Structure and morphology control in thin films of regioregular poly(3‐hexylthiophene)

This review focuses on the structural control in thin films of regioregular poly(3‐hexylthiophene) (P3HT), a workhorse among conjugated semiconducting polymers. It highlights the correlation existing between processing conditions and the resulting structures formed in thin films and in solution. Particular emphasis is put on the control of nucleation, crystallinity and orientation. P3HT can generate a large palette of morphologies in thin films including crystalline nanofibrils, spherulites, interconnected semicrystalline morphologies and nanostructured fibers, depending on the elaboration method and on the macromolecular parameters of the polymer. Effective means developed in the recent literature to control orientation of crystalline domains in thin films, especially by using epitaxial crystallization and controlled nucleation conditions are emphasized. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1218–1233, 2011     

Molecular dynamics simulations of a poly(p-phenylene) oligomer

We have studied the conformation and coefficient of thermal expansion in the poly(p-phenylene) oligomer p-sexiphenyl (C₃₆H₂₆) by molecular dynamics simulations. Studies of the backbone phenyl–phenyl torsion angle in a simulated p-sexiphenyl crystal at room temperature indicate the presence of torsional librations of approximately ±20°. Further analysis of the phenyl–phenyl backbone torsion angle in less closely packed regions of the simulated crystal (crystal ends) indicate the presence of 180° phenyl ring flips, in agreement with solid-state deuterium NMR data on poly(p-phenylene oligomers). The linear coefficient of thermal expansion was also calculated and found to be negative, in qualitative agreement with experimental data on rigid-rod compounds. © 1993 John Wiley & Sons, Inc.     

Approach of the mechanism of poly(3-octyl thiophene) crosslinking under electron beam

Poly(3-octylthiophene) was used as a negative resist in e-beam microlithography. This conducting polymer fulfills the main requirements placed on materials which can be useful in this type of process. However, chemical modifications leading to crosslinking are not clearly established at this time. Approach of a mechanism is proposed in this paper which is supported by spectroscopic results obtained from the irradiated materials: it seems reasonable that crosslinking might occur between lateral alkyl groups eventually on carbon atoms in allylic position with the formation of a carbon - carbon double bond between locally stacked Poly(3-octylthiophene) chains.     

Photo- and thermo-oxidation of poly(p-phenylene-vinylene) and phenylene-vinylene oligomer

This paper reports a study of the photo- and thermo-degradation of poly(p-phenylene-vinylene)-type (PPVs) materials, including a five-ring n-octyloxy substituted phenylene-vinylene oligomer (Ooct-OPV5) and poly(p-phenylene-vinylene) (PPV). The modifications in the chemical structure of the thin films submitted to UV-visible light irradiation and thermal oxidation were analysed with infrared spectroscopy, and the oxidation products were identified by derivatisation reactions. Results showed that the photochemical and thermal behaviour of the Ooct-OPV5 oligomer was similar to that of MDMO-PPV (poly[2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylenevinylene), which is a polymer used in organic solar cells. Additionally, the identification of the products resulting from the oxidation of the vinylene bonds was simpler in Ooct-OPV5 and PPV compared to MDMO-PPV In contrast, the oxidation mechanisms of PPV, which has no ether substituent, and MDMO-PPV are not identical; the disappearance of the double bonds in PPV does not involve the formation of aromatic ketones. It was also shown that the absence of ether substituents does not decrease the rate of photo-oxidation of PPV compared to MDMO-PPV. Finally, as the same mechanisms proposed for Ooct-OPV5 and PPV occur under both photo- and thermo-oxidative conditions of ageing, this confirms that singlet oxygen does not play a decisive role in the photo-oxidation of PPVs.     

Preparation of polypyrrole/polyvinylalcohol (PPy/PVA) composite foam electrode material

<正>Polypyrrole/polyvinylalcohol(PPy/PVA) foam was prepared by direct foam polymerization in water and then it was coated on the indium-tin oxide transparent conductive glass(ITO) to form conventional three-electrode cell.FTIR and UV-vis spectra were adopted to characterize the molecular structure and the absorption spectra of foam material,respectively.The porous structure of PPy/PVA foams and their photoelectric conversion behaviors were studied.The dimension of the pores is bigger than 100μm in diameter.Compared with the smooth film,the V_(oc) and I_(sc) of the foam film enhanced by 1.58-fold and 5.59-fold,respectively.     

