Modification of a desktop FFF printer via NIR laser addition for upconversion 3D printing.

Traditional photopolymer-based 3D printing methods require sequential printing of thin layers, due to short penetration depths of UV or blue light sources used by these techniques. In contrast, upconversion 3D printing circumvents the layer-by-layer limitation by taking advantage of upconversion luminescence processes and the high penetration depths offered by near-infrared (NIR) lasers, allowing for selective crosslinking of voxels at any depth or position within the resin container. The implementation of this technique required the construction of a 3D printer with the ability of focusing the laser on any point of the space. For this, a low-cost fused filament fabrication (FFF) printer was modified by incorporating a 980 nm laser and laser control circuit. The total cost of the parts required for modification was £180. With enhanced penetration depths up to 5.8 cm, this method also allows for printing inside or through existing 3D printed parts. This opens doors for restoration of broken items, in situ bioprinting, 3D-circuitry, and notably, 3D printing inside cavities of a different material, illustrating numerous opportunities for practical applications.

Low-power laser manufacturing of copper tracks on 3D printed geometry using liquid polyimide coating.

Silver nanoparticle photoreduction synthesis by direct laser writing is a process that enables copper micro-track production on very specific polymers. However, some important 3D printing polymers, such as acrylonitrile butadiene styrene (ABS) and acrylates, do not accept this treatment on their surface. This work presents an approach to produce copper microcircuitry on 3D substrates from these materials by using direct laser writing at low power (32 mW CW diode laser). We show that by coating a thin layer of polyimide (PI) on a 3D-printed geometry, followed by a sequence of chemical treatments and low-power laser-induced photoreduction, copper tracks can be produced using silver as catalyst. The surface chemistry of the layer through the different stages of the process is monitored by FTIR and X-ray photoelectron spectroscopy. The copper tracks are selectively grown on the laser-patterned areas by electroless copper deposition, with conductivity (1.2 ± 0.7) × 107 S m-1 and a width as small as 28 µm. The patterns can be written on 3D structures and even inside cavities. The technique is demonstrated by integrating different circuits, including a LED circuit on 3D printed photopolymer acrylate and a perovskite solar cell on an ABS 3D curved geometry.

Regioselective electrophilic aromatic borylation as a method for synthesising sterically hindered benzothiadiazole fluorophores.

Regioselective stepwise phenylation of 4,7-diarylbenzo[c][1,2,5]thiadiazole fluorophores has been achieved through a facile one-pot, three-step synthetic strategy involving sequential borylation, hydroxydechlorination and Suzuki-Miyaura cross-coupling reactions. Crucial to the selectivity was the use of BCl3 to regioselectively install a boronic acid group in the ortho-position of only one of the diaryl groups. The subsequent introduction of ortho-phenyl groups through Suzuki-Miyaura cross-coupling gave rise to twisted structures with hindered intramolecular rotation, providing a structural lever with which the fluorophore absorption and emission properties could be adjusted.

Cubic versus hexagonal - phase, size and morphology effects on the photoluminescence quantum yield of NaGdF4:Er3+/Yb3+ upconverting nanoparticles.

Upconverting nanoparticles (UCNPs) are well-known for their capacity to convert near-infrared light into UV/visible light, benefitting various applications where light triggering is required. At the nanoscale, loss of luminescence intensity is observed and thus, a decrease in photoluminescence quantum yield (PLQY), usually ascribed to surface quenching. We evaluate this by measuring the PLQY of NaGdF4:Er3+,Yb3+ UCNPs as a function of size (ca. 15 to 100 nm) and shape (spheres, cubes, hexagons). Our results show that the PLQY of α-phase NaGdF4 Er3+,Yb3+ surpasses that of ß-NaGdF4 for sizes below 20 nm, an observation related to distortion of the crystal lattice when the UCNPs become smaller. The present study also underlines that particle shape must not be neglected as a relevant parameter for PLQY. In fact, based on a mathematical nucleus/hull volumetric model, shape was found to be particularly relevant in the 20 to 60 nm size range of the investigated UCNPs.

Spectroscopic ellipsometric study datasets of the fluorinated polymers: Bifunctional urethane methacrylate perfluoropolyether (PFPE) and polyvinylidene fluoride (PVDF).

