Deposition and characterization of AZO thin films on flexible glass substrates using DC magnetron sputtering technique

Al-doped zinc oxide (AZO) thin films were deposited onto flexible ultra-thin glass substrates by using a direct current (DC) magnetron sputtering process. The effects of sputtering power, working pressure and substrate temperature on the morphology and optoelectronic performances of AZO films were investigated. The optimal sputtering power, working pressure and substrate temperature for AZO film were determined to be 100 W, 0.9 Pa and 150 ℃, respectively. Further increasing or decreasing the sputtering power, working pressure and substrate temperature degrades the quality of AZO films. XRD patterns show all as-sputtered AZO thin films are preferred to grow along <0002> direction. Moreover, the largest grain size, which depicts the best microstructure of AZO films, matches with the smallest stress value. It can be seen from SEM images that the surface is smooth and dense. The smallest value of the resistivity is 1.784×10⁻³ Ω cm and the average transmittance of all AZO films in the visible range is about 80%. The X-ray photoelectron spectroscopy spectra show that the amount of Al element in the AZO film is very small.     

Room temperature preparation of high performance AZO films by MF sputtering

Aluminum-doped zinc oxide (AZO) thin films have been deposited by MF magnetron sputtering from a ceramic oxide target without heating the substrates. This study has investigated effects of sputtering power on the structural, electrical and optical properties of the AZO films. The films delivered a hexagonal wurtzite structure with (002) preferential orientation and uniform surface morphology with 27–33 nm grain size. The results indicate that residual stress and grain size of the AZO films are dependent on sputtering power. The minimum resistivity of 7.56×10^?4 Ω cm combined with high transmittance of 83% were obtained at deposited power of 1600 W. The films delivered the advantages of a high deposition rate at low substrate temperature and should be suitable for the fabrication of low-cost transparent conductive oxide layer.     

Improving the electrical properties of niobium-doped titania sputtering targets by sintering in oxygen-deficient atmospheres

Niobium-doped titania (TNO) film can be used as a transparent conductive oxide (TCO) film due to its excellent conductivity and visible transparency. The performances of TNO sputtering targets are thus critical issues in optimizing sputtered films. This study clarifies the influences of inert and reducing atmospheres on the microstructure, densification, crystal structure, and electrical properties of TNO sputtering targets. The results indicate that a sintering atmosphere of 90% Ar–10% H₂ can result in a lower sintered density, larger grain size, and lower resistivity than can an atmosphere of Ar, followed by one of air. Sintering in 90% Ar–10% H₂ or Ar obviously decreases the resistivity of TiO₂, from >10⁸ Ω cm to <10⁻¹ Ω cm, and the TNO target, from >10¹ Ω cm to <10⁻¹ Ω cm. The resistivity of TNO target sintered at 1200 °C in 90% Ar–10% H₂ is as low as 1.8×10⁻² Ω cm.     

Study of Cu-based Al-doped ZnO multilayer thin films with different annealing conditions

AZO/Cu/AZO multilayer thin films produced under different annealing conditions are studied in this paper, to examine the effects of atmosphere and annealing temperature on their optical and electrical properties. The multilayer thin films are prepared by simultaneous RF magnetron sputtering (for AZO) and DC magnetron sputtering (for Cu). The thin films were annealed in a vacuum or an atmosphere of oxygen at temperatures ranging from 100 to 400 °C in steps of 100 °C for 3 min. High-quality multilayer films (at Cu layer thickness of 15 nm) with resistivity of 1.99×10⁻⁵ Ω-cm and maximum optical transmittance of 76.23% were obtained at 400 °C annealing temperature in a vacuum. These results show the films to be good candidates for use as high quality electrodes in various displays applications.     

Influence of negative bias voltage on structural and mechanical properties of nanocrystalline TiNx thin films treated in hot cathode arc discharge plasma system

Ti thin films were grown by DC sputtering on a glass substrate and then nitrided in a hot cathode arc discharge plasma system, which is an effective approach to independently monitoring the plasma and nitriding parameters. The hardness of pristine Ti thin film is found to be ~3.06 GPa, which increases upto ~16.08 GPa with an increase in negative bias voltage to −140 V and then decreases to ~15.05 GPa for higher of −240 V bias voltage. Similar kind of variation has been observed in crystallite size and surface roughness. Crystallite size is found to increase from 11.1 nm (pristine Ti) to 14.8 nm (for −140 V) and then reduces to 11.9 nm for –240 V. Surface roughness increases from 2.78 nm (pristine) to 6.84 nm (for –140 V), which is found to be 4.14 nm for –240 V. Optical and electrical measurements also reveal the strong impact of negative bias voltage on the bandgap and resistivity of the films. Above results are understood on the basis of diffusion of nitrogen ions for lower voltages and saturation of nitrogen ions in the host lattice for high voltages.     

