Tunable greenish-to-reddish light

generation via energy transfer in

Tb3+/Sm3+-codoped PbGeO3 :PbF2 :
CdF2 glass under UV excitation

Rafaela T. Alves
Luciano A. Bueno
Artur Da S. Gouveia-Neto

Rafaela T. Alves, Luciano A. Bueno, Artur Da S. Gouveia-Neto, “Tunable greenish-to-reddish light

generation via energy transfer in Tb3+/Sm3+-codoped PbGeO3 : PbF2 :CdF2 glass under UV
excitation,” Opt. Eng. 58(1), 017105 (2019), doi: 10.1117/1.OE.58.1.017105.

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 Optical Engineering 58(1), 017105 (January 2019)

Tunable greenish-to-reddish light generation via energy

transfer in Tb3+/Sm3+-codoped PbGeO3 :PbF2 :CdF2 glass
under UV excitation
Rafaela T. Alves,a Luciano A. Bueno,b and Artur Da S. Gouveia-Netoa,*
a
Universidade Federal de Alagoas, Instituto de Física, Maceió, Alagoas, Brazil
b
Universidade Federal do ABC, Centro de Engenharia, Modelagem e Ciências Sociais Aplicadas, São Paulo, Brazil

Abstract. Generation of tunable greenish–yellowish–reddish luminescence mediated by energy transfer in

Tb3þ ∕Sm3þ -codoped fluorogermanate glass under UV light excitation is reported. Fluorescence emissions
around 487, 542, 561, 582, 600, 620, 645, 650, and 706 nm were obtained in double-doped samples under
355- and 375-nm excitation wavelengths. The relative intensity of the Sm3þ and Tb3þ ions’ individual distinctive
emissions depends upon the excitation wavelength, relative ions concentration, and the energy transfer of
Tb3þ to Sm3þ mechanism, which lead to the tonality tunable overall luminescent color. The CIE-1931 chromaticity
coordinates of the overall luminescence resided in the range (0.31; 0.59) to (0.62; 0.37). Time decay measure-
ments indicated efficient Tb3þ to Sm3þ energy-transfer process with a substantial decrease (1.65 to 0.85 ms) of
Tb3þ emitting levels due to the presence of Sm3þ ions in the host matrix. © 2019 Society of Photo-Optical Instrumentation
Engineers (SPIE) [DOI: 10.1117/1.OE.58.1.017105]
Keywords: multicolor; tunability; luminescence; phosphor; energy transfer; glass.
Paper 181522 received Oct. 24, 2018; accepted for publication Dec. 27, 2018; published online Jan. 23, 2019.

