Study on changes in the structure of HfSiO and HfSiON dielectrics with different annealing temperature by photoelectron spectroscopy

We have investigated changes of the structure for HfSiO and HfSiON film with different annealing temperature by photoelectron spectroscopy. Core level photoelectron spectra have revealed the mechanism of metallization reaction at the bottom interface between the HfSiO(N) film and Si substrate under vacuum annealing. Silicidation action occurs by annealing at 850 and 900 °C for HfSiO and HfSiON film, respectively, indicating the incorporation of nitrogen enhances the thermal stability. By annealing at 900 °C, metallization reaction is rapidly promoted for the HfSiO film. For HfSiON film, Hf-nitride clusters or Hf-nitride layer and metal-silicide are formed at the bottom and upper interface, respectively, upon annealing at 950 °C.     

Atomic transport and chemical stability of nitrogen in ultrathin HfSiON gate dielectrics

HfSiO and HfSiON films with thicknesses compatible with the requirements for gate dielectrics alternatives to SiO₂ in ultra-large scale integration silicon-based CMOSFET devices were deposited on an ultrathin HfSiO¹⁵N interfacial layer on Si(001). These structures were submitted to thermal processing routines typical of post-deposition annealing and dopant activation steps in fabrication technology, namely at 450 or 1000 °C, respectively, and in atmospheres of N₂ and/or O₂. N transport and loss were determined by nuclear reaction analysis, including sub-nanometric depth resolution profiling with narrow nuclear reaction resonances. The chemical states of N were accessed by angle-resolved X-ray photoelectron spectroscopy. After annealing at 450 °C, N is seen to be mobile, whereas the chemical environment of N is not changed at this temperature. Annealing at 1000 °C renders N mobile and its most abundant chemical state in near-surface regions is unstable. Annealing in O₂ atmosphere promotes incorporation of O from the gas phase into the films, partly in exchange for N and O atoms and partly by net incorporation of oxygen in the films. The profiles of the newly incorporated O atoms are also determined with sub-nanometric depth resolution by narrow nuclear reaction resonance profiling. PACS 68.60.-p; 68.55.-a; 73.61.Ng; 73.40.Qv     

Oxidation of ultra-thin Ti films on Mo(100): Soft X-ray photoelectron spectroscopy study

Titanium oxide films grown on Mo(100) have been investigated by low-energy electron diffraction (LEED) and soft X-ray photoelectron spectroscopy (PES). The film was grown by Ti deposition on Mo(100) and subsequent oxidation of the film by 12 L of O₂ exposure at room temperature. As the film was annealed at 700–1000 °C, the film in which the Ti atoms were in a Ti³⁺ oxidation state was formed. As the film was annealed at 1100–1500 °C, the oxidation state of Ti in the film was converted to Ti²⁺. The valence electronic structure of the film was measured under the condition that the emission from the Mo substrate was minimized due to a Cooper minimum of the Mo 4 d photoionization cross sections (hν = 100 eV). It was found that the Ti 3 d band in normal-emission spectra was increased in intensity when the film was annealed at 1100–1500 °C. As the film was annealed at 1300 °C for 10 s and 20 s, the film-covered Mo(100) gave (2 × 2) and (4 × 1) LEED patterns, respectively. The two-dimensional band structure of the (2 × 2) system was investigated by angle-resolved PES, and it was found that the film with a (1 × 1) periodicity with respect to the Mo(100) substrate existed in the (2 × 2) system.     

Thermally induced effects on structural and electrical properties of selenium-rich Cd-Se thin films

The effect of annealing in nitrogen atmosphere on structural and electrical properties of selenium rich CdSe (SR-CdSe) thin films deposited by thermal evaporation onto glass substrates were studied. X-ray diffraction (XRD) patterns showed that the as-prepared films were amorphous, whereas the annealed films were polycrystalline. Analyzing XRD patterns reveals the coexistence of both Se and CdSe crystalline phases which exhibits a hexagonal structure. The microstructure parameters (crystallite size, microstrain and dislocation density) were calculated for annealed films.Temperature dependence (300–500 K) of d.c. conductivity was studied for as-prepared and annealed thin films. The experimental results indicate that the electrical conduction taking place through thermally activated process. At higher temperatures, electrical conduction for as-prepared film is taking place in the extended states while localized states conduction in the band tails is most likely to take place for annealed films. Regarding the lower temperature range, conduction by hopping in the localized states near the Fermi level is found to be dominant. Thus, conductivity data in this range was analyzed using Mott's variable range hopping conduction, where Mott's parameters were calculated for SR-CdSe thin films.     

