Accepted Manuscript

Title: Energy transfer and color-tunable luminescence

properties of NaCaBO3 :RE3+ (RE3+ = Tm3+ , Dy3+ ,
Tm3+ /Dy3+ ) phosphors
Author: Peng Du Jae Su Yu
PII:
DOI:
Reference:

S0025-5408(16)30480-9
http://dx.doi.org/doi:10.1016/j.materresbull.2016.08.002
MRB 8882

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MRB

Received date:
Revised date:
Accepted date:

20-6-2016
1-8-2016
2-8-2016

Please cite this article as: Peng Du, Jae Su Yu, Energy transfer
and
color-tunable
luminescence
properties
of
NaCaBO3:RE3+
(RE3+=Tm3+, Dy3+, Tm3+/Dy3+) phosphors, Materials Research Bulletin
http://dx.doi.org/10.1016/j.materresbull.2016.08.002
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<AT>Energy transfer and color-tunable luminescence properties of NaCaBO3:RE3+ (RE3+ =

Tm3+, Dy3+, Tm3+/Dy3+) phosphors
<AU>Peng Du, Jae Su Yu* ##Email##jsyu@khu.ac.kr##/Email##
<AFF>Department of Electronics and Radio Engineering, Kyung Hee University, Yongin 446-701, Republic of Korea
<PA>* Corresponding author. Tel.: 82 31 201 3820; fax: 82 31 206 2820.
<ABS-Head><ABS-HEAD>Graphical abstract
<ABS-P>
<ABS-P><xps:span class="xps_Image">fx1</xps:span>
<ABS-HEAD>Highlight The optimum doping content for Tm3+- and Dy3+-doped NaCaBO3
phosphors was 2 and 3 mol%, respectively. The emission color of the phosphors was tuned
from blue to white by adjusting the Dy3+ ion content. The ET efficiency in
NaCaBO3:0.02Tm3+/zDy3+ phosphors was up to 89.4% when z = 0.07. The ET mechanism
between Tm3+ and Dy3+ ions was dipole-dipole interaction. The obtained samples possessed
excellent CL properties with stable CIE chromaticity coordinates.
<ABS-HEAD>Abstract
<ABS-P>The Tm3+-doped, Dy3+-doped and Tm3+/Dy3+-codoped NaCaBO3 compounds were
produced via a solid-state reaction process. The optimum doping concentrations for Tm3+ and
Dy3+ ions in NaCaBO3 were determined to be 2 and 3 mol%, respectively. Under 358 nm
excitation, the characteristic emission bands of the dopants were detected in the synthesized
compounds. Besides, the emitting-color of the obtained products was shifted from blue to pure
white as a result of the efficient energy transfer (ET) from Tm3+ to Dy3+ ions. According to the
PL emission intensity, the ET efficiency was calculated and found to be elevated with the
introduction of the activators and the maximum efficiency was around 89.4%. The dipole-dipole
interaction contributed to ET from Tm3+ to Dy3+ ions. Additionally, the temperature-dependent
PL spectra suggested that the as-synthesized phosphors possessed good thermal stability. Also,
the as-prepared phosphors possessed strong CL properties.
<KWD>Keywords: Optical materials; Phosphors; Luminescence; Optical properties; Oxides.
<H1>1. Introduction
In recent years, considerable interests in the rare-earth (RE) ions activated phosphors, which
demonstrates good prospects of applications in various fields, such as, white light-emitting
1

