Effect of deposition angle on the structure and properties of pulsed-DC magnetron sputtered TiAlN thin films

This article reports the comparison of structure and properties of titanium aluminum nitride (TiAlN) films deposited onto Si(100) substrates under normal and oblique angle depositions using pulsed-DC magnetron sputtering. The substrate temperature was set at room temperature, 400 °C and 650 °C, and the bias was kept at 0, − 25, − 50, and − 80 V for both deposition angles. The surface and cross-section of the films were observed by scanning electron microscopy. It was found that as the deposition temperature increases, films deposited under normal incidence exhibit distinct faceted crystallites, whereas oblique angle deposited (OAD) films develop a kind of “tiles of a roof” or “stepwise structure”, with no facetted crystallites. The OAD films showed an inclined columnar structure, with columns tilting in the direction of the incident flux. As the substrate temperature was increased, the tilting of columns nearly approached the substrate normal. Both hardness and Young's modulus decreases when the flux angle was changed from α = 0° to 45° as measured by nanoindentation. This was attributed to the voids formed due to the shadowing effect. The crystallographic properties of these coatings were studied by θ-2θ scan and pole figure X-ray diffraction. Films deposited at α = 0° showed a mixed (111) and (200) out-of-plane orientation with random in-plane alignment. On the other hand, films deposited at α = 45° revealed an inclined texture with (111) orientation moving towards the incident flux direction and the (200) orientation approaching the substrate normal, showing substantial in-plane alignment.     

Structure evolution of the biaxial alignment in sputter-deposited MgO and Cr

The growth of biaxially aligned layers, i.e. layers with both a preferential out-of-plane and an in-plane crystallographic orientation, on non-aligned metallic substrates is investigated. Unbalanced magnetron sputtering on an inclined substrate is used to deposit the layers.This method enables us to grow biaxially aligned layers for different classes of materials with different physical and chemical properties. The results for biaxially aligned MgO which is a cubic metal oxide (FCC rocksalt structure), and pure metallic chromium films (BCC) are presented.A comparison between biaxially aligned MgO and Cr concerning the microstructure and crystallographic texture is discussed. A correlation between the sputter deposition parameters on the biaxial alignment of both materials is observed. Both materials have a columnar V-shape structure with a faceted surface, corresponding to zone T of the well known structure zone model of Thornton. The MgO layers exhibit a [111] out-of-plane orientation, while Cr layers have an [100] preferential orientation. MgO as well as Cr show a strong in-plane alignment.     

Ion beam assisted texturing of polycrystalline Y2O3 films deposited via electron-beam evaporation

Ion-beam assisted deposition of polycrystalline Y₂O₃ films using e-beam evaporation was investigated. For growth on non-crystalline substrates, low temperature growth yields randomly oriented polycrystalline material. At elevated temperature, surface energy anisotropy yields a (111) uniaxial texture. For film deposition with irradiation from an Ar ion beam, the out-of-plane texture remained (111) in orientation. The incident Ar ion beam induces an in-plane alignment of the Y₂O₃ films that is relatively broad. A six-fold symmetry in the out-of-plane X-ray diffraction phi-scans was observed for the (111) textured Y₂O₃ films, indicating a multi-variant in-plane texture and suggesting anisotropic damage along both the (110) and (100) projections. The lack of a sharp, single variant in-plane texture with ion beam irradiation is consistent with the relatively weak bond strength in Y₂O₃.     

Hydrothermal deposition and characterization of heteroepitaxial BaTiO3 films on SrTiO3 and LaAlO3 single crystals

Heteroepitaxial BaTiO₃ thin films were deposited in an aqueous solution under hydrothermal conditions on single crystal substrates of (100) SrTiO₃ and (012) LaAlO₃. The reactants consisted of fine TiO₂ particles in a strongly alkaline solution of Ba(OH)₂ at a temperature of 150°C. The growth of the films was studied by atomic force microscopy, high resolution scanning electron microscopy, and X-ray diffraction. The formation of the films occurred by nucleation of {001} faceted islands followed by three-dimensional growth of the islands to cover the substrate. Repeated hydrothermal treatment improved the film thickness and the surface coverage of the substrate at the expense of increased surface roughness. X-ray diffraction coupled with pole figure analysis showed that the films had the same in-plane and out-of-plane orientation as the substrate.     

