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.     

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.     

Synthesis and field emission of patterned ZnO nanorods

A simple and self-catalytic method has been developed for synthesizing finely patterned ZnO nanorods on ITO-glass substrates under a low temperature of 500 °C. The patterned ZnO nanorod arrays, a unit area is of 400 × 100 μm², are synthesized via vapor phase transport method. The surface morphology and composition of the as-synthesized ZnO nanorods are characterized by means of scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). The mechanism of formation of ZnO nanorods is also discussed. The measurement of field emission (FE) reveals that the as-synthesized ZnO nanorods arrays have a turn-on field of 3.3 V/μm at the current density of 0.1 μA/cm² and a low threshold field of 6.2 V/μm at the current density of 1 mA/cm². So this approach must have a potential application of fabricating micropatterned oxide thin films used in FE-based flat panel displays.     

Field emission and room temperature ferromagnetism properties of triangle-like ZnO nanosheets

Triangle-like ZnO nanosheets have been synthesized via conventional thermal evaporation method at a low temperature of 550 °C using CuO as catalyst. The obtained samples were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), energy dispersive X-ray spectroscopy (EDX) and photoluminescence (PL) spectra. The great influences of Cu catalyst on the morphology of the obtained ZnO nanostructures were investigated. The field emission measurements confirmed that the ZnO nanosheets possessed good performance with a turn-on field of 3.1 V μm⁻¹ and a field enhancement factor of 3250, which have promising application as a competitive cathode material in FE microelectronic devices. Room temperatures ferromagnetism has been observed in the triangle-like ZnO nanosheets, although the products consist of only nonmagnetic elements.     

Epitaxial growth of highly transparent and conducting Sc-doped ZnO films on c-plane sapphire by sol–gel process without buffer

Highly transparent and conductive scandium doped zinc oxide (ZnO:Sc) films were deposited on c-plane sapphire substrates by sol–gel technique using zinc acetate dihydrate [Zn(CH₃COO)₂·2H₂O] as precursor, 2-methoxyethanol as solvent and monoethanolamine as a stabilizer. The doping with scandium is achieved by adding 0.5 wt% of scandium nitrate hexahydrate [(ScNO₃·6H₂O)] in the solution. The influence of annealing temperature (300–550 °C) on the structural, optical and electrical properties was investigated. X-ray Diffraction study revealed that highly c-axis oriented films with full-width half maximum of 0.16° are obtained at an annealing temperature of 400 °C. The surface morphology of the films was judged by SEM and AFM images which indicated formation of grains. The average transmittance was found to be above 92% in the visible region. ZnO:Sc film, annealed at 400 °C exhibited minimum resistivity of 1.91 × 10⁻⁴ Ω cm. Room-temperature photoluminescence measurements of the ZnO:Sc films annealed at 400 °C showed ultraviolet peak at 3.31eV with a FWHM of 11.2 meV, which are comparable to those found in high-quality ZnO films. Reflection high-energy electron diffraction pattern confirmed the epitaxial nature of the films even without introducing any buffer layer.     

Arsenic-related recombination in MOVPE-grown ZnO/GaAs films

In this paper, ZnO films grown by metalorganic vapour phase epitaxy on various substrates (GaAs, silicon, sapphire) and using different VI /II ratios, are investigated by photoluminescence (PL) spectroscopy. The PL spectra of layers grown on GaAs show significant recombination at 3.320 eV, 3.305 eV and 3.270 eV. These energies are remarkably similar to what have been reported for hybrid beam deposited ZnO:As [Y.R. Ryu, T.S. Lee, H.W. White, Appl. Phys. Lett. 83 (2003) 87] and arsenic-implanted ZnO crystals [T.S. Jeong, M.S. Han, C.J. Youn, Y.S. Park, J. Appl. Phys. 96 (2004) 175], and the lines are ascribed to the incorporation of arsenic, which diffuses from the substrate into the films. Two acceptor levels are deduced at 120 meV and at 140–150 meV.     

Optical and structural properties of Eu-diffused and doped ZnO nanowires

Single crystal ZnO nanowires diffused with europium (Eu) from a solid source at 900 °C for 1 h or doped with Eu during growth have been characterized. The ZnO nanowires were grown by chemical vapor deposition on Si substrates employing Au as a catalyst. The diameter of the resulting nanowires was 200 nm with a length of 1 μm. Photoluminescence spectra excited by a He–Cd laser at room temperature showed the green luminescence at 515 nm in Eu-diffused nanowires. A small red shift of near-band-edge emission of ZnO nanowires was observed in the diffused wires, but sharp emission from Eu³ ions was not present. Transmission electron microscopy shows crystalline Eu₂O₃ formation on the diffused nanowire surface, which forms a coaxial heterostructure system. When Eu was incorporated during the nanowire growth, the sharp ⁵D_O–⁷F₂ transition of the Eu³⁺ ion at around 615 nm was observed.     

