Thermal oxidation of n-type ZnN films made by -sputtering from a zinc nitride target, and their conversion into p-type films

Transparent p-type thin films, containing zinc oxide phases, have been fabricated from the oxidation of n-type zinc nitride films. The zinc nitride thin films were deposited by rf-magnetron sputtering from a zinc nitride target in pure N₂ and pure Ar plasma. Films deposited in Ar plasma were conductive (resistivity 4.7×10⁻² Ω cm and carrier concentrations around 10²⁰ cm⁻³) Zn-rich Zn_xN_y films of low transmittance, whereas Zn_xN_y films deposited in N₂ plasma showed high transmittance (>80%), but five orders of magnitude lower conductivity. Thermal oxidation up to 550 C converted all films into p-type materials, exhibiting high resistivity, 10²–10³ Ω cm, and carrier concentration around 10¹³ cm⁻³. However, upon oxidation, the Zn_xN_y films did not show the zinc oxide phase, whereas Zn-rich Zn_xN_y films were converted into films containing ZnO and ZnO₂ phases. All films exhibited transmittance >85% with a characteristic excitonic dip in the transmittance curve at 365 nm. Low temperature photoluminescence revealed the existence of exciton emissions at 3.36 and 3.305 eV for the p-type zinc oxide film.     

Fabrication and properties of ZnO:Cu and ZnO:Ag thin films

Thin films of ZnS and ZnO:Cu were grown by an original metal–organic chemical vapour deposition (MOCVD) method under atmospheric pressure onto glass substrates. Pulse photo-assisted rapid thermal annealing of ZnO:Cu films in ambient air and at the temperature of 700–800 C was used instead of the common long-duration annealing in a vacuum furnace. ZnO:Ag thin films were prepared by oxidation and Ag doping of ZnS films. At first a closed space sublimation technique was used for Ag doping of ZnO films. The oxidation and Ag doping were carried out by a new non-vacuum method at a temperature >500 C. Crystal quality and optical properties were investigated using X-ray diffraction (XRD), atomic force microscopy (AFM), and photoluminescence (PL). It was found that the doped films have a higher degree of crystallinity than undoped films. The spectra of as-deposited ZnO:Cu films contained the bands typical for copper, i.e. the green band and the yellow band. After pulse annealing at high temperature the 410 and 435 nm photoluminescent peaks were observed. This allows changing of the emission colour from blue to white. Flat-top ZnO:Ag films were obtained with the surface roughness of 7 nm. These samples show a strong ultraviolet (UV) emission at room temperature. The 385 nm photoluminescent peak obtained is assigned to the exciton–exciton emission.     

Ni–Al ohmic contact to p-type 4H-SiC

Investigations on Ni/Al alloys to form ohmic contacts to p-type 4H-SiC are presented in this paper. Different ratios of Ni/Al were examined. Rapid thermal annealing was performed in argon atmosphere at 400 C for 1 min, followed by an annealing at 1000 C for 2 min. In order to extract the specific contact resistance, TLM test structures were fabricated. A specific contact resistance of 3×10⁻⁵ Ω cm² was obtained reproducibly on Al²⁺ implanted p-type layers, having a doping concentration of 1×10¹⁹ cm⁻³. The lowest specific contact resistance value measured amounts to 8×10⁻⁶ Ω cm².     

Electrical characterisation of phosphorus-doped ZnO thin films grown by pulsed laser deposition

Phosphorus-doped ZnO films were grown by pulsed laser deposition using a ZnO:P₂O₅-doped target as the phosphorus source with the aim of producing p-type ZnO material. ZnO:P layers (with phosphorus concentrations of between 0.01 to 1 wt%) were grown on a pure ZnO buffer layer. The electrical properties of the films were characterised from temperature dependent Hall-effect measurements. The samples typically showed weak n-type conduction in the dark, with a resistivity of 70 Ω cm, a Hall mobility of μ_n0.5 cm² V ⁻¹ s⁻¹ and a carrier concentration of n3×10¹⁷ cm⁻³ at room temperature. After exposure to an incandescent light source, the samples underwent a change in conduction from n- to p-type, with an increase in mobility and decrease in concentration for temperatures below 300 K.     

The effect on the annealing temperature of Li doped ZnO thin film for a film bulk acoustic resonator

We investigated the material and electrical properties of Li doped ZnO thin film (ZLO) with variation of the annealing temperature. In the 500 C sample, ZLO film showed well defined (002) c-axis orientation and a full width half-maximum property of 0.25. The electrical properties of ZLO thin films showed the excellent specific resistance of 1.5×10¹¹ Ω cm. Finally, the frequency characteristics of the ZLO thin film FBAR, according to the annealing temperature, showed improvement of the return loss from 24.48 to 30.02 dB at a resonant frequency of 1.17 GHz.     

