掺AlZnO纳米线阵列的光致发光特性研究

采用化学气相沉积方法，以金做催化剂，在Si (100)衬底上制备了掺AlZnO纳米线阵列.扫描电子显微镜(SEM)表征发现ZnO纳米线的直径在30nm左右.X射线衍射(XRD)图谱上只存在ZnO的(002)衍射峰，说明ZnO纳米线沿c轴择优取向.掺AlZnO纳米线阵列的室温光致发光(PL)谱中出现了3个带边激子发射峰：373nm，375nm，389nm.运用激子理论推算出掺AlZnO纳米线的禁带宽度为3.343eV ，束缚激子结合能为0.156eV；纯ZnO纳米线阵列PL谱中3个带边激子发射 关键词： 光致发光 化学气相沉积(CVD) 激子 ZnO纳米线阵列     

水热合成ZnO:Cd纳米棒的微结构及光致发光特性

采用水热法制备了ZnO和不同掺杂浓度的ZnO:Cd纳米棒,通过SEM,XRD、拉曼光谱等的分析,研究了ZnO和ZnO:Cd的微结构并测试分析了其光致发光特性.结果表明,ZnO和ZnO:Cd纳米棒呈六角纤锌矿结构,Cd掺杂使得纳米棒体积更小.由于内部张应力的影响,Cd掺杂使得材料光学带隙减少.当掺杂浓度为2%时,合成的材料光致发光谱中出现了位于2.67 eV处,由导带底和Zn空位(VZn)缺陷能级跃迁造成的蓝光发射峰,并且Cd的掺入使得位于2.90 eV附近的紫光发射峰强度增强,对于研究ZnO蓝紫发光器件具有重要的意义.     

The structure and optical properties of SiC film on Si (111) substrate with a ZnO buffer layer by RF-magnetron sputtering technique

We have fabricated a multiply layer SiC/ZnO on Si substrates using the RF-magnetron sputtering technique with the targets of a single crystalline SiC and a polycrystalline ZnO. The as-deposited films were annealed in the temperature range of 600–1000 °C under nitrogen ambient. We have observed a strong ultraviolet (UV) emission (370 nm) from the as-deposited SiC/ZnO film and an intense violet emission (412 nm) from the film annealed at high temperature (1000 °C) under nitrogen ambient. The SiC film quality and the PL intensities are considered to be strongly dependent on the crystalline quality of the ZnO buffer layer. With the increase of the annealing temperature, the crystalline quality of the ZnO buffer layer is improved, resulting in the improvement of the SiC film quality and the increase of the PL intensities. The thin films have been characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) to provide the evidences of photoluminescence (PL). We suggest that the UV emission could be attributed to the nanocrystal silicon particles, that the 395 nm band is related to ZnO buffer layer and has a great relation to the crystalline quality of the ZnO film, and that the violet emission is associated with the emission luminescence from 6H-SiC, which bears on the SiC film quality. The obtained results are expected to have important applications in modern optoelectronic devices.     

衬底对原位氧化制备的ZnO薄膜结构和光学性质的影响

 采用射频反应溅射法在不同衬底上制备Zn₃N₂薄膜,然后对其原位氧化制备ZnO薄膜。利用X射线衍射分析(XRD)、扫描电子显微镜(SEM)和光致发光谱(PL)等表征技术研究了不同衬底对ZnO薄膜的结晶特性和发光性能的影响。XRD研究结果显示:Zn₃N₂薄膜在500 ℃原位氧化3 h后完全转变为ZnO薄膜,在玻璃和熔融石英衬底上制备的多晶ZnO薄膜无择优取向,而单晶硅（100）衬底上的多晶ZnO薄膜具有较好的沿（002）方向的择优取向。PL测试结果显示:硅和熔融石英衬底上的多晶ZnO薄膜发光性能良好,激子复合产生的紫外发光峰很强,且半高宽较窄,而来自于深能级发射的绿色发光峰很弱;而玻璃衬底上的多晶ZnO薄膜发光性能较差。     