Thin films of molecule-based charge transfer complex cobalt tetracyanoethylene: In situ X-ray photoemission study

Thin films of molecule-based charge transfer magnet, cobalt tetracyanoethylene [Co(TCNE)_x, x ~ 2] consisting of the transition metal Co, and an organic molecule viz. tetracyanoethylene (TCNE) have been deposited by using physical vapor deposition method under ultra-high vacuum conditions at room temperature. X-ray photoelectron spectroscopy (XPS) technique has been used extensively to investigate the electronic properties of the Co(TCNE)_x thin films. The XPS measurements show that the prepared Co(TCNE)_x films are clean, and oxygen free. The stoichiometries of the films, based on atomic sensitive factors, are obtained, and yields a ~ 1:2 ratio between metal Co and TCNE for all films. Interestingly, the positive shift of binding energy position for Co(2p), and negative shifts for C(1s) and N(1s) peaks suggest a charge-transfer from Co to TCNE, and cobalt is assigned to its Co(II) valence state. In the valence band investigation, the highest occupied molecular orbital (HOMO) of Co(TCNE)_x is found to be at ~ 2.4 eV with respect to the Fermi level, and it is derived either from the TCNE^? singly occupied molecular orbital (SOMO) or Co(3d) states. The peaks located at ~ 6.8 eV and ~ 8.8 eV are due to TCNE derived electronic states. The obtained core level and valence band results of Co(TCNE)_x, films are compared with those of V(TCNE)_x thin film magnet: a well known system of M(TCNE)_x type of organic magnet, and important points regarding their electronic properties have been brought out.     

Study of band offsets in InN/Ge heterojunctions

InN layers were directly grown on Ge substrate by plasma-assisted molecular beam epitaxy (PAMBE). The valence band offset (VBO) of wurtzite InN/Ge heterojunction is determined by X-ray photoemission spectroscopy (XPS). The valence band of Ge is found to be 0.18 ± 0.04 eV above that of InN and a type-II heterojunction with a conduction band offset (CBO) of ~ 0.16 eV is found. The accurate determination of the VBO and CBO is important for the design of InN/Ge based electronic devices.     

Post-annealing influence on electrical properties and photoluminescence of B-N codoping ZnO thin films

B-N codoped ZnO (ZnO:(B,N)) films were grown on quartz substrate by radio-frequency (rf) magnetron sputtering. The influence of post-annealing ambient on electrical and optical properties of ZnO:(B,N) films were investigated using Hall and Photoluminescence (PL) measurement, respectively. Electrical properties studies indicate that both post-annealing ZnO:(B,N) showed p-type conduction. However, compared with ZnO:(B,N) annealed in oxygen, the ZnO:(B,N) annealed in vacuum have low resistivity and high concentration. The PL spectra indicate that two new emission bands located at 3.303 and 3.208 eV originate from the recombination of A⁰X and FA related to N acceptor for the annealed p-ZnO:(B,N) in vacuum, but of A⁰X, FA related to Zn vacancy for the annealed p-ZnO:(B,N) in oxygen. The mechanism of influence of post-annealing on the electrical and optical properties of the ZnO:(B,N) film is discussed in this work.     

Annealing temperature dependent on structural,optical and electrical properties of indium oxide thin films deposited by electron beam evaporation method

In the present work the influence of annealing temperature on the structural and optical properties of the In₂O₃ films deposited by electron beam evaporation technique in the presence of oxygen was studied. The deposited films were annealed from 350 to 550 °C in air. The chemical compositions of In₂O₃ films were carried out by X-ray photoelectron spectroscopy (XPS). The film structure and surface morphologies were investigated as a function of annealing temperature by X-ray diffraction (XRD) and atomic force microscopy (AFM). The structural studies by XRD reveal that films exhibit preferential orientation along (2 2 2) plane. The refractive index (n), packing density and porosity (%) of films were arrived from transmittance spectral data obtained in the range 250–1000 nm by UV–vis-spectrometer. The optical band gap of In₂O₃ film was observed and found to be varying from 3.67 to 3.85 eV with the annealing temperature.     

