Journal of Alloys and Compounds 852 (2021) 157074

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Red luminescence with controlled rise time in La2MgTiO6: Eu3þ

B. Bondzior *, D. Stefan

ska , T.H.Q. Vu
~ , N. Miniajluk-Gaweł , P.J. Deren


Institute of Low Temperature and Structure Research Polish Academy of Sciences, Wrocław, Poland

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

Article history: La2MgTiO6 (LMT) doped with Eu3þ ions has been prepared for the first time by the co-precipitation
Received 16 July 2020 method. All samples crystallize in the same orthorhombic crystal structure and the unit cell volume
Received in revised form decreases with increasing dopant concentration.
2 September 2020
The Eu3þ luminescence can be excited either into O2 / Eu3þ Charge Transfer State (CTS) with a
Accepted 5 September 2020
maximum at 320 nm or into 4f levels and exhibits the emission spectrum characteristic for Eu3þ ions at
the low symmetry site. TiO6 groups are also optically active with absorption at 305 nm and a weak
Keywords:
broadband emission at 478 nm. The configurational coordinate diagram was constructed based on the
Titanate
Eu3þ
absorption, emission and thermal quenching energy values. The relative thermal sensitivity of the in-
Red phosphor tensity ratio between luminescence excited at 532 nm and 266 nm is above 1% for temperatures below
Rise time 230 K and 3% for 77 K.
Co-precipitation The rise time of the 5D0 luminescence after the pulse excitation of the 5D1, resulting from both the
multiphonon relaxation and the cross-relaxation, strongly depends on the Eu3þ concentration and goes
from 94.1 ms for 0.1% Eu3þ down to 39.6 ms for 7% Eu3þ. It is only observed when the sample is excited at
532 nm (into the 5D1 level). When the sample is excited into the CTS, the rise time is not observed.
© 2020 Elsevier B.V. All rights reserved.

1. Introduction
A soaring trend in the number of publications on double pe-
rovskites has been witnessed for the last two decades due to the
flexible modification of crystal structure and thermal stability [1e3].
Based on an ideal cubic structure, ABX3, the substitution of partial
cation occurs in either A or B site, forming an ordered double
perovskite, A’A00 B’B00 O6 in which A0 and A00 are surrounded by several
oxygen atoms and connected with B’O6 and B00 O6 octahedron [1].
One representative of the double perovskites family, La2MgTiO6
(from here on referred to as LMT) has been known as an excellent
host for rare earth ions [4e11] and transition metal ions [12,13].
Due to the strong absorption bands of the TiO6 groups associ-
ated with an efficient energy transfer to the energy states of rare
earth ions stemming from the unfilled f orbital, this host can be
excited easily in the UV-VIS range. Additionally, Eu3þ ions were
chosen because they can exhibit an intense and narrow red emis-
sion originated from the 5D0 e 7F2 transition in the case of low
symmetry location. However, in some specific cases, the cross-
relaxation takes place between Eu3þ ion pairs by transferring
* Corresponding author. Oko
lna 2, 50-422, Wrocław, Poland.
E-mail address: b.bondzior@intibs.pl (B. Bondzior).
excited-state energy from one ion to another one in the ground
state causing inefficient emission.
To our best knowledge, up to now, there have been less than a
dozen of publications related to this host, one of them regarding a
solid-solution of La2MgTiO6 and Ba2MgWO6 for dielectric ceramics
[14]; two papers dealt with Mn4þ emission [12,13]; and the others
discussed photoluminescence of rare earth elements [4e11]. All of
them were aimed to develop the new red-emitting phosphor from
a perovskite-type titanate system doped by single or dual dopants.
A lack of detailed studies on the luminescence dynamics of LMT-
based materials can be understandable because the rise time -
defined as the initial time right after the excitation pulse - is shorter
than decay times and hence very difficult to obtain with optimized
concentration [15].
Generally, the conventional solid-state method is very common
for oxides preparation due to its simplicity. However, it has a lot of
drawbacks, such as larger grain size, high sintering temperature
and a long preparation time due to the need for several repetitions
of annealing. In contrast to the solid-state method, the co-
precipitation method possesses several appreciable advantages
including short time, smaller grain size and the increased homo-
geneity of its distribution.
In this study, a series of Eu3þ doped La2MgTiO6 materials with a
double-perovskite structure have been successfully prepared for

