Formation of polypyrrole and polythiophene within Cu2+- and H+-mordenite hosts studied by EPR and UV-VIS spectroscopy

The reactions of pyrrole and thiophene monomers in copper-exchanged mordenite have been investigated using EPR and UV–VIS absorption spectroscopy. The EPR spectra show a decrease in the intensity of the Cu2+ signal and the appearance of a radical signal due to the formation of oxidatively coupled oligomeric and/or polymeric species in the zeolite host. The reaction ceases when ca. 50% of the copper has reacted and differences in the form of the residual Cu2+ signal between the thiophene and pyrrole reactions suggest a greater degree of penetration of the reaction into the zeolite host for pyrrole, in agreement with previous XPS measurements. The EPR signal intensities show that the average length of the polymer chain that is associated with each radical centre is 15–20 and 5–7 monomer units for polypyrrole and polythiophene, respectively. The widths of the EPR signals suggest that these are at least partly due to small oligomers. The UV–VIS absorption spectra of the thiophene system show bands in three main regions: 2.8–3.0 eV (A), 2.3 eV (B) and 1.6–1.9 eV (D, E, F). Bands A and D–F occur in regions which have previously been observed for small oligomers, 4–6 monomer units in length. Band B is assigned to longer chain polythiophene molecules. We therefore conclude that the reaction between thiophene and copper-loaded mordenite produces a mixture of short oligomers together with some long chain polythiophene. The UV–VIS spectra of the pyrrole system show bands in the regions 3.6 eV (A), 2.7–3.0 eV (B, C) and 1.5–1.9 eV (D, F). Assignments of these bands are less certain than for the thiophene case because of the lack of literature data on the spectra of pyrrole oligomers.

A density matrix renormalization group study of low-lying excitations of polythiophene within a Pariser-Parr-Pople model

Symmetrized density-matrix-renormalization-group calculations have been carried out, within Pariser-Parr-Pople Hamiltonian, to explore the nature of the ground and low-lying excited states of long polythiophene oligomers. We have exploited C-2 symmetry and spin parity of the system to obtain excited states of experimental interest, and studied the lowest dipole allowed excited state and lowest dipole forbidden two photon state, for different oligomer sizes. In the long system limit, the dipole allowed excited state always lies below the lowest dipole forbidden two-photon state which implies, by Kasha rule, that polythiophene fluoresces strongly. The lowest triplet state lies below two-photon state as usual in conjugated polymers. We have doped the system with a hole and an electron and obtained the charge excitation gap and the binding energy of the 1(1)B(u)(-) exciton. We have calculated the charge density of the ground, one-photon and two-photon states for the longer system size of 10 thiophene rings to characterize these states. We have studied bond order in these states to get an idea about the equilibrium excited state geometry of the system. We have also studied the charge density distribution of the singly and doubly doped polarons for longer system size, and observe that polythiophenes do not support bipolarons.

High performance nanocomposite thin film transistors with bilayer carbon nanotube-polythiophene active channel by ink-jet printing

Nanocomposite thin film transistors (TFTs) based on nonpercolating networks of single-walled carbon nanotubes (CNTs) and polythiophene semiconductor [poly [5, 5′ -bis(3-dodecyl-2-thienyl)- 2, 2′ -bithiophene] (PQT-12)] thin film hosts are demonstrated by ink-jet printing. A systematic study on the effect of CNT loading on the transistor performance and channel morphology is conducted. With an appropriate loading of CNTs into the active channel, ink-jet printed composite transistors show an effective hole mobility of 0.23 cm 2 V-1 s-1, which is an enhancement of more than a factor of 7 over ink-jet printed pristine PQT-12 TFTs. In addition, these devices display reasonable on/off current ratio of 105-10 6, low off currents of the order of 10 pA, and a sharp subthreshold slope (<0.8 V dec-1). The work presented here furthers our understanding of the interaction between polythiophene polymers and nonpercolating CNTs, where the CNT density in the bilayer structure substantially influences the morphology and transistor performance of polythiophene. Therefore, optimized loading of ink-jet printed CNTs is crucial to achieve device performance enhancement. High performance ink-jet printed nanocomposite TFTs can present a promising alternative to organic TFTs in printed electronic applications, including displays, sensors, radio-frequency identification (RFID) tags, and disposable electronics. © 2009 American Institute of Physics.

