Downshifting Luminescence Research Articles

The Important Round-Trip Energy Transfer for Excitation of the Red Emission in the Er3+/Yb3+ System.

Round-trip energy transfer (RTET) in the popular Er3+/Yb3+ upconversion (UC) system is a newly discovered mechanism for the red emission of Er3+ through Yb3+ as an intermediate ion. However, the importance of the RTET still remains a question. Here, we show in cubic Y2O3 that the new mechanism defeats conventional ones and dominates the red emission in both UC and down-shifting (DS) luminescence for a wide concentration range of Yb3+. The RTET enables the red UC emission to exhibit a similar time evolution as the green UC emission for Yb3+ concentration ≤10%, and its contribution to the red DS emission exceeds 90% for Yb3+ concentration ≥10%. As a unique feature, the temporal profile of the entire RTET process is presented for the first time. Our findings provide new physical insight into the regulation of color and temporal behavior of UC luminescence in the Yb3+/Er3+ system.

Near-infrared downshifting luminescence of Ca2LaTaO6:Nd3+/Yb3+/K+ phosphors and their applications: solar cells and anti-counterfeiting.

A series of Nd3+/Yb3+ co-doped Ca2LaTaO6 (CLTO) phosphors are synthesized by a high temperature solid phase method. Structural characterization confirms the successful incorporation of Nd3+ and Yb3+ ions into the CLTO host lattice. The photoluminescence excitation (PLE) spectra and photoluminescence (PL) spectra of CLTO:Nd3+ and CLTO:Nd3+/Yb3+ are investigated in detail. Under the excitation of ultraviolet (UV) and visible (VIS) light, the CLTO:Nd3+/Yb3+ phosphor emits broadband near infrared (NIR) luminescence. In particular, the luminescence intensity of the Yb3+ ion is increased through an energy transfer (ET) process from Nd3+ to Yb3+. The luminescence mechanism of the CLTO:Nd3+/Yb3+ sample is analyzed based on the decay lifetime and PL spectra. In addition, the NIR emission intensity of Yb3+ ions is also enhanced by doping K+ ions. The broadband luminescence (850-1050 nm) of the CLTO:Nd3+/Yb3+/K+ phosphor has good application in solar cells and anti-counterfeiting.

Upconverting Luminescent MOF for Highly Sensitive Dual-Mode Recognition of Synthetic Dyes.

Lanthanide-based luminescent materials hold promise in sensing applications due to their distinct optical properties. Though advancements in lanthanide-based metal-organic frameworks (MOFs) have enhanced downshifting luminescence, achieving upconversion remains challenging. In this effort, we prepared upconverting ytterbium-doped europium MOFs (x%Yb3+-EuMOFs; x = 10, 20, and 30) via the solvothermal method using 2,6-naphthalenedicarboxylic acid (NDC) as an organic linker. Upconversion (UC) luminescence studies revealed that 30%Yb3+-EuMOF (MOF-3) rapidly detects malachite green (MG, a textile dye) and brilliant green (BG, a food colorant) with excellent sensitivity (λex = 980 nm). Notably, UC luminescence offers a lower detection limit (MG: 36.33 nM, BG: 287.9 nM) compared to the downconverting sensing approach (λex 270 nm), while the related dual-mode luminescence minimizes the risk of false positives from interfering ultraviolet-visible (UV-vis) light-absorbing substances. Upconversion quenching has been linked to the FRET process, with its luminescence assay accurately detecting MG in fish, water, and soil samples under 980 nm excitation (98-105% recovery).

Visible to infrared wide wavelength range luminescence of Sr2LaNbO6: Yb3+/Nd3+/Ho3+ phosphor under 808/980 nm excitation and temperature sensing application

