Back Energy Transfer Research Articles

Dynamic exciton-to-dopant energy transfer tuning of Mn2+-Doped perovskite nanocrystals by PBG effect

Cesium lead halide perovskite nanocrystals (CsPbX3 NCs) doped with Mn2+ brings attractive long-wavelength emission and flexible color tunability. However, modulating the exciton-to-Mn2+ energy transfer efficiency poses a challenge, particularly when relying on traditional methods such as changing halogen composition or incorporating external cations, which often complicate the process. In this work, a simple photonic bandgap (PBG)-modulation strategy is applied to modulate the exciton-to-Mn2+ energy transfer by constructing a sandwich “PC-Perovskite-PC” structure with two photonic crystal (PC) films and Mn2+ doped CsPb(ClBr)3 NPs. When the PBG and the host emission band change from deviation to coincidence, the lifetime of Mn2+ decreases from 0.54 ms to 0.36 ms owing to the enhancing energy transfer efficiency by PBG effect. Meanwhile, the ratios of orange and blue emissions (O/B) increase from 1.36 to 1.6. In addition, the back energy transfer also can be modulated. When the PBG matches well with the Mn2+ emission band, the lifetime of the host emission exhibits the largest value (1.25 ns) owing to back energy transfer from Mn2+ the host. Meanwhile, the O/B value shows the smallest value (0.52) attributed to the decreased spontaneous radiation of Mn2+ and the enhanced host emission. When PBG deviates from the Mn2+ emission band, the lifetime of the host emission decreases but O/B value increases gradually. This work provides new strategy for the modulation of energy transfer in Mn2+ doped CsPb(ClBr)3 NPs.

Unusual Tm3+ sensitization-induced white-emitting and thermostable improvement in Ba2Y2Ge4O13:Dy3+ phosphor for solid-state lighting and optical thermometry

Currently, the development of single-phase white emitters is an interesting research topic. Researchers have paid much attention to tune white-emitting of Dy3+-activated phosphors via Tm3+ sensitization strategy. However, the role of Tm3+ sensitization on luminescence thermostability was usually underestimated. Herein, color-tunable germanate phosphors Ba2Y2Ge4O13 (BYGO):Tm3+,Dy3+ were prepared. The white light emission is achieved due to the effective energy transfer from Tm3+ to Dy3+. A BYGO:Tm3+,Dy3+-based w-LED exhibits warm white-emitting. Moreover, the back-energy transfer of Dy3+→Tm3+ contributes to the improvement of luminescence thermal stability. Meanwhile, the difference of temperature-dependent Tm3+ and Dy3+ emissions realizes satisfactory temperature sensing properties. This work provides a deep understanding for the role of Tm3+ sensitization strategy on color tuning and thermostable improvement, promoting multifunctional utilizations of Dy3+-activated phosphors.

Designing Polychromatic Er3+/Yb3+-Codoped Bi2WO6 Upconverting Nanoparticles with Enhanced Visible-Light-Triggered Photocatalytic Properties toward Tetracycline Degradation.

To address the unsatisfactory photodegradation capacities of photocatalysts, Er3+/Yb3+-codoped Bi2WO6 (Bi2WO6:Er3+/xYb3+) nanoparticles (NPs) with polychromatic upconversion (UC) emission and boosted visible-light-triggered photocatalytic abilities were designed. First-principles density functional theory was employed to study the impact of Er3+ and Yb3+ codoping on the electronic structure of Bi2WO6. Upon 980 nm excitation, the resultant NPs emitted polychromatic UC emissions caused by energy back transfer from Er3+ to Yb3+. Moreover, the involved UC emission mechanism was clarified through examining the pump power related to UC emission spectra. By investigating the visible-light-induced tetracycline (TC) decomposition, the photocatalytic activities of developed NPs were explored, where Bi2WO6:Er3+/0.07Yb3+ NP can degrade 81.76% of TC within 30 min, with a k value of 0.0552 min-1. Both the theoretical calculation and trapping results reveal that the •O2-, h+, and •OH were formed during the pollutant removal process. Additionally, the toxic TC can be photodegraded to nontoxic products via the synthesized photocatalysts, leading to wastewater purification. These achievements manifest that Bi2WO6:Er3+/xYb3+ NPs are promising visible-light-triggered photocatalysts to degrade pollutants, and our findings also propose a facile approach to regulate the photocatalytic activities of photocatalysts via utilizing doping and UC emission strategies.

