Interface‐tailored and nanoengineered polymeric materials for (opto)electronic devices

For plastic (opto)electronic devices such as light‐emitting diodes (LEDs), photovoltaic (PV) cells and field‐effect transistors (FETs), the processes of charge (hole/electron) injection, charge transport, charge recombination (exciton formation), charge separation (exciton diffusion and dissociation) and charge collection are critical to enhance their performance. Most of these processes are relevant to nanoscale and interfacial phenomena. In this review, we highlight the state‐of‐the‐art developments of interface‐tailored and nanoengineered polymeric materials to optimize the performance of (opto)electronic devices. These include (1) interfacial engineering of anode and cathode for polymer LEDs; (2) nanoengineered (C₆₀ and inorganic semiconductor nanoparticles) π‐conjugated polymeric materials for PV cells; and (3) polymer and monolayer dielectrics/interfaces for FETs and light‐emitting and nano‐FETs. Copyright © 2009 Society of Chemical Industry     

Synthesis of oxadiazole‐based polymers containing a carbazole–vinylene or fluorene–vinylene group and their hole‐injection/transport behavior in light‐emitting diodes

A series of conjugated (poly{N‐(2‐ethylhexyl)‐3,6‐carbazole–vinylene‐alt‐[(2,5‐bisphenyl)‐1,3,4‐oxadiazole]}) and nonconjugated (poly{N‐(2‐ethylhexyl)‐3,6‐carbazole–vinylene‐alt‐[(2,5‐bisphenol)‐1,3,4‐oxadiazole]}) and poly{9,9‐dihexyl‐2,7‐fluorene–vinylene‐alt‐[(2,5‐bisphenol)‐1,3,4‐oxadiazole]}) polymers containing oxadiazole and carbazole or fluorene moieties in the polymer backbone were synthesized with a multiple‐step procedure. The properties of the polymers, including the photophysical and electrochemical characteristics, could be fine‐tuned by adjustment of the components or structures in the polymer chains. The polymers were used to examine the hole‐injection/transport behavior as hole‐injection/hole‐transport layers in double‐layer indium tin oxide (ITO)/polymer/aluminum tris(8‐hydroxyquinoline)/LiF/Al devices by the determination of their energy levels. The effects of the polymers in these devices on the charge‐transport behavior were compared with a control device fabricated with poly(ethylenedioxythiophene) (PEDOT)–poly(styrene sulfonate) (PSS). Devices containing the synthesized polymers showed comparable adhesion to the ITO anode and good hole‐injection/transport performance. In addition, they exhibited higher electroluminescence over an identical range of current densities than the control device. This was attributed to the prevention of radiative exciton quenching caused by the PEDOT–PSS interfaces and the improvement of electron/exciton blocking due to the higher electron affinity of the synthesized polymers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Theoretical investigations of electronic structure and charge transport properties in polythiophene‐based organic field‐effect transistors

Regioregular poly(3‐hexylthiophene) (P3HT) is a hole transport polymer material used in organic field‐effect transistors (OFETs) and can reach mobilities as high as 0.1 cm² V^?1 s^?1. Factors that affect the charge mobility and the transport mechanisms of P3HT‐based OFET systems are therefore of great importance. We use quantum mechanical methods to interpret the charge mobility and the transport properties of self‐assembled P3HT molecules along the intra‐chain and inter‐chain directions. Our approach is illustrated by a hopping transport model, in which we examine the variation of charge mobility with torsional angle and the intermolecular distance between two adjacent thiophene segments. We also simulate packed P3HT structures via molecular dynamics (MD) simulations. The MD results indicate that the resultant mobility along the π?π inter‐chain direction is significantly less than that along the intra‐chain direction. Accordingly, the main charge‐transfer route within the P3HT ordered domains is an intra‐chain rather than an inter‐chain one. The calculation result for the inter‐chain hole mobility is around 10^?2 cm² V^?1 s^?1, which is consistent with experimental data from P3HT single fibril. Copyright © 2009 Society of Chemical Industry     

Effect of side‐chain functionality on the organic field‐effect transistor performance of oligo(p‐phenylenevinylene) derivatives

In order to observe the effects of the substitution of electronegative flourine with aromatic groups in oligo(p ‐phenylenevinylene) compounds on their packing, morphology, and charge carrier mobility, we have synthesized napthol‐substituted oligo(p ‐phenylenevinylene) compounds and examined their solubility, redox properties, thin film morphologies, and charge carrier properties. To date, very few examples of conjugated oligomers bearing napthol side groups have been reported in the literature. After annealing at 150 °C, the mobility of S1, S2, and S3 was 4.0 × 10^?2 cm² V^?1 s^?1, 1.2 × 10^?2 cm² V^?1 s^?1, and 2.6 × 10^?3 cm² V^?1 s^?1, respectively. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44825.     

