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Communication—Luminescent Properties of Mn 4+ -Activated K 3 HfF 7 Red

Phosphor

Article · January 2018

DOI: 10.1149/2.0051805jss

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Communication—Luminescent Properties of Mn4+ -Activated

K3 HfF7 Red Phosphor
z
Qianwen Wei, Zhiyu Yang, Zhaofeng Yang, Qiang Zhou, and Zhengliang Wang
Key Laboratory of Comprehensive Utilization of Mineral Resource in Ethnic Regions, School of Chemistry &
Environment, Yunnan Minzu University, Kunming 650500, People’s Republic of China

Herein, a new red-emitting phosphor K3 HfF7 :Mn4+ was successfully synthesized. The crystal structure and morphology were
investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Mn4+ in K3 HfF7 exhibits excellent luminescent
properties with red emission at ∼630 nm and broad excitation band around ∼460 nm. The white light-emitting diode fabricated with
K3 HfF7 :Mn4+ red phosphor shows intense warm white light with appropriate optical properties, the correlated color temperature of
3535 K and color rendering index of 86.2.
© 2018 The Electrochemical Society. [DOI: 10.1149/2.0051805jss]

Manuscript submitted February 14, 2018; revised manuscript received March 28, 2018. Published April 24, 2018.

White light-emitting diodes (w-LEDs) have attracted increasing fuse reflectance spectrum (DRS) and the decay curve were obtained
attentions to replace traditional solid-state lighting, due to their many on a Cary 5000 UV-Vis-NIR spectrophotometer and an Edinburgh
advantages.1,2 In order to make up for the shortcomings of commercial FLS920 combined fluorescence lifetime and steady state spectrome-
w-LEDs with high correlated color temperature (CCT) and low color ter. Excitation and emission spectra were measured on a Cary Eclipse
rendering index (CRI), some red phosphors (such as Eu2+ -activated PL1011M003 (Varian) spectrofluorometer. The electroluminescent
(oxy)nitride phosphors and Mn4+ -activated fluorides) were added into (EL) properties of LEDs were investigated on an array spectrome-
the w-LEDs.3–6 Compared with red phosphors doped with rare-earth ter (HSP6000).
ions, the fluoride phosphors doped with Mn4+ exhibit many excellent
performances in w-LED applications. They not only can improve
CCT and CRI qualities, but also avoid the consumption of expensive Results and Discussion
rare-earth ions and harsh synthesis conditions.6 Fig. 1a exhibits the XRD pattern of K3 HfF7 :Mn4+ with the corre-
In recent years, many Mn4+ -activated hexafluorides for w-LEDs sponding standard diffraction card of K3 HfF7 . It can be clearly found
have been developed in detail.7–13 It is well known that Mn4+ ex- that these diffraction peaks of K3 HfF7 :Mn4+ perfectly meet with the
hibits red emission when it is located at the center of one regular or pure cubic K3 HfF7 (JCPDS No. 78-1827; space group of Fm-3 m;
disordered octahedron in fluorides. These fluoride hosts are usually
a = b = c = 8.97 Å). No extra diffraction peaks of the residual
of XF6 2− (X4+ = Si4+ , Ge4+ , or Ti4+ ) groups. Recently, Mn4+ ions
K2 MnF6 , residual KF and other impurities can be found. This result in-
in some hepta-fluorides (such as K3 ZrF7 , K2 NbF7 and K2 TaF7 ) also
dicates that Mn4+ can be introduced into the crystal lattices of K3 HfF7
exhibit excellent luminescent properties.14–16 Due to their disordered
to replace the crystal sites of Hf4+ , due to the same valence state and
structures for doping Mn4+ , intense zero phonon line (ZPL) can be ob-
similar ionic radius between Mn4+ and Hf4+ . The representative sur-
served in such red-emitting phosphors, which is beneficial to improve
face morphology and composition results of the K3 HfF7 :Mn4+ were
color-purity of such fluoride phosphors.
examined by SEM and EDX, as displayed in Fig. 1b. K3 HfF7 :Mn4+
