Using Graphene Oxide to Enhance the Barrier Properties of Poly(lactic acid) Film

The ultra‐thin (polyethyleneimine/graphene oxide)_n [(PEI/GO)_n]multilayer films on poly(lactic acid) (PLA) were constructed via the layer‐by‐layer assembly. Here, the electrostatic interactions between PEI and GO were used to obtain the nanoscale composite membrane of (PEI/GO)_n on the surface of PLA film. With the number of assembling layers increased, the oxygen permeability (PO₂) of PLA film decreased substantially. As a 0.06 wt% GO solution was used with only four layers, the PO₂ decreased from 53.8 to 0.377 × 10^?4 cm³/m²/d/Pa, only 0.7% of the original PLA film. At the same time, the coated PLA film also presented a good transparency and better mechanical properties. It is a novel way to use GO on biodegradable packaging materials. Copyright © 2014 John Wiley & Sons, Ltd.     

Biopolymer-manganese oxide nanoflake nanocomposite films fabricated by electrostatic layer-by-layer assembly

Bio-nanocomposite films based on chitosan and manganese oxide nanoflake have been fabricated via the layer-by-layer (LBL) self-assembly technique. UV–vis absorption spectra showed that the subsequent growth of the nanocomposite film was regular and highly reproducible from layer to layer. X-ray photoelectron spectroscopy (XPS) spectra confirmed the incorporation of chitosan and manganese oxide nanoflake into the films. Scanning electron microscopy (SEM) images revealed that the nanocomposite film had a continuous surface and a layered structure. A sensitive hydrogen peroxide (H₂O₂) amperometric sensor was fabricated with the chitosan–manganese oxide nanoflake nanocompoite film. The sensor showed a rapid and linear response to H₂O₂ over the range from 2.5 × 10^? 6 to 1.05 × 10^? 3 M, with a sensitivity of 0.038 A M^? 1 cm^? 2.     

AuCl4 ions-assisted fabrication of bimetallic {Poly(ethylenimine)-Ag/Au} multilayer polyelectrolyte film and application in electrocatalysis

Bimetallic {Poly(ethylenimine) (PEI)-Ag/Au} multilayer film was in situ simultaneously fabricated by alternating immersions of a substrate in PEI-Ag⁺ and AuCl₄⁻ solutions followed by chemical reduction with NaBH₄ solution. In the process, the AuCl₄⁻ ions not only play an important role of a reaction reagent, but also served as an assembly reagent. Au, Ag nanoparticles (NPs) were observed with a spherical morphology and well-dispersed in the composite multilayer film, and the size of Au NPs in the bimetallic {PEI-Ag/Au} multilayer film was smaller than that of the single Au NPs formed in {PEI/Au} multilayer films. It was also very interesting to observe that this bimetallic {PEI-Ag/Au} multilayer film exhibited more efficient electrocatalytic activity for the oxidation of ascorbic acid than the multilayer film containing only single Au or Ag NPs. These results indicated that this bimetallic composite multilayer film may be potentially applied in electrochemical biosensors.     

Self-assembled PMo12 3-DODA+ composite superlattice thin films with photochromic properties

A layered superlattice PMo₁₂ ^3-DODA⁺ self-assembled composite film has been successfully prepared. Infrared (IR) spectra revealed that the Keggin structure characteristic of the PMo₁₂O₄₀ ^3- anion was preserved in the composite film. A well-ordered superlattice structure, d spacing of 2.945 nm, was identified by X-ray diffraction (XRD). The superlattice film showed good photochromic properties. On irradiation with UV light, the transparent film changed from light yellow to blue. Then, bleaching occurred when the film was in contact with ambient air or O₂ in the dark. The photochromic mechanism was studied by electron spin resonance (ESR), IR spectra, and UV-Vis spectra.     

