra are wide. It is
The main structural units in the glass with composition G3 are expected, as the glasses are not with a clear structure in opposite
BO3, BO4 and GeO4 units again. Band at 680 cm-1exists, so boron to the crystalline spices. Peaks locations are not dependent on
and the germanium groups are connected. The band at about the Tb3+ ion concentration, as well as the glass composition, but
425 cm 1, which is connected with LiO4 units, is more clearly pre- some splitting appears. Splitting of different transitions is pre-
sented compared with another two glasses. No significant changes sented in Fig. 6.
are observed in the IR spectra up to 2 at% Tb3+ concentration. In

3
I. Koseva, V. Nikolov, M. Gancheva et al. Materials Today: Proceedings xxx (xxxx) xxx

Fig. 3. Excitation (a) and emission (b) spectra of Tb3+ doped glasses with
Fig. 4. Excitation (a) and emission (b) spectra of Tb3+ doped glasses with
composition G1 and (c) influence of the dopant concentration on the luminescence
composition G2 and (c) influence of the dopant concentration on the luminescence
intensity of the 5D4?7F5 transition in the emission spectra.
intensity of the 5D4?7F5 transition in the emission spectra.

According to Aspinall [27] and Ligner [28], 5D4 ?7F6 transition mation of BO4 to BO3 groups and braking of the Ge-O-B bonds
and 5D4 ?7F4 transition in the terbium emission spectrum are sen- are detected.
sitive to the close active ion surrounding. It was mentioned above, Examination of the 5D4 ?7F4 transition show changes in the
that glasses with composition G1 consist of BO3, BO4, GeO4 units glasses spectra at the same concentrations of the active ion. In
and B-O-Ge linkages; glasses with composition G2 consist of BO3, the glass spectra with composition G1 a new splitting appears at
BO4, GeO4 and CaO units; glasses with composition G3 consist of 584 nm when the dopant concentration reaches 3 at%. In the spec-
BO3, BO4, GeO4, LiO4 units and Ge-O-B bonds. tra of the glass with composition G2 a weak shoulder appears at
As can be seen, 5D4 ?7F6 transition splitting depends both on 589 nm above 4 at% Tb3+ concentration. In the same time a small
the glass composition and Tb3+ concentration. In the glass spectra peak at 590 nm disappears. In the spectra of the glass with compo-
with composition G1 a weak shoulder appears at 496 nm in the sition G3 a weak shoulder appears at 584 nm when the active ion
peak at 488 nm when the concentration of active ion reaches 3 concentration reaches 2 at%.
at%. In the IR spectra transformation of BO4 groups to BO3 ones is For glasses with composition G1 concentration quenching is
indicates. In the spectra of the glass composition G2 four-fold split observed above 3 at% Tb3+. For glasses with composition G2 and
presents. The shoulder at 483 nm disappears when the dopant con- G3 concentration quenching appear above 4 and 2 at% Tb3+
centration reaches 4 at%. In the IR spectra band for BO4-BO3 con- respectively.
nection appears. In the spectra of the glass composition G3 six- The Commission International de I’Eclairage (CIE) 1931 chro-
fold splitting appears. Shoulder at 495 nm disappears when the maticity coordinates (x, y) of the invested glasses are presented
active ion concentration reaches 2 at%. In the IR spectra transfor- in Fig. 7 and Table 3. As it is seen, they are placed in a green and

4
I. Koseva, V. Nikolov, M. Gancheva et al. 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
Fig. 5. Excitation (a) and emission (b) spectra of Tb3+ doped glasses with & editing. L. Aleksandrov: Data curation, Writing – review &
composition G3 and (c) influence of the dopant concentration on the luminescence editing. P. Ivanov: Formal analysis. P. Petrova: Formal analysis.
intensity of the 5D4?7F5 transition in the emission spectra.
R. Iordanova: Formal analysis, Writing – review & editing. R.
Tomova: Formal analysis, Writing – review & editing.

