Journal of Luminescence 166 (2015) 130136

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Journal of Luminescence
journal homepage: www.elsevier.com/locate/jlumin

JuddOfelt analysis of Tm3 doped in CaSc2O4 ceramic samples

erban Georgescu a, Angela tefan a,b, Ana-Maria Voiculescu a, Octavian Toma a,n
a
National Institute for Laser, Plasma and Radiation Physics, 409 Atomitilor Street, 077125 Mgurele-Ilfov, Romania
b
University of Bucharest, Faculty of Physics, 405 Atomistilor Street, 077125 Mgurele-Ilfov, Romania

art ic l e i nf o a b s t r a c t

Article history: The JuddOfelt analysis is applied to light-scattering ceramic CaSc2O4 doped with Tm3 . The calibration
Received 5 January 2015 of the JuddOfelt parameters is performed by two approaches: (i) using the known magnetic-dipole
Received in revised form contribution to the transition intensity of 3H6-3H5; (ii) using the radiative lifetime of an energy level
27 April 2015
supposed to decay mainly radiatively (1G4 or 3F4). The following results were obtained:
Accepted 13 May 2015
Available online 22 May 2015
2 1.55  10  20 cm2; 4 1.71  10  20 cm2; 6 0.98  10  20 cm2, using the rst approach;
2 1.70  10  20 cm2, 4 1.84  10  20 cm2, 6 1.13  10  20 cm2 (calibration using 1G4);
Keywords: 2 1.57  10  20 cm2, 4 1.70  10  20 cm2, 6 1.04  10  20 cm2 (calibration using 3F4). The
CaSc2O4 obtained JuddOfelt parameters are used to calculate the radiative lifetimes and quantum efciencies of
JuddOfelt
several Tm3 levels, spontaneous emission probabilities and branching ratios of various Tm3 transi-
Tm3
tions. A fairly good agreement was obtained between the results of these methods.
& 2015 Elsevier B.V. All rights reserved.

1. Introduction radiative lifetimes (and quantum efciencies) of various excited

CaSc2O4 is a very promising host for efcient up-/down-con-
version ([1] and references therein) due to low-energy phonons
(540 cm  1 [2]), short distances between positions that can be
occupied by the dopants (assuring an efcient energy transfer) and
high solubility of ytterbium ions. Efcient visible upconversion
luminescence was obtained in CaSc2O4 codoped with Er3 and
Yb3 [3], Tm3 and Yb3 [1], and with Ho3 and Yb3 [4].
Cooperative down-conversion and near infrared luminescence
were obtained in CaSc2O4 doped with Tm3 and Yb3 [5].
Recently, we estimated an increase of 30% of the number of
photons emitted in the wavelength domain 5001600 nm, for
pumping in blue (at 488 nm), due to the presence of Yb3 in
CaSc2O4 ceramic samples doped with Ho3 and Yb3 [6].
The JuddOfelt (JO) theory [7,8] was successfully applied for
the characterization of the luminescent materials doped with tri-
valent rare-earth ions. A recent review (from the experimentalists
point of view) was given by Hehlen et al. [9]. A classic paper
concerning the JO theory was published by Peacock [10]. The great
advantage of the JO theory is the possibility to obtain the prob-
ability of any transition between two 4f n states with only three
parameters (2, 4, 6, JO parameters) which can usually be
obtained from the absorption spectra. Knowing these probabilities,
n
Corresponding author. Tel.: 40 21 457 45 50.
E-mail address: octavian.toma@inpr.ro (O. Toma).
levels as well as branching ratios can be calculated.
Obtaining the JO parameters for the characterization of phos-
phors doped with rare-earth ions, which are usually powders, is
difcult due to the absorption or emission spectra being affected
by light scattering in this kind of samples. In order to obtain the
values of the JO parameters, the absorption or emission spectra
must be calibrated. For materials with good transparency (crystals,
transparent ceramics or glasses), the absorption cross-section can
be calculated knowing the sample thickness and dopant con-
centration; in this way, the absorption spectrum is calibrated. For
Eu3 -doped phosphors, the JO parameters can be calculated using
the luminescence spectra calibrated with the strength of the pure
magnetic-dipole transition 5D0-7F1 which is practically inde-
pendent of the host [1113].
For phosphors doped with other rare-earth ions, various
methods to replace the absorption spectrum with some equiva-
lents were proposed: (i) using the excitation spectra [14,15], (ii)
measuring diffuse reectance spectra [16], (iii) dispersing the
powder doped with rare-earth ions in KBr pellets and measuring
the IR absorption spectra [17], (iv) embedding the nanocrystals
powder in a transparent epoxy [18], (v) measuring the photo-
acoustic spectra [19], and (vi) using the emission spectrum
5
D4-7FJ of Tb3 [20].
One of the major problems when dealing with excitation or
diffuse reectance spectra is the calibration of the spectra. The
authors of Refs. [14,15] selected for their analysis the energy levels
that relaxed very fast nonradiatively to a lower-lying excited level

