The mechanism of reactive sputtering

The reactive sputtering of tantalum in mixed argon/oxygen atmospheres at a total pressure of 3.0×10^–4 torr has been investigated by means of measurements on deposition and growth rates, density, electrical properties and electron diffraction. The main controlling factor on all of the parameters was found to be the partial pressure of oxygen.The deposition rate was determined by the partial pressure of oxygen and assumed one of two values — either that associated with a clean tantalum target or that characteristic of an oxidised target. In the former region the oxygen content of the sputtered film was mainly dependent on the partial pressure of oxygen in the sputtering atmosphere and could range from zero to 100%. In the latter region, the films were always oxidised, but were deposited at a rate which was a fifth of that of the oxidised films sputtered under the former conditions.It is concluded that there is a critical oxygen pressure, below which tantalum metal is sputtered and undergoes reaction at the substrate, and above which tantalum oxide is sputtered from an oxide surface as the result of reaction at the target.     

Ion beam reactively sputtered silicon nitride coatings

An ion beam source was used to deposit silicon nitride films by reactive sputtering a silicon target with an Ar+N₂ beam. The nitrogen fraction in the sputtering gas was 0.05 to 0.80 at a total pressure of 6 to 20×10^?5 torr. The ion beam current was 50 mA at 500 V. A rate of deposition of about 2 nm min^?1 (0.12 μm h^?1) was found, and the spectra indicated that Si₃N₄ was obtained for a fraction of nitrogen higher than 0.50. However, the AES spectra also indicated that the sputtered silicon nitride films were contaminated with oxygen and carbon and contained significant amounts of iron, nickel, and chromium, most probably sputtered from the holder of the substrate and target.     

In situ investigation of magnetron sputtering plasma used for the deposition of multiferroic BiFeO<Subscript>3</Subscript> thin films

Somrani et al. (J. Mater. Sci. 26:3316–3323, 2015) have recently investigated the BiFeO₃ (BFO) thin films growth by RF magnetron sputtering. The role of the processing parameters especially the oxygen flow, deposition temperature and annealing on the microstructure and optical properties of the deposited films has been extensively studied. In this work a detailed investigation of the plasma deposition dynamics of BFO films is presented. A plasma sampling mass spectrometer was inserted into the magnetron sputtering reactor to analyze the nature and energy distribution of each ion species impinging onto the substrate surface. It was find that at very low pressure (<5 mTorr), the ion energy spectra of the sputtered species showed a wide, bimodal distribution with a low energy component corresponding to the sheath potential and a much higher energy component arising from particles ejected from the target and only slightly thermalized in the gas phase. At higher pressure, all energy distributions became narrower due to a nearly complete thermalization. The Bi⁺-to-Fe⁺ ratio was also found to decrease with increasing pressure, going from about 4 at 3 to 1 at 30 mTorr. A similar feature was observed for the O⁺-to-O₂ ⁺ ratio. The plasma dynamic results have been correlated to the Rutherford backscattering spectroscopy characterization of BFO thin films.     

The influence of substrate temperature and sputtering gas atmosphere on the electrical properties of reactively sputtered indium tin oxide films

Tin-doped indium oxide (ITO) films were prepared by d.c. magnetron sputtering of an In-Sn alloy target, and the influence of the sputtering gas atmosphere and substrate temperature on their electrical properties was studied.The conditions for the deposition of the transparent ITO films were divided into three regions by varying the sputtering gas pressure. The first region was characterized by a high efficiency of oxygen gas consumption for film formation and a high deposition rate. In the second region the as-deposited films contained slightly less than the stoichiometric amount of oxygen. The third region was characterized by a low efficiency of oxygen consumption and a low deposition rate. The ratio of the amount of oxygen consumed to the amount of oxygen admitted to the sputtering chamber was about 15% when films with resistivities as low as 6 × 10^-4Ω cm were prepared at the optimum oxygen partial pressure.In the case of metallic deposited in an oxygen-poor atmosphere the carrier mobility, which mainly depends on the crystal structure, increased and the carrier concentration, which depends on the number of oxygen vacancies and donor centres, decreased with increasing substrate temperature. The opposite results were obtained for films deposited in an oxygen-rich atmosphere. Well-defined grain growth was observed, particularly for metallic films deposited at high substrate temperatures, and this caused the low carrier mobility.Subsequent heat treatment improved the resistivity of films deposited at substrate temperatures below 100°C, mainly because of the increase in carrier mobility, but it had little effect on the resistivity of films deposited at substrate temperatures above 150 °C because the increase in carrier mobility was cancelled by the decrease in carrier concentration.     

