title: Benzodipyrrolidone (BDP)-based polymer semiconductors containing a series of chalcogen atoms: comprehensive investigation of the effect of heteroaromatic blocks on intrinsic semiconducting properties.
abstract: In order to determine the effects of actual 'chalcogen atoms' on semiconducting properties for application in a variety of optoelectronic devices, a class of donor (D)-acceptor (A) polymer semiconductors, namely PBDP-Fu, PBDP-Th, and PBDP-Se, containing the recently formulated benzodipyrrolidone (BDP) accepting unit and furan (Fu), thiophene (Th), or selenophene (Se) as a donating unit has been synthesized, characterized, and used in an active layer of organic field-effect transistors (OFETs). With the LUMO levels being comparatively consistent for all three polymers (-3.58 to -3.60 eV) due to the dominant BDP contribution to the polymer backbone, the HOMO energies are somewhat sensitive to the structurally distinctive feature of the donor counits used. Utilizing a combination of X-ray diffraction (XRD) and atomic force microscopy (AFM), it is apparent that further crystalline domains occur with edge-on orientation for the polymers (PBDP-Th and PBDP-Se) with relatively heavier chalcogen atoms such as Th and Se, compared with PBDP-Fu which has a rather amorphous nature. Investigation of their OFET performance indicates that all the polymers show well balanced ambipolar operations. The desirable morphological structures of both the PBDP-Th and PBDP-Se result in higher mobilities in OFETs than those of PBDP-Fu. In particular, 200 °C annealed PBDP-Se OFETs results in ambipolarity being mobile for both holes of up to 1.7 × 10(-2) cm(2)/V·s and electrodes of up to 1.9 × 10(-2) cm(2)/V·s. In addition, OFETs with PBDP-Th show nearly equivalent charge carrier mobilities for both holes (μ(h) = 1.2 × 10(-2) cm(2)/V·s) and electrons (μ(e) = 1.1 × 10(-2) cm(2)/V·s). Consequently, we systematically demonstrate how the manipulation of existing heteroaromatics can modulate the electronic properties of conjugated D-A polymers, elucidating structure-property relationships that are desirable for the rational design of next generation materials.
authors.affiliation: School of Energy and Chemical Engineering, KIER-UNIST Advanced Center for Energy, Low Dimensional Carbon Materials Center, Ulsan National Institute of Science and Technology (UNIST) , Banyeon-ri 100, Eonyang-eup, Ulju-gun, Ulsan, 689-798 South Gyeongsang, South Korea.
authors.forename: Kyu Cheol
authors.initials: KC
authors.lastname: Lee
authors.forename: Won-Tae
authors.initials: WT
authors.lastname: Park
authors.forename: Yong-Young
authors.initials: YY
authors.lastname: Noh
authors.forename: Changduk
authors.initials: C
authors.lastname: Yang