The datasets in this work contain the experimentally measured (real) refractive indices, optical transmission intensity, and optical absorption spectra of bifunctional urethane methacrylate perfluoropolyether (PFPE; Fluorolink® MD700) substrate of (0.98 ± 0.13) mm thickness and polyvinylidene fluoride (PVDF; Kynar® 705) thin-film of (4.47 ± 0.29) µm thickness over a spectral range from 300 nm to 1000 nm, as measured via variable angle spectroscopic ellipsometry. The refractive indices data were determined by employing a single Cauchy optical constants function based layer using a Levenberg-Marquardt multi-iterative regression algorithm for all model minimizations. The mean-squared error (MSE) was used as the maximum likelihood estimator, with a convergence of the Levenberg-Marquardt algorithm reached when successive iterations were unable to improve the MSE. The resulting best-fit parameter values were evaluated for sensitivity (expressed as a confidence limit), and possible correlations. Furthermore, the experimentally measured optical transmission intensity and determined optical absorption of PFPE and PVDF, over a spectral range from 300 nm to 1000 nm, is also presented, as measured via ellipsometry and corrected using Fresnel equations to accommodate surface interference. Given the high transmission of (88.4 ± 0.5)% for PFPE and (95.6 ± 0.6) % for PVDF found, and the low refractive index 1.27 (λ = 589.3 nm) found for PFPE; it is thought that these datasets may be useful for optical applications, such as for photo-curable synthesis processes, or being used as a host-matrix material for photoluminescent compounds.

Optimized photoluminescence quantum yield in upconversion composites considering the scattering, inner-filter effects, thickness, self-absorption, and temperature.

Optimizing upconversion (UC) composites is challenging as numerous effects influence their unique emission mechanism. Low scattering mediums increase the number of dopants excited, however, high scattering mediums increase the UC efficiency due to its non-linear power dependency. Scattering also leads to greater thermal effects and emission saturation at lower excitation power density (PD). In this work, a photoluminescence quantum yield (PLQY) increase of 270% was observed when hexagonal NaYF4:(18%)Yb3+,(2%)Er3+ phosphor is in air compared to a refractive index-matched medium. Furthermore, the primary inner-filter effect causes a 94% PLQY decrease when the excitation focal point is moved from the front of the phosphor to 8.4 mm deep. Increasing this effect limits the maximum excitation PD, reduces thermal effects, and leads to emission saturation at higher excitation PDs. Additionally, self-absorption decreases the PLQY as the phosphor's thickness increases from 1 to 9 mm. Finally, in comparison to a cuboid cuvette, a 27% PLQY increase occurs when characterizing the phosphor in a cylindrical cuvette due to a lensing effect of the curved glass, as supported by simulations. Overall, addressing the effects presented in this work is necessary to both maximize UC composite performance as well as report their PLQY more reliably.

8,8'-(Benzo[c][1,2,5]thiadiazole-4,7-diyl)bis(quinolin-4(1H)-one): a twisted photosensitizer with AIE properties.

A new benzothiadiazole (BTZ) luminogen is prepared via the Suzuki-Miyaura Pd-catalysed C-C cross-coupling of 8-iodoquinolin-4(1H)-one and a BTZ bispinacol boronic ester. The rapid reaction (5 min) affords the air-, thermo-, and photostable product in 97% yield as a yellow precipitate that can be isolated by filtration. The luminogen exhibits aggregated-induced emission (AIE) properties, which are attributed to its photoactive BTZ core and nonplanar geometry. It also behaves as a molecular heterogeneous photosensitizer for the production of singlet oxygen under continuous flow conditions.

The upconversion quantum yield (UCQY): a review to standardize the measurement methodology, improve comparability, and define efficiency standards.

Advancing the upconversion materials field relies on accurate and contrastable photoluminescence efficiency measurements, which are characterised by the absolute upconversion quantum yield (UCQY). However, the methodology for such measurements cannot be extrapolated directly from traditional photoluminescence quantum yield techniques, primarily due to issues that arise from the non-linear behaviour of the UC process. Subsequently, no UCQY standards exist, and significant variations in their reported magnitude can occur between laboratories. In this work, our aim is to provide a path for determining and reporting the most reliable UCQYs possible, by addressing all the effects and uncertainties that influence its value. Here the UCQY standard, at a given excitation power density, is defined under a range of stated experimental conditions, environmental conditions, material properties, and influential effects that have been estimated or corrected for. A broad range of UCQYs reported for various UC materials are scrutinized and categorized based on our assertion of the provided information associated with each value. This is crucial for improved comparability with other types of photoluminescent materials, and in addition, the next generation of UC materials can be built on top of these reliable standards.

