Upconversion Emission Research Articles

Expanding the Anti-Stokes Shift of TTA-UC to 1.04 eV by Chemical Tuning of BODIPY-Based Organic Photosensitizers.

A series of BODIPY-derivatives B-1 ∼ B-5 were synthesized as metal-free photosensitizers in triplet-triplet annihilation (TTA) upconversion (UC) with the purpose of finely tuning the excited state properties to reduce the energy loss during intersystem crossing (ISC), and hence to expand the anti-Stokes shift of TTA-UC. It was revealed that B-5 showed a ΔEST of as small as 0.28 eV, thus, providing a large anti-Stokes shift of 1.04 eV in TTA-UC with organic sensitizers. A deep red-blue upconversion emission with UC quantum yields of up to 10.7% (out of a 50% maximum) was observed.

Upconversion photoluminescence of monolayer WSe2 with biaxial strain tuning.

Mechanical strain can be used to tune the optical properties of monolayer transition metal dichalcogenides (1L-TMDs). Here, upconversion photoluminescence (UPL) from 1L-WSe2 flakes is tuned with biaxial strain induced by cruciform bending and indentation method. It is found that the peak position of UPL is redshifted by around 24 nm as the applied biaxial strain increases from 0% to 0.51%. At the same time, the UPL intensity increases exponentially for the upconversion energy difference that lies within a broad range between -157 meV to -37 meV. The observed linear and sublinear power dependence of UPL emission in 1L-WSe2 with and without biaxial strain at three different excitation wavelengths of 784 nm, 800 nm, and 820 nm indicates the multiphonon-assisted one-photon upconversion emission process. The results of strain-dependent UPL emission from 1L-TMDs pave a unique path to the advances in photon upconversion applications and optoelectronic devices.

Aggregation-Induced Fluorescence Upconversion of Pyrene under Low Fluence: In Solutions and Polymeric Nanoparticles.

In this study, aggregation-induced photon upconversion (iPUC) is demonstrated in the small polyaromatic molecule, pyrene. In binary-solvent mixtures, water, which induces the aggregation of polyaromatic molecules, assisted in triplet-triplet annihilation-based upconversion. No upconverted emission was observed in a dry solvent. Although upconverted emission in the absence of a triplet sensitizer was assigned to pyrene-aggregate-induced sensitization, the presence of a triplet sensitizer enhanced the upconversion efficiency. This experimental finding was further simulated to explore the possibility of iPUC in the condensed-phase polymer matrix. We studied 2-aminoethyl methacrylate hydrochloride-polystyrene copolymer nanoparticles embedded with the molecular upconversion system. The nanoparticle iPUC agreed with the proposition that water domains were present in polymer nanoparticles and helped aggregate pyrene in the host polymer. Despite the low systemic upconversion efficiency, this study provides a method for achieving fluorescence upconversion in relatively simple systems.

Near infrared emissions from both high efficient quantum cutting (173%) and nearly-pure-color upconversion in NaY(WO4)2:Er3+/Yb3+ with thermal management capability for silicon-based solar cells

Raising photoelectric conversion efficiency and enhancing heat management are two critical concerns for silicon-based solar cells. In this work, efficient Yb3+ infrared emissions from both quantum cutting and upconversion were demonstrated by adjusting Er3+ and Yb3+ concentrations, and thermo-manage-applicable temperature sensing based on the luminescence intensity ratio of two super-low thermal quenching levels was discovered in an Er3+/Yb3+ co-doped tungstate system. The quantum cutting mechanism was clearly decrypted as a two-step energy transfer process from Er3+ to Yb3+. The two-step energy transfer efficiencies, the radiative and nonradiative transition rates of all interested 4 f levels of Er3+ in NaY(WO4)2 were confirmed in the framework of Föster-Dexter theory, Judd-Ofelt theory, and energy gap law, and based on these obtained efficiencies and rates the quantum cutting efficiency was furthermore determined to be as high as 173% in NaY(WO4)2: 5 mol% Er3+/50 mol% Yb3+ sample. Strong and nearly pure infrared upconversion emission of Yb3+ under 1550 nm excitation was achieved in Er3+/Yb3+ co-doped NaY(WO4)2 by adjusting Yb3+ doping concentrations. The Yb3+ induced infrared upconversion emission enhancement was attributed to the efficient energy transfer 4I11/2 (Er3+) + 2F7/2 (Yb3+) → 4I15/2 (Er3+) + 2F5/2 (Yb3+) and large nonradiative relaxation rate of 4I9/2. Analysis on the temperature sensing indicated that the NaY(WO4)2:Er3+/Yb3+ serves well the solar cells as thermos-managing material. Moreover, it was confirmed that the fluorescence thermal quenching of 2H11/2/4S3/2 was caused by the nonradiative relaxation of 4S3/2. All the obtained results suggest that NaY(WO4)2:Er3+/Yb3+ is an excellent material for silicon-based solar cells to improve photoelectric conversion efficiency and thermal management.

