A parametric study of AlN thin films grown by pulsed laser deposition

High quality AlN thin films were grown at 200–450°C on sapphire substrates by laser ablation of Al targets in nitrogen reactive atmosphere. The nitrogen pressure was varied between 10⁻³ and 10⁻¹ mbar. The reactive gas pressure during irradiation and the temperature of the substrate were found to essentially influence the quality of the layers. X-ray diffraction analysis evidenced the formation of highly orientated layers for a very restrictive set of parameters. Other analysis techniques, like X-ray photoelectron spectroscopy, secondary ion mass spectroscopy, optical transmission spectroscopy have been used to evidence the good stoichiometry and purity of the films. The characteristics of these films were compared with those of AlN thin films deposited in similar experimental conditions, on Si (100) and Si (111) substrates.     

Deposition and structural characterization of poly-Si thin films on Al-coated glass substrates using hot-wire chemical vapor deposition

The growth of polycrystalline Si films onto Al-coated Corning 7059 glass substrates using hot-wire chemical vapor deposition (HW-CVD) was investigated. The crystalline fraction, grain structure and average grain size of the films were compared as a function of the growth rate and the Si/Al thickness ratio. Micrometre-size Si grains were achieved with a Si/Al ratio of 2 and Si thickness of 2 μm at a growth rate of 1 μm h⁻¹. It was found that the films had a bimodal grain size distribution, which included nanocrystalline Si, and that the growth of micrometre-size crystallites does not continue as the thickness of Si film increases. At a growth rate of 5 μm h⁻¹, films are similar to those grown on glass with an average grain size less than 60 nm and crystalline fraction of 75%.     

Al2O3 formation on Si by catalytic chemical vapor deposition

Catalytic chemical vapor deposition (Cat-CVD) has been developed to deposit alumina (Al₂O₃) thin films on silicon (Si) crystals using N₂ bubbled tri-methyl aluminum [Al(CH₃)₃, TMA] and molecular oxygen (O₂) as source species and tungsten wires as a catalyzer. The catalyzer dissociated TMA at approximately 600 °C. The maximum deposition rate was 18 nm min⁻¹ at a catalyzer temperature of 1000 °C and substrate temperature of 800 °C. Metal oxide semiconductor (MOS) diodes were fabricated using gates composed of 32.5-nm-thick alumina film deposited at a substrate temperature of 400 °C. The capacitance measurements resulted in a relative dielectric constant of 7.4, fixed charge density of 1.74×10¹² cm⁻², small hysteresis voltage of 0.12 V, and very few interface trapping charges. The leakage current was 5.01×10⁻⁷ A cm⁻² at a gate bias of 1 V.     

Dielectric properties of AlN films prepared by laser-induced chemical vapour deposition

The dielectric properties and electrical conductivity of AlN films deposited by laser-induced chemical vapour deposition (LCVD) are studied for a range of growth conditions. The static dielectric constant is 8.0 ± 0.2 over the frequency range 10²−10⁷ Hz and breakdown electric fields better than 10⁶ V cm⁻¹ are found for all films grown at temperatures above 130°C. The resistivity of the films grown under optimum conditions (substrate temperature above 170°C, NH₃/TMA flow rate ratio greater than 300 and a deposition pressure of 1–2 Torr) is about 10¹⁴ Ω cm and two conduction mechanisms can be identified. At low fields, F < 5 × 10⁵ V cm⁻¹ and conductivity is ohmic with a temperature dependence showing a thermal activation energy of 50–100 meV, compatible with the presumed shallow donor-like states. At high fields, F > 1 × 10⁶ V cm⁻¹, a Poole-Frenkel (field-induced emission) process dominates, with electrons activated from traps at about 0.7–1.2 eV below the conduction band edge. A trap in this depth region is well-known in AlN. At fields between 4 and 7 × 10⁵ V cm⁻¹ both conduction paths contribute significantly. The degradation of properties under non-ideal growth conditions of low temperature or low precursor V/III ratio is described.     

