Formation process of Al2O3 thin film by reactive sputtering

Al and Al₂O₃ films were deposited by RF magnetron sputtering using a mixed gas of Ar and O₂. The surface of the Al target was changed from the metallic mode to the oxide mode at a critical O₂ flow ratio of 8%. The atomic ratio of sputtered Al atoms to supplied oxygen atoms was found to be approximately 2:3 at the critical O₂ flow ratio. The oxide layer thickness formed on the Al target was estimated to be 5-7 nm at an O₂ flow ratio of 100% by ellipsometry.     

Angular distribution and sputtering yield of Al and Al2O3 during 40 key argon ion bombardment

The angular distribution and sputtering yield of Al and Al₂O₃ during 40 keV argon ion bombardment have been measured by collecting the sputtered particles on a semi-cylindrical collector and analysing them by Rutherford backscattering spectrometry (RBS). It was found that due to the relatively high residual pressures (1–4 · 1O^?4Pa) in the sputtering chamber not only aluminium but also oxygen atoms are deposited on the collector through the mechanism of reactive sputtering both when sputtering the oxide and the metal target. The angular distribution of the collected aluminium and oxygen atoms in the case of pure aluminium sputtering follows a cosine law while in the case of Al₂O₃ sputtering a considerable deviation from the cosine law is observed. This deviation is explained by a preferred orientation (texture) of the crystallites in the polycrystalline oxide targets. It was found that the very thin films deposited on the collector when sputtering both types of targets have a composition close to AlO₂. The sputtering yield of Al and Al₂O₃ by 40 keV argon ions has been determined. On the basis of the obtained values an estimation of the productivity of the reactive sputter deposition of Al₂O₃ films from oxidized and non-oxidized targets is made.     

Direct current reactive sputtering of aluminium

The influence of the oxygen content in the gas flow on the discharge current and on the chemical composition of sputtered AlO_x was investigated. Unlike SiO₂, Al₂O₃ films are formed on the substrate only for oxygen contents sufficient for full oxidation of the target surface. The minimum oxygen content can be determined by the sharp change in discharge current at constant working voltage and total gas pressure. Infrared spectra confirming this statement are given. The kinetics of the processes of forming and sputtering off of an oxide layer on the aluminium target surface were also investigated. Some speculations about the interrelation between oxide formation on the substrate and on the target for direct current reactive sputtering are given.     

High rate reactive deposition of TiO2 films using two sputtering sources

We propose a new high-rate reactive sputter-deposition method with two sputtering sources for fabricating TiO₂ films. One source operates in a metal mode sputtering condition and supplies titanium atoms to the substrate. The other source operates in oxide mode and works as an oxygen radical source for supplying oxygen radicals to the substrate surface for promoting oxidization of titanium atoms. Each sputtering source is separated with a mesh grid from the deposition chamber, and Ar and oxygen gas are introduced separately through the titanium supply and oxygen radical sources, respectively. By using this reactive sputtering system, a deposition rate above 80 nm/min can be obtained for the deposition of TiO₂ films with rutile structure.     

High rate reactive deposition of TiO2 films using two sputtering sources

We propose a new high-rate reactive sputter-deposition method with two sputtering sources for fabricating TiO₂ films. One source operates in a metal mode sputtering condition and supplies titanium atoms to the substrate. The other source operates in oxide mode and works as an oxygen radical source for supplying oxygen radicals to the substrate surface for promoting oxidization of titanium atoms. Each sputtering source is separated with a mesh grid from the deposition chamber, and Ar and oxygen gas are introduced separately through the titanium supply and oxygen radical sources, respectively. By using this reactive sputtering system, a deposition rate above 80 nm/min can be obtained for the deposition of TiO₂ films with rutile structure.     

