Upconversion Quantum Yield Research Articles

Efficient Triplet-Triplet Annihilation Upconversion with an Anti-Stokes Shift of 1.08 eV Achieved by Chemically Tuning Sensitizers.

A series of Pt(II)-Schiff base complexes were synthesized as triplet sensitizers for the purpose of tuning the singlet and triplet energy levels so as to minimize energy loss during triplet-triplet annihilation (TTA) upconversion (UC). A deep-red to blue TTA-UC was achieved with an unprecedentedly large anti-Stokes shift of 1.08 eV. UC quantum yields of up to 21% (with a theoretical maximum efficiency of 50%) were observed in solution. The complexes also showed efficient UC emission in air-saturated hydrogels with a UC quantum yield up to 14.8%, which is much higher than the highest previously reported value. The low threshold excitation intensity provided by the present system offers promising potential for application in terrestrial solar energy conversion.

Bodipy−Corrole dyad with truxene bridge: Photophysical Properties and Application in Triplet−Triplet Annihilation upconversion

Free base corrole can generate triplet state without relying on the heavy-atom effect, however, its absorption in the visible spectral range (430–650 nm) is very weak which makes corrole not an ideal triplet photosensitizer. Herein, we prepared a novel truxene-bridged Bodipy−corrole dyad (B−T−Co) which have strong, broad absorption in Uv–visible spectral range (300 nm − 676 nm, the maximum molar absorption coefficient is up to 1.09 − 105 M−1 cm−1 at 426 nm). The dyad showed fast singlet-singlet energy transfer from Bodipy moiety to corrole moiety (2.16 − 108 s−1), high strong singlet-oxygen (1O2) photosensitizing ability (70%), prolonged triplet state lifetimes (149 μs) and high triplet state energy levels (1.41 eV) as compared to corrole (singlet-oxygen photosensitizing ability: 58%; triplet lifetimes: 116 μs; triplet energy levels: 1.32 eV). Moreover, the dyad used as triplet photosensitizer for triplet−triplet annihilation upconversion, with red excitation at 589 nm, the upconversion emission intensity is higher than the corrole itselef and the upconversion quantum yield (2.57%) increases by ca. 2-folds.

Hetero-bichromophore Dyad as a Highly Efficient Triplet Acceptor for Polarity Tuned Triplet–Triplet Annihilation Upconversion

Triplet-triplet annihilation upconversion (TTA UC) was intensively investigated for developing efficient photosensitizers and emitters. But an emission wavelength tunable TTA UC system with only one emitter was rarely reported. A novel hetero-bichromophore dyad, HB-An, showing solvatochromic emission and high fluorescence quantum yields in weakly polar solvents (such as n-hexane, dichloromethane (DCM), and so on) was used as triplet energy acceptor/emitter for polarity tuned TTA UC. A high TTA UC quantum yield up to 25% was achieved and the UC emission wavelengths can be fine-tuned from cyan to yellow by changing the media polarity. This information will be useful for constructing efficient emitting-light-tunable TTA UC system.

Small Alkaline-Earth-based Core/Shell Nanoparticles for Efficient Upconversion.

The optical efficiency of lanthanide-based upconversion is intricately related to the crystalline host lattice. Different crystal fields interacting with the electron clouds of the lanthanides can significantly affect transition probabilities between the energy levels. Here, we investigate six distinct alkaline-earth rare-earth fluoride host materials (M1- xLn xF2+x, MLnF) for infrared-to-visible upconversion, focusing on nanoparticles of CaYF, CaLuF, SrYF, SrLuF, BaYF, and BaLuF doped with Yb3+ and Er3+. We first synthesize ∼5 nm upconverting cores of each material via a thermal decomposition method. Then we introduce a dropwise hot-injection method to grow optically inert MYF shell layers around the active cores. Five distinct shell thicknesses are considered for each host material, resulting in 36 unique, monodisperse upconverting nanomaterials each with size below ∼15 nm. The upconversion quantum yield (UCQY) is measured for all core/shell nanoparticles as a function of shell thickness and compared with hexagonal (β-phase) NaGdF4, a traditional upconverting host lattice. While the UCQY of core nanoparticles is below the detection limit (<10-5%), it increases by 4 to 5 orders of magnitude as the shell thickness approaches 4-6 nm. The UCQY values of our cubic MLnF nanoparticles meet or exceed the β-NaGdF4 reference sample. Across all core/shell samples, SrLuF nanoparticles are the most efficient, with UCQY values of 0.53% at 80 W/cm2 for cubic nanoparticles with ∼11 nm edge length. This efficiency is 5 times higher than our β-NaGdF4 reference material with comparable core size and shell thickness. Our work demonstrates efficient and bright upconversion in ultrasmall alkaline-earth-based nanoparticles, with applications spanning biological imaging and optical sensing.

