Electrical properties of a calix[4]acid/amine Langmuir–Blodgett thin film

In this work the DC and AC characteristics for metal-LB film-metal structures deposited by a standard Langmuir–Blodgett film deposition technique are investigated. The conduction mechanism has been studied for a thin film structure in which a calix[4]arene substituted with carboxylic acid groups has been deposited alternately with a calix[4]arene molecule substituted with amine groups. This LB film structure shows a typical insulating behaviour for low voltage values and the Schottky effect becomes dominant when the voltage increases. The conductivity at low voltage values was found to be 1.34 × 10⁻¹³ S cm⁻¹. The height of the potential barrier was determined to be 1.65 eV for this alternate layer LB film system.     

Electrical characterisation of stearic acid/calix[4]amine Langmuir–Blodgett thin film

Within this work we deposited 16 monolayers of stearic acid alternated with 15 monolayers of calix[4]amine to form a non-centrosymmetric Langmuir–Blodgett (LB) thin film onto an aluminized (50 nm coated) glass microscopic slide. Dielectric constant and dielectric loss for the film were determined using C-f and tan (δ-f) measurements. The value of the pyroelectric figure of merit was determined as 1.73 μC m⁻² K⁻¹. To elucidate the conduction mechanism of stearic acid/calix[4]amine LB film, DC current–voltage measurements between −4 and +4 V were carried out. The I(V) behaviour shows a symmetrical and highly non-linear behaviour. Analysis of this behaviour of the stearic acid/calix[4]amine LB film showed a conductivity value of 1.12 × 10⁻¹³ S m⁻¹ for ohmic region. The exponential part of I(V) dependence obeyed the Schottky conduction mechanism with a barrier height of 1.67 eV. This LB film structure shows a typical insulating behaviour for low voltage values and the Schottky effect becomes dominant when the voltage increases. The frequency dependence of conductivity shows a power law relationship between conductance and frequency.     

Optimal deposition condition of chlorophyll a Langmuir–Blodgett film

The optimal deposition condition of chlorophyll a (Chl a) Langmuir–Blodgett (LB) film were investigated based on π–a isotherms, absorption spectrum and scanning tunneling microscopy (STM) observation. The π–a isotherms of Chl a LB film at various air temperatures and subphase pHs were obtained. Optimum temperature and pH for dense packing of Chl a LB layers are 25 °C and 7.0, respectively. The formation of J- and H-aggregations of the ordered chlorophyll a molecules was confirmed by absorption spectrum measurements. The well-ordered structure of Chl a LB layer was observed by STM. Thus, the densely packed Chl a LB layer could be fabricated by the proposed optimal deposition condition.     

Electrical conductivity properties of boron containing Langmuir–Blodgett thin films

Electrical characterisations of Mesitylene-2-boronic acid (MBA), Phenylboronic acid (PBA) and 1-Naphthylboronic acid (NBA) are investigated using C-f and I–V measurements. All materials are used to fabricate Langmuir–Blodgett (LB) thin film by vertical dipping method. Metal/LB film/Metal sandwich structure is prepared to investigate electrical properties of boron containing LB films. For evaluation of electrical measurements, the theoretical thickness is determined using ChemDraw software and experimental thickness value is calculated from surface plasmon resonance (SPR) curves. Dielectric measurements are used to determine the dielectric constant (ε) and to compare refractive index value which is determined from SPR results. The values of ε are determined as 2.79, 2.70, 2.82 for MBA, PBA and NBA respectively. The refractive indexes of three materials are calculated to be around 1.6. I–V results are used to study the conduction mechanism of these LB films. The low voltage region shows an ohmic characteristic for each LB film and conductivity values are calculated as 0.55 × 10^?11 S m^?1, 0.42 × 10^?11 S m^?1 and 3.62 × 10^?11 S m^?1 for MBA, PBA and NBA respectively. In the high voltage region of I–V curves that show Schottky type conduction mechanisms with the barrier heights estimated for each LB film as 0.77, 0.79 and 0.76 eV respectively.     

