Journal of Alloys and Compounds 879 (2021) 160461

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Journal of Alloys and Compounds

journal homepage: www.elsevier.com/locate/jalcom

Investigation of a phosphor mixture of LiAl5O8: Cr3+ and LuPO4: Tb3+ as a

dual-mode temperature sensor with high sensitivity ]]
]]]]]]
]]

⁎ ⁎
Liting Qiu a, Peng Wang a, Xiantao Wei b, Fengfeng Chi c,d, Yonghu Chen a, , Min Yin a,
a
Key Laboratory of Strongly-Coupled Quantum Matter Physics, Chinese Academy of Sciences, School of Physical Sciences, University of Science and Technology of
China, No. 96 Jinzhai Road, Hefei, Anhui Province 230026, China
b
Physics Experiment Teaching Center, School of Physical Sciences, University of Science and Technology of China, Hefei 230026, China
c
New Energy Technology Engineering Laboratory of Jiangsu Province & School of Science, Nanjing University of Posts and Telecommunications, Nanjing 210023,
China
d
National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093, China

a r t i cl e i nfo a bstr ac t

Article history: A mixture of Cr3+-doped phosphor (LiAl5O8: Cr3+) and Tb3+-doped phosphor (LuPO4: Tb3+), named as SAMIX,
Received 30 March 2021 was successfully prepared by the traditional high-temperature solid-state method, and its luminescence
Received in revised form 12 May 2021 properties for temperature sensing were investigated. Under a resonance excitation of 543.8 nm corre­
Accepted 16 May 2021
sponding to the 7F5 → 5D4 transition of Tb3+, both the emissions of Cr3+ and Tb3+ were observed, and their
Available online 19 May 2021
temperature-dependent intensity exhibits opposite tendency. Consequently, the fluorescence intensity ratio
technique for temperature sensing based on the luminescence of Tb3+ and Cr3+ yields an excellent per­
Keywords:
Mixture formance with a maximum relative sensitivity of 3.68% K−1 at 300 K. In addition, the lifetime of Cr3+ at
Fluorescence intensity ratio 714 nm is strongly affected by the temperature. When the temperature rises from 300 to 600 K, the lifetime
Lifetime of Cr3+ at 714 nm will decrease monotonically from 6.34 to 1.12 ms. The maximum value of relative sen­
Temperature sensing sitivity based on the lifetime of Cr3+ reaches 0.80% K−1 at 520 K. All these investigations indicate that the
SAMIX phosphor is one of the promising candidate materials for a dual-mode high-sensitivity temperature
sensor.
© 2021 Elsevier B.V. All rights reserved.

1. Introduction the spectral overlap of the TCELs as well as prevent thermal de­
coupling of the TCELs, the ∆E between the TCELs is usually limited to
Recently, non-contact optical temperature sensing has received the range of 200 – 2000 cm−1. This means that the sensitivity of
much attention for its advantages of non-invasive detect mode, rapid temperature sensing based on the conventional TCELs scheme is
time response and high spatial resolution [1]. Temperature sensing limited and hard to be improved. However, with the rapid devel­
strategies employing temperature-dependent luminescent proper­ opment of modern technology and industry, the fields such as pre­
ties such as spectral position [2–4], emission intensity [5–8], fluor­ cise instrument, micro-electronics and biomedicine, all raise the
escence intensity ratio (FIR) [9–19] and fluorescence lifetime requirements for more accurate temperature measurements. Ob­
[2,11,13,14,18,20] have been widely investigated. In particular, the FIR viously, the larger the SR, the more favorable to improve the accuracy
technique based on relative intensity of the emission in two regimes of temperature measurement [23–25]. Therefore, searching for a
is considered to be the most promising, because it is immune to scheme to enhance the sensitivity of temperature sensing is still
fluorescence loss, external interferences and fluctuations of excita­ urgent [26].
tion power [21]. Such optical thermometry based on FIR technique As a promising scheme, the rare earth (RE) and transition metal
usually involves two nearby energy level of rare earth (RE) ions, (TM) ions co-doped luminescent materials for temperature sensing
namely thermally-coupled energy levels (TCELs) with an energy have been rapidly developed due to their completely different
difference (∆E), whose value proportionally determines the sensi­ thermal quenching behaviors [10,14,17,18]. In 2016, Chen et al. [10]
tivity of temperature measurement [22]. However, in order to avoid realized a high temperature sensitivity of 15 – 20% K−1 in RE3+/ TM3+
(RE = Eu, Tb, Dy; TM = Cr) co-doped GdF3/Ga2O3 transparent glass
ceramics. In 2020, Piotrowski et al. [17] developed a Mn4+/Tb3+ co-
⁎
Corresponding authors. doped luminescent nanomaterial, of which the maximum value of
E-mail addresses: [email protected] (Y. Chen), [email protected] (M. Yin). relative sensitivity SR reached 2.8% K−1 at 403 K. It is well known that

