XPS study of the a-C:H/Ti and a-C:H/a-Si interfaces

In this study ultrathin hydrogenated amorphous carbon (a-C:H) films have been grown onto the titanium and amorphous silicon (a-Si) overlayers by direct ion beam deposition using acetylene gas as a hydrocarbon source. X-ray photoelectron spectroscopy (XPS) was used for study of the DLC-Ti and DLC-Si interfaces. It was revealed that a-Si is a good interlayer for improvement of adhesion in the case of diamond-like carbon film deposition onto the steel substrate at room temperature. a-C:H film growth without substantial intermixing occurred on the a-Si. On the other hand, adhesion between the Ti interlayer and the diamond like carbon film was very sensitive to the deposition conditions (presence of the pump oil) as well as structure and stress level of the Ti film. It was explained by strong intermixing between the growing carbon film and Ti. Bad adhesion between the growing DLC film and Ti interlayer was observed despite formation of the TiC. At the same time, formation of the TiO_x was not an obstacle for good adhesion. It is shown that composition of the used hydrocarbon gas, structure of the Ti thin film and mechanical stress in it had greater influence on adhesion with a-C:H film than elemental composition of the Ti interlayer surface.     

Catalytic CVD growth and properties of a-C:H and a-C:N

Hydrogenated amorphous carbon (a-C:H) and nitrided amorphous carbon (a-C:N) films have been synthesized on quartz substrates at a substrate temperature of 700 °C using a catalytic chemical vapor deposition (Cat-CVD) method. Raman spectra of a-C:H films showed two principal bands, the G-band at 1600 cm⁻¹ and the D-band at 1350 cm⁻¹. Those of a-C:N films showed similar spectra, with a G′ band at 1640 cm⁻¹, the peak energy of which is higher than that of the G-band in a-C:H. The intensity ratio /I_D, which is a measure of the degree of order in a-C:H, decreased for a-C:H with increasing CH₄/H₂ gas-flow ratio. On the contrary, the /I_D ratio increased with increasing CH₄/H₂ gas-flow ratio.     

MBE growth and characterization of buried silicon oxide films on Si(100)

Silicon molecular beam epitaxy (Si-MBE) has been used to produce silicon oxide (SiO_x) films by evaporating Si on a heated Si(100) substrate in an ultra high vacuum system with an O₂ pressure of 10⁻⁶ to 10⁻⁴ mbar. Then the SiO_x films were overgrown with pure Si. The influence of the substrate temperature, the O₂ pressure and the Si deposition rate on the oxygen content in the SiO_x films and on the crystalline quality of the Si top-layer was investigated by Rutherford backscattering spectrometry and ion channeling. Epitaxial growth of the Si top-layer was observed up to a maximum concentration of ≈20 at.% oxygen content in the SiO_x film. Cross-sectional transmission electron microscopy shows that the structure of the SiO_x film changes duringa subsequent annealing procedure. Electron energy loss spectrometry proves that amorphous SiO₂ is formed and the development of holes indicates that the density of the as-grown SiO_x film is much lower than that of SiO₂. The specific for the as-grown SiO_x films was determined by I–V measurements.     

Preparation of B-doped a-Si1−xCx:H films and heterojunction p–i–n solar cells by the Cat-CVD method

B-doped a-Si_1−xC_x:H films for a window layer of Si thin film solar cells have been prepared by the Cat-CVD method. It is found that C is effectively incorporated into the films by using C₂H₂ as a C source gas, where an only little C incorporation is observed from CH₄ and C₂H₆ under similar deposition conditions. Using a-Si_1−xC_x:H films grown from C₂H₂, heterojunction p–i–n solar cells have been prepared by the Cat-CVD method. The cell structure is (SnO₂ Asahi-U)/ZnO/a-Si_1−xC_x:H(p)/a-Si:H(i)/μc-Si:H(n)/Al. The obtained conversion efficiency was 5.4%.     

