Mid-frequency deposition of a-C:H films using five different precursors

The plasma-enhanced chemical vapour deposition (PECVD) of amorphous hydrogenated carbon films from pulsed discharges with frequencies in the range from 50 kHz to 250 kHz was investigated. Five different hydrocarbons (acetylene C₂H₂, isobutene C₄H₈, cyclopentene C₅H₈, toluene C₇H₈ and cycloheptatriene C₇H₈) were probed as film growth precursors. In addition, two types of pulse-generators with somewhat different waveforms were used to power the discharges in the so called mid-frequency range. The a-C:H films deposited in a parallel-plate reactor were characterised for their thickness/deposition rate, hardness and hydrogen content. The hydrogen concentration in the films varied between 19 at.-% and 37 at.-%. With the substrate temperature held constant, it is roughly in inverse proportion to the hardness. The film with the highest hardness of 25 GPa was formed at a deposition rate of 0.8 μm/h in the C₂H₂ discharge at the lowest investigated pressure of 2 Pa. With increasing molecular mass of the precursor mostly weaker films were deposited. Relatively high values of both deposition rate and hardness were achieved using the precursor isobutene: a hardness of 21 GPa combined with a deposition rate of 4.1 μm/h. From the probed precursors, isobutene is also most advantageous for a-C:H deposition at higher pressures (up to 50 Pa investigated). But, as an over-all trend, the a-C:H hardness decreases with increasing deposition rate.     

Mid-frequency deposition of a-C:H films using five different precursors

The plasma-enhanced chemical vapour deposition (PECVD) of amorphous hydrogenated carbon films from pulsed discharges with frequencies in the range from 50 kHz to 250 kHz was investigated. Five different hydrocarbons (acetylene C₂H₂, isobutene C₄H₈, cyclopentene C₅H₈, toluene C₇H₈ and cycloheptatriene C₇H₈) were probed as film growth precursors. In addition, two types of pulse-generators with somewhat different waveforms were used to power the discharges in the so called mid-frequency range. The a-C:H films deposited in a parallel-plate reactor were characterised for their thickness/deposition rate, hardness and hydrogen content. The hydrogen concentration in the films varied between 19 at.-% and 37 at.-%. With the substrate temperature held constant, it is roughly in inverse proportion to the hardness. The film with the highest hardness of 25 GPa was formed at a deposition rate of 0.8 μm/h in the C₂H₂ discharge at the lowest investigated pressure of 2 Pa. With increasing molecular mass of the precursor mostly weaker films were deposited. Relatively high values of both deposition rate and hardness were achieved using the precursor isobutene: a hardness of 21 GPa combined with a deposition rate of 4.1 μm/h. From the probed precursors, isobutene is also most advantageous for a-C:H deposition at higher pressures (up to 50 Pa investigated). But, as an over-all trend, the a-C:H hardness decreases with increasing deposition rate.     

Diamond-like a-C:H coatings deposited in a non-self-sustained discharge with plasma cathode

Hydrogenated amorphous carbon (a-C:H) coatings have been obtained by means of acetylene decomposition in a non-self-sustained periodic pulse discharge (2A, 50 kHz, 10 μs) with hollow cathode. The discharge operation was maintained by plasma cathode emission with grid stabilization based on dc glow discharge. Using the proposed method, it is possible to control the deposition conditions (total pressure of the Ar + C₂H₂ mixture, partial pressure of C₂H₂, ion current density, carbon ion energy) within broad limits, to apply a-C:H coatings onto large-area articles, and to perform deposition in one technological cycle with ion etching and ion implantation treatments aimed at improving the adhesion of coatings to substrates (Ti, Al, stainless steel, VK8 hard alloy) at temperatures below 150°C. Results of determining the deposition rate (1–8 μm), the nanohardness of coatings (up to 70 GPa), and the fraction of sp ³ bonds (25–70%) in the diamond-like coating material are presented.     

