Triplet-triplet Annihilation-based Photon Upconversion Research Articles

Ligand-Directed Self-Assembly of Organic-Semiconductor/Quantum-Dot Blend Films Enables Efficient Triplet Exciton-Photon Conversion.

Blends comprising organic semiconductors and inorganic quantum dots (QDs) are relevant for many optoelectronic applications and devices. However, the individual components in organic-QD blends have a strong tendency to aggregate and phase-separate during film processing, compromising both their structural and electronic properties. Here, we demonstrate a QD surface engineering approach using electronically active, highly soluble semiconductor ligands that are matched to the organic semiconductor host material to achieve well-dispersed inorganic-organic blend films, as characterized by X-ray and neutron scattering, and electron microscopies. This approach preserves the electronic properties of the organic and QD phases and also creates an optimized interface between them. We exemplify this in two emerging applications, singlet-fission-based photon multiplication (SF-PM) and triplet-triplet annihilation-based photon upconversion (TTA-UC). Steady-state and time-resolved optical spectroscopy shows that triplet excitons can be transferred with near unity efficiently across the organic-inorganic interface, while the organic films maintain efficient SF (190% yield) in the organic phase. By changing the relative energy between organic and inorganic components, yellow upconverted emission is observed upon 790 nm NIR excitation. Overall, we provide a highly versatile approach to overcome longstanding challenges in the blending of organic semiconductors with QDs that have relevance for many optical and optoelectronic applications.

Triplet-triplet annihilation-based photon upconversion using nanoparticles and nanoclusters.

The phenomenon of photon upconversion (UC), generating high-energy photons from low-energy photons, has attracted significant attention. In particular, triplet-triplet annihilation-based UC (TTA-UC) has been achieved by combining the excitation states of two types of molecules, called the sensitizer and emitter (or annihilator). With TTA-UC, it is possible to convert weak, incoherent near-infrared (NIR) light, which constitutes half of the solar radiation intensity, into ultraviolet and visible light that are suitable for the operation of light-responsive functional materials or devices such as solar cells and photocatalysts. Research on TTA-UC is being conducted worldwide, often employing materials with high intersystem crossing rates, such as metal porphyrins, as sensitizers. This review summarizes recent research and trends in triplet energy transfer and TTA-UC for semiconductor nanoparticles or nanocrystals with diameters in the nanometer range, also known as quantum dots, and for ligand-protected metal nanoclusters, which have even smaller well-defined sub-nanostructures. Concerning nanoparticles, transmitter ligands have been applied on the surface of the nanoparticles to efficiently transfer triplet excitons formed inside the nanoparticles to emitters. Applications are expanding to solid-state UC devices that convert NIR light to visible light. Additionally, there is active research in the development of sensitizers using more cost-effective and environmentally friendly elements. Regarding metal nanoclusters, methods have been established for the evaluation of excited states, deepening the understanding of luminescent properties and excited relaxation processes.

Enhanced chiroptic properties of nanocomposites of achiral plasmonic nanoparticles decorated with chiral dye-loaded micelles

The development of circularly polarized luminescence (CPL)-active materials with both large luminescence dissymmetry factor (glum) and high emission efficiency continues to be a major challenge. Here, we present an approach to improve the overall CPL performance by integrating triplet-triplet annihilation-based photon upconversion (TTA-UC) with localized surface plasmon resonance. Dye-loaded chiral micelles possessing TTA-UC ability are designed and attached on the surface of achiral gold nanorods (AuNRs). The longitudinal and transversal resonance peaks of AuNRs overlap with the absorption and emission of dye-loaded chiral micelles, respectively. Typically, 43-fold amplification of glum value accompanied by 3-fold enhancement of upconversion are obtained simultaneously when Au@Ag nanorods are employed in the composites. More importantly, transient absorption spectra reveal a fast accumulation of spin-polarized triplet excitons in the composites. Therefore, the enhancement of chirality-induced spin polarization should be in charge of the amplification of glum value. Our design strategy suggests that combining plasmonic nanomaterials with chiral organic materials could aid in the development of chiroptical nanomaterials.

A supramolecular assembly-based strategy towards the generation and amplification of photon up-conversion and circularly polarized luminescence.