Photophysics of Phosphorus Corroles and Application of the Compounds in Triplet-Triplet Annihilation Upconversion

Triplet-triplet annihilation upconversion (TTA-UC) is in particular of interest, due to the strong absorption of the excitation light and the high upconversion quantum yields.[1,2] For TTA-UC, a proper triplet photosensitizer and a triplet acceptor are combined to perform the cascade photophysical processes to convert the photons with lower energy to photons with higher energy. Triplet photosensitizers are crucial for TTA-UC. The conventional triplet photosensitizers used for TTA-UC are transition metal complexes or organic compounds containing iodine or bromine atoms.[3] The rationales to use the heavy atoms are to employ the heavy atom effect to facilitate the ISC for triplet state formation upon photoexcitation. Heavy atom-free organic compounds were rarely used as triplet photosensitizers because the ISC is almost unpredictable without the heavy atom effect.[4] Free base corrole is tetrapyrrolic macrocycle with one meso carbon less than porphyrins. Corrole compounds usually show strong absorption of visible light and high photo-stability, as well as efficient ISC. However, corroles were rarely used as triplet photosensitizers for TTA-UC. Herein we studied the photophysical properties of series of corroles with steady state and time-resolved spectroscopies. The corroles were used as triplet photosensitizers for TTA-UC, with perylenebisimide (PBI) as the triplet acceptor. Upon 589 nm cw-laser excitation, upconversion emission at 520 nm was observed. The upconversion quantum yield was determined as 1%.

Band Gap Engineering Improves the Efficiency of Double Quantum Dot Upconversion Nanocrystals

AbstractSolution‐processed core/multishell semiconductor quantum dots (QDs) could be tailored to facilitate the carrier separation, promotion, and recombination mechanisms necessary to implement photon upconversion. In contrast to other upconversion schemes, upconverting QDs combine the stability of an inorganic crystalline structure with the spectral tunability afforded by quantum confinement. Nevertheless, their upconversion quantum yield (UCQY) is fairly low. Here, design rules are uncovered that enable to significantly enhance the performance of double QD upconversion systems, and these findings are leveraged to fabricate upconverting QDs with increased photon upconversion efficiency and reduced saturation intensities under pulsed excitation. The role of the intra‐QD band alignment is exemplified by comparing the upconversion process in PbS/CdS/ZnSe QDs with that of PbS/CdS/CdSe ones with variable CdSe shell thicknesses. It is shown that electron delocalization into the shell leads to a longer‐lived intermediate state in the QDs, facilitating further absorption of photons, and enhancing the upconversion process. The performance of these upconversion QDs under pulsed excitation versus continuous pumping is also compared; the reasons for the significant differences between these two regimes are discussed. The results show how one can overcome some of the limitations of previous upconverting QDs, with potential applications in biophotonics and infrared detection.

