A study on the formation and characteristics of the Si---O---C---H composite thin films with low dielectric constant for advanced semiconductor devices

The Si---O---C---H composite thin films were deposited on a p-type Si(100) substrate using bis-trimethylsilane (BTMSM) and O₂ mixture gases by an inductively coupled plasma chemical vapor deposition (ICPCVD). High density plasma of approximately 10¹² cm⁻³ is obtained at low pressure (<320 mtorr) with an RF power of approximately 300 W in the inductively coupled plasma source where the BTMSM and oxygen gases are greatly dissociated. Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) spectra show that the film has Si---CH₃ and O---H related bonds. The CH₃ groups formed the void in the film and the Si atoms in the annealed sample have different chemical states from those in the deposited sample. It means that the void is formed due to the removing of O---H related bonds during the annealing process. The relative dielectric constant of the annealed sample with the flow rate ratio O₂/BTMSM as 0.3 at 500°C for 30 min is approximately 2.5.     

R.f. plasma deposition from hexamethyldisiloxane-oxygen mixtures

Hexamethyldisiloxane (HMDSO) has been used as a precursor for the deposition of silicon dioxide films at low substrate temperature (25–400°C) by plasma enhanced chemical vapour deposition processing. Effects of the partial pressure of oxygen in the discharge on the deposition rate and the composition of the films are investigated. The deposition rate is found to decrease with increasing oxygen concentration in the HMDSO/O₂ mixture. The chemical composition of the formed films was characterized by X-ray photoelectron spectroscopy and infrared spectroscopy. Over 40% of the oxygen in the gas phase the carbon content of films deposited from HMDSO/O₂ mixtures is less than 5%.     

Characterization of Cat-CVD grown Si–C and Si–C–O dielectric films for ULSI applications

Si–C films with the Si compositions ranging from 40 to 70% have been grown by Cat-CVD using dimethylsilane [DMSi, Si(CH₃)₂H₂] compounds. Tetraethoxysilane [TEOS, Si(OC₂H₅)₄] and dimethyldimethoxysilane [DMDMOS, Si(CH₃)₂(OCH₃)₂] gas source gave us Si–C–O (C-doped SiO_x) films with wide ternary alloy compositions. The dielectric constant of a Si–C film has been evaluated by C–V measurements (at 1 MHz) using Al/Si–C/n-Si(001)/Cu MIS structure. The relative dielectric constant value of a Si–C film was estimated to be 3.0. The resistivity of the Si–C layer with 1 mm diameter and 0.24 μm thickness was estimated to be more than 24.5 Gohm·cm. These results gave us promising characteristics of Si–C and Si–C–O films grown by alkylsilane- and alcoxysilane-based Cat-CVD.     

Shallow defect states in hydrogenated amorphous silicon oxide

The theoretical cluster-Bethe-lattice method is used in this study to investigate the shallow defect states in hydrogenated amorphous silicon oxide. The electronic density of states (DOS) for the SiO₂ Bethe lattice of various Si–O–Si angles, non-bridging oxygen Si–O^√, peroxyl radical Si–O–O^√, threefold coordinated O₃ and Si–H bonds are calculated. The variation of the Si–O–Si bond angle causes the bandgap fluctuation and induces tail states near the conduction band minimum. The Si–O^√ and Si–O–O^√ bonds introduce shallow defect states in the energy gap near the top of the valence band. The Si–H bond induces a defect state, in the energy gap near the conduction band minimum, in a-SiO_x with high oxygen concentration, but not low oxygen concentration. The O₃ bond itself does not induce defect state in the energy gap. The O₃⁺D⁻ complex, formed by the O₃ and threefold coordinated silicon, induces shallow state in the energy gap near the conduction band minimum. This defect state can explain the energy shift of photoluminescence of a-SiO_x:H under annealing.     

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.     

