Thin film fabrication of nano-porous 12CaO·7Al2O3 crystal and its conversion into transparent conductive films by light illumination

Thin film fabrication of crystalline 12CaO·7Al₂O₃ (C12A7) with zeolitic structure was examined, and their electrical and optical properties were measured. Polycrystalline thin films were prepared by post-annealing of amorphous films in oxygen atmosphere at temperatures above 800 °C. Choice of substrates was crucial for obtaining single-phase thin films. Although various oxide substrates (single crystals of Al₂O₃, Y-stabilized ZrO₂, MgO and silica glass) were examined, single-phase films were obtained only for MgO substrates and the other substrates reacted with the CaO component in the films during post-annealing. The optical band gap of C12A7 was evaluated to be 5.9 eV. Hydride ions were incorporated into the film by a thermal treatment in a hydrogen atmosphere at 1200 °C. The resulting transparent thin films were converted into transparent persistent electronic conductors exhibiting an electrical conductivity 6.2×10⁻¹ S cm⁻¹ at 300 K by ultraviolet light illumination. This is the first example of transparent conductive thin film in which conductive areas can be patterned directly by light.     

Fabrication of a n-ZnO/p-Si heterojunction diode by ultra-high vacuum magnetron sputtering

Heterojunction diodes of n-type ZnO were fabricated on a p-type Si(100) substrate using an ultra-high vacuum radio frequency magnetron sputtering method at room temperature. A short-time post-annealing process was performed to prevent inter-diffusion of Zn, dopants, and Si atoms. The post-annealing process at 600 °C enhanced the crystallinity of ZnO films and produced a high forward to reverse current ratio of the heterojunction diode with a barrier height of approximately 0.336 eV. A thin SiO_x layer at the interface of the ZnO film and Si substrate appeared distinctly at the 600 °C annealing, however the post-annealing at 700 °C showed an a-(Zn_2xSi_1 − xO₂) structure caused by diffusion of silicon into the ZnO film. In the n-ZnO/p-Si sample annealed at 700 °C, a rapid change in the barrier height was considered due to the effect of the dopant segregation from the substrate and deformation of the a-SiO_x structure.     

Preparation of LaNiO3 thin films with very low room-temperature electrical resistivity by room temperature sputtering and high oxygen-pressure processing

LaNiO₃ (LNO) thin films were deposited by radio frequency magnetron sputtering on n-type Si (100) wafers at room temperature (RT). The as-sputtered LNO thin films were amorphous and had very high RT electrical resistivity even after post-annealing at 800 °C. The amorphous as-sputtered LNO films could be transformed to polycrystalline LNO films in rhombohedral phase by heating at 400 °C in an O₂ atmosphere at pressure ranging from 1.5 to 8.0 MPa. Very low RT resistivity of LNO films were obtained by this high oxygen-pressure processing. The lowest value was as low as 1.09 × 10^− 4 Ω cm by processing at oxygen pressure of 8 MPa. Such preparation of LNO thin films is compatible with the Si-based readout integrated circuits. Highly (100)-oriented perovskite structure of Pb(Zr_0.52Ti_0.48)O₃ thin films was formed on this rhombohedral phase LNO, and good ferroelectricity could also be obtained on these HOPP-processed rhombohedral phase LNO films.     

The effects of post-annealing on the performance of ZnO thin film transistors

In this study, we investigated the effects of a post-annealing process on the performance and stability of zinc oxide thin film transistors fabricated by atomic layer deposition. After the post-annealing process in ambient air at 250 °C for 2 h, the value of the saturation mobility increased from 1.2 to 1.8 cm/Vs, the subthreshold swing decreased from 0.53 to 0.34 V/decade, and the I_on/I_off ratio increased from 3.1 × 10⁶ to 1.7 × 10⁷. The positive bias stability was also enhanced after post-annealing. These results are related to the formation of another phase in which the difference of enthalpy between the semiconductor material and contact metal electrode causes the carrier concentration at the metal/semiconductor interface to increase, leading to decreased contact resistivity. Additionally, internal modification of the semiconductor/dielectric interface and/or improving the semiconductor structure, which is related to a change in the oxidation state of Zn through the incorporation of oxygen and/or hydroxide, can result in improved device performance.     

