Article

Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX pubs.acs.org/IC

Tunable Optical Properties and Enhanced Thermal Quenching of

Non-Rare-Earth Double-Perovskite (Ba1−xSrx)2YSbO6:Mn4+ Red
Phosphors Based on Composition Modulation
Jiasong Zhong,† Daqin Chen,*,†,‡ Shuo Yuan,† Meijiao Liu,§ Yongjun Yuan,† Yiwen Zhu,† Xinyue Li,†
and Zhenguo Ji†
†
College of Materials and Environmental Engineering, Hangzhou Dianzi University, Hangzhou 310018, China
‡
College of Physics and Energy, Fujian Normal University, Fuzhou, 350117, P. R. China
§
Department of Chemistry, Key Laboratory of Advanced Textile Materials and Manufacturing Technology of Education Ministry,
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

Zhejiang Sci-Tech University, Hangzhou 310018, China

*
Downloaded via KAOHSIUNG MEDICAL UNIV on July 23, 2018 at 19:38:52 (UTC).

S Supporting Information

ABSTRACT: Non-rare-earth Mn4+-doped double-perovskite

(Ba1−xSrx)2YSbO6:Mn4+ red-emitting phosphors with adjustable
photoluminescence are fabricated via traditional high-temper-
ature sintering reaction. The structural evolution, variation of
Mn4+ local environment, luminescent properties, and thermal
quenching are studied systematically. With elevation of Sr2+ sub-
stituting content, the major diffraction peak moves up to a higher
angle gradually. Impressively, with increasing the substitution of
Ba2+ with Sr2+ cation from 0 to 100%, the emission band shifts to
short-wavelength in a systematic way resulting from the higher
transition energy from excited states to ground states. Besides,
this blue-shift appearance can be illuminated adequately using the
crystal field strength. The thermal quenching of the obtained
solid solution is dramatically affected by the composition, with
the PL intensity increasing 16% at 423 K going from x = 0 to 1.0. The w-LEDs component constructed by coupling the
UV-LED chip with red/green/blue phosphors demonstrate an excellent correlated color temperature (CCT) of 3404 K, as well
as color rendering index (CRI) of 86.8.

■ INTRODUCTION
In comparison to incandescent and fluorescent lamps using
tungsten filament and mercury vapor sources, semiconductor-
based LEDs are extensively used in various illumination fields
because of the many excellent characteristics, such as higher
energy efficiency, smaller size, longer lifetime, and more envi-
ronmentally friendly.1−5 Currently, the commercial white LEDs
(w-LEDs) are phosphor-converted LEDs, which structured by
coupling a Y3Al5O12:Ce3+(YAG:Ce3+) yellow phosphor with a
blue LED chip.6 Although it has been commercialized and is
widely used, it suffers from major shortcomings, for instance a
high CCT and poor CRI on account of the deficiency of red
components.7 As a consequence, its broader applications is
restricted, such as indoor lighting and medical lighting.8
To achieve high CRI and low CCT, a phosphor with preferable
red-emitting performance is demand to be added into the sys-
tem.9 Therefore, considerable efforts are devoted to discover
red-emitting phosphors suitable for the application of w-LEDs;
Usually, they are rare earth ions, such as Eu3+ and Eu2+, activated
(oxy)nitride compounds. However, several challenging issues
still exist in the commercial Eu2+-doped nitride red phosphors,
such as unsatisfactory luminescence involve photon reabsorption
and broad band emission, as well as harsh fabrication process,
which restrict their widespread applications.10−12 Therefore,
development and investigation of non-rare-earth doped
phosphors for illumination and other optoelectronic device is
significant.
Lately, Mn4+ ion as an effective non-rare-earth activator for
red-emitting phosphor has attracted great interest because of its
special spectroscopic properties.9,13 It is well-known that Mn4+-
doped phosphors exhibit broad absorption from UV to blue
region ascribed to the 4A2g → (4T1g, 2T2g, and 4T2g) transitions
and show a red emitting within the range of 620−780 nm
originated from the Mn4+:2E → 4A2g transition.13−16 Further-
more, the Mn4+ activators usual occupy in octahedral site and
the red-emitting is affected by coordination surroundings.9,17
As a result, various Mn4+-doped materials, such as oxides and
fluoride, are commonly used for the host structure of phos-
phors.18 Fluoride compounds, exhibiting a red emission peak
situated at ∼630 nm, are deemed to be suitable matrix for
Mn4+ because of their outstanding thermal stability and optical
Received: April 9, 2018