http://dx.doi.org/10.1016/j.jlumin.2015.05.025
0022-2313/& 2015 Elsevier B.V. All rights reserved.
 . Georgescu et al. / Journal of Luminescence 166 (2015) 130136
used as a monitoring level. In these conditions, the authors have
shown that the excitation spectra are proportional with the
absorption spectra. For calibration, they used the lifetime of a level
known to decay mostly radiatively (4I13/2 for Er3 and 4F3/2 for
Nd3 ). Fischer et al. [16] converted the diffuse reectance spectra
of Er3 :NaYF4 in absorption spectra, using the KubelkaMunk
theory [21,22]. In order to separate the absorption from the dif-
fusion, they used powder samples of various thicknesses. Monteiro
et al. [17] used an integration sphere to measure the IR absorption
spectrum of Sm3 complexes (as powder diluted in KBr). Zhang
et al. [20] calibrated the emission spectrum of 1D4 in Tb:KY3F10 by
its lifetime (very close to the radiative lifetime in diluted samples).
In conclusion, the luminescence and excitation spectra can be
calibrated using additional information: the strength of a mag-
netic-dipole transition (as for Eu3 luminescence spectra [1113])
or the lifetime of an energy level known to decay mainly radia-
tively (4I13/2 for Er3 , 4F3/2 for Nd3 [14,15], or 5D4, for Tb3 [20]).
In the above cases, no information about the sample thickness or
dopant concentration was necessary.
In a recent paper [23], we proposed to use the magnetic-dipole
contribution to the Tm3 transition 3H6-3H5 to calibrate the
absorption spectrum of Tm3 in a langatate (La3Ga5.5Ta0.5O14)
ceramic sample. This material, having a granular structure, scatters
the transmitted light and thus the effective thickness of the
sample is not known. Therefore, the absorption cross-section
could not be calculated and additional information (in this case,
the strength of the magnetic-dipole contribution to the absorption
transition 3H6-3H5) was necessary.
In this paper, we aim to obtain the spectroscopic data of Tm3
in this new material by performing a JO analysis of this system.
The JO analysis is performed on absorption spectra obtained using
light-scattering samples due to the difculties that hinder the
growth of single CaSc2O4 crystals. We cannot use the lumines-
cence spectra (as for Eu3 -doped materials) for obtaining the JO
parameters of the upconversion phosphors, due to overlap of the
luminescence bands. This overlap is the result of the peculiar
structure of the energy levels of the dopant (energetic resonances)
that ensures the upconversion itself.
A method based on the magnetic-dipole transition 3H5-3H6 is
used here for the calibration of the JO parameters. The results
obtained using this method are then compared with the results of
the calibration method proposed in Refs. [14,15], based on the
knowledge of the lifetimes of energy levels that decay mostly
radiatively (1G4 and 3F4, in this paper).
We note that a JO analysis of Tm3 in CaSc2O4 was not per-
formed until now. The results are then used to calculate the
radiative lifetimes of the energy levels and the probabilities and
branching ratios of Tm3 transitions in CaSc2O4. The lifetimes of
several metastable levels are measured and the corresponding
quantum efciencies are calculated.
2. Experiment
The CaSc2O4 ceramic samples doped with Tm3 (atomic con-
centrations 0.05% and 4% compared with Sc3 ) were synthesized
by a solid-state reaction. The sample with 4 at% Tm3 was used in
absorption measurements while the samples with 0.05 at%
