Influence of the methyl group on the dielectric constant of boron carbon nitride films containing it

LSI interconnect insulators made using low dielectric constant (low-k) materials are required for high performance devices with a small RC delay. We investigated a boron carbon nitride film containing the methyl group (Me–BCN) using tris-di-methyl-amino-boron (TMAB: B[N(CH₃)₂]₃) gas as a low-k material. In addition, we studied the influence of the methyl group on the dielectric constant (k-value) and the properties of the Me–BCN films. It was found that the k-value of the Me–BCN films decreases with increasing number of C–H bonds due to the methyl group (CH₃). The number of O–H bonds due to water incorporation is suppressed by increasing the number of C–H bonds. Consequently, we suggested that a lower k-value can be realized by the suppression of water invasion by a hydrophobic surface due to methyl bonds. Thus, the control of the methyl group is important to achieve a low-k material using Me–BCN films.     

Influence of atomic bonds on electrical property of boron carbon nitride films synthesized by remote plasma-assisted chemical vapor deposition

Boron carbon nitride (BCN) films are synthesized with various growth conditions by remote plasma-assisted chemical vapor deposition method. The chemical bonding in the BCN film is modified by the growth condition. Optical and electrical properties are investigated for BCN films with various chemical bonding. Electrical characterization is carried out for the BCN films which have the same bandgap energy and different C composition ratio and have the same C composition ratio and different bandgap energy.     

Molybdenum-containing carbon films deposited using the screen grid technique in an electron cyclotron resonance chemical vapor deposition system

A novel technique involving the incorporation of two molybdenum (Mo) screen grids embedded in an electron cyclotron resonance chemical vapor deposition (ECR–CVD) system is presented in this paper. A comprehensive set of film deposition experiments based on this screen grid sputtering technique has been carried out. The Mo-containing carbon films were characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS). The film resistivity, optical bandgap and hardness were evaluated as a function of the gas flow ratio (CH₄/Ar). XPS analysis showed that the fraction of Mo incorporated in the carbon film decreased drastically from 15.11 to 0.32% following an increase in the CH₄/Ar flow ratio. The optical absorption also decreases strongly and the film with the lowest Mo fraction has a bandgap of 2.0 eV. The film resistivity was found to increase by 11 orders of magnitude following the decrease in the metal fraction. It is found that Mo can exist in the forms of MoC, Mo₂C, Mo, and even MoO₃ in the films, the last being mainly due to air exposure. The results showed that our ECR-based screen grid technique for Me-C:H deposition is highly effective and flexible with good control over the amount of metal incorporated.     

Synthesis of BCN thin films by nitrogen ion beam assisted pulsed laser deposition from a B4C target

Using sintered B₄C as target material, ternary BCN thin films were synthesized on Si(100) substrates by means of reactive pulsed laser deposition assisted by nitrogen ion beam. The composition, bonding configuration and crystalline structure of the synthesized films were characterized by X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and transmission electron microscopy. The prepared films contain several bonds including B–C, N–C, B–N with B–C–N atomic hybridization. The ablation of the B₄C target results in the deposition of a film with B:C ratio about 3:1, deficient in boron compared with the target material. Nitrogen provided by the ion beam is incorporated in the film and bonded to boron and carbon. Heating of the substrate enhances the incorporation of nitrogen and influences the bonding configuration and crystalline structure of the film as well.     

Characterization of BCN film after wet process for interconnection integration

In this study, we investigate the influence of the wet chemical processes involved in the chemical treatment of boron carbon nitride (BCN) films deposited by plasma-assisted chemical vapor deposition (PACVD). BCN film is expected to be a low dielectric constant (low-K) material useful in fabricating future generation LSI devices. BCN film with less than 10% oxygen was hardly etched. The etching rate of the BCN film with an oxygen composition ratio more than 10% depends on the pH of the solution. The relationship between the film etching rate and the atomic bonds in BCN film is also investigated using XPS and FTIR. It was found that the BCN films without C–O and B–O bonds are not etched by acid and alkaline solutions. Therefore, suppression of oxygen concentration in the BCN film is important for LSI integration.     

