Upconversion Process Research Articles

Visible-light photocatalytic activity of rare-earth-metal-doped TiO2: Experimental analysis and machine learning for virtual design

Modification with rare-earth (RE) metals has emerged as an important approach for enhancing the properties of titanium dioxide. Herein, the visible-light photocatalytic activity of RE-TiO2 (RE: Tm, Er, Nd, Dy, Lu, La, Ho, Pr, Tb, Sc, Ce, Yb, Sm, Gd, Y, or Eu) was investigated using a combination of computer simulations and experimental techniques. The RE-TiO2 photocatalysts were characterised using advanced experimental techniques, including X-ray diffraction, X-ray photoelectron spectroscopy, luminescence, diffuse reflectance spectroscopy, and specific surface area measurements. Furthermore, a quantitative structure–activity relationship analysis was conducted by applying a partial least-squares machine learning algorithm. The Ho-TiO2 sample exhibited the highest photocatalytic activity under visible-light irradiation. Notably, the observed activity was not due to an up-conversion process, originating instead from slight bandgap narrowing caused by new sub-bandgap states from the RE 4 f levels.

Ultraviolet Circularly Polarized Luminescence in Chiral Perovskite Nanoplatelet-Molecular Hybrids: Direct Binding Versus Efficient Triplet Energy Transfer.

The development of ultraviolet circularly polarized light (UVCPL) sources has the potential to benefit plenty of practical applications but remains a challenge due to limitations in available material systems and a limited understanding of the excited state chirality transfer. Herein, by constructing hybrid structures of the chiral perovskite CsPbBr3 nanoplatelets and organic molecules, excited state chirality transfer is achieved, either via direct binding or triplet energy transfer, leading to efficient UVCPL emission. The underlying photophysical mechanisms of these two scenarios are clarified by comprehensive optical studies. Intriguingly, UVCPL realized via the triple energy transfer, followed by the triplet-triplet annihilation upconversion processes, demonstrates a 50-fold enhanced dissymmetry factor glum. Furthermore, stereoselective photopolymerization of diacetylene monomer is demonstrated by using such efficient UVCPL. This study provides both novel insights and a practical approach for realizing UVCPL, which can also be extended to other material systems and spectral regions, such as visible and near-infrared.

Uniaxial Strain Tuning of Upconversion Photoluminescence in Monolayer WSe2

Strain engineering is one of the leading mechanical ways to tune the optical properties of monolayer transition metal dichalcogenides among different techniques. Here, uniaxial strain is applied on exfoliated 1L‐WSe2 flakes transferred on flexible polycarbonate substrates to study the strain tuning of upconversion photoluminescence. It is demonstrated that the peak position of upconversion photoluminescence is redshifted by around 20 nm as the applied uniaxial strain increases from 0% to 1.17%, while the intensity of upconversion photoluminescence increases exponentially for the upconversion energy difference ranging from −155 to −32 meV. The linear and sublinear power dependence of upconversion photoluminescence is observed for different excitation wavelengths with and without uniaxial strain, suggesting the multiphonon‐assisted mechanism in one‐photon regime for the upconversion process. These results offer the potential to advance 2D material‐based optical upconversion applications in night vision, strain‐tunable infrared detection, and flexible optoelectronics.

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.

Preparation and strong green upconversion luminescence of Ca9Y(VO4)7: Yb3+/Er3+ phosphor

Exploring novel oxysalt compounds remains significant due to their affordability and versatile applications, such as serving as laser crystals, piezoelectric crystals, frequency-doubling crystals, and luminescent materials. Specifically, this study introduces a new near-single green upconversion luminescent Ca9(VO4)7: Yb3+/Er3+ material, synthesized through high-temperature solid-phase methods. When subjected to 980 nm near-infrared laser irradiation, the Ca9(VO4)7: 0.3 Yb3+, 0.02 Er3+ phosphor demonstrates robust green luminescence at 531 nm (2H11/2 → 4I15/2) and 558 nm (4S3/2 → 4I15/2), accompanied by faint red luminescence at 665 nm (4F9/2 → 4I15/2). The optimal doping concentrations for Yb3+ and Er3+ ions, yielding the highest upconversion luminescence intensity, are determined to be 0.3 and 0.02, respectively. The investigation elucidates the upconversion luminescence mechanism through the downward shift spectrum in photoluminescence and the pumping power dependence of upconversion green-red luminescence. The primary excitation pathway identified for the upconversion process in Ca9Y(VO4)7: 0.3 Yb3+, 0.02 Er3+ involves Yb3+ (2F5/2) + Er3+ (4I11/2) → Yb3+ (2F7/2) + Er3+ (4F7/2). This research contributes to the exploration of new materials, injecting vitality into modern industries and production processes.

