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Magnetic dipolar interaction between correlated triplets created by singlet fission in tetracene crystals.

ABSTRACT: Singlet fission can potentially break the Shockley-Queisser efficiency limit in single-junction solar cells by splitting one photoexcited singlet exciton (S1) into two triplets (2T1) in organic semiconductors. A dark multiexciton state has been proposed as the intermediate connecting S1 to 2T1. However, the exact nature of this multiexciton state, especially how the doubly excited triplets interact, remains elusive. Here we report a quantitative study on the magnetic dipolar interaction between singlet-fission-induced correlated triplets in tetracene crystals by monitoring quantum beats relevant to the multiexciton sublevels at room temperature. The resonances of multiexciton sublevels approached by tuning an external magnetic field are observed to be avoided, which agrees well with the theoretical predictions considering a magnetic dipolar interaction of ∼ 0.008 GHz. Our work quantifies the magnetic dipolar interaction in certain organic materials and marks an important step towards understanding the underlying physics of the multiexciton state in singlet fission.

SUBMITTER: Wang R

PROVIDER: S-EPMC4633952 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Using temperature dependent fluorescence to evaluate singlet fission pathways in tetracene single crystals.

Project description:The temperature-dependent fluorescence spectrum, decay rate, and spin quantum beats are examined in single tetracene crystals to gain insight into the mechanism of singlet fission. Over the temperature range of 250 K-500 K, the vibronic lineshape of the emission indicates that the singlet exciton becomes localized at 400 K. The fission process is insensitive to this localization and exhibits Arrhenius behavior with an activation energy of 550 ± 50 cm-1. The damping rate of the triplet pair spin quantum beats in the delayed fluorescence also exhibits an Arrhenius temperature dependence with an activation energy of 165 ± 70 cm-1. All the data for T > 250 K are consistent with direct production of a spatially separated 1(T⋯T) state via a thermally activated process, analogous to spontaneous parametric downconversion of photons. For temperatures in the range of 20 K-250 K, the singlet exciton continues to undergo a rapid decay on the order of 200 ps, leaving a red-shifted emission that decays on the order of 100 ns. At very long times (≈1 µs), a delayed fluorescence component corresponding to the original S1 state can still be resolved, unlike in polycrystalline films. A kinetic analysis shows that the redshifted emission seen at lower temperatures cannot be an intermediate in the triplet production. When considered in the context of other results, our data suggest that the production of triplets in tetracene for temperatures below 250 K is a complex process that is sensitive to the presence of structural defects.

| S-EPMC9533257 | biostudies-literature

Polymorphism influences singlet fission rates in tetracene thin films.

Project description:We report the effect of crystal structure and crystallite grain size on singlet fission (SF) in polycrystalline tetracene, one of the most widely studied SF and organic semiconductor materials. SF has been comprehensively studied in one polymoprh (Tc I), but not in the other, less stable polymorph (Tc II). Using carefully controlled thermal evaporation deposition conditions and high sensitivity ultrafast transient absorption spectroscopy, we found that for large crystallite size samples, SF in nearly pure Tc II films is significantly faster than SF in Tc I films. We also discovered that crystallite size has a minimal impact on the SF rate in Tc II films, but a significant influence in Tc I films. Large crystallites exhibit SF times of 125 ps and 22 ps in Tc I and Tc II, respectively, whereas small crystallites have SF times of 31 ps and 33 ps. Our results demonstrate first, that attention must be paid to polymorphism in obtaining a self-consistent rate picture for SF in tetracene and second, that control of polymorphism can play a significant role towards achieving a mechanistic understanding of SF in polycrystalline systems. In this latter context we show that conventional theory based on non-covalent tetracene couplings is insufficient, thus highlighting the need for models that capture the delocalized and highly mobile nature of excited states in elucidating the full photophysical picture.

| S-EPMC5975788 | biostudies-literature

Electrical Detection of Singlet Fission in Single Crystal Tetracene Transistors.

Project description:We present the electrical detection of singlet fission in tetracene by using a field-effect transistor (FET). Singlet fission is a photoinduced spin-dependent process, yielding two triplet excitons from the absorption of a single photon. In this study, we engineered a more deterministic platform composed of an organic single crystal FET rather than amorphous or polycrystalline FETs to elucidate spin-dependent processes under magnetic fields. Despite the unipolar operation and relatively high mobility of single crystal tetracene FETs, we were able to manipulate spin dependent processes to detect magnetoconductance (MC) at room temperature by illuminating the FETs and tuning the bias voltage to adjust majority charge carrier density and trap occupancy. In considering the crystalline direction and magnetic field interactions in tetracene, we show the MC response observed in tetracene FETs to be the result of the singlet fission process.

| S-EPMC6541755 | biostudies-literature

Change in Tetracene Polymorphism Facilitates Triplet Transfer in Singlet Fission-Sensitized Silicon Solar Cells.

Project description:Singlet fission in tetracene generates two triplet excitons per absorbed photon. If these triplet excitons can be effectively transferred into silicon (Si), then additional photocurrent can be generated from photons above the bandgap of Si. This could alleviate the thermalization loss and increase the efficiency of conventional Si solar cells. Here, we show that a change in the polymorphism of tetracene deposited on Si due to air exposure facilitates triplet transfer from tetracene into Si. Magnetic field-dependent photocurrent measurements confirm that triplet excitons contribute to the photocurrent. The decay of tetracene delayed photoluminescence was used to determine a transfer efficiency of ∼36% into Si. Our study suggests that control over the morphology of tetracene during the deposition will be of great importance to boost the triplet transfer yield further.

| S-EPMC7569671 | biostudies-literature

Resolving electron injection from singlet fission-borne triplets into mesoporous transparent conducting oxides.

