Graduate student, University of Cincinnati
Improving triplet-tripet annihilation upconversion in solid state applications
Solar panels are fairly inefficient, usually reaching no higher than 30% of their capability. Triplet-triplet annihilation upconversion is a process that turns lower energy light into higher energy light. This process could be used to improve solar panels by reusing some of the light that is not used by the solar panel material and making it usable. However, this process is usually done in solution, which is not feasible for application in solar panels. So my research is focused on improving the results from materials as solids. Our strategy is to bind the molecules responsible for the process to a polymer which can be easily made into a film without the usual separation of the molecules. The triplet-triplet annihilation upconversion process requires the molecules to be close together, but separation of those molecules usually occurs in the solid state. Attaching the molecules to a polymer locks them into position so they cannot separate when put in the solid state, allowing the process to be as efficient as possible. We are trying to vary the amount of the molecules attached to each polymer to determine the best performing combination, which can be used as an additional layer in solar panels to make them more efficient and potentially cheaper.
Abstract: Solar power production and solar energy storage are important research areas for development of technologies that can facilitate a transition to a future society independent of fossil fuel based energy sources. Devices for direct conversion of solar photons suffer from poor efficiencies due to spectrum losses, which are caused by energy mismatch between the optical absorption of the devices and the broadband irradiation provided by the sun. In this context, photon-upconversion technologies are becoming increasingly interesting since they might offer an efficient way of converting low energy solar energy photons into higher energy photons, ideal for solar power production and solar energy storage. This perspective discusses recent progress in triplet-triplet annihilation (TTA) photon-upconversion systems and devices for solar energy applications. Furthermore, challenges with evaluation of the efficiency of TTA-photon-upconversion systems are discussed and a general approach for evaluation and comparison of existing systems is suggested.
Pub.: 16 Apr '14, Pinned: 29 Jun '17
Abstract: Materials capable to perform upconversion of light transform the photon spectrum and can be used to increase the efficiency of solar cells by upconverting sub-bandgap photons, increasing the density of photons able to generate an electron-hole pair in the cell. Incoherent solar radiation suffices to activate upconverters based on sensitized triplet-triplet annihilation, which makes them particularly suited for this task. This process requires two molecular species, sensitizers absorbing low energy photons, and emitters generating higher frequency photons. Successful implementations exist in solutions and solids. However, solid upconverters exhibit lower efficiency than those in solution, which poses a serious problem for real applications. In the present work, we suggest a new strategy to increase the efficiency of sensitized upconverters that exploits the solid nature of the material. We show that an upconversion model system with molecules distributed as clusters outperforms a system with a random distribution of molecules, as used in current upconverters. Our simulations reveal a high potential for improvement of upconverter systems by exploring different structural configurations of the molecules. The implementation of advanced structures can push the performance of solid upconverters further towards the theoretical limit and a step closer to technological application of low power upconversion.
Pub.: 17 Nov '14, Pinned: 29 Jun '17
Abstract: We report an investigation of triplet-triplet annihilation upconversion (TTA-UC) based on polymeric emitters with tunable inter-chromophore distances. Poly[(9-anthrylmethyl methacrylate)-co-(methyl methacrylate)] (poly(AnMMA-co-MMA)) with different percentages of AnMMA was synthesized using reversible addition-fragmentation chain transfer (RAFT) polymerization, and used as an emitter in association with platinum octaethylporphyrin as a sensitizer to form TTA-UC systems. It is observed that the TTA-UC intensity first increases with increasing AnMMA percentage in the polymers then decreases, and ultimately disappears, upon further increasing the AnMMA percentage. The results shed light on the key factors affecting TTA-UC in polymers, and have implications for the design of polymer-based TTA-UC systems.
