Pulsed laser deposited ZrAlON films for high-k gate dielectric applications

ZrAlON films were fabricated using the reactive ablation of a ceramic ZrAlO target in N₂ ambient by pulsed laser deposition (PLD) technique. ZrAlON films were deposited directly on n-Si(100) substrates and Pt coated silicon substrates, respectively, at 500 °C in a 20 Pa N₂ ambient, and rapid thermal annealed (RTA) in N₂ ambient at 1000 °C for 1 min. Cross sectional high-resolution transmission electron microscopy (HRTEM) images clearly show that the ZrAlON/Si interface is atomically sharp without an interfacial layer, and the films are completely amorphous. The electron diffraction pattern of TEM also indicates the amorphous structure of the RTA ZrAlON film. X-ray photoelectron spectroscopy (XPS) measurement was performed to confirm the effective incorporation of nitrogen with a content of about 6 at. %, and to reveal the N–O bonding in ZrAlON films. The dielectric constant of amorphous ZrAlON was determined to be about 18.2 which is more than 16.8 for ZrAlO by measuring the Pt/films/Pt capacitors. Capacitance–voltage (C–V) measurements show that a small equivalent oxide thickness (EOT) of 1.03 nm for 4 nm ZrAlON film on the n-Si substrate with a leakage current of 28.7 mA/cm² at 1 V gate voltage was obtained. PACS 77.55.+f; 81.15.Fg; 73.40.Qv     

Comparative study of pulsed laser deposited HfO2 and Hf–aluminate films for high-k gate dielectric applications

The thermal stability and the electrical properties of HfO₂ and Hf–aluminate films prepared by the pulsed laser deposition technique have been investigated by X-ray diffraction, differential thermal analysis, capacitance–voltage correlation, leakage-current measurements and high-resolution transmission electron microscopy observation, respectively. A crystallization transformation from HfO₂ amorphous phase to polycrystalline monoclinic structure occurs at about 500 °C. In contrast, the amorphous structure of Hf–aluminate films remains stable at higher temperatures up to 900 °C. Rapid thermal annealing at 1000 °C for 3 min leads to a phase separation in Hf–aluminate films. Tetragonal HfO₂(111) is predominant, and Al₂O₃ separates from Hf–aluminate and is still in the amorphous state. The dielectric constant of amorphous HfO₂ and Hf–aluminate films was determined to be about 26 and 16.6, respectively, by measuring a Pt/dielectric film/Pt capacitor structure. A very small equivalent oxide thickness (EOT) value of 0.74 nm for a 3-nm physical thickness Hf–aluminate film on a n-Si substrate with a leakage current of 0.17 A/cm² at 1-V gate voltage was obtained. The interface at Hf–aluminate/Si is atomically sharp, while a thick interface layer exists between the HfO₂ film and the Si substrate, which makes it difficult to obtain an EOT of less than 1 nm. PACS 77.55.+f; 81.15.Fg; 73.40.Qv     

Effect of poly silicon thickness on the formation of Ni-FUSI gate by using atomic layer deposited nickel film

The effect of poly-Si thickness on silicidation of Ni film was investigated by using X-ray diffraction, auger electron spectroscopy, cross-sectional scanning transmission electron microscopy, resistivity, I–V, and C–V measurements. The poly-Si films with various thickness of 30–200 nm were deposited by LPCVD on thermally grown 50 nm thick SiO₂, followed by deposition of Ni film right after removing the native oxide. The Ni film was prepared by using atomic layer deposition with a N²-hydroxyhexafluoroisopropyl-N¹ (Bis-Ni) precursor. Rapid thermal process was then applied for a formation of fully silicide (FUSI) gate at temperature of 500 °C in N₂ ambient during 30 s. The resultant phase of Ni-silicide was strongly dependent on the thickness of poly-Si layer, continuously changing its phase from Ni-rich (Ni₃Si₂) to Si-rich (NiSi₂) with increasing the thickness of the poly-Si layer, which is believed to be responsible for the observed flat band voltage shift, ΔV_FB, in C–V curves.     

