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Ultrahigh sensitivity upconversion low

temperature sensors via manipulating the
Cite this: J. Mater. Chem. C, 2023,
11, 8758 non-thermally coupled levels of Er3+ ions†
Received 27th March 2023,
Accepted 12th June 2023 Weitao Ying,a Jingyi He,a Xuemei Fan,a Shiqing Xu,*a Jianmin Gu *ab and
Shimin Liu *a
DOI: 10.1039/d3tc01062g

rsc.li/materials-c

Realizing high-sensitivity, accurate non-contact cryogenic optical sensors on the basis of thermocoupling and thermal resistance
thermometry based on upconversion (UC) luminescence holds commonly demand physical contact and heat transfer, and have
significant application value in numerous advanced technology serious limitations in low temperature environments.5 Optical
fields. Here, we report a novel temperature sensing strategy using thermometry, as a noncontact temperature measurement
the non-thermally coupled levels (NTCLs) formed by the blue emission method, can convert the temperature signal into an optical
level (2H9/2) based on Er3+ ions, which exhibit ultrahigh sensitivity signal for further output and display, which is better adapted
under the excitation of two lasers (980 or 1550 nm). The prepared to cryogenics, high voltage, corrosive environments and other
glass-ceramic (GC) containing Er,Yb:NaYF4 possesses excellent UC extreme conditions.6,7 The work based on rare earth upconver-
luminescence performance, and could respond to 980 and 1550 nm sion (UC) luminescence could offer a non-contact temperature
wavelength excitation and produce apparent blue emission. The measurement method by utilizing fluorescence intensity ratio
fluorescence intensity ratio (FIR) optical thermometry of NTCLs con- (FIR) technology,8–10 possessing high spatial resolution, fast
taining blue emission levels (2H11/2–2H9/2, 4
F9/2–2H9/2) has higher response speed, and strong anti-interference ability thanks to
absolute and relative sensitivity, thanks to the more pronounced the narrow emission band, high stability and large anti-Stokes
difference in response to temperature of NTCLs that absorb different shift.11–14 Most UC optical thermometry typically uses the
numbers of photons. Based on the 2H11/2–2H9/2 NTCL, the maximal thermally coupled levels (TCLs) of rare earth or transition metal
value of SR is 5.608% K1 (5.339% K1) under 980 (1550 nm) excitation, ions, where the TCL population abides by the Boltzmann
which is greater than that of the TCL and traditional 4F9/2–4S3/2 NTCL. distribution and the energy gap should be between about 200
The results indicate that the prepared GC material has a great and 2000 cm1.15–17 Transition metal ions, such as Cr3+, could
improvement in the sensitivity of temperature sensing, while providing also be used for optical temperature measurement based on the
a novel strategy for realizing ultrahigh sensitivity dual-mode optical Boltzmann distribution, which combines the flexibility of the
thermometry. relative energy gap between the 4T2–2E couple, possessing higher
sensitivities and better thermal resolutions.18–21 In addition, the
non-thermally coupled levels (NTCLs) originate from two excited
levels with different temperature-dependence characteristics,
Introduction which may lead to higher relative sensitivity due to not being
Temperature measurement, especially low temperature limited by energy gap and depending on temperature controlled
measurement, is of great significance in various fields such energy transfer and thermal quenching rate.22,23
as medicine, bioengineering, aerospace, infrared detectors and Rare earth ions, particularly Er3+ ions with abundant ladder-
energy technology.1–4 Conventional contact temperature like arranged energy level structures, can provide a variety of
emission energy levels used for optical temperature sensing,24–26
a
State Key Laboratory of Metastable Materials Science and Technology (MMST), such as 4F9/2, 4S3/2, 2H11/2, and 2H9/2 levels,27 where 2H11/2–4S3/2
Yanshan University, Qinhuangdao 066004, China. E-mail: [email protected], belongs to TCL, and 4F9/2–4S3/2, 4S3/2–2H9/2, and 4F9/2–2H9/2
[email protected] belong to NTCL. However, the 2H11/2–4S3/2 TCL is mainly used
b
Hebei Key Laboratory of Applied Chemistry, School of Environmental and
for high temperature sensing, and the optical temperature
Chemical Engineering, Yanshan University, Qinhuangdao 066004, China.
E-mail: [email protected]
sensitivity of the 4F9/2–4S3/2 NTCL is difficult to be further
† Electronic supplementary information (ESI) available. See DOI: https://doi.org/ enhanced due to the limitation of the emission energy levels.
10.1039/d3tc01062g The 4S3/2–2H9/2 or 4F9/2–2H9/2 emission levels are NTCLs that

