Characterization of zirconium oxynitride films obtained by radio frequency magnetron reactive sputtering

Thin ZrN_xO_y films are deposited on Si (100) substrates by radio frequency (RF) reactive magnetron sputtering of a zirconium target in an argon-oxygen-nitrogen mixture. The Φ_N2/Φ_{(Ar + N2 + O2)} ratio was varied in the range 2.5%-100% while the oxygen flux was kept constant. The films were characterized by combining several techniques: X-ray photoelectron spectroscopy, X-ray diffraction and Secondary Ion Mass Spectroscopy. The relationship between structural and compositional properties and the sputtering parameters was investigated. Increasing nitrogen partial pressure in the gas mixture, a chemical and structural evolution happens. At lowest nitrogen flux, ZrN cubic phase is formed with a very small amount of amorphous zirconium oxynitride. At highest nitrogen flux, only crystalline ZrON phases were found. For the films obtained between these two extremes, a co-presence of ZrN and ZrON can be detected. In particular, chemical analysis revealed the co-presence of ZrO₂, ZrN, ZrON and N-rich zirconium nitride which is correlated with the Φ_N2/Φ_{(Ar + N2 + O2)} values. A zirconium nitride crystal structure with metal vacancies model has been considered in order to explain the different chemical environment detected by X-ray photoelectron spectroscopy measurements. The metal vacancies are a consequence of the deposition rate decreasing due to the target poisoning. It's evident that the growth process is strongly influenced by the zirconium atoms flux. This parameter can explain the structural evolution.     

Thin films of tetragonal zirconia (3Y-TZ) deposited by reactive sputtering

Thin films of tetragonal zirconia (TZ), comprised of 3 mol% Y₂O₃ (3Y-TZ), were deposited onto silicon, oxide-coated silicon, slide glass and aluminum oxide substrates by reactive sputtering of metallic targets in mixtures of oxygen and argon. The texture of deposited films varied with oxygen-to-argon flow ratios with which the target surface altered between metal and oxide compound constituents. Thin films of TZP with (2 0 0) preferred orientation were obtained from sputter deposition in the metallic mode whereas (1 1 1) texture was obtained in the compound mode at ambient temperature. The film texture tends to align along the 〈1 1 1〉 direction while the substrate was heated to 300 °C during the deposition. The texture of all these films was stable upon annealing at 900 °C in air. The reasons for the texture development are discussed.     

Mechanical properties of superhard TiB2 coatings prepared by DC magnetron sputtering

Superhard titanium diboride (TiB₂) coatings (H_v> 40 GPa) were deposited in Ar atmosphere from stoichiometric TiB₂ target using an unbalanced direct current (d. c.) magnetron. Polished Si (0 0 1), stainless steel, high-speed steel (HSS) and tungsten carbide (WC) substrates were used for deposition. The influence of negative substrate bias, U_s, and substrate temperature, T_s, on mechanical properties of TiB₂ coatings was studied. X-ray diffraction (XRD) analysis showed hexagonal TiB₂ structure with (0 0 01) preferred orientation. The texture of TiB₂ coatings was dependent upon the ion bombardment (U_s increased from 0 to −300 V) and the substrate heating (T_s increased from room temperature (RT) to 700 °C). All TiB₂ coatings were measured using microhardness tester Fischerscope H100 equipped with Vickers and Berkovich diamond indenters and exhibited high values of hardness H_v up to 34 GPa, effective Young's modulus E*=E/(1-ν) ranging from 450 to 600 GPa; here E and ν are the Young's modulus and Poisson's ratio, respectively, and elastic recovery W_e≈80%. TiB₂ coating with a maximum hardness H_v≈73 GPa and E*≈580 GPa was sputtered at U_s=−200 V and T_s=RT. Macrostresses of coatings σ were measured by an optical wafer curvature technique and evaluated by Stoney equation. All TiB₂ coatings exhibited compressive macrostresses.     