Structural and optical properties of Ti-doped ZnO thin films prepared by the cathodic vacuum arc technique with different annealing processes

Highly transparent Ti-doped ZnO thin films were prepared on glass substrates at a deposition rate of approximately 33 nm/min using the cathodic vacuum arc technique with a Zn target power of 550 W and a Ti target power of 750 W, respectively. X-ray diffraction measurements have shown that the Ti-doped ZnO thin film with a vacuum post-annealing condition is c-axis oriented but an amorphous phase at the other post-annealing atmosphere and as-deposited condition. Transmittance measurements show that the best optical quality of the Ti-doped ZnO thin films occurred at a post-annealing atmosphere of N₂/H₂ mixed gases. Additionally, the optical transmittance of all films has been found more than 85% in a range of 500-700 nm. The lowest electrical resistivity was 3.48 × 10⁻³ Ω cm, obtained on as-deposited films. However, the post-annealing condition greatly increased the resistivity.     

Preparation of anatase TiO2 thin films for dye-sensitized solar cells by DC reactive magnetron sputtering technique

Anatase titanium dioxide (TiO₂) thin films are prepared by DC reactive magnetron sputtering using Ti target as the source material. In this work argon and oxygen are used as sputtering and reactive gas respectively. DC power is used at 100 W per 1 h. The distance between the target and substrate is fixed at 4 cm. The glass substrate temperature value varies from room temperature to 400 °C. The crystalline structure of the films is determined by X-ray diffraction analysis. All the films deposited at temperatures lower than 300 °C were amorphous, whereas films obtained at higher temperature grew in crystalline anatase phase. Phase transition from amorphous to anatase is observed at 400 °C annealing temperature. Transmittances of the TiO₂ thin films were measured using UV-visible NIR spectrophotometer. The direct and indirect optical band gap for room temperature and substrate temperature at 400 °C is found to be 3.50, 3.41 eV and 3.50, 3.54 eV respectively. The transmittance of TiO₂ thin films is noted higher than 75%. A comparison among all the films obtained at room temperature showed a transmittance value higher for films obtained at substrate temperature of 400 °C. The morphology of the films and the identification of the surface chemical stoichiometry of the deposited film at 400 °C were studied respectively, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The surface roughness and the grain size are measured using AFM.     

Effect of post-annealing treatment in oxygen on dielectric properties of K0.5Na0.5NbO3 thin films prepared by chemical solution deposition

K_0.5Na_0.5NbO₃ thin films were prepared on Pt/Ti/SiO₂/Si substrates by chemical solution deposition method with different annealing temperatures of 550 °C, 600 °C, 700 °C. The post-annealing treatment was introduced at 550 °C for 3 min in oxygen ambient. It is found that the films were composed of pure provskite phase, and the post-annealing treatment promoted the crystallization and improved the quality of the films, which resulted in the enhancement of the dielectric property of the films. The effect of the post-annealing on the dielectric properties of the films was also discussed.     

Influence of annealing on humidity response of RF sputtered nanocrystalline MgFe2O4 thin films

Humidity response of Radio Frequency sputtered MgFe₂O₄ thin films onto alumina substrate, annealed at 400 °C, 600 °C and 800 °C has been investigated. Crystalline phase formation of thin films annealed at different temperature was analyzed by X-ray Diffraction. A particle/grain like microstructure in the grown thin films was observed by Scanning Electron Microscope and Atomic Force Microscope images. Film thickness for different samples was measured in the range 820-830 nm by stylus profiler. Log R (Ω) response measurement was taken for all thin films for 10-90% relative humidity (% RH) change at 25 °C. Resistance of the film increased from 5.9 × 10¹⁰ to 3 × 10¹² at 10% RH with increase in annealing temperature from 400 °C to 800 °C. A three-order magnitude, 10¹² Ω to 10⁹ Ω drop in resistance was observed for the change of 10 to 90% RH for 800 °C annealed thin film. A good linear humidity response, negligible humidity hysteresis and minimum response/recovery time of 4 s/6 s have been measured for 800 °C annealed thin film.     