Effect of light scattering on upconversion photoluminescence quantum yield in microscale-to-nanoscale materials.

Scattering affects excitation power density, penetration depth and upconversion emission self-absorption, resulting in particle size -dependent modifications of the external photoluminescence quantum yield (ePLQY) and net emission. Micron-size NaYF4:Yb3+, Er3+ encapsulated phosphors (∼4.2 µm) showed ePLQY enhancements of >402%, with particle-media refractive index disparity (Δn): 0.4969, and net emission increases of >70%. In sub-micron phosphor encapsulants (∼406 nm), self-absorption limited ePLQY and emission as particle concentration increases, while appearing negligible in nanoparticle dispersions (∼31.8 nm). These dependencies are important for standardising PLQY measurements and optimising UC devices, since the encapsulant can drastically enhance UC emission.

Spectral characterization of LiYbF4 upconverting nanoparticles.

In light of the recent developments on Yb3+-based upconverting rare-earth nanoparticles (RENPs), we have systematically explored the spectral features of LiYbF4:RE3+/LiYF4 core/shell RENPs doped with various amounts of Tm3+, Er3+, or Ho3+. Tm3+-RENPs displayed photoluminescence from the UV to near-infrared (NIR), and the dominant high-photon-order upconversion emission of these RENPs was tunable by Tm3+ doping. Similarly, Er3+- and Ho3+-RENPs with green and red upconversion showed wide color tuning, depending on the doping amount and excitation power density. From steady-state power plot and photoluminescence decay studies we have observed respective changes in upconversion photon order and average lifetime that attest to a number of cross-relaxation processes occurring at higher RE3+ doping concentration. Particularly in the case of Tm3+-RENPs, cross-relaxation promotes four- and five-photon order upconversion emission in the UV and blue spectral regions. The quantum yield of high-order upconversion emission was on par with classic Yb3+/Tm3+-doped systems, yet due to the high number of sensitizer ions in the LiYbF4 host these RENPs are expected to be brighter and thus better suited for applications such as controlled drug delivery or optogenetics. Overall, LiYbF4:RE3+/LiYF4 RENPs are promising systems to effectively generate high-order upconversion emissions, owing to excitation energy confinement within the Yb3+ network and its efficient funneling to the activator dopants.

Morphology control, spectrum modification and extended optical applications of rare earth ion doped phosphors.

Rare earth ion (RE3+) doped nano-phosphors with controllable morphologies have a wide range of applications in laser crystals, LEDs, bio-probes, photo-catalysis, three-dimensional displays, sensors, and flash memories. This review summarizes the morphology control strategy, phase transfer theory, spectrum modulation, and extended optical applications of RE3+-doped phosphors. The roles of surfactants in the morphology control in the liquid-solid-solution phase transfer process for RE3+-doped fluorides, oxides and other compounds are discussed. The relevant mechanisms of controlling morphologies are illustrated. The size- and shape-dependent optical properties of RE3+ doped phosphors, including the emission intensities, intensity ratios of adjacent emission bands, decay times and thermal stability, are analyzed. The extended optical applications and main challenges of RE3+-doped phosphors are also discussed.

Ultrafast photochemistry produces superbright short-wave infrared dots for low-dose in vivo imaging.

Optical probes operating in the second near-infrared window (NIR-II, 1,000-1,700 nm), where tissues are highly transparent, have expanded the applicability of fluorescence in the biomedical field. NIR-II fluorescence enables deep-tissue imaging with micrometric resolution in animal models, but is limited by the low brightness of NIR-II probes, which prevents imaging at low excitation intensities and fluorophore concentrations. Here, we present a new generation of probes (Ag2S superdots) derived from chemically synthesized Ag2S dots, on which a protective shell is grown by femtosecond laser irradiation. This shell reduces the structural defects, causing an 80-fold enhancement of the quantum yield. PEGylated Ag2S superdots enable deep-tissue in vivo imaging at low excitation intensities (<10 mW cm-2) and doses (<0.5 mg kg-1), emerging as unrivaled contrast agents for NIR-II preclinical bioimaging. These results establish an approach for developing superbright NIR-II contrast agents based on the synergy between chemical synthesis and ultrafast laser processing.

