A magnetron sputtering technique to prepare a-C:H films: Effect of substrate bias

Amorphous hydrogenated carbon (a-C:H) films were deposited by magnetron sputtering with a mixture gas of Ar and CH₄. The a-C:H films deposited by this method have relatively low internal stress (<1 GPa) compared to some films deposited by conventional deposition process. The effects of substrate bias voltage on microstructure, surface morphology and mechanical properties of the films were investigated by various techniques. It has been found that the polymer-like structure is dominated at low bias voltage (−100 V), while the diamond-like structure with the highest hardness and internal stress is the main feature of the a-C:H films deposited under high bias voltage (−300 V). With increasing the bias voltage further, the feature of diamond-like structure decreases associating with the increase of graphitization. The frictional test shows that the friction coefficient and wear rate of the a-C:H films are depended strongly on structure and mechanical properties, which were ultimately influenced by the deposition method and bias voltage.     

Effect of Cr incorporation on the structural and optoelectronic properties of TiO2:Cr deposited by means of a magnetron co-sputtering process

In this work, we report on the effect of Cr incorporation on the microstructural and optical properties of TiO₂:Cr thin films deposited by the RF-magnetron sputtering method. The structural, morphological, chemical bonding and optoelectronic properties of the sputter-deposited TiO₂:Cr films were systematically investigated, as a function the incorporated Cr content, by means of various techniques including X-ray diffraction (XRD), atomic force microscopy (AFM), Fourier-Transform Infra-Red (FTIR) absorption, X-ray Photoelectron Spectroscopy (XPS) and ellipsometry. The Cr incorporation into the TiO₂ films was controlled by adjusting the RF power (P_Cr) on the Cr target during the co-sputtering process of TiO₂ and Cr. We were thus able to demonstrate that by varying P_Cr from 8 W to 150 W, the Cr content of the TiO₂:Cr films can be fairly controlled from ∼2 at.% to ∼18 at.% and their associated bandgap engineered from 3.3 eV to 1.5 eV. The room-temperature deposited TiO₂:Cr are mainly amorphous with the presence of some TiO₂ nanocrystallites, and their density increases as their Cr content is increased. The Cr inclusions were found to coexist under both metallic and oxidized forms in the films. By subjecting the TiO₂:Cr films to post-annealing treatment (at 550 °C), their crystalline structure was found to be sensitive to their Cr content. Indeed, an anatase-to-rutile phase transformation has been pointed out to occur at a Cr content of ∼7 at.%. Likewise, the Cr-content dependence of the bandgap of annealed TiO₂:Cr films undergoes a transition around the 7 at.% of Cr. Our results demonstrate the ability to control the Cr-content of TiO₂:Cr films, which leads to tune their optoelectronic properties, such as bandgap or optical absorption edge.     

Properties of barium hexa-ferrite thin films dependent on sputtering pressure

M-type barium ferrite thin films were deposited onto sapphire (0 0 l) substrates by radio frequency magnetron sputtering. An ultra-thin layer about 20 nm was deposited and annealed before continuous deposition of the films up to 500 nm under different sputtering pressures: 0.2, 0.5, 0.8 and 1.0 Pa, respectively. It was found that the atomic ratios of Fe to Ba increased from 9.3 to 15.0 with the increase of the pressure. The films sputtered at all pressures have c-axis normal to the film plane by a four circle X-ray diffractometer, which is an improvement of the films directly sputtered on the substrate. Needle-like grains were formed on the surface of the films under higher sputter pressure with bubble domains, which is originated from high magnetocrystalline anisotropy of the film. Magnetic hysteresis loops recorded by vibrating sample magnetometer agree with them, where in-plane and out-of-plane loops of the samples prepared under high sputtering pressures are quite different, while they are almost identical of the samples under low pressures. The influence of the sputtering pressure was understood by that with the increase of the pressure, resputtering of the films was increased. Nucleation with c-axis normal to the film plane was deteriorated. Thus samples prepared under high pressure have more needle-like crystallites which have c-axis parallel to the film plane.     