In this work, a new red-emitting phosphor K3 HfF7 :Mn4+ was syn-
is composed of a number of irregular rod-like particles with clear
thesized by a cation exchange method. It exhibits intense red emission
edges and corner. This means that the sample has been well crystal-
under the blue light illumination. The fabricated warm w-LEDs with
lized. The length of particles is about 25 μm. The EDX spectrum of
K3 HfF7 :Mn4+ show better CCT and CRI values.
K3 HfF7 :Mn4+ shows the existence of K, Hf, K, and Mn elements,
and the absence of O element. Moreover, the content of Mn4+ in
Experimental K3 HfF7 :Mn4+ is about 9.6 mol% according to the EDX analysis.
The excitation and emission spectra of the K3 HfF7 :Mn4+ sample
All reagents were of analytical grade and used without fur-
are shown in Fig. 2. There are two excitation bands which are located
ther purification in this work. The commercial yellow phosphor
at ∼356 nm and ∼464 nm. Such bands are due to the transitions of
Y3 Al5 O12 :Ce3+ (YAG) was purchased from Shenzhen Quanjing pho-
Mn4+ from 4 A2g to 4 T1g and 4 T2g , this is in according with that of some
ton Co. Ltd, China. K2 MnF6 was synthesized according to our pre-
hexa-fluorides doped with Mn4+ .17,18 The excitation band at ∼464 nm
vious work.11 K3 HfF7 :Mn4+ was synthesized via a cation exchange
covers perfectly the emission of commercial GaN chip (∼460 nm), in-
method. Firstly, 2.7 ml HF (40%) solution was put into a plastic beaker,
dicating that K3 HfF7 :Mn4+ can be effectively excited by the emission
and 0.537 g HfO2 was added into the HF solution with magnetic stir-
of blue GaN-LED chip. Moreover, the diffuse reflectance spectrum
ring until completely dissolved. Then 0.041 g K2 MnF6 and 1.015 g KF
(DRS) of K3 HfF7 :Mn4+ exhibits two obvious absorption bands in the
were added into the above transparent solution with vigorous stirring.
UV and blue light regions. This result also proves that the phosphor
The obtained precipitates were collected and washed with acetic acid
is suitable for excitation by blue LED chip. K3 HfF7 :Mn4+ exhibits
and alcohol for two times. The finally products of K3 HfF7 :Mn4+ were
intense red emission with six groups of sharp peaks under 464 nm
dried at 60◦ C for 24 h. A series of LED devices were fabricated by
light excitation. These emission peaks at 608, 612, 620, 629, 633,
coating the obtained K3 HfF7 :Mn4+ on 460 nm GaN chips and tested
and 646 nm are ascribed to the transitions of anti-Stokes υ4 , υ6 , zero
under the 20 mA current.
phonon line (ZPL) and Stokes υ6 , υ4 and υ3 vibronic modes, respec-
The crystal structures of the as-prepared samples were character-
tively. As same as some hepta-fluoride red phosphors,14,15 intense
ized by powder X-ray diffraction (XRD D8 Advance, Bruker, Ger-
ZPL can be easily observed. This result shows Mn4+ occupies the
many) with Cu Kα radiation (λ = 0.15406 nm). The morphology
disordered center of polyhedron. The CIE chromaticity coordinates
and composition of the samples were observed using a scanning elec-
of this emission spectrum are calculated to be x = 0.689, y = 0.311,
tron microscope (SEM, FEI Quanta 200 Thermal FE Environment
indicating that K3 ZrF7 :Mn4+ can emit red light with high color purity.
scanning electron microscopy, America) equipped with an energy-
Fig. 3 is the temperature-dependent emission spectra of
dispersive X-ray spectrometer (EDX, Octane Pro, EDAX). The dif-
K3 HfF7 :Mn4+ upon 464 nm light excitation. All the emission spec-
tra exhibit similar shapes with six groups of emission peaks and the
z
E-mail: wangzhengliang@foxmail.com positions of their emission peaks have no obvious shift. However, the

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 R40 ECS Journal of Solid State Science and Technology, 7 (5) R39-R41 (2018)

(a) K3HfF7:Mn
4+ 700
4000
JCPDS card 78-1827 600 EX DRS
80
Intensity (a.u.)

