Effect of substrate temperature on the growth of ITO thin films

Indium tin oxide (ITO) thin films were deposited onto glass substrates by rf magnetron sputtering of ITO target and the influence of substrate temperature on the properties of the films were investigated. The structural characteristics showed a dependence on the oxygen partial pressure during sputtering. Oxygen deficient films showed (4 0 0) plane texturing while oxygen-incorporated films were preferentially oriented in the [1 1 1] direction. ITO films with low resistivity of 2.05 × 10⁻³ Ω cm were deposited at relatively low substrate temperature (150 °C) which shows highest figure of merit of 2.84 × 10⁻³ square/Ω⋅     

Optimization of parameters for deposition of Ga-doped ZnO films by DC reactive magnetron sputtering using Taguchi method

Ga-doped ZnO (ZnO:Ga) transparent conductive films were deposited on glass substrates by DC reactive magnetron sputtering. Taguchi method was used to find the optimal deposition parameters including oxygen partial pressure, argon partial pressure, substrate temperature, and sputtering power. By employing the analysis of variance, we found that the oxygen and argon partial pressures were the most influencing parameters on the electrical properties of ZnO:Ga films. Under the optimized deposition conditions, the ZnO:Ga films showed acceptable crystal quality, lowest electrical resistivity of 2.61 × 10⁻⁴ Ω cm, and high transmittance of 90% in the visible region.     

A study of the optical properties of titanium oxide films prepared by dc reactive magnetron sputtering

TiO₂ thin films were deposited on the glass substrates by dc reactive magnetron sputtering technique at different sputtering pressures (2 × 10⁻³ to 2 × 10⁻² mbar). The films prepared at low pressures have an anatase phase, and the films prepared at high pressures have an amorphous phase. The optical properties were studied by measuring the transmittance and the ellipsometric spectra. The optical constants of the films in the visible range were obtained by fitting the transmittance combined with the ellipsometry measurements using the classical model with one oscillator. The refractive index of the films decreases from 2.5 until 2.1 as the sputtering pressure increases from 2 × 10⁻³ to 2 × 10⁻² mbar. The films prepared at the pressure higher than 6 × 10⁻³ mbar show a volume inhomogeneity. This volume inhomogeneity has been calculated by fitting the transmittance and the ellipsometric spectra. The volume inhomogeneity of the film prepared at the highest sputtering pressure is about 10%. Although the films prepared at high pressures show a large volume inhomogeneity, they have low extinction coefficients. It is suggested that the anatase phase results in more light scattering than amorphous phase does, and then a high extinction coefficient.     

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.     

Indium zinc oxide thin films deposited by sputtering at room temperature

The deposition of amorphous indium zinc oxide (IZO) thin films on glass substrates with n-type carrier concentrations between 10¹⁴ and 3 × 10²⁰ cm⁻³ by sputtering from single targets near room temperature was investigated as a function of power and process pressure. The resistivity of the films with In/Zn of ∼0.7 could be controlled between 5 × 10⁻³ and 10⁴ Ω cm by varying the power during deposition. The corresponding electron mobilities were 4-18 cm² V⁻¹ s⁻¹.The surface root-mean-square roughness was <1 nm under all conditions for film thicknesses of 200 nm. Thin film transistors with 1 μm gate length were fabricated on these IZO layers, showing enhancement mode operation with good pitch-off characteristics, threshold voltage 2.5 V and a maximum transconductance of 6 mS/mm. These films look promising for transparent thin film transistor applications.     

Deposition of sputtered iridium oxide—Influence of oxygen flow in the reactor on the film properties

Thin films of iridium oxide have been deposited by reactive magnetron sputtering. The influence of oxygen partial pressure in the sputtering plasma on the composition, surface structure and morphology of the films has been studied by XRD, SEM and AFM analysis. An optimal combination of sputtering parameters yields stable microporous amorphous films with highly extended fractal surface. The electrochemical properties of these films have been investigated in view of their application as catalysts for water splitting, using the electrochemical techniques of cyclovoltammetry, electrochemical impedance spectroscopy, and steady state polarization. The SIROFs have shown an excellent electrochemical reversibility and a high catalytic activity toward the oxygen evolution reaction in 0.5 M H₂SO₄. A current density of 150 mA cm⁻² at potential of 1.7 V (versus Ag/AgCl) has been obtained at catalyst load of only 100 μg cm⁻². These results combined with the established long-term mechanical stability of the sputtered iridium oxide films (SIROFs) proved the advantages of the reactive magnetron sputtering as simple and reliable method for preparation of catalysts with precisely controlled composition, loading, and surface characteristics.     

