Upconversion Nanocrystal Doped Polymer Fiber Thermometer.

In recent years, lanthanide-doped nanothermometers have been mainly used in thin films or dispersed in organic solvents. However, both approaches have disadvantages such as the short interaction lengths of the active material with the pump beam or complicated handling, which can directly affect the achievable temperature resolution. We investigated the usability of a polymer fiber doped with upconversion nanocrystals as a thermometer. The fiber was excited with a wavelength stabilized diode laser at a wavelength of 976 nm. Emission spectra were recorded in a temperature range from 10 to 35 ∘C and the thermal emission changes were measured. Additionally, the pump power was varied to study the effect of self-induced heating on the thermometer specifications. Our fiber sensor shows a maximal thermal sensitivity of 1.45%/K and the minimal thermal resolution is below 20 mK. These results demonstrate that polymer fibers doped with nanocrystals constitute an attractive alternative to conventional fluorescence thermometers, as they add a long pump interaction length while also being insensitive to strong electrical fields or inert to bio-chemical environments.

Highly Sensitive Temperature Sensors Resulting from the Luminescent Behavior of Sm3+-Doped Ba2MgMoO6 High-Symmetry Double-Perovskite Molybdate Phosphors.

We present double-perovskite molybdate with the formula of Ba2MgMoO6 doped with Sm3+ ions as a potential red phosphor to improve the color characteristics of white-light-emitting dioded (wLEDs). The new orange-red phosphor was synthesized using the co-precipitation (CP) method, and then its structural and spectroscopic properties were determined. Red emission at 642.6 nm dominates, which results from the electric dipole (ED) transition of the 4G5/2 → 6H9/2 type, and the materials are characterized by short luminescence decay times. BMM:Sm3+ is, to our best knowledge, the clearest example of dominant red emission of Sm3+ resulting from the location of the dopant in octahedral sites of high-symmetry cubic structure. In the sample containing 0.1% Sm3+, Sm3+ ions are located in both Mg2+ and Ba2+ sites, while at higher concentrations the Ba2+ site is less preferable for doping, as a result of which the emission becomes more uniform and single-site. The relative sensitivity calculated from FIR has a maximum of 2.7% K-1 at -30 °C and another local maximum of 1.6% K-1 at 75 °C. Such value is, to the best of our knowledge, one of the highest achieved for luminescent thermometry performed using only Sm3+ ions. To sum up, the obtained materials are good candidates as red phosphor to improve the color characteristics of wLEDs, obtaining a color-rendering index (CRI) of 91 and coordinated color temperature (CCT) of 2943 K, constituting a warm white emission. In addition to this, a promising precedent for temperature sensing using high-symmetry perovskite materials is the high sensitivity achieved, which results from the high symmetry of the BMM host.

Highly-sensitive optical thermometer developed based on an intervalence charge transfer mashup.

Optical thermometers based on lanthanide thermal-coupled levels have attracted great attention owing to its fundamental importance in the fields of public health, biology, and integrated circuit. However, the inherent structural properties (shielded effect on 4f configurations, intense non-radiation relaxation) strictly suppress the sensing performance, limiting the relative temperature sensitivity (SR). To circumvent these limitations, we propose an intervalence charge transfer mashup strategy by inducing d0 electron configured transition metals. Specifically, transition metals Ta5+ is incorporated in Tm3+/Eu3+:LiNbO3, which improves the SR from 5.30 to 11.16% K-1. The validity of this component-modulation behavior is observed on other oxide crystals (NaY(Mo1-zWzO4)2) as well. Furthermore, the observed regulation is well explained by DFT calculation that indicates the d-orbit component at valence band minimum remains the core factor governing the electron transfer process. We successfully relate the SR to the band structure of luminescence carrier, offering a novel perspective for the collocation design of lanthanide configurations.

Visual ratiometric optical thermometer with high sensitivity and excellent signal discriminability based on LiScSiO4:Ce3+, Tb3+ thermochromic phosphor.

