-
Dual-Mode Luminescent Thermometry in LiYO2:Nd3+,Yb3+ Enabled by Structural Phase Transition and Phonon-Assisted Energy Transfer
Authors:
M. Tahir Abbas,
M. Szymczak,
D. Szymanski,
M. Drozd,
G. Chen,
L. Marciniak
Abstract:
In this work, a dual-mode luminescent thermometer operating via both ratiometric and lifetime-based readout strategies was developed, enabled by the coexistence of two thermally driven effects: a structural phase transition in LiYO2 and a phonon-assisted energy transfer from Yb3+ to Nd3+. As demonstrated, changes in the shape of the emission band of Yb3+ ions corresponding to the 2F5/2 -> 2F7/2 el…
▽ More
In this work, a dual-mode luminescent thermometer operating via both ratiometric and lifetime-based readout strategies was developed, enabled by the coexistence of two thermally driven effects: a structural phase transition in LiYO2 and a phonon-assisted energy transfer from Yb3+ to Nd3+. As demonstrated, changes in the shape of the emission band of Yb3+ ions corresponding to the 2F5/2 -> 2F7/2 electronic transition, induced by the phase transition, enabled the design of a ratiometric thermometer with a maximum relative sensitivity (SR) of 3.1% K^-1 for LiYO2 doped with 10% Yb3+ and 1% Nd3+ at 290 K. In contrast, the temperature-dependent Yb3+ -> Nd3+ energy transfer facilitated the development of a lifetime-based thermometer with a maximum SR of 1.5% K^-1 for 20% Nd3+ at 378 K. In both approaches, tuning the Nd3+ concentration allowed modulation of both the sensitivity and the temperature at which the maximum SR occurred. This was achieved by shifting the phase transition temperature and increasing the probability of interionic energy transfer, respectively.
Notably, the temperature ranges corresponding to the maximum SR for the ratiometric and lifetime modes were distinct, effectively broadening the thermal operating window of the sensor. Additionally, it was shown that LiYO2 doped with Nd3+ and Yb3+ can also be used as a temperature sensor through the ratio of luminescence intensities recorded at two different time gates. Furthermore, the results confirmed that the phonon-assisted energy transfer process plays the dominant role in shaping the luminescence kinetics, surpassing the influence of the structural phase transition. Overall, this study identifies LiYO2:Nd3+,Yb3+ as a promising candidate for multimodal luminescent temperature sensing applications.
△ Less
Submitted 13 November, 2025;
originally announced November 2025.
-
Phase Transition Under Control: Toward Application-Oriented Luminescence Thermometry and Thermally Activated Emission
Authors:
M. T. Abbas,
M. Szymczak,
D. Szymanski,
J. Zeler,
M. Drozd,
L. T. K Giang,
L. Marciniak
Abstract:
Phase-transition-based luminescent thermometers are characterized by two inherent limitations: a narrow thermal operating range and the presence of a hysteresis loop in the thermometric parameter. In this work, we demonstrate that controlling the particle size of LaGaO3:Eu3+ phosphors enables significant enhancement of thermometric performance. Specifically, a reduction in grain size dispersion le…
▽ More
Phase-transition-based luminescent thermometers are characterized by two inherent limitations: a narrow thermal operating range and the presence of a hysteresis loop in the thermometric parameter. In this work, we demonstrate that controlling the particle size of LaGaO3:Eu3+ phosphors enables significant enhancement of thermometric performance. Specifically, a reduction in grain size dispersion leads to an increase in relative thermal sensitivity and significantly narrows the hysteresis loop. As a result of this approach, the relative sensitivity was increased to 18.2% K-1 for LaGaO3:Eu3+ synthesized via the solid-state method, compared to 3.0% K-1 for the counterpart prepared using the Pechini method. Furthermore, we show that the intentional incorporation of Al3+ and Sc3+ co-dopant ions allows for continuous tuning of the structural phase transition temperature from 165 K for 15% Al3+ to 491 K for 2% Sc3+, without significantly affecting the low-temperature spectroscopic properties of Eu3+ ions. This ability to shift the phase transition temperature in LaGaO3 offers a practical route to modulate the thermal response range of the luminescent thermometer, enabling its adaptation to specific application requirements. The empirical relationship established in this study between the phase transition temperature and the ionic radius mismatch parameter provides a predictive tool for the rational design of phase-transition-based phosphors with tailored thermometric performance. The ability to systematically tune the phase transition temperature via ionic radius mismatch, together with enhanced thermometric performance resulting from reduced grain size dispersion, establishes a coherent strategy for the rational design of high-sensitivity, low-hysteresis thermal sensors.
△ Less
Submitted 18 July, 2025;
originally announced July 2025.