Colour-optimized quantum yields of Yb, Tm Co-doped upconversion nanocrystals

We present here a systematic analysis of the influence of Tm3+ doping concentrations (xTm) on the excitation power (P)-dependent upconversion luminescence and -performance of hexagonal-phase NaYF4: 20% Yb3+, xTm % Tm3+ upconversion nanoparticles (UCNPs) for xTm of 0.2, 0.5, 0.8, 1.2, and 2.0, respectively. Our results reveal the influence of these different Tm3+ doping concentrations with respect to optimized upconversion quantum yield (ΦUC) values of the various Tm3+ upconversion emission bands, with the highest ΦUC values of the Tm3+ emission bands above 700 nm resulting for different xTm values as the Tm3+ emission bands below 700 nm. This underlines the potential of Tm3+ dopant concentration for colour tuning. Special emphasis was dedicated to the spectroscopic parameters that can be linked to the (de)population pathways of the various Tm3+ energy levels, like the P- and xTm-dependent slope factors and the intensity ratios of selected emission bands. The evaluation of all parameters indicates that not only energy transfer upconversion-, but also cross-relaxation processes between neighbouring Tm3+ ions play a vital role in the (de)population of the excited energy levels of Yb3+, Tm3+ codoped nanocrystals.

Phosphorus corrole complexes: from property tuning to applications in photocatalysis and triplet-triplet annihilation upconversion.

Efficient triplet photosensitizers are important for fundamental photochemical studies and applications such as triplet-triplet annihilation upconversion (TTA UC), photoredox catalytic organic reactions and photovoltaics. We now report a series of phosphorus corrole compounds as efficient visible light-harvesting metal-free triplet photosensitizers. While the heavy-atom-free phosphorus corroles show absorption in the visible spectral region (centered at 573 nm) and have a decent triplet state quantum yield (Φ Δ = 49%), iodo-substitution on the corrole core induces red-shifted absorption (589 nm) and improves intersystem crossing significantly (Φ Δ = 67%). Nanosecond transient absorption spectra confirm triplet state formation upon photoexcitation (τ T = 312 μs) and the iodinated derivatives also display near IR phosphorescence in fluid solution at room temperature (λ em = 796 nm, τ p = 412 μs). Both singlet oxygen (1O2) and superoxide radical anions (O2 -˙) may be produced with the phosphorus corroles, which are competent photocatalysts for the oxidative coupling of benzylamine (the Aza Henry reaction). Very efficient TTA UC was observed with the phosphorus corroles as triplet photosensitizers and perylene as the triplet acceptor, with upconversion quantum yields of up to Φ UC = 38.9% (a factor of 2 was used in the equation) and a very large anti-Stokes effect of 0.5 eV.

High Quantum Yield Single‐Band Green Upconversion in La2O3:Yb3+, Ho3+ Microcrystals for Anticounterfeiting and Plastic Recycling

AbstractSingle‐band green upconversion (UC) with high green purity and color stability is urgently required for plastic recycling and anticounterfeiting. However, it is very difficult to obtain single‐band green emission for benchmark Yb3+/Er3+ activated UC materials (such as NaYF4:Yb3+,Er3+) due to the strong accompanying red UC. Herein, highly efficient and stable single‐band green UC is reported in La2O3:Yb3+/Ho3+ (LYH) microcrystals with record high absolute UC quantum yield (UCQY) of 2.6% for single‐band green UC. LYH yields pure green UC with large and stable intensity ratio, IGreen/IRed ≈ 18. LYH presents not only higher UCQY for a single‐band green UC but also much more pure and stable green UC than the benchmark UC materials such as NaYF4:Yb3+,Er3+ and Gd2O2S:Yb3+,Er3+. These results suggest that the newly developed LYH can, in principle, be promising for anticounterfeiting and plastic recycling. Its proof‐of‐concept is demonstrated as a security label based on a transparent institute logo.

Efficient Radical-Enhanced Intersystem Crossing in an NDI-TEMPO Dyad: Photophysics, Electron Spin Polarization, and Application in Photodynamic Therapy.