1 Introduction has been investigated recently.37–40 However, the main inter-

New host materials doped with rare-earth ions for application
in LED-based illumination technology are the subject of
enormous scientific and technological interest in the last
few decades. Applications range from lasers, optical ampli-
fiers, and waveguides to white-light-emitting diodes and
field-emission displays, among others.1–10 The main goal
is pursuing the generation of either the primary RGB colors
or a combination of colors possessing the capability of being
modulated in time, space, intensity, color tone, and/or color
temperature, yielding the so-called “smart light.” Rare-earth
ions are very efficient light emitters, particularly in the vis-
ible spectral region when excited either by downconversion
using UV-blue sources7–10 or via frequency upconversion
exploiting near-infrared (NIR) excitation.11–17 Multicolor
luminescence is generated exploiting a combination of red
(Eu3þ , Sm3þ , and Er3þ ), green (Er3þ , Ho3þ , and Tb3þ ),
and blue (Tm3þ ) light emitters as activating ions incorpo-
rated into a phosphor material. So, it is very important
to study and evaluate the effect of interionic interaction
involving activating ions in multidoped phosphors. In
the past few years, several reports have been devoted to
the search for warm-light emission phosphors using
combinations of rare-earth doping including Eu3þ ∕Tb3þ ,
Eu3þ ∕Dy3þ , Eu3þ ∕Ce3þ , Eu3þ ∕Er3þ , Tm3þ ∕Dy3þ , Tm3þ ∕
Dy3þ ∕Sm3þ ,18–26 and in Tb3þ ∕Dy3þ -codoped silicate,27
CaO − Al2 O3 − B2 O3 − RE2 O3 ,28 lead borate,29 and zinc
phosphate30,31 glasses. Recently, the generation of tunable
polychromatic light mediated by energy-transfer processes
involving active ions has been demonstrated.32–36 The gen-
eration of polychromatic luminescence and interionic inter-
action involving Tb3þ and Sm3þ in several glassy systems
*Address all correspondence to Artur Da S. Gouveia-Neto, E-mail:
asgouveianeto@hotmail.com
est in the reports resides in the analysis of the energy-transfer
mechanism connecting both active ions. This paper reports
on the energy-transfer mechanism and the generation of tun-
able polychromatic light emission in the greenish-to-reddish
CIE-1931 color coordinates region in Tb3þ ∕Sm3þ codoped
PbGeO3 ∶PbF2 ∶CdF2 glass under UV excitation.
2 Experiment
The base glass in the chemical composition 80%PbGeO3 ∶
10%PbF2 ∶10%CdF2 was prepared with reagent grade
PbF2 (P.A. Aldrich) and CdF2 (P.A. Aldrich) and glassy
PbGeO3 . Starting reagents were mixed in an agate mortar
using n-heptane as homogenizing medium. After melting
in an open Pt–Au crucible at 800°C for 30 min in air, liquids
were quenched at room temperature in graphite molds. Some
30-min annealing treatments at temperatures around the
glass transition were performed. Rare-earth ions were intro-
duced in the form of oxides (in different concentrations).
The samples had doping contents as mono-doped (1.0Sm3þ ,
1.0Tb3þ , and 1.5Tb3þ ) and double-doped: 1.0Sm3þ ∕xTb3þ
(x ¼ 0.25, 0.50, 0.75, 1.0, 1.25, and 1.50) and
1.5Tb3þ ∕ySm3þ (y ¼ 0.2, 1.0) in mol. %, respectively.
The host material presents very good optical quality; it is
stable against atmospheric moisture, and it exhibits low
optical attenuation in the 0.4 to 5.0 μm spectral region.
The maximum phonon energy for the 80%PbGeO3 ∶
10%PbF2 ∶10%CdF2 host material is ∼800 cm−1 . LED-
based excitation sources operating at 355 and 375 nm were
employed. The luminescence signal was collected and
directed to a fiber integrated UV–VIS–NIR spectrograph
(Ocean Optics HR4000) with operating resolution of
≤1.0 nm. All spectra presented in this communication
0091-3286/2019/$25.00 © 2019 SPIE

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 Alves, Bueno, and Gouveia-Neto: Tunable greenish-to-reddish light generation via energy transfer. . .

3+ 4 6
were handled employing the proper software of the spec- 1.2 Sm (λ em = 600 nm) - G 5/2 H 7/2
trometer (Ocean Optics, SpectraSuite). The data were stored 3+ 4 7
and analyzed in a personal computer employing a commer- Tb (λ em = 545 nm) - D 4 F5
1.0
cially available software. The spectra were converted into
CIE-1931 coordinates using a specially designed software excitation

Intensity (a.u.)
(SPECTRA LUX, Ponto Quântico/RENAMI, Recife, 0.8

355 nm

375 nm
Brazil).16,17 The time-resolved measurement apparatus con-
sisted of a spectrofluorometer (Horiba, TCSPC Nanolog), 0.6
a pulsed pump lamp (Horiba-FL1040-1457B-3714), an
iHR 320 spectrometer connected to a SpectrAcq2 Data 0.4
Acquisition Module (Horiba), and a photomultiplier tube
detector. The lifetimes were measured using the expression 0.2
τeff ¼ ½I em ðtÞdt∕I em ð0Þ,15 where τeff is the calculated effec-
tive lifetime, I em ðtÞ stands for the time dependence of emis- 0.0
sion intensity, and I em ð0Þ is the initial intensity. The effective 350 400 450 500
lifetime, obtained by integrating the normalized decay curve, Wavelength (nm)
gives a better description of radiative decays that are not
described by a single exponential function.19,20 Fig. 2 Excitation spectra of Sm3þ (λem ¼ 600 nm) and Tb3þ
(λem ¼ 545 nm) single-doped samples.
3 Results and Discussion
Figure 1 shows the absorption spectra of the single-doped (a) 1.2 3+
ðSm3þ ; Tb3þ Þ and codoped Sm3þ ∕Tb3þ samples. The Sm (1.0 mol. %)

