Layer-by-layer assembled graphene oxide/polydiallydimethylammonium chloride composites for hydrogen gas barrier application

Poly(diallyldimethylammoium chloride) (PDDA)/acid or base modified graphene oxide (MGO) composite (PDDA/MGO)-based gas barrier films were prepared by layer-by-layer (LBL) assembly method on polyethylene terephthalate (PET) substrate using a spray coating assisted deposition. The effect of pH on the hydrogen gas permeability (H₂GP) values of the different MGO-based films was investigated to determine the optimum pH value of the MGO solution for the preparation of PDDA/MGO-based LBL assembly. Accordingly, the different numbers of bilayers based LBL-assembled films were prepared using alternate deposition of PDDA and MGO solutions and the H₂GP values were measured for those assemblies. The films were characterized by XRD, FT-IR, and Raman spectroscopy analyses. The morphology of the LBL-assembled film was observed by cross-sectional field emission scanning electron microscopy which confirms densely packed layered structure. The H₂GP of six bilayers PDDA/MGO composite film is 5.7 cc/m²?d?atm, which is much lower than that of pure PET substrate (170.7 cc/m²?d?atm), indicating 96.7% decrease in H₂GP. This result suggests that the PDDA/MGO composite film could be used as a potential candidate to fabricate hydrogen gas barrier coating material.     

Fabrication and characterization of multilayer films based on Keggin-type polyoxometalate and chitosan

Multilayer films based on Keggin-type polyoxometalate (POM) α-[SiW₁₂O₄₀]⁴⁻ (α-SiW₁₂), α-[PMo₁₂O₄₀]³⁻ (α-PMo₁₂) and cationic chitosan have been fabricated in aqueous solution via the layer-by-layer self-assembly technique (LBL). The resulting films were characterized by UV–Vis spectra, X-ray photoelectron spectra (XPS), atomic force microscopy (AFM) and cyclic voltammetry (CV) measurements. UV–Vis spectra show that the absorbance values at characteristic wavelengths of the multilayer films increase almost linearly with the number of chitosan/POM bilayers, suggesting that the deposition process is regular and highly reproducible from layer to layer. XPS spectra confirm the incorporation of chitosan and POMs into the films. AFM images indicate that the surface of the multilayer films is rather uniform and smooth. The antibacterial activities against Escherichia coli of the LBL films have also been investigated by optical density method.     

Low-indium content bilayer transparent conducting oxide thin films as effective anodes in organic photovoltaic cells

Bilayer In-doped CdO/Sn-doped In₂O₃ (CIO/ITO) transparent conducting oxide (TCO) thin films were prepared by depositing thin ITO films by ion-assisted deposition on CIO films grown by metal-organic chemical vapor deposition. The optical, electrical, and microstructural properties of these bilayer TCO films were investigated in detail. A low sheet resistance of ~ 4.9 Ω/□ is achieved for the CIO/ITO (170/40 nm) bilayers without annealing. With a significantly lower In content (20 vs. ~ 93 at.%) and a much higher conductivity (> 12,000 vs. 3000-5000 S/cm) than commercial ITO, these bilayer films were investigated as anodes in bulk-heterojunction organic photovoltaic (OPV) devices having a poly(2-methoxy-5-(3,7-dimethyloctyloxy)-1,4-phenylenevinylene) + [6,6]-phenyl C₆₁ butyric acid methyl ester active layer. Device performance metrics in every way comparable to those of devices fabricated on commercial ITO are achieved, demonstrating that CIO/ITO bilayers are promising low-In content, highly conductive and transparent electrode candidates for OPV cells.     