Characteristic Study of Silicon Nitride Films Deposited by LPCVD and PECVD

This paper analyzes and compares the characteristics of silicon nitride films deposited by low pressure chemical vapor deposition (LPCVD) and plasma enhanced chemical vapor deposition (PECVD), with special attention to the hydrogenation and chemical composition of silicon nitride films. Three different LPCVD processes at various DCS and NH₃ gas flow rates and deposition temperatures, together with PECVD using SiH₄ and NH₃ and ICP CVD using SiH₄ and N₂, were compared. The silicon nitride film deposition rate decreases with an increasing NH₃/DCS ratio in LPCVD, which also leads to an increase in the refractive index and a decrease in the residual stress in the film. There is nearly no hydrogen incorporated in the LPCVD films, which differs from PECVD and ICP CVD that show significant Si-H and N-H bonds. The chemical composition of silicon nitride films is mostly Si-rich, except for the LPCVD process at high NH₃/DCS ratio with near stoichiometric chemistry.     

Micromechanical properties of BN and B–C–N coatings obtained by r.f. plasma-assisted CVD

We have obtained highly transparent and hard BN films in a capacitively coupled r.f. plasma-assisted CVD reactor from three different gas mixtures: B₂H₆–H₂–NH₃, B₂H₆–N₂ and B₂H₆–N₂–Ar. It was found that the films were smooth, dense, and had a textured hexagonal structure with the basal planes perpendicular to the film surface. The microhardness, friction coefficient and adhesion of these coatings were measured by nanoindentation and microscratching. BC_xN_y films were also prepared in the same plasma-assisted CVD reactor from B₂H₆–N₂–CH₄ gas mixtures. The carbon content in the films was varied by using different CH₄ flow rates. These films had a less ordered structure. The mechanical properties of these films had been compared to those of hexagonal BN films. Microhardness measurements showed that there is a correlation between film composition and hardness of the BCN films.     

Bonding defects and optical band gaps of DLC films deposited by microwave surface-wave plasma CVD

The effects of CH₄ / C₂H₄ flow ratio and annealing temperature on the defect states and optical properties of diamond-like carbon (DLC) films deposited by novel microwave surface-wave plasma chemical vapour deposition (MW SWP CVD) are studied through UV/VIS/NIR measurements, atomic force microscopy, Raman spectroscopy and electron spin resonance analysis. The optical band gap of DLC has been tailored between a relatively narrow range, 2.65–2.5 eV by manipulating CH₄ / C₂H₄ flow ratio and a wide range, 2.5–0.95 by thermal annealing. The ESR spin density varied between 10¹⁹ to 10¹⁷ spins/cm³ depending on the CH₄ / C₂H₄ flow ratio (1 : 3 to 3 : 1). The defect density increased with increasing annealing temperature. Also, there is a strong dependence of spin density on the optical band gap of the annealed-DLC films, and this dependency has been qualitatively understood from Raman spectra of the films as a result of structural changes due to sp³/sp² carbon bonding network. The surfaces of the films are found to be very smooth and uniform (RMS roughness < 0.5 nm).     

Effects of nitrogen addition on morphology and mechanical property of DC arc plasma jet CVD diamond films

Nitrogen-doped diamond films have been synthesized by 100 KW DC arc plasma jet chemical vapor deposition using a CH₄/Ar/H₂ gas mixture. The effect of nitrogen addition into the feed gases on the growth and surface morphology and mechanical property of diamond film was investigated. The reactant gas composition was determined by the gas flow rates. At a constant flow rate of hydrogen (5000 sccm) and methane (100 sccm), the nitrogen to carbon ratio (N/C) were varied from 0.06 to 0.68. The films were grown under a constant pressure (4 KPa) and a constant substrate temperature (1073 K). The deposited films were characterized by scanning electron microscopy, Raman spectroscopy and X-ray diffraction. The fracture strength of diamond films was tested by three point bending method. The results have shown that nitrogen addition to CH₄/H₂/Ar mixtures had led to a significant change of film morphology, growth rate, crystalline orientation, nucleation density and fracture strength for free-standing diamond films prepared by DC arc plasma jet.     

