Deposition and properties of B-N codoped p-type ZnO thin films by RF magnetron sputtering

B-N codoped p-type ZnO thin films have been realized by radio frequency (rf) magnetron sputtering using a mixture of argon and oxygen as sputtering gas. Types of conduction and electrical properties in codoped ZnO films were found to be dependent on oxygen partial pressure ratios in the sputtering gas mixture. When oxygen partial pressure ratio was 70%, the codoped ZnO film showed p-type conduction and had the best electrical properties. Additionally, the p-ZnO/n-Si heterojunction showed a clear p-n diode characteristic. XRD results indicate that the B-N codoped ZnO film prepared in 70% oxygen partial pressure ratio has high crystal quality with (0 0 2) preferential orientation. Meanwhile, the B-N codoped ZnO film has high optical quality and displays the stronger near band edge (NBE) emission in the temperature-dependent photoluminescence spectrum, the acceptor energy level was estimated to be located at 125 meV above the valence band.     

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.     

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.     

Ultra smooth NiO thin films on flexible plastic (PET) substrate at room temperature by RF magnetron sputtering and effect of oxygen partial pressure on their properties

Transparent p-type nickel oxide thin films were grown on polyethylene terephthalate (PET) and glass substrates by RF magnetron sputtering technique in argon + oxygen atmosphere with different oxygen partial pressures at room temperature. The morphology of the NiO thin films grown on PET and glass substrates was studied by atomic force microscope. The rms surface roughnesses of the films were in the range 0.63-0.65 nm. These ultra smooth nanocrystalline NiO thin films are useful for many applications. High resolution transmission electron microscopic studies revealed that the grains of NiO films on the highly flexible PET substrate were purely crystalline and spherical in shape with diameters 8-10 nm. XRD analysis also supported these results. NiO films grown on the PET substrates were found to have better crystalline quality with fewer defects than those on the glass substrates. The sheet resistances of the NiO films deposited on PET and glass substrates were not much different; having values 5.1 and 5.3 kΩ/□ and decreased to 3.05, 3.1 kΩ/□ respectively with increasing oxygen partial pressure. The thicknesses of the films on both substrates were ∼700 nm. It was also noted that further increase in oxygen partial pressure caused increase in resistivity due to formation of defects in NiO.     

Effect of ambient gas on structural and optical properties of titanium oxynitride films

Titanium oxynitride films have been deposited on glass substrates by reactive RF magnetron sputtering of titanium target. The influence of oxygen partial pressure in N₂ + Ar and N₂ + He mixtures was examined on structural and optical properties of titanium oxynitride films. The prepared samples were characterized by X-ray diffraction, EDS, surface profilometer, AFM and contact angle measurement system. With increase in oxygen partial pressure, the grain size decreases from ∼70 nm to ∼50 nm in N₂ + Ar mixture, while from ∼60 nm to ∼37 nm in N₂ + He mixture. The thickness calculated from optical transmission data and surface profilometer is in good agreement with each other. The deposited samples are hydrophobic by nature and the contact angle was found to decrease with increase in oxygen partial pressure. Samples prepared in oxygen partial pressure ≥5.5% show transmittance of about 97% in the visible region of the spectrum in both N₂ + Ar and N₂ + He mixtures. The atomic mass of the sputtering gas (Ar and He) significantly affects the primary crystallite size, orientation as well as band gap. We were able to relate the better crystallisation of titanium atoms with low partial pressure of oxygen when films are deposited in helium instead of argon due to Penning ionization.     

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.     

Effects of oxygen partial pressure and substrate temperature on the structure and optical properties of MgxZn1−xO thin films prepared by magnetron sputtering

Deposited with different oxygen partial pressures and substrate temperatures, Mg_xZn_1−xO thin films were prepared using a Mg_0.6Zn_0.4O ceramic target by magnetron sputtering. The structural and optical properties of the prepared thin films were investigated. The X-ray diffraction spectra reveal that all the films on quartz substrate are grown along (2 0 0) orientation with cubic structure. The lattice constant decreases and the crystallite size increases with the increase of substrate temperature. Both energy dispersive X-ray spectroscopy and calculated results suggest the ratio of Mg/Zn increases with increasing substrate temperature. The thin film deposited with T_s = 500 °C has a minimal rms roughness of 7.37 nm. The transmittance of all the films is higher than 85% in the visual region. The optical band gap is not sensitive to the oxygen partial pressure, while it increases from 5.63 eV for T_s = 100 °C to 5.95 eV for T_s = 700 °C. In addition, the refractive indices calculated from transmission spectra are sensitive to the substrate temperature. The photoluminescence spectra of Mg_xZn_1−xO thin films excited by 330 nm ultraviolet light indicate that the peak intensity of the spectra is influenced by the oxygen partial pressure and substrate temperature.     

