An extreme change in structural and optical properties of indium oxynitride deposited by reactive gas-timing RF magnetron sputtering

The indium oxynitride (InON) films were achieved by reactive RF magnetron sputtering indium target which has the purity of 99.999% with a novel reactive gas-timing technique. The structural, optical and electrical properties in a series of polycrystalline InON films affected by gas-timing of reactive N₂ and O₂ gases introduced to the chamber were observed. The X-ray photoelectron spectroscopy revealed that the oxygen content in thin films that compounded to indium and nitrogen, which increased from 10% in indium nitride (InN) to 66% in indium oxide (In₂O₃) films. The X-ray diffraction peaks show that the phase of deposited films changes from InN to InON and to In₂O₃ with an increasing oxygen timing. The hexagonal structure of InN films with predominant (0 0 2) and (0 0 4) orientation was observed when pure nitrogen is only used as sputtering gas, while InON and In₂O₃ seem to demonstrate body-center cubic polycrystalline structures depending on gas-timing. The surface morphologies investigated from atomic force microscope of deposited films with varying gas-timing of O₂:N₂ show indifferent. The numerical algorithm method was used to define the optical bandgap of films from transmittance results. The increasing oxygen gas-timing affects extremely to the change of crystallinity phase from InN to InON and to In₂O₃, the increase of optical bandgap from 1.4 to 3.4 eV and the rise of sheet resistance from 15 Ω/□ to insulator.     

Influence of sputtering power and Ar–N2 flow on the structure and optical properties of indium nitride films prepared by magnetron sputtering

ABSTRACT

This paper discusses the deposition of indium nitride (InN) thin films on Si (100) substrates by using pulsed DC magnetron sputtering. Effects of varying sputtering power and Ar–N₂ flow ratio on the structural, morphological, and optical properties of indium nitride (InN) films were investigated. The structural characterization indicated nanocrystalline InN film with preferred orientation towards (101) plane that exhibited the optimum crystalline quality at 130?W and for 40:60 Ar–N₂ ratio. The surface morphology of InN, as observed through FESEM, contained irregularly shaped nanocrystals with size that increases with higher sputtering power and Ar:N₂ flow ratio. The optical properties of InN films were studied using ellipsometer at room temperature. The band gap of InN was decreased with the increase of sputtering power to 130?W, whereas an increase in the band gap was noticed with the increase of the Ar:N₂ flow ratio.     

Preparation and characterization of nitrogen-incorporated SnO2 films

Nitrogen-incorporated SnO₂ thin films have been grown on Si(100) and quartz substrates by reactive sputtering of a Sn target in gas mixtures of N₂–O₂. The structure of the nitrogen-incorporated SnO₂ thin films was studied by X-ray diffraction, and the changes in the chemical bonds and atomic binding states of the nitrogen-incorporated SnO₂ thin films were analyzed by X-ray photoelectron spectroscopy. It was found that the binding energy of Sn 3d and O 1s shifts 0.65 eV and 0.35 eV, respectively, toward the lower-energy side after nitrogen was incorporated into the SnO₂ thin films as a comparison with that of pure SnO₂ film. The indirect optical band gap gradually decreases from 3.42 eV to 3.23 eV, i.e. from the UV to the edge of the visible-light range, with increasing nitrogen flux content in the N₂–O₂ gas mixtures. PACS 81.15.Cd; 78.20.-e; 68.37.Xy; 81.05.Je     

Growth and surface characterization of sputter-deposited molybdenum oxide thin films

Molybdenum oxide thin films were produced by magnetron sputtering using a molybdenum (Mo) target. The sputtering was performed in a reactive atmosphere of an argon-oxygen gas mixture under varying conditions of substrate temperature (T_s) and oxygen partial pressure (pO₂). The effect of T_s and pO₂ on the growth and microstructure of molybdenum oxide films was examined in detail using reflection high-energy electron diffraction (RHEED), Rutherford backscattering spectrometry (RBS), energy-dispersive X-ray spectrometry (EDS), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM) measurements. The analyses indicate that the effect of T_s and pO₂ on the microstructure and phase of the grown molybdenum oxide thin films is remarkable. RHEED and RBS results indicate that the films grown at 445 °C under 62.3% O₂ pressure were stoichiometric and polycrystalline MoO₃. Films grown at lower pO₂ were non-stoichiometric MoO_x films with the presence of secondary phase. The microstructure of the grown Mo oxide films is discussed and conditions were optimized to produce phase pure, stoichiometric, and highly textured polycrystalline MoO₃ films.     

