Ordering and growth of Langmuir–Blodgett films: X-ray scattering studies

The interplay of ordering, confinement and growth in ultrathin films gives rise to various interesting phenomena not observed in bulk materials. The nature of ordering and interfacial morphology present in these films, in turn, depends on their growth mechanism. Well-ordered metal–organic films, deposited using an enigmatic Langmuir–Blodgett (LB) technique, are not only ideal systems for understanding the interplay between growth and structure of ultrathin films but also for studying chemical reactions and phase transitions in confined geometries. Studies on these LB films also enhance our understanding of the fundamental interactions of amphiphilic molecules important for biological systems. Advent of grazing incidence X-ray scattering techniques has enabled us to probe the interfacial structure of these multilayer films at very high resolution and as a result has improved our knowledge about the mechanism of growth processes and about physical/chemical properties of ultrathin films. In this review we will focus our attention on recent results obtained using these X-ray scattering techniques to understand the mechanism of growth leading to formation of remarkably well-ordered LB films after giving a brief outline of these scattering techniques. In addition, we also review recent results on growth and structure of nanoparticles formed by suitable chemical processes within the ordered matrix of LB films. Finally, we will discuss the work done on melting of LB films and its implications in our understanding of melting process in lower dimensions. In all these studies, especially those on as-deposited LB films results of atomic force microscopy measurements have provided important complementary morphological information.     

Structural and surface morphological studies of long chain fatty acid thin films deposited by Langmuir–Blodgett technique

In the present work we aim to study the structural and surface morphological characteristics of divalent cation (cadmium ion, Cd²⁺) induced thin mono- to multilayer films of fatty acids such as arachidic acid and stearic acid prepared by the Langmuir–Blodgett (LB) technique. These ultra thin films of various numbers of layers were studied by X-ray diffraction (XRD), X-ray reflectivity (XRR) and Atomic Force Microscopy (AFM). In this specific Y-type deposition, it was found that as the individual layer thickness increases, the corresponding layer by layer interfacial electron density of the thin films decreases. Since the fatty acid chain tries to maintain its minimum value of cross-sectional area, tilting occurs with respect to its nearest neighbor. The tilt angle calculated for 9 layers of cadmium arachidate (CdA₂) and cadmium stearate (CdSt₂) are 18° and 19.5°, respectively. An asymmetric air gap of thickness ∼3 Å was also seen between the tail parts of 2 molecular chains. The RMS roughness and average height factors calculated through AFM studies show non-uniform surface morphology of both CdA₂ and CdSt₂, although the calculated topographic variations were found to have more irregularity in case of CdSt₂ than in case of CdA₂.     

Exponential temperature dependence and low-bias conductance anomaly in transport through Langmuir–Blodgett monolayer devices

Current–voltage characteristics are reported as a function of temperature (2–300 K) for 2.8-nm-thick eicosanoic acid (C₂₀) Langmuir–Blodgett organic monolayers sandwiched between planar platinum electrodes of area 5–200 m². An exponential temperature dependence observed between 60 and 300 K does not fit standard activated conduction, but can be described by thermionic field emission through a thin 0.1-eV barrier. A second model of tunneling through a vibrationally excited harmonic oscillator barrier also fits the data. A broad 200 meV dip in conductance at V=0 suggests strong inelastic tunneling, supporting the vibrational model. PACS 73.40.Gk; 68.47.Pe; 73.63.-b     

Relation between 2p X-ray photoelectron and Kα X-ray emission spectra of manganese and iron oxides

The high resolution Mn and Fe Kα X-ray emission spectra (XES), and Mn and Fe 2p X-ray photoelectron spectra (XPS) for manganese and iron oxides were measured. The spectra were compared with those of [MnO₄]⁻, [Fe(CN)₆]⁴⁻ and [Fe(CN)₆]³⁻ ions. As the electronic structure of the latter compounds do not change with electron hole creation in the core levels, satellite peaks due to charge transfer are not observed in the 2p XPS spectra, and the peak profiles of metal 2p XPS and Kα XES are governed by the exchange splitting between 2p and valence electrons. The metal 2p XPS spectra of the oxides had satellite peaks, but the XES spectra had no satellites. FWHMs of the metal 2p_3/2 main peaks of the compounds being low spin states are smaller than those of metal Kα₁ XES spectra. However, FWHMs of Mn 2p_3/2 of the manganese oxide were nearly equal to those of Mn Kα₁ XES spectra, and those of Fe 2p_3/2 XPS spectra of the iron oxides are greater than those of Fe Kα₁ XES spectra.     