Site Preference Induced Dual‐Wavelength Mn2+ Upconversion in K2NaScF6:Yb3+, Mn2+ and Its Application in Temperature Sensing

AbstractThe realization of dual‐wavelength Mn2+ upconversion (UC) luminescence that exhibits different thermal responsive behaviors is promising for non‐invasive optical temperature sensing applications. However, it remains challenging to achieve such luminescence of Mn2+ ions. Herein, due to the site preference characteristics of Mn2+, color tunable and dual‐wavelength Mn2+ UC luminescence is achieved in K2NaScF6:Yb3+, Mn2+ by simply adjusting the Mn2+ doping concentration. Structural and spectral analysis as well as theoretical calculations reveal that the green and red UC emissions originate from two kinds of face‐sharing Yb3+‐Mn2+ dimers, which exhibit different luminescence properties, including different emission wavelength, excited state lifetime, full width at half maximum (FWHM), and luminescence thermal stability. This unique dual‐wavelength UC luminescence of Mn2+ provides a new type of fluorescence intensity ratio thermometer with absolute and relative sensitivities of up to 0.018 K−1 and 0.525% K−1, respectively. This work not only demonstrates the potential application of K2NaScF6:Yb3+, Mn2+ material in the field of optical thermometry but also provides new perspectives for designing multi‐band Mn2+ UC luminescence.

PEG-coated NaYF4:Tm3+/Yb3+ upconversion nanoparticles for OCT image contrast enhancer, optical thermometry, and security applications

Polyethylene glycol (PEG) coated NaYF4:Tm3+/Yb3+ upconversion nanoparticles (UCNPs) were synthesized, and their usefulness in improving image contrast in Swept source optical coherence tomography (SS-OCT) and photo-thermal (PT-OCT) imaging was assessed. Synthesized UCNPs have shown biocompatibility with a cell survival rate of more than 90% after 24 h of incubation of HeLa cells. Prepared particles have shown intense blue upconversion emission along with a photo-thermal conversion efficiency of 30.4%. Leveraging these UCNPs, enhancements in image quality were achieved in both SS-OCT and PT-OCT imaging modalities, manifesting improved scattering coefficients and contrast-to-noise ratios. Temperature-dependent upconversion emission spectra were used to assess temperature sensing and thermal sensitivity of 107×10-3 K-1 at 300 K is obtained for the synthesized nanoparticles. Additionally, these UCNPs have demonstrated utility in latent finger-marks detection and anti-counterfeiting applications.

Design and synthesis of a UV–vis-NIR response heterostructure system: For efficient solar energy conversion and BPA photocatalytic degradation