Tm3 -in decay measurements. Details concerning the synthesis
can be found elsewhere [6]. The ceramic sample of CaSc2O4:
Tm(4 at%) is a 12 mm diameter disk with 0.22 mm thickness. The
fact that the CaSc2O4 sample is not opaque enabled us to measure
the absorption spectrum. In order to increase the intensity of the
transmitted light, the sample was cut as thin as allowed by its
mechanical properties. The visible part of the absorption spectrum
was measured on a Horiba Jobin-Yvon (1000M series II)
131
monochromator equipped with an S-20 photomultiplier (EMI
9658B). The IR part of the absorption spectrum was measured with
a 1 m Jarrell-Ash monochromator equipped with a Germanium
(Judson J16D) or PbS (Thorlabs PDA30G) detectors. The signal from
the detectors was processed by a lock-in amplier (SR830 from
Stanford Research Systems). The base line for the absorption
spectra was measured on a non-doped CaSc2O4 ceramic sample
synthesized in similar conditions and having the same dimensions.
For decay measurements, the luminescence was excited in blue (at
465 nm), in red (at 700 and 705 nm), and in near IR (at 795 nm)
with a Quantel Rainbow OPO and analyzed with a Tektronix 2024C
oscilloscope. To measure the luminescence decays of 1D2, 1G4 and
3
H4, we used a photomultiplier as detector, while for the decay of
3
F4 we used a TE-cooled InGaAs PIN photodiode (Hamamatsu). All
the measurements were performed at room temperature.
3. Results and discussion
CaSc2O4 crystallizes with the CaFe2O4 structure, having space
group Pnam (D16 2h ), Z 4, with the unit cell parameters a 9.461 ,
b11.122 , and c 3.143 [24]. The volume of the unit cell is
V330.723 3. There are two octahedral Sc3 positions and one
eightfold coordinated Ca2 position. Although Tm3 ions have
larger ionic radius than Sc3 (0.88 compared with 0.745 [25]),
Tm3 ions enter the Sc3 positions [2]. There are 2.419  1022
Sc3 positions per cm3.
Unfortunately, there is only one report concerning the refrac-
tive index of CaSc2O4, without any information regarding the
dispersion [26]. The reported value is n 1.9. In the following, we
will consider this value when calculating the crystal eld correc-
tions, neglecting the dispersion of the refractive index.
In Fig. 1 we show the absorption spectrum (absorbance,
A ( ) = ln (I ( ) /I0 )) of Tm3 in a CaSc2O4:Tm(4 at%) ceramic
sample. Seven absorption bands (3H6-1D2, 1G4, 3F2, 3F3, 3H6, 3H5,
3
F4) were observed. In fact, only six absorption bands can be used
in the JO analysis, since the transitions 3H6-3F2 and 3H6-3F3 are
overlapped. Except for 3H6-3H5, the transitions are pure electric-
dipole transitions. The features observed in the long wavelength
side of the 3H6-3F4 absorption band are due to the incomplete
removal of the water absorption lines.
The absorption spectrum recorded on the ceramic sample is
averaged on the polarization directions due to the random orien-
tation of the constituent crystallites. The polycrystalline structure
of the sample results in light scattering and the absorption spectra
were consequently obtained in arbitrary units. Although the
optical path lengths of various light rays in the sample can vary
with the wavelength, the limits of our methods force us to neglect
the variation of the effective sample thickness with the wave-
length. Approximations of this kind are implicitly made when
Fig. 1. Absorption spectrum of Tm3 in CaSc2O4:Tm(4 at%). Except for 3H6-3H5,
the transitions are pure electric-dipole.
132 . Georgescu et al. / Journal of Luminescence 166 (2015) 130136

