Influence ofβ-cyclodextrin as an encapsule and as an inclusion complex dopant on conducting polyaniline

An investigation on the effect ofβ-cyclodextrin (CD) in both free and inclusion-complexed forms with a guest anionic metal complex, dioxalatodiaquochromate(III) (DDC), on the characteristics of conducting polyaniline (PANI) is carried out. Four materials, PANI (i.e. PANI-SO ₄ ²⁻ ), PANI-DDC, PANI-CD and PANI-CD + DDC were prepared byin situ chemical oxidative polymerization in aqueous H ₂SO₄ at pH 1 and subjected to electrical conductivity and spectral (IR and UV-vis bd measurements. DDC and CD when separately incorporated, reduce the conductivity of PANI by about half whilst their inclusion complex CD + DDC enhances it. Spectral characterization reveals that DDC as a dopant and CD as an encapsule exhibit their effects through adverse interaction with imine-amine N centres and benzenoid moiety of PANI. The inclusion complex CD + DDC, on the contrary, functions as a dopant by lying in between the chains and seems to promote the extended conformation of PANI chain and hence theπ -electron delocalization. Exposure of the material to methanol vapour causes a decrease in conductivity in PANI and PANI-CD while an increase in PANI-CD + DDC. This study makes explicit the distinct role of CD as an encapsule and CD + DDC inclusion complex as a dopant in altering the electrical property of PANI.     

Effect of iodine solutions on polyaniline films

Polyaniline (PANI) emeraldine-base films have been exposed to iodine solutions. The interaction between the films and the iodine solution was studied using the quartz-crystal microbalance (QCM) technique and the UV-visible absorption spectroscopy. The iodine-treated film of emeraldine base was subjected to dedoping process using 0.1 M ammonia solution. The resulting film was exposed again to the previously used iodine solution. Iodine was found to play multiple roles: the ring-iodination of PANI film, the oxidation of PANI to pernigraniline base, and iodine doping to PANI salt. A sensor based on PANI-coated electrode of QCM was developed to monitor the presence of iodine in solution.     

Transferring and Retaining of Different Polyaniline Nanofeatures via Electrophoretic Deposition for Enhanced Sensing Performance

Nanofeatured polyaniline (PANI) electrodes have demonstrated impressive sensing performance due to the enhanced electrolyte diffusion and ion transport. However, the retaining of these nanostructures on substrates via electrophoretic deposition (EPD) faces an insurmountable challenge from the involved dedoping process. Here, camphorsulfonic acid is utilized with high steric effects to dope PANI (PANI-CSA) that can be directly used EPD without involving a dedoping process. Five different nanofeatures (sea cucumber-like, nanofiber, amorphous, nanotube, and nanorod) are synthesized, and they have been all successfully transferred onto indium tin oxide substrate in a formic acid/acetonitrile system, namely a morphology memory effect. The mechanism of retaining these nanofeatures is revealed, which is realized via the processes of dissolution of PANI-CSA, codoping and solvation, and reassembly of basic units into the original nanofeature. The enhanced protonation level by the codoping of formic acid and solvation of acetonitrile plays the key role in retaining these nanofeatures. This method is also applicable to transfer PANI/gold nanorod composites (PANI-CSA/AuNRs). The PANI-CSA/AuNRs electrode as an ascorbic acid sensor has shown an excellent sensing performance with a sensitivity up to 872.7 µA mm ⁻¹ cm⁻² and a detection limit of as low as 0.18 × 10⁻⁶ m .     

Enhancing Molecular n‐Type Doping of Donor–Acceptor Copolymers by Tailoring Side Chains

