Low-temperature epitaxial growth of conductive LaNiO3 thin films by RF magnetron sputtering

Epitaxial growth of LaNiO₃ (LNO) thin films was successful on CeO₂/YSZ/Si(100), MgO(100) and SrTiO₃ (STO)(100) substrates by RF magnetron sputtering at 300 °C, although pulsed laser deposition requires 600 °C to prepare epitaxial LNO films according to the literature. Epitaxial LNO films deposited on CeO₂/YSZ/Si(100) and STO(100) had single orientation of LNO[100]//CeO₂[110]//YSZ[110]//Si[110]) and LNO[100]//STO[100], respectively. On the other hand, epitaxial LNO films deposited on MgO(100) had mixed orientations of LNO[100]//MgO[100] and LNO[100]//MgO[110]. The lattice parameter, composition and resistivity of the LNO thin films were strongly dependent on the substrate temperature. The minimum resistivity of LNO films was approximately 5×10⁻⁶ Ω m, which value almost agrees with the resistivity in the literature. It was found that the temperature to achieve minimum resistivity was 200 °C, irrespective of the type of substrate. The surface of the LNO films was smooth and flat.     

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.     

Effects of deposition parameters on the crystallinity of CeO2 thin films deposited on Si(100) substrates by r.f.-magnetron sputtering

Deposition temperature, r.f.-power and seed layer deposition time were important parameters effecting the crystallinity of CeO₂ thin films deposited by r.f.-magnetron sputtering on Si(100) substrates. The CeO₂ (200) peak was notable for a deposition temperature above 600°C. With decreased r.f.-power and thus lower deposition rate, the intensity of the CeO₂(200) peak increased. When the seed layer deposition time was less than 20 s, the CeO₂(200) peak dominated. Transmission electron microscopy (TEM) diffraction revealed that the deposited CeO₂ thin film had a polycrystalline structure. Annealing at 950°C in O₂ atmosphere for 30 min increased and sharpened the CeO₂(200) peak.     

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.     

Growth of calcium carbonate by the atomic layer chemical vapour deposition technique

Thin films of CaCO₃ (calcite) have been grown with the atomic layer chemical vapour deposition (ALCVD) technique, using Ca(thd)₂ (Hthd=2,2,6,6-tetramethylheptan-3,5-dione), CO₂, and ozone as precursors. Pulse parameters for the ALCVD-type growth are found and self-limiting reaction conditions are established between 200 and 400 °C. Calcium carbonate films have been deposited on soda-lime glass, Si(100), -Al₂O₃(001), -Al₂O₃(012), -SiO₂(001), and MgO(100) substrates. The observed textures were: in-plane oriented films with [100](001)CaCO₃ [100](001)Al₂O₃ and [100](001)CaCO₃[110](001)Al₂O₃ on -Al₂O₃(001), amorphous films on -Al₂O₃(012) when grown at 250 °C, and columnar oriented films on soda-lime glass, Si(001), -SiO₂(001), and MgO(100) substrates with (00l) and (104) parallel to the substrate plane at 250 and 350 °C, respectively. The film topography was studied by atomic force microscopy and AC impedance characteristics were measured on as-deposited films at room temperature. The films were found to be insulating with a dielectric constant (_r) typically approximately 8. Thin films of CaO were obtained by heat treatment of the carbonate films at 670 °C in a CO₂-free atmosphere, but the thermal decomposition led to a significant increase in surface roughness.     

Relaxation of extrinsic and intrinsic stresses in germanium substrates with silicon films

Si films were deposited on Ge substrates at 400°C by two different Physical Vapor Deposition techniques: (A) ion beam sputtering and (B) magnetron sputtering. The intrinsic stresses in the as-deposited films were measured to be compressive and much greater in samples (A), about −1500 to −2000 MPa than in samples (B), about −300 to −500 MPa. The substrates were subsequently exposed to thermal treatments for varying times at 800°C. In the lower stressed (B) samples, the films had relaxed and reduced the overall curvature of the structure whereas in the high stresses (A) samples, an irreversible large increase in the substrate curvature was found to occur. This indicated that plastic deformation in the Ge substrates itself had occurred.     