X-ray standing wave studies of metal ions incorporation in Langmuir–Blodgett films

The molecular organization in Langmuir–Blodgett films of phospholipids and metallomesogen deposited on silicon has been studied by the X-ray standing-wave method at the synchrotron radiation source BESSY (Germany). Analysis of the experimental data obtained made it possible to determine the composition of the organic multilayer nanosystems and localize the position of metal ions incorporated in organic layers from the aqueous subphase during film deposition.     

Formation of nanoscale aggregates of a coumarin derivative in Langmuir–Blodgett film

In the present communication, we report the formation of organized nanoscale aggregates of a coumarin derivative 7 Hydroxy-N-Octadecyl Coumarin-3-Carboxamide (7HNO3C) at the air–water interface and in Langmuir–Blodgett (LB) films in the presence and absence of stearic acid (SA). A pressure-area isotherm reveals that the 7HNO3C form stable monolayer at the air–water interface. However, the stability can be improved by mixing it with a fatty acid stearic acid (SA). The miscibility study shows that the nature of interaction is strongly dependent on the mixing ratio and surface pressure. At a mole fraction of 0.4 of 7HNO3C in SA, the attractive and repulsive interaction between these two molecules balance each other forming a stable film with nanoscale aggregates. UV-Vis absorption spectroscopic studies reveal the nature of the aggregates in LB films. Scanning electron microscopy gives compelling visual evidence of formation of nanoscale aggregates in the mixed LB films.     

Langmuir–Blodgett films and optical second-harmonic generation of a crowned [60]fulleropyrrolidine

The Langmuir and Langmuir–Blodgett (LB) films of a novel crowned [60]fullero-pyrrolidine (CFP) were produced in different conditions. Macroscopic second-harmonic generation of the LB film was investigated by means of AM1 Hamiltonian as well as experiments. The monolayer LB film displayed a periodic fringe pattern. A linear dependence of second-harmonic intensity on the number of layers was observed. The second-order molecular susceptibility χ⁽²⁾ and hyperpolarizability β were evaluated to be 3.2×10⁻⁸ and 8.3×10⁻²⁹ esu. Received: 21 October 1999 / Revised version: 30 March 2000 / Published online: 2 August 2000     

Nature of luminescence of PbS quantum dots synthesized in a Langmuir–Blodgett matrix

We calculate current (shot) noise in a metallic diffusive conductor generated by spin imbalance in the absence of a net electric current. This situation is modeled in an idealized three-terminal setup with two biased ferromagnetic leads (F-leads) and one normal lead (N-lead). Parallel magnetization of the F-leads gives rise to spin-imbalance and finite shot noise at the N-lead. Finite spin relaxation results in an increase in the shot noise, which depends on the ratio of the length of the conductor (L) and the spin relaxation length (l _s). For L >> l _s the shot noise increases by a factor of two and coincides with the case of the antiparallel magnetization of the F-leads.     

An X-ray photoelectron spectroscopy investigation of a novel Pd–Pt colloid catalyst

A Bi-promoted charcoal-supported Pd–Pt oxidation catalyst prepared from colloidal NOct₄Cl-stabilized Pd–Pt nanoparticles was investigated by means of X-ray photoelectron spectroscopy (XPS). Pd 3d, Pt 4f, Bi 4f, C 1s and O 1s spectra of the colloid, the supported colloid catalyst and a conventional charcoal-supported Pd–Pt/Bi coimpregnation catalyst (Degussa, CEF 196 RA/W) were measured. Both catalysts were explored unused (as-prepared) and after deactivation in the heterogeneous catalytic oxidation of glucose to gluconic acid. The spectra are analyzed to elucidate the higher starting activity of the Pd–Pt/Bi/C colloid catalyst, especially the role of the promotor Bi and the mechanisms leading to catalyst deactivation. The higher starting activity of the colloid catalyst is explained by the presence of completely reduced Pd and Pt, threevalent Bi and a smaller particle size in contrast to the conventional catalyst which contains partly oxidized Pd and a non-unique chemical state of Bi. The deactivation of both catalysts is suggested to be due to metal dissolution, particle growth and chemical poisoning.     