Na-Mg共掺杂ZnO薄膜的结构和光学性质

利用溶胶-凝胶法,在普通载玻片上使用旋转涂膜技术制备了具有c轴择优取向生长的Na-Mg共掺杂的ZnO薄膜。用XRD、SEM、光致发光(PL)及透射光谱对薄膜样品进行了表征。结果表明:Na-Mg共掺杂有利于ZnO薄膜的c轴择优取向生长,并且随着Na+掺杂浓度的增加,晶粒尺寸先增大后减小;通过比较不同掺杂浓度ZnO薄膜的PL谱,推测发光峰值位于380nm的紫外发射与ZnO的自由激子复合有关;发现掺入Mg的确能使ZnO禁带宽度增大,掺杂组分为Na0.04Mg0.2Zn0.76O时,其PL谱只有一个很强的紫光发射峰,其近带边紫外光发射强度较未掺杂的ZnO增强了近10倍,极大地提高了薄膜紫外发光性能;并且随Na+浓度增加薄膜透光性减弱。     

Density functional investigation of structural, electronic and optical properties of Ge-doped ZnO

Recent experiments reported fascinating phenomenon of photoluminescence (PL) blueshift in Ge-doped ZnO. To understand it, we examined the structural, electronic and optical properties of Ge-doped ZnO (ZnO:Ge) systematically by means of density functional theory calculations. Our results show that Ge atoms tend to cluster in heavily doped ZnO. Ge clusters can limit the conductivity of doped ZnO but reinforce the near-band-edge emission. The substitutional Ge for Zn leads to Fermi level pinning in the conduction band, which indicates Ge-doped ZnO is of n-type conductivity character. It is found that the delocalized Ge 4s states hybridize with conduction band bottom, and is dominant in the region near the Fermi level, suggesting that Ge-4s states provides major free carriers in ZnO:Ge crystal. The observed blueshift of PL in Ge-doped ZnO originates from the electron transition energy from the valence band to the empty levels above Fermi level larger than the gap of undoped ZnO. The electron transition between the gap states induced by oxygen vacancy and conduction band minimum may be the origin of the new PL peak at 590 nm.     

Effects of high-dose Ge ion implantation and post-implantation annealing on ZnO thin films

This paper reports that ion implantation to a dose of 1×10¹⁷ ions/cm² was performed on c-axis-orientated ZnO thin films deposited on (0001) sapphire substrates by the sol-gel technique. After ion implantation, the as-implanted ZnO films were annealed in argon ambient at different temperatures from 600-900℃. The effects of ion implantation and post-implantation annealing on the structural and optical properties of the ZnO films were investigated by x-ray diffraction (XRD), photoluminescence (PL). It was found that the intensities of (002) peak and near band edge (NBE) exitonic ultraviolet emission increased with increasing annealing temperature from 600-900℃. The defect related deep level emission (DLE) firstly increased with increasing annealing temperature from 600- 750℃, and then decreased quickly with increasing annealing temperature. The recovery of the intensities of NBE and DLE occurs at \sim 850℃ and \sim 750℃ respectively. The relative PL intensity ratio of NBE to DLE showed that the quality of ZnO films increased continuously with increasing annealing temperature from 600 - 900℃.     