H7/2
F7/2
λem = 600 nm

6
absorption peaks indicated in Fig. 1 are related to the intra-

4
1.0

G 5/2
λexc = 375 nm

H5/2
configurational (f–f) electronic transitions departing from the

4
Sm3þ ð6 H5∕2 Þ and Tb3þ ð7 F6 Þ ground state, respectively. It is

6
0.8
important to point out the overlap of the Sm3þ ∶6 H5∕2 − 4 I9∕2 ,
Intensity (a.u.)

I13/2
M 19/2
5∕2 − G7∕2 absorption band and the double-peak Tb ∶

H9/2
6H 4 3þ

4
0.6

6
7
F6 − D4 transition absorption/emission spectral band.
5

H5/2

H5/2
H5/2

G 5/2
6
A few transitions are not labeled in the absorption spectrum,

6
D3/2, 1/2

4
0.4

G 5/2
owing to their low absorption cross section, and as such are

G 9/2

H11/2
4

4
H9/2

overshadowed by the strong UV absorption of glass matrix.

4

F3/2
H5/2

6
4

H5/2
To obtain the proper excitation wavelength for this study, we 0.2

G 5/2
6
H5/2

6
have carried out the excitation spectrum measurement and

H5/2

4
6

the results are depicted in Fig. 2. As indicated in Fig. 2,

6
0.0
two different UV excitation wavelengths were utilized to 300 400 500 600 700
activate each ion separately depending upon the intent of Wavelength (nm)
the measurement. Figure 3 shows typical emission along
with excitation spectra of the 80PbGeO3 ∶10PbF2 ∶10CdF2 (b) 1.2
3+
Tb (1.0 mol. %)
phosphors single-doped with Sm3þ ð3aÞ and Tb3þ ð3bÞ.
λem = 545 nm
F5

With the help of the simplified Tb-Sm ion pair energy-

D4

1.0
7

λexc = 375 nm
5

level diagram depicted in Fig. 4, one identifies that the

D4
F6

terbium emissions are located around 487 (blue), 542

7

0.8
Intensity (a.u.)

L10
5

1.2 3+ 3+
1.0 Sm /0.0 Tb 0.6
I9/2

F6
7
4

3+ 3+
0.0 Sm /1.5 Tb
1.0
G7/2

3+ 3+
1.0 Sm /1.0 Tb
Sm : H5/2

0.4
4
3+ 6

F7/2

F4
I11/2

F5/2
G5/2

F3

0.8
7
Sm : H5/2

L9

F6
6
F9/2
Intensity (a.u.)