diodes (WLEDs), solar cells, field-emission displays (FEDs), cell imaging and thermal detectors,
have been gaining [1-5]. Compared with other applications, the development of phosphorsconverted WLEDs has accumulated much attention owing to their characteristics of high
luminous efficiency, low electric consumption, long working time and environmental protection
feature [6,7]. Nowadays, the single-component RE-doped phosphors excited by ultraviolet (UV)
light, in which different RE ions acting as sensitizer and activator are doped in the same host, are
regarded as a feasible scheme to generate the high-quality white lights [8,9]. Up to date, the
white lights which are produced through adjusting the energy transfer (ET) between sensitizer
and activator have been obtained in abundant single-component compounds, such as
Sr3Lu(PO4)3:Eu2+/Mn2+ [10], Mg3(PO4)2:Eu2+/Mn2+ [11], BaMg2Al6Si9O30:Eu2+/Tb3+/Mn2+ [12],
and (Sr3,Ca,Ba)(PO4)3Cl:Eu2+/Tb3+/Mn2+ [13]. It is evident that some harsh reaction conditions,
taking the reducing atmosphere for example, are required to prepare these bivalent RE ions
doped phosphors, resulting in high power cost as well as high investment. Hence, searching for a
new single-component compound, which can be calcined at a relatively low temperature, is
necessary. As a vital part of the RE ions, thulium (Tm3+) ions are usually used as the blue light
emissive activators due to their characteristic emission in blue region due to the 1D2 3F4
transition [14,15]. Meanwhile, the dysprosium (Dy3+) ions have two characteristic emissions
which are assigned to the 4F9/2 6H15/2 (blue) and 4F9/2 6H13/2 (yellow) transitions [16,17]. As
we know, the 4F9/2 6H13/2 transition pertains to the forced electric dipole transition and it is
hypersensitive to the surrounding environment [18,19]. Furthermore, because of the superior
spectral overlap between the 1D2 3F4 transition of Tm3+ ions and the 6H15/2 4I15/2 transition
of Dy3+ ions, the ET between Tm3+ and Dy3+ ions is available, leading to the white light
emissions in Tm3+/Dy3+-codoped compounds [20-22].

The orthoborates with the general formula of AMBO3 (A = Li, Na, K; M = Ca, Sr, Ba) were
widely reported as the luminescent host lattices because of their preponderance of low
fabrication temperature and high stability [23-25]. Liang et al. revealed that the bright emissions
from Eu3+ ions were achieved in NaSrBO3:Eu3+ phosphors and they may have potential
applications in WLEDs [26]. Furthermore, through monitoring the doping content between Dy3+
and Eu3+ ions, color-tunable luminescence was achieved in KCaBO3:Dy3+/Eu3+ phosphors [27].
Shen et al. pointed out that the blue-white-orange color-tunable emissions can be realized in
Ce3+/Mn2+-codoped NaCaBO3 phosphors by changing the Ce3+/Mn2+ ratio [28]. Also, the
luminescence properties of the Eu3+-doped, Ce3+-doped and Ce3+/Tb3+/Mn2+-tridoped NaCaBO3
phosphors have been systematically studied by Zhangs group [29-31]. Nevertheless, as far as we
know, the research on the Tm3+- and Dy3+-doped NaCaBO3 phosphors, including especially the
ET processes between dopant ions in Tm3+/Dy3+-codoped NaCaBO3 phosphors is still deficient.
In the work, the conventional solid-state reaction approach was applied to synthesize the Tm3+doped, Dy3+-doped and Tm3+/Dy3+-codoped NaCaBO3 phosphors. The phase composition,
microstructure and photoluminescence (PL) characteristics of the obtained phosphors as well as
the ET mechanism between Tm3+ and Dy3+ ions were analyzed. Meanwhile, to explore the
potential application of the as-prepared samples in FEDs, the cathodoluminescence (CL)
performance was minutely evaluated.
<H1>2. Experimental
A series of NaCaBO3:xTm3+ (x = 0.005, 0.01, 0.02, 0.03, 0.04 and 0.05), NaCaBO3:yDy3+ (y
= 0.01, 0.03, 0.05, 0.07 and 0.09) and NaCaBO3:0.02Tm3+/zDy3+ (z = 0, 0.01, 0.03, 0.05 and
0.07) compounds were calcined by means of a simple high temperature solid-state reaction
technique. The high-purity powders, such as, sodium carbonate (Na2CO3), calcium carbonate

