Low-temperature MOVPE growth of ZnO thin films by using a buffer layer

ZnO thin films have been grown on a-plane (1,1,−2,0) sapphire substrates by metalorganic vapor phase epitaxy (MOVPE) at low substrate temperature of 350 °C. It is showed that the crystal and electrical quality of the thin films was improved by using a ZnO buffer layer. The photoluminescence (PL) measurements indicate that the ZnO thin films grown at such a low substrate temperature have a strong UV emission.     

The structural and optical properties of ZnO/Si thin films by RTA treatments

ZnO/Si thin films were prepared by rf magnetron sputtering method and some of the samples were treated by rapid thermal annealing (RTA) process at different temperatures ranging from 400 to 800 °C. The effects of RTA treatment on the structural properties were studied by using X-ray diffraction and atomic force microscopy while optical properties were studied by the photoluminescence measurements. It is observed that the ZnO film annealed at 600 °C reveals the strongest UV emission intensity and narrowest full width at half maximum among the temperature ranges studied. The enhanced UV emission from the film annealed at 600 °C is attributed to the improved crystalline quality of ZnO film due to the effective relaxation of residual compressive stress and achieving maximum grain size.     

Epitaxial ZnO films grown on ZnO-buffered c-plane sapphire substrates by hydrothermal method

ZnO films are hydrothermally grown on ZnO-buffered c-plane sapphire substrates at a low temperature of 70 °C. A radio-frequency (RF) reactive magnetron sputtering has been used to grow the ZnO buffer layers. X-ray diffraction, scanning electron microscopy, and room temperature photoluminescence are carried out to characterize the structure, morphology and optical property of the films. It is found that the films are stress-free. The epitaxial relationship between the ZnO film and the c-plane sapphire substrate is found to be ZnO (0 0 0 1)||Al₂O₃ (0 0 0 1) in the surface normal and in plane. Sapphire treatment, as such acid etching, nitridation, and oxidation are found to influence the nucleation of the film growth, and the buffer layers determine the crystalline quality of the ZnO films. The maximum PL quantum efficiency of ZnO films grown with hydrothermal method is found to be about 80% of single-crystal ZnO.     

Near infrared to UV dielectric functions of Al doped ZnO films deposited on c-plane sapphire substrate using pulsed laser deposition

Transparent conducting polycrystalline Al-doped ZnO (AZO) films were deposited on sapphire substrates at substrate temperatures ranging from 200 to 300 °C by pulsed laser deposition (PLD). X-ray diffraction measurement shows that the crystalline quality of AZO films was improved with increased substrate temperature. The electrical and optical properties of the AZO films have been systematically studied via various experimental tools. The room-temperature micro-photoluminescence (µ-PL) spectra show a strong ultraviolet (UV) excitonic emission and weak deep-level emission, which indicate low structural defects in the films. A Raman shift of about 11 cm⁻¹ is observed for the first-order longitudinal-optical (LO) phonon peak for AZO films when compared to the LO phonon peak of bulk ZnO. The Raman spectra obtained with UV resonant excitation at room temperature show multi-phonon LO modes up to third order. Optical response due to free electrons of the AZO films was characterized in the photon energy range from 0.6 to 6.5 eV by spectroscopic ellipsometry (SE). The free electron response was expressed by a simple Drude model combined with the Cauchy model are reported.     

Effects of sapphire substrate annealing on ZnO epitaxial films grown by MOCVD

The annealing effects of sapphire substrate on the quality of epitaxial ZnO films grown by metalorganic chemical vapor deposition (MOCVD) were studied. The atomic steps formed on (0 0 0 1) sapphire (α-Al₂O₃) substrate surface by annealing at high temperature was analyzed by atomic force microscopy (AFM). The annealing effects of sapphire substrate on the ZnO films were examined by X-ray diffraction (XRD), AFM and photoluminescence (PL) measurements. Experimental results indicate that the film quality is strongly affected by annealing treatment of the sapphire substrate surface. The optimum annealing temperature of sapphire substrates is given.     

Temperature effect on the electrical, structural and optical properties of N-doped ZnO films by plasma-free metal organic chemical vapor deposition

N-doped p-type ZnO films were grown by plasma-free metal-organic chemical vapor deposition (MOCVD). The effect of substrate temperature on the electrical, optical, and structural properties of the N-doped ZnO films was investigated by Hall-effect, photoluminescence, X-ray diffraction measurements. The electrical properties of the films were extremely sensitive to the substrate temperature and the conduction type could be reversed in a narrow range from 380 °C to 420 °C. Based on X-ray photoelectron spectroscopy, a high compensation effect in the N-doped ZnO films grown by plasma-free MOCVD was suggested to explain the temperature-dependent phenomenon.     