Impact of excitation pulse width on the upconversion luminescence lifetime of NaYF4:Yb3+,Er3+ nanoparticles.

The upconversion luminescence (UCL) lifetime has a wide range of applications, serving as a critical parameter for optimizing the performance of upconversion nanoparticles (UCNPs) in various fields. It is crucial to understand that this lifetime does not directly correlate with the decay time of the emission level; rather, it represents a compilation of all the physical phenomena taking place in the upconversion process. To delve deeper into this, we analyzed the dependence of the UCL lifetime on the excitation pulse width for β-NaYF4:Yb3+,Er3+ nanoparticles. The results revealed a significant increase in the UCL lifetime with both the excitation pulse width and the excitation intensity. The laser fluence was identified as the parameter governing the UCL decay dynamics. We showcased the universality of the pulse-width-dependent UCL lifetime phenomenon by employing UCNPs of various sizes, surface coatings, host matrices, Yb3+ and Er3+ ratios, and dispersing UCNPs in different solvents. Theoretical explanations for the experimental findings were derived through a rate equation analysis. Finally, we discussed the implications of these results in UCNP-FRET (Förster resonance energy transfer)-based applications.

Up-conversion photoluminescence of transition metal chalcogenide monolayers under high pressure

The up-conversion photoluminescence (UPL) phenomena of transition metal chalcogenides (TMDCs) materials have been studied in the recent years, but high-pressure tuning effect remains unclear. In this work, we applied pressure to the monolayer WS2 by Diamond Anvil Cell (DAC). The PL and UPL of monolayer WS2 under ambient pressure and tuning from 0.96GPa to 4.48GPa were investigated using various excitation energies. We found that with the increase of applied pressure, the intensity of UPL decreased dramatically. Under the same pressure, the peak of UPL is shifted compared with that of normal PL. This tuning is promising for realizing photodetection by using of the up-conversion process.

Localized three-photon upconversion enhancement in silver nanowire networks and its effect in thermal sensing.

The quest for enhancing the upconversion luminescence (UCL) efficiency of rare-earth doped materials has been a common target in nanophotonics research. Plasmonic nanoarchitectures have proven potential for amplifying UCL signals, prompting investigations into localized enhancement effects within noble metal nanostructures. In this work we investigate the localized enhancement of UCL in silver nanowire (AgNW) networks coated with upconversion nanoparticles (UCNPs) by employing hyperspectral microscopy to unveil distinctive regions of local enhancement. Our study reveals that three-photon upconversion processes predominantly occur at hot-spots in nanowire junctions, contributing to heightened luminescence intensity on AgNW networks. Intriguingly, our findings demonstrate that enhancement on AgNWs introduces significant artifacts for thermometry based on ratiometric analysis of the emission spectra, resulting in the observation of artificial thermal gradients. To address this challenge, we developed correction methods that were successfully applied to mitigate this effect, enabling the generation of accurate thermal maps and the realization of dynamic thermal measurements. We quantified the distance-dependent enhancement profiles and studied the effect of temperature by exploiting the heat dissipation under varying electrical voltages across the electrically percolated AgNW networks. The observations were confirmed through numerical calculations of the enhancement factor and the energy transfer rates. This comprehensive investigation sheds light on the complex interplay between plasmonic nanostructures, three-photon upconversion processes, and their influence on thermal sensing applications. The presented hyperspectral method not only allows a direct visualization of plasmonic hot-spots but also advances our understanding of localized enhancements. The correction methods applied to analyze the emission spectra also contribute to the refinement of accurate temperature mapping using UCNPs, thereby enhancing the reliability of this thermal sensing technology.

Frequency Analysis of Pulse-Width Modulation on All-Digital Transmitters

This work investigates the frequency spectrum in the modulator and up-conversion outputs of a generic all-digital transmitter architecture. Considering the modulator is implemented as a pulse-width modulation (PWM), it is verified that this up-conversion process introduces a series of impulses resembling the spectrum of a unipolar return-to-zero (RZ) waveform in addition to the PWM impulses. Simulations show the minimum bit resolution of PWM signals where the impulses introduced are almost unnoticed, thus their influence is not distinguished from random background noise. An all-digital transmitter is designed on a field-programmable gate array to verify it experimentally. Experimental results show that reducing power from PWM harmonics leads to a power increase in the RZ harmonics, and vice-versa. These harmonic’s power present an energy trade-off relation, a novelty demonstrated in this paper. Finally, but not least, it is observed that filtering the carrier wave out causes a considerable amount of power to be lost.