8758 | J. Mater. Chem. C, 2023, 11, 8758–8766 This journal is © The Royal Society of Chemistry 2023
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respond to different photon numbers, where the electron transition 2

H11/2–2H9/2, while 1.128 K1 and 1.872% K1 on the basis of
and non-radiative relaxation process would change more obviously the 4F9/2–2H9/2 NTCL under 1550 nm excitation, which are both
with temperature, which could be utilized to further improve the higher than the common NTCL pair of 4F9/2–4S3/2. The FIR
temperature sensing sensitivity. The 2H9/2 level of Er3+ is usually method based on NTCL that contains 2H9/2 levels also possess
difficult to provide UC emission due to the more photon (three or higher sensitivity upon 980 nm excitation, which could be com-
four photons) absorption processes and the strong lattice scatter- bined with a 1550 nm excitation source to realize dual-mode
ing. Embedding Er,Yb:NaYF4 crystals into oxide glass could form optical temperature measurement, completing self-calibration
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the oxyfluoride glass-ceramic (GC),28,29 where the glass network under the premise of high sensitivity. The results provide a novel
structure could better transmit photons and improve the utilization strategy for dual-mode temperature sensing with ultrahigh
rate of infrared excitation sources,30 which could promote the sensitivity.
electron transition to higher emission energy levels (2H9/2 levels),
improving the combination of NTCLs. Moreover, the glass network
structure of GC encapsulates the fluoride crystals, which could Results and discussion
maintain stability at low temperature and in special environments
(high humidity, acid environment), further expanding the applica- The prime UC temperature measurement material demands
tion field of optical thermometers. strong physical and chemical stability to meet the harsh environ-
Herein, we report a strategy to design ultrahigh sensitivity ment, while low phonon energy to minimize non-radiation relaxa-
cryogenic temperature sensing based on Er3+ ions, which is tion and increase UC luminescence intensity.31,32 Therefore, the
realized by FIR of NTCLs containing blue emission levels (2H9/2). oxyfluoride GC was selected as the host material, which is
The Er,Yb:NaYF4 GC material is successfully prepared via the composed by amorphous glass phase (high mechanical stability)
melting-quenching method, which exhibits excellent UC lumi- and fluoride nanocrystal phase (low phonon energy). Fluoride
nescence properties that produce obvious blue emission under nanocrystals doped with rare earth ions can be gradually pre-
980 nm or 1550 nm single excitation, providing the novel cipitated and uniformly distributed in the glass phase after the
combination mode of the NTCL. The temperature-dependent subsequent heat treatment process on PG prepared through
characteristics are produced in the low temperature range of the traditional conventional melting-quenching method. An
90 K–300 K under the excitation of both wavelength lasers, where amorphous hump was observed in the XRD pattern, which is
the FIR value of NTCL formed by green-blue (2H11/2–2H9/2) and the typical feature of PG (Fig. 1a). The diffraction peak of the cubic
red-blue (4F9/2–2H9/2) emission levels exhibit the more remark- NaYF4 phase (PDF#77-2042) appeared after glass crystallization at
able change, providing higher temperature sensing sensitivity. 600 1C for 2 hours, indicating the successful formation of NaYF4
The maximum absolute (SA) and relative (SR) sensitivity are nanocrystals. According to the Debye-Scherrer equation, the aver-
calculated to be 0.194 K1 and 5.339% K1 based on NTCL of age particle size of Er,Yb:NaYF4 nanocrystals is calculated to be

Fig. 1 (a) XRD patterns of PG and a-NaYF4 GC. (b) Schematic illustration of the NaYF4:Er,Yb crystal structure. (c) Photographs of the GC sample and
photographs of UC luminescence. (d) TEM micrographs of the GC sample. (e) HRTEM micrograph of a single particle in the GC sample, and the insert is
the SAED pattern. (f) Corresponding average particle size distribution histogram of the GC sample. (g) STEM micrographs of the GC sample and (h) the
related element mapping of Si, Al, Na, Y, F and Er. The scale bar is (c) 10 mm, (d) and (g) 200 nm, (e) 2 nm, and (h) 100 nm.

