Article

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

Optical Thermometry Based on Vibration Sidebands in

Y2MgTiO6:Mn4+ Double Perovskite
Peiqing Cai,† Lin Qin,† Cuili Chen,† Jing Wang,† Shala Bi,† Sun Il Kim,† Yanlin Huang,‡
and Hyo Jin Seo*,†
†
Department of Physics and Interdisciplinary Program of Biomedical, Mechanical and Electrical Engineering, Pukyong National
University, Busan 608-737, Republic of Korea
‡
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China

ABSTRACT: Mn4+-doped Y2MgTiO6 phosphors are synthesized by

the traditional solid-state method. Powder X-ray diffraction, scanning
electron microscope, and energy-dispersive X-ray spectrometer are
employed to characterize the samples. The Mn4+-doped Y2MgTiO6
phosphors show the far-red emission at ∼715 nm, which is assigned to
the 2Eg → 4A2 spin-forbidden transition of Mn4+. The temperature-
dependent luminescent dynamics of Mn4+ is described by a complete
model associated with electron−lattice interaction and spin−orbit
coupling. The noncontact optical thermometry of Y2MgTiO6:Mn4+ is
discussed based on the fluorescence intensity ratio of thermally
coupled anti-Stokes and Stokes sidebands of the efficient ∼715 nm
far-red emission in the temperature range of 10−513 K. The
maximum sensor sensitivity of Y2MgTiO6:Mn4+ is determined to be as
high as 0.001 42 K−1 at 153 K, which demonstrates potential
applications for the optical thermometry at low-temperature environments.

■ INTRODUCTION
Recently, the noncontact optical thermometry based on the
fluorescence intensity ratio (FIR) has been a matter of interest
due to the small size, good biological compatibility, high
sensitivity, and wide range of the temperature response in
different application areas.1−4 Until now, the candidates of the
universal optical sensing are the phosphors doped with
lanthanides, such as Tm3+, Pr3+, Ho3+, and Er3+,5−8 in which
the FIR is obtained by the peak emission from a pair of
thermally coupled states in up-conversion processes. However,
in the up-conversion process in the rare-earth doped
phosphors, the IR laser diode with high power is usually
necessary as a pumping source, because the luminescence
quantum efficiency (QE) of the up-conversion emission is low.9
As a result, the application of the lanthanide-doped optical
thermometry is restricted by the complicated experimental
setups of the IR system to characterize the optical temperature
behaviors of the samples and the heavy use of the costly rare-
earth. Hence, it is necessary to blaze new trails in discovering
the optical thermometry with low-cost, energy conservation,
and high sensitivity.
Currently, to overcome the weakness of the red range in
commercial white light-emitting diodes (LEDs; strategy:
InGaN blue chips combining with yellow YAG: Ce 3+
phosphors),10 several kinds of novel Mn4+-doped fluoride
phosphors have been developed, such as A2XF6 and BXF6,
where A = K, Na, Cs, and Rb, B = Ba and Zn, and X = Ti, Si,
Ge, and Zr.11−17 These Mn4+-doped fluoride phosphors exhibit
the effective red emission in the range of 600−650 nm under
near-UV and blue LED excitations. However, the Mn4+-
activated fluoride phosphors are unstable at high temperature
and harmful to the environment during the material
preparation due to the heavy use of HF,18−21 which restricts
the practical application of these phosphors. In contrast, the
Mn4+-activated oxide compounds are environmentally friendly
during the preparation procedure. Currently, several Mn4+-
activated double perovskites have been discovered and applied
to plant cultivation and illumination, such as Mn4+-doped
Ba2LaNbO6,22 La2MgTiO6,23 Gd2ZnTiO6,24 and Gd2Mg-
TiO6.25 Nevertheless, the significant thermal quenching
property and near-infrared emission (>650 nm) of Mn4+-
doped double perovskites indicate that this kind of material is
not suitable for use in LED phosphors but can be employed as
optical thermometry sensors.26 The A2BB′O6-type double
perovskite is flexible and adjustable by crystal structure
engineering. The luminescence properties of luminescent ions
are strongly influenced by the surrounding environmental
factors such as B site cation ordering, octahedral distorting and
tilting, etc. The sensor sensitivity of FIR-based optical
thermometry can be easily adjustable by changing the crystal
field of the double perovskite. More recently, the Mn4+-
activated oxyfluoride Cs2WO2F427 was introduced as an optical
thermometry, but the synthetic route is also harmful, and the
Received: November 20, 2017