Fluorohydrogenated amorphous carbon (a-C:H, F) films prepared by the r.f. plasma decomposition of 1,3-butadiene and carbon tetrafluoride

Amorphous fluorohydrogenated carbon films (a-C:H, F) were prepared by the r.f. glow discharge decomposition of a hydrocarbon (C₄H₆) diluted with a fluorocarbon (CF₄). An increase in the CF₄ content of the deposition gas mixture was accompanied by a corresponding increase in the fluorine content and a decrease in the hydrogen content of the films. The IR spectra indicate fluorine incorporation in the film primarily via the monofluoride mode. No absorption owing to CF₂ and CF₃ could be detected. The film density and optical bandgap stayed fairly constant until about 40–50% dilution with CF₄. Further dilution of the hydrocarbon with CF₄ resulted in a large drop in the deposition rate, film density, optical bandgap, oxygen plasma etch resistance and thermal stability. These film properties differ from those of a-C:H, F films obtained by the r.f. plasma decomposition of substituted benzenes (Sah et al., Appl. Phys. Lett., 46 (1992) 739).     

Fabrication of a-Si1−xCx:H thin films for solar cells by the Cat-CVD method using a carbon catalyzer

We propose a new approach to fabrication of hydrogenated amorphous silicon carbide (a-Si_1−xC_x:H) thin films for solar cells by the catalytic chemical vapor deposition (Cat-CVD) method using a carbon catalyzer, which is more stable than tungsten or tantalum. It was found that by using the carbon catalyzer, undoped and boron-doped a-Si_1−xC_x:H films were easily obtained from a SiH₄, CH₄ and B₂H₆ mixture without any change in the catalyzer surface, even after deposition for longer than 30 h.     

退火温度对a-C:H膜结构及摩擦学性能的影响

为研究环境温度对含氢无定形碳(a-C:H)膜结构和性能的影响,将a-C:H膜在大气环境中进行高温退火处理,并借助红外光谱、拉曼光谱、X射线光电子能谱、3D表面分析仪和球盘摩擦试验机等手段对退火前后a-C:H膜的结构、组成和性能进行了系统地考察.研究发现,在较低的退火温度下(300℃),a-C:H膜结构无明显变化,而其内应力降低,摩擦学性能显著提高;在400℃和500℃下退火,膜结构发生明显变化并伴随严重氧化,同时摩擦学性能降低甚至完全失效.结果表明,退火温度的选择对a-C:H膜的结构、组成及性能具有重要影响.     

Adherent amorphous hydrogenated carbon films on metals deposited by plasma enhanced chemical vapor deposition

This paper reports the findings of a study of the structural, mechanical, and tribological properties of amorphous hydrogenated carbon (a-C:H) coatings for industrial applications. These thin films have proven quite advantageous in many tribological applications, but for others, thicker films are required. In this study, in order to overcome the high residual stress and low adherence of a-C:H films on metal substrates, a thin amorphous silicon interlayer was deposited as an interface. Amorphous silicon and a-C:H films were grown by using a radio frequency plasma enhanced chemical vapor deposition system at 13.56 MHz in silane and methane atmospheres, respectively. The X-ray photoelectron spectroscopy technique was employed to analyze the chemical bonding within the interfaces. The chemical composition and atomic density of the a-C:H films were determined by ion beam analysis. The film microstructure was studied by means of Raman scattering spectroscopy. The total stress was determined through the measurement of the substrate curvature, using a profilometer, while micro-indentation experiments helped determine the films' hardness. The friction coefficient and critical load were evaluated by using a tribometer. The results showed that the use of the amorphous silicon interlayer improved the a-C:H film deposition onto metal substrates, producing good adhesion, low compressive stress, and a high degree of hardness. SiC was observed in the interface between the amorphous silicon and a-C:H films. The composition, the microstructure, the mechanical and tribological properties of the films were strongly dependent on the self-bias voltages. The tests confirmed the importance of the intensity of ion bombardment during film growth on the mechanical and tribological properties of the films.     