In-situ analysis of positive and negative energetic ions generated during Sn-doped In2O3 deposition by reactive sputtering

Using a quadrupole mass spectrometer combined with an energy analyser, we have investigated the in-situ energy distribution of highly energetic ions generated during reactive sputtering of In-Sn alloy (IT) targets and non-reactive sputtering of Sn-doped In₂O₃ (ITO) ceramic targets. Ar⁺, In⁺, O⁺, O⁻, O₂⁻, InO⁻ and InO₂⁻ ions with kinetic energies greater than 40 eV were clearly observed. Upon increasing the O₂ flow ratio for reactive sputtering, the surface of the IT target changes from metal (metal mode) to oxide (oxide mode) via a state of mixed metal and oxide (transition region). O⁻ ions with the kinetic energy corresponding to cathode voltage are generated at the oxide layer, which expands upon the target surface with increasing O₂ flow ratio in the metal mode and the transition region. In contrast, the flux of 60-eV Ar⁺ ions decreases with increasing O₂ flow ratio. The presence of 125- and 200-eV In⁺ ions is attributed to the dissociation of InSnO₂⁻ and InO₂⁻ with the kinetic energy corresponding to cathode voltage, respectively, while the presence of 40- and 150-eV O⁺ ions is attributed to the dissociation of InO₂⁻ and O₂⁻ with the kinetic energy corresponding to cathode voltage, respectively.     

Time-dependent variation of the target mode in reactive sputtering of Al–O2 system

Reactive sputtering techniques have been widely used for forming compound thin films. In this study, the time-dependent variation of the target mode of an Al–O₂ system was investigated by measuring the target voltage for various reactive O₂ gas flow ratios and presputtering (i.e., sputtering in pure Ar gas to clean the target surface) times. The Al target remains in metallic mode for a certain period of time after being exposed to an Ar–O₂ plasma before it begins to be oxidized. This period increases with decreasing O₂ flow ratio and with increasing the presputtering time. It is considered that the period is caused by the gettering of O₂ gas by Al films deposited on the substrate and the chamber wall during presputtering.     

Hysteresis-free reactive high power impulse magnetron sputtering

High power impulse magnetron sputtering (HIPIMS) of an Al target in Ar/O₂ mixtures has been studied. The use of HIPIMS is shown to drastically influence the process characteristics compared to conventional sputtering. Under suitable conditions, oxide formation on the target as the reactive gas flow is increased is suppressed, and the hysteresis effect commonly observed as the gas flow is varied during conventional sputtering can be reduced, or even completely eliminated, using HIPIMS. Consequently, stoichiometric alumina can be deposited under stable process conditions at high rates. Possible explanations for this behavior as well as a model qualitatively describing the process are presented.     

Time-dependent variation of the target mode in reactive sputtering of Al-O2 system

Reactive sputtering techniques have been widely used for forming compound thin films. In this study, the time-dependent variation of the target mode of an Al-O₂ system was investigated by measuring the target voltage for various reactive O₂ gas flow ratios and presputtering (i.e., sputtering in pure Ar gas to clean the target surface) times. The Al target remains in metallic mode for a certain period of time after being exposed to an Ar-O₂ plasma before it begins to be oxidized. This period increases with decreasing O₂ flow ratio and with increasing the presputtering time. It is considered that the period is caused by the gettering of O₂ gas by Al films deposited on the substrate and the chamber wall during presputtering.     

Advantages of inductively coupled plasma-assisted sputtering for preparation of stoichiometric VO2 films with metal-insulator transition

Inductively coupled plasma (ICP)-assisted sputtering with an internal coil enabled deposition of stoichiometric crystalline vanadium dioxide (VO₂) films on a sapphire (Al₂O₃) (001) substrate under widely various deposition conditions. The films showed a metal-insulator (M-I) transition around temperatures of 68 °C with several orders of change in resistivity. Particularly, low-temperature (250 °C) growth of VO₂ film with two orders transition decade was achieved in ICP-assisted sputtering, in contrast with conventional sputtering, which required 400 °C for VO₂ growth. Rutherford back scattering (RBS) measurements revealed that the VO₂ film prepared by ICP-assisted sputtering was exactly stoichiometric, containing no impurity atoms from the inserted coil material. The ICP-assisted sputtering was examined in comparison to conventional sputtering in view of plasma characteristics.     