© XXXX American Chemical Society A DOI: 10.1021/acs.inorgchem.7b02938

Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry Article

sample is toxic. To investigate the materials with outstanding

sensing features, the novel material exploitation is still going on.
In this work, a comprehensive research is made on the Mn4+-
doped Y2MgTiO6 synthesized by conventional solid-state
reaction at 1400 °C. The samples are characterized by X-ray
diffraction (XRD) and refined by the Rietveld refinement
method. The surface properties are studied in detail. The
luminescence properties are investigated by excitation and
emission spectra and decay curves at various temperatures. The
luminescence characteristics are discussed on the basis of
crystal field analysis. Finally, the Mn4+-doped Y2MgTiO6
phosphor as an optical thermometry based on the FIR
technique is discussed to evaluate the temperature-sensing
properties of the perovskite-type ceramics.

■ EXPERIMENTAL SECTION
Preparations. A series of Y2MgTO6:x%Mn4+ (x = 0−1) phosphors
were synthesized by the conventional high-temperature solid-state
reaction method. The starting materials Y2O3 (99.9%), MgO (99.9%),
TiO2 (99.9%), and MnO2 (99.9%) were weighed according to the
stoichiometric ratio with 2 wt % excess H2BO3 as a flux. The mixed
powders were thoroughly ground with a small quantity of ethanol in
an agate mortar for 20 min, prefired at 1000 °C for 8 h, reground for
20 min, pressed to a certain thickness with a manual pill tablet press,
and sintered at 1400 °C for 24 h in ambient atmosphere. After the
furnace cooled to room temperature, the products were fully ground
again to obtain the resulting phosphor powders.
Characterization. The phase of the Y2MgTiO6:Mn4+ powders was
identified by using an X-ray Rigaku D/Max diffractometer operating at
40 kV and 30 mA and equipped by Cu Kα radiation (λ = 1.5405 Å).
The Rietveld refinement of the XRD data was performed with the
General Structure Analysis System (GSAS) software.28 The scanning Figure 1. (a) The Rietveld refinement fit of the XRD patterns of
rate used for the Rietveld analysis was 8 s per step with a step size of Y2MgTiO6:0.2%Mn4+ by using the GSAS program. (b) Crystal
0.02°. The microstructures and elementary compositions were structure of the Y2MgTiO6:0.2%Mn4+ double perovskite.
observed by a scanning electron microscope (SEM) FEI Quanta 400
attached at an S-2700 energy-dispersive X-ray spectrometer (EDS). Table 1. Refined Atomic Coordinate Parameters Data of
Diffuse reflection spectra were taken on a Cary 5000 UV−Vis−NIR
spectrophotometer with BaSO4 powders as a standard reference. The
Y2MgTiO6:0.2%Mn4+ at Room Temperature
samples were cooled in a closed-cycle helium cryostat in the space group: P21/n (No. 14): a = 5.292 Å, b = 5.584 Å, c = 7.614 Å, β = 90.26°
temperature range of 7−300 K. A homemade temperature control
system was introduced to take measurement at temperatures above atom site x y z occupancy Uiso (Å2)
300 K. Excitation and emission spectra were recorded using a 450 W Y 4e 0.5148 0.5664 0.2486 1 0.0042(7)
Xe lamp dispersed by the 25 cm monochromator (Acton Research Mg 2c 0.0000 0.5000 0.0000 1 0.0021(1)
Corp. Pro-250). For decay measurements, the luminescence signal was Ti 2d 0.5000 0.0000 0.0000 1 0.0023(1)
digitized and saved by means of a 500 MHz Tektronix DPO 3054 O1 4e 0.1838 0.2036 −0.0610 1 0.0038(2)
oscilloscope. The excitation source for luminescence decays was a 355 O2 4e 0.3009 0.6924 −0.0531 1 0.0012(6)
nm pulsed laser with a pulse width of 5 ns and a repetition rate of 10
O3 4e 0.3891 −0.0369 0.2553 1 0.0016(9)
Hz (Spectron Laser Sys. SL802G) in which the luminescence was
dispersed by a 75 cm monochromator (Acton Research Corp. Pro- Rwp = 11.44%, Rp = 8.96, χ2=1.694, vol = 225.027 Å3
750) and observed with a photomultiplier tube (PMT; Hamamatsu
R928).