Role of metal ions of Langmuir–Blodgett film in hydrophobic to hydrophilic transition of HF-treated Si surface

Hydrophobic to hydrophilic transition of HF-treated Si surface strongly depends upon the metal ions, which are present in the headgroups of the deposited Langmuir–Blodgett (LB) film. Structure of LB films studied by X-ray reflectivity technique and chemical analysis of LB film–substrate interfaces studied by X-ray photoelectron spectroscopy combinedly suggest that the partial transition or partial oxidation of the HF-treated Si surface takes place under the subphase water but further transition or oxidation is possible only in the presence of metal ions. Electrovalent and covalent natures of the metal ions tune this transition or oxidation. Ni ions, for which bonding with headgroups are electrovalent in nature, are favorable for such transition/oxidation and as a result, complete transition/oxidation takes place when nickel arachidate LB film is deposited. On the other hand, Cd ions, for which bonding with headgroups show covalent nature, is not favorable for such transition and can not oxidize the underlying H-passivated Si substrate totally when cadmium arachidate LB film is deposited on such HF-treated Si surface. This ion-specific hydrophobic to hydrophilic transition is visualized by X-ray reflectivity, contact angle and X-ray photoelectron spectroscopy measurements.     

Preparation and conductivity of dithiolene complex Langmuir–Blodgett films

The d.c. electrical property of the dithiolene complex, or bis(4-diethyannodithiobenzil)nickel (BDN) and stearyl alcohol (SA) mixed Langmuir–Blodgett films was investigated. The conductivity of the LB films as a function of the thickness of the films and the ratio of BDN:SA as well as the current versus voltage (I–V) characteristics have been measured. The conductivity of the LB films is about 3.5 x 10^-10 S cm^-1 which is less than the bulk conductivity of BDN, and the conductivity of the LB films is strongly influenced by BDN concentration. The I–V property of Al-LB films is governed by the thickness of oxide layers at the LB films with Al electrodes after Auger depth profiling analysis.     

Block copolymer assisted self-assembly of nanoparticles into Langmuir–Blodgett films: Effect of polymer concentration

We propose to use the self-assembly ability of a block copolymer to obtain CdSe quantum dots (QDs) structures of different morphology. The methodology proposed consist in transferring mixed Langmuir monolayers of QDs and the polymer poly (styrene-co-maleic anhydride) partial 2 buthoxy ethyl ester cumene terminated, PS-MA-BEE onto mica by the Langmuir–Blodgett (LB) methodology. The morphology of the LB films was analyzed by AFM and TEM measurements. Our results show that it is possible to modulate the self-assembly process by modifying the composition of the mixed Langmuir monolayer precursor of the LB film. The different morphologies are interpreted according to two different dewetting mechanisms, growth of holes and spinodal-like dewetting. The growth of holes dewetting process is driven by gravitatory effects and was observed for LB films obtained by transferring Langmuir monolayer of the smallest elasticity values in which the polymer is in brush conformation. The spinodal dewetting mechanism prevailed when the Langmuir monolayer presents the highest elasticity values.     

A heterostructured SnO2–TiO2 thin film prepared by Langmuir–Blodgett technique

SnO₂–TiO₂ heterostructure films were prepared through Langmuir–Blodgett (LB) route. LB films of octadecyl amine (ODA)–titanyl oxalate multilayer deposited on Si (100) and decomposed at 600 °C showed rutile and anatase phases of ultrathin TiO₂ film. Subsequently, multilayer LB film of ODA–stannate deposited on the pre deposited TiO₂ film after decomposition at 600 °C resulted in thin SnO₂ films on the TiO₂ thin film. The phase analysis of the SnO₂–TiO₂ film showed cassiterite phase of SnO₂ as well as the rutile/anatase mixture of TiO₂ indicating a SnO₂–TiO₂ heterostructured film. Surface morphology of the pure TiO₂ film and SnO₂–TiO₂ film were analyzed by using AFM. Electrical characterization by AC impedance analysis suggested SnO₂–TiO₂ heterostructure formation. DC current voltage measurement showed increase in photocurrent indicating visible light absorption and efficient charge separation under the sunlight type radiation.     

Circular patterns of calcium oxalate monohydrate induced by defective Langmuir–Blodgett film on quartz substrates

The defective Langmuir–Blodgett (LB) film of dipalmitoylphosphatidylcholine (DPPC) on quartz injured by potassium oxalate (K₂C₂O₄) was used as a model system to induce growth of calcium oxalate crystals. Atomic force microscopy (AFM) indicated that circular defective domains with a diameter of 1–200 μm existed in the LB film. Scanning electron microscopy (SEM) showed circular patterns of aggregated calcium oxalate monohydrate (COM) crystallites were induced by these defective domains. It was ascribed to that the interaction between the negatively-charged oxalate ions and the phosphatidyl groups in DPPC headgroups makes the phospholipid molecules rearranged and exist in an out-of-order state in the LB film, especially at the boundaries of liquid-condensed (LC)/liquid-expanded (LE) phases, which provide much more nucleating sites for COM crystals.     

