AlNxOy thin films deposited by DC reactive magnetron sputtering

AlN_xO_y thin films were produced by DC reactive magnetron sputtering, using an atmosphere of argon and a reactive gas mixture of nitrogen and oxygen, for a wide range of partial pressures of reactive gas. During the deposition, the discharge current was kept constant and the discharge parameters were monitored. The deposition rate, chemical composition, morphology, structure and electrical resistivity of the coatings are strongly correlated with discharge parameters. Varying the reactive gas mixture partial pressure, the film properties change gradually from metallic-like films, for low reactive gas partial pressures, to stoichiometric amorphous Al₂O₃ insulator films, at high pressures. For intermediate reactive gas pressures, sub-stoichiometric AlN_xO_y films were obtained, with the electrical resistivity of the films increasing with the non-metallic/metallic ratio.     

Effect of nitrogen content on the properties of CrNxOyCz coating prepared by DC reactive magnetron sputtering

The CrN_xO_yC_z coatings were deposited by planar DC reactive magnetron sputtering onto AZ31 Mg alloy and high speed tool steel (HSTS) substrates at a substrate temperature of 200 °C. The effect of N₂ content on composition and structure of the CrN_xO_yC_z coatings was investigated. The structure of the CrN_xO_yC_z coatings was analyzed by a glancing angle X-ray diffraction (GXRD). The cross-section morphology and thickness of the CrN_xO_yC_z coatings were checked by a field emission scanning electron microscope (FESEM), and the composition profile and chemical state were carried out by an X-ray photoelectron spectroscopy (XPS). The experimental results showed that the structure and phase composition of the CrN_xO_yC_z coatings depended on N₂ content. The evolution of the structure of CrN_xO_yC_z coatings was consistent with CrN_x-based coatings, and the CrN_xO_yC_z coatings contained Cr₂O₃, CrO₂, CrO, Cr₃C₂, CrN_x (Cr, CrN, Cr₂N), as well as different chromium oxynitride. However, the carbide and oxynitride were oxidized after annealing.     

Electrical behaviour of SiOxNy thin films and correlation with structural defects

Silicon oxynitride thin films were deposited by reactive r.f. sputtering from a silicon target. Different Ar:O₂:N₂ gas atmospheres were used at fixed power density (3.18 W cm⁻²) and pressure (0.4 Pa) to obtain various film composition. Pt-SiO_xN_y-Pt sandwich type structure was realised for electrical property investigations. The C-V measurements showed the absence of a Schottky barrier and thus confirmed that Pt electrode provides an ohmic contact. The evolution of the current density showed a decrease of the film conductivity when the oxygen concentration in the films increases. The various layer composition leads to two different conduction mechanisms which were identified as space charge limited current (SCLC) and Poole-Frenkel effect. Finally, the structural defects of the films were studied by EPR analysis and the spin densities were correlated to both the composition and the electrical behaviour of the films.     

Activation energy of water vapor and oxygen transmission through TiNxOy/PET gas barrier films

Titanium oxynitride (TiN_xO_y) films were deposited on polyethylene terephthalate (PET) substrates by means of a reactive radio frequency (RF) magnetron sputtering system in which the power density was the varied parameter. Experimental results show that the deposited TiN_xO_y films with a thickness of about 55 nm have similar contents of TiN, TiN_xO_y and TiO₂ bonds, although they are deposited at different power densities. The TiN_xO_y films deposited at a lower power density have fewer internal defects and grain boundaries and possess higher activation energy and a lower rate of water vapor and oxygen transmission through TiN_xO_y/PET films.     

Surface morphology of DyxOy films grown on Si

The crystalline structure and surface morphology of Dy_xO_y dielectric films grown on Si substrates were studied by grazing incidence diffraction and absorption with use of synchrotron radiation and by atomic force microscopy. The crystalline structure and the roughness of Dy_xO_y films were found to be strongly dependent on the deposition rate. The dielectric-silicon interface depends on the type of gas used in the annealing process. Moreover, results from the near edge X-ray absorption studies, have revealed that none of the examined films has a stoichiometry close to the Dy₂O₃. The level of stoichiometry is determined by the technological conditions. Nevertheless, MOS structures with Dy_xO_y films (EOT ∼ 23 Å) have shown a rather good Dy_xO_y-Si interface properties, which can be further improve by thermal annealing, and introducing of several additives, therefore Dy_xO_y films can be considered as suitable candidates for gate dielectric in MOS devices.     