From Zn microspheres to hollow ZnO microspheres: A simple route to the growth of large scale metallic Zn microspheres and hollow ZnO microspheres

Large scale metallic Zn microspheres and hollow ZnO microspheres are synthesized by thermal evaporation and vapor transport by heating a ZnO/graphite mixture at 1000 °C. Firstly, metallic Zn microspheres are fabricated with diameters in the range of 1–10 μm. The Zn microspheres are then annealed at 600 °C in air, which form hollow semiconducting ZnO microspheres. EDX and XRD spectra reveal that the oxidized material is indeed ZnO. Room temperature photoluminescence spectra of the oxidized material show a sharp peak at 380 nm and a wider broad peak centered at 490 nm. This growth mechanism is discussed and further investigated for other metallic and metal oxide microstructures.     

Catalyst-free synthesis and luminescence of aligned ZnO nanorods

Quasi-aligned undoped ZnO nanorods with diameter in the range 100–300 nm and length of several micrometers have been grown catalyst-free on Si(1 0 0) wafer in a one-step process by direct heating of Zn powders. All nanowires are single crystals and are aligned vertically to the substrate surface with c-axis preferred orientation. XRD, HRTEM and Raman studies revealed that the ZnO nanorods have wurtzite phase, are highly crystalline and well aligned with the lattice parameters a=0.32 nm and c=0.52 nm. The PL spectra measured at different temperatures are dominated by excitonic emission at 380 nm and less intense below band gap emission band centered at 520 nm.     

The pure rotational spectrum of ZnS (XΣ)

The pure rotational spectrum of ZnS (X¹Σ⁺) has been measured using direct-absorption millimeter/sub-millimeter techniques in the frequency range 372–471 GHz. This study is the first spectroscopic investigation of this molecule. Spectra originating in four zinc isotopologues (⁶⁴ZnS, ⁶⁶ZnS, ⁶⁸ZnS, and ⁶⁷ZnS) were recorded in natural abundance in the ground vibrational state, and data from the v = 1 state were also measured for the two most abundant zinc species. Spectroscopic constants have been subsequently determined, and equilibrium parameters have been estimated. The equilibrium bond length was calculated to be r_e  2.0464 Å, which agrees well with theoretical predictions. In contrast, the dissociation energy of D_E  3.12 eV calculated for ZnS, assuming a Morse potential, was significantly higher than past experimental and theoretical estimates, suggesting diabatic interaction with other potentials that lower the effective dissociation energy. Although ZnS is isovalent with ZnO, there appear to be subtle differences in bonding between the two species, as suggested by their respective force constants and bond length trends in the 3d series.     

Laser gain by electron collisional pumping of Ar VII–V XII

Gain coefficients have been calculated for transitions of singlet levels ns–np of orbital n=4 and n=5 in magnesium-like ions with atomic numbers Z=18, 19, 20, 21, 22 and 23. Population inversions for 4p and 5p levels in these ions were also calculated, via electron collisional excitation, for electron temperature range of 93–231 eV and electron density range of 10¹⁶–10¹⁷ cm⁻³. Under these plasma conditions, the maximum gain that occurred for 4s–4p transition was at electron temperature of 231 eV and electron density of 4×10¹⁷ cm⁻³. Scaling of the maximum gain coefficients with atomic number Z and the plasma parameters is also presented.     

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.     

Effect of excimer laser annealing on the properties of ZnO thin film prepared by sol-gel method

Pristine ZnO thin films have been deposited with zinc acetate [Zn(CH₃COO)₂], mono-ethanolamine (stabilizer), and isopropanol solutions by sol-gel method. After deposition, pristine ZnO thin films have been irradiated by excimer laser (λ = 248, KrF) source with energy density of 50 mJ/cm² for 30 sec. The effect of excimer laser annealing on the optical and structural properties of ZnO thin films are investigated by photoluminescence and field emission scanning electron microscope. As-grown ZnO thin films show a huge peak of visible region and a wide full width at half maximum (FWHM) of UV region due to low quality with amorphous ZnO thin films. After KrF excimer laser annealing, ZnO thin films show intense near-band-edge (NBE) emission and weak deep-level emission. The optically improved pristine ZnO thin films have demonstrated that excimer laser annealing is novel treatment process at room temperature.     

