Effect of growth time on the structure, Raman shift and photoluminescence of Al and Sb codoped ZnO nanorod ordered array thin films

Al and Sb codoped ZnO nanorod ordered array thin films have been deposited on glass substrate with a ZnO seed layer by hydrothermal method at different growth time. The effect of growth time on structure, Raman shift, and photoluminescence (PL) was studied. The thin films at growth time of 5 h consist of nanorods growth vertically oriented with ZnO seed layer, and the nanorods with an average diameter of 27.8 nm and a length of 1.02 μm consist of single crystalline wurtzite ZnO crystal and grow along [0 0 1] direction. Raman scattering analysis demonstrates that the thin films at the growth time of 5 h have great Raman shift of 15 cm⁻¹ to lower wavenumber and have low asymmetrical factor Г_a/Г_b of 1.17. Room temperature photoluminescence reveals that there is more donor-related PL in films with growth time of 5 h.     

Effects of seed layer on the structure and property of zinc oxide thin films electrochemically deposited on ITO-coated glass

ZnO films with different morphologies were deposited on the ITO-coated glass substrate from zinc nitrate aqueous solution at 65 °C by a seed-layer assisted electrochemical deposition route. The seed layers were pre-deposited galvanostatically at different current densities (i_sl) ranging from −1.30 to −3.0 mA/cm², and the subsequent ZnO films had been done using the potentiostatic technique at the cathode potential of −1.0 V. Densities of nucleation centers in the seed layers varied with increasing the current density, and the ZnO films on them showed variable morphologies and optical properties. The uniform and compact nanocrystalline ZnO film with (0 0 2) preferential orientation was obtained on seed layer that was deposited under the current density (i_sl) of −1.68 mA/cm², which exhibited good optical performances.     

Room-temperature electrosynthesized ZnO thin film with strong (0 0 2) orientation and its optical properties

ZnO thin film with strong orientation (0 0 2) and smooth surface morphology was electrosynthesized on ITO-coated glass substrate at room temperature under pulsed voltage. Photoluminescence (PL) shows two obvious peaks: violet band and strong green band. The former is due to the free-excitonic transition and the latter is believed to arise from the single ionized oxygen vacancy (V_O⁺). Raman scattering reveals that the 580 cm⁻¹ mode and the shoulder peak mode at 550 cm⁻¹ originate from the N-related local vibration mode (LVM) and E₁ (LO) mode, respectively.     

Growth of carbon nanofibers on aligned zinc oxide nanorods and their field emission properties

Carbon nanofibers were grown by electrodeposition technique onto aligned zinc oxide (ZnO) nanorods deposited by hybrid wet chemical route on glass substrates. X-ray diffraction traces indicated very strong peak for reflections from (0 0 2) planes of ZnO. The Raman spectra were dominated by the presence of G band at about 1597 cm⁻¹ corresponding to the E_2g tangential stretching mode of an ordered graphitic structure with sp² hybridization and a D band at about 1350 cm⁻¹ originating from disordered carbon. Fourier transformed infrared studies indicated the presence of a distinct characteristic absorption peak at ∼511 cm⁻¹ for Zn-O stretching mode. Photoluminescence spectra indicated band edge luminescence of ZnO at ∼3.146 eV along with a low intensity peak at ∼0.877 eV arising out of carbon nanofibers. Field emission properties of these films and their dependence on the CNF coverage on ZnO nanorods are reported here. The average field enhancement factor as determined from the slope of the FN plot was found to vary between 1 × 10³ and 3 × 10³. Both the values of turn-on field and threshold field for CNF/ZnO were lower than pure ZnO nanorods.     

Structural and optical properties of ZnO nanorods grown on MgxZn1−xO buffer layers

ZnO nanorod arrays were synthesized by chemical-liquid deposition techniques on Mg_xZn_1−xO (x = 0, 0.07 and 0.15) buffer layers. It is found that varying the Mg concentration could control the diameter, vertical alignment, crystallization, and density of the ZnO nanorods. The X-ray diffraction (XRD), transmission electron microscopy (TEM), and selected area electron diffraction (SAED) data show the ZnO nanorods prefer to grow in the (0 0 2) c-axis direction better with a larger Mg concentration. The photoluminescence (PL) spectra of ZnO nanorods exhibit that the ultraviolet (UV) emission becomes stronger and the defect emission becomes weaker by increasing the Mg concentration in Mg_xZn_1−xO buffer layers.     

