Accepted Manuscript

3+
Structure, energy transfer and tunable photoluminescence of Sr7Zr(PO4)6:Tb ,
3+
Eu phosphors for near-UV white LEDs

Yaomiao Feng, Jinping Huang, Chunmei Li, Gang Hu, Jie Liu, Xibin Yu
PII: S0925-8388(17)30645-X
DOI: 10.1016/j.jallcom.2017.02.199
Reference: JALCOM 40927

To appear in: Journal of Alloys and Compounds

Received Date: 6 January 2017

Revised Date: 16 February 2017
Accepted Date: 18 February 2017

Please cite this article as: Y. Feng, J. Huang, C. Li, G. Hu, J. Liu, X. Yu, Structure, energy transfer and
3+ 3+
tunable photoluminescence of Sr7Zr(PO4)6:Tb , Eu phosphors for near-UV white LEDs, Journal of
Alloys and Compounds (2017), doi: 10.1016/j.jallcom.2017.02.199.

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 ACCEPTED MANUSCRIPT

Graphic Abstract

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Structure, Energy Transfer and Tunable Photoluminescence of

Sr7Zr(PO4)6:Tb3+, Eu3+ Phosphors for Near-UV White LEDs

Yaomiao Feng, Jinping Huang*, Chunmei Li, Gang Hu, Jie Liu, Xibin Yu

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Shanghai Key Laboratory of Rare Earth Functional Materials, Department of

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Chemistry, Shanghai Normal University, Shanghai 200234, China

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Corresponding author. E-mail address: [email protected]
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Abstract

A series of Sr7Zr(PO4)6:Tb3+, Eu3+ phosphors of eulytite-type structure have been

synthesized via a high temperature solid-state reaction. The crystal structure and

luminescence property of the samples was systematically investigated by XRD

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Rietveld refinement, excitation and photoluminescence, respectively. For Tb3+ and

Eu3+ ions single doped phosphor, the characteristic emission from f-f transitions of

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Tb3+ at 544 nm and Eu3+ at 613 nm was observed, while for Tb3+ and Eu3+ co-doped

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phosphor Sr7Zr(PO4)6:Tb3+, xEu3+, various emission color from green to red can be

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achieved by trimming the relative ratio of Eu3+ to Tb3+ in Sr7Zr(PO4)6 host. Moreover,
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a warm white light emission of single phased with CIE coordinates at (0.359, 0.327)

and correlated color temperature (CCT) at 4264 K was realized under 374 nm
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excitation. The energy transfer process from Tb3+ to Eu3+ in Sr7Zr(PO4)6 was verified
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by fluorescence spectra and decay time, where a resonant type via a dipole-dipole
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mechanism was demonstrated. In addition, the Sr7Zr(PO4)6:Tb3+, Eu3+ phosphors

exhibited an excellent thermal quenching luminescence property owing to the

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structural stability. These results indicate that Sr7Zr(PO4)6:Tb3+, Eu3+ could be

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anticipated as color-tunable and direct white-light-emitting phosphor for

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near-UV-pumped w-LEDs application.

Keywords Color-tunable emission, Single-phased white-light-emitting phosphor,

Sr7Zr(PO4)6:Tb3+, Eu3+, near-ultraviolet w-LEDs

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1 Introduction

Phosphor-converted white-light-emitting diodes (w-LEDs) have been considered

as the most promising green lighting source because of their unique characteristics

such as long operation lifetime, low power consumption, high reliability and

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environmental friendliness [1-3]. Luminescent materials play a significant role in

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fabricating high performance lighting and display devices. In the last few years, many

researches have focused on exploring new types of phosphors with

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high luminous efficiency and excellent thermal stability to improve the performance

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of w-LED devices. In commercial w-LEDs devices, the way to obtain white light is
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by combination of blue GaN-based LED chips with a yellow phosphor Y3Al5O12:Ce3+