X-ray determination of strain and texture in sputtered molybdenum and titanium films on silicon

Molybdenum and titanium films prepared with a rotating r.f. diode system were examined by X-ray diffraction for strain and texture. Both films were deposited onto (111)-oriented silicon crystal substrates. Molybdenum films 1.13 μm thick sputtered with a target voltage of -2.7 kV, a zero substrate bias and an average temperature of 180°C were in compression on cooling to room temperature. Pole density plots for the (200), (211), (220), (222), (301) and (321) planes gave relatively sharp peaks. The (220) plane showed a strong peak parallel to the (111) plane on silicon. In contrast, a 1.25 μm titanium film was found to be in tension after sputtering at -2.7 kV, a substrate bias of -50 V and an average temperature of 180°C. Relatively broad pole density plots were found for the (002) and (110) planes. The (100) and (110) planes gave peaks parallel to (111) Si. Intrinsic strains from embedded argon were determined from χ scan X-ray data.     

The morphology and texture of Cu nanorod films grown by controlling the directional flux in physical vapor deposition

We report the creation of unusual biaxial textures in Cu nanorod films, through the control of the incident vapor flux during oblique angle deposition. High-density twin boundaries were formed using a periodic azimuthal swing rotation of the substrate while the incident angle of the Cu flux was fixed at 85° with respect to the surface normal. In contrast, depositions on stationary substrates resulted in nanorod films with a much lower density of twinned crystals. From transmission electron microscopy and x-ray pole figure analysis, the nanorod axis was shown to coincide approximately with the [Formula: see text] crystallographic directions. We also observed the branching of these nanostructures into 'nanotrees'. This branching was attributed to the creation of edge dislocations during the deposition and was particularly prevalent for the case of swing rotation. The mechanisms for the development of texture, twinning, and branching in these nanostructures are discussed.     

Preferential growth of ZnO thin films by the atomic layer deposition technique

Preferred orientation of ZnO thin films deposited by the atomic layer deposition (ALD) technique could be manipulated by deposition temperature. In this work, diethyl zinc (DEZn) and deionized water (H(2)O) were used as a zinc source and oxygen source, respectively. The results demonstrated that (10.0) dominant ZnO thin films were grown in the temperature range of 155-220?°C. The c-axis crystal growth of these films was greatly suppressed. Adhesion of anions (such as fragments of an ethyl group) on the (00.2) polar surface of the ZnO thin film was believed to be responsible for this suppression. In contrast, (00.2) dominant ZnO thin films were obtained between 220 and 300?°C. The preferred orientations of (10.0) and (00.2) of the ZnO thin films were examined by XRD texture analysis. The texture analysis results agreed well with the alignments of ZnO nanowires (NWs) which were grown from these ZnO thin films. In this case, the nanosized crystals of ZnO thin films acted as seeds for the growth of ZnO nanowires (NWs) by chemical vapor deposition (CVD) process. The highly (00.2) textured ZnO thin films deposited at high temperatures, such as 280?°C, contained polycrystals with the c?axis perpendicular to the substrate surface and provided a good template for the growth of vertically aligned ZnO NWs.     

Optical and structural properties of LaF3 thin films

LaF(3) thin films of different thicknesses were deposited on CaF(2) (111) and silicon substrates at a relatively low substrate temperature of 150 degrees C. Optical (transmittance, reflectance, refractive index, and extinction coefficient) and mechanical (morphology and crystalline structure) properties have been investigated and are discussed. It is shown that LaF(3) thin films deposited on CaF(2) (111) substrates are monocrystalline and have a bulklike dense structure. Furthermore, it is presented that low-loss LaF(3) thin films can be deposited not only by boat evaporation but also by electron beam evaporation.     

Structural investigation of silicon films chemically vapour deposited onto amorphous SiO2 substrates

The influence of substrate temperature and the silane-to-nitrogen ratio on the structure of silicon films 0.5–0.6 μm thick deposited onto amorphous SiO₂ substrates was investigated by X-ray diffraction. The investigations were carried out for silicon films deposited at various temperatures in the range 500–750 °C and with various silane-to-nitrogen ratios in the range 3.04 × 10^-4-2.84 × 10^-3 by volume. The silicon films deposited at 500 °C were amorphous while the films deposited at 550 °C were randomly oriented polycrystalline. The films deposited in the temperature range 600–700 °C were polycrystalline with a preferred orientation that changed from 〈110〉 through 〈100〉 to 〈111〉. The structure of the films deposited at 750 °C was randomly oriented polycrystalline. Investigations of the influence of the silane-to-nitrogen ratio on the silicon film structure revealed that the structure of films deposited at a substrate temperature of 500 °C was independent of the silane-to-nitrogen ratio. The structure of the films deposited at 600 °C depended on the silane-to-nitrogen ratio and changed from polycrystalline with a 〈110〉 preferred orientation to randomly oriented polycrystalline when the ratio was increased. The structure of films deposited at 700 °C also depended on the silane-to-nitrogen ratio and changed from randomly oriented polycrystalline to polycrystalline with double preferred orientation (〈100〉 and 〈111〉) when the ratio was increased.     