Temperature-dependent growth mode of W-doped ZnO nanostructures

We report on the effects of glass substrate temperature on the crystal structure and morphology of tungsten (W)-doped ZnO nanostructures synthesized by pulsed-laser deposition. X-ray diffraction analysis data shows that the W-doped ZnO thin films exhibit a strongly preferred orientation along a c-axis (0 0 0 L) plane, while scanning electron and atomic force microscopes reveal that well-aligned W-doped ZnO nanorods with unique shape were directly and successfully synthesized at substrate temperature of 550 °C and 600 °C without any underlying catalyst or template. Possible growth mechanism of these nanorods is suggested and discussed.     

Characteristics of ZnO:Al thin films co-doped with hydrogen and fluorine

Fluorine and hydrogen co-doped ZnO:Al (AZO) films were prepared by radio frequency (rf) magnetron sputtering of ZnO targets containing 1 wt.% Al₂O₃ on Corning glass at substrate temperature of 150 °C with Ar/CF₄/H₂ gas mixtures, and the structural, electrical and optical properties of the as-deposited and the vacuum-annealed films were investigated. In as-deposited state, films with fairly low resistivity of 3.9-4 × 10⁻⁴ Ω cm and very low absorption coefficient below 900 cm⁻¹ when averaged in 400-800 nm could be fabricated. After vacuum-heating at 300 °C, the minimum resistivity of 2.9 × 10⁻⁴ Ω cm combined with low absorption loss in visible region, which enabled the figure of merit to uplift as high as 4 Ω⁻¹, could be obtained for vacuum-annealed film. It was shown that, unlike hydrogenated ZnO films which resulted in degradation upon heating in vacuum at moderately high temperature, films with fluorine addition could yield improved electrical properties mostly due to enhanced Hall mobility while preserving carrier concentration level. Furthermore, stability in oxidizing environment could be improved by fluorine addition, which was ascribed to the filling effect of dangling bonds at the grain boundaries. These results showed that co-doping of hydrogen and fluorine into AZO films with low Al concentration could be remarkably compatible with thin film solar cell applications.     

Stable p-ZnO thin films by oxygen control using reverse spray dynamics

Semiconducting ZnO thin films were deposited on glass substrates by a modified CVD method using reverse spray of the precursor solutions. The films were characterized by X-ray diffraction (XRD) and Hall effect measurements at room temperature. The results of XRD analysis revealed polycrystalline nature of the grown films with different crystallographic orientations. The type of conductivity and the carrier concentration as determined from Hall effect measurements were dependent on the deposition temperature and annealing conditions. Oxygen control at 220 °C produced p-ZnO film with high hole mobility (193 cm²/V s). The electrical conductivity was correlated to the stoichiometry of the grown films.     

Epitaxial growth of Sc-doped ZnO films on Si by sol-gel route

The epitaxial growth of doped ZnO films is of great technological importance. Present paper reports a detailed investigation of Sc-doped ZnO films grown on (1 0 0) silicon p-type substrates. The films were deposited by sol-gel technique using zinc acetate dihydrate as precursor, 2-methoxyethanol as solvent and monoethanolamine (MEA) as a stabilizer. Scandium was introduced as dopant in the solution by taking 0.5 wt%¹ of scandium nitrate hexahydrate. The effect of annealing on structural and photoluminescence properties of nano-textured Sc-doped films was investigated in the temperature range of 300-550 °C. Structural investigations were carried out using X-ray diffraction, scanning electron microscopy and atomic force microscopy. X-ray diffraction study revealed that highly c-axis oriented films with full-width half maximum of 0.21° are obtained at an annealing temperature of 400 °C. The SEM images of ZnO:Sc films have revealed that coalescence of ZnO grains occurs due to annealing. Ostwald ripening was found to be the dominant mass transport mechanism in the coalescence process. A surface roughness of 4.7 nm and packing density of 0.93 were observed for the films annealed at 400 °C. Room temperature photoluminescence (PL) measurements of ZnO:Sc films annealed at 400 °C showed ultraviolet peak at about (382 nm) with FWHM of 141 meV, which are comparable to those found in high-quality ZnO films. The films annealed below or above 400 °C exhibited green emission as well. The presence of green emission has been correlated with the structural changes due to annealing. Reflection high energy electron diffraction pattern confirmed the nearly epitaxial growth of the films.     

