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.

Structure and luminescence properties of Dy3+ doped quaternary tungstate Li3Ba2Gd3(WO4)8 for application in wLEDs.

Quaternary tungstates with the composition Li3Ba2Gd3(WO4)8 doped with different concentrations of Dy3+ (from 0.5 to 10 at%) were prepared by the solid-state reaction method at 900 °C. Their structural, spectroscopic and optical properties were studied systematically in this work. X-ray diffraction analysis confirmed the crystallization of Li3Ba2Gd3(WO4)8 to have a monoclinic structure (sp. gr. C2/c); the lattice constants for 1 at% doping concentration of Dy3+ are a = 5.2126(2) Å, b = 12.7382(1) Å, c = 19.1884(3) Å, Vcalc = 1273,40(4) Å3 and ß = a × c = 91.890(9)°. The first principles calculations for the undoped crystal revealed a direct bandgap of 2.45 eV, which is very close to the experimental one. The identified broad, and strong excitation peak at 450 nm indicates that Li3Ba2Gd3(WO4)8:Dy3+ phosphors are suitable to be pumped by a blue laser diode (LD). Under excitation at 445 nm, the phosphor showed a stronger luminescence peak at 575 nm which corresponds to the Dy3+:4F9/2 → 6H13/2 transition, and three weaker emissions peaks at 477, 661, and 750 nm. Meanwhile, the effect of different Dy3+ contents on the luminescence properties was investigated. The optimum concentration to minimize the quenching effect was 4 at% and the critical distance is 31.209 Å. The phosphor emitted strong greenish-yellow light situated at (0.425, 0.472) in CIE coordinates with a color temperature of 3652 K. All the measured luminescence lifetime curves exhibited a single-exponential nature. Excellent thermal stability was found for this tungstate phosphor (the activation energy is 0.352 ± 0.01 eV). The measured absolute photoluminescence quantum yield was around 10.5%. The results presented in this work show that Li3Ba2Gd3(WO4)8:Dy3+ phosphors with strong yellow emission are promising candidates for white-light emitting LED (wLED) applications.

Absolute quantum yield for understanding upconversion and downshift luminescence in PbF2:Er3+,Yb3+ crystals.

The search for new materials capable of efficient upconversion continues to attract attention. In this work, a comprehensive study of the upconversion luminescence in PbF2:Er3+,Yb3+ crystals with different concentrations of Yb3+ ions in the range of 2 to 7.5 mol% (Er3+ concentration was fixed at 2 mol%) was carried out. The highest value of upconversion quantum yield (ϕUC) 5.9% (at 350 W cm-2) was found in the PbF2 crystal doped with 2 mol% Er3+ and 3 mol% Yb3+. Since it is not always easy to directly measure ϕUC and estimate the related key figure of merit parameter, saturated photoluminescence quantum yield (ϕUCsat), a method to reliably predict ϕUCsat can be useful. Judd-Ofelt theory provides a convenient way to determine the radiative lifetimes of the excited states of rare-earth ions based on absorption measurements. When the luminescence decay times after direct excitation of a level are also measured, ϕUCsat for that level can be calculated. This approach is tested on a series of PbF2:Er3+,Yb3+ crystals. Good agreement between the estimates obtained as above and the directly experimentally measured ϕUCsat values is demonstrated. In addition, three methods of Judd-Ofelt calculations on powder samples were tested and the results were compared with Judd-Ofelt calculations on single crystals, which served as the source of the powder samples. Taken together, the results presented in our work for PbF2:Er3+,Yb3+ crystals contribute to a better understanding of the UC phenomena and provide a reference data set for the use of UC materials in practical applications.

BODIPY-pyrene donor-acceptor sensitizers for triplet-triplet annihilation upconversion: the impact of the BODIPY-core on upconversion efficiency.

