Upconversion Luminescence Materials Research Articles

Dynamic modulation of multicolor upconversion luminescence of Er3+ via excitation pulse width.

Lanthanide-doped upconversion (UC) luminescent materials display multicolor emissions, making them ideal for a variety of applications, such as multi-channel biological imaging, fluorescence encryption, anti-counterfeiting, and 3D display. Manipulating the UC emissions of the luminescent materials with a fixed composition is crucial for their applications. Herein, we propose a facile strategy to achieve pulse-width-dependent multicolor UC emissions in NaYF4:Yb/Er/Tm nanocrystals. Upon excitation with a 980nm continuous-wave laser diode, Er3+ ions in NaYF4:20%Yb,15%Er,1%Tm nanocrystals exhibited UC emissions with a red-to-green (R/G) ratio of 11.3. Nevertheless, by employing a 980nm pulse laser with pulse widths from 0.1 to 10ms, the UC R/G ratio can be easily adjusted from 0.9 to 11.3, resulting in continuous and remarkable color transformation from green, yellow, orange, to red. By virtue of the dynamic luminescence color variation of these NaYF4:20%Yb,15%Er,1%Tm nanocrystals, we demonstrated their potential applications in the areas of anti-counterfeiting and information encryption. These findings provide deep insights into the excited-state dynamics and energy transfer of Er3+ in NaYF4:Yb/Er/Tm nanocrystals upon 980nm pulse excitation, which may pave the way for designing multicolor UC materials toward versatile applications.

Experimental Optimization, Design Synthesis, and Up-Conversion Luminescence Properties of Y4GeO8: Er3+/Yb3+ Red Phosphors

The Er3+/Yb3+ co-doped Y4GeO8 crystal powders were successfully synthesized us-ing a high-temperature solid-phase method. The crystal structure of the obtained phosphors was confirmed to be pure Y4GeO8 through X-ray diffraction (XRD) analysis. A regression equation correlating Er3+/Yb3+ doping concentrations with luminescent intensity was estab-lished based on the optimized theoretical model derived from experimental design. The op-timal concentrations of Er3+ and Yb3+ under 980 nm laser excitation were determined as 7.41% and 21.34%, respectively, while under 1550 nm laser excitation, the concentrations were 2.66% and 17.42%, respectively. The fluorescence emission spectra of the up-conver-sion samples were measured, revealing intense green and red emissions with peaks at 542, 546, and 654 nm under 980 nm excitation, and peaks at 546, 557, and 663 nm under 1550 nm excitation. These peaks correspond to transitions from 2H11/2 to 4I15/2, 4S3/2 to 4I15/2, and 4F9/2 to 4I15/2 energy levels. The relationship between up-conversion luminescence and laser op-erating current for the optimal samples under 980 nm and 1550 nm was investigated, uncov-ering that up-conversion luminescence occurs through both two-photon and three-photon processes. A detailed analysis and discussion of the up-conversion luminescence mecha-nisms were conducted. Furthermore, the relationship between up-conversion fluorescence and temperature for the optimal samples was studied, revealing excellent temperature-sens-ing characteristics under 980 nm and 1550 nm laser excitations. The calculated illumination region coordinates for the optimal samples under 980 nm and 1550 nm wavelength excitations were (0.5558, 0.4362) and (0.5256, 0.4687), respectively. The research highlights the potential of rare-earth ion-doped up-conversion luminescent materials for diverse anti-coun-terfeiting applications. In particular, the Y4GeO8: Yb3+/Er3+ phosphors, incorporating a dual-excitation mechanism, enhance the security of anticounterfeiting strategies in multifaceted scenarios. The study underscores the promising developments in this field.