Impact of the anion on electrochemically doped regioregular and regiorandom poly(3-hexylthiophene)

Chemical and electrochemical doping of π-conjugated polymers is an important aspect in determining the performance and enabling the operation of many organic electronic devices, from organic light emitting diodes and thermoelectrics to organic electrochemical transistors. In both chemical doping and electrochemical doping an ionized dopant or counterion is present along with the doped π-conjugated polymer. This dopant or counterion is not a benign spectator, rather, its presence can significantly impact the optical, electronic, and thermoelectric properties of the resulting material. Here, we investigate how counterion structure impacts the electrochemical doping ability, oxidation potential, ionization energy, and polaron absorbance of regioregular (rr) and regiorandom (rra) P3HT. We find that in most cases the anion has a small effect on the polymer oxidation potential, except for in the case of rr-P3HT with the large tetrakis[3,5-bis(trifluoromethyl)phenyl]borate anion. We propose that this large anion is excluded from the crystalline regions and thus the oxidation potential is similar to that of rra-P3HT. The anions also result in significant differences in polaron absorbance and ionization energies, thereby emphasizing the important role of the counterion in determining the optical and electronic properties of doped π-conjugated polymers.     

Photophysical properties of sexi(3-methoxythiophene): evidence for energy migration in a conducting oligomer, based on fluorescence quenching

The electronic absorption and fluorescence excitation and emission spectra of poly(3-methoxythiophene) (PMOT), a soluble, electroactive oligomer mainly constituted of hexamer, were investigated in dimethylsulfoxide at room temperature. The study of PMOT photophysical properties suggests the existence of important pi-electronic delocalization in the oxidized and reduced form of the oligomer. A significant fluorescence quenching of PMOT takes place in the presence of various quenchers such as dimethylterephthalate, potassium iodide and thallium acetate. Quenching mechanisms implying a quencher-induced intersystem-crossing step are proposed. Modified Stern-Volmer relationships were obtained with large quenching bimolecular rate constants (2.7 x 10(9)-6.1 x 10(11) l mol(-1) s(-1)), which suggests electronic energy migration throughout the repeat units of the PMOT hexamer.     

Structural transitions of nanocrystalline domains in regioregular poly(3‐hexyl thiophene) thin films

The effects of solution processing and thermal annealing on thin film morphology and crystalline structures of regioregular poly(3‐hexyl thiophene) (RR P3HT) are studied in terms of molecular weight (M_w). Using grazing‐incidence X‐ray diffraction, π‐conjugated planes in drop‐cast films from chloroform solutions are found to be preferentially oriented parallel to the substrates regardless of M_w. However, the mesoscale nanocrystalline morphology of the drop‐cast films is significantly affected by M_w, exhibiting a distinctive morphological transition from short nanorods to long nanofibrils above a critical number‐averaged M_w (～ 3.6 kDa). This is probably due to the change in a conformation change from an extended‐chain to a folded‐chain, as M_w of RR P3HT increases. In contrast, spin‐casting of high M_w RR P3HT produces less ordered films with a lower crystallinity and mixed parallel/perpendicular orientations of π‐conjugated planes. The crystallinity and parallel π‐conjugated orientation of RR P3HT in spin‐cast films could be improved by thermal treatments at high‐temperatures either (1) above the glass transition temperature or (2) above the melting temperature of RR 3PHT followed by recrystallization upon cooling under vacuum. However, the charge mobility of the spin‐cast films for a field‐effect transistor application is still lower than that of the drop‐cast films. This would be attributed to the chain oxidation and the development of distinct grain boundaries between RR P3HT nanofibrils during the thermal treatments. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1303–1312, 2007     

聚噻吩的光电化学研究

导电聚合物是由一些具有共轭π键的聚合物经化学或电化学掺杂后形成的导电率可从绝缘体延伸到导体范围的一类高分子材料。其中噻吩及其衍生物具有导电率高、环境稳定性好、成膜性好、禁带宽度小等特点,是用做光伏电池的理想材料。相继报道的有聚3-甲噻吩[1]、聚3-己基噻吩[2],聚(3-十一烷基-2,2’-并噻吩)[3]等。对于聚噻吩的光电化学性质的研究,在国际上很少见报道,国内尚未见报道,本文对聚噻吩(PTh)的光电化学性质进行了研究。1实验部分1.1仪器与试剂光电化学实验采用带石英窗口的三电极电解池,工作电极为ITO/PTh膜电极,参比电极为饱和…     

