Electrochemically nanopatterned conducting coronas of a conjugated polymer precursor: SPM parameters and polymer composition

Here we describe the formation of precisely controlled corona-type nanopatterns on electroactive polymer precursor films using scanning probe microscopy (SPM) methods. The binary composition of electroactive groups in the polymer triggers the formation of corona-type nanopatterns at particular voltages and tip writing speeds through the electrooxidation of the polymer precursor film. Various parameters such as tip speed and applied bias were explored in the nanopatterning process, and the formation of a conductive nanopattern was investigated using conducting atomic force microscopy (C-AFM). The formation of the nanopattern was attributed to the flow of electrons from the AFM tip to the polymer film in a controlled electric field distribution. We also report a new method to distinguish the polymer composition and distribution of a polymer blend film by characterizing biasing differences in the patterning of a polymer film.     

Nanopatterning and fabrication of memory devices from layer-by-layer poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) ultrathin films

A write-read-erasable memory device was fabricated on layer-by-layer (LbL) ultrathin films prepared from poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) (PEDOT-PSS) and poly(diallyldimethylammonium chloride) (PDDA). By use of current-sensing atomic force microscopy (CS-AFM), nanopatterns were formed by applying a bias voltage between a conductive tip (Pt-coated Si3N4 cantilever) in contact with the polymer film and gold substrate. The dependence of the nanopatterns on film thickness, applied bias, and writing speed was studied. Moreover, the height of the patterns was 3-5 times higher than the original thickness of the films, opening the possibility for three-dimensional nanopatterning. The ability of the patterns to be erased after nanowriting was also investigated. By comparing the I-V characteristics under ambient conditions and under N2 environment, a joule-heating activated, water meniscus-assisted anion doping mechanism for the nanopatterning process was determined. Write-read-erase memory device capability was demonstrated on the nanopatterns.     

Vapor phase polymerization of EDOT from submicrometer scale oxidant patterned by dip-pen nanolithography

Some of the most exciting recent advances in conducting polymer synthesis have centered around the method of vapor phase polymerization (VPP) of thin films. However, it is not known whether the VPP process can proceed using significantly reduced volumes of oxidant and therefore be implemented as part of nanolithography approach. Here, we present a strategy for submicrometer scale patterning of the conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) via in situ VPP. Attolitre (10(-18) L) volumes of oxidant "ink" are controllably deposited using dip-pen nanolithography (DPN). DPN patterning of the oxidant ink is facilitated by the incorporation of an amphiphilic block copolymer thickener, an additive that also assists with stabilization of the oxidant. When exposed to EDOT monomer in a VPP chamber, each deposited feature localizes the synthesis of conducting PEDOT structures of several micrometers down to 250 nm in width. PEDOT patterns are characterized by atomic force microscopy (AFM), conductive AFM, two probe electrical measurement, and micro-Raman spectroscopy, evidencing in situ vapor phase synthesis of conducting polymer at a scale (picogram) which is much smaller than that previously reported. Although the process of VPP on this scale was achieved, we highlight some of the challenges that need to be overcome to make this approach feasible in an applied setting.     

Study of electrochemical stability of conducting polymers by bidimensional spectroelectrochemistry: p- and n-doping of poly(4,4′-bis(butylthio)-2,2′-bithiophene) films

UV-vis bidimensional spectroelectrochemistry has been applied to the study of the electrochemical stability of conducting polymer films during p- and n-doping processes. Specifically, poly(4,4′-bis(butylthio)-2,2′-bithiophene) has been chosen as example to prove the usefulness and suitability of this multi-response technique to characterize polymer stability during p- and n-doping. It was found that oxidative doping and corresponding de-doping alone did not result in noticeable polymer film degradation. However, in experiments involving both p- and n-doping of this conducting polymer, soluble species arising from the polymer film were detected in solution for the first time, indicating a lower electrochemical stability of the film under these experimental conditions. Moreover, bidimensional spectroelectrochemistry has enabled us not only to detect the soluble degradation products, but also the potential range in which the degradation takes place.     