Triplet-triplet annihilation upconversion (TTA-UC) is an important type of optical process with applications in biophotonics, solar energy harvesting and photochemistry. In most of the TTA-UC systems, the formation of triplet excited states takes place via spin-orbital interactions promoted by heavy atoms. Given the crucial role of heavy atoms (especially noble metals, such as Pd and Pt) in promoting intersystem crossing (ISC) and, therefore, in production of UC luminescence, the feasibility of using more readily available and inexpensive sensitizers without heavy atoms remains a challenge. Here, we investigated sensitization of TTA-UC using BODIPY-pyrene heavy-atom-free donor-acceptor dyads with different numbers of alkyl groups in the BODIPY scaffold. The molecules with four and six alkyl groups are unable to sensitize TTA-UC in the investigated solvents (tetrahydrofuran (THF) and dichloromethane (DCM)) due to negligible ISC. In contrast, the dyad with two methyl groups in the BODIPY scaffold and the dyad with unsubstituted BODIPY demonstrate efficient intersystem crossing (ISC) of 49-58%, resulting in TTA-UC with quantum yields of 4.7% and 6.9%, respectively. The analysis of the elementary steps of the TTA-UC process indicates that heavy-atom-free donor-acceptor dyads are less effective than their noble metal counterparts, but may equal them in the future if the right combination of solvent, donor-acceptor sensitizer structure, and new luminescent molecules as TTA-UC emitters can be found.

Harvesting Sub-bandgap Photons via Upconversion for Perovskite Solar Cells.

Lanthanide-based upconversion (UC) allows harvesting sub-bandgap near-infrared photons in photovoltaics. In this work, we investigate UC in perovskite solar cells by implementing UC single crystal BaF2:Yb3+, Er3+ at the rear of the solar cell. Upon illumination with high-intensity sub-bandgap photons at 980 nm, the BaF2:Yb3+, Er3+ crystal emits upconverted photons in the spectral range between 520 and 700 nm. When tested under terrestrial sunlight representing one sun above the perovskite's bandgap and sub-bandgap illumination at 980 nm, upconverted photons contribute a 0.38 mA/cm2 enhancement in the short-circuit current density at lower intensity. The current enhancement scales non-linearly with the incident intensity of sub-bandgap illumination, and at higher intensity, 2.09 mA/cm2 enhancement in current was observed. Hence, our study shows that using a fluoride single crystal like BaF2:Yb3+, Er3+ for UC is a suitable method to extend the response of perovskite solar cells to near-infrared illumination at 980 nm with a subsequent enhancement in current for very high incident intensity.

Photon Upconversion for Photovoltaics and Photocatalysis: A Critical Review.

Opportunities for enhancing solar energy harvesting using photon upconversion are reviewed. The increasing prominence of bifacial solar cells is an enabling factor for the implementation of upconversion, however, when the realistic constraints of current best-performing silicon devices are considered, many challenges remain before silicon photovoltaics operating under nonconcentrated sunlight can be enhanced via lanthanide-based upconversion. A photophysical model reveals that >1-2 orders of magnitude increase in the intermediate state lifetime, energy transfer rate, or generation rate would be needed before such solar upconversion could start to become efficient. Methods to increase the generation rate such as the use of cosensitizers to expand the absorption range and the use of plasmonics or photonic structures are reviewed. The opportunities and challenges for these approaches (or combinations thereof) to achieve efficient solar upconversion are discussed. The opportunity for enhancing the performance of technologies such as luminescent solar concentrators by combining upconversion together with micro-optics is also reviewed. Triplet-triplet annihilation-based upconversion is progressing steadily toward being relevant to lower-bandgap solar cells. Looking toward photocatalysis, photophysical modeling indicates that current blue-to-ultraviolet lanthanide upconversion systems are very inefficient. However, hope remains in this direction for organic upconversion enhancing the performance of visible-light-active photocatalysts.

Expanding excitation wavelengths for azobenzene photoswitching into the near-infrared range via endothermic triplet energy transfer.

Developing azobenzene photoswitches capable of selective and efficient photoisomerization by long-wavelength excitation is an enduring challenge. Herein, rapid isomerization from the Z- to E-state of two ortho-functionalized bistable azobenzenes with near-unity photoconversion efficiency was driven by triplet energy transfer upon red and near-infrared (up to 770 nm) excitation of porphyrin photosensitizers in catalytic micromolar concentrations. We show that the process of triplet-sensitized isomerization is efficient even when the sensitizer triplet energy is substantially lower (>200 meV) than that of the azobenzene used. This makes the approach applicable for a wide variety of sensitizer-azobenzene combinations and enables the expansion of excitation wavelengths into the near-infrared spectral range. Therefore, indirect excitation via endothermic triplet energy transfer provides efficient and precise means for photoswitching upon 770 nm near-infared light illumination with no chemical modification of the azobenzene chromophore, a desirable feature in photocontrollable biomaterials.