https://doi.org/10.1016/j.jallcom.2020.157074
0925-8388/© 2020 Elsevier B.V. All rights reserved.
2 B. Bondzior et al. / Journal of Alloys and Compounds 852 (2021) 157074

the first time by the co-precipitation method. Both the excitation

and absorption of Eu3þ were examined. Besides, the emission
spectra under 266 nm and 532 nm excitation wavelength were
investigated. Most importantly, the decay times and rise times at
300 K were analysed with an increasing of Eu3þ concentration. The
responsibility of the cross-relaxation process in the aforemen-
tioned phenomenon was demonstrated. Our work presents
extended spectroscopic studies in LMT: Eu3þ and the promising
application of the as-prepared phosphor in various fields including
lighting, displays, thermal sensing and also a niche application, e.g.
phosphors for anti-counterfeit applications.

2. Methods

2.1. Sample synthesis

LMT doped with Eu3þ ions was prepared for the first time by the
co-precipitation method. In this method the aqueous solution of
lanthanum acetate (La(CH3COO)3∙1.5 H2O), magnesium nitrate
(Mg(NO3)2∙6H2O) and europium acetate (Eu(CH3COO)3∙1.5 H2O)
were added dropwise to an aqueous solution of titanium isoprop-
oxide (Ti(C3H7O)4) (diluted in acid nitric solution (1.5 mol)). Due to
the likelihood of the sublimation of magnesium ions, the 10% excess
of magnesium nitrate was applied. The white precipitate was Fig. 1. The XRD results of LMT: Eu3þ with ICSD-86852 pattern. Inset: Unit cell volume
formed immediately after adding NH4OH (1 ml) and then was dried for samples doped with different Eu3þ concentration.
at 80  C for 24 h. The prepared precipitate was ground and pre-
sintered at 600  C for 12 h. The final annealing was carried out at
pm for 9-coord. [17]) for larger La3þ (121.6 pm for 9-coord. [17])
1300  C for 8 h.
causes the crystal structure to contract for a higher dopant
concentration.
2.2. Sample characterization

The XRD spectra were measured with an X’Pert PRO powder 3.2. Emission and excitation
diffractometer (PANalitycal, The Netherlands) equipped with a
linear PIXcel detector and using Cu Ka radiation (l ¼ 1.54056 Å). To The photoluminescence spectra of the representative sample of
measure the excitation spectrum, a McPherson spectrometer LMT: 4% of Eu3þ ions under an excitation of 532 nm are presented in
equipped with a Xe lamp and a Hamamatsu R928 photomultiplier Fig. 2 right. The red line shows the emission recorded at 300 K
was used. For emission measurements at 300 K and 77 K, the which consists of several peaks related to the forced-electric dipole
Hamamatsu photonic multichannel analyser PMA-12 equipped transitions (5D0 to 7FJ, where J ¼ 0, 2, 3, 4) as well as to the magnetic
with a BT-CCD linear image sensor and the Nd:YAG laser as the dipole (5D0 / 7F1). Due to the low La3þ symmetry site in the
excitation source were applied. A temperature of 77 K was obtained
using liquid nitrogen and a Dewar flask. The decay profiles were
recorded with a Lecroy digital oscilloscope and the Nd:YAG laser.
The emission spectra as a function of temperature were measured
with the Hamamatsu photonic multichannel analyser PMA-12
equipped with a BT-CCD linear image sensor. The temperature of
the samples during emission measurements was controlled by
applying Linkam THMS 600 Heating/Freezing Stage.