Structural and magnetic properties of NiZn ferrite films with high saturation magnetization deposited by magnetron sputtering

NiZn ferrite films with well-defined spinel crystal structure were in situ fabricated by radio frequency magnetron sputtering at room temperature. The microstructures and static magnetic properties of the films’ dependence on the partial pressure ratio of argon to oxygen gas were investigated. Scanning electron microscope images indicated that all the films consisted of particles nanocrystalline in nature and the sizes increase as the ratio increases in the range of 10-25 nm. A large saturation magnetization (237.2 emu/cm³) and a minimum of coercivity (68 Oe) were obtained when the ferrite film was deposited in the ratio of 4:1. The complex permeability values (μ = μ′−iμ″) of the film were measured at frequency up to 5 GHz. It was shown that the film exhibited a large real part of permeability μ′ of 18 and a very high resonance frequency f_r of 1.2 GHz. The results suggested that the NiZn ferrite film as-deposited in the ratio of 4:1 may be promised as magnetic medium in the application of integrated circuits operating at microwave frequencies.     

Influence of charged particle bombardment and sputtering parameters on the properties of HfO2 films prepared by dc reactive magnetron sputtering

HfO₂ films prepared on glass substrates by dc reactive magnetron sputtering in an Ar + O₂ atmosphere are investigated. The films are polycrystallized with a pure monoclinic phase, and the crystallization strongly relates to the technology environment. Charged particle bombardment mainly caused by negative oxygen ions during sputtering on the films results in rougher surface morphology and worse crystalline property. Influence of sputtering pressure, substrate temperature and Ar:O₂ flow ratio is studied. The main orientations of the films are (−1 1 1) and (1 1 1). The (−1 1 1) orientation is stable, but (1 1 1) orientation is very sensitive to the sputtering condition, and it can be suppressed effectively by introducing charged particle bombardment, lowing sputtering pressure and increasing oxygen concentration.     

Structure, magnetic and magnetostrictive properties of as-deposited Fe-Ga thin films

Polycrystalline Fe_100−xGa_x (19?x?23) films were grown on Si(1 0 0) substrates at different partial pressures of sputtering gas ranging from 3 to 7 μbar. Microstructural, magnetic and magnetostrictive properties were studied using X-ray diffraction (XRD), atomic force microscopy (AFM), energy dispersive spectroscopy (EDS) and magneto-optic Kerr effect (MOKE) magnetometry respectively. X-ray diffraction showed that all films have the body-centered cubic (bcc) Fe-Ga phase with the 〈1 1 0〉 direction out of the film plane. Magnetic characterization of the films showed that the films prepared at 3 μbar had weak uniaxial anisotropy whereas films grown at Ar pressures in the range 4-7 μbar were magnetically isotropic. The effective saturation magnetostriction constants (λ_eff) of the films were measured using the Villari effect. It was found that effective saturation magnetostriction constants were almost constant over the Ga composition range achieved by varying the sputtering pressure. The measured effective magnetostriction constants fit closely to the calculated saturation magnetostriction constants of 〈1 1 0〉 textured polycrystalline films with the 〈1 1 0〉 directions slightly canted with respect to the normal to the sample surface. It was found that a high pressure of the sputtering gas effected the magnetic softness of the films. The saturation field increased and remanence ratio decreased with increase in pressure.     

Effects of the oxygen partial pressure and annealing atmospheres on the microstructures and optical properties of Cu-doped ZnO films

Cu-doped zinc oxide (ZnO:Cu) films were deposited on p-Si (1 0 0) substrates at 200 °C under various oxygen partial pressures by using radio frequency reactive magnetron sputtering. The properties of the films were characterized by the X-ray diffraction spectroscopy (XRD), energy dispersive spectrometer, X-ray photoelectron spectroscopy (XPS) and fluorescence spectrophotometer with the emphasis on the evolution of microstructures, element composition, valence state of Cu, optical properties. The results indicated that the properties of ZnO:Cu films were significantly affected by oxygen partial pressures. XRD measurements revealed that the sample prepared at the ratio of O₂:Ar of 15:10 sccm had the best crystal quality among all ZnO:Cu films. XPS analysis results suggested that the valence of Cu in the ZnO films was a mixed state of +1 and +2, and the integrated intensity ratio of Cu²⁺ to Cu⁺ increased with the increment of oxygen partial pressure. The photoluminescence measurements at room temperature revealed a violet, two blue and a green emission. We considered that the origin of green emission came from various oxygen defects when the ZnO:Cu films grew in oxygen poor and enriched environment. Furthermore, the influence of annealing atmosphere on the microstructures and optical properties of ZnO:Cu films were discussed.     

