Monolayer,bilayer, multilayers: evolving magnetic behavior in Langmuir-Blodgett films containing a two-dimensional iron-nickel cyanide square grid network

The assembly of two-dimensional cyanide-bridged Fe(III)-Ni(II) square grid networks at the air-water interface and subsequent transfer of these networks as isolated monolayer, isolated bilayer, and multiple bilayer (multilayer) films via the Langmuir-Blodgett technique results in novel low-dimensional systems in which the effects of dimensionality on magnetic behavior in molecule-based materials can be observed. The magnetic response of these films between 2 < T < 300 K in dc fields from -50 < H < 50 kG and in 4 G ac fields from 1 Hz to 1 kHz are reported. The results show the presence of ferromagnetic domains with characteristic hysteresis in each of the three systems. The magnetic response for all three samples is anisotropic with a stronger field-cooled magnetization observed when the planes of the films are aligned parallel to the applied field. Additionally, each of the three samples shows frequency dependence in both the real and imaginary components of the ac susceptibility. This behavior is interpreted as being characteristic of spin glass-type ordering of ferromagnetic domains to form a cluster glass. A lower glass temperature (T(g)) is observed in the isolated monolayer film relative to the bilayer and multilayer samples. The bilayer sample shows two glass transitions at T(g1) = 3.8 K and T(g2) = 5.4 K, whereas only one transition at T(g) = 5.4 K is observed in the multilayer sample. The different magnetic responses of the three films are attributed to different in-plane, interplane, and long-range dipolar exchange interactions.     

Electrical and magnetic properties of thin films containing metal clusters

A large variety of granular polymer thin films can be synthetized in a capacitively coupled coplanar diode radiofrequency (r.f.) discharge system in which an argon-monomer mixture is injected at low pressure (20 mTorr). This approach offers several advantages over the other techniques, e.g. easy control of the metal content in the film from a few % up to 100%. The d.c. electrical properties of gold containing plasma polymerized tetrafluoroethylene (PPTFE) and the magnetic behavior of cobalt containing plasma polymerized propane (PPP) are reported in this paper.     

Carbon nanotube thin films modified with a mixture of Prussian blue and ruthenium purple: combining materials and properties

Thin films of iron-filled carbon nanotubes prepared through the liquid/liquid interfacial method were modified with a mixture of hexacyanometallates (HCMs) Prussian blue and ruthenium purple. Two different approaches were used in order to obtain both materials in the composites, based on a direct reaction starting from a mixture of both precursors or a step-by-step deposition of each compound. The modified films were characterized by cyclic voltammetry, Raman spectroscopy, X-ray diffraction, scanning electron microscopy, and UV-Vis spectroscopy, confirming the formation of a mixture of HCMs in both methods of synthesis. Stability studies were evaluated in different supporting electrolytes, and composites presented good performances due to carbon nanotube stabilization. Electrochromic properties were also evaluated for selected composites, showing high electrochromic efficiency and stability.

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Metal-to-ligand and ligand-to-metal charge transfer in thin films of Prussian blue analogues investigated by X-ray absorption spectroscopy

A series of thin films of Prussian blue analogues is investigated by X-ray absorption spectroscopy (XAS) at the Fe, Co and Mn L(2,3)-edges. The ligand field multiplet theory enables us to examine accurately the electronic structure of these materials. Experimental XAS spectra of CoFe Prussian blue analogues are successfully reproduced using a ground state configuration including metal-to-ligand (MLCT) and ligand-to-metal charge transfer (LMCT) at the Co and Fe L(2,3)-edges. In particular, a huge improvement is achieved for satellite peaks at the Co(iii) L(2,3)-edges compared to previous calculations in the literature based on LMCT effects only. On the other hand, XAS spectra of MnFe analogues synthesized for the first time, can be reproduced conveniently by taking into account either MLCT or LMCT depending on the conditions of the sample preparation. For each thin film, the proportion of the different oxidation states of Co, Fe and Mn is evaluated. Unexpectedly, this analysis reveals the presence of a significant amount of a reduced phase, which turns out to be strongly dependent on the sample synthesis and storage conditions.     