Thermal stability and crystallization kinetics of sputtered amorphous Si3N4 films

The crystallization of thin silicon nitride (Si₃N₄) films deposited on polycrystalline SiC substrates was investigated by X-ray diffractometry as a function of annealing time. The amorphous Si₃N₄ films were produced by means of reactive r.f. magnetron sputtering. Annealing at temperatures between 1300 and 1700 °C led to the formation of crystalline films composed of -Si₃N₄ and β-Si₃N₄. The fraction of β-Si₃N₄ in the films reaches approximately 40% at temperatures above 1550 °C. Both polymorphic modifications were formed simultaneously during the crystallization process. A transformation of -Si₃N₄ to β-Si₃N₄ could not be observed in the time and temperature range investigated. The crystallization process of amorphous Si₃N₄ can be described according to the Johnson–Mehl–Avrami–Kolmogorov (JMAK) formalism, assuming a three-dimensional, interface controlled grain growth from pre-existing nuclei. The rate constants show an Arrhenius behaviour with an activation enthalpy of approximately 5.5 eV.     

Synthesis of AlN by reactive sputtering

We present a systematic study of the sub-band gap optical absorption coefficients (hν) in the range 1.2–6 eV vs. deposition-temperature (T_s from 27 to 450°C) films deposited on silica by 13.6 MHz magnetron sputtering of an Al target with 53 and 72% N₂ in the reactive mixture. X-ray diffraction, infrared absorption and Raman diffusion are also presented, mainly on films deposited on Si in the same run to help in the characterisation of the films. All signals are specific of AlN polycrystalline films, which are of better quality when deposited with 72% N₂. The lowest sub-band gap optical absorption around 5×10² cm⁻¹ is obtained for deposition on silica at T_s=300°C with 72% N₂ and is close to that of heteroepitaxial films deposited on sapphire.     

Microstructure modification of amorphous titanium oxide thin films during annealing treatment

Thin films of titanium oxide have been deposited on (100) silicon wafers and on quartz substrates by reactive r.f. magnetron sputtering from a 99.6% pure Titanium target. Amorphous and overoxidised coatings (TiO_2.2) have been obtained from this technique. The influence of the post-deposition annealing between 300 °C and 1100 °C on the structural and optical properties and on the surface morphology has been investigated. The results of X-ray diffraction showed that films annealed from 300 to 500 °C have an anatase crystalline structure whereas those annealed at 1100 °C have a rutile crystalline structure. Optical analyses showed that UV-Vis transmission spectra are strongly modified by the annealing temperature and refractive index of TiO_x layers also changes. Atomic force microscopy measurements corroborate optical and structural analyses and showed that the surface of the coatings can have various appearances and morphologies for the annealing temperatures investigated.     

Low-temperature growth and orientational control in RuO2 thin films by metal-organic chemical vapor deposition

For growth temperatures in the range of 275°C to 425°C, highly conductive RuO₂ thin films with either (110)- or (101)-textured orientations have been grown by metal-organic chemical vapor deposition (MOCVD) on both SiO₂/Si(001) and Pt/Ti/SiO₂/Si(001) substrates. Both the growth temperature and growth rate were used to control the type and degree of orientational texture of the RuO₂ films. In the upper part of this growth temperature range ( 350°C) and at a low growth rate (< 3.0 nm/min.), the RuO₂ films favored a (110)-textured orientation. In contrast, at the lower part of this growth temperature range ( 300°C) and at a high growth rate (> 3.0 nm/min.), the RuO₂ films favored a (101)-textured orientation. In contrast, higher growth temperatures (> 425°C) always produced randomly-oriented polycrystalline films. For either of these low-temperature growth processes, the films produced were crack-free, well-adhered to the substrates, and had smooth, specular surfaces. Atomic force microscopy showed that the films had a dense microstructure with an average grain size of 50–80 nm and a rms. surface roughness of 3–10 nm. Four-probe electrical transport measurements showed that the films were highly conductive with resistivities of 34–40 μΩ-cm (at 25°C).     

