Processing temperature dependent morphological and optical properties of ZnO nanorods

Zinc Oxide (ZnO) nanorods were synthesized by thermal decomposition of zinc acetate dihydrate at various processing temperatures. The morphology of samples, examined using transmission electron microscopy and field emission scanning electron microscopy, revealed large variations in length and diameter of nanorods. As temperature was increased from 300 °C to 450 °C, ZnO nanocrystal morphology changed from wire-like to rod-like. This morphology change is a result of competition between nucleation and growth rate in the vapor–solid growth mechanism of nanorods. Photoluminescence spectrum of the nanorods showed both band edge emission as well as native defect related visible emission. Relative intensity of UV and visible emission indicated crystal quality of the nanorods, the ratio increased upto 400 °C and deteriorated at higher processing temperature. It is argued that process induced defects dominate at processing temperatures ≤400 °C, whereas equilibrium concentration of native defects is high at temperatures >400 °C.     

Effect of Ni-doping concentration on structural,optical and magnetic properties of CdSe nanorods

Cd_1−xNi_xSe (x=0.00, 0.05, 0.10 and 0.15) nanorods have been synthesized using solvothermal route. X-ray diffraction (XRD) studies show that the nanorods possess wurtzite phase having hexagonal structure. Transmission electron microscopy (TEM) reveals the formation of nanorods having lengths 150–200 nm and diameters 10–15 nm. This has been further confirmed by high-resolution transmission electron microscopy (HRTEM) wherein lattice fringes corresponding to CdSe have been well observed. Reflectance measurements illustrate the red-shift in band gap with increase of Ni-doping concentration. Raman spectra display the shifting of longitudinal optical (LO) phonon modes, and modes activation due to doping in CdSe nanorods. Magnetic hysteresis (M–H) loops at room temperature reveal the ferromagnetism in nanorods. The saturation magnetization values have been observed to increase upto 10% due to carrier mediated exchange interactions, whereas a decrease has been observed for 15% Ni-doping concentration due to super-exchange interactions.     

溶液浓度对ZnO纳米棒形貌和发光的影响

为了获取高质量、高取向排列规则的ZnO纳米棒,玻璃衬底预先用脉冲激光沉积方法制备一层ZnO薄膜作为籽晶层,应用水热法在玻璃衬底上生长ZnO纳米棒。探究了籽晶层及不同溶液浓度对ZnO纳米棒结构和发光的影响,用扫描电子显微镜和X射线衍射仪测量样品的形貌和结构,用组建的光致发光测试系统对样品的室温光致发光光谱进行测定。结果表明,ZnO纳米棒具有高度取向且分布致密均匀;光致发光光谱显示ZnO的近带边发射比深能级发光略低;随着溶液浓度的增加,近带边发光和深能级发光相对强度的比值依次降低。     

掺杂浓度对Co掺杂ZnO纳米棒的铁磁性的影响

采用化学气相沉积(CVD)方法制备出3种掺杂浓度的Co掺杂ZnO纳米棒。使用EDX(en-ergy dispersive X-ray)能谱,测得3种ZnO纳米棒中Co元素的掺杂浓度分别为0.4、1.4和2.4%。X射线衍射(XRD)分析表明,三个样品均为ZnO的六方铅锌矿结构,并沿着c轴取向择优生长。磁化曲线显示,掺杂浓度为0.4%的Co掺杂ZnO纳米棒为顺磁性,随着掺杂浓度的增大,Co掺杂ZnO纳米棒转变为铁磁性。扩展X射线吸收精细结构谱表明,Co掺杂ZnO纳米棒的铁磁性源于ZnO纳米棒中的Co金属团簇。     

Effect of hydrogenation on the cathodoluminescence properties of ZnO single crystals

The effect of hydrogenation on the intensity evolution of ZnO single crystal under electron beam irradiation was investigated by cathodoluminescence (CL). Without hydrogenation, the ultraviolet (UV) emission for O-face decreases exponentially and reaches a constant value with e-beam irradiation, while that for Zn-face once increases and then decreases. The hydrogenation significantly increases the UV emission for both faces. On the other hand, the amplitude of the decreasing component of the O-face becomes larger, while the increasing component is not affected. These results suggest that hydrogen only affects the decreasing component of the UV intensity evolution.     

