Effect of annealing on the composition, structure and mechanical properties of carbon nitride films deposited by middle-frequency magnetron sputtering

Carbon nitride films were deposited by middle-frequency reactive magnetron sputtering and annealed at different temperatures in nitrogen ambient. X-ray photoelectron spectroscopy, Raman scattering, transmission electron microscopy, and nano-indenter were used to characterize the as-deposited and annealed films. The analysis showed that annealing resulted in the dissociation of N and C in the films. The dissociation of C happened after 500 °C and lagged behind that of N. With the increase of annealing temperature, the disorder of sp² C decreased and the films were gradually graphitized. The microstructure changed from amorphous to fullerene-like CN_x with the annealing temperature increasing to 500 °C, and then to nitridized graphite nanocrystals at 600 °C. The graphitization resulted in a drastic decreasing of hardness and modulus of the films.     

Mechanical characterization of LiPON films using nanoindentation

Nanoindentation has been used to characterize the elastic modulus and hardness of LiPON films ranging in thickness from 1 to 10 μm. Four fully dense, amorphous films were deposited on glass and sapphire substrates with one film annealed at 200 °C for 20 min. The modulus of LiPON is found to be approximately 77 GPa, and argued to be independent of the substrate type, film thickness, and annealing. Based on the numerical analysis of Monroe and Newman, this value may be sufficiently high to mechanically suppress dendrite formation at the lithium/LiPON interface in thin film batteries [1]. Using Sneddon's stiffness equation and assuming the modulus is 77 GPa, the hardness is found to be approximately 3.9 GPa for all but the annealed film. The hardness of the annealed film is approximately 5% higher, at 4.1 GPa. Atomic force microscopy images of the residual hardness impressions confirm the unexpected increase in hardness of the annealed film. Surprisingly, the indentation data also reveal time-dependent behavior in all four films. This indicates that creep may also play a significant role in determining how LiPON responds to complex loading conditions and could be important in relieving stresses as they develop during service.     

X-ray absorption spectroscopy study of thermally annealed Cu–Al–O thin films

Cu–Al–O thin films are deposited on (0001) sapphire substrates by radio-frequency sputtering using an Al–Cu mosaic target. The Cu/Al atomic ratio of as-deposited Cu–Al–O films is measured to be 1.1. After deposition, the Cu–Al–O films are annealed at 600, 800, and 1000 °C, respectively, for 1 h in a N₂ atmosphere. The film crystal structure, electronic structure, valence band, and electrical properties are studied. The as-deposited films are amorphous and films annealed at 600 °C contain the crystallized CuO phase; the structure becomes crystallized CuAlO₂ after annealing at 800 °C and 1000 °C. The 800 °C annealed film grows along the (00l) plane. The crystallization decreases with the growth of the (012) and (018) planes for films annealed at 1000 °C. The resistivity values of the 800 °C and 1000 °C annealed films were measured as 1.07 Ω-cm and 864.01 Ω-cm, respectively. The lower resistivity of the 800 °C annealed film is attributed to preferred (00l) growth orientation and a reduction of the energy band gap.     

Annealing effects on microstructure and mechanical properties of sputtered multilayer Cr(1 − x)AlxN films

Multilayer Cr_(1 − x)Al_xN films with a total thickness of 2 μm were deposited on high-speed steel by medium frequency magnetron sputtering from Cr and Al-Cr (70 at.% Al) targets. The samples were annealed in air at 400 °C, 600 °C, 800 °C and 1000 °C for 1 hour. Films were characterized by cross-sectional scanning electron microscopy and X-ray diffraction analysis. The grain size of the as-deposited multilayer films is about 10 nm, increasing with the annealing temperature up to 100 nm. Interfacial reactions have clearly changed at elevated annealing temperatures. As-deposited films' hardness measured by nanoindentation is 22.6 GPa, which increases to 26.7 GPa when the annealing temperature goes up to 400 and 600 °C, but hardness decreases to 21.2 GPa with further annealing temperature increase from 600 to 1000 °C. The multilayer film adhesion was measured by means of the scratch test combined with acoustic emission for detecting the fracture load. The critical normal load decreased from 49.7 N for the as-deposited films to 21.2 N for the films annealed at 1000 °C.     