Low temperature (< 100 °C) deposited P-type cuprous oxide thin films: Importance of controlled oxygen and deposition energy

With the emergence of transparent electronics, there has been considerable advancement in n-type transparent semiconducting oxide (TSO) materials, such as ZnO, InGaZnO, and InSnO. Comparatively, the availability of p-type TSO materials is more scarce and the available materials are less mature. The development of p-type semiconductors is one of the key technologies needed to push transparent electronics and systems to the next frontier, particularly for implementing p-n junctions for solar cells and p-type transistors for complementary logic/circuits applications. Cuprous oxide (Cu₂O) is one of the most promising candidates for p-type TSO materials. This paper reports the deposition of Cu₂O thin films without substrate heating using a high deposition rate reactive sputtering technique, called high target utilisation sputtering (HiTUS). This technique allows independent control of the remote plasma density and the ion energy, thus providing finer control of the film properties and microstructure as well as reducing film stress. The effect of deposition parameters, including oxygen flow rate, plasma power and target power, on the properties of Cu₂O films are reported. It is known from previously published work that the formation of pure Cu₂O film is often difficult, due to the more ready formation or co-formation of cupric oxide (CuO). From our investigation, we established two key concurrent criteria needed for attaining Cu₂O thin films (as opposed to CuO or mixed phase CuO/Cu₂O films). First, the oxygen flow rate must be kept low to avoid over-oxidation of Cu₂O to CuO and to ensure a non-oxidised/non-poisoned metallic copper target in the reactive sputtering environment. Secondly, the energy of the sputtered copper species must be kept low as higher reaction energy tends to favour the formation of CuO. The unique design of the HiTUS system enables the provision of a high density of low energy sputtered copper radicals/ions, and when combined with a controlled amount of oxygen, can produce good quality p-type transparent Cu₂O films with electrical resistivity ranging from 10² to 10⁴ Ω-cm, hole mobility of 1-10 cm²/V-s, and optical band-gap of 2.0-2.6 eV. These material properties make this low temperature deposited HiTUS Cu₂O film suitable for fabrication of p-type metal oxide thin film transistors. Furthermore, the capability to deposit Cu₂O films with low film stress at low temperatures on plastic substrates renders this approach favourable for fabrication of flexible p-n junction solar cells.     

1.6 Composition and stress state of thin films deposited by ion beam sputtering

The ion beam sputtering technique offers several advantages over conventional sputtering systems. This technique operates at a lower pressure and substrate temperature than conventional sputtering. In addition, the angle of deposition which is easily varied with ion beam sputtering is essentially fixed in dc and rf diode sputtering. As a result of these advantages, many of the parameters which effect film stress, resistivity, and grain size can be varied independently.Several properties of ion beam sputtered Ni, Al, Ni₃Al and Au thin films have been evaluated as a function of ion beam current density, target material, and the angle and distance of the substrate from the target.The grain size and stress were found to vary with the angle of deposition. There is an apparent correlation between electrical resistivity and the oxygen content in the films. Both properties depend upon the grain size. The stress levels of the films are shown to be influenced by the oxygen content. These experimental results are discussed in light of models proposed to explain the origin of stress in thin films.     