ZnO@CdS core–shell thin film: fabrication and enhancement of exciton life time by CdS nanoparticle

In the present study photoluminescence behavior of ZnO and ZnO@CdS core–shell nanorods film has been reported. ZnO nanorods were grown on the glass coated indium tin oxide (ITO) surface by seeding ZnO particle followed with nanorods growth. These nanorods were coated with CdS by chemical bath deposition techniques to have ZnO@CdS thin film and further annealed at 200 °C for their adherence to the ITO surface. The coating was characterized for surface morphology using SEM and optical behavior using UV–visible spectrophotometer. Energy dispersive X-ray (EDX) was used for compositional analysis and time resolve photoluminescence decay for excitons life time measurement. The absorption spectrum reveals that the absorption edge of ZnO@CdS core–shell heterostructure shifted to 480 nm in the visible region whereas ZnO nanorods have absorption maxima at 360 nm. The excitons lifetime of ZnO@CdS was found to be increased with the thickness of the CdS layer on ZnO nanorod. These ZnO@CdS core–shell nanostructures will be of great use in the field of photovoltaic cell and photocatalysis in a UV–visible region.     

Preparation and characterization of CdS–Bi2S3 nanocomposite thin film by successive ionic layer adsorption and reaction (SILAR) method

CdS, Bi₂S₃ and CdS–Bi₂S₃ nanocomposite thin films were grown by successive ionic layer adsorption and reaction method (SILAR) onto the glass substrates at room temperature. These films were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and electrical measurement systems. A comparative study was made between CdS, Bi₂S₃ and CdS–Bi₂S₃ nanocomposite thin films. The XRD patterns reveal that CdS, Bi₂S₃ and CdS–Bi₂S₃ nanocomposite thin film have hexagonal, orthorhombic and mixed phase of hexagonal CdS and orthorhombic Bi₂S₃ crystal structure, respectively. SEM images showed uniform deposition of the material over the entire glass substrate. The energy band gap for CdS, Bi₂S₃ and CdS–Bi₂S₃ thin films were revealed from the optical studies and were found to be 2.4, 1.6 and 1.69 eV, respectively. The thermoemf measurements of CdS–Bi₂S₃ nanocomposite thin film revealed n-type electrical conductivity, while the I–V measurement of CdS, Bi₂S₃ and CdS–Bi₂S₃ nanocomposite thin film under dark and illumination condition (100 mW/cm²) exhibited photoconductivity phenomena suggesting its applicability in photosensors devices.     

Growth and optical properties of Sn–Si nanocomposite thin films

The growth and optical properties of nanocomposite thin films comprising of nanocrystalline Sn and Si are reported. The nanocomposite films are produced by thermal annealing of bilayers of Sn and Si deposited on borosilicate glass substrates at various temperatures from 300 to 500 °C for 1 h in air. X-ray diffraction reveals that the as-deposited bilayers consist of nanocrystalline Sn films with a crystallite size of 30 nm, while the Si thin films are amorphous. There is onset of crystallinity in Si on annealing to 300 °C with the appearance of the (111) peak of the diamond cubic structure. The crystallite size of Si increases from 5 to 18 nm, whereas the Sn crystallite size decreases with increase in annealing temperature. Significantly, there is no evidence for any Sn–Si compound, and therefore it is concluded that the films are nanocomposites of Sn and Si. Measured spectral transmittance curves show that the films have high optical absorption in the as-deposited form which decreases on annealing to 300 °C. The films show almost 80 % transmission in the visible-near infrared region when the annealing temperature is increased to 500 °C. There is concomitant decrease in refractive index from 4.0, at 1750 nm, for the as-deposited film, to 1.88 for the film annealed at 500 °C. The optical band gap of the films increases on annealing (from 1.8 to ~2.9 eV at 500 °C). The Sn-Si nanocomposites have high refractive index, large band gap, and low optical absorption, and can therefore be used in many optical applications.     

Poly(acrylonitrile-co-itaconic acid)–poly(3,4-ethylenedioxythiophene) and poly(3-methoxythiophene) nanoparticles and nanofibres

This work aimed to produce poly(acrylonitrile-co-itaconic acid) (P(AN-co-IA)) nanocomposites with poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(3-methoxythiophene) (PMOT). An anionic surfactant sodium dodecyl benzene sulphonate was used in emulsion polymerization for nanocomposite production. Incorporations of PEDOT and PMOT on the nanoparticles were characterized by scanning electron microscopy (SEM), atomic force microscopy, Fourier transform infrared-attenuated total reflectance spectroscopy and ultra-violet spectroscopy. These nanoparticles were blended with PAN and the blends were electrospun to produce P(AN-co-IA)–polythiophene-derivative-based nanofibres, and the obtained nanofibres were characterized by SEM and energy dispersive spectroscopy. In addition, electrochemical impedance studies conducted on nanofibres showed that PEDOT and PMOT in matrix polymer P(AN-co-IA) exhibited capacitive behaviour comparable to that of ITO–PET. Their capacitive behaviour changed with the amount of electroactive polymer.     