Up-conversion luminescent properties of CaGdAl3O7: Er3+, Yb3+, Lu3+ as a ratio optical thermometer

Rare earth doped up-conversion luminescent materials have been extensively studied for ratio optical thermometry. Compared with commonly used fluorides, oxides have low up-conversion luminous efficiencies but good thermal stability and are more suitable for high temperature environments. In this paper, a series of CaGdAl3O7: x% Er3+, y% Yb3+, z% Lu3+ phosphors were successfully prepared by high temperature solid-state reaction. Upon 980 nm laser excitation, the optimal CaGdAl3O7: 5% Er3+, 35% Yb3+, 1.5% Lu3+ shows bright characteristic emission peaks of Er3+. CaGdAl3O7: 5% Er3+, 35% Yb3+, 1.5% Lu3+ shows good temperature sensing performance from 303 K to 503 K. The absolute sensitivity reaches the maximum value at 428 K (Sa=0.292 % K-1). The maximum relative sensitivity is 0.917% K-1 at 303 K. Moreover, CaGdAl3O7: 5% Er3+, 35% Yb3+, 1.5% Lu3+ shows superior repeatability and reversibility. The results suggest that it is potential candidates as temperature sensors.

Simultaneous evolutions in composition, structure, morphology, and upconversion luminescence of BiOxFy:Yb/Er microcrystals and their application for ratiometric temperature sensing

Lanthanide upconversion luminescent materials featuring multi-peak and tunable emissions allow for ratiometric luminescence thermometry in a remote detection manner. However, wide explorations are still required to develop relevant materials for efficient thermometric performances. Herein, Yb3+/Er3+ co-doped non-stoichiometric analogues of bismuth oxyfluoride were obtained by simply tuning the F−/(Bi3+ + Ln3+) molar ratio of the reactants in a solid-state reaction method, for the first time. We achieved simultaneous regulations in composition, structure, morphology, and upconversion luminescence properties of BiOxFy:Yb/Er (2/1 mol%) microcrystals. Compositional analysis revealed not only the predictable increase of fluorine content, but also the constant O/(Bi + Ln) atomic ratios in all nominal BiOxFy:Yb/Er. Experimental results showed the structure and morphology evolutions from hexagonal-phase micro-flowers, to tetragonal-phase microplates, and further to orthorhombic-phase irregular microcrystals. Benefiting from adjustable composition, structure and morphology, up-conversion luminescence with adjustable intensity and color was obtained. Temperature dependent upconversion properties and ratiometric thermometric performances based on the thermally coupled levels, 2H11/2 and 4S3/2 of Er3+, were explored. BiOF:Yb/Er, BiO0.67F1.66:Yb/Er, and BiF3:Yb/Er microcrystals were found as suitable temperature sensing candidates with operating temperature range as wide as 298−673/723 K, high relative sensitivity up to 1.24% K-1, and minimum temperature uncertainty of 0.15 K. These results benefit not only further explorations for high-performance lanthanide-based luminescence thermometers, but also the chemistry of fluorides made from the solid-state reaction method.

Upconversion luminescence through dynamically regulating the depletion of Ho3+: 5I6 level for speed sensing

In this work, a strategy for dynamically adjusting the upconversion luminescence (UCL) color of NaGdF4:Yb3+/Ho3+/Ce3+/Sc3+ is reported based on a phosphor wheel. It has been demonstrated that the rotation-dependent UCL mainly originated from the regulation of depletion mode for the Ho3+: 5I6 level. Due to the dominant linear decay, a high-pure red UCL is observed under the steady-state excitation. However, as the proportion of the steady-state excitation decreases, the green–red emission intensity ratio gradually increases, followed by the color conversion from red to green. An approximate physical model is proposed to understand the dependence of IG/IR on rotation speed. We not only report a UCL material that shows potential application in velocity sensing but also provide new insights into wheel-based dynamic UCL regulation.