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21.8 nm. Cubic NaYF4 exhibits a fluorite-type crystal structure, in Y3+ ions have similar ionic radius, where Er3+,Yb3+ ions would
which Na+ and Y3+ ions randomly replace the cationic crystal sites be preferentially enriched in NaYF4 nanocrystals due to the
in a 1 : 1 ratio, and rare earth Er3+ ions will occupy the Y3+ site to characteristics of replacement solid solution substitution.34
produce excellent UC luminescence (Fig. 1b). The prepared GC An optical thermometer based on the NTCL of rare earth
material can be further mechanically cut into different shapes ions is regarded as a promising approach for temperature
(such as flakes) without rupture, exhibiting excellent mechanical determination with higher relative sensitivity. However, the
stability while maintaining bright luminescence (Fig. 1c). thermometers based on NTCL also suffer from uncontrollable
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The TEM images (Fig. 1d) of the nanostructured GC sample environment fluctuation factors including refractive index var-
clearly present the even distribution of NaYF4 nanocrystals in iations, probe inhomogeneity, and excitation angle change,
the aluminosilicate glass matrix, where the average size of the which may ultimately lead to inaccurate measurement. Among
nanocrystals is about 22.65 nm (Fig. 1f), dovetailing with the most rare-earth ions, Er3+ ions could well match with NIR-II and
particle size results based on XRD data. The high-resolution NIR-III photons because of the specific energy level structure,
lattice fringes emerge in the HRTEM image with a measured which has a variety of effective electronic transition pathways,35–37
interplanar spacing of 0.312 nm, which is a perfect match with providing a basis for realizing dual-mode optical temperature
the (111) lattice plane of a-NaYF4, indicating the successful sensing, and improving the accuracy of temperature detection to a
crystallization of glass (Fig. 1e). Meanwhile, the SAED pattern of certain extent. The dual-mode temperature sensing concept is
the GC sample exhibits apparent polycrystalline electron dif- based on the UC luminescence process of the Er3+ ion-doped GC
fraction rings (Fig. 1e, inset), further verifying the precipitation sample under different excitation wavelengths (980 or 1550 nm),
of the a-NaYF4 nanocrystals.33 In the HAADF-STEM, the con- and the response mechanism to temperature (Fig. 2a).
trast of the nanocrystals is brighter than that of the alumino- The thermochromism luminescence properties of the GC
silicate glass matrix due to the Y atomic number in the NaYF4 material were investigated with a home-made optical test plat-
crystal being larger than the Si/Al atomic number distributed in form under the excitation of 980 nm (21.6 mW mm2) and
glass (Fig. 1g), which would be used to ascertain the distribu- 1550 nm (28.0 mW mm2) lasers, respectively (Fig. 2b and
tion of elements. Elements of Na, Y and Er are mainly dis- Fig. S1, ESI†). One blue emission (B), two green emissions
tributed in the nanocrystals, while F, Al and Si are maintained (G1, G2) and one red emission (R) band at 409, 530, 542 and
in the glass matrix, indicating that the Er3+ activators are 656 nm are observed, which respectively correspond to the 2H9/2,
successfully introduced into the NaYF4 crystalline lattice after 2
H11/2, 4S3/2, 4F9/2 - 4I15/2 transitions of Er3+ ions,38 under
glass crystallization (Fig. 1h). And the rare earth Er3+, Yb3+and 980 nm laser excitation (Fig. 2c). The presence of blue emission

Fig. 2 (a) Possible electronic transition and UC emission process of Er ions excited by 980 and 1550 nm lasers. (b) Schematic diagram of the UC
luminescence spectra test platform with a temperature control system. (c) Emission spectra of the GC sample at 90 K and 300 K excited by a 980 nm
laser. Normalized UC emission spectra of the GC sample upon (d) 980 nm and (e) 1550 nm excitation at various temperatures. Integrated UC intensities
of B, G1 and R emission at different temperatures under (f) 980 nm and (g) 1550 nm excitation. (h) CIE chromaticity coordinates at various temperatures
upon 1550 nm excitation.

