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.     

Effects of crystalline quality on the ultraviolet emission and electrical properties of the ZnO films deposited by magnetron sputtering

The ZnO films were deposited on c-plane sapphire, Si (0 0 1) and MgAl₂O₄ (1 1 1) substrates in pure Ar ambient at different substrate temperatures ranging from 400 to 750 °C by radio frequency magnetron sputtering. X-ray diffraction, photoluminescence and Hall measurements were used to evaluate the growth temperature and the substrate effects on the properties of ZnO films. The results show that the crystalline quality of the ZnO films improves with increasing the temperature up to 600 °C, the crystallinity of the films is degraded as the growth temperature increasing further, and the ZnO film with the best crystalline quality is obtained on sapphire at 600 °C. The intensity of the photoluminescence and the electrical properties strongly depend on the crystalline quality of the ZnO films. The ZnO films with the better crystallinity have the stronger ultraviolet emission, the higher mobility and the lower residual carrier concentration. The effects of crystallinity on light emission and electrical properties, and the possible origin of the n-type conductivity of the undoped ZnO films are also discussed.     

The role of oxygen and hydrogen partial pressures on structural and optical properties of ITO films deposited by reactive rf-magnetron sputtering

Sn doped In₂O₃ films are deposited by rf-magnetron sputtering at 300 °C under Ar, Ar + O₂ and Ar + H₂ gas ambients. For the film prepared under argon ambient, electrical resistivity 6.5 × 10⁻⁴ Ω cm and 95% optical transmission in the visible region have been achieved optimizing the power and chamber pressure during the film deposition. X-ray diffraction spectra of the ITO film reveal (2 2 2) and (4 0 0) crystallographic planes of In₂O₃. With the introduction of 1.33% oxygen in argon, (2 2 2) peak of In₂O₃ decreases and resistivity increases for the deposited film. With further increase of oxygen in the sputtering gas mixture crystallinity in the film deteriorates and both the peaks disappeared. On the other hand, when 1.33% hydrogen is mixed with argon, the resistivity of the deposited film decreases to 5.5 × 10⁻⁴ Ω cm and the crystallinity remains almost unchanged. In case of reactive sputtering, the deposition rate is lower compared to that in case of non-reactive sputtering. HRTEM and first Fourier patterns show the highly crystalline structure of the samples deposited under Ar and Ar + H₂ ambients. Crystallinity of the film becomes lower with the introduction of oxygen in argon but refractive index increases from 1.86 to 1.9. The surface morphology of the ITO films have been studied by high resolution scanning electron microscopy.     

Influence of substrate temperature on electrical and optical properties of p-type semitransparent conductive nickel oxide thin films deposited by radio frequency sputtering

Nickel oxide thin films were deposited on fused silica and Si(1 0 0) substrates at different substrate temperatures ranging from room temperature to 400 °C using radio frequency reactive magnetron sputtering from a Ni metal target in a mixture of O₂ and Ar. With the increase of substrate temperature, nickel oxide films deposited on the Si substrates exhibit transition from amorphous to poly-crystalline structures with different preferred orientations of NiO(2 0 0) and (1 1 1). The films deposited at higher temperature exhibit higher Ni²⁺/Ni³⁺ ratio. With substrate temperature increasing from room temperature to 400 °C, the electrical resistivities of nickel oxide films increase from (2.8 ± 0.1) × 10⁻² to (8.7 ± 0.1) Ω cm, and the optical band-gap energies increase from 3.65 to 3.88 eV. A p-nickel oxide/n-zinc oxide heterojunction was fabricated to confirm the p-type conduction of nickel oxide thin film, which exhibited a steadily rectifying behavior.     

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 substrate temperature and post-treatment on the properties of ZnO:Al thin films prepared by pulsed laser deposition

Highly transparent conductive Al₂O₃ doped zinc oxide (AZO) thin films have been deposited on the glass substrate by pulsed laser deposition technique. The effects of substrate temperature and post-deposition annealing treatment on structural, electrical and optical properties of AZO thin films were investigated. The experimental results show that the electrical resistivity of films deposited at 240 °C is 6.1 × 10⁻⁴ Ω cm, which can be further reduced to as low as 4.7 × 10⁻⁴ Ω cm by post-deposition annealing at 400 °C for 2 h in argon. The average transmission of AZO films in the visible range is 90%. The optical direct band gap of films was dependent on the substrate temperature and the annealing treatment in argon. The optical direct band gap value of AZO films increased with increasing annealing temperature.     

