Bactericidal and biocompatible properties of TiN/Ag multilayered films by ion beam assisted deposition

Nanoscale TiN/Ag multilayered films of thickness 500 nm were synthesized on AISI317 stainless steel by ion beam assisted deposition (IBAD) with the modulation period of 4, 5, 6, 7.5, and 12 nm. The bactericidal and biocompatible properties of TiN/Ag multilayered films were investigated through Gram negative E. coli bacteria and L929 cells (mice fibroblast) as well as human umbilical vein endothelial cells (HUVEC). The results show that the TiN/Ag multilayered films with the modulation period of 7.5 nm possess the strongest bactericidal property. The cytotoxicity grade of TiN/Ag multilayered coating with the modulation periods of 7.5 nm, 12 nm is in 0–1 scope, which indicates this film has no cytotoxicity to L929. HUVEC on TiN/Ag multilayered film grows well and shows good cellularity. Auger electronic spectroscopy reveals the relationship between the structure of TiN/Ag multilayered film and the biomedical properties.     

Biaxially textured Ag films by grazing ion beam assisted deposition

The effect of grazing incidence 4 keV Ar⁺ ion irradiation on the early stage of Ag thin film growth on amorphous Si was investigated. The double effect of axial and surface channeling resulted in grains oriented along the 〈110〉 axis in-plane, while the (111) out-of-plane texture was maintained. A slight average tilt of the (111) out-of-plane texture axis towards the ion beam direction is proposed to result from the difference between terrace and step edge sputtering yield. The observed tilt is consistent with a minimum erosion orientation of the surface profile.     

Characterization of Hafnium-Zirconium-Oxide-Nitride films grown by ion beam assisted deposition

Hafnium-Zirconium-Oxide-Nitride (Hf_1−xZr_xO_1−yN_y) films are prepared by ion beam assisted deposition on p-Si and quartz substrates with a composite target of sintered high-purity HfO₂ and ZrO₂. The thermal stability and microstructure characteristics for Hf_1−xZr_xO_1−yN_y films have been investigated. EDS results confirmed that nitrogen was successfully incorporated into the Hf_1−xZr_xO₂ films. XRD and Raman analyses showed that the Hf_1−xZr_xO_1−yN_y films remain amorphous after 1100 °C under vacuum ambient, and monoclinic HfO₂ and ZrO₂ crystals separate from Hf_1−xZr_xO_1−yN_y films with a increase of the annealing temperature up to 1300 °C. Meanwhile, the Hf_1−xZr_xO_1−yN_y films can also effectively suppress oxygen diffusion during high temperature annealing. AFM measurements demonstrated that surface roughness of the Hf_1−xZr_xO_1−yN_y films increase slightly. Then the optical properties of the samples were observed in the ultraviolet-visible range at room temperature. The variation in E_g from 5.64 to 6.09 eV as a function of annealing temperature has also been discussed briefly.     

Photocatalytic properties of Cr-doped TiO2 films prepared by oxygen cluster ion beam assisted deposition

We prepared Cr-doped titanium dioxide (TiO₂) films by oxygen (O₂) cluster ion beam assisted deposition method, and investigated photocatalytic properties of the films as well as crystallographic property, optical property and surface morphology. The films prepared at a substrate temperature below 200 °C were found to be amorphous from the X-ray diffraction measurement. For the substrate temperatures such as 300 °C and 400 °C, the films exhibited rutile and/or anatase structures. The film surface measured by the atomic force microscope (AFM) was smooth at an atomic level. Furthermore, the optical band gap decreased with increase of Cr-composition, and it was approximately 3.3 eV for the non-doped films, 3.2 eV for the 1% Cr-doped films and 3.1 eV for the 10% Cr-doped films, respectively. With regard to the photocatalytic properties of the Cr-doped TiO₂ films, we measured the change of contact angle as well as the photocatalytic degradation of methylene blue by the UV light irradiation. Compared with the non-doped films, the 1% Cr-doped films prepared at a substrate temperature of 400 °C showed high degradation efficiency. In addition, the contact angle of the 1% Cr-doped films with an initial value of 60° decreased to 10° by the UV light irradiation for 20 min, and the films exhibited the predominant properties of photocatalytic hydrophilicity even for the UV light irradiation with longer wavelengths.     