Enhancement of surface morphology and optical properties of nanocolumnar ZnO films

Nanocolumnar ZnO films were prepared by electrodeposition (ED) on a glass substrate covered with a conductive layer of thin oxide doped with fluorine (FTO). After deposition the samples were annealed in oxidizing or reducing atmosphere, at temperatures between 100 to 500 C, in order to follow the evolution of optical properties and morphology. The optical properties of these films were studied by means of photoluminescence spectroscopy (PL) and the morphology by scanning electron microscopy (SEM). Films annealed at 300 C exhibit a higher ultraviolet emission peak, originating from exciton transitions. A green band related to deep-level emission centered at 500 nm, shows a drastic increase at 500 C. These results are independent of the annealing atmosphere. An increase of coalescence is also observed after annealing at 500 C. These results are explained taking into account the contribution of different point defects.     

Lattice location of implanted As in ZnO

Radioactive ⁷³As ions were implanted into a ZnO single crystal at room temperature with 60 keV up to a fluence of 2×10¹³ cm⁻². Subsequently, the angular emission channeling patterns of emitted conversion electrons were recorded by means of a position-sensitive detector in the as-implanted state and following annealing up to 900 C, and were compared to simulated emission yields for a variety of different lattice sites. We find that As does not occupy substitutional O sites, but mainly occupies the substitutional Zn sites. The fraction of As on O sites was at most a few per cent. Arsenic in ZnO is thus an interesting example of an impurity in a semiconductor where the major impurity lattice site is determined by atomic size and electronegativity rather than its position in the periodic system. Possible consequences with respect to the role of arsenic as a p-type dopant in ZnO are being discussed.     

Effects of annealing ambience on ZnO:N films grown by MOCVD and the p-type doping mechanism of ZnO:N films investigated by XANES

ZnO:N thin films were deposited on sapphire substrate by metal organic chemical vapor deposition with NH₃ as N-doping sources. The reproducible p-type ZnO:N film with hole concentration of ∼10¹⁷ cm⁻³ was successfully achieved by subsequent in situ thermal annealing in N₂O plasma protective ambient, while only weak p-type ZnO:N film with remarkably lower hole concentration of ∼10¹⁵ cm⁻³ was obtained by annealing in O₂ ambient. To understand the mechanism of the p-type doping behavior of ZnO:N film, X-ray photoelectron spectroscopy (XPS) and soft X-ray absorption near-edge spectroscopy (XANES) measurements have been applied to investigate the local electronic structure and chemical states of nitrogen atoms in ZnO:N films.     

Atomic layer deposition and characterization of Ga-doped ZnO thin films

Low-resistivity n-type ZnO thin films were grown by atomic layer deposition (ALD) using diethylzinc (DEZ) and H₂O as Zn and O precursors. ZnO thin films were grown on c-plane sapphire (c- Al₂O₃) substrates at 300 C. For undoped ZnO thin films, it was found that the intensity of ZnO () reflection peak increased and the electron concentration increased from 6.8×10¹⁸ to 1.1×10²⁰ cm⁻³ with the increase of DEZ flow rate, which indicates the increase of O vacancies () and/or Zn interstitials (Zn_i). Ga-doping was performed under Zn-rich growth conditions using triethylgallium (TEG) as Ga precursor. The resistivity of 8.0×10⁻⁴ Ω cm was achieved at the TEG flow rate of 0.24 μmol/min.     

ZnO films grown by laser ablation with and without oxygen CVD

In the present work we have studied the properties of zinc oxide (ZnO) thin films grown by laser ablation of ZnO targets under different substrate temperature and background oxygen conditions. The ZnO layers were deposited with a Pulsed Laser Deposition (PLD) system on pre-nitrided (0001) sapphire (Al₂O₃), using the base line of a Nd:YAG laser at 1064 nm. The films were characterized by different structural and optical methods, including X-ray diffraction (XRD), scanning electron microscopy (SEM), optical transmission spectroscopy, and steady-state photoluminescence (PL). XRD analysis with rocking curves and θ–2θ scans indicates preferential growth along the c-axis direction with a full width at half maximum (FWHM) smaller than 1.5. Low-temperature photoluminescence (PL) showed strong excitonic emission near 3.36 eV between 9 and 65 K.     