Color tunable luminescence in ThO2:Er3+,Yb3+ nanocrystals: a promising new platform for upconversion.

Lanthanide-doped luminescent nanoparticles are an appealing system for many applications in the area of biomedical, solar cell, thermometry, anti-counterfeiting, etc. due to their sensitivity, reliability, high photochemical stability, and high optical transparency in the visible-NIR range. A color-tunable upconversion-luminescence (UCL) in a new low phonon energy ThO2 host based on modulating sensitizer concentration has been realized in this work and it may work as a potential candidate to replace corrosive and toxic fluoride based hosts in the future. Er3+-Yb3+ co-doped thoria nanoparticles were prepared using a gel combustion route and their structural and luminescence properties were determined as a function of the Yb3+ concentration. Phonon dispersion measurements have established the dynamic structural stability of the thoria nanoparticles. Density functional theory (DFT) was used to calculate the defect formation energy, highlighting the feasibility of dual ion (Er3+ and Yb3+) doping in thoria. The morphology and average size of the doped thoria was studied using high resolution transmission electron microscopy (HRTEM), and any defects evolving as a result of aliovalent doping were probed using positron annihilation lifetime spectroscopy (PALS). With 980 nm laser excitation, the nanothoria emits green and near-red light. A significant enhancement of the red-to-green intensity ratio of Er3+ ions in nanothoria was observed with an increase in Yb3+ concentration which resulted in beautiful color tunability from green to yellow light in going from lower (up to ∼5 mol%) to higher (10 and 15 mol%) Yb3+ concentration. The power dependence and the dynamics of the upconverted emission confirm the existence of two-photon upconversion processes for the green and red emissions.

Intense green up/down conversion emission and high-sensitivity optical thermometry of NaYb(WO4)2:Er3+ stoichiometric phosphors

Optical thermometry based on fluorescence intensity ratio (FIR) has garnered significant interest among researchers due to its rapid, non-contact, and high sensitivity characteristics. In this study, stoichiometric NaYb(WO4)2 phosphors, doped with varying concentrations of Er3+, were successfully synthesized using the high-temperature solid-state method. Under both 980 nm and 266 nm excitation, the samples exhibited strong green and very weak red upconversion (UC) and downconversion (DC) luminescence. The structural and morphological properties of the prepared samples were thoroughly characterized using techniques such as X-ray diffraction (XRD), XRD Rietveld refinement, scanning electron microscopy (SEM), and Fourier transform infrared (FT-IR) spectroscopy. The phosphors demonstrated high-purity UC and DC emission, with maximum green-to-red ratios of 60.9 and 77.0, respectively. This discovery opens up vast possibilities for their application as pure green color converters. The UC emission of Er3+ ions in the stoichiometric NaYb(WO4)2 phosphor was identified as a two-photon UC process, as evidenced by the relationship between the luminescence intensity and the excitation power of the sample. Moreover, the temperature-dependent emission spectra of UC and DC were monitored, and investigated the fluorescence intensity ratios (FIRs) of 2H11/2 → 4I15/2 and 4S3/2 → 4I15/2 transitions of Er3+ ions to assess the optical temperature sensing behavior of NaYb(WO4)2:Er3+. The experimental results revealed that the maximum absolute sensitivities (SA) of NaYb(WO4)2 phosphors were 0.0120 K-1 (UC) and 0.0077 K-1 (DC), and the maximum relative sensitivities (SR) were 0.0089 K-1 (UC) and 0.0092 K-1 (DC), respectively. These findings highlight the promising of Er3+-doped Yb3+ stoichiometric NaYb(WO4)2 phosphors in optical temperature sensors.

Near-infrared to visible up-conversion in Er3+ doped LaAlO3 phosphors and their assessment as an optical temperature sensor

The present work studies the optical temperature sensing in micro and nanospheres of LaAlO3, synthesized by a Pechini sol-gel method. The optical properties focus on the up-conversion emission and optical temperature sensing properties of thermally and non-thermally coupled levels. Exciting at 975 nm, the up-conversion produces three emissions bands centered at 533, 545, and 670 nm. When the concentration of Er ion increases, the intensity of emission increases up to 5 %. The mechanism shows the absorption of two photons and the energy transfer up-conversion process. Optical temperature sensing is studied in the range of 299–327 K based on thermal coupled and non-thermal coupled levels by the luminescence intensity ratio technique. The absolute sensitivity, relative sensitivity, and uncertainty temperature values were obtained to study the material's performance and applicability. The maximum absolute and relative sensitivity values are 5.21 × 10−3 K−1 at 327 K for I670/I545 and 0.87 % at 299 K for I533/545. On the other hand, the temperature uncertainty is 0.2 K, indicating that the present material may be used as an effective temperature-sensing device using thermal coupled and non-thermal coupled levels.