Effect of substrate temperature on the structural, optical and electrical properties of dc magnetron sputtered tantalum oxide films

dc reactive magnetron sputtering technique was employed for deposition of tantalum oxide films on quartz and silicon substrates by sputtering of pure tantalum target in the presence of oxygen and argon gases under various substrate temperatures in the range 303-973 K. The variation of cathode potential with the oxygen partial pressure was systematically studied. The influence of substrate temperature on the chemical binding configuration, crystal structure and optical properties was investigated. X-ray photoelectron spectroscopic studies indicated that the films formed at oxygen partial pressures ≥1 × 10⁻⁴ mbar were stoichiometric. The Fourier transform infrared spectroscopic studies revealed that the films formed up to substrate temperatures <673 K showed a broad absorption band at 750-1000 cm⁻¹ and a sharp band at 630 cm⁻¹ indicated the presence of amorphous phase while at higher substrate temperatures the appearance of bands at about 810 and 510 cm⁻¹ revealed the polycrystalline nature. The effect of substrate temperature on the electrical characteristics of Al/Ta₂O₅/Si structure was investigated. The dielectric constant values were in the range 17-29 in the substrate temperature range of 303-973 K. The current-voltage characteristics showed modified Poole-Frenkel conduction mechanism with a tendency for reduction of the compensation level. The optical band gap of the films decreased from 4.44 to 4.25 eV and the refractive index increased from 1.89 to 2.25 with the increase of substrate temperature from 303 to 973 K.     

On the phase formation of titanium oxide thin films deposited by reactive DC magnetron sputtering: influence of oxygen partial pressure and nitrogen doping

This work describes about the control on phase formation in titanium oxide thin films deposited by reactive dc magnetron sputtering. Various phases of titanium oxide thin films were deposited by controlling the oxygen partial pressure during the sputtering process. By adding nitrogen gas to sputter gas mixture of oxygen and argon, the oxygen partial pressure was decreased further below the usual critical value, below and above which the sputtering yields metallic and oxide films, respectively. Furthermore, nitrogen addition eliminated the typical hysteretic behaviour between the flow rate and oxygen partial pressure, and significantly influenced the sputter rate. On increasing the oxygen partial pressure, the ratio between anatase and rutile fraction and grain size increases. The fracture cross-sectional scanning electron microscopy together with the complementary information from X-ray diffraction and micro-Raman investigations revealed the evolution and spatial distribution of the anatase and rutile phases. Both the energy delivered to the growing film and oxygen vacancy concentrations are correlated with the formation of various phases upon varying the oxygen partial pressure.     

氧分压对磁控溅射制备ZnO薄膜的结构及光学特性的影响

采用射频反应磁控溅射法在玻璃衬底上成功制备出具有c轴高择优取向的ZnO薄膜,利用X射线衍射及紫外-可见吸收和透射光谱研究了氧分压变化对ZnO薄膜的微观结构及光吸收特性的影响。结果表明,当工作气压恒定时,用射频反应磁控溅射制备的ZnO薄膜的生长行为主要取决于成膜空间中氧的密度,合适的氧分压能够提高ZnO薄膜的结晶质量;薄膜在可见光区的平均透过率达到90%以上,且随着氧分压的增大,薄膜的光学带隙发生了一定程度的变化。采用量子限域模型对薄膜的光学带隙作了相应的理论计算,计算结果与对样品吸收谱所作的拟合结果符合较好,二者的变化趋势完全一致,表明ZnO纳米晶粒较小时,薄膜光学带隙的变化与量子限域效应有很大关系。     

The preparation and refractive index of BST thin films

Radio-frequency magnetron sputtering technique is used to deposit Ba_0.65Sr_0.35TiO₃ (BST) thin films on fused quartz substrates. In order to prepare the high-quality BST thin films, the crystallization and microstructure of the films were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM). More intense characteristic diffraction peaks and better crystallization can be observed in BST thin films deposited at 600 °C and subsequently annealed at 700 °C. The refractive index of the films is determined from the measured transmission spectra. The dependences of the refractive index on the deposition parameters of BST thin films are different. The refractive index of the films increases with the substrate temperature. At lower sputtering pressure, the refractive index increases from 1.797 to 2.197 with pressure increase. However, when the pressure increases up to 3.9 Pa, the refractive index reduces to 1.86. The oxygen to argon ratio also plays an important effect on the refractive index of the films. It has been found that the refractive index increases with increase in the ratio of oxygen to argon. The refractive index of BST thin films is strongly dependent on the annealing temperature, which also increases as the annealing temperature ascends. In a word, the refractive index of BST thin films is finally affected by the films’ microstructure and texture.     