(YAG:Ce3+) [4]. However, white light produced by this device generally exhibits a
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poor color rendering index (Ra < 80) and a high correlated color temperature (Tc >
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7000 K) because the emission peak of Ce3+ in this compound centered at 540 nm, less
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coverage in the red spectral region. As an alternative, the strategy based on

near-ultraviolet (n-UV) LEDs coupled with tricolor phosphors of red, green and blue
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was proposed to generate white light by adjusting the ratios of tricolor phosphors [5-7].
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Nevertheless, LED device based on mixing multiple phosphors shows an inevitable

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problem of fluorescence re-absorption between different components and

non-uniformity of the luminescence property, which causes the decrease of luminous

efficiency and the deviation from color point upon time for w-LEDs [8-10].

To circumvent these drawbacks, many researches have focused on single-phased

phosphors assembled with near-UV LEDs chips. Based on the principle of energy

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transfer from the sensitizer to the activator, white-light emission can be directly

achieved by co-doping multiple emissive ions into a single-phased crystalline

matrices under excitation of n-UV light. Compared to the tricolor scheme of LED

system, the single-phased white-light-emitting phosphors have the advantages such as

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easy fabrication, perfect stability and color reproducibility [11-13]. Up to now, the

associated sensitizers and activators have involved in Eu2+/Mn2+, Eu2+/Dy3+,

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Ce3+/Eu2+, Ce3+/Tb3+, Ce3+/Mn2+ and Eu2+/Tb3+/Mn2+ or Ce3+/Mn2+/Tb3+ etc, by which

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various tunable full-color emitting phosphors and single phase white-emitting

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phosphors have been prepared [14-16]. Some of them present excellent luminescence
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performance and show potential application in w-LEDs. However, new and efficient

white-light phosphors of single-phased compound are still highly demanded. For the
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co-doped phosphors, an appropriate host material plays an important role in

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accommodation of sensitizer and activator，rendering an efficient energy transfer and

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luminescence performance [17-19]. Recently, eulytite-type orthophosphate

compounds M3Ln(PO4)3 (where M = divalent ions and Ln = trivalent lanthanum ions)

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acting as host matrices doped with various activators have drawn increasing attention
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due to their chemical stability and mild synthesis condition [20,21]. The series of
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M3Ln(PO4)3 crystallizes in cubic system, space group I 43d [220]. The Ln3+/M2+

pairs of cations randomly reside in a single crystallographic site (C3 point group

symmetry), while the oxygen atoms of the phosphate groups are distributed over

several partially occupied sites. This type of compound was found to show disorder

not only in the cations but also in the oxygen sub-lattice. The disordered structures

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provide abundant crystal field environments for various doping ions, making it

possible to finely tune the luminescent properties of phosphors. In addition to

M3Ln(PO4)3, the series of M7B(PO4)6 represent another eulytite-type compounds,

while B is tetravalent Zr4+, Hf4+ and Sn4+ ions. Generally, heavy metal ions such as

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Zr4+ in hosts have great influence on the properties, such as nonlinear optical,

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dielectric, ferroelectric and the valence states of activators [22]. Moreover,

zirconium-containing phosphors always present admirable thermal stability. The

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self-activated luminescent M7Zr(PO4)6 (M = Ca, Sr, Ba) was reported by Qin et al [23]

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and the luminescence was ascribed to the charge transfer transition of Zr-O. Tb3+ ions
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act as a good sensitizer to enhance the luminescence efficiency of Eu3+ ions in the

co-doped host have been well reported [24, 25]. In this paper, we synthesized a series
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of novel green to red emission color-tunable phosphors Sr7Zr(PO4)6:Tb3+, Eu3+. The

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mechanism of energy transfer from Tb3+ to Eu3+ in Sr7Zr(PO4)6 was systematically

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investigated by the emission spectra and lifetime measurements based on the detailed

analysis of the crystal structure for eulytite-type Sr7Zr(PO4)6. Moreover, the thermal
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resistance of phosphor was measured to ascertain the thermal stability and

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temperature quenching property of the phosphors. It is expected that by combination

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of the temperature quenching-proof feature and the efficient color-tunable

luminescence, the single-phased Sr7Zr(PO4)6:Tb3+, Eu3+ phosphor may find promising

application for n-UV-pumped w-LEDs.