Temperature dependent biaxial texture evolution in Ge films under oblique angle vapor deposition

The morphology and texture of Ge films grown under oblique angle vapor deposition on native oxide covered Si(001) substrates at temperatures ranging from 230 °C to 400 °C were studied using scanning electron microscopy, X-ray diffraction and X-ray pole figure techniques. A transition from polycrystalline to {001}<110> biaxial texture was observed within this temperature range. The Ge films grown at substrate temperatures < 375 °C were polycrystalline. At substrate temperatures of 375 °C and 400 °C, a mixture of polycrystalline and biaxial texture was observed. The 230 °C sample consisted of isolated nanorods, while all other films were continuous. The observed biaxial texture is proposed to be a result of the loss of the interface oxide layer, resulting in epitaxial deposition of Ge on the Si and a texture following that of the Si(001) substrates used. The rate of oxide loss was found to increase under oblique angle vapor deposition.     

Evolution of texture of CeO2 thin film buffer layers prepared by ion-assisted deposition

Evolution of texture in CeO₂ thin films was studied using biased magnetron sputtering and ion beam assisted magnetron sputtering. Films deposited onto polycrystalline Hastelloy metal substrates by biased magnetron sputtering develop preferential (002) growth as the energy of the ions is increased from zero to above 100 eV. For ion beam assisted magnetron sputtering (magnetron IBAD), with the ion beam directed at 55° to the substrate normal, the evolution of biaxial alignment is controlled by the ion beam energy and the ion/atom arrival rate ratio. Ion beam energies >200 eV and ion/atom ratios >0.3 lead to perfect biaxial alignment with one pole aligned along the ion beam direction. Epitaxial growth of CeO₂ films was observed for MgO(001) substrates at 750°C without any ion assistance, and on yttria-stabilised zirconia (001) buffer layers at room temperature and a bias of −80 V.     

Structure and microstructure of EB-PVD yttria thin films grown on Si (111) substrate

Structure and microstructure of yttria thin films grown by electron beam physical vapour deposition on a stationary Si (111) substrate at room temperature (RT), 500° and 700 °C, were investigated by the grazing-incidence X-ray diffraction and scanning electron microscopy, respectively. X-ray photoelectron spectroscopy provided information on the surface contamination from the atmosphere and the Y oxidation state. A strong effect of the deposition temperature and the vapour flux incidence angle was found. The film deposited at RT is polycrystalline with very fine grains of the body-centered cubic (bcc) crystallographic symmetry. An increase of deposition temperature results in a rapid growth of bcc grains with an improved crystalline structure. Moreover, the based-centered monoclinic phase appears for the deposition temperature of 700 °C. Preferred grain orientation (texture) with two main components, (400) and (622), was observed in the films deposited at 500 °C whereas no texture was found for 700 °C. The microstructure exhibits the columnar feather-like structure of different degrees of perfection which can be explained by the shadowing effects caused by an oblique vapour flux incidence angle. Surface morphology of the films is governed by a combination of the triangular and four-sided (square) columns. All films were found to be dense with a little porosity between the columns.     

Crystal texture selection in epitaxies of orthorhombic antiferromagnetic YMnO3 films

The orthorhombic phase of YMnO₃ has been epitaxially stabilized on SrTiO₃ single crystal substrates. Changing the substrate orientation, the out-of-plane orientation of the epitaxial films can be tuned to (001), (101), or (100). Depending on the orientation, the films present varied crystal domain structures and lattice strains. Single domain YMnO₃(100) films have been grown on SrTiO₃(110) substrates, whereas they present two and three crystal variants on SrTiO₃(001) and SrTiO₃(111), respectively. Epitaxial stress in each domain is anisotropic, tensile in one direction and compressive in the other. It has consequences in the texture selection when domains with different out-of-plane orientation can grow epitaxially. Antiferromagnetism of YMnO₃ films has been confirmed by measuring the exchange bias field induced in an underlying ferromagnetic SrRuO₃ layer.     