Hf1−xSixOy dielectric films deposited by UV-photo-induced chemical vapour deposition (UV-CVD)

Hf_1−xSi_xO_y is an attractive candidate material for high-k dielectrics. We report in this work the deposition of ultra-thin Hf_1−xSi_xO_y films (0.1 ≤ x ≥ 0.6) on silicon substrate at 450 °C by UV-photo-induced chemical vapour deposition (UV-CVD) using 222 nm excimer lamps. Silicon(IV) and hafnium(IV) organic compounds were used as the precursors. Films from around 5 to 40 nm in thickness with refractive indices from 1.782 to 1.870 were grown. The deposition rate was found to be of 6 nm/min at a temperature of 450 °C. The physical, interfacial and electrical properties of hafnium silicate (Hf_1−xSi_xO_y) thin films were investigated by using X-ray photoelectron spectroscopy, ellipsometry, FT-IR, C-V and I-V measurements. XRD showed that they were basically amorphous, while Fourier transform infrared spectroscopy (FT-IR), clearly revealed Hf-O-Si absorption in the photo-CVD deposited Hf_1−xSi_xO_y films. Surface and interfacial properties were analysed by TEM and XPS. It is found that carbon content in the films deposited by UV-CVD is very low and it also decreases with increasing Si/(Si + Hf) ratio, as low as about 1 at.% at the Si/(Si + Hf) ratio of 60 at.%.     

Characterization of HfOxNy gate dielectrics using a hafnium oxide as target

Hafnium oxynitride (HfO_xN_y) gate dielectric has been deposited on Si (1 0 0) by means of radio frequency (rf) reactive sputtering using directly a HfO₂ target in N₂/Ar ambient. The thermal stability and microstructural characteristics for the HfO_xN_y films have been investigated. XPS results confirmed that nitrogen was successfully incorporated into the HfO₂ films. XRD analyses showed that the HfO_xN_y films remain amorphous after 800 °C annealing in N₂ ambient. Meanwhile the HfO_xN_y films can also effectively suppress oxygen diffusion during high temperature annealing and prevent interface layer from forming between HfO_xN_y films and Si substrates. AFM measurements demonstrated that surface roughness of the HfO_xN_y films increase slightly as compared to those pure HfO₂ films after post deposition annealing. By virtue of building reasonable model structure, the optical properties of the HfO_xN_y films have been discussed in detail.     

Influence of growth and anneal conditions on the surface roughness of L10 Fe50PdxPt50−x thin films

We deposit Fe₅₀Pd_xPt_50−x alloy thin films by magnetron sputtering onto a TiN seed layer. Chemically ordered L1₀ films are obtained which display large perpendicular magnetic anisotropy. We find that the surface roughness of the film depends strongly on the growth and anneal conditions as well as the Pd composition of the film. Smooth films are obtained by deposition above the chemical ordering temperature and by removing Pd from the alloy.     

Electrical properties of pulsed laser-deposited SrxBiyTa2O9 thin films on Bi/Sr ratios

The dependence of the electrical properties of Sr_xBi_yTa₂O₉ thin films on the (Bi/Sr ratio 1.6, 2.3, 2.8, 3.4) has been investigated. The Sr_xBi_yTa₂O₉ ferroelectric thin films were synthesized on Pt/Ti/SiO₂/Si substrates using the pulsed laser deposition method. Saturation polarization (P_st) and coercive field (2E_c) depend on the Bi/Sr ratio. P_st increases while E_c decreases with an increase in Bi/Sr ratio. Atomic Force Microscopy images show that the grain size grows with increasing Bi/Sr ratio. It is observed that the impedance behavior in Sr_xBi_yTa₂O₉ thin film, conforms to the Constant Phase Element (CPE) model. It is believed that the diffuse charges at the grain boundary build up a surface polarization because the impedance behavior close to pure capacitor with grain size increased.     

Properties of MgxZn1−xO thin films sputtered in different gases

Mg_xZn_1−xO alloy films were prepared on sapphire substrates using Ar and N₂ as the sputtering gases. The effect of the sputtering gas on the structural, optical and electrical properties of the Mg_xZn_1−xO films was studied. By using N₂ as the sputtering gas, the Mg_xZn_1−xO film shows p-type conductivity and the band gap is larger than that employing Ar as the sputtering gas. The reason for this phenomenon is thought to be related to the reaction between N-O or N-Zn, and the N-doping.     

