Cathodoluminescence of CaWO4 and SrWO4 thin films prepared by spray pyrolysis

Thin films of CaWO₄ and SrWO₄ were prepared on glass substrates by spray pyrolysis. The effects of preparation conditions and monovalent, bivalent and trivalent cation doping on cathodoluminescence (CL) properties of the films were studied. Polycrystalline CaWO₄ and SrWO₄ films formed a scheelite structure after being annealed above 300°C. They exhibited analogous cathodoluminescence consisting of a blue emission band at 447 nm and a blue-green emission band at 487 nm. The blue and blue-green emission intensities increased with substrate and annealing temperature. Annealing atmosphere and doping with Ag⁺, Pb²⁺ and La³⁺ did not influence the characteristics of the blue and blue-green emissions, whereas Eu³⁺ did. The results indicated both the blue and blue-green emissions originated from the WO₄²⁻ molecular complex. The luminance and efficiency for CaWO₄ film were 150 cd/m² and 0.7 lm/W at 5 kV and 57 μA/cm².     

Characterization of gallium-nitrogen co-doped zinc oxide thin films prepared by RF diode sputtering

We investigated the possibility of achieving p-type zinc oxide (ZnO) by RF diode sputtering and gallium-nitrogen co-doping. ZnO:Ga:N thin films were prepared with a different N₂ content in Ar/N₂ working gas, ranging from 0 to 100%, and at a varying substrate temperature, from room temperature (RT) to 300 °C. A hole conduction with maximum carrier concentration of 2.6 × 10¹⁸ cm⁻³, mobility of 2 cm²/Vs and resistivity of 1.5 Ω cm resulted from deposition at RT with 100% N₂. It arose from N incorporation and formation of N_O acceptors. In the secondary ion mass spectrometry (SIMS) depth profiles of the co-doped films were observed NO/NO₂ negative ions. Average transmittance (including Corning glass substrate) across the visible spectrum varied (60 ÷ 66%) with increasing nitrogen content (50 ÷ 100% N₂). As the substrate temperature increased (RT - 300 °C), highly transparent (T ∼72-83%) and conductive (electron concentrations of 10¹⁷-10¹⁹ cm⁻³) n-type ZnO:Ga:N films were attained. Reduction of optical band gap (E_g) (∼3.13-3.08 eV) was observed for co-doped ZnO films. Atomic force microscopy (AFM) images revealed that the films grown at RT have roughness of approximately 5.3 nm while roughness of those grown at 300 °C is approximately 3.9 nm.     

Electrical and optical properties of amorphous indium zinc oxide films

Valence electron control and electron transport mechanisms on the amorphous indium zinc oxide (IZO) films were investigated. The amorphous IZO films were deposited by dc magnetron sputtering using an oxide ceramic IZO target (89.3 wt.% In₂O₃ and 10.7 wt.% ZnO). N-type impurity dopings, such as Sn, Al or F, could not lead to the increase in carrier density in the IZO. Whereas, H₂ introduction into the IZO deposition process was confirmed to be effective to increase carrier density. By 30% H₂ introduction into the deposition process, carrier density increased from 3.08 × 10²⁰ to 7.65 × 10²⁰ cm^− 3, which must be originated in generations of oxygen vacancies or interstitial Zn²⁺ ions. Decrease in the transmittance in the near infrared region and increase in the optical band gap were observed with the H₂ introduction, which corresponded to the increase in carrier density. The lowest resistivity of 3.39 × 10^− 4 Ω cm was obtained by 10% H₂ introduction without substrate heating during the deposition.     

Properties of nanocrystalline zinc oxide thin films prepared by thermal decomposition of electrodeposited zinc peroxide

Zinc peroxide thin films were electrodeposited from aqueous solution at room temperature using H₂O₂ as the oxidation agent. Nanocrystalline zinc oxide thin films were then obtained from thermal decomposition of zinc peroxide thin films. The grain sizes of ZnO through thermal decomposition of ZnO₂ at 200 °C, 300 °C and 400 °C were estimated from the peak width of ZnO(110) obtained from X-ray diffraction and were 6.3 nm, 9.1 nm and 12.9 nm, respectively. The optical properties of zinc oxide thin films have been studied. The photoluminescence results indicate that ZnO thin films have low Stokes blue shift (about 110 meV) and low oxygen vacancies.     