Combining upconversion materials with narrow-wide bandgap semiconductors to construct heterostructured composite photocatalysts effectively improves solar energy conversion efficiency. NYF:Ln3+(Ln = Yb,Er,Tm)@BiOX(X = Cl,Br,I) heterostructures were prepared by a two-step hydrothermal method. This work explores the effects of different lanthanide ion doping and narrow-wide bandgap bismuth oxyhalides on the performance of the heterostructures system. Under near-infrared (NIR) light irradiation, NYF:Yb,Er,Tm@BiOI degraded 94 % BPA within 160 min. Significantly, compared with NYF:Yb,Er@BiOCl, NYF:Yb,Er@BiOBr and the NYF:Yb,Er,Tm/BiOI mechanical mixtures, the photocatalytic activity of NYF:Yb,Er,Tm@BiOI was increased by 9.4 times, 3.7 times and 1.8 times, respectively. The enhanced photocatalytic activity is attributed to the doping of Er-Tm double-activated ions, which provides multiple upconversion emissions and forms more overlap in the narrow bandgap BiOI absorption spectrum, making it advantageous to utilize upconversion light fully. Eventually, an underlying mechanism was proposed that the existence of FRET in the NYF:Yb,Er,Tm@BiOI heterostructure leads to enhanced photocatalytic activity. This work provides new insights into the design of advanced structures for NIR-responsive photocatalysts.

NaYF4:Yb3+/Ho3+ up-conversion luminescence and its low temperature sensing characteristics

Pure hexagonal [Formula: see text]-NaYF4 micron crystals were synthesized by the hydrothermal method with the up-conversion luminescence properties studied by doping Yb[Formula: see text]/Ho[Formula: see text]. The up-conversion fluorescence spectra and fluorescence lifetime of [Formula: see text]-NaYF4 micron crystals were determined by FLS-980 transient fluorescence spectrometer. By changing the doping concentration of Yb[Formula: see text]/Ho[Formula: see text], the optimal doping concentration was confirmed to be 20%Yb[Formula: see text]/2%Ho[Formula: see text]. The fluorescence spectrum was obtained by changing pump power, the relationship between power and intensity was analyzed, and the [Formula: see text]-NaYF4 micron crystal green and red emission up-conversion process was obtained into a two-photon process. The 5F[Formula: see text]I8 and 5S[Formula: see text]I8 of the sample were thermally coupled to obtain a large absolute sensitivity (Sa) of low temperature. The maximum absolute sensitivity within the range of 64–194[Formula: see text]K is 0.0097[Formula: see text]K[Formula: see text] at 144[Formula: see text]K, while maximum absolute sensitivity at 333[Formula: see text]K is 0.00335[Formula: see text]K[Formula: see text] in the range of 293–493[Formula: see text]K. The experimental results show that the sensing characteristics of [Formula: see text]-NaYF4:Yb[Formula: see text]/Ho[Formula: see text] at low temperature are better than those at high temperature, and it has the potential to be used in the field of temperature sensing.

Gum Arabic-stabilized upconverting nanoparticles for printing applications

Upconverting nanoparticles (UCNPs) have been proposed for a variety of applications ranging from biomedical probes to luminescent sensors and security tags. Yet, bringing UCNPs into real-life, technologically relevant products requires implementation into industry-friendly processes. The need for stable dispersions, clean films or dry powders challenges users who look for a way to use UCNPs. In this work, an ink formulation was developed that offers a straightforward way to print UCNPs on glass and metallic substrates. The use of Gum Arabic as biocompatible emulsifier allowed to implement the NaGdF4:Er,Yb/NaGdF4 core/shell UCNPs into water-based ink formulations without the need of complex surface chemistry. The formulation, based on water, glycerin, and propanediol, exhibited good stability and applicability for printing with a commercial aerosol jet printer. Bright upconversion emission was retained upon printing, and the obtained UCNP films were used in proof-of-concept luminescent thermal sensing.

Blue and green upconverted emission in fluoroindate glasses under 808 nm excitation