Synthesis of Al-Cr-O-N thin films in corundum and f.c.c. structure by reactive r.f. magnetron sputtering

Advanced PVD coatings for metal cutting applications must exhibit a multifunctional property profile including high hardness, chemical inertness and high temperature stability. Recently, ternary Al-Cr-O thin films with mechanical properties similar or superior to conventional aluminium oxide thin films have been suggested as potential materials meeting such demands. These coatings can be deposited at moderate temperatures in PVD processes. In this work, new quaternary Al-Cr-O-N coatings are suggested as alternative for offering thin film materials of high strength, hardness and even toughness. A combinatorial approach to the synthesis of Al-Cr-O-N thin films by means of reactive r.f. magnetron sputtering is presented. A thorough phase analysis of deposited coatings covering a wide range of elemental compositions revealed a well-defined phase transition from a corundum-type α-(Al_1 − x,Cr_x)_2 + δ(O_1 − y,N_y)₃ structure to a CrN-type f.c.c.-(Al_1 − x,Cr_x)_1 + θ(O_1 − y,N_y) structure as a function of the Al/Cr ratio and the nitrogen gas flow ratio. Detailed results on the coatings composition, constitution and microstructure are discussed compared to ternary Al-Cr-O thin films deposited by reactive r.f. magnetron sputtering under nearly identical conditions.     

Mechanisms of reactive sputtering of indium II: Growth of indium oxynitride in mixed N2-O2 discharges

The reactive sputtering of indium in mixed N₂-O₂ discharges was investigated using in situ optical absorption and emission spectroscopic analyses of plasma processes. All measured discharge parameters including the target sputtering rate, the target current and the sputtered indium emission intensity and neutral atom density exhibited abrupt changes with oxygen concentration at a critical value C¹. For a total pressure of 50 mTorr C¹ was approximately 2.5 mol.%. The abrupt change was caused by the formation of an indium oxide layer on the target surface over a very narrow range of O₂ partial pressures. The nitrogen coverage on the target was small at all gas compositions because of rapid preferential sputtering.X-ray photoelectron spectroscopy, Auger electron spectroscopy and X-ray diffraction were used to characterize the deposited film chemistry and structure as functions of the growth conditions. All films were n-type semiconductors and could be classified into the following three groups: (1) films grown at 0<C₀₂<2.5 mol.% were InN-based alloys with the wurtzite structure containing oxygen in solid solution; (2) films grown at 2.5 mol.% <C_O2<6 mol.% were two-phase mixtures; (3) films grown at C_O2>6 mol.% were cubic In₂O₃-based alloys with nitrogen in solid solution. Optical band gap measurements showed that E_g ranged from 1.7 to 2.4 eV for films of type (1) and from 2.4 to 3.6 eV for films of type (3).     

Overview of optical properties of Al2O3 films prepared by various techniques

We study optical properties of Al₂O₃ films prepared by various techniques using spectroscopic ellipsometry. The film preparation techniques include conventional pulsed magnetron sputtering in various gas mixtures, high power impulse magnetron sputtering, annealing of as-deposited Al₂O₃ in an inert atmosphere and annealing of as-deposited Al in air. We focus on the effect of the preparation technique, deposition parameters and annealing temperature on the refractive index, n, and extinction coefficient, k, of stoichiometric Al₂O₃. At a wavelength of 550 nm we find n of 1.50-1.67 for amorphous deposited Al₂O₃, 1.65-1.67 for amorphous Al₂O₃ obtained by Al annealing, 1.46-1.69 for γ-Al₂O₃ and decreasing n for Al₂O₃ annealing temperature increasing up to 890 °C. The results facilitate correct interpretation of optical characterization of Al₂O₃, as well as selection of a preparation technique corresponding to a required Al₂O₃ structure and properties.     