Rare-earth coordination polymers with multimodal luminescence on the nano-, micro-, and milli-second time scales.

We present a coordination polymer based on rare-earth metal centers and carboxylated 4,4'-diphenyl-2,2'-bipyridine ligands. We investigate Y3+, Lu3+, Eu3+, and a statistical mixture of Y3+ with Eu3+ as metal centers. When Y3+ or Lu3+ is exclusively present in the coordination polymer, biluminescence from the ligand is observed: violet emission from the singlet state (417 nm, 0.9 ns lifetime) and orange emission from the triplet state (585 nm, 76 ms (Y3+) and 31 ms (Lu3+)). When Eu3+ is present in a statistical mixture with Y3+, red emission from the Eu3+ (611 nm, ∼ 500 µs ) is observed in addition to the ligand emissions. We demonstrate that this multi-mode emission is enabled by the immobility of singlet and triplet states on the ligand. Eu3+ only receives energy from adjacent ligands. Meanwhile, in the broad inhomogeneous distribution of ligand energies, higher energy states favor singlet emission, whereas faster intersystem crossing in the more stabilized ligands enhances their contribution to triplet emission.

Enhancing Singlet Oxygen Generation in Conjugates of Silicon Nanocrystals and Organic Photosensitizers.

Silicon nanocrystals (SiNCs) are regarded as a green and environmentally friendly material when compared with other semiconductor nanocrystals. Ultra-small SiNCs (with the size 4.6-5.2 nm) demonstrate strong UV absorption and photoluminescence in the near infrared (NIR) range with the high photoluminescence quantum yield (PLQY) up to 60%. In contrast to nanoporous silicon, ultra-small SiNCs do not possess an intrinsic ability to generate singlet oxygen (1O2). However, we demonstrate that SiNC-dye conjugates synthesized via microwave assistant hydrosilylation reaction produce 1O2 with moderate quantum yield (ΦΔ) up to 27% in cyclohexane. These interesting results were obtained via measurements of singlet oxygen phosphorescence at 1,270 nm. SiNCs play an important role in the production of singlet oxygen as SiNCs harvest UV and blue radiation and transfer absorbed energy to a triplet state of the attached dyes. It increases the population of the triplet states and leads to the enhancement of the singlet oxygen generation. Simultaneously, the SiNC-dye conjugates demonstrate NIR luminescence with the PLQY up to 22%. Thus, the luminescence behavior and photosensitizing properties of the SiNC-dye conjugates can attract interest as a new multifunctional platform in the field of bio-applications.

Determination of Upconversion Quantum Yields Using Charge-Transfer State Fluorescence of Heavy-Atom-Free Sensitizer as a Self-Reference.

The efficiency of photon upconversion via triplet-triplet annihilation is characterized by an upconversion quantum yield (ΦUC); however, uncertainties remain for its determination. Here, we present a new approach for the relative measurement of ΦUC for green-to-blue upconversion using BODIPY-pyrene donor-acceptor dyad (BD1) as a heavy-atom-free triplet sensitizer. This new approach exploits broad fluorescence from a charge-transfer (CT) state of BD1, which possesses (i) a significant Stokes shift of 181 nm in dichloromethane and (ii) a comparably high CT-fluorescence quantum yield (Φref = 7.0 ± 0.2%), which is independent from oxygen presence and emitter (perylene) concentration while also exhibiting a linear intensity dependence. On the basis of this, we developed an upconversion reference using the BD1 sensitizer mixed with perylene (1 × 10-5 M/1 × 10-4 M) in dichloromethane. With this reference system, we investigated the performance of three BODIPY donor-acceptor dyads in the upconversion process and achieved one of the highest ΦUC of 6.9 ± 0.2% observed for heavy-atom-free sensitizers to date.