离子束辅助脉冲激光沉积硼碳氮薄膜

以烧结B4C为靶材料、在氮离子束辅助下用脉冲激光沉积方法制备了三元化合物硼碳氮（BCN）薄膜.用X光电子谱和傅立叶变换红外谱方法表征了制备的薄膜.结果表明,膜层中包含B-C、N-C、B-N键等复合结构,以B-C-N原子杂化的形式结合成键,而并非各种成分的简单混合.还探讨了成膜过程和相关机理,离子束中的活性氮有效地和脉冲激光对B4C靶烧蚀产生的硼和碳结合成键,氮离子束的辅助还能在一定程度上抑制氧杂质进入膜层,给衬底适当加温有利于提高氮的含量并影响薄膜的化学结构.     

Texture evolution of transition-metal nitride thin films by ion beam assisted deposition

TiN, VN and CrN were systematically deposited on silicon substrates using ion beam assisted deposition (IBAD) technique at temperatures and ion (N₂⁺) energy ranging from 300 °C to 500 °C and 100 eV to 650 eV, respectively. The results showed that the texture could be controlled by the ion beam energy, flux, and its incident angle, in conjunction with the deposition temperature. For the 0° angle of ion incidence, fiber textures were formed and could be controlled between (111) and (200) surface plane orientation by adjusting ion flux or ion energy. Three types of in-plane textures were produced, when the ion beam was incident at 45° angle, for which cases ion channeling played an important role in the formation of in-plane texture. Using the strain-energy perturbation method, the stability of texture can be further understood. Among the three in-plane textures, the (200) in-plane texture is strain-energy stable, and the others are not.     

The effect of the ion beam energy on the properties of indium tin oxide thin films prepared by ion beam assisted deposition

Indium tin oxide (ITO) thin films have been deposited onto polycarbonate substrates by ion beam assisted deposition technique at room temperature. The structural, optical and electrical properties of the films have been characterized by X-ray diffraction, atomic force microscopy, optical transmittance, ellipsometric and Hall effect measurements. The effect of the ion beam energy on the properties of the films has been studied. The optical parameters have been obtained by fitting the ellipsometric spectra. It has been found that high quality ITO film (low electrical resistivity and high optical transmittance) can be obtained at low ion beam energy. In addition, the ITO film prepared at low ion beam energy gives a high reflectance in IR region that is useful for some electromagnetic wave shielding applications.     

High energy xenon ion beam assisted deposition of TiN film and its industrial application

TiN films have been synthesized by ion beam assisted deposition employing xenon ions with an energy of 40 keV. The formed TiN films were investigated systematically in respect of surface morphology, composition, structure and mechanical properties. Then, they were applied to surface protection of scoring dies. Atomic force microscopy and interferometric observation showed that the TiN film is relatively smooth. Rutherford backscattering spectroscopy analysis indicated that few xenon atoms are retained in the film. It was found by transmission electron microscopy and X-ray diffraction experiments that the formed TiN is a nanocrystal (< 10 nm) film and exhibits slightly (200) preferred orientation. An ultra low load microhardness indentor system was used to examine the plastic property of the film and a hardness of 2300 kgf mm^–2 was calculated from the measured data. Scratch tests showed that the adhesion of TiN film deposited by ion beam assisted deposition at ambient temperature is superior to that of high temperature physical vapour deposited (PVD) TiN film. Both a pin-on-dick tribotest and SRV wear test revealed that the wear resistance of the specimen can be greatly improved by TiN coating. A five times increase of service life of different scoring dies could be obtained by protection of TiN coating.     