All-optical output power stabilization of double-clad Er:Yb amplifiers using 1064 nm signal injection

We present a novel technique for all-optical stabilization of the output power of telecom band amplifiers based on double-clad (DC) erbium-ytterbium (Er:Yb) doped fibers. The proposed method relies on the utilization of the undesirable energy back-transfer effect which occurs in DC Er:Yb active fibers. A feedback loop is built based on a low-power 1064 nm laser, which is coupled into the Er:Yb fiber along with the 1550 nm seed. The auxiliary 1 µm signal partially extracts the Yb-ion energy, altering the gain at the design wavelength. The stabilization technique was verified for two types of fibers, to demonstrate the feasibility of our approach regardless of the type of DC Er:Yb fiber used, its characteristics, and the amplifier configuration. A long-term stability improvement by a factor of 117 was achieved, reaching a deviation of 0.8 µ W, for 100 s integration time.

Influence of Yb3+/Ho3+ codoping on optical and thermal properties of TeO2-ZnO glass

This paper reports the effect of incorporation of Yb3+ ions on the frequency downconversion luminescence and thermal properties of triply ionised Ho3+ doped zinc tellurite (TZ) glasses. The photoluminescence spectra of both the Ho3+/Yb3+ doped and codoped glasses have been recorded and observed a green emission band corresponding to the 5F4, 5S2 → 5I8 (∼550 nm) transition upon various excitations. In the downconversion (DC) emission process, the back energy transfer (BET) mechanism from Ho3+ ions to Yb3+ ions has also been explored. The colour emitted in the downconversion process is found to be non-tunable at different excitations. Thus, the Ho3+:TZ glass can be utilised for non-colour tunable optical devices under various UV excitations. Also the glass transition (Tg) and crystallisation (Tc) temperatures have been measured for both the doped and codoped glasses and found to be increased in the codoped glass. The singly Ho3+ions doped TZ glass shows better optical downconversion and glass forming ability.

Upconversion, downshifting, quantum cutting and back energy trasfer from Yb3+ to Er3+ in Er3+/Yb3+ co-doped CaTiO3 phosphor, intense NIR generation for communication

The perovskite based phosphor materials are widely used to increase the efficiency of solar cells. In this work, Er3+ doped and Er3+/Yb3+ co-doped CaTiO3 perovskite phosphor samples have been synthesized by solid state reaction technique at 1473 K. The phosphor samples show orthorhombic phase with Pnma (62) space group. The average crystallites and particles size of CaTiO3 are increased in presence of Er3+ and Yb3+ ions. Er3+ doped CaTiO3 phosphor samples give downshifting emission under 379 nm excitation. Though upconversion emission is seen in Er3+ under 980 nm excitation without Yb3+ ions in this host. The emission intensity of Er3+ ion is enhanced by 46 and 16 times for green and red emissions, respectively in presence of Yb3+. An intense quantum cutting (QC) emission is observed at 980 nm in presence of Yb3+ in CaTiO3:0.5Er3+ phosphor under 379 nm excitation. The QC efficiency has been found to be 119 % for CaTiO3:0.5Er3+/5 Yb3+ phosphor. Further an interesting phenomenon of back energy transfer (BEnT) from Yb3+ to Er3+ giving an intense NIR emission from Er3+ at 1002 and 1550 nm have been observed. The phosphor sample also shows an intrinsic optical bistablity (IOB) by upconversion. Thus, the prepared phosphor samples may be useful to increase the efficiency of c-Si solar cell, NIR emission for communication, bistable material and green light emitting source.

