Li doped NiO (LixNi1−xO) thin films were epitaxially grown along [111] orientation on c-sapphire by pulsed laser deposition. The structural, electrical, and optical properties of the films were investigated using x-ray diffraction, four probe technique, and UV-visible spectra, respectively. The epitaxial growth of [111] Li doped NiO on [0001] sapphire was determined by using high resolution x-ray Φ scan. Effects of the deposition condition and Li doping concentration variations on the electrical and optical properties of Li doped NiO films were also investigated. The analysis of the resistivity data show that doped Li ions occupy the substitutional sites in the films, enhancing the p-type conductivity. The minimum resistivity of 0.15 Ω cm was obtained for Li0.07Ni0.93O film. The activation energy of Li doped NiO films were estimated to be in the range of 0.11–0.14 eV. Based upon these values, a possible electrical transport mechanism is discussed. A p-n heterojunction has also been fabricated for the optimized p-Li doped NiO with n-ZnO. The insertion of i-MgZnO between the p and n layer led to improved current-voltage characteristics due to reduced leakage current. In the diode architecture, a heteroepitaxial relationship of [111]NiO‖[0001]MgZnO‖[0001]ZnO‖[0001]GZO‖[0001]Al2O3 among the layers was obtained. The p-i-n heterojunction showed good rectification behavior with turn on voltage of 2.8 V and breakdown voltage of 8.0 V.

We report the systematic changes in structural, electrical, and optical properties of NiO thin films on c-sapphire introduced by nanosecond ultraviolet excimer laser pulses. Epitaxial nature of as deposited NiO was determined by x-ray diffraction phi scans and transmission electron microscopy (TEM) and it was established that NiO film growth takes place with twin domains on sapphire where two types of domains have 60° in-plane rotation with respect to each other about the [111] growth direction. We determined that at pulsed laser energy density of 0.275 J/cm2, NiO films exhibited conversion from p-type semiconducting to n-type conductive behavior with three orders of magnitude decrease in resistivity, while maintaining its cubic crystal structure and good epitaxial relationship. Our TEM and electron-energy-loss spectroscopy studies conclusively ruled out the presence of any Ni clustering or precipitation due to the laser treatment. The laser-induced n-type carrier transport and conductivity enhancement were shown to be reversible through subsequent thermal annealing in oxygen. This change in conductivity behavior was correlated with the nonequilibrium concentration of laser induced Ni0-like defect states.

Transition metal containing ZnO powders (Zn 1−x M x O, 0 x 0.30; M = Ni, Mn, Co) have been synthesized by a sol-gel process using zinc acetate dihydrate, respective acetate and oxalic acid as precursors with ethanol as a solvent. The process essentially involves gel formation, drying at 80 • C for 24 h to provide the oxalate, and calcination at 500 • C for 2 h to undergo an exothermic reaction and yield Zn 1−x M x O powder. Their XRD patterns correspond to a wurtzite hcp structure similar to that of pure ZnO, but with the lattice parameters varying slightly with type and extent of doping. It is shown that the dissolution of nickel and cobalt in ZnO is less than 10 at.%, whereas that of manganese lies between 10 and 15 at.%. Other phases that emerge include NiO (hexagonal, a = 2.954 Å, c = 7.236 Å), ZnCo 2 O 4 (cubic, a = 8.094 Å) and ZnMnO 3 (cubic, a = 8.35 Å) in the Ni, Co and Mn containing ZnO systems, respectively. Observations of hysteresis loops both at 10 and 320 K and the nature of ESR spectra provide evidence for the ferromagnetic state in nickel containing ZnO powder. Besides, the deviation occurs in the magnetization versus temperature curves in zero field cooled (ZFC) and field cooled (FC) conditions (blocking temperature T B being 32 K for 5 at.% Ni). The magnetic behaviour of manganese and cobalt doped zinc oxide is, however, different, namely, (i) no hysteresis loops, (ii) decrease in magnetization with increase of Mn or Co content, and (iii) identical M-T curves under ZFC and FC conditions. The inverse susceptibility versus temperature curves of Zn 1−x Mn x O compounds reveal ferrimagnetism with Néel temperature T N of 4 K for x = 0.02, but antiferromagnetism for x = 0.15 and 0.25 with Curie-Weiss temperature of −43 and −30 K, respectively.

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