The single near-infrared upconversion luminescence of a novel KYb (MoO4)2: Er3+ phosphor for the temperature sensing

The rare earth doping upconversion luminescence (UCL) materials exhibit multimodal emission, which has huge potential applications. However, it is still a difficult problem to obtain a single emission by modulating UCL, especially the modulation of single red light and single near-infrared light. In this work, we report a novel UCL KYb (MoO4)2: Er3+ phosphor, which can achieve a single near-infrared emission (804 nm) under rare earth Er3+ doping. Its pure phase was successfully prepared by high-temperature solid-state method, and its optimal Er3+ doping concentration was found to be 0.1 %. Excited at 980 nm laser, KYb (MoO4)2: Er3+ exhibit a single near-infrared UCL attributed to the 4I9/2 → 4I15/2 transition of Er3+ ions. To further explain its UCL mechanism, the power dependence, ultraviolet-visible-near-infrared absorption spectrum, excitation spectrum and emission spectrum of KYb (MoO4)2: Er3+ was measured. Due to the excellent near-infrared emission, the temperature-dependent UCL properties of the KYb (MoO4)2: Er3+ material is investigated in the temperature range from 298 K to 673 K. The linear relationship between the UCL and the temperature, And the sensitivity of KYb (MoO4)2: Er3+ phosphor reaches the maximum value at 673 K, which is 0.0078 K−1. The single near-infrared luminescence with good penetrability and large sensitivity makes KYb (MoO4)2: Er3+ have a promising application prospect in the fields of non-contact temperature sensing and bioimaging.

Effect of vacuum annealing on the upconversion luminescence of β-Ba2ScAlO5: Yb3+, Ho3+ phosphor

Upconversion luminescence (UCL) materials with narrow emission peaks, long fluorescence lifetime, and large anti-Stokes shift have attracted considerable attention in biomedical, display, anti-counterfeiting, and solid-state lasers. This study presents a new synthesis method, combining air sintering and vacuum annealing, to obtain intense green UCL emission β-Ba2ScAlO5: 0.15 Yb3+, 0.005Ho3+ phosphor. After vacuum annealing, the green, red, and near-infrared emissions of Ho3+ are enhanced by factors of 40, 133, and 37, respectively. The diffuse reflectance spectra demonstrate that there is a defect energy band ranging from 330 to 860 nm in the air-treated samples, and it is reduced dramatically after vacuum annealing. This defect band covers the three wavelengths of Ho3+ emissions in the visible range and results in the reabsorption of UCL by the host lattice. X-ray Rietveld refinements and EPR spectra reveal the difference in the oxygen defects of the air-synthesized and vacuum-annealed phosphors and reflect that the absorption band is related to the oxygen defects. This research provides a new approach to obtain intense UCL emission of β-Ba2ScAlO5 hosted phosphors and offers an excellent green phosphor for application in anti-counterfeiting or displays.

Enhanced up-conversion luminescence and temperature sensing performance of NaBiF4: Er3+, Yb3+, Al3+

Rare earth doped fluoride-based up-conversion luminescent materials have been widely studied in non-contact temperature sensing technology. However, the luminous intensity of the fluoride at high temperature still needs to be improved. Here, enhanced up-conversion luminescence and temperature sensing performance of NaBiF4: Er3+, Yb3+ is realized by Al3+ substitution. The samples exhibit the characteristic green (521 nm and 540 nm) and red (654 nm) emissions of Er3+ ion under 980 nm excitation. When the concentration of Al3+ is 5%, the green emission is enhanced by about 10 times, and the red light is enhanced by about 7 times. Obvious lattice shrinkage caused by the introduction of Al3+ is responsible for the enhancement. In addition, the optimal sample is highly thermally stable from 303 K to 443 K. The maximum relative sensitivity at 303 K increases from 0.791% K−1 to 1.106% K−1. The results indicate that NaBiF4: Er3+, Yb3+, Al3+ be a potential thermosensitive material.

