Discontinuous Thin Films Research Articles

Case study of fluorite mineralization using traditional and laser spectroscopic techniques, homret akarem area south eastern desert, Egypt

Green fluorite samples from Homret Akarem, eastern desert Egypt, were investigated by laser-based Raman spectroscopy to study the effect of rare earth elements (REEs) and natural radiation from the surrounding environment on their physico-chemical properties, taking into consideration the geological setting. Geochemical data of trace elements display fluorite enrichment with Y, Pb, Sr, Sn, and other REEs. XRD showed lattice parameters with values higher than those for synthetic fluorite due to the substitution of Ca by Sr and less likely by radiation from U. A considerable shift in the binding energy (BE) for Ca and F obtained from the XPS spectrum indicates that U carried by the hydrothermal solutions formed a discontinuous thin film on the surface of fluorite. Laser-Raman spectroscopy showed strong peaks below 500 cm−1 and both shallow and weak peaks above 500 cm−1. The strong peaks indicate that the substitution of Ca by Sr, point defects, and natural radiation caused by U have a stronger effect on the crystal structure than REEs. Raman spectroscopy supported the initial reports of uranium minerals like Rutherfordine, Kasolite, Soddyite, and Uranophane-alpha.

In English

Zinc oxide nanostructures (NS) were grown on thin discontinuous films of noble metals of silver and gold in order to study their structure, optical properties as well as photocatalytic and antiviral activity. The paper presents the results of X-ray diffraction study, scanning electron microscopy study, photoluminescence and Raman measurements. X-ray diffraction experiments demonstrate similar patterns for all grown ZnO nanostructures. The SEM images of ZnO NS grown on Ag/Si and Au/Si wafers demonstrate more dense surface microstructure compared to ZnO NS grown on bare Si wafers. The most intensive ultraviolet and deep level emissions are observed for ZnO NS grown on Ag/Si wafers. Increase in thicknesses of Ag island film from 5 nm to 10 nm gives significant increase in intensity of ultraviolet and deep level emissions. Photocatalysis of grown ZnO nanostructures was studied by methyl orange dye degradation. Superior photocatalytic results are demonstrated by ZnO nanostructures grown on Ag/Si wafers, for which constants of dye degradation were twice higher than for ZnO nanostructures grown on Si and Au/Si substrates. The photocatalytic results correlates with photoluminescence spectra: more intensive photoluminescence in ultraviolet and visible ranges of optical spectrum leads to better photocatalytic performance. The cytotoxic effect of ZnO nanostructures was studied without photoactivation by the help of cell cultures MDCK and Hep-2 while the virucidal effect of ZnO nanostructures was studied by the help of Influenza A virus (H1N1) (strain FM / 1/47) and human adenovirus serotype 2 (HAdV2). ZnO nanostructures in a 1:10 dilution were not toxic to Hep-2 and MDCK cells. Most of the tested ZnO nanostructures exhibited no virucidal activity against human adenovirus serotype 2 (HAdV2) and influenza A virus (H1N1) (strain FM / 1/47) in the absence of photoexcitation.

Electron transport in discontinuous metal thin films

The structure and basic experimental electrical properties of vacuum evaporated discontinuous (island) metal thin films of discrete metal nanoparticles on insulating substrates are briefly reviewed. Then the widely accepted Neugebauer and Webb (N&W) electrostatically activated electron tunneling conduction model is covered (with enhancements) before the numerous discrepancies between this model and experimental observations are identified, e.g. minimal substrate bias effect, non-linear field distribution, anomalous AC effects, asymmetrical contact effects, and switching. A modified model, based on contact electron injection and extraction, and computer simulations are introduced which explain these discrepancies at a qualitative level. However, quantitative experimental verification of the model is not possible without stable, reproducible films of known structures. The paper concludes with a review of possible preparation techniques which could yield satisfactory samples, especially self-assembly of organically protected metal nanoparticles. One of these has already demonstrated electrostatically activated conduction.