For the molecular properties in which energy transfer/migration is determinantal, such as triplet-triplet annihilation-based photon up-conversion (TTAUC), the overall performance is largely affected by the intermolecular distance and relative molecular orientations. In such scenarios, tools that may steer the intermolecular interactions and provide control over molecular organisation in the bulk, become most valuable. Often these non-covalent interactions, found predominantly in supramolecular assemblies, enable pre-programming of the molecular network in the assembled structures. In other words, by employing supramolecular chemistry principles, an arrangement where molecular units are arranged in a desired fashion, very much like a Lego toy, could be achieved. This leads to enhanced energy transfer from one molecule to other. In recent past, chiral luminescent systems have attracted huge attention for producing circularly polarized luminescence (CPL). In such systems, chirality is a necessary requirement. Chirality induction/transfer through supramolecular interactions has been known for a long time. It was realized recently that it may help in the generation and amplification of CPL signals as well. In this review article we have discussed the applicability of self-/co-assembly processes for achieving maximum TTA-UC and CPL in various molecular systems.

Photon Upconversion with a Low Threshold Excitation Intensity in Plain Water.

A triplet-triplet annihilation-based photon upconversion (TTA-UC) system with a low threshold excitation intensity (Ith) in plain water was developed. Water-soluble anionic porphyrin (PdTPPS4-) and diphenylanthracene (DCDPA2-) derivatives were used as light absorbers and emitter molecules, respectively, and no additives such as surfactants were required. The phosphorescence emission from PdTPPS4- under an excitation wavelength of 528 nm was quenched by DCDPA2-, resulting in triplet energy transfer, whereas fluorescence from DCDPA2- was observed in a short wavelength region (400-500 nm). Three independent emission studies utilizing different excitation light sources validated the TTA-UC process in a simple aqueous solution. TTA occurred after the triplet energy transfer, according to the time profiles of phosphorescence and fluorescence detected following pulse laser excitation. The Ith for TTA-UC was estimated to be lower than 6 mW cm-2, although it could not be exactly determined due to the sensitivity limit of the experimental setup. The upper limit of Ith for the aqueous solution of DCDPA2- and PdTPPS4- is the smallest value obtained to date for aqueous systems and comparable to that of high-performance TTA-UC systems in organic solutions.

Design Guidelines for Rigid Epoxy Resins with High Photon Upconversion Efficiency: Critical Role of Emitter Concentration.

For the practical application of triplet-triplet annihilation-based photon upconversion (TTA-UC), the development of rigid, transparent, air-stable, and moldable materials with a high TTA-UC efficiency remains a challenging issue. In addition to the noncovalent introduction of ionic liquid emitters into the epoxy network, we covalently introduce emitters with polymerization sites to increase the emitter concentration to 35.6 wt %. A TTA-UC quantum yield ΦUC of 5.7% (theoretical maximum: 50%) or a TTA-UC efficiency ηUC of 11.4% (theoretical maximum: 100%) is achieved, which is the highest value ever achieved for a rigid polymer material. More importantly, the high emitter concentration speeds up the triplet diffusion and suppresses the back energy transfer from the emitter to sensitizer so that the sensitized emitter triplet can be effectively utilized for TTA. The generality of our finding is also confirmed for epoxy resins of similar emitter unit concentrations without the ionic liquid. This work provides important design guidelines for achieving highly efficient TTA-UC in rigid solid materials, which has been very difficult to achieve in the past. Furthermore, the solid-state TTA-UC exhibits high air stability, reflecting the high oxygen barrier performance of epoxy resins. The high moldability of epoxy resins allows the construction of upconversion materials with complex geometries at nano- to macroscopic scales.

Block Copolymer Stabilized Liquid Nanodroplets Facilitate Efficient Triplet Fusion-Based Photon Upconversion in Solid Polymer Matrices.