Project description:Photoinduced electron transfer into mesoporous oxide substrates is well-known to occur efficiently for both singlet and triplet excited states in conventional metal-to-ligand charge transfer (MLCT) dyes. However, in all-organic dyes that have the potential for producing two triplet states from one absorbed photon, called singlet fission dyes, the dynamics of electron injection from singlet vs. triplet excited states has not been elucidated. Using applied bias transient absorption spectroscopy with an anthradithiophene-based chromophore (ADT-COOH) adsorbed to mesoporous indium tin oxide (nanoITO), we modulate the driving force and observe changes in electron injection dynamics. ADT-COOH is known to undergo fast triplet pair formation in solid-state films. We find that the electronic coupling at the interface is roughly one order of magnitude weaker for triplet vs. singlet electron injection, which is potentially related to the highly localized nature of triplets without significant charge-transfer character. Through the use of applied bias on nanoITO:ADT-COOH films, we map the electron injection rate constant dependence on driving force, finding negligible injection from triplets at zero bias due to competing recombination channels. However, at driving forces greater than -0.6 eV, electron injection from the triplet accelerates and clearly produces a trend with increased applied bias that matches predictions from Marcus theory with a metallic acceptor.

| S-EPMC8386672 | biostudies-literature

Singlet Heterofission in Tetracene-Pentacene Thin-Film Blends.

Project description:Heterofission is a photophysical process of fundamental and applied interest whereby an excited singlet state is converted into two triplets on chemically distinct chromophores. The potential of this process lies in the tuning of both the optical band gap and the splitting between singlet and triplet energies. Herein, we report the time-domain observation of heterofission in mixed thin films of the prototypical singlet fission chromophores pentacene and tetracene using excitation wavelengths above and below the tetracene band gap. We found a time constant of 26 ps for endothermic heterofission of a singlet exciton on pentacene in blends with low pentacene fractions, which was outcompeted by pentacene homofission for increasing pentacene concentrations. Direct excitation of tetracene lead to fast energy transfer to pentacene and subsequent singlet fission, which prevented homo- or heterofission of a singlet exciton on tetracene.

| S-EPMC7820980 | biostudies-literature

Opposite Anisotropy Effects of Singlet and Triplet Exciton Diffusion in Tetracene Crystal.

Project description:We observe the diffusion anisotropy difference between singlet and triplet excitons in organic crystals; that is, singlet and triplet excitons may have completely different spatial direction preference for diffusion. This phenomenon can be ascribed to the distinct dependence of different excitonic couplings (Coulomb Förster vs. exchange Dexter) existing in singlet and triplet excitons on their intermolecular distance and intermolecular orientation. Such a discovery provides insights for understanding the fundamental photophysical process in a vast range of organic condensed-phase systems and optimizing the efficiency of organic optoelectronic materials.

| S-EPMC5126140 | biostudies-literature

Singlet fission initiating organic photosensitizations.

Project description:The feasibility of singlet fission (SF) in organic photosensitizers is investigated through spin-flip long-range corrected time-dependent density functional theory. This study focuses on four major organic photosensitizer molecules: benzophenone, boron-dipyrromethene, methylene blue, and rose bengal. Calculations demonstrate that all these molecules possess moderate [Formula: see text]-stacking energies and closely-lying singlet (S) and quintet (triplet-triplet, TT) excitations, satisfying the essential conditions for SF: (1) Near-degenerate low-lying S and (TT) excitations with a significant S-T energy gap, and (2) Moderate [Formula: see text]-stacking energy of chromophores, slightly higher than solvation energy, enabling dissociation for triplet-state chromophore generation. Moreover, based on the El-Sayed rule, intersystem crossing is found to simultaneously proceed at very slow rates in all these photosensitizers. This is attributed to the fact that the lowest singlet excitation of the monomers partly involves [Formula: see text] transitions alongside the main [Formula: see text] transitions. The proposed mechanisms are strongly substantiated by comparisons with experimental studies.

| S-EPMC10774408 | biostudies-literature

Oxygen-catalysed sequential singlet fission.

Project description:Singlet fission is the photoinduced conversion of a singlet exciton into two triplet states of half-energy. This multiplication mechanism has been successfully applied to improve the efficiency of single-junction solar cells in the visible spectral range. Here we show that singlet fission may also occur via a sequential mechanism, where the two triplet states are generated consecutively by exploiting oxygen as a catalyst. This sequential formation of carriers is demonstrated for two acene-like molecules in solution. First, energy transfer from the excited acene to triplet oxygen yields one triplet acene and singlet oxygen. In the second stage, singlet oxygen combines with a ground-state acene to complete singlet fission. This yields a second triplet molecule. The sequential mechanism accounts for approximately 40% of the triplet quantum yield in the studied molecules; this process occurs in dilute solutions and under atmospheric conditions, where the single-step SF mechanism is inactive.

| S-EPMC6858316 | biostudies-literature

Generating Triplets in Organic Semiconductor Tetracene upon Photoexcitation of Transition Metal Dichalcogenide ReS<sub>2</sub>.

Project description:We studied the dynamics of transfer of photoexcited electronic states in a bilayer of the two-dimensional transition metal dichalcogenide ReS2 and tetracene, with the aim to produce triplets in the latter. This material combination was used as the band gap of ReS2 (1.5 eV) is slightly larger than the triplet energy of tetracene (1.25 eV). Using time-resolved optical absorption spectroscopy, transfer of photoexcited states from ReS2 to triplet states in tetracene was found to occur within 5 ps with an efficiency near 38%. This result opens up new possibilities for heterostructure design of two-dimensional materials with suitable organics to produce long-lived triplets. Triplets are of interest as sensitizers in a wide variety of applications including optoelectronics, photovoltaics, photocatalysis, and photon upconversion.

| S-EPMC8201445 | biostudies-literature

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