Quantitative analysis of multi-element oxide thin films by angle-resolved XPS: Application to ultra-thin oxide films on MgAl substrates

An original procedure has been developed for the quantitative analysis and microstructural interpretation of angle-resolved X-ray photoelectron spectra (AR-XPS) of very thin (<6 nm), multi-element oxide films as grown on metallic binary alloy substrates by, e.g., thermal or plasma oxidation. To this end, first an approach has been given to retrieve the different metallic, oxidic and oxygen primary zero-loss (PZL) intensities from the measured AR-XPS spectra of the bare and oxidized alloy. The principal equations for the determination of the oxide-film thickness, composition and constitution from the resolved PZL intensities have been presented. On this basis, various corresponding calculation routes have been distinguished. The procedure has been applied to the case of very thin (<6 nm), mixed (Mg, Al)-oxide films on bare Mg-based MgAl substrates as grown by dry, thermal oxidation at room temperature. The results obtained on the thickness, composition, defect structure and constitution of the oxide-film have been discussed as function of the bulk Al alloying content and the applied partial pressure of oxygen.     

Perpendicular magnetic anisotropy of ultrathin FeCo alloy films on Pd(0 0 1) surface: First principles study

Using the full potential linearized augmented plane wave (FLAPW) method, thickness dependent magnetic anisotropy of ultrathin FeCo alloy films in the range of 1 monolayer (ML) to 5 ML coverage on Pd(0 0 1) surface has been explored. We have found that the FeCo alloy films have close to half metallic state and well-known surface enhancement in thin film magnetism is observed in Fe atom, whereas the Co has rather stable magnetic moment. However, the largest magnetic moment in Fe and Co is found at 1 ML thickness. Interestingly, it has been observed that the interface magnetic moments of Fe and Co are almost the same as those of surface elements. The similar trend exists in orbital magnetic moment. This indicates that the strong hybridization between interface FeCo alloy and Pd gives rise to the large magnetic moment. Theoretically calculated magnetic anisotropy shows that the 1 ML FeCo alloy has in-plane magnetization, but the spin reorientation transition (SRT) from in-plane to perpendicular magnetization is observed above 2 ML thickness with huge magnetic anisotropy energy. The maximum magnetic anisotropy energy for perpendicular magnetization is as large as 0.3 meV/atom at 3 ML film thickness with saturation magnetization of . Besides, the calculated X-ray magnetic circular dichroism (XMCD) has been presented.     

Substrate effect on electronic sputtering yield in polycrystalline fluoride (LiF, CaF2 and BaF2) thin films

Influence of substrate on electronic sputtering of fluoride (LiF, CaF₂ and BaF₂) thin films, 10 and 100 nm thin, under dense electronic excitation of 120 MeV Ag²⁵⁺ ions irradiation is investigated. The sputtering yield of the films deposited on insulating (glass) and semiconducting (Si) substrates are determined by elastic recoil detection analysis technique. Results revealed that sputtering yield is higher, up to 7.4 × 10⁶ atoms/ion for LiF film on glass substrate, than that is reported for bulk materials/crystals (∼10⁴ atoms/ion), while a lower value of the yield (2.3 × 10⁶ atoms/ion) is observed for film deposited on Si substrate. The increase in the yield for thin films as compared to bulk material is a combined effect of the insulator substrate used for deposition and reduced film dimension. The results are explained in the framework of thermal spike model along with substrate and size effects in thin films. It is also observed that the material with higher band gap showed higher sputtering yield.     

AFM lateral force imagining of modified polychloroprene: A study based on roughness analysis

Films of a binary polymer blends comprising polychloroprene (PCP) and piperylene-styrene copolymer (PSC) have been prepared by solution casting. The dependence of the surface morphology of the free blend films on PSC content was studied with both roughness and correlation analysis of lateral force microscopy (LFM) images. Significant changes in roughness and lateral parameter values of different blend film sides have been observed depending on the blend composition. It was shown that up to 15 wt.% PSC is distributed continuously in PCP bulk. The increase of roughness and lateral parameter values at the air/film surface shows the enrichment of PCP in the blends containing 25 wt.% or more PSC. The enrichment of PCP on the air/film surface favours the increase of PSC concentration at the backing/film surface. The films underside morphology becomes similar to that of PSC, when its content reaches 40 wt.%.     