Nonlinear growth of zinc tin oxide thin films prepared by atomic layer deposition

Zinc tin oxide (ZTO) thin films can be deposited by atomic layer deposition (ALD) with adjustable electrical, optical and structural properties. However, the ternary ALD processes usually suffer from low growth rate and difficulty in controlling film thickness and elemental composition, due to the interaction of ZnO and SnO₂ processes. In this work, ZTO thin films with different Sn levels are prepared by ALD super cycles using diethylzinc, tetrakis(dimethylamido)tin, and water. It is observed that both the film growth rate and atom composition show nonlinear variation versus [Sn]/([Sn]+[Zn]) cycle ratio. The experimental thickness measured by spectroscopic ellipsometry and X-ray reflectivity are much lower than the expected thickness linearly interpolated from pure ZnO and SnO_x films. The [Sn]/([Sn]+[Zn]) atom ratios estimated by X-ray photoelectron spectroscopy have higher values than that expected from the cycle ratios. Hence, to characterize the film growth behavior versus cycle ratio, a numerical method is proposed by simulating the effect of reduced density and reactivity of surface hydroxyls and surface etching reactions. The structure, electrical and optical properties of ZTO with different Sn levels are also examined by X-ray diffraction, atomic force microscope, Hall measurements and ultraviolet–visible–infrared transmittance spectroscopy. The ZTO turns out to be transparent nanocrystalline or amorphous films with smooth surface. With more Sn contents, the film resistivity gets higher (>1 Ω cm) and the optical bandgap rises from 3.47 to 3.83 eV.     

Amorphous Ge‐Sb‐Se thin films fabricated by co‐sputtering: Properties and photosensitivity

Amorphous Ge–Sb–Se thin films were fabricated by a rf‐magnetron co‐sputtering technique employing the following cathodes: GeSe₂, Sb₂Se₃, and Ge₂₈Sb₁₂Se₆₀. The influence of the composition, determined by energy‐dispersive X‐ray spectroscopy, on the optical properties was studied. Optical properties were analyzed based on variable angle spectroscopic ellipsometry and UV‐Vis‐NIR spectrophotometry. The results show that the optical bandgap range 1.35‐2.08 eV with corresponding refractive index ranging from 3.33 to 2.36 can be reliably covered. Furthermore, morphological and topographical properties of selenide‐sputtered films studied by scanning electron microscopy and atomic force microscopy showed a good quality of fabricated films. In addition, structure of the films was controlled using Raman scattering spectroscopy. Finally, irreversible photoinduced changes by means of change in optical bandgap energy and refractive index of co‐sputtered films were studied revealing the photobleaching effect in Ge‐rich films when irradiated by near‐bandgap light under Ar atmosphere. The photobleaching effect tends to decrease with increasing antimony content.     

Growth of GaN Thin Films Using Plasma Enhanced Atomic Layer Deposition: Effect of Ammonia-Containing Plasma Power on Residual Oxygen Capture

In recent years, the application of (In, Al, Ga)N materials in photovoltaic devices has attracted much attention. Like InGaN, it is a direct band gap material with high absorption at the band edge, suitable for high efficiency photovoltaic devices. Nonetheless, it is important to deposit high-quality GaN material as a foundation. Plasma-enhanced atomic layer deposition (PEALD) combines the advantages of the ALD process with the use of plasma and is often used to deposit thin films with different needs. However, residual oxygen during growth has always been an unavoidable issue affecting the quality of the resulting film, especially in growing gallium nitride (GaN) films. In this study, the NH₃-containing plasma was used to capture the oxygen absorbed on the growing surface to improve the quality of GaN films. By diagnosing the plasma, NH₂, NH, and H radicals controlled by the plasma power has a strong influence not only on the oxygen content in growing GaN films but also on the growth rate, crystallinity, and surface roughness. The NH and NH₂ radicals contribute to the growth of GaN films while the H radicals selectively dissociate Ga-OH bonds on the film surface and etch the grown films. At high plasma power, the GaN film with the lowest Ga-O bond ratio has a saturated growth rate, a better crystallinity, a rougher surface, and a lower bandgap. In addition, the deposition mechanism of GaN thin films prepared with a trimethylgallium metal source and NH₃/Ar plasma PEALD involving oxygen participation or not is also discussed in the study.     