Characteristics of carbon coatings on optical fibers prepared by radio-frequency plasma enhanced chemical vapor deposition with different H2/C2H2 ratios

Characteristics of carbon coatings on optical fibers prepared by radio-frequency plasma enhanced chemical vapor deposition with different H₂/C₂H₂ ratios are investigated. Five kinds of carbon coatings are prepared with H₂/C₂H₂ ratios of 2, 4, 6, 8, and 10. Experimental results show that the deposition rate and surface roughness of carbon coatings decrease as the H₂/C₂H₂ ratio increases. When the H₂/C₂H₂ ratio changes from 2 to 8, the increase of H₂/C₂H₂ ratios detrimentally yields sp³ carbon atoms and sp³-CH₃ bonds in the carbon coatings. However, when the H₂/C₂H₂ ratio exceeds 8, the hydrogen retards the growth of the graphite structure. Moreover, the redundant hydrogen radicals favor bonding with the dangling bonds in the coating surface. Therefore, when the H₂/C₂H₂ ratio increases from 8 to 10, the amounts of sp³ carbon atoms and sp³-CH₃ bonds in the carbon coatings increase. At an H₂/C₂H₂ ratio of 8, the carbon coating exhibits excellent water-repellency and thermal-loading resistance, and so this ratio is the best for producing a hermetically sealed optical fiber coating.     

Preparation and characterization of diamond films

Diamond films were deposited by magnetron sputtering of vitreous carbon disc and also by plasma CVD technique using C₂H₂ + H₂ or CO₂ + H₂ gas mixtures. The films were characterized by measuring the electrical, optical and microstructural properties. FTIR and Raman studies were carried out to study the effect ofsp ² andsp ³ bonds present in the films. The films had a high mechanical stress which was determined from the broadening of the optical absorption tail in the films.     

High growth rate of a-SiC:H films using ethane carbon source by HW-CVD method

Hydrogenated amorphous silicon carbide (a-SiC:H) thin films were prepared using pure silane (SiH₄) and ethane (C₂H₆), a novel carbon source, without hydrogen dilution using hot wire chemical vapour deposition (HW-CVD) method at low substrate temperature (200 °C) and at reasonably higher deposition rate (19·5 Å/s < r _d < 3·2 Å/s). Formation of a-SiC:H films has been confirmed from FTIR, Raman and XPS analysis. Influence of deposition pressure on compositional, structural, optical and electrical properties has been investigated. FTIR spectroscopy analysis revealed that there is decrease in C–H and Si–H bond densities while, Si–C bond density increases with increase in deposition pressure. Total hydrogen content drops from 22·6 to 14·4 at.% when deposition pressure is increased. Raman spectra show increase in structural disorder with increase in deposition pressure. It also confirms the formation of nearly stoichiometric a-SiC:H films. Bandgap calculated using both Tauc’s formulation and absorption at 10⁴ cm^?1 shows decreasing trend with increase in deposition pressure. Decrease in refractive index and increase in Urbach energy suggests increase in structural disorder and microvoid density in the films. Finally, it has been concluded that C₂H₆ can be used as an effective carbon source in HW-CVD method to prepare stoichiometric a-SiC:H films.     

Effects of different acetylene/nitrogen ratios on characteristics of carbon coatings on optical fibers prepared by thermal chemical vapor deposition

The effects of C₂H₂/(C₂H₂ + N₂) ratios on the characteristics of carbon coatings on optical fibers prepared by thermal chemical vapor deposition are investigated. The C₂H₂/(C₂H₂ + N₂) ratios are set to 60, 70, 80, 90, and 100%. Additionally, the deposition temperature, working pressure, and mass flow rate are 1003 K, 133 kPa, and 40 sccm, respectively. The deposition rate, microstructure, and electrical resistivity of carbon coatings are measured. The low-temperature surface morphology of carbon-coated optical fibers is elucidated. Experimental results indicate that the deposition rate increases with increasing the C₂H₂/(C₂H₂ + N₂) ratio, and the deposition process is located at a surface controlled regime. As the deposition rate increases, the electrical resistivity of carbon coatings increases, while the ordered degree, nano-crystallite size, and sp² carbon atoms of the carbon coatings decrease. Additionally, the low-temperature surface morphology of the carbon coatings shows that if the carbon coating thickness is not smaller than 289 nm, decreasing the deposition rate is good for producing hermetic optical fiber coatings.     