Effect of nitrogen content on the degradation mechanisms of thin Ta–Si–N diffusion barriers for Cu metallization

The effect of the nitrogen content on the thermal stability and degradation mechanisms of Ta–Si–N diffusion barriers was studied using methods that prove Cu interdiffusion. On the one hand, glancing angle X-ray diffraction was applied to detect Cu₃Si formation after annealing of Cu/Ta–Si–N/Si layer stacks. On the other hand, a combined secondary ion mass spectroscopy and transmission electron microscopy analysis of Ta–Si–N/Cu/Ta–Si–N/SiO₂/Si samples was performed. For a detailed investigation of the microstructure evolution, the crystallization behavior of both Cu-capped and uncapped Ta–Si–N/Si samples was analyzed using X-ray diffraction. In the case of an uncapped Ta₇₃Si₂₇ film, Si interdiffusion from the substrate precedes the layer crystallization. The substrate influence on the crystallization process decreases with increasing N content x_N of the Ta–Si–N layer. Using Cu/Ta–Si–N/Si samples, a critical temperature for Cu silicide formation was determined. This temperature increases with increasing N content of the Ta–Si–N barrier. In the case of Ta–Si–N films with x_N > 25 at.%, Cu interdiffusion into the substrate occurs before a significant barrier crystallization is observed. For Ta–Si–N layers with x_N ≤ 25 at.%, no indications for Cu diffusion before crystalline phase formation were detected.     

Improved fatigue properties of lead zirconate titanate films made on oxygen-implanted platinum electrodes

Pb(Zr_0.3Ti_0.7)O₃ (PZT) thin film capacitors fabricated on an oxygen-implanted Pt bottom electrode were studied. Oxygen was implanted at a low acceleration voltage (40 kV) and dose (1×10¹⁵ cm⁻²). Structural examination by grazing-incident X-ray diffraction (GIXD) and chemical analysis by X-ray photoelectron spectroscopy (XPS) revealed that the implantation generated a very thin amorphous top surface layer (approx. 20 nm), which contained approximately 7% of oxygen that stayed in the film in the form of PtO bonding. The amorphous layer, however, resumed the crystalline structure accompanied by the dissociation of PtO under the rapid thermal annealing at 600 °C for 5 min. The remnant polarization of sol–gel derived Pb(Zr_0.3Ti_0.7)O₃ (PZT) films fabricated on the oxygen-implanted Pt was slightly reduced from 11.92 μC/cm² for the PZT capacitors fabricated on a Pt electrode without implanted oxygen to 9.07 μC/cm². Nevertheless, the fatigue endurance was significantly increased. The switching polarization of PtO_x/PZT/Pt (O-implanted) capacitors remained within 95% of the starting value after 4×10¹⁰ switching cycles, which is comparable to that of PZT capacitors made with other conducting oxides.     

SiO2/TiO2 thin films with variable refractive index prepared by ion beam induced and plasma enhanced chemical vapor deposition

SiO₂/TiO₂ optical thin films with variable compositions have been prepared by ion beam induced and plasma enhanced chemical vapour deposition (IBICVD and PECVD). While the films obtained by IBICVD were very compact, the PECVD ones with a high content of Ti presented a columnar microstructure. The formation of Si–O–Ti bonds and a change in the environment around titanium from four- to six-coordinated has been proved by vibrational and X-ray absorption spectroscopies. The refractive index increased with the titanium content from 1.45 to 2.46 or 2.09 for, respectively, the IBICVD and PECVD films. Meanwhile, the band gap decreased, first sharply and then more smoothly up to the value of pure TiO₂. It is concluded that the optical properties of SiO₂/TiO₂ thin films can be properly tailored by using these two procedures.     

Influence of substrate properties on the growth of titanium films: part III

The growth of thin Ti-oxide films (12 nm) on alumina substrate films formed by reactive evaporation of Ti in an oxygen atmosphere was studied by in situ internal stress measurements under ultra high vacuum conditions and transmission electron microscopy. Oxygen pressure and substrate temperatures were the varied parameters of the reactive evaporation. These Ti-oxide-films with different oxygen content (O₂/Ti-films) were then used as substrate films for the deposition of a clean titanium film. The growth stress of the titanium film on the as-deposited O₂/Ti-substrate films is comparable with that previously found for H₂O/Ti-substrates and indicates island growth and the formation of polycrystalline titanium films. Annealing (400°C, 20 min) of the as-deposited – amorphous – O₂/Ti-films gives rise to the formation of crystalline TiO₂. The amount of TiO₂ formed during annealing is strongly dependent on the oxygen content of the O₂/Ti-film. The oxygen content, in return, is dependent on oxygen partial pressure and substrate temperature during O₂/Ti-film deposition. The corresponding changes in the substrate film properties (oxygen content, crystallinity, etc.) are reflected in significant changes in the growth stress of the titanium film. The stress vs. thickness curve of these titanium films appears to indicate a superposition of the growth stress of two different growth modes, i.e. growth of a polycrystalline film with island growth on the as-deposited, amorphous oxide substrate and epitaxial growth of a quasi single crystalline film on the crystalline TiO₂-substrate.     