Influence of annealing temperature on the structural, mechanical and wetting property of TiO2 films deposited by RF magnetron sputtering

TiO₂ films have been deposited on silicon substrates by radio frequency magnetron sputtering of a pure Ti target in Ar/O₂ plasma. The TiO₂ films deposited at room temperature were annealed for 1 h at different temperatures ranging from 400 °C to 800 °C. The structural, morphological, mechanical properties and the wetting behavior of the as deposited and annealed films were obtained using Raman spectroscopy, atomic force microscopy, transmission electron microscopy, nanoindentation and water contact angle (CA) measurements. The as deposited films were amorphous, and the Raman results showed that anatase phase crystallization was initiated at annealing temperature close to 400 °C. The film annealed at 400 °C showed higher hardness than the film annealed at 600 °C. In addition, the wettability of film surface was enhanced with an increase in annealing temperature from 400 °C to 800 °C, as revealed by a decrease in water CA from 87° to 50°. Moreover, the water CA of the films obtained before and after UV light irradiation revealed that the annealed films remained more hydrophilic than the as deposited film after irradiation.     

Structural characteristics and mechanical properties of Ti(Cr) films produced on Si substrate

A series of nanogranular Ti₉₀Cr₁₀ thin films have been fabricated by pulsed-laser deposition on Si substrates at different temperatures. The crystal structure and mechanical properties of these films were investigated. The X-ray diffraction and transmission electron microscope images with selected area diffraction showed that the structure of as-prepared films is dependent on film thickness and deposition temperature. It was found that the Ti₉₀Cr₁₀ films consisted of fine hexagonal close packed microstructure with columnar grains, while body close-packed cubic structure of Cr films are composed of irregular grains, meanwhile, a chromium disilicide (CrSi₂) layer formed in the interface between the substrate and Cr films which deposited at temperature of greater than 600 °C. The crystalline and columnar grains improved with an increase of the thickness of the films and an optimum microstructure is obtained under the present experimental condition of about 50 nm thickness and deposited temperature of 500 °C for Ti₉₀Cr₁₀ films. Deposited at 300 °C, the Ti₉₀Cr₁₀ films have hardness of 12.7 GPa and elastic modulus of 174.6 GPa. Improved to 600 °C the sample shows higher hardness of 13.1 GPa and higher elastic modulus of 183.2 GPa. Using Benjamin-Weaver model, adhesion shearing force can be calculated as 34.9 MPa for 300 °C Ti₉₀Cr₁₀ film while higher value of 44.4 MPa for higher temperature of 600 °C.     

Properties of aluminum oxide thin films deposited by pulsed laser deposition and plasma enhanced chemical vapor deposition

The chemical, structural, mechanical and optical properties of thin aluminum oxide films deposited at room temperature (RT) and 800 °C on (100) Si and Si-SiO₂ substrates by pulsed laser deposition and plasma enhanced chemical vapor deposition are investigated and compared. All films are smooth and near stoichiometric aluminum oxide. RT films are amorphous, whereas γ type nano-crystallized structures are pointed out for films deposited at 800 °C. A dielectric constant of ∼ 9 is obtained for films deposited at room temperature and 11-13 for films deposited at 800 °C. Young modulus and hardness are in the range 116-254 GPa and 6.4-28.8 GPa respectively. In both cases, the results show that the deposited films have very interesting properties opening applications in mechanical, dielectric and optical fields.     

Mechanical properties of amorphous and microcrystalline silicon films

Hydrogen-free amorphous silicon (a-Si) films with thickness of 4.5-6.5 μm were prepared by magnetron sputtering of pure silicon. Mechanical properties (hardness, intrinsic stress, elastic modulus), and film structure (Raman spectra, electron diffraction) were investigated in dependence on the substrate bias and temperature. The increasing negative substrate bias or Ar pressure results in simultaneous reducing compressive stress, the film hardness and elastic modulus. Vacuum annealing or deposition of a-Si films at temperatures up to 600 °C saving amorphous character of the films, results in reducing compressive stress and increasing the hardness and elastic modulus. The latter value was always lower than that for monocrystalline Si(111). The crystalline structure (c-Si) starts to be formed at deposition temperature of ∼ 700 °C. The hardness and elastic modulus of c-Si films were very close to monocrystalline Si(111). Phase transformations observed in the samples at indentation depend not only on the load and loading rate but also on the initial phase of silicon. However, the film hardness is not too sensitive to the presence of phase transformations.     