Here, the Sr2LaNbO6: Yb3+/Nd3+/Ho3+ phosphors are prepared through solid-state route. The upconversion (UC)/downshifting (DS) luminescence and temperature performances of all samples are investigated in detail. Under 808 nm excitation, the infrared emission band (∼2000 nm) of Ho3+ ions is obtained. Especially, the energy transfer process of Nd3+ → Yb3+ → Ho3+ has increased the emission intensity of ∼2000 nm. Moreover, the infrared emission band presents thermal enhancement. Under 980 nm excitation, the UC emission band 500–960 nm is investigated. The green and red light of Ho3+ ion, near infrared light of Nd3+ ions are achieved. In addition, the possible luminescence mechanism of Sr2LaNbO6: Yb3+/Nd3+/Ho3+ phosphor is discussed. At last, the optical temperature sensing characteristics of the phosphor are studied according to the luminescence intensity ratio (LIR) technology. The maximum relative sensitivity of Sr2LaNbO6: Yb3+/Nd3+/Ho3+ reaches 5.476 % K−1 at 293 K. These results prove that the Sr2LaNbO6: Yb3+/Nd3+/Ho3+ phosphor presents the luminescence in infrared and visible range. The Sr2LaNbO6:Yb3+/Nd3+/Ho3+ phosphor also can be applied to design optical temperature sensor.

Engineering Visible to Near-Infrared Luminescence through a Selective Doping Strategy for High-Performance Temperature Sensing.

Luminescence nanothermometers have garnered considerable attention due to their noncontact measurement, high spatial resolution, and rapid response. However, many nanothermometers employing single-mode measurement encounter challenges regarding their relative sensitivity. Herein, a unique class of tunable upconversion (UC) and downshifting (DS) luminescence covering the visible to near-infrared range (400-1700 nm) is reported, characterized by the superior Tm3+, Ho3+, and Er3+ emissions induced by efficient energy transfer. The outstanding negative thermal expansion characteristic of ScF3 nanocrystals has been found to guide excitation energy toward the relevant emitting states in the Yb3+-Ho3+-Tm3+-codoped system, consequently resulting in remarkable near-infrared III (NIR-III) luminescence at ∼1625 nm (Tm3+:3F4 → 3H6 transition), which in turn presents numerous opportunities for designing multimode ratiometric luminescence thermometry. Furthermore, by facilitating phonon-assisted energy transfer in Er3+-Ho3+-codoped systems, the luminescence intensity ratio (LIR) of 4I13/2 of Er3+ and 5I6 of Ho3+ in ScF3:Yb3+/Ho3+/Er3+ exhibits a strong temperature dependence, enabling NIR-II/III luminescence thermometry with superior thermal sensitivity and resolution (Sr = 0.78% K-1, δT = 0.64 K). These findings not only underscore the distinctive and ubiquitous attributes of lanthanide ion-doped nanomaterials but also hold significant implications for crafting luminescence thermometers with unparalleled sensitivity.

Sequential up-conversion and down-shifting luminescence with a tandem luminescent solar concentrator based on rare-earth and organic materials

Conventional photovoltaic systems frequently struggle to fully exploit the vast solar spectrum, falling short in efficiently converting the entire potential of each photon into electricity. This quest for maximizing solar spectrum utilization emerges as a cutting-edge research frontier within the realm of photovoltaics. In this context, we introduce a tandem luminescent solar concentrator featuring rare-earth materials (Yb3+-Er3+ doped ZBLAN) and organic dyes (Lumogen yellow and Lumogen pink) embedded within EVA polymer matrices. The incorporation of various luminescent entities plays a pivotal role in augmenting energy capture across different parts of the solar spectrum (UV, visible, and NIR). At the same time, our approach targets the synergistic integration of up-conversion and down-shifting mechanisms to achieve an optimal spectral alignment with the response profile of amorphous silicon solar cells. This involves converting UV–visible photons from incoming sunlight and visible up-converted photons from near-infrared radiation into the orange-red segment of the spectrum. Notably, this marks the initial demonstration, to the best of our knowledge, of a proof-of-concept employing a tandem luminescent solar concentrator wherein up-conversion and down-shifting photonic processes collaboratively operate in a sequential manner.

Negative Thermal Expansion Materials as Anti-Thermal-Quenching Phosphor Matrixes: Status, Opportunities, and Challenges.