Review of electronic and optical properties of semiconducting π‐conjugated polymers: applications in optoelectronics

A general overview of the optoelectronic properties of π‐conjugated polymers is presented. Two types of polymer are discerned: interchangeable structures of the same energy (degenerate), such as polyacetylene; and non‐degenerate polymers, such as poly(para‐phenylene). The band structures of degenerate and non‐degenerate polymers are related to their conductivities in doped and non‐doped states. In both cases, disorder and impurities play an important role in conductivity. Polarons, bipolarons and excitons are detailed with respect to doping and charge transfers. Given the fibrillic nature of these materials, the variable range hopping (VRH) law for semiconducting polymers is modified to account for metallic behaviours. Optoelectronic properties—electroluminescence and photovoltaic activity—are explained in terms of HOMO and LUMO bands, polaron‐exciton and charge movement over one or more molecules. The properties of H‐ or J‐type aggregates and their effects on transitions are related to target applications. Device structures of polymer light‐emitting diodes are explicitly linked to optimising polaron recombinations and overall quantum efficiencies. The particularly promising use of π‐conjugated polymers in photovoltaic devices is discussed. Copyright © 2004 Society of Chemical Industry     

Anionic triphenylamine‐ and fluorene‐based conjugated polyelectrolyte as a hole‐transporting material for polymer light‐emitting diodes

BACKGROUND: Hole‐transport layers (HTLs) play a crucial role in multilayer polymeric light‐emitting diodes (PLEDs) for the achievement of satisfactory device performance. During the fabrication of multilayer PLEDs via solution processing, the fabricated HTLs encounter the risk of erosion during the film‐forming process of subsequent emitting layers (EMLs). In contrast to the widely investigated crosslinkable HTLs, much less attention has been paid to the preparation of polar‐solvent‐soluble HTLs, which is a straightforward solution to overcome the interfacial mixing between HTLs and EMLs during solution processing. RESULTS: Alternating triphenylamine‐ and fluorene‐based anionic copolymer poly[9,9‐bis(4′‐sulfonatobutyl)fluorene‐alt‐N‐(p‐trifluoromethyl)phenyl‐4,4′‐diphenylamine]sodium salt (PFT‐CF3) was synthesized via a palladium‐catalyzed Suzuki coupling reaction. This polyelectrolyte is soluble only in polar solvents such as methanol, dimethylformamide and dimethylsulfoxide rather than in non‐polar solvents such as toluene, chloroform and xylene. The relatively high HOMO (?5.22 eV) and LUMO (?2.26 eV) levels of this polymer endow it simultaneously with good hole‐transporting and electron‐blocking capabilities. The performance of red‐, green‐ and blue‐emitting devices utilizing this polyelectrolyte as HTL was investigated. CONCLUSION: The anionic conjugated polyelectrolyte based on triphenylamine and fluorene, PFT‐CF₃, can serve as a promising hole‐transporting/electron‐blocking layer in multilayer PLEDs. Copyright © 2009 Society of Chemical Industry     

Synthesis,characterization, and electro‐optical properties of a soluble conjugated polymer containing an oxadiazole unit in the main chain

A novel copolymer, poly{[2,5‐diphenylene‐1,3,4‐oxadiazole‐vinylene]‐alt‐[2‐methoxy‐5‐(2‐ethylhexyloxy)‐1,4‐phenylenevinylene]}(MEH‐OPPV) containing a high‐electron‐affinity unit of aromatic oxadiazole in the main chain is synthesized through the Wittig condensation reaction. The obtained copolymer is easily soluble in conventional organic solvents. The structure of the copolymer was characterized by Fourier transform infrared, ¹H nuclear magnetic resonance, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and ultraviolet‐visible and photoluminescence spectroscopy. The TGA result indicates that the copolymer has very high thermal stability (stable up to 310°C in nitrogen), while DSC investigation demonstrates that the glass transition temperature (T_g) is 143°C, which might be a merit for the long‐life operation of light‐emitting devices. The absorption spectrum of film sample of the copolymer reveals two peaks at 310 and 370 nm, respectively, and the edge absorption corresponds to a band gap of 2.46 eV. A single‐layer light‐emitting diode device ITO/MEH‐OPPV/Al is successfully fabricated. The device emits visible yellowish‐green light above the bias voltage of 4.0 V under ambient condition. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2618–2623, 2003     