Synthesis and properties of ferrocene-functionalised polythiophene derivatives

The ferrocene-functionalised thiophene derivatives (TFn) with different length of oxyethylene chains were synthesized and polymerized chemically with iron (III) chloride as an oxidant. The resulting ferrocene-functionalised polythiophenes (PTFn) show good solubility in most solvents, such as chloroform (CHCl3) tetrahydrofuran (THF), acetone, etc. The structure and properties of the PTFn polymers were confirmed by IR, H-1 NMR, AFM and photoluminescence (PL). The polymers PTFn show good redox activity with no attenuation of the electroactivity after multiple potential cycling. (C) 2009 Elsevier B.V. All rights reserved.

Constructing Thin Polythiophene Film Composed of Aligned Lamellae via Controlled Solvent Vapor Treatment

Thin poly(3-butylthiophene) (P3BT) film composed of aligned lamellae attached to the edge of the original film has been achieved via a controlled solvent vapor treatment (C-SVT) method. The polarized optical microscopy operated at both single-polarization and cross-polarization modes has been used to investigate the alignment of the fiber-like lamellae. A numerical simulation method is used to quantitatively calculate angle distributions of the lamellae deviated from the film growth direction. Prepatterned P3BT film edge acts as nuclei which densely initialize subsequent crystal growth by exhausting the materials transported from the partially dissolved film. The growth of new film upon crystallization is actually a self-healing process where the two-dimensional geometric confinement is mainly responsible for this parallel alignment of P3BT crystals. The solvent vapor pressure should be carefully chosen so as to induce crystal growth but avoid liquid instability which will destroy the continuity of the film.

Achieving perpendicular alignment of rigid polythiophene backbones to the substrate by using solvent-vapor treatment

The rigid backbone of the poly(3-butylthiophene) molecule adopts a perpendicular orientation with respect to the substrate by using a solvent-vapor treatment (see figure). Small and closely contacting spherulites instead of conventional whisker-like crystals are achieved. This could be utilized to improve charge-carrier mobility particularly in the direction normal to the film plane by designing and constructing thick crystalline domains in the functional layer.

Enhanced electrical conductivity of highly crystalline polythiophene/insulating-polymer composite

Poly(3-butylthiophene) (P3BT)/insulating-polymer composites with high electrical conductivity have been prepared directly from the solution. These composites exhibit much higher conductivity compared to pure P3BT with the same preparation method provided that P3BT content is higher than 10 wt %. Morphological studies on both the pure P3BT and the composites with insulating polymer show that P3BT highly crystallizes and develops into whisker-like crystals. These nanowires are homogeneously distributed within the insulating polymer matrix and form conductive networks, which provide both extremely large interface area between conjugated polymer and insulating polymer matrix and highly efficient conductive channels through out the whole composite. In contrast, the conductivity enhancement of P3HT/PS composite is not so obvious and drops down immediately with increased PS content due mainly to the absence of highly crystalline whisker-like crystals and much larger scale phase separation between the components. The results presented here could further illuminate the origin of conductivity formation in organic semiconducting composites and promote applications of these polymer semiconductor/insulator composites in the fields of organic (opto-)electronics, electromagnetic shielding, and antistatic materials.

In-situ microscopic FT-IR spectroelectrochemical investigation of polythiophene film modified electrode

A polythiophene film was electrochemically deposited on a Pt micro-plate electrode and investigated by cyclic voltammetry and in-situ reflection microscopic FTIR spectroscopy. The FTIR analysis showed that the electropolymerization of thiophene on the Pt surface was affected Lv the surface adsorption processes of thiophene molecules. Two adsorption modes were identified. Two structure models of the polythiophene chain were observed simultaneously. It was proposed that the good conductibility of the polythiophene film was originated from a co-vibratory equilibrium of the link part of model I and model II.