Structural properties of SiO2 films prepared by plasma-enhanced chemical vapor deposition

SiO₂ thin films have been prepared by plasma-enhanced chemical vapor deposition from SiH₄ and N₂O precursors by using different values of the N₂O/SiH₄ flow ratio (γ). Rutherford backscattering spectrometry has been employed to obtain the O/Si atomic ratio of the films. Infrared spectroscopy has demonstrated that oxides having the same O/Si atomic ratio are characterized by a different structure. Indeed, from the analysis of the Si–O–Si stretching peaks, we have found that the peak frequency and full-width at half-maximum (FWHM) are dependent on γ. Peak position and FWHM have been used to calculate the bond angle distribution of the films. The results have demonstrated the occurrence of a Si–O–Si bond angle relaxation phenomenon in films deposited by using a larger excess of N₂O.     

Plasma-enhanced chemical-vapor deposition oxide prepared at low-flow conditions for course wavelength-division multiplexing optical-waveguide devices

Silicon oxide (SiO_x) films grown by plasma-enhanced chemical-vapor deposition (PECVD) were investigated for applications in a course wavelength-division multiplexing (CWDM) network. The SiO_x films were deposited on 4-in. silicon wafers based on the reaction of N₂O/SiH₄ precursors. After postdeposition annealing at 1,150°C, the transmission spectra of the films prepared at different flow rates of the precursor were compared. We found that the transmission spectrum of the films deposited at the low-flow conditions can be flattened to a ripple of less than 0.5 dB ranging from visible up to 1,470 nm. In addition, the material losses at wavelengths around 1,500 nm caused by absorption of Si-H and N-H bonds were significantly reduced.     

Properties of thin LPCVD silicon oxynitride films

Thin, uniform silicon oxynitride films with films thicknesses of ≤ 10 nm were successfully deposited by low pressure chemical vapor deposition (LPCVD). The reactant gases were SiH₂Cl₂, N₂O, and NH₃. The compositional uniformity of these films as a function of depth was good. The structure of these oxynitride films was found to be dominated by the mixed matrix of Si, N, and 0, rather than a physical mixture of SiO₂ and Si₃N₄ clusters. N-H bonding was observed and the total amount of hydrogen in the as-deposited film was on the order of 5 x l0²⁰/cm³. No H-OH or Si-OH bonds were detected. Excellent dielectric breakdown distributions were found for oxynitride films with equivalent oxide film thicknesses as low as 7.5 nm. The conduction of Si-N-0 films depended on film composition. A small capacitor-voltage (C-V) window (< 0.1 V) was observed for the Si-N-O/Si structures. The midgap surface state density was on the order of 5 x 10¹⁰/cm² /eV. Either trapping of holes or the generation of positive states were found after high field stressing of the oxynitride films.     

Bulk passivation of multicrystalline silicon solar cells induced by high‐rate‐deposited (> 1 nm/s) silicon nitride films

Silicon nitride (a‐SiN_x:H) films deposited by the expanding thermal plasma at high rate (> 1 nm/s) have been studied for application as anti‐reflection coatings for multicrystalline silicon (mc‐Si) solar cells. Internal quantum efficiency measurements have revealed that bulk passivation is achieved after a firing‐through process of the a‐SiN_x:H as deposited from NH₃/SiH₄ and N₂/SiH₄ plasmas. However, the a‐SiN_x:H films deposited from N₂/SiH₄ show a lower passivation quality than those deposited from NH₃/SiH₄. This has been attributed to a poorer thermal stability of the films deposited from the N₂/SiH₄ plasma, resulting in structural changes within the film during the firing step. Copyright © 2002 John Wiley & Sons, Ltd.     

Effect of thermal annealing on physical properties of vacuum evaporated In2S3 buffer layer for eco-friendly photovoltaic applications