Investigation of stress behaviors and mechanism of void formation in sputtered TiSix films

We have investigated the stress behaviors and a mechanism of void formation in TiSi_x films during annealing. TiSi_x thin films were prepared by DC magnetron sputtering using a TiSi_2.1 target in the substrate temperature range of 200–500 °C. The as-deposited TiSi_x films at low substrate temperature (<300 °C) have an amorphous structure with low stress of 1×10⁸ dynes/cm². When the substrate temperature increases to 500 °C, the as-deposited TiSi_x film has a mixture of C49 and C54 TiSi₂ phase with stress of 8×10⁹ dynes/cm². No void was observed in the as-deposited TiSi_x film. Amorphous TiSi_x film transforms to C54 TiSi₂ phase with a random orientation of (311) and (040) after annealing at 750 °C. The C49 and C54 TiSi₂ mixture phase transforms to (040) preferred C54 TiSi₂ phase after annealing over 650 °C. By increasing substrate temperature, the transformation temperature for C54 TiSi₂ can be reduced, resulting in relieved stress of TiSi₂ film. The easy nucleation of the C54 phase was attributed to an avoidance of amorphous TiSi_x phase. We found that amorphous TiSi_x→C54 TiSi₂ transformation caused higher tensile stress of 2×10¹⁰ dynes/cm², resulting in more voids in the films, than C49→C54 transformation. It was observed that void formation was increased with thermal treatment. The high tensile stress caused by volume decreases in the silicide must be relieved to retard voids and cracks during C54 TiSi₂ formation.     

Thermal stability of nanocomposite CrC/a-C:H thin films

The thermal stability of low-friction Me-C/a-C:H coatings is important for their potential applications in the tool and automotive industry. Recently we showed that CrC_x/a-C:H coatings prepared by unbalanced magnetron sputtering of a Cr target in Ar + CH₄ glow discharges exhibit a nanocomposite structure where metastable fcc CrC nanocrystals are encapsulated by an a-C:H phase. Here, we present the structural evolution of these nanocomposite CrC/a-C:H coatings during annealing. High-temperature X-ray diffraction in vacuum and differential scanning calorimetry (DSC) combined with thermo-gravimetric analysis in Ar atmosphere indicate decomposition of the formed metastable fcc CrC phase and subsequent formation of Cr₃C₂ and Cr₇C₃ and structural transformation of the a-C:H matrix phase towards higher sp² bonding contents at temperatures above 450 °C. Combined DSC and mass spectrometer analysis as well as elemental profiling after annealing in vacuum by elastic recoil detection analysis relate this transformation to the loss of bonded hydrogen at temperatures above 200 °C.Due to these structural changes the coefficient of friction depends on the annealing temperature of the nanocomposite a-C:H coatings and shows a minimum of ∼ 0.13 for T = 200 °C. The more complex tribochemical reactions, influenced by the hydrogen loss from the coating during in-situ high temperatures ball-on disc tests, result in coefficient of friction values below 0.05 for T < 120 °C.     

On the chemistry at the Si,Ti-doped a-C:H/TiC interface

Silicon-titanium-doped a-C:H, deposited via plasma assisted chemical vapor deposition and its chemistry at the titanium carbide interface has been studied via X-ray photoelectron spectroscopy. In the a-C:H film, as well as at the interface, the carbide species TiSiC is formed. Thermal treatment of Si,Ti-a-C:H films on TiC causes an increase in TiSiC at the interface leading to a better adhesion performance.     