(CaCO3), boiric acid (H3BO3), thulium oxide (Tm2O3) and dysprosium oxide (Dy2O3), were
bought from Sigma-Aldrich and used as the raw materials. According to the above formulas, the
Na2CO3, CaCO3, H3BO3, Tm2O3 and Dy2O3 were weighted and thoroughly mixed in an agate
mortar for 30 min. After that, these homogeneous mixtures were shifted to the alumina based
crucibles and sintered in the furnace at 850 C for 6 h (the heating rate was 3 C/min). After
cooling downing, the final products were grinded and collected for further characterization.
The phase structure of the obtained phosphors was analyzed through a X-ray diffractometer
(Bruker D8 Advance) in the 2 range of 20-80. The morphological behaviors of the synthesized
samples were characterized by field-emission scanning electron microscope (FE-SEM) (LEO
SUPPA 55, Carl Zeiss) and a transmission electron microscope (TEM) (JEM-2100F, JEOL). The
fluorescence spectrophotometer (SCINCO FS-2) was used to detect the ambient-temperature PL
and PL excitation (PLE) spectra of the samples. The temperature-dependent PL spectra were
detected by the SCINCO FS-2 system and the temperature was commanded by a temperature
controlled chamber (NOVA ST540). The CL properties, in which the phosphors were excited by
the electron beam at an accelerating voltage from 5 to 9 kV and filament current from 33 to 55
A, were measured by the Gatan (UK) MonoCL3 system attached with the scanning electron
microscope (Hitachi S-4300 SEM).
<H1>3. Results and Discussion
To identify the phase composition and crystal structure of the studied compounds, the X-ray
diffraction (XRD) patterns were measured. Figure 1 shows the representative XRD patterns of
NaCaBO3,

NaCaBO3:0.02Tm3+,

NaCaBO3:0.03Dy3+

and

NaCaBO3:0.02Tm3+/0.03Dy3+

phosphors. As presented in Fig. 1, all the samples exhibited the similar result and the diffraction
peaks were in good agreement with the previous result reported by Wu et al. [32]. indicating that

the obtained samples possessed single pure phase and the doping of Tm3+ and Dy3+ ions did not
produce any impurity or induce any distinct variations in the host structure. Recently, Wu et al.
revealed that the NaCaBO3 has an orthorhombic phase (space group Pmmn (59)) with lattice
constants of approximately a = 16.093 , b = 10.210 , c = 3.498 , V = 574.78 3 and Z = 2
[32]. Therefore, it is reasonable to conclude that the Tm3+-doped, Dy3+-doped and Tm3+/Dy3+codoped NaCaBO3 phosphors have pure orthorhombic phase.
The morphologies of the NaCaBO3:0.02Tm3+/0.03Dy3+ phosphors were characterized by FESEM and TEM. From the FE-SEM image (Fig. 2 (a)), one knows that the product was made up
of aggregated and amorphous microparticles with the size of approximately 5-30 m.
Furthermore, the conglomeration phenomenon was further conformed by the TEM image, as
depicted in Fig. 2(b). The lattice spacing calculated from the high-resolution TEM (HR-TEM)
image (Fig. 2(c)) was about 2.54 which matched well with the interplanar distance of the (321)
plane of orthorhombic NaCaBO3. The selected area electron diffraction (SAED) pattern (Fig.
2(d)) shows the bright diffraction spots, revealing that the synthesized particles were a single
crystal structure. The elemental mapping (Fig. 2(e)) revealed that the compositions of the
compounds of Na, Ca, B, Tm, Dy and O were evenly distributed.
The PLE and PL spectra of the NaCaBO3:0.02Tm3+ phosphors are presented in Fig. 3. From
Fig. 3, it can be seen that the PLE spectrum monitored at 458 nm (black line) had a sharp
absorption peak at 358 nm, which agrees with the commercial UV-LED chips, owing to 3H6
1

D2 transition of Tm3+ ions [15,19]. Meanwhile, under 358 nm excitation, the

NaCaBO3:0.02Tm3+ phosphors exhibited an intense blue emission centered at about 458 nm

corresponding to 1D2 3H6 transition of Tm3+ ions [20,21], revealing its potential application in
blue-emitting LEDs. Moreover, the other two relatively weak blue and red emissions, which

were attributed to the 4f-4f transitions of Tm3+ ions, namely, 1G4 3H6 and 1G4 3F4 [33],
respectively, were also observed (blue line).
Figure 4 displays the PL spectra of NaCaBO3:xTm3+ (x = 0.005, 0.01, 0.02, 0.03, 0.04 and
0.05) phosphors under 358 nm excitation. As presented in Fig. 4, all the samples exhibited the
characteristic emissions of Tm3+ ions and the emission intensity was dependent on the dopant
concentration. The PL emission intensity increased as the Tm3+ ion concentration increased,
reaching its maximum value when x = 0.02. However, it sharply decreased when the Tm3+ ion
content was over 2 mol% and the concentration quenching effect was the main reason for this
phenomenon, as displayed in Fig. 4 [21]. As we know, the non-radiative energy transfer (ET)
between the activators contributes to the concentration quenching effect. Based on Dexters
energy transfer expression for multipolar interaction and Reisfelds approximation, one knows
that [34]:
I x x /3 or lg I x c 3 lg x , (1)
1