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suggests that the prepared GC is an excellent UC luminescence FIR technology. The obtained CIE chromaticity diagrams indi-
material, because the blue emission usually disappears thanks to cate that the emission color of the GC material gradually shifts
the strong scattering of the main lattice and three or four photon from green to yellow, which is due to the change of electron
processes in the Er3+,Yb3+ doped system. Interestingly, at a low distribution on emission levels caused by the temperature
temperature of 90 K, the G1 emission ascribed to the 2H11/2 level effect (Fig. 2h and Fig. S5, Tables S1, S2, ESI†).
shows a marked decrease, while the B emission ascribed to the The dependence of UC luminescence on pumping power
2
H9/2 level increases, which suggests that the UC emission was analyzed so as to understand the UC emission process of
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intensities are highly dependent on temperature. the GC material under different lasers excitations,39 where all
The UC spectra regulation behaviors by temperature and emission intensities increased gradually with increasing power
the emission intensity ratio were systematically studied under density (Fig. S6 and S7, ESI†). The emission intensity IUC and
980 (1550) nm excitation at a low temperature range of 90– pumping power density P follow the formula log(I) = n log(P) +
300 K (Fig. 2d, e and Fig. S2, ESI†). The B, G2, and R emission constant, where n is the number of UC photons required to fill
intensity decreased monotonously with increasing tempera- the specific emission levels.40,41 Excited via 980 nm laser at low
ture, while the G1 emission intensity increased, under the or room temperature, the values n of blue emission are all close
condition of either 980 nm or 1550 nm laser excitation to 3, which illuminates that the blue emission process requires
(Fig. 2f, g and Fig. S3, ESI†). Compared with the common the absorbance of three photons (Fig. 3a–c). The slopes n for
Er3+/Yb3+ doped UC system, the blue emission peak of the green and red emissions are close to 2, indicating that green
prepared GC material also exhibits a temperature-dependent and red emission processes need to absorb two photons.
change behavior, which provides more energy level options for Analogously, under 1550 nm excitation (low or room tempera-
temperature sensing based on FIR technology. The emission ture), the blue luminescence is a four-photon process, and the
intensity ratios between the four emission peaks: G1/G2, R/B, green and red emissions are three-photon processes (Fig. 3d–f),
R/G2, G1/B all tend to increase to a certain extent with the raise where the four-photon process of blue luminescence further
of temperature (Fig. S4, ESI†). The GC material exhibits a expresses that the prepared GC is a prime UC material. The value
significant change in emission intensity ratio under 980 or n decreases slightly with increasing temperature, affecting the
1550 nm laser excitation, offering a guarantee for the subse- variety of luminescence intensity. There are two main reasons for
quent realisation of multimode optical thermometry based on the influence of temperature on the value of n: one is because

Fig. 3 The 980 nm laser excitation power dependence with UC emission at (a) 90 K, (b) 180 K, and (c) 270 K. The 1550 nm laser excitation power
dependence with UC emission at (d) 90 K, (e) 180 K, and (f) 270 K. (g) UC luminescence mechanism of Er,Yb:NaYF4 GC upon 980 and 1550 nm excitation.
(h) Schematic illustration diagram based on TCL and NTCL of UC emission dependent on temperature.

