View Article Online

Dalton
View Journal

Transactions
An international journal of inorganic chemistry
Accepted Manuscript

This article can be cited before page numbers have been issued, to do this please use: J. Zhong, W. Xu,
Q. Chen, S. Yuan, Z. Ji and D. Chen, Dalton Trans., 2017, DOI: 10.1039/C7DT02090B.

Volume 45 Number 1 7 January 2016 Pages 1–398 This is an Accepted Manuscript, which has been through the

Dalton Royal Society of Chemistry peer review process and has been
accepted for publication.
Transactions
An international journal of inorganic chemistry Accepted Manuscripts are published online shortly after
www.rsc.org/dalton

acceptance, before technical editing, formatting and proof reading.

Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.

You can find more information about Accepted Manuscripts in the

author guidelines.

Please note that technical editing may introduce minor changes

to the text and/or graphics, which may alter content. The journal’s
ISSN 1477-9226 standard Terms & Conditions and the ethical guidelines, outlined
PAPER
in our author and reviewer resource centre, still apply. In no
Joseph T. Hupp, Omar K. Farha et al.
Efficient extraction of sulfate from water using a Zr-metal–organic
framework
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.

rsc.li/dalton
 Page 1 of 20 Dalton Transactions
View Article Online
DOI: 10.1039/C7DT02090B

Mn4+,Li+ co-doped SrMgAl10O17 phosphor-in-glass: Application in

high-power warm w-LEDs

Jiasong Zhong, Wei Xu, Qingli Chen, Shuo Yuan, Zhengguo Ji, Daqin Chen*

College of Materials and Environmental Engineering, Hangzhou Dianzi University, Hangzhou 310018, China

Dalton Transactions Accepted Manuscript

Published on 04 July 2017. Downloaded by Cornell University Library on 14/07/2017 04:28:02.

Abstract: Currently, the shortage of red component and easy aging of organic silicone still remain

challenge for high-power phosphor-converted warm white light emitting diodes (w-LEDs).

Aiming to alleviate these issues, phosphor-in-glass (PiG), fabricated by co-sintering red- and

yellow-emitting phosphors and low-melting glass, has been regarded as a promising color

converter for w-LEDs. In this study, Li+, Mn4+ co-doped SrMgAl10O17 red phosphor was

synthesized by a conventional solid-state reaction. The as-prepared phosphor exhibits a deep red

emission ascribed to Mn4+: 2Eg→4A2g spin-forbidden transition in the rage of 600-700 nm with a

narrow-band full width at half maximum of 55 nm, and gives an ideal broadband excitation

extending from 250 to 530 nm. Impressively, Li+ additive used as charge compensation is

beneficial to enhance Mn4+ luminescence by allowing more Mn4+ to replace Al3+. Furthermore, the

developed SrMgAl10O17:Mn4+,Li+ red phosphor and commercial YAG:Ce3+ yellow phosphor

co-doped inorganic PiG was successfully fabricated as the color converter to substitute organic

silicone. The w-LED was fabricated by combining an InGaN blue LED chip with a PiG plate.

Importantly, the constructed w-LEDs exhibited superior optical performance and tuned

chromaticity feature with the correlated color temperature evolved from bluish cool white (6903 K)

to yellowish warm white (3717 K) and the color rendering index increased from 69.4 to 85.5,

meeting the requirements for indoor lighting.

Keywords: Phosphor-in-glass; White light-emitting diodes; Mn4+; Red phosphor

1. Introduction

With the fast development of the industrialization and continuous growth in world’s

population inevitably results in an energy crisis and environmental issue, energy efficiency to be

one of the most important indexes for prospective products.1-5 Because of approximately 19% of

the global electricity consumption requires in lighting, thus, great efforts have been paid to

develop an alternative lighting devices to replace traditional incandescent and fluorescent.6 White

Corresponding authors:
E-Mail: dqchen@hdu.edu.cn (D. Q. Chen)
 Dalton Transactions Page 2 of 20
View Article Online
DOI: 10.1039/C7DT02090B

light-emitting diodes (w-LEDs), the next generation solid-state lighting, have attracted extensive

attentions due to their superior merits such as small volume, low energy consumption, long

lifetime, good stability and environmentally friendly, etc.7-9 Currently, commercially available

phosphor-converted w-LEDs are produced by combining the Y3Al5O12:Ce3+ (YAG:Ce3+) yellow

phosphor with blue LEDs packed on the chip surface using epoxy resin or silicone through a low

Dalton Transactions Accepted Manuscript

Published on 04 July 2017. Downloaded by Cornell University Library on 14/07/2017 04:28:02.

cost and simple procedure. Although the conversion efficiency of YAG:Ce-based w-LEDs is high,

this design suffers from a poor color rendering index (CRI) and high color temperature (CCT) due

to the innate deficiency of red emission component.10-12 Thus, to relieve the disadvantage of the

design, red phosphor excited by blue light is naturally thought to supplement into the system. In

addition, thermally-unstable silicone or organic resin used in the commercial w-LEDs would

result in luminous efficiency degradation and chromaticity shift under a long-term heat

radiation.13,14 Therefore, it is highly desired to develop an inorganic material as alternative to

organic sealing polymer.

In the past few decades, numerous efforts have devoted to developing novel red phosphors

activated by rare earth ions, such as Eu2+, Eu3+, Sm3+ and Pr3+. Noticeably, most of these rare earth

ions are very expensive, which limits their wide applications in w-LEDs.15 Because of the soaring

price of the rare earths and the strong desire to minimize the cost of the LED device, non rare

earth-based eco-friendly phosphors have received great interest.16 As an alternative candidate,

transition metal Mn4+ doped red phosphors usually exhibits a broad absorption between 300 and

480 nm and emits light between 600 to 760 nm due to its unique 3d3 electron configuration.17

According to Tanabe–Sugano diagram, the Mn4+ emission is significantly influenced by different

host lattice due to its electrons located in an outer orbit. Generally, Mn4+ emission is dominated by

the spin-forbidden transition Mn4+: 2

Eg→4A2g, which highly dependent on Mn4+-ligand

bonding.16,18 Although the photoluminescence of Mn4+ activated phosphor has been extensively

studied in various systems, only 3.5MgO·0.5MgF2·GeO2: Mn4+ has been used as commercial red

phosphor.19 Unfortunately, this phosphor has been restricted to limited applications due to the high

price of GeO2. Over past decade, the luminescence of Mn4+ ions in various hosts such as

aluminate, germanate, and hexafluorostantanate etc., has been reported.16-18,20,21 Compared with

other hosts, aluminate is cheaper, less toxic and more environmentally friendly.16 It has been