Magnetization reversal in bulk and thin films of the ferrimagnetic ErCo0.50Mn0.50O3 perovskite

We present herein a comparison of the magnetic properties of bulk ceramics and thin films of the ferrimagnetic ErCo_0.50Mn_0.50O₃ compound. Epitaxial thin films were deposited onto (1 0 0) SrTiO₃ substrates by pulsed-laser ablation while bulk ceramics were prepared by solid state reaction. When cooling under low applied fields, a spin reversal is observed in both thin film and bulk due to the competition between two magnetic sublattices (Co/Mn and Er) coupled by a negative exchange interaction. Original features are observed in the M(H) loops for bulk materials: abrupt jumps at 4 T due to a reorientation of domains, while in the low field region, the increasing and decreasing branches of the magnetization intersect each other. In the thin film, the ordering temperature increased from 69 to 75 K, and the ZFC anomaly (AF transition) became sharper, compared to the bulk specimen. The oxygen content and the microstructure are crucial to observe the intersection of the magnetization branches.     

Morphology and composition of nanoscale surface oxides on Fe–20Cr–18Ni{1 1 1} austenitic stainless steel

Surface oxidation ranging from initial stages to the onset of passive oxide layer formation have been investigated on Fe–20Cr–18Ni{1 1 1} single crystal surface by X-ray photoelectron spectroscopy (XPS). Surface segregation of the alloying elements and the morphology of the surface oxide nanostructure were characterized quantitatively by inelastic electron background analysis. Our results demonstrate that by increasing the oxidation temperature the relative concentrations of Fe²⁺ and Fe³⁺ cations increase due to their enhanced mobility. Higher temperature also improves the mobility of chromium, thus enhancing its segregation to the oxygen-rich surface and thereby reinforcing the passive layer on the alloy. This is in agreement with the results showing the sudden decrease in oxide film thickness at the oxidation temperatures exceeding 600 K. Additionally, a pronounced segregation of metallic nickel is found in the interface between the surface oxide layer and the bulk alloy.     

Mechanical properties of sol-gel derived lead zirconate titanate thin films by nanoindentation

Lead zirconate titanate (PZT) thin films are deposited on platinized silicon substrate by sol-gel process. The crystal structure and surface morphology of PZT thin films are characterized by X-ray diffraction and atomic force microscopy. Depth-sensing nanoindentation system is used to measure mechanical characteristics of PZT thin films. X-ray diffraction analyses confirm the single-phase perovskite structures of all PZT thin films. Nanoindentation measurements reveal that the indentation modulus and hardness of PZT thin films are related with the grain size and crystalline orientation. The increases of the indentation modulus and hardness with grain size are observed, indicating the reverse Hall-Petch effect. Furthermore, the indentation modulus of (1 1 1)-oriented PZT thin film is higher than those of (1 0 0)- and random-oriented films. The consistency between experimental data and numerical results of the effective indentation moduli for fiber-textured PZT thin films using Voigt-Reuss-Hill model is obtained.     

Field emission measured from nanostructured germanium and silicon thin films

We have prepared nanostructured thin films of germanium and silicon. The films were grown by an ion beam sputtering technique followed by a rapid annealing step using an electron beam annealer. The annealing temperature is a comparatively low 500 °C, resulting in well defined nano-islands on the film surface. Electron field emission has been measured from the surfaces under high vacuum. The threshold electric field value for significant current flow was measured as 2.5 V μm⁻¹ for a silicon thin film which is comparable to other silicon technologies. A value of 0.5 V μm⁻¹ for a germanium thin film represents an order of magnitude improvement for related germanium nanostructured systems.     

