FTIR and spectroscopic ellipsometry investigations of the electron beam evaporated silicon oxynitride thin films

FTIR and variable angle spectroscopic ellipsometer in conjunction with computer simulation were employed to investigate the electron beam evaporated SiO_xN_y thin films. FTIR showed a large absorption band located between 600 and 1250 cm⁻¹, which indicates that Si-O and Si-N bands are overlap in SiO_xN_y films. A three layers model was used to fit the calculated data to the experimental ellipsometric spectra. The main layer was described by Cauchy model while the interface layer and the surface layer were described using Tauc-Lorenz oscillator and Bruggeman effective medium approximation, respectively. The thickness, the refractive index and the extinction coefficient were accurately determined. The refractive index at 630 nm was found to increase from 1.74 to 1.85 with increasing the film thickness from 191.6 to 502.2 nm. The absorption coefficient was calculated from the obtained extinction coefficient values and it has been used to calculate the Tauc and Urbach energies.     

Post-annealing effect upon optical properties of electron beam evaporated molybdenum oxide thin films

Molybdenum oxide (MoO₃) thin films were deposited by electron beam evaporation. The chemical composition, microstructure, optical and electrical properties of MoO₃ thin films depend on the annealing temperature and ambient atmosphere. X-ray diffraction (XRD) shows that crystalline MoO₃ films can be obtained at various post-annealing temperatures from 200 to 500 °C in N₂ and O₂. X-ray photoelectron spectroscopy (XPS) results reveal that the O-1s emission peak was shifted slightly toward lower binding energies as the annealing temperature in N₂ was increased. The oxygen vacancies and conductivity of MoO₃ film increased with the annealing temperature. However, when the MoO₃ films were annealed in an atmosphere of O₂, the optical transmission, the O/Mo ratio and the photon energy increased with the annealing temperature. The results differ from those for films annealed in a N₂ atmosphere.     

Cathodoluminescence properties of silicon nanocrystallites embedded in silicon oxide thin films

Cathodoluminescence (CL) spectra for the Si nanocrystallites embedded in a matrix of silicon oxide films are measured at room temperature. The CL spectra consist of two principal bands whose peak energies are in a near-infrared (NIR) region (<1.6 eV) and in a blue region (2.6 eV), respectively. The spectral feature of the NIR CL band is similar to the corresponding PL spectra. The strong correlation between the presence of Si nanocrystallites and the formation of the NIR CL band are found as well as the PL spectrum. The peak energy of the blue CL band is slightly lower than that of the luminescence band originating from oxygen vacancies (≡Si–Si≡) in SiO₂. Therefore, the blue CL band is considered to come from Si_n clusters with n3 in the oxide matrix. Under irradiation of electron beams, degradation of the intensity is observed for both the CL bands but the decay characteristics are different.     

Photoluminescence from Er-doped silicon rich oxide thin films

 Photoluminescence (PL) properties of Er-doped silicon rich oxide thin films deposited on Si substrate by co-evaporation of silicon monoxide and Er under different atmospheres are investigated. The samples exhibit luminescence peak at 1.54 μm which could be assigned to the recombination in intra-4f Er³⁺ transition. PL shows that this transition is highest when ammonia atmosphere is used during deposition followed by an annealing temperature at 850 °C in 95% N₂+5% H₂ gas (forming gas). In fact, we believe that the presence of the N atoms around Er ions increases the intensity of the 1.54 μm luminescence.     

Low reflectance sputtered vanadium oxide thin films on silicon

Vanadium oxide thin films on silicon (Si) substrate are grown by pulsed radio frequency (RF) magnetron sputtering technique at RF power in the range of 100–700 W at room temperature. Deposited thin films are characterized by field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) techniques to investigate microstructural, phase, electronic structure and oxide state characteristics. The reflectance and transmittance spectra of the films and the Si substrate are recorded at the solar region (200–2300 nm) of the spectral window. Substantial reduction in reflectance and increase in transmittance is observed for the films grown beyond 200 W. Further, optical constants viz. absorption coefficient, refractive index and extinction coefficient of the deposited vanadium oxide films are evaluated.     