A compact naphthalenediimide (NDI)-2,2,6,6-tetramethylpiperidinyloxy (TEMPO) dyad has been prepared with the aim of studying radical-enhanced intersystem crossing (EISC) and the formation of high spin states as well as electron spin polarization (ESP) dynamics. Compared with the previously reported radical-chromophore dyads, the present system shows a very high triplet state quantum yield (ΦT =74 %), a long-lived triplet state (τT =8.7 μs), fast EISC (1/kEISC =338 ps), and absorption in the red spectral region. Time-resolved electron paramagnetic resonance (TREPR) spectroscopy showed that, upon photoexcitation in fluid solution at room temperature, the D0 state of the TEMPO moiety produces strong emissive (E) polarization owing to the quenching of the excited singlet state of NDI by the radical moiety (electron exchange J>0). The emissive polarization then inverts into absorptive (A) polarization within about 3 μs, and then relaxes to a thermal equilibrium while quenching the triplet state of NDI. The formation and decay of the quartet state were also observed. The dyad was used as a three-spin triplet photosensitizer for triplet-triplet annihilation upconversion (quantum yield ΦUC =2.6 %). Remarkably, when encapsulated into liposomes, the red-light-absorbing dyad-liposomes show good biocompatibility and excellent photodynamic therapy efficiency (phototoxicity EC50 =3.22 μm), and therefore is a promising candidate for future less toxic and multifunctional photodynamic therapeutic reagents.

Synergetic Effects of Triplet-Triplet Annihilation and Directional Triplet Exciton Migration in Organic Crystals for Photon Upconversion.

In condensed solids, triplet exciton migration and succeeding triplet-triplet annihilation (TTA) are major bottleneck processes for efficient photon upconversion (UC) using sunlight excitation. We theoreticallyinvestigatedthe reaction times of TTA and the triplet-triplet energy transfer (TTET) as the elementary processes of triplet exciton migration in organic crystals of two molecular species: 9,10-diphenylanthracene (DPA) and its double-strapped alkyl derivative (C7-sDPA)as the models of a recently reported crystalline system of TTA-UC by Kamada et al. The reaction times calculated based on Marcus theory clarified that the dimensionality of TTET and synergetic effects of TTA and TTET are responsible for the high UC quantum yield as well as their triplet lifetimes.

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

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

Supramolecular Assembly-Improved Triplet-Triplet Annihilation Upconversion in Aqueous Solution.

Water-soluble 9,10-diphenylanthracene-modified γ-cyclodextrin derivatives A1 and A2, in which the γ-cyclodextrin unit serves as a molecular host for a binding sensitizer, and the 9,10-diphenylanthracene moiety plays a role as an emitter/annihilator, were synthesized to investigate the supramolecular triplet-triplet annihilation (TTA) upconversion in aqueous solution. Both A1 and A2 readily aggregate and form nanoscale assemblies in water as a combined result of host-guest complexation and π-π stacking among the 9,10-diphenylanthracenes. The aggregation behavior of the supramolecular emitters was fully characterized by using a diversity of methods, including dynamic light scattering (DLS), SEM, NMR, fluorescence, and circular dichroism studies. Fluorescence spectroscopic analysis reveals that the emitters have high fluorescence quantum yields in water (82 and 90 % for A1 and A2, respectively), thus demonstrating that aggregation does not quench the fluorescence. By using a coordinated ruthenium sensitizer, a high TTA upconversion quantum yield of up to 6.9 % was observed for this supramolecular TTA system, which is significantly higher than the value (<0.5 %) obtained with nonassembled emitters in organic solvent and in contrast to the fact that TTA upconversion emission in aqueous solution is usually low or negligible. We ascribe the strong TTA upconversion emission in the present supramolecular assembly system to an efficient TTA process, which is facilitated along the stacked emitters by triplet energy migration and improved triplet-triplet energy transfer through host-guest complexation.

Semiconductor Nanocrystal Light Absorbers for Photon Upconversion.

Semiconductor nanocrystals (NCs) can initiate energy and charge transfer in multiple applications with their unique optical and electronic properties. In particular, NCs are excellent light absorbers for initiating triplet energy transfer (TET) to organic molecules, a key step in triplet-fusion-based photon upconversion. Triplet energy transfer across this inorganic-organic interface is one of the bottlenecks that currently limits the overall photon upconversion quantum yield. In this Perspective, we summarize the progress made in the past three years on this hybrid photon upconversion platform. We discuss the effects of NC size, composition, and surface states on TET. Nanocrystal surface engineering may address the loss mechanisms arising from defect states and exciton-phonon coupling. Alternative materials for NC triplet photosensitizers that do not contain toxic heavy metals will be especially useful for various biological applications.