https://doi.org/10.1016/j.jallcom.2021.160461
0925-8388/© 2021 Elsevier B.V. All rights reserved.
L. Qiu, P. Wang, X. Wei et al. Journal of Alloys and Compounds 879 (2021) 160461

the intra-4 f transitions of the rare earth (RE) ions with 4 fn elec­ phosphor was used for the subsequent temperature-dependent in­
tronic configuration, due to the shielding by outer 5 s25p6 electrons, vestigation.
are hardly affected by the external environment, while the lumi­ An X-ray diffractometer (Rigaku-TTR-III) with nickel-filtered Cu
nescence of the transition metal (TM) ions with unshielded 3dn Kα radiation (λ = 0.15418 nm) was utilized to identify the crystal
electronic configuration are extremely sensitive to surroundings. In a structures of LiAl5O8: 0.1% Cr3+ and LuPO4: 6% Tb3+ samples. The
word, the thermal quenching of luminescence for TM ions is much photoluminescence emission (PL) and excitation (PLE) spectra were
stronger than trivalent RE ions, which are beneficial for obtaining a measured at room temperature through a HITACHI 850 Fluorescence
RE3+/TM co-doped high-sensitivity temperature sensor. Recently, a Spectrophotometer (Hitachi Ltd.), which utilized a 150 W Xenon
novel scheme for temperature sensing was proposed, in which the lamp as its excitation light source. The temperature-dependent PL
abnormal thermal quenching behaviors of RE3+ emissions were ap­ spectra were detected by using a double monochromator (Model
plied [5–7,15]. For example, Zhou et al. [5] demonstrated that under Jobin-Yvon HRD-1) equipped with a Hamamatsu R928 photo­
a resonance excitation at 611.2 nm corresponding to the 7F2 → 5D0 multiplier. The temperature-dependent decay curves were recorded
transition of Eu3+, the emission intensities of Eu3+ from 5D0 → 7F4 through a Tektronix TDS2024 digital storage oscilloscope connected
transition will rapidly increase with the temperature rising. Actually, in parallel with a 50 KΩ resistor and the final response time of the
such abnormal thermal quenching behavior of the Eu3+ emission is oscilloscope is about 0.01 ms. A tunable laser system (Model
attributed to the fact that the excitation wavelength is specifically Opolette 355 LD OPO system) with a laser linewidth of 4 – 7 cm−1
designed to make Eu3+ ions jump to the 5D0 state from the thermally and a pulse duration of 7 ns was used as an excitation source for the
populated 7F2 state rather than from the ground state 7F0. As a result, temperature-dependent PL spectra and decay curves. The sample
with the temperature rising, the Eu3+ ions populated at the 7F2 state temperature in the range of 300 – 600 K was controlled by a tem­
will increase via thermal excitation from ground state to 7F2 state. perature controller (Lake Shore Model 335) equipped with a type-K
Hence, an abnormal thermal quenching behavior of the Eu3+ emis­ thermocouple and a heating tube.
sion can be observed when excited at 611.2 nm (7F2 → 5D0). In fact,
when excited by a resonance wavelength from a low-lying thermally
3. Results and discussion
populated level, not only Eu3+ emission exhibits the abnormal
temperature quenching behavior, so do Tb3+ and Sm3+ [6,7,15].
3.1. Phase and crystal structure analysis
According to the above analysis, it is very promising to attempt to
use TM (Cr3+, Mn4+) and RE3+ (Tb3+, Sm3+, Eu3+) activators with op­
The XRD patterns of the LiAl5O8: Cr3+ and the LuPO4: Tb3+ sam­
posite thermal quenching behaviors to realize a temperature sensor
ples and the corresponding JCPDS cards are presented in Fig. 1(a) and
with a higher sensitivity. In our paper, in order to avoid spectral
(b), respectively. The diffraction peaks of LiAl5O8: Cr3+ are consistent
overlap between TM and trivalent RE ions, and to enable TM and
with the cubic LiAl5O8 phase (JCPDS No. 71-736) with P4332 (No.
RE3+ ions to be excited simultaneously under the resonance excita­
212) space group and the diffraction peaks of LuPO4: Tb3+ agree well
tion of RE3+, Cr3+ and Tb3+ ions were finally selected as temperature
with tetragonal LuPO4 phase (No. 70–1282) with I41/amd (No. 141)
sensing probes. Meanwhile, to prevent the adverse effect of energy
space group, indicating that the pure products of LiAl5O8: Cr3+ and
transfer from Tb3+ to Cr3+ ions [11], we chose to dope Tb3+ and Cr3+
LuPO4: Tb3+ are successfully synthesized. As demonstrated in
ions into different hosts, respectively. Finally, a mixture of LiAl5O8:
Fig. 1(c), the structure of LiAl5O8 is composed of 4- and 6-fold co­
Cr3+ and LuPO4: Tb3+ phosphor noted as SAMIX was successfully
ordinated Al3+ ions. However, due to the similar ionic radii between
prepared by the traditional high-temperature solid-state method
Cr3+ (r = 0.615 Å, CN = 6) and Al3+ (r = 0.535 Å, CN = 6) and the strong
[27,28], and the opposite thermal quenching behaviors of Cr3+ and
ligand-field stabilization energy of Cr3+ in the 6-fold coordination,
Tb3+ in SAMIX were observed from the temperature-dependent
the Cr3+ dopants tend to occupy the octahedral Al3+ site [29].
spectra when excited by a resonance excitation corresponding to the
7 Fig. 1(d) reveals that the structure of LuPO4 consists of 8-fold co­
F5 → 5D4 transition of Tb3+, which is very beneficial for SAMIX as a
ordinated Lu3+ ions and the Tb3+ dopants are easily partitioned into
FIR-mode temperature sensor. In addition, the temperature-depen­
the dodecahedral Lu3+ site owing to the approximate ionic radii of
dent lifetime of Cr3+ at 714 nm in SAMIX was also measured. All
Tb3+ (r = 1.04 Å, CN = 8) and Lu3+ ions (r = 0.977 Å, CN = 8).
these investigations reveal that the SAMIX is one of the most pro­
mising materials for optical thermometry application with dual de­
tection modes and a high temperature sensitivity. 3.2. Photoluminescence analysis

