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1.
    
All conjugated polymers examined to date exhibit significant cumulative lattice disorder, although the origin of this disorder remains unclear. Using atomistic molecular dynamics (MD) simulations, the detailed structures for single crystals of a commonly studied conjugated polymer, poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) are obtained. It is shown that thermal fluctuations of thiophene rings lead to cumulative disorder of the lattice with an effective paracrystallinity of about 0.05 in the π–π stacking direction. The thermal‐fluctuation‐induced lattice disorder can in turn limit the apparent coherence length that can be observed in diffraction experiments. Calculating mobilities from simulated crystal structures demonstrates that thermal‐fluctuation‐induced lattice disorder even enhances charge transport in P3HT. The mean inter‐chain charge transfer integral is enhanced with increasing cumulative lattice disorder, which in turn leads to pathways for fast charge transport through crystals.  相似文献   

2.
The photoconductivity and electro-optic response of a self-organised nanostructured poly[(ethynediyl)(arylene)(ethynediyl)silylene]/N-ethylcarbazole/polyphenylsilsesquioxane composite have been investigated with a cw diode laser at a wavelength of 1500 nm. For electric field 25 V µm–1 and beam intensity 18 W cm–2, the photosensitivity was 0.5 pS cm–1 (W cm–2)–1. The dark conductivity was found to be much less than the photoconductivity and the composite shows photo charge generation at this wavelength. The value of the composite electro-optic coefficient is in agreement with data for polymeric materials active in the visible range. Orientational effects have been observed with modulation frequencies down to several Hz, and quite slow dynamics of the response can be expected.Based on the report presented at the International Conference Modern Trends in Organoelement and Polymer Chemistry dedicated to the 50th anniversary of the A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences (Moscow, May 30–June 4, 2004).Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1897–1901, September, 2004.  相似文献   

3.
    
We successfully synthesized new D‐A copolymers that employ 1,10‐bithienopyrrolodione (biTPD), thiophene, and selenophene‐based donor monomeric units. Two polymers, PBTPDEBT and PBTPDEBS , exhibited high degrees of crystallinity and unique polymer chain arrangements on the substrate, which is attributed to their enhanced coplanarity and intermolecular interactions between the polymer chains. Among the thin‐film transistor devices made of PBTPDEBT and PBTPDEBS , the annealed PBTPDEBS device displayed relatively high hole mobility, which was twice that of the PBTPDEBT ‐based device. In addition, an organic photovoltaic device based on a PBTPDEBS :PC71BM blend displayed the maximum power conversion efficiency of 3.85%. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1228–1235  相似文献   

4.
In this study, we demonstrate how the intrinsic properties of a polymer can influence the electrical characteristics of organic field‐effect transistors (OFETs). OFETs fabricated with three batches of poly[2‐methoxy,5‐(3′,7′‐dimethyl‐octyloxy)]‐p‐phenylene vinylene (MDMO‐PPV) were investigated. The properties of the polymers were initially investigated using Fourier transform infrared spectroscopy (FTIR), impedance spectroscopy (IS), gel permeation chromotography (GPC), and cyclic voltammetry (CV), respectively. The structure and purity of the polymer batches were found to be very comparable, but the molecular weight (Mn and Mw) and polydispersity (PDI = Mw/Mn), varied between the samples and the HOMO and LUMO levels of the polymers were found to depend on the molecular weight properties. OFETs were then fabricated with the polymers and electrically characterized. It was observed that the channel current and the field‐effect mobility increase with increasing polymer molecular weight. The output characteristics of the transistors, on the other hand, were found to depend on the PDI of the polymer. Saturation of the channel current occurs at higher source–drain voltages and short‐channel behavior was observed to start at longer channel lengths for polymers with a higher PDI. This behavior is observed to be thickness dependent, and the short‐channel behavior was more pronounced for thicker MDMO‐PPV films. These results are explained in terms of influences of chain packing and ordering and high bulk currents on the FET output and transistor parameters. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 50: 117–124, 2012  相似文献   

5.
    