diffuse reectance or excitation spectra measured on powder depending on ) entering Eqs. (1) and (2) (including the refractive
samples are used for the calculation of the JO parameters [14,15]. index n 1.9) were collected, for convenience, in the calibration
In the following, we calibrate the absorption spectrum of Tm3 parameter K:
in CaSc2O4 using the magnetic-dipole contribution to the 3H5-3H6
3ch (2J + 1) 9n 1
transition; then, a calibration method based on the lifetimes of 1G4 K=
8 3e2 2 N0 deff
and 3F4 levels is applied for comparison. (
n2 +2 ) (3)

We note that K depends on the product N0deff. This parameter is

3.1. Calibration based on the magnetic-dipole contribution to the unknown due to the lack of knowledge of the samples effective
3
H6-3H5 transition
thickness deff. The intensity parameters and the calibration para-
meter K are solutions of the following system:
According to the JO theory, the strength of an electric-dipole
transition relates to the absorption spectrum by 1
m 3H6 U (m) 3H5 ~ K abs.line A ( ) d
2 m = 2,4,6
Sed (H, 3
6
2S + 1
)
LJ = m H6 3
U (m) 2S + 1L J
9n2
m = 2,4,6 =
2
Smd (H, H)
3
6
3
5

=
9n 3ch (2J + 1)
~ abs.line k ( ) d (n2 +2 )
2
8N0 e2 3
(n 2 +2 ) (1)
2 1
m 3H6 U (m) 2S + 1L J ~ K abs.line A ( ) d
m = 2,4.6
where k() is the absorption coefcient, N0 is the concentration (in
cm  3) of the rare-earth ions in the sample, is the transition =0 (4)
average wavelength, n is the refractive index of the material and where 2S 1LJ 3F4, 3H4, 3F2,3, 1G4, and 1D2.
2 2
( )
n2 + 2 /9n is the crystal eld correction [27]. U (m) are the There are four parameters to be determined: 2, 4, 6, and K
squares of the reduced matrix elements of the unitary operators in (included in the vector X), and six equations. The best solution in
intermediate coupling, and m are the three JO parameters. The the least squares approximation is given by the matrix equation
remaining constants (e, c, h) have the usual meaning. The neces- X (ATA)  1ATB, where A is the system matrix, AT its transpose and
2 B is the free terms vector with only one non-zero component
sary reduced matrix elements U (m) for both absorption and
emission were taken from Ref. [28]. In our absorption experiments, 9n2
N0 9.676  1020 cm  3 (4 at%).
B1 =
2
Smd (H, H)
3
6
3
5

If the transition consists of both electric- and magnetic-dipole

( n2 +2 ) (5)
contributions (3H6-3H5, in our case), the strength of the electric-  22

dipole transition is
with Smd ( H , H )= 40.02  10
3
6
3
5
2
cm [28].
Solving Eq. (4), we found: 2 1.55  10  20 cm2, 4
9n 3ch 2J + 1
( ) 1.71  10  20 cm2, 6 0.98  10  20 cm2, and K 5.97
Sed (H , H)=
3
6
3
5 2

8N0 e2 3~
abs.line k ( ) d  10  19
cm . Knowing N0 9.676  1020 cm  3, deff 1.27 mm is
2

(n 2 +2 ) obtained.
nSmd ( H , H )
3
6
3
5 (2)
3.2. Calibration based on the radiative lifetimes of 1G4 and 3F4 levels
Smd ( H , H ) is the strength of the magnetic-dipole transition. The
3
6
3
5
Except for 3H6-3H5, the transitions shown in Fig. 1 are pure
allowed magnetic-dipole transition strength practically does not
depend on the host material. electric-dipole transitions. The strength of an electric-dipole
Due to the scattering of the transmitted light, the path of the transition is given by Eq. (1). With k()A()/deff and K dened in
light in the sample is longer than the sample thickness; the Eq. (3), Eq. (1) becomes
effective thickness (deff from now on) of the ceramic sample is not 2 K
known and remains to be determined. For this reason, we decided m 3H6 U (m) 2S + 1L J = ~ abs.line A ( ) d
(6)
to use the absorbance (A()) instead of the absorption coefcient;
m = 2,4,6

k() was replaced with A()/deff, supposing that the effective where 2S 1 3
LJ F4, H4, F2,3, G4, and D2.3 3 1 1

thickness depends only weakly on the light wavelength. Dividing Eq. (6) by K, only three unknown parameters
The values of the measured areas abs . line A ( ) d of the transi- m = m /K remain to be determined in the least squares approx-
tions shown in Fig. 1 are given in Table 1. The constants (i.e. not imation. The results are: 2 2.62  10  2, 4 2.85  10  2, and

Table 1
Absorption transitions, average wavelength ( ), and measured and calculated absorption integrals for the absorption transitions of Tm3 in CaSc2O4 shown in Fig. 1.

Transition (m) measured A () d (cm) calculated A () da (cm) calculated A () d|b,c (cm)

3
H6-3F4 1.681 70.76  10  7 71.27  10  7 71.66  10  7
-3H5 1.183 30.05  10  7 32.96  10  7
-3H4 0.785 15.36  10  7 14.31  10  7 14.78  10  7
-3F2,3 0.686 19.17  10  7 18.72  10  7 19.41  10  7
-1G4 0.467 2.94  10  7 1.60  10  7 1.60  10  7
-1D2 0.361 4.09  10  7 3.82  10  7 3.83  10  7
2.44  10  7 1.24  10  7

a
Calibration based on the magnetic-dipole contribution to the 3H6-3H5 transition.
b,c
Calibration based on the radiative lifetime of 1G4/3F4.
 . Georgescu et al. / Journal of Luminescence 166 (2015) 130136 133