The room temperature PL and PLE spectra of the Cr3+ doped

2. Experimental LiAl5O8 and the Tb3+ doped LuPO4 samples excited by Xenon lamp
are plotted in Fig. 2(a) and (b), respectively. Under 565 nm (4A2 →
The powder samples of LiAl5O8 doped with Cr3+ ions and LuPO4 4
T2) excitation, the PL spectrum of LiAl5O8: Cr3+ shows two sharp
doped with Tb3+ ions were prepared by the solid state reaction at emission lines centered at 701 nm and 714 nm, both of which are
high temperature [27,28]. For LiAl5O8: Cr3+ sample, the raw powders assigned to the spin-forbidden 2E → 4A2 transition. What’s more, a
of LiCO3 (99.99%), Al2O3 (99.99%) and Cr2O3 (99%) were weighed weak broadband emission in the wavelength range of 650 – 850 nm
according to the stoichiometric molar ratio of sample and then assigned to the phonon sidebands of 4T2 → 4A2 transition is also
thoroughly ground for 30 min. After fully grinding, the mixed raw observed from Fig. 2(a). When monitoring 714 nm emission, the PLE
powders were sintered at 1350 °C for 6 h in air to form the product. spectrum of LiAl5O8: Cr3+ shows two broad excitation bands cen­
For LuPO4: Tb3+ sample, the non-stoichiometric amounts of Lu2O3 tered at 407 nm and 565 nm, which are corresponding to the spin-
(99.99%), Tb4O7 (99.99%) and NH4H2PO4 (99%) were thoroughly allowed 4A2 → 4T1 and 4A2 → 4T2 transitions of Cr3+, respectively. In
ground in an agate mortar. After thoroughly grinding, the mixed raw fact, the luminescence processes of Cr3+ ions with 3d3 electron
powder were preheated to 800 °C for 12 h. Then, the preheated configuration is highly dependent on the crystal-field strength (Dq)
powder was subjected to a two-step sintering of first at 1000 °C for [2,10–12,16,30]. A Tanabe - Sugano diagram provided in Fig. 2(d) are
12 h and subsequently at 1300 °C for 12 h in order to obtain pure used to describe the energy level of Cr3+ ions in LiAl5O8 matrix.
phase LuPO4: Tb3+ sample. Finally, we mixed the LiAl5O8: 0.1% Cr3+ Combined with the PLE spectrum of Cr3+ in Fig. 2(a), the crystal field
and LuPO4: 6% Tb3+ in a molar ratio of 1–200 and ground again to strength (Dq) of Cr3+ in LiAl5O8 matrix can be calculated by the
make the mixed sample (SAMIX) homogeneous. The obtained SAMIX following equations:

2
L. Qiu, P. Wang, X. Wei et al. Journal of Alloys and Compounds 879 (2021) 160461

Fig. 1. XRD patterns and the corresponding JCPDS cards of (a) LiAl5O8: Cr3+ and (b) LuPO4: Tb3+ samples, and cell structures of (c) LiAl5O8 and (d) LuPO4.

with the excitation band of Cr3+ in Fig. 2(a), which implies that the
4 4
E A2 T2 Cr3+ and Tb3+ can be excited simultaneously under a resonance ex­
Dq = citation corresponding to the 7F5 → 5D4 transition of Tb3+. However,
10 (1)
