Systematic side-chain engineering through adjustment of spacer groups in diketopyrrolopyrrole-thiophene vinylene thiophene (DPP-TVT) polymers reveals odd–even dependence of device performance.

Semiconducting polymer nanoparticles dispersed in water are synthesized by a novel method utilizing non-ionic surfactants. By developing a smart surfactant engineering technique involving a selective post-removal process of surfactants, an unprecedentedly high mobility of 2.51 cm(2) V(-1) s(-1) from a water-borne colloid is demonstrated for the first time.

To improve the charge carrier mobility of diketopyrrolopyrrole donor−acceptor copolymer semiconductors, the length of the donor building block is controlled using vinylene moieties, and its effects on crystalline structure and charge transport are systematically studied. We synthesize P29-DPP-TBT with two vinylene linkages between thiophene units and compare it with P29-DPP-TVT with single vinylene linkage. Density functional theory calculations predict enhanced backbone planarity of P29-DPP-TBT compared to P29-DPP-TVT, which can be related to the increased conjugation length of P29-DPP-TBT as proved by the increased free exciton bandwidth extracted from UV−vis absorption spectra and the wavenumber shift of the C−C peaks to higher values in Raman spectra. From two-dimensional grazing incident X-ray diffraction studies, it is turned out that the paracrystalline disorder is lower in P29-DPP-TBT than in P29-DPP-TVT. Near-edge X-ray absorption fine structure spectroscopy reveal that more edge-on structure of polymer backbone is formed in the case of P29-DPP-TBT. By measuring the temperature dependence of the charge carrier mobilities, it is turned out that the activation energy for charge hopping is lower for P29-DPP-TBT than for P29-DPP-TVT. Collectively, these results imply that the substitution of extended π-conjugated donor moiety of polymeric semiconductors can yield a more planar backbone structure and thus enhanced intermolecular interaction which enables more perfect crystalline structure as well as enhanced charge transport behavior.

To evaluate the effect of side chain characteristics on the photovoltaic performance of small molecules containing both benzodithiophene (BDT) and thienopyrroledione (TPD), we designed and synthesized two such molecules, one containing a branched 2-ethylhexyl (2EH) side chain on the BDT unit (BDTEH-TTPD) and the other containing a linear n-octyl (C8) side chain on the BDT unit (BDTO-TTP). The optical and electrochemical properties and crystalline structures of these molecules were examined. Compared to BDTO-TTPD, BDTEH-TTPD, showed stronger light absorption, longer-range ordering and shorter π-π stacking distances between backbones. As a result, the power conversion efficiency of a bulk heterojunction solar cell based on BDTEH-TTPD (2.40%) was substantially higher than that of the BDTO-TTPD device (1.12%).

We show that selenophene-substitution can be an efficient synthetic strategy toward high charge carrier mobility of isoindigo (IID)-based copolymers when their side chains are optimized. A high mobility of 5.8 cm(2) V(-1) s(-1) is demonstrated by a strategically designed IID-based polymer, with both side-chain adjustment and selenophene-substitution.

Two novel semiconducting polymers based on benzodithiophene and dithienophosphole oxide (DTP) units are designed and synthesized. A novel electron‐deficient DTP moiety is developed. Surprisingly, the introduction of DTP units brings highly polarizable characteristics, which is beneficial for the photocurrent in solar cells. Thus, the donor–acceptor type of conjugated polymers based on this novel acceptor has superior charge transfer properties and highly efficient PL quenching efficiencies. As a result, polymer solar cells (PSCs) with high power conversion efficiencies of 6.10% and 7.08% are obtained from poly(3,5‐didodecyl‐4‐phenylphospholo[3,2‐b:4,5‐b']dithiophene–4‐oxide‐alt‐4,8‐bis(5‐decylthiophen‐2‐yl)benzo[1,2‐b:4,5‐b']dithiophene) (PDTP–BDTT) and PDTP–4‐oxide‐alt‐4,8‐bis(5‐decylselenophen‐2‐yl)benzo[1,2‐b:4,5‐b']dithiophene) (PDTP–BDTSe), respectively, when the photoactive layer is processed with the 1,8‐octanedithiol (ODT) additive. The PDTP–BDTSe copolymer is now the best performing DTP‐based material for PSCs. Using the polarizable unit strategy determined in this study for the molecular design of conjugated polymers is expected to greatly advance the development of organic electronic devices.

Although high power conversion efficiency of over 14% has been achieved using nonfullerene acceptors (NFAs) in organic photovoltaics (OPVs), securing their insensitive device performance to the thickness of the photoactive layer remains an indispensable requirement for their successful commercialization via printing technologies. In this study, by synthesizing a new series of ITIC‐based NFAs having alkyl or alkoxy groups, it is found that the bulk heterojunction morphology dependence on the thickness of the photoactive layer becomes more severe as the difference in the surface energy of the donor and acceptor increases. It is believed that this observation is the origin that yields the device performance dependence on the thickness of the photoactive layer. Through sensitive control of the surface energy of these ITIC‐based NFAs, it is demonstrated that thickness‐insensitive OPVs can be achieved even using a doctor blade technique under air without using any additives. It is believed that present approach provides an important insight into the design of photoactive materials and morphology control for the printable OPVs using NFAs.

We report two newly synthesized naphthalene diimide (NDI)-based conjugated polymers, poly[(E)-2,7-bis(2-decyltetradecyl)benzo [lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone-vinylene-thiophene-vinylene] (PNDI-VTV) and poly[(E)-2,7-bis(2-decyltetradecyl)benzo [lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone-vinylene-selenophene-vinylene] (PNDI-VSV) with different donor units as electron-transporting organic semiconductors for organic fieldeffect transistors (OFETs). Furthermore, we study the effect of vinylene position on electron transport in the NDI polymers by using two similar polymers but with thiophene-vinylene-thiophene (PNDI-TVT) instead of vinylene-thiophene-vinylene or selenophene-vinylene-selenophene (PNDI-SVS) instead of vinyleneselenophene-vinylene. By incorporating vinylene between thiophene (or selenophene) units, the resulting NDI-based polymers PNDI-VTV and PNDI-VSV show larger backbone planarity than PNDI-TVT and PNDI-SVS. The polymers with a shorter acceptor monomer unit (PNDI-VTV and PNDI-VSV) show a strong face-on orientation, whereas those with a longer monomer unit (PNDI-TVT and SVS) exhibit a mixed face-on and edge-on orientation by two-dimensional grazing incidence X-ray diffraction. Optimized PNDI-VTV and PNDI-VSV OFETs exhibit electron mobilities of 0.043 and 0.7 cm 2 /(V•s), which is quite lower than those of PNDI-TVT and PNDI-SVS. In addition, the activation energies for electron transport of PNDI-VTV and PNDI-VSV were larger than those of PNDI-TVT and PNDI-SVS. Overall, this research provides the insight that the molecular alignment on the substrate can be controlled by the sequence of rigid acceptor monomer molecules for improving the electron transport of NDI polymers.