Impedance change induced by varying polymerization temperature of conducting polymer thin films

In this study, we use a conducting polymer precursor to build layer-by-layer (LbL) films. Thermal conversion of the polymer precursor to conducting polymer makes the LbL films intractable, so the LbL films can be used as protective layers in salt solution. The conducting polymer LbL film shows stabilizing effect on top of another LbL thin film that contains nanoparticles. The LbL film prepared in this study shows a 35-fold increase of conductivity than the literature values obtained from non-conducting polymer films. The stabilization of the films is the result of the polymerization of the conducting polymer, so other anionic polymers or nanoparticles may be used to afford additional functionalities.     

Block copolymer-templated chemical nanopatterning on pyrolyzed photoresist carbon films

Block copolymer nanolithography has been extended to the nanopatterning of organic functionalities on pyrolyzed photoresist carbon films (PPFs) via diazonium chemistry, using PS-b-P4VP as the template.     

Influence of the magnitude and direction of electric field on the transport and growth property of deposited polyaniline films

Polyaniline (PANI) films were deposited by electrochemical polymerization of aniline monomer on a fluorine-doped glass substrate at room temperature under different electric field directions. The as-synthesized PANI films obtained at different growth cycles were characterized by AC impedance spectroscopy and scanning electron microscopy (SEM). The results revealed that the film morphology, transport kinetics, and electrical properties are strongly dependent on the electric field direction and magnitude of the applied field during electropolymerization. The SEM morphology and AC impedance (modulus spectroscopy) indicate that a more homogeneous, high-porous, and conducting PANI film is induced by horizontal electric field direction (HEFD) electrodeposition, whereas the modulus spectroscopy of the PANI film deposited by vertical electric field direction (VEFD) reveals that VEFD deposition favours two-dimensional growth of PANI. The obtained polymer is more of dielectric in nature due to preferable dendritic growth which is supported by SEM analysis.     

Covalent immobilization of glucose oxidase on films prepared by electrochemical copolymerization of 3-methylthiophene and thiophene-3-acetic acid for amperometric sensing of glucose: Effects of polymerization conditions on sensing properties

For the purpose of glucose sensing, enzyme electrodes were fabricated via covalent immobilization of glucose oxidase on the films of conducting polymer. The films were prepared electrochemically by the copolymerization of 3-methylthiophene and thiophene-3-acetic acid. The properties of the films were investigated by taking into account the polymerization conditions (the kind of supporting electrodes, the current, the amount of passed charge, and the monomer concentration) and the dedoping treatment. The glucose sensing performance of the enzyme electrode was found to be affected markedly by the following three factors of the conducting polymer film: surface morphology, conductivity and cohesion with support electrodes. It was suggested that the ideal conducting polymer used for the enzyme electrode should be a thin film having high conductivity and ordered nanostructure.     

Solvent-assisted soft nanoimprint lithography for structured bilayer heterojunction organic solar cells

We introduce a novel method to easily fabricate nanopatterns at ambient conditions using solvent-assisted soft nanolithography. For this purpose, a P3HT/PCBM bilayer, one of well-known standard models of solar cell systems, was chosen to optimize bilayer solar cells using the new lithographic technique. The nanopatterns of P3HT made using this method have improved device efficiency compared to planar bilayer heterojunction of the solar cell. The new patterning process creates solar cell devices with a greater than 2-fold increase in power conversion efficiency (PCE) compared to an otherwise equivalent, flat device. This improvement in efficiency is due to the increased interfacial area created by the patterning process. This result demonstrates the feasibility of extensive applications toward nanolithography, relevant to device fabrication, such as electronic devices.     