Ionic conductivity study on electron beam irradiated polyacrylonitrile-polyethylene oxide gel

Different mass percent polyacrylonitrile (PAN)-polyethylene oxide (PEO) gels were prepared and irradiated by an electron beam (EB) with energy of 1.0 MeV to the dose ranging from 13 kGy to 260 kGy.The gels were analysed by using Fourier transform infrared spectrum,gel fraction and ionic conductivity (IC) measurement.The results show that the gel is crosslinked by EB irradiation,the crosslinking degree rises with the increasing EB irradiation dose (ID) and the mass percents of both PAN and PEO contribute a lot to the crosslinking;in addition,EB irradiation can promote the IC of PAN-PEO gels.There exists an optimum irradiation dose,at which the IC can increase dramatically.The IC changes of the PAN-PEO gels along with ID are divided into three regions:IC rapidly increasing region,IC decreasing region and IC balanced region.The cause of the change can be ascribed to two aspects,gel capturing electron degree and crosslinking degree.By comparing the IC-ID curves of different mass percents of PAN and PEO in gel,we found that PAN plays a more important role for gel IC promotion than PEO,since addition of PAN in gel causes the IC-ID curve sharper,while addition of PEO in gel causes the curve milder.     

Deep UV laser induced luminescence in oxide thin films

Time-resolved luminescence experiments have been set up in order to study the interaction of 193-nm laser radiation with dielectric thin films. At room temperature, Al₂O₃ coatings show photoluminescence upon ArF excimer laser irradiation, with significant intensity contributions besides the known substrate emission. Time- and energy-resolved measurements indicate the presence of oxygen-defect centers in Al₂O₃ coatings, which suggests a strong single-photon interaction at 193 nm by F⁺ and F center absorption. Measurements on highly reflective thin-film stacks, consisting of quarter-wave Al₂O₃ and SiO₂ layers, indicate similar UV excitations, mainly from color centers of Al₂O₃. Received: 20 February 2002 / Accepted: 11 April 2002 / Published online: 5 July 2002     

The Rayleigh law in silicon doped hafnium oxide ferroelectric thin films

A wealth of studies have confirmed that the low‐field hysteresis behaviour of ferroelectric bulk ceramics and thin films can be described using Rayleigh relations, and irreversible domain wall motion across the array of pining defects has been commonly accepted as the underlying micro‐mechanism. Recently, HfO₂ thin films incorporated with various dopants were reported to show pronounced ferroelectricity, however, their microscopic domain structure remains unclear till now. In this work, the effects of the applied electric field amplitude, frequency and temperature on the sub‐coercive polarization reversal properties were investigated for 10 nm thick Si‐doped HfO₂ thin films. The applicability of the Rayleigh law to ultra‐thin ferroelectric films was first confirmed, indicating the existence of a multi‐domain structure. Since the grain size is about 20–30 nm, a direct observation of domain walls within the grains is rather challenging and this indirect method is a feasible approach to resolve the domain structure. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Epitaxial ZnO thin films grown by pulsed electron beam deposition

In this work, the pulsed electron beam deposition method (PED) is evaluated by studying the properties of ZnO thin films grown on c-cut sapphire substrates. The film composition, structure and surface morphology were investigated by means of Rutherford backscattering spectrometry, X-ray diffraction and atomic force microscopy. Optical absorption, resistivity and Hall effect measurements were performed in order to obtain the optical and electronic properties of the ZnO films. By a fine tuning of the deposition conditions, smooth, dense, stoichiometric and textured hexagonal ZnO films were epitaxially grown on (0001) sapphire at 700 °C with a 30° rotation of the ZnO basal plane with respect to the sapphire substrate. The average transmittance of the films reaches 90% in the visible range with an optical band gap of 3.28 eV. Electrical characterization reveals a high density of charge carrier of 3.4 × 10¹⁹ cm^?3 along with a mobility of 11.53 cm²/Vs. The electrical and optical properties are discussed and compared to ZnO thin films prepared by the similar and most well-known pulsed laser deposition method.     