Peculiarities of electron field emission from ZnO nanocrystals and nanostructured films

ZnO microcrystals and nanocrystals were grown on silicon substrates by condensation from vapour phase. Nanostructured ZnO films were deposited by plasma enhanced metal organic chemical vapour deposition (PEMOCVD). The parameters of field emission, namely form-factor β and work function , were calculated for ZnO structures by the help of the Fowler–Nordheim equation. The work functions from ZnO nanostructured films were evaluated by a comparison method. The density of emission current from ZnO nanostructures reaches 0.6 mA/cm² at electric force F=2.110⁵ V/cm. During repeatable measurements β changes from 5.810⁴ to 2.310⁶ cm⁻¹, indicating improvement of field emission. Obtained values of work functions were 3.7±0.37 eV and 2.9–3.2 eV for ZnO nanostructures and ZnO films respectively.     

Investigation of p-type behavior in Ag-doped ZnO thin films by E-beam evaporation

Ag-doped ZnO (ZnO:Ag) thin films were grown on glass substrates by E-beam evaporation technique. The structural, electrical and optical properties of the films were investigated as a function of annealing temperature. The films were subjected to post annealing at different temperatures in the range of 350-650 °C in an air ambient. All the as grown and annealed films at temperature of 350 °C showed p-type conduction. The films lost p-type conduction after post annealing treatment temperature of above 350 °C, suggesting a narrow post annealing temperature window for the fabrication of p-type ZnO:Ag films. ZnO:Ag film annealed at 350 °C revealed lowest resistivity of 7.25 × 10⁻² Ω cm with hole concentration and mobility of 5.09 × 10¹⁹ cm⁻³ and 1.69 cm²/V s, respectively. Observation of a free-to-neutral-acceptor (e,A^o) and donor-acceptor-pair (DAP) emissions in the low temperature photoluminescence measurement confirms p-type conduction in the ZnO:Ag films.     

Al Schottky contact on p-GaSe

A new Schottky diode, Al/p-GaSe, was presented in this study. It shows an effective barrier height of 0.96 eV with an ideality factor of 1.24 over five decades and a reverse leakage current density of 4.12×10⁻⁷ A/cm² at −2 V after rapid thermal annealing at 400 C for 30 s. The generation–recombination effect of the Schottky diode was decreased as the annealing temperature was increased. The formation of Al_1.33Se₂ was observed by X-ray diffraction analysis after the diode was annealed at 400 C for 30 s. Owing to the grains’ growth, the surface morphology of the 400 C-annealed diode was rougher than that of the unannealed diode, which was observed both by the AFM and the SEM analysis.     

p-Type conduction in phosphorus-doped ZnO thin films by MOCVD and thermal activation of the dopant

Phosphorus-doped p-type ZnO thin films have been realized by metalorganic chemical vapor deposition (MOCVD). The conduction type of ZnO films is greatly dependent on the growth temperature. ZnO films have the lowest resistivity of 11.3 Ωcm and the highest hole concentration of 8.84 × 10¹⁸ cm⁻³ at 420 °C. When the growth temperature is higher than 440 °C, p-type ZnO films cannot be achieved. All the films exhibited p-type conduction after annealing, and the electrical properties were improved comparing with the as-grown samples. Secondary ion mass spectroscopy (SIMS) test proved that phosphorus (P) has been incorporated into ZnO.     

Conductivity increase of ZnO:Ga films by rapid thermal annealing

Due to a constant increase in demands for transparent electronic devices the search for alternative transparent conducting oxides (TCO) is a major field of research now. New materials should be low-cost and have comparable or better optical and electrical characteristics in comparison to ITO. The use of n-type ZnO was proposed many years ago, but until now the best n-type dopant and its optimal concentration is still under discussion. Ga was proposed as the best dopant for ZnO due to similar atomic radius of Ga³⁺ compared to Zn²⁺ and its lower reactivity with oxygen. The resistivity ρ of ZnO:Ga/Si (100) films grown by PEMOCVD was found to be 3×10⁻² Ω cm. Rapid thermal annealing (RTA) was applied to increase the conductivity of ZnO:Ga (1 wt%) films and the optimal regime was determined to be 800  C in oxygen media for 35 s. The resistivity ratio before and after the annealing and the corresponding surface morphologies were investigated. The resistivity reduction () was observed after annealing at optimal regime and the final film resistivity was approximately ≈4×10⁻⁴ Ω cm, due to effective Ga dopant activation. The route mean square roughness (R_q) of the films was found to decrease with increasing annealing time and the grain size has been found to increase slightly for all annealed samples. These results allow us to prove that highly conductive ZnO films can be obtained by simple post-growth RTA in oxygen using only 1% of Ga precursor in the precursor mix.     