7
D4

F3/2

0.2
6
4

D4
5

7
3+ 6

H15/2

D4
6

H13/2

5
6

F6
Sm : H5/2

D4
Tb : F6

F11/2

Sm : H5/2

5
Sm : H5/2

0.6
5
3+ 7

6
Tb : F6

Sm : H5/2
3+ 6

6
Sm : H5/2
3+ 6

0.0
6
3+ 6
3+ 7

3+ 6

Sm : H5/2

300 400 500 600 700

3+ 6

Sm : H5/2
Sm : H5/2

0.4
3+ 6

Wavelength (nm)
3+ 6
3+ 6

3+ 3+
Tb /Sm
0.2 Tb
3+
Fig. 3 Excitation and emission spectra of (a) Sm3þ and (b) Tb3þ sin-
gle-doped samples under excitation at 375 nm. The emissions are
3+
Sm the ones with the highest intensity.
0.0
400 600 800 1000 1200 1400 1600 1800
(green), 582 (yellow-red), and 620 nm (red) originated from
Wavelength (nm)
the 5 D3 → 7 F6 , 5 D4 → 7 F6 , 5 D4 → 7 F5 , 5 D4 → 7 F4 , and
5 D → 7 F transitions, as portrayed in Fig. 3(a). The emis-
Fig. 1 Absorption spectra of the single-doped samples with Sm3þ and 4 3
Tb3þ . Concentrations are presented in mol. %. sion spectrum of Fig. 3(b) exhibits four distinct visible

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 Alves, Bueno, and Gouveia-Neto: Tunable greenish-to-reddish light generation via energy transfer. . .

5 6
30 L10 P3/2, 5/2
5 4
G M17/2
5 6 4
D3 F
4 5/2
25 I13/2, 11/2, 9/2
5
D4 4

Energy (x 10 cm )
G7/2

-1
20 4
F3/2

650 nm
582 nm
487 nm
542 nm

620 nm
-4
4
G5/2

706 nm
645 nm
600 nm
561 nm
15

375nm
355nm
375nm
355nm
6
Fj=11/2
10 9/2
7 7/2
Fj=0 5/2
1 6
5 2 Hj=13/2
3
4 11/2
5 9/2
7/2
0 6 5/2
3+ 3+
Tb Sm

Fig. 4 Simplified energy-level diagram of the excitation and downconversion emission for the
Tb3þ − Sm3þ ion pair excited using UV light. Upward arrows indicate excitation, downward arrows
stand for luminescence emission, and curved arrow and double arrow denote energy transfer and
multiphonon relaxation processes, respectively.

emission bands around 561 (yellowish), 600 (orange), 645 (a) 8 3+

Tb (1.5 mol. %)

F5
(red), and 706 nm which were assigned, respectively, to

7
3+
the electric dipole samarium 4 G5∕2 → 6 H5∕2 , 4 G5∕2 → 6 H7∕2 , 7 0.0Sm

Tb : D4
3+
0.2Sm
5∕2 → H9∕2 , and G5∕2 → H11∕2 transitions.
4G 6 4 6

3+ 5
6 1.0Sm
3+

Figure 5 shows typical emission spectra of codoped sam- λexc = 355 nm

Intensity (a.u.)

H7/2
ples under both excitation wavelengths for a fixed terbium 5

6
concentration and varying the samarium content. As can

Sm : G5/2
4
be inferred from spectra, for both excitation wavelengths,

H9/2
F6

H5/2

3+ 4
the terbium characteristic emissions decrease with increasing
7

F3

6
F4

H11/2
3
6

7
7

Sm : G5/2
samarium concentration, and as expected the samarium
Tb : D4

Sm : G5/2

6
Tb : D4
3+ 5

Tb : D4

3+ 4
distinct emissions increase. In Fig. 5, one exhibits the emis- 2
3+ 5
3+ 4

Sm : G5/2
3+ 5

sions for the excitation wavelengths around (a) 355 and

3+ 4
1
(b) 375 nm, which activate both Tb3þ and Sm3þ ions present
in the host matrix and the spectra present emissions charac- 0
teristic of either ions. For the 355-nm excitation, nondetect- 450 500 550 600 650 700 750
able emission associated to samarium is not expected though Wavelength (nm)
it is observed owing to the fact that for this wavelength one
basically excites terbium ions only as indicated in the exci- (b) 7 3+
Tb (1.5 mol. %)
H7/2

tation spectrum of Fig. 2. However, the almost resonant

F5

3+
7

0.0Sm
energy-transfer Tb3þ ½5 D4  to Sm3þ ½4 F3∕2 ; 4 G5∕2  enhances
6

6 3+
Tb : D4

Sm : G 5/2

0.2Sm
population in the samarium ions excited state 4 G5∕2 from
3+ 5

3+
3+ 4

5 1.0Sm
where the emitting transitions produce luminescence. One λexc = 375 nm
Intensity (a.u.)