In this study, the upconversion (UC) luminescence of fluoroindate glasses (InF3G) co-doped with Yb-Nd-Er (Tm) ions excited in the NIR-I biological window was analyzed. In the first system, UC emission of singly Er3+ doped InF3G under 808 nm excitation occurred to be more efficient than those observed in InF3G co-doped with Yb–Er and Yb-Nd-Er. The intensity of UC emission (InF3G-Er) was 22 % higher than InF3G-Yb-Er, and even more than two times higher than in the InF3G-Yb-Nd-Er sample. The effective energy transfer (η) between Nd3+- Yb3+ (η = 45 %) and Yb3+-Er3+ (η = 68 %), was reflected in the emission observed in the NIR region mainly, ascribed to Yb3+:2F5/2 → 2F7/2 (978 and 999 nm) and Nd3+:4F3/2 → 4I9/2 (1053 nm) transitions. Meanwhile, the samples co-doped with Tm3+ exhibited a strong dependence on Yb-Nd-Tm co-doping. Samples without Yb and Nd did not exhibit any UC emission due to the absence of pumping channel. This contrasts with the downshifting NIR emission, which was at least two times higher than those exhibited in samples co-doped Yb-Nd-Er. These results suggest that Tm3+ plays a crucial role in populating the lower-lying exited levels of Yb and Nd, influencing the overall emission behavior.

Constructing micro/nano-photonics barcodes based on micro-region upconversion emission spectrum of single core-shell microcrystal

The construction of core-shell structures with different structural properties based on the epitaxial growth technique has become an effective technique for regulating the luminescence properties of micro/nanocrystals. In order to obtain richer spectral information, NaYF<sub>4</sub>:50%Yb<sup>3+</sup>/2%Tm<sup>3+</sup>@NaYF<sub>4</sub>@NaYF<sub>4</sub>:20%Yb<sup>3+</sup>/2%Er<sup>3+</sup>@NaYF<sub>4</sub>@NaYbF<sub>4</sub>:2%Er<sup>3+</sup> multilayered core-shell microcrystals are prepared by using multiple epitaxial growth through introducing surface modifiers and controlling their reaction conditions. The XRD and SEM results clearly show that the core-shell microcrystals possess a pure hexagonal crystal structure in the form of a disk. The microdesk has a thickness of about 2.32 μm and a diameter of about 28.31 μm. The upconversion luminescence characteristics of different single microcrystal structures are investigated by a confocal microspectroscopy system. In order to realize the selective excitation and emission of a single microcrystal, the spatial distribution of luminescent ions can be controlled through introducing an intermediate isolation layer. Under 980 nm laser excitation, different excitation sites of the single microdisk exhibit different upconversion emission characteristics. The significant blue (450 and 475 nm), red (648 nm) and green (524 and 540 nm) emissions are observed, which mainly originat from Tm<sup>3+</sup> and Er<sup>3+</sup> radiative transitions. Meanwhile, the red and blue upconversion emission intensities of the microcrystals are improved by using various shell layers. In addition, the luminescence and energy-transfer features of single microcrystals are explored by changing the excitation position. The experimental results demonstrate that the incorporation of NaYF<sub>4</sub> inert shells between luminescent layers can regulate luminescence and prevent ions from interacting. By utilizing the spectral fingerprint data of dopant ions in various shell layers, we create customizable micro-nano photonic barcodes and employ them for optical anti-counterfeiting detection. This study explores the use of constructed core-shell structures with luminescent tunable micron core-shell structures to acquire diverse spectral information and maintain stability through their structural properties. Thus, this core-shell structure provides a novel method for using upconversion luminescent microcrystals into micro- and nanophotonics to achieve anti-counterfeiting and display purposes.

Thermal properties of nanofluids using hydrophilic and hydrophobic LiYF4:Yb/Er upconverting nanoparticles.

Luminescent nanoparticles have shown great potential for thermal sensing in bio-applications. Nonetheless, these materials lack water dispersibility that can be overcome by modifying their surface properties with water dispersible molecules such as cysteine. Herein, we employ LiYF4:Er3+/Yb3+ upconverting nanoparticles (UCNPs) capped with oleate or modified with cysteine dispersed in cyclohexane or in water, respectively, as thermal probes. Upconversion emission was used to sense temperature with a relative thermal sensitivity of ∼1.24% K-1 (at 300 K) and a temperature uncertainty of 0.8 K for the oleate capped and of 0.5 K for cysteine modified NPs. To study the effect of the cysteine modification in the heat transfer processes, the thermal conductivity of the nanofluids was determined, yielding 0.123(6) W m-1 K-1 for the oleate capped UCNPs dispersed in cyclohexane and 0.50(7) W m-1 K-1 for the cysteine modified UCNPs dispersed in water. Moreover, through the heating curves, the nanofluids' thermal resistances were estimated, showing that the cysteine modification partially prevents heat transfer.