■
RESULTS AND DISCUSSION
Phase Formation and Structure Characteristics. The
representative 0.2%Mn4+-doped Y2MgTiO6 sample was verified
by the powder X-ray diffraction (XRD), and the XRD data were
analyzed by the Rietveld refinement technique as shown in
Figure 1a. Because of the lack of the structural information on
Y2MgTiO6 in the crystallographic database, the reported
crystallographic data of Dy2MgTiO6 with analogous structure29
was adopted as the initial structure model. Table 1 lists the
refined structural parameters of Y2MgTiO6. The XRD patterns
of Y2MgTiO6:0.2%Mn4+ are indexed to the crystal structure
with a monoclinic unit cell with cell parameters a = 5.292 Å, b =
5.584 Å, c = 7.614 Å, and β = 90.26°, indicating a double
perovskite structure with P21/n space group.30 The antisite
B DOI: 10.1021/acs.inorgchem.7b02938
disorder usually occurs when the transition-metal cations
occupy the Wyckoff position 2c (B2+ site) and 2d (B′4+ site)
interchangeably and influence significantly the ferromagnetic
property of the A2BB′X6 double perovskite.31−33 Although
perfect order is seldom achieved in as-prepared samples, the
charge exchange interaction might be barely effective between
Mg2+ and Ti4+ in nearly ordered rock-salt type Y2MgTiO6
double perovskite. The superlattice diffraction peaks at 19.70°
and 20.45° also indicate a rock-salt type cation ordering of
Mg2+ and Ti4+.29,34 The deeper investigation of the existence of
antisite disorder in B/B′ sites could be done by neutron
diffraction method in further work.
Figure 1b displays the schematic illustration of the
monoclinic Y2MgTiO6 structure. The Ti4+ and Mg2+ ions
form the alternative arrangement of TiO6 and MgO6 octahedra
in two interleaved face-centered cubic (fcc) sublattices. The Y3+
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Inorganic Chemistry Article

Figure 2. (a) EDS spectrum of Y2MgTiO6:0.2%Mn4+ double perovskite. Elemental mapping of (b) Y, (c) Mg, (d) Ti, (e) O, and (f) integration of
(b−e). (g) SEM image of Y2MgTiO6:0.2%Mn4+, (h) high-resolution XPS spectrum of Mn4+ in Y2MgTiO6:1%Mn4+.

ions occupy the cavities constructed by the tilted TiO6 and of the Mn4+ ions in the host, the XPS spectrum for the valence
MgO6 octahedra, which are linked through the corners. In the state of manganese in Y2MgTiO6 was recorded. As shown in
Y2MgTiO6 host matrix, the Mn4+ ions may not substitute for Figure 2h, the two weak peaks are assigned to 2P1/2 and 2P3/2 of
the Y3+ ions due to the large difference in ionic radii between the Mn4+ ions,37 indicating the presence of Mn4+ ions in the
Y3+ (1.08 Å) and Mn4+ (0.53 Å). However, there is an host.
opportunity for the Mn4+ ions to occupy simultaneously the Luminescence Properties of Y2MgTiO6:Mn4+. The
Ti4+ and Mg2+ sites. In some hosts such as MgO35 and diffuse reflection spectra (DRS) of the Y2MgTiO6:x%Mn4+ (x
SrTiO3,36 the Mn4+ ions could perform as luminescent centers. = 0−0.8) phosphors are shown in Figure 3. Three relevant
Zhou et al.23 calculated the formation energy to estimate the absorption bands are observed in the spectra. Two obvious
possibility of the Mn4+ ions to enter the Ti4+ or Mg2+ sites. The stronger bands due to the spin-allowed transitions peaking at
results show that the formation energy of the Mn−Ti mutual ∼350 and 500 nm correspond to the 4A2 → 4T1 transition and
replacement is lower than the substitution of Mg2+ by Mn4+.
Moreover, considering the identical ionic valence (4+) and the
closer ionic radius of Ti4+ (0.604 Å for Ti4+ and 0.72 Å for
Mg2+), it is reasonable that the Mn4+ (r = 0.53 Å) ion is more
stable in the Ti4+ site.
The EDS scanning spectra in Figure 2a−f displays the
element compositions of the as-prepared Y2MgTiO6:0.2%Mn4+.
The different color spots over the dark background represent
the uniform distribution of the relative elements on the external
surface of the particles. The result in the element analysis shows
that the atomic ratios of Y, Mg, Ti, and O are 21.2, 8.40, 11.2,
and 59.2%, respectively, which corresponds approximately to
the stoichiometric content of Y2MgTiO6:0.2%Mn4+. Figure 2g
shows a typical granular morphology of Y2MgTiO6 with the size
distribution in the range of 4−8 μm. The content of the Mn
element cannot be detected by the EDS analysis due to the low
doping level (∼1%). Generally, the content of Mn element
should be consistent with the stoichiometric ratio of the initial
weighing process, due to the Mn element is not easy to Figure 3. DRS of Y2MgTiO6:x%Mn4+ (x = 0, 0.05, 0.2, 0.8) samples at
volatilize at the sintering temperature. To confirm the existence room temperature.