Preparation of Er3+, Ho3+, Yb3+-doped Bi2WO6 upconversion luminescent materials and their temperature sensing properties

A high-temperature solid-phase method was used to prepare codoped Bi2WO6 upconversion luminescent materials with different concentrations of Er3+, Ho3+, and Yb3+. The microstructure, upconversion luminescence and temperature sensing properties of the synthesized powders were analyzed. X-ray diffraction (XRD) patterns showed that the doping of Er3+, Ho3+, and Yb3+ did not affect the orthorhombic crystal structure of the Bi2WO6 matrix material. As the calcination temperature increased from 800 °C to 1000 °C for 3h, the average particle sizes of the 1% Er3+, 1% Ho3+, 1% Yb3+: Bi2WO6 samples decreased, and the luminescence weakened. Scanning electron microscopy (SEM) images showed that the morphology of the sample for 1% Er3+, 1% Ho3+, 1% Yb3+: Bi2WO6 with calcination at 800 °C was nearly spherical, with particle sizes ranging from 1 to 5 μm and some agglomeration. SEM mapping showed that the elements were more uniformly distributed on the surfaces of the sample particles, and energy-dispersive X-ray spectroscopy (EDS) analysis showed that each element was distributed with in the particles. Er3+, Ho3+, and Yb3+ codoping was used to regulate the Yb3+ doping concentration, and under 980 nm excitation, the strongest upconversion emission was obtained for the prepared 1% Er3+, 1% Ho3+, 1% Yb3+ samples. Compared with that for the Er3+, Yb3+-doped Bi2WO6 sample, the luminescence intensity of the characteristic emission peak of Er3+ at 525 nm for the Er3+, Ho3+, Yb3+-doped sample was weakened, while the luminescence of the characteristic emission peak of Ho3+ was enhanced; these results indicated that energy transfer from Er3+ to Ho3+ occurred. The intensities of the four emission peaks at 525 nm, 546 nm, 660 nm, and 756 nm in the 1% Er3+, 1% Ho3+, 1% Yb3+-doped Bi2WO6 sample increased with increasing excitation pump power from 45 mW to 233 mW. Based on the relationship between the excitation pump power and the emission intensity, all four luminescence peaks originated from two-photon absorption. The fluorescence intensity ratio versus temperature was fitted using three different nonthermally coupled energy level pairs in the range from 298 K to 573 K. The maximum absolute temperature sensitivity of 0.296 K-1 was obtained at 573 K for the Ho3+ nonthermally coupled energy level pair, and the maximum relative temperature sensitivity of 0.279 K-1 was obtained at 298 K. The temperature resolution for characterization using the above nonthermally coupled energy level pairs was calculated, with the temperature resolution δT yielding a minimum value of 0.03 K. The CIE color coordinates at different temperatures were calculated, and the color coordinates gradually moved from the green region to the red region.

Upconversion luminescence and temperature sensing performance of Zn2+-doped Ba2GdAlO5: Yb3+, Er3+ phosphors

Although upconversion luminescence (UCL) materials have attracted considerable attention in biomedical, lighting, anti-counterfeiting, and solar cells due to their excellent fluorescence properties, reports of the dibarium gadolinium aluminum oxide (Ba2GdAlO5) are scarce. Herein, we synthesized the single-phase Ba2GdAlO5 material with non-stoichiometric Ba2Gd1.06Al0.94O5 (denoted as BGAO, hereafter). The X-ray Rietveld refinement reveals that the substitution of Gd for Al accounts for the non-stoichiometry. Notably, the UCL properties of BGAO are realized by doping with Yb3+ and Er3+ ion pair, and it can be further enhanced significantly by co-doping with appropriate Zn2+ ions. The SEM images show that the particle size increases as the concentration of Zn2+ ions increases. The X-ray Rietveld refinement results of the Zn-doped BGAO: 0.1 Yb3+, 0.03Er3+ phosphor indicate the substitution of Zn2+ for Ba2+ and Al3+ ions simultaneously. Grain growth and lattice distortion account for the improvement of UCL properties after Zn2+ ions doping. In addition, the temperature sensing performance of the Zn2+-doped sample has been researched based on the fluorescence intensity ratio (FIR) technique, and the maximum absolute and relative sensitivities (SA-max and SR-max) are obtained to be 4.8 × 10−3 K−1 at 498 K and 1.1% K−1 at 298 K, respectively. This work provides a candidate with high UCL intensity for potential applications in optical temperature sensors.