2
 Page 3 of 20 Dalton Transactions
View Article Online
DOI: 10.1039/C7DT02090B

reported that Sr4Al14O25:Mn4+ are potential red phosphors for w-LEDs, and Mn4+ luminescence

can be enhanced upon the inclusion of Mg2+.22 SrMgAl10O17 (SAM), a β-Al2O3-type crystal

structure, which crystallizes in a hexagonal system with the P63/mmc space group.23,24 As show in

Fig. 1, the structure is built of two spinel blocks of MgAl10O16 separated by one mirror plane

(SrO). In such unit cell, there are large numbers of [AlO6] octahedral coordinated sites, in which

Dalton Transactions Accepted Manuscript

Published on 04 July 2017. Downloaded by Cornell University Library on 14/07/2017 04:28:02.

great Mn4+ ions can be accommodated and stabilized. Furthermore, the [AlO6] layer is separated

by the [AlO4] and [SrO8] layer in the direction along the c-axis, which allows various substitutions,

such as SAM:Eu2+, SAM:Mn2+, and SAM:Eu2+, Mn2+, etc.23-26 Especially, this structure is

favorable to isolate Mn4+ ions from nonradiative perturbations, which is regarded as a promising

host to prepare red phosphors for w-LEDs.18,22

Fig. 1 Schematic illustration of the SrMgAl10O17 crystal structure, and the coordination

environments of [AlO4] tetrahedron and [AlO6] octahedron.

On the other hand, to overcome the weaknesses of organic binders, phosphor-in-glass (PiG) has

been considered as a feasible substitute. PiG is fabricated through a simple mixing of phosphors

with glass frit and sintered at an optimal temperature to form a stable matrix.18, 27 During the

low-temperature co-sintering process, the specially designed glass components are totally melted

while the phosphors remain solid.28, 29 Therefore, excellent luminescent performance of the doping

phosphor can be retained in the glass matrix. Especially, the PiG based w-LEDs demonstrate

excellent thermal resistance and long lifetime under the extreme operating conditions of the LED.

3
 Dalton Transactions Page 4 of 20
View Article Online
DOI: 10.1039/C7DT02090B

However, most of the PiG color converters still exhibit high CCT and low CRI due to the lack of

red component, which greatly restricts PiG based w-LEDs application in indoor lighting.30 Aiming

to compensate for the red deficiency, the newly prepared non rare earth activated SAM red

phosphor with various concentrations has incorporated into the YAG:Ce3+-based PiG. The CCT

and CRI can be effectively tuned by varying the weight ratio of red phosphor to yellow phosphor

Dalton Transactions Accepted Manuscript

Published on 04 July 2017. Downloaded by Cornell University Library on 14/07/2017 04:28:02.

and/or the PiG thickness.

2. Experimental and characterization

2.1 Preparation

A series of SrMgAl10O17:xMn4+,xLi+ (x=0.0002-0.003) phosphors were synthesized by a

conventional solid-state reaction method. Stoichiometric amounts of strontium carbonate (SrCO3,

AR), magnesium carbonate (MgCO3, AR), lithium carbonate (Li2CO3, AR), aluminium oxide

(Al2O3, AR), boric acid (H3BO3, AR) and manganese monoxide (MnO, AR) were accurately

weighed and ground thoroughly in an agate mortar. Subsequently, well-mixed powders were

preheated at 800 °C for 6 h, cooled, reground thoroughly and sintered in air for 6 h at 1300 °C.

Finally, the products were cooled to room temperature naturally and then ground for further used.

The glass ceramics were fabricated by a low-temperature co-sintering route, and the prepared

process including two key steps: (1) precursor glasses fabricated; (2) inserting the blend of

SAM:Mn4+,Li+ red phosphors and YAG:Ce3+ yellow phosphors to the mother glass. Firstly, the

precursor glass with the composition of TeO2–ZnO–Sb2O3–Al2O3–B2O3–Na2O was melted in an

alumina crucible at 1000oC for 30 min. Then, the molten glass poured into a cold copper mold,

cooled, and milled to powder. Afterwards, mixing the obtained SAM:Mn4+,Li+ red phosphors,

commercial YAG:Ce3+ yellow phosphors and the precursor glass frit thoroughly, and followed by

sintering at 600 oC for 30 min. After that, the melt rapidly poured into a 300 oC preheated copper

mold, immediately annealed in a muffle furnace at 230 oC for 5 h to relinquish inner stress, and

slowly cooled down to room temperature. Finally, the obtained PiGs were sliced and polished into

pieces with various shapes and thicknesses for optical measurement and further LED application.

2.2 Characterization

The phase structure of all obtained samples was measured by X-ray diffraction (XRD, Bruker

D8, Germany) using the Cu Ka radiation (λ= 1.54056 Å) in the 2θ range of 10° to 70°. The

4
 Page 5 of 20 Dalton Transactions
View Article Online
DOI: 10.1039/C7DT02090B

structural refinement data was achieved at intervals of 0.01o in the 2θ range 15o-120o and

performed using a MAUD system. The surface morphologies and compositions of the PiG

samples were studied using scanning electron microscopy (SEM, JSM-6700F, JEOL, Japan)

equipped with an energy dispersive X-ray (EDX) spectroscopy system. The photoluminescence

excitation and emission spectra were recorded on a FS5 (Edinburgh, UK) fluorescence

Dalton Transactions Accepted Manuscript

Published on 04 July 2017. Downloaded by Cornell University Library on 14/07/2017 04:28:02.

spectrophotometer equipped with a 150 W continuous and pulsed Xenon lamp as light sources.

The Mn4+ decay curves were recorded on a spectrofluorometer (Edinburgh, FS5) equipped with a

microseconds pulsed diode laser. Meanwhile, the average lifetimes can be calculated using the

∞ ∞
following equation: τ avg = ∫
0
t I (t )dt ∫
0
I (t )dt , where τ is the lifetime value and I(t) is the

emission intensity at time t. Temperature-dependent emission spectra of the obtained phosphor

were measured by the same spectrophotometer combined with a homemade temperature

controlling stage. Luminous efficacy, CCT, CRI and Commission International de I’Eclairage

(CIE) chromaticity coordinates of the fabricated w-LEDs were measured on a HAAS-2000

(Everfine Photo-E-Info Co. Ltd, Hangzhou, China) spectroradiometer combined with an

integrating sphere.

