Structure and UV emission of nanocrystal ZnO films by thermal oxidation of ZnS films

ZnO films prepared by the thermal oxidation of the ZnS films through thermal evaporation are reported. The as-deposited ZnS films have transformed to ZnO films completely at 400 degrees C. The 400-700 degrees C annealed films with a preferential c-axis (002) orientation have a hexagonal wurtzite structure. The band gap of ZnO films shifts towards longer wavelength with the increase of the annealing temperature. The relationship between the band gap energy of ZnO films and the grain size is discussed. The shift of the band gap energy can be ascribed to the quantum confinement effect in nanocrystal ZnO films. The photoluminescence spectra of ZnO films show a dominant ultraviolet emission and no deep level or trap state defect emission in the green region. It confirms the absence of interstitial zinc or oxygen vacancies in ZnO films. These results indicate that ZnO film prepared by this simple thermal oxidation method is a promising candidate for optoelectronic devices and UV laser. (c) 2005 Elsevier BN. All rights reserved.

The effects of oxygen partial pressure on the optical absorption edge and the UV emission energy of ZnO films

The optical absorption edge and ultraviolet (UV) emission energy of ZnO films deposited by direct current (DC) reactive magnetron sputtering at room temperature have been investigated. With the oxygen ratio increasing, the structure of films changes from zinc and zinc oxide coexisting phase to single-phase ZnO and finally to the highly (002) orientation. Both the grain size and the stress of ZnO film vary with the oxygen partial pressure. Upon increasing the oxygen partial pressure in the growing ambient, the visible emission in the room-temperature photoluminescence spectra was suppressed without sacrificing the band-edge emission intensity in the ultraviolet region. The peaks of photoluminescence spectra were located at 3.06---3.15 eV. From optical transmittance spectra of ZnO films, the optical band gap edge was observed to shift towards shorter wavelength with the increase of oxygen partial pressure.

Low temperature annealing effects on the structure and optical properties of ZnO films grown by pulsed laser deposition

ZnO thin films were deposited on glass substrates at room temperature (RT) similar to 500 degrees C by pulsed laser deposition (PLD) technique and then were annealed at 150-450 degrees C in air. The effects of annealing temperature on the microstructure and optical properties of the thin films deposited at each substrate temperature were investigated by XRD, SEM, transmittance spectra, and photoluminescence (PL). The results showed that the c-axis orientation of ZnO thin films was not destroyed by annealing treatments: the grain size increased and stress relaxed for the films deposited at 200-500 degrees C, and thin films densified for the films deposited at RT with increasing annealing temperature. The transmittance spectra indicated that E-g of thin films showed a decreased trend with annealing temperature. From the PL measurements, there was a general trend, that is UV emission enhanced with lower annealing temperature and disappeared at higher annealing temperature for the films deposited at 200-500 degrees C; no UV emission was observed for the films deposited at RT regardless of annealing treatment. Improvement of grain size and stoichiometric ratio with annealing temperature can be attributed to the enhancement of UV emission, but the adsorbed oxygen species on the surface and grain boundary of films are thought to contribute the annihilation of UV emission. It seems that annealing at lower temperature in air is an effective method to improve the UV emission for thin films deposited on glass substrate at substrate temperature above RT.

Effects of the morphology of ZnO/Ag interface on the surface-plasmon-enhanced emission of ZnO films

The effects of the surface morphology of Ag on the surface-plasmon-enhanced emission of ZnO films have been studied for a ZnO/Ag/Si system by photoluminescence spectroscopy and atomic force microscopy. The results indicate that the enhancement of ZnO ultraviolet emission is dependent on the deposition conditions of the Ag interlayers. By examining the dependence of the enhancement ratio of surface-plasmon-mediated emission on the characteristic parameters of Ag surface morphology, we found that the surface plasmon coupling to light is determined by both the Ag particle size and density.