Achieving Orthogonal Upconversion Luminescence of a Single Lanthanide Ion in Crystals for Optical Encryption.

Optical encryption shows great potential in meeting the growing demand for advanced anti-counterfeiting in the information age. The development of upconversion luminescence (UCL) materials capable of emitting different colors of light in response to different external stimuli holds great promise in this field. However, the effective realization of multicolor UCL materials usually requires complex structural designs. In this work, orthogonal UCL is achieved in crystals with a simple structure simply by introducing modulator Tm3+ ions to control the photon transition processes between different energy levels of activator Er3+ ions. The obtained crystals emit red and green UCL when excited by 980nm and 808nm lasers, respectively. The orthogonal excitation-emission properties of crystals are shown to be very suitable for high-level optical encryption, which is important for information security and anti-counterfeiting. This work provides an effective strategy for obtaining orthogonal UCL in simple structural materials, which will encourage researchers to further explore novel orthogonal UCL materials and their applications, and has important implications for the development of the frontier photonic upconversion fields.

Strong green upconversion emission from submicron spindle-shaped SrMoO4:Yb3+,Er3.

Upconversion luminescence (UCL) is a fluorescence process where two or more lower-energy photons convert into a higher-energy photon. Lanthanide (Ln3+)-doped UCL materials often suffer from weak luminescence, especially when directly synthesized by a hydrothermal (HT) process due to the existing hydroxyl group and undesirable arrangement of dopants within host lattices which quench luminescence and limit energy transfer. Therefore, additional heat treatment processes are required to enhance their UCL emission, even though direct hydrothermal synthesis without further heat treatment has the advantages of low energy consumption, fast synthesis, and wide applicability to generate UCL materials. In this study, via a HT process without annealing, we have produced Yb3+ and Er3+ co-doped SrMoO4 submicron spindles with a strong green UCL emission which can be seen with the naked eye, which HT produced oxide-based UCL materials often fail to demonstrate. We have investigated different HT synthesis conditions, such as temperature, time, pH and dopant composition, which control the nucleation, growth, lattice structure arrangement, and ultimately their UCL properties through XRD, SEM, EDS and UCL measurements. The bright green UCL from the SrMoO4:Yb,Er submicron spindles is further enhanced by post-synthesis annealing within a molten NaNO3/KNO3 system to prevent particle size growth. The green UCL intensity from the annealed SrMoO4:Yb,Er submicron spindles surpasses samples produced by the solid-state method and is comparable to that from the commercial NaYF4:Yb,Er sample. We have further studied the temperature-dependent luminescence of both the HT-prepared and molten-salt annealed SrMoO4:Yb,Er submicron spindle samples. The strong UCL from our SrMoO4:Yb,Er submicron spindles could warrant their candidacy for bioimaging and anticounterfeiting applications.

Synthesis and luminescence properties of Yb3+/Er3+-doped Bi2(MoO4)3−z(WO4)z phosphors for optical thermometry

A novel Bi2(MoO4)3−z(WO4)z:Yb3+/Er3+ upconversion luminescent material was synthesized via a hydrothermal method combined with subsequent calcination, which has potential applications in the fields of green displays and temperature sensing.

Simultaneously tuning the luminescent color and realizing an optical temperature sensor by negative thermal expansion in Sc2(WO4)3:Tb/Eu phosphors.