Oxidation behavior of (Ti1 − xAlx)N films perpared by r.f. reactive sputtering

(Ti, Al)N films have drawn much attention as alternatives for TiN coatings, which are oxidized easily in air above 500 °C. We have investigated the effect of Al content on the oxidation resistance of (Ti_{1 − x}Al_x)N films prepared by r.f. reactive sputtering.(Ti_{1 − x}Al_xN films (O ≤ x ≤ 0.55) were deposited onto fused quartz substrates by r.f. reactive sputtering. Composite targets with five kinds of Al-to-Ti area ratio were used. The sputtering gas was Ar (purity, 5 N) and N₂ (5 N). The flow rate of Ar and N₂ gas was kept constant at 0.8 and 1.2 sccm, respectively, resulting in a sputtering pressure of 0.4 Pa. The r.f. power was 300 W for all experiments. Substrates were not intentionally heated during deposition. The deposited films (thickness, 300 nm) were annealed in air at 600 900 °C and then subjected to X-ray diffractometer and Auger depth profiling.The as-deposited (Ti_{1 − x}Al_x)N films had the same crystal structure as TiN (NaCl type). Al atoms seemed to substitute for Ti in lattice sites. The preferential orientation of the films changed with the Al content of the film, x. Oxide layers of the films grew during annealing and became thicker as the annealing temperature increased. The thickness of the oxide layer grown on the film surface decreased with increasing Al content in the film. For high Al content films an Al-rich oxide layer was grown on the surface, which seemed to prevent further oxidation. All of the films, however, were oxidized by 900 °C annealing, even if the Al content was increased up to 0.55.     

Energetic negative ions in titanium oxide deposition by reactive sputtering in Ar/O2

The flux of energetic negative ions was measured during the preparation of TiO₂ in Ar/O₂ as a function of oxygen partial pressure. The Ti surface was so active that the small amount of O₂ contained in Ar was sufficient to oxidize the target surface. Ti target is also oxidized as similarly to the other metals such as Zr and Zn. Oxide islands form, which coalesce and cover the target surface with an oxide layer. The thickness of the Ti oxide layer on the target surface increased with increasing target current and Ar/O₂ gas pressure, which increased the oxygen flux incident on the target. This is due to the high reactivity of the Ti surface with oxygen. The data revealed that the flux of energetic negative ions in reactive sputtering of Ti in Ar/O₂ is fairly small compared with the sputtering of Zr and Zn. This indicates that the generation rate of negative ions on the Ti target during the reactive sputtering is very small.     

Discharge power dependence of structural and electrical properties of Al-doped ZnO conducting film by magnetron sputtering (for PDP)

In order to investigate the possible application of ZnO films as a transparent conducting oxide (TCO) electrode for AC PDP, ZnO:Al films were prepared by DC magnetron sputtering method. The effects of discharge power and doping concentration on the structural and electrical properties of ZnO films were mainly studied experimentally. Five-inch PDP cells using either a ZnO:Al or indium tin oxide (ITO) electrode were also fabricated separately under the same manufacturing conditions. The luminous properties of both the PDP cells were measured and compared with each other.By doping the ZnO target with 2 wt% of Al₂O₃, the film deposited at a discharge power of 40 W resulted in the minimum resistivity of 8.5 × 10⁻⁴ Ω-cm and a transmittance of 91.7%. However, a high doping concentration of 3 wt% of Al₂O₃ and excessive sputtering power over 40 W may induce high defect density and limit the growth of small grains. Although the luminance and luminous efficiency of the cell using ZnO:Al are lower than those of the cell with the ITO electrode by about 10%, these values are sufficient enough to be considered for the normal operation of AC PDP.     