has also examined the Tb3þ to Sm3þ energy-transfer process

in samples with fixed samarium concentration and variable 4
H5/2

H9/2

Tb3þ content in the codoped samples at two excitation wave-

6

6
F6

3
Sm : G 5/2

lengths, and the results are portrayed in the series of spectra

Sm : G 5/2
7

F4

H11/2
F3

of Fig. 6. For increasing Tb3þ ions content, both terbium

3+ 4

3+ 4
Tb : D4

6
Tb : D4

2
3+ 5

and samarium distinct emissions increase, with the more

Tb : D4

Sm : G 5/2
3+ 5

3+ 5

pronounced growth taking place when 375-nm excitation

3+ 4

1
was employed. Time-resolved luminescence measurements
were carried out and the results indicated a substantial
0
decrease in the lifetime of the 5 D4 energy level associated 450 500 550 600 650 700 750
with the 545-nm emission of Tb3þ ions due to the presence Wavelength (nm)
of Sm3þ codoping, as indicated in data portrayed in Fig. 7.
As it can be observed from data, the 545-nm emission life- Fig. 5 Emission spectra of 1.5Tb3þ ∕x Sm3þ (x ¼ 0.0, 0.2, and
time reduced substantially when the samarium concentration 1.0 mol. %) under excitation at (a) 355 nm and (b) 375 nm.

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 Alves, Bueno, and Gouveia-Neto: Tunable greenish-to-reddish light generation via energy transfer. . .

(a) 4 3+
1.0 3+
Sm (1.0 mol. %) Tb (1.5 mol. %)

F5

H7/2
3+ 3+
0.25Tb

7
0.0Sm

6
3+

Tb : D4
0.75Tb 0.8 3+

Sm : G 5/2
0.2Sm

3+ 5
3+ 1.8
3 1.25Tb

Normalized intensity
3+ 4
3+
1.50Tb
3+
1.6 1.0Sm
Intensity (a.u.)

λexc = 355 nm 0.6 λexc = 375 nm

1.4

Lifetime (ms)
λem = 545 nm

H9/2
H5/2
2 1.2

6
6
F6

F4

Sm : G 5/2
Sm : G 5/2
0.4
7

F3
7

H11/2
1.0

7
Tb : D4

3+ 4
3+ 4
Tb : D4

6
3+ 5
0.8
3+ 5

Tb : D4
1

Sm : G 5/2
3+ 5
0.2 τ = 1.65 ms 0.0 0.2 0.4 0.6 0.8 1.0

3+ 4
1 3+
Sm concentration (mol. %)
τ = 1.30 ms
2

0
τ = 0.85 ms
3
0.0
450 500 550 600 650 700 750 1 2 3 4 5 6 7
Wavelength (nm) Time (ms)

(b) 3+ Fig. 7 Decay curves for the 545-nm (5 D4 − 7 F5 ) emission, for a

H7/2

5 Sm (1.0 mol. %)
fixed 1.5 Tb3þ ∕x Sm3þ samples with x ¼ 0.0, 0.2, and 1.0 mol. %.
F5

3+
6

0.25Tb
7

Excitation wavelength at 375 nm.

Sm : G5/2

3+
Tb : D4

0.75Tb
3+ 4
3+ 5

4 1.25Tb
3+
H9/2

3+
1.50Tb
6
Intensity (a.u.)

λexc = 375 nm 1
H5/2

Sm : G5/2

3 2
6

3+ 4

3
Sm : G5/2
F6

3+ 4

F4

F3

H11/2
7

2
7

7
Tb : D4
Tb : D4

6
Tb : D4
3+ 5
3+ 5

Sm : G5/2
3+ 5

1 4
3+ 4

1
0 2
450 500 550 600 650 700 750 1
3
Wavelength (nm) 4
2 5 5
3
Fig. 6 (a) Emission spectra of 1.0Sm3þ ∕x Tb3þ (x ¼ 0.25, 0.75, 1.25, 4
and 1.50 mol. %) under excitation at (a) 355 nm (20 mW) and 5
(b) 375 nm (18 mW).