Optical and electrical properties of ZnO films prepared by URT-IP method

Optical and electrical properties were studied on thin polycrystalline ZnO films (200-nm thick) deposited on glass substrates at 200 °C by a DC-arc ion plating method (URamoto-Tanaka-type ion plating method). Effects of the oxygen flow rate (OFR) on film properties were examined. The resistivity of undoped films changed from 4.2×10⁻³ to 9.6×10⁻¹ Ω cm, corresponding to the carrier concentration of 1.0×10²⁰-1.2×10¹⁸ cm⁻³, depending on the increase in OFR from 0 to 40 sccm. The Hall mobility tends to be the maximum value of 28 cm² (V s)⁻¹ at OFR of 10 sccm. Photoluminescence (PL) spectra exhibited a dominant near-band-edge (NBE) emission together with weak PL bands at 2.2 and 3.2 eV. Intensity of NBE was maximum at OFR of 10 sccm. Intensity of the PL band at 2.2 eV increased with increase in OFR. As a result of Ga-doping, the resistivity decreased and the carrier concentration increased by one order of magnitude. The optical transmittance was more than 90% in 400-1200 nm. The ZnO:Ga (3 and 4 wt.% Ga-doped) thin films with the lowest resistivity of 2.6×10⁻⁴ Ω cm, the highest mobility of 25 cm² (V s)⁻¹, and the highest PL intensity were obtained at OFR of 10 sccm. Further increase of OFR led to the decrease in both mobility and PL intensity.     

Pulsed laser deposition and photoluminescence measurements of ZnO thin films on flexible polyimide substrates

In order to assess the potential of zinc oxide (ZnO) in flexible electronics applications, we created continuous ZnO films on polymeric substrates for evaluation of structural and optical properties. Specifically, we have used pulsed laser deposition to deposit ZnO films with thickness of several microns on flexible free-standing polyimide substrates. A KrF excimer laser (248 nm) operated at fluences of 3.0-6.2 J/cm² was used. ZnO films were deposited at temperatures between room temperature and 300 °C under O₂ atmosphere at a pressure of 50 Pa. Good flexibility characterizes the obtained layers and X-ray diffraction measurements show that films present all reflections of hexagonal ZnO. We discuss luminescence measurements on the films in relation to the complex interface phenomena expected in our samples.     

Oxygen pressure and measurement temperature dependence of defects related bands in zinc oxide films

The ZnO films were fabricated by pulsed laser deposition at various oxygen pressure on single crystal silicon substrate. The structural and optical properties were investigated at various measurement temperature. The results showed that all the films have good c-axis preferred orientation. The different defects in films were fabricated which can be caused by various oxygen pressure. The films deposited at 1 Pa oxygen pressure have the most intense and narrow UV emission, and did not exhibit the deep band emission at the various measurement temperature. With the decrease of measurement temperature, the V_O-, O_i- and O_Zn-related band energy decreases, which is opposed to the V_Zn-related defects, meanwhile, the intensity of O_i-related emission peak has a sharp increase.     

High quality amorphous indium zinc oxide thin films synthesized by pulsed laser deposition

Indium zinc oxide films were grown from targets with two different In atomic concentration [In/(In + Zn)] of 40% and 80% by the pulsed laser deposition technique on glass substrates from room temperature up to 100 °C. X-ray diffraction and reflectometry investigations showed that films were amorphous and dense. Thin films (thickness < 100 nm) exhibited higher optical transmittance and resistivities than thick films (thickness > 1000 nm), probably caused by a significant decrease of oxygen vacancies due to atmosphere exposure. Films deposited from the In rich target under an oxygen pressure of 1 Pa exhibited optical transmittance higher than 85%, resistivities around 5- 7 × 10^− 4 Ω cm and mobilities in the 47-54 cm²/V s range.     

