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.     

Preparation and comparison of a-C:H coatings using reactive sputter techniques

Amorphous hydrogenated carbon (a-C:H) coatings are widely used in several industrial applications. These coatings commonly will be prepared by plasma activated chemical vapor deposition (PACVD). The main method used to prepare a-C:H coating in industrial scale is based on a glow discharge in a hydrocarbon gas like acetylene or methane using a substrate electrode powered with medium frequency (m.f. — some 10 to 300 kHz). Some aims of further development are adhesion improvement, increase of hardness and high coating quality on complex geometries. A relatively new and promising technique to fulfil these requirements is the deposition of a-C:H coatings by a reactive d.c. magnetron sputter deposition from a graphite target with acetylene as reactive gas. An advancement of this technique is the deposition in a pulsed magnetron sputter process. Using these three mentioned techniques a-C:H coatings were prepared in the same deposition machine. For adhesion improvement different interlayer systems were applied. The effect of different substrate bias voltages (d.c. and d.c. pulse) was investigated. By applying the magnetron sputter technique in the d.c. pulse mode, plastic hardness values up to 40 GPa could be reached. Besides hardness other mechanical properties like resistance against abrasive wear were measured and compared. Cross sectional SEM images showed the growth structure of the coatings.     

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.     

Tribological behaviour a-C and a-C:H films doped with Ti in biological solutions

The coatings were deposited in a multi magnetron Teer sputtering device with two C targets and a Ti target in Ar atmosphere, on steel and Si substrates. To deposit hydrogenated coatings methane was introduced in the discharge atmosphere. The films were deposited in a range of 7-14 at.% Ti content. X-ray diffraction patterns revealed the presence of a nanocrystalline TiC phase. The hardness varied from 8 to 9 GPa. The tribological tests were performed under dry sliding and lubricated (0.9% NaCl water solution, physiological solution, PS, and 10% fetal bovine serum dissolved in Ringer’s saline solution, FBS) conditions, using a 100Cr6 steel balls with a diameter of 6 mm, in a pin-on-disc wear test apparatus.     

Kinetic modeling of laser annealing processes in a-C:H films

In this research work, a nanosecond-pulsed YAG:Nd laser was used to modify the properties of an amorphous hydrogenated carbon film, which was deposited on c-Si substrate. Experimental examination has revealed that the primary effect of irradiation is diamond-to-graphite transformation or, more specifically, carbon sp³-to-sp² hybridization transition. These findings were qualitatively verified by numerical simulation of kinetic processes that proceed in the film under laser irradiation.     

Effects of applied power on hydrogenated amorphous carbon (a-C:H) film deposition by low frequency (60 Hz) plasma-enhanced chemical vapor deposition (PECVD)

Hydrogenated amorphous carbon (a-C:H) films were deposited onto glass substrates using low frequency (60 Hz) plasma-enhanced chemical vapor deposition and the effects of the applied power on a-C:H films deposition were investigated. During deposition, the electron temperature and the density of CH₄-H₂ plasma were 2.4-3.1 eV and about 10⁸ cm⁻³, respectively. The main optical emission peak of the carbon species observed in the CH₄-H₂ plasma is shown to be excited carbon CH* at 431 nm. The sp³/sp² ratio, band gap, hydrogen content, and refractive index of a-C:H films gradually increased up to a power of 25 W and then saturated at higher power. This tendency is similar to the variation of plasma parameters with varying applied power, thereby indicating that a strong relationship exists between the properties of the films and the plasma discharge.     

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.     

Mechanical properties of a-C:H thin films deposited by r.f. PECVD method

Internal stress, hardness and deposition rate were evaluated for hydrogenated amorphous carbon (a-C:H) films prepared by conventional r.f. plasma-enhanced chemical vapour deposition. The internal stress, hardness and deposition rate of 0.9, 18 and 58 nm/min, respectively, achieved at 40 Pa gas pressure for negative self-bias voltages (V_b) window (from −370 to −550 V). It was found that the negative self-bias voltage window was associated with the existence of two turning points, which shift to higher wavenumber of G band peak position of Raman spectroscopy (Raman) at different V_b in relation to the internal stress and hardness, and rapid decreasing of the relative total peak areas of Fourier Transform Infra-red absorption spectroscopy (FT-IR).The internal stress relaxed from approximately 35 eV ion energy when the energy is increased and rapidly decreased in comparison with the stress relaxation equation.     

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.     

a－C：H膜折射率的变化规律及红外应用

本文对ａ－Ｃ：Ｈ膜的性质如折射率和生长速率的变化规律进行了研究，并且在增透原理的指导下制备了具有高红外透过率的单波段、双波段和宽波段的ａ－Ｃ：Ｈ增透保护膜     

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.     

Characterization of Si:O:C:H films fabricated using electron emission enhanced chemical vapour deposition

Silicon-based polymers and oxides may be formed when vapours of oxygen-containing organosilicone compounds are exposed to energetic electrons drawn from a hot filament by a bias potential applied to a second electrode in a controlled atmosphere in a vacuum chamber. As little deposition occurs in the absence of the bias potential, electron impact fragmentation is the key mechanism in film fabrication using electron-emission enhanced chemical vapour deposition (EEECVD). The feasibility of depositing amorphous hydrogenated carbon films also containing silicon from plasmas of tetramethylsilane or hexamethyldisiloxane has already been shown. In this work, we report the deposition of diverse films from plasmas of tetraethoxysilane (TEOS)-argon mixtures and the characterization of the materials obtained. The effects of changes in the substrate holder bias (V_S) and of the proportion of TEOS in the mixture (X_T) on the chemical structure of the films are examined by infrared-reflection absorption spectroscopy (IRRAS) at near-normal and oblique incidence using unpolarised and p-polarised, light, respectively. The latter is particularly useful in detecting vibrational modes not observed when using conventional near-normal incidence. Elemental analyses of the film were carried out by X-ray photoelectron spectroscopy (XPS), which was also useful in complementary structural investigations. In addition, the dependencies of the deposition rate on V_S and X_T are presented.     