10-Fold Quantum Yield Improvement of Ag2S Nanoparticles by Fine Compositional Tuning.

Ag2S semiconductor nanoparticles (NPs) are near-infrared luminescent probes with outstanding properties (good biocompatibility, optimum spectral operation range, and easy biofunctionalization) that make them ideal probes for in vivo imaging. Ag2S NPs have, indeed, made possible amazing challenges including in vivo brain imaging and advanced diagnosis of the cardiovascular system. Despite the continuous redesign of synthesis routes, the emission quantum yield (QY) of Ag2S NPs is typically below 0.2%. This leads to a low luminescent brightness that avoids their translation into the clinics. In this work, an innovative synthetic methodology that permits a 10-fold increment in the absolute QY from 0.2 up to 2.3% is presented. Such an increment in the QY is accompanied by an enlargement of photoluminescence lifetimes from 184 to 1200 ns. The optimized synthetic route presented here is based on a fine control over both the Ag core and the Ag/S ratio within the NPs. Such control reduces the density of structural defects and decreases the nonradiative pathways. In addition, we demonstrate that the superior performance of the Ag2S NPs allows for high-contrast in vivo bioimaging.

Synthesis and characterization of Ag2S and Ag2S/Ag2(S,Se) NIR nanocrystals.

Syntheses of metal sulfide nanocrystals (NCs) by heat-up routes in the presence of thiols yield NC arrangements difficult to further functionalize and transfer to aqueous media. By means of different NMR techniques, and exemplified by Ag2S NCs, a metal-organic polymer formed during the synthesis acting as a ligand has been identified to be responsible for such aggregation. In this work, a new synthetic hot-injection strategy is presented to synthesize Ag2S NCs which are easily ligand exchangeable in water. Furthermore, the hot-injection route allows an extra NC treatment with Se to produce Ag2S/Ag2(S,Se) NCs with improved optical properties with respect to the Ag2S cores, and better resistance to oxidation, as demonstrated by X-ray absorption experiments.

Particle separation by phase modulated surface acoustic waves.

High efficiency isolation of cells or particles from a heterogeneous mixture is a critical processing step in lab-on-a-chip devices. Acoustic techniques offer contactless and label-free manipulation, preserve viability of biological cells, and provide versatility as the applied electrical signal can be adapted to various scenarios. Conventional acoustic separation methods use time-of-flight and achieve separation up to distances of quarter wavelength with limited separation power due to slow gradients in the force. The method proposed here allows separation by half of the wavelength and can be extended by repeating the modulation pattern and can ensure maximum force acting on the particles. In this work, we propose an optimised phase modulation scheme for particle separation in a surface acoustic wave microfluidic device. An expression for the acoustic radiation force arising from the interaction between acoustic waves in the fluid was derived. We demonstrated, for the first time, that the expression of the acoustic radiation force differs in surface acoustic wave and bulk devices, due to the presence of a geometric scaling factor. Two phase modulation schemes are investigated theoretically and experimentally. Theoretical findings were experimentally validated for different mixtures of polystyrene particles confirming that the method offers high selectivity. A Monte-Carlo simulation enabled us to assess performance in real situations, including the effects of particle size variation and non-uniform acoustic field on sorting efficiency and purity, validating the ability to separate particles with high purity and high resolution.

Improving Optical Temperature Sensing Performance of Er3+ Doped Y2O3 Microtubes via Co-doping and Controlling Excitation Power.

This work presents a new method to effectively improve the optical temperature behavior of Er3+ doped Y2O3 microtubes by co-doping of Tm3+ or Ho3+ ion and controlling excitation power. The influence of Tm3+ or Ho3+ ion on optical temperature behavior of Y2O3:Er3+ microtubes is investigated by analyzing the temperature and excitation power dependent emission spectra, thermal quenching ratios, fluorescence intensity ratios, and sensitivity. It is found that the thermal quenching of Y2O3:Er3+ microtubes is inhibited by co-doping with Tm3+ or Ho3+ ion, moreover the maximum sensitivity value based on the thermal coupled 4S3/2/2H11/2 levels is enhanced greatly and shifts to the high temperature range, while the maximum sensitivity based on 4F9/2(1)/4F9/2(2) levels shifts to the low temperature range and greatly increases. The sensitivity values are dependent on the excitation power, and reach two maximum values of 0.0529/K at 24 K and 0.0057/K at 457 K for the Y2O3:1%Er3+, 0.5%Ho3+ at 121 mW/mm2 excitation power, which makes optical temperature measurement in wide temperature range possible. The mechanism of changing the sensitivity upon different excitation densities is discussed.