Self-assembly of ultrathin composite TiO2/polymer films

A wet layer-by-layer self-assembly of composite TiO₂/polymer films on Si and Al₂O₃/Al, substrates has been studied by AFM, STM, and ellipsometry techniques. The quality of the first adsorbed TiO₂ layer has been found to be the governing factor in multilayer film growth. The first layer consists of single particles and particle agglomerates 30–120 nm wide The surface coverage in the layer is determined by the chemical composition of the substrate surface and water pH in post-adsorption rinsing procedure. Well-packed TiO₂/polymer film completely covering the surface has been prepared in five adsorption cycle on Al₂O₃/Al substrate. The film remained crack-free after heat treatment at 300°C. I–V curves measurement reveals high resistivity (R∼10¹⁰ O in the voltage range from −2 to +3 V) of TiO₂/polymer films prepared in ten adsorption cycles.     

Fabrication of a 12-tungstophosphate and cadmium oxide composite film and its properties

A multilayer composite film of the 12-tungstophosphate H₃[PW₁₂O₄₀]³⁻ (PW₁₂) and cadmium oxide nanoparticles (CdO) was fabricated on quartz and silicon by the layer-by-layer (LBL) self-assembly method. The film was characterized by UV–vis spectroscopy, atomic force microscopy (AFM) and luminescence spectra. The proposed composite film exhibits higher photocatalytic activity toward methyl orange (MO) solution at pH 3.5, compared to single PW₁₂ and CdO films. The degradation rate was affected by initial concentration of PW₁₂, pH value of MO solution, inorganic ions concentration and type in MO solution. In addition, the composite film displays luminescent property and reversible electrochromic property with fast response time.     

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.     

Morphological characterization and analytical application of poly(3,4-ethylenedioxythiophene)-Prussian blue composite films electrodeposited in situ on platinum electrode chips

Electrochemical in situ preparation and morphological characterization of inorganic redox material-organic conducting polymer coatings as thin films on platinum electrodes are presented. Composite inorganic-organic coatings consist of Prussian blue (PB) and [poly(3,4-ethylenedioxythiophene)] (PEDOT), and PEDOT organic polymers doped with ferricyanide (PEDOT-FeCN). The PEDOT coating deposited from an aqueous solution containing the 3,4-ethylenedioxythiophene monomer and LiClO₄ as supporting electrolyte was used as a “reference” material (PEDOT-ClO₄). The composite coatings were prepared by electrochemical methods on platinum electrode chips, which consist of a 150 nm Pt layer deposited on 100-oriented standard 3″ silicon wafers. Electrochemical behavior of the composite inorganic-organic coatings is based mainly on inorganic component redox reactions. Different surface properties of the composite materials were studied. Thus, the roughness of the deposited films was measured by both atomic force microscopy (AFM) and profilometry, leading to roughness values ranging from 3 nm to 217 nm for PEDOT-ClO₄, and PEDOT-FeCN and PEDOT-PB coatings, respectively. AFM and Scanning Electron Microscopy pictures were also produced to characterize the film morphologies, and revealed a granular pattern of the deposited inorganic component inside the organic polymer matrix. Moreover, the adhesion properties of the composites were studied by AFM and proved to be very different from one material to the other depending on the film structure. The electrochemical responses of these composite coatings to H₂O₂ reduction were also investigated using chronoamperometry. A linear response over a concentration range from 1 × 10^− 4 to 1 × 10^− 5 M and a detection limit of 10 μM were obtained.     

Two-step electrochemical synthesis of Au nanoparticles decorated polyaniline nanofiber

The present work reports the electrochemical synthesis of H₂SO₄-doped polyaniline nanofibers (PANINFs) on conducting ITO substrate. The subsequent dissociation of HAuCl₄ in an acidic solution of HNO₃ and deposition of Au particles was carried out by using cyclic voltammetery (CV) to form Au particles decorated PANINFs (Au–PANINFs) composite film. Electrical conductivity of the Au particles decorated PANINFs has been measured by a two-probe method. Scanning electron microscopy (SEM) investigations of PANINFs and Au–PANINFs samples revealed good porous and fibrous structure with identical distribution of gold nanoparticles coupled with the surface of PANINFs. The average diameter of the PANINFs ranges from 184 nm to 210 nm. X-ray diffraction (XRD) and EDAX spectra also supported the formation of Au particles on the surface of PANINFs. The structural analysis was carried out by Raman spectroscopic technique. A possible mechanism for the formation of Au–PANINFs composite has been proposed.     