-
Modulating Thermometric Performance via Dopant Concentration and Morphology in Luminescence Thermometer Exhibiting Dual Structural Phase Transitions
Authors:
Malgorzata Kubicka,
Maja Szymczak,
Maciej Ptak,
Damian Szymanski,
Vasyl Kinzhybahlo,
Marek Drozd,
Lukasz Marciniak
Abstract:
Expanding the operational range of luminescent thermometers that utilize thermally induced structural phase transitions in lanthanide-doped materials necessitates the exploration of novel host matrices with diverse thermal behaviors. In line with this objective, the present study offers a comprehensive analysis of the temperature-dependent spectroscopic properties of Li3Sc2(PO4)3:Eu3+. The finding…
▽ More
Expanding the operational range of luminescent thermometers that utilize thermally induced structural phase transitions in lanthanide-doped materials necessitates the exploration of novel host matrices with diverse thermal behaviors. In line with this objective, the present study offers a comprehensive analysis of the temperature-dependent spectroscopic properties of Li3Sc2(PO4)3:Eu3+. The findings reveal that the studied material undergoes two reversible phase transitions: γLT - α/\b{eta} phase transition at approximately 160 K, followed by an \b{eta} HT transition around 550 K. These transitions are evidenced by notable alterations in the emission spectra and luminescence decay kinetics of Eu3+ ions. By employing an appropriate luminescence intensity ratio, the sensitivity was determined to be 7.8 % K-1 at 160 K for 0.1%Eu3+ and 0.65 % K-1 at 550 K for 0.5%Eu3+. Furthermore, the study demonstrates that the phase transition temperature in Li3Sc2(PO4)3:Eu3+ can be modulated through variations in dopant ion concentration and annealing conditions, which in turn influence the material's morphology. These strategies enable the fine-tuning of thermometric performance in phase transition-based luminescent thermometers. To the best of our knowledge, this represents the first report in the literature of a luminescent thermometer exhibiting dual thermal operating ranges.
△ Less
Submitted 20 May, 2025;
originally announced May 2025.
-
Breaking Sensitivity Barriers in Luminescence Thermometry: Synergy Between Structural Phase Transition and Luminescence Thermal Quenching
Authors:
M. Tahir Abbas,
M. Szymczak,
M. Drozd,
D. Szymanski,
A. Owczarek,
A. Musialek,
L. Marciniak
Abstract:
One of the key parameters determining the performance of a luminescent thermometer is its relative sensitivity. In ratiometric luminescence thermometry, high relative sensitivity to temperature variations is typically achieved when the two monitored emission bands exhibit opposite thermal monotonicity. However, realizing a thermal enhancement in the luminescence intensity of one of the emission ba…
▽ More
One of the key parameters determining the performance of a luminescent thermometer is its relative sensitivity. In ratiometric luminescence thermometry, high relative sensitivity to temperature variations is typically achieved when the two monitored emission bands exhibit opposite thermal monotonicity. However, realizing a thermal enhancement in the luminescence intensity of one of the emission bands remains a significant challenge. In this study, we present a novel approach that leverages the synergistic effect of two phenomena: (1) the high thermal sensitivity of Mn4+ ion luminescence, and (2) a thermally induced structural phase transition in LaGaO3, which facilitates the enhancement of the luminescence signal from Tb3+ ions in the high-temperature phase of the host material. This dual effect not only led to an increased maximum relative sensitivity but also extended the temperature range over which the sensitivity exceeded 1% K-1. The highest recorded sensitivity was 4.5 K-1 at 400 K. Additionally, to the best of our knowledge, the luminescence of Mn4+ ions in the high-temperature phase of LaGaO3:Mn4+ was observed and reported here for the first time. The thermally induced modifications in the emission profile of LaGaO3:Mn4+,Tb3+ enabled the development of a quadruple ratiometric luminescence thermometer, with complementary operating ranges, offering enhanced versatility and accuracy across a broad temperature span.
△ Less
Submitted 19 May, 2025;
originally announced May 2025.