Dual lanthanide Complexes-Loaded ratiometric nanothermometer for elucidating intracellular variations of temperature and calcium transport

Herein, we report a ratiometric nanothermometer to study the correlation of heat/temperature and intracellular calcium transport. Firstly, poly(methyl methacrylate)-based copolymeric nanoparticles (NPs) from nanoprecipitation encapsulates two lanthanide complexes (Eu(DNPD)3Phen and Sm(DBM)3Phen) to enhance fluorescence of lanthanide ions (Ln3+). NPs were thereafter coated with an amphiphilic block copolymer pluronic F-127 to prevent nonspecific interaction between NPs and proteins, which ensures internalization of the nanothermometer into living cells. The back energy transfer (BET) from the excited state of Ln3+ to the triplet energy levels of ligand endows the temperature dependence on ratiometric fluorescence of Eu3+ and Sm3+. This nanothermometer has excellent anti-interference ability, ensuring accurate cell temperature measurement within a range of 29.0–40.0℃. It exhibits a maximum relative thermal sensitivity of 1.9 % ℃-1 at 29.0℃ and a minimum temperature resolution of 0.1℃ at 39.0℃ in live HeLa cells. The nanothermometer was applied for studying temperature or heat induced intracellular Ca2+ transport. It illustrated that free cytoplasmic Ca2+ concentration ([Ca2+]i) increased only when the cell temperature reached a certain threshold under photothermal stimulation, and the rise of temperature corresponds to the increase of [Ca2+]i. Furthermore, Ca2+ burst induced Ca2+ transport from cytoplasm to endoplasmic reticulum, which promoted ATP hydrolysis along with the rise of intracellular temperature. 200 s stimulation with FCCP enhanced ca. 1.7℃ of intracellular temperature along with 2.2 folds increment of [Ca2+]i, as FCCP induces Ca2+ efflux from mitochondria by increasing proton concentration therein. These results indicate that a close relationship between intracellular temperature and Ca2+ transport, which is of great significance for further understanding the role of temperature in signaling pathways and neurotransmitter release events.

Enhanced thermal stability and luminous properties of Dy3+/Tm3+/Eu3+ doped glass ceramics containing Sr4Bi(PO4)3O crystalline phases based on back energy transfer

White light emitting and optical temperature sensing materials with high thermal stability have broad market development prospects. The use of substrates with excellent thermal stability is a common idea to improve thermal stability, while the modulation of dopants to enhance thermal stability has been less studied. Therefore, in this work, Tm3+/Dy3+/Eu3+ doped transparent glass ceramics containing Sr4Bi(PO4)3O crystalline-phase were prepared by melt-crystallization method to achieve warm white light emission and optical temperature sensing with good thermal stability. Since the Tm3+-Dy3+ doped samples can only achieve cold white light emission, warm white light emission is obtained by adding Eu3+, which can emit red light. The application scenario of the material is expanded. The luminous intensities of Tm3+, Dy3+, and Eu3+ were 109.4 %, 89.1 %, and 70.7 % of those at room temperature, at 473 K. The increase in the emission intensity of Tm3+ was explained by the presence of back energy transfer (BET) from Dy3+ and Eu3+ to Tm3+. The chromaticity shift (Δε) of the samples was 2.43 × 10−4 and the luminescent colour was stable. The absolute sensitivity of the material can reach 0.69 K−1 at 473 K, and the relative sensitivity of the material can reach 1.60 % K−1 at 293 K. This work provides new ideas for the study of improving the thermal stability of materials.

