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Journal ArticleDOI

Luminescence and cathodoluminescence properties of MIPr(PO3)4 (MI=Na, Li, K) and PrP5O14

01 Feb 2019-Physica B-condensed Matter (North-Holland)-Vol. 554, pp 121-125

Abstract: Poly-crystals of praseodymium phosphate MIPr(PO3)4 (MI = Na, Li, K) and PrP5O14 have been synthesized by the flux method. All of these hosts crystallized in the monoclinic structures with different space groups. The spectroscopic properties of trivalent praseodymium ions in these compounds have been characterized. The emission spectra under laser excitation at 488 nm show several characteristic emission bands of Pr3+ resulting from intra-configurational transitions between 3P0 and 4f2 lower lying levels. All the studied compounds exhibit two strong parity-allowed 4f15 d1→4f2 emission bands located in the near ultraviolet domain using electrons as source for optical excitation. Therefore, these materials are of interest for applications in lighting and scintillating applications.
Topics: Cathodoluminescence (53%), Praseodymium (53%), Emission spectrum (53%), Luminescence (51%)

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Accepted Manuscript
Luminescence and cathodoluminescence properties of M Pr(PO ) (M =Na, Li, K)
I
3 4
I
and PrP O
5 14
S. Gharouel, L. Labrador-Páez, A. Urbieta, P. Fernández, P. Haro-González, K. Horchani-Naifer,
M. Férid
PII: S0921-4526(18)30739-7
DOI: 10.1016/j.physb.2018.11.037
Reference: PHYSB 311172
To appear in:
Physica B: Physics of Condensed Matter
Received Date: 17 September 2018
Accepted Date: 17 November 2018
Please cite this article as: S. Gharouel, L. Labrador-Páez, A. Urbieta, P. Fernández, P. Haro-
González, K. Horchani-Naifer, M. Férid, Luminescence and cathodoluminescence properties of M
I
Pr(PO ) (M =Na, Li, K) and PrP O , (2018), doi:
3 4
I
5 14
Physica B: Physics of Condensed Matter
10.1016/j.physb.2018.11.037
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ACCEPTED MANUSCRIPT
1
1
2 Luminescence and cathodoluminescence properties
3 of M
I
Pr(PO
3
)
4
(M
I
=Na, Li, K) and PrP
5
O
14
4
5
6
7 By
8
9 S. Gharouel
a,
*, L. Labrador-Páez
b
, A. Urbieta
c
, P. Fernández
c
, P. Haro-
10 González
b
, K. Horchani-Naifer
a
, and M. Férid
a
11
12
13
a
Laboratoire de Physico-Chimie des Matériaux Minéraux et leurs Applications, Centre
14 National des Recherches en Sciences des Matériaux, B.P.73 Soliman, 8027, Technopole Borj
15 Cedria, Tunisia.
16
b
Fluorescence Imaging Group, Departamento de Física de Materiales, Universidad
17 Autónoma de Madrid, C/Francisco Tomás y Valiente, 7, Madrid 28049, Spain.
18
c
Departamento Física de Materiales, Fac. Física, Universidad Complutense, Plaza de Ciencias, 1,
19 Ciudad Universitaria, 28040 Madrid, Spain
20
21
22
23
24
25
26 * E-mail : saidagharouel@gmail.com
27

ACCEPTED MANUSCRIPT
2
1
2 ABSTRACT
3 Poly-crystals of praseodymium phosphate M
I
Pr(PO
3
)
4
(M
I
=Na, Li, K) and PrP
5
O
14
have
4 been synthesized by the flux method. All of these hosts crystallized in the monoclinic structures
5 with different space groups. The spectroscopic properties of trivalent praseodymium ions in
6 these compounds have been characterized. The emission spectra under laser excitation at 488
7 nm show several characteristic emission bands of Pr
3+
resulting from intra-configurational
8 transitions between
3
P
0
and 4f
2
lower lying levels. All the studied compounds exhibit two
9 strong parity-allowed 4f
1
5d
1
4f
2
emission bands located in the near ultraviolet domain using
10 electrons as source for optical excitation. Therefore, these materials are of interest for
11 applications in lighting and scintillating applications.
12
13 Keywords: polyphosphate, ultraphosphate, praseodymium, luminescence, scintillator.
14
15
16
17
18
19
20
21
22
23
24
25