© XXXX American Chemical Society A DOI: 10.1021/acs.inorgchem.8b00947

Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
Figure 1. XRD Rietveld refinement results of Ba2YSbO6: Mn4+ and Sr2YSbO6: Mn4+. The experimental data are black crosses. The Rietveld fit and
difference curve are given in red and blue lines, respectively. Bragg reflections are indicated with green short vertical lines.
properties. Regretfully, it has poor tolerance to humidity.
Although such shortcoming can be partially addressed by
covering the hydrophobic materials on the surface of phosphors,
the procedure probably leads to a loss in luminescence and
increase the cost.12,19 In addition, the requirement of toxic hydro-
fluoric acid also limits its practical usage and quantity
production.11,12,20 As an alternative, Mn4+-activated oxide com-
pounds have been developed for its ecofriendly preparation
procedure and high chemical stability.
Generally, PL peak of Mn4+-doped oxide phosphors vary with
host structures and locate in the red waveband range of 650−
730 nm (e.g., Sr4Al14O25:Mn4+ (652 nm),21 SrMgAl10O17:
Mn4+ ,Li+ (663 nm),22 Y3Al5O 12:Mn4+ (673 nm),23 LiA-
l 5 O 8 :Mn 4+ (680 nm), 24 Gd 2 ZnTiO 6 :Mn 4+ (705 nm), 25
MgAl2Si2O8:Mn4+(710 nm),26 and SrTiO3:Mn4+(723 nm)27).
Thus, to blue-shift their photoluminescence peak toward
650 nm, the host structures can be changed due to the covalence
of “Mn4+-ligand” bonding can strongly influence the emission.9
Recently, one promising strategy for modifying the composition
of the host lattice is substitution, including neighboring cation/
anion (e.g., Al3+−Si4+, O2−−F−), same family (e.g., Li+−Na+−
K+, Ca2+−Sr2+−Ba2+), and anionic group (e.g., (PO4)3−−
(BO3)3−, (PO4)3−−(SiO4)4−) substitution.28 By appropriate
substitution, the spectral range, chemical/thermal stability, as
well as quantum efficiency, can be optimized because of the
modification of activator environment. Using these strategies,
a large number of significant phosphor materials have been
discovered, and new products with adjustable optical perform-
ances are endlessly developed by scientists.29 To date, many
researchers devoted their interesting to modify the luminescent
properties of Eu2+/Ce3+ by varying the structural composition
and crystal structure of solid solution host.30−32 However, there
is little report on studying the structural property of the Mn4+
site through color-tuning technique. Cao et al. reported the red-
shift of emission from 668 to 672 nm through substitution on
the Lu3+ site with the large Y3+ in Lu3−xYxAl5O12: Mn4+, resulting
from the stronger crystal field strength of LuAG than that of
YAG.33 Regrettably, there is no systematical study on the rela-
tionship of structural composition, thermal stability and lumi-
nescent property.
Herein, Mn4+-activated double-perovskite type antimonate
Ba2YSbO6 red phosphor have been prepared. The structural
evolution, PL performance, stability against temperature, decay
times, and CRI values are thoroughly investigated. Specifically,
with the substitution of Ba2+(1.36 Å, CN = 6) by Sr2+(1.13 Å,
B DOI: 10.1021/acs.inorgchem.8b00947
Article
CN = 6), the bond length between Sb5+ and O2− ions decreases
from 2.233 to 2.002 Å. The enhanced interaction between ions
generates a stronger crystal field (CF) environment in
Sr2YSbO6:Mn4+ phosphor than that in Ba2YSbO6:Mn4+ one,
leading to blue-shift of Mn4+ luminescence.
■
EXPERIMENTAL SECTION
Materials Synthesis. A series of (Ba1−xSrx)2YSbO6:Mn4+ samples
with various Sr2+ contents ranging from 0 to 100% were prepared
successfully by a conventional high-temperature sintering reaction. All
the products were prepared under the same condition. The starting
materials, including BaCO3 (99.9%), SrCO3 (99.9%), Y2O3(99.99%),
Sb2O5(99.99%), and MnCO3 (99.9%), were used without any
purification. The starting materials were weighted with stoichiometric
and mixed thoroughly in an agate mortar, and then put it into a
corundum crucible. Subsequently, the mixture sintered at 1500 °C for
8 h. Finally, these samples were cooled to room temperature naturally
and grounded for further measurements.
Fabrication of LED Devices. The w-LEDs devices were fabricated
by combing UV-LED chip (∼365 nm) with the mixture of blue
phosphor (BaMgAl10O17:Eu2+), green phosphor [Ba3La6(SiO4)6:Eu2+],
and red phosphor (Sr2YSbO6:Mn4+), as well as epoxy resin. First, the
mixed phosphors were blended with epoxy resin, and then deposited on
the surface of the LED chip. Lastly, the w-LEDs were obtained by
solidifying at 80 °C for 2 h.
Structure and Optical Characterization. The phase composi-
tions of the as-synthesized products were studied by X-ray diffraction
(XRD) on a Bruker D8 advance diffractometer (40 kV, 30 mA). The
XRD patterns were recorded from 10° to 80° at a scanning rate of
0.05 deg/s. The X-ray Rietveld refinement data were collected over 2θ
in the range of 10°−120° at intervals of 0.01° and analyzed using the
General Structure Analysis System (GSAS) program.34 The band
structure for Ba2YSbO6 was calculated based on the density functional