3. Results and discussion

3.1 Crystal structures

The XRD patterns of SAM: x mol%Mn4+, x mol%Li+ (x=0-0.3) is presented in Fig. 2(a). It is

obvious that all diffraction peaks are in agreement with those of the standard profile of

SrMgAl10O17 (SAM, JCPDS no.26-0879), demonstrating that the introducing of Mn4+ ions do not

induce any impurities or cause any significant changes in the SAM host crystal structure. However,

compare to that of undopped SAM, the dominated diffraction peaks regular slightly shift to the

small angle with the increase of Mn4+ concentrations, resulting from the larger Mn4+(r = 0.54 Ǻ,

CN = 6) ions substituting for the smaller Al3+(r = 0.535 Ǻ, CN = 6), as shown in Fig. 2(b).

To further gain more information about the crystal structure and site occupancy of the

as-synthesized sample, the Rietveld refinement of SAM:0.05%Mn4+,0.05%Li+ is analyzed by

using SrMgAl10O17 (ICSD-155527) as the initial model, and structural refinement of XRD is

performed using the MAUD system. The experimental and refined XRD patterns of

SAM:0.05%Mn4+,0.05%Li+ is illustrated in Fig. 2(c). As seen from Fig. 2(c), we clearly found that

5
 Dalton Transactions Page 6 of 20
View Article Online
DOI: 10.1039/C7DT02090B

each peak from the experimental spectrum is well agreement with the calculated data, no impurity

or secondary phases are observed, indicating that the obtained sample is single phase. The

obtained residual factors are Rwnb = 7.31 %, Rw = 7.29 %, Rexp = 2.48 %, and Rb = 5.95 %,

revealing that a good quality of refinement results. The lattice parameters of

SAM:0.05%Mn4+,0.05%Li+ are confirmed to be a=b=5.59 Ǻ, c=22.38 Ǻ and cell volume

Dalton Transactions Accepted Manuscript

Published on 04 July 2017. Downloaded by Cornell University Library on 14/07/2017 04:28:02.

V=605.62 Ǻ3, which are smaller than that of SAM (a=b=5.63 Ǻ, c=22.47 Ǻ and cell volume

V=616.80 Ǻ3). This phenomenon can be explained by the different ionic radius between Al3+ and

Mn4+ ions.

(a) (b)
x=0.3

x=0.25
Intensity (a.u.)

x=0.2

x=0.15

x=0.1

x=0.05

x=0.02

x=0
JCPDS no. 26-0879

10 20 30 40 50 60 70 32 33 34 35 36 37
2 θ /degree 2θ/degree

(c) Experiment Data

Calulated Data
Diference
Intensity (a.u.)

20 40 60 80 100 120
2θ/degree
Fig. 2 (a) XRD patterns of SAM: x mol%Mn4+, x mol%Li+ (x=0-0.3) sample with various Mn4+

concentrations. The reference data is sourced from SrMgAl10O17 (JCPDS no.26-0879). (b) The

enlarge patterns from 31.5o to 37o. (c) Rietveld refinement result of SAM:0.05%Mn4+,0.05%Li+

phosphor, showing the observed (black diamond) and calculated (red cross) profiles, and the

difference between the observed and calculated patterns (blue triangle).

3.2 Luminescence properties of SAM:Mn4+,Li+ phosphor

The typical PLE (λem=663 nm) and PL (λex=450 nm) spectra of SAM:0.05%Mn4+, 0.05%Li+

6
 Page 7 of 20 Dalton Transactions
View Article Online
DOI: 10.1039/C7DT02090B

sample is depicted in Fig. 3. The PLE spectrum monitored at 663 nm contains several excitation

bands ranging from 250 to 530 nm, which can be fitted by three Gaussian curves. The broadband

with the maximum intensity at about 295 nm in the region of 250-400 nm is assigned to the

overlap of Mn4+:4A2g→4T1g and a charge transfer band (CTB) of Mn4+−O2−, which is well

consistent with the previous reported.2, 13 Other excitation bands lactated at 366 and 450 nm are

Dalton Transactions Accepted Manuscript

Published on 04 July 2017. Downloaded by Cornell University Library on 14/07/2017 04:28:02.

attributed to 4A2g→2T2g and 4T2g transitions of Mn4+ ion, indicating its potential application in

n-UV and blue pumped w-LEDs. It’s worth noting that the spectral overlap between the emission

of commercial YAG:Ce3+ and the excitation of SAM:Mn4+,Li+ is rather small, therefore, the

probability of photon re-absorption which usually occur between YAG:Ce3+ yellow phosphors and

nitride red phosphors is considerably reduced.16,31 Under 450 nm excitation, the emission

spectrum shows a red emission band ranging from 620 to 770 nm with a maximum located at

663nm. Surprisingly, the red emission band in SAM:Mn4+,Li+ phosphor shows an

undistinguishable broad asymmetric band, which is different from many Mn4+ doped oxides with

some distinguishable sharp R lines and stokes/anti-stokes sidepeaks.2 In addition, the full width at

half maximum (FWHM) of the emissive band is about 55 nm, which is narrower than that of

commercial Sr2Si5N8:Eu2+ (94 nm) and CaAlSiN3:Eu2+ (90 nm)，and similar to that of Mn4+-doped

fluoride phosphors (~50 nm) and Sr[LiAl3N4]:Eu2+ (53 nm).32-34 Such narrow-band is benefit for

improve the luminous efficiency of the radiation, color rendition and visual energy efficiency.34 In

the SAM structure, the [AlO6] layer is separated by the [AlO4] and [SrO8] layer, resulting in the

enhancement of nephelauxetic effect and chemical bond strength, which may cause the emission

band of SAM:Mn4+,Li+ broadened. Furthermore, compared with the previous reports by Cao et

al.35 and Meng et al.24, the zero-phonon line and sidepeaks are not easy to be identified due to the

characteristic of parity- and spin-forbidden of Mn4+: 2Eg→4A2g transition and rigorous phonon

vibrations.16 Furthermore, the excitation wavelength-dependent emission mapping of the

SAM:0.05%Mn4+, 0.05%Li+ sample is presented in Fig. S1. Notably, the profiles of emission

spectra are the similar when it excited at various wavelengths, indicating the Mn4+ ion is occupied

at one site.

7
 Dalton Transactions Page 8 of 20
View Article Online
DOI: 10.1039/C7DT02090B

4 4 2 4
CTB and A2g→ T1g Eg→ A2g

λex= 450 nm

Relative Intensity (a.u.)

3+
YAG:Ce
λem= 663 nm

4 2
A2g→ T1g

Dalton Transactions Accepted Manuscript

55nm
Published on 04 July 2017. Downloaded by Cornell University Library on 14/07/2017 04:28:02.