Surface chemical states of barium zirconate titanate thin films prepared by chemical solution deposition

Ba(Zr_0.05Ti_0.95)O₃ (BZT) thin films grown on Pt/Ti/SiO₂/Si(1 0 0) substrates were prepared by chemical solution deposition. The structural and surface morphology of BZT thin films has been studied by X-ray diffraction (XRD) and scanning electron microscope (SEM). The results showed that the random oriented BZT thin film grown on Pt/Ti/SiO₂/Si(1 0 0) substrate with a perovskite phase. The SEM surface image showed that the BZT thin film was crack-free. And the average grain size and thickness of the BZT film are 35 and 400 nm, respectively. Furthermore, the chemical states and chemical composition of the films were determined by X-ray photoelectron spectroscopy (XPS) near the surface. The XPS results show that Ba, Ti, and Zr exist mainly in the forms of BZT perovskite structure.     

The effect of heat treatment on the physical properties of sol-gel derived ZnO thin films

Zinc oxide (ZnO) thin films were deposited on microscope glass substrates by sol-gel spin coating method. Zinc acetate (ZnAc) dehydrate was used as the starting salt material source. A homogeneous and stable solution was prepared by dissolving ZnAc in the solution of monoethanolamine (MEA). ZnO thin films were obtained after preheating the spin coated thin films at 250 °C for 5 min after each coating. The films, after the deposition of the eighth layer, were annealed in air at temperatures of 300 °C, 400 °C and 500 °C for 1 h. The effect of thermal annealing in air on the physical properties of the sol-gel derived ZnO thin films are studied. The powder and its thin film were characterized by X-ray diffractometer (XRD) method. XRD analysis revealed that the annealed ZnO thin films consist of single phase ZnO with wurtzite structure (JCPDS 36-1451) and show the c-axis grain orientation. Increasing annealing temperature increased the c-axis orientation and the crystallite size of the film. The annealed films are highly transparent with average transmission exceeding 80% in the visible range (400-700 nm). The measured optical band gap values of the ZnO thin films were between 3.26 eV and 3.28 eV, which were in the range of band gap values of intrinsic ZnO (3.2-3.3 eV). SEM analysis of annealed thin films has shown a completely different surface morphology behavior.     

Microstructure of epitaxial SrRuO3 thin films on MgO substrates

SrRuO₃ thin films have been grown on singular (1 0 0) MgO substrates using pulsed laser deposition (PLD) in 30 Pa oxygen ambient and at a temperature of 400-700 °C. Ex situ reflection high-energy electron diffraction (RHEED) as well as X-ray diffraction (XRD) θ/2θ scan indicated that the films deposited above 650 °C were well crystallized though they had a rough surface as shown by atom force microscopy (AFM). XRD Φ scans revealed that these films were composed of all three different types of orientation domains, which was further confirmed by the RHEED patterns. The heteroepitaxial relationship between SrRuO₃ and MgO was found to be [1 1 0] SRO//[1 0 0] MgO and 45°-rotated cube-on-cube [0 0 1] SRO//[1 0 0] MgO. These domain structures and surface morphology are similar to that of ever-reported SrRuO₃ thin films deposited on the (0 0 1) LaAlO₃ substrates, and different from those deposited on (0 0 1) SrTiO₃ substrates that have an atomically flat surface and are composed of only the [1 1 0]-type domains. The reason for this difference was ascribed to the effect of lattice mismatch across the film/substrate interface. The room temperature resistivity of SrRuO₃ films fabricated at 700 °C was 300 μΩ cm. Therefore, epitaxial SrRuO₃ films on MgO substrate could serve as a promising candidate of electrode materials for the fabrication of ferroelectric or dielectric films.     

Electrical transport and magnetic properties of perovskite-type electron-doped La–Pr–Mn–O epitaxial films

La_1−xPr_xMnO₃ (LPrMO) thin films have been epitaxially grown on (1 0 0)SrTiO₃ single-crystal substrates by pulsed-laser deposition. The films have a perovskite structure and give rise to the colossal magnetoresistance effect with the maximum magnetoresistance ratio of 10³% (at 240 K and 5 T). The electrical transport and magnetic properties have been investigated for the La_0.8Pr_0.2MnO₃ film with thickness 3000 Å. The results indicate that the films have quite a distinctive magnetotransport behavior compared to the bulk. The analysis of X-ray photoemission spectroscopy suggests that the valence state of Pr is 4+ in LPrMO film. Therefore, the epitaxial film is most likely an electron-doped colossal magnetoresistance system.     

