Upconversion Mechanism Research Articles

Scotch yoke structure inspired piezoelectric-electromagnetic hybrid harvester for wave energy harvesting

This paper presents a piezoelectric-electromagnetic hybrid harvester for wave energy harvesting inspired by a scotch yoke structure for obtaining energy from irregular and low-frequency waves. Through simplification of the energy harvester model, the kinematic equations of the scotch yoke are established. One of the advantages of the harvester is that the wave energy can be harvested by an up-conversion mechanism, The piezoelectric transducer (PZT) and electromagnetic generator (EMG) transform the wave excitation into electricity, and by utilizing the frequency up-conversion mechanism, the PZTs’ harvesting efficiency is increased, the influencing factors of the output power of the harvester are explored by simulation and experimental studies, The results of the experiment demonstrate that this harvester could generate an ultimate output power of 286.36 mW at ultra-low frequency (1.4 Hz) operating frequency. This study offers a practical solution for harvesting low-frequency and disordered wave energy and makes significant progress in harvesting low-frequency and irregular wave energy.

Ultrasensitive and Adjustable Nanothermometers Based on Er3+-Sensitized Core@Shell Nanoparticles for Use in the First Biological Window.

In recent years, intensive research has focused on lanthanide-doped nanoparticles (NPs) used as noncontact temperature sensors, particularly in nanomedicine. These NPs must be capable of excitation and emission within biological windows, where biological materials usually show better transparency for radiation. In this article, we propose that NPs sensitized with Er3+ ions can be applied as temperature sensors in biological materials. We synthesized the NPs through a reaction in high-boiling solvents and confirmed their crystal structure and the formation of core@shell NPs by using X-ray diffraction, high-resolution transmission electron microscopy, and element distribution mapping within the NPs. NaErF4@NaYF4, NaYF4:12.5% Er3+, 2.5% Tm3+@NaYF4, NaYF4:7.5% Er3+@NaYF4, and NaYF4:12.5% Er3+, 2.5% Ho3+@NaYF4 exhibited intense upconversion (UC) emission under 1532 nm laser excitation detectable also in the whole human blood. We propose that this UC results from energy transfer between Er3+ ions and from Er3+ to Tm3+ or Ho3+ codopants. To determine the mechanism of UC, we measured the dependence of the emission band intensities on the laser power densities. Importantly, we also analyzed the temperature-dependent emission of the NPs within the 295-360 K range. Based on the collected emission spectra, we calculated the luminescence intensity ratios (LIRs) of the emission bands to assess their potential for optical temperature sensing. The temperature-sensing properties varied with the concentration of Er3+ ions and the presence of additional Tm3+ or Ho3+ codopants. Depending on the NP composition and the emission bands used for luminescence ratio calculations, the maximum relative temperature sensitivity ranged from 4.55%·K-1 to 1.12%·K-1, with temperature resolution between 0.05 and 2.53 K at room temperature. Finally, as proof of using NPs as temperature sensors in biomedicine, we successfully measured the temperature-dependent emission of NaYF4:7.5% Er3+@NaYF4 NPs dispersed in whole blood under 1532 nm excitation. We demonstrated that the ratio of Er3+ ion emission bands changes with temperature, indicating that these NPs have potential applications in temperature sensing within biological environments. We also confirmed the properties of NPs as temperature sensors by measuring the temperature reading uncertainty and the repeatability of the LIR readings during heating-cooling cycles, thereby confirming the excellent properties of the studied systems as temperature sensors.

Distortion Engineering: A Strategy to Modulate Molecular Upconversion with Molecular Cluster-Aggregates.

The rational engineering of molecules is a powerful chemistry tool of pivotal importance in the fields of molecular magnetism and luminescence. Hence, systems that can be modulated via molecular engineering and composition control are expected to present extra versatility regarding the tunability of their properties. This is the case with molecular cluster aggregates (MCAs), high nuclearity molecular compounds. Herein, we demonstrate how the union of both strategies, namely, composition control and molecular engineering, can be employed to enhance molecular upconversion in MCAs. This was achieved by doping a {Gd8Er2Yb10} MCA with CeIII ions. By replacement of the optically silent GdIII ions with CeIII, the upconversion mechanism is modified due to CeIII-mediated cross-relaxation. In addition to this effect, we could also engineer the degree of metal site distortion due to the larger size of CeIII ions, relaxing the selection rules and impacting the upconversion quantum yield and luminescent thermometry. Opto-structural correlations demonstrate that the presented molecular engineering strategy can be used to enhance the performance of molecular upconverters.

