Study of graded Ni-Ti shape memory alloy film growth on Si(100) substrate

In-situ X-ray diffraction (XRD) was employed to study the effect of the deliberate change of the Ti/Ni ratio during the deposition of Ni-Ti films. Thus, graded films were deposited exhibiting distinctive composition and crystalline structure along the growth direction. The as-sputtered films were ex-situ characterized by Auger electron spectroscopy (AES), cross-sectional transmission electron microscopy (XTEM), and electrical resistivity (ER) measurements (during thermal cycling). In this paper results are presented concerning a film (thickness of ≈ 420 nm) with a Ti-rich composition in the central part (ranging from 50 to ≈60 at. %) and near-equiatomic composition in the extremities, following four distinct deposition periods (different Ti target powers). During the initial deposition step (near-equiatomic composition) the Ni-Ti B2 phase starts by stacking onto (h00) planes on the naturally oxidized Si(100) substrate due to the presence of the native Si oxide (2–3 nm). The increase of the power of the Ti target in the second and third steps induced the precipitation of Ti₂Ni. When stopping the Ti co-sputtering, Ti₂Ni dissolves and, thus, plays the role of a Ti reservoir for the formation of B2 phase now preferentially stacking onto (110) with the system approaching again the equiatomic composition. The ex-situ study of the morphology of the interface has shown the presence of NiSi₂ silicides (A-NiSi₂ and B-NiSi₂), Ti₄Ni₄Si₇, Ti₂Ni and a non-identified phase constituted by Ni, Ti and Si, most likely amorphous. During thermal cycling, ER measurements revealed phase transitions associated with the B2, R-phase and B19^′ phases. These type of studies allow the identification of intermediate states during deposition and annealing, and the correlation with the final structure of the film, being useful for the optimisation of the deposition parameters in order to fabricate films with a two-way reversible actuation. PACS 81.15.Cd; 61.10.Nz; 68.55.Jk     

MFM and AFM study of thin cobalt films modified by fluorosilane

Polycrystalline cobalt films 100 nm thick were thermally evaporated on oxidized Si(100) substrates. Then 1H, 1H, 2H, 2H perfluorodecyltrichlorosilane (FDTS) films of various thicknesses, in the range of about 2 nm to 30 nm, were grown on cobalt surfaces by vapor phase deposition (VPD). The cobalt films modified by FDTS were investigated using magnetic force microscopy (MFM) and atomic force microscopy (AFM). MFM observation showed that the magnetic structure of the cobalt films modified by FDTS is composed of domains with a considerable component of magnetization perpendicular to the film surface. This in turn indicates that the cobalt films on oxidized Si(100) substrates crystallize in the hexagonal close-packed (HCP) phase and exhibit a texture with the hexagonal axis perpendicular to the film surface. The magnetic domains formed a maze structure. The domain width increased from typically 80–120 nm to 400–500 nm with increasing the thickness of FDTS films from about 2 nm to 30 nm. AFM imaging of the surfaces of FDTS films revealed the presence of an agglomerate morphology. The agglomerates varied in size from typically 30–70 nm to 150–300 nm as the film thickness was increased from about 2 nm to 30 nm.     

Influence of Si substrate preparation on surface chemistry and morphology of L-CVD SnO2 thin films studied by XPS and AFM

Results of experimental studies of the influence of substrate preparation on the surface chemistry and surface morphology of the laser-assisted chemical vapour deposition (L-CVD) SnO₂ thin films are presented in this paper. The native Si(1 0 0) substrate cleaned by UHV thermal annealing (TA) as well as thermally oxidized Si(1 0 0) substrate cleaned by ion bombardment (IBA) have been used as the substrates. X-ray photoemission spectroscopy (XPS) has been used for the control of surface chemistry of the substrates as well as of deposited films. Atomic force microscopy (AFM) has been used to control the surface morphology of the L-CVD SnO₂ thin films deposited on differently prepared substrates. Our XPS shows that the L-CVD SnO₂ thin films deposited on thermally oxidized Si(1 0 0) substrate after cleaning with ion bombardment exhibit the same stoichiometry, i.e. ratio [O]/[Sn] = 1.30 as that of the layers deposited on Si(1 0 0) substrate previously cleaned by UHV prolonged heating. AFM shows that L-CVD SnO₂ thin films deposited on thermally oxidized Si(1 0 0) substrate after cleaning with ion bombardment exhibit evidently increasing rough surface topography with respect to roughness, grain size range and maximum grain height as the L-CVD SnO₂ thin films deposited on atomically clean Si substrate at the same surface chemistry (nonstoichiometry) reflect the higher substrate roughness after cleaning with ion bombardment.     