2 Experimental

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2.1 Sample Preparation. A series of Sr7Zr(PO4)6:0.01Tb3+,xEu3+ phosphors were

synthesized by solid-state reaction between stoichiometric ratio of raw material

(SrCO3, ZrO2, (NH4)2HPO4, Tb2O3 and Eu2O3 of analytical purity). These powders

were homogeneously mixed in an agate mortar for 30 min, and the mixtures were

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transferred to a corundum crucible and sintered in a tubular furnace at 1250 ˚C for 4 h.

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When the temperature drops to room temperature naturally, the polycrystalline

products were obtained.

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2.2 Measurements and Characterization. The material characterizations and the

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photoluminescence (PL) and excitation (PLE) spectra measurements of the
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as-synthesized phosphors were according to our previous work [26]. The decay curves

were recorded on an Edinburgh Instrument FLS980 spectrometer equipped with µF2

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flash lamp as the excitation source, Red PMT detector with the channel TCC Det 1,
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bandwidth 1 nm and frequency 5Hz. All the measurements were carried out at room
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temperature except for thermoluminescence measurements.

3 Results and discussion

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3.1 Phase Identification. Different content of Eu3+ ions (x=0-0.02) were doped in
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Sr7Zr(PO4)6:0.01Tb3+ for the purpose of optimizing the luminescent property. By

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comparing the diffraction spectra in Figure 1, the powder XRD patterns of the

as-prepared samples are identical and match well with the reported Sr7Zr(PO4)6

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(PDF# 34-0065), in cubic structure, I 4 3d space group, indicating that all the

obtained compounds are single phased. Tb3+/Eu3+ doping did not bring discernable

impurity when the molar ratio of Tb3+ ions is fixed at 0.01, until the content of Eu3+

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ions gradually increased up to x=0.02. This phenomenon means the Tb3+ and Eu3+

ions have been incorporated into the lattice of Sr7Zr(PO4)6.

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Figure 1 XRD patterns of the as-synthesized Sr7Zr(PO4)6: 0.01Tb3+, xEu3+ (x=0-0.02)
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doped with different content of Eu3+ ions , respectively.

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In order to verify the rare earth ions Tb3+ and Eu3+ have successfully implanted
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the site of Sr2+, the detailed crystal structure analysis on Sr7Zr(PO4)6: 0.01Tb3+, xEu3+
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(x=0-0.02) was conducted by the XRD Rietveld refinements. The crystallographic

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data of Sr3La(PO4)3 (ICSD# 69432) in cubic crystal system, space group I 43d was
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used as initial model, because the crystallographic information of Sr7Zr(PO4)6 is

unavailable. As illustrated in Figure 2, the eulytite-type structure of Sr7Zr(PO4)6 host

consists of a three-dimensional packing of [PO4] tetrahedrons and strongly distorted

mixed [Sr/ZrO6] octahedrons. Sr/Zr ions are located at the single 16c Wyckoff sites

(C3 symmetry) and are distributed at random, keeping the site occupancy at 4: 1 for

Sr to Zr in the unit cell. The oxygen atoms of the phosphate groups are distributed
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over several partially occupied sites, and thus, both the cation/anion sites are distorted

in the host lattice. When Tb3+ and Eu3+ ions doped, they are supposed to substitute Sr2+

ions entering the 16c site in Sr7Zr(PO4)6 crystal structure due to the similar ionic radius

and charge (when CN = 8, for Eu3+ ions: r = 1.07 Å; for Tb3+ ions: r =1.04 Å and Sr2+

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ions: r =1.26 Å). In the refinement process, it is found that under the circumstances of

Tb3+ and Eu3+ at the Zr4+ sites, the reliability parameters of refinement is degraded,

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which may suggest a preferring occupation of Tb3+ and Eu3+ to the Sr2+ sites.