compared to Cr3+, the excitation of Tb3+ is from the thermally po­
pulated 7F5 state rather than from the ground state. As a result, when
Dq 15 (m 8)
= 2 the temperature is not high, the emission intensity of Tb3+ will be
B m 10m (2)
much lower than that of Cr3+, which will result in a large mea­
surement error when using FIR technique for temperature sensing
4 4 4 4
E A2 T1 E A2 T2 based on the luminescence of Tb3+ and Cr3+ [33]. In fact, in our paper,
we have adjusted the concentrations of Cr3+-doped phosphor and
m=
Dq (3) Tb3+-doped phosphor as well as the molar ratio of the mixture
4 4 4 4
phosphors to make the emission intensity of Tb3+ and Cr3+ at the
where the value of the E ( A2 → T1) and the E ( A2 → T2) are
same order of magnitude. Besides, finding the most optimal excita­
24570 cm−1 and 17699 cm−1, respectively. Thus the parameter of the tion wavelength corresponding to the 7F5 → 5D4 transition of Tb3+
crystal field strength Dq, the Racah parameter B and Dq/B are eval­ can further improve the emission intensity of Tb3+. It can be found in
uated to be 1770 cm−1, 681 cm−1 and 2.63, respectively. The inter­
Fig. 2(c) that this optimal excitation wavelength for the 7F5 → 5D4
mediate crystal field strength (Dq/B = 2.63) indicates that the
transition of Tb3+ is 543.8 nm. Moreover, it is clear that although the
dominant R-line emission (2E → 4A2) and a weaker broadband
characteristic emission peak of Tb3+ overlaps with the excitation
emission (4T2 → 4A2) of Cr3+ ions in LiAl5O8 host can be observed at band of Cr3+, the probability of reabsorption of Tb3+ by Cr3+ can be
the same time, which is confirmed by the PL spectrum shown in greatly reduced by mixing the two different phosphors, which is
Fig. 2(a). For LuPO4: Tb3+, when monitoring at 545 nm (5D4 → 7F5)
attributed to the fact that the Cr3+ and Tb3+ are doped into different
emission of Tb3+, the PLE spectrum of LuPO4: Tb3+ exhibits several
hosts.
characteristic strong excitation peaks at 344, 353, 361, 371 and
379 nm, which are attributed to the f-f transitions of Tb3+ ions. For
example, the peak at 371 nm can be assigned to 7F6 → 5G6. In ad­ 3.3. Temperature-dependent luminescence analysis
dition, the PL spectrum of LuPO4: Tb3+ under the excitation of
371 nm shows several sharp emission peaks at 490, 545, 589 and To study the luminescence mechanism of our SAMIX sample for
623 nm, which originate from 5D4 → 7FJ ( J = 6 – 3) transitions and thermometry application, the schematic energy level diagram of
can be easily identified [32]. In addition, it is worth noting that the Tb3+ and the configurational coordinate diagram of Cr3+ are depicted
characteristic emission peak of Tb3+ at 545 nm in Fig. 2(b) overlaps in Fig. 3. As revealed above, the Cr3+ and Tb3+ ions can be excited at