ZnO纳米线的快速生长机理及其场发射性能研究

为了快速制备具有优良场发射性能的ZnO纳米线,对ZnO纳米线的生长机理及场发射性能进行研究。首先采用优化的两步法制备出高长径比的ZnO纳米线,其次采用SEM对ZnO的微观形貌进行表征,然后,在分析形貌特点的基础上,说明了强碱体系下ZnO纳米线薄膜的快速生长机理。最后,对典型样品的场发射性能进行了测试。测试果表明,优化后的两步法,只需3h即可获得直径为40~50nm,长度为2.2~2.7μm,长径比高达54的纳米线。薄膜的开启电场为3.6V/μm,阈值场强为9.1V/um,场增强因子β高达3 391。研究表明,高pH值溶液可以加快ZnO纳米线沿C轴方向的择优生长,获得高长径比的ZnO纳米线,进而获得优良的场发射性能。     

AZO种子层朝向对ZnO纳米棒形貌和发光特性的影响

在水平管式炉中,采用热蒸发锌粉的方法,在镀有掺铝氧化锌(AZO)薄膜的石英基片上制备了大量高密度的ZnO纳米棒,AZO膜面分别正对和背对锌源。利用扫描电子显微镜、X射线衍射仪以及荧光光谱仪分析AZO膜面朝向对ZnO纳米棒的形貌、微结构及光学性能的影响。结果表明,不同朝向的AZO膜面上所生长的纳米棒具有相似的形貌和微结构。保温时间10min样品的氧空位的缺陷态发光为绿光,强度较强;保温时间15min样品的纳米棒长度较长、相对垂直衬底,其近带边发光较强,氧间隙的缺陷态发光较弱。正对锌源衬底上且保温时间15min样品的近带边发光最强,且缺陷态发光最弱。     

Influence of growth time on crystalline structure, conductivity and optical properties of ZnO thin films

This paper examines the growth of ZnO thin films on glass substrate at 350 ℃ using an ultrasonic spray technique. We have investigated the influence of growth time ranging from 1 to 4 min on structural, optical and electrical properties of ZnO thin films. The as-grown films exhibit a hexagonal structure wurtzite and are (002) oriented. The maximum value of grain size G = 63.99 nm is attained for ZnO films grown at 2 min. The average transmittance is about 80%, thus the films are transparent in the visible region. The optical gap energy is found to increase from 3.26 to 3.37 eV with growth time increased from 1 to 2 min. The minimum value of electrical resistivity of the films is 0.13 Ω·cm obtained at 2 min. A systematic study on the influence of growth time on the properties of ZnO thin films deposited by ultrasonic spray at 350 ℃ has been reported.     

生长时间对氧化锌纳米棒发光性能的影响

为了研究氧化锌纳米棒的生长机理,先用脉冲激光沉积方法在玻璃衬底上制备一层氧化锌薄膜作为种子层,然后用水热法在种子层上生长氧化锌纳米棒,研究了不同反应时间对其结构、形貌及发光特性的影响。利用X射线衍射仪和扫描电子显微镜测定样品的结构和形貌,用自组建的光致发光系统对样品的光致发光光谱进行了测量。结果表明,氧化锌纳米棒沿c轴高度取向并呈六角纤锌矿结构;随着生长时间的增加,氧化锌纳米棒结晶质量明显改善,纳米棒均匀、致密性和取向性均提高,样品的缺陷发光增强而激子发光减弱。     

Nb_2O_5掺杂量对ZnO压敏电阻器性能的影响

通过掺杂微量Nb2O5制备了ZnO压敏电阻器,运用扫描电子显微镜(SEM)和电性能测试手段分析了Nb2O5掺杂对ZnO压敏电阻器微观结构和电性能的影响,测量了晶界势垒高度φH,并探讨了其对ZnO压敏电阻器性能的影响。结果表明:掺杂适量的Nb2O5可以明显改善ZnO压敏电阻器的微观结构和电性能;当Nb2O5的掺杂量为摩尔分数0.10%时,所制ZnO压敏电阻器的晶粒尺寸最大,且压敏电压V1mA、非线性系数α和φH值分别为174V,30和0.463 eV。     

The effect of growth conditions,point defects and hydrogen on the electronic structure and properties of p-type (Al,N) codoped ZnO: A first principles study

The effects of point defects, hydrogen, and growth conditions on the electronic structure and properties of the (Al,N) codoped p-type ZnO have been investigated using the first principles method. The obtained results showed that the Al_Zn–N_O–V_Zn complex is a shallow acceptor that can play an important role in achieving the p-type conductivity in the (Al,N) codoped ZnO films. Our results showed also that the electrical conductivity type in the (Al,N) codoped ZnO films strongly depends on the donor/acceptor concentrations ratio. The codoped ZnO films prepared under both Zn-rich and O-rich growth conditions with a donors/acceptors ratio of 1:2 have a p-type conductivity, while those prepared with a ratio of 1:1 cannot be p-type unless if they are prepared under O-rich conditions. The achieved p-type quality depends also on the used nitrogen doping source. To prepare p-type ZnO film of high quality using the (Al,N) codoping method, the use of NO or NO₂ is recommended. The presence of donor defects such as oxygen vacancies and hydrogen will significantly affect the electronic properties of the (Al,N) codoped ZnO films, and if the concentration of these defects in the sample is high enough, the material can be easily converted to n-type.     