theory (DFT) and carried out using the Cambridge Serial Total Energy
Package (CASTEP) code.35 Meanwhile, the exchange and correlation
potentials were treated by the local-density approximation (LDA).36,37
The diffuse reflectance (DR) spectra were recorded on an UV−vis-NIR
spectrometer (Shimadzu UV-3600), using BaSO4 white powder as a
standard reference. The PLE and PL spectra, as well as decay curves at
room temperature, were determined using a fluorescence spectrometer
(Edinburgh Instrument FS5) with a 150 W continuous and pulsed
xenon lamp. The temperature-dependent properties of the as-obtained
products were examined by a computer-controlled electric furnace
measured from 303 to 513 K, which set up a FS5 spectrophotometer.
The photoelectric parameters of the fabricated LEDs devices, including
CCT, CRI, luminous efficacy (LE), and Commission International de
l’Eclairage (CIE) chromaticity coordinates were recorded from an
integrating sphere (HAAS-2000; Hangzhou, China) at an operating
current of 60 mA.
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry Article

Table 1. Structure Parameters of the Obtained Ba2YSbO6:0.005Mn4+ and Sr2YSbO6:0.005Mn4+ Phosphors

Ba2YSbO6 Ba2YSb0.995Mn0.005O6 Sr2YSbO6 Sr2YSb0.995Mn0.005O6
crystal system cubic cubic cubic cubic
space group Fm3̅m Fm3̅m Fm3̅m Fm3̅m
units, Z 4 4 4 4
a (Å) 8.4117 8.4084 8.405 8.4003
V (Å3) 595.18 594.48 593.76 592.77
Rp (%) 4.81 5.74
Rwp (%) 7.17 8.19
Re (%) 4.53 5.11
x2 2.499 2.568

Figure 2. (a) Representative XRD patterns of (Ba1−xSrx)2YSbO6:0.005Mn4+ (0 ≤ x ≤ 1.0). (b) The unit cell parameters show a shrinkage in the lattice
constants a and V with the increases of Sr2+ concentration in the (Ba1−xSrx)2YSbO6 (0 ≤ x ≤ 1.0) solid solution.

■ RESULTS AND DISCUSSION

Phase Analysis and Structure Characteristics. XRD
Rietveld refinements for Ba2YSbO6:0.005Mn4+ and Sr2YSbO6:
0.005Mn4+ are conducted using high intensity, high resolution
XRD data, as presented in Figure 1. Crystal structure data of
Ba2YSbO6 (ICSD no. 155253) and Sr2YSbO6 (ISCD no. 157887)
are applied as the original structure pattern. Rietveld refinements
illustrate that the experimental data are well consistent with the
structural model. Meanwhile, the final refinement details as well as
the standard cell parameters of Ba2YSbO6 (ICSD no. 155253)
and Sr2YSbO6 (ISCD no. 157887) are summarized in Table 1.
It is confirmed that Ba2YSbO6:Mn4+ and Sr2YSbO6:Mn4+
crystallizes in a cubic system with the unit cell volume slightly
smaller than those of pure Ba2YSbO6 (V = 595.18 Å3) and
Sr2YSbO6 (V = 593.76 Å3) crystal, respectively. The shrinkage
of cell volume is attributed to the substitution of Sb5+ (0.61 Å,
CN = 6) by Mn4+ (0.54 Å, CN = 6) with smaller ionic radius.
The XRD patterns of (Ba1−xSrx)2YSbO6:0.005Mn4+ (0 ≤ x ≤
1.0) phosphors are depicted in Figure 2a. The diffraction peaks
of the synthesized products are in good agreement with
Ba2YSbO6 (ICSD no. 155253) and Sr2YSbO6 (ISCD no.
157887), suggesting that the prepared samples are single phase
without other impurities. Interestingly, as the amount of Sr2+
increases, the diffraction peaks gradually move up to a higher
angle since the small Sr2+(1.13 Å, CN = 6) ion replaces large
Ba2+(1.36 Å, CN = 6) one. To gain further information, the
lattice parameter (a), as well as crystal cell volume (V), for the
C DOI: 10.1021/acs.inorgchem.8b00947
as-prepared (Ba1−xSrx)2YSbO6:0.005Mn4+ (0 ≤ x ≤ 1.0)
phosphors are plotted in Figure 2b, in which both a and
V linearly decrease with increase of Sr2+ content. As the smaller
Sr2+ is substituted for Ba2+, the a and V decreasing from 8.4084
to 8.4003 Å and 594.48 to 592.77 Å3, respectively, indicating
that Sr2+ ions have entered into Ba2YSbO6 lattice via substituting
Ba2+ ones.
Crystal structures of the studied phosphors have great
influence on their emissive performance. Both Ba2YSbO6 and
Sr2YSbO6 belong to A2BB′O6 double perovskite structure
(Figures 3a and 3b and Figure S1). They have a cubic Fm3̅
(225) space group with the corresponding cell parameters are
a = b = c = 8.417 Å and a = b = c = 8.405 Å, respectively. The
crystal structure of Sr2YSbO6 is isostructural with Ba2YSbO6 as
well as the reported Ba2GdNbO6 and Ba2YNbO6, in which
[YO6] and [SbO6] octahedrons are cross-linked each other
through sharing O2− ion in the corner and Ba2+/Sr2+ ions are
present in the cubic vacancies between octahedrons, as dis-
played in Figure S2.38,39 In general, Mn4+ ions prefer to occu-
pying octahedral site, in which the splitting of Mn4+ 3d state is
confirmed by CF strength.25 Herein, there are two types of
cation ions, [YO6] and [SbO6], coordinated by six oxygen,
which are suitable for Mn4+ substitution. Based on similar ionic
radius, Mn4+(0.54 Å, CN = 6) will replace Sb5+ (0.61 Å, CN = 6)
site, rather than Y3+ one (0.90 Å, CN = 6). The bond lengths
between Sb5+ and O2− in Ba2YSbO6 and Sr2YSbO6 matrix are
2.233 and 2.002 Å, respectively, as presented in Figure 3c and 3d.
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry Article