3
L. Qiu, P. Wang, X. Wei et al. Journal of Alloys and Compounds 879 (2021) 160461

Fig. 2. The PL and PLE spectra of (a) LiAl5O8: Cr3+ and (b) LuPO4: Tb3+ samples at room temperature by using Xenon lamp as the excitation source (Here, the color labels for the
emission and the excitation spectra are blue and purple respectively), (c) The PLE spectrum of LuPO4: Tb3+ sample at room temperature by using OPO as the excitation source
(Here, the excitation and emission are corresponding to the 7F5 → 5D4 and 5D4 → 7F4 transitions, respectively.), (d) Tanabe - Sugano energy level diagram of Cr3+ ions (left) and
the schematic energy level diagram of Cr3+ ions in LiAl5O8 matrix (right).

are very advantageous for the SAMIX to be used for temperature

sensing. For Tb3+ ions, as the temperature increases, the emission
intensity of 5D4 → 7FJ ( J = 0 – 4) transition becomes stronger. This is
because the energy levels of 7F5 and 7F6 of Tb3+ are thermally cou­
pled energy levels that obey the Boltzmann distribution, so the
number of Tb3+ ions occupying 7F5 state will increase with tem­
perature rising due to thermal excitation, thereby monotonically
increasing the emission intensity of 5D4 → 7FJ ( J = 0 – 4). For Cr3+
ions, due to the intermediate crystal field strength (Dq/B = 2.63) that
the 2E energy level of Cr3+ ions is also thermally coupled with the 4T2
energy level. Therefore, at low temperature, the Cr3+ ions are mainly
populated at the lowest 2E excited state, so that a strong emission
and a long lifetime related to the spin-forbidden 2E → 4A2 transition
are obtained. However, as the temperature rises, the population of 2E
Fig. 3. Proposed luminescence mechanism of the SAMIX phosphor. (The left and the
state decreases while that of 4T2 state will increase due to thermal
right respectively show the schematic energy level diagram of Tb3+ ions and the excitation, thus reducing the emission intensity of 2E → 4A2 transi­
configurational coordinate diagram of Cr3+ ions.). tion as well as shortening the lifetime of Cr3+ ions. According to the
above analysis, we can preliminary infer that a highly sensitivity
the same time under 543.8 nm laser. When excited by 543.8 nm temperature sensor could be obtained by employing the FIR tech­
laser, the Tb3+ ions are jumped to the 5D4 state from the thermally nique based on the emission of Tb3+ (5D4 → 7FJ) and the emission of
populated 7F5 state, while simultaneously the Cr3+ ions are jumped Cr3+ (2E → 4A2). What’s more, the lifetime of Cr3+ that varies with
to the 4T2 state from the 4A2 ground state. Subsequently, the Tb3+ temperature can be also used for temperature sensing.
ions produce 5D4 → 7FJ ( J = 0 – 4) emissions, while the Cr3+ ions The PL spectra and the histogram of integrated emission in­
produce the dominant 2E → 4A2 emission after non-radiative re­ tensities at different temperatures under the 543.8 nm laser excita­
laxation from 4T2 state to the 2E state. The emission intensities of tion are plotted in Fig. 4(a) and (b). Here, the emissions in the
Tb3+ and Cr3+ ions show opposite temperature dependence, which wavelength region of 580 – 600 nm related to the 5D4 → 7F4