Yb3+/Ho3+ doped Ba3Y2B4O12 phosphors: Upconversion luminescence and temperature sensing properties

Optical thermometry achieved by luminescent materials with good stability and high sensitivity has attracted much attention. In this article, Ba3Y2B4O12, a borate with good chemical stability and high laser threshold was chosen to be host material for preparing a series of Ba3Y2-x-yYbxHoyB4O12 (BYBO:xYb3+/yHo3+; 0.01 ≤ x ≤ 0.35, 0.005 ≤ y ≤ 0.035) upconversion phosphors by a facile solid-state method. Under 980 nm excitation, phosphors show strong 551 nm green emission, weak 668 nm red emission, and 755 nm near-infrared emission, while bright greenlight can be observed by naked eye. When x = 0.15, y = 0.01, luminescent intensity obtains the maximum value. At higher doping concentration, the reduction of cell parameters caused by doping can accelerate the decrease of distance between dopants, so that the energy back transfer process is more likely to occur, weakening the green emission. The intensified non-radiative relaxation results in an increased red emission proportion at higher temperature. According to this rule, the temperature sensing properties based on the fluorescence intensity ratio I668/I551 and I688/I755 are studied. The maximum relative sensitivity (SR) reaches 1.53 % K−1 at 478 K, which is higher than most of reported materials. It shows that BYBO:Yb3+/Ho3+ has application potential in temperature sensing.

The Influence of Concentrations of Sensitizers and Activators on Luminescence Kinetics Parameters of Up-Conversion Nanocomplexes NaYF4:Yb3+/Tm3+

For colloids of NaYF4:Yb3+/Tm3+ nanoparticles in DMSO, by the method of time-resolved luminescence spectroscopy with nanosecond pulsed excitation at a wavelength of 975 nm, the photophysical processes that determine the course of kinetic curves have been revealed. It has been found that the luminescence rise time decreases with an increase in the concentration of activators and sensitizers due to the increase in the efficiency of energy transfer from sensitizers to activators. The cross-relaxation of the excited states of activators provides a decrease in the luminescence decay time with an increase in the concentration of activators and a constant concentration of the sensitizer. There is no correlation between the time of luminescence decay with the change in the concentration of sensitizers and the constant concentration of activators due to the competition of the processes of energy back transfer from activators to sensitizers and the “feeding” of activators by excitations coming from remote sensitizer ions.

Near-infrared light driven highly efficient and thermally stable Gd2Ti2O7:Er3+/Yb3+ sub-microspheres for photocatalytic and plant growth LED applications

Photocatalysis is a technique that can help address various global challenges of energy and environment by utilizing solar energy. Photocatalysts that can capture light from different regions of the electromagnetic spectrum, such as ultraviolet, visible or near-infrared, are required to optimize the use of solar energy. Therefore, researchers have been developing various strategies to design such photocatalysts. Herein, we report the NIR-induced photocatalytic performance of pyrochlore-structured Gd2Ti2O7:1Er3+/10Yb3+ (GT:Er3+/Yb3+) sub-microspheres by using rhodamine B (RhB), a commom organic dye, as a probe molecule. A facile solvothermal process was used to prepare the sub-microspheres that emitted strong red light when irradiated by a 980 nm laser. The luminescence mechanism was attributed to cross-relaxation and back energy transfer processes. Furthermore, the GT:Er3+/Yb3+ sub-microspheres exhibited remarkable thermal stability and durability under 980 nm laser irradiation and the catalytic studies showed in the presence of laser light of only 1 W input power. The sub-microspheres completely broke down RhB dye into H2O and CO2 in 10 h. This study offers a novel approach to exploit NIR-driven lanthanide materials for LED and photocatalytic applications.

Tuning white light emission using single-component tetrachroic Dy3+ metallacrowns: the role of chromophoric building blocks.