Studies of structural evolution and sensing properties of ZnO nanocrystalline films

ZnO nanocrystalline films have been prepared on Si(1 0 0) substrate using direct current (D.C) magnetron sputtering technique at room temperature. The thickness of nanocrystalline films almost linearly increased with deposition duration and the sizes of crystalline grains almost kept unchanged. After deposition, thermal annealing was performed at 800 °C in atmosphere for 2 h in order to improve the qualities of ZnO thin films. Scanning electron microscope (SEM) images showed the surface roughness of the films less than 45 nm. X-ray diffraction (XRD) patterns revealed the slight evolution of the crystal structures. Raman scattering spectra confirmed the data obtained from X-ray diffraction measurements.With these ZnO nanocrystalline films, prototypic gas sensors were fabricated. Both sensitivity and response of the sensors to different gases (H₂ and CH₄) were investigated. A quick response of time, less than 1 second to CH₄ gas sensor has been achieved.     

Microstructure development and properties of the AlCuFe quasicrystalline coating on near-α titanium alloy

A protective quasicrystalline AlFeCu coating was deposited on TIMETAL 834 substrate by nonreactive magnetron sputtering in order to improve resistance of the alloy to oxidation. Microstructure characterisation of the substrate and the coating was performed by analytical scanning- and transmission electron microscopy as well as X-ray diffractometry. Depending on annealing temperature and time, the deposited coating (2.7 μm thick) has a different microstructure. The coating in Specimen 1 (annealed 600 °C/4 h in vacuum) consisted of two zones: outer, composed of Al₅Fe₂ and Al₂Cu₃ phases and inner, in which only quasicrystalline ψ phase was present. The coating in Specimen 2 (annealed 600 °C/4 h + 700 °C/2 h in vacuum) was fully quasicrystalline and consisted of icosahedral ψ phase.Both coatings exhibit higher microhardness than the substrate material. It was established that the applied surface treatment essentially improves oxidation resistance of the alloy tested at 750 °C during 250 h in static air. Sample weight gain was 60% lower than in the case of uncoated sample. Oxide scale spallation occurred for uncoated alloy while the coated one did not show any spallation. It was found that the very brittle scale formed during oxidation on the uncoated alloy was consisting of TiO₂, while that on the coated one consisted mainly of α-Al₂O₃.     

Dielectric properties of continuous composition spreaded MgO-Ta2O5 thin films

The dielectric properties of MgO-Ta₂O₅ continuous composition spread (CCS) thin films were investigated. The MgO-Ta₂O₅ CCS thin films were deposited on Pt/Ti/SiO₂/Si substrates by off-Axis RF magnetron sputtering system, and then the films were annealed at 350 °C with rapid thermal annealing system in vacuum. The dielectric constant and loss of MgO-Ta₂O₅ CCS thin films were plotted via 1500 micron-step measuring. The specific point of Ta₂O₅-MgO CCS thin film (post annealed at 350 °C) showing superior dielectric properties of high dielectric constant (k ∼ 28) and low dielectric loss (tan δ < 0⋅004) at 1 MHz were found in the area of 3-5 mm apart from Ta₂O₅ side on the substrate. The cation's composition of thin film was Mg:Ta = 0.4:2 at%.     

Silicon oxynitride thin films synthesised by the reactive gas pulsing process using rectangular pulses

