Upconversion Applications Research Articles

Uncovering upconversion photoluminescence in layered PbI2 above room temperature.

As a van der Waals (vdW) layered semiconductor material, lead iodide (PbI2) possessing a direct bandgap with strong photoluminescence emission in visible range has gained wide attention in applications of photonic and optoelectronic devices. Here, upconversion photoluminescence (UPL) in exfoliated PbI2 flakes is demonstrated at room temperature and elevated temperatures. The linear power dependence of UPL emission with 532nm excitation suggests the one-photon involved multiphonon-assisted UPL emission process, which is revealed by the temperature-dependent UPL emission measurement. Meanwhile, the nonlinear power dependence of UPL emission with 561nm excitation indicates the transition of UPL emission mechanism from linear to nonlinear regime, and the temperature-dependent UPL emission study further shows that the upconversion is contributed by both the multiphonon-assisted UPL process and the two-photon absorption induced PL process. This study will provide an insight to the understanding of photon upconversion in vdW layered semiconductors and advancing applications in temperature-controlled photon upconversion, tunable photonics, photodetection and imaging.

(Invited) Innovative MOF-Based Strategies for Assembling Chromophores: Perspectives for Next-Generation Organic Electronics

In the realm of organic electronics, such as photovoltaics, photodetectors, and light-emitting devices, the integration of organic chromophores into solid-state assemblies and their connection with electrodes is crucial. A notable development in this area is the use of metal-organic frameworks (MOFs), also referred to as the MOF method [1], which has been gaining traction. This approach involves using organic chromophores like anthracene and other planar aromatics, including Hexa-peri-hexabenzocoronene (HBC), equipped with coupling units, to create ditopic linkers that connect with metal-oxo nodes in MOFs. In view of the challenges of integrating MOF powders into devices, recent advancements have led to the development of layer-by-layer methods yielding high-quality, monolithic MOF thin films [2]. These films offer exceptional optical qualities and show, in many cases, a reduced density of defects.MOFs' periodic structures enable the deliberate design of chromophore assemblies, impacting optical absorption through inter-molecular interactions. This design approach has facilitated the creation of structures like J-aggregates, initially simulated in silico and later realized experimentally [3]. Additionally, MOFs enable the realization of band-structure phenomena, such as indirect band gaps [4], and chiroptical effects, including circularly polarized light emission [5] and the helical sensitivity in photodetectors [6].We've also explored lbl architectures for constructing heterostructures, useful in photon up-conversion applications. This involves leveraging MOFs' porous nature, as seen in the integration of C60 into SURMOF pores for applications like photoconductivity [7] and organic diodes [8]. Recent efforts have also focused on assembling non-centrosymmetric SURMOFs for nonlinear optical properties, demonstrating substantial second harmonic generation (SHG) activity [9].Our presentation will showcase key instances of successfully incorporating organic chromophores into SURMOFs for device fabrication, emphasizing the synergy with theoretical models. Given the vast number (> 120,000) of known MOFs, a theoretical approach is essential to guide experimental efforts efficiently.

Copper oxide coupled with photon upconversion for solar water splitting

Photoelectrochemical water splitting is a promising solution for harnessing solar radiation for hydrogen production. Copper oxide semiconductors, particularly materials based on cuprous oxide, have attracted attention due to their abundant elemental availability and scalable synthesis methods. To improve the generated photocurrent of the photoelectrode system, photon upconversion materials can be implemented into water-splitting devices. Here, we demonstrate the potential application of triplet-triplet annihilation-based upconversion in solar-assisted water splitting and highlight the significance of photonic designs to improve the light-harnessing properties of photoactive materials. The triplet-triplet annihilation mechanism is particularly suitable due to its efficient conversion at low photon intensity, namely under 1-sun illumination. Our results show that Cu2O coupled with an upconverter outperforms bare Cu2O by 56% in terms of produced photocurrent density. We construct a hybrid water-splitting device with an extended absorption range by utilizing a semi-transparent 600 nm Cu2O film with a 5 nm Au underlayer.

Engineering Metal Halide Perovskite Nanocrystals with BODIPY Dyes for Photosensitization and Photocatalytic Applications.