5
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

References [14] R.C. Lucacel, C. Marcus, V. Timar, I. Ardelean, FT-IR and Raman spectroscopic
studies on B2O3–PbO–Ag2O glasses doped with manganese ions, Solid State
Sci. 9 (2007) 850–854, https://doi.org/10.1016/
[1] Yasaka P, Kaewkhao J. Luminescence from lanthanides-doped glasses and
j.solidstatesciences.2007.07.006.
applications: A review. In 2015 4th International Conference on
[15] F. He, J. Wang, D. Deng, Effect of Bi2O3 on structure and wetting studies of
Instrumentation, Communications, Information Technology, and Biomedical
Bi2O3–ZnO–B2O3 glasses, J. Alloys Compd. 509 (21) (2011) 6332–6336, https://
Engineering (ICICI-BME). IEEE 2015; 4-15. DOI 10.1109/ICICI-
doi.org/10.1016/j.jallcom.2011.03.087.
BME.2015.7401304.
[16] A. Edukondalu, A. Hameed, B. Kavitha, R.V. Kumar, K.S. Kumar, Vibrational
[2] W.M. Hua, P.S. Wong, T.Y. Eeu, Z. Ibrahim, R. Hussin, Structural and
spectra and structure of Li2O-K2O-WO3-B2O3 glasses, Mater. Today: Proc. 2 (3)
Luminescence Properties of Borate Glass with Lithium and Strontium
(2015) 913–917, https://doi.org/10.1016/j.matpr.2015.06.008.
Modifier Doped with Transition Metal Ions, Adv. Mater. Res. 501 (2012) 71–
[17] E. Mansour, Structure and electrical conductivity of new Li2O–CeO2–B2O3
75, https://doi.org/10.4028/www.scientific.net/AMR.501.71.
glasses, J Non Cryst Solids 357 (5) (2011) 1364–1369, https://doi.org/10.1016/
[3] P.P. Pawar, S.R. Munishwar, R.S. Gedam, Intense white light luminescent Dy3+
j.jnoncrysol.2010.09.026.
doped lithium borate glasses for W-LED: a correlation between physical,
[18] K. Błaszczak, W. Jelonek, A. Adamczyk, Infrared studies of glasses in the Li2O–
thermal, structural and optical properties, Solid State Sci. 64 (2017) 41–50,
B2O3–GeO2 (SiO2) systems, J. Mol. Struct. 511 (1999) 163–166, https://doi.org/
https://doi.org/10.1016/j.solidstatesciences.2016.12.009.
10.1016/S0022-2860(99)00155-6.
[4] P. Guo, F. Zhao, G. Li, F. Liao, S. Tian, X. Jing, Novel phosphors of Eu3+, Tb3+ or
[19] I. Ardelean, I. Todor, P. Pascutaa, I. Bratu, IR structural investigations of Bi2O3-
Bi3+ activated Gd2GeO5, J. Lumin. 105 (1) (2003) 61–67, https://doi.org/
GeO2 glasses containing manganese ions, Mod. Phys. Lett. B 17 (2003) 311–
10.1016/S0022-2313(03)00098-X.
315, https://doi.org/10.1142/S0217984903005342.
[5] Keiser G. Optical fiber communications. Wiley Encyclopedia of
[20] L.Y. Zhang, H. Li, L.L. Hu, Statistical structure analysis of GeO2 modified Yb3+:
Telecommunications; 2003. https://doi.org/10.1002/0471219282.eot158.
Phosphate glasses based on Raman and FTIR study, J. Alloys Compd 698 (2017)
[6] D. Di Martino, L.F. Santos, A.C. Marques, R.M. Almeida, Vibrational spectra and
103–113, https://doi.org/10.1016/j.jallcom.2016.12.175.
structure of alkali germanate glasses, J. Non Cryst. Solids 293 (2001) 394–401,