Figure 3. (a, b) Unit cell structure of Ba2YSbO6 and Sr2YSbO6 viewed along a-axis. The coordination environment of Sb sites and the [SbO6]
octahedron in Ba2YSbO6 (c) and Sr2YSbO6 (d) is also depicted.

Figure 4. (a) Calculated energy band structure of Ba2YSbO6. (b) PDOS and TDOS for Ba2YSbO6.

The shorting of distance between atoms is result from the
decrease of lattice parameter as the number of atomic in each
cell remains constant.33 Therefore, since the Mn4+ interaction
between atoms is strengthened, the Mn4+ experience a stronger
CF when Sr2+ doping content increases.
Electronic Band Structure. DR spectra of the obtained
(Ba1−xSrx)2YSbO6:0.005Mn4+ with different Sr2+ concentrations
are depicted in Figure S3. Obviously, two typical discernible
peaks located at ∼350 (28571 cm−1) and ∼510 nm (19608 cm−1)
assigned to the spin-allowed Mn4+:4A2g → (4T1g and 4T2g)
transitions, and an inconspicuous peak situated at ∼390 nm
(25641 cm−1) derived from spin-forbidden Mn4+:4A2g →4T2g
transition can be observed. Furthermore, the broad band between
230 and 320 nm is originated from Mn4+−O2− charge transfer
(CT) band and host absorption. Meanwhile, based on those DR
spectra, the band gaps of the prepared (Ba1−xSrx)2YSbO6:
0.005Mn4+ products can be derived by the Tauc relation, as
depicted in Figure S3b. When Sr2+ contents increase from
D DOI: 10.1021/acs.inorgchem.8b00947
x = 0 to 1.0, the band gap changes from 4.50 to 4.72 eV, indi-
cating the variation of crystal field environments. With the help
of the refinement data, the electronic structure of the Ba2YSbO6
host can be calculated based on DFT method using the CASTEP
module.29−31 Moreover, the density function is used the LDA as
the theoretical basis, and the distribution curves are displayed in
Figure 4a. Obviously, the maximum value of valence band (VB)
on the top point and the minimum one of conduction band (CB)
on the bottom point are found almost at Γ spot, indicating that the
matrix is a direct band gap semiconductor.40 Compared to the
band gap of experimental value (4.50−4.72 eV), the value of
Ba2YSbO6 matrix (∼3.57 eV) is small. This is reasonable since
the LDA generally underestimates the scale of band gap.40,41
To further resolve the components for the evaluated energy band,
the total density of states (TDOS) and partial density of states
(PDOS) of Ba2YSbO6 are depicted in Figure 4b. The region
below the Fermi level is divided to four zones. The VB region on
the bottom-most from −25 to −18 eV is consisted of Y-4p states.
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
Figure 5. (a) PLE and PL spectra of Ba2YSbO6:Mn4+ and Sr2YSbO6: Mn4+ phosphors (λex = 350 nm; λem = 685 nm). (b) Tanabe−Sugano energy level
diagram.
The second band region from −18 to −13 eV is mostly composed
of O-2s and Sb-5s5p states. The third band at −11 eV is primarily
originated from the states of Ba-5p. The fourth region from −10
to 0 eV is mainly originated from Sb-5s5p and O-2p states.
Obviously, the VB predominantly originates from the states of
O-2s, O-2p, Y-4p, Sb-5p, and Ba-5p, while the CB is mainly
constituted of Sb-5p and Ba-4d states. Herein, we can predict that
the energy levels of Mn4+ ions in Ba2YSbO6 share insignificantly
interference with the conduction and valence bands owing to the
large band gap, demonstrating that Ba2YSbO6 should provide an
appropriate band gap for Mn4+ and be a suitable emissive host for
Mn4+.42,43
Luminescent Properties. PL and PLE spectra of Mn4+-
doped Ba2YSbO6 and Sr2YSbO6 products are measured at room
temperature and shown in Figure 5a. When monitored at
685 nm, several excitation bands attributing to the Mn4+ dipole−
dipole (d−d) transitions and Mn4+−O2− CT band in the range
of 250 to 570 nm are observed.44 As displayed in Figure 5a,
four Gaussian peaks situated at 323 (30960 cm−1, CT), 355
(28169 cm−1, 4A2 → 4T1), 398 (25126 cm−1, spin-forbidden
4
A2 → 2T2), and 528 nm (18939 cm−1, spin-allowed 4A2 → 4T2)
for Ba2YSbO6:Mn4+ and 303 (33003 cm−1, CT), 346 (28902 cm−1,
4
A2 → 4T1), 387 (25840 cm−1, spin-forbidden 4A2 → 2T2), and
510 nm (19608 cm−1, spin-allowed 4A2 → 4T2) for Sr2YSbO6:Mn4+
are decomposed.45 Upon 350 nm excitation, the strongest PL peak
at 681 nm for Sr2YSbO6:Mn4+ and 691 nm for Ba2YSbO6:Mn4+
in the range of 620 to 750 nm, originating from Mn4+:2E →
4
A2g transition in a [SbO6] octahedral environment, can be
found.46 Compared to Ba2YSbO6:Mn4+(691 nm), a blue shift
occurs in Sr2YSbO6:Mn4+(681 nm), implying the different CF
environment on Mn4+. As is well-known, Mn4+ ion is sensitive to
CF environments due to its special 3d3 electron configuration.
Therefore, to comprehend the influence of CF strength on the
luminescence properties of Ba2YSbO6:Mn4+ and Sr2YSbO6:
Mn4+, the Racah parameters (B, C) and CF strength (Dq) are
calculated. The value of Dq is evaluated with the assistance of the
energy of 4A2g → 4T2g transition47,48
E(4 A 2g → 4 T 2g )
Dq =
10 (1)
E DOI: 10.1021/acs.inorgchem.8b00947
Article
where the mean peaks energy gap of Ba2YSbO6:Mn4+ and
Sr2YSbO6:Mn4+ are 18939 and 19608 cm−1, respectively.
Besides, the value of B is evaluated according to the difference
of peak energy between 4A2g → 4T1g and 4A2g → 4T2g transitions
(9230 cm−1 for Ba2YSbO6:Mn4+ and 9294 cm−1 for Sr2YSbO6:
Mn4+), as the following equation:49
Dq 15(δ − 8)
= 2
B δ − 10δ (2)
δ can be obtained as follows:
E(4 A 2g → 4 T1g ) − E(4 A 2g → 4 T 2g )
δ=
Dq (3)
Finally, based on the energy of 2Eg → 4A2g (14684 and
14472 cm−1 for Ba2YSbO6:Mn4+ and Sr2YSbO6:Mn4+, respec-
tively), the value of C is estimated as follows:
E(2 E g → 4 A 2g) 3.05C 1.8B
= − + 7.9
B B Dq (4)
On the basis of the eqs 1−4, the final calculated Dq, B and C in
Ba2YSbO6:Mn4+ and Sr2YSbO6:Mn4+ products are 1894, 1007,
3480 cm−1 and 1961, 1000, 3354 cm−1, respectively. Thus, Dq
versus B can be calculated to be 1.88 and 1.96 for Ba2YSbO6 and
Sr2YSbO6, respectively. Therefore, owing to the decreased lat-
tice parameter with increasing of Sr2+ concentrations, the inter-
actions of Mn4+−Mn4+ and Mn4+−O2− are enhanced, resulting
in a stronger crystal field of Mn4+. From the calculated
Dq/B values, we can find that Sr2YSbO6 has stronger CF strength
than that of Ba2YSbO6. This result is well agreement with the
above conclusions.
Generally, Mn4+ ion only situated in an octahedral, which can
offer complex spectral characteristic in various CF environments
because of its special 3d3 electron configuration.50 Therefore,
owing to the different site symmetry and CF strength of the
doped host, the luminescence of Mn4+ is diverse from each
other. The electron transitions of Mn4+ in different energy levels
can be described using the well-known Tanabe−Sugano energy
diagram, as depicted in Figure 5b. Notably, except for 2Eg and
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry Article