Plasma Deposition and Properties of Silicon Carbonitride Films

A variety of advanced analytical techniques were used to characterize silicon carbonitride films grown from new volatile nitrogen-rich silyl derivatives of asymmetrical dimethylhydrazine: (CH₃)₂HSiNHN(CH₃)₂ (DMDMSH) and Me₂Si(NHNMe₂)₂ (bisDMHDMS). The results demonstrate that the films contain only Si-C, Si-N, and C(sp ³)-N bonds, in relative amounts that depend on the molecular structure of the precursor and deposition conditions. The Si-C/[Si-N + C(sp ³)-N] ratio is considerably larger in the films grown from DMDMSH. The data obtained by a variety of spectroscopic techniques provide solid evidence that some of the films contain C(sp ³)-N bonds, characteristic of superhard materials, and that the films have a complex, framework structure, rather than being a mixture of Si₃N₄, SiC, and C₃N₄. The structure of the films depends on the N : Si ratio in the precursor: at N : Si = 2, the films are amorphous and contain nanocrystalline inclusions with a tetragonal structure; at N : Si = 4, the films are purely amorphous. The ability to control the chemical composition and structure of deposits allowed us to produce films with various physicochemical and electrical properties.__________Translated from Neorganicheskie Materialy, Vol. 41, No. 7, 2005, pp. 808–815.Original Russian Text Copyright © 2005 by Smirnova, Badalyan, Borisov, Kaichev, Bakhturova, Kichai, Rakhlin, Shainyan.     

Synthesis of carbon coatings employing a plasma torch from an argon-acetylene gas mixture at reduced pressure

Amorphous hydrogenated carbon films (a-C:H) were formed on Si (1 1 1) wafers from an argon-acetylene gas mixture at a reduced pressure of 1000 Pa using a direct current (DC) plasma torch discharge. The Ar/C₂H₂ gas volume ratio varied from 1:1 to 8:1, the distance between plasma torch exit and the samples 0.04-0.095 m. The DC plasma torch technique allows the production of thick (∼90 μm) coatings at 0.3 μm/s growth rates. Raman spectra shape, D and G peak positions and the intensity ratio (I_D/I_G) show an increase of sp³ bond fraction with decreasing acetylene flow in argon plasma. Reflectance of the coatings deposited at Ar/C₂H₂=8:1 is high (∼97%) and slightly increases with increasing distance between samples and plasma torch exit.     

Characteristics of nano-crystalline diamond films prepared in Ar/H2/CH4 microwave plasma

Characteristics of nano-crystalline diamond (NCD) thin films prepared with microwave plasma chemical vapor deposition (CVD) were studied in Ar/H₂/CH₄ gas mixture with a CH₄ gas ratio of 1-10% and H₂ gas ratio of 0-15%. From the Raman measurements, a pair of peaks at 1140 cm^− 1 and 1473 cm^− 1 related to the trans-polyacetylene components peculiar to nano-crystalline diamond films was clearly observed when the H₂ gas ratio of 5% was added in Ar/H₂/CH₄ mixture. With an increase of H₂ gas content up to 15%, their peaks decreased, while a G-peak at roughly 1556 cm^− 1 significantly increased. The degradation of NCD film quality strongly correlates with the decrease of C₂ optical emission intensity with the increase of hydrogen gas contents. From the surface analysis with atomic force microscopy (AFM), it was found that grain sizes of NCD films were typically of 10-100 nm in case of 5% H₂ gas addition.     

A comparative analysis of a-C:H films deposited from five hydrocarbons by thermal desorption spectroscopy

Thermal induced gas evolution studies were performed on hydrogenated amorphous carbon (a-C:H) films deposited by plasma enhanced chemical vapour deposition (PECVD). The hydrocarbon-argon discharges were powered by asymmetric bipolar voltage pulses. Five different hydrocarbons (acetylene C₂H₂, isobutene C₄H₈, cyclopentene C₅H₈, toluene C₇H₈ and cycloheptatriene C₇H₈) were compared as film growth precursors.The films were heated in vacuum upto 1000 °C and at the same time the gaseous effusion products were measured with a quadrupole mass spectrometer (QMS). The release of hydrogen, water, argon and different hydrocarbons from CH₄ upto C₇H₈ was proved. Large hydrocarbons were detected only when heating up soft films. When annealing hard films, they almost only lost hydrogen - mainly as H₂ but also in remarkable portion as H₂O. Possibly, the water in the a-C:H films contains the main fraction of hydrogen unbounded to carbon.The characteristic temperatures for the onset of gas evolution of the molecular gases and of argon were found to be strictly correlated with the film hardness - independent of the film growth precursor. The threshold temperature for the release of the dominating effusion product, molecular hydrogen, is significantly higher than that of argon only for films with hardness below about 13 GPa.     