Nature of oxygen in the passive film on stainless steels in 0.1 M NaCl solution

Three different oxygen species, O^2–, OH^–, and H₂O, are introduced into the deconvolution of the oxygen peaks measured in the prior study and their true concentrations are investigated in the depth profile. It is found that H₂O exists mainly in the outermost part of the passive film at the interface of solution and the passive film. OH^– and O^2– are found throughout the passive film; they have a maximum concentration in the outer layer at around 10 to 20 Å depth, with a concentration of 40 at.% for the stainless steel 29-4-2 and 50 at.% for 18-12. After the maximum the concentrations are sharply reduced with increasing sputtering time and remain at a constant concentration of about 10 at.% at 35 Å depth. Both species still exist at this concentration even after long time sputtering.     

Rapid growth of ultra thin SiO2 films by a large-area electron beam

Rapid growth of ultra thin oxide films (40–180Å) of silicon using a low-energy large-area electron beam has been performed with a pressure ratio of 31 (O₂/He) and a total pressure of 0.5–0.7 Torr. A higher oxidation rate of about 625Ų/s is found for shorter irradiation time of the e-beam in the e-beam dose range 0.75–3 Coulomb/cm² and at lower substrate temperature 540–740°C. AES and XPS demonstrated a rapid electron-stimulated oxidation process of the Si surface. For the grown ultra thin oxide films, C-V characteristics, dielectric strength, uniformity of the film over the entire Si wafer and its thickness as a function of the processing time of the e-beam are also presented.     

Electron microscope study of aluminium films evaporated on air-cleaved sodium chloride

The article deals with the structure of thin aluminium films evaporated on air-cleaved NaCl substrates. The effect of the substrate temperature and the film thickness on the structure, the orientation and the grain size of the films was studied at a deposition rate of 10 Å/see (ev. 50 Å/see) in a vacuum of about 7. 10^–5 torr. The optimum temperature for epitaxial growth was found to be about 420°C. An almost regular arrangement of grains was found in the thickness region of 90–150 Å.     

Surface analysis for catalyst layer (PT/PTFE/C) and diffusion layer (PTFE/C) for proton exchange membrane fuel cells systems (PEMFCs)

X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) studies have been used to analyze the surface of diffusion layer (PTFE/C) and catalyst layer (Pt/C/PTFE) of electrode. Detail analysis of carbon C_1s peak showed that the carbon was of the form of C, C-O, CO, CF, CF₂ and CF₃ with CF₂ is more dominated on the surface compared to CF and CF₃. The oxygen O_1s photoelectron peak showed that the oxygen was of the form of CO and C-O. The platinum was of the form of Pt⁰ with some Pt oxidized to PtO. The scanning electron microscopy was used to observe the dispersion of Teflon in the diffusion layer, the distribution of platinum in the catalyst layer loaded with 0.38 mg Pt/cm² and also the cross section of the membrane electrode assembly. The prepared electrode delivers a superior performance compared with the commercial electrode (E-TEK). The difference in performance between the two electrodes is due to the good localization of the platinum particles.     

Properties of reactively sputtered Mo1−x O x films

Molybdenum oxide (Mo_1–xO_x) films were prepared by reactive rf sputtering of a Mo target in O₂/Ar plasma. The dependence of film properties on various sputtering parameters is investigated. The atomic percentage of oxygen (x) in the Mo_1–xO_x films decreases with sputtering power and increases with the partial pressure of oxygen. Mo_1–xO_x films that exhibit metallic conductivities can be obtained over a wide range of sputtering conditions. The intrinsic film stress of conducting Mo_1–xO_x is compressive. Such M_1–xO_x films were shown by backscattering spectrometry to be excellent diffusion barriers between Al and Si up to 600 °C annealing for 30 min.     