Figure 6. (a) Integrated emission intensity of the Mn4+ at various Sr2+ doping contents. Inset is the digital images of the obtained phosphors under
sunlight and 365 nm UV light. (b) Normalized PL spectra of the as-prepared (Ba1−xSrx)2YSbO6:0.005Mn4+ (0 ≤ x ≤ 1.0) phosphors. Inset is the
corresponding amplification PL spectra ranging from 670 to 700 nm. (c) Decay curves of the Mn4+: 2E → 4A2 in (Ba1−xSrx)2YSbO6:0.005Mn4+
(0 ≤ x ≤ 1.0) samples under 350 nm excitation.
2
T1g levels, most multiplets are highly rely on the CF strength.51 indicated with red and green short vertical lines, respectively.
The 4T1g and 4T2g levels are originated from the t22 electronic Compared to Ba2YSbO6 one, the stronger CF strength observed
orbital, while others come from t23e orbital, including 4A2g, 2T1g, in Sr2YSbO6 is ascribed to the shorter band length of Mn4+−O2−
2
T2g, and 2Eg levels. A large spectral bandwidth for the transition ligand in Sr2YSbO6 (2.002 Å) than that of Ba2YSbO6 (2.233 Å).
can be observed due to the large lateral displacement between This result is consistent with the above conclusions.
ground state 4A2g and 4T1g(or 4T2g).52 Furthermore, on the basis To determine the optimal Mn4+ concentration, PL spectra
of the spin selection rule, 4A2g → (4T1g and 4T2g) transitions are of Ba2YSbO6:xMn4+ (0.001≤ x ≤ 0.02) are measured under
spin-allowed; hence, the relatively large bandwidths of the strong 350 nm excitation, as shown in Figure S4. It can be found that
excitation or absorption between these transitions can be the position of emission peak keeps almost unchanged with
expected. Meanwhile, the sharp emission lines derived from the increment of Mn4+ concentrations from 0.1 mol % to 2 mol %.
spin-forbidden 2Eg → 4A2 transition can be found. As presented PL intensity decline gradually as the concentrations of Mn4+
in Figure 5b, the Dq/B values of Sr2YSbO6 than Ba2YSbO6 are exceed 0.5 mol % owing to concentration quenching. Hence, we
F DOI: 10.1021/acs.inorgchem.8b00947
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
Figure 7. Temperature-dependent emission spectra of as-prepared (Ba1−xSrx)2YSbO6:Mn4+(0 ≤ x ≤ 1.0) with varying Sr2+ concentrations (x):
(a) x = 0, (b) x = 0.5, and (c) x = 1.0 from 303 to 513 K. (d) The integrated PL intensities versus temperature for the (Ba1−xSrx)2YSbO6:Mn4+
phosphors. Inset shows the fitted lines based on the Arrhenius equation to determine activation energy.
keep Mn4+ content at 0.5 mol % and tuned regularly the molar
ratio of Ba:Sr between 2:0 and 0:2 to discuss our design of shift-
ing and enhancing the emission of Mn4+ systematically. The rela-
tive intensities of the Mn4+ emission bands gradually enhance as the
enlargement of x. When x = 1.0, and the emission intensity of
Sr2YSbO6: Mn4+ displays 3.53 times than that of Ba2YSbO6: Mn4+,
as revealed in Figure 6a. Additionally, the normalized PL spectra
of (Ba1−xSrx)2YSbO6:0.005Mn4+(0 ≤ x ≤ 1.0) are depicted in
Figure 6b. Impressively, the PL spectra exhibit a blue shift from
691 to 681 nm as the Ba2+ ions are substituted by Sr2+ ones in
Ba2YSbO6. After cation substitution, the energy gap between
4
A2g level and 2E one of Mn4+can be neglected since these two
levels are insensitive to the modification of crystal field.53 Com-
pared with the reported Lu3−xYxAl5O12:Mn4+ red phosphor with a
red shift of 4 nm,33 the obtained (Ba1−xSrx)2YSbO6: Mn4+ products
exhibit a great progress with a blue shift of 10 nm. The major blue
shift is mainly attributed to the higher CF strength of Mn4+ in
Sr2YSbO6 (1.96) than that in Ba2YSbO6 (1.88). Higher-energy
splitting results in higher transition energy from excited states to
ground ones, which leads to blue-shift of emission.54
Additionally, the luminescence decay curves of (Ba1−xSrx)2
YSbO6:0.005Mn4+ (0 ≤ x ≤ 1.0) samples measured at excitation
wavelength of 350 nm with λem= 680 nm are displayed in Figure 6c.
The lifetime is increased from 0.1592 to 0.3458 ms with increasing
of Sr2+ contents. As above-mentioned, the variation trend of fluores-
cence lifetime is similar to that of PL intensity, confirming that
difference CF strength produces diverse effects on Mn4+ decay
times for the (Ba1−xSrx)2YSbO6:0.005Mn4+(0 ≤ x ≤ 1.0) samples.
Furthermore, the quantum efficiency of the as-prepared samples
is determined to 32.8%−46.2% under 350 nm excitation according
to two measurement approaches.55
To realize their possible application in w-LEDs, the thermal
stability is one of important factors needing consideration.
G DOI: 10.1021/acs.inorgchem.8b00947
Article
Temperature-dependent PL spectra of (Ba1−xSrx)2YSbO6:
0.005Mn4+ with various Sr2+ concentrations (x) are presented
in Figures 7a−7c. Evidently, as the temperature elevates from
303 to 513 K, the emission intensity descends gradually without
any shifting or broadening for three typical Ba2YSbO6:
0.005Mn4+, BaSrYSbO6:0.005Mn4+, and Sr2YSbO6:0.005Mn4+
phosphors. Interestingly, the body color of the obtained
Sr2YSbO6:Mn4+ sample shows the better temperature stability
than the other members under the 350 nm UV excitation. The
tendency is depicted more apparently in Figure 7d, in which
the emission intensity reduced gradually as the temperature
increasing above 303 K. When the temperature raised up to
423 K, the PL intensity of Ba2YSbO6:0.005Mn4+, BaSrYSbO6:
0.005Mn4+ and Sr2YSbO6:0.005Mn4+ drops to 69%, 74%, and
85% of the initial intensity at 303 K, respectively. Compared with
other reported Mn4+-activated oxide phosphor, the as-prepared
sample exhibits a relatively high thermal quenching temperature.
Additionally, this phenomenon can be elaborated by the activation
energy (ΔE) using the Arrhenius equation56
I0
IT =
1 + exp( −ΔE /kT ) (5)
where I0 and IT stand for the emission intensity at initial and
given temperature (303−513 K), respectively. On basis of above
equation, a plot of ln(I0/IT − 1) to 1/kT can be gained, as
depicted in inset of Figure 7d. The ΔE values are 0.2104, 0.2640,