Influence of argon ambience on the structural,morphological and optical properties of pulsed laser ablated zinc sulfide thin films

Nanostructured zinc suplhide thin films are successfully deposited on quartz substrates using pulsed laser deposition (PLD) under different argon pressures (0, 5, 10, 15 and 20 Pa). The influence of argon ambience on the microstructural, optical and luminescence properties of zinc sulfide (ZnS) thin films is systematically investigated. The GIXRD data suggests rhombohedral structure for ZnS films prepared under different argon ambience. Self-assembly of grains into well-defined patterns along the y direction is observed in the AFM image of the film deposited under argon pressure 20 Pa. All the films show a blue shift in optical band gap. This can be due to the quantum confinement effect and less widening of conduction and valence band for the films with less thickness and smaller grain size. The PL spectra of the different films are recorded at excitation wavelengths 250 nm and 325 nm and the spectra are interpreted. The PL spectra of the films recorded at excitation wavelength 325 nm show intense yellow emission. The film deposited under an argon pressure of 15 Pa shows the highest PL intensity for excitation wavelength 325 nm. For the PL spectra (excitation at 250 nm), the highest PL intensity is observed for the film prepared under argon free ambience. In our study, 15 Pa is the optimum argon pressure for better crystallinity and intense yellow emission when excited at 325 nm.     

Visible-light photocatalytic activity of nitrogen-doped TiO2 thin film prepared by pulsed laser deposition

Nitrogen-doped titanium dioxide (TiO_2−xN_x) thin films have been prepared by pulse laser deposition on quartz glass substrates by ablated titanium dioxide (rutile) target in nitrogen atmosphere. The x value (nitrogen concentration) is 0.567 as determined by X-ray photoelectron spectroscopy measurements. UV-vis spectroscopy measurements revealed two characteristic deep levels located at 1.0 and 2.5 eV below the conduction band. The 1.0 eV level is attributable to the O vacancy state and the 2.5 eV level is introduced by N doping, which contributes to narrowing the band-gap by mixing with the O2p valence band. The enhanced degradation efficiency in a broad visible-light range was observed from the degradation of methylene blue and methylene orange by the TiO_2−xN_x film.     

Investigation of reduced graphene oxide effects on ultra-violet detection of ZnO thin film

The reduced graphene oxide (rGO) incorporated ZnO thin films were fabricated by dip-coating method. The Raman and FT-IR spectra of 0.075 wt% incorporated composite film showed reduction of GO in composite film. The transmittanceProd. Type: FTP spectra have shown that rGO incorporation increase the visible light absorption of ZnO thin film while the calculated band gaps of samples were decreased from 3.28 to 3.25 eV by increasing the rGO content. The linear trend of I–V curve suggests an ohmic contact between ZnO and rGO. Besides, it was found that by increasing the rGO content, the electrical resistivity was decreased from 4.32×10² Ω cm for pure ZnO film to 2.4×10¹ Ω cm for 0.225 wt% rGO incorporated composite film. The composite photodetectors not only possessed a desirable UV photosensitivity, but also the response time of optimum sample containing 0.075 wt% rGO was reduced to about one-half of pure ZnO thin film. Also, the calculated signal to noise (SNR) showed that highly conductive rGO in composite thin films facilitate the carrier transportation by removing the trapping centers. The mechanism of photoresponsivity improvement of composite thin films was proposed by carrier transportation process.     

Tunable electronic structure in stained two dimensional van der Waals g-C2N/XSe2 (X = Mo,W) heterostructures

The electronic structure of the strained g-C₂N/XSe₂ (X=Mo, W) van der Waals heterostructures are investigated by first-principles calculations. The g-C₂N/MoSe₂ heterostructure is an indirect band gap semiconductor at a strain from 0% to 8%, where its band gap is 0.66, 0.61, 0.73, 0.60 and 0.33 eV. At K point, the spin splitting is 186, 181, 39, 13 and 9 meV, respectively. For g-C₂N/WSe₂ heterostructures, the band gap is 0.32, 0.37, 0.42, 0.45 and 0.36 eV, and the conduction band minimum is shifted from Г-M region to K-Г region as the strain increases from 0% to 8%. Its spin splitting monotonically decreases as a strain raises to 8%, which is 445, 424, 261, 111 and 96 meV, respectively. Moreover, at a strain less than 4%, the conduction band mainly comes from g-C₂N, but it comes from XSe₂ (X=Mo, W) above 6%. Our results show that the g-C₂N/XSe₂ heterostructures have tunable electronic structures, which makes it a potential candidate for novel electronic devices.     