Broad spectral response of Y-NaBi(MoO4)2@NaYF4:Yb, Tm photocatalysts for efficient degradation of ciprofloxacin: Upconversion mechanism and theoretical calculations

In this work, a novel Y-NaBi(MoO4)2@NaYF4:Yb, Tm composite was successfully synthesized for the first time by hydrothermal method. The lamellar Y-NaBi(MoO4)2 was dispersed on the surface of the hexagonal prism NaYF4:Yb, Tm without aggregation. The composite achieved a broad spectral response. The NaYF4:Yb, Tm absorbed near-infrared light and emitted ultraviolet and visible light by the energy transfer upconversion process. The emitted light was reabsorbed by Y-NaBi(MoO4)2 through the fluorescence resonance energy transfer process. Moreover, the doping of Y3+ ions enhanced the light response capability of the composite. The experimental results revealed that the photocatalytic degradation efficiency of ciprofloxacin (CIP) reached 96.2 % after 180 min of illumination under simulated sunlight. Meanwhile, the degradation pathways and attack sites of CIP were intensively investigated by liquid chromatography-mass spectrometry analysis and density functional theory theoretical calculations. The upconversion process, the separation of photogenerated carriers and rare earth metal ion doping all contributed to the high effective photodegradation. This work provided a new strategy for effective utilization of solar energy for the degradation of emerging pollutants to mitigate environmental pollution.

NIR‐induced upconversion‐assisted photopolymerization: Key factors, challenges, and future directions

AbstractNIR‐induced upconversion‐assisted photopolymerization has gained growing attention in the past two decades because of its numerous advantages over conventional UV/visible photopolymerization and two‐photon polymerization processes. However, research in this area is still in its early stages. To extend the practical application of NIR‐induced radiation curing, it is essential to optimize the factors affecting the photopolymerization reactions. Researchers have been constantly trying to improve these factors to tune the photo‐physical characteristics (luminescence intensity and color) of upconversion particles (UCPs), enhance curing depths and degree of double bond conversion (DC), and investigate the application of UCPs in emerging fields. In this review, first, a brief discussion of the upconversion mechanisms and upconversion efficiency is provided. Then, a detailed discussion of the factors influencing the upconversion‐assisted photopolymerization comprising UCP nature and characteristics, UCP content, presence of fillers/pigments/additives, laser intensity, photoinitiator content, and maximum absorption wavelength of photoinitiator is provided, and recent progress in improving these factors is presented. Finally, the advantages and drawbacks of the UC‐initiated polymerization are discussed, and perspectives for future directions are suggested.Highlights NIR‐induced upconversion‐assisted photopolymerization garners growing interest. Influential factors in upconversion‐assisted photopolymerization are thoroughly discussed. The recent progress on improving these factors and the future directions are provided.

Low blue-hazard white-light emission based on color-tunable triplet-triplet annihilation upconversion

The commonly used artificial light sources, such as fluorescent lamps and white light-emitting diodes, often have a high ratio of blue light emission, which poses potential blue light hazards, especially one of the main culprits leading to eye diseases. Therefore, developing novel white lighting sources with low blue-hazard is highly appreciated. In this work, an air-stable and color-tunable triplet–triplet annihilation upconversion (TTA-UC) mechanism was proposed to realize the low blue-hazard white-light emission. The proposed design was composed of three primary RGB colors from the annihilator (9,10-diphenylanthracene, DPA), the laser excitation source, and the photosensitizer (palladium (II) octaetylporphyrin, PdOEP), respectively. The introduction of oil-in-water (o/w) microemulsion can effectively block the potential oxygen-induced triplet-quenching and benefit high UC efficiency. Moreover, either raising ambient temperatures or adding isobutanol can activate the UC process to yield white-light emission. Notably, the white-light emission with a Commission Internationale de l’Eclairage (CIE) coordinate of (0.33, 0.33) as well as a low ratio of blue emission (14.2 %) was achieved at an ambient temperature of 42 °C. Therefore, the proposed air-stable TTA-UC mechanism can significantly lower the blue-hazard and provide a novel solution for applications in lighting and display.

Near UV photon upconversion in cast solid with quantum dot

Abstract CdS/ZnS core-shell semiconductor quantum dots (QDs) were hybridized with1-naphthalenecarboxylic acid, a triplet transmitter, by a ligand exchange method. UV emission peaked at 340 nm or longer was obtained by visible continuous-wave excitation at 405 nm in n-hexane solution by mixing the hybridized QD with 2,5-diphenyloxazole (PPO) as UV emitter, based on triplet-triplet annihilation upconversion (TTA-UC) mechanism. The same mixture but in tetrahydrofuran gave solid film by solution casting, and the solid showed upconversion emission in near UV spectral region (380-395 nm) by 405-nm excitation.