Epitaxial growth of RuO2 thin films by metal-organic chemical vapor deposition

Conductive RuO₂ thin films were epitaxially grown on LaAlO₃(100) and MgO(100) substrates by metal-organic chemical vapor deposition (MOCVD). The deposited RuO₂ films were crack-free, and well adhered to the substrates. The RuO₂ film is (200) oriented on LaAlO₃ (100) substrates at deposition temperature of 600°C and (110) oriented on MgO(100) substrates at deposition temperature of 350°C and above. The epitaxial growth of RuO₂ on MgO and LaAlO₃ is demonstrated by strong in-plane orientation of thin films with respect to the major axes of the substrates. The RuO₂ films on MgO(100) contain two variants and form an orientation relationship with MgO given by RuO₂(110)//MgO(100) and RuO₂[001]//MgO[011]. The RuO₂ films on LaAlO₃(100), on the other hand, contain four variants and form an orientation relationship with LaAlO₃ given by RuO₂(200)//LaAlO₃(100) and RuO₂[011]//LaAlO₃[011]. Electrical measurements on the RuO₂ thin films deposited at 600°C show room-temperature resistivities of 40 and 50 μΩ cm for the films deposited on the MgO and LaAlO₃ substrates, respectively.     

Sputtered Ta2O5 antireflection coatings for silicon solar cells

Ta₂O₅ thin films were deposited onto monocrystalline silicon surfaces by magnetron reactive sputtering. When the Ta₂O₅ films are employed as antireflection coatings, the reflectance of the original silicon surface diminishes from about 30% to approximately 3%. At the same time, a very low absorption coefficient (less than 10³ cm^-1) for the Ta₂O₅ films below their fundamental absorption edge (hv < 4.2 eV) is obtained from reflectance and transmittance spectra of Ta₂O₅ deposited onto quartz substrates. Finally, the technique of reactive sputtering is considered from the point of view of preparing antireflection coatings for solar cells.     

Preparation and characteristics of Y2O3-doped CeO2 film by r.f. magnetron sputtering

Properties and applications as a pH sensor of Y₂O₃-doped CeO₂ films prepared by r.f. magnetron sputtering were studied. The CeO₂-Y₂O₃ films exhibited higher electric conductivity than yttria-stabilized zirconia. Films deposited on an MgO single-crystal (100) substrate without substrate heating had a more dense structure. The microstructure of the samples deposited at a substrate temperature of 873 K was shown to be columnar by scanning electron microscope. X-ray diffraction studies showed that a (111) diffraction peak assigned to CeO₂ was much greater and the films exhibited preferential orientation to the (111) plane with increasing r.f. power or substrate temperature. The pH electrode was made by a double layer of Y₂O₃-doped CeO₂ and Cu/Cu₂O redox films deposited onto the MgO substrate. pH response was measured in various pH buffer solutions at room temperature. It showed good agreement with a nernstian response in the pH range 9–13.     

Preparation of (001)-oriented Pb(Zr,Ti)O/sub 3/ thin films and their piezoelectric applications

Preparation of (001)-oriented Pb(Zr,Ti)O₃ (PZT) thin films and their applications to a sensor and actuators were investigated. These thin films, which have a composition close to the morphotropic phase boundary, were epitaxially grown on (100)MgO single-crystal substrates by RF magnetron sputtering. These (001)-oriented PZT thin films could be obtained on various kinds of substrates, such as glass and Si, by introducing (100)-oriented MgO buffer layers. In addition, the (001)-oriented PZT thin films could be obtained on Si substrates without buffer layers by optimizing the sputtering conditions. All of these thin films showed excellent piezoelectric properties without the need for poling treatment. The PZT thin films on the MgO substrates had a high piezoelectric coefficient, d₃₁, of -100 pm/V, and an extremely low relative dielectric constant, epsiv_r, of 240. The PZT thin films on Si substrate had a very high d₃₁ of -150 pm/V and an epsiv_r = 700. These PZT thin films were applied to an angular rate sensor with a tuning fork in a car navigation system, to a dual-stage actuator for positioning the magnetic head of a high-density hard disk drive, and to an actuator for an inkjet printer head for industrial on-demand printers.     

Tungsten–carbon films prepared by reactive sputtering from argon–benzene discharges

Tungsten–carbon thin films have been deposited by reactive (Ar+C₆H₆) DC magnetron sputtering onto various substrates. Deposition onto glass, monocrystalline silicon, tantalum and stainless steel at room temperature yielded W–C films, having XRD patterns corresponding to the structure of heavily disordered W₂C or WC_1−x carbides. The samples deposited upon the Au or Cu foils were nanocrystalline cubic WC_1−x with the grain size of 2.9 nm. Disordered tungsten–carbon films were stable up to 1200°C. Microhardness of the films with disordered W₂C phase was about 5–6 GPa while that of the films with disordered WC_1−x phase was about 17 GPa. The characteristics of films can be understood considering the effects of the incorporation of free carbon and/or carbon–hydrogen fragments into the tungsten carbide layer.     