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the probability of non radiative relaxation between energy levels various combinations of emission intensity ratio, such as G1/G2
increases with the temperature rise; the other is that the excited (TCL) and R/G2, R/B, and G1/B (NTCLs) (Fig. 3h). The opposite
state energy levels of Er3+ ions gradually saturate, which leads to changes in G1 and G2 emission intensities originate from the
a slight reduction of the photons absorbed.42 And the blue evolution of the electron populations on their emission levels
emission process of Er3+ ions at room temperature has higher (2H11/2 and 4S3/2), where their small energy gap allows the 2H11/2 level
probability of non-radiative relaxation, resulting in a low value of to be filled through thermal excitation from the 4S3/2 level (Fig. S8,
n (3.18), while still belongs to a four photon process. ESI†). According to the Boltzmann distribution theory, the FIR for
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Based on the number of photons absorbed by different G1 and G2 emissions with temperature could be expressed as46,47
emission levels, the UC luminescence mechanism of the GC  
IG1 DE
material under different excitation conditions is specifically FIRT ¼ ¼ C exp  (1)
IG2 KT
analyzed (Fig. 3g). Under 980 nm laser excitation, Er3+ ions
transit from the 4I15/2 energy level to the 4I11/2, 4F9/2 and 4F7/2 where IG1 and IG2 are the two green emission intensities. C, K, and T
energy levels via utilizing two 980 nm photons transmitted are the pre-exponential constant, Boltzmann constant, and absolute
from Yb3+ ions, which results in corresponding green emis- temperature; and DE is the energy gap between the 2H11/2/4S3/2 TCLs.
sions (2H11/2/4S3/2 - 4I15/2) and red emission (4F9/2 - 4I15/2). In terms of optical temperature sensing analysis, the 980 nm laser
While the electrons at the 4F9/2 and 4S3/2 levels absorb one power density is 21.6 mW mm2, and the 1550 nm laser power
980 nm photon and continue upward transiting to the 4G11/2 density is 28.0 mW mm2, which is consistent with the previous UC
and 2H9/2 levels, resulting in blue emission (2H9/2 - 4I15/2). For spectra analysis. The low excitation power density could minimize
1550 nm excitation, the electrons on the 2H11/2 and 4S3/2 levels the impact of the laser thermal effect on temperature measurement
are completed via continuously absorbing three 1550 nm accuracy.
photons; while the population of 4F9/2 levels could be realized The single-exponential fitting to the experimental data
by absorbing two photons jumping to the 4I9/2 level, relaxing to yields the energy gap DE between the 2H11/2 and 4S3/2 levels of
4
I11/2 level, and finally absorbing another photon to reach 4F9/2. Er3+ ions based on eqn (1), where the values are 690.8 cm1
The 4I11/2 level would also transfer its energy to Yb3+ ions and under 980 nm excitation and 715.9 cm1 upon 1550 nm excita-
make the Yb3+ ions jump to the 2F5/2 level, where the excited Yb3+ tion (Fig. S9, ESI†). The obtained energy gaps of TCL under the
could further transfer the energy to Er3+ ions, and the electrons on excitation of the two different wavelengths are basically identical,
4
I13/2 are gradually excited to the 4F9/2 level. Similarly, the electrons which further illustrates the accuracy of the data fitting. For the
at the 4S3/2 energy level continue to absorb one 1550 nm photon evaluation of the optical temperature sensor properties, the
and upward transition to the 2H9/2 level, realizing blue emission. absolute (SA) and relative (SR) sensitivity are very important
The emission of the 2H11/2 level (530 nm) is observed to be parameters, which can be calculated as follows48,49
weak at ultralow temperature under both 980 nm and 1550 nm
dðFIRÞ
laser excitation, which would be used to analyze the electronic SA ¼ (2)
dT
layout process in detail. We deduce that the principal reason is
because of the energy on the 2H11/2 level requiring thermal
1 dðFIRÞ
population from the 4S3/2 level. The electrons at the 2H11/2 level SR ¼  100% (3)
FIR dT
are restrained at low temperature because they demand thermal
activation to fill, causing a weak emission of the 2H11/2 level.43 The SR is more practical compared with SA, which could quantify
Under 980 nm laser excitation, the electrons transitioning to the and compare the sensitivity of different thermometers.50 And the
4
F7/2 energy level would preferentially non-radiatively relax to the temperature uncertainty (dT) that indicates the smallest detect-
4
S3/2 level, where with temperature increasing, the electrons are able temperature change is essentially determined by SR, where
populated to the 2H11/2 level from 4S3/2 through a thermalization the dT values could increase with the decrease of the SR value.51
process. Similarly, for 1550 nm laser excitation, we suppose that The temperature sensitivity of the TCL (G1/G2) is calculated,
the Er3+ ions would imbibe three 1550 nm photons directly to where SA gradually increases and SR keeps decreasing with
populate the 4S3/2 level, and further reach the 2H11/2 level an increase under either 980 nm or 1550 nm laser excitation
through the process of thermalization. Therefore, the G1 emis- (Fig. S10, ESI†). Interestingly, the maximum SA and SR of the GC
sion intensity of the GC material is enhanced with increasing material are also identical under different wavelength laser
temperature based on the thermal coupling effect, where the excitations, indicating that the temperature sensing property
electrons at the 4S3/2 levels can efficiently jump to 2H11/2 levels on the basis of TCL is independent of the excitation source.
at higher temperatures (Fig. 3h). The decrease of other emission Compared with TCL-based temperature measurement, FIR
(B, G2, R) intensities is because of the thermal quenching effect technology using NTCLs could be not limited by the energy gap
resulting in increasing temperature,44,45 in which the lumines- and has higher sensitivity, while the signal discrimination is
cence center in the excited state returns to the ground state high due to the large distance between the emission peaks of
through non-radiative means. the two NTCLs, which is more conducive to practical applica-
The prepared Er,Yb:NaYF4 GC material possesses abundant tions. The glass network of the GC material encapsulates the
emission energy levels under NIR-II and NIR-III pumping, while Er,Yb:NaYF4 crystals to protect them from external environ-
all have obvious temperature response characteristics, providing mental influences, which possess obvious advantages in the