White light production is of major importance for ambient lighting and technological displays. White light can be obtained by several types of materials and their combinations, but single component emitters remain rare and desirable towards thinner devices that are, therefore, easier to control and that require fewer manufacturing steps. We have designed a series of dysprosium(iii)-based luminescent metallacrowns (MCs) to achieve this goal. The synthesized MCs possess three main structural types LnGa4(L')4(L'')4 (type A), Ln2Ga8(L')8(L''')4 (type B) and LnGa8(L')8(OH)4 (type C) (H3L', HL'' and H2L''' derivatives of salicylhydroxamic, benzoic and isophthalic acids, respectively). The advantage of these MCs is that, within each structural type, the nature of the organic building blocks does not affect the symmetry around Dy3+. By detailed studies of the photophysical properties of these Dy3+-based MCs, we have demonstrated that CIE coordinates can be tuned from warm to neutral to cold white by (i) defining the symmetry about Dy3+, and (ii) choosing appropriate chromophoric building blocks. These organic building blocks, without altering the coordination geometry around Dy3+, influence the total emission profile through changing the probability of different energy transfer processes including the 3T1 ← Dy3+* energy back transfer and/or by generating ligand-centered fluorescence in the blue range. This work opens new perspectives for the creation of white light emitting devices using single component tetrachroic molecular compounds.

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 Yb3+ concentration on the upconversion emission properties of sub 10 nm RbY2F7:Yb, Er nanoparticles.

Upconversion nanoparticles (UCNPs) are a fascinating group of luminescent materials known for their ability to convert low-energy photons to high-energy photons. Many inorganic UCNPs have been studied to understand the underlying mechanism of upconversion phenomena, out of which alkali rare-earth fluorides (AREFs) such as NaREF4, LiREF4 and KREF4 were found to exhibit high upconversion efficiencies. This work investigates a similar AREF upconversion nanoparticle viz RbY2F7:Yb, Er. This UCNP system was synthesised by a modified thermal decomposition method by varying the Yb concentration from 20% to 98%. Structural analysis using XRD revealed that all the synthesised samples were found to be formed in the orthorhombic phase irrespective of the increasing Yb concentration. The thermal decomposition method greatly aided in the reduction of particle size. HRTEM analysis revealed that the as-synthesised UCNPs have a spherical morphology with an average particle size of 7.9 ± 0.2 nm. The upconversion emission studies taken by exciting the samples with a 975 nm laser show three distinct peaks at 527, 542 and 656 nm. The experimental results indicate that the increased Yb3+ concentration improves the red to green intensity ratio by supporting the 4F9/2 → 4I15/2 transition of Er3+ through the energy back transfer process between Er3+ and Yb3+. Notably, there is a reduction in the overall emission intensity with increasing Yb3+ concentration. Furthermore, the decay lifetime studies show a decreasing trend at 542 nm and 656 nm emission lines with an increase in the Yb concentration, which is because of the concentration quenching effect of the increasing Yb concentration.

Blue emission-dominated NaYbF4@NaYF4:2%Ho@NaYF4 upconversion nanoparticles for detecting ascorbic acid.

The blue emission-dominated NaYbF4@NaYF4:2%Ho@NaYF4 (CSS) upconversion nanoparticles (UCNPs) were designed to detect ascorbic acid (AA). The blue emission of CSS was increased, ∼34 and ∼8 times higher than that of NaYF4:2%Ho@NaYbF4@NaYF4 (CSS (I)) and NaYbF4@NaYF4:20%Yb,2%Ho@ NaYF4 (CSS (II)), respectively. The dominant blue emission of CSS might be attributed to three aspects: (1) the protected NaYbF4 core for high near-infrared absorption, (2) the spatial separation of Yb3+ and Ho3+ preventing back energy transfer, and (3) their inert shell inhibiting surface quenching. It is worth noting that the fluorescence resonance energy transfer (FRET) of the CSS (donor) to MnO2 nanosheets (acceptor) was developed to trace AA. The detection limit is 0.75 μM and the detection range is 0.5-100 μM. In summary, our work not only explored the blue emission mechanism of Ho3+, but also constructed a CSS/MnO2-based nanosensing platform for the rapid and sensitive detection of AA. The blue emission of Ho3+ has promising applications in the field of sensing and detection.

