ZnO缓冲层上低温生长Al掺杂的ZnO薄膜

采用射频磁控溅射法在ZnO缓冲层上制备了不同Al掺杂量的ZnO（AZO）薄膜。利用X射线衍射（XRD）、扫描电子显微镜（SEM）和光致发光（PL）等表征技术,研究了AZO薄膜的微观结构、表面形貌和发光特性。结果表明,随着Al掺杂量的增加,ZnO薄膜的择优取向性发生了改变,且当Al的掺杂量为0.81%（原子分数）时,（002）衍射峰与其它衍射峰强度的比值达到最大,表明适合的Al掺杂使ZnO薄膜的择优取向性得到了改善。在可见光范围内薄膜的平均透过率超过70%。通过对样品光致发光（PL）谱的研究,发现所有样品出现了3个发光峰,分别对应于以444nm（2.80eV）、483nm（2.57eV）为中心的蓝光发光峰和以521nm（2.38eV）为中心较弱的绿光峰。并对样品的发光机理进行了详细的探讨。     

High quality epitaxial ZnO films grown on solid-phase crystallized buffer layers

High quality epitaxial ZnO films on sapphire (110) plane have been fabricated on ZnO homo-buffer layers crystallized via solid-phase epitaxially (SPE). The SPE-ZnO films are fabricated by annealing of amorphous ZnON (a-ZnON) films deposited by RF magnetron sputtering. During annealing, the a-ZnON films are oxidized and converted to ZnO crystal. X-ray diffraction (XRD) analysis shows that the resultant films are epitaxially grown on the sapphire substrates. By using the SPE-ZnO films as homo-buffer layers, the ZnO films with high crystallinity, which are deposited by RF magnetron sputtering, are fabricated. The full width at half-maximum of XRD patterns for 2θ-ω and ω scan of (002) plane are 0.094° and 0.12°, respectively, being significantly small compared with 0.24° and 0.55° for the films without buffer layers. Thus utilizing SPE buffer layers is very promising to obtain epitaxial ZnO films with high crystallinity.     

Study on ZnO thin films deposited on sol-gel grown ZnO buffer by RF magnetron sputtering

ZnO thin films with preferential C-orientation and dense microstructure have been prepared using RF magnetron sputtering method by the insertion of a sol-gel grown ZnO buffer layer. The XRD results show that the C-orientation of the film deposited on ZnO buffer is obviously better than that deposited directly on lime-glass substrate. With an increase of the RF power from 100 to 380 W, C-orientation of the films with ZnO buffer improves and the grain size increases. When the RF power equals 550 W, the orientation of the film changes to (1 0 0) and the grain size decreases. The crystalline and microstructure quality of the films can be improved after annealing, however, the grain size is not much dependent on the annealing temperature in the range of 560-610 °C.     

Influence of VI/II ratios on the growth of ZnO thin films on sapphire substrates by low temperature MOCVD

We investigated the structural, electrical, and optical properties of ZnO thin films grown at different VI/II ratios on sapphire substrates by metalorganic chemical vapor deposition. Transmission electron microscopy and X-ray diffraction revealed the epitaxial nature with a reduced dislocation density of the ZnO films grown at increased VI/II ratios. The carrier concentration of the films increased to 4.9 × 10¹⁸ cm^− 3 and their resistivity decreased to 1.4 × 10^− 1 Ω cm at a VI/II ratio of 513.4 μmol/min. The ZnO films also showed good optical transmittance (> 80%) in the visible and near-infrared wavelength regions. The room temperature PL revealed a strong band-edge emission with a weak deep level emission, suggesting the good crystalline quality of the ZnO films on the sapphire substrates. Furthermore, the intensity ratio of the band-edge emission to the deep-level emission (I_UV/I_Vis) increased with increasing VI/II ratio.     

Effect of inserting a buffer layer on the characteristics of transparent conducting impurity-doped ZnO thin films prepared by dc magnetron sputtering

In transparent conducting impurity-doped ZnO thin films prepared on glass substrates by a dc magnetron sputtering (dc-MS) deposition, the obtainable lowest resistivity and the spatial resistivity distribution on the substrate surface were improved by a newly developed MS deposition method. The decrease of obtainable lowest resistivity as well as the improvement of spatial resistivity distribution on the substrate surface in Al- or Ga-doped ZnO (AZO or GZO) thin films were successfully achieved by inserting a very thin buffer layer, prepared using the same MS apparatus with the same target, between the thin film and the glass substrate. The deposition of the buffer layer required a more strongly oxidized target surface than possible to attain during a conventional dc-MS deposition. The optimal thickness of the buffer layer was found to be about 10 nm for both GZO and AZO thin films. The resistivity decrease is mainly attributed to an increase of Hall mobility rather than carrier concentration, resulting from an improvement of crystallinity coming from insertion of the buffer layer. Resistivities of 3 × 10^− 4 and 4 × 10^− 4Ω cm were obtained in 100 nm-thick-GZO and AZO thin films, respectively, incorporating a 10 nm-thick-buffer layer prepared at a substrate temperature around 200 °C.     