Cellular Uptake of Upconversion Nanoparticles Based on Surface Polymer Coatings and Protein Corona.

Upconversion nanoparticles (UCNPs) are materials that provide unique advantages for biomedical applications. There are constantly emerging customized UCNPs with varying compositions, coatings, and upconversion mechanisms. Cellular uptake is a key parameter for the biological application of UCNPs. Uptake experiments have yielded highly varying results, and correlating trends between cellular uptake with different types of UCNP coatings remains challenging. In this report, the impact of surface polymer coatings on the formation of protein coronas and subsequent cellular uptake of UCNPs by macrophages and cancer cells was investigated. Luminescence confocal microscopy and elemental analysis techniques were used to evaluate the different coatings for internalization within cells. Pathway inhibitors were used to unravel the specific internalization mechanisms of polymer-coated UCNPs. Coatings were chosen as the most promising for colloidal stability, conjugation chemistry, and biomedical applications. PIMA-PEG (poly(isobutylene-alt-maleic) anhydride with polyethylene glycol)-coated UCNPs were found to have low cytotoxicity, low uptake by macrophages (when compared with PEI, poly(ethylenimine)), and sufficient uptake by tumor cells for surface-loaded drug delivery applications. Inductively coupled plasma-optical emission spectroscopy (ICP-OES) studies revealed that PIMA-coated NPs were preferentially internalized by the clathrin- and caveolar-independent pathways, with a preference for clathrin-mediated uptake at longer time points. PMAO-PEG (poly(maleic anhydride-alt-1-octadecene) with polyethylene glycol)-coated UCNPs were internalized by energy-dependent pathways, while PAA- (poly(acrylic acid)) and PEI-coated NPs were internalized by multifactorial mechanisms of internalization. The results indicate that copolymers of PIMA-PEG coatings on UCNPs were well suited for the next-generation of biomedical applications.

Er3+/ Yb3+ co-doped multi-functional silica phosphate glass films for integrated photonic applications

The multi-component silicate glasses co-doped with Er3+/Yb3+ were fabricated as thin films by the spin coating technique, which was analyzed for their optoelectronic response. Their monolith counterparts synthesized by the sol-gel route were used for the electrical studies. The films evidenced nanocristobalite phases at low levels of doping. The film micrographs explicated gas-trapped circular dimensions on the surface, due to the spreading of the sol on the substrate during the spin coating process. The glasses show a decrease in the number of polarizable non-bridging oxygen units with doping, reducing the polarizability and optical basicity. The films exhibit prominent green lasing in the downshifting process. The energy transfer from the Yb3+ ions endows the glasses with significant red lasing, suppressing the green emissions by the upconversion mechanism, which is also validated by the colorimetric chromaticity analysis. The gain cross-section of the glass doped with 1.5 mol% of Yb3+ is 23.3 × 10−20 cm2 in the S-band telecommunication domain. The glass film evidences its potential for NIR lasers, beyond a population inversion of 40 %, and a decreasing metastable lifetime of 6.6 μs. Beyond 1.5 mol% of the co-dopant Yb3+, energy transfer dominates, due to the dipole-quadrupole interactions, which has been corroborated by the Inokuti-Hirayama model. The conductivity in the glasses shows a decreasing trend with doping. The Randle's equivalent circuitry of the Nyquist impedance plots, predicts Warburg diffusion impedance that deters the space charge polarization. The consequential decrease in the dielectric constant and capacitance makes the glasses suggestive of multi-layer dielectric substrates in the integrated microelectronic technology for soldering of the printed circuit boards (PCB) that demand low signal losses.

