Spectroscopic and electrical properties of 3-alkyl pyrrole-pyrrole copolymers

Three types of copolymers composed of pyrrole and 3-alkyl pyrroles (with alkyl being pentyl, nonyl and undecyl) have been synthesized. A strong linear dependency of the alkyl chain length on the as-prepared copolymer physical properties is demonstrated via (a) DSC (for phase transition temperatures and enthalpy changes) and (b) UV-vis (for wavelengths of the polaronic and bipolaronic electronic transitions, and ratio of the corresponding absorbances). A trend in the copolymers' doping level vs alkyl chain length is also estimated, via IR, by taking the ratio of band intensities of the stretching modes of the polaronic and bipolaronic species. The copolymers are found to be soluble in organic solvents and their solutions can be cast onto glass substrates or metals resulting in thin films, which can be used as the electroactive component of Schottky diodes. The electrical properties of these diodes are also found to be dependent on increasing 3-alkyl chain length.     

Temperature effect on polaron recombination in conjugated polymers

The microcosmic mechanism of electroluminescence in polymer light emitting diodes (PLEDs) is the recombination of the oppositely charged polarons. In previous studies, it has been demonstrated that the temperature-induced irregular lattice vibration may have non-negligible influence on polaron dynamics. Nevertheless, there are few reports about thermal effect on recombination process between polaron pair, although it is very important for the performance of PLEDs. In this paper, we adopt the modified one-dimensional tight-binding model, including to which the thermal random force, and explore the temperature effect on polaron collision driven by electric field with different strengths. The dynamical simulation is performed by using the non-adiabatic evolution method. The results show that under the influence of electric field, the oppositely charged polarons could recombine into either an exciton with one lattice distortion, or the mixed state of polaron pair and exciton with two lattice distortions. It depends on both field strength and temperature. Anyway, after including temperature effect, a significant improvement of exciton yield is obtained. In addition, the new-formed exciton could perform a random walk along the polymer chain driven by the thermal random force when its strength is large enough. If we further increase the temperature, the stability of exciton would become worse.     

Photo- and electroluminescence of ambipolar,high-mobility,donor-acceptor polymers

Donor-acceptor polymers with narrow bandgaps are promising materials for bulk heterojunction solar cells and high-mobility field-effect transistors. They also emit light in the near-infrared. Here we investigate and compare the photoluminescence and electroluminescence properties of different narrow bandgap (<1.5 eV) donor-acceptor polymers with diketopyrrolopyrrole (DPP), isoindigo (IGT) and benzodipyrrolidone (BPT) cores, respectively. All of them show near-infrared photoluminescence quantum yields of 0.03–0.09% that decrease with decreasing bandgap. Bottom-contact/top-gate field-effect transistors show ambipolar charge transport with hole and electron mobilities between 0.02 and 0.7 cm² V⁻¹ s⁻¹ and near-infrared electroluminescence. Their external quantum efficiencies reach up to 0.001%. The effect of polaron quenching and other reasons for the low electroluminescence efficiency of these high mobility polymers are investigated.     

Theoretical investigation of voltage effect on magnetoresistance in an organic small molecule device

We theoretically study the voltage effect on organic magnetoresistance (OMAR) in a weak disordered small molecule device on the basis of the quantum dynamics. It is found that with the increase of the voltage, the OMAR effect is reduced. The results show a good agreement with the experimental data. In addition, the carrier density effect on OMAR has also been discussed.     

A Model for Liquid-Striped Liquid Phase Separation in Liquids of Anisotropic Polarons

The phase separation between a striped polaron liquid at the particular density and a high density polaron liquid is described by a modified Van der Waals scheme. The striped polaron liquid represents the pseudo gap matter or Wigner-like polaron phase at 1/8 doping in cuprate superconductors. The model includes the tendency of pseudo-Jahn-Teller polarons to form anisotropic directional bonds at a preferential volume with the formation of different “liquid phases”. The model gives the coexistence of a first low density polaron striped liquid and a second high density liquid that appears in cuprate superconductors for doping larger than 1/8. We discuss how the strength of anisotropic bonds controls the variation the phase separation scenarios for complex systems in the presence of a quantum critical point where the phase separation vanishes.     

Phase-breaking effect on polaron transport in organic conjugated polymers

Despite intense investigations and many accepted viewpoints on theory and experiment, the coherent and incoherent carrier transport in organic semiconductors remains an unsettled topic due to the strong electron-phonon coupling. Based on the tight-binding Su-Schrieffer-Heeger (SSH) model combined with a non-adiabatic dynamics method, we study the effect of phase-breaking on polaron transport by introducing a group of phase-breaking factors into π-electron wave-functions in organic conjugated polymers. Two approaches are applied: the modification of the transfer integral and the phase-breaking addition to the wave-function. Within the former, it is found that a single site phase-breaking can trap a polaron. However, with a larger regular phase-breaking a polaron becomes more delocalized and lighter. Additionally, a group of disordered phase-breaking factors can make the polaron disperse in transport process. Within the latter approach, we show that the phase-breaking can render the delocalized state in valence band discrete and the state in the gap more localized. Consequently, the phase-breaking frequency and intensity can reduce the stability of a polaron. Overall, the phase-breaking in organic systems is the main factor that degrades the coherent transport and destroys the carrier stability.     