4 4
A2g→ T2g

250 300 350 400 450 500 550 600 650 700 750 800 850
Wavelength (nm)

Fig. 3 PLE (λem=663 nm) and PL (λex=450 nm) spectra of SAM:0.05%Mn4+, 0.05%Li+ phosphor

and the emission spectrum of YAG:Ce3+. Insets show photographs of as-obtained

SAM:0.05%Mn4+, 0.05%Li+ phosphor in daylight and under 365 nm lamp illumination.

The PL spectra of the SAM: Mn4+,Li+ phosphors with different Mn4+ doping concentrations

are displayed in Fig. S2. Upon 450 nm blue light excitation, all emission spectra of the samples

are consists of an asymmetric board band centered at 663 nm, originating from the 2Eg→4A2g

transitions of Mn4+. The luminescence intensities first increase with increasing Mn4+

concentrations, reaching a maximum at x=0.05 mol%, and then decrease gradually due to

concentration quenching effect. Generally, nonradiative energy transfer may occur by exchange

interaction, radiation re-absorption or multipole–multipole interaction. Considering the energy

transfer mechanism in SAM: Mn4+,Li+, the critical distance (Rc) among Mn4+ ions is necessary to

obtain, and the value can be estimated using the following equation given by Blasse:36

13
 3V 
Rc ≈ 2  
 4π XC N  (1)

Where V means the volume of unit cell, Xc represents the critical concentration of Mn4+ ions and N

is the number of host cations in the unit cell. For the SAM host, V=612.6 Å3, Xc=0.0005, and N=2;

accordingly, the value of Rc is estimated to be 105.37 Å. Thus, the major mechanism is the electric

multipolar interaction. Furthermore, as we all know, the multipolar-multipolar interaction

containing three types: dipole-dipole(d-d), dipole-quadrupole(d-q), and quadrupole-quadrupole

8
 Page 9 of 20 Dalton Transactions
View Article Online
DOI: 10.1039/C7DT02090B

(q-q) interactions. In order to confirm the precise interaction among Mn4+ ions, the PL intensity (I)

per Mn4+ ion concentration (x) can be expressed by Dexter theory as following:37

I K
=
χ 1 + β( χ )θ 3 (2)

Where K and β are constants for the same excitation condition and a given host crystal,

Dalton Transactions Accepted Manuscript

Published on 04 July 2017. Downloaded by Cornell University Library on 14/07/2017 04:28:02.

respectively; θ = 3 is defined as the exchange interaction, and θ = 6, 8, 10 corresponding to d-d,

d-q, and q-q interactions, respectively. It is clearly observed from Fig. 4(a) that the dependence of

log(I/x) on log(x) can be fitted linearly, and the slope is equal to -1.25. In consequence, the value

of θ is calculated to be 3.75 and close to 6, indicating that the concentration quenching mechanism

in SAM: Mn4+,Li+ is mainly originated from the electric d-d interaction. Besides, the quantum

efficiency of the optimized red-emitting SAM:0.05%Mn4+, 0.05%Li+ phosphor is determined to be

26.2% under 450 nm excitation.

Generally, PL decay curve is an important approach to discuss the energy transfer process.

Therefore, the concentration-dependent fluorescence decay curves of Mn4+ in SAM host excited at

450 nm and monitored at 663 nm are presented in Fig. 4(b). The average lifetimes of Mn4+ of

SAM:x%Mn4+, x%Li+ (x=0.02, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3) are calculated to be 0.558, 0.541,

0.523, 0.516, 0.472, 0.446, and 0.43 ms, respectively. Evidently, the decay lifetimes of Mn4+

gradually decreased with increasing of doping concentrations, which is ascribed to the increased

non-radiation energy migration probability among the Mn4+ ions in the matrix.

x=0.3
(a) (b) τ =0.430 ms
2
R =1.0002
Logarithmic Intensity (a.u.)
PL intensity (a.u.)

x=0.2
τ =0.472 ms
2
R =1.0002
Log (I/x)

x=0.1
τ =0.523 ms
2
R =1.0006
Slope=-1.25
2
R =0.9912
x=0.02
τ =0.558 ms
2
-1.8 -1.6 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 R =1.0012
Log (x)

0.00 0.05 0.10

4+
0.15 0.20 0.25 0.30 1 2 3 4 5 6
Mn concentrations (mol%) Decay time (ms)

Fig.4 (a) The PL intensity as a function of Mn4+ concentration in SAM:x%Mn4+, x%Li+

(0.02≤x≤0.3). Inset is the dependence of log (I/x) versus log (x). (b) Luminescence decay curves

9
 Dalton Transactions Page 10 of 20
View Article Online
DOI: 10.1039/C7DT02090B

of Mn4+ ions in SAM:x%Mn4+, x%Li+ samples excited at 450 nm and monitored at 663 nm.

As pre-reported, in order to improve the luminescence properties of optical materials, alkaline

metal ions (Li+, Na+ and K+) can usually use as charge compensations for phosphors. Therefore, to

investigate the effect of Li+, Na+ and K+ additives on the luminescence performance of

SAM:0.05%Mn4+, we study the emissive characteristics of Mn4+ in absence or presence of

Dalton Transactions Accepted Manuscript

Published on 04 July 2017. Downloaded by Cornell University Library on 14/07/2017 04:28:02.

alkaline mental ions under 450 nm excitation, as display in Fig.S3. There are no obvious changes

in the emission spectra profiles and peak positions except PL intensities. The luminescence

intensities of SAM: 0.05%Mn4+, R+ (R+= Li+, Na+ and K+) are 2.06 (Li), 1.90 (Na) and 1.07 (K)

times higher than that of SAM: 0.05%Mn4+, which assigned to the charge compensation of Li+,

Na+ and K+ ions. In the SAM:Mn4+ phosphor, as the Mn4+ ion replaces Al3+ ion, it is difficult to

maintain charge balance in the host lattice due to their different valences. Therefore, Mn4+ ions

cannot be entered into the Al3+ ions site fully in the SAM host lattice. As discussed above, Mn4+

ions preferred to occupy the Al3+ sites in [AlO6] octahedral, and Al3+ (0.0535 nm) is supposed to

be replaced by Li+ (0.076 nm) based on the similar ionic radii, while Na+ (0.102 nm) and K+

(0.133 nm) ion tends to occupy Sr2+ (0.118 nm) sites.24,38,39 Thus, the charge balance is maintained

by introducing alkaline mental ions coupling with Mn4+, and then the luminescence properties of

SAM:Mn4+ phosphor are enhanced effectively. In addition, compared to the influence of Na+ and

K+, Li+ ions as charge compensator are more effective to tune the luminescence intensity of

SAM:Mn4+ phosphor.