Harnessing bright upconversion luminescence from PEG-coated NaGdF4:Ho3+/Yb3+ nanoparticles for contrast enhancement in dual mode OCT imaging and optical temperature sensing

In this work, authors synthesized the Polyethylene Glycol (PEG) coated NaGdF4:Ho3+/Yb3+ nanoparticles using the thermal decomposition reaction route. Our primary objective was to comprehensively evaluate their suitability for augmenting image contrast, particularly within the intricate domain of Swept Source Optical Coherence Tomography (SSOCT) and photo-thermal Optical Coherence Tomography (PTOCT) imaging modalities. Our meticulous inquiry yielded the revelation of extraordinary upconversion emissions, which emanated from the distinct transitions of Ho3+ ions, most notably the 5F4(5S2)→ 5I8 and 5F5→ 5I8 transitions. These transitions manifested as strikingly vibrant green emissions, precisely at the 539 nm and 661 nm wavelengths. Furthermore, we investigated the underlying upconversion mechanism, delving deeply into the elucidation of decay times and the nanoparticles' ability to transform incident radiation into thermal energy. Impressively, these nanoparticles exhibited a noteworthy photo-thermal conversion efficiency, specifically measured at an impressive 47.4 % along with the bright green luminescence. Our study also extended to bio-compatibility, where we achieved highly encouraging outcomes. Following 24 h of incubation with HeLa cells treated with UCNP-PEG, we ascertained a compelling cell survival rate exceeding 80 %, underscoring the favorable biocompatibility of these nanoparticles. Moreover, these nanoparticles demonstrated a conspicuous thermal sensitivity, quantified at 5.1 × 10−3 K−1 at 380K, thus signaling their potential for precision temperature monitoring and could be applied at the cellular level.

A Blade-Type Triboelectric-Electromagnetic Hybrid Generator with Double Frequency Up-Conversion Mechanism for Harvesting Breeze Wind Energy.

Triboelectric nanogenerators (TENGs) have garnered substantial attention in breeze wind energy harvesting. However, how to improve the output performance and reduce friction and wear remain challenging. To this end, a blade-type triboelectric-electromagnetic hybrid generator (BT-TEHG) with a double frequency up-conversion (DFUC) mechanism is proposed. The DFUC mechanism enables the TENG to output a high-frequency response that is 15.9 to 300 times higher than the excitation frequency of 10 to 200 rpm. Coupled with the collisions between tribomaterials, a higher surface charge density and better generating performance are achieved. The magnetization direction and dimensional parameters of the BT-TEHG were optimized, and its generating characteristics under varying rotational speeds and electrical boundary conditions were studied. At wind speeds of 2.2 and 10 m/s, the BT-TEHG can generate, respectively, power of 1.30 and 19.01 mW. Further experimentation demonstrates its capacity to charge capacitors, light up light emitting diodes (LEDs), and power wireless temperature and humidity sensors. The demonstrations show that the BT-TEHG has great potential applications in self-powered wireless sensor networks (WSNs) for environmental monitoring of intelligent agriculture.

The impact of high pressure on the number of photons involved in upconversion luminescence of NaYF4:Er3+@NaYF4 and NaYF4:Yb3+,Er3+@NaYF4 core@shell nanoparticles and application as contactless pressure sensor

Inorganic nanomaterials doped with lanthanide ions and exhibiting upconversion (UC) luminescence are leading in research of nonlinear optical materials. Extreme conditions, such as high-pressure compression (in the GPa range), may influence the physicochemical properties of various compounds. In this work, we investigated the optical properties of upconverting NaYF4:Er3+@NaYF4 and NaYF4:Yb3+,Er3+@NaYF4 core@shell nanoparticles (NPs), focusing on the impact of high pressure on the number of photons involved in the UC mechanism. We measured the UC emission spectra of the synthesized NPs under high-pressure conditions, which allowed us to observe the pressure-induced intensity changes, band centroids spectral shifts, and band intensity ratios alterations. Importantly, by measuring the power-dependent UC emission spectra as a function of pressure, we determined and analyzed the number of photons (n) involved in the UC processes for the first time. It turned out that the n value changes with pressure as a result of diverse multi-phonon relaxation processes enhanced under high-pressure conditions. The results show potential adjustment of UC mechanisms with the use of high-pressure. The calculated band intensity ratios were also used for pressure sensing applications, resulting in the relative sensitivity reaching almost ≈20 % GPa−1 for the Er3+-doped core@shell NPs.