[21] O.N. Koroleva, M.V. Shtenberg, R.T. Zainullina, S.M. Lebedeva, L.A. Nevolina,
https://doi.org/10.1016/S0022-3093(01)00690-1.
Vibrational spectroscopy and density of K2O–B2O3–GeO2 glasses with variable
[7] W.M. Yen, S. Shionoya, H. Yamamoto (Eds.), Phosphor Handbook, CRC Press,
B/Ge ratio, Phys. Chem. Chem. Phys. 21 (23) (2019) 12676–12684, https://doi.
Boca Raton, 1998.
org/10.1039/C9CP01374A.
[8] R.-S. Liu (Ed.), Phosphors, Up Conversion Nano Particles, Quantum Dots and
[22] I.N. Chakraborty, R.A. Condrate, The vibrational spectra of B2O3-GeO2 glasses, J.
Their Applications, Springer Berlin Heidelberg, Berlin, Heidelberg, 2017.
Non Cryst. Solids 81 (3) (1986) 271–284, https://doi.org/10.1016/0022-3093
[9] N.L. Salvaggio, N. Salvaggio, L.D. Stroebel, R.D. Zakia, Basic photographic
(86)90496-5.
materials and processes, Taylor & Francis (2009), https://doi.org/10.4324/
[23] R. Amaravel, G. Venkatesh, L. Balu, R.E. Pavai, Structural and Thermal
9780080927664.
Properties of B2O3-Bi2O3-CaO Glasses, J. Adv. Phys. Sci. 1 (2017) 7–9.
[10] I. Koseva, P. Tzvetkov, P. Ivanov, A. Yordanova, V. Nikolov, Terbium and
[24] G. Padmaja, P. Kistaiah, Infrared and Raman spectroscopic studies on alkali
europium co-doped NaAlSiO4 nano glass-ceramics for LED application, Optik
borate glasses: evidence of mixed alkali effect, J. Phys. Chem. A 113 (11) (2009)
137 (2017) 45–50, https://doi.org/10.1016/j.ijleo.2017.02.098.
2397–2404, https://doi.org/10.1021/jp809318e.
[11] I. Koseva, V. Nikolov, P. Tzvetkov, M. Gancheva, P. Ivanov, P. Petrova, R.
[25] A. Adamczyk, M. Handke, W. Mozgawa, FTIR studies of BPO4
2SiO2, BPO4
SiO2
Tomova, Glass formation and glass ceramics in the system CaO-GeO2-Li2O-
and 2BPO4
SiO2 joints in amorphous and crystalline forms, J. Mol. Struct. 511–
B2O3-Re2O3 (Re= Eu3+, Tb3+, Dy3+), J. Non Cryst. Solids 552 (2021) 120442,
512 (1999) 141–144, https://doi.org/10.1016/S0022-2860(99)00152-0.
https://doi.org/10.1016/j.jnoncrysol.2020.120442.
[26] G. Blasse, B.C. Grabmaier (Eds.), Luminescent Materials, Springer Berlin
[12] I. Koseva, P. Tzvetkov, P. Ivanov, P. Petrova, R. Tomova, A. Yordanova, V.
Heidelberg, Berlin, Heidelberg, 1994.
Nikolov, Terbium-doped calcium germanate (Ca2GeO4) as a potential
[27] H.C. Aspinall, Chemistry of the f-Block Elements. Vol. 5. CRC Press; 2001.
candidate for LED application, J. Opt. 49 (3) (2020) 403–407, https://doi.org/
https://doi.org/10.1201/9781315139258.
10.1007/s12596-020-00634-2.
[28] G. Ligner, R. Mohan, S. Knittel, G. Duportail, Hypersensitivity of terbium and
[13] I. Koseva, P. Tzvetkov, P. Ivanov, V. Nikolov, P. Petrova, R. Tomova,
europium ions luminescence in biological substrates, Spectrochim. Acta A Mol.
Photoluminescent properties of terbium doped Li2CaGeO4 and Ca5Ge3O11
Biomol. Spectrosc. 46 (5) (1990) 797–802, https://doi.org/10.1016/0584-8539
(unpublished).
(90)80037-Y.