Pub.: 22 Nov '14, Pinned: 29 Jun '17
Abstract: A photoswitchable fluorescent triad based on two 9,10-diphenylanthracene (DPA) and one dithienylethene (DTE) moiety is prepared for photoswitching of triplet-triplet annihilation upconversion. The DPA and DTE moieties in the triad were connected via Click reaction. The DPA unit in the triad was used as the triplet energy acceptor and upconverted fluorescence emitter. The fluorescence of the triad is switched ON with the DTE moiety in open form [DTE-(o)] (upconversion quantum yield ΦUC = 1.2%). Upon UV irradiation, photocyclization of the DTE-(o) moiety produces the closed form [DTE-(c)], as a result the fluorescence of DPA moiety was switched off (ΦUC is negligible). Three different mechanisms are responsible for the upconverted fluorescence photoswitching effect (i.e., the photoactivated fluorescence resonance energy transfer, the intramolecular electron transfer, as well as the photoactivated intermolecular triplet energy transfer between the photosensitizer and DTE-(c) moiety). Previously, the photoswitching of TTA upconversion was accomplished with only one mechanism (i.e., the triplet state quenching of the photosensitizer by DTE-(c) via either the intermolecular or intramolecular energy transfer). The photophysical processes involved in the photochromism and photoswitching of TTA upconversion were studied with steady-state UV-vis absorption and fluorescence emission spectroscopies, nanosecond transient absorption spectroscopy, electrochemical characterization, and DFT/TDDFT calculations.
Pub.: 17 Dec '14, Pinned: 29 Jun '17
Abstract: We report four supermolecular chromophores based on (porphinato)zinc(II) (PZn) and (polypyridyl)metal units bridged via ethyne connectivity (Pyr1RuPZn2, Pyr1RuPZnRuPyr1, Pyr1RuPZn2RuPyr1, and OsPZn2Os) that fulfill critical sensitizer requirements for NIR-to-vis triplet-triplet annihilation upconversion (TTA-UC) photochemistry. These NIR sensitizers feature: (i) broad, high oscillator strength NIR absorptivity (700 nm < λ(max(NIR)) < 770 nm; 6 × 10(4) M(-1) cm(-1) < extinction coefficient (λ(max(NIR))) < 1.6 × 10(5) M(-1) cm(-1); 820 cm(-1) < fwhm < 1700 cm(-1)); (ii) substantial intersystem crossing quantum yields; (iii) long, microsecond time scale T1 state lifetimes; and (iv) triplet states that are energetically poised for exergonic energy transfer to the molecular annihilator (rubrene). Using low-power noncoherent illumination at power densities (1-10 mW cm(-2)) similar to that of terrestrial solar photon illumination conditions, we demonstrate that Pyr1RuPZn2, Pyr1RuPZn2RuPyr1, and Pyr1RuPZnRuPyr1 sensitizers can be used in combination with the rubrene acceptor/annihilator to achieve TTA-UC: these studies represent the first examples whereby a low-power noncoherent NIR light source drives NIR-to-visible upconverted fluorescence centered in a spectral window within the bandgap of amorphous silicon.
Pub.: 12 May '15, Pinned: 29 Jun '17
Abstract: To meet the world's demands on the development of sunlight-powered renewable energy production, triplet-triplet annihilation-based photon upconversion (TTA-UC) has raised great expectations. However, an ideal highly efficient, low-power, and in-air TTA-UC has not been achieved. Here, we report a novel self-assembly approach to achieve this, which enabled highly efficient TTA-UC even in the presence of oxygen. A newly developed lipophilic 9,10-diphenylanthracene-based emitter molecule functionalized with multiple hydrogen-bonding moieties spontaneously coassembled with a triplet sensitizer in organic media, showing efficient triplet sensitization and subsequent triplet energy migration among the preorganized chromophores. This supramolecular light-harvesting system shows a high UC quantum yield of 30% optimized at low excitation power in deaerated conditions. Significantly, the UC emission largely remains even in an air-saturated solution, and this approach is facilely applicable to organogel and solid-film systems.