where x is the activator concentration of Tm3+ ions, and c are the constants, is the electric
multipolar character and it stands for dipole-dipole interaction, dipole-quadrupole interaction and
quadrupole-quadrupole interaction when its value is 6, 8 and 10, respectively. From the plot of
lg(I/x) vs. lg(x) for the 1D2 3H6 transition (see the inset of Fig. 4), one knows that the relation
between lg(I/x) and lg(x) was linear and can be fitted with a slope of about -1.65. Hence, the
value was determined to be around 4.95 which was approached to 6, indicating that the nonradiative ET between Tm3+ ions in NaCaBO3:xTm3+ phosphors was dipole-dipole interaction.
Figure 5 shows the PLE and PL spectra of the NaCaBO3:0.03Dy3+ phosphor. The excitation
spectrum (black line) was composed of a sequence of sharp bands centered at about 324, 350,
364, 388, 426, 450 and 471 nm which were attributed to the 4f-4f transitions of Dy3+ ions from
6

the ground state 6H15/2 to the excited states of 6P3/2, 6P7/2, 6P5/2, 4I13/2, 4G11/2, 4I15/2 and 6H15/2,
respectively [17,35]. The emission spectrum (orange line) excited at 350 nm possessed three
emissions located at 482 (blue), 577 (yellow) and 664 (red) nm corresponding to the 4F9/2
6

H15/2, 4F9/2 6H13/2 and 4F9/2 6H11/2 transitions of Dy3+ ions, respectively [16,36]. Among

these transitions, the 4F9/2 6H15/2 transition is the magnetic dipole transition and its intensity is
little affected by the crystal field strength or the coordination environment surrounding the Dy3+
ions. On the contrast, the 4F9/2 6H13/2 transition pertains to the electric dipole transition which
is sensitive to the chemical environment around the Dy3+ ions in host lattices [19]. In general,
when the Dy3+ ions occupy the sites with low symmetry, the 4F9/2 6H13/2 transition takes the
domination in the luminescent emission spectrum [37]. The stronger yellow emission in this
work, as shown in Fig. 5, demonstrated that the Dy3+ ions were entered into the NaCaBO3 host
lattices by occupying the sites with non-inversion center.
To find out the optimum doping concentration of Dy3+ ions in NaCaBO3, the
NaCaBO3:yDy3+ phosphors with different Dy3+ ion concentrations were prepared and their
luminescent properties were systematically investigated, as presented in Fig. 6. Note that, the
shape and position of the emission peaks were unalterable with the adding of Dy3+ ion content
apart from their intensities. It is can be seen that the emission intensity first increased with the
increasing of the Dy3+ ion concentration and then started to be quenched when the doping
concentration was over 3 mol% (see Fig. 6). With the increment of doping concentration, the
distance among Dy3+ ions became small enough to allow the resonance-type ET, leading to the
concentration quenching effect, and the population of the 4F9/2 level could be declined through
the following cross relaxation (CR) processes (CR1, CR2 and CR3) (see Fig. 9) [37,38]:
4

