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Adjustment of Bi3+ Luminescence and Thermal Quenching

Properties by B′-Site Ion Substitution Strategy in Double Perovskite
CaLaMgSb/TaO6:Bi3+ Phosphor
Ran Xiao, Ning Guo,* Chengzheng Jia, Qincan Ma, Ruoting Liu, and Ruizhuo Ouyang
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ABSTRACT: Thermal quenching has always been one of the

most difficult issues in creating high-quality phosphor conversion
light-emitting diodes (pc-LED), and a family of strategies are
urgently needed to improve the luminescence performance of
phosphors at high temperatures. In this contribution, a novel B′-
site substitution CaLaMgSbxTa1−xO6:Bi3+ phosphor was con-
structed using an ion substitution strategy in the matrix with a
green activator Bi3+ and a novel double perovskite material. When
Sb5+ replaces Ta5+, a surprising increase in luminescence intensity
occurs and the thermal quenching properties are greatly improved.
The shift of the Raman characteristic peak to a smaller
wavenumber and the reduction of the Bi−O bond length confirm
that the crystal field environment around Bi3+ changes, which has a
substantial effect on the crystal field splitting and nepheline effect of Bi3+ ions, affecting the crystal field splitting energy (Dq). This
results in a corresponding increase of the band gap and the thermal quenching activation energy (ΔE) of the activator Bi3+. From the
perspective of Dq, the intrinsic relationships among the activator ion band gap, bond length, and Raman characteristic peak changes
were analyzed, and a mechanism for regulating luminescence thermal quenching properties was constructed, which provides an
effective strategy for improving the promising new materials such as double perovskite.

1. INTRODUCTION and the thermal stability of SrxCa1−xAlSiN3:Eu2+ was improved

The usage of phosphor-converted light-emitting diodes (pc- by about 10% at 200 °C. The Na3GaxAl1−xF6:Cr3+ NIR
phosphor was investigated by Yang et al.21 Adjusting the
LEDs) in electrical gadgets, security systems, backlit displays,
crystal field strength by Ga/Al substitution can modulate the
and solid-state lighting has sparked a lot of exploration in
thermal stability and is 95% of the initial intensity at 150 °C.
recent years.1−8 Yet, one of the key obstacles preventing the
The thermal quenching resistance of the cyan-emitting
widespread usage of phosphors is thermal quenching brought
Ba2(Zn/Mg)Ge2O7:Bi3+ phosphor was reported by Wei et
on by nonradiative relaxation. Most of the current studies have
al.22 The artificial creation of zinc and oxygen vacancy defects
focused on developing the thermal quenching resistance of rare
by ion substitution resulted in combined emission intensities of
earth activated phosphors, but substrates with great thermal
138, 148, and 134% at 150, 200, and 250 °C, respectively. By
stability and superior structural rigidity are still rare, so a series
substituting Al for Sc, Xia et al.23 increased the structural
of strategies are urgently needed to improve the luminescence
rigidity and local symmetry of Cr3+ and suppressed its
of phosphors at high temperatures.9−13 Combined with
nonradiative relaxation. Nevertheless, due to the diversity of
previous studies, ion substitution strategy (homo- or
activator ions and their various luminescent thermal quenching
heterovalent) in the matrix is an effective strategy, and the behaviors in different lattice environments, there is still no
radius, charge, and electronegativity of matrix cations regular and ideal scheme to achieve the accurate regulation of
significantly influence the luminescence characteristics of phosphor luminescent thermal quenching behaviors. By
activator ions, although previous researchers have used ion
substitution to modulate the luminescent thermal quenching
properties of some phosphors.14−18 For example, Kim et al.19 Received: March 24, 2023
constructed Lu3−xCaxAl2−2xMg2xAl3−3xSi3xO12:Ce3+ solid sol- Published: May 26, 2023
utions with Ba2+-substituted Ca2+/Mg2+ sites. The thermal
stability was significantly improved (95% of the initial strength
at 150 °C). Tsai et al.20 reduced the intensity of crystal field
splitting in CaAlSiN3:Eu2+ by replacing Ca2+ with Sr2+ cations,

© 2023 American Chemical Society https://doi.org/10.1021/acs.inorgchem.3c00964

9120 Inorg. Chem. 2023, 62, 9120−9129
Inorganic Chemistry
Figure 1. (a) Crystal structure unit of CaLaMgSb/TaO6:Bi3+. (b) XRD spectrum of CaLa0.99MgSbxTa1−xO6:0.01Bi3+ (x = 0, 0.25, 0.5, 0.75, 1.0).