Photochromism and electrochemistry of a dithienylcyclopentene electroactive polymer

A bifunctional substituted dithienylcyclopentene photochromic switch bearing electropolymerisable methoxystyryl units, which enable immobilization of the photochromic unit on conducting substrates, is reported. The spectroscopic, electrochemical, and photochemical properties of a monomer in solution are compared with those of the polymer formed through oxidative electropolymerization. The electroactive polymer films prepared on gold, platinum, glassy carbon, and indium titanium oxide (ITO) electrodes were characterized by cyclic voltammetry, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). The thickness of the films formed is found to be limited to several monolayer equivalents. The photochromic properties and stability of the polymer films have been investigated by UV/vis spectroscopy, electrochemistry, and XPS. Although the films are electrochemically and photochemically stable, their mechanical stability with respect to adhesion to the electrode was found to be sensitive to both the solvent and the electrode material employed, with more apolar solvents, glassy carbon, and ITO electrodes providing good adhesion of the polymer film. The polymer film is formed consistently as a thin film and can be switched both optically and electrochemically between the open and closed state of the photochromic dithienylethene moiety.     

Gradient doping of conducting polymer films by means of bipolar electrochemistry

In this paper, we report a novel electrochemical doping method for conducting polymer films based on bipolar electrochemistry. The electrochemical doping of conducting polymers such as poly(3-methylthiophene) (PMT), poly(3,4-ethylenedioxythiophene) (PEDOT), and poly(aniline) (PANI) on a bipolar electrode having a potential gradient on its surface successfully created gradually doped materials. In the case of PEDOT film, the color change at the anodic side was also observed to be gradually transparent. PANI film treated by the bipolar doping gave a multicolored gradation across the film. The results of UV-vis and energy dispersive X-ray analyses for the doped films supported the distribution of dopants in the polymer films reflecting the potential gradient on the bipolar electrode. Furthermore, the reversibility of the bipolar doping of the PMT film was demonstrated by a spectroelectrochemical investigation.     

Athermal and Soft Multi-Nanopatterning of Azopolymers: Phototunable Mechanical Properties

Imprinting nanopatterns on flexible substrates has diverse applications in advanced fabrication. However, the traditional thermal nanoimprint lithography (T-NIL) often causes shrinkage upon cooling. Here, a simple yet versatile method is introduced to fabricate multiple nanopatterns on a flexible substrate coated with an azopolymer by combining athermal nanoimprint lithography (AT-NIL) and photolithography. The azopolymer has various mechanical properties upon photoirradiation: 1) phototunable glass-transition temperatures (T_g) and concomitantly photoinduced switch from glassy plastic to viscoplastic polymer; 2) prominent modulation of viscoplasticity under light illumination at different wavelengths. Regionally selective multiple nanopatterns are conveniently fabricated, presenting angle-dependent structural color images on poly(ethylene terephthalate) (PET) substrates. The flexible, athermal and multiple nanopatterning method has the potential for on-demand fabrication of complex nanopatterns.     

Athermal and Soft Multi‐Nanopatterning of Azopolymers: Phototunable Mechanical Properties

Imprinting nanopatterns on flexible substrates has diverse applications in advanced fabrication. However, the traditional thermal nanoimprint lithography (T‐NIL) often causes shrinkage upon cooling. Here, a simple yet versatile method is introduced to fabricate multiple nanopatterns on a flexible substrate coated with an azopolymer by combining athermal nanoimprint lithography (AT‐NIL) and photolithography. The azopolymer has various mechanical properties upon photoirradiation: 1) phototunable glass‐transition temperatures (T_g) and concomitantly photoinduced switch from glassy plastic to viscoplastic polymer; 2) prominent modulation of viscoplasticity under light illumination at different wavelengths. Regionally selective multiple nanopatterns are conveniently fabricated, presenting angle‐dependent structural color images on poly(ethylene terephthalate) (PET) substrates. The flexible, athermal and multiple nanopatterning method has the potential for on‐demand fabrication of complex nanopatterns.     