Orientation selective growth of MgO films on Si (100) by pulsed laser deposition

Selective growth of single-oriented (110), (100) and (111) MgO films on Si (100) substrates without buffer layers was obtained via a two-step method by pulsed laser deposition. It was found that the orientation of the films was determined at the initial deposition stage by the substrate temperature only. The ambient pressure during deposition, the laser fluence and the etching of the Si substrates have no apparent effect on the orientation of the films, but affect their crystalline quality. Under the present deposition conditions, the surfaces of all three different single-oriented films were very smooth and devoid of any particulates. Received: 23 January 2001 / Accepted: 6 June 2001 / Published online: 2 October 2001     

Structural, electrical and mechanical properties of NiO thin films grown by pulsed laser deposition

Nickel oxide (NiO) thin films were prepared by reactive pulsed laser deposition on thermally oxidized Si substrates in 10 Pa oxygen pressure. The substrate temperature during deposition was varied and its influence on the structural, electrical and nanomechanical properties was studied. It was proved that the structural properties were affected by the increase of substrate temperature improving the crystalline structure. Furthermore, a higher substrate temperature resulted in a thicker NiO film, which was attributed to an increased grain size. This effect influenced the electrical properties, too. Resistivity measurements showed that it increased with the increase of substrate temperature. For the first time, the nanomechanical properties of NiO films were studied. The formation and improvement of crystalline structure affected the nanomechanical properties. Nanoindentation testing of NiO thin films revealed an increase of hardness (H) and elastic modulus (E) and a decrease of surface roughness when increasing the substrate temperature.     

Deposition of NiFe(200) and NiFe(111) textured films onto Si/SiO<Subscript>2</Subscript> substrates by DC magnetron sputtering

The effect of substrate temperature T_sub and bias voltage U_bias on the texture of NiFe films with thickness d ～ 30–340 nm deposited by DC magnetron sputtering onto Si(111)/SiO₂ substrates under working gas pressure ～ 0.2 Pa has been investigated. It has been demonstrated that films grown at room substrate temperature have the (111) texture that is refined under a negative bias voltage. The deposition of films onto a grounded (U_bias ～ 0) substrate heated to T_sub ～ 440–640 K results in the formation of textured NiFe(200) films.     

Effect of substrate bias voltages on the diffusion barrier properties of Zr-N films in Cu metallization

Zr-N diffusion barriers were deposited on the Si substrates by rf reactive magnetron sputtering under various substrate bias voltages. Cu films were subsequently sputtered onto the Zr-N films by dc pulse magnetron sputtering without breaking vacuum. The Cu/Zr-N/Si specimens were then annealed up to 650 °C in N₂ ambient for an hour. The effects of deposition bias on growth rate, film resistivity, microstructure, and diffusion barrier properties of Zr-N films were investigated. An increase in negative substrate bias resulted in a decrease in deposition rate together with a decrease in resistivity. It was found that the sheet resistances of Cu/Zr-N(−200 V)/Si contact system were lower than those of Cu/Zr-N(−50 V)/Si specimens after annealing at 650 °C. Cu/Zr-N(−200 V)/Si contact systems showed better thermal stability so that the Cu₃Si phase could not be detected.     

