Thin film of a porphyrin‐end‐functionalized poly(cyclohexane)/fullerene‐end‐functionalized poly(4‐diphenylaminostyrene) blend: Control of microphase separation in a light‐harvesting system for polymer solar cells

Abstract

Thin films of a tetraphenylporphyrin‐end‐functionalized polycyclohexane zinc complex (ZnTPP‐PCHE)/fullerene‐C60 (C60) end‐functionalized poly(4‐diphenylaminostyrene) (C60‐PDAS) were prepared to investigate their potential as a light‐harvesting system for polymer solar cells (PSCs). The microphase separation in the ZnTPP‐PCHE/C60‐PDAS blends had a significant effect on the optical properties; the absorption band of the microphase separation structure that overlaps the visible‐light region was considerably enhanced with an increase in the C60 concentration in the polymer film, although both pristine ZnTPP‐PCHE and C60‐PDAS thin films had only weak absorption bands in that region. Therefore, this polymer blend is considered to be suitable for use as a light‐harvesting system for PSCs. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

Controlled self-assembly of porphyrin/fullerene donor-acceptor complex in a polymer thin film

“…17,18 However, the incorporation of porphyrin molecules into the polymer chain with covalent bonding has been difficult to achieve and a very complicated synthetic route was required. [16][17][18] The next topic of interest was, therefore, the controlled self-assembly of porphyrin/fullerene donor-acceptor complex (layer) from a combination of polymers, fullerenes, and free porphyrin molecules.…”

Controlled dispersion of a porphyrin/fullerene donor‐acceptor complex in semiconducting polymer thin films: Intermolecular interactions of polymers with porphyrin and fullerene

“…Figure presents AFM images of the 60/10/30 PVNP/ZnTNpP/PCBM [Figure (a)], PDAS/ZnTNpP/PCBM [Figure (b)], PVPY/ZnTNpP/PCBM [Figure (c)], and P3HT/ZnTNpP/PCBM [Figure (d)] blend films. On the basis of the results of our previous studies, the bright and dark regions in these images correspond to the polymer and PCBM phases, respectively …”

“…Accordingly, the ZnTNpP molecules seemed to have been well dispersed throughout the PVNP phase, even though excess PCBM molecules were added in the blend, as in the 60/10/30 PVNP/ZnTNpP/PCBM blend [Figure (d)]. In such cases, when the strength of the intermolecular interactions between the ZnTNpP and the PCBM was sufficiently strong compared to that between the PVNP/PCBM and PVNP/ZnTNpP, one would expect that all of the ZnTNpP molecules would be dispersed in the PVNP phase in the form of ZnTNpP/PCBM donor–accepter complexes . To examine the strengths of the intermolecular interactions of the porphyrin/fullerene system in the PVNP/ZnTNpP/PCBM blend, the PL spectra of the polymer thin films were acquired.…”

“…Recently, we proposed the tuning of the molecular compatibilities (i.e., intermolecular interactions) of polymer/fullerene, polymer/porphyrin, and porphyrin/fullerene (Scheme ) systems as a new concept for the controlled dispersion of porphyrin molecules into polymer thin films . For example, when polycyclohexane (PCHE; a hydrocarbon polymer), zinc(II)−5,10,15,20‐ tetra ‐(2‐naphthyl)porphyrin (ZnTNpP; a porphyrin derivative), and [6,6]‐phenyl‐C 61 ‐butyric acid methyl ester (PCBM; a fullerene derivative) were blended, a clear microphase separation of PCHE and PCBM was observed, and a ZnTNpP/PCBM donor–acceptor complex layer was formed between the PCHE and PCBM phases .…”

“…For example, when polycyclohexane (PCHE; a hydrocarbon polymer), zinc(II)−5,10,15,20‐ tetra ‐(2‐naphthyl)porphyrin (ZnTNpP; a porphyrin derivative), and [6,6]‐phenyl‐C 61 ‐butyric acid methyl ester (PCBM; a fullerene derivative) were blended, a clear microphase separation of PCHE and PCBM was observed, and a ZnTNpP/PCBM donor–acceptor complex layer was formed between the PCHE and PCBM phases . Furthermore, we have demonstrated the ready formation of porphyrin/fullerene donor–acceptor complexes in various polymer thin films, in which the intermolecular interactions caused by charge‐transfer from porphyrin to fullerene within the porphyrin/fullerene complex appear to be very strong . In addition, we noticed that the tracking location of maxima of the Soret band of porphyrin acted as a good indicator to reveal the degree of its aggregation in polymer/porphyrin blends.…”