Structural and electrical properties of sputtered indium-zinc oxide thin films

In this study, indium-zinc oxide (IZO) thin films have been prepared at a room temperature, 200 and 300 °C by radio frequency magnetron sputtering from a In₂O₃-12 wt.% ZnO sintered ceramic target, and their dependence of electrical and structural properties on the oxygen content in sputter gas, the substrate temperature and the post-heat treatment was investigated. X-ray diffraction measurements showed that amorphous IZO films were formed at room temperature (RT) regardless of oxygen content in sputter gas, and micro-crystalline and In₂O₃-oriented crystalline films were obtained at 200 and 300 °C, respectively. From the analysis on the electrical and the structural properties of annealed IZO films under Ar atmosphere at 200, 300, 400 and 500 °C, it was shown that oxygen content in sputter gas is a critical parameter that determines the local structure of amorphous IZO film, stability of amorphous phase as well as its eventual crystalline structure, which again decide the electrical properties of the IZO films. As-prepared amorphous IZO film deposited at RT gave specific resistivity as low as 4.48 × 10^− 4 Ω cm, and the highest mobility value amounting to 47 cm²/V s was obtained from amorphous IZO film which was deposited in 0.5% oxygen content in sputter gas and subsequently annealed at 400 °C in Ar atmosphere.     

Effects of post-deposition surface treatment on the optical, structural and hydrogen sensing properties of TiO2 thin films

TiO₂ thin films were prepared by DC reactive magnetron sputtering in a mixture of oxygen and argon on glass and oxidized silicon substrates. The effect of post-deposition annealing (300 °C, 500 °C and 700 °C for 8 h in air) on the structural and morphological properties of TiO₂ thin films is presented. In addition, the effect of Pt surface modification (1, 3 and 5 nm) on hydrogen sensing was studied. XRD patterns have shown that in the range of annealing temperatures from 300 °C to 500 °C crystallization starts and the thin film structure changes from amorphous to polycrystalline (anatase phase). In the case of samples on glass substrate, optical transmittance spectra were recorded. TiO₂ thin films were tested as sensors of hydrogen at concentrations 10,000-1000 ppm and operating temperatures within the 180-200 °C range. The samples with 1 nm and in particular with 3 nm of Pt on the surface responded to hydrogen fast and with high sensitivity.     

Effect of annealing temperature on magnetic property of Si1 − xCrx thin films

Polycrystalline Si_1 − xCr_x thin films have been prepared by magnetron sputtering followed by rapid thermal annealing (RTA) for crystallization. RTA was performed at 800 °C for 5 min, 1200 °C for 30 s and 1200 °C for 2 min, in a N₂ flow. The magnetic hysteresis loops were observed at room temperature in all the samples except for RTA at 800 °C for 5 min, and the annealing caused the decrease of saturation magnetization relative to the as-grown film. X-ray diffraction spectra and Raman spectra showed that the annealing process lead the deposited amorphous film to be crystallized and CrSi₂ phase formed. The magnetism of the films was determined by the competition between crystallinity and precipitation of diamagnetic CrSi₂ phase.     

Microstructure formation during the annealing of iron nitrides

The thermal metastability of iron nitride was exploited to fabricate thin-film microstructures applicable to left-handed metamaterials. A granular thin film containing dispersed iron particles was prepared by post-annealing an rf-sputter-deposited Fe_0.5Al_0.5N thin film with a wurtzite-type structure in a nitrogen atmosphere at 450 °C. The obtained samples showed magnetic resonance in the microwave region. Laser direct writing was also applied in a nitrogen atmosphere to an rf-sputter-deposited Fe_0.7Al_0.3N thin film. 200 μm-wide, 300 Ω cm iron metal lines were drawn in a host nitride film of approximately 2 kΩ cm. Combining and optimizing the above negative permeability and permittivity values should provide left-handed materials with a negative refractive index.     