Self-trapping and Binding of Particles from Singular Pockets in Weakly Doped AFM Mott Insulator

We consider effects of binding and self-trapping of particles added or excited over the insulating state of an antiferromagnetic Mott insulator. The state of an electron or a hole (as appears in ARPES), or of their bound pair (as appears in optics) can be modified by interactions with collective degrees of freedom—deformations of the lattice or of the spin environment. The resulting self-localized state lowers the total particle energy, enhances its effective mass and splits off the electronic level below the nominal insulating gap. We show theoretically that the effect is particularly pronounced for states near the antinodal (π, 0) type point of the Brillouin zone of the CuO₂ because of proximity to the van Hove singularity. We study also the van Hove enhancements for bound states of the electron with neutral and charged impurities and for inter-gap excitons. The results are clearly important for undoped and electron-doped cuprates where the antinodal points correspond to the spectrum bottom for electrons. The effect is indirectly important for lightly hole-doped cuprates concerning the ARPES spectrum transfer between the nodal arcs and the dark antinodal regions.     

Quantum chemical modelling of point defects in KNbO3 perovskite crystals

We present results of semi-empirical quantum chemical calculations for several perovskite KNb_xTa_1−xO₃ (KTN) solid solutions, as well as point intrinsic defects – F centers and hole polarons bound to K vacancy – in KNbO₃. Method of the intermediate neglect of the differential overlap (INDO) was combined with typically 320-atom supercells and atomic geometry optimization. Analysis of the optimized atomic and electronic structure has clearly demonstrated that several nearest Nb atoms substituting for Ta in KTaO₃ – unlike Ta impurities in KNbO₃ – reveal the self-ordering effect, which probably triggers the ferroelectricity observed in KTN. We predict co-existence of one-site (atomic) and two-site (molecular) polarons with close absorption energies (≈1 eV). When available, the INDO results are compared with ab initio calculations. The relevant experimental data are discussed.     

Structural effect of electron acceptor on charge transfer in poly(3-hexylthiophene)/methanofullerene bulk heterojunctions

Radical pairs, polarons and fullerene anion radicals photoinduced by photons with energy of 1.98-2.73 eV in bulk heterojunctions formed by poly(3-hexylthiophene) (P3HT) with bis(1-[3-(methoxycarbonyl)propyl]-1-phenyl)-[6.6]C₆₂ (bis-PCBM) methanofullerene have been studied as compared with P3HT/PCBM composite by direct light-induced EPR (LEPR) method in a wide temperature range. A part of spin polarons and methanofullerene anion radicals are pinned in trap sites which number and depth are governed by an ordering of the polymer/fullerene system and energy of initiating photons. It has been shown that dynamics and recombination of mobile polarons and counter methanofullerene anion radicals are governed by their exchange- and multi-trap assisted diffusion. Relaxation and dynamics of both the charge carriers determined by the steady-state saturation method are governed by structure and conformation of their microenvironment as well as by the photon energy. Longitudinal diffusion of polarons was shown to depend on lattice phonons of crystalline domains embedded into an amorphous polymer matrix. The energy barrier required for polaron interchain hopping is higher than its intrachain diffusion. Pseudorotation of fullerene derivatives in a polymer matrix was shown to follow the activation Pike model. The replacement of PCBM by bis-PCBM provides higher anisotropy of polaron dynamics and decreases its selectivity to the photon energy. This makes spin dynamics easier and minimizes energy dispersion at charge transfer.     

Redox doping behaviour of poly(3,4-ethylenedithiothiophene) - The counterion effect

Poly(3,4-ethylenedithiothiophene) - PEDTT, an alkylene sulphur derivative of PEDOT, presents itself as an interesting polymer with a number of disparate redox and chromic properties compared to its close analogue - PEDOT. In this study we present the results of an investigation into the electrochemical doping process of PEDTT, using four different electrolyte solutions, differing in anion content of the chosen salt. The results show that the anion identity plays a key role in the redox reactions accompanying these processes in what could be interpreted as anion ionochromism. In situ UV-Vis spectroelectrochemical experiments reveal an intriguing double electrochromic transition of PEDTT films during their oxidative doping, going from golden-yellow through green to pomegranate - a quality not so common within the family of electroactive conjugated polymers. The evolution of each UV-Vis spectrum over a potential range indicates that different redox states of the polymer are responsible for the chromatic changes. In the reduction half-cycle, the dedoping process of PEDTT appears to follow a path dissimilar to the p-doping one, featuring only one, direct electrochromic transition of the film’s colour, bypassing the green state, and a distinct two-step bleaching process of doping-induced charge carrier bands. The observed electrochemical and spectral phenomena have been accredited to the specific redox behaviour of doping-induced radical cation and cationic defect states interacting with the dithioalkylene sulphur atom.