Silicon oxynitride thin films were synthesised by the reactive gas pulsing process using an argon, oxygen and nitrogen gas mixture from a semiconductor Si target. Argon and nitrogen were introduced at a constant mass flow rate, whereas oxygen gas was periodically supplied using a rectangular pulsed flow rate. The O₂ injection time T_ON (or duty cycle α) was the only varied parameter. The influences of this parameter on the discharge behaviour, on the Si target voltage, and on the resulting chemical composition of the films were investigated. The temporal evolution of the total pressure exhibits exponential shape differing from the rectangular oxygen pulse shape, due to the response time of the gas flowmeter and to the progressive oxidation of the target and the chamber walls. During the T_ON time, the preferential adsorption of the introduced O₂ induces a decay in Si target voltage. Reversion to the nitrided mode is still possible as soon as the O₂ injection is stopped. The elemental analyses assessed by secondary neutral mass spectrometry (SNMS) showed that the O/N ratio within silicon oxynitride films linearly depends on the T_ON time. Increasing the duty cycle α over a certain value results in an oxidised steady state formation during the T_ON time. This formation was observed by real time measurements of the emission lines ratio I(O^*)/I(Ar^*) indicative of the O₂ partial pressure and confirmed by the time derivative of the target voltage. During the T_OFF time, the alternation with the nitrided mode becomes impossible, leading to the specific synthesis of stoichiometric SiO₂ films.     

BiFeO3/Zn1−xMnxO bilayered thin films

BiFeO₃/Zn_1−xMn_xO (x = 0-0.08) bilayered thin films were deposited on the SrRuO₃/Pt/TiO₂/SiO₂/Si(1 0 0) substrates by radio frequency sputtering. A highly (1 1 0) orientation was induced for BiFeO₃/Zn_1−xMn_xO. BiFeO₃/Zn_1−xMn_xO thin films demonstrate diode-like and resistive hysteresis behavior. A remanent polarization in the range of 2P_r ∼ 121.0-130.6 μC/cm² was measured for BiFeO₃/Zn_1−xMn_xO. BiFeO₃/Zn_1−xMn_xO (x = 0.04) bilayer exhibits a highest M_s value of ∼15.2 emu/cm³, owing to the presence of the magnetic Zn_0.96Mn_0.04O layer with an enhanced M_s value.     

Mo/Si软X射线多层膜中厚度均匀性的精细控制

为了获得光学性质均匀的大面积软X射线多层膜,必须控制好周期结构中单层膜的厚度均匀性。为此建立了磁控溅射薄膜沉积技术中单层膜厚度均匀性的分析和控制模型,解释了基底变速转动法可用来获得膜厚均匀的多层膜,并根据理论分析获得了基底的变速路径。将其应用于基底公转速度变速法来制备均匀性可控的大面积Mo/Si软X射线多层膜。小角X射线衍射测试结果表明,采用优化后的变速路径制备的多层膜,样品不同位置的各级次衍射峰位都能很好吻合,说明多层膜的周期厚度基本一致。计算表明该方法在直径200mm范围内可将周期结构中Mo层的不均匀性从20.6%修正到1.1%,Si层的不均匀性从27.0%修正到1.6%。     

Effects of the substrate and oxygen partial pressure on the microstructures and optical properties of Ti-doped ZnO thin films

Ti-doped ZnO (ZnO:Ti) thin films were deposited on the glass and Si substrates using radio frequency reactive magnetron sputtering. The effects of substrate on the microstructures and optical properties of ZnO:Ti thin films were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and a fluorescence spectrophotometer. The structural analyses of the films indicated that they were polycrystalline and had a hexagonal wurtzite structure on different substrates. When ZnO:Ti thin film was deposited on Si substrate, the film had a c-axis preferred orientation, while preferred orientation of ZnO:Ti thin film deposited on glass substrate changed towards (1 0 0). Finally, we discussed the influence of the oxygen partial pressures on the structural and optical properties of glass-substrate ZnO:Ti thin films. At a high ratio of O₂:Ar of 18:10 sccm, the intensity of (0 0 2) diffraction peak was stronger than that of (1 0 0) diffraction peak, which indicated that preferred orientation changed with the increase of O₂:Ar ratios. The average optical transmittance with over 93% in the visible range was obtained independent of the O₂:Ar ratio. The photoluminescence (PL) spectra measured at room temperature revealed four main emission peaks located at 428, 444, 476 and 527 nm. Intense blue-green luminescence was obtained from the sample deposited at a ratio of O₂:Ar of 14:10 sccm. The results showed that the oxygen partial pressures had an important influence for PL spectra and the origin of these emissions was discussed.