Sensitized triplet-triplet annihilation-based photon upconversion is a photophysical process that affords anti-Stokes-shifted emission after annihilation of two metastable triplet excitons of an emitter dye and the formation of a fluorescent singlet state. While this process readily occurs in solutions under conditions where the mobility of the dye molecules is high, particular architectures are required to facilitate efficient energy transfers in solid polymers. One possibility is to incorporate liquid upconverting domains into solid polymer matrices. Another possibility is to reduce the intermolecular distance between the dyes below the Dexter radius, allowing exciton migration via triplet hopping. We introduce herein nanostructured materials that combine both of these features. These glassy nanostructured polymer systems contain liquid upconverting nanodroplets that are stabilized with a block copolymer surfactant and are fabricated under ambient conditions in a facile one-step protocol. The dyes concentrate in the nanostructured liquid domains, and this enables hopping-mediated ET and TTA between the dyes and leads to an upconversion efficiency of ∼20%.

Singlet-to-Triplet Absorption for Near-Infrared-to-Visible Photon Upconversion

Abstract This review highlights the advancement of molecular triplet donors showing singlet-to-triplet (S–T) absorption and their utilization for triplet-triplet annihilation-based photon upconversion (TTA-UC). Circumvention of thermal energy loss associated with intersystem crossing (ISC) through the use of S–T absorption results in UC from near-infrared (NIR) light to yellow, blue, and even violet light, achieving an unprecedentedly large UC spectral shift. Taking advantage of the molecular donor's ability to be dispersed in solids without aggregation, efficient solid-state UC materials are also achieved.

Green-to-UV photon upconversion enabled by new perovskite nanocrystal-transmitter-emitter combination.

The first example of triplet-triplet annihilation-based photon upconversion (TTA-UC) from green light to ultraviolet (UV) light sensitized by lead halide perovskite nanocrystals is demonstrated. The combination of a new transmitter that extracts triplet energy from perovskite and a UV emitter with a low triplet energy level lengthens the excitation wavelength of perovskite-sensitized upconverted UV emission.

Discovery of Key TIPS‐Naphthalene for Efficient Visible‐to‐UV Photon Upconversion under Sunlight and Room Light**

While many studies have been done on triplet-triplet annihilation-based photon upconversion (TTA-UC) to produce visible light with high efficiency, the efficient TTA-UC from visible to UV light, despite its importance for a variety of solar and indoor applications, remains a challenging task. Here, we report the highest visible-to-UV TTA-UC efficiency of 20.5 % based on the discovery of an excellent UV emitter, 1,4-bis((triisopropylsilyl)ethynyl)naphthalene (TIPS-Nph). TIPS-Nph is an acceptor with desirable features of high fluorescence quantum yield and high singlet generation efficiency by TTA. TIPS-Nph has a low enough triplet energy level to be sensitized by Ir(C6)2 (acac), a superior donor that does not quench UV emission. The combination of TIPS-Nph and Ir(C6)2 (acac) realizes the efficient UV light production even with weak light sources such as an AM 1.5 solar simulator and room LEDs.

On the size-dependence of CdSe nanocrystals for photon upconversion with anthracene.

In triplet-triplet annihilation based photon upconversion, controlling triplet energy transfer (TET) through the system is key to unlocking higher efficiencies. In this work, we vary the size of colloidally synthesized CdSe nanocrystals (NCs) to examine the effects on TET during photon upconversion, using steady-state measurements and transient absorption spectroscopy. As the CdSe NC size increases, the photon upconversion quantum yield (QY) decreases due to the decrease in the rate of TET from CdSe to the surface bound anthracene transmitter ligand, as expected for the Marcus description of energy transfer from the transmitter to the NC. Long microsecond transmitter lifetimes are critical to high photon upconversion QYs.

Perovskite-sensitized upconversion bingo: Stoichiometry, composition, solvent, or temperature?

Triplet-triplet annihilation-based photon upconversion (UC) using bulk perovskite sensitizers has been previously shown to facilitate efficient UC at low fluences. However, the fabrication of the UC devices has not been fully optimized; thus, there is room for improvement. Here, we apply techniques that have been successful in enhancing the performance of perovskite solar cells in order to also improve perovskite-sensitized UC devices. In particular, we investigate the use of a post-fabrication thermal annealing step, overstoichiometric vs stoichiometric addition of PbI2 to the perovskite precursors, methylammonium vs formamidinium cation-rich lead halide perovskite compositions, and the use of different solvents for the annihilator molecules on the perovskite/annihilator interface. We find that excess PbI2 does not significantly affect the UC process, while the perovskite composition is crucial for the yield of extracted carriers across the interface. Comparing toluene and chlorobenzene, we find that the solvent used to deposit the annihilator is also a key factor in the overall device performance. Moreover, we find that thermal annealing of the whole device architecture significantly improves the UC performance by a factor of three.