Deposition of Al-doped ZnO films on polyethylene naphthalate substrate with radio frequency magnetron sputtering

100 nm Al-doped ZnO (AZO) thin films were deposited on polyethylene naphthalate (PEN) substrates with radio frequency magnetron sputtering using 2 wt.% Al-doped ZnO target at various deposition conditions including sputtering power, target to substrate distance, working pressure and substrate temperature. When the sputtering power, target to substrate distance and working pressure were decreased, the resistivity was decreased due to the improvement of crystallinity with larger grain size. As the substrate temperature was increased from 25 to 120 °C, AZO films showed lower electrical resistivity and better optical transmittance due to the significant improvement of the crystallinity. 2 wt.% Al-doped ZnO films deposited on glass and PEN substrates at sputtering power of 25 W, target to substrate distance of 6.8 cm, working pressure of 0.4 Pa and substrate temperature of 120 °C showed the lowest resistivity (5.12 × 10^− 3 Ω cm on PEN substrate, 3.85 × 10^− 3 Ω cm on glass substrate) and high average transmittance (> 90% in both substrates). AZO films deposited on PEN substrate showed similar electrical and optical properties like AZO films deposited on glass substrates.     

Structural, optical, and electrical properties of AZO films by tilted angle sputtering method

We investigate the structural, optical, and electrical properties of aluminum-doped zinc oxide (AZO) films on Si substrate by a tilted angle sputtering method. The substrate holder is tilted by varying the angle from θ_sh = 0° to θ_sh = 80° during the sputtering process. As the tilted angle is increased, the deposition rate is increased due to the decreased distance between the substrate and the target. Without substrate rotation, the deposited AZO films exhibit apparently the inclined nanocolumnar structures, depending on the tilted angle. The refractive index, which is related to the porosity within films, is reduced for the larger inclined nanocolumnar structure while the extinction coefficient remains almost the same in the visible wavelength range. The inclination of nanocolumns disappears when the substrate is rotated. On glass substrate, the electrical properties as well as optical transmittance of AZO films are also dependant on the tilted angle.     

Effect of deposition distance and temperature on electrical, optical and structural properties of radio-frequency magnetron-sputtered gallium-doped zinc oxide

Films of gallium-doped zinc oxide (GZO) were deposited on glass substrates by radio-frequency magnetron sputtering using a ceramic target of Ga:ZnO (4 at.% Ga vs. Zn). Both the substrate temperature (T_s) and the target-substrate distance (d_ts) were varied and the effect on electrical, optical and structural properties of the resulting films were measured. The highest conductivity of 3200 S/cm was obtained at a deposition temperature of 250 °C, at a d_ts of 51 mm. This sample had the highest carrier concentration in this study, 9.6 × 10²⁰/cm³. Optical transmittance of all films was <90% in the visible range. The grain size of the film grown at d_ts = 51 mm was smaller than the grain size for films grown with a shorter d_ts; moreover, the films with d_ts = 51 mm exhibited the smoothest surface, with a root mean square surface roughness of 2.7 nm. Changes in T_s have a more pronounced effect on conductivity compared to changes in d_ts; however, variations in structure do not appear to be well-correlated with conductivity for samples in the 2000-3200 S/cm range. These results suggest that incorporation and activation of Ga is of key importance when attempting to obtain GZO films with conductivities greater than 2000 S/cm.     

On the zinc nitride properties and the unintentional incorporation of oxygen

Zinc nitride films were prepared by radio-frequency magnetron sputtering in N₂/Ar ambient using different substrates (glass and thermally-oxidized-Si) and buffer layers (low-temperature Zn₃N₂ and ZnO). Resonant Rutherford backscattering (RBS) allowed determining Zn_xN_y stoichiometry and thickness. Despite the sputtering system was operated in high vacuum conditions, unintentional oxygen incorporation during growth was detected. Calculations of the relative oxygen concentration showed that the oxygen content was very dependent on the growth rate. Ex-situ oxidation was also analyzed by resonant RBS and compared with the results of as-grown layers. Scanning electron microscopy and X-ray diffraction revealed that surface morphology and crystal orientation were strongly dependent on the substrate temperature (T_s). In addition, optical transmission measurements show a reduction of the optical energy band gap from 1.46 to 1.25 eV as T_s increased. The electrical properties were examined as a function of growth rate, total working gas flux and T_s aiming to maximize electron mobility. From those studies, it was found that Hall mobility increased significantly as the growth rate decreased. A maximum mobility of 100 cm²/Vs and a minimum carrier concentration of 3.2 × 10¹⁸ cm⁻³ were achieved at a T_s of 423 K and a growth rate of 4.44 nm/min.     