The conformation of poly(3-dodecyl thiophene) within methacrylic polymer matrix

Blends of poly(3-dodecyl thiophene) (PDDT) with poly(methyl methacrylate), poly(butyl methacrylate) (PBMA), and poly(methyl methacrylate-co-butyl methacrylate) (PMMA/PBMA) were studied by polarization optical microscopy, atomic-force microscopy, and absorption spectroscopy and were modeled using molecular dynamics (MD) simulations. The observed thermochromic transitions are shown to be host-matrix dependent, with PDDT/PBMA absorption spectra differing substantially from pristine PDDT. The dispersion of PDDT within PBMA matrix is observed to be greater than in the other host polymers. MD calculations of both individual PDDT molecules and molecular aggregates suggest that the distribution of dihedral angles present in the PDDT backbone is the narrowest for aggregates of PDDT embedded within a polymer matrix. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2909–2917, 1999     

The effect of concentration in electrochemical oxidation of thiocyanate on platinum electrode

Electrochemical oxidation of thiocyanate (SCN⁻) on platinum electrode in the sulfuric acid medium was studied using cyclic voltammetry, in situ UV-visible absorption measurement, rotating ring-disc electrode voltammetry, and electrical impedance spectroscopy. Two oxidation processes are involved in the electrochemical oxidation of SCN⁻ in sulfuric acid medium. The adsorbed SCN⁻ undergoes oxidation at potential values higher than 0.900 V versus saturated calomel electrode (SCE). Trithiocyanate, , is formed as a relatively stable product during the first oxidation process. The potential range of formation increases with increase in concentration of SCN⁻, and it is exclusively produced in the potential range of 0.550 to 1.40 V versus SCE with 1.0 M NH₄SCN solution. The second oxidation process does not produce any stable product, and the products of second oxidation passivate the electrode surface.     

Characteristics of photoexcitations and interfacial energy levels of regioregular poly(3-hexythiophene-2,5-diyl) on gold.

We have studied characteristics of photoexcitations and interfacial electronic structures of regioregular poly(3-hexlythiophene-2,5-diyl) (P3HT) on gold using two-photon photoemission (2PPE) spectroscopy. The vacuum level threshold is decreased by 1.3 eV from that of bare gold, attributable to interface dipole effects. The 2PPE spectral width narrows as the film thickness increases. We tentatively understand that this is due to destabilization of long-lived localized polaron, attributed to strong interchain interactions. On the basis of the analysis of the 2PPE distribution as a function of photon energy and laser power, the polaron level is located at 3.1 eV below the vacuum level. Using this value and a polaron level of 1.75 eV above the HOMO, we indirectly estimate an ionization potential of 4.85 eV for P3HT. An increase in two-photon photoemission yield with increasing photon energy is attributed to an enhanced electron-hole pair dissociation yield at higher photo-excitation levels. The decrease in power law slope with increasing film thickness is understood by Langevin recombination kinetics and saturation of photoexcitations.     

Novel hybrid materials consisting of regioregular poly(3-octylthiophene)s covalently attached to single-wall carbon nanotubes

Facile routes for the synthesis of hybrid materials consisting of regioregular poly(3-octylthiophene)s covalently attached to single-wall carbon nanotubes are presented for the first time. These materials are easily processable using common organic solvents, and at the same time combine the properties of regioregular poly(3-alkylthiophene)s with those of single-wall carbon nanotubes. Moreover, studies of the properties of these materials have provided strong evidence for an electron transfer from the regioregular poly(3-octylthiophene) to the single-wall carbon nanotube.     

A UV-Visible/Raman spectroelectrochemical study of the stability of poly(3,4-ethylendioxythiophene) films

Poly(3,4-ethylendioxythiophene) films were electropolymerized in aqueous medium without using any surfactant, on glassy carbon electrodes. UV/Vis and Raman spectroelectrochemical techniques were used to analyze the degradation of the polymer film occurring at different pH values. Spectroelectrochemistry has proven to be a very useful analytical tool for this purpose, thanks to its ability to provide information not only about the extent of degradation, but also about mechanistic aspects of the process. From our results we extracted important information about the main factors that play a role in the degradation, in particular about the influence of repetitive doping and de-doping cycles and of photo-induced processes, as a function of the characteristics of the solution, i.e. of pH.     

