A photochemical layer-by-layer solution process for preparing organic semiconducting thin films having the right material at the right place.

The synergistic action of properly integrated semiconducting materials can bring about sophisticated electronic processes and functions. However, it is often a great challenge to achieve optimal performance in organic devices because of the limited control over the distribution of different materials in active layers. Here, we employ a unique photoreaction-based layer-by-layer solution process for preparing ternary organic photovoltaic layers. This process is applicable to a variety of compounds from wide-band-gap small molecules to narrow-band-gap π-extended systems, and enables the preparation of multicomponent organic semiconducting thin films having the right compound at the right place. The resulting ternary photovoltaic devices afford high internal quantum efficiencies, leading to an approximately two times higher power-conversion efficiency as compared to the corresponding binary bulk-heterojunction system. This work opens up new possibilities in designing materials and active layers for solution-processed organic electronic devices.

Photoprecursor Approach Enables Preparation of Well-Performing Bulk-Heterojunction Layers Comprising a Highly Aggregating Molecular Semiconductor.

Active-layer morphology critically affects the performance of organic photovoltaic cells, and thus its optimization is a key toward the achievement of high-efficiency devices. However, the optimization of active-layer morphology is sometimes challenging because of the intrinsic properties of materials such as strong self-aggregating nature or low miscibility. This study postulates that the "photoprecursor approach" can serve as an effective means to prepare well-performing bulk-heterojunction (BHJ) layers containing highly aggregating molecular semiconductors. In the photoprecursor approach, a photoreactive precursor compound is solution-deposited and then converted in situ to a semiconducting material. This study employs 2,6-di(2-thienyl)anthracene (DTA) and [6,6]-phenyl-C71-butyric acid methyl ester as p- and n-type materials, respectively, in which DTA is generated by the photoprecursor approach from the corresponding α-diketone-type derivative DTADK. When only chloroform is used as a cast solvent, the photovoltaic performance of the resulting BHJ films is severely limited because of unfavorable film morphology. The addition of a high-boiling-point cosolvent, o-dichlorobenzene (o-DCB), to the cast solution leads to significant improvement such that the resulting active layers afford up to approximately 5 times higher power conversion efficiencies. The film structure is investigated by two-dimensional grazing-incident wide-angle X-ray diffraction, atomic force microscopy, and fluorescence microspectroscopy to demonstrate that the use of o-DCB leads to improvement in film crystallinity and increase in charge-carrier generation efficiency. The change in film structure is assumed to originate from dynamic molecular motion enabled by the existence of solvent during the in situ photoreaction. The unique features of the photoprecursor approach will be beneficial in extending the material and processing scopes for the development of organic thin-film devices.

Photoprecursor approach as an effective means for preparing multilayer organic semiconducting thin films by solution processes.

The vertical composition profile of active layer has a major effect on the performance of organic photovoltaic devices (OPVs). While stepwise deposition of different materials is a conceptually straightforward method for controlled preparation of multi-component active layers, it is practically challenging for solution processes because of dissolution of the lower layer. Herein, we overcome this difficulty by employing the photoprecursor approach, in which a soluble photoprecursor is solution-deposited then photoconverted in situ to a poorly soluble organic semiconductor. This approach enables solution-processing of the p-i-n triple-layer architecture that has been suggested to be effective in obtaining efficient OPVs. We show that, when 2,6-dithienylanthracene and a fullerene derivative PC71BM are used as donor and acceptor, respectively, the best p-i-n OPV affords a higher photovoltaic efficiency than the corresponding p-n device by 24% and bulk-heterojunction device by 67%. The photoprecursor approach is also applied to preparation of three-component p-i-n films containing another donor 2,6-bis(5'-(2-ethylhexyl)-(2,2'-bithiophen)-5-yl)anthracene in the i-layer to provide a nearly doubled efficiency as compared to the original two-component p-i-n system. These results indicate that the present approach can serve as an effective means for controlled preparation of well-performing multi-component active layers in OPVs and related organic electronic devices.