At present, many researchers are focusing on trivalent lanthanide (Ln3+)-doped thermally enhanced upconversion luminescent (UCL) materials with negative thermal expansion (NTE) properties. However, selective anti-thermal quenching downshifting emissions of the activator and thermal quenching of the sensitizer in a phosphor with NTE properties are not implemented. Herein, Tb3+/Eu3+ co-doped Sc2(WO4)3 phosphors synthesized by the solid-state method are explored in selectively enhanced red emission (Eu3+:5D0 → 7F2) due to the energy-transfer efficiency from Tb3+ to Eu3+ and the promoted radiative transition probability. The selective thermally quenched green emission (Tb3+:5D4 → 7F5) is owing to the change of energy transfer from Tb3+ to Eu3+ as the temperature increased. Moreover, under ultraviolet 365 nm excitation, the thermally stimulated color emission tuned from yellow to red with the increase in temperature. Based on the radically different thermal response downshifting the luminescence of the activator and sensitizer, the luminescence intensity ratio (LIR) of non-thermally coupled levels (NTCLs) for 5D0 (Eu3+) and 5D4 (Tb3+) is adopted for optical temperature sensing. The optimal relative sensitivity of temperature sensing in the Sc2(WO4)3:25%Tb3+/3%Eu3+ sample could reach 2.94% K-1 at 347 K. All these indicate that this Sc2(WO4)3:Tb3+/Eu3+ material is a promising candidate for high-sensitivity optical temperature sensing.

Upconversion luminescence and temperature sensing properties of Ho3+,Yb3+-codoped Bi2WO6.

Ho3+ and Yb3+-codoped Bi2WO6 upconversion luminescent materials at different concentrations were prepared via a high-temperature solid-phase method. The X-ray diffraction patterns showed that Ho3+ and Yb3+ doping basically did not affect the orthorhombic crystal system structure of the Bi2WO6 matrix material. Scanning electron microscopy images showed that 3%Ho3+,10%Yb3+:Bi2WO6 consisted of irregular bulk particles with sizes in the range of 0.5-2 μm and some powder agglomeration. SEM mapping and EDS measurements of the powder showed that the elements were relatively uniformly distributed. Under 980 nm excitation, the emission intensity of Ho3+ was the largest for the 3%Ho3+- and 10%Yb3+-doped sample. With an excitation power ranging from 45 mW to 283 mW for the 3%Ho3+,10%Yb3+:Bi2WO6 sample, the relationship between the luminescence intensity and pump power was determined; the results indicated that the Ho3+ (538 nm, 546 nm, 660 nm, 756 nm) emission peaks originated from two-photon absorption. In the temperature range of 298 K-573 K, under 980 nm laser excitation, the maximum absolute temperature sensitivity Sa was 0.029% K-1 (373 K), the maximum relative temperature sensitivity Sr was 0.034% K-1 (348 K) for the Ho3+ thermally coupled energy levels 5F4/5S2, and the minimum temperature resolution δT was 1.2857 K (298 K). Under the same conditions, the maximum Sa was 51.02% K-1 (573 K), the maximum Sr was 1.85% K-1 (523 K) for the Ho3+ nonthermally coupled energy levels 5F5/5F4, and the minimum δT is 0.2477 K (448 K). The colour coordinates showed that the luminescence of the 3%Ho3+,10%Yb3+:Bi2WO6 sample gradually shifted from the green region to the red region with increasing temperature.

Enhancement mechanism of red up-conversion emission in single NaYbF<sub>4</sub>:2%Er<sup>3+</sup>@NaYbF<sub>4 </sub>micron core-shell structure