Composite Nanostructure Construction on the Grain Surface of Li-Rich Layered Oxides

Li-rich layered oxides (LLOs) are fascinating high-energy cathodes for lithium-ion batteries (LIBs), but still suffer from critical drawbacks that retard their practical applications. Although surface modification is effective to protect LLOs from structural deterioration, the delicate design of structures on a grain surface with promising scalability for industrial application is still challenging. Herein, using the atomic layer deposition (ALD) technique, a composite nanostructure comprising a uniform LiTaO₃ coating layer (≈3 nm) and a spinel interlayer structure (≈1 nm) is constructed on the grain surface of industrial LLO (Li_1.13Mn_0.517Ni_0.256Co_0.097O₂) agglomerated spheres. The surface composite nanostructure can not only enhance the structural/interfacial stability of the LLO, but also facilitates Li⁺ diffusion, thereby significantly improving its cycle stability, rate performance, thermal stability, and voltage maintenance. Specifically, the LLO coated with 10 ALD cycles exhibits a small voltage decay rate of 0.9 mV per cycle, a reversible capacity of 272.8 mAh g⁻¹ at 0.1 C, and a capacity retention of 85% after 200 cycles at 1 C, suggesting the important role of surface composite nanostructure for improving the electrochemical performance. This work provides new insights into the composite nanostructure design on the grain surface of cathode materials for high-performance LIBs.     

Chemical synthesis of highly stable PVA/PANI films for supercapacitor application

Polyvinyl alcohol (PVA)/polyaniline (PANI) thin films were chemically synthesized by adopting two step process: initially a thin layer (200 nm) of PVA was spin coated by using an aqueous PVA solution onto fluorine doped tin oxide (FTO) coated glass substrate, afterwards PANI was chemically polymerized from aniline monomer and dip coated onto the precoated substrate. The thickness of PANI layer was varied from 293 nm to 2367 nm by varying deposition cycles onto the precoated PVA thin film. The resultant PVA/PANI films were characterized for their optical, morphological and electrochemical properties. The FT-IR and Raman spectra revealed characteristic features of the PANI phase. The SEM study showed porous spongy structure. Electrochemical properties were studied by electrochemical impedance measurement and cyclic voltammetry. The electrochemical performance of PVA/PANI thin films was investigated in 1 M H₂SO₄ aqueous electrolyte. The highest specific capacitance of 571 Fg⁻¹ was observed for the optimized thickness of 880 nm. The film was found to be stable for more than 20,000 cycles. The samples degraded slightly (25% decrement in specific capacitance) for the first 10,000 cycles. The degradation becomes much slower (10.8% decrement in specific capacitance) beyond 10,000 cycles. This dramatic improvement in the electrochemical stability of the PANI samples, without sacrificing specific capacitance was attributed to the optimized PVA layer.     

Formation and characterization of cobalt oxide layers on polyimide films via surface modification and ion-exchange technique

Polyimide (PI) films with thin cobalt oxide (Co₃O₄) layers on both film sides have been prepared via a surface modification and ion-exchange technique. The method works by hydrolyzing the PI film surfaces in aqueous potassium hydroxide solution and incorporating Co²⁺ into the hydrolyzed layers of PI film via subsequent ion exchange, and followed by thermal treatment in ambient atmosphere. The PI composite films were characterized by Attenuated total reflection-Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, X-ray diffractions, scanning electron microscopy, transmission electron microscopy and thermogravimetric analyses, as well as surface resistance and mechanical measurements. By varying the absorbed cobalt ion content, a series of PI/Co₃O₄ composite films with insulative to semiconductive surfaces were obtained. The room temperature surface resistances of the semiconductive composite films reached to about 10⁷ Ω. The Co₃O₄ particle formed on PI film surfaces was in the range of 10-40 nm. The final composite films maintained the essential mechanical properties and thermal stability of the pristine PI films. The adhesion between surface Co₃O₄ layers and PI matrix was acceptable.     

