Sean T. Roberts

Efficient Singlet Fission Discovered in a Disordered Acene Film

Singlet exciton fission is a process that occurs in select organic semiconductors and entails the splitting of a singlet excited state into two lower triplet excitons located on adjacent chromophores. Research examining this phenomenon has recently seen a renaissance due to the potential to exploit singlet fission within the context of organic photovoltaics to prepare devices with the ability to circumvent the Shockley-Queisser limit. To date, high singlet fission yields have only been reported for crystalline or polycrystalline materials, suggesting that molecular disorder inhibits singlet fission. Here, we report the results of ultrafast transient absorption and time-resolved emission experiments performed on 5,12-diphenyl tetracene (DPT). Unlike tetracene, which tends to form polycrystalline films when vapor deposited, DPTs pendant phenyl groups frustrate crystal growth, yielding amorphous films. Despite the high level of disorder in these films, we find that DPT exhibits a surprisingly high singlet fission yield, with 1.22 triplets being created per excited singlet. This triplet production occurs over two principal time scales, with ~50% of the triplets appearing within 1 ps after photoexcitation followed by a slower phase of triplet growth over a few hundred picoseconds. To fit these kinetics, we have developed a model that assumes that due to molecular disorder, only a subset of DPT dimer pairs adopt configurations that promote fission. Singlet excitons directly excited at these sites can undergo fission rapidly, while singlet excitons created elsewhere in the film must diffuse to these sites to fission.

Singlet and Triplet Excitation Management in a Bichromophoric Near-Infrared-Phosphorescent BODIPY-Benzoporphyrin Platinum Complex

Multichromophoric arrays provide one strategy for assembling molecules with intense absorptions across the visible spectrum but are generally focused on systems that efficiently produce and manipulate singlet excitations and therefore are burdened by the restrictions of (a) unidirectional energy transfer and (b) limited tunability of the lowest molecular excited state. In contrast, we present here a multichromophoric array based on four boron dipyrrins (BODIPY) bound to a platinum benzoporphyrin scaffold that exhibits intense panchromatic absorption and efficiently generates triplets. The spectral complementarity of the BODIPY and porphryin units allows the direct observation of fast bidirectional singlet and triplet energy transfer processes (k(ST)((1)BDP→(1)Por) = 7.8 × 10(11) s(-1), k(TT)((3)Por→(3)BDP) = 1.0 × 10(10) s(-1), k(TT)((3)BDP→(3)Por) = 1.6 × 10(10) s(-1)), leading to a long-lived equilibrated [(3)BDP][Por]⇌[BDP][(3)Por] state. This equilibrated state contains approximately isoenergetic porphyrin and BODIPY triplets and exhibits efficient near-infrared phosphorescence (λ(em) = 772 nm, Φ = 0.26). Taken together, these studies show that appropriately designed triplet-utilizing arrays may overcome fundamental limitations typically associated with core-shell chromophores by tunable redistribution of energy from the core back onto the antennae.

Fused Porphyrin–Single-Walled Carbon Nanotube Hybrids: Efficient Formation and Photophysical Characterization

A systematic study of the interaction between π-extended porphyrins and single-walled carbon nanotubes (SWNTs) is reported here. Zinc porphyrins with 1-pyrenyl groups in the 5,15-meso positions, 1, as well as compounds where one or both of the pyrene groups have been fused at the meso and β positions of the porphyrin core, 2 and 3, respectively, have been examined. The strongest binding to SWNTs is observed for porphyrin 3, leading to debundling of the nanotubes and formation of stable suspensions of 3-SWNT hybrids in a range of common organic solvents. Absorption spectra of 3-SWNT suspensions are broad and continuous (λ=400-1400 nm), and the Q-band of 3 displays a significant bathochromic shift of 33 nm. The surface coverage of the SWNTs in the nanohybrids was estimated by spectroscopic and analytical methods and found to reach 64% for (7,6) nanotubes. The size and shape of π-conjugated porphyrins were found to be important factors in determining the strength of the π-π interactions, as the linear anti-3 isomer displays more than 90% binding selectivity compared to the bent syn-3 isomer. Steady-state photoluminescence measurements show quenching of porphyrin emission from the nanohybrids. Femtosecond transient absorption spectroscopy reveals that this quenching results from ultrafast electron transfer from the photoexcited porphyrin to the SWNT (1/kCT=260 fs) followed by rapid charge recombination on a picosecond time scale. Overall, our data demonstrate that direct π-π interaction between fused porphyrins and SWNTs leads to electronically coupled stable nanohybrids.

Observation of Triplet Exciton Formation in a Platinum-Sensitized Organic Photovoltaic Device.

Organic photovoltaics (OPVs) constitute a promising new technology due to their low production costs. However, OPV efficiencies remain low because excitons typically diffuse only ∼5-20 nm during their lifetime, limiting the effective thickness of the light-absorbing layer. One strategy to improve OPVs is to increase exciton lifetimes by converting them into triplet states, which typically persist 10(3)-10(5) times longer than singlet excitons. We present femtosecond transient absorption and steady-state photovoltaic measurements of a model OPV system consisting of diphenyltetracene (DPT) films doped with platinum tetraphenylbenzoporphyrin (Pt(TPBP)). Photoexcitation of Pt(TPBP) creates a singlet excitation that rapidly intersystem crosses to a triplet state before transferring to the DPT host matrix. This transfer is rapid and efficient, occurring in 35 ps with an 85% conversion ratio of porphyrin singlets to DPT triplets. These triplet excitons lead to enhanced photocurrent response that increases with device thickness.