Effects of hydrogen dilution on CNx film properties deposited using rf PECVD from a mixture of ethane,nitrogen and hydrogen

Carbon nitride (CN_x) thin films were deposited using radio frequency plasma enhanced chemical vapor deposition (rf PECVD) from a mixture of ethane (C₂H₆), nitrogen (N₂) and hydrogen (H₂) gases. The C₂H₆ and N₂ flow rates were kept constant, while the H₂ flow rate was varied. The effects of hydrogen dilution on the growth rate and structural properties of the films were studied. It was found that a significant increase in the films growth rate was observed with the introduction of H₂ at as low as 25 standard cubic centimeters per minute (sccm). A set of CN_x films deposited from C₂H₆:N₂ mixture without any inclusions of H₂ were also presented in this work as a reference to compare the differences between those two sets and to understand the roles of H₂ to the films properties. At highest H₂ flow rate, the structure of the films changed from polymeric to graphitic and the quenching of PL was observed. Furthermore, higher N incorporation with lower E_g was obtained for these films compared to those of C₂H₆:N₂ films. The change in the structure of the films corresponds to changes in their chemical bonding. As N incorporation increased, the porosity of the films increases and thus affects the disorder in the film structures.     

High aspect ratio contact hole etching using relatively transparent amorphous carbon hard mask deposited from propylene

In this study, a high aspect ratio contact pattern, beyond 70 nm technology, in a very-large-scale integrated circuit, was achieved using hydrogenated amorphous carbon (a-C:H) film as the dry etching hard mask. The effect of temperature on the a-C:H deposits prepared by plasma enhanced chemical vapor deposition was studied. The a-C:H films resulting from propylene (C₃H₆) decomposition exhibited high transparency incorporated rich hydrogen concentration with a decreasing deposition temperature. A matrix of dispersed cross-linked sp³ clusters in a-C:H films, which has an increasing optical band gap and higher hydrogen content, is attributed to reduce the defect density of status and obtain high transmittance rate. Moreover, the higher transparency of a-C:H films could afford lithographic aligned capability as well as compressive stress and dry etching resistance. These explorations provided insights into the role of hydrogen in a-C film and also into the practicality of its future nano-scale device applications.     

Influence of PECVD parameters on the properties of diamond-like carbon films

The properties of diamond-like carbon (DLC) are strongly affected by the amount of carbon atoms bonded in sp² and sp³ electronic hybridizations. Also the amount of incorporated hydrogen and oxygen plays an important role in the final properties of DLC films. Usually, the structure and chemical composition of thin DLC films can be changed by varying the deposition parameters. Therefore, the influence of PECVD process parameters on the properties of DLC films, grown on Si substrates, was investigated in this work.Thin DLC films were deposited in a CH₄/H₂ plasma by using Ar as a gas carrier. Different ratios of gas flows were used as a variable parameter of the PECVD process. The effect of cathodic ion bombardment was also investigated.The chemical composition of DLC specimens was studied by X-ray photoelectron spectroscopy (XPS). The ratio of carbon in sp² and sp³ hybridizations was determined by analyzing the first derivative of Auger C KLL spectra. These results were also confirmed by the measurements of electrical resistivity. The changes of surface morphology and microadhesion were analyzed by Atomic Force Microscopy (AFM).     

Effect of heating on the behaviors of hydrogen in C-TiC films with auger electron spectroscopy and secondary ion mass spectroscopy analyses

C-TiC films with a content of 75% TiC were prepared with magnetron sputtering deposition followed by Ar⁺ ion bombardment. Effect of heating on the behaviors of hydrogen in C-TiC films before and after heating was studied with Auger Electron Spectroscopy and Secondary Ion Mass Spectroscopy (SIMS) analyses. SIMS depth profiles of hydrogen after H⁺ ion implantation and thermal treatment show different hydrogen concentrations in C-TiC coatings and stainless steel. SIMS measurements show the existence of TiH, TiH₂, CH₃, CH₄, C₂H₂ bonds in the films after H⁺ ion irradiation and the changes in the Ti LMM, Ti LMV and C KLL Auger line shape reveal that they have a good hydrogen retention ability after heating up to the temperature 393 K. All the results show that C-TiC coatings can be used as a hydrogen retainer or hydrogen permeable barrier on stainless steel to protect it from hydrogen brittleness.     

Influence of hydrogen on the mechanical properties and microstructure of DLC films synthesized by r.f.-PECVD

This paper aims to investigate the influence of hydrogen on the variation of mechanical properties and microstructure of diamond-like carbon (DLC) films synthesized by radio frequency plasma chemical vapor deposition (r.f.-PECVD). The DLC films were deposited on a silicon substrate (p-type). The reactant gases employed in this paper are a mixture of acetylene and hydrogen. The ratio of hydrogen in the gas mixture was successively varied to clarify its influence on the roughness, thickness, microstructure, hardness, modulus, residual stress and wear depth for the DLC films. The results reveal that increasing the concentration of hydrogen decreases thickness and roughness. Meanwhile, increasing the hydrogen concentration causes the decrease of sp³ ratio, hardness as well as modulus. Finally, wear behavior is correlated to the surface morphology and hydrogen concentration for deposition with hydrogen-containing reactant gas.     