Structural, optical and electrical properties of Al-N codoped ZnO films by RF-assisted MOCVD method

N-doped ZnO films were produced using N₂ as N source by metal-organic chemical vapor deposition (MOCVD) system which has been improved with radio-frequency (RF)-assisted equipments. The data of secondary ion mass spectroscopy (SIMS) indicate that the concentration of N in N-doped ZnO films is around 5 × 10²⁰ cm⁻³, implying that sufficient incorporation of N into ZnO can be obtained by RF-assisted equipment. On this basis, the structural, optical and electrical properties of Al-N codoped ZnO films were studied. Then, the effect of RF power on crystal quality, surface morphologies, optical properties was analyzed using X-ray diffraction, atomic force microscopy and photo-luminescence methods. The results illustrate that the RF plasma is the key factor for the improvement of crystal quality. Then the observation of A⁰X recombination associated with N_O acceptor in low-temperature PL spectrum proved that some N atoms have occupied the positions of O atoms in ZnO films. Hall measurements shown that p-type ZnO film deposited on quartz glasses was obtained when RF power was 150 W for the Al-N codoped ZnO films, while the resistivity of N-doped ZnO films was rather high. Compared with the Al-doped ZnO film, the obviously increased resistivity of codoped films indicates that the formation of N_O acceptors compensate some donors in ZnO films effectively.     

Transparent and conducting Zn-Sn-O thin films prepared by combinatorial approach

Zn-Sn-O (ZTO) films with continuous compositional gradient of Sn 16-89 at.% were prepared by co-sputtering of two targets of ZnO and SnO₂ in a combinatorial method. The resistivities of the ZTO films were severely dependent on oxygen content in sputtering gas and Zn/Sn ratio. Except for the films with Sn 16 at.%, all the as-prepared films were amorphous and maintaining the stable amorphous states up to the annealing temperature of 450 °C. Annealing at 650 °C resulted in crystallization for all the composition, in which ZnO, Zn₂SnO₄, ZnSnO₃, and SnO₂ peaks were appeared successively with increasing Sn content. Above Sn 54 at.%, the ZTO films were deduced to have a local structure mixed with ZnSnO₃ and SnO₂ phases which were more conductive and stable in thermal oxidation than ZnO and Zn₂SnO₄ phases. The lowest resistivity of 1.9 × 10⁻³ Ω cm was obtained for the films with Sn 89 at.% when annealed at 450 °C in a vacuum. The carrier concentrations of the amorphous ZTO films that contained Sn contents higher than 36 at.% and annealed at 450 °C in a vacuum were proportional to the Sn contents, while the Hall mobilities were insensitive to Sn contents and leveling in the range of 23-26 cm²/V s.     

Ar irradiation of Si nanocrystal-doped SiO2: Evolution of photoluminescence

We report the evolution of photoluminescence (PL) of Si nanocrystals (nc-Si) embedded in a matrix of SiO₂ during Ar⁺ ion bombardment. The integrated intensity of nc-Si PL falls down drastically before the Ar⁺ ion fluence of 10¹⁵ ions cm⁻², and then decreases slowly with the increasing ion fluence. At the meantime, the PL peak position blueshifts steadily before the fluence of 10¹⁵ ions cm⁻², and then changes in an oscillatory manner. Also it is found that the nc-Si PL of the Ar⁺-irradiated sample can be partly recovered after annealing at 800 °C in nitrogen, but can be almost totally recovered after annealing in oxygen. The results confirm that the ion irradiation-induced defects are made up of oxygen vacancies, which absorb light strongly. The oscillatory peak shift of nc-Si can be related to a size-distance distribution of nc-Si in SiO₂.     