Micelles Embedded in Multiphasic Protein Hydrogel Enable Efficient and Air-Tolerant Triplet Fusion Upconversion with Heavy-Atom and Spin-Orbit Charge-Transfer Sensitizers.

The applications of triplet-triplet annihilation-based photon upconversion (TTA-UC) in solar devices have been limited by the challenges in designing a TTA-UC system that is efficient under aerobic conditions. Efficient TTA-UC under aerobic conditions is typically accomplished by using soft matter or solid-state media, which succeed at protecting the triplet excited states of upconverters (sensitizer and annihilator) from quenching by molecular oxygen but fail at preserving their mobility, thus limiting the TTA-UC efficiency (ΦUC). We showcase a protein/lipid hydrogel that succeeded in doing both of the above due to its unique multiphasic design, with a high ΦUC of 19.0 ± 0.7% using a palladium octaethylporphyrin sensitizer. This hydrogel was made via an industrially compatible method using low-cost and eco-friendly materials: bovine serum albumin (BSA), sodium dodecyl sulfate (SDS), and water. A dense BSA network provided oxygen protection while the encapsulation of upconverters within a micellar SDS environment preserved upconverter mobility, ensuring near-unity triplet energy transfer efficiency. In addition to heavy atom-containing sensitizers, several completely organic, spin-orbit charge-transfer intersystem crossing (SOCT-ISC) Bodipy-based sensitizers were also studied; one of which achieved a ΦUC of 3.5 ± 0.2%, the only reported SOCT-ISC-sensitized ΦUC in soft matter to date. These high efficiencies showed that our multiphasic design was an excellent platform for air-tolerant TTA-UC and that it can be easily adapted to a variety of upconverters.

Visible-to-UV Photon Upconversion in Nanostructured Chromophoric Ionic Liquids.

Invited for this month's cover picture is the group of Professor Nobuhiro Yanai and Nobuo Kimizuka at Kyushu University. The cover picture shows visible-to-ultraviolet (vis-to-UV) triplet-triplet annihilation-based photon upconversion (TTA-UC) via triplet exciton diffusion in a chromophoric ionic liquid (IL). Chromophore moieties spontaneously form continuous arrays in non-polar nano-domains of the IL. The close arrangement of the chromophores in the IL allowed effective diffusion of triplet excitons, resulting in the vis-to-UV TTA-UC at a low excitation intensity. Read the full text of their Communication at https://doi.org/10.1002/open.201900304.

Visible-to-UV Photon Upconversion in Nanostructured Chromophoric Ionic Liquids.

Visible‐to‐ultraviolet (vis‐to‐UV) triplet‐triplet annihilation based photon upconversion (TTA‐UC) is achieved in a non‐volatile chromophoric ionic liquid (IL) for the first time. A novel IL is synthesized by combining UV‐emitting anion 4‐(2‐phenyloxazol‐5‐yl)benzenesulfonate (PPOS) and trihexyltetradecylphosphonium cation (P66614). The nanostructured organization of chromophoric anions is demonstrated by synchrotron X‐ray and optical measurements. When the IL is doped with a triplet sensitizer tris(2‐phenylpyridinato)iridium(III) (Ir(ppy)3), the visible‐to‐UV TTA‐UC with a relatively low threshold excitation intensity of 61 mW cm−2 is achieved. This is due to a large triplet diffusion coefficient in the IL (1.4×10−7 cm2 s−1) as well as a high absorption coefficient 15 cm−1 and a long PPOS triplet lifetime of 1.55 ms, all implemented in the condensed IL system. This work demonstrates the unique potential of ILs to control chromophore arrangements for desired functions.

Recent Progress in Photon Upconverting Gels.