Preparation and probe analysis of Langmuir–Blodgett films with metal-containing dendritic and cluster structures

We aim to reveal the influence of?pH values of the working solution on spatial arrangement of metal-containing inclusions in the monolayer coatings prepared by Langmuir?CBlodgett (LB) technology and transferred to solid substrates with consequent modification of surface electrical properties. Consequently, films with inclusions in the form of dendrites and cluster shapes have been obtained. Submicron and micron lead-containing formations in Langmuir?CBlodgett films have been characterized by using the atomic force microscopy, Kelvin probe microscopy, and scanning electron microscopy methods. The results show that increasing?pH value of the subphase has caused the significant changes in the shape and composition of the inclusions in Langmuir?CBlodgett films. The synthesized inclusions on the solid substrate surface resulted in formation of the regions with the local electric fields and, as consequence, to significant modification of the structure and electrical properties. The location and length of the regions with surface potential disturbance depend on the shape of inclusions, and consequently, on?pH value of the subphase used in LB technology.     

Optical investigation of CdS quantum dots in Langmuir–Blodgett films

Structures with CdS quantum dots produced by the Langmuir–Blodgett (LB) technique were investigated by Raman, IR, and UV spectroscopies. The confinement effect of longitudinal optical (LO) phonons in CdS quantum dots was investigated by Raman spectroscopy. Surface vibrational modes of CdS quantum dots were observed in IR spectra. It was shown experimentally that the frequency of the surface vibrational modes depends on the properties of the surrounding media. An average size of CdS quantum dots of about 3–6.4 nm was obtained from the analysis of UV measurements. Received: 1 February 1999 / Accepted: 1 April 1999 / Published online: 19 May 1999     

IR Dichroism of Langmuir–Blodgett Films Based on Fatty Acids

We propose a method of measurement and quantitative estimation of dichroic ratios of submicron laminated Langmuir–Blodgett films by the IR spectra of multiple attenuated internal reflection. The method has been used in calculating the angles of orientation of molecular chains of stearic and palmitic acids in the process of their molecular deposition on an optical substrate. It has been found that in the process of structural self-organization of ensembles the degree of orientation of macromolecules is the higher, the greater the number of links entering into the aliphatic chain.     

Photochemical behaviour of an acid-terminated azopolymer in solution and in Langmuir–Blodgett films

Trans–cis–trans isomerization processes of an acid-terminated azopolymer have been investigated in mono and multilayered Langmuir–Blodgett (LB) films and the results compared with the behaviour of this azopolymer in solution. UV–vis spectroscopy was used to determine the apparent extent of photoisomerization at the photostationary state, as well as the order and rate constant of the cis → trans thermal isomerization, whilst structural changes of the LB films during photoisomerization have been monitored by AFM microscopy. From these studies it was concluded that the trans → cis photoisomerization extent largely depends on the free volume around the azobenzene chromophores, with the smaller apparent extent of photoisomerization obtained for a well-organized 10-layer LB film. Data also revealed a first-order kinetics for the thermal cis → trans isomerization process of the azopolymer both in solution and in LB films. The cis → trans isomerization process depends on the balance between the stress produced by the larger cross-section of cis-isomers inside the system and the interactions between cis-isomers and neighbouring molecules. The slowest cis → trans isomerization process takes place in a 35-layer LB film, whilst LB films with well-packed azobenzene layers show faster cis → trans isomerization processes.     

Immobilization of glucose oxidase onto Langmuir–Blodgett films of poly-3-hexylthiophene

Monolayers of poly(3-hexyl thiophene) (P3HT) were obtained by dispensing a solution of P3HT with stearic acid (SA) in chloroform at air-water interface using Joyce–Loebl LB trough. These films were transferred onto indium-tin-oxide coated glass plate by vertical dipping method. Enzyme glucose oxidase (GOX) was immobilized on the films using LB technique. These films were characterized by X-ray diffraction and atomic force microscopic techniques. Photometric response of these P3HT/SA/GOX films was obtained as a function of glucose concentration. These P3HT/SA/GOX LB films show a linearity from 100 to 500 mg/dl of glucose concentration.     