Preparation and characterization of polyoxometalate-Ag nanoparticles composite multilayer films

The multifunctional thin films (BW₁₂/Ag NPs)_n (BW₁₂ = BW₁₂O₄₀, NPs = nanoparticles) were prepared by layer-by-layer self-assembly method. The (BW₁₂/PEI-Ag⁺)_n (PEI = polyethylenimine) composite films were achieved through alternately depositing anionic BW₁₂ and cationic PEI-Ag⁺ complex. The deposition process of (BW₁₂/PEI-Ag⁺)₁₀ multilayer is linear layer-by-layer self-assembly. Under UV irradiation, Ag ions in (BW₁₂/PEI-Ag⁺)_n multilayer films were reduced photochemically into Ag NPs and (BW₁₂/Ag NPs)₁₀ films were obtained. Through UV-vis measurements, the presence of surface plasma absorption peak at 445 nm demonstrated the formation of silver NPs. The electrochemical and antibacterial activities of (BW₁₂/Ag NPs)_n films were investigated. The electrochemical results indicate that the glassy carbon electrode modified with (BW₁₂/Ag NP)_n film exhibits the electroreduction toward O₂. Moreover, the (BW₁₂/Ag NP)₁₀ multilayer films exhibit long-lasting antibacterial properties toward Escherichia coli (E. coli).     

Electrochemical fabrication of polythiophene film coated metallic nanowire arrays

Metallic gold (Au) and silver (Ag) nanowire arrays coated with polythiophene (PTh) films were fabricated by successive electrochemical depositions of PTh and metal into the pores of a microporous alumina membrane. The diameter of the composite nanowires was 200 nm and that of the metallic nanowires was about 100 nm. They are adhered to a thin gold film and aligned in a high density of ca. 10¹⁰ wires/cm². The morphology of the composite nanowires has been characterized by an optical microscope, Raman spectroscopy, scanning and transmission electron microscopies. Their electrochemical property has also been investigated.     

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.     

Nonlinear optical properties of gold nanoparticles synthesized by ion implantation in sapphire matrix

Single crystal Al₂O₃ substrates have been implanted with 160-keV Au⁺ to a dose of 0.6 × 10¹⁷ or 1.0 × 10¹⁷ cm⁻², with a postimplantation annealing for 1 h at 800°C in air. The obtained composite layers were studied by the method of linear optical reflection; the nonlinear optical characteristics were determined by the RZ-scan technique using picosecond radiation pulses of an Nd:YAG laser operating at 1064 nm. The appearance of a characteristic surface optical plasmon resonance band in the linear reflection spectra was indicative of the formation of gold nanoparticles in a subsurface layer of ion-irradiated Al₂O₃. It is shown that the synthesized particles are responsible for the observed manifestations of nonlinear refraction. The composite layers were characterized by the nonlinear refractive index (n ₂) and the real part of the third-order nonlinear susceptibility (Reϰ ⁽³⁾).     

Preparation and characterization of novel CuClSe2 semiconductor thin film

CuClSe₂ was synthesized by solid-state reaction between copper chloride and selenium at 300 °C. CuClSe₂ thin film was prepared on a glass substrate by pulsed laser deposition (PLD) method. XRD (X-ray diffraction) analysis revealed that the CuClSe₂ thin film has a preferred surface orientation parallel to (006). The transmittance and reflectance spectra of the film indicated that the compound is an indirect band gap material; the energy band gap is about 1.45 eV; its absorption coefficients are in the range of 10⁴-10⁵ cm^− 1 when the wavelength is shorter than 720 nm. The melting point of CuClSe₂ is about 328 °C. These results show that CuClSe₂ is a potential absorber layer material applied in solar cells.     