In this contribution, for the first time, the molecular n‐doping of a donor–acceptor (D–A) copolymer achieving 200‐fold enhancement of electrical conductivity by rationally tailoring the side chains without changing its D–A backbone is successfully improved. Instead of the traditional alkyl side chains for poly{[N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl](NDI)‐alt‐5,5′‐(2,2′‐bithiophene)} (N2200), polar triethylene glycol type side chains is utilized and a high electrical conductivity of 0.17 S cm^?1 after doping with (4‐(1,3‐dimethyl‐2,3‐dihydro‐1H‐benzoimidazol‐2‐yl)phenyl)dimethylamine is achieved, which is the highest reported value for n‐type D–A copolymers. Coarse‐grained molecular dynamics simulations indicate that the polar side chains can significantly reduce the clustering of dopant molecules and favor the dispersion of the dopant in the host matrix as compared to the traditional alkyl side chains. Accordingly, intimate contact between the host and dopant molecules in the NDI‐based copolymer with polar side chains facilitates molecular doping with increased doping efficiency and electrical conductivity. For the first time, a heterogeneous thermoelectric transport model for such a material is proposed, that is the percolation of charge carriers from conducting ordered regions through poorly conductive disordered regions, which provides pointers for further increase in the themoelectric properties of n‐type D–A copolymers.     

D.C. conductivity and spectroscopic studies of polyaniline doped with binary dopant ZrOCl<Subscript>2</Subscript>/AgI

Aqueous binary dopant (ZrOCl₂/AgI) is used in different ratios such as 1:1, 1:2 and 2:1 (w/w) for chemical doping to enhance the conductivity of synthesized polyaniline (PANI). The doping of polyaniline is carried out using tetrahydrofuran as a solvent. Doped samples are characterized using various techniques such as I–V characteristics, UV-visible spectroscopy, X-ray diffractometry (XRD), FTIR and photoluminescence (PL) studies. A significant enhancement in d.c. conductivity has been observed with the introduction of binary dopant. UV-visible study shows that optical parameters change considerably after doping. Interestingly, both direct and indirect bandgaps are observed in the doped samples. XRD patterns show the semi-crystalline nature of doped polyaniline. FTIR study shows structural modifications in functional groups with doping in PANI. Photoluminescence spectra exhibit emission properties of the samples.     

Preparation and characterization of soluble and DBSA doped polyaniline grafted multi-walled carbon nanotubes nano-composite

Soluble and highly doped polyaniline (PANI) grafted multi-walled carbon nanotubes (MWNTs) nano-composite was synthesized by in situ oxidation polymerization, de-doping with ammonium hydroxide and doping the PANI-Emeraldine base (PANI-EB) grafted MWNTs nano-composite in N-methyl-2-pyrrolidinone (NMP) with Dodecyl benzene sulfonic acid (DBSA). Transmission electron microscope (TEM), Raman spectra, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and standard four-probe methods were employed to characterize morphology, chemical structure and electronic conductivity of the nano-composite. The results show that oxidized phenylamine groups of phenylamine groups contained MWNTs (p-MWNTs) initiate PANI polymerization on the surface of p-MWNTs. PANI coatings graft on the surface of p-MWNTs via amide bond forming homogeneous core (p-MWNTs)–shell (PANI) nano-structures. After doping PANI-EB grafted MWNTs nano-composite with DBSA, the attachment of soluble DBSA doped PANI chains on the surface of p-MWNTs via covalent bonding renders p-MWNTs compatible with polymer matrix and lead to DBSA doped PANI grafted MWNTs nano-composite soluble and stable in NMP. Owing to incorporation of p-MWNTs and chemical bridges between p-MWNTs and PANI chains, conductivity of DBSA doped PANI grafted MWNTs nano-composite at room temperature is increased by about two orders of magnitude over neat DBSA doped PANI.     

Synthesis and characterization of polyaniline-camphorsulphonic acid nanotube film

Polyaniline (PANI) nanotubes were prepared in the bulk solution and as films using the aniline oxidation with ammonium peroxydisulfate in aqueous solutions of camphorsulfonic acid (CSA). The in situ PANI films produced during the oxidation of aniline in CSA and also in hydrochloric acid solutions were followed by monitoring the frequency changes of quartz crystal microbalance (QCM). The kinetics of the film formation were discussed. The scanning electron microscopy (SEM) and scanning transmission electron microscopy (STEM) showed PANI nanotubes. In addition, nanorods and nanoflowers composed from nanofibers and nanoflakes are also present to some extent. The nanotubes were characterized using UV-Vis spectroscopy.     