Pub.: 10 Jun '15, Pinned: 29 Jun '17
Abstract: High-efficiency upconverted light would be a desirable stimulus for triggered drug delivery. Here we present a general strategy to achieve photoreactions based on triplet-triplet annihilation upconversion (TTA-UC) and Förster resonance energy transfer (FRET). We designed PLA-PEG micellar nanoparticles containing in their cores hydrophobic photosensitizer and annihilator molecules which, when stimulated with green light, would undergo TTA-UC. The upconverted energy was then transferred by FRET to a hydrophobic photocleavable group (DEACM), also in the core. The DEACM was bonded to (and thus inactivated) the cell-binding peptide cyclo-(RGDfK), which was bound to the PLA-PEG chain. Cleavage of DEACM by FRET reactivated the PLA-PEG-bound peptide and allowed it to move from the particle core to the surface. TTA-UC followed by FRET allowed photocontrolled binding of cell adhesion with green light LED irradiation at low irradiance for short periods. These are attractive properties in phototriggered systems.
Pub.: 15 Jul '15, Pinned: 29 Jun '17
Abstract: The sensitized triplet–triplet annihilation-based upconversion in bicomponent systems is currently considered the most promising strategy for increasing the light-harvesting ability of solar cells. Flexible, manageable, inexpensive up-converting devices become possible by implementing this process in elastomers. Here, we report a study combining optical spectroscopy data of the light conversion process with the nano- and macroscopic viscoelastic characterization of the host material embedding the active dyes, in order to find a rationale for the fabrication of efficient solid-state upconverting systems. By using the poly(n-alkyl acrylates) as a model of the monophasic elastomers, we demonstrate that the yield of the bimolecular interactions at the base of the upconversion process, namely, energy transfer and triplet–triplet annihilation, is mainly determined by the glass transition temperature (Tg) of the polymer. By employing the polyoctyl acrylate (Tg = 211 K), we achieved a conversion yield at the solid state larger than 10% at an irradiance of 1 sun, showing the potential of the elastomer-based upconverting materials for developing real-world devices.
Pub.: 18 Jan '16, Pinned: 29 Jun '17
Abstract: Efficient visible-to-UV photon upconversion via triplet–triplet annihilation (TTA) is accomplished in polyurethane (PU) films by developing new, powerful photosensitizers fully functional in the solid-state matrix. These rationally designed triplet sensitizers feature a bichromophoric scaffold comprising a tris-cyclometalated iridium(III) complex covalently tethered to a suitable organic small molecule. The very rapid intramolecular triplet energy transfer from the former to the latter is pivotal for achieving the potent sensitizing ability, because this process out-competes the radiative and nonradiative decays inherent to the metal complex and produces long-lived triplet excitons localized with the acceptor moiety readily available for intermolecular transfer and TTA. Nonetheless, compared to the solution state, the molecular diffusion is greatly limited in solid matrices, which even creates difficulty for the Dexter-type intramolecular energy transfer. This is proven by the experimental results showing that the sensitizing performance of the bichromophoric molecules strongly depends on the spatial distance separating the donor (D) and acceptor (A) units and that incorporating a longer linker between the D and A evidently curbs the TTA upconversion efficiency in PU films. Using a rationally optimized sensitizer structure in combination with 2,7-di-tert-butylpyrene as the annihilator/emitter, the doped polyurethane (PU) films demonstrate effective visible-to-UV upconverted emission signal under noncoherent-light irradiation, attaining an upconversion quantum yield of 2.6%. Such quantum efficiency is the highest value so far reported for the visible-to-UV TTA systems in solid matrices.
Pub.: 15 Apr '16, Pinned: 29 Jun '17
Abstract: We present a red-to-blue upconversion system based on triplet–triplet annihilation in a solid-state film configuration that significantly enhances the photocurrent of a model solar cell device. The film is robust against oxygen quenching and can be readily tailored to existing solar cell architectures. The photovoltaic performance of upconversion-assisted dye-sensitized photoelectrochemical cells was measured under both high-power coherent laser and low-power incoherent light irradiation (light-emitting diode and simulated AM1.5G sunlight). By utilizing low-energy photons that would otherwise be wasted, the photocurrent is enhanced by as much as 35% under one-sun light intensity when a model solar cell device is coupled with a TTA film and a reflector.