(c) Rietveld refinement patterns for X-ray diffraction patterns of CaLaMgTaO6:Bi3+. (d) Variation of lattice parameters of CaLaMgSb/TaO6:Bi3+.
investigating the main factors influencing the luminescent
thermal quenching of different activator ion-doped fluorescent
materials and constructing a mechanism to regulate their
luminescent thermal quenching performance, it takes urgent
significance to explore innovative and high-quality phosphors
for LED applications.
As a possible substitute for halide perovskite, double
perovskite oxides with good structural rigidity and chemical
stability, such as AA′BB′O6 and other general types, have been
reported by many researchers.24−28 Among them, ion
substitution strategies have been undertaken by previous
researchers to study the substitution of various sites of double
perovskite, e.g., Ca2BB′O6 (B = Y, Gd, La; B′ = Sb, Nb);29
(Ca,Sr) 2 InNbO 6 :Mn 4+ ; 24 BaLaCa 1−x Mg x SbO 6 :Mn 4+ ; 25
Ca2Gd0.5Nb1−xW5x/6O6:0.5Eu3+;30 BaLaMg(Sb,Nb)O6:Eu3+,31
etc. The most novel research approach is to use B′ site
substitution to improve the luminescence properties of double
perovskite. Currently, CaLaMgTaO6 and CaLaMgSbO6 are an
excellent luminescent host materials. Due to their better
chemical stability, strong and wide charge-transfer band (CTB)
in the NUV-blue region has seen some studies,32−34 but the
study of its thermal stability has been limited by severe thermal
quenching and no breakthrough has been made. For example,
the CaLaMgTaO6:Bi3+ system reported presents a fast
quenching trend with increasing temperature,32,35 and the
equivalent BaLaCa1−xMgxSbO6:Mn4+ system shows basically
complete quenching at 473 K.25 Therefore, it is significant to
explore the thermal quenching and tuning mechanism of
double perovskite.
Considering the similar crystal structure of CaLaMgSbO6
and CaLaMgTaO6, and the similar ionic radius between Sb5+
and Ta5+, a novel B′-site substitution double perovskite
structure antimony-tantalate CaLaMgSbxTa1−xO6 (x = 0,
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0.25, 0.5, 0.75, 1) luminescent substrate material was
constructed in this work and doped with 1 mol % Bi3+ as an
activator ion. Among the common activator ions, bismuth ion
is a highly potential activator ion as a substitute for rare earth
elements in luminescent materials with the advantages of
green, environmental protection.36−41 As the luminescence
properties of the 6s electrons of Bi3+ are extremely sensitive to
the surrounding local crystal field environment,42,43 employing
a B′ ion substitution strategy to modify the chemical
environment around Bi3+ might result in significant effects
on its emission excitation band position and thermal stability.
When Ta5+ is replaced by Sb5+, the octahedron in the double
perovskite crystal structure tilts and the bond length between
the activator and the ligand changes, which effectively proves
that the local crystal field environment of the crystal changes.
The regular changes of band-gap value Eg and thermal
quenching activation energy ΔE significantly improve the
luminescence intensity and thermal quenching performance of
Bi3+. The internal relationship between the changes of activator
ion band gap and the microscopic environment was analyzed
from the perspective of Dq to realize the regulation of
luminescence thermal quenching of phosphors and construct
the mechanism of regulating luminescence thermal quenching
performance. It provides an effective strategy for improving
promising new materials such as double perovskite.
2. EXPERIMENTAL SECTION
2.1. Preparation Method. CaLa0.99MgSbxTa1−xO6:0.01Bi3+ (x =
0, 0.25, 0.5, 0.75, 1) phosphors were obtained by high-temperature
solid-phase method. The raw materials CaCO3 (AR 99%), La2O3 (AR
99.9%), 4MgCO3·Mg(OH)2·5H2O (AR 99%), Ta2O5 (AR 99.99%),
Sb2O3 (AR 99.5%), and Bi2O3 (AR 99.99%) were added according to
the stoichiometric ratios, and 1 mol % was added as a flux Li2CO3
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Inorganic Chemistry
Figure 2. (a) Typical SEM image of CaLaMgSb0.5Ta0.5O6:Bi3+. (b) Elemental mapping of CaLaMgSb0.5Ta0.5O6:Bi3+. (c) EDS energy spectrum of
CaLaMgSb0.5Ta0.5O6:Bi3,+ with the inset showing the relative elemental content.