and 0.3237 eV for Ba2YSbO6:Mn4+, BaSrYSbO6:Mn4+, and
Sr2YSbO6:Mn4+, respectively, which comparable to that of
CaAlSiN3:Eu2+ (0.20−0.24). Therefore, the retained intensities
at 150 °C for these two phosphors are found to be similar (about
80−90%).57,58 Both high thermal quenching temperature and
high activation energy of Mn4+ luminescence are originated
from the decrease of ionic distance between O2− and Sb5+ in the
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
Figure 8. (a) CIE chromaticity diagram of five constructed w-LEDs devices via combining UV LED chip with the mixture of blue and green phosphors
without (b) and with (c−f) red phosphor. (b−f) EL spectra of the constructed w-LEDs with various weight ratios of red/green/blue (0, 5:47.5:47.5,
10:45:45, 15:42.5:42.5, 20:40:40). Inset shows the photograph of their corresponding LED images under 60 mA forward bias currents.
[SbO6] octahedron, resulting in the increase of activation barrier
for thermal quenching.59
Performance of LED Devices. On the basis of the above
results, we can find that the as-prepared (Ba1−xSrx)2YSbO6:Mn4+
phosphors are of superior luminescence performances and
excellently thermal quenching resistances. Therefore, investigat-
ing their potential application on the LED devices is very sig-
nificance. To validate the available application, we chose
Sr2YSbO6:Mn4+ phosphor for the example to fabricate the
w-LEDs. Herein, the w-LEDs are constructed by mixing blue
phosphor (BaMgAl10 O 17 :Eu 2+ ), green phosphor [Ba3 La 6
(SiO4)6:Eu2+]60 and red phosphor (Sr2YSbO6:Mn4+) with a
UV-LED chip. Figure 8 shows the CIE chromaticity coordinates
and typical electroluminescence (EL) spectra of the fabricated
w-LEDs under 60 mA forward bias current. Herein, when the
content of Sr2YSbO6:Mn4+ phosphor is chosen, the other phos-
phors are equally included. Apparently, significant difference can
be found for the w-LEDs constructed with various ratios of red/
green/blue phosphors, as presented in Figure 8b−8f. Their
corresponding important photoelectric parameters with various
ratios of R/(R+G+B) are tabulated in Table S1. When the
amount of Sr2YSbO6:Mn4+ phosphor increases, the red emission
peak at ∼685 nm originated from Mn4+:2Eg → 4A2g transition
becomes obvious. Meanwhile, the performance of the fabricated
w-LEDs experience decreasing CCT from 7618 to 3404 K and
increasing CRI from 68.7 to 86.8 by enhancing the weight ratio
of Sr2YSbO6:Mn4+ from 0 wt % to 20 wt %. Unfortunately, the
LE declines from 31.08 to 15.51 lm/W, probably owing to the
reduction in light extraction after the addition of red phosphors.
Specially, the chromaticity coordinates of these five LED are
(0.2918, 0.3307), (0.32378, 0.3476), (0.3587, 0.3644), (0.3774,
0.3720), and (0.4082, 0.3831), respectively, which all locate in or
near the blackbody locus (Figure 8a). Correspondingly, the yielded
H DOI: 10.1021/acs.inorgchem.8b00947
Article
white light turns from cool to warm. Fortunately, the values of CCT
(4021−3404 K), CRI (83.7−86.8), and LE (18.61−15.51 lm/W)
in LED devices including 15% or 20% Sr2YSbO6:Mn4+ red phos-
phors are still accredited for indoor illumination.
■
CONCLUSIONS
Mn -doped double perovskite (Ba1−xSrx)2YSbO6:Mn4+ solid-
4+
solutions with adjustable PL emissions were prepared through a
conventional high-temperature sintering reaction. Rietveld refine-
ments confirmed that these solid-solutions belonged to a cubic
Fm3̅m space group. The substitution of Ba2+ by Sr2+ inducedual
shift of diffraction peaks toward a higher angle, monotonous
decrease of lattice parameter from 8.4084 to 8.4003 Å and
increase of band gap from 4.50 to 4.72 eV. Correspondingly, Mn4+
emission peaks blue-shifted from 691 to 681 nm upon 350 nm
light excitation, owing to the promotion of Mn4+2 Eg energy state
position. This result is mainly ascribed to the alteration of Mn4+
CF strength by cationic substitution in the (Ba1−xSrx)2YSbO6:
Mn4+ hosts. Impressively, the thermal stability is significantly
improved after complete replacement of Ba2+ by Sr2+, where 69%
to 85% of the initial PL intensities were retained at 423 K, res-
pectively. Finally, w-LEDs were fabricated by coupling the
mixed red/green/blue phosphors with UV-LED chip, and the
corresponding CCT and CRI can be easily tuned from 7618 to
3404 K and from 68.7 to 86.8 by simply modifying the contents
of Sr2YSbO6:Mn4+. All the results manifest that the prepared com-
position series may find promising application in warm LED.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the ACS
Publications website at DOI: 10.1021/acs.inorgchem.8b00947.
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
Crystal structure of Ba2YSbO6, Ba2GdNbO6, and Ba2YNbO6;
diffuse reflectance spectra; PL spectra of Ba2YSbO6:xMn4+;
and photoelectric parameters (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: dqchen@hdu.edu.cn.
ORCID
Daqin Chen: 0000-0003-0088-2480
Yongjun Yuan: 0000-0002-1823-3174
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was supported by Zhejiang Province Natural Science
Foundation of China (LY18E020006), the Natural Science
Foundation of Zhejiang for Distinguished Young Scholars
(LR15E020001), and National Nature Science Foundation of
China (51502066 and 51572065).
■
REFERENCES
(1) Xia, Z. G.; Liu, Q. L. Progress in discovery and structural design of
color conversion phosphors for LEDs. Prog. Mater. Sci. 2016, 84, 59−
117.
(2) Ye, S.; Xiao, F.; Pan, Y. X.; Ma, Y. Y.; Zhang, Q. Y. Phosphors in
phosphor-converted white light-emitting diodes: Recent advances in
materials, techniques and properties. Mater. Sci. Eng., R 2010, 71, 1−34.
(3) Li, K.; Shang, M. M.; Lian, H. Z.; Lin, J. Recent development in
phosphors with different emitting colors via energy transfer. J. Mater.
Chem. C 2016, 4, 5507−5530.
(4) Lin, C. C.; Meijerink, A.; Liu, R. S. Critical Red Components for
Next-Generation White LEDs. J. Phys. Chem. Lett. 2016, 7, 495−503.
(5) Schubert, E. F.; Kim, J. K. Solid-State Light Sources Getting Smart.