All-optical free-space routing of upconverted light by metasurfaces via nonlinear interferometry.

All-optical modulation yields the promise of high-speed information processing. In this field, metasurfaces are rapidly gaining traction as ultrathin multifunctional platforms for light management. Among the featured functionalities, they enable light-wavefront manipulation and more recently demonstrated the ability to perform light-by-light manipulation through nonlinear optical processes. Here, by employing a nonlinear periodic metasurface, we demonstrate the all-optical routing of telecom photons upconverted to the visible range. This is achieved via the interference between two frequency-degenerate upconversion processes, namely, third-harmonic and sum-frequency generation, stemming from the interaction of a pump pulse with its frequency-doubled replica. By tuning the relative phase and polarization between these two pump beams, we route the upconverted signal among the diffraction orders of the metasurface with a modulation efficiency of up to 90%. This can be achieved by concurrently engineering the nonlinear emission of the individual elements (meta-atoms) of the metasurface along with its pitch. Owing to the phase control and ultrafast dynamics of the underlying nonlinear processes, free-space all-optical routing could be potentially performed at rates close to the employed optical frequencies divided by the quality factor of the optical resonances at play. Our approach adds a further twist to optical interferometry, which is a key enabling technique employed in a wide range of applications, such as homodyne detection, radar interferometry, light detection and ranging technology, gravitational-wave detection and molecular photometry. In particular, the nonlinear character of light upconversion combined with phase sensitivity is extremely appealing for enhanced imaging and biosensing.

Phonon-assisted upconversion photoluminescence in Mn-doped two-dimensional hybrid metal halides

Phonon-assisted upconversion process is one of the important means to generate upconversion photoluminescence (UCPL), and has important applications in laser refrigeration and other fields. However, until now, the studies on UCPL behavior are still insufficient. Herein, this work synthesizes a series of Mn-doped two-dimensional hybrid metal halide (2D HMH) thin films and investigates their optical properties using various spectral techniques. Raman spectroscopic measurement confirms that Mn-doping is achieved via interstitial doping rather than Pb-substitution. By the measurement of the temperature-dependent PL spectrum, it is found that Mn-doping will weaken the thermal expansion effect of 2D HMHs, but will enhance the electron–phonon coupling strength. More importantly, both two-photon-excited and phonon-assisted UCPL are observed in Mn-doped 2D HMHs, with an extremely large phonon-assisted energy gain (approximately 500[Formula: see text]meV). Our experimental results are of significance for designing phonon-assisted UCPL materials and expanding their applications.

The real-time temperature of Ag2S PTT was monitored through a non-contact upconversion thermometer in a composite structure

In this study, a multifunctional Ba2GdF7:Yb3+, Er3+/Ag2S NCs was synthesized, which could realize temperature measurement and photothermal conversion. The temperature sensing properties of Ba2GdF7:Yb3+, Er3+/Ag2S NCs based on FIR technology were investigated in the range of 300K–360K. The results indicate that the maximum values of Sa and Sr are 0.073 K−1@360K and 1.406%K−1@300K, respectively. Next, the photothermal effect of the content of Ba2GdF7: Yb3+, Er3+ on Ag2S in the composites was evaluated. Appropriate amount of Ba2GdF7: Yb3+, Er3+ can enhance the photothermal efficiency of Ag2S, which is attributed to Ag2S absorbing visible light emitted from the up-conversion process of Ba2GdF7:Yb3+, Er3+ and releasing heat. Then, in egg white, Ba2GdF7:Yb3+, Er3+ based on FIR technology can monitor temperature of Ag2S photothermal therapy. Ultimately, the cytotoxicity test on HeLa cells using methyl thiazolyl tetrazolium (MTT) assay showed good biocompatibility of the Ba2GdF7:Yb3+, Er3+/Ag2S NCs.