Photocatalytic activities of TiO2 thin films prepared on Galvanized Iron substrate by plasma-enhanced atomic layer deposition

Titanium dioxide (TiO₂) thin films were prepared on Galvanized Iron (GI) substrate by plasma-enhanced atomic layer deposition (PE-ALD) using tetrakis-dimethylamido titanium and O₂ plasma to investigate the photocatalytic activities. The PE-ALD TiO₂ thin films exhibited relatively high growth rate and the crystal structures of TiO₂ thin films depended on the growth temperatures. TiO₂ thin films deposited at 200 °C have amorphous phase, whereas those with anatase phase and bandgap energy about 3.2 eV were deposited at growth temperature of 250 °C and 300 °C. From contact angles measurement of water droplet, TiO₂ thin films with anatase phase and Activ™ glass exhibited superhydrophilic surfaces after UV light exposure. And from photo-induced degradation test of organic solution, anatase TiO₂ thin films and Activ™ glass decomposed organic solution under UV illumination. The anatase TiO₂ thin film on GI substrate showed higher photocatalytic efficiency than Activ™ glass after 5 h UV light exposure. Thus, we suggest that the anatase phase in TiO₂ thin film contributes to both superhydrophilicity and photocatalytic decomposition of 4-chlorophenol solution and anatase TiO₂ thin films are suitable for self-cleaning applications.     

Growth and characterization of Bi2Se3 thin films by pulsed laser deposition using alloy target

Bi₂Se₃ thin films were deposited on the (100) oriented Si substrates by pulsed laser deposition technique at different substrate temperatures (room temperature −400 °C). The effects of the substrate temperature on the structural and electrical properties of the Bi₂Se₃ films were studied. The film prepared at room temperature showed a very poor polycrystalline structure with the mainly orthorhombic phase. The crystallinity of the films was improved by heating the substrate during the deposition and the crystal phase of the film changed to the rhombohedral phase as the substrate temperature was higher than 200 °C. The stoichiometry of the films and the chemical state of Bi and Se elements in the films were studied by fitting the Se 3d and the Bi 4d5/2 peaks of the X-ray photoelectron spectra. The hexagonal structure was seen clearly for the film prepared at the substrate temperature of 400 °C. The surface roughness of the film increased as the substrate temperature was increased. The electrical resistivity of the film decreased from 1 × 10⁻³ to 3 × 10⁻⁴ Ω cm as the substrate temperature was increased from room temperature to 400 °C.     

Structure and microwave dielectric properties of Bi1.5Zn1.0Nb1.5O7 thin films deposited on alumina substrates by pulsed laser deposition

Bi_1.5Zn_1.0Nb_1.5O₇ (BZN) thin films were deposited on polycrystalline alumina substrates by pulsed laser deposition at different substrate temperatures. The phase structure and surface morphology were characterized using X-ray diffractometer (XRD) and atomic force microscopy. Microwave dielectric properties were performed using split-post dielectric resonator method at spot frequencies of 10, 15 and 19 GHz, respectively. The XRD results indicate that the as-deposited Bi_1.5Zn_1.0Nb_1.5O₇ thin films deposited at 650 °C are amorphous in nature. The dielectric permittivity and loss tangent of the amorphous BZN thin films are 75.5 and 0.013 at 10 GHz, respectively. As the measure frequency increased to 19 GHz, the dielectric permittivity slightly decreases and loss tangent slightly increases. BZN thin films were crystallized after the post-annealing by a rapid thermal annealing in air for 30 min. The crystallized BZN thin films exhibit the excellent dielectric properties and frequency responses. The dielectric permittivity and loss tangent of the crystallized BZN thin films are 154 and 0.038 at 10 GHz, respectively.     

Crystallization behavior and resistance change in eutectic Si15Te85 amorphous films

Crystallization process and the corresponding electrical resistance change were investigated in eutectic Si₁₅Te₈₅ amorphous thin films. The Si₁₅Te₈₅ amorphous film showed two-stage crystallization process upon heating. In the first stage, the Si₁₅Te₈₅ amorphous crystallized into Te crystals at 175 °C. In the second stage, the residual amorphous phase crystallized into Si₂Te₃ crystals at above 300 °C accompanying the resistance drop. Before the second crystallization, the electrical resistance once increased in the temperature range of about 250-295 °C. This phenomenon can be explained by considering the formation of amorphous phase with a high electrical resistivity.     