3. Results and discussion

3.1. Structure

All the studied samples crystallize in the same orthorhombic

crystal structure (ICSD 86852) in space-group Pbnm (62) (see Fig. 1)
with lattice parameters a ¼ 5.5609(1) Å, b ¼ 5.5738(1) Å and
c ¼ 7.8623(2) Å [16]. The structure has one La site coordinated by 10
oxygen ions with site symmetry CS and one site for Mg and Ti co-
ordinated by oxygen forming a distorted octahedron with site
symmetry C1. No additional phases were found in the material
studied and the quality of crystallization is very high.
Eu3þ ions enter the La site due to the charge and size match. This
can be evidenced by the fact that the unit cell volume (equal
Fig. 2. The 300 K excitation and the 77 and 300 K emission spectra of LMT: 4% Eu3þ. In
243.69(1) Å3 for the undoped host), calculated by the indexing the inset transitions from 5D1 levels and one peak of the 5D0 / 7F0 transition regis-
method, decreases with increasing Eu3þ concentration (see Fig. 1 tered at 77 K. (color available online). (For interpretation of the references to color in
inset). The substitution of smaller Eu3þ ions (ionic radius 106.2 this figure legend, the reader is referred to the Web version of this article.)
 B. Bondzior et al. / Journal of Alloys and Compounds 852 (2021) 157074
structure studied occupied by Eu3þ, the main emission peaks
located at 615.4 and 625.4 nm can be assigned to the forced-electric
dipole transition from 5D0 to 7F2 level. As can be seen, at low
temperature the peaks become more structured and the most
intensive one splits into three lines centred at 609.3, 614.9 and
624.7 nm. The full width at half maximum (FWHM) of band at
615.4 nm decrease from 137.4 cm1 to 52.9 cm1 for the 300 and
77 K, respectively. Additionally, smaller intensity bands attributed
to the transition from 5D1 to 7F1, 7F2 and 7F3 ground levels can be
also visible at 77 K (Inset of Fig. 2).
The excitation spectrum of the LMT monitored at the 5D0 / 7F2
transition (616 nm) shows a broad and intensive band centred at
316 nm (Fig. 2 left). Besides, the f-f bands of Eu3þ assigned to
transitions from 7F0 into 5L6, 5D3, 5D2 and 5D1 excitation states were
also observed in the form of four bands located at 386, 412, 458 and
533 nm, respectively.
The broad band on the excitation spectrum centred at 316 nm is
actually a convolution of two bands (see Fig. 3). The two bands can
be ascribed to the O2 / Eu3þ charge transfer band (at 327 nm)
(lower energy band e also reported by others [4,9]), measured as an
absorption of the LMT: Eu3þ sample and divided by the absortion of
undoped LMT, and to the absorption of the TiO6 groups (at 313 nm)
creating the conduction band of LMT.
The 77 K emission spectrum excited at 266 nm (see Fig. 4) re-
veals the presence of the TiO6 groups luminescence e broad
emission band located at 400e550 nm with the maximum at
478 nm (see Fig. 4 left inset). The excitation at 266 nm (corre-
sponding to the energy of 4.7 eV) is an excitation into the con-
duction band of the material (bandgap is reported to be 3.98 eV [6]),
which very quickly relaxes non-radiatively onto the available en-
ergy levels within the bandgap e both TiO6 groups and CTS. This
emission is easily thermally quenched with an activation energy
estimated 0.06 eV (480 cm1) (see Fig. 4 right inset) using the
following equation (1) [18]:
Fig. 3. The excitation spectrum (lem ¼ 616 nm) (solid black) and the O2 / Eu3þ
charge transfer band absorption (solid red). The red dashed line was fitted as a residual
excitation resulting from the excitation of Eu3þ via TiO6 groups. The absorption
spectrum of LMT: Eu3þ was corrected for the absorption of the undoped LMT host to
obtain the absorption purely linked to the europium ions. (For interpretation of the
references to color in this figure legend, the reader is referred to the Web version of
this article.)
3
Fig. 4. The 77 K emission spectrum of LMT: Eu3þ excited at 266 nm into the absorption
band of TiO6 group. Left inset: The TiO6 group emission band. Right inset: The TiO6
group emission thermal quenching.
I0
IðTÞ ¼ (1)
1 þ AeDE=kT
where I0 is the emission intensity at low temperature, A ¼ GG0n where
G0 is an attempt rate for thermal quenching and Gn is the radiative
decay rate of the transition, it can altogether be treated as a fitting
parameter, and DE is activation energy.
The probable cause of the quenching can be thermal excitation
to the conduction band. There are two excited levels of octahedrally
coordinated TiO6 [19]; the lower-lying Eg level may be located
0.06 eV below the other energy states constituting the conduction
band.
The temperature dependence of the intensity of the LMT: Eu3þ
emission excited at 266 nm (see Fig. 5 right) demonstrates that
even at low temperatures, the emission is quenched both from the
5
D1 and 5D0 level and there is more than one process contributing
to the thermal quenching of the Eu3þ luminescence. The experi-
mental data from Fig. 5 can be fitted by applying equation (1).
It turn outs that the activation energy is the same in the low
temperature range (<200 K), i.e. 0.06 eV for both the 5D0 and 5D1
emission, which is the same as for the host emission and confirms
the occurrence of an energy transfer between TiO6 groups and Eu3þ
ions. The mechanism of temperature quenching of the Eu3þ emis-
sion was depicted schematically in the configurational coordinate
model (see Fig. 5 left). The excitation at 266 nm (37594 cm1)
corresponding to the energy of 4.7 eV, is actually an excitation into
the conduction band of the material, which is formed by the energy
levels of TiO6 groups. The energy is then transferred to the Charge
Transfer State (CTS). A part of the 266 nm pumping excites the 5D1
and 5D0 levels (see Fig. 5 left - green lines).
In addition to excitation via the CTS, two other processes popu-
late the 5D0 level - the multi-phonon relaxation (MPR) from the 5D1
level and the cross-relaxation process (CR). The latter strongly de-
pends on the concentration of doping ions, its contribution increases
with the increase in their concentration (this problem will be tackled
in more detail in the discussion of emission decay curves).
The probability of multi-phonon relaxation WMPR between two
levels J and J0 depends on the distance between them DEJJ’ and on
the maximum energy of the phonons -6max, which for LMT is
4 B. Bondzior et al. / Journal of Alloys and Compounds 852 (2021) 157074