Investigation of thermal stability, phase formation, electrical, and microstructural properties of sputter-deposited titanium aluminide thin films

Titanium aluminide thin films are being considered as coating materials for high temperature applications due to their high melting points and high oxidation resistance. In this study, Ti₃₇Al₆₃ and Ti₅₃Al₄₇ thin films are deposited onto SiO₂ substrates by RF magnetron sputtering using compound targets and then annealed in vacuum to investigate the properties of the films. Rutherford backscattering spectrometry, X-ray diffractometry, transmission electron microscopy, and four-point probe measurements are used to analyze the characteristics of Ti₃₇Al₆₃ and Ti₅₃Al₄₇ thin films for high temperature electronics applications. The films show good thermal stability up to 700 °C for 1 h in vacuum. Reasonable resistivity is obtained when appropriate compositions and anneal conditions are used.     

Preparation of Pt-PtOx thin films as electrode for memory capacitors

Pt-PtO_x thin films were prepared on Si(100) substrates at temperatures from 30 to 700°C by reactive r.f. magnetron sputtering with platinum target. Deposition atmosphere was varied with O₂/Ar flow ratio. The deposited films were characterized by X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy. Resistively of the deposited films was measured by d.c. four probe method. The films mainly consisted of amorphous PtO and Pt₃O₄ (or Pt₂O₃) below 400°C, and amorphous Pt was increased in the film as a deposition temperature increased to 600°C. When deposition temperature was thoroughly increased, (111) oriented pure Pt films were formed at 700°C. Compounds included in the films strongly depended on substrate temperature rather than O₂/Ar flow ratio. Electrical resistivity of Pt-PtO_x films was measured to be from the order of 10⁻¹ Ω cm to 10⁻⁵ Ω cm, which was related to the amount of Pt phase included in the deposited films.     

Study of HfO2 films prepared by ion-assisted deposition using a gridless end-hall ion source

HfO₂ thin films were deposited using e-beam gun evaporation with ion assisted deposition (IAD) of low energy oxygen ions (40–100 eV) from an end-Hall ion source. A comparison was made using Hf and HfO₂ starting materials. The index of refraction was measured as a function of the ion source voltage and compared to results without IAD. Application to high power laser mirrors was verified by measurements of laser damage thresholds at 1.06 μm.     

DC magnetron reactive sputtered InN thin film electrodes as photoanodes in aqueous solution. A study of as prepared and nitrogen annealed electrodes

Thin films of indium nitride, InN, were produced by reactive magnetron DC sputtering. By post treatment in dinitrogen, N₂, in the temperature range 350–500 °C a set of films gradually going from InN to indium oxide, In₂O₃ was obtained (due to dioxygen impurities in the annealing gas). Those films were characterized by X-ray diffraction, optical-, resistivity- and photoelectrochemical measurements for the aim of direct watersplitting in a photoelectrochemical cell.

Surprisingly, the caused change in the film composition by annealing gave no significant change in the room temperature resistivity, but the free electron density and the optical properties were affected. In 0.1 M NaOH annealing improved the photoresponse of the thin films. A pronounced optimum was observed for films annealed at 425 °C. Even for those films the quantum efficiency was low; at most 2% of the photons at 350 nm were transformed into readable photoelectrons. The onset wavelength for photocurrent was located around 600 nm (2.1 eV), which is far off from the onset of absorption 900 nm (1.4 eV).     

Ni-Al2O3 selective cermet coatings for photothermal conversion up to 500°C

Spectrally selective Ni-Al₂O₃ composite films were prepared by r.f. planar magnetron sputtering using hot-pressed targets of two different compositions. The composition of the films were varied by co-sputtering the target with additional nickel pellets distributed uniformly on the target. The composition of the films were analysed by energy-dispersive X-ray analysis. Optical simulations were carried out with the experimentally measured n and k and the published n and k of the metallic substrate. R.f.-sputtered SiO₂ and Al₂O₃ were used as antireflection coatings. From the computer optimization studies we found that = 0.94 and (100°C) = 0.07 could be obtained with 650 Å of Ni-Al₂O₃ (f = 0.61) antireflected with 780 Å SiO₂ on a nickel-coated glass substrate. When molybdenum-coated nickel-plated stainless steel substrates were used, the films were found to be stable up to 500°C in air.