C DOI: 10.1021/acs.inorgchem.7b02938
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Inorganic Chemistry
the 4A2 → 4T2 transition of Mn4+, respectively. Another weak
distinguishable band located at ∼420 nm is assigned to the
spin-forbidden Mn4+: 4A2 → 2T2 transition.38 In addition, the
band of the Mn4+: 4A2 → 4T1 transition overlaps partially with
the band of the Mn4+−O2− charge transfer (CT) transition in
the range of 300−400 nm. Figure 4a,b shows the room-
Figure 4. (a) Room-temperature excitation spectra of Y2MgTiO6:x%
Mn4+ (x = 0−1) obtained by monitoring the 698 nm emission of the
2
Eg → 4A2 transition. (b) Room-temperature emission spectra of
Y2MgTiO6:x%Mn4+ (x = 0−1) under the 365 nm excitation.
temperature excitation and emission spectra of the
Y2MgTiO6:Mn4+, respectively. The excitation spectra exhibit
the broad band absorption in the near-UV and blue-green
spectral regions from 250 to 600 nm, which is well-consistent
to the DRS spectra. An obvious red shift could be identified in
the range of CT band with increasing Mn4+ concentration,
which is similar to that observed for Gd2ZnTiO6:Mn4+.24
Moreover, the two dips located at 477.7 and 489.3 nm in the
excitation band of the 4A2 → 4T2 transition should be noticed.
The shapes of these dips seem to be caused by the reduction of
peak absorption suggested as “Fano-Antiresonances”. This
could be interpreted in terms of an interaction of the 2E and
2
T1 states with the vibrationally broadened 4T2 state.39,40
Figure 4b shows the emission spectra of the spin-forbidden
2
Eg → 4A2 transition of Y2MgTiO6:Mn4+ as functions of the
D DOI: 10.1021/acs.inorgchem.7b02938
Article
Mn4+ concentration. All the specific bands of the emission
spectra in the range of 620−740 nm consist of several peaks
with the maxima at 698 nm. The emission peaks are assigned to
the vibronic sidebands and zero phonon line (ZPL) at 676
nm,27 originating from the nature of the parity-forbidden d−d
transitions.41 Theoretically, the pure electronic 2Eg → 4A2
transition is both spin- and parity-forbidden; however, the 2Eg
→ 4A2 electric dipole transition can take place when the odd
parity 4T2u and 4T1u states mix the even-parity d wave function
of the 2Eg state.42 As a result, the selection rules are broken, and
effective emission intensities are obtained from the 2Eg state
(ZPL) and the phonon-associated sidebands with energies
shifted from the ZPL to both high energy side (anti-Stokes
sideband) and low-energy side (Stokes sideband) by the energy
values of the relevant phonons. The emission intensity is
significantly influenced by the Mn4+ concentration. No peak
shift is observed with increasing Mn4+ concentration indicating
the effect of the Mn4+ concentration on the crystal structure
could be neglected. According to Figure 5a, the emission
Figure 5. (a) Integrated emission intensity of Y2MgTiO6:Mn4+ as a
function of Mn4+ concentration. (b) Relation of log(I/xMn4+) and
log(xMn4+) for the 2Eg → 4A2 transition of Mn4+.
intensity increases and then quenches beyond 0.2% with
increasing Mn4+ concentration. The energy-transfer mechanism
of the concentration quenching belongs to the exchange
interaction or multipolar−multipolar interaction.37 A rough
critical distance (Rc) is introduced to estimate the energy-
transfer process between two nearest Mn4+ ions. The equation
is given by Blasse:43 Rc ≈ 2(3V/4πxcN)1/3, where V is the
volume of the unit cell, xc is the critical concentration of
activator ions, and N is the number of lattice sites in the unit
cell. Referring to the structural data obtained by the refinement
V = 225.02 Å3, N = 2, and xc = 0.002, Rc is calculated to be
47.53 Å. The calculated value is longer than 5 Å; as a result, the
electric multipolar−multipolar interaction should be suitable