Highly conductive and transparent ZnO:Al thin films prepared on high-temperature substrates by d.c. magnetron sputtering

Highly conductive and transparent aluminium-doped ZnO (AZO) thin films have been prepared on high-temperature substrates using d.c. magnetron sputtering. In AZO films, the spatial distribution of resistivity across substrates placed parallel to the target was improved by deposition at substrate temperatures above 300 °C. AZO films with resistivities of 2−5 x 10⁻⁴ Ω cm were prepared under sputter gas pressures of between 0.6 and 3.0 Pa and at a substrate temperature of 350 °C. In addition, milky AZO films with a textured surface were prepared on high-temperature substrates under sputtering conditions which suppressed the c-axis orientation. A total transmittance of 72% and a haze factor of 63% at a wavelength of 500 nm and a sheet resistance as low as 2.0 Ω sq⁻¹ were obtained in milky AZO films 3 μm thick prepared at a sputter gas pressure of 12 Pa and a substrate temperature of 350 °C.     

Electrical properties of evaporated polycrystalline Ge thin-films

Electrical properties of Ge thin films evaporated on Si₃N₄ CVD-coated Si substrate were improved by introducing a heat treatment after the deposition of Ge films. Evaporation conditions were optimized by changing the substrate temperature and deposition rate, and then, heat treatment was performed. At substrate temperatures during the evaporation lower than 300 °C and higher than 400 °C, deposited films were amorphous and polycrystalline, respectively. At substrate temperatures lower than 400 °C, Ge films were evaporated without degrading the surface roughness. The Hall mobility of films evaporated at room temperature increased with increasing the substrate and heating temperature and showed about 400 cm² V⁻¹ s⁻¹ for the hole concentration of 4 × 10¹⁷ cm⁻³ at the heating temperature of 900 °C. This value was almost comparable to that of p-type Ge single crystal.     

Development of textures during the growth of silver films condensed in vacuum on glass

The crystal orientation of silver films evaporated onto glass in a vacuum of better than 1.33 × 10⁻³ Pa was studied as a function of the film thickness in the range 0.1–10 μm by means of the X-ray texture goniometer technique. When the substrate was at room temperature and the deposition rate was high (200 and 100 nm s⁻¹), the 111 orientation was prominent at small film thicknesses. Further film growth led to a rapid increase in the 100 orientation, which became predominant. Elevation of the substrate temperature at the same deposition rates resulted in a decrease in the number of crystallites oriented along the 100 axis, and at temperatures above 473 K the 111 orientation was dominant over the whole thickness range investigated. At a comparatively low deposition rate of 5 nm s⁻¹ at both room temperature and 573 K the crystallites were oriented with their (111) planes parallel to the substrate independent of the film thickness.     

Semiconducting and structural properties of CrSi2 A-type epitaxial films on Si(111)

Chromium disilicide (CrSi₂) films 1 000 Å thick have been prepared by molecular beam epitaxy on CrSi₂ templates grown on Si(111) substrate. The effect of the substrate temperature on the structural, electrical and optical properties of CrSi₂ films has been studied by transmission and scanning electron microscopies, optical microscopy, electrical resistivity and Hall effect measurements and infrared optical spectrometry. The optimal temperature for the formation of the epitaxial A-type CrSi₂ film have been found to be about 750°C. The electrical measurement have shown that the epitaxial A-type CrSi₂ film is p-type semiconductor having a hole concentration of 1 × 10¹⁷cm⁻³ and Hall mobility of 2 980 cm² V⁻¹ s⁻¹ at room temperature. Optical absorption coefficient data have indicated a minimum, direct energy gap of 0.34 eV. The temperature dependence of the Hall mobility (μ) in the temperature range of T = 180–500 K can be expressed as μ = 7.8 × 10¹⁰T⁻³cm²V⁻¹s⁻¹.     