富勒烯作为过渡层生长金刚石薄膜研究

采用微波等离子体化学气相淀积法，以Ｃ６０膜过渡层，在光滑的单晶Ｓｉ衬底（１００）表面的研磨的石英衬底表面等光学衬底上，首次在无衬底负偏压条件下生长出多晶金刚石薄膜，通过扫描电镜观察到生长膜晶粒呈莱花状，生长表面为金刚石（１００）界面。     

The influence of a poly-Si intermediate layer on the crystallization behaviour of Ni-Ti SMA magnetron sputtered thin films

Shape memory alloy Ni-Ti thin films as sputtered are amorphous if the substrate is not intentionally heated during deposition. Therefore, these films have to be heat treated to induce crystallization in order to exhibit the shape-memory effect. Several films have been prepared by dc magnetron sputtering and then studied concerning the influence of the type of substrate (single-crystal Si, polycrystalline Si) on the crystallization kinetics and the final structure. The structural development of the films during crystallization (at a constant temperature of 430 °C) has been studied by X-ray diffraction in grazing incidence geometry off-plane (GIXD) at a synchrotron-radiation beamline. These experiments allow us to establish a correlation between the deposition conditions and the kinetics of crystallization. For films deposited at an electrode distance of 70 mm on a Si(100) substrate, a longer crystallization time is needed compared with films obtained at 40 mm, for otherwise fixed deposition parameters. The analysis of the nucleation kinetics by using the Johnson–Mehl–Avrami equation leads to exponents between 2.6 and 3. The presence of an intermediate layer of poly-Si drastically enhances the crystallization process. Additionally, ex situ annealing of identical samples at 500 °C during 1 h and complementary characterization of the structure and morphology of the films by cross-sectional transmission electron microscopy and selected-area electron diffraction were performed. The temperature dependence of the electrical resistivity was measured, identifying the phase transformation temperature ranges. An increase of the overall resistivity with the precipitation of Ni₄Ti₃ has been detected. Results obtained by X-ray reflectometry and GIXD suggest that during crystallization excess nickel is driven into an amorphous region ahead of the crystal/amorphous interface, thus leading to a higher concentration of Ni at the surface and further precipitation of Ni₄Ti₃. PACS 81.15.Cd; 61.10.Nz; 68.55.Jk     

直流磁控溅射制备AlN薄膜的结构和表面粗糙度

采用直流磁控反应溅射法,在Si(111)基底上成功制备了多晶六方相AlN薄膜.研究了溅射过程中溅射气压对薄膜结构和表面粗糙度的影响.结果表明:当溅射气压低于0.6 Pa时,薄膜为非晶态,在傅里叶变换红外光谱中,没有明显的吸收峰;当溅射气压不低于0.6 Pa时,薄膜的X射线衍射图中均出现了六方相的AlN(100)、(11...     

Characterization of epitaxial MgO growth on Si(001) surface

MgO epitaxial growth on a Si(001) surface by ultrahigh-vacuum molecular beam epitaxy was investigated. Epitaxial orientation and crystalline quality were characterized based on the three-dimensional reciprocal map obtained by Weissenberg RHEED. The epitaxial orientation and crystallinity were strongly dependent on the initial condition of the substrate. When MgO was deposited on a clean Si(001) surface at room temperature a MgO(001) film grew on the Si(001) substrate with two in-plane orientations:MgO[110]//Si[100] and MgO[100]//Si[100]. This is the first observation of MgO epitaxy with the former orientation, which has a smaller mismatch than the latter orientation. When the substrate was exposed to O₂ or thermally oxidized, the latterorientation predominantly grew on the substrate. Deposition of Mg on the substrate also produced the latter orientation. These results imply that nucleation sites on the initial substrate play an important role in determining the epitaxial orientation.     

Epitaxial growth of non-c-oriented ferroelectric SrBi2Ta2O9 thin films on Si(100) substrates

Epitaxial SrBi₂Ta₂O₉ (SBT) thin films with well-defined (116) orientation have been grown by pulsed laser deposition on Si(100) substrates covered with an yttria-stabilized ZrO₂ (YSZ) buffer layer and an epitaxial layer of electrically conductive SrRuO₃. Studies on the in-plane crystallographic relations between SrRuO₃ and YSZ revealed a rectangle-on-cube epitaxy with respect to the substrate. X-ray diffraction pole figure measurements revealed well-defined orientation relations, viz. SBT(116)SrRuO₃(110)YSZ(100)Si(100), SBT[110]SrRuO₃[001], and SrRuO₃[111]YSZ[110]Si[110].     