X-ray diffraction analysis of thermally-induced stress relaxation in ZnO films deposited by magnetron sputtering on (100) Si substrates

Residual stresses in sputtered ZnO films on Si are determined and discussed. By means of X-ray diffraction, we show that as-deposited ZnO films are highly compressively stressed. Moreover, a transition of stress is observed as a function of the post-deposition annealing temperature. After an 800 °C annealing, ZnO films are tensily stressed while ZnO films encapsulated by Si₃N₄ are stress-free. With the aid of in-situ X-ray diffraction under ambient and argon atmosphere, we argue that this thermally activated stress relaxation may be attributed to a variation of the stoichiometry of the ZnO films.     

Heteroepitaxy of Ir films on silicon with a ceria/yttria stabilized zirconia buffer layer

Heteroepitaxial Ir films on Si(001) with a double ceria/yttria stabilized zirconia heteroepitaxial buffer layer were grown by magnetron sputtering. As-deposited CeO₂ films covered with {111} faceted pyramids resulted in iridium films with the [001] axis normal to the substrate plane. The buffered substrates annealed at 1115 °C have a smooth surface; Ir films on such substrates have the (111) orientation and consist of grains turned at 90° toward each other.     

Effects of low temperature ZnO and MgO buffer thicknesses on properties of ZnO films grown on (0001) Al2O3 substrates by plasma-assisted molecular beam epitaxy

We investigated the structural properties of Zn-polar ZnO films with low temperature (LT) ZnO and MgO buffer layers grown by plasma-assisted molecular beam epitaxy on (0001) c-Al₂O₃ substrates using X-ray diffraction and transmission electron microscopy (TEM). The effects of MgO buffer layer thickness and LT ZnO buffer layer thickness were also examined. The optimum thicknesses for better crystal quality were 8 and 40 nm. One-pair and two-pair LT ZnO/MgO buffer layers were employed, and the changes in the structural properties of the high-temperature (HT) ZnO films using such buffer layers were studied. Contrary to the general tendency of c-ZnO films, the HT ZnO films on the LT ZnO/MgO buffer layers showed higher full width at half maximum (FWHM) values for X-ray rocking curves (XRCs) with (0002) reflection than those with (101?1) reflection. Compared with the one-pair LT ZnO/MgO buffer layers, the FWHM values of (0002) XRCs markedly decreased, whereas those of (101?1) XRCs slightly increased due to the insertion of one more pair of LT ZnO/MgO buffer layers into the previous film with one-pair LT ZnO/MgO buffer layers. The cross-sectional TEM observations with the two-beam condition confirmed that the screw dislocation was the dominant threading dislocation type—a finding that agreed well with the XRC results. On the basis of the plan-view TEM observations, the densities of the total threading dislocations for the HT ZnO films with the one- and two-pair LT ZnO/MgO buffer layers were determined as 2.3 × 10⁹ cm^− 2 and 1.6 × 10⁹ cm^− 2, respectively. The results imply that the crystal quality of Zn-polar ZnO films can be improved by two-pair LT ZnO/MgO buffer layers, and types of threading dislocations can be modified by adjusting the buffer system.     

Structural and optical properties of high quality ZnO thin film on Si with SiC buffer layer

ZnO thin films are grown on Si substrates with SiC buffer layer using ion plasma high frequency magnetron sputtering. These substrates are fabricated using a technique of solid phase epitaxy. With this technique SiC layer of thickness 20-200 nm had been grown on Si substrates consisting pores of sizes 0.5-5 μm at SiC and Si interface. Due to mismatching in lattice constants as well as thermal expansion coefficients, elastic stresses have been developed in ZnO film. Pores at the interface of SiC and Si are acting as the elastic stress reliever of the ZnO films making them strain free epitaxial. ZnO film grown on this especially fabricated Si substrate with SiC buffer layer exhibits excellent crystalline quality as characterized using X-ray diffraction. Surface topography of the film has been characterized using Atomic Force Microscopy as well as Scanning Electron Microscopy. Chemical compositions of the films have been analyzed using Energy Dispersive X-ray Spectroscopy. Optical properties of the films are investigated using Photoluminescence Spectroscopy which also shows good optical quality.     