The sensitization of surface-anchored organic dyes on semiconductor nanocrystals through energy transfer mechanisms has received increasing attention owing to their potential applications in photodynamic therapy, photocatalysis, and photon upconversion. Here, we investigate the sensitization mechanisms through visible-light excitation of two nanohybrids based on CsPbBr3 perovskite nanocrystals (NC) functionalized with borondipyrromethene (BODIPY) dyes, specifically 8-(4-carboxyphenyl)-1,3,5,7-tetramethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BDP) and 8-(4-carboxyphenyl)-2,6-diiodo-1,3,5,7-tetramethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (I2-BDP), named as NC@BDP and NC@I2-BDP, respectively. The ability of I2-BDP dyes to extract hot hole carriers from the perovskite nanocrystals is comprehensively investigated by combining steady-state and time-resolved fluorescence as well as femtosecond transient absorption spectroscopy with spectroelectrochemistry and quantum chemical theoretical calculations, which together provide a complete overview of the phenomena that take place in the nanohybrid. Förster resonance energy transfer (FRET) dominates (82%) the photosensitization of the singlet excited state of BDP in the NC@BDP nanohybrid with a rate constant of 3.8 ± 0.2 × 1010 s-1, while charge transfer (64%) mediated by an ultrafast charge transfer rate constant of 1.00 ± 0.08 × 1012 s-1 from hot states and hole transfer from the band edge is found to be mainly responsible for the photosensitization of the triplet excited state of I2-BDP in the NC@I2-BDP nanohybrid. These findings suggest that the NC@I2-BDP nanohybrid is a unique energy transfer photocatalyst for oxidizing α-terpinene to ascaridole through singlet oxygen formation.

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.

Janus Micromotors for Photophoretic Motion and Photon Upconversion Applications Using a Single Near-Infrared Wavelength.

External stimuli can trigger changes in temperature, concentration, and momentum between micromotors and the medium, causing their propulsion and enabling them to perform different tasks with improved kinetic efficiencies. Light-activated micromotors are attractive systems that achieve improved motion and have the potential for high spatiotemporal control. Photophoretic swarming motion represents an attractive means to induce micromotor movement through the generation of temperature gradients in the medium, enabling the micromotors to move from cold to hot regions. The micromotors studied herein are assembled with Fe3O4 nanoparticles, and NaGdF4:Yb3+,Er3+/NaGdF4:Yb3+ and LiYF4:Yb3+,Tm3+ upconverting nanoparticles. The Fe3O4 nanoparticles were localized to one hemisphere to produce a Janus architecture that facilitates improved upconversion luminescence with the upconverting nanoparticles distributed throughout. Under 976 nm excitation, Fe3O4 nanoparticles generate the temperature gradient, while the upconverting nanoparticles produce visible light that is used for micromotor motion tracking and triggering of reactive oxygen species generation. As such, the motion and application of the micromotors are achieved using a single excitation wavelength. To demonstrate the practicality of this system, curcumin was adsorbed to the micromotor surface and degradation of Rhodamine B was achieved with kinetic rates that were over twice as fast as the static micromotors. The upconversion luminescence was also used to track the motion of the micromotors from a single image frame, providing a convenient means to understand the trajectory of these systems. Together, this system provides a versatile approach to achieving light-driven motion while taking advantage of the potential applications of upconversion luminescence such as tracking and detection, sensing, nanothermometry, particle velocimetry, photodynamic therapy, and pollutant degradation.

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.

Photophysics and its application in photon upconversion.

Photoluminescence (PL) upconversion is a phenomenon involving light-matter interaction, where the energy of the emitted photons is higher than that of the incident photons. PL upconversion has promising applications in optoelectronic devices, displays, photovoltaics, imaging, diagnosis and treatment. In this review, we summarize the mechanism of PL upconversion and ultrafast PL physical processes. In particular, we highlight the advances in laser cooling, biological imaging, volumetric displays and photonics.

Structure and luminescence of Pr3+-doped oxyfluoride glass-ceramics containing Na5Y9F32: Pr3+ nanocrystals

Oxyfluoride glass-ceramics have become a focal point of recent research, positioned to advance significantly in areas such as LED illumination and optical data storage, etc. This study successfully prepared Pr3+-doped fluorosilicate glass and glass-ceramics embedded Na5Y9F32 nanocrystals. The introduction of Pr2O3 into the glass matrix disturbs the network structure, leading to a reduction in the band gap from 3.66 eV to 3.42 eV. When subjected to 443 nm light excitation, the 1.0 mol% Pr3+-doped glass-ceramics crystallized at 690 °C for 1.0 h exhibit the most potent luminescence, displaying seven emission peaks resulting from the radiative transition of Pr3+ ions, manifesting yellowish-pink hues. Furthermore, when stimulated by a 450 nm LD, the glass-ceramics display a distinct emission peak at approximately ∼247 nm, attributed to the electron transitions of 4f5d → 3H4 for Pr3+ ions. The luminescent properties of these glass-ceramics embedded with Na5Y9F32 nanocrystals illustrate potential applications in up-conversion and down-conversion luminescence.