(AR 99.99%) was quantitatively weighed. After full grinding in an
agate mortar for 30 min, the mixed powder was transferred to an
alumina crucible and heated to 450 °C at a rate of 10 °C/min in an air
atmosphere. After constant temperature for 20 min, the powder was
heated to 1450 °C at the same rate and calcinated at the same
temperature for 4 h. It was subsequently cooled to 500 °C at a cooling
rate of 10 °C/min and then cooled to room temperature naturally.
The calcination was repeated once with the same procedure, and the
powder was ground again for 30 min for subsequent characterization.
2.2. Characterization Method. Scanning electron microscopy
(SEM, Zeiss Sigma 300) and energy-dispersive X-ray spectrometry
(EDS, Oxford Xplore 30) were used for morphology and elemental
mapping. X-ray photoelectron spectroscopy (XPS) was performed on
a Thermo Scientific K-Alpha with Al Kα rays (1486.6 eV) as the
excitation source. In addition, detailed instrument information and
parameters used for XRD testing, Rietveld refinement, UV−visible
diffuse reflectance spectroscopy, Raman spectroscopy, excitation and
emission spectra, and temperature-dependent spectroscopy could be
referred to in the previous work.16
3. RESULTS AND DISCUSSION
3.1. Phase and Structure Analysis. CaLaMgSb/TaO6, as
shown in Figure 1a, has a typical AA′BB′O6 double perovskite
structure and belongs to the P21/n-monoclinic space group.
Among them, Mg and Sb/Ta connect six O atoms to form an
octahedron [MgO6] and [Sb/TaO6], which are arranged
alternately by O atoms on a shared corner. Ca and La are
randomly distributed at the 4e-position in a 1:1 ratio, located
in the gap of the cross-connected octahedra, and are
coordinated with eight atoms to form a [Ca/LaO 8 ]
polyhedron. Considering the charge balance corresponding
and similar ionic radius matching (r[Bi3+] = 1.17 Å, CN = 8;
r[La3+] = 1.16 Å, CN = 8; r[Ca2+] = 1.12 Å, CN = 8; r[Sb5+] =
0.60 Å, CN = 6; r[Ta5+] = 0.64 Å, CN = 6), when the Bi3+ ion
is doped more inclined to occupy the La3+ site without
breaking the charge balance, and only at high Bi 3+
concentrations would they be considered to occupy the Ca2+
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site. The XRD analysis of the CaLa0.99MgSbxTa1−xO6:0.01Bi3+
(x = 0, 0.25, 0.5, 0.75, 1.0) sample is shown in Figure 1b. All
diffraction peak positions can be overlapped with the structure
of the standard card (PDF #30-0261 and PDF #43-0043),
which proves that the synthesized phosphor is still pure phase
after doping. The detailed crystal structure data of
CaLa0.99MgSbxTa1−xO6:0.01Bi3+ were clearly elucidated by
XRD Rietveld refinement (Figures 1c and S1), and the
refinement results are shown in Table S1, with low confidence
coefficients for Rp, Rwp, and χ2, indicating that the obtained
refinement results are plausible, and with increasing sub-
stitution x, the lattice parameters (a, b, c, β, and V) show a
linearly decreasing trend (Figure 1d), in which parameter a
showed an abnormal change at x = 0.5. The reason may be that
the cation disorder in the matrix at x = 0.5 was larger than that
at x = 1, resulting in a larger deformation of the whole cell in a
certain direction and a larger change trend of parameter a. It
indicates that the successful formation of phosphor and the
entry of substitution ions into the occupied positions do not
destroy the crystal structure.
To investigate the morphology and composition of the
phosphors, SEM images of CaLa0.99MgSb0.5Ta0.5O6:0.01Bi3+
were taken (Figures 2a and S2). As shown, all phosphors are
well-crystallized irregular particles with a grain size of around
1.2 μm on average and distinct grain boundaries. Ca, La, Mg,
Sb, Ta, O, and Bi are uniformly distributed within the sample
particle in the elemental mapping analysis (Figure 2b) from
the electron image of the sample. In the EDS spectra, the
relative content and energy peaks of each element are clearly
visible (Figure 2c), and no other impurity element peaks are
found, which further proves the feasibility of the cationic Sb/
Ta replacement strategy and the successful incorporation of
Bi3+ ions into the matrix lattice.