Separation and degradation detection of nanogram-per-litre concentrations of radiolabelled steroid hormones using combined liquid chromatography and flow scintillation analysis.

Detection of micropollutants such as steroid hormones occurring in the aquatic environment at concentrations between ng/L and µg/L remains a major challenge, in particular when treatment efficiency is to be evaluated. Steroid hormones are typically analysed using mass-spectrometry methods, requiring pre-concentration and/or derivatisation procedures to achieve required detection limits. Free of sample preparation steps, the use of radiolabelled contaminants with liquid scintillation counting is limited to single-compound systems and require a separation of hormone mixtures before detection. In this work, a method was developed coupling ultra-high-pressure liquid chromatography (UHPLC) with flow scintillation analysis (FSA) for separation and detection of radiolabelled estrone, 17ß-estradiol, testosterone and progesterone. Adjustment of the flow rate of scintillation liquid and UHPLC mobile phase, gradient time, column temperature, and injection volume allowed the separation of steroid hormones and degradation products. The limit-of-detection (LOD = 1.5-2.4 ng/L) and limit-of-quantification (LOQ = 3.4-4.3 ng/L) for steroid hormones were comparable with the current state-of-the-art technique (LC-MS/MS) for non-derivatised compounds. Although the method cannot be applied to real water samples (unless spiked with radiotracers), it serves as a useful tool for the development of water treatment technologies at laboratory scale as demonstrated via: i) adsorption on polymer-based spherical activated carbon, ii) retention in nanofiltration, iii) photodegradation using a photocatalytic membrane.

Lanthanide Sensitizers for Large Anti-Stokes Shift Near-Infrared-to-Visible Triplet-Triplet Annihilation Photon Upconversion.

The upconversion of near-infrared (NIR) to visible (vis) photons is of interest for display technologies and energy conversion. Although triplet-triplet annihilation (TTA) offers a mechanism for upconversion that works efficiently at low incident irradiance flux densities, current strategies for NIR-vis upconversion based on TTA have fundamental limitations. Herein, we report a strategy for NIR-vis TTA based on lanthanide-containing complexes to sensitize the upconversion. We demonstrate a ß-diketonate complex of Yb3+ paired with rubrene that emits yellow (λem = 559 nm) under NIR excitation (λexc = 980 nm). This corresponds to an exceptional anti-Stokes shift of just less than 1 eV. Thus, lanthanide complexes could unlock high-performance NIR-vis upconversion, with lanthanide sensitizers overcoming the energy loss, reabsorption, and short triplet lifetime that fundamentally limit porphyrin, nanocrystals, and direct S0-T1 sensitizers.

Improved photon absorption in dye-functionalized silicon nanocrystals synthesized via microwave-assisted hydrosilylation.

Herein, we report a method to produce luminescent silicon nanocrystals (SiNc) that strongly absorb ultraviolet-visible light (300-550 nm) and emit in the near-infrared range (700-1000 nm) with a high photoluminescence quantum yield (PLQY). Using microwave-assisted hydrosilylation and employing reactive chromophores - such as ethenyl perylene, ethynyl perylene and ethylene-m-phenyl BODIPY - we are able to achieve a 10- and 3-fold enhancement of the absorption in the blue and green spectral range, respectively. The investigated dyes function both as passivating agents and highly efficient antenna, which absorb visible light and transfer the energy to SiNc with an efficiency of >95%. This enhanced absorption leads to a significant photoluminescence enhancement, up to ∼270% and ∼140% under excitation with blue and green light, respectively. Despite the gain in absolute brightness of the emission, we demonstrate that back energy transfer from the SiNc to the dyes leads to a decrease in the PLQY for dye-modified SiNc, as compared to unmodified SiNc. The synthesis of the SiNc-dye conjugates opens up new possibilities for applications of this abundant and non-toxic material in the field of solar energy harvesting, optical sensing and bioimaging via achieving strong NIR PL excited with visible light.

Efficient Photocatalytic Removal of Methylene Blue Using a Metalloporphyrin-Poly(vinylidene fluoride) Hybrid Membrane in a Flow-Through Reactor.