Measurement procedure for absolute broadband infrared up-conversion photoluminescent quantum yields: correcting for absorption/re-emission.

The internal photoluminescent quantum yield (iPLQY)--defined as the ratio of emitted photons to those absorbed--is an important parameter in the evaluation and application of luminescent materials. The iPLQY is rarely reported due to the complexities in the calibration of such a measurement. Herein, an experimental method is proposed to correct for re-emission, which leads to an underestimation of the absorption under broadband excitation. Although traditionally the iPLQY is measured using monochromatic sources for linear materials, this advancement is necessary for nonlinear materials with wavelength dependent iPLQY, such as the application of up-conversion to solar energy harvesting. The method requires an additional measurement of the emission line shape that overlaps with the excitation and absorption spectra. Through scaling of the emission spectrum, at the long wavelength edge where an overlap of excitation does not occur, it is possible to better estimate the value of iPLQY. The method has been evaluated for a range of nonlinear material concentrations and under various irradiances to analyze the necessity and boundary conditions that favor the proposed method. Use of this refined method is important for a reliable measurement of iPLQY under a broad illumination source such as the Sun.

Self-absorption in upconverter luminescent layers: impact on quantum yield measurements and on designing optimized photovoltaic devices.

This Letter details a theoretical investigation of self-absorption within an upconverter (UC) material, consisting of trivalent erbium (Er3+)-doped hexagonal sodium yttrium fluoride (ß-NaYF4) and its implications on two experimental situations: the case of a quantum yield measurement, and on the effective performance in a UC-enhanced photovoltaic (PV) device. The study demonstrates that an optimization of the thickness is essential in order to reduce the effect of self-absorption and maximize the possible additional photocurrent that could be harvested. It also has been found that the external photoluminescence quantum yield (ePLQY) measured through an integrating sphere may result in an underestimation with respect to the performance that the UC material could achieve in a UC-PV device. Finally, it has been found the optimal thickness and the molar concentration of Er3+ ions are inversely proportional, suggesting that an optimal number (1.3-2.9·10(17)) of Er3+ ions should be contained within the UC layer.

Enhanced up-conversion for photovoltaics via concentrating integrated optics.

Concentrating optics are integrated into up-conversion photovoltaic (UC-PV) devices to independently concentrate sub-band-gap photons on the up-conversion layer, without affecting the full solar concentration on the overlying solar cell. The UC-PV devices consist of silicon solar cells optimized for up-conversion, coupled with tapered and parabolic dielectric concentrators, and hexagonal sodium yttrium fluoride (ß-NaYF4) up-converter doped with 25% trivalent erbium (Er³âº). A normalized external quantum efficiency of 1.75x10⁻² cm²/W and 3.38x10⁻² cm²/W was obtained for the UC-PV device utilizing tapered and parabolic concentrators respectively. Although low to moderate concentration was shown to maximize UC, higher concentration lead to saturation and reduced external quantum efficiency. The presented work highlights some of the implications associated with the development of UC-PV devices and designates a substantial step for integration in concentrating PV.

Ultra-high photoluminescent quantum yield of ß-NaYF4: 10% Er3+ via broadband excitation of upconversion for photovoltaic devices.

The upconversion photoluminescent quantum yield (PLQY) of erbium-doped hexagonal sodium yttrium fluoride (ß-NaYF(4): 10% Er(3+) was measured under broadband excitation with full width half maxima ranging from 12 to 80 nm. A novel method was developed to increase the bandwidth of excitation, while remaining independent of power via normalization to the air mass 1.5 direct solar spectrum. The measurements reveal that by broadening the excitation spectrum a higher PLQY can be achieved at lower solar concentrations. The highest PLQY of 16.2 ± 0.5% was achieved at 2270 ± 100 mW mm(-2) and is the highest ever measured.