Novel protocol for rapid evaluation of plasmonic enhancement for up-converting phosphors applied to Y2O3 doped with Er3+ and Er3+/Yb3+

A novel technique was created to quickly evaluate the impact of various ratios on the efficiency of up-conversion emission using a combination of up-conversion nanophosphors (UCNPs) and gold nanoparticles (Au NPs). Four different types of Y2O3 UCNPs with different Er3+ or Er3+/Yb3+ doping, which affects the emission colour as well as the up-conversion mechanism, were prepared via the microwave-assisted hydrothermal method. Au NPs were produced independently using the reduction technique. Different ratios of UCNPs were mixed with the Au NPs in water. The mixed powder composites were extracted for analysis. X-ray powder diffraction was utilized to study the structure of UCNPs with and without Au NPs, while transmission electron microscopy was used to study the morphology and size of Au NPs. Absorption and up-conversion measurements were also made. The novel protocol allowed rapid evaluation of four different Y2O3 UCNPs of Er3+ and Er3+/Yb3+ doped with concentrations optimized for red and green emission over a range of Au/UCNP concentrations, which might usually be done in four separate studies. Despite the wide range of variables, only a decrease in UC emission was measured in the presence of Au NPs, suggesting that the conditions for plasmonic enhancement are limited and not easy to attain. In spite of this, in many phosphor/metal NP systems, the innovative prototyping process can enable quick assessment of possible plasmonic enhancement.

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.

Photon Upconversion Cooperates with Downshifting in Chiral Systems: Modulation, Amplification, and Applications of Circularly Polarized Luminescence

AbstractCircularly polarized luminescence (CPL)‐active materials are increasingly recognized for their potential applications such as 3D imaging, data storage, and optoelectronic devices. Typically, CPL materials have required high‐energy (HE) photons for excitation to emit low‐energy (LE) circularly polarized light, a process known as downshifting CPL (DSCPL). However, the emergence of upconverted CPL (UCCPL), where the absorption of multi LE photons results in the emission of a single HE photon with circular polarization, has recently attracted considerable attention. This minireview highlights the intricate relationship between upconversion and CPL phenomena. During upconversion, the dissymmetry factor (glum) value can be improved in certain systems. Additionally, the integration of both LE and HE photons in upconversion‐downshifting‐synergistic systems offers avenues for dual‐excitation or dual‐emission CPL functionalities. More in detail, the emerging UCCPL based on various photon upconversion mechanisms and their synergy with DSCPL are introduced. Additionally, several examples that demonstrate the applications of UCCPL are presented to highlight the future opportunities.

Photon Upconversion Cooperates with Downshifting in Chiral Systems: Modulation, Amplification, and Applications of Circularly Polarized Luminescence.

Circularly polarized luminescence (CPL)-active materials are increasingly recognized for their potential applications such as 3D imaging, data storage, and optoelectronic devices. Typically, CPL materials have required high-energy (HE) photons for excitation to emit low-energy (LE) circularly polarized light, a process known as downshifting CPL (DSCPL). However, the emergence of upconverted CPL (UCCPL), where the absorption of multi LE photons results in the emission of a single HE photon with circular polarization, has recently attracted considerable attention. This minireview highlights the intricate relationship between upconversion and CPL phenomena. During upconversion, the dissymmetry factor (glum) value can be improved in certain systems. Additionally, the integration of both LE and HE photons in upconversion-downshifting-synergistic systems offers avenues for dual-excitation or dual-emission CPL functionalities. More in detail, the emerging UCCPL based on various photon upconversion mechanisms and their synergy with DSCPL are introduced. Additionally, several examples that demonstrate the applications of UCCPL are presented to highlight the future opportunities.

Piezo stack energy harvesters with protection components for railway applications

Piezo stack energy harvesting from railway vibrations shows substantial potential for powering wireless sensor networks responsible for monitoring railway infrastructure. Nevertheless, assuring the safety and durability of these energy harvesters in the condition of the dynamically fluctuating railway vibrations remains a considerable challenge. In this paper, we present two innovative protection methods designed for piezo stack energy harvesters with a frequency up-conversion mechanism. These methods involve the incorporation of ring-type and circular stoppers within the resonant system and the utilisation of proposed impact protection components within the impact system. Two distinct harvesters incorporating the proposed protection components, Harvester Types I and II, are designed to align with their respective operating acceleration targets, which are determined based on the amplitudes of railway vibration acceleration. Finite element modelling is used to guide the design process, involving the evaluation and selection of various design parameters aligned with the acceleration target and stress limits. The protection mechanisms’ effectiveness and impact on energy harvesting performance have been validated through experimental testing under measured rail vibration signals, and their performance has been further assessed through stress analyses. Harvester Type I operates seamlessly within a 5 g threshold, effectively mitigating the increase in maximum output acceleration and stress beyond this limit. In contrast, Harvester Type II efficiently dissipates excess energy, enabling the harvester to operate at a 15 g acceleration while reducing the rate of acceleration and stress growth. The results demonstrate that both proposed harvesters provide effective protection from unexpected railway vibration overloads. This research makes a significant impact on the practical, real-world implementation of piezo stack energy harvesters operating within the dynamic environment of railway vibrations.