Structural characterization of vacuum evaporated ZnSe thin films

Thermally evaporated ZnSe thin films deposited on glass substrates within substrate temperatures (T _s)at 303 K-623 K are of polycrystalline nature having f.c.c. zincblende structure. The most preferential orientation is along [111] direction for all deposited films together with other abundant planes [220] and [311]. The lattice parameter, grain size, average internal stress, microstrain, dislocation density and degree of preferred orientation in the film are calculated and correlated with T _s.     

Optical characteristics of thin ZnSe films of different thicknesses

Polycrystalline ZnSe films of thicknesses 54–785 nm deposited on glass substrates by thermal evaporation were investigated. X-ray diffraction analysis was carried out on as-deposited and annealed films to determine their structure. The ZnSe films were polycrystalline of cubic structure with preferred [111] orientation. Transmission and reflection at normal incidence were performed on ZnSe films in the wavelength range 350–2500 nm to determine the optical constants and optical energy gap. The optical gaps of ZnSe films show remarkable dependence on the film thickness. Analysis of the absorption data revealed the existence of two transition processes (with energy gaps at 2.7 and 2.22 eV for the bulk ZnSe).     

氧化铝陶瓷衬底上金刚石[100]织构生长的氦增强刻蚀

用微波等离子体化学气相沉积法（MPCVD）在氧化铝陶瓷衬底上成功地制备出具有[100]织构的金刚石薄膜,并对该薄膜进行了X射线衍射（XRD）、扫描电子显微镜（SEM）和Raman光谱分析。由于氦原子具有高的电离能,因此本工作在反应气氛中引入了少量的氦。以提高氢等离子体的刻蚀效率,实验结果表明,少量氦气的引入促进了等离子体对非（100）面的选择性刻蚀,从而也有利于金刚石薄膜的[100]织构生长。     

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.     

Biaxial CdTe/CaF2 films growth on amorphous surface

A continuous and highly biaxially textured CdTe film was grown by metal organic chemical vapor deposition on an amorphous substrate using biaxial CaF₂ nanorods as a buffer layer. The interface between the CdTe film and CaF₂ nanorods and the morphology of the CdTe film were studied by transmission electron microscopy (TEM) and scanning electron microscopy. Both the TEM and X-ray pole figure analysis clearly reveal that the crystalline orientation of the continuous CdTe film followed the {111}<121> biaxial texture of the CaF₂ nanorods. A high density of twin faults was observed in the CdTe film. Furthermore, the near surface texture of the CdTe thin film was investigated by reflection high-energy electron diffraction (RHEED) and RHEED surface pole figure analysis. Twinning was also observed from the RHEED surface pole figure analysis.     

Preparation of AlN thin films by nitridation of Al-coated Si substrate

AlN thin films have been grown on Al-coated Si(100) and Si(111) substrates by using nitridation in high-purity nitrogen ambient, where the Al layer was previously deposited on Si by ultra-high vacuum (UHV) electron beam evaporation. The temperature of nitridation was found to play an important role in the formation of AlN films. XRD results showed AlN films formed by nitridation at 1000°C for 30 min exhibited good crystallinity with the preferred orientation of (002) for both Si(111) and Si(100) cases. Other analysis techniques, like Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy have been used to evidence the formation and purity of the AlN films. Scanning electron microscope observations of the films revealed a closely-packed granular texture.     

二氧化钛过渡层对脉冲激光沉积钛酸锶钡薄膜微结构和介电性质的影响

选取极薄Ti02作为过渡层,采用脉冲激光沉积法分别在Si(100)和Pt(111)/Ti/SiO2/Si(100)基底上制备了Bao.6Sro.4TiO3(BST)薄膜,研究过渡层对BST薄膜微结构及电学性质的影响.发现厚度20纳米以内的锐钛矿相结晶TiO2过渡层可使BST薄膜由无规则取向转变为(111)择优取向,而非晶和较厚TiO2过渡层对BST薄膜的取向无影响.结晶的TiO2过渡层也使薄膜的表面颗粒变细.还研究了不同厚度TiO2对BST薄膜电学性质的影响,结果表明BST薄膜在Pt(111)底电极上加入极薄的结晶TiO2过渡层后电学性质有明显改善,薄膜的介电常数和可调谐度提高,而介电损耗降低.加入膜厚约5nm的TiO2过渡层后,测试频率为10 kHz时薄膜相应介电常数、介电损耗及可调谐度分别为513、0.053和36.7%.