Growth of thin Fe(0 0 1) films for terahertz emission experiments

The electrical and magnetic properties of thin iron (Fe) films have sparked significant scientific interest. Our interest, however, is in the fundamental interactions between light and matter. We have discovered a novel application for thin Fe films. These films are sources of terahertz (THz) radiation when stimulated by an incident laser pulse. After intense femtosecond pulse excitation by a Ti:sapphire laser, these films emit picosecond, broadband THz frequencies. The terahertz emission provides a direct measure of the induced ultrafast change in magnetization within the Fe film. The THz generation experiments and the growth of appropriate thin Fe films for these experiments are discussed. Several criteria are used to select the substrate and film growth conditions, including that the substrate must permit the epitaxial growth of a continuous, monocrystalline or single crystal film, yet must also be transparent to the emitted THz radiation. An Fe(0 0 1) film grown on the (0 0 1) surface of a magnesium oxide (MgO) substrate makes an ideal sample. The Fe films are grown by physical vapor deposition (PVD) in an ultrahigh vacuum (UHV) system. Low energy electron diffraction (LEED) and Auger electron spectroscopy (AES) are used to characterize the Fe(0 0 1) films. Two substrate surface preparation methods are investigated. Fe(0 0 1) films grown on MgO(0 0 1) substrates that are used as-received and films grown on MgO(0 0 1) substrates that have been UV/ozone-cleaned ex vacuo and annealed in vacuo produce the same results in the THz generation experiments. Either substrate preparation method permits the growth of samples suitable for the THz emission experiments.     

Epitaxial growth and structural characterization of Pb(Fe1/2Nb1/2)O3 thin films

We have grown lead iron niobate thin films with composition Pb(Fe_1/2Nb_1/2)O₃ (PFN) on (0 0 1) SrTiO₃ substrates by pulsed laser deposition. The influence of the deposition conditions on the phase purity was studied. Due to similar thermodynamic stability spaces, a pyrochlore phase often coexists with the PFN perovskite phase. By optimizing the kinetic parameters, we succeeded in identifying a deposition window which resulted in epitaxial perovskite-phase PFN thin films with no identifiable trace of impurity phases appearing in the X-ray diffractograms. PFN films having thicknesses between 20 and 200 nm were smooth and epitaxially oriented with the substrate and as demonstrated by RHEED streaks which were aligned with the substrate axes. X-ray diffraction showed that the films were completely c-axis oriented and of excellent crystalline quality with low mosaicity (X-ray rocking curve FWHM?0.09°). The surface roughness of thin films was also investigated by atomic force microscopy. The root-mean-square roughness varies between 0.9 nm for 50-nm-thick films to 16 nm for 100-nm-thick films. We also observe a correlation between grain size, surface roughness and film thickness.     

Structural properties of CuInSe2 films prepared by selenization of metallic precursors on MoNx film substrates

The aim of this work was to study the effect of MoN_x film substrates on the structural properties of CuInSe₂ films prepared by selenization of metallic Cu-In alloy precursors. MoN_x films were prepared by reactive dc-magnetron sputtering. All the CuInSe₂ films exhibit single phase chalcopyrite structure with (1 1 2) preferred orientation, which can be explained by the reduction of lattice mismatch between CuInSe₂ and MoN_x. The bulk composition of selenized CuInSe₂ films are near stoichiometric, but the surface composition analysis suggests Cu deficiency on surface area. Furthermore, ordered defect compound, CuIn₂Se_3.5 is found on the surface of CuInSe₂ films. The results will be helpful for fabricating Cd-free ZnO buffer layer CuInSe₂ and Cu(In_1−xGa_x)Se₂ based thin film solar cells.     