Preparation of Pt-PtOx thin films as electrode for memory capacitors

Pt-PtO_x thin films were prepared on Si(100) substrates at temperatures from 30 to 700°C by reactive r.f. magnetron sputtering with platinum target. Deposition atmosphere was varied with O₂/Ar flow ratio. The deposited films were characterized by X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy. Resistively of the deposited films was measured by d.c. four probe method. The films mainly consisted of amorphous PtO and Pt₃O₄ (or Pt₂O₃) below 400°C, and amorphous Pt was increased in the film as a deposition temperature increased to 600°C. When deposition temperature was thoroughly increased, (111) oriented pure Pt films were formed at 700°C. Compounds included in the films strongly depended on substrate temperature rather than O₂/Ar flow ratio. Electrical resistivity of Pt-PtO_x films was measured to be from the order of 10⁻¹ Ω cm to 10⁻⁵ Ω cm, which was related to the amount of Pt phase included in the deposited films.     

Reactions in Au/Nb bilayer thin films

The interdiffusion and intermetallic compound formation of Au/Nb bilayer thin films annealed at 200–400 °C have been investigated. The bilayer thin films were prepared by electron beam deposition. The Nb film was 50 nm thick and the Au film was 50–200 nm thick. The interdiffusion of annealed specimens was examined by measuring the electrical resistance and depth-composition profile and by transmission electron microscopy. Interdiffusion between the thin films was detected at temperatures above 325 °C in a vacuum of 10^-4 Pa. The intermetallic compound Au₂Nb₃ and other unknown phases form during annealing at over 400 °C. The apparent diffusion constants, determined from the penetration depth for annealing at 350 °C, are 3.5 × 10⁻¹⁵ m² s⁻¹ for Nb in Au and 8.6 × 110^7minus;15 m² s⁻¹ for Au in Nb. The Au surface of the bilayer films becomes uneven after annealing at over 400 °C due to the reaction.     

Atomic-layer doping in Si by alternately supplied PH3 and SiH4

Atomic-layer doping of P in Si epitaxial growth by alternately supplied PH₃ and SiH₄ was investigated using ultraclean low-pressure chemical vapor deposition. Three atomic layers of P adsorbed on Si(100) are formed by PH₃ exposure at a partial pressure of 0.26 Pa at 450°C. By subsequent SiH₄ exposure at 220 Pa at 450°C, Si is epitaxially grown on the P-adsorbed surface. Furthermore, by 12-cycles of exposure to PH₃ at 300–450°C and SiH₄ at 450°C followed by 20-nm thick capping Si deposition, the multi-layer P-doped epitaxial Si films of average P concentrations of 10²¹ cm⁻³ are formed. The resistivity of the film is as low as 2.4×10⁻⁴ Ω cm. By annealing the sample at 550°C and above, it is found that the resistivity increases and the surface may become rough, which may be due to formation of SiP precipitates at 550°C and above. These results suggest that the epitaxial growth of very low-resistive Si is achieved only at a very low-temperature such as 450°C.     

Growth of GaN and AlN thin films by laser induced molecular beam epitaxy

Hexagonal GaN and AlN thin films were grown by laser induced molecular beam epitaxy using Al or Ga metal as target material and N₂as nitrogen source. The films were deposited on sapphire (0001) and SiC (0001) substrates. Epitaxial growth of GaN has been achieved at 730°C and 10⁻³ mbar N₂ pressure. The AlN films were polycrystalline with predominant (0001) orientation.     

Self-assembled growth and magnetotransport investigations on strained Si/SiGe multilayers on vicinal (113)-Si surfaces

We have reported on the growth and magnetotransport properties of modulation p-doped Si_1−xGe_x quantum wells on strained multilayers of 2.5 nm Si_1−xGe_x/10 nm Si on vicinal (113) Si surfaces. Owing to the strong step-bunching properties of the (113) Si surface, both the Si_1−xGe_x and the Si layers exhibited a regular pattern of large steps. Low-temperature magnetotransport measurements revealed a hole density (6–9×10¹¹ cm⁻²) independent of direction, whereas a pronounced mobility anisotropy was found. The mobility (1000–2000 cm²/Vs) was approximately two times higher along the [33-2] direction compared to a perpendicular [−110] direction. This is attributed to anisotropic hole scattering caused by anisotropic shear strain which is always present in strained layers on (113) Si. No influence of the large regular steps, whose direction is given by the direction of the substrate miscut, on the mobility was found.     