Effects of different ions implantation on yellow luminescence from GaN

The influence of C, N, O, Mg, Si and co-implants (Mg+Si) ions implantation with fluences in the wide range 10¹³-10¹⁷ cm⁻² on the yellow luminescence (YL) properties of wurtzite GaN has been studied by photoluminescence (PL) spectroscopy. Two types of n-type GaN samples grown by metal-organic chemical vapor deposition method (MOCVD) and labeled as No-1 and No-2 were studied. In their as-grown states, No-1 samples had strong YL, while No-2 samples had weak YL. Results of the frontside and backside PL measurements in one of the as-grown GaN epifilms are also presented. Comparing the intensity of YL between frontside and backside PL spectra, the backside PL spectrum shows the more intense YL intensity. This implies that most of the intrinsic defects giving rise to YL exist mainly near the interface between the epilayer and buffer layer. Our experimental results show that the intensity ratio of YL to near-band-edge UV emission (I_YL/I_UV) decreases gradually by increasing the C implantation fluence from 10¹³ to 10¹⁶ cm⁻² for No-1 samples after annealing at 900 °C. When the fluence is 10¹⁷ cm⁻², a distinct change of the I_YL/I_UV is observed, which is strongly increased after annealing. For No-2 samples, after annealing the I_YL/I_UV decreases gradually with increase in the C implantation fluence from 10¹³ to 10¹⁵ cm⁻². The I_YL/I_UV is gradually increased with increasing C fluence from 10¹⁶ to 10¹⁷ cm⁻² after annealing, while I_YL/I_UV for other ions-implanted GaN samples decreases monotonically with increase in the ions implantation fluences from 10¹³ to 10¹⁷ cm⁻² for both No-1 samples and No-2 samples. It is noted that for annealed C-implanted No-2 samples I_YL/I_UV is much higher than that of the as-grown one and other ion-implanted ones. In addition, I_YL/I_UV for the Mg, Si, and co-implants (Mg+Si) implanted No-2 samples with a fluence of 10¹³ cm⁻² after being annealed at 900 °C is higher than that of the as-grown one. Based on our experimental data and literature results reported previously, the origins of the YL band have been discussed.     

Electron transport in high quality undoped ZnO film grown by plasma-assisted molecular beam epitaxy

High quality ZnO films were grown on c-plane sapphire substrate using low temperature ZnO buffer layer by plasma-assisted molecular beam epitaxy. The film deposited at 720 °C showed the lowest value of full-width at half maximum for the symmetric (0002) diffraction peak of about 86 arcsec. The highest electron mobility in the films was about 103-105 cm²/V s. From temperature-dependent Hall effect measurements, the mobility strongly depends on the dislocation density at low temperature region and the polar optical phonon scattering at high temperature, respectively. Moreover, by obtaining the activation energy of the shallow donors, it was supposed that hydrogen was source of n-type conductivity in as-grown ZnO films.     

Effect of composition and deposition temperature on the characteristics of Ga doped ZnO thin films

ZnO films doped with Ga (GZO) of varying composition were prepared on Corning glass substrate by radio frequency magnetron sputtering at various deposition temperatures of room temperature, 150, 250 and 400 °C, and their temperature dependent photoelectric and structural properties were correlated with Ga composition. With increasing deposition temperature, the Ga content, at which the lowest electrical resistivity and the best crystallinity were observed, decreased. Films with optimal electrical resistivity of 2-3 × 10⁻⁴ Ω cm and with good crystallinity were obtained in the substrate temperature range from 150 to 250 °C, and the corresponding C_Ga/(C_Ga + C_Zn) atomic ratio was about 0.049. GZO films grown at room temperature had coarse columnar structure and low optical transmittance, while films deposited at 400 °C yielded the highest figure of merit (FOM) due to very low optical absorption despite rather moderate electrical resistivity slightly higher than 4 × 10⁻⁴ Ω cm. The optimum Ga content at which the maximum figure of merit was obtained decreased with increasing deposition temperature.     