3.2. Photoluminescence (PL) and Thermal Quenching
Properties. The excitation and emission spectra of the
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Figure 3. (a) PLE and PL spectra of CaLa0.99MgSbxTa1−xO6:0.01Bi3+ (x = 0−1). (b) Gaussian fitting to the photoluminescence excitation
spectrum of CaLaMgSbO6:Bi3+. The horizontal coordinate is the wavelength converted to photon energy (eV). The vertical coordinate is converted
to energy form according to I(E) = I(λ) × λ2.

Figure 4. (a) Normalized emission spectra of CaLa0.99MgSbxTa1−xO6:0.01Bi3+ (x = 0−1) at a 308 nm excitation and (b) integral intensity, emission
peak, and half-peak width variation curves.

phosphor are shown in Figure 3a. Monitoring the excitation
spectrum of the phosphor at 404 nm shows that the spectrum
exhibits a small peak at 200−270 nm and a large peak around
270−350 nm with increasing substitution, and the peak pattern
does not change. In order to investigate the source of
excitation, the excitation spectrum of CaLaMgSbO6:Bi was
analyzed by Gaussian splitting (Figure 3b), and it can be seen
that the excitation spectrum can be better fitted to three
Gaussian peaks 5.128 eV (242 nm), 4.156 eV (298 nm), and
3.905 eV (317 nm), which correspond to the [SbO6] charge-
transfer band of the matrix (CTB) and the 1S0 → 1P1/3P1 leap
of Bi3+. It is noteworthy that in the normalized emission
spectrum (Figure 4a), it can be observed that the spectrum
shows a clear blue-shift trend from 413 nm to 395 nm as the
substitution amount x changes from 0 to 1, and the peak
position of the emission spectrum shows a good linearity with
the substitution amount (Figure 4b), and the full half-peak
width height (FWHM) decreases from 63 to 38 nm. More
importantly, it is found that the integral intensity of Bi3+
luminescence changes surprisingly from 23.4% at x = 0−100%
at x = 1. The CIE chromatogram (Figure S3) clearly shows
that the phosphor can be tuned from blue to blue-violet light at
room temperature. Subsequently, the emission spectra (Figure
S4) were further measured at (280−330 nm) excitation
wavelengths for different substitution amounts, and all samples
showed a tendency to red-shift the emission peak with
increasing excitation wavelength, and the intensity reached its
maximum in the range of 300−310 nm.
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Usually, the luminescence intensity of Bi3+ shows a drastic
decrease with the increase of temperature, which is commonly
referred to as thermal quenching. Here, we tested the thermal
stability of CaLa0.99MgSbxTa1−xO6:0.01Bi3+ (x = 0, 0.25, 0.5,
0.75, 1.0), and the variable temperature spectrograms (Figures
5a−e and S5a−e) show that the resistance to thermal
quenching tends to enhance as Sb gradually replaces Ta, as
can be seen from the graph of the change in the integral
intensity curve in Figure 5f at 403 K; the integral intensity of x
= 0 is 20.89% of the initial value, while x = 1 is 38.59%, and the
thermal quenching resistance is improved by nearly twice. The
tendency of CIE with temperature could be used as a symbol
of thermal quenching. Figure S6 shows that with the increase
of replacement amount, CIE decreases, which corresponds to
the strengthening of Bi3+ thermal quenching resistance. In
evaluating the thermal stability of phosphors, T0.5 (the
temperature at half of the original intensity) was used to
evaluate T0.5 values of 356.4, 358.8, 362.0, 371.9, and 381.1 K
for x = 0−1 (Figure S4f). It can be seen that the T0.5 shows a
growing enhancement with the amount of substitution. In
addition, we conducted a heat−cooling cycle experiment for
phosphors with x = 0 (Figure S7), and there was little
discrepancy among emission spectra and integral fitting curves
under heating and cooling, indicating that the phosphors
prepared had good repeatability. The thermal quenching
activation energy (ΔE) is also an indispensable index. It is the
thermal energy required for electrons to conquer a specific
energy potential barrier (Ea) in the process of leapfrogging.