Synthesis of AlN by reactive sputtering

We present a systematic study of the sub-band gap optical absorption coefficients (hν) in the range 1.2–6 eV vs. deposition-temperature (T_s from 27 to 450°C) films deposited on silica by 13.6 MHz magnetron sputtering of an Al target with 53 and 72% N₂ in the reactive mixture. X-ray diffraction, infrared absorption and Raman diffusion are also presented, mainly on films deposited on Si in the same run to help in the characterisation of the films. All signals are specific of AlN polycrystalline films, which are of better quality when deposited with 72% N₂. The lowest sub-band gap optical absorption around 5×10² cm⁻¹ is obtained for deposition on silica at T_s=300°C with 72% N₂ and is close to that of heteroepitaxial films deposited on sapphire.     

Characterization of FeS2-pyrite thin films synthesized by sulphuration of amorphous iron oxide films pre-deposited by spray pyrolysis

FeS₂-thin films with good crystallinity were synthesized by a simple method which consists of sulphuration, under vacuum, of amorphous iron oxide thin films pre-deposited by spray pyrolysis of FeCl₃·6H₂O (0.03 M)-based aqueous solution onto glass substrates heated at 350 °C. At optimum sulphuration temperature (450 °C) and duration (6 h), black green layers having granular structure and high absorption coefficient (5.10⁴ cm⁻¹) were obtained. The study of the electrical properties of the as-prepared films vs. the temperature variations showed three temperature domain dependence of the conductivity behaviour. The first one corresponds to the high temperature range (330 K–550 K) for which an Arrhenius plot type was obtained. The activation energy value was estimated at about 61.47 meV. The second domain corresponding to the intermediate temperature range (80 K–330 K) showed a variable activation energy between the grain boundaries. The barrier height, q¯, was estimated to 27±0.5 meV, and the standard deviation, qσ, was evaluated at about 14±0.5 meV. We found that at lower temperatures (20 K–80 K), the conductivity is governed by two conduction types. The density of localised states, was about 2.45×10²⁰ eV⁻¹ cm⁻³.     

Influence of conventional furnace and rapid thermal annealing on the quality of polycrystalline β-FeSi2 thin films grown from vapor-deposited Fe/Si multilayers

Thin films of polycrystalline β-FeSi₂ were grown on (100) Si substrates of high resistivity by electron beam evaporation of Si/Fe ultrathin multilayers and subsequent annealing by conventional vacuum furnace (CVF) and rapid thermal annealing (RTA) for 1 h and 30 s, respectively, in the temperature range from 600 to 900°C. X-ray diffraction, Raman spectroscopy, spectroscopic ellipsometry, resistivity and Hall measurements were employed for characterization of the silicide layers quality in terms of the annealing conditions. For the silicide layers prepared by CVF annealing, although the grain size increase with increasing the annealing temperature, the optimum temperature to obtain the higher material quality (carrier mobility of the order of 100 cm² Vs⁻¹ and carrier concentration of about 1 × 10¹⁷ cm⁻³) is about 700°C. At higher annealing temperatures, the quality of the material is degraded due to the presence of the oxide Fe₂O₃. In the case of the silicides prepared by RTA, the quality of the material is improved progressively with increasing the annealing temperature up to 900°C.     