F9/2 + 6H15/2 6H9/2/6F11/2 + 6F5/2

F9/2 + 6H15/2 6H7/2/6F9/2 + 6F3/2

F9/2 + 6H15/2 6F1/2 + 6H9/2/6F11/2

Because of these above CR routes, the 2F9/2 level was quenched as well as its emission intensity.
To further investigate the resonance ET involved in NaCaBO3:yDy3+ phosphors, the relation
between lg(I/y) and lg(y) was analyzed (here y is the activator concentration of Dy3+ ions), as
shown in inset of Fig. 6. By fitting the experimental data with Eq. (1), the slope value was found
to be approximately -1.85, and the value was determined to be 5.55 which was close to 6,
confirming that the dipole-dipole interaction took the domination in the resonance-type ET
between the Dy3+ ions in NaCaBO3:yDy3+ phosphors.
As aforementioned, under UV light excitation, the Tm3+-doped NaCaBO3 phosphors can
exhibit strong blue light, and bright yellow emissions from the 4F9/2 6H13/2 transition were
gained in Dy3+-doped NaCaBO3 phosphors. Therefore, white light emissions were expected to be
achieved in Tm3+/Dy3+-coactivated NaCaBO3 phosphors through the combination of the blue and
yellow emissions. From the comparison of the excitation spectrum of the NaCaBO3:0.03Dy3+
phosphor and the emission spectrum of the NaCaBO3:0.02Tm3+ phosphor as depicted in Fig. S1,
one knows that there was an obvious spectral overlap between the dopant ions. Thus, the energy
transfer from Tm3+ to Dy3+ ions in the Tm3+/Dy3+-codoped NaCaBO3 phosphors in avaiable. For
the purpose of analyzing the ET processes from Tm3+ to Dy3+ ions and luminescent properties of
Tm3+/Dy3+-codoped NaCaBO3 phosphors, a series of NaCaBO3:0.02Tm3+/zDy3+ (z = 0, 0.01,
0.03, 0.05 and 0.07) phosphors were synthesized. The PL spectra of NaCaBO3:0.02Tm3+/zDy3+
excited at 358 nm are illustrated in Figs. 7(a)-7(e). Upon 358 nm excitation, the Tm3+/Dy3+codoped NaCaBO3 phosphors exhibited the characteristic emissions of Tm3+ and Dy3+ ions.
Meanwhile, it was found that the emission intensity of Tm3+ ions showed a decreasing tendency

with arising the Dy3+ ion content, whereas that of the Dy3+ ions first increased, and then began to
decease when the doping content was exceeded 3 mol% which was assigned to the concentration
quenching effect (see Fig. 7(f)) [17]. The result further proved that the ET from Tm3+ to Dy3+
ions was efficient which was consistent well with the result from the Fig. S1.
Figure 8 shows the energy level scheme of Tm3+ and Dy3+ ions along with the probable
luminescent routes. Upon 358 nm excitation, the Tm3+ ions absorbed the energy of the incident
photon and were pumped to the 1D2 level from the ground state 3H6 (3H6 + a photon (358 nm)
1

D2). Meanwhile, a part of the electrons at the 1D2 level relaxed to the lower excited level of 1G4

because of the nonradiative (NR) transition process. Finally, the characteristic emissions of Tm3+
ions were produced as a result of the following radiative transitions: 1D2 3F4 (458nm), 1G4
3

H6 (481nm) and 1G4 3F4 (664nm). On the other hand, since the intrinsic ET between Tm3+

and Dy3+ ions (1D2 (Tm3+) + 6H15/2 (Dy3+) 3F4 (Tm3+) + 4I15/2 (Dy3+)), the 4I15/2 level of the
Dy3+ ions was populated, as shown in Fig. 8. Subsequently, the NR transition took place, leading
to the population of 4F9/2 level. Ultimately, blue, yellow and red emission peaks, which were
ascribed to the 4F9/2 6H15/2, 4F9/2 6H13/2 and 4F9/2 6H11/2 transitions of Dy3+ ions,
respectively, were achieved. As a result, under 358 nm excitation, the Tm3+/Dy3+-codoped
NaCaBO3 phosphors could emit the featured luminescence of Tm3+ and Dy3+ ions (see Fig. 7).
To better understand the above ET process, it is necessary to analyze the energy transfer
efficiency (ET) which could be calculated from the fluorescence emission intensity by using the
following formula [35,39]:

ET 1

IS
. (2)
IS 0

Here, IS and IS0 are the fluorescence emission intensity of Tm3+ ions with and without the
addition of Dy3+ ions, respectively. The ET (Tm3+ Dy3+) value as a function of Dy3+ ion
9

content were calculated and presented in Fig. 9. It is can be seen that the ET value presented an
upward trend with elevating the Dy3+ ion content and the maximum value was around 89.4%
(see Fig. 9). The result suggested that the energy transfer from Tm3+ to Dy3+ ions in
NaCaBO3:0.02Tm3+/zDy3+ phosphors was efficient. On the other hand, for the resonance-type
ET from a sensitizer to an activator, there are two disparate mechanisms, that is, exchange
interaction and multipole-multipole interaction [34,40]. In general, when the critical distance is
below 5 , the dipole-dipole interaction takes the domination in the ET mechanism. If not, the
multipole-multipole interaction prevails. On the basis of Blasses report, the critical distance (Rc)
between the Tm3+ and Dy3+ ions can be estimated utilizing the following formula [41]:
1/3