increased. Furthermore, as samarium ions are added into

the Tb3þ -doped sample, the decay curve is deviated from
an exponential evolution, and shortens, indicating that
nonradiative energy transfer from Tb3þ to Sm3þ is taking
place.39,40 For the highest Sm3þ concentration (1.0 mol. %),
a reduction by a factor of ∼2 was observed. The lifetime Fig. 8 CIE-1931 chromaticity diagram light emanating from the sam-
reduction observed in Fig. 7 reinforces the major role played ples, indicating tunability across the greenish, yellowish, and orange-
by the energy-transfer pathway, indicated in Fig. 3, because red tone. Inset table indicates coordinates for each sample. Photos
it depletes population of the terbium 5 D4 level. The results illustrate actual colors of the samples.
corroborate with the proposed excitation mechanism of the
emitting levels as indicated in the energy-level diagram of enhance the emission of one ion to the detriment of the other,
Fig. 4. For the highest Sm3þ concentration, one has observed as also presented in Fig. 8. However, for the 355-nm exci-
the onset of cross relaxation involving Sm3þ − Sm3þ taking tation wavelength, the contribution of the samarium emis-
place, as indicated by the behavior of decay curve depicted in sions component is produced mainly through the efficient
Fig. 7, when one uses logarithmic scale. The color compo- Tb to Sm energy-transfer mechanism, owing to the fact
sition of the light emanating from the single-doped, and that Sm3þ ions absorb very little energy from the excitation
codoped samples was examined and results are portrayed source as can be inferred from excitation spectra depicted in
in the CIE-1931 chromaticity diagram and tables depicted Fig. 2. Furthermore, the 355-nm excitation wavelength
in Fig. 8. As one sees, the color coordinates can be tuned yields better efficiency when compared to the 375 nm one.
by adjusting the concentration of the codoping ions to
enhance either greenish (Tb3þ ) or reddish (Sm3þ ) tone com-
ponents of the overall luminescence. Furthermore, one may 4 Conclusion
also tune the overall emission emanating from the samples Tunable greenish–yellowish–reddish luminescence in Tb3þ
by choosing different excitation wavelengths, to selectively and Sm3þ codoped fluorogermanate glass under UV light

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 Alves, Bueno, and Gouveia-Neto: Tunable greenish-to-reddish light generation via energy transfer. . .
excitation was generated. Fluorescence emissions around
487, 542, 561, 582, 600, 620, 645, 650, and 706 nm
were obtained in double-doped samples under 355- and
375-nm excitation wavelengths. The relative intensity of
the Sm3þ and Tb3þ ions’ individual distinctive emissions
depends upon the excitation wavelength, relative ion concen-
tration, and the energy-transfer Tb to Sm mechanism, as well
as the allowed tonality tenability of overall luminescence
emission. The CIE-1931 chromaticity coordinates of the
overall luminescence resided in the range (0.31; 0.59) to
(0.62; 0.37). Time decay measurements indicated efficient
nonradiative Tb3þ to Sm3þ energy-transfer mechanism.
Acknowledgments
The financial support for this research by Conselho Nacional
de Desenvolvimento Científico e Tecnológico (CNPq) Grant
No. 483338/2013-9, Financiadora de Estudos e Projetos
(FINEP) CTInfra, Infraspeq 11 and 12, and Coordenação
de Aperfeiçoamento de Pessoal de Ensino Superior
(CAPES) PVE-AO77/2013, is gratefully acknowledged.
Rafaela T. Alves was supported by a graduate studentship
from Coordenação de Aperfeiçoamento de Pessoal de
Ensino Superior (CAPES). We gratefully acknowledge
Professor C. Jacinto (IF-UFAL) for allowing us to exploit
his laboratory facility for the decay-time measurements and
Mr. Tasso O. Sals for technical support with the equipment.
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Biographies of the authors are not available.
January 2019 • Vol. 58(1)