The Impact of Chiral Citronellyl‐Functionalization on Indolenine and Anilino Squaraine Thin Films

AbstractThe impact on chiral aggregation in solution processed and thermally annealed thin films of two indolenine and one anilino squaraines with chiral (S)‐citronellyl functionalization at the nitrogen of the squaraine backbone is investigated. A pseudo polymorphic crystal structure is obtained for one of the indolenine squaraines, but thin films of both compounds are basically non‐aggregated and truly isotropic as evidenced by spectroscopic ellipsometry. The anilino squaraine coalesces and readily aggregates to circular dichroic but discontinuous thin films. The extent of circular dichroism correlates with the morphology of the samples, which is quantified by Mueller matrix polarimetry in combination with atomic force microscopy. The shape of the CD spectra reinforces the hybrid Frenkel and charge‐transfer excitonic nature of the characteristic double hump signatures within unpolarized absorbance spectra of previously investigated non‐chiral anilino squaraines with linear alkyl chain functionalization. Such excitonic CD offers an additional design parameter for next‐generation opto‐electronic devices.

In-situ Transmission Electron Microscope Investigation of Atomic-scale Titanium Silicide Monolayer Superlattice

In this work, the titanium germanosilicide (TiSiGex) superlattice (SL) has been successfully fabricated. A monolayer of silicon atoms and bilayer of inversed titanium silicide constructed this novel superlattice periodically. A localized strain field has been found as a crucial factor via high resolution Annular Dark Field Scanning Transmission Electron Microscope (ADF-STEM) images, being generated by gradual segregation of germanium atoms. Germanium atoms would be excluded during the formation of the transition silicide. This phenomenon could be interpreted by thermodynamic preference. There was a substitution reaction between silicon and germanium, resulting from similar atomic volumes of both. In other words, germanium segregation pathway was based on where substitution occurred. Eventually, the excluded germanium atoms tended to accumulate at the boundary of TiSiGex-SL, contributing to a discontinuous thin film layer.

Observing and controlling a Tamm plasmon at the interface with a metasurface

Abstract We demonstrate experimentally that Tamm plasmons in the near infrared can be supported by a dielectric mirror interfaced with a metasurface, a discontinuous thin metal film periodically patterned on the sub-wavelength scale. More crucially, not only do Tamm plasmons survive the nanopatterning of the metal film but they also become sensitive to external perturbations as a result. In particular, by depositing a nematic liquid crystal on the outer side of the metasurface, we were able to red shift the spectral position of Tamm plasmon by 35 nm, while electrical switching of the liquid crystal enabled us to tune the wavelength of this notoriously inert excitation within a 10-nm range.

MWCNTs patterning by thermally enhanced and confined evaporation for transparent and conductive thin film

Conductive and transparent thin film structures are useful in flexible electronics. In this paper, we report multi-walled carbon nanotubes (MWCNTs) patterning into gradient regular patterns with large area of about several square centimeters on silicon or wafer glass slide via thermally enhanced evaporative self-assembly under wedge-shaped geometric confinement. The morphologies, electrical and optical properties of the MWCNTs thin film were characterized. The findings reveal that the conductance would increase with depositing times, meanwhile the transparency would decrease. The resistance of the grid patterning films of MWCNTs has a nearly linear relation to the transmittance in a relatively large range. The MWCNTs can be easily transferred to flexible substrate such as PET films or an adhesive tape. In comparison, SWCNTs could hardly be deposited into stripes or grid patterns, but the continuous thick films and discontinuous thin films could demonstrate better electrical and mechanical performance.

Growth Behavior Evolution of Al2O3 Deposited on HOPG by Atomic Layer Deposition

Abstract Al2O3 dielectrics were fabricated on highly ordered pyrolytic graphite (HOPG) by atomic layer deposition (ALD) and the effects of growth temperatures and number of ALD cycles on growth behaviors were studied. It is found that Al2O3 preferentially grows along the step edges which promote the formation of Al2O3 nanowires at the initial stage. Al2O3 nanowires can exist after 100 ALD cycles at 50, 150, and 200 °C, but discontinuous Al2O3 thin films rather than nanowires are evidenced at 100 °C. Moreover, the Al2O3 layers evolve into continuous thin films with increasing number of ALD cycles. It suggests the growth behavior undergoes a transition from three-dimensional mode to quasi two-dimensional mode with increasing number of ALD cycles. The rates of transition and lateral growth are dependent on growth temperatures. Raman spectra indicate that HOPG maintains undamaged and greatly reserves its original properties after the deposition of Al2O3. The results are of great significance to the fabrication of high-quality dielectric layers on graphene as well as the related devices.