As-grown preparation of FePt-ordered alloy thin films from Pt/Fe bi-layered structure

A novel method to fabricate FePt-ordered alloy thin films with (0 0 1) preferential orientation from Pt/Fe bi-layered films has been developed. It is able to omit post-annealing with a furnace, and the whole process can be conducted in a chamber without exposing samples to air. In this method, the inter-diffusion and the hetero-epitaxial relation between Fe and Pt are key factors to attain an FePt-ordered alloy thin film with (0 0 1) preferential orientation. An FePt-ordered alloy thin film with (0 0 1) preferential orientation fabricated from Pt[3 nm]/Fe[3 nm] bi-layer employing this method exhibited a relatively large coercivity of 5.6 kOe and high squareness ratio of 0.94 on perpendicular magnetization property. This novel method has a potential to fabricate FePt-based perpendicular magnetic recording media more easily than several conventional methods.     

Effect of temperature on pulsed laser deposition of HgCdTe films

HgCdTe thin films have been deposited on Si(1 1 1) substrates at different substrate temperatures by pulsed laser deposition (PLD). An Nd:YAG pulsed laser with a wavelength of 1064 nm was used as laser source. The influences of the substrate temperature on the crystalline quality, surface morphology and composition of HgCdTe thin films were characterized by X-ray diffraction (XRD), selected area electron diffraction (SAED), atomic force microscopy (AFM) and energy dispersive X-ray spectroscopy (EDS). The results show that in our experimental conditions, the HgCdTe thin films deposited at 200 °C have the best quality. When the substrate temperature is over 250 °C, the HgCdTe film becomes thermodynamically unstable and the quality of the film is degraded.     

Properties of CuIn(SxSe1−x)2 polycrystalline thin films prepared by chemical spray pyrolysis

CuIn(S_xSe_1−x)₂ thin polycrystalline films were grown by the chemical spray pyrolysis method on the glass substrate at 280-400°C. The alloy composition in the film was studied with relation to that in the splay solution. Films were characterized by X-ray diffraction, optical absorption, Raman spectroscopy, resistivity and surface morphology. The CuInSe₂-rich alloy films grown at high substrate temperature had chalcopyrite structure, while, the CuInS₂-rich films grown at low substrate temperature exhibited sphalerite structure. Optical-gap energies were smaller than that of the bulk crystal by 0.1-0.2 eV for CuInS₂-rich films. Raman spectra exhibited both CuInSe₂-like and CuInS₂-like A₁ modes, and their relative changed systematically with alloy composition.     

Effect of substrate temperature and annealing temperature on the structural, electrical and microstructural properties of thin Pt films by rf magnetron sputtering

Influence of both substrate temperature, T_s, and annealing temperature, T_a, on the structural, electrical and microstructural properties of sputtered deposited Pt thin films have been investigated. X-ray diffraction results show that as deposited Pt films (T_s = 300, 400 °C) are preferentially oriented along (1 1 1) direction. A little growth both along (2 0 0) and (3 1 1) directions are also noticed in the as deposited Pt films. After annealing in air (T_a = 500-700 °C), films become strongly oriented along (1 1 1) plane. With annealing temperature, average crystallite size, D, of the Pt films increases and micro-strain, e, and lattice constant, a₀, decreases. Residual strain observed in the as deposited Pt films is found to be compressive in nature while that in the annealed films is tensile. This change in the strain from compressive to tensile upon annealing is explained in the light of mismatch between the thermal expansion coefficients of the film material and substrate. Room temperature resistivity of Pt films is dependant on both the T_s and T_a of the films. Observed decrease in the film resistivity with T_a is discussed in terms of annihilation of film defects and grain-boundary. Scanning electron microscopic study reveals that as the annealing temperature increases film densification improves. But at an annealing temperature of ∼600 °C, pinholes appear on the film surface and the size of pinhole increases with further increase in the annealing temperature. From X-ray photoelectron spectroscopic analysis, existence of a thin layer of chemisorbed atomic oxygen is detected on the surfaces of the as deposited Pt films. Upon annealing, coverage of this surface oxygen increases.