Multi-dimensional tailoring of the thermometric behaviors of Er3+/Yb3+-codoped Y2W3O12 polychromatic upconverting microparticles for multi-mode visual optical thermometry

To combat the thermal quenching and inadequate sensitivities of luminous materials, the Y1.98–2xW3O12:0.02Er3+/2xYb3+ (YWO:Er3+/2xYb3+; 0.01 ≤ x ≤ 0.11) microparticles with splendid negative thermal expansion (NTE) effect were designed. Excited at 980 nm, the produced samples emit polychromatic upconversion (UC) emissions triggered by the energy back transfer from Er3+ to Yb3+ and it has been systematically discussed via steady-state rate theory. The thermally enhanced UC emissions are accomplished in YWO:Er3+/2xYb3+ microparticles due to the distinctive NTE properties. Moreover, according to the temperature-associated UC emissions of Er3+ arising from its thermally coupled levels (TCLs) and non-thermally coupled levels (non-TCLs), the thermometric properties of synthesized microparticles are investigated. When non-TCLs are adopted, the absolute and relative sensitivities of resultant microparticles are 0.0129% and 1.7875% K−1, respectively. Furthermore, through manipulating doping content and spatial mode, the temperature sensing capacities of YWO:Er3+/2xYb3+ microparticles are multi-dimensionally regulated. In addition, contactless temperature recognition can also be realized through analyzing the thermochromic features of final products and its relative sensitivity is 2.1604% K−1. Ultimately, visual optical temperature detection is obtained in designed microparticles via its temperature-related emitting colour. Our findings may provide an important insight into the design of luminescent materials with high sensitivities for multi-mode visual optical thermometry.

Ultrasensitive NIR-II Ratiometric Nanothermometers for 3D In Vivo Thermal Imaging.

Luminescent nanothermometry, particularly the one based on ratiometric, has sparked intense research for non-invasive in vivo or intracellular temperature mapping, empowering their uses as diagnosis tools in biomedicine. However, ratiometric detection still suffers from biased sensing induced by wavelength-dependent tissue absorption and scattering, low thermal sensitivity (Sr ), and lack of imaging depth information. Herein, this work constructs an ultrasensitive NIR-II ratiometric nanothermometer with self-calibrating ability for 3D in vivo thermographic imaging, in which temperature-insensitive lanthanide nanocrystals and strongly temperature-quenched Ag2 S quantum dots are co-assembled to form a hybrid nanocomposite material. Precise control over the amount ratio between two sub-materials enables the manipulation of heat-activated back energy transfer from Ag2 S to Yb3+ in lanthanide nanoparticles, thereby rendering Sr up to 7.8% °C-1 at 43.5 °C, and higher than 6.5% °C-1 over the entire physiological temperature range. Moreover, the luminescence intensity ratio between two separated spectral regions within the narrow Yb3+ emission peak is used to determine the depth information of nanothermometers in living mice and correct the effect of tissue depth on 2D thermographic imaging, and therefore allows a proof-of-concept demonstration of accurate 3D in vivo thermographic imaging, constituting a solid step toward the development of advanced ratiometric nanothermometry for biological applications.

Highly‐Doped Lanthanide‐Based Nanocrystals with Cooperative Core‐Shell Upconversion Emission for Multicomponent One‐Pot Chemical Transformations