Peculiarity of magnetoresistance of discontinuous ferromagnetic thin films

The magnetoresistive properties of discontinuous ferromagnetic Fe and Co thin films deposited by electron-beam sputtering onto glass substrates at room temperature were investigated. Tunnel magnetoresistance (MR) was observed for all of the as-deposited samples. The maximum MR was observed for Fe thin films with an effective thickness of 17 nm. In the case of the Co thin films, the annealing process led to a change of the type of MR to anisotropic at Co film thicknesses (dCo) of 15 ≤ dCo ≤ 25 nm and to positive isotropic at thicknesses of dCo < 15 nm. By contrast, the MR type of Fe thin films did not change.

One step ‘dip’ and ‘use’ Ag nanostructured thin films for ultrahigh sensitive SERS Detection

A simple one step galvanic displacement method which involves dipping of the silicon substrate in the AgNO3/HF solution and using it for SERS application without any further process is demonstrated. The size and shape of the Ag nanoparticles changes as the deposition time is increased. Initially the shape of the particles was nearly spherical and as it grows, becomes oblong and then coalesce to form a discontinuous film with vertically grown hierarchical Ag nanostructures. The sizes of the deposited particles were in the ranges from 30nm to a discontinuous film. It also demonstrated a highly sensitive chemical detection by surface-enhanced Raman scattering of rhodamine 6G dye, down to 10−16M concentration. Prepared samples were able to detect lower concentrations of Melamine. Discontinuous thin films with hierarchical Ag nanostructures were obtained for 5min Ag deposition. The formation of Hot spots between the discontinuous islands and also along the hierarchical structures is responsible for the high SERS enhancement. This simple one step, fast, non-lithographic and cost effective method can be applied for various label free detection of analytes of importance.

Texture evolution and microstructural changes during solid-state dewetting: A correlative study by complementary in situ TEM techniques

The transition of a thin film into an energetically favorable set of particles at temperatures below the melting point of the bulk material is known as solid-state dewetting. In this work the dewetting behavior of 16 nm thick discontinuous Au thin films on amorphous silicon nitride membranes is quantitatively studied by complementary in situ transmission electron microscopy techniques taking advantage of the unique capabilities of a chip-based heating system. The combination of dedicated imaging and diffraction techniques is used to investigate the interplay of grain growth and texture evolution with the process of dewetting. The results show an initial coarsening of the microstructure preceding the other processes. Texture evolution is highly correlated to material retraction and agglomeration during the following dewetting process. In-plane grain rotation has been observed, acting as an additional mechanism for orientation changes. From a methodological perspective this work demonstrates the capabilities of today’s transmission electron microscopy in combination with state-of-the-art in situ instrumentation. In particular the combination of complementary information from different dedicated techniques in one and the same setup is demonstrated to be highly beneficial.

CO and D2O chemistry on continuous and discontinuous samaria thin films on Pt(111)

The chemistry of CO and D2O, individually adsorbed or co-adsorbed, on epitaxial thin films of samaria on Pt(111) was studied by temperature-programmed desorption spectroscopy (TPD). Continuous thin films as well as discontinuous films composed of samaria islands on bare Pt(111) were prepared. Their comparative study indicates that Sm2O3 islands provide lattice oxygen at their perimeter for CO oxidation on adjacent exposed Pt area where CO adsorption takes place. CO2 production was observed only on as-prepared discontinuous films. While, in particular on thermally reduced samaria islands, TPD after D2O adsorption revealed D2 production which indicates a pathway for D2O dissociation, no evidence for the water gas shift reaction of CO and residual OD species on the surface was found after co-adsorption of CO and D2O. Instead, interaction between CO and OD species at the perimeter of islands on reduced discontinuous SmOx thin films obviously promotes D2 formation without yielding CO2 as desorbing product.