Optical transition properties, 1550-to-980 nm upconversion, and temperature sensing of NaEr(WO4)2:Yb3+ phosphors synthesized via the microwave-assisted hydrothermal method

Improving photoelectric conversion efficiency and enhancing heat management are two critical considerations for silicon-based solar cells. In this study, efficient Yb3+ infrared emissions through the upconversion process were achieved by adjusting the concentrations of Yb3+ in Er3+ highly condensed NaEr(WO4)2 phosphor. Additionally, the temperature sensing based on the fluorescence intensity ratio (FIR) was also studied in this tungstate system. Moreover, the radiative transition rates for all relevant transitions of Er3+ in NaEr(WO4)2:Yb3+ phosphors were calculated in the framework of Judd-Ofelt theory, and the optical transition properties of Yb3+ were also revealed by taking Er3+ as a reference. It was found that the radiative transition rate of Yb3+:2F5/2→2F7/2 (2977.52s−1) is significantly higher than that of Er3+:4I11/2→4I15/2 (303.50s−1), thus suggesting the feasibility for the strong emission at 980 nm of Yb3+ in assistance of the energy transfer 4I11/2+2F7/2→4I15/2+2F5/2. Finally, strong and nearly pure NIR emissions of Yb3+ were experimentally observed under 1550 nm excitation, and possible upconversion mechanisms were proposed. The temperature sensing performance of the studied materials was also assessed. All the results imply that NaEr(WO4)2:Yb3+ constitutes an excellent material for enhancing both the photoelectric conversion efficiency and thermal management of silicon-based solar cells.

Harnessing Heavy-Atom Effects in Multiple Resonance Thermally Activated Delayed Fluorescence (MR-TADF) Sensitizers: Unlocking High-Performance Visible-to-Ultraviolet (Vis-to-UV) Triplet Fusion Upconversion.

Ultraviolet (UV) light plays a crucial role in various applications, but currently, the efficiency of generating artificial UV light is low. The visible-to-ultraviolet (Vis-to-UV) system based on the triplet-triplet annihilation upconversion (TTA-UC) mechanism can be a viable solution. Metal-free multiple resonance thermally activated delayed fluorescence (MR-TADF) materials are ideal photosensitizers (PSs) apart from the drawback of high photoluminescence quantum yields (PLQYs). Herein, we systematically investigated the impact of the heavy-atom effect (HAE) on the MR-TADF sensitizers. BNCzBr was then synthesized by incorporating a bromine atom into the skeleton of the precursor BNCz. Impressively, the internal HAE (iHAE) leads to a significantly decreased PLQY and a remarkably increased intersystem crossing quantum yield (ΦISC). Consequently, a higher upconversion quantum efficiency of 12.5% was realized. While the external HAE (eHAE) harms the UC performance. This work guides the further development of MR-TADF sensitizers for high-performance Vis-to-UV TTA-UC systems.

Effect of Pr3+ concentration in luminescence properties & upconversion mechanism of triple doped NaYF4: Yb3+, Er3+, Pr3+

Lanthanide-doped fluoride nanocrystals (NCs) exhibit excellent optical features, including upconversion and downconversion luminescence (UCL and DCL), that can be utilized in a variety of applications. In this study, we have successfully demonstrated the photoluminescence behavior of triple-doped NaYF4: Yb3+, Er3+, Pr3+ NCs in the Vis-NIR region. Herein, highly monodisperse hexagonal phase NaYF4: Yb0.2, Er0.02, Prx nanocrystals in various Pr3+ (x = 0, 0.1, 0.5, and 1 mol %) concentration with ∼22 nm diameter synthesized by thermal decomposition technique. The photoluminescence studies for all samples were performed under 980 nm laser excitation. The luminescence intensity of Er3+ including blue (407 nm), green (520 and 540 nm), red (654 nm), and near-infrared (845 nm and 1530 nm) emissions was significantly quenched and Pr3+ emission intensity at 1290 nm (Pr3+:1G4→3H5) changes irregularly upon doping with Pr3+ ions. Furthermore, we performed the excitation power dependence and decay time analysis to investigate the energy transfer and upconversion mechanisms of samples. These findings indicate that the presence of praseodymium strongly reduces emission intensities due to abundant cross-relaxation channels. In addition, particle size is an efficient factor, shedding light on the influence of Pr3+ on the energy transfer and upconversion mechanisms of the fluorides.