Fig. 5. Left: The single configurational coordinate diagram of the Eu3þ in LMT. Right: Thermal quenching profiles of 5D1 e 7FJ and 5D0 e 7FJ transition of Eu3þ luminescence in LMT
under 266 nm and 532 nm excitation. (color available online). (For interpretation of the references to color in this figure legend, the reader is referred to the Web version of this
article.)

741 cm1 [20]. It can be described using the following equation (2)
[21]:
 p
Z6
WMPR ¼ WMPR ð0Þ 1  e kT ; 
(2)
where p ¼ DE/-6 is the number of phonons coupling the energy
distance DE and WMPR(0) is multiphonon transfer rate for T ¼ 0 K. The
distance between levels 5D1 and 5D0 in LMT is equal to 1673 cm1
(0.2 eV), so more than two phonons at temperatures higher than 77 K
are enough to transfer nonradiatively energy to level 5D0, which
result in rather low rate of non-radiative transitions [22].
With the rise in temperature, the probability of this process
increases, but at the same time the occupation of vibronic levels of
the 5D1 and 5D0 grows, too. Consequently, the probability of the
nonradiative drainage (dark orange arrows in Fig. 5 left) of these
two levels through the CTS increases. The activation energies Ea1
and Ea0 of this process are pictured in Fig. 5 left as the distance
between the minimum of the 5D1 (or 5D0) parabola and its inter-
section with the CTS curve. For 5D1, the activation energy Ea1 is
equal to 0.3 eV and is 0.2 eV smaller (equal to the value of energy
difference between 5D1 and 5D0) than the activation energy Ea0 of
the 5D0 state (see Fig. 5 left).
In addition to the decrease in the emission intensity as a func-
tion of temperature, Fig. 5 right also clearly evidences population of
5
D0 from 5D1. This process reaches its maximum at around 400 K. It
the 7F0 e 7F3 energy gap is ~1850 cm1), the mismatch is
compensated by the filling of the crystal fields levels of 7F1 ac-
cording to the relationship (4):