Aqueous colloidal acene nanoparticles: a new platform for studying singlet fission.

Singlet fission is a process that occurs in select molecular systems wherein a singlet excited state divides its energy to form two triplet excitations on neighboring chromophores. While singlet fission has been largely studied in molecular crystals, colloidal nanoparticles offer the ability to investigate fission using liquid suspensions, allowing questions regarding the importance of molecular arrangement and charge transfer to be assessed. Herein, we report the synthesis of aqueous colloidal nanoparticles of 5,12-diphenyltetracene (DPT), a material recently demonstrated to undergo singlet fission in disordered films. Upon synthesis, nanoparticles display absorption features that lie between those of monomeric DPT and disordered DPT films. These features evolve over a few days in a manner that suggests an increase in the degree of association between neighboring molecules within the nanoparticles. Transient absorption and time-resolved emission experiments indicate that photoexcited DPT nanoparticles undergo fission, but produce a lower triplet yield than disordered films.

Local and collective reaction coordinates in the transport of the aqueous hydroxide ion.

We investigate local and collective reaction coordinates for the structural diffusion of the hydroxide ion in dilute aqueous NaOH solution using a multistate empirical valence bond (MS-EVB) simulation. We characterize a 15 fs time scale associated with shifting of the equally shared proton within a Zundel-like H3O2(-) ion to form a water molecule, a 550 fs relaxation from this transition state largely guided by electrostatic fluctuations of the surrounding environment, and a 9.6 ps time scale that corresponds to the solvation of the water molecule formed by the proton transfer event. When individual proton transfer events are examined, we are unable to identify a unique transition state solely on the basis of a decrease in the hydroxide ions coordination number. Instead, we find that the collective electric field along the proton transfer direction is better suited to describe the creation and relaxation of Zundel-like transition states that allow structural diffusion of the hydroxide ion.

Extracting the Density of States of Copper Phthalocyanine at the SiO2 Interface with Electronic Sum Frequency Generation.

Organic semiconductors (OSCs) constitute an attractive platform for optoelectronics design due to the ease of their processability and chemically tunable properties. Incorporating OSCs into electrical circuits requires forming junctions between them and other materials, yet the change in dielectric properties about these junctions can strongly perturb the electronic structure of the OSC. Here we adapt an interface-selective optical technique, electronic sum frequency generation (ESFG), to the study of a model OSC thin-film system, copper phthalocyanine (CuPc) deposited on SiO2. We find that by modeling the thickness dependence of our measured spectra, we can identify changes in CuPcs electronic density of states at both its buried interface with SiO2 and air-exposed surface. Our work demonstrates that ESFG can be used to noninvasively probe the interfacial electronic structure of optically thick OSC films, indicating that it can be used for the study of OSC-based optoelectronics in situ.

Charge carrier concentration dependence of ultrafast plasmonic relaxation in conducting metal oxide nanocrystals

Electronically doped metal oxide nanocrystals exhibit tunable infrared localized surface plasmon resonances (LSPRs). Despite the many benefits of IR resonant LSPRs in solution processable nanocrystals, the ways in which the electronic structure of the host semiconductor material impact metal oxide LSPRs are still being investigated. Semiconductors provide an alternative dielectric environment than metallically bonded solids, such as noble metals, which can impact how these materials undergo electronic relaxation following photoexcitation. Understanding these differences is key to developing applications that take advantage of the unique optical and electronic properties offered by plasmonic metal oxide NCs. Here, we use the two-temperature model in conjunction with femtosecond transient absorption experiments to describe how the internal temperature of two representative metal oxide nanocrystal systems, cubic WO3−x and bixbyite Sn-doped In2O3, change following LSPR excitation. We find that the low free carrier concentrations of metal oxide NCs lead to less efficient heat generation as compared to metallic nanocrystals such as Ag. This suggests that metal oxide NCs may be ideal for applications wherein untoward heat generation may disrupt the applications overall performance, such as solar energy conversion and photonic gating.

Photon quenching in InGaN quantum well light emitting devices

This work provides experimental evidence for photon quenching in InGaN and discusses its relevance to efficiency droop problem in InGaN-based light emitters. An equilibrium rate equation model demonstrates that radiative efficiency for this loss mechanism not only has a similar dependence on carrier density as Auger recombination process, but it also possesses the right magnitude making it difficult to distinguish between the two and possibly leading to errors in interpretation. The impact of photon quenching processes on device performance is emphasized by demonstrating loss of efficiency for spectral regions where there is experimental evidence for photon quenching.

Energy transport: Singlet to triplet and back again.

Spin-triplet excitations commonly migrate through direct electron exchange between neighbouring molecules. Now, experiments show that back-and-forth interconversion between spin-triplet and spin-singlet states can significantly speed up triplet migration in organic crystals.