The present communication reports the effect of thermal annealing on the physical properties of In₂S₃ thin films for eco-friendly buffer layer photovoltaic applications. The thin films of thickness 150 nm were deposited on glass and indium tin oxide (ITO) coated glass substrates employing thermal vacuum evaporation technique followed by post-deposition thermal annealing in air atmosphere within a low temperature range 150–450 °C. These as-deposited and annealed films were subjected to the X-ray diffraction (XRD), UV–vis spectrophotometer, current–voltage tests and scanning electron microscopy (SEM) for structural, optical, electrical and surface morphological analysis respectively. The compositional analysis of as-deposited film is also carried out using energy dispersive spectroscopy (EDS). The XRD patterns reveal that the as-deposited and annealed films (≤300 °C) have amorphous nature while films annealed at 450 °C show tetragonal phase of β-In₂S₃ with preferred orientation (109) and polycrystalline in nature. The crystallographic parameters like lattice constant, inter-planner spacing, grain size, internal strain, dislocation density and number of crystallites per unit area are calculated for thermally annealed (450 °C) thin films. The optical band gap was found in the range 2.84–3.04 eV and observed to increase with annealing temperature. The current–voltage characteristics show that the as-deposited and annealed films exhibit linear ohmic behavior. The SEM studies show that the as-deposited and annealed films are uniform, homogeneous and free from crystal defects and voids. The grains in the thin films are similar in size and densely packed and observed to increase with thermal annealing. The experimental results reveal that the thermal annealing play significant role in the structural, optical, electrical and morphological properties of deposited In₂S₃ thin films and may be used as cadmium-free eco-friendly buffer layer for thin films solar cells applications.     

Silicon oxynitride integrated waveguide for on-chip optical interconnects applications

This work explores the microfabrication technology for realizing miniature waveguide structure for on-chip optical interconnects applications. Thick oxynitride films were prepared by plasma enhanced chemical vapor deposition (PECVD) with N₂O, NH₃ and SiH₄ precursors. The composition and the bonding structure of the oxynitride films were investigated with Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and secondary ion mass spectroscopy. Results showed that the silicon oxynitride deposited with gas flow rates of NH₃/N₂O/SiH₄ = 10/400/10 (sccm) has favorable properties for integrated waveguide applications. The refractive index of this layer is about 1.5 and the layer has comparative low densities of O–H and N–H bonds. The hydrogen bonds can be further eliminated with high temperature annealing of the as-deposited film in nitrogen ambient and the propagation loss can be reduced significantly with thermal annealing. An integrated miniature waveguide with cross-section of 2 μm × 3 μm was realized with the proposed technology. The waveguide is able to transmit signal in either TE or TM mode with propagation loss <0.6 dB/cm (at 1550 nm) and bending radius of about 6 μm.     

Effects of annealing in O2 and N2 on the electrical properties of tantalum oxide thin films prepared by electron cyclotron resonance plasma enhanced chemical vapor deposition

The tantalum oxide thin films with a thickness of 14 nm were deposited at 95°C by electron cyclotron resonance plasma enhanced chemical vapor deposition (ECRPECVD), and annealed at various temperatures (700∼850°C) in O₂ and N₂ ambients. The microstructure and composition of the tantalum oxide thin films and the growth of interfacial silicon oxide layer were investigated and were related to the electrical characteristics of the film. Annealing in an O₂ ambient led to a high dielectric constant (ε_r(Ta₂O₅) = 24) as well as a small leakage current (E_bd = 2.3 MV/cm), which were due to the improved stoichiometry and the decreased impurity carbon content. Annealing in an N₂ ambient resulted in poor and nonuniform leakage current characteristics. The as-deposited tantalum oxide films were crystallized into δ-Ta₂O₅ after annealing at above 750°C regardless of the ambient. The leakage current of the film abruptly increased after annealing at 850°C probably because of the stress caused by thermal expansion or contraction.     

Post deposition UV-induced O2 annealing of HfO2 thin films

UV-assisted annealing processes for thin oxide films is an alternative to conventional thermal annealing and has shown many advantages such as low annealing temperature, reducing annealing time and easy to control. We report in this work the deposition of ultra-thin HfO₂ films on silicon substrate by two CVD techniques, namely thermal CVD and photo-induced CVD using 222 nm excimer lamps at 400 °C. As-deposited films of around 10 nm in thickness with refractive indices from 1.72 to 1.80 were grown. The deposition rate measured by ellipsometry was found to be about 2 nm/min by UV-CVD, while the deposition rate by thermal CVD is 20% less than that by UV-CVD. XRD showed that the as-deposited HfO₂ films were amorphous. This work focuses on the effect of post deposition UV annealing in oxygen on the structural, optical and electrical properties of the HfO₂ films at low temperature (400 °C). Investigation of the interfacial layer by FTIR revealed that thickness of the interfacial SiO₂ layer slightly increases with the UV-annealing time and UV annealing can convert sub-oxides at the interface into stoichiometric SiO₂, leading to improved interfacial qualities. The permittivity ranges in 8–16, are lower than theoretical values. However, the post deposition UV O₂ annealing results in an improvement in effective breakdown field and calculated permittivity, and a reduction in leakage current density for the HfO₂ films.     