gA DE
NA ¼ NB exp (4)
gB kT
where NA(B) is the population of the initial (final) level and gA(B) is
the degeneration of state A (B), DE is the energy difference between
these levels. As the temperature increases up to 400 K, the subse-
quent Stark levels of states 7F0, 1 are populated. With the further
rise in temperature, 5D0 is emptied with the activation energy Ea0
previously found. The value E’a0 greater than 0.5 eV determined
from the fitting (see Fig. 5 right) is due to the fact that the increase
in temperature also results in additional drainage from level 5D0, as
described in Equation (4).
3.3. Temperature sensing behaviour
Making use of the unusual thermal quenching profile of the
emission under 532 nm excitation, one can consider the fluores-
cence intensity ratio (FIR) between the emission excited at 532 nm
and the one excited at 266 nm, as a temperature indicator for
luminescent thermometry. Its value changes from almost 0 to 5 in
the range 77e450 K (see Fig. 6 black line). Then the values of thermal
sensitivity can be derived from the following formulae [24]:
is particularly well manifested when the Eu3þ ions are excited  
directly by bypassing the CTS. Similar phenomenon for Eu3þ was vFIR
Sa ¼   (5)
observed by Tian et al. [23]. The 532 nm excitation reaches the 5D1 vT 
level, which populates 5D0 via two processes - MNR and CR. The
 
former has already been discussed, the latter is more effective for  1 vFIR
higher concentrations of Eu3þ, described by the relation (3): Sr ¼  ,   100% (6)
[5D1, 7F0] / [5D0, 7F3]
The CR involves level 7F3. Although the energy difference of
the levels do not match (5D1 e 5D0 energy gap is 1673 cm1 and
FIR vT 
(3) The maximum of absolute Sa is at 212 K and is close to 0.02 K-1,
while the relative sensitivity Sr is increasing with decreasing tem-
perature with the maximum of 3% K1 for 77 K (see Fig. 6 red dash)
and is above 1% K1 for temperatures below 230 K (see Fig. 6 red
 B. Bondzior et al. / Journal of Alloys and Compounds 852 (2021) 157074 5

Table 1
Rise and decay time values for 5D0 luminescence in LMT: Eu3þ under 532 nm
excitation.

Eu3þ concentration (%) 5

D0

Rise (ms) Decay (ms)

0.1 94.1 566

0.5 91.4 597
1 89.6 583
3 59.9 557
4 59.0 527
5 49.7 530
7 39.6 531

    
t t
IðtÞ ¼ I0 exp  exp (7)
td tr

Fig. 6. The intensity ratio of Eu3þ emission excited at 532 nm to the one excited at
266 nm (black) along with derived values of absolute sensitivity Sa (red dash) and relative
intensity Sr (red solid). (color available online). (For interpretation of the references to
color in this figure legend, the reader is referred to the Web version of this article.)
line). For similar double-perovskite compounds, the sensitivities of
temperature determination Sr were equal to 0.8% K1 at 448 K
(LaMg0.402Nb0.598O3: Pr3þ), 1.73% K1 at 473 K (Gd2ZnTiO6: Tm3þ,
Yb3þ) and 8.52% K1 at 323 K (Ca2MgWO6: Bi2þ, Eu3þ), respectively
[25e27].
3.4. Decay curves
The decay curves of the Eu3þ emission reveals two processes
influencing the emission dynamics of the 5D0 / 7FJ transition. One
is a simple single-exponential emission decay (Fig. 7 left) and the
other is the population of the emitting level after the initial exci-
tation pulse by some non-radiative mechanism (Fig. 7 right). This
results in the decay curve, which can be described by the rise-decay
equation (7) [28]:
where I0 is the maximal emission intensity and tr, td are rise and
decay times, respectively. The values of rise and decay times are
listed in Table 1.
Similar luminescence dynamics in Eu3þ has been reported in
titanate materials [29] as well as other hosts [30], and it is usually
described and analysed in a similar manner.
While the decay time slightly decrease with an increase of Eu3þ
concentration, the rise time is heavily influenced by it and de-
creases more than twofold (see Table 1) from 94.1 ms for 0.1% Eu3þ
down to 39.6 ms for 7% Eu3þ.
The 5D0 level is efficiently populated from 5D1 via a multi-
phonon relaxation and cross-relaxation. This is manifested by the
characteristic rise time of the 5D0 emission decay curve. The
populating of the 5D0 level from the higher-lying 5D1 has been
discussed above and presented in Fig. 5 left. It can also be proved by
contrasting the decay curve resulting from the resonant excitation
of the 5D1 level with the decay curve of the same sample excited
into the CTS (see Fig. 8). In the latter case, the decay curve is a single
exponential and does not exhibit any rise time as the excitation into
the CTS populates the 5D0 level through the intercrossing of these
levels (as presented on the coordinate diagram Fig. 5 e left). The
same phenomenon was observed in Sr0.99La1.01Zn0.99O3.495 doped