A series of donor/acceptor carbazole copolymers comprising alternating 6,7‐diphenyl‐4,9‐bis‐(thiophen‐2‐yl)‐[1,2,5]thiadiazolo[3,4‐g]quinoxaline and 3,6‐dimethyl‐9‐alkyl‐9H‐carbazole repeat units ( P1 ), or 3,6‐dimethyl‐9‐triarylamino‐9H‐carbazole repeat units ( P2 ), or 9‐triarylamino‐9H‐carbazole repeat units ( P3 ) has been prepared following Suzuki polymerization procedures. P3 absorbs light up to 1 200 nm and has an energy gap of 1.1 eV, while P1 and P2 have energy gaps of 1.3 and 1.25 eV, respectively. Photovoltaic cells with ITO/PEDOT:PSS/ P3 :PCBM (1:1 w/w)/Ca showed an open‐circuit voltage of 0.4 V under white light illumination, power conversion efficiency of 0.61%, and short‐circuit current of 5.2 mA · cm−2.

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6.
    
A series of donor‐acceptor low‐bandgap conjugated polymers, that is, HThmBT (m = 3, 6, 9, 12, 15), composed of regioregular 3‐hexylthiophene segments and 2,1,3‐benzothiadiazole units, were synthesized through the Stille coupling polymerization to optimize the π‐conjugation length of the polymer and the intramolecular charge transfer (ICT) effect in the polymer backbone. The polymers had relatively low optical bandgaps ranging from 1.6 to 1.72 eV. Among these polymers, HTh6BT exhibited the best device performance with a power conversion efficiency (PCE) of 1.6%. Moreover, despite being based on thiophene, HTh6BT exhibited a high‐open circuit voltage (VOC) of over 0.8 V because of its low high occupied molecular orbital (HOMO) energy level. These results provided an effective strategy for designing and synthesizing low‐bandgap conjugated polymers with broad absorption ranges and well‐balanced energy levels. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010  相似文献   

7.
    
We demonstrated a simple patterning method for the deposition of polymer electrodes such as poly(3,4‐ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT/PSS). We made use of the difference in wettability between hydrophobic surfaces and hydrophilic surfaces to make the patterns. However, the patterns made with our patterning method created undesirable ring‐like stains, which were caused by the outward flow of the solute within the PEDOT/PSS solution drop. To achieve homogenous device performance, we proposed a simple process for removing this ring‐like stain by making the surface tension gradient with dual solvent system in the PEDOT/PSS solution drop. Because this surface tension gradient causes the inward flow of the solute within the PEDOT/PSS solution drop, the ring‐like stain is removed. Finally, we confirmed the potential of our patterning method for polymer electrodes such as the PEDOT/PSS by fabricating pentacene thin‐film transistors (TFTs) and measuring the electrical properties of the pentacene TFTs. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1590–1596, 2011  相似文献   

8.
    
The charge transport characteristics of organic semiconductors are one of the key attributes that impacts the performance of organic electronic and optoelectronic devices in which they are utilized. For improved performance in organic photovoltaic cells, light-emitting diodes, and field-effect transistors (FETs), efficient transport of the charge carriers within the organic semiconductor is especially critical. Characterization of charge transport in these organic semiconductors is important both from scientific and technological perspectives. In this review, we shall mainly discuss the techniques for measuring the charge carrier mobility and not the theoretical underpinnings of the mechanism of charge transport. Mobility measurements in organic semiconductors and particularly in conjugated polymers, using space-charge-limited current, time of flight, carrier extraction by linearly increasing voltage, double injection, FETs, and impedance spectroscopy are discussed. The relative merits, as well as limitations for each of these techniques are reviewed. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012  相似文献   

9.
    