Bimetallic Pt–Au thin film electrocatalysts with hierarchical structures for the oxidation of formic acid

A series of bimetallic Pt–Au thin films with different Pt/Au ratios were fabricated on glassy carbon (GC) substrates through galvanic replacement reactions between hierarchical Co thin films prepared by cyclic voltammetric deposition and mixed solutions of HAuCl₄ and H₂PtCl₆. The morphologies of the as-prepared Pt–Au thin films resemble those of the sacrificial Co templates, and the Pt/Au ratios in the films are dependent on the HAuCl₄/H₂PtCl₆ molar ratios in the mixed solutions. Because of good stability and excellent synergistic effect of Au and Pt, the bimetallic films with novel structures display unexpected high catalytic activity for the oxidation of formic acid. The as-prepared hierarchical Pt–Au micro/nanostructures are expected to find applications as catalysts in direct formic acid fuel cells (DFAFCs).     

Fabrication,characterization and sensing properties of Cu(II) ion imprinted sol–gel thin film on QCM

Cu(II)-molecularly imprinted sol–gel films (Cu(II)-MISGF), coated on a quartz crystal microbalance (QCM) chip, were fabricated using a sol–gel procedure. Co-hydrolysis and co-condensation of Cu(II) (templates), 3-aminopropyltrimethoxysilane (APTS, functional monomer) and tetraethoxysilane (TEOS, cross-linking agent) were performed with acid and base catalysis. The properties of the Cu(II)-MISGF were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and the electrochemical methods of cyclic voltammetry (CV). Microstructural observations revealed that the acid-catalyzed system yielded more mechanically stable thin films. A combined Cu(II)-MISGF-QCM with flow injection analysis (FIA) method was utilized to investigate the sensing performance of the Cu(II)-MISGF, with special emphasis on the most important properties of sensitivity, selectivity and response time. The Cu(II)-MISGF-QCM sensor, at a TEOS/APTS molar ratio of 10, exhibited excellent selectivity and rapidly responded to Cu(II) ions.     

Preparation and characterization of poly(3,4-ethylenedioxythiophene)–poly(styrene sulfonate) composite thin films highly loaded with platinum nanoparticles

In this work, we propose a simple and efficient, low-temperature (∼120 °C) process to prepare transparent thin films of poly(3,4-ethylenedioxythiophene)–poly(styrenesulfonate) (PEDOT:PSS) loaded with high concentration (up to 22.5 wt%) of platinum (Pt) nanoparticles. Firstly, an improved polyol method was modified to synthesize nano-sized (∼5 nm) and mono-dispersed Pt particles. These nanoparticles were incorporated into the matrix of PEDOT:PSS thin films via a spin coating/drying procedure. The electrochemical activities of the PEDOT:PSS thin film modified electrodes with respect to the I⁻/I₃⁻ redox reactions were investigated. It was found that the modified electrode of PEDOT:PSS thin film containing 22.5 wt% Pt exhibited the electrochemical activity comparable to the conventional Pt thin film electrode, suggesting that this electrode has good potential to serve as a counter electrode in dye-sensitized solar cells.     

One-step synthesis of poly(2-hexadecyloxyaniline)/selenium nanocomposite Langmuir–Blogett film by in situ redox reaction

Poly(2-hexadecyloxyaniline)/selenium (Se) nanocomposite monolayer was successfully prepared by spreading 2-hexadecyloxyaniline (2-C₁₆OAn) on selenious acid aqueous solution without additional oxidant and reductant. The formation of Se nanoparticles and the polymerization of 2-C₁₆OAn in the monolayer occurred simultaneously. The results showed that the limiting area per repeat unit on selenious acid subphase was larger than that on pure water, which indicated the formation of poly(2-hexadecyloxyaniline)/Se nanocomposite monolayer at air/water interface. The amorphous spherical Se nanoparticles and triangular single-crystal ones in the Langmuir–Blogett (LB) films were formed at 20 ± 1 °C and 35 ± 1 °C, respectively. Poly(2-hexadecyloxyaniline)/Se nanocomposite LB films with excellent quality could be obtained on different substrates, indicating that the transfer ratio of monolayer was close to unity. Furthermore, poly(2-hexadecyloxyaniline)/Se nanocomposite LB films possessed high conductivity with the current of 10⁻⁵ A cm⁻¹.     