Structural and electronic properties of monolayer hydrogenated honeycomb III–V sheets from first-principles

Using first-principles calculations, we investigate the structural and electronic properties of monolayer hydrogenated honeycomb III–V sheets. The lattice constants and cohesive energies of the hydrogenated III–V (XY H₂, X=B, Al, Ga, and Y =N, P, As) sheets depend on the III–V elements and follow the same trend as the atomic radii of the elements. We find that the short lattice constants correspond to the large cohesive energies of the hydrogenated III–V sheets. Similar to the graphane sheet, the hydrogenated BP and BAs sheets prefer the chair conformation. While for the hydrogenated BN, AlN, AlP, and GaN sheets, the boat conformation is favored. For the hydrogenated AlAs, GaP, and GaAs sheets, the chair and boat conformations are degenerate structures. We obtain that all the hydrogenated III–V sheets are wide-gap semiconductors. With GW corrections, the band gaps of hydrogenated III–V sheets follow the order of nitrogen > phosphorous > arsenic compounds for both the chair and boat conformations.     

Nonlinear optical properties of nanometer-size silver coated polydiacetylene composite vesicles and resulting Langmuir–Blodgett films

Noble metal-coated PDA composite vesicles were expected to increase the effective third-order nonlinear optical susceptibility χ ⁽³⁾(ω), due to the enhancement of the optical electric field induced by localized surface plasmon resonance. Different size (20, 50 and 80 nm) Ag colloidal nanoparticles were coated on the outer surface of polydiacetylene (PDA) vesicles to form PDA/Ag nanocomposite vesicles and the size-dependent effect of Ag colloidal nanoparticles on NLO properties enhancement has been explored. The explanation based on the competition of a size-dependent light-confinement effect and a size-dependent dielectric constant of Ag particles had been presented. Furthermore, these PDA/Ag composite vesicles were successfully immobilized onto the solid substrate by the Langmuir–Blodgett (LB) method and their linear and nonlinear optical properties were characterized, respectively. Obviously, PDA/Ag composite vesicles Langmuir–Blodgett (LB) films promoted the enhancement of the third-order NLO properties.     

Template growth of vertically aligned carbon nanotubes using self-assembled monolayers of SiO2 particles by Langmuir–Blodgett technique

The thermal stability of nanocrystalline 3R-CuCrO₂ obtaining by hydrothermal method was investigated by annealing treatment, XRD, FT-IR, XPS and TG. The three temperature domains corresponding to thermal stability of 3R-CuCrO₂ nanocrystals (25–400 °C), destabilization of nanocrystalline 3R-CuCrO₂ phase (400–800 °C) and recrystallization of 3R-CuCrO₂ in microcrystalline state over 800 °C, were determined by the specific hydrothermal synthesis conditions. This study has indicated that nanocrystals with delafossite structure synthesized by hydrothermal method exhibit nanocrystalline state up to a reasonably high temperature, about 390 °C, which could be interesting for technical applications and the classical theory of the grain growth.     

Analysis of the Properties of Metal Sulfide Nanocrystals Synthesized by the Langmuir—Blodgett Technique

JETP Letters - Nanocrystals of metal sulfides (CdS, ZnS, CdZnS, CuS, and PbS) are formed upon the interaction of gaseous hydrogen sulfide with Langmuir—Blodgett films of metal behenates. To...     

Pump–probe studies of EUV and X-ray emission dynamics of laser-irradiated noble gas droplets

The interaction of high intensity 100-ps laser pulses with micron-sized noble gas (argon and krypton) droplets is experimentally investigated via a series of pump–probe experiments monitoring the delay-dependent X-ray and extreme ultraviolet (EUV) emission, and by imaging frequency-doubled probe light scattered from the interaction region. An understanding of the time scales for this interaction is important for optimization of EUV sources for next-generation lithography that utilizes laser-produced plasmas (LPP). Depending on the spectral region of interest, the type of emission, and the droplet characteristics, the effective emission lifetime was found to extend from a few hundred picoseconds to as long as several nanoseconds, in agreement with the expected plasma expansion, EUV excitation, and recombination emission time scales. Received: 22 August 2002 / Accepted: 8 February 2003 / Published online: 28 May 2003 RID="*" ID="*"Corresponding author. Fax: +1-301/3149-363, E-mail: riq@wam.umd.edu     

Atomic composition and stability of Langmuir–Blodgett monolayers based on siloxane dimer of quaterthiophene on the surface of polycrystalline gold

Physics of the Solid State - Atomic composition of monolayers based on siloxane dimer of quaterthiophene deposited by Langmuir–Blodgett technique on a silicon dioxide surface partially...