真空退火对a-C:F:H薄膜的结构与光学带隙的影响

使用CF4和CH4为源气体,利用射频等离子体增强化学气相沉积(RF-PECVD)法制备了掺氟非晶碳(a-C:F:H)薄膜,并在N2气氛中进行了不同温度的退火.用原子力显微镜(AFM)观察了薄膜在退火前后表面形貌的变化,发现退火后薄膜表面变得平坦,疏松.用紫外-可见光透射光谱(UV-VIS)并结合傅里叶变换红外光谱(FTIR)和喇曼(Raman)光谱对薄膜进行了分析,获得了薄膜化学键结构和光学带隙的变化情况;发现薄膜的化学键结构和光学带隙与真空退火密切相关,高温退火后薄膜化学键结构:CHx(x=1,2,3下同)、F-芳基、CF2和CF等基团的含量改变;薄膜的光学带隙决定于CHx、退火后CHx含量减少导致薄膜光学带隙的减小.     

Multilayer amorphous hydrogenated carbon (a-C:H) and SiOx doped a-C:H films for optical applications

In this study SiO_x doped amorphous hydrogenated carbon (a-C:H) films were formed from hexamethyldisiloxane (with hydrogen transport gas) by closed drift ion beam deposition applying variable ion beam energy (300-800 eV). The band gap dependence on the deposition energy was determined and used in production of SiO_x doped a-C:H and a-C:H (formed from acetylene gas) multilayer (two and four layers) stack. Optical properties of the multilayer structures as well as individual layers were analysed in the UV-VIS-NIR range (200-1000 nm). It was shown that employing double or four layer systems, the reflectivity of the multilayer structure-crystalline silicon can be tuned to almost 0% at specific wavelength range (550-950 nm), important in solar cell applications.     

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.     

Raman analysis of DLC coated engine components with complex shape: Understanding wear mechanisms

Hydrogenated amorphous carbon (a-C:H) films were deposited on flat samples and engine components using an industrial scale reactor. Characterization of the coating allowed validating its application on engine parts due to high hardness (32 GPa) and high level of adhesion achieved using sublayers. The original approach of this work concerned the use of Raman analysis not only on flat samples after tribometer tests but also directly on coated engine parts with complex shape (like cam/follower system), in order to understand wear mechanisms occurring in motorsport engines. As wear could lead to a coating thickness decrease, a particular attention was paid on the Raman signal of the sublayers. Among the different values extracted from Raman spectrum to characterize structural organization, the value of G peak intensity appeared as a criterion of validity of analyses because it is directly linked to the remaining thickness of the a-C:H layer. For flat samples tested on ball-on-disc tribometer, structure of a-C:H film observed by Raman spectroscopy in the wear track remained stable in depth. Then, a-C:H coated engine components were studied before and after working in real conditions. Two different wear mechanisms were identified. The first one did not show any structural modification of the bulk a-C:H layer. In the second one, the high initial roughness of samples (R_t = 1.15 µm) lead to coating delaminations after sliding. Massive graphitization which decreases drastically mechanical properties of the coatings was observed by Raman analyses on the contact area. The increase of the temperature on rough edges of the scratches could explain this graphitization.     

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.     

a-C∶H/a-Se 复合膜结构的红外及喇曼谱研究

a-C∶H/a-Se/Al 是一种优良的新型复印感光体。我们在 KCl 和 Si 单晶上制备了 a-C∶H/a-Se 复合膜,以进行红外和喇曼谱分析。结果表明,a-Se 上 a-C∶H 层中 CH_n 键型(n=1～3)的比例为:sp~1∶sp~2∶sp~3=0.10∶0.09∶0.81;而 sp~3键型中各功能团比例为:sp~3CH∶sp~3CH_2∶sp~3CH_3=0.28∶0.38∶0.34。在同样工艺条件下制备的 KCl 上 a-C∶H 中的相应比例则为 sp~1∶sp~2∶sp~3=0∶0∶1;sp~3CH∶sp~3CH_2∶sp~3CH_3=0.45∶0.33∶0.22。二者相比,可认为 a-Se(?)衬底上的 a-C∶H 层中主要由 sp~3CH_2和 sp~2CH 构成的“长链型”近程有序成分大大增加。由此可解释复合膜的性能并寻找改进复合膜的途径。     

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.     

a-C∶H/a-Se复合膜非平衡晶化分形特征的SEM观测

a-C∶H/a-Se/Al 感光体的 a-C:H 层在能流密度的6.4×10~(14)eV/mm~2·s 的离子流轰击下发生了非平衡晶化凝聚。晶体凝聚物为“链环状分形”。用盒子计数法测得其分数维 D_0=1.35±0.04;用相关函数法测得其关联维为 D_2=1.39±0.03。这与我们用计算机模拟的结果很好地符合。本文同时讨论了这一系列文章([2][3]及本文)对发展一种新的非平衡晶化分析方法的意义。