4
L. Qiu, P. Wang, X. Wei et al. Journal of Alloys and Compounds 879 (2021) 160461

1 d (FIR)
SR FIR = × 100 %
FIR dT (6)
The calculated results show that the SA-FIR monotonically in­
creases with the increase of the temperature in the region we stu­
died, while the SR-FIR decreases and SR-FIR reaches a maximum value
of 3.68% K−1 at 300 K. It is worth noting that the SR-FIR value of the
SAMIX is relatively high over the whole physiological temperature
range (300 – 330 K), gradually decreasing from 3.68% K−1 at 300 K to
3.04% K−1 at 330 K, which recommends its potential use in bio-
medicine field.
Another important parameter to evaluate the performance of the
SAMIX as a temperature sensor is the temperature resolution δT,
which can be defined as follows [23]:
1
T=
SR (7)

2 2
I I
= +
ITb ICr (8)
The δI represents the intensity fluctuation and in our work, the
value of δI is about 612. Finally, according to Eqs. (7) and (8), the
temperature resolution of our sample at different temperature were
calculated, as shown in Fig. 5(c). It can be seen from the Fig. 5(c) that
the minimum temperature resolution δT of our sample based on the
FIR-mode temperature measurement is 0.05 K at 420 K, which is
comparable with the previous reported results [23–25,34,35].
In addition, the reliability and practicability of our SAMIX in
temperature measurement based on FIR mode was also checked
upon two heating and cooling cycles in the temperature range of
300–600 K. The normalized curve of the temperature-dependent
Fig. 4. (a) Temperature-dependent PL spectra of the SAMIX phosphor excited by
integrated FIR in Fig. 5(d) shows that the integrated FIR between the
543.8 nm, (b) Histogram of emission intensities (the integrated ranges, Tb3+: 580 –
600 nm and Cr3+: 706 – 723 nm). emissions of Tb3+ at 589 nm and Cr3+ at 714 nm has good repeat­
ability and reversibility at any temperature after two heating and
cooling cycles, which further confirms the temperature sensing
capability of our sample in FIR mode.
transition of Tb3+ and the emission in the wavelength region of 706 –
The normalized decay curves of Cr3+ emission in the SAMIX
723 nm related to the 2E → 4A2 transition of Cr3+ were selected to
under 543.8 laser pulse excitation at various temperatures in the
investigate the temperature dependence of the SAMIX in order to
range of 300–600 K are plotted in Fig. 6. All recorded curves can be
improve the signal-to-noise ratio and effectively avoid the overlap of
well fitted by single-exponential equation. The lifetimes derived
the luminescence of the Tb3+ and Cr3+ ions. As expected, with the
from the curves exhibit that under the 543.8 laser excitation, the
increasing of temperature from 300 to 600 K, the integrated emis­
lifetime of Cr3+ decreases monotonically from 6.34 to 1.12 ms when
sion intensities of the 5D4 → 7F4 transition of Tb3+ increase rapidly
the temperature rises from 300 K to 600 K, implying that tempera­
while the integrated emission intensities of the 2E → 4A2 transition
ture-dependent lifetime of the SAMIX can be also used for tem­
of Cr3+ decrease, which are very favorable for the SAMIX to be a
perature sensing. As analyzed above, the reason for the change in
highly sensitive temperature sensor material.
lifetime of Cr3+ ions can be attributed to the competition of radiation