Microstructural and photoluminescence properties of Co-doped ZnO films fabricated using a simple solution growth method

Nanocrystalline 2% cobalt doped ZnO films were successfully prepared using a simple chemical solution method on glass substrates and subsequently annealed in air at 300 and 500 °C. Structural, morphology, chemical composition and photoluminescence properties of the films were characterized using X-ray diffractometry (XRD), scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS) and Fourier transform infra-red spectroscopy (FTIR) and photoluminescence (PL) spectroscopy. X-ray diffraction studies of the annealed films reveal the formation of polycrystalline hexagonal wurtzite structure of ZnO crystals without any co-related secondary phases. SEM micrographs of the films show the formation of spherical nanoparticles. Photoluminescence of the films showed a weak UV and defect related visible emissions like blue, blue–green, yellow and relatively intense orange–red emissions and their mechanism was discussed in detail.     

Effect of seed layers (Al,Ti) on optical and morphology of Fe-doped ZnO thin film nanowires grown on Si substrate via electron beam evaporation

The effects of Al and Ti seed layers were studied for undoped and Fe-doped ZnO thin films deposited on n-type Si substrates by electron beam (e-beam) evaporation. The films were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). The films grown on seed layers showed wurtzite hexagonal crystal nanorod and nanowire structures. A higher angle phase shift was observed in the doped thin films compared to the pristine ZnO films. Microstructural studies confirmed the growth of nanorods and nanowires with average widths of ~32 nm and ~8–29 nm, respectively. The nanostructures were denser and more crystalline on the Al seed layer than on the Ti seed layer for the doped thin films. However, in the undoped thin films, a more crystalline nature was observed on the Ti seeded layer than the Al seeded layer.     

Ultra-violet photo-response characteristics of p-Si/i-SiO2/n-ZnO heterojunctions based on hydrothermal ZnO nanorods

Hydrothermal zinc oxide (ZnO) nanorod (NR)-based p-Si/n-ZnO and p-Si/i-SiO₂/n-ZnO heterojunctions were fabricated, and the effects of interfacial native SiO₂ (~4 nm) on the I-V characteristics of heterojunctions under dark and ultra-violet illumination conditions were investigated. First, the structural and optical properties of ZnO seed crystals grown by sol-gel method and hydrothermal ZnO NRs on two different substrates of p-Si and p-Si/i-SiO₂ were examined, and more improved optical and crystalline quality was obtained as revealed by photoluminescence and X-ray diffraction. The p-i-n heterojunctions showed ~3 times greater forward-bias currents and enhanced rectifying property than those of p-n junctions, which is attributed to the role of native SiO₂ in carrier confinement by promoting the electron-hole recombination current through the deep level states of ZnO crystal. The measured ratios of photocurrent to dark current of the p-i-n structure were also greater under reverse bias (92–260) and forward bias (2.3–7.1) conditions than those (28–225 for reverse bias, 1.6–6.8 for forward bias) of p-n structure, and the improved photosensitivity of the p-i-n structure under reverse bias is due to lower density of recombination centers in the ZnO NR crystals. Fabricated ZnO NR heterojunction showed repeatable and fast photo-response transients under forward bias condition of which response and recovery times were 7.2 and 3.5 s for p-i-n and 4.3 and 1.7 s for p-n structures, respectively.     

Co、Mn的掺杂形式对低压氧化锌压敏陶瓷电性能的影响

研究了Co、Mn的不同掺杂形式对低压ZnO压敏电阻显微结构和电性能的影响。发现以Co(NO3 ) 2 、Mn (NO3 ) 2 溶液代替CoO、MnO2 掺杂 ,可以降低压敏电压 ,增大非线性系数。这主要与钴的高价态有关 ,利于压敏电阻的低压化。     

MBE growth and properties of ZnO on sapphire and SiC substrates

Molecular beam epitaxy (MBE) of ZnO on both sapphire and SiC substrates has been demonstrated. ZnO was used as a buffer layer for the epitaxial growth of GaN. ZnO is a würtzite crystal with a close lattice match (<2% mismatch) to GaN, an energy gap of 3.3 eV at room temperature, a low predicted conduction band offset to both GaN and SiC, and high electron conductivity. ZnO is relatively soft compared to the nitride semiconductors and is expected to act as a compliant buffer layer. Inductively coupled radio frequency plasma sources were used to generate active beams of nitrogen and oxygen for MBE growth. Characterization of the oxygen plasma by optical emission spectroscopy clearly indicated significant dissociation of O₂ into atomic oxygen. Reflected high energy electron diffraction (RHEED) of the ZnO growth surface showed a two-dimensional growth. ZnO layers had n-type carrier concentration of 9 × 10¹⁸ cm⁻³ with an electron mobility of 260 cm²/V-s. Initial I-V measurements displayed ohmic behavior across the SiC/ZnO and the ZnO/GaN heterointerfaces. RHEED of GaN growth by MBE on the ZnO buffer layers also exhibited a two-dimensional growth. We have demonstrated the viability of using ZnO as a buffer layer for the MBE growth of GaN.     