Novel type of indium oxide thin films sputtering for opto-electronic applications

Transparent conductive oxide (TCO) thin films play a significant role in recent optical technologies. Displays of various types, photovoltaic systems, and opto-electronic devices use these films as transparent signal electrodes. They are used as heating surfaces and active control layers. Oxides of TCO materials such as: tin, indium, zinc, cadmium, titanium and the like, exhibit their properties. However, indium oxide and indium oxide doped with tin (ITO) coatings are the most used in this technology.In this work, we present conductive transparent indium oxide thin films which were prepared using a novel triode sputtering method. A pure In₂O₃ target of 2 in. in diameter was used in a laboratory triode sputtering system. This system provided plane plasma discharge at a relatively low pressure 0.5-5 mTorr of pure argon. The substrate temperature was varied during the experiments from room temperature up to 200 °C. The films were deposited on glass, silicon, and flexible polyimide substrates. The films were characterized for optical and electrical properties and compared with the indium oxide films deposited by magnetron sputtering.     

Growth of InN films on (1 1 1)GaAs substrates by reactive magnetron sputtering

Indium nitride (InN) films were grown on (1 1 1)GaAs substrates by reactive magnetron sputtering using an indium target. It was found that the crystal quality of InN films depends strongly on the substrate temperature and sputtering gas pressure, and highly c-axis preferred wurtzite InN films can be obtained at growth temperature as low as 100°C. Based on these results, the growth mechanism of InN films in the reactive magnetron sputtering was discussed.     

Electrical and optical properties of silver doped indium oxide thin films prepared by reactive DC magnetron sputtering

Silver doped indium oxide (In_2−x Ag_x O_3−y) thin films have been prepared on glass and silicon substrates at room temperature (300 K) by reactive DC magnetron sputtering technique using an alloy target of pure indium and silver (80: 20 atomic %. The magnetron power (and hence the metal atom sputter flux) is varied in the range 40-80 W. The energy dispersive analysis of X-ray (EDAX) results show that the silver content in the film decreases with increasing magnetron power. The grain size of these films is of the order of 100 nm. The resistivity of these films is in the range 10⁻²-10⁻³ Ω cm. The work function of the silver-indium oxide films (by Kelvin Probe) are in the range: 4.64-4.55 eV. The refractive index of these films (at 632.8 nm) varies in the range: 1.141-1.195. The optical band gap of indium oxide (3.75 eV) shrinks with silver doping. Calculations of the partial ionic charge (by Sanderson's theory) show that silver doping in indium oxide thin films enhance the ionicity.     

Niobium based coatings for dental implants

Niobium based thin films were deposited on stainless steel (SS) substrates to evaluate them as possible biocompatible surfaces that might improve the biocompatibility and extend the life time of stainless steel dental implants. Niobium nitride and niobium oxide thin films were deposited by reactive unbalanced magnetron sputtering under standard deposition conditions without substrate bias or heating. The biocompatibility of the surfaces was evaluated by testing the cellular adhesion and viability/proliferation of human cementoblasts during different culture times, up to 7 days. The response of the films was compared to the bare substrate and pieces of Ti6Al4V; the most commonly used implant material for orthopedics and osteo-synthesis applications. The physicochemical properties of the films were evaluated by different means; X-ray diffraction, Rutherford backscattering spectroscopy and contact angle measurements. The results suggested that the niobium oxide films were amorphous and of stoichiometric Nb₂O₅ (a-Nb₂O₅), while the niobium nitride films were crystalline in the FCC phase (c-NbN) and were also stoichiometric with an Nb to N ratio of one. The biological evaluation showed that the biocompatibility of the SS could be improved by any of the two films, but neither was better than the Ti6Al4V alloy. On the other hand, comparing the two films, the c-NbN seemed to be a better surface than the oxide in terms of the adhesion and proliferation of human cemetoblasts.     