Synthesis and characterization of photo‐crosslinkable polyfluorene with acrylate side‐chains

A photo‐crosslinkable polymer, poly[2,7‐(9,9‐dioctylfluorene)‐co‐2,7‐(9‐hexyl‐9‐(2‐acrylate ethyl)‐9H‐fluorene)] (P3), was synthesized and the photo‐crosslinkable acrylate groups were introduced into the side‐chains of the polyfluorene derivative after its polymerization. This method avoids the possible crosslinkage of the crosslinkable groups on the monomers during polymerization in the traditional synthesis route by the polymerization of the monomers with the crosslinkable side‐chains. The soluble and processable polymer P3 could be crosslinked via the acrylate groups in its side‐chains upon exposure to UV light in nitrogen atmosphere. The crosslinking was confirmed by IR spectroscopy: the IR peak of C?C bond at 1635 cm^?1 decreased and that of the vinyl C? H bond at 742 cm^?1 disappeared after the UV exposure. The absorption spectra of P3 remain unchanged after crosslinking, but a longer wavelength emission at 517 nm appeared in the photoluminescent and electroluminescent spectra of the crosslinked P3, which could be attributed to the formation of keto defects during the photo crosslinking. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2336–2342, 2006     

Synthesis and characterization of novel phenyl‐substituted poly(p‐phenylene vinylene) derivatives

Two novel phenyl‐substituted poly(p‐phenylene vinylene) derivatives, poly{2‐[3′,4′‐(2″‐ethylhexyloxy)(3″,7″‐dimethyloctyloxy)benzene]‐1,4‐phenylenevinylene} (EDP‐PPV) and poly{2‐[3′,4′‐(2″‐ethylhexyloxy)(3″,7″‐dimethyloctyloxy)benzene]‐5‐methoxy‐1,4‐phenylenevinylene} (EDMP‐PPV), and their copolymer, poly{2‐[3′,4′‐(2″‐ethylhexyloxy)(3″,7″‐dimethyloctyloxy)benzene]‐1,4‐phenylene‐vinylene‐co‐2‐[3′,4′‐(2″‐ethylhexyloxy)(3″,7″‐dimethyloctyloxy)benzene]‐5‐methoxy‐1,4‐phenylenevinylene} (EDP‐co‐EDMP‐PPV; 4:1, 1:1, and 1:4), were successfully synthesized according to the Gilch route. The structures and properties of the monomers and the resulting conjugated polymers were characterized with ¹H‐NMR, ¹³C‐NMR, elemental analysis, gel permeation chromatography, thermogravimetric analysis, ultraviolet–visible absorption spectroscopy, and photoluminescence and electroluminescence (EL) spectroscopy. The EL polymers possessed excellent solubility in common solvents and good thermal stability with a 5% weight loss temperature of more than 380°C. The weight‐average molecular weights and polydispersity indices of EDP‐PPV, EDMP‐PPV, and EDP‐co‐EDMP‐PPV were 1.40–2.58 × 10⁵, and 1.19–1.52, respectively. Double‐layer light‐emitting diodes with the configuration of indium tin oxide/polymer/tris(8‐hydroxyquinoline)aluminum/Al devices were fabricated, and EDP‐co‐EDMP‐PPV (1:1) showed the highest EL performance and exhibited a maximum luminance of 1050 cd/m² at 19.5 V. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1259–1266, 2005     

Excimer and electromer suppression of tetraphenylsilane‐based blue‐light‐emitting polymers

Excimer and electromer suppression of tetraphenylsilane‐derivative‐based blue polymer light‐emitting devices (PLEDs) was investigated. Tetraphenylsilane with a rigid bulky structure certainly but not completely suppressed excimer formation among polymer‐chain segments. A poor solvent, toluene, resulted in excimer formation in the solid film during the spin‐coating process, which could not be suppressed by the incorporation of a bulky moiety onto the polymer backbone. In addition, electromers or electroplexes formed by the strong interaction between the oxadiazole and diphenyl(4‐tolyl)amine groups could not be prevented by the tetraphenylsilane moiety. The influences of the bulky moiety, bipolar unit, and device fabrication conditions on the suppression of excimers or electromers in PLEDs are discussed in detail. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Star‐Shaped,Dendrimeric and Polymeric Triarylamines as Photoconductors and Hole Transport Materials for Electro‐Optical Applications