Preparation of tetrahedral amorphous carbon films by filtered cathodic vacuum arc deposition

Tetrahedrally bonded amorphous carbon (ta-C) and nitrogen doped (ta-C:N) films were obtained at room temperature in a filtered cathodic vacuum arc (FCVA) system incorporating an off-plane double bend (S-bend) magnetic filter. The influence of the negative bias voltage applied to substrates (from −20 to −350 V) and the nitrogen background pressure (up to 10⁻³ Torr) on film properties was studied by scanning electron microscopy (SEM), electron energy loss spectroscopy (EELS), Raman spectroscopy, X-ray photoemission spectroscopy (XPS), secondary ion mass spectroscopy (SIMS) and X-ray reflectivity (XRR). The ta-C films showed sp³ fractions between 84% and 88%, and mass densities around 3.2 g/cm³ in the wide range of bias voltage studied. In contrast, the compressive stress showed a maximum value of 11 GPa for bias voltages around −90 V, whereas for lower and higher bias voltages the stress decreased to 6 GPa. As for the ta-C:N films grown at bias voltages below −200 V and with N contents up to 7%, it has been found that the N atoms were preferentially sp³ bonded to the carbon network with a reduction in stress below 8 GPa. Further increase in bias voltage or N content increased the sp² fraction, leading to a reduction in film density to 2.7 g/cm³.     

Transparent and high infrared reflection film having sandwich structure of SiO2/Al:ZnO/SiO2

New transparent and high infrared reflection films having the sandwich structure of SiO₂/Al:ZnO(AZO)/SiO₂ were deposited on the soda-lime silicate glass at room temperature by radio frequency (R.F.) magnetron sputtering. The optical and electrical properties of SiO₂ (110 nm)/AZO (860 nm)/SiO₂ (110 nm) sandwich films were compared with those of single layer AZO (860 nm) films and double layer SiO₂ (110 nm)/AZO (860 nm) films. The results show that these sandwich films exhibit high transmittance of over 85% in the visible light range (380–760 nm), and low reflection rate of below 4.5% in the wavelength range of 350–525 nm, which is not shown in the conventional single layer AZO (860 nm) films and double layer SiO₂ (110 nm)/AZO (860 nm) films. Further these sandwich films display a low sheet resistance of 20 Ω/sq by sheet resistance formula and high infrared reflection rate of above 80% in the wavelength range of 15–25 μm. In addition, the infrared reflection property of these sandwich films is determined mainly by the AZO film. The outer SiO₂ film can diminish the interference coloring and increase transparency; the inner SiO₂ film improves the adhesion of the coating to the glass substrate and prevents Ca²⁺ and Na⁺ in the glass substrate from entering the AZO film.     

Effect of bias voltage on microstructure and phase evolution of Cr–Mo–N coatings by an arc bonded sputter system

Cr–Mo–N hard coatings were deposited on SKD11 and silicon wafer substrates at various substrate bias voltages by hybrid PVD consisting of arc ion plating and unbalanced magnetron sputtering. The results showed that the microstructure, phase evolution, and mechanical properties of the coatings were significantly altered at the different substrate bias voltage ranging from 0 to −400 V. The X-ray diffraction analysis results revealed that most of the diffraction peaks originated from the Cr–N phase. These peaks were observed at lower positions with no substrate bias and were shifted to higher positions with increasing substrate bias power. The preferred orientation of the (200) plane became dominant accompanying the (220) plane as the bias voltage was increased. Maximum hardness of approximately 30 GPa was obtained at a bias voltage of −200 V. Additionally, wear test results reveal that the lowest coefficient of friction, between 0.4 and 0.5, was obtained from the Cr–Mo–N film formed at a bias voltage of −200 V.     