6 1.74  10  2. Using the m parameters, we can calculate the The radiative lifetime is given by
probability of the radiative transition from a Tm3 level known to
( G ) = A ( G ) + A ( G )
1
emit mostly radiatively. We have chosen the level 1G4 since the rad 1
4 ed
1
4 md
1
4 (8)
energy gap between 1G4 and 3F2 levels is large enough
3
(  6500 cm  1) and approximately 12 phonons of 540 cm  1 [2] are Most of the emitting levels of Tm are involved in cross-
necessary to bridge this gap. The 3F4 level was also chosen due to relaxation processes [3136]. In order to reduce their inuence on
the gap between 3F4 and 3H6 being comparatively large (  8 the kinetics of 1G4 level, its decay was measured on a
phonons). Therefore, the probability of the multiphonon decay of CaSc2O4:Tm(0.05 at%, i.e. 1.21  1019 cm  3) sample. The decay of
these two levels can be considered negligibly low. the 1G4 level excited at 465 nm (transition 3H6-1G4) and mea-
sured at 657.5 nm (transition 1G4-3F4) is given in Fig. 2. For this
very low Tm3 concentration, the decay of 1G4 is close to expo-
3.2.1. 1G4 nential with a lifetime 372 s. Thus, Aed(1G4)1/Amd(1G4)
The electric-dipole transition probability from 1G4 to the lower 2466 s  1 and K 6.47  10  19 cm2 is obtained. Knowing K, the
energy levels is values of the JO parameters are calibrated: 2 1.70  10  20 cm2;

2
64 4e2 (
n n2 + 2 )
Aed (G ,1
4
2S + 1
LJ = ) ~3
3h (2J + 1) 9
1 2
K m G4 U (m) 2S + 1L J
m = 2,4.6 (7)

where 2S 1LJ 3F2, 3F3, 3H4, 3H5, 3F4, and 3H6.

For the magnetic-dipole transitions, the probability was
obtained using the relation Amd = (n/n)3Amd where n is the
refractive index of CaSc2O4 and Amd , n are the magnetic-dipole

transition probability and refractive index for a reference material;

we used as reference materials Tm:YLiF4 for 1D2 [29] and Tm:
TZPPN glass [30] for the remaining transitions. The values of the
Fig. 2. Kinetics of 1G4 level in CaSc2O4:Tm(0.05 at%). ex 465 nm (3H6-1G4),
probability of the magnetic-dipole transitions are given in Table 2. lum 657 nm (1G4-3F4). Symbols: experiment; continuous gray line: exponential
1
We obtained Amd ( G ) 222.6 s
1
4 . t (exp 372 s). Inset: luminescence spectrum 1G4-3F4.

Table 2
Average wavelengths (em ), electric-dipole ( Aed a, Aed b, Aed c) and magnetic-dipole (Amd) transition probabilities, radiative lifetimes (rad a,rad b, rad c), experimental lifetime
(exp) and the branching ratios (a, b, c) for Tm3 in CaSc2O4.

Transition em (m) Aed a (s  1) Aed b (s  1) Aed c (s  1) Amd (s  1) rad a (s) rad b (s) rad c (s) exp (s) a (%) b (%) c (%)

1
D2-1G4 1.540 153.95 167.01 154.52 0 36 33 36 12.5 0.56 0.56 0.55
-3F2 0.783 1259.89 1358.62 1257.02 70.49 4.82 4.75 4.77
-3F3 0.753 845.58 919.75 850.96 116.58 3.49 3.45 3.48
-3H4 0.663 1410.71 1582.20 1463.87 0 5.11 5.26 5.26
-3H5 0.515 133.61 151.94 140.58 0 0.48 0.51 0.50
-3F4 0.456 10985.28 11993.59 11096.66 0 39.79 39.88 39.86
-3H6 0.363 12631.46 13716.83 12691.03 0 45.75 45.61 45.58
1
G4-3F2 1.593 22.11 24.18 22.37 0 410 372 399 372 0.91 0.90 0.89
-3F3 1.475 70.03 78.83 72.93 4.67 3.06 3.11 3.10
-3H4 1.166 205.44 231.40 214.09 42.43 10.15 10.19 10.25
-3H5 0.774 720.85 820.13 758.80 161.81 36.15 36.53 36.77
-3F4 0.648 198.83 223.07 206.39 13.69 8.70 8.81 8.79
-3H6 0.475 1001.66 1087.96 1006.60 0 41.03 40.47 40.20
3
F2-3F3 19.794 0.02 0.02 0.02 0.04 656 582 629 0.00 0.00 0.00
-3H4 4.343 10.15 11.09 10.26 0 0.67 0.65 0.65
-3H5 1.506 302.74 337.42 312.18 0 19.85 19.64 19.64
-3F4 1.094 425.71 466.08 431.22 0 27.91 27.13 27.13
-3H6 0.677 786.60 903.33 835.78 0 51.57 52.58 52.58
3
F3-3H4 5.563 4.10 4.50 4.16 0.33 320 287 310 0.14 0.14 0.14
-3H5 1.630 248.86 270.45 250.22 0 7.97 7.77 7.75
-3F4 1.157 74.82 85.75 79.34 72.66 4.72 4.55 4.71
-3H6 0.701 2722.94 3048.27 2820.31 0 87.17 87.54 87.40
3
H4-3H5 2.305 36.57 39.40 36.45 11.13 779 699 754 540 3.71 3.53 3.59
-3F4 1.462 108.95 120.52 111.51 23.84 10.35 10.09 10.21
-3H6 0.802 1102.93 1235.14 1142.77 0 85.94 86.37 86.20
3
H5-3F4 3.994 2.88 3.14 2.90 0.19 2610 2404 2548 257 0.80 0.80 0.79
-3H6 1.229 279.73 312.29 288.94 100.42 99.20 99.20 99.21
3
F4-3H6 1.775 229.01 249.56 230.89 0 4367 4007 4331 4331 100 100 100

