TiO2 chemical vapor deposition on Si(111) in ultrahigh vacuum: Transition from interfacial phase to crystalline phase in the reaction limited regime

The interaction between the metal organic precursor molecule titanium(IV) isopropoxide (TTIP) and three different surfaces has been studied: Si(111)-(7 × 7), SiO_x/Si(111) and TiO₂. These surfaces represent the different surface compositions encountered during TTIP mediated TiO₂ chemical vapor deposition on Si(111). The surface chemistry of the titanium(IV) isopropoxide precursor and the film growth have been explored by core level photoelectron spectroscopy and x-ray absorption spectroscopy using synchrotron radiation. The resulting film morphology has been imaged with scanning tunneling microscopy. The growth rate depends on both surface temperature and surface composition. The behavior can be rationalized in terms of the surface stability of isopropoxy and isopropyl groups, confirming that growth at 573 K is a reaction limited process.     

Properties of thin manganite films grown on semiconducting substrates for spintronics applications

La_0.7Sr_0.3MnO₃ (LSMO) manganite thin films were grown by pulsed plasma deposition on silicon (Si) and gallium arsenide (GaAs) substrates covered by an amorphous oxide. Manganite films are characterized by polycrystalline structure. Ferromagnetic transition is above room temperature and for 50 nm thick film the Curie temperature was as high as 325 K and 305 K for LSMO/SiO_x/Si and LSMO/AlO_x/GaAs, respectively.     

Growth and characterization of CoSi2 films on Si (1 0 0) substrates

In the present work, a special solid phase epitaxy method has been adapted for the preparation of CoSi₂ film. This method includes an epitaxial growth of Co films on Si (1 0 0) substrate, and in situ annealing of the Co/Si films in vacuum. It has been found that at the substrate temperature of 360°C, fcc cobalt film grows epitaxially on the Si (1 0 0) surface. The crystallographic orientation relations between fcc Co film and Si substrate determined from the electron diffraction result are: (0 0 1) Co//(0 0 1) Si, [1 0 0] Co//[1 1 0]Si. Upon annealing at temperatures range from 500 to 600°C, Co film reacts with Si substrate and transforms into CoSi₂. The CoSi₂ films prepared by this way are characterized by XTEM, XPS and AFM.     

Attenuation lengths of high energy photoelectrons in compact and mesoporous SiO2 films

We have experimentally evaluated attenuation lengths (AL) of photoelectrons traveling in compact and micro and mesoporous (~ 45% voids) SiO₂ thin films with high (8.2–13.2 keV) kinetic energies. The films were grown on polished Si(100) wafers. ALs were deduced from the intensity ratio of the Si 1s signal from the SiO₂ film and Si substrate using the two-peaks overlayer method. We obtain ALs of 15–22 nm and 23–32 nm for the compact and porous SiO₂ films for the range of kinetic energies considered. The observed AL values follow a power law dependence on the kinetic energy of the electrons where the exponent takes the values 0.81 ± 0.13 and 0.72 ± 0.12 for compact and porous materials, respectively.     

Influence of porosity on laser damage threshold of sol–gel ZrO2 and SiO2 monolayer films

Monolayer ZrO₂ sol–gel and physical vapor deposition (PVD) films were prepared by spin method and electron beam evaporation method, respectively. Monolayer sol–gel SiO₂ films were prepared with the dip-coating method from acid and base catalyzed SiO₂ sols, respectively. Some of the SiO₂ base films were subsequently treated in saturated ammonia gas for 20 h. The laser induced damage threshold (LIDT) of each film was measured. Properties of the films were analyzed by using Stanford photo-thermal solutions (SPTSs), ellipsometer, atomic force microscopy (AFM) and optical microscopy. The experimental results showed that porous ratio is an essential factor to decide the LIDT for sol–gel films, which benefits the pressure exerted on the film or substrate by the moving particle to dissipate. The films with lower thermal absorption and higher porous ratio have higher LIDT.     

The improvement of pyroelectric properties of PZT thick films on Si substrate by TiOx barrier layer

The effects of TiO_x diffusion barrier layer thickness on the microstructure and pyroelectric characteristics of PZT thick films were studied in this paper. The TiO_x layer was prepared by thermal oxidation of Ti thin film in air and the PZT thick films were fabricated by electrophoresis deposition method (EPD). To demonstrate the barrier effect of TiO_x layer, the electrode/substrate interface and Si content in PZT thick films were characterized by scanning electron microscope (SEM) and X-ray energy dispersive spectroscopy (EDS), respectively. The TiO_x barrier thickness shows significant influence on the bottom electrode and the pyroelectric performance of the PZT thick films. The average pyroelectric coefficient of PZT films deposited on 400 nm TiO_x layer was about 8.94 × 10⁻⁹ C/(cm² K), which was improved by 70% than those without diffusion barrier layer. The results showed in this study indicate that TiO_x barrier layer has great potential in fabrication of PZT pyroelectric device.     