Inorganic phosphor materials often face the common phenomenon of luminescence thermal quenching (TQ), which deteriorates their device performance and consequently limits their applicability for broad applications. Thus, exploring thermally stable and even anti-TQ phosphors is viable to meet the urgent requirements of lighting technology and many other luminescence-based applications. One of the emerging approaches devoted to solving the TQ issue of phosphors, especially at elevated temperatures, is to employ negative thermal expansion (NTE) properties occurring in some unique inorganic materials. The present Review focuses on the progress of exploring NTE-based inorganic phosphor materials that have demonstrated unusual negative TQ with enhancing upconversion and downshift luminescence upon elevating temperature. We have also provided a brief history of exploring NTE phosphors for thermally stable and enhanced emission along with the investigation methods and proposed mechanisms of these unusual phenomena. To summarize, we have further discussed some opportunities and challenges that NTE materials face as host matrixes for anti-TQ phosphors. Overall, the aim of this Review is to stimulate the exploration of new NTE-based inorganic phosphors, the correlation of their fundamental structural changes with varying temperature, and the investigation of their potential for broad applications.

The size-dependent thermal enhancement of down-shifting luminescence based on non-Yb3+-mediated energy migration

The past few years have witnessed extensive attention to the size-dependent up-conversion luminescence thermal enhancement of Ln3+ doped nanoparticles, where the involvement of Yb3+ ions seem to be essential. In this work, a size-dependent down-shifting luminescence thermal enhancement behavior of NaGdF4:Ce3+/Tb3+ has been reported. Specifically, it is the first time to realize the size-dependent luminescence thermal enhancement with a non-Yb3+-involved luminescence process. We demonstrate that the size-dependent luminescence behavior is ascribed to the establishment of energy migration channels via Gd3+ sublattice. These findings offer a feasible way to design the luminescence thermal behavior of nanophosphors with a broader range in terms of both chemical composition and luminescence mechanism.

The Down-Shifting Luminescence of Rare-Earth Nanoparticles for Multimodal Imaging and Photothermal Therapy of Breast Cancer.

Nanotheranostic agents capable of simultaneously enabling real-time tracking and precise treatment at tumor sites play an increasingly pivotal role in the field of medicine. In this article, we report a novel near-infrared-II window (NIR-II) emitting downconversion rare-earth nanoparticles (RENPs) to improve image-guided therapy for breast cancer. The developed α-NaErF4@NaYF4 nanoparticles (α-Er NPs) have a diameter of approximately 24.1 nm and exhibit superior biocompatibility and negligible toxicity. RENPs exhibit superior imaging quality and photothermal conversion efficiency in the NIR-II range compared to clinically approved indocyanine green (ICG). Under 808 nm laser irradiation, the α-Er NPs achieve significant tumor imaging performance and photothermal effects in vivo in a mouse model of breast cancer. Simultaneously, it combines X-ray computed tomography (CT) and ultrasound (US) tri-modal imaging to guide therapy for cancer. The integration of NIR-II imaging technology and RENPs establishes a promising foundation for future medical applications.

Anti-thermal quenching of luminescence in Y2W3O12:Yb3+/RE3+ (RE = Er/Ho/Tm) and its temperature sensing application.

Herein, a series of Y2W3O12:10%Yb3+/x%RE3+ (RE = Er/Ho/Tm) phosphors is prepared via a solid-state reaction. The upconversion and downshift luminescence properties of the phosphors were investigated under an excitation of 980 nm. The bright blue light emission from Tm3+ ion and the green and red light emissions from Ho3+(Er3+) ions were observed. The near-infrared light intensity of NIR-I (Tm3+, ∼850 nm), NIR-II (Er3+: ∼1550 nm; Tm3+: ∼1783 nm) and NIR-III (Ho3+: ∼2050 nm) were analyzed. In particular, the dramatic thermal enhancement phenomenon in visible and NIR regions was exhibited by the Y2W3O12:10%Yb3+/x%RE3+ (RE = Er/Ho/Tm) phosphors. Among them, the green light intensity of Er3+ ions increased 26.77 times, from 303 to 573 K. The NIR-II emission band (∼1783 nm) intensity of Tm3+ ions at 533 K increased 168.7 times compared to that at 313 K. The possible thermal enhancement mechanism is illustrated by the negative thermal expansion (NTE) and Frenkel defect of the Y2W3O12 host. Finally, the optical temperature sensing performances of Y2W3O12:10%Yb3+/x%RE3+ (RE = Er/Ho/Tm) samples are investigated according to the luminescence intensity dependence relationship on temperature. The maximum value of SR reached 4.24% K-1 at 353 K for Y2W3O12:10%Yb3+/0.6%Ho3+ phosphor. The results indicate that the Y2W3O12:10%Yb3+/x%RE3+ (RE = Er/Ho/Tm) phosphors possess anti-thermal quenching properties and are suitable for developing optical temperature sensors.