Preparation of nanostructured TiO2 thin films by aerosol flame deposition process

Titania thin films were prepared by using aerosol flame deposition process via the pyrolysis of titanium tetra-isopropoxide (TTIP) precursor. We analyzed the specific surface area, primary and secondary particle sizes, crystal structure, thin film morphology and thickness by BET method, electrophoretic light scattering, X-ray diffraction and scanning electron microscopy, respectively. The specific surface area of TiO₂ particles deposited is over three-times larger than that of commercial Degussa P25. Crystallite structure of TiO₂ particles can be controlled by changing the ratio of CH₄/O₂ flow rates. We could prepare TiO₂ thin films with single anatase phase by keeping the ratio of CH₄/O₂ flow rates at 200 ml/min: 1,000ml/min. As N₂ carrier gas flow rate to bubbler increases, the primary and secondary particle sizes increase, but decrease with increasing total N₂ gas flow rate through the central tube. The shorter the deposition height is, the smaller the deposition area is, but the thin film becomes thicker in the central region.     

Microstructure and tribological properties of ternary BCN thin films with different carbon contents

Boron carbon nitrogen (BCN) thin films with different carbon contents are deposited on high-speed steel substrates by reactive magnetron sputtering (RMS) and their microstructure and tribological properties are studied. The BCN films with carbon contents from 26.9 wt.% to 61.3 wt.% have an amorphous structure with variable amounts of carbon bonds (sp²C–C, sp²C–N and sp³C–N bonds). A higher carbon content enhances the film hardness but reduces the friction coefficient against GCr15 steel balls in air. BCN films with higher hardness, lower friction coefficient, and better wear resistance can be obtained by increasing the carbon content.     

Boron doped amorphous carbon thin films grown by r.f. PECVD under different partial pressure

Boron doped hydrogenated amorphous carbon (a-C) thin films have been deposited by r.f.-plasma CVD with a frequency of 13.56 MHz at room temperature using pure methane as a precursor of carbon source mixed with hydrogen (H₂) as a carrier gas. The films were prepared by varying the r.f. power, different flow rates of CH₄, and partial pressure of mixed gas (CH₄/H₂) using solid boron as a target. The thickness, structural, bonding and optical properties of the as-deposited films were studied by Alpha step surface profiler, Raman, FT-IR, XPS and UV–visible spectroscopy. It was found that changing the deposition pressure in presence of solid boron dopant in the r.f. PECVD process has a profound effect on the properties of the deposited films, as evidenced from their Raman scattering and optical results. The grown p-C: B films were found very smooth and thickness in the range of 240 to 360 nm for 1 h deposition. Films deposited at lower pressure appear brownish color whereas those deposited at higher pressure appear pale yellowish. The as-deposited film is found to be dominated by sp² rather than sp³, which might be due to the formation of small crystallites. The optical band gap is found to be reduced from 2.601.58 eV as the partial pressure of CH₄/H₂ gas is reduced.     

Structure and characteristics of amorphous (Ti,Si)–C:H films deposited by reactive magnetron sputtering

The hydrogenated amorphous carbon films doped with Ti and Si ((Ti,Si)–C:H) were deposited on silicon substrates using reactive magnetron sputtering Ti₈₀Si₂₀ composite target in an argon and methane gas mixture. The structures of the films were analyzed by X-ray photoelectron spectroscopy and Visible Raman spectroscopy. The morphologies were observed by atomic force microscope. The friction coefficients of the films were tested on the ball-on-disc tribometer. The results indicate that the sp³/sp² ratios in the films can be varied from 0.18 to 0.63 by changing Ti and Si contents at various CH₄ flow rates. The surface of the films becomes smoother and more compact as the CH₄ flow rate increases. The lowest friction coefficient is as low as 0.0139 for the film with Ti of 4.5 at.% and Si of 1.0 at.%. Especially, the film exhibits a superlow value (μ < 0.01) under ambient air with 40% relative humidity in friction process. The superlow friction coefficient in ambient air may be, attributable to synergistic effects of a combination of Ti and Si in the film.     