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(a)
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(c)
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Figure 2 The unit cell of Sr7Zr(PO4)6 (a); [PO4] tetrahedron when O atoms distribute

over several partially occupied sites randomly (b); the distorted [Sr/ZrO6] octahedron

coordination surroundings of Sr2+/Zr4+ ions (c).

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The corresponding refinement profiles of Sr7Zr(PO4)6: 0.01Tb3+, 0.02Eu3+ are

presented in Figure 3. The reliability parameters of the refinement on all the observed

reflections Rp =7.62%，Rwp =8.17%, Rexp = 6.25% and χ2 = 1.09 give a satisfying

result, considering that a slight amount of impurity peaks exists. The intensities and

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positions are assigned to the hexagonal Sr3(PO4)2 (PDF 24-1008). The refinement

factors and the lattice parameters of Sr7Zr(PO4)6: 0.01Tb3+, xEu3+ are summarized in

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Table 1. From Table 1, it can be seen that with incorporation of Tb3+ and Eu3+ ions,

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the unit cell volume decreases, and when the Eu3+ content increases to x=0.02, the cell

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volume drops to 1057.1 Å3 (Figure 4). This phenomenon demonstrates the successful
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introduction of Tb3+ and Eu3+ into the structure of Sr7Zr(PO4)6 host, which in turn

leads to the shrinkage of unit cell volume, because both the ionic radii of Tb3+ and
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Eu3+ are smaller than that of Sr2+ under the given coordination number.
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Figure 3 XRD refinement patterns of the samples Sr7Zr(PO4)6: 0.01Tb3+, 0.02Eu3+,

experimental (black cross), calculated (red line), and difference (blue line in the

bottom).

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Table 1 The structural parameters and refinement factors of the Sr7Zr(PO4)6-based

samples.

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Formula a/b/c (Å) V(Å3) Rwp(%)

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Sr7Zr(PO4)6 10.254 1059.8 8.22

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Sr7Zr(PO4)6: 0.01Tb3+ 10.239 1058.0 8.29

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Sr7Zr(PO4)6: 0.01Tb3+,0.02Eu3+ 10.151 1057.1 8.17
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Figure 4 The dependence of lattice cell volume on Eu3+ content for Sr7Zr(PO4)6:

0.01Tb3+, xEu3+ (x =0, 0.005, 0.010, 0.015 and 0.020), respectively.

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3.2 Photoluminescence Properties. Figure 5A shows the excitation and emission

spectrum of Tb3+ singly activated Sr7Zr(PO4)6. Monitored the emission at 544 nm, the

PLE of Sr7Zr(PO4)6:Tb3+ shows a series of spectra bands in the range of 290 to 420

nm, which is attributed to the transitions of Tb3+ ions for 7F6-5H6 (303 nm),

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F6-5H7(317 nm), 7F6-5D2 (341 and 350 nm), 7F6-5D3 (368 and 374 nm), respectively.

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Corresponded to the prominent excitation at 374 nm, the intense green emission

Sr7Zr(PO4)6: 0.01Tb3+ is found at 544 nm. The emission spectra ranging from blue to

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green region are also observed maximum at 418, 439, 489, 544, 584 and 624 nm,

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which are assigned to the transitions of 5D3–7F5, 5D3–7F4, 5D4-7F6, 5D4-7F5, 5D4-7F4,
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D4-7F3, respectively.
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Figure 5 PLE and PL spectra of Sr7Zr(PO4)6: 0.01Tb3+ (A), Sr7Zr(PO4)6: 0.01Eu3+ (B),

and Sr7Zr(PO4)6: 0.01Tb3+, 0.02Eu3+ (C)

The PLE and PL of Eu3+ ions singly doped Sr7Zr(PO4)6: 0.01Eu3+ are displayed

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in Figure 5B. Monitored 613 nm emission of Eu3+ ions, the excitation spectra in

325-545 nm are ascribed to intra-transitions within 4f6 electronic configuration of Eu3+.