Enhancement of field emission properties in La-doped ZnO films prepared by magnetron sputtering

Field emissions (FE) from La-doped zinc oxide (ZnO) films are both experimentally and theoretically investigated. Owing to the La-doped effect, the FE characteristic of ZnO films is remarkably enhanced compared with an undoped sample, and a startling low turn-on electric field of about 0.4 V/mu m (about 2.5 V/mu m for the undoped ZnO films) is obtained at an emission current density of 1 mu A/cm(2) and the stable current density reaches 1 mA/cm(2) at an applied field of about 2.1 V/mu m. A self-consistent theoretical analysis shows that the novel FE enhancement of the La-doped sample may be originated from its smaller work function. Due to the effect of doping with La, the Fermi energy level lifts, electrons which tunnelling from surface barrier are consumedly enhancing, and then leads to a huge change of field emission current. Interestingly, it suggests a new effective method to improve the FE properties of film materials.

Oxygen pressure dependences of structure and properties of ZnO films deposited on amorphous glass substrates by pulsed laser deposition

ZnO films are prepared on glass substrates by pulsed laser deposition (PLD) at different oxygen pressures, and the effects of oxygen pressure on the structure and optoelectrical properties of as-grown ZnO films are investigated. The results show that the crystallite size and surface roughness of the films increase, but the carrier concentration and optical energy gap E-g decrease with increasing oxygen pressure. Only UV emission is found in the photoluminescence (PL) spectra of all the samples, and its intensity increases with oxygen pressure. Furthermore, there are marked differences in structure and properties between the films grown at low oxygen pressures (0.003 and 0.2 Pa) and the films grown at high oxygen pressures (24 and 150 Pa), which is confirmed by the fact that the crystallite size and UV emission intensity markedly increase, but the carrier concentration markedly decreases as oxygen pressure increases from 0.2 to 24 Pa. These results show that the crystal quality, including the microstructural quality and stoichiometry proportion, of the prepared ZnO films improves as oxygen pressure increases, particularly from 0.2 to 24 Pa.

Effects of disk rotation rate on the growth of ZnO films by low-pressure metal-organic chemical vapor deposition

ZnO films were grown at low pressure in a vertical metal-organic vapor deposition (MOCVD) reactor with a rotating disk. The structural and morphological properties of the ZnO films grown at different disk rotation rate (DRR) were investigated. The growth rate increases with the increase of DRR. The ZnO film grown at the DRR of 450 revolutions per minute (rpm) has the lowest X-ray rocking curve full width at half maximum and shows the best crystalline quality and morphology. In addition, the crystalline quality and morphology are improved as the DRR increased but both are degraded when the DRR is higher than 450 rpm. These results can help improve in understanding the rotation effects on the ZnO films grown by MOCVD. (C) 2007 Elsevier B.V. All rights reserved.

The effects of substrate temperature on the structure and properties of ZnO films prepared by pulsed laser deposition

ZnO thin films were prepared by pulsed laser deposition (PLD) on glass substrates with growth temperature from room temperature (RT) to 500 degrees C. The effects of substrate temperature on the structural and optical properties of ZnO films have been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission spectra, and RT photoluminescence (PL) measurements. The results showed that crystalline and (0 0 2)-oriented ZnO films were obtained at all substrate temperatures. As the substrate temperature increased from RT to 500 degrees C, the ratio of grain size in height direction to that in the lateral direction gradually decreased. The same grain size in two directions was obtained at 200 degrees C, and the size was smallest in all samples, which may result in maximum E, and E-0 of the films. UV emission was observed only in the films grown at 200 degrees C, which is probably because the stoichiometry of ZnO films was improved at a suitable substrate temperature. It was suggested that the UV emission might be related to the stoichiometry in the ZnO film rather than the grain size of the thin film. (c) 2007 Elsevier Ltd. All rights reserved.

Surface plasmon enhanced ultraviolet emission from ZnO films deposited on Ag/Si(001) by magnetron sputtering

The ZnO films were grown on Ag/Si(001) substrates by sputtering Ag and ZnO targets successively in a pure Ar ambient. A significant enhancement of ZnO ultraviolet emission and a reduction of its full width of half maximum have been observed while introducing a 100 nm Ag interlayer between ZnO film and Si substrate. Furthermore, a complete suppression of the defect related visible emission was also found for the ZnO/Ag/Si sample. This improved optical performance of ZnO is attributed to the resonant coupling between Ag surface plasmon and ultraviolet emission of ZnO. (c) 2007 American Institute of Physics.