Effects of substrate temperature and Zn addition on the properties of Al-doped ZnO films prepared by magnetron sputtering

Al-doped ZnO (AZO) films prepared at different substrate temperature and AZO films with intentional Zn addition (ZAZO) during deposition at elevated substrate temperature were fabricated by radio frequency magnetron sputtering on glass substrate, and the resulting structural, electrical, optical properties together with the etching characteristics and annealing behavior were comparatively examined. AZO films deposited at 150 °C showed the optimum electrical properties and the largest grain size. XPS analysis revealed that AZO films deposited at elevated temperature of 450 °C contained large amount of Al content due to Zn deficiency, and that intentional Zn addition during deposition could compensate the deficiency of Zn to some extent. It was shown that the electrical, optical and structural properties of ZAZO films were almost comparable to those of AZO film deposited at 150 °C, and that ZAZO films had much smaller etching rate together with better stability in severe annealing conditions than AZO films due possibly to formation of dense structure.     

Effect of annealing temperature on the decomposition of reactively sputtered Ag2Cu2O3 films

Ag₂Cu₂O₃ films were deposited on glass substrates by reactive sputtering of a composite silver-copper target. The deposited films were annealed in air at 100, 200 and 300 °C. The structure of the films was studied using X-ray diffraction (XRD), their surface morphology was characterised using scanning electron microscopy (SEM) and their electrical resistivity at room temperature was measured using the four point probe method. The 100 °C annealing did not modify either the film structure or the film morphology. On the other hand, Ag₂Cu₂O₃ films were partially decomposed into Ag and CuO after a 200 °C annealing. The decomposition was complete for a 300 °C annealing. The evolution of the film surface morphology as a function of the annealing temperature was discussed in connection to the evolution of the molar volume of the phases constituting the films.     

Effect of sputtering anisotropic ejection on the optical properties and residual stress of Nb2O5 thin films

The effect of sputtering anisotropic ejection on the optical properties and internal stress of niobium pentoxide (Nb₂O₅) films prepared by ion-beam sputtering deposition (IBSD) was investigated experimentally. Thin films were deposited on unheated BK7 glass substrates and silicon wafers at different ejection angles surrounding a metal target. The ejection angles varied from 0° to 75° in increments of 15° for each substrate. It was found that the optical constants of the Nb₂O₅ films were significantly influenced by the sputtering ejection angle. The surface roughness and residual stress in the Nb₂O₅ thin films were also found to vary with the ejection angle. In this work, Nb₂O₅ films had a higher refractive index, lower absorption, lower stress and lower roughness when films deposited at an ejection angle of 30°.     

Structure and electrical properties of CdIn2O4 thin films prepared by DC reactive magnetron sputtering

CdIn₂O₄ thin films were prepared by direct-current (DC) reactive magnetron sputtering. The structure, surface morphology and the chemical composition of the thin films were analyzed by X-ray diffraction (XRD), atomic force microscope (AFM) and X-ray photoelectron spectroscopy (XPS), respectively. The electrical properties of the films prepared in different oxygen concentration and annealing treatment were determined, and the effects of the preparing conditions on the structure and electrical properties were also explored. It indicates that the CdIn₂O₄ thin films with uniform and dense surface morphology contain mainly CdIn₂O₄, In₂O₃ phases, and CdO phase is also observed. The XPS analysis confirms the films are in oxygen-deficient state. The electrical properties of these films significantly depend on the preparing conditions, the resistivity of the films with the oxygen concentration of 4.29% is 2.95 × 10⁻⁴ Ω cm and the Hall mobility is as high as 60.32 cm²/V s. Annealing treatment can improve the electrical performance of the films.     