Recent developments in the synthesis and application of hole conducting oligomeric and polymeric triarylamines are reviewed. The materials are classified as Star‐shaped molecules, Spiros and dendrimers, Side‐chain polymers, and Main‐chain polymers and copolymers. This paper concentrates on the research results of our group on the synthesis of a variety of such compounds, their structure‐property relationship and their application in devices like organic light emitting diodes, solar cells and photorefractive systems. The thermal properties and electronic properties of these compounds were varied by changing the chemical structure and nature of substituents. In the case of low molecular weight star‐shaped molecules the glass transition temperature could be increased to above 140°C by suitable structural design. Similarly, for polymeric triarylamines the variation of glass transition temperature was achieved over a wide range from 92 to 237°C. This is especially necessary for the wide spectrum of applications of these materials as hole conductors in low‐T_g photorefractive composites to high‐T_g materials in OLEDs. Moreover, the electronic energy levels and the band gap in these compounds can be manipulated to optimize the hole injection or electron transfer or emission properties or even photocurrent generation to make them suitable for various applications. Especially, the concept of copolymerization with other functional monomers results in multifunctional copolymers with good hole injection and transport properties. The polymer networks involving triarylamine structures are not included in this Review, because this constitutes the subject‐matter of insoluble hole transport materials and will be published elsewhere.     

Eu3+‐doped CsPbBr1.5I1.5 quantum dots glasses: A strong competitor among red fluorescence solid materials

CsPbBr_1.5I_1.5 quantum dots (QDs) glasses are synthesized by traditional melting and thermal treated method, CsPbBr_1.5I_1.5 QDs glasses show vast potential as red fluorescence component in warm WLED applications due to their moderate emission wavelength as well as good opacity property. However, the quantum yield of QDs glasses is still low, therefore, Eu³⁺ ions is chosen to introduce into CsPbBr_1.5I_1.5 QDs, the quantum yield is enhanced to 64.7%. After a sequence of testing operations, we find that 6.5%CsPbBr_1.5I_1.5:0.28%Eu³⁺ QDs glasses is a strong competitor among red fluorescence solid materials.     

Electroluminescence and photovoltaic properties of poly(p‐phenylene vinylene) derivatives with dendritic pendants

A copolymer of dendronized poly(p‐phenylene vinylene) (PPV), poly{2‐[3′,5′‐bis (2′‐ethylhexyloxy) bnenzyloxy]‐1,4‐phenylene vinylene}‐co‐poly[2‐methoxy‐5‐(2′‐ethylhexyloxy)‐1,4‐phenylene vinylene] (BE‐co‐MEH–PPV), was synthesized with the Gilch route to improve the electroluminescence and photovoltaic properties of the dendronized PPV homopolymer. The polymer was characterized by ultraviolet–visible absorption spectroscopy, photoluminescence spectroscopy, and electrochemical cyclic voltammetry and compared with the homopolymers poly{2‐[3′, 5′‐bis(2‐ethylhexyloxy) benzyloxy‐1,4‐phenylene vinylene} (BE–PPV) and poly[2‐methoxy‐5‐(2′‐ethylhexyloxy)‐1,4‐phenylenevinylene] (MEH–PPV). Polymer light‐emitting diodes based on the polymers with the configuration of indium tin oxide (ITO)/poly(3,4‐ethylene dioxythiophene) : poly(styrene sulfonate) (PEDOT : PSS)/polymer/Ca/Al were fabricated. The electroluminescence efficiency of BE‐co‐MEH–PPV reached 1.64 cd/A, which was much higher than that of BE–PPV (0.68 cd/A) and a little higher than that of MEH–PPV (1.59 cd/A). Photovoltaic properties of the polymer were studied with the device configuration of ITO/PEDOT : PSS/polymer : [6,6J‐phenyl‐C₆₁‐butyric acid methyl ester] (PCBM)/Mg/Al. The power conversion efficiency of the device based on the blend of BE‐co‐MEH–PPV and PCBM with a weight ratio of 1 : 3 reached 1.41% under the illumination of air mass 1.5 (AM1.5) (80 mW/cm²), and this was an improvement in comparison with 0.24% for BE–PPV and 1.32% for MEH–PPV under the same experimental conditions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and light‐emitting properties of new poly(p‐phenylenevinylene) derivatives containing oxadiazole moiety