Growth of Ga-doped ZnO films with ZnO buffer layer by sputtering at room temperature

Gallium-doped zinc oxide films have been grown on glass substrates with and without ZnO buffer layers by r.f. magnetron sputtering at room temperature. In this approach, the grey relational Taguchi method analysis is adopted to solve the coating process with multiple deposition qualities. Optimal coating parameters can then be determined by using the gray relational grade as a performance index. The GZO coating parameters (r.f. power, sputtering pressure, O₂/(Ar+O₂) flow-rate ratios, and deposition time) are optimized, by taking into account the multiple performance characteristics (structural, morphological, deposition rate, electrical resistivity, and optical transmittance). The results indicate that with the grey relational Taguchi method, the electrical resistivity of GZO films is reduced from 9.23×10⁻³ to 5.77×10⁻³ Ω cm and optical transmittance increases from 79.42% to 82.95%, respectively. The ZnO buffer layer can reduce the electrical resistivity of GZO films from 5.77×10⁻³ to 2.38×10⁻³ Ω cm. It can be anticipated that room temperature deposition enables film deposition onto polymeric substrates for flexible optoelectronic devices.     

Low temperature ITO thin film deposition on PES substrate using pulse magnetron sputtering

Experiments were conducted using pulse magnetron sputtering (PMS) to deposit transparent conducting indium tin oxide (ITO) thin film onto flexible polyethersulfone (PES) plastic substrates. The thin film microstructure, optoelectronic and residual stress were analyzed using the modulating PMS power, work pressure, pulse frequency, duty cycle and cycle time process parameters. The residual stress of the thin film was determined by scanning electron microscopy (SEM) combined with the Sony equation. The experimental results show that PMS has a lower process temperature, higher deposition rate and lower resistivity compared with the radio frequency process at the same output power. The duty cycle increase produces the optimum optoelectronic characteristics. When the pressure, power, duty cycle and sputter time are increased, the thin film stress will also increase, causing flexural distortion in the PES plastic substrate. When the deposition thickness reaches 1.5 μm, ITO thin film will appear with a distinct split. Under 5 mtorr work pressure, 60 W power, 33 μs duty time and 2 μs pulse reverse time at duty cycle 95%, thin film with an optimized electrical 3.0 × 10⁻⁴ Ω-cm, RMS surface roughness of 0.85 nm and visible region optical transmittance will be achieved with acquisition of over 85%.     

Development of structural and optical properties of WOx films upon increasing oxygen partial pressure during reactive sputtering

WO_x films were prepared by reactive dc magnetron sputtering using tungsten target. Sputtering was carried out at a total pressure of 1.2 Pa using a mixture of argon plus oxygen in an effort to determine the influence of the oxygen partial pressure on structural and optical properties of the films. The deposition rate decreases significantly as the surface of the target is oxidized. X-Ray diffraction revealed the amorphous nature of all the films prepared at oxygen partial pressures higher than 1.71×10⁻³ Pa. For higher oxygen partial pressures, fully transparent films were deposited, which showed a slight increase in optical band gap with increasing oxygen partial pressure, while the refractive index was simultaneously decreased.     

Properties of dc magnetron sputtered Cu2O films prepared at different sputtering pressures

The sputtering pressures maintained during the deposition of Cu₂O films, by dc reactive magnetron sputtering, influence the structural, electrical and optical properties. The crystalline orientation mainly depends on the sputtering pressure. The films deposited at a sputtering pressure of 4 Pa showed single-phase Cu₂O films along (1 1 1) direction. The electrical resistivity of the films increased from 1.1 × 10¹ Ω cm to 3.2 × 10³ Ω cm. The transmittance of the films increased from 69% to 88% with the increase of sputtering pressure from 2.5 Pa to 8 Pa.     

Transparent conducting molybdenum-doped zinc oxide films deposited by RF magnetron sputtering

A new transparent conducting oxide (TCO) film with low resistivity and high transmittance in the visible range, molybdenum-doped zinc oxide (MZO), was successfully prepared by RF magnetron sputtering method on glass substrates at room temperature. The structural, electrical, and optical properties as a function of film thickness were investigated. All the samples have a preferred orientation with the (0 0 2) planes parallel to the substrates. The resistivity initially decreases and then shows an increase with the increase of the film thickness. When the thickness is 400 nm, the film has its best crystallinity and lowest resistivity 9.2 × 10⁻⁴ Ω cm with a Hall mobility of 30 cm² V⁻¹ s⁻¹ and a carrier concentration of 2.3 × 10²⁰ cm⁻³. The average transmittance in the visible range exceeds 84% for all thickness films.     