NIR-triggered upconversion and sensitized NIR-emission in Yb-based Eosin Y lake doped latex nanoparticles.

Here, Yb-based Eosin Y lakes (EOS-Yb) have been encapsulated in organic nanoparticles (NPs) by microemulsion radical polymerization of methacrylate-based copolymers. These photoactive EOS-Yb NPs emit in the visible and near infrared (NIR) upon excitation at 530 nm and can also display NIR-to-visible upconversion emission upon excitation at 980 nm.

EuIII and TbIII upconversion intermediated by interparticle energy transfer in functionalized NaLnF4 nanoparticles.

Lanthanide (LnIII)-doped sodium gadolinium tetrafluoride (NaGdF4) nanoparticles have been excelled as attractive upconversion systems for anti-counterfeiting or energy conversion for instance, with a special interest in the visible upconversion of EuIII and TbIII. The core@shell architecture has enabled the bright upconversion of EuIII and TbIII in this matrix by interfacial energy transfer sensibilized by the TmIII/YbIII pair. Another approach to enable EuIII and TbIII upconversion could be the interparticle energy transfer (IPET) between LnIII-doped sensitizer and acceptor nanoparticles. Yet, the low molar absorptivity of the LnIII through 4f ↔ 4f electronic transitions and the large distance between the nanoparticles are shortcomings that should decrease the energy transfer efficiency. On the other hand, it is feasible to predict that the association of organic ligands displaying large molar absorptivity on the acceptor nanoparticle surface could help to overcome the absorption limitation. Inspired by this exciting possibility, herein, we present the EuIII/TbIII upconversion intermediated by IPET between the donor TmIII, YbIII-doped NaGdF4 nanoparticle and the acceptor LnIII-doped NaGdF4 (Ln = Eu and/or Tb) nanoparticles functionalized with a series organic ligands on the surface (tta- = thenoyltrifluoroacetonate, acac- = acetylacetonate, or 3,5-bbza- = 3,5-dibromebenzoate). Either in solid state or in suspension, upon excitation at 980 nm, visible EuIII/TbIII upconversion could be observed. This emission comes from the absorption of the TmIII, YbIII pair in the donor nanoparticle, followed by IPET from the TmIII excited levels to the ligand singlet/triplet states on the acceptor nanoparticle surface, ligand-to-EuIII/TbIII energy transfer, and upconversion emission. Spectroscopic evidences from the analysis of the donor level lifetimes indicate the contribution of non-radiative energy transfer for the IPET mechanism; the radiative mechanism also contributes for the IPET. Moreover, the design herein introduced enables the development of luminescence temperature probes with relative thermal sensitivity as high as 1.67% K-1 at 373 K. Therefore, this new upconversion pathway opens an avenue of possibilities in an uncharted territory to tune the visible upconversion of LnIII ions.

Lanthanide-based nanomaterials for temperature sensing in the near-infrared spectral region: illuminating progress and challenges.

Being first proposed as a method to overcome limitations associated with conventional contact thermometers, luminescence thermometry has been extensively studied over the past two decades as a sensitive and fast approach to remote and minimally invasive thermal sensing. Herein, lanthanide (Ln)-doped nanoparticles (Ln-NPs) have been identified as particularly promising candidates, given their outstanding optical properties. Known primarily for their upconversion emission, Ln-NPs have also been recognized for their ability to be excited with and emit in the near-infrared (NIR) regions matching the NIR transparency windows. This sparked the emergence of the development of NIR-NIR Ln-NPs for a wide range of temperature-sensing applications. The shift to longer excitation and emission wavelengths resulted in increased efforts being put into developing nanothermometers for biomedical applications, however most research is still preclinical. This mini-review outlines and addresses the challenges that limit the reliability and implementation of luminescent nanothermometers to real-life applications. Through a critical look into the recent developments from the past 4 years, we highlight attempts to overcome some of the limitations associated with excitation wavelength, thermal sensitivity, calibration, as well as light-matter interactions. Strategies range from use of longer excitation wavelengths, brighter emitters through strategic core/multi-shell architectures, exploitation of host phonons, and a shift from double- to single-band ratiometric as well as lifetime-based approaches to innovative methods based on computation and machine learning. To conclude, we offer a perspective on remaining gaps and where efforts should be focused towards more robust nanothermometers allowing a shift to real-life, e.g., in vivo, applications.