纳米ZnO薄膜可见发射机制研究

利用溶胶－凝胶法 （Sol-Gel）制备了纳米ZnO薄膜，获得了高强的近紫外发射室温下测量了样品的光致发光谱(PL )、吸收谱(ABS)、X射线衍射谱(XRD).X射线衍射(XRD)的结果表明：纳米ZnO薄膜呈多晶态，具有六角纤锌矿结构和良好的C轴取向；发现随退火温度升高，（002）衍射峰强度显著增强，衍射峰的半高宽（FWHM）减小、纳米颗粒的粒径增大.由吸收谱(ABS)给出了样品室温下带隙宽度为3.30 eV.在PL谱中观察到二个荧光发射带，一个是中心波长位于392 nm附近强而尖的紫带，另一个是519 nm附近弱而宽的绿带研究了不同退火温度样品的光致发光峰值强度的变化关系，发现随退火温度升高，紫带峰值强度增强、绿带峰值强度减弱，均近似呈线性变化.证实了纳米ZnO薄膜绿光发射主要来自氧空位(Vo)形成的浅施主能级与锌空位(VZn)形成的浅受主能级之间的复合，或氧空位(Vo)形成的深施主能级上的电子至价带顶的跃迁；紫带来自于导带中的电子与价带中的空位形成的激子复合.     

Effect of Mn doping on the structural and optical properties of sol-gel derived ZnO nanoparticles

Un-doped and Mn-doped ZnO nanoparticles were successfully synthesized in an ethanolic solution by using a sol-gel method. Material properties of the samples dependence on preparation conditions and Mn concentrations were investigated while other parameters were controlled to ensure reproducibility. It was observed that the structural properties, particle size, band gap, photoluminescence intensity and wavelength of maximum intensity were influenced by the amount of Mn ions present in the precursor. The XRD spectra for ZnO nanoparticles show the entire peaks corresponding to the various planes of wurtzite ZnO, indicating a single phase. The diffraction peaks of doped samples are slightly shifted to lower angles with an increase in the Mn ion concentration, signifying the expansion of the lattice constants and increase in the band gap of ZnO. All the samples show the absorption in the visible region. The absorbance spectra show that the excitonic absorption peak shifts towards the lower wavelength side with the Mn-doped ZnO nanoparticles. The PL spectra of undoped ZnO consist of UV emission at 388 nm and broad visible emission at 560 nm with varying relative peak intensities. The doping of ZnO with Mn quenches significantly the green emission while UV luminescence is slightly affected.     

Optical and electrical properties of undoped and (Mn, Co) co-doped ZnO nanoparticles synthesized by DC thermal plasma method

The undoped and (Mn, Co) co-doped ZnO nanopowders were synthesized through DC thermal plasma method. The pellets of this powder were annealed at 450, 550 and 650 °C for 1 h. Structural, chemical and optical properties of the samples were studied by XRD, SEM, EDX, UV–Vis and PL analysis. XRD spectra showed that all the samples were hexagonal wurtzite structure and as the annealing temperature increases the material becomes purer and more crystalline. It is seen that the optical band gap decreases when the ZnO is doped with manganese and cobalt. Photoluminescence intensity varies with doping because of the increment of oxygen vacancies. DC conductivity studies of the pellets were carried out at different temperatures (25–100 °C) and it was found that the activation energy for the electrical transport is high for (Mn, Co) co-doped ZnO than undoped ZnO.     

Structural and optical properties of Au-implanted ZnO films

The structural and luminescence related optical behaviours of Au ion implanted ZnO films grown by magnetic sputtering and their post implantation annealing behaviours in the temperature range of 100-700 °C have been investigated. Optical absorption and transmittance spectra of the films indicate that band edge of Au-implanted ZnO has shifted to high energy range and optical band gap has increased, because the sharp difference of thermal expansion induces the lattice mismatch between ZnO and SiO₂. PL spectra reveal that UV and visible luminescence bands of ZnO films can be improved after thermal annealing due to recovery of defects and Au ions incorporation. Importantly, green luminescence band of 530 nm has been only observed in the Au-implanted and subsequently annealed ZnO films and it enhances with the increasing annealing temperature, which can be related to Au atoms or clusters in ZnO films. Furthermore, X-ray photoelectron spectroscopy measurements reveal that the Au⁰ is dominant state in Au implanted and annealed ZnO films. Possible mechanisms, such as optical transitions of Au atoms or clusters and deep level luminescence of ZnO, have been proposed for green emission.     