Effect of substrate bias voltages on the diffusion barrier properties of Zr-N films in Cu metallization

Zr-N diffusion barriers were deposited on the Si substrates by rf reactive magnetron sputtering under various substrate bias voltages. Cu films were subsequently sputtered onto the Zr-N films by dc pulse magnetron sputtering without breaking vacuum. The Cu/Zr-N/Si specimens were then annealed up to 650 °C in N₂ ambient for an hour. The effects of deposition bias on growth rate, film resistivity, microstructure, and diffusion barrier properties of Zr-N films were investigated. An increase in negative substrate bias resulted in a decrease in deposition rate together with a decrease in resistivity. It was found that the sheet resistances of Cu/Zr-N(−200 V)/Si contact system were lower than those of Cu/Zr-N(−50 V)/Si specimens after annealing at 650 °C. Cu/Zr-N(−200 V)/Si contact systems showed better thermal stability so that the Cu₃Si phase could not be detected.     

Structure and properties of GZO thin films grown on ZnO buffer layers

Thin gallium-doped zinc oxide (in GZO the Ga₂O₃ contents are approximately 3 wt%) films having different ZnO buffer layers were deposited using radio frequency (rf) magnetron sputtering. The use of a grey-based Taguchi method to determine the processing parameters of ZnO buffer layer deposition has been studied by considering multiple performance characteristics. A Taguchi method with an L₉ orthogonal array, signal-to-noise (S/N) ratio, and analysis of variance (ANOVA) is employed to investigate the performance characteristics in the deposition operations. The effect and optimization of ZnO buffer deposition parameters (rf power, sputtering pressure, thickness, and annealing) on the structure, morphology, electrical resistivity, and optical transmittance of the GZO films are studied. Annealing treatment and reduction in thickness resulted in a decrease in root-mean-square (RMS) surface roughness of the ZnO buffer layer. Using the optimal ZnO buffer layer obtained by the application of the grey-based Taguchi method, the electrical resistivity of GZO films was decreased from 2.94×10⁻³ to 9.44×10⁻⁴ Ω cm and the optical transmittance in the visible region was slightly increased from 84.81% to 85.82%.     

The luminescence and optoelectrical properties of ITO films prepared by a sputter type negative metal ion deposition

Transparent conducting indium tin oxide (ITO) thin films were prepared on glass substrates by a magnetron sputter type negative ion source which requires cesium (Cs) vapor injection for surface negative ionization on the ITO target surface. Although the film was prepared at 70 °C, it attained high optical transmittance, 88% and low resistivity, 2.03 × 10⁻⁴ Ω cm, at an optimized Cs partial pressure of P_Cs = 1.7 × 10⁻³ Pa. The as-deposited ITO films have a poly-crystalline structure with (2 1 1), (2 2 2), (4 0 0), (4 1 1) and (4 4 0) reflections.Also, ITO films prepared at P_Cs = 1.7 × 10⁻³ Pa were post-deposition vacuum annealed at 300 °C for 30 min. The films had a resistivity of 1.8 × 10⁻⁴ Ω cm and a transparency of 89.2%. The post-deposition vacuum annealed ITO film was used as an anode for a transparent organic light emitting diode (TOLED). A maximum luminance of 19,000 cd/m² was obtained.     

Electrical and structural properties of In-doped ZnO films deposited by RF superimposed DC magnetron sputtering system

Zinc-indium-oxide (ZIO) films were deposited on non-alkali glass substrates by RF superimposed DC magnetron sputtering with a ZIO (9.54 wt% In₂O₃ content) high-density, sintered target at room temperature. The electrical, structural and optical properties of the ZIO films deposited with different sputtering parameters were examined. The total power for RF superimposed DC magnetron sputtering was 80 W. The RF power ratio in the total sputtering power was changed from 0 to 100% in steps of 25%. The ZIO films deposited with a 100% RF discharge showed the lowest resistivity, 1.28×10⁻³ Ω cm, due to the higher carrier concentration. The ZIO film deposited at 50% RF power showed a relatively larger grain size and smaller FWHM. XPS suggested an increase in the level of In³⁺ substitution for Zn²⁺ in the ZnO lattice with increasing RF/(DC+RF) due to the low damage process. The average transmittance of all ZIO films in the visible light region was >80%. The increasing RF power portion of the total sputtering power led to a broadening of the optical band gap, which was attributed to the increase in carrier density according to Burstein-Moss shift theory.     