Selective growth and directed integration of ZnO nanobridge devices on si substrates without a metal catalyst using a ZnO seed layer

Directed assembly and integration of ZnO nanobridges (NBs) into working devices on Si substrates was achieved. Metal catalysts were not used, and the “harvest and disperse” method of nanorod (NR) integration was avoided. High-quality ZnO NRs were grown via a vapor-solid method selectively on a patterned thin-film ZnO seed layer. ZnO NRs exhibited a single-crystalline structure with c-axis preferred orientation, were aligned roughly perpendicular to the surface, and showed a strong intrinsic near-band edge photoluminescence peak at 380 nm with no detectable visible photoluminescence. These ZnO NRs were grown to span gaps between separated electrodes, terminate on an opposing surface, and effectively form electrically accessible vertical or horizontal ZnO NB devices. Operation of the directly grown horizontal ZnO NB devices as gas and UV sensors was performed, demonstrating a significant step toward practical large-scale integration of nanodevices into Si microelectronics.     

Synthesis and characterization of cerium oxide nano-particles in chloride bath: Effect of the H2O2 concentration and bath temperature on morphology

Cerium oxide has been used extensively for various applications over the past two decades. The use of cerium oxide nanoparticles is beneficial in present applications and can open new avenues for future uses. In this paper, some samples of cerium hydroxide/oxide have been synthesized by cathodic deposition on steel electrode in chloride bath in two electrode systems by the galvanostatic mode. The effects of bath temperature and H₂O₂ concentration on particle size and morphology were studied. The effect of calcination temperature on the crystallite growth of cerium oxide nano-powders was investigated by X-ray diffraction. The results were characterized by the differential scanning calorimetry (DSC), thermogramimetric analysis (TGA), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The SEM results show that the samples synthesized at low bath temperature have an average size of 40 nm. In the presence of H₂O₂, the cerium oxide films are adherent and smooth. They present very thin cracks whereas with the increase of H₂O₂ concentration the size and number of cracks are reduced. The results show that the as-prepared nanoparticles are essentially amorphous and after heat treatment, the obtained oxide product is well crystallized.     

Influence of N2 introduction on structural and optical properties of V-doped ZnO thin films grown by low-temperature reactive RF magnetron sputtering

The influences of N₂ introduction to a sputtering gas on structural and optical properties of vanadium-doped ZnO (VZO) films, grown by using reactive RF magnetron sputtering on a quartz substrate at room temperature, were investigated. In the VZO films, V doping caused to form a large number of O vacancies (V_O) and degraded both the c-axis orientation and optical transmittance. While, on the contrary, the ZnO(002) diffraction intensity of 3.5-at.% VZO films increased adding N₂ with a partial pressure ratio (α_N2) >2% reaching a maximum at α_N2 =5%. The average optical transmittance (wavelengths: 450−800 nm) of the 3.5-at.% VZO films was also improved by the N₂ introduction and reached 74% at α_N2 =5%. As a result of the analyses of the chemical binding states of the incorporated N atoms via the Raman spectroscopy and XPS, it was confirmed that the O sites were substituted by the N atoms and the amount of incorporated N increased by the high V doping. From the above, the N₂ introduction was effective to suppress the V_O formation even in room-temperature-grown VZO films, so it enables to improve both the c-axis orientation and optical transmittance.     

衬底退火温度对ZnO纳米结构形貌和发光特性的影响

利用热蒸发Zn粉的方法,在Au/掺铝氧化锌(AZO) /石英衬底上生长ZnO纳米结构。为了研究不同 温度退火后的衬底对生长的ZnO纳米结构的影响,Au/AZO/石英衬底在生长纳米结构前分别在 300、500和700℃真空下退火。Au/AZO/石英衬底的表面形貌用原子力显微镜(AFM)观测 。ZnO纳米结构的微结构、形貌和 光学性能分别用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和荧光光 谱仪进行测量。结果表明,在未退火和300 ℃ 退火衬底上生长了大量的ZnO纳米棒,而在500℃退火衬底上沉积了大量ZnO纳米颗粒。单晶结构 的纳米棒的平均直径分别约50nm,其 生长机制为蒸气-液体-固体(VLS)生长机制。荧光光谱显示所有的样品 都存在紫外发光峰和深能级发射带,随着退火温度的升高,生长的纳米结构的紫外发光峰相 对强度增强,而深能级发射强度减弱。