Growth of epitaxial c ‐plane ZnO film on a ‐plane sapphire by radio frequency reactive magnetron sputtering

In this Letter, we report the successful growth of high quality c ‐plane oriented epitaxial ZnO films on a ‐plane sapphire substrates by using radio frequency reactive magnetron sputtering. The effect of substrate temperature on the structural and optical properties has been investigated. X‐ray diffraction (XRD) studies reveal that the ZnO film is grown epitaxially on a ‐plane sapphire substrate, and the film quality is improv‐ ed as the substrate temperature is increased. Photoluminescence (PL) results manifest that screw dislocations can exert great influence on the optical properties. It is found that the line width of the near‐band‐edge emission of PL decreases linearly with increase in screw density. In addition, a simple and effective method is proposed to assess the defect density in epitaxial ZnO films by performing PL measurement. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

高分子网络凝胶法制备ZnO超细粉体及其光学性能

采用高分子网络凝胶法制备球形ZnO超细粉体。通过聚乙烯醇(PVA)亚浓溶液交联网络的空间位阻作用,经过烧结,获得了具有球形形貌的粒径为1~3μm的ZnO粉体颗粒。利用X射线衍射(XRD)、扫描电镜(SEM)分析了不同PVA浓度以及退火温度对产物形貌、结构的影响,发现在PVA溶液浓度为5%,并且经500℃热处理所形成的ZnO球形颗粒最为均匀规整。研究了球形ZnO粉体的光致发光性能,室温下经325nm波长激发,观察到两个中心波长分别位于407,468nm的微弱的荧光发射带,在合适温度下,在385nm处还出现了较强的紫外峰。PL光谱表明,退火温度对ZnO的光致发光影响较大,随着退火温度升高,由于表面缺陷和结晶性能发生变化,407nm处发射峰逐渐减弱消失,而紫外发光先增强后减弱,经500℃热处理样品的紫外发光性能达到最佳。     

Influence of buffer layer thickness on the structure and optical properties of ZnO thin films

A series of ZnO thin films were deposited on ZnO buffer layers by DC reactive magnetron sputtering. The buffer layer thickness determination of microstructure and optical properties of ZnO films was investigated by X-ray diffraction (XRD), photoluminescence (PL), optical transmittance and absorption measurements. XRD results revealed that the stress of ZnO thin films varied with the buffer layer thickness. With the increase of buffer layer thickness, the band gap edge shifted toward longer wavelength. The near-band-edge (NBE) emission intensity of ZnO films deposited on ZnO buffer layer also varied with the increase of thickness due to the spatial confinement increasing the Coulomb interaction between electrons and holes. The PL measurement showed that the optimum thickness of the ZnO buffer layer was around 12 nm.     

Ti缓冲层及退火处理对Si(111)基片上生长的ZnO薄膜结构和发光特性的影响

采用反应磁控溅射法在Si（111）基片上制备了带有Ti缓冲层的高c轴取向ZnO薄膜.通过X射线衍射分析和光致荧光光谱测量,研究了Ti缓冲层厚度和退火处理对ZnO薄膜结晶质量和光致荧光特性的影响.研究结果表明,Ti缓冲层的引入可以有效改善Si基片上ZnO薄膜的发光性能,但缓冲层存在一个最佳的厚度.薄膜应力是影响ZnO薄膜紫外荧光发射性能的重要因素,较小的残余应力对ZnO薄膜的紫外荧光发射是有利的,残余应力的存在可以改变ZnO薄膜紫外荧光发射能量.随着退火温度的增加,薄膜中的张应力增大,导致带隙宽度减小以及激子复合跃迁峰逐渐向低能方向移动. 关键词： ZnO薄膜 缓冲层 退火处理 应力分析     

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.     