The dynamic of the Mn4+ luminescence properties in SAM lattice matrix is investigated via the

temperature behavior of as-obtained phosphor. The PL spectra for SAM: 0.05%Mn4+, 0.05%Li+ in

the temperature ranging from 77 to 300K is presented in Fig. 5(a). With increasing of temperature

from 77 to 300 K, the emission intensity decrease gradually due to the nonradiative transition of

Mn4+ ion enhanced. Impressively, the structured peaks are observed gradually decreased and the

emission band is found thermally broadened, originating from the fact that added restricted

phonon vibrations involved in the luminescence process and strengthen coupling of Mn4+ to the

O-Mn-O and Mn-O vibration modes.2,40 In addition, to evaluate the potential application in LED,

the thermal stability of the prepared phosphor is measured, as shown in Fig.5(b). It can be clearly

seen that the PL intensity decreased gradually with increasing temperature due to the thermal

10
 Page 11 of 20 Dalton Transactions
View Article Online
DOI: 10.1039/C7DT02090B

quenching effect. When the temperature increases to 423 K, the emission intensity maintains

approximately 48% of that at room temperature, indicating the SAM: Mn4+, Li+ red phosphor

possesses a good thermal stability properties. In order to get a better understating of the thermal

quenching behavior, the activation energy ∆E as a crucial parameter can be calculated using the

Arrhenius equation.41 As displayed in Fig. 5(c), the relationship of ln[(I0/I)-1] versus 1/kT yields a

Dalton Transactions Accepted Manuscript

Published on 04 July 2017. Downloaded by Cornell University Library on 14/07/2017 04:28:02.

straight line, and the value of ∆E is determined to be about 0.436 eV, which is higher than that of

Mn4+ in Sr4Al14O25(0.097eV) 22, Mg3Ga2GeO8(0.216 eV) 41, and Li2MgTiO4(0.34eV) 2. Meanwhile,

the schematic configuration coordinates is used to explain the thermal quenching mechanism, as

illustrated in Fig. 5(d). Upon excitation at 450 nm, Mn4+ is excited from the ground state to 4T2g.

Then, red emission can be produced by the electrons return to the lowest excited state 2Eg and

ground state 4A2g as a way of nonradiactive relaxation and radiative transition, respectively.

However, as the temperature is increased, most electrons in 2Eg state absorbing ∆E return to the

ground state along the cross point of between states of 4A2g and 2Eg with a nonradiative transition,

which will induce Mn4+ emission decrease.20, 27,37

4
9x10
(a) 8x10
4
77 K
100 K
(b)
4 130 K
7x10
160 K
PL intensity (a.u.)

4
6x10 190 K
4
220 K
5x10 250 K
4x10
4 280 K
300 K
4
3x10
4
2x10
4
1x10

0
600 625 650 675 700 725 750
Wavelength (nm)

(c) 2 (d)E 2
1
Eg 4
T2
0
Ln (I0/IT-1)

data
-1
linear fit
slope=-0.436
-2 2 ∆ E = 0 .4 3 6 e V
R =0.999
-3 -Ea/kT=Ln(I0/IT-1)
4
-4
22 24 26 28 30 32 34 36 38
A2
-1 R
1/kT (eV )
4+ +
Fig.5 Temperature dependence of the spectral emission of SAM:Mn ,Li upon 450 nm excitation:

(a) blow room temperature (77-300K) and (b) above room temperature (303-483K). (c) The

dependence of ln[(I0/I)-1] versus 1/kT. (d) The schematic configuration coordinates diagram of the

Mn4+ ion in SAM host.

11
 Dalton Transactions Page 12 of 20
View Article Online
DOI: 10.1039/C7DT02090B

3.3 Microstructure and luminescence of PiG sample

To overcome the weaknesses of organic binders, the all-inorganic phosphor-in-glass (PiG) is

considered to be a feasible substitute. Furthermore, to compensate for the red deficiency, non rare

earth activated SAM red phosphors accompanied by commercial YAG:Ce3+ yellow phosphors

have incorporated into the TO2-based glass matrix. In Fig. 6, the XRD curves of the

Dalton Transactions Accepted Manuscript

Published on 04 July 2017. Downloaded by Cornell University Library on 14/07/2017 04:28:02.

SAM:Mn4+,Li+ PiG, and SAM:Mn4+,Li+ and YAG:Ce3+ PiG exhibits the diffraction peaks are well

accordance with the standard data, indicating that the phosphor particles have been successfully

incorporated into the TeO2-based glass matrix. Besides, the amorphous hump is ascribed to the

glass matrix. The morphology and microstructure of the SAM:Mn4+,Li+ and YAG:Ce3+ phosphor

particles in the glass matrix are inspected using SEM, as depicted in Fig. 7(a). One can clearly

seen that the fabricated PiG compose of two kinds of particles with different size. The irregular

particles (labeled by red circles) with the size ranging from 3 to 8 µm are designated as the

as-prepared SAM:Mn4+,Li+, whereas the regular ones (marked by yellow circles) with small size

are ascribed to the commercial YAG:Ce3+. It can be also clearly found that the doped phosphor

particles distribute homogeneous with no obvious agglomeration in the glass matrix. To further

distinguish the doping particles, the energy dispersive X-ray spectroscopy (EDX) line scans across

two particles, marked by a green frame in SEM image, are depicted in Figs. 7(b-g). Along a line

through one particle to another, the profiles of elements Al and Y are originated from the

YAG:Ce3+ phosphor particles, as marked in yellow circle in SEM image, while elements Sr, Al,

and Mn signals are detected in another particle, as denoted with red circle, indicating that the

YAG:Ce3+ and SAM:Mn4+,Li+ phosphor particles are effectively incorporated into the glass matrix.

As a comparison, Te and Zn signals are absent on the two phosphor particles, but detected in glass

matrix.

12
 Page 13 of 20 Dalton Transactions
View Article Online
DOI: 10.1039/C7DT02090B

Y3Al5O12 JCPDS no.33-0040

4+ +
(b) SAM:Mn ,Li PiG
4+ + 3+
SAM:Mn ,Li + YAG:Ce PiG

Intensity (a.u.)

Dalton Transactions Accepted Manuscript

Published on 04 July 2017. Downloaded by Cornell University Library on 14/07/2017 04:28:02.