Pulsed laser deposition of conductive indium tin oxide thin films

Thin indium tin oxide (ITO) films have been grown on quartz glass substrates by pulsed laser deposition. The influence of ablation target composition and deposition conditions on the growth rate, optical transmission spectra, and carrier mobility and concentration of the films has been examined. The average surface roughness of the ITO films grown at substrate temperatures above 300°C is 2 nm. The films grown at an oxygen partial pressure of 5 mTorr using ablation targets with Sn/(In + Sn) = 5% possess high transmission (85-95%) in the visible range and low resistivity (1.8 × 10⁻⁴ Ω cm).     

Ion beam sputter-deposition of LiCoO2 films

LiCoO₂ films, 200 nm in thickness, are produced by ion beam sputter-deposition. The structural, electrical and electrochemical properties of the films are studied by means of X-ray diffraction (XRD), electrical direct-current-measurements, and electron energy loss spectroscopy (EELS). The influence of preparation parameters like substrate temperature or oxygen partial pressure, are explored. While an oxygen deficiency was observed in films sputtered under pure argon atmosphere, the oxygen content of the thin films increases, significantly, in case of films sputtered under addition of O₂. At substrate temperatures below 300 °C, XRD measurements reveal a lattice structure similar to the low-temperature-phase, while the formation of the high-temperature-phase is clearly observed at temperatures above 500 °C and an Argon/Oxygen ratio of 3/2. Furthermore, the EELS technique is demonstrated to be a sensitive tool to characterize the lithiation state of the sputter-deposited thin films.     

R.F. diode sputtered platinum films

Platinum films have been deposited using the technique of r.f. sputtering. The properties of the sputtered films were studied as a function of experimental sputtering power, ambient gas pressure, substrate temperature and bias. As a result of these studies it was possible to deposit platinum films of resistivity as low as approximately 13 μΩcm. It was found that the stress in these films can be varied from about 5x10⁹ dyn/cm² compressive to about 5x10⁹ dyn/cm² tensile depending upon the deposition conditions.     

Characterization of CuAlO2 films prepared by dc reactive magnetron sputtering

Thin films of copper aluminum oxide (CuAlO₂) were prepared on glass substrates by dc magnetron sputtering at a substrate temperature of 523 K under various oxygen partial pressures in the range 1 × 10⁻⁴–3 × 10⁻³ mbar. The dependence of cathode potential on the oxygen partial pressure was explained in terms of oxidation of the sputtering target. The influence of oxygen partial pressure on the structural, electrical and optical properties was systematically studied. p-Type CuAlO₂ films with polycrystalline nature, electrical resistivity of 3.1 Ω cm, Hall mobility of 13.1 cm² V⁻¹ s⁻¹ and optical band gap of 3.54 eV were obtained at an oxygen partial pressure of 6 × 10⁻⁴ mbar.     

Characterization of iridium oxide thin films deposited by pulsed-direct-current reactive sputtering

Thin films of iridium oxide were deposited on silicon and borosilicate glass substrates by pulsed-direct-current (pulsed-DC) reactive sputtering of iridium metal in an oxygen-containing atmosphere. Optimum deposition conditions were identified in terms of plasma pulsing conditions, oxygen partial pressures, and substrate temperature. The films were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, and Rutherford backscattering spectroscopy. According to the results, it was possible to obtain films that are near-stoichiometric, smooth and uniform in texture. The films deposited without substrate heating were amorphous, and those deposited at substrate temperatures above 300 °C were found to have a homogeneous polycrystalline structure. The results also showed that pulsed-DC sputtered iridium oxide films were smoother and had lower micro-inclusions density than DC-sputtered films obtained under otherwise similar deposition conditions. This improvement in the film quality is at the expense of a tolerable decrease in the deposition rate.     