4 nm Gate dielectrics prepared by RTP low pressure oxidation in O2 and N2O atmosphere

Extensive experimental results are reported about the rapid thermal O₂ and N₂O oxidation of silicon at pressures as low as 25 Torr. The decrease of the oxidation rate in N₂O is smaller than in O₂ atmosphere with decreasing pressure. Therefore, almost equal oxidation rates for the oxidation in O₂ and N₂O atmospheres were found at the lowest investigated pressure of 25 Torr. In addition, the low pressure oxides show better oxide homogeneities across the wafer; this is especially true for N₂O oxides. Ultra-thin (down to 4 nm) dielectric films for application in metal-oxide-semiconductor (MOS) devices have been fabricated and electrically characterized. The low pressure oxides exhibit higher charge to breakdown values and dielectric breakdown fields than atmospheric pressure oxides.     

Minimizing hydrogen content in silicon oxynitride by thermal oxidation of silicon-rich silicon nitride

This work reports a detailed study of the re-oxidation effects on the hydrogen content and optical properties of silicon oxynitride films grown by plasma enhanced chemical vapor deposition (PECVD) with N₂O, NH₃ and SiH₄ as the precursors. Results showed that the silicon oxynitride deposited with gas flow rates of NH₃/N₂O/SiH₄ = 20/500/20 (sccm) has favorable properties for integrated waveguide applications. The refractive index of this layer is about 1.57 at 632.8 nm wavelength and the layer has a comparative low density of NH bonds. With a high temperature re-oxidation of the as-deposited film, the hydrogen content of the oxynitride film was reduced from 2.255 × 10²² to 6.98 × 10²⁰ cm⁻³ which is attributed to the removal of excess silicon oxidation and hydrogen bonds.     

Silica deposition by excimer-laser-induced chemical vapour deposition in perpendicular configuration

Silicon oxide films have been deposited on silicon wafers at low temperature by irradiation of the substrates with an ArF (λ = 193 nm) excimer laser beam in a SiH₄ and N₂O atmosphere. A systematic study of the growth rate and properties of the films as a function of the processing parameters (gas composition, substrate temperature, laser pulse energy, pulse repetition rate, total pressure and gas flow rate) has been performed. The process is photolytically activated in the gas phase and the diffusion of photodecomposed precursor species towards the surface plays an important limiting role. The N₂O/SiH₄ ratio mainly controls the film composition; for ratios above 40, stoichiometric silica may be obtained, as confirmed by Rutherford backscattering (RBS) measurements. The role of the surface temperature in the growth kinetics is not critical, so that deposition of films is possible down to substrate temperatures as low as 70°C. Nevertheless, the density of the films varies greatly with the substrate temperature. The fact that no Si(SINGLE BOND)H vibration was detected with Fourier transform infrared (FTIR) spectrophotometry is surprising, since hydrogen incorporation is a very typical phenomenon encountered in most silane systems. This effect is probably associated with the ultraviolet photon irradiation of the adsorbed species and the film as it grows, thus breaking bonds and affecting the bond structure of the film.     

Electrical properties of composite gate oxides formed by rapidthermal processing

In this study, oxide stacks formed by combinations of rapid thermal chemical vapor deposition and rapid thermal oxidation have been investigated as gate dielectrics. This was achieved by performing various types of in situ rapid thermal oxidations both prior to and after oxide deposition to form composite stacked structures. The oxidation ambient and temperature was varied to study the effect on electrical properties such as mobility, leakage current, charge trapping, breakdown and hot carrier degradation. It was found that pre-oxidation prior to depositing an oxide results in a composite structure that greatly reduces the defect density by mismatching pores and weak spots in each film. The mobility behavior of these films was also found to be improved over as-deposited oxides. Post-deposition oxidation in O₂ and N₂O was also found to improve the mobility characteristics. Additionally, post-annealing in N₂ O was effective in improving the reliability of deposited oxides. These N₂O annealed films had low interface trap densities, improved high field mobility, very low charge trapping characteristics and enhanced resistance to hot carrier induced interface state generation. These improvements are attributed to 1) the presence of nitrogen at the interface and 2) to the reduction of nitrogen and hydrogen concentrations in the bulk of the oxide. The role of atomic oxygen during the post-anneal in N₂O is discussed along with differences in annealing ambients     