(a)

SrMgAl10O17 JCPDS no. 26-0879

10 20 30 40 50 60 70
2θ/degree

Fig.6 XRD patterns of PiG sample with different phosphor particles: (a) 3 wt% SAM:Mn4+,Li+

phosphor, and (b) 3 wt% SAM:Mn4+, Li+ and 3 wt% YAG:Ce3+ co-doped phosphors.

(a) (b) (c)

0 5 10 15 20 25 0 5 10 15 20 25

Aluminum Yttrium
(d) (e)

0 5 10 15 20 25 0 5 10 15 20 25
Tellurium Sodium
(f) (g)

0 5 10 15 20 25 0 5 10 15 20 25
Strontium Magnesium

Fig. 7 (a) SEM image result of YAG:Ce3+ yellow phosphor and SAM:Mn4+,Li+ red phosphor

particles in PiG sample. EDX line scan curves across two phosphor particles (marked by blue

frame) including: (b) Al, (c) Y, (d) Te, (e) Na, (f) Sr, and (g) Mn elements profiles.

The PLE and PL spectra of the SAM:Mn4+,Li+ phosphor powder and its corresponding PiG

sample, YAG:Ce3+ doped PiG sample, and SAM:Mn4+,Li+ and YAG:Ce3+ co-doped PiG sample

are presented in Fig. 8(a). It can be clearly seen that the SAM:Mn4+,Li+ phosphor powder and its

corresponding PiG sample have the similar spectral features. However, the excitation intensity

reduced greatly in the UV region (250-400 nm), which mainly ascribed to the strong absorption of

13
 Dalton Transactions Page 14 of 20
View Article Online
DOI: 10.1039/C7DT02090B

the glass matrix.16,30 For the SAM:Mn4+,Li+ and YAG:Ce3+ co-doped PiG sample, except a typical

Ce3+:4f↔5d broadband excitation and emission, the characteristic spin and parity forbidden

transition of Mn4+:2Eg→4A2g can also be observed. Especially, under 450 nm blue light excitation,

the Mn4+:2Eg→4A2g red-emitting and Ce3+:5d→4f yellow-emitting can be simultaneously attained,

demonstrating that the fabricated PiG sample could be a feasible candidate for warm w-LEDs.

Dalton Transactions Accepted Manuscript

Published on 04 July 2017. Downloaded by Cornell University Library on 14/07/2017 04:28:02.

Besides, the luminescent dynamical study in Fig.8(b) manifests that the profiles of decay curve

and lifetime value of Mn4+ in PiG sample are almost constantly compared with those of the

corresponding phosphors.
4+
(a) SAM phosphor
(b) SAM:0.05% Mn phosphor
λex=450 nm
λem=663 nm

Logarithmic Intensity (a.u.)

τ=0.541 ms
Intensity (a.u.)

10 wt% SAM PiG

λex=450 nm
4+
SAM:0.05% Mn PiG
λem=663 nm
3 wt% YAG PiG
3 wt% YAG+
4+ 2 4
τ=0.548 ms
10 wt% SAM PiG Mn : E→ A2g
3+
Ce :5d→4f
250 300 350 400 450 500 550 600 650 700 750 800
Wavelength (nm) 1 2 3 4 5 6
Decay time (ms)

Fig. 8 (a) PLE and PL spectra of SAM:Mn4+,Li+ phosphor powder, SAM:Mn4+,Li+ doped PiG

sample, YAG:Ce3+ doped PiG sample, and SAM:Mn4+,Li+ and YAG:Ce3+ co-doped PiG sample

upon 450 nm blue light excitation. (b) Decay curves of the SAM:0.05%Mn4+,0.05%Li+ phosphor

powder and the corresponding PiG sample.

3.4 Fabrication of w-LEDs

To validate the availability of SAM:Mn4+,Li+ red phosphor compensate the red deficiency in

YAG:Ce-based PiG and demonstrate the potential application of the fabricated YAG:Ce3+ and

SAM:Mn4+,Li+ co-doped PiG, the w-LEDs are constructed by coupling these PiG plates to a

commercial InGaN blue chip. The electroluminescent (EL) spectra of the PiG sample at different

concentrations of (0-15 wt%) SAM:Mn4+,Li+ under 460 nm blue LED excited are presented in

Fig.9(a). Obviously, the 460 nm band ascribed to the emission of the blue LED and the broad

emission band around 550 nm attributed to the Ce3+:4f→5d emission can be observed. Especially,

the Mn4+:2Eg→4A2g red emissive component intensifies gradually with the increase of

14
 Page 15 of 20 Dalton Transactions
View Article Online
DOI: 10.1039/C7DT02090B

SAM:Mn4+,Li+ contents from 0 to 15 wt%. Consequently, the corresponding photoelectric

parameters of these constructed w-LEDs under 60 mA driving current are summarized in Table 1.

Besides, the color coordinates of these w-LEDs are marked on the CIE 1931 chromaticity diagram,

as depicted in Fig. 9(b). Noticeably, the tuned luminescent color of the constructed w-LEDs

progresses from bluish cool to yellowish warm light, as displayed in the insets of Fig. 9(b).

Dalton Transactions Accepted Manuscript

Published on 04 July 2017. Downloaded by Cornell University Library on 14/07/2017 04:28:02.

Meanwhile, the CIE chromaticity coordinates shift from (0.3063, 0.3380) to (0.3947, 0.4048), the

luminous efficacy(LE) decreases from 113.3 to 58.2 lm/W, the correlated color temperature (CCT)

declines from 6903 to 3717 K, and the color rendering index (Ra) increases from 69.4 to 85.5. All

these results demonstrate that the CCT and Ra can be effectively adjusted by introducing

SAM:Mn4+,Li+ red phosphor into YAG:Ce3+-based LED. Especially, the chromaticity parameters

require for commercial warm w-LEDs can be achieved, indicating that the SAM:Mn4+,Li+

phosphor is a promising red supplement for warm w-LEDs.

(a) x = 15.0 wt% (b)

Normalized EL Intensity (a.u.)

x = 12.5 wt%

x = 10.0 wt%

x = 7.5 wt%

x = 5.0 wt%

x = 2.5 wt%

x = 0 wt%
400 450 500 550 600 650 700 750
Wavelength (nm)

Fig.9 (a) EL spectra of the constructed w-LEDs utilizing PiG composite with 3 wt% YAG: Ce3+

and y wt% SAM: Mn4+,Li+ (y=0, 2.5, 5, 7.5, 10, 12.5, 15) under a 60 mA driving current. (b) CIE

coordinates of PiG-based LEDs with different SAM:Mn4+,Li+ contents. The insets show the

photographs of PiG-based LEDs under or out 460 nm LED excitation.

