Intermixing at the interface of the system Nb/Fe(1 1 0) investigated by STM

The growth of niobium on the Fe(1 1 0) surface at a deposition temperature between room temperature (RT) and 680 K was studied using in situ STM and LEED. At RT we observe no indication of intermixing. Although a final roughness of only 1.7 Å is reached, the crystalline quality is low. At elevated growth temperatures the development of a surface alloy was observed, whose formation is ascribed to an exchange mechanism through which Nb adatoms are incorporated into the Fe surface. These Nb atoms arrange themselves in chains along the [0 0 1] direction. The expelled Fe atoms form islands on the Nb/Fe-alloy substrate. At higher coverage additionally a Nb wetting layer and intermixed 3D islands evolve.     

Compositional origin of surface roughness variations in air-annealed ZnO single crystals

We directly investigated the chemical compositional origin of surface roughness variations in air-annealed ZnO single crystal samples for annealing temperatures up to 1000 °C. Atomic Force Microscopy (AFM) showed temperature-dependent changes in surface roughness and morphology, with a maximum in surface roughness of 2 nm found for samples annealed at 400 °C. The O(1s) line, measured by X-ray Photoelectron Spectroscopy (XPS) showed a maximum for Zn(OH)₂ and a minimum for off-stoichiometric ZnO at 400 °C; while the Zn(2p) peaks show an increase in slope at that temperature. These results indicate that the roughness arises from Zn diffusion and loss of surface oxygen.     

Room-temperature-adsorption behavior of acetic anhydride on a TiO2(1 1 0) surface

We have studied the adsorption structure of acetic anhydride on a TiO₂(1 1 0) surface using XPS (X-ray photoelectron spectroscopy), LEED (low energy electron diffraction) and HREELS (high resolution electron energy loss spectroscopy) to determine the origins of the unique adsorption properties of carboxylic acids on a TiO₂(1 1 0) surface. The C 1s XPS data indicated that the saturation carbon amount of adsorbed acetic anhydride was 12 ± 3% larger than that of the adsorbed acetic acid. LEED showed p(2 × 1) weak spots for the acetic anhydride adsorbed surface. The HREELS spectra revealed the dissociative adsorption of acetic anhydride. Based on these findings, we concluded that the neutralization of the bridging oxygen atoms associated with the dissociative adsorption is necessary for the stable adsorption of carboxylates on the 5-fold Ti sites.     

Surface cleaning procedures for thin films of indium gallium nitride grown on sapphire

Surface preparation procedures for indium gallium nitride (InGaN) thin films were analyzed for their effectiveness for carbon and oxide removal as well as for the resulting surface roughness. Aqua regia (3:1 mixture of concentrated hydrochloric acid and concentrated nitric acid, AR), hydrofluoric acid (HF), hydrochloric acid (HCl), piranha solution (1:1 mixture of sulfuric acid and 30% H₂O₂) and 1:9 ammonium sulfide:tert-butanol were all used along with high temperature anneals to remove surface contamination. X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) were utilized to study the extent of surface contamination and surface roughness, respectively. The ammonium sulfide treatment provided the best overall removal of oxygen and carbon. Annealing over 700 °C after a treatment showed an even further improvement in surface contamination removal. The piranha treatment resulted in the lowest residual carbon, while the ammonium sulfide treatment leads to the lowest residual oxygen. AFM data showed that all the treatments decreased the surface roughness (with respect to as-grown specimens) with HCl, HF, (NH₄)₂S and RCA procedures giving the best RMS values (∼0.5-0.8 nm).     

Magnetic structure and collective Jahn-Teller distortions in nanostructured particles of CuFe2O4

The aim of the present work is to compare the structural, the composition and chemical state of the surface and magnetic properties of different nanosized CuFe₂O₄ powders exhibiting collective Jahn-Teller effect. The samples under examination consist of edged nanosized particles (needle like) with average length 1300 ± 20 nm and diameter 300 ± 20 nm obtained after high temperature synthesis, and superparamagnetic (at room temperature) spherical particles (d = 6 ± 2 nm), obtained by soft chemistry techniques. The surface composition of the particles was investigated by X-ray photoelectron spectroscopy (XPS). Mössbauer spectroscopy (MöS), including at high magnetic field up to 5 T and 4.2 K, was used for characterization of cation distribution in the samples. The data yielded by the XPS and MöS analyses for spherical nanosized particles led us to the assumption for the existence of a Jahn-Teller effect gradient—from the B-sublattice on the surface to a compensation of the tetragonal distortion in the two sublattices in the core. The analysis of the contribution of the anisotropy energy in edged and spherical nanoparticles shows that it must be considered as an effective value reflecting the influence of the individual factors depending on the particle shape and surface.     

