Kyohei Nakano

Organic Planar Heterojunctions: From Models for Interfaces in Bulk Heterojunctions to High-Performance Solar Cells

Recent progress regarding planar heterojunctions (PHJs) is reviewed, with respect to the fundamental understanding of the photophysical processes at the donor/acceptor interfaces in organic photovoltaic devices (OPVs). The current state of OPV research is summarized and the advantages of PHJs as models for exploring the relationship between organic interfaces and device characteristics described. The preparation methods and the characterization of PHJ structures to provide key points for the appropriate handling of PHJs. Next, we describe the effects of the donor/acceptor interface on each photoelectric conversion process are reviewed by examining various PHJ systems to clarify what is currently known and not known. Finally, it is discussed how we the knowledge obtained by studies of PHJs can be used to overcome the current limits of OPV efficiency.

Roles of Energy/Charge Cascades and Intermixed Layers at Donor/Acceptor Interfaces in Organic Solar Cells

The secret to the success of mixed bulk heterojunctions (BHJs) in yielding highly efficient organic solar cells (OSCs) could reside in the molecular structures at their donor/acceptor (D/A) interfaces. In this study, we aimed to determine the effects of energy and charge cascade structures at the interfaces by using well-defined planar heterojunctions (PHJs) as a model system. The results showed that (1) the charge cascade structure enhanced VOC because it shuts down the recombination pathway through charge transfer (CT) state with a low energy, (2) the charge cascade layer having a wider energy gap than the bulk material decreased JSC because the diffusion of the excitons from the bulk to D/A interface was blocked; the energy of the cascade layers must be appropriately arranged for both the charges and the excitons, and (3) molecular intermixing in the cascade layer opened the recombination path through the low-energy CT state and decreased VOC. Based on these findings, we propose improved structures for D/A interfaces in BHJs.

Organic Solar Cells with Controlled Nanostructures Based on Microphase Separation of Fullerene-Attached Thiophene-Selenophene Heteroblock Copolymers

Heteroblock copolymers consisting of poly(3-hexylthiophene) and fullerene-attached poly(3-alkylselenophene) (T-b-Se-PCBP) were synthesized for organic photovoltaic applications by quasi-living catalyst transfer polycondensation and subsequent conversion reactions. Characterization of the polymers confirmed the formation of well-defined diblock structures with high loading of the fullerene at the side chain (∼40 wt %). Heteroblock copolymer cast as a thin film showed a clear microphase-separated nanostructure approximately 30 nm in repeating unit after thermal annealing, which is identical to the microphase-separated nanostructure of diblock copolymer consisting of poly(3-hexylthiophene) and fullerene-attached poly(3-alkylthiophene) (T-b-T-PCBP). These heteroblock copolymers provide an ideal platform for investigating the effects of nanostructures and interfacial energetics on the performance of organic photovoltaic devices.

Crystallization and Polymorphism of Organic Semiconductor in Thin Film Induced by Surface Segregated Monolayers

Preparation of highly crystalline organic semiconductor films is vital to achieving high performance in electronic devices. Here we report that surface segregated monolayers (SSMs) on top of phenyl-C61-butyric acid methyl ester (PCBM) thin films induce crystal growth in the bulk, resulting in a dramatic change in the structure to form a new crystal phase. Highly ordered crystalline films with large domain sizes of several hundreds of nanometers are formed with uniaxial orientation of the crystal structure perpendicular to the substrate. The molecular rearrangements in SSMs trigger the nucleation at a lower temperature than that for the spontaneous nucleation in PCBM. The vertical charge mobility in the SSM-induced crystal domains of PCBM is five times higher than in the ordinary polycrystalline domains. Using surface monolayers may be a new strategy for controlling crystal structures and obtaining high-quality organic thin films by post-deposition crystallization.

Quantitative Evaluation of Molecular Diffusion in Organic Planar Heterojunctions by Time-of-Flight Secondary Ion Mass Spectroscopy

Understanding molecular diffusion across the interfaces in planar heterojunctions is fundamentally important to improving the performance and stability of organic electronic devices. In this study, we quantitatively evaluated the diffusion of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) across the interface of planar heterojunctions into the polymer layers by time-of-flight secondary ion mass spectroscopy. Careful calibration allowed the concentration of PCBM to be determined in the polymer layer at concentrations as low as 0.01 wt %. We found that approximately 1 wt % PCBM was present in the poly(3-hexylthiophene) layer in the planar heterojunction with no thermal treatments, indicating that a small amount of PCBM diffused into the polymer layer even at room temperature. The diffusion behavior depended strongly on the crystallinity of the PCBM layer and the properties of the polymer layers such as glass transition temperature. Further analysis suggested that the diffusion of PCBM into the polymer layers was also related to the interface free energy between the layers.

Drawing organic photovoltaics using paint marker pens

Active layers for organic photovoltaic devices (OPVs) were prepared by hand drawing with paint marker pens containing solutions of the materials. Although the pen-coated organic films were visually non-uniform with quite high surface roughness, OPV devices using these films exhibited similar or slightly better performances than those using spin-coated films. As such, the pen-coating technique represents an easily accessible, inexpensive, and highly material-efficient method for fabricating OPVs.

High Sensitivity Tuning of Work Function of Self-Assembled Monolayers Modified Electrodes Using Vacuum Ultraviolet Treatment

We demonstrate systematic work function tuning of thiol-based SAM-modified gold electrodes with high controllability and sensitivity as high as 0.05 eV using vacuum ultraviolet technique (VUV). Under different irradiation times, both work function and wettability of the metal surface is modified. Fine tuning of the electrode work function is demonstrated by observable changes in the reverse current of a polymer Schottky diode. Additionally, the change in SAM chemical functionality validates the work function changes of VUV-irradiated electrodes. Our selective work function patterning on a single Au electrode via VUV could also reduce the required fabrication steps for more complex circuits.