Interface modification of ITO thin films: organic photovoltaic cells

In this paper we review our recent studies of the surface characterization of commercially available indium-tin-oxide (ITO) thin films, using photoelectron spectroscopies (XPS and UPS) and electrochemistry of chemisorbed probe molecules such as ferrocene dicarboxylic acid (Fc(COOH)₂). The modification of these ITO films through chemisorption of carboxylic acid-substituted small molecules, such as Fc(COOH)₂, 3-thiophene acetic acid (3-TAA), and the subsequent modification of these interfaces with electrochemically grown conducting polymer (CP) films is also introduced. We report preliminary results of our studies changes in performance of vacuum deposited organic photovoltaic (PV) cells as a result of these ITO substrate modification steps. The surfaces of as-received ITO films, and those cleaned by various solution and plasma-etching processes, are unavoidably hydrolyzed to In(OH)₃-like and InOOH-like surface species, which leaves the ITO surface with at most 40-50% of the electronically active sites available for electron transfer reactions. Modification of the ITO surface with electroactive small molecules such as Fc(COOH)₂ and 3-TAA provides for better wettability of organic layers to the polar ITO surface and enhanced electrical contact (lower series resistance, R_S) between the ITO anode, spin-cast or electrodeposited PEDOT:PSS layers and copper phthalocyanine (CuPc) layers in multilayer (CuPc/C₆₀/BCP) excitonic PV cells. Improvements in PV J/V (current/voltage) responses are noted mainly through increases in short-circuit photocurrent and lowered series resistances (R_S) when electroactive small molecules are chemisorbed to the ITO surface, prior to spin-casting of conducting polymer, PEDOT:PSS, layers.     

Influence of polyaniline and phthalocyanine hole-transport layers on the electrical performance of light-emitting diodes using MEH-PPV as emissive material

The influence of layer-by-layer films of polyaniline and Ni-tetrasulfonated phthalocyanine (PANI/Ni-TS-Pc) on the electrical performance of polymeric light-emitting diodes (PLED) made from (poly[2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene vinylene]) (MEH-PPV) is investigated by using current versus voltage measurements and impedance spectroscopy. The PLED is composed by a thin layer of MEH-PPV sandwiched between indium tin oxide (ITO) and aluminum electrodes, resulting in the device structure ITO/(PANI/Ni-TS-Pc)_n/MEH-PPV/Al, where n stands for the number of PANI/Ni-TS-Pc bilayers. The deposition of PANI/Ni-TS-Pc leads to a decrease in the driving voltage of the PLEDs, which reaches a minimum when n = 5 bilayers. In addition, impedance spectroscopy data reveal that the PLED impedance decreases as more PANI/Ni-TS-Pc bilayers are deposited. The PLED structure is further described by an equivalent circuit composed by two R-C combinations, one for the bulk and other for the interface components, in series with a resistance originated in the ITO contact. From the impedance curves, the values for each circuit element is determined and it is found that both, bulk and interface resistances are decreased upon PANI/Ni-TS-Pc deposition. The results indicate that PANI/Ni-TS-Pc films reduce the contact resistance at ITO/MEH-PPV interface, and for that reason improve the hole-injection within the PLED structure.     

Photoresponsive layer-by-layer ultrathin films prepared from a hyperbranched azobenzene-containing polymeric diazonium salt

In this work, a hyperbranched diazonium salt (HB-DAS), prepared through azo-coupling reaction of an AB₂ monomer (N, N-bis[2-(4-aminobenzoyloxy)ethyl]aniline), was used to prepare self-assembled multilayers and ultrathin films. Multilayer films were fabricated by dipping substrates in HB-DAS and other polyelectrolyte solutions alternately in a layer-by-layer (LBL) manner. It was somewhat surprising to observe that HB-DAS forms multilayer films with either a polyanion (poly(styrenesulfonate sodium salt), PSS) or a polycation (poly(diallyldimethylammonium chloride), PDAC) through alternate deposition in the solutions. Ultrathin films were formed in a sequential growth manner by dipping the substrates in the HB-DAS solution, washing with deionized water and drying repeatedly. In all the processes, the absorbance and thickness of the thin films linearly increase as the number of the dipping cycle increases. HB-DAS/PSS multilayer possesses an obviously larger bilayer thickness and lower density compared with the other two counterparts. The drying step after each deposition is necessary for the HB-DAS ultrathin film growth through the repeated dip-coating of HB-DAS. The multilayer and ultrathin films prepared by the above methods all show high resistance to erosion by organic solvents. The multilayers and ultrathin films exhibit photoinduced dichroism upon the irradiation of a polarized Ar⁺ laser beam.     

MoO3 buffer layer effect on photovoltaic properties of interpenetrating heterojunction type organic solar cells

Photovoltaic cells, with a conducting polymer/fullerene (C₆₀) interpenetrating heterojunction structure fabricated by spin-coating a conducting polymer onto a C₆₀ thin film, have been investigated and demonstrated a high efficiency as solar cells based on organic materials. The photovoltaic properties of the solar cells with a structure of indium-tin-oxide (ITO)/C₆₀/poly(3-hexylthiophene) (PAT6)/Au have been improved by the insertion of a molybdenum trioxide (VI) (MoO₃) layer as a cathode buffer layer. In the solar cells with the structure of ITO/C₆₀/PAT6/MoO₃/Au, the energy conversion efficiency has been improved to 1.15% under AM1.5 (100 mW/cm²) illumination.     

