Electron Lifetime of Over One Month in Disordered Organic Solid-State Films.

Understanding intrinsic carrier lifetime in disordered organic solid-state semiconductors is essential for improving device performance in not only molecule-based optoelectronic devices such as organic solar cells (OSC) but also photocatalysts used for producing solar fuel cells. Carriers in disordered films are generally thought to have short lifetimes on a scale ranging from nanoseconds to milliseconds. These short carrier lifetimes cause loss of charges in OSCs and low quantum yields in photocatalysts and impede the future application of organic semiconductors to, for example, charge-storage-based memory devices. This study reports an ultralong intrinsic carrier lifetime of more than one month in a disordered film of an organic semiconductor stored at room temperature without external power. This extraordinary lifetime, which is several orders of magnitude longer than that generally believed possible in conventional organic semiconductors, arises from carrier stabilization by spontaneous orientation polarization, excited spin-triplet recycling, and blocking of recombination processes in disordered films.

Significant role of spin-triplet state for exciton dissociation in organic solids.

Clarification of the role of the spin state that initiates exciton dissociation is critical to attaining a fundamental understanding of the mechanism of organic photovoltaics. Although an excited spin-triplet state with an energy lower than that of excited spin-singlet state is disadvantageous in exciton dissociation, a small electron exchange integral results in small singlet-triplet energy splitting in some material systems. This energy splitting leads to a nearly isoenergetic alignment of both excited states, raising a question about the role of excited spin states in exciton dissociation. Herein, we show that the spin-triplet rather than the spin-singlet plays a critical role in the exciton dissociation that leads to the formation of free carriers. This result indicates that the spin-triplet inherently acts as an intermediate, leading to exciton dissociation. Thus, our demonstration provides a fundamental understanding of the role of excited spin states of organic molecular systems in photoinduced charge-carrier generation.

Slow recombination of spontaneously dissociated organic fluorophore excitons.

The harvesting of excitons as luminescence by organic fluorophores forms the basis of light-emitting applications. Although high photoluminescence quantum yield is essential for efficient light emission, concentration-dependent quenching of the emissive exciton is generally observed. Here we demonstrate generation and accumulation of concentration-dependent "long-lived" (i.e., over 1 h) photo-generated carriers and the successive release of their energy as electroluminescence in a solid-state film containing a polar fluorophore. While fluorophore excitons are generally believed to be stable because of their high exciton binding energies, our observations show that some of the excitons undergo spontaneous exciton dissociation in a solid-state film by spontaneous orientation polarization even without an external electric field. These results lead to the reconsideration of the meaning of "luminescence quantum yield" for the solid films containing polar organic molecules because it can differ for optical and electrical excitation.

A narrow band-rejection filter based on block copolymers.

We demonstrate filtering characteristics of a polymer band-rejection filter (PBRF) with highly-ordered microphase-separated structure of block copolymers (BCPs). This PBRF is characterized by an Optical Density > 5 blocking at the center wavelength and narrow blocking full bandwidth of 8 nm. Moreover, the wavelength is easily tuned by blending two BCPs with different molecular-weight. A low frequency Raman shift of 200 cm(-1) are, in fact, detected with a sufficient resolution by using this filter in Raman spectroscopy.