SrBi2Ta2O9 ferroelectric thin film capacitors: degradation in a hydrogen ambient

The effects of annealing in forming gas 5% hydrogen, 95% nitrogen; FGA) are studied on spin-coated SrBi₂Ta₂O₉ (SBT) thin films. SBT films on a platinum bottom electrode are characterized with and without a platinum top electrode. Films are characterized by residual stress measurements, scanning electron microscopy (SEM), Auger electron spectroscopy (AES), high-temperature X-ray diffraction (HT-XRD) and secondary ion mass spectrometry (SIMS). To determine the degree of strain, lattice constants of Pt are measured by X-ray diffraction (XRD). HT-XRD of blanket SBT/Pt/Ti films in forming gas revealed that the bismuth-layered perovskite structure of SBT is stable up to approximately 500 °C. After formation of an intermediate phase between 550 °C and 700 °C, SBT changes its structure to an amorphous phase. SIMS analysis of Pt/SBT/Pt samples annealed in deuterated forming gas (5% D₂, 95% N₂) showed that hydrogen accumulates in the SBT layer and at the platinum interfaces next to the SBT. After FGA of blanket SBT films, tall platinum–bismuth whiskers are seen on the SBT surface. It is confirmed that these whiskers originate from the platinum bottom electrode and grow through the SBT layer. FGA of the entire Pt/SBT/Pt/Ti stack shows two different results. For the samples with a high-temperature annealing (HTA) step in oxygen after top electrode patterning, peeling of the top electrode is observed after FGA. For the samples without a HTA step, no peeling is observed after FGA. The residual stress at room temperature is measured for blanket platinum wafers deposited at different temperatures. It is found that an increase in tensile stress caused by the HTA step in oxygen is followed by a decrease in stress caused by the hydrogen in the forming gas. Without HTA, however, an increase of stress is observed after FGA. PACS 77.84.-s; 81.40.-z; 77.55.+f     

Reflectance and ellipsometric study of anodic film on platinum electrode

The anodic films on platinum electrode in 0.05 M sulfuric acid solution were examined by means of ellipsometry. By measuring the relative phase retardation (Δ), relative amplitude reduction (tanψ) and also the intensity of the reflected polarized light, the optical constants of the films (n, k) and thickness (τ) at various potentials were obtained. The results showed that the optical properties of the film remain nearly constant (n = 2.8, k = 1.7) while the thickness increases from 2 Å to 5 Å with anodic potential. From this evidence, it is concluded that the film is made of an oxide of platinum forming a definite phase.     

Structure and electrical properties of thin films of copper selenide

Electron-diffraction and electron-microscope methods were used to investigate the structure of Cu₂Se films of close to stoichiometric composition. It is shown that in polycrystalline and single-crystal films of thickness >400Å at room temperature, the tetragonal modification is stable, which at temperatures above 400°K is transformed into the cubical modification. In thinner films d<400 Å the cubical modification of copper selenide is stable at room temperature. A sharp peak is observed at 400°K on the temperature dependence of the resistance; this is connected with the phase transition. At room temperature, copper selenide is a degenerate p-type semiconductor with carrier concentration 5 · 10²²–8 · 10²⁰ cm^–3, depending on the thickness of the film.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 8, pp. 90–94, August, 1973.     

Study of interfacial oxide layer of LaAlO3 gate dielectrics on Si for metal–insulator–semiconductor devices

Lanthanum aluminate (LAO) thin films were deposited on silicon by pulsed-laser deposition. It was found that oxygen partial pressure played an essential role in the formation of an interfacial layer. The films deposited in nitrogen at a pressure of 20 Pa had no interfacial layer. However, an interfacial layer was observed in the films deposited in 1×10^-2 Pa atmosphere. According to the thickness of the LAO film and interfacial layer and the measured capacitance, it could be deduced that the interfacial layer was not pure SiO₂. Auger electron spectroscopy, secondary ion mass spectroscopy and X-ray photoelectron spectroscopy depth analyses indicated that the interfacial layer was La–Al–silicate rather than pure silicon oxide and that the La and Al concentrations in the interfacial layer had gradients from the LAO layer to the substrate. PACS 79.61.Jv; 77.55.+f; 81.15.Gh     