Nanomechanical properties of FePtPd ternary alloy thin films

Presented in this study are crystalline structure and mechanical properties of FePt_0.75Pd_0.25 ternary alloy thin films deposited under the various annealing temperatures, obtained by means of transmission electron microscopy (TEM) and nanoindentation techniques. FePtPd ternary alloy thin films are deposited on Si substrates using a multi-target DC magnetron sputtering system. Results indicate that the grain size increase from 40 to 135 nm as the annealing temperature increases from 400 to 600 °C. From nanoindentation measurements, the hardness of FePtPd ternary alloy thin films are 11.6 ± 0.4, 10.4 ± 0.1 and 8.8 ± 0.3 GPa for the annealed temperatures of 400, 500 and 600 °C, respectively. And, the corresponding Young's moduli are 175.4, 152.2 and 142.6 GPa, respectively. Hardness for FePtPd ternary alloy thin films decreased slightly in accordance with the increase of the grain size. By fitting experimental results with the Hall-Petch equation, a probable lattice friction stress of 5.15 ± 0.05 GPa and Hall-Petch constant of 44.25 ± 2.55 GPa nm^1/2 are obtained.     

Tungsten-oxide thin films as novel materials with high sensitivity and selectivity to NO2, O3 and H2S. Part I: Preparation and microstructural characterization of the tungsten-oxide thin films

Tungsten-oxide thin films are promising materials for use in highly effective gas-sensing devices for NO₂, ozone and H₂S detection in ambient air. In this work tungsten-oxide thin films were obtained by electron-beam deposition and annealed in the temperature range 350–800 °C for 1–3 h. The structure, morphology and phase composition of the as-deposited and annealed films were characterized by X-ray diffraction, SEM and AFM. The changes of phase composition and the microstructure in dependence of the annealing conditions are described in detail. The direction of the phase transformations for different annealing conditions is influenced by the very high macrostresses that appear as an additional, independent thermodynamic factor. During annealing at 350–400 °C for 1–3 h and at 800 °C for 1 h predominantly semiconductor phases are formed, whereas the thin films annealed at 500–600 °C for 1–3 h and 800 °C for 2 h consist mainly of phases with more pronounced metallic properties. The processes of realignment of crystal structures during solid-phase transformation lead not only to the growth of new crystallites with a preferential orientation but also to a change in the direction of preferred growth with increasing annealing temperature and time. The films can be divided into two main groups: compact (as-deposited and annealed at 350–500 °C for 1–3 h) and porous (annealed at 600–800 °C for 1–3 h) layers. The gas-sensing properties of these films and the correlation between microstructure and sensing properties will be described in the second part of this paper.     

Effect of underlying silicon film on the evolution of microstructure and hardness of the high-temperature annealed carbon film on Si substrate

Effects of an amorphous silicon underlayer on the evolution of microstructure and hardness of an amorphous carbon film annealed at 900 °C for 0.5-1.5 h were investigated. The two-layer carbon/silicon film after annealing resulted in higher sp²/sp³ bonding ratio but lower hardness reduction compared to the single carbon film at the same total film thickness. The improved hardness reduction of the high-temperature annealed carbon film is attributed to the formation of polycrystals of the amorphous silicon together with the residual compressive stress of the two-layer C/Si films.     

Structural and electrical characteristics of chemical solution derived (Bi3.2La0.4Nd0.4)Ti3O12 thin films

(Bi_3.2La_0.4Nd_0.4)Ti₃O₁₂ (BLNT) thin films were prepared on Pt/Ti/SiO₂/Si substrates by using chemical solution deposition technique, and the effects of annealing temperatures in the range of 550-750 °C on structure and electrical properties of the thin films were investigated. X-ray diffraction analysis shows that the thin films have a bismuth-layered perovskite structure with preferred (117) orientation. The surface morphology observation by field-emission scanning electron microscopy confirms that films are dense and smooth with uniformly distributed grains. The grain size of the thin films increases with increasing annealing temperature; meanwhile, the structural distortion of the thin films also increases. It was demonstrated that the thin films show good electrical properties. The dielectric constant and dielectric loss are 191 and 0.028, respectively, at 10 kHz for the thin film annealed at 600 °C, and the 2Pr value of the thin film annealed at 700 °C is 20.5 μC/cm² at an electric field of 500 kV/cm.     

