Optical Materials 80 (2018) 62–64

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Optical Materials
journal homepage: www.elsevier.com/locate/optmat

Luminescence investigation and thermal stability of blue-greenish emission T

generated from Ca3MgSi2O8: Eu2+ phosphor
D. Stefańska∗, P.J. Dereń
Institute of Low Temperature and Structure Research Polish Academy of Science, Wroclaw, Poland

A R T I C LE I N FO A B S T R A C T

Keywords: Europium-doped silicate Ca3MgSi2O8 has been successfully obtained using solid-state reaction at 1400 °C in a
Eu2+ vacuum atmosphere. The photoluminescence study of Eu2+ in investigated host showed broad emission band
Silicates with a maximum at 480 nm attributed to the allowed 5d → 4f electron transition of Eu2+ located in two different
Ca3MgSi2O8 crystallographic sites. The excitation, emission spectra as well as the luminescence decays were analyzed.
4f-5d luminescence
Thermal quenching process begins at 240 K, however, the emission stability of investigated compound is quite
good, and emission intensity reached to 70% of its initial value at 100 °C. The QE of Ca3MgSi2O8: 0.5% Eu2+
excited at 365 nm equal to 47%.

1. Introduction Mg2+ and Ca2+ ions [6–8]. Ca2+ ions are located in three different
positions: 8 - fold Ca(1), 9 - fold Ca(2) and 8 - fold Ca(3). Mg2+ has one
Silicates are excellent candidates for optical materials due to its high 6-fold coordinated site in Ca3MgSi2O8 matrix. A few years ago Lihui
chemical and thermal stability. What is more, their substrates are not et al. [8]. obtained Ca3MgSi2O8 activated by Ce3+ ions. They showed
expensive and readily available. Silicates are abundant on the Earth and that there are only two types of Ce3+ emission centers. Theoretical
form stable compounds with the alkaline earth metals. In such com- calculations proved that these centers correspond to cerium ions which
pounds, because of excellent compatibility of valence state and ionic substituted two different 8- fold coordinated calcium sites.
radii, the alkaline earth ions could be replaced with Eu2+. Many hosts In this study, a new blue-greenish emitting Ca3MgSi2O8: Eu2+
doped with Eu2+ are the subject of intense investigation nowadays phosphor was synthesized for the first time. The excitation and emission
because they exhibit intense and broad emission due to the allowed by spectra, as well as the luminescence decay times of europium ions, have
the Laporte rule transition from the lowest excited state 4f65d to the 4f7 been studied. The emission spectra measured in function of temperature
(8S7/2) ground state. Even small changes in the nearest environment of allowed to analyze thermal properties of the prepared compound.
Eu2+ affect its spectroscopic properties since the 5d electrons are not According to the results obtained one may conclude that marwinite
shielded. Therefore, the positions of the excitation and emission bands doped with Eu2+ ions could be applied as a blue phosphor.
of Eu2+ varies from blue to red spectrum region, depending on the
structure in which they are incorporated. For example, the maximum of 2. Experimental
Eu2+ emission in BaMgSiO4 is located at 440 nm while for Sr2MgSi2O7
it is at 470 nm [1]. In other barium silicates Ba2SiO4 and BaSi2O5 2.1. Preparation of Ca3MgSi2O8
emission are centered at 505 and 520 nm, respectively [1].
Blasse and co-workers studied the luminescence properties of Eu2+ Merwinite Ca3MgSi2O8 was synthesized by solid-state reaction. The
in many compounds, especially in silicates [1,2]. Their investigations stoichiometric amounts of Mg(CH3COO)2·4H2O (99.5%), CaCO3
were focused on optical properties of Eu2+ located in two different (99.99%), SiO2 (99.5%), Eu2O3 (99.99%) were weighed and mixed in
optical sites in orthosilicates as well as on the emission thermal stability an agate mortar to obtain a homogeneous powder. Prepared mixture
of Eu2+ depending on the host composition [3–5]. was annealed at 1400 °C for 5 h in a vacuum atmosphere.
In this work, we present the results of spectroscopic investigations
of Ca3MgSi2O8 marwinite. The structure of marwinite Ca3MgSi2O8 was 2.2. Instruments
described in details first by Moore in 1972 [6]. Then two other works
described the structure in details especially the coordination number of The XRD spectra were measured with X'Pert PRO powder

∗
Corresponding author.
E-mail address: [email protected] (D. Stefańska).

https://doi.org/10.1016/j.optmat.2018.04.031
Received 11 February 2018; Received in revised form 16 April 2018; Accepted 17 April 2018
Available online 24 April 2018
0925-3467/ © 2018 Elsevier B.V. All rights reserved.
D. Stefańska, P.J. Dereń Optical Materials 80 (2018) 62–64