Therefore, when ΔE is larger, the more energy is required for
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Figure 5. (a−e) CaLa0.99MgSbxTa1−xO6:0.01Bi3+ (x = 0−1) from 303 to 523 K at different temperatures of PL-dependent spectra. (f) Relative
emission intensity curves of phosphors at different temperatures.

Figure 6. (a−e) Thermal quenching activation energy (ΔE) of CaLa0.99MgSbxTa1−xO6:0.01Bi3+ (x = 0−1). (f) Fitting relation between thermal
quenching activation energy (ΔE), T0.5 and x.

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Inorganic Chemistry
the electron to complete the leap, which can reduce the
quenching process and thus enhance the thermal quenching
resistance. This can be calculated by the following Arrhenius
formula16
I0
I (T ) =
1 + A × exp( E /KBT ) (1)
where I0 is the integrated intensity at the incipient temperature,
I(T) is the integrated intensity at T temperature, and KB and A
are constants (KB = 8.629 × 10−5 eV·K−1 is the Boltzmann
constant). When x = 0−1, the values of ΔE are 0.2658, 0.2655,
0.2738, 0.3120, and 0.3301 eV, respectively (Figure 6a−e). It is
obvious that the increase in ΔE corresponds to the increase of
thermal quenching resistance. Comparing the fitted curves of
T0.5 and ΔE (Figure 6f), it can be seen that both show a similar
trend of variation. The slow growth is reflected in x = 0−0.5,
while a large difference occurs when x is greater than 0.5, as the
crystal type in the lattice changes from [TaO6] to [SbO6]
octahedron dominated. It indicates that changing the amount x
of Sb5+/Ta5+ substitution in the substrate, the purpose of
modulating the thermal quenching performance of Bi3+ can be
achieved.
3.3. Mechanism of PL Luminescence and Thermal
Quenching Property Tuning. To explore the blue-shift
trend and the reason for the change in thermal quenching
properties, a series of characterization experiments were done.
First, X-ray photoelectron spectroscopy was performed for x =
0.5 and x = 1 phosphors, and the core energy levels of Ca 2s2p,
La 3d, Mg 2p, Sb 3d, Ta 4p 4f, and O 1s in the full XPS
spectrum (Figure S8) can be clearly observed in the spectrum.
The characteristic peaks of XPS of Bi3+ are shown in Figure 7,
Figure 7. XPS spectra of the Bi 4f electron energy (x = 0.5 and x = 1).
both of which have characteristic peaks displayed at 164 and
159 eV, corresponding to the 4f5/2 and 4f7/2 structures of Bi3+,
respectively, which indicate that the doped Bi is in the trivalent
state in the different doped main lattices and is confirmed to be
luminescent for Bi3+. The 4f7/2 and 4f5/2 configuration
photoelectron binding energies of Bi3+ in x = 1 (159.5 and
164.8 eV) are greater than those in x = 0.5 (159.3 and 164.7
eV). The reason for the elevation may be due to the increase in
lattice distortion in the main substrate, which changes the
crystal field environment around Bi3+ and reduces the density
of the electron cloud. Furthermore, by measuring the Raman
spectra of CaLa0.99MgSbxTa1−xO6:0.01Bi3+ (x = 0−1) (Figure
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8a), with increasing substitution, the vibrational peaks
belonging to [Sb/TaO6] between 650 and 850 cm−1 show a
series of corresponding shape changes, and the vibrational
peaks of [LaO8] at 70−170 cm−1 showed no significant
changes. For the Raman vibrational peaks of Bi3+, the three
vibrational peaks belonging to [BiO8] can be seen in the
magnified figure (Figure 8b), moving toward lower wave-
number with increasing substitution, corresponding to the
translational vibration of Bi−O1 (225.9 cm−1), the stretching
vibration of Bi−O2 (362.7 cm−1), and the O1−Bi−O2 (443.2
cm−1). Specifically, the shift of Raman vibration peaks can
reflect the change of chemical bond vibration frequencies, and
the stronger the chemical bond, the higher the corresponding
molecular vibration frequency. The shift of the Raman
characteristic peak to lower wavenumber confirms that the
coupling vibration frequency of the Bi−O bond in the internal
structure of the crystal decreases, and the tensile stress
subjected to it tends to decrease and thus the bond length
increases. Then, the UV−vis diffuse reflectance spectrum of
the phosphor was measured and the results are shown in
Figure 9a, where there is an absorption peak at 200−250 nm
and another absorption peak at 250−350 nm, which
corresponds to the excitation spectrum of the phosphor and
the excitation origin also corresponds to the excitation
spectrum. The optical band gap of Bi3+ was calculated using
the Kubelka−Munk formula17,44
F(R ) = (1 R )2 /2R (2)
[F(R ) × h ]1/2 = A(h Eg) (3)
where R is the reflectance (%) and hν is the photon energy.