TEOS-based PECVD of silicon dioxide for VLSI applications

Silicon dioxide films deposited from tetraethylorthosilicate (TEOS) using plasma-enhanced chemical vapour deposition (PECVD) are reviewed. The effect of the presence of oxygen on the film deposition rate and mechanism and the physical properties of the films, particularly the step coverage properties (conformality), are discussed in detail. Structural characterisation of the films has been carried out via etch rate measurements, infrared transmission spectroscopy, X-ray photoelectron spectroscopy (XPS) and Auger and secondary ion mass spectroscopy (SIMS) analysis. Electrical properties, i.e. resistivity, breakdown strength, fixed oxide charge density, interface state density and trapping behaviour, have been evaluated using metal-oxide-semiconductor (MOS) structures fabricated using the deposited oxides. Films deposited by microwave plasma-enhanced decomposition of TEOS in the presence of oxygen have been found to be comparable with standard silane-based low-pressure chemical vapour deposition (LPCVD) and PECVD oxides. It has been shown that films deposited on thin native oxides grown by either in situ plasma oxidation or low-temperature thermal oxidation exhibit excellent electrical properties.     

Investigation of the electrical transport mechanism in VOx thin films

Vanadium oxide VO₂ is a material that transforms from semiconductor to a metal state at a temperature of 67 °C. This phase transformation is accompanied by a dramatic change in its electrical and optical properties. Therefore, vanadium oxide thin films are most attractive for switching applications. Non-stoichiometric thin films of VO_x, including VO₂, also present such thermal response.This paper presents the optical and electrical properties of vanadium oxide thin films deposited by vacuum thermal evaporation of a metal vanadium with follows oxidation. We have studied the electro-physical behavior of these films during their phase transition. It was shown that the electrical transport mechanism of the obtained vanadium oxide films differ in low and high electrical fields. In low electrical fields, conductivity is obtained by the Schottky transport mechanism, whereas in high electrical fields, conductivity ranges from Ohmic, for medium fields, to Poole-Frenkel for higher fields. Also, FTIR and near IR reflectance characteristics of the obtained films are presented.     

ArF excimer laser induced CVD of aluminum oxide films

The authors have demonstrated photochemical deposition of aluminum oxides from Trimethylaluminum (TMA) and N₂O by using a pulsed ArF excimer laser (193 nm). Both TMA and N₂O are efficiently photodissociated by the 193 nm light. The films are grown on Si and InP wafers contained in a low pressure flowing cell with a heated substrate. The incident laser beam is focused and parallel to the substrate surface. Typical deposition rates are 80–150 A/min. Stripes of aluminum oxide 30 mm wide are uniformly grown on 7.5 cm Si-wafers. The film composition and purity have been investigated using Auger and Infra-red spectroscopy analysis. Surprising results are the relatively low concentration of carbon. Refractive index and thickness have been determined by an ellipsometer. Typical values for the films are 1.54–1.62. Metal-oxide-semiconductor capacitors have been fabricated and characterized. The C-V curves for n-InP/aluminum oxide have clockwise hysteresis, and minimum loop width is less than 0.5 V. The surface state densities are 1 × 10¹¹ cm^-2 eV⁻¹ at the mid band gap.     

Effect of microwave power and reactive gas ratio on the properties of silicon nitride thin films deposited by ECR PECVD

Silicon nitride films were deposited at room temperature on a single crystal silicon substrate by ECR PECVD (electron cyclotron resonance plasma enhanced chemical vapor deposition). Effects of the microwave power and the reactive gas ratio (SiH₄/N₂) on the film properties, such as, refractive index and breakdown field were investigated. It turned out that the microwave power was closely related to the change in refractive index of the silicon nitride films, while breakdown field did not change much from 6 MV/cm. It was also found that the deposition rate, refractive index, and breakdown field were changed in a certain way with respect to the change in SiH₄/N₂ ratio, which could be explained in terms of the activated chemical species concentrations in the plasma during deposition.     