Intensity (a.u.)
500

Reflectance(%)
EM
400 60
2000
300

200 40

0 100
20
10 20 30 40 50 60 70 0
300 400 500 600 700
2 theta (deg.)
Wavelength (nm)
(b) Figure 2. Excitation (λem = 629 nm), emission (λex = 464 nm) and diffuse
reflectance ultraviolet-visible spectra of K3 HfF7 :Mn4+ .

emission component from K3 HfF7 :Mn4+ appears in the EL spectrum

Intensity / a.u.

of the w-LED. The bright warm white light can be obtained from this
— 30 µm — warm w-LED with optimized CCT of 3535 K and CRI of 86.2.
Element wt% atom% Intensity
FK 25.93 57.74 78.58
KK 28.32 30.64 192.51
MnK 1.44 1.11 5.26
Conclusions
HfL 44.31 10.50 46.70
In conclusion, a new K3 HfF7 :Mn4+ phosphor prepared by the
cation exchange method at room temperature exhibits broad excitation
band in the blue region and sharp red emission with high color purity,
which can be used to optimize the optical performances of w-LED.
Hence, this red-emitting phosphor maybe find application to warm
0 2 4 6 8
w-LEDs.
E / keV
Figure 1. XRD pattern of K3 HfF7 :Mn4+ (a), EDX spectrum and SEM image Acknowledgment
of K3 HfF7 :Mn4+ (b). This work was financially supported by the National Natural Sci-
ence Foundation of China (21661033), the Applied Basic Research
emission intensity reduces gradually with an increase of temperature Project of Yunnan Province (2017FB017), research grant from the
from 20◦ C to 160◦ C. In order to further investigate the relationship Ministry of Education of Yunnan province (2017YJS057) and 2016
between the luminescence and the temperature, the thermal quenching Undergraduate Training Program for Innovation and Entrepreneurship
energy (Eq ) can be calculated via the following Arrhenius equation:16 of Yunnan Province.
I0
IT =   [1]
−E q
1 + A exp kT
Intensity (a.u.)

800 8000
o
20 C
o
where I0 and IT are the emission intensity of K3 HfF7 :Mn at room 4+ 40 C
700 o
60 C
temperature and at different given temperatures T, respectively. A is 4000
o
a constant and k is the Boltzmann constant (8.629 × 10−5 eV•K−1 ).
Intensity (a.u.)

80 C
600 o
Finally, Eq was calculated to be ∼0.60 ev, which is smaller than 0
100 C
o
that of some fluoride phosphors (such as ∼0.8 ev for Rb2 GeF6 :Mn4+ 500 0 20 40 60 80 100 120 140 160 180
120 C
o o
140 C
and BaTiF6 :Mn4+ ), but is larger than that of the Eu2+ red-emitting Temperature ( C)
400 o
phosphor values (Eq ∼ 0.3 ev or less) .16 160 C

A series of LED devices were fabricated based on GaN chips, and 300
their electro-luminescent (EL) spectra at 20 mA current excitation
are shown in Fig. 4. The EL spectrum of pink-emitting LED based 200
on K3 HfF7 :Mn4+ is composed of two parts which are located at the
blue light and red light region. The blue emission band is due to the 100
emission of GaN chip and the red emission peaks are due to the 2 Eg 0
→ 4 A2g transitions of K3 HfF7 :Mn4+ . This result indicates that the 575 600 625 650 675
K3 HfF7 :Mn4+ phosphor cannot only efficiently absorb the blue light
produced by the GaN but also remain a part of blue emission which Wavelength (nm)
can be absorbed by the yellow phosphor encapsulated into the w-LED.
Curve c is EL spectrum of w-LED based on YAG. The cold bright Figure 3. Temperature-dependent emission spectra of K3 HfF7 :Mn4+ upon
white light was observed from this w-LED with CCT of 6258 K and 464 nm light excitation. The inset shows the temperature-dependent emission
CRI of 77.4. With introducing of K3 HfF7 :Mn4+ red phosphor, the red intensity of K3 HfF7 :Mn4+ .

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 ECS Journal of Solid State Science and Technology, 7 (5) R39-R41 (2018) R41

Figure 4. EL spectra of LED chip (a), pink-emitting LED based on
K3 HfF7 :Mn4+ (b), w-LED based on YAG (c), and w-LED based on the mixture
YAG of and K3 HfF7 :Mn4+ (d) under 20 mA current.
ORCID
Zhengliang Wang https://orcid.org/0000-0002-5908-4427
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