A multiswitchable poly(terthiophene) bearing a spiropyran functionality: understanding photo- and electrochemical control

An electroactive nitrospiropyran-substituted polyterthiophene, poly(2-(3,3'-dimethylindoline-6'-nitrobenzospiropyranyl)ethyl 4,4'-didecyloxy-2,2':5',2'-terthiophene-3'-acetate), has been synthesized for the first time. The spiropyran, incorporated into the polymer backbone by covalent attachment to the alkoxyterthiophene monomer units, leads to multiple colored states as a result of both photochemical and electrochemical isomerization of the spiropyran moiety to merocyanine forms as well as electrochemical oxidation of the polyterthiophene backbone and the merocyanine substituents. While electrochemical polymerization of the terthiophene monomer can take place without oxidation of the spiropyran, increasing the oxidation potential leads to complex electrochemistry that clearly involves this substituent. To understand this complex behavior, the first detailed electrochemical study of the oxidation of the precursor spiropyran, 1-(2-hydroxyethyl)-3,3-dimethylindoline-6'-nitrobenzospiropyran, was undertaken, showing that, in solution, an irreversible electrochemical oxidation of the spiropyran occurs leading to reversible redox behavior of at least two merocyanine isomers. With these insights, an extensive electrochemical and spectroelectrochemical study of the nitrospiropyran-substituted polyterthiophene films reveals an initial irreversible electrochemical oxidative ring-opening of the spiropyran to oxidized merocyanine. Subsequent reduction and cyclic voltammetry of the resulting nitromerocyanine-substituted polyterthiophene film gives rise to the formation of both merocyanine π-dimers or oligomers and π-radical cation dimers, between polymer chains. Although merocyanine formation is not electrochemically reversible, the spiropyran can be photochemically regenerated, through irradiation with visible light. Subsequent electrochemical oxidation of the nitrospiropyran-substituted polymer reduces the efficiency of the spiropyran to merocyanine isomerization, providing electrochemical control over the polymer properties. SEM and AFM images support the conclusion that the bulky spiropyran substituent is electrochemically isomerized to the planar merocyanine moiety, affording a smoother polymer film. The conductivity of the freestanding polymer film was found to be 0.4 S cm(-1).     

Competition between Polymerization and Dissolution of Poly(3-methylthiophene) Films

Films of electrically conducting polymer, poly(3-methylthiophene), are dissolved in monomer-free solutions at positive potentials to become thin, whereas they are polymerized in monomer-rich solutions at the same potentials as for the dissolution. A question arises whether they are dissolved or polymerized in solutions including a given concentration of the monomer when a positive potential is applied to the film. Conditions of the competition between the polymerization and the dissolution were searched at potentiostatic experiments for poly(3-methylthiophene) films at various concentrations of monomers and potentials. The dissolution prevailed over the polymerization as the concentration decreased and the potential was less positive. Chronoamperometric currents exhibited oscillation under the competition conditions. The oscillation was explained in terms of the Lotka–Volterra model for a simple oscillation reaction, in which competitive species were the conducting polymer and the monomer.     

Ac-electrogravimetry study of ionic exchanges on a polypyrrole modified electrode in various electrolytes

For many years, polypyrrole films have appeared to be the most studied conducting polymer. Unfortunately, shadows still remain concerning the electrochemical mechanisms of these films and in particular, the aspect which concerns the limiting step which governs the electrochemical response. Different possibilities are available such as the transport of ionic species in the film, the electron transfer at the electrode/film or the electron motion in the film, the ionic exchanges at the film/interface electrolyte. Classical electrochemical methods do not permit to discriminate between these effects. Ac-electrogravimetry technique was used here to demonstrate that the electrochemical behaviour of thin pPy films is governed by the ionic insertion without any doubt. Particular parameters were modified as the ionic atomic weight or the electrolyte concentration to corroborate this idea.     