Effect of sputtered films on morphology of vertical aligned ZnO nanowires

Vertical aligned ZnO nanowires were grown by MOCVD technique on silicon substrate using ZnO and AlN thin films as seed layers. The shape of nanostructures was greatly influenced by the under laying surface. Vertical nanopencils were observed on ZnO/Si, whereas the nanowires on both sapphire and AlN/Si substrate have the similar aspect ratio. XRD patterns suggest that the nanostructures have good crystallinity. High-resolution transmission electron microscopy (HRTEM) confirmed the single crystalline growth of the ZnO nanowires along [0 0 1] direction. Room-temperature photoluminescence (PL) spectra of ZnO nanowires on AlN/Si clearly show a band-edge luminescence accompanied with a visible emission. More interestingly, no visible emission for the nanopencils on ZnO/Si substrates, were observed.     

Effect of annealing temperature and annealing atmosphere on the structure and optical properties of ZnO thin films on sapphire (0 0 0 1) substrates by magnetron sputtering

ZnO thin films were epitaxially grown on sapphire (0 0 0 1) substrates by radio frequency magnetron sputtering. ZnO thin films were then annealed at different temperatures in air and in various atmospheres at 800 °C, respectively. The effect of the annealing temperature and annealing atmosphere on the structure and optical properties of ZnO thin films are investigated by X-ray diffraction (XRD), atomic force microscopy (AFM), photoluminescence (PL). A strong (0 0 2) diffraction peak of all ZnO thin films shows a polycrystalline hexagonal wurtzite structure and high preferential c-axis orientation. XRD and AFM results reveal that the better structural quality, relatively smaller tensile stress, smooth, uniform of ZnO thin films were obtained when annealed at 800 °C in N₂. Room temperature PL spectrum can be divided into the UV emission and the Visible broad band emission. The UV emission can be attributed to the near band edge emission (NBE) and the Visible broad band emission can be ascribed to the deep level emissions (DLE). By analyzing our experimental results, we recommend that the deep-level emission correspond to oxygen vacancy (V_O) and interstitial oxygen (O_i). The biggest ratio of the PL intensity of UV emission to that of visible emission (I_NBE/I_DLE) is observed from ZnO thin films annealed at 800 °C in N₂. Therefore, we suggest that annealing temperature of 800 °C and annealing atmosphere of N₂ are the most suitable annealing conditions for obtaining high quality ZnO thin films with good luminescence performance.     

Effect of temperature on pulsed laser deposition of ZnO films

ZnO thin films have been deposited on Si(1 1 1) substrates at different substrate temperature by pulsed laser deposition (PLD) of ZnO target in oxygen atmosphere. An Nd:YAG pulsed laser with a wavelength of 1064 nm was used as laser source. The influences of the deposition temperature on the thickness, crystallinity, surface morphology and optical properties of ZnO films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), selected area electron diffraction (SAED), photoluminescence (PL) spectrum and infrared spectrum. The results show that in our experimental conditions, the ZnO thin films deposited at 400 °C have the best surface morphology and crystalline quality. And the PL spectrum with the strongest ultraviolet (UV) peak and blue peak is observed in this condition.     

Influence of annealing temperature on structural and optical properties of ZnO: In thin films prepared by ultrasonic spray technique

Transparent conducting indium doped zinc oxide was deposited on glass substrate by ultrasonic spray method. The In doped ZnO samples with indium concentration of 3 wt.% were deposited at 300, 350 and 400 °C with 2 min of deposition time. The effects of substrate temperature and annealing temperature on the structural, electrical and optical properties were examined. The DRX analyses indicated that In doped ZnO films have polycrystalline nature and hexagonal wurtzite structure with (0 0 2) preferential orientation and the maximum average crystallite size of ZnO: In before and annealed at 500 °C were 45.78 and 55.47 nm at a substrate temperature of 350 °C. The crystallinity of the thin films increased by increasing the substrate temperature up 350 °C, the crystallinity improved after annealing temperature at 500 °C. The film annealed at 500 °C and deposited at 350 °C show lower absorption within the visible wavelength region. The band gap energy increased from E_g = 3.25 to 3.36 eV for without annealing and annealed films at 500 °C, respectively, indicating that the increase in the transition tail width. This is due to the increase in the electrical conductivity of the films after annealing temperature.     