a
Calibration based on the magnetic-dipole contribution to the 3H6-3H5 transition.
b
Calibration based on the radiative lifetime of 1G4.
c
Calibration based on the radiative lifetime of 3F4.
134 . Georgescu et al. / Journal of Luminescence 166 (2015) 130136

4 1.84  10  20 cm2; 6 1.13  10  20 cm2 and deff 1.17 mm is
obtained using Eq. (3) (geometric thickness 0.22 mm).
3.2.2. 3F4
The decay of the 3F4 level measured at 1750 nm on a
CaSc2O4:Tm(0.05 at%) sample for the excitation at 795 nm
(3H6-3H4) is given in Fig. 3. To minimize the effect of the strong
reabsorption, the sample was diluted in KBr. The lifetime is
4331 ms (for the undiluted sample, a lifetime of 5750 ms was
obtained). The risetime in Fig. 3 is due to the pump conditions (to
be discussed below).
The calibration based on the radiative lifetime of 3F4 is per-
formed on the same set of parameters found from Eq. (6)
considering that the radiative lifetime of 3F4 is equal to its lumi-
nescence lifetime (4331 ms). The results are 2 1.57  10  20 cm2;
4 1.70  10  20 cm2; 6 1.04  10  20 cm2 (with K 5.99
 10  19 cm2) and deff 1.27 mm.
3.3. Discussion
An estimation of the accuracy of the calculations of t is given
1/2
by the rms deviation = ( ( ) / (q p ) )
2 where is the dif-
ference between the calculated and the experimental values of the
integrals of the absorption spectra, q is the number of the transi-
tions analyzed and p is the number of parameters. For the cali-
bration method based on the magnetic-dipole contribution to the
3
H6-3H5 transition, q 6, p 4, and 2.44  10  7 cm. For the
calibration methods based on the radiative lifetimes of 1G4 and 3F4,
q 5, p 3, and 1.24  10  7 cm. The calculated integrals of the
absorption spectra are given in Table 1 for both calibration
methods, together with the experimental ones. For the calibration
method based on the radiative lifetimes, the values of the integrals
of the absorption spectra were calculated using the parameters.
The values of are listed in the last line of Table 1; they denote a
rather good agreement between the calculated and the experi-
mental data and, consequently, a rather good precision in the
determination of the intensity parameters. An advantage of the
calibration method based on the magnetic dipole is that this
method does not require additional measurements that would
introduce supplementary sources of measurement errors.
There is much data published in the scientic literature
regarding the dependence of the JuddOfelt parameters on various
material parameters; these results are obtained mainly on rare-
earth-doped glasses where the variation of the JO parameters is
correlated with the controlled changes of the glass composition. To
our best knowledge, there is no available data about the Judd
Ofelt parameters of Tm3 in hosts with similar structures
(CaFe2O4 structure). We have chosen, for comparison with our
data, Sc2O3 [37] (in which Tm3 substitutes Sc3 , also) and Y2O3
[11,38,39], which is isomorphous to the former. The results
reported in the literature for the Tm3 intensity parameters in
these hosts are presented in Table 3, together with our results. It
can be easily noticed that the results can be very different even for
the same host (see, for example, Y2O3 [11,38,39] in Table 3).
However, a general trend that can be observed is that 6 is the
smallest of the three intensity parameters; our data follow this
trend.
The JO parameter 6 is generally related to the rigidity of the
host [9], decreasing with the increase of rigidity. Since the oxides
have high rigidity [40], we expect a rather low value of 6, which
is experimentally observed. The values we found for 6 are rather
close to the value obtained for Sc2O3 (Table 3). According to [41],
4 can also be correlated with hosts rigidity. The JO parameter 2
is related to the covalence and site symmetry [4244]. Never-
theless, the spread of the values of the 2 and 4 parameters
presented in Table 3 for various oxides and even for the same
oxide (for example, Y2O3 [11,38,39]), makes the drawing of a clear
conclusion a very difcult task.
Knowing the JO parameters, we can calculate the probabilities of
( )
the radiative transitions A 2S + 1L J , 2S + 1LJ (as the sum of electric- and
magnetic-dipole contributions), radiative lifetime rad 2S + 1L J of an ( )
excited state (using an equation similar to Eq. (8)) and the branching
ratios as 2S + 1L J , 2S + 1LJ = A 2S + 1L J , 2S + 1LJ rad 2S + 1L J . The
( ) ( ) ( )
results are given in Table 2.
In order to compare the results of the JO analysis with the
experiment, we measured, besides the lifetimes of 1G4 and 3F4, the
lifetimes of 1D2 and 3H4 Tm3 levels. All lifetime measurements
were performed on a CaSc2O4:Tm(0.05 at%) sample. The results are
presented in Table 2.
The luminescence of 1D2 level can be excited at 355 nm with
the third harmonic of a Nd:YAG laser (direct pumping). The UV
excitation light activates, besides the Tm3 luminescence, the
hosts or, possibly, the random impurities luminescence that
obscures the 1D2 emission. An inspection of the energy level
scheme of Tm3 (Fig. 4) suggests that the 1D2 level can be popu-
lated by upconversion, for pumping in 3F2,3. At low Tm3 con-
centrations (0.05 at%) the main upconversion process is excited-
state absorption (ESA); the ground state absorption (GSA)
3
H6-3F2,3 is followed by the rapid multiphonon transition to 3H4,
and by ESA 3H4-1D2. The kinetics of 1D2 was measured for
705 nm pumping (3H6-3F2,3). The decay of 1D2 level, recorded at
364 nm, is shown in Fig. 5. The 364 nm wavelength corresponds to
the 1D2-3H6 transition. (Transition 1D2-3F4 can also be used for
recording the decay of 1D2, but it can overlap with transition
1
G4-3H6.) The decay is exponential with a lifetime exp 12.5 ms.
No risetime is observed in the decay of 1D2, conrming that ESA is