The process of solid-state dewetting of Au thin films studied by in situ scanning transmission electron microscopy

Solid-state dewetting describes the transformation of thin films into a set of particles or droplets at temperatures well below the melting temperature of the bulk. In this work in situ scanning transmission electron microscopy has been used to study the dewetting behavior of discontinuous Au thin films (15nm and 22nm thick) on amorphous silicon nitride membranes at temperatures ranging from 300°C to 600°C. The combination of microscopic and statistical information enabled not only the qualitative discussion of the observed processes but also the quantification of the kinetics as well as the development of a model of the underlying morphological mechanism. A model-free master curve approach to the temporal evolution of the covered area at different temperatures is used to determine the activation energy of dewetting (1.04±0.14eV for the 15nm thick film). A closer inspection reveals a multiple power law behavior, which is discussed in the frame of depercolation. Retraction of finger-like structures is found to be the dominant morphological mechanism based on the observed linear relationship between covered area and boundary length.

Deposition and characterization of Pt nanocluster films by means of gas aggregation cluster source

In this study we report on the deposition of Pt nanocluster films prepared by gas aggregation source that was operated with argon as working gas. The aim of this study was optimization of deposition process as well as determination of properties of deposited nanocluster films and their temporal stability. It was found that the production of Pt nanoclusters reached maximum value for pressure of 100Pa and increases monotonously with magnetron current. The deposition rate at optimized deposition conditions was 0.7nm of the Pt nanocluster film per second. Deposited films were porous and composed of 4nm Pt nanoclusters. The nanoclusters were metallic and no sights of their oxidation were observed after 1year on open air as witnessed by X-ray photoelectron spectroscopy. Regarding the electrical properties, a dramatic decrease of the resistivity was observed with increasing amount of deposited nanoclusters. This decrease saturated for the films approximately 50nm thick. Such behavior indicates transition between different mechanisms of electrical conductivity: charge hopping for thin discontinuous films and current conduction through conducting path formed when higher amount of nanoclusters is deposited. Different mechanisms of electrical conduction for thin and thick layers of Pt were confirmed by subsequent investigation of temperature dependence of resistivity. In addition, no changes in resistivity were observed after one year on open air that confirms stability of produced Pt nanocluster films.

Huge hydrogen-induced resistive switching in percolating palladium thin films

Hydrogen absorption in metals causes volume expansion, which increases abruptly with phase transformation. This effect can stimulate hydrogen-induced percolation of discontinuous palladium thin films, yielding a drop in the films’ electrical resistance. Long-term exposure to air and cyclic hydrogen loading of palladium films with optimized morphology (meander films of 15 nm thickness, islands gaps of about 14 nm) are shown to change the meander connectivity and, thereby, increase the films’ resistance switching to −5900% in a narrow pressure range.

Silver Metallization of Polyimide Surfaces Using Environmentally Friendly Reducing Agents

Two environmentally friendly reducing agents, ascorbic acid and glucose, were employed to fabricate Ag-thin-film-coated polyimide (PI) films. Ascorbic acid is an acidic reducing agent, whereas glucose is an alkaline reducing agent. Both of these reducing agents are capable of reducing Ag+ ions doped in poly(amic acid) (PAA) formed by hydrolysis of a PI surface. Only glucose can produce a continuous and dense Ag thin film on a PAA surface. Granular and discontinuous Ag thin films were obtained when ascorbic acid was employed as a reducing agent. This difference in reactivity is attributed to the pH values of these reducing solutions. © 2013 The Electrochemical Society. [DOI: 10.1149/2.001311eel] All rights reserved.