To quantitatively study the property of the SAMIX as a tem­
transitions from the thermally-coupled 2E and 4T2 energy levels of
perature sensor, the temperature-dependent integrated intensity
Cr3+ ions. At low temperature, the spin-forbidden 2E → 4A2 transition
ratio of Tb3+ luminescence at 589 and Cr3+ luminescence at 714 nm
plays a dominant role, so a long lifetime is obtained. However, with
are presented in Fig. 5(a). This temperature-dependent integrated
the increase of temperature, more and more Cr3+ ions will populate
FIR increases monotonically with increasing temperature, which can
at 4T2 state due to thermal excitation. Finally, more spin-allowed 4T2
be well approximated by the exponential equation as follows:
→ 4A2 transition and fewer spin-forbidden 2E → 4A2 transition are
I589 3314 obtained, which leads to a shortened lifetime of Cr3+ ions.
FIR (T ) = = 1700 × exp
I714 T (4) According to previous works, the temperature-dependent life­
time of Cr3+ can be well fitted by the following equation, which
Here, I589 and I714 represent the integrated emission intensities of obeys the two-level kinetic model [11,31]:
5
D4 → 7F4 transition of Tb3+ and the 2E → 4A2 transition of Cr3+, re­
spectively.
= ×
1 + 3 × exp ( E
kB T )
The sensitivity is a significant parameter to assess the tempera­ s
ture sensing ability of the SAMIX. Consequently, the temperature- 1+3× s
i
× exp ( E
kB T ) (9)
dependent absolute sensitivity (SA-FIR) and relative sensitivity (SR-FIR) 3+
curves plotted in Fig. 5(b) are obtained by following equations: here τ is the lifetime of Cr at the temperature T, τs and τi are the
lifetimes of 2E and 4T2 states, ∆E is the energy gap between 2E and
4
d (FIR) T2 states of Cr3+, kB is the Boltzmann constant. As revealed in
SA FIR = Fig. 7(a), the agreement between the experimental data and the
dT (5) fitted curve is quite high, which can be proved by the high value of

5
L. Qiu, P. Wang, X. Wei et al. Journal of Alloys and Compounds 879 (2021) 160461

Fig. 5. Temperature-dependent (a) FIR of Tb3+: 5D4 → 7F4 to Cr3+: 2E → 4A2 and the fitting line, (b) absolute sensitivity (SA) and relative sensitivity (SR) of the SAMIX phosphor. (c)
Temperature resolution of different temperatures. (d) Normalized curve of the temperature-dependent integrated FIR under two heating and cooling cycles in the temperature
range of 300–600 K.

1d
SR lifetime = × 100%
dT (11)
It can be seen from Fig. 7(b) that both SA-lifetime and SR-lifetime of
Cr3+ at first increases with the temperature rising from 300 K to
600 K and then decreases. Finally, the maximal SA-lifetime and SR-lifetime
of the SAMIX phosphor are determined to be 2.57% ms·K−1 at 432 K
and 0.80% K−1 at 520 K, respectively. In addition, the emission peak
of Cr3+ in the lifetime measurement is located at the first near in­
frared window of biological tissue, which further favors its appli­
cation in biological temperature sensing.
The Table 1 shows the temperature measurement ranges, tem­
perature detection modes and the maximum SR values of several
optical temperature sensing materials. And it can be found that our
SAMIX exhibits excellent temperature sensing performance. In par­
ticular, the SR value obtained by the FIR-mode temperature sensing
method has been significantly improved, which confirms the feasi­
bility of our work design.