Pub.: 02 May '16, Pinned: 29 Jun '17
Abstract: A series of directly meso‐meso‐linked Pd–porphyrin oligomers (PdDTP‐M, PdDTP‐D, and PdDTP‐T) have been prepared. The absorption region and the light‐harvesting ability of the Pd–porphyrin oligomers are broadened and enhanced by increasing the number of Pd–porphyrin units. Triplet–triplet annihilation upconversion (TTA‐UC) systems were constructed by utilizing the Pd–porphyrin oligomers as the sensitizer and 9,10‐diphenylanthracene (DPA) as the acceptor in deaerated toluene and green‐to‐blue photon upconversion was observed upon excitation with a 532 nm laser. The triplet–triplet annihilation upconversion quantum efficiencies were found to be 6.2 %, 10.5 %, and 1.6 % for the [PdDTP‐M]/DPA, [PdDTP‐D]/DPA, and [PdDTP‐T]/DPA systems, respectively, under an excitation power density of 500 mW cm−2. The photophysical processes of the TTA‐UC systems have been investigated in detail. The higher triplet–triplet annihilation upconversion quantum efficiency observed in the [PdDTP‐D]/DPA system can be rationalized by the enhanced light‐harvesting ability of PdDTP‐D at 532 nm. Under the same experimental conditions, the [PdDTP‐D]/DPA system produces more 3DPA* than the other two TTA‐UC systems, benefiting the triplet–triplet annihilation process. This work provides a useful way to develop efficient TTA‐UC systems with broad spectral response by using Pd–porphyrin oligomers as sensitizers.
Pub.: 03 May '16, Pinned: 29 Jun '17
Abstract: Triplet–triplet annihilation photon upconversion (TTA-UC) systems contain both an absorbing and an emitting molecule, the sensitizer and annihilator, respectively. Through a series of energy-transfer steps, two low frequency photons can be combined into one high frequency photon. In organic solvents, the required energy transfer steps are limited by diffusion and are relatively efficient. In solid-state systems, however, the diffusion is slower, which usually results in lower efficiencies for these systems. An interesting way around this is to connect the sensitizer and annihilator. In order to increase understanding of the TTA-UC process in supramolecular systems, we synthesized four pyridine-substituted anthracene annihilators capable of coordinating axially to a zinc octaethylporphyrin sensitizer with a maximum binding constant of 6000 M–1 in toluene. This is a first example of a sensitizer–annihilator coordination complex for TTA-UC. Both the upconversion efficiency and the parasitic quenching of excited annihilator singlets by the sensitizer through Förster resonant energy transfer (FRET) were studied. On the basis of the findings herein, possible strategies for future supramolecular TTA systems with minimized FRET quenching are discussed.
Pub.: 09 Aug '16, Pinned: 29 Jun '17
Abstract: An important challenge when developing materials for triplet–triplet annihilation upconversion (TTA-UC) is achieving efficient and well-functioning solid-state systems. We here explore the effect of intramolecular TTA in oligomers and dendrimers based on the 9,10-diphenylanthracene (DPA) chromophore. The macromolecules are sensitized using palladium porphyrin, both in solution and in solid poly(methyl methacrylate) (PMMA), demonstrating a positive effect on overall upconversion in the solid state correlating with the well-controlled size of the DPA constructs. The UC kinetics is modeled and fit to steady-state and time-resolved emission data to give further insight into the intramolecular excited-state migration and annihilation in the macromolecular annihilator systems.
Pub.: 22 Sep '16, Pinned: 29 Jun '17
Abstract: We report highly efficient sensitized triplet–triplet annihilation based upconversion in aqueous suspensions of nanoparticles prepared from 9,10-diphenylanthracene-terminated poly(ε-caprolactone) and with platinum octaethylporphyrin as the sensitizer. The particles upconversion characteristics are strongly temperature-dependent. This feature gives insights into the mechanisms enabling the process in the nanoparticle environment, and the specific temperature range in which the photophysical parameters change is suitable for live cell and in vivo temperature sensing.