Fig. 1. XRD diagrams of Ca3MgSi2O8: x % Eu2+. The standard pattern ICSD#

43-078 is presented as a reference.
Fig. 3. The PLE spectra of Ca3MgSi2O8: 0.5% Eu2+ monitored at 480 nm.

diffractometer (PANalitycal, The Netherlands) equipped with a linear

PIXcel detector and using Cu Kα radiation (λ = 1.54056 Å). To mea-
sure excitation spectra a McPherson spectrometer equipped with Xe
lamp was used. The emission spectra, as well as emission decay profiles,
were excited by a Ti-Saphire pulse laser pumped by a Nd: YAG laser.
The decay curves were recorded on a digital oscilloscope RIGOL
DS4052. The temperature of the samples during emission measure-
ments was controlled applying Linkam THMS 600 Heating/Freezing
Stage.

3. Results and discussion

3.1. Structural data

Fig. 4. Luminescence decay curves of Ca3MgSi2O8: x % Eu2+ recorded at

The investigated compound crystallizes in monoclinic space group
360 nm excitation line monitored at 480 nm. The inset presents calculated
in P1 21/c 1 space system. Fig. 1 shows XRD diagram of Ca3MgSi2O8
decay times of Eu2+ emission in μs.
doped with Eu2+. All diffraction lines of the prepared Ca3MgSi2O8
phosphor are in good agreement with the ICSD pattern (no. 43 - 078)
which means that obtained samples are pure without additional phases. spectra, as well as the redshift of the emission are presented in the
However, when the Eu2+ concentration exceeds 2%, unwanted phases supplementary materials (Fig. S1. and S2) [9–11].
of Ca3SiO5 (ICSD no. 13 - 0209), and CaO (ICSD no. 82–1691) were The sample with 0.5% of dopant generates the most intense emis-
observed. Therefore the luminescent characterization was carried out sion (Fig. 2 b), then The PL intensity decrease due to concentration
only for Ca3MgSi2O8 doped with 0.1–2.0% of Eu2+. quenching process. The FWHM of emission band for these compound is
equal to 2967 cm−1. Deconvolution of PL spectrum showed that re-
gistered band is a sum of two emissions with peak maxima at 476 nm
3.2. Luminescence properties (21 008 cm−1) and 503 nm (19 881 cm−1) observed from two different
optical sites of Eu2+(Fig. 2 c). This is a similar result to the one pre-
Emission spectra of prepared samples doped with different con- sented for merwinite doped with Ce3+ [8], where dopants were located
centrations of Eu2+ measured under 360 nm excitation line consist of as well in two sites replaced 8- fold coordinated Ca2+ ions (Ca(1) and
one broad asymmetric band from 430 to 650 nm (Fig. 2 a). The ob- Ca(3)). Consideration about the bond length shows that the average
served band is associated with the allowed electron transition from the distance for Ca2+(1) – O2− and Ca2+(3) – O2− is equal to 2.5186 and
lowest 4f65 d1 excitation state to the 4f7 ground state. 2.7636 Å, respectively. It can be conclude that the strongest crystal field
The maximum of the emission band moves from 474 to 480 and around Eu2+ in Ca(1) site is correlated with lower energetic band at
484 nm for the samples doped with 0.1%, 0.5%, and 2.0%, respectively 19 881 cm−1, while the Eu2+ in Ca(3) one corresponds to the emission
due to reabsorption. The overlap region of the emission and absorption

Fig. 2. a) The emission spectra of Ca3MgSi2O8: x % Eu2+ excited at 360 nm b) integrated intensity as a function of Eu2+ concentration and c) fitting curves of
emission spectra of sample doped with 0.5% of Eu2+.

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D. Stefańska, P.J. Dereń Optical Materials 80 (2018) 62–64

Above this value, the concentration quenching process occurred. The

Eu2+ ions in the investigated compound exhibit blue-greenish emission
centered at 480 nm. The PL and PLE, as well as luminescence decay
curves, showed that activators are located in two different crystal-
lographic positions and replace 8- fold coordinated Ca2+ ions. The re-
lative emission intensity does not change significantly up to 100 °C. The
QE of Ca3MgSi2O8: 0.5% Eu2+ excited at 365 nm equal to 47%.

Acknowledgements

This work was supported by The National Science Centre under

Grant No. DEC- 2013/11/N/ST5/01986, which is gratefully acknowl-
edged. The authors thank M. Sc. E. Bukowska for the XRD measure-
ments.

Fig. 5. a) Temperature dependent emission spectra of Ca3MgSi2O8: 0.5% Eu2+

Appendix A. Supplementary data
under 360 nm excitation recorded from 77 K to 600 K b) integrated emission
intensity as a function of temperature.
Supplementary data related to this article can be found at http://dx.
doi.org/10.1016/j.optmat.2018.04.031.
at 21 008 cm−1.
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