Effect of Pb2+ and Cu2+ as a codopant on the structure,morphology and conductivity of nanostructured polyaniline

Polyaniline (PANI) has been successively synthesized in aqueous diethylene glycol solution medium by chemical oxidative polymerization of aniline using ammonium peroxidisulfate [(NH₄)₂S₂O₈] as an oxidant in an aqueous solution of 0.5 M acetic acid (CH₃COOH) as a dopant. Polyaniline–lead (PANI–Pb) and polyaniline–copper (PANI–Cu) nanocomposites have been chemically prepared for the first time by oxidative polymerization of aniline in aqueous diethylene glycol/acetic acidic medium. The synthesized PANI and nanocomposites were characterized by Fourier transform infrared spectroscopy (FTIR). Conductivity measurements of the polymer and nanocomposites were performed using the four-probe technique. Morphology changes of the composites were investigated by scanning electron microscopy (SEM). PANI nanotubes were formed without added codopant, but when Pb(CH₃COO)₂ or Cu(CH₃COO)₂ was added as a codopant, the morphology of PANI obviously changed. The PANI–Cu and PANI–Pb nanocomposites exhibit higher conductivity than the PANI homopolymer, but the conductivity of the composites slightly decreased on increasing the metal concentrations.     

Effect of different carbon fillers and dopant acids on electrical properties of polyaniline nanocomposites

Electrically conducting nanocomposites of polyaniline (PANI) with carbon-based fillers have evinced considerable interest for various applications such as rechargeable batteries, microelectronics, sensors, electrochromic displays and light-emitting and photovoltaic devices. The nature of both the carbon filler and the dopant acid can significantly influence the conductivity of these nanocomposites. This paper describes the effects of carbon fillers like carbon black (CB), graphite (GR) and muti-walled carbon nanotubes (MWCNT) and of dopant acids like methane sulfonic acid (MSA), camphor sulfonic acid (CSA), hydrochloric acid (HCl) and sulfuric acid (H₂SO₄) on the electrical conductivity of PANI. The morphological, structural and electrical properties of neat PANI and carbon–PANI nanocomposites were studied using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT–IR), UV–Vis spectroscopy and the four-point probe technique, respectively. Thermogravimetric analysis (TGA) and X-ray diffraction (XRD) studies were also conducted for different PANI composites. The results show that PANI and carbon–PANI composites with organic acid dopants show good thermal stability and higher electrical conductivity than those with inorganic acid dopants. Also, carbon–PANI composites generally show higher electrical conductivity than neat PANI, with highest conductivities for PANI–CNT composites. Thus, in essence, PANI–CNT composites prepared using organic acid dopants are most suitable for conducting applications.     

Electrodeposition of graphene layers doped with Brϕnsted acids

A simple and fast method is demonstrated for the preparation of a thin film of graphene layers by the electrodeposition of positively doped graphene dispersion onto desired electrode substrates. A thin film of graphene layers was obtained by applying negative potentials according to the electrophoretic deposition mechanism. The doped graphene dispersion was prepared from expanded graphite treatment with various acids (HCl, HNO₃, and H₂SO₄) and an ultrasonication process. The doping and deposition processes are strongly dependent on the type of acid and the applied potential, which were monitored by Raman spectroscopy and quartz crystal microbalance, respectively. The morphology and electrochemical properties of the graphene film were characterized by scanning electron microscopy and cyclic voltammetry. The electrochemical performance of graphene film obtained using nitric acid or hydrochloric acid dopant is superior to that obtained with sulfuric acid doping. This technique could be a facile tool for the fabrication of a thin film of graphene layers on a desired substrate.     

Synthesis of oriented polyaniline flake arrays

We first report the synthesis of oriented polyaniline (PANI) flake arrays by a self-assembly method with inorganic acid as a dopant. It is found that the morphology and molecular structure depend on aniline concentration. FTIR and XRD results reveal that the oriented PANI flake arrays are in high conductive emeraldine state, which is expected to show excellent electrochemical properties. Cyclic voltammograms of I₂/I^- system measurement shows that the oriented PANI flake arrays present small charge-transfer resistance and high electrocatalytic activity. The oriented PANI flake arrays are expected to be useful in electrical, optical and electrochemical devices.     