A study of hard diamond-like carbon films in mid-frequency dual-magnetron sputtering

A series of hydrogen-free diamond-like carbon (DLC) films were deposited by a mid-frequency dual-magnetron sputtering under basic conditions of Cr and C target power density between 6 and 18 W/cm², bias voltage in a range of − 100 V to − 200 V, and a pure argon atmosphere. Microstructure, microhardness, adhesion, friction and wear properties were investigated for the DLC films to be used as protective films on cutting tools and forming dies, etc. The DLC films exhibited some combined superior properties: high hardness of 30–46 GPa, good adhesion of critical load of 50–65 N, and friction coefficient about 0.1 in air condition. Properties of the magnetron-sputtered carbon films showed a strong dependence on flux and energy of ion bombardment during growth of the films.     

Influence of a Ni interlayer on the optical and electrical properties of trilayer GZO/Ni/GZO films

Trilayer GZO/Ni/GZO films were deposited onto polycarbonate (PC) substrates with RF and DC magnetron sputtering, and then the influence of a Ni interlayer on the optical and electrical properties of the films was investigated. A 2-nm-thick Ni interlayer decreased the resistivity to 6.4×10⁻⁴ Ω cm and influenced the optical transmittance.Although optical transmittance deteriorated with Ni insertion, the films showed a relatively high optical transmittance of 74.5% in the visible wavelength region. The figure of merit (FOM) of a GZO single layer film was 1.2×10⁻⁴ Ω⁻¹, while that of the GZO/Ni/GZO films reached a maximum of 8.2×10⁻⁴ Ω⁻¹.Since a higher FOM results in higher quality transparent-conductive oxide (TCO) films, it is concluded that GZO films with a 2 nm Ni interlayer have better optoelectrical performance than single-layer GZO films.     

Effects of bias voltage on microwave plasma used for diamond growth

A tungsten-needle substrate was perpendicularly set onto a substrate holder. Diamond films were grown on the substrate by varying the length of the needle inserted into plasma. The results demonstrated that when the bias voltage was −50 V and the methane concentration was 5%, a diamond thin film grew for a needle length of 0.5 mm, and granular diamond grew for a needle length of 1 mm. Plasma potentials were measured while the bias voltage was varied. The plasma potential became negative at bias voltage of 0 V, and it changed to positive as the negative bias voltage increased. These results revealed that diamonds were grown near the boundary between the transition region surrounding the plasma ball and the ion sheath. In addition, the results also indicated that the bias voltage can control the density and energy of ions, electrons and radicals near the plasma, and therefore plays a role in providing optimal conditions for diamond growth.     

Aluminum doped zinc oxide sputtering targets obtained from nanostructured powders: Processing and application

This work reports the production of ceramic targets based on nanostructured Al-doped ZnO (AZO) powders for sputtering applications. The nanostructured powder is obtained by a new patented process based on the detonation of an emulsion containing both Zn and Al metal precursors in the final proportion of 98:2 wt% (ZnO:Al₂O₃), through which the Al contains is highly uniform distributed over ZnO. Due to the nanostructured powder characteristics, the targets can be sintered at substantially lower temperatures (1150–1250 °C) by conventional sintering, contributing to production costs reduction of ceramic targets and consequently the costs of photovoltaic and displays industries. Electrical resistivity values around 3.0–7.0 × 10^?3 Ω cm have been obtained depending on final microstructure of the targets. The electro-optical properties of the films produced at room temperature with thicknesses around 360 nm, besides being highly uniform exhibit a resistivity of about 1 × 10^?3 Ω cm and a transmittance in the visible range above 90%.     

Structure and electrical properties of a-C:H thin films deposited by RF sputtering

We investigated the film structure and the electrical properties of hydrogenated amorphous carbon (a-C:H) thin films. a-C:H thin films were prepared by RF magnetron sputtering. Two different RF power sources of 13.56 MHz and 60 MHz were used to deposit the a-C:H films. The bonding hydrogen concentration varied from 1.6 × 10²² cm^? 3 to 8.6 × 10²² cm^? 3. The concentration of incorporated hydrogen atoms varied from 18 to 57 at.%. The optical gap increased from 1.58 eV to 2.56 eV with increasing the hydrogen concentration. The resistivity increased from 10¹³ Ω cm to 10¹⁵ Ω cm with increasing the hydrogen concentration. The permittivity measured at 1 MHz decreased from 5.6 to 2.3 with increasing the hydrogen concentration. These results suggest that the film structure and electrical properties can be controlled by the hydrogen concentration.     