Spectral properties of TMPyP intercalated in thin films of layered silicates

The objective of this study was to investigate the spectral characteristics of tetracationic porphyrin dye (TMPyP), intercalated into films of three smectites. The smectites represented the specimens of high (Fluorohectorite; FHT), medium (Kunipia F montmorillonite; KF), and low layer charge (Laponite; LAP). Intercalation of TMPyP molecules was proven by XRD measurements. The molecular orientations of the dye cations were studied by means of linearly polarized ultraviolet-visible (UV-vis) and infrared (IR) spectroscopies. Both the UV-vis and the IR spectroscopy proved the anisotropic character of the films. The spectral analysis of the polarized UV-vis spectra and consequent calculations of tilting angles of the transition moments in the region of Soret band transitions were in the range of 25-35 degrees . The determined angles indicated that the molecular orientation of the dye cations was almost parallel to the surface of the silicates. Slightly higher values, determined for a FHT film, indicated either a slightly more tilted orientation of the dye cations or the change of molecular conformation after the intercalation of the dye. Quenching of TMPyP fluorescence was observed, resulting from the formation of bimolecular layer arrangements with sandwich-type assemblies of the dye molecules.     

Electrical and mechanical properties of thin metal films: Size effects

A general expression for the function of electron scattering in thin films of a grain structure is derived which takes account of both the external and internal size effects. Limiting and particular values of this function are given for polycrystalline and single-crystal films. Theoretical results are compared to the experimental results obtained for aluminium and tin. The relationship between size effects and resistivity, temperature coefficient of resistance, longitudinal and transverse strain coefficient of resistance and thermoelectric power is studied. The dependence of the orientation of monocrystalline copper and aluminium films on thermal stress, the direction of the energy density of elastic strains and the anistropy of elastoresistance coefficients in these films are examined. An expression for the gauge factor in single-crystal metal films of given orientations is derived.     

Properties of Prussian blue materials manifested in molecular complexes: observation of cyanide linkage isomerism and spin-crossover behavior in pentanuclear cyanide clusters

Pentanuclear, cyanide-bridged clusters [M(tmphen)2]3[M'(CN)6]2 (M/M' = Zn/Cr (1), Zn/Fe (2), Fe/Fe (3), Fe/Co (4), and Fe/Cr (5); tmphen = 3,4,7,8-tetramethyl-1,10-phenanthroline) were prepared by combining [M'III(CN)6]3- anions with mononuclear complexes of MII ions with two capping tmphen ligands. The clusters consist of a trigonal bipyramidal (TBP) core with three MII ions in the equatorial positions and two M'III ions in the axial positions. Compounds 1-4 are isostructural and crystallize in the monoclinic space group P21/c. Complex 5 crystallizes in the enantiomorphic space group P3221. The magnetic properties of compounds 1 and 2 reflect the contributions of the individual [CrIII(CN)6]3- and [FeIII(CN)6]3- ions. The FeII ions in compounds 3 and 4 exhibit a gradual, temperature-induced spin transition between high spin (HS) and low spin (LS), as determined by the combination of M?ssbauer spectroscopy, magnetic measurements, and single-crystal X-ray studies. The investigation of compound 5 by these methods and by IR spectroscopy indicates that cyanide linkage isomerism occurs during cluster formation. The magnetic behavior of 5 is determined by weak ferromagnetic coupling between the axial CrIII centers mediated by the equatorial diamagnetic FeII ions. M?ssbauer spectra collected in the presence of a high applied field have allowed, for the first time, the direct experimental observation of uncompensated spin density at diamagnetic metal ions that bridge paramagnetic metal ions.     