Optical properties of ZnO and ZnO:Ce layers grown by spray pyrolysis

In this paper, zinc oxide (ZnO) and cerium-doped zinc oxide (ZnO:Ce) films were deposited by reactive chemical pulverization spray pyrolysis technique using zinc and cerium chlorides as precursors. The effects of Ce concentration on the structural and optical properties of ZnO thin films were investigated in detail. These films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence (PL) measurements. All deposited ZnO layers at the temperature 450 °C are polycrystalline and indicate highly c-axis oriented structure. The dimension of crystallites depends on incorporation of Ce atoms into the ZnO films. The photoluminescence spectra of the films have been studied as a function of the deposition parameters such as doping concentrations and post grows annealing. Photoluminescence spectra were measured at the temperature range from 13 K to 320 K.     

Enhanced ferroelectric properties of vanadium doped bismuth titanate (BTV) thin films grown by pulsed laser ablation technique

Bi_3.99Ti_2.97V_0.03O₁₂ (BTV) thin films were grown by pulsed laser deposition at substrate temperatures ranging between 650 and 750 °C. The structural phase, and orientation of the deposited films were investigated in order to understand the effect of the deposition parameters on the properties of the BTV films. As the substrate temperature was increased to 700 °C, the films started showing a tendency of assuming a c-axis preferred orientation, while at lower temperatures polycrystalline films were formed. The Au/BTV/Pt capacitor showed an interesting dependence of the remnant polarization (P_r) as well as dc leakage current values on the growth temperature. The film deposited at 675 °C showed a very large 2P_r of 42 μC cm⁻², which is the largest for BTV thin films among the values reported so far.     

Influence of B2O3 to the inhomogeneous broadening and spectroscopic properties of Er/Yb codoped fluorophosphate glasses

In a three-components fluorophosphate glass system, the introduction of H₃BO₃ brings some valuable influence to the spectroscopic and thermal properties of the glasses. With H₃BO₃ increases from 2 to 20 mol%, Ω₆, S_ed4I13/2, FWHM, T_g and fluorescence lifetime change from 3.21×10⁻²⁰ cm², 1.77×10⁻²⁰ cm², 45 nm, 480 °C and 8.8 ms to 4.66×10⁻²⁰ cm², 2.11×10⁻²⁰ cm², 50 nm, 541 °C and 7.4 ms, respectively. σ_abs, σ_emi, FWHM×τ_f×σ_emi has a maximum when H₃BO₃ is 11 mol%. T_g and T_x−T_g increases with H₃BO₃ introduction. Results showed that in fluorophosphate glasses, proper amount of B₂O₃ can be used as a modifier to suppress upconversion and improve spectroscopic properties, broadband property and crystallization stability of the glasses while keeps the fluorescence lifetime relatively high.     

The structural and optical properties of ZnO nanorod arrays

High quality vertical-aligned ZnO nanorod arrays were synthesized by a simple vapor transport process on Si (111) substrate at a low temperature of 520 °C. Field-emission scanning electron microscopy (FESEM) showed the nanorods have a uniform length of about 1 μm with diameters of 40-120 nm. X-ray diffraction (XRD) analysis confirmed that the nanorods are c-axis orientated. Selected area electron diffraction (SAED) analysis demonstrated the individual nanorod is single crystal. Photoluminescence (PL) measurements were adopted to analyze the optical properties of the nanorods both a strong UV emission and a weak deep-level emission were observed. The optical properties of the samples were also tested after annealing in oxygen atmosphere under different temperatures, deep-level related emission was found disappeared at 600 °C. The dependence of the optical properties on the annealing temperatures was also discussed.     

Lanthanide-doped titanium dioxide layers as photocatalysts

Films (∼0.5 mg/cm²) from TiO₂ doped with 1-10 mol% Ln³⁺ (Ln = La or Gd) are deposited on different types of substrates by spray-pyrolysis using ethylene glycol solutions of Ti⁴⁺-Ln³⁺ citric complexes as starting material and O₂ as a carrier gas. The films are post-deposition heated at 500 °C. Their phase composition, crystal structure, morphology, sorption ability and photocatalytic activity are studied. Aqueous solution of methylene blue is applied as a model pollutant. A film with 5 mol% La on Ti-coated stainless steel substrate shows significantly higher photocatalytic activity than the best performing samples produced from commercially available titania.