Oxygen and carbon incorporation in low temperature epitaxial Si films grown by rapid thermal chemical vapor deposition (RTCVD)

Using SIMS analysis, we have measured oxygen and carbon concentrations in epitaxial Si films grown between 550 and 900° C. The films were grown by rapid thermal chemical vapor deposition from SiH₄ as well as several different SiH₂Cl₂ sources. We have found that at low deposition temperatures (∼750° C or lower), oxygen incorporation is first dictated by source gas impurities and then by residual chamber gases. For the case of SiH₂Cl₂, which can have substantial oxygen content due to its reactivity with H₂O, oxygen concentrations of about 10²⁰ cm^-3 are typical at low deposition temperatures. SiH₄, however, can be obtained in higher purity, and oxygen concentrations of 10¹⁸ cm^-3 can be realized at low temperatures. At higher deposition temperatures (750-900° C), SiO volatilizes, leaving the films grown from all sources with low oxygen concentrations, typically less than 5 × 10¹⁷ cm^-3. Carbon incorporation is much less of a problem since it is present to a lesser extent both in the chamber background and in the source gases. Carbon levels less than or equal to 10¹⁸ cm^-3 can be obtained at all deposition temperatures greater than about 650° C. The performance ofp/n junctions is shown to degrade significantly for junctions grown below 850° C. We conclude that for growth of long lifetime Si films in the temperature range <800° C, that low residual H₂O partial pressures (<10^-10 Torr) are desired. Therefore, CVD chambers should be loadlocked and also capable of base pressures as low as about 10^-9 Torr.     

Growth of epitaxial Si1-xGex layers at 750° C by VLPCVD

Silicon-germanium epitaxial layers have been grown on (100) silicon at 750° C by very low pressure chemical vapor deposition (VLPCVD). Pure SiH₄ and GeH₄ were used as the processing gases. Commensurate films of Si_1-x withx < 0.13 have been deposited up to a critical thickness about 2-4 times larger than the equilibrium value. Interrupted growth, controlled by gas switching, was employed to improve interfacial abruptness. The films have been characterized as a function of SiH₄ and GeH₄ flow rates and germanium content. Growth rate and germanium incorporation as a function of GeH₄:SiH₄ input ratio and total gas flow rate have been studied. We observed that the growth rate of the Si_1-x Ge _x layer decreases as the germanium content in the film or the GeH₄:SiH₄ ratio increases at 750° C using VLPCVD. We also found that, for a given GeH₄:SiH₄ ratio, the germanium incorporated in the solid is independent of the total gas flow rate.     

Residual stress in silicon nitride films

The mechanical stress caused by Si₃N₄ films on (111) oriented Si wafers was studied as a function of the Si₃N₄ film thickness, deposition rate, deposition temperature and film composition. The Si₃N₄ films were prepared by the reaction of gaseous SiH₄ and NH₃ in the temperature range 700–1000°C. The curvature of the Si substrates caused by the Si₃N₄. films is related to the film stress; the substrate curvature was measured by an optical interference technique. The measured Si₃N₄. film stress was found to be highly tensile with a magnitude of about 10¹⁰ dynes/cm². For the thickness range of 2000–5000Å, there was no change in the measured stress. The total film stress was observed to decrease for decreasing deposition rate and increasing deposition temperature. A large change in film stress was observed for films containing excess Si; the stress decreased with increasing Si content. Based on published values for the thermal expansion coefficients for Si and Si₃N₄, a published value for Young’s Modulus for Si₃N₄, and the measured total stress values, a consistent argument is developed in which the total stress consists of a compressive component due to thermal expansion coefficient mismatch and a larger tensile intrinsic stress component. Both the thermal and intrinsic stress components vary with film deposition temperature in directions which decrease the total room temperature stress for higher deposition temperatures.     

Optimization of SiNX:H films deposited by PECVD for reliability of electronic, microsystems and optical applications

This paper presents the correlation between the optical properties and the chemical and electrical properties of amorphous silicon nitride (SiN_X:H) films prepared by reactor Plasma-Enhanced Chemical Vapor Deposition (PECVD). The effects of temperature and mixture of gases (NH₃/SiH₄/N₂) on these dielectric films are investigated in this study. Silane (SiH₄) and ammonia (NH₃) are used as the reactive species, while nitrogen (N₂) is used as a dilution gas. A particular focus is made on the improvement of the electrical properties that are strongly correlated to the physicochemical bonds films properties. The incorporation of the N₂ dilution leads to the deposition rate and hydrogen content reductions in the film. An optimal gases mixture with N₂ is obtained to improve the breakdown voltage at low temperature, 200 °C. Fundamental properties of these fabricated films are characterized by their elemental composition, chemical specification, residual stress, optical and electrical properties. The results experimentally show that this film can be used to improve some of the key deposition parameters for the reliability of semiconductor, microsystems and optical applications.