Substrate effects on ZnO nanostructure growth via nanoparticle-assisted pulsed-laser deposition

The effects of various substrate conditions on the morphology, crystal structure and photoluminescence of ZnO nanostructures synthesized by nanoparticle-assisted pulsed-laser ablation deposition were investigated. It is concluded that the sapphire substrate with a 1 h anneal at 1000 °C is the most favorable to the vertical growth of ZnO nanostructures. SEM analysis indicates that the well-aligned diameter-modulated ZnO nanonails with unique shape were successfully synthesized on the annealed sapphire substrate. The as-synthesized ZnO nanostructures exhibit an ultraviolet emission at around 390 nm and the absent green emission under room temperature, indicating that there is a very low concentration of deep-level defects inside ZnO lattices. The novel ZnO nanostructures could offer novel opportunities for both fundamental research and technological applications.     

The Al-doping and post-annealing treatment effects on the structural and optical properties of ZnO:Al thin films deposited on Si substrate

Al-doped ZnO (ZnO:Al) thin films with different Al contents were deposited on Si substrates using the radio frequency reactive magnetron sputtering technique. X-ray diffraction (XRD) measurements showed that the crystallinity of the films was promoted by appropriate Al content (0.75 wt.%). Then the ZnO:Al film with Al content of 0.75 wt.% was annealed in vacuum at different temperatures. XRD patterns revealed that the residual compressive stress decreased at higher annealing temperatures. While the surface roughness of the ZnO:Al film annealed at 300 °C became smoother, those of the ZnO:Al films annealed at 600 and 750 °C became rougher. The photoluminescence (PL) measurements at room temperature revealed a violet, two blue and a green emission. The origin of these emissions was discussed and the mechanism of violet and blue emission of ZnO:Al thin films were suggested. We concluded that the defect centers are mainly ascribed to antisite oxygen and interstitial Zn in annealed (in vacuum) ZnO:Al films.     

Effect of Ag doping on the photoluminescence properties of ZnO films

ZnO:Ag films were grown on Si (1 0 0) substrates by ultrasonic spray pyrolysis at various substrate temperatures. The effect of deposition temperature on the structural and the room temperature photoluminescence (RT-PL) properties of ZnO:Ag films was studied. With the deposition temperature rising to 550 °C, the intensity of the near-band edge (NBE) emission at 378 nm decreased and a new emission peak at 399 nm was observed. On the basis of the X-ray diffraction pattern (XRD), the X-ray photoelectron (XPS) spectra of ZnO:Ag films, and the effects of annealing on the PL, we suggest that the 399 nm emission should be attributed to the electron transition from the conduction band to Ag_Zn-related complexes defects radiative centers above the valence band.     

Effect of substrate temperature on the structural and optical properties of ZnO and Al-doped ZnO thin films prepared by dc magnetron sputtering

ZnO and Al-doped ZnO(ZAO) thin films have been prepared on glass substrates by direct current (dc) magnetron sputtering from 99.99% pure Zn metallic and ZnO:3 wt%Al₂O₃ ceramic targets, the effects of substrate temperature on the crystallization behavior and optical properties of the films have been studied. It shows that the surface morphologies of ZAO films exhibit difference from that of ZnO films, while their preferential crystalline growth orientation revealed by X-ray diffraction remains always the (0 0 2). The optical transmittance and photoluminescence (PL) spectra of both ZnO and ZAO films are obviously influenced by the substrate temperature. All films exhibit a transmittance higher than 86% in the visible region, while the optical transmittance of ZAO films is slightly smaller than that of ZnO films. More significantly, Al-doping leads to a larger optical band gap (E_g) of the films. It is found from the PL measurement that near-band-edge (NBE) emission and deep-level (DL) emission are observed in pure ZnO thin films. However, when Al was doped into thin films, the DL emission of the thin films is depressed. As the substrate temperature increases, the peak of NBE emission has a blueshift to region of higher photon energy, which shows a trend similar to the E_g in optical transmittance measurement.     