A novel combination of a poly(vinylidene fluoride) (PVDF) membrane with pore size 0.2 µm and a photosensitizer 5,10,15,20-tetrakis (pentafluorophenyl)-21H,23H-porphine palladium(II) (PdTFPP) makes a promising hybrid material for the generation of singlet oxygen (1O2) and, thus, water treatment applications. The fabricated photocatalytic membrane exhibits permeability of 4280 ± 250 L·m-2·h-1·bar-1 and stable photocatalytic degradation performance over a 90 h period, when illuminated with green light (528 ± 20 nm) and operated in a dead-end, single-pass configuration. Methylene blue (MB) degradation of 83% was achieved for MB concentration of 1 mg·L-1 under the flow rate of 0.1 × 10-3 L·min-1 (flux of 30 L·m-2·h-1), light intensity of 21 mW·cm-2, and PdTFPP loading of 25 µmol·g-1. Due to an enhanced mass transfer, the reaction rate of MB removal (with apparent rate constant of kapp = 6.52 min-1) results in an efficient photodegradation of MB inside the PdTFPP-PVDF membrane. The influence of experimental parameters such as catalyst loading, flow rate, light intensity, and solute concentration on MB removal was investigated. This research enables the application of photocatalytic PdTFPP-PVDF membranes as a potential technology for water decontamination under visible-light illumination.

Critical Power Density: A Metric To Compare the Excitation Power Density Dependence of Photon Upconversion in Different Inorganic Host Materials.

In photon upconversion (UC) based on triplet-triplet annihilation, the upconversion photoluminescent quantum yield (UC-PLQY) depends on the excitation power density in a way that can be described by a single figure of merit. This figure of merit, the threshold value, allows the excitation power density required for efficient UC-PLQY to be compared between different triplet-triplet annihilation systems. Here, we investigate the excitation power density dependence of two-photon UC processes in a series of four lanthanide-doped inorganic host materials (oxides, fluorides, and chlorides) all doped with 18 mol % Yb3+ sensitizer ions and 2 mol % Er3+ activator ions. We demonstrate that an analogous figure of merit, which we call the critical power density (CPD), accurately describes the UC power dependence of these samples. Better CPD values are obtained when the lifetime of the intermediate states is long. The UC-PLQY at the CPD is linked to the saturation UC-PLQY. Thus, a measurement of the UC-PLQY at this low power density can be used to estimate the theoretical saturation UC-PLQY in the absence of deleterious effects such as laser-induced heating. This is compared to another method to estimate the saturation based on the CPD model, namely, taking half of the level's PLQY under direct excitation. Our careful analysis of the upconversion spectra as a function of excitation power density gives several insights into the differing upconversion pathways in the hosts and proves to be a useful tool for their comparison.

Efficient Ytterbium Near-Infrared Luminophore Based on a Nondeuterated Ligand.

A novel molecular ytterbium complex is reported with a new tetradentate ligand based on the 2,2'-bipyridine-6,6'-dicarboxylic acid scaffold. The photophysical properties are investigated, especially with respect to near-infrared luminescence. The ytterbium complex shows a rather high absolute luminescence quantum yield of Φ = 3.0% and a luminescence lifetime of τobs = 72 µs at room temperature in CD3OD solution.

Highly Efficient One-Dimensional Triplet Exciton Transport in a Palladium-Porphyrin-Based Surface-Anchored Metal-Organic Framework.

Efficient photon-harvesting materials require easy-to-deposit materials exhibiting good absorption and excited-state transport properties. We demonstrate an organic thin-film material system, a palladium-porphyrin-based surface-anchored metal-organic framework (SURMOF) thin film that meets these requirements. Systematic investigations using transient absorption spectroscopy confirm that triplets are very mobile within single crystalline domains; a detailed analysis reveals a triplet transfer rate on the order of 1010 s-1. The crystalline nature of the SURMOFs also allows a thorough theoretical analysis using the density functional theory. The theoretical results reveal that the intermolecular exciton transfer can be described by a Dexter electron exchange mechanism that is considerably enhanced by virtual charge-transfer exciton intermediates. On the basis of the photophysical results, we predict exciton diffusion lengths on the order of several micrometers in perfectly ordered, single-crystalline SURMOFs. In the presently available samples, strong interactions of excitons with domain boundaries present in these metal-organic thin films limit the diffusion length to the diameter of these two-dimensional grains, which amount to about 100 nm. Our results demonstrate high potential of SURMOFs for light-harvesting applications.