Negative and positive thermal expansion effects regulate the upconversion and near-infrared downshift luminescence for multiparametric temperature sensing

Negative and positive thermal expansion effects regulate the upconversion and near-infrared downshift luminescence for multiparametric temperature sensing

Er3+-Sensitized Upconversion/Down-Shifting Luminescence in Metal-Organic Frameworks.

Photoluminescent metal-organic frameworks (MOFs) are used as optical materials with excellent properties, of which the lanthanide-doped MOFs are able to emit in a broad region from visible to near-infrared due to their unique 4f-orbital electronic structure. Herein, Er3+ and Y3+ ions are selected as the metal centers of the MOFs and Er3+ is used as a sensitizer to absorb 980 nm excitation light. At the same time, Er3+ ions also act as activators that emit upconverting visible light and down-shifting near-infrared light. In addition, Tm3+, Ho3+, and Eu3+ ions were individually doped into the Er3+-doped MOFs to investigate the variation of energy-transfer paths in the presence of different lanthanide activators. Finally, the pathway of energy transfer in these Er3+-sensitized luminescent-MOFs was summarized. This work provides new insights for further development of both upconversion and down-shifting luminescence of MOFs.

Over 104 -fold amplified upconversion luminescence of lanthanide nanocrystals through optical oscillator-like system.

Recently, lanthanide (Ln) luminescent nanocrystals have attracted increasing attention in various fields such as biomedical imaging, lasers, and anticounterfeiting. However, due to the forbidden 4f-4f transition of lanthanide ions, the absorption cross-section and luminescence brightness of lanthanide nanocrystals are limited. To address the challenge, we constructed an optical oscillator-like system to repeatedly simulate lanthanide nanocrystals to enhance the absorption efficiency of lanthanide ions on excitation photons. In this optical system, the upconversion luminescence (UCL) of Tm3+ emission of ~450 nm excited by a 980 nm laser can be amplified by a factor beyond 104 . The corresponding downshifting luminescence of Tm3+ at 1460 nm was enhanced by three orders of magnitude. We also demonstrated that the significant luminescence enhancement in the designed optical oscillator-like system was general for various lanthanide nanocrystals including NaYF4 :Yb3+ /Ln3+ , NaErF4 @NaYF4 and NaYF4 :Yb3+ /Ln3+ @NaYF4 :Yb3+ @NaYF4 (Ln = Er, Tm, Ho) regardless of the wavelengths of excitation sources (808 and 980 nm). The mechanism study revealed that both elevated laser power in the optical system and multiple excitations on lanthanide nanocrystals were the main reason for the luminescence amplification. Our findings may benefit the future development of low-threshold upconversion and downshifting luminescence of lanthanide nanocrystals and expand their applications.

Reengineering the thermometric behaviors of Er3+/Yb3+-codoped Gd2Mo3O12 microparticles via dual-mode luminescence manipulation

Series of Er3+/Yb3+-codoped Gd2Mo3O12 (GMO:Er3+/2xYb3+) microparticles with dual-mode luminescence were fabricated with the assistance of sol-gel method. The phase structure, morphological information, upconversion (UC) and down-shifting luminescence properties of the final products were systematically investigated. At 980 nm light irradiation, strong UC emissions rise in all the products and their intensities depend on the dopant concentration, where the optimum status occurs at x = 0.25 and the two-photon capture procedure results in the UC emission mechanism. Besides, excited at 378 nm, the down-shifting photoluminescence is also gained in resulting samples. By means of the fluorescence intensity ratio technique, the thermometric properties of the studied samples were investigated through analyzing the diverse thermal quenching features of the green emissions from thermally coupled levels of Er3+. When the UC emission is selected, the maximum absolute and relative sensitivities of the GMO:Er3+/2xYb3+ microparticles are 0.0076 and 1.15% K−1, respectively, whereas they shift to 0.0036 and 0.89% K−1, respectively, when the down-shifting photoluminescence is adopted. Note that, the sensor sensitivities of developed microparticles are related to the luminescence mode, while they do not depend on Yb3+ content. These results suggest that the GMO:Er3+/2xYb3+ microparticles are promising thermosensitive luminescent materials for optical thermometry and their thermometric features can be tuned through changing luminescence mode.