氧化物薄膜研制中的电子能谱技术

随着科学技术的不断发展，人们正在寻求更新的实用材料．金属氧化物，包括金属氧化物薄膜的各种实用材料，在工业界、信息产业界和能源开发等方面的应用前景，早已引起国内外学者的极大关注．例如，由于氧化物具有各种特殊的介电和光学性质，研究和开发基于氧化物薄膜的气敏材料非常热门．如何制备出有实用价值的各种薄膜材料，是科学家们一直关心和深入研究的课题．电子能谱技术在各种材料的基础研究和实际应用中起着重要的作用．本文以有序金属氧化物薄膜研制为例，简要评述了电子能谱技术（包括X射线光电子能谱（XPS），紫外光电子能谱（UPS），俄歇电子能谱（AES）和高分辨电子能量损失谱（HREELS）），以及低能电子衍射（LEED）等技术在氧化物薄膜材料制备和表征中的应用．     

氧化物薄膜研制中的电子能谱技术

随着科学技术的不断发展,人们正在寻求更新的实用材料.金属氧化物,包括金属氧化物薄膜的各种实用材料,在工业界、信息产业界和能源开发等方面的应用前景,早已引起国内外学者的极大关注.例如,由于氧化物具有各种特殊的介电和光学性质,研究和开发基于氧化物薄膜的气敏材料非常热门.如何制备出有实用价值的各种薄膜材料,是科学家们一直关心和深入研究的课题.电子能谱技术在各种材料的基础研究和实际应用中起着重要的作用.本文以有序金属氧化物薄膜研制为例,简要评述了电子能谱技术（包括X射线光电子能谱（XPS）,紫外光电子能谱（UPS）,俄歇电子能谱（AES）和高分辨电子能量损失谱（HREELS））,以及低能电子衍射（LEED）等技术在氧化物薄膜材料制备和表征中的应用.     

A reassessment of electron escape depths in silicon and thermally grown silicon dioxide thin films

The escape depths of electrons with kinetic energies of approximately 1150 and 1380 eV in Si and thermally grown SiO₂ thin films have been calculated, using three methods, from X-ray photoelectron spectra of samples which have been characterized by high resolution transmission electron microscopy (HRTEM). The most reliable and reproducible escape depths derived in this study are significantly less than the average of those reported in the literature. It is believed that this is due principally to inaccurate characterization of the samples previously used for escape depths measurements.     

Nanocomposite oxide thin films grown by pulsed energy beam deposition

Highly non-stoichiometric indium tin oxide (ITO) thin films were grown by pulsed energy beam deposition (pulsed laser deposition-PLD and pulsed electron beam deposition-PED) under low oxygen pressure. The analysis of the structure and electrical transport properties showed that ITO films with a large oxygen deficiency (more than 20%) are nanocomposite films with metallic (In, Sn) clusters embedded in a stoichiometric and crystalline oxide matrix. The presence of the metallic clusters induces specific transport properties, i.e. a metallic conductivity via percolation with a superconducting transition at low temperature (about 6 K) and the melting and freezing of the In-Sn clusters in the room temperature to 450 K range evidenced by large changes in resistivity and a hysteresis cycle. By controlling the oxygen deficiency and temperature during the growth, the transport and optical properties of the nanocomposite oxide films could be tuned from metallic-like to insulating and from transparent to absorbing films.     

Ionic conductivity study on electron beam irradiated polyacrylonitrileben polyethylene oxide gel

Different mass percent polyacrylonitrile (PAN)—polyethylene oxide (PEO) gels were prepared and irradiated by an electron beam (EB) with energy of 1.0 MeV to the dose ranging from 13 kGy to 260 kGy. The gels were analysed by using Fourier transform infrared spectrum, gel fraction and ionic conductivity (IC) measurement. The results show that the gel is crosslinked by EB irradiation, the crosslinking degree rises with the increasing EB irradiation dose (ID) and the mass percents of both PAN and PEO contribute a lot to the crosslinking; in addition, EB irradiation can promote the IC of PAN—PEO gels. There exists an optimum irradiation dose, at which the IC can increase dramatically. The IC changes of the PAN—PEO gels along with ID are divided into three regions: IC rapidly increasing region, IC decreasing region and IC balanced region. The cause of the change can be ascribed to two aspects, gel capturing electron degree and crosslinking degree. By comparing the IC—ID curves of different mass percents of PAN and PEO in gel, we found that PAN plays a more important role for gel IC promotion than PEO, since addition of PAN in gel causes the IC—ID curve sharper, while addition of PEO in gel causes the curve milder.     