Fig. 6. Temperature-dependent decay curves of Cr3+ in the temperature range of 4. Conclusions

300–600 K when monitored at 714 nm under 543.8 nm excitation.
A dual-mode high-sensitivity temperature sensor was developed
2 by mixing a Cr3+-doped phosphor and a Tb3+-doped phosphor to­
correlation coefficient (R = 0.99935). Finally, the ∆E, τs and τi are
gether. The temperature-dependent PL spectra of Cr3+ and Tb3+ and
estimated to be 2233 cm−1, 6.42 ms and 19 μs, respectively.
temperature-dependent lifetime of Cr3+ were carefully investigated
Similarly, the temperature dependence of absolute sensitivity
in our paper. Under a resonant excitation of 543.8 nm laser, the
(SA-lifetime) and relative sensitivity (SR-lifetime) based on lifetime of Cr3+
emission intensity of Tb3+ corresponding to 5D4 → 7FJ (J = 0 – 4)
plotted in Fig. 7(b) can be obtained by the following equations:
transitions increases with the temperature rising in the region of
d 300 – 600 K, while the emission intensity of Cr3+ corresponding to
SA lifetime = × 100% 2
E → 4A2 transition decreases. Finally, the relative sensitivity (SR-FIR)
dT (10) and the minimum δT of our SAMIX based on FIR-mode temperature

6
L. Qiu, P. Wang, X. Wei et al. Journal of Alloys and Compounds 879 (2021) 160461

Fig. 7. Temperature-dependent (a) lifetime of Cr3+ in the temperature range of 300–600 K and the fitting line, (b) absolute sensitivity (SA) and relative sensitivity (SR) based on the
emission lifetime of Cr3+.

Table 1
Temperature measurement ranges, temperature detection modes, and maximum SR values of several optical temperature sensing materials.

Materials Temperature range (K) Mode Max. SR (% K−1) Ref.

3+ 3+
CaBi4Ti4O15: Tm /Yb Ceramics 163–503 FIR 1.6 [36]
NaMgBO3: Ce3+/Mn2+ 298–473 FIR 0.69 [34]
CsNa2Ln2(BO3)(PO4)2(Ln = Ho, Er, Tm, Yb) 303–573 FIR 1.10 [37]
Gd2(MoO4)3: Eu3+/Tb3+ 80–450 FIR 0.5 [38]
YNbO4: Eu3+/Er3+ 63–393 FIR 2.9 [25]
CaGdMgSbO6: Mn4+/Sm3+ 298–573 FIR 1.54 [14]
Lifetime 1.23
La2MgTiO6: Pr3+/Dy3+ 298–548 FIR 2.36 [13]
Lifetime 1.81
3+
Na2La2Ti3O10: Pr 303–543 FIR 1.96 [39]
Gd3Al5−xGaxO12: Cr3+/Nd3+ 123–573 FIR 1.9 [16]
LiAl5O8: Cr3+/LuPO4: Tb3+ 300–600 FIR 3.68 This work
Lifetime 0.8 This work

sensing were carefully calculated. The results show that the SR-FIR is Acknowledgments
as high as 3.68% K−1 at 300 K, and the minimum δT also reaches an
accuracy of 0.05 K at 420 K. In addition, the reliability of our SAMIX This work was supported by the National Key Research and
in temperature measurement based on FIR mode has been also Development Program of China [Grant No. 2016YFB0701001]; the
verified. Simultaneously, the lifetime of Cr3+ also exhibits a strong National Natural Science Foundation of China [Grant Nos. 11574298,
temperature dependence, and its relative sensitivity (SR-lifetime) value 61635012, 11974338 and 12004194]; the Natural Science Foundation
reaches 0.80% K−1 at 520 K. Most importantly, the emission peak of of Jiangsu Province [No. BK20190725]; and NUPTSF [Grant No.
Cr3+ related to the lifetime-mode temperature measurement is lo­ NY219139].
cated at the first near infrared window of biological tissue, which
supports its application in biological temperature sensing. All these References
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