Influence of the microstructure on the mechanical and tribological behavior of TiC/a-C nanocomposite coatings

The performance of protective thin films is clearly influenced by their microstructure. The objective of this work is to study the influence of the structure of TiC/a-C nanocomposite coatings with a-C contents ranging from ~ 0% to 100% on their mechanical and tribological properties measured by ultramicroindentation and pin-on-disks tests at ambient air, respectively. The microstructure evolves from a polycrystalline columnar structure consisting of TiC crystals to an amorphous and dense TiC/a-C nanocomposite structure when the amount of a-C is increased. The former samples show high hardness, moderate friction and high wear rates, while the latter ones show a decrease in hardness but an improvement in tribological performance. No apparent direct correlation is found between hardness and wear rate, which is controlled by the friction coefficient. These results are compared to the literature and explained according to the different film microstructures and chemical bonding nature. The film stress has also been measured at the macro and micro levels by the curvature and Williamson-Hall methods respectively. Other mechanical properties of the coating such as resilience and toughness were evaluated by estimating the H³/E?² and H/E? ratios and the percentage of elastic work (W_e). None of these parameters showed a tendency that could explain the observed tribological results, indicating that for self-lubricant nanocomposite systems this correlation is not so simple and that the assembly of different factors must be taken into account.     

Properties of nitrogen diluted hydrogenated amorphous carbon (n-type a-C:H) films and their realization in n-type a-C:H/p-type crystalline silicon heterojunction diodes

Nitrogen incorporated hydrogenated amorphous carbon (a-C:N:H) films were grown in an asymmetric rf PECVD system using C₂H₂ and N₂ gaseous mixture. Deposition rate, stress, hardness, optical bandgap, refractive index, and electrical characteristics have been studied as a function of self bias. Microstructures of these films were also studied using LASER Raman technique. Finally nitrogen diluted a-C:H films were realized as n-type semiconductor in n-type a-C:H/p-type crystalline silicon hetrojunction diodes. Current-voltage (I-V) and capacitance-voltage (C-V) characteristics have also been studied as a function of self bias on these heterojunction diodes.     

Transmission electron microscopy of annealed a-Si1−xCx:H/Al films with different Al grain sizes

The crystallization behavior of a-Si_1−xC_x:H/Al films after annealing has been investigated by transmission electron microscopy and Raman scattering. It is found that the crystallization process is complex and non-uniform, and that both equiaxial and branching Si grains with many twins and stacking faults arise at annealing temperatures as low as 250 °C. Both fine polycrystalline β-SiC grains and fractal-like -SiC aggregates are first observed in a few regions in a-Si_1−xC_x:H/Al films annealed at 350 °C. The increase of the Al grain size can cause a decrease in the crystallization temperature and a rise in the grain growth rate of Si. At higher annealing temperatures, the reaction process SiC+Al→Al₄C₃+Si is predominant.     

Effect of deposition temperature and thermal annealing on the dry etch rate of a-C: H films for the dry etch hard process of semiconductor devices

The effect of deposition and thermal annealing temperatures on the dry etch rate of a-C:H films was investigated to increase our fundamental understanding of the relationship between thermal annealing and dry etch rate and to obtain a low dry etch rate hard mask. The hydrocarbon contents and hydrogen concentration were decreased with increasing deposition and annealing temperatures. The I(D)/I(G) intensity ratio and extinction coefficient of the a-C:H films were increased with increasing deposition and annealing temperatures because of the increase of sp² bonds in the a-C:H films. There was no relationship between the density of the unpaired electrons and the deposition temperature, or between the density of the unpaired electrons and the annealing temperature. However, the thermally annealed a-C:H films had fewer unpaired electrons compared with the as-deposited ones. Transmission electron microscopy analysis showed the absence of any crystallographic change after thermal annealing. The density of the as-deposited films was increased with increasing deposition temperature. The density of the 600 °C annealed a-C:H films deposited under 450 °C was decreased but at 550 °C was increased, and the density of all 800 °C annealed films was increased. The dry etch rate of the as-deposited a-C:H films was negatively correlated with the deposition temperature. The dry etch rate of the 600 °C annealed a-C:H films deposited at 350 °C and 450 °C was faster than that of the as-deposited film and that of the 800 °C annealed a-C:H films deposited at 350 °C and 450 °C was 17% faster than that of the as-deposited film. However, the dry etch rate of the 550 °C deposited a-C:H film was decreased after annealing at 600 °C and 800 °C. The dry etch rate of the as-deposited films was decreased with increasing density but that of the annealed a-C:H films was not. These results indicated that the dry etch rate of a-C:H films for dry etch hard masks can be further decreased by thermal annealing of the high density, as-deposited a-C:H films. Furthermore, not only the density itself but also the variation of density with thermal annealing need to be elucidated in order to understand the dry etch properties of annealed a-C:H films.     