Structures and luminescence properties of polymer-like a-CNx:H films

Polymer-like hydrogenated amorphous carbon nitride (a-CNx:H) films were prepared in CH₄/N₂ r.f. plasma with different CH₄/N₂ mixing ratio and r.f. power input, and the structural and luminescence properties of these films were examined. Both optical band gap and PL peak energies of the a-CNx:H films were shifted with a variation of nitrogen content in the film. The theoretical PL efficiency described well the experimental data, and it was suggested that the PL of the a-CNx:H films arise from tail-to-tail electron-hole recombination in the localized π and π* states. From the FT-IR measurements, it was found that the films with lower nitrogen content included a large amount of sp³C–H bond, while in the film with higher nitrogen content, N–H, C=N and CN bonds were predominantly formed. From the EL devices fabricated using both a-CNx:H film and thin organic layers, EL spectra with a broad band of 350–700 nm were observed. Both EL and PL from the a-CNx:H film indicated almost the same behavior, and the components observed in the PL spectrum of each organic material were not included in the EL spectrum.     

Improved electrical and optical properties in epitaxial Cd2SnO4 films

Epitaxial Cd₂SnO₄ films were fabricated on MgO(00l) single crystalline substrates by pulsed laser deposition technique at various substrate temperatures and growth oxygen pressures. The microstructure, transport, and optical properties of the films were studied in detail. High-resolution X-ray diffraction and high-resolution transmission electron microscopy results demonstrate that all the Cd₂SnO₄ films are grown epitaxially on MgO(00l) substrates. Atomic force microscope images indicate that the films have smooth surface morphologies. Hall-effect measurements reveal that the epitaxial film grown at 680^°C and 40 Pa presents the minimum resistivity value of 0.61 mΩcm and maximal Hall mobility of 32.87 cm² V⁻¹ s⁻¹. The metal–semiconductor transitions of Cd₂SnO₄ films were observed and explained by competitive effects of two conductive mechanisms. The optical transmittance of the Cd₂SnO₄ films is higher than 75% in the visible and near-infrared range, and the optical bandgap was determined to be about 3.09 eV for the film grown at optimal condition. The band structure and density of states of the Cd₂SnO₄ were calculated by the density functional theory.     

Mechanical and tribological properties of boron,nitrogen-coincorporated diamond-like carbon films prepared by reactive radio-frequency magnetron sputtering

We have deposited boron- and/or nitrogen-incorporated DLC films by radio-frequency magnetron sputtering, and systematically investigated the structure and the mechanical and tribological properties. The N content in DLC films increased with increasing N₂ flow ratio [N₂/(Ar + N₂)], and it tended to be saturated at higher N₂ flow ratios. The N content further increased with an increase in the B content of the targets. The B/C ratios of the films were almost the same as those of the B-containing targets regardless of the N content. Scratch tests revealed that the adhesion strength of N-incorporated DLC films decreased with increasing N₂ flow ratio and the critical loads of B-incorporated films were lower than that of an unincorporated film. It was found that for B, N-coincorporated films there was an optimum N₂ flow ratio at which the critical load became a maximum value, which was higher than that of the unincorporated film. The optimum N₂ flow ratio increased with an increase in the B composition of the targets. The N-incorporated films peeled off during ball-on-plate friction tests. On the other hand, the B, N-coincorporated films showed good wear-resistant properties that the specific wear rates were lower than those of the unincorporated and B-incorporated films.     

Homoepitaxial diamond film with an atomically flat surface over a large area

Homoepitaxial diamond films with atomically flat surface were grown using the microwave plasma chemical vapor deposition method at a low CH₄ concentration of less than 0.05% in a CH₄ and H₂ mixed gas system. In Ib (001) diamond substrates having misorientation angles of 0.5°, atomic force microscope image on the surface of film grown at 0.025% CH₄ concentration showed that the films had atomically flat surface with mean roughness of 0.04 nm in area as large as 4×4 mm² (the whole region of the substrate).