Influence of magnetic annealing on high-frequency magnetic properties of FeCoNd films

FeCoNd thin film with thickness of 166 nm has been fabricated on silicon (1 1 1) substrates by magnetron co-sputtering and annealed for one hour under magnetic field at different temperatures (T_a) from 200 °C to 700 °C. The As-deposited and annealed FeCoNd film samples at T_a ≤ 500 °C were amorphous while the ones obtained at T_a ≥ 600 °C were crystallized. We found that the perpendicular anisotropy field gradually decreases as the annealing temperature increases from room temperature to 300 °C. A well induced in-plane uniaxial anisotropy is achieved at the annealing temperature between 400 and 600 °C. The variation of the dynamic magnetic properties of annealed FeCoNd films can be well explained by the Landau-Lifshitz equation with the variation of the anisotropy field re-distribution and the damping constant upon magnetic annealing. The magnetic annealing might be a powerful post treatment method for high frequency application of magnetic thin films.     

High-temperature growth and in-situ annealing of MgZnO thin films by RF sputtering

We report the effect of growth temperature and annealing on microstructural, elemental and emission properties of as-grown and in-situ annealed MgZnO thin films, containing ∼ 10 at. % Mg, grown at high temperature by RF sputtering. Microstructural analysis carried out by TEM reveals formation of thin oxide layer with increased layer thickness on growth temperature, in the interface between Si substrate and MgZnO thin film. Irrespective of growth temperature, increase in Mg mole fraction with increase in thickness of MgZnO thin film is observed from EDX and AES spectroscopy, and a maximum of 14 at. % Mg is observed at 800 °C. The photoluminescence investigation shows blue shift of 104 meV in MgZnO film grown at 800 °C, compared to the film grown at 600 °C, which is due to the enhancement of the Mg incorporation at higher temperature. In addition, annealing at the growth temperature enhanced the intensity ratio of the UV/deep level emission and increased the grain size. Thermal treatment in a vacuum improved the emission efficiency and changed the origin of the point defects.     

Post deposition annealing of aluminum oxide deposited by atomic layer deposition using tris(diethylamino)aluminum and water vapor on Si(100)

Thin stoichiometric aluminum oxide films were deposited using tris(diethylamino)aluminum precursor and water. Changes in aluminum oxide film and interfacial regions were studied after post deposition annealing under inert ambience at 600, 800 and 1000 °C using Fourier Transform InfraRed (FTIR) spectroscopy, X-ray Photoelectron Spectroscopy, and Scanning Transmission Electron Microscopy (STEM)/Electron Energy Loss spectroscopy (EELS) techniques. STEM/EELS analyses were also done on samples annealed in situ, i.e., inside the electron microscope at temperatures as high as 800 °C. Up to an annealing temperature of 600 °C, the atomic layer deposited alumina film was thermally stable and remained amorphous with no interfacial silica growth observed. After annealing at 800 °C for 5 min, the only change observed was a small increase in the interfacial layer thickness which was found to be mainly silicon oxide without any significant silicate content. Annealing at 1000 °C induced a significant increase in the interfacial layer thickness which consisted of a mixture of silicon oxide and aluminum silicate. The composition of the interfacial layer was found to change with depth, with silicate concentration decreasing with distance from the Si substrate. Also, the FTIR spectra exhibited strong absorption features due to Al-O stretching in condensed AlO₆ octahedra which indicate crystallization of the alumina film after annealing at 1000 °C for 5 min.     

Combinatorial investigation of Fe–B thin-film nanocomposites

Combinatorial magnetron sputter deposition from elemental targets was used to create Fe–B composition spread type thin film materials libraries on thermally oxidized 4-in. Si wafers. The materials libraries consisting of wedge-type multilayer thin films were annealed at 500 or 700 °C to transform the multilayers into multiphase alloys. The libraries were characterized by nuclear reaction analysis, Rutherford backscattering, nanoindentation, vibrating sample magnetometry, x-ray diffraction (XRD) and transmission electron microscopy (TEM). Young''s modulus and hardness values were related to the annealing parameters, structure and composition of the films. The magnetic properties of the films were improved by annealing in a H₂ atmosphere, showing a more than tenfold decrease in the coercive field values in comparison to those of the vacuum-annealed films. The hardness values increased from 8 to 18 GPa when the annealing temperature was increased from 500 to 700 °C. The appearance of Fe₂B phases, as revealed by XRD and TEM, had a significant effect on the mechanical properties of the films.     