ACCEPTED MANUSCRIPT
3
1 1. INTRODUCTION
2 Emissions from the 4f
N-1
5d4f
N
interconfigurational transitions of trivalent lanthanide ions
3 have received great interest for its potential applications in both ultraviolet (UV) tunable solid-
4 state laser and scintillator devices [1-3]. Scintillators are luminescent materials which absorb
5 ionizing radiation, including -, -, electron, ion, X- and -rays, and emit the absorbed energy
6 in form of UV or visible light. Scintillators, used to detect X- or -rays, find several industrial
7 applications including process control, geophysical exploration, container scanning, radiation
8 monitoring, detection of radioactive materials, and medical imaging [4]. Cerium compounds
9 are actively investigated because of its good scintillation performance [5-7].
10 In the last two decades, several works have been devoted to the spectroscopic characteristics of
11 the trivalent praseodymium (Pr
3+
) ion in diverse inorganic compounds. Indeed, they are
12 promising candidates for applications such as optical thermometry [8-11], luminophors [12],
13 and optical fiber communications [13-14]. In addition to their efficient intraconfigurational
14 4f
2
4f
2
transitions, Pr
3+
-doped materials are well known for exhibiting strong intensity of
15 emission from the electric dipole allowed inter-configurational 4f
1
5d
1
4f
2
transitions, with
16 short decay time, in the order of nanoseconds [15-17]. Therefore, Pr
3+
-doped compounds have
17 received a great interest, owing to their diverse potential applications. In fact, Pr
3+
hosts that
18 support the 4f
1
5d
1
4f
2
fluorescent emissions can conduct to the development of
19 fast scintillators [18,19], and, in particular, to application in medical diagnostic technics such as
20 positron emission tomographies (PET)[20,21]. Moreover, phosphors based on the Pr
3+
21 4f
1
5d
1
4f
2
interconfigurational transition can be employed for some other commercial
22 applications, such as for germicidal purposes [22], detecting alpha and beta particles [23], UV
23 tunable solid state lasers [24,25], and for therapeutical application in medicine [26].
24 Numerous inorganic materials such as molybdates [27], tungstates [28], aluminates [29],
25 silicates [30] and phosphates [31-33] are activated by Pr
3+
ions. Among them, Pr
3+
-doped

ACCEPTED MANUSCRIPT
4
1 phosphates crystals have been the subject of several investigations in the past years, owing to
2 their excellent characteristics for the development of potential laser applications [34-36], non-
3 contact optical temperature sensing applications [8], and, especially, for fast scintillating
4 materials [37,38]. Phosphates exhibit a relatively high stability under standard conditions of
5 temperature and humidity. They also show good crystallinity, they are mechanically rigid, and
6 not soluble in most acids and water. Owing to these interesting characteristics, many works
7 have been devoted to the investigation of spectroscopic properties of Pr
3+
-doped phosphates,
8 especially concerning ultraphosphates and polyphosphates [39-43]. Because of the relatively
9 large distances between rare earth ions in the host, ultraphosphates and polyphosphates are
10 appropriate as hosts for lanthanide ions showing a strong concentration quenching of
11 fluorescence [44-45].
12 In this work, we report the synthesis by flux method and the characterization of M
I
Pr(PO
3
)
4
13 polyphosphate and
PrP
5
O
14
ultraphosphate. The emissions originating from Pr
3+
4f-4f and 5d-4f
14 transitions in these crystalline hosts are also studied with the purpose of characterizing them as
15 promising materials for lighting and scintillator technologies.
16 The comparison of luminescence and scintillation properties of four praseodymium
17 concentrated phosphates NaPr(PO
3
)
4
(P2
1
/n), LiPr(PO
3
)
4
(C2/c), KPr(PO
3
)
4
(P2
1
)
18 polyphosphates and PrP
5
O
14
(P2
1
/c) ultraphosphate was also presented with special emphasis
19 on the influence of the structural differences and monovalent alkali ions on the optical
20 properties.
21 2. EXPERIMENTAL
22 2.1. Synthesis method
23 The M
I
Pr(PO
3
)
4
(M
I
=Na, Li, K) and PrP
5
O
14
poly-crystals were synthesized by using the flux
24 method described in previous works [46,47]. A mixture of alkali metal ions carbonates M
I
2
CO
3
25 and praseodymium oxide (Pr
6
O
11
) were dissolved in phosphoric acid (H
3
PO
4
85%) with

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Abstract: We have discovered a new inorganic single crystal scintillator [1], lutetium oxyorthosilicate doped with cerium, Lu2(SiO4)O:Ce (or “LSO”), which has a unique combination of properties including high emission intensity, fast decay time, high density, and high atomic number. These properties result in excellent signal-to-noise, fast coincidence timing, high count-rate capability, and high detection efficiency making LSO superior to any other known scintillator for many applications. This new scintillator has several important advantages over the scintillator crystals currently used for the detection of gamma rays or X-rays in applications such as medical imaging, nuclear and particle physics, and geophysical exploration. Here we compare the properties of LSO to those of the two most widely used scintillators, namely thallium-doped sodium iodide and bismuth germanate.

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