-
Luminescent Platform for Thermal Sensing and Imaging Based on Structural Phase-Transition
Authors:
Anam Javaid,
Maja Szymczak,
Malgorzata Kubicka,
Vasyl Kinzhybalo,
Marek Drozd,
Damian Szymanski,
Lukasz Marciniak
Abstract:
The remarkable sensitivity of the luminescent properties of Eu3+ ions to structural changes in host materials has been well-explored for years. However, the application of this feature of Eu3+ in materials exhibiting thermally induced structural phase transitions for the development of luminescent thermometers has only recently been proposed. The narrow operating range of such thermometers necessi…
▽ More
The remarkable sensitivity of the luminescent properties of Eu3+ ions to structural changes in host materials has been well-explored for years. However, the application of this feature of Eu3+ in materials exhibiting thermally induced structural phase transitions for the development of luminescent thermometers has only recently been proposed. The narrow operating range of such thermometers necessitates the exploration of new host materials. In response to this demand, this study carefully analyzes the spectroscopic properties of X as a function of temperature and dopant ion concentration. As demonstrated, X undergoes a phase transition from a low-temperature monoclinic phase to a high-temperature trigonal structure, resulting in significant changes in both the emission spectrum shape of Eu ions and the depopulation kinetics of the 5D0 level. Consequently, X can be utilized as both a ratiometric and a lifetime-based luminescence thermometer, achieving maximal relative sensitivities of 3.4 and 1.0 or the respective approaches. Additionally, this work highlights how increasing the concentration of Eu3+ ions enables the tuning of the thermal operating range to achieve optimal thermometric performance. Moreover, an implementation of ratiometric approach of temperature sensing and imaging with X using digital camera without filters was demonstrated. This is the first report that demonstrates thermal imaging using Eu3+-solely doped phosphor. This finding underscores the potential of X as a versatile host material for advanced luminescent thermometry applications.
△ Less
Submitted 9 May, 2025;
originally announced May 2025.
-
NIR-to-NIR ratiometric and lifetime based luminescence thermometer on a structural phase transition in Na3Sc2(PO4)3:Yb3+
Authors:
Anam Javaid,
Maja Szymczak,
Malgorzata Kubicka,
Justyna Zeler,
Vasyl Kinzhybalo,
Marek Drozd,
Damian Szymanski,
Lukasz Marciniak
Abstract:
The ratiometric approach is the most commonly employed readout technique in luminescence thermometry. To address the trade-off between the risk of measurement disturbance in thermometers with high spectral separation of emission bands (due to dispersion in the surrounding medium) and the low sensitivity observed in ratiometric thermometers based on Stark level thermalization, we propose a thermome…
▽ More
The ratiometric approach is the most commonly employed readout technique in luminescence thermometry. To address the trade-off between the risk of measurement disturbance in thermometers with high spectral separation of emission bands (due to dispersion in the surrounding medium) and the low sensitivity observed in ratiometric thermometers based on Stark level thermalization, we propose a thermometer based on the structural phase transition in . The use of Yb3+ ions as dopants and the changes in Stark level energies associated with the thermally induced monoclinic-to-trigonal phase transition enable the development of a thermometer with high relative sensitivity, achieving at 340K for N. Additionally, as demonstrated, the structural transition alters the probability of radiative depopulation of the 2F5/2 state of Yb3+, allowing the development of a lifetime-based luminescence thermometer. Furthermore, the phase transition temperature and consequently the thermometric performance of can be modulated by varying the Yb3+ ion concentration, offering additional tunability for specific applications.
△ Less
Submitted 2 April, 2025;
originally announced April 2025.
-
Expanding the Horizons of Phase Transition-Based Luminescence Thermometry
Authors:
M. Tahir Abbas,
M. Szymczak,
V. Kinzhybalo,
D. Szymanski,
M. Drozd,
L. Marciniak
Abstract:
The limited operational range of phase transition-based luminescence thermometers necessitates the exploration of new host materials exhibiting first-order structural phase transitions to broaden the applicability of this approach. Addressing this need, the present study investigates the spectroscopic properties of as a function of temperature. A thermally induced structural transition from the lo…
▽ More
The limited operational range of phase transition-based luminescence thermometers necessitates the exploration of new host materials exhibiting first-order structural phase transitions to broaden the applicability of this approach. Addressing this need, the present study investigates the spectroscopic properties of as a function of temperature. A thermally induced structural transition from the low-temperature orthorhombic phase to the high-temperature trigonal phase, occurring at approximately 430 K, significantly alters the spectroscopic properties of Eu3 ions. Specifically, a reduction in the number of Stark lines due to changes in the point symmetry of Eu3 ions enables the development of a ratiometric luminescence thermometer with sensitivity as high as K. Furthermore, it was demonstrated that increasing the concentration of Eu3 ions shifts the phase transition temperature, allowing for modulation of the thermometric performance of this luminescence thermometer. The findings presented here not only expand the repertoire of phase transition-based luminescence thermometers but also illustrate how the luminescence properties of Eu3 ions can be employed to accurately monitor structural changes in the host material.
△ Less
Submitted 2 April, 2025;
originally announced April 2025.