Developments and Challenges Involving Triplet Transfer across Organic/Inorganic Heterojunctions for Singlet Fission and Photon Upconversion.

In this Perspective, we provide an overview of recent advances in harvesting triplets for photovoltaic and photon upconversion applications from two angles. In singlet fission-sensitized solar cells, the triplets are harvested through a low band gap semiconductor such as Si. Recent literature has shown how a thin interlayer or orientation of the singlet fission molecule can successfully lead to triplet transfer. On the other hand, the integration of transition metal dichalcogenides (TMDCs) with suitable organic molecules has shown triplet-triplet annihilation upconversion (TTA-UC) of near-infrared photons. We consider the theoretical aspect of the triplet transfer process between a TMDC and organic semiconductors. We discuss possible bottlenecks that can limit the harvesting of energy from triplets and perspectives to overcome these.

Uncovering the Mechanisms of Triplet-Triplet Annihilation Upconversion Enhancement via Plasmonic Nanocavity Tuning.

The nonlinear conversion of photons from lower to higher energy is important for a wide range of applications, from quantum communications and optoelectronics to solar energy conversion and medicine. Triplet-triplet annihilation upconversion (TTA UC), which utilizes an absorber/emitter molecular pair, is a promising tool for upconversion applications requiring low intensity light such as photovoltaics, photocatalysis, and bioimaging. Despite demonstrations of efficient TTA UC in solution, practical applications have proven difficult, as thin films retard the necessary energy transfer steps and result in low emission yields. In this work, TTA UC emission from a thin film is greatly enhanced through integration into plasmonic nanogap cavities consisting of a silver mirror, a nanometer-scale polymer spacer containing a TTA molecular pair, and colloidally synthesized silver nanocubes. Mechanistic studies performed by varying the nanocube side length (45-150 nm) to tune the nanogap cavity resonance paired with simulations reveal absorption rate enhancement to be the primary operative mechanism in overall TTA UC emission enhancement. This absorption enhancement decreases the TTA UC threshold intensity by an order of magnitude and allows TTA UC emission to be excited with light up to 120 nm redder than the usable wavelength range for the control samples. Further, combined nanogap cavities composed of two distinct nanocube sizes result in surfaces which simultaneously enhance the absorption rate and emission rate. These dual-size nanogap cavities result in 45-fold TTA UC emission enhancement. In total, these studies present TTA UC emission enhancement, illustrate how the usable portion of the spectrum can be expanded for a given sensitizer-emitter pair, and develop both mechanistic understanding and design rules for TTA UC emission enhancement by plasmonic nanostructures.

Uncovering the mechanisms of efficient upconversion in two-dimensional perovskites with anti-Stokes shift up to 220 meV.

Phonon-assisted photon upconversion holds great potential for numerous applications, e.g., optical refrigeration. However, traditional semiconductors face energy gain limitations due to thermal energy, typically achieving only ~25 milli-electron volts at room temperature. Here, we demonstrate that quasi-two-dimensional perovskites, with a soft hybrid organic-inorganic lattice, can efficiently upconvert photons with an anti-Stokes shift exceeding 200 milli-electron volts. By using microscopic transient absorption measurements and density functional theory calculations, we explicate that the giant energy gain stems from strong lattice fluctuation leading to a picosecond timescale transient band energy renormalization with a large energy variation of around ±180 milli-electron volts at room temperature. The motion of organic molecules drives the deformation of inorganic framework, providing energy and local states necessary for efficient upconversion within a time constant of around 1 ps. These results establish a deep understanding of perovskite-based photon upconversion and offer previously unknown insights into the development of various upconversion applications.

Phonon-assisted upconversion photoluminescence of monolayer MoS2 at elevated temperatures.