Pub.: 21 Sep '16, Pinned: 29 Jun '17
Abstract: Anti-Stokes shift luminescence is a special optical process, which converts long-wavelength excitation to short-wavelength emission. This unique ability is especially helpful for bio-applications, because the longer-wavelength light source, usually referring to near infrared light, has a larger penetration depth offering a longer working distance for in vivo applications. The anti-Stokes shift luminescence signal can also be distinguished from the auto-fluorescence of biological tissues, thus reducing background interference during bioimaging. Herein, we summarize recent advances in anti-Stokes shift luminescent materials, including lanthanide and triplet-triplet-annihilation-based upconversion nanomaterials, and newly improved hot-band absorption-based luminescent materials. We focus on the synthetic strategies, optical optimization and biological applications as well as present comparative discussions on the luminescence mechanisms and characteristics of these three types of luminescent materials.
Pub.: 15 Dec '16, Pinned: 29 Jun '17
Abstract: Understanding the temperature dependency of triplet-triplet annihilation upconversion (TTA-UC) is important for optimizing biological applications of upconversion. Here the temperature dependency of red-to-blue TTA-UC is reported in a variety of neutral PEGylated phospholipid liposomes. In these systems a delicate balance between lateral diffusion rate of the dyes, annihilator aggregation, and sensitizer self-quenching, leads to a volcano plot, with the maximum upconversion intensity occurring near the main order-disorder transition temperature of the lipid membrane.
Pub.: 07 Jan '17, Pinned: 29 Jun '17
Abstract: Photochemical upconversion (UC) of low-energy photons that would otherwise be wasted could drastically improve the efficiency of solar technologies by allowing them to harness a greater fraction of the solar spectrum. Although UC through the triplet–triplet annihilation (TTA) mechanism operates efficiently under low-power irradiation such as sunlight, its ability to improve solar device efficiencies is limited by the narrow light absorption bands of its sensitizer chromophores. This bottleneck on UC performance can be overcome by employing multiple sensitizers in tandem, but such an approach has thus far been studied exclusively in solution-based TTA-UC systems requiring intensive deoxygenation and sealing procedures. This study presents the first dual-sensitizer TTA-UC system in a solid-state host suitable for practical applications. We fabricate thin polyurethane films containing two benchmark TTA-UC sensitizers in a range of different concentrations and characterize their red-to-blue and green-to-blue UC performance as a function of excitation intensity. The broadband absorption of the dual-sensitizer films significantly enhances their performance under simultaneous low-intensity excitation of the two sensitizers, giving rise to anti-Stokes fluorescence surpassing the combined anti-Stokes fluorescence of the films’ single-sensitizer analogues. We circumvent trade-offs between light absorption and TTA-UC performance at high sensitizer concentrations by harnessing the films’ unique versatility to produce an alternative “multijunction” TTA-UC system comprising overlaid single-sensitizer films, thereby achieving strong broadband light absorption and superior TTA-UC performance.
Pub.: 20 Dec '16, Pinned: 29 Jun '17
Abstract: Triplet-triplet annihilation based upconversion emission (TTA-UC), through energy transfer processes among organic dyes, has been achieving great attentions for the potential applications in different fields; an important step forward the application of TTA-UC systems in real devices is the incorporation of the dye couple into solid supports.
Pub.: 10 Mar '17, Pinned: 29 Jun '17
Abstract: Triplet excitons are key players in multi-excitonic processes like singlet fission and triplet-triplet annihilation based photon upconversion, which may be useful in next-generation photovoltaic devices, photocatalysis and bioimaging. Here, we present an overview of experimental and theoretical work on triplet energy transfer, with a focus on triplet transport in thin films. We start with the theory describing Dexter-mediated triplet energy transfer and the fundamental parameters controlling this process. Then we summarize current experimental methods used to measure the triplet exciton diffusion length. Finally, the use of hierarchically ordered structures to improve the triplet diffusion length is presented, before concluding with an outlook on the remaining challenges.
Pub.: 06 Apr '17, Pinned: 29 Jun '17
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