Compact 120 TW Ti:sapphire laser system with a high gain final amplifier

A 120 TW/36 fs laser system based on Ti:sapphire chirped-pulse amplification (CPA) has been successfully established in our lab. The final four pass Ti:sapphire amplifier pumped by an energetic single-shot Nd:YAG—Nd:glass laser was designed and optimized. With 24 J/8 ns pump energy at 532 nm, 300 mJ/220 ps chirped pulse was amplified to 5.98 J in this amplifier, and a total saturated gain of 20 was achieved. The focused intensity of compressed beam could reach to 10²⁰ W/cm² with the M² of 2.0.     

Structure and properties of the one-dimensional cobalt oxide CaCo2O4

We have studied crystal structure and transport properties of the quasi one-dimensional cobalt oxide CaCo₂O₄. The CaCo₂O₄ phase crystallizes in calcium-ferrite type structure, which consists of a corner- and edge-shared CoO₆ octahedron network including one-dimensional double chains. Large thermoelectric power (S  150 μV/K at 390 K) with metallic temperature dependence of S, moderate resistivity (ρ  2.9 × 10⁻¹ Ω cm at 390 K) with carrier localization at low temperature, and normal thermal conductivity (κ  6.3 W/Km at 390 K) were observed. The phonon mean-free path was calculated from the observed data, as a function of temperature. The long phonon mean-free path (l  24 Å at 300 K) implies that the thermal conductivity could be suppressed by impurity scattering of phonons with partial element substitution.     

Fabrication of ZnO nanorod array-based photodetector with high sensitivity to ultraviolet

Large scale densely packed and vertically oriented ZnO nanorod arrays were grown on F-doped SnO₂ (FTO) substrates through a simple hydrothermal synthesis route. Based on the arrays of hexagonal ZnO nanorod with size of 60100 nm in diameter, and 1.5 μm in length, a prototypical photoelectrical device was fabricated for ultraviolet detection, showing good reproducibility and a large photocurrent of around 6.71 mA at the applied voltage of 0.4 V. The large photocurrent and the ohmic I–V characteristics of the ZnO nanorods under the illumination could be ascribed to the decrease of the barrier height among the ZnO nanorods and the Schottky barrier between the nanorods and the Au electrodes and, in particular, to the accumulation of conduction electrons, resulted from the neutralization between photogenerated holes and negatively charged oxygen ions. The photoresponse curve is well fitted to an exponential curve with the relaxation time constant of 9 s in rising edge and 90 s in decaying one, representing the accumulation of conduction electrons. These well-aligned ZnO nanostructures of high quality could be easily fabricated by a cost-effective chemical route and used for constructing nanoscale devices with excellent performances.     

Scanning tunneling microscopy/spectroscopy on multi-layered cuprate superconductor Ba2Ca5Cu6O12 (O1−x Fx)2

Scanning tunneling microscopy/spectroscopy (STM/STS) measurements on multi-layered cuprate superconductor Ba₂Ca₅Cu₆O₁₂ (O_1−x F_x)₂ are carried out. STM topographies show randomly distributed bright spot structures with a typical spot size of 0.8 nm. These bright spots are occupied about 28% per one unit cell of c-plane, which is comparable to the regular amount of apical oxygen of 20% obtained from element analysis. Tunneling spectra simultaneously show both the small and the large gap structures. These gap sizes at 4.9 K are about Δ 15 meV and 90 meV, respectively. The small gap structure disappears at the temperature close to T_C, while the large gap persists up to 200 K. Therefore, these features correspond to the superconducting gap and pseudogap, respectively. These facts give evidence for some ordered state with large energy scale even in the superconducting state. For the superconducting gap, the ratio of 2Δ/K_BT_C = 4.9 is obtained with T_C = 70 K, which is determined from temperature dependence of the tunneling spectra.     

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.     

High-performance pyroelectric single crystals for uncooled infrared detection applications

Uncooled pyroelectric infrared detectors based on ferroelectric single crystals 0.74Pb(Mg_1/3Nb_2/3)O₃–0.26PbTiO₃ (PMN–0.26PT) were fabricated. The performances of pyroelectric detectors dependence on detector fabrication temperature, absorption layer, and element thickness were compared. The room-temperature voltage responsivity (R_v) of 200 V/W and specific detectivity (D^*) of 10⁸ cm Hz^1/2/W at 12.5 Hz have been achieved. The results reveal that the better pyroelectric response can be expected by controlling temperature below 70 °C during the fabrication of the pyroelectric detectors, selecting absorption layer with high absorption coefficient, and decreasing the thickness of the elements.     

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.