Developing optical thermometer phosphors with high sensitivity, high signal discriminability and strong fluorescence intensity is ongoing. A dual-emitting thermochromic phosphor, LiScSiO4:Ce3+, Tb3+, was successfully synthesized via solid-state reaction method. The crystal structure, electronic structure, luminescent performance and thermal luminescence behaviors as well as the luminescence mechanism of LiScSiO4:Ce3+, Tb3+ were systematically investigated. Due to the energy transfer and different thermoluminescence behaviors between Ce3+ and Tb3+, high relative sensitivity (2.2 % K-1@473 K), excellent signal discriminability (5747 cm-1), outstanding temperature resolution (0.067 K) and good repeatability, as well as efficient emission at high temperatures were achieved based on the fluorescence intensity ratio of Ce3+ and Tb3+, indicating its potential in ratiometric optical thermometer. Moreover, the excellent visualizing thermochromic enable LiScSiO4:Ce3+, Tb3+ to be used as safety sign in variable temperature environment to monitor temperature distribution.

Metal-Organic Framework Optical Thermometer Based on Cr3+ Ion Luminescence.

Metal-organic frameworks with perovskite structures have recently attracted increasing attention due to their structural, optical, and phonon properties. Herein, we report the structural and luminescence studies of a series of six heterometallic perovskite-type metal-organic frameworks with the general formula [EA]2NaCrxAl1-x(HCOO)6, where x = 1, 0.78, 0.57, 0.30, 0.21, and 0. The diffuse reflectance spectral analysis provided valuable information, particularly on crystal field strength (Dq/B) and energy band gap (Eg). We showed that the Dq/B varies in the 2.33-2.76 range depending on the composition of the sample. Performed Raman, XRD, and lifetime decay analyses provided information on the relationship between those parameters and the chemical composition. We also performed the temperature-dependent luminescence studies within the 80-400 K range, which was the first attempt to use an organic-inorganic framework luminescence thermometer based solely on the luminescence of Cr3+ ions. The results showed a strong correlation between the surrounding temperature, composition, and spectroscopic properties, allowing one to design a temperature sensing model. The temperature-dependent luminescence of the Cr3+ ions makes the investigated materials promising candidates for noncontact thermometers.

Photoluminescence properties of Ca9La(PO4)5SiO4F2:Ce3+/Tb3+/Mn2+ phosphors for applications in white light-emitting diodes and optical thermometers.

A series of Ca9La(PO4)5SiO4F2:Ce3+,Tb3+,Mn2+ (CLPSF:Ce3+,Tb3+,Mn2+) phosphors were obtained by a conventional solid-state reaction method, and the luminescence properties excited by ultraviolet light were investigated in detail. The Ce3+-doped CLPSF samples show near-ultraviolet luminescence with the dominant peaks around 361 nm. Different Ce3+ emission centers were identified from the emission spectra. When the Ce3+ and Mn2+ are codoped into the host, an energy transfer (ET) from Ce3+ to Mn2+ was found, owing to which the visible emitting-light-color has been tuned from blue to light brown. The corresponding ET mechanism was studied by employing Dexter's theory. In the Ce3+-Tb3+ codoped CLPSF phosphors, the tunable emission was realized on the basis of the ET between Ce3+ and Tb3+. To further obtain the white emissions with tunable correlated color temperature, the Ce3+-Tb3+-Mn2+ tridoped CLPSF samples were designed, and the ET relationship in these phosphors were discussed. By studying the thermally luminescent properties, it was found that the Ce3+ and Mn2+ emission intensities in the CLPSF:Ce3+,Mn2+ samples showed different decrease rates with increasing temperature. The fluorescence intensity ratio (FIR) technique was used to investigate the temperature-sensing performance. On the other hand, the CLPSF:Ce3+,Tb3+ and CLPSF:Ce3+,Tb3+,Mn2+ phosphors exhibit relatively high thermally luminescent stability. The above discoveries indicate that the developed phosphors could have potential applications in LEDs and optical thermometer.