Direct bonding of silicon wafers with a diffusion layer

The possibility of solid-phase direct bonding of silicon wafers having p ⁺-or n ⁺-type diffusion layers with a high surface dopant concentration has been demonstrated for the first time. Pis’ma Zh. Tekh. Fiz. 24, 1–5 (March 26, 1998)     

Potentiometric study of polyaniline film synthesized with various dopants and composite-dopant: A comparative study

The potentiometric study of polyaniline (PANI) film synthesized with dopants viz. polyvinyl sulfonic acid (PVS),p-toluene sulfonic acid (p TS), dodecyl benzene sulfonic acid (DBS) and composite-dopants viz. PVS-p TS and PVS-DBS, has been carried out. The synthesized PANI films were characterized by electrochemical technique, UV-visible spectroscopy, Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM) and conductivity measurement. It was found that the PANI doped with PVS gives good electrochemical properties, conductivity as well as surface morphology as compared to p TS and DBS, whereas in composite dopants the PANI doped with PVS-pTS gives good polymer matrix as compared to PVS-DBS.     

Vibrational and AFM studies of adsorption of glycine on DLC and silicon-doped DLC

A better understanding of protein adsorption onto surfaces of materials is required to control biocompatibility and bioactivity. Diamond-like carbon (DLC) is known to have excellent biocompatibility. Various samples of a-C:H and silicon-doped a-C:H thin films (Si-DLC) were deposited onto silicon substrates using plasma-enhanced chemical vapour deposition (PECVD). Subsequently, the adsorption of the simplest amino acid glycine onto the surfaces of the thin films was investigated to elucidate the mechanisms involved in protein adhesion. The physicochemical characteristics of the surfaces, before and after adsorption of glycine, were investigated using Raman spectroscopy and atomic force microscopy (AFM). The Raman study highlighted a slight decrease in the I _D/I _G ratio with increasing the silicon dopant levels. Following exposure to glycine solutions, the presence of bands at ~1735 and ~1200 cm⁻¹ indicates that the adsorption of glycine onto the surfaces has taken place. Glycine was bound to the surfaces via both deprotonated carboxyl and protonated amino groups whilst, as the silicon content in the DLC film increased the adsorption of glycine decreased. AFM analysis showed that the surface roughness increased following exposure to glycine. These results show that at low silicon doping the adsorption of the amino acid was enhanced whilst increased doping levels led to a reduced adsorption compared to undoped DLC. Therefore, doping of DLC may provide an approach to control the protein adsorption.     

Diffusion of Phosphorus in silicon dioxide from a spin-on source

The diffusion of phosphorus in silicon dioxide was investigated. A phosphosilicate glass which was deposited from a solution containing a silicic ester was used as the source. Using radioactive ³²P it was possible to determine the dopant profile in silicon dioxide by measuring the β activity. The profiles obtained cannot be described by the usual solution of the diffusion equation. The phosphorus mobility in silicon dioxide was found to be markedly dependent on the oxygen content of the ambient gas during diffusion. Pre-annealing in nitrogen of the SiO₂ layer into which the diffusion took place similarly influences the diffusion profile. It is presumed that a free acid of phosphorus from the doping solution participates in the diffusion process.     

Synthesis and characterization of HCl doped polyaniline grafted multi-walled carbon nanotubes core-shell nano-composite

Multi-walled carbon nanotubes (MWNTs) was modified with p-phenylenediamine (p-PDA) and hydrochloric acid (HCl) doped polyaniline (PANI) grafted MWNTs nano-composite was synthesized by in situ oxidation polymerization. Raman spectra, XPS, TEM and XRD reveal that modification does not decrease the integrity of outer graphite sheets in p-PDA modified MWNTs (p-MWNTs) excessively and results in phenylamine groups with concentration of 3.7% covalently grafted on the surface of p-MWNTs via amide bond. Oxidized phenylamine groups initiate polymerization and contribute to the formation of inner layer of PANI coatings. As self-assembly templates, p-MWNTs are encapsulated by PANI forming a homogeneous core (p-MWNTs)-shell (HCl doped PANI) nano-structure with controlled organization. In earlier reaction period, polymer chains are highly ordered and microcrystalline domains are enriched in the inner PANI layers. When deposition of PANI chains under less restriction, more amorphous parts are distributed in the outer layers of PANI coatings. TGA and conductivity data reveal that although chemical modification affects the performance of p-MWNTs, thermal stability and electronic conductivity at room temperature of HCl doped PANI grafted MWNTs nano-composite are highly improved owing to incorporation of p-MWNTs and covalent bindings between PANI and carbon nanotubes.     