Two new poly(p‐phenylenevinylene) (PPV) derivatives containing oxadiazole moiety (OXA‐PPV1 and OXA‐PPV2) were synthesized by the Wittig condensation polymerization reaction. Their thermal and light‐emitting properties were investigated. The single‐ and triple‐layer electroluminescent (EL) devices with configurations of ITO/polymer/Al and ITO/polymer/OXD‐7/Alq₃/Al were fabricated. They exhibited blue emission at 470 nm for OXA‐PPV1 and green emission at 560 nm for OXA‐PPV2. The turn‐on voltages of triple‐layer device were 11 V for OXA‐PPV1 and 8 V for OXA‐PPV2. The triple‐layer EL devices showed much better performance than did the single‐layer devices. The spectra indicated energy transfer occurred from segments of side chain to polymer backbone. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 422–428, 2002     

Synthesis and electroluminescent properties of a novel copolymer with short alternating conjugated and non‐conjugated blocks

A new electroluminescent copolymer [poly(1,5‐di(3,5‐dimethyloxystyrylene)naphthalene‐block‐tri(ethylene oxide)) (DSN–TEO)], containing alternating rigid, conjugated light‐emitting units and flexible tri(ethylene oxide) ionic conductive units, was synthesized via the Wittig reaction. The polymer has fairly good solubility in chloroform, tetrahydrofuran, toluene, etc, and excellent film‐forming ability. The decomposition temperature and the glass transition temperature were 409 °C and 42.2 °C, respectively. A light‐emitting diode (LED) device with configuration ITO/PEDOT–PSS/DSN–TEO/Ca(Al) and light‐emitting electrochemical cell (LEC) device with ITO/DSN–TEO + PEO (LiTf)/Al were prepared, and the photoluminescence and electroluminescence (EL) properties were investigated. Efficient blue‐green light emission (EL maximum emissive wavelength at 508 nm) was found with onset voltage at 6 V. The maximum light efficiency was 0.107 cd A^?1 at 20 V for LED, and the onset voltage 2.5 V and the maximum light efficiency was 4.2 cd A^?1 at 2.8 V for LEC, respectively. The response time of the LEC was less than 5 s. The EL efficiency of LEC device was improved by 44 as compared with the relative LED device. © 2003 Society of Chemical Industry     

New fluorene–pyrazino[2,3‐g]quinoxaline‐conjugated copolymers: Synthesis,optoelectronic properties,and electroluminescence characteristics

New donor–acceptor conjugated copolymers called poly}2,7‐(9,9′‐dihexylfluorene)‐co‐5,10‐[pyrazino(2,3‐g)quinoxaline]{s or PFPQs [where F represents the 2,7‐(9,9′‐dihexylfluorene) moiety and PQ represents the 5,10‐(pyrazino[2,3‐g]quinoxaline) moiety], synthesized by the palladium‐catalyzed Suzuki coupling reaction, are reported. The PQ contents in the PFPQ copolymers were 0.3, 1, 5, and 50 mol %, and the resulting copolymers were named PFPQ0.3, PFPQ01, PFPQ05, and PFPQ50, respectively. Absorption spectra showed a progressive redshift as the PQ acceptor content increased. The relatively small optical band gap of 2.08 eV for PFPQ50 suggested strong intramolecular charge transfer (ICT) between the F and PQ moieties. The photoluminescence emission peaks of the PFPQ copolymer films also exhibited a large redshift with enhanced PQ contents, ranging from 551 nm for PFPQ0.3 to 592 nm for PFPQ50. However, the PFPQ copolymer based electroluminescence (EL) devices showed poor device performances probably due to the strong confinement of the electrons in the PQ moiety or significant ICT. This problem was resolved with a binary blend of poly[2,7‐(9,9‐dihexylfluorene)] (PF) and PFPQ with a volume ratio of 95/5 (BPQ05). Multiple emission peaks were observed at 421, 444, 480, 516, and 567 nm in the BPQ05‐based EL devices because the low PQ content led to incomplete energy transfer. The Commission Internationale de L'Eclairage 1931 coordinates of the BPQ05‐based EL device were (0.31, 0.32), which were very close to the standard white emission of (0.33, 0.33). Furthermore, the maximum luminescence intensity and luminescence yield were 524 cd/m² and 0.33 cd/A, respectively. This study suggested that a pure white light emission was achieved with the PFPQ copolymers or PF/PFPQ blends through the control of the energy transfer between F and PQ. Such PFPQ copolymers or PF/PFPQ blends would be interesting for electronic and optoelectronic devices. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and properties of polyether with short alternating conjugated and nonconjugated blocks containing oxadiazole units