Photoelectrochemical effect with poly(p-phenylene sulfide) films

Poly(p-phenylene sulfide) films coated on conducting SnO₂ and Pt surfaces were found to attain p-type semiconducting properties on electrochemical cycling. Upon illumination of these films with visible light (λ < 500 nm) a photoelectrochemical effect was observed. The performance of a photoelectrochemical cell employing this polymer film coated electrode is discussed.     

Polyaniline/poly(vinyl alcohol) (PAN/PVA) composite films: the synergy of film structural stiffening, redox amplification, and mobile species compositional dynamics

In this work, we report an unexpected but significant improvement of the redox behavior of conducting polyaniline (PAN) films by trapping intrinsically nonconducting poly(vinyl alcohol) (PVA) in the matrix of the polymer acting as stiffening and/or cross-linking agents. Film structural stiffening of PAN/PVA inclusion was studied in relation to film compositional dynamics. PAN and PAN/PVA composite films were potentiodynamically deposited using high-frequency electrochemical quartz crystal microbalance under electrochemical potentiodynamic control. From the simultaneously obtained measurements of nanogravimetric and cyclic voltammetric data, it has been found that the presence of PVA in the deposition solution increased the rate of PAN film growth as a function of PVA concentration. Characterization of the resultant composite films in monomer-free acidic electrolyte solutions showed significantly enhanced redox behavior of PAN/PVA composite films (with different PVA contents) compared to pure PAN by a factor of ～2–4. For the study of structure–composition relationships of composite polymer films, fluxes of instantaneous mobile species dynamics (ion/solvent) as a function of film redox conversion and potential cycling were correlated with film structural stiffening and the observed unusual redox enhancement of PAN/PVA composite films. Using various experimental timescales, we were able to resolve bound (associated with ion transfer) and free solvent compositional dynamics (associated with thermodynamic activity balance).     

Ultrathin conjugated polymer network films of carbazole functionalized poly(p-phenylenes) via electropolymerization

Ultrathin films of a cross-linked and chemically distinct conjugated poly(p-phenylene) network via electropolymerization are described. The amphiphilic network precursor was synthesized by incorporating the alkoxy carbazole group (-O(CH2)5Cb) to a poly(p-phenylene) (C6PPPOH) backbone. In order to investigate the combined thin film electrochemical and photophysical properties of poly(p-phenylene)s and polycarbazole conjugated polymers, C6PPPC5Cb was deposited on substrates using the Langmuir Blodgett Kuhn (LBK) method. The monolayer isotherm of the polymer, C6PPPC5Cb, showed a liquid expanded region slightly different from the parent polymer C6PPPOH. Multilayers (up to 30 layers) were transferred to different substrates such as quartz, gold coated LaSFN9 and ITO substrates for analysis. For conversion to a conjugated polymer network (CPN) film, the electroactive carbazole group was electropolymerized using cyclic voltammetry (CV) resulting in polycarbazole linking units. The differences in the film properties and corresponding changes in the electrochemical behavior indicate the importance of film thickness and electron/ion transport process in cross linked network films. From the electrochemical studies, the scan rate was found to have a considerable effect on electropolymerization with higher oxidation and reduction peak values found for the rigid network polymer compared to the uncrosslinked polymers.     

聚丙烯酸修饰咔唑的电化学聚合及表征

合成了侧链带有咔唑的N-丙烯酰氧己基咔唑(MACZ),通过自由基聚合得到聚N-丙烯酰氧己基咔唑(PMACZ),在四氢呋喃含10%三氟化硼乙醚与四氟化硼四丁基胺的混合电解质溶液中,直接阳极氧化PMACZ获得自支撑交联网状的聚(聚N-丙烯酰氧己基咔唑)(PPMACZ)薄膜.PPMACZ薄膜具有良好的氧化还原性和热稳定性,电导率为1.34×10-5S·cm-1.1HNMR和红外光谱表明PMACZ二次聚合反应发生在咔唑单元的3,6位上,荧光光谱表明PPMACZ薄膜是一种良好的蓝色发光材料.