Table 1. Performances of w-LEDs utilizing PiG composite with different SAM:Mn4+,Li+ contents

SAM:Mn4+,Li+ Chromaticity coordinate

LE (lm/W) CCT (K) Ra
No. content (wt%) X Y

15
 Dalton Transactions Page 16 of 20
View Article Online
DOI: 10.1039/C7DT02090B

a 0 0.3063 0.3380 113.3 6903 69.4

b 2.5 0.3246 0.3535 110.8 5814 71.5

c 5.0 0.3404 0.3644 102.4 5105 74.3

d 7.5 0.3558 0.3752 91.9 4611 77.6

e 10.0 0.3708 0.3874 80.9 4218 80.6

Dalton Transactions Accepted Manuscript

Published on 04 July 2017. Downloaded by Cornell University Library on 14/07/2017 04:28:02.

f 12.5 0.3846 0.3991 68.6 4046 82.2

g 15.0 0.3947 0.4048 58.2 3717 85.5

To further evaluated the influence of PiG thickness on the performance of LED device, the

PiG thickness dependent EL spectra and corresponding photometric/chromaticity parameters of

the w-LEDs are presented in Fig. 10. Obviously, with the increase of thickness from 0.6 to 1.6 mm,

the broad emission band between 500 and 700 nm enhances dramatically at expense of the band

centered at 460 nm, which is ascribed to the longer interaction pathway between blue light and

PiG sample.30 Furthermore, with the thickness increases from 0.6 to 1.6 mm, CIE color

coordinates evolve from (0.295,0.3021) to (0.3865,0.4032) and the CCT decreases from 8172 to

4026 K, which mainly caused by the Ce3+ concentration absorbing more blue light.

Correspondingly, the thinner the PiG plate, the bluer the hue; while the thicker one, the yellower

the hue. These results demonstrate that the photometric/chromaticity parameters of the w-LEDs

can be easily tuned by changing the ratio of red component and thickness of the PiG.

(a)1.0 1.6 mm (b)

1.4 mm
Normalized EL Intensity (a.u.)

1.2 mm
0.8
1.0 mm
0.8 mm
0.6 0.6 mm

0.4

0.2

0.0
400 450 500 550 600 650 700 750
Wavelength (nm)

Fig. 10 (a) EL spectra of the 3 wt% YAG: Ce3+ and 12.5 wt% SAM: Mn4+,Li+ co-doped

PiG-based w-LEDs with various thickness under a 60 mA driving current. (b) CIE coordinates of

16
 Page 17 of 20 Dalton Transactions
View Article Online
DOI: 10.1039/C7DT02090B

the fabricated PiG-based LED devices. Insets show the corresponding photograph in operation.

The color stability of the as-fabricated PiG sample for high-quality lighting applications is

detected as a function of varying the applied current is displayed in Fig.11. With increasing the

current from 20 to 400 mA, the CIE coordinates shifted slightly blue-shifted from (0.3848,

0.4007) to (0.3824, 0.3928), which is probably caused by the increasing ratio of the blue to

Dalton Transactions Accepted Manuscript

Published on 04 July 2017. Downloaded by Cornell University Library on 14/07/2017 04:28:02.

yellow components. In addition, the CCT and CRI are a normal value of ∼4040 K and ∼81.5,

respectively. These results reveal that the constructed PiG-based w-LEDs possess excellent color

stability.
0.402 4400 110
(a) 20 mA
(b)
4200
0.400
100
60 mA 4000
100 mA
0.398
140 mA Tc (K) 3800
CIE Y

180 mA

Ra
90
0.396 220 mA 3600
260 mA
3400
80
0.394 350 mA 300 mA 3200

0.392 400 mA 3000 70

0.3820 0.3825 0.3830 0.3835 0.3840 0.3845 0.3850 0 50 100 150 200 250 300 350 400 450
CIE X Current (mA)

Fig. 11 (a) The variation of CIE coordinates of the fabricated w-LEDs driven by various currents.

(b) The corresponding CCT and CRI operated at different currents.

4. Conclusions

In summary, a series of Mn4+,Li+ co-doped SrMgAl10O17 phosphors with deep red-emitting

has been successfully prepared by a high-temperature solid-state reaction. These phosphors could

be effectively excited by near-UV/blue light and exhibit an abnormal band emission centered at

~663 nm with the FWHM of 55 nm. The optimal doping concentration of Mn4+ in the SAM is

determined to be about 0.05 mol%, beyond which the concentration quenching mechanism is

confirmed to be quadrupole-quadrupole interaction. Importantly, Li+ additive used as charge

compensation and significantly enhance Mn4+ emission intensity. Furthermore, to evaluate the

suitability of the developed phosphors as red converter, SAM:Mn4+,Li+ red phosphor, mixed with

YAG:Ce3+ yellow ones, are successfully incorporated into the low-melting TeO2-based precursor

glass to form PiG composite. Impressively, the obvious effect of the doping phosphor particles is

avoided and the optical performance is retained. Finally, the w-LEDs device, constructed by

combining an InGaN blue chip with the PiG plate, demonstrates a tunable LE of 58.2-113.3 lm/W,

17
 Dalton Transactions Page 18 of 20
View Article Online
DOI: 10.1039/C7DT02090B

a CCT of 6903-3717 K and a CRI of 85.5-69.4. All the results indicate that the present

SAM:Mn4+,Li+ red phosphors and the corresponding PiGs has potential applications in the

high-power warm w-LEDs.

Acknowledgments

This work was supported by the National Natural Science Foundation of China (51502066 and

Dalton Transactions Accepted Manuscript

Published on 04 July 2017. Downloaded by Cornell University Library on 14/07/2017 04:28:02.

51572065), Natural Science Foundation of Zhejiang Province (LR15E020001 and LQ14E020006),

the 151 talent’s projects in the second level of Zhejiang Province, and the college students’

activities of science and technology innovation in Zhejiang Province (2016R407038).

Notes and References

1 Z.G. Xia and Q.L. Liu, Prog. Mater. Sci. 2016, 84, 59–117.

2 Y.H. Jin, Y.H. Hu, H.Y. Wu, H. Duan, L. Chen, Y.R. Fu, G.F. Ju, Z.F. Mu and M. He, Chem.

Eng. J. 2016, 288, 596–607.

3 L. Huang, Y.W. Zhu, X.J. Zhang, R. Zou, F.J. Pan, J. Wang and M.M. Wu, Chem. Mater. 2016,

28, 1495–1502.