Surface oxidation kinetics of sputtering targets

Films of compounds can be deposited by sputtering a metal or alloy target in an atmosphere containing a suitable reactive gas. Both Al and 90 : 10 In : Sn targets have been sputtered in argon/oxygen mixtures to obtain Al₂O₃ and indium tin oxide films. The experiments were carried out in a planar magnetron sputtering system with both dc and rf excitation. To investigate the kinetics of the reactive sputtering process, the time dependence of the total gas pressure was measured after a change in oxygen flow rate or sputtering power; a capacitance manometer gave accurate and reproducible results. There were simultaneous changes in the rf matching conditions when rf excitation was used. These changes can be attributed to the formation of an oxide on the target surface. The time dependence of the oxygen pressure measured for the Al and In : Sn targets have been used to compare various models of the reactive sputtering process. Fitting of the experimental values to these models yields values of the equilibrium oxide thickness on the target and these have been compared with measured values. For rf sputtering of an Al target at 500 W with flow rates of $\text{3}\text{ml}\text{min}$ and $\text{2.2}\text{ml}\text{min}$ for argon and oxygen respectively, both the calculated and the measured value of the oxide thickness is 100 nm.     

Photomodulated reflectance study on optical property of InN thin films grown by reactive gas-timing rf magnetron sputtering

The photoreflectance (PR) spectroscopy has been applied to investigate the band-gap energy (E_g) of indium nitride (InN) thin films grown by rf magnetron sputtering. A novel reactive gas-timing technique applied for the sputtering process has been successfully employed to grow InN thin films without neither substrate heating nor post annealing. The X-ray diffraction (XRD) patterns exhibit strong peaks in the orientation along (0 0 2) and (1 0 1) planes, corresponding to the polycrystalline hexagonal-InN structure. The band-gap transition energy of InN was determined by fitting the PR spectra to a theoretical line shape. The PR results show the band-gap energy at 1.18 eV for hexagonal-InN thin films deposited at the rf powers of 100 and 200 W. The high rf sputtering powers in combination with the gas-timing technique should lead to a high concentration of highly excited nitrogen ions in the plasma, which enables the formation of InN without substrate heating. Auger electron spectroscopy (AES) measurements further reveal traces of oxygen in these InN films. This should explain the elevated band-gap energy, in reference to the band-gap value of 0.7 eV for pristine InN films.     

Influence of substrate crystallography on the room temperature synthesis of AlN thin films by reactive sputtering

A pulsed DC reactive ion beam sputtering system has been used to synthesize aluminium nitride (AlN) thin films at room temperature by reactive sputtering. After systematic study of the processing variables, high-quality polycrystalline films with preferred c-axis orientation have been grown successfully on silicon and Au/Si substrates with an Al target under a N₂/(N₂ + Ar) gas flow ratio of 55%, 2 mTorr processing pressure and keeping the temperature of the substrate holder at room temperature. The crystalline quality of the AlN layer as well as the influence of the substrate crystallography on the AlN orientation has been characterized by high-resolution X-ray diffraction (HR-XRD). Best ω-FWHM (Full Width at Half Maximum) values of the (0 0 0 2) reflection rocking curve in the 1 μm thick AlN layers are 1.3°. Atomic Force Microscopy (AFM) measurements have been used to study the surface morphology of the AlN layer and Transmission Electron Microscopy (TEM) measurements to investigate the AlN/substrate interaction. AlN grew off-axis from the Si substrate but on-axis to the surface normal. When the AlN thin film is deposited on top of an Au layer, it grows along the [0 0 0 1] direction but showing a two-domain structure with two in-plane orientations rotated 30° between them.     