Interface controlled growth of nanostructures in discontinuous Ag and Au thin films fabricated by ion beam sputter deposition for plasmonic applications

The growth of discontinuous thin films of Ag and Au by low energy ion beam sputter deposition is reported. The study focuses on the role of the film–substrate in determining the shape and size of nanostructures achieved in such films. Ag films were deposited using Ar ion energy of 150 eV while the Au films were deposited with Ar ion energies of 250–450 eV. Three types of interfaces were investigated in this study. The first set of film–substrate interfaces consisted of Ag and Au films grown on borosilicate glass and carbon coated Cu grids used as substrates. The second set of films was metallic bilayers in which one of the metals (Ag or Au) was grown on a continuous film of the other metal (Au or Ag). The third set of interfaces comprised of discontinuous Ag and Au films deposited on different dielectrics such as SiO2, TiO2 and ZrO2. In each case, a rich variety of nanostructures including self organized arrays of nanoparticles, nanoclusters and nanoneedles have been achieved. The role of the film–substrate interface is discussed within the framework of existing theories of thin film nucleation and growth. Interfacial nanostructuring of thin films is demonstrated to be a viable technique to realize a variety of nanostructures. The use of interfacial nanostructuring for plasmonic applications is demonstrated. It is shown that the surface Plasmon resonance of the metal nanostructures can be tuned over a wide range of wavelengths from 400 to 700 nm by controlling the film–substrate interface.

Ultra-slow relaxation in discontinuous-film–based electron glasses

We present field effect measurements on discontinuous 2D thin films which are composed of a sub-monolayer of nano-grains of Au, Ni, Ag or Al. Like other electron glasses these systems exhibit slow conductance relaxation and memory effects. However, unlike other systems, the discontinuous films exhibit a dramatic slowing-down of the dynamics upon lowering the temperature below a characteristic, sample-dependent temperature, T*. For T < T* the sample exhibits a few peculiar features such as repeatable conductance fluctuations in millimeter-size samples. We suggest that the enhanced system sluggishness is related to the current-carrying network becoming very dilute in discontinuous films so that the system contains many parts which are electrically very weakly connected and the transport is dominated by very few weak links. The results provide new insight into the underlying physics of electron glasses.

Partial rectification of the plasmon-induced electrical tunnel current in discontinuous thin gold film at optical frequency

The effect of plasmon oscillations, induced by pulsed laser irradiation, on the DC tunnel current between islands in a discontinuous thin gold film is studied. The tunnel current is found to be strongly enhanced by partial rectification of the plasmon-induced AC tunnel currents flowing between adjacent gold islands. The DC tunnel current enhancement is found to increase approximately linearly with the laser intensity and the applied DC bias voltage. The experimental data can be well described by an electron tunnelling model which takes the plasmon-induced AC voltage into account. Thermal heating seems not to contribute to the tunnel current enhancement.

Chemical and spatial analysis of protein loaded PLGA microspheres for drug delivery applications

Polymer microspheres for controlled release of therapeutic protein from within an implantable scaffold were produced and analysed using complimentary techniques to probe the surface and bulk chemistry of the microspheres. Time of Flight – Secondary Ion Mass Spectrometry (ToF-SIMS) surface analysis revealed a thin discontinuous film of polyvinyl alcohol (PVA) surfactant (circa 4.5nm thick) at the surface which was readily removed under sputtering with C60. Atomic Force Microscopy (AFM) imaging of microspheres before and after sputtering confirmed that the PVA layer was removed after sputtering revealing poly(lactic-co-glycolic) acid(PLGA). Scanning electron microscopy showed the spheres to be smooth with some shallow and generally circular depressions, often with pores in their central region. The occurrence of the protein at the surface was limited to areas surrounding these surface pores. This surface protein distribution is believed to be related to a burst release of the protein on dissolution. Analysis of the bulk properties of the microspheres by confocal Raman mapping revealed the 3D distribution of the protein showing large voids within the pores. Protein was found to be adsorbed at the interface with the PLGA oil phase following deposition on evaporation of the solvent. Protein was also observed concentrated within pores measuring approximately 2μm across. The presence of protein in large voids and concentrated pores was further scrutinised by ToF-SIMS of sectioned microspheres. This paper demonstrates that important information for optimisation of such complex bioformulations, including an understanding of the release profile can be revealed by complementary surface and bulk analysis allowing optimisation of the therapeutic effect of such formulations.