4 Y. Li, M. Gecevicius and J.R. Qiu, Chem. Soc. Rev. 2016, 45, 2090–2136.

5 X.Y. Huang, J. Alloys Compd., 2017, 690, 356–359.

6 C.C. Lin, A. Meijerink and R.S. Liu, J. Phys. Chem. Lett. 2016, 7, 495−503.

7 K. Li, M.M. Shang, H.Z. Lian and J. Lin, J. Mater. Chem. C 2016, 4, 5507–5530.

8 X.Y. Huang, Nat. Photonics 2014, 8,748–749.

9 X.J. Zhang, J. Wang, L. Huang, F.J. Pan, Y. Chen, B.F. Lei, M.Y. Peng and M.M. Wu, ACS

Appl. Mater. Interfaces 2015, 7, 10044–10054.

10 J.S. Zhong, D.Q. Chen, H.X. Xu, W.G. Zhao, J. Sun and Z.G. Ji, J. Alloys Compd., 2017, 695,

311–318.

11 J.H. Li, J. Yan, D.W. Wen, W.U. Khan, J.X. Shi, M.M. Wu, Q. Su and P.A. Tanner, J. Mater.

Chem. C 2016, 4, 8611–8623.

12 Z.G. Xia, Z.H. Xu, M.Y. Chen and Q.L. Liu, Dalton Trans. 2016, 45, 11214-11232.

13 H. Chen, H. Lin, J. Xu, B. Wang, Z.B. Lin, J.C. Zhou and Y.S. Wang, J. Mater. Chem. C 2015,

3, 8080–8089.

14 J.S. Zhong, D.Q. Chen, Y. Zhou, Z.Y. Wan, M.Y. Ding and Z.G. Ji, J. Eur. Ceram. Soc., 2016,

18
 Page 19 of 20 Dalton Transactions
View Article Online
DOI: 10.1039/C7DT02090B

36, 1705–1713.

15 T.N. Ye, S. Li, X.Y. Wu, M. Xu, X. Wei, K.X. Wang, H.L. Bao, J.Q. Wang and J.S. Chen, J.

Mater. Chem. C 2013, 1, 4327–4333.

16 B. Wang, H. Lin, F. Huang, J. Xu, H. Chen, Z.B. Lin and Y.S. Wang, Chem. Mater. 2016, 28,

3515–3524.

Dalton Transactions Accepted Manuscript

Published on 04 July 2017. Downloaded by Cornell University Library on 14/07/2017 04:28:02.

17 D.Q. Chen, Y. Zhou and J.S. Zhong, RSC Adv. 2016, 6, 86285–86296.

18 B. Wang, H. Lin, J. Xu, H. Chen and Y.S. Wang, ACS Appl. Mater. Interfaces 2014, 6,

22905−22913.

19 G. Kemeny and C.H. Hakke, J. Chem. Phys. 1960, 33, 783−789.

20 H.D. Nguyena and R.S. Liu, J. Mater. Chem. C 2016, 4, 10759−10775.

21 Z. Zhou, N. Zhou, M. Xia, M. Yokoyamab and H.T. Hintzen, J. Mater. Chem. C 2016, 4,

9143−9161.

22 M.Y. Peng, X.W. Yin, P.A. Tanner, M.G. Brik and P.F. Li, Chem. Mater. 2015, 27,

2938−2945.

23 G.F. Ju, Y.H. Hu, L. Chen and X.J. Wang, J. Lumin. 2012, 132, 1792–1797.

24 L.L. Meng, L.F. Liang and Y.X. Wen, J Mater Sci: Mater Electron. 2014, 25, 2676−2681.

25 V. Singh, T.G. Rao and J.J. Zhu, J. Lumin. 2008, 128, 583–588.

26 D.S. Xing, K.W. Cheah, P.Y. Cheng, J. Xu, J.X. Shi, H.B. Liang and M.L. Gong, Solid State

Commun. 2005, 134, 809–813.

27 D.Q. Chen, W.D. Xiang, X.J. Liang, J.S. Zhong, H. Yu, M.Y. Ding, H.W. Lu and Z.G. Ji, J.

Eur. Ceram. Soc. 2015, 35, 859–869.

28 D.Q. Chen, Y. Zhou, W. Xu, J.S. Zhong, Z.G. Ji and W.D. Xiang, J. Mater. Chem. C 2016, 4,

1704−1712.

29 J.S. Zhong, D.Q. Chen, Y. Zhou, Z.Y. Wan, M.Y. Ding, W.F Bai and Z.G. Ji, Dalton Trans.

2016, 45, 4762−4770.

30 Z.B. Lin, H. Lin, J. Xu, F. Huang, H. Chen, B. Wang and Y.S. Wang, J. Eur. Ceram. Soc. 2016,

36, 1723–1729.

31 X. Ding, Q. Wang and Y.H. Wang, Phys. Chem. Chem. Phys. 2016, 18, 8088−8097.

32 K. Uheda, N. Hirosaki and H. Yamamoto, Phys. Status Solidi A 2006, 203, 2712−2717.

19
 Dalton Transactions Page 20 of 20
View Article Online
DOI: 10.1039/C7DT02090B

33 R.J. Xie and N. Hirosaki, Sci. Technol. Adv. Mater. 2007, 8, 588−600.

34 J.H. Oh, Y.J. Eo, H.C. Yoon, Y.D. Huh and Y.R. Do, J. Mater. Chem. C 2016, 4, 8326−8348.

35 R.P. Cao, H.D. Xue, X.G. Yu, F. Xiao, D.L. Wu and F.X. Zhang, J. Nanosci. Nanotechnol.

2016, 16, 3489−3493.

36 D. L. Dexter, J. Chem. Phys. 1953, 21, 836–850.

Dalton Transactions Accepted Manuscript

Published on 04 July 2017. Downloaded by Cornell University Library on 14/07/2017 04:28:02.

37 G. Blasse, Philips Res. Rep. 1969, 24, 131–144.

38 R.P. Cao, Q.Q. Xiong, W.J. Luo, D.L. Wu, F. Xiao and X.G. Yu, Ceram. Int. 2015, 41, 7191–

7196.

39 J.Q. Long, Y.Z. Wang, R. Ma, C.Y. Ma, X.Y. Yuan, Z.C. Wen, M.M. Du and Y.G. Cao, Inorg.

Chem. 2017, 56, 3269–3275.

40 P.F. Li, M.G. Brik, L.J. Li, J. Han, X.M. Li and M.Y. Peng, J. Am. Ceram. Soc. 2016, 99,

2388–2394.

41 X. Ding, G. Zhu, W.Y. Geng, Q. Wang and Y.H. Wang, Inorg. Chem. 2015, 55, 154–162.

20