Flexible composite film with enhanced upconversion emission for ultrasensitive gas detection

Lanthanide-doped upconversion nanoparticles (UCNPs) were found promising in photovoltaic devices and nanoscale sensing due to their excellent optical properties. However, the low quantum yields severely limit their practical applications. In this work, we reported the enhanced upconversion emission by near-field modulation on all dielectric interfaces. The flexible polystyrene (PS) sphere array @UCNPs composite was fabricated by self-assembly and the NIR excitation can be highly localized and amplified in the array with proper sphere size, thus promoting the upconversion process. Based on this efficient upconversion composite film, the sensing performance on acetic acid gas were discussed in detail. The good linear relationship between the upconversion luminescence intensity and acetic acid concentration can be achieved with a detection limit of 5.2 ppm at room temperature, which is comparable with the best level reported so far. In addition, such optical signal-based sensors possessed other unique advantages such as easy fabrication, high sensitivity, long-term stability, reusability and flexibility. And the fluorescence signal enhancement factor showed less dependence on the excitation power and can emit effectively at low pump power. This all dielectric fluorescent composite with high efficiency and sensing performance can be helpful in biosensor and flexible security label applications.

33.8 W Mid-infrared 2.8 μm Er-doped fiber laser with high optical efficiency

We demonstrate an efficient, high-power single-end-pumped Er-doped ZBLAN (Er:ZBLAN) fiber laser operating at 2.8 μm. A maximum laser power of 33.8 W at a wavelength of 2.87 μm was achieved with an optical efficiency of 26.4 %. A maximum slope efficiency of 32.8 % was obtained, which approaches the Stokes efficiency of the intrinsic Er3+ energy transfer up-conversion process. We examine both experimentally and theoretically, the change in optical efficiency in relation to output coupling ratios, laser wavelength, and pump power. Simulations demonstrate that the Er:ZBLAN fiber laser system exhibits high gain at 2.8 μm, and red-shifting of the laser wavelength results in reduced laser field reabsorption and increased laser efficiency. To the best of our knowledge, this work demonstrates the highest output power generated from a single-end-pumped Er-doped fluoride fiber laser.

Multimode Luminescent Properties from Tb3+-Yb3+ Codoped CaMoO4 for Solar Cell Spectral Conversion

NIR and visible emitting CaMoO4:Tb3+/Tb3+-Yb3+ phosphors were synthesized to harness the energy losses attribute to wavelength mismatch between response spectrum of incident solar photons and solar cells. The X-ray diffraction (XRD), field emission scanning microscopy (FE-SEM), fourier transform infrared spectroscopy (FTIR), UV–vis diffuse reflectance spectroscopy, photoluminescence (PL), up-conversion and life time measurements were used to characterized the prepared phosphors. XRD study followed by Rietveld refinement confirms the tetragonal crystal structure with space group I41a(88). The phosphors exhibit strong green emission (5D4→7F4) in visible region after an excitation wavelengths 378 nm and 980 nm, respectively through down-shifting (DS) and up-conversion (UC) processes. The UV photons (378 nm) are also split it into two NIR photons (2F7/2→2F5/2) through down-conversion process. Fluorescence quenching was observed by increasing concentration of Tb3+ and Yb3+ ions. Lifetime measurements clearly illustrates the energy transfer from Tb3+ to Yb3+ ions and mechanism involved is co-operative energy transfer. The estimated values of energy transfer efficiency (ETE) and corresponding theoretical internal quantum efficiency are achieved as 69% and 169% respectively.

Line Verification in Luminescence Spectra of Fluorophosphate Glass Doped with Ytterbium and Thulium Ions by the Degree of Nonlinearity of Up-Conversion Processes

Line Verification in Luminescence Spectra of Fluorophosphate Glass Doped with Ytterbium and Thulium Ions by the Degree of Nonlinearity of Up-Conversion Processes

Magnetic Field Effects in Triplet-Triplet Annihilation Upconversion: Revisiting Atkins and Evans' Theory.

In their seminal description of magnetic field effects on chemiluminescent fluid solutions, Atkins and Evans considered the spin-dependent interactions between two triplets, incorporating the effects of the diffusion of the molecules in the liquid phase. Their results, crucial for the advancement of photochemical upconversion, have received renewed attention due to the increasing interest in triplet-triplet annihilation for photovoltaic and optoelectronic applications. Here we revisit their approach, using a modern formulation of open quantum system dynamics and extend their results. We provide corrections to the theory of the magnetic field response of the fluorescent triplet pair state with singlet multiplicity. These corrections are timely, as improvements in the precision and range of available experimental methods are supported by the determination of quantitatively accurate rotational and interaction model parameters. We then extend Atkins and Evans' theory to obtain the magnetic field response of triplet pair states with triplet and quintet multiplicity. Although these states are not optically active, transitions between them are becoming imperative to study the working mechanism of spin-mediated upconversion and downconversion processes, thanks to advances in electron spin resonance and time-resolved transient absorption spectroscopy.