In situ fabrication of Bi2S3 nanocrystal film for photovoltaic devices

A facile wet-chemical method to prepare Bi₂S₃ thin films with flake nanostructures directly on ITO glass substrate is presented in this paper for the first time. The product was characterized by X-ray powder diffractometer (XRD), Raman spectrometer, scanning electron microscope (SEM), and atomic force microscope (AFM). The one-step solvothermal elements treatment on the ITO substrate spare time to form film by spin-coating process and the film could be tightly attached to the ITO electrode. A conjugated polymer, poly 3-hexylthiophene (P3HT), was then spin-coated on the as-prepared Bi₂S₃ film to form an inorganic-organic hybrid thin film. The photovoltaic performance of the resulting solar cell device was also investigated.     

pH-sensing properties of poly(aniline) ultrathin films self-assembled on indium-tin oxide

The structural and functional properties of ultrathin (<5 nm) poly(aniline) (PANI) films deposited on indium-tin oxide (ITO) have been investigated using electrochemical and attenuated total reflection (ATR) spectroscopy methods. Layer-by-layer (LbL) self-assembly was used to form films composed of one and two bilayers of PANI and poly(acrylic acid) (PAA), as well as single PANI layers of approximately monolayer thickness. PANI deposited on an ITO electrode is electroactive at neutral pH, both with and without codeposition of an acid dopant such as PAA. In the absence of PAA, it is hypothesized that the acidic surface groups on ITO can function as the counterion. The pH response of PANI single layer, (PANI/PAA)(1), and (PANI/PAA)(2) films was examined using both potentiometry and ATR spectroscopy. Near-Nernstian potentiometric responses over pH 3-9 were observed for all three types of films, consistent with the weak acid-base behavior expected of polymers assembled in a LbL film. The ATR spectral sensitivity to pH increases as the number of layers in the film increases, with the highest sensitivity achieved by monitoring the absorbance at 800 nm (predominately due to the emeraldine salt form) of (PANI/PAA)(2) films. Codeposition of PANI and PAA appears to produce a wide distribution of strengths of acidic and basic sites in the film and thus a large linear dynamic range, up to six pH units. The water contact angle of (PANI/PAA)(2) is approximately 16 degrees, which is considerably more hydrophilic than either the PANI single layer or (PANI/PAA)(1) films ( approximately 40 degrees ). This film is shown to be a suitable substrate for deposition of a planar supported phospholipid bilayer. The supported membrane is highly impermeable to protons, which makes this architecture useful for monitoring transmembrane charge transport.     

Aqueous Metal Oxide Inks for Modifying Electrode Work Function in Polymer Solar Cells

A method to prepare aqueous metal oxide inks for tuning the work function (WF) of electrodes is demonstrated. Thin films prepared from the metal oxide ink based on vanadium oxide (V₂O₅) nanoparticles are found to increase the WF of an indium‐tin‐oxide (ITO) electrode. ITO substrates modified with V₂O₅ films are applied as a hole selective layer (HSL) in polymer solar cells (PSCs) using a poly(3‐hexylthiophene) and [6,6]‐phenyl‐C61 butyric acid methyl ester blend as a photoactive layer. The PSCs prepared with V₂O₅‐modified ITO show better device performance, achieving a power conversion efficiency of 3.6%, demonstrating 15% enhancement compared to conventional ITO/poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT‐PSS) based devices. Furthermore, ITO/V₂O₅‐modified devices exhibit better ambient stability with 60% improvement in device lifetime than those using PEDOT:PSS as an HSL. This solution‐processable and highly stable WF‐modifying metal oxide film can be a potential alternative material for engineering interfaces in optoelectronic devices.     

Comparative study of In2S3-ITO bilayers deposited on glass and different plastic substrates

In this work ITO thin films have been grown onto glass, polyethylene terephthalate (PET) and Arylite polymer substrates by sputtering at room temperature.The In₂S₃ films were chemically deposited on ITO during different times, forming bilayers for subsequent photovoltaic applications. Optical properties of the films were investigated from the transmittance and the structural properties by XRD. Transmittance of the films varies with deposition time and the different substrates used, the same as the adherence and the homogeneity of the films.     