Deposition of optical thin films by ion beam sputtering

The use of sputtering from diode or magnetron sources has been investigated thoroughly in the last few years in order to replace traditional evaporation methods for optical thin film deposition. The kinetic energy of sputtered materials, higher than that of evaporated atoms, is one of the most important causes of the superior adherence, hardness and mechanical stability of sputtered thin films. Present technology evolution is tending to develop new techniques, allowing higher and more controllable energies of materials impinging on the substrate. In the ion beam sputter deposition (IBSD) technique the working pressure in the deposition chamber may be lower than 10^-2 Pa, so thermalization of sputtered materials is avoided and the energies of depositing atoms are higher than in plasma sputtering, where thermalization takes place. This work describes the investigations carried out for realizing optical treatments by means of IBSD. The apparatus used for this study is described with details of the experiments carried out and the results obtained in the deposition of TiO₂, Y₂O₃, Al₂O₃, SiO₂ and ZnS. The films are characterized optically, mechanically and for the determination of the damage threshold from 1064 nm laser radiation.     

Structural and optical studies on dc reactive magnetron sputtered Cu2O films

Cuprous oxide (Cu₂O) thin films were deposited by dc reactive magnetron sputtering technique onto glass substrates by sputtering of pure copper target in a mixture of argon and oxygen gases under various oxygen partial pressures in the range 8 × 10^− 3–1 × 10^− 1 Pa at a constant substrate temperature of 473 K and a sputtering pressure of 4 Pa. The dependence of cathode potential on the oxygen partial pressure was explained in terms of cathode poisoning effect. The influence of oxygen partial pressure on the structural and optical properties of Cu₂O films was systematically studied. Single phase films of Cu₂O were obtained at an oxygen partial pressure of 2 × 10^− 2 Pa. The films formed at an oxygen partial pressure of 2 × 10^− 2 Pa were polycrystalline with cubic structure and exhibited an optical band gap of 2.04 eV.     

Elaboration and characterization of Fe1-xO thin films sputter deposited from magnetite target

Majority of the authors report elaboration of iron oxide thin films by reactive magnetron sputtering from an iron target with Ar-O₂ gas mixture. Instead of using the reactive sputtering of a metallic target we report here the preparation of Fe_1-xO thin films, directly sputtered from a magnetite target in a pure argon gas flow with a bias power applied. This oxide is generally obtained at very low partial oxygen pressure and high temperature. We showed that bias sputtering which can be controlled very easily can lead to reducing conditions during deposition of oxide thin film on simple glass substrates. The proportion of wustite was directly adjusted by modifying the power of the substrate polarization. Atomic force microscopy was used to observe these nanostructured layers. Mössbauer measurements and electrical properties versus bias polarization and annealing temperature are also reported.     

Effect of oxygen partial pressure on the electrical and optical properties of highly (200) oriented p-type Ni<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>O films by DC sputtering

Thin films of NiO (bunsenite) with (200) preferential orientation were synthesized on glass substrates by direct current sputtering technique in Ar+O₂ atmosphere. Nanostructural properties of the NiO films were investigated by X-ray diffraction and also by atomic force microscopic (AFM) studies. Electrical and optical properties of the deposited films were investigated as a function of different partial pressure of oxygen in the sputtering gas mixture during deposition. The films showed p-type electrical conduction and the conductivity depends on the partial pressure of oxygen. The electrical conductivity (σ_RT) was found to be .0615 S cm⁻¹ for films deposited with 100% O₂ and its value sharply decreased with the decrease the partial pressure of O₂; for example σ_RT for 50% O₂ was 6.139 × 10⁻⁵ S cm^-1. The mechanism of the origin of p-type electrical conductivity in the NiO film is discussed from the viewpoint of nickel or oxygen vacancies, which generate holes and electrons respectively. X-ray photoelectron spectroscopic studies supported the above argument. Corresponding optical properties showed that the transparency decreases with increasing oxygen partial pressure and the bandgap also decreases.     