ZnO薄膜的制备和发光特性的研究

用射频磁控溅射的方法在石英衬底上沉积了氧化锌薄膜，在室温下测量了样品的XRD曲线、吸收光谱以及光致发光光谱。探讨了气氛中氧气与氩气比对制备薄膜的影响，从XRD谱中可以看出，样品具有较好的结晶状态。另外，样品在紫外有较强的吸收，而其光致发光也是较强的紫外发射，这表明带间跃迁占了主导地位，以上结果说明：用溅射方法制备的ZnO薄膜结晶质量较好，富锌状态有所改善。     

Ultrasonic induced photoluminescence decay in sonochemically obtained cauliflower-like ZnO nanostructures with surface 1D nanoarrays

Cauliflower-like ZnO nanostructures with average crystallite size of about 55 nm which have surface one dimensional (1D) nanoarrays with 10 nm diameter were successfully fabricated through a simple sonochemical route. X-ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and room temperature photoluminescence (PL) characterizations were performed to investigate the morphological and structural properties of the obtained nanostructures. It has been shown that the synthesized cauliflower-like ZnO nanostructures irradiated UV luminescence and a green peak in visible band. Ultrasonic post-treatment of the particles for about 2 h increased the density of surface defects resulted in an increase in the green emission intensity.     

A study on morphology control and optical properties of ZnO nanorods synthesized by microwave heating

In this study, we present morphology control investigations on zinc oxide (ZnO) nanorods synthesized by microwave heating of a mixture of zinc nitrate hexahydrate and hexamethylenetetramine (HMTA) precursors in deionized water (DI water). To study the morphology and structural variations of the obtained ZnO nanorods in different molar ratio of zinc nitrate hexahydrate to HMTA, X-ray diffraction (XRD), scanning electron microscopy (SEM) images, Raman scattering, and photoluminescence (PL) spectroscopy were measured. XRD and SEM images are utilized to examine the crystalline quality as well as the morphological properties of the ZnO nanorods. It is found that morphology control can be achieved by simply adjusting the reactant concentrations and the molar ratio of zinc nitrate hexahydrate to HMTA. Raman scattering and PL spectroscopy measurements were demonstrated to study the size- and shape-dependent optical response of the ZnO nanorods. The Raman scattering result shows that the intensity of LO mode at around 576 cm^?1 decreases with the increase in the molar ratio of zinc nitrate hexahydrate to HMTA, indicating the reduction of defect concentrations in the synthesized ZnO nanorods. Room temperature PL spectrum of the synthesized ZnO nanorods reveals an ultraviolet (UV) emission peak and a broad visible emission. An enhancement of UV emission appears in the PL spectra as the molar ratio of zinc nitrate hexahydrate to HMTA increases, indicating that the defect concentration of the synthesized ZnO nanorods can be reduced by increasing the molar ratio.     

Temperature dependence of the optical band gap and electrical conductivity of sol-gel derived undoped and Li-doped ZnO films

Undoped and lithium (Li)-doped ZnO films were prepared by sol-gel method using spin coating technique. The effects of Li content on the crystallinity and morphological properties of ZnO films were assessed by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM). XRD patterns of the films showed the hexagonal wurtzite type polycrystalline structure and that the incorporation of lithium leads to substantial changes in the structural characteristics of ZnO films. The SEM and AFM measurements showed that the surface morphology of the films was affected from the lithium incorporation. The wrinkle network was observed on the surface from both SEM and AFM results for undoped ZnO. The wrinkle structure disappeared with increasing Li content. The absorption spectra of the ZnO and 5% Li-doped ZnO (LZO5) films were carried out between 140 and 400 K temperatures. The optical band gap of ZnO and LZO5 films (calculated at various temperatures) showed a linear dependence on the temperature. The absolute zero value optical band gap and the rate of change of the band gap with temperature of the ZnO and LZO5 films were found to be 3.339 and 3.322 eV, and 2.95 × 10⁻⁴ and 1.60 × 10⁻⁴ eV/K, respectively. The transport mechanisms in the ZnO and LZO5 films have been investigated by analyzing of the temperature (80-300 K) dependence of the conductivity. The activation energies of the ZnO film increased with Li content.