Properties of solution-processed MgInZnO semiconductor thin films and photodetectors fabricated at a low temperature using UV-assisted thermal annealing

Ultraviolet (UV) irradiation-assisted thermal annealing is used for the fabrication of Mg doped InZnO (MIZO) semiconductor thin films and metal-semiconductor-metal (MSM) type photodetectors on alkali-free glasses at a low temperature of 300 °C. In this study, the effects of UV irradiation time on the structural features and the optical and electrical properties of sol-gel derived MIZO thin films were investigated, and the photoresponse properties of MIZO photodetectors fabricated using UV-assisted thermal annealing (UV-TA) and conventional thermal annealing (CTA) were compared. The molar ratio of In:Zn was fixed at 3:2, and the Mg content was maintained at 20 at% ([Mg]/[In+Zn]) in the precursor solution. After a spin-coating and drying procedure was performed twice, the dried sol-gel films were heated on a hotplate at 300 °C and exposed to UV irradiation in ambient air. The UV irradiation time was adjusted to 1, 2, 3, and 4 h. All annealed MIZO thin films had a dense microstructure, uniform film thickness, and flat surface and exhibited good optical transmittance (> 86.0%). The mean resistivity decreased with increasing irradiation time, and the samples irradiated for 4 h exhibited the lowest mean resistivity of 4.4×10² Ω-cm. Current-voltage (I-V) characteristics showed that the MIZO photodetectors operated in the photoconductive mode. Under illumination with UVC light, the MIZO photodetectors exhibited an I_light-to-I_dark ratio of 7.7 × 10² and had a photoresponsivity of 5.0 A/W at a bias of 5 V.     

Deposition of mechanically hard amorphous carbon nitride films with high [N] / ([N] + [C]) ratio

Mechanically hard amorphous carbon nitride films were prepared by a combination of negative radio frequency (RF) bias voltage (− V_RF) applied to a substrate and chemical vapor deposition using a decomposition reaction of BrCN with a microwave discharge flow of Ar. A pulsed operation of − V_RF was effective when − V_RF > 40 V to avoid excess sputtering of films. The [N] / ([N] + [C]) ratios of films were ≈ 0.5 irrespective of the application of − V_RF. The maximum hardness was 36 ± 10 GPa for the film obtained under the conditions of − V_RF = 100 V, a pulse period of 1000 s, and a pulse-on time of 800 s. According to the IR spectra, the intensity of the stretching vibration of the CN bond increased by the application of − V_RF. The Raman spectra showed increases in the relative intensity and width of the D-band. From these observations, the mechanism of film hardening was discussed.     

Structure and electrochemical characterization of carbon films formed by unbalanced magnetron (UBM) sputtering method

We previously reported nanocarbon films formed by the electron cyclotron resonance (ECR) sputtering method. The films contain a nanocrystalline structure consisting of sp³ and sp² bonds with an extremely flat surface (Ra = 0.07 nm). The film also has a wider potential window than glassy carbon and superior electrochemical activity to boron doped diamond for certain species. However, ECR sputtering equipment is much more expensive than that used for conventional sputtering and requires a ring-shaped target. Therefore, it is difficult to use this method to develop new electrode materials such as metal-carbon hybrid film. Here, we describe a nanocarbon film electrode that we developed with a potential window and electrochemical activity equivalent to those of ECR nanocarbon films by using unbalanced magnetron (UBM) sputtering equipment. Our approach uses conventional equipment and has widely controllable sputtering conditions including a high sputtering rate, a large sputtering area and the capacity for co-sputtering multiple materials. The film can contain a maximum of 53% sp³ bonds by increasing the substrate bias voltage between the target and substrate, and also exhibits a potential window equivalent to that of the ECR nanocarbon film. However, the electrode surface is about one order of magnitude rougher than that of the ECR nanocarbon film due to the effect of reflected Ar⁺ ions caused by the fact that the target surface is facing the substrate surface. By employing transmission electron microscopy, we could observe nanocrystalline graphene structures in the UBM nanocarbon film, which are difficult to observe in conventional diamond-like carbon film. The electron transfer rate at the UBM nanocarbon film is similar to those of ECR nanocarbon film for Ru(NH₃)₆^3 + and Fe(CN)₆^4 −, suggesting that the nanocrystalline structure could contribute to a relatively fast electron transfer rate. The UBM nanocarbon films were successfully used for detecting kynurenic acid, which has a high oxidation potential and is difficult to detect with a conventional glassy carbon electrode.     