Table 3
JuddOfelt parameters of Tm3 in CaSc2O4 and in several oxide crystals.

Crystal 2 (10  20 cm2) 4 (10  20 cm2) 6 (10  20 cm2) Reference

CaSc2O4 1.55 1.71 0.98 This worka

CaSc2O4 1.70 1.84 1.13 This workb
CaSc2O4 1.57 1.70 1.04 This workc
Sc2O3 2.92 1.30 0.90 [37]
Y2O3 4.07 1.46 0.61 [11]
Y2O3 1.44 2.13 1.22 [38]
Y2O3 2.47 0.59 0.29 [39]

Fig. 3. Kinetics of 3F4 level in CaSc2O4:Tm(0.05 at%) diluted in KBr. ex 795 nm a

Calibration with magnetic-dipole component of 3H6-3H5 transition.
(3H6-3H4), lum 1750 nm. Symbols: experiment; continuous gray line: t. b
Calibration with the lifetime of 1G4 level.
exp 4331 ms (descending part). Inset: luminescence spectrum 3F4-3H6. c
Calibration with the lifetime of 3F4 level.
 . Georgescu et al. / Journal of Luminescence 166 (2015) 130136
Fig. 4. Part of the energy level scheme of Tm3 in CaSc2O4. Upward solid arrows:
pump transitions; downward solid arrows: luminescent transitions; dashed
arrows: multiphonon transitions.
Fig. 5. Kinetics of 1D2 level in CaSc2O4:Tm(0.05 at%). Symbols: experiment; con-
tinuous gray line: exponential t. ex 705 nm, lum 364 nm. exp 12.5 ms. Inset:
luminescence spectrum 1D2-3H6.
Fig. 6. Kinetics of 3H4 level in CaSc2O4:Tm(0.05 at%). Symbols: experiment; con-
tinuous gray line: exponential t. ex 700 nm (3H6-3F2), lum 809 nm.
exp 540 ms. Inset: luminescence spectrum 3H4-3H6.
the dominant upconversion process [45]. Similar methods were
used in Refs. [4648] for the excitation of 1D2 luminescence.
The decay of 3H4 level in CaSc2O4:Tm (0.05 at%) is shown in
Fig. 6. The pump transition is 3H6-3F2,3 (at 700 nm) (see Fig. 4).
Due to the narrow energy gap between 3F3 and 3H4, the excitation
is transferred rapidly to 3H4 and no rise-time is observed in the
decay of this level. The rst steeper part of the decay is due to the
scattered pump light inside the monochromator. The decay is
exponential with a lifetime 540 ms.
The energy gaps between 1D2 and 1G4, and between 1G4 and 3F2
correspond to approximately 10 lattice phonons (of 540 cm  1);
the energy gap between 3F2,3 and 3H4 correspond to  2 phonons,
that between 3H4 and 3H5 corresponds to 7 phonons, between
135
3
H5 and 3F4 to  3 phonons while the gap between 3F4 and 3H6
corresponds to  8 phonons. At very low Tm3 concentration,
where the effect of the cross-relaxation processes is negligible, we
expect 1D2, 1G4, 3H4, and 3F4 levels to decay mainly radiatively
while 3F2,3 and 3H5, mainly non-radiatively. In fact, no risetime was
observed in the decay of 3H4 for pumping in 3F2,3 i.e. 3F2,3 decays
very rapidly.
Since part of the excitation from 3H4 (pump level) arrives on 3F4
via 3H5, a rough estimation of the lifetime of 3H5 level can be done
by analyzing the risetime of 3F4 kinetics in Fig. 3 for pumping in
3
H4, taking into account that the lifetime of 3F4 is 4331 ms and the
lifetime of 3H4 is 540 ms. A good description of the 3F4 kinetics is
I (t ) = 1.348exp(t /4331)0.479exp(t /540)