Lateral inhomogeneity of unoccupied states for PbPc films

Micro-spot two-photon photoemission (micro-2PPE) spectroscopy is used to probe unoccupied electronic levels at sub-monolayer (ML) films of lead phthalocyanine (PbPc) on graphite (HOPG). The high-energy resolution (30 meV) 2PPE spectra with high-lateral resolution (0.4 μm) show well-resolved features due to molecule-derived occupied/unoccupied levels and the image potential state (IPS). The surface images based on photoemission from the highest occupied molecular orbital (HOMO) become laterally uniform after an annealing procedure. By contrast, the images based on the peak due to the lowest unoccupied molecular orbital (LUMO) and the next LUMO (LUMO + 1) are laterally inhomogeneous even after the annealing. The IPS peak is broadened to higher energy by 0.3 eV for sub-ML films and becomes sharp when a 1 ML film is formed. The broadening indicates that the electron in the IPS is scattered by molecules within the mean free path in the range from 1 to 10 nm. PbPc molecules are randomly distributed including nm-clusters. The LUMO and LUMO + 1 levels are stabilized as the cluster size increases. The inhomogeneity of the surface image due to the LUMO + 1 peak arises from the size distribution of the nm-clusters. The present results demonstrate that the unoccupied levels are more sensitive to the environment than the occupied levels.     

Effect of GZO thickness and annealing temperature on the structural,electrical and optical properties of GZO/Ag/GZO sandwich films

The GZO/Ag/GZO sandwich films were deposited on glass substrates by RF magnetron sputtering of Ga-doped ZnO (GZO) and ion-beam sputtering of Ag at room temperature. The effect of GZO thickness and annealing temperature on the structural, electrical and optical properties of these sandwich films was investigated. The microstructures of the films were studied by X-ray diffraction (XRD). X-ray diffraction measurements indicate that the GZO layers in the sandwich films are polycrystalline with the ZnO hexagonal structure and have a preferred orientation with the c-axis perpendicular to the substrates. For the sandwich film with upper and under GZO thickness of 40 and 30 nm, respectively, it owns the maximum figure of merit of 5.3 × 10⁻² Ω⁻¹ with a resistivity of 5.6 × 10⁻⁵ Ω cm and an average transmittance of 90.7%. The electrical property of the sandwich films is improved by post annealing in vacuum. Comparing with the as-deposited sandwich film, the film annealed in vacuum has a remarkable 42.8% decrease in resistivity. The sandwich film annealed at the temperature of 350 °C in vacuum shows a sheet resistance of 5 Ω/sq and a transmittance of 92.7%, and the figure of merit achieved is 9.3 × 10⁻² Ω⁻¹.     

Structure,optical spectroscopy and dispersion parameters of ZnGa2Se4 thin films at different annealing temperatures

Thin films of ZnGa₂Se₄ were deposited by thermal evaporation method of pre-synthesized ingot material onto highly cleaned microscopic glass substrates. The chemical composition of the investigated compound thin film form was determined by means of energy-dispersive X-ray spectroscopy. X-ray diffraction XRD analysis revealed that the powder compound is polycrystalline and the as-deposited and the annealed films at T_a = 623 and 673 K have amorphous phase, while that annealed at T_a = 700 K is polycrystalline with a single phase of a defective chalcopyrite structure similar to that of the synthesized material. The unit-cell lattice parameters were determined and compared with the reported data. Also, the crystallite size L, the dislocation density δ and the main internal strain ε were calculated. Analyses of the AFM images confirm the nanostructure of the prepared annealed film at 700 K. The refractive index n and the film thickness d were determined from optical transmittance data using Swanepoel's method. It was found that the refractive index dispersion data obeys the single oscillator model from which the dispersion parameters were determined. The electric susceptibility of free carriers and the carrier concentration to the effective mass ratio were determined according to the model of Spitzer and Fan. The analysis of the optical absorption revealed both the indirect and direct energy gaps. The indirect optical gaps are presented in the amorphous films (as-deposited, annealed at 623 and 673 K), while the direct energy gap characterized the polycrystalline film at 700 K. Graphical representations of ε₁, ε₂, tan δ, ? Im[1/ε*] and ? Im[(1/ε* + 1)] are also presented. ZnGa₂Se₄ is a good candidate for optoelectronic and solar cell devices.     

Investigation of electronic states of infinite-layer SrFeO2 epitaxial thin films by X-ray photoemission and absorption spectroscopies

We investigated the electronic states of a single-crystal SrFeO₂ epitaxial thin film in the valence-band and conduction-band regions using synchrotron-radiation X-ray photoemission and absorption spectroscopies. Fe 2p–3d resonant photoemission measurements revealed that the Fe 3d states have higher densities of states at binding energies of 3–5 eV and 5–8.5 eV in the valence-band region. The O K-edge X-ray absorption spectrum exhibited three peaks in the Fe 3d-derived conduction band hybridized with O 2p states; these can be assigned to Fe 3d_xy, 3d_xz + 3d_yz, and 3d_x²_–y². In addition, the indirect bandgap value of the SrFeO₂ film was determined to be 1.3 eV by transmission and absorption spectroscopies.     