Tuning the upconversion photoluminescence lifetimes of NaYF4:Yb3+, Er3+ through lanthanide Gd3+ doping

The multiplexing capacity of conventional fluorescence materials are significantly limited by spectral overlap and background interference, mainly due to their short-lived fluorescence lifetimes. Here, we adopt a novel Gd3+ doping strategy in NaYF4 host materials, realized tuning of upconversion photoluminescence (UCPL) lifetimes at selective emissions. Time-correlated single-photon counting (TCSPC), was applied to measure the photoluminescence lifetimes accurately. We demonstrated the large dynamic range of lifetimes of upconversion nanoparticles with good upconversion quantum yields, mainly owing to the dominance of high efficient energy transfer upconversion mechanism. The exceptional tunable properties of upconversion materials allow great potential for them to be utilized in biotechnology and life sciences.

Intramolecular Energy and Electron Transfers in Bodipy Naphthalenediimide Triads

Borondipyrromethene (BDP) naphthalenediimide (NDI) triads (BDP-NDI) and diiodo-BDP derivative (DiiodoBDP-NDI)) were synthesized to study the Förster resonance energy transfer (FRET) and its impact on the triplet state formation and dynamics. In these triads, diiodo-BDP and BDP are the energy donors and NDI is the energy acceptor. Nanosecond transient absorption spectra of triads indicated that triplet state is localized on NDI moiety, either by selective photoexcitation of the Diiodo-BDP or NDI unit. The intersystem crossing (ISC) is attributed to intramolecular heavy atom effect. The triplet state quantum yield was found to be 54% with a lifetime of 38 μs. However, no triplet state is observed for BDP-NDI system either by exciting BDP or NDI unit. Thus, we confirmed that charge recombination does not produce a triplet state. Interestingly, DiiodoBDP-NDI can be used as broadband excitable (500-620 nm) triplet photosensitizer, and high triplet-triplet annihilation (TTA) upconversion quantum yield of ΦUC = 2.8% was observed with 9,10-bis(phenylethynyl)-anthracene (BPEA) as a triplet acceptor/emitter.

Bright, Mechanosensitive Upconversion with Cubic-Phase Heteroepitaxial Core-Shell Nanoparticles.

Lanthanide-doped nanoparticles are an emerging class of optical sensors, exhibiting sharp emission peaks, high signal-to-noise ratio, photostability, and a ratiometric color response to stress. The same centrosymmetric crystal field environment that allows for high mechanosensitivity in the cubic-phase (α), however, contributes to low upconversion quantum yield (UCQY). In this work, we engineer brighter mechanosensitive upconverters using a core-shell geometry. Sub-25 nm α-NaYF4:Yb,Er cores are shelled with an optically inert surface passivation layer of ∼4.5 nm thickness. Using different shell materials, including NaGdF4, NaYF4, and NaLuF4, we study how compressive to tensile strain influences the nanoparticles' imaging and sensing properties. All core-shell nanoparticles exhibit enhanced UCQY, up to 0.14% at 150 W/cm2, which rivals the efficiency of unshelled hexagonal-phase (β) nanoparticles. Additionally, strain at the core-shell interface can tune mechanosensitivity. In particular, the compressive Gd shell results in the largest color response from yellow-green to orange or, quantitatively, a change in the red to green ratio of 12.2 ± 1.2% per GPa. For all samples, the ratiometric readouts are consistent over three pressure cycles from ambient to 5 GPa. Therefore, heteroepitaxial shelling significantly improves signal brightness without compromising the core's mechano-sensing capabilities and further, promotes core-shell cubic-phase nanoparticles as upcoming in vivo and in situ optical sensors.

Ligand-Tuneable, Red-Emitting Iridium(III) Complexes for Efficient Triplet-Triplet Annihilation Upconversion Performance.

