Temperature Dependence of Magnetophotoconductance in One-Dimensional Molecular Assembly of Hexabenzocoronene

Temperature dependencies of transient photocharge and magnetophotoconductance effect of columnar self-assemblies of the hexabenzocoronene derivative (HBC-C14), which is a prospective one-dimensional photoconductor, presented different thermal activation processes for carrier generation and transportation, respectively. Thermal equilibrium between the low-lying short distance and high-lying long-distance geminate electron–hole (e–h) pairs is the origin for activation in carrier generation. The energy difference between these e–h pairs is estimated to be 7 meV, which was mainly due to the Coulomb interaction. On the other hand, the carrier transport with thermal activation was understood by the multiple trapping model. Carrier detrapping from localized states located in the band gap causes the thermal activation in the carrier transport. The shallow energy depth at the density peak of the localized state from the mobility edge (10 ± 3 meV) is a unique nature of HBC-C14 self-assemblies. A very narrow Gaussian distribution for density of the localized states was also clarified

Mechanism of Intersystem Crossing of Thermally Activated Delayed Fluorescence Molecules

The spin sublevel dynamics of the excited triplet state in thermally activated delayed fluorescence (TADF) molecules have not been investigated for high-intensity organic light-emitting diode materials. Understanding the mechanism for intersystem crossing (ISC) is thus important for designing novel TADF materials. We report the first study on the ISC dynamics of the lowest excited triplet state from the lowest excited singlet state with charge-transfer (CT) character of TADF molecules with different external quantum efficiencies (EQEs) using time-resolved electron paramagnetic resonance methods. Analysis of the observed spin polarization indicates a strong correlation of the EQE with the population rate due to ISC induced by hyperfine coupling with the magnetic nuclei. It is concluded that molecules with high EQE have an extremely small energy gap between the ¹CT and ³CT states, which allows an additional ISC channel due to the hyperfine interactions

Temperature Dependence of Magnetophotoconductance in One-Dimensional Molecular Assembly of Hexabenzocoronene

Temperature dependencies of transient photocharge and magnetophotoconductance effect of columnar self-assemblies of the hexabenzocoronene derivative (HBC-C14), which is a prospective one-dimensional photoconductor, presented different thermal activation processes for carrier generation and transportation, respectively. Thermal equilibrium between the low-lying short distance and high-lying long-distance geminate electron–hole (e–h) pairs is the origin for activation in carrier generation. The energy difference between these e–h pairs is estimated to be 7 meV, which was mainly due to the Coulomb interaction. On the other hand, the carrier transport with thermal activation was understood by the multiple trapping model. Carrier detrapping from localized states located in the band gap causes the thermal activation in the carrier transport. The shallow energy depth at the density peak of the localized state from the mobility edge (10 ± 3 meV) is a unique nature of HBC-C14 self-assemblies. A very narrow Gaussian distribution for density of the localized states was also clarified

Effect of Acceptor Lamination on Photocarrier Dynamics in Hole Transporting Hexabenzocoronene Nanotubular Self-Assembly

Measurements of transient photoconductance under an external magnetic field were used to investigate photocarrier dynamics in low-dimensional hexabenzocoronene (HBC) self-assemblies, which are a promising material group for highly efficient solar cells achieved by bottom-up technology, and to clarify the effect of lamination with electron acceptor layer on the surfaces of HBC nanotubes. In an HBC column without an acceptor, the carrier generation yield from a geminate electron–hole (e-h) pair is dependent on the external electric and magnetic fields. The time dependence of the magnetic field effect on geminate e-h pair dynamics in the HBC column structure was analyzed to estimate the recombination rate constants of the singlet and triplet e-h pairs (<i>k</i>_r^S and <i>k</i>_r^T), which were 1.5 × 10⁸ and 1.2 × 10⁸ s^–1 respectively. The same kinetic analysis with consideration of the electric field effect on the photocarrier generation yield provided an electric field dependent dissociation rate constant in the range of 10⁷–10⁸ s^–1 in the HBC column structure. However, neither electric nor magnetic field effects on the carrier generation process were observed in acceptor-appended HBC nanotubes. The disappearance of the external field effects in acceptor-appended HBC indicates that the geminate recombination is reduced substantially by a well-organized donor/acceptor heterojunction with an interval of a few nanometers due to some σ-bonds. However, efficient nongeminate recombination with a ratio of <i>k</i>_r^S:<i>k</i>_r^T = 1.0:0.8 in the acceptor-appended HBC nanotubes was also elucidated by the incident photon density and magnetic field effects, which is an inherent nature in materials with high carrier density

What Can Be Learned from Magnetic Field Effects on Singlet Fission: Role of Exchange Interaction in Excited Triplet Pairs

Magnetic field effects (MFEs) on singlet fission were studied by observing fluorescence from organic crystal of 1,6-diphenyl-1,3,5-hexatriene under magnetic fields of up to 5 T. We found anomalous MFE dips at magnetic fields higher than 2 T, in addition to the known MFEs which saturated around 1 T. The observed results were analyzed by using the stochastic Liouville equation (SLE) in which a distance-dependent exchange interaction (<i>J</i>) in triplet pair, hopping of triplet, and geminate fusion in contacted triplet pair were incorporated. The SLE analysis revealed that the observed dips were caused by a MFE due to the level crossing mechanism and strongly suggested that the contacted triplet pair has a large <i>J</i>, which has been ignored in the previous model of MFEs on the singlet fission. Present results lead to the conclusion that the initial dissociation of the singlet exciton to the contacted triplet pair does not show the MFE and the triplet pair at a <i>separated</i> distance produced by hopping of the triplet plays an important role on the generation of the MFE on the singlet fission

Solvent Viscosity Effect on Triplet–Triplet Pair in Triplet Fusion

The effect of the solvent viscosity dependence of time-resolved magnetoluminescence (ML) on the delayed fluorescence of 9,10-diphenylanthracene (DPA) sensitized by platinum octaethylporphyrin has clarified the structure and dynamics of the triplet–triplet pair (TT), i.e., the transition state of triplet fusion. Phase inversion of the ML effect with time provides evidence for the recycle dynamics of the excited triplet state for DPA in triplet fusion. The electron spin-relaxation by random molecular rotation causes intersystem crossing among the different spin states of the triplet–triplet pair and allows the ^3,5TT to engage in triplet fusion. Therefore, slow-down of the molecular diffusion by an increase in the solvent viscosity can enhance the triplet fusion yield. However, the reduction of the ML effect observed in quite high viscosity solvents suggests that the substantially slow rotational motion decreases the triplet fusion yield due to steric factors in electron exchange from the triplet–triplet pair

Carrier Dynamics in Pentacene|C₆₀ Bilayer Solar Cell Investigated through the Magnetoconductance

We demonstrate the magnetoconductance (MC) effect originated from depressing the spin mixing in encounter pairs under the external magnetic field provides quantitative information about the singlet fission, the charge recombination, and the trap-related dynamics with triplet exciton in a bilayer device of pentacene (Pen) and fullerene (C₆₀). Three MC effects in low-, moderate-, and high-fields were detected in the bilayer device at room temperature. Kinetic analysis of the low-field MC effect showed that the charge recombination yield at the Pen|C₆₀ interface is ∼1%. Quantum mechanical simulations for dynamics of spin-carrying pairs following the conservation rule of spin angular momentum in recombination showed that the moderate- and high-field MC effects are caused by, respectively, the trap-related dynamics with triplet exciton and the singlet fission with a maximum yield of 52% in the layers. The quantitative information obtained by investigating the MC effect will contribute to the development of high-efficiency organic solar cells devices