Modifications in physical,optical and electrical properties of tin oxide by swift heavy Au8+ ion bombardment

Tin oxide thin films were deposited by a novel technique called as modified-SILAR. The preparative parameters were optimized to obtain good quality thin films. As-deposited films were annealed in O₂ atmosphere for 1 h at 500 °C. The annealed films were irradiated using Au⁸⁺ ions with energy of 100 MeV at different fluencies of 1 × 10¹¹, 1 × 10¹², 5 × 10¹² and 1 × 10¹³ ions/cm² using tandem pelletron accelerator. The irradiation-induced modifications in tin oxide thin films were studied using XRD, AFM, optical band gap, photoluminescence and I–V measurements. XRD studies showed formation of tin oxide with tetragonal structure. AFM revealed uniform deposition of the material with increase in grain size after irradiation. Decrease in band gap from 3.51 eV to 2.82 eV was seen with increases in fluency. A decrease in PL intensity, and an additional peak was observed after irradiation. I–V measurements showed a decrease in resistance with fluency.     

The growth and field evaporation of Er and deuterated Er films

The morphological structure of clean and deuterated Er films deposited on W substrates and their removal by field evaporation have been investigated as part of a program directed toward the development of deuterium ion sources for neutron generators. Annealed Er films up to ~ 20 monolayers in thickness deposited on W < 110 > substrates appear pseudomorphic. Thicker annealed films form a hexagonal close-packed < 0001 > orientated over-layer with the Pitsch–Schrader orientation relation. The pseudomorphic and hexagonal close-packed character of the films is retained up to the last atomic layer that forms the film-substrate interface. Deuterated Er films appear polycrystalline. At 77 K in Ar, annealed Er films field evaporate at 2.5 V/Å primarily as Er^2 + and deuterated Er films evaporate at ~ 2.4 V/Å primarily as ErD_x^2 +. Field evaporation of both clean and deuterated Er films shows signs of space charge induced field lowering when film thicknesses exceeding ~ 10 layers were field evaporated using 20 ns duration voltage pulses.     

A spectroscopic ellipsometry study of TiO2 thin films prepared by ion-assisted electron-beam evaporation

Film characterization based on variable-angle spectroscopic ellipsometry (VASE) is desirable in order to understand physical and optical characteristics of thin films. A number of TiO₂ film samples were prepared by ion-assisted electron-beam evaporation with 200-nm nominal thickness, 2.0 Å/s deposition rate and 8 sccm oxygen flow rate. The samples were maintained at 250 °C during the deposition, and annealed in air atmosphere afterwards. As-deposited and annealed films were analyzed by VASE, spectrophotoscopy and X-ray diffractometry. From ellipsometry modeling process, the triple-layer physical model and the Cody–Lorentz dispersion model offer the best results. The as-deposited films are inhomogeneous, with luminous transmittance and band gap of 62.37% and 2.95 eV. The 300 °C and 500 °C are transition temperatures toward anatase and rutile phases, respectively. Increasing temperature results in an increase of refractive index, transmittance percentage and band gap energy. At 500 °C, the highest refractive index and band gap energy are obtained at 2.62 and 3.26 eV, respectively. The developed VASE-modeling process should be able to characterize other TiO₂ films, using similar physical and optical modeling considerations.     

Study of HfSiO film prepared by electron beam evaporation for high-k gate dielectric applications

The purpose of this paper is to report some experimental results with HfSiO films formed on silicon substrates by electron beam evaporation (EB-PVD) and annealed at different temperatures. The images of atomic force microscope (AFM) indicated that HfSiO film annealed at 900 °C was still amorphous, with a surface roughness of 0.173 nm. X-ray photoelectron spectroscopy (XPS) analysis revealed that the chemical composition of the film was (HfO₂)₃(SiO₂) and Hf-Si-O bonds existed in the annealed film. Electrical measurements showed that the equivalent oxide thickness (EOT) was 4 nm, the dielectric constant was around 6, the breakdown voltage was 10 MV/cm, the fixed charge density was −1.2 × 10¹² cm⁻², and the leakage current was 0.4 μA/cm² at the gate bias of 2 V for 6 nm HfSiO film. The annealing after deposition effectively reduced trapping density and the leakage current, and eliminated hysteresis in the C-V curves. Annealing also induced SiO₂ growth at the interface.