The prominent excitation of Sr7Zr(PO4)6: 0.01Eu3+ at 394 nm well matches with the

output wavelengths of near-UV LED chips. Upon excitation of 394 nm, the PL

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spectra of Sr7Zr(PO4)6: 0.01Eu3+ ranging in 545-720 nm with the hypersensitive

emission at 613 nm are assigned to the transitions: 5D0–7F0 (583 nm), 5D0–7F1 (591

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nm), 5D0–7F2 (613 nm), 5D0–7F3(651 nm), 5D0–7F4 (701 nm), respectively. By

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comparing Figure 5A with 5B, the overlap of the excitation spectra of Sr7Zr(PO4)6:

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0.01Eu3+ and the emission spectra of Sr7Zr(PO4)6: 0.01Tb3+ is observed, suggesting a
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possibility of an effective resonance-type energy transfer (ET) from the Tb3+ to Eu3+

ions.
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For the PLE and PL spectra of Tb3+ and Eu3+ co-activated Sr7Zr(PO4)6 phosphor
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in Figure 5C, the excitation spectra monitored at 613 and 544 nm is consistent with
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the PLE of Eu3+ and Tb3+ single doped Sr7Zr(PO4)6 phosphor. From Figure 5C, it is

clearly found that for the co-activated sample, the excitation intensity of Eu3+ is
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stronger than that of Eu3+ single doped Sr7Zr(PO4)6 phosphor, while the excitation
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intensity of Tb3+ is attenuated relative to Tb3+ single doped Sr7Zr(PO4)6 phosphor.

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This phenomenon manifests an energy transfer (ET) occurs from Tb3+ to Eu3+ ions in

co-doped Sr7Zr(PO4)6: 0.01Tb3+, 0.02Eu3+ phosphor. Under 374 nm excitation, the PL

spectra of Sr7Zr(PO4)6: 0.01Tb3+, 0.01Eu3+ exhibit two prominent peaks at 613 and

544 nm derived from the characteristic emission of Eu3+ and Tb3+ ions, respectively.

On the basis of above results, a schematic energy-level diagram and the energy

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transfer between Tb3+ and Eu3+ in Sr7Zr(PO4)6 is shown in Figure 6. It is known that

the exchange and electrostatic interaction are generated from physical interaction

between the sensitizer and activator ions during the energy transfer process. After

multistep relaxations, the excited electrons shift to the 5D4 or 5D3 excited state of Tb3+

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under 374 nm excitation. The emission spectra of Sr7Zr(PO4)6: 0.01Tb3+ in blue or

green region result from the electrons of the Tb3+ ions shift from the 5D4 or 5D3

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excited state to the 7FJ ground state. The rest of the Tb3+ ions with 5D4 excited state

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transfer their energy to the 5D1 excited state of Eu3+ ions, leading to red emission from

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Eu3+ ions through 5D0–7FJ (J = 0–6) transitions.
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Figure 6 Schematic energy-level diagram of Tb3+ and Eu3+ in Sr7Zr(PO4)6 and the
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energy transfer from Tb3+ to Eu3+

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To better understanding the sensitization effect between Tb3+ and Eu3+ ions, a

series of Sr7Zr(PO4)6: 0.01Tb3+, xEu3+samples with different content of Eu3+ ions (x =

0–0.02) have been prepared. In Figure 7, under 374 nm excitation, the emission

intensity of Eu3+ at 613 nm enhances with increasing Eu3+ doping concentration,

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whereas that of Tb3+ at 544 nm decreases simultaneously because of the energy

transfer from Tb3+ to Eu3+. As a result, the emission color can be trimmed by adjusting

the ratio between the Eu3+ and Tb3+ ions in the host lattice. Relative intensity variation

of Tb3+ and Eu3+ emission in Sr7Zr(PO4)6: 0.01Tb3+, xEu3+ can be directly observed in

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the inset of Figure 7.