Upconverting Lanthanide Fluoride Core@Shell Nanorods for Luminescent Thermometry in the First and Second Biological Windows: ß-NaYF4:Yb3+- Er3+@SiO2 Temperature Sensor.

Upconverting core@shell type ß-NaYF4:Yb3+-Er3+@SiO2 nanorods have been obtained by a two-step synthesis process, which encompasses hydrothermal and microemulsion routes. The synthesized nanomaterial forms stable aqueous colloids and exhibits a bright dual-center emission (λex = 975 nm), i.e., upconversion luminescence of Er3+ and down-shifting emission of Yb3+, located in the first (I-BW) and the second (II-BW) biological windows of the spectral range, respectively. The intensity ratios of the emission bands of Er3+ and Yb3+ observed in the vis-near-infrared (NIR) range monotonously change with temperature, i.e., the thermalized Er3+ levels (2H11/2 → 4I15/2/4S3/2 → 4I15/2) and the nonthermally coupled Yb3+/Er3+ levels (2F5/2 → 2F7/2/4I9/2 → 4I15/2 or 4F9/2 → 4I15/2). Hence, their thermal evolutions have been correlated with temperature using the Boltzmann type distribution and second-order polynomial fits for temperature-sensing purposes, i.e., Er3+ 525/545 nm (max Sr = 1.31% K-1) and Yb3+/Er3+ 1010/810 nm (1.64% K-1) or 1010/660 nm (0.96% K-1). Additionally, a fresh chicken breast was used as a tissue imitation in the performed ex vivo experiment, showing the advantage of the use of NIR Yb3+/Er3+ bands, vs. the typically used Er3+ 525/545 nm band ratio, i.e., better penetration of the luminescence signal through the tissue in the I-BW and II-BW. Such nanomaterials can be utilized as accurate and effective, broad-range vis-NIR optical, contactless sensors of temperature.

Enzyme activity deviates due to spatial and temporal temperature profiles in commercial microtiter plate readers.

Microtiter plates (MTP) and automatized techniques are increasingly applied in the field of biotechnology. However, the susceptibility of MTPs to edge effects such as thermal gradients can lead to high variation of measured enzyme activities. In an effort to enhance experimental reliability, to quantify, and to minimize instrument-caused deviations in enzyme kinetics between two MTP-readers, we comprehensively quantified temperature distribution in 96-well MTPs. We demonstrated the robust application of the absorbance dye cresol red as easily applicable temperature indicator in cuvettes and MTPs and determined its accuracy to ±0.16°C. We then quantified temperature distributions in 96-well MTPs revealing temperature deviations over single MTP of up to 2.2°C and different patterns in two commercial devices (BioTek Synergy 4 and Synergy Mx). The obtained liquid temperature was shown to be substantially controlled by evaporation. The temperature-induced enzyme activity variation within MTPs amounted to about 20 %. Activity deviations between MTPs and to those in cuvettes were determined to 40 % due to deviations from the set temperature in MTPs. In conclusion, we propose a better control of experimental conditions in MTPs or alternative experimental systems for reliable determination of kinetic parameters for bioprocess development.

Building a highly concentration responsive optical thermometer via tunable electron transfer pathways supported by intervalence charge transfer states.

The thermal-coupled levels (TCLs) of lanthanides have attracted great attention in the field of optical thermometer, offering an efficient method to achieve non-contect temperatuer feedback in complex environment. However, the iner 4f electrons are shielded, which becomes the core obstacle in improving the sensing performance. This issue is now circumvented by constructing an electron transfer pathway between Tm3+(1D2) and Eu3+(5D0) configurations. As a result, the electron transfer barrier is related to the relative temperature sensitivity, giving an insight into the modulation mechanism. Compared to the conventional TCLs systems, the relative temperature sensitivity of this strategy is highly concentration-responsive, increasing from 5.56 to 10.1 % K-1 as the Eu3+ molar concentration rises from 0.3 to 0.5 mol%. This work reveals the inner emission mechanism based on IVCT-supported emission mode, and presents the highly adjustability of sensing performance.