Effect of Li incorporation on the structural and optical properties of ZnO

This paper presents the structural and optical properties of the as-prepared and lithium-doped ZnO at different percentages of Li incorporation (5%–15%) in ZnO. Effect of doping with various percentages of Li at a particular annealing temperature of 600 C is studied. The samples are characterized by X-ray diffraction, absorption spectroscopy, photoluminescence and Raman spectroscopy. The X-ray diffraction and micro-Raman spectroscopy confirm that the lithium substituted zinc and retains the wurtzitic structure of the lattice. Such substitutional Li in ZnO gives rise to shallow acceptor levels and contributes to the p-type conductivity. From the results of the absorption spectroscopy we observed the evidence of shallow levels upon doping and we also determined the bandgap of the materials which is found to be 3.36 eV. Photoluminescence studies reveal that no deep level is formed. The electrical measurements show that the Li-doped samples are p-type in nature and this is due to substitutional Li.     

Dependences of structural and electrical properties on thickness of polycrystalline Ga-doped ZnO thin films prepared by reactive plasma deposition

Polycrystalline Ga-doped (Ga content: 4 wt%) ZnO (GZO) thin films were deposited on glass substrates at 200 C by a reactive plasma deposition with DC arc discharge technique. The dependences of structural and electrical properties of GZO films on thickness, ranging from 30 to 560 nm, were investigated. Carrier concentration, n, and Hall mobility, μ, increases with increasing film thickness below 100 nm, and then the n remains nearly constant and the μ gradually increases until the thickness reaches 560 nm. The resistivity obtained of the order of 10⁻⁴ Ω cm for these films decreases with increasing film thickness: The highest resistivity achieved is 4.4×10⁻⁴ Ω cm with n of 7.6×10²⁰ cm⁻³ and μ of 18.5 cm²/V s for GZO films with a thickness of 30 nm and the lowest one is 1.8×10⁻⁴ Ω cm with n of 1.1×10²¹ cm⁻³ and μ of 31.7 cm²/V s for the GZO film with a thickness of 560 nm. X-ray diffraction pattern for all the films shows a hexagonal wurtzite structure with its strongly preferred orientation along the c-axis. Full width at half maximum of the (002) preferred orientation diffraction peak of the films decreases with increasing film thickness below 100 nm.     

Effects of annealing temperature on morphologies and optical properties of ZnO nanostructures

The effects of annealing temperature on the morphologies and optical properties of ZnO nanostructures synthesized by sol–gel method were investigated in detail. The SEM results showed that uniform ZnO nanorods formed at 900 C. The PL results showed an ultraviolet emission peak and a relatively broad visible light emission peak for all ZnO nanostructures sintered at different temperature. The increase of the crystal size and decrease of tensile stress resulted in the UV emission peak shifted from 386 to 389 nm when annealing temperature rose from 850 to 1000 C. The growth mechanism of the ZnO nanorods is discussed.     

p-type conduction in ZnO dual-acceptor-doped with nitrogen and phosphorus

A dual-acceptor doping method was proposed to produce p-type conduction in ZnO. Both nitrogen and phosphorus were used as the p-type doping agents. ZnO:(N, P) films were prepared by spray pyrolysis. The p-type conduction was achieved by thermal annealing at appropriate temperatures (500-700 ^°C) for 20 min in O₂ ambient. The lowest resistivity of , with a hole concentration and Hall mobility of 5.3×10¹⁷ cm⁻³ and 0.94 cm² V ⁻¹ s⁻¹, respectively, was obtained at an optimal annealing temperature of 600 ^°C. The p-type behavior was reproducible and stable. The introduction of nitrogen and phosphorus in ZnO were identified by secondary ion mass spectroscopy.     

A novel deposition method to grow ZnO nanorods: Spray pyrolysis

ZnO layers were deposited by chemical spray pyrolysis (CSP) using zinc chloride aqueous solutions onto indium tin oxide (ITO) glass substrates at growth temperatures in the region of 400–580 C. The layers were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and low-temperature () photoluminescence (PL) measurements. The flat film of ZnO obtained at 400 C evolves to a structured layer by raising the temperature up to 500 C. Deposition around 550 C and above results in a layer comprising well-shaped hexagonal ZnO nanorods with diameter of 100–150 nm and length of up to 1 micron. XRD shows strong c-axis orientation of ZnO being in accordance with the SEM study. Deposition of nanorods was successful using ITO with grain size around 100 nm, whereas on fine-grained ITO (grain size < 50 nm) with smooth surface fat crystals with diameter up to 400 nm and length of about 300 nm were formed. Sharp near band edge (NBE) emission peaks centered at 3.360 and 3.356 eV dominated the PL spectra of ZnO at , originating from the exciton transition bound to neutral donors. PL and XRD results suggest that ZnO rods prepared by spray pyrolysis are of high optical and crystalline quality.