Science 2005, 308, 1274.
(6) Cai, P. Q.; Qin, L.; Chen, C. L.; Wang, J.; Bi, S. L.; Kim, S. I.;
Huang, Y. L.; Seo, H. J. Optical Thermometry Based on Vibration
Sidebands in Y2MgTiO6:Mn4+ Double Perovskite. Inorg. Chem. 2018,
57, 3073−3081.
(7) Li, J. H.; Yan, J.; Wen, D. W.; Khan, W. U.; Shi, J. X.; Wu, M. M.;
Su, Q.; Tanner, P. A. Advanced red phosphors for white light-emitting
diodes. J. Mater. Chem. C 2016, 4, 8611−8623.
(8) Tang, Z. B.; Wang, D. Y.; Khan, W. U.; Du, S. S.; Wang, X. C.;
Wang, Y. H. Novel zirconium silicate phosphor K2ZrSi2O7: Eu2+ for
white light-emitting diodes and field emission displays. J. Mater. Chem.
C 2016, 4, 5307−5313.
(9) Zhou, Z.; Zhou, N.; Xia, M.; Yokoyama, M.; Hintzen, H. T.
Research progress and application prospects of transition metal Mn4+-
activated luminescent material. J. Mater. Chem. C 2016, 4, 9143−9161.
(10) Chen, Y. B.; Wu, K. L.; He, J.; Tang, Z. B.; Shi, J. X.; Xu, Y. Q.;
Liu, Z. Q. A Bright and Moisture-Resistant Red-Emitting Lu3Al5O12:
Mn4+,Mg2+ Garnet Phosphor for High-Quality Phosphor-Converted
White LEDs. J. Mater. Chem. C 2017, 5, 8828−8835.
(11) Huang, C. S.; Huang, C. L.; Liu, Y. C.; Lin, S. K.; Chan, T. S.; Tu,
H. W. Ab Initio-Aided Sensitizer Design for Mn4+-Activated Mg2TiO4
as an Ultrabright Fluoride-Free Red-Emitting Phosphor. Chem. Mater.
2018, 30, 1769−1775.
(12) Wang, B.; Lin, H.; Huang, F.; Xu, J.; Chen, H.; Lin, Z. B.; Wang,
Y. S. Non-Rare-Earth BaMgAl10−2xO17:xMn4+,xMg2+: A Narrow-Band
Red Phosphor for Use as a High-Power Warm w-LED. Chem. Mater.
2016, 28, 3515−3524.
(13) Zhong, J. S.; Zhou, S.; Chen, D. Q.; Li, J. J.; Zhu, Y. W.; Li, X. Y.;
Chen, L. F.; Ji, Z. G. Enhanced Luminescence of Ba2GdSbO6:Mn4+ red
phosphor via cation doping for warm white light-emitting diodes.
Dalton Trans. 2018, 47, 8248−8256.
(14) Liang, S. S.; Shang, M. M.; Lian, H. Z.; Li, K.; Zhang, Y.; Lin, J. An
efficient rare-earth free deep red emitting phosphor for improving the
I DOI: 10.1021/acs.inorgchem.8b00947
Article
color rendering of white light-emitting diodes. J. Mater. Chem. C 2017,
5, 2927−2935.
(15) Lü, W.; Lv, W. Z.; Zhao, Q.; Jiao, M. M.; Shao, B. Q.; You, H. P. A
Novel Efficient Mn4+ Activated Ca14Al10Zn6O35 Phosphor:Application
in Red-Emitting and White LEDs. Inorg. Chem. 2014, 53, 11985−
11990.
(16) Zhong, J. S.; Chen, D. Q.; Chen, X.; Wang, K. Y.; Li, X. Y.; Zhu, Y.
W.; Ji, Z. G. An efficient rare-earth free red-emitting
Ca2YSbO6:Mn4+,M(M = Li+, Na+, K+, Mg2+) phosphors for white
light-emitting diodes. Dalton Trans. 2018, 47, 6528−6537.
(17) Cao, R. P.; Ye, Y. J.; Peng, Q. Y.; Zheng, G. T.; Ao, H.; Fu, J. W.;
Guo, Y. M.; Guo, B. Synthesis and luminescence characteristics of novel
red-emitting Ba2TiGe2O8:Mn4+ phosphor. Dyes Pigm. 2017, 146, 14−
19.
(18) Huang, L.; Zhu, Y. W.; Zhang, X. J.; Zou, R.; Pan, F. J.; Wang, J.;
Wu, M. M. HF-Free Hydrothermal Route for Synthesis of Highly
Efficient Narrow-Band Red Emitting Phosphor K2Si1−xF6:xMn4+ for
Warm White Light-Emitting Diodes. Chem. Mater. 2016, 28, 1495−
1502.
(19) Nguyen, H. D.; Lin, C. C.; Liu, R. S. Waterproof Alkyl Phosphate
Coated Fluoride Phosphors for Optoelectronic Materials. Angew.
Chem., Int. Ed. 2015, 54, 10862−10866.
(20) Wang, B.; Lin, H.; Xu, J.; Chen, H.; Wang, Y. S.
CaMg2Al16O27:Mn4+-based Red Phosphor: A Potential Color Con-
verter for High-Powered Warm W-LED. ACS Appl. Mater. Interfaces
2014, 6, 22905−22913.
(21) Peng, M.; Yin, X.; Tanner, P. A.; Liang, C.; Li, P.; Zhang, Q.; Qiu,
J. Orderly-Layered Tetravalent Manganese-Doped Strontium Alumi-
nate Sr4Al14O25: Mn4+: An Efficient Red Phosphor for Warm White
Light Emitting Diodes. J. Am. Ceram. Soc. 2013, 96, 2870−2876.
(22) Zhong, J. S.; Xu, W.; Chen, Q. L.; Yuan, S.; Ji, Z. G.; Chen, D. Q.
Mn4+,Li+ co-doped SrMgAl10O17 phosphor-in-glass: Application in
high-power warm w-LEDs. Dalton Trans. 2017, 46, 9959−9968.
(23) Chen, D. Q.; Zhou, Y.; Xu, W.; Zhong, J. S.; Ji, Z. G.; Xiang, W. D.
Enhanced luminescence of Mn4+:Y3Al5O12 red phosphor via impurity
doping. J. Mater. Chem. C 2016, 4, 1704−1712.
(24) McNicol, B.; Pott, G. Luminescence of Mn ions in ordered and
disordered LiAl5O8. J. Lumin. 1973, 6, 320−334.
(25) Chen, H.; Lin, H.; Huang, Q. M.; Huang, F.; Xu, J.; Wang, B.; Lin,
Z. B.; Zhou, J. C.; Wang, Y. S. A novel double-perovskite Gd2ZnTiO6:
Mn4+ red phosphor for UV-based w-LEDs: structure and luminescence
properties. J. Mater. Chem. C 2016, 4, 2374−2381.
(26) Kalaycioglu, N. O.; Ç ırçır, E. Red phosphors in MgAl2Si2O8
doping with Mn4+, Gd3+ and Lu3+ and host-sensitized luminescence
properties. J. Therm. Anal. Calorim. 2013, 111, 273−277.
(27) Bryknar, Z.; Trepakov, V.; Potů če k, Z.; Jastrabík, L.
Luminescence spectra of SrTiO3: Mn4+. J. Lumin. 2000, 87-89, 605−
607.
(28) Li, Z. L.; Wang, Z. J.; Li, P. L.; Cheng, J. G.; Tian, M. M.; Wang,
C.; Yang, Z. P. Improvement of thermal stability and photo-
luminescence in Sr0.8Ca0.2Al2Si2O8:Eu2+ by the substitution of Si−
Na# Al−Sr and Ca# Sr for structural modifications. Dalton Trans. 2017,
46, 14310−14317.
(29) Xia, Z. G.; Miao, S. H.; Molokeev, M. S.; Chen, M. Y.; Liu, Q. L.
Structure and luminescence properties of Eu 2 + doped
LuxSr2−xSiNxO4−x phosphors evolved from chemical unit cosubstitu-
tion. J. Mater. Chem. C 2016, 4, 1336−1344.
(30) Xia, Z. G.; Ma, C. G.; Molokeev, M. S.; Liu, Q. L.; Rickert, K.;
Poeppelmeier, K. R. Chemical Unit Cosubstitution and Tuning of
Photoluminescence in the Ca2(Al1−xMgx)(Al1−xSi1+x)O7:Eu2+ Phos-
phor. J. Am. Chem. Soc. 2015, 137, 12494−12497.
(31) Xia, Z. G.; Liu, G. K.; Wen, J. G.; Mei, Z. G.; Balasubramanian,
M.; Molokeev, M. S.; Peng, L. C.; Gu, L.; Miller, D. J.; Liu, Q. L.;
Poeppelmeier, K. R. Tuning of Photoluminescence by Cation
Nanosegregation in the (CaMg)x(NaSc)1−xSi2O6 Solid Solution. J.
Am. Chem. Soc. 2016, 138, 1158−1161.
(32) Khan, S. A.; Zhong, H.; Ji, W. W.; Hao, L. Y.; Abadikhah, H.; Xu,
X.; Khan, N. Z.; Agathopoulos, S. Single-Phase White Light-Emitting
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry Article