for the energy-transfer mechanism of the concentration
quenching process. In addition, according to the Dexter’s
theory,44 the multipolar interaction between Mn4+ can be
reflected by the following equation:
I /x = K[1 + β(x)θ /3 ]−1 (1)
where x is the activator concentration, K and β are constants, I
represents the emission intensity, θ is an electric multipole
index with θ = 6, 8, and 10 corresponding to the dipole−dipole
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
(d-d), dipole−quadrupole (d-q), and quadrupole−quadrupole
(q-q) interactions, respectively. In Figure 5b, the relationship
between log(x) and log(I/x) appears to be fitted well as linear
with a slope of −(θ/3) ≈ −1.21, and the value of θ is nearly 6,
indicating that the quenching mechanism is due to d-d
interactions among Mn4+ ions.
The spectroscopic properties of the Mn4+ ions depend
strongly on the surroundings of Mn4+ in an octahedral
environment in solids. The well-known Tanabe−Sugano
diagram (Figure 6a) could be used to explain the splitting of
Figure 6. (a) Tanabe−Sugano diagram of a 3d3 system in an
octahedral crystal field of Mn4+. (b) Schematic configuration
coordinate diagram for Mn4+ ions in the Y2MgTiO6 double perovskite
host.
the energy level of Mn4+ in an ideal octahedral crystal field. The
crystal-field strength (10Dq) is determined by the peak energy
of the 4A2 → 4T2 transition:45
4 4
Dq = E( A 2 − T2)/10 (2)
On the basis of the energy difference between the A2 → T2
4 4
and 4A2 → 4T1 transitions in the excitation spectra, the Racah
parameter B can be evaluated by the following equation:46
E DOI: 10.1021/acs.inorgchem.7b02938
Article
Dq 15(x − 8)
=
B (x 2 − 10x) (3)
where parameter x is defined as
E(4A 2 − 4 T1) − E(4A 2 − 4 T2)
x=
Dq (4)
From the peak energy of the 2Eg → 4A2 transition derived
from the emission spectra, the Racah parameter C can be
calculated by the expression
E(2 E g − 4A 2)/B = 3.05C /B + 7.9 − 1.8B /Dq (5)
According the above equations, the crystal field parameters of
Dq, B, and C are calculated to be 2070, 724, and 3123 cm−1,
respectively. As shown in Figure 6a, the 2E and 4T2 levels have a
crossover point at Dq/B ≈ 2.3 in the energy-level diagram;
above or below this value means the 3d3 transition-metal ions
are in weak crystal field or strong crystal field, respectively.46 In
our case, the value of Dq/B is calculated to be ∼2.9, indicating
the Mn4+ ions in the Y2MgTiO6 host matrix is located at the
strong crystal field. The value (2.9) of Dq/B is comparable to
those in fluoride Na2SiF6:Mn4+ (Dq/B ≈ 2.8)13 and perovskite
LaAlO3:Mn4+ (Dq/B ≈ 3.0).47
The luminescence decay curves as functions of temperature
are presented in Figure 7a. The decays are slightly
nonexponential and become shorter with increasing temper-
ature. The total kinetic processes could be characterized by the
average decay time (τ), which can be calculated as
∫ tI(t )dt
τavg =
∫ I(t )dt (6)
where I is the intensity at time t, t is the time, and τavg is the
average decay time. The calculated τavg as a function of
temperature is depicted in Figure 7b. Wu48 and Grinberg49 et
al. discussed the spin−orbit interaction with the odd-parity
vibration in the 3d3 system and proposed a complete model to
describe the luminescent dynamics of Mn4+ at different
temperatures. The temperature-dependent decay times in
Figure 7b can be fitted by the following equation:
ℏω
τE =
(
1 + exp − kT ) + 3exp(− kTΔ )
2⎡ ℏω ⎤
τ {( Δ ′ ) ⎣
1 + p′exp(− kT )⎦ + 3exp(− kT )}
1 W S−O Δ
T
(7)
where τE is the decay time of the 2E → 4A2 emission, WS−O is
the spin−orbit coupling quantity, τT−1 is the radiative transition
probability of the 4T2 → 4A2 emission, and ℏω is the effective
energy of phonons. Δ′ is the energy difference between the 2E
and 4T2 excited levels, and Δ is the energy difference between