Evolution of texture in electrodeposited Ni/Cu layered nanostructures

The objective of this research was to study the evolution of crystallographic texture in electrodeposited Ni/Cu laminated nanostructures. Thick films (14-40 µm) consisting of nickel and copper nanolayers (7-27 nm) were fabricated on annealed polycrystalline copper substrates using an electodeposition technique. The microstructure of the deposits was varied by changing the deposition time of each layer and the electrolyte temperature. X-ray diffraction, transmission electron microscopy and scanning electron microscopy were applied to characterize the deposits. Three microstructural behaviours were observed. The deposit with a very fine bilayer thickness (7 nm) was composed of coherent layers parallel to the substrate surface. This deposit replicated the cube orientation of the substrate and showed a strong ?100? texture throughout the thickness of the deposit. An increase in the bilayer thickness (17 and 27 nm) caused a change in the texture from ?100? on the substrate side to ?111? on the solution side. This change in texture is suggested to be associated with a change in the deposition front orientation from {100} to {110} and the subsequent twinning of the cube-oriented crystals. A decrease in the electrolyte temperature inhibited faceting of the interface and hence no twinning was observed.     

SrTiO3(110) thin films grown directly on different oriented silicon substrates

We have grown (110)-oriented SrTiO₃ (STO) thin films on silicon without any buffer layer, by means of pulsed laser deposition technique. The crystal structures of the grown films were examined by X-ray diffraction analysis including θ–2θ scan and rocking curve as well as Laue diffraction methods. STO films with single (110) out-of-plane orientation were formed on all (100), (110) and (111)-oriented Si substrates. The in-plane alignments for the epitaxial STO films grown directly on Si (100) were found as STO[001]//Si[001] and STO[11̄0]//Si[010]. The results should be of interest for better understanding of the growth of perovskite oxide thin films on silicon wafers. PACS 77.55.+f; 68.55.JK; 81.15Fg     

Preparation and crystallization of Pb(Zr0.95Ti0.05)O3 thin films deposited by radio-frequency magnetron sputtering with a stoichiometric ceramic target

0.95 Ti_0.05)O₃ (PZT 95/5) thin films of perovskite structure were prepared on various substrates by the radio-frequency magnetron sputtering with a stoichiometric ceramic target. The crystal structure of the films showed a strong dependency on the crystal structure of the substrates. After conventional-furnace annealing at 750 °C, crack-free and transparent epitaxial PZT 95/5 films were successfully obtained on SrTiO₃(100) substrates, and highly oriented films on LaAlO₃(012). The films on r-sapphire exhibit slightly preferred orientation along both the (040) and (122) axes of the orthorhombic PZT 95/5 phase. The films on YSZ(100) consist principally of the perovskite PZT 95/5 phase with random orientation with a small portion of unknown phase. However, the formation of the perovskite PZT 95/5 phase was not observed in the films on Si(110) or (111)Pt-coated Si substrates. The crystallization of the perovskite PZT 95/5 on these substrates could be improved by rapid thermal annealing (RTA). Single perovskite phase was obtained in the films on (111)Pt/Si which had RTA at 750 °C for 1 min. No tangible loss of Pb from the films occurred during either the sputtering or annealing. Received: 17 April 1997/Accepted: 18 November 1997     

Oxygen-segregation-controlled epitaxy of Y2O3 films on Nb(110)