Oxidation of Ni(Pt)Si by molecular vs. atomic oxygen

X-ray photoelectron spectroscopy (XPS) has been used to characterize the oxidation of a clean Ni(Pt)Si surface under two distinct conditions: exposure to a mixed flux of atomic and molecular oxygen (O + O₂; PO+O₂ = 5 × 10⁻⁶ Torr) and pure molecular oxygen (O₂; PO₂ = 10⁻⁵ Torr) at ambient temperatures. Formation of the clean, stoichiometric (nickel monosilicide) phase under vacuum conditions results in the formation of a surface layer enriched in PtSi. Oxidation of this surface in the presence of atomic oxygen initially results in formation of a silicon oxide overlayer. At higher exposures, kinetically limited oxidation of Pt results in Pt silicate formation. No passivation of oxygen uptake of the sample is observed for total O + O₂ exposure <8 × 10⁴ L, at which point the average oxide/silicate overlayer thickness is 23 (3) Å (uncertainty in the last digit in parentheses). In contrast, exposure of the clean Ni(Pt)Si surface to molecular oxygen only (maximum exposure: 5 × 10⁵ L) results in slow growth of a silicon oxide overlayer, without silicate formation, and eventual passivation at a total average oxide thickness of 8(1) Å, compared to a oxide average thickness of 17(2) Å (no silicate formation) for the as-received sample (i.e., exposed to ambient.) The aggressive silicon oxidation by atomic oxygen, results in Ni-rich silicide formation in the substrate and the kinetically limited oxidation of the Pt.     

Dielectric properties of SrZrO3 thin films prepared by pulsed laser deposition

SrZrO₃ (SZO) thin films have been prepared on Pt-coated silicon substrates and directly on Si substrates by pulsed laser deposition (PLD) using a ZrSrO target at a substrate temperature of 400 °C in 20 Pa oxygen ambient. X-ray –2 scans showed that the as-deposited films remain amorphous at a substrate temperature of 400 °C. The dielectric constant of SZO has been determined to be in the range 24–27 for the Pt/SZO/Pt structure. Capacitance–voltage (C–V) characteristics of a metal-oxide-semiconductor (MOS) structure for SZO films deposited in 20 Pa oxygen ambient and 20 Pa nitrogen ambient (SZON) indicated that incorporation of nitrogen during the substrate heating and film deposition can suppress the formation of an interfacial SiO₂ layer, and the SZON films have a lower equivalent oxide thickness (EOT) than that of the SZO films. However, the leakage current of the SZON films is larger than that of the SZO films. The EOT is about 1.2 nm for a 5-nm SZON film deposited at 400 °C. The leakage-current characteristics of as-deposited SZON films and SZON films post-annealed in oxygen ambient by rapid thermal annealing (RTA) have been studied comparatively. The films post-annealed with RTA have a lower leakage current than the as-deposited SZON films. Optical transmittance measurements showed that the band gap of the films is about 5.7 eV. It is proposed that SrZrO₃ films prepared at 400 °C are potential materials for alternative high-k gate-dielectric applications. PACS 77.84.Bw; 77.84.-s; 77.55.+f     

Characterization and structure study of the anodic oxide film on Zircaloy-4 synthesized using NaOH electrolytes at room temperature

Thick crystalline zirconium oxide films were synthesized on Zircaloy-4 substrates by anodic oxidation at room temperature in NaOH solution with a stable applied voltage (300 V). The film is approximately 4.7 μm in thickness. The XPS and SEM analysis shows that the film is a three-layer structure in water, hydroxide and oxide parts. The thickness of that order is ∼0.01 μm, ∼1 μm, ∼3.7 μm, respectively. The oxide layer is composed of tetragonal and monoclinic phases with the volume ratio about 0.2. Furthermore, the thick anodic film acts as a barrier to oxygen and zirconium migrations. It effectively protects zirconium alloys against the worse corrosion. An extremely low passive current density of ∼0.018 μA/cm² and a low oxidation weight gain of ∼0.411 mg/cm² were also observed in the films.     

Optical and electrical properties of optimized thin gold films as top layer of MIS solar cells

The optical spectral response between 340–860 nm and electrical conductivity measurements were made on thermally evaporated gold films in the thickness range 50–130 Å in order to identify optimal properties for their use as the top layer of MIS solar cells. Films of lower evaporation rate and thickness range 70–100 Å were found to have high transmittance and low reflectance, which is desirable for the above purpose. Films thinner than 70 Å had poor electrical conductivity and thicker than 100 Å had poor solar transmittance, hence were rejected. Improved transmittance and conductivity were obtained upon annealing the film at 250°C for about two hours.     