Plasma enhanced chemical vapor deposition of titanium (IV) ethoxide–oxygen–helium mixtures

Thin films were deposited by plasma enhanced chemical vapor deposition from titanium (IV) ethoxide (TEOT)–oxygen–helium mixtures. Actinometric optical emission spectroscopy was used to obtain the relative plasma concentrations of the species H, CH, O and CO as a function of the percentage of oxygen in the feed, R_ox. The concentrations of these species rise with increasing R_ox and tend to fall for R_ox greater than about 45%. As revealed by a strong decline in the emission intensity of the actinometer Ar as R_ox was increased, the electron mean energy or density (or both) decreased as greater proportions of oxygen were fed to the chamber. This must tend to reduce gas-phase fragmentation of the monomer by plasma electrons. As the TEOT flow rate was fixed, however, and since the species H and CH do not contain oxygen, the rise in their plasma concentrations with increasing R_ox is explained only by intermediate reactions involving oxygen or oxygen-containing species. Transmission infrared (IRS) and X-ray photoelectron (XPS) spectroscopies were employed to investigate film structure and composition. The presence of CH₂, CH₃, CC, C–O and CO groups was revealed by IRS. In addition, the presence of C–O and CO groups was confirmed by XPS, which also revealed titanium in the + 4 valence state. The Ti content of the films, however, was found to be much less than that of the monomer material itself.     

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.     

Atomic layer deposition of tungsten using sequential surface chemistry with a sacrificial stripping reaction

Tungsten (W) films were grown with atomic layer control using a novel sequence of self-limiting surface reactions. The tungsten film growth was achieved by dividing the binary reaction WF₆+Si₂H₆→W+2SiHF₃+2H₂ into two separate half-reactions. Alternating exposures to WF₆ and Si₂H₆ in an ABAB… sequence produced tungsten deposition at temperatures between 425 and 600 K. The Si₂H₆ reactant served only a sacrificial role to strip fluorine from tungsten without incorporating into the film. FTIR spectroscopic investigations demonstrated that the WF₆ and Si₂H₆ half-reactions were complete and self-limiting at T>400 K. In situ spectroscopic ellipsometry measurements determined a tungsten growth rate of 2.5 Å/AB cycle with WF₆ and Si₂H₆ reactant exposures sufficient for complete half-reactions. The surface topography of the deposited tungsten films was flat indicating smooth film growth. The tungsten films were either amorphous or composed of very small crystalline grains and contained no measurable silicon or fluorine. These results represent the first demonstration of atomic layer deposition of smooth single-element metal films using sequential surface chemistry.     

Electrical characterization of Ta2O5 films deposited by laser reactive ablation of metallic Ta

Tantalum oxide films have been deposited by 355 nm pulsed laser ablation of metallic Ta target in O₃/O₂ ambient. The structure and the composition of as-deposited and annealed films were examined by X-ray diffraction and Fourier transform infrared spectroscopy. The measurements of the current–voltage and capacitance–voltage characteristics of the Al/Ta₂O₅/Si capacitors were performed to reveal the electrical properties of the Ta₂O₅ films. The effects of annealing temperature on the characteristics of thin films have been studied. The results suggest that the films annealed above 700°C have the structure of orthorhombic β-Ta₂O₅, thc annealing treatment at high temperature decreases the bulk trap charge, the border trap, and the interface trap densities of as-deposited films, and improves significantly the dielectric and electrical properties of Ta₂O₅ film.     