Control of a- and c-plane preferential orientations of ZnO thin films

We report orientation-controllable growth of ZnO thin films and their orientation-dependent electrical characteristics. ZnO thin films were deposited on single-crystalline (1 0 0) LaAlO₃ and (1 0 0) SrTiO₃ substrates using pulsed laser deposition (PLD) at different substrate temperatures (400-800 °C). It was found that the orientation of ZnO films could be controlled by using different substrates of single-crystalline (1 0 0) LaAlO₃ and (1 0 0) SrTiO₃. The a-plane () and c-plane (0 0 0 2) oriented ZnO films are formed on LaAlO₃ and SrTiO₃, respectively. In both cases, the degree orientation increased with increasing deposition temperature T_s. Both the surface free energy and the degree of lattice mismatch are ascribed to play an important role for the orientation-controllable growth. Further characterization show that the grain size of the films with both orientations increases for a substrate temperature increase (i.e. from T_s = 400 °C to T_s = 800 °C), whereas the electrical properties of ZnO thin films depend upon their crystalline orientation, showing lower electrical resistivity values for a-plane oriented ZnO films.     

Effects of growth temperature on Li-N dual-doped p-type ZnO thin films prepared by pulsed laser deposition

Li-N dual-doped p-type ZnO (ZnO:(Li,N)) thin films have been prepared by pulsed laser deposition. The introduction of Li and N was confirmed by secondary ion mass spectrometry measurements. The structural, electrical, and optical properties as a function of growth temperature were investigated in detail. The lowest room-temperature resistivity of 3.99 Ω cm was achieved at the optimal temperature of 450 °C, with a Hall mobility of 0.17 cm²/V s and hole concentration of 9.12 × 10¹⁸ cm⁻³. The ZnO:(Li,N) films exhibited good crystal quality with a complete c-axis orientation, a high transmittance (about 90%) in the visible region, and a predominant UV emission at room temperature. The two-layer-structure p-ZnO:(Li,N)/n-ZnO homojunctions were fabricated on a sapphire substrate. The current-voltage characteristics exhibited the rectifying behavior of a typical p-n junction.     

Improvement of electrical and optical properties of Ga and N co-doped p-type ZnO thin films with thermal treatment

Ga and N co-doped p-type ZnO thin films were epitaxially grown on sapphire substrate using magnetron sputtering technique. The process of synthesized Ga and N co-doped ZnO films was performed in ambient gas of N₂O. Hall measurement shows a significant improvement of p-type characteristics with rapid thermal annealing (RTA) process in N₂ gas flow, where more N acceptors are activated. The film rapid thermal annealed at 900 °C in N₂ ambient revealed the highest carrier concentration of 9.36 × 10¹⁹ cm⁻³ and lowest resistivity of 1.39 × 10⁻¹ Ω cm. In room and low temperature photoluminescence measurements of the as grown and RTA treated film, donor acceptor pair emission and exciton bound to acceptor recombination at 3.25 and 3.357 eV, respectively, were observed.     

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.     

Characterization of SnO2 obtained from the thermal oxidation of vacuum evaporated Sn thin films

Tin oxide has been prepared by thermal oxidation of evaporated tin thin films onto pyrex glass substrates. Films oxidation was achieved in air at a temperature of 600 °C with varied duration from 20min to 3 h. Structural, optical and electrical properties of the films were characterized by means of X-ray diffraction, UV–vis spectroscopy and electrical resistivity measurements respectively. The X-ray analysis revealed the transformation of Sn into SnO₂ with preferential orientation along (101) plans. No intermediate phases such as SnO and Sn₃O₄ were evidenced. It was also found that the SnO₂ crystallites orientation changed with the annealing time due to the strain energy effect. Both band gap energy and electrical resistivity decrease with annealing time due to the crystalline quality improvement and films densification. We have noticed that oxidation at 600 °C for 3 h leads to transparent and conductive films with suitable properties for photovoltaic applications.     

Structural, morphological and photoluminescence properties of W-doped ZnO nanostructures

W-doped ZnO nanostructures were synthesized at substrate temperature of 600 °C by pulsed laser deposition (PLD), from different wt% of WO₃ and ZnO mixed together. The resulting nanostructures have been characterized by X-ray diffraction, scanning electron microscopy, atomic force microscopy and photoluminescence for structural, surface morphology and optical properties as function of W-doping. XRD results show that the films have preferred orientation along a c-axis (0 0 L) plane. We have observed nanorods on all samples, except that W-doped samples show perfectly aligned nanorods. The nanorods exhibit near-band-edge (NBE) ultraviolet (UV) and violet emissions with strong deep-level blue emissions and green emissions at room temperature.