Preparation of aluminum doped zinc oxide films and the study of their microstructure, electrical and optical properties

Aluminum doped zinc oxide (AZO) polycrystalline thin films were prepared by sol-gel dip-coating process on optical glass substrates. Zinc acetate solutions of 0.5 M in isopropanol stabilized by diethanolamine and doped with a concentrated solution of aluminum nitrate in ethanol were used. The content of aluminum in the sol was varied from 1 to 3 at.%. Crystalline ZnO thin films were obtained following an annealing process at temperatures between 300 °C and 500 °C for 1 h. The coatings have been characterized by X-ray diffraction, UV-Visible spectrophotometry, scanning electron microscopy, and electrical resistance measurement. The ZnO:Al thin films are transparent (∼ 90%) in near ultraviolet and visible regions. With the annealing temperature increasing from 300 °C to 500 °C, the film was oriented more preferentially along the (0 0 2) direction, the grain size of the film increased, the transmittance also became higher and the electrical resistivity decreased. The X-ray diffraction analysis revealed single-phase ZnO hexagonal wurtzite structure. The best conductors were obtained for the AZO films containing 1 at.% of Al, annealed at 500 °C, 780 nm film thickness.     

C-Ti nanocomposite thin films: Structure, mechanical and electrical properties

Carbon-titanium nanocomposite thin films were deposited by DC magnetron sputtering on oxidized silicon substrates in argon. The films were prepared at different deposition temperatures between 25 and 800 °C. Transmission electron microscopy was used to determine the structure of the films. All the C-Ti nanocomposites consisted of columnar TiC structure with average column width ∼10 and 20 nm and a thin carbon matrix. The thickness of the carbon matrix between adjacent TiC columns was ∼2-5 nm.Mechanical properties (hardness, reduced modulus) of C-Ti films showed a distinct variation depending on the deposition temperature. Films deposited at 200 °C had the highest hardness ∼18 GPa and the highest reduced modulus ∼205 GPa.Temperature dependence of the film resistance was measured between 80 and 330 K. C-Ti nanocomposites have a non-metallic conduction mechanism characterized by a negative temperature coefficient of resistivity (TCR). The most negative TCR was observed for films showing high hardness and reduced modulus of elasticity.     

Hydrophilic properties of nano-TiO2 thin films deposited by RF magnetron sputtering

Microstructure and hydrophilicity of nano-titanium dioxide (TiO₂) thin films, deposited by radio frequency magnetron sputtering, annealed at different temperatures, were studied by field emission scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and water contact angle methods. It is found that the crystal phase transforms from amorphous to rutile structure with increase of annealing temperature from room temperature to 800 °C. It is also indicated that the organic contaminants on the surface of the films can be removed and the oxygen vacancies can be reduced by the annealing treatment. Annealed at the temperature below 300 °C, amorphous TiO₂ thin films show rather poor hydrophilicity, and annealed at the temperature range from 400 to 650 °C, the super hydrophilicity anatase of TiO₂ thin films can be observed. However, when the annealing temperature reaches 800 °C, the hydrophilicity of the films declines mainly derived from the appearance of rutile.     

Structures and properties of titania thin films annealed under different atmosphere

The effects of crystallinity, phase and oxygen vacancies on optical and photocatalytic properties of titania (TiO₂) thin films were systematically studied. The as-deposited amorphous titania films were prepared by reactive sputtering titanium metal targets in argon–oxygen plasma at 100 °C and subsequently annealed at various temperatures of 400–800 °C in air, vacuum and H₂ atmosphere. The results indicate that in general the crystallinity of the annealed films is enhanced with the increasing annealing temperature. At the same temperature, the H₂ annealed films achieve better crystallinity but containing more oxygen vacancies than the films annealed in air and in vacuum. In H₂ or in vacuum, the concentration of oxygen vacancies in the annealed films increases with increasing temperature, while in air it remains constant. Oxygen vacancies in titania film not only facilitate phase transformation but also lower the band gap of titania, and make the film visible-light responsive. Photocatalytic properties of the TiO₂ films were characterized in UV and visible light irradiation by following the Ag reduction and degradation of methylene blue. The films annealed at 600–700 °C in H₂ possess the best film crystallinity and the proper concentration of oxygen vacancies and exhibit the best photocatalytic performance under both UV and visible light.