Anti-counterfeiting and Optical storage applications based on reversible modulated Down-shift Luminescence in photocoloration of MoO3: Eu3+ phosphor

Reversible and repeatable control of rare earth ions doped down-shift luminescence materials induced by the external field stimulation can be applied more widely. However, there is still a challenge on reversible luminescence regulation of photochromism-induced rare earth ions doped down-shift luminescence materials by light fields stimulation. The MoO3: Eu3+ phosphors changed color from light green to blue due to the formation of color centers caused by the trapping of electrons by oxygen vacancy defects under near infrared irradiation at 808 nm, and recovered from blue to initial light green after heating at 500 °C, showing a reversible change in color. The down-shift luminescence intensity of MoO3: Eu3+ phosphors reaches the maximum quenching degree, about 87%, after 20 s irradiation by 808 nm laser, which has the characteristics of fast response and great regulation rate. Moreover, the down-shift luminescence intensity can recover to the initial intensity after heating at 500 °C for 90 s, indicating reversible regulation of photochromism-induced down-shift luminescence. The application of MoO3: Eu3+ phosphors as the anti-counterfeiting labels and information storage of binary encoding was designed, these results suggest that it have certain potential applications in anti-counterfeiting and optical storage field.

High Quantum Yield Shortwave Infrared Luminescent Tracers for Improved Sorting of Plastic Waste.

More complete recycling of plastic waste is possible only if new technologies that go beyond state-of-the-art near-infrared (NIR) sorting are developed. For example, tracer-based sorting is a new technology that explores the upconversion or down-shift luminescence of special tracers based on inorganic materials codoped with lanthanide ions. Specifically, down-shift tracers emit in the shortwave infrared (SWIR) spectral range and can be detected using a SWIR camera preinstalled in a state-of-the-art sorting machine for NIR sorting. In this study, we synthesized a very efficient SWIR tracer by codoping Li3Ba2Gd3 (MoO4)8 with Yb3+ and Er3+, where Yb3+ is a synthesizer ion (excited near 976 nm) and Er3+ emits near 1550 nm. Fine-tuning of the doping concentration resulted in a tracer (Li3Ba2Gd(3-x-y)(MoO4)8:xYb3+, yEr3+, where x = 0.2 and y = 0.4) with a high photoluminescence quantum yield for 1550 nm emission of 70% (using 976 nm excitation). This tracer was used to mark plastic objects. When the object was illuminated by a halogen lamp and a 976 nm laser, the three parts could be easily distinguished based on reflectance and luminescence spectra in the SWIR range: a plastic bottle made of polyethylene terephthalate, a bottle cap made of high-density polyethylene, and a label made of the tracer Li3Ba2Gd3(MoO4)8:Yb3+, Er3+. Importantly, the use of the tracer in sorting may require only the installation of a 976 nm laser in a state-of-the-art NIR sorting system.

Modulated upconversion luminescence of WO3: Yb3+/Ho3+ through non-equivalence substitution of Bi3+ ions

The upconversion luminescence (UCL) of inorganic materials doped with activators and sensitizers has great application, but its luminescence intensity always impose restrictions on its development. Herein, an obvious enhancement in luminescence intensity of the WO3: Yb3+, Ho3+ phosphor was realized through non-equivalence substitution of Bi3+ ions. The single pure phase of the synthesized WO3: Yb3+, Ho3+, and Bi3+ phosphors has been confirmed by the XRD pattern. The morphology of phosphors and valence state of elements have been performed by SEM and XPS techniques. The sample on excitation with 980 nm performs forceful green emission and weak red emission at 543 nm and 662 nm, separately. The concentrations for doped Yb3+ and Ho3+ to obtain the optimal UCL in WO3 are 8% and 1%, respectively. The optimized doping concentration for Bi3+ ions is 3%. Compared to samples without Bi3+ ions, the Yb3+/Ho3+/Bi3+ doped WO3 obtains 1.59 and 2.33 times increase in emission intensity of green and red, respectively. We also explored the UCL mechanism and enhancement mechanism on the basis of the power dependency, the UCL and the downshift luminescence. These results based on Yb3+/Ho3+ UCL phosphors research is of great significance.