Fracture toughness of exponential layer-by-layer polyurethane/poly(acrylic acid) nanocomposite films

This paper characterizes the fracture toughness of layer-by-layer (LBL) manufactured thin films with elastic polyurethane, a tough polymer, and poly(acrylic acid) as a stiffening agent. A single-edge-notch tension (SENT) specimen is used to study mode I crack propagation as a function of applied loading. Experimental results for the full-field time histories of the strain maps in the fracturing film have been analyzed to obtain R-curve parameters for the nanocomposite. In particular, by using the strain maps, details of the traction law are measured. A validated finite strain phenomenological visco-plastic constitutive model is used to characterize the nanocomposite film while a discrete cohesive zone model (DCZM) is implemented to model the fracture behavior. The LBL manufactured nanocomposite is found to display a higher fracture toughness than the unstiffened base polymer.     

Electrodeposition of SmS optical thin films on ITO glass substrate

SmS optical thin films were deposited on the surface of ITO glass with an electrodeposition method using aqueous solution containing SmCl₃·6H₂O and Na₂S₂O₃·5H₂O. The phase composition was analyzed by X-ray diffraction (XRD) and microstructure of the film was characterized by atomic force microscope (AFM). It is showed that SmS thin film could be obtained in the solution with n(Sm)/n(S) = 1:4, pH = 4.0 and annealing in Ar atmosphere at 200 °C for 0.5 h. The as-prepared thin films on the ITO glass exhibit a dense microstructure. The band gap of the thin film has been found to be 3.6 eV.     

Rapid fabrication of bio-inspired, mineralized polysaccharide coatings

Bio-inspired, mineralized polysaccharide coatings consisting of interspaced alginate–chitosan and calcium phosphate carbonate planar composite films were rapidly fabricated via electrostatic layer-by-layer (LBL) self-assembly and organic-matrix-mediated nucleation and growth. Experimental design, a fractional factorial design (2^8-4), was used to identify the optimum LBL film process parameters for fast film growth. Calcium phosphate carbonates rapidly precipitated on the fast growing LBL films from a supersaturated solution in around 15 min. The number of bilayers of LBL films and soaking time in calcium phosphate carbonate solution were found to affect the morphology of calcium phosphate carbonates, indicating a complex, organic matrix mediated mineralization process. The coating protocol in the current study was readily transferable to a variety of template geometries and materials. The resulting planar composite coatings could be applied for the modification of orthopaedic and periodontal implant surfaces and also for controlled growth of hematopoietic or mesenchymal stem cells.     

Decreased degradation of poly(<Emphasis Type="Italic">p</Emphasis>-phenylene vinylene) films at the indium–tin oxide interface

This article discusses a strategy to reduce the degradation of a poly(p-phenylene vinylene) (PPV) film at the interface with an indium–tin oxide (ITO) electrode. It consists of using a less aggressive leaving group, the sodium dodecylbenzenesulfonate salt (DBS), in the chemical synthesis of PPV starting with the polymer precursor, and performing the thermal conversion into PPV at a lower temperature (100 °C) than in the conventional synthesis. The absorbance spectrum for an ITO/PPV + DBS film indicated that the polymer is less degraded and has the emission efficiency increased by ca. 4.5 times in comparison to ITO/PPV films obtained with the conventional procedures, i.e., with thermal conversion at 200 °C, in vacuum, during 2 h. The main reason for the enhanced performance of the route reported in this article is a decrease in the oxygen concentration at the ITO/PPV interface, as inferred with X-ray Photoelectron Spectroscopy which corroborates the optical properties.     

Colorimetric response of fluorescein-modified multilayer thin films induced by electrolysis of water

The surface of an indium–tin oxide (ITO) electrode was coated with layer-by-layer (LbL) thin films composed of fluorescein-modified poly(allylamine) (F-PAH) and poly(styrenesulfonic acid) (PSS) and their UV–visible absorption spectra were recorded under the influence of electrode potential. The LbL films were prepared by an alternate deposition of F-PAH and PSS on the surface of ITO electrode through an electrostatic force of attraction. The intensity of the absorption band around 500 nm originating from fluorescein residues in the LbL film depended on the pH of the solution in which the LbL film is immersed. The intensity of the absorption band decreased when the electrode potential higher than + 1.2 V was applied, while virtually no response was observed at lower electrode potential. The spectral change was suppressed in solutions with higher buffer capacity. The results were discussed in terms of the changes in local pH in the vicinity of the electrode surface, which in turn was induced by electrolysis of H₂O on the electrode surface.     