A polyether, poly[(2,5‐dimethylene‐1,3,4‐oxadiazole)dioxy‐1,4‐phenylene‐1,2‐ethenylene‐1,4‐phenylene‐1,2‐ethenylene‐1,4‐phenylene], based on short alternating conjugated oxadiazole units, has been synthesized, which is a kind of PPV derivative that emits blue light. The resulting polymer is fairly soluble in chloroform. The synthesized polymer shows a UV–visible absorbency maximum wavelength around 310 nm in solution. The photoluminescence maximum wavelength for the resulting polymer appears around 470 nm. The polymer also exhibits good thermal stability up to 300°C under N₂ atmosphere. It is also observed that the onset temperature of thermal decomposition is as high as 355°C. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2682–2686, 2002     

Studies on the electronic transport and optical properties of some new chelate modified polysulfones in thin films

The studied polymers (chelate modified polysulfones) have been prepared by the polycondensation reaction between chloro‐end‐capped polysulfones and bis(2,4‐dihydroxybenzaldehyde)Cu²⁺ in the dymethyl sulfoxide/dichlormethane system, in the presence of an aqueous sodium hydroxide solution. The temperature dependence of electrical conductivity and Seebeck coefficient of the respective polymers was investigated using thin‐film samples, deposited from chloroform solutions onto glass substrates. The polymers under study have typical semiconducting properties. The values of some characteristic parameters of the investigated polymers (for example, activation energy of electrical conduction, ratio of carrier mobilities, etc.) have been determined. The nature of the electrical conduction mechanism is discussed. The values of the optical bandgap energy are determined from the absorption spectra. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 100–106, 2006     

Nanofiber organic semiconductors: The effects of nanosize on the electrical charge transport and optical properties of bulk polyanilines

The electrical transport, optical, and microstructural properties of bulk polyaniline (PANI) and nano‐PANIs were investigated. A field emission scanning electron microscopy (SEM) image of bulk PANI showed macroscopic and aggregated granular particles. A SEM image of the nanostructured PANI showed the formation of one‐dimensional nano/microstructures. The formation of nanofibers was observed from the transmission electron microscopy image. The electrical conductivities of the bulk and nanostructured PANIs increased with increasing temperature, which indicated semiconductor behavior. The electrical conductivities of the bulk and nanostructured PANIs at room temperature were found to be 2.12 × 10^?5 and 1.80 × 10^?2 S/cm, respectively. The electrical conductivity of the nanostructured PANI was about 850 times higher than that of the bulk PANI. The obtained band gaps of the bulk and nanostructured PANIs were determined from diffuse reflectance measurements and were found to be 3.27 and 2.41 eV, respectively. The refractive index of the PANI samples changed from 1.3 to 1.61. The obtained results indicate that the electrical and optical properties of the PANI were inherently dependent on the nanostructure. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Design of polymeric materials: Experiences and prescriptions

As process engineering has matured, research interest has shifted towards polymer product quality. In the past 20 years or so, the shift has progressed even further, as interest in polymer product quality has morphed into polymer product design. Product design is intended to be a targeted pursuit of optimal conditions that will yield polymers with desirable properties for a specific application. This can be achieved by following a systematic design framework that employs sequential, iterative steps informed by prior knowledge and experience. This overview provides some background information regarding the need for design (including some examples from previous experience), especially in terms of structure‐property relationships. When links between kinetics (synthesis conditions), polymer structure, and application properties are well‐understood, it becomes possible to essentially reverse‐engineer the polymeric material; the researcher can start with known application requirements and synthesize polymers with tailor‐made properties using an optimized recipe (according to the polymerization kinetics). A suggested design approach is presented herein, followed by the application of the design approach to two large case studies. The number of applications for polymeric materials is essentially limitless; the current work provides typical examples of a systematic polymeric material design framework (and related case studies).