Preparation and properties of AZO/PS/AZO tri-layer transparent conductive film with a light-trapping structure

The light-trapping structure is an effective method to increase solar light capture efficiency in the solar cells. In this study, Al-doped ZnO (AZO)/polystyrene (PS)/AZO tri-layer transparent conductive film with light-trapping structure was fabricated by magnetron sputtering and liquid phase methods. The structural, optical and electrical properties of the AZO films could be controlled by different growth conditions. When the sputtering pressure of the under-layer AZO film was 0.2 Pa, the discharge voltage was around 80 V, which was within the optimal process window for obtaining AZO film with high crystallinity. The optimal under-layer AZO film had a large surface roughness and a very low static water contact angle of 75.71°, promoting the relatively uniform distribution of PS spheres. Under this sputtering condition, the prepared AZO/PS/AZO tri-layer film had the highest crystallinity and least point defects. The highest carrier concentration and Hall mobility are 3.0 × 10²¹ cm^-3and 5.39 cm² V^-1 s^-1, respectively. Additionally, a transparent conductive film with the lowest resistivity value (3.88 × 10^-4 Ω cm) and the highest average haze value (26.5%) was obtained by optimizing the process parameters. These properties were comparable to or exceed the reported values of surface-textured SnO₂-based as well as ZnO-based TCOs films, making our films suitable for transparent electrode applications, especially in thin-film solar cells.     

Structural and optoelectronic properties of transparent conductive c-axis-oriented ZnO based multilayer thin films with Ru interlayer

ZnO and Ru multilayer thin films are deposited using the sputtering deposition technique at room temperature. The effects of the Ru interlayer thickness and annealing temperature on the properties of multilayer thin films have been studied. An X-ray diffraction study reveals that ZnO layers are highly c-axis-oriented. The use of an Ru interlayer improves the crystalline quality of the subsequently deposited ZnO layers. Moreover, the crystalline quality of the entire structure is further enhanced through thermal annealing in a vacuum. Atomic force microscopy images show that the surface roughness of the multilayer thin films increases with a Ru interlayer thickness greater than 6 nm. The roughness of the film surface increases in correlation with annealing temperatures. This accounts for the decreased optical transmittance of the multilayer thin films annealed at temperatures higher than 450 °C. The electrical resistivity of multilayer thin films decreases with an increase in the metallic interlayer thickness. Thermal annealing at 450 °C causes low resistivity in multilayer thin films. The lowest resistivity reached ～5.4 × 10^?4 Ω cm for multilayer films with a 10-nm-thick Ru interlayer annealed at 450 °C.     

Silicon carbide films from polycarbosilane and their usage as buffer layers for diamond deposition

Thin films of polycarbosilane (PCS) were coated on a Si (100) wafer and converted to silicon carbide (SiC) by pyrolyzing them between 800 and 1150 °C. Granular SiC films were derived between 900 and 1100 °C whereas smooth SiC films were developed at 800 and 1150 °C. Enhancement of diamond nucleation was exhibited on the Si (100) wafer with the smooth SiC layer generated at 1150 °C, and a nucleation density of 2 × 10¹¹ cm^− 2 was obtained. Nucleation density reduced to 3 × 10¹⁰ cm^− 2 when a bias voltage of − 100 V was applied on the SiC-coated Si substrate. A uniform diamond film with random orientations was deposited to the PCS-derived SiC layer. Selective growth of diamond film on top of the SiC buffer layer was demonstrated.     

Enhancing optical and electrical properties of Al-doped ZnO coated polyethylene terephthalate substrates by laser annealing using overlap rate controlling strategy

Aluminum-doped zinc oxide (AZO) layers were deposited on polyethylene terephthalate (PET) flexible substrates and optimized by laser annealing using a 532 nm nanosecond pulsed laser. Effects of overlap rates, i.e. laser spot overlap rate (SO_R) and laser scan line overlap rate (LO_R), on AZO/PET films were investigated by X-ray diffractometer (XRD), scanning electron microscope (SEM), UV–visible transmittance spectra and digital four-point probe instrument, respectively. Laser annealing could greatly enhance grain crystallinity, increase crystallite size and avoid damage to the PET flexible substrates, thus effectively enhance transmittance and conductivity of the films. The results showed that the AZO/PET film annealed by using 85% SO_R and 60% LO_R presented the highest average visible transmittance of 76.2% and the lowest resistivity of 1.95×10⁻³ Ω cm, which respectively improved by approximately 23% and 75% compared to those of the as-deposited AZO/PET film. This work may be of great importance from the viewpoint of performance optimization of transparent conductive oxide (TCO) flexible films.