Fully dense, non-faceted 111-textured high power impulse magnetron sputtering TiN films grown in the absence of substrate heating and bias

We demonstrate the deposition of fully dense, stoichiometric TiN films on amorphous SiO₂ by reactive high power impulse magnetron sputtering (HiPIMS) in the absence of both substrate heating and applied bias. Contrary to the highly underdense layers obtained by reactive dc magnetron sputtering (dcMS) under similar conditions, the film nanostructure exhibits neither intra- nor intergrain porosity, exhibiting a strong 111 preferred orientation with flat surfaces. Competitive grain growth occurs only during the early stages of deposition (< 100 nm). The strong differences in the kinetically-limited nanostructural evolution for HiPIMS vs. dcMS are explained by high real-time deposition rates with long relaxation times, high ionization probabilities for Ti, and broad ion energy distributions.     

Deposition and characterization of c-axis oriented aluminum nitride films by radio frequency magnetron sputtering without external substrate heating

Aluminum nitride (AlN) films were deposited on a variety of substrates (glass, Si, oxidized Si, Al-SiO₂-Si, Cr-SiO₂-Si, and Au-Cr-SiO₂-Si) by radio frequency (RF) magnetron sputtering using an AlN target. The films were deposited without external substrate heating. The effect of RF power, ambient gas (Ar and Ar-N₂) and sputtering pressure on deposition rate and crystallinity were investigated. The structure and morphology of the films were studied by X-ray diffraction, scanning electron microscopy and atomic force microscopy techniques. These investigations revealed that the AlN films prepared in mixed gas ambient (Ar-N₂) were highly c-axis oriented with moderate surface roughness on all the substrate. A strong IR absorption band was observed around 670 cm^− 1 which confirms the presence of Al-N bond in the film. The dc resistivity of the films was measured to be in the range of 10¹¹ to 10¹² Ω-cm at moderate electric fields. The application of these films in piezoelectric based micro-electro-mechanical systems is discussed.     

Modulated pulse power sputtered chromium coatings

Cr coatings were deposited using continuous dc magnetron sputtering (dcMS) and modulated pulse power sputtering (MPP) techniques in a closed field unbalanced magnetron sputtering system at equivalent average target powers. It was found that MPP sputtering exhibited higher deposition rates than in dcMS when the average target power density was above 14 W cm^− 2 for the Cr coating depositions. Plasma diagnostics confirmed a significant increase in the numbers of both target material (Cr) and gas (Ar) ions in the MPP plasma as compared to the dc plasma. The substrate peak current densities measured in the MPP depositions (104-324 mA cm^− 2) have been increased by over a factor of 50 to those in the dcMS conditions (2-5.5 mA cm^− 2). The enhanced ion flux bombardment from the highly ionized MPP plasma led to the formation of denser microstructure and finer grain size in the MPP Cr coatings than in the dcMS Cr coatings. In addition, MPP sputtered Cr coatings exhibited improved hardness and adhesion.     

In-situ deposition of superconducting YBCO thin films by magnetron sputtering from powder target

We have used stoichiometric Y₁Ba₂Cu₃O_7–x powder as magnetron sputtering target to deposit high-quality high-T _c superconducting thin films on MgO, SrTiO₃, and ZrO₂ substrates. The zero-resistance temperatures are 86–88 K, and the 77 K zero-field critical current density is 8 × 10⁵ A/cm². The films are highlyc-axis oriented. Films deposited on 10 × 10 × 1 mm³ ZrO₂ substrates have surface resistances below 25 m at 77 K and 94 GHz. Using powder targets instead of bulk targets has the following advantages: simple and low-cost target preparation, simple target replacement, and versatility for large-area deposition.     

Time and energy resolved ion mass spectroscopy studies of the ion flux during high power pulsed magnetron sputtering of Cr in Ar and Ar/N2 atmospheres

Mass spectroscopy was used to analyze the energy and composition of the ion flux during high power pulsed magnetron sputtering (HIPIMS/HPPMS) of a Cr target in an industrial deposition system. The ion energy distribution functions were recorded in the time-averaged and time-resolved mode for Ar⁺, Ar²⁺, Cr⁺, Cr²⁺, N₂⁺ and N⁺ ions. In the metallic mode the dependence on pulse energy (equivalent of peak target current) was studied. In the case of reactive sputtering in an Ar/N₂ atmosphere, variations in ion flux composition were investigated for varying N₂-to-Ar flow ratio at constant pressure and HIPIMS power settings. The number of doubly charged Cr ions is found to increase linearly with increasing pulse energy. An intense flux of energetic N⁺ ions was observed during deposition in the reactive mode. The time evolution of ion flux composition is analyzed in detail and related to the film growth process. The ionization of working gas mixture is hampered during the most energetic phase of discharge by a high flux of sputter-ejected species entering the plasma, causing both gas rarefaction and quenching of the electron energy distribution function. It is suggested that the properties (composition and energy) of the ion flux incident on the substrate can be intentionally adjusted not only by varying the pulse energy (discharge peak current), but also by taking advantage of the observed time variations in the composition of ion flux.     