3V
Rc 2
, (3)
4

x
N
c

where V is the volume of the unit cell, xc is the total concentration of Tm3+ and Dy3+, at which
the PL emission intensity of Tm3+ ions is half of the sample without Dy3+ ions, and N is the
number of the available sites for the dopant in the unit cell. In present work, N = 2, V = 574.78
3 and xc = 0.041 (see inset of Fig. 9). Thus, the Rc value was determined to be around 23.55
(> 5 ), and the ET from Tm3+ to Dy3+ ions in NaCaBO3:0.02Tm3+/zDy3+ phosphors was
dominated by the multipole-multipole interaction.
From the Dexters energy transfer formula for multipole interaction and Reisfelds
approximation, one obtains the following formula [34,42]:

S 0
C n /3 , (4)
S
where S0 and S represent the luminescence quantum efficiencies of Tm3+ ions without and with
the addition of Dy3+ ions, respectively, and C is the sum content of Tm3+ and Dy3+ ions. n equals
6, 8 or 10 presents the dipole-dipole interaction, dipole-quadrupole interaction or quadrupole10

quadrupole interaction, respectively. The values of S0/S can be roughly calculated by the ratio
of fluorescence emission intensities (IS0/IS), so the Eq. (4) can be written as [28,40]:

S 0 I S 0

C n /3 , (5)
S
IS
Here, the IS0 and IS have the same meaning as in Eq. (2). Figure 10 shows the plots of IS0/IS
versus Cn/3. As presented in Fig. 10, when n = 6, the fitting result was the optimal, revealing that
the dipole-dipole interaction took the domination in the ET between Tm3+ and Dy3+ ions.
To investigate the color tone properties of the obtained compounds, the Commission
Internationable de IEclairgae (CIE) values were studied. The CIE chromaticity coordinates of
NaCaBO3:0.02Tm3+/zDy3+ phosphors, which were calculated from the PL spectra, are displayed
in Fig. 11 and Table. 1. It is clear that the NaCaBO3:0.02Tm3+ phosphor exhibited the blue light
(see point a1 in Fig. 11). However, with the introduction of Dy3+ ions, the emitting-color was
altered from blue to white along with the varied CIE chromaticity coordinates from (0.155,0.039)
to (0.348,0.323) (see Fig. 11 and Table 1). These color-tunable emissions demonstrated that the
NaCaBO3:0.02Tm3+/zDy3+ phosphors may have promising applications in UV-excited WLEDs
as a white light source.
For detecting the suitability of the synthesized samples for their applications in solid-state
lighting, the thermal stability of phosphors is an important technological parameter owing to its
effect on the light output and color rendering index [12,35]. The temperature-dependent PL
spectra of the NaCaBO3:0.02Tm3+/0.03Dy3+ phosphor in the temperature range of 30-200 C
under the excitation of 358 nm were measured and illustrated in Fig. 12(a). Clearly, owing to the
thermal quenching effect, the PL emission intensity exhibited a decreasing tendency with the
increment of temperature, and the emission intensities of Tm3+ and Dy3+ ions declined to 76.1
and 89.4% compared to those at 30 C, respectively (see Figs. 12(b) and 12(c)), demonstrating
11

that the obtained compounds had good thermal stability. To better elaborate the thermal
quenching behavior, the activation energy based on Mott equation [44,45]:

I0
, (6)
1 c exp E kT

where I0 is the PL emission intensity of the phosphor at initial temperature, I is the PL emission
intensities at different temperatures, c is the constant, E is the activation energy of the thermal
quenching and k is the Boltzmann constant (8.62 10-5 eV/K). On the basis of Eq. (6), one
knows that the activation energy (E) can be obtained from the plot of ln(I0/I-1) versus 1/T. As
shown in Fig. 12(d), the values of E for Tm3+ and Dy3+ ions were found to be about 0.173 and
0.181 eV, respectively. The relatively high activation energy obtained in this work suggested that
the as-prepared phosphors had good thermal stability and were promising candidates for highpowered LEDs applications.
In order to judge the appropriateness of obtained samples for their applications in FEDs, the
CL properties of the NaCaBO3:0.02Tm3+/0.03Dy3+ phosphor were investigated. Figure 13 shows
the CL spectra of the NaCaBO3:0.02Tm3+/0.03Dy3+ phosphor at different accelerating voltages
and filament currents. It is evident that the CL spectra of the NaCaBO3:0.02Tm3+/0.03Dy3+
phosphor, which were composed of four emission bands at 458, 482, 577 and 664 nm
corresponding to the featured emission peaks of Tm3+ and Dy3+ ions, were matched well with the
PL spectrum (see Fig. 8c). Moreover, when the filament current was fixed at 55 A, the CL
emission intensity increased rapidly with the increased accelerating voltage from 5 to 9 kV (see
Fig. 13(a)). Similarly, with the changing of the filament current from 33 to 55 A, the CL
emission intensity was also enhanced when the accelerating voltage was 9 kV, as displayed in
Fig. 13(b). For CL emission, the RE ions are excited by the plasmons created by the incident
electrons. In general, the higher the accelerating voltage and filament current, the more plasmons
12

will be produced, leading to more RE ions being excited and the elevated CL emission intensity
[43]. Furthermore, the deeper penetration of the electrons into the phosphor body and the larger
electron beam current density were the other reason for the increased CL emission intensities.
Based on the previous works [46,47], the electron penetration depth (L) is expressed as:

A E
1.2
L 250 1/2 , and n
, (7)
1 0.29lg Z
Z
n

where A stands for molecular weight of the material, is the bulk density, E presents the
accelerating voltage and Z is the atomic number. For the NaCaBO3:0.02Tm3+/0.03Dy3+
phosphor, the values of A, and Z are constants. Therefore, from Eq. (7), one obtains that the
electron penetration depth is in proportion to the accelerating voltage and it can be enhanced
with elevating the accelerating voltage, resulting in the increment of the CL emission intensity. It
is noticeable that, with increasing the accelerating voltage or filament current, no obvious
saturation phenomenon for the CL emission intensity was observed (see Fig. 13). The CIE
chromaticity coordinates calculated from the CL spectra are summarized and presented in Table
S1 and Fig. S2. As displayed in Table S1, the CIE chromaticity coordinates was slightly changed
with the increment of accelerating voltage or filament current. These CIE chromaticity
coordinates were located in the white light region (see Fig. S2). Consequently, the
NaCaBO3:0.02Tm3+/0.03Dy3+ phosphor exhibited excellent CL properties with stable CIE
chromaticity coordinates.
<H1>4. Conclusions
In summary, the NaCaBO3:RE3+ (RE3+ = Tm3+, Dy3+, Tm3+/Dy3+) phosphors were prepared
through a solid-state reaction technique. Under UV light excitation, the NaCaBO3:xTm3+ and
NaCaBO3:yDy3+ phosphors emitted the featured luminescence of Tm3+ and Dy3+ ions,
respectively. Furthermore, when excited at 358 nm, which matches with commercial UV-LED
13