the minimum energy of the 2E and 4T2 states, which could be
identified and calculated from the excitation and emission
spectra (4A2 → 4T2 and 2E → 4A2) as shown in Figure 6b.
Another process is a radiative transition τanti−1, which is
associated with the anti-Stokes sideband and related with τT as
|W |2
the following equation: τanti−1 ≈ τT−1 (ΔS−′O)2 p′, where p′ is a free
parameter related with anti-Stokes sideband. Detail derivation
process is shown in ref 49. In our case, Δ′ = 5846 cm−1 and Δ
= 2400 cm−1, and the fitting parameters are ℏω = 225 cm−1, τT
= 0.609 μs, WS−O = 87.8 cm−1, τanti = 0.69 ms, and p′ = 3.9.
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Inorganic Chemistry
Figure 7. (a) Temperature-dependent decay curves of the 698 nm
emission in Y2MgTiO6:0.2%Mn4+ under the 355 nm pulsed YAG:Nd
laser. (b) Calculated decay times of Y2MgTiO6:0.2%Mn4+ as a function
of temperature, the red solid line represents the fitting curve.
The results show that the value of ℏω in this work is close to
that in Cr3+-doped LiTaO3 (200 cm−1),50 which belongs to the
analogous perovskite structure. The calculated radiative lifetime
(τT = 0.609 μs) is shorter than that in Rb2GeF6:Mn4+ (1.15 μs),
indicating a little faster radiative transition of 4A2 → 4T2 in the
Mn4+-doped oxide compounds.48 The spin−orbit coupling
constant WS−O (87.8 cm−1) is induced by the perturbation
approach, and the value is comparable to that in Cr3+-doped
Garnets (105 cm−1).51 The obtained value of τanti (0.69 ms)
represents the nature of spin- and parity-forbidden 2E → 4A2
transition with a millisecond scale. The value of parameter p′
(3.9) means that the contribution of the probability of the
radiative transition induced by anti-Stokes phonon is ∼4 times
larger than that caused by static crystal field for the 2E → 4A2
radiative transition probability.27,49
Application of Y2MgTiO6:Mn4+ in Optical Temper-
ature Sensing. Generally, the transition-metal (3d3) ions of
Mn4+ are strongly susceptible to the temperature because of the
unshielded 3d electrons. As shown in Figure 8a, the total
emission intensity (Itotal) of Y2MgTiO6:0.2%Mn4+ increases first
and then decreases with increasing temperature. Such a trend in
the sharp intensity change indicates that the Y2MgTiO6:Mn4+
phosphor is suitable for the optical temperature sensing. Figure
F DOI: 10.1021/acs.inorgchem.7b02938
Article
Figure 8. (a) Integrated emission intensity of Ianti‑S (620−673 nm), IS
(673−760), and Itotal (620−760 nm) as a function of temperature. (b)
Normalized temperature-dependent emission spectra of
Y2MgTiO6:0.2%Mn4+ under the 355 nm excitation.
8b depicts normalized emission spectra as functions of
temperature from 10 to 513 K. The strongest peak position
of each curve is located at the region of Stokes sideband. The
anti-Stokes sideband represents the continual increase in
intensity in the normalized emission spectra. The thermal
equilibrium usually exists in some trivalent rare-earth ions with
adjacent energy gap in the range of 100−2000 cm−1.52 The
intensity ratio of the anti-Stokes sideband and the Stokes
sideband should obey the Boltzmann’s law, because the
phonon-coupled sidebands can be considered as a couple of
adjacent levels (∼600 cm−1). When the temperature increases,
the anti-Stokes sideband (upper levels) can be thermally
depopulated from the Stokes sideband (lower levels) to reach
thermal equilibrium; as a result, the intensity of the anti-Stokes
sideband elevates with increasing temperature. The relationship
between the integrated intensity of the anti-Stokes sideband
(Ianti‑S: 620−673 nm) and the Stokes sideband (IS: 673−760
nm) has the following formula:
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Inorganic Chemistry Article