Fig. 7. The 300 K luminescence decay curves of LMT: Eu3þ under 266 nm excitation in logarithmic (left) and linear scale (right).
6 B. Bondzior et al. / Journal of Alloys and Compounds 852 (2021) 157074

D1 in function of Eu3þ concentration with linear

Fig. 8. The decay curves of the LMT:Eu3þ luminescence excited at 532 nm (black) and Fig. 9. The cross-relaxation rate WCR
266 nm (red). (color available online). (For interpretation of the references to color in fitting of logarithm plot.
this figure legend, the reader is referred to the Web version of this article.)

based on the fact that the 5D0 / 7F1 magnetic-dipole transition is

with Eu3þ [31]. independent of the environment and its coefficient can be calcu-
We believe that the rise time results from the lifetime of the lated from (11) to be equal to 112 s1 [38], while the rest of the
higher level 5D1. Similar relationships have been observed, e.g. to coefficients can be calculated from relation (12) [39]. The Ul pa-
LaAlO3: Er3þ [32] or LaF3: Er3þ [33]. Therefore, the rise time can be rameters are listed in Table 2.
considered as the lifetime of the 5D1 multiplet (see Table 1).
The measured total emission decay rate WtotD1 of the 5D level can
1 A01 ¼ ðA01 Þvac ,n3 (11)
be described as follows:
I0J Zn01
D1
Wtot ¼ WRD1 þ WMP
D1 D1
þ WCR (8) A0J ¼ A01 (12)
I01 Zn0J
Where: WRD1 ¼ t1R is the radiative depopulation rate of the 5D1 Using the Ul parameters one can calculate the Einstein co-
level and tR is the radiative lifetime of this level, WMP
D1 is the mul- efficients of the 5D1 / 7FJ transitions [40]. The 5D1 / 7F0 is a
D1 is the depopulation rate of level magnetic-dipole type and can be obtained from the constant
tiphonon relaxation rate and WCR
5 relation of its dipole strength with the dipole strength of 5D0 / 7F1
D1 following cross-relaxation.
transition [40].
The energy transfer rate as a function of the Eu3þ concentration
can be estimated from the graph of the dependence on WDCR as a
D10
function of the Eu3þ concentration: MD
¼ 0:1875 (13)
D01
MD
D1 D1
WCR ð% EuÞ ¼ Wtot ð% EuÞ  WRD1  WMP
D1
(9)
The 5D1/7F2 transition, due to its mixed type, cannot be ob-
tained from the electric dipole strength only, therefore, it was ob-
Where it is assumed that the radiative and the multiphonon tran-
tained from the intensity ratio with the 5D1/7F3 transition
sition rates are independent of Eu3þ concentration. Thus the order
analogically to the 5D0/7F2,4,6 transitions using (12). All the Ein-
of energy transfer interaction by linear fitting of the lnðWCR D1 Þ
stein coefficients are listed in Table 3. From them, and the transition
against ln(Eu3þ concentration) can be analysed e see Fig. 9. The rate for the sample with 0.1% Eu3þ (assuming that the cross-
slope of the fitted line is close to 2, which indicates a two ion relaxation process is absent for this sample), one can calculate
process and is typical for the cross-relaxation. the radiative depopulation rate of the 5D0 and 5D1 levels WRD0 and
WRD1 , equal to 994 s1 and 1.026∙103 s1, respectively. From the
3.5. Judd e Ofelt analysis total emission decay rate and the relation presented in Fig. 9, the
multi-phonon energy transfer rate WMP D1 and the cross-relaxation
The Judd-Ofelt parameters Ul [34,35] were calculated from (10) D1 ð7%ÞÞ can be calculated to be equal to
depopulation rate WCR
     9.6∙103 s1 and 14.6∙103 s1, respectively. This illustrates, that out
64p4 v3 e2 1   2
A0J ¼ , , cUJ , 5 D0 U J 7 F J (10) of these three processes, the cross relaxation is the most efficient
3h 4pε0