Upconversion photoluminescence (UPL) lies at the heart of optical refrigeration and energy harvesting. Monolayer transition metal dichalcogenides (TMDCs) have been identified as an excellent platform with robust phonon-exciton coupling for studying the phonon-assisted UPL process. Herein, we investigate the multiphonon-assisted UPL emission in monolayer MoS2 at elevated temperatures and the temperature-dependent phonon contributions in the UPL process. When temperature goes up from 295 K to 460 K, the enhancement of the integrated UPL intensity is demonstrated due to the increased phonon population and the reduced phonon numbers involved in the UPL process. Our findings reveal the underlying mechanism of phonon-assisted UPL at high temperatures, and pave the way for the applications of photon upconversion in display, nanoscale thermometry, anti-Stokes energy harvesting, and optical refrigeration.

Optical coherence in the upconversion luminescence of Er[formula omitted

Trivalent lanthanide ions exhibit the ability to convert near-infrared absorption into visible radiation through photon upconversion. Despite decades of extensive investigations, the role of optical coherence in this process has been overlooked. Here, we investigate the spatial coherence of upconversion photoluminescence from Erbium (Er3+) ions. Experimental results and simulations reveal that the emitted light displays correlations over longer distances than expected from an incoherent source. Moreover, the Er3+ emission profile exhibits two prominent spectral features at room temperature. Leveraging the bimodal nature of Er3+ luminescence, we observe coherence-induced modifications in the far-field spectrum, typically associated with broadband sources. These findings highlight the overlooked coherence properties of trivalent lanthanide ions and their potential impact on photon upconversion applications.

High-Level Reverse Intersystem Crossing and Molecular Rigidity Improve Spin Statistics for Triplet-Triplet Annihilation Upconversion.

The structural factors affecting triplet-triplet annihilation (TTA) at the molecular level are not well-understood. Here, our steady-state photoluminescence and transient absorption results demonstrate that the spin statistical factor, η, decreases from 0.60 to 0.46 and 0.14 going from 9,10-diphenylanthracene (DPA) to the 1,5-DPA and 2,6-DPA isomers, respectively, during photon upconversion with a platinum octaethylporphyrin sensitizer. Density functional theory (DFT) shows that η depends on the energetics of hot triplet states and molecular rigidity. The significantly high conical intersection energy between the S0 and T1 states for 9,10-DPA gives its longer triplet lifetime. Time-dependent DFT calculations show that 9,10-DPA and 1,5-DPA can undergo high-level reverse intersystem crossing from their T2 and T3 states, respectively, to the bright S1 state, increasing the limit of the spin statistical factor. Both factors ultimately serve to enhance the TTA efficiency. This work provides insight into designing molecules for efficient light-emitting and photon upconversion applications.

Role of Semiconductor Nanostructures in Photon Upconversion Applications

Role of Semiconductor Nanostructures in Photon Upconversion Applications

Growth phase diagram and X-ray excited luminescence properties of NaLuF4:Tb3+ nanoparticles

X-rays are energy sources exhibiting extended penetration depths, and they have attracted increasing attention in industry and for clinical application. With the rapid development of nanomaterials and X-ray excited luminescent nanoparticles (XLNPs), new modalities for bioimaging and cancer therapy have been developed, such as X-ray luminescent computed tomography (XLCT) and X-ray excited photodynamic therapy (X-PDT). To meet the requirements of biomedical applications, XLNPs must exhibit high luminescence intensities, appropriate size distributions (less than100 nm) and negligible cytotoxicity. Due to the optical properties associated with f-electrons, rear earth (RE) elements are highly suitable for creating XLNPs. NaREF4 nanoparticles (NPs) have been shown to be suitable hosts with high luminescence intensities, controllable sizes, and biocompatibility for X-ray-based biomedical applications. Syntheses of NaLuF4 NPs doped with rare earth elements for upconversion applications have been systematically studied. However, for X-ray excited applications, the doping levels of the NPs must be totally different, which greatly affects the morphologies and sizes of the NaLuF4 NPs. Thus, in this paper, nucleation, phase transitions, morphologies and sizes, and luminescence properties of Tb3+-doped NaLuF4 NPs were systematically studied. OA-capped NaLuF4:Tb3+ NPs were synthesized via coprecipitation processes with different reaction temperatures and reaction times to study the nucleation mechanism systematically, and the morphologies, size distributions and crystal phases were characterized with TEM and XRD. The morphologies, size distributions and crystal phases of these NPs were seriously influenced by the reaction temperature and reaction time. At 295 ℃, the NP sizes increased with prolonged reaction time, and the crystalline phase was a mixture of cubic and hexagonal phases. At 300 ℃ and 310 ℃, the pure hexagonal phase was obtained after 20 min and 35 min reaction times, respectively. The luminescence strengths of these NPs were associated with the particle sizes, crystalline phases, and Tb3+ doping levels. Stronger luminescence was achieved with larger particle sizes and purer hexagonal crystal phases. In addition, the 15 % doping level for Tb3+ provided the maximum luminescence intensity. The present work provides insights into the mechanism of NaLuF4:Tb3+ nanocrystal growth.