Investigation of thermal sensitivity and radiation resistance of SiOx〈Ti〉 metal-dielectric films

In this investigation the composite SiO_x〈Ti〉 films were prepared by the thermal evaporation of a mixture of silicon oxide (SiO₂) and Тi powders. The optical transmission of the films in the IR spectral range and their temperature-sensitive properties are studied. By varying the contents of the metal in vaporizer and time of evaporation it is possible to obtain SiO_x〈Ti〉 layers with resistance (for monopixel of 0.8 × 1 mm) from tens kOhms to MOhms and a value of the temperature coefficient of resistance (TCR) is equal to −2.22% K⁻¹. IR spectrum of SiO_x〈Ti〉 film is characterized by a broad absorption band in the range of 8–12 μm which is associated with the Si–O–Si stretching mode.Investigations of the effect of gamma irradiation on SiO_x〈Ti〉 films have shown that their temperature-sensitive properties, in particular TCR does not change up to a dose of 10⁶ Gy.These results suggest that SiO_x〈Ti〉 films can be used as materials for production of radiation-resistant thermosensitive detectors operated in radiation fields of γ-radiation and combining functions of IR-absorption and formation of an electric signal.     

Photoemission study of interfacial reactions during annealing of ultrathin yttrium on SiO2/Si(1 0 0)

X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS) and work-function measurements have been used to investigate the Y/SiO₂/Si(1 0 0) interfaces in situ as a function of annealing temperature. The results show that yttrium is very reactive with SiO₂ and can react with SiO₂ to form Y silicate and Y₂O₃ even at room temperature. Annealing leads to the continual growth of the Y silicate. Two distinctive reaction mechanisms are suggested for the annealing processes below and above 600 K. The reaction between metallic yttrium and SiO₂ dominates the annealing processes below 600 K, while at annealing temperatures above 600 K, a reaction between the new-formed Y₂O₃ and SiO₂ becomes dominant. No Y silicide is formed during Y deposition and subsequent annealing processes. UPS valence-band spectra indicate the silicate layer is formed at the top surface. After 1050 K annealing, a Y-silicate/SiO₂/Si structure free of Y₂O₃ is finally formed.     

Advanced ion beam technology for versatile oxide thin film formation

Various oxide films, such as SnO₂, In₂O₃, Al₂O₃, SiO₂, ZnO, and Sn-doped In₂O₃ (ITO) have been deposited on glass and polymer substrates by advanced ion beam technologies including ion-assisted deposition (IAD), hybrid ion beam, ion beam sputter deposition (IBSD), and ion-assisted reaction (IAR). Physical and chemical properties of the oxide films and adhesion between films and substrates were improved significantly by these technologies. By using the IAD method, non-stoichiometry, crystallinity, and microstructure of the films were controlled by changing assisted oxygen ion energy and arrival ratio of assisted oxygen ion to evaporated atoms. IBSD method has been carried out for understanding the growth mode of the films on glass and polymer substrate. Relationships between microstructure and electrical properties in ITO films on polymer and glass substrates were intensively investigated by changing ion energy, reactive gas environment, substrate temperature, etc. Smooth-surface ITO films (R_rms ⩽ 1 nm and R_p−v ⩽ 10 nm) for organic light-emitting diodes were developed with a combination of deposition conditions with controlling microstructure of a seed layer on glass. IAR surface treatment enormously enhanced the adhesion of oxide films to polymer substrate. In the case of Al₂O₃ and SiO₂ films, the oxygen and moisture barrier properties were also improved by IAR surface treatment. The experimental results of the oxide films prepared by the ion beam technologies and its applications will be represented in detail.     

Effect of nitrogen partial pressure on Al–Ti–N films deposited by arc ion plating

AlTiN films with different nitrogen partial pressures were deposited using arc ion plating (AIP) technique. In this study, we systematically investigated the effect of the nitrogen partial pressure on composition, deposition efficiency, microstructure, macroparticles (MPs), hardness and adhesion strength of the AlTiN films. The results showed that with increasing the nitrogen partial pressure, the deposition rate exhibited a maximum at 1.2 Pa. Results of X-ray photoelectron spectroscopy (XPS) analysis revealed that AlTiN films were comprised of Ti–N and Al–N bonds. XRD results showed that the films exhibited a (1 1 1) preferred growth, and AlTi₃N and TiAl_x phases were observed in the film deposited at 1.7 Pa. Analysis of MPs statistics showed MPs decreased with the increase in the nitrogen partial pressure. In addition, the film deposited at 1.2 Pa possessed the maximum hardness of 38 GPa and the better adhesion strength.     