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field of temperature sensing. As a proof-of-concept illustration, and the maximal SA and SR are 0.015 K1 (300 K) and 1.564% K1
we design a dual-mode temperature sensing strategy, where the (170 K) upon 1550 nm excitation (Fig. S14, ESI†).
980 and 1550 nm laser source excites the GC sensing device The prepared GC material exhibits excellent blue emission
through a commercial fiber, and the generated UC emission signal under 980 or 1550 nm laser excitation, which provides more
is further collected and passed back to spectra detection equipment options for FIR technology based on NTCLs. Therefore, the R
by the fiber (Fig. S11, ESI†). The two sets of temperature-dependent and B emissions (4F9/2–2H9/2), as well as G1 and B emissions
FIR information could be obtained through using two lasers, (2H11/2–2H9/2) can also constitute NTCLs, and their emission
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980 nm and 1550 nm, as excitation light sources. By using these ratios change more significantly with increasing temperature.
two different FIR and temperature relationships, corresponding Based on the R/B and G1/B emission ratios, the FIRs of the
4
temperature information (temperature value) can be obtained F9/2–2H9/2 NTCL and 2H11/2–2H9/2 NTCL are fitted under either
respectively, which can be mutually verified to achieve the self- 980 or 1550 nm excitation (Fig. 4a, b and Fig. S15, S16, ESI†).
calibration function. The FIR based on NTCL can be fitted via the The temperature sensitivities (SA and SR) of the two NTCL
fourth-order polynomial function:52,53 systems are further investigated under two different excitation
sources. Based on the 4F9/2–2H9/2 NTCL, the maximal values of
I2
FIRNT ¼ ¼ B0 þ B1 T þ B2 T 2 þ B3 T 3 þ B4 T 4 (4) SA and SR are obtained to be 0.132 K1 (300 K) and 1.269% K1
I1
(130 K) under 980 nm excitation, and the maximal values of
where Ii is luminescence intensity, Bi is the fitting constant of the SA and SR are 1.128 K1 (300 K) and 1.872% K1 (160 K) under
polynomial, and T is the absolute temperature. For the 4F9/2 and 1550 nm excitation (Fig. 4c and d). For 2H11/2–2H9/2 NTCL,
4
S3/2 NTCL, the value of FIR can be obtained from the emission the maximal value of SA is 0.062 K1 and the maximal SR is
ratio R/G2, where the FIR increases with temperature and could be 5.608% K1 under 980 nm excitation, and the maximal SA is
well fitted with the polynomial function (Fig. S12 and S13, ESI†). 0.194 K1 and the maximal SR is 5.339% K1 under 1550 nm
The temperature sensitivities for R/G2 (SA and SR) are calculated excitation. The temperature sensitivity of the FIR designed
according to eqn (2) and (3). The maximal values of SA and SR are based on NTCLs involving blue emission is greater than that
0.005 K1 (300 K) and 1.102% K1 (130 K) under 980 nm excitation, of the traditional TCL and 4F9/2–4S3/2 NTCL, indicating that our