The construction of core-shell structure can effectively reduce the quenching effect on the surface of material and regulate ion-ion interaction, which has become one of the effective ways to enhance and regulate the spectral characteristics of rare-earth upconversion luminescent materials. In this paper, a variety of NaYbF<sub>4</sub>: 2%Er<sup>3+</sup> micron core-shell structures are constructed with the help of epitaxial growth technology, effectively improving the red up-conversion emission of Er<sup>3+</sup> ions. The prepared microcrystals with core-shell structures are of hexagonal phase microdisks, and their sizes are relatively uniform. In order to better obtain the material spectral data, a confocal microscopic spectroscopy is used to study spectral properties. Under 980 nm near-infrared laser excitation, the red emission intensity of single NaYbF<sub>4</sub>:2%Er<sup>3+</sup>@NaYbF<sub>4</sub>@NaYF<sub>4</sub> core-shell-shell microdisk is 4.6 times higher than that of NaYbF<sub>4</sub>:2%Er<sup>3+</sup> micron disk, and the red-to-green ratio increases from 6.3 to 8.1. Meanwhile, Ho<sup>3+</sup> ions are introduced into the NaYbF<sub>4</sub>:2%Er<sup>3+</sup>@NaYbF<sub>4</sub>: 2%Ho<sup>3+</sup> @NaYF<sub>4</sub> core-shell-shell microdisk, and the red emission intensity is nearly 6.7 times higher than that of single NaYbF<sub>4</sub>: 2%Er<sup>3+</sup> microdisk, and the red-to-green ratio increases from 6.3 to 9.4 through the interaction between ions. The microcrystal spectral characteristics and luminescence kinetics of different core-shell structures are studied, showing that the red emission enhancement of Er<sup>3+</sup> ions is mainly derived from the construction of different core-shell structures, which can effectively enhance the cross-relaxation between Er<sup>3+</sup> ions, the energy back transfer between Yb<sup>3+</sup> and Er<sup>3+</sup> ions, and the energy transfer from Ho<sup>3+</sup> ions to Er<sup>3+</sup> ions. The micron core-shell structures with efficient red emission in this study has great application prospects in the fields of luminescence, anti-counterfeiting and optoelectronic devices.

Effect of the local environment on the luminescence of Er3+/Yb3+-doped aluminate upconversion phosphors

In recent years, trivalent rare-earth ion (RE3+) doped upconversion luminescent (UCL) materials have been studied extensively owing to their potential applications. The structure of the material is the main factor affecting the UCL performance. In this study, three structurally identical Er3+/Yb3+ co-doped aluminates CaYAlO4, CaGdAlO4, and CaLaAlO4 (CYA, CGA, and CLA) phosphors were synthesized, and the effects of the local environment on the UCL performance of Er3+ ions were investigated. The morphology and phonon energy of the samples were not the main factors affecting the luminescence performance in the same structural material. The difference in the crystal field strength was the main reason for the difference in the UCL of the three phosphors, which was attributed mainly to the difference in the crystal field strength and the difference in the degree of distortion of the Al–O octahedra that changes the transition probabilities of the parity forbidden intra-4fN–4fN electronic transitions of Er3+. A comparison of the distances between the RE3+ and the lifetimes of the 4I11/2 and 4I13/2 energy levels in the three materials showed that the red–green ratio of the materials was affected by the energy transfer. Finally, an analysis of the changes in the energy band structure and density of states (DOS) distribution before and after Er3+/Yb3+ doping of CYA, CGA, and CLA found that the effect of the bandgap on the UCL can be neglected when the bandgap of the matrix is larger than the energy difference from the 4I15/2 energy level to the 2H11/2 energy level of the Er3+ ion.

Luminescence properties and temperature sensing characteristics of Bi2WO6: Er3+, Tm3+, Yb3+ phosphors