PZT thin film preparation by pulsed DC magnetron sputtering

Pulsed DC magnetron sputtering was used in this study to prepare lead zirconate titanate (Pb(Zr_xTi_1−x)O₃, PZT) thin films. A single metallic target was used for the deposition onto a Pt/Ti/SiO₂/Si substrate and parameters such as: pulse frequency, duty cycle, O₂/Ar flow ratio controlled so as to analyze the effect of the parameters on thin film deposition rate, crystalline structure and morphology. After the deposition, the thin film was annealed in a rapid thermal annealing (RTA) furnace. The experimental results showed that, when the pulse frequency was in the range of 10 kHz-100 kHz, along with the lowering of frequency and the oxygen argon flow rate ratio, the deposition rate gradually increased and the formation of PZT thin film perovskite phase was enhanced; however, if the oxygen argon flow rate ratio was too high, it caused the PZT thin film to generate a pyrochlore phase. However, when the duty cycle was in the range of 95%-75%, the highest deposition rate and better perovskite phase could be obtained in the range of 75%-80%.     

Study of the structural and optical properties of GaPN thin films grown by magnetron RF sputtering

GaP_1−xN_x thin films were deposited on glass substrates by RF sputtering employing a nitrogen-argon atmosphere in a partial pressure of 2×10⁻² Torr. We varied the growth temperature in the range 420-520 °C. The film's optical properties were studied by transmittance and absorbance spectroscopy. Characterization by scanning electron microscopy in cross-sectional view, atomic force microscopy, and X-ray diffraction was performed to determinate the film thickness, surface morphology, and crystal structure, respectively. Raman spectroscopy was employed to analyze the structural properties of samples. The GaP_1−xN_x films presented a cubic polycrystalline structure with a preferential orientation along the [1 1 1] direction. By varying the growth conditions we were able to change the band gap energy between 1.35 and 1.98 eV.     

Temperature effect on structure and surface morphology of indium tin oxide films deposited by reactive ion-beam sputtering

Indium tin oxide (ITO) films were deposited by reactive ion-beam sputtering. The relationship among the surface morphology, the resistivity ρ of the films, the substrate temperature T_S and the film thickness t_F was investigated. The heat power from the ion source during the sputtering was 265 W. T_S increased from 30 to 145 °C with an increase of t_F. The films thinner than 187 nm at T_S lower than 120 °C were amorphous, the film surface was as smooth as the substrate. The films deposited at T_S in the range between 135 and 145 °C were polycrystalline. So, the films thicker than 375 nm were in a multilayer structure of a polycrystalline layer on an amorphous layer. The surface of the polycrystalline films became rough. ρ of the films suddenly decreased at t_F of 375 nm, where the structure of the films changed. Next, the amorphous films with t_F of 39 nm were annealed in the atmosphere. The film structure changed to a polycrystalline structure at annealing temperature T_A of 350 °C. However, the surface roughness of all the films was almost same. As a result, the substrate temperature during the sputtering was important for the deposition of the films with a very smooth surface.     

High-rate deposition of high-quality Sn-doped In2O3 films by reactive magnetron sputtering using alloy targets

Sn-doped In₂O₃ (ITO) films were deposited on heated (200 °C) fused silica glass substrates by reactive DC sputtering with mid-frequency pulsing (50 kHz) and a plasma control unit combined with a feedback system of the optical emission intensity for the atomic O* line at 777 nm. A planar In-Sn alloy target was connected to the switching unit, which was operated in the unipolar pulse mode. The power density on the target was maintained at 4.4 W cm^− 2 during deposition. The feedback system precisely controlled the oxidation of the target surface in “the transition region.” The ITO film with lowest resistivity (3.1 × 10^− 4 Ω cm) was obtained with a deposition rate of 310 nm min^− 1 and transmittance in the visible region of approximately 80%. The deposition rate was about 6 times higher than that of ITO films deposited by conventional sputtering using an oxide target.     