Hydro-oleophobic silica antireflective films with high laser-damage threshold

A simple method of preparing hydro-oleophobic anitreflective films with high laser-damage threshold is reported in this article. By adding fluoroalkylsilanes (FAS) into reactant mixture as a co-precursor, FAS modified SiO₂ was obtained under base catalyzed hydrolysis and condensation of tetraethoxysilane. The dip-coating films were deposited on two sides of fused silica substrates.The experimental results on the effect of adding fluoroalkylsilanes (FAS) as a co-precursor on the hydro-oleophobicity and optical properties of tetraethoxysilane (TEOS) based silica AR films, are reported. The hydro-oleophobicity of the films was tested by the contact angle measurements and the highest water contact angle of 136° and oil (peanut) contact angle of 93° were obtained. The surface chemical modification of the hydro-oleophobic films was confirmed using Fourier transform infrared spectroscopy (FTIR). For the films based on FAS and TEOS, additional absorption bands at 1100 cm^?1 corresponding to C–F bond presented, clearly indicating the organic modification of the films. The highest optical transmittance of the hydro-oleophobic films was found to be 99.5%. By a Nd:YAG lasers the laser-damage threshold of as-deposited films was measured at 351 nm wavelength (1 ns). The laser-damage threshold was as high as 22.6 J/cm².     

Aging effect of SiO2 xerogel film on its microstructure and dielectric properties

The properties of porous SiO₂ xerogel film strongly depend on the aging process. The morphology of the surface modified SiO₂ xerogel film pre-aged for 1 hr at 70°C showed a two-dimensional structure. Aging for 12 h at 70°C and successive modification of the film induced some particle growth and a three-dimensional network structure. The microstructure of the modified SiO₂ xerogel films reflects the preformed structure during aging. The surface modification induced the changes of surface coverage from –OC₂H₅ and –OH bonds to –CH₃. However the content of surface chemical species was almost same regardless of aging time. The porosity of the modified sample pre-aged for 12 h at 70°C was 89%. The calculated/measured dielectric constants were 1.31/1.42, respectively     

Characterization of LSGM films obtained by electrophoretic deposition (EPD)

The application of the electrophoretic deposition (EPD) technique to the preparation of high quality electrolyte films for intermediate temperature solid oxide fuel cells (IT-SOFCs) was investigated. Films of La_0.83Sr_0.17Ga_0.83Mg_0.17O_2.83 (LSGM) were deposited on Pt and La_0.8Sr_0.2MnO₃ (LSM) substrates from suspensions in acetone/ethanol (3:1 by volume) mixture solvent and sintered at 1300 °C. Pt supported LSGM films, 10–20 μm thick, exhibited good adhesion to the Pt substrate, well-distributed microporosity and some surface roughness. LSM supported films exhibited cracking after sintering at 1300 °C for 3 h. Up to 900 °C the bulk conductivity of the Pt supported LSGM film showed the same behaviour of LSGM pellet (E_a = 0.93 eV and 0.99 eV, respectively). The LSGM film exhibited lower bulk electrical conductivity than the latter (4.1 × 10^− 3 and 4.4 × 10^− 2 Ω^− 1 cm^− 1, respectively, at 700 °C). This difference should be ascribed to the slight Ga depletion in the LSGM film. An important issue remains the selection of adequate electrode for LSGM electrolyte films.     

H adsorption at Ag/Si interfaces in epitaxially grown Ag(1 1 1) films on Si(1 1 1)7 × 7 substrates

The interaction of atomic H with Ag(1 1 1)/Si(1 1 1)7 × 7 surfaces was studied by thermal desorption (TD) spectroscopy and scanning tunneling microscopy (STM) at room temperature. TD spectroscopy revealed an intense peak from mono H–Si bonds, even though the Si surface was covered by the Ag atoms. This peak was not observed from Ag-coated SiO₂/Si substrates. STM observation showed no clear change of the Ag surface morphology resulting from H exposure. All these results indicate that the atomic H adsorbs at neither the Ag surfaces nor Ag bulk sites, but at the Ag/Si interface by diffusing through the Ag film.     