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.     

Vanadium oxide thin films deposited on indium tin oxide glass by radio—frequency magnetron sputtering

Highly oriented VO₂(B), VO₂(B) + V₆O₁₃ films were grown on indium tin oxide glass by radio-frequency magnetron sputtering. Single phase V₆O₁₃ films were obtained from VO₂(B) +V₆O₁₃ films by annealing at 480℃ in vacuum. The vanadium oxide films were characterized by x-ray diffraction and x-ray photoelectron spectra (XPS). It was found that the formation of vanadium oxide films was affected by substrate temperature and annealing time, because high substrate temperature and annealing were favourable to further oxidation. Therefore, the formation of high valance vanadium oxide films was realized. The V₆O₁₃ crystalline sizes become smaller with the increase of annealing time. XPS analysis revealed that the energy position for all the samples was almost constant, but the broadening of the V_2p3/2 line of the annealed sample was due to the smaller crystal size of V₆O₁₃.     

Atomic transport during growth of ultrathin dielectrics on silicon

Atomic transport in thermal growth of thin and ultrathin silicon oxide, nitride, and oxynitride films on Si is reviewed. These films constitute the gate dielectrics, the “heart” of silicon metal-oxide-semiconductor field-effect transistor (MOSFET) and dynamic random-access memory (DRAM) devices, which are usually thermally grown on the active region of the semiconductor Si substrate. The drive of ultra-large scale integration towards the 0.18 μm channel length and below requires gate dielectrics with thicknesses of 3–4 nm and less, establishing new and very strict material requirements. Knowledge on an atomic scale of dielectric film growth promoted by thermally activated transport mechanisms is essential to the engineering of this fabrication step. In the case of thermal growth of silicon oxide films on Si in dry O₂, the mobile species is O₂ and growth is essentially a diffusion–reaction phenomenon. The thermal growth of silicon nitride and oxynitride films on Si in NH₃, NO and N₂O, on the other hand, involves catalytic dissociation of the original gas molecules at the surfaces and interfaces and diffusion–reaction of different resulting species, like NH₂, NH, H, N, NO, O, and O₂. Hydrogen transport and incorporation is a crucial, ubiquitous issue in thermally grown dielectric films on Si which is also addressed here. A recall is made of the physico-chemical constitution of the involved surfaces and interfaces for each different dielectric material, as well as complementary studies of the gas, gas-surface, and solid phase chemistry. An outline of the unique tools of isotopic substitution and high resolution depth profiling is included.     

Ellipsometric study of a-Be3N2 thin films prepared by radio frequency magnetron sputtering

The ellipsometric characterizations of amorphous beryllium nitride (a-Be₃N₂) thin films deposited on Si (1 0 0) and quartz at temperature <50 °C using reactive RF sputtering deposition were examined in the wavelength range 280-1600 nm. X-ray diffraction of the films showed no structure, suggesting the Be₃N₂ films grown on the substrates are amorphous. The composition and chemical structures of the amorphous thin films were determined by using electron spectroscopy for chemical analysis. The surface morphology of a-Be₃N₂ was characterized by atomic force microscopy. The thicknesses and optical constants of the films were derived from spectroscopic ellipsometry measurements. The variation of the optical constants with thickness of the deposited films has been investigated. From the angle dependence of the polarized reflectivity we deduced a Brewster angle of 64°. At any angle of incidence, the a-Be₃N₂ shown high transmissivity (80-99%) and low reflectivity (<18%) in the visible and near infrared regions. Hence, the a-Be₃N₂ could be a good candidate for antireflection optical coatings under conditions of optimized the type of polarization and the angle of incidence.     