Surface free energy of CrNx films deposited using closed field unbalanced magnetron sputtering

CrN_x thin films have attracted much attention for semiconductor IC packaging molding dies and forming tools due to their excellent hardness, thermal stability and non-sticking properties (low surface free energy). However, few data has been published on the surface free energy (SFE) of CrN_x films at temperatures in the range 20-170 °C. In this study CrN_x thin films with CrN, Cr(N), Cr₂N (and mixture of these phases) were prepared using closed field unbalanced magnetron sputtering at a wide range of Cr⁺² emission intensity. The contact angles of water, di-iodomethane and ethylene glycol on the coated surfaces were measured at temperatures in the range 20-170 °C using a Dataphysics OCA-20 contact angle analyzer. The surface free energy of the CrN_x films and their components (e.g., dispersion, polar) were calculated using the Owens-Wendt geometric mean approach. The influences of CrN_x film surface roughness and microstructure on the surface free energy were investigated by atomic force microscopy (AFM) and X-ray diffraction (XRD), respectively. The experimental results showed that the lowest total SFE was obtained corresponding to CrN at temperature in 20 °C. This is lower than that of Cr(N), Cr₂N (and mixture of these phases). The total SFE, dispersive SFE and polar SFE of CrN_x films decreased with increasing surface temperature. The film roughness has an obvious effect on the SFE and there is tendency for the SFE to increase with increasing film surface roughness.     

Modelling and Optimization for Deposition of SiOxNy Films by Radio-Frequency Reactive Sputtering

SiOxNy films are deposited by reactive sputtering from a Si target in Ar/O2/N2 atmospheres. In order to achieve the control of film composition and to keep a high deposition rate at the same time, a new sputtering model based on Berg＇s work is provided for the condition of double reactive gases. Analysis based on this model shows that the deposition process can easily enter the target-poisoning mode when the preset gas flow （N2 in this work） is too high, and the film composition will change from nitrogen-rich to SiO2-like with the increase of oxygen supply while keeping the N2 supply constant. The modelling results are confirmed in the deposition process of SiOxNy. Target self-bias voltages during sputtering are measured to characterize the different sputtering modes. FTIR-spectra and dielectric measurements are used to testify the model prediction of composition. Finally, an optimized sputtering condition is selected with the O2/N2 flow ratio varying from 0 to I and N2 supply fixed at I sccm. Average deposition rate of 17nm/min is obtained under this selected condition, which has suggested the model validity and potential for industry applications.     

Correlation between processing and properties of TiOxNy thin films sputter deposited by the reactive gas pulsing technique

Titanium oxynitride thin films were deposited by d.c. reactive magnetron sputtering from titanium metallic target and from oxygen and nitrogen as reactive gases. The nitrogen mass flow rate was maintained constant whereas that of the oxygen was pulsed during the deposition. A constant pulsing period was used and the introduction time of the oxygen was systematically changed from 0 to 100% of the period time. The reactive gas pulsing technique allowed to prepare TiO_xN_y films with various metalloid concentrations (0≤x≤2.0 and 0≤y≤1.0) and led to changes of the crystallographic structure from f.c.c. TiN to tetragonal TiO₂. The variations of the metalloid content in the films result in changes in the electrical and optical properties and the reverse evolution of the oxygen and nitrogen content correlates with the transition from metallic to semiconducting behavior. The sputtering conditions were investigated taking into account the poisoning phenomena of the surface of the target from real time measurements of the target potential and from the reactive atmosphere, followed by mass spectrometry. Such diagnostics allowed to understand and to control better the advantageous role of the reactive gas pulsing technique and conducted to close relationships between the process parameters and the film properties.     

Structural, optical properties and band gap alignments of ZrOxNy thin films on Si (1 0 0) by radio frequency sputtering at different deposition temperatures

ZrO_xN_y thin films have been prepared by radio frequency magnetron sputtering at various substrate temperatures. The effect of substrate temperature on structural, optical properties and energy-band alignments of as-deposited ZrO_xN_y thin films are investigated. Atomic force microscopy results indicate the decreased root-mean-square (rms) values with substrate temperature. Fourier transform infrared spectroscopy spectra indicate that an interfacial layer has been formed between Si substrate and ZrO_xN_y thin films during deposition. X-ray photoelectron spectroscopy and spectroscopy ellipsometry (SE) results indicate the increased nitrogen incorporation in ZrO_xN_y thin films and therefore, the decreased optical band gap (E_g) values as a result of the increased valence-band maximum and lowered conduction-band minimum.     

Reactive sputtering: A method to modify the metallic ratio in the novel silver-copper oxides

Composite silver-copper targets were sputtered for the first time in various reactive Ar-O₂ mixtures to deposit the novel silver-copper oxides on glass substrates. The effect of two deposition parameters (oxygen flow rate and target composition) on the films structure was investigated. Depending on these two deposition parameters, three types of silver-copper oxides were synthesised using the reactive sputtering process: Ag_xCu_2−xO, Ag_xCu_4−xO₃ and Ag_1−xCu_1+xO₂. Although conventional processes led to the formation of silver-copper oxides with stoichiometric Cu/Ag atomic ratio, it was demonstrated that the reactive sputtering process was suitable to modify this ratio in the deposited films. Finally, the optical and electrical properties of the silver-copper oxides were investigated and compared to that of copper oxides exhibiting similar structures.     