X-ray diffraction study of thermal stress relaxation in ZnO films deposited by magnetron sputtering

X-ray diffraction stress analyses have been performed on two different thin films deposited onto silicon substrate: ZnO and ZnO encapsulated into Si₃N₄ layers. We showed that both as-deposited ZnO films are in a high compressive stress state. In situ X-ray diffraction measurements inside a furnace revealed a relaxation of the as-grown stresses at temperatures which vary with the atmosphere in the furnace and change with Si₃N₄ encapsulation. The observations show that Si₃N₄ films lying on both sides of the ZnO film play an important role in the mechanisms responsible for the stress relaxation during heat treatment. The different temperatures observed for relaxation in ambient and argon atmospheres suggest that the thermally activated stress relaxation may be attributed to a variation of the stoichiometry of the ZnO films. The present observations pave the way to fine tuning of the residual stresses through thermal treatment parameters.     

Sputter deposition of ZnO thin films at high substrate temperatures

ZnO thin films have been deposited on GaN and ZnO substrates at substrate temperatures up to 750 °C by radio-frequency sputtering using ZnO ceramic targets in pure argon or in a mixture of argon and oxygen. By optimizing the sputter parameters, such as sputtering power, Ar/O₂ sputtering gas ratio and temperature of the substrates high quality films were obtained as judged from the X-ray rocking curve half width and luminescence line width. The crystallinity of the ZnO films increases with increasing substrate temperature. Yet there are distinct differences between films grown on GaN templates and on O- and Zn-polar ZnO substrates.     

Effects of buffer layer thickness on properties of ZnO thin films grown on porous silicon by plasma-assisted molecular beam epitaxy

ZnO thin films with different buffer layer thicknesses were grown on Si and porous silicon (PS) by plasma-assisted molecular beam epitaxy (PA-MBE). The effects of PS and buffer layer thickness on the structural and optical properties of ZnO thin films were investigated by atomic force microscopy (AFM), scanning electron microscopy (SEM), X-ray diffraction (XRD), and photoluminescence (PL). The ZnO buffer layers, the intensity of the (002) diffraction peak for the ZnO thin films and its full width at half maximum (FWHM) decreased with an increase in the thickness of the ZnO buffer layers, indicating an improvement in the crystal quality of the films. On introducing PS as a substrate, the grain sizes of the ZnO thin films became larger and their residual stress could be relaxed compared with the ZnO thin films grown on Si. The intensity ratio of the ultraviolet (UV) to visible emission peak in the PL spectra of the ZnO thin films increased with an increase in buffer layer thickness. Stronger and narrower UV emission peaks were observed for ZnO thin films grown on PS. Their structural and optical properties were enhanced by increasing the buffer layer thickness. In addition, introduction of PS as a substrate enhanced the structural and optical properties of the ZnO thin films and also suppressed Fabry-Perot interference.     

Low-temperature deposited Titanium-doped zinc oxide thin films on the flexible PET substrate by DC magnetron sputtering

Transparent conducting Titanium-doped zinc oxide thin films (TZO) with high transparency and relatively low resistivity were firstly deposited on water-cooled polyethylene terephthalate (PET) substrates at room temperature by DC magnetron sputtering. The microstructure, optical and electrical properties of the deposited films were investigated and discussed. The XRD patterns show that all the deposited films are polycrystalline with a hexagonal structure and have a preferred orientation along the c-axis perpendicular to the substrate. The electrical resistivity decreases when the sputtering power increases from 45 W to 60 W. However, as the puttering power continue increases from 60 W to 90 W, the electrical resistivity increases rapidly. When the puttering power is 60 W, the films deposited on PET substrate have the lowest resistivity of 4.72 × 10⁻⁴ Ω cm and a relatively high transmittance of above 92% in the visible range.     

Growth of ZnO/sapphire heteroepitaxial thin films by radio-frequency sputtering with a raw powder target

Epitaxial ZnO thin films were deposited by radio-frequency sputtering. In contrast to typical sputter growth, in which a ZnO sintered target was used, raw ZnO powder with a particle size smaller than 1 μm is used as the source material. In order to verify this approach, ZnO thin films were deposited on sapphire(0001) substrates and characterized by X-ray diffraction, atomic force microscopy, ultraviolet-visible-near-infrared (near-IR) transmission spectroscopy, and photoluminescence spectroscopy. The as-deposited ZnO thin films grew epitaxially on the sapphire(0001) substrate. A crossover in the growth mode from an initial 2-dimensional planar layer to later 3-dimensional islands was observed, which is consistent with the results obtained using a ZnO sintered target. The ZnO films showed band-edge emission with a bandgap energy of 3.27 eV and a high optical transmittance > 80% from visible to near-IR region. This shows that ZnO powder targets can be an alternative to relatively expensive sintered ones in the fabrication of ZnO nano-structures and doped ZnO.     