Biosynthesis of gold nanoparticles using marine bacteria and Box–Behnken design optimization

Gold nanoparticles are exciting materials because of their potential applications in optics, electronics, biomedical, and pharmaceutical fields. In recent years, environmentally friendly, low-cost biosynthesis methods with bio-applicable features have continued to be developed for the synthesis of gold nanoparticles. In the present study, an actinobacterial strain was isolated from the Petrosia ficiformis (Poiret 1798) sponge, which was collected from a marine environment, and the gold nanoparticle synthesis was performed for the first time from the bacteria type belonging to the Citricoccus genus. The synthesis conditions were optimized using the Box–Behnken experimental design, with a statistical method that included three independent variables (temperature, time, and mixture ratio) to affect the synthesis at three levels (+1, 0, and ?1). Accordingly, the conditions proposed for the biosynthesis of gold nanoparticles at the maximum optical density values that are specific for the Citricoccus sp. K1D109 strain were estimated as 35°C temperature, 24?h, and 1/5 mixture ratio (cell-free extract/HAuCl₄?·?3H₂O). When recommended conditions were applied, it was determined that the maximum absorbance of the synthesized gold nanoparticles is 1.258 at 545?nm, and their sizes are in the range of 25–65?nm, according to transmission electron microscopy (TEM) data.     

Growth and characterization of ceria thin films and Ce-doped γ-Al2O3 nanowires using sol-gel techniques

γ-Al(2)O(3) is a well known catalyst support. The addition of Ce to γ-Al(2)O(3) is known to beneficially retard the phase transformation of γ-Al(2)O(3) to α-Al(2)O(3) and stabilize the γ-pore structure. In this work, Ce-doped γ-Al(2)O(3) nanowires have been prepared by a novel method employing an anodic aluminium oxide (AAO) template in a 0.01 M cerium nitrate solution, assisted by urea hydrolysis. Calcination at 500?°C for 6 h resulted in the crystallization of the Ce-doped AlOOH gel to form Ce-doped γ-Al(2)O(3) nanowires. Ce(3+) ions within the nanowires were present at a concentration of < 1 at.%. On the template surface, a nanocrystalline CeO(2) thin film was deposited with a cubic fluorite structure and a crystallite size of 6-7 nm. Characterization of the nanowires and thin films was performed using scanning electron microscopy, transmission electron microscopy, electron energy loss spectroscopy, x-ray photoelectron spectroscopy and x-ray diffraction. The nanowire formation mechanism and urea hydrolysis kinetics are discussed in terms of the pH evolution during the reaction. The Ce-doped γ-Al(2)O(3) nanowires are likely to find useful applications in catalysis and this novel method can be exploited further for doping alumina nanowires with other rare earth elements.     

Study on the characteristics and relative properties of Langmuir–Blodgett films based on substituted bis[phthalocyaninato] rare earth(III) complexes

A new kind of sandwich-like bis[2,3,9,10,16,17,23,24-octakis(octyloxy)phthalocyaninato] rare earth(III) complexes RE(Pc*)₂ (Pc*=Pc(OC₈H₁₇)₈, RE=Er, Sm, Tb) are used as film-forming materials. Pure RE(Pc*)₂ ultrathin films and RE(Pc*)₂ and octadecanol (OA)/stearic acid (SA) mixed ultrathin films were prepared by the Langmuir–Blodgett (LB) technique. The LB films were characterized by ultraviolet/visible (UV/Vis) spectroscopy and X-ray photoelectron spectroscopy (XPS). The NO₂ gas-sensing properties of Sm(Pc*)₂/OA LB film are studied compared with that of (i-PrO)₄CuPc LB film by XPS spectra and valence band spectra. It is found that the interaction between Sm(Pc*)₂ LB film and NO₂ gas is stronger than that between (i-PrO)₄CuPc LB film and NO₂ gas. Experimental results indicate that bis(phthalocyaninato) rare earth(III) complexes show more remarkable sensitivity than monophthalocyanine, which can be used in high-sensitive gas sensor applications. At the same time, the mechanism of sensitivity of Sm(Pc*)₂/OA mixed LB film to NO₂ gas is also studied in this paper.