Pulsed electron beam deposition of highly oriented thin films of polytetrafluoroethylene

Thin films of polytetrafluoroethylene (PTFE) were deposited by pulsed electron deposition (PED) technique. The transmission electron microscopy (TEM) image of the RT fabricated (20 Å thick) film on carbon coated copper grid shows crystalline nature. Infrared spectra show one to one correspondence between PED ablated film and the PTFE bulk target. The asymmetrical and symmetrical -CF₂- stretching modes were observed at 1220 and 1156 cm⁻¹, respectively. The -CF₂- wagging and bending modes occur at 644 and 512 cm⁻¹, respectively. X-ray diffraction patterns of the film deposited at room temperature (RT) show oriented film along (1 0 0) plane of hexagonal structure and the crystalline nature is retained up to 300 °C on vacuum annealing. The room temperature fabricated film shows smooth and pin hole free surface whereas post-annealing brings discontinuity, roughness and pin holes.     

Effect of energetic electron beam treatment on Ga-doped ZnO thin films

Transparent conductive zinc oxide (ZnO) thin films were synthesized by a sol–gel spin coating method with the addition of Ga(NO₃)₃ in a Zn(CH₃COO)₂ solution and exposed to electron beam treatment. The UV–Vis spectra demonstrated that all of the films had transmittances of over 85% in the visible region. When Ga(NO₃)₃ was added to the ZnO precursor solution, the resistivity of the ZnO thin film decreased and the carrier concentration increased significantly. After electron beam treatment was performed on the 0.4 at.% Ga-doped ZnO film, the optical band gap increased and the resistivity significantly decreased resulting from the increases of the carrier concentration and mobility. By combining Ga doping and electron beam treatment, the resistivity of the ZnO thin film was reduced by a factor of nine hundred.     

Changes in the silicon microhardness induced by a low-intensity electron beam

It is shown that nonequilibrium point defects are of primary importance in the changes in the silicon microhardness induced by a low-intensity (I ～ 10⁵ cm^?2 s^?1) electron beam. It is found that the necessary condition for softening under low-intensity electron irradiation is the presence of an oxide layer on the surface. The thickness of the surface layer in which anomalous changes in the microhardness are observed is determined by the layer-by-layer etching technique.     

Anomalous temperature dependence of the electrical conductivity of zinc oxide thin films

The temperature dependence of the conductivity of Ga-doped ZnO thin films was examined in humid and dry atmospheres. The conductivity initially increases to the maximum (range 1) and then decreases to the minimum (range 2) and again increases (range 3) in the heating run under humid air atmosphere. The subsequent cooling reduces the conductivity to less than that for the heating run. The extent of the reduction becomes large as the cooling rate increases. The extrema character in the conductivity versus temperature curves does not disappear under nitrogen gas atmosphere provided it is humid. On the other hand, the conductivity in the ranges 1 and 2 decreases so significantly that the extrema character disappears in the driest air as possible. These behaviors are explained by assuming that the dissociatively chemisorbed states of water vapor act as electron donors and desorb at the higher temperature, and the desorption as well as the chemisorption require a time for attaining equilibrium. With this in view, a theoretical analysis is given of semiconducting films thinner than the depletion boundary layer thickness, and numerical curves fitting to the experimental results are obtained. The heat of chemisorption of nonionized water q° is 1.35 eV and the energy levels of water chemisorption donors and oxygen chemisorption acceptors are at 0.66 and 0.59 eV below the conduction band edge, respectively.     

Tuning of surface properties of thin polymer films by electron beam treatment

The aim of our work was to understand the impact of electron treatment on polymer thin films, particularly on their surface properties as well as the possibilities and limitations to tune these properties. Two different polymers, polystyrene (PS) and poly-2-vinlypyridine (P2VP), were chosen to form thin polymer films by grafting of end-terminated linear polymer chains to a surface with sufficient grafting density, forming so called “polymer brushes”. We were able to identify the surface properties and specify ongoing physico-chemical changes after electron beam treatment by using zeta potential and contact angle measurements. By varying the absorbed dose it was possible to tune the surface properties over a wide range. The detailed knowledge about the latitude of functionalization of the tested polymers was a prerequisite for the creation of wettability gradients by electron beam treatment by adapting a special mask of known thickness and density. Hence, electron beam treatment opens an easy reproducible way to generate surface gradients in functionality.