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.     

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。     

a-Si∶H及其多层膜光致发光某些性质的研究

本文研究了 a-Si∶H 及 a-Si∶H/a-SiN_x∶H 多层膜光致发光的某些性质。实验研究表明,a-Si∶H 及其多层膜的光致发光峰值能量强烈地依赖于沉积偏压、a-Si∶H 层厚度和内应力,并对这些结果进行了讨论。     

氢化非晶硅薄膜光衰退稳定性的影响因素

用热丝辅助微波电子回旋共振化学气相沉积制备样品,通过红外吸收谱图和光衰退图,分析影响a-SiH薄膜光衰退稳定性的因素一方面,非晶硅网格中氢含量、氢硅键合方式以及氢的运动情况均对非晶硅材料的稳定性起着十分重要的作用,另一方面,在非晶硅的基体上生长少量微晶硅,可提高薄膜的稳定性.最终希望能通过两者的结合来探讨如何制备高光敏性和低光致衰退的非晶硅薄膜.     

Doping effects on the optical properties of evaporated a-Si:H films

Thin films of a-Si:H are deposited on substrates at 300°C by a conventional thermal evaporation technique. The electrical conductivity of these films is modified by the addition of antimony giving n-type films. The optical properties of the films are investigated using spectrophotometric measurements of the transmittance and reflectance in the wavelength range 200–3000 nm. Both the refractive index n and the absorption coefficient increase when the Sb content is increased. The absorption edge shifts to lower energies for doped films. The optical gap E_g is evaluated using three different plots for comparison, namely; (hν)^1/2, (/hν)^1/2 and (hν)^1/3. The value of E_g decreases with doping for the three expressions. The Urbach parameter E₀ is calculated and found to increase with doping from 74 meV for the undoped film to 183 meV for concentrations of 9.4 at.% Sb.     

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.     

掺硼a-Si:H薄膜脉冲快速光热退火(PRPTA)的研究

采用射频等离子体增强化学气相沉积（RF-PECVD）法制备掺硼非晶硅（a-Si：H）薄膜,然后用脉冲快速光热退火（PRPTA）法对其进行固相晶化。研究结果表明：掺硼a-Si：H薄膜在550℃恒温条件下退火3h后,其结晶状况无明显变化;而通过加高温热脉冲可以在玻璃衬底上获得晶化较好的P型多晶硅薄膜。另外,非晶硅薄膜的掺硼浓度及脉冲条件对脉冲快速光热退火的效果有一定影响。     

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.     

低介电常数a-C:F薄膜结构和热稳定性研究

采用电子回旋共振等离子体化学气相沉积的方法以C4F8和CH4为源气体制备了非晶氟化碳(a-C:F)薄膜.采用傅里叶变换红外光谱(FTIR)和X光电子能谱(XPS)技术分析了a-C:F薄膜化学组分.FTIR分析表明a-C:F薄膜中存在CF=C(1680 cm-1)和位于a-C:F薄膜交联结构末端的CF2=CF (1780 cm-1)结构.C1s峰高斯解叠后结合态与结合能对应关系为:CF3(295 eV),CF2(293 eV),CF(291 eV),C-O(289 eV),C-CFx(x=1～3)(287 eV),以及位于a-C:F薄膜交联结构末端的C-C结合态(285 eV).位于a-C:F薄膜交联结构末端的CF3和C-C结构热稳定性较差,退火后容易生成气态挥发物并导致a-C:F薄膜厚度减小.当C-CFx交联结构增多,且位于a-C:F薄膜交联结构末端的CF3和C-C结构减少时,a-C:F薄膜热稳定性提高.     

微波等离子体化学气相沉积的 a-Si∶H 性能研究

本文着重对微波等离子体化学气相沉积法高速沉积的 a-Si∶H 膜的物理性能进行评价研究.测量了沉积膜的光电性能、暗电导激活能、光禁带宽度、光吸收特性、沉积膜中悬键态密度以及氢含量等,并讨论沉积条件对膜性能的影响.结果表明,在沉积速率高达30～90(?)/s 情况下,膜的光电导(光照强度10~5Lux)与暗电导比值可达10~3～10~5,暗电导率从10~(-3)到10~(-11)((?)cm)~(-1),其激活能在0.23～0.88eV 之间(0～200℃温度范围内),光禁带宽度为1.40～2.20eV,氢含量约为2～20%.     

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.     

Created defect under illumination in a-Si:H: hydrogenated or isolated dangling bond ?

The present paper deals with dangling bonds creation in a-Si:H thin films under continuous light illumination with moderate intensity. Taking into account the equilibrium conditions of defect density given by the defect pool model, we propose that hydrogenated dangling bond is the dominant defect in good quality a-Si:H samples and the recombination occurs not only at weak SiSi bonds but also at SiHHSi configurations. The obtained dangling bonds creation kinetic according our model is in good agreement with experiments.     

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。     

a-C∶H/a-Se复合膜晶化分形凝聚的计算机模拟研究

本文基于红外透射及喇曼谱分析的结果提出了一个 a-C:H/a-Se 复合膜的 a-C∶H 层非平衡晶化凝聚模型,并做了计算机模拟研究。模拟得到的图形是具有良好的无标度性的链环状分形。其分维值为1.37±0.02,此结果得到了实验的肯定。这对非晶膜的结构及晶化机理的研究均富有价值。     

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.     

双元素掺杂的a-Si∶H光电特性研究

本文研究由氮(N)、硼(B)以及卤素(X)元素掺杂的 a-Si∶H 膜在静电场下的光电特性.实验结果表明,(B+N)、(B+X)双元素掺杂比单元素更明显地提高 a-Si∶H 膜的表面电位 V_(?),降低残余电位V_R,并在 X/Si=10~(-2),B_2H_6/SiH_4=0.3×10~(-4)时,得到了 V_(?)=60V/μm,σ_D=10~(-4)((?)cm)~(-1)的静电复印用a-Si∶H 材料.     

H+辐照前后Mo涂层表面的XPS分析

对离子束混合技术在不锈钢基体上沉积的钼膜进行了H 辐照前后的XPS分析,研究了H 辐照对钼膜的结合能的影响.分析结果表明,沉积的钼膜中除了单质钼外,还有部分钼的氧化物;H 辐照结果表明,H 的辐照使钼的结合能向低能方向偏移;钼的氧化物有所减少,说明污染的氧化物在一定程度上被择优溅射掉.     

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.     

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.