Effects of the sputtering time of ZnO buffer layer on the quality of GaN thin films

ZnO thin films with different thickness (the sputtering time of ZnO buffer layers was 10 min, 15 min, 20 min, and 25 min, respectively) were first prepared on Si substrates using radio frequency magnetron sputtering system and then the samples were annealed at 900 °C in oxygen ambient. Subsequently, a GaN epilayer about 500 nm thick was deposited on ZnO buffer layer. The GaN/ZnO films were annealed in NH₃ ambient at 950 °C. X-ray diffraction (XRD), atom force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL) were used to analyze the structure, morphology, composition and optical properties of GaN films. The results show that their properties are investigated particularly as a function of the sputtering time of ZnO layers. For the better growth of GaN films, the optimal sputtering time is 15 min.     

The influence of substrate on the properties of Er2O3 films grown by magnetron sputtering

The structural properties and the room temperature luminescence of Er₂O₃ thin films deposited by RF magnetron sputtering have been studied. Films characterized by good morphological properties have been obtained by using a SiO₂ interlayer between the film and the Si substrate. The evolution of the properties of the Er₂O₃ films due to rapid thermal annealing processes in O₂ ambient performed at temperatures in the range 800-1200 °C has been investigated in details. The existence of well-defined annealing conditions (temperature of 1100 °C or higher) allowing to avoid the occurrence of extensive chemical reactions with the oxidized substrate has been demonstrated and an increase of the photoluminescence (PL) intensity by about a factor of 40 with respect to the as deposited material has been observed. The enhanced efficiency of the photon emission process has been correlated with the longer lifetime of the PL signal. The same annealing processes are less effective when Er₂O₃ is deposited on Si. In this latter case interfacial reactions and pit formation occur, leading to a material characterized by stronger non-radiative phenomena that limit the PL efficiency.     

Effect of composition and deposition temperature on the characteristics of Ga doped ZnO thin films

ZnO films doped with Ga (GZO) of varying composition were prepared on Corning glass substrate by radio frequency magnetron sputtering at various deposition temperatures of room temperature, 150, 250 and 400 °C, and their temperature dependent photoelectric and structural properties were correlated with Ga composition. With increasing deposition temperature, the Ga content, at which the lowest electrical resistivity and the best crystallinity were observed, decreased. Films with optimal electrical resistivity of 2-3 × 10⁻⁴ Ω cm and with good crystallinity were obtained in the substrate temperature range from 150 to 250 °C, and the corresponding C_Ga/(C_Ga + C_Zn) atomic ratio was about 0.049. GZO films grown at room temperature had coarse columnar structure and low optical transmittance, while films deposited at 400 °C yielded the highest figure of merit (FOM) due to very low optical absorption despite rather moderate electrical resistivity slightly higher than 4 × 10⁻⁴ Ω cm. The optimum Ga content at which the maximum figure of merit was obtained decreased with increasing deposition temperature.     

Preparation of Cu2ZnSnS4 thin films by hybrid sputtering

In order to fabricate Cu₂ZnSnS₄ thin films, hybrid sputtering system with two sputter sources and two effusion cells is used. The Cu₂ZnSnS₄ films are fabricated by the sequential deposition of metal elements and annealing in S flux, varying the substrate temperature. The Cu₂ZnSnS₄ films with stoichiometric composition are obtained at the substrate temperature up to 400 °C, whereas the film composition becomes quite Zn-pool at the substrate temperature above 450 °C. The Cu₂ZnSnS₄ film shows p-type conductivity, and the optical absorption coefficient and the band gap of the Cu₂ZnSnS₄ film prepared in this experiment are suitable for fabricating a thin film solar cell.     

Synthesis and materials properties of transparent conducting In2O3 films prepared by sol-gel-spin coating technique

Transparent conducting indium oxide (In₂O₃) thin films have been prepared on glass substrates by the simple sol-gel-spin coating technique. These films have been characterized by X-ray diffraction, resistivity and Hall effect measurements, optical transmission, scanning electron microscopy and atomic force microscopy for their structural, electrical, optical and morphological properties. The influence of spin parameters, number of coating, process temperature on the quality of In₂O₃ films are studied. In the operating range of deposition, 400-475 °C, all the films showed predominant (2 2 2) orientation. Films deposited at optimum process conditions exhibited a resistivity of 2×10⁻² Ω cm along with the average transmittance of about 80% in the visible spectral range (400-700 nm).     