Structural and magnetic properties of nano-crystalline FeCoNiN thin films

Iron cobalt nickel nitride (FeCoNiN) thin films are prepared by sol-gel spin coating route. The structural, magnetic and surface properties of the thin films are evaluated. The crystalline nature of thin films was enhanced upon annealing, leading to increased crystallite size. The X-ray diffraction shows mixed phases with crystallite size in the range of 20–26.93 nm. Thin films show ferromagnetism at room temperature. Coercivity and saturation magnetization are in the range of 642–716 Oe and 2.5–7.5 emu/cm³ respectively. Both coercivity and saturation magnetization increased with annealing of thin films. Magnetic properties are related to the crystallinity of thin films. The increase in crystallite size results into an increase of magnetic properties. Rectangular shaped particles are seen on the surface of thin films. The same type of grains can be seen on the surface of thin films which confirmed the formation of FeCoNiN as predicted by XRD. These novel thin films might be used in memory devices and optoelectronic applications.     

Cyclic voltammetric studies of Prussian blue and viologens within a paper matrix for electrochromic printing applications

The apparent redox response of Prussian blue (PB, iron(III) hexacyanoferrate(II)) within a paper matrix is similar to that found in conventional liquid electrolyte voltammetry using a PB-modified electrode; however part of the response is from PB which adsorbs onto the glassy carbon (GC) working electrode. Application of a Nafion® coating to the PB-impregnated paper matrix prevents transfer of PB to the GC surface. In contrast to the PB system, the redox response of the 1,1′-dimethyl-4,4′-bipyridilium (MV, methyl viologen) system, where both redox states examined are soluble, is confined wholly to the paper matrix. For the case of 1,1′-diheptyl-4,4′-bipyridilium (HV, heptyl viologen), the electrogenerated insoluble radical cation salt adsorbs onto the GC electrode, the KCl-impregnated paper acting simply as the electrolyte medium. PB can be electrogenerated within a paper matrix, with the possible application in monochrome electrochromic printing systems.     

Electrochemical and electrocatalytic stability of Prussian blue/Berlin green redox transformation in Prussian blue-polypyrrole composite films

Redox transformation of Prussian blue to Berlin green (PB/BG) in Prussian blue-polypyrrole (PB-PPy) composites synthesized via original one-step method has been studied. It was shown that the nature of anion and composition of background electrolyte play an important role for both the stability and the shape of electrochemical response of composite film during redox transfer of Prussian blue to Berlin green. Nitric acid, phosphoric acid, malic acid and citric acid 0.05 N (eq/L) solutions and the same acids partially neutralized with 0.01 N KOH were used as electrolyte to study the role of potassium ions presence in solution. The most stable electrochemical response of PB/BG redox transfer was obtained for the nitrate anions containing solutions in the presence of potassium ions. Nevertheless, the stability of the electrochemical transformation PB/BG in composite films in other media is enough to detect the sulphite ions content in wine samples via electrocatalytic reaction at the potentials of PB/BG redox transformation.

     

Observation of the anisotropic photoinduced magnetization effect in Co-Fe Prussian blue thin films fabricated by using clay Langmuir-Blodgett films as a template

Thin films of cobalt-iron cyanide (Co-Fe Prussian blue) have been fabricated by means of the modified Langmuir-Blodgett (LB) method using a smectite clay mineral (montmorillonite). In this combined method, clay LB films play a template role in the formation of the Co-Fe Prussian blue thin layer. The films were revealed to possess a well-organized structure not only in perpendicular directions to the film surface but also in parallel directions to the film surface. The photoinduced electron transfer from the iron ion to the cobalt through the bridging cyanide in the films occurred at low temperature (8 K), similar to that in the bulk Co-Fe Prussian blue. The films clearly exhibited magnetic anisotropy with regards to the direction of the applied magnetic field. Moreover, the photoinduced magnetization effect in the films was also found to be anisotropic.     

Structural and magnetic properties of thin manganite films grown on silicon substrates

Polycrystalline La_0.7Sr_0.3MnO₃ manganite thin films were grown on silicon substrates covered by SiO_x amorphous native oxide. Unusual splitting of the manganite layer was found: on the top of an intermediate layer characterised by lower crystalline order, a magnetic robust layer is formed. Curie temperatures of about 325 K were achieved for 70 nm thick films. A strong room temperature XMCD signal was detected indicating high spin polarisation near the surface.     