Fig. 4 Dependence of FIR and temperature based on the NTCL of 4F9/2/2H9/2 and 2H11/2/2H9/2 upon (a) 980 nm and (c) 1550 nm excitation. Absolute and
relative sensitivities of temperature sensing based on 4F9/2/2H9/2 and 2H11/2/2H9/2 NTCLs under (b) 980 nm and (d) 1550 nm excitation. (e) Comparison of
the thermometric performance of rare earth-doped materials based on FIR technology. Ma: Er3+/Yb3+:NaLa(WO4)2;54 Mb: La2Mo3O12:Yb/Er;55 Mc:
NaSrPO4:Er3+/Yb3+ GC;56 Md: BiF3:Yb3+/Er3+;57 Me: Er3+:Y3Ga5O12:Er3+;58 Mf: NaGdF4:Yb3+/Er3+;59 Mg: KLa(MoO4)2:Ho3+/Yb3+;53 Mh: NaYF4:Er3+.5

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prepared material has a great improvement in the sensitivity of and blue emissions (4F9/2–2H9/2), as well as the green and blue
optical temperature sensing (Fig. 4e). emissions (2H11/2–2H9/2) can also constitute NTCLs, where their
The temperature uncertainty (dT), also known as the tempera- emission ratios change more significantly with increasing
ture resolution or thermal resolution (DT), is another important temperature, which further enhances the temperature sensitiv-
parameter in optical temperature sensing, which represents the ity. The maximum SA and SR are calculated to be 0.194 K1 and
smallest detectable temperature change.19,60–62 We further analyze 5.339% K1 based on the NTCL of 2H11/2–2H9/2, while 1.128 K1
the temperature resolution based on 2H11/2–2H9/2 NTCL (G1/B) and 1.872% K1 on the basis of 4F9/2–2H9/2 NTCL under 1550 nm
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temperature measurement through the following formula17,21 excitation. Moreover, two excitation sources can be employed to
excite the GC for dual-mode optical thermometry, which realizes
1 dFIR
dT ¼ DT ¼ (5) mutual verification and self-calibration of the temperature,
SR FIR
further ensuring the accuracy of temperature measurement.
where the dFIR/FIR is the uncertainty in the calculation of FIR, and The results provide a novel strategy for dual-mode ultrahigh
can be written as18 sensitivity optical thermometry based on UC luminescence.
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
 2  2
dFIR dI1 dI2
FIR
¼
I1
þ
I2
(6) Author contributions
Shiqing Xu, Jianmin Gu and Shimin Liu conceived the idea and
where the dI1/I1 and dI2/I2 values could be calculated through
supervised the project. Weitao Ying and Jingyi He carried out
dividing the readout fluctuations of the baseline by the average
the experiment and sample characterization. Weitao Ying and
emission intensity value of 530 nm (G1) and 409 nm (B), respec-
Xuemei Fan analyzed the data. Weitao Ying, Shiqing Xu, Jianmin
tively. At 90 K, the GC material has the minimum temperature
Gu and Shimin Liu wrote the manuscript. All authors discussed
resolution values of 0.51 K (980 nm) and 0.56 K (1550 nm), which
the results and commented on the manuscript. All authors have
indicates its excellent ability to distinguish small temperature
given approval to the final version of the manuscript.
changes and ensure sufficient reliability at low temperature
(Fig. S17, ESI†). Traditional Boltzmann thermometers based on
Nd3+ and Cr3+ also exhibit excellent optical temperature measure- Conflicts of interest
ment performance in terms of relative and absolute sensitivity, as
There are no conflicts to declare.
well as thermal resolution.17–21,63–66 Compared with these excel-
lent Boltzmann thermometers, the performance of the Er,Yb:-
NaYF4 GC sensor based on 2H11/2–2H9/2 NTCL has higher relative Acknowledgements
sensitivity and slightly poorer thermal resolution. At low tempera-
ture (90 K), the GC sensor has thermal resolution comparable to This work was supported by the National Natural Science
Nd3+ and Cr3+ based thermometers, indicating that it possesses Foundation of China (No. 52072331).
certain advantages in low temperature measurement.
Meanwhile, the repeatability of GC temperature sensor read-
Notes and references
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