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Figure 7 Under 374 nm excitation, the emission spectra of Sr7Zr(PO4)6: 0.01Tb3+,

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xEu3+ with different content of Eu3+ ions (x=0-0.02); the inset indicates the relative
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intensity of Tb3+ and Eu3+ emission in Sr7Zr(PO4)6: 0.01Tb3+, xEu3+ phosphors .

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Under the excitation of 374 nm, the CIE chromaticity coordinates and energy

transfer efficiency of Sr7Zr(PO4)6: 0.01Tb3+, xEu3+ (x = 0-0.02) are presented in Table

2. With increase of Eu3+ doping concentration, the emission color from green turns to

orange, the corresponding CIE chromaticity coordinates from A to E in Figure 8. The

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energy transfer efficiency ηT from Tb3+ to Eu3+ ions in Sr7Zr(PO4)6: 0.01Tb3+, xEu3+

can be expressed by the equation [27, 28]:

Is
ηT = 1- (1)
Iso

Where ηT is the energy transfer efficiency, and Iso and Is are the luminescence

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intensity of Tb3+ ions in the absence and presence of Eu3+ ions, respectively. It can be

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seen from Table 2 that the energy transfer efficiency is consistently raised by

increment of Eu3+ ions concentration.

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Table 2 CIE Chromaticity Coordinates (x, y) and energy efficiency (ηT) of
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Sr7Zr(PO4)6: 0.01Tb3+, xEu3+ (x = 0-0.020) under 374 nm excitation.
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Sample X Y ηT
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Sr7Zr(PO4)6:0.01Tb3+ 0.265 0.320 －

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Sr7Zr(PO4)6:0.01Tb3+,0.005Eu3+ 0.309 0.322 45.4%

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Sr7Zr(PO4)6:0.01Tb3+,0.01Eu3+ 0.337 0.322 54.3%

Sr7Zr(PO4)6:0.01Tb3+,0.015Eu3+ 0.359 0.327 60.6%

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Sr7Zr(PO4)6:0.01Tb3+,0.02Eu3+
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0.386 0.330 68.2%

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Figure 8 The CIE chromaticity diagram of Sr7Zr(PO4)6: 0.01Tb3+, xEu3+ (x = 0-0.02)
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under the excitation of 374 nm.
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The energy transfer from a sensitizer to an activator in the host may via a
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resonance-type mechanism derived from exchange interaction and electric multi-polar

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interactions have been well discussed [29,30]. If the critical distance between the
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sensitizers and activators was shorter than 3-4 Å, the mechanism of exchange

interaction is assumed [31]. The concentration quenching was evaluated by

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calculation of the critical distance for energy transfer between the twin doped ions.

The following formula proposed by Blasse was used to estimate the critical distance

RC between Tb3+ and Eu3+ [32].

1/ 3
 3V 
REu −Tb = 2  (2)
 4πxc N 

In the formula, V is the volume of the unit cell, and N is number of formula units

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per unit cell, and xc is the critical concentration of dopant ions. The unit cell parameters

of the Sr7Zr(PO4)6 host are obtained from XRD Rietveld refinement by using

Sr3La(PO4)3 as initial mode, where the values of V and N are 1059.8 Å3 and 2,

respectively. Since no concentration quenching occurs in Tb3+ and Eu3+ co-doped

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Sr7Zr(PO4)6 phosphor, the value of xc is 1. Thus, the critical distance Rc is calculated to

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be 12.65 Å. This value is much longer than 5 Å, which may suggest the energy

transfer mechanism between Tb3+ and Eu3+ adopt electric multi-polar interactions.