Evaporation-induced self-assembly of organic–inorganic ordered nanocomposite thin films that mimic nacre

The present study attempts to incorporate acrylate-based polymers into ordered lamellar organic–inorganic nanocomposite thin films composed of alternating Poly(TPGDA)/ITO layers. The films were prepared by dip-coating from a homogeneous solution containing the soluble inorganic metal salts (InCl₃·4H2O and SnCl₂·2H₂O), surfactant, cross-linkers, organic monomers, and initiators, thus leading to composite lamellar nanocomposite materials through evaporation-induced self-assembly method. The final polymer/ITO nanocomposite thin film was obtained by a separate free-radical polymerization step, initiated by UV exposure. Structures and composition of the films were characterized using FTIR, XRD, UV–Vis spectrophotometer and TEM. The results indicated that the films were composed of organic and inorganic layers with orderly interlaced arrangement.     

Layer-by-layer assembly of titanate nanosheets/poly- (ethylenimine) on PEN films

Alternating layers of TiO₂ nanosheets and poly(ethylenimine) were sequentially dip coated onto a polyethylene naphthalate substrate (PEN) using layer-by-layer assembly. UV-vis spectroscopy shows a linear growth of the PEI/nanosheets bilayer on the PEN substrate. The cross-section microstructure of the LBL film was studied using scanning electron microscopy (SEM). Helium permeability measurement showed that the titania nanosheet/PEI bilayers reduced the permeation rate of He through the coated PEN film.     

Exponential growth of LBL films with incorporated inorganic sheets

The fastest growth pattern of layer-by-layer (LBL) assembled films is exponential LBL (e-LBL), which has both fundamental and practical importance. It is associated with "in-and-out" diffusion of flexible polymers and thus was considered to be impossible for films containing clay sheets with strong barrier function, preventing diffusion. Here, we demonstrate that e-LBL for inorganic sheets is possible in a complex tricomponent film of poly(ethyleneimine) (PEI), poly(acrylic acid) (PAA), and Na(+)-montmorillonite (MTM). This system displayed clear e-LBL patterns in terms of both initial accumulation of materials and unusually thick individual bilayers later in the deposition process with film thicknesses reaching 200 microm for films composed of 200 pairs of layers. Successful incorporation of MTM layers was observed by scanning electron microscopy and thermo-gravimetric analysis. Surprisingly, the growth rate was found to be nearly identical in films with and without clay layers, which suggests fast permeation/reptation of polyelectrolytes between the nanosheets during the "in-and-out" diffusion of polymer. In considering these findings, e-LBL growth property is expected for a wide array of available inorganic nanoscale components and have a potential to greatly expand the e-LBL field and LBL field altogether. The large thickness and rapid growth of the films affords fast preparation of nanostructured materials which is essential for multiple practical applications ranging from optical devices to ultrastrong composites.     

Electronic and junction properties of poly(2,5-dimethoxyaniline)-polyethylene oxide blend/metal Schottky diodes

Schottky barrier diode devices were fabricated in a sandwich configuration with a blend film consisting of a conducting polymer, poly(2,5-dimethoxyaniline), PDMA in an insulating matrix, polyethylene oxide (PEO). The influence of two different dopants, sulphate anion (SA) or methane sulfonate anion (MSA), in the electronic properties of the device was followed using the devices: ITO/PDMA (SA)-PEO/Al and ITO/PDMA (MSA)-PEO/Al. Current (I)-Voltage (V) characteristics were recorded for making a comparative evaluation of the electronic and junction properties of the devices. The junction and electronic parameters were analyzed and compared in the light of differences in the electronic state, morphology and transport of carriers. The device turn on voltage was found to be higher for Al/ PEO-PDMA (MSA)/ITO (∼3.0 V) in comparison to Al/ PEO-PDMA (SA)/ITO (∼2.85 V). The electronic states of PDMA doped with SA or MSA dopant were ascertained by optical UV-Visible spectroscopy. AC-impedance measurements were made for the devices and the values of bulk resistance (R_c), depletion resistance (R_d) and depletion layer width (W) were deduced through a proposed equivalent circuit. W for the device with PEO-PDMA (MSA) is more (∼24 nm) than the device with PEO-PDMA (SA) (∼8.5 nm). The observed higher Φ_B for PDMA-PEO (MSA) is consistent with this observation.