Growth of poly(3,4‐ethylenedioxythiophene) films prepared by base‐inhibited vapor phase polymerization

Transparent [90% transmittance at 550 nm at a sheet resistance (R_s) of 279 Ω sq^?1] poly(3,4‐ethylenedioxythiophene) (PEDOT) films with electrical conductivities up to 1354 S cm^?1 are prepared using base‐inhibited vapor phase polymerization at atmospheric pressure. The influence of reaction conditions, such as temperature and growth time, on the film formation is investigated. A simple and convenient two‐electrode method is used for the in situ measurement of resistance, enabling to investigate the growth mechanism of polymer films and the influence of different parameters (relative humidity and the amount of oxidant) on the film growth. Low humidity exerts a detrimental effect on film growth and conductivity. In situ R_s measurements suggest that a large structural change occurs upon washing the PEDOT‐oxidant film. © 2014 Wiley Periodicals, Inc. J Polym Sci Part B: Polym. Phys. 2014 , 52, 561–571     

Complexes in polymers II: FT-IR spectra,iodine oxidation,and photochemistry of [(η5-C5H)Fe(CO)2]2, [(η5-C5H5)Mo(CO)3]2 and Mn2(CO)10 in polystyrene,poly(methyl methacrylate) and polystyrene–polyacrylonitrile copolymer

The infrared spectra of [CpFe(CO)₂]₂, [CpMo(CO)₃]₂ and Mn₂(CO)₁₀ (Cp=η-C₅H₅) embedded in films of polystyrene (PS), poly(methyl methacrylate) (PMMA), and polystyrene-polyacrylonitrile (PS? AN), are comparable with those of the dimers in toluene, ethyl acetate and acetonitrile, respectively. Irradiation of the embedded dimers with UV light led to decomposition in PS and PMMA, while in PS? AN the complexes Cp₂Fe₂(CO)₃PS? AN and Mn₂(CO)₉PS? AN were formed, wherein a pendant nitrile group is coordinated to one of the metal atoms. Exposure of the embedded dimers to iodine vapour gave CpFe(CO)₂I, CpMo(CO)₃I and Mn(CO)₅I with the reaction being much slower in PMMA than in PS.     

Synthesis and properties of oxynitrides (La,Sr)Ti(O,N)3 thin films

We report on the synthesis, optical and electrical properties of thin films of La_xSr_(1−x)Ti(O,N)₃, x = 0, 0.25, 0.50, 0.75 and 1. The films were grown by a soft chemistry process from polymeric precursor solutions, which were deposited by spin coating on 100-oriented SrTiO₃ substrates. After drying, the organic matrix was burned at 400 °C. These steps were repeated six times to obtain a reasonable thickness of the films. Afterwards, the samples were heated in a tube furnace at 950 °C in flowing ammonia. The oxynitride films showed different colours from red-orange for LaTiO₂N to greenish-blue for SrTiO₃:N. The films were characterised by X-ray diffraction, scanning electron microscopy, atomic force microscopy, UV–vis spectroscopy, secondary ion mass spectrometry and electrical measurements. The results show that the films are polycrystalline and have the perovskite structure. Their thickness is about 440 nm and the average roughness value is 7.5 nm. UV–vis transmittance measurements showed a strong decrease in the band gap values for the oxynitrides compared to the respective oxides. The values change from approximately 3.2 eV for the oxides to an average value of 2.4 eV for the oxynitrides. The electrical measurements indicate a change in the electrical behaviour from insulator for LaTiO₂N to semiconductor for SrTiO₃:N.     

Non‐Resonant z‐Scan Characterization of the Third‐Order Nonlinear Optical Properties of Conjugated Poly(thiophene azines)

The nonlinear optical properties of a functionalized poly(thiophene azine), namely, poly(3,4‐didodecylthiophene azine), PAZ, at the optical telecommunication wavelength of 1550 nm are investigated by means of the closed‐aperture z‐scan technique in both thin films and solutions. Values of χ⁽³⁾=(2.4±0.4)×10^?13 esu, n₂=(4.0±0.7)×10^?15 cm² W^?1, and γ=(4.5±0.7)×10^?34 esu are estimated for the third‐order (Kerr) susceptibility, the intensity‐dependent refractive index, and the molecular second hyperpolarizability of solution samples, respectively. A very small dependence on the polymer chain length is found. Markedly higher values of (4.4±1.1)×10^?11 esu, (6.6±1.0)×10^?13 cm² W^?1, and (5.0±0.8)×10^?33 esu are measured for the corresponding quantities in thick (up to 20 μm) polymer films cast on quartz plates. The enhancement of the NLO responses on going from solution to solid samples is attributed to a partially ordered structure and to the presence of interchain interactions leading to greater π‐electron delocalization in the cast polymer films. The results are compared with those previously obtained by using third‐harmonic generation (THG), taking into account that those data were measured under conditions of three‐photon resonance, whereas our z‐scan measurements are fully off‐resonance.