In-situ analyses on the reactive sputtering process to deposit Al-doped ZnO films using an Al-Zn alloy target

The kinetic energies of generated ions were investigated during the reactive sputtering process to deposit Al-doped ZnO (AZO) films using an Al-Zn alloy target. The sputtering system was equipped with specially designed double feedback system to stabilise the reactive sputtering processes and analysis was performed with a quadrupole mass spectrometer combined with an energy analyser. Negative ions O⁻, O₂⁻, AlO⁻ and AlO₂⁻ with high kinetic energies corresponding to cathode voltage are generated at the partially oxidised target surface, after which some of the ions undergo subsequent charge exchange and/or dissociation. Positive ions O⁺, Ar⁺, Zn⁺ and Al⁺ with lower kinetic energies (around 10 eV) are generated by charge exchange of sputtered neutral O, Ar, Zn and Al atoms, respectively. As the target surface oxidises, cathode voltage decrease, the flux of high-energy negative ions increases and the electrical properties of the AZO degrade by ion bombardment as well as the AZO films that are deposited by conventional magnetron sputtering using an AZO target.     

Tungsten oxide with different oxygen contents: Sliding properties

In this study, tungsten oxide coatings with 13 and 75 at% of oxygen were prepared by DC reactive magnetron sputtering from a pure W target in an Ar+O₂ atmosphere. The coating hardness (H) decreased with increasing oxygen content from 25 to 7.7 GPa. The values of H/E ratio were 0.08 and 0.07 for W₈₇O₁₃ and W₂₅O₇₅, respectively.The tribological measurements were carried out on a pin-on-disc tribometer at room temperature, with a load of 5 N and steel 100Cr6, ceramic Si₃N₄ and Al₂O₃ balls as sliding partners. The wear track and wear debris were visualised by scanning electron microscopy and the chemical composition of the later was estimated by energy-dispersive X-ray analysis. The friction coefficient was rather high in case of the W₈₇O₁₃ coating reaching values in the range from 0.7 to 0.75 for both counterpart materials, and slightly lower for W₂₅O₇₅ (∼0.50). The coating wear rate decreased with increasing oxygen content with the Al₂O₃ ball, while using Si₃N₄ ball as a counterpart showed an opposite trend. The coating with low oxygen content was more resistant to abrasive wear.     

Atomistic Modeling of Corrosion Resistance: A First Principles Study of O2 Reduction on the Al(111) Surface Covered with a Thin Hydroxylated Alumina Film

In the early stage of corrosion of Al or Al alloys (i.e., during the initiation of localized corrosion), an oxide film is generally present on the surface. This work investigates the possibility for a cathodic reaction to occur on these oxide films. We discuss realistic models of supported oxide films on Al(111) in order to disentangle the factors determining the reactivity towards O₂. Three components of the complex film formed on Al(111) can be identified: an ultrathin under‐stoichiometric Al_xO_y interface layer, an intermediate Al₂O₃ phase with γ‐alumina structure, and an hydroxylated AlOOH surface termination with boehmite structure. The electron transfer to O₂ molecules depends on the workfunction, Φe, of the metal/oxide interface and on the thickness of the inner Al₂O₃ phase. The electron transfer takes place both from the metal‐oxide interface and the oxide surface to the adsorbed O₂ molecule. Very important is the role of the hydroxyl groups at the surface: they eliminate the Al surface states and stabilize the surface; they allow the reduced O₂ ⁻ species to capture protons and transform into hydrogen peroxide in a non‐activated process. H₂O₂ is further reduced to two water molecules, in a series of two‐electron mechanisms. These reactions take place only when the internal alumina phase is ultrathin (here 0.2 nm). As soon as an Al₂O₃ inner layer develops (film thickness of about 1 nm), the film becomes unreactive and passivates the Al(111) surface. The results help to shed light on the complex reactions responsible for metal corrosion.