Structural, electrical, and optical properties of ZnInO alloy thin films

Indium zinc oxide (IZO) thin films with different percentages of In content (In/[In+Zn]) are synthesized on glass substrates by magnetron sputtering, and the structural, electrical and optical properties of IZO thin films deposited at different In₂O₃ target powers are investigated. IZO thin films grown at different In₂O₃ target sputtering powers show evident morphological variation and different grain sizes. As the In₂O₃ sputtering power rises, the grain size becomes larger and electrical mobility increases. The film grown with an In₂O₃ target power of 100 W displays the highest electrical mobility of 13.5 cm·V^-1·s^-1 and the lowest resistivity of 2.4 × 10^-3 Ω·cm. The average optical transmittance of the IZO thin film in the visible region reaches 80% and the band gap broadens with the increase of In₂O₃ target power, which is attributed to the increase in carrier concentration and is in accordance with Burstein-Moss shift theory.     

Influence of a dopant source on the structural and optical properties of Mn doped ZnGa<Subscript>2</Subscript>O<Subscript>4</Subscript> thin films

Thin films of ZnGa₂O₄:Mn²⁺ were deposited on quartz substrates using an rf magnetron sputtering technique. The sputtering target, ZnGa₂O₄ doped with 2 at. % manganese, was synthesized by a high temperature solid state reaction. Two different dopant sources were used to incorporate the dopant ions into the target, namely, manganese acetate and manganese oxide. The structural and optical properties of the thin films were studied using XRD, PL and transmission spectra. Polycrystalline ZnGa₂O₄:Mn with a spinel structure could be grown at an optimized substrate–target distance even at room temperature. No luminescence was observed in the as-deposited films grown using (CH₃COO)₂Mn as the dopant source in the target. Substrate heating or post-deposition annealing in the reducing ambient didn’t impart any luminescence to the films, ruling out the possibility of Mn²⁺ incorporation in the films. However, when using MnO as the manganese source in the target, the as-deposited films exhibited green photoluminescent emission (peak maximum at 508 nm) for substrate temperatures at and above 500 °C. This suggests that, in thin films, Mn incorporation and subsequent luminescent outcome is strongly influenced by the dopant source, which is quite different from the bulk phosphor behavior. PACS 81.15.Cd; 78.55.-m; 85.60.-q     

Preparation and characterization of CrNxOy thin films: The effect of composition and structural features on the electrical behavior

Metallic oxynitrides have attracted the attention of several researchers in the last decade due to their versatile properties. Through the addition of a small amount of oxygen into a transition metal nitride film, the material's bonding states between ionic and covalent types can be tailored, thus opening a wide range of electrical, optical, mechanical and tribological responses. Among the oxynitrides, chromium oxynitride (CrN_xO_y) has many interesting applications in different technological fields. In the present work the electrical behavior of CrN_xO_y thin films, deposited by DC reactive magnetron sputtering, were investigated and correlated with their compositional and structural properties. The reactive gas flow, gas pressure, and target potential were monitored during the deposition in order to control the chemical composition, which depend strongly on reactive sputtering process. Depending on the particular deposition parameters that were selected, it was possible to identify three types of films with different growth conditions and physical properties. The electrical resistivity of the films, measured at room temperature, was found to depend strongly on the chemical composition of the samples.     

Magnetic and structural properties of nanocomposite Co-Ni-Cr-Al-Y-N thin films

The relation between structural and magnetic properties of Co-Ni-Cr-Al-Y-N thin films deposited by reactive r.f. magnetron sputtering was investigated. A marked change in the magnetic behaviour of the films with the different nitrogen partial pressure in the Ar/N₂ deposition atmosphere was observed and qualitatively explained in correlation with the phase composition. The nanocrystalline metal solid-solution obtained at low N₂ content and the nanocrystalline nitride/amorphous composite obtained at high N₂ content are not magnetic, whereas the amorphous phase produced for intermediate N₂ pressures behaves like a ferromagnetic semi-permanent material. The results demonstrate the possibility of modulating the magnetic properties of r.f. magnetron sputtered Co-Ni-Cr-Al-Y-N thin films, thus opening a new route for magnetic multilayer deposition. PACS 68.55.-a; 75.70.Ak; 75.75.+a; 85.70.-w     

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.