Highly thermal stable transparent conducting SnO2:Sb epitaxial films prepared on α-Al2O3 (0 0 0 1) by MOCVD

Antimony-doped tin oxide (SnO₂:Sb) single crystalline films have been prepared on α-Al₂O₃ (0 0 0 1) substrates by metal organic chemical vapor deposition (MOCVD). The antimony doping was varied from 2% to 7% (atomic ratio). Post-deposition annealing of the SnO₂:Sb films was carried out at 700-1100 °C for 30 min in atmosphere ambient. The effect of annealing on the structural, electrical and optical properties of the films was investigated in detail. All the SnO₂:Sb films had good thermal stability under 900 °C, and the 5% Sb-doped SnO₂ film exhibited the best opto-electrical properties. Annealed above 900 °C, the 7% Sb-doped SnO₂ film still kept high thermal stability and showed good electrical and optical properties even at 1100 °C.     

Structure and electrical transport properties of bismuth thin films prepared by RF magnetron sputtering

Bismuth thin films were prepared on glass substrates with RF magnetron sputtering and the effects of deposition temperature on surface morphology and their electrical transport properties were investigated. Grain growth of bismuth and the coalescence of grains were observed above 393 K with field emission secondary electron microscopy. Continuous thin films could not be obtained above 448 K because of the segregation of grains. Hall effect measurements showed that substrate heating yields the decrease of carrier density and the increase of mobility in exponential ways until 403 K. Resistivity of sputter deposited bismuth films has its minimum (about 0.7 × 10⁻³ Ω cm) in range of 403-433 K. Annealing of bismuth films deposited at room temperature was carried out in a radiation furnace with flowing hydrogen gas. The change of resistivity was not significant due to the cancellation of the decrease of carrier density and the increase of mobility. However, the abrupt change of electrical properties of film annealed above 523 K was observed, which is caused by the oxidation of bismuth layer.     

Effects of the substrate temperature on the properties of CuIn5S8 thin films

Structural, optical and electrical properties of CuIn₅S₈ thin films grown by thermal evaporation have been studied relating the effects of substrate heating conditions of these properties. The CuIn₅S₈ thin films were carried out at substrate temperatures in the temperature range 100-300 °C. The effects of heated substrate on their physico-chemical properties were investigated using X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX), optical transmission and hot probe method. X-ray diffraction revealed that the films are strong preferred orientation along the (3 1 1) plane upon substrate temperature 200 °C and amorphous for the substrate temperatures below 200 °C. No secondary phases are observed for all the films. The composition is greatly affected by heated substrate. From the optical transmission and reflection, an important absorption coefficient exceeds 10⁵ cm⁻¹ at 800 nm was found. As increasing the substrate temperature, the optical energy band gap decreases from 1.70 eV for the unheated films to 1.25 eV for the deposited films at 300 °C. It was found that CuIn₅S₈ thin film is an n-type semiconductor at 250° C.     

Effect of environment and heat treatment on the optical properties of RF-sputtered SnO2 thin films

Thin films of SnO₂ were deposited by RF-magnetron sputtering on quartz substrates at room temperature in an environment of Ar and O₂. The XRD pattern shows amorphous nature of the as-deposited films. The optical properties were studied using the reflectance and transmittance spectra. The estimated optical band gap (E_g) values increase from 4.15 to 4.3 eV as the Ar gas content decreases in the process gas environment. The refractive index exhibits an oscillatory behavior that is strongly dependent on the sputtering gas environment. The Urbach energy is found to decrease with increase in band gap. The band gap is found to decrease on annealing the film. The role of oxygen defects is explored in explaining the variation of optical parameters.     

Structural properties and electrical characteristics of high-k Dy2O3 gate dielectrics

This paper describes the structural properties and electrical characteristics of thin Dy₂O₃ dielectrics deposited on silicon substrates by means of reactive sputtering. The structural and morphological features of these films after postdeposition annealing were studied by X-ray diffraction and X-ray photoelectron spectroscopy. It is found that Dy₂O₃ dielectrics annealed at 700 °C exhibit a thinner capacitance equivalent thickness and better electrical properties, including the interface trap density and the hysteresis in the capacitance-voltage curves. Under constant current stress, the Weibull slope of the charge-to-breakdown of the 700 °C-annealed films is about 1.6. These results are attributed to the formation of well-crystallized Dy₂O₃ structure and the reduction of the interfacial SiO₂ layer.