F(R) represents the generalized formula of reflectance. The
optical band-gap Eg value is obtained by plotting the intercept
of [F(R) × hν]1/2 of the diffuse reflectance spectrum against
the linear part of the hν plot. From Figure 9b, the optical band
gaps are 3.02, 3.10, 3.18, 3.53, and 3.75 eV for the substitution
x = 0−1. It can be seen that the variation of the Eg is slow and
then sharply increases, which has a similar trend to the
aforementioned T0.5 and ΔE (Figure S9). In general, the
optical band gap is affected by several crystal structure factors,
and here, we speculate that the change in band gap can be
attributed to the variation in the field strength (Dq) of the Bi3+
crystal due to the Sb/Ta substitution. Dq in the matrix is
obtained from the following formula45,46
Ze 2r 4
Dq =
6R5 (4)
where R is the bond length between the ligand and the central
cation, Z is the valence state of the anion, e represents the
charge, and r is the radius of the wave function. Since the ionic
radius of Sb5+ is slightly smaller than that of Ta5+ and the
electronegativity difference is larger (Sb: 2.05; Ta: 1.5), it
attracts the surrounding ligand oxygen ions to bind more
intensively, leading to a decrease in the average bond length of
Sb−O in the lattice compared to that of Ta−O. Thus, the Bi−
O bond length, with which the vertex cation is shared, shows a
trend of a distorted stretching increase (Table 1 shows the
results of Rietveld′s calculations with an average bond length
of 2.182 Å for Ta−O and 2.176 Å for Sb−O, and the Bi−O
bond increases from 2.53157 to 2.57611 Å). Therefore, Dq
tends to decrease with the amount of substitution.
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Figure 8. (a) Raman spectra of CaLa0.99MgSbxTa1−xO6:0.01Bi3+ (x = 0−1). (b) Raman spectra of the local 150−550 cm−1 amplification.

Figure 9. (a) UV-diffuse reflectance spectrum of CaLa0.99MgSbxTa1−xO6:0.01Bi3+ (x = 0−1). (b) Calculated spectrum of band gap fitted by the
Kubelka−Munk formula.

Table 1. Average Bond Length in GSAS Refined Phosphors This results in an enhancement of the value of the optical band
3+ 3+
gap between the 1S0 state and the 3P1 state, which is consistent
bond length (Å) CaLa0.99MgTaO6:0.01Bi CaLa0.99MgSbO6:0.01Bi
with the experimental measurements. In addition, the energy
Ta−O1 2.07088 level splitting leads to lower energy required to excite the
Ta−O2 2.29131 electrons to the 1P1 energy level, and thus the luminescence
Ta−O3 2.18389 intensity shows an increasing trend coinciding with that in
average 2.18203 Figure 4b. Similarly, the 3P1 energy level position will keep
Sb−O1 2.370 increasing, leading to a corresponding increase in the energy
Sb−O2 2.216 emitted by the electron leap to the ground state, and therefore
Sb−O3 1.943 a blue-shift change in the emission peak will be observed
average 2.176 (Figure 4a). Moreover, for the cross-relaxation mechanism of
Bi−O1 2.70126 2.90500 Bi3+ thermal quenching, at high temperature, the electrons on
Bi−O2 2.49263 2.10000 the 3P1 energy level gain thermal energy to transcend the
Bi−O3 2.40082 2.72333 energy potential barrier ΔE to leap to the energy level cross
average 2.53157 2.57611 position, which leads to the thermal quenching of lumines-
cence by nonradiative relaxation to the 1S0 ground state. When
The mechanism of tuning the luminescence and thermal Sb/Ta substitution occurs, the reduction in crystal field
quenching properties of Bi3+ induced by Sb/Ta substitution is splitting elevates the 3P1 energy level position, making ΔE
revealed, as shown in Figure 10. When the Bi3+ ions are doped increase, and thus the electrons on 3P1 absorb thermal energy
into the main host lattice, the 6s2 electron layer will split into with a lower probability to achieve nonradiative relaxation,
several subenergy levels. As the substitution of B′-site cations leading to improved thermal quenching properties.