Structural and electrical properties of LuMnO3 thin film prepared by chemical solution method

Hexagonal LuMnO₃ thin films have been prepared based on a chemical solution deposition method. These films were deposited by spin-coating technique and annealed at different temperatures from 750 °C up to 850 °C, based on the thermogravimetric and differential thermal analysis results. An amorphous phase is observed in the film annealed at 750 °C, while a pure LuMnO₃ hexagonal phase is reached in the films annealed at 800 °C and 850 °C, along with a visible enhancement in the grain morphology as the annealing temperature increase. Low temperature magnetic analysis of the LuMnO₃ films annealed at 850 °C reveals several magnetic transitions, which are consistent with those reported for both LuMnO₃ ceramics and single crystals. Moreover, the emergence of a canted spin arrangement was evidenced from the temperature dependence of the specific induced magnetization and magnetic hysteretic cycles. No significant effect of the substrate on the magnetic properties was also sorted out. Dielectric measurements reveal the existence of a complex frequency behavior of the dielectric permittivity, which can be associated with relaxation processes arising from the interfaces film/electrodes.     

Sputtering deposition of amorphous cadmium stannate as transparent conducting oxide

In this work we studied deposition conditions by RF sputtering of ternary oxides of Cd and Sn, starting from Cd₂SnO₄ target and varying substrate temperature, sputtering power and deposition gas (from inert Ar to oxidizing 50% Ar-50% O₂ atmosphere). The aim of this study was to obtain thin films for use as Transparent Conducting Oxide (TCO). TCOs are oxides that couples low sheet resistance and high transparency that find application in many fields like solar cells, light emitting diodes and transparent thin film transistors.Thin films functional properties were characterised by means of sheet resistance and transmittance measurements in the visible region, and film composition and structure were investigated by total reflection X ray fluorescence and glancing incidence X ray diffraction. Morphology was studied by Atomic Force Microscopy and Scanning Electron Microscope and showed very smooth surface suitable for solar cells application. Composition and phase analysis allowed us to discuss possible correlation of film structure with functional properties. Deposition in inert atmosphere at 400 °C substrate temperature was selected for its low sheet resistance and high transparency that are comparable to the ones of commercial TCOs like indium tin oxide or SnO₂: F. The thin film obtained in these conditions was amorphous, and it crystallized into CdSnO₃ ilmenite phase when annealed at 700 °C; segregation of Sn₃O₄ was also observed. Since sheet resistance of thin films increases after annealing treatments, amorphous thin film was selected for future applications.     

Hydrophilic properties of nano-TiO2 thin films deposited by RF magnetron sputtering

Microstructure and hydrophilicity of nano-titanium dioxide (TiO₂) thin films, deposited by radio frequency magnetron sputtering, annealed at different temperatures, were studied by field emission scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and water contact angle methods. It is found that the crystal phase transforms from amorphous to rutile structure with increase of annealing temperature from room temperature to 800 °C. It is also indicated that the organic contaminants on the surface of the films can be removed and the oxygen vacancies can be reduced by the annealing treatment. Annealed at the temperature below 300 °C, amorphous TiO₂ thin films show rather poor hydrophilicity, and annealed at the temperature range from 400 to 650 °C, the super hydrophilicity anatase of TiO₂ thin films can be observed. However, when the annealing temperature reaches 800 °C, the hydrophilicity of the films declines mainly derived from the appearance of rutile.     

Structural and mechanical properties of multi-element (AlCrMoTaTiZr)Nx coatings by reactive magnetron sputtering

(AlCrMoTaTiZr)N_x high-entropy films were deposited on silicon wafer and cemented carbide substrates from a single alloy target by reactive RF magnetron sputtering under a mixed atmosphere of Ar and N₂. The effect of nitrogen flow ratio R_N on chemical composition, morphology, microstructure, and mechanical properties of the (AlCrMoTaTiZr)N_x films was investigated. Nitrogen-free alloy film had an amorphous structure, while nitride films with at least 37 at.% N exhibited a simple NaCl-type FCC (face-centered cubic) structure. Mixed structures occurred in films with lower nitrogen contents. Films with the FCC structure were thermally stable without phase decomposition at 1000 °C after 10 h. The (AlCrMoTaTiZr)N film deposited at R_N = 40% exhibited the highest hardness of 40.2 GPa which attains the superhard grade. The main strengthening mechanisms for this film were grain-size and solid-solution strengthening. A residual compressive stress of 1.04 GPa was small to account for the observed hardness. The nitride film was wear resistant, with a wear rate of 2.8 × 10^− 6 mm³/N m against a loaded 100Cr6 steel ball in the sliding wear test. These high-entropy films have potential in hard coating applications.