CaxBa(9−x)Lu2Si6O24:Eu2+/Mn2+ Phosphors. ACS Omega 2017, 2, Mg3Ga2GeO8:Mn4+ Phosphor Excited by Near-UV Light for White-
6270−6277. Light-Emitting Diodes. Inorg. Chem. 2016, 55, 154−162.
(33) Long, J. Q.; Wang, Y. Z.; Ma, R.; Ma, C. Y.; Yuan, X. Y.; Wen, Z. (53) Blasse, G.; Grabmaier, B. C. Luminescent Materials; Springer:
C.; Du, M. M.; Cao, Y. G. Enhanced Luminescence Performances of Berlin, Germany, 1994.
Tunable Lu3−xYxAl5O12:Mn4+ Red Phosphor by Ions of Rn+ (Li+, Na+, (54) Long, J. Q.; Chu, F. J.; Wang, Y. Z.; Zhao, C.; Dong, W. F.; Yuan,
Ca2+, Mg2+, Sr2+, Sc3+). Inorg. Chem. 2017, 56, 3269−3275. X. Y.; Ma, C. Y.; Wen, Z. C.; Ma, R.; Du, M. M.; Cao, Y. G.
(34) Toby, B. H. EXPGUI, a graphical user interface for GSAS. J. Appl. M8MgSc(PO4)7:xDy3+ (M = Ca/Sr) Single-Phase Full-Color Phosphor
Crystallogr. 2001, 34, 210−213. with High Thermal Emission Stability. Inorg. Chem. 2017, 56, 10381−
(35) Zhang, N. M.; Guo, C. F.; Zheng, J. M.; Su, X. Y.; Zhao, J. 10386.
Synthesis, electronic structures and luminescent properties of Eu3+ (55) Leyre, S.; Coutino-Gonzalez, E.; Joos, J. J.; Ryckaert, J.; Meuret,
doped KGdTiO4. J. Mater. Chem. C 2014, 2, 3988−3994. Y.; Poelman, D.; Smet, P. F.; Durinck, G.; Hofkens, J.; Deconinck, G.;
(36) Kohn, W.; Sham, L. J. Self-Consistent Equations Including Hanselaer, P. Absolute Determination of Photoluminescence Quantum
Exchange and Correlation Effects. Phys. Rev. 1965, 140, A1133−A1138. Efficiency Using an Integrating Sphere Setup. Rev. Sci. Instrum. 2014,
(37) Perdew, J. P.; Zunger, A. Self-interaction Correction to Density- 85, 123115.
functional Approximations for Many-electron Systems. Phys. Rev. B: (56) Wang, X. C.; Zhao, Z. Y.; Wu, Q. S.; Li, Y. Y.; Wang, Y. H. A
Condens. Matter Mater. Phys. 1981, 23, 5048−5079. Garnet-Based Ca2YZr2Al3O12:Eu3+ Red-Emitting Phosphor for n-UV
(38) Fu, A. J.; Zhou, C. Y.; Chen, Q.; Lu, Z. Z.; Huang, T. J.; Wang, H.; Light Emitting Diodes and Field Emission Displays: Electronic
Zhou, L. Y. Preparation and optical properties of a novel double- Structure and Luminescence Properties. Inorg. Chem. 2016, 55,
perovskite phosphor, Ba2GdNbO6:Mn4+, for light-emitting diodes. 11072−11077.
Ceram. Int. 2017, 43, 6353−6362. (57) Li, S. X.; Wang, L.; Zhu, Q. Q.; Tang, D. M.; Liu, X. J.; Cheng, G.
(39) Fu, A. J.; Pang, Q.; Yang, H.; Zhou, L. Y. Ba2YNbO6Mn4+-based F.; Lu, L.; Takeda, T.; Hirosaki, N.; Huang, Z. G.; Xie, R. J. Crystal
structure, tunable emission and applications of
red phosphor for warm white light-emitting diodes (WLEDs):
Ca1−xAl1−xSi1+xN3−xOx:RE (x = 0−0.22, RE = Ce3+, Eu2+) solid
Photoluminescent and thermal characteristics. Opt. Mater. 2017, 70,
solution phosphors for white light-emitting diodes. J. Mater. Chem. C
144−152.
2016, 4, 11219−11230.
(40) Jansen, T.; Gorobez, J.; Kirm, M.; Brik, M. G.; Vielhauer, S.; Oja,
(58) Piao, X. Q.; Machida, K.; Horikawa, T.; Hanzawa, H.;
M.; Khaidukov, N. M.; Makhov, V. N.; Jüstel, T. Narrow Band Deep Shimomura, Y.; Kijima, N. Preparation of CaAlSiN3:Eu2+ Phosphors
Red Photoluminescence of Y2Mg3Ge3O12:Mn4+,Li+ Inverse Garnet for by the Self-Propagating High-Temperature Synthesis and Their
High Power Phosphor Converted LEDs. ECS J. Solid State Sci. Technol. Luminescent Properties. Chem. Mater. 2007, 19, 4592−4599.
2018, 7, R3086−R3092. (59) Jansen, T.; Jüstel, T.; Kirm, M.; Vielhauer, S.; Khaidukov, N. M.;
(41) Kim, D.; Park, S.; Choi, B. C.; Park, S. H.; Jeong, J. H.; Kim, J. H. Makhov, V. N. Composition Dependent Spectral Shift of Mn4+
The tetravalent manganese activated SrLaMgTaO6 phosphor for w- Luminescence in Silicate Garnet Hosts CaY2M2Al2SiO12(M = Al, Ga,
LED applications. Mater. Res. Bull. 2018, 97, 115−120. Sc). J. Lumin. 2018, 198, 314−319.
(42) Ding, X.; Wang, Q.; Wang, Y. H. Rare-earth-free red-emitting (60) Zhong, J. S.; Chen, D. Q.; Yuan, Y. J.; Chen, L. F.; Yu, H.; Ji, Z. G.
K2Ge4O9: Mn4+ phosphor excited by blue light for warm white LEDs. Synthesis and spectroscopic investigation of Ba3La6(SiO4)6: Eu2+ green
Phys. Chem. Chem. Phys. 2016, 18, 8088−8097. phosphors for white light-emitting diodes. Chem. Eng. J. 2017, 309,
(43) Wang, Z. L.; Wang, N.; Yang, Z. Y.; Yang, Z. F.; Wei, Q. W.; 795−801.
Zhou, Q.; Liang, H. B. Luminescent properties of novel red-emitting
phosphor Na3TaF8 with non-equivalent doping of Mn4+ for LED
backlighting. J. Lumin. 2017, 192, 690−694.
(44) Jin, Y. H.; Hu, Y. H.; Wu, H. Y.; Duan, H.; Chen, L.; Fu, Y. R.; Ju,
G. F.; Mu, Z. F.; He, M. A deep red phosphor Li2MgTiO4:Mn4+
exhibiting abnormal emission: Potential application as color converter
for warm w-LEDs. Chem. Eng. J. 2016, 288, 596−607.
(45) Li, K.; Zhu, D. M.; Van Deun, R. Photoluminescence properties
and crystal field analysis of a novel red emitting phosphor
K2BaGe8O18:Mn4+. Dyes Pigm. 2017, 142, 69−76.
(46) Zhou, Z.; Zheng, J.; Shi, R.; Zhang, N.; Chen, J.; Zhang, R.; Suo,
H.; Goldys, E. M.; Guo, C. Ab initio site occupancy and far-red emission
of Mn4+ in cubic-phase La(MgTi)1/2O3 for plant cultivation. ACS Appl.
Mater. Interfaces 2017, 9, 6177−6185.
(47) Reisfeld, M. J.; Matwiyoff, N. A.; Asprey, L. B. Electronic
spectrum of cesium hexafluoromanganese (IV). J. Mol. Spectrosc. 1971,
39, 8−20.
(48) Brik, M. G.; Camardello, S. J.; Srivastava, A. M. Influence of
covalency on the Mn4+2Eg→4A2g emission energy in crystals. ECS J.
Solid State Sci. Technol. 2015, 4, R39−R43.
(49) Brik, M. G.; Camardello, S. J.; Srivastava, A. M.; Avram, N. M.;
Suchocki, A. Spinforbidden transitions in the spectra of transition metal
ions and nephelauxetic effect. ECS J. Solid State Sci. Technol. 2016, 5,
R3067−R3077.
(50) Henderson, B.; Imbrush, G. F. Optical Spectroscopy of Inorganic
Solids; Clarendon Press: Oxford, 1989.
(51) Liang, S.; Shang, M.; Lian, H.; Li, K.; Zhang, Y.; Lin, J. Deep red
MGe4O9:Mn4+(M = Sr,Ba) phosphors: structure, luminescence
properties and application in warm white light emitting diodes. J.
Mater. Chem. C 2016, 4, 6409−6416.
(52) Ding, X.; Zhu, G.; Geng, W. Y.; Wang, Q.; Wang, Y. H. Rare-
Earth-Free High-Efficiency Narrow-Band Red-Emitting

J DOI: 10.1021/acs.inorgchem.8b00947
Inorg. Chem. XXXX, XXX, XXX−XXX