Enhanced field emission from ZnO nanoneedles on chemical vapour deposited diamond films

ZnO nanoneedles were coated on hot filament chemical vapour deposited diamond thin films to enhance the field emission properties of ZnO nanoneedles. The virgin diamond films and ZnO nanoneedles on diamond films were characterized using scanning electron microscopy, X-ray photoelectron spectroscopy and Raman spectroscopy. The field emission studies reveal that the ZnO nanoneedles coated on diamond film exhibit better emission characteristics, with minimum threshold field (required to draw a current density ~ 1 μA/cm²) as compared to ZnO needles on silicon and virgin diamond films. The better emission characteristic of ZnO nanoneedles on diamond film is attributed to the high field-enhancement factor resulting due to the combined effect of the ZnO nanoneedles and diamond film.     

Power and pressure effects upon magnetron sputtered aluminum doped ZnO films properties

In this work, polycrystalline aluminum doped zinc oxide (ZnO:Al) films with c-axis (002) orientation have been grown on glass and silicon substrates by RF (radio frequency) magnetron sputtering technique, at room temperature. A systematic study of the effect of sputtering deposition parameters (i.e. RF power and argon gas pressure) on the structural, optical and electrical properties of the films was carried out. We observed that, with increasing RF power the growth rate increased, while it decreased with increasing gas pressure. As mentioned above, the films were polycrystalline in nature with a strong preferred (002) orientation. The intrinsic compressive stress was found to decrease with both increasing RF power and gas pressure, and near stress-free film was obtained at 200 W RF power and 2 × 10^− 1 Pa gas pressure. The obtained ZnO:Al films, not only have an average transmittance greater than 90% in the visible region, but also have an optical band gap between 3.33 and 3.47 eV depending on the sputtering parameters. Moreover, a low value of the electrical resistivity (~ 1.25 × 10^− 3 Ω cm) was obtained for the film deposited at 200 W and 2 × 10^− 3 mbar.     

Evolution of the properties of ZnO thin films subjected to heating treatments

Structural and optical properties of ZnO thin films (200 nm thickness) deposited using magnetron sputtering technique are influenced by structural defects. Therefore, we applied various heating treatments in order to control and improve the crystallinity of the samples. These treatments were realized in air at temperatures of 350 °C, 550 °C and 700 °C respectively, each for a duration of 1 h. The properties of the samples were investigated both before and after the heating treatment. Modern methods like X-ray Diffraction, Atomic Force Microscopy and Scanning Electron Microscopy were used to analyze the structure and morphology of the heated ZnO thin films. These heating treatments may be held responsible for rearrangements in the morphology of the thin films. Thus, it was observed that an increase of porosity and agglomeration of the crystallites is followed by an increase in the size of the crystallites. Inter-crystalline borders will migrate determining a coalescence of several crystallites during the heating process, as well. As a consequence, an increase of the band gap width from 3.26 eV to 3.30 eV (at 350 °C) and 3.32 eV (at 550 °C) respectively, occurred.     

The thermal treatment effects of CrN buffer layer on crystal quality of Zn-polar ZnO films

We report on the annealing effects of CrN buffer layers on the crystal quality of Zn-polar ZnO films grown by plasma assisted molecular beam epitaxy. The high-temperature (HT) annealing of CrN buffer layer improved the crystallinity of ZnO films. The full width at half maximums of (0002) and (10-11) ZnO ω-scan X-ray diffraction show 574 and 1296 arcsec, respectively, which show the 3 and 2 times narrower values than those of ZnO films without the annealing process. Moreover, the HT annealing can be effective method to improve the surface smoothness of ZnO film and reduce the crystal tilting.     

在p-Si(100)上溅射法生长ZnO的结构和光学特性

室温下在ｐ－Ｓｉ（１００）上采用直流反应磁控溅射法外延生长了ＺｎＯ薄膜。ＸＲＤ测量表明了ＺｎＯ是高度ｃ轴单一取向生长的,ＸＲＣ测量则表明了ＺｎＯ的高质量在室温下的ＰＬ测量中见到了带边发射,其强度与晶体质量有关。     

Nitrogen-doped p-type ZnO thin films and ZnO/ZnSe p-n heterojunctions grown on ZnSe substrate by radical beam gettering epitaxy

We investigate the p-type doping in ZnO prepared by the method of radical beam gettering epitaxy using NO gas as the oxygen source and nitrogen dopant. Secondary ion mass spectroscopy measurements demonstrate that N is incorporated into ZnO film in concentration of about 8 × 10¹⁸ cm^− 3. The hole concentration of the N-doped p-type ZnO films was between 1.4 × 10¹⁷ and 7.2 × 10¹⁷ cm^− 3, and the hole mobility was 0.9-1.2 cm²/Vs as demonstrated by Hall effect measurements. The emission peak of 3.312 eV is observed in the photoluminescence spectra at 4.2  of N-doped p-type ZnO films, probably neutral acceptor bound. The activation energy of the nitrogen acceptor was obtained by temperature-dependent Hall-effect measurement and equals about 145 meV. The p-n heterojunctions ZnO/ZnSe were grown on n-type ZnSe substrate and have a turn-on voltage of about 3.5 V.