Simultaneously Achieving Multicolor Emission of Down‐Shifting and Up‐Conversion in Yb3+, Er3+ ‐Codoped Cs2NaGdCl6 Double Perovskites

AbstractUltraviolet (UV) excited down‐shifting (DS) double perovskites with broad emission have potential applications in anti‐counterfeiting. However, discovering new materials and achieving multimode luminescence present significant challenges. In this work, a novel double perovskite, Cs2NaGdCl6 is synthesized, with sky‐blue self‐trapped exciton (STE) emission under UV excitation using a solvothermal method. By incorporating Er3+ ions into Cs2NaGdCl6, green DS and green up‐conversion (UC) luminescence are achieved under UV and near‐infrared (NIR) excitation. The addition of the sensitizer Yb3+ ion led to a significant enhancement of 21.5‐fold in DS red luminescence and 7.5‐fold in UC green luminescence. The color of both DS and UC luminescence in Cs2NaGdCl6:Yb3+, Er3+ is further adjusted from green‐dominated to red‐dominated, due to the cross‐relaxation process between Er3+ and Yb3+, Er3+ and Er3+, respectively. The combination of UC and DS luminescence, along with the ability to modulate emission color in rare‐earth‐based materials, opens new possibilities for high security anti‐counterfeiting applications.

Photoluminescence of Eu3+ in silicate-based phosphors by near-infrared and near-ultraviolet excitation for multifunctional applications

In this work, a series of Eu3+/Yb3+ doped La1.55SiO4.33 (LSO) phosphors were prepared by solid state reaction method for multifunctional applications. The phase purity and particle morphology were characterized with XRD and SEM technique, respectively. Upon ultraviolet light excitation, the downshifting luminescence of Eu3+ was observed in the red region, and the strongest emission peak located at 612 nm is attributed to the forced electric dipole 5D0→7F2 transition. The optimal Eu3+ doping concentration was determined to be 20 mol%, for which the internal quantum efficiency of the phosphor reaches 75.1%. The temperature-dependent emission spectra of LSO:20%Eu3+ revealed that the quenching temperature T0.5 is 483 K. For the upconversion (UC) luminescence, the Yb3+-Eu3+ codoped LSO phosphors were designed, where the Yb3+ ion was used as a sensitizer. The UC mechanism for a cooperative energy transfer was learnt from the pump-power-dependent emission spectra. By excitation at various temperatures, the intensities of emissions from different excited states showed different changes with temperature. All the above spectral characteristics indicate that the LSO:Eu3+/Yb3+ phosphors can show potential applications in LEDs, anticounterfeiting and optical thermometer.

Enhanced upconversion luminescence and single-band red emission in β-Ba2ScAlO5: Yb3+/Er3+ phosphor through doping Cu2+

This study reports on a single-band red upconversion emission of Er3+ in a pure-phase β-Ba2ScAlO5: Yb3+/Er3+ fluorescent powder by doping Cu2+. The optimum concentration of Cu2+ ions in β-Ba2ScAlO5: Yb3+/Er3+ powder was 0.20. The red and green emission intensity of β-Ba2ScAlO5: Yb3+/Er3+ sample with optimum concentration of Cu2+ ions increased by 19.1 and 3.6 times, respectively, relative to the β-Ba2ScAlO5:Yb3+/Er3+ material lacking Cu2+ ions. The red-green integral intensity ratio of the β-Ba2ScAlO5:Yb3+/Er3+/Cu2+ phosphor reached 141.9. The potential upconversion luminescence (UCL) mechanism was explored by analyzing the down-shift luminescence (DS) spectra, upconversion luminescence spectra, and upconversion fluorescence lifetime decay curves of Yb3+/Er3+/Cu2+ triple-doped β-Ba2ScAlO5. Enhanced red emission and green upconversion emission are achieved by energy transfer between defect band by the oxygen vacancy and Er3+ energy levels. This study's findings establish the foundation for developing novel phosphors with single UC red light emission, which has potential applications in illumination displays, optical thermometry, and biomedicine.