Polymer photoelectronic device based on interaction between π-conjugated polymer matrices and photochromic molecules was fabricated. The theoretical and experimental studies proved that the photochromic reaction in studied devices should eventuate in changes of optical and electrical properties of polymers such as luminescence and conductivity. The quantum chemical calculations showed that the presence of dipolar species in the vicinity of a polymer chain modifies the on-chain site energies and consequently increases the width of the distribution of hopping transport states. Optical switching was studied using standard absorption and photoluminescence spectroscopy. A strong photoluminescence quenching after the photochromic conversion caused by radiative energy transfer was observed. The influence of photoswitchable charge carrier traps on charge transport were evaluated by Space Charge Limited Current (SCLC) method. It was shown that deep traps may significantly affect the energy of the transport level, and thus modulate the transport of charge carriers.  相似文献   

10.
    
Lowering of the optical band gap of conjugated polymers in bulk heterojunction solar cells not only leads to an increased absorption but also to an increase of the optimal active layer thickness due to interference effects at longer wavelengths. The increased carrier densities due to the enhanced absorption and thicker active layers make low band gap solar cells more sensitive to formation of space charges and recombination. By systematically red shifting the optical parameters of poly[2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐p‐phenylenevinylene] and 6,6‐phenyl C61‐butyric acid methyl ester, we simulate the effect of a reduced band gap on the solar cell efficiencies. We show that especially the fill factor of low band gap cells is very sensitive to the balance of the charge transport. For a low band gap cell with an active layer thickness of 250 nm, the fill factor of 50% for balanced transport is reduced to less than 40% by an imbalance of only one order of magnitude. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011  相似文献   

11.
    
We use frequency dependent capacitance measurements to probe carrier mobilities and transport parameters of six representative semiconducting polymers and some of their bulk heterojunction (BHJ) blends. With a suitable choice of a hole injection layer, well-defined signals for hole transport characterization can be obtained for the pristine polymers [J. Appl. Phys. 99, 013706 (2006)]. However, ill-defined signals with negative capacitances, arising from undesirable electron leakages, are obtained for the BHJ blends. The problem of electron leakage can be circumvented by inserting an electron blocking and trapping layer under the cathode. As a result, hole transport properties of BHJ blends can be obtained. For the BHJ of poly(3-hexylthiophene) blended with [6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PC61BM), the hole mobilities seem to be insensitive to the composition of the BHJ, indicating the P3HT component in the BHJ is well connected. On the other hand, for poly[N-9“-hepta-decanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadia zole)] doped with [6,6]-phenyl-C71-butyric acid methyl ester (PCDTBT:PC71BM), a clear reduction of the hole mobility is observed as the polymer composition is reduced. Temperature dependent experiments were performed. The data are analyzed by the Gaussian Disorder Model. We found that the energetic disorder is independent of the composition of the BHJ. Organic photovoltaic performances of BHJ blends are also measured in this contribution. The correlation between device performance and energetic disorder of the BHJ will be discussed. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013  相似文献   

12.
Polyaniline (PANI) base was protonated in aqueous solutions of an organic acid, 3-nitro-1,2,4-triazol-5(4H)-one (NTO). The temperature dependence of DC conductivity of PANI-NTO seems to correspond to the theory of variable range hopping (VRH) in three dimensions. The frequency dependence of AC conductivity also reflects the hopping nature of mobile charges. The activation energy for the polymers with protonation degree above 0.12 remains constant with increasing dopant concentration and DC conductivity. The value of this constant may correspond to the energy needed for the ionization of dopant counterion. The fit of the electric relaxation function to the stretched exponential function ϕ(t) = exp[−(t/τ)β] gives the stretch parameter β about 0.35, which shows that the distribution of relaxation times is broad and indicates a high inhomogeneity in the distribution of a dopant.  相似文献   