AbstractIn order to apply near infrared (NIR) light‐activated upconversion nanocrystals (UCNCs) in photochemistry, extremely bright luminescence is needed to excite the ultraviolet (UV)‐visible light absorbing photocatalyst/substrate. In this study, a multilayered UCNC consisting of a β‐NaYF4:Yb0.2, Tm0.005 core, heavily Yb3+‐doped β‐NaYbF4:Y0.09, Tm0.01 intermediate shell, and inert β‐NaYF4 outer shell is prepared. By compartmentalizing the sensitizer (Yb3+)‐activator (Tm3+) pair in the core and intermediate shell with different concentration ratios, a cooperative luminescence effect is discovered. Apart from core emission, energy harvesting followed by sequential energy transfer from a high density of neighboring Yb3+ to Tm3+ in the intermediate shell induces a large population of excited emitter ions. Furthermore, after back energy transfer from the core to intermediate shell, the energy is not quenched by intrinsic trap sites but is instead transferred to Tm3+, further boosting emission in the UV, blue, and NIR regions. The exceptionally bright UCNC is then used to drive NIR‐light‐activated one‐pot multicomponent reactions involving the upconversion energy transfer from UCNC to UV‐visible light absorbing photocatalyst/substrate, Lewis acid catalytic activity of the lanthanide ions (Y3+) on the surface, and photothermal property of the UCNC. The reactions studied include the deacetalization‐Knoevenagel condensation reaction, photooxidation‐cyanation reaction, and hydrodehalogenation‐cyanosilylation reaction.

Photosensitizing deep-seated cancer cells with photoprotein-conjugated upconversion nanoparticles

To resolve the problem of target specificity and light transmission to deep-seated tissues in photodynamic therapy (PDT), we report a cancer cell-targeted photosensitizer using photoprotein-conjugated upconversion nanoparticles (UCNPs) with high target specificity and efficient light transmission to deep tissues. Core-shell UCNPs with low internal energy back transfer were conjugated with recombinant proteins that consists of a photosensitizer (KillerRed; KR) and a cancer cell-targeted lead peptide (LP). Under near infrared (NIR)-irradiating condition, the UCNP-KR-LP generated superoxide anion radicals as reactive oxygen species via NIR-to-green light conversion and exhibited excellent specificity to target cancer cells through receptor-mediated cell adhesion. Consequently, this photosensitizing process facilitated rapid cell death in cancer cell lines (MCF-7, MDA-MB-231, and U-87MG) overexpressing integrin beta 1 (ITGB1) receptors but not in a cell line (SK-BR-3) with reduced ITGB1 expression and a non-invasive normal breast cell line (MCF-10A). In contrast to green light irradiation, NIR light irradiation exhibited significant PDT efficacy in cancer cells located beneath porcine skin tissues up to a depth of 10 mm, as well as in vivo tumor xenograft mouse models. This finding suggests that the designed nanocomposite is useful for sensing and targeting various deep-seated tumors.

Ultrapure single-band red upconversion luminescence in Er3+ doped sensitizer-rich ytterbium oxide transparent ceramics for solid-state lighting and temperature sensing.

Achieving single-band upconversion (UC) is a challenging but rewarding approach to attain optimal performance in diverse applications. In this paper, we successfully achieved single-band red UC luminescence in Yb2O3: Er transparent ceramics (TCs) through the utilization of a sensitizer-rich design. The Yb2O3 host, which has a maximum host lattice occupancy by Yb3+ sensitizers, facilitates the utilization of excitation light and enhances energy transfer to activators, resulting in improved UC luminescence. Specifically, by shortening the ionic spacing between sensitizer and activator, the energy back transfer and the cross-relaxation process are promoted, resulting in weakening of green energy level 4S3/2 and 2H11/2 emission and enhancement of red energy level 4F9/2 emission. The prepared Yb2O3: Er TCs exhibited superior optical properties with in-line transmittance over 80% at 600 nm. Notably, in the 980nm-excited UC spectrum, green emission does not appear, thus Yb2O3: Er TCs exhibit ultra-pure single band red emission, with CIE coordinates of (0.72, 0.28) and color purity exceeding 99.9%. To the best of our knowledge, this is the first demonstration of pure red UC luminescence in TCs. Furthermore, the luminescent intensity ratio (LIR) technique was utilized to apply this pure red-emitting TCs for temperature sensing. The absolute sensitivity of Yb2O3: Er TCs was calculated to be 0.319% K-1 at 304 K, which is the highest level of optical thermometry based on 4F9/2 levels splitting of Er3+ known so far. The integration between pure red UC luminescence and temperature sensing performance opens up new possibilities for the development of multi-functional smart windows.