Determination of electrical types in the P-doped ZnO thin films by the control of ambient gas flow

Phosphorus (P)-doped ZnO thin films with amphoteric doping behavior were grown on c-sapphire substrates by radio frequency magnetron sputtering with various argon/oxygen gas ratios. Control of the electrical types in the P-doped ZnO films was achieved by varying the gas ratio without post-annealing. The P-doped ZnO films grown at a argon/oxygen ratio of 3/1 showed p-type conductivity with a hole concentration and hole mobility of 1.5 × 10¹⁷ cm⁻³ and 2.5 cm²/V s, respectively. X-ray diffraction showed that the ZnO (0 0 0 2) peak shifted to lower angle due to the positioning of P³⁻ ions with a larger ionic radius in the O²⁻ sites. This indicates that a p-type mechanism was due to the substitutional P_O. The low-temperature photoluminescence of the p-type ZnO films showed p-type related neutral acceptor-bound exciton emission. The p-ZnO/n-Si heterojunction light emitting diode showed typical rectification behavior, which confirmed the p-type characteristics of the ZnO films in the as-deposited status, despite the deep-level related electroluminescence emission.     

Development of rf plasma sputtered Al2O3-TiO2 multilayer broad band antireflecting coatings and its correlation with plasma parameters

TiO₂/Al₂O₃/TiO₂/Al₂O₃ multilayer structures were obtained at different oxygen:argon gas ratios of 20:80, 30:70, 50:50 and 60:40 sccm and constant rf power of 200 W using reactive magnetron sputtering. Grain size and elemental distribution in the films were studied from AFM image and XPS spectra respectively. The deposited grain size increased with increasing oxygen:argon gas ratio. The optical band gap, refractive index, extinction coefficient were calculated from UV-vis transmittance and reflectance spectra. It was observed that the value of refractive index, extinction coefficient and band gap increased with increasing oxygen. These variations are due to the defects levels generated by the heterostructure and explained by the PL spectrum. The antireflecting (AR) efficiency of the films was estimated from the reflectance spectra of the films. Broad band antireflecting coating for the visible range was achieved by varying oxygen content in the film. The plasma chemistry controlled the antireflecting property by the interface interdiffusion of atoms during layer transition in multilayer deposition. The in situ investigation of the plasma chemistry was performed using optical emission spectroscopy. The plasma parameters were estimated and correlated with the characteristics of the films.     

Deposition of nanostructured crystalline and corrosion resistant alumina film on bell metal at low temperature by rf magnetron sputtering

Aluminium oxide films deposited by rf magnetron sputtering for protective coatings have been investigated. The alumina films are found to exhibit grainy surface microstructure. The grain size, structure and density depend on different system parameters such as argon and/or oxygen flow rate and applied rf power etc. The effect of transition of the discharge from metallic to reactive mode on the surface characteristics of the alumina film is studied. X-ray diffractometry reveals that in poisoned mode of sputtering and under optimized power and pressure, crystalline alumina film can be grown. Different system conditions are optimized for corrosion resistant aluminium oxide films with good adhesion properties. Nanostructured alumina film is obtained at lower pressure (8 × 10⁻⁴ to 9 × 10⁻⁴ Torr) by rf reactive magnetron sputtering.     

Effects of O2/Ar flow ratio on the alcohol sensitivity of tin oxide film

The aim of this study is to find the effects of oxygen flow rate during manufacturing on the sensitivity of SnO₂ (tin oxide) thin films to ethanol (C₂H₅OH). In this study, an RF sputtering process was employed to fabricate the SnO₂ thin films. The SnO₂ was deposited on gold electrode silicon microchips. A target composed of SnO₂ doped with 1 at.% Li was used with a working pressure of 3 mTorr. The RF power was fixed at 150 W. The reaction gas was a mixture of argon and oxygen. The total flow rate was constant at 50 sccm with the O₂/Ar ratio varying from 0.2 to 0.8. An annealing heat treatment was employed at 400 °C for 1 h to stabilize the properties of the films. The sensitivity of the film to ethanol was tested by placing the micro-reactor device on a hot plate, heated to 300 °C, and measuring the variation of electrical resistivity of the film with and without the presence of ethanol. The results show that an O₂/Ar flow ratio of 0.2 produces films with the highest ethanol sensitivity. Before heat treating, the ethanol sensitivity was 126. After heat treating at 400 °C for 1 h, the sensitivity decreased to 104.     

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.