Structure, hardness and thermal stability of nanolayered TiN/CrN multilayer coatings

Nanolayered TiN/CrN multilayer coatings were deposited on silicon substrates using a reactive DC magnetron sputtering process at various modulation wavelengths (Λ), substrate biases (V_B) and substrate temperatures (T_S). X-ray diffraction (XRD), nanoindentation and atomic force microscopy (AFM) were used to characterize the coatings. The XRD confirmed the formation of superlattice structure at low modulation wavelengths. The maximum hardness of the TiN/CrN multilayers was 3800 kg/mm² at Λ=80  Å, V_B=−150 V and T_S=400°C. Thermal stability of TiN, CrN and TiN/CrN multilayer coatings was studied by heating the coatings in air in the temperature range (T_A) of 400-800°C. The XRD data revealed that TiN/CrN multilayers retained superlattice structure even up to 700°C and oxides were detected only after T_A?750°C, whereas for single layer TiN and CrN coatings oxides were detected even at 550°C and 600°C, respectively. Nanoindentation measurements showed that TiN/CrN multilayers retained a hardness of 2800 kg/mm² upon annealing at 700°C, and this decrease in the hardness was attributed to interdiffusion at the interfaces.     

Thermochromic properties of vanadium oxide films prepared by dc reactive magnetron sputtering

A transparent vanadium oxide film has been one of the most studied electrochromic (EC) and Thermochromic (TC) materials. Vanadium oxide films were deposited at different substrate temperatures up to 400 °C and different ratios of the oxygen partial pressure (P_O2). SEM, AFM and X-ray diffraction's results show detail structure data of the films. IR mode assignments of the films measured by IR reflection-absorbance in NGIA (near grazing incidence angle) are given. It is found that the film has V₂O₅ and VO₂ combined structures. The films exhibit clear changes in transmittance when the environment temperature (T_e) is varied, especially in the 3600-4000 cm^− 1 range. Applying a T_e that is higher than a critical temperature (T_c) to the samples, the as-RT (room temperature) deposited film with 9% P_O2 has a transmittance variation of 30%, but the films that were deposited on a heated substrate of 400 °C have little variation. There is tendency of bigger variation in transmittance for the sample deposited at a larger P_O2, when it is applied by 200 °C T_e.     

Structure and properties of ternary manganese nitride Mn3CuNy thin films fabricated by facing target magnetron sputtering

Deposition of Mn₃CuN_y thin films on single crystal Si (1 0 0) at various substrate temperatures (T_sub) by facing target magnetron sputtering is reported. The crystal structure and composition were characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results confirmed that the crystalline antiperovskite Mn₃CuN_y thin film with (2 0 0) highly preferred texture had been obtained at T_sub = 180 °C. Furthermore, for the resulting Mn₃CuN_y thin film, it showed different properties compared with the bulk counterpart. There was a paramagnetic to ferrimagnetic transition at 225 K with decreasing temperature. The change of the lattice constant with temperature presented positive thermal expansion behavior and no structural transition was observed. The average linear thermal expansion coefficient (α) is 2.49 × 10⁻⁵ K⁻¹ from 123 K to 298 K. More interestingly, the temperature dependence of resistivity displayed a semiconductor-like behavior, i.e. an obvious monotonous decrease of resistivity with increasing temperature.     

Effects of heat treatment on properties of ITO films prepared by rf magnetron sputtering

Indium tin oxide (ITO) films were deposited on glass substrates by rf magnetron sputtering using a ceramic target (In₂O₃-SnO₂, 90-10 wt%) without extra heating. The post annealing was done in air and in vacuum, respectively. The effects of annealing on the structure, surface morphology, optical and electrical properties of the ITO films were studied. The results show that the increase of the annealing temperature improves the crystallinity of the films, increases the surface roughness, and improves the optical and electrical properties. The transmittance of the films in visible region is increased over 90% after the annealing process in air or in vacuum. The resistivity of the films deposited is about 8.125×10⁻⁴ Ω cm and falls down to 2.34×10⁻⁴ Ω cm as the annealing temperature is increased to 500°C in vacuum. Compared with the results of the ITO films annealed in air, the properties of the films annealed in vacuum is better.