Preparation and Properties of Thin HfO<Subscript>2</Subscript> Films

HfO₂ layers were grown on silicon by metalorganic chemical vapor deposition using (C₅H₅)₂Hf(CH₃)₂, (C₅H₅)₂Hf(N(C₂H₅)₂)₂, and Hf(dpm)₄ as volatile precursors and were characterized by x-ray diffraction, x-ray photoelectron spectroscopy, and IR spectroscopy. The films were shown to consist of monoclinic HfO₂ and to contain hafnium silicide and silicate at the HfO₂/Si interface. The presence of hafnium silicide was attributed to oxygen deficiency produced by argon ion milling. Hafnium silicate was formed as a result of the reaction between hafnium and silicon oxides during annealing. Current-voltage and capacitance-voltage measurements on Al/HfO₂/Si test structures were used to determine the dielectric permittivity and electrical resistivity of the films: ? = 15–20, ρ ～ 10¹⁵ cm.     

Effects of methane flow rate on the optical properties and chemical bonding of germanium carbon films deposited by reactive sputtering

Amorphous hydrogenated germanium carbon (a-Ge_1−xC_x:H) films were prepared by radio frequency (RF) reactive magnetron sputtering of a pure Ge (111) target in a CH₄ + H₂+Ar mixture and their composition, optical properties, chemical bonding were investigated as a function of gas flow rate ratio of CH₄/(Ar + H₂). The results showed that the deposition rate first increased and then decreased as gas flow rate ratio of CH₄/(Ar + H₂) was increased from 0.125 to 0.625. And the optical gap of the a-Ge_1−xC_x:H films increased from 1.1 to 1.58 eV accompanied with the increase in the carbon content and the decrease in the relative content of Ge–C bonds of the films as the CH₄ flow rate ratio was increased, while refractive index of the films decreased and the absorption edge shifted to high energy. Through the analysis of X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy, it was found that the formation of Ge–C bonds in the films was promoted by low CH₄ flow rate which is connected with relatively high H₂ concentration and Ge content. Especially in low CH₄ concentration, the formation of sp²-hybridised C–C bonds was suppressed considerably both due to the etching effect on weak bonds of H and the fact that chemical bonding for germanium can be only sp³ hybridization.     

Growth and thermal annealing of amorphous germanium carbide obtained by X-ray chemical vapor deposition

The growth of amorphous hydrogenated germanium carbide (a-GeCx:H) alloys was performed with high deposition rates by radiolysis chemical vapor deposition (X-ray) of germane/allene (GeH₄/C₃H₄, 70/30 %) mixtures at different irradiation times. The experimental deposition parameters were correlated to the composition, the structural features, and the optical coefficients of the films, as studied by different spectroscopic techniques, namely, IR, Raman, and UV–Vis. It was observed that the increase of irradiation time yields a more hydrogenated and more disordered material, with abundant formation of sp³ CH₂ groups, characterized by high band-gap values. In addition, we report the effects of thermal annealing on bonding structures and optical properties of the amorphous germanium carbon alloys. The decrease of hydrogen extent, together with the enhancement of sp² C bonds present and amorphous-to-crystalline germanium phase transition, contribute to a larger structural order of the material and to the reduction of the optical gap at higher temperatures.     

Crystalline carbon nitride films prepared by microwave plasma chemical vapour deposition

Crystalline carbon nitride films have been synthesized on Si (100) substrates by a microwave plasma chemical vapour deposition technique, using mixture of N₂, CH₄ and H₂ as precursor. Scanning electron microscopy shows that the films consisted of hexagonal bars, tetragonal bars, rhombohedral bars, in which the bigger bar is about 20 μm long and 6 μm wide. The X-ray photoelectron spectroscopy suggests that nitrogen and carbon in the films are bonded through hybridized sp² and sp³ configurations. The x-ray diffraction pattern indicates that the films are composed of α-, β-, pseudocubic and cubic C₃N₄ phase and an unidentified phase. Raman spectra also support the existence of α- and β-C₃N₄ phases. Vickers microhardness of about 41.9 GPa measured for the films.