Surface characterization of Pd/Ag23 wt% membranes after different thermal treatments

Hydrogen permeation measurements of 1.5-10 μm thick Pd/Ag23 wt% membranes before and after thermal treatments at 300 °C in air (both sides) or in the temperature range 300-450 °C in N₂ (feed side) and Ar (permeate side) were performed. Accompanying changes in surface topography and chemical composition were subsequently investigated by atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) depth profiling. For a 2 μm thick membrane, the surface roughness increased for all annealing temperatures applied, while a temperature of 450 °C was required for an increase in roughness of both membrane surfaces to occur for the 5 μm membrane. The thickest membrane, of 10 μm, showed changed surface roughness on one side of the membrane only and a slight decrease in hydrogen permeance after all heat treatments in N₂/Ar. X-ray photoelectron spectroscopy investigations performed after treatment and subsequent permeation measurements revealed segregation of silver to the membrane surfaces for all annealing temperatures applied. In comparison, heat treatment at 300 °C in air resulted in significantly increased hydrogen permeance accompanied by increasing surface roughness. Upon exposure to oxygen, Pd segregates to the surface to form a 2-3 nm thick oxide layer (PdO), with more complex segregation behavior after subsequent reduction and permeance measurements in pure hydrogen. The available permeance data for the Pd/Ag23 wt% membranes after heat treatment in air at 300 °C is found to depend linearly on the inverse membrane thickness, implying bulk limited hydrogen permeation for thicknesses down to 1.5-2.0 μm.     

Ultraviolet irradiation induced changes in the surface of phenolphthalein poly(ether sulfone) film

Changes in surface characteristics of phenolphthalein poly(ether sulfone) (PES-C) film induced by ultraviolet (UV) irradiation were investigated. The surface properties of the pristine and irradiated films were studied by attenuated total-reflection FTIR (FTIR-ATR), X-ray photoelectron spectroscopy (XPS), contact angle measurements and atomic force microscopy (AFM). It was found that photooxidation degradation took place on the sample surface after irradiation and the oxygen content in the surface increased as evidenced by FTIR-ATR and XPS results. The water contact angle of the irradiated films decreased with increasing irradiation time, which was ascribed to the increased polarity of the surface induced by photooxidation. The etching of ultraviolet irradiation induced the roughening of PES-C surface after irradiation with its root-mean-square roughness (RMS) determined by AFM increased from 2.097 nm before irradiation to 7.403 nm in the area of 25 μm × 25 μm.     

Composition and structure of chemically prepared GaAs(1 1 1)A and (1 1 1)B surfaces

The (1 1 1)A and (1 1 1)B surfaces of GaAs chemically treated in HCl-isopropanol solution (HCl-iPA) and annealed in vacuum were studied by means of X-ray photoelectron spectroscopy (XPS), low-energy electron diffraction (LEED) and electron energy loss spectroscopy (EELS). To avoid uncontrolled contamination, chemical treatment and sample transfer into UHV were performed under pure nitrogen atmosphere. The HCl-iPA treatment removes gallium and arsenic oxides, with about 0.5-3 ML of elemental arsenic being left on the surface, depending on the crystallographic orientation. With the increase of the annealing temperature, a sequence of reconstructions were identified by LEED: (1 × 1) and (2 × 2) on the (1 1 1)A surface and (1 × 1), (2 × 2), (1 × 1), (3 × 3), (√19 × √19) on the (1 1 1)B surface. These sequences of reconstructions correspond to the decrease of surface As concentration. The structural properties of chemically prepared GaAs(1 1 1) surfaces were found to be similar to those obtained by decapping of As-capped epitaxial layers.     

Interface evolution during electrochemical oxidation-dissolution

We present results from an experimental study on the roughening of Al thin film during electrochemical oxidation reduction. The surface reaction occurred in two stages. Anodic alumina forms during oxidation of aluminum followed by immediate dissolution of alumina. The surface image using AFM showed randomly oriented grains with lateral feature size ∼280 nm at early stage (30 s) of oxidation-dissolution (OD). As farther dissolution of alumina (90 s) progressed, oriented rectangular grains were observed with lateral feature size ∼400 nm, indicating a disordered to ordered transition at the surface. The roughness exponent at the earlier stage found to be 0.44 ± 0.02, consistent with nonlinear KPZ equation. However, for the later case, roughness exponent increased to 0.84 ± 0.03, which is close to the value derived in continuum model. The value of dissolution exponent (growth exponent) β found to be 0.47 ± 0.1. These values are slightly different from the theoretical values but they are consistent with the theoretical models within the experimental error. Shadow instability found to be a dominant feature in this experiment and contributed to the discrepancy. Interface instabilities are discussed in terms of local and non-local effects.     