Enhancement of conductivity and transmittance of ZnO films by post hydrogen plasma treatment

We studied the effects of hydrogen plasma treatment on the electrical and optical properties of ZnO films deposited by radio frequency magnetron sputtering. It is found that the ZnO H film is highly transparent with the average transmittance of 92% in the visible range. Both carrier concentration and mobility are increased after hydrogen plasma treatment, correspondingly, the resistivity of the ZnO H films achieves the order of 10(-3) cm. We suggest that the incorporated hydrogen not only passivates most of the defects and/or acceptors present, but also introduces shallow donor states such as the V-O-H complex and the interstitial hydrogen H-i. Moreover, the annealing data indicate that H-i is unstable in ZnO, while the V-O-H complex remains stable on the whole at 400 degrees C, and the latter diffuses out when the annealing temperature increases to 500 degrees C. These results make ZnO H more attractive for future applications as transparent conducting electrodes.

Effects of crystalline quality on the ultraviolet emission and electrical properties of the ZnO films deposited by magnetron sputtering

The ZnO films were deposited on c-plane sapphire, Si (0 0 1) and MgAl2O4 (1 1 1) substrates in pure Ar ambient at different substrate temperatures ranging from 400 to 750 degrees C by radio frequency magnetron sputtering. X-ray diffraction, photoluminescence and Hall measurements were used to evaluate the growth temperature and the substrate effects on the properties of ZnO films. The results show that the crystalline quality of the ZnO films improves with increasing the temperature up to 600 degrees C, the crystallinity of the films is degraded as the growth temperature increasing further, and the ZnO film with the best crystalline quality is obtained on sapphire at 600 degrees C. The intensity of the photoluminescence and the electrical properties strongly depend on the crystalline quality of the ZnO films. The ZnO films with the better crystallinity have the stronger ultraviolet emission, the higher mobility and the lower residual carrier concentration. The effects of crystallinity on light emission and electrical properties, and the possible origin of the n-type conductivity of the undoped ZnO films are also discussed. (C) 2009 Elsevier B. V. All rights reserved.

Growth of c-oriented ZnO films on (001) SMO3 substrates by MOCVD

The growth direction of ZnO thin films grown by metal-organic chemical vapor deposition (MOCVD) is modulated by pretreatment of (001) SMO3 (STO) substrates. ZnO films show a-oriented smooth surface with epitaxial relationship of < 001 > ZnO//< 110 > STO on as-received SfO, and c-axis columnar growth with < 010 > ZnO//< 110 > STO on etched STO, respectively. The orientation alteration of ZnO films is supposed to be caused by the change of STO surface polarity. In addition, the c-ZnO films exhibit an enhanced photoluminescence (PL) intensity due to the improved crystal quality, while the blueshift of PL peak is attributed to the smaller tensile strain. These results show that high quality c-ZnO, which is essential for electronic and optoelectronic device applications, can be grown on (001) SfO by MOCVD. (C) 2008 Elsevier B.V. All rights reserved.

Structural and optical properties of ZnO films on SrTiO3 substrates by MOCVD

ZnO films have been fabricated on (0 0 1), (0 1 1) and (1 1 1) SrTiO3 (STO) substrates by metal-organic chemical vapour deposition (MOCVD). It is interesting that the ZnO films on (0 0 1) and (0 1 1) STO substrates show polar and semipolar orientations, which are different from previous reports, while the same growing direction of polar ZnO with previous results is found on (1 1 1) STO. For the atomic arrangements, two orthogonal domains and a single domain are observed on (0 0 1) and (1 1 1) STO, respectively. Photoluminescence spectra show that every sample has a sharp near-band-edge emission peak at about 3.28 eV without any deep-level emission band between 1.5 and 2.8 eV, implying a high optical quality. A violet emission around 3.0 eV is observed only in ZnO films on (0 0 1) and (0 1 1) STO substrates grown at 600 degrees C, which is discussed briefly. Additionally, the semipolar ZnO does not weaken the emission efficiency along with the reduction in the polarization effect compared with polar ZnO. These results show that high-quality polar and semipolar ZnO films can be grown on STO substrates by MOCVD.