0.864exp(t /257) (9)
3
where the 257 ms lifetime could be associated with H5. The
quantum efciencies of the 1D2, 1G4, 3H4, 3F4, and 3H5 levels can be
calculated using the data given in Table 2.
A large difference between radiative and experimental lifetime
was obtained for 1D2 level. At present, we cannot explain this dif-
ference because the large energy gap between 1D2 and 1G4 precludes
the multiphonon relaxation and the very low Tm3 concentration
(0.05 at% or 1.21  1019 cm  3) leads to negligible contributions of
energy-transfer processes. On the other hand, the presence of
energy transfer to random impurities would deviate the 1D2 decay
from an exponential. Depending on the calibration method, the
quantum efciency of this level is between 35% and 38%.
The intensity parameters obtained using the above calibration
methods are presented together in Table 3. The three sets are close
to one another; the closest two sets are the one calibrated using
the magnetic dipole and the one calibrated using the lifetime of
3
F4, although these sets are obtained from two independent
equation systems. A look at Table 2 can also show that these two
methods both yield a subunitary quantum efciency for 1G4 (91%,
respectively 93%); the method based on the assumption that 1G4
has quantum efciency equal to 1 yields a supraunitary quantum
efciency for 3F4 while the calibration method based on the
magnetic dipole yields for 3F4 a quantum efciency of 99%. Func-
tion of the calibration method, the quantum efciency of 3H4 is
between 69% and 77%. A roughly-estimated quantum efciency of
3
H5 is 1011%. The other results (radiative lifetimes, spontaneous
emission probabilities, branching ratios) obtained from the three
JO parameters sets and listed in Table 2 are very close to one
another.
We note that the used calibration methods yield the JO para-
meters without requiring the knowledge of the Tm3 concentra-
tion or of the sample thickness. Both these parameters are con-
tained in the calibration parameter K; knowledge of one of them
enables the nding of the other.
4. Conclusion
The JuddOfelt parameters of Tm3 in CaSc2O4 ceramic were
obtained from the absorption spectrum. In order to increase the
transparency of the ceramic sample, the absorption spectrum was
measured on a thin (0.22 mm) but relatively concentrated (4 at%)
Tm:CaSc2O4 sample.
Due to the granular structure of the ceramic sample, the trans-
mitted light is scattered and the effective thickness of the sample is
not known and should be determined. Two independent methods
were used to calculate the JuddOfelt parameters: (i) direct calibration
based on the known magnetic-dipole contribution to the intensity of
the 3H6-3H5 transition; (ii) calibration using the lifetime of the 1G4 or
3
F4 level measured in a very diluted Tm:CaSc2O4 ceramic sample
136 . Georgescu et al. / Journal of Luminescence 166 (2015) 130136

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