The spin diffusion coefficient of3He in3He-4He solutions

The transport properties of³He in³He-⁴He solutions with molar concentrations of 5, 9, 14, and 24% have been studied for 0.9 KT2.5 K. The spin diffusion coefficientD _s and the longitudinal relaxation timeT ₁ were measured by the spin-echo method for temperatures both above and below the solution lambda temperatureT . The spin-echo method measures the diffusion coefficient for magnetizationD _s, which differs from the usual diffusion coefficient for particlesD belowT .D _s depends on the³He-³He scattering cross section _FF and the³He-roton/phonon cross section _FB, whileD depends only on _FB. The distinction betweenD _s andD is elaborated in terms of a simple mutual-friction model for diffusion. The two scattering mechanisms are clearly evident in the behavior ofD _s as a function of concentrationx and temperature. The contribution due to the³He-³He scattering is inversely proportional tox, indicating that the³He can be treated in first approximation as a classical gas (the Pomeranchuk model). The predictions of various theoretical models are compared with the results, where possible, but most of the previous theoretical work is not applicable to the concentration range and temperatures of these measurements.Supported in part by the National Science Foundation and the U.S. Office of Naval Research.     

Deep diffusion doping of macroporous silicon

An investigation is made of the diffusion of boron and phosphorus impurities in macroporous silicon with a regular structure of deep cylindrical pores, for which through doping of the walls was achieved. The ∼150 μm layers obtained were quasiuniformly doped and had a planar diffusion front, and their electric parameters were very similar to those of the doped single crystal. It is demonstrated that deep diffusion of phosphorus may be used to fabricate n-n ⁺ structures. Pis’ma Zh. Tekh. Fiz. 25, 72–79 (December 12, 1999)     

Observations of polyaniline surface morphology modification during doping and de-doping using atomic force microscopy

Chemically synthesized 30 m thick polyaniline films were studied during the doping and dedoping process by imaging the polymer surface using in situ atomic force microscopy (AFM). The polymer, which was initially in the base non-conducting form, was doped using aqueous solutions of both tosylic acid (pH = 0.2) and HCl (pH = 0.2 and 1.0). De-doping was accomplished by exposing the same doped polymer surface to NH₄OH (pH = 12) base solution. AFM images showed that it was necessary to cycle the polymer surface three times between acid and base before a reproducible surface morphology was established. For the case of doping with tosylic acid, AFM images showed that the polyaniline surface was immediately roughened; the changes in mean roughness for the base and acid conditions were ~ 5.4 and ~ 6.7 nm, respectively. In addition there appeared to be an increase in the size of surface channels and cracks. When doping with HCl (pH = 1.0), no change in surface morphology was observed; however, noticeable surface roughening occurred over 10 min for the case of the lower pH = 0.2 solution; mean roughness changes for the base and acid conditions were ~ 17.9 and 39.2 nm. Radio frequency measurements, which determined the polymer complex permittivity, and d.c. conductivity measurements were used to determine the level of doping in the samples studied by AFM which were exposed to acid solutions.     

QCM Measurements of Superfluid Response in 4He Films up to 180 MHz

At finite frequencies, a dynamic Kosterlitz–Thouless (KT) theory predicts a frequency dependence of the superfluid transition in ⁴He films on planar surfaces. We report results of QCM measurements to study the superfluid response on planar gold surfaces for very high frequencies up to 180 MHz in the temperature range of 0.6–1.0 K. As the frequency is increased, we observed the expected KT behavior that the superfluid transition shifts to a higher temperature from the static transition temperature T _KT and the transition temperature region broadens. The frequency dependence of the dissipation peak temperature at the transition agrees with a simple equation of the frequency dependence based on the dynamic KT theory. The microscopic parameter for the dynamic transition, the ratio of the diffusion constant to the square of the vortex core radius D/r ₀ ², is estimated to be on the order of 10¹⁰ s⁻¹.