Revealing the role of a unique local structure in lanthanide-doped Cs2LiInCl6 in boosting visible and NIR-II luminescence

The local symmetry breaking and presence of two independent active sites in Cs2LiInCl6:Yb3+,Er3+ double perovskites are beneficial for the luminescence enhancement, thus guiding the designing of highly-efficient visible and NIR-II emitters.

Multicolor and multimodal luminescence in an Er3+ single-doped double perovskite for advanced anti-counterfeiting and encryption

The Er3+ single-doped NaGdTi1.8Al0.2O6 double perovskite material achieves multicolor luminescence, afterglow, and upconversion emission by responding to several types of excitation ranging from UV to NIR and thermal disturbance.

Tailoring sensitization properties and improving near-infrared photon upconversion performance through alloying in superatomic molecular Au25 nanoclusters.

Noble-metal nanoclusters (NCs) protected by organic ligands have recently come to the forefront as potent triplet sensitizers for photon upconversion (UC) via triplet-triplet annihilation (TTA), owing to their capacity for atomic-level photophysical property customization. Among these, the rod-shaped bi-icosahedral [Au25(PPh3)10(S-C2H4Ph)5Cl2]2+ (Au-rod) NC is a particularly iconic superatomic molecular NC, recently identified as a near-infrared (NIR)-absorbing sensitizer for TTA-UC. In this study, we synthesized Cu-doped NCs, [Au25-xCux(PPh3)10(S-C2H4Ph)5Cl2]2+ (AuCu-rod), and paired them with 9,10-bis(phenylethynyl)anthracene (BPEA) annihilator/emitter to explore the impact of Cu-doping on the triplet sensitization and NIR-UC performance. The triplet state of AuCu-rod, with lifetime of 3 μs, exhibited a modest blue shift compared to the Au-rod, resulting in the increment in the driving force for triplet energy transfer (TET) to the BPEA acceptor. The TET rate constant was determined to be 5.0 × 107 M-1 s-1, which is an order of magnitude higher than the rate constant for the Au-rod/BPEA pair. This improvement has led to a remarkable increase in the TET efficiency. Notably, the AuCu-rod/BPEA pair facilitated the efficient UC of 805 nm NIR light into 510 nm visible light, realizing a large anti-Stokes shift close to 0.9 eV. The UC internal quantum yield of this combination was determined to be 2.33 ± 0.05%, marking a fivefold enhancement over the Au-rod sensitizer (0.49%). Thus, alloying NC sensitizers offers a promising route to enhance UC performance by tuning the triplet state energy and optimizing the compatibility between the sensitizer and annihilator. Additionally, in this series of experiments, the formation of small amounts of BPEA microaggregates was observed. These aggregates did not undergo singlet fission and could retain multiple long-lived triplet excitons. This characteristic facilitated TTA among triplet excitons, resulting in efficient NIR-to-visible UC emission.

Dominant red upconversion emission in LiErF4-based nanoparticles by reducing spontaneous emission of Yb3+

The achievement of dominant red upconversion emission by reducing spontaneous emission from Yb3+.

Unleashing the glow: upconverting nanoparticles recharge persistent luminescent materials – applications in 3D-printing and optical coding

In this study, composite materials composed of LiYbF4:Tm3+@LiYF4 and SrAl2O4:Eu2+ or ZnGa2O4:Cr3+ compounds were used for 3D-printed polymer items for optical coding operating in the afterglow and upconversion emission modes.