chips, the emission color of NaCaBO3:0.02Tm3+/zDy3+ phosphors can be tuned from blue to
white by adjusting the concentration ratio of Tm3+/Dy3+ because of the effective ET from Tm3+
to Dy3+ ions and the ET efficiency was around 89.4% when z = 0.07. Besides, the ET between
Tm3+ and Dy3+ ions was proved to be dipole-dipole interaction and Rc value was about 23.55 .
The fluorescence intensities of Tm3+ and Dy3+ ions declined to 76.1 and 89.4% at 150 C, as
compared to room temperature, respectively, confirming that the sintered products had good
thermal stability. In addition, the CL properties were also achieved in the synthesized products
and the emission intensities were enhanced with elevating the accelerating voltage and filament
current. These results suggested that the color-tunable Tm3+/Dy3+-codoped NaCaBO3 phosphors
with good thermal stability may have potential applications in UV-excited WLEDs and FEDs.
<ACK>Acknowledgement
This work was supported by the National Research Foundation of Korea (NRF) Grant funded by
the Korea government (MSIP) (No. 2015R1A5A1037656).
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<Figure>Fig. 1. XRD patterns of (a) NaCaBO3, (b) NaCaBO3:0.02Tm3+, (c) NaCaBO3:0.03Dy3+
and (d) NaCaBO3:0.02Tm3+/0.03Dy3+ phosphors.
<Figure>Fig. 2. (a) SEM image, (b) TEM image, (c) HR-TEM image and (d) SAED pattern of
NaCaBO3:0.02Tm3+/0.03Dy3+ phosphor. (e) Elemental mapping of Na, Ca, B, Tm, Dy and O.
<Figure>Fig. 3. PLE (black line) and PL (blue line) spectra of the NaCaBO3:0.02Tm3+ phosphor.
<Figure>Fig. 4. PL spectra of NaCaBO3:xTm3+ phosphors as a function of Tm3+ ion
concentration excited at 358 nm. Inset depicts the plot of lg(I/x) vs. lg(x) for the 1D2 3F4
transition of Tm3+ ions in NaCaBO3:xTm3+ phosphors.
<Figure>Fig. 5. PLE (black line) and PL (orange line) spectra of the NaCaBO3:0.03Dy3+
phosphor.
<Figure>Fig. 6. PL spectra of NaCaBO3:yDy3+ (y = 0.01, 0.03, 0.05, 0.07 and 0.09) phosphors
excited at 350 nm. Inset shows the plot of lg(I/y) vs. lg(y) for the 4F9/2 6H13/2 transition of Dy3+
ions in NaCaBO3:yDy3+ phosphors.

17

<Figure>Fig. 7. (a)-(e) PL spectra of NaCaBO3:0.02Tm3+/zDy3+ (z = 0, 0.01, 0.03, 0.05 and

0.07) phosphors excited at 358 nm. (f) PL emission intensity of Tm3+ and Dy3+ ions as a function
of Dy3+ ion concentration.
<Figure>Fig. 8. Energy level diagram of Tm3+ and Dy3+ ions as well as the proposed ET
processes.
<Figure>Fig. 9. Dependence of Dy3+ ion concentration on the energy transfer efficiency in
NaCaBO3:0.02Tm3+/zDy3+ phosphors. Inset shows the normalized PL emission intensity of Tm3+
ion as a function of Dy3+ ion concentration.
6/3

8/3

10/3

<Figure>Fig. 10. The dependence of IS0/IS of Tm3+ ions on (a) Ctotal , (b) Ctotal and (c) Ctotal .
<Figure>Fig. 11. CIE chromaticity coordinates of NaCaBO3:0.02Tm3+/zDy3+ phosphors with
different Dy3+ ion concentrations. Inset shows the corresponding luminescent images excited at
358 nm.
<Figure>Fig. 12. (a) Temperature-dependent PL spectra of NaCaBO3:0.02Tm3+/0.03Dy3+
phosphor. (b) and (c) Normalized PL emission intensities of Tm3+ and Dy3+ ions as a function of
temperature, respectively. (d) Plots of ln(I0/I-1) vs. 1/T for NaCaBO3:0.02Tm3+/0.03Dy3+
phosphor.
<Figure>Fig. 13. CL spectra of the NaCaBO3:0.02Tm3+/0.03Dy3+ phosphor as a function of (a)
accelerating voltage with a fixed filament current at 55 A and (b) filament current with a fixed
accelerating voltage at 9 kV.

Tables
<Table>Table 1 CIE chromaticity coordinates of NaCaBO3:0.02Tm3+/zDy3+ phosphors
calculated from PL spectra.

18

Points Phosphors

Excitation wavelength (nm)

CIE (x,y)

a1

NaCaBO3:Tm3+

358

(0.155,0.039)

a2

NaCaBO3:Tm3+/0.01Dy3+

358

(0.242,0.165)

a3

NaCaBO3:Tm3+/0.03Dy3+

358

(0.308,0.260)

a4

NaCaBO3:Tm3+/0.05Dy3+

358

(0.334,0.302)

a5

NaCaBO3:Tm3+/0.07Dy3+

358

(0.348,0.323)

TDENDOFDOCTD

19