Bi2WO6:x%Er3+, y%Tm3+, 6%Yb3+ (x = 0, 0.5, 1, 2, 4, 6; y = 0, 1) upconversion luminescent materials were prepared via a high-temperature solid-state method. XRD studies showed that Er3+, Tm3+ and Yb3+ doping at various concentrations had little effect on the orthorhombic structure of the Bi2WO6 crystal system. SEM images showed that the morphologies of the Bi2WO6: 1%Tm3+, 6%Yb3+ and Bi2WO6: 4%Er3+, 1%Tm3+, 6%Yb3+ powder samples were uneven, with agglomeration of nearly spherical particles and particle sizes of 0.5–5 μm. The average granularities of the samples were slightly smaller after Er3+ codoping. With 980 nm excitation (power: 500 mW), Bi2WO6: 4%Er3+, 6%Tm3+, 6%Yb3+samples exhibited the strongest luminescence upconversion. With increasing Er3+ doping levels, the intensity of Er3+ luminescence in the Bi2WO6: x%Er3+, 1%Tm3+, 6%Yb3+ samples first increased and then decreased, whereas the Tm3+ luminescence significantly decreased, indicating energy transfer from Tm3+ to Er3+. For Bi2WO6: 4%Er3+, 1%Tm3+, 6%Yb3+ samples excited with 100–500 mW powers and at 980 nm, the 525 nm and 530 nm green emission peaks for Er3+ and 685 nm and 705 nm red emission peaks for Tm3+ resulted from two-photon absorption. For the Bi2WO6: 4%Er3+, 1%Tm3+, 6%Yb3+ sample excited at 980 nm, the temperature was characterized by the I543nm/I705nm fluorescence intensity ratio; at 298 K, the maximum Sa was 0.806 K-1, and the maximum Sr was 0.0243 K-1. When the temperature was characterized by the I705nm/I525nm fluorescence intensity ratio, Sa was 0.0256 K−1 at 573 K, and the maximum Sr was 0.0382 K-1. At 298 K, the sample showed a minimum temperature resolution of 0.026 K. As the temperature increased from 298 K to 573 K, the luminescence color of the sample gradually shifted from the green to orange-yellow.

Control upconversion decay dynamics from the perspective of collective response

Very recently, upconversion luminescence (UCL) lifetime, as a powerful optical dimension, has attracted tremendous research interest due to its advantages of high information capacity and high photophysical stability. With the implementation and emergence of endlessly fascinating UCL features, it is particularly meaningful to understand the photophysical mechanisms inside UCL materials to enable rational subdivision-level structure design, which is however currently far from sufficient. In this work, we take an ordinary upconversion nanoparticle as an example to prove that the UCL decay curves and corresponding lifetimes are indeed a collective response of the entire UCL system to excitations, that exhibits correlated, yet quite different properties from individual ions. A specially developed theoretical random walk model combined with an experimental lifetime control for Yb3+/Er3+ UCL demonstrates that energy diffusion principally alters the decay rate. Moreover, the different extent of the influence of energy diffusion on the emissions of 2H11/2/4S3/2 (green) and 4F9/2 (red) leads to an extremely uncommon cross-over comparison of decay rates. This work provides new ideas for understanding decay dynamics and practical UCL lifetime manipulation methods.

Upconversion luminescence and temperature sensing properties of CaF2-crystal-contained silicate glass-ceramics doped with Er3+/Yb3+

Rare earth upconversion luminescent materials have a wide range of applications in the fields of anti-counterfeiting, imaging, temperature sensing, spectral conversion and so on. CaF2-crystal-contained glass-ceramics possess low phonon energy and good stability. Therefore, as a matrix material doped with rare earth, CaF2-crystal-contained glass-ceramics should have better upconversion luminescence properties. In this paper, the upconversion luminescence properties of Yb[Formula: see text]/Er[Formula: see text]-co-doped CaF2-crystal-contained silicate glass-ceramics were studied. Er[Formula: see text]/Yb[Formula: see text]-co-doped CaF2-crystal-contained silicate glass-ceramics were synthesized by melt-cooling method. XRD proved that CaF2 crystals were successfully precipitated in the glass. Comparing the upconversion luminescence intensity of different samples, the optimum heat treatment temperature was determined to be 660∘C. The upconversion process was analyzed by analyzing the relationship between fluorescence intensity and excitation power. Finally, the relationship between the fluorescence intensity ratio of the sample at 521[Formula: see text]nm and 538[Formula: see text]nm with the temperature change was discussed, the absolute sensitivity and relative sensitivity of the sample to temperature were determined. The results show that the sample is expected to be used as a no-contact thermometer.