Recent progress in the development of gels showing triplet-triplet annihilation based photon upconversion (TTA-UC) is reviewed. Among the two families of upconverting gels reported, those display TTA-UC based on molecular diffusion show performances comparable to those in solutions, and the TTA-UC therein are affected by dissolved molecular oxygen. Meanwhile, air-stable TTA-UC is achieved in organogels and hydrogels by suitably accumulating TTA-UC chromophores which are stabilized by hydrogen bonding networks of the gelators. The unique feature of the air-stable upconverting gels is that the self-assembled nanostructures are protected from molecular oxygen dissolved in the microscopically interconnected solution phase. The presence of the bicontinuous structures formed by the upconverting fibrous nanoassemblies and the solution phase is utilized to design photochemical reaction systems induced by TTA-UC. Future challenges include in vivo applications of hydrogels showing near infrared-to-visible TTA-UC.

Front Cover: Supramolecular Crowding Can Avoid Oxygen Quenching of Photon Upconversion in Water (Chem. Eur. J. 24/2019)

Air-stable, triplet-triplet annihilation-based photon upconversion (TTA-UC) has been achieved in water by reinforcing cationic acceptor self-assemblies with fatty acid anions. More than 70% of the TTA-UC emission is maintained in air-saturated water, indicating that the supramolecular crowding by ion-paring provided a physical barrier to the partition of dissolved oxygen to the self-assembled chromophores. More information can be found in the Full Paper by N. Yanai, N. Kimizuka, et al. on page 6124.

Oligo(ethylene glycol)/alkyl-modified Chromophore Assemblies for Photon Upconversion in Water.

Molecular self-assembly is a powerful means to construct nanoscale materials with advanced photophysical properties. Although the protection of the photo-excited states from oxygen quenching is a critical issue, it still has been in an early phase of development. In this work, we demonstrate that a simple and typical molecular design for aqueous supramolecular assembly, modification of the chromophoric unit with hydrophilic oligo(ethylene glycol) chains and hydrophobic alkyl chains, is effective to avoid oxygen quenching of triplet-triplet annihilation-based photon upconversion (TTA-UC). While a TTA-UC emission is completely quenched when the donor and acceptor are molecularly dispersed in chloroform, their aqueous co-assemblies exhibit a clear upconverted emission in air-saturated water even under extremely low chromophore concentrations down to 40 μm. The generalization of this nano-encapsulation approach offers new functions and applications using oxygen-sensitive species for supramolecular chemistry.

Direct triplet sensitization of oligothiophene by quantum dots.

Effective sensitization of triplet states is essential to many applications, including triplet-triplet annihilation based photon upconversion schemes. This work demonstrates successful triplet sensitization of a CdSe quantum dot (QD)-bound oligothiophene carboxylic acid (T6). Transient absorption spectroscopy provides direct evidence of Dexter-type triplet energy transfer from the QD to the acceptor without populating the singlet excited state or charge transfer intermediates. Analysis of T6 concentration dependent triplet formation kinetics shows that the intrinsic triplet energy transfer rate in 1 : 1 QD-T6 complexes is 0.077 ns-1 and the apparent transfer rate and efficiency can be improved by increasing the acceptor binding strength. This work demonstrates a new class of triplet acceptor molecules for QD-based upconversion systems that are more stable and tunable than the extensively studied polyacenes.

Solid-State Photon Upconversion Materials: Structural Integrity and Triplet-Singlet Dual Energy Migration.

Triplet-triplet annihilation-based photon upconversion (TTA-UC) is a process wherein longer-wavelength light (lower-energy photons) is converted into shorter-wavelength light (higher-energy photons) under low excitation intensity in multichromophore systems. There have been many reports on highly efficient TTA-UC in solution; however, significant challenges remain in the development of solid-state upconverters in order to explore real-world applications. In this Perspective, we discuss the advantages and challenges of different approaches for TTA-UC in solvent-free solid systems. We consider that the energy migration-based TTA-UC has the potential to achieve ideal materials with high UC efficiency at weak solar irradiance. While the UC performance of such systems is still limited at this moment, we introduce recently developed important concepts to improve it, including kinetic/thermodynamic donor dispersion in acceptor assemblies, defectless crystals, and triplet-singlet dual energy migration. Future integration of these concepts into a single material would realize the ideal TTA-UC system.