Crystallization of isotactic poly(methylmethacrylate) in monolayers and thin films

Langmuir-Blodgett monolayers of isotactic PMMA exhibit a pressure-induced transition upon compression, that can be described in terms of a two-dimensional crystallization process, analogous to a normal melt crystallization. These water surface crystallized monolayers can be used to prepare highly crystalline thin films of isotactic PMMA with tailor-made orientational characteristics.     

Annealing effect on the structural and magnetic properties of nickel ferrite thin films

Nickel ferrite is a soft magnetic material with inverse spinel structure. Soft ferrite films are used in microwave devices, integrated planar circuits, etc., because of their high resistivity. In this work, thin films of nickel ferrite were deposited on Si (100) substrate by using pulsed laser deposition (PLD) technique. The thickness of the film was measured by surface profilometer and also by X‐ray reflectivity (XRR). The films were annealed at three different temperatures to observe the effect on the structural and magnetic properties of the film. The films were characterised by X‐ray diffraction (XRD), Raman spectroscopy and vibrating sample magnetometer (VSM) to study the structural and magnetic properties. Copyright © 2010 John Wiley & Sons, Ltd.     

Multilayer assembly of Prussian blue nanoclusters and enzyme-immobilized poly(toluidine blue) films and its application in glucose biosensor construction

A multilayered glucose biosensor via sequential deposition of Prussian blue (PB) nanoclusters and enzyme-immobilized poly(toluidine blue) films was constructed on a bare Au electrode using electrochemical methods. The whole configuration of the present biosensor can be considered as an integration of several independent hydrogen peroxide sensing elements. In each sensing element, the poly(toluidine blue) film functioned as both the supporting matrix for the glucose oxidase immobilization and the inhibitor for the diffusion of interferences, such as ascorbic acid and uric acid. Meanwhile, the deposited Prussian blue nanocluster layers acts as a catalyst for the electrochemical reduction of hydrogen peroxide formed from enzymatic reaction. Performance of the whole multilayer configuration can be tailored by artificially arranging the sensing elements assembled on the electrode. Under optimal conditions, the biosensors exhibit a linear relationship in the range of 1 x 10(-4) to 1 x 10(-2) mol/L with the detection limit down to 10(-5) mol/L. A rapid response for glucose could be achieved in less than 3 s. For 1 mM glucose, 0.5 mM acetaminophen, 0.2 mM uric acid, and 0.1 mM ascorbic acid have no obvious interferences (<5%) for glucose detection at an optimized detection potential. The present multilayered glucose biosensor with a high selectivity and sensitivity is promising for practical applications.     

Fabrication and nanoindentation properties of TiN/NiTi thin films and their applications in electrochemical sensing

Nanocrystalline TiN/NiTi thin films have been grown on silicon substrate by dc magnetron sputtering to improve the corrosion and mechanical properties of NiTi based shape memory alloys without sacrificing the phase transformation effect. Interestingly, the preferential orientation of the TiN films was observed to change from (1 1 1) to (2 0 0) with change in nature of sputtering gas from 70% Ar + 30% N₂ to 100% N₂. In present study the influence of crystallographic orientation of TiN on mechanical and corrosion properties of TiN/NiTi thin films was investigated. TiN (2 0 0)/NiTi films were found to exhibit high hardness, high elastic modulus, and thereby better wear resistance as compared to pure NiTi and TiN (1 1 1)/NiTi films. Electrochemical test revealed that TiN coated NiTi film exhibits better corrosion resistance in 1 M NaCl solution as compared to uncoated NiTi film. The application of TiN/NiTi films in the electrochemical sensing of dopamine, which has a critical physiological importance in Parkinson's disease, has been demonstrated. A comparison of voltammetric response of dopamine at silicon based electrodes modified with different nanocrystalline coatings indicated that these films catalyze the oxidation of dopamine.     