occurs in the substrate, the nephelauxetic effect will cause their
energy difference, specifically in the form of a variation of Dq. 4. CONCLUSIONS
Therefore, replacing the larger [TaO6] octahedron with the In summary, a novel B′-site substitution double perovskite
smaller [SbO6] octahedron will reduce the lattice volume structure antimony-tantalate CaLaMgSbxTa1−xO6 host material
(Table S1). Subsequently, the activator Bi3+−ligand bond was constructed by the ion substitution design strategy for the
length increases under the influence of cationic substitution of luminescent ion Bi-doped phosphor matrix. When the
the linked main lattice, which weakens the covalent interaction coordination cation Sb5+ is replaced with Ta5+, a surprising
and reduces the Dq. When Dq decreases, the splitting of the 3P increase in the integral intensity change of Bi3+ luminescence
state energy level of Bi3+ decreases, resulting in a lower 1P1 from 23.4% at x = 0−100% at x = 1 was observed, as well as an
energy level position and a higher 3P1 energy level position. increase in thermal stability from 20.38 to 38.59% of the initial
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Inorganic Chemistry
Figure 10. Mechanisms of luminescence and thermal quenching tuning.
intensity at 403 K. The Raman spectrum shifted in the small
wavenumber direction confirms the increase in stretching
stress on the Bi−O bond in the matrix, and the bond length of
the activator and ligand Bi−O bond was calculated from the
Rietveld refinement specifically from 2.53157 to 2.57611 Å. As
the Dq is weakened by the bond length, the band gap of the
activator Bi3+ increases from 3.02 to 3.75 eV; the value of the
ΔE increases from 0.2658 to 0.3301 eV; T0.5 also increases
from 356.4 to 381.1 K. In this contribution, we analyze the
intrinsic relationship between band-gap increase, Raman
wavenumber shift, and ligand bond length change of Bi3+
ions from the perspective of crystal field splitting energy and
construct a mechanism to regulate the thermal quenching
properties of its luminescence. It can provide an effective
strategy to enhance promising new materials such as double
perovskite.
■
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ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.inorgchem.3c00964.
Rietveld refinement; SEM image; CIE chromaticity
diagram; PL spectrum; PL variable temperature
spectrum; variable temperature chromaticity coordinates
(x, y); heating and cooling cycle curves; X-ray
photoelectron spectroscopy; ΔE, T0.5, and Eg diagram;
and Rietveld refinement parameters and crystallographic
data (Figures S1−S9 and Table S1) (PDF)
■ AUTHOR INFORMATION
Corresponding Author
Ning Guo − Department of Chemistry, University of Shanghai
for Science and Technology, Shanghai 200093, P. R. China;
orcid.org/0000-0001-5295-2589; Phone: +86-21-
65711344; Email: guoning@usst.edu.cn
Authors
Ran Xiao − Department of Chemistry, University of Shanghai
for Science and Technology, Shanghai 200093, P. R. China;
orcid.org/0000-0002-1959-8626
9127
pubs.acs.org/IC Article
Chengzheng Jia − Department of Chemistry, University of
Shanghai for Science and Technology, Shanghai 200093, P.
R. China
Qincan Ma − Department of Chemistry, University of
Shanghai for Science and Technology, Shanghai 200093, P.
R. China; orcid.org/0000-0002-4560-740X
Ruoting Liu − Department of Chemistry, University of
Shanghai for Science and Technology, Shanghai 200093, P.
R. China
Ruizhuo Ouyang − Department of Chemistry, University of
Shanghai for Science and Technology, Shanghai 200093, P.
R. China; orcid.org/0000-0001-5091-6816
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.inorgchem.3c00964
Author Contributions
R.X.: methodology, validation, formal analysis, investigation,
data curation, writing�original draft, and writing�review and
editing. N.G.: conceptualization, methodology, resources,
supervision, and funding acquisition. C.J.: resources, super-
vision, and project administration. Q.M.: methodology,
validation, and investigation. R.L.: methodology and inves-
tigation. R.O.: resources, supervision, and project adminis-
tration.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was financially supported by the National Natural
Science Foundation of China (Grant No. 21401130) and the
Opening Research Fund of the State Key Laboratory of Rare
Earth Resource Utilization, Changchun Institute of Applied
Chemistry, Chinese Academy of Sciences (RERU2014005).
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