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According to Dexter’s energy transfer expression of multi-polar interaction and

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Reisfeld approximation, the following relation can be given as [33]:
η
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0
∝ C n / 3 (3)
η s

In the formula, η0 and ηs are the luminescence quantum efficiencies of Tb3+ in the
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absence and presence of Eu3+, respectively. The value of η0/ηs can be estimated
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approximately by the ratio of the relative luminescence intensities Is0/Is, C represents

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the total concentration of Tb3+ and Eu3+, and n = 6, 8, and 10 correspond to the

electric multipolar interaction of the electric dipole–dipole, dipole–quadrupole and

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quadrupole–quadrupole interactions, respectively. The relationships between Is0/Is and

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C(n/3
Eu 3+ +Tb3+ )
are illustrated in Figure 9. By comparing the R values of the fitting factors,
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the optimal linear relationship is obtained from Is 0 ∝ C n / 3 in Figure 9 (R = 0.9869),

Is

which implies that the energy transfer from Tb3+ to Eu3+ obeys a dipole–dipole

interaction.

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Figure 9 The correlations between Is0/Is and C(n/3
Eu 3+ + Tb 3+ )

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To gain further insight into the energy transfer processes from Tb3+ to Eu3+, the

photoluminescence decay curves of Sr7Zr(PO4)6:0.01Tb3+,xEu3+ with x=0, 0.005,

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0.010, 0.015, 0.020 (λex=374 nm, λem=544 nm) were depicted in Figure 10. It can be
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seen that the curves were well fitted by a second exponential decay mode by using the
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following equation [34]:

I (t) = I1exp (−t/τ1) + I2exp (−t/τ2) (4)

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Where I1 and I2 refer to intensities at different time, and τ1 and τ2 represent the
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corresponding decay time for the exponential components, respectively.

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Based on equation 4, the average lifetime τ can be obtained using the formula

[35]:

τ= (I1τ1+ I2τ2) / (I1 + I2) (5)

Thus, the obtained average decay lifetimes are determined to be 3.97, 2.85, 2.30,

1.96, and 1.72 ms with increasing concentration of Eu3+ ions from 0 to 0.020. These

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decay lifetimes suggest Sr7Zr(PO4)6:0.01Tb3+,0.02Eu3+ suitable for solid-state lighting

phosphors of w-LED. It is noticed that the decay lifetime of Tb3+ ions decreased with

increasing the concentration of Eu3+, which strongly demonstrates the existence of

energy transfer process from Tb3+ to Eu3+ ions. As the Eu3+concentration increasing,

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the possibility of energy transfer from Tb3+ to Eu3+ ions increases, and thus leads to a

faster decay of the excited state for Tb3+ as sensitizer.

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The energy transfer efficiency (ηT) between the Tb3+ and Eu3+ ions can also be

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expressed by the following equation [36]:
τs

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ηT=1- (6)
τso
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Where ηT is the energy transfer efficiency, and τs and τso represent the lifetime

values of sensitizer Tb3+ with and without the activator Eu3+, respectively.
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From Figure 11, it is clearly observed that the energy transfer efficiencies of the
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sample increase gradually. When the content of Eu3+ is up to 0.02, ηT value reaches
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56.7%, in coincidence with the former result (68.2%).

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Figure 10 Fluorescent decay curves of Tb3+ ions in Sr7Zr(PO4)6:0.01Tb3+,xEu3+

(x=0-0.02) monitored at 544 nm under 374 nm excitation.

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Figure 11 Dependences of decay time and corresponding energy transfer efficiency

upon different concentration of Eu3+ ions in Sr7Zr(PO4)6:0.01Tb3+,xEu3+ (x=0-0.02).

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The thermal stability of phosphor is one of the crucial parameter for the potential
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application in LEDs. It also has a directly impact on light output and CRI value. The

temperature-dependent PL spectra of Sr7Zr(PO4)6:0.01Tb3+,0.01Eu3+ phosphors

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measured from 50 to 250˚C under 374 nm excitation was shown in Figure 12. It can

be seen that the luminance intensity of the as-prepared phosphors decreased with the

increasing temperature. When the temperature rises to 250 ˚C, the

fluorescence intensity of Tb3+ and Eu3+ drops to 70.23% and 54.20% relative to that

measured in ambient atmosphere (25˚C). These results indicate that the

Sr7Zr(PO4)6:0.01Tb3+,0.01Eu3+ phosphors have a good thermal quenching

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luminescence behavior, predicting a potential application in high power LEDs

devices.