We demonstrate a very simple and reliable method of manufacturing clean, single-crystalline Y₂O₃ films on Nb(110) substrates in situ. The method exploits the oxygen bulk contamination of Nb as a source of clean oxygen. For substrate temperatures above 800 K oxygen segregation to the Nb surface is so efficient, that yttrium becomes oxidized during deposition without any background oxygen pressure required in the ultrahigh vacuum system. The crystallinity and stoichiometry of these films can be tuned by the deposition temperature. For Y deposition at 1300 K the formation of well-ordered (111)-oriented Y₂O₃ films is achieved. Received: 19 April 2000 / Accepted: 20 April 2000 / Published online: 23 August 2000     

Observation of defects and growth orientations of YBa2Cu3Ox thin films with YSZ buffer layers on Si

We have investigated defects and in-plate orientations of YBa₂Cu₃O_x thin films prepared by pulsed laser deposition (PLD) with YSZ as a buffer layer. The films showed c-axis oriented growth with the transition temperature T_co up to 87 K. Several types of defects including thermally induced cracks, grain boundaries and outgrowths were observed by scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM). The grain boundary provided a favorable path for crack propagation. The outgrowths nucleated on the YSZ surface grew with stoichiometric composition. According to X-ray diffraction (XRD) and HRTEM studies the YSZ buffer layer grew with the orientation relationship, YSZ110//Si110 and YSZ(001)//Si(001) up to the YBCO/YSZ interface. The superconducting YBCO films on top grew mainly with YBCO100//Si110 and YBCO(001)//Si(001), with some minor portions of YBCO110//Si110 and YBCO(001)//Si(001).     

Characterization of the interfacial reaction between sputter-deposited Ni film and Si substrate

In the present work, we report the interfacial reaction characteristics between sputter-deposited Ni film and a single crystalline Si substrate. The effect of substrate bias during the deposition process on the interfacial reaction is also discussed. It was found that sputter deposition with a substrate bias can promote the interfacial reaction between Ni film and Si substrate. Under our experimental conditions, Ni₂Si (orthorhombic) with good crystallinity formed in the film when it was deposited at 200 °C and with a -80 V substrate bias. Such films had relatively low resistivity. Upon thermal annealing at 500 °C, NiSi formed through further reaction, however there is almost no change in resistivity. PACS 67.57.Np; 68.55.-a; 68.35.Fx     

ZnO薄膜的自组织设计及形貌控制

采用单源化学气相沉积(SSCVD)法,在Si(100)基片上通过改变前驱反应体与基片的入射角度,获得了可控柱状取向的ZnO薄膜.研究发现,入射角度的改变可使沉积薄膜中的柱状结构的生成方向倾斜.但X射线衍射(XRD)分析表明:ZnO薄膜的c轴(002)取向与入射角无关,且不沿ZnO柱状结构的生长方向取向.由于ZnO的(002)面为其表面自由能最低且原子密度高的晶面,ZnO薄膜的生长更易于在垂直于基片表面的方向c轴取向生长.     

Influence of substrate temperature and ion-beam energy on the syntheses of aluminium nitride thin films by nitrogen-ion-assisted pulsed-laser deposition

Aluminium nitride (AlN) thin films have been grown on Si(100), Si(111) and Sapphire Al₂O₃(001) substrates by pulsed KrF excimer laser (wavelength 248 nm, duration 30 ns) ablation of an AlN target with the assistance of nitrogen-ion-beam bombardment. The influence of process parameters such as substrate temperature and ion-beam energy has been investigated in order to obtain high-quality AlN films. The AlN films deposited by pulsed-laser deposition (PLD) have been characterized by X-ray diffraction (XRD) to determine the crystalline quality, grain size and growth orientation with respect to the substrate. The XRD spectra of AlN films on Si(100), Si(111) and Sapphire substrates yield full-width-half-maximum (FWHM) values of approximately 1.6. The bonding characteristics in the films have been evaluated by Raman spectroscopy. The chemical composition of the films has been characterized by X-ray photoelectron spectroscopy (XPS). The surface morphology of the films has been measured by atomic force microscopy (AFM). At a substrate temperature of at least 600 °C, polycrystalline AlN films with orientations of AlN(100) and AlN(101) have been synthesized. PACS 68.55.-a; 81.15.Fg; 77.84.Bw