Reaction of porphyrin-based surface-anchored metal-organic frameworks caused by prolonged illumination.

Crystalline surface-anchored metal-organic framework (SURMOF) thin films made from porphyrin-based organic linkers have recently been used in both photon upconversion and photovoltaic applications. While these studies showed promising results, the question of photostability in this organic-inorganic hybrid material has to be investigated before applications can be considered. Here, we combine steady-state photoluminescence, transient absorption, and time-resolved electron paramagnetic resonance spectroscopy to examine the effects of prolonged illumination on a palladium-porphyrin based SURMOF thin film. We find that phototreatment leads to a change in the material's photoresponse caused by the creation of stable products of photodecomposition - likely chlorin - inside the SURMOF structure. When the mobile triplet excitons encounter such a defect site, a short-lived (80 ns) cation-anion radical pair can be formed by electron transfer, wherein the charges are localized at a porphyrin and the photoproduct site, respectively.

Highly Efficient La2O3:Yb3+,Tm3+ Single-Band NIR-to-NIR Upconverting Microcrystals for Anti-Counterfeiting Applications.

Efficient single-band NIR-to-NIR upconversion (UC) emission is strongly desired for many applications such as fluorescent markers, plastic recycling, and biological imaging. Herein, we report highly efficient single-band NIR-to-NIR UC emission in La2O3:Yb3+,Tm3+ (LYT) microcrystals. Under 980 nm laser excitation, LYT exhibits a NIR UC emission at ∼795 nm (Tm3+: 3H4 → 3H6) and blue UC emission at ∼476 nm; the NIR UC emission is dominant, with the intensity ratio of the NIR to blue INIR/ Iblue > 100. Remarkably, a high absolute UC quantum yield (UCQY) of 3.4% is obtained for the single-band NIR UC emission of LYT at a relatively low excitation power density of 7.6 W/cm2. This value is much higher than the reported values of a single-band NIR UC for rare-earth-based UC materials in literature, such as the well-known benchmark UC materials of ß-NaYF4:Yb3+,Er3+ (∼0.9%, with a excitation power density of 9 W/cm2) and Gd2O2S:Yb3+,Er3+ (∼1.9%, with a excitation power density of 20 W/cm2). The high absolute UCQY of single-band NIR UC emission combined with their facile preparation hints at their potential application in anti-counterfeiting, verified by the proof-of-concept demonstration of fluorescent labeling of a transparent IMT pattern.

Absolute upconversion quantum yields of blue-emitting LiYF4:Yb3+,Tm3+ upconverting nanoparticles.

The upconversion quantum yield (ΦUC) is an essential parameter for the characterization of the optical performance of lanthanoid-doped upconverting nanoparticles (UCNPs). Despite its nonlinear dependence on excitation power density (Pexc), it is typically reported only as a single number. Here, we present the first measurement of absolute upconversion quantum yields of the individual emission bands of blue light-emitting LiYF4:Yb3+,Tm3+ UCNPs in toluene. Reporting the quantum yields for the individual emission bands is required for assessing the usability of UCNPs in various applications that require upconverted light of different wavelengths, such as bioimaging, photocatalysis and phototherapy. Here, the reliability of the ΦUC measurements is demonstrated by studying the same batch of UCNPs in three different research groups. The results show that whereas the total upconversion quantum yield of these UCNPs is quite high-typically 0.02 at a power density of 5 W cm-2-most of the upconverted photon flux is emitted in the 794 nm upconversion band, while the blue emission band at 480 nm is very weak, with a much lower quantum yield of ∼6 × 10-5 at 5 W cm-2. Overall, although the total upconversion quantum yield of LiYF4:Yb3+,Tm3+ UCNPs seems satisfying, notably for NIR bioimaging, blue-light demanding phototherapy applications will require better-performing UCNPs with higher blue light upconversion quantum yields.