Growth and surface characterization of magnetron sputtered zinc nitride thin films

Zinc nitride films were deposited on Si(100) substrates at room temperature using RF-magnetron sputtering in pure N₂ and in Ar + N₂ atmospheres. Two active phonon modes (270.81 and 569.80 cm^− 1) are observed in Raman spectra for films deposited in Ar + N₂ atmosphere. Atomic force microscopy showed that the average surface roughness of the films deposited in pure N₂ atmosphere (1.3-3.33 nm) was less than for those deposited in a mixed Ar + N₂ atmosphere (10.3-12.8 nm). Low temperature cathodoluminescence showed two emission bands centered at 2.05 eV and 3.32 eV for both types of films.     

Pulsed laser deposition of crystalline ZrC thin films

ZrC thin films were grown on Si substrates by the pulsed laser deposition (PLD) technique under various conditions. X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), X-ray diffraction and reflectivity, spectroscopic ellipsometry, and four point probe measurements were used to characterize the properties of the deposited films. It has been found that crystalline films could be grown only by using laser fluences higher than 5 J/cm² and substrate temperatures in excess of 500 °C. For a fluence of 10 J/cm² and a substrate temperature of 700 °C, cubic ZrC films (a = 0.469 nm) exhibiting a (200)-texture were deposited under vacuum or low pressure C₂H₂ atmosphere. These films were smooth, with surface roughness values below 1.0 nm and mass densities around the tabulated value of 6.7 g/cm³. AES depth profiling investigations showed oxygen contamination around 7% in the bulk region. Despite the relatively high levels of oxygen contamination, the deposited ZrC films were very conductive. The use of a low C₂H₂ pressure atmosphere during deposition had a small beneficial effect on crystallinity and stoichiometry of the films.     

Study of structural and optical properties of Ge doped ZnO films

The Ge doped ZnO films were deposited on quartz substrates by radio frequency magnetron sputtering. The effects of doping and substrate temperature on the structural and optical properties of the Ge doped ZnO films were investigated by means of X-ray diffraction (XRD), UV-visible transmission spectra, X-ray photoelectron spectroscopy and photoluminescence (PL) spectra. The XRD patterns showed that Zn₂GeO₄ phases were formed in the films. With the increase of substrate temperature the crystallization of Zn₂GeO₄ was improved, and that of ZnO phases turned worse, and no diffraction peak of ZnO was observed when the substrate temperature was 700 °C. Obvious ultraviolet (UV) light emission was found due to ZnO grains, and it was much stronger than that of un-doped ZnO films. The enhancement of UV light emission at about 380 nm may be caused by excitons which were formed at the interface between Zn₂GeO₄ and ZnO grains. In the visible region of the PL spectra, the green light emission peak of samples at about 512 nm was associated with defects in ZnO. A red shift of the green light emission peak was observed which can be explained by the fact that there is a luminescence center at about 548 nm taking the place of the defect emission of ZnO with the increase of substrate temperature. The red shift of the green light emission peak and the 548 nm green light emission peaks of the PL spectrum show that some Ge²⁺ should replace the Zn²⁺ positions during the Zn₂GeO₄ grains growth and form the Ge²⁺ luminescence centers in Zn₂GeO₄ grains.     

Ultrathin Al-doped transparent conducting zinc oxide films fabricated by pulsed laser deposition

Al-doped transparent conducting zinc oxide (AZO) films, approximately 20-110 nm-thick, were deposited on glass substrates at substrate temperatures between 200 and 300 °C by pulsed laser deposition (PLD) using an ArF excimer laser (λ = 193 nm). When fabricated at a substrate temperature of 260 °C, a 40-nm-thick AZO film showed a low resistivity of 2.61 × 10^− 4 Ω·cm, carrier concentration of 8.64 × 10²⁰ cm^− 3, and Hall mobility of 27.7 cm²/V·s. Furthermore, for an ultrathin 20-nm-thick film, a resistivity of 3.91 × 10^− 4 Ω·cm, carrier concentration of 7.14 × 10²⁰ cm^− 3, and Hall mobility of 22.4 cm²/V·s were obtained. X-ray diffraction (XRD) spectra, obtained by the θ-2θ method, of the AZO films grown at a substrate temperature of 260 °C showed that the diffraction peak of the ZnO (0002) plane increased as the film thickness increased from 20 to 110 nm. The full-width-at-half-maximum (FWHM) values were 0.5500°, 0.3845°, and 0.2979° for film thicknesses of 20, 40, and 110 nm, respectively. For these films, the values of the average transmittance in visible light wavelengths (400-700 nm) were 95.1%, 94.2%, and 96.6%, respectively. Field emission scanning electron microscopy (FE-SEM) and atomic force microscopy (AFM) observations showed that even the 20-nm-thick films did not show island structures. In addition, exfoliated areas or vacant and void spaces were not observed for any of the films.     