Local thermal-mechanical analysis of ultrathin interfacially mixed poly(ethylene oxide)/poly(acrylic acid) layer-by-layer electrolyte assemblies

Ion conductivities of layer-by-layer (LBL) assemblies of solid thin film polyelectrolyte systems involving poly(ethylene oxide) (PEO) and poly(acrylic acid) (PAA) were found to be a strong function of the number of bilayer stacks, n, with conductivities approaching 10^− 7 S/cm for n < 10, compared to 10^− 9 S/cm for n ≥ 10 and 10^− 10 S/cm for bulk PEO. Increased ion conductivity for low LBL stack numbers (n < 10) originated to part from an effective suppression of the PEO crystallization via PEO/PAA blending, which could be inferred from local glass transition temperature measurements involving shear modulation force microscopy. Another phenomenon responsible for high conductivity in thin films was found in the in-plane phase heterogeneity of PEO and PAA. Increased ion conductivity for larger LBL stacks (n ≥ 10) were attributed to low concentration autoblending caused by PEO-PAA hydrogen bonding, and an average layer thickness of noticeably less than 100 nm. The effect of interfacial constraints was evident in the degree of intermixing, addressed by a thin film extended Fox blend analysis, in the glass and melting transitions of PEO and PAA pure film components. While the glass transition value of PAA decreased by 55% to 46 °C for an 8 nm film, the melting transition for PEO decreased by 15% to 64 °C caused by surface tension effects.     

Properties of pulse plated SnSe films

In this work, the pulse electrodeposition technique has been employed for the first time to deposit SnSe films from a bath containing Analar grade 50?mM tin chloride (SnCl₄) and 5?mM SeO₂. The XRD profile of SnSe thin films deposited at different duty cycles indicate the peaks corresponding to SnSe. Atomic force microscopy studies indicated that the surface roughness increased from 0.5 to 1.5?nm with duty cycle. The transmission spectra exhibited interference fringes. The value of refractive index at 780?nm was 2.1, this value decreased to 1.95 with decrease of duty cycle. The room temperature resistivity increased from 0.1 to 10?Ωcm with decrease of duty cycle. Photo electrochemical cell studies were made using the films deposited at different duty cycles. For duty cycles greater than 15% photo output was observed. For a film deposited at 50% duty cycle, an open circuit voltage of 0.55?V and a short circuit current density of 5.0?mA?cm^?2 at 60 mW?cm^?2 illumination. Capacitance voltage measurements indicated V_fb?=?0.67?V (SCE) and p type, carrier density?=?6.98?×?10¹⁶?cm^?3.     

Epitaxial growth and properties of cubic Zn0.7Mg0.3O films on TiN-buffered Si(100) substrates by in situ pulsed laser deposition

A novel cubic Zn_0.7Mg_0.3O film on silicon substrate is conducted by KrF excimer pulsed-laser ablation system. By introducing a thin TiN buffer, layer-by-layer growth of cubic Zn_0.7Mg_0.3O film epilayer has been realized. The overall growth process was monitored in situ by reflection high-energy electron diffraction (RHEED) method. It was found that the crystallinity and surface morphology of the Zn_0.7Mg_0.3O films were strongly affected by the TiN buffer layer. The Zn_0.7Mg_0.3O film obtained at an optimal buffer layer exhibited high quality and good surface. For the metal-insulator-metal (MIM) structure of Pt/Zn_0.7Mg_0.3O (200 nm)/TiN (20 nm)/Si (400 μm) prepared at the optimal growth conditions achieved a very low leak current density of ∼10⁻⁶ A cm⁻² at an electric field of 9 × 10⁵ V cm⁻¹ and the permittivity (?_r) of about 8.1, agreed well with that of acquired MgO film and MgO single crystal.