Effect of microstructure on degradation of AlN films prepared by ion beam assisted deposition

Two kinds of aluminum nitride (AlN) films were prepared by ion beam assisted deposition (IBAD) by changing the nitrogen ion beam energy; one was deposited with a 0.2 keV ion beam, showing a columnar structure, and the other was deposited with a 1.5 keV ion beam, showing a granular structure. The effect of microstructure on degradation of AlN films was studied by immersing them in aqueous HNO₃, HCl, and NaOH solutions at room temperature. Degradation was examined mainly in terms of changes in optical transmittance and surface morphology. After immersion in HNO₃ and HCl solutions, the average transmittance of the columnar film decreased gradually from the beginning of immersion, while that of the granular film maintained the initial level of transmittance for about 60 h immersion in HNO₃ solution and about 80 h immersion in HCl solution. In NaOH solution, both films were detached readily from the substrate and no remarkable difference in the degradation behavior was observed between the two films. It is concluded that the IBAD AlN films with the granular structure show higher durability against aqueous acid solutions than the films with the columnar structure.     

Deposition of titanium nitride films onto silicon by an ion beam assisted deposition method

Titanium nitride (TiN) films were deposited onto silicon wafers using an ion beam assisted deposition (IBAD) method with an electron cyclotron resonance (ECR) ion source for ionizing the nitrogen (N₂) gas under a condition of high nitrogen ion to titanium neutral ratio. The deposition rate of the TiN films was strongly dependent on the evaporation rate, d_Ti, of Ti metal and decreased with increasing nitrogen ion current. The deposition rate can be approximated as d=βd_Ti?_N2/{1/k+?_N2}−αI, where β, k and α are proportional constants, ?_N2 is the sum rate of neutral and ionized nitrogen impinging onto the substrate, and I is the nitrogen ion current.     

Titanium oxy-nitride films deposited on stainless steel by an ion beam assisted deposition technique

Surfaces of stainless steel SUS304 were coated with titanium oxy-nitride (TiON) films at temperatures of 400–770°C using an ion-beam assisted deposition technique constructed from an electron beam evaporator for Ti evaporation and a microwave ion source for ionizing nitrogen gas. The N ions were accelerated at energies of 0.5–2.0 keV. Most of the deposited TiON films consisted of (60–80)% TiN and (40–20)% TiO₂, and the fraction of TiO₂ increased with increasing substrate temperature. Hardness of the TiNO films varied in the range from 160 GPa to 260 GPa with increasing substrate temperature. The titanium oxy-nitride film could be deposited on stainless steel without a significant deterioration surface layer at 600°C. However, when TiNO films were deposited at temperatures higher than 700°C, the thickness of the TiNO films were significantly thinner and a thick layer containing nitride such as Cr₂N, CrFe, Fe₂N and Fe₄N was formed in a near surface region of stainless steel because more nitrogen diffused into stainless steel.     

Effect of beam voltage on the properties of aluminium nitride prepared by ion beam assisted deposition

The effects of nitrogen-beam voltage on the structure, stress, energy band gap and hardness of AIN thin films deposited on Si (111), Si (100) and sapphire (0001) by ion beam assisted deposition (IBAD) are reported. As the nitrogen-beam voltage was increased from 50 to 200 V, the stress and disorder in the AIN films increased as determined by X-ray diffraction, FTIR and Raman spectroscopy. The preferred orientation of the film's c-axis changed from completely normal to the film at 100 V, to a mixture of normal and in the plane of the film at 200 V. For AIN films deposited under the same conditions, the films were more highly oriented on sapphire (0001) than in Si (111). The hardness of the films increased from 18.2 to 23.7 GPa with the nitrogen-beam voltage, and possible reasons for this change in hardness are considered.     