Thickness measurement of SiO2 films thinner than 1 nm by X-ray photoelectron spectroscopy

The thickness measurement of ultra-thin SiO₂ films thinner than 1 nm was studied by X-ray photoelectron spectroscopy (XPS). Amorphous SiO₂ thin films were grown on amorphous Si films to avoid the thickness difference due to the crystalline structure of a substrate. SiO₂ thin films were grown by ion beam sputter deposition under oxygen gas flow and the thickness was measured by in situ XPS. The attenuation length was determined experimentally by a SiO₂ film with a known thickness. The straight line fit between the measured thickness using XPS and the nominal thickness showed a good linear relation with a gradient of 0.969 and a small offset of 0.126 nm. The gradient measured at the range of 3.4–0.28 nm was very close to that measured at sub-nanometer range of 1.13–0.28 nm. This result means that the reliable measurement of SiO₂ film thickness below 1 nm is possible by XPS.     

Co-deposition of cobalt disilicide on silicon–germanium thin films

The formation of CoSi₂ on strained epitaxial Si_0.8Ge_0.2/Si(100) films has been studied as a function of the deposition method and annealing temperature. Two types of deposition processes were used: a direct method, where 5 nm of pure Co metal were deposited at room temperature onto a strained 80 nm thick Si_0.8Ge_0.2 layer; and a co-deposition method, where 5 nm Co and 18.2 nm Si were simultaneously deposited in a 1:2 ratio onto a strained Si_0.8Ge_0.2 layer at 450°C. Samples were then annealed at temperatures ranging from 500 to 800°C. Extended X-ray absorbance fine structure spectroscopy (EXAFS) and X-ray diffraction (XRD) were used to characterize the structure of the resulting films. It was found that the samples prepared via the direct deposition method did not convert to CoSi₂ at any annealing temperature up to 800°C, while the co-deposited samples formed epitaxial CoSi₂ at even the lowest annealing temperature of 500°C. These results are discussed in terms of proposed reaction mechanisms of the different deposition methods, based on consideration of the Co–Si–Ge ternary phase diagram.     

CVD of hard DLC films in a radio frequency inductively coupled plasma source

Chemical vapor deposition (CVD) of hard diamond-like carbon (DLC) films on silicon (100) substrates from methane was successfully carried out using a radio frequency (r.f.) inductively coupled plasma source (ICPS). Different deposition parameters such as bias voltage, r.f. power, gas flow and pressure were involved. The structures of the films were characterized by Fourier transform infrared (FTIR) spectroscopy and Raman spectroscopy. The hardness of the DLC films was measured by a Knoop microhardness tester. The surface morphology of the films was characterized by atomic force microscope (AFM) and the surface roughness (R_a) was derived from the AFM data. The films are smooth with roughness less than 1.007 nm. Raman spectra shows that the films have typical diamond-like characteristics with a D line peak at 1331 cm⁻¹ and a G line peak at 1544 cm⁻¹, and the low intensity ratio of I_D/I_G indicate that the DLC films have a high ratio of sp³ to sp² bonding, which is also in accordance with the results of FTIR spectra. The films hardness can reach approximately 42 GPa at a comparatively low substrate bias voltage, which is much greater than that of DLC films deposited in a conventional r.f. capacitively coupled parallel-plate system. It is suggested that the high plasma density and the suitable deposition environment (such as the amount and ratio of hydrocarbon radicals to atomic or ionic hydrogen) obtained in the ICPS are important for depositing hard and high quality DLC films.     

Deposition kinetics of silicon dioxide from tetraethylorthosilicate by PECVD

Tetraethylorthosilicate (TEOS)-based SiO₂ films were prepared in an RF reactor at various discharge powers and two substrate temperatures, and infra-red absorption spectra were taken for each deposited film using an FTIR spectrometer. Based on the FTIR observations, a model for the plasma and surface kinetics was developed. Using a proposed three-step reaction mechanism at the surface of a two-dimensional lattice, the growth rate of the films and the incorporation rate of Si---O---Si bridges into the films were derived as functions of the densities of the film precursors, oxygen atoms and molecular oxygen ions. The densities are further given by the uniform discharge model of our previous work as a function of the discharge power. According to the model, in the regime of high ratio of oxygen to TEOS flow the growth rate is governed by the film precursors generated from TEOS, and the incorporation rate is additionally determined by oxygen radicals and molecular oxygen ions and by the dehydration process. The growth rate was measured in μm/min and the relative incorporation rate was obtained from the absorption intensity of Si---O---Si rocking mode in FTIR spectra. The formulation of the model was compared with the experimental results, and on the validity of the model was discussed.     