Figure 9. (a) FIR between Ianti‑S and IS as a function of temperature. (b) Calculated relative sensitivity SR at different temperatures.

Ianti − S g σ2ω2 ⎛ ΔE ⎞ that the Y2MgTiO6:0.2%Mn4+ has a wide and effective

FIR = ≈ 2 exp⎜ − ⎟ + B
IS g1σ1ω1 ⎝ kT ⎠ temperature sensing range from 10 to 513 K with the highest
sensitivity at 153 K. When compared with the toxic
⎛ ΔE ⎞ Cs2WO2F4:Mn4+ (0.0021 K−1 at 167 K) of our previous
= A exp⎜ − ⎟ + B
⎝ kT ⎠ (8) work,27 the Y2MgTiO6:Mn4+ is a fluoride-free material and
more environmentally friendly. Similar compound such as Pr-
where Ianti‑S and IS are the luminescence intensities originated doped La2MgTiO6 exhibits much better efficiency of the
from upper and lower thermally coupled states, respectively. g, sensitivity at higher temperatures (0.072 K−1 at 450 K);53
σ, and ω are the degeneracy, the emission cross section, and the however, we use Mn element instead of the costly Pr element
angular frequency of luminescence transitions, respectively. A is as the activator, indicating the advantage in economy.

the proportional parameter, k is the Boltzmann constant, ΔE is
the energy gap between the two coupled states, and B is an
offset parameter.54 As shown in Figure 9a, the fit result of the
experimental data is well-consistent with the theory with the
parameters A = 0.81, B = 0.02, and ΔE = 211 cm−1. The rate of
change of the luminescence intensity ratio with temperature
(dFIR/dT), named as temperature sensitivity (SR), is important
to evaluate the suitability for thermometry and is given by
dFIR ⎛ −ΔE ⎞⎛ ΔE ⎞
SR = = A exp⎜ ⎟⎜ ⎟
dT ⎝ kT ⎠⎝ kT 2 ⎠
The simulated results are displayed in Figure 9b. The
sensitivity increases with increasing temperature and reaches
the maximum at 153 K with 0.001 42 K−1; with further increase
in temperature, the sensitivity decreases. The results indicate
■
CONCLUSION
The Mn4+-doped Y2MgTiO6 phosphors were synthesized by a
conventional high-temperature solid-state reaction method.
Rietveld refinement method was performed to confirm the
crystal structure. We deem that the credible crystal structure of
Y2MgTiO6 is monoclinic double perovskite with space group
P21/n. The excitation and emission spectra of Y2MgTiO6:Mn4+
illustrate wide absorption in the near-UV and blue light regions
(9) and exhibited deep red 2 E g → 4 A 2 emission. The
Y2MgTiO6:Mn4+ phosphor with strong thermal quenching
property has great potential as the optical thermometry with
high thermal stability under UV excitation. The highest relative
temperature sensitivity SR was calculated to be 0.001 42 K−1 at
153 K. Results exhibit that the commercial UV chips fabricated
G DOI: 10.1021/acs.inorgchem.7b02938
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
Y2MgTiO6:Mn4+ is a potential noncontact optical thermometry
in cryogenic industry.
■
AUTHOR INFORMATION
Corresponding Author
*Phone: +82 51 629 5568. Fax: +82 51 629 5549. E-mail:
hjseo@pknu.ac.kr.
ORCID
Hyo Jin Seo: 0000-0002-0490-8484
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This research was supported by Basic Science Research
Program through the National Research Foundation of Korea
funded by the Ministry of Education
(2017R1D1A1B03029432).
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I DOI: 10.1021/acs.inorgchem.7b02938
Inorg. Chem. XXXX, XXX, XXX−XXX