SiOxNy thin films with variable refraction index: Microstructural, chemical and mechanical properties

In this work amorphous silicon oxynitride films with similar composition (ca. Si_0.40N_0.45O_0.10) were deposited by reactive magnetron sputtering from a pure Si target under different N₂-Ar mixtures. Rutherford backscattering (RBS) studies revealed that the coatings presented similar composition but different density. The mechanical properties evaluated by nanoindentation show also a dependence on the deposition conditions that does not correlate with a change in composition. An increase in nitrogen content in the gas phase results in a decrease of hardness and Young's modulus.The microstructural study by high resolution scanning electron microscopy (SEM-FEG) on non-metalized samples allowed the detection of a close porosity in the form of nano-voids (3-15 nm in size), particularly in the coatings prepared under pure N₂ gas. It has been shown how the presence of the close porosity allows tuning the refraction index of the films in a wide range of values without modifying significantly the chemical, thermal and mechanical stability of the film.     

Electrical property of HfOxNy-HfO2-HfOxNy sandwich-stack films

The effects of HfO_xN_y on the electrical property of HfO_xN_y-HfO₂-HfO_xN_y sandwich-stack (signed as SS) films were investigated. Excellent electrical performances were achieved in SS films, with a high dielectric constant of 16 and a low leakage current of ∼2 × 10⁻⁸ A/cm² at 1 MV/cm. Schottky (SK) emission and Frenkel-Poole (PF) emission are found to be the dominant mechanisms for the current conduction behavior. After a long time stress, the flat-band voltage shift in the SS film is much smaller than that in a pure HfO_xN_y film indicating fewer charge traps existed in the SS film. Based on the experiments, the new SS structure is more favorable for the improvement of electrical performances than a pure HfO_xN_y or HfO₂ structure.     

Sputter deposition of high transparent TiO2−xNx/TiO2/ZnO layers on glass for development of photocatalytic self-cleaning application

In this study, TiO_2−xN_x/TiO₂ double layers thin film was deposited on ZnO (80 nm thickness)/soda-lime glass substrate by a dc reactive magnetron sputtering. The TiO₂ film was deposited under different total gas pressures of 1 Pa, 2 Pa, and 4 Pa with constant oxygen flow rate of 0.8 sccm. Then, the deposition was continued with various nitrogen flow rates of 0.4, 0.8, and 1.2 sccm in constant total gas pressure of 4 Pa. Post annealing was performed on as-deposited films at various annealing temperatures of 400, 500, and 600 °C in air atmosphere to achieve films crystallinity. The structure and morphology of deposited films were evaluated by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and atomic force microscopy (AFM). The chemical composition of top layer doped by nitrogen was evaluated by X-ray photoelectron spectroscopy (XPS). Photocatalytic activity of samples was measured by degradation of Methylene Blue (MB) dye. The optical transmittance of the multilayer film was also measured using ultraviolet-visible light (UV-vis) spectrophotometer. The results showed that by nitrogen doping of a fraction (∼1/5) of TiO₂ film thickness, the optical transmittance of TiO_2−xN_x/TiO₂ film was compared with TiO₂ thin film. Deposited films showed also good photocatalytic and hydrophilicity activity at visible light.     

Improving mechanical properties of a-CNx films by Ti-TiN/CNx gradient multilayer

Amorphous carbon nitride (a-CN_x) films with functional gradient Ti-TiN/CN_x underlayer were deposited by direct current magnetron sputtering. Microstructure and composition of the films were characterized by means of X-ray diffraction (XRD), Raman spectroscopy, atomic force microscope (AFM) and transmission electron microscopy (TEM). Mechanical and tribological properties were investigated by nanoindenter, scratch and ball-on-disk tribometer. The a-CN_x-based films suffer a graphitization process with the increasing deposition temperature, thus the hardness and elastic modulus decrease. With the design of the Ti-TiN/CN_x gradient underlayers, some important advantages of relatively thick CN_x films can be achieved, such as increased hardness, improved adhesion strength, and the wear resistance of the a-CN_x-based films can be also improved significantly.     

Field electron emission from HfNxOy thin films deposited by direct current sputtering

HfN_xO_y thin films were deposited on Si substrates by direct current sputtering at room temperature. The samples were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD). SEM indicates that the film is composed of nanoparticles. AFM indicates that there are no sharp protrusions on the surface of the film. XRD pattern shows that the films are amorphous. The field electron emission properties of the film were also characterized. The turn-on electric field is about 14 V/μm at the current density of 10 μA/cm², and at the electric field of 24 V/μm, the current density is up to 1 mA/cm². The field electron emission mechanism of the HfN_xO_y thin film is also discussed.