13.
14.
含四-苯基卟啉基团聚酰亚胺膜的光电导性能研究   总被引:2,自引:0,他引:2  
分剐以均苯四酸二酐(PMDA)与四(4-氨基苯基)卟啉(TAPP)/4,4′-二苯醚(ODA)、TAPP/3,6-二氨基-N-甲基咔唑(DACz)聚合得到两个系列含四-苯基卟啉基团(TPP)聚酰亚胺(PI)共聚膜,并时其作为载流子发生层(CGL)制成的感光体的光电导性能进行了测试。结果表明:PI共聚膜的光电导性能随分子链中TPP基团含量的提高而增强;当TPP基团含量相同时,PMDA/TAPP/ODA系列的光电导性能较PMDA/TAPP/DACz系列好;含TPP基团PI共聚膜的光电导性能明显优于四-苯基卟啉分子掺杂体系;在CGL与导电铝基间引入聚甲基丙烯酸甲酯(PMMA)阻挡层(CBL)不能提高感光体的光电导性能。从光电导机理分析了TPP基团、四-苯基卟啉分子的聚集结构与PI膜光电导性能的关系。  相似文献   

15.
    
The charge transport properties of polymer matrix–carbon black composites are investigated in this study. Direct current conductivity is examined with varying parameters: the temperature and the conductive filler content. Conductivity data are analyzed by means of percolation theory, and both percolation threshold and critical exponent are determined at each of the examined temperatures. The temperature dependence of conductivity and the agreement of experimental results with the variable range hopping model reveal hopping conduction as the predominant transport mechanism, below and in the vicinity of the critical concentration of carbon black particles. At higher concentrations, the contribution of hopping transport to the overall conductivity is reduced and a balance between hopping and conduction via geometrical contact occurs. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2535–2545, 2007  相似文献   

16.
17.
    
The present review focuses on the recent progress made in thin film orientation of semi‐conducting polymers with particular emphasis on methods using epitaxy and shear forces. The main results reported in this review deal with regioregular poly(3‐alkylthiophene)s and poly(dialkylfluorenes). Correlations existing between processing conditions, macromolecular parameters and the resulting structures formed in thin films are underlined. It is shown that epitaxial orientation of semi‐conducting polymers can generate a large palette of semi‐crystalline and nanostructured morphologies by a subtle choice of the orienting substrates and growth conditions.

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18.
A polarizable molecular dynamics simulation and calculation scheme for site energy disorder is presented in amorphous tris(8‐hydroxyquinolinato)aluminum (Alq3) by means of the charge response kernel (CRK) method. The CRK fit to the electrostatic potential and the tight‐binding approximation are introduced, which enables modeling of the polarizable electrostatic interaction for a large molecule systematically from an ab initio calculation. The site energy disorder for electron and hole transfers is calculated in amorphous Alq3 and the effect of the polarization on the site energy disorder is discussed.  相似文献   

19.
    
The protection of the 3,6‐positions of 9‐alkyl‐9H‐carbazole repeat units with fluorine substituents in 2,7‐linked main‐chain polymers as well as in copolymers with triaryl amine repeat units affords blue emitting materials with enhanced electrolytic stability. The electronic conjugation of this new class of materials is more extended than that of the equivalent polymers where the 3,6‐positions are protected with methyl substitutions as a result of the smaller steric hindrance of their fluorine substituents. Attachment of fluorine‐protecting groups at the 3,6‐positions of carbazole repeat units in the homopolymers resulted in materials with relatively high ionization potentials (5.71 eV). However, introduction of triaryl amine comonomers as alternating repeat units provided carbazole/triaryl amine copolymers with a low ionization potential (5.25 eV), a very high quantum yield of fluorescence in solution (0.96), and narrow emission bands [full width at half maximum (FWHM) = 52 nm]. The preparation of this new class of materials together with a study of their electronic and photophysical properties is presented. Copyright © 2007 John Wiley & Sons, Ltd.  相似文献   

20.
The electric conductivity and photoconductivity of films based on polyvinylbutyral and containing Fe2O3 and CdS nanoparticles and an organic compound with intramolecular charge transfer as photoconductivity sensitizer in the visible and near infrared regions were investigated. In the absorption region of the sensitizer the activation energy of the photocurrent is somewhat greater than 0.1 eV and is close to the activation energy of the electric conductivity current.  相似文献   

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