Electrical performance of Ti/Pt thin films on glass-ceramic substrates after high temperature loading

In this study, the influence of post-deposition annealings (PDA) up to temperatures of T _PDA=700°C on the room-temperature resistivity of e-beam evaporated titanium/platinum (Ti/Pt) bi-layers on low temperature co-fired (LTCC) substrates covered with a glass encapsulate is investigated. The thickness of the platinum top layer is varied between 24 and 95 nm (titanium film thickness: 5 nm) and between 23 and 90 nm (titanium film thickness: 15 nm), respectively. In the “as-deposited” state and up to post-deposition annealing temperatures of T _PDA=450°C, the film resistivity is linearly correlated with the reciprocal value of the platinum film thickness according to the size effect. When applying, however, solely the Fuchs-Sondheimer model for evaluation, the effective mean free path for electrons is substantially above the value reported for crystalline platinum at room temperature. Compared to similar investigations on smooth Si/SiO₂ substrates yielding interpretable results within this theoretical approach, this is due to the increase of the thickness-dependent fraction in film resistivity which is strongly affected by the enhanced LTCC/glass surface roughness. At T _PDA>600°C, diffusion of titanium into the platinum top layer and the roughening of the LTCC/glass substrate dominate the electrical behavior, both causing an increase in film resistivity above average. In contrast to Si/SiO₂ substrates, thermal induced grooving effects in the Pt top layer play a minor role as the temperature coefficients of expansion of metallization and glass-ceramic substrate match better and the effective temperature difference for stress generation is lower due a glass softening temperature of about 450°C.     

Fabrication and characterization of Pt intermediate transparent and conducting ITO/Pt/ITO multilayer films

Platinum intermediate transparent and conducting ITO/metal/ITO (IMI) multilayered films were deposited by RF and DC magnetron sputtering on polycarbonate substrates without intentional substrate heating. Changes in the microstructure and optoelectrical properties of the films were investigated with respect to the thickness of the intermediate Pt layer in the IMI films. The thickness of Pt film was varied from 5 to 20 nm.In XRD measurements, neither ITO single-layer films nor IMI multilayer films showed any characteristic diffraction peaks for In₂O₃ or SnO₂. Only a weak diffraction peak for Pt (1 1 1) was obtained in the XRD spectra. Thus, it can be concluded that the Pt-intermediated films in the IMI films did not affect the crystallinity of the ITO films. However, equivalent resistivity was dependent on the presence and thickness of the Pt-intermediated layer. It decreased as low as 3.3×10⁻⁴ Ω cm for ITO 50 nm/Pt 20 nm/ITO 30 nm films. Optical transmittance was also strongly influenced by the Pt-intermediated layer. As Pt thickness in the IMI films increased, optical transmittance decreased to as low as 30% for ITO 50 nm/Pt 20 nm/ITO 30 nm films.     

Characterization of thin silicon oxide obtained by lamp heating

Ultrathin gate oxides (90–300 Å) have been grown on silicon under dry oxygen using a lamp light heater. The oxidation kinetics is quite different from that expected in conventional furnace oxidation since the process is shown to be diffusion limited.Infrared absorption analysis shows neither shift nor broadening of the Si-O stretching mode, indicating that the rapid oxide is stoichiometric with a good structural order. The electrical characteristics of Al-gate capacitors assessed byC-V andG-V measurements with thickness as parameter shows a good quality for oxide films thinner than 100 Å. For thicknesses higher than this value, cleaning techniques and post-oxidation annealing must be used.     

Investigation of ferromagnetic coupling between Co layers in a Co/Pt multilayer with perpendicular anisotropy

The coercivity of a Co/Pt multilayer with out-of-plane anisotropy can be lowered greatly if it is grown onto an ultrathin NiO underlayer . By making use of this characteristic, a series of samples glass/NiO(10 Å)/[Co(4 Å)/Pt(5 Å)]₃/Pt(x Å)/[Co(4 Å)/Pt(5 Å)]₃ with different Pt spacer thickness have been prepared to determine the ferromagnetic (FM) coupling between Co layers across the Pt layer. The measurements of major and minor hysteresis loops have shown that the FM coupling between the top and bottom Co/Pt multilayers decreases monotonically with the Pt layer thickness and disappears above the Pt layer thickness of 40 Å. This thickness of 40 Å is much larger than that in the literature. In addition to the FM coupling between the top and bottom Co/Pt multilayers across the Pt spacer, there exists a weak biquadratic coupling, which induces the broad transition of the bottom Co/Pt multilayer.