A series of substituted 2-phenylquinoxaline ligands have been explored to finely tune the visible emission properties of a corresponding set of cationic, cyclometallated iridium(III) complexes. The electronic and redox properties of the complexes were investigated through experimental (including time-resolved luminescence and transient absorption spectroscopy) and theoretical methods. The complexes display absorption and phosphorescent emissions in the visible region that are attributed to metal to ligand charge-transfer transitions. The different substitution patterns of the ligands induce variations in these parameters. Time-dependent DFT studies support these assignments and show that there is likely to be a strong spin-forbidden contribution to the visible absorption bands at λ=500-600 nm. Calculations also reliably predict the magnitude and trends in triplet emitting wavelengths for the series of complexes. The complexes were assessed as potential sensitisers in triplet-triplet annihilation upconversion experiments by using 9,10-diphenylanthracene as the acceptor; the methylated variants performed especially well with impressive upconversion quantum yields of up to 39.3 %.

Formation Mechanism, Structural, and Upconversion Properties of Alkaline Rare-Earth Fluoride Nanocrystals Doped With Yb3+/Er3+ Ions.

Ultrasmall (9-30 nm) Yb3+/Er3+-doped, upconverting alkaline rare-earth fluorides that are promising for future applications were synthesized by the microwave-assisted hydrothermal method. The formation mechanism was proposed, indicating the influence of the stability of metal ions complexes with ethylenediaminetetraacetic acid on the composition of the product and tendency to form M2REF7 (M0.67RE0.33F2.33) cubic compounds in the M-RE-F systems. Their physicochemical properties (structure, morphology, and spectroscopic properties) are compared and discussed. The obtained nanoparticles exhibited emission of light in the visible spectra under excitation by 976 nm laser radiation. Excitation and emission spectra, luminescence decays, laser energy dependencies, and upconversion quantum yields were measured to determine the spectroscopic properties of prepared materials. The Yb3+/Er3+ pair of ions used as dopants was responsible for an intense yellowish-green emission. The upconversion quantum yields determined for the first time for M2REF7-based materials were 0.0192 ± 0.001% and 0.0176 ± 0.001% for Sr2LuF7:Yb3+,Er3+ and Ba2LuF7:Yb3+,Er3+ respectively, the two best emitting samples. These results indicated the prepared materials are good and promising alternatives for the most studied NaYF4:Yb3+,Er3+ nanoparticles.

Ping-Pong Energy Transfer in a Boron Dipyrromethane Containing Pt(II)-Schiff Base Complex: Synthesis, Photophysical Studies, and Anti-Stokes Shift Increase in Triplet-Triplet Annihilation Upconversion.

A boron dipyrromethane (BDP)-containing Pt(II)-Schiff base complex (Pt-BDP), showing ping-pong singlet-triplet energy transfer, was synthesized, and the detailed photophysical properties were investigated using various steady-state and time-resolved transient spectroscopies. Femtosecond/nanosecond transient absorption spectroscopies demonstrated that, upon selective excitation of the BDP unit in Pt-BDP at 490 nm, Förster resonance energy transfer from the BDP unit to the Pt(II) coordination center occurred (6.7 ps), accompanied by an ultrafast intersystem crossing at the Pt(II) coordination center (<1 ps) and triplet-triplet energy transfer back to the BDP moiety (148 ps). These processes generated a triplet state localized at BDP, and the lifetime was 103.2 μs, much longer than the triplet-state lifetime of Pt-Ph (3.5 μs), a complex without the BDP moiety. Finally, Pt-BDP was used as a triplet photosensitizer for triplet-triplet annihilation (TTA) upconversion through selective excitation of the BDP unit or the Pt(II) coordination center at lower excitation energy. An upconversion quantum yield of up to 10% was observed with selective excitation of the BDP moiety, and a large anti-Stokes shift of 0.65 eV was observed upon excitation of the lower-energy band of the Pt(II) coordination center. We propose that using triplet photosensitizers with the ping-pong energy-transfer process may become a useful method for increasing the anti-Stokes shift of TTA upconversion.