Structural and optical properties of zinc nitride films prepared by rf magnetron sputtering

Zinc nitride films were prepared on quartz substrates by rf magnetron sputtering using pure zinc target in N₂-Ar plasma. X-ray diffraction (XRD) analysis indicates that the films just after deposition are polycrystalline with a cubic structure and a preferred orientation of (4 0 0). X-ray photoelectron spectroscopy (XPS) analysis also confirms the formation of N-Zn bonds and the substitution incorporation of oxygen for nitrogen on the surface of the films. The optical band gap is calculated from the transmittance spectra of films just after deposition, and a direct band gap of 1.01 ± 0.02 eV is obtained. Room temperature PL measurement is also performed to investigate the effect of defect on the band gap and quality of the zinc nitride films.     

Molecular adsorption and growth of naphthalene films on Ag(1 0 0)

The adsorption of naphthalene, vacuum deposited on a Ag(1 0 0) surface, was comprehensively investigated by means of low-energy electron diffraction (LEED), temperature-programmed thermal desorption (TPD) spectroscopy, X-ray photoelectron spectroscopy (XPS), and polarization-dependent near-edge X-ray absorption fine structure (NEXAFS) spectroscopy in the mono- and multilayer regime. A growth of long-range ordered monolayer at 140 K is observed with LEED. The polarization-dependent C 1s NEXAFS shows that the naphthalene molecules in the monolayer lie almost parallel to the Ag(1 0 0) surface. With increasing film thickness, the molecular orientation turns to upright position. Furthermore, NEXAFS measurements show that in the multilayer regime the molecular orientation depends on the substrate temperature during deposition.     

Pentacene islands grown on ultra-thin SiO2

Ultra-thin oxide (UTO) films were grown on Si(1 1 1) in ultrahigh vacuum at room temperature and characterized by scanning tunneling microscopy. The ultra-thin oxide films were then used as substrates for room temperature growth of pentacene. The apparent height of the first layer is 1.57 ± 0.05 nm, indicating “standing up” pentacene grains in the thin film phase were formed. Pentacene is molecularly resolved in the second and subsequent molecular layers. The measured in-plane unit cell for the pentacene (0 0 1) plane (ab plane) is a = 0.76 ± 0.01 nm, b = 0.59 ± 0.01 nm, and γ = 87.5 ± 0.4°. The films are unperturbed by the UTO’s short-range spatial variation in tunneling probability, and reduce its corresponding effective roughness and correlation exponent with increasing thickness. The pentacene surface morphology follows that of the UTO substrate, preserving step structure, the long range surface rms roughness of ∼0.1 nm, and the structural correlation exponent of ∼1.     

Surface modification of porous poly(tetrafluoraethylene) film by a simple chemical oxidation treatment

A simple, inexpensive and environmental chemical treatment process, i.e., treating porous poly(tetrafluoroethylene) (PTFE) films by a mixture of potassium permanganate solution and nitric acid, was proposed to improve the hydrophilicity of PTFE. To evaluate the effectiveness of this strong oxidation treatment, contact angle measurement was performed. The effects of treatment time and temperature on the contact angle of PTFE were studied as well. The results showed that the chemical modification decreased contact angle of as-received PTFE film from 133 ± 3° to 30 ± 4° treated at 100 °C for 3 h, effectively converting the hydrophobic PTFE to a hydrophilic PTFE matrix. The changes in chemical structure, surface compositions and crystal structure of PTFE were examined by attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), environmental scanning electron microscopy (ESEM), X-ray diffraction (XRD), respectively. It was found that the F/C atomic ratio decreased from untreated 1.65-0.10 treated by the mixture at 100 °C for 3 h. Hydrophilic groups such as carbonyl (CO) and hydroxyl (OH) were introduced on the surface of PTFE after treatment. Furthermore, hydrophilic compounds K_0.27MnO₂·0.54H₂O was absorbed on the surface of porous PTFE film. Both the introduction of hydrophilic groups and absorption of hydrophilic compounds contribute to the significantly decreased contact angle of PTFE.     

Generation of oxygen vacancies in the surface of ferroelectric Pb(Nb,Zr,Ti)O3

Controlled generation of oxygen vacancies in the surface of ferroelectric thin films is crucial to study how surface reduction affects molecular adsorption and catalysis of gas-surface phenomena. We demonstrate the effective reduction in the surface of 4% niobium doped 20/80 PZT (PNZT) thin films. The sample was characterized by X-ray diffraction (XRD), Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM), and heated at 200, 250 and 300 °C in a high vacuum system at 10⁻⁵ T of H₂. Auger peak-to-peak intensities was used to study the elemental concentrations during the reduction experiment. High-resolution XPS spectra were acquired before and after reduction process for detecting the changes of the oxygen signal. Vacancies production rates as slow as 0.21% per minute were achieved and the temperature was not a key parameter in the process. Experiments at higher hydrogen pressures and lower temperatures might improve the control of the vacancies production.     