Growth and characterization of electrosynthesised zinc oxide thin films

Zinc oxide (ZnO) films have been electrodeposited from an aqueous solution containing 0.1 M zinc nitrate as the electrolyte with pH around 5±0.1. The deposition was carried out by galvanostatic reduction with an applied cathodic current density in the range between 5 and 20 mA cm⁻². The influence of bath composition on the preparation of ZnO films is studied. The effects of zinc nitrate concentration and cathodic current density on the deposition rate of ZnO films were also studied. An optimum current density of 10 mA cm⁻² is identified for the growth of ZnO film with improved crystallinity and optical transmittance. The crystalline structure of the deposits studied by X-ray diffraction reveals the possibility of growing hexagonal ZnO films under suitable electrochemical conditions. The surface morphological studies by scanning electron micrographs revealed the presence of nodular appearance for films deposited at 800 °C bath temperatures.     

Transparent conductive ZnO:B films deposited by magnetron sputtering

This paper focuses on the preparation of boron doped ZnO (ZnO:B) films prepared by nonreactive mid-frequency magnetron sputtering from ceramic target with 2 wt.% doping source. Adjusting power density, ZnO:B film with low resistivity (1.54 × 10^− 3 Ω cm) and high transparency (average transparency from 400 to 1100 nm over 85%) was obtained. Different deposition conditions were introduced as substrate fixed in the target center and hydrogen mediation. Hall mobility increased from 11 to above 26 cm²/V·s, while carrier concentration maintained almost the same, leading to low resistivity of 6.45 × 10^− 4 Ω cm. Transmission spectra of ZnO:B films grown at various growth conditions were determined using a UV-visible-NIR spectrophotometer. An obvious blue-shift of absorption edge was obtained while transmittances between 600 nm and 1100 nm remained almost the same. Optical band baps extracted from transmission spectra showed irregular enhancement due to the Burstein-Moss effect and band gap renormalization. Photoluminescence spectra also showed a gradual increase at UV emission peak due to free exciton transition near band gap. We contributed this enhancement in both optical band gap and UV photoluminescence emission to the lattice structure quality melioration.     

Al-doped ZnO films by pulsed laser deposition at room temperature

Polycrystalline Al-doped ZnO films with good photoluminescence property were successfully deposited on quartz glass substrates by pulsed laser deposition (PLD) at room temperature. The films were obtained by ablating a metallic target (Zn:Al 3 wt%) at various laser energy densities (1.0-2.1 J/cm²) in oxygen atmosphere (9 Pa). The structure of the films was characterized by XRD. Ultraviolet photoluminescence centered at 359-361 nm was observed in the room temperature PL spectra of the Al-doped ZnO films.     

ZnO ultra-fine powders and films: hydrothermal synthesis,luminescence and UV lasing at room temperature

Zinc oxide ultra-fine crystalline powders and polycrystalline films of high optical quality were synthesized under soft hydrothermal conditions. The phase composition, crystal morphology, and luminescent properties of submicron ZnO powders and films were studied depending on synthesis conditions (system composition, precursor kind, solvent type and concentration, temperature). For the systems containing metallic zinc, the ZnO growth mechanism was suggested. The most intensive UV luminescence and the highest values of I_UV/I_VIS were observed for polycrystalline films grown on Zn substrates. Low-threshold UV lasing at room temperature was found for ZnO-films, grown in hydrothermal systems with hydroxide or halide solutions as solvents, E _th = 1–5 MW/cm². The lowest threshold was observed on the ZnO films grown using LiOH as a solvent and zinc nitrate as ZnO-precursor. Clear mode structures with line-width 0.3 nm are characteristic of the lasing spectra.     