Growth of CNx/BN:C multilayer films by magnetron sputtering

Symmetric CN_x/BN:C multilayer thin films, with nominal compositional modulation periods of Λ=2.5, 5, and 9 nm were deposited by unbalanced dual cathode magnetron sputtering from C (graphite) and B₄C targets in an Ar/N₂ (60/40) discharge. The multilayers and single-layer of the constituent CN_x and BN:C compounds were grown to a total thickness of 0.5 μm onto Si(001) substrates held at 225°C and a negative floating potential of 30 V (E_i≈24 eV). Layer characterizations were performed by TEM, X-ray reflectivity, RBS, and nanoindentation measurements. Results show that CN_0.33 and BN:C (35, 50, and 15 at.% of B, N, and C, respectively) layers were prepared at the above conditions. It is suggested that all films exhibit a three-dimensional interlocked structure with a cylindrical texture in the film growth direction. The structure was continuous over relatively well defined and smooth CN_x/BN:C interfaces. All coatings exhibit extreme elasticity with elastic recoveries as high as 85–90% (10 mN maximum load) attributed to the observed structure. However, the multilayers were stiffer and more elastic compared to that of the single-layers and thus shows promise for improved protective properties.     

Improved crystallization characteristics of ZnO thin film grown onto a-C:H film used as a buffer layer

We employed a-C:H buffer layer to improve the crystalline property of ZnO thin film for the membrane film bulk acoustic resonator (FBAR). The a-C:H film as a buffer layer is prepared by applying dc bias of 200 V and also this sample showed a smoother surface roughness, higher hardness and Young's modulus when compared to the other samples. In addition, the FWHM value was improved from 7.5 to 4.3° on a-C:H film. The fabricated FBAR device showed the resistivity of 0.73 × 10⁸ Ω when compared with no buffer layer and the frequency characteristics of the FBAR were finally confirmed to be 1.15 GHz and 21.24 dB, respectively.     

Deposition of a-C:N films and evaluation of their robustness in electrochemical applications

A multilayer a-C:N film electrode deposition process has been developed using the filtered cathodic vacuum arc (FCVA) system based on the highly conductive silicon wafer with a Ti interlayer for ohmic contacts. Its robustness has been evaluated under the practical electrochemical conditions and shows that it has no pin-hole and no breaking point happened when voltages are applied on it. Extremely large errors will arise in the electrochemical characterizing a-C:N film electrodes (hydrogen and oxygen evolutions and oxygen reduction) when there is a pin-hole or a broken point in the films. And the error caused by the non-ohmic contact amplifies at a high potential range. It is expected that non-robust a-C:N film electrodes and non-ohmic contacts mislead the electrochemical characterizing on a-C:N films.     

Microstructure and optical properties of chromium containing amorphous hydrogenated carbon thin films (a-C:H/Cr)

Chromium containing amorphous hydrogenated carbon thin films was deposited using a dc sputter deposition technique under various mixtures of methane and Ar. The microstructure, composition, and optical properties of the resulting films were investigated. We show that a-C:H/Cr thin films exhibiting absorptance in certain wavelengths are greater than 95% and the average absorptance was 86% in the 0.3 to 2.5 µm wavelength can be obtained by using appropriate methane/Ar ratios and deposition times.     

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.