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Figure 12 Dependence of emission spectra of Sr7Zr(PO4)6:0.01Tb3+,0.01Eu3+ on

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temperature under 374 nm excitation; the inset shows the emission intensities of Tb3+

and Eu3+ as a function of temperature, respectively.

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In general, the emission intensities of phosphors gradually decline with rising the
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operating temperature. It is caused by thermal quenching due to thermal activation of

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the crossing point between the ground and the excited states [37]. The discrepant

intensity decrease tendency of Tb3+ and Eu3+ ions in Sr7Zr(PO4)6 matrix with the

rising temperature may attributed to their different sensitivity to temperature and the

energy transfer efficiency from Tb3+ to Eu3+ ions in the hosts. Activation energy is

often used to explicate the thermal stability of luminescence in phosphors. The

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thermal quenching linear relationship of Sr7Zr(PO4)6: 0.01Tb3+,0.01Eu3+ fitted by

Arrhenius formula as below [38]:

Ln(IO/I)= LnA- Ea/KT (7)

Where Io and I represent intensity measured at room temperature (25˚C) and the

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test temperature, respectively. A is a constant and K is the Boltzmann constant. T and

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Ea correspond to the temperature (K) and the estimated activation energy.

The graph of Ln (Io/I-1) versus 1/kT activation energy based on equation 7 in

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Figure 13 illustrates the thermal quenching of the Sr7Zr(PO4)6:0.01Tb3+,0.01Eu3+. The

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slope of the fitting line is 0.305. Thus, the activation energy Ea is approximately 0.305
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eV.
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Figure 13 Linear fitting of Ln (Io/I − 1) versus 1/kT activation energy for Sr7Zr(PO4)6:

0.01Tb3+,0.01 Eu3+.

4 Conclusions

In summary, we have successfully synthesized a series of color-tunable

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Sr7Zr(PO4)6: 0.01Tb3+, xEu3+ phosphors with cubic structure, I 43d space group via

high-temperature solid state reaction. The luminescence properties and energy-transfer

mechanism of the phosphors were also studied based on the detailed structure analysis

by powder X-ray diffraction Rietveld refinement. Because of the spectra overlap

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between the emission spectra of Tb3+ and the excitation spectra of Eu3+. An effective

energy transfer between Tb3+ and Eu3+ occurs under the excitation of 374 nm. Thus,

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the emission color of Sr7Zr(PO4)6: Tb3+, Eu3+ phosphors can be modulated from green

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(0.2648, 0.3204) to orange (0.5345, 0.3694) by adjusting the ratio of Eu3+ to Tb3+.

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Meanwhile, a warm white light emission of single phased Sr7Zr(PO4)6: 0.01Tb3+,
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0.015Eu3+ with CIE coordinates at (0.3592, 0.3273) and correlated color temperature

(CCT) at 4264 K was achieved under 374 nm excitation. These results indicate that
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with the excellent thermal stability and efficient color-tunable and warm white light
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luminescence, Sr7Zr(PO4)6: Tb3+, Eu3+ series phosphors may hold great promise for
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application in near-ultraviolet w-LEDs.

Acknowledgments
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This work is supported by National Major Scientific Instrument and Equipment

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Development Project (2013YQ15055708).

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Highlights

1. A series of single phased warm-white-emissive and color-tunable phosphors were

prepared.

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2. The crystal structure and photoluminescence property of the phosphors were
systematically investigated.

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3. The energy transfer process from Tb3+ to Eu3+ in Sr7Zr(PO4)6 was verified by
fluorescence spectra and decay time.

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4. Excellent thermal quenching property predicts the promising application in
near-UV LEDs.

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