Luminescent properties of Al2O3:Tb3+ powders embedded in polyethylene terephthalate films

The luminescent properties of Al₂O₃:Tb³⁺ powders embedded in polyethylene terephthalate (PET) films have been studied. Luminescent Al₂O₃:Tb³⁺ polycrystalline powders were synthesized by a simple evaporation method. The powder embedded films were obtained by the spray pyrolysis technique. The photoluminescence and cathodoluminescence emission spectra from these samples show, in both cases, luminescence peaks associated with transitions within the electronic energy levels of Tb³⁺ ions. The dominant peak is at 544 nm corresponding to the ⁵D₄ to ⁷F₅ transition. In the case of the powder embedded films, the CIE coordinates depend on the excitation wavelength because there is a blue emission contribution from the PET host. UV–Vis% transmission measurements on these films show that they are transparent (∼80% and 95% T).     

Application of pulsed laser deposited zinc oxide films to thin film transistor device

Transparent zinc oxide (ZnO) thin films were deposited on various substrates using a pulsed laser deposition (PLD) technique. During the PLD, oxygen pressure and substrate temperature were varied in order to find an optimal preparation condition of ZnO for thin film transistor (TFT) application. Dependence of optical, electrical and crystalline properties on the deposition conditions was investigated. The ZnO thin films were then deposited on SiN/c-Si layer structures in order to fabricate a TFT device. The pulsed laser deposited ZnO films showed a remarkable TFT performance: field effect mobility (μ_FE) of 2.4-12.85 cm²/V s and ratio of on and off current (R_on/off) in 2-6 order range. Influence of ZnO preparation conditions on the resulting TFT performance was discussed.     

Effect of the oxygen pressure on the photoluminescence properties of ZnO thin films by PLD

ZnO thin films on Si(111) substrate were deposited by laser ablation of Zn target in oxygen reactive atmosphere; Nd-YAG laser with wavelength of 1064 nm was used as laser source. The experiments were performed at laser energy density of 31 J/cm², substrate temperature of 400 °C and various oxygen pressures (5–65 Pa). X-ray diffraction was applied to characterize the structure of the deposited ZnO films and the optical properties of the ZnO thin films were characterized by photoluminescence with an Ar ion laser as a light source using an excitation wavelength of 325 nm. The influence of the oxygen pressure on the structural and optical properties of ZnO thin films was investigated. It was found that ZnO film with random growth grains can be obtained under the condition of oxygen pressure 5–65 Pa. It will be clearly shown that the grain size and the formation of intrinsic defects depend on the oxygen partial pressure and that high optical quality of the ZnO films is obtained under low oxygen pressure (5 Pa, 11 Pa) conditions.     

RF diode reactive sputtering of n- and p-type zinc oxide thin films

We present the relationship between parameters of reactive RF diode sputtering from a zinc oxide (ZnO) target and the crystalline, electrical and optical properties of n-/p-type ZnO thin films. The properties of the ZnO thin films depended on RF power, substrate temperature and, particularly, on working gas mixtures of Ar/O₂ and of Ar/N₂. Sputtering in Ar+O₂ working gas (up to 75% of O₂) improved the structure of an n-type ZnO thin film, from fibrous ZnO grains to columnar crystallites, both preferentially oriented along the c-axis normally to the substrate (〈0 0 2〉 direction). These films had good piezoelectric properties but also high resistivity (ρ≈10³ Ω cm). ZnO:N p-type films exhibited nanograin structure with preferential 〈0 0 2〉 orientation at 25% N₂ and 〈1 0 0〉 orientation for higher N₂ content. The presence of nitrogen N_O at O-sites forming N_O-O acceptor complexes in ZnO was proven by SIMS and Raman spectroscopy. A minimum value of resistivity of 790 Ω cm, a p-type carrier concentration of 3.6×10¹⁴ cm⁻³ and a Hall mobility of 22 cm² V⁻¹ s⁻¹ were obtained at 75% N₂.