Controlled nanostructuring of Ag films by ion beam sputter deposition for surface plasmon resonance applications

The growth of Ag nanostrucutres on borosilicate glass substrates by ion beam sputter deposition in the Ar ion energy range from 150 to 600 eV is demonstrated. Rates of deposition as low as 0.01 nm/s are achieved at an Ar ion energy of 150 eV. This leads to the formation of a random array of nearly spherical Ag particles with a mean size of approximately 100 nm, separated by distances of similar order of magnitude. The particles organize themselves into arrays over lengths of at least 10 microm. As the thickness is increased from 3 to 18 nm there is a transition in morphology from an array to linear chains and finally a dense continuous film. There is a similar microstructural evolution as a function of increasing ion energy. The plasmon resonances can be tuned depending on shape, size and interparticle distances. As the thickness of the films increase, the main plasmon peaks can be tuned from 380 to 680 nm. The spheroidal shape of the particles induces additional peaks (localized surface plasmons) centered around 430 +/- 10 nm. Detailed simulations have been carried out based on Maxwell Garnett theory to distinguish the effects of shape and size on plasmon resonances. It is demonstrated that shape rather than the size of the particles has a stronger influence on the shift in plasmon resonances.     

Thick TiN films prepared by vacuum arc deposition and high energetic nitrogen ion beam dynamic mixing implantation

TiN films have many features, such as high wear resistance, high corrosion resistance and good oxidization resistance. With the technology of vacuum arc deposition and high current density nitrogen ion beam dynamic mixing implantation (DMI), the TiN film with a thickness of 33 μm and adhesion 58 N is synthesized on hard alloy and high-speed steel substrates. X-ray diffraction has been used to examine the crystal structure of the films. The results showed that the main phases presented in DMI films are TiN and Ti₂N and that the films revealed random growth. Cross-sectional scanning electron microscopy revealed the dense morphology and the thickness of the films. Micro-hardness tests showed that the average hardness of the films was about 2500 HK. Electrochemical experimental results indicated that DMI-TiN film had excellent corrosion resistance both in 3% NaCl solution and in 0.5 Mol H₂SO₄ solution.     

不同能量离子束辅助沉积对形成氮化钛薄膜性能的影响

用不同能量离子束辅助沉积方法在医用不锈钢317L和Si(100)基底上沉积TiN薄膜。通过X射线光电子能谱(XPS)、X射线衍射(XRD)和俄歇电子能谱(AES)分析研究了薄膜的结构特征;测试了薄膜与基底的附着力和耐磨性;用电化学腐蚀的方法检测了薄膜在Hank’s模拟体液中的耐腐蚀性能;最后采用成纤堆细胞、骨髓细胞体外培养试验考察了生长于不同薄膜表面的细胞粘附、增殖、展布情况及细胞的形态。研究结果表明：用高、低能氮离子兼用的IBAD方法制备的TiN多晶薄膜比只用高能或低能沉积的薄膜具有更强的附着力和耐磨性,在Hank’s模拟体液中显示出更强的抗腐蚀能力,并在细胞体外培养中显示出良好的细胞相容性。     

An orientation competition in yttria-stabilized zirconia thin films fabricated by ion beam assisted sputtering deposition

A previously found orientation competition in ion beam sputtered yttria-stabilized zirconia thin films was studied in detail. The effects of sputtering energy and deposition angle were analyzed in ion sputtered films without assisting ions bombardment. It is found that for normally deposited films, (001) and (011) orientations are favored at low and high sputtering energy respectively. For inclined substrate deposited films, as deposition angle increases, (001), (011) and (111) orientations are advantaged in turn. The results can be attributed to the in-plane energy exchange of deposition atom and adatoms. In ion beam assisting deposited YSZ films of low assisting ions energy and current, a (001) oriented biaxial texture is gradually induced as ion energy increased. In the case of ion beam assisted inclined deposition of 45°, (001) orientation is enhanced and two preferential in-plane orientations are found coexist.     

TiN／Ag多层膜的生物相容性研究

使用离子束辅助沉积（IBAD）的方法，在医用不锈钢317L的基底上制备TiN／Ag多层膜．在TiN／Ag多层膜具有良好的抗茵性和抗腐蚀性的研究基础上，通过细胞毒性试验和溶血试验评价了TiN／Ag多层膜的生物相容性．试验结果表明：TiN／Ag多层膜样品的细胞毒性等级在0～1之间；溶血率〈5％，符合生物医学材料的标准．这些说明TIN／Ag多层膜不仅具有抗菌性和抗腐蚀性，而且具有良好的生物相容性．