Surface chemistry of atmospheric plasma modified polycarbonate substrates

Surface of polycarbonate substrates were activated by atmospheric plasma torch using different gas pressure, distance from the substrates, velocity of the torch and number of treatments. The modifications were analyzed by contact angle measurements, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and UV-vis spectrophotometry. Plasma treatment caused the surface characteristics to become more hydrophilic as measured by the water contact angle, which decreased from 88° to 18°. The decrease in contact angle was mainly due to oxidation of the surface groups, leading to formation of polar groups with hydrophilic property. XPS results showed an increase in the intensity of -(C-O)- groups and also introduction of new functional groups i.e. -(O-CO)- after the treatment process. AFM topographic images demonstrated an increase in the rms roughness of the surface from 2.0 nm to 4.0 nm caused by the treatment. Increase in rms roughness of the surface caused relevant decrease in transmission up to ∼2-5%.     

Evaluation of nanoscale roughness measurements on a plasma treated SU-8 polymer surface by atomic force microscopy

A comparison between roughness data obtained with an atomic force microscope (AFM) on different surfaces requires reliable roughness parameters. In order to specify the appropriate parameters for nanoscale roughness measurements, we compared the root mean square (rms) roughness and the relative surface area (sdr) as function of varying scan size, speed and pixel size. By using oxygen plasma (24 kJ) treated SU-8 with an average rms roughness of 2.6 ± 0.5 nm as reference surface, the repeatability of the method was evaluated for dynamic (tapping) and contact mode. The evaluation of AFM images indicated a decrease of the effective tip radius after a few measurements. This degradation of the tip lowers the resolution of the image and can affect roughness measurements.     

Oxidation studies of niobium thin films at room temperature by X-ray reflectivity

We report the results of growth kinetics of oxidation process on niobium thin film surfaces exposed to air at room temperature by using a surface sensitive non-destructive X-ray reflectivity technique. The oxidation process follows a modified Cabrera-Mott model of thin films. We have shown that the oxide growth is limited by the internal field due to the contact potential which develops during the initial stage of oxidation. The calculated contact potential for 100 and 230 Å thick films is 0.81 ± 0.14 and 1.20 ± 0.11 V respectively. We report that 40% increase in the contact potential increases the growth rate for the first few mono layers of Nb₂O₅ from ∼2.18 to ∼2790 Å/s. The growth rates of oxidation on these samples become similar after the oxide thicknesses of ∼25 Å are reached. We report on the basis of our studies that a protective layer should be grown in situ to avoid oxidation of Nb thin film surface of Nb/Cu cavities.     

Self-assembled monolayers of flufenaminate anions on mild steel surface formed in aqueous solution

Adsorption of derivative of phenylanthranilic acid - flufenamic acid (FFA) on the “oxide-free” and oxidized surface of mild steel in neutral borate buffer solution was studied by ellipsometry and XPS. Anodic polarization curves reveal that complete suppression of the anodic dissolution of iron is achieved at FFA concentration C_in = 3.8 mM. Besides, adding FFA substantially shifts the pitting potential from 0.06 V to 0.67 V. Ellipsometric studies have shown that at the applied potential −0.65 V, when the surface is free from the oxide layer, FFA forms monomolecular layer. To characterize the surface layers formed after exposing the sample in 5 mM FFA solution the XPS was used to assess the composition and the thickness of the layers. Using the intensities of the Fe 2p, Fe 3p, N 1s, F 1s, O 1s and C 1s and analyzing the angle resolved XPS data the FFA molecules have been shown to form monomolecular layer in which FFA is (vertically or slightly inclined) anchored by iron cations through oxygen atoms of carboxyl group to the surface and the fluorine atoms of CF₃ groups form the utmost layer. Similar orientation is also assumed for FFA molecules adsorbed on the oxidized iron surface. It seems that the layer formed by FFA or similar molecules may serve a robust interface for grafting other substances on such a functionalized surface.     

Investigation of chemical mechanical polishing of zinc oxide thin films

Zinc oxide has become an important material for various applications. Commercially available zinc oxide single crystals and as-grown zinc oxide thin films have high surface roughness which has detrimental effects on the growth of subsequent layers and device performance. A chemical mechanical polishing (CMP) process was developed for the polishing of zinc oxide polycrystalline thin films. Highly smooth surfaces with RMS roughness <6 Å (as compared to the initial roughness of 26 ± 6 Å) were obtained under optimized conditions with removal rates as high as 670 Å/min. Effects of various CMP parameters on removal rate and surface roughness were evaluated. The role of pH on the polishing characteristics was investigated in detail.