等离子体辅助反应式脉冲激光熔蚀制备AlN薄膜的低温生长

使用等离子体辅助反应式脉冲激光溅射沉积薄膜的方法在Ｓｉ（１１１）和Ｓｉ（１００）基片上已经成功地低温制备出ＡｌＮ多晶膜。实验表明,当脉冲能量密度ＤＥ＝１．０Ｊ·ｃｍ－２,脉冲频率ｆ＝５Ｈｚ,氮气气压ＰＮ２＝１．３３×１０４Ｐａ,基底温度ｔｓｕｂ＝２００℃,放电电压Ｖ＝６５０Ｖ,基靶距离ｄＳ－Ｔ＝４ｃｍ时薄膜的生长速度等于６ｎｍ／ｍｉｎ。ＡｌＮ薄膜的折射率为２．０５,和基底的取向关系分别为：ＡｌＮ（１１０）∥Ｓｉ（１１１）和ＡｌＮ（１００）∥Ｓｉ（１００）。     

Growth of PbS and CdS thin films by low-pressure chemical vapour deposition using dithiocarbamates

Thin films of cadmium and lead sulphides grown by chemical vapour deposition (CVD) and remote plasma enhanced chemical vapour deposition (RPECVD) using dithiocarbamates as precursors were prepared on fused silica, sapphire, (111)Si and (111)InP substrates. These films were deposited in the temperature range 473–873 K. It was established that the activation energy of the CVD process is 191.5±1.5 kJ mol⁻¹. The structure of polycrystalline films was halenide for PbS and wurtzite for CdS. It was also found that r.f.-plasma activation of the gas phase decreases remarkably the growth temperature and orders the film structure. RPECVD sulphide films had a high degree of preferred orientation.     

Structural, electrical, and optical studies on rapid thermally processed ferroelectric BaTiO3 thin films prepared by metallo-organic solution deposition technique

Polycrystalline BaTiO₃ thin films having the perovskite structure were successfully produced on platinum coated silicon, bare silicon, and fused quartz substrate by the combination of the metallo-organic solution deposition technique and post-deposition rapid thermal annealing treatment. The films exhibited good structural, electrical, and optical properties. The electrical measurements were conducted on metal-ferroelectric-metal (MFM) and metal-ferroelectric-semiconductor (MFS) capacitors. The typical measured small signal dielectric constant and dissipation factor at a frequency of 100 kHz were 255 and 0.025, respectively, and the remanent polarization and coercive field were 2.2 μC cm⁻² and 25 kV cm⁻¹, respectively. The resistivity was found to be in the range 10¹⁰–10¹² Ω·cm, up to an applied electric field of 100 kV cm⁻¹, for films annealed in the temperature range 550–700 °C. The films deposited on bare silicon substrates exhibited good film/substrate interface characteristics. The films deposited on fused quartz were highly transparent. An optical band gap of 3.5 eV and a refractive index of 2.05 (measured at 550 nm) was obtained for polycrystalline BaTiO₃ thin film on fused quartz substrate. The optical dispersion behavior of BaTiO₃ thin films was found to fit the Sellmeir dispersion formula well.     

Preparation and properties of TiN and AlN films from alkoxide solution by thermal plasma CVD method

Single phase TiN and AlN films were prepared on a Si wafer from titanium tetra-etoxide and aluminum tri-butoxide solutions dissolved in ethanol and toluene, respectively, using an Ar/N₂/H₂ radio-frequency (r.f.) inductive thermal plasma chemical vapor deposition (CVD) method. The films were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, measurement of electrical resistivity and Vickers microhardness. Factors affecting the formation of the films (lattice parameter, chemical composition, oxygen/carbon content, and deposition rate of the films) were examined in terms of the N₂ flow rate (2.5–4.5 slm), substrate temperature (300–700°C), feed rate of the solution (0.025–0.3 ml/min), and the mole ratio of the alkoxide solution (1:1–1:3). The optimum conditions for preparation of TiN films produced a film 0.2–3 μm thick with an oxygen content of 8 at.% and a free carbon content of 4 at.%, showing an electrical resistivity of 370 μΩ cm. The optimum conditions for AlN films produced a film 0.3 μm thick containing 14 at.% oxygen and 8 wt.% carbon. The deposition rate of the TiN film was determined to be 30–35 nm/min. The Vickers microhardness of the TiN and AlN films was found to be 10±1 and 13±3 GPa, respectively.