Characterization of indium zinc oxide thin films prepared by pulsed laser deposition using a Zn3In2O6 target

Using a Zn₃In₂O₆ target, indium-zinc oxide films were prepared by pulsed laser deposition. The influence of the substrate deposition temperature and the oxygen pressure on the structure, optical and electrical properties were studied. Crystalline films are obtained for substrate temperatures above 200°C. At the optimum substrate deposition temperature of 500°C and the optimum oxygen pressure of 10⁻³ mbar, both conditions that indeed lead to the highest conductivity, Zn₃In₂O₆ films exhibit a transparency of 85% in the visible region and a conductivity of 1000 S/cm. Depositions carried out in oxygen and reducing gas, 93% Ar/7% H₂, result in large discrepancies between the target stoichiometry and the film composition. The Zn/In (at.%) ratio of 1.5 is only preserved for oxygen pressures of 10⁻²–10⁻³ mbar and a 93% Ar/7% H₂ pressure of 10⁻² mbar. The optical properties are basically not affected by the type of atmosphere used during the film deposition, unlike the conductivity which significantly increases from 80 to 1400 S/cm for a film deposited in 10⁻² mbar of O₂ and in 93% Ar/7% H₂, respectively.     

Marangoni convection and weld shape variations in Ar–O2 and Ar–CO2 shielded GTA welding

Increasing the oxygen or the carbon dioxide concentration in the argon-based shielding gas leads to an increase in the weld metal oxygen content when the oxygen or carbon dioxide concentration is to be lower than 0.6 vol.% in the shielding gas. However, when the O₂ or CO₂ concentration is higher than 0.6 vol.% in the Ar-based shielding gas, the weld metal oxygen is maintained around 200 ppm–250 ppm. An inward Marangoni convection mode in the weld pool occurs when the weld metal oxygen content is more than 100 ppm. When it is lower than 100 ppm, the Marangoni convection would change to the outward direction and the weld shape varies from a deep narrow to a shallow wide shape. The effective ranges of O₂ and CO₂ concentrations for deep penetration are same. A heavy layer of oxides is formed when the O₂ or CO₂ concentration in the shielding gas is more than 0.6 vol.%. Based on the thermodynamic calculation of the equilibrium reactions of Fe, Si, Cr and Mn with oxygen in liquid iron for the oxide products, FeO, SiO₂, Cr₂O₃ and MnO and the experimental oxygen content in the weld metal, Cr₂O₃ and SiO₂ oxides are possibly formed at the periphery area of the liquid pool surface under the arc column during the welding process. One model is proposed to illustrate the role of the oxide layer on the Marangoni convection on the pool surface at elevated temperature. The heavy oxide layer inhibited the fluid flow induced by the Marangoni convection and also became a barrier for the oxygen absorption into the molten weld pool.     

Chemical analysis of NiAlFe thin films sputter deposited onto sapphire substrates

NiAlFe thin films were prepared onto sapphire single crystals by physical vapour deposition (PVD) and these were analysed by X-ray photoelectron spectroscopy (XPS) in combination with argon ion etching to determine the composition depth profile and interfacial characteristics of the samples. Non-linear least square fitting (NLLSF) analysis of the data was required due to the conflict of several peaks of interest. XPS depth profiles show that, for non-annealed NiAlFe–Al₂O₃, the interface is sharp and oxygen diffusion occurs at different annealing temperatures. Ni remains chemically unaffected by the presence of oxygen while the formation of aluminium oxide compounds occur. Two iron species are present in the film thickness where the low binding energy component is attributed to Fe–Fe or Fe–Al interactions and the higher one to the NiAlFe compound. The reduction-dissolution of the sapphire substrate leads to depletion of oxygen in the sapphire surface layer and the formation of alumina at the NiAlFe–Al₂O₃ interface. Within the film, aluminium and nickel are present as an intermetallic compound. Annealing of the samples induces surface oxidation and the subsequent formation of an Al₂O₃ layer. This type of interphase morphology should lead to optimal fibre/matrix (F–M) adhesion, and therefore optimal load transfer between the matrix and reinforcement.