Structural, electrical and optical properties of indium tin oxide thin films prepared by RF sputtering using different density ceramic targets

There is an active demand for the commercial indium tin oxide (ITO) target with density above 99% of the theoretical density (TD). Some works found the increase of the target density could lead to a slight decrease of the resistivity of the direct current (DC) sputtered ITO films, however, the possible effect of target density on the radio frequency (RF) sputtered ITO films is not clear. In this paper, ITO targets with different densities are successfully prepared. The structural, electrical and optical properties of the thin films deposited from these targets are studied at the substrate temperature of 750 °C. It is found that the target density has no effect on the above properties and the deposition rate of the RF sputtered ITO thin films, different from the DC sputtered films. So for the RF sputtered process, the target needs not high density so that the used target can be just compacted from the powders without sintering. All the as-prepared ITO films with different densities have a resistivity of 1.56 × 10⁻⁴ Ω cm and a transmittance of ∼87%, which are lower than the ITO films prepared at temperatures lower than 400 °C.     

Ion plasma deposition of oxide films with graded-stoichiometry composition: Experiment and simulation

A method of ion plasma deposition is proposed for obtaining thin multicomponent films with continuously graded composition in depth of the film. The desired composition–depth profile is obtained by varying the working gas pressure during deposition in the presence of an additional adsorbing screen in the drift space between a sputtered target and substrate. Efficiency of the proposed method is confirmed by Monte Carlo simulation of the deposition of thin films of Ba _x Sr_1–x TiO₃ (BSTO) solid solution. It is demonstrated that, during sputtering of a Ba_0.3Sr_0.7TiO₃ target, the parameter of composition stoichiometry in the growing BSTO film varies in the interval of x = 0.3–0.65 when the gas pressure is changed within 2–60 Pa.

     

Nanoindentation and atomic force microscopy measurements on reactively sputtered TiN coatings

Titanium nitride (TiN) coatings were deposited by d.c. reactive magnetron sputtering process. The films were deposited on silicon (111) substrates at various process conditions, e.g. substrate bias voltage (V_B) and nitrogen partial pressure. Mechanical properties of the coatings were investigated by a nanoindentation technique. Force vs displacement curves generated during loading and unloading of a Berkovich diamond indenter were used to determine the hardness (H) and Young’s modulus (Y) of the films. Detailed investigations on the role of substrate bias and nitrogen partial pressure on the mechanical properties of the coatings are presented in this paper. Considerable improvement in the hardness was observed when negative bias voltage was increased from 100–250 V. Films deposited at |V _B| = 250 V exhibited hardness as high as 3300 kg/mm². This increase in hardness has been attributed to ion bombardment during the deposition. The ion bombardment considerably affects the microstructure of the coatings. Atomic force microscopy (AFM) of the coatings revealed fine-grained morphology for the films prepared at higher substrate bias voltage. The hardness of the coatings was found to increase with a decrease in nitrogen partial pressure.     

Effect of the oxygen pressure on the photoluminescence properties of ZnO thin films by PLD

ZnO thin films on Si(111) substrate were deposited by laser ablation of Zn target in oxygen reactive atmosphere; Nd-YAG laser with wavelength of 1064 nm was used as laser source. The experiments were performed at laser energy density of 31 J/cm², substrate temperature of 400 °C and various oxygen pressures (5–65 Pa). X-ray diffraction was applied to characterize the structure of the deposited ZnO films and the optical properties of the ZnO thin films were characterized by photoluminescence with an Ar ion laser as a light source using an excitation wavelength of 325 nm. The influence of the oxygen pressure on the structural and optical properties of ZnO thin films was investigated. It was found that ZnO film with random growth grains can be obtained under the condition of oxygen pressure 5–65 Pa. It will be clearly shown that the grain size and the formation of intrinsic defects depend on the oxygen partial pressure and that high optical quality of the ZnO films is obtained under low oxygen pressure (5 Pa, 11 Pa) conditions.     

中频反应磁控溅射沉积Al2O3薄膜中迟滞回线的研究

采用中频磁控反应溅射工艺进行氧化铝薄膜的沉积实验,对该工艺过程中溅射电压和沉积速率与氧流量的“迟滞回线”现象进行了研究。通过对实验现象的分析讨论,解释了薄膜沉积速率变化的原因。