Mechanical reliability of transparent conducting IZTO film electrodes for flexible panel displays

The mechanical reliability of transparent In-Zn-Sn-O (IZTO) films grown using pulsed DC magnetron sputtering with a single oxide alloyed ceramic target on a transparent polyimide (PI) substrate at room temperature is investigated. All IZTO films deposited at room temperature have an amorphous structure. However, their optical and electrical properties change depending on the oxygen partial pressure applied during depositing process. At an oxygen partial pressure of 3%, the films exhibit a resistivity of 8.3 × 10⁻⁴ Ω cm and an optical transmittance of 86%. Outer bending tests show that the critical bending radius decreases from 10 mm to 7.5 mm when the oxygen partial pressure increases from 1% to 3%. In the inner bending test, the critical bending radius is independent of oxygen partial pressure at 3.5 mm, indicating excellent film flexibility. In the dynamic fatigue test, the electrical resistance of the films reduces by less than 1% for more than 2000 bending cycles. These results suggest that IZTO films have excellent mechanical durability and flexibility in comparison to ITO films.     

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.     

Structural and transport properties of cubic spinel ZnCo2O4 thin films grown by reactive magnetron sputtering

We report on the growth of cubic spinel ZnCo₂O₄ thin films by reactive magnetron sputtering and bipolarity of their conduction type by tuning of oxygen partial pressure ratio in the sputtering gas mixture. Crystal structure of zinc cobalt oxide films sputtered in an oxygen partial pressure ratio of 90% was found to change from wurtzite Zn_1−xCo_xO to spinel ZnCo₂O₄ with an increase of the sputtering power ratio between the Co and Zn metal targets, D_Co/D_Zn, from 0.1 to 2.2. For a fixed D_Co/D_Zn of 2.0 yielding single-phase spinel ZnCo₂O₄ films, the conduction type was found to be dependent on the oxygen partial pressure ratio: n-type and p-type for the oxygen partial pressure ratio below ∼70% and above ∼85%, respectively. The electron and hole concentrations for the ZnCo₂O₄ films at 300 K were as high as 1.37×10²⁰ and 2.81×10²⁰ cm⁻³, respectively, with a mobility of more than 0.2 cm²/V s and a conductivity of more than 1.8 S cm⁻¹.     

Deposition of quasi-crystal Al-doped ZnO thin films for photovoltaic device applications

Quasi-crystal aluminum-doped zinc oxide (AZO) films were prepared by in situ radio frequency (RF) magnetron sputtering (sputtering without annealing) on glass substrates. The influence of deposition parameters on the optoelectronic and structural properties of the in situ deposited quasi-crystal AZO films was investigated in order to compare resulting samples. X-ray diffraction (XRD) patterns show that the quasi-crystal AZO thin films have excellent crystallization improved with increase of the RF power and substrate temperature, with an extremely preferential c-axis orientation exhibit sharp and narrow XRD pattern similar to that of single-crystal. Field emission scanning electron microscopy (FESEM) images show that quasi-crystal AZO thin films have uniform grains and the grain size increase with the increase of RF power and substrate temperature. Craters of irregular size with the columnar structure are observed in the quasi-crystal AZO thin films at a lower substrate temperature while many spherical shaped grains appeared at a higher substrate temperature. The average optical transmittance of all the quasi-crystal AZO films was over 85% in the 400-800 nm wavelength range. The resistivity of 4.176 × 10⁻⁴ Ω cm with the grain size of 76.4891 nm was obtained in the quasi-crystal AZO thin film deposited at 300 °C, under sputtering power of 140 W.     

Rapid thermal annealing of ITO films

Tin-doped indium oxide (ITO) films with 200 nm thickness were deposited on glass substrates by DC magnetron sputtering at room temperature. And they were annealed by rapid thermal annealing (RTA) method in vacuum ambient at different temperature for 60 s. The effect of annealing temperature on the structural, electrical and optical properties of ITO films was investigated. As the RTA temperature increases, the resistivity of ITO films decreases dramatically, and the transmittance in the visible region increases obviously. The ITO film annealed at 600 °C by RTA in vacuum shows a resistivity of 1.6 × 10⁻⁴ Ω cm and a transmittance of 92%.