-
NIR-to-NIR lifetime based thermometry with the thermally elongated luminescence kinetics driven by structural phase transition in LiYO2:Yb3+
Authors:
M. T. Abbas,
M. Szymczak,
V. Kinzhybalo,
M. Drozd,
L. Marciniak
Abstract:
Among the various techniques used in luminescence thermometry, luminescence kinetics is considered the least sensitive to perturbations related to the optical properties of the medium containing the phosphor. For this reason, temperature sensing and imaging using lifetime-based luminescence thermometers is of high interest for wide range of specific applications. However, for most such thermometer…
▽ More
Among the various techniques used in luminescence thermometry, luminescence kinetics is considered the least sensitive to perturbations related to the optical properties of the medium containing the phosphor. For this reason, temperature sensing and imaging using lifetime-based luminescence thermometers is of high interest for wide range of specific applications. However, for most such thermometers, an increase in temperature leads to a shortening in lifetime, which can hinder the specificity and accuracy of the readout. In this work, we present an approach that utilizes a thermally induced increase in the symmetry of the host material associated with a structural phase transition in LiYO2:Yb3+. Consequently, the lifetime of the excited level 2F5/2 of the Yb3+ ion is thermally prolonged, achieving a relative sensitivity of 0.5%/K. The phase transition temperature can be controlled by adjusting the dopant concentration. Additionally, thermal changes in the emission spectrum enable the use of LiYO2:Yb3+ for ratiometric temperature readout with a relative sensitivity of 5.3%/K at 280K for LiYO2:5%Yb3+.
△ Less
Submitted 4 December, 2024;
originally announced December 2024.
-
Phase transition facilitated highly sensitive luminescence nanothermometry and thermal imaging
Authors:
Lukasz Marciniak,
Wojciech Piotrowski,
Marcin Szalkowski,
Vasyl Kinzhybalo,
Marek Drozd,
Miroslav Dramicanin,
Artur Bednarkiewicz
Abstract:
Currently available temperature measurements or imaging at nano-micro scale are limited to fluorescent molecules and luminescent nanocrystals, whose spectral properties respond to temperature variation. The principle of operation of these conventional temperature probes is typically related to temperature induced multiphonon quenching or temperature dependent energy transfers, therefore, above 12%…
▽ More
Currently available temperature measurements or imaging at nano-micro scale are limited to fluorescent molecules and luminescent nanocrystals, whose spectral properties respond to temperature variation. The principle of operation of these conventional temperature probes is typically related to temperature induced multiphonon quenching or temperature dependent energy transfers, therefore, above 12%/K sensitivity and high thermal resolution remain a serious challenge. Here we demonstrate a novel class of highly sensitive thermographic phosphors operating in room temperature range with milikelvin thermal resolution, whose temperature readings are reproducible, luminescence is photostable and brightness is not compromised by thermal quenching. Corroborated with phase transition structural characterization and high spatio-temporal temperature imaging, we demonstrated that optically active europium ions are highly and smoothly susceptible to monoclinic to tetragonal phase transition in LiYO2 host, which is evidenced by changed number and the splitting of Stark components as well as by smooth variation of contribution between magnetic and electric dipole transitions. Further, reducing the size of phosphor from bulk to nanocrystalline matrix, shifted the phase transition temperature from 100oC down to room temperature. These findings provide insights into the mechanism underlaying phase transition based luminescence nanothermometry and motivate future research toward new, highly sensitive, high temporal and spatial resolution nano-thermometers aiming at precise studying heat generation or diffusion in numerous biological and technology applications.
△ Less
Submitted 2 April, 2021;
originally announced April 2021.
-
Structural phase transitions and their influence on Cu+ mobility in superionic ferroelastic Cu6PS5I single crystals
Authors:
A. Gagor,
A. Pietraszko,
M. Drozd,
M. Polomska,
D. Kaynts
Abstract:
The structural origin of Cu+ ions conductivity in Cu6PS5I single crystals is described in terms of structural phase transitions studied by X-ray diffraction, polarizing microscope and calorimetric measurements. Below the phase transition at Tc=(144-169) K Cu6PS5I belongs to monoclinic, ferroelastic phase, space group Cc. Above Tc crystal changes the symmetry to cubic superstructure, space group…
▽ More
The structural origin of Cu+ ions conductivity in Cu6PS5I single crystals is described in terms of structural phase transitions studied by X-ray diffraction, polarizing microscope and calorimetric measurements. Below the phase transition at Tc=(144-169) K Cu6PS5I belongs to monoclinic, ferroelastic phase, space group Cc. Above Tc crystal changes the symmetry to cubic superstructure, space group F-43c (a=19.528); finally at 274K disordering of the Cu+ ions increases the symmetry to F-43m, (a=9.794). The phase transition at 274K coincides well with a strong anomaly in electrical conductivity observed in the Arrhenius plot. Diffusion paths for Cu+ ions are evidenced by means of the atomic displacement factors and split model. Influence of the copper stechiometry on the Tc is also discussed.
△ Less
Submitted 13 July, 2005;
originally announced July 2005.