In-situ monitoring of the dielectric and electrostrictive properties of anodised thin films for biochip applications

Further improving the performance of capacitance-based DNA microsensors will depend on the ability to synthesize simply, at a low cost, thin films of high dielectric permittivity with a well-controlled growth morphology. Anodisation of the valve metals Ti, Zr and Ta is a promising route for preparing such films. In this paper, we propose a new method for following the evolution of the dielectric properties of such anodised metallic oxide thin films in-situ during their growth. The technique relies on measuring the evolution of the electrostatic stress developing in the film. Measurements have been carried out on anodic TiO₂ films grown galvanostatically in HNO₃ at 1 and 3 mA/cm² and in H₃PO₄ at 0.5 mA/cm². The dielectric permittivity of the films was observed to decrease during the initial stage of anodisation, characterised by a steady increase of the cell voltage with time. The permittivity then reached a constant value when the oxide entered a second growth regime, characterised by a stabilisation of the cell voltage. The origin of the observed permittivity evolution is interpreted in terms of the evolution of the growth morphology of the films during anodisation.     

Spectroelectrochemical identity of Prussian blue films in various electrolytes: comparison of time-derivative voltabsorptometric responses with conventional cyclic voltammetry

Using Prussian blue (PB) electrodeposited on gold-covered foil as a model system, we have demonstrated the usefulness of the time-derivative measurements of absorbance versus potential (linear potential-scan voltabsorptometry) for spectroelectrochemical characterization of thin electrochromic films. The time-derivative signals were monitored for PB at 680 and 420 nm in potassium, sodium and lithium electrolytes. Information obtained from cyclic voltabsorptometry is equivalent or complementary to that from conventional cyclic voltammetry. In the case of PB films investigated in lithium electrolyte, the voltabsorptometric time-derivative peaks are better defined than the respective voltammetric peaks. The combination of voltabsorptometry with voltammetry enables molar absorptivity and/or film loading to be determined. Also, concentration changes of differently colored mixed-valence redox centers can be monitored as a function of applied potential. Received: 16 January 1997 / Accepted: 11 March 1997     

Self-assembly of linear and cyclic siloxane-containing mesogens: investigation of layered structures in bulk and thin films

Silicon-containing materials which possess the ability to form mesophases are promising systems for applications in the fields of electro-optical devices, nonlinear optics, and information storage media. In this work, the formation of supramolecular assemblies of a series of low molecular weight siloxane-containing mesogens is presented. Besides a novel synthesis route via Ru(II) -catalyzed hydrosilylation of phenyl acetylene derivatives, mesophase characterization by modern analysis techniques is performed. As linker groups, leading to bi- and tetramesogens, linear disiloxane and cyclic tetrasiloxane are utilized. In the resulting class of materials, high thermal stability, induced by the formation of layered smectic-type structures, is predominant. The smectic-type phases were found to be monotropic. Layer distances in the assemblies, as well as the phase transition temperatures, can be controlled by the substitution motif on the mesogens (number and length of alkyl chains). In spin-cast thin films, the layered domains are visualized by atomic force microscopy; furthermore, domain dimensions and electron densities are determined by grazing-incidence small-angle X-ray scattering.     

Recent advances in ZnO nanostructures and thin films for biosensor applications: Review

Biosensors have shown great potential for health care and environmental monitoring. The performance of biosensors depends on their components, among which the matrix material, i.e., the layer between the recognition layer of biomolecule and transducer, plays a crucial role in defining the stability, sensitivity and shelf-life of a biosensor. Recently, zinc oxide (ZnO) nanostructures and thin films have attracted much interest as materials for biosensors due to their biocompatibility, chemical stability, high isoelectric point, electrochemical activity, high electron mobility, ease of synthesis by diverse methods and high surface-to-volume ratio. ZnO nanostructures have shown the binding of biomolecules in desired orientations with improved conformation and high biological activity, resulting in enhanced sensing characteristics. Furthermore, compatibility with complementary metal oxide semiconductor technology for constructing integrated circuits makes ZnO nanostructures suitable candidate for future small integrated biosensor devices. This review highlights recent advances in various approaches towards synthesis of ZnO nanostructures and thin films and their applications in biosensor technology.