Highly Efficient Triplet–Triplet Annihilation Upconversion with a Thermally Activated Delayed Fluorescence Molecule as Triplet Photosensitizer

Thermally activated delayed fluorescence (TADF) molecules have great potential for practical applications as triplet photosensitizers, owing to their long triplet lifetimes, almost negligible energy loss in intersystem crossing, and excellent light-harvesting ability. Recently, several triplet–triplet annihilation (TTA) upconversion systems using the TADF photosensitizer have been reported. To provide comprehensive dynamic information for designing an optimized system in the future, more experiments with the new TADF photosensitizers are necessary. Herein, we conducted a new TTA upconversion system with a recently developed TADF molecule, DMACPDO, as the triplet photosensitizer and 9,10-diphenylanthracene (DPA) as the annihilator. The overall upconversion yield was determined to be relatively high, e.g., 22.3% in toluene, 21.9% in benzene, and 8.1% in chlorobenzene. By examining elementary photophysical and photochemical processes with time-resolved transient absorption and fluorescence emission spectroscopy, we revealed the influence of solvent polarity and viscosity on each step. Our conclusion highlights the elusive solvent effect in TTA upconversion application of the TADF photosensitizer.

Electric field induced release of guest molecules from clathrate hydrates and its consequences for electrochemical CO2 conversion

When CO2 is encapsulated in clathrate hydrate, where the concentration is nearly-two orders of magnitude greater than in saturated aqueous solution, the rate of the CO2 reduction reaction (CO2RR) increases, and the corresponding Faradaic efficiency becomes up to three times higher than that of the competing hydrogen evolution reaction (HER) at applied potential of −0.5 to −0.7 vs RHE. The energy efficiency of the CO2RR is correspondingly increased. The enhanced CO2RR in clathrate is ascribed to non-equilibrium release of the CO2 due to the electric field near the electrode, analogous to what has been observed recently for tetrahydrofuran [Li et al. J. Phys. Chem. Letters 125, 13802 (2021)]. This raises the chemical potential of CO2 beyond that of saturated aqueous solution, thereby reversing the relative rates of the CO2RR and the HER. The experimental demonstration of this release mechanism for the application of CO2 up-conversion illustrates how the electric field can not only influence electrochemical reactions at the surface but also the reactant supply from clathrate hydrates to the surface. Experimental focus rests on the low applied-potential regime, where the consequences of the reactant release mechanism are well-observable unobscured by mass-transport effects.

Triplet generation at the CdTe quantum dot/anthracene interface mediated by hot and thermalized electron exchange for enhanced production of singlet oxygen.

Triplet energy transfer (TET) from semiconductor quantum dots (QDs) to molecular triplets has potential applications in photon up-conversion and singlet oxygen generation. Here, we have constructed a complex consisting of CdTe QDs as the donor and 9-anthracenecarboxylic acid (ACA) as the triplet acceptor, and studied the TET pathways and enhanced singlet oxygen generation properties. The results from steady-state and time-resolved spectroscopy demonstrate efficient TET with a total efficiency of over 80% from photoexcited CdTe QDs to ACA. Dynamical analysis clearly indicates two distinctive TET channels - hot electron exchange and thermalized electron exchange - mediating the TET process in the CdTe QDs-ACA complex. The TET efficiencies from hot electron exchange at high energetic levels and thermalized electron exchange on the lowest exciton state can reach ∼27% and ∼85%, respectively, following 530 nm excitation. This efficient TET endows the CdTe QDs-ACA complex with a good capability of generating singlet oxygen species with a yield of up to ∼59%. These findings contribute further insights to the mechanisms of interfacial TET processes and are significant in designing efficient TET systems based on semiconductor nanoparticles and triplet molecules.