Electron-energy-loss spectroscopy of C60 monolayer films on active and inactive surfaces

The characteristics of interaction between C₆₀ molecules and Si(1 1 1)-7×7, Ag/Si(1 1 1)-√3×√3 R30° and layered material MoS₂ surfaces have been investigated using electron-energy-loss spectroscopy (EELS). The EEL spectrum of C₆₀/Si(1 1 1)-7×7 shows a new peak at loss energy of 2.7 eV. This indicates the existence of charge transfer from the substrate to C₆₀ molecules. The EEL spectrum of a C₆₀ monolayer film grown on a cleaved surface of MoS₂ is almost the same as that of bulk C₆₀. The EEL spectrum of a C₆₀ monolayer film on an Ag/Si(1 1 1) surface is quite different from that on a clean Si(1 1 1)-7×7 surface, although the films on those substrates have the same epitaxial arrangement. Furthermore, intensities of energy-loss peaks of C₆₀/Ag/Si(1 1 1) are slightly smaller than those of C₆₀/MoS₂ in spite of having the same loss-energy. This suggests that the interaction between C₆₀ molecules and the Ag/Si(1 1 1) surface is stronger than that between C₆₀ molecules and the MoS₂ surface.     

Adsorption of O2 and CO2 on the Si(111)-7 × 7 surfaces

The interaction of O₂ and CO₂ with the Si(111)-7 × 7 surface has been studied with X-ray photoelectron spectroscopy (XPS). It was found that both O₂ and CO₂ molecules can readily oxidize the Si(111)-7 × 7 surface to form thin oxide films. Two oxygen species were identified in the oxide film: oxygen atoms binding to on-top sites of adatom/rest atoms with an O 1s binding energy of ~ 533 eV as well as to bridge sites of adatom/rest atom backbonds at ~ 532 eV. These two oxygen species can be interconverted thermally during the annealing process. Due to the low oxidation capability, the silicon oxide film formed by CO₂ has a lower O/Si ratio than that of O₂.     

Preparation and characterization of iron–molybdate thin films

Mixed Fe–Mo oxides are used in industrial catalytic processes of selective oxidation of methanol to formaldehyde. For better understanding of the structure-reactivity relationships of these catalysts we aim to prepare well-ordered iron–molybdate thin films as model catalysts. Here we have studied Mo deposition onto Fe₃O₄ (111) thin films produced on Pt(111) as a function of Mo coverage and annealing temperature using LEED, AES, STM and IRAS. At low temperatures, the iron oxide film is covered by Mo = O terminated molybdena nanoparticles. Upon oxidation at elevated temperatures (T > 900 K), Mo species migrate into the film and form new bonds with oxygen in the film. The resulting films maintain the crystal structure of Fe₃O₄, and the surface undergoes a (√3 × √3)R30° reconstruction. The structure is rationalized in terms of Fe substitution by Mo in the surface layers.     

New approach to the growth of SiOx nanowire bunch using Au catalyst and SiNx film on Si substrate

SiO_x nanowire bunches were fabricated on a SiN_x film with Au catalytic metal in the presence of an Ar flow of 50 sccm at 1150 °C. The resulting samples were characterized by field-emission scanning electron microscopy, transmission electron microscopy and energy dispersive X-ray spectroscopy. A SiN_x film serves as a barrier to the diffusion of Si atoms from the Si substrate to the catalytic Au metal, where a substrate is a Si source material for SiO_x nanowire (NW) growth. Using this process, we could temporally control the initial growth step of SiO_x NWs and easily grow the NW bunch.     

Growth of atomically flat ultra-thin Ag films on Si surfaces

A two-step growth with deposition at low temperature and subsequent slow annealing to room temperature (RT) has been widely used to obtain atomically flat metal thin films on semiconductor substrates. In the case of Ag films, almost atomically flat films were obtained at a thickness of six monolayers (ML) on Si and GaAs. The flatness then gradually degraded with an increase in thickness. The existence of the critical thickness has been well explained by the “electronic growth theory”, which considers thickness-dependent change of vertically quantized electrons and their spilling out at the interfaces. However, several questions remain unanswered. How does the electronically grown Ag flat film accommodate the large misfit energy between the film and substrate? Up to what deposition temperature is the two-step growth effective to obtain atomically flat films? In this article, we review previous studies on the electronic growth of Ag films on Si(1 1 1) substrates, paying special attention to these two points. In addition, we also discuss the possibility of engineering electronic growth for artificial control of the critical thickness.     

Exploring surface processes by coaxial impact-collision ion scattering spectroscopy and time-of-flight elastic recoil detection analysis

The usefulness of coaxial impact-collision ion scattering spectroscopy and time-of-flight elastic recoil detection analysis for in situ surface analysis, especially for elucidation of surface processes, is demonstrated by taking the following studies as examples: (1) self-restoration processes of oxygen vacancies at vacuum-annealed TiO₂(1 1 0) surface, (2) effects of Mn incorporation on MBE growth of GaMnN film, (3) growth process in hydrogen-surfactant mediated epitaxy of Ge/Si(0 0 1), and (4) structure analysis of the Si(0 0 1)2×3-Ag surface.