where c is equal to n(n2 þ 2)2/9 and the matrix elements were Table 2
taken from the paper by Carnall et al. [36]. Judd-Ofelt parameters for LMT.
The calculations were based on the 300 K emission spectrum of
U2 U4 U6
LMT: 4% Eu3þ. The refractive index used in the calculation was
20 20
derived from the chemical composition [37] and equalled 1.9713. (10 2
cm ) (10 2
cm ) (1020 cm2)
7.4 0.6 9.4
The Einstein coefficients of spontaneous emission were calculated
 B. Bondzior et al. / Journal of Alloys and Compounds 852 (2021) 157074
Table 3
Transition rates AJJ’ and total radiative transition rates
form 5D0 and 5D1 level for Eu3þ in LMT.
transition rate (s1)
A01 112
A02 556
A04 311
A06 15
WD0R 994
A10 31
A11 226
A12 428
A13 311
A14 13
A15 3 measurements.
A16 15
WD1R 1026
process depopulating the 5D1 level and its rate is typical of fast
cross-relaxation [41,42]. Besides, the multi-phonon energy transfer
is one order of magnitude faster than the radiative transition, as
usual in the case of this system [29].
4. Conclusions
The samples of orthorhombic La2MgTiO6 doped with Eu3þ were
synthesized by the co-precipitation method. Eu3þ ions enter the La
site with CS symmetry. Under the 266 nm laser excitation both TiO6
groups and Eu3þ ions exhibit emission with maxima at 478 nm and
615 nm, respectively, however, the former is quenched at 200 K.
There are two broad absorption bands at 305 nm and 320 nm
assigned to TiO6 group absorption and O2 / Eu3þ charge-transfer
transition, respectively. The emitting 5D0 level can be populated by
a multitude of processes, among which there are the multiphonon
relaxation, cross-relaxation process and the non-radiative relaxa-
tion from the CT state. The first two processes are responsible for
the evolution of the rise time on the decay curves, while the latter
process is not. The rise time is Eu3þ concentration-dependent and
shortens with the Eu3þ concentration from 94.1 ms for 0.1% Eu3þ
down to 39.6 ms for 7%. The cross-relaxation is also the probable
cause of the increasing Eu3þ emission intensity with the temper-
ature up to 400 K when excited at 532 nm (into the 5D1 level). The
latter phenomenon gives rise to the possibility of luminescent
thermal sensing, which is characterized by the relative sensitivity
above 1% for low temperatures up to 230 K.
Due to the high specificity of the concentration-rise time
dependence in an Eu3þ doped host, it is possible to know the Eu3þ
concentration in the europium-doped ceramic or the powder ma-
terial, by simply measuring the rise time of luminescence. When
the material is excited by 266 nm the rise time of luminescence
does not occur, which creates the on-off behaviour of the rise time
depending on the excitation wavelength. It seems to us that such
unusual properties can be useful for the use of this phosphor as an
anti-counterfeit technology.
CRediT authorship contribution statement
B. Bondzior: Conceptualization, Methodology, Validation,
Investigation, Resources, Writing - original draft, Visualization,
Writing - review & editing. D. Stefan
ska: Conceptualization,
Methodology, Resources, Writing - review & editing. T.H.Q. Vu ~:
Methodology, Validation, Investigation, Writing - review & editing.
N. Miniajluk-Gaweł: Investigation, Writing - review & editing. P.J.
Deren
: Conceptualization, Writing - review & editing, Supervision,
Project administration, Funding acquisition.
7
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgement
This work was supported by the Polish National Science Centre
under Grant no. 2017/25/B/ST5/02670, as part of the research
project OPUS13. The authors would also like to thank E. Bukowska
for the XRD measurements and B. Macalik, PhD for the absorption
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