The effects of thermal annealing in NH3 -ambient on the p-type ZnO films

Thermal annealing in NH₃-ambient was carried out to form p-type ZnO films. The properties were examined by X-ray diffraction (XRD), Hall-effect measurement, photoluminescence (PL), and secondary ion mass spectrometry (SIMS). Electron concentrations in ZnO films were in the range of 10¹⁵–10¹⁷/cm³ with thermal annealing in NH₃-ambient. The activation thermal annealing process was needed at 800 C under N₂-ambient to obtain p-type ZnO. The electrical properties of the p-type ZnO showed a hole concentration of 1.06×10¹⁶/cm³, a mobility of 15.8 cm²/V s, and a resistivity of 40.18 Ω cm. The N-doped ZnO films showed a strong photoluminescence peak at 3.306 eV at 13 K, which is closely related to neutral acceptor bound excitons of the p-type ZnO. The incorporation of nitrogen was confirmed in the SIMS spectra.     

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.     

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.     

Photoluminescence of ZnO nanostructures grown by the aqueous chemical growth technique

Zinc oxide nanostructured films were grown by the aqueous chemical growth technique using equimolar aqueous solutions of zinc nitrate and hexamethylenetetramine as precursors. Silicon(100) and glass substrates were placed in Pyrex glass bottles with polypropylene autoclavable screw caps containing the precursors described above, and heated at 95 C for several hours. X-ray diffraction 2θ/θ scans showed that the only crystallographic phase present was the hexagonal wurtzite structure. Scanning electron microscopy showed the formation of flowerlike ZnO nanostructures, consisting of hexagonal nanorods with a diameter of a few hundred nanometers. The photoluminescence spectra of the ZnO nanostructures were recorded at 18–295 K using a cw He–Cd laser (325 nm) and a pulsed laser (266 nm). The ZnO nanostructures exhibit an ultraviolet emission band centered at 3.192 eV in the vicinity of the band edge, which is attributed to the well-known excitonic transition in ZnO.     

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.     

ZnO nanostructured thin films grown by pulsed laser deposition in mixed O2 / Ar background gas

We report on the properties of ZnO nanostructured thin films grown on either bare or gold patterned a-plane sapphire substrates. The pulsed laser deposition technique was used to deposit all the films at a temperature of 700 C in a mixture of oxygen and argon under a total pressure of 35 Pa. SEM surface characterizations typically showed pyramidal nanostructures with hexagonal symmetry and a coverage density strongly dependent on the O₂ partial pressure. For the patterned samples, wall-like structures of nanoneedles were observed. For all samples, x-ray diffraction results confirmed the high crystalline quality of the nanostructures, with the rocking curve widths of the (0002) reflection as low as 0.09. Similarly, photoluminescence results at room temperature testified to the high optical quality of the material.     

Study of structural, optical and electrical properties of ZnO and SnO2 thin films

The investigation of structure, optical and electrical properties of tin and zinc oxide films on glass substrates by using magnetron sputtering are carried out. X-ray data show the formation of textured tin oxides film during deposition and its transformation to SnO₂ polycrystalline film at low temperature (200 C) if the concentration of oxygen in the chamber is high (O₂ — 100%, Ar — 0%). Optimal conditions of SnO₂ polycrystalline film deposition (pressure of Ar–O₂ mixture in chamber — 2.7 Pa, concentration of O₂ — 10%) are determined. Low resistivity of as-deposited ZnO film and increasing ZnO crystallite sizes and phase volume at temperatures higher than the melting point of Zn (419.5 C) are explained by formation of conductive Zn and ZnO particle chains and their destruction, respectively.     

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.     

The role of a ZnO buffer layer in the growth of ZnO thin film on Al2O3 substrate

A ZnO buffer layer and ZnO thin film have been deposited by the pulsed laser deposition technique at the temperatures of 200 C and 400 C, respectively. Structural, electrical and optical properties of ZnO thin films grown on sapphire (Al₂O₃) substrate with 1, 5, and 9 nm thick ZnO buffer layers were investigated. A minute shift of the (101) peak was observed which indicates that the lattice parameter was changed by varying the thickness of the buffer layer. High resolution transmission electron microscopy (TEM) was used to investigate the thickness of the ZnO buffer layer and the interface involving a thin ZnO buffer between the film and substrate. Selected area electron diffraction (SAED) patterns show high quality hexagonal ZnO thin film with 30 in-plane rotation with respect to the sapphire substrate. The use of the buffer can reduce the lattice mismatch between the ZnO thin film and sapphire substrate; therefore, the lattice constant of ZnO thin film grown on sapphire substrate became similar to that of bulk ZnO with increasing thickness of the buffer layer.     

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.     

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.     

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.     

The effect of the aminating temperature on the synthesis of gallium nitride nanowires doped with magnesium

GaN nanowires doped with Mg have been synthesized at different temperature through ammoniating the magnetron-sputtered Ga₂O₃/Au layered films deposited on Si substrates. X-ray diffraction (XRD), Scanning electron microscope (SEM), high-resolution TEM (HRTEM) equipped with an energy-dispersive X-ray (EDX) spectrometer and photoluminescence (PL) were used to analyze the structure, morphology, composition and optical properties of the as-synthesized sample. The results show that the ammoniating temperature has a great impact on the properties of GaN. The optimally ammoniating temperature of Ga₂O₃/Au layer is 900 C for the growth of GaN nanowires(NWs). The band gap emission (358 nm) relative to that (370 nm) of undoped GaN NWs has an apparent blueshift, which can be ascribed to the doping of Mg. Finally, the growth mechanism is also briefly discussed.     

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.     

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.     

Dielectric/piezoelectric properties and temperature dependence of domain structure evolution in lead free single crystal

(K_0.5Na_0.5)NbO₃ (KNN) single crystals were grown using a high temperature flux method. The dielectric permittivity was measured as a function of temperature for [001]-oriented KNN single crystals. The ferroelectric phase transition temperatures, including the rhombohedral–orthorhombic T_R−O, orthorhombic–tetragonal T_O−T and tetragonal–cubic T_C were found to be located at −149  C, 205 C and 393 C, respectively. The domain structure evolution with an increasing temperature in [001]-oriented KNN single crystal was observed using polarized light microscopy (PLM), where three distinguished changes of the domain structures were found to occur at −150  C, 213 C and 400 C, corresponding to the three phase transition temperatures.     

Structural characterization of ZnO/ Er2O3 core/shell nanowires

Zinc oxide/erbium oxide core/shell nanowires are of great potential value to optoelectronics because of the possible demonstration of laser emission in the 1.5 μm range. In this paper we present a convenient technique to obtain structures of this composition. ZnO core nanowires were first obtained by a vapor–liquid–solid (VLS) method using gold as a catalyst. ZnO nanowires ranging from 50 to 100 nm in width were grown on the substrates. Erbium was incorporated into these nanowires by their exposure to Er(tmhd)₃ at elevated temperatures. After annealing at 700 C in air, the nanowires presented 1.54 μm emission when excited by any of the lines of an Ar⁺ laser. An investigation of nanowire structure by HRTEM indicates that indeed the cores consist of hexagonal ZnO grown in the 001 direction while the surface contains randomly oriented Er₂O₃ nanoparticles. EXAFS analysis reveals that the Er atoms possess a sixfold oxygen coordination environment, almost identical to that of Er₂O₃. Taken collectively, these data suggest that the overall architectures of these nanowires are discrete layered ZnO/ Er₂O₃ core/shell structures whereby erbium atoms are not incorporated into the ZnO core geometry.     

Study of the MOCVD growth of ZnO on GaAs substrates: Influence of the molar ratio of the precursors on structural and morphological properties

ZnO thin films were grown by metal-organic chemical vapour deposition (MOCVD) on GaAs(100) and GaAs(111)A substrates. The growth experiments were performed at temperatures ranging from 290 to 500 C and atmospheric pressure. Diethylzinc (DEZn) and tertiary butanol (tBuOH) were used as Zn and O precursors, respectively. The crystallinity of the grown films was studied by X-Ray Diffraction (XRD) and the thickness and morphology were investigated by Scanning Electron Microscopy (SEM). The influence of substrate orientation and molar ratio of the precursors on the crystalline orientation and morphology of the ZnO grown films was analysed.     

Control of diameter of ZnO nanorods grown by chemical vapor deposition with laser ablation of ZnO

We made a study of controlling diameters of well-aligned ZnO nanorods grown by low-pressure thermal chemical vapor deposition combined with laser ablation of a sintered ZnO target, which was developed by us. Until now, it has been impossible to control diameters of ZnO nanorods, while the growth orientation was maintained well-aligned. In this study we developed a multi-step growth method to fabricate well-aligned nanorods whose diameters could be controlled. Metal Zn vapor and O₂ are used as precursors to grow ZnO nanorods. N₂ is used as a carrier gas for the precursors. A substrate is an n-Si (111) wafer. A sintered ZnO target is placed near the substrate and ablated by a Nd–YAG pulsed laser during ZnO nanorod growth. The growth temperature is 530 C and the pressure is 66.5 Pa. A vertical growth orientation of ZnO nanorods to the substrate is realized in the first-step growth although the diameter cannot be controlled in this step. When an O₂ flow rate is 1.5 sccm, well-aligned nanorods with 100 nm diameter are grown. Next, the second-step nanorods are grown on only the flat tip of the first-step nanorods. The diameters of the second-step nanorods can be controlled by adjusting the O₂ flow rate, and the growth direction is kept the same as that of the first-step nanorods. When the O₂ flow rate in second-step growth is smaller than 0.6 sccm, the diameter of the second-step nanorods is 30–50 nm. When the O₂ flow rate is between 0.75 and 3.0 sccm, the diameter is almost same as that of the first-step nanorods. When the O₂ flow rate is larger than 4.5 sccm, the diameter is increased with increasing O₂ flow rate. Further, the third-step ZnO nanorods with gradually increased diameters can be grown on the second-step nanorods with 1.5 sccm O₂ flow rate and without laser ablation.     

Integration of GaN thin films to SiO2–Si(100) substrates by laser lift-off and wafer fusion method

A process methodology has been adopted to bond GaN thin films to Si(100) substrates using the combination of laser lift-off and direct wafer fusion. Using optimum excimer laser conditions, 2–10 μm of GaN is lifted-off from sapphire. The lifted-off thin film is cleared from gallium residual and then suitably treated in a hydrofluoric, nitric and acetic acid mixture to render the surface hydrophilic. This treatment provides van der Waals bonds to immediately contact bond with SiO₂–Si(100) substrate at room temperature. The bonds are further strengthened by a high temperature annealing at 650 C for 2 h. The structural and mechanical characteristics of the bonded structure reveal uniform and high quality bonding. The optical characteristics of the transferred bonded film on SiO₂–Si(